Upload
others
View
1
Download
0
Embed Size (px)
Citation preview
Research ArticleAnomalous Fluctuation of Halogens in Relation to the PollutionStatus along Lake Mariout Egypt
Ghada F El-Said Gehan M El Zokm Abeer A El Sayed Ahmed A El Ashmawy and Mohamed A Shreadah
National Institute of Oceanography amp Fisheries NIOF Cairo Egypt
Correspondence should be addressed to Gehan M El Zokm gehanelzokmyahoocom
Received 23 May 2020 Revised 19 October 2020 Accepted 8 December 2020 Published 30 December 2020
Academic Editor Mohamed Azaroual
Copyright copy 2020 Ghada F El-Said et al -is is an open access article distributed under the Creative Commons AttributionLicense which permits unrestricted use distribution and reproduction in any medium provided the original work isproperly cited
-is paper aimed to study the anomalous fluctuation of halogens with respect to the pollution status in surface water (w) porewater (p) and sediments (s) of Lake Mariout It provided a framework for understanding the distribution of dissolved andprecipitated halogen salts related to the pollution status of the lake -e study cleared out that bromide was only the mostabundant halogen in the three studied partitions On contrast sedimentrsquos partition contained the lowest chloride contentFluoride minerals especially fluorapatites and carbonate-fluorapatite (FAP and CFAP) had high Saturation Index (SI) values insurface water (4277ndash5195 and 1604ndash6089 respectively) and in pore water (5126ndash5460 and 1752ndash7833 respectively) Bromideand chloride were mainly found in the soluble forms in the surface water and pore waters Iodide salts (Ca(IO3)2 andCa(IO3)26H2O) were moderately precipitated in surface and pore waters -us SI content reflected that halogens especiallyfluoride and iodide played a vital role in reducing lake pollution Fluorite (CaF2) and sellaıte (MgF2) could only be formed in porewater while calcite and aragonite could be deposited from surface water In addition Cl was mainly found in the forms of NaClCaCl2 MgCl2 and KCl in surface and pore waters -e multivariate analysis revealed that fluoride precipitate may serve indecreasing the dissolved salt pollution Multivariate analysis showed that in the long run the fluoride precipitation in FAP andCFAP can significantly adsorb and absorb various pollutants and can protect the lake from pollution -e ecological risk as-sessment conducted by calculating the enrichment factor (EF) showed that the lake was still unpolluted Regarding human healthrisks at appropriate levels of human health and safety the hazard quotient (HQ) and hazard index (HI) of halogens found to belower than these reported levels Hence ingestion and dermal absorption routes of halogens by surface water and sediments didnot pose any adverse effects to population reflecting uncontaminated status of Lake Mariout
1 Introduction
-e water ecosystem in Egypt is rapidly deteriorating due tothe increased discharge of heavily polluted domestic sewageagricultural runoff and industrial wastewater generated byhuman activities [1ndash10] Egyptian lakes are currently de-graded by natural and human activities such as degradationhabitat loss pollution as they receive great amounts of in-dustrial municipal and agricultural wastewater withouttreatment and the spread of aquatic plants [11ndash16] Al-though Lake Mariout has recently received governmentattention there is still an urgent need for an action plan forsustainable development
Lake Mariout is recognized as the main part of the oldLake Mareotis [17] It extends from 2983degndash2998deg E to3105degndash3117deg N with a surface area of approximately 60 km2
and a shallow depth of approximately 15m (Figure 1) Itslocation is about 20 km away from the Mediterranean Sea atthe southern part of Alexandria City It is directly discon-nected from theMediterranean Sea along El-Mex Bay becauseit is located 28m below sea level -e El-Mex pumpingstation pours large amounts of lake water into the Medi-terranean Sea through the bay [17] In the past few years LakeMariout has been heavily affected by various human activitieswhich usually reduce its specific area However over the lasteighty years its area decreased drastically from 248 to
HindawiJournal of ChemistryVolume 2020 Article ID 8102081 20 pageshttpsdoiorg10115520208102081
6302 km2 due to the land reclamation and the constructionof a series of roads in addition to drainage and navigationcanals that divided the lake into basins-ese roads and canalshave become a physical barrier that prevented the trans-portation of lake water fish and fishermen from a basin toanother [17] Unfortunately the lake receives large amountsof untreated urban municipal industrial wastewater efflu-ents drainage water and domestic wastewater from differentdrains such as El Umoum drain which directly dischargesindustrial effluents from different companies such as the Petrojet Company El-Amreya Petroleum Company and El-Amreya Company of spinning and weaving besides theEgyptian Petrochemical Company in addition to domesticand agricultural wastewater into the lake -e El-Qalaadrainage channel discharges 676000m3 dayminus1 of primarytreatment municipal sewage and agricultural wastewaterevery day the El Nubaria Canal discharges industrial agri-cultural and household waste [18] In addition some builtroads had divided the lake into four separate basins and eacharea of the physical features and these basins are as followsthe Main Basin the South West Basin the North West Basinand the Fishery Basin with areas of 252 210 126 and42 km2 respectively [18 19] -ese basins affect the watercycle in the lake so their role is to minimize the negativeimpact on lake water quality Due to the economic impor-tance of Lake Mariout officials active civil society the publicand international development organizations are facing manychallenges of sustainable development and environmentalimprovement-ey all share a common interest in developinga set of indicators that play an important role in guiding theplanning of this precious ecosystem and overcoming thevulnerability of human health to waste
Halogens mainly concentrate in the earthrsquos surfacereservoirs including seawater and sediments -e halogenelements show great resemblances to one another in theirgeneral chemical behavior and in the properties of theircompounds with other elements -ey carry out significantroles in the global transformation processes [20] In addi-tion halogens naturally exist in the form of monovalentanions metal-bound salts silicate minerals and nonsilicateminerals [20] Amongst the other halogens chloride (Cl)exhibits systematically different behavior due to its ionic sizeor its elemental abundance Fluorine is strongly electro-negative being the only element in the periodic table that ismore electronegative than oxygen Fluorides (such asfluorite cryolite and fluorapatite) traditionally combine themost naturally distributed minerals and usually have manyeconomic uses [21] -erefore it enters the social envi-ronment through alternative methods (gradual erosion andweathering process) and industry (locally produced phos-phate fertilizers semiconductors aluminum special drugscosmetics etc) [22] Fluoride has been recorded an ab-normal concentration in the seawater along the Mediter-ranean coast of Egypt In addition to the large amount ofminerals that may be dissolved in the sediment-water in-terface the Mediterranean coast of Egypt is also adverselyaffected by raw sewage domestic agricultural and industrialwaste [23] Bromine is used in the manufacture of agri-cultural pesticides disinfectants film photography lampsdyes textiles cosmetics etc [24]
Iodine is a weakly electronegative redox sensitive ele-ment which is very important in many biochemical path-ways With its low abundance it is considered an essentialelement for life [25] Fluoride (F) is considered as an es-sential element for oral health and bone formation [26] Inaddition fluoride is functionally an effective metabolic in-hibitor However it has a constructive interference with themetabolism of proteins lipids and carbohydrates in livingorganisms [27] Both bromide (Br) and chloride (Cl) exist inthe body fluids of animals and mortals and their abundancedepends on their intake and excretion [28] Although hal-ogens have effective biological functions high levels ofhalogens may be toxic Large amounts of bromide (Br) maycause some adverse symptoms including nausea andvomiting abdominal pain coma and paralysis [28] Ex-cessive iodide (I) may cause goiter hypothyroidism orhyperthyroidism in exposed people [28] Ingestion offluoride can cause nausea vomiting abdominal pain di-arrhea fatigue drowsiness coma convulsions cardiac ar-rest and eventual death [29] It can also affect physiologicalprocesses such as metabolism growth and reproduction
In order to determine the pollution source of a lake it isuseful to analyze the chemical properties of the water andstudy the main solute sources-e pollution by dissolved saltis related to the large increase of several dissolved saltscaused by human activities [30] that is the total dissolvedcontent in the water system and the increase in the contentof anions and cations -e gradual increase in dissolved saltcan play an important role in the aquatic environment butexcessive salt may have harmful effects on the ecosystemSimilarly the chemical balance in the aquatic system as well
Figure 1 Sampling sites along Lake Mariout
2 Journal of Chemistry
as the solubility and precipitation of the salt contained alsohelps to track pollution [31] -e formation and internalinteraction of different soluble and insoluble salts in aquaticsystems are affected by the physical and chemical factors ofthe ecosystem [31] -e behavior of soluble salts in theaquatic systems can provide information about the forma-tion of precipitated salts -e stability of the precipitated saltis affected by the product of the molar concentration of itsions and the equilibrium solubility constant of the precip-itated salt According to previous studies under alkalineconditions fluorapatite minerals had an important role inreducing the solubility of calcite in the apatite supernatantand solving the destructive effects of fluoride pollution onLake Edku in Egypt [32] Small amounts of bromine arefound in certain minerals (such as apatite amphibole andbiotite) [24] In addition calcium hydroxyapatite canremove toxic ions from the water environment [33]
By multivariate analysis the ecological and environ-mental multivariate data can assess the environmental im-pacts and monitor large-scale biodiversity changes [34]Multivariate analysis is widely used in environmental sci-ence It can help ecologists discover the structure of manycharacteristics of the data and the previous relatively ob-jective summary for easy understanding However it is verycomplicated in theoretical structure and operation methods
To the best of our knowledge relatively little studies havebeen evaluated for the long-term changes in concentrationsof halogens ie bromine fluorine chlorine and iodine andtheir relative to pollution status in surface water pore waterand sediments partitions in the polluted Lake Mariout -eaims of this work are to present an overview of the evalu-ation of halogenrsquos content and to examine the relation ofpollution by halogens as well as to find out their possibleinteractions with dissolved and precipitated salts in MarioutLake which is suffering from the huge amounts of differenttypes of waste waters
2 Materials and Methods
21 Sampling Sites -irteen sampling sites were selected torepresent the survey area of Lake Mariout and the incomingdrainage (Figure 1) Surface water sediment pore water andsediment samples were collected from the thirteen sites Site 1and site 2 were affected by the parallel pumping station(pumping water from the Abis drainageasymp 400000 m3dayminus1 andother openings from El Drain [19] Site 3 represented thecombined discharge of El-Qalaa drainage and WesternWastewater Treatment Plant (WWTP) Sites 4ndash6 belonged tothe Main Basin area and were affected by the drainage of El-Qalaa and El Umoum Site 6 represented the contaminated areabefore the El-Mex pumping station Site 7 was located in theNorthWest Basin In addition to saltmarshes it was also directlyaffected by many industrial and petrochemical companies -eSouth West shallow basin was adversely affected by the localwater sources of El Umoum and El Nubaria drains and its sitewas 8ndash10 Stations 11ndash13 were located in the El-Qalaa the ElNubaria and the El Umoum drains outside the lake -e lastthree locations were chosen as reference locations to describe thepotential pollution of the water discharged into the lake
22 Sampling Processes Surface water and bottom sedimentsamples were collected from thirteen selected sites along thelake and the drains of depth range 15ndash20m by a rubber boatduring autumn 2019 (Figure 1) Nitrile gloves were usedduring the sampling duration
For water sampling thirty-nine airtight clean 5 L poly-ethylene bottles for water sampling were rinsed three timeswith double distilled water and then dried Triplicate col-lected surface water samples were collected by the Niskinwater sampler from each sampling site However thesesurface water samples were not filled in 5 L cleaned poly-ethylene bottles in which they can be preserved Each watersample from the study site was divided into two portions-e first portion was stored in a brown closed polyethyleneplastic bottle the second part was stored in a closed whitebottle for the determination of heavy metals -e subdividedsamples were carefully transported to the laboratory in an icebox However surface water temperature (Tw) pH salinityand TDS value of water samples weremeasured on-site usingportable equipment (CTD YSI 566) -e dissolved oxygen(DO) sample was fixed in a closed brown glass bottle on-siteTurbidity was measured by using the conventional whiteenameled Secchi-disc
For sediment sampling three replicate sediment sampleswere collected from 13 sampling sites using a Van-Veen grabsampler stored in a clean polyethylene bag and transportedto the laboratory in an ice box
23 Sample Preparation In the laboratory the first portionof the subdivided surface water was stored in a brownairtight polyethylene plastic bottle at minus20degC for halogenanalysis -e second portion was divided into two parts andone of which was stored in a plastic colorless bottle at minus20degCto determine phosphorus and silicon in the form of phos-phate and silicate -e other part was kept in the refrigeratoruntil the main water components (calcium magnesiumsodium potassium lithium sulfate and boron) and heavymetals (copper manganese zinc and iron) were analyzed
In addition pore water was extracted from each sedi-ment sample by a centrifuge (Hettich Zentrifugen Universal320 R Andreas Hettich GmbH amp CoKG 78532 TuttlingenGermany) for 20min and at a speed of 10000 rpm [35]
First in each extracted pore water sample pH and Spermilwere detected -en one-third of each extracted pore watersample was preserved in a brown polyethylene plastic bottlewith a stopper and kept at minus20degC for halogen determinationWhile two-third portion was preserved in colorless well-closed plastic bottles and kept at minus20degC for analysis ofphosphorus silicon calcium magnesium sodium potas-sium lithium sulfate and boron calcium magnesiumsulfate boron and heavy metals concentrations (Cu MnZn and Fe)
On the other hand the sediment samples were spread ona clean plastic plate at room temperature and then air driedAfter that the particle size of the air-dried sediment samplewas accurately estimated [36] -e digestion of the sedimentsample was performed by heating the sample with an acidmixture (3mL HNO3 2mL HClO4 and 1mL HF) at 70degC in
Journal of Chemistry 3
a closed Teflon container -e extraction of fluoride bro-mide and iodide from sediment samples was carried outafter the fusion of Na2CO3 with each sediment sample[37 38]
24 Samples Analyses -e carbonate and bicarbonate ofsurface and pore waters were determined in the laboratory bythe titration method [39 40] pH and TDS values of the porewater were measured in the laboratory using portableequipment (CTDYSI 566) From the salinity value chlorosity(Cl) in the surface and pore waters and chlorinity (Clpermil)wereeffectively calculated [39] -e DO of water samples wasaccurately measured by Winklerrsquos method [41] Porosity wasmeasured based on the weight difference between dry and wetsediment samples [42] Calcium and magnesium in surfaceand pore waters and digested sediment samples were carefullydetermined by the titrimetricmethod using Eriochrome BlackT and Murexide indicators [43] Sodium potassium andlithium contents in surface and pore waters and digestedsediment samples were estimated by the flame photometerinstrument (lame139 photometer PFP JENWAY 7) Inor-ganic phosphorus and total phosphorus contents in thesurface and pore waters and sediment samples were deter-mined [43 44] Silicate was measured in the surface and porewaters and digested sediment samples by the calorimetricmethod [39] Curcumin colorimetry was used to determineboron in surface water pore water and digested sediment[43] -e turbidity method was used to estimate sulfate in thesurface water and pore water and digested sediment samples[43] -e heavy metals (Cu Mn Zn and Fe) dissolved in thesurface and pore water samples were extracted with chelatingresin and measured with an atomic absorption spectropho-tometer (GBC Savant AA Scientific equipment serial no A7275 GBC) [45] Fluoride concentration was determined bythe colorimetric method using the zirconium alizarin red Smethod [46] -e bromide was determined by titration usinga thiosulfate solution [41] -e catalytic reduction methodusing the Ce(IV)-As(III) was applied to determine the iodineconcentration [43] -e chloride content in sediments wasestablished by Mohrrsquos method [47]
25 Quality Control and Quality Assurance A sedimentreference material (IAEA-405 International Atomic EnergyAgency Vienna Austria) was used to determine the sedi-ment samplersquos quality controlquality assurance -e re-covery percentages for the selected metals from the standardreference material were in the range of 970ndash1011 Foreach variable an examined calibration procedure of threeexternal standards was performed One of the externalstandards must be of a concentration near but above themethod detection limit -e other concentrations shouldcorrespond to the range of a variable concentration expectedin the sample -e working calibration curve was verified oneach working shift by the measurement of one or morecalibration standards
26 Saturation Index (SI) -e Saturation Index (SI) of 23and 15 structures in surface water and pore water sampleswere calculated respectively [23 48]
It can be calculated from the division of the product of themolar concentrations (IAP [49]) of their component by theirequilibrium solubility constant (Table 1) Moreover SI of someminerals such as anhydrite (CaSO4) gypsum (CaSO42H2O)calcium phosphate (Ca3(PO4)2) magnesium phosphate(Mg3(PO4)2) calcite (CaCO3) aragonite (CaCO3) dolomite(CaMg(CO3)2) magnesite (MgCO3) fluorapatite (FAPCa5(PO4)3F) hydroxyapatite (HAP Ca5(PO4)3OH) octacal-cium phosphate (OCP Ca4H(PO4)325H2O) and carbonate-fluorapatite (CFAP Ca10(PO4)5(CO3)F272(OH)028) besidessome precipitated salts (Fe(OH)2 Fe(OH)3 FePO42H2OMg(OH)2 Mg3(PO4)2 Mn(IO3)2 KIO4 KCIO4 ZnCO3ZnCO3H2O Zn(OH)2 and Zn(IO3)22H2O) was calculatedby the following equation [23 48]
SI logIAPKsp
1113888 1113889 (1)
where IAP and Ksp were the product of the ion activity andthe equilibrium solubility constant of each precipitated saltor mineral SI values represented the under saturation(SIlt 1) or over saturation (SIgt 1) situation of each pre-cipitated salt or mineral
27 Palmerrsquos Method and Piper Ternary Diagram -e dis-solved salts in the surface and pore waters in the in-vestigated area were utilized by Palmerrsquos method andpiper ternary diagram Palmerrsquos method by using the millequivalent percentage of the major anions (Clminus SO4
minus2and HCO3
minus) and cations (K+ Na+ Ca+2 and Mg+2) [50]-is method assumed that the concentration of positiveions and negative ions are in equilibrium ie the sum ofthe concentrations of positive ions in meq Lminus1 is equal tothe sum of the concentrations of negative of ions con-sidering only the major ions -is hypothesis can beverified by converting the average ion concentration ofsurface water and pore water along the study areafrom mg Lminus1 in Table 2 to meq Lminus1 -en the concen-trations were further converted into a percentage of eachion in relation to the total concentration of positive ionsin the case of a positive ion and in relation to the totalconcentration of negative ions in the case of a negativeion -e percentage of each cation and anion was rep-resented in two rectangles in cm to evaluate the relativeformed soluble salts Piper ternary diagram explores theorigin of the dissolved salts in surface and pore waters ofthe lake water besides the effects of drainage sources onthem [55]
28 Multivariate Analysis Multivariate analysis includingcorrelation multiple stepwise linear regression and clusteranalysis has been used to predict the role of halogens in thepollution status of Lake Mariout Multivariate analysis canbe used in monitoring research because they can reduce the
4 Journal of Chemistry
cost of further environmental investigations [56ndash58] -emultivariate analysis using the correlation matrix with acorrelation coefficient (r) multiple stepwise linear regressionwith a coefficient (R) and cluster (tree clustering) at asignificance level of ple 005 is estimated by STATISTICA 99edition At the same time the principal component (PCA)can be estimated through SPSS 15 evaluation
29 Enrichment Factor (EF) EF of the determined elements(Ca Mg Na K Li B P Cu Zn Mn Fe F Cl Br and I) wascalculated by using the equations described (equations (2)and (3)) [59 60]
EF Cm sample
MedianCm Background + 2 times MADCm Background( 1113857
(2)
where Cm was the element concentration Median CmBackground represented median concentration of an ele-ment in the background and MAD Cm Background was themedian absolute deviation from the median calculated fromthe given equation
MAD median xi minus medianj xj1113872 111387311138681113868111386811138681113868
111386811138681113868111386811138681113874 1113875 (3)
-e EF values were classified into five categories defi-ciency tominimal (EFlt 2) moderate (2ltEFlt 5) significant(5ltEFlt 20) very high (20ltEFlt 40) and extremely highenrichment (EFgt 40)
210 Human Health Risk Assessment -e human healthhazard of surface water and sediment ingestion and dermalcontact was assessed by using the estimated daily intake
Table 1 -e hypothetical precipitated salts in surface and pore waters along Lake Mariout
Site 1 2 3 4 5 6 7 8 9 10 11 12 13SI of precipitated salts and minerals
Surface waterCalcite 128 138 340 146 236 303 295 297 205 258 312 126 311Aragonite 103 112 315 120 211 278 270 272 180 233 287 101 286CaSO405 H2O 208 188 126 157 156 155 170 179 199 171 115 075 181CaSO42H2O 196 176 114 144 143 143 158 167 187 158 103 063 169Ca3(PO4)2 2486 2424 2424 2424 2424 2424 2424 2424 2424 2424 2424 2424 2424Ca(IO3)2 157 137 137 137 137 137 137 137 137 137 137 137 137Ca(IO3)26H2O 1006 986 986 986 986 986 986 986 986 986 986 986 986OCP 3964 3569 3569 3569 3569 3569 3569 3569 3569 3569 3569 3569 3569HAP 4574 4349 4349 4349 4349 4349 4349 4349 4349 4349 4349 4349 4349FAP 4277 5036 5038 5195 5171 5131 5090 4982 5131 5081 4903 5095 5163CFAP 6089 1685 1786 1818 1784 1902 1883 1785 1764 1859 1604 1824 1914Fe(OH)2 1196 1217 1196 1189 1208 1059 1176 1158 1007 1192 1205 1199 1152Fe(OH)3 3544 3564 3543 3536 3555 3407 3524 3505 3354 3539 3552 3546 3499FePO42H2O 1053 1074 1053 1046 1065 916 1033 1015 864 1049 1062 1056 1008Mg(OH)2 1215 1206 1131 1171 1173 1159 1179 1188 1170 1183 1151 1152 1168Mg3(PO4)2 085 1345 1121 1240 1245 1205 1264 1291 1236 1276 1180 1184 1229Mn(IO3)2 025 243 354 303 247 312 226 055 183 198 064 262 042KIO4 576 570 552 549 565 564 559 554 551 560 489 551 548KCIO4 495 489 471 468 484 483 478 473 470 479 408 470 467ZnCO3 414 404 613 455 560 560 586 573 491 530 659 472 581ZnCO3H2O minus018 minus027 181 024 128 128 154 142 060 099 227 041 149Zn(OH)2 1198 1189 1199 1210 1254 1194 1223 1232 1216 1207 1249 1227 1203Zn(IO3)22H2O 366 357 367 378 422 362 391 400 383 375 417 395 371Pore waterFluorite 200 211 106 195 346 309 345 317 228 246 307 365 277CaSO405 H2O 370 177 190 200 168 178 202 255 203 212 191 179 211CaSO42H2O 358 165 178 188 155 166 190 243 191 200 178 167 199Ca3(PO4)2 2958 2424 2424 2424 2424 2424 2424 2424 2424 2424 2424 2424 2424Ca(IO3)2 315 137 137 137 137 137 137 137 137 137 137 137 137Ca(IO3)26H2O 1164 986 986 986 986 986 986 986 986 986 986 986 986OCP 4594 3569 3569 3569 3569 3569 3569 3569 3569 3569 3569 3569 3569HAP 5361 4349 4349 4349 4349 4349 4349 4349 4349 4349 4349 4349 4349FAP 5126 5295 5399 5270 5460 5318 5327 5338 5321 5311 5420 5373 5391CFAP 7833 1775 2068 1752 2049 2078 1990 2015 1963 2026 2121 2024 2060MgF2 299 138 177 060 262 232 095 209 212 243 222 251 203Mg(OH)2 1395 1439 1408 1400 1428 1420 1346 1425 1418 1438 1412 1391 1414Mg3(PO4)2 987 2442 2417 2355 2469 2207 2128 2317 2243 2260 2387 2132 2378KIO4 564 568 575 557 561 560 570 566 558 571 551 543 564KCIO4 483 487 494 476 480 479 489 485 477 490 470 461 483
Journal of Chemistry 5
(EDI) hazard quotient (HQ) and hazard index (HI) as givenin equations (4)ndash(11)
2101 For Surface Water Estimated daily intake of surfacewater ingestion and dermal contact (EDIIngw and EDIDermw)were computed by the following equations [61]
EDIIngw(mgkgday) (CW times CR times ET times EF times ED)
(AT times BW) (4)
EDIDermw(mgkgday) (CW times SA times PC times ET times EF times ED times CF)
(AT times BW)
(5)
where CWwas the element concentration in water (mg Lminus1)CR was the contact time (50mL hminus1) ET was the exposuretime (26 h dayminus1) EF was the exposure frequency (7 dayyearminus1) ED was the exposure duration (60 year) ATwas theaverage time (60times 365 day yearminus1) BWwas (707 kg) SAwas
the skin surface area (5700 cmminus2) PC was the dermalpermeability constant (0001 cm hminus1) and CF was theconversion factor for water (10times10minus6 kg mgminus1) [62ndash65]
2102 For Sediment Estimated daily intake of sediment byingestion and dermal contact (EDIIngs and EDIDerms) werecalculated according to the following equations [60]
EDIIngS(mgkgday) CS times IngS times RAFS times EFS( 1113857
(AT times BW) (6)
EDIDermS(mgkgday) CS times IngS times ED times SA times AF times ABS( 1113857
(AT times BW)
(7)
where CS was the concentration of the contaminant insediment (mg gminus1) IngS was the ingestion rated of sediment(80times10minus5mg kgminus1) RAFS was the relative absorption factorof sediment (058) EFS was the exposure frequency (30 day
Table 2 Distribution of the studied variables in surface water (w) and their chlorinity ratios along Lake Mariout
Determined variables Minimum Site Maximum Site Average SD Seawatera Lake Marioutbcd
Physicochemical variablesTw 137 10 1534 11 1759 134Salinity (Spermilw) 23 13 79 1 489 152Chlorinity (Clpermilw) 205 13 71 1 438 137 1898TDSw (mg Lminus1l) 24635 13 7683 1 48503 152874Turbidity (NTU) 166 8 385 12 1296 1174DOw (mg Lminus1l) 0 6 1241 2 605 483 214ndash563d
pHw 744 13 899 2 710ndash860d
CO3w (mg Lminus1) 12 1 amp 2 1152 3 31 388HCO3w (mg Lminus1) 7808 3 19032 12 1147 321Bw (mg Lminus1) 05 7 1661 1 691 411 45Pw (μg Lminus1) 003 8 126 5 029 033Siw (μg Lminus1) 009 12 699 4 317 191Caw (mg Lminus1) 6092 12 3527 8 17703 735 400 549 818ndash1464d
Mgw (mg Lminus1) 9725 3 66615 1 28684 16002 1272 1201Naw (mg Lminus1) 231 11 1420 1 101115 2972 10556 10332Kw (mg Lminus1) 8 11 59 1 3769 123 380 585Liw(mg Lminus1) 0139 11 017 1 0154 001 017SO4w (mg Lminus1) 1978 12 34111 9 16856 9488 2649 4245Cuw (μg Lminus1) 204 3 621 7 317 113 7Mnw (μg Lminus1) 001 8 amp13 198 3 315 554 10Few (μg Lminus1) 009 9 1392 13 69 419 40Znw (μg Lminus1) 527 2 2367 5 1085 578 20Fw (mg Lminus1) 015 11 396 12 204 117 13Clw (mg Lminus1) 2048 13 7284 1 4397 1400 18980Brw (mg Lminus1) 506 12amp13 541 5 1813 1891 65 592Iw (μg Lminus1) 566 10 541 4 1108 1296 60Ion chlorinity ratioCawClw 170Eminus 02 12 100Eminus 01 13 440Eminus 02 240Eminus 02 213Eminus 02 335Eminus 02MgwClw 250Eminus 02 3 110Eminus 01 13 640Eminus 02 230Eminus 02 669Eminus 02 733Eminus 02NawClw 650Eminus 02 11 380Eminus 01 13 240Eminus 01 720Eminus 02 560Eminus 01 635Eminus 01KwClw 220Eminus 03 11 150Eminus 02 13 890Eminus 03 290Eminus 03 210Eminus 02 360Eminus 02LiwClw 240Eminus 05 1 700Eminus 05 13 380Eminus 05 110Eminus 05 939Eminus 06SO4wClw 540Eminus 03 12 110Eminus 01 13 420Eminus 02 310Eminus 02 140Eminus 01 260Eminus 01BwClw 978Eminus 05 7 332Eminus 03 9 670Eminus 03 170Eminus 03 895Eminus 04FwClw 430Eminus 05 11 140Eminus 03 13 540Eminus 04 420Eminus 04 670Eminus 05BrwClw 140Eminus 03 12 160Eminus 02 9 440Eminus 03 500Eminus 03 350Eminus 03 360Eminus 05IwClw 940Eminus 04 1 160Eminus 02 4 300Eminus 03 400Eminus 03a[51] b and c[52 53] d[54]
6 Journal of Chemistry
yearminus1) AF was the adherence factor (007mg cmminus2) andABS was the dermal absorption factor (0001 unit less)[65 66]
Hazard index (HI) is the total chronic hazard attribut-able to exposure to all determined contaminants (i) througha single exposure pathway of the ingestion and dermalcontact of water (HIIngw and HIDermw) and sediment (HIIngsand HIDerms) was given as follows [60]
HIIngW 1113944HQ IngW( 1113857i (8)
HIDermW 1113944HQ DermW( 1113857i (9)
HIIngS 1113944HQ IngS( 1113857i (10)
HIDermS 1113944HQ DermS( 1113857i (11)
3 Results and Discussion
31 Distribution of Halogens and Tested Variables in SurfaceWater
311 Distribution of Halogens in Surface Water -e rangeand average value of halogens in the surface water in thisstudy show a sequence of ClwgtBrwgt Fwgt Iw (Table 2 andFigure 2)-e current study indicate that the water sample ofpumping station (site 6) attained high concentrations offluoride (28mg Lminus1) chloride (38878mg Lminus1) and bromide(181mg Lminus1) and low iodide (641 μg Lminus1) contents (Fig-ure 2) High levels of F Br and I are detected in the MainBasin region which is affected by the drainage of El-Qalaaand El Umoum containing the agricultural and industrialwastes However halogens are involved in the manufactureof pesticides (herbicides fungicides insecticidesacaricidesand nematicides) [67] Plus halogens are produced in theproduction of fertilizers products [67] -e presented resultsof halogens in the studied lake region reflect anomalousdistribution and are mainly affected by water dischargedfrom the drainage sources However the highest fluoridebromide and iodide contents of 377mg Lminus1 6553mg Lminus1and 5410 μg Lminus1 respectively are recorded in the MainBasin affected by El-Qalaa and El Umoum drains Amongthe halogens chloride shows high levels in surface waterespecially in site 1 (72837mg Lminus1) site 2 (65218mg Lminus1)and site 10 (51687mg Lminus1) which are also related to theirlevels in the water of the drains (Figure 2) On the meantimethe lowest Spermilw and Clpermilw are observed at site 13 (ElUmoum Drain) Most of the studied variables have chlo-rinity ratios relatively lower than those measured for LakeMariout andor seawater [51ndash53 68 69] -is is mainly dueto the accumulation of wastewater from Abis and ElUmoum where agricultural products such as fertilizers andbiocides are deposited in industrial products [19]
Due to the increase in chloride content in surface watersamples the conservativeness of the chlorinity ratio is usedto describe the contamination precipitation and dissolutionof sediment components [70] -e FCl ratio in the studyarea is higher than open seawater (430Eminus 05) of a range
430Eminus 05ndash140Eminus 03 and average 540Eminus 04 -e BrClratio is relatively similar to that of seawater (Table 2) -ehighest FCl BrCl and ICl ratios in surface water140Eminus 03 160E ndash 02 and 160Eminus 02 are recorded in site 13(El Umoum drain outside the lake) site 9 (South West Basinin the lake) and site 4 (Main Basin in the lake) -erefore itcan be concluded that the distribution of halogens in thesurveyed area is greatly affected by the drainage of the El-Qalaa El Umoum and the El Nubaria drains
312 Distribution of Tested Variables in Surface Water-e range and average values of the tested variables (Tw Spermilw Clpermilw TDSw turbidity DOw pHw CO3w HCO3w BwPw Siw Caw Mgw Naw Kw Liw SO4w Cuw Mnw Few andZnw) in surface waters of the present study are listed inTable 2 Turbidity fluctuates from 166 to 3850 NTU at sites8 and 12 respectively DO is completely depleted at sites 5 6and 11 and has the highest amount 1241mg Lminus1 at site 2with an average 605mg Lminus1 relatively similar to the reportedLake Mariout value (214ndash563mg Lminus1 [54]) (Table 2) -eaverage content of DO in the lake is higher than those re-ported for the ocean seawater (32ndash48mgL) [71] -e levelsof DO probably relate to the oxygen-producing processes ofthe photosynthesis processes of phytoplankton and mac-rophytes [72] -e presented results indicate that site 1(affect by Abis drainage) is the most affected area in the lakeas it shows the highest contents of Bw Clw Mgw Naw KwLiw and SO4w -e most important feature in the concen-trations of heavy metals Cuw Mnw and Znw in surface wateris that they possess average values lower than those reportedfor the threshold guideline (10 100 and 50 μg Lminus1) [73 74]
-e present study clears out a descending trend in thesurface water average concentrations of halogens andtested variables in the lake as follows TDSw gtClw gtNaw gtMgw gtCaw gt SO4w gtHCO3wgtKw gtCO3w gt Bw gt Brwgt FwgtLiw gt Znw gt Few asymp Siw gtMnw gt Pw gt Iw (Table 2)
313 Interactions of Halogens and Tested Variables inSurface Water Chloride in surface water is significantlyrelated to the drainage water content showing good cor-relations with Tw (r 0631 ple 0028) and pHw (r 0769ple 0003) (Supplementary Table 1) -e negative moderaterelation of Fw and Ip (r 0606 ple 0037) may indicatereplacement of iodine in pore water by fluoride of the surfacewater-emoderate relationship between fluoride in surfacewater and CO3w (r minus0632 ple 0027) and HCO3w(r 0593 ple 0042) may be related to carbonate exchangeand the formation of fluorite minerals (CaF2) [23]
-e correlation matrix reflects that the observed ex-traordinary levels of Bw in the surface water samples aremost probably due to its exchange with the different sedi-ment components not related to the discharged waters(Supplementary Table 1) -is findings is supported by theweak B correlation with Cuw (r minus0587 ple 0045) andgood correlation with Fs (r minus0666 ple 0018) [75 76]However Cuw is one of the pollutants that can be exchangedin drainage water -e correlations of Mgw amp Naw (r 0629
Journal of Chemistry 7
1
23
4
56
7
8
9
10
2986degE 2988degE 2990degE 2992degE
310
8degN
311
0degN
311
2degN
311
4degN
311
6degN
El-mex
pumping
statio
n Main Basin
of Lake Maryout
Southwest Basin
Qalaa Drain
El Umoum Drain
Northwest BasinFish
ery Basi
nEl Nubaria Drain
3311 to 38883888 to 43934393 to 5115
5115 to 65226522 to 7284
(a)
1
23
4
56
7
8
9
10
2986degE 2988degE 2990degE 2992degE
310
8degN
311
0degN
311
2degN
311
4degN
311
6degN
El-mex
pumping
statio
n
Main Basinof Lake Maryout
Southwest Basin
Qalaa Drain
El Umoum Drain
Northwest Basin
Fishery
BasinEl Nubaria Drain
069 to 127127 to 169169 to 242
242 to 277277 to 377
(b)
El-mex
pumping
statio
n
Main Basin of Lake Maryout
South west Basin
North west Basin
1
23
4
56
7
8
9
10
2986degE 2988degE 2990degE 2992degE
310
8degN
311
0degN
311
2degN
311
4degN
311
6degN
Qalaa Drain
El Umoum Drain
Fishery
BasinEl Nubaria Drain
613 to 852852 to 14381438 to 1732
1732 to 52745274 to 6554
(c)
El-mex
pumping
statio
n
Main Basin of Lake Maryout
Southwest Basin
Northwest Basin
1
23
4
56
7
8
9
10
2986degE 2988degE 2990degE 2992degE
310
8degN
311
0degN
311
2degN
311
4degN
311
6degN
Qalaa Drain
El Umoum Drain
Fishery
BasinEl Nubaria Drain
566 to 671671 to 761761 to 817
817 to 922922 to 5411
(d)
Figure 2 Distribution of halogens (Cl F Br and I in surface water of LakeMariout (a) Cl (mg Lminus1) (b) F (mg Lminus1) (c) Br (mg Lminus1) and (d) I(μg Lminus1)
8 Journal of Chemistry
ple 0028) Mgw amp Liw (r 0790 ple 0002) Naw amp Kw(r 0955 ple 0000 Naw amp Liw (r 0835 ple 0001) Naw ampCO3w (r minus0701 ple 0011) Kw amp Liw (r 0712 ple 0009)Kw amp CO3w (r minus0580 ple 0048) CO3w amp HCO3w(r minus0613 ple 0034) and Mgw amp SO4w (r 0631ple 0028) indicate that all these variables have some geo-chemical behaviors [77] Mg Na and Li are some com-ponents of the discharged waters however they havepositive correlations with the chlorinity and salinity of thedischarged water sources (r 0743 0619 and 0815 re-spectively) and (r 0743 0619 and 0815 respectively)Mgw and Liw contents in water samples are affected bytemperature dissolved oxygen and pH with high correla-tions of r minus0650 0677 and 0743 and minus0702 0659 and0815 respectively
32 Distribution of Halogens and Tested Variables in PoreWater
321 Distribution of Halogens in Pore Water -e averagehalogen contents in the pore water are higher than theircontents in the surface water but in the same orderClpgtBpgt Fpgt Ip (Table 3) Current research shows that thelowest and highest average values of Spermilp and Clp have beenmeasured in the pore water of site 6 and site 8 respectively Itis worth mentioning that site 6 is a mixed water of El-Qalaadrainage sewage WWTP treatment plant and lake waterInterestingly the high concentrations of fluoride chloridebromide and iodide in the pore water at site 6 are 123mgLminus1 40321mg Lminus1 11739mg Lminus1 and 24339 μg Lminus1 re-spectively (Table 3) -e salinity and chloride content in thepore water of site 8 are related to the discharge water of manypetrochemical and oil companies besides some fish farms
322 Distribution of Tested Variables in Pore Water -etested variables in the pore water (p) give the followingdescending order MgpgtNapgtCapgt SO4pgtBpgtKpgtBrpgt Fpgt LipgtPpgt Ipgt Sip (Table 3) Interestingly the deter-mined variables in the pore water have higher values thanthe surface water along the lake According to previousstudies pore water is responsible for biogeochemical reac-tions the migration and transformation of partitioned andformed compounds and the transportation of colloidalspecies [78 79] In addition pore water can explore thepotential risks of man-made pollution sources [80] -etested variables in the pore water (p) are given in a differentorder of surface water of ClpgtMgpgtNapgtCapgt SO4pgtBpgtKpgtBrpgt Fpgt Lipgt Ppgt Ipgt Sip (Tables 2and 3)
323 Interactions of Halogens and Tested Variables in PoreWater -e following interactions of halogens CO3w amp Ip Ipamp Fw Brw amp Sip Fp amp Siw and Fp amp Nap give correlationvalues (r 0706 ple 0010 r minus0606 ple 0037 r 0826ple 0001 r minus0704 ple 0011 and r 0670 ple 0017respectively) (Supplementary Table 1) However these re-lationships may indicate their precipitation andor
adsorption on the colloidal particles besides the formation ofsome chemical species [78 79] Extraordinarily large cor-relations of Nap amp HCO3w Kp amp HCO3w Spermilw amp Bp Spermilp ampKp Spermilp amp Lip and Spermilp amp Clp (r 0692 minus0609 minus07410696 0910 and 1000) may refer to the release of theseelements from sediment particles andor precipitation oradsorption [77] In the matrix the negative correlationbetween Cap and Mgp (r minus0592 ple 0042) may be relatedto the release of Mg during the recrystallization of calcite[79]-e relationship between Caw amp SO4p Cuw amp Cap Pw ampPp and Nap amp pHw (r 0744 ple 0006 r 0719 ple 0008r 0647 ple 0023 and r minus0640 ple 0025 respectively)may be due to the chemical interactions in the pore fluidsand the formation certain compounds
33Distribution ofHalogens andTestedVariables in Sediment
331 Distribution of Halogens in Sediment -e averagehalogenrsquos content in the sediment shows a different orderfrom the surface and pore waters of Brsgt FsgtClsgt Is (Ta-ble 4) -e sediment results show that the average bromidecontent is higher than fluoride followed by chloride contentand iodide with average values of 452mg gminus1 040mg gminus1029mg gminus1 and 450 μg gminus1 respectively
-e fluoride concentration in the sediment ranges from001 to 120mg gminus1 with an average value of 04plusmn 035mggminus1 -ese values are lower than reported marine sedimentvalues and higher than the El-Bardawil Lagoon [60]Amongst the halogens the study reveals that Br is the mostabundant ion in surface water pore water and sedimentsamples due to the excessive amounts of organic matter [81]On the contrary the concentration of Cl ions in sedimentsamples is lower than that in surface water and pore watersamples indicating that it exists in soluble salts -e currentresults indicate that the sediments collected from the mostaffected area by the Mediterranean Sea (site 6) contain el-evated levels of fluoride (070mg gminus1) bromide (852mggminus1) and chloride (020mg gminus1) and a reduced amount ofiodide (209 μg gminus1) (Table 4)
332 Distribution of Tested Variables in Sediment -eaverage value of test variables in the determined sedimentsamples shows a significant change from site to site with adescending order CO3sgtMgsgtCasgtNasgt SO4s gt FesgtBsgtKsgtTPsgtMn sgtZnsgtCusgt Lis (Table 4) Plus this studyclears out that the percent of sand and mud of the differentsediment samples ranges from 4 at sites 1 amp 13 to 85 atsite 11 and from 15 at site 11 to 96 at sites 1amp13 re-spectively with averages 25 and 75 respectively Plusthe porosity shows a trend opposite to the particle size andvaries from 4676 to 8214 with an average value of5609plusmn 1114 -e results of the current study reveal mod-erate amounts of CO3 in the sediment samples fluctuatingbetween 1639 and 5736 at sites 6 and 2 respectively -eresults of sand mud porosity and CO3 percentage reflect thatthe texture of the sediment is mainly composed of mud mixedwith carbonate compounds Comprehensively the large storageof sediments with carbonate (359plusmn1280) magnesium
Journal of Chemistry 9
Tabl
e3
Distribu
tionof
thestud
iedvariablesin
thepo
rewater
(p)alon
gLake
Mariout
Site
Spermilp
pHP
Ca p
(mgLminus
1 )Mg p
(mgLminus
1 )Na p
(mgLminus
1 )Kp
(mgLminus
1 )Li
p(m
gLminus
1 ))
SO4P
(mgLminus
1 ))
B P(m
gLminus
1 ))
P P(μgLminus
1 ))
SiP
(microgLminus
1 ))
F p(m
gLminus
1 ))
Cl P
(mgLminus
1 ))
Brp
(mgLminus
1 ))
I p(μgLminus
1 )1
1034
787
481
42303
1097
453
042
2944
8043
363
0045
323
95419
959
7104
2934
809
5611
115725
1050
498
039
2056
663
553
0036
338
8398
1385
24698
31272
717
100
5689
1195
577
053
2778
8949
1204
0034
754
114469
2291
26347
483
796
9619
47652
974
384
043
350
19312
77
0054
215
74599
693
8393
51099
782
5611
89711
1128
42041
1667
16739
1112
0081
1698864
1332
8333
645
775
4008
75367
736
41024
2111
11739
071
0037
1231
40321
799
24339
71125
782
39278
13615
1155
516
056
3667
6051
369
006
6101209
1279
8123
8148
775
9299
84314
1355
468
055
12444
942
212
0056
892
133232
1172
7643
9684
78
962
72109
880
393
036
3778
21341
114
0087
1061429
2131
9981
10114
764
1122
113586
1195
524
049
4667
8007
071
0041
1138
102562
1332
8572
11639
742
4008
61996
915
332
033
2833
11594
754
0026
1215
67834
746
37587
125
702
481
38413
8703
274
028
2167
13913
081
0025
2154
44832
1438
9891
13755
807
3206
6467
817
446
039
4556
17246
635
0042
954
5737
533
1097
Minim
um45
702
962
13615
736
274
024
1667
6051
071
0025
215
40321
533
7104
Maxim
um148
809
39278
115725
8703
577
056
12444
21341
1204
0087
2154
133232
2291
37587
Average
919
77
718
67412
163077
4381
041
3782
1223
485
0048
955
82779
1238
14768
SD308
032
10027
29209
2132
825
01
2769
5047
391
0019
542
27891
524
9917
10 Journal of Chemistry
Tabl
e4
Distribu
tionof
thestud
iedvariablesin
thesediment(s)alon
gLake
Mariout
Site
Sand
()
Mud ()
Porosity
()
CO3s
()
B s(m
ggminus
1 )P s
(mg
gminus1 )
Ca s
(mg
gminus1 )
Mg s
(mg
gminus1 )
Na s
(mg
gminus1 )
Ks
(mg
gminus1 )
Lis(m
ggminus
1 )
SO4s
(mg
gminus1 )
Fes
(mg
gminus1 )
Cu s (μg
gminus1 )
Mn s
(μg
gminus1 )
Zns(μg
gminus1 )
F s(m
ggminus
1 )
Cl s
(mg
gminus1 )
Brs
(mg
gminus1 )
I s(μg
gminus1 )
14
964915
183
299
044
1670
811
2583
408
0028
4861
828
963
5617
1272
034
041
128
1686
244
564925
574
196
028
1002
1419
2717
269
0015
662
257
793
4350
1313
057
054
123
358
319
816667
299
246
073
1670
1216
3125
336
0022
463
487
1228
4330
1677
044
034
448
516
418
824853
3813
1111
032
668
2229
3425
365
0094
2222
770
922
4637
1245
030
020
309
296
512
884697
482
614
012
501
1115
1833
091
0040
1713
243
600
27933
1223
082
034
245
254
65
954667
164
370
157
835
1257
2958
388
0030
5648
890
1927
5347
3117
070
020
852
209
75
954762
375
524
024
367
2047
3133
256
0102
1157
546
883
4185
1393
120
020
341
259
838
626143
457
697
039
668
1621
3550
347
0145
4167
598
737
4157
1412
022
034
144
1277
918
826000
349
083
054
401
1094
3358
369
0025
2454
701
868
5702
3065
036
027
250
172
1036
645070
441
296
002
935
1763
3117
246
0045
2685
369
790
4533
1315
012
047
1012
224
1185
157000
325
240
074
969
2250
3508
328
0193
1343
1026
735
3890
1070
005
007
533
128
1237
638214
463
291
032
334
1824
3008
358
0018
556
340
728
2475
827
001
007
852
281
134
965000
177
211
054
2338
1621
3925
599
0068
833
1687
1187
6492
1853
004
027
639
194
Min
415
4667
164
083
002
334
811
1833
091
0015
463
243
600
2475
827
001
007
123
128
Max
8596
8214
574
1111
157
2338
2250
3925
599
0193
6620
1687
1927
6492
3117
120
054
1012
1686
Av
2575
5609
359
398
048
951
1559
3096
335
0063
2671
672
951
4500
1599
040
029
452
450
SD23
231114
128
276
039
603
455
522
115
0055
2030
393
343
1120
708
035
014
303
475
Minm
inim
umM
axm
axim
uma
ndAv
averageSD
stand
arddeviation
Journal of Chemistry 11
(1559plusmn455mg gminus1) and calcium (951plusmn603mg gminus1) com-ponents may be attributed to the abundance of calcium min-erals [4] However in general the average amounts of allvariables in sediment samples showmarked variations fromonesite to another with a descending order of CO3sgtMgsgtCasgtNasgtSO4sgtFesgt BrsgtBsgtKsgtTPsgtFs gtClsgtMnsgtZnsgtCusgtLisgt Is (Table 4) -e measured concentra-tions of Mn Zn Cu and Fe in the sediment samples are stilllower than the reported values and also lower than the back-ground levels of crust and the toxicological reference contents ofUS DOE (US Department of Energy) US EPA (US Envi-ronmental Protection Agency) and CEQG (Canadian Envi-ronmental Quality Guidelines) [82]
Contrasting the obtained levels for the halogens withthose previously reported ones the present study indicatesthat surface and pore waters incorporate more considerableamounts of fluoride compared to the formerly reported onesin Lake Edku (Tables 2 and 3) and lower levels in theMarioutarea than those measured along the Egyptian MediterraneanSea coast [27] Compared with the sediments previouslyfound on the Mediterranean coast of Egypt the chloridecontent in the sediments of the Mariout area is lower [83]Compared with those observed in seawater the studiedsurface water and pore water samples have lower bromidecontent and higher levels than previously reported in LakeMariout [52 53] -e concentration of iodide in surfacewater pore water and sediments is equivalent to the con-centration of rivers and lakes in the world [84]
333 Interactions of Halogens and Tested Variables inSediment -e correlation matrix shows the important roleof halogens in the formation and precipitationdissolution ofsalts and minerals produced along the lake (SupplementaryTable 1) However it shows that chloride seems to be in thesoluble forms along the surface and pore waters of studiedarea showing good relations with Caw (r 0666 ple 0018)Clp (r 0677 ple 0016) and SO4p (r 0858 ple 0000)Also Cls gives good correlations with Mgw (r 0710ple 0010) Naw (r 0602 ple 0038) Clw (r 0619ple 0032) Mgp (r 0774 ple 0003) and Kp (r 0731ple 0007) Chloride in the surface and pore waters plays animportant role in the dissolution association and formationof various salts along the lake -e good relationship be-tween Is and Caw (r 0666 ple 0018) may reflect the de-positionrelease of CaI+ during the formationdissolution ofcalcium carbonate [85] In addition these correlations maybe related to organic-I which formed by bacterial species andtheir remineralization in bottom sediments [86] -emoderate relationship between Nas and Brw (r minus0622ple 0031) may indicate the possible formation of BrClspecies and the precipitation or adsorption of Na minerals insediments [87] -e results of this study also reflect thestrong negative correlation between Fs and Bw (r minus0666ple 0018) which may be related to the release of fluoridefrom sediment and the formation of soluble fluoridecomplexes ((BFn[OH]4minusn)minus) with the excessive boron con-centration in the water [88] -e negative relation betweenKs and Spermilw (r minus0673 ple 0016) possibly reflect that Kw
preferentially chooses to exist in the soluble form of KClrather than being adsorbed andor bound by some richminerals in the sediment
-e significant correlations between CO3s and Mgw(r 0637 ple 0026) CO3s and Clw (r 0723 ple 0008)CO3s and pHw (r 0833 ple 0001) CO3s and Spermilw(r 0723 ple 0008) and between CO3s and Ks (r minus0673ple 0016) may be accompanied by the possible formationdissolution of the dolomite mineral in the presence ofsufficient Mgw which is usually affected by optimal pHsalinity and the potassium salts (Supplementary Table 1)-ese observed results are matching with the previouslyreported studies [32] Significant negative correlation be-tween TPs and CO3s (r minus0744 ple 0006) may indicate theextended release of P from carbonate minerals and for-mation of apatites [32]
-e correlation matrix also refers to other possible in-teractions between the remaining determined variables(Supplementary Table 1) -e significant correlation be-tween SO4s andMgw (r 0706 ple 0010) and Liw (r 0633ple 0027) may be associated to the formation of Mg-sulfateand the pollution of sediments by discharged waters con-taining excessive sulfate and Li [89] In the contrary thestrong positive correlation between TPs and Cus and be-tween TPs and Zns may be related to the same source ofpolluted discharge water [23 83]
-e high negative correlations of Zns with Few(r minus0785 ple 0003) CO3s (r minus0601 ple 0039) and Cus(r 0698 ple 0012) may indicate that Zn Cu and CO3depositions in sediment samples are linked to the soluble Feform in water (ferrous) ie the release of Fe upwards in thewater column in the anoxic conditions (SupplementaryTable 1) [90] -e excellent relations found between Fesand CO3s (r minus0799 ple 0002) Fes and Cas (r 0637ple 0026) Fes and Clw (r minus0752 ple 0005) Fes and Nas(r 0720 ple 0008) and between Fes and Ks (r 0833ple 0001) may reflect the dissolution of the chelating Feassociation with the soluble organic compounds in thewater-sediment interface and the formation of the sol-uble ferrous form in low dissolved oxygen within theareas affected by untreated discharged waters [90] -estrong correlations of Mns with SO4w Nap Nas Ks CO3sZns and Fes (r minus0585 0608 0611 0698 minus0655 0691and 0716 respectively) may associate with the solubilityof abundant Mn minerals and P-Mn forms in the sedi-ment because of its possible reduction to Mn+2 solublespecies under anoxic conditions [90] It is worth men-tioning that the results of this study indicate that ap-proximately 333 of the survey sites indicate thedepletion of dissolved oxygen in their surface watersamples Under such anoxic conditions bacteria are mostlikely to use sulfate instead of oxygen to break downorganic matter and cause the release of iron and phos-phorus into the water column
-e significant direct correlation between Ks and Nas(r 0832 plt 0001) clearly reflects the transport of solublesalts of K and Na between the pore water phase of thesediment and water-sediment surface phase (SupplementaryTable 1) -e good correlation between porosity and Nas
12 Journal of Chemistry
indicates the possible transfer of Na between pore water andsediment partitions
34 Interactions of Precipitated Halogenated Compounds inSurface and Pore Waters -e Saturation Index (SI) [23 60]of twenty-three and fifteen structures in surface water andpore water samples respectively are listed (Table 1) -ecorrelation matrix of the calculated Saturation Indices withthe presented data shows the different factors affecting theinteraction of the halogenated compound with other pre-cipitated salts and minerals Table 1 explores the precipitationof the phosphate minerals and salts are most abundantfollowed by the hydroxidesrsquo salts iodate salts sulfate andcarbonate minerals and salts in surface waters Amongst thehalogens precipitated salts fluoride minerals especiallyfluorapatites and carbonate-fluorapatite (FAP and CFAP)have high SI values in surface water (4277ndash5195 and1604ndash6089 respectively) and in pore water (5126ndash5460 and1752ndash7833 respectively) Bromide and chloride are mainlyfound in the soluble forms in surface and pore waters Iodidesalts (Ca(IO3)2 and Ca(IO3)26H2O) moderately precipitatein surface and pore Iron salts precipitate in surface waterwhile in pore water they are not formed -us SI contentreflects that halogens especially fluoride and iodide play avital role in reducing lake pollution
In addition Table 1 shows that the precipitation com-pounds that may be formed in surface water are relativelydifferent from those in sediment pore water For examplefluorite (CaF2) and sellaıte (MgF2) may be only formed inpore water while calcite and aragonite may be deposited insurface water However the formation of fluorite in surfacewater is related to Naw (r 0778 ple 0003) Kw (r 0704ple 0011) CO3w (r minus0718 ple 0009) Fw (r 0770ple 0003) and Ip (r minus0785 ple 0003) (SupplementaryTable 1)
-e formation of calcium sulfate hemihydrate calciumsulfate and anhydrite in water is related to the increase in theamounts of Caw Mgw SO4w Nap Fp Sip Cls and Mns andthe decrease in porosity values On the other hand pre-cipitation of calcium phosphate is related to Brw (r 0751ple 0005) Znw (r 0668 ple 0018) Pw (r 0881ple 0001) and Ks (r 0881 ple 0001) ie it is affected bythe discharged water composition (Supplementary Table 1)
-e formation of calcite and aragonite in surface water isrelated to the formation of CO3w (r 0753 ple 0005) anddissociation of HCO3w (r minus0660 ple 0020) pHw values(r minus0654 ple 0021) and their dissolution in sediment(r minus0620 ple 0032) (Supplementary Table 1)
-e dolomite formation in water may be affected by theincrease of CO3w (r 0817 ple 0001) and the decrease ofHCO3w (r minus0658 ple 0020) increase in TDSw (r 0599ple 0040) and increase in pHw (r minus0656 ple 0021)besides the possible release of CO3s from abundant sediment(r minus0624 ple 0030) and the precipitation of calcite(r 0984 ple 0000) and aragonite (r 0984 ple 0000) intosediment fraction (Supplementary Table 1)
Generally in the current study the possible formedhalogenated minerals and salts are affected by their
abundance in different components of the lake besides theirpossible dissolution or formation on the sediment texturesgeochemistry of the sediments and physicochemical vari-ables of water in addition to the components of the dis-charged waters
35 Interactions of Dissolved Halogenated Compounds inSurface and PoreWaters -e utilization of dissolved salts insurface and pore waters by utilizing Palmerrsquos method andpiper ternary diagram [50] indicates that Na is the richestcation in surface water followed by Mg Ca and K At thesame time Mg is the most predominate one in the porewater (Figures 3 and 4) Obviously Cl is the most importantanion in surface water and pore waters samples Howeverthe piper ternary diagrams of surface water and pore waterclearly shows that NaCl is the most dominant in surfacewater while MgCl2 is the most abundant in pore waterCoincidently Palmerrsquos method also reflects that NaCl(574) is the most existent species in surface water fol-lowed by MgCl2 (304) CaCl2 (71) CaSO4 (29)Ca(HCO3)2 (14) and KCl (12) (Figure 3) At the sametime MgCl2 (760) is the most present species in porewater followed by NaCl (73)asympMg(HCO3)2 (73)Ca(HCO3)2 (52) and MgSO4 (31) (Figure 4)
36 Multivariate Analysis
361 Principal Component (PCA) By applying Varimaxrotation and Kaiser normalization to 98 variables in the PCAfor halogens and tested variables and calculated parametervalues 7 extracted PCs with eigenvalues higher than 1 areobtained However it is important that the eigenvalue mustbe greater than 1 Its seven PCs explain 8558 of the totalvariance
-e first principle component (PC1) is 1473 of thetotal variance and shows positive coefficient factor loadingsfor CO3w TDSw Kp calcite aragonite dolomite FeCO3MgCO3 ZnCO3 and ZnCO3H2O (0804 0547 05320938 0938 0947 0741 0940 0866 and 0866 respec-tively) In addition it provides negative factor loadings forHCO3w pHw Bw Nap and CO3s (minus0782 minus0610 minus0595minus0532 and minus0572 respectively) PC1 is related to thefactors affecting the carbonate compounds that may beformed in the area under consideration
PC2 accounts to 1458 of the total variance and alsoshows positive and negative coefficient factor loadingsrepresenting the different interactions between the CawMgw Liw SO4wMgp Nap pHp Cls SO4s Brs and porosityin water pore water and sediment that are responsible forthe composition of sulfate magnesium and phosphateprecipitates besides the effect of the discharged waters onwater-pore water-sediment componentsrsquo cycles
PC3 typically shows 1377 of the total variance withpositive and negative loadings which can properly explorethe effect of the principal sources of local pollution on thedissolving of heavy metals B and P from sediment into thewater column and the probable formation of Fe(OH)2Fe(OH)3) and FePO4
Journal of Chemistry 13
Similarly the coefficient factor loadings of PC4 with1355 are related to the influence of the polluted dischargewater and sediment texture on the formation of F Cl and Isalt besides the precipitation of halogenated compounds(FeF2 Mn(IO3)2 KIO4 and KCIO4) besides their minerals(CaF2 MgF2 FAP and CFAP)
Simultaneously PC5 gives 1092 of the total variancewith positive and negative loadings which explains therelations between the physicochemical limits of the surfacewater pore water and sediment components and theprecipitation of minerals and salts (OCP HAP CuBrZn(OH)2 and Zn(IO3)22H2O) -is is also associated tothe influence of the sedimentary material on the release ofMn Fe and P from sediment into pore water and watercolumn and formation of Ca3(PO4)2 OCP and HAPminerals
However PC6 associates with 100 of the total variancegiving positive and negative coefficient factor loadingswhich explain that the sediments (minerals andor organic-iodine compounds) are only the acting sink for iodine andiodine species (Iminus and IOminus
3 ) in the water as previously re-ported [84] PC6 also reflects the precipitation of severalhalogenated compounds such as calcium iodate (Ca(IO3)2and Ca(IO3)26H2O) and copper iodate (CuI andCuIO3H2O) besides Cu3(PO4)2 species in the lake watercolumn
-e loadings of PC7 contribute by 804 and show thatthe release of calcium in pore water into the water column isresponsible for the precipitation of halogenated compounds(CuCl and Zn(IO3)22H2O) as well as copper and Zn salts(Cu3(PO4)2 and Zn(OH)2)
362 Cluster Analysis On the other hand cluster analysisshows that the similarity of sites 1amp4 5amp8 6amp9 2amp10 and11amp13 is due to the texture of sediment
363 Multiple Regression Multiple regression equations ofhalogens as dependent variables and the other determinedand calculated parameters as independent variables insurface water pore water and sediment partitions are listed(Table 5)-e amount of fluoride in water samples is affectedby the discharged watersrsquo fundamental components espe-cially Zn and Cu besides its surface water-pore water in-teractions Its content in pore water seems to be stronglyaffected by its substitution competition with other halogensin surface water-spore water-sediment cycle due to its highelectronegativity Generally in the affected area the type ofpollutant in the discharged water plays an important role inthe dissolution andor precipitation of fluoride and otherhalogens in the surface water-pore water-sediment cycle
574
147129
300
12
Ca(HCO3)2CaSO4CaCl2
MgCl2KClNaCl
(a)
SO4
2 + CIndash Ca 2+ + Mg 2+
CO32ndash + HCO3
ndashNa+ + K+
Mg2+ SO42ndash
Ca2+ CIndash
(b)
Figure 3 (a) distribution and (b) piper ternary diagram of the formed dissolved salts in surface water of Lake Mariout
Ca(HCO3)2Mg(HCO3)2MgSO4
NaClMgCI2KCl
760 1052
7373 31
(a)
SO4
2ndash + C
Indash
Ca 2+ + Mg 2+
CO32ndash + HCO3
ndashNa+ + K+
Mg2+ SO42ndash
CIndashCa2+
(b)
Figure 4 (a) distribution and (b) piper ternary diagram of the formed dissolved salts in pore water of Lake Mariout
14 Journal of Chemistry
Table 5 -e multiple regression analyses of each halogen as dependent variable and other tested variables in the surface water pore waterand sediment partitions besides the precipitated salts in surface water along Lake Mariout
Dependentvariable Multiple regression equation R2
FluorideLake water FW 3162 + 092 Zn F2 minus 033 SiP + 021 CuIminus 017 SpermilP 09911
Pore water Fp minus2567minus117 SiW minus 033 LiP minus 062 CuClminus 028 IS + 023 TDSW+ 017 KIO4 minus 012 BrW minus 004porosity + 004 PW
10000
Sediment FS 088 CAPminus 049 MgS minus 046 DOW+039MgW+ 027 Mn(IO3)2 + 015 Cu3(PO4)2 + 004 HAP+ 002 pHP 10000ChlorideLake water No relation 00000Pore water No relation 00000Sediment ClS minus116 + 046 MgP + 077 Kp minus 049 dolomite + 017 TDSW minus 011 CuI + 005 NaS + 002 BS + 001 FeF2 10000Bromide
Lake water BrW 1563 + 110 CuBrminus 057 CuClminus 021 KS minus 014 pHP minus 011 TPS + 014 FeW+ 007 ZnSminus 002 PP + 001turbidity 10000
Pore water BrP minus1516minus 055 FeS minus 073 BS + 061 MnW+ 083 SiP + 049 NaS minus 031MnS minus 015 CuBr + 011 pHW minus 001CaW
10000
Sediment BrS 015 SiP + 195 CFAP+ 002 FP minus 045 IS + 192 sand+ 037 MnW minus 029 MgS minus 012 LiP + 005Ca3(PO4)2 minus 002 ZnF2
10000
IodideLake water IW 099 Ca(IO3)6H2O 09999
Pore water IP minus097 ZnF2 minus 057 Li3PO4 minus 053 BP + 034 FAP+ 015 Ca(IO3)2 +MnW+ 005 KS minus 009 turbidity + 055CaS
09999
Sediment IS minus072 + 135 SO4P + 023 Mn(IO3)2 + 063 FeW+ 031 TPS minus 035 MgP minus 012 Zn(CO3)22H2O 09993
40E + 0135E + 0130E + 0125E + 0120E + 0115E + 0110E + 0150E + 0000E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
12345
678910
111213
(a)
10E + 0090E ndash 0180E ndash 0170E ndash 0160E ndash 0150E ndash 0140E ndash 0130E ndash 0120E ndash 0110E ndash 0100E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
12345
678910
111213
(b)
12345
678910
111213
40E ndash 0235E ndash 0230E ndash 0225E ndash 0220E ndash 0215E ndash 0210E ndash 0250E ndash 0300E ndash 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
(c)
12345
678910
111213
80E ndash 0670E ndash 0660E ndash 0650E ndash 0640E ndash 0630E ndash 0620E ndash 0610E ndash 0600E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
(d)
Figure 5 Hazard quotient of ingestion and dermal contact of surface water and sediment of LakeMariout (a) ingestion of water (b) dermalcontact of water (c) ingestion of sediment and (d) dermal contact of sediment
Journal of Chemistry 15
Minerals and precipitated salts in the different partitions(surface water pore water and sediment) play an importantrole in the deposition and release of halogens in sedimentsAdditionally the texture and the porosity of the sedimentsplay a key role in the distribution of halogens in the threepartitions Interestingly chloride is the only halogen that hasnegligible interactions along the surface water and porewater partitions because it is present in large quantities inthe form of soluble salts (NaCl and MgCl2)
37 Pollution Status
371 Enrichment Factor (EF) Twowell-knownmethods areused to assess environmental pollution public health sig-nificance of ingestion and dermal contact with water andsediment components and sediment enrichment factor (EF)[59 60]
-e average EF values of the determined elements CaMg Na K Li B P Cu Zn Mn Fe F Cl Br and I are alllower than the value that is less than the minimum en-richment value (EFlt 2)-us the area under investigation isstill ecologically considered as an unpolluted region
372 Human Health Risk Assessment -e EDI HQ and HIshow the variable values of all pollutants in the surface waterand sediments along the lake region and in drains (sites11ndash13) under study Among all the calculated variables ofsurface water ingestion (EDIIngw) and dermal contact(EDIDermw) Cl is still the only variable that shows high levels(average 1551 and 43mg kgminus1 dayminus1 respectively) -eestimation daily intake of sediment ingestion (EDIIngs) anddermal contact (EDIDerms) of Mg Ca and Na give maximumaverage amounts of 841Eminus 02 513E ndash 02 and167Eminus 03mg kgminus1 dayminus1 respectively
Among the HQ of the calculated detection variables thecontent of HQB of ingestion and dermal contact with waterand sediment is the highest However 70 of sites have HQBvalues more than 10 (Figure 5) Comparing the HQ values ofall the determined variables HQB of the ingestion of surfacewater shows values higher (gt10) However due to the impactof drainage the HQB values of stations 1ndash4 8ndash10 12 and 13
are higher than 10 -erefore these sites can be consideredas the area with the most serious boron pollution caused byuntreated discharged water disposal In addition the HIIngwlevel of water ingestion for the studied variables in all sites ismuch higher than 10 (Figure 6) Except for boron it isusually concluded that the study area does not pose any riskto the population due to halogens or other variables Ac-cordingly this information may help the official authoritiesoptimize management plans and strengthen their pollutioncontrol actions in Lake Mariout
4 Conclusions
-e effects of halogen salts and minerals on the pollution ofLake Mariout were studied Halogens and some physico-chemical variables in three partitions surface water porewater and sediment in Lake Mariout were evaluated -ehalogen content was variable between different sites andchloride was the main halogen in surface water and porewater but it was very rare in the lakersquos sediment partitionPiper ternary diagram and Palmerrsquos method reflected thatNaCl was the dominant salt in surface water while MgCl2was the main dissolve salt in pore water-e chlorinity ratiosof halogens and tested variables were directly matched to thefeeding drain sources
Moreover the Saturation Index (SI) reveals that 23 and 15precipitated salts and minerals are formed in surface water andpore water respectively -e SI value indicated the formationof phosphate minerals in surface water and pore water es-pecially octacalcium phosphate (OCP Ca4H(PO4)325H2O)and hydroxyapatite (HAP Ca5(PO4)3OH) In addition tofluoride minerals especially fluorapatite (FAP) and carbonate-fluorapatite (CFAP) were obviously precipitated from surfacewater and pore water Soluble salts of bromide and chloridewere formed in surface water and pore water Iodide salts(Ca(IO3)2 and Ca(IO3)26H2O) were moderately precipitatedin the surface water and pore water
Moreover the multivariate analysis including the cor-relation matrix multiple stepwise linear regression treeclustering and principle component (PCA) of all the de-termined and calculated variables was applied to estimatethe proposed interaction between halogens and other tested
10E + 02
16E + 0214E + 0212E + 02
80E + 0160E + 0140E + 0120E + 0100E + 00
1 2 3 4 5 6 7 8 9 10 11 12 13
HIIngHIDerm
(a)
1 2 3 4 5 6 7 8 9 10 11 12 13
HIIngHIDerm
40E ndash 0235E ndash 0230E ndash 0225E ndash 0220E ndash 0215E ndash 0210E ndash 0250E ndash 0300E + 01
(b)
Figure 6 Hazard index of ingestion and dermal contact of the studied variables in surface water and sediment of Lake Mariout (a) waterand (b) sediment
16 Journal of Chemistry
variables in the polluted area under study -e multivariateanalysis showed that there were many interactions betweenhalogens and tested variables High levels of fluoride bro-mide and chloride in surface water were related to thecomposition of drainage waters -e enrichment factor (EF)showed that Lake Mariout was not polluted However thehuman health adverse effects calculated for surface waterand sediment did not reflect any possible likelihood hazardeffects from halogens
Interestingly the current study concluded that halogencompounds especially fluorides are most likely to be de-posited from surface lakes in the form of many minerals andprecipitation thereby reducing the adverse pollution effectson human health -e results obtained through this workhelp to find the correlations between the sampling sites andthe variables obtained by physical and chemical measure-ments which can be used to construct a fast decision modelfor separating different water quality samples -is infor-mation may help the official authorities optimize manage-ment plans and strengthen their pollution control measuresin Lake Mariout
Data Availability
-e data used to support the findings of this research areincluded within the paper
Conflicts of Interest
-e authors declare that there are no conflicts of interestregarding the publication of this manuscript
Supplementary Materials
Supplementary Table 1 correlation matrix of variable insurface water pore water and sediment partitions besidesthe precipitated salts in surface water along Lake Mariout(Supplementary Materials)
References
[1] M S Masoud T O Said G El-Zokm and M A ShreadahldquoAssesment of heavy metals contamination in surface sedi-ments of the Egyptian Red Sea Coastsrdquo Australian Journal ofBasic and Applied Sciences vol 6 pp 44ndash58 2012
[2] M A Shreadah M I Abdel Moneim T O SaidE M I Fathallah and M E Mahmoud ldquoPAHs in seawater ofthe semi-closed areas along the Alexandria coast of EgyptianMediterranean seardquo Journal of Environmental Protectionvol 4 no 11 p 11 Article ID 40298 2013
[3] S Abdel Ghani G El Zokm A Shobier T Othman andM Shreadah ldquoMetal pollution in surface sediments of Abu-Qir bay and Eastern harbour of Alexandria Egyptrdquo EgyptianJournal of Aquatic Research vol 39 no 1 pp 1ndash12 2013
[4] G F El-Said ldquoBioaccumulation of key metals and othercontaminants by seaweeds from the Egyptian MediterraneanSea Coast in relation to human health riskrdquo Human andEcological Risk Assessment An International Journal vol 19no 5 pp 1285ndash1305 2013
[5] M A Shreadah A H Shobier S Abdel Ghani G M El-Zokm and T O Said ldquoMajor ions anomalies and
contamination status by trace metals in sediments from twohot spots along the Mediterranean Coast of Egyptrdquo Envi-ronmental Monitoring and Assessment vol 187 no 280pp 1ndash18 2015
[6] A El Nemr G F El-Said A Khaled and S Ragab ldquoDis-tribution and ecological risk assessment of some heavy metalsin coastal surface sediments along the Red Sea Egyptrdquo In-ternational Journal of Sediment Research vol 31 no 2pp 164ndash172 2016
[7] A El Nemr G F El-Said S Ragab A Khaled and A El-Sikaily ldquo-e distribution contamination and risk assessmentof heavy metals in sediment and shellfish from the Red Seacoast Egyptrdquo Chemosphere vol 165 pp 369ndash380 2016
[8] A El Nemr and G F El-Said ldquoAssessment and ecological riskof heavy metals in sediment and molluscs from the Medi-terranean coastrdquo Water Environment Research vol 89 no 3pp 195ndash210 2017
[9] M A Sheradah A A El-Sikaily N M Abd El MoneamN E Abd El Maguid and M G Zaki ldquoChemical and bio-chemical evaluation of marine pollution by polychlorinatedbiphenyls and pesticides in two regions along the EgyptianMediterranean Seardquo International Journal of EnvironmentalMonitoring and Analysis vol 6 no 3 pp 95ndash109 2018
[10] M A Shreadah A A-M M El-Sayed A A S TahaA-M M Ahmed and H H Abdel Rahman ldquoEvaluation ofdifferent anthropogenic effluents impacts on the water qualityusing principal component analysis a case study of Abu-QirBay-Alexandria-Egyptrdquo International Journal of Environ-mental Monitoring and Analysis vol 7 no 3 pp 56ndash67 2019
[11] G F El-Said M M El-Sadaawy A H Shobier andS E Ramadan ldquoHuman health implication of major and traceelements present in commercial crustaceans of a traditionalseafood marketing region Egyptrdquo Biological Trace ElementResearch vol 199 pp 315ndash328 2020
[12] M A Shreadah S A A Ghani H B I HawashA A E Samie and A E M M Ahmed ldquoOrganotin com-pounds in sediments of northern lakes Egyptrdquo Journal ofEnvironmental Protection vol 05 no 17 pp 1654ndash1666 2014
[13] A M Younis G M El-Zokm and M A Okbah ldquoSpatialvariation of acid-volatile sulfide and simultaneously extractedmetals in Egyptian Mediterranean Sea lagoon sedimentsrdquoEnvironmental Monitoring and Assessment vol 186 no 6pp 3567ndash3579 2014
[14] G F El-Said S E O Draz M M El-Sadaawy andA A Moneer ldquoSedimentology geochemistry pollution statusand ecological risk assessment of some heavy metals insurficial sediments of an Egyptian lagoon connecting to theMediterranean Seardquo Journal of Environmental Science andHealth Part A vol 49 no 9 pp 1029ndash1044 2014
[15] G M El Zokm M A Okbah and A M Younis ldquoAssessmentof heavy metals pollution using AVS-SEM and fractionationtechniques in Edku Lagoon sediments Mediterranean SeaEgyptrdquo Journal of Environmental Science and Health PartAvol 50 no 6 pp 571ndash584 2015
[16] G M El Zokm H R Z Tadros M A Okbah andG H Ibrahim ldquoldquoEutrophication assessment using TRIX andCarlsonrsquos indices in Lake Mariout water Egyptrdquo EgyptianJournal of Aquatic Biology and Fisheries vol 22 no 5pp 331ndash349 2018
[17] N Donia ldquoLake Maryut monitoring using remote sensingrdquo inProceedings of the gypt Eighteenth International WaterTechnology Conference IWTC18 Sharm El Sheikh Abu DhabiUAE March 2015
Journal of Chemistry 17
[18] M A Khairy ldquoAssessment of priority phenolic compounds insediments from an extremely polluted coastal wetland (LakeMaryut Egypt)rdquo Environmental Monitoring and Assessmentvol 185 no 1 pp 441ndash455 2013
[19] N A El-Naggar and E A Rifaat ldquoEgyptian coastal lakes andwetlands part Imdashcharacteristics and hydrodynamicsrdquo in eHandbook of Environmental Chemistry A M Negm EdSpringer International Publishing AG Berlin Germany 2017
[20] J J Hanley and K T Koga ldquoChapter 2 ldquohalogens in terrestrialand cosmic geochemical systems abundances Geochemicalbehaviors and analytical methodsrdquordquo in e Role of Halogensin Terrestrial and Extraterrestrial Geochemical ProcessesD E Harlov and L Aranovich Eds Springer InternationalPublishing AG Berlin Germany pp 21ndash121 2018
[21] A Ghosh K Mukherjee S K Ghosh and B Saha ldquoSourcesand toxicity of fluoride in the environmentrdquo Research onChemical Intermediates vol 39 no 7 pp 2881ndash2915 2013
[22] M M Naim A A Moneer and G F El-Said ldquoPredictiveequations for the defluoridation by electrocoagulation tech-nique using bipolar aluminum electrodes in the absence andpresence of additives a multivariate studyrdquo Desalination andWater Treatment vol 57 no 14 pp 6320ndash6332 2016
[23] G F El-Said N A Shaltout M M El-Sadaawy andA M H Morsy ldquo-e precipitation of fluoride calcium andmagnesium minerals from Egyptian Mediterranean Sea coastin relation to discharged watersrdquo Desalination and WaterTreatment vol 57 no 5 pp 2113ndash2124 2016
[24] H Bureau ldquoIodine encyclopedia of geochemistry A com-prehensive reference source on the chemistry of the earthrdquo inEncyclopedia of Earth Sciences Series W M White Ed copySpringer International Publishing AG 2016
[25] F C Kupper and C J Carrano ldquoKey aspects of the iodinemetabolism in brown algae a brief critical reviewrdquo Metal-lomics vol 11 pp 756ndash764 2019
[26] R Liteplo R Gomes P Howe and H Malcolm Fluorides-Environmental Health Criteria 227 p 290 World HealthOrganization (WHO) Geneva Switzerland 2002
[27] G F El-Said and M M El-Sadaawy ldquoSeasonal variation ofboron and fluoride in Tilapia nilotica from an Egyptian fishfarm in relation to Human health hazard assessmentrdquoHumanand Ecological Risk Assessment An International Journalvol 19 no 4 pp 930ndash943 2013
[28] WHO (World Health Organization) Bromide in Drinking-Water Background Document for Development of WHOGuidelines for Drinking-Water Quality WHO Press WorldHealth Organization Geneva Switzerland 2009
[29] G F El-Said and N A Sallam ldquo-e uptake of fluorideconcentration and its effects on the growth rate of shrimps(Palaemon elegans Rathke)rdquo Chemistry and Ecology vol 24no 3 pp 191ndash205 2008
[30] X Zhang J He B He and J Sun ldquoAssessment formationmechanism and different source contributions of dissolvedsalt pollution in the shallow groundwater of Hutuo Riveralluvial-pluvial fan in the North China Plainrdquo EnvironmentalScience and Pollution Research vol 26 no 35 pp 35742ndash35756 2019
[31] Y Zhu B Huang Z Zhu et al ldquoldquoCharacterization disso-lution and solubility of the hydroxypyromorphitendashhydroxyapatite solid solution [(PbxCa1minusx)5(PO4)3OH] at25 degC and pH 2ndash9rdquo Geochemical Transactions vol 17 no 2pp 1ndash18 2016
[32] G F El-Said M M El-Sadaawy A A Moneer andN A Shaltout ldquo-e effect of fluoride on the distribution ofsome minerals in the surface water of an Egyptian lagoon at
the Mediterranean Seardquo Egyptian Journal of Aquatic Researchvol 41 no 1 pp 31ndash39 2015
[33] Y Zhu Z Zhu X Zhao Y Liang and Y Huang ldquoChar-acterization dissolution and solubility of lead hydroxypyr-omorphite [Pb5(PO4)3OH] at 25ndash45degCrdquo Journal ofChemistry vol 2015 Article ID 269387 10 pages 2015
[34] M A Z Chahouki ldquoMultivariate analysis techniques inenvironmental sciencerdquo in Earth and Environmental SciencesDr Imran Ahmad Dar Ed InTech Open London UK 2011httpwwwintechopencombooksearth-and-environmental-sciencesmultivariate-analysis-techniques-inenvironmental-science
[35] J V Klump and C S Martens ldquoBiogeochemical cycling in anorganic-rich coastal marine basin 5 Sedimentary nitrogenand phosphorus budgets based upon kinetic models massbalances and the stoichiometry of nutrient regenerationrdquoGeochimica et Cosmochimica Acta vol 51 no 5 pp 1161ndash1173 1987
[36] R L Folk Petrology of Sedimentary Rocks University of TexasAustin TX USA 1974
[37] P Saenger ldquoA rapid spectrophotometric method for thedetermination of bromine in seawater and in the ash ofmarine algaerdquo Helgolander Wissenschaftliche Meer-esuntersuchungen vol 23 no 1 pp 32ndash37 1972
[38] P G Jeffery Chemical Methods of Rock Analysis PergamonPress New York NY USA 2nd edition 1975
[39] J D H Strickland and T R Parsons ldquoA practical handbook ofseawater analysisrdquo in Fisheries Research Board of CanadaBulletin 167p 311 Second edition Wiley Ottawa Canada1972
[40] B Horvath O Opara-Nadi and F Beese ldquoA simple methodfor measuring the carbonate content of soilsrdquo Soil ScienceSociety of America Journal vol 69 no 4 pp 1066ndash1068 2005
[41] K Grasshoff Methods of Seawater Analysis p 317 VerlagChemie Weinkeim Germany 1976
[42] R Danovaro D Marrale N Della Croce P Parodi andM Fabiano ldquoBiochemical composition of sedimentary or-ganic matter and bacterial distribution in the Aegean Seatrophic state and pelagic-benthic couplingrdquo Journal of SeaResearch vol 42 no 2 pp 117ndash129 1999
[43] APHA-AWWA-WPCF (American Public Health Associa-tion) Standard Methods for the Examination of Water andWaste Water American Public Health Association Wash-ington DC USA 20th edition 1999
[44] K I Aspila H Agemian and A S Y Chau ldquoA semi-auto-mated method for the determination of inorganic organicand total phosphate in sedimentsrdquo e Analyst vol 101no 1200 pp 187ndash197 1976
[45] J P Riley and D Taylor ldquoChelating resins for the concen-tration of trace elements from sea water and their analyticaluse in conjunction with atomic absorption spectrophotom-etryrdquo Analytica Chimica Acta vol 40 pp 479ndash485 1968
[46] G F El-Said and A El-Sikaily ldquoChemical composition ofsome seaweed from Mediterranean Sea coast Egyptrdquo Envi-ronmental Monitoring and Assessment vol 185 no 7pp 6089ndash6099 2013
[47] Directorate General of Health Services Ministry of Health andFamilyWelfare Government of India ldquoManual of methods ofanalysis of foodsrdquo in Fruit and Vegetable Productsp 57Directorate General of Health Services Ministry of Health andFamily Welfare Government of India New Delhi India2005
[48] A Gunnars S Blomqvist and C Martinsson ldquoInorganicformation of apatite in brackish seawater from the Baltic Sea
18 Journal of Chemistry
an experimental approachrdquo Marine Chemistry vol 91 no 1-4 pp 15ndash26 2004
[49] W M Haynes D R Lide and T J Bruno CRC Handbook ofChemistry and Physics A Ready Reference Book of Chemicaland Physical Data CRC Press Taylor amp Frances Group BocaRaton FL USA 97th edition 2017
[50] M S Masoud M I El-Samra and M M El-Sadawy ldquoWaterchemistry of el-mex bay west of Alexandria Egyptrdquo eEgypian Science Magazine vol 2 pp 70ndash78 2005
[51] F J Millero R Feistel D G Wright and T J McDougallldquo-e composition of standard seawater and the definition ofthe reference-composition salinity scalerdquo Deep Sea ResearchPart I Oceanographic Research Papers vol 55 no 1pp 50ndash72 2008
[52] S K El-Wakeel S A Morcos and A M Mahlis ldquo-e majorcations in Lake Maryut watersrdquo Hydrobiologia vol 36 no 2pp 253ndash274 1970
[53] A M Mahlis S A Morcos and S K El-Wakeel ldquo-e majoranions in Lake Maryut watersrdquo Hydrobiologia vol 36 no 2pp 275ndash294 1970
[54] A S Saad M A Massoud R A Amer and M A GhorabldquoAssessment of the physico-chemical characteristics andwater quality analysis of Mariout Lake southern of Alexan-dria Egyptrdquo Journal of Environmental and Analytical Toxi-cology vol 7 no 1 p 421 2017
[55] R Rumuri ldquoDataset on hydrogeochemical characteristics ofgroundwater and surface water in Kattumannarkoil TalukIndiardquo Data in Brief vol 32 Article ID 106058 2020
[56] P Szefer S W Fowler K Ikuta et al ldquoA comparative as-sessment of heavy metal accumulation in soft parts and byssusof mussels from subarctic temperate subtropical and tropicalmarine environmentsrdquo Environmental Pollution vol 139no 1 pp 70ndash78 2006
[57] N F Soliman G M El Zokm and M A Okbah ldquoRisk as-sessment and chemical fractionation of selected elements insurface sediments from Lake Qarun Egypt using modifiedBCR techniquerdquo Chemosphere vol 191 pp 262ndash271 2018
[58] G M El Zokm M I A Ibrahim L A Mohamed and M El-Mamoney ldquoCritical geochemical insight into Alexandria coastwith special reference to diagnostic ratios (TOCTN amp SrCa)and heavy metals ecotoxicological hazardsrdquo Egyptian Journalof Aquatic Research vol 46 no 1 pp 27ndash33 2020
[59] A S Likuku K B Mmolawa and G K GaboutloeloeldquoAssessment of heavy metal enrichment and degree of con-tamination around the copper-nickel mine in the SelebiPhikwe Region Eastern Botswanardquo Environment and EcologyResearch vol 1 no 2 pp 32ndash40 2013
[60] M K Khalil S E O Draz G M El Zokm and G F El-SaidldquoApportionment of geochemistry texturersquos properties and riskassessment of some elements in surface sediments from Bar-dawil Lagoon Egyptrdquo Human and Ecological Risk AssessmentAn International Journal vol 22 no 3 pp 775ndash791 2016
[61] M M El-Sadaawy and G F El-Said ldquoAssessment of fluoridein three selected polluted environments along the EgyptianMediterranean Sea effects on local populationsrdquo Human andEcological Risk Assessment An International Journal vol 20no 6 pp 1643ndash1658 2014
[62] USEPA ldquoSuperfund exposure assessment manualrdquo inOSWER Directive 92855-1EPA540l-88001Office of Emer-gency and Remedial Response Washington DC USA 1988
[63] USEPA ldquoExposure factors handbookrdquo in EPA6008-89043Office of Health and Environmental Assessment Wash-ington DC USA 1989
[64] Health Canada ldquoFederal Contaminated Site Risk Assessmentin Canadardquo Part II Health Canada Toxicological ReferenceValues (TRVs) Cat H46-204-368E Calgary Health CanadaOttawa Canada 2007
[65] J Iqbal S A Tirmizi and M H Shah ldquoStatistical appor-tionment and risk assessment of selected metals in sedimentsfrom Rawal Lake (Pakistan)rdquo Environmental Monitoring andAssessment vol 185 no 1 pp 729ndash743 2013
[66] USEPA (US Environmental Protection Agency) Region 6USAEPA ldquoMultimedia Planning and Permitting DivisionrdquoOffice of Solid Waste Center for Combustion Science andEngineering Washington DC USA 2005
[67] P Jeschke ldquoLatest generation of halogen-containing pesti-cidesrdquo Pest Management Science vol 73 no 6 pp 1053ndash10662017
[68] M A Shreadah O A El-Rayis N A Shaaban andA M Hamdan ldquoWater quality assessment and phosphorusbudget of a lake (Mariut Egypt) after diversion of wastewaterseffluentsrdquo Environmental Science and Pollution Researchvol 27 no 21 pp 26786ndash26799 2020
[69] J P Riley and M Tongudai ldquo-e major cationchlorinityratios in sea waterrdquo Chemical Geology vol 2 pp 263ndash2691967
[70] R B McCleskey D K Nordstrom D D Susong J W Balland J M Holloway ldquoSource and fate of inorganic solutes inthe gibbon river yellowstone national park Wyoming USArdquoJournal of Volcanology and Geothermal Research vol 193no 3-4 pp 189ndash202 2010
[71] G T F Wong and K-Y Li ldquoWinklerrsquos method overestimatesdissolved oxygen in seawater iodate interference and itsoceanographic implicationsrdquo Marine Chemistry vol 115no 1-2 pp 86ndash91 2009
[72] B S R V Prasad P D N Srinivasu P S VarmaA V Raman and S Ray ldquoDynamics of dissolved oxygen inrelation to saturation and health of an aquatic body a case forChilka Lagoon Indiardquo Journal of Ecosystems vol 2014 Ar-ticle ID 526245 17 pages 2014
[73] China Environmental Protection Agency EnvironmentalQuality Standards for Surface Water (GB3838ndash2002) NationalEnvironmental Protection Agency of China Beijing China2002
[74] Y Jia L Wang Z Qu and Z Yang ldquoDistribution con-tamination and accumulation of heavy metals in watersediments and freshwater shellfish from Liuyang RiverSouthern Chinardquo Environmental Science and Pollution Re-search vol 25 no 7 pp 7012ndash7020 2018
[75] A Moneer M El-Sadawy G El-Said and A Radwan ldquoBoronhuman health risk assessment relative to the environmentalpollution of Lake Edku Egyptrdquo Journal of King AbdulazizUniversity vol 23 no 2 pp 41ndash55 2012
[76] C B Tabelin T Igarashi T Arima D Sato T Tatsuhara andS Tamoto ldquoCharacterization and evaluation of arsenic andboron adsorption onto natural geologic materials and theirapplication in the disposal of excavated altered rockrdquo Geo-derma vol 213 pp 163ndash172 2014
[77] G Aloisi K Wallmann M Drews and G BohrmannldquoEvidence for the submarine weathering of silicate minerals inBlack Sea sediments possible implications for the marine Liand B cyclesrdquo Geochemistry Geophysics Geosystems vol 5no 4 pp 1ndash22 2004
[78] C Degueldre and V Cloet ldquoPore water colloid properties inargillaceous sedimentary rocksrdquo Science of e Total Envi-ronment vol 569-570 pp 423ndash433 2016
Journal of Chemistry 19
[79] J A Higgins and D P Schrag ldquoRecords of Neogene seawaterchemistry and diagenesis in deep-sea carbonate sedimentsand pore fluidsrdquo Earth and Planetary Science Letters vol 357-358 pp 386ndash396 2012
[80] H Schroeder A-L Fabricius D Ecker T A Ternes andL Duester ldquoMetal(loid) speciation and size fractionation insediment pore water depth profiles examined with a newmesoprofiling systemrdquo Chemosphere vol 179 pp 185ndash193 2017
[81] Y Song and G Muller ldquoFreshwater sediments sinks andsources of brominerdquo Naturwissenschaften vol 80 no 12pp 558ndash560 1993
[82] M E Goher H I Farhat M H Abdo and S G Salem ldquoMetalpollution assessment in the surface sediment of Lake NasserEgyptrdquo Egyptian Journal of Aquatic Research vol 40 no 3pp 213ndash224 2014
[83] G F El-Said M M El-Sadawy and A A Moneer ldquoIncor-poration of fluoride and boron into surface sediments alongthe Egyptian Mediterranean coastrdquo Egyptian Journal ofAquatic Research vol 36 no 4 pp 569ndash583 2010
[84] B Gilfedder G M Petri M Wessels and H Biester ldquoAniodine mass-balance for Lake Constance Germany insightsinto iodine speciation changes and fluxesrdquo Geochimica etCosmochimica Acta vol 74 no 11 pp 3090ndash3111 2010
[85] E Korobova L Kolmykova B Ryzhenko et al ldquoDistributionand speciation of iodine in drinking waters from geochem-ically different areas of Bryansk region contaminated after theChernobyl accident in relation to health and remediationaspectsrdquo Journal of Geochemical Exploration vol 184pp 311ndash317 2018
[86] V Zic V W Truesdale and N Cukrov ldquo-e distribution ofiodide and iodate in anchialine cave watersmdashevidence forsustained localised oxidation of iodide to iodate in marinewaterrdquoMarine Chemistry vol 112 no 3-4 pp 168ndash178 2008
[87] M B Heeb J Criquet S G Zimmermann-Steffens andU Von Gunten ldquoOxidative treatment of bromide-containingwaters formation of bromine and its reactions with inorganicand organic compoundsmdasha critical reviewrdquo Water Researchvol 48 pp 15ndash42 2014
[88] V Sivasankar A K Darchen and R Omine SakthivelldquoChapter 2 ldquofluoride a world ubiquitous compound itschemistry and ways of contaminationrdquo in Surface ModifiedCarbons as Scavengers for Fluoride fromWater V SivasankarEd pp 5ndash32 copy Springer International Publishing Switzer-land Cham Switzerland 2016
[89] O Cabestrero P Del Buey and M E Sanz-Montero ldquoBio-sedimentary and geochemical constraints on the precipitationof mineral crusts in shallow sulphate lakesrdquo SedimentaryGeology vol 366 pp 32ndash46 2018
[90] M A Hassaan O A El-Rayis and E I Hemada ldquoEstimationof the redox potential of lake mariut drainage system (Qalaaand Umum drains)rdquoHydrology vol 5 no 6 pp 82ndash85 2017
20 Journal of Chemistry
6302 km2 due to the land reclamation and the constructionof a series of roads in addition to drainage and navigationcanals that divided the lake into basins-ese roads and canalshave become a physical barrier that prevented the trans-portation of lake water fish and fishermen from a basin toanother [17] Unfortunately the lake receives large amountsof untreated urban municipal industrial wastewater efflu-ents drainage water and domestic wastewater from differentdrains such as El Umoum drain which directly dischargesindustrial effluents from different companies such as the Petrojet Company El-Amreya Petroleum Company and El-Amreya Company of spinning and weaving besides theEgyptian Petrochemical Company in addition to domesticand agricultural wastewater into the lake -e El-Qalaadrainage channel discharges 676000m3 dayminus1 of primarytreatment municipal sewage and agricultural wastewaterevery day the El Nubaria Canal discharges industrial agri-cultural and household waste [18] In addition some builtroads had divided the lake into four separate basins and eacharea of the physical features and these basins are as followsthe Main Basin the South West Basin the North West Basinand the Fishery Basin with areas of 252 210 126 and42 km2 respectively [18 19] -ese basins affect the watercycle in the lake so their role is to minimize the negativeimpact on lake water quality Due to the economic impor-tance of Lake Mariout officials active civil society the publicand international development organizations are facing manychallenges of sustainable development and environmentalimprovement-ey all share a common interest in developinga set of indicators that play an important role in guiding theplanning of this precious ecosystem and overcoming thevulnerability of human health to waste
Halogens mainly concentrate in the earthrsquos surfacereservoirs including seawater and sediments -e halogenelements show great resemblances to one another in theirgeneral chemical behavior and in the properties of theircompounds with other elements -ey carry out significantroles in the global transformation processes [20] In addi-tion halogens naturally exist in the form of monovalentanions metal-bound salts silicate minerals and nonsilicateminerals [20] Amongst the other halogens chloride (Cl)exhibits systematically different behavior due to its ionic sizeor its elemental abundance Fluorine is strongly electro-negative being the only element in the periodic table that ismore electronegative than oxygen Fluorides (such asfluorite cryolite and fluorapatite) traditionally combine themost naturally distributed minerals and usually have manyeconomic uses [21] -erefore it enters the social envi-ronment through alternative methods (gradual erosion andweathering process) and industry (locally produced phos-phate fertilizers semiconductors aluminum special drugscosmetics etc) [22] Fluoride has been recorded an ab-normal concentration in the seawater along the Mediter-ranean coast of Egypt In addition to the large amount ofminerals that may be dissolved in the sediment-water in-terface the Mediterranean coast of Egypt is also adverselyaffected by raw sewage domestic agricultural and industrialwaste [23] Bromine is used in the manufacture of agri-cultural pesticides disinfectants film photography lampsdyes textiles cosmetics etc [24]
Iodine is a weakly electronegative redox sensitive ele-ment which is very important in many biochemical path-ways With its low abundance it is considered an essentialelement for life [25] Fluoride (F) is considered as an es-sential element for oral health and bone formation [26] Inaddition fluoride is functionally an effective metabolic in-hibitor However it has a constructive interference with themetabolism of proteins lipids and carbohydrates in livingorganisms [27] Both bromide (Br) and chloride (Cl) exist inthe body fluids of animals and mortals and their abundancedepends on their intake and excretion [28] Although hal-ogens have effective biological functions high levels ofhalogens may be toxic Large amounts of bromide (Br) maycause some adverse symptoms including nausea andvomiting abdominal pain coma and paralysis [28] Ex-cessive iodide (I) may cause goiter hypothyroidism orhyperthyroidism in exposed people [28] Ingestion offluoride can cause nausea vomiting abdominal pain di-arrhea fatigue drowsiness coma convulsions cardiac ar-rest and eventual death [29] It can also affect physiologicalprocesses such as metabolism growth and reproduction
In order to determine the pollution source of a lake it isuseful to analyze the chemical properties of the water andstudy the main solute sources-e pollution by dissolved saltis related to the large increase of several dissolved saltscaused by human activities [30] that is the total dissolvedcontent in the water system and the increase in the contentof anions and cations -e gradual increase in dissolved saltcan play an important role in the aquatic environment butexcessive salt may have harmful effects on the ecosystemSimilarly the chemical balance in the aquatic system as well
Figure 1 Sampling sites along Lake Mariout
2 Journal of Chemistry
as the solubility and precipitation of the salt contained alsohelps to track pollution [31] -e formation and internalinteraction of different soluble and insoluble salts in aquaticsystems are affected by the physical and chemical factors ofthe ecosystem [31] -e behavior of soluble salts in theaquatic systems can provide information about the forma-tion of precipitated salts -e stability of the precipitated saltis affected by the product of the molar concentration of itsions and the equilibrium solubility constant of the precip-itated salt According to previous studies under alkalineconditions fluorapatite minerals had an important role inreducing the solubility of calcite in the apatite supernatantand solving the destructive effects of fluoride pollution onLake Edku in Egypt [32] Small amounts of bromine arefound in certain minerals (such as apatite amphibole andbiotite) [24] In addition calcium hydroxyapatite canremove toxic ions from the water environment [33]
By multivariate analysis the ecological and environ-mental multivariate data can assess the environmental im-pacts and monitor large-scale biodiversity changes [34]Multivariate analysis is widely used in environmental sci-ence It can help ecologists discover the structure of manycharacteristics of the data and the previous relatively ob-jective summary for easy understanding However it is verycomplicated in theoretical structure and operation methods
To the best of our knowledge relatively little studies havebeen evaluated for the long-term changes in concentrationsof halogens ie bromine fluorine chlorine and iodine andtheir relative to pollution status in surface water pore waterand sediments partitions in the polluted Lake Mariout -eaims of this work are to present an overview of the evalu-ation of halogenrsquos content and to examine the relation ofpollution by halogens as well as to find out their possibleinteractions with dissolved and precipitated salts in MarioutLake which is suffering from the huge amounts of differenttypes of waste waters
2 Materials and Methods
21 Sampling Sites -irteen sampling sites were selected torepresent the survey area of Lake Mariout and the incomingdrainage (Figure 1) Surface water sediment pore water andsediment samples were collected from the thirteen sites Site 1and site 2 were affected by the parallel pumping station(pumping water from the Abis drainageasymp 400000 m3dayminus1 andother openings from El Drain [19] Site 3 represented thecombined discharge of El-Qalaa drainage and WesternWastewater Treatment Plant (WWTP) Sites 4ndash6 belonged tothe Main Basin area and were affected by the drainage of El-Qalaa and El Umoum Site 6 represented the contaminated areabefore the El-Mex pumping station Site 7 was located in theNorthWest Basin In addition to saltmarshes it was also directlyaffected by many industrial and petrochemical companies -eSouth West shallow basin was adversely affected by the localwater sources of El Umoum and El Nubaria drains and its sitewas 8ndash10 Stations 11ndash13 were located in the El-Qalaa the ElNubaria and the El Umoum drains outside the lake -e lastthree locations were chosen as reference locations to describe thepotential pollution of the water discharged into the lake
22 Sampling Processes Surface water and bottom sedimentsamples were collected from thirteen selected sites along thelake and the drains of depth range 15ndash20m by a rubber boatduring autumn 2019 (Figure 1) Nitrile gloves were usedduring the sampling duration
For water sampling thirty-nine airtight clean 5 L poly-ethylene bottles for water sampling were rinsed three timeswith double distilled water and then dried Triplicate col-lected surface water samples were collected by the Niskinwater sampler from each sampling site However thesesurface water samples were not filled in 5 L cleaned poly-ethylene bottles in which they can be preserved Each watersample from the study site was divided into two portions-e first portion was stored in a brown closed polyethyleneplastic bottle the second part was stored in a closed whitebottle for the determination of heavy metals -e subdividedsamples were carefully transported to the laboratory in an icebox However surface water temperature (Tw) pH salinityand TDS value of water samples weremeasured on-site usingportable equipment (CTD YSI 566) -e dissolved oxygen(DO) sample was fixed in a closed brown glass bottle on-siteTurbidity was measured by using the conventional whiteenameled Secchi-disc
For sediment sampling three replicate sediment sampleswere collected from 13 sampling sites using a Van-Veen grabsampler stored in a clean polyethylene bag and transportedto the laboratory in an ice box
23 Sample Preparation In the laboratory the first portionof the subdivided surface water was stored in a brownairtight polyethylene plastic bottle at minus20degC for halogenanalysis -e second portion was divided into two parts andone of which was stored in a plastic colorless bottle at minus20degCto determine phosphorus and silicon in the form of phos-phate and silicate -e other part was kept in the refrigeratoruntil the main water components (calcium magnesiumsodium potassium lithium sulfate and boron) and heavymetals (copper manganese zinc and iron) were analyzed
In addition pore water was extracted from each sedi-ment sample by a centrifuge (Hettich Zentrifugen Universal320 R Andreas Hettich GmbH amp CoKG 78532 TuttlingenGermany) for 20min and at a speed of 10000 rpm [35]
First in each extracted pore water sample pH and Spermilwere detected -en one-third of each extracted pore watersample was preserved in a brown polyethylene plastic bottlewith a stopper and kept at minus20degC for halogen determinationWhile two-third portion was preserved in colorless well-closed plastic bottles and kept at minus20degC for analysis ofphosphorus silicon calcium magnesium sodium potas-sium lithium sulfate and boron calcium magnesiumsulfate boron and heavy metals concentrations (Cu MnZn and Fe)
On the other hand the sediment samples were spread ona clean plastic plate at room temperature and then air driedAfter that the particle size of the air-dried sediment samplewas accurately estimated [36] -e digestion of the sedimentsample was performed by heating the sample with an acidmixture (3mL HNO3 2mL HClO4 and 1mL HF) at 70degC in
Journal of Chemistry 3
a closed Teflon container -e extraction of fluoride bro-mide and iodide from sediment samples was carried outafter the fusion of Na2CO3 with each sediment sample[37 38]
24 Samples Analyses -e carbonate and bicarbonate ofsurface and pore waters were determined in the laboratory bythe titration method [39 40] pH and TDS values of the porewater were measured in the laboratory using portableequipment (CTDYSI 566) From the salinity value chlorosity(Cl) in the surface and pore waters and chlorinity (Clpermil)wereeffectively calculated [39] -e DO of water samples wasaccurately measured by Winklerrsquos method [41] Porosity wasmeasured based on the weight difference between dry and wetsediment samples [42] Calcium and magnesium in surfaceand pore waters and digested sediment samples were carefullydetermined by the titrimetricmethod using Eriochrome BlackT and Murexide indicators [43] Sodium potassium andlithium contents in surface and pore waters and digestedsediment samples were estimated by the flame photometerinstrument (lame139 photometer PFP JENWAY 7) Inor-ganic phosphorus and total phosphorus contents in thesurface and pore waters and sediment samples were deter-mined [43 44] Silicate was measured in the surface and porewaters and digested sediment samples by the calorimetricmethod [39] Curcumin colorimetry was used to determineboron in surface water pore water and digested sediment[43] -e turbidity method was used to estimate sulfate in thesurface water and pore water and digested sediment samples[43] -e heavy metals (Cu Mn Zn and Fe) dissolved in thesurface and pore water samples were extracted with chelatingresin and measured with an atomic absorption spectropho-tometer (GBC Savant AA Scientific equipment serial no A7275 GBC) [45] Fluoride concentration was determined bythe colorimetric method using the zirconium alizarin red Smethod [46] -e bromide was determined by titration usinga thiosulfate solution [41] -e catalytic reduction methodusing the Ce(IV)-As(III) was applied to determine the iodineconcentration [43] -e chloride content in sediments wasestablished by Mohrrsquos method [47]
25 Quality Control and Quality Assurance A sedimentreference material (IAEA-405 International Atomic EnergyAgency Vienna Austria) was used to determine the sedi-ment samplersquos quality controlquality assurance -e re-covery percentages for the selected metals from the standardreference material were in the range of 970ndash1011 Foreach variable an examined calibration procedure of threeexternal standards was performed One of the externalstandards must be of a concentration near but above themethod detection limit -e other concentrations shouldcorrespond to the range of a variable concentration expectedin the sample -e working calibration curve was verified oneach working shift by the measurement of one or morecalibration standards
26 Saturation Index (SI) -e Saturation Index (SI) of 23and 15 structures in surface water and pore water sampleswere calculated respectively [23 48]
It can be calculated from the division of the product of themolar concentrations (IAP [49]) of their component by theirequilibrium solubility constant (Table 1) Moreover SI of someminerals such as anhydrite (CaSO4) gypsum (CaSO42H2O)calcium phosphate (Ca3(PO4)2) magnesium phosphate(Mg3(PO4)2) calcite (CaCO3) aragonite (CaCO3) dolomite(CaMg(CO3)2) magnesite (MgCO3) fluorapatite (FAPCa5(PO4)3F) hydroxyapatite (HAP Ca5(PO4)3OH) octacal-cium phosphate (OCP Ca4H(PO4)325H2O) and carbonate-fluorapatite (CFAP Ca10(PO4)5(CO3)F272(OH)028) besidessome precipitated salts (Fe(OH)2 Fe(OH)3 FePO42H2OMg(OH)2 Mg3(PO4)2 Mn(IO3)2 KIO4 KCIO4 ZnCO3ZnCO3H2O Zn(OH)2 and Zn(IO3)22H2O) was calculatedby the following equation [23 48]
SI logIAPKsp
1113888 1113889 (1)
where IAP and Ksp were the product of the ion activity andthe equilibrium solubility constant of each precipitated saltor mineral SI values represented the under saturation(SIlt 1) or over saturation (SIgt 1) situation of each pre-cipitated salt or mineral
27 Palmerrsquos Method and Piper Ternary Diagram -e dis-solved salts in the surface and pore waters in the in-vestigated area were utilized by Palmerrsquos method andpiper ternary diagram Palmerrsquos method by using the millequivalent percentage of the major anions (Clminus SO4
minus2and HCO3
minus) and cations (K+ Na+ Ca+2 and Mg+2) [50]-is method assumed that the concentration of positiveions and negative ions are in equilibrium ie the sum ofthe concentrations of positive ions in meq Lminus1 is equal tothe sum of the concentrations of negative of ions con-sidering only the major ions -is hypothesis can beverified by converting the average ion concentration ofsurface water and pore water along the study areafrom mg Lminus1 in Table 2 to meq Lminus1 -en the concen-trations were further converted into a percentage of eachion in relation to the total concentration of positive ionsin the case of a positive ion and in relation to the totalconcentration of negative ions in the case of a negativeion -e percentage of each cation and anion was rep-resented in two rectangles in cm to evaluate the relativeformed soluble salts Piper ternary diagram explores theorigin of the dissolved salts in surface and pore waters ofthe lake water besides the effects of drainage sources onthem [55]
28 Multivariate Analysis Multivariate analysis includingcorrelation multiple stepwise linear regression and clusteranalysis has been used to predict the role of halogens in thepollution status of Lake Mariout Multivariate analysis canbe used in monitoring research because they can reduce the
4 Journal of Chemistry
cost of further environmental investigations [56ndash58] -emultivariate analysis using the correlation matrix with acorrelation coefficient (r) multiple stepwise linear regressionwith a coefficient (R) and cluster (tree clustering) at asignificance level of ple 005 is estimated by STATISTICA 99edition At the same time the principal component (PCA)can be estimated through SPSS 15 evaluation
29 Enrichment Factor (EF) EF of the determined elements(Ca Mg Na K Li B P Cu Zn Mn Fe F Cl Br and I) wascalculated by using the equations described (equations (2)and (3)) [59 60]
EF Cm sample
MedianCm Background + 2 times MADCm Background( 1113857
(2)
where Cm was the element concentration Median CmBackground represented median concentration of an ele-ment in the background and MAD Cm Background was themedian absolute deviation from the median calculated fromthe given equation
MAD median xi minus medianj xj1113872 111387311138681113868111386811138681113868
111386811138681113868111386811138681113874 1113875 (3)
-e EF values were classified into five categories defi-ciency tominimal (EFlt 2) moderate (2ltEFlt 5) significant(5ltEFlt 20) very high (20ltEFlt 40) and extremely highenrichment (EFgt 40)
210 Human Health Risk Assessment -e human healthhazard of surface water and sediment ingestion and dermalcontact was assessed by using the estimated daily intake
Table 1 -e hypothetical precipitated salts in surface and pore waters along Lake Mariout
Site 1 2 3 4 5 6 7 8 9 10 11 12 13SI of precipitated salts and minerals
Surface waterCalcite 128 138 340 146 236 303 295 297 205 258 312 126 311Aragonite 103 112 315 120 211 278 270 272 180 233 287 101 286CaSO405 H2O 208 188 126 157 156 155 170 179 199 171 115 075 181CaSO42H2O 196 176 114 144 143 143 158 167 187 158 103 063 169Ca3(PO4)2 2486 2424 2424 2424 2424 2424 2424 2424 2424 2424 2424 2424 2424Ca(IO3)2 157 137 137 137 137 137 137 137 137 137 137 137 137Ca(IO3)26H2O 1006 986 986 986 986 986 986 986 986 986 986 986 986OCP 3964 3569 3569 3569 3569 3569 3569 3569 3569 3569 3569 3569 3569HAP 4574 4349 4349 4349 4349 4349 4349 4349 4349 4349 4349 4349 4349FAP 4277 5036 5038 5195 5171 5131 5090 4982 5131 5081 4903 5095 5163CFAP 6089 1685 1786 1818 1784 1902 1883 1785 1764 1859 1604 1824 1914Fe(OH)2 1196 1217 1196 1189 1208 1059 1176 1158 1007 1192 1205 1199 1152Fe(OH)3 3544 3564 3543 3536 3555 3407 3524 3505 3354 3539 3552 3546 3499FePO42H2O 1053 1074 1053 1046 1065 916 1033 1015 864 1049 1062 1056 1008Mg(OH)2 1215 1206 1131 1171 1173 1159 1179 1188 1170 1183 1151 1152 1168Mg3(PO4)2 085 1345 1121 1240 1245 1205 1264 1291 1236 1276 1180 1184 1229Mn(IO3)2 025 243 354 303 247 312 226 055 183 198 064 262 042KIO4 576 570 552 549 565 564 559 554 551 560 489 551 548KCIO4 495 489 471 468 484 483 478 473 470 479 408 470 467ZnCO3 414 404 613 455 560 560 586 573 491 530 659 472 581ZnCO3H2O minus018 minus027 181 024 128 128 154 142 060 099 227 041 149Zn(OH)2 1198 1189 1199 1210 1254 1194 1223 1232 1216 1207 1249 1227 1203Zn(IO3)22H2O 366 357 367 378 422 362 391 400 383 375 417 395 371Pore waterFluorite 200 211 106 195 346 309 345 317 228 246 307 365 277CaSO405 H2O 370 177 190 200 168 178 202 255 203 212 191 179 211CaSO42H2O 358 165 178 188 155 166 190 243 191 200 178 167 199Ca3(PO4)2 2958 2424 2424 2424 2424 2424 2424 2424 2424 2424 2424 2424 2424Ca(IO3)2 315 137 137 137 137 137 137 137 137 137 137 137 137Ca(IO3)26H2O 1164 986 986 986 986 986 986 986 986 986 986 986 986OCP 4594 3569 3569 3569 3569 3569 3569 3569 3569 3569 3569 3569 3569HAP 5361 4349 4349 4349 4349 4349 4349 4349 4349 4349 4349 4349 4349FAP 5126 5295 5399 5270 5460 5318 5327 5338 5321 5311 5420 5373 5391CFAP 7833 1775 2068 1752 2049 2078 1990 2015 1963 2026 2121 2024 2060MgF2 299 138 177 060 262 232 095 209 212 243 222 251 203Mg(OH)2 1395 1439 1408 1400 1428 1420 1346 1425 1418 1438 1412 1391 1414Mg3(PO4)2 987 2442 2417 2355 2469 2207 2128 2317 2243 2260 2387 2132 2378KIO4 564 568 575 557 561 560 570 566 558 571 551 543 564KCIO4 483 487 494 476 480 479 489 485 477 490 470 461 483
Journal of Chemistry 5
(EDI) hazard quotient (HQ) and hazard index (HI) as givenin equations (4)ndash(11)
2101 For Surface Water Estimated daily intake of surfacewater ingestion and dermal contact (EDIIngw and EDIDermw)were computed by the following equations [61]
EDIIngw(mgkgday) (CW times CR times ET times EF times ED)
(AT times BW) (4)
EDIDermw(mgkgday) (CW times SA times PC times ET times EF times ED times CF)
(AT times BW)
(5)
where CWwas the element concentration in water (mg Lminus1)CR was the contact time (50mL hminus1) ET was the exposuretime (26 h dayminus1) EF was the exposure frequency (7 dayyearminus1) ED was the exposure duration (60 year) ATwas theaverage time (60times 365 day yearminus1) BWwas (707 kg) SAwas
the skin surface area (5700 cmminus2) PC was the dermalpermeability constant (0001 cm hminus1) and CF was theconversion factor for water (10times10minus6 kg mgminus1) [62ndash65]
2102 For Sediment Estimated daily intake of sediment byingestion and dermal contact (EDIIngs and EDIDerms) werecalculated according to the following equations [60]
EDIIngS(mgkgday) CS times IngS times RAFS times EFS( 1113857
(AT times BW) (6)
EDIDermS(mgkgday) CS times IngS times ED times SA times AF times ABS( 1113857
(AT times BW)
(7)
where CS was the concentration of the contaminant insediment (mg gminus1) IngS was the ingestion rated of sediment(80times10minus5mg kgminus1) RAFS was the relative absorption factorof sediment (058) EFS was the exposure frequency (30 day
Table 2 Distribution of the studied variables in surface water (w) and their chlorinity ratios along Lake Mariout
Determined variables Minimum Site Maximum Site Average SD Seawatera Lake Marioutbcd
Physicochemical variablesTw 137 10 1534 11 1759 134Salinity (Spermilw) 23 13 79 1 489 152Chlorinity (Clpermilw) 205 13 71 1 438 137 1898TDSw (mg Lminus1l) 24635 13 7683 1 48503 152874Turbidity (NTU) 166 8 385 12 1296 1174DOw (mg Lminus1l) 0 6 1241 2 605 483 214ndash563d
pHw 744 13 899 2 710ndash860d
CO3w (mg Lminus1) 12 1 amp 2 1152 3 31 388HCO3w (mg Lminus1) 7808 3 19032 12 1147 321Bw (mg Lminus1) 05 7 1661 1 691 411 45Pw (μg Lminus1) 003 8 126 5 029 033Siw (μg Lminus1) 009 12 699 4 317 191Caw (mg Lminus1) 6092 12 3527 8 17703 735 400 549 818ndash1464d
Mgw (mg Lminus1) 9725 3 66615 1 28684 16002 1272 1201Naw (mg Lminus1) 231 11 1420 1 101115 2972 10556 10332Kw (mg Lminus1) 8 11 59 1 3769 123 380 585Liw(mg Lminus1) 0139 11 017 1 0154 001 017SO4w (mg Lminus1) 1978 12 34111 9 16856 9488 2649 4245Cuw (μg Lminus1) 204 3 621 7 317 113 7Mnw (μg Lminus1) 001 8 amp13 198 3 315 554 10Few (μg Lminus1) 009 9 1392 13 69 419 40Znw (μg Lminus1) 527 2 2367 5 1085 578 20Fw (mg Lminus1) 015 11 396 12 204 117 13Clw (mg Lminus1) 2048 13 7284 1 4397 1400 18980Brw (mg Lminus1) 506 12amp13 541 5 1813 1891 65 592Iw (μg Lminus1) 566 10 541 4 1108 1296 60Ion chlorinity ratioCawClw 170Eminus 02 12 100Eminus 01 13 440Eminus 02 240Eminus 02 213Eminus 02 335Eminus 02MgwClw 250Eminus 02 3 110Eminus 01 13 640Eminus 02 230Eminus 02 669Eminus 02 733Eminus 02NawClw 650Eminus 02 11 380Eminus 01 13 240Eminus 01 720Eminus 02 560Eminus 01 635Eminus 01KwClw 220Eminus 03 11 150Eminus 02 13 890Eminus 03 290Eminus 03 210Eminus 02 360Eminus 02LiwClw 240Eminus 05 1 700Eminus 05 13 380Eminus 05 110Eminus 05 939Eminus 06SO4wClw 540Eminus 03 12 110Eminus 01 13 420Eminus 02 310Eminus 02 140Eminus 01 260Eminus 01BwClw 978Eminus 05 7 332Eminus 03 9 670Eminus 03 170Eminus 03 895Eminus 04FwClw 430Eminus 05 11 140Eminus 03 13 540Eminus 04 420Eminus 04 670Eminus 05BrwClw 140Eminus 03 12 160Eminus 02 9 440Eminus 03 500Eminus 03 350Eminus 03 360Eminus 05IwClw 940Eminus 04 1 160Eminus 02 4 300Eminus 03 400Eminus 03a[51] b and c[52 53] d[54]
6 Journal of Chemistry
yearminus1) AF was the adherence factor (007mg cmminus2) andABS was the dermal absorption factor (0001 unit less)[65 66]
Hazard index (HI) is the total chronic hazard attribut-able to exposure to all determined contaminants (i) througha single exposure pathway of the ingestion and dermalcontact of water (HIIngw and HIDermw) and sediment (HIIngsand HIDerms) was given as follows [60]
HIIngW 1113944HQ IngW( 1113857i (8)
HIDermW 1113944HQ DermW( 1113857i (9)
HIIngS 1113944HQ IngS( 1113857i (10)
HIDermS 1113944HQ DermS( 1113857i (11)
3 Results and Discussion
31 Distribution of Halogens and Tested Variables in SurfaceWater
311 Distribution of Halogens in Surface Water -e rangeand average value of halogens in the surface water in thisstudy show a sequence of ClwgtBrwgt Fwgt Iw (Table 2 andFigure 2)-e current study indicate that the water sample ofpumping station (site 6) attained high concentrations offluoride (28mg Lminus1) chloride (38878mg Lminus1) and bromide(181mg Lminus1) and low iodide (641 μg Lminus1) contents (Fig-ure 2) High levels of F Br and I are detected in the MainBasin region which is affected by the drainage of El-Qalaaand El Umoum containing the agricultural and industrialwastes However halogens are involved in the manufactureof pesticides (herbicides fungicides insecticidesacaricidesand nematicides) [67] Plus halogens are produced in theproduction of fertilizers products [67] -e presented resultsof halogens in the studied lake region reflect anomalousdistribution and are mainly affected by water dischargedfrom the drainage sources However the highest fluoridebromide and iodide contents of 377mg Lminus1 6553mg Lminus1and 5410 μg Lminus1 respectively are recorded in the MainBasin affected by El-Qalaa and El Umoum drains Amongthe halogens chloride shows high levels in surface waterespecially in site 1 (72837mg Lminus1) site 2 (65218mg Lminus1)and site 10 (51687mg Lminus1) which are also related to theirlevels in the water of the drains (Figure 2) On the meantimethe lowest Spermilw and Clpermilw are observed at site 13 (ElUmoum Drain) Most of the studied variables have chlo-rinity ratios relatively lower than those measured for LakeMariout andor seawater [51ndash53 68 69] -is is mainly dueto the accumulation of wastewater from Abis and ElUmoum where agricultural products such as fertilizers andbiocides are deposited in industrial products [19]
Due to the increase in chloride content in surface watersamples the conservativeness of the chlorinity ratio is usedto describe the contamination precipitation and dissolutionof sediment components [70] -e FCl ratio in the studyarea is higher than open seawater (430Eminus 05) of a range
430Eminus 05ndash140Eminus 03 and average 540Eminus 04 -e BrClratio is relatively similar to that of seawater (Table 2) -ehighest FCl BrCl and ICl ratios in surface water140Eminus 03 160E ndash 02 and 160Eminus 02 are recorded in site 13(El Umoum drain outside the lake) site 9 (South West Basinin the lake) and site 4 (Main Basin in the lake) -erefore itcan be concluded that the distribution of halogens in thesurveyed area is greatly affected by the drainage of the El-Qalaa El Umoum and the El Nubaria drains
312 Distribution of Tested Variables in Surface Water-e range and average values of the tested variables (Tw Spermilw Clpermilw TDSw turbidity DOw pHw CO3w HCO3w BwPw Siw Caw Mgw Naw Kw Liw SO4w Cuw Mnw Few andZnw) in surface waters of the present study are listed inTable 2 Turbidity fluctuates from 166 to 3850 NTU at sites8 and 12 respectively DO is completely depleted at sites 5 6and 11 and has the highest amount 1241mg Lminus1 at site 2with an average 605mg Lminus1 relatively similar to the reportedLake Mariout value (214ndash563mg Lminus1 [54]) (Table 2) -eaverage content of DO in the lake is higher than those re-ported for the ocean seawater (32ndash48mgL) [71] -e levelsof DO probably relate to the oxygen-producing processes ofthe photosynthesis processes of phytoplankton and mac-rophytes [72] -e presented results indicate that site 1(affect by Abis drainage) is the most affected area in the lakeas it shows the highest contents of Bw Clw Mgw Naw KwLiw and SO4w -e most important feature in the concen-trations of heavy metals Cuw Mnw and Znw in surface wateris that they possess average values lower than those reportedfor the threshold guideline (10 100 and 50 μg Lminus1) [73 74]
-e present study clears out a descending trend in thesurface water average concentrations of halogens andtested variables in the lake as follows TDSw gtClw gtNaw gtMgw gtCaw gt SO4w gtHCO3wgtKw gtCO3w gt Bw gt Brwgt FwgtLiw gt Znw gt Few asymp Siw gtMnw gt Pw gt Iw (Table 2)
313 Interactions of Halogens and Tested Variables inSurface Water Chloride in surface water is significantlyrelated to the drainage water content showing good cor-relations with Tw (r 0631 ple 0028) and pHw (r 0769ple 0003) (Supplementary Table 1) -e negative moderaterelation of Fw and Ip (r 0606 ple 0037) may indicatereplacement of iodine in pore water by fluoride of the surfacewater-emoderate relationship between fluoride in surfacewater and CO3w (r minus0632 ple 0027) and HCO3w(r 0593 ple 0042) may be related to carbonate exchangeand the formation of fluorite minerals (CaF2) [23]
-e correlation matrix reflects that the observed ex-traordinary levels of Bw in the surface water samples aremost probably due to its exchange with the different sedi-ment components not related to the discharged waters(Supplementary Table 1) -is findings is supported by theweak B correlation with Cuw (r minus0587 ple 0045) andgood correlation with Fs (r minus0666 ple 0018) [75 76]However Cuw is one of the pollutants that can be exchangedin drainage water -e correlations of Mgw amp Naw (r 0629
Journal of Chemistry 7
1
23
4
56
7
8
9
10
2986degE 2988degE 2990degE 2992degE
310
8degN
311
0degN
311
2degN
311
4degN
311
6degN
El-mex
pumping
statio
n Main Basin
of Lake Maryout
Southwest Basin
Qalaa Drain
El Umoum Drain
Northwest BasinFish
ery Basi
nEl Nubaria Drain
3311 to 38883888 to 43934393 to 5115
5115 to 65226522 to 7284
(a)
1
23
4
56
7
8
9
10
2986degE 2988degE 2990degE 2992degE
310
8degN
311
0degN
311
2degN
311
4degN
311
6degN
El-mex
pumping
statio
n
Main Basinof Lake Maryout
Southwest Basin
Qalaa Drain
El Umoum Drain
Northwest Basin
Fishery
BasinEl Nubaria Drain
069 to 127127 to 169169 to 242
242 to 277277 to 377
(b)
El-mex
pumping
statio
n
Main Basin of Lake Maryout
South west Basin
North west Basin
1
23
4
56
7
8
9
10
2986degE 2988degE 2990degE 2992degE
310
8degN
311
0degN
311
2degN
311
4degN
311
6degN
Qalaa Drain
El Umoum Drain
Fishery
BasinEl Nubaria Drain
613 to 852852 to 14381438 to 1732
1732 to 52745274 to 6554
(c)
El-mex
pumping
statio
n
Main Basin of Lake Maryout
Southwest Basin
Northwest Basin
1
23
4
56
7
8
9
10
2986degE 2988degE 2990degE 2992degE
310
8degN
311
0degN
311
2degN
311
4degN
311
6degN
Qalaa Drain
El Umoum Drain
Fishery
BasinEl Nubaria Drain
566 to 671671 to 761761 to 817
817 to 922922 to 5411
(d)
Figure 2 Distribution of halogens (Cl F Br and I in surface water of LakeMariout (a) Cl (mg Lminus1) (b) F (mg Lminus1) (c) Br (mg Lminus1) and (d) I(μg Lminus1)
8 Journal of Chemistry
ple 0028) Mgw amp Liw (r 0790 ple 0002) Naw amp Kw(r 0955 ple 0000 Naw amp Liw (r 0835 ple 0001) Naw ampCO3w (r minus0701 ple 0011) Kw amp Liw (r 0712 ple 0009)Kw amp CO3w (r minus0580 ple 0048) CO3w amp HCO3w(r minus0613 ple 0034) and Mgw amp SO4w (r 0631ple 0028) indicate that all these variables have some geo-chemical behaviors [77] Mg Na and Li are some com-ponents of the discharged waters however they havepositive correlations with the chlorinity and salinity of thedischarged water sources (r 0743 0619 and 0815 re-spectively) and (r 0743 0619 and 0815 respectively)Mgw and Liw contents in water samples are affected bytemperature dissolved oxygen and pH with high correla-tions of r minus0650 0677 and 0743 and minus0702 0659 and0815 respectively
32 Distribution of Halogens and Tested Variables in PoreWater
321 Distribution of Halogens in Pore Water -e averagehalogen contents in the pore water are higher than theircontents in the surface water but in the same orderClpgtBpgt Fpgt Ip (Table 3) Current research shows that thelowest and highest average values of Spermilp and Clp have beenmeasured in the pore water of site 6 and site 8 respectively Itis worth mentioning that site 6 is a mixed water of El-Qalaadrainage sewage WWTP treatment plant and lake waterInterestingly the high concentrations of fluoride chloridebromide and iodide in the pore water at site 6 are 123mgLminus1 40321mg Lminus1 11739mg Lminus1 and 24339 μg Lminus1 re-spectively (Table 3) -e salinity and chloride content in thepore water of site 8 are related to the discharge water of manypetrochemical and oil companies besides some fish farms
322 Distribution of Tested Variables in Pore Water -etested variables in the pore water (p) give the followingdescending order MgpgtNapgtCapgt SO4pgtBpgtKpgtBrpgt Fpgt LipgtPpgt Ipgt Sip (Table 3) Interestingly the deter-mined variables in the pore water have higher values thanthe surface water along the lake According to previousstudies pore water is responsible for biogeochemical reac-tions the migration and transformation of partitioned andformed compounds and the transportation of colloidalspecies [78 79] In addition pore water can explore thepotential risks of man-made pollution sources [80] -etested variables in the pore water (p) are given in a differentorder of surface water of ClpgtMgpgtNapgtCapgt SO4pgtBpgtKpgtBrpgt Fpgt Lipgt Ppgt Ipgt Sip (Tables 2and 3)
323 Interactions of Halogens and Tested Variables in PoreWater -e following interactions of halogens CO3w amp Ip Ipamp Fw Brw amp Sip Fp amp Siw and Fp amp Nap give correlationvalues (r 0706 ple 0010 r minus0606 ple 0037 r 0826ple 0001 r minus0704 ple 0011 and r 0670 ple 0017respectively) (Supplementary Table 1) However these re-lationships may indicate their precipitation andor
adsorption on the colloidal particles besides the formation ofsome chemical species [78 79] Extraordinarily large cor-relations of Nap amp HCO3w Kp amp HCO3w Spermilw amp Bp Spermilp ampKp Spermilp amp Lip and Spermilp amp Clp (r 0692 minus0609 minus07410696 0910 and 1000) may refer to the release of theseelements from sediment particles andor precipitation oradsorption [77] In the matrix the negative correlationbetween Cap and Mgp (r minus0592 ple 0042) may be relatedto the release of Mg during the recrystallization of calcite[79]-e relationship between Caw amp SO4p Cuw amp Cap Pw ampPp and Nap amp pHw (r 0744 ple 0006 r 0719 ple 0008r 0647 ple 0023 and r minus0640 ple 0025 respectively)may be due to the chemical interactions in the pore fluidsand the formation certain compounds
33Distribution ofHalogens andTestedVariables in Sediment
331 Distribution of Halogens in Sediment -e averagehalogenrsquos content in the sediment shows a different orderfrom the surface and pore waters of Brsgt FsgtClsgt Is (Ta-ble 4) -e sediment results show that the average bromidecontent is higher than fluoride followed by chloride contentand iodide with average values of 452mg gminus1 040mg gminus1029mg gminus1 and 450 μg gminus1 respectively
-e fluoride concentration in the sediment ranges from001 to 120mg gminus1 with an average value of 04plusmn 035mggminus1 -ese values are lower than reported marine sedimentvalues and higher than the El-Bardawil Lagoon [60]Amongst the halogens the study reveals that Br is the mostabundant ion in surface water pore water and sedimentsamples due to the excessive amounts of organic matter [81]On the contrary the concentration of Cl ions in sedimentsamples is lower than that in surface water and pore watersamples indicating that it exists in soluble salts -e currentresults indicate that the sediments collected from the mostaffected area by the Mediterranean Sea (site 6) contain el-evated levels of fluoride (070mg gminus1) bromide (852mggminus1) and chloride (020mg gminus1) and a reduced amount ofiodide (209 μg gminus1) (Table 4)
332 Distribution of Tested Variables in Sediment -eaverage value of test variables in the determined sedimentsamples shows a significant change from site to site with adescending order CO3sgtMgsgtCasgtNasgt SO4s gt FesgtBsgtKsgtTPsgtMn sgtZnsgtCusgt Lis (Table 4) Plus this studyclears out that the percent of sand and mud of the differentsediment samples ranges from 4 at sites 1 amp 13 to 85 atsite 11 and from 15 at site 11 to 96 at sites 1amp13 re-spectively with averages 25 and 75 respectively Plusthe porosity shows a trend opposite to the particle size andvaries from 4676 to 8214 with an average value of5609plusmn 1114 -e results of the current study reveal mod-erate amounts of CO3 in the sediment samples fluctuatingbetween 1639 and 5736 at sites 6 and 2 respectively -eresults of sand mud porosity and CO3 percentage reflect thatthe texture of the sediment is mainly composed of mud mixedwith carbonate compounds Comprehensively the large storageof sediments with carbonate (359plusmn1280) magnesium
Journal of Chemistry 9
Tabl
e3
Distribu
tionof
thestud
iedvariablesin
thepo
rewater
(p)alon
gLake
Mariout
Site
Spermilp
pHP
Ca p
(mgLminus
1 )Mg p
(mgLminus
1 )Na p
(mgLminus
1 )Kp
(mgLminus
1 )Li
p(m
gLminus
1 ))
SO4P
(mgLminus
1 ))
B P(m
gLminus
1 ))
P P(μgLminus
1 ))
SiP
(microgLminus
1 ))
F p(m
gLminus
1 ))
Cl P
(mgLminus
1 ))
Brp
(mgLminus
1 ))
I p(μgLminus
1 )1
1034
787
481
42303
1097
453
042
2944
8043
363
0045
323
95419
959
7104
2934
809
5611
115725
1050
498
039
2056
663
553
0036
338
8398
1385
24698
31272
717
100
5689
1195
577
053
2778
8949
1204
0034
754
114469
2291
26347
483
796
9619
47652
974
384
043
350
19312
77
0054
215
74599
693
8393
51099
782
5611
89711
1128
42041
1667
16739
1112
0081
1698864
1332
8333
645
775
4008
75367
736
41024
2111
11739
071
0037
1231
40321
799
24339
71125
782
39278
13615
1155
516
056
3667
6051
369
006
6101209
1279
8123
8148
775
9299
84314
1355
468
055
12444
942
212
0056
892
133232
1172
7643
9684
78
962
72109
880
393
036
3778
21341
114
0087
1061429
2131
9981
10114
764
1122
113586
1195
524
049
4667
8007
071
0041
1138
102562
1332
8572
11639
742
4008
61996
915
332
033
2833
11594
754
0026
1215
67834
746
37587
125
702
481
38413
8703
274
028
2167
13913
081
0025
2154
44832
1438
9891
13755
807
3206
6467
817
446
039
4556
17246
635
0042
954
5737
533
1097
Minim
um45
702
962
13615
736
274
024
1667
6051
071
0025
215
40321
533
7104
Maxim
um148
809
39278
115725
8703
577
056
12444
21341
1204
0087
2154
133232
2291
37587
Average
919
77
718
67412
163077
4381
041
3782
1223
485
0048
955
82779
1238
14768
SD308
032
10027
29209
2132
825
01
2769
5047
391
0019
542
27891
524
9917
10 Journal of Chemistry
Tabl
e4
Distribu
tionof
thestud
iedvariablesin
thesediment(s)alon
gLake
Mariout
Site
Sand
()
Mud ()
Porosity
()
CO3s
()
B s(m
ggminus
1 )P s
(mg
gminus1 )
Ca s
(mg
gminus1 )
Mg s
(mg
gminus1 )
Na s
(mg
gminus1 )
Ks
(mg
gminus1 )
Lis(m
ggminus
1 )
SO4s
(mg
gminus1 )
Fes
(mg
gminus1 )
Cu s (μg
gminus1 )
Mn s
(μg
gminus1 )
Zns(μg
gminus1 )
F s(m
ggminus
1 )
Cl s
(mg
gminus1 )
Brs
(mg
gminus1 )
I s(μg
gminus1 )
14
964915
183
299
044
1670
811
2583
408
0028
4861
828
963
5617
1272
034
041
128
1686
244
564925
574
196
028
1002
1419
2717
269
0015
662
257
793
4350
1313
057
054
123
358
319
816667
299
246
073
1670
1216
3125
336
0022
463
487
1228
4330
1677
044
034
448
516
418
824853
3813
1111
032
668
2229
3425
365
0094
2222
770
922
4637
1245
030
020
309
296
512
884697
482
614
012
501
1115
1833
091
0040
1713
243
600
27933
1223
082
034
245
254
65
954667
164
370
157
835
1257
2958
388
0030
5648
890
1927
5347
3117
070
020
852
209
75
954762
375
524
024
367
2047
3133
256
0102
1157
546
883
4185
1393
120
020
341
259
838
626143
457
697
039
668
1621
3550
347
0145
4167
598
737
4157
1412
022
034
144
1277
918
826000
349
083
054
401
1094
3358
369
0025
2454
701
868
5702
3065
036
027
250
172
1036
645070
441
296
002
935
1763
3117
246
0045
2685
369
790
4533
1315
012
047
1012
224
1185
157000
325
240
074
969
2250
3508
328
0193
1343
1026
735
3890
1070
005
007
533
128
1237
638214
463
291
032
334
1824
3008
358
0018
556
340
728
2475
827
001
007
852
281
134
965000
177
211
054
2338
1621
3925
599
0068
833
1687
1187
6492
1853
004
027
639
194
Min
415
4667
164
083
002
334
811
1833
091
0015
463
243
600
2475
827
001
007
123
128
Max
8596
8214
574
1111
157
2338
2250
3925
599
0193
6620
1687
1927
6492
3117
120
054
1012
1686
Av
2575
5609
359
398
048
951
1559
3096
335
0063
2671
672
951
4500
1599
040
029
452
450
SD23
231114
128
276
039
603
455
522
115
0055
2030
393
343
1120
708
035
014
303
475
Minm
inim
umM
axm
axim
uma
ndAv
averageSD
stand
arddeviation
Journal of Chemistry 11
(1559plusmn455mg gminus1) and calcium (951plusmn603mg gminus1) com-ponents may be attributed to the abundance of calcium min-erals [4] However in general the average amounts of allvariables in sediment samples showmarked variations fromonesite to another with a descending order of CO3sgtMgsgtCasgtNasgtSO4sgtFesgt BrsgtBsgtKsgtTPsgtFs gtClsgtMnsgtZnsgtCusgtLisgt Is (Table 4) -e measured concentra-tions of Mn Zn Cu and Fe in the sediment samples are stilllower than the reported values and also lower than the back-ground levels of crust and the toxicological reference contents ofUS DOE (US Department of Energy) US EPA (US Envi-ronmental Protection Agency) and CEQG (Canadian Envi-ronmental Quality Guidelines) [82]
Contrasting the obtained levels for the halogens withthose previously reported ones the present study indicatesthat surface and pore waters incorporate more considerableamounts of fluoride compared to the formerly reported onesin Lake Edku (Tables 2 and 3) and lower levels in theMarioutarea than those measured along the Egyptian MediterraneanSea coast [27] Compared with the sediments previouslyfound on the Mediterranean coast of Egypt the chloridecontent in the sediments of the Mariout area is lower [83]Compared with those observed in seawater the studiedsurface water and pore water samples have lower bromidecontent and higher levels than previously reported in LakeMariout [52 53] -e concentration of iodide in surfacewater pore water and sediments is equivalent to the con-centration of rivers and lakes in the world [84]
333 Interactions of Halogens and Tested Variables inSediment -e correlation matrix shows the important roleof halogens in the formation and precipitationdissolution ofsalts and minerals produced along the lake (SupplementaryTable 1) However it shows that chloride seems to be in thesoluble forms along the surface and pore waters of studiedarea showing good relations with Caw (r 0666 ple 0018)Clp (r 0677 ple 0016) and SO4p (r 0858 ple 0000)Also Cls gives good correlations with Mgw (r 0710ple 0010) Naw (r 0602 ple 0038) Clw (r 0619ple 0032) Mgp (r 0774 ple 0003) and Kp (r 0731ple 0007) Chloride in the surface and pore waters plays animportant role in the dissolution association and formationof various salts along the lake -e good relationship be-tween Is and Caw (r 0666 ple 0018) may reflect the de-positionrelease of CaI+ during the formationdissolution ofcalcium carbonate [85] In addition these correlations maybe related to organic-I which formed by bacterial species andtheir remineralization in bottom sediments [86] -emoderate relationship between Nas and Brw (r minus0622ple 0031) may indicate the possible formation of BrClspecies and the precipitation or adsorption of Na minerals insediments [87] -e results of this study also reflect thestrong negative correlation between Fs and Bw (r minus0666ple 0018) which may be related to the release of fluoridefrom sediment and the formation of soluble fluoridecomplexes ((BFn[OH]4minusn)minus) with the excessive boron con-centration in the water [88] -e negative relation betweenKs and Spermilw (r minus0673 ple 0016) possibly reflect that Kw
preferentially chooses to exist in the soluble form of KClrather than being adsorbed andor bound by some richminerals in the sediment
-e significant correlations between CO3s and Mgw(r 0637 ple 0026) CO3s and Clw (r 0723 ple 0008)CO3s and pHw (r 0833 ple 0001) CO3s and Spermilw(r 0723 ple 0008) and between CO3s and Ks (r minus0673ple 0016) may be accompanied by the possible formationdissolution of the dolomite mineral in the presence ofsufficient Mgw which is usually affected by optimal pHsalinity and the potassium salts (Supplementary Table 1)-ese observed results are matching with the previouslyreported studies [32] Significant negative correlation be-tween TPs and CO3s (r minus0744 ple 0006) may indicate theextended release of P from carbonate minerals and for-mation of apatites [32]
-e correlation matrix also refers to other possible in-teractions between the remaining determined variables(Supplementary Table 1) -e significant correlation be-tween SO4s andMgw (r 0706 ple 0010) and Liw (r 0633ple 0027) may be associated to the formation of Mg-sulfateand the pollution of sediments by discharged waters con-taining excessive sulfate and Li [89] In the contrary thestrong positive correlation between TPs and Cus and be-tween TPs and Zns may be related to the same source ofpolluted discharge water [23 83]
-e high negative correlations of Zns with Few(r minus0785 ple 0003) CO3s (r minus0601 ple 0039) and Cus(r 0698 ple 0012) may indicate that Zn Cu and CO3depositions in sediment samples are linked to the soluble Feform in water (ferrous) ie the release of Fe upwards in thewater column in the anoxic conditions (SupplementaryTable 1) [90] -e excellent relations found between Fesand CO3s (r minus0799 ple 0002) Fes and Cas (r 0637ple 0026) Fes and Clw (r minus0752 ple 0005) Fes and Nas(r 0720 ple 0008) and between Fes and Ks (r 0833ple 0001) may reflect the dissolution of the chelating Feassociation with the soluble organic compounds in thewater-sediment interface and the formation of the sol-uble ferrous form in low dissolved oxygen within theareas affected by untreated discharged waters [90] -estrong correlations of Mns with SO4w Nap Nas Ks CO3sZns and Fes (r minus0585 0608 0611 0698 minus0655 0691and 0716 respectively) may associate with the solubilityof abundant Mn minerals and P-Mn forms in the sedi-ment because of its possible reduction to Mn+2 solublespecies under anoxic conditions [90] It is worth men-tioning that the results of this study indicate that ap-proximately 333 of the survey sites indicate thedepletion of dissolved oxygen in their surface watersamples Under such anoxic conditions bacteria are mostlikely to use sulfate instead of oxygen to break downorganic matter and cause the release of iron and phos-phorus into the water column
-e significant direct correlation between Ks and Nas(r 0832 plt 0001) clearly reflects the transport of solublesalts of K and Na between the pore water phase of thesediment and water-sediment surface phase (SupplementaryTable 1) -e good correlation between porosity and Nas
12 Journal of Chemistry
indicates the possible transfer of Na between pore water andsediment partitions
34 Interactions of Precipitated Halogenated Compounds inSurface and Pore Waters -e Saturation Index (SI) [23 60]of twenty-three and fifteen structures in surface water andpore water samples respectively are listed (Table 1) -ecorrelation matrix of the calculated Saturation Indices withthe presented data shows the different factors affecting theinteraction of the halogenated compound with other pre-cipitated salts and minerals Table 1 explores the precipitationof the phosphate minerals and salts are most abundantfollowed by the hydroxidesrsquo salts iodate salts sulfate andcarbonate minerals and salts in surface waters Amongst thehalogens precipitated salts fluoride minerals especiallyfluorapatites and carbonate-fluorapatite (FAP and CFAP)have high SI values in surface water (4277ndash5195 and1604ndash6089 respectively) and in pore water (5126ndash5460 and1752ndash7833 respectively) Bromide and chloride are mainlyfound in the soluble forms in surface and pore waters Iodidesalts (Ca(IO3)2 and Ca(IO3)26H2O) moderately precipitatein surface and pore Iron salts precipitate in surface waterwhile in pore water they are not formed -us SI contentreflects that halogens especially fluoride and iodide play avital role in reducing lake pollution
In addition Table 1 shows that the precipitation com-pounds that may be formed in surface water are relativelydifferent from those in sediment pore water For examplefluorite (CaF2) and sellaıte (MgF2) may be only formed inpore water while calcite and aragonite may be deposited insurface water However the formation of fluorite in surfacewater is related to Naw (r 0778 ple 0003) Kw (r 0704ple 0011) CO3w (r minus0718 ple 0009) Fw (r 0770ple 0003) and Ip (r minus0785 ple 0003) (SupplementaryTable 1)
-e formation of calcium sulfate hemihydrate calciumsulfate and anhydrite in water is related to the increase in theamounts of Caw Mgw SO4w Nap Fp Sip Cls and Mns andthe decrease in porosity values On the other hand pre-cipitation of calcium phosphate is related to Brw (r 0751ple 0005) Znw (r 0668 ple 0018) Pw (r 0881ple 0001) and Ks (r 0881 ple 0001) ie it is affected bythe discharged water composition (Supplementary Table 1)
-e formation of calcite and aragonite in surface water isrelated to the formation of CO3w (r 0753 ple 0005) anddissociation of HCO3w (r minus0660 ple 0020) pHw values(r minus0654 ple 0021) and their dissolution in sediment(r minus0620 ple 0032) (Supplementary Table 1)
-e dolomite formation in water may be affected by theincrease of CO3w (r 0817 ple 0001) and the decrease ofHCO3w (r minus0658 ple 0020) increase in TDSw (r 0599ple 0040) and increase in pHw (r minus0656 ple 0021)besides the possible release of CO3s from abundant sediment(r minus0624 ple 0030) and the precipitation of calcite(r 0984 ple 0000) and aragonite (r 0984 ple 0000) intosediment fraction (Supplementary Table 1)
Generally in the current study the possible formedhalogenated minerals and salts are affected by their
abundance in different components of the lake besides theirpossible dissolution or formation on the sediment texturesgeochemistry of the sediments and physicochemical vari-ables of water in addition to the components of the dis-charged waters
35 Interactions of Dissolved Halogenated Compounds inSurface and PoreWaters -e utilization of dissolved salts insurface and pore waters by utilizing Palmerrsquos method andpiper ternary diagram [50] indicates that Na is the richestcation in surface water followed by Mg Ca and K At thesame time Mg is the most predominate one in the porewater (Figures 3 and 4) Obviously Cl is the most importantanion in surface water and pore waters samples Howeverthe piper ternary diagrams of surface water and pore waterclearly shows that NaCl is the most dominant in surfacewater while MgCl2 is the most abundant in pore waterCoincidently Palmerrsquos method also reflects that NaCl(574) is the most existent species in surface water fol-lowed by MgCl2 (304) CaCl2 (71) CaSO4 (29)Ca(HCO3)2 (14) and KCl (12) (Figure 3) At the sametime MgCl2 (760) is the most present species in porewater followed by NaCl (73)asympMg(HCO3)2 (73)Ca(HCO3)2 (52) and MgSO4 (31) (Figure 4)
36 Multivariate Analysis
361 Principal Component (PCA) By applying Varimaxrotation and Kaiser normalization to 98 variables in the PCAfor halogens and tested variables and calculated parametervalues 7 extracted PCs with eigenvalues higher than 1 areobtained However it is important that the eigenvalue mustbe greater than 1 Its seven PCs explain 8558 of the totalvariance
-e first principle component (PC1) is 1473 of thetotal variance and shows positive coefficient factor loadingsfor CO3w TDSw Kp calcite aragonite dolomite FeCO3MgCO3 ZnCO3 and ZnCO3H2O (0804 0547 05320938 0938 0947 0741 0940 0866 and 0866 respec-tively) In addition it provides negative factor loadings forHCO3w pHw Bw Nap and CO3s (minus0782 minus0610 minus0595minus0532 and minus0572 respectively) PC1 is related to thefactors affecting the carbonate compounds that may beformed in the area under consideration
PC2 accounts to 1458 of the total variance and alsoshows positive and negative coefficient factor loadingsrepresenting the different interactions between the CawMgw Liw SO4wMgp Nap pHp Cls SO4s Brs and porosityin water pore water and sediment that are responsible forthe composition of sulfate magnesium and phosphateprecipitates besides the effect of the discharged waters onwater-pore water-sediment componentsrsquo cycles
PC3 typically shows 1377 of the total variance withpositive and negative loadings which can properly explorethe effect of the principal sources of local pollution on thedissolving of heavy metals B and P from sediment into thewater column and the probable formation of Fe(OH)2Fe(OH)3) and FePO4
Journal of Chemistry 13
Similarly the coefficient factor loadings of PC4 with1355 are related to the influence of the polluted dischargewater and sediment texture on the formation of F Cl and Isalt besides the precipitation of halogenated compounds(FeF2 Mn(IO3)2 KIO4 and KCIO4) besides their minerals(CaF2 MgF2 FAP and CFAP)
Simultaneously PC5 gives 1092 of the total variancewith positive and negative loadings which explains therelations between the physicochemical limits of the surfacewater pore water and sediment components and theprecipitation of minerals and salts (OCP HAP CuBrZn(OH)2 and Zn(IO3)22H2O) -is is also associated tothe influence of the sedimentary material on the release ofMn Fe and P from sediment into pore water and watercolumn and formation of Ca3(PO4)2 OCP and HAPminerals
However PC6 associates with 100 of the total variancegiving positive and negative coefficient factor loadingswhich explain that the sediments (minerals andor organic-iodine compounds) are only the acting sink for iodine andiodine species (Iminus and IOminus
3 ) in the water as previously re-ported [84] PC6 also reflects the precipitation of severalhalogenated compounds such as calcium iodate (Ca(IO3)2and Ca(IO3)26H2O) and copper iodate (CuI andCuIO3H2O) besides Cu3(PO4)2 species in the lake watercolumn
-e loadings of PC7 contribute by 804 and show thatthe release of calcium in pore water into the water column isresponsible for the precipitation of halogenated compounds(CuCl and Zn(IO3)22H2O) as well as copper and Zn salts(Cu3(PO4)2 and Zn(OH)2)
362 Cluster Analysis On the other hand cluster analysisshows that the similarity of sites 1amp4 5amp8 6amp9 2amp10 and11amp13 is due to the texture of sediment
363 Multiple Regression Multiple regression equations ofhalogens as dependent variables and the other determinedand calculated parameters as independent variables insurface water pore water and sediment partitions are listed(Table 5)-e amount of fluoride in water samples is affectedby the discharged watersrsquo fundamental components espe-cially Zn and Cu besides its surface water-pore water in-teractions Its content in pore water seems to be stronglyaffected by its substitution competition with other halogensin surface water-spore water-sediment cycle due to its highelectronegativity Generally in the affected area the type ofpollutant in the discharged water plays an important role inthe dissolution andor precipitation of fluoride and otherhalogens in the surface water-pore water-sediment cycle
574
147129
300
12
Ca(HCO3)2CaSO4CaCl2
MgCl2KClNaCl
(a)
SO4
2 + CIndash Ca 2+ + Mg 2+
CO32ndash + HCO3
ndashNa+ + K+
Mg2+ SO42ndash
Ca2+ CIndash
(b)
Figure 3 (a) distribution and (b) piper ternary diagram of the formed dissolved salts in surface water of Lake Mariout
Ca(HCO3)2Mg(HCO3)2MgSO4
NaClMgCI2KCl
760 1052
7373 31
(a)
SO4
2ndash + C
Indash
Ca 2+ + Mg 2+
CO32ndash + HCO3
ndashNa+ + K+
Mg2+ SO42ndash
CIndashCa2+
(b)
Figure 4 (a) distribution and (b) piper ternary diagram of the formed dissolved salts in pore water of Lake Mariout
14 Journal of Chemistry
Table 5 -e multiple regression analyses of each halogen as dependent variable and other tested variables in the surface water pore waterand sediment partitions besides the precipitated salts in surface water along Lake Mariout
Dependentvariable Multiple regression equation R2
FluorideLake water FW 3162 + 092 Zn F2 minus 033 SiP + 021 CuIminus 017 SpermilP 09911
Pore water Fp minus2567minus117 SiW minus 033 LiP minus 062 CuClminus 028 IS + 023 TDSW+ 017 KIO4 minus 012 BrW minus 004porosity + 004 PW
10000
Sediment FS 088 CAPminus 049 MgS minus 046 DOW+039MgW+ 027 Mn(IO3)2 + 015 Cu3(PO4)2 + 004 HAP+ 002 pHP 10000ChlorideLake water No relation 00000Pore water No relation 00000Sediment ClS minus116 + 046 MgP + 077 Kp minus 049 dolomite + 017 TDSW minus 011 CuI + 005 NaS + 002 BS + 001 FeF2 10000Bromide
Lake water BrW 1563 + 110 CuBrminus 057 CuClminus 021 KS minus 014 pHP minus 011 TPS + 014 FeW+ 007 ZnSminus 002 PP + 001turbidity 10000
Pore water BrP minus1516minus 055 FeS minus 073 BS + 061 MnW+ 083 SiP + 049 NaS minus 031MnS minus 015 CuBr + 011 pHW minus 001CaW
10000
Sediment BrS 015 SiP + 195 CFAP+ 002 FP minus 045 IS + 192 sand+ 037 MnW minus 029 MgS minus 012 LiP + 005Ca3(PO4)2 minus 002 ZnF2
10000
IodideLake water IW 099 Ca(IO3)6H2O 09999
Pore water IP minus097 ZnF2 minus 057 Li3PO4 minus 053 BP + 034 FAP+ 015 Ca(IO3)2 +MnW+ 005 KS minus 009 turbidity + 055CaS
09999
Sediment IS minus072 + 135 SO4P + 023 Mn(IO3)2 + 063 FeW+ 031 TPS minus 035 MgP minus 012 Zn(CO3)22H2O 09993
40E + 0135E + 0130E + 0125E + 0120E + 0115E + 0110E + 0150E + 0000E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
12345
678910
111213
(a)
10E + 0090E ndash 0180E ndash 0170E ndash 0160E ndash 0150E ndash 0140E ndash 0130E ndash 0120E ndash 0110E ndash 0100E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
12345
678910
111213
(b)
12345
678910
111213
40E ndash 0235E ndash 0230E ndash 0225E ndash 0220E ndash 0215E ndash 0210E ndash 0250E ndash 0300E ndash 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
(c)
12345
678910
111213
80E ndash 0670E ndash 0660E ndash 0650E ndash 0640E ndash 0630E ndash 0620E ndash 0610E ndash 0600E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
(d)
Figure 5 Hazard quotient of ingestion and dermal contact of surface water and sediment of LakeMariout (a) ingestion of water (b) dermalcontact of water (c) ingestion of sediment and (d) dermal contact of sediment
Journal of Chemistry 15
Minerals and precipitated salts in the different partitions(surface water pore water and sediment) play an importantrole in the deposition and release of halogens in sedimentsAdditionally the texture and the porosity of the sedimentsplay a key role in the distribution of halogens in the threepartitions Interestingly chloride is the only halogen that hasnegligible interactions along the surface water and porewater partitions because it is present in large quantities inthe form of soluble salts (NaCl and MgCl2)
37 Pollution Status
371 Enrichment Factor (EF) Twowell-knownmethods areused to assess environmental pollution public health sig-nificance of ingestion and dermal contact with water andsediment components and sediment enrichment factor (EF)[59 60]
-e average EF values of the determined elements CaMg Na K Li B P Cu Zn Mn Fe F Cl Br and I are alllower than the value that is less than the minimum en-richment value (EFlt 2)-us the area under investigation isstill ecologically considered as an unpolluted region
372 Human Health Risk Assessment -e EDI HQ and HIshow the variable values of all pollutants in the surface waterand sediments along the lake region and in drains (sites11ndash13) under study Among all the calculated variables ofsurface water ingestion (EDIIngw) and dermal contact(EDIDermw) Cl is still the only variable that shows high levels(average 1551 and 43mg kgminus1 dayminus1 respectively) -eestimation daily intake of sediment ingestion (EDIIngs) anddermal contact (EDIDerms) of Mg Ca and Na give maximumaverage amounts of 841Eminus 02 513E ndash 02 and167Eminus 03mg kgminus1 dayminus1 respectively
Among the HQ of the calculated detection variables thecontent of HQB of ingestion and dermal contact with waterand sediment is the highest However 70 of sites have HQBvalues more than 10 (Figure 5) Comparing the HQ values ofall the determined variables HQB of the ingestion of surfacewater shows values higher (gt10) However due to the impactof drainage the HQB values of stations 1ndash4 8ndash10 12 and 13
are higher than 10 -erefore these sites can be consideredas the area with the most serious boron pollution caused byuntreated discharged water disposal In addition the HIIngwlevel of water ingestion for the studied variables in all sites ismuch higher than 10 (Figure 6) Except for boron it isusually concluded that the study area does not pose any riskto the population due to halogens or other variables Ac-cordingly this information may help the official authoritiesoptimize management plans and strengthen their pollutioncontrol actions in Lake Mariout
4 Conclusions
-e effects of halogen salts and minerals on the pollution ofLake Mariout were studied Halogens and some physico-chemical variables in three partitions surface water porewater and sediment in Lake Mariout were evaluated -ehalogen content was variable between different sites andchloride was the main halogen in surface water and porewater but it was very rare in the lakersquos sediment partitionPiper ternary diagram and Palmerrsquos method reflected thatNaCl was the dominant salt in surface water while MgCl2was the main dissolve salt in pore water-e chlorinity ratiosof halogens and tested variables were directly matched to thefeeding drain sources
Moreover the Saturation Index (SI) reveals that 23 and 15precipitated salts and minerals are formed in surface water andpore water respectively -e SI value indicated the formationof phosphate minerals in surface water and pore water es-pecially octacalcium phosphate (OCP Ca4H(PO4)325H2O)and hydroxyapatite (HAP Ca5(PO4)3OH) In addition tofluoride minerals especially fluorapatite (FAP) and carbonate-fluorapatite (CFAP) were obviously precipitated from surfacewater and pore water Soluble salts of bromide and chloridewere formed in surface water and pore water Iodide salts(Ca(IO3)2 and Ca(IO3)26H2O) were moderately precipitatedin the surface water and pore water
Moreover the multivariate analysis including the cor-relation matrix multiple stepwise linear regression treeclustering and principle component (PCA) of all the de-termined and calculated variables was applied to estimatethe proposed interaction between halogens and other tested
10E + 02
16E + 0214E + 0212E + 02
80E + 0160E + 0140E + 0120E + 0100E + 00
1 2 3 4 5 6 7 8 9 10 11 12 13
HIIngHIDerm
(a)
1 2 3 4 5 6 7 8 9 10 11 12 13
HIIngHIDerm
40E ndash 0235E ndash 0230E ndash 0225E ndash 0220E ndash 0215E ndash 0210E ndash 0250E ndash 0300E + 01
(b)
Figure 6 Hazard index of ingestion and dermal contact of the studied variables in surface water and sediment of Lake Mariout (a) waterand (b) sediment
16 Journal of Chemistry
variables in the polluted area under study -e multivariateanalysis showed that there were many interactions betweenhalogens and tested variables High levels of fluoride bro-mide and chloride in surface water were related to thecomposition of drainage waters -e enrichment factor (EF)showed that Lake Mariout was not polluted However thehuman health adverse effects calculated for surface waterand sediment did not reflect any possible likelihood hazardeffects from halogens
Interestingly the current study concluded that halogencompounds especially fluorides are most likely to be de-posited from surface lakes in the form of many minerals andprecipitation thereby reducing the adverse pollution effectson human health -e results obtained through this workhelp to find the correlations between the sampling sites andthe variables obtained by physical and chemical measure-ments which can be used to construct a fast decision modelfor separating different water quality samples -is infor-mation may help the official authorities optimize manage-ment plans and strengthen their pollution control measuresin Lake Mariout
Data Availability
-e data used to support the findings of this research areincluded within the paper
Conflicts of Interest
-e authors declare that there are no conflicts of interestregarding the publication of this manuscript
Supplementary Materials
Supplementary Table 1 correlation matrix of variable insurface water pore water and sediment partitions besidesthe precipitated salts in surface water along Lake Mariout(Supplementary Materials)
References
[1] M S Masoud T O Said G El-Zokm and M A ShreadahldquoAssesment of heavy metals contamination in surface sedi-ments of the Egyptian Red Sea Coastsrdquo Australian Journal ofBasic and Applied Sciences vol 6 pp 44ndash58 2012
[2] M A Shreadah M I Abdel Moneim T O SaidE M I Fathallah and M E Mahmoud ldquoPAHs in seawater ofthe semi-closed areas along the Alexandria coast of EgyptianMediterranean seardquo Journal of Environmental Protectionvol 4 no 11 p 11 Article ID 40298 2013
[3] S Abdel Ghani G El Zokm A Shobier T Othman andM Shreadah ldquoMetal pollution in surface sediments of Abu-Qir bay and Eastern harbour of Alexandria Egyptrdquo EgyptianJournal of Aquatic Research vol 39 no 1 pp 1ndash12 2013
[4] G F El-Said ldquoBioaccumulation of key metals and othercontaminants by seaweeds from the Egyptian MediterraneanSea Coast in relation to human health riskrdquo Human andEcological Risk Assessment An International Journal vol 19no 5 pp 1285ndash1305 2013
[5] M A Shreadah A H Shobier S Abdel Ghani G M El-Zokm and T O Said ldquoMajor ions anomalies and
contamination status by trace metals in sediments from twohot spots along the Mediterranean Coast of Egyptrdquo Envi-ronmental Monitoring and Assessment vol 187 no 280pp 1ndash18 2015
[6] A El Nemr G F El-Said A Khaled and S Ragab ldquoDis-tribution and ecological risk assessment of some heavy metalsin coastal surface sediments along the Red Sea Egyptrdquo In-ternational Journal of Sediment Research vol 31 no 2pp 164ndash172 2016
[7] A El Nemr G F El-Said S Ragab A Khaled and A El-Sikaily ldquo-e distribution contamination and risk assessmentof heavy metals in sediment and shellfish from the Red Seacoast Egyptrdquo Chemosphere vol 165 pp 369ndash380 2016
[8] A El Nemr and G F El-Said ldquoAssessment and ecological riskof heavy metals in sediment and molluscs from the Medi-terranean coastrdquo Water Environment Research vol 89 no 3pp 195ndash210 2017
[9] M A Sheradah A A El-Sikaily N M Abd El MoneamN E Abd El Maguid and M G Zaki ldquoChemical and bio-chemical evaluation of marine pollution by polychlorinatedbiphenyls and pesticides in two regions along the EgyptianMediterranean Seardquo International Journal of EnvironmentalMonitoring and Analysis vol 6 no 3 pp 95ndash109 2018
[10] M A Shreadah A A-M M El-Sayed A A S TahaA-M M Ahmed and H H Abdel Rahman ldquoEvaluation ofdifferent anthropogenic effluents impacts on the water qualityusing principal component analysis a case study of Abu-QirBay-Alexandria-Egyptrdquo International Journal of Environ-mental Monitoring and Analysis vol 7 no 3 pp 56ndash67 2019
[11] G F El-Said M M El-Sadaawy A H Shobier andS E Ramadan ldquoHuman health implication of major and traceelements present in commercial crustaceans of a traditionalseafood marketing region Egyptrdquo Biological Trace ElementResearch vol 199 pp 315ndash328 2020
[12] M A Shreadah S A A Ghani H B I HawashA A E Samie and A E M M Ahmed ldquoOrganotin com-pounds in sediments of northern lakes Egyptrdquo Journal ofEnvironmental Protection vol 05 no 17 pp 1654ndash1666 2014
[13] A M Younis G M El-Zokm and M A Okbah ldquoSpatialvariation of acid-volatile sulfide and simultaneously extractedmetals in Egyptian Mediterranean Sea lagoon sedimentsrdquoEnvironmental Monitoring and Assessment vol 186 no 6pp 3567ndash3579 2014
[14] G F El-Said S E O Draz M M El-Sadaawy andA A Moneer ldquoSedimentology geochemistry pollution statusand ecological risk assessment of some heavy metals insurficial sediments of an Egyptian lagoon connecting to theMediterranean Seardquo Journal of Environmental Science andHealth Part A vol 49 no 9 pp 1029ndash1044 2014
[15] G M El Zokm M A Okbah and A M Younis ldquoAssessmentof heavy metals pollution using AVS-SEM and fractionationtechniques in Edku Lagoon sediments Mediterranean SeaEgyptrdquo Journal of Environmental Science and Health PartAvol 50 no 6 pp 571ndash584 2015
[16] G M El Zokm H R Z Tadros M A Okbah andG H Ibrahim ldquoldquoEutrophication assessment using TRIX andCarlsonrsquos indices in Lake Mariout water Egyptrdquo EgyptianJournal of Aquatic Biology and Fisheries vol 22 no 5pp 331ndash349 2018
[17] N Donia ldquoLake Maryut monitoring using remote sensingrdquo inProceedings of the gypt Eighteenth International WaterTechnology Conference IWTC18 Sharm El Sheikh Abu DhabiUAE March 2015
Journal of Chemistry 17
[18] M A Khairy ldquoAssessment of priority phenolic compounds insediments from an extremely polluted coastal wetland (LakeMaryut Egypt)rdquo Environmental Monitoring and Assessmentvol 185 no 1 pp 441ndash455 2013
[19] N A El-Naggar and E A Rifaat ldquoEgyptian coastal lakes andwetlands part Imdashcharacteristics and hydrodynamicsrdquo in eHandbook of Environmental Chemistry A M Negm EdSpringer International Publishing AG Berlin Germany 2017
[20] J J Hanley and K T Koga ldquoChapter 2 ldquohalogens in terrestrialand cosmic geochemical systems abundances Geochemicalbehaviors and analytical methodsrdquordquo in e Role of Halogensin Terrestrial and Extraterrestrial Geochemical ProcessesD E Harlov and L Aranovich Eds Springer InternationalPublishing AG Berlin Germany pp 21ndash121 2018
[21] A Ghosh K Mukherjee S K Ghosh and B Saha ldquoSourcesand toxicity of fluoride in the environmentrdquo Research onChemical Intermediates vol 39 no 7 pp 2881ndash2915 2013
[22] M M Naim A A Moneer and G F El-Said ldquoPredictiveequations for the defluoridation by electrocoagulation tech-nique using bipolar aluminum electrodes in the absence andpresence of additives a multivariate studyrdquo Desalination andWater Treatment vol 57 no 14 pp 6320ndash6332 2016
[23] G F El-Said N A Shaltout M M El-Sadaawy andA M H Morsy ldquo-e precipitation of fluoride calcium andmagnesium minerals from Egyptian Mediterranean Sea coastin relation to discharged watersrdquo Desalination and WaterTreatment vol 57 no 5 pp 2113ndash2124 2016
[24] H Bureau ldquoIodine encyclopedia of geochemistry A com-prehensive reference source on the chemistry of the earthrdquo inEncyclopedia of Earth Sciences Series W M White Ed copySpringer International Publishing AG 2016
[25] F C Kupper and C J Carrano ldquoKey aspects of the iodinemetabolism in brown algae a brief critical reviewrdquo Metal-lomics vol 11 pp 756ndash764 2019
[26] R Liteplo R Gomes P Howe and H Malcolm Fluorides-Environmental Health Criteria 227 p 290 World HealthOrganization (WHO) Geneva Switzerland 2002
[27] G F El-Said and M M El-Sadaawy ldquoSeasonal variation ofboron and fluoride in Tilapia nilotica from an Egyptian fishfarm in relation to Human health hazard assessmentrdquoHumanand Ecological Risk Assessment An International Journalvol 19 no 4 pp 930ndash943 2013
[28] WHO (World Health Organization) Bromide in Drinking-Water Background Document for Development of WHOGuidelines for Drinking-Water Quality WHO Press WorldHealth Organization Geneva Switzerland 2009
[29] G F El-Said and N A Sallam ldquo-e uptake of fluorideconcentration and its effects on the growth rate of shrimps(Palaemon elegans Rathke)rdquo Chemistry and Ecology vol 24no 3 pp 191ndash205 2008
[30] X Zhang J He B He and J Sun ldquoAssessment formationmechanism and different source contributions of dissolvedsalt pollution in the shallow groundwater of Hutuo Riveralluvial-pluvial fan in the North China Plainrdquo EnvironmentalScience and Pollution Research vol 26 no 35 pp 35742ndash35756 2019
[31] Y Zhu B Huang Z Zhu et al ldquoldquoCharacterization disso-lution and solubility of the hydroxypyromorphitendashhydroxyapatite solid solution [(PbxCa1minusx)5(PO4)3OH] at25 degC and pH 2ndash9rdquo Geochemical Transactions vol 17 no 2pp 1ndash18 2016
[32] G F El-Said M M El-Sadaawy A A Moneer andN A Shaltout ldquo-e effect of fluoride on the distribution ofsome minerals in the surface water of an Egyptian lagoon at
the Mediterranean Seardquo Egyptian Journal of Aquatic Researchvol 41 no 1 pp 31ndash39 2015
[33] Y Zhu Z Zhu X Zhao Y Liang and Y Huang ldquoChar-acterization dissolution and solubility of lead hydroxypyr-omorphite [Pb5(PO4)3OH] at 25ndash45degCrdquo Journal ofChemistry vol 2015 Article ID 269387 10 pages 2015
[34] M A Z Chahouki ldquoMultivariate analysis techniques inenvironmental sciencerdquo in Earth and Environmental SciencesDr Imran Ahmad Dar Ed InTech Open London UK 2011httpwwwintechopencombooksearth-and-environmental-sciencesmultivariate-analysis-techniques-inenvironmental-science
[35] J V Klump and C S Martens ldquoBiogeochemical cycling in anorganic-rich coastal marine basin 5 Sedimentary nitrogenand phosphorus budgets based upon kinetic models massbalances and the stoichiometry of nutrient regenerationrdquoGeochimica et Cosmochimica Acta vol 51 no 5 pp 1161ndash1173 1987
[36] R L Folk Petrology of Sedimentary Rocks University of TexasAustin TX USA 1974
[37] P Saenger ldquoA rapid spectrophotometric method for thedetermination of bromine in seawater and in the ash ofmarine algaerdquo Helgolander Wissenschaftliche Meer-esuntersuchungen vol 23 no 1 pp 32ndash37 1972
[38] P G Jeffery Chemical Methods of Rock Analysis PergamonPress New York NY USA 2nd edition 1975
[39] J D H Strickland and T R Parsons ldquoA practical handbook ofseawater analysisrdquo in Fisheries Research Board of CanadaBulletin 167p 311 Second edition Wiley Ottawa Canada1972
[40] B Horvath O Opara-Nadi and F Beese ldquoA simple methodfor measuring the carbonate content of soilsrdquo Soil ScienceSociety of America Journal vol 69 no 4 pp 1066ndash1068 2005
[41] K Grasshoff Methods of Seawater Analysis p 317 VerlagChemie Weinkeim Germany 1976
[42] R Danovaro D Marrale N Della Croce P Parodi andM Fabiano ldquoBiochemical composition of sedimentary or-ganic matter and bacterial distribution in the Aegean Seatrophic state and pelagic-benthic couplingrdquo Journal of SeaResearch vol 42 no 2 pp 117ndash129 1999
[43] APHA-AWWA-WPCF (American Public Health Associa-tion) Standard Methods for the Examination of Water andWaste Water American Public Health Association Wash-ington DC USA 20th edition 1999
[44] K I Aspila H Agemian and A S Y Chau ldquoA semi-auto-mated method for the determination of inorganic organicand total phosphate in sedimentsrdquo e Analyst vol 101no 1200 pp 187ndash197 1976
[45] J P Riley and D Taylor ldquoChelating resins for the concen-tration of trace elements from sea water and their analyticaluse in conjunction with atomic absorption spectrophotom-etryrdquo Analytica Chimica Acta vol 40 pp 479ndash485 1968
[46] G F El-Said and A El-Sikaily ldquoChemical composition ofsome seaweed from Mediterranean Sea coast Egyptrdquo Envi-ronmental Monitoring and Assessment vol 185 no 7pp 6089ndash6099 2013
[47] Directorate General of Health Services Ministry of Health andFamilyWelfare Government of India ldquoManual of methods ofanalysis of foodsrdquo in Fruit and Vegetable Productsp 57Directorate General of Health Services Ministry of Health andFamily Welfare Government of India New Delhi India2005
[48] A Gunnars S Blomqvist and C Martinsson ldquoInorganicformation of apatite in brackish seawater from the Baltic Sea
18 Journal of Chemistry
an experimental approachrdquo Marine Chemistry vol 91 no 1-4 pp 15ndash26 2004
[49] W M Haynes D R Lide and T J Bruno CRC Handbook ofChemistry and Physics A Ready Reference Book of Chemicaland Physical Data CRC Press Taylor amp Frances Group BocaRaton FL USA 97th edition 2017
[50] M S Masoud M I El-Samra and M M El-Sadawy ldquoWaterchemistry of el-mex bay west of Alexandria Egyptrdquo eEgypian Science Magazine vol 2 pp 70ndash78 2005
[51] F J Millero R Feistel D G Wright and T J McDougallldquo-e composition of standard seawater and the definition ofthe reference-composition salinity scalerdquo Deep Sea ResearchPart I Oceanographic Research Papers vol 55 no 1pp 50ndash72 2008
[52] S K El-Wakeel S A Morcos and A M Mahlis ldquo-e majorcations in Lake Maryut watersrdquo Hydrobiologia vol 36 no 2pp 253ndash274 1970
[53] A M Mahlis S A Morcos and S K El-Wakeel ldquo-e majoranions in Lake Maryut watersrdquo Hydrobiologia vol 36 no 2pp 275ndash294 1970
[54] A S Saad M A Massoud R A Amer and M A GhorabldquoAssessment of the physico-chemical characteristics andwater quality analysis of Mariout Lake southern of Alexan-dria Egyptrdquo Journal of Environmental and Analytical Toxi-cology vol 7 no 1 p 421 2017
[55] R Rumuri ldquoDataset on hydrogeochemical characteristics ofgroundwater and surface water in Kattumannarkoil TalukIndiardquo Data in Brief vol 32 Article ID 106058 2020
[56] P Szefer S W Fowler K Ikuta et al ldquoA comparative as-sessment of heavy metal accumulation in soft parts and byssusof mussels from subarctic temperate subtropical and tropicalmarine environmentsrdquo Environmental Pollution vol 139no 1 pp 70ndash78 2006
[57] N F Soliman G M El Zokm and M A Okbah ldquoRisk as-sessment and chemical fractionation of selected elements insurface sediments from Lake Qarun Egypt using modifiedBCR techniquerdquo Chemosphere vol 191 pp 262ndash271 2018
[58] G M El Zokm M I A Ibrahim L A Mohamed and M El-Mamoney ldquoCritical geochemical insight into Alexandria coastwith special reference to diagnostic ratios (TOCTN amp SrCa)and heavy metals ecotoxicological hazardsrdquo Egyptian Journalof Aquatic Research vol 46 no 1 pp 27ndash33 2020
[59] A S Likuku K B Mmolawa and G K GaboutloeloeldquoAssessment of heavy metal enrichment and degree of con-tamination around the copper-nickel mine in the SelebiPhikwe Region Eastern Botswanardquo Environment and EcologyResearch vol 1 no 2 pp 32ndash40 2013
[60] M K Khalil S E O Draz G M El Zokm and G F El-SaidldquoApportionment of geochemistry texturersquos properties and riskassessment of some elements in surface sediments from Bar-dawil Lagoon Egyptrdquo Human and Ecological Risk AssessmentAn International Journal vol 22 no 3 pp 775ndash791 2016
[61] M M El-Sadaawy and G F El-Said ldquoAssessment of fluoridein three selected polluted environments along the EgyptianMediterranean Sea effects on local populationsrdquo Human andEcological Risk Assessment An International Journal vol 20no 6 pp 1643ndash1658 2014
[62] USEPA ldquoSuperfund exposure assessment manualrdquo inOSWER Directive 92855-1EPA540l-88001Office of Emer-gency and Remedial Response Washington DC USA 1988
[63] USEPA ldquoExposure factors handbookrdquo in EPA6008-89043Office of Health and Environmental Assessment Wash-ington DC USA 1989
[64] Health Canada ldquoFederal Contaminated Site Risk Assessmentin Canadardquo Part II Health Canada Toxicological ReferenceValues (TRVs) Cat H46-204-368E Calgary Health CanadaOttawa Canada 2007
[65] J Iqbal S A Tirmizi and M H Shah ldquoStatistical appor-tionment and risk assessment of selected metals in sedimentsfrom Rawal Lake (Pakistan)rdquo Environmental Monitoring andAssessment vol 185 no 1 pp 729ndash743 2013
[66] USEPA (US Environmental Protection Agency) Region 6USAEPA ldquoMultimedia Planning and Permitting DivisionrdquoOffice of Solid Waste Center for Combustion Science andEngineering Washington DC USA 2005
[67] P Jeschke ldquoLatest generation of halogen-containing pesti-cidesrdquo Pest Management Science vol 73 no 6 pp 1053ndash10662017
[68] M A Shreadah O A El-Rayis N A Shaaban andA M Hamdan ldquoWater quality assessment and phosphorusbudget of a lake (Mariut Egypt) after diversion of wastewaterseffluentsrdquo Environmental Science and Pollution Researchvol 27 no 21 pp 26786ndash26799 2020
[69] J P Riley and M Tongudai ldquo-e major cationchlorinityratios in sea waterrdquo Chemical Geology vol 2 pp 263ndash2691967
[70] R B McCleskey D K Nordstrom D D Susong J W Balland J M Holloway ldquoSource and fate of inorganic solutes inthe gibbon river yellowstone national park Wyoming USArdquoJournal of Volcanology and Geothermal Research vol 193no 3-4 pp 189ndash202 2010
[71] G T F Wong and K-Y Li ldquoWinklerrsquos method overestimatesdissolved oxygen in seawater iodate interference and itsoceanographic implicationsrdquo Marine Chemistry vol 115no 1-2 pp 86ndash91 2009
[72] B S R V Prasad P D N Srinivasu P S VarmaA V Raman and S Ray ldquoDynamics of dissolved oxygen inrelation to saturation and health of an aquatic body a case forChilka Lagoon Indiardquo Journal of Ecosystems vol 2014 Ar-ticle ID 526245 17 pages 2014
[73] China Environmental Protection Agency EnvironmentalQuality Standards for Surface Water (GB3838ndash2002) NationalEnvironmental Protection Agency of China Beijing China2002
[74] Y Jia L Wang Z Qu and Z Yang ldquoDistribution con-tamination and accumulation of heavy metals in watersediments and freshwater shellfish from Liuyang RiverSouthern Chinardquo Environmental Science and Pollution Re-search vol 25 no 7 pp 7012ndash7020 2018
[75] A Moneer M El-Sadawy G El-Said and A Radwan ldquoBoronhuman health risk assessment relative to the environmentalpollution of Lake Edku Egyptrdquo Journal of King AbdulazizUniversity vol 23 no 2 pp 41ndash55 2012
[76] C B Tabelin T Igarashi T Arima D Sato T Tatsuhara andS Tamoto ldquoCharacterization and evaluation of arsenic andboron adsorption onto natural geologic materials and theirapplication in the disposal of excavated altered rockrdquo Geo-derma vol 213 pp 163ndash172 2014
[77] G Aloisi K Wallmann M Drews and G BohrmannldquoEvidence for the submarine weathering of silicate minerals inBlack Sea sediments possible implications for the marine Liand B cyclesrdquo Geochemistry Geophysics Geosystems vol 5no 4 pp 1ndash22 2004
[78] C Degueldre and V Cloet ldquoPore water colloid properties inargillaceous sedimentary rocksrdquo Science of e Total Envi-ronment vol 569-570 pp 423ndash433 2016
Journal of Chemistry 19
[79] J A Higgins and D P Schrag ldquoRecords of Neogene seawaterchemistry and diagenesis in deep-sea carbonate sedimentsand pore fluidsrdquo Earth and Planetary Science Letters vol 357-358 pp 386ndash396 2012
[80] H Schroeder A-L Fabricius D Ecker T A Ternes andL Duester ldquoMetal(loid) speciation and size fractionation insediment pore water depth profiles examined with a newmesoprofiling systemrdquo Chemosphere vol 179 pp 185ndash193 2017
[81] Y Song and G Muller ldquoFreshwater sediments sinks andsources of brominerdquo Naturwissenschaften vol 80 no 12pp 558ndash560 1993
[82] M E Goher H I Farhat M H Abdo and S G Salem ldquoMetalpollution assessment in the surface sediment of Lake NasserEgyptrdquo Egyptian Journal of Aquatic Research vol 40 no 3pp 213ndash224 2014
[83] G F El-Said M M El-Sadawy and A A Moneer ldquoIncor-poration of fluoride and boron into surface sediments alongthe Egyptian Mediterranean coastrdquo Egyptian Journal ofAquatic Research vol 36 no 4 pp 569ndash583 2010
[84] B Gilfedder G M Petri M Wessels and H Biester ldquoAniodine mass-balance for Lake Constance Germany insightsinto iodine speciation changes and fluxesrdquo Geochimica etCosmochimica Acta vol 74 no 11 pp 3090ndash3111 2010
[85] E Korobova L Kolmykova B Ryzhenko et al ldquoDistributionand speciation of iodine in drinking waters from geochem-ically different areas of Bryansk region contaminated after theChernobyl accident in relation to health and remediationaspectsrdquo Journal of Geochemical Exploration vol 184pp 311ndash317 2018
[86] V Zic V W Truesdale and N Cukrov ldquo-e distribution ofiodide and iodate in anchialine cave watersmdashevidence forsustained localised oxidation of iodide to iodate in marinewaterrdquoMarine Chemistry vol 112 no 3-4 pp 168ndash178 2008
[87] M B Heeb J Criquet S G Zimmermann-Steffens andU Von Gunten ldquoOxidative treatment of bromide-containingwaters formation of bromine and its reactions with inorganicand organic compoundsmdasha critical reviewrdquo Water Researchvol 48 pp 15ndash42 2014
[88] V Sivasankar A K Darchen and R Omine SakthivelldquoChapter 2 ldquofluoride a world ubiquitous compound itschemistry and ways of contaminationrdquo in Surface ModifiedCarbons as Scavengers for Fluoride fromWater V SivasankarEd pp 5ndash32 copy Springer International Publishing Switzer-land Cham Switzerland 2016
[89] O Cabestrero P Del Buey and M E Sanz-Montero ldquoBio-sedimentary and geochemical constraints on the precipitationof mineral crusts in shallow sulphate lakesrdquo SedimentaryGeology vol 366 pp 32ndash46 2018
[90] M A Hassaan O A El-Rayis and E I Hemada ldquoEstimationof the redox potential of lake mariut drainage system (Qalaaand Umum drains)rdquoHydrology vol 5 no 6 pp 82ndash85 2017
20 Journal of Chemistry
as the solubility and precipitation of the salt contained alsohelps to track pollution [31] -e formation and internalinteraction of different soluble and insoluble salts in aquaticsystems are affected by the physical and chemical factors ofthe ecosystem [31] -e behavior of soluble salts in theaquatic systems can provide information about the forma-tion of precipitated salts -e stability of the precipitated saltis affected by the product of the molar concentration of itsions and the equilibrium solubility constant of the precip-itated salt According to previous studies under alkalineconditions fluorapatite minerals had an important role inreducing the solubility of calcite in the apatite supernatantand solving the destructive effects of fluoride pollution onLake Edku in Egypt [32] Small amounts of bromine arefound in certain minerals (such as apatite amphibole andbiotite) [24] In addition calcium hydroxyapatite canremove toxic ions from the water environment [33]
By multivariate analysis the ecological and environ-mental multivariate data can assess the environmental im-pacts and monitor large-scale biodiversity changes [34]Multivariate analysis is widely used in environmental sci-ence It can help ecologists discover the structure of manycharacteristics of the data and the previous relatively ob-jective summary for easy understanding However it is verycomplicated in theoretical structure and operation methods
To the best of our knowledge relatively little studies havebeen evaluated for the long-term changes in concentrationsof halogens ie bromine fluorine chlorine and iodine andtheir relative to pollution status in surface water pore waterand sediments partitions in the polluted Lake Mariout -eaims of this work are to present an overview of the evalu-ation of halogenrsquos content and to examine the relation ofpollution by halogens as well as to find out their possibleinteractions with dissolved and precipitated salts in MarioutLake which is suffering from the huge amounts of differenttypes of waste waters
2 Materials and Methods
21 Sampling Sites -irteen sampling sites were selected torepresent the survey area of Lake Mariout and the incomingdrainage (Figure 1) Surface water sediment pore water andsediment samples were collected from the thirteen sites Site 1and site 2 were affected by the parallel pumping station(pumping water from the Abis drainageasymp 400000 m3dayminus1 andother openings from El Drain [19] Site 3 represented thecombined discharge of El-Qalaa drainage and WesternWastewater Treatment Plant (WWTP) Sites 4ndash6 belonged tothe Main Basin area and were affected by the drainage of El-Qalaa and El Umoum Site 6 represented the contaminated areabefore the El-Mex pumping station Site 7 was located in theNorthWest Basin In addition to saltmarshes it was also directlyaffected by many industrial and petrochemical companies -eSouth West shallow basin was adversely affected by the localwater sources of El Umoum and El Nubaria drains and its sitewas 8ndash10 Stations 11ndash13 were located in the El-Qalaa the ElNubaria and the El Umoum drains outside the lake -e lastthree locations were chosen as reference locations to describe thepotential pollution of the water discharged into the lake
22 Sampling Processes Surface water and bottom sedimentsamples were collected from thirteen selected sites along thelake and the drains of depth range 15ndash20m by a rubber boatduring autumn 2019 (Figure 1) Nitrile gloves were usedduring the sampling duration
For water sampling thirty-nine airtight clean 5 L poly-ethylene bottles for water sampling were rinsed three timeswith double distilled water and then dried Triplicate col-lected surface water samples were collected by the Niskinwater sampler from each sampling site However thesesurface water samples were not filled in 5 L cleaned poly-ethylene bottles in which they can be preserved Each watersample from the study site was divided into two portions-e first portion was stored in a brown closed polyethyleneplastic bottle the second part was stored in a closed whitebottle for the determination of heavy metals -e subdividedsamples were carefully transported to the laboratory in an icebox However surface water temperature (Tw) pH salinityand TDS value of water samples weremeasured on-site usingportable equipment (CTD YSI 566) -e dissolved oxygen(DO) sample was fixed in a closed brown glass bottle on-siteTurbidity was measured by using the conventional whiteenameled Secchi-disc
For sediment sampling three replicate sediment sampleswere collected from 13 sampling sites using a Van-Veen grabsampler stored in a clean polyethylene bag and transportedto the laboratory in an ice box
23 Sample Preparation In the laboratory the first portionof the subdivided surface water was stored in a brownairtight polyethylene plastic bottle at minus20degC for halogenanalysis -e second portion was divided into two parts andone of which was stored in a plastic colorless bottle at minus20degCto determine phosphorus and silicon in the form of phos-phate and silicate -e other part was kept in the refrigeratoruntil the main water components (calcium magnesiumsodium potassium lithium sulfate and boron) and heavymetals (copper manganese zinc and iron) were analyzed
In addition pore water was extracted from each sedi-ment sample by a centrifuge (Hettich Zentrifugen Universal320 R Andreas Hettich GmbH amp CoKG 78532 TuttlingenGermany) for 20min and at a speed of 10000 rpm [35]
First in each extracted pore water sample pH and Spermilwere detected -en one-third of each extracted pore watersample was preserved in a brown polyethylene plastic bottlewith a stopper and kept at minus20degC for halogen determinationWhile two-third portion was preserved in colorless well-closed plastic bottles and kept at minus20degC for analysis ofphosphorus silicon calcium magnesium sodium potas-sium lithium sulfate and boron calcium magnesiumsulfate boron and heavy metals concentrations (Cu MnZn and Fe)
On the other hand the sediment samples were spread ona clean plastic plate at room temperature and then air driedAfter that the particle size of the air-dried sediment samplewas accurately estimated [36] -e digestion of the sedimentsample was performed by heating the sample with an acidmixture (3mL HNO3 2mL HClO4 and 1mL HF) at 70degC in
Journal of Chemistry 3
a closed Teflon container -e extraction of fluoride bro-mide and iodide from sediment samples was carried outafter the fusion of Na2CO3 with each sediment sample[37 38]
24 Samples Analyses -e carbonate and bicarbonate ofsurface and pore waters were determined in the laboratory bythe titration method [39 40] pH and TDS values of the porewater were measured in the laboratory using portableequipment (CTDYSI 566) From the salinity value chlorosity(Cl) in the surface and pore waters and chlorinity (Clpermil)wereeffectively calculated [39] -e DO of water samples wasaccurately measured by Winklerrsquos method [41] Porosity wasmeasured based on the weight difference between dry and wetsediment samples [42] Calcium and magnesium in surfaceand pore waters and digested sediment samples were carefullydetermined by the titrimetricmethod using Eriochrome BlackT and Murexide indicators [43] Sodium potassium andlithium contents in surface and pore waters and digestedsediment samples were estimated by the flame photometerinstrument (lame139 photometer PFP JENWAY 7) Inor-ganic phosphorus and total phosphorus contents in thesurface and pore waters and sediment samples were deter-mined [43 44] Silicate was measured in the surface and porewaters and digested sediment samples by the calorimetricmethod [39] Curcumin colorimetry was used to determineboron in surface water pore water and digested sediment[43] -e turbidity method was used to estimate sulfate in thesurface water and pore water and digested sediment samples[43] -e heavy metals (Cu Mn Zn and Fe) dissolved in thesurface and pore water samples were extracted with chelatingresin and measured with an atomic absorption spectropho-tometer (GBC Savant AA Scientific equipment serial no A7275 GBC) [45] Fluoride concentration was determined bythe colorimetric method using the zirconium alizarin red Smethod [46] -e bromide was determined by titration usinga thiosulfate solution [41] -e catalytic reduction methodusing the Ce(IV)-As(III) was applied to determine the iodineconcentration [43] -e chloride content in sediments wasestablished by Mohrrsquos method [47]
25 Quality Control and Quality Assurance A sedimentreference material (IAEA-405 International Atomic EnergyAgency Vienna Austria) was used to determine the sedi-ment samplersquos quality controlquality assurance -e re-covery percentages for the selected metals from the standardreference material were in the range of 970ndash1011 Foreach variable an examined calibration procedure of threeexternal standards was performed One of the externalstandards must be of a concentration near but above themethod detection limit -e other concentrations shouldcorrespond to the range of a variable concentration expectedin the sample -e working calibration curve was verified oneach working shift by the measurement of one or morecalibration standards
26 Saturation Index (SI) -e Saturation Index (SI) of 23and 15 structures in surface water and pore water sampleswere calculated respectively [23 48]
It can be calculated from the division of the product of themolar concentrations (IAP [49]) of their component by theirequilibrium solubility constant (Table 1) Moreover SI of someminerals such as anhydrite (CaSO4) gypsum (CaSO42H2O)calcium phosphate (Ca3(PO4)2) magnesium phosphate(Mg3(PO4)2) calcite (CaCO3) aragonite (CaCO3) dolomite(CaMg(CO3)2) magnesite (MgCO3) fluorapatite (FAPCa5(PO4)3F) hydroxyapatite (HAP Ca5(PO4)3OH) octacal-cium phosphate (OCP Ca4H(PO4)325H2O) and carbonate-fluorapatite (CFAP Ca10(PO4)5(CO3)F272(OH)028) besidessome precipitated salts (Fe(OH)2 Fe(OH)3 FePO42H2OMg(OH)2 Mg3(PO4)2 Mn(IO3)2 KIO4 KCIO4 ZnCO3ZnCO3H2O Zn(OH)2 and Zn(IO3)22H2O) was calculatedby the following equation [23 48]
SI logIAPKsp
1113888 1113889 (1)
where IAP and Ksp were the product of the ion activity andthe equilibrium solubility constant of each precipitated saltor mineral SI values represented the under saturation(SIlt 1) or over saturation (SIgt 1) situation of each pre-cipitated salt or mineral
27 Palmerrsquos Method and Piper Ternary Diagram -e dis-solved salts in the surface and pore waters in the in-vestigated area were utilized by Palmerrsquos method andpiper ternary diagram Palmerrsquos method by using the millequivalent percentage of the major anions (Clminus SO4
minus2and HCO3
minus) and cations (K+ Na+ Ca+2 and Mg+2) [50]-is method assumed that the concentration of positiveions and negative ions are in equilibrium ie the sum ofthe concentrations of positive ions in meq Lminus1 is equal tothe sum of the concentrations of negative of ions con-sidering only the major ions -is hypothesis can beverified by converting the average ion concentration ofsurface water and pore water along the study areafrom mg Lminus1 in Table 2 to meq Lminus1 -en the concen-trations were further converted into a percentage of eachion in relation to the total concentration of positive ionsin the case of a positive ion and in relation to the totalconcentration of negative ions in the case of a negativeion -e percentage of each cation and anion was rep-resented in two rectangles in cm to evaluate the relativeformed soluble salts Piper ternary diagram explores theorigin of the dissolved salts in surface and pore waters ofthe lake water besides the effects of drainage sources onthem [55]
28 Multivariate Analysis Multivariate analysis includingcorrelation multiple stepwise linear regression and clusteranalysis has been used to predict the role of halogens in thepollution status of Lake Mariout Multivariate analysis canbe used in monitoring research because they can reduce the
4 Journal of Chemistry
cost of further environmental investigations [56ndash58] -emultivariate analysis using the correlation matrix with acorrelation coefficient (r) multiple stepwise linear regressionwith a coefficient (R) and cluster (tree clustering) at asignificance level of ple 005 is estimated by STATISTICA 99edition At the same time the principal component (PCA)can be estimated through SPSS 15 evaluation
29 Enrichment Factor (EF) EF of the determined elements(Ca Mg Na K Li B P Cu Zn Mn Fe F Cl Br and I) wascalculated by using the equations described (equations (2)and (3)) [59 60]
EF Cm sample
MedianCm Background + 2 times MADCm Background( 1113857
(2)
where Cm was the element concentration Median CmBackground represented median concentration of an ele-ment in the background and MAD Cm Background was themedian absolute deviation from the median calculated fromthe given equation
MAD median xi minus medianj xj1113872 111387311138681113868111386811138681113868
111386811138681113868111386811138681113874 1113875 (3)
-e EF values were classified into five categories defi-ciency tominimal (EFlt 2) moderate (2ltEFlt 5) significant(5ltEFlt 20) very high (20ltEFlt 40) and extremely highenrichment (EFgt 40)
210 Human Health Risk Assessment -e human healthhazard of surface water and sediment ingestion and dermalcontact was assessed by using the estimated daily intake
Table 1 -e hypothetical precipitated salts in surface and pore waters along Lake Mariout
Site 1 2 3 4 5 6 7 8 9 10 11 12 13SI of precipitated salts and minerals
Surface waterCalcite 128 138 340 146 236 303 295 297 205 258 312 126 311Aragonite 103 112 315 120 211 278 270 272 180 233 287 101 286CaSO405 H2O 208 188 126 157 156 155 170 179 199 171 115 075 181CaSO42H2O 196 176 114 144 143 143 158 167 187 158 103 063 169Ca3(PO4)2 2486 2424 2424 2424 2424 2424 2424 2424 2424 2424 2424 2424 2424Ca(IO3)2 157 137 137 137 137 137 137 137 137 137 137 137 137Ca(IO3)26H2O 1006 986 986 986 986 986 986 986 986 986 986 986 986OCP 3964 3569 3569 3569 3569 3569 3569 3569 3569 3569 3569 3569 3569HAP 4574 4349 4349 4349 4349 4349 4349 4349 4349 4349 4349 4349 4349FAP 4277 5036 5038 5195 5171 5131 5090 4982 5131 5081 4903 5095 5163CFAP 6089 1685 1786 1818 1784 1902 1883 1785 1764 1859 1604 1824 1914Fe(OH)2 1196 1217 1196 1189 1208 1059 1176 1158 1007 1192 1205 1199 1152Fe(OH)3 3544 3564 3543 3536 3555 3407 3524 3505 3354 3539 3552 3546 3499FePO42H2O 1053 1074 1053 1046 1065 916 1033 1015 864 1049 1062 1056 1008Mg(OH)2 1215 1206 1131 1171 1173 1159 1179 1188 1170 1183 1151 1152 1168Mg3(PO4)2 085 1345 1121 1240 1245 1205 1264 1291 1236 1276 1180 1184 1229Mn(IO3)2 025 243 354 303 247 312 226 055 183 198 064 262 042KIO4 576 570 552 549 565 564 559 554 551 560 489 551 548KCIO4 495 489 471 468 484 483 478 473 470 479 408 470 467ZnCO3 414 404 613 455 560 560 586 573 491 530 659 472 581ZnCO3H2O minus018 minus027 181 024 128 128 154 142 060 099 227 041 149Zn(OH)2 1198 1189 1199 1210 1254 1194 1223 1232 1216 1207 1249 1227 1203Zn(IO3)22H2O 366 357 367 378 422 362 391 400 383 375 417 395 371Pore waterFluorite 200 211 106 195 346 309 345 317 228 246 307 365 277CaSO405 H2O 370 177 190 200 168 178 202 255 203 212 191 179 211CaSO42H2O 358 165 178 188 155 166 190 243 191 200 178 167 199Ca3(PO4)2 2958 2424 2424 2424 2424 2424 2424 2424 2424 2424 2424 2424 2424Ca(IO3)2 315 137 137 137 137 137 137 137 137 137 137 137 137Ca(IO3)26H2O 1164 986 986 986 986 986 986 986 986 986 986 986 986OCP 4594 3569 3569 3569 3569 3569 3569 3569 3569 3569 3569 3569 3569HAP 5361 4349 4349 4349 4349 4349 4349 4349 4349 4349 4349 4349 4349FAP 5126 5295 5399 5270 5460 5318 5327 5338 5321 5311 5420 5373 5391CFAP 7833 1775 2068 1752 2049 2078 1990 2015 1963 2026 2121 2024 2060MgF2 299 138 177 060 262 232 095 209 212 243 222 251 203Mg(OH)2 1395 1439 1408 1400 1428 1420 1346 1425 1418 1438 1412 1391 1414Mg3(PO4)2 987 2442 2417 2355 2469 2207 2128 2317 2243 2260 2387 2132 2378KIO4 564 568 575 557 561 560 570 566 558 571 551 543 564KCIO4 483 487 494 476 480 479 489 485 477 490 470 461 483
Journal of Chemistry 5
(EDI) hazard quotient (HQ) and hazard index (HI) as givenin equations (4)ndash(11)
2101 For Surface Water Estimated daily intake of surfacewater ingestion and dermal contact (EDIIngw and EDIDermw)were computed by the following equations [61]
EDIIngw(mgkgday) (CW times CR times ET times EF times ED)
(AT times BW) (4)
EDIDermw(mgkgday) (CW times SA times PC times ET times EF times ED times CF)
(AT times BW)
(5)
where CWwas the element concentration in water (mg Lminus1)CR was the contact time (50mL hminus1) ET was the exposuretime (26 h dayminus1) EF was the exposure frequency (7 dayyearminus1) ED was the exposure duration (60 year) ATwas theaverage time (60times 365 day yearminus1) BWwas (707 kg) SAwas
the skin surface area (5700 cmminus2) PC was the dermalpermeability constant (0001 cm hminus1) and CF was theconversion factor for water (10times10minus6 kg mgminus1) [62ndash65]
2102 For Sediment Estimated daily intake of sediment byingestion and dermal contact (EDIIngs and EDIDerms) werecalculated according to the following equations [60]
EDIIngS(mgkgday) CS times IngS times RAFS times EFS( 1113857
(AT times BW) (6)
EDIDermS(mgkgday) CS times IngS times ED times SA times AF times ABS( 1113857
(AT times BW)
(7)
where CS was the concentration of the contaminant insediment (mg gminus1) IngS was the ingestion rated of sediment(80times10minus5mg kgminus1) RAFS was the relative absorption factorof sediment (058) EFS was the exposure frequency (30 day
Table 2 Distribution of the studied variables in surface water (w) and their chlorinity ratios along Lake Mariout
Determined variables Minimum Site Maximum Site Average SD Seawatera Lake Marioutbcd
Physicochemical variablesTw 137 10 1534 11 1759 134Salinity (Spermilw) 23 13 79 1 489 152Chlorinity (Clpermilw) 205 13 71 1 438 137 1898TDSw (mg Lminus1l) 24635 13 7683 1 48503 152874Turbidity (NTU) 166 8 385 12 1296 1174DOw (mg Lminus1l) 0 6 1241 2 605 483 214ndash563d
pHw 744 13 899 2 710ndash860d
CO3w (mg Lminus1) 12 1 amp 2 1152 3 31 388HCO3w (mg Lminus1) 7808 3 19032 12 1147 321Bw (mg Lminus1) 05 7 1661 1 691 411 45Pw (μg Lminus1) 003 8 126 5 029 033Siw (μg Lminus1) 009 12 699 4 317 191Caw (mg Lminus1) 6092 12 3527 8 17703 735 400 549 818ndash1464d
Mgw (mg Lminus1) 9725 3 66615 1 28684 16002 1272 1201Naw (mg Lminus1) 231 11 1420 1 101115 2972 10556 10332Kw (mg Lminus1) 8 11 59 1 3769 123 380 585Liw(mg Lminus1) 0139 11 017 1 0154 001 017SO4w (mg Lminus1) 1978 12 34111 9 16856 9488 2649 4245Cuw (μg Lminus1) 204 3 621 7 317 113 7Mnw (μg Lminus1) 001 8 amp13 198 3 315 554 10Few (μg Lminus1) 009 9 1392 13 69 419 40Znw (μg Lminus1) 527 2 2367 5 1085 578 20Fw (mg Lminus1) 015 11 396 12 204 117 13Clw (mg Lminus1) 2048 13 7284 1 4397 1400 18980Brw (mg Lminus1) 506 12amp13 541 5 1813 1891 65 592Iw (μg Lminus1) 566 10 541 4 1108 1296 60Ion chlorinity ratioCawClw 170Eminus 02 12 100Eminus 01 13 440Eminus 02 240Eminus 02 213Eminus 02 335Eminus 02MgwClw 250Eminus 02 3 110Eminus 01 13 640Eminus 02 230Eminus 02 669Eminus 02 733Eminus 02NawClw 650Eminus 02 11 380Eminus 01 13 240Eminus 01 720Eminus 02 560Eminus 01 635Eminus 01KwClw 220Eminus 03 11 150Eminus 02 13 890Eminus 03 290Eminus 03 210Eminus 02 360Eminus 02LiwClw 240Eminus 05 1 700Eminus 05 13 380Eminus 05 110Eminus 05 939Eminus 06SO4wClw 540Eminus 03 12 110Eminus 01 13 420Eminus 02 310Eminus 02 140Eminus 01 260Eminus 01BwClw 978Eminus 05 7 332Eminus 03 9 670Eminus 03 170Eminus 03 895Eminus 04FwClw 430Eminus 05 11 140Eminus 03 13 540Eminus 04 420Eminus 04 670Eminus 05BrwClw 140Eminus 03 12 160Eminus 02 9 440Eminus 03 500Eminus 03 350Eminus 03 360Eminus 05IwClw 940Eminus 04 1 160Eminus 02 4 300Eminus 03 400Eminus 03a[51] b and c[52 53] d[54]
6 Journal of Chemistry
yearminus1) AF was the adherence factor (007mg cmminus2) andABS was the dermal absorption factor (0001 unit less)[65 66]
Hazard index (HI) is the total chronic hazard attribut-able to exposure to all determined contaminants (i) througha single exposure pathway of the ingestion and dermalcontact of water (HIIngw and HIDermw) and sediment (HIIngsand HIDerms) was given as follows [60]
HIIngW 1113944HQ IngW( 1113857i (8)
HIDermW 1113944HQ DermW( 1113857i (9)
HIIngS 1113944HQ IngS( 1113857i (10)
HIDermS 1113944HQ DermS( 1113857i (11)
3 Results and Discussion
31 Distribution of Halogens and Tested Variables in SurfaceWater
311 Distribution of Halogens in Surface Water -e rangeand average value of halogens in the surface water in thisstudy show a sequence of ClwgtBrwgt Fwgt Iw (Table 2 andFigure 2)-e current study indicate that the water sample ofpumping station (site 6) attained high concentrations offluoride (28mg Lminus1) chloride (38878mg Lminus1) and bromide(181mg Lminus1) and low iodide (641 μg Lminus1) contents (Fig-ure 2) High levels of F Br and I are detected in the MainBasin region which is affected by the drainage of El-Qalaaand El Umoum containing the agricultural and industrialwastes However halogens are involved in the manufactureof pesticides (herbicides fungicides insecticidesacaricidesand nematicides) [67] Plus halogens are produced in theproduction of fertilizers products [67] -e presented resultsof halogens in the studied lake region reflect anomalousdistribution and are mainly affected by water dischargedfrom the drainage sources However the highest fluoridebromide and iodide contents of 377mg Lminus1 6553mg Lminus1and 5410 μg Lminus1 respectively are recorded in the MainBasin affected by El-Qalaa and El Umoum drains Amongthe halogens chloride shows high levels in surface waterespecially in site 1 (72837mg Lminus1) site 2 (65218mg Lminus1)and site 10 (51687mg Lminus1) which are also related to theirlevels in the water of the drains (Figure 2) On the meantimethe lowest Spermilw and Clpermilw are observed at site 13 (ElUmoum Drain) Most of the studied variables have chlo-rinity ratios relatively lower than those measured for LakeMariout andor seawater [51ndash53 68 69] -is is mainly dueto the accumulation of wastewater from Abis and ElUmoum where agricultural products such as fertilizers andbiocides are deposited in industrial products [19]
Due to the increase in chloride content in surface watersamples the conservativeness of the chlorinity ratio is usedto describe the contamination precipitation and dissolutionof sediment components [70] -e FCl ratio in the studyarea is higher than open seawater (430Eminus 05) of a range
430Eminus 05ndash140Eminus 03 and average 540Eminus 04 -e BrClratio is relatively similar to that of seawater (Table 2) -ehighest FCl BrCl and ICl ratios in surface water140Eminus 03 160E ndash 02 and 160Eminus 02 are recorded in site 13(El Umoum drain outside the lake) site 9 (South West Basinin the lake) and site 4 (Main Basin in the lake) -erefore itcan be concluded that the distribution of halogens in thesurveyed area is greatly affected by the drainage of the El-Qalaa El Umoum and the El Nubaria drains
312 Distribution of Tested Variables in Surface Water-e range and average values of the tested variables (Tw Spermilw Clpermilw TDSw turbidity DOw pHw CO3w HCO3w BwPw Siw Caw Mgw Naw Kw Liw SO4w Cuw Mnw Few andZnw) in surface waters of the present study are listed inTable 2 Turbidity fluctuates from 166 to 3850 NTU at sites8 and 12 respectively DO is completely depleted at sites 5 6and 11 and has the highest amount 1241mg Lminus1 at site 2with an average 605mg Lminus1 relatively similar to the reportedLake Mariout value (214ndash563mg Lminus1 [54]) (Table 2) -eaverage content of DO in the lake is higher than those re-ported for the ocean seawater (32ndash48mgL) [71] -e levelsof DO probably relate to the oxygen-producing processes ofthe photosynthesis processes of phytoplankton and mac-rophytes [72] -e presented results indicate that site 1(affect by Abis drainage) is the most affected area in the lakeas it shows the highest contents of Bw Clw Mgw Naw KwLiw and SO4w -e most important feature in the concen-trations of heavy metals Cuw Mnw and Znw in surface wateris that they possess average values lower than those reportedfor the threshold guideline (10 100 and 50 μg Lminus1) [73 74]
-e present study clears out a descending trend in thesurface water average concentrations of halogens andtested variables in the lake as follows TDSw gtClw gtNaw gtMgw gtCaw gt SO4w gtHCO3wgtKw gtCO3w gt Bw gt Brwgt FwgtLiw gt Znw gt Few asymp Siw gtMnw gt Pw gt Iw (Table 2)
313 Interactions of Halogens and Tested Variables inSurface Water Chloride in surface water is significantlyrelated to the drainage water content showing good cor-relations with Tw (r 0631 ple 0028) and pHw (r 0769ple 0003) (Supplementary Table 1) -e negative moderaterelation of Fw and Ip (r 0606 ple 0037) may indicatereplacement of iodine in pore water by fluoride of the surfacewater-emoderate relationship between fluoride in surfacewater and CO3w (r minus0632 ple 0027) and HCO3w(r 0593 ple 0042) may be related to carbonate exchangeand the formation of fluorite minerals (CaF2) [23]
-e correlation matrix reflects that the observed ex-traordinary levels of Bw in the surface water samples aremost probably due to its exchange with the different sedi-ment components not related to the discharged waters(Supplementary Table 1) -is findings is supported by theweak B correlation with Cuw (r minus0587 ple 0045) andgood correlation with Fs (r minus0666 ple 0018) [75 76]However Cuw is one of the pollutants that can be exchangedin drainage water -e correlations of Mgw amp Naw (r 0629
Journal of Chemistry 7
1
23
4
56
7
8
9
10
2986degE 2988degE 2990degE 2992degE
310
8degN
311
0degN
311
2degN
311
4degN
311
6degN
El-mex
pumping
statio
n Main Basin
of Lake Maryout
Southwest Basin
Qalaa Drain
El Umoum Drain
Northwest BasinFish
ery Basi
nEl Nubaria Drain
3311 to 38883888 to 43934393 to 5115
5115 to 65226522 to 7284
(a)
1
23
4
56
7
8
9
10
2986degE 2988degE 2990degE 2992degE
310
8degN
311
0degN
311
2degN
311
4degN
311
6degN
El-mex
pumping
statio
n
Main Basinof Lake Maryout
Southwest Basin
Qalaa Drain
El Umoum Drain
Northwest Basin
Fishery
BasinEl Nubaria Drain
069 to 127127 to 169169 to 242
242 to 277277 to 377
(b)
El-mex
pumping
statio
n
Main Basin of Lake Maryout
South west Basin
North west Basin
1
23
4
56
7
8
9
10
2986degE 2988degE 2990degE 2992degE
310
8degN
311
0degN
311
2degN
311
4degN
311
6degN
Qalaa Drain
El Umoum Drain
Fishery
BasinEl Nubaria Drain
613 to 852852 to 14381438 to 1732
1732 to 52745274 to 6554
(c)
El-mex
pumping
statio
n
Main Basin of Lake Maryout
Southwest Basin
Northwest Basin
1
23
4
56
7
8
9
10
2986degE 2988degE 2990degE 2992degE
310
8degN
311
0degN
311
2degN
311
4degN
311
6degN
Qalaa Drain
El Umoum Drain
Fishery
BasinEl Nubaria Drain
566 to 671671 to 761761 to 817
817 to 922922 to 5411
(d)
Figure 2 Distribution of halogens (Cl F Br and I in surface water of LakeMariout (a) Cl (mg Lminus1) (b) F (mg Lminus1) (c) Br (mg Lminus1) and (d) I(μg Lminus1)
8 Journal of Chemistry
ple 0028) Mgw amp Liw (r 0790 ple 0002) Naw amp Kw(r 0955 ple 0000 Naw amp Liw (r 0835 ple 0001) Naw ampCO3w (r minus0701 ple 0011) Kw amp Liw (r 0712 ple 0009)Kw amp CO3w (r minus0580 ple 0048) CO3w amp HCO3w(r minus0613 ple 0034) and Mgw amp SO4w (r 0631ple 0028) indicate that all these variables have some geo-chemical behaviors [77] Mg Na and Li are some com-ponents of the discharged waters however they havepositive correlations with the chlorinity and salinity of thedischarged water sources (r 0743 0619 and 0815 re-spectively) and (r 0743 0619 and 0815 respectively)Mgw and Liw contents in water samples are affected bytemperature dissolved oxygen and pH with high correla-tions of r minus0650 0677 and 0743 and minus0702 0659 and0815 respectively
32 Distribution of Halogens and Tested Variables in PoreWater
321 Distribution of Halogens in Pore Water -e averagehalogen contents in the pore water are higher than theircontents in the surface water but in the same orderClpgtBpgt Fpgt Ip (Table 3) Current research shows that thelowest and highest average values of Spermilp and Clp have beenmeasured in the pore water of site 6 and site 8 respectively Itis worth mentioning that site 6 is a mixed water of El-Qalaadrainage sewage WWTP treatment plant and lake waterInterestingly the high concentrations of fluoride chloridebromide and iodide in the pore water at site 6 are 123mgLminus1 40321mg Lminus1 11739mg Lminus1 and 24339 μg Lminus1 re-spectively (Table 3) -e salinity and chloride content in thepore water of site 8 are related to the discharge water of manypetrochemical and oil companies besides some fish farms
322 Distribution of Tested Variables in Pore Water -etested variables in the pore water (p) give the followingdescending order MgpgtNapgtCapgt SO4pgtBpgtKpgtBrpgt Fpgt LipgtPpgt Ipgt Sip (Table 3) Interestingly the deter-mined variables in the pore water have higher values thanthe surface water along the lake According to previousstudies pore water is responsible for biogeochemical reac-tions the migration and transformation of partitioned andformed compounds and the transportation of colloidalspecies [78 79] In addition pore water can explore thepotential risks of man-made pollution sources [80] -etested variables in the pore water (p) are given in a differentorder of surface water of ClpgtMgpgtNapgtCapgt SO4pgtBpgtKpgtBrpgt Fpgt Lipgt Ppgt Ipgt Sip (Tables 2and 3)
323 Interactions of Halogens and Tested Variables in PoreWater -e following interactions of halogens CO3w amp Ip Ipamp Fw Brw amp Sip Fp amp Siw and Fp amp Nap give correlationvalues (r 0706 ple 0010 r minus0606 ple 0037 r 0826ple 0001 r minus0704 ple 0011 and r 0670 ple 0017respectively) (Supplementary Table 1) However these re-lationships may indicate their precipitation andor
adsorption on the colloidal particles besides the formation ofsome chemical species [78 79] Extraordinarily large cor-relations of Nap amp HCO3w Kp amp HCO3w Spermilw amp Bp Spermilp ampKp Spermilp amp Lip and Spermilp amp Clp (r 0692 minus0609 minus07410696 0910 and 1000) may refer to the release of theseelements from sediment particles andor precipitation oradsorption [77] In the matrix the negative correlationbetween Cap and Mgp (r minus0592 ple 0042) may be relatedto the release of Mg during the recrystallization of calcite[79]-e relationship between Caw amp SO4p Cuw amp Cap Pw ampPp and Nap amp pHw (r 0744 ple 0006 r 0719 ple 0008r 0647 ple 0023 and r minus0640 ple 0025 respectively)may be due to the chemical interactions in the pore fluidsand the formation certain compounds
33Distribution ofHalogens andTestedVariables in Sediment
331 Distribution of Halogens in Sediment -e averagehalogenrsquos content in the sediment shows a different orderfrom the surface and pore waters of Brsgt FsgtClsgt Is (Ta-ble 4) -e sediment results show that the average bromidecontent is higher than fluoride followed by chloride contentand iodide with average values of 452mg gminus1 040mg gminus1029mg gminus1 and 450 μg gminus1 respectively
-e fluoride concentration in the sediment ranges from001 to 120mg gminus1 with an average value of 04plusmn 035mggminus1 -ese values are lower than reported marine sedimentvalues and higher than the El-Bardawil Lagoon [60]Amongst the halogens the study reveals that Br is the mostabundant ion in surface water pore water and sedimentsamples due to the excessive amounts of organic matter [81]On the contrary the concentration of Cl ions in sedimentsamples is lower than that in surface water and pore watersamples indicating that it exists in soluble salts -e currentresults indicate that the sediments collected from the mostaffected area by the Mediterranean Sea (site 6) contain el-evated levels of fluoride (070mg gminus1) bromide (852mggminus1) and chloride (020mg gminus1) and a reduced amount ofiodide (209 μg gminus1) (Table 4)
332 Distribution of Tested Variables in Sediment -eaverage value of test variables in the determined sedimentsamples shows a significant change from site to site with adescending order CO3sgtMgsgtCasgtNasgt SO4s gt FesgtBsgtKsgtTPsgtMn sgtZnsgtCusgt Lis (Table 4) Plus this studyclears out that the percent of sand and mud of the differentsediment samples ranges from 4 at sites 1 amp 13 to 85 atsite 11 and from 15 at site 11 to 96 at sites 1amp13 re-spectively with averages 25 and 75 respectively Plusthe porosity shows a trend opposite to the particle size andvaries from 4676 to 8214 with an average value of5609plusmn 1114 -e results of the current study reveal mod-erate amounts of CO3 in the sediment samples fluctuatingbetween 1639 and 5736 at sites 6 and 2 respectively -eresults of sand mud porosity and CO3 percentage reflect thatthe texture of the sediment is mainly composed of mud mixedwith carbonate compounds Comprehensively the large storageof sediments with carbonate (359plusmn1280) magnesium
Journal of Chemistry 9
Tabl
e3
Distribu
tionof
thestud
iedvariablesin
thepo
rewater
(p)alon
gLake
Mariout
Site
Spermilp
pHP
Ca p
(mgLminus
1 )Mg p
(mgLminus
1 )Na p
(mgLminus
1 )Kp
(mgLminus
1 )Li
p(m
gLminus
1 ))
SO4P
(mgLminus
1 ))
B P(m
gLminus
1 ))
P P(μgLminus
1 ))
SiP
(microgLminus
1 ))
F p(m
gLminus
1 ))
Cl P
(mgLminus
1 ))
Brp
(mgLminus
1 ))
I p(μgLminus
1 )1
1034
787
481
42303
1097
453
042
2944
8043
363
0045
323
95419
959
7104
2934
809
5611
115725
1050
498
039
2056
663
553
0036
338
8398
1385
24698
31272
717
100
5689
1195
577
053
2778
8949
1204
0034
754
114469
2291
26347
483
796
9619
47652
974
384
043
350
19312
77
0054
215
74599
693
8393
51099
782
5611
89711
1128
42041
1667
16739
1112
0081
1698864
1332
8333
645
775
4008
75367
736
41024
2111
11739
071
0037
1231
40321
799
24339
71125
782
39278
13615
1155
516
056
3667
6051
369
006
6101209
1279
8123
8148
775
9299
84314
1355
468
055
12444
942
212
0056
892
133232
1172
7643
9684
78
962
72109
880
393
036
3778
21341
114
0087
1061429
2131
9981
10114
764
1122
113586
1195
524
049
4667
8007
071
0041
1138
102562
1332
8572
11639
742
4008
61996
915
332
033
2833
11594
754
0026
1215
67834
746
37587
125
702
481
38413
8703
274
028
2167
13913
081
0025
2154
44832
1438
9891
13755
807
3206
6467
817
446
039
4556
17246
635
0042
954
5737
533
1097
Minim
um45
702
962
13615
736
274
024
1667
6051
071
0025
215
40321
533
7104
Maxim
um148
809
39278
115725
8703
577
056
12444
21341
1204
0087
2154
133232
2291
37587
Average
919
77
718
67412
163077
4381
041
3782
1223
485
0048
955
82779
1238
14768
SD308
032
10027
29209
2132
825
01
2769
5047
391
0019
542
27891
524
9917
10 Journal of Chemistry
Tabl
e4
Distribu
tionof
thestud
iedvariablesin
thesediment(s)alon
gLake
Mariout
Site
Sand
()
Mud ()
Porosity
()
CO3s
()
B s(m
ggminus
1 )P s
(mg
gminus1 )
Ca s
(mg
gminus1 )
Mg s
(mg
gminus1 )
Na s
(mg
gminus1 )
Ks
(mg
gminus1 )
Lis(m
ggminus
1 )
SO4s
(mg
gminus1 )
Fes
(mg
gminus1 )
Cu s (μg
gminus1 )
Mn s
(μg
gminus1 )
Zns(μg
gminus1 )
F s(m
ggminus
1 )
Cl s
(mg
gminus1 )
Brs
(mg
gminus1 )
I s(μg
gminus1 )
14
964915
183
299
044
1670
811
2583
408
0028
4861
828
963
5617
1272
034
041
128
1686
244
564925
574
196
028
1002
1419
2717
269
0015
662
257
793
4350
1313
057
054
123
358
319
816667
299
246
073
1670
1216
3125
336
0022
463
487
1228
4330
1677
044
034
448
516
418
824853
3813
1111
032
668
2229
3425
365
0094
2222
770
922
4637
1245
030
020
309
296
512
884697
482
614
012
501
1115
1833
091
0040
1713
243
600
27933
1223
082
034
245
254
65
954667
164
370
157
835
1257
2958
388
0030
5648
890
1927
5347
3117
070
020
852
209
75
954762
375
524
024
367
2047
3133
256
0102
1157
546
883
4185
1393
120
020
341
259
838
626143
457
697
039
668
1621
3550
347
0145
4167
598
737
4157
1412
022
034
144
1277
918
826000
349
083
054
401
1094
3358
369
0025
2454
701
868
5702
3065
036
027
250
172
1036
645070
441
296
002
935
1763
3117
246
0045
2685
369
790
4533
1315
012
047
1012
224
1185
157000
325
240
074
969
2250
3508
328
0193
1343
1026
735
3890
1070
005
007
533
128
1237
638214
463
291
032
334
1824
3008
358
0018
556
340
728
2475
827
001
007
852
281
134
965000
177
211
054
2338
1621
3925
599
0068
833
1687
1187
6492
1853
004
027
639
194
Min
415
4667
164
083
002
334
811
1833
091
0015
463
243
600
2475
827
001
007
123
128
Max
8596
8214
574
1111
157
2338
2250
3925
599
0193
6620
1687
1927
6492
3117
120
054
1012
1686
Av
2575
5609
359
398
048
951
1559
3096
335
0063
2671
672
951
4500
1599
040
029
452
450
SD23
231114
128
276
039
603
455
522
115
0055
2030
393
343
1120
708
035
014
303
475
Minm
inim
umM
axm
axim
uma
ndAv
averageSD
stand
arddeviation
Journal of Chemistry 11
(1559plusmn455mg gminus1) and calcium (951plusmn603mg gminus1) com-ponents may be attributed to the abundance of calcium min-erals [4] However in general the average amounts of allvariables in sediment samples showmarked variations fromonesite to another with a descending order of CO3sgtMgsgtCasgtNasgtSO4sgtFesgt BrsgtBsgtKsgtTPsgtFs gtClsgtMnsgtZnsgtCusgtLisgt Is (Table 4) -e measured concentra-tions of Mn Zn Cu and Fe in the sediment samples are stilllower than the reported values and also lower than the back-ground levels of crust and the toxicological reference contents ofUS DOE (US Department of Energy) US EPA (US Envi-ronmental Protection Agency) and CEQG (Canadian Envi-ronmental Quality Guidelines) [82]
Contrasting the obtained levels for the halogens withthose previously reported ones the present study indicatesthat surface and pore waters incorporate more considerableamounts of fluoride compared to the formerly reported onesin Lake Edku (Tables 2 and 3) and lower levels in theMarioutarea than those measured along the Egyptian MediterraneanSea coast [27] Compared with the sediments previouslyfound on the Mediterranean coast of Egypt the chloridecontent in the sediments of the Mariout area is lower [83]Compared with those observed in seawater the studiedsurface water and pore water samples have lower bromidecontent and higher levels than previously reported in LakeMariout [52 53] -e concentration of iodide in surfacewater pore water and sediments is equivalent to the con-centration of rivers and lakes in the world [84]
333 Interactions of Halogens and Tested Variables inSediment -e correlation matrix shows the important roleof halogens in the formation and precipitationdissolution ofsalts and minerals produced along the lake (SupplementaryTable 1) However it shows that chloride seems to be in thesoluble forms along the surface and pore waters of studiedarea showing good relations with Caw (r 0666 ple 0018)Clp (r 0677 ple 0016) and SO4p (r 0858 ple 0000)Also Cls gives good correlations with Mgw (r 0710ple 0010) Naw (r 0602 ple 0038) Clw (r 0619ple 0032) Mgp (r 0774 ple 0003) and Kp (r 0731ple 0007) Chloride in the surface and pore waters plays animportant role in the dissolution association and formationof various salts along the lake -e good relationship be-tween Is and Caw (r 0666 ple 0018) may reflect the de-positionrelease of CaI+ during the formationdissolution ofcalcium carbonate [85] In addition these correlations maybe related to organic-I which formed by bacterial species andtheir remineralization in bottom sediments [86] -emoderate relationship between Nas and Brw (r minus0622ple 0031) may indicate the possible formation of BrClspecies and the precipitation or adsorption of Na minerals insediments [87] -e results of this study also reflect thestrong negative correlation between Fs and Bw (r minus0666ple 0018) which may be related to the release of fluoridefrom sediment and the formation of soluble fluoridecomplexes ((BFn[OH]4minusn)minus) with the excessive boron con-centration in the water [88] -e negative relation betweenKs and Spermilw (r minus0673 ple 0016) possibly reflect that Kw
preferentially chooses to exist in the soluble form of KClrather than being adsorbed andor bound by some richminerals in the sediment
-e significant correlations between CO3s and Mgw(r 0637 ple 0026) CO3s and Clw (r 0723 ple 0008)CO3s and pHw (r 0833 ple 0001) CO3s and Spermilw(r 0723 ple 0008) and between CO3s and Ks (r minus0673ple 0016) may be accompanied by the possible formationdissolution of the dolomite mineral in the presence ofsufficient Mgw which is usually affected by optimal pHsalinity and the potassium salts (Supplementary Table 1)-ese observed results are matching with the previouslyreported studies [32] Significant negative correlation be-tween TPs and CO3s (r minus0744 ple 0006) may indicate theextended release of P from carbonate minerals and for-mation of apatites [32]
-e correlation matrix also refers to other possible in-teractions between the remaining determined variables(Supplementary Table 1) -e significant correlation be-tween SO4s andMgw (r 0706 ple 0010) and Liw (r 0633ple 0027) may be associated to the formation of Mg-sulfateand the pollution of sediments by discharged waters con-taining excessive sulfate and Li [89] In the contrary thestrong positive correlation between TPs and Cus and be-tween TPs and Zns may be related to the same source ofpolluted discharge water [23 83]
-e high negative correlations of Zns with Few(r minus0785 ple 0003) CO3s (r minus0601 ple 0039) and Cus(r 0698 ple 0012) may indicate that Zn Cu and CO3depositions in sediment samples are linked to the soluble Feform in water (ferrous) ie the release of Fe upwards in thewater column in the anoxic conditions (SupplementaryTable 1) [90] -e excellent relations found between Fesand CO3s (r minus0799 ple 0002) Fes and Cas (r 0637ple 0026) Fes and Clw (r minus0752 ple 0005) Fes and Nas(r 0720 ple 0008) and between Fes and Ks (r 0833ple 0001) may reflect the dissolution of the chelating Feassociation with the soluble organic compounds in thewater-sediment interface and the formation of the sol-uble ferrous form in low dissolved oxygen within theareas affected by untreated discharged waters [90] -estrong correlations of Mns with SO4w Nap Nas Ks CO3sZns and Fes (r minus0585 0608 0611 0698 minus0655 0691and 0716 respectively) may associate with the solubilityof abundant Mn minerals and P-Mn forms in the sedi-ment because of its possible reduction to Mn+2 solublespecies under anoxic conditions [90] It is worth men-tioning that the results of this study indicate that ap-proximately 333 of the survey sites indicate thedepletion of dissolved oxygen in their surface watersamples Under such anoxic conditions bacteria are mostlikely to use sulfate instead of oxygen to break downorganic matter and cause the release of iron and phos-phorus into the water column
-e significant direct correlation between Ks and Nas(r 0832 plt 0001) clearly reflects the transport of solublesalts of K and Na between the pore water phase of thesediment and water-sediment surface phase (SupplementaryTable 1) -e good correlation between porosity and Nas
12 Journal of Chemistry
indicates the possible transfer of Na between pore water andsediment partitions
34 Interactions of Precipitated Halogenated Compounds inSurface and Pore Waters -e Saturation Index (SI) [23 60]of twenty-three and fifteen structures in surface water andpore water samples respectively are listed (Table 1) -ecorrelation matrix of the calculated Saturation Indices withthe presented data shows the different factors affecting theinteraction of the halogenated compound with other pre-cipitated salts and minerals Table 1 explores the precipitationof the phosphate minerals and salts are most abundantfollowed by the hydroxidesrsquo salts iodate salts sulfate andcarbonate minerals and salts in surface waters Amongst thehalogens precipitated salts fluoride minerals especiallyfluorapatites and carbonate-fluorapatite (FAP and CFAP)have high SI values in surface water (4277ndash5195 and1604ndash6089 respectively) and in pore water (5126ndash5460 and1752ndash7833 respectively) Bromide and chloride are mainlyfound in the soluble forms in surface and pore waters Iodidesalts (Ca(IO3)2 and Ca(IO3)26H2O) moderately precipitatein surface and pore Iron salts precipitate in surface waterwhile in pore water they are not formed -us SI contentreflects that halogens especially fluoride and iodide play avital role in reducing lake pollution
In addition Table 1 shows that the precipitation com-pounds that may be formed in surface water are relativelydifferent from those in sediment pore water For examplefluorite (CaF2) and sellaıte (MgF2) may be only formed inpore water while calcite and aragonite may be deposited insurface water However the formation of fluorite in surfacewater is related to Naw (r 0778 ple 0003) Kw (r 0704ple 0011) CO3w (r minus0718 ple 0009) Fw (r 0770ple 0003) and Ip (r minus0785 ple 0003) (SupplementaryTable 1)
-e formation of calcium sulfate hemihydrate calciumsulfate and anhydrite in water is related to the increase in theamounts of Caw Mgw SO4w Nap Fp Sip Cls and Mns andthe decrease in porosity values On the other hand pre-cipitation of calcium phosphate is related to Brw (r 0751ple 0005) Znw (r 0668 ple 0018) Pw (r 0881ple 0001) and Ks (r 0881 ple 0001) ie it is affected bythe discharged water composition (Supplementary Table 1)
-e formation of calcite and aragonite in surface water isrelated to the formation of CO3w (r 0753 ple 0005) anddissociation of HCO3w (r minus0660 ple 0020) pHw values(r minus0654 ple 0021) and their dissolution in sediment(r minus0620 ple 0032) (Supplementary Table 1)
-e dolomite formation in water may be affected by theincrease of CO3w (r 0817 ple 0001) and the decrease ofHCO3w (r minus0658 ple 0020) increase in TDSw (r 0599ple 0040) and increase in pHw (r minus0656 ple 0021)besides the possible release of CO3s from abundant sediment(r minus0624 ple 0030) and the precipitation of calcite(r 0984 ple 0000) and aragonite (r 0984 ple 0000) intosediment fraction (Supplementary Table 1)
Generally in the current study the possible formedhalogenated minerals and salts are affected by their
abundance in different components of the lake besides theirpossible dissolution or formation on the sediment texturesgeochemistry of the sediments and physicochemical vari-ables of water in addition to the components of the dis-charged waters
35 Interactions of Dissolved Halogenated Compounds inSurface and PoreWaters -e utilization of dissolved salts insurface and pore waters by utilizing Palmerrsquos method andpiper ternary diagram [50] indicates that Na is the richestcation in surface water followed by Mg Ca and K At thesame time Mg is the most predominate one in the porewater (Figures 3 and 4) Obviously Cl is the most importantanion in surface water and pore waters samples Howeverthe piper ternary diagrams of surface water and pore waterclearly shows that NaCl is the most dominant in surfacewater while MgCl2 is the most abundant in pore waterCoincidently Palmerrsquos method also reflects that NaCl(574) is the most existent species in surface water fol-lowed by MgCl2 (304) CaCl2 (71) CaSO4 (29)Ca(HCO3)2 (14) and KCl (12) (Figure 3) At the sametime MgCl2 (760) is the most present species in porewater followed by NaCl (73)asympMg(HCO3)2 (73)Ca(HCO3)2 (52) and MgSO4 (31) (Figure 4)
36 Multivariate Analysis
361 Principal Component (PCA) By applying Varimaxrotation and Kaiser normalization to 98 variables in the PCAfor halogens and tested variables and calculated parametervalues 7 extracted PCs with eigenvalues higher than 1 areobtained However it is important that the eigenvalue mustbe greater than 1 Its seven PCs explain 8558 of the totalvariance
-e first principle component (PC1) is 1473 of thetotal variance and shows positive coefficient factor loadingsfor CO3w TDSw Kp calcite aragonite dolomite FeCO3MgCO3 ZnCO3 and ZnCO3H2O (0804 0547 05320938 0938 0947 0741 0940 0866 and 0866 respec-tively) In addition it provides negative factor loadings forHCO3w pHw Bw Nap and CO3s (minus0782 minus0610 minus0595minus0532 and minus0572 respectively) PC1 is related to thefactors affecting the carbonate compounds that may beformed in the area under consideration
PC2 accounts to 1458 of the total variance and alsoshows positive and negative coefficient factor loadingsrepresenting the different interactions between the CawMgw Liw SO4wMgp Nap pHp Cls SO4s Brs and porosityin water pore water and sediment that are responsible forthe composition of sulfate magnesium and phosphateprecipitates besides the effect of the discharged waters onwater-pore water-sediment componentsrsquo cycles
PC3 typically shows 1377 of the total variance withpositive and negative loadings which can properly explorethe effect of the principal sources of local pollution on thedissolving of heavy metals B and P from sediment into thewater column and the probable formation of Fe(OH)2Fe(OH)3) and FePO4
Journal of Chemistry 13
Similarly the coefficient factor loadings of PC4 with1355 are related to the influence of the polluted dischargewater and sediment texture on the formation of F Cl and Isalt besides the precipitation of halogenated compounds(FeF2 Mn(IO3)2 KIO4 and KCIO4) besides their minerals(CaF2 MgF2 FAP and CFAP)
Simultaneously PC5 gives 1092 of the total variancewith positive and negative loadings which explains therelations between the physicochemical limits of the surfacewater pore water and sediment components and theprecipitation of minerals and salts (OCP HAP CuBrZn(OH)2 and Zn(IO3)22H2O) -is is also associated tothe influence of the sedimentary material on the release ofMn Fe and P from sediment into pore water and watercolumn and formation of Ca3(PO4)2 OCP and HAPminerals
However PC6 associates with 100 of the total variancegiving positive and negative coefficient factor loadingswhich explain that the sediments (minerals andor organic-iodine compounds) are only the acting sink for iodine andiodine species (Iminus and IOminus
3 ) in the water as previously re-ported [84] PC6 also reflects the precipitation of severalhalogenated compounds such as calcium iodate (Ca(IO3)2and Ca(IO3)26H2O) and copper iodate (CuI andCuIO3H2O) besides Cu3(PO4)2 species in the lake watercolumn
-e loadings of PC7 contribute by 804 and show thatthe release of calcium in pore water into the water column isresponsible for the precipitation of halogenated compounds(CuCl and Zn(IO3)22H2O) as well as copper and Zn salts(Cu3(PO4)2 and Zn(OH)2)
362 Cluster Analysis On the other hand cluster analysisshows that the similarity of sites 1amp4 5amp8 6amp9 2amp10 and11amp13 is due to the texture of sediment
363 Multiple Regression Multiple regression equations ofhalogens as dependent variables and the other determinedand calculated parameters as independent variables insurface water pore water and sediment partitions are listed(Table 5)-e amount of fluoride in water samples is affectedby the discharged watersrsquo fundamental components espe-cially Zn and Cu besides its surface water-pore water in-teractions Its content in pore water seems to be stronglyaffected by its substitution competition with other halogensin surface water-spore water-sediment cycle due to its highelectronegativity Generally in the affected area the type ofpollutant in the discharged water plays an important role inthe dissolution andor precipitation of fluoride and otherhalogens in the surface water-pore water-sediment cycle
574
147129
300
12
Ca(HCO3)2CaSO4CaCl2
MgCl2KClNaCl
(a)
SO4
2 + CIndash Ca 2+ + Mg 2+
CO32ndash + HCO3
ndashNa+ + K+
Mg2+ SO42ndash
Ca2+ CIndash
(b)
Figure 3 (a) distribution and (b) piper ternary diagram of the formed dissolved salts in surface water of Lake Mariout
Ca(HCO3)2Mg(HCO3)2MgSO4
NaClMgCI2KCl
760 1052
7373 31
(a)
SO4
2ndash + C
Indash
Ca 2+ + Mg 2+
CO32ndash + HCO3
ndashNa+ + K+
Mg2+ SO42ndash
CIndashCa2+
(b)
Figure 4 (a) distribution and (b) piper ternary diagram of the formed dissolved salts in pore water of Lake Mariout
14 Journal of Chemistry
Table 5 -e multiple regression analyses of each halogen as dependent variable and other tested variables in the surface water pore waterand sediment partitions besides the precipitated salts in surface water along Lake Mariout
Dependentvariable Multiple regression equation R2
FluorideLake water FW 3162 + 092 Zn F2 minus 033 SiP + 021 CuIminus 017 SpermilP 09911
Pore water Fp minus2567minus117 SiW minus 033 LiP minus 062 CuClminus 028 IS + 023 TDSW+ 017 KIO4 minus 012 BrW minus 004porosity + 004 PW
10000
Sediment FS 088 CAPminus 049 MgS minus 046 DOW+039MgW+ 027 Mn(IO3)2 + 015 Cu3(PO4)2 + 004 HAP+ 002 pHP 10000ChlorideLake water No relation 00000Pore water No relation 00000Sediment ClS minus116 + 046 MgP + 077 Kp minus 049 dolomite + 017 TDSW minus 011 CuI + 005 NaS + 002 BS + 001 FeF2 10000Bromide
Lake water BrW 1563 + 110 CuBrminus 057 CuClminus 021 KS minus 014 pHP minus 011 TPS + 014 FeW+ 007 ZnSminus 002 PP + 001turbidity 10000
Pore water BrP minus1516minus 055 FeS minus 073 BS + 061 MnW+ 083 SiP + 049 NaS minus 031MnS minus 015 CuBr + 011 pHW minus 001CaW
10000
Sediment BrS 015 SiP + 195 CFAP+ 002 FP minus 045 IS + 192 sand+ 037 MnW minus 029 MgS minus 012 LiP + 005Ca3(PO4)2 minus 002 ZnF2
10000
IodideLake water IW 099 Ca(IO3)6H2O 09999
Pore water IP minus097 ZnF2 minus 057 Li3PO4 minus 053 BP + 034 FAP+ 015 Ca(IO3)2 +MnW+ 005 KS minus 009 turbidity + 055CaS
09999
Sediment IS minus072 + 135 SO4P + 023 Mn(IO3)2 + 063 FeW+ 031 TPS minus 035 MgP minus 012 Zn(CO3)22H2O 09993
40E + 0135E + 0130E + 0125E + 0120E + 0115E + 0110E + 0150E + 0000E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
12345
678910
111213
(a)
10E + 0090E ndash 0180E ndash 0170E ndash 0160E ndash 0150E ndash 0140E ndash 0130E ndash 0120E ndash 0110E ndash 0100E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
12345
678910
111213
(b)
12345
678910
111213
40E ndash 0235E ndash 0230E ndash 0225E ndash 0220E ndash 0215E ndash 0210E ndash 0250E ndash 0300E ndash 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
(c)
12345
678910
111213
80E ndash 0670E ndash 0660E ndash 0650E ndash 0640E ndash 0630E ndash 0620E ndash 0610E ndash 0600E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
(d)
Figure 5 Hazard quotient of ingestion and dermal contact of surface water and sediment of LakeMariout (a) ingestion of water (b) dermalcontact of water (c) ingestion of sediment and (d) dermal contact of sediment
Journal of Chemistry 15
Minerals and precipitated salts in the different partitions(surface water pore water and sediment) play an importantrole in the deposition and release of halogens in sedimentsAdditionally the texture and the porosity of the sedimentsplay a key role in the distribution of halogens in the threepartitions Interestingly chloride is the only halogen that hasnegligible interactions along the surface water and porewater partitions because it is present in large quantities inthe form of soluble salts (NaCl and MgCl2)
37 Pollution Status
371 Enrichment Factor (EF) Twowell-knownmethods areused to assess environmental pollution public health sig-nificance of ingestion and dermal contact with water andsediment components and sediment enrichment factor (EF)[59 60]
-e average EF values of the determined elements CaMg Na K Li B P Cu Zn Mn Fe F Cl Br and I are alllower than the value that is less than the minimum en-richment value (EFlt 2)-us the area under investigation isstill ecologically considered as an unpolluted region
372 Human Health Risk Assessment -e EDI HQ and HIshow the variable values of all pollutants in the surface waterand sediments along the lake region and in drains (sites11ndash13) under study Among all the calculated variables ofsurface water ingestion (EDIIngw) and dermal contact(EDIDermw) Cl is still the only variable that shows high levels(average 1551 and 43mg kgminus1 dayminus1 respectively) -eestimation daily intake of sediment ingestion (EDIIngs) anddermal contact (EDIDerms) of Mg Ca and Na give maximumaverage amounts of 841Eminus 02 513E ndash 02 and167Eminus 03mg kgminus1 dayminus1 respectively
Among the HQ of the calculated detection variables thecontent of HQB of ingestion and dermal contact with waterand sediment is the highest However 70 of sites have HQBvalues more than 10 (Figure 5) Comparing the HQ values ofall the determined variables HQB of the ingestion of surfacewater shows values higher (gt10) However due to the impactof drainage the HQB values of stations 1ndash4 8ndash10 12 and 13
are higher than 10 -erefore these sites can be consideredas the area with the most serious boron pollution caused byuntreated discharged water disposal In addition the HIIngwlevel of water ingestion for the studied variables in all sites ismuch higher than 10 (Figure 6) Except for boron it isusually concluded that the study area does not pose any riskto the population due to halogens or other variables Ac-cordingly this information may help the official authoritiesoptimize management plans and strengthen their pollutioncontrol actions in Lake Mariout
4 Conclusions
-e effects of halogen salts and minerals on the pollution ofLake Mariout were studied Halogens and some physico-chemical variables in three partitions surface water porewater and sediment in Lake Mariout were evaluated -ehalogen content was variable between different sites andchloride was the main halogen in surface water and porewater but it was very rare in the lakersquos sediment partitionPiper ternary diagram and Palmerrsquos method reflected thatNaCl was the dominant salt in surface water while MgCl2was the main dissolve salt in pore water-e chlorinity ratiosof halogens and tested variables were directly matched to thefeeding drain sources
Moreover the Saturation Index (SI) reveals that 23 and 15precipitated salts and minerals are formed in surface water andpore water respectively -e SI value indicated the formationof phosphate minerals in surface water and pore water es-pecially octacalcium phosphate (OCP Ca4H(PO4)325H2O)and hydroxyapatite (HAP Ca5(PO4)3OH) In addition tofluoride minerals especially fluorapatite (FAP) and carbonate-fluorapatite (CFAP) were obviously precipitated from surfacewater and pore water Soluble salts of bromide and chloridewere formed in surface water and pore water Iodide salts(Ca(IO3)2 and Ca(IO3)26H2O) were moderately precipitatedin the surface water and pore water
Moreover the multivariate analysis including the cor-relation matrix multiple stepwise linear regression treeclustering and principle component (PCA) of all the de-termined and calculated variables was applied to estimatethe proposed interaction between halogens and other tested
10E + 02
16E + 0214E + 0212E + 02
80E + 0160E + 0140E + 0120E + 0100E + 00
1 2 3 4 5 6 7 8 9 10 11 12 13
HIIngHIDerm
(a)
1 2 3 4 5 6 7 8 9 10 11 12 13
HIIngHIDerm
40E ndash 0235E ndash 0230E ndash 0225E ndash 0220E ndash 0215E ndash 0210E ndash 0250E ndash 0300E + 01
(b)
Figure 6 Hazard index of ingestion and dermal contact of the studied variables in surface water and sediment of Lake Mariout (a) waterand (b) sediment
16 Journal of Chemistry
variables in the polluted area under study -e multivariateanalysis showed that there were many interactions betweenhalogens and tested variables High levels of fluoride bro-mide and chloride in surface water were related to thecomposition of drainage waters -e enrichment factor (EF)showed that Lake Mariout was not polluted However thehuman health adverse effects calculated for surface waterand sediment did not reflect any possible likelihood hazardeffects from halogens
Interestingly the current study concluded that halogencompounds especially fluorides are most likely to be de-posited from surface lakes in the form of many minerals andprecipitation thereby reducing the adverse pollution effectson human health -e results obtained through this workhelp to find the correlations between the sampling sites andthe variables obtained by physical and chemical measure-ments which can be used to construct a fast decision modelfor separating different water quality samples -is infor-mation may help the official authorities optimize manage-ment plans and strengthen their pollution control measuresin Lake Mariout
Data Availability
-e data used to support the findings of this research areincluded within the paper
Conflicts of Interest
-e authors declare that there are no conflicts of interestregarding the publication of this manuscript
Supplementary Materials
Supplementary Table 1 correlation matrix of variable insurface water pore water and sediment partitions besidesthe precipitated salts in surface water along Lake Mariout(Supplementary Materials)
References
[1] M S Masoud T O Said G El-Zokm and M A ShreadahldquoAssesment of heavy metals contamination in surface sedi-ments of the Egyptian Red Sea Coastsrdquo Australian Journal ofBasic and Applied Sciences vol 6 pp 44ndash58 2012
[2] M A Shreadah M I Abdel Moneim T O SaidE M I Fathallah and M E Mahmoud ldquoPAHs in seawater ofthe semi-closed areas along the Alexandria coast of EgyptianMediterranean seardquo Journal of Environmental Protectionvol 4 no 11 p 11 Article ID 40298 2013
[3] S Abdel Ghani G El Zokm A Shobier T Othman andM Shreadah ldquoMetal pollution in surface sediments of Abu-Qir bay and Eastern harbour of Alexandria Egyptrdquo EgyptianJournal of Aquatic Research vol 39 no 1 pp 1ndash12 2013
[4] G F El-Said ldquoBioaccumulation of key metals and othercontaminants by seaweeds from the Egyptian MediterraneanSea Coast in relation to human health riskrdquo Human andEcological Risk Assessment An International Journal vol 19no 5 pp 1285ndash1305 2013
[5] M A Shreadah A H Shobier S Abdel Ghani G M El-Zokm and T O Said ldquoMajor ions anomalies and
contamination status by trace metals in sediments from twohot spots along the Mediterranean Coast of Egyptrdquo Envi-ronmental Monitoring and Assessment vol 187 no 280pp 1ndash18 2015
[6] A El Nemr G F El-Said A Khaled and S Ragab ldquoDis-tribution and ecological risk assessment of some heavy metalsin coastal surface sediments along the Red Sea Egyptrdquo In-ternational Journal of Sediment Research vol 31 no 2pp 164ndash172 2016
[7] A El Nemr G F El-Said S Ragab A Khaled and A El-Sikaily ldquo-e distribution contamination and risk assessmentof heavy metals in sediment and shellfish from the Red Seacoast Egyptrdquo Chemosphere vol 165 pp 369ndash380 2016
[8] A El Nemr and G F El-Said ldquoAssessment and ecological riskof heavy metals in sediment and molluscs from the Medi-terranean coastrdquo Water Environment Research vol 89 no 3pp 195ndash210 2017
[9] M A Sheradah A A El-Sikaily N M Abd El MoneamN E Abd El Maguid and M G Zaki ldquoChemical and bio-chemical evaluation of marine pollution by polychlorinatedbiphenyls and pesticides in two regions along the EgyptianMediterranean Seardquo International Journal of EnvironmentalMonitoring and Analysis vol 6 no 3 pp 95ndash109 2018
[10] M A Shreadah A A-M M El-Sayed A A S TahaA-M M Ahmed and H H Abdel Rahman ldquoEvaluation ofdifferent anthropogenic effluents impacts on the water qualityusing principal component analysis a case study of Abu-QirBay-Alexandria-Egyptrdquo International Journal of Environ-mental Monitoring and Analysis vol 7 no 3 pp 56ndash67 2019
[11] G F El-Said M M El-Sadaawy A H Shobier andS E Ramadan ldquoHuman health implication of major and traceelements present in commercial crustaceans of a traditionalseafood marketing region Egyptrdquo Biological Trace ElementResearch vol 199 pp 315ndash328 2020
[12] M A Shreadah S A A Ghani H B I HawashA A E Samie and A E M M Ahmed ldquoOrganotin com-pounds in sediments of northern lakes Egyptrdquo Journal ofEnvironmental Protection vol 05 no 17 pp 1654ndash1666 2014
[13] A M Younis G M El-Zokm and M A Okbah ldquoSpatialvariation of acid-volatile sulfide and simultaneously extractedmetals in Egyptian Mediterranean Sea lagoon sedimentsrdquoEnvironmental Monitoring and Assessment vol 186 no 6pp 3567ndash3579 2014
[14] G F El-Said S E O Draz M M El-Sadaawy andA A Moneer ldquoSedimentology geochemistry pollution statusand ecological risk assessment of some heavy metals insurficial sediments of an Egyptian lagoon connecting to theMediterranean Seardquo Journal of Environmental Science andHealth Part A vol 49 no 9 pp 1029ndash1044 2014
[15] G M El Zokm M A Okbah and A M Younis ldquoAssessmentof heavy metals pollution using AVS-SEM and fractionationtechniques in Edku Lagoon sediments Mediterranean SeaEgyptrdquo Journal of Environmental Science and Health PartAvol 50 no 6 pp 571ndash584 2015
[16] G M El Zokm H R Z Tadros M A Okbah andG H Ibrahim ldquoldquoEutrophication assessment using TRIX andCarlsonrsquos indices in Lake Mariout water Egyptrdquo EgyptianJournal of Aquatic Biology and Fisheries vol 22 no 5pp 331ndash349 2018
[17] N Donia ldquoLake Maryut monitoring using remote sensingrdquo inProceedings of the gypt Eighteenth International WaterTechnology Conference IWTC18 Sharm El Sheikh Abu DhabiUAE March 2015
Journal of Chemistry 17
[18] M A Khairy ldquoAssessment of priority phenolic compounds insediments from an extremely polluted coastal wetland (LakeMaryut Egypt)rdquo Environmental Monitoring and Assessmentvol 185 no 1 pp 441ndash455 2013
[19] N A El-Naggar and E A Rifaat ldquoEgyptian coastal lakes andwetlands part Imdashcharacteristics and hydrodynamicsrdquo in eHandbook of Environmental Chemistry A M Negm EdSpringer International Publishing AG Berlin Germany 2017
[20] J J Hanley and K T Koga ldquoChapter 2 ldquohalogens in terrestrialand cosmic geochemical systems abundances Geochemicalbehaviors and analytical methodsrdquordquo in e Role of Halogensin Terrestrial and Extraterrestrial Geochemical ProcessesD E Harlov and L Aranovich Eds Springer InternationalPublishing AG Berlin Germany pp 21ndash121 2018
[21] A Ghosh K Mukherjee S K Ghosh and B Saha ldquoSourcesand toxicity of fluoride in the environmentrdquo Research onChemical Intermediates vol 39 no 7 pp 2881ndash2915 2013
[22] M M Naim A A Moneer and G F El-Said ldquoPredictiveequations for the defluoridation by electrocoagulation tech-nique using bipolar aluminum electrodes in the absence andpresence of additives a multivariate studyrdquo Desalination andWater Treatment vol 57 no 14 pp 6320ndash6332 2016
[23] G F El-Said N A Shaltout M M El-Sadaawy andA M H Morsy ldquo-e precipitation of fluoride calcium andmagnesium minerals from Egyptian Mediterranean Sea coastin relation to discharged watersrdquo Desalination and WaterTreatment vol 57 no 5 pp 2113ndash2124 2016
[24] H Bureau ldquoIodine encyclopedia of geochemistry A com-prehensive reference source on the chemistry of the earthrdquo inEncyclopedia of Earth Sciences Series W M White Ed copySpringer International Publishing AG 2016
[25] F C Kupper and C J Carrano ldquoKey aspects of the iodinemetabolism in brown algae a brief critical reviewrdquo Metal-lomics vol 11 pp 756ndash764 2019
[26] R Liteplo R Gomes P Howe and H Malcolm Fluorides-Environmental Health Criteria 227 p 290 World HealthOrganization (WHO) Geneva Switzerland 2002
[27] G F El-Said and M M El-Sadaawy ldquoSeasonal variation ofboron and fluoride in Tilapia nilotica from an Egyptian fishfarm in relation to Human health hazard assessmentrdquoHumanand Ecological Risk Assessment An International Journalvol 19 no 4 pp 930ndash943 2013
[28] WHO (World Health Organization) Bromide in Drinking-Water Background Document for Development of WHOGuidelines for Drinking-Water Quality WHO Press WorldHealth Organization Geneva Switzerland 2009
[29] G F El-Said and N A Sallam ldquo-e uptake of fluorideconcentration and its effects on the growth rate of shrimps(Palaemon elegans Rathke)rdquo Chemistry and Ecology vol 24no 3 pp 191ndash205 2008
[30] X Zhang J He B He and J Sun ldquoAssessment formationmechanism and different source contributions of dissolvedsalt pollution in the shallow groundwater of Hutuo Riveralluvial-pluvial fan in the North China Plainrdquo EnvironmentalScience and Pollution Research vol 26 no 35 pp 35742ndash35756 2019
[31] Y Zhu B Huang Z Zhu et al ldquoldquoCharacterization disso-lution and solubility of the hydroxypyromorphitendashhydroxyapatite solid solution [(PbxCa1minusx)5(PO4)3OH] at25 degC and pH 2ndash9rdquo Geochemical Transactions vol 17 no 2pp 1ndash18 2016
[32] G F El-Said M M El-Sadaawy A A Moneer andN A Shaltout ldquo-e effect of fluoride on the distribution ofsome minerals in the surface water of an Egyptian lagoon at
the Mediterranean Seardquo Egyptian Journal of Aquatic Researchvol 41 no 1 pp 31ndash39 2015
[33] Y Zhu Z Zhu X Zhao Y Liang and Y Huang ldquoChar-acterization dissolution and solubility of lead hydroxypyr-omorphite [Pb5(PO4)3OH] at 25ndash45degCrdquo Journal ofChemistry vol 2015 Article ID 269387 10 pages 2015
[34] M A Z Chahouki ldquoMultivariate analysis techniques inenvironmental sciencerdquo in Earth and Environmental SciencesDr Imran Ahmad Dar Ed InTech Open London UK 2011httpwwwintechopencombooksearth-and-environmental-sciencesmultivariate-analysis-techniques-inenvironmental-science
[35] J V Klump and C S Martens ldquoBiogeochemical cycling in anorganic-rich coastal marine basin 5 Sedimentary nitrogenand phosphorus budgets based upon kinetic models massbalances and the stoichiometry of nutrient regenerationrdquoGeochimica et Cosmochimica Acta vol 51 no 5 pp 1161ndash1173 1987
[36] R L Folk Petrology of Sedimentary Rocks University of TexasAustin TX USA 1974
[37] P Saenger ldquoA rapid spectrophotometric method for thedetermination of bromine in seawater and in the ash ofmarine algaerdquo Helgolander Wissenschaftliche Meer-esuntersuchungen vol 23 no 1 pp 32ndash37 1972
[38] P G Jeffery Chemical Methods of Rock Analysis PergamonPress New York NY USA 2nd edition 1975
[39] J D H Strickland and T R Parsons ldquoA practical handbook ofseawater analysisrdquo in Fisheries Research Board of CanadaBulletin 167p 311 Second edition Wiley Ottawa Canada1972
[40] B Horvath O Opara-Nadi and F Beese ldquoA simple methodfor measuring the carbonate content of soilsrdquo Soil ScienceSociety of America Journal vol 69 no 4 pp 1066ndash1068 2005
[41] K Grasshoff Methods of Seawater Analysis p 317 VerlagChemie Weinkeim Germany 1976
[42] R Danovaro D Marrale N Della Croce P Parodi andM Fabiano ldquoBiochemical composition of sedimentary or-ganic matter and bacterial distribution in the Aegean Seatrophic state and pelagic-benthic couplingrdquo Journal of SeaResearch vol 42 no 2 pp 117ndash129 1999
[43] APHA-AWWA-WPCF (American Public Health Associa-tion) Standard Methods for the Examination of Water andWaste Water American Public Health Association Wash-ington DC USA 20th edition 1999
[44] K I Aspila H Agemian and A S Y Chau ldquoA semi-auto-mated method for the determination of inorganic organicand total phosphate in sedimentsrdquo e Analyst vol 101no 1200 pp 187ndash197 1976
[45] J P Riley and D Taylor ldquoChelating resins for the concen-tration of trace elements from sea water and their analyticaluse in conjunction with atomic absorption spectrophotom-etryrdquo Analytica Chimica Acta vol 40 pp 479ndash485 1968
[46] G F El-Said and A El-Sikaily ldquoChemical composition ofsome seaweed from Mediterranean Sea coast Egyptrdquo Envi-ronmental Monitoring and Assessment vol 185 no 7pp 6089ndash6099 2013
[47] Directorate General of Health Services Ministry of Health andFamilyWelfare Government of India ldquoManual of methods ofanalysis of foodsrdquo in Fruit and Vegetable Productsp 57Directorate General of Health Services Ministry of Health andFamily Welfare Government of India New Delhi India2005
[48] A Gunnars S Blomqvist and C Martinsson ldquoInorganicformation of apatite in brackish seawater from the Baltic Sea
18 Journal of Chemistry
an experimental approachrdquo Marine Chemistry vol 91 no 1-4 pp 15ndash26 2004
[49] W M Haynes D R Lide and T J Bruno CRC Handbook ofChemistry and Physics A Ready Reference Book of Chemicaland Physical Data CRC Press Taylor amp Frances Group BocaRaton FL USA 97th edition 2017
[50] M S Masoud M I El-Samra and M M El-Sadawy ldquoWaterchemistry of el-mex bay west of Alexandria Egyptrdquo eEgypian Science Magazine vol 2 pp 70ndash78 2005
[51] F J Millero R Feistel D G Wright and T J McDougallldquo-e composition of standard seawater and the definition ofthe reference-composition salinity scalerdquo Deep Sea ResearchPart I Oceanographic Research Papers vol 55 no 1pp 50ndash72 2008
[52] S K El-Wakeel S A Morcos and A M Mahlis ldquo-e majorcations in Lake Maryut watersrdquo Hydrobiologia vol 36 no 2pp 253ndash274 1970
[53] A M Mahlis S A Morcos and S K El-Wakeel ldquo-e majoranions in Lake Maryut watersrdquo Hydrobiologia vol 36 no 2pp 275ndash294 1970
[54] A S Saad M A Massoud R A Amer and M A GhorabldquoAssessment of the physico-chemical characteristics andwater quality analysis of Mariout Lake southern of Alexan-dria Egyptrdquo Journal of Environmental and Analytical Toxi-cology vol 7 no 1 p 421 2017
[55] R Rumuri ldquoDataset on hydrogeochemical characteristics ofgroundwater and surface water in Kattumannarkoil TalukIndiardquo Data in Brief vol 32 Article ID 106058 2020
[56] P Szefer S W Fowler K Ikuta et al ldquoA comparative as-sessment of heavy metal accumulation in soft parts and byssusof mussels from subarctic temperate subtropical and tropicalmarine environmentsrdquo Environmental Pollution vol 139no 1 pp 70ndash78 2006
[57] N F Soliman G M El Zokm and M A Okbah ldquoRisk as-sessment and chemical fractionation of selected elements insurface sediments from Lake Qarun Egypt using modifiedBCR techniquerdquo Chemosphere vol 191 pp 262ndash271 2018
[58] G M El Zokm M I A Ibrahim L A Mohamed and M El-Mamoney ldquoCritical geochemical insight into Alexandria coastwith special reference to diagnostic ratios (TOCTN amp SrCa)and heavy metals ecotoxicological hazardsrdquo Egyptian Journalof Aquatic Research vol 46 no 1 pp 27ndash33 2020
[59] A S Likuku K B Mmolawa and G K GaboutloeloeldquoAssessment of heavy metal enrichment and degree of con-tamination around the copper-nickel mine in the SelebiPhikwe Region Eastern Botswanardquo Environment and EcologyResearch vol 1 no 2 pp 32ndash40 2013
[60] M K Khalil S E O Draz G M El Zokm and G F El-SaidldquoApportionment of geochemistry texturersquos properties and riskassessment of some elements in surface sediments from Bar-dawil Lagoon Egyptrdquo Human and Ecological Risk AssessmentAn International Journal vol 22 no 3 pp 775ndash791 2016
[61] M M El-Sadaawy and G F El-Said ldquoAssessment of fluoridein three selected polluted environments along the EgyptianMediterranean Sea effects on local populationsrdquo Human andEcological Risk Assessment An International Journal vol 20no 6 pp 1643ndash1658 2014
[62] USEPA ldquoSuperfund exposure assessment manualrdquo inOSWER Directive 92855-1EPA540l-88001Office of Emer-gency and Remedial Response Washington DC USA 1988
[63] USEPA ldquoExposure factors handbookrdquo in EPA6008-89043Office of Health and Environmental Assessment Wash-ington DC USA 1989
[64] Health Canada ldquoFederal Contaminated Site Risk Assessmentin Canadardquo Part II Health Canada Toxicological ReferenceValues (TRVs) Cat H46-204-368E Calgary Health CanadaOttawa Canada 2007
[65] J Iqbal S A Tirmizi and M H Shah ldquoStatistical appor-tionment and risk assessment of selected metals in sedimentsfrom Rawal Lake (Pakistan)rdquo Environmental Monitoring andAssessment vol 185 no 1 pp 729ndash743 2013
[66] USEPA (US Environmental Protection Agency) Region 6USAEPA ldquoMultimedia Planning and Permitting DivisionrdquoOffice of Solid Waste Center for Combustion Science andEngineering Washington DC USA 2005
[67] P Jeschke ldquoLatest generation of halogen-containing pesti-cidesrdquo Pest Management Science vol 73 no 6 pp 1053ndash10662017
[68] M A Shreadah O A El-Rayis N A Shaaban andA M Hamdan ldquoWater quality assessment and phosphorusbudget of a lake (Mariut Egypt) after diversion of wastewaterseffluentsrdquo Environmental Science and Pollution Researchvol 27 no 21 pp 26786ndash26799 2020
[69] J P Riley and M Tongudai ldquo-e major cationchlorinityratios in sea waterrdquo Chemical Geology vol 2 pp 263ndash2691967
[70] R B McCleskey D K Nordstrom D D Susong J W Balland J M Holloway ldquoSource and fate of inorganic solutes inthe gibbon river yellowstone national park Wyoming USArdquoJournal of Volcanology and Geothermal Research vol 193no 3-4 pp 189ndash202 2010
[71] G T F Wong and K-Y Li ldquoWinklerrsquos method overestimatesdissolved oxygen in seawater iodate interference and itsoceanographic implicationsrdquo Marine Chemistry vol 115no 1-2 pp 86ndash91 2009
[72] B S R V Prasad P D N Srinivasu P S VarmaA V Raman and S Ray ldquoDynamics of dissolved oxygen inrelation to saturation and health of an aquatic body a case forChilka Lagoon Indiardquo Journal of Ecosystems vol 2014 Ar-ticle ID 526245 17 pages 2014
[73] China Environmental Protection Agency EnvironmentalQuality Standards for Surface Water (GB3838ndash2002) NationalEnvironmental Protection Agency of China Beijing China2002
[74] Y Jia L Wang Z Qu and Z Yang ldquoDistribution con-tamination and accumulation of heavy metals in watersediments and freshwater shellfish from Liuyang RiverSouthern Chinardquo Environmental Science and Pollution Re-search vol 25 no 7 pp 7012ndash7020 2018
[75] A Moneer M El-Sadawy G El-Said and A Radwan ldquoBoronhuman health risk assessment relative to the environmentalpollution of Lake Edku Egyptrdquo Journal of King AbdulazizUniversity vol 23 no 2 pp 41ndash55 2012
[76] C B Tabelin T Igarashi T Arima D Sato T Tatsuhara andS Tamoto ldquoCharacterization and evaluation of arsenic andboron adsorption onto natural geologic materials and theirapplication in the disposal of excavated altered rockrdquo Geo-derma vol 213 pp 163ndash172 2014
[77] G Aloisi K Wallmann M Drews and G BohrmannldquoEvidence for the submarine weathering of silicate minerals inBlack Sea sediments possible implications for the marine Liand B cyclesrdquo Geochemistry Geophysics Geosystems vol 5no 4 pp 1ndash22 2004
[78] C Degueldre and V Cloet ldquoPore water colloid properties inargillaceous sedimentary rocksrdquo Science of e Total Envi-ronment vol 569-570 pp 423ndash433 2016
Journal of Chemistry 19
[79] J A Higgins and D P Schrag ldquoRecords of Neogene seawaterchemistry and diagenesis in deep-sea carbonate sedimentsand pore fluidsrdquo Earth and Planetary Science Letters vol 357-358 pp 386ndash396 2012
[80] H Schroeder A-L Fabricius D Ecker T A Ternes andL Duester ldquoMetal(loid) speciation and size fractionation insediment pore water depth profiles examined with a newmesoprofiling systemrdquo Chemosphere vol 179 pp 185ndash193 2017
[81] Y Song and G Muller ldquoFreshwater sediments sinks andsources of brominerdquo Naturwissenschaften vol 80 no 12pp 558ndash560 1993
[82] M E Goher H I Farhat M H Abdo and S G Salem ldquoMetalpollution assessment in the surface sediment of Lake NasserEgyptrdquo Egyptian Journal of Aquatic Research vol 40 no 3pp 213ndash224 2014
[83] G F El-Said M M El-Sadawy and A A Moneer ldquoIncor-poration of fluoride and boron into surface sediments alongthe Egyptian Mediterranean coastrdquo Egyptian Journal ofAquatic Research vol 36 no 4 pp 569ndash583 2010
[84] B Gilfedder G M Petri M Wessels and H Biester ldquoAniodine mass-balance for Lake Constance Germany insightsinto iodine speciation changes and fluxesrdquo Geochimica etCosmochimica Acta vol 74 no 11 pp 3090ndash3111 2010
[85] E Korobova L Kolmykova B Ryzhenko et al ldquoDistributionand speciation of iodine in drinking waters from geochem-ically different areas of Bryansk region contaminated after theChernobyl accident in relation to health and remediationaspectsrdquo Journal of Geochemical Exploration vol 184pp 311ndash317 2018
[86] V Zic V W Truesdale and N Cukrov ldquo-e distribution ofiodide and iodate in anchialine cave watersmdashevidence forsustained localised oxidation of iodide to iodate in marinewaterrdquoMarine Chemistry vol 112 no 3-4 pp 168ndash178 2008
[87] M B Heeb J Criquet S G Zimmermann-Steffens andU Von Gunten ldquoOxidative treatment of bromide-containingwaters formation of bromine and its reactions with inorganicand organic compoundsmdasha critical reviewrdquo Water Researchvol 48 pp 15ndash42 2014
[88] V Sivasankar A K Darchen and R Omine SakthivelldquoChapter 2 ldquofluoride a world ubiquitous compound itschemistry and ways of contaminationrdquo in Surface ModifiedCarbons as Scavengers for Fluoride fromWater V SivasankarEd pp 5ndash32 copy Springer International Publishing Switzer-land Cham Switzerland 2016
[89] O Cabestrero P Del Buey and M E Sanz-Montero ldquoBio-sedimentary and geochemical constraints on the precipitationof mineral crusts in shallow sulphate lakesrdquo SedimentaryGeology vol 366 pp 32ndash46 2018
[90] M A Hassaan O A El-Rayis and E I Hemada ldquoEstimationof the redox potential of lake mariut drainage system (Qalaaand Umum drains)rdquoHydrology vol 5 no 6 pp 82ndash85 2017
20 Journal of Chemistry
a closed Teflon container -e extraction of fluoride bro-mide and iodide from sediment samples was carried outafter the fusion of Na2CO3 with each sediment sample[37 38]
24 Samples Analyses -e carbonate and bicarbonate ofsurface and pore waters were determined in the laboratory bythe titration method [39 40] pH and TDS values of the porewater were measured in the laboratory using portableequipment (CTDYSI 566) From the salinity value chlorosity(Cl) in the surface and pore waters and chlorinity (Clpermil)wereeffectively calculated [39] -e DO of water samples wasaccurately measured by Winklerrsquos method [41] Porosity wasmeasured based on the weight difference between dry and wetsediment samples [42] Calcium and magnesium in surfaceand pore waters and digested sediment samples were carefullydetermined by the titrimetricmethod using Eriochrome BlackT and Murexide indicators [43] Sodium potassium andlithium contents in surface and pore waters and digestedsediment samples were estimated by the flame photometerinstrument (lame139 photometer PFP JENWAY 7) Inor-ganic phosphorus and total phosphorus contents in thesurface and pore waters and sediment samples were deter-mined [43 44] Silicate was measured in the surface and porewaters and digested sediment samples by the calorimetricmethod [39] Curcumin colorimetry was used to determineboron in surface water pore water and digested sediment[43] -e turbidity method was used to estimate sulfate in thesurface water and pore water and digested sediment samples[43] -e heavy metals (Cu Mn Zn and Fe) dissolved in thesurface and pore water samples were extracted with chelatingresin and measured with an atomic absorption spectropho-tometer (GBC Savant AA Scientific equipment serial no A7275 GBC) [45] Fluoride concentration was determined bythe colorimetric method using the zirconium alizarin red Smethod [46] -e bromide was determined by titration usinga thiosulfate solution [41] -e catalytic reduction methodusing the Ce(IV)-As(III) was applied to determine the iodineconcentration [43] -e chloride content in sediments wasestablished by Mohrrsquos method [47]
25 Quality Control and Quality Assurance A sedimentreference material (IAEA-405 International Atomic EnergyAgency Vienna Austria) was used to determine the sedi-ment samplersquos quality controlquality assurance -e re-covery percentages for the selected metals from the standardreference material were in the range of 970ndash1011 Foreach variable an examined calibration procedure of threeexternal standards was performed One of the externalstandards must be of a concentration near but above themethod detection limit -e other concentrations shouldcorrespond to the range of a variable concentration expectedin the sample -e working calibration curve was verified oneach working shift by the measurement of one or morecalibration standards
26 Saturation Index (SI) -e Saturation Index (SI) of 23and 15 structures in surface water and pore water sampleswere calculated respectively [23 48]
It can be calculated from the division of the product of themolar concentrations (IAP [49]) of their component by theirequilibrium solubility constant (Table 1) Moreover SI of someminerals such as anhydrite (CaSO4) gypsum (CaSO42H2O)calcium phosphate (Ca3(PO4)2) magnesium phosphate(Mg3(PO4)2) calcite (CaCO3) aragonite (CaCO3) dolomite(CaMg(CO3)2) magnesite (MgCO3) fluorapatite (FAPCa5(PO4)3F) hydroxyapatite (HAP Ca5(PO4)3OH) octacal-cium phosphate (OCP Ca4H(PO4)325H2O) and carbonate-fluorapatite (CFAP Ca10(PO4)5(CO3)F272(OH)028) besidessome precipitated salts (Fe(OH)2 Fe(OH)3 FePO42H2OMg(OH)2 Mg3(PO4)2 Mn(IO3)2 KIO4 KCIO4 ZnCO3ZnCO3H2O Zn(OH)2 and Zn(IO3)22H2O) was calculatedby the following equation [23 48]
SI logIAPKsp
1113888 1113889 (1)
where IAP and Ksp were the product of the ion activity andthe equilibrium solubility constant of each precipitated saltor mineral SI values represented the under saturation(SIlt 1) or over saturation (SIgt 1) situation of each pre-cipitated salt or mineral
27 Palmerrsquos Method and Piper Ternary Diagram -e dis-solved salts in the surface and pore waters in the in-vestigated area were utilized by Palmerrsquos method andpiper ternary diagram Palmerrsquos method by using the millequivalent percentage of the major anions (Clminus SO4
minus2and HCO3
minus) and cations (K+ Na+ Ca+2 and Mg+2) [50]-is method assumed that the concentration of positiveions and negative ions are in equilibrium ie the sum ofthe concentrations of positive ions in meq Lminus1 is equal tothe sum of the concentrations of negative of ions con-sidering only the major ions -is hypothesis can beverified by converting the average ion concentration ofsurface water and pore water along the study areafrom mg Lminus1 in Table 2 to meq Lminus1 -en the concen-trations were further converted into a percentage of eachion in relation to the total concentration of positive ionsin the case of a positive ion and in relation to the totalconcentration of negative ions in the case of a negativeion -e percentage of each cation and anion was rep-resented in two rectangles in cm to evaluate the relativeformed soluble salts Piper ternary diagram explores theorigin of the dissolved salts in surface and pore waters ofthe lake water besides the effects of drainage sources onthem [55]
28 Multivariate Analysis Multivariate analysis includingcorrelation multiple stepwise linear regression and clusteranalysis has been used to predict the role of halogens in thepollution status of Lake Mariout Multivariate analysis canbe used in monitoring research because they can reduce the
4 Journal of Chemistry
cost of further environmental investigations [56ndash58] -emultivariate analysis using the correlation matrix with acorrelation coefficient (r) multiple stepwise linear regressionwith a coefficient (R) and cluster (tree clustering) at asignificance level of ple 005 is estimated by STATISTICA 99edition At the same time the principal component (PCA)can be estimated through SPSS 15 evaluation
29 Enrichment Factor (EF) EF of the determined elements(Ca Mg Na K Li B P Cu Zn Mn Fe F Cl Br and I) wascalculated by using the equations described (equations (2)and (3)) [59 60]
EF Cm sample
MedianCm Background + 2 times MADCm Background( 1113857
(2)
where Cm was the element concentration Median CmBackground represented median concentration of an ele-ment in the background and MAD Cm Background was themedian absolute deviation from the median calculated fromthe given equation
MAD median xi minus medianj xj1113872 111387311138681113868111386811138681113868
111386811138681113868111386811138681113874 1113875 (3)
-e EF values were classified into five categories defi-ciency tominimal (EFlt 2) moderate (2ltEFlt 5) significant(5ltEFlt 20) very high (20ltEFlt 40) and extremely highenrichment (EFgt 40)
210 Human Health Risk Assessment -e human healthhazard of surface water and sediment ingestion and dermalcontact was assessed by using the estimated daily intake
Table 1 -e hypothetical precipitated salts in surface and pore waters along Lake Mariout
Site 1 2 3 4 5 6 7 8 9 10 11 12 13SI of precipitated salts and minerals
Surface waterCalcite 128 138 340 146 236 303 295 297 205 258 312 126 311Aragonite 103 112 315 120 211 278 270 272 180 233 287 101 286CaSO405 H2O 208 188 126 157 156 155 170 179 199 171 115 075 181CaSO42H2O 196 176 114 144 143 143 158 167 187 158 103 063 169Ca3(PO4)2 2486 2424 2424 2424 2424 2424 2424 2424 2424 2424 2424 2424 2424Ca(IO3)2 157 137 137 137 137 137 137 137 137 137 137 137 137Ca(IO3)26H2O 1006 986 986 986 986 986 986 986 986 986 986 986 986OCP 3964 3569 3569 3569 3569 3569 3569 3569 3569 3569 3569 3569 3569HAP 4574 4349 4349 4349 4349 4349 4349 4349 4349 4349 4349 4349 4349FAP 4277 5036 5038 5195 5171 5131 5090 4982 5131 5081 4903 5095 5163CFAP 6089 1685 1786 1818 1784 1902 1883 1785 1764 1859 1604 1824 1914Fe(OH)2 1196 1217 1196 1189 1208 1059 1176 1158 1007 1192 1205 1199 1152Fe(OH)3 3544 3564 3543 3536 3555 3407 3524 3505 3354 3539 3552 3546 3499FePO42H2O 1053 1074 1053 1046 1065 916 1033 1015 864 1049 1062 1056 1008Mg(OH)2 1215 1206 1131 1171 1173 1159 1179 1188 1170 1183 1151 1152 1168Mg3(PO4)2 085 1345 1121 1240 1245 1205 1264 1291 1236 1276 1180 1184 1229Mn(IO3)2 025 243 354 303 247 312 226 055 183 198 064 262 042KIO4 576 570 552 549 565 564 559 554 551 560 489 551 548KCIO4 495 489 471 468 484 483 478 473 470 479 408 470 467ZnCO3 414 404 613 455 560 560 586 573 491 530 659 472 581ZnCO3H2O minus018 minus027 181 024 128 128 154 142 060 099 227 041 149Zn(OH)2 1198 1189 1199 1210 1254 1194 1223 1232 1216 1207 1249 1227 1203Zn(IO3)22H2O 366 357 367 378 422 362 391 400 383 375 417 395 371Pore waterFluorite 200 211 106 195 346 309 345 317 228 246 307 365 277CaSO405 H2O 370 177 190 200 168 178 202 255 203 212 191 179 211CaSO42H2O 358 165 178 188 155 166 190 243 191 200 178 167 199Ca3(PO4)2 2958 2424 2424 2424 2424 2424 2424 2424 2424 2424 2424 2424 2424Ca(IO3)2 315 137 137 137 137 137 137 137 137 137 137 137 137Ca(IO3)26H2O 1164 986 986 986 986 986 986 986 986 986 986 986 986OCP 4594 3569 3569 3569 3569 3569 3569 3569 3569 3569 3569 3569 3569HAP 5361 4349 4349 4349 4349 4349 4349 4349 4349 4349 4349 4349 4349FAP 5126 5295 5399 5270 5460 5318 5327 5338 5321 5311 5420 5373 5391CFAP 7833 1775 2068 1752 2049 2078 1990 2015 1963 2026 2121 2024 2060MgF2 299 138 177 060 262 232 095 209 212 243 222 251 203Mg(OH)2 1395 1439 1408 1400 1428 1420 1346 1425 1418 1438 1412 1391 1414Mg3(PO4)2 987 2442 2417 2355 2469 2207 2128 2317 2243 2260 2387 2132 2378KIO4 564 568 575 557 561 560 570 566 558 571 551 543 564KCIO4 483 487 494 476 480 479 489 485 477 490 470 461 483
Journal of Chemistry 5
(EDI) hazard quotient (HQ) and hazard index (HI) as givenin equations (4)ndash(11)
2101 For Surface Water Estimated daily intake of surfacewater ingestion and dermal contact (EDIIngw and EDIDermw)were computed by the following equations [61]
EDIIngw(mgkgday) (CW times CR times ET times EF times ED)
(AT times BW) (4)
EDIDermw(mgkgday) (CW times SA times PC times ET times EF times ED times CF)
(AT times BW)
(5)
where CWwas the element concentration in water (mg Lminus1)CR was the contact time (50mL hminus1) ET was the exposuretime (26 h dayminus1) EF was the exposure frequency (7 dayyearminus1) ED was the exposure duration (60 year) ATwas theaverage time (60times 365 day yearminus1) BWwas (707 kg) SAwas
the skin surface area (5700 cmminus2) PC was the dermalpermeability constant (0001 cm hminus1) and CF was theconversion factor for water (10times10minus6 kg mgminus1) [62ndash65]
2102 For Sediment Estimated daily intake of sediment byingestion and dermal contact (EDIIngs and EDIDerms) werecalculated according to the following equations [60]
EDIIngS(mgkgday) CS times IngS times RAFS times EFS( 1113857
(AT times BW) (6)
EDIDermS(mgkgday) CS times IngS times ED times SA times AF times ABS( 1113857
(AT times BW)
(7)
where CS was the concentration of the contaminant insediment (mg gminus1) IngS was the ingestion rated of sediment(80times10minus5mg kgminus1) RAFS was the relative absorption factorof sediment (058) EFS was the exposure frequency (30 day
Table 2 Distribution of the studied variables in surface water (w) and their chlorinity ratios along Lake Mariout
Determined variables Minimum Site Maximum Site Average SD Seawatera Lake Marioutbcd
Physicochemical variablesTw 137 10 1534 11 1759 134Salinity (Spermilw) 23 13 79 1 489 152Chlorinity (Clpermilw) 205 13 71 1 438 137 1898TDSw (mg Lminus1l) 24635 13 7683 1 48503 152874Turbidity (NTU) 166 8 385 12 1296 1174DOw (mg Lminus1l) 0 6 1241 2 605 483 214ndash563d
pHw 744 13 899 2 710ndash860d
CO3w (mg Lminus1) 12 1 amp 2 1152 3 31 388HCO3w (mg Lminus1) 7808 3 19032 12 1147 321Bw (mg Lminus1) 05 7 1661 1 691 411 45Pw (μg Lminus1) 003 8 126 5 029 033Siw (μg Lminus1) 009 12 699 4 317 191Caw (mg Lminus1) 6092 12 3527 8 17703 735 400 549 818ndash1464d
Mgw (mg Lminus1) 9725 3 66615 1 28684 16002 1272 1201Naw (mg Lminus1) 231 11 1420 1 101115 2972 10556 10332Kw (mg Lminus1) 8 11 59 1 3769 123 380 585Liw(mg Lminus1) 0139 11 017 1 0154 001 017SO4w (mg Lminus1) 1978 12 34111 9 16856 9488 2649 4245Cuw (μg Lminus1) 204 3 621 7 317 113 7Mnw (μg Lminus1) 001 8 amp13 198 3 315 554 10Few (μg Lminus1) 009 9 1392 13 69 419 40Znw (μg Lminus1) 527 2 2367 5 1085 578 20Fw (mg Lminus1) 015 11 396 12 204 117 13Clw (mg Lminus1) 2048 13 7284 1 4397 1400 18980Brw (mg Lminus1) 506 12amp13 541 5 1813 1891 65 592Iw (μg Lminus1) 566 10 541 4 1108 1296 60Ion chlorinity ratioCawClw 170Eminus 02 12 100Eminus 01 13 440Eminus 02 240Eminus 02 213Eminus 02 335Eminus 02MgwClw 250Eminus 02 3 110Eminus 01 13 640Eminus 02 230Eminus 02 669Eminus 02 733Eminus 02NawClw 650Eminus 02 11 380Eminus 01 13 240Eminus 01 720Eminus 02 560Eminus 01 635Eminus 01KwClw 220Eminus 03 11 150Eminus 02 13 890Eminus 03 290Eminus 03 210Eminus 02 360Eminus 02LiwClw 240Eminus 05 1 700Eminus 05 13 380Eminus 05 110Eminus 05 939Eminus 06SO4wClw 540Eminus 03 12 110Eminus 01 13 420Eminus 02 310Eminus 02 140Eminus 01 260Eminus 01BwClw 978Eminus 05 7 332Eminus 03 9 670Eminus 03 170Eminus 03 895Eminus 04FwClw 430Eminus 05 11 140Eminus 03 13 540Eminus 04 420Eminus 04 670Eminus 05BrwClw 140Eminus 03 12 160Eminus 02 9 440Eminus 03 500Eminus 03 350Eminus 03 360Eminus 05IwClw 940Eminus 04 1 160Eminus 02 4 300Eminus 03 400Eminus 03a[51] b and c[52 53] d[54]
6 Journal of Chemistry
yearminus1) AF was the adherence factor (007mg cmminus2) andABS was the dermal absorption factor (0001 unit less)[65 66]
Hazard index (HI) is the total chronic hazard attribut-able to exposure to all determined contaminants (i) througha single exposure pathway of the ingestion and dermalcontact of water (HIIngw and HIDermw) and sediment (HIIngsand HIDerms) was given as follows [60]
HIIngW 1113944HQ IngW( 1113857i (8)
HIDermW 1113944HQ DermW( 1113857i (9)
HIIngS 1113944HQ IngS( 1113857i (10)
HIDermS 1113944HQ DermS( 1113857i (11)
3 Results and Discussion
31 Distribution of Halogens and Tested Variables in SurfaceWater
311 Distribution of Halogens in Surface Water -e rangeand average value of halogens in the surface water in thisstudy show a sequence of ClwgtBrwgt Fwgt Iw (Table 2 andFigure 2)-e current study indicate that the water sample ofpumping station (site 6) attained high concentrations offluoride (28mg Lminus1) chloride (38878mg Lminus1) and bromide(181mg Lminus1) and low iodide (641 μg Lminus1) contents (Fig-ure 2) High levels of F Br and I are detected in the MainBasin region which is affected by the drainage of El-Qalaaand El Umoum containing the agricultural and industrialwastes However halogens are involved in the manufactureof pesticides (herbicides fungicides insecticidesacaricidesand nematicides) [67] Plus halogens are produced in theproduction of fertilizers products [67] -e presented resultsof halogens in the studied lake region reflect anomalousdistribution and are mainly affected by water dischargedfrom the drainage sources However the highest fluoridebromide and iodide contents of 377mg Lminus1 6553mg Lminus1and 5410 μg Lminus1 respectively are recorded in the MainBasin affected by El-Qalaa and El Umoum drains Amongthe halogens chloride shows high levels in surface waterespecially in site 1 (72837mg Lminus1) site 2 (65218mg Lminus1)and site 10 (51687mg Lminus1) which are also related to theirlevels in the water of the drains (Figure 2) On the meantimethe lowest Spermilw and Clpermilw are observed at site 13 (ElUmoum Drain) Most of the studied variables have chlo-rinity ratios relatively lower than those measured for LakeMariout andor seawater [51ndash53 68 69] -is is mainly dueto the accumulation of wastewater from Abis and ElUmoum where agricultural products such as fertilizers andbiocides are deposited in industrial products [19]
Due to the increase in chloride content in surface watersamples the conservativeness of the chlorinity ratio is usedto describe the contamination precipitation and dissolutionof sediment components [70] -e FCl ratio in the studyarea is higher than open seawater (430Eminus 05) of a range
430Eminus 05ndash140Eminus 03 and average 540Eminus 04 -e BrClratio is relatively similar to that of seawater (Table 2) -ehighest FCl BrCl and ICl ratios in surface water140Eminus 03 160E ndash 02 and 160Eminus 02 are recorded in site 13(El Umoum drain outside the lake) site 9 (South West Basinin the lake) and site 4 (Main Basin in the lake) -erefore itcan be concluded that the distribution of halogens in thesurveyed area is greatly affected by the drainage of the El-Qalaa El Umoum and the El Nubaria drains
312 Distribution of Tested Variables in Surface Water-e range and average values of the tested variables (Tw Spermilw Clpermilw TDSw turbidity DOw pHw CO3w HCO3w BwPw Siw Caw Mgw Naw Kw Liw SO4w Cuw Mnw Few andZnw) in surface waters of the present study are listed inTable 2 Turbidity fluctuates from 166 to 3850 NTU at sites8 and 12 respectively DO is completely depleted at sites 5 6and 11 and has the highest amount 1241mg Lminus1 at site 2with an average 605mg Lminus1 relatively similar to the reportedLake Mariout value (214ndash563mg Lminus1 [54]) (Table 2) -eaverage content of DO in the lake is higher than those re-ported for the ocean seawater (32ndash48mgL) [71] -e levelsof DO probably relate to the oxygen-producing processes ofthe photosynthesis processes of phytoplankton and mac-rophytes [72] -e presented results indicate that site 1(affect by Abis drainage) is the most affected area in the lakeas it shows the highest contents of Bw Clw Mgw Naw KwLiw and SO4w -e most important feature in the concen-trations of heavy metals Cuw Mnw and Znw in surface wateris that they possess average values lower than those reportedfor the threshold guideline (10 100 and 50 μg Lminus1) [73 74]
-e present study clears out a descending trend in thesurface water average concentrations of halogens andtested variables in the lake as follows TDSw gtClw gtNaw gtMgw gtCaw gt SO4w gtHCO3wgtKw gtCO3w gt Bw gt Brwgt FwgtLiw gt Znw gt Few asymp Siw gtMnw gt Pw gt Iw (Table 2)
313 Interactions of Halogens and Tested Variables inSurface Water Chloride in surface water is significantlyrelated to the drainage water content showing good cor-relations with Tw (r 0631 ple 0028) and pHw (r 0769ple 0003) (Supplementary Table 1) -e negative moderaterelation of Fw and Ip (r 0606 ple 0037) may indicatereplacement of iodine in pore water by fluoride of the surfacewater-emoderate relationship between fluoride in surfacewater and CO3w (r minus0632 ple 0027) and HCO3w(r 0593 ple 0042) may be related to carbonate exchangeand the formation of fluorite minerals (CaF2) [23]
-e correlation matrix reflects that the observed ex-traordinary levels of Bw in the surface water samples aremost probably due to its exchange with the different sedi-ment components not related to the discharged waters(Supplementary Table 1) -is findings is supported by theweak B correlation with Cuw (r minus0587 ple 0045) andgood correlation with Fs (r minus0666 ple 0018) [75 76]However Cuw is one of the pollutants that can be exchangedin drainage water -e correlations of Mgw amp Naw (r 0629
Journal of Chemistry 7
1
23
4
56
7
8
9
10
2986degE 2988degE 2990degE 2992degE
310
8degN
311
0degN
311
2degN
311
4degN
311
6degN
El-mex
pumping
statio
n Main Basin
of Lake Maryout
Southwest Basin
Qalaa Drain
El Umoum Drain
Northwest BasinFish
ery Basi
nEl Nubaria Drain
3311 to 38883888 to 43934393 to 5115
5115 to 65226522 to 7284
(a)
1
23
4
56
7
8
9
10
2986degE 2988degE 2990degE 2992degE
310
8degN
311
0degN
311
2degN
311
4degN
311
6degN
El-mex
pumping
statio
n
Main Basinof Lake Maryout
Southwest Basin
Qalaa Drain
El Umoum Drain
Northwest Basin
Fishery
BasinEl Nubaria Drain
069 to 127127 to 169169 to 242
242 to 277277 to 377
(b)
El-mex
pumping
statio
n
Main Basin of Lake Maryout
South west Basin
North west Basin
1
23
4
56
7
8
9
10
2986degE 2988degE 2990degE 2992degE
310
8degN
311
0degN
311
2degN
311
4degN
311
6degN
Qalaa Drain
El Umoum Drain
Fishery
BasinEl Nubaria Drain
613 to 852852 to 14381438 to 1732
1732 to 52745274 to 6554
(c)
El-mex
pumping
statio
n
Main Basin of Lake Maryout
Southwest Basin
Northwest Basin
1
23
4
56
7
8
9
10
2986degE 2988degE 2990degE 2992degE
310
8degN
311
0degN
311
2degN
311
4degN
311
6degN
Qalaa Drain
El Umoum Drain
Fishery
BasinEl Nubaria Drain
566 to 671671 to 761761 to 817
817 to 922922 to 5411
(d)
Figure 2 Distribution of halogens (Cl F Br and I in surface water of LakeMariout (a) Cl (mg Lminus1) (b) F (mg Lminus1) (c) Br (mg Lminus1) and (d) I(μg Lminus1)
8 Journal of Chemistry
ple 0028) Mgw amp Liw (r 0790 ple 0002) Naw amp Kw(r 0955 ple 0000 Naw amp Liw (r 0835 ple 0001) Naw ampCO3w (r minus0701 ple 0011) Kw amp Liw (r 0712 ple 0009)Kw amp CO3w (r minus0580 ple 0048) CO3w amp HCO3w(r minus0613 ple 0034) and Mgw amp SO4w (r 0631ple 0028) indicate that all these variables have some geo-chemical behaviors [77] Mg Na and Li are some com-ponents of the discharged waters however they havepositive correlations with the chlorinity and salinity of thedischarged water sources (r 0743 0619 and 0815 re-spectively) and (r 0743 0619 and 0815 respectively)Mgw and Liw contents in water samples are affected bytemperature dissolved oxygen and pH with high correla-tions of r minus0650 0677 and 0743 and minus0702 0659 and0815 respectively
32 Distribution of Halogens and Tested Variables in PoreWater
321 Distribution of Halogens in Pore Water -e averagehalogen contents in the pore water are higher than theircontents in the surface water but in the same orderClpgtBpgt Fpgt Ip (Table 3) Current research shows that thelowest and highest average values of Spermilp and Clp have beenmeasured in the pore water of site 6 and site 8 respectively Itis worth mentioning that site 6 is a mixed water of El-Qalaadrainage sewage WWTP treatment plant and lake waterInterestingly the high concentrations of fluoride chloridebromide and iodide in the pore water at site 6 are 123mgLminus1 40321mg Lminus1 11739mg Lminus1 and 24339 μg Lminus1 re-spectively (Table 3) -e salinity and chloride content in thepore water of site 8 are related to the discharge water of manypetrochemical and oil companies besides some fish farms
322 Distribution of Tested Variables in Pore Water -etested variables in the pore water (p) give the followingdescending order MgpgtNapgtCapgt SO4pgtBpgtKpgtBrpgt Fpgt LipgtPpgt Ipgt Sip (Table 3) Interestingly the deter-mined variables in the pore water have higher values thanthe surface water along the lake According to previousstudies pore water is responsible for biogeochemical reac-tions the migration and transformation of partitioned andformed compounds and the transportation of colloidalspecies [78 79] In addition pore water can explore thepotential risks of man-made pollution sources [80] -etested variables in the pore water (p) are given in a differentorder of surface water of ClpgtMgpgtNapgtCapgt SO4pgtBpgtKpgtBrpgt Fpgt Lipgt Ppgt Ipgt Sip (Tables 2and 3)
323 Interactions of Halogens and Tested Variables in PoreWater -e following interactions of halogens CO3w amp Ip Ipamp Fw Brw amp Sip Fp amp Siw and Fp amp Nap give correlationvalues (r 0706 ple 0010 r minus0606 ple 0037 r 0826ple 0001 r minus0704 ple 0011 and r 0670 ple 0017respectively) (Supplementary Table 1) However these re-lationships may indicate their precipitation andor
adsorption on the colloidal particles besides the formation ofsome chemical species [78 79] Extraordinarily large cor-relations of Nap amp HCO3w Kp amp HCO3w Spermilw amp Bp Spermilp ampKp Spermilp amp Lip and Spermilp amp Clp (r 0692 minus0609 minus07410696 0910 and 1000) may refer to the release of theseelements from sediment particles andor precipitation oradsorption [77] In the matrix the negative correlationbetween Cap and Mgp (r minus0592 ple 0042) may be relatedto the release of Mg during the recrystallization of calcite[79]-e relationship between Caw amp SO4p Cuw amp Cap Pw ampPp and Nap amp pHw (r 0744 ple 0006 r 0719 ple 0008r 0647 ple 0023 and r minus0640 ple 0025 respectively)may be due to the chemical interactions in the pore fluidsand the formation certain compounds
33Distribution ofHalogens andTestedVariables in Sediment
331 Distribution of Halogens in Sediment -e averagehalogenrsquos content in the sediment shows a different orderfrom the surface and pore waters of Brsgt FsgtClsgt Is (Ta-ble 4) -e sediment results show that the average bromidecontent is higher than fluoride followed by chloride contentand iodide with average values of 452mg gminus1 040mg gminus1029mg gminus1 and 450 μg gminus1 respectively
-e fluoride concentration in the sediment ranges from001 to 120mg gminus1 with an average value of 04plusmn 035mggminus1 -ese values are lower than reported marine sedimentvalues and higher than the El-Bardawil Lagoon [60]Amongst the halogens the study reveals that Br is the mostabundant ion in surface water pore water and sedimentsamples due to the excessive amounts of organic matter [81]On the contrary the concentration of Cl ions in sedimentsamples is lower than that in surface water and pore watersamples indicating that it exists in soluble salts -e currentresults indicate that the sediments collected from the mostaffected area by the Mediterranean Sea (site 6) contain el-evated levels of fluoride (070mg gminus1) bromide (852mggminus1) and chloride (020mg gminus1) and a reduced amount ofiodide (209 μg gminus1) (Table 4)
332 Distribution of Tested Variables in Sediment -eaverage value of test variables in the determined sedimentsamples shows a significant change from site to site with adescending order CO3sgtMgsgtCasgtNasgt SO4s gt FesgtBsgtKsgtTPsgtMn sgtZnsgtCusgt Lis (Table 4) Plus this studyclears out that the percent of sand and mud of the differentsediment samples ranges from 4 at sites 1 amp 13 to 85 atsite 11 and from 15 at site 11 to 96 at sites 1amp13 re-spectively with averages 25 and 75 respectively Plusthe porosity shows a trend opposite to the particle size andvaries from 4676 to 8214 with an average value of5609plusmn 1114 -e results of the current study reveal mod-erate amounts of CO3 in the sediment samples fluctuatingbetween 1639 and 5736 at sites 6 and 2 respectively -eresults of sand mud porosity and CO3 percentage reflect thatthe texture of the sediment is mainly composed of mud mixedwith carbonate compounds Comprehensively the large storageof sediments with carbonate (359plusmn1280) magnesium
Journal of Chemistry 9
Tabl
e3
Distribu
tionof
thestud
iedvariablesin
thepo
rewater
(p)alon
gLake
Mariout
Site
Spermilp
pHP
Ca p
(mgLminus
1 )Mg p
(mgLminus
1 )Na p
(mgLminus
1 )Kp
(mgLminus
1 )Li
p(m
gLminus
1 ))
SO4P
(mgLminus
1 ))
B P(m
gLminus
1 ))
P P(μgLminus
1 ))
SiP
(microgLminus
1 ))
F p(m
gLminus
1 ))
Cl P
(mgLminus
1 ))
Brp
(mgLminus
1 ))
I p(μgLminus
1 )1
1034
787
481
42303
1097
453
042
2944
8043
363
0045
323
95419
959
7104
2934
809
5611
115725
1050
498
039
2056
663
553
0036
338
8398
1385
24698
31272
717
100
5689
1195
577
053
2778
8949
1204
0034
754
114469
2291
26347
483
796
9619
47652
974
384
043
350
19312
77
0054
215
74599
693
8393
51099
782
5611
89711
1128
42041
1667
16739
1112
0081
1698864
1332
8333
645
775
4008
75367
736
41024
2111
11739
071
0037
1231
40321
799
24339
71125
782
39278
13615
1155
516
056
3667
6051
369
006
6101209
1279
8123
8148
775
9299
84314
1355
468
055
12444
942
212
0056
892
133232
1172
7643
9684
78
962
72109
880
393
036
3778
21341
114
0087
1061429
2131
9981
10114
764
1122
113586
1195
524
049
4667
8007
071
0041
1138
102562
1332
8572
11639
742
4008
61996
915
332
033
2833
11594
754
0026
1215
67834
746
37587
125
702
481
38413
8703
274
028
2167
13913
081
0025
2154
44832
1438
9891
13755
807
3206
6467
817
446
039
4556
17246
635
0042
954
5737
533
1097
Minim
um45
702
962
13615
736
274
024
1667
6051
071
0025
215
40321
533
7104
Maxim
um148
809
39278
115725
8703
577
056
12444
21341
1204
0087
2154
133232
2291
37587
Average
919
77
718
67412
163077
4381
041
3782
1223
485
0048
955
82779
1238
14768
SD308
032
10027
29209
2132
825
01
2769
5047
391
0019
542
27891
524
9917
10 Journal of Chemistry
Tabl
e4
Distribu
tionof
thestud
iedvariablesin
thesediment(s)alon
gLake
Mariout
Site
Sand
()
Mud ()
Porosity
()
CO3s
()
B s(m
ggminus
1 )P s
(mg
gminus1 )
Ca s
(mg
gminus1 )
Mg s
(mg
gminus1 )
Na s
(mg
gminus1 )
Ks
(mg
gminus1 )
Lis(m
ggminus
1 )
SO4s
(mg
gminus1 )
Fes
(mg
gminus1 )
Cu s (μg
gminus1 )
Mn s
(μg
gminus1 )
Zns(μg
gminus1 )
F s(m
ggminus
1 )
Cl s
(mg
gminus1 )
Brs
(mg
gminus1 )
I s(μg
gminus1 )
14
964915
183
299
044
1670
811
2583
408
0028
4861
828
963
5617
1272
034
041
128
1686
244
564925
574
196
028
1002
1419
2717
269
0015
662
257
793
4350
1313
057
054
123
358
319
816667
299
246
073
1670
1216
3125
336
0022
463
487
1228
4330
1677
044
034
448
516
418
824853
3813
1111
032
668
2229
3425
365
0094
2222
770
922
4637
1245
030
020
309
296
512
884697
482
614
012
501
1115
1833
091
0040
1713
243
600
27933
1223
082
034
245
254
65
954667
164
370
157
835
1257
2958
388
0030
5648
890
1927
5347
3117
070
020
852
209
75
954762
375
524
024
367
2047
3133
256
0102
1157
546
883
4185
1393
120
020
341
259
838
626143
457
697
039
668
1621
3550
347
0145
4167
598
737
4157
1412
022
034
144
1277
918
826000
349
083
054
401
1094
3358
369
0025
2454
701
868
5702
3065
036
027
250
172
1036
645070
441
296
002
935
1763
3117
246
0045
2685
369
790
4533
1315
012
047
1012
224
1185
157000
325
240
074
969
2250
3508
328
0193
1343
1026
735
3890
1070
005
007
533
128
1237
638214
463
291
032
334
1824
3008
358
0018
556
340
728
2475
827
001
007
852
281
134
965000
177
211
054
2338
1621
3925
599
0068
833
1687
1187
6492
1853
004
027
639
194
Min
415
4667
164
083
002
334
811
1833
091
0015
463
243
600
2475
827
001
007
123
128
Max
8596
8214
574
1111
157
2338
2250
3925
599
0193
6620
1687
1927
6492
3117
120
054
1012
1686
Av
2575
5609
359
398
048
951
1559
3096
335
0063
2671
672
951
4500
1599
040
029
452
450
SD23
231114
128
276
039
603
455
522
115
0055
2030
393
343
1120
708
035
014
303
475
Minm
inim
umM
axm
axim
uma
ndAv
averageSD
stand
arddeviation
Journal of Chemistry 11
(1559plusmn455mg gminus1) and calcium (951plusmn603mg gminus1) com-ponents may be attributed to the abundance of calcium min-erals [4] However in general the average amounts of allvariables in sediment samples showmarked variations fromonesite to another with a descending order of CO3sgtMgsgtCasgtNasgtSO4sgtFesgt BrsgtBsgtKsgtTPsgtFs gtClsgtMnsgtZnsgtCusgtLisgt Is (Table 4) -e measured concentra-tions of Mn Zn Cu and Fe in the sediment samples are stilllower than the reported values and also lower than the back-ground levels of crust and the toxicological reference contents ofUS DOE (US Department of Energy) US EPA (US Envi-ronmental Protection Agency) and CEQG (Canadian Envi-ronmental Quality Guidelines) [82]
Contrasting the obtained levels for the halogens withthose previously reported ones the present study indicatesthat surface and pore waters incorporate more considerableamounts of fluoride compared to the formerly reported onesin Lake Edku (Tables 2 and 3) and lower levels in theMarioutarea than those measured along the Egyptian MediterraneanSea coast [27] Compared with the sediments previouslyfound on the Mediterranean coast of Egypt the chloridecontent in the sediments of the Mariout area is lower [83]Compared with those observed in seawater the studiedsurface water and pore water samples have lower bromidecontent and higher levels than previously reported in LakeMariout [52 53] -e concentration of iodide in surfacewater pore water and sediments is equivalent to the con-centration of rivers and lakes in the world [84]
333 Interactions of Halogens and Tested Variables inSediment -e correlation matrix shows the important roleof halogens in the formation and precipitationdissolution ofsalts and minerals produced along the lake (SupplementaryTable 1) However it shows that chloride seems to be in thesoluble forms along the surface and pore waters of studiedarea showing good relations with Caw (r 0666 ple 0018)Clp (r 0677 ple 0016) and SO4p (r 0858 ple 0000)Also Cls gives good correlations with Mgw (r 0710ple 0010) Naw (r 0602 ple 0038) Clw (r 0619ple 0032) Mgp (r 0774 ple 0003) and Kp (r 0731ple 0007) Chloride in the surface and pore waters plays animportant role in the dissolution association and formationof various salts along the lake -e good relationship be-tween Is and Caw (r 0666 ple 0018) may reflect the de-positionrelease of CaI+ during the formationdissolution ofcalcium carbonate [85] In addition these correlations maybe related to organic-I which formed by bacterial species andtheir remineralization in bottom sediments [86] -emoderate relationship between Nas and Brw (r minus0622ple 0031) may indicate the possible formation of BrClspecies and the precipitation or adsorption of Na minerals insediments [87] -e results of this study also reflect thestrong negative correlation between Fs and Bw (r minus0666ple 0018) which may be related to the release of fluoridefrom sediment and the formation of soluble fluoridecomplexes ((BFn[OH]4minusn)minus) with the excessive boron con-centration in the water [88] -e negative relation betweenKs and Spermilw (r minus0673 ple 0016) possibly reflect that Kw
preferentially chooses to exist in the soluble form of KClrather than being adsorbed andor bound by some richminerals in the sediment
-e significant correlations between CO3s and Mgw(r 0637 ple 0026) CO3s and Clw (r 0723 ple 0008)CO3s and pHw (r 0833 ple 0001) CO3s and Spermilw(r 0723 ple 0008) and between CO3s and Ks (r minus0673ple 0016) may be accompanied by the possible formationdissolution of the dolomite mineral in the presence ofsufficient Mgw which is usually affected by optimal pHsalinity and the potassium salts (Supplementary Table 1)-ese observed results are matching with the previouslyreported studies [32] Significant negative correlation be-tween TPs and CO3s (r minus0744 ple 0006) may indicate theextended release of P from carbonate minerals and for-mation of apatites [32]
-e correlation matrix also refers to other possible in-teractions between the remaining determined variables(Supplementary Table 1) -e significant correlation be-tween SO4s andMgw (r 0706 ple 0010) and Liw (r 0633ple 0027) may be associated to the formation of Mg-sulfateand the pollution of sediments by discharged waters con-taining excessive sulfate and Li [89] In the contrary thestrong positive correlation between TPs and Cus and be-tween TPs and Zns may be related to the same source ofpolluted discharge water [23 83]
-e high negative correlations of Zns with Few(r minus0785 ple 0003) CO3s (r minus0601 ple 0039) and Cus(r 0698 ple 0012) may indicate that Zn Cu and CO3depositions in sediment samples are linked to the soluble Feform in water (ferrous) ie the release of Fe upwards in thewater column in the anoxic conditions (SupplementaryTable 1) [90] -e excellent relations found between Fesand CO3s (r minus0799 ple 0002) Fes and Cas (r 0637ple 0026) Fes and Clw (r minus0752 ple 0005) Fes and Nas(r 0720 ple 0008) and between Fes and Ks (r 0833ple 0001) may reflect the dissolution of the chelating Feassociation with the soluble organic compounds in thewater-sediment interface and the formation of the sol-uble ferrous form in low dissolved oxygen within theareas affected by untreated discharged waters [90] -estrong correlations of Mns with SO4w Nap Nas Ks CO3sZns and Fes (r minus0585 0608 0611 0698 minus0655 0691and 0716 respectively) may associate with the solubilityof abundant Mn minerals and P-Mn forms in the sedi-ment because of its possible reduction to Mn+2 solublespecies under anoxic conditions [90] It is worth men-tioning that the results of this study indicate that ap-proximately 333 of the survey sites indicate thedepletion of dissolved oxygen in their surface watersamples Under such anoxic conditions bacteria are mostlikely to use sulfate instead of oxygen to break downorganic matter and cause the release of iron and phos-phorus into the water column
-e significant direct correlation between Ks and Nas(r 0832 plt 0001) clearly reflects the transport of solublesalts of K and Na between the pore water phase of thesediment and water-sediment surface phase (SupplementaryTable 1) -e good correlation between porosity and Nas
12 Journal of Chemistry
indicates the possible transfer of Na between pore water andsediment partitions
34 Interactions of Precipitated Halogenated Compounds inSurface and Pore Waters -e Saturation Index (SI) [23 60]of twenty-three and fifteen structures in surface water andpore water samples respectively are listed (Table 1) -ecorrelation matrix of the calculated Saturation Indices withthe presented data shows the different factors affecting theinteraction of the halogenated compound with other pre-cipitated salts and minerals Table 1 explores the precipitationof the phosphate minerals and salts are most abundantfollowed by the hydroxidesrsquo salts iodate salts sulfate andcarbonate minerals and salts in surface waters Amongst thehalogens precipitated salts fluoride minerals especiallyfluorapatites and carbonate-fluorapatite (FAP and CFAP)have high SI values in surface water (4277ndash5195 and1604ndash6089 respectively) and in pore water (5126ndash5460 and1752ndash7833 respectively) Bromide and chloride are mainlyfound in the soluble forms in surface and pore waters Iodidesalts (Ca(IO3)2 and Ca(IO3)26H2O) moderately precipitatein surface and pore Iron salts precipitate in surface waterwhile in pore water they are not formed -us SI contentreflects that halogens especially fluoride and iodide play avital role in reducing lake pollution
In addition Table 1 shows that the precipitation com-pounds that may be formed in surface water are relativelydifferent from those in sediment pore water For examplefluorite (CaF2) and sellaıte (MgF2) may be only formed inpore water while calcite and aragonite may be deposited insurface water However the formation of fluorite in surfacewater is related to Naw (r 0778 ple 0003) Kw (r 0704ple 0011) CO3w (r minus0718 ple 0009) Fw (r 0770ple 0003) and Ip (r minus0785 ple 0003) (SupplementaryTable 1)
-e formation of calcium sulfate hemihydrate calciumsulfate and anhydrite in water is related to the increase in theamounts of Caw Mgw SO4w Nap Fp Sip Cls and Mns andthe decrease in porosity values On the other hand pre-cipitation of calcium phosphate is related to Brw (r 0751ple 0005) Znw (r 0668 ple 0018) Pw (r 0881ple 0001) and Ks (r 0881 ple 0001) ie it is affected bythe discharged water composition (Supplementary Table 1)
-e formation of calcite and aragonite in surface water isrelated to the formation of CO3w (r 0753 ple 0005) anddissociation of HCO3w (r minus0660 ple 0020) pHw values(r minus0654 ple 0021) and their dissolution in sediment(r minus0620 ple 0032) (Supplementary Table 1)
-e dolomite formation in water may be affected by theincrease of CO3w (r 0817 ple 0001) and the decrease ofHCO3w (r minus0658 ple 0020) increase in TDSw (r 0599ple 0040) and increase in pHw (r minus0656 ple 0021)besides the possible release of CO3s from abundant sediment(r minus0624 ple 0030) and the precipitation of calcite(r 0984 ple 0000) and aragonite (r 0984 ple 0000) intosediment fraction (Supplementary Table 1)
Generally in the current study the possible formedhalogenated minerals and salts are affected by their
abundance in different components of the lake besides theirpossible dissolution or formation on the sediment texturesgeochemistry of the sediments and physicochemical vari-ables of water in addition to the components of the dis-charged waters
35 Interactions of Dissolved Halogenated Compounds inSurface and PoreWaters -e utilization of dissolved salts insurface and pore waters by utilizing Palmerrsquos method andpiper ternary diagram [50] indicates that Na is the richestcation in surface water followed by Mg Ca and K At thesame time Mg is the most predominate one in the porewater (Figures 3 and 4) Obviously Cl is the most importantanion in surface water and pore waters samples Howeverthe piper ternary diagrams of surface water and pore waterclearly shows that NaCl is the most dominant in surfacewater while MgCl2 is the most abundant in pore waterCoincidently Palmerrsquos method also reflects that NaCl(574) is the most existent species in surface water fol-lowed by MgCl2 (304) CaCl2 (71) CaSO4 (29)Ca(HCO3)2 (14) and KCl (12) (Figure 3) At the sametime MgCl2 (760) is the most present species in porewater followed by NaCl (73)asympMg(HCO3)2 (73)Ca(HCO3)2 (52) and MgSO4 (31) (Figure 4)
36 Multivariate Analysis
361 Principal Component (PCA) By applying Varimaxrotation and Kaiser normalization to 98 variables in the PCAfor halogens and tested variables and calculated parametervalues 7 extracted PCs with eigenvalues higher than 1 areobtained However it is important that the eigenvalue mustbe greater than 1 Its seven PCs explain 8558 of the totalvariance
-e first principle component (PC1) is 1473 of thetotal variance and shows positive coefficient factor loadingsfor CO3w TDSw Kp calcite aragonite dolomite FeCO3MgCO3 ZnCO3 and ZnCO3H2O (0804 0547 05320938 0938 0947 0741 0940 0866 and 0866 respec-tively) In addition it provides negative factor loadings forHCO3w pHw Bw Nap and CO3s (minus0782 minus0610 minus0595minus0532 and minus0572 respectively) PC1 is related to thefactors affecting the carbonate compounds that may beformed in the area under consideration
PC2 accounts to 1458 of the total variance and alsoshows positive and negative coefficient factor loadingsrepresenting the different interactions between the CawMgw Liw SO4wMgp Nap pHp Cls SO4s Brs and porosityin water pore water and sediment that are responsible forthe composition of sulfate magnesium and phosphateprecipitates besides the effect of the discharged waters onwater-pore water-sediment componentsrsquo cycles
PC3 typically shows 1377 of the total variance withpositive and negative loadings which can properly explorethe effect of the principal sources of local pollution on thedissolving of heavy metals B and P from sediment into thewater column and the probable formation of Fe(OH)2Fe(OH)3) and FePO4
Journal of Chemistry 13
Similarly the coefficient factor loadings of PC4 with1355 are related to the influence of the polluted dischargewater and sediment texture on the formation of F Cl and Isalt besides the precipitation of halogenated compounds(FeF2 Mn(IO3)2 KIO4 and KCIO4) besides their minerals(CaF2 MgF2 FAP and CFAP)
Simultaneously PC5 gives 1092 of the total variancewith positive and negative loadings which explains therelations between the physicochemical limits of the surfacewater pore water and sediment components and theprecipitation of minerals and salts (OCP HAP CuBrZn(OH)2 and Zn(IO3)22H2O) -is is also associated tothe influence of the sedimentary material on the release ofMn Fe and P from sediment into pore water and watercolumn and formation of Ca3(PO4)2 OCP and HAPminerals
However PC6 associates with 100 of the total variancegiving positive and negative coefficient factor loadingswhich explain that the sediments (minerals andor organic-iodine compounds) are only the acting sink for iodine andiodine species (Iminus and IOminus
3 ) in the water as previously re-ported [84] PC6 also reflects the precipitation of severalhalogenated compounds such as calcium iodate (Ca(IO3)2and Ca(IO3)26H2O) and copper iodate (CuI andCuIO3H2O) besides Cu3(PO4)2 species in the lake watercolumn
-e loadings of PC7 contribute by 804 and show thatthe release of calcium in pore water into the water column isresponsible for the precipitation of halogenated compounds(CuCl and Zn(IO3)22H2O) as well as copper and Zn salts(Cu3(PO4)2 and Zn(OH)2)
362 Cluster Analysis On the other hand cluster analysisshows that the similarity of sites 1amp4 5amp8 6amp9 2amp10 and11amp13 is due to the texture of sediment
363 Multiple Regression Multiple regression equations ofhalogens as dependent variables and the other determinedand calculated parameters as independent variables insurface water pore water and sediment partitions are listed(Table 5)-e amount of fluoride in water samples is affectedby the discharged watersrsquo fundamental components espe-cially Zn and Cu besides its surface water-pore water in-teractions Its content in pore water seems to be stronglyaffected by its substitution competition with other halogensin surface water-spore water-sediment cycle due to its highelectronegativity Generally in the affected area the type ofpollutant in the discharged water plays an important role inthe dissolution andor precipitation of fluoride and otherhalogens in the surface water-pore water-sediment cycle
574
147129
300
12
Ca(HCO3)2CaSO4CaCl2
MgCl2KClNaCl
(a)
SO4
2 + CIndash Ca 2+ + Mg 2+
CO32ndash + HCO3
ndashNa+ + K+
Mg2+ SO42ndash
Ca2+ CIndash
(b)
Figure 3 (a) distribution and (b) piper ternary diagram of the formed dissolved salts in surface water of Lake Mariout
Ca(HCO3)2Mg(HCO3)2MgSO4
NaClMgCI2KCl
760 1052
7373 31
(a)
SO4
2ndash + C
Indash
Ca 2+ + Mg 2+
CO32ndash + HCO3
ndashNa+ + K+
Mg2+ SO42ndash
CIndashCa2+
(b)
Figure 4 (a) distribution and (b) piper ternary diagram of the formed dissolved salts in pore water of Lake Mariout
14 Journal of Chemistry
Table 5 -e multiple regression analyses of each halogen as dependent variable and other tested variables in the surface water pore waterand sediment partitions besides the precipitated salts in surface water along Lake Mariout
Dependentvariable Multiple regression equation R2
FluorideLake water FW 3162 + 092 Zn F2 minus 033 SiP + 021 CuIminus 017 SpermilP 09911
Pore water Fp minus2567minus117 SiW minus 033 LiP minus 062 CuClminus 028 IS + 023 TDSW+ 017 KIO4 minus 012 BrW minus 004porosity + 004 PW
10000
Sediment FS 088 CAPminus 049 MgS minus 046 DOW+039MgW+ 027 Mn(IO3)2 + 015 Cu3(PO4)2 + 004 HAP+ 002 pHP 10000ChlorideLake water No relation 00000Pore water No relation 00000Sediment ClS minus116 + 046 MgP + 077 Kp minus 049 dolomite + 017 TDSW minus 011 CuI + 005 NaS + 002 BS + 001 FeF2 10000Bromide
Lake water BrW 1563 + 110 CuBrminus 057 CuClminus 021 KS minus 014 pHP minus 011 TPS + 014 FeW+ 007 ZnSminus 002 PP + 001turbidity 10000
Pore water BrP minus1516minus 055 FeS minus 073 BS + 061 MnW+ 083 SiP + 049 NaS minus 031MnS minus 015 CuBr + 011 pHW minus 001CaW
10000
Sediment BrS 015 SiP + 195 CFAP+ 002 FP minus 045 IS + 192 sand+ 037 MnW minus 029 MgS minus 012 LiP + 005Ca3(PO4)2 minus 002 ZnF2
10000
IodideLake water IW 099 Ca(IO3)6H2O 09999
Pore water IP minus097 ZnF2 minus 057 Li3PO4 minus 053 BP + 034 FAP+ 015 Ca(IO3)2 +MnW+ 005 KS minus 009 turbidity + 055CaS
09999
Sediment IS minus072 + 135 SO4P + 023 Mn(IO3)2 + 063 FeW+ 031 TPS minus 035 MgP minus 012 Zn(CO3)22H2O 09993
40E + 0135E + 0130E + 0125E + 0120E + 0115E + 0110E + 0150E + 0000E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
12345
678910
111213
(a)
10E + 0090E ndash 0180E ndash 0170E ndash 0160E ndash 0150E ndash 0140E ndash 0130E ndash 0120E ndash 0110E ndash 0100E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
12345
678910
111213
(b)
12345
678910
111213
40E ndash 0235E ndash 0230E ndash 0225E ndash 0220E ndash 0215E ndash 0210E ndash 0250E ndash 0300E ndash 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
(c)
12345
678910
111213
80E ndash 0670E ndash 0660E ndash 0650E ndash 0640E ndash 0630E ndash 0620E ndash 0610E ndash 0600E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
(d)
Figure 5 Hazard quotient of ingestion and dermal contact of surface water and sediment of LakeMariout (a) ingestion of water (b) dermalcontact of water (c) ingestion of sediment and (d) dermal contact of sediment
Journal of Chemistry 15
Minerals and precipitated salts in the different partitions(surface water pore water and sediment) play an importantrole in the deposition and release of halogens in sedimentsAdditionally the texture and the porosity of the sedimentsplay a key role in the distribution of halogens in the threepartitions Interestingly chloride is the only halogen that hasnegligible interactions along the surface water and porewater partitions because it is present in large quantities inthe form of soluble salts (NaCl and MgCl2)
37 Pollution Status
371 Enrichment Factor (EF) Twowell-knownmethods areused to assess environmental pollution public health sig-nificance of ingestion and dermal contact with water andsediment components and sediment enrichment factor (EF)[59 60]
-e average EF values of the determined elements CaMg Na K Li B P Cu Zn Mn Fe F Cl Br and I are alllower than the value that is less than the minimum en-richment value (EFlt 2)-us the area under investigation isstill ecologically considered as an unpolluted region
372 Human Health Risk Assessment -e EDI HQ and HIshow the variable values of all pollutants in the surface waterand sediments along the lake region and in drains (sites11ndash13) under study Among all the calculated variables ofsurface water ingestion (EDIIngw) and dermal contact(EDIDermw) Cl is still the only variable that shows high levels(average 1551 and 43mg kgminus1 dayminus1 respectively) -eestimation daily intake of sediment ingestion (EDIIngs) anddermal contact (EDIDerms) of Mg Ca and Na give maximumaverage amounts of 841Eminus 02 513E ndash 02 and167Eminus 03mg kgminus1 dayminus1 respectively
Among the HQ of the calculated detection variables thecontent of HQB of ingestion and dermal contact with waterand sediment is the highest However 70 of sites have HQBvalues more than 10 (Figure 5) Comparing the HQ values ofall the determined variables HQB of the ingestion of surfacewater shows values higher (gt10) However due to the impactof drainage the HQB values of stations 1ndash4 8ndash10 12 and 13
are higher than 10 -erefore these sites can be consideredas the area with the most serious boron pollution caused byuntreated discharged water disposal In addition the HIIngwlevel of water ingestion for the studied variables in all sites ismuch higher than 10 (Figure 6) Except for boron it isusually concluded that the study area does not pose any riskto the population due to halogens or other variables Ac-cordingly this information may help the official authoritiesoptimize management plans and strengthen their pollutioncontrol actions in Lake Mariout
4 Conclusions
-e effects of halogen salts and minerals on the pollution ofLake Mariout were studied Halogens and some physico-chemical variables in three partitions surface water porewater and sediment in Lake Mariout were evaluated -ehalogen content was variable between different sites andchloride was the main halogen in surface water and porewater but it was very rare in the lakersquos sediment partitionPiper ternary diagram and Palmerrsquos method reflected thatNaCl was the dominant salt in surface water while MgCl2was the main dissolve salt in pore water-e chlorinity ratiosof halogens and tested variables were directly matched to thefeeding drain sources
Moreover the Saturation Index (SI) reveals that 23 and 15precipitated salts and minerals are formed in surface water andpore water respectively -e SI value indicated the formationof phosphate minerals in surface water and pore water es-pecially octacalcium phosphate (OCP Ca4H(PO4)325H2O)and hydroxyapatite (HAP Ca5(PO4)3OH) In addition tofluoride minerals especially fluorapatite (FAP) and carbonate-fluorapatite (CFAP) were obviously precipitated from surfacewater and pore water Soluble salts of bromide and chloridewere formed in surface water and pore water Iodide salts(Ca(IO3)2 and Ca(IO3)26H2O) were moderately precipitatedin the surface water and pore water
Moreover the multivariate analysis including the cor-relation matrix multiple stepwise linear regression treeclustering and principle component (PCA) of all the de-termined and calculated variables was applied to estimatethe proposed interaction between halogens and other tested
10E + 02
16E + 0214E + 0212E + 02
80E + 0160E + 0140E + 0120E + 0100E + 00
1 2 3 4 5 6 7 8 9 10 11 12 13
HIIngHIDerm
(a)
1 2 3 4 5 6 7 8 9 10 11 12 13
HIIngHIDerm
40E ndash 0235E ndash 0230E ndash 0225E ndash 0220E ndash 0215E ndash 0210E ndash 0250E ndash 0300E + 01
(b)
Figure 6 Hazard index of ingestion and dermal contact of the studied variables in surface water and sediment of Lake Mariout (a) waterand (b) sediment
16 Journal of Chemistry
variables in the polluted area under study -e multivariateanalysis showed that there were many interactions betweenhalogens and tested variables High levels of fluoride bro-mide and chloride in surface water were related to thecomposition of drainage waters -e enrichment factor (EF)showed that Lake Mariout was not polluted However thehuman health adverse effects calculated for surface waterand sediment did not reflect any possible likelihood hazardeffects from halogens
Interestingly the current study concluded that halogencompounds especially fluorides are most likely to be de-posited from surface lakes in the form of many minerals andprecipitation thereby reducing the adverse pollution effectson human health -e results obtained through this workhelp to find the correlations between the sampling sites andthe variables obtained by physical and chemical measure-ments which can be used to construct a fast decision modelfor separating different water quality samples -is infor-mation may help the official authorities optimize manage-ment plans and strengthen their pollution control measuresin Lake Mariout
Data Availability
-e data used to support the findings of this research areincluded within the paper
Conflicts of Interest
-e authors declare that there are no conflicts of interestregarding the publication of this manuscript
Supplementary Materials
Supplementary Table 1 correlation matrix of variable insurface water pore water and sediment partitions besidesthe precipitated salts in surface water along Lake Mariout(Supplementary Materials)
References
[1] M S Masoud T O Said G El-Zokm and M A ShreadahldquoAssesment of heavy metals contamination in surface sedi-ments of the Egyptian Red Sea Coastsrdquo Australian Journal ofBasic and Applied Sciences vol 6 pp 44ndash58 2012
[2] M A Shreadah M I Abdel Moneim T O SaidE M I Fathallah and M E Mahmoud ldquoPAHs in seawater ofthe semi-closed areas along the Alexandria coast of EgyptianMediterranean seardquo Journal of Environmental Protectionvol 4 no 11 p 11 Article ID 40298 2013
[3] S Abdel Ghani G El Zokm A Shobier T Othman andM Shreadah ldquoMetal pollution in surface sediments of Abu-Qir bay and Eastern harbour of Alexandria Egyptrdquo EgyptianJournal of Aquatic Research vol 39 no 1 pp 1ndash12 2013
[4] G F El-Said ldquoBioaccumulation of key metals and othercontaminants by seaweeds from the Egyptian MediterraneanSea Coast in relation to human health riskrdquo Human andEcological Risk Assessment An International Journal vol 19no 5 pp 1285ndash1305 2013
[5] M A Shreadah A H Shobier S Abdel Ghani G M El-Zokm and T O Said ldquoMajor ions anomalies and
contamination status by trace metals in sediments from twohot spots along the Mediterranean Coast of Egyptrdquo Envi-ronmental Monitoring and Assessment vol 187 no 280pp 1ndash18 2015
[6] A El Nemr G F El-Said A Khaled and S Ragab ldquoDis-tribution and ecological risk assessment of some heavy metalsin coastal surface sediments along the Red Sea Egyptrdquo In-ternational Journal of Sediment Research vol 31 no 2pp 164ndash172 2016
[7] A El Nemr G F El-Said S Ragab A Khaled and A El-Sikaily ldquo-e distribution contamination and risk assessmentof heavy metals in sediment and shellfish from the Red Seacoast Egyptrdquo Chemosphere vol 165 pp 369ndash380 2016
[8] A El Nemr and G F El-Said ldquoAssessment and ecological riskof heavy metals in sediment and molluscs from the Medi-terranean coastrdquo Water Environment Research vol 89 no 3pp 195ndash210 2017
[9] M A Sheradah A A El-Sikaily N M Abd El MoneamN E Abd El Maguid and M G Zaki ldquoChemical and bio-chemical evaluation of marine pollution by polychlorinatedbiphenyls and pesticides in two regions along the EgyptianMediterranean Seardquo International Journal of EnvironmentalMonitoring and Analysis vol 6 no 3 pp 95ndash109 2018
[10] M A Shreadah A A-M M El-Sayed A A S TahaA-M M Ahmed and H H Abdel Rahman ldquoEvaluation ofdifferent anthropogenic effluents impacts on the water qualityusing principal component analysis a case study of Abu-QirBay-Alexandria-Egyptrdquo International Journal of Environ-mental Monitoring and Analysis vol 7 no 3 pp 56ndash67 2019
[11] G F El-Said M M El-Sadaawy A H Shobier andS E Ramadan ldquoHuman health implication of major and traceelements present in commercial crustaceans of a traditionalseafood marketing region Egyptrdquo Biological Trace ElementResearch vol 199 pp 315ndash328 2020
[12] M A Shreadah S A A Ghani H B I HawashA A E Samie and A E M M Ahmed ldquoOrganotin com-pounds in sediments of northern lakes Egyptrdquo Journal ofEnvironmental Protection vol 05 no 17 pp 1654ndash1666 2014
[13] A M Younis G M El-Zokm and M A Okbah ldquoSpatialvariation of acid-volatile sulfide and simultaneously extractedmetals in Egyptian Mediterranean Sea lagoon sedimentsrdquoEnvironmental Monitoring and Assessment vol 186 no 6pp 3567ndash3579 2014
[14] G F El-Said S E O Draz M M El-Sadaawy andA A Moneer ldquoSedimentology geochemistry pollution statusand ecological risk assessment of some heavy metals insurficial sediments of an Egyptian lagoon connecting to theMediterranean Seardquo Journal of Environmental Science andHealth Part A vol 49 no 9 pp 1029ndash1044 2014
[15] G M El Zokm M A Okbah and A M Younis ldquoAssessmentof heavy metals pollution using AVS-SEM and fractionationtechniques in Edku Lagoon sediments Mediterranean SeaEgyptrdquo Journal of Environmental Science and Health PartAvol 50 no 6 pp 571ndash584 2015
[16] G M El Zokm H R Z Tadros M A Okbah andG H Ibrahim ldquoldquoEutrophication assessment using TRIX andCarlsonrsquos indices in Lake Mariout water Egyptrdquo EgyptianJournal of Aquatic Biology and Fisheries vol 22 no 5pp 331ndash349 2018
[17] N Donia ldquoLake Maryut monitoring using remote sensingrdquo inProceedings of the gypt Eighteenth International WaterTechnology Conference IWTC18 Sharm El Sheikh Abu DhabiUAE March 2015
Journal of Chemistry 17
[18] M A Khairy ldquoAssessment of priority phenolic compounds insediments from an extremely polluted coastal wetland (LakeMaryut Egypt)rdquo Environmental Monitoring and Assessmentvol 185 no 1 pp 441ndash455 2013
[19] N A El-Naggar and E A Rifaat ldquoEgyptian coastal lakes andwetlands part Imdashcharacteristics and hydrodynamicsrdquo in eHandbook of Environmental Chemistry A M Negm EdSpringer International Publishing AG Berlin Germany 2017
[20] J J Hanley and K T Koga ldquoChapter 2 ldquohalogens in terrestrialand cosmic geochemical systems abundances Geochemicalbehaviors and analytical methodsrdquordquo in e Role of Halogensin Terrestrial and Extraterrestrial Geochemical ProcessesD E Harlov and L Aranovich Eds Springer InternationalPublishing AG Berlin Germany pp 21ndash121 2018
[21] A Ghosh K Mukherjee S K Ghosh and B Saha ldquoSourcesand toxicity of fluoride in the environmentrdquo Research onChemical Intermediates vol 39 no 7 pp 2881ndash2915 2013
[22] M M Naim A A Moneer and G F El-Said ldquoPredictiveequations for the defluoridation by electrocoagulation tech-nique using bipolar aluminum electrodes in the absence andpresence of additives a multivariate studyrdquo Desalination andWater Treatment vol 57 no 14 pp 6320ndash6332 2016
[23] G F El-Said N A Shaltout M M El-Sadaawy andA M H Morsy ldquo-e precipitation of fluoride calcium andmagnesium minerals from Egyptian Mediterranean Sea coastin relation to discharged watersrdquo Desalination and WaterTreatment vol 57 no 5 pp 2113ndash2124 2016
[24] H Bureau ldquoIodine encyclopedia of geochemistry A com-prehensive reference source on the chemistry of the earthrdquo inEncyclopedia of Earth Sciences Series W M White Ed copySpringer International Publishing AG 2016
[25] F C Kupper and C J Carrano ldquoKey aspects of the iodinemetabolism in brown algae a brief critical reviewrdquo Metal-lomics vol 11 pp 756ndash764 2019
[26] R Liteplo R Gomes P Howe and H Malcolm Fluorides-Environmental Health Criteria 227 p 290 World HealthOrganization (WHO) Geneva Switzerland 2002
[27] G F El-Said and M M El-Sadaawy ldquoSeasonal variation ofboron and fluoride in Tilapia nilotica from an Egyptian fishfarm in relation to Human health hazard assessmentrdquoHumanand Ecological Risk Assessment An International Journalvol 19 no 4 pp 930ndash943 2013
[28] WHO (World Health Organization) Bromide in Drinking-Water Background Document for Development of WHOGuidelines for Drinking-Water Quality WHO Press WorldHealth Organization Geneva Switzerland 2009
[29] G F El-Said and N A Sallam ldquo-e uptake of fluorideconcentration and its effects on the growth rate of shrimps(Palaemon elegans Rathke)rdquo Chemistry and Ecology vol 24no 3 pp 191ndash205 2008
[30] X Zhang J He B He and J Sun ldquoAssessment formationmechanism and different source contributions of dissolvedsalt pollution in the shallow groundwater of Hutuo Riveralluvial-pluvial fan in the North China Plainrdquo EnvironmentalScience and Pollution Research vol 26 no 35 pp 35742ndash35756 2019
[31] Y Zhu B Huang Z Zhu et al ldquoldquoCharacterization disso-lution and solubility of the hydroxypyromorphitendashhydroxyapatite solid solution [(PbxCa1minusx)5(PO4)3OH] at25 degC and pH 2ndash9rdquo Geochemical Transactions vol 17 no 2pp 1ndash18 2016
[32] G F El-Said M M El-Sadaawy A A Moneer andN A Shaltout ldquo-e effect of fluoride on the distribution ofsome minerals in the surface water of an Egyptian lagoon at
the Mediterranean Seardquo Egyptian Journal of Aquatic Researchvol 41 no 1 pp 31ndash39 2015
[33] Y Zhu Z Zhu X Zhao Y Liang and Y Huang ldquoChar-acterization dissolution and solubility of lead hydroxypyr-omorphite [Pb5(PO4)3OH] at 25ndash45degCrdquo Journal ofChemistry vol 2015 Article ID 269387 10 pages 2015
[34] M A Z Chahouki ldquoMultivariate analysis techniques inenvironmental sciencerdquo in Earth and Environmental SciencesDr Imran Ahmad Dar Ed InTech Open London UK 2011httpwwwintechopencombooksearth-and-environmental-sciencesmultivariate-analysis-techniques-inenvironmental-science
[35] J V Klump and C S Martens ldquoBiogeochemical cycling in anorganic-rich coastal marine basin 5 Sedimentary nitrogenand phosphorus budgets based upon kinetic models massbalances and the stoichiometry of nutrient regenerationrdquoGeochimica et Cosmochimica Acta vol 51 no 5 pp 1161ndash1173 1987
[36] R L Folk Petrology of Sedimentary Rocks University of TexasAustin TX USA 1974
[37] P Saenger ldquoA rapid spectrophotometric method for thedetermination of bromine in seawater and in the ash ofmarine algaerdquo Helgolander Wissenschaftliche Meer-esuntersuchungen vol 23 no 1 pp 32ndash37 1972
[38] P G Jeffery Chemical Methods of Rock Analysis PergamonPress New York NY USA 2nd edition 1975
[39] J D H Strickland and T R Parsons ldquoA practical handbook ofseawater analysisrdquo in Fisheries Research Board of CanadaBulletin 167p 311 Second edition Wiley Ottawa Canada1972
[40] B Horvath O Opara-Nadi and F Beese ldquoA simple methodfor measuring the carbonate content of soilsrdquo Soil ScienceSociety of America Journal vol 69 no 4 pp 1066ndash1068 2005
[41] K Grasshoff Methods of Seawater Analysis p 317 VerlagChemie Weinkeim Germany 1976
[42] R Danovaro D Marrale N Della Croce P Parodi andM Fabiano ldquoBiochemical composition of sedimentary or-ganic matter and bacterial distribution in the Aegean Seatrophic state and pelagic-benthic couplingrdquo Journal of SeaResearch vol 42 no 2 pp 117ndash129 1999
[43] APHA-AWWA-WPCF (American Public Health Associa-tion) Standard Methods for the Examination of Water andWaste Water American Public Health Association Wash-ington DC USA 20th edition 1999
[44] K I Aspila H Agemian and A S Y Chau ldquoA semi-auto-mated method for the determination of inorganic organicand total phosphate in sedimentsrdquo e Analyst vol 101no 1200 pp 187ndash197 1976
[45] J P Riley and D Taylor ldquoChelating resins for the concen-tration of trace elements from sea water and their analyticaluse in conjunction with atomic absorption spectrophotom-etryrdquo Analytica Chimica Acta vol 40 pp 479ndash485 1968
[46] G F El-Said and A El-Sikaily ldquoChemical composition ofsome seaweed from Mediterranean Sea coast Egyptrdquo Envi-ronmental Monitoring and Assessment vol 185 no 7pp 6089ndash6099 2013
[47] Directorate General of Health Services Ministry of Health andFamilyWelfare Government of India ldquoManual of methods ofanalysis of foodsrdquo in Fruit and Vegetable Productsp 57Directorate General of Health Services Ministry of Health andFamily Welfare Government of India New Delhi India2005
[48] A Gunnars S Blomqvist and C Martinsson ldquoInorganicformation of apatite in brackish seawater from the Baltic Sea
18 Journal of Chemistry
an experimental approachrdquo Marine Chemistry vol 91 no 1-4 pp 15ndash26 2004
[49] W M Haynes D R Lide and T J Bruno CRC Handbook ofChemistry and Physics A Ready Reference Book of Chemicaland Physical Data CRC Press Taylor amp Frances Group BocaRaton FL USA 97th edition 2017
[50] M S Masoud M I El-Samra and M M El-Sadawy ldquoWaterchemistry of el-mex bay west of Alexandria Egyptrdquo eEgypian Science Magazine vol 2 pp 70ndash78 2005
[51] F J Millero R Feistel D G Wright and T J McDougallldquo-e composition of standard seawater and the definition ofthe reference-composition salinity scalerdquo Deep Sea ResearchPart I Oceanographic Research Papers vol 55 no 1pp 50ndash72 2008
[52] S K El-Wakeel S A Morcos and A M Mahlis ldquo-e majorcations in Lake Maryut watersrdquo Hydrobiologia vol 36 no 2pp 253ndash274 1970
[53] A M Mahlis S A Morcos and S K El-Wakeel ldquo-e majoranions in Lake Maryut watersrdquo Hydrobiologia vol 36 no 2pp 275ndash294 1970
[54] A S Saad M A Massoud R A Amer and M A GhorabldquoAssessment of the physico-chemical characteristics andwater quality analysis of Mariout Lake southern of Alexan-dria Egyptrdquo Journal of Environmental and Analytical Toxi-cology vol 7 no 1 p 421 2017
[55] R Rumuri ldquoDataset on hydrogeochemical characteristics ofgroundwater and surface water in Kattumannarkoil TalukIndiardquo Data in Brief vol 32 Article ID 106058 2020
[56] P Szefer S W Fowler K Ikuta et al ldquoA comparative as-sessment of heavy metal accumulation in soft parts and byssusof mussels from subarctic temperate subtropical and tropicalmarine environmentsrdquo Environmental Pollution vol 139no 1 pp 70ndash78 2006
[57] N F Soliman G M El Zokm and M A Okbah ldquoRisk as-sessment and chemical fractionation of selected elements insurface sediments from Lake Qarun Egypt using modifiedBCR techniquerdquo Chemosphere vol 191 pp 262ndash271 2018
[58] G M El Zokm M I A Ibrahim L A Mohamed and M El-Mamoney ldquoCritical geochemical insight into Alexandria coastwith special reference to diagnostic ratios (TOCTN amp SrCa)and heavy metals ecotoxicological hazardsrdquo Egyptian Journalof Aquatic Research vol 46 no 1 pp 27ndash33 2020
[59] A S Likuku K B Mmolawa and G K GaboutloeloeldquoAssessment of heavy metal enrichment and degree of con-tamination around the copper-nickel mine in the SelebiPhikwe Region Eastern Botswanardquo Environment and EcologyResearch vol 1 no 2 pp 32ndash40 2013
[60] M K Khalil S E O Draz G M El Zokm and G F El-SaidldquoApportionment of geochemistry texturersquos properties and riskassessment of some elements in surface sediments from Bar-dawil Lagoon Egyptrdquo Human and Ecological Risk AssessmentAn International Journal vol 22 no 3 pp 775ndash791 2016
[61] M M El-Sadaawy and G F El-Said ldquoAssessment of fluoridein three selected polluted environments along the EgyptianMediterranean Sea effects on local populationsrdquo Human andEcological Risk Assessment An International Journal vol 20no 6 pp 1643ndash1658 2014
[62] USEPA ldquoSuperfund exposure assessment manualrdquo inOSWER Directive 92855-1EPA540l-88001Office of Emer-gency and Remedial Response Washington DC USA 1988
[63] USEPA ldquoExposure factors handbookrdquo in EPA6008-89043Office of Health and Environmental Assessment Wash-ington DC USA 1989
[64] Health Canada ldquoFederal Contaminated Site Risk Assessmentin Canadardquo Part II Health Canada Toxicological ReferenceValues (TRVs) Cat H46-204-368E Calgary Health CanadaOttawa Canada 2007
[65] J Iqbal S A Tirmizi and M H Shah ldquoStatistical appor-tionment and risk assessment of selected metals in sedimentsfrom Rawal Lake (Pakistan)rdquo Environmental Monitoring andAssessment vol 185 no 1 pp 729ndash743 2013
[66] USEPA (US Environmental Protection Agency) Region 6USAEPA ldquoMultimedia Planning and Permitting DivisionrdquoOffice of Solid Waste Center for Combustion Science andEngineering Washington DC USA 2005
[67] P Jeschke ldquoLatest generation of halogen-containing pesti-cidesrdquo Pest Management Science vol 73 no 6 pp 1053ndash10662017
[68] M A Shreadah O A El-Rayis N A Shaaban andA M Hamdan ldquoWater quality assessment and phosphorusbudget of a lake (Mariut Egypt) after diversion of wastewaterseffluentsrdquo Environmental Science and Pollution Researchvol 27 no 21 pp 26786ndash26799 2020
[69] J P Riley and M Tongudai ldquo-e major cationchlorinityratios in sea waterrdquo Chemical Geology vol 2 pp 263ndash2691967
[70] R B McCleskey D K Nordstrom D D Susong J W Balland J M Holloway ldquoSource and fate of inorganic solutes inthe gibbon river yellowstone national park Wyoming USArdquoJournal of Volcanology and Geothermal Research vol 193no 3-4 pp 189ndash202 2010
[71] G T F Wong and K-Y Li ldquoWinklerrsquos method overestimatesdissolved oxygen in seawater iodate interference and itsoceanographic implicationsrdquo Marine Chemistry vol 115no 1-2 pp 86ndash91 2009
[72] B S R V Prasad P D N Srinivasu P S VarmaA V Raman and S Ray ldquoDynamics of dissolved oxygen inrelation to saturation and health of an aquatic body a case forChilka Lagoon Indiardquo Journal of Ecosystems vol 2014 Ar-ticle ID 526245 17 pages 2014
[73] China Environmental Protection Agency EnvironmentalQuality Standards for Surface Water (GB3838ndash2002) NationalEnvironmental Protection Agency of China Beijing China2002
[74] Y Jia L Wang Z Qu and Z Yang ldquoDistribution con-tamination and accumulation of heavy metals in watersediments and freshwater shellfish from Liuyang RiverSouthern Chinardquo Environmental Science and Pollution Re-search vol 25 no 7 pp 7012ndash7020 2018
[75] A Moneer M El-Sadawy G El-Said and A Radwan ldquoBoronhuman health risk assessment relative to the environmentalpollution of Lake Edku Egyptrdquo Journal of King AbdulazizUniversity vol 23 no 2 pp 41ndash55 2012
[76] C B Tabelin T Igarashi T Arima D Sato T Tatsuhara andS Tamoto ldquoCharacterization and evaluation of arsenic andboron adsorption onto natural geologic materials and theirapplication in the disposal of excavated altered rockrdquo Geo-derma vol 213 pp 163ndash172 2014
[77] G Aloisi K Wallmann M Drews and G BohrmannldquoEvidence for the submarine weathering of silicate minerals inBlack Sea sediments possible implications for the marine Liand B cyclesrdquo Geochemistry Geophysics Geosystems vol 5no 4 pp 1ndash22 2004
[78] C Degueldre and V Cloet ldquoPore water colloid properties inargillaceous sedimentary rocksrdquo Science of e Total Envi-ronment vol 569-570 pp 423ndash433 2016
Journal of Chemistry 19
[79] J A Higgins and D P Schrag ldquoRecords of Neogene seawaterchemistry and diagenesis in deep-sea carbonate sedimentsand pore fluidsrdquo Earth and Planetary Science Letters vol 357-358 pp 386ndash396 2012
[80] H Schroeder A-L Fabricius D Ecker T A Ternes andL Duester ldquoMetal(loid) speciation and size fractionation insediment pore water depth profiles examined with a newmesoprofiling systemrdquo Chemosphere vol 179 pp 185ndash193 2017
[81] Y Song and G Muller ldquoFreshwater sediments sinks andsources of brominerdquo Naturwissenschaften vol 80 no 12pp 558ndash560 1993
[82] M E Goher H I Farhat M H Abdo and S G Salem ldquoMetalpollution assessment in the surface sediment of Lake NasserEgyptrdquo Egyptian Journal of Aquatic Research vol 40 no 3pp 213ndash224 2014
[83] G F El-Said M M El-Sadawy and A A Moneer ldquoIncor-poration of fluoride and boron into surface sediments alongthe Egyptian Mediterranean coastrdquo Egyptian Journal ofAquatic Research vol 36 no 4 pp 569ndash583 2010
[84] B Gilfedder G M Petri M Wessels and H Biester ldquoAniodine mass-balance for Lake Constance Germany insightsinto iodine speciation changes and fluxesrdquo Geochimica etCosmochimica Acta vol 74 no 11 pp 3090ndash3111 2010
[85] E Korobova L Kolmykova B Ryzhenko et al ldquoDistributionand speciation of iodine in drinking waters from geochem-ically different areas of Bryansk region contaminated after theChernobyl accident in relation to health and remediationaspectsrdquo Journal of Geochemical Exploration vol 184pp 311ndash317 2018
[86] V Zic V W Truesdale and N Cukrov ldquo-e distribution ofiodide and iodate in anchialine cave watersmdashevidence forsustained localised oxidation of iodide to iodate in marinewaterrdquoMarine Chemistry vol 112 no 3-4 pp 168ndash178 2008
[87] M B Heeb J Criquet S G Zimmermann-Steffens andU Von Gunten ldquoOxidative treatment of bromide-containingwaters formation of bromine and its reactions with inorganicand organic compoundsmdasha critical reviewrdquo Water Researchvol 48 pp 15ndash42 2014
[88] V Sivasankar A K Darchen and R Omine SakthivelldquoChapter 2 ldquofluoride a world ubiquitous compound itschemistry and ways of contaminationrdquo in Surface ModifiedCarbons as Scavengers for Fluoride fromWater V SivasankarEd pp 5ndash32 copy Springer International Publishing Switzer-land Cham Switzerland 2016
[89] O Cabestrero P Del Buey and M E Sanz-Montero ldquoBio-sedimentary and geochemical constraints on the precipitationof mineral crusts in shallow sulphate lakesrdquo SedimentaryGeology vol 366 pp 32ndash46 2018
[90] M A Hassaan O A El-Rayis and E I Hemada ldquoEstimationof the redox potential of lake mariut drainage system (Qalaaand Umum drains)rdquoHydrology vol 5 no 6 pp 82ndash85 2017
20 Journal of Chemistry
cost of further environmental investigations [56ndash58] -emultivariate analysis using the correlation matrix with acorrelation coefficient (r) multiple stepwise linear regressionwith a coefficient (R) and cluster (tree clustering) at asignificance level of ple 005 is estimated by STATISTICA 99edition At the same time the principal component (PCA)can be estimated through SPSS 15 evaluation
29 Enrichment Factor (EF) EF of the determined elements(Ca Mg Na K Li B P Cu Zn Mn Fe F Cl Br and I) wascalculated by using the equations described (equations (2)and (3)) [59 60]
EF Cm sample
MedianCm Background + 2 times MADCm Background( 1113857
(2)
where Cm was the element concentration Median CmBackground represented median concentration of an ele-ment in the background and MAD Cm Background was themedian absolute deviation from the median calculated fromthe given equation
MAD median xi minus medianj xj1113872 111387311138681113868111386811138681113868
111386811138681113868111386811138681113874 1113875 (3)
-e EF values were classified into five categories defi-ciency tominimal (EFlt 2) moderate (2ltEFlt 5) significant(5ltEFlt 20) very high (20ltEFlt 40) and extremely highenrichment (EFgt 40)
210 Human Health Risk Assessment -e human healthhazard of surface water and sediment ingestion and dermalcontact was assessed by using the estimated daily intake
Table 1 -e hypothetical precipitated salts in surface and pore waters along Lake Mariout
Site 1 2 3 4 5 6 7 8 9 10 11 12 13SI of precipitated salts and minerals
Surface waterCalcite 128 138 340 146 236 303 295 297 205 258 312 126 311Aragonite 103 112 315 120 211 278 270 272 180 233 287 101 286CaSO405 H2O 208 188 126 157 156 155 170 179 199 171 115 075 181CaSO42H2O 196 176 114 144 143 143 158 167 187 158 103 063 169Ca3(PO4)2 2486 2424 2424 2424 2424 2424 2424 2424 2424 2424 2424 2424 2424Ca(IO3)2 157 137 137 137 137 137 137 137 137 137 137 137 137Ca(IO3)26H2O 1006 986 986 986 986 986 986 986 986 986 986 986 986OCP 3964 3569 3569 3569 3569 3569 3569 3569 3569 3569 3569 3569 3569HAP 4574 4349 4349 4349 4349 4349 4349 4349 4349 4349 4349 4349 4349FAP 4277 5036 5038 5195 5171 5131 5090 4982 5131 5081 4903 5095 5163CFAP 6089 1685 1786 1818 1784 1902 1883 1785 1764 1859 1604 1824 1914Fe(OH)2 1196 1217 1196 1189 1208 1059 1176 1158 1007 1192 1205 1199 1152Fe(OH)3 3544 3564 3543 3536 3555 3407 3524 3505 3354 3539 3552 3546 3499FePO42H2O 1053 1074 1053 1046 1065 916 1033 1015 864 1049 1062 1056 1008Mg(OH)2 1215 1206 1131 1171 1173 1159 1179 1188 1170 1183 1151 1152 1168Mg3(PO4)2 085 1345 1121 1240 1245 1205 1264 1291 1236 1276 1180 1184 1229Mn(IO3)2 025 243 354 303 247 312 226 055 183 198 064 262 042KIO4 576 570 552 549 565 564 559 554 551 560 489 551 548KCIO4 495 489 471 468 484 483 478 473 470 479 408 470 467ZnCO3 414 404 613 455 560 560 586 573 491 530 659 472 581ZnCO3H2O minus018 minus027 181 024 128 128 154 142 060 099 227 041 149Zn(OH)2 1198 1189 1199 1210 1254 1194 1223 1232 1216 1207 1249 1227 1203Zn(IO3)22H2O 366 357 367 378 422 362 391 400 383 375 417 395 371Pore waterFluorite 200 211 106 195 346 309 345 317 228 246 307 365 277CaSO405 H2O 370 177 190 200 168 178 202 255 203 212 191 179 211CaSO42H2O 358 165 178 188 155 166 190 243 191 200 178 167 199Ca3(PO4)2 2958 2424 2424 2424 2424 2424 2424 2424 2424 2424 2424 2424 2424Ca(IO3)2 315 137 137 137 137 137 137 137 137 137 137 137 137Ca(IO3)26H2O 1164 986 986 986 986 986 986 986 986 986 986 986 986OCP 4594 3569 3569 3569 3569 3569 3569 3569 3569 3569 3569 3569 3569HAP 5361 4349 4349 4349 4349 4349 4349 4349 4349 4349 4349 4349 4349FAP 5126 5295 5399 5270 5460 5318 5327 5338 5321 5311 5420 5373 5391CFAP 7833 1775 2068 1752 2049 2078 1990 2015 1963 2026 2121 2024 2060MgF2 299 138 177 060 262 232 095 209 212 243 222 251 203Mg(OH)2 1395 1439 1408 1400 1428 1420 1346 1425 1418 1438 1412 1391 1414Mg3(PO4)2 987 2442 2417 2355 2469 2207 2128 2317 2243 2260 2387 2132 2378KIO4 564 568 575 557 561 560 570 566 558 571 551 543 564KCIO4 483 487 494 476 480 479 489 485 477 490 470 461 483
Journal of Chemistry 5
(EDI) hazard quotient (HQ) and hazard index (HI) as givenin equations (4)ndash(11)
2101 For Surface Water Estimated daily intake of surfacewater ingestion and dermal contact (EDIIngw and EDIDermw)were computed by the following equations [61]
EDIIngw(mgkgday) (CW times CR times ET times EF times ED)
(AT times BW) (4)
EDIDermw(mgkgday) (CW times SA times PC times ET times EF times ED times CF)
(AT times BW)
(5)
where CWwas the element concentration in water (mg Lminus1)CR was the contact time (50mL hminus1) ET was the exposuretime (26 h dayminus1) EF was the exposure frequency (7 dayyearminus1) ED was the exposure duration (60 year) ATwas theaverage time (60times 365 day yearminus1) BWwas (707 kg) SAwas
the skin surface area (5700 cmminus2) PC was the dermalpermeability constant (0001 cm hminus1) and CF was theconversion factor for water (10times10minus6 kg mgminus1) [62ndash65]
2102 For Sediment Estimated daily intake of sediment byingestion and dermal contact (EDIIngs and EDIDerms) werecalculated according to the following equations [60]
EDIIngS(mgkgday) CS times IngS times RAFS times EFS( 1113857
(AT times BW) (6)
EDIDermS(mgkgday) CS times IngS times ED times SA times AF times ABS( 1113857
(AT times BW)
(7)
where CS was the concentration of the contaminant insediment (mg gminus1) IngS was the ingestion rated of sediment(80times10minus5mg kgminus1) RAFS was the relative absorption factorof sediment (058) EFS was the exposure frequency (30 day
Table 2 Distribution of the studied variables in surface water (w) and their chlorinity ratios along Lake Mariout
Determined variables Minimum Site Maximum Site Average SD Seawatera Lake Marioutbcd
Physicochemical variablesTw 137 10 1534 11 1759 134Salinity (Spermilw) 23 13 79 1 489 152Chlorinity (Clpermilw) 205 13 71 1 438 137 1898TDSw (mg Lminus1l) 24635 13 7683 1 48503 152874Turbidity (NTU) 166 8 385 12 1296 1174DOw (mg Lminus1l) 0 6 1241 2 605 483 214ndash563d
pHw 744 13 899 2 710ndash860d
CO3w (mg Lminus1) 12 1 amp 2 1152 3 31 388HCO3w (mg Lminus1) 7808 3 19032 12 1147 321Bw (mg Lminus1) 05 7 1661 1 691 411 45Pw (μg Lminus1) 003 8 126 5 029 033Siw (μg Lminus1) 009 12 699 4 317 191Caw (mg Lminus1) 6092 12 3527 8 17703 735 400 549 818ndash1464d
Mgw (mg Lminus1) 9725 3 66615 1 28684 16002 1272 1201Naw (mg Lminus1) 231 11 1420 1 101115 2972 10556 10332Kw (mg Lminus1) 8 11 59 1 3769 123 380 585Liw(mg Lminus1) 0139 11 017 1 0154 001 017SO4w (mg Lminus1) 1978 12 34111 9 16856 9488 2649 4245Cuw (μg Lminus1) 204 3 621 7 317 113 7Mnw (μg Lminus1) 001 8 amp13 198 3 315 554 10Few (μg Lminus1) 009 9 1392 13 69 419 40Znw (μg Lminus1) 527 2 2367 5 1085 578 20Fw (mg Lminus1) 015 11 396 12 204 117 13Clw (mg Lminus1) 2048 13 7284 1 4397 1400 18980Brw (mg Lminus1) 506 12amp13 541 5 1813 1891 65 592Iw (μg Lminus1) 566 10 541 4 1108 1296 60Ion chlorinity ratioCawClw 170Eminus 02 12 100Eminus 01 13 440Eminus 02 240Eminus 02 213Eminus 02 335Eminus 02MgwClw 250Eminus 02 3 110Eminus 01 13 640Eminus 02 230Eminus 02 669Eminus 02 733Eminus 02NawClw 650Eminus 02 11 380Eminus 01 13 240Eminus 01 720Eminus 02 560Eminus 01 635Eminus 01KwClw 220Eminus 03 11 150Eminus 02 13 890Eminus 03 290Eminus 03 210Eminus 02 360Eminus 02LiwClw 240Eminus 05 1 700Eminus 05 13 380Eminus 05 110Eminus 05 939Eminus 06SO4wClw 540Eminus 03 12 110Eminus 01 13 420Eminus 02 310Eminus 02 140Eminus 01 260Eminus 01BwClw 978Eminus 05 7 332Eminus 03 9 670Eminus 03 170Eminus 03 895Eminus 04FwClw 430Eminus 05 11 140Eminus 03 13 540Eminus 04 420Eminus 04 670Eminus 05BrwClw 140Eminus 03 12 160Eminus 02 9 440Eminus 03 500Eminus 03 350Eminus 03 360Eminus 05IwClw 940Eminus 04 1 160Eminus 02 4 300Eminus 03 400Eminus 03a[51] b and c[52 53] d[54]
6 Journal of Chemistry
yearminus1) AF was the adherence factor (007mg cmminus2) andABS was the dermal absorption factor (0001 unit less)[65 66]
Hazard index (HI) is the total chronic hazard attribut-able to exposure to all determined contaminants (i) througha single exposure pathway of the ingestion and dermalcontact of water (HIIngw and HIDermw) and sediment (HIIngsand HIDerms) was given as follows [60]
HIIngW 1113944HQ IngW( 1113857i (8)
HIDermW 1113944HQ DermW( 1113857i (9)
HIIngS 1113944HQ IngS( 1113857i (10)
HIDermS 1113944HQ DermS( 1113857i (11)
3 Results and Discussion
31 Distribution of Halogens and Tested Variables in SurfaceWater
311 Distribution of Halogens in Surface Water -e rangeand average value of halogens in the surface water in thisstudy show a sequence of ClwgtBrwgt Fwgt Iw (Table 2 andFigure 2)-e current study indicate that the water sample ofpumping station (site 6) attained high concentrations offluoride (28mg Lminus1) chloride (38878mg Lminus1) and bromide(181mg Lminus1) and low iodide (641 μg Lminus1) contents (Fig-ure 2) High levels of F Br and I are detected in the MainBasin region which is affected by the drainage of El-Qalaaand El Umoum containing the agricultural and industrialwastes However halogens are involved in the manufactureof pesticides (herbicides fungicides insecticidesacaricidesand nematicides) [67] Plus halogens are produced in theproduction of fertilizers products [67] -e presented resultsof halogens in the studied lake region reflect anomalousdistribution and are mainly affected by water dischargedfrom the drainage sources However the highest fluoridebromide and iodide contents of 377mg Lminus1 6553mg Lminus1and 5410 μg Lminus1 respectively are recorded in the MainBasin affected by El-Qalaa and El Umoum drains Amongthe halogens chloride shows high levels in surface waterespecially in site 1 (72837mg Lminus1) site 2 (65218mg Lminus1)and site 10 (51687mg Lminus1) which are also related to theirlevels in the water of the drains (Figure 2) On the meantimethe lowest Spermilw and Clpermilw are observed at site 13 (ElUmoum Drain) Most of the studied variables have chlo-rinity ratios relatively lower than those measured for LakeMariout andor seawater [51ndash53 68 69] -is is mainly dueto the accumulation of wastewater from Abis and ElUmoum where agricultural products such as fertilizers andbiocides are deposited in industrial products [19]
Due to the increase in chloride content in surface watersamples the conservativeness of the chlorinity ratio is usedto describe the contamination precipitation and dissolutionof sediment components [70] -e FCl ratio in the studyarea is higher than open seawater (430Eminus 05) of a range
430Eminus 05ndash140Eminus 03 and average 540Eminus 04 -e BrClratio is relatively similar to that of seawater (Table 2) -ehighest FCl BrCl and ICl ratios in surface water140Eminus 03 160E ndash 02 and 160Eminus 02 are recorded in site 13(El Umoum drain outside the lake) site 9 (South West Basinin the lake) and site 4 (Main Basin in the lake) -erefore itcan be concluded that the distribution of halogens in thesurveyed area is greatly affected by the drainage of the El-Qalaa El Umoum and the El Nubaria drains
312 Distribution of Tested Variables in Surface Water-e range and average values of the tested variables (Tw Spermilw Clpermilw TDSw turbidity DOw pHw CO3w HCO3w BwPw Siw Caw Mgw Naw Kw Liw SO4w Cuw Mnw Few andZnw) in surface waters of the present study are listed inTable 2 Turbidity fluctuates from 166 to 3850 NTU at sites8 and 12 respectively DO is completely depleted at sites 5 6and 11 and has the highest amount 1241mg Lminus1 at site 2with an average 605mg Lminus1 relatively similar to the reportedLake Mariout value (214ndash563mg Lminus1 [54]) (Table 2) -eaverage content of DO in the lake is higher than those re-ported for the ocean seawater (32ndash48mgL) [71] -e levelsof DO probably relate to the oxygen-producing processes ofthe photosynthesis processes of phytoplankton and mac-rophytes [72] -e presented results indicate that site 1(affect by Abis drainage) is the most affected area in the lakeas it shows the highest contents of Bw Clw Mgw Naw KwLiw and SO4w -e most important feature in the concen-trations of heavy metals Cuw Mnw and Znw in surface wateris that they possess average values lower than those reportedfor the threshold guideline (10 100 and 50 μg Lminus1) [73 74]
-e present study clears out a descending trend in thesurface water average concentrations of halogens andtested variables in the lake as follows TDSw gtClw gtNaw gtMgw gtCaw gt SO4w gtHCO3wgtKw gtCO3w gt Bw gt Brwgt FwgtLiw gt Znw gt Few asymp Siw gtMnw gt Pw gt Iw (Table 2)
313 Interactions of Halogens and Tested Variables inSurface Water Chloride in surface water is significantlyrelated to the drainage water content showing good cor-relations with Tw (r 0631 ple 0028) and pHw (r 0769ple 0003) (Supplementary Table 1) -e negative moderaterelation of Fw and Ip (r 0606 ple 0037) may indicatereplacement of iodine in pore water by fluoride of the surfacewater-emoderate relationship between fluoride in surfacewater and CO3w (r minus0632 ple 0027) and HCO3w(r 0593 ple 0042) may be related to carbonate exchangeand the formation of fluorite minerals (CaF2) [23]
-e correlation matrix reflects that the observed ex-traordinary levels of Bw in the surface water samples aremost probably due to its exchange with the different sedi-ment components not related to the discharged waters(Supplementary Table 1) -is findings is supported by theweak B correlation with Cuw (r minus0587 ple 0045) andgood correlation with Fs (r minus0666 ple 0018) [75 76]However Cuw is one of the pollutants that can be exchangedin drainage water -e correlations of Mgw amp Naw (r 0629
Journal of Chemistry 7
1
23
4
56
7
8
9
10
2986degE 2988degE 2990degE 2992degE
310
8degN
311
0degN
311
2degN
311
4degN
311
6degN
El-mex
pumping
statio
n Main Basin
of Lake Maryout
Southwest Basin
Qalaa Drain
El Umoum Drain
Northwest BasinFish
ery Basi
nEl Nubaria Drain
3311 to 38883888 to 43934393 to 5115
5115 to 65226522 to 7284
(a)
1
23
4
56
7
8
9
10
2986degE 2988degE 2990degE 2992degE
310
8degN
311
0degN
311
2degN
311
4degN
311
6degN
El-mex
pumping
statio
n
Main Basinof Lake Maryout
Southwest Basin
Qalaa Drain
El Umoum Drain
Northwest Basin
Fishery
BasinEl Nubaria Drain
069 to 127127 to 169169 to 242
242 to 277277 to 377
(b)
El-mex
pumping
statio
n
Main Basin of Lake Maryout
South west Basin
North west Basin
1
23
4
56
7
8
9
10
2986degE 2988degE 2990degE 2992degE
310
8degN
311
0degN
311
2degN
311
4degN
311
6degN
Qalaa Drain
El Umoum Drain
Fishery
BasinEl Nubaria Drain
613 to 852852 to 14381438 to 1732
1732 to 52745274 to 6554
(c)
El-mex
pumping
statio
n
Main Basin of Lake Maryout
Southwest Basin
Northwest Basin
1
23
4
56
7
8
9
10
2986degE 2988degE 2990degE 2992degE
310
8degN
311
0degN
311
2degN
311
4degN
311
6degN
Qalaa Drain
El Umoum Drain
Fishery
BasinEl Nubaria Drain
566 to 671671 to 761761 to 817
817 to 922922 to 5411
(d)
Figure 2 Distribution of halogens (Cl F Br and I in surface water of LakeMariout (a) Cl (mg Lminus1) (b) F (mg Lminus1) (c) Br (mg Lminus1) and (d) I(μg Lminus1)
8 Journal of Chemistry
ple 0028) Mgw amp Liw (r 0790 ple 0002) Naw amp Kw(r 0955 ple 0000 Naw amp Liw (r 0835 ple 0001) Naw ampCO3w (r minus0701 ple 0011) Kw amp Liw (r 0712 ple 0009)Kw amp CO3w (r minus0580 ple 0048) CO3w amp HCO3w(r minus0613 ple 0034) and Mgw amp SO4w (r 0631ple 0028) indicate that all these variables have some geo-chemical behaviors [77] Mg Na and Li are some com-ponents of the discharged waters however they havepositive correlations with the chlorinity and salinity of thedischarged water sources (r 0743 0619 and 0815 re-spectively) and (r 0743 0619 and 0815 respectively)Mgw and Liw contents in water samples are affected bytemperature dissolved oxygen and pH with high correla-tions of r minus0650 0677 and 0743 and minus0702 0659 and0815 respectively
32 Distribution of Halogens and Tested Variables in PoreWater
321 Distribution of Halogens in Pore Water -e averagehalogen contents in the pore water are higher than theircontents in the surface water but in the same orderClpgtBpgt Fpgt Ip (Table 3) Current research shows that thelowest and highest average values of Spermilp and Clp have beenmeasured in the pore water of site 6 and site 8 respectively Itis worth mentioning that site 6 is a mixed water of El-Qalaadrainage sewage WWTP treatment plant and lake waterInterestingly the high concentrations of fluoride chloridebromide and iodide in the pore water at site 6 are 123mgLminus1 40321mg Lminus1 11739mg Lminus1 and 24339 μg Lminus1 re-spectively (Table 3) -e salinity and chloride content in thepore water of site 8 are related to the discharge water of manypetrochemical and oil companies besides some fish farms
322 Distribution of Tested Variables in Pore Water -etested variables in the pore water (p) give the followingdescending order MgpgtNapgtCapgt SO4pgtBpgtKpgtBrpgt Fpgt LipgtPpgt Ipgt Sip (Table 3) Interestingly the deter-mined variables in the pore water have higher values thanthe surface water along the lake According to previousstudies pore water is responsible for biogeochemical reac-tions the migration and transformation of partitioned andformed compounds and the transportation of colloidalspecies [78 79] In addition pore water can explore thepotential risks of man-made pollution sources [80] -etested variables in the pore water (p) are given in a differentorder of surface water of ClpgtMgpgtNapgtCapgt SO4pgtBpgtKpgtBrpgt Fpgt Lipgt Ppgt Ipgt Sip (Tables 2and 3)
323 Interactions of Halogens and Tested Variables in PoreWater -e following interactions of halogens CO3w amp Ip Ipamp Fw Brw amp Sip Fp amp Siw and Fp amp Nap give correlationvalues (r 0706 ple 0010 r minus0606 ple 0037 r 0826ple 0001 r minus0704 ple 0011 and r 0670 ple 0017respectively) (Supplementary Table 1) However these re-lationships may indicate their precipitation andor
adsorption on the colloidal particles besides the formation ofsome chemical species [78 79] Extraordinarily large cor-relations of Nap amp HCO3w Kp amp HCO3w Spermilw amp Bp Spermilp ampKp Spermilp amp Lip and Spermilp amp Clp (r 0692 minus0609 minus07410696 0910 and 1000) may refer to the release of theseelements from sediment particles andor precipitation oradsorption [77] In the matrix the negative correlationbetween Cap and Mgp (r minus0592 ple 0042) may be relatedto the release of Mg during the recrystallization of calcite[79]-e relationship between Caw amp SO4p Cuw amp Cap Pw ampPp and Nap amp pHw (r 0744 ple 0006 r 0719 ple 0008r 0647 ple 0023 and r minus0640 ple 0025 respectively)may be due to the chemical interactions in the pore fluidsand the formation certain compounds
33Distribution ofHalogens andTestedVariables in Sediment
331 Distribution of Halogens in Sediment -e averagehalogenrsquos content in the sediment shows a different orderfrom the surface and pore waters of Brsgt FsgtClsgt Is (Ta-ble 4) -e sediment results show that the average bromidecontent is higher than fluoride followed by chloride contentand iodide with average values of 452mg gminus1 040mg gminus1029mg gminus1 and 450 μg gminus1 respectively
-e fluoride concentration in the sediment ranges from001 to 120mg gminus1 with an average value of 04plusmn 035mggminus1 -ese values are lower than reported marine sedimentvalues and higher than the El-Bardawil Lagoon [60]Amongst the halogens the study reveals that Br is the mostabundant ion in surface water pore water and sedimentsamples due to the excessive amounts of organic matter [81]On the contrary the concentration of Cl ions in sedimentsamples is lower than that in surface water and pore watersamples indicating that it exists in soluble salts -e currentresults indicate that the sediments collected from the mostaffected area by the Mediterranean Sea (site 6) contain el-evated levels of fluoride (070mg gminus1) bromide (852mggminus1) and chloride (020mg gminus1) and a reduced amount ofiodide (209 μg gminus1) (Table 4)
332 Distribution of Tested Variables in Sediment -eaverage value of test variables in the determined sedimentsamples shows a significant change from site to site with adescending order CO3sgtMgsgtCasgtNasgt SO4s gt FesgtBsgtKsgtTPsgtMn sgtZnsgtCusgt Lis (Table 4) Plus this studyclears out that the percent of sand and mud of the differentsediment samples ranges from 4 at sites 1 amp 13 to 85 atsite 11 and from 15 at site 11 to 96 at sites 1amp13 re-spectively with averages 25 and 75 respectively Plusthe porosity shows a trend opposite to the particle size andvaries from 4676 to 8214 with an average value of5609plusmn 1114 -e results of the current study reveal mod-erate amounts of CO3 in the sediment samples fluctuatingbetween 1639 and 5736 at sites 6 and 2 respectively -eresults of sand mud porosity and CO3 percentage reflect thatthe texture of the sediment is mainly composed of mud mixedwith carbonate compounds Comprehensively the large storageof sediments with carbonate (359plusmn1280) magnesium
Journal of Chemistry 9
Tabl
e3
Distribu
tionof
thestud
iedvariablesin
thepo
rewater
(p)alon
gLake
Mariout
Site
Spermilp
pHP
Ca p
(mgLminus
1 )Mg p
(mgLminus
1 )Na p
(mgLminus
1 )Kp
(mgLminus
1 )Li
p(m
gLminus
1 ))
SO4P
(mgLminus
1 ))
B P(m
gLminus
1 ))
P P(μgLminus
1 ))
SiP
(microgLminus
1 ))
F p(m
gLminus
1 ))
Cl P
(mgLminus
1 ))
Brp
(mgLminus
1 ))
I p(μgLminus
1 )1
1034
787
481
42303
1097
453
042
2944
8043
363
0045
323
95419
959
7104
2934
809
5611
115725
1050
498
039
2056
663
553
0036
338
8398
1385
24698
31272
717
100
5689
1195
577
053
2778
8949
1204
0034
754
114469
2291
26347
483
796
9619
47652
974
384
043
350
19312
77
0054
215
74599
693
8393
51099
782
5611
89711
1128
42041
1667
16739
1112
0081
1698864
1332
8333
645
775
4008
75367
736
41024
2111
11739
071
0037
1231
40321
799
24339
71125
782
39278
13615
1155
516
056
3667
6051
369
006
6101209
1279
8123
8148
775
9299
84314
1355
468
055
12444
942
212
0056
892
133232
1172
7643
9684
78
962
72109
880
393
036
3778
21341
114
0087
1061429
2131
9981
10114
764
1122
113586
1195
524
049
4667
8007
071
0041
1138
102562
1332
8572
11639
742
4008
61996
915
332
033
2833
11594
754
0026
1215
67834
746
37587
125
702
481
38413
8703
274
028
2167
13913
081
0025
2154
44832
1438
9891
13755
807
3206
6467
817
446
039
4556
17246
635
0042
954
5737
533
1097
Minim
um45
702
962
13615
736
274
024
1667
6051
071
0025
215
40321
533
7104
Maxim
um148
809
39278
115725
8703
577
056
12444
21341
1204
0087
2154
133232
2291
37587
Average
919
77
718
67412
163077
4381
041
3782
1223
485
0048
955
82779
1238
14768
SD308
032
10027
29209
2132
825
01
2769
5047
391
0019
542
27891
524
9917
10 Journal of Chemistry
Tabl
e4
Distribu
tionof
thestud
iedvariablesin
thesediment(s)alon
gLake
Mariout
Site
Sand
()
Mud ()
Porosity
()
CO3s
()
B s(m
ggminus
1 )P s
(mg
gminus1 )
Ca s
(mg
gminus1 )
Mg s
(mg
gminus1 )
Na s
(mg
gminus1 )
Ks
(mg
gminus1 )
Lis(m
ggminus
1 )
SO4s
(mg
gminus1 )
Fes
(mg
gminus1 )
Cu s (μg
gminus1 )
Mn s
(μg
gminus1 )
Zns(μg
gminus1 )
F s(m
ggminus
1 )
Cl s
(mg
gminus1 )
Brs
(mg
gminus1 )
I s(μg
gminus1 )
14
964915
183
299
044
1670
811
2583
408
0028
4861
828
963
5617
1272
034
041
128
1686
244
564925
574
196
028
1002
1419
2717
269
0015
662
257
793
4350
1313
057
054
123
358
319
816667
299
246
073
1670
1216
3125
336
0022
463
487
1228
4330
1677
044
034
448
516
418
824853
3813
1111
032
668
2229
3425
365
0094
2222
770
922
4637
1245
030
020
309
296
512
884697
482
614
012
501
1115
1833
091
0040
1713
243
600
27933
1223
082
034
245
254
65
954667
164
370
157
835
1257
2958
388
0030
5648
890
1927
5347
3117
070
020
852
209
75
954762
375
524
024
367
2047
3133
256
0102
1157
546
883
4185
1393
120
020
341
259
838
626143
457
697
039
668
1621
3550
347
0145
4167
598
737
4157
1412
022
034
144
1277
918
826000
349
083
054
401
1094
3358
369
0025
2454
701
868
5702
3065
036
027
250
172
1036
645070
441
296
002
935
1763
3117
246
0045
2685
369
790
4533
1315
012
047
1012
224
1185
157000
325
240
074
969
2250
3508
328
0193
1343
1026
735
3890
1070
005
007
533
128
1237
638214
463
291
032
334
1824
3008
358
0018
556
340
728
2475
827
001
007
852
281
134
965000
177
211
054
2338
1621
3925
599
0068
833
1687
1187
6492
1853
004
027
639
194
Min
415
4667
164
083
002
334
811
1833
091
0015
463
243
600
2475
827
001
007
123
128
Max
8596
8214
574
1111
157
2338
2250
3925
599
0193
6620
1687
1927
6492
3117
120
054
1012
1686
Av
2575
5609
359
398
048
951
1559
3096
335
0063
2671
672
951
4500
1599
040
029
452
450
SD23
231114
128
276
039
603
455
522
115
0055
2030
393
343
1120
708
035
014
303
475
Minm
inim
umM
axm
axim
uma
ndAv
averageSD
stand
arddeviation
Journal of Chemistry 11
(1559plusmn455mg gminus1) and calcium (951plusmn603mg gminus1) com-ponents may be attributed to the abundance of calcium min-erals [4] However in general the average amounts of allvariables in sediment samples showmarked variations fromonesite to another with a descending order of CO3sgtMgsgtCasgtNasgtSO4sgtFesgt BrsgtBsgtKsgtTPsgtFs gtClsgtMnsgtZnsgtCusgtLisgt Is (Table 4) -e measured concentra-tions of Mn Zn Cu and Fe in the sediment samples are stilllower than the reported values and also lower than the back-ground levels of crust and the toxicological reference contents ofUS DOE (US Department of Energy) US EPA (US Envi-ronmental Protection Agency) and CEQG (Canadian Envi-ronmental Quality Guidelines) [82]
Contrasting the obtained levels for the halogens withthose previously reported ones the present study indicatesthat surface and pore waters incorporate more considerableamounts of fluoride compared to the formerly reported onesin Lake Edku (Tables 2 and 3) and lower levels in theMarioutarea than those measured along the Egyptian MediterraneanSea coast [27] Compared with the sediments previouslyfound on the Mediterranean coast of Egypt the chloridecontent in the sediments of the Mariout area is lower [83]Compared with those observed in seawater the studiedsurface water and pore water samples have lower bromidecontent and higher levels than previously reported in LakeMariout [52 53] -e concentration of iodide in surfacewater pore water and sediments is equivalent to the con-centration of rivers and lakes in the world [84]
333 Interactions of Halogens and Tested Variables inSediment -e correlation matrix shows the important roleof halogens in the formation and precipitationdissolution ofsalts and minerals produced along the lake (SupplementaryTable 1) However it shows that chloride seems to be in thesoluble forms along the surface and pore waters of studiedarea showing good relations with Caw (r 0666 ple 0018)Clp (r 0677 ple 0016) and SO4p (r 0858 ple 0000)Also Cls gives good correlations with Mgw (r 0710ple 0010) Naw (r 0602 ple 0038) Clw (r 0619ple 0032) Mgp (r 0774 ple 0003) and Kp (r 0731ple 0007) Chloride in the surface and pore waters plays animportant role in the dissolution association and formationof various salts along the lake -e good relationship be-tween Is and Caw (r 0666 ple 0018) may reflect the de-positionrelease of CaI+ during the formationdissolution ofcalcium carbonate [85] In addition these correlations maybe related to organic-I which formed by bacterial species andtheir remineralization in bottom sediments [86] -emoderate relationship between Nas and Brw (r minus0622ple 0031) may indicate the possible formation of BrClspecies and the precipitation or adsorption of Na minerals insediments [87] -e results of this study also reflect thestrong negative correlation between Fs and Bw (r minus0666ple 0018) which may be related to the release of fluoridefrom sediment and the formation of soluble fluoridecomplexes ((BFn[OH]4minusn)minus) with the excessive boron con-centration in the water [88] -e negative relation betweenKs and Spermilw (r minus0673 ple 0016) possibly reflect that Kw
preferentially chooses to exist in the soluble form of KClrather than being adsorbed andor bound by some richminerals in the sediment
-e significant correlations between CO3s and Mgw(r 0637 ple 0026) CO3s and Clw (r 0723 ple 0008)CO3s and pHw (r 0833 ple 0001) CO3s and Spermilw(r 0723 ple 0008) and between CO3s and Ks (r minus0673ple 0016) may be accompanied by the possible formationdissolution of the dolomite mineral in the presence ofsufficient Mgw which is usually affected by optimal pHsalinity and the potassium salts (Supplementary Table 1)-ese observed results are matching with the previouslyreported studies [32] Significant negative correlation be-tween TPs and CO3s (r minus0744 ple 0006) may indicate theextended release of P from carbonate minerals and for-mation of apatites [32]
-e correlation matrix also refers to other possible in-teractions between the remaining determined variables(Supplementary Table 1) -e significant correlation be-tween SO4s andMgw (r 0706 ple 0010) and Liw (r 0633ple 0027) may be associated to the formation of Mg-sulfateand the pollution of sediments by discharged waters con-taining excessive sulfate and Li [89] In the contrary thestrong positive correlation between TPs and Cus and be-tween TPs and Zns may be related to the same source ofpolluted discharge water [23 83]
-e high negative correlations of Zns with Few(r minus0785 ple 0003) CO3s (r minus0601 ple 0039) and Cus(r 0698 ple 0012) may indicate that Zn Cu and CO3depositions in sediment samples are linked to the soluble Feform in water (ferrous) ie the release of Fe upwards in thewater column in the anoxic conditions (SupplementaryTable 1) [90] -e excellent relations found between Fesand CO3s (r minus0799 ple 0002) Fes and Cas (r 0637ple 0026) Fes and Clw (r minus0752 ple 0005) Fes and Nas(r 0720 ple 0008) and between Fes and Ks (r 0833ple 0001) may reflect the dissolution of the chelating Feassociation with the soluble organic compounds in thewater-sediment interface and the formation of the sol-uble ferrous form in low dissolved oxygen within theareas affected by untreated discharged waters [90] -estrong correlations of Mns with SO4w Nap Nas Ks CO3sZns and Fes (r minus0585 0608 0611 0698 minus0655 0691and 0716 respectively) may associate with the solubilityof abundant Mn minerals and P-Mn forms in the sedi-ment because of its possible reduction to Mn+2 solublespecies under anoxic conditions [90] It is worth men-tioning that the results of this study indicate that ap-proximately 333 of the survey sites indicate thedepletion of dissolved oxygen in their surface watersamples Under such anoxic conditions bacteria are mostlikely to use sulfate instead of oxygen to break downorganic matter and cause the release of iron and phos-phorus into the water column
-e significant direct correlation between Ks and Nas(r 0832 plt 0001) clearly reflects the transport of solublesalts of K and Na between the pore water phase of thesediment and water-sediment surface phase (SupplementaryTable 1) -e good correlation between porosity and Nas
12 Journal of Chemistry
indicates the possible transfer of Na between pore water andsediment partitions
34 Interactions of Precipitated Halogenated Compounds inSurface and Pore Waters -e Saturation Index (SI) [23 60]of twenty-three and fifteen structures in surface water andpore water samples respectively are listed (Table 1) -ecorrelation matrix of the calculated Saturation Indices withthe presented data shows the different factors affecting theinteraction of the halogenated compound with other pre-cipitated salts and minerals Table 1 explores the precipitationof the phosphate minerals and salts are most abundantfollowed by the hydroxidesrsquo salts iodate salts sulfate andcarbonate minerals and salts in surface waters Amongst thehalogens precipitated salts fluoride minerals especiallyfluorapatites and carbonate-fluorapatite (FAP and CFAP)have high SI values in surface water (4277ndash5195 and1604ndash6089 respectively) and in pore water (5126ndash5460 and1752ndash7833 respectively) Bromide and chloride are mainlyfound in the soluble forms in surface and pore waters Iodidesalts (Ca(IO3)2 and Ca(IO3)26H2O) moderately precipitatein surface and pore Iron salts precipitate in surface waterwhile in pore water they are not formed -us SI contentreflects that halogens especially fluoride and iodide play avital role in reducing lake pollution
In addition Table 1 shows that the precipitation com-pounds that may be formed in surface water are relativelydifferent from those in sediment pore water For examplefluorite (CaF2) and sellaıte (MgF2) may be only formed inpore water while calcite and aragonite may be deposited insurface water However the formation of fluorite in surfacewater is related to Naw (r 0778 ple 0003) Kw (r 0704ple 0011) CO3w (r minus0718 ple 0009) Fw (r 0770ple 0003) and Ip (r minus0785 ple 0003) (SupplementaryTable 1)
-e formation of calcium sulfate hemihydrate calciumsulfate and anhydrite in water is related to the increase in theamounts of Caw Mgw SO4w Nap Fp Sip Cls and Mns andthe decrease in porosity values On the other hand pre-cipitation of calcium phosphate is related to Brw (r 0751ple 0005) Znw (r 0668 ple 0018) Pw (r 0881ple 0001) and Ks (r 0881 ple 0001) ie it is affected bythe discharged water composition (Supplementary Table 1)
-e formation of calcite and aragonite in surface water isrelated to the formation of CO3w (r 0753 ple 0005) anddissociation of HCO3w (r minus0660 ple 0020) pHw values(r minus0654 ple 0021) and their dissolution in sediment(r minus0620 ple 0032) (Supplementary Table 1)
-e dolomite formation in water may be affected by theincrease of CO3w (r 0817 ple 0001) and the decrease ofHCO3w (r minus0658 ple 0020) increase in TDSw (r 0599ple 0040) and increase in pHw (r minus0656 ple 0021)besides the possible release of CO3s from abundant sediment(r minus0624 ple 0030) and the precipitation of calcite(r 0984 ple 0000) and aragonite (r 0984 ple 0000) intosediment fraction (Supplementary Table 1)
Generally in the current study the possible formedhalogenated minerals and salts are affected by their
abundance in different components of the lake besides theirpossible dissolution or formation on the sediment texturesgeochemistry of the sediments and physicochemical vari-ables of water in addition to the components of the dis-charged waters
35 Interactions of Dissolved Halogenated Compounds inSurface and PoreWaters -e utilization of dissolved salts insurface and pore waters by utilizing Palmerrsquos method andpiper ternary diagram [50] indicates that Na is the richestcation in surface water followed by Mg Ca and K At thesame time Mg is the most predominate one in the porewater (Figures 3 and 4) Obviously Cl is the most importantanion in surface water and pore waters samples Howeverthe piper ternary diagrams of surface water and pore waterclearly shows that NaCl is the most dominant in surfacewater while MgCl2 is the most abundant in pore waterCoincidently Palmerrsquos method also reflects that NaCl(574) is the most existent species in surface water fol-lowed by MgCl2 (304) CaCl2 (71) CaSO4 (29)Ca(HCO3)2 (14) and KCl (12) (Figure 3) At the sametime MgCl2 (760) is the most present species in porewater followed by NaCl (73)asympMg(HCO3)2 (73)Ca(HCO3)2 (52) and MgSO4 (31) (Figure 4)
36 Multivariate Analysis
361 Principal Component (PCA) By applying Varimaxrotation and Kaiser normalization to 98 variables in the PCAfor halogens and tested variables and calculated parametervalues 7 extracted PCs with eigenvalues higher than 1 areobtained However it is important that the eigenvalue mustbe greater than 1 Its seven PCs explain 8558 of the totalvariance
-e first principle component (PC1) is 1473 of thetotal variance and shows positive coefficient factor loadingsfor CO3w TDSw Kp calcite aragonite dolomite FeCO3MgCO3 ZnCO3 and ZnCO3H2O (0804 0547 05320938 0938 0947 0741 0940 0866 and 0866 respec-tively) In addition it provides negative factor loadings forHCO3w pHw Bw Nap and CO3s (minus0782 minus0610 minus0595minus0532 and minus0572 respectively) PC1 is related to thefactors affecting the carbonate compounds that may beformed in the area under consideration
PC2 accounts to 1458 of the total variance and alsoshows positive and negative coefficient factor loadingsrepresenting the different interactions between the CawMgw Liw SO4wMgp Nap pHp Cls SO4s Brs and porosityin water pore water and sediment that are responsible forthe composition of sulfate magnesium and phosphateprecipitates besides the effect of the discharged waters onwater-pore water-sediment componentsrsquo cycles
PC3 typically shows 1377 of the total variance withpositive and negative loadings which can properly explorethe effect of the principal sources of local pollution on thedissolving of heavy metals B and P from sediment into thewater column and the probable formation of Fe(OH)2Fe(OH)3) and FePO4
Journal of Chemistry 13
Similarly the coefficient factor loadings of PC4 with1355 are related to the influence of the polluted dischargewater and sediment texture on the formation of F Cl and Isalt besides the precipitation of halogenated compounds(FeF2 Mn(IO3)2 KIO4 and KCIO4) besides their minerals(CaF2 MgF2 FAP and CFAP)
Simultaneously PC5 gives 1092 of the total variancewith positive and negative loadings which explains therelations between the physicochemical limits of the surfacewater pore water and sediment components and theprecipitation of minerals and salts (OCP HAP CuBrZn(OH)2 and Zn(IO3)22H2O) -is is also associated tothe influence of the sedimentary material on the release ofMn Fe and P from sediment into pore water and watercolumn and formation of Ca3(PO4)2 OCP and HAPminerals
However PC6 associates with 100 of the total variancegiving positive and negative coefficient factor loadingswhich explain that the sediments (minerals andor organic-iodine compounds) are only the acting sink for iodine andiodine species (Iminus and IOminus
3 ) in the water as previously re-ported [84] PC6 also reflects the precipitation of severalhalogenated compounds such as calcium iodate (Ca(IO3)2and Ca(IO3)26H2O) and copper iodate (CuI andCuIO3H2O) besides Cu3(PO4)2 species in the lake watercolumn
-e loadings of PC7 contribute by 804 and show thatthe release of calcium in pore water into the water column isresponsible for the precipitation of halogenated compounds(CuCl and Zn(IO3)22H2O) as well as copper and Zn salts(Cu3(PO4)2 and Zn(OH)2)
362 Cluster Analysis On the other hand cluster analysisshows that the similarity of sites 1amp4 5amp8 6amp9 2amp10 and11amp13 is due to the texture of sediment
363 Multiple Regression Multiple regression equations ofhalogens as dependent variables and the other determinedand calculated parameters as independent variables insurface water pore water and sediment partitions are listed(Table 5)-e amount of fluoride in water samples is affectedby the discharged watersrsquo fundamental components espe-cially Zn and Cu besides its surface water-pore water in-teractions Its content in pore water seems to be stronglyaffected by its substitution competition with other halogensin surface water-spore water-sediment cycle due to its highelectronegativity Generally in the affected area the type ofpollutant in the discharged water plays an important role inthe dissolution andor precipitation of fluoride and otherhalogens in the surface water-pore water-sediment cycle
574
147129
300
12
Ca(HCO3)2CaSO4CaCl2
MgCl2KClNaCl
(a)
SO4
2 + CIndash Ca 2+ + Mg 2+
CO32ndash + HCO3
ndashNa+ + K+
Mg2+ SO42ndash
Ca2+ CIndash
(b)
Figure 3 (a) distribution and (b) piper ternary diagram of the formed dissolved salts in surface water of Lake Mariout
Ca(HCO3)2Mg(HCO3)2MgSO4
NaClMgCI2KCl
760 1052
7373 31
(a)
SO4
2ndash + C
Indash
Ca 2+ + Mg 2+
CO32ndash + HCO3
ndashNa+ + K+
Mg2+ SO42ndash
CIndashCa2+
(b)
Figure 4 (a) distribution and (b) piper ternary diagram of the formed dissolved salts in pore water of Lake Mariout
14 Journal of Chemistry
Table 5 -e multiple regression analyses of each halogen as dependent variable and other tested variables in the surface water pore waterand sediment partitions besides the precipitated salts in surface water along Lake Mariout
Dependentvariable Multiple regression equation R2
FluorideLake water FW 3162 + 092 Zn F2 minus 033 SiP + 021 CuIminus 017 SpermilP 09911
Pore water Fp minus2567minus117 SiW minus 033 LiP minus 062 CuClminus 028 IS + 023 TDSW+ 017 KIO4 minus 012 BrW minus 004porosity + 004 PW
10000
Sediment FS 088 CAPminus 049 MgS minus 046 DOW+039MgW+ 027 Mn(IO3)2 + 015 Cu3(PO4)2 + 004 HAP+ 002 pHP 10000ChlorideLake water No relation 00000Pore water No relation 00000Sediment ClS minus116 + 046 MgP + 077 Kp minus 049 dolomite + 017 TDSW minus 011 CuI + 005 NaS + 002 BS + 001 FeF2 10000Bromide
Lake water BrW 1563 + 110 CuBrminus 057 CuClminus 021 KS minus 014 pHP minus 011 TPS + 014 FeW+ 007 ZnSminus 002 PP + 001turbidity 10000
Pore water BrP minus1516minus 055 FeS minus 073 BS + 061 MnW+ 083 SiP + 049 NaS minus 031MnS minus 015 CuBr + 011 pHW minus 001CaW
10000
Sediment BrS 015 SiP + 195 CFAP+ 002 FP minus 045 IS + 192 sand+ 037 MnW minus 029 MgS minus 012 LiP + 005Ca3(PO4)2 minus 002 ZnF2
10000
IodideLake water IW 099 Ca(IO3)6H2O 09999
Pore water IP minus097 ZnF2 minus 057 Li3PO4 minus 053 BP + 034 FAP+ 015 Ca(IO3)2 +MnW+ 005 KS minus 009 turbidity + 055CaS
09999
Sediment IS minus072 + 135 SO4P + 023 Mn(IO3)2 + 063 FeW+ 031 TPS minus 035 MgP minus 012 Zn(CO3)22H2O 09993
40E + 0135E + 0130E + 0125E + 0120E + 0115E + 0110E + 0150E + 0000E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
12345
678910
111213
(a)
10E + 0090E ndash 0180E ndash 0170E ndash 0160E ndash 0150E ndash 0140E ndash 0130E ndash 0120E ndash 0110E ndash 0100E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
12345
678910
111213
(b)
12345
678910
111213
40E ndash 0235E ndash 0230E ndash 0225E ndash 0220E ndash 0215E ndash 0210E ndash 0250E ndash 0300E ndash 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
(c)
12345
678910
111213
80E ndash 0670E ndash 0660E ndash 0650E ndash 0640E ndash 0630E ndash 0620E ndash 0610E ndash 0600E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
(d)
Figure 5 Hazard quotient of ingestion and dermal contact of surface water and sediment of LakeMariout (a) ingestion of water (b) dermalcontact of water (c) ingestion of sediment and (d) dermal contact of sediment
Journal of Chemistry 15
Minerals and precipitated salts in the different partitions(surface water pore water and sediment) play an importantrole in the deposition and release of halogens in sedimentsAdditionally the texture and the porosity of the sedimentsplay a key role in the distribution of halogens in the threepartitions Interestingly chloride is the only halogen that hasnegligible interactions along the surface water and porewater partitions because it is present in large quantities inthe form of soluble salts (NaCl and MgCl2)
37 Pollution Status
371 Enrichment Factor (EF) Twowell-knownmethods areused to assess environmental pollution public health sig-nificance of ingestion and dermal contact with water andsediment components and sediment enrichment factor (EF)[59 60]
-e average EF values of the determined elements CaMg Na K Li B P Cu Zn Mn Fe F Cl Br and I are alllower than the value that is less than the minimum en-richment value (EFlt 2)-us the area under investigation isstill ecologically considered as an unpolluted region
372 Human Health Risk Assessment -e EDI HQ and HIshow the variable values of all pollutants in the surface waterand sediments along the lake region and in drains (sites11ndash13) under study Among all the calculated variables ofsurface water ingestion (EDIIngw) and dermal contact(EDIDermw) Cl is still the only variable that shows high levels(average 1551 and 43mg kgminus1 dayminus1 respectively) -eestimation daily intake of sediment ingestion (EDIIngs) anddermal contact (EDIDerms) of Mg Ca and Na give maximumaverage amounts of 841Eminus 02 513E ndash 02 and167Eminus 03mg kgminus1 dayminus1 respectively
Among the HQ of the calculated detection variables thecontent of HQB of ingestion and dermal contact with waterand sediment is the highest However 70 of sites have HQBvalues more than 10 (Figure 5) Comparing the HQ values ofall the determined variables HQB of the ingestion of surfacewater shows values higher (gt10) However due to the impactof drainage the HQB values of stations 1ndash4 8ndash10 12 and 13
are higher than 10 -erefore these sites can be consideredas the area with the most serious boron pollution caused byuntreated discharged water disposal In addition the HIIngwlevel of water ingestion for the studied variables in all sites ismuch higher than 10 (Figure 6) Except for boron it isusually concluded that the study area does not pose any riskto the population due to halogens or other variables Ac-cordingly this information may help the official authoritiesoptimize management plans and strengthen their pollutioncontrol actions in Lake Mariout
4 Conclusions
-e effects of halogen salts and minerals on the pollution ofLake Mariout were studied Halogens and some physico-chemical variables in three partitions surface water porewater and sediment in Lake Mariout were evaluated -ehalogen content was variable between different sites andchloride was the main halogen in surface water and porewater but it was very rare in the lakersquos sediment partitionPiper ternary diagram and Palmerrsquos method reflected thatNaCl was the dominant salt in surface water while MgCl2was the main dissolve salt in pore water-e chlorinity ratiosof halogens and tested variables were directly matched to thefeeding drain sources
Moreover the Saturation Index (SI) reveals that 23 and 15precipitated salts and minerals are formed in surface water andpore water respectively -e SI value indicated the formationof phosphate minerals in surface water and pore water es-pecially octacalcium phosphate (OCP Ca4H(PO4)325H2O)and hydroxyapatite (HAP Ca5(PO4)3OH) In addition tofluoride minerals especially fluorapatite (FAP) and carbonate-fluorapatite (CFAP) were obviously precipitated from surfacewater and pore water Soluble salts of bromide and chloridewere formed in surface water and pore water Iodide salts(Ca(IO3)2 and Ca(IO3)26H2O) were moderately precipitatedin the surface water and pore water
Moreover the multivariate analysis including the cor-relation matrix multiple stepwise linear regression treeclustering and principle component (PCA) of all the de-termined and calculated variables was applied to estimatethe proposed interaction between halogens and other tested
10E + 02
16E + 0214E + 0212E + 02
80E + 0160E + 0140E + 0120E + 0100E + 00
1 2 3 4 5 6 7 8 9 10 11 12 13
HIIngHIDerm
(a)
1 2 3 4 5 6 7 8 9 10 11 12 13
HIIngHIDerm
40E ndash 0235E ndash 0230E ndash 0225E ndash 0220E ndash 0215E ndash 0210E ndash 0250E ndash 0300E + 01
(b)
Figure 6 Hazard index of ingestion and dermal contact of the studied variables in surface water and sediment of Lake Mariout (a) waterand (b) sediment
16 Journal of Chemistry
variables in the polluted area under study -e multivariateanalysis showed that there were many interactions betweenhalogens and tested variables High levels of fluoride bro-mide and chloride in surface water were related to thecomposition of drainage waters -e enrichment factor (EF)showed that Lake Mariout was not polluted However thehuman health adverse effects calculated for surface waterand sediment did not reflect any possible likelihood hazardeffects from halogens
Interestingly the current study concluded that halogencompounds especially fluorides are most likely to be de-posited from surface lakes in the form of many minerals andprecipitation thereby reducing the adverse pollution effectson human health -e results obtained through this workhelp to find the correlations between the sampling sites andthe variables obtained by physical and chemical measure-ments which can be used to construct a fast decision modelfor separating different water quality samples -is infor-mation may help the official authorities optimize manage-ment plans and strengthen their pollution control measuresin Lake Mariout
Data Availability
-e data used to support the findings of this research areincluded within the paper
Conflicts of Interest
-e authors declare that there are no conflicts of interestregarding the publication of this manuscript
Supplementary Materials
Supplementary Table 1 correlation matrix of variable insurface water pore water and sediment partitions besidesthe precipitated salts in surface water along Lake Mariout(Supplementary Materials)
References
[1] M S Masoud T O Said G El-Zokm and M A ShreadahldquoAssesment of heavy metals contamination in surface sedi-ments of the Egyptian Red Sea Coastsrdquo Australian Journal ofBasic and Applied Sciences vol 6 pp 44ndash58 2012
[2] M A Shreadah M I Abdel Moneim T O SaidE M I Fathallah and M E Mahmoud ldquoPAHs in seawater ofthe semi-closed areas along the Alexandria coast of EgyptianMediterranean seardquo Journal of Environmental Protectionvol 4 no 11 p 11 Article ID 40298 2013
[3] S Abdel Ghani G El Zokm A Shobier T Othman andM Shreadah ldquoMetal pollution in surface sediments of Abu-Qir bay and Eastern harbour of Alexandria Egyptrdquo EgyptianJournal of Aquatic Research vol 39 no 1 pp 1ndash12 2013
[4] G F El-Said ldquoBioaccumulation of key metals and othercontaminants by seaweeds from the Egyptian MediterraneanSea Coast in relation to human health riskrdquo Human andEcological Risk Assessment An International Journal vol 19no 5 pp 1285ndash1305 2013
[5] M A Shreadah A H Shobier S Abdel Ghani G M El-Zokm and T O Said ldquoMajor ions anomalies and
contamination status by trace metals in sediments from twohot spots along the Mediterranean Coast of Egyptrdquo Envi-ronmental Monitoring and Assessment vol 187 no 280pp 1ndash18 2015
[6] A El Nemr G F El-Said A Khaled and S Ragab ldquoDis-tribution and ecological risk assessment of some heavy metalsin coastal surface sediments along the Red Sea Egyptrdquo In-ternational Journal of Sediment Research vol 31 no 2pp 164ndash172 2016
[7] A El Nemr G F El-Said S Ragab A Khaled and A El-Sikaily ldquo-e distribution contamination and risk assessmentof heavy metals in sediment and shellfish from the Red Seacoast Egyptrdquo Chemosphere vol 165 pp 369ndash380 2016
[8] A El Nemr and G F El-Said ldquoAssessment and ecological riskof heavy metals in sediment and molluscs from the Medi-terranean coastrdquo Water Environment Research vol 89 no 3pp 195ndash210 2017
[9] M A Sheradah A A El-Sikaily N M Abd El MoneamN E Abd El Maguid and M G Zaki ldquoChemical and bio-chemical evaluation of marine pollution by polychlorinatedbiphenyls and pesticides in two regions along the EgyptianMediterranean Seardquo International Journal of EnvironmentalMonitoring and Analysis vol 6 no 3 pp 95ndash109 2018
[10] M A Shreadah A A-M M El-Sayed A A S TahaA-M M Ahmed and H H Abdel Rahman ldquoEvaluation ofdifferent anthropogenic effluents impacts on the water qualityusing principal component analysis a case study of Abu-QirBay-Alexandria-Egyptrdquo International Journal of Environ-mental Monitoring and Analysis vol 7 no 3 pp 56ndash67 2019
[11] G F El-Said M M El-Sadaawy A H Shobier andS E Ramadan ldquoHuman health implication of major and traceelements present in commercial crustaceans of a traditionalseafood marketing region Egyptrdquo Biological Trace ElementResearch vol 199 pp 315ndash328 2020
[12] M A Shreadah S A A Ghani H B I HawashA A E Samie and A E M M Ahmed ldquoOrganotin com-pounds in sediments of northern lakes Egyptrdquo Journal ofEnvironmental Protection vol 05 no 17 pp 1654ndash1666 2014
[13] A M Younis G M El-Zokm and M A Okbah ldquoSpatialvariation of acid-volatile sulfide and simultaneously extractedmetals in Egyptian Mediterranean Sea lagoon sedimentsrdquoEnvironmental Monitoring and Assessment vol 186 no 6pp 3567ndash3579 2014
[14] G F El-Said S E O Draz M M El-Sadaawy andA A Moneer ldquoSedimentology geochemistry pollution statusand ecological risk assessment of some heavy metals insurficial sediments of an Egyptian lagoon connecting to theMediterranean Seardquo Journal of Environmental Science andHealth Part A vol 49 no 9 pp 1029ndash1044 2014
[15] G M El Zokm M A Okbah and A M Younis ldquoAssessmentof heavy metals pollution using AVS-SEM and fractionationtechniques in Edku Lagoon sediments Mediterranean SeaEgyptrdquo Journal of Environmental Science and Health PartAvol 50 no 6 pp 571ndash584 2015
[16] G M El Zokm H R Z Tadros M A Okbah andG H Ibrahim ldquoldquoEutrophication assessment using TRIX andCarlsonrsquos indices in Lake Mariout water Egyptrdquo EgyptianJournal of Aquatic Biology and Fisheries vol 22 no 5pp 331ndash349 2018
[17] N Donia ldquoLake Maryut monitoring using remote sensingrdquo inProceedings of the gypt Eighteenth International WaterTechnology Conference IWTC18 Sharm El Sheikh Abu DhabiUAE March 2015
Journal of Chemistry 17
[18] M A Khairy ldquoAssessment of priority phenolic compounds insediments from an extremely polluted coastal wetland (LakeMaryut Egypt)rdquo Environmental Monitoring and Assessmentvol 185 no 1 pp 441ndash455 2013
[19] N A El-Naggar and E A Rifaat ldquoEgyptian coastal lakes andwetlands part Imdashcharacteristics and hydrodynamicsrdquo in eHandbook of Environmental Chemistry A M Negm EdSpringer International Publishing AG Berlin Germany 2017
[20] J J Hanley and K T Koga ldquoChapter 2 ldquohalogens in terrestrialand cosmic geochemical systems abundances Geochemicalbehaviors and analytical methodsrdquordquo in e Role of Halogensin Terrestrial and Extraterrestrial Geochemical ProcessesD E Harlov and L Aranovich Eds Springer InternationalPublishing AG Berlin Germany pp 21ndash121 2018
[21] A Ghosh K Mukherjee S K Ghosh and B Saha ldquoSourcesand toxicity of fluoride in the environmentrdquo Research onChemical Intermediates vol 39 no 7 pp 2881ndash2915 2013
[22] M M Naim A A Moneer and G F El-Said ldquoPredictiveequations for the defluoridation by electrocoagulation tech-nique using bipolar aluminum electrodes in the absence andpresence of additives a multivariate studyrdquo Desalination andWater Treatment vol 57 no 14 pp 6320ndash6332 2016
[23] G F El-Said N A Shaltout M M El-Sadaawy andA M H Morsy ldquo-e precipitation of fluoride calcium andmagnesium minerals from Egyptian Mediterranean Sea coastin relation to discharged watersrdquo Desalination and WaterTreatment vol 57 no 5 pp 2113ndash2124 2016
[24] H Bureau ldquoIodine encyclopedia of geochemistry A com-prehensive reference source on the chemistry of the earthrdquo inEncyclopedia of Earth Sciences Series W M White Ed copySpringer International Publishing AG 2016
[25] F C Kupper and C J Carrano ldquoKey aspects of the iodinemetabolism in brown algae a brief critical reviewrdquo Metal-lomics vol 11 pp 756ndash764 2019
[26] R Liteplo R Gomes P Howe and H Malcolm Fluorides-Environmental Health Criteria 227 p 290 World HealthOrganization (WHO) Geneva Switzerland 2002
[27] G F El-Said and M M El-Sadaawy ldquoSeasonal variation ofboron and fluoride in Tilapia nilotica from an Egyptian fishfarm in relation to Human health hazard assessmentrdquoHumanand Ecological Risk Assessment An International Journalvol 19 no 4 pp 930ndash943 2013
[28] WHO (World Health Organization) Bromide in Drinking-Water Background Document for Development of WHOGuidelines for Drinking-Water Quality WHO Press WorldHealth Organization Geneva Switzerland 2009
[29] G F El-Said and N A Sallam ldquo-e uptake of fluorideconcentration and its effects on the growth rate of shrimps(Palaemon elegans Rathke)rdquo Chemistry and Ecology vol 24no 3 pp 191ndash205 2008
[30] X Zhang J He B He and J Sun ldquoAssessment formationmechanism and different source contributions of dissolvedsalt pollution in the shallow groundwater of Hutuo Riveralluvial-pluvial fan in the North China Plainrdquo EnvironmentalScience and Pollution Research vol 26 no 35 pp 35742ndash35756 2019
[31] Y Zhu B Huang Z Zhu et al ldquoldquoCharacterization disso-lution and solubility of the hydroxypyromorphitendashhydroxyapatite solid solution [(PbxCa1minusx)5(PO4)3OH] at25 degC and pH 2ndash9rdquo Geochemical Transactions vol 17 no 2pp 1ndash18 2016
[32] G F El-Said M M El-Sadaawy A A Moneer andN A Shaltout ldquo-e effect of fluoride on the distribution ofsome minerals in the surface water of an Egyptian lagoon at
the Mediterranean Seardquo Egyptian Journal of Aquatic Researchvol 41 no 1 pp 31ndash39 2015
[33] Y Zhu Z Zhu X Zhao Y Liang and Y Huang ldquoChar-acterization dissolution and solubility of lead hydroxypyr-omorphite [Pb5(PO4)3OH] at 25ndash45degCrdquo Journal ofChemistry vol 2015 Article ID 269387 10 pages 2015
[34] M A Z Chahouki ldquoMultivariate analysis techniques inenvironmental sciencerdquo in Earth and Environmental SciencesDr Imran Ahmad Dar Ed InTech Open London UK 2011httpwwwintechopencombooksearth-and-environmental-sciencesmultivariate-analysis-techniques-inenvironmental-science
[35] J V Klump and C S Martens ldquoBiogeochemical cycling in anorganic-rich coastal marine basin 5 Sedimentary nitrogenand phosphorus budgets based upon kinetic models massbalances and the stoichiometry of nutrient regenerationrdquoGeochimica et Cosmochimica Acta vol 51 no 5 pp 1161ndash1173 1987
[36] R L Folk Petrology of Sedimentary Rocks University of TexasAustin TX USA 1974
[37] P Saenger ldquoA rapid spectrophotometric method for thedetermination of bromine in seawater and in the ash ofmarine algaerdquo Helgolander Wissenschaftliche Meer-esuntersuchungen vol 23 no 1 pp 32ndash37 1972
[38] P G Jeffery Chemical Methods of Rock Analysis PergamonPress New York NY USA 2nd edition 1975
[39] J D H Strickland and T R Parsons ldquoA practical handbook ofseawater analysisrdquo in Fisheries Research Board of CanadaBulletin 167p 311 Second edition Wiley Ottawa Canada1972
[40] B Horvath O Opara-Nadi and F Beese ldquoA simple methodfor measuring the carbonate content of soilsrdquo Soil ScienceSociety of America Journal vol 69 no 4 pp 1066ndash1068 2005
[41] K Grasshoff Methods of Seawater Analysis p 317 VerlagChemie Weinkeim Germany 1976
[42] R Danovaro D Marrale N Della Croce P Parodi andM Fabiano ldquoBiochemical composition of sedimentary or-ganic matter and bacterial distribution in the Aegean Seatrophic state and pelagic-benthic couplingrdquo Journal of SeaResearch vol 42 no 2 pp 117ndash129 1999
[43] APHA-AWWA-WPCF (American Public Health Associa-tion) Standard Methods for the Examination of Water andWaste Water American Public Health Association Wash-ington DC USA 20th edition 1999
[44] K I Aspila H Agemian and A S Y Chau ldquoA semi-auto-mated method for the determination of inorganic organicand total phosphate in sedimentsrdquo e Analyst vol 101no 1200 pp 187ndash197 1976
[45] J P Riley and D Taylor ldquoChelating resins for the concen-tration of trace elements from sea water and their analyticaluse in conjunction with atomic absorption spectrophotom-etryrdquo Analytica Chimica Acta vol 40 pp 479ndash485 1968
[46] G F El-Said and A El-Sikaily ldquoChemical composition ofsome seaweed from Mediterranean Sea coast Egyptrdquo Envi-ronmental Monitoring and Assessment vol 185 no 7pp 6089ndash6099 2013
[47] Directorate General of Health Services Ministry of Health andFamilyWelfare Government of India ldquoManual of methods ofanalysis of foodsrdquo in Fruit and Vegetable Productsp 57Directorate General of Health Services Ministry of Health andFamily Welfare Government of India New Delhi India2005
[48] A Gunnars S Blomqvist and C Martinsson ldquoInorganicformation of apatite in brackish seawater from the Baltic Sea
18 Journal of Chemistry
an experimental approachrdquo Marine Chemistry vol 91 no 1-4 pp 15ndash26 2004
[49] W M Haynes D R Lide and T J Bruno CRC Handbook ofChemistry and Physics A Ready Reference Book of Chemicaland Physical Data CRC Press Taylor amp Frances Group BocaRaton FL USA 97th edition 2017
[50] M S Masoud M I El-Samra and M M El-Sadawy ldquoWaterchemistry of el-mex bay west of Alexandria Egyptrdquo eEgypian Science Magazine vol 2 pp 70ndash78 2005
[51] F J Millero R Feistel D G Wright and T J McDougallldquo-e composition of standard seawater and the definition ofthe reference-composition salinity scalerdquo Deep Sea ResearchPart I Oceanographic Research Papers vol 55 no 1pp 50ndash72 2008
[52] S K El-Wakeel S A Morcos and A M Mahlis ldquo-e majorcations in Lake Maryut watersrdquo Hydrobiologia vol 36 no 2pp 253ndash274 1970
[53] A M Mahlis S A Morcos and S K El-Wakeel ldquo-e majoranions in Lake Maryut watersrdquo Hydrobiologia vol 36 no 2pp 275ndash294 1970
[54] A S Saad M A Massoud R A Amer and M A GhorabldquoAssessment of the physico-chemical characteristics andwater quality analysis of Mariout Lake southern of Alexan-dria Egyptrdquo Journal of Environmental and Analytical Toxi-cology vol 7 no 1 p 421 2017
[55] R Rumuri ldquoDataset on hydrogeochemical characteristics ofgroundwater and surface water in Kattumannarkoil TalukIndiardquo Data in Brief vol 32 Article ID 106058 2020
[56] P Szefer S W Fowler K Ikuta et al ldquoA comparative as-sessment of heavy metal accumulation in soft parts and byssusof mussels from subarctic temperate subtropical and tropicalmarine environmentsrdquo Environmental Pollution vol 139no 1 pp 70ndash78 2006
[57] N F Soliman G M El Zokm and M A Okbah ldquoRisk as-sessment and chemical fractionation of selected elements insurface sediments from Lake Qarun Egypt using modifiedBCR techniquerdquo Chemosphere vol 191 pp 262ndash271 2018
[58] G M El Zokm M I A Ibrahim L A Mohamed and M El-Mamoney ldquoCritical geochemical insight into Alexandria coastwith special reference to diagnostic ratios (TOCTN amp SrCa)and heavy metals ecotoxicological hazardsrdquo Egyptian Journalof Aquatic Research vol 46 no 1 pp 27ndash33 2020
[59] A S Likuku K B Mmolawa and G K GaboutloeloeldquoAssessment of heavy metal enrichment and degree of con-tamination around the copper-nickel mine in the SelebiPhikwe Region Eastern Botswanardquo Environment and EcologyResearch vol 1 no 2 pp 32ndash40 2013
[60] M K Khalil S E O Draz G M El Zokm and G F El-SaidldquoApportionment of geochemistry texturersquos properties and riskassessment of some elements in surface sediments from Bar-dawil Lagoon Egyptrdquo Human and Ecological Risk AssessmentAn International Journal vol 22 no 3 pp 775ndash791 2016
[61] M M El-Sadaawy and G F El-Said ldquoAssessment of fluoridein three selected polluted environments along the EgyptianMediterranean Sea effects on local populationsrdquo Human andEcological Risk Assessment An International Journal vol 20no 6 pp 1643ndash1658 2014
[62] USEPA ldquoSuperfund exposure assessment manualrdquo inOSWER Directive 92855-1EPA540l-88001Office of Emer-gency and Remedial Response Washington DC USA 1988
[63] USEPA ldquoExposure factors handbookrdquo in EPA6008-89043Office of Health and Environmental Assessment Wash-ington DC USA 1989
[64] Health Canada ldquoFederal Contaminated Site Risk Assessmentin Canadardquo Part II Health Canada Toxicological ReferenceValues (TRVs) Cat H46-204-368E Calgary Health CanadaOttawa Canada 2007
[65] J Iqbal S A Tirmizi and M H Shah ldquoStatistical appor-tionment and risk assessment of selected metals in sedimentsfrom Rawal Lake (Pakistan)rdquo Environmental Monitoring andAssessment vol 185 no 1 pp 729ndash743 2013
[66] USEPA (US Environmental Protection Agency) Region 6USAEPA ldquoMultimedia Planning and Permitting DivisionrdquoOffice of Solid Waste Center for Combustion Science andEngineering Washington DC USA 2005
[67] P Jeschke ldquoLatest generation of halogen-containing pesti-cidesrdquo Pest Management Science vol 73 no 6 pp 1053ndash10662017
[68] M A Shreadah O A El-Rayis N A Shaaban andA M Hamdan ldquoWater quality assessment and phosphorusbudget of a lake (Mariut Egypt) after diversion of wastewaterseffluentsrdquo Environmental Science and Pollution Researchvol 27 no 21 pp 26786ndash26799 2020
[69] J P Riley and M Tongudai ldquo-e major cationchlorinityratios in sea waterrdquo Chemical Geology vol 2 pp 263ndash2691967
[70] R B McCleskey D K Nordstrom D D Susong J W Balland J M Holloway ldquoSource and fate of inorganic solutes inthe gibbon river yellowstone national park Wyoming USArdquoJournal of Volcanology and Geothermal Research vol 193no 3-4 pp 189ndash202 2010
[71] G T F Wong and K-Y Li ldquoWinklerrsquos method overestimatesdissolved oxygen in seawater iodate interference and itsoceanographic implicationsrdquo Marine Chemistry vol 115no 1-2 pp 86ndash91 2009
[72] B S R V Prasad P D N Srinivasu P S VarmaA V Raman and S Ray ldquoDynamics of dissolved oxygen inrelation to saturation and health of an aquatic body a case forChilka Lagoon Indiardquo Journal of Ecosystems vol 2014 Ar-ticle ID 526245 17 pages 2014
[73] China Environmental Protection Agency EnvironmentalQuality Standards for Surface Water (GB3838ndash2002) NationalEnvironmental Protection Agency of China Beijing China2002
[74] Y Jia L Wang Z Qu and Z Yang ldquoDistribution con-tamination and accumulation of heavy metals in watersediments and freshwater shellfish from Liuyang RiverSouthern Chinardquo Environmental Science and Pollution Re-search vol 25 no 7 pp 7012ndash7020 2018
[75] A Moneer M El-Sadawy G El-Said and A Radwan ldquoBoronhuman health risk assessment relative to the environmentalpollution of Lake Edku Egyptrdquo Journal of King AbdulazizUniversity vol 23 no 2 pp 41ndash55 2012
[76] C B Tabelin T Igarashi T Arima D Sato T Tatsuhara andS Tamoto ldquoCharacterization and evaluation of arsenic andboron adsorption onto natural geologic materials and theirapplication in the disposal of excavated altered rockrdquo Geo-derma vol 213 pp 163ndash172 2014
[77] G Aloisi K Wallmann M Drews and G BohrmannldquoEvidence for the submarine weathering of silicate minerals inBlack Sea sediments possible implications for the marine Liand B cyclesrdquo Geochemistry Geophysics Geosystems vol 5no 4 pp 1ndash22 2004
[78] C Degueldre and V Cloet ldquoPore water colloid properties inargillaceous sedimentary rocksrdquo Science of e Total Envi-ronment vol 569-570 pp 423ndash433 2016
Journal of Chemistry 19
[79] J A Higgins and D P Schrag ldquoRecords of Neogene seawaterchemistry and diagenesis in deep-sea carbonate sedimentsand pore fluidsrdquo Earth and Planetary Science Letters vol 357-358 pp 386ndash396 2012
[80] H Schroeder A-L Fabricius D Ecker T A Ternes andL Duester ldquoMetal(loid) speciation and size fractionation insediment pore water depth profiles examined with a newmesoprofiling systemrdquo Chemosphere vol 179 pp 185ndash193 2017
[81] Y Song and G Muller ldquoFreshwater sediments sinks andsources of brominerdquo Naturwissenschaften vol 80 no 12pp 558ndash560 1993
[82] M E Goher H I Farhat M H Abdo and S G Salem ldquoMetalpollution assessment in the surface sediment of Lake NasserEgyptrdquo Egyptian Journal of Aquatic Research vol 40 no 3pp 213ndash224 2014
[83] G F El-Said M M El-Sadawy and A A Moneer ldquoIncor-poration of fluoride and boron into surface sediments alongthe Egyptian Mediterranean coastrdquo Egyptian Journal ofAquatic Research vol 36 no 4 pp 569ndash583 2010
[84] B Gilfedder G M Petri M Wessels and H Biester ldquoAniodine mass-balance for Lake Constance Germany insightsinto iodine speciation changes and fluxesrdquo Geochimica etCosmochimica Acta vol 74 no 11 pp 3090ndash3111 2010
[85] E Korobova L Kolmykova B Ryzhenko et al ldquoDistributionand speciation of iodine in drinking waters from geochem-ically different areas of Bryansk region contaminated after theChernobyl accident in relation to health and remediationaspectsrdquo Journal of Geochemical Exploration vol 184pp 311ndash317 2018
[86] V Zic V W Truesdale and N Cukrov ldquo-e distribution ofiodide and iodate in anchialine cave watersmdashevidence forsustained localised oxidation of iodide to iodate in marinewaterrdquoMarine Chemistry vol 112 no 3-4 pp 168ndash178 2008
[87] M B Heeb J Criquet S G Zimmermann-Steffens andU Von Gunten ldquoOxidative treatment of bromide-containingwaters formation of bromine and its reactions with inorganicand organic compoundsmdasha critical reviewrdquo Water Researchvol 48 pp 15ndash42 2014
[88] V Sivasankar A K Darchen and R Omine SakthivelldquoChapter 2 ldquofluoride a world ubiquitous compound itschemistry and ways of contaminationrdquo in Surface ModifiedCarbons as Scavengers for Fluoride fromWater V SivasankarEd pp 5ndash32 copy Springer International Publishing Switzer-land Cham Switzerland 2016
[89] O Cabestrero P Del Buey and M E Sanz-Montero ldquoBio-sedimentary and geochemical constraints on the precipitationof mineral crusts in shallow sulphate lakesrdquo SedimentaryGeology vol 366 pp 32ndash46 2018
[90] M A Hassaan O A El-Rayis and E I Hemada ldquoEstimationof the redox potential of lake mariut drainage system (Qalaaand Umum drains)rdquoHydrology vol 5 no 6 pp 82ndash85 2017
20 Journal of Chemistry
(EDI) hazard quotient (HQ) and hazard index (HI) as givenin equations (4)ndash(11)
2101 For Surface Water Estimated daily intake of surfacewater ingestion and dermal contact (EDIIngw and EDIDermw)were computed by the following equations [61]
EDIIngw(mgkgday) (CW times CR times ET times EF times ED)
(AT times BW) (4)
EDIDermw(mgkgday) (CW times SA times PC times ET times EF times ED times CF)
(AT times BW)
(5)
where CWwas the element concentration in water (mg Lminus1)CR was the contact time (50mL hminus1) ET was the exposuretime (26 h dayminus1) EF was the exposure frequency (7 dayyearminus1) ED was the exposure duration (60 year) ATwas theaverage time (60times 365 day yearminus1) BWwas (707 kg) SAwas
the skin surface area (5700 cmminus2) PC was the dermalpermeability constant (0001 cm hminus1) and CF was theconversion factor for water (10times10minus6 kg mgminus1) [62ndash65]
2102 For Sediment Estimated daily intake of sediment byingestion and dermal contact (EDIIngs and EDIDerms) werecalculated according to the following equations [60]
EDIIngS(mgkgday) CS times IngS times RAFS times EFS( 1113857
(AT times BW) (6)
EDIDermS(mgkgday) CS times IngS times ED times SA times AF times ABS( 1113857
(AT times BW)
(7)
where CS was the concentration of the contaminant insediment (mg gminus1) IngS was the ingestion rated of sediment(80times10minus5mg kgminus1) RAFS was the relative absorption factorof sediment (058) EFS was the exposure frequency (30 day
Table 2 Distribution of the studied variables in surface water (w) and their chlorinity ratios along Lake Mariout
Determined variables Minimum Site Maximum Site Average SD Seawatera Lake Marioutbcd
Physicochemical variablesTw 137 10 1534 11 1759 134Salinity (Spermilw) 23 13 79 1 489 152Chlorinity (Clpermilw) 205 13 71 1 438 137 1898TDSw (mg Lminus1l) 24635 13 7683 1 48503 152874Turbidity (NTU) 166 8 385 12 1296 1174DOw (mg Lminus1l) 0 6 1241 2 605 483 214ndash563d
pHw 744 13 899 2 710ndash860d
CO3w (mg Lminus1) 12 1 amp 2 1152 3 31 388HCO3w (mg Lminus1) 7808 3 19032 12 1147 321Bw (mg Lminus1) 05 7 1661 1 691 411 45Pw (μg Lminus1) 003 8 126 5 029 033Siw (μg Lminus1) 009 12 699 4 317 191Caw (mg Lminus1) 6092 12 3527 8 17703 735 400 549 818ndash1464d
Mgw (mg Lminus1) 9725 3 66615 1 28684 16002 1272 1201Naw (mg Lminus1) 231 11 1420 1 101115 2972 10556 10332Kw (mg Lminus1) 8 11 59 1 3769 123 380 585Liw(mg Lminus1) 0139 11 017 1 0154 001 017SO4w (mg Lminus1) 1978 12 34111 9 16856 9488 2649 4245Cuw (μg Lminus1) 204 3 621 7 317 113 7Mnw (μg Lminus1) 001 8 amp13 198 3 315 554 10Few (μg Lminus1) 009 9 1392 13 69 419 40Znw (μg Lminus1) 527 2 2367 5 1085 578 20Fw (mg Lminus1) 015 11 396 12 204 117 13Clw (mg Lminus1) 2048 13 7284 1 4397 1400 18980Brw (mg Lminus1) 506 12amp13 541 5 1813 1891 65 592Iw (μg Lminus1) 566 10 541 4 1108 1296 60Ion chlorinity ratioCawClw 170Eminus 02 12 100Eminus 01 13 440Eminus 02 240Eminus 02 213Eminus 02 335Eminus 02MgwClw 250Eminus 02 3 110Eminus 01 13 640Eminus 02 230Eminus 02 669Eminus 02 733Eminus 02NawClw 650Eminus 02 11 380Eminus 01 13 240Eminus 01 720Eminus 02 560Eminus 01 635Eminus 01KwClw 220Eminus 03 11 150Eminus 02 13 890Eminus 03 290Eminus 03 210Eminus 02 360Eminus 02LiwClw 240Eminus 05 1 700Eminus 05 13 380Eminus 05 110Eminus 05 939Eminus 06SO4wClw 540Eminus 03 12 110Eminus 01 13 420Eminus 02 310Eminus 02 140Eminus 01 260Eminus 01BwClw 978Eminus 05 7 332Eminus 03 9 670Eminus 03 170Eminus 03 895Eminus 04FwClw 430Eminus 05 11 140Eminus 03 13 540Eminus 04 420Eminus 04 670Eminus 05BrwClw 140Eminus 03 12 160Eminus 02 9 440Eminus 03 500Eminus 03 350Eminus 03 360Eminus 05IwClw 940Eminus 04 1 160Eminus 02 4 300Eminus 03 400Eminus 03a[51] b and c[52 53] d[54]
6 Journal of Chemistry
yearminus1) AF was the adherence factor (007mg cmminus2) andABS was the dermal absorption factor (0001 unit less)[65 66]
Hazard index (HI) is the total chronic hazard attribut-able to exposure to all determined contaminants (i) througha single exposure pathway of the ingestion and dermalcontact of water (HIIngw and HIDermw) and sediment (HIIngsand HIDerms) was given as follows [60]
HIIngW 1113944HQ IngW( 1113857i (8)
HIDermW 1113944HQ DermW( 1113857i (9)
HIIngS 1113944HQ IngS( 1113857i (10)
HIDermS 1113944HQ DermS( 1113857i (11)
3 Results and Discussion
31 Distribution of Halogens and Tested Variables in SurfaceWater
311 Distribution of Halogens in Surface Water -e rangeand average value of halogens in the surface water in thisstudy show a sequence of ClwgtBrwgt Fwgt Iw (Table 2 andFigure 2)-e current study indicate that the water sample ofpumping station (site 6) attained high concentrations offluoride (28mg Lminus1) chloride (38878mg Lminus1) and bromide(181mg Lminus1) and low iodide (641 μg Lminus1) contents (Fig-ure 2) High levels of F Br and I are detected in the MainBasin region which is affected by the drainage of El-Qalaaand El Umoum containing the agricultural and industrialwastes However halogens are involved in the manufactureof pesticides (herbicides fungicides insecticidesacaricidesand nematicides) [67] Plus halogens are produced in theproduction of fertilizers products [67] -e presented resultsof halogens in the studied lake region reflect anomalousdistribution and are mainly affected by water dischargedfrom the drainage sources However the highest fluoridebromide and iodide contents of 377mg Lminus1 6553mg Lminus1and 5410 μg Lminus1 respectively are recorded in the MainBasin affected by El-Qalaa and El Umoum drains Amongthe halogens chloride shows high levels in surface waterespecially in site 1 (72837mg Lminus1) site 2 (65218mg Lminus1)and site 10 (51687mg Lminus1) which are also related to theirlevels in the water of the drains (Figure 2) On the meantimethe lowest Spermilw and Clpermilw are observed at site 13 (ElUmoum Drain) Most of the studied variables have chlo-rinity ratios relatively lower than those measured for LakeMariout andor seawater [51ndash53 68 69] -is is mainly dueto the accumulation of wastewater from Abis and ElUmoum where agricultural products such as fertilizers andbiocides are deposited in industrial products [19]
Due to the increase in chloride content in surface watersamples the conservativeness of the chlorinity ratio is usedto describe the contamination precipitation and dissolutionof sediment components [70] -e FCl ratio in the studyarea is higher than open seawater (430Eminus 05) of a range
430Eminus 05ndash140Eminus 03 and average 540Eminus 04 -e BrClratio is relatively similar to that of seawater (Table 2) -ehighest FCl BrCl and ICl ratios in surface water140Eminus 03 160E ndash 02 and 160Eminus 02 are recorded in site 13(El Umoum drain outside the lake) site 9 (South West Basinin the lake) and site 4 (Main Basin in the lake) -erefore itcan be concluded that the distribution of halogens in thesurveyed area is greatly affected by the drainage of the El-Qalaa El Umoum and the El Nubaria drains
312 Distribution of Tested Variables in Surface Water-e range and average values of the tested variables (Tw Spermilw Clpermilw TDSw turbidity DOw pHw CO3w HCO3w BwPw Siw Caw Mgw Naw Kw Liw SO4w Cuw Mnw Few andZnw) in surface waters of the present study are listed inTable 2 Turbidity fluctuates from 166 to 3850 NTU at sites8 and 12 respectively DO is completely depleted at sites 5 6and 11 and has the highest amount 1241mg Lminus1 at site 2with an average 605mg Lminus1 relatively similar to the reportedLake Mariout value (214ndash563mg Lminus1 [54]) (Table 2) -eaverage content of DO in the lake is higher than those re-ported for the ocean seawater (32ndash48mgL) [71] -e levelsof DO probably relate to the oxygen-producing processes ofthe photosynthesis processes of phytoplankton and mac-rophytes [72] -e presented results indicate that site 1(affect by Abis drainage) is the most affected area in the lakeas it shows the highest contents of Bw Clw Mgw Naw KwLiw and SO4w -e most important feature in the concen-trations of heavy metals Cuw Mnw and Znw in surface wateris that they possess average values lower than those reportedfor the threshold guideline (10 100 and 50 μg Lminus1) [73 74]
-e present study clears out a descending trend in thesurface water average concentrations of halogens andtested variables in the lake as follows TDSw gtClw gtNaw gtMgw gtCaw gt SO4w gtHCO3wgtKw gtCO3w gt Bw gt Brwgt FwgtLiw gt Znw gt Few asymp Siw gtMnw gt Pw gt Iw (Table 2)
313 Interactions of Halogens and Tested Variables inSurface Water Chloride in surface water is significantlyrelated to the drainage water content showing good cor-relations with Tw (r 0631 ple 0028) and pHw (r 0769ple 0003) (Supplementary Table 1) -e negative moderaterelation of Fw and Ip (r 0606 ple 0037) may indicatereplacement of iodine in pore water by fluoride of the surfacewater-emoderate relationship between fluoride in surfacewater and CO3w (r minus0632 ple 0027) and HCO3w(r 0593 ple 0042) may be related to carbonate exchangeand the formation of fluorite minerals (CaF2) [23]
-e correlation matrix reflects that the observed ex-traordinary levels of Bw in the surface water samples aremost probably due to its exchange with the different sedi-ment components not related to the discharged waters(Supplementary Table 1) -is findings is supported by theweak B correlation with Cuw (r minus0587 ple 0045) andgood correlation with Fs (r minus0666 ple 0018) [75 76]However Cuw is one of the pollutants that can be exchangedin drainage water -e correlations of Mgw amp Naw (r 0629
Journal of Chemistry 7
1
23
4
56
7
8
9
10
2986degE 2988degE 2990degE 2992degE
310
8degN
311
0degN
311
2degN
311
4degN
311
6degN
El-mex
pumping
statio
n Main Basin
of Lake Maryout
Southwest Basin
Qalaa Drain
El Umoum Drain
Northwest BasinFish
ery Basi
nEl Nubaria Drain
3311 to 38883888 to 43934393 to 5115
5115 to 65226522 to 7284
(a)
1
23
4
56
7
8
9
10
2986degE 2988degE 2990degE 2992degE
310
8degN
311
0degN
311
2degN
311
4degN
311
6degN
El-mex
pumping
statio
n
Main Basinof Lake Maryout
Southwest Basin
Qalaa Drain
El Umoum Drain
Northwest Basin
Fishery
BasinEl Nubaria Drain
069 to 127127 to 169169 to 242
242 to 277277 to 377
(b)
El-mex
pumping
statio
n
Main Basin of Lake Maryout
South west Basin
North west Basin
1
23
4
56
7
8
9
10
2986degE 2988degE 2990degE 2992degE
310
8degN
311
0degN
311
2degN
311
4degN
311
6degN
Qalaa Drain
El Umoum Drain
Fishery
BasinEl Nubaria Drain
613 to 852852 to 14381438 to 1732
1732 to 52745274 to 6554
(c)
El-mex
pumping
statio
n
Main Basin of Lake Maryout
Southwest Basin
Northwest Basin
1
23
4
56
7
8
9
10
2986degE 2988degE 2990degE 2992degE
310
8degN
311
0degN
311
2degN
311
4degN
311
6degN
Qalaa Drain
El Umoum Drain
Fishery
BasinEl Nubaria Drain
566 to 671671 to 761761 to 817
817 to 922922 to 5411
(d)
Figure 2 Distribution of halogens (Cl F Br and I in surface water of LakeMariout (a) Cl (mg Lminus1) (b) F (mg Lminus1) (c) Br (mg Lminus1) and (d) I(μg Lminus1)
8 Journal of Chemistry
ple 0028) Mgw amp Liw (r 0790 ple 0002) Naw amp Kw(r 0955 ple 0000 Naw amp Liw (r 0835 ple 0001) Naw ampCO3w (r minus0701 ple 0011) Kw amp Liw (r 0712 ple 0009)Kw amp CO3w (r minus0580 ple 0048) CO3w amp HCO3w(r minus0613 ple 0034) and Mgw amp SO4w (r 0631ple 0028) indicate that all these variables have some geo-chemical behaviors [77] Mg Na and Li are some com-ponents of the discharged waters however they havepositive correlations with the chlorinity and salinity of thedischarged water sources (r 0743 0619 and 0815 re-spectively) and (r 0743 0619 and 0815 respectively)Mgw and Liw contents in water samples are affected bytemperature dissolved oxygen and pH with high correla-tions of r minus0650 0677 and 0743 and minus0702 0659 and0815 respectively
32 Distribution of Halogens and Tested Variables in PoreWater
321 Distribution of Halogens in Pore Water -e averagehalogen contents in the pore water are higher than theircontents in the surface water but in the same orderClpgtBpgt Fpgt Ip (Table 3) Current research shows that thelowest and highest average values of Spermilp and Clp have beenmeasured in the pore water of site 6 and site 8 respectively Itis worth mentioning that site 6 is a mixed water of El-Qalaadrainage sewage WWTP treatment plant and lake waterInterestingly the high concentrations of fluoride chloridebromide and iodide in the pore water at site 6 are 123mgLminus1 40321mg Lminus1 11739mg Lminus1 and 24339 μg Lminus1 re-spectively (Table 3) -e salinity and chloride content in thepore water of site 8 are related to the discharge water of manypetrochemical and oil companies besides some fish farms
322 Distribution of Tested Variables in Pore Water -etested variables in the pore water (p) give the followingdescending order MgpgtNapgtCapgt SO4pgtBpgtKpgtBrpgt Fpgt LipgtPpgt Ipgt Sip (Table 3) Interestingly the deter-mined variables in the pore water have higher values thanthe surface water along the lake According to previousstudies pore water is responsible for biogeochemical reac-tions the migration and transformation of partitioned andformed compounds and the transportation of colloidalspecies [78 79] In addition pore water can explore thepotential risks of man-made pollution sources [80] -etested variables in the pore water (p) are given in a differentorder of surface water of ClpgtMgpgtNapgtCapgt SO4pgtBpgtKpgtBrpgt Fpgt Lipgt Ppgt Ipgt Sip (Tables 2and 3)
323 Interactions of Halogens and Tested Variables in PoreWater -e following interactions of halogens CO3w amp Ip Ipamp Fw Brw amp Sip Fp amp Siw and Fp amp Nap give correlationvalues (r 0706 ple 0010 r minus0606 ple 0037 r 0826ple 0001 r minus0704 ple 0011 and r 0670 ple 0017respectively) (Supplementary Table 1) However these re-lationships may indicate their precipitation andor
adsorption on the colloidal particles besides the formation ofsome chemical species [78 79] Extraordinarily large cor-relations of Nap amp HCO3w Kp amp HCO3w Spermilw amp Bp Spermilp ampKp Spermilp amp Lip and Spermilp amp Clp (r 0692 minus0609 minus07410696 0910 and 1000) may refer to the release of theseelements from sediment particles andor precipitation oradsorption [77] In the matrix the negative correlationbetween Cap and Mgp (r minus0592 ple 0042) may be relatedto the release of Mg during the recrystallization of calcite[79]-e relationship between Caw amp SO4p Cuw amp Cap Pw ampPp and Nap amp pHw (r 0744 ple 0006 r 0719 ple 0008r 0647 ple 0023 and r minus0640 ple 0025 respectively)may be due to the chemical interactions in the pore fluidsand the formation certain compounds
33Distribution ofHalogens andTestedVariables in Sediment
331 Distribution of Halogens in Sediment -e averagehalogenrsquos content in the sediment shows a different orderfrom the surface and pore waters of Brsgt FsgtClsgt Is (Ta-ble 4) -e sediment results show that the average bromidecontent is higher than fluoride followed by chloride contentand iodide with average values of 452mg gminus1 040mg gminus1029mg gminus1 and 450 μg gminus1 respectively
-e fluoride concentration in the sediment ranges from001 to 120mg gminus1 with an average value of 04plusmn 035mggminus1 -ese values are lower than reported marine sedimentvalues and higher than the El-Bardawil Lagoon [60]Amongst the halogens the study reveals that Br is the mostabundant ion in surface water pore water and sedimentsamples due to the excessive amounts of organic matter [81]On the contrary the concentration of Cl ions in sedimentsamples is lower than that in surface water and pore watersamples indicating that it exists in soluble salts -e currentresults indicate that the sediments collected from the mostaffected area by the Mediterranean Sea (site 6) contain el-evated levels of fluoride (070mg gminus1) bromide (852mggminus1) and chloride (020mg gminus1) and a reduced amount ofiodide (209 μg gminus1) (Table 4)
332 Distribution of Tested Variables in Sediment -eaverage value of test variables in the determined sedimentsamples shows a significant change from site to site with adescending order CO3sgtMgsgtCasgtNasgt SO4s gt FesgtBsgtKsgtTPsgtMn sgtZnsgtCusgt Lis (Table 4) Plus this studyclears out that the percent of sand and mud of the differentsediment samples ranges from 4 at sites 1 amp 13 to 85 atsite 11 and from 15 at site 11 to 96 at sites 1amp13 re-spectively with averages 25 and 75 respectively Plusthe porosity shows a trend opposite to the particle size andvaries from 4676 to 8214 with an average value of5609plusmn 1114 -e results of the current study reveal mod-erate amounts of CO3 in the sediment samples fluctuatingbetween 1639 and 5736 at sites 6 and 2 respectively -eresults of sand mud porosity and CO3 percentage reflect thatthe texture of the sediment is mainly composed of mud mixedwith carbonate compounds Comprehensively the large storageof sediments with carbonate (359plusmn1280) magnesium
Journal of Chemistry 9
Tabl
e3
Distribu
tionof
thestud
iedvariablesin
thepo
rewater
(p)alon
gLake
Mariout
Site
Spermilp
pHP
Ca p
(mgLminus
1 )Mg p
(mgLminus
1 )Na p
(mgLminus
1 )Kp
(mgLminus
1 )Li
p(m
gLminus
1 ))
SO4P
(mgLminus
1 ))
B P(m
gLminus
1 ))
P P(μgLminus
1 ))
SiP
(microgLminus
1 ))
F p(m
gLminus
1 ))
Cl P
(mgLminus
1 ))
Brp
(mgLminus
1 ))
I p(μgLminus
1 )1
1034
787
481
42303
1097
453
042
2944
8043
363
0045
323
95419
959
7104
2934
809
5611
115725
1050
498
039
2056
663
553
0036
338
8398
1385
24698
31272
717
100
5689
1195
577
053
2778
8949
1204
0034
754
114469
2291
26347
483
796
9619
47652
974
384
043
350
19312
77
0054
215
74599
693
8393
51099
782
5611
89711
1128
42041
1667
16739
1112
0081
1698864
1332
8333
645
775
4008
75367
736
41024
2111
11739
071
0037
1231
40321
799
24339
71125
782
39278
13615
1155
516
056
3667
6051
369
006
6101209
1279
8123
8148
775
9299
84314
1355
468
055
12444
942
212
0056
892
133232
1172
7643
9684
78
962
72109
880
393
036
3778
21341
114
0087
1061429
2131
9981
10114
764
1122
113586
1195
524
049
4667
8007
071
0041
1138
102562
1332
8572
11639
742
4008
61996
915
332
033
2833
11594
754
0026
1215
67834
746
37587
125
702
481
38413
8703
274
028
2167
13913
081
0025
2154
44832
1438
9891
13755
807
3206
6467
817
446
039
4556
17246
635
0042
954
5737
533
1097
Minim
um45
702
962
13615
736
274
024
1667
6051
071
0025
215
40321
533
7104
Maxim
um148
809
39278
115725
8703
577
056
12444
21341
1204
0087
2154
133232
2291
37587
Average
919
77
718
67412
163077
4381
041
3782
1223
485
0048
955
82779
1238
14768
SD308
032
10027
29209
2132
825
01
2769
5047
391
0019
542
27891
524
9917
10 Journal of Chemistry
Tabl
e4
Distribu
tionof
thestud
iedvariablesin
thesediment(s)alon
gLake
Mariout
Site
Sand
()
Mud ()
Porosity
()
CO3s
()
B s(m
ggminus
1 )P s
(mg
gminus1 )
Ca s
(mg
gminus1 )
Mg s
(mg
gminus1 )
Na s
(mg
gminus1 )
Ks
(mg
gminus1 )
Lis(m
ggminus
1 )
SO4s
(mg
gminus1 )
Fes
(mg
gminus1 )
Cu s (μg
gminus1 )
Mn s
(μg
gminus1 )
Zns(μg
gminus1 )
F s(m
ggminus
1 )
Cl s
(mg
gminus1 )
Brs
(mg
gminus1 )
I s(μg
gminus1 )
14
964915
183
299
044
1670
811
2583
408
0028
4861
828
963
5617
1272
034
041
128
1686
244
564925
574
196
028
1002
1419
2717
269
0015
662
257
793
4350
1313
057
054
123
358
319
816667
299
246
073
1670
1216
3125
336
0022
463
487
1228
4330
1677
044
034
448
516
418
824853
3813
1111
032
668
2229
3425
365
0094
2222
770
922
4637
1245
030
020
309
296
512
884697
482
614
012
501
1115
1833
091
0040
1713
243
600
27933
1223
082
034
245
254
65
954667
164
370
157
835
1257
2958
388
0030
5648
890
1927
5347
3117
070
020
852
209
75
954762
375
524
024
367
2047
3133
256
0102
1157
546
883
4185
1393
120
020
341
259
838
626143
457
697
039
668
1621
3550
347
0145
4167
598
737
4157
1412
022
034
144
1277
918
826000
349
083
054
401
1094
3358
369
0025
2454
701
868
5702
3065
036
027
250
172
1036
645070
441
296
002
935
1763
3117
246
0045
2685
369
790
4533
1315
012
047
1012
224
1185
157000
325
240
074
969
2250
3508
328
0193
1343
1026
735
3890
1070
005
007
533
128
1237
638214
463
291
032
334
1824
3008
358
0018
556
340
728
2475
827
001
007
852
281
134
965000
177
211
054
2338
1621
3925
599
0068
833
1687
1187
6492
1853
004
027
639
194
Min
415
4667
164
083
002
334
811
1833
091
0015
463
243
600
2475
827
001
007
123
128
Max
8596
8214
574
1111
157
2338
2250
3925
599
0193
6620
1687
1927
6492
3117
120
054
1012
1686
Av
2575
5609
359
398
048
951
1559
3096
335
0063
2671
672
951
4500
1599
040
029
452
450
SD23
231114
128
276
039
603
455
522
115
0055
2030
393
343
1120
708
035
014
303
475
Minm
inim
umM
axm
axim
uma
ndAv
averageSD
stand
arddeviation
Journal of Chemistry 11
(1559plusmn455mg gminus1) and calcium (951plusmn603mg gminus1) com-ponents may be attributed to the abundance of calcium min-erals [4] However in general the average amounts of allvariables in sediment samples showmarked variations fromonesite to another with a descending order of CO3sgtMgsgtCasgtNasgtSO4sgtFesgt BrsgtBsgtKsgtTPsgtFs gtClsgtMnsgtZnsgtCusgtLisgt Is (Table 4) -e measured concentra-tions of Mn Zn Cu and Fe in the sediment samples are stilllower than the reported values and also lower than the back-ground levels of crust and the toxicological reference contents ofUS DOE (US Department of Energy) US EPA (US Envi-ronmental Protection Agency) and CEQG (Canadian Envi-ronmental Quality Guidelines) [82]
Contrasting the obtained levels for the halogens withthose previously reported ones the present study indicatesthat surface and pore waters incorporate more considerableamounts of fluoride compared to the formerly reported onesin Lake Edku (Tables 2 and 3) and lower levels in theMarioutarea than those measured along the Egyptian MediterraneanSea coast [27] Compared with the sediments previouslyfound on the Mediterranean coast of Egypt the chloridecontent in the sediments of the Mariout area is lower [83]Compared with those observed in seawater the studiedsurface water and pore water samples have lower bromidecontent and higher levels than previously reported in LakeMariout [52 53] -e concentration of iodide in surfacewater pore water and sediments is equivalent to the con-centration of rivers and lakes in the world [84]
333 Interactions of Halogens and Tested Variables inSediment -e correlation matrix shows the important roleof halogens in the formation and precipitationdissolution ofsalts and minerals produced along the lake (SupplementaryTable 1) However it shows that chloride seems to be in thesoluble forms along the surface and pore waters of studiedarea showing good relations with Caw (r 0666 ple 0018)Clp (r 0677 ple 0016) and SO4p (r 0858 ple 0000)Also Cls gives good correlations with Mgw (r 0710ple 0010) Naw (r 0602 ple 0038) Clw (r 0619ple 0032) Mgp (r 0774 ple 0003) and Kp (r 0731ple 0007) Chloride in the surface and pore waters plays animportant role in the dissolution association and formationof various salts along the lake -e good relationship be-tween Is and Caw (r 0666 ple 0018) may reflect the de-positionrelease of CaI+ during the formationdissolution ofcalcium carbonate [85] In addition these correlations maybe related to organic-I which formed by bacterial species andtheir remineralization in bottom sediments [86] -emoderate relationship between Nas and Brw (r minus0622ple 0031) may indicate the possible formation of BrClspecies and the precipitation or adsorption of Na minerals insediments [87] -e results of this study also reflect thestrong negative correlation between Fs and Bw (r minus0666ple 0018) which may be related to the release of fluoridefrom sediment and the formation of soluble fluoridecomplexes ((BFn[OH]4minusn)minus) with the excessive boron con-centration in the water [88] -e negative relation betweenKs and Spermilw (r minus0673 ple 0016) possibly reflect that Kw
preferentially chooses to exist in the soluble form of KClrather than being adsorbed andor bound by some richminerals in the sediment
-e significant correlations between CO3s and Mgw(r 0637 ple 0026) CO3s and Clw (r 0723 ple 0008)CO3s and pHw (r 0833 ple 0001) CO3s and Spermilw(r 0723 ple 0008) and between CO3s and Ks (r minus0673ple 0016) may be accompanied by the possible formationdissolution of the dolomite mineral in the presence ofsufficient Mgw which is usually affected by optimal pHsalinity and the potassium salts (Supplementary Table 1)-ese observed results are matching with the previouslyreported studies [32] Significant negative correlation be-tween TPs and CO3s (r minus0744 ple 0006) may indicate theextended release of P from carbonate minerals and for-mation of apatites [32]
-e correlation matrix also refers to other possible in-teractions between the remaining determined variables(Supplementary Table 1) -e significant correlation be-tween SO4s andMgw (r 0706 ple 0010) and Liw (r 0633ple 0027) may be associated to the formation of Mg-sulfateand the pollution of sediments by discharged waters con-taining excessive sulfate and Li [89] In the contrary thestrong positive correlation between TPs and Cus and be-tween TPs and Zns may be related to the same source ofpolluted discharge water [23 83]
-e high negative correlations of Zns with Few(r minus0785 ple 0003) CO3s (r minus0601 ple 0039) and Cus(r 0698 ple 0012) may indicate that Zn Cu and CO3depositions in sediment samples are linked to the soluble Feform in water (ferrous) ie the release of Fe upwards in thewater column in the anoxic conditions (SupplementaryTable 1) [90] -e excellent relations found between Fesand CO3s (r minus0799 ple 0002) Fes and Cas (r 0637ple 0026) Fes and Clw (r minus0752 ple 0005) Fes and Nas(r 0720 ple 0008) and between Fes and Ks (r 0833ple 0001) may reflect the dissolution of the chelating Feassociation with the soluble organic compounds in thewater-sediment interface and the formation of the sol-uble ferrous form in low dissolved oxygen within theareas affected by untreated discharged waters [90] -estrong correlations of Mns with SO4w Nap Nas Ks CO3sZns and Fes (r minus0585 0608 0611 0698 minus0655 0691and 0716 respectively) may associate with the solubilityof abundant Mn minerals and P-Mn forms in the sedi-ment because of its possible reduction to Mn+2 solublespecies under anoxic conditions [90] It is worth men-tioning that the results of this study indicate that ap-proximately 333 of the survey sites indicate thedepletion of dissolved oxygen in their surface watersamples Under such anoxic conditions bacteria are mostlikely to use sulfate instead of oxygen to break downorganic matter and cause the release of iron and phos-phorus into the water column
-e significant direct correlation between Ks and Nas(r 0832 plt 0001) clearly reflects the transport of solublesalts of K and Na between the pore water phase of thesediment and water-sediment surface phase (SupplementaryTable 1) -e good correlation between porosity and Nas
12 Journal of Chemistry
indicates the possible transfer of Na between pore water andsediment partitions
34 Interactions of Precipitated Halogenated Compounds inSurface and Pore Waters -e Saturation Index (SI) [23 60]of twenty-three and fifteen structures in surface water andpore water samples respectively are listed (Table 1) -ecorrelation matrix of the calculated Saturation Indices withthe presented data shows the different factors affecting theinteraction of the halogenated compound with other pre-cipitated salts and minerals Table 1 explores the precipitationof the phosphate minerals and salts are most abundantfollowed by the hydroxidesrsquo salts iodate salts sulfate andcarbonate minerals and salts in surface waters Amongst thehalogens precipitated salts fluoride minerals especiallyfluorapatites and carbonate-fluorapatite (FAP and CFAP)have high SI values in surface water (4277ndash5195 and1604ndash6089 respectively) and in pore water (5126ndash5460 and1752ndash7833 respectively) Bromide and chloride are mainlyfound in the soluble forms in surface and pore waters Iodidesalts (Ca(IO3)2 and Ca(IO3)26H2O) moderately precipitatein surface and pore Iron salts precipitate in surface waterwhile in pore water they are not formed -us SI contentreflects that halogens especially fluoride and iodide play avital role in reducing lake pollution
In addition Table 1 shows that the precipitation com-pounds that may be formed in surface water are relativelydifferent from those in sediment pore water For examplefluorite (CaF2) and sellaıte (MgF2) may be only formed inpore water while calcite and aragonite may be deposited insurface water However the formation of fluorite in surfacewater is related to Naw (r 0778 ple 0003) Kw (r 0704ple 0011) CO3w (r minus0718 ple 0009) Fw (r 0770ple 0003) and Ip (r minus0785 ple 0003) (SupplementaryTable 1)
-e formation of calcium sulfate hemihydrate calciumsulfate and anhydrite in water is related to the increase in theamounts of Caw Mgw SO4w Nap Fp Sip Cls and Mns andthe decrease in porosity values On the other hand pre-cipitation of calcium phosphate is related to Brw (r 0751ple 0005) Znw (r 0668 ple 0018) Pw (r 0881ple 0001) and Ks (r 0881 ple 0001) ie it is affected bythe discharged water composition (Supplementary Table 1)
-e formation of calcite and aragonite in surface water isrelated to the formation of CO3w (r 0753 ple 0005) anddissociation of HCO3w (r minus0660 ple 0020) pHw values(r minus0654 ple 0021) and their dissolution in sediment(r minus0620 ple 0032) (Supplementary Table 1)
-e dolomite formation in water may be affected by theincrease of CO3w (r 0817 ple 0001) and the decrease ofHCO3w (r minus0658 ple 0020) increase in TDSw (r 0599ple 0040) and increase in pHw (r minus0656 ple 0021)besides the possible release of CO3s from abundant sediment(r minus0624 ple 0030) and the precipitation of calcite(r 0984 ple 0000) and aragonite (r 0984 ple 0000) intosediment fraction (Supplementary Table 1)
Generally in the current study the possible formedhalogenated minerals and salts are affected by their
abundance in different components of the lake besides theirpossible dissolution or formation on the sediment texturesgeochemistry of the sediments and physicochemical vari-ables of water in addition to the components of the dis-charged waters
35 Interactions of Dissolved Halogenated Compounds inSurface and PoreWaters -e utilization of dissolved salts insurface and pore waters by utilizing Palmerrsquos method andpiper ternary diagram [50] indicates that Na is the richestcation in surface water followed by Mg Ca and K At thesame time Mg is the most predominate one in the porewater (Figures 3 and 4) Obviously Cl is the most importantanion in surface water and pore waters samples Howeverthe piper ternary diagrams of surface water and pore waterclearly shows that NaCl is the most dominant in surfacewater while MgCl2 is the most abundant in pore waterCoincidently Palmerrsquos method also reflects that NaCl(574) is the most existent species in surface water fol-lowed by MgCl2 (304) CaCl2 (71) CaSO4 (29)Ca(HCO3)2 (14) and KCl (12) (Figure 3) At the sametime MgCl2 (760) is the most present species in porewater followed by NaCl (73)asympMg(HCO3)2 (73)Ca(HCO3)2 (52) and MgSO4 (31) (Figure 4)
36 Multivariate Analysis
361 Principal Component (PCA) By applying Varimaxrotation and Kaiser normalization to 98 variables in the PCAfor halogens and tested variables and calculated parametervalues 7 extracted PCs with eigenvalues higher than 1 areobtained However it is important that the eigenvalue mustbe greater than 1 Its seven PCs explain 8558 of the totalvariance
-e first principle component (PC1) is 1473 of thetotal variance and shows positive coefficient factor loadingsfor CO3w TDSw Kp calcite aragonite dolomite FeCO3MgCO3 ZnCO3 and ZnCO3H2O (0804 0547 05320938 0938 0947 0741 0940 0866 and 0866 respec-tively) In addition it provides negative factor loadings forHCO3w pHw Bw Nap and CO3s (minus0782 minus0610 minus0595minus0532 and minus0572 respectively) PC1 is related to thefactors affecting the carbonate compounds that may beformed in the area under consideration
PC2 accounts to 1458 of the total variance and alsoshows positive and negative coefficient factor loadingsrepresenting the different interactions between the CawMgw Liw SO4wMgp Nap pHp Cls SO4s Brs and porosityin water pore water and sediment that are responsible forthe composition of sulfate magnesium and phosphateprecipitates besides the effect of the discharged waters onwater-pore water-sediment componentsrsquo cycles
PC3 typically shows 1377 of the total variance withpositive and negative loadings which can properly explorethe effect of the principal sources of local pollution on thedissolving of heavy metals B and P from sediment into thewater column and the probable formation of Fe(OH)2Fe(OH)3) and FePO4
Journal of Chemistry 13
Similarly the coefficient factor loadings of PC4 with1355 are related to the influence of the polluted dischargewater and sediment texture on the formation of F Cl and Isalt besides the precipitation of halogenated compounds(FeF2 Mn(IO3)2 KIO4 and KCIO4) besides their minerals(CaF2 MgF2 FAP and CFAP)
Simultaneously PC5 gives 1092 of the total variancewith positive and negative loadings which explains therelations between the physicochemical limits of the surfacewater pore water and sediment components and theprecipitation of minerals and salts (OCP HAP CuBrZn(OH)2 and Zn(IO3)22H2O) -is is also associated tothe influence of the sedimentary material on the release ofMn Fe and P from sediment into pore water and watercolumn and formation of Ca3(PO4)2 OCP and HAPminerals
However PC6 associates with 100 of the total variancegiving positive and negative coefficient factor loadingswhich explain that the sediments (minerals andor organic-iodine compounds) are only the acting sink for iodine andiodine species (Iminus and IOminus
3 ) in the water as previously re-ported [84] PC6 also reflects the precipitation of severalhalogenated compounds such as calcium iodate (Ca(IO3)2and Ca(IO3)26H2O) and copper iodate (CuI andCuIO3H2O) besides Cu3(PO4)2 species in the lake watercolumn
-e loadings of PC7 contribute by 804 and show thatthe release of calcium in pore water into the water column isresponsible for the precipitation of halogenated compounds(CuCl and Zn(IO3)22H2O) as well as copper and Zn salts(Cu3(PO4)2 and Zn(OH)2)
362 Cluster Analysis On the other hand cluster analysisshows that the similarity of sites 1amp4 5amp8 6amp9 2amp10 and11amp13 is due to the texture of sediment
363 Multiple Regression Multiple regression equations ofhalogens as dependent variables and the other determinedand calculated parameters as independent variables insurface water pore water and sediment partitions are listed(Table 5)-e amount of fluoride in water samples is affectedby the discharged watersrsquo fundamental components espe-cially Zn and Cu besides its surface water-pore water in-teractions Its content in pore water seems to be stronglyaffected by its substitution competition with other halogensin surface water-spore water-sediment cycle due to its highelectronegativity Generally in the affected area the type ofpollutant in the discharged water plays an important role inthe dissolution andor precipitation of fluoride and otherhalogens in the surface water-pore water-sediment cycle
574
147129
300
12
Ca(HCO3)2CaSO4CaCl2
MgCl2KClNaCl
(a)
SO4
2 + CIndash Ca 2+ + Mg 2+
CO32ndash + HCO3
ndashNa+ + K+
Mg2+ SO42ndash
Ca2+ CIndash
(b)
Figure 3 (a) distribution and (b) piper ternary diagram of the formed dissolved salts in surface water of Lake Mariout
Ca(HCO3)2Mg(HCO3)2MgSO4
NaClMgCI2KCl
760 1052
7373 31
(a)
SO4
2ndash + C
Indash
Ca 2+ + Mg 2+
CO32ndash + HCO3
ndashNa+ + K+
Mg2+ SO42ndash
CIndashCa2+
(b)
Figure 4 (a) distribution and (b) piper ternary diagram of the formed dissolved salts in pore water of Lake Mariout
14 Journal of Chemistry
Table 5 -e multiple regression analyses of each halogen as dependent variable and other tested variables in the surface water pore waterand sediment partitions besides the precipitated salts in surface water along Lake Mariout
Dependentvariable Multiple regression equation R2
FluorideLake water FW 3162 + 092 Zn F2 minus 033 SiP + 021 CuIminus 017 SpermilP 09911
Pore water Fp minus2567minus117 SiW minus 033 LiP minus 062 CuClminus 028 IS + 023 TDSW+ 017 KIO4 minus 012 BrW minus 004porosity + 004 PW
10000
Sediment FS 088 CAPminus 049 MgS minus 046 DOW+039MgW+ 027 Mn(IO3)2 + 015 Cu3(PO4)2 + 004 HAP+ 002 pHP 10000ChlorideLake water No relation 00000Pore water No relation 00000Sediment ClS minus116 + 046 MgP + 077 Kp minus 049 dolomite + 017 TDSW minus 011 CuI + 005 NaS + 002 BS + 001 FeF2 10000Bromide
Lake water BrW 1563 + 110 CuBrminus 057 CuClminus 021 KS minus 014 pHP minus 011 TPS + 014 FeW+ 007 ZnSminus 002 PP + 001turbidity 10000
Pore water BrP minus1516minus 055 FeS minus 073 BS + 061 MnW+ 083 SiP + 049 NaS minus 031MnS minus 015 CuBr + 011 pHW minus 001CaW
10000
Sediment BrS 015 SiP + 195 CFAP+ 002 FP minus 045 IS + 192 sand+ 037 MnW minus 029 MgS minus 012 LiP + 005Ca3(PO4)2 minus 002 ZnF2
10000
IodideLake water IW 099 Ca(IO3)6H2O 09999
Pore water IP minus097 ZnF2 minus 057 Li3PO4 minus 053 BP + 034 FAP+ 015 Ca(IO3)2 +MnW+ 005 KS minus 009 turbidity + 055CaS
09999
Sediment IS minus072 + 135 SO4P + 023 Mn(IO3)2 + 063 FeW+ 031 TPS minus 035 MgP minus 012 Zn(CO3)22H2O 09993
40E + 0135E + 0130E + 0125E + 0120E + 0115E + 0110E + 0150E + 0000E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
12345
678910
111213
(a)
10E + 0090E ndash 0180E ndash 0170E ndash 0160E ndash 0150E ndash 0140E ndash 0130E ndash 0120E ndash 0110E ndash 0100E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
12345
678910
111213
(b)
12345
678910
111213
40E ndash 0235E ndash 0230E ndash 0225E ndash 0220E ndash 0215E ndash 0210E ndash 0250E ndash 0300E ndash 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
(c)
12345
678910
111213
80E ndash 0670E ndash 0660E ndash 0650E ndash 0640E ndash 0630E ndash 0620E ndash 0610E ndash 0600E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
(d)
Figure 5 Hazard quotient of ingestion and dermal contact of surface water and sediment of LakeMariout (a) ingestion of water (b) dermalcontact of water (c) ingestion of sediment and (d) dermal contact of sediment
Journal of Chemistry 15
Minerals and precipitated salts in the different partitions(surface water pore water and sediment) play an importantrole in the deposition and release of halogens in sedimentsAdditionally the texture and the porosity of the sedimentsplay a key role in the distribution of halogens in the threepartitions Interestingly chloride is the only halogen that hasnegligible interactions along the surface water and porewater partitions because it is present in large quantities inthe form of soluble salts (NaCl and MgCl2)
37 Pollution Status
371 Enrichment Factor (EF) Twowell-knownmethods areused to assess environmental pollution public health sig-nificance of ingestion and dermal contact with water andsediment components and sediment enrichment factor (EF)[59 60]
-e average EF values of the determined elements CaMg Na K Li B P Cu Zn Mn Fe F Cl Br and I are alllower than the value that is less than the minimum en-richment value (EFlt 2)-us the area under investigation isstill ecologically considered as an unpolluted region
372 Human Health Risk Assessment -e EDI HQ and HIshow the variable values of all pollutants in the surface waterand sediments along the lake region and in drains (sites11ndash13) under study Among all the calculated variables ofsurface water ingestion (EDIIngw) and dermal contact(EDIDermw) Cl is still the only variable that shows high levels(average 1551 and 43mg kgminus1 dayminus1 respectively) -eestimation daily intake of sediment ingestion (EDIIngs) anddermal contact (EDIDerms) of Mg Ca and Na give maximumaverage amounts of 841Eminus 02 513E ndash 02 and167Eminus 03mg kgminus1 dayminus1 respectively
Among the HQ of the calculated detection variables thecontent of HQB of ingestion and dermal contact with waterand sediment is the highest However 70 of sites have HQBvalues more than 10 (Figure 5) Comparing the HQ values ofall the determined variables HQB of the ingestion of surfacewater shows values higher (gt10) However due to the impactof drainage the HQB values of stations 1ndash4 8ndash10 12 and 13
are higher than 10 -erefore these sites can be consideredas the area with the most serious boron pollution caused byuntreated discharged water disposal In addition the HIIngwlevel of water ingestion for the studied variables in all sites ismuch higher than 10 (Figure 6) Except for boron it isusually concluded that the study area does not pose any riskto the population due to halogens or other variables Ac-cordingly this information may help the official authoritiesoptimize management plans and strengthen their pollutioncontrol actions in Lake Mariout
4 Conclusions
-e effects of halogen salts and minerals on the pollution ofLake Mariout were studied Halogens and some physico-chemical variables in three partitions surface water porewater and sediment in Lake Mariout were evaluated -ehalogen content was variable between different sites andchloride was the main halogen in surface water and porewater but it was very rare in the lakersquos sediment partitionPiper ternary diagram and Palmerrsquos method reflected thatNaCl was the dominant salt in surface water while MgCl2was the main dissolve salt in pore water-e chlorinity ratiosof halogens and tested variables were directly matched to thefeeding drain sources
Moreover the Saturation Index (SI) reveals that 23 and 15precipitated salts and minerals are formed in surface water andpore water respectively -e SI value indicated the formationof phosphate minerals in surface water and pore water es-pecially octacalcium phosphate (OCP Ca4H(PO4)325H2O)and hydroxyapatite (HAP Ca5(PO4)3OH) In addition tofluoride minerals especially fluorapatite (FAP) and carbonate-fluorapatite (CFAP) were obviously precipitated from surfacewater and pore water Soluble salts of bromide and chloridewere formed in surface water and pore water Iodide salts(Ca(IO3)2 and Ca(IO3)26H2O) were moderately precipitatedin the surface water and pore water
Moreover the multivariate analysis including the cor-relation matrix multiple stepwise linear regression treeclustering and principle component (PCA) of all the de-termined and calculated variables was applied to estimatethe proposed interaction between halogens and other tested
10E + 02
16E + 0214E + 0212E + 02
80E + 0160E + 0140E + 0120E + 0100E + 00
1 2 3 4 5 6 7 8 9 10 11 12 13
HIIngHIDerm
(a)
1 2 3 4 5 6 7 8 9 10 11 12 13
HIIngHIDerm
40E ndash 0235E ndash 0230E ndash 0225E ndash 0220E ndash 0215E ndash 0210E ndash 0250E ndash 0300E + 01
(b)
Figure 6 Hazard index of ingestion and dermal contact of the studied variables in surface water and sediment of Lake Mariout (a) waterand (b) sediment
16 Journal of Chemistry
variables in the polluted area under study -e multivariateanalysis showed that there were many interactions betweenhalogens and tested variables High levels of fluoride bro-mide and chloride in surface water were related to thecomposition of drainage waters -e enrichment factor (EF)showed that Lake Mariout was not polluted However thehuman health adverse effects calculated for surface waterand sediment did not reflect any possible likelihood hazardeffects from halogens
Interestingly the current study concluded that halogencompounds especially fluorides are most likely to be de-posited from surface lakes in the form of many minerals andprecipitation thereby reducing the adverse pollution effectson human health -e results obtained through this workhelp to find the correlations between the sampling sites andthe variables obtained by physical and chemical measure-ments which can be used to construct a fast decision modelfor separating different water quality samples -is infor-mation may help the official authorities optimize manage-ment plans and strengthen their pollution control measuresin Lake Mariout
Data Availability
-e data used to support the findings of this research areincluded within the paper
Conflicts of Interest
-e authors declare that there are no conflicts of interestregarding the publication of this manuscript
Supplementary Materials
Supplementary Table 1 correlation matrix of variable insurface water pore water and sediment partitions besidesthe precipitated salts in surface water along Lake Mariout(Supplementary Materials)
References
[1] M S Masoud T O Said G El-Zokm and M A ShreadahldquoAssesment of heavy metals contamination in surface sedi-ments of the Egyptian Red Sea Coastsrdquo Australian Journal ofBasic and Applied Sciences vol 6 pp 44ndash58 2012
[2] M A Shreadah M I Abdel Moneim T O SaidE M I Fathallah and M E Mahmoud ldquoPAHs in seawater ofthe semi-closed areas along the Alexandria coast of EgyptianMediterranean seardquo Journal of Environmental Protectionvol 4 no 11 p 11 Article ID 40298 2013
[3] S Abdel Ghani G El Zokm A Shobier T Othman andM Shreadah ldquoMetal pollution in surface sediments of Abu-Qir bay and Eastern harbour of Alexandria Egyptrdquo EgyptianJournal of Aquatic Research vol 39 no 1 pp 1ndash12 2013
[4] G F El-Said ldquoBioaccumulation of key metals and othercontaminants by seaweeds from the Egyptian MediterraneanSea Coast in relation to human health riskrdquo Human andEcological Risk Assessment An International Journal vol 19no 5 pp 1285ndash1305 2013
[5] M A Shreadah A H Shobier S Abdel Ghani G M El-Zokm and T O Said ldquoMajor ions anomalies and
contamination status by trace metals in sediments from twohot spots along the Mediterranean Coast of Egyptrdquo Envi-ronmental Monitoring and Assessment vol 187 no 280pp 1ndash18 2015
[6] A El Nemr G F El-Said A Khaled and S Ragab ldquoDis-tribution and ecological risk assessment of some heavy metalsin coastal surface sediments along the Red Sea Egyptrdquo In-ternational Journal of Sediment Research vol 31 no 2pp 164ndash172 2016
[7] A El Nemr G F El-Said S Ragab A Khaled and A El-Sikaily ldquo-e distribution contamination and risk assessmentof heavy metals in sediment and shellfish from the Red Seacoast Egyptrdquo Chemosphere vol 165 pp 369ndash380 2016
[8] A El Nemr and G F El-Said ldquoAssessment and ecological riskof heavy metals in sediment and molluscs from the Medi-terranean coastrdquo Water Environment Research vol 89 no 3pp 195ndash210 2017
[9] M A Sheradah A A El-Sikaily N M Abd El MoneamN E Abd El Maguid and M G Zaki ldquoChemical and bio-chemical evaluation of marine pollution by polychlorinatedbiphenyls and pesticides in two regions along the EgyptianMediterranean Seardquo International Journal of EnvironmentalMonitoring and Analysis vol 6 no 3 pp 95ndash109 2018
[10] M A Shreadah A A-M M El-Sayed A A S TahaA-M M Ahmed and H H Abdel Rahman ldquoEvaluation ofdifferent anthropogenic effluents impacts on the water qualityusing principal component analysis a case study of Abu-QirBay-Alexandria-Egyptrdquo International Journal of Environ-mental Monitoring and Analysis vol 7 no 3 pp 56ndash67 2019
[11] G F El-Said M M El-Sadaawy A H Shobier andS E Ramadan ldquoHuman health implication of major and traceelements present in commercial crustaceans of a traditionalseafood marketing region Egyptrdquo Biological Trace ElementResearch vol 199 pp 315ndash328 2020
[12] M A Shreadah S A A Ghani H B I HawashA A E Samie and A E M M Ahmed ldquoOrganotin com-pounds in sediments of northern lakes Egyptrdquo Journal ofEnvironmental Protection vol 05 no 17 pp 1654ndash1666 2014
[13] A M Younis G M El-Zokm and M A Okbah ldquoSpatialvariation of acid-volatile sulfide and simultaneously extractedmetals in Egyptian Mediterranean Sea lagoon sedimentsrdquoEnvironmental Monitoring and Assessment vol 186 no 6pp 3567ndash3579 2014
[14] G F El-Said S E O Draz M M El-Sadaawy andA A Moneer ldquoSedimentology geochemistry pollution statusand ecological risk assessment of some heavy metals insurficial sediments of an Egyptian lagoon connecting to theMediterranean Seardquo Journal of Environmental Science andHealth Part A vol 49 no 9 pp 1029ndash1044 2014
[15] G M El Zokm M A Okbah and A M Younis ldquoAssessmentof heavy metals pollution using AVS-SEM and fractionationtechniques in Edku Lagoon sediments Mediterranean SeaEgyptrdquo Journal of Environmental Science and Health PartAvol 50 no 6 pp 571ndash584 2015
[16] G M El Zokm H R Z Tadros M A Okbah andG H Ibrahim ldquoldquoEutrophication assessment using TRIX andCarlsonrsquos indices in Lake Mariout water Egyptrdquo EgyptianJournal of Aquatic Biology and Fisheries vol 22 no 5pp 331ndash349 2018
[17] N Donia ldquoLake Maryut monitoring using remote sensingrdquo inProceedings of the gypt Eighteenth International WaterTechnology Conference IWTC18 Sharm El Sheikh Abu DhabiUAE March 2015
Journal of Chemistry 17
[18] M A Khairy ldquoAssessment of priority phenolic compounds insediments from an extremely polluted coastal wetland (LakeMaryut Egypt)rdquo Environmental Monitoring and Assessmentvol 185 no 1 pp 441ndash455 2013
[19] N A El-Naggar and E A Rifaat ldquoEgyptian coastal lakes andwetlands part Imdashcharacteristics and hydrodynamicsrdquo in eHandbook of Environmental Chemistry A M Negm EdSpringer International Publishing AG Berlin Germany 2017
[20] J J Hanley and K T Koga ldquoChapter 2 ldquohalogens in terrestrialand cosmic geochemical systems abundances Geochemicalbehaviors and analytical methodsrdquordquo in e Role of Halogensin Terrestrial and Extraterrestrial Geochemical ProcessesD E Harlov and L Aranovich Eds Springer InternationalPublishing AG Berlin Germany pp 21ndash121 2018
[21] A Ghosh K Mukherjee S K Ghosh and B Saha ldquoSourcesand toxicity of fluoride in the environmentrdquo Research onChemical Intermediates vol 39 no 7 pp 2881ndash2915 2013
[22] M M Naim A A Moneer and G F El-Said ldquoPredictiveequations for the defluoridation by electrocoagulation tech-nique using bipolar aluminum electrodes in the absence andpresence of additives a multivariate studyrdquo Desalination andWater Treatment vol 57 no 14 pp 6320ndash6332 2016
[23] G F El-Said N A Shaltout M M El-Sadaawy andA M H Morsy ldquo-e precipitation of fluoride calcium andmagnesium minerals from Egyptian Mediterranean Sea coastin relation to discharged watersrdquo Desalination and WaterTreatment vol 57 no 5 pp 2113ndash2124 2016
[24] H Bureau ldquoIodine encyclopedia of geochemistry A com-prehensive reference source on the chemistry of the earthrdquo inEncyclopedia of Earth Sciences Series W M White Ed copySpringer International Publishing AG 2016
[25] F C Kupper and C J Carrano ldquoKey aspects of the iodinemetabolism in brown algae a brief critical reviewrdquo Metal-lomics vol 11 pp 756ndash764 2019
[26] R Liteplo R Gomes P Howe and H Malcolm Fluorides-Environmental Health Criteria 227 p 290 World HealthOrganization (WHO) Geneva Switzerland 2002
[27] G F El-Said and M M El-Sadaawy ldquoSeasonal variation ofboron and fluoride in Tilapia nilotica from an Egyptian fishfarm in relation to Human health hazard assessmentrdquoHumanand Ecological Risk Assessment An International Journalvol 19 no 4 pp 930ndash943 2013
[28] WHO (World Health Organization) Bromide in Drinking-Water Background Document for Development of WHOGuidelines for Drinking-Water Quality WHO Press WorldHealth Organization Geneva Switzerland 2009
[29] G F El-Said and N A Sallam ldquo-e uptake of fluorideconcentration and its effects on the growth rate of shrimps(Palaemon elegans Rathke)rdquo Chemistry and Ecology vol 24no 3 pp 191ndash205 2008
[30] X Zhang J He B He and J Sun ldquoAssessment formationmechanism and different source contributions of dissolvedsalt pollution in the shallow groundwater of Hutuo Riveralluvial-pluvial fan in the North China Plainrdquo EnvironmentalScience and Pollution Research vol 26 no 35 pp 35742ndash35756 2019
[31] Y Zhu B Huang Z Zhu et al ldquoldquoCharacterization disso-lution and solubility of the hydroxypyromorphitendashhydroxyapatite solid solution [(PbxCa1minusx)5(PO4)3OH] at25 degC and pH 2ndash9rdquo Geochemical Transactions vol 17 no 2pp 1ndash18 2016
[32] G F El-Said M M El-Sadaawy A A Moneer andN A Shaltout ldquo-e effect of fluoride on the distribution ofsome minerals in the surface water of an Egyptian lagoon at
the Mediterranean Seardquo Egyptian Journal of Aquatic Researchvol 41 no 1 pp 31ndash39 2015
[33] Y Zhu Z Zhu X Zhao Y Liang and Y Huang ldquoChar-acterization dissolution and solubility of lead hydroxypyr-omorphite [Pb5(PO4)3OH] at 25ndash45degCrdquo Journal ofChemistry vol 2015 Article ID 269387 10 pages 2015
[34] M A Z Chahouki ldquoMultivariate analysis techniques inenvironmental sciencerdquo in Earth and Environmental SciencesDr Imran Ahmad Dar Ed InTech Open London UK 2011httpwwwintechopencombooksearth-and-environmental-sciencesmultivariate-analysis-techniques-inenvironmental-science
[35] J V Klump and C S Martens ldquoBiogeochemical cycling in anorganic-rich coastal marine basin 5 Sedimentary nitrogenand phosphorus budgets based upon kinetic models massbalances and the stoichiometry of nutrient regenerationrdquoGeochimica et Cosmochimica Acta vol 51 no 5 pp 1161ndash1173 1987
[36] R L Folk Petrology of Sedimentary Rocks University of TexasAustin TX USA 1974
[37] P Saenger ldquoA rapid spectrophotometric method for thedetermination of bromine in seawater and in the ash ofmarine algaerdquo Helgolander Wissenschaftliche Meer-esuntersuchungen vol 23 no 1 pp 32ndash37 1972
[38] P G Jeffery Chemical Methods of Rock Analysis PergamonPress New York NY USA 2nd edition 1975
[39] J D H Strickland and T R Parsons ldquoA practical handbook ofseawater analysisrdquo in Fisheries Research Board of CanadaBulletin 167p 311 Second edition Wiley Ottawa Canada1972
[40] B Horvath O Opara-Nadi and F Beese ldquoA simple methodfor measuring the carbonate content of soilsrdquo Soil ScienceSociety of America Journal vol 69 no 4 pp 1066ndash1068 2005
[41] K Grasshoff Methods of Seawater Analysis p 317 VerlagChemie Weinkeim Germany 1976
[42] R Danovaro D Marrale N Della Croce P Parodi andM Fabiano ldquoBiochemical composition of sedimentary or-ganic matter and bacterial distribution in the Aegean Seatrophic state and pelagic-benthic couplingrdquo Journal of SeaResearch vol 42 no 2 pp 117ndash129 1999
[43] APHA-AWWA-WPCF (American Public Health Associa-tion) Standard Methods for the Examination of Water andWaste Water American Public Health Association Wash-ington DC USA 20th edition 1999
[44] K I Aspila H Agemian and A S Y Chau ldquoA semi-auto-mated method for the determination of inorganic organicand total phosphate in sedimentsrdquo e Analyst vol 101no 1200 pp 187ndash197 1976
[45] J P Riley and D Taylor ldquoChelating resins for the concen-tration of trace elements from sea water and their analyticaluse in conjunction with atomic absorption spectrophotom-etryrdquo Analytica Chimica Acta vol 40 pp 479ndash485 1968
[46] G F El-Said and A El-Sikaily ldquoChemical composition ofsome seaweed from Mediterranean Sea coast Egyptrdquo Envi-ronmental Monitoring and Assessment vol 185 no 7pp 6089ndash6099 2013
[47] Directorate General of Health Services Ministry of Health andFamilyWelfare Government of India ldquoManual of methods ofanalysis of foodsrdquo in Fruit and Vegetable Productsp 57Directorate General of Health Services Ministry of Health andFamily Welfare Government of India New Delhi India2005
[48] A Gunnars S Blomqvist and C Martinsson ldquoInorganicformation of apatite in brackish seawater from the Baltic Sea
18 Journal of Chemistry
an experimental approachrdquo Marine Chemistry vol 91 no 1-4 pp 15ndash26 2004
[49] W M Haynes D R Lide and T J Bruno CRC Handbook ofChemistry and Physics A Ready Reference Book of Chemicaland Physical Data CRC Press Taylor amp Frances Group BocaRaton FL USA 97th edition 2017
[50] M S Masoud M I El-Samra and M M El-Sadawy ldquoWaterchemistry of el-mex bay west of Alexandria Egyptrdquo eEgypian Science Magazine vol 2 pp 70ndash78 2005
[51] F J Millero R Feistel D G Wright and T J McDougallldquo-e composition of standard seawater and the definition ofthe reference-composition salinity scalerdquo Deep Sea ResearchPart I Oceanographic Research Papers vol 55 no 1pp 50ndash72 2008
[52] S K El-Wakeel S A Morcos and A M Mahlis ldquo-e majorcations in Lake Maryut watersrdquo Hydrobiologia vol 36 no 2pp 253ndash274 1970
[53] A M Mahlis S A Morcos and S K El-Wakeel ldquo-e majoranions in Lake Maryut watersrdquo Hydrobiologia vol 36 no 2pp 275ndash294 1970
[54] A S Saad M A Massoud R A Amer and M A GhorabldquoAssessment of the physico-chemical characteristics andwater quality analysis of Mariout Lake southern of Alexan-dria Egyptrdquo Journal of Environmental and Analytical Toxi-cology vol 7 no 1 p 421 2017
[55] R Rumuri ldquoDataset on hydrogeochemical characteristics ofgroundwater and surface water in Kattumannarkoil TalukIndiardquo Data in Brief vol 32 Article ID 106058 2020
[56] P Szefer S W Fowler K Ikuta et al ldquoA comparative as-sessment of heavy metal accumulation in soft parts and byssusof mussels from subarctic temperate subtropical and tropicalmarine environmentsrdquo Environmental Pollution vol 139no 1 pp 70ndash78 2006
[57] N F Soliman G M El Zokm and M A Okbah ldquoRisk as-sessment and chemical fractionation of selected elements insurface sediments from Lake Qarun Egypt using modifiedBCR techniquerdquo Chemosphere vol 191 pp 262ndash271 2018
[58] G M El Zokm M I A Ibrahim L A Mohamed and M El-Mamoney ldquoCritical geochemical insight into Alexandria coastwith special reference to diagnostic ratios (TOCTN amp SrCa)and heavy metals ecotoxicological hazardsrdquo Egyptian Journalof Aquatic Research vol 46 no 1 pp 27ndash33 2020
[59] A S Likuku K B Mmolawa and G K GaboutloeloeldquoAssessment of heavy metal enrichment and degree of con-tamination around the copper-nickel mine in the SelebiPhikwe Region Eastern Botswanardquo Environment and EcologyResearch vol 1 no 2 pp 32ndash40 2013
[60] M K Khalil S E O Draz G M El Zokm and G F El-SaidldquoApportionment of geochemistry texturersquos properties and riskassessment of some elements in surface sediments from Bar-dawil Lagoon Egyptrdquo Human and Ecological Risk AssessmentAn International Journal vol 22 no 3 pp 775ndash791 2016
[61] M M El-Sadaawy and G F El-Said ldquoAssessment of fluoridein three selected polluted environments along the EgyptianMediterranean Sea effects on local populationsrdquo Human andEcological Risk Assessment An International Journal vol 20no 6 pp 1643ndash1658 2014
[62] USEPA ldquoSuperfund exposure assessment manualrdquo inOSWER Directive 92855-1EPA540l-88001Office of Emer-gency and Remedial Response Washington DC USA 1988
[63] USEPA ldquoExposure factors handbookrdquo in EPA6008-89043Office of Health and Environmental Assessment Wash-ington DC USA 1989
[64] Health Canada ldquoFederal Contaminated Site Risk Assessmentin Canadardquo Part II Health Canada Toxicological ReferenceValues (TRVs) Cat H46-204-368E Calgary Health CanadaOttawa Canada 2007
[65] J Iqbal S A Tirmizi and M H Shah ldquoStatistical appor-tionment and risk assessment of selected metals in sedimentsfrom Rawal Lake (Pakistan)rdquo Environmental Monitoring andAssessment vol 185 no 1 pp 729ndash743 2013
[66] USEPA (US Environmental Protection Agency) Region 6USAEPA ldquoMultimedia Planning and Permitting DivisionrdquoOffice of Solid Waste Center for Combustion Science andEngineering Washington DC USA 2005
[67] P Jeschke ldquoLatest generation of halogen-containing pesti-cidesrdquo Pest Management Science vol 73 no 6 pp 1053ndash10662017
[68] M A Shreadah O A El-Rayis N A Shaaban andA M Hamdan ldquoWater quality assessment and phosphorusbudget of a lake (Mariut Egypt) after diversion of wastewaterseffluentsrdquo Environmental Science and Pollution Researchvol 27 no 21 pp 26786ndash26799 2020
[69] J P Riley and M Tongudai ldquo-e major cationchlorinityratios in sea waterrdquo Chemical Geology vol 2 pp 263ndash2691967
[70] R B McCleskey D K Nordstrom D D Susong J W Balland J M Holloway ldquoSource and fate of inorganic solutes inthe gibbon river yellowstone national park Wyoming USArdquoJournal of Volcanology and Geothermal Research vol 193no 3-4 pp 189ndash202 2010
[71] G T F Wong and K-Y Li ldquoWinklerrsquos method overestimatesdissolved oxygen in seawater iodate interference and itsoceanographic implicationsrdquo Marine Chemistry vol 115no 1-2 pp 86ndash91 2009
[72] B S R V Prasad P D N Srinivasu P S VarmaA V Raman and S Ray ldquoDynamics of dissolved oxygen inrelation to saturation and health of an aquatic body a case forChilka Lagoon Indiardquo Journal of Ecosystems vol 2014 Ar-ticle ID 526245 17 pages 2014
[73] China Environmental Protection Agency EnvironmentalQuality Standards for Surface Water (GB3838ndash2002) NationalEnvironmental Protection Agency of China Beijing China2002
[74] Y Jia L Wang Z Qu and Z Yang ldquoDistribution con-tamination and accumulation of heavy metals in watersediments and freshwater shellfish from Liuyang RiverSouthern Chinardquo Environmental Science and Pollution Re-search vol 25 no 7 pp 7012ndash7020 2018
[75] A Moneer M El-Sadawy G El-Said and A Radwan ldquoBoronhuman health risk assessment relative to the environmentalpollution of Lake Edku Egyptrdquo Journal of King AbdulazizUniversity vol 23 no 2 pp 41ndash55 2012
[76] C B Tabelin T Igarashi T Arima D Sato T Tatsuhara andS Tamoto ldquoCharacterization and evaluation of arsenic andboron adsorption onto natural geologic materials and theirapplication in the disposal of excavated altered rockrdquo Geo-derma vol 213 pp 163ndash172 2014
[77] G Aloisi K Wallmann M Drews and G BohrmannldquoEvidence for the submarine weathering of silicate minerals inBlack Sea sediments possible implications for the marine Liand B cyclesrdquo Geochemistry Geophysics Geosystems vol 5no 4 pp 1ndash22 2004
[78] C Degueldre and V Cloet ldquoPore water colloid properties inargillaceous sedimentary rocksrdquo Science of e Total Envi-ronment vol 569-570 pp 423ndash433 2016
Journal of Chemistry 19
[79] J A Higgins and D P Schrag ldquoRecords of Neogene seawaterchemistry and diagenesis in deep-sea carbonate sedimentsand pore fluidsrdquo Earth and Planetary Science Letters vol 357-358 pp 386ndash396 2012
[80] H Schroeder A-L Fabricius D Ecker T A Ternes andL Duester ldquoMetal(loid) speciation and size fractionation insediment pore water depth profiles examined with a newmesoprofiling systemrdquo Chemosphere vol 179 pp 185ndash193 2017
[81] Y Song and G Muller ldquoFreshwater sediments sinks andsources of brominerdquo Naturwissenschaften vol 80 no 12pp 558ndash560 1993
[82] M E Goher H I Farhat M H Abdo and S G Salem ldquoMetalpollution assessment in the surface sediment of Lake NasserEgyptrdquo Egyptian Journal of Aquatic Research vol 40 no 3pp 213ndash224 2014
[83] G F El-Said M M El-Sadawy and A A Moneer ldquoIncor-poration of fluoride and boron into surface sediments alongthe Egyptian Mediterranean coastrdquo Egyptian Journal ofAquatic Research vol 36 no 4 pp 569ndash583 2010
[84] B Gilfedder G M Petri M Wessels and H Biester ldquoAniodine mass-balance for Lake Constance Germany insightsinto iodine speciation changes and fluxesrdquo Geochimica etCosmochimica Acta vol 74 no 11 pp 3090ndash3111 2010
[85] E Korobova L Kolmykova B Ryzhenko et al ldquoDistributionand speciation of iodine in drinking waters from geochem-ically different areas of Bryansk region contaminated after theChernobyl accident in relation to health and remediationaspectsrdquo Journal of Geochemical Exploration vol 184pp 311ndash317 2018
[86] V Zic V W Truesdale and N Cukrov ldquo-e distribution ofiodide and iodate in anchialine cave watersmdashevidence forsustained localised oxidation of iodide to iodate in marinewaterrdquoMarine Chemistry vol 112 no 3-4 pp 168ndash178 2008
[87] M B Heeb J Criquet S G Zimmermann-Steffens andU Von Gunten ldquoOxidative treatment of bromide-containingwaters formation of bromine and its reactions with inorganicand organic compoundsmdasha critical reviewrdquo Water Researchvol 48 pp 15ndash42 2014
[88] V Sivasankar A K Darchen and R Omine SakthivelldquoChapter 2 ldquofluoride a world ubiquitous compound itschemistry and ways of contaminationrdquo in Surface ModifiedCarbons as Scavengers for Fluoride fromWater V SivasankarEd pp 5ndash32 copy Springer International Publishing Switzer-land Cham Switzerland 2016
[89] O Cabestrero P Del Buey and M E Sanz-Montero ldquoBio-sedimentary and geochemical constraints on the precipitationof mineral crusts in shallow sulphate lakesrdquo SedimentaryGeology vol 366 pp 32ndash46 2018
[90] M A Hassaan O A El-Rayis and E I Hemada ldquoEstimationof the redox potential of lake mariut drainage system (Qalaaand Umum drains)rdquoHydrology vol 5 no 6 pp 82ndash85 2017
20 Journal of Chemistry
yearminus1) AF was the adherence factor (007mg cmminus2) andABS was the dermal absorption factor (0001 unit less)[65 66]
Hazard index (HI) is the total chronic hazard attribut-able to exposure to all determined contaminants (i) througha single exposure pathway of the ingestion and dermalcontact of water (HIIngw and HIDermw) and sediment (HIIngsand HIDerms) was given as follows [60]
HIIngW 1113944HQ IngW( 1113857i (8)
HIDermW 1113944HQ DermW( 1113857i (9)
HIIngS 1113944HQ IngS( 1113857i (10)
HIDermS 1113944HQ DermS( 1113857i (11)
3 Results and Discussion
31 Distribution of Halogens and Tested Variables in SurfaceWater
311 Distribution of Halogens in Surface Water -e rangeand average value of halogens in the surface water in thisstudy show a sequence of ClwgtBrwgt Fwgt Iw (Table 2 andFigure 2)-e current study indicate that the water sample ofpumping station (site 6) attained high concentrations offluoride (28mg Lminus1) chloride (38878mg Lminus1) and bromide(181mg Lminus1) and low iodide (641 μg Lminus1) contents (Fig-ure 2) High levels of F Br and I are detected in the MainBasin region which is affected by the drainage of El-Qalaaand El Umoum containing the agricultural and industrialwastes However halogens are involved in the manufactureof pesticides (herbicides fungicides insecticidesacaricidesand nematicides) [67] Plus halogens are produced in theproduction of fertilizers products [67] -e presented resultsof halogens in the studied lake region reflect anomalousdistribution and are mainly affected by water dischargedfrom the drainage sources However the highest fluoridebromide and iodide contents of 377mg Lminus1 6553mg Lminus1and 5410 μg Lminus1 respectively are recorded in the MainBasin affected by El-Qalaa and El Umoum drains Amongthe halogens chloride shows high levels in surface waterespecially in site 1 (72837mg Lminus1) site 2 (65218mg Lminus1)and site 10 (51687mg Lminus1) which are also related to theirlevels in the water of the drains (Figure 2) On the meantimethe lowest Spermilw and Clpermilw are observed at site 13 (ElUmoum Drain) Most of the studied variables have chlo-rinity ratios relatively lower than those measured for LakeMariout andor seawater [51ndash53 68 69] -is is mainly dueto the accumulation of wastewater from Abis and ElUmoum where agricultural products such as fertilizers andbiocides are deposited in industrial products [19]
Due to the increase in chloride content in surface watersamples the conservativeness of the chlorinity ratio is usedto describe the contamination precipitation and dissolutionof sediment components [70] -e FCl ratio in the studyarea is higher than open seawater (430Eminus 05) of a range
430Eminus 05ndash140Eminus 03 and average 540Eminus 04 -e BrClratio is relatively similar to that of seawater (Table 2) -ehighest FCl BrCl and ICl ratios in surface water140Eminus 03 160E ndash 02 and 160Eminus 02 are recorded in site 13(El Umoum drain outside the lake) site 9 (South West Basinin the lake) and site 4 (Main Basin in the lake) -erefore itcan be concluded that the distribution of halogens in thesurveyed area is greatly affected by the drainage of the El-Qalaa El Umoum and the El Nubaria drains
312 Distribution of Tested Variables in Surface Water-e range and average values of the tested variables (Tw Spermilw Clpermilw TDSw turbidity DOw pHw CO3w HCO3w BwPw Siw Caw Mgw Naw Kw Liw SO4w Cuw Mnw Few andZnw) in surface waters of the present study are listed inTable 2 Turbidity fluctuates from 166 to 3850 NTU at sites8 and 12 respectively DO is completely depleted at sites 5 6and 11 and has the highest amount 1241mg Lminus1 at site 2with an average 605mg Lminus1 relatively similar to the reportedLake Mariout value (214ndash563mg Lminus1 [54]) (Table 2) -eaverage content of DO in the lake is higher than those re-ported for the ocean seawater (32ndash48mgL) [71] -e levelsof DO probably relate to the oxygen-producing processes ofthe photosynthesis processes of phytoplankton and mac-rophytes [72] -e presented results indicate that site 1(affect by Abis drainage) is the most affected area in the lakeas it shows the highest contents of Bw Clw Mgw Naw KwLiw and SO4w -e most important feature in the concen-trations of heavy metals Cuw Mnw and Znw in surface wateris that they possess average values lower than those reportedfor the threshold guideline (10 100 and 50 μg Lminus1) [73 74]
-e present study clears out a descending trend in thesurface water average concentrations of halogens andtested variables in the lake as follows TDSw gtClw gtNaw gtMgw gtCaw gt SO4w gtHCO3wgtKw gtCO3w gt Bw gt Brwgt FwgtLiw gt Znw gt Few asymp Siw gtMnw gt Pw gt Iw (Table 2)
313 Interactions of Halogens and Tested Variables inSurface Water Chloride in surface water is significantlyrelated to the drainage water content showing good cor-relations with Tw (r 0631 ple 0028) and pHw (r 0769ple 0003) (Supplementary Table 1) -e negative moderaterelation of Fw and Ip (r 0606 ple 0037) may indicatereplacement of iodine in pore water by fluoride of the surfacewater-emoderate relationship between fluoride in surfacewater and CO3w (r minus0632 ple 0027) and HCO3w(r 0593 ple 0042) may be related to carbonate exchangeand the formation of fluorite minerals (CaF2) [23]
-e correlation matrix reflects that the observed ex-traordinary levels of Bw in the surface water samples aremost probably due to its exchange with the different sedi-ment components not related to the discharged waters(Supplementary Table 1) -is findings is supported by theweak B correlation with Cuw (r minus0587 ple 0045) andgood correlation with Fs (r minus0666 ple 0018) [75 76]However Cuw is one of the pollutants that can be exchangedin drainage water -e correlations of Mgw amp Naw (r 0629
Journal of Chemistry 7
1
23
4
56
7
8
9
10
2986degE 2988degE 2990degE 2992degE
310
8degN
311
0degN
311
2degN
311
4degN
311
6degN
El-mex
pumping
statio
n Main Basin
of Lake Maryout
Southwest Basin
Qalaa Drain
El Umoum Drain
Northwest BasinFish
ery Basi
nEl Nubaria Drain
3311 to 38883888 to 43934393 to 5115
5115 to 65226522 to 7284
(a)
1
23
4
56
7
8
9
10
2986degE 2988degE 2990degE 2992degE
310
8degN
311
0degN
311
2degN
311
4degN
311
6degN
El-mex
pumping
statio
n
Main Basinof Lake Maryout
Southwest Basin
Qalaa Drain
El Umoum Drain
Northwest Basin
Fishery
BasinEl Nubaria Drain
069 to 127127 to 169169 to 242
242 to 277277 to 377
(b)
El-mex
pumping
statio
n
Main Basin of Lake Maryout
South west Basin
North west Basin
1
23
4
56
7
8
9
10
2986degE 2988degE 2990degE 2992degE
310
8degN
311
0degN
311
2degN
311
4degN
311
6degN
Qalaa Drain
El Umoum Drain
Fishery
BasinEl Nubaria Drain
613 to 852852 to 14381438 to 1732
1732 to 52745274 to 6554
(c)
El-mex
pumping
statio
n
Main Basin of Lake Maryout
Southwest Basin
Northwest Basin
1
23
4
56
7
8
9
10
2986degE 2988degE 2990degE 2992degE
310
8degN
311
0degN
311
2degN
311
4degN
311
6degN
Qalaa Drain
El Umoum Drain
Fishery
BasinEl Nubaria Drain
566 to 671671 to 761761 to 817
817 to 922922 to 5411
(d)
Figure 2 Distribution of halogens (Cl F Br and I in surface water of LakeMariout (a) Cl (mg Lminus1) (b) F (mg Lminus1) (c) Br (mg Lminus1) and (d) I(μg Lminus1)
8 Journal of Chemistry
ple 0028) Mgw amp Liw (r 0790 ple 0002) Naw amp Kw(r 0955 ple 0000 Naw amp Liw (r 0835 ple 0001) Naw ampCO3w (r minus0701 ple 0011) Kw amp Liw (r 0712 ple 0009)Kw amp CO3w (r minus0580 ple 0048) CO3w amp HCO3w(r minus0613 ple 0034) and Mgw amp SO4w (r 0631ple 0028) indicate that all these variables have some geo-chemical behaviors [77] Mg Na and Li are some com-ponents of the discharged waters however they havepositive correlations with the chlorinity and salinity of thedischarged water sources (r 0743 0619 and 0815 re-spectively) and (r 0743 0619 and 0815 respectively)Mgw and Liw contents in water samples are affected bytemperature dissolved oxygen and pH with high correla-tions of r minus0650 0677 and 0743 and minus0702 0659 and0815 respectively
32 Distribution of Halogens and Tested Variables in PoreWater
321 Distribution of Halogens in Pore Water -e averagehalogen contents in the pore water are higher than theircontents in the surface water but in the same orderClpgtBpgt Fpgt Ip (Table 3) Current research shows that thelowest and highest average values of Spermilp and Clp have beenmeasured in the pore water of site 6 and site 8 respectively Itis worth mentioning that site 6 is a mixed water of El-Qalaadrainage sewage WWTP treatment plant and lake waterInterestingly the high concentrations of fluoride chloridebromide and iodide in the pore water at site 6 are 123mgLminus1 40321mg Lminus1 11739mg Lminus1 and 24339 μg Lminus1 re-spectively (Table 3) -e salinity and chloride content in thepore water of site 8 are related to the discharge water of manypetrochemical and oil companies besides some fish farms
322 Distribution of Tested Variables in Pore Water -etested variables in the pore water (p) give the followingdescending order MgpgtNapgtCapgt SO4pgtBpgtKpgtBrpgt Fpgt LipgtPpgt Ipgt Sip (Table 3) Interestingly the deter-mined variables in the pore water have higher values thanthe surface water along the lake According to previousstudies pore water is responsible for biogeochemical reac-tions the migration and transformation of partitioned andformed compounds and the transportation of colloidalspecies [78 79] In addition pore water can explore thepotential risks of man-made pollution sources [80] -etested variables in the pore water (p) are given in a differentorder of surface water of ClpgtMgpgtNapgtCapgt SO4pgtBpgtKpgtBrpgt Fpgt Lipgt Ppgt Ipgt Sip (Tables 2and 3)
323 Interactions of Halogens and Tested Variables in PoreWater -e following interactions of halogens CO3w amp Ip Ipamp Fw Brw amp Sip Fp amp Siw and Fp amp Nap give correlationvalues (r 0706 ple 0010 r minus0606 ple 0037 r 0826ple 0001 r minus0704 ple 0011 and r 0670 ple 0017respectively) (Supplementary Table 1) However these re-lationships may indicate their precipitation andor
adsorption on the colloidal particles besides the formation ofsome chemical species [78 79] Extraordinarily large cor-relations of Nap amp HCO3w Kp amp HCO3w Spermilw amp Bp Spermilp ampKp Spermilp amp Lip and Spermilp amp Clp (r 0692 minus0609 minus07410696 0910 and 1000) may refer to the release of theseelements from sediment particles andor precipitation oradsorption [77] In the matrix the negative correlationbetween Cap and Mgp (r minus0592 ple 0042) may be relatedto the release of Mg during the recrystallization of calcite[79]-e relationship between Caw amp SO4p Cuw amp Cap Pw ampPp and Nap amp pHw (r 0744 ple 0006 r 0719 ple 0008r 0647 ple 0023 and r minus0640 ple 0025 respectively)may be due to the chemical interactions in the pore fluidsand the formation certain compounds
33Distribution ofHalogens andTestedVariables in Sediment
331 Distribution of Halogens in Sediment -e averagehalogenrsquos content in the sediment shows a different orderfrom the surface and pore waters of Brsgt FsgtClsgt Is (Ta-ble 4) -e sediment results show that the average bromidecontent is higher than fluoride followed by chloride contentand iodide with average values of 452mg gminus1 040mg gminus1029mg gminus1 and 450 μg gminus1 respectively
-e fluoride concentration in the sediment ranges from001 to 120mg gminus1 with an average value of 04plusmn 035mggminus1 -ese values are lower than reported marine sedimentvalues and higher than the El-Bardawil Lagoon [60]Amongst the halogens the study reveals that Br is the mostabundant ion in surface water pore water and sedimentsamples due to the excessive amounts of organic matter [81]On the contrary the concentration of Cl ions in sedimentsamples is lower than that in surface water and pore watersamples indicating that it exists in soluble salts -e currentresults indicate that the sediments collected from the mostaffected area by the Mediterranean Sea (site 6) contain el-evated levels of fluoride (070mg gminus1) bromide (852mggminus1) and chloride (020mg gminus1) and a reduced amount ofiodide (209 μg gminus1) (Table 4)
332 Distribution of Tested Variables in Sediment -eaverage value of test variables in the determined sedimentsamples shows a significant change from site to site with adescending order CO3sgtMgsgtCasgtNasgt SO4s gt FesgtBsgtKsgtTPsgtMn sgtZnsgtCusgt Lis (Table 4) Plus this studyclears out that the percent of sand and mud of the differentsediment samples ranges from 4 at sites 1 amp 13 to 85 atsite 11 and from 15 at site 11 to 96 at sites 1amp13 re-spectively with averages 25 and 75 respectively Plusthe porosity shows a trend opposite to the particle size andvaries from 4676 to 8214 with an average value of5609plusmn 1114 -e results of the current study reveal mod-erate amounts of CO3 in the sediment samples fluctuatingbetween 1639 and 5736 at sites 6 and 2 respectively -eresults of sand mud porosity and CO3 percentage reflect thatthe texture of the sediment is mainly composed of mud mixedwith carbonate compounds Comprehensively the large storageof sediments with carbonate (359plusmn1280) magnesium
Journal of Chemistry 9
Tabl
e3
Distribu
tionof
thestud
iedvariablesin
thepo
rewater
(p)alon
gLake
Mariout
Site
Spermilp
pHP
Ca p
(mgLminus
1 )Mg p
(mgLminus
1 )Na p
(mgLminus
1 )Kp
(mgLminus
1 )Li
p(m
gLminus
1 ))
SO4P
(mgLminus
1 ))
B P(m
gLminus
1 ))
P P(μgLminus
1 ))
SiP
(microgLminus
1 ))
F p(m
gLminus
1 ))
Cl P
(mgLminus
1 ))
Brp
(mgLminus
1 ))
I p(μgLminus
1 )1
1034
787
481
42303
1097
453
042
2944
8043
363
0045
323
95419
959
7104
2934
809
5611
115725
1050
498
039
2056
663
553
0036
338
8398
1385
24698
31272
717
100
5689
1195
577
053
2778
8949
1204
0034
754
114469
2291
26347
483
796
9619
47652
974
384
043
350
19312
77
0054
215
74599
693
8393
51099
782
5611
89711
1128
42041
1667
16739
1112
0081
1698864
1332
8333
645
775
4008
75367
736
41024
2111
11739
071
0037
1231
40321
799
24339
71125
782
39278
13615
1155
516
056
3667
6051
369
006
6101209
1279
8123
8148
775
9299
84314
1355
468
055
12444
942
212
0056
892
133232
1172
7643
9684
78
962
72109
880
393
036
3778
21341
114
0087
1061429
2131
9981
10114
764
1122
113586
1195
524
049
4667
8007
071
0041
1138
102562
1332
8572
11639
742
4008
61996
915
332
033
2833
11594
754
0026
1215
67834
746
37587
125
702
481
38413
8703
274
028
2167
13913
081
0025
2154
44832
1438
9891
13755
807
3206
6467
817
446
039
4556
17246
635
0042
954
5737
533
1097
Minim
um45
702
962
13615
736
274
024
1667
6051
071
0025
215
40321
533
7104
Maxim
um148
809
39278
115725
8703
577
056
12444
21341
1204
0087
2154
133232
2291
37587
Average
919
77
718
67412
163077
4381
041
3782
1223
485
0048
955
82779
1238
14768
SD308
032
10027
29209
2132
825
01
2769
5047
391
0019
542
27891
524
9917
10 Journal of Chemistry
Tabl
e4
Distribu
tionof
thestud
iedvariablesin
thesediment(s)alon
gLake
Mariout
Site
Sand
()
Mud ()
Porosity
()
CO3s
()
B s(m
ggminus
1 )P s
(mg
gminus1 )
Ca s
(mg
gminus1 )
Mg s
(mg
gminus1 )
Na s
(mg
gminus1 )
Ks
(mg
gminus1 )
Lis(m
ggminus
1 )
SO4s
(mg
gminus1 )
Fes
(mg
gminus1 )
Cu s (μg
gminus1 )
Mn s
(μg
gminus1 )
Zns(μg
gminus1 )
F s(m
ggminus
1 )
Cl s
(mg
gminus1 )
Brs
(mg
gminus1 )
I s(μg
gminus1 )
14
964915
183
299
044
1670
811
2583
408
0028
4861
828
963
5617
1272
034
041
128
1686
244
564925
574
196
028
1002
1419
2717
269
0015
662
257
793
4350
1313
057
054
123
358
319
816667
299
246
073
1670
1216
3125
336
0022
463
487
1228
4330
1677
044
034
448
516
418
824853
3813
1111
032
668
2229
3425
365
0094
2222
770
922
4637
1245
030
020
309
296
512
884697
482
614
012
501
1115
1833
091
0040
1713
243
600
27933
1223
082
034
245
254
65
954667
164
370
157
835
1257
2958
388
0030
5648
890
1927
5347
3117
070
020
852
209
75
954762
375
524
024
367
2047
3133
256
0102
1157
546
883
4185
1393
120
020
341
259
838
626143
457
697
039
668
1621
3550
347
0145
4167
598
737
4157
1412
022
034
144
1277
918
826000
349
083
054
401
1094
3358
369
0025
2454
701
868
5702
3065
036
027
250
172
1036
645070
441
296
002
935
1763
3117
246
0045
2685
369
790
4533
1315
012
047
1012
224
1185
157000
325
240
074
969
2250
3508
328
0193
1343
1026
735
3890
1070
005
007
533
128
1237
638214
463
291
032
334
1824
3008
358
0018
556
340
728
2475
827
001
007
852
281
134
965000
177
211
054
2338
1621
3925
599
0068
833
1687
1187
6492
1853
004
027
639
194
Min
415
4667
164
083
002
334
811
1833
091
0015
463
243
600
2475
827
001
007
123
128
Max
8596
8214
574
1111
157
2338
2250
3925
599
0193
6620
1687
1927
6492
3117
120
054
1012
1686
Av
2575
5609
359
398
048
951
1559
3096
335
0063
2671
672
951
4500
1599
040
029
452
450
SD23
231114
128
276
039
603
455
522
115
0055
2030
393
343
1120
708
035
014
303
475
Minm
inim
umM
axm
axim
uma
ndAv
averageSD
stand
arddeviation
Journal of Chemistry 11
(1559plusmn455mg gminus1) and calcium (951plusmn603mg gminus1) com-ponents may be attributed to the abundance of calcium min-erals [4] However in general the average amounts of allvariables in sediment samples showmarked variations fromonesite to another with a descending order of CO3sgtMgsgtCasgtNasgtSO4sgtFesgt BrsgtBsgtKsgtTPsgtFs gtClsgtMnsgtZnsgtCusgtLisgt Is (Table 4) -e measured concentra-tions of Mn Zn Cu and Fe in the sediment samples are stilllower than the reported values and also lower than the back-ground levels of crust and the toxicological reference contents ofUS DOE (US Department of Energy) US EPA (US Envi-ronmental Protection Agency) and CEQG (Canadian Envi-ronmental Quality Guidelines) [82]
Contrasting the obtained levels for the halogens withthose previously reported ones the present study indicatesthat surface and pore waters incorporate more considerableamounts of fluoride compared to the formerly reported onesin Lake Edku (Tables 2 and 3) and lower levels in theMarioutarea than those measured along the Egyptian MediterraneanSea coast [27] Compared with the sediments previouslyfound on the Mediterranean coast of Egypt the chloridecontent in the sediments of the Mariout area is lower [83]Compared with those observed in seawater the studiedsurface water and pore water samples have lower bromidecontent and higher levels than previously reported in LakeMariout [52 53] -e concentration of iodide in surfacewater pore water and sediments is equivalent to the con-centration of rivers and lakes in the world [84]
333 Interactions of Halogens and Tested Variables inSediment -e correlation matrix shows the important roleof halogens in the formation and precipitationdissolution ofsalts and minerals produced along the lake (SupplementaryTable 1) However it shows that chloride seems to be in thesoluble forms along the surface and pore waters of studiedarea showing good relations with Caw (r 0666 ple 0018)Clp (r 0677 ple 0016) and SO4p (r 0858 ple 0000)Also Cls gives good correlations with Mgw (r 0710ple 0010) Naw (r 0602 ple 0038) Clw (r 0619ple 0032) Mgp (r 0774 ple 0003) and Kp (r 0731ple 0007) Chloride in the surface and pore waters plays animportant role in the dissolution association and formationof various salts along the lake -e good relationship be-tween Is and Caw (r 0666 ple 0018) may reflect the de-positionrelease of CaI+ during the formationdissolution ofcalcium carbonate [85] In addition these correlations maybe related to organic-I which formed by bacterial species andtheir remineralization in bottom sediments [86] -emoderate relationship between Nas and Brw (r minus0622ple 0031) may indicate the possible formation of BrClspecies and the precipitation or adsorption of Na minerals insediments [87] -e results of this study also reflect thestrong negative correlation between Fs and Bw (r minus0666ple 0018) which may be related to the release of fluoridefrom sediment and the formation of soluble fluoridecomplexes ((BFn[OH]4minusn)minus) with the excessive boron con-centration in the water [88] -e negative relation betweenKs and Spermilw (r minus0673 ple 0016) possibly reflect that Kw
preferentially chooses to exist in the soluble form of KClrather than being adsorbed andor bound by some richminerals in the sediment
-e significant correlations between CO3s and Mgw(r 0637 ple 0026) CO3s and Clw (r 0723 ple 0008)CO3s and pHw (r 0833 ple 0001) CO3s and Spermilw(r 0723 ple 0008) and between CO3s and Ks (r minus0673ple 0016) may be accompanied by the possible formationdissolution of the dolomite mineral in the presence ofsufficient Mgw which is usually affected by optimal pHsalinity and the potassium salts (Supplementary Table 1)-ese observed results are matching with the previouslyreported studies [32] Significant negative correlation be-tween TPs and CO3s (r minus0744 ple 0006) may indicate theextended release of P from carbonate minerals and for-mation of apatites [32]
-e correlation matrix also refers to other possible in-teractions between the remaining determined variables(Supplementary Table 1) -e significant correlation be-tween SO4s andMgw (r 0706 ple 0010) and Liw (r 0633ple 0027) may be associated to the formation of Mg-sulfateand the pollution of sediments by discharged waters con-taining excessive sulfate and Li [89] In the contrary thestrong positive correlation between TPs and Cus and be-tween TPs and Zns may be related to the same source ofpolluted discharge water [23 83]
-e high negative correlations of Zns with Few(r minus0785 ple 0003) CO3s (r minus0601 ple 0039) and Cus(r 0698 ple 0012) may indicate that Zn Cu and CO3depositions in sediment samples are linked to the soluble Feform in water (ferrous) ie the release of Fe upwards in thewater column in the anoxic conditions (SupplementaryTable 1) [90] -e excellent relations found between Fesand CO3s (r minus0799 ple 0002) Fes and Cas (r 0637ple 0026) Fes and Clw (r minus0752 ple 0005) Fes and Nas(r 0720 ple 0008) and between Fes and Ks (r 0833ple 0001) may reflect the dissolution of the chelating Feassociation with the soluble organic compounds in thewater-sediment interface and the formation of the sol-uble ferrous form in low dissolved oxygen within theareas affected by untreated discharged waters [90] -estrong correlations of Mns with SO4w Nap Nas Ks CO3sZns and Fes (r minus0585 0608 0611 0698 minus0655 0691and 0716 respectively) may associate with the solubilityof abundant Mn minerals and P-Mn forms in the sedi-ment because of its possible reduction to Mn+2 solublespecies under anoxic conditions [90] It is worth men-tioning that the results of this study indicate that ap-proximately 333 of the survey sites indicate thedepletion of dissolved oxygen in their surface watersamples Under such anoxic conditions bacteria are mostlikely to use sulfate instead of oxygen to break downorganic matter and cause the release of iron and phos-phorus into the water column
-e significant direct correlation between Ks and Nas(r 0832 plt 0001) clearly reflects the transport of solublesalts of K and Na between the pore water phase of thesediment and water-sediment surface phase (SupplementaryTable 1) -e good correlation between porosity and Nas
12 Journal of Chemistry
indicates the possible transfer of Na between pore water andsediment partitions
34 Interactions of Precipitated Halogenated Compounds inSurface and Pore Waters -e Saturation Index (SI) [23 60]of twenty-three and fifteen structures in surface water andpore water samples respectively are listed (Table 1) -ecorrelation matrix of the calculated Saturation Indices withthe presented data shows the different factors affecting theinteraction of the halogenated compound with other pre-cipitated salts and minerals Table 1 explores the precipitationof the phosphate minerals and salts are most abundantfollowed by the hydroxidesrsquo salts iodate salts sulfate andcarbonate minerals and salts in surface waters Amongst thehalogens precipitated salts fluoride minerals especiallyfluorapatites and carbonate-fluorapatite (FAP and CFAP)have high SI values in surface water (4277ndash5195 and1604ndash6089 respectively) and in pore water (5126ndash5460 and1752ndash7833 respectively) Bromide and chloride are mainlyfound in the soluble forms in surface and pore waters Iodidesalts (Ca(IO3)2 and Ca(IO3)26H2O) moderately precipitatein surface and pore Iron salts precipitate in surface waterwhile in pore water they are not formed -us SI contentreflects that halogens especially fluoride and iodide play avital role in reducing lake pollution
In addition Table 1 shows that the precipitation com-pounds that may be formed in surface water are relativelydifferent from those in sediment pore water For examplefluorite (CaF2) and sellaıte (MgF2) may be only formed inpore water while calcite and aragonite may be deposited insurface water However the formation of fluorite in surfacewater is related to Naw (r 0778 ple 0003) Kw (r 0704ple 0011) CO3w (r minus0718 ple 0009) Fw (r 0770ple 0003) and Ip (r minus0785 ple 0003) (SupplementaryTable 1)
-e formation of calcium sulfate hemihydrate calciumsulfate and anhydrite in water is related to the increase in theamounts of Caw Mgw SO4w Nap Fp Sip Cls and Mns andthe decrease in porosity values On the other hand pre-cipitation of calcium phosphate is related to Brw (r 0751ple 0005) Znw (r 0668 ple 0018) Pw (r 0881ple 0001) and Ks (r 0881 ple 0001) ie it is affected bythe discharged water composition (Supplementary Table 1)
-e formation of calcite and aragonite in surface water isrelated to the formation of CO3w (r 0753 ple 0005) anddissociation of HCO3w (r minus0660 ple 0020) pHw values(r minus0654 ple 0021) and their dissolution in sediment(r minus0620 ple 0032) (Supplementary Table 1)
-e dolomite formation in water may be affected by theincrease of CO3w (r 0817 ple 0001) and the decrease ofHCO3w (r minus0658 ple 0020) increase in TDSw (r 0599ple 0040) and increase in pHw (r minus0656 ple 0021)besides the possible release of CO3s from abundant sediment(r minus0624 ple 0030) and the precipitation of calcite(r 0984 ple 0000) and aragonite (r 0984 ple 0000) intosediment fraction (Supplementary Table 1)
Generally in the current study the possible formedhalogenated minerals and salts are affected by their
abundance in different components of the lake besides theirpossible dissolution or formation on the sediment texturesgeochemistry of the sediments and physicochemical vari-ables of water in addition to the components of the dis-charged waters
35 Interactions of Dissolved Halogenated Compounds inSurface and PoreWaters -e utilization of dissolved salts insurface and pore waters by utilizing Palmerrsquos method andpiper ternary diagram [50] indicates that Na is the richestcation in surface water followed by Mg Ca and K At thesame time Mg is the most predominate one in the porewater (Figures 3 and 4) Obviously Cl is the most importantanion in surface water and pore waters samples Howeverthe piper ternary diagrams of surface water and pore waterclearly shows that NaCl is the most dominant in surfacewater while MgCl2 is the most abundant in pore waterCoincidently Palmerrsquos method also reflects that NaCl(574) is the most existent species in surface water fol-lowed by MgCl2 (304) CaCl2 (71) CaSO4 (29)Ca(HCO3)2 (14) and KCl (12) (Figure 3) At the sametime MgCl2 (760) is the most present species in porewater followed by NaCl (73)asympMg(HCO3)2 (73)Ca(HCO3)2 (52) and MgSO4 (31) (Figure 4)
36 Multivariate Analysis
361 Principal Component (PCA) By applying Varimaxrotation and Kaiser normalization to 98 variables in the PCAfor halogens and tested variables and calculated parametervalues 7 extracted PCs with eigenvalues higher than 1 areobtained However it is important that the eigenvalue mustbe greater than 1 Its seven PCs explain 8558 of the totalvariance
-e first principle component (PC1) is 1473 of thetotal variance and shows positive coefficient factor loadingsfor CO3w TDSw Kp calcite aragonite dolomite FeCO3MgCO3 ZnCO3 and ZnCO3H2O (0804 0547 05320938 0938 0947 0741 0940 0866 and 0866 respec-tively) In addition it provides negative factor loadings forHCO3w pHw Bw Nap and CO3s (minus0782 minus0610 minus0595minus0532 and minus0572 respectively) PC1 is related to thefactors affecting the carbonate compounds that may beformed in the area under consideration
PC2 accounts to 1458 of the total variance and alsoshows positive and negative coefficient factor loadingsrepresenting the different interactions between the CawMgw Liw SO4wMgp Nap pHp Cls SO4s Brs and porosityin water pore water and sediment that are responsible forthe composition of sulfate magnesium and phosphateprecipitates besides the effect of the discharged waters onwater-pore water-sediment componentsrsquo cycles
PC3 typically shows 1377 of the total variance withpositive and negative loadings which can properly explorethe effect of the principal sources of local pollution on thedissolving of heavy metals B and P from sediment into thewater column and the probable formation of Fe(OH)2Fe(OH)3) and FePO4
Journal of Chemistry 13
Similarly the coefficient factor loadings of PC4 with1355 are related to the influence of the polluted dischargewater and sediment texture on the formation of F Cl and Isalt besides the precipitation of halogenated compounds(FeF2 Mn(IO3)2 KIO4 and KCIO4) besides their minerals(CaF2 MgF2 FAP and CFAP)
Simultaneously PC5 gives 1092 of the total variancewith positive and negative loadings which explains therelations between the physicochemical limits of the surfacewater pore water and sediment components and theprecipitation of minerals and salts (OCP HAP CuBrZn(OH)2 and Zn(IO3)22H2O) -is is also associated tothe influence of the sedimentary material on the release ofMn Fe and P from sediment into pore water and watercolumn and formation of Ca3(PO4)2 OCP and HAPminerals
However PC6 associates with 100 of the total variancegiving positive and negative coefficient factor loadingswhich explain that the sediments (minerals andor organic-iodine compounds) are only the acting sink for iodine andiodine species (Iminus and IOminus
3 ) in the water as previously re-ported [84] PC6 also reflects the precipitation of severalhalogenated compounds such as calcium iodate (Ca(IO3)2and Ca(IO3)26H2O) and copper iodate (CuI andCuIO3H2O) besides Cu3(PO4)2 species in the lake watercolumn
-e loadings of PC7 contribute by 804 and show thatthe release of calcium in pore water into the water column isresponsible for the precipitation of halogenated compounds(CuCl and Zn(IO3)22H2O) as well as copper and Zn salts(Cu3(PO4)2 and Zn(OH)2)
362 Cluster Analysis On the other hand cluster analysisshows that the similarity of sites 1amp4 5amp8 6amp9 2amp10 and11amp13 is due to the texture of sediment
363 Multiple Regression Multiple regression equations ofhalogens as dependent variables and the other determinedand calculated parameters as independent variables insurface water pore water and sediment partitions are listed(Table 5)-e amount of fluoride in water samples is affectedby the discharged watersrsquo fundamental components espe-cially Zn and Cu besides its surface water-pore water in-teractions Its content in pore water seems to be stronglyaffected by its substitution competition with other halogensin surface water-spore water-sediment cycle due to its highelectronegativity Generally in the affected area the type ofpollutant in the discharged water plays an important role inthe dissolution andor precipitation of fluoride and otherhalogens in the surface water-pore water-sediment cycle
574
147129
300
12
Ca(HCO3)2CaSO4CaCl2
MgCl2KClNaCl
(a)
SO4
2 + CIndash Ca 2+ + Mg 2+
CO32ndash + HCO3
ndashNa+ + K+
Mg2+ SO42ndash
Ca2+ CIndash
(b)
Figure 3 (a) distribution and (b) piper ternary diagram of the formed dissolved salts in surface water of Lake Mariout
Ca(HCO3)2Mg(HCO3)2MgSO4
NaClMgCI2KCl
760 1052
7373 31
(a)
SO4
2ndash + C
Indash
Ca 2+ + Mg 2+
CO32ndash + HCO3
ndashNa+ + K+
Mg2+ SO42ndash
CIndashCa2+
(b)
Figure 4 (a) distribution and (b) piper ternary diagram of the formed dissolved salts in pore water of Lake Mariout
14 Journal of Chemistry
Table 5 -e multiple regression analyses of each halogen as dependent variable and other tested variables in the surface water pore waterand sediment partitions besides the precipitated salts in surface water along Lake Mariout
Dependentvariable Multiple regression equation R2
FluorideLake water FW 3162 + 092 Zn F2 minus 033 SiP + 021 CuIminus 017 SpermilP 09911
Pore water Fp minus2567minus117 SiW minus 033 LiP minus 062 CuClminus 028 IS + 023 TDSW+ 017 KIO4 minus 012 BrW minus 004porosity + 004 PW
10000
Sediment FS 088 CAPminus 049 MgS minus 046 DOW+039MgW+ 027 Mn(IO3)2 + 015 Cu3(PO4)2 + 004 HAP+ 002 pHP 10000ChlorideLake water No relation 00000Pore water No relation 00000Sediment ClS minus116 + 046 MgP + 077 Kp minus 049 dolomite + 017 TDSW minus 011 CuI + 005 NaS + 002 BS + 001 FeF2 10000Bromide
Lake water BrW 1563 + 110 CuBrminus 057 CuClminus 021 KS minus 014 pHP minus 011 TPS + 014 FeW+ 007 ZnSminus 002 PP + 001turbidity 10000
Pore water BrP minus1516minus 055 FeS minus 073 BS + 061 MnW+ 083 SiP + 049 NaS minus 031MnS minus 015 CuBr + 011 pHW minus 001CaW
10000
Sediment BrS 015 SiP + 195 CFAP+ 002 FP minus 045 IS + 192 sand+ 037 MnW minus 029 MgS minus 012 LiP + 005Ca3(PO4)2 minus 002 ZnF2
10000
IodideLake water IW 099 Ca(IO3)6H2O 09999
Pore water IP minus097 ZnF2 minus 057 Li3PO4 minus 053 BP + 034 FAP+ 015 Ca(IO3)2 +MnW+ 005 KS minus 009 turbidity + 055CaS
09999
Sediment IS minus072 + 135 SO4P + 023 Mn(IO3)2 + 063 FeW+ 031 TPS minus 035 MgP minus 012 Zn(CO3)22H2O 09993
40E + 0135E + 0130E + 0125E + 0120E + 0115E + 0110E + 0150E + 0000E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
12345
678910
111213
(a)
10E + 0090E ndash 0180E ndash 0170E ndash 0160E ndash 0150E ndash 0140E ndash 0130E ndash 0120E ndash 0110E ndash 0100E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
12345
678910
111213
(b)
12345
678910
111213
40E ndash 0235E ndash 0230E ndash 0225E ndash 0220E ndash 0215E ndash 0210E ndash 0250E ndash 0300E ndash 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
(c)
12345
678910
111213
80E ndash 0670E ndash 0660E ndash 0650E ndash 0640E ndash 0630E ndash 0620E ndash 0610E ndash 0600E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
(d)
Figure 5 Hazard quotient of ingestion and dermal contact of surface water and sediment of LakeMariout (a) ingestion of water (b) dermalcontact of water (c) ingestion of sediment and (d) dermal contact of sediment
Journal of Chemistry 15
Minerals and precipitated salts in the different partitions(surface water pore water and sediment) play an importantrole in the deposition and release of halogens in sedimentsAdditionally the texture and the porosity of the sedimentsplay a key role in the distribution of halogens in the threepartitions Interestingly chloride is the only halogen that hasnegligible interactions along the surface water and porewater partitions because it is present in large quantities inthe form of soluble salts (NaCl and MgCl2)
37 Pollution Status
371 Enrichment Factor (EF) Twowell-knownmethods areused to assess environmental pollution public health sig-nificance of ingestion and dermal contact with water andsediment components and sediment enrichment factor (EF)[59 60]
-e average EF values of the determined elements CaMg Na K Li B P Cu Zn Mn Fe F Cl Br and I are alllower than the value that is less than the minimum en-richment value (EFlt 2)-us the area under investigation isstill ecologically considered as an unpolluted region
372 Human Health Risk Assessment -e EDI HQ and HIshow the variable values of all pollutants in the surface waterand sediments along the lake region and in drains (sites11ndash13) under study Among all the calculated variables ofsurface water ingestion (EDIIngw) and dermal contact(EDIDermw) Cl is still the only variable that shows high levels(average 1551 and 43mg kgminus1 dayminus1 respectively) -eestimation daily intake of sediment ingestion (EDIIngs) anddermal contact (EDIDerms) of Mg Ca and Na give maximumaverage amounts of 841Eminus 02 513E ndash 02 and167Eminus 03mg kgminus1 dayminus1 respectively
Among the HQ of the calculated detection variables thecontent of HQB of ingestion and dermal contact with waterand sediment is the highest However 70 of sites have HQBvalues more than 10 (Figure 5) Comparing the HQ values ofall the determined variables HQB of the ingestion of surfacewater shows values higher (gt10) However due to the impactof drainage the HQB values of stations 1ndash4 8ndash10 12 and 13
are higher than 10 -erefore these sites can be consideredas the area with the most serious boron pollution caused byuntreated discharged water disposal In addition the HIIngwlevel of water ingestion for the studied variables in all sites ismuch higher than 10 (Figure 6) Except for boron it isusually concluded that the study area does not pose any riskto the population due to halogens or other variables Ac-cordingly this information may help the official authoritiesoptimize management plans and strengthen their pollutioncontrol actions in Lake Mariout
4 Conclusions
-e effects of halogen salts and minerals on the pollution ofLake Mariout were studied Halogens and some physico-chemical variables in three partitions surface water porewater and sediment in Lake Mariout were evaluated -ehalogen content was variable between different sites andchloride was the main halogen in surface water and porewater but it was very rare in the lakersquos sediment partitionPiper ternary diagram and Palmerrsquos method reflected thatNaCl was the dominant salt in surface water while MgCl2was the main dissolve salt in pore water-e chlorinity ratiosof halogens and tested variables were directly matched to thefeeding drain sources
Moreover the Saturation Index (SI) reveals that 23 and 15precipitated salts and minerals are formed in surface water andpore water respectively -e SI value indicated the formationof phosphate minerals in surface water and pore water es-pecially octacalcium phosphate (OCP Ca4H(PO4)325H2O)and hydroxyapatite (HAP Ca5(PO4)3OH) In addition tofluoride minerals especially fluorapatite (FAP) and carbonate-fluorapatite (CFAP) were obviously precipitated from surfacewater and pore water Soluble salts of bromide and chloridewere formed in surface water and pore water Iodide salts(Ca(IO3)2 and Ca(IO3)26H2O) were moderately precipitatedin the surface water and pore water
Moreover the multivariate analysis including the cor-relation matrix multiple stepwise linear regression treeclustering and principle component (PCA) of all the de-termined and calculated variables was applied to estimatethe proposed interaction between halogens and other tested
10E + 02
16E + 0214E + 0212E + 02
80E + 0160E + 0140E + 0120E + 0100E + 00
1 2 3 4 5 6 7 8 9 10 11 12 13
HIIngHIDerm
(a)
1 2 3 4 5 6 7 8 9 10 11 12 13
HIIngHIDerm
40E ndash 0235E ndash 0230E ndash 0225E ndash 0220E ndash 0215E ndash 0210E ndash 0250E ndash 0300E + 01
(b)
Figure 6 Hazard index of ingestion and dermal contact of the studied variables in surface water and sediment of Lake Mariout (a) waterand (b) sediment
16 Journal of Chemistry
variables in the polluted area under study -e multivariateanalysis showed that there were many interactions betweenhalogens and tested variables High levels of fluoride bro-mide and chloride in surface water were related to thecomposition of drainage waters -e enrichment factor (EF)showed that Lake Mariout was not polluted However thehuman health adverse effects calculated for surface waterand sediment did not reflect any possible likelihood hazardeffects from halogens
Interestingly the current study concluded that halogencompounds especially fluorides are most likely to be de-posited from surface lakes in the form of many minerals andprecipitation thereby reducing the adverse pollution effectson human health -e results obtained through this workhelp to find the correlations between the sampling sites andthe variables obtained by physical and chemical measure-ments which can be used to construct a fast decision modelfor separating different water quality samples -is infor-mation may help the official authorities optimize manage-ment plans and strengthen their pollution control measuresin Lake Mariout
Data Availability
-e data used to support the findings of this research areincluded within the paper
Conflicts of Interest
-e authors declare that there are no conflicts of interestregarding the publication of this manuscript
Supplementary Materials
Supplementary Table 1 correlation matrix of variable insurface water pore water and sediment partitions besidesthe precipitated salts in surface water along Lake Mariout(Supplementary Materials)
References
[1] M S Masoud T O Said G El-Zokm and M A ShreadahldquoAssesment of heavy metals contamination in surface sedi-ments of the Egyptian Red Sea Coastsrdquo Australian Journal ofBasic and Applied Sciences vol 6 pp 44ndash58 2012
[2] M A Shreadah M I Abdel Moneim T O SaidE M I Fathallah and M E Mahmoud ldquoPAHs in seawater ofthe semi-closed areas along the Alexandria coast of EgyptianMediterranean seardquo Journal of Environmental Protectionvol 4 no 11 p 11 Article ID 40298 2013
[3] S Abdel Ghani G El Zokm A Shobier T Othman andM Shreadah ldquoMetal pollution in surface sediments of Abu-Qir bay and Eastern harbour of Alexandria Egyptrdquo EgyptianJournal of Aquatic Research vol 39 no 1 pp 1ndash12 2013
[4] G F El-Said ldquoBioaccumulation of key metals and othercontaminants by seaweeds from the Egyptian MediterraneanSea Coast in relation to human health riskrdquo Human andEcological Risk Assessment An International Journal vol 19no 5 pp 1285ndash1305 2013
[5] M A Shreadah A H Shobier S Abdel Ghani G M El-Zokm and T O Said ldquoMajor ions anomalies and
contamination status by trace metals in sediments from twohot spots along the Mediterranean Coast of Egyptrdquo Envi-ronmental Monitoring and Assessment vol 187 no 280pp 1ndash18 2015
[6] A El Nemr G F El-Said A Khaled and S Ragab ldquoDis-tribution and ecological risk assessment of some heavy metalsin coastal surface sediments along the Red Sea Egyptrdquo In-ternational Journal of Sediment Research vol 31 no 2pp 164ndash172 2016
[7] A El Nemr G F El-Said S Ragab A Khaled and A El-Sikaily ldquo-e distribution contamination and risk assessmentof heavy metals in sediment and shellfish from the Red Seacoast Egyptrdquo Chemosphere vol 165 pp 369ndash380 2016
[8] A El Nemr and G F El-Said ldquoAssessment and ecological riskof heavy metals in sediment and molluscs from the Medi-terranean coastrdquo Water Environment Research vol 89 no 3pp 195ndash210 2017
[9] M A Sheradah A A El-Sikaily N M Abd El MoneamN E Abd El Maguid and M G Zaki ldquoChemical and bio-chemical evaluation of marine pollution by polychlorinatedbiphenyls and pesticides in two regions along the EgyptianMediterranean Seardquo International Journal of EnvironmentalMonitoring and Analysis vol 6 no 3 pp 95ndash109 2018
[10] M A Shreadah A A-M M El-Sayed A A S TahaA-M M Ahmed and H H Abdel Rahman ldquoEvaluation ofdifferent anthropogenic effluents impacts on the water qualityusing principal component analysis a case study of Abu-QirBay-Alexandria-Egyptrdquo International Journal of Environ-mental Monitoring and Analysis vol 7 no 3 pp 56ndash67 2019
[11] G F El-Said M M El-Sadaawy A H Shobier andS E Ramadan ldquoHuman health implication of major and traceelements present in commercial crustaceans of a traditionalseafood marketing region Egyptrdquo Biological Trace ElementResearch vol 199 pp 315ndash328 2020
[12] M A Shreadah S A A Ghani H B I HawashA A E Samie and A E M M Ahmed ldquoOrganotin com-pounds in sediments of northern lakes Egyptrdquo Journal ofEnvironmental Protection vol 05 no 17 pp 1654ndash1666 2014
[13] A M Younis G M El-Zokm and M A Okbah ldquoSpatialvariation of acid-volatile sulfide and simultaneously extractedmetals in Egyptian Mediterranean Sea lagoon sedimentsrdquoEnvironmental Monitoring and Assessment vol 186 no 6pp 3567ndash3579 2014
[14] G F El-Said S E O Draz M M El-Sadaawy andA A Moneer ldquoSedimentology geochemistry pollution statusand ecological risk assessment of some heavy metals insurficial sediments of an Egyptian lagoon connecting to theMediterranean Seardquo Journal of Environmental Science andHealth Part A vol 49 no 9 pp 1029ndash1044 2014
[15] G M El Zokm M A Okbah and A M Younis ldquoAssessmentof heavy metals pollution using AVS-SEM and fractionationtechniques in Edku Lagoon sediments Mediterranean SeaEgyptrdquo Journal of Environmental Science and Health PartAvol 50 no 6 pp 571ndash584 2015
[16] G M El Zokm H R Z Tadros M A Okbah andG H Ibrahim ldquoldquoEutrophication assessment using TRIX andCarlsonrsquos indices in Lake Mariout water Egyptrdquo EgyptianJournal of Aquatic Biology and Fisheries vol 22 no 5pp 331ndash349 2018
[17] N Donia ldquoLake Maryut monitoring using remote sensingrdquo inProceedings of the gypt Eighteenth International WaterTechnology Conference IWTC18 Sharm El Sheikh Abu DhabiUAE March 2015
Journal of Chemistry 17
[18] M A Khairy ldquoAssessment of priority phenolic compounds insediments from an extremely polluted coastal wetland (LakeMaryut Egypt)rdquo Environmental Monitoring and Assessmentvol 185 no 1 pp 441ndash455 2013
[19] N A El-Naggar and E A Rifaat ldquoEgyptian coastal lakes andwetlands part Imdashcharacteristics and hydrodynamicsrdquo in eHandbook of Environmental Chemistry A M Negm EdSpringer International Publishing AG Berlin Germany 2017
[20] J J Hanley and K T Koga ldquoChapter 2 ldquohalogens in terrestrialand cosmic geochemical systems abundances Geochemicalbehaviors and analytical methodsrdquordquo in e Role of Halogensin Terrestrial and Extraterrestrial Geochemical ProcessesD E Harlov and L Aranovich Eds Springer InternationalPublishing AG Berlin Germany pp 21ndash121 2018
[21] A Ghosh K Mukherjee S K Ghosh and B Saha ldquoSourcesand toxicity of fluoride in the environmentrdquo Research onChemical Intermediates vol 39 no 7 pp 2881ndash2915 2013
[22] M M Naim A A Moneer and G F El-Said ldquoPredictiveequations for the defluoridation by electrocoagulation tech-nique using bipolar aluminum electrodes in the absence andpresence of additives a multivariate studyrdquo Desalination andWater Treatment vol 57 no 14 pp 6320ndash6332 2016
[23] G F El-Said N A Shaltout M M El-Sadaawy andA M H Morsy ldquo-e precipitation of fluoride calcium andmagnesium minerals from Egyptian Mediterranean Sea coastin relation to discharged watersrdquo Desalination and WaterTreatment vol 57 no 5 pp 2113ndash2124 2016
[24] H Bureau ldquoIodine encyclopedia of geochemistry A com-prehensive reference source on the chemistry of the earthrdquo inEncyclopedia of Earth Sciences Series W M White Ed copySpringer International Publishing AG 2016
[25] F C Kupper and C J Carrano ldquoKey aspects of the iodinemetabolism in brown algae a brief critical reviewrdquo Metal-lomics vol 11 pp 756ndash764 2019
[26] R Liteplo R Gomes P Howe and H Malcolm Fluorides-Environmental Health Criteria 227 p 290 World HealthOrganization (WHO) Geneva Switzerland 2002
[27] G F El-Said and M M El-Sadaawy ldquoSeasonal variation ofboron and fluoride in Tilapia nilotica from an Egyptian fishfarm in relation to Human health hazard assessmentrdquoHumanand Ecological Risk Assessment An International Journalvol 19 no 4 pp 930ndash943 2013
[28] WHO (World Health Organization) Bromide in Drinking-Water Background Document for Development of WHOGuidelines for Drinking-Water Quality WHO Press WorldHealth Organization Geneva Switzerland 2009
[29] G F El-Said and N A Sallam ldquo-e uptake of fluorideconcentration and its effects on the growth rate of shrimps(Palaemon elegans Rathke)rdquo Chemistry and Ecology vol 24no 3 pp 191ndash205 2008
[30] X Zhang J He B He and J Sun ldquoAssessment formationmechanism and different source contributions of dissolvedsalt pollution in the shallow groundwater of Hutuo Riveralluvial-pluvial fan in the North China Plainrdquo EnvironmentalScience and Pollution Research vol 26 no 35 pp 35742ndash35756 2019
[31] Y Zhu B Huang Z Zhu et al ldquoldquoCharacterization disso-lution and solubility of the hydroxypyromorphitendashhydroxyapatite solid solution [(PbxCa1minusx)5(PO4)3OH] at25 degC and pH 2ndash9rdquo Geochemical Transactions vol 17 no 2pp 1ndash18 2016
[32] G F El-Said M M El-Sadaawy A A Moneer andN A Shaltout ldquo-e effect of fluoride on the distribution ofsome minerals in the surface water of an Egyptian lagoon at
the Mediterranean Seardquo Egyptian Journal of Aquatic Researchvol 41 no 1 pp 31ndash39 2015
[33] Y Zhu Z Zhu X Zhao Y Liang and Y Huang ldquoChar-acterization dissolution and solubility of lead hydroxypyr-omorphite [Pb5(PO4)3OH] at 25ndash45degCrdquo Journal ofChemistry vol 2015 Article ID 269387 10 pages 2015
[34] M A Z Chahouki ldquoMultivariate analysis techniques inenvironmental sciencerdquo in Earth and Environmental SciencesDr Imran Ahmad Dar Ed InTech Open London UK 2011httpwwwintechopencombooksearth-and-environmental-sciencesmultivariate-analysis-techniques-inenvironmental-science
[35] J V Klump and C S Martens ldquoBiogeochemical cycling in anorganic-rich coastal marine basin 5 Sedimentary nitrogenand phosphorus budgets based upon kinetic models massbalances and the stoichiometry of nutrient regenerationrdquoGeochimica et Cosmochimica Acta vol 51 no 5 pp 1161ndash1173 1987
[36] R L Folk Petrology of Sedimentary Rocks University of TexasAustin TX USA 1974
[37] P Saenger ldquoA rapid spectrophotometric method for thedetermination of bromine in seawater and in the ash ofmarine algaerdquo Helgolander Wissenschaftliche Meer-esuntersuchungen vol 23 no 1 pp 32ndash37 1972
[38] P G Jeffery Chemical Methods of Rock Analysis PergamonPress New York NY USA 2nd edition 1975
[39] J D H Strickland and T R Parsons ldquoA practical handbook ofseawater analysisrdquo in Fisheries Research Board of CanadaBulletin 167p 311 Second edition Wiley Ottawa Canada1972
[40] B Horvath O Opara-Nadi and F Beese ldquoA simple methodfor measuring the carbonate content of soilsrdquo Soil ScienceSociety of America Journal vol 69 no 4 pp 1066ndash1068 2005
[41] K Grasshoff Methods of Seawater Analysis p 317 VerlagChemie Weinkeim Germany 1976
[42] R Danovaro D Marrale N Della Croce P Parodi andM Fabiano ldquoBiochemical composition of sedimentary or-ganic matter and bacterial distribution in the Aegean Seatrophic state and pelagic-benthic couplingrdquo Journal of SeaResearch vol 42 no 2 pp 117ndash129 1999
[43] APHA-AWWA-WPCF (American Public Health Associa-tion) Standard Methods for the Examination of Water andWaste Water American Public Health Association Wash-ington DC USA 20th edition 1999
[44] K I Aspila H Agemian and A S Y Chau ldquoA semi-auto-mated method for the determination of inorganic organicand total phosphate in sedimentsrdquo e Analyst vol 101no 1200 pp 187ndash197 1976
[45] J P Riley and D Taylor ldquoChelating resins for the concen-tration of trace elements from sea water and their analyticaluse in conjunction with atomic absorption spectrophotom-etryrdquo Analytica Chimica Acta vol 40 pp 479ndash485 1968
[46] G F El-Said and A El-Sikaily ldquoChemical composition ofsome seaweed from Mediterranean Sea coast Egyptrdquo Envi-ronmental Monitoring and Assessment vol 185 no 7pp 6089ndash6099 2013
[47] Directorate General of Health Services Ministry of Health andFamilyWelfare Government of India ldquoManual of methods ofanalysis of foodsrdquo in Fruit and Vegetable Productsp 57Directorate General of Health Services Ministry of Health andFamily Welfare Government of India New Delhi India2005
[48] A Gunnars S Blomqvist and C Martinsson ldquoInorganicformation of apatite in brackish seawater from the Baltic Sea
18 Journal of Chemistry
an experimental approachrdquo Marine Chemistry vol 91 no 1-4 pp 15ndash26 2004
[49] W M Haynes D R Lide and T J Bruno CRC Handbook ofChemistry and Physics A Ready Reference Book of Chemicaland Physical Data CRC Press Taylor amp Frances Group BocaRaton FL USA 97th edition 2017
[50] M S Masoud M I El-Samra and M M El-Sadawy ldquoWaterchemistry of el-mex bay west of Alexandria Egyptrdquo eEgypian Science Magazine vol 2 pp 70ndash78 2005
[51] F J Millero R Feistel D G Wright and T J McDougallldquo-e composition of standard seawater and the definition ofthe reference-composition salinity scalerdquo Deep Sea ResearchPart I Oceanographic Research Papers vol 55 no 1pp 50ndash72 2008
[52] S K El-Wakeel S A Morcos and A M Mahlis ldquo-e majorcations in Lake Maryut watersrdquo Hydrobiologia vol 36 no 2pp 253ndash274 1970
[53] A M Mahlis S A Morcos and S K El-Wakeel ldquo-e majoranions in Lake Maryut watersrdquo Hydrobiologia vol 36 no 2pp 275ndash294 1970
[54] A S Saad M A Massoud R A Amer and M A GhorabldquoAssessment of the physico-chemical characteristics andwater quality analysis of Mariout Lake southern of Alexan-dria Egyptrdquo Journal of Environmental and Analytical Toxi-cology vol 7 no 1 p 421 2017
[55] R Rumuri ldquoDataset on hydrogeochemical characteristics ofgroundwater and surface water in Kattumannarkoil TalukIndiardquo Data in Brief vol 32 Article ID 106058 2020
[56] P Szefer S W Fowler K Ikuta et al ldquoA comparative as-sessment of heavy metal accumulation in soft parts and byssusof mussels from subarctic temperate subtropical and tropicalmarine environmentsrdquo Environmental Pollution vol 139no 1 pp 70ndash78 2006
[57] N F Soliman G M El Zokm and M A Okbah ldquoRisk as-sessment and chemical fractionation of selected elements insurface sediments from Lake Qarun Egypt using modifiedBCR techniquerdquo Chemosphere vol 191 pp 262ndash271 2018
[58] G M El Zokm M I A Ibrahim L A Mohamed and M El-Mamoney ldquoCritical geochemical insight into Alexandria coastwith special reference to diagnostic ratios (TOCTN amp SrCa)and heavy metals ecotoxicological hazardsrdquo Egyptian Journalof Aquatic Research vol 46 no 1 pp 27ndash33 2020
[59] A S Likuku K B Mmolawa and G K GaboutloeloeldquoAssessment of heavy metal enrichment and degree of con-tamination around the copper-nickel mine in the SelebiPhikwe Region Eastern Botswanardquo Environment and EcologyResearch vol 1 no 2 pp 32ndash40 2013
[60] M K Khalil S E O Draz G M El Zokm and G F El-SaidldquoApportionment of geochemistry texturersquos properties and riskassessment of some elements in surface sediments from Bar-dawil Lagoon Egyptrdquo Human and Ecological Risk AssessmentAn International Journal vol 22 no 3 pp 775ndash791 2016
[61] M M El-Sadaawy and G F El-Said ldquoAssessment of fluoridein three selected polluted environments along the EgyptianMediterranean Sea effects on local populationsrdquo Human andEcological Risk Assessment An International Journal vol 20no 6 pp 1643ndash1658 2014
[62] USEPA ldquoSuperfund exposure assessment manualrdquo inOSWER Directive 92855-1EPA540l-88001Office of Emer-gency and Remedial Response Washington DC USA 1988
[63] USEPA ldquoExposure factors handbookrdquo in EPA6008-89043Office of Health and Environmental Assessment Wash-ington DC USA 1989
[64] Health Canada ldquoFederal Contaminated Site Risk Assessmentin Canadardquo Part II Health Canada Toxicological ReferenceValues (TRVs) Cat H46-204-368E Calgary Health CanadaOttawa Canada 2007
[65] J Iqbal S A Tirmizi and M H Shah ldquoStatistical appor-tionment and risk assessment of selected metals in sedimentsfrom Rawal Lake (Pakistan)rdquo Environmental Monitoring andAssessment vol 185 no 1 pp 729ndash743 2013
[66] USEPA (US Environmental Protection Agency) Region 6USAEPA ldquoMultimedia Planning and Permitting DivisionrdquoOffice of Solid Waste Center for Combustion Science andEngineering Washington DC USA 2005
[67] P Jeschke ldquoLatest generation of halogen-containing pesti-cidesrdquo Pest Management Science vol 73 no 6 pp 1053ndash10662017
[68] M A Shreadah O A El-Rayis N A Shaaban andA M Hamdan ldquoWater quality assessment and phosphorusbudget of a lake (Mariut Egypt) after diversion of wastewaterseffluentsrdquo Environmental Science and Pollution Researchvol 27 no 21 pp 26786ndash26799 2020
[69] J P Riley and M Tongudai ldquo-e major cationchlorinityratios in sea waterrdquo Chemical Geology vol 2 pp 263ndash2691967
[70] R B McCleskey D K Nordstrom D D Susong J W Balland J M Holloway ldquoSource and fate of inorganic solutes inthe gibbon river yellowstone national park Wyoming USArdquoJournal of Volcanology and Geothermal Research vol 193no 3-4 pp 189ndash202 2010
[71] G T F Wong and K-Y Li ldquoWinklerrsquos method overestimatesdissolved oxygen in seawater iodate interference and itsoceanographic implicationsrdquo Marine Chemistry vol 115no 1-2 pp 86ndash91 2009
[72] B S R V Prasad P D N Srinivasu P S VarmaA V Raman and S Ray ldquoDynamics of dissolved oxygen inrelation to saturation and health of an aquatic body a case forChilka Lagoon Indiardquo Journal of Ecosystems vol 2014 Ar-ticle ID 526245 17 pages 2014
[73] China Environmental Protection Agency EnvironmentalQuality Standards for Surface Water (GB3838ndash2002) NationalEnvironmental Protection Agency of China Beijing China2002
[74] Y Jia L Wang Z Qu and Z Yang ldquoDistribution con-tamination and accumulation of heavy metals in watersediments and freshwater shellfish from Liuyang RiverSouthern Chinardquo Environmental Science and Pollution Re-search vol 25 no 7 pp 7012ndash7020 2018
[75] A Moneer M El-Sadawy G El-Said and A Radwan ldquoBoronhuman health risk assessment relative to the environmentalpollution of Lake Edku Egyptrdquo Journal of King AbdulazizUniversity vol 23 no 2 pp 41ndash55 2012
[76] C B Tabelin T Igarashi T Arima D Sato T Tatsuhara andS Tamoto ldquoCharacterization and evaluation of arsenic andboron adsorption onto natural geologic materials and theirapplication in the disposal of excavated altered rockrdquo Geo-derma vol 213 pp 163ndash172 2014
[77] G Aloisi K Wallmann M Drews and G BohrmannldquoEvidence for the submarine weathering of silicate minerals inBlack Sea sediments possible implications for the marine Liand B cyclesrdquo Geochemistry Geophysics Geosystems vol 5no 4 pp 1ndash22 2004
[78] C Degueldre and V Cloet ldquoPore water colloid properties inargillaceous sedimentary rocksrdquo Science of e Total Envi-ronment vol 569-570 pp 423ndash433 2016
Journal of Chemistry 19
[79] J A Higgins and D P Schrag ldquoRecords of Neogene seawaterchemistry and diagenesis in deep-sea carbonate sedimentsand pore fluidsrdquo Earth and Planetary Science Letters vol 357-358 pp 386ndash396 2012
[80] H Schroeder A-L Fabricius D Ecker T A Ternes andL Duester ldquoMetal(loid) speciation and size fractionation insediment pore water depth profiles examined with a newmesoprofiling systemrdquo Chemosphere vol 179 pp 185ndash193 2017
[81] Y Song and G Muller ldquoFreshwater sediments sinks andsources of brominerdquo Naturwissenschaften vol 80 no 12pp 558ndash560 1993
[82] M E Goher H I Farhat M H Abdo and S G Salem ldquoMetalpollution assessment in the surface sediment of Lake NasserEgyptrdquo Egyptian Journal of Aquatic Research vol 40 no 3pp 213ndash224 2014
[83] G F El-Said M M El-Sadawy and A A Moneer ldquoIncor-poration of fluoride and boron into surface sediments alongthe Egyptian Mediterranean coastrdquo Egyptian Journal ofAquatic Research vol 36 no 4 pp 569ndash583 2010
[84] B Gilfedder G M Petri M Wessels and H Biester ldquoAniodine mass-balance for Lake Constance Germany insightsinto iodine speciation changes and fluxesrdquo Geochimica etCosmochimica Acta vol 74 no 11 pp 3090ndash3111 2010
[85] E Korobova L Kolmykova B Ryzhenko et al ldquoDistributionand speciation of iodine in drinking waters from geochem-ically different areas of Bryansk region contaminated after theChernobyl accident in relation to health and remediationaspectsrdquo Journal of Geochemical Exploration vol 184pp 311ndash317 2018
[86] V Zic V W Truesdale and N Cukrov ldquo-e distribution ofiodide and iodate in anchialine cave watersmdashevidence forsustained localised oxidation of iodide to iodate in marinewaterrdquoMarine Chemistry vol 112 no 3-4 pp 168ndash178 2008
[87] M B Heeb J Criquet S G Zimmermann-Steffens andU Von Gunten ldquoOxidative treatment of bromide-containingwaters formation of bromine and its reactions with inorganicand organic compoundsmdasha critical reviewrdquo Water Researchvol 48 pp 15ndash42 2014
[88] V Sivasankar A K Darchen and R Omine SakthivelldquoChapter 2 ldquofluoride a world ubiquitous compound itschemistry and ways of contaminationrdquo in Surface ModifiedCarbons as Scavengers for Fluoride fromWater V SivasankarEd pp 5ndash32 copy Springer International Publishing Switzer-land Cham Switzerland 2016
[89] O Cabestrero P Del Buey and M E Sanz-Montero ldquoBio-sedimentary and geochemical constraints on the precipitationof mineral crusts in shallow sulphate lakesrdquo SedimentaryGeology vol 366 pp 32ndash46 2018
[90] M A Hassaan O A El-Rayis and E I Hemada ldquoEstimationof the redox potential of lake mariut drainage system (Qalaaand Umum drains)rdquoHydrology vol 5 no 6 pp 82ndash85 2017
20 Journal of Chemistry
1
23
4
56
7
8
9
10
2986degE 2988degE 2990degE 2992degE
310
8degN
311
0degN
311
2degN
311
4degN
311
6degN
El-mex
pumping
statio
n Main Basin
of Lake Maryout
Southwest Basin
Qalaa Drain
El Umoum Drain
Northwest BasinFish
ery Basi
nEl Nubaria Drain
3311 to 38883888 to 43934393 to 5115
5115 to 65226522 to 7284
(a)
1
23
4
56
7
8
9
10
2986degE 2988degE 2990degE 2992degE
310
8degN
311
0degN
311
2degN
311
4degN
311
6degN
El-mex
pumping
statio
n
Main Basinof Lake Maryout
Southwest Basin
Qalaa Drain
El Umoum Drain
Northwest Basin
Fishery
BasinEl Nubaria Drain
069 to 127127 to 169169 to 242
242 to 277277 to 377
(b)
El-mex
pumping
statio
n
Main Basin of Lake Maryout
South west Basin
North west Basin
1
23
4
56
7
8
9
10
2986degE 2988degE 2990degE 2992degE
310
8degN
311
0degN
311
2degN
311
4degN
311
6degN
Qalaa Drain
El Umoum Drain
Fishery
BasinEl Nubaria Drain
613 to 852852 to 14381438 to 1732
1732 to 52745274 to 6554
(c)
El-mex
pumping
statio
n
Main Basin of Lake Maryout
Southwest Basin
Northwest Basin
1
23
4
56
7
8
9
10
2986degE 2988degE 2990degE 2992degE
310
8degN
311
0degN
311
2degN
311
4degN
311
6degN
Qalaa Drain
El Umoum Drain
Fishery
BasinEl Nubaria Drain
566 to 671671 to 761761 to 817
817 to 922922 to 5411
(d)
Figure 2 Distribution of halogens (Cl F Br and I in surface water of LakeMariout (a) Cl (mg Lminus1) (b) F (mg Lminus1) (c) Br (mg Lminus1) and (d) I(μg Lminus1)
8 Journal of Chemistry
ple 0028) Mgw amp Liw (r 0790 ple 0002) Naw amp Kw(r 0955 ple 0000 Naw amp Liw (r 0835 ple 0001) Naw ampCO3w (r minus0701 ple 0011) Kw amp Liw (r 0712 ple 0009)Kw amp CO3w (r minus0580 ple 0048) CO3w amp HCO3w(r minus0613 ple 0034) and Mgw amp SO4w (r 0631ple 0028) indicate that all these variables have some geo-chemical behaviors [77] Mg Na and Li are some com-ponents of the discharged waters however they havepositive correlations with the chlorinity and salinity of thedischarged water sources (r 0743 0619 and 0815 re-spectively) and (r 0743 0619 and 0815 respectively)Mgw and Liw contents in water samples are affected bytemperature dissolved oxygen and pH with high correla-tions of r minus0650 0677 and 0743 and minus0702 0659 and0815 respectively
32 Distribution of Halogens and Tested Variables in PoreWater
321 Distribution of Halogens in Pore Water -e averagehalogen contents in the pore water are higher than theircontents in the surface water but in the same orderClpgtBpgt Fpgt Ip (Table 3) Current research shows that thelowest and highest average values of Spermilp and Clp have beenmeasured in the pore water of site 6 and site 8 respectively Itis worth mentioning that site 6 is a mixed water of El-Qalaadrainage sewage WWTP treatment plant and lake waterInterestingly the high concentrations of fluoride chloridebromide and iodide in the pore water at site 6 are 123mgLminus1 40321mg Lminus1 11739mg Lminus1 and 24339 μg Lminus1 re-spectively (Table 3) -e salinity and chloride content in thepore water of site 8 are related to the discharge water of manypetrochemical and oil companies besides some fish farms
322 Distribution of Tested Variables in Pore Water -etested variables in the pore water (p) give the followingdescending order MgpgtNapgtCapgt SO4pgtBpgtKpgtBrpgt Fpgt LipgtPpgt Ipgt Sip (Table 3) Interestingly the deter-mined variables in the pore water have higher values thanthe surface water along the lake According to previousstudies pore water is responsible for biogeochemical reac-tions the migration and transformation of partitioned andformed compounds and the transportation of colloidalspecies [78 79] In addition pore water can explore thepotential risks of man-made pollution sources [80] -etested variables in the pore water (p) are given in a differentorder of surface water of ClpgtMgpgtNapgtCapgt SO4pgtBpgtKpgtBrpgt Fpgt Lipgt Ppgt Ipgt Sip (Tables 2and 3)
323 Interactions of Halogens and Tested Variables in PoreWater -e following interactions of halogens CO3w amp Ip Ipamp Fw Brw amp Sip Fp amp Siw and Fp amp Nap give correlationvalues (r 0706 ple 0010 r minus0606 ple 0037 r 0826ple 0001 r minus0704 ple 0011 and r 0670 ple 0017respectively) (Supplementary Table 1) However these re-lationships may indicate their precipitation andor
adsorption on the colloidal particles besides the formation ofsome chemical species [78 79] Extraordinarily large cor-relations of Nap amp HCO3w Kp amp HCO3w Spermilw amp Bp Spermilp ampKp Spermilp amp Lip and Spermilp amp Clp (r 0692 minus0609 minus07410696 0910 and 1000) may refer to the release of theseelements from sediment particles andor precipitation oradsorption [77] In the matrix the negative correlationbetween Cap and Mgp (r minus0592 ple 0042) may be relatedto the release of Mg during the recrystallization of calcite[79]-e relationship between Caw amp SO4p Cuw amp Cap Pw ampPp and Nap amp pHw (r 0744 ple 0006 r 0719 ple 0008r 0647 ple 0023 and r minus0640 ple 0025 respectively)may be due to the chemical interactions in the pore fluidsand the formation certain compounds
33Distribution ofHalogens andTestedVariables in Sediment
331 Distribution of Halogens in Sediment -e averagehalogenrsquos content in the sediment shows a different orderfrom the surface and pore waters of Brsgt FsgtClsgt Is (Ta-ble 4) -e sediment results show that the average bromidecontent is higher than fluoride followed by chloride contentand iodide with average values of 452mg gminus1 040mg gminus1029mg gminus1 and 450 μg gminus1 respectively
-e fluoride concentration in the sediment ranges from001 to 120mg gminus1 with an average value of 04plusmn 035mggminus1 -ese values are lower than reported marine sedimentvalues and higher than the El-Bardawil Lagoon [60]Amongst the halogens the study reveals that Br is the mostabundant ion in surface water pore water and sedimentsamples due to the excessive amounts of organic matter [81]On the contrary the concentration of Cl ions in sedimentsamples is lower than that in surface water and pore watersamples indicating that it exists in soluble salts -e currentresults indicate that the sediments collected from the mostaffected area by the Mediterranean Sea (site 6) contain el-evated levels of fluoride (070mg gminus1) bromide (852mggminus1) and chloride (020mg gminus1) and a reduced amount ofiodide (209 μg gminus1) (Table 4)
332 Distribution of Tested Variables in Sediment -eaverage value of test variables in the determined sedimentsamples shows a significant change from site to site with adescending order CO3sgtMgsgtCasgtNasgt SO4s gt FesgtBsgtKsgtTPsgtMn sgtZnsgtCusgt Lis (Table 4) Plus this studyclears out that the percent of sand and mud of the differentsediment samples ranges from 4 at sites 1 amp 13 to 85 atsite 11 and from 15 at site 11 to 96 at sites 1amp13 re-spectively with averages 25 and 75 respectively Plusthe porosity shows a trend opposite to the particle size andvaries from 4676 to 8214 with an average value of5609plusmn 1114 -e results of the current study reveal mod-erate amounts of CO3 in the sediment samples fluctuatingbetween 1639 and 5736 at sites 6 and 2 respectively -eresults of sand mud porosity and CO3 percentage reflect thatthe texture of the sediment is mainly composed of mud mixedwith carbonate compounds Comprehensively the large storageof sediments with carbonate (359plusmn1280) magnesium
Journal of Chemistry 9
Tabl
e3
Distribu
tionof
thestud
iedvariablesin
thepo
rewater
(p)alon
gLake
Mariout
Site
Spermilp
pHP
Ca p
(mgLminus
1 )Mg p
(mgLminus
1 )Na p
(mgLminus
1 )Kp
(mgLminus
1 )Li
p(m
gLminus
1 ))
SO4P
(mgLminus
1 ))
B P(m
gLminus
1 ))
P P(μgLminus
1 ))
SiP
(microgLminus
1 ))
F p(m
gLminus
1 ))
Cl P
(mgLminus
1 ))
Brp
(mgLminus
1 ))
I p(μgLminus
1 )1
1034
787
481
42303
1097
453
042
2944
8043
363
0045
323
95419
959
7104
2934
809
5611
115725
1050
498
039
2056
663
553
0036
338
8398
1385
24698
31272
717
100
5689
1195
577
053
2778
8949
1204
0034
754
114469
2291
26347
483
796
9619
47652
974
384
043
350
19312
77
0054
215
74599
693
8393
51099
782
5611
89711
1128
42041
1667
16739
1112
0081
1698864
1332
8333
645
775
4008
75367
736
41024
2111
11739
071
0037
1231
40321
799
24339
71125
782
39278
13615
1155
516
056
3667
6051
369
006
6101209
1279
8123
8148
775
9299
84314
1355
468
055
12444
942
212
0056
892
133232
1172
7643
9684
78
962
72109
880
393
036
3778
21341
114
0087
1061429
2131
9981
10114
764
1122
113586
1195
524
049
4667
8007
071
0041
1138
102562
1332
8572
11639
742
4008
61996
915
332
033
2833
11594
754
0026
1215
67834
746
37587
125
702
481
38413
8703
274
028
2167
13913
081
0025
2154
44832
1438
9891
13755
807
3206
6467
817
446
039
4556
17246
635
0042
954
5737
533
1097
Minim
um45
702
962
13615
736
274
024
1667
6051
071
0025
215
40321
533
7104
Maxim
um148
809
39278
115725
8703
577
056
12444
21341
1204
0087
2154
133232
2291
37587
Average
919
77
718
67412
163077
4381
041
3782
1223
485
0048
955
82779
1238
14768
SD308
032
10027
29209
2132
825
01
2769
5047
391
0019
542
27891
524
9917
10 Journal of Chemistry
Tabl
e4
Distribu
tionof
thestud
iedvariablesin
thesediment(s)alon
gLake
Mariout
Site
Sand
()
Mud ()
Porosity
()
CO3s
()
B s(m
ggminus
1 )P s
(mg
gminus1 )
Ca s
(mg
gminus1 )
Mg s
(mg
gminus1 )
Na s
(mg
gminus1 )
Ks
(mg
gminus1 )
Lis(m
ggminus
1 )
SO4s
(mg
gminus1 )
Fes
(mg
gminus1 )
Cu s (μg
gminus1 )
Mn s
(μg
gminus1 )
Zns(μg
gminus1 )
F s(m
ggminus
1 )
Cl s
(mg
gminus1 )
Brs
(mg
gminus1 )
I s(μg
gminus1 )
14
964915
183
299
044
1670
811
2583
408
0028
4861
828
963
5617
1272
034
041
128
1686
244
564925
574
196
028
1002
1419
2717
269
0015
662
257
793
4350
1313
057
054
123
358
319
816667
299
246
073
1670
1216
3125
336
0022
463
487
1228
4330
1677
044
034
448
516
418
824853
3813
1111
032
668
2229
3425
365
0094
2222
770
922
4637
1245
030
020
309
296
512
884697
482
614
012
501
1115
1833
091
0040
1713
243
600
27933
1223
082
034
245
254
65
954667
164
370
157
835
1257
2958
388
0030
5648
890
1927
5347
3117
070
020
852
209
75
954762
375
524
024
367
2047
3133
256
0102
1157
546
883
4185
1393
120
020
341
259
838
626143
457
697
039
668
1621
3550
347
0145
4167
598
737
4157
1412
022
034
144
1277
918
826000
349
083
054
401
1094
3358
369
0025
2454
701
868
5702
3065
036
027
250
172
1036
645070
441
296
002
935
1763
3117
246
0045
2685
369
790
4533
1315
012
047
1012
224
1185
157000
325
240
074
969
2250
3508
328
0193
1343
1026
735
3890
1070
005
007
533
128
1237
638214
463
291
032
334
1824
3008
358
0018
556
340
728
2475
827
001
007
852
281
134
965000
177
211
054
2338
1621
3925
599
0068
833
1687
1187
6492
1853
004
027
639
194
Min
415
4667
164
083
002
334
811
1833
091
0015
463
243
600
2475
827
001
007
123
128
Max
8596
8214
574
1111
157
2338
2250
3925
599
0193
6620
1687
1927
6492
3117
120
054
1012
1686
Av
2575
5609
359
398
048
951
1559
3096
335
0063
2671
672
951
4500
1599
040
029
452
450
SD23
231114
128
276
039
603
455
522
115
0055
2030
393
343
1120
708
035
014
303
475
Minm
inim
umM
axm
axim
uma
ndAv
averageSD
stand
arddeviation
Journal of Chemistry 11
(1559plusmn455mg gminus1) and calcium (951plusmn603mg gminus1) com-ponents may be attributed to the abundance of calcium min-erals [4] However in general the average amounts of allvariables in sediment samples showmarked variations fromonesite to another with a descending order of CO3sgtMgsgtCasgtNasgtSO4sgtFesgt BrsgtBsgtKsgtTPsgtFs gtClsgtMnsgtZnsgtCusgtLisgt Is (Table 4) -e measured concentra-tions of Mn Zn Cu and Fe in the sediment samples are stilllower than the reported values and also lower than the back-ground levels of crust and the toxicological reference contents ofUS DOE (US Department of Energy) US EPA (US Envi-ronmental Protection Agency) and CEQG (Canadian Envi-ronmental Quality Guidelines) [82]
Contrasting the obtained levels for the halogens withthose previously reported ones the present study indicatesthat surface and pore waters incorporate more considerableamounts of fluoride compared to the formerly reported onesin Lake Edku (Tables 2 and 3) and lower levels in theMarioutarea than those measured along the Egyptian MediterraneanSea coast [27] Compared with the sediments previouslyfound on the Mediterranean coast of Egypt the chloridecontent in the sediments of the Mariout area is lower [83]Compared with those observed in seawater the studiedsurface water and pore water samples have lower bromidecontent and higher levels than previously reported in LakeMariout [52 53] -e concentration of iodide in surfacewater pore water and sediments is equivalent to the con-centration of rivers and lakes in the world [84]
333 Interactions of Halogens and Tested Variables inSediment -e correlation matrix shows the important roleof halogens in the formation and precipitationdissolution ofsalts and minerals produced along the lake (SupplementaryTable 1) However it shows that chloride seems to be in thesoluble forms along the surface and pore waters of studiedarea showing good relations with Caw (r 0666 ple 0018)Clp (r 0677 ple 0016) and SO4p (r 0858 ple 0000)Also Cls gives good correlations with Mgw (r 0710ple 0010) Naw (r 0602 ple 0038) Clw (r 0619ple 0032) Mgp (r 0774 ple 0003) and Kp (r 0731ple 0007) Chloride in the surface and pore waters plays animportant role in the dissolution association and formationof various salts along the lake -e good relationship be-tween Is and Caw (r 0666 ple 0018) may reflect the de-positionrelease of CaI+ during the formationdissolution ofcalcium carbonate [85] In addition these correlations maybe related to organic-I which formed by bacterial species andtheir remineralization in bottom sediments [86] -emoderate relationship between Nas and Brw (r minus0622ple 0031) may indicate the possible formation of BrClspecies and the precipitation or adsorption of Na minerals insediments [87] -e results of this study also reflect thestrong negative correlation between Fs and Bw (r minus0666ple 0018) which may be related to the release of fluoridefrom sediment and the formation of soluble fluoridecomplexes ((BFn[OH]4minusn)minus) with the excessive boron con-centration in the water [88] -e negative relation betweenKs and Spermilw (r minus0673 ple 0016) possibly reflect that Kw
preferentially chooses to exist in the soluble form of KClrather than being adsorbed andor bound by some richminerals in the sediment
-e significant correlations between CO3s and Mgw(r 0637 ple 0026) CO3s and Clw (r 0723 ple 0008)CO3s and pHw (r 0833 ple 0001) CO3s and Spermilw(r 0723 ple 0008) and between CO3s and Ks (r minus0673ple 0016) may be accompanied by the possible formationdissolution of the dolomite mineral in the presence ofsufficient Mgw which is usually affected by optimal pHsalinity and the potassium salts (Supplementary Table 1)-ese observed results are matching with the previouslyreported studies [32] Significant negative correlation be-tween TPs and CO3s (r minus0744 ple 0006) may indicate theextended release of P from carbonate minerals and for-mation of apatites [32]
-e correlation matrix also refers to other possible in-teractions between the remaining determined variables(Supplementary Table 1) -e significant correlation be-tween SO4s andMgw (r 0706 ple 0010) and Liw (r 0633ple 0027) may be associated to the formation of Mg-sulfateand the pollution of sediments by discharged waters con-taining excessive sulfate and Li [89] In the contrary thestrong positive correlation between TPs and Cus and be-tween TPs and Zns may be related to the same source ofpolluted discharge water [23 83]
-e high negative correlations of Zns with Few(r minus0785 ple 0003) CO3s (r minus0601 ple 0039) and Cus(r 0698 ple 0012) may indicate that Zn Cu and CO3depositions in sediment samples are linked to the soluble Feform in water (ferrous) ie the release of Fe upwards in thewater column in the anoxic conditions (SupplementaryTable 1) [90] -e excellent relations found between Fesand CO3s (r minus0799 ple 0002) Fes and Cas (r 0637ple 0026) Fes and Clw (r minus0752 ple 0005) Fes and Nas(r 0720 ple 0008) and between Fes and Ks (r 0833ple 0001) may reflect the dissolution of the chelating Feassociation with the soluble organic compounds in thewater-sediment interface and the formation of the sol-uble ferrous form in low dissolved oxygen within theareas affected by untreated discharged waters [90] -estrong correlations of Mns with SO4w Nap Nas Ks CO3sZns and Fes (r minus0585 0608 0611 0698 minus0655 0691and 0716 respectively) may associate with the solubilityof abundant Mn minerals and P-Mn forms in the sedi-ment because of its possible reduction to Mn+2 solublespecies under anoxic conditions [90] It is worth men-tioning that the results of this study indicate that ap-proximately 333 of the survey sites indicate thedepletion of dissolved oxygen in their surface watersamples Under such anoxic conditions bacteria are mostlikely to use sulfate instead of oxygen to break downorganic matter and cause the release of iron and phos-phorus into the water column
-e significant direct correlation between Ks and Nas(r 0832 plt 0001) clearly reflects the transport of solublesalts of K and Na between the pore water phase of thesediment and water-sediment surface phase (SupplementaryTable 1) -e good correlation between porosity and Nas
12 Journal of Chemistry
indicates the possible transfer of Na between pore water andsediment partitions
34 Interactions of Precipitated Halogenated Compounds inSurface and Pore Waters -e Saturation Index (SI) [23 60]of twenty-three and fifteen structures in surface water andpore water samples respectively are listed (Table 1) -ecorrelation matrix of the calculated Saturation Indices withthe presented data shows the different factors affecting theinteraction of the halogenated compound with other pre-cipitated salts and minerals Table 1 explores the precipitationof the phosphate minerals and salts are most abundantfollowed by the hydroxidesrsquo salts iodate salts sulfate andcarbonate minerals and salts in surface waters Amongst thehalogens precipitated salts fluoride minerals especiallyfluorapatites and carbonate-fluorapatite (FAP and CFAP)have high SI values in surface water (4277ndash5195 and1604ndash6089 respectively) and in pore water (5126ndash5460 and1752ndash7833 respectively) Bromide and chloride are mainlyfound in the soluble forms in surface and pore waters Iodidesalts (Ca(IO3)2 and Ca(IO3)26H2O) moderately precipitatein surface and pore Iron salts precipitate in surface waterwhile in pore water they are not formed -us SI contentreflects that halogens especially fluoride and iodide play avital role in reducing lake pollution
In addition Table 1 shows that the precipitation com-pounds that may be formed in surface water are relativelydifferent from those in sediment pore water For examplefluorite (CaF2) and sellaıte (MgF2) may be only formed inpore water while calcite and aragonite may be deposited insurface water However the formation of fluorite in surfacewater is related to Naw (r 0778 ple 0003) Kw (r 0704ple 0011) CO3w (r minus0718 ple 0009) Fw (r 0770ple 0003) and Ip (r minus0785 ple 0003) (SupplementaryTable 1)
-e formation of calcium sulfate hemihydrate calciumsulfate and anhydrite in water is related to the increase in theamounts of Caw Mgw SO4w Nap Fp Sip Cls and Mns andthe decrease in porosity values On the other hand pre-cipitation of calcium phosphate is related to Brw (r 0751ple 0005) Znw (r 0668 ple 0018) Pw (r 0881ple 0001) and Ks (r 0881 ple 0001) ie it is affected bythe discharged water composition (Supplementary Table 1)
-e formation of calcite and aragonite in surface water isrelated to the formation of CO3w (r 0753 ple 0005) anddissociation of HCO3w (r minus0660 ple 0020) pHw values(r minus0654 ple 0021) and their dissolution in sediment(r minus0620 ple 0032) (Supplementary Table 1)
-e dolomite formation in water may be affected by theincrease of CO3w (r 0817 ple 0001) and the decrease ofHCO3w (r minus0658 ple 0020) increase in TDSw (r 0599ple 0040) and increase in pHw (r minus0656 ple 0021)besides the possible release of CO3s from abundant sediment(r minus0624 ple 0030) and the precipitation of calcite(r 0984 ple 0000) and aragonite (r 0984 ple 0000) intosediment fraction (Supplementary Table 1)
Generally in the current study the possible formedhalogenated minerals and salts are affected by their
abundance in different components of the lake besides theirpossible dissolution or formation on the sediment texturesgeochemistry of the sediments and physicochemical vari-ables of water in addition to the components of the dis-charged waters
35 Interactions of Dissolved Halogenated Compounds inSurface and PoreWaters -e utilization of dissolved salts insurface and pore waters by utilizing Palmerrsquos method andpiper ternary diagram [50] indicates that Na is the richestcation in surface water followed by Mg Ca and K At thesame time Mg is the most predominate one in the porewater (Figures 3 and 4) Obviously Cl is the most importantanion in surface water and pore waters samples Howeverthe piper ternary diagrams of surface water and pore waterclearly shows that NaCl is the most dominant in surfacewater while MgCl2 is the most abundant in pore waterCoincidently Palmerrsquos method also reflects that NaCl(574) is the most existent species in surface water fol-lowed by MgCl2 (304) CaCl2 (71) CaSO4 (29)Ca(HCO3)2 (14) and KCl (12) (Figure 3) At the sametime MgCl2 (760) is the most present species in porewater followed by NaCl (73)asympMg(HCO3)2 (73)Ca(HCO3)2 (52) and MgSO4 (31) (Figure 4)
36 Multivariate Analysis
361 Principal Component (PCA) By applying Varimaxrotation and Kaiser normalization to 98 variables in the PCAfor halogens and tested variables and calculated parametervalues 7 extracted PCs with eigenvalues higher than 1 areobtained However it is important that the eigenvalue mustbe greater than 1 Its seven PCs explain 8558 of the totalvariance
-e first principle component (PC1) is 1473 of thetotal variance and shows positive coefficient factor loadingsfor CO3w TDSw Kp calcite aragonite dolomite FeCO3MgCO3 ZnCO3 and ZnCO3H2O (0804 0547 05320938 0938 0947 0741 0940 0866 and 0866 respec-tively) In addition it provides negative factor loadings forHCO3w pHw Bw Nap and CO3s (minus0782 minus0610 minus0595minus0532 and minus0572 respectively) PC1 is related to thefactors affecting the carbonate compounds that may beformed in the area under consideration
PC2 accounts to 1458 of the total variance and alsoshows positive and negative coefficient factor loadingsrepresenting the different interactions between the CawMgw Liw SO4wMgp Nap pHp Cls SO4s Brs and porosityin water pore water and sediment that are responsible forthe composition of sulfate magnesium and phosphateprecipitates besides the effect of the discharged waters onwater-pore water-sediment componentsrsquo cycles
PC3 typically shows 1377 of the total variance withpositive and negative loadings which can properly explorethe effect of the principal sources of local pollution on thedissolving of heavy metals B and P from sediment into thewater column and the probable formation of Fe(OH)2Fe(OH)3) and FePO4
Journal of Chemistry 13
Similarly the coefficient factor loadings of PC4 with1355 are related to the influence of the polluted dischargewater and sediment texture on the formation of F Cl and Isalt besides the precipitation of halogenated compounds(FeF2 Mn(IO3)2 KIO4 and KCIO4) besides their minerals(CaF2 MgF2 FAP and CFAP)
Simultaneously PC5 gives 1092 of the total variancewith positive and negative loadings which explains therelations between the physicochemical limits of the surfacewater pore water and sediment components and theprecipitation of minerals and salts (OCP HAP CuBrZn(OH)2 and Zn(IO3)22H2O) -is is also associated tothe influence of the sedimentary material on the release ofMn Fe and P from sediment into pore water and watercolumn and formation of Ca3(PO4)2 OCP and HAPminerals
However PC6 associates with 100 of the total variancegiving positive and negative coefficient factor loadingswhich explain that the sediments (minerals andor organic-iodine compounds) are only the acting sink for iodine andiodine species (Iminus and IOminus
3 ) in the water as previously re-ported [84] PC6 also reflects the precipitation of severalhalogenated compounds such as calcium iodate (Ca(IO3)2and Ca(IO3)26H2O) and copper iodate (CuI andCuIO3H2O) besides Cu3(PO4)2 species in the lake watercolumn
-e loadings of PC7 contribute by 804 and show thatthe release of calcium in pore water into the water column isresponsible for the precipitation of halogenated compounds(CuCl and Zn(IO3)22H2O) as well as copper and Zn salts(Cu3(PO4)2 and Zn(OH)2)
362 Cluster Analysis On the other hand cluster analysisshows that the similarity of sites 1amp4 5amp8 6amp9 2amp10 and11amp13 is due to the texture of sediment
363 Multiple Regression Multiple regression equations ofhalogens as dependent variables and the other determinedand calculated parameters as independent variables insurface water pore water and sediment partitions are listed(Table 5)-e amount of fluoride in water samples is affectedby the discharged watersrsquo fundamental components espe-cially Zn and Cu besides its surface water-pore water in-teractions Its content in pore water seems to be stronglyaffected by its substitution competition with other halogensin surface water-spore water-sediment cycle due to its highelectronegativity Generally in the affected area the type ofpollutant in the discharged water plays an important role inthe dissolution andor precipitation of fluoride and otherhalogens in the surface water-pore water-sediment cycle
574
147129
300
12
Ca(HCO3)2CaSO4CaCl2
MgCl2KClNaCl
(a)
SO4
2 + CIndash Ca 2+ + Mg 2+
CO32ndash + HCO3
ndashNa+ + K+
Mg2+ SO42ndash
Ca2+ CIndash
(b)
Figure 3 (a) distribution and (b) piper ternary diagram of the formed dissolved salts in surface water of Lake Mariout
Ca(HCO3)2Mg(HCO3)2MgSO4
NaClMgCI2KCl
760 1052
7373 31
(a)
SO4
2ndash + C
Indash
Ca 2+ + Mg 2+
CO32ndash + HCO3
ndashNa+ + K+
Mg2+ SO42ndash
CIndashCa2+
(b)
Figure 4 (a) distribution and (b) piper ternary diagram of the formed dissolved salts in pore water of Lake Mariout
14 Journal of Chemistry
Table 5 -e multiple regression analyses of each halogen as dependent variable and other tested variables in the surface water pore waterand sediment partitions besides the precipitated salts in surface water along Lake Mariout
Dependentvariable Multiple regression equation R2
FluorideLake water FW 3162 + 092 Zn F2 minus 033 SiP + 021 CuIminus 017 SpermilP 09911
Pore water Fp minus2567minus117 SiW minus 033 LiP minus 062 CuClminus 028 IS + 023 TDSW+ 017 KIO4 minus 012 BrW minus 004porosity + 004 PW
10000
Sediment FS 088 CAPminus 049 MgS minus 046 DOW+039MgW+ 027 Mn(IO3)2 + 015 Cu3(PO4)2 + 004 HAP+ 002 pHP 10000ChlorideLake water No relation 00000Pore water No relation 00000Sediment ClS minus116 + 046 MgP + 077 Kp minus 049 dolomite + 017 TDSW minus 011 CuI + 005 NaS + 002 BS + 001 FeF2 10000Bromide
Lake water BrW 1563 + 110 CuBrminus 057 CuClminus 021 KS minus 014 pHP minus 011 TPS + 014 FeW+ 007 ZnSminus 002 PP + 001turbidity 10000
Pore water BrP minus1516minus 055 FeS minus 073 BS + 061 MnW+ 083 SiP + 049 NaS minus 031MnS minus 015 CuBr + 011 pHW minus 001CaW
10000
Sediment BrS 015 SiP + 195 CFAP+ 002 FP minus 045 IS + 192 sand+ 037 MnW minus 029 MgS minus 012 LiP + 005Ca3(PO4)2 minus 002 ZnF2
10000
IodideLake water IW 099 Ca(IO3)6H2O 09999
Pore water IP minus097 ZnF2 minus 057 Li3PO4 minus 053 BP + 034 FAP+ 015 Ca(IO3)2 +MnW+ 005 KS minus 009 turbidity + 055CaS
09999
Sediment IS minus072 + 135 SO4P + 023 Mn(IO3)2 + 063 FeW+ 031 TPS minus 035 MgP minus 012 Zn(CO3)22H2O 09993
40E + 0135E + 0130E + 0125E + 0120E + 0115E + 0110E + 0150E + 0000E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
12345
678910
111213
(a)
10E + 0090E ndash 0180E ndash 0170E ndash 0160E ndash 0150E ndash 0140E ndash 0130E ndash 0120E ndash 0110E ndash 0100E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
12345
678910
111213
(b)
12345
678910
111213
40E ndash 0235E ndash 0230E ndash 0225E ndash 0220E ndash 0215E ndash 0210E ndash 0250E ndash 0300E ndash 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
(c)
12345
678910
111213
80E ndash 0670E ndash 0660E ndash 0650E ndash 0640E ndash 0630E ndash 0620E ndash 0610E ndash 0600E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
(d)
Figure 5 Hazard quotient of ingestion and dermal contact of surface water and sediment of LakeMariout (a) ingestion of water (b) dermalcontact of water (c) ingestion of sediment and (d) dermal contact of sediment
Journal of Chemistry 15
Minerals and precipitated salts in the different partitions(surface water pore water and sediment) play an importantrole in the deposition and release of halogens in sedimentsAdditionally the texture and the porosity of the sedimentsplay a key role in the distribution of halogens in the threepartitions Interestingly chloride is the only halogen that hasnegligible interactions along the surface water and porewater partitions because it is present in large quantities inthe form of soluble salts (NaCl and MgCl2)
37 Pollution Status
371 Enrichment Factor (EF) Twowell-knownmethods areused to assess environmental pollution public health sig-nificance of ingestion and dermal contact with water andsediment components and sediment enrichment factor (EF)[59 60]
-e average EF values of the determined elements CaMg Na K Li B P Cu Zn Mn Fe F Cl Br and I are alllower than the value that is less than the minimum en-richment value (EFlt 2)-us the area under investigation isstill ecologically considered as an unpolluted region
372 Human Health Risk Assessment -e EDI HQ and HIshow the variable values of all pollutants in the surface waterand sediments along the lake region and in drains (sites11ndash13) under study Among all the calculated variables ofsurface water ingestion (EDIIngw) and dermal contact(EDIDermw) Cl is still the only variable that shows high levels(average 1551 and 43mg kgminus1 dayminus1 respectively) -eestimation daily intake of sediment ingestion (EDIIngs) anddermal contact (EDIDerms) of Mg Ca and Na give maximumaverage amounts of 841Eminus 02 513E ndash 02 and167Eminus 03mg kgminus1 dayminus1 respectively
Among the HQ of the calculated detection variables thecontent of HQB of ingestion and dermal contact with waterand sediment is the highest However 70 of sites have HQBvalues more than 10 (Figure 5) Comparing the HQ values ofall the determined variables HQB of the ingestion of surfacewater shows values higher (gt10) However due to the impactof drainage the HQB values of stations 1ndash4 8ndash10 12 and 13
are higher than 10 -erefore these sites can be consideredas the area with the most serious boron pollution caused byuntreated discharged water disposal In addition the HIIngwlevel of water ingestion for the studied variables in all sites ismuch higher than 10 (Figure 6) Except for boron it isusually concluded that the study area does not pose any riskto the population due to halogens or other variables Ac-cordingly this information may help the official authoritiesoptimize management plans and strengthen their pollutioncontrol actions in Lake Mariout
4 Conclusions
-e effects of halogen salts and minerals on the pollution ofLake Mariout were studied Halogens and some physico-chemical variables in three partitions surface water porewater and sediment in Lake Mariout were evaluated -ehalogen content was variable between different sites andchloride was the main halogen in surface water and porewater but it was very rare in the lakersquos sediment partitionPiper ternary diagram and Palmerrsquos method reflected thatNaCl was the dominant salt in surface water while MgCl2was the main dissolve salt in pore water-e chlorinity ratiosof halogens and tested variables were directly matched to thefeeding drain sources
Moreover the Saturation Index (SI) reveals that 23 and 15precipitated salts and minerals are formed in surface water andpore water respectively -e SI value indicated the formationof phosphate minerals in surface water and pore water es-pecially octacalcium phosphate (OCP Ca4H(PO4)325H2O)and hydroxyapatite (HAP Ca5(PO4)3OH) In addition tofluoride minerals especially fluorapatite (FAP) and carbonate-fluorapatite (CFAP) were obviously precipitated from surfacewater and pore water Soluble salts of bromide and chloridewere formed in surface water and pore water Iodide salts(Ca(IO3)2 and Ca(IO3)26H2O) were moderately precipitatedin the surface water and pore water
Moreover the multivariate analysis including the cor-relation matrix multiple stepwise linear regression treeclustering and principle component (PCA) of all the de-termined and calculated variables was applied to estimatethe proposed interaction between halogens and other tested
10E + 02
16E + 0214E + 0212E + 02
80E + 0160E + 0140E + 0120E + 0100E + 00
1 2 3 4 5 6 7 8 9 10 11 12 13
HIIngHIDerm
(a)
1 2 3 4 5 6 7 8 9 10 11 12 13
HIIngHIDerm
40E ndash 0235E ndash 0230E ndash 0225E ndash 0220E ndash 0215E ndash 0210E ndash 0250E ndash 0300E + 01
(b)
Figure 6 Hazard index of ingestion and dermal contact of the studied variables in surface water and sediment of Lake Mariout (a) waterand (b) sediment
16 Journal of Chemistry
variables in the polluted area under study -e multivariateanalysis showed that there were many interactions betweenhalogens and tested variables High levels of fluoride bro-mide and chloride in surface water were related to thecomposition of drainage waters -e enrichment factor (EF)showed that Lake Mariout was not polluted However thehuman health adverse effects calculated for surface waterand sediment did not reflect any possible likelihood hazardeffects from halogens
Interestingly the current study concluded that halogencompounds especially fluorides are most likely to be de-posited from surface lakes in the form of many minerals andprecipitation thereby reducing the adverse pollution effectson human health -e results obtained through this workhelp to find the correlations between the sampling sites andthe variables obtained by physical and chemical measure-ments which can be used to construct a fast decision modelfor separating different water quality samples -is infor-mation may help the official authorities optimize manage-ment plans and strengthen their pollution control measuresin Lake Mariout
Data Availability
-e data used to support the findings of this research areincluded within the paper
Conflicts of Interest
-e authors declare that there are no conflicts of interestregarding the publication of this manuscript
Supplementary Materials
Supplementary Table 1 correlation matrix of variable insurface water pore water and sediment partitions besidesthe precipitated salts in surface water along Lake Mariout(Supplementary Materials)
References
[1] M S Masoud T O Said G El-Zokm and M A ShreadahldquoAssesment of heavy metals contamination in surface sedi-ments of the Egyptian Red Sea Coastsrdquo Australian Journal ofBasic and Applied Sciences vol 6 pp 44ndash58 2012
[2] M A Shreadah M I Abdel Moneim T O SaidE M I Fathallah and M E Mahmoud ldquoPAHs in seawater ofthe semi-closed areas along the Alexandria coast of EgyptianMediterranean seardquo Journal of Environmental Protectionvol 4 no 11 p 11 Article ID 40298 2013
[3] S Abdel Ghani G El Zokm A Shobier T Othman andM Shreadah ldquoMetal pollution in surface sediments of Abu-Qir bay and Eastern harbour of Alexandria Egyptrdquo EgyptianJournal of Aquatic Research vol 39 no 1 pp 1ndash12 2013
[4] G F El-Said ldquoBioaccumulation of key metals and othercontaminants by seaweeds from the Egyptian MediterraneanSea Coast in relation to human health riskrdquo Human andEcological Risk Assessment An International Journal vol 19no 5 pp 1285ndash1305 2013
[5] M A Shreadah A H Shobier S Abdel Ghani G M El-Zokm and T O Said ldquoMajor ions anomalies and
contamination status by trace metals in sediments from twohot spots along the Mediterranean Coast of Egyptrdquo Envi-ronmental Monitoring and Assessment vol 187 no 280pp 1ndash18 2015
[6] A El Nemr G F El-Said A Khaled and S Ragab ldquoDis-tribution and ecological risk assessment of some heavy metalsin coastal surface sediments along the Red Sea Egyptrdquo In-ternational Journal of Sediment Research vol 31 no 2pp 164ndash172 2016
[7] A El Nemr G F El-Said S Ragab A Khaled and A El-Sikaily ldquo-e distribution contamination and risk assessmentof heavy metals in sediment and shellfish from the Red Seacoast Egyptrdquo Chemosphere vol 165 pp 369ndash380 2016
[8] A El Nemr and G F El-Said ldquoAssessment and ecological riskof heavy metals in sediment and molluscs from the Medi-terranean coastrdquo Water Environment Research vol 89 no 3pp 195ndash210 2017
[9] M A Sheradah A A El-Sikaily N M Abd El MoneamN E Abd El Maguid and M G Zaki ldquoChemical and bio-chemical evaluation of marine pollution by polychlorinatedbiphenyls and pesticides in two regions along the EgyptianMediterranean Seardquo International Journal of EnvironmentalMonitoring and Analysis vol 6 no 3 pp 95ndash109 2018
[10] M A Shreadah A A-M M El-Sayed A A S TahaA-M M Ahmed and H H Abdel Rahman ldquoEvaluation ofdifferent anthropogenic effluents impacts on the water qualityusing principal component analysis a case study of Abu-QirBay-Alexandria-Egyptrdquo International Journal of Environ-mental Monitoring and Analysis vol 7 no 3 pp 56ndash67 2019
[11] G F El-Said M M El-Sadaawy A H Shobier andS E Ramadan ldquoHuman health implication of major and traceelements present in commercial crustaceans of a traditionalseafood marketing region Egyptrdquo Biological Trace ElementResearch vol 199 pp 315ndash328 2020
[12] M A Shreadah S A A Ghani H B I HawashA A E Samie and A E M M Ahmed ldquoOrganotin com-pounds in sediments of northern lakes Egyptrdquo Journal ofEnvironmental Protection vol 05 no 17 pp 1654ndash1666 2014
[13] A M Younis G M El-Zokm and M A Okbah ldquoSpatialvariation of acid-volatile sulfide and simultaneously extractedmetals in Egyptian Mediterranean Sea lagoon sedimentsrdquoEnvironmental Monitoring and Assessment vol 186 no 6pp 3567ndash3579 2014
[14] G F El-Said S E O Draz M M El-Sadaawy andA A Moneer ldquoSedimentology geochemistry pollution statusand ecological risk assessment of some heavy metals insurficial sediments of an Egyptian lagoon connecting to theMediterranean Seardquo Journal of Environmental Science andHealth Part A vol 49 no 9 pp 1029ndash1044 2014
[15] G M El Zokm M A Okbah and A M Younis ldquoAssessmentof heavy metals pollution using AVS-SEM and fractionationtechniques in Edku Lagoon sediments Mediterranean SeaEgyptrdquo Journal of Environmental Science and Health PartAvol 50 no 6 pp 571ndash584 2015
[16] G M El Zokm H R Z Tadros M A Okbah andG H Ibrahim ldquoldquoEutrophication assessment using TRIX andCarlsonrsquos indices in Lake Mariout water Egyptrdquo EgyptianJournal of Aquatic Biology and Fisheries vol 22 no 5pp 331ndash349 2018
[17] N Donia ldquoLake Maryut monitoring using remote sensingrdquo inProceedings of the gypt Eighteenth International WaterTechnology Conference IWTC18 Sharm El Sheikh Abu DhabiUAE March 2015
Journal of Chemistry 17
[18] M A Khairy ldquoAssessment of priority phenolic compounds insediments from an extremely polluted coastal wetland (LakeMaryut Egypt)rdquo Environmental Monitoring and Assessmentvol 185 no 1 pp 441ndash455 2013
[19] N A El-Naggar and E A Rifaat ldquoEgyptian coastal lakes andwetlands part Imdashcharacteristics and hydrodynamicsrdquo in eHandbook of Environmental Chemistry A M Negm EdSpringer International Publishing AG Berlin Germany 2017
[20] J J Hanley and K T Koga ldquoChapter 2 ldquohalogens in terrestrialand cosmic geochemical systems abundances Geochemicalbehaviors and analytical methodsrdquordquo in e Role of Halogensin Terrestrial and Extraterrestrial Geochemical ProcessesD E Harlov and L Aranovich Eds Springer InternationalPublishing AG Berlin Germany pp 21ndash121 2018
[21] A Ghosh K Mukherjee S K Ghosh and B Saha ldquoSourcesand toxicity of fluoride in the environmentrdquo Research onChemical Intermediates vol 39 no 7 pp 2881ndash2915 2013
[22] M M Naim A A Moneer and G F El-Said ldquoPredictiveequations for the defluoridation by electrocoagulation tech-nique using bipolar aluminum electrodes in the absence andpresence of additives a multivariate studyrdquo Desalination andWater Treatment vol 57 no 14 pp 6320ndash6332 2016
[23] G F El-Said N A Shaltout M M El-Sadaawy andA M H Morsy ldquo-e precipitation of fluoride calcium andmagnesium minerals from Egyptian Mediterranean Sea coastin relation to discharged watersrdquo Desalination and WaterTreatment vol 57 no 5 pp 2113ndash2124 2016
[24] H Bureau ldquoIodine encyclopedia of geochemistry A com-prehensive reference source on the chemistry of the earthrdquo inEncyclopedia of Earth Sciences Series W M White Ed copySpringer International Publishing AG 2016
[25] F C Kupper and C J Carrano ldquoKey aspects of the iodinemetabolism in brown algae a brief critical reviewrdquo Metal-lomics vol 11 pp 756ndash764 2019
[26] R Liteplo R Gomes P Howe and H Malcolm Fluorides-Environmental Health Criteria 227 p 290 World HealthOrganization (WHO) Geneva Switzerland 2002
[27] G F El-Said and M M El-Sadaawy ldquoSeasonal variation ofboron and fluoride in Tilapia nilotica from an Egyptian fishfarm in relation to Human health hazard assessmentrdquoHumanand Ecological Risk Assessment An International Journalvol 19 no 4 pp 930ndash943 2013
[28] WHO (World Health Organization) Bromide in Drinking-Water Background Document for Development of WHOGuidelines for Drinking-Water Quality WHO Press WorldHealth Organization Geneva Switzerland 2009
[29] G F El-Said and N A Sallam ldquo-e uptake of fluorideconcentration and its effects on the growth rate of shrimps(Palaemon elegans Rathke)rdquo Chemistry and Ecology vol 24no 3 pp 191ndash205 2008
[30] X Zhang J He B He and J Sun ldquoAssessment formationmechanism and different source contributions of dissolvedsalt pollution in the shallow groundwater of Hutuo Riveralluvial-pluvial fan in the North China Plainrdquo EnvironmentalScience and Pollution Research vol 26 no 35 pp 35742ndash35756 2019
[31] Y Zhu B Huang Z Zhu et al ldquoldquoCharacterization disso-lution and solubility of the hydroxypyromorphitendashhydroxyapatite solid solution [(PbxCa1minusx)5(PO4)3OH] at25 degC and pH 2ndash9rdquo Geochemical Transactions vol 17 no 2pp 1ndash18 2016
[32] G F El-Said M M El-Sadaawy A A Moneer andN A Shaltout ldquo-e effect of fluoride on the distribution ofsome minerals in the surface water of an Egyptian lagoon at
the Mediterranean Seardquo Egyptian Journal of Aquatic Researchvol 41 no 1 pp 31ndash39 2015
[33] Y Zhu Z Zhu X Zhao Y Liang and Y Huang ldquoChar-acterization dissolution and solubility of lead hydroxypyr-omorphite [Pb5(PO4)3OH] at 25ndash45degCrdquo Journal ofChemistry vol 2015 Article ID 269387 10 pages 2015
[34] M A Z Chahouki ldquoMultivariate analysis techniques inenvironmental sciencerdquo in Earth and Environmental SciencesDr Imran Ahmad Dar Ed InTech Open London UK 2011httpwwwintechopencombooksearth-and-environmental-sciencesmultivariate-analysis-techniques-inenvironmental-science
[35] J V Klump and C S Martens ldquoBiogeochemical cycling in anorganic-rich coastal marine basin 5 Sedimentary nitrogenand phosphorus budgets based upon kinetic models massbalances and the stoichiometry of nutrient regenerationrdquoGeochimica et Cosmochimica Acta vol 51 no 5 pp 1161ndash1173 1987
[36] R L Folk Petrology of Sedimentary Rocks University of TexasAustin TX USA 1974
[37] P Saenger ldquoA rapid spectrophotometric method for thedetermination of bromine in seawater and in the ash ofmarine algaerdquo Helgolander Wissenschaftliche Meer-esuntersuchungen vol 23 no 1 pp 32ndash37 1972
[38] P G Jeffery Chemical Methods of Rock Analysis PergamonPress New York NY USA 2nd edition 1975
[39] J D H Strickland and T R Parsons ldquoA practical handbook ofseawater analysisrdquo in Fisheries Research Board of CanadaBulletin 167p 311 Second edition Wiley Ottawa Canada1972
[40] B Horvath O Opara-Nadi and F Beese ldquoA simple methodfor measuring the carbonate content of soilsrdquo Soil ScienceSociety of America Journal vol 69 no 4 pp 1066ndash1068 2005
[41] K Grasshoff Methods of Seawater Analysis p 317 VerlagChemie Weinkeim Germany 1976
[42] R Danovaro D Marrale N Della Croce P Parodi andM Fabiano ldquoBiochemical composition of sedimentary or-ganic matter and bacterial distribution in the Aegean Seatrophic state and pelagic-benthic couplingrdquo Journal of SeaResearch vol 42 no 2 pp 117ndash129 1999
[43] APHA-AWWA-WPCF (American Public Health Associa-tion) Standard Methods for the Examination of Water andWaste Water American Public Health Association Wash-ington DC USA 20th edition 1999
[44] K I Aspila H Agemian and A S Y Chau ldquoA semi-auto-mated method for the determination of inorganic organicand total phosphate in sedimentsrdquo e Analyst vol 101no 1200 pp 187ndash197 1976
[45] J P Riley and D Taylor ldquoChelating resins for the concen-tration of trace elements from sea water and their analyticaluse in conjunction with atomic absorption spectrophotom-etryrdquo Analytica Chimica Acta vol 40 pp 479ndash485 1968
[46] G F El-Said and A El-Sikaily ldquoChemical composition ofsome seaweed from Mediterranean Sea coast Egyptrdquo Envi-ronmental Monitoring and Assessment vol 185 no 7pp 6089ndash6099 2013
[47] Directorate General of Health Services Ministry of Health andFamilyWelfare Government of India ldquoManual of methods ofanalysis of foodsrdquo in Fruit and Vegetable Productsp 57Directorate General of Health Services Ministry of Health andFamily Welfare Government of India New Delhi India2005
[48] A Gunnars S Blomqvist and C Martinsson ldquoInorganicformation of apatite in brackish seawater from the Baltic Sea
18 Journal of Chemistry
an experimental approachrdquo Marine Chemistry vol 91 no 1-4 pp 15ndash26 2004
[49] W M Haynes D R Lide and T J Bruno CRC Handbook ofChemistry and Physics A Ready Reference Book of Chemicaland Physical Data CRC Press Taylor amp Frances Group BocaRaton FL USA 97th edition 2017
[50] M S Masoud M I El-Samra and M M El-Sadawy ldquoWaterchemistry of el-mex bay west of Alexandria Egyptrdquo eEgypian Science Magazine vol 2 pp 70ndash78 2005
[51] F J Millero R Feistel D G Wright and T J McDougallldquo-e composition of standard seawater and the definition ofthe reference-composition salinity scalerdquo Deep Sea ResearchPart I Oceanographic Research Papers vol 55 no 1pp 50ndash72 2008
[52] S K El-Wakeel S A Morcos and A M Mahlis ldquo-e majorcations in Lake Maryut watersrdquo Hydrobiologia vol 36 no 2pp 253ndash274 1970
[53] A M Mahlis S A Morcos and S K El-Wakeel ldquo-e majoranions in Lake Maryut watersrdquo Hydrobiologia vol 36 no 2pp 275ndash294 1970
[54] A S Saad M A Massoud R A Amer and M A GhorabldquoAssessment of the physico-chemical characteristics andwater quality analysis of Mariout Lake southern of Alexan-dria Egyptrdquo Journal of Environmental and Analytical Toxi-cology vol 7 no 1 p 421 2017
[55] R Rumuri ldquoDataset on hydrogeochemical characteristics ofgroundwater and surface water in Kattumannarkoil TalukIndiardquo Data in Brief vol 32 Article ID 106058 2020
[56] P Szefer S W Fowler K Ikuta et al ldquoA comparative as-sessment of heavy metal accumulation in soft parts and byssusof mussels from subarctic temperate subtropical and tropicalmarine environmentsrdquo Environmental Pollution vol 139no 1 pp 70ndash78 2006
[57] N F Soliman G M El Zokm and M A Okbah ldquoRisk as-sessment and chemical fractionation of selected elements insurface sediments from Lake Qarun Egypt using modifiedBCR techniquerdquo Chemosphere vol 191 pp 262ndash271 2018
[58] G M El Zokm M I A Ibrahim L A Mohamed and M El-Mamoney ldquoCritical geochemical insight into Alexandria coastwith special reference to diagnostic ratios (TOCTN amp SrCa)and heavy metals ecotoxicological hazardsrdquo Egyptian Journalof Aquatic Research vol 46 no 1 pp 27ndash33 2020
[59] A S Likuku K B Mmolawa and G K GaboutloeloeldquoAssessment of heavy metal enrichment and degree of con-tamination around the copper-nickel mine in the SelebiPhikwe Region Eastern Botswanardquo Environment and EcologyResearch vol 1 no 2 pp 32ndash40 2013
[60] M K Khalil S E O Draz G M El Zokm and G F El-SaidldquoApportionment of geochemistry texturersquos properties and riskassessment of some elements in surface sediments from Bar-dawil Lagoon Egyptrdquo Human and Ecological Risk AssessmentAn International Journal vol 22 no 3 pp 775ndash791 2016
[61] M M El-Sadaawy and G F El-Said ldquoAssessment of fluoridein three selected polluted environments along the EgyptianMediterranean Sea effects on local populationsrdquo Human andEcological Risk Assessment An International Journal vol 20no 6 pp 1643ndash1658 2014
[62] USEPA ldquoSuperfund exposure assessment manualrdquo inOSWER Directive 92855-1EPA540l-88001Office of Emer-gency and Remedial Response Washington DC USA 1988
[63] USEPA ldquoExposure factors handbookrdquo in EPA6008-89043Office of Health and Environmental Assessment Wash-ington DC USA 1989
[64] Health Canada ldquoFederal Contaminated Site Risk Assessmentin Canadardquo Part II Health Canada Toxicological ReferenceValues (TRVs) Cat H46-204-368E Calgary Health CanadaOttawa Canada 2007
[65] J Iqbal S A Tirmizi and M H Shah ldquoStatistical appor-tionment and risk assessment of selected metals in sedimentsfrom Rawal Lake (Pakistan)rdquo Environmental Monitoring andAssessment vol 185 no 1 pp 729ndash743 2013
[66] USEPA (US Environmental Protection Agency) Region 6USAEPA ldquoMultimedia Planning and Permitting DivisionrdquoOffice of Solid Waste Center for Combustion Science andEngineering Washington DC USA 2005
[67] P Jeschke ldquoLatest generation of halogen-containing pesti-cidesrdquo Pest Management Science vol 73 no 6 pp 1053ndash10662017
[68] M A Shreadah O A El-Rayis N A Shaaban andA M Hamdan ldquoWater quality assessment and phosphorusbudget of a lake (Mariut Egypt) after diversion of wastewaterseffluentsrdquo Environmental Science and Pollution Researchvol 27 no 21 pp 26786ndash26799 2020
[69] J P Riley and M Tongudai ldquo-e major cationchlorinityratios in sea waterrdquo Chemical Geology vol 2 pp 263ndash2691967
[70] R B McCleskey D K Nordstrom D D Susong J W Balland J M Holloway ldquoSource and fate of inorganic solutes inthe gibbon river yellowstone national park Wyoming USArdquoJournal of Volcanology and Geothermal Research vol 193no 3-4 pp 189ndash202 2010
[71] G T F Wong and K-Y Li ldquoWinklerrsquos method overestimatesdissolved oxygen in seawater iodate interference and itsoceanographic implicationsrdquo Marine Chemistry vol 115no 1-2 pp 86ndash91 2009
[72] B S R V Prasad P D N Srinivasu P S VarmaA V Raman and S Ray ldquoDynamics of dissolved oxygen inrelation to saturation and health of an aquatic body a case forChilka Lagoon Indiardquo Journal of Ecosystems vol 2014 Ar-ticle ID 526245 17 pages 2014
[73] China Environmental Protection Agency EnvironmentalQuality Standards for Surface Water (GB3838ndash2002) NationalEnvironmental Protection Agency of China Beijing China2002
[74] Y Jia L Wang Z Qu and Z Yang ldquoDistribution con-tamination and accumulation of heavy metals in watersediments and freshwater shellfish from Liuyang RiverSouthern Chinardquo Environmental Science and Pollution Re-search vol 25 no 7 pp 7012ndash7020 2018
[75] A Moneer M El-Sadawy G El-Said and A Radwan ldquoBoronhuman health risk assessment relative to the environmentalpollution of Lake Edku Egyptrdquo Journal of King AbdulazizUniversity vol 23 no 2 pp 41ndash55 2012
[76] C B Tabelin T Igarashi T Arima D Sato T Tatsuhara andS Tamoto ldquoCharacterization and evaluation of arsenic andboron adsorption onto natural geologic materials and theirapplication in the disposal of excavated altered rockrdquo Geo-derma vol 213 pp 163ndash172 2014
[77] G Aloisi K Wallmann M Drews and G BohrmannldquoEvidence for the submarine weathering of silicate minerals inBlack Sea sediments possible implications for the marine Liand B cyclesrdquo Geochemistry Geophysics Geosystems vol 5no 4 pp 1ndash22 2004
[78] C Degueldre and V Cloet ldquoPore water colloid properties inargillaceous sedimentary rocksrdquo Science of e Total Envi-ronment vol 569-570 pp 423ndash433 2016
Journal of Chemistry 19
[79] J A Higgins and D P Schrag ldquoRecords of Neogene seawaterchemistry and diagenesis in deep-sea carbonate sedimentsand pore fluidsrdquo Earth and Planetary Science Letters vol 357-358 pp 386ndash396 2012
[80] H Schroeder A-L Fabricius D Ecker T A Ternes andL Duester ldquoMetal(loid) speciation and size fractionation insediment pore water depth profiles examined with a newmesoprofiling systemrdquo Chemosphere vol 179 pp 185ndash193 2017
[81] Y Song and G Muller ldquoFreshwater sediments sinks andsources of brominerdquo Naturwissenschaften vol 80 no 12pp 558ndash560 1993
[82] M E Goher H I Farhat M H Abdo and S G Salem ldquoMetalpollution assessment in the surface sediment of Lake NasserEgyptrdquo Egyptian Journal of Aquatic Research vol 40 no 3pp 213ndash224 2014
[83] G F El-Said M M El-Sadawy and A A Moneer ldquoIncor-poration of fluoride and boron into surface sediments alongthe Egyptian Mediterranean coastrdquo Egyptian Journal ofAquatic Research vol 36 no 4 pp 569ndash583 2010
[84] B Gilfedder G M Petri M Wessels and H Biester ldquoAniodine mass-balance for Lake Constance Germany insightsinto iodine speciation changes and fluxesrdquo Geochimica etCosmochimica Acta vol 74 no 11 pp 3090ndash3111 2010
[85] E Korobova L Kolmykova B Ryzhenko et al ldquoDistributionand speciation of iodine in drinking waters from geochem-ically different areas of Bryansk region contaminated after theChernobyl accident in relation to health and remediationaspectsrdquo Journal of Geochemical Exploration vol 184pp 311ndash317 2018
[86] V Zic V W Truesdale and N Cukrov ldquo-e distribution ofiodide and iodate in anchialine cave watersmdashevidence forsustained localised oxidation of iodide to iodate in marinewaterrdquoMarine Chemistry vol 112 no 3-4 pp 168ndash178 2008
[87] M B Heeb J Criquet S G Zimmermann-Steffens andU Von Gunten ldquoOxidative treatment of bromide-containingwaters formation of bromine and its reactions with inorganicand organic compoundsmdasha critical reviewrdquo Water Researchvol 48 pp 15ndash42 2014
[88] V Sivasankar A K Darchen and R Omine SakthivelldquoChapter 2 ldquofluoride a world ubiquitous compound itschemistry and ways of contaminationrdquo in Surface ModifiedCarbons as Scavengers for Fluoride fromWater V SivasankarEd pp 5ndash32 copy Springer International Publishing Switzer-land Cham Switzerland 2016
[89] O Cabestrero P Del Buey and M E Sanz-Montero ldquoBio-sedimentary and geochemical constraints on the precipitationof mineral crusts in shallow sulphate lakesrdquo SedimentaryGeology vol 366 pp 32ndash46 2018
[90] M A Hassaan O A El-Rayis and E I Hemada ldquoEstimationof the redox potential of lake mariut drainage system (Qalaaand Umum drains)rdquoHydrology vol 5 no 6 pp 82ndash85 2017
20 Journal of Chemistry
ple 0028) Mgw amp Liw (r 0790 ple 0002) Naw amp Kw(r 0955 ple 0000 Naw amp Liw (r 0835 ple 0001) Naw ampCO3w (r minus0701 ple 0011) Kw amp Liw (r 0712 ple 0009)Kw amp CO3w (r minus0580 ple 0048) CO3w amp HCO3w(r minus0613 ple 0034) and Mgw amp SO4w (r 0631ple 0028) indicate that all these variables have some geo-chemical behaviors [77] Mg Na and Li are some com-ponents of the discharged waters however they havepositive correlations with the chlorinity and salinity of thedischarged water sources (r 0743 0619 and 0815 re-spectively) and (r 0743 0619 and 0815 respectively)Mgw and Liw contents in water samples are affected bytemperature dissolved oxygen and pH with high correla-tions of r minus0650 0677 and 0743 and minus0702 0659 and0815 respectively
32 Distribution of Halogens and Tested Variables in PoreWater
321 Distribution of Halogens in Pore Water -e averagehalogen contents in the pore water are higher than theircontents in the surface water but in the same orderClpgtBpgt Fpgt Ip (Table 3) Current research shows that thelowest and highest average values of Spermilp and Clp have beenmeasured in the pore water of site 6 and site 8 respectively Itis worth mentioning that site 6 is a mixed water of El-Qalaadrainage sewage WWTP treatment plant and lake waterInterestingly the high concentrations of fluoride chloridebromide and iodide in the pore water at site 6 are 123mgLminus1 40321mg Lminus1 11739mg Lminus1 and 24339 μg Lminus1 re-spectively (Table 3) -e salinity and chloride content in thepore water of site 8 are related to the discharge water of manypetrochemical and oil companies besides some fish farms
322 Distribution of Tested Variables in Pore Water -etested variables in the pore water (p) give the followingdescending order MgpgtNapgtCapgt SO4pgtBpgtKpgtBrpgt Fpgt LipgtPpgt Ipgt Sip (Table 3) Interestingly the deter-mined variables in the pore water have higher values thanthe surface water along the lake According to previousstudies pore water is responsible for biogeochemical reac-tions the migration and transformation of partitioned andformed compounds and the transportation of colloidalspecies [78 79] In addition pore water can explore thepotential risks of man-made pollution sources [80] -etested variables in the pore water (p) are given in a differentorder of surface water of ClpgtMgpgtNapgtCapgt SO4pgtBpgtKpgtBrpgt Fpgt Lipgt Ppgt Ipgt Sip (Tables 2and 3)
323 Interactions of Halogens and Tested Variables in PoreWater -e following interactions of halogens CO3w amp Ip Ipamp Fw Brw amp Sip Fp amp Siw and Fp amp Nap give correlationvalues (r 0706 ple 0010 r minus0606 ple 0037 r 0826ple 0001 r minus0704 ple 0011 and r 0670 ple 0017respectively) (Supplementary Table 1) However these re-lationships may indicate their precipitation andor
adsorption on the colloidal particles besides the formation ofsome chemical species [78 79] Extraordinarily large cor-relations of Nap amp HCO3w Kp amp HCO3w Spermilw amp Bp Spermilp ampKp Spermilp amp Lip and Spermilp amp Clp (r 0692 minus0609 minus07410696 0910 and 1000) may refer to the release of theseelements from sediment particles andor precipitation oradsorption [77] In the matrix the negative correlationbetween Cap and Mgp (r minus0592 ple 0042) may be relatedto the release of Mg during the recrystallization of calcite[79]-e relationship between Caw amp SO4p Cuw amp Cap Pw ampPp and Nap amp pHw (r 0744 ple 0006 r 0719 ple 0008r 0647 ple 0023 and r minus0640 ple 0025 respectively)may be due to the chemical interactions in the pore fluidsand the formation certain compounds
33Distribution ofHalogens andTestedVariables in Sediment
331 Distribution of Halogens in Sediment -e averagehalogenrsquos content in the sediment shows a different orderfrom the surface and pore waters of Brsgt FsgtClsgt Is (Ta-ble 4) -e sediment results show that the average bromidecontent is higher than fluoride followed by chloride contentand iodide with average values of 452mg gminus1 040mg gminus1029mg gminus1 and 450 μg gminus1 respectively
-e fluoride concentration in the sediment ranges from001 to 120mg gminus1 with an average value of 04plusmn 035mggminus1 -ese values are lower than reported marine sedimentvalues and higher than the El-Bardawil Lagoon [60]Amongst the halogens the study reveals that Br is the mostabundant ion in surface water pore water and sedimentsamples due to the excessive amounts of organic matter [81]On the contrary the concentration of Cl ions in sedimentsamples is lower than that in surface water and pore watersamples indicating that it exists in soluble salts -e currentresults indicate that the sediments collected from the mostaffected area by the Mediterranean Sea (site 6) contain el-evated levels of fluoride (070mg gminus1) bromide (852mggminus1) and chloride (020mg gminus1) and a reduced amount ofiodide (209 μg gminus1) (Table 4)
332 Distribution of Tested Variables in Sediment -eaverage value of test variables in the determined sedimentsamples shows a significant change from site to site with adescending order CO3sgtMgsgtCasgtNasgt SO4s gt FesgtBsgtKsgtTPsgtMn sgtZnsgtCusgt Lis (Table 4) Plus this studyclears out that the percent of sand and mud of the differentsediment samples ranges from 4 at sites 1 amp 13 to 85 atsite 11 and from 15 at site 11 to 96 at sites 1amp13 re-spectively with averages 25 and 75 respectively Plusthe porosity shows a trend opposite to the particle size andvaries from 4676 to 8214 with an average value of5609plusmn 1114 -e results of the current study reveal mod-erate amounts of CO3 in the sediment samples fluctuatingbetween 1639 and 5736 at sites 6 and 2 respectively -eresults of sand mud porosity and CO3 percentage reflect thatthe texture of the sediment is mainly composed of mud mixedwith carbonate compounds Comprehensively the large storageof sediments with carbonate (359plusmn1280) magnesium
Journal of Chemistry 9
Tabl
e3
Distribu
tionof
thestud
iedvariablesin
thepo
rewater
(p)alon
gLake
Mariout
Site
Spermilp
pHP
Ca p
(mgLminus
1 )Mg p
(mgLminus
1 )Na p
(mgLminus
1 )Kp
(mgLminus
1 )Li
p(m
gLminus
1 ))
SO4P
(mgLminus
1 ))
B P(m
gLminus
1 ))
P P(μgLminus
1 ))
SiP
(microgLminus
1 ))
F p(m
gLminus
1 ))
Cl P
(mgLminus
1 ))
Brp
(mgLminus
1 ))
I p(μgLminus
1 )1
1034
787
481
42303
1097
453
042
2944
8043
363
0045
323
95419
959
7104
2934
809
5611
115725
1050
498
039
2056
663
553
0036
338
8398
1385
24698
31272
717
100
5689
1195
577
053
2778
8949
1204
0034
754
114469
2291
26347
483
796
9619
47652
974
384
043
350
19312
77
0054
215
74599
693
8393
51099
782
5611
89711
1128
42041
1667
16739
1112
0081
1698864
1332
8333
645
775
4008
75367
736
41024
2111
11739
071
0037
1231
40321
799
24339
71125
782
39278
13615
1155
516
056
3667
6051
369
006
6101209
1279
8123
8148
775
9299
84314
1355
468
055
12444
942
212
0056
892
133232
1172
7643
9684
78
962
72109
880
393
036
3778
21341
114
0087
1061429
2131
9981
10114
764
1122
113586
1195
524
049
4667
8007
071
0041
1138
102562
1332
8572
11639
742
4008
61996
915
332
033
2833
11594
754
0026
1215
67834
746
37587
125
702
481
38413
8703
274
028
2167
13913
081
0025
2154
44832
1438
9891
13755
807
3206
6467
817
446
039
4556
17246
635
0042
954
5737
533
1097
Minim
um45
702
962
13615
736
274
024
1667
6051
071
0025
215
40321
533
7104
Maxim
um148
809
39278
115725
8703
577
056
12444
21341
1204
0087
2154
133232
2291
37587
Average
919
77
718
67412
163077
4381
041
3782
1223
485
0048
955
82779
1238
14768
SD308
032
10027
29209
2132
825
01
2769
5047
391
0019
542
27891
524
9917
10 Journal of Chemistry
Tabl
e4
Distribu
tionof
thestud
iedvariablesin
thesediment(s)alon
gLake
Mariout
Site
Sand
()
Mud ()
Porosity
()
CO3s
()
B s(m
ggminus
1 )P s
(mg
gminus1 )
Ca s
(mg
gminus1 )
Mg s
(mg
gminus1 )
Na s
(mg
gminus1 )
Ks
(mg
gminus1 )
Lis(m
ggminus
1 )
SO4s
(mg
gminus1 )
Fes
(mg
gminus1 )
Cu s (μg
gminus1 )
Mn s
(μg
gminus1 )
Zns(μg
gminus1 )
F s(m
ggminus
1 )
Cl s
(mg
gminus1 )
Brs
(mg
gminus1 )
I s(μg
gminus1 )
14
964915
183
299
044
1670
811
2583
408
0028
4861
828
963
5617
1272
034
041
128
1686
244
564925
574
196
028
1002
1419
2717
269
0015
662
257
793
4350
1313
057
054
123
358
319
816667
299
246
073
1670
1216
3125
336
0022
463
487
1228
4330
1677
044
034
448
516
418
824853
3813
1111
032
668
2229
3425
365
0094
2222
770
922
4637
1245
030
020
309
296
512
884697
482
614
012
501
1115
1833
091
0040
1713
243
600
27933
1223
082
034
245
254
65
954667
164
370
157
835
1257
2958
388
0030
5648
890
1927
5347
3117
070
020
852
209
75
954762
375
524
024
367
2047
3133
256
0102
1157
546
883
4185
1393
120
020
341
259
838
626143
457
697
039
668
1621
3550
347
0145
4167
598
737
4157
1412
022
034
144
1277
918
826000
349
083
054
401
1094
3358
369
0025
2454
701
868
5702
3065
036
027
250
172
1036
645070
441
296
002
935
1763
3117
246
0045
2685
369
790
4533
1315
012
047
1012
224
1185
157000
325
240
074
969
2250
3508
328
0193
1343
1026
735
3890
1070
005
007
533
128
1237
638214
463
291
032
334
1824
3008
358
0018
556
340
728
2475
827
001
007
852
281
134
965000
177
211
054
2338
1621
3925
599
0068
833
1687
1187
6492
1853
004
027
639
194
Min
415
4667
164
083
002
334
811
1833
091
0015
463
243
600
2475
827
001
007
123
128
Max
8596
8214
574
1111
157
2338
2250
3925
599
0193
6620
1687
1927
6492
3117
120
054
1012
1686
Av
2575
5609
359
398
048
951
1559
3096
335
0063
2671
672
951
4500
1599
040
029
452
450
SD23
231114
128
276
039
603
455
522
115
0055
2030
393
343
1120
708
035
014
303
475
Minm
inim
umM
axm
axim
uma
ndAv
averageSD
stand
arddeviation
Journal of Chemistry 11
(1559plusmn455mg gminus1) and calcium (951plusmn603mg gminus1) com-ponents may be attributed to the abundance of calcium min-erals [4] However in general the average amounts of allvariables in sediment samples showmarked variations fromonesite to another with a descending order of CO3sgtMgsgtCasgtNasgtSO4sgtFesgt BrsgtBsgtKsgtTPsgtFs gtClsgtMnsgtZnsgtCusgtLisgt Is (Table 4) -e measured concentra-tions of Mn Zn Cu and Fe in the sediment samples are stilllower than the reported values and also lower than the back-ground levels of crust and the toxicological reference contents ofUS DOE (US Department of Energy) US EPA (US Envi-ronmental Protection Agency) and CEQG (Canadian Envi-ronmental Quality Guidelines) [82]
Contrasting the obtained levels for the halogens withthose previously reported ones the present study indicatesthat surface and pore waters incorporate more considerableamounts of fluoride compared to the formerly reported onesin Lake Edku (Tables 2 and 3) and lower levels in theMarioutarea than those measured along the Egyptian MediterraneanSea coast [27] Compared with the sediments previouslyfound on the Mediterranean coast of Egypt the chloridecontent in the sediments of the Mariout area is lower [83]Compared with those observed in seawater the studiedsurface water and pore water samples have lower bromidecontent and higher levels than previously reported in LakeMariout [52 53] -e concentration of iodide in surfacewater pore water and sediments is equivalent to the con-centration of rivers and lakes in the world [84]
333 Interactions of Halogens and Tested Variables inSediment -e correlation matrix shows the important roleof halogens in the formation and precipitationdissolution ofsalts and minerals produced along the lake (SupplementaryTable 1) However it shows that chloride seems to be in thesoluble forms along the surface and pore waters of studiedarea showing good relations with Caw (r 0666 ple 0018)Clp (r 0677 ple 0016) and SO4p (r 0858 ple 0000)Also Cls gives good correlations with Mgw (r 0710ple 0010) Naw (r 0602 ple 0038) Clw (r 0619ple 0032) Mgp (r 0774 ple 0003) and Kp (r 0731ple 0007) Chloride in the surface and pore waters plays animportant role in the dissolution association and formationof various salts along the lake -e good relationship be-tween Is and Caw (r 0666 ple 0018) may reflect the de-positionrelease of CaI+ during the formationdissolution ofcalcium carbonate [85] In addition these correlations maybe related to organic-I which formed by bacterial species andtheir remineralization in bottom sediments [86] -emoderate relationship between Nas and Brw (r minus0622ple 0031) may indicate the possible formation of BrClspecies and the precipitation or adsorption of Na minerals insediments [87] -e results of this study also reflect thestrong negative correlation between Fs and Bw (r minus0666ple 0018) which may be related to the release of fluoridefrom sediment and the formation of soluble fluoridecomplexes ((BFn[OH]4minusn)minus) with the excessive boron con-centration in the water [88] -e negative relation betweenKs and Spermilw (r minus0673 ple 0016) possibly reflect that Kw
preferentially chooses to exist in the soluble form of KClrather than being adsorbed andor bound by some richminerals in the sediment
-e significant correlations between CO3s and Mgw(r 0637 ple 0026) CO3s and Clw (r 0723 ple 0008)CO3s and pHw (r 0833 ple 0001) CO3s and Spermilw(r 0723 ple 0008) and between CO3s and Ks (r minus0673ple 0016) may be accompanied by the possible formationdissolution of the dolomite mineral in the presence ofsufficient Mgw which is usually affected by optimal pHsalinity and the potassium salts (Supplementary Table 1)-ese observed results are matching with the previouslyreported studies [32] Significant negative correlation be-tween TPs and CO3s (r minus0744 ple 0006) may indicate theextended release of P from carbonate minerals and for-mation of apatites [32]
-e correlation matrix also refers to other possible in-teractions between the remaining determined variables(Supplementary Table 1) -e significant correlation be-tween SO4s andMgw (r 0706 ple 0010) and Liw (r 0633ple 0027) may be associated to the formation of Mg-sulfateand the pollution of sediments by discharged waters con-taining excessive sulfate and Li [89] In the contrary thestrong positive correlation between TPs and Cus and be-tween TPs and Zns may be related to the same source ofpolluted discharge water [23 83]
-e high negative correlations of Zns with Few(r minus0785 ple 0003) CO3s (r minus0601 ple 0039) and Cus(r 0698 ple 0012) may indicate that Zn Cu and CO3depositions in sediment samples are linked to the soluble Feform in water (ferrous) ie the release of Fe upwards in thewater column in the anoxic conditions (SupplementaryTable 1) [90] -e excellent relations found between Fesand CO3s (r minus0799 ple 0002) Fes and Cas (r 0637ple 0026) Fes and Clw (r minus0752 ple 0005) Fes and Nas(r 0720 ple 0008) and between Fes and Ks (r 0833ple 0001) may reflect the dissolution of the chelating Feassociation with the soluble organic compounds in thewater-sediment interface and the formation of the sol-uble ferrous form in low dissolved oxygen within theareas affected by untreated discharged waters [90] -estrong correlations of Mns with SO4w Nap Nas Ks CO3sZns and Fes (r minus0585 0608 0611 0698 minus0655 0691and 0716 respectively) may associate with the solubilityof abundant Mn minerals and P-Mn forms in the sedi-ment because of its possible reduction to Mn+2 solublespecies under anoxic conditions [90] It is worth men-tioning that the results of this study indicate that ap-proximately 333 of the survey sites indicate thedepletion of dissolved oxygen in their surface watersamples Under such anoxic conditions bacteria are mostlikely to use sulfate instead of oxygen to break downorganic matter and cause the release of iron and phos-phorus into the water column
-e significant direct correlation between Ks and Nas(r 0832 plt 0001) clearly reflects the transport of solublesalts of K and Na between the pore water phase of thesediment and water-sediment surface phase (SupplementaryTable 1) -e good correlation between porosity and Nas
12 Journal of Chemistry
indicates the possible transfer of Na between pore water andsediment partitions
34 Interactions of Precipitated Halogenated Compounds inSurface and Pore Waters -e Saturation Index (SI) [23 60]of twenty-three and fifteen structures in surface water andpore water samples respectively are listed (Table 1) -ecorrelation matrix of the calculated Saturation Indices withthe presented data shows the different factors affecting theinteraction of the halogenated compound with other pre-cipitated salts and minerals Table 1 explores the precipitationof the phosphate minerals and salts are most abundantfollowed by the hydroxidesrsquo salts iodate salts sulfate andcarbonate minerals and salts in surface waters Amongst thehalogens precipitated salts fluoride minerals especiallyfluorapatites and carbonate-fluorapatite (FAP and CFAP)have high SI values in surface water (4277ndash5195 and1604ndash6089 respectively) and in pore water (5126ndash5460 and1752ndash7833 respectively) Bromide and chloride are mainlyfound in the soluble forms in surface and pore waters Iodidesalts (Ca(IO3)2 and Ca(IO3)26H2O) moderately precipitatein surface and pore Iron salts precipitate in surface waterwhile in pore water they are not formed -us SI contentreflects that halogens especially fluoride and iodide play avital role in reducing lake pollution
In addition Table 1 shows that the precipitation com-pounds that may be formed in surface water are relativelydifferent from those in sediment pore water For examplefluorite (CaF2) and sellaıte (MgF2) may be only formed inpore water while calcite and aragonite may be deposited insurface water However the formation of fluorite in surfacewater is related to Naw (r 0778 ple 0003) Kw (r 0704ple 0011) CO3w (r minus0718 ple 0009) Fw (r 0770ple 0003) and Ip (r minus0785 ple 0003) (SupplementaryTable 1)
-e formation of calcium sulfate hemihydrate calciumsulfate and anhydrite in water is related to the increase in theamounts of Caw Mgw SO4w Nap Fp Sip Cls and Mns andthe decrease in porosity values On the other hand pre-cipitation of calcium phosphate is related to Brw (r 0751ple 0005) Znw (r 0668 ple 0018) Pw (r 0881ple 0001) and Ks (r 0881 ple 0001) ie it is affected bythe discharged water composition (Supplementary Table 1)
-e formation of calcite and aragonite in surface water isrelated to the formation of CO3w (r 0753 ple 0005) anddissociation of HCO3w (r minus0660 ple 0020) pHw values(r minus0654 ple 0021) and their dissolution in sediment(r minus0620 ple 0032) (Supplementary Table 1)
-e dolomite formation in water may be affected by theincrease of CO3w (r 0817 ple 0001) and the decrease ofHCO3w (r minus0658 ple 0020) increase in TDSw (r 0599ple 0040) and increase in pHw (r minus0656 ple 0021)besides the possible release of CO3s from abundant sediment(r minus0624 ple 0030) and the precipitation of calcite(r 0984 ple 0000) and aragonite (r 0984 ple 0000) intosediment fraction (Supplementary Table 1)
Generally in the current study the possible formedhalogenated minerals and salts are affected by their
abundance in different components of the lake besides theirpossible dissolution or formation on the sediment texturesgeochemistry of the sediments and physicochemical vari-ables of water in addition to the components of the dis-charged waters
35 Interactions of Dissolved Halogenated Compounds inSurface and PoreWaters -e utilization of dissolved salts insurface and pore waters by utilizing Palmerrsquos method andpiper ternary diagram [50] indicates that Na is the richestcation in surface water followed by Mg Ca and K At thesame time Mg is the most predominate one in the porewater (Figures 3 and 4) Obviously Cl is the most importantanion in surface water and pore waters samples Howeverthe piper ternary diagrams of surface water and pore waterclearly shows that NaCl is the most dominant in surfacewater while MgCl2 is the most abundant in pore waterCoincidently Palmerrsquos method also reflects that NaCl(574) is the most existent species in surface water fol-lowed by MgCl2 (304) CaCl2 (71) CaSO4 (29)Ca(HCO3)2 (14) and KCl (12) (Figure 3) At the sametime MgCl2 (760) is the most present species in porewater followed by NaCl (73)asympMg(HCO3)2 (73)Ca(HCO3)2 (52) and MgSO4 (31) (Figure 4)
36 Multivariate Analysis
361 Principal Component (PCA) By applying Varimaxrotation and Kaiser normalization to 98 variables in the PCAfor halogens and tested variables and calculated parametervalues 7 extracted PCs with eigenvalues higher than 1 areobtained However it is important that the eigenvalue mustbe greater than 1 Its seven PCs explain 8558 of the totalvariance
-e first principle component (PC1) is 1473 of thetotal variance and shows positive coefficient factor loadingsfor CO3w TDSw Kp calcite aragonite dolomite FeCO3MgCO3 ZnCO3 and ZnCO3H2O (0804 0547 05320938 0938 0947 0741 0940 0866 and 0866 respec-tively) In addition it provides negative factor loadings forHCO3w pHw Bw Nap and CO3s (minus0782 minus0610 minus0595minus0532 and minus0572 respectively) PC1 is related to thefactors affecting the carbonate compounds that may beformed in the area under consideration
PC2 accounts to 1458 of the total variance and alsoshows positive and negative coefficient factor loadingsrepresenting the different interactions between the CawMgw Liw SO4wMgp Nap pHp Cls SO4s Brs and porosityin water pore water and sediment that are responsible forthe composition of sulfate magnesium and phosphateprecipitates besides the effect of the discharged waters onwater-pore water-sediment componentsrsquo cycles
PC3 typically shows 1377 of the total variance withpositive and negative loadings which can properly explorethe effect of the principal sources of local pollution on thedissolving of heavy metals B and P from sediment into thewater column and the probable formation of Fe(OH)2Fe(OH)3) and FePO4
Journal of Chemistry 13
Similarly the coefficient factor loadings of PC4 with1355 are related to the influence of the polluted dischargewater and sediment texture on the formation of F Cl and Isalt besides the precipitation of halogenated compounds(FeF2 Mn(IO3)2 KIO4 and KCIO4) besides their minerals(CaF2 MgF2 FAP and CFAP)
Simultaneously PC5 gives 1092 of the total variancewith positive and negative loadings which explains therelations between the physicochemical limits of the surfacewater pore water and sediment components and theprecipitation of minerals and salts (OCP HAP CuBrZn(OH)2 and Zn(IO3)22H2O) -is is also associated tothe influence of the sedimentary material on the release ofMn Fe and P from sediment into pore water and watercolumn and formation of Ca3(PO4)2 OCP and HAPminerals
However PC6 associates with 100 of the total variancegiving positive and negative coefficient factor loadingswhich explain that the sediments (minerals andor organic-iodine compounds) are only the acting sink for iodine andiodine species (Iminus and IOminus
3 ) in the water as previously re-ported [84] PC6 also reflects the precipitation of severalhalogenated compounds such as calcium iodate (Ca(IO3)2and Ca(IO3)26H2O) and copper iodate (CuI andCuIO3H2O) besides Cu3(PO4)2 species in the lake watercolumn
-e loadings of PC7 contribute by 804 and show thatthe release of calcium in pore water into the water column isresponsible for the precipitation of halogenated compounds(CuCl and Zn(IO3)22H2O) as well as copper and Zn salts(Cu3(PO4)2 and Zn(OH)2)
362 Cluster Analysis On the other hand cluster analysisshows that the similarity of sites 1amp4 5amp8 6amp9 2amp10 and11amp13 is due to the texture of sediment
363 Multiple Regression Multiple regression equations ofhalogens as dependent variables and the other determinedand calculated parameters as independent variables insurface water pore water and sediment partitions are listed(Table 5)-e amount of fluoride in water samples is affectedby the discharged watersrsquo fundamental components espe-cially Zn and Cu besides its surface water-pore water in-teractions Its content in pore water seems to be stronglyaffected by its substitution competition with other halogensin surface water-spore water-sediment cycle due to its highelectronegativity Generally in the affected area the type ofpollutant in the discharged water plays an important role inthe dissolution andor precipitation of fluoride and otherhalogens in the surface water-pore water-sediment cycle
574
147129
300
12
Ca(HCO3)2CaSO4CaCl2
MgCl2KClNaCl
(a)
SO4
2 + CIndash Ca 2+ + Mg 2+
CO32ndash + HCO3
ndashNa+ + K+
Mg2+ SO42ndash
Ca2+ CIndash
(b)
Figure 3 (a) distribution and (b) piper ternary diagram of the formed dissolved salts in surface water of Lake Mariout
Ca(HCO3)2Mg(HCO3)2MgSO4
NaClMgCI2KCl
760 1052
7373 31
(a)
SO4
2ndash + C
Indash
Ca 2+ + Mg 2+
CO32ndash + HCO3
ndashNa+ + K+
Mg2+ SO42ndash
CIndashCa2+
(b)
Figure 4 (a) distribution and (b) piper ternary diagram of the formed dissolved salts in pore water of Lake Mariout
14 Journal of Chemistry
Table 5 -e multiple regression analyses of each halogen as dependent variable and other tested variables in the surface water pore waterand sediment partitions besides the precipitated salts in surface water along Lake Mariout
Dependentvariable Multiple regression equation R2
FluorideLake water FW 3162 + 092 Zn F2 minus 033 SiP + 021 CuIminus 017 SpermilP 09911
Pore water Fp minus2567minus117 SiW minus 033 LiP minus 062 CuClminus 028 IS + 023 TDSW+ 017 KIO4 minus 012 BrW minus 004porosity + 004 PW
10000
Sediment FS 088 CAPminus 049 MgS minus 046 DOW+039MgW+ 027 Mn(IO3)2 + 015 Cu3(PO4)2 + 004 HAP+ 002 pHP 10000ChlorideLake water No relation 00000Pore water No relation 00000Sediment ClS minus116 + 046 MgP + 077 Kp minus 049 dolomite + 017 TDSW minus 011 CuI + 005 NaS + 002 BS + 001 FeF2 10000Bromide
Lake water BrW 1563 + 110 CuBrminus 057 CuClminus 021 KS minus 014 pHP minus 011 TPS + 014 FeW+ 007 ZnSminus 002 PP + 001turbidity 10000
Pore water BrP minus1516minus 055 FeS minus 073 BS + 061 MnW+ 083 SiP + 049 NaS minus 031MnS minus 015 CuBr + 011 pHW minus 001CaW
10000
Sediment BrS 015 SiP + 195 CFAP+ 002 FP minus 045 IS + 192 sand+ 037 MnW minus 029 MgS minus 012 LiP + 005Ca3(PO4)2 minus 002 ZnF2
10000
IodideLake water IW 099 Ca(IO3)6H2O 09999
Pore water IP minus097 ZnF2 minus 057 Li3PO4 minus 053 BP + 034 FAP+ 015 Ca(IO3)2 +MnW+ 005 KS minus 009 turbidity + 055CaS
09999
Sediment IS minus072 + 135 SO4P + 023 Mn(IO3)2 + 063 FeW+ 031 TPS minus 035 MgP minus 012 Zn(CO3)22H2O 09993
40E + 0135E + 0130E + 0125E + 0120E + 0115E + 0110E + 0150E + 0000E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
12345
678910
111213
(a)
10E + 0090E ndash 0180E ndash 0170E ndash 0160E ndash 0150E ndash 0140E ndash 0130E ndash 0120E ndash 0110E ndash 0100E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
12345
678910
111213
(b)
12345
678910
111213
40E ndash 0235E ndash 0230E ndash 0225E ndash 0220E ndash 0215E ndash 0210E ndash 0250E ndash 0300E ndash 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
(c)
12345
678910
111213
80E ndash 0670E ndash 0660E ndash 0650E ndash 0640E ndash 0630E ndash 0620E ndash 0610E ndash 0600E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
(d)
Figure 5 Hazard quotient of ingestion and dermal contact of surface water and sediment of LakeMariout (a) ingestion of water (b) dermalcontact of water (c) ingestion of sediment and (d) dermal contact of sediment
Journal of Chemistry 15
Minerals and precipitated salts in the different partitions(surface water pore water and sediment) play an importantrole in the deposition and release of halogens in sedimentsAdditionally the texture and the porosity of the sedimentsplay a key role in the distribution of halogens in the threepartitions Interestingly chloride is the only halogen that hasnegligible interactions along the surface water and porewater partitions because it is present in large quantities inthe form of soluble salts (NaCl and MgCl2)
37 Pollution Status
371 Enrichment Factor (EF) Twowell-knownmethods areused to assess environmental pollution public health sig-nificance of ingestion and dermal contact with water andsediment components and sediment enrichment factor (EF)[59 60]
-e average EF values of the determined elements CaMg Na K Li B P Cu Zn Mn Fe F Cl Br and I are alllower than the value that is less than the minimum en-richment value (EFlt 2)-us the area under investigation isstill ecologically considered as an unpolluted region
372 Human Health Risk Assessment -e EDI HQ and HIshow the variable values of all pollutants in the surface waterand sediments along the lake region and in drains (sites11ndash13) under study Among all the calculated variables ofsurface water ingestion (EDIIngw) and dermal contact(EDIDermw) Cl is still the only variable that shows high levels(average 1551 and 43mg kgminus1 dayminus1 respectively) -eestimation daily intake of sediment ingestion (EDIIngs) anddermal contact (EDIDerms) of Mg Ca and Na give maximumaverage amounts of 841Eminus 02 513E ndash 02 and167Eminus 03mg kgminus1 dayminus1 respectively
Among the HQ of the calculated detection variables thecontent of HQB of ingestion and dermal contact with waterand sediment is the highest However 70 of sites have HQBvalues more than 10 (Figure 5) Comparing the HQ values ofall the determined variables HQB of the ingestion of surfacewater shows values higher (gt10) However due to the impactof drainage the HQB values of stations 1ndash4 8ndash10 12 and 13
are higher than 10 -erefore these sites can be consideredas the area with the most serious boron pollution caused byuntreated discharged water disposal In addition the HIIngwlevel of water ingestion for the studied variables in all sites ismuch higher than 10 (Figure 6) Except for boron it isusually concluded that the study area does not pose any riskto the population due to halogens or other variables Ac-cordingly this information may help the official authoritiesoptimize management plans and strengthen their pollutioncontrol actions in Lake Mariout
4 Conclusions
-e effects of halogen salts and minerals on the pollution ofLake Mariout were studied Halogens and some physico-chemical variables in three partitions surface water porewater and sediment in Lake Mariout were evaluated -ehalogen content was variable between different sites andchloride was the main halogen in surface water and porewater but it was very rare in the lakersquos sediment partitionPiper ternary diagram and Palmerrsquos method reflected thatNaCl was the dominant salt in surface water while MgCl2was the main dissolve salt in pore water-e chlorinity ratiosof halogens and tested variables were directly matched to thefeeding drain sources
Moreover the Saturation Index (SI) reveals that 23 and 15precipitated salts and minerals are formed in surface water andpore water respectively -e SI value indicated the formationof phosphate minerals in surface water and pore water es-pecially octacalcium phosphate (OCP Ca4H(PO4)325H2O)and hydroxyapatite (HAP Ca5(PO4)3OH) In addition tofluoride minerals especially fluorapatite (FAP) and carbonate-fluorapatite (CFAP) were obviously precipitated from surfacewater and pore water Soluble salts of bromide and chloridewere formed in surface water and pore water Iodide salts(Ca(IO3)2 and Ca(IO3)26H2O) were moderately precipitatedin the surface water and pore water
Moreover the multivariate analysis including the cor-relation matrix multiple stepwise linear regression treeclustering and principle component (PCA) of all the de-termined and calculated variables was applied to estimatethe proposed interaction between halogens and other tested
10E + 02
16E + 0214E + 0212E + 02
80E + 0160E + 0140E + 0120E + 0100E + 00
1 2 3 4 5 6 7 8 9 10 11 12 13
HIIngHIDerm
(a)
1 2 3 4 5 6 7 8 9 10 11 12 13
HIIngHIDerm
40E ndash 0235E ndash 0230E ndash 0225E ndash 0220E ndash 0215E ndash 0210E ndash 0250E ndash 0300E + 01
(b)
Figure 6 Hazard index of ingestion and dermal contact of the studied variables in surface water and sediment of Lake Mariout (a) waterand (b) sediment
16 Journal of Chemistry
variables in the polluted area under study -e multivariateanalysis showed that there were many interactions betweenhalogens and tested variables High levels of fluoride bro-mide and chloride in surface water were related to thecomposition of drainage waters -e enrichment factor (EF)showed that Lake Mariout was not polluted However thehuman health adverse effects calculated for surface waterand sediment did not reflect any possible likelihood hazardeffects from halogens
Interestingly the current study concluded that halogencompounds especially fluorides are most likely to be de-posited from surface lakes in the form of many minerals andprecipitation thereby reducing the adverse pollution effectson human health -e results obtained through this workhelp to find the correlations between the sampling sites andthe variables obtained by physical and chemical measure-ments which can be used to construct a fast decision modelfor separating different water quality samples -is infor-mation may help the official authorities optimize manage-ment plans and strengthen their pollution control measuresin Lake Mariout
Data Availability
-e data used to support the findings of this research areincluded within the paper
Conflicts of Interest
-e authors declare that there are no conflicts of interestregarding the publication of this manuscript
Supplementary Materials
Supplementary Table 1 correlation matrix of variable insurface water pore water and sediment partitions besidesthe precipitated salts in surface water along Lake Mariout(Supplementary Materials)
References
[1] M S Masoud T O Said G El-Zokm and M A ShreadahldquoAssesment of heavy metals contamination in surface sedi-ments of the Egyptian Red Sea Coastsrdquo Australian Journal ofBasic and Applied Sciences vol 6 pp 44ndash58 2012
[2] M A Shreadah M I Abdel Moneim T O SaidE M I Fathallah and M E Mahmoud ldquoPAHs in seawater ofthe semi-closed areas along the Alexandria coast of EgyptianMediterranean seardquo Journal of Environmental Protectionvol 4 no 11 p 11 Article ID 40298 2013
[3] S Abdel Ghani G El Zokm A Shobier T Othman andM Shreadah ldquoMetal pollution in surface sediments of Abu-Qir bay and Eastern harbour of Alexandria Egyptrdquo EgyptianJournal of Aquatic Research vol 39 no 1 pp 1ndash12 2013
[4] G F El-Said ldquoBioaccumulation of key metals and othercontaminants by seaweeds from the Egyptian MediterraneanSea Coast in relation to human health riskrdquo Human andEcological Risk Assessment An International Journal vol 19no 5 pp 1285ndash1305 2013
[5] M A Shreadah A H Shobier S Abdel Ghani G M El-Zokm and T O Said ldquoMajor ions anomalies and
contamination status by trace metals in sediments from twohot spots along the Mediterranean Coast of Egyptrdquo Envi-ronmental Monitoring and Assessment vol 187 no 280pp 1ndash18 2015
[6] A El Nemr G F El-Said A Khaled and S Ragab ldquoDis-tribution and ecological risk assessment of some heavy metalsin coastal surface sediments along the Red Sea Egyptrdquo In-ternational Journal of Sediment Research vol 31 no 2pp 164ndash172 2016
[7] A El Nemr G F El-Said S Ragab A Khaled and A El-Sikaily ldquo-e distribution contamination and risk assessmentof heavy metals in sediment and shellfish from the Red Seacoast Egyptrdquo Chemosphere vol 165 pp 369ndash380 2016
[8] A El Nemr and G F El-Said ldquoAssessment and ecological riskof heavy metals in sediment and molluscs from the Medi-terranean coastrdquo Water Environment Research vol 89 no 3pp 195ndash210 2017
[9] M A Sheradah A A El-Sikaily N M Abd El MoneamN E Abd El Maguid and M G Zaki ldquoChemical and bio-chemical evaluation of marine pollution by polychlorinatedbiphenyls and pesticides in two regions along the EgyptianMediterranean Seardquo International Journal of EnvironmentalMonitoring and Analysis vol 6 no 3 pp 95ndash109 2018
[10] M A Shreadah A A-M M El-Sayed A A S TahaA-M M Ahmed and H H Abdel Rahman ldquoEvaluation ofdifferent anthropogenic effluents impacts on the water qualityusing principal component analysis a case study of Abu-QirBay-Alexandria-Egyptrdquo International Journal of Environ-mental Monitoring and Analysis vol 7 no 3 pp 56ndash67 2019
[11] G F El-Said M M El-Sadaawy A H Shobier andS E Ramadan ldquoHuman health implication of major and traceelements present in commercial crustaceans of a traditionalseafood marketing region Egyptrdquo Biological Trace ElementResearch vol 199 pp 315ndash328 2020
[12] M A Shreadah S A A Ghani H B I HawashA A E Samie and A E M M Ahmed ldquoOrganotin com-pounds in sediments of northern lakes Egyptrdquo Journal ofEnvironmental Protection vol 05 no 17 pp 1654ndash1666 2014
[13] A M Younis G M El-Zokm and M A Okbah ldquoSpatialvariation of acid-volatile sulfide and simultaneously extractedmetals in Egyptian Mediterranean Sea lagoon sedimentsrdquoEnvironmental Monitoring and Assessment vol 186 no 6pp 3567ndash3579 2014
[14] G F El-Said S E O Draz M M El-Sadaawy andA A Moneer ldquoSedimentology geochemistry pollution statusand ecological risk assessment of some heavy metals insurficial sediments of an Egyptian lagoon connecting to theMediterranean Seardquo Journal of Environmental Science andHealth Part A vol 49 no 9 pp 1029ndash1044 2014
[15] G M El Zokm M A Okbah and A M Younis ldquoAssessmentof heavy metals pollution using AVS-SEM and fractionationtechniques in Edku Lagoon sediments Mediterranean SeaEgyptrdquo Journal of Environmental Science and Health PartAvol 50 no 6 pp 571ndash584 2015
[16] G M El Zokm H R Z Tadros M A Okbah andG H Ibrahim ldquoldquoEutrophication assessment using TRIX andCarlsonrsquos indices in Lake Mariout water Egyptrdquo EgyptianJournal of Aquatic Biology and Fisheries vol 22 no 5pp 331ndash349 2018
[17] N Donia ldquoLake Maryut monitoring using remote sensingrdquo inProceedings of the gypt Eighteenth International WaterTechnology Conference IWTC18 Sharm El Sheikh Abu DhabiUAE March 2015
Journal of Chemistry 17
[18] M A Khairy ldquoAssessment of priority phenolic compounds insediments from an extremely polluted coastal wetland (LakeMaryut Egypt)rdquo Environmental Monitoring and Assessmentvol 185 no 1 pp 441ndash455 2013
[19] N A El-Naggar and E A Rifaat ldquoEgyptian coastal lakes andwetlands part Imdashcharacteristics and hydrodynamicsrdquo in eHandbook of Environmental Chemistry A M Negm EdSpringer International Publishing AG Berlin Germany 2017
[20] J J Hanley and K T Koga ldquoChapter 2 ldquohalogens in terrestrialand cosmic geochemical systems abundances Geochemicalbehaviors and analytical methodsrdquordquo in e Role of Halogensin Terrestrial and Extraterrestrial Geochemical ProcessesD E Harlov and L Aranovich Eds Springer InternationalPublishing AG Berlin Germany pp 21ndash121 2018
[21] A Ghosh K Mukherjee S K Ghosh and B Saha ldquoSourcesand toxicity of fluoride in the environmentrdquo Research onChemical Intermediates vol 39 no 7 pp 2881ndash2915 2013
[22] M M Naim A A Moneer and G F El-Said ldquoPredictiveequations for the defluoridation by electrocoagulation tech-nique using bipolar aluminum electrodes in the absence andpresence of additives a multivariate studyrdquo Desalination andWater Treatment vol 57 no 14 pp 6320ndash6332 2016
[23] G F El-Said N A Shaltout M M El-Sadaawy andA M H Morsy ldquo-e precipitation of fluoride calcium andmagnesium minerals from Egyptian Mediterranean Sea coastin relation to discharged watersrdquo Desalination and WaterTreatment vol 57 no 5 pp 2113ndash2124 2016
[24] H Bureau ldquoIodine encyclopedia of geochemistry A com-prehensive reference source on the chemistry of the earthrdquo inEncyclopedia of Earth Sciences Series W M White Ed copySpringer International Publishing AG 2016
[25] F C Kupper and C J Carrano ldquoKey aspects of the iodinemetabolism in brown algae a brief critical reviewrdquo Metal-lomics vol 11 pp 756ndash764 2019
[26] R Liteplo R Gomes P Howe and H Malcolm Fluorides-Environmental Health Criteria 227 p 290 World HealthOrganization (WHO) Geneva Switzerland 2002
[27] G F El-Said and M M El-Sadaawy ldquoSeasonal variation ofboron and fluoride in Tilapia nilotica from an Egyptian fishfarm in relation to Human health hazard assessmentrdquoHumanand Ecological Risk Assessment An International Journalvol 19 no 4 pp 930ndash943 2013
[28] WHO (World Health Organization) Bromide in Drinking-Water Background Document for Development of WHOGuidelines for Drinking-Water Quality WHO Press WorldHealth Organization Geneva Switzerland 2009
[29] G F El-Said and N A Sallam ldquo-e uptake of fluorideconcentration and its effects on the growth rate of shrimps(Palaemon elegans Rathke)rdquo Chemistry and Ecology vol 24no 3 pp 191ndash205 2008
[30] X Zhang J He B He and J Sun ldquoAssessment formationmechanism and different source contributions of dissolvedsalt pollution in the shallow groundwater of Hutuo Riveralluvial-pluvial fan in the North China Plainrdquo EnvironmentalScience and Pollution Research vol 26 no 35 pp 35742ndash35756 2019
[31] Y Zhu B Huang Z Zhu et al ldquoldquoCharacterization disso-lution and solubility of the hydroxypyromorphitendashhydroxyapatite solid solution [(PbxCa1minusx)5(PO4)3OH] at25 degC and pH 2ndash9rdquo Geochemical Transactions vol 17 no 2pp 1ndash18 2016
[32] G F El-Said M M El-Sadaawy A A Moneer andN A Shaltout ldquo-e effect of fluoride on the distribution ofsome minerals in the surface water of an Egyptian lagoon at
the Mediterranean Seardquo Egyptian Journal of Aquatic Researchvol 41 no 1 pp 31ndash39 2015
[33] Y Zhu Z Zhu X Zhao Y Liang and Y Huang ldquoChar-acterization dissolution and solubility of lead hydroxypyr-omorphite [Pb5(PO4)3OH] at 25ndash45degCrdquo Journal ofChemistry vol 2015 Article ID 269387 10 pages 2015
[34] M A Z Chahouki ldquoMultivariate analysis techniques inenvironmental sciencerdquo in Earth and Environmental SciencesDr Imran Ahmad Dar Ed InTech Open London UK 2011httpwwwintechopencombooksearth-and-environmental-sciencesmultivariate-analysis-techniques-inenvironmental-science
[35] J V Klump and C S Martens ldquoBiogeochemical cycling in anorganic-rich coastal marine basin 5 Sedimentary nitrogenand phosphorus budgets based upon kinetic models massbalances and the stoichiometry of nutrient regenerationrdquoGeochimica et Cosmochimica Acta vol 51 no 5 pp 1161ndash1173 1987
[36] R L Folk Petrology of Sedimentary Rocks University of TexasAustin TX USA 1974
[37] P Saenger ldquoA rapid spectrophotometric method for thedetermination of bromine in seawater and in the ash ofmarine algaerdquo Helgolander Wissenschaftliche Meer-esuntersuchungen vol 23 no 1 pp 32ndash37 1972
[38] P G Jeffery Chemical Methods of Rock Analysis PergamonPress New York NY USA 2nd edition 1975
[39] J D H Strickland and T R Parsons ldquoA practical handbook ofseawater analysisrdquo in Fisheries Research Board of CanadaBulletin 167p 311 Second edition Wiley Ottawa Canada1972
[40] B Horvath O Opara-Nadi and F Beese ldquoA simple methodfor measuring the carbonate content of soilsrdquo Soil ScienceSociety of America Journal vol 69 no 4 pp 1066ndash1068 2005
[41] K Grasshoff Methods of Seawater Analysis p 317 VerlagChemie Weinkeim Germany 1976
[42] R Danovaro D Marrale N Della Croce P Parodi andM Fabiano ldquoBiochemical composition of sedimentary or-ganic matter and bacterial distribution in the Aegean Seatrophic state and pelagic-benthic couplingrdquo Journal of SeaResearch vol 42 no 2 pp 117ndash129 1999
[43] APHA-AWWA-WPCF (American Public Health Associa-tion) Standard Methods for the Examination of Water andWaste Water American Public Health Association Wash-ington DC USA 20th edition 1999
[44] K I Aspila H Agemian and A S Y Chau ldquoA semi-auto-mated method for the determination of inorganic organicand total phosphate in sedimentsrdquo e Analyst vol 101no 1200 pp 187ndash197 1976
[45] J P Riley and D Taylor ldquoChelating resins for the concen-tration of trace elements from sea water and their analyticaluse in conjunction with atomic absorption spectrophotom-etryrdquo Analytica Chimica Acta vol 40 pp 479ndash485 1968
[46] G F El-Said and A El-Sikaily ldquoChemical composition ofsome seaweed from Mediterranean Sea coast Egyptrdquo Envi-ronmental Monitoring and Assessment vol 185 no 7pp 6089ndash6099 2013
[47] Directorate General of Health Services Ministry of Health andFamilyWelfare Government of India ldquoManual of methods ofanalysis of foodsrdquo in Fruit and Vegetable Productsp 57Directorate General of Health Services Ministry of Health andFamily Welfare Government of India New Delhi India2005
[48] A Gunnars S Blomqvist and C Martinsson ldquoInorganicformation of apatite in brackish seawater from the Baltic Sea
18 Journal of Chemistry
an experimental approachrdquo Marine Chemistry vol 91 no 1-4 pp 15ndash26 2004
[49] W M Haynes D R Lide and T J Bruno CRC Handbook ofChemistry and Physics A Ready Reference Book of Chemicaland Physical Data CRC Press Taylor amp Frances Group BocaRaton FL USA 97th edition 2017
[50] M S Masoud M I El-Samra and M M El-Sadawy ldquoWaterchemistry of el-mex bay west of Alexandria Egyptrdquo eEgypian Science Magazine vol 2 pp 70ndash78 2005
[51] F J Millero R Feistel D G Wright and T J McDougallldquo-e composition of standard seawater and the definition ofthe reference-composition salinity scalerdquo Deep Sea ResearchPart I Oceanographic Research Papers vol 55 no 1pp 50ndash72 2008
[52] S K El-Wakeel S A Morcos and A M Mahlis ldquo-e majorcations in Lake Maryut watersrdquo Hydrobiologia vol 36 no 2pp 253ndash274 1970
[53] A M Mahlis S A Morcos and S K El-Wakeel ldquo-e majoranions in Lake Maryut watersrdquo Hydrobiologia vol 36 no 2pp 275ndash294 1970
[54] A S Saad M A Massoud R A Amer and M A GhorabldquoAssessment of the physico-chemical characteristics andwater quality analysis of Mariout Lake southern of Alexan-dria Egyptrdquo Journal of Environmental and Analytical Toxi-cology vol 7 no 1 p 421 2017
[55] R Rumuri ldquoDataset on hydrogeochemical characteristics ofgroundwater and surface water in Kattumannarkoil TalukIndiardquo Data in Brief vol 32 Article ID 106058 2020
[56] P Szefer S W Fowler K Ikuta et al ldquoA comparative as-sessment of heavy metal accumulation in soft parts and byssusof mussels from subarctic temperate subtropical and tropicalmarine environmentsrdquo Environmental Pollution vol 139no 1 pp 70ndash78 2006
[57] N F Soliman G M El Zokm and M A Okbah ldquoRisk as-sessment and chemical fractionation of selected elements insurface sediments from Lake Qarun Egypt using modifiedBCR techniquerdquo Chemosphere vol 191 pp 262ndash271 2018
[58] G M El Zokm M I A Ibrahim L A Mohamed and M El-Mamoney ldquoCritical geochemical insight into Alexandria coastwith special reference to diagnostic ratios (TOCTN amp SrCa)and heavy metals ecotoxicological hazardsrdquo Egyptian Journalof Aquatic Research vol 46 no 1 pp 27ndash33 2020
[59] A S Likuku K B Mmolawa and G K GaboutloeloeldquoAssessment of heavy metal enrichment and degree of con-tamination around the copper-nickel mine in the SelebiPhikwe Region Eastern Botswanardquo Environment and EcologyResearch vol 1 no 2 pp 32ndash40 2013
[60] M K Khalil S E O Draz G M El Zokm and G F El-SaidldquoApportionment of geochemistry texturersquos properties and riskassessment of some elements in surface sediments from Bar-dawil Lagoon Egyptrdquo Human and Ecological Risk AssessmentAn International Journal vol 22 no 3 pp 775ndash791 2016
[61] M M El-Sadaawy and G F El-Said ldquoAssessment of fluoridein three selected polluted environments along the EgyptianMediterranean Sea effects on local populationsrdquo Human andEcological Risk Assessment An International Journal vol 20no 6 pp 1643ndash1658 2014
[62] USEPA ldquoSuperfund exposure assessment manualrdquo inOSWER Directive 92855-1EPA540l-88001Office of Emer-gency and Remedial Response Washington DC USA 1988
[63] USEPA ldquoExposure factors handbookrdquo in EPA6008-89043Office of Health and Environmental Assessment Wash-ington DC USA 1989
[64] Health Canada ldquoFederal Contaminated Site Risk Assessmentin Canadardquo Part II Health Canada Toxicological ReferenceValues (TRVs) Cat H46-204-368E Calgary Health CanadaOttawa Canada 2007
[65] J Iqbal S A Tirmizi and M H Shah ldquoStatistical appor-tionment and risk assessment of selected metals in sedimentsfrom Rawal Lake (Pakistan)rdquo Environmental Monitoring andAssessment vol 185 no 1 pp 729ndash743 2013
[66] USEPA (US Environmental Protection Agency) Region 6USAEPA ldquoMultimedia Planning and Permitting DivisionrdquoOffice of Solid Waste Center for Combustion Science andEngineering Washington DC USA 2005
[67] P Jeschke ldquoLatest generation of halogen-containing pesti-cidesrdquo Pest Management Science vol 73 no 6 pp 1053ndash10662017
[68] M A Shreadah O A El-Rayis N A Shaaban andA M Hamdan ldquoWater quality assessment and phosphorusbudget of a lake (Mariut Egypt) after diversion of wastewaterseffluentsrdquo Environmental Science and Pollution Researchvol 27 no 21 pp 26786ndash26799 2020
[69] J P Riley and M Tongudai ldquo-e major cationchlorinityratios in sea waterrdquo Chemical Geology vol 2 pp 263ndash2691967
[70] R B McCleskey D K Nordstrom D D Susong J W Balland J M Holloway ldquoSource and fate of inorganic solutes inthe gibbon river yellowstone national park Wyoming USArdquoJournal of Volcanology and Geothermal Research vol 193no 3-4 pp 189ndash202 2010
[71] G T F Wong and K-Y Li ldquoWinklerrsquos method overestimatesdissolved oxygen in seawater iodate interference and itsoceanographic implicationsrdquo Marine Chemistry vol 115no 1-2 pp 86ndash91 2009
[72] B S R V Prasad P D N Srinivasu P S VarmaA V Raman and S Ray ldquoDynamics of dissolved oxygen inrelation to saturation and health of an aquatic body a case forChilka Lagoon Indiardquo Journal of Ecosystems vol 2014 Ar-ticle ID 526245 17 pages 2014
[73] China Environmental Protection Agency EnvironmentalQuality Standards for Surface Water (GB3838ndash2002) NationalEnvironmental Protection Agency of China Beijing China2002
[74] Y Jia L Wang Z Qu and Z Yang ldquoDistribution con-tamination and accumulation of heavy metals in watersediments and freshwater shellfish from Liuyang RiverSouthern Chinardquo Environmental Science and Pollution Re-search vol 25 no 7 pp 7012ndash7020 2018
[75] A Moneer M El-Sadawy G El-Said and A Radwan ldquoBoronhuman health risk assessment relative to the environmentalpollution of Lake Edku Egyptrdquo Journal of King AbdulazizUniversity vol 23 no 2 pp 41ndash55 2012
[76] C B Tabelin T Igarashi T Arima D Sato T Tatsuhara andS Tamoto ldquoCharacterization and evaluation of arsenic andboron adsorption onto natural geologic materials and theirapplication in the disposal of excavated altered rockrdquo Geo-derma vol 213 pp 163ndash172 2014
[77] G Aloisi K Wallmann M Drews and G BohrmannldquoEvidence for the submarine weathering of silicate minerals inBlack Sea sediments possible implications for the marine Liand B cyclesrdquo Geochemistry Geophysics Geosystems vol 5no 4 pp 1ndash22 2004
[78] C Degueldre and V Cloet ldquoPore water colloid properties inargillaceous sedimentary rocksrdquo Science of e Total Envi-ronment vol 569-570 pp 423ndash433 2016
Journal of Chemistry 19
[79] J A Higgins and D P Schrag ldquoRecords of Neogene seawaterchemistry and diagenesis in deep-sea carbonate sedimentsand pore fluidsrdquo Earth and Planetary Science Letters vol 357-358 pp 386ndash396 2012
[80] H Schroeder A-L Fabricius D Ecker T A Ternes andL Duester ldquoMetal(loid) speciation and size fractionation insediment pore water depth profiles examined with a newmesoprofiling systemrdquo Chemosphere vol 179 pp 185ndash193 2017
[81] Y Song and G Muller ldquoFreshwater sediments sinks andsources of brominerdquo Naturwissenschaften vol 80 no 12pp 558ndash560 1993
[82] M E Goher H I Farhat M H Abdo and S G Salem ldquoMetalpollution assessment in the surface sediment of Lake NasserEgyptrdquo Egyptian Journal of Aquatic Research vol 40 no 3pp 213ndash224 2014
[83] G F El-Said M M El-Sadawy and A A Moneer ldquoIncor-poration of fluoride and boron into surface sediments alongthe Egyptian Mediterranean coastrdquo Egyptian Journal ofAquatic Research vol 36 no 4 pp 569ndash583 2010
[84] B Gilfedder G M Petri M Wessels and H Biester ldquoAniodine mass-balance for Lake Constance Germany insightsinto iodine speciation changes and fluxesrdquo Geochimica etCosmochimica Acta vol 74 no 11 pp 3090ndash3111 2010
[85] E Korobova L Kolmykova B Ryzhenko et al ldquoDistributionand speciation of iodine in drinking waters from geochem-ically different areas of Bryansk region contaminated after theChernobyl accident in relation to health and remediationaspectsrdquo Journal of Geochemical Exploration vol 184pp 311ndash317 2018
[86] V Zic V W Truesdale and N Cukrov ldquo-e distribution ofiodide and iodate in anchialine cave watersmdashevidence forsustained localised oxidation of iodide to iodate in marinewaterrdquoMarine Chemistry vol 112 no 3-4 pp 168ndash178 2008
[87] M B Heeb J Criquet S G Zimmermann-Steffens andU Von Gunten ldquoOxidative treatment of bromide-containingwaters formation of bromine and its reactions with inorganicand organic compoundsmdasha critical reviewrdquo Water Researchvol 48 pp 15ndash42 2014
[88] V Sivasankar A K Darchen and R Omine SakthivelldquoChapter 2 ldquofluoride a world ubiquitous compound itschemistry and ways of contaminationrdquo in Surface ModifiedCarbons as Scavengers for Fluoride fromWater V SivasankarEd pp 5ndash32 copy Springer International Publishing Switzer-land Cham Switzerland 2016
[89] O Cabestrero P Del Buey and M E Sanz-Montero ldquoBio-sedimentary and geochemical constraints on the precipitationof mineral crusts in shallow sulphate lakesrdquo SedimentaryGeology vol 366 pp 32ndash46 2018
[90] M A Hassaan O A El-Rayis and E I Hemada ldquoEstimationof the redox potential of lake mariut drainage system (Qalaaand Umum drains)rdquoHydrology vol 5 no 6 pp 82ndash85 2017
20 Journal of Chemistry
Tabl
e3
Distribu
tionof
thestud
iedvariablesin
thepo
rewater
(p)alon
gLake
Mariout
Site
Spermilp
pHP
Ca p
(mgLminus
1 )Mg p
(mgLminus
1 )Na p
(mgLminus
1 )Kp
(mgLminus
1 )Li
p(m
gLminus
1 ))
SO4P
(mgLminus
1 ))
B P(m
gLminus
1 ))
P P(μgLminus
1 ))
SiP
(microgLminus
1 ))
F p(m
gLminus
1 ))
Cl P
(mgLminus
1 ))
Brp
(mgLminus
1 ))
I p(μgLminus
1 )1
1034
787
481
42303
1097
453
042
2944
8043
363
0045
323
95419
959
7104
2934
809
5611
115725
1050
498
039
2056
663
553
0036
338
8398
1385
24698
31272
717
100
5689
1195
577
053
2778
8949
1204
0034
754
114469
2291
26347
483
796
9619
47652
974
384
043
350
19312
77
0054
215
74599
693
8393
51099
782
5611
89711
1128
42041
1667
16739
1112
0081
1698864
1332
8333
645
775
4008
75367
736
41024
2111
11739
071
0037
1231
40321
799
24339
71125
782
39278
13615
1155
516
056
3667
6051
369
006
6101209
1279
8123
8148
775
9299
84314
1355
468
055
12444
942
212
0056
892
133232
1172
7643
9684
78
962
72109
880
393
036
3778
21341
114
0087
1061429
2131
9981
10114
764
1122
113586
1195
524
049
4667
8007
071
0041
1138
102562
1332
8572
11639
742
4008
61996
915
332
033
2833
11594
754
0026
1215
67834
746
37587
125
702
481
38413
8703
274
028
2167
13913
081
0025
2154
44832
1438
9891
13755
807
3206
6467
817
446
039
4556
17246
635
0042
954
5737
533
1097
Minim
um45
702
962
13615
736
274
024
1667
6051
071
0025
215
40321
533
7104
Maxim
um148
809
39278
115725
8703
577
056
12444
21341
1204
0087
2154
133232
2291
37587
Average
919
77
718
67412
163077
4381
041
3782
1223
485
0048
955
82779
1238
14768
SD308
032
10027
29209
2132
825
01
2769
5047
391
0019
542
27891
524
9917
10 Journal of Chemistry
Tabl
e4
Distribu
tionof
thestud
iedvariablesin
thesediment(s)alon
gLake
Mariout
Site
Sand
()
Mud ()
Porosity
()
CO3s
()
B s(m
ggminus
1 )P s
(mg
gminus1 )
Ca s
(mg
gminus1 )
Mg s
(mg
gminus1 )
Na s
(mg
gminus1 )
Ks
(mg
gminus1 )
Lis(m
ggminus
1 )
SO4s
(mg
gminus1 )
Fes
(mg
gminus1 )
Cu s (μg
gminus1 )
Mn s
(μg
gminus1 )
Zns(μg
gminus1 )
F s(m
ggminus
1 )
Cl s
(mg
gminus1 )
Brs
(mg
gminus1 )
I s(μg
gminus1 )
14
964915
183
299
044
1670
811
2583
408
0028
4861
828
963
5617
1272
034
041
128
1686
244
564925
574
196
028
1002
1419
2717
269
0015
662
257
793
4350
1313
057
054
123
358
319
816667
299
246
073
1670
1216
3125
336
0022
463
487
1228
4330
1677
044
034
448
516
418
824853
3813
1111
032
668
2229
3425
365
0094
2222
770
922
4637
1245
030
020
309
296
512
884697
482
614
012
501
1115
1833
091
0040
1713
243
600
27933
1223
082
034
245
254
65
954667
164
370
157
835
1257
2958
388
0030
5648
890
1927
5347
3117
070
020
852
209
75
954762
375
524
024
367
2047
3133
256
0102
1157
546
883
4185
1393
120
020
341
259
838
626143
457
697
039
668
1621
3550
347
0145
4167
598
737
4157
1412
022
034
144
1277
918
826000
349
083
054
401
1094
3358
369
0025
2454
701
868
5702
3065
036
027
250
172
1036
645070
441
296
002
935
1763
3117
246
0045
2685
369
790
4533
1315
012
047
1012
224
1185
157000
325
240
074
969
2250
3508
328
0193
1343
1026
735
3890
1070
005
007
533
128
1237
638214
463
291
032
334
1824
3008
358
0018
556
340
728
2475
827
001
007
852
281
134
965000
177
211
054
2338
1621
3925
599
0068
833
1687
1187
6492
1853
004
027
639
194
Min
415
4667
164
083
002
334
811
1833
091
0015
463
243
600
2475
827
001
007
123
128
Max
8596
8214
574
1111
157
2338
2250
3925
599
0193
6620
1687
1927
6492
3117
120
054
1012
1686
Av
2575
5609
359
398
048
951
1559
3096
335
0063
2671
672
951
4500
1599
040
029
452
450
SD23
231114
128
276
039
603
455
522
115
0055
2030
393
343
1120
708
035
014
303
475
Minm
inim
umM
axm
axim
uma
ndAv
averageSD
stand
arddeviation
Journal of Chemistry 11
(1559plusmn455mg gminus1) and calcium (951plusmn603mg gminus1) com-ponents may be attributed to the abundance of calcium min-erals [4] However in general the average amounts of allvariables in sediment samples showmarked variations fromonesite to another with a descending order of CO3sgtMgsgtCasgtNasgtSO4sgtFesgt BrsgtBsgtKsgtTPsgtFs gtClsgtMnsgtZnsgtCusgtLisgt Is (Table 4) -e measured concentra-tions of Mn Zn Cu and Fe in the sediment samples are stilllower than the reported values and also lower than the back-ground levels of crust and the toxicological reference contents ofUS DOE (US Department of Energy) US EPA (US Envi-ronmental Protection Agency) and CEQG (Canadian Envi-ronmental Quality Guidelines) [82]
Contrasting the obtained levels for the halogens withthose previously reported ones the present study indicatesthat surface and pore waters incorporate more considerableamounts of fluoride compared to the formerly reported onesin Lake Edku (Tables 2 and 3) and lower levels in theMarioutarea than those measured along the Egyptian MediterraneanSea coast [27] Compared with the sediments previouslyfound on the Mediterranean coast of Egypt the chloridecontent in the sediments of the Mariout area is lower [83]Compared with those observed in seawater the studiedsurface water and pore water samples have lower bromidecontent and higher levels than previously reported in LakeMariout [52 53] -e concentration of iodide in surfacewater pore water and sediments is equivalent to the con-centration of rivers and lakes in the world [84]
333 Interactions of Halogens and Tested Variables inSediment -e correlation matrix shows the important roleof halogens in the formation and precipitationdissolution ofsalts and minerals produced along the lake (SupplementaryTable 1) However it shows that chloride seems to be in thesoluble forms along the surface and pore waters of studiedarea showing good relations with Caw (r 0666 ple 0018)Clp (r 0677 ple 0016) and SO4p (r 0858 ple 0000)Also Cls gives good correlations with Mgw (r 0710ple 0010) Naw (r 0602 ple 0038) Clw (r 0619ple 0032) Mgp (r 0774 ple 0003) and Kp (r 0731ple 0007) Chloride in the surface and pore waters plays animportant role in the dissolution association and formationof various salts along the lake -e good relationship be-tween Is and Caw (r 0666 ple 0018) may reflect the de-positionrelease of CaI+ during the formationdissolution ofcalcium carbonate [85] In addition these correlations maybe related to organic-I which formed by bacterial species andtheir remineralization in bottom sediments [86] -emoderate relationship between Nas and Brw (r minus0622ple 0031) may indicate the possible formation of BrClspecies and the precipitation or adsorption of Na minerals insediments [87] -e results of this study also reflect thestrong negative correlation between Fs and Bw (r minus0666ple 0018) which may be related to the release of fluoridefrom sediment and the formation of soluble fluoridecomplexes ((BFn[OH]4minusn)minus) with the excessive boron con-centration in the water [88] -e negative relation betweenKs and Spermilw (r minus0673 ple 0016) possibly reflect that Kw
preferentially chooses to exist in the soluble form of KClrather than being adsorbed andor bound by some richminerals in the sediment
-e significant correlations between CO3s and Mgw(r 0637 ple 0026) CO3s and Clw (r 0723 ple 0008)CO3s and pHw (r 0833 ple 0001) CO3s and Spermilw(r 0723 ple 0008) and between CO3s and Ks (r minus0673ple 0016) may be accompanied by the possible formationdissolution of the dolomite mineral in the presence ofsufficient Mgw which is usually affected by optimal pHsalinity and the potassium salts (Supplementary Table 1)-ese observed results are matching with the previouslyreported studies [32] Significant negative correlation be-tween TPs and CO3s (r minus0744 ple 0006) may indicate theextended release of P from carbonate minerals and for-mation of apatites [32]
-e correlation matrix also refers to other possible in-teractions between the remaining determined variables(Supplementary Table 1) -e significant correlation be-tween SO4s andMgw (r 0706 ple 0010) and Liw (r 0633ple 0027) may be associated to the formation of Mg-sulfateand the pollution of sediments by discharged waters con-taining excessive sulfate and Li [89] In the contrary thestrong positive correlation between TPs and Cus and be-tween TPs and Zns may be related to the same source ofpolluted discharge water [23 83]
-e high negative correlations of Zns with Few(r minus0785 ple 0003) CO3s (r minus0601 ple 0039) and Cus(r 0698 ple 0012) may indicate that Zn Cu and CO3depositions in sediment samples are linked to the soluble Feform in water (ferrous) ie the release of Fe upwards in thewater column in the anoxic conditions (SupplementaryTable 1) [90] -e excellent relations found between Fesand CO3s (r minus0799 ple 0002) Fes and Cas (r 0637ple 0026) Fes and Clw (r minus0752 ple 0005) Fes and Nas(r 0720 ple 0008) and between Fes and Ks (r 0833ple 0001) may reflect the dissolution of the chelating Feassociation with the soluble organic compounds in thewater-sediment interface and the formation of the sol-uble ferrous form in low dissolved oxygen within theareas affected by untreated discharged waters [90] -estrong correlations of Mns with SO4w Nap Nas Ks CO3sZns and Fes (r minus0585 0608 0611 0698 minus0655 0691and 0716 respectively) may associate with the solubilityof abundant Mn minerals and P-Mn forms in the sedi-ment because of its possible reduction to Mn+2 solublespecies under anoxic conditions [90] It is worth men-tioning that the results of this study indicate that ap-proximately 333 of the survey sites indicate thedepletion of dissolved oxygen in their surface watersamples Under such anoxic conditions bacteria are mostlikely to use sulfate instead of oxygen to break downorganic matter and cause the release of iron and phos-phorus into the water column
-e significant direct correlation between Ks and Nas(r 0832 plt 0001) clearly reflects the transport of solublesalts of K and Na between the pore water phase of thesediment and water-sediment surface phase (SupplementaryTable 1) -e good correlation between porosity and Nas
12 Journal of Chemistry
indicates the possible transfer of Na between pore water andsediment partitions
34 Interactions of Precipitated Halogenated Compounds inSurface and Pore Waters -e Saturation Index (SI) [23 60]of twenty-three and fifteen structures in surface water andpore water samples respectively are listed (Table 1) -ecorrelation matrix of the calculated Saturation Indices withthe presented data shows the different factors affecting theinteraction of the halogenated compound with other pre-cipitated salts and minerals Table 1 explores the precipitationof the phosphate minerals and salts are most abundantfollowed by the hydroxidesrsquo salts iodate salts sulfate andcarbonate minerals and salts in surface waters Amongst thehalogens precipitated salts fluoride minerals especiallyfluorapatites and carbonate-fluorapatite (FAP and CFAP)have high SI values in surface water (4277ndash5195 and1604ndash6089 respectively) and in pore water (5126ndash5460 and1752ndash7833 respectively) Bromide and chloride are mainlyfound in the soluble forms in surface and pore waters Iodidesalts (Ca(IO3)2 and Ca(IO3)26H2O) moderately precipitatein surface and pore Iron salts precipitate in surface waterwhile in pore water they are not formed -us SI contentreflects that halogens especially fluoride and iodide play avital role in reducing lake pollution
In addition Table 1 shows that the precipitation com-pounds that may be formed in surface water are relativelydifferent from those in sediment pore water For examplefluorite (CaF2) and sellaıte (MgF2) may be only formed inpore water while calcite and aragonite may be deposited insurface water However the formation of fluorite in surfacewater is related to Naw (r 0778 ple 0003) Kw (r 0704ple 0011) CO3w (r minus0718 ple 0009) Fw (r 0770ple 0003) and Ip (r minus0785 ple 0003) (SupplementaryTable 1)
-e formation of calcium sulfate hemihydrate calciumsulfate and anhydrite in water is related to the increase in theamounts of Caw Mgw SO4w Nap Fp Sip Cls and Mns andthe decrease in porosity values On the other hand pre-cipitation of calcium phosphate is related to Brw (r 0751ple 0005) Znw (r 0668 ple 0018) Pw (r 0881ple 0001) and Ks (r 0881 ple 0001) ie it is affected bythe discharged water composition (Supplementary Table 1)
-e formation of calcite and aragonite in surface water isrelated to the formation of CO3w (r 0753 ple 0005) anddissociation of HCO3w (r minus0660 ple 0020) pHw values(r minus0654 ple 0021) and their dissolution in sediment(r minus0620 ple 0032) (Supplementary Table 1)
-e dolomite formation in water may be affected by theincrease of CO3w (r 0817 ple 0001) and the decrease ofHCO3w (r minus0658 ple 0020) increase in TDSw (r 0599ple 0040) and increase in pHw (r minus0656 ple 0021)besides the possible release of CO3s from abundant sediment(r minus0624 ple 0030) and the precipitation of calcite(r 0984 ple 0000) and aragonite (r 0984 ple 0000) intosediment fraction (Supplementary Table 1)
Generally in the current study the possible formedhalogenated minerals and salts are affected by their
abundance in different components of the lake besides theirpossible dissolution or formation on the sediment texturesgeochemistry of the sediments and physicochemical vari-ables of water in addition to the components of the dis-charged waters
35 Interactions of Dissolved Halogenated Compounds inSurface and PoreWaters -e utilization of dissolved salts insurface and pore waters by utilizing Palmerrsquos method andpiper ternary diagram [50] indicates that Na is the richestcation in surface water followed by Mg Ca and K At thesame time Mg is the most predominate one in the porewater (Figures 3 and 4) Obviously Cl is the most importantanion in surface water and pore waters samples Howeverthe piper ternary diagrams of surface water and pore waterclearly shows that NaCl is the most dominant in surfacewater while MgCl2 is the most abundant in pore waterCoincidently Palmerrsquos method also reflects that NaCl(574) is the most existent species in surface water fol-lowed by MgCl2 (304) CaCl2 (71) CaSO4 (29)Ca(HCO3)2 (14) and KCl (12) (Figure 3) At the sametime MgCl2 (760) is the most present species in porewater followed by NaCl (73)asympMg(HCO3)2 (73)Ca(HCO3)2 (52) and MgSO4 (31) (Figure 4)
36 Multivariate Analysis
361 Principal Component (PCA) By applying Varimaxrotation and Kaiser normalization to 98 variables in the PCAfor halogens and tested variables and calculated parametervalues 7 extracted PCs with eigenvalues higher than 1 areobtained However it is important that the eigenvalue mustbe greater than 1 Its seven PCs explain 8558 of the totalvariance
-e first principle component (PC1) is 1473 of thetotal variance and shows positive coefficient factor loadingsfor CO3w TDSw Kp calcite aragonite dolomite FeCO3MgCO3 ZnCO3 and ZnCO3H2O (0804 0547 05320938 0938 0947 0741 0940 0866 and 0866 respec-tively) In addition it provides negative factor loadings forHCO3w pHw Bw Nap and CO3s (minus0782 minus0610 minus0595minus0532 and minus0572 respectively) PC1 is related to thefactors affecting the carbonate compounds that may beformed in the area under consideration
PC2 accounts to 1458 of the total variance and alsoshows positive and negative coefficient factor loadingsrepresenting the different interactions between the CawMgw Liw SO4wMgp Nap pHp Cls SO4s Brs and porosityin water pore water and sediment that are responsible forthe composition of sulfate magnesium and phosphateprecipitates besides the effect of the discharged waters onwater-pore water-sediment componentsrsquo cycles
PC3 typically shows 1377 of the total variance withpositive and negative loadings which can properly explorethe effect of the principal sources of local pollution on thedissolving of heavy metals B and P from sediment into thewater column and the probable formation of Fe(OH)2Fe(OH)3) and FePO4
Journal of Chemistry 13
Similarly the coefficient factor loadings of PC4 with1355 are related to the influence of the polluted dischargewater and sediment texture on the formation of F Cl and Isalt besides the precipitation of halogenated compounds(FeF2 Mn(IO3)2 KIO4 and KCIO4) besides their minerals(CaF2 MgF2 FAP and CFAP)
Simultaneously PC5 gives 1092 of the total variancewith positive and negative loadings which explains therelations between the physicochemical limits of the surfacewater pore water and sediment components and theprecipitation of minerals and salts (OCP HAP CuBrZn(OH)2 and Zn(IO3)22H2O) -is is also associated tothe influence of the sedimentary material on the release ofMn Fe and P from sediment into pore water and watercolumn and formation of Ca3(PO4)2 OCP and HAPminerals
However PC6 associates with 100 of the total variancegiving positive and negative coefficient factor loadingswhich explain that the sediments (minerals andor organic-iodine compounds) are only the acting sink for iodine andiodine species (Iminus and IOminus
3 ) in the water as previously re-ported [84] PC6 also reflects the precipitation of severalhalogenated compounds such as calcium iodate (Ca(IO3)2and Ca(IO3)26H2O) and copper iodate (CuI andCuIO3H2O) besides Cu3(PO4)2 species in the lake watercolumn
-e loadings of PC7 contribute by 804 and show thatthe release of calcium in pore water into the water column isresponsible for the precipitation of halogenated compounds(CuCl and Zn(IO3)22H2O) as well as copper and Zn salts(Cu3(PO4)2 and Zn(OH)2)
362 Cluster Analysis On the other hand cluster analysisshows that the similarity of sites 1amp4 5amp8 6amp9 2amp10 and11amp13 is due to the texture of sediment
363 Multiple Regression Multiple regression equations ofhalogens as dependent variables and the other determinedand calculated parameters as independent variables insurface water pore water and sediment partitions are listed(Table 5)-e amount of fluoride in water samples is affectedby the discharged watersrsquo fundamental components espe-cially Zn and Cu besides its surface water-pore water in-teractions Its content in pore water seems to be stronglyaffected by its substitution competition with other halogensin surface water-spore water-sediment cycle due to its highelectronegativity Generally in the affected area the type ofpollutant in the discharged water plays an important role inthe dissolution andor precipitation of fluoride and otherhalogens in the surface water-pore water-sediment cycle
574
147129
300
12
Ca(HCO3)2CaSO4CaCl2
MgCl2KClNaCl
(a)
SO4
2 + CIndash Ca 2+ + Mg 2+
CO32ndash + HCO3
ndashNa+ + K+
Mg2+ SO42ndash
Ca2+ CIndash
(b)
Figure 3 (a) distribution and (b) piper ternary diagram of the formed dissolved salts in surface water of Lake Mariout
Ca(HCO3)2Mg(HCO3)2MgSO4
NaClMgCI2KCl
760 1052
7373 31
(a)
SO4
2ndash + C
Indash
Ca 2+ + Mg 2+
CO32ndash + HCO3
ndashNa+ + K+
Mg2+ SO42ndash
CIndashCa2+
(b)
Figure 4 (a) distribution and (b) piper ternary diagram of the formed dissolved salts in pore water of Lake Mariout
14 Journal of Chemistry
Table 5 -e multiple regression analyses of each halogen as dependent variable and other tested variables in the surface water pore waterand sediment partitions besides the precipitated salts in surface water along Lake Mariout
Dependentvariable Multiple regression equation R2
FluorideLake water FW 3162 + 092 Zn F2 minus 033 SiP + 021 CuIminus 017 SpermilP 09911
Pore water Fp minus2567minus117 SiW minus 033 LiP minus 062 CuClminus 028 IS + 023 TDSW+ 017 KIO4 minus 012 BrW minus 004porosity + 004 PW
10000
Sediment FS 088 CAPminus 049 MgS minus 046 DOW+039MgW+ 027 Mn(IO3)2 + 015 Cu3(PO4)2 + 004 HAP+ 002 pHP 10000ChlorideLake water No relation 00000Pore water No relation 00000Sediment ClS minus116 + 046 MgP + 077 Kp minus 049 dolomite + 017 TDSW minus 011 CuI + 005 NaS + 002 BS + 001 FeF2 10000Bromide
Lake water BrW 1563 + 110 CuBrminus 057 CuClminus 021 KS minus 014 pHP minus 011 TPS + 014 FeW+ 007 ZnSminus 002 PP + 001turbidity 10000
Pore water BrP minus1516minus 055 FeS minus 073 BS + 061 MnW+ 083 SiP + 049 NaS minus 031MnS minus 015 CuBr + 011 pHW minus 001CaW
10000
Sediment BrS 015 SiP + 195 CFAP+ 002 FP minus 045 IS + 192 sand+ 037 MnW minus 029 MgS minus 012 LiP + 005Ca3(PO4)2 minus 002 ZnF2
10000
IodideLake water IW 099 Ca(IO3)6H2O 09999
Pore water IP minus097 ZnF2 minus 057 Li3PO4 minus 053 BP + 034 FAP+ 015 Ca(IO3)2 +MnW+ 005 KS minus 009 turbidity + 055CaS
09999
Sediment IS minus072 + 135 SO4P + 023 Mn(IO3)2 + 063 FeW+ 031 TPS minus 035 MgP minus 012 Zn(CO3)22H2O 09993
40E + 0135E + 0130E + 0125E + 0120E + 0115E + 0110E + 0150E + 0000E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
12345
678910
111213
(a)
10E + 0090E ndash 0180E ndash 0170E ndash 0160E ndash 0150E ndash 0140E ndash 0130E ndash 0120E ndash 0110E ndash 0100E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
12345
678910
111213
(b)
12345
678910
111213
40E ndash 0235E ndash 0230E ndash 0225E ndash 0220E ndash 0215E ndash 0210E ndash 0250E ndash 0300E ndash 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
(c)
12345
678910
111213
80E ndash 0670E ndash 0660E ndash 0650E ndash 0640E ndash 0630E ndash 0620E ndash 0610E ndash 0600E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
(d)
Figure 5 Hazard quotient of ingestion and dermal contact of surface water and sediment of LakeMariout (a) ingestion of water (b) dermalcontact of water (c) ingestion of sediment and (d) dermal contact of sediment
Journal of Chemistry 15
Minerals and precipitated salts in the different partitions(surface water pore water and sediment) play an importantrole in the deposition and release of halogens in sedimentsAdditionally the texture and the porosity of the sedimentsplay a key role in the distribution of halogens in the threepartitions Interestingly chloride is the only halogen that hasnegligible interactions along the surface water and porewater partitions because it is present in large quantities inthe form of soluble salts (NaCl and MgCl2)
37 Pollution Status
371 Enrichment Factor (EF) Twowell-knownmethods areused to assess environmental pollution public health sig-nificance of ingestion and dermal contact with water andsediment components and sediment enrichment factor (EF)[59 60]
-e average EF values of the determined elements CaMg Na K Li B P Cu Zn Mn Fe F Cl Br and I are alllower than the value that is less than the minimum en-richment value (EFlt 2)-us the area under investigation isstill ecologically considered as an unpolluted region
372 Human Health Risk Assessment -e EDI HQ and HIshow the variable values of all pollutants in the surface waterand sediments along the lake region and in drains (sites11ndash13) under study Among all the calculated variables ofsurface water ingestion (EDIIngw) and dermal contact(EDIDermw) Cl is still the only variable that shows high levels(average 1551 and 43mg kgminus1 dayminus1 respectively) -eestimation daily intake of sediment ingestion (EDIIngs) anddermal contact (EDIDerms) of Mg Ca and Na give maximumaverage amounts of 841Eminus 02 513E ndash 02 and167Eminus 03mg kgminus1 dayminus1 respectively
Among the HQ of the calculated detection variables thecontent of HQB of ingestion and dermal contact with waterand sediment is the highest However 70 of sites have HQBvalues more than 10 (Figure 5) Comparing the HQ values ofall the determined variables HQB of the ingestion of surfacewater shows values higher (gt10) However due to the impactof drainage the HQB values of stations 1ndash4 8ndash10 12 and 13
are higher than 10 -erefore these sites can be consideredas the area with the most serious boron pollution caused byuntreated discharged water disposal In addition the HIIngwlevel of water ingestion for the studied variables in all sites ismuch higher than 10 (Figure 6) Except for boron it isusually concluded that the study area does not pose any riskto the population due to halogens or other variables Ac-cordingly this information may help the official authoritiesoptimize management plans and strengthen their pollutioncontrol actions in Lake Mariout
4 Conclusions
-e effects of halogen salts and minerals on the pollution ofLake Mariout were studied Halogens and some physico-chemical variables in three partitions surface water porewater and sediment in Lake Mariout were evaluated -ehalogen content was variable between different sites andchloride was the main halogen in surface water and porewater but it was very rare in the lakersquos sediment partitionPiper ternary diagram and Palmerrsquos method reflected thatNaCl was the dominant salt in surface water while MgCl2was the main dissolve salt in pore water-e chlorinity ratiosof halogens and tested variables were directly matched to thefeeding drain sources
Moreover the Saturation Index (SI) reveals that 23 and 15precipitated salts and minerals are formed in surface water andpore water respectively -e SI value indicated the formationof phosphate minerals in surface water and pore water es-pecially octacalcium phosphate (OCP Ca4H(PO4)325H2O)and hydroxyapatite (HAP Ca5(PO4)3OH) In addition tofluoride minerals especially fluorapatite (FAP) and carbonate-fluorapatite (CFAP) were obviously precipitated from surfacewater and pore water Soluble salts of bromide and chloridewere formed in surface water and pore water Iodide salts(Ca(IO3)2 and Ca(IO3)26H2O) were moderately precipitatedin the surface water and pore water
Moreover the multivariate analysis including the cor-relation matrix multiple stepwise linear regression treeclustering and principle component (PCA) of all the de-termined and calculated variables was applied to estimatethe proposed interaction between halogens and other tested
10E + 02
16E + 0214E + 0212E + 02
80E + 0160E + 0140E + 0120E + 0100E + 00
1 2 3 4 5 6 7 8 9 10 11 12 13
HIIngHIDerm
(a)
1 2 3 4 5 6 7 8 9 10 11 12 13
HIIngHIDerm
40E ndash 0235E ndash 0230E ndash 0225E ndash 0220E ndash 0215E ndash 0210E ndash 0250E ndash 0300E + 01
(b)
Figure 6 Hazard index of ingestion and dermal contact of the studied variables in surface water and sediment of Lake Mariout (a) waterand (b) sediment
16 Journal of Chemistry
variables in the polluted area under study -e multivariateanalysis showed that there were many interactions betweenhalogens and tested variables High levels of fluoride bro-mide and chloride in surface water were related to thecomposition of drainage waters -e enrichment factor (EF)showed that Lake Mariout was not polluted However thehuman health adverse effects calculated for surface waterand sediment did not reflect any possible likelihood hazardeffects from halogens
Interestingly the current study concluded that halogencompounds especially fluorides are most likely to be de-posited from surface lakes in the form of many minerals andprecipitation thereby reducing the adverse pollution effectson human health -e results obtained through this workhelp to find the correlations between the sampling sites andthe variables obtained by physical and chemical measure-ments which can be used to construct a fast decision modelfor separating different water quality samples -is infor-mation may help the official authorities optimize manage-ment plans and strengthen their pollution control measuresin Lake Mariout
Data Availability
-e data used to support the findings of this research areincluded within the paper
Conflicts of Interest
-e authors declare that there are no conflicts of interestregarding the publication of this manuscript
Supplementary Materials
Supplementary Table 1 correlation matrix of variable insurface water pore water and sediment partitions besidesthe precipitated salts in surface water along Lake Mariout(Supplementary Materials)
References
[1] M S Masoud T O Said G El-Zokm and M A ShreadahldquoAssesment of heavy metals contamination in surface sedi-ments of the Egyptian Red Sea Coastsrdquo Australian Journal ofBasic and Applied Sciences vol 6 pp 44ndash58 2012
[2] M A Shreadah M I Abdel Moneim T O SaidE M I Fathallah and M E Mahmoud ldquoPAHs in seawater ofthe semi-closed areas along the Alexandria coast of EgyptianMediterranean seardquo Journal of Environmental Protectionvol 4 no 11 p 11 Article ID 40298 2013
[3] S Abdel Ghani G El Zokm A Shobier T Othman andM Shreadah ldquoMetal pollution in surface sediments of Abu-Qir bay and Eastern harbour of Alexandria Egyptrdquo EgyptianJournal of Aquatic Research vol 39 no 1 pp 1ndash12 2013
[4] G F El-Said ldquoBioaccumulation of key metals and othercontaminants by seaweeds from the Egyptian MediterraneanSea Coast in relation to human health riskrdquo Human andEcological Risk Assessment An International Journal vol 19no 5 pp 1285ndash1305 2013
[5] M A Shreadah A H Shobier S Abdel Ghani G M El-Zokm and T O Said ldquoMajor ions anomalies and
contamination status by trace metals in sediments from twohot spots along the Mediterranean Coast of Egyptrdquo Envi-ronmental Monitoring and Assessment vol 187 no 280pp 1ndash18 2015
[6] A El Nemr G F El-Said A Khaled and S Ragab ldquoDis-tribution and ecological risk assessment of some heavy metalsin coastal surface sediments along the Red Sea Egyptrdquo In-ternational Journal of Sediment Research vol 31 no 2pp 164ndash172 2016
[7] A El Nemr G F El-Said S Ragab A Khaled and A El-Sikaily ldquo-e distribution contamination and risk assessmentof heavy metals in sediment and shellfish from the Red Seacoast Egyptrdquo Chemosphere vol 165 pp 369ndash380 2016
[8] A El Nemr and G F El-Said ldquoAssessment and ecological riskof heavy metals in sediment and molluscs from the Medi-terranean coastrdquo Water Environment Research vol 89 no 3pp 195ndash210 2017
[9] M A Sheradah A A El-Sikaily N M Abd El MoneamN E Abd El Maguid and M G Zaki ldquoChemical and bio-chemical evaluation of marine pollution by polychlorinatedbiphenyls and pesticides in two regions along the EgyptianMediterranean Seardquo International Journal of EnvironmentalMonitoring and Analysis vol 6 no 3 pp 95ndash109 2018
[10] M A Shreadah A A-M M El-Sayed A A S TahaA-M M Ahmed and H H Abdel Rahman ldquoEvaluation ofdifferent anthropogenic effluents impacts on the water qualityusing principal component analysis a case study of Abu-QirBay-Alexandria-Egyptrdquo International Journal of Environ-mental Monitoring and Analysis vol 7 no 3 pp 56ndash67 2019
[11] G F El-Said M M El-Sadaawy A H Shobier andS E Ramadan ldquoHuman health implication of major and traceelements present in commercial crustaceans of a traditionalseafood marketing region Egyptrdquo Biological Trace ElementResearch vol 199 pp 315ndash328 2020
[12] M A Shreadah S A A Ghani H B I HawashA A E Samie and A E M M Ahmed ldquoOrganotin com-pounds in sediments of northern lakes Egyptrdquo Journal ofEnvironmental Protection vol 05 no 17 pp 1654ndash1666 2014
[13] A M Younis G M El-Zokm and M A Okbah ldquoSpatialvariation of acid-volatile sulfide and simultaneously extractedmetals in Egyptian Mediterranean Sea lagoon sedimentsrdquoEnvironmental Monitoring and Assessment vol 186 no 6pp 3567ndash3579 2014
[14] G F El-Said S E O Draz M M El-Sadaawy andA A Moneer ldquoSedimentology geochemistry pollution statusand ecological risk assessment of some heavy metals insurficial sediments of an Egyptian lagoon connecting to theMediterranean Seardquo Journal of Environmental Science andHealth Part A vol 49 no 9 pp 1029ndash1044 2014
[15] G M El Zokm M A Okbah and A M Younis ldquoAssessmentof heavy metals pollution using AVS-SEM and fractionationtechniques in Edku Lagoon sediments Mediterranean SeaEgyptrdquo Journal of Environmental Science and Health PartAvol 50 no 6 pp 571ndash584 2015
[16] G M El Zokm H R Z Tadros M A Okbah andG H Ibrahim ldquoldquoEutrophication assessment using TRIX andCarlsonrsquos indices in Lake Mariout water Egyptrdquo EgyptianJournal of Aquatic Biology and Fisheries vol 22 no 5pp 331ndash349 2018
[17] N Donia ldquoLake Maryut monitoring using remote sensingrdquo inProceedings of the gypt Eighteenth International WaterTechnology Conference IWTC18 Sharm El Sheikh Abu DhabiUAE March 2015
Journal of Chemistry 17
[18] M A Khairy ldquoAssessment of priority phenolic compounds insediments from an extremely polluted coastal wetland (LakeMaryut Egypt)rdquo Environmental Monitoring and Assessmentvol 185 no 1 pp 441ndash455 2013
[19] N A El-Naggar and E A Rifaat ldquoEgyptian coastal lakes andwetlands part Imdashcharacteristics and hydrodynamicsrdquo in eHandbook of Environmental Chemistry A M Negm EdSpringer International Publishing AG Berlin Germany 2017
[20] J J Hanley and K T Koga ldquoChapter 2 ldquohalogens in terrestrialand cosmic geochemical systems abundances Geochemicalbehaviors and analytical methodsrdquordquo in e Role of Halogensin Terrestrial and Extraterrestrial Geochemical ProcessesD E Harlov and L Aranovich Eds Springer InternationalPublishing AG Berlin Germany pp 21ndash121 2018
[21] A Ghosh K Mukherjee S K Ghosh and B Saha ldquoSourcesand toxicity of fluoride in the environmentrdquo Research onChemical Intermediates vol 39 no 7 pp 2881ndash2915 2013
[22] M M Naim A A Moneer and G F El-Said ldquoPredictiveequations for the defluoridation by electrocoagulation tech-nique using bipolar aluminum electrodes in the absence andpresence of additives a multivariate studyrdquo Desalination andWater Treatment vol 57 no 14 pp 6320ndash6332 2016
[23] G F El-Said N A Shaltout M M El-Sadaawy andA M H Morsy ldquo-e precipitation of fluoride calcium andmagnesium minerals from Egyptian Mediterranean Sea coastin relation to discharged watersrdquo Desalination and WaterTreatment vol 57 no 5 pp 2113ndash2124 2016
[24] H Bureau ldquoIodine encyclopedia of geochemistry A com-prehensive reference source on the chemistry of the earthrdquo inEncyclopedia of Earth Sciences Series W M White Ed copySpringer International Publishing AG 2016
[25] F C Kupper and C J Carrano ldquoKey aspects of the iodinemetabolism in brown algae a brief critical reviewrdquo Metal-lomics vol 11 pp 756ndash764 2019
[26] R Liteplo R Gomes P Howe and H Malcolm Fluorides-Environmental Health Criteria 227 p 290 World HealthOrganization (WHO) Geneva Switzerland 2002
[27] G F El-Said and M M El-Sadaawy ldquoSeasonal variation ofboron and fluoride in Tilapia nilotica from an Egyptian fishfarm in relation to Human health hazard assessmentrdquoHumanand Ecological Risk Assessment An International Journalvol 19 no 4 pp 930ndash943 2013
[28] WHO (World Health Organization) Bromide in Drinking-Water Background Document for Development of WHOGuidelines for Drinking-Water Quality WHO Press WorldHealth Organization Geneva Switzerland 2009
[29] G F El-Said and N A Sallam ldquo-e uptake of fluorideconcentration and its effects on the growth rate of shrimps(Palaemon elegans Rathke)rdquo Chemistry and Ecology vol 24no 3 pp 191ndash205 2008
[30] X Zhang J He B He and J Sun ldquoAssessment formationmechanism and different source contributions of dissolvedsalt pollution in the shallow groundwater of Hutuo Riveralluvial-pluvial fan in the North China Plainrdquo EnvironmentalScience and Pollution Research vol 26 no 35 pp 35742ndash35756 2019
[31] Y Zhu B Huang Z Zhu et al ldquoldquoCharacterization disso-lution and solubility of the hydroxypyromorphitendashhydroxyapatite solid solution [(PbxCa1minusx)5(PO4)3OH] at25 degC and pH 2ndash9rdquo Geochemical Transactions vol 17 no 2pp 1ndash18 2016
[32] G F El-Said M M El-Sadaawy A A Moneer andN A Shaltout ldquo-e effect of fluoride on the distribution ofsome minerals in the surface water of an Egyptian lagoon at
the Mediterranean Seardquo Egyptian Journal of Aquatic Researchvol 41 no 1 pp 31ndash39 2015
[33] Y Zhu Z Zhu X Zhao Y Liang and Y Huang ldquoChar-acterization dissolution and solubility of lead hydroxypyr-omorphite [Pb5(PO4)3OH] at 25ndash45degCrdquo Journal ofChemistry vol 2015 Article ID 269387 10 pages 2015
[34] M A Z Chahouki ldquoMultivariate analysis techniques inenvironmental sciencerdquo in Earth and Environmental SciencesDr Imran Ahmad Dar Ed InTech Open London UK 2011httpwwwintechopencombooksearth-and-environmental-sciencesmultivariate-analysis-techniques-inenvironmental-science
[35] J V Klump and C S Martens ldquoBiogeochemical cycling in anorganic-rich coastal marine basin 5 Sedimentary nitrogenand phosphorus budgets based upon kinetic models massbalances and the stoichiometry of nutrient regenerationrdquoGeochimica et Cosmochimica Acta vol 51 no 5 pp 1161ndash1173 1987
[36] R L Folk Petrology of Sedimentary Rocks University of TexasAustin TX USA 1974
[37] P Saenger ldquoA rapid spectrophotometric method for thedetermination of bromine in seawater and in the ash ofmarine algaerdquo Helgolander Wissenschaftliche Meer-esuntersuchungen vol 23 no 1 pp 32ndash37 1972
[38] P G Jeffery Chemical Methods of Rock Analysis PergamonPress New York NY USA 2nd edition 1975
[39] J D H Strickland and T R Parsons ldquoA practical handbook ofseawater analysisrdquo in Fisheries Research Board of CanadaBulletin 167p 311 Second edition Wiley Ottawa Canada1972
[40] B Horvath O Opara-Nadi and F Beese ldquoA simple methodfor measuring the carbonate content of soilsrdquo Soil ScienceSociety of America Journal vol 69 no 4 pp 1066ndash1068 2005
[41] K Grasshoff Methods of Seawater Analysis p 317 VerlagChemie Weinkeim Germany 1976
[42] R Danovaro D Marrale N Della Croce P Parodi andM Fabiano ldquoBiochemical composition of sedimentary or-ganic matter and bacterial distribution in the Aegean Seatrophic state and pelagic-benthic couplingrdquo Journal of SeaResearch vol 42 no 2 pp 117ndash129 1999
[43] APHA-AWWA-WPCF (American Public Health Associa-tion) Standard Methods for the Examination of Water andWaste Water American Public Health Association Wash-ington DC USA 20th edition 1999
[44] K I Aspila H Agemian and A S Y Chau ldquoA semi-auto-mated method for the determination of inorganic organicand total phosphate in sedimentsrdquo e Analyst vol 101no 1200 pp 187ndash197 1976
[45] J P Riley and D Taylor ldquoChelating resins for the concen-tration of trace elements from sea water and their analyticaluse in conjunction with atomic absorption spectrophotom-etryrdquo Analytica Chimica Acta vol 40 pp 479ndash485 1968
[46] G F El-Said and A El-Sikaily ldquoChemical composition ofsome seaweed from Mediterranean Sea coast Egyptrdquo Envi-ronmental Monitoring and Assessment vol 185 no 7pp 6089ndash6099 2013
[47] Directorate General of Health Services Ministry of Health andFamilyWelfare Government of India ldquoManual of methods ofanalysis of foodsrdquo in Fruit and Vegetable Productsp 57Directorate General of Health Services Ministry of Health andFamily Welfare Government of India New Delhi India2005
[48] A Gunnars S Blomqvist and C Martinsson ldquoInorganicformation of apatite in brackish seawater from the Baltic Sea
18 Journal of Chemistry
an experimental approachrdquo Marine Chemistry vol 91 no 1-4 pp 15ndash26 2004
[49] W M Haynes D R Lide and T J Bruno CRC Handbook ofChemistry and Physics A Ready Reference Book of Chemicaland Physical Data CRC Press Taylor amp Frances Group BocaRaton FL USA 97th edition 2017
[50] M S Masoud M I El-Samra and M M El-Sadawy ldquoWaterchemistry of el-mex bay west of Alexandria Egyptrdquo eEgypian Science Magazine vol 2 pp 70ndash78 2005
[51] F J Millero R Feistel D G Wright and T J McDougallldquo-e composition of standard seawater and the definition ofthe reference-composition salinity scalerdquo Deep Sea ResearchPart I Oceanographic Research Papers vol 55 no 1pp 50ndash72 2008
[52] S K El-Wakeel S A Morcos and A M Mahlis ldquo-e majorcations in Lake Maryut watersrdquo Hydrobiologia vol 36 no 2pp 253ndash274 1970
[53] A M Mahlis S A Morcos and S K El-Wakeel ldquo-e majoranions in Lake Maryut watersrdquo Hydrobiologia vol 36 no 2pp 275ndash294 1970
[54] A S Saad M A Massoud R A Amer and M A GhorabldquoAssessment of the physico-chemical characteristics andwater quality analysis of Mariout Lake southern of Alexan-dria Egyptrdquo Journal of Environmental and Analytical Toxi-cology vol 7 no 1 p 421 2017
[55] R Rumuri ldquoDataset on hydrogeochemical characteristics ofgroundwater and surface water in Kattumannarkoil TalukIndiardquo Data in Brief vol 32 Article ID 106058 2020
[56] P Szefer S W Fowler K Ikuta et al ldquoA comparative as-sessment of heavy metal accumulation in soft parts and byssusof mussels from subarctic temperate subtropical and tropicalmarine environmentsrdquo Environmental Pollution vol 139no 1 pp 70ndash78 2006
[57] N F Soliman G M El Zokm and M A Okbah ldquoRisk as-sessment and chemical fractionation of selected elements insurface sediments from Lake Qarun Egypt using modifiedBCR techniquerdquo Chemosphere vol 191 pp 262ndash271 2018
[58] G M El Zokm M I A Ibrahim L A Mohamed and M El-Mamoney ldquoCritical geochemical insight into Alexandria coastwith special reference to diagnostic ratios (TOCTN amp SrCa)and heavy metals ecotoxicological hazardsrdquo Egyptian Journalof Aquatic Research vol 46 no 1 pp 27ndash33 2020
[59] A S Likuku K B Mmolawa and G K GaboutloeloeldquoAssessment of heavy metal enrichment and degree of con-tamination around the copper-nickel mine in the SelebiPhikwe Region Eastern Botswanardquo Environment and EcologyResearch vol 1 no 2 pp 32ndash40 2013
[60] M K Khalil S E O Draz G M El Zokm and G F El-SaidldquoApportionment of geochemistry texturersquos properties and riskassessment of some elements in surface sediments from Bar-dawil Lagoon Egyptrdquo Human and Ecological Risk AssessmentAn International Journal vol 22 no 3 pp 775ndash791 2016
[61] M M El-Sadaawy and G F El-Said ldquoAssessment of fluoridein three selected polluted environments along the EgyptianMediterranean Sea effects on local populationsrdquo Human andEcological Risk Assessment An International Journal vol 20no 6 pp 1643ndash1658 2014
[62] USEPA ldquoSuperfund exposure assessment manualrdquo inOSWER Directive 92855-1EPA540l-88001Office of Emer-gency and Remedial Response Washington DC USA 1988
[63] USEPA ldquoExposure factors handbookrdquo in EPA6008-89043Office of Health and Environmental Assessment Wash-ington DC USA 1989
[64] Health Canada ldquoFederal Contaminated Site Risk Assessmentin Canadardquo Part II Health Canada Toxicological ReferenceValues (TRVs) Cat H46-204-368E Calgary Health CanadaOttawa Canada 2007
[65] J Iqbal S A Tirmizi and M H Shah ldquoStatistical appor-tionment and risk assessment of selected metals in sedimentsfrom Rawal Lake (Pakistan)rdquo Environmental Monitoring andAssessment vol 185 no 1 pp 729ndash743 2013
[66] USEPA (US Environmental Protection Agency) Region 6USAEPA ldquoMultimedia Planning and Permitting DivisionrdquoOffice of Solid Waste Center for Combustion Science andEngineering Washington DC USA 2005
[67] P Jeschke ldquoLatest generation of halogen-containing pesti-cidesrdquo Pest Management Science vol 73 no 6 pp 1053ndash10662017
[68] M A Shreadah O A El-Rayis N A Shaaban andA M Hamdan ldquoWater quality assessment and phosphorusbudget of a lake (Mariut Egypt) after diversion of wastewaterseffluentsrdquo Environmental Science and Pollution Researchvol 27 no 21 pp 26786ndash26799 2020
[69] J P Riley and M Tongudai ldquo-e major cationchlorinityratios in sea waterrdquo Chemical Geology vol 2 pp 263ndash2691967
[70] R B McCleskey D K Nordstrom D D Susong J W Balland J M Holloway ldquoSource and fate of inorganic solutes inthe gibbon river yellowstone national park Wyoming USArdquoJournal of Volcanology and Geothermal Research vol 193no 3-4 pp 189ndash202 2010
[71] G T F Wong and K-Y Li ldquoWinklerrsquos method overestimatesdissolved oxygen in seawater iodate interference and itsoceanographic implicationsrdquo Marine Chemistry vol 115no 1-2 pp 86ndash91 2009
[72] B S R V Prasad P D N Srinivasu P S VarmaA V Raman and S Ray ldquoDynamics of dissolved oxygen inrelation to saturation and health of an aquatic body a case forChilka Lagoon Indiardquo Journal of Ecosystems vol 2014 Ar-ticle ID 526245 17 pages 2014
[73] China Environmental Protection Agency EnvironmentalQuality Standards for Surface Water (GB3838ndash2002) NationalEnvironmental Protection Agency of China Beijing China2002
[74] Y Jia L Wang Z Qu and Z Yang ldquoDistribution con-tamination and accumulation of heavy metals in watersediments and freshwater shellfish from Liuyang RiverSouthern Chinardquo Environmental Science and Pollution Re-search vol 25 no 7 pp 7012ndash7020 2018
[75] A Moneer M El-Sadawy G El-Said and A Radwan ldquoBoronhuman health risk assessment relative to the environmentalpollution of Lake Edku Egyptrdquo Journal of King AbdulazizUniversity vol 23 no 2 pp 41ndash55 2012
[76] C B Tabelin T Igarashi T Arima D Sato T Tatsuhara andS Tamoto ldquoCharacterization and evaluation of arsenic andboron adsorption onto natural geologic materials and theirapplication in the disposal of excavated altered rockrdquo Geo-derma vol 213 pp 163ndash172 2014
[77] G Aloisi K Wallmann M Drews and G BohrmannldquoEvidence for the submarine weathering of silicate minerals inBlack Sea sediments possible implications for the marine Liand B cyclesrdquo Geochemistry Geophysics Geosystems vol 5no 4 pp 1ndash22 2004
[78] C Degueldre and V Cloet ldquoPore water colloid properties inargillaceous sedimentary rocksrdquo Science of e Total Envi-ronment vol 569-570 pp 423ndash433 2016
Journal of Chemistry 19
[79] J A Higgins and D P Schrag ldquoRecords of Neogene seawaterchemistry and diagenesis in deep-sea carbonate sedimentsand pore fluidsrdquo Earth and Planetary Science Letters vol 357-358 pp 386ndash396 2012
[80] H Schroeder A-L Fabricius D Ecker T A Ternes andL Duester ldquoMetal(loid) speciation and size fractionation insediment pore water depth profiles examined with a newmesoprofiling systemrdquo Chemosphere vol 179 pp 185ndash193 2017
[81] Y Song and G Muller ldquoFreshwater sediments sinks andsources of brominerdquo Naturwissenschaften vol 80 no 12pp 558ndash560 1993
[82] M E Goher H I Farhat M H Abdo and S G Salem ldquoMetalpollution assessment in the surface sediment of Lake NasserEgyptrdquo Egyptian Journal of Aquatic Research vol 40 no 3pp 213ndash224 2014
[83] G F El-Said M M El-Sadawy and A A Moneer ldquoIncor-poration of fluoride and boron into surface sediments alongthe Egyptian Mediterranean coastrdquo Egyptian Journal ofAquatic Research vol 36 no 4 pp 569ndash583 2010
[84] B Gilfedder G M Petri M Wessels and H Biester ldquoAniodine mass-balance for Lake Constance Germany insightsinto iodine speciation changes and fluxesrdquo Geochimica etCosmochimica Acta vol 74 no 11 pp 3090ndash3111 2010
[85] E Korobova L Kolmykova B Ryzhenko et al ldquoDistributionand speciation of iodine in drinking waters from geochem-ically different areas of Bryansk region contaminated after theChernobyl accident in relation to health and remediationaspectsrdquo Journal of Geochemical Exploration vol 184pp 311ndash317 2018
[86] V Zic V W Truesdale and N Cukrov ldquo-e distribution ofiodide and iodate in anchialine cave watersmdashevidence forsustained localised oxidation of iodide to iodate in marinewaterrdquoMarine Chemistry vol 112 no 3-4 pp 168ndash178 2008
[87] M B Heeb J Criquet S G Zimmermann-Steffens andU Von Gunten ldquoOxidative treatment of bromide-containingwaters formation of bromine and its reactions with inorganicand organic compoundsmdasha critical reviewrdquo Water Researchvol 48 pp 15ndash42 2014
[88] V Sivasankar A K Darchen and R Omine SakthivelldquoChapter 2 ldquofluoride a world ubiquitous compound itschemistry and ways of contaminationrdquo in Surface ModifiedCarbons as Scavengers for Fluoride fromWater V SivasankarEd pp 5ndash32 copy Springer International Publishing Switzer-land Cham Switzerland 2016
[89] O Cabestrero P Del Buey and M E Sanz-Montero ldquoBio-sedimentary and geochemical constraints on the precipitationof mineral crusts in shallow sulphate lakesrdquo SedimentaryGeology vol 366 pp 32ndash46 2018
[90] M A Hassaan O A El-Rayis and E I Hemada ldquoEstimationof the redox potential of lake mariut drainage system (Qalaaand Umum drains)rdquoHydrology vol 5 no 6 pp 82ndash85 2017
20 Journal of Chemistry
Tabl
e4
Distribu
tionof
thestud
iedvariablesin
thesediment(s)alon
gLake
Mariout
Site
Sand
()
Mud ()
Porosity
()
CO3s
()
B s(m
ggminus
1 )P s
(mg
gminus1 )
Ca s
(mg
gminus1 )
Mg s
(mg
gminus1 )
Na s
(mg
gminus1 )
Ks
(mg
gminus1 )
Lis(m
ggminus
1 )
SO4s
(mg
gminus1 )
Fes
(mg
gminus1 )
Cu s (μg
gminus1 )
Mn s
(μg
gminus1 )
Zns(μg
gminus1 )
F s(m
ggminus
1 )
Cl s
(mg
gminus1 )
Brs
(mg
gminus1 )
I s(μg
gminus1 )
14
964915
183
299
044
1670
811
2583
408
0028
4861
828
963
5617
1272
034
041
128
1686
244
564925
574
196
028
1002
1419
2717
269
0015
662
257
793
4350
1313
057
054
123
358
319
816667
299
246
073
1670
1216
3125
336
0022
463
487
1228
4330
1677
044
034
448
516
418
824853
3813
1111
032
668
2229
3425
365
0094
2222
770
922
4637
1245
030
020
309
296
512
884697
482
614
012
501
1115
1833
091
0040
1713
243
600
27933
1223
082
034
245
254
65
954667
164
370
157
835
1257
2958
388
0030
5648
890
1927
5347
3117
070
020
852
209
75
954762
375
524
024
367
2047
3133
256
0102
1157
546
883
4185
1393
120
020
341
259
838
626143
457
697
039
668
1621
3550
347
0145
4167
598
737
4157
1412
022
034
144
1277
918
826000
349
083
054
401
1094
3358
369
0025
2454
701
868
5702
3065
036
027
250
172
1036
645070
441
296
002
935
1763
3117
246
0045
2685
369
790
4533
1315
012
047
1012
224
1185
157000
325
240
074
969
2250
3508
328
0193
1343
1026
735
3890
1070
005
007
533
128
1237
638214
463
291
032
334
1824
3008
358
0018
556
340
728
2475
827
001
007
852
281
134
965000
177
211
054
2338
1621
3925
599
0068
833
1687
1187
6492
1853
004
027
639
194
Min
415
4667
164
083
002
334
811
1833
091
0015
463
243
600
2475
827
001
007
123
128
Max
8596
8214
574
1111
157
2338
2250
3925
599
0193
6620
1687
1927
6492
3117
120
054
1012
1686
Av
2575
5609
359
398
048
951
1559
3096
335
0063
2671
672
951
4500
1599
040
029
452
450
SD23
231114
128
276
039
603
455
522
115
0055
2030
393
343
1120
708
035
014
303
475
Minm
inim
umM
axm
axim
uma
ndAv
averageSD
stand
arddeviation
Journal of Chemistry 11
(1559plusmn455mg gminus1) and calcium (951plusmn603mg gminus1) com-ponents may be attributed to the abundance of calcium min-erals [4] However in general the average amounts of allvariables in sediment samples showmarked variations fromonesite to another with a descending order of CO3sgtMgsgtCasgtNasgtSO4sgtFesgt BrsgtBsgtKsgtTPsgtFs gtClsgtMnsgtZnsgtCusgtLisgt Is (Table 4) -e measured concentra-tions of Mn Zn Cu and Fe in the sediment samples are stilllower than the reported values and also lower than the back-ground levels of crust and the toxicological reference contents ofUS DOE (US Department of Energy) US EPA (US Envi-ronmental Protection Agency) and CEQG (Canadian Envi-ronmental Quality Guidelines) [82]
Contrasting the obtained levels for the halogens withthose previously reported ones the present study indicatesthat surface and pore waters incorporate more considerableamounts of fluoride compared to the formerly reported onesin Lake Edku (Tables 2 and 3) and lower levels in theMarioutarea than those measured along the Egyptian MediterraneanSea coast [27] Compared with the sediments previouslyfound on the Mediterranean coast of Egypt the chloridecontent in the sediments of the Mariout area is lower [83]Compared with those observed in seawater the studiedsurface water and pore water samples have lower bromidecontent and higher levels than previously reported in LakeMariout [52 53] -e concentration of iodide in surfacewater pore water and sediments is equivalent to the con-centration of rivers and lakes in the world [84]
333 Interactions of Halogens and Tested Variables inSediment -e correlation matrix shows the important roleof halogens in the formation and precipitationdissolution ofsalts and minerals produced along the lake (SupplementaryTable 1) However it shows that chloride seems to be in thesoluble forms along the surface and pore waters of studiedarea showing good relations with Caw (r 0666 ple 0018)Clp (r 0677 ple 0016) and SO4p (r 0858 ple 0000)Also Cls gives good correlations with Mgw (r 0710ple 0010) Naw (r 0602 ple 0038) Clw (r 0619ple 0032) Mgp (r 0774 ple 0003) and Kp (r 0731ple 0007) Chloride in the surface and pore waters plays animportant role in the dissolution association and formationof various salts along the lake -e good relationship be-tween Is and Caw (r 0666 ple 0018) may reflect the de-positionrelease of CaI+ during the formationdissolution ofcalcium carbonate [85] In addition these correlations maybe related to organic-I which formed by bacterial species andtheir remineralization in bottom sediments [86] -emoderate relationship between Nas and Brw (r minus0622ple 0031) may indicate the possible formation of BrClspecies and the precipitation or adsorption of Na minerals insediments [87] -e results of this study also reflect thestrong negative correlation between Fs and Bw (r minus0666ple 0018) which may be related to the release of fluoridefrom sediment and the formation of soluble fluoridecomplexes ((BFn[OH]4minusn)minus) with the excessive boron con-centration in the water [88] -e negative relation betweenKs and Spermilw (r minus0673 ple 0016) possibly reflect that Kw
preferentially chooses to exist in the soluble form of KClrather than being adsorbed andor bound by some richminerals in the sediment
-e significant correlations between CO3s and Mgw(r 0637 ple 0026) CO3s and Clw (r 0723 ple 0008)CO3s and pHw (r 0833 ple 0001) CO3s and Spermilw(r 0723 ple 0008) and between CO3s and Ks (r minus0673ple 0016) may be accompanied by the possible formationdissolution of the dolomite mineral in the presence ofsufficient Mgw which is usually affected by optimal pHsalinity and the potassium salts (Supplementary Table 1)-ese observed results are matching with the previouslyreported studies [32] Significant negative correlation be-tween TPs and CO3s (r minus0744 ple 0006) may indicate theextended release of P from carbonate minerals and for-mation of apatites [32]
-e correlation matrix also refers to other possible in-teractions between the remaining determined variables(Supplementary Table 1) -e significant correlation be-tween SO4s andMgw (r 0706 ple 0010) and Liw (r 0633ple 0027) may be associated to the formation of Mg-sulfateand the pollution of sediments by discharged waters con-taining excessive sulfate and Li [89] In the contrary thestrong positive correlation between TPs and Cus and be-tween TPs and Zns may be related to the same source ofpolluted discharge water [23 83]
-e high negative correlations of Zns with Few(r minus0785 ple 0003) CO3s (r minus0601 ple 0039) and Cus(r 0698 ple 0012) may indicate that Zn Cu and CO3depositions in sediment samples are linked to the soluble Feform in water (ferrous) ie the release of Fe upwards in thewater column in the anoxic conditions (SupplementaryTable 1) [90] -e excellent relations found between Fesand CO3s (r minus0799 ple 0002) Fes and Cas (r 0637ple 0026) Fes and Clw (r minus0752 ple 0005) Fes and Nas(r 0720 ple 0008) and between Fes and Ks (r 0833ple 0001) may reflect the dissolution of the chelating Feassociation with the soluble organic compounds in thewater-sediment interface and the formation of the sol-uble ferrous form in low dissolved oxygen within theareas affected by untreated discharged waters [90] -estrong correlations of Mns with SO4w Nap Nas Ks CO3sZns and Fes (r minus0585 0608 0611 0698 minus0655 0691and 0716 respectively) may associate with the solubilityof abundant Mn minerals and P-Mn forms in the sedi-ment because of its possible reduction to Mn+2 solublespecies under anoxic conditions [90] It is worth men-tioning that the results of this study indicate that ap-proximately 333 of the survey sites indicate thedepletion of dissolved oxygen in their surface watersamples Under such anoxic conditions bacteria are mostlikely to use sulfate instead of oxygen to break downorganic matter and cause the release of iron and phos-phorus into the water column
-e significant direct correlation between Ks and Nas(r 0832 plt 0001) clearly reflects the transport of solublesalts of K and Na between the pore water phase of thesediment and water-sediment surface phase (SupplementaryTable 1) -e good correlation between porosity and Nas
12 Journal of Chemistry
indicates the possible transfer of Na between pore water andsediment partitions
34 Interactions of Precipitated Halogenated Compounds inSurface and Pore Waters -e Saturation Index (SI) [23 60]of twenty-three and fifteen structures in surface water andpore water samples respectively are listed (Table 1) -ecorrelation matrix of the calculated Saturation Indices withthe presented data shows the different factors affecting theinteraction of the halogenated compound with other pre-cipitated salts and minerals Table 1 explores the precipitationof the phosphate minerals and salts are most abundantfollowed by the hydroxidesrsquo salts iodate salts sulfate andcarbonate minerals and salts in surface waters Amongst thehalogens precipitated salts fluoride minerals especiallyfluorapatites and carbonate-fluorapatite (FAP and CFAP)have high SI values in surface water (4277ndash5195 and1604ndash6089 respectively) and in pore water (5126ndash5460 and1752ndash7833 respectively) Bromide and chloride are mainlyfound in the soluble forms in surface and pore waters Iodidesalts (Ca(IO3)2 and Ca(IO3)26H2O) moderately precipitatein surface and pore Iron salts precipitate in surface waterwhile in pore water they are not formed -us SI contentreflects that halogens especially fluoride and iodide play avital role in reducing lake pollution
In addition Table 1 shows that the precipitation com-pounds that may be formed in surface water are relativelydifferent from those in sediment pore water For examplefluorite (CaF2) and sellaıte (MgF2) may be only formed inpore water while calcite and aragonite may be deposited insurface water However the formation of fluorite in surfacewater is related to Naw (r 0778 ple 0003) Kw (r 0704ple 0011) CO3w (r minus0718 ple 0009) Fw (r 0770ple 0003) and Ip (r minus0785 ple 0003) (SupplementaryTable 1)
-e formation of calcium sulfate hemihydrate calciumsulfate and anhydrite in water is related to the increase in theamounts of Caw Mgw SO4w Nap Fp Sip Cls and Mns andthe decrease in porosity values On the other hand pre-cipitation of calcium phosphate is related to Brw (r 0751ple 0005) Znw (r 0668 ple 0018) Pw (r 0881ple 0001) and Ks (r 0881 ple 0001) ie it is affected bythe discharged water composition (Supplementary Table 1)
-e formation of calcite and aragonite in surface water isrelated to the formation of CO3w (r 0753 ple 0005) anddissociation of HCO3w (r minus0660 ple 0020) pHw values(r minus0654 ple 0021) and their dissolution in sediment(r minus0620 ple 0032) (Supplementary Table 1)
-e dolomite formation in water may be affected by theincrease of CO3w (r 0817 ple 0001) and the decrease ofHCO3w (r minus0658 ple 0020) increase in TDSw (r 0599ple 0040) and increase in pHw (r minus0656 ple 0021)besides the possible release of CO3s from abundant sediment(r minus0624 ple 0030) and the precipitation of calcite(r 0984 ple 0000) and aragonite (r 0984 ple 0000) intosediment fraction (Supplementary Table 1)
Generally in the current study the possible formedhalogenated minerals and salts are affected by their
abundance in different components of the lake besides theirpossible dissolution or formation on the sediment texturesgeochemistry of the sediments and physicochemical vari-ables of water in addition to the components of the dis-charged waters
35 Interactions of Dissolved Halogenated Compounds inSurface and PoreWaters -e utilization of dissolved salts insurface and pore waters by utilizing Palmerrsquos method andpiper ternary diagram [50] indicates that Na is the richestcation in surface water followed by Mg Ca and K At thesame time Mg is the most predominate one in the porewater (Figures 3 and 4) Obviously Cl is the most importantanion in surface water and pore waters samples Howeverthe piper ternary diagrams of surface water and pore waterclearly shows that NaCl is the most dominant in surfacewater while MgCl2 is the most abundant in pore waterCoincidently Palmerrsquos method also reflects that NaCl(574) is the most existent species in surface water fol-lowed by MgCl2 (304) CaCl2 (71) CaSO4 (29)Ca(HCO3)2 (14) and KCl (12) (Figure 3) At the sametime MgCl2 (760) is the most present species in porewater followed by NaCl (73)asympMg(HCO3)2 (73)Ca(HCO3)2 (52) and MgSO4 (31) (Figure 4)
36 Multivariate Analysis
361 Principal Component (PCA) By applying Varimaxrotation and Kaiser normalization to 98 variables in the PCAfor halogens and tested variables and calculated parametervalues 7 extracted PCs with eigenvalues higher than 1 areobtained However it is important that the eigenvalue mustbe greater than 1 Its seven PCs explain 8558 of the totalvariance
-e first principle component (PC1) is 1473 of thetotal variance and shows positive coefficient factor loadingsfor CO3w TDSw Kp calcite aragonite dolomite FeCO3MgCO3 ZnCO3 and ZnCO3H2O (0804 0547 05320938 0938 0947 0741 0940 0866 and 0866 respec-tively) In addition it provides negative factor loadings forHCO3w pHw Bw Nap and CO3s (minus0782 minus0610 minus0595minus0532 and minus0572 respectively) PC1 is related to thefactors affecting the carbonate compounds that may beformed in the area under consideration
PC2 accounts to 1458 of the total variance and alsoshows positive and negative coefficient factor loadingsrepresenting the different interactions between the CawMgw Liw SO4wMgp Nap pHp Cls SO4s Brs and porosityin water pore water and sediment that are responsible forthe composition of sulfate magnesium and phosphateprecipitates besides the effect of the discharged waters onwater-pore water-sediment componentsrsquo cycles
PC3 typically shows 1377 of the total variance withpositive and negative loadings which can properly explorethe effect of the principal sources of local pollution on thedissolving of heavy metals B and P from sediment into thewater column and the probable formation of Fe(OH)2Fe(OH)3) and FePO4
Journal of Chemistry 13
Similarly the coefficient factor loadings of PC4 with1355 are related to the influence of the polluted dischargewater and sediment texture on the formation of F Cl and Isalt besides the precipitation of halogenated compounds(FeF2 Mn(IO3)2 KIO4 and KCIO4) besides their minerals(CaF2 MgF2 FAP and CFAP)
Simultaneously PC5 gives 1092 of the total variancewith positive and negative loadings which explains therelations between the physicochemical limits of the surfacewater pore water and sediment components and theprecipitation of minerals and salts (OCP HAP CuBrZn(OH)2 and Zn(IO3)22H2O) -is is also associated tothe influence of the sedimentary material on the release ofMn Fe and P from sediment into pore water and watercolumn and formation of Ca3(PO4)2 OCP and HAPminerals
However PC6 associates with 100 of the total variancegiving positive and negative coefficient factor loadingswhich explain that the sediments (minerals andor organic-iodine compounds) are only the acting sink for iodine andiodine species (Iminus and IOminus
3 ) in the water as previously re-ported [84] PC6 also reflects the precipitation of severalhalogenated compounds such as calcium iodate (Ca(IO3)2and Ca(IO3)26H2O) and copper iodate (CuI andCuIO3H2O) besides Cu3(PO4)2 species in the lake watercolumn
-e loadings of PC7 contribute by 804 and show thatthe release of calcium in pore water into the water column isresponsible for the precipitation of halogenated compounds(CuCl and Zn(IO3)22H2O) as well as copper and Zn salts(Cu3(PO4)2 and Zn(OH)2)
362 Cluster Analysis On the other hand cluster analysisshows that the similarity of sites 1amp4 5amp8 6amp9 2amp10 and11amp13 is due to the texture of sediment
363 Multiple Regression Multiple regression equations ofhalogens as dependent variables and the other determinedand calculated parameters as independent variables insurface water pore water and sediment partitions are listed(Table 5)-e amount of fluoride in water samples is affectedby the discharged watersrsquo fundamental components espe-cially Zn and Cu besides its surface water-pore water in-teractions Its content in pore water seems to be stronglyaffected by its substitution competition with other halogensin surface water-spore water-sediment cycle due to its highelectronegativity Generally in the affected area the type ofpollutant in the discharged water plays an important role inthe dissolution andor precipitation of fluoride and otherhalogens in the surface water-pore water-sediment cycle
574
147129
300
12
Ca(HCO3)2CaSO4CaCl2
MgCl2KClNaCl
(a)
SO4
2 + CIndash Ca 2+ + Mg 2+
CO32ndash + HCO3
ndashNa+ + K+
Mg2+ SO42ndash
Ca2+ CIndash
(b)
Figure 3 (a) distribution and (b) piper ternary diagram of the formed dissolved salts in surface water of Lake Mariout
Ca(HCO3)2Mg(HCO3)2MgSO4
NaClMgCI2KCl
760 1052
7373 31
(a)
SO4
2ndash + C
Indash
Ca 2+ + Mg 2+
CO32ndash + HCO3
ndashNa+ + K+
Mg2+ SO42ndash
CIndashCa2+
(b)
Figure 4 (a) distribution and (b) piper ternary diagram of the formed dissolved salts in pore water of Lake Mariout
14 Journal of Chemistry
Table 5 -e multiple regression analyses of each halogen as dependent variable and other tested variables in the surface water pore waterand sediment partitions besides the precipitated salts in surface water along Lake Mariout
Dependentvariable Multiple regression equation R2
FluorideLake water FW 3162 + 092 Zn F2 minus 033 SiP + 021 CuIminus 017 SpermilP 09911
Pore water Fp minus2567minus117 SiW minus 033 LiP minus 062 CuClminus 028 IS + 023 TDSW+ 017 KIO4 minus 012 BrW minus 004porosity + 004 PW
10000
Sediment FS 088 CAPminus 049 MgS minus 046 DOW+039MgW+ 027 Mn(IO3)2 + 015 Cu3(PO4)2 + 004 HAP+ 002 pHP 10000ChlorideLake water No relation 00000Pore water No relation 00000Sediment ClS minus116 + 046 MgP + 077 Kp minus 049 dolomite + 017 TDSW minus 011 CuI + 005 NaS + 002 BS + 001 FeF2 10000Bromide
Lake water BrW 1563 + 110 CuBrminus 057 CuClminus 021 KS minus 014 pHP minus 011 TPS + 014 FeW+ 007 ZnSminus 002 PP + 001turbidity 10000
Pore water BrP minus1516minus 055 FeS minus 073 BS + 061 MnW+ 083 SiP + 049 NaS minus 031MnS minus 015 CuBr + 011 pHW minus 001CaW
10000
Sediment BrS 015 SiP + 195 CFAP+ 002 FP minus 045 IS + 192 sand+ 037 MnW minus 029 MgS minus 012 LiP + 005Ca3(PO4)2 minus 002 ZnF2
10000
IodideLake water IW 099 Ca(IO3)6H2O 09999
Pore water IP minus097 ZnF2 minus 057 Li3PO4 minus 053 BP + 034 FAP+ 015 Ca(IO3)2 +MnW+ 005 KS minus 009 turbidity + 055CaS
09999
Sediment IS minus072 + 135 SO4P + 023 Mn(IO3)2 + 063 FeW+ 031 TPS minus 035 MgP minus 012 Zn(CO3)22H2O 09993
40E + 0135E + 0130E + 0125E + 0120E + 0115E + 0110E + 0150E + 0000E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
12345
678910
111213
(a)
10E + 0090E ndash 0180E ndash 0170E ndash 0160E ndash 0150E ndash 0140E ndash 0130E ndash 0120E ndash 0110E ndash 0100E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
12345
678910
111213
(b)
12345
678910
111213
40E ndash 0235E ndash 0230E ndash 0225E ndash 0220E ndash 0215E ndash 0210E ndash 0250E ndash 0300E ndash 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
(c)
12345
678910
111213
80E ndash 0670E ndash 0660E ndash 0650E ndash 0640E ndash 0630E ndash 0620E ndash 0610E ndash 0600E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
(d)
Figure 5 Hazard quotient of ingestion and dermal contact of surface water and sediment of LakeMariout (a) ingestion of water (b) dermalcontact of water (c) ingestion of sediment and (d) dermal contact of sediment
Journal of Chemistry 15
Minerals and precipitated salts in the different partitions(surface water pore water and sediment) play an importantrole in the deposition and release of halogens in sedimentsAdditionally the texture and the porosity of the sedimentsplay a key role in the distribution of halogens in the threepartitions Interestingly chloride is the only halogen that hasnegligible interactions along the surface water and porewater partitions because it is present in large quantities inthe form of soluble salts (NaCl and MgCl2)
37 Pollution Status
371 Enrichment Factor (EF) Twowell-knownmethods areused to assess environmental pollution public health sig-nificance of ingestion and dermal contact with water andsediment components and sediment enrichment factor (EF)[59 60]
-e average EF values of the determined elements CaMg Na K Li B P Cu Zn Mn Fe F Cl Br and I are alllower than the value that is less than the minimum en-richment value (EFlt 2)-us the area under investigation isstill ecologically considered as an unpolluted region
372 Human Health Risk Assessment -e EDI HQ and HIshow the variable values of all pollutants in the surface waterand sediments along the lake region and in drains (sites11ndash13) under study Among all the calculated variables ofsurface water ingestion (EDIIngw) and dermal contact(EDIDermw) Cl is still the only variable that shows high levels(average 1551 and 43mg kgminus1 dayminus1 respectively) -eestimation daily intake of sediment ingestion (EDIIngs) anddermal contact (EDIDerms) of Mg Ca and Na give maximumaverage amounts of 841Eminus 02 513E ndash 02 and167Eminus 03mg kgminus1 dayminus1 respectively
Among the HQ of the calculated detection variables thecontent of HQB of ingestion and dermal contact with waterand sediment is the highest However 70 of sites have HQBvalues more than 10 (Figure 5) Comparing the HQ values ofall the determined variables HQB of the ingestion of surfacewater shows values higher (gt10) However due to the impactof drainage the HQB values of stations 1ndash4 8ndash10 12 and 13
are higher than 10 -erefore these sites can be consideredas the area with the most serious boron pollution caused byuntreated discharged water disposal In addition the HIIngwlevel of water ingestion for the studied variables in all sites ismuch higher than 10 (Figure 6) Except for boron it isusually concluded that the study area does not pose any riskto the population due to halogens or other variables Ac-cordingly this information may help the official authoritiesoptimize management plans and strengthen their pollutioncontrol actions in Lake Mariout
4 Conclusions
-e effects of halogen salts and minerals on the pollution ofLake Mariout were studied Halogens and some physico-chemical variables in three partitions surface water porewater and sediment in Lake Mariout were evaluated -ehalogen content was variable between different sites andchloride was the main halogen in surface water and porewater but it was very rare in the lakersquos sediment partitionPiper ternary diagram and Palmerrsquos method reflected thatNaCl was the dominant salt in surface water while MgCl2was the main dissolve salt in pore water-e chlorinity ratiosof halogens and tested variables were directly matched to thefeeding drain sources
Moreover the Saturation Index (SI) reveals that 23 and 15precipitated salts and minerals are formed in surface water andpore water respectively -e SI value indicated the formationof phosphate minerals in surface water and pore water es-pecially octacalcium phosphate (OCP Ca4H(PO4)325H2O)and hydroxyapatite (HAP Ca5(PO4)3OH) In addition tofluoride minerals especially fluorapatite (FAP) and carbonate-fluorapatite (CFAP) were obviously precipitated from surfacewater and pore water Soluble salts of bromide and chloridewere formed in surface water and pore water Iodide salts(Ca(IO3)2 and Ca(IO3)26H2O) were moderately precipitatedin the surface water and pore water
Moreover the multivariate analysis including the cor-relation matrix multiple stepwise linear regression treeclustering and principle component (PCA) of all the de-termined and calculated variables was applied to estimatethe proposed interaction between halogens and other tested
10E + 02
16E + 0214E + 0212E + 02
80E + 0160E + 0140E + 0120E + 0100E + 00
1 2 3 4 5 6 7 8 9 10 11 12 13
HIIngHIDerm
(a)
1 2 3 4 5 6 7 8 9 10 11 12 13
HIIngHIDerm
40E ndash 0235E ndash 0230E ndash 0225E ndash 0220E ndash 0215E ndash 0210E ndash 0250E ndash 0300E + 01
(b)
Figure 6 Hazard index of ingestion and dermal contact of the studied variables in surface water and sediment of Lake Mariout (a) waterand (b) sediment
16 Journal of Chemistry
variables in the polluted area under study -e multivariateanalysis showed that there were many interactions betweenhalogens and tested variables High levels of fluoride bro-mide and chloride in surface water were related to thecomposition of drainage waters -e enrichment factor (EF)showed that Lake Mariout was not polluted However thehuman health adverse effects calculated for surface waterand sediment did not reflect any possible likelihood hazardeffects from halogens
Interestingly the current study concluded that halogencompounds especially fluorides are most likely to be de-posited from surface lakes in the form of many minerals andprecipitation thereby reducing the adverse pollution effectson human health -e results obtained through this workhelp to find the correlations between the sampling sites andthe variables obtained by physical and chemical measure-ments which can be used to construct a fast decision modelfor separating different water quality samples -is infor-mation may help the official authorities optimize manage-ment plans and strengthen their pollution control measuresin Lake Mariout
Data Availability
-e data used to support the findings of this research areincluded within the paper
Conflicts of Interest
-e authors declare that there are no conflicts of interestregarding the publication of this manuscript
Supplementary Materials
Supplementary Table 1 correlation matrix of variable insurface water pore water and sediment partitions besidesthe precipitated salts in surface water along Lake Mariout(Supplementary Materials)
References
[1] M S Masoud T O Said G El-Zokm and M A ShreadahldquoAssesment of heavy metals contamination in surface sedi-ments of the Egyptian Red Sea Coastsrdquo Australian Journal ofBasic and Applied Sciences vol 6 pp 44ndash58 2012
[2] M A Shreadah M I Abdel Moneim T O SaidE M I Fathallah and M E Mahmoud ldquoPAHs in seawater ofthe semi-closed areas along the Alexandria coast of EgyptianMediterranean seardquo Journal of Environmental Protectionvol 4 no 11 p 11 Article ID 40298 2013
[3] S Abdel Ghani G El Zokm A Shobier T Othman andM Shreadah ldquoMetal pollution in surface sediments of Abu-Qir bay and Eastern harbour of Alexandria Egyptrdquo EgyptianJournal of Aquatic Research vol 39 no 1 pp 1ndash12 2013
[4] G F El-Said ldquoBioaccumulation of key metals and othercontaminants by seaweeds from the Egyptian MediterraneanSea Coast in relation to human health riskrdquo Human andEcological Risk Assessment An International Journal vol 19no 5 pp 1285ndash1305 2013
[5] M A Shreadah A H Shobier S Abdel Ghani G M El-Zokm and T O Said ldquoMajor ions anomalies and
contamination status by trace metals in sediments from twohot spots along the Mediterranean Coast of Egyptrdquo Envi-ronmental Monitoring and Assessment vol 187 no 280pp 1ndash18 2015
[6] A El Nemr G F El-Said A Khaled and S Ragab ldquoDis-tribution and ecological risk assessment of some heavy metalsin coastal surface sediments along the Red Sea Egyptrdquo In-ternational Journal of Sediment Research vol 31 no 2pp 164ndash172 2016
[7] A El Nemr G F El-Said S Ragab A Khaled and A El-Sikaily ldquo-e distribution contamination and risk assessmentof heavy metals in sediment and shellfish from the Red Seacoast Egyptrdquo Chemosphere vol 165 pp 369ndash380 2016
[8] A El Nemr and G F El-Said ldquoAssessment and ecological riskof heavy metals in sediment and molluscs from the Medi-terranean coastrdquo Water Environment Research vol 89 no 3pp 195ndash210 2017
[9] M A Sheradah A A El-Sikaily N M Abd El MoneamN E Abd El Maguid and M G Zaki ldquoChemical and bio-chemical evaluation of marine pollution by polychlorinatedbiphenyls and pesticides in two regions along the EgyptianMediterranean Seardquo International Journal of EnvironmentalMonitoring and Analysis vol 6 no 3 pp 95ndash109 2018
[10] M A Shreadah A A-M M El-Sayed A A S TahaA-M M Ahmed and H H Abdel Rahman ldquoEvaluation ofdifferent anthropogenic effluents impacts on the water qualityusing principal component analysis a case study of Abu-QirBay-Alexandria-Egyptrdquo International Journal of Environ-mental Monitoring and Analysis vol 7 no 3 pp 56ndash67 2019
[11] G F El-Said M M El-Sadaawy A H Shobier andS E Ramadan ldquoHuman health implication of major and traceelements present in commercial crustaceans of a traditionalseafood marketing region Egyptrdquo Biological Trace ElementResearch vol 199 pp 315ndash328 2020
[12] M A Shreadah S A A Ghani H B I HawashA A E Samie and A E M M Ahmed ldquoOrganotin com-pounds in sediments of northern lakes Egyptrdquo Journal ofEnvironmental Protection vol 05 no 17 pp 1654ndash1666 2014
[13] A M Younis G M El-Zokm and M A Okbah ldquoSpatialvariation of acid-volatile sulfide and simultaneously extractedmetals in Egyptian Mediterranean Sea lagoon sedimentsrdquoEnvironmental Monitoring and Assessment vol 186 no 6pp 3567ndash3579 2014
[14] G F El-Said S E O Draz M M El-Sadaawy andA A Moneer ldquoSedimentology geochemistry pollution statusand ecological risk assessment of some heavy metals insurficial sediments of an Egyptian lagoon connecting to theMediterranean Seardquo Journal of Environmental Science andHealth Part A vol 49 no 9 pp 1029ndash1044 2014
[15] G M El Zokm M A Okbah and A M Younis ldquoAssessmentof heavy metals pollution using AVS-SEM and fractionationtechniques in Edku Lagoon sediments Mediterranean SeaEgyptrdquo Journal of Environmental Science and Health PartAvol 50 no 6 pp 571ndash584 2015
[16] G M El Zokm H R Z Tadros M A Okbah andG H Ibrahim ldquoldquoEutrophication assessment using TRIX andCarlsonrsquos indices in Lake Mariout water Egyptrdquo EgyptianJournal of Aquatic Biology and Fisheries vol 22 no 5pp 331ndash349 2018
[17] N Donia ldquoLake Maryut monitoring using remote sensingrdquo inProceedings of the gypt Eighteenth International WaterTechnology Conference IWTC18 Sharm El Sheikh Abu DhabiUAE March 2015
Journal of Chemistry 17
[18] M A Khairy ldquoAssessment of priority phenolic compounds insediments from an extremely polluted coastal wetland (LakeMaryut Egypt)rdquo Environmental Monitoring and Assessmentvol 185 no 1 pp 441ndash455 2013
[19] N A El-Naggar and E A Rifaat ldquoEgyptian coastal lakes andwetlands part Imdashcharacteristics and hydrodynamicsrdquo in eHandbook of Environmental Chemistry A M Negm EdSpringer International Publishing AG Berlin Germany 2017
[20] J J Hanley and K T Koga ldquoChapter 2 ldquohalogens in terrestrialand cosmic geochemical systems abundances Geochemicalbehaviors and analytical methodsrdquordquo in e Role of Halogensin Terrestrial and Extraterrestrial Geochemical ProcessesD E Harlov and L Aranovich Eds Springer InternationalPublishing AG Berlin Germany pp 21ndash121 2018
[21] A Ghosh K Mukherjee S K Ghosh and B Saha ldquoSourcesand toxicity of fluoride in the environmentrdquo Research onChemical Intermediates vol 39 no 7 pp 2881ndash2915 2013
[22] M M Naim A A Moneer and G F El-Said ldquoPredictiveequations for the defluoridation by electrocoagulation tech-nique using bipolar aluminum electrodes in the absence andpresence of additives a multivariate studyrdquo Desalination andWater Treatment vol 57 no 14 pp 6320ndash6332 2016
[23] G F El-Said N A Shaltout M M El-Sadaawy andA M H Morsy ldquo-e precipitation of fluoride calcium andmagnesium minerals from Egyptian Mediterranean Sea coastin relation to discharged watersrdquo Desalination and WaterTreatment vol 57 no 5 pp 2113ndash2124 2016
[24] H Bureau ldquoIodine encyclopedia of geochemistry A com-prehensive reference source on the chemistry of the earthrdquo inEncyclopedia of Earth Sciences Series W M White Ed copySpringer International Publishing AG 2016
[25] F C Kupper and C J Carrano ldquoKey aspects of the iodinemetabolism in brown algae a brief critical reviewrdquo Metal-lomics vol 11 pp 756ndash764 2019
[26] R Liteplo R Gomes P Howe and H Malcolm Fluorides-Environmental Health Criteria 227 p 290 World HealthOrganization (WHO) Geneva Switzerland 2002
[27] G F El-Said and M M El-Sadaawy ldquoSeasonal variation ofboron and fluoride in Tilapia nilotica from an Egyptian fishfarm in relation to Human health hazard assessmentrdquoHumanand Ecological Risk Assessment An International Journalvol 19 no 4 pp 930ndash943 2013
[28] WHO (World Health Organization) Bromide in Drinking-Water Background Document for Development of WHOGuidelines for Drinking-Water Quality WHO Press WorldHealth Organization Geneva Switzerland 2009
[29] G F El-Said and N A Sallam ldquo-e uptake of fluorideconcentration and its effects on the growth rate of shrimps(Palaemon elegans Rathke)rdquo Chemistry and Ecology vol 24no 3 pp 191ndash205 2008
[30] X Zhang J He B He and J Sun ldquoAssessment formationmechanism and different source contributions of dissolvedsalt pollution in the shallow groundwater of Hutuo Riveralluvial-pluvial fan in the North China Plainrdquo EnvironmentalScience and Pollution Research vol 26 no 35 pp 35742ndash35756 2019
[31] Y Zhu B Huang Z Zhu et al ldquoldquoCharacterization disso-lution and solubility of the hydroxypyromorphitendashhydroxyapatite solid solution [(PbxCa1minusx)5(PO4)3OH] at25 degC and pH 2ndash9rdquo Geochemical Transactions vol 17 no 2pp 1ndash18 2016
[32] G F El-Said M M El-Sadaawy A A Moneer andN A Shaltout ldquo-e effect of fluoride on the distribution ofsome minerals in the surface water of an Egyptian lagoon at
the Mediterranean Seardquo Egyptian Journal of Aquatic Researchvol 41 no 1 pp 31ndash39 2015
[33] Y Zhu Z Zhu X Zhao Y Liang and Y Huang ldquoChar-acterization dissolution and solubility of lead hydroxypyr-omorphite [Pb5(PO4)3OH] at 25ndash45degCrdquo Journal ofChemistry vol 2015 Article ID 269387 10 pages 2015
[34] M A Z Chahouki ldquoMultivariate analysis techniques inenvironmental sciencerdquo in Earth and Environmental SciencesDr Imran Ahmad Dar Ed InTech Open London UK 2011httpwwwintechopencombooksearth-and-environmental-sciencesmultivariate-analysis-techniques-inenvironmental-science
[35] J V Klump and C S Martens ldquoBiogeochemical cycling in anorganic-rich coastal marine basin 5 Sedimentary nitrogenand phosphorus budgets based upon kinetic models massbalances and the stoichiometry of nutrient regenerationrdquoGeochimica et Cosmochimica Acta vol 51 no 5 pp 1161ndash1173 1987
[36] R L Folk Petrology of Sedimentary Rocks University of TexasAustin TX USA 1974
[37] P Saenger ldquoA rapid spectrophotometric method for thedetermination of bromine in seawater and in the ash ofmarine algaerdquo Helgolander Wissenschaftliche Meer-esuntersuchungen vol 23 no 1 pp 32ndash37 1972
[38] P G Jeffery Chemical Methods of Rock Analysis PergamonPress New York NY USA 2nd edition 1975
[39] J D H Strickland and T R Parsons ldquoA practical handbook ofseawater analysisrdquo in Fisheries Research Board of CanadaBulletin 167p 311 Second edition Wiley Ottawa Canada1972
[40] B Horvath O Opara-Nadi and F Beese ldquoA simple methodfor measuring the carbonate content of soilsrdquo Soil ScienceSociety of America Journal vol 69 no 4 pp 1066ndash1068 2005
[41] K Grasshoff Methods of Seawater Analysis p 317 VerlagChemie Weinkeim Germany 1976
[42] R Danovaro D Marrale N Della Croce P Parodi andM Fabiano ldquoBiochemical composition of sedimentary or-ganic matter and bacterial distribution in the Aegean Seatrophic state and pelagic-benthic couplingrdquo Journal of SeaResearch vol 42 no 2 pp 117ndash129 1999
[43] APHA-AWWA-WPCF (American Public Health Associa-tion) Standard Methods for the Examination of Water andWaste Water American Public Health Association Wash-ington DC USA 20th edition 1999
[44] K I Aspila H Agemian and A S Y Chau ldquoA semi-auto-mated method for the determination of inorganic organicand total phosphate in sedimentsrdquo e Analyst vol 101no 1200 pp 187ndash197 1976
[45] J P Riley and D Taylor ldquoChelating resins for the concen-tration of trace elements from sea water and their analyticaluse in conjunction with atomic absorption spectrophotom-etryrdquo Analytica Chimica Acta vol 40 pp 479ndash485 1968
[46] G F El-Said and A El-Sikaily ldquoChemical composition ofsome seaweed from Mediterranean Sea coast Egyptrdquo Envi-ronmental Monitoring and Assessment vol 185 no 7pp 6089ndash6099 2013
[47] Directorate General of Health Services Ministry of Health andFamilyWelfare Government of India ldquoManual of methods ofanalysis of foodsrdquo in Fruit and Vegetable Productsp 57Directorate General of Health Services Ministry of Health andFamily Welfare Government of India New Delhi India2005
[48] A Gunnars S Blomqvist and C Martinsson ldquoInorganicformation of apatite in brackish seawater from the Baltic Sea
18 Journal of Chemistry
an experimental approachrdquo Marine Chemistry vol 91 no 1-4 pp 15ndash26 2004
[49] W M Haynes D R Lide and T J Bruno CRC Handbook ofChemistry and Physics A Ready Reference Book of Chemicaland Physical Data CRC Press Taylor amp Frances Group BocaRaton FL USA 97th edition 2017
[50] M S Masoud M I El-Samra and M M El-Sadawy ldquoWaterchemistry of el-mex bay west of Alexandria Egyptrdquo eEgypian Science Magazine vol 2 pp 70ndash78 2005
[51] F J Millero R Feistel D G Wright and T J McDougallldquo-e composition of standard seawater and the definition ofthe reference-composition salinity scalerdquo Deep Sea ResearchPart I Oceanographic Research Papers vol 55 no 1pp 50ndash72 2008
[52] S K El-Wakeel S A Morcos and A M Mahlis ldquo-e majorcations in Lake Maryut watersrdquo Hydrobiologia vol 36 no 2pp 253ndash274 1970
[53] A M Mahlis S A Morcos and S K El-Wakeel ldquo-e majoranions in Lake Maryut watersrdquo Hydrobiologia vol 36 no 2pp 275ndash294 1970
[54] A S Saad M A Massoud R A Amer and M A GhorabldquoAssessment of the physico-chemical characteristics andwater quality analysis of Mariout Lake southern of Alexan-dria Egyptrdquo Journal of Environmental and Analytical Toxi-cology vol 7 no 1 p 421 2017
[55] R Rumuri ldquoDataset on hydrogeochemical characteristics ofgroundwater and surface water in Kattumannarkoil TalukIndiardquo Data in Brief vol 32 Article ID 106058 2020
[56] P Szefer S W Fowler K Ikuta et al ldquoA comparative as-sessment of heavy metal accumulation in soft parts and byssusof mussels from subarctic temperate subtropical and tropicalmarine environmentsrdquo Environmental Pollution vol 139no 1 pp 70ndash78 2006
[57] N F Soliman G M El Zokm and M A Okbah ldquoRisk as-sessment and chemical fractionation of selected elements insurface sediments from Lake Qarun Egypt using modifiedBCR techniquerdquo Chemosphere vol 191 pp 262ndash271 2018
[58] G M El Zokm M I A Ibrahim L A Mohamed and M El-Mamoney ldquoCritical geochemical insight into Alexandria coastwith special reference to diagnostic ratios (TOCTN amp SrCa)and heavy metals ecotoxicological hazardsrdquo Egyptian Journalof Aquatic Research vol 46 no 1 pp 27ndash33 2020
[59] A S Likuku K B Mmolawa and G K GaboutloeloeldquoAssessment of heavy metal enrichment and degree of con-tamination around the copper-nickel mine in the SelebiPhikwe Region Eastern Botswanardquo Environment and EcologyResearch vol 1 no 2 pp 32ndash40 2013
[60] M K Khalil S E O Draz G M El Zokm and G F El-SaidldquoApportionment of geochemistry texturersquos properties and riskassessment of some elements in surface sediments from Bar-dawil Lagoon Egyptrdquo Human and Ecological Risk AssessmentAn International Journal vol 22 no 3 pp 775ndash791 2016
[61] M M El-Sadaawy and G F El-Said ldquoAssessment of fluoridein three selected polluted environments along the EgyptianMediterranean Sea effects on local populationsrdquo Human andEcological Risk Assessment An International Journal vol 20no 6 pp 1643ndash1658 2014
[62] USEPA ldquoSuperfund exposure assessment manualrdquo inOSWER Directive 92855-1EPA540l-88001Office of Emer-gency and Remedial Response Washington DC USA 1988
[63] USEPA ldquoExposure factors handbookrdquo in EPA6008-89043Office of Health and Environmental Assessment Wash-ington DC USA 1989
[64] Health Canada ldquoFederal Contaminated Site Risk Assessmentin Canadardquo Part II Health Canada Toxicological ReferenceValues (TRVs) Cat H46-204-368E Calgary Health CanadaOttawa Canada 2007
[65] J Iqbal S A Tirmizi and M H Shah ldquoStatistical appor-tionment and risk assessment of selected metals in sedimentsfrom Rawal Lake (Pakistan)rdquo Environmental Monitoring andAssessment vol 185 no 1 pp 729ndash743 2013
[66] USEPA (US Environmental Protection Agency) Region 6USAEPA ldquoMultimedia Planning and Permitting DivisionrdquoOffice of Solid Waste Center for Combustion Science andEngineering Washington DC USA 2005
[67] P Jeschke ldquoLatest generation of halogen-containing pesti-cidesrdquo Pest Management Science vol 73 no 6 pp 1053ndash10662017
[68] M A Shreadah O A El-Rayis N A Shaaban andA M Hamdan ldquoWater quality assessment and phosphorusbudget of a lake (Mariut Egypt) after diversion of wastewaterseffluentsrdquo Environmental Science and Pollution Researchvol 27 no 21 pp 26786ndash26799 2020
[69] J P Riley and M Tongudai ldquo-e major cationchlorinityratios in sea waterrdquo Chemical Geology vol 2 pp 263ndash2691967
[70] R B McCleskey D K Nordstrom D D Susong J W Balland J M Holloway ldquoSource and fate of inorganic solutes inthe gibbon river yellowstone national park Wyoming USArdquoJournal of Volcanology and Geothermal Research vol 193no 3-4 pp 189ndash202 2010
[71] G T F Wong and K-Y Li ldquoWinklerrsquos method overestimatesdissolved oxygen in seawater iodate interference and itsoceanographic implicationsrdquo Marine Chemistry vol 115no 1-2 pp 86ndash91 2009
[72] B S R V Prasad P D N Srinivasu P S VarmaA V Raman and S Ray ldquoDynamics of dissolved oxygen inrelation to saturation and health of an aquatic body a case forChilka Lagoon Indiardquo Journal of Ecosystems vol 2014 Ar-ticle ID 526245 17 pages 2014
[73] China Environmental Protection Agency EnvironmentalQuality Standards for Surface Water (GB3838ndash2002) NationalEnvironmental Protection Agency of China Beijing China2002
[74] Y Jia L Wang Z Qu and Z Yang ldquoDistribution con-tamination and accumulation of heavy metals in watersediments and freshwater shellfish from Liuyang RiverSouthern Chinardquo Environmental Science and Pollution Re-search vol 25 no 7 pp 7012ndash7020 2018
[75] A Moneer M El-Sadawy G El-Said and A Radwan ldquoBoronhuman health risk assessment relative to the environmentalpollution of Lake Edku Egyptrdquo Journal of King AbdulazizUniversity vol 23 no 2 pp 41ndash55 2012
[76] C B Tabelin T Igarashi T Arima D Sato T Tatsuhara andS Tamoto ldquoCharacterization and evaluation of arsenic andboron adsorption onto natural geologic materials and theirapplication in the disposal of excavated altered rockrdquo Geo-derma vol 213 pp 163ndash172 2014
[77] G Aloisi K Wallmann M Drews and G BohrmannldquoEvidence for the submarine weathering of silicate minerals inBlack Sea sediments possible implications for the marine Liand B cyclesrdquo Geochemistry Geophysics Geosystems vol 5no 4 pp 1ndash22 2004
[78] C Degueldre and V Cloet ldquoPore water colloid properties inargillaceous sedimentary rocksrdquo Science of e Total Envi-ronment vol 569-570 pp 423ndash433 2016
Journal of Chemistry 19
[79] J A Higgins and D P Schrag ldquoRecords of Neogene seawaterchemistry and diagenesis in deep-sea carbonate sedimentsand pore fluidsrdquo Earth and Planetary Science Letters vol 357-358 pp 386ndash396 2012
[80] H Schroeder A-L Fabricius D Ecker T A Ternes andL Duester ldquoMetal(loid) speciation and size fractionation insediment pore water depth profiles examined with a newmesoprofiling systemrdquo Chemosphere vol 179 pp 185ndash193 2017
[81] Y Song and G Muller ldquoFreshwater sediments sinks andsources of brominerdquo Naturwissenschaften vol 80 no 12pp 558ndash560 1993
[82] M E Goher H I Farhat M H Abdo and S G Salem ldquoMetalpollution assessment in the surface sediment of Lake NasserEgyptrdquo Egyptian Journal of Aquatic Research vol 40 no 3pp 213ndash224 2014
[83] G F El-Said M M El-Sadawy and A A Moneer ldquoIncor-poration of fluoride and boron into surface sediments alongthe Egyptian Mediterranean coastrdquo Egyptian Journal ofAquatic Research vol 36 no 4 pp 569ndash583 2010
[84] B Gilfedder G M Petri M Wessels and H Biester ldquoAniodine mass-balance for Lake Constance Germany insightsinto iodine speciation changes and fluxesrdquo Geochimica etCosmochimica Acta vol 74 no 11 pp 3090ndash3111 2010
[85] E Korobova L Kolmykova B Ryzhenko et al ldquoDistributionand speciation of iodine in drinking waters from geochem-ically different areas of Bryansk region contaminated after theChernobyl accident in relation to health and remediationaspectsrdquo Journal of Geochemical Exploration vol 184pp 311ndash317 2018
[86] V Zic V W Truesdale and N Cukrov ldquo-e distribution ofiodide and iodate in anchialine cave watersmdashevidence forsustained localised oxidation of iodide to iodate in marinewaterrdquoMarine Chemistry vol 112 no 3-4 pp 168ndash178 2008
[87] M B Heeb J Criquet S G Zimmermann-Steffens andU Von Gunten ldquoOxidative treatment of bromide-containingwaters formation of bromine and its reactions with inorganicand organic compoundsmdasha critical reviewrdquo Water Researchvol 48 pp 15ndash42 2014
[88] V Sivasankar A K Darchen and R Omine SakthivelldquoChapter 2 ldquofluoride a world ubiquitous compound itschemistry and ways of contaminationrdquo in Surface ModifiedCarbons as Scavengers for Fluoride fromWater V SivasankarEd pp 5ndash32 copy Springer International Publishing Switzer-land Cham Switzerland 2016
[89] O Cabestrero P Del Buey and M E Sanz-Montero ldquoBio-sedimentary and geochemical constraints on the precipitationof mineral crusts in shallow sulphate lakesrdquo SedimentaryGeology vol 366 pp 32ndash46 2018
[90] M A Hassaan O A El-Rayis and E I Hemada ldquoEstimationof the redox potential of lake mariut drainage system (Qalaaand Umum drains)rdquoHydrology vol 5 no 6 pp 82ndash85 2017
20 Journal of Chemistry
(1559plusmn455mg gminus1) and calcium (951plusmn603mg gminus1) com-ponents may be attributed to the abundance of calcium min-erals [4] However in general the average amounts of allvariables in sediment samples showmarked variations fromonesite to another with a descending order of CO3sgtMgsgtCasgtNasgtSO4sgtFesgt BrsgtBsgtKsgtTPsgtFs gtClsgtMnsgtZnsgtCusgtLisgt Is (Table 4) -e measured concentra-tions of Mn Zn Cu and Fe in the sediment samples are stilllower than the reported values and also lower than the back-ground levels of crust and the toxicological reference contents ofUS DOE (US Department of Energy) US EPA (US Envi-ronmental Protection Agency) and CEQG (Canadian Envi-ronmental Quality Guidelines) [82]
Contrasting the obtained levels for the halogens withthose previously reported ones the present study indicatesthat surface and pore waters incorporate more considerableamounts of fluoride compared to the formerly reported onesin Lake Edku (Tables 2 and 3) and lower levels in theMarioutarea than those measured along the Egyptian MediterraneanSea coast [27] Compared with the sediments previouslyfound on the Mediterranean coast of Egypt the chloridecontent in the sediments of the Mariout area is lower [83]Compared with those observed in seawater the studiedsurface water and pore water samples have lower bromidecontent and higher levels than previously reported in LakeMariout [52 53] -e concentration of iodide in surfacewater pore water and sediments is equivalent to the con-centration of rivers and lakes in the world [84]
333 Interactions of Halogens and Tested Variables inSediment -e correlation matrix shows the important roleof halogens in the formation and precipitationdissolution ofsalts and minerals produced along the lake (SupplementaryTable 1) However it shows that chloride seems to be in thesoluble forms along the surface and pore waters of studiedarea showing good relations with Caw (r 0666 ple 0018)Clp (r 0677 ple 0016) and SO4p (r 0858 ple 0000)Also Cls gives good correlations with Mgw (r 0710ple 0010) Naw (r 0602 ple 0038) Clw (r 0619ple 0032) Mgp (r 0774 ple 0003) and Kp (r 0731ple 0007) Chloride in the surface and pore waters plays animportant role in the dissolution association and formationof various salts along the lake -e good relationship be-tween Is and Caw (r 0666 ple 0018) may reflect the de-positionrelease of CaI+ during the formationdissolution ofcalcium carbonate [85] In addition these correlations maybe related to organic-I which formed by bacterial species andtheir remineralization in bottom sediments [86] -emoderate relationship between Nas and Brw (r minus0622ple 0031) may indicate the possible formation of BrClspecies and the precipitation or adsorption of Na minerals insediments [87] -e results of this study also reflect thestrong negative correlation between Fs and Bw (r minus0666ple 0018) which may be related to the release of fluoridefrom sediment and the formation of soluble fluoridecomplexes ((BFn[OH]4minusn)minus) with the excessive boron con-centration in the water [88] -e negative relation betweenKs and Spermilw (r minus0673 ple 0016) possibly reflect that Kw
preferentially chooses to exist in the soluble form of KClrather than being adsorbed andor bound by some richminerals in the sediment
-e significant correlations between CO3s and Mgw(r 0637 ple 0026) CO3s and Clw (r 0723 ple 0008)CO3s and pHw (r 0833 ple 0001) CO3s and Spermilw(r 0723 ple 0008) and between CO3s and Ks (r minus0673ple 0016) may be accompanied by the possible formationdissolution of the dolomite mineral in the presence ofsufficient Mgw which is usually affected by optimal pHsalinity and the potassium salts (Supplementary Table 1)-ese observed results are matching with the previouslyreported studies [32] Significant negative correlation be-tween TPs and CO3s (r minus0744 ple 0006) may indicate theextended release of P from carbonate minerals and for-mation of apatites [32]
-e correlation matrix also refers to other possible in-teractions between the remaining determined variables(Supplementary Table 1) -e significant correlation be-tween SO4s andMgw (r 0706 ple 0010) and Liw (r 0633ple 0027) may be associated to the formation of Mg-sulfateand the pollution of sediments by discharged waters con-taining excessive sulfate and Li [89] In the contrary thestrong positive correlation between TPs and Cus and be-tween TPs and Zns may be related to the same source ofpolluted discharge water [23 83]
-e high negative correlations of Zns with Few(r minus0785 ple 0003) CO3s (r minus0601 ple 0039) and Cus(r 0698 ple 0012) may indicate that Zn Cu and CO3depositions in sediment samples are linked to the soluble Feform in water (ferrous) ie the release of Fe upwards in thewater column in the anoxic conditions (SupplementaryTable 1) [90] -e excellent relations found between Fesand CO3s (r minus0799 ple 0002) Fes and Cas (r 0637ple 0026) Fes and Clw (r minus0752 ple 0005) Fes and Nas(r 0720 ple 0008) and between Fes and Ks (r 0833ple 0001) may reflect the dissolution of the chelating Feassociation with the soluble organic compounds in thewater-sediment interface and the formation of the sol-uble ferrous form in low dissolved oxygen within theareas affected by untreated discharged waters [90] -estrong correlations of Mns with SO4w Nap Nas Ks CO3sZns and Fes (r minus0585 0608 0611 0698 minus0655 0691and 0716 respectively) may associate with the solubilityof abundant Mn minerals and P-Mn forms in the sedi-ment because of its possible reduction to Mn+2 solublespecies under anoxic conditions [90] It is worth men-tioning that the results of this study indicate that ap-proximately 333 of the survey sites indicate thedepletion of dissolved oxygen in their surface watersamples Under such anoxic conditions bacteria are mostlikely to use sulfate instead of oxygen to break downorganic matter and cause the release of iron and phos-phorus into the water column
-e significant direct correlation between Ks and Nas(r 0832 plt 0001) clearly reflects the transport of solublesalts of K and Na between the pore water phase of thesediment and water-sediment surface phase (SupplementaryTable 1) -e good correlation between porosity and Nas
12 Journal of Chemistry
indicates the possible transfer of Na between pore water andsediment partitions
34 Interactions of Precipitated Halogenated Compounds inSurface and Pore Waters -e Saturation Index (SI) [23 60]of twenty-three and fifteen structures in surface water andpore water samples respectively are listed (Table 1) -ecorrelation matrix of the calculated Saturation Indices withthe presented data shows the different factors affecting theinteraction of the halogenated compound with other pre-cipitated salts and minerals Table 1 explores the precipitationof the phosphate minerals and salts are most abundantfollowed by the hydroxidesrsquo salts iodate salts sulfate andcarbonate minerals and salts in surface waters Amongst thehalogens precipitated salts fluoride minerals especiallyfluorapatites and carbonate-fluorapatite (FAP and CFAP)have high SI values in surface water (4277ndash5195 and1604ndash6089 respectively) and in pore water (5126ndash5460 and1752ndash7833 respectively) Bromide and chloride are mainlyfound in the soluble forms in surface and pore waters Iodidesalts (Ca(IO3)2 and Ca(IO3)26H2O) moderately precipitatein surface and pore Iron salts precipitate in surface waterwhile in pore water they are not formed -us SI contentreflects that halogens especially fluoride and iodide play avital role in reducing lake pollution
In addition Table 1 shows that the precipitation com-pounds that may be formed in surface water are relativelydifferent from those in sediment pore water For examplefluorite (CaF2) and sellaıte (MgF2) may be only formed inpore water while calcite and aragonite may be deposited insurface water However the formation of fluorite in surfacewater is related to Naw (r 0778 ple 0003) Kw (r 0704ple 0011) CO3w (r minus0718 ple 0009) Fw (r 0770ple 0003) and Ip (r minus0785 ple 0003) (SupplementaryTable 1)
-e formation of calcium sulfate hemihydrate calciumsulfate and anhydrite in water is related to the increase in theamounts of Caw Mgw SO4w Nap Fp Sip Cls and Mns andthe decrease in porosity values On the other hand pre-cipitation of calcium phosphate is related to Brw (r 0751ple 0005) Znw (r 0668 ple 0018) Pw (r 0881ple 0001) and Ks (r 0881 ple 0001) ie it is affected bythe discharged water composition (Supplementary Table 1)
-e formation of calcite and aragonite in surface water isrelated to the formation of CO3w (r 0753 ple 0005) anddissociation of HCO3w (r minus0660 ple 0020) pHw values(r minus0654 ple 0021) and their dissolution in sediment(r minus0620 ple 0032) (Supplementary Table 1)
-e dolomite formation in water may be affected by theincrease of CO3w (r 0817 ple 0001) and the decrease ofHCO3w (r minus0658 ple 0020) increase in TDSw (r 0599ple 0040) and increase in pHw (r minus0656 ple 0021)besides the possible release of CO3s from abundant sediment(r minus0624 ple 0030) and the precipitation of calcite(r 0984 ple 0000) and aragonite (r 0984 ple 0000) intosediment fraction (Supplementary Table 1)
Generally in the current study the possible formedhalogenated minerals and salts are affected by their
abundance in different components of the lake besides theirpossible dissolution or formation on the sediment texturesgeochemistry of the sediments and physicochemical vari-ables of water in addition to the components of the dis-charged waters
35 Interactions of Dissolved Halogenated Compounds inSurface and PoreWaters -e utilization of dissolved salts insurface and pore waters by utilizing Palmerrsquos method andpiper ternary diagram [50] indicates that Na is the richestcation in surface water followed by Mg Ca and K At thesame time Mg is the most predominate one in the porewater (Figures 3 and 4) Obviously Cl is the most importantanion in surface water and pore waters samples Howeverthe piper ternary diagrams of surface water and pore waterclearly shows that NaCl is the most dominant in surfacewater while MgCl2 is the most abundant in pore waterCoincidently Palmerrsquos method also reflects that NaCl(574) is the most existent species in surface water fol-lowed by MgCl2 (304) CaCl2 (71) CaSO4 (29)Ca(HCO3)2 (14) and KCl (12) (Figure 3) At the sametime MgCl2 (760) is the most present species in porewater followed by NaCl (73)asympMg(HCO3)2 (73)Ca(HCO3)2 (52) and MgSO4 (31) (Figure 4)
36 Multivariate Analysis
361 Principal Component (PCA) By applying Varimaxrotation and Kaiser normalization to 98 variables in the PCAfor halogens and tested variables and calculated parametervalues 7 extracted PCs with eigenvalues higher than 1 areobtained However it is important that the eigenvalue mustbe greater than 1 Its seven PCs explain 8558 of the totalvariance
-e first principle component (PC1) is 1473 of thetotal variance and shows positive coefficient factor loadingsfor CO3w TDSw Kp calcite aragonite dolomite FeCO3MgCO3 ZnCO3 and ZnCO3H2O (0804 0547 05320938 0938 0947 0741 0940 0866 and 0866 respec-tively) In addition it provides negative factor loadings forHCO3w pHw Bw Nap and CO3s (minus0782 minus0610 minus0595minus0532 and minus0572 respectively) PC1 is related to thefactors affecting the carbonate compounds that may beformed in the area under consideration
PC2 accounts to 1458 of the total variance and alsoshows positive and negative coefficient factor loadingsrepresenting the different interactions between the CawMgw Liw SO4wMgp Nap pHp Cls SO4s Brs and porosityin water pore water and sediment that are responsible forthe composition of sulfate magnesium and phosphateprecipitates besides the effect of the discharged waters onwater-pore water-sediment componentsrsquo cycles
PC3 typically shows 1377 of the total variance withpositive and negative loadings which can properly explorethe effect of the principal sources of local pollution on thedissolving of heavy metals B and P from sediment into thewater column and the probable formation of Fe(OH)2Fe(OH)3) and FePO4
Journal of Chemistry 13
Similarly the coefficient factor loadings of PC4 with1355 are related to the influence of the polluted dischargewater and sediment texture on the formation of F Cl and Isalt besides the precipitation of halogenated compounds(FeF2 Mn(IO3)2 KIO4 and KCIO4) besides their minerals(CaF2 MgF2 FAP and CFAP)
Simultaneously PC5 gives 1092 of the total variancewith positive and negative loadings which explains therelations between the physicochemical limits of the surfacewater pore water and sediment components and theprecipitation of minerals and salts (OCP HAP CuBrZn(OH)2 and Zn(IO3)22H2O) -is is also associated tothe influence of the sedimentary material on the release ofMn Fe and P from sediment into pore water and watercolumn and formation of Ca3(PO4)2 OCP and HAPminerals
However PC6 associates with 100 of the total variancegiving positive and negative coefficient factor loadingswhich explain that the sediments (minerals andor organic-iodine compounds) are only the acting sink for iodine andiodine species (Iminus and IOminus
3 ) in the water as previously re-ported [84] PC6 also reflects the precipitation of severalhalogenated compounds such as calcium iodate (Ca(IO3)2and Ca(IO3)26H2O) and copper iodate (CuI andCuIO3H2O) besides Cu3(PO4)2 species in the lake watercolumn
-e loadings of PC7 contribute by 804 and show thatthe release of calcium in pore water into the water column isresponsible for the precipitation of halogenated compounds(CuCl and Zn(IO3)22H2O) as well as copper and Zn salts(Cu3(PO4)2 and Zn(OH)2)
362 Cluster Analysis On the other hand cluster analysisshows that the similarity of sites 1amp4 5amp8 6amp9 2amp10 and11amp13 is due to the texture of sediment
363 Multiple Regression Multiple regression equations ofhalogens as dependent variables and the other determinedand calculated parameters as independent variables insurface water pore water and sediment partitions are listed(Table 5)-e amount of fluoride in water samples is affectedby the discharged watersrsquo fundamental components espe-cially Zn and Cu besides its surface water-pore water in-teractions Its content in pore water seems to be stronglyaffected by its substitution competition with other halogensin surface water-spore water-sediment cycle due to its highelectronegativity Generally in the affected area the type ofpollutant in the discharged water plays an important role inthe dissolution andor precipitation of fluoride and otherhalogens in the surface water-pore water-sediment cycle
574
147129
300
12
Ca(HCO3)2CaSO4CaCl2
MgCl2KClNaCl
(a)
SO4
2 + CIndash Ca 2+ + Mg 2+
CO32ndash + HCO3
ndashNa+ + K+
Mg2+ SO42ndash
Ca2+ CIndash
(b)
Figure 3 (a) distribution and (b) piper ternary diagram of the formed dissolved salts in surface water of Lake Mariout
Ca(HCO3)2Mg(HCO3)2MgSO4
NaClMgCI2KCl
760 1052
7373 31
(a)
SO4
2ndash + C
Indash
Ca 2+ + Mg 2+
CO32ndash + HCO3
ndashNa+ + K+
Mg2+ SO42ndash
CIndashCa2+
(b)
Figure 4 (a) distribution and (b) piper ternary diagram of the formed dissolved salts in pore water of Lake Mariout
14 Journal of Chemistry
Table 5 -e multiple regression analyses of each halogen as dependent variable and other tested variables in the surface water pore waterand sediment partitions besides the precipitated salts in surface water along Lake Mariout
Dependentvariable Multiple regression equation R2
FluorideLake water FW 3162 + 092 Zn F2 minus 033 SiP + 021 CuIminus 017 SpermilP 09911
Pore water Fp minus2567minus117 SiW minus 033 LiP minus 062 CuClminus 028 IS + 023 TDSW+ 017 KIO4 minus 012 BrW minus 004porosity + 004 PW
10000
Sediment FS 088 CAPminus 049 MgS minus 046 DOW+039MgW+ 027 Mn(IO3)2 + 015 Cu3(PO4)2 + 004 HAP+ 002 pHP 10000ChlorideLake water No relation 00000Pore water No relation 00000Sediment ClS minus116 + 046 MgP + 077 Kp minus 049 dolomite + 017 TDSW minus 011 CuI + 005 NaS + 002 BS + 001 FeF2 10000Bromide
Lake water BrW 1563 + 110 CuBrminus 057 CuClminus 021 KS minus 014 pHP minus 011 TPS + 014 FeW+ 007 ZnSminus 002 PP + 001turbidity 10000
Pore water BrP minus1516minus 055 FeS minus 073 BS + 061 MnW+ 083 SiP + 049 NaS minus 031MnS minus 015 CuBr + 011 pHW minus 001CaW
10000
Sediment BrS 015 SiP + 195 CFAP+ 002 FP minus 045 IS + 192 sand+ 037 MnW minus 029 MgS minus 012 LiP + 005Ca3(PO4)2 minus 002 ZnF2
10000
IodideLake water IW 099 Ca(IO3)6H2O 09999
Pore water IP minus097 ZnF2 minus 057 Li3PO4 minus 053 BP + 034 FAP+ 015 Ca(IO3)2 +MnW+ 005 KS minus 009 turbidity + 055CaS
09999
Sediment IS minus072 + 135 SO4P + 023 Mn(IO3)2 + 063 FeW+ 031 TPS minus 035 MgP minus 012 Zn(CO3)22H2O 09993
40E + 0135E + 0130E + 0125E + 0120E + 0115E + 0110E + 0150E + 0000E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
12345
678910
111213
(a)
10E + 0090E ndash 0180E ndash 0170E ndash 0160E ndash 0150E ndash 0140E ndash 0130E ndash 0120E ndash 0110E ndash 0100E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
12345
678910
111213
(b)
12345
678910
111213
40E ndash 0235E ndash 0230E ndash 0225E ndash 0220E ndash 0215E ndash 0210E ndash 0250E ndash 0300E ndash 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
(c)
12345
678910
111213
80E ndash 0670E ndash 0660E ndash 0650E ndash 0640E ndash 0630E ndash 0620E ndash 0610E ndash 0600E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
(d)
Figure 5 Hazard quotient of ingestion and dermal contact of surface water and sediment of LakeMariout (a) ingestion of water (b) dermalcontact of water (c) ingestion of sediment and (d) dermal contact of sediment
Journal of Chemistry 15
Minerals and precipitated salts in the different partitions(surface water pore water and sediment) play an importantrole in the deposition and release of halogens in sedimentsAdditionally the texture and the porosity of the sedimentsplay a key role in the distribution of halogens in the threepartitions Interestingly chloride is the only halogen that hasnegligible interactions along the surface water and porewater partitions because it is present in large quantities inthe form of soluble salts (NaCl and MgCl2)
37 Pollution Status
371 Enrichment Factor (EF) Twowell-knownmethods areused to assess environmental pollution public health sig-nificance of ingestion and dermal contact with water andsediment components and sediment enrichment factor (EF)[59 60]
-e average EF values of the determined elements CaMg Na K Li B P Cu Zn Mn Fe F Cl Br and I are alllower than the value that is less than the minimum en-richment value (EFlt 2)-us the area under investigation isstill ecologically considered as an unpolluted region
372 Human Health Risk Assessment -e EDI HQ and HIshow the variable values of all pollutants in the surface waterand sediments along the lake region and in drains (sites11ndash13) under study Among all the calculated variables ofsurface water ingestion (EDIIngw) and dermal contact(EDIDermw) Cl is still the only variable that shows high levels(average 1551 and 43mg kgminus1 dayminus1 respectively) -eestimation daily intake of sediment ingestion (EDIIngs) anddermal contact (EDIDerms) of Mg Ca and Na give maximumaverage amounts of 841Eminus 02 513E ndash 02 and167Eminus 03mg kgminus1 dayminus1 respectively
Among the HQ of the calculated detection variables thecontent of HQB of ingestion and dermal contact with waterand sediment is the highest However 70 of sites have HQBvalues more than 10 (Figure 5) Comparing the HQ values ofall the determined variables HQB of the ingestion of surfacewater shows values higher (gt10) However due to the impactof drainage the HQB values of stations 1ndash4 8ndash10 12 and 13
are higher than 10 -erefore these sites can be consideredas the area with the most serious boron pollution caused byuntreated discharged water disposal In addition the HIIngwlevel of water ingestion for the studied variables in all sites ismuch higher than 10 (Figure 6) Except for boron it isusually concluded that the study area does not pose any riskto the population due to halogens or other variables Ac-cordingly this information may help the official authoritiesoptimize management plans and strengthen their pollutioncontrol actions in Lake Mariout
4 Conclusions
-e effects of halogen salts and minerals on the pollution ofLake Mariout were studied Halogens and some physico-chemical variables in three partitions surface water porewater and sediment in Lake Mariout were evaluated -ehalogen content was variable between different sites andchloride was the main halogen in surface water and porewater but it was very rare in the lakersquos sediment partitionPiper ternary diagram and Palmerrsquos method reflected thatNaCl was the dominant salt in surface water while MgCl2was the main dissolve salt in pore water-e chlorinity ratiosof halogens and tested variables were directly matched to thefeeding drain sources
Moreover the Saturation Index (SI) reveals that 23 and 15precipitated salts and minerals are formed in surface water andpore water respectively -e SI value indicated the formationof phosphate minerals in surface water and pore water es-pecially octacalcium phosphate (OCP Ca4H(PO4)325H2O)and hydroxyapatite (HAP Ca5(PO4)3OH) In addition tofluoride minerals especially fluorapatite (FAP) and carbonate-fluorapatite (CFAP) were obviously precipitated from surfacewater and pore water Soluble salts of bromide and chloridewere formed in surface water and pore water Iodide salts(Ca(IO3)2 and Ca(IO3)26H2O) were moderately precipitatedin the surface water and pore water
Moreover the multivariate analysis including the cor-relation matrix multiple stepwise linear regression treeclustering and principle component (PCA) of all the de-termined and calculated variables was applied to estimatethe proposed interaction between halogens and other tested
10E + 02
16E + 0214E + 0212E + 02
80E + 0160E + 0140E + 0120E + 0100E + 00
1 2 3 4 5 6 7 8 9 10 11 12 13
HIIngHIDerm
(a)
1 2 3 4 5 6 7 8 9 10 11 12 13
HIIngHIDerm
40E ndash 0235E ndash 0230E ndash 0225E ndash 0220E ndash 0215E ndash 0210E ndash 0250E ndash 0300E + 01
(b)
Figure 6 Hazard index of ingestion and dermal contact of the studied variables in surface water and sediment of Lake Mariout (a) waterand (b) sediment
16 Journal of Chemistry
variables in the polluted area under study -e multivariateanalysis showed that there were many interactions betweenhalogens and tested variables High levels of fluoride bro-mide and chloride in surface water were related to thecomposition of drainage waters -e enrichment factor (EF)showed that Lake Mariout was not polluted However thehuman health adverse effects calculated for surface waterand sediment did not reflect any possible likelihood hazardeffects from halogens
Interestingly the current study concluded that halogencompounds especially fluorides are most likely to be de-posited from surface lakes in the form of many minerals andprecipitation thereby reducing the adverse pollution effectson human health -e results obtained through this workhelp to find the correlations between the sampling sites andthe variables obtained by physical and chemical measure-ments which can be used to construct a fast decision modelfor separating different water quality samples -is infor-mation may help the official authorities optimize manage-ment plans and strengthen their pollution control measuresin Lake Mariout
Data Availability
-e data used to support the findings of this research areincluded within the paper
Conflicts of Interest
-e authors declare that there are no conflicts of interestregarding the publication of this manuscript
Supplementary Materials
Supplementary Table 1 correlation matrix of variable insurface water pore water and sediment partitions besidesthe precipitated salts in surface water along Lake Mariout(Supplementary Materials)
References
[1] M S Masoud T O Said G El-Zokm and M A ShreadahldquoAssesment of heavy metals contamination in surface sedi-ments of the Egyptian Red Sea Coastsrdquo Australian Journal ofBasic and Applied Sciences vol 6 pp 44ndash58 2012
[2] M A Shreadah M I Abdel Moneim T O SaidE M I Fathallah and M E Mahmoud ldquoPAHs in seawater ofthe semi-closed areas along the Alexandria coast of EgyptianMediterranean seardquo Journal of Environmental Protectionvol 4 no 11 p 11 Article ID 40298 2013
[3] S Abdel Ghani G El Zokm A Shobier T Othman andM Shreadah ldquoMetal pollution in surface sediments of Abu-Qir bay and Eastern harbour of Alexandria Egyptrdquo EgyptianJournal of Aquatic Research vol 39 no 1 pp 1ndash12 2013
[4] G F El-Said ldquoBioaccumulation of key metals and othercontaminants by seaweeds from the Egyptian MediterraneanSea Coast in relation to human health riskrdquo Human andEcological Risk Assessment An International Journal vol 19no 5 pp 1285ndash1305 2013
[5] M A Shreadah A H Shobier S Abdel Ghani G M El-Zokm and T O Said ldquoMajor ions anomalies and
contamination status by trace metals in sediments from twohot spots along the Mediterranean Coast of Egyptrdquo Envi-ronmental Monitoring and Assessment vol 187 no 280pp 1ndash18 2015
[6] A El Nemr G F El-Said A Khaled and S Ragab ldquoDis-tribution and ecological risk assessment of some heavy metalsin coastal surface sediments along the Red Sea Egyptrdquo In-ternational Journal of Sediment Research vol 31 no 2pp 164ndash172 2016
[7] A El Nemr G F El-Said S Ragab A Khaled and A El-Sikaily ldquo-e distribution contamination and risk assessmentof heavy metals in sediment and shellfish from the Red Seacoast Egyptrdquo Chemosphere vol 165 pp 369ndash380 2016
[8] A El Nemr and G F El-Said ldquoAssessment and ecological riskof heavy metals in sediment and molluscs from the Medi-terranean coastrdquo Water Environment Research vol 89 no 3pp 195ndash210 2017
[9] M A Sheradah A A El-Sikaily N M Abd El MoneamN E Abd El Maguid and M G Zaki ldquoChemical and bio-chemical evaluation of marine pollution by polychlorinatedbiphenyls and pesticides in two regions along the EgyptianMediterranean Seardquo International Journal of EnvironmentalMonitoring and Analysis vol 6 no 3 pp 95ndash109 2018
[10] M A Shreadah A A-M M El-Sayed A A S TahaA-M M Ahmed and H H Abdel Rahman ldquoEvaluation ofdifferent anthropogenic effluents impacts on the water qualityusing principal component analysis a case study of Abu-QirBay-Alexandria-Egyptrdquo International Journal of Environ-mental Monitoring and Analysis vol 7 no 3 pp 56ndash67 2019
[11] G F El-Said M M El-Sadaawy A H Shobier andS E Ramadan ldquoHuman health implication of major and traceelements present in commercial crustaceans of a traditionalseafood marketing region Egyptrdquo Biological Trace ElementResearch vol 199 pp 315ndash328 2020
[12] M A Shreadah S A A Ghani H B I HawashA A E Samie and A E M M Ahmed ldquoOrganotin com-pounds in sediments of northern lakes Egyptrdquo Journal ofEnvironmental Protection vol 05 no 17 pp 1654ndash1666 2014
[13] A M Younis G M El-Zokm and M A Okbah ldquoSpatialvariation of acid-volatile sulfide and simultaneously extractedmetals in Egyptian Mediterranean Sea lagoon sedimentsrdquoEnvironmental Monitoring and Assessment vol 186 no 6pp 3567ndash3579 2014
[14] G F El-Said S E O Draz M M El-Sadaawy andA A Moneer ldquoSedimentology geochemistry pollution statusand ecological risk assessment of some heavy metals insurficial sediments of an Egyptian lagoon connecting to theMediterranean Seardquo Journal of Environmental Science andHealth Part A vol 49 no 9 pp 1029ndash1044 2014
[15] G M El Zokm M A Okbah and A M Younis ldquoAssessmentof heavy metals pollution using AVS-SEM and fractionationtechniques in Edku Lagoon sediments Mediterranean SeaEgyptrdquo Journal of Environmental Science and Health PartAvol 50 no 6 pp 571ndash584 2015
[16] G M El Zokm H R Z Tadros M A Okbah andG H Ibrahim ldquoldquoEutrophication assessment using TRIX andCarlsonrsquos indices in Lake Mariout water Egyptrdquo EgyptianJournal of Aquatic Biology and Fisheries vol 22 no 5pp 331ndash349 2018
[17] N Donia ldquoLake Maryut monitoring using remote sensingrdquo inProceedings of the gypt Eighteenth International WaterTechnology Conference IWTC18 Sharm El Sheikh Abu DhabiUAE March 2015
Journal of Chemistry 17
[18] M A Khairy ldquoAssessment of priority phenolic compounds insediments from an extremely polluted coastal wetland (LakeMaryut Egypt)rdquo Environmental Monitoring and Assessmentvol 185 no 1 pp 441ndash455 2013
[19] N A El-Naggar and E A Rifaat ldquoEgyptian coastal lakes andwetlands part Imdashcharacteristics and hydrodynamicsrdquo in eHandbook of Environmental Chemistry A M Negm EdSpringer International Publishing AG Berlin Germany 2017
[20] J J Hanley and K T Koga ldquoChapter 2 ldquohalogens in terrestrialand cosmic geochemical systems abundances Geochemicalbehaviors and analytical methodsrdquordquo in e Role of Halogensin Terrestrial and Extraterrestrial Geochemical ProcessesD E Harlov and L Aranovich Eds Springer InternationalPublishing AG Berlin Germany pp 21ndash121 2018
[21] A Ghosh K Mukherjee S K Ghosh and B Saha ldquoSourcesand toxicity of fluoride in the environmentrdquo Research onChemical Intermediates vol 39 no 7 pp 2881ndash2915 2013
[22] M M Naim A A Moneer and G F El-Said ldquoPredictiveequations for the defluoridation by electrocoagulation tech-nique using bipolar aluminum electrodes in the absence andpresence of additives a multivariate studyrdquo Desalination andWater Treatment vol 57 no 14 pp 6320ndash6332 2016
[23] G F El-Said N A Shaltout M M El-Sadaawy andA M H Morsy ldquo-e precipitation of fluoride calcium andmagnesium minerals from Egyptian Mediterranean Sea coastin relation to discharged watersrdquo Desalination and WaterTreatment vol 57 no 5 pp 2113ndash2124 2016
[24] H Bureau ldquoIodine encyclopedia of geochemistry A com-prehensive reference source on the chemistry of the earthrdquo inEncyclopedia of Earth Sciences Series W M White Ed copySpringer International Publishing AG 2016
[25] F C Kupper and C J Carrano ldquoKey aspects of the iodinemetabolism in brown algae a brief critical reviewrdquo Metal-lomics vol 11 pp 756ndash764 2019
[26] R Liteplo R Gomes P Howe and H Malcolm Fluorides-Environmental Health Criteria 227 p 290 World HealthOrganization (WHO) Geneva Switzerland 2002
[27] G F El-Said and M M El-Sadaawy ldquoSeasonal variation ofboron and fluoride in Tilapia nilotica from an Egyptian fishfarm in relation to Human health hazard assessmentrdquoHumanand Ecological Risk Assessment An International Journalvol 19 no 4 pp 930ndash943 2013
[28] WHO (World Health Organization) Bromide in Drinking-Water Background Document for Development of WHOGuidelines for Drinking-Water Quality WHO Press WorldHealth Organization Geneva Switzerland 2009
[29] G F El-Said and N A Sallam ldquo-e uptake of fluorideconcentration and its effects on the growth rate of shrimps(Palaemon elegans Rathke)rdquo Chemistry and Ecology vol 24no 3 pp 191ndash205 2008
[30] X Zhang J He B He and J Sun ldquoAssessment formationmechanism and different source contributions of dissolvedsalt pollution in the shallow groundwater of Hutuo Riveralluvial-pluvial fan in the North China Plainrdquo EnvironmentalScience and Pollution Research vol 26 no 35 pp 35742ndash35756 2019
[31] Y Zhu B Huang Z Zhu et al ldquoldquoCharacterization disso-lution and solubility of the hydroxypyromorphitendashhydroxyapatite solid solution [(PbxCa1minusx)5(PO4)3OH] at25 degC and pH 2ndash9rdquo Geochemical Transactions vol 17 no 2pp 1ndash18 2016
[32] G F El-Said M M El-Sadaawy A A Moneer andN A Shaltout ldquo-e effect of fluoride on the distribution ofsome minerals in the surface water of an Egyptian lagoon at
the Mediterranean Seardquo Egyptian Journal of Aquatic Researchvol 41 no 1 pp 31ndash39 2015
[33] Y Zhu Z Zhu X Zhao Y Liang and Y Huang ldquoChar-acterization dissolution and solubility of lead hydroxypyr-omorphite [Pb5(PO4)3OH] at 25ndash45degCrdquo Journal ofChemistry vol 2015 Article ID 269387 10 pages 2015
[34] M A Z Chahouki ldquoMultivariate analysis techniques inenvironmental sciencerdquo in Earth and Environmental SciencesDr Imran Ahmad Dar Ed InTech Open London UK 2011httpwwwintechopencombooksearth-and-environmental-sciencesmultivariate-analysis-techniques-inenvironmental-science
[35] J V Klump and C S Martens ldquoBiogeochemical cycling in anorganic-rich coastal marine basin 5 Sedimentary nitrogenand phosphorus budgets based upon kinetic models massbalances and the stoichiometry of nutrient regenerationrdquoGeochimica et Cosmochimica Acta vol 51 no 5 pp 1161ndash1173 1987
[36] R L Folk Petrology of Sedimentary Rocks University of TexasAustin TX USA 1974
[37] P Saenger ldquoA rapid spectrophotometric method for thedetermination of bromine in seawater and in the ash ofmarine algaerdquo Helgolander Wissenschaftliche Meer-esuntersuchungen vol 23 no 1 pp 32ndash37 1972
[38] P G Jeffery Chemical Methods of Rock Analysis PergamonPress New York NY USA 2nd edition 1975
[39] J D H Strickland and T R Parsons ldquoA practical handbook ofseawater analysisrdquo in Fisheries Research Board of CanadaBulletin 167p 311 Second edition Wiley Ottawa Canada1972
[40] B Horvath O Opara-Nadi and F Beese ldquoA simple methodfor measuring the carbonate content of soilsrdquo Soil ScienceSociety of America Journal vol 69 no 4 pp 1066ndash1068 2005
[41] K Grasshoff Methods of Seawater Analysis p 317 VerlagChemie Weinkeim Germany 1976
[42] R Danovaro D Marrale N Della Croce P Parodi andM Fabiano ldquoBiochemical composition of sedimentary or-ganic matter and bacterial distribution in the Aegean Seatrophic state and pelagic-benthic couplingrdquo Journal of SeaResearch vol 42 no 2 pp 117ndash129 1999
[43] APHA-AWWA-WPCF (American Public Health Associa-tion) Standard Methods for the Examination of Water andWaste Water American Public Health Association Wash-ington DC USA 20th edition 1999
[44] K I Aspila H Agemian and A S Y Chau ldquoA semi-auto-mated method for the determination of inorganic organicand total phosphate in sedimentsrdquo e Analyst vol 101no 1200 pp 187ndash197 1976
[45] J P Riley and D Taylor ldquoChelating resins for the concen-tration of trace elements from sea water and their analyticaluse in conjunction with atomic absorption spectrophotom-etryrdquo Analytica Chimica Acta vol 40 pp 479ndash485 1968
[46] G F El-Said and A El-Sikaily ldquoChemical composition ofsome seaweed from Mediterranean Sea coast Egyptrdquo Envi-ronmental Monitoring and Assessment vol 185 no 7pp 6089ndash6099 2013
[47] Directorate General of Health Services Ministry of Health andFamilyWelfare Government of India ldquoManual of methods ofanalysis of foodsrdquo in Fruit and Vegetable Productsp 57Directorate General of Health Services Ministry of Health andFamily Welfare Government of India New Delhi India2005
[48] A Gunnars S Blomqvist and C Martinsson ldquoInorganicformation of apatite in brackish seawater from the Baltic Sea
18 Journal of Chemistry
an experimental approachrdquo Marine Chemistry vol 91 no 1-4 pp 15ndash26 2004
[49] W M Haynes D R Lide and T J Bruno CRC Handbook ofChemistry and Physics A Ready Reference Book of Chemicaland Physical Data CRC Press Taylor amp Frances Group BocaRaton FL USA 97th edition 2017
[50] M S Masoud M I El-Samra and M M El-Sadawy ldquoWaterchemistry of el-mex bay west of Alexandria Egyptrdquo eEgypian Science Magazine vol 2 pp 70ndash78 2005
[51] F J Millero R Feistel D G Wright and T J McDougallldquo-e composition of standard seawater and the definition ofthe reference-composition salinity scalerdquo Deep Sea ResearchPart I Oceanographic Research Papers vol 55 no 1pp 50ndash72 2008
[52] S K El-Wakeel S A Morcos and A M Mahlis ldquo-e majorcations in Lake Maryut watersrdquo Hydrobiologia vol 36 no 2pp 253ndash274 1970
[53] A M Mahlis S A Morcos and S K El-Wakeel ldquo-e majoranions in Lake Maryut watersrdquo Hydrobiologia vol 36 no 2pp 275ndash294 1970
[54] A S Saad M A Massoud R A Amer and M A GhorabldquoAssessment of the physico-chemical characteristics andwater quality analysis of Mariout Lake southern of Alexan-dria Egyptrdquo Journal of Environmental and Analytical Toxi-cology vol 7 no 1 p 421 2017
[55] R Rumuri ldquoDataset on hydrogeochemical characteristics ofgroundwater and surface water in Kattumannarkoil TalukIndiardquo Data in Brief vol 32 Article ID 106058 2020
[56] P Szefer S W Fowler K Ikuta et al ldquoA comparative as-sessment of heavy metal accumulation in soft parts and byssusof mussels from subarctic temperate subtropical and tropicalmarine environmentsrdquo Environmental Pollution vol 139no 1 pp 70ndash78 2006
[57] N F Soliman G M El Zokm and M A Okbah ldquoRisk as-sessment and chemical fractionation of selected elements insurface sediments from Lake Qarun Egypt using modifiedBCR techniquerdquo Chemosphere vol 191 pp 262ndash271 2018
[58] G M El Zokm M I A Ibrahim L A Mohamed and M El-Mamoney ldquoCritical geochemical insight into Alexandria coastwith special reference to diagnostic ratios (TOCTN amp SrCa)and heavy metals ecotoxicological hazardsrdquo Egyptian Journalof Aquatic Research vol 46 no 1 pp 27ndash33 2020
[59] A S Likuku K B Mmolawa and G K GaboutloeloeldquoAssessment of heavy metal enrichment and degree of con-tamination around the copper-nickel mine in the SelebiPhikwe Region Eastern Botswanardquo Environment and EcologyResearch vol 1 no 2 pp 32ndash40 2013
[60] M K Khalil S E O Draz G M El Zokm and G F El-SaidldquoApportionment of geochemistry texturersquos properties and riskassessment of some elements in surface sediments from Bar-dawil Lagoon Egyptrdquo Human and Ecological Risk AssessmentAn International Journal vol 22 no 3 pp 775ndash791 2016
[61] M M El-Sadaawy and G F El-Said ldquoAssessment of fluoridein three selected polluted environments along the EgyptianMediterranean Sea effects on local populationsrdquo Human andEcological Risk Assessment An International Journal vol 20no 6 pp 1643ndash1658 2014
[62] USEPA ldquoSuperfund exposure assessment manualrdquo inOSWER Directive 92855-1EPA540l-88001Office of Emer-gency and Remedial Response Washington DC USA 1988
[63] USEPA ldquoExposure factors handbookrdquo in EPA6008-89043Office of Health and Environmental Assessment Wash-ington DC USA 1989
[64] Health Canada ldquoFederal Contaminated Site Risk Assessmentin Canadardquo Part II Health Canada Toxicological ReferenceValues (TRVs) Cat H46-204-368E Calgary Health CanadaOttawa Canada 2007
[65] J Iqbal S A Tirmizi and M H Shah ldquoStatistical appor-tionment and risk assessment of selected metals in sedimentsfrom Rawal Lake (Pakistan)rdquo Environmental Monitoring andAssessment vol 185 no 1 pp 729ndash743 2013
[66] USEPA (US Environmental Protection Agency) Region 6USAEPA ldquoMultimedia Planning and Permitting DivisionrdquoOffice of Solid Waste Center for Combustion Science andEngineering Washington DC USA 2005
[67] P Jeschke ldquoLatest generation of halogen-containing pesti-cidesrdquo Pest Management Science vol 73 no 6 pp 1053ndash10662017
[68] M A Shreadah O A El-Rayis N A Shaaban andA M Hamdan ldquoWater quality assessment and phosphorusbudget of a lake (Mariut Egypt) after diversion of wastewaterseffluentsrdquo Environmental Science and Pollution Researchvol 27 no 21 pp 26786ndash26799 2020
[69] J P Riley and M Tongudai ldquo-e major cationchlorinityratios in sea waterrdquo Chemical Geology vol 2 pp 263ndash2691967
[70] R B McCleskey D K Nordstrom D D Susong J W Balland J M Holloway ldquoSource and fate of inorganic solutes inthe gibbon river yellowstone national park Wyoming USArdquoJournal of Volcanology and Geothermal Research vol 193no 3-4 pp 189ndash202 2010
[71] G T F Wong and K-Y Li ldquoWinklerrsquos method overestimatesdissolved oxygen in seawater iodate interference and itsoceanographic implicationsrdquo Marine Chemistry vol 115no 1-2 pp 86ndash91 2009
[72] B S R V Prasad P D N Srinivasu P S VarmaA V Raman and S Ray ldquoDynamics of dissolved oxygen inrelation to saturation and health of an aquatic body a case forChilka Lagoon Indiardquo Journal of Ecosystems vol 2014 Ar-ticle ID 526245 17 pages 2014
[73] China Environmental Protection Agency EnvironmentalQuality Standards for Surface Water (GB3838ndash2002) NationalEnvironmental Protection Agency of China Beijing China2002
[74] Y Jia L Wang Z Qu and Z Yang ldquoDistribution con-tamination and accumulation of heavy metals in watersediments and freshwater shellfish from Liuyang RiverSouthern Chinardquo Environmental Science and Pollution Re-search vol 25 no 7 pp 7012ndash7020 2018
[75] A Moneer M El-Sadawy G El-Said and A Radwan ldquoBoronhuman health risk assessment relative to the environmentalpollution of Lake Edku Egyptrdquo Journal of King AbdulazizUniversity vol 23 no 2 pp 41ndash55 2012
[76] C B Tabelin T Igarashi T Arima D Sato T Tatsuhara andS Tamoto ldquoCharacterization and evaluation of arsenic andboron adsorption onto natural geologic materials and theirapplication in the disposal of excavated altered rockrdquo Geo-derma vol 213 pp 163ndash172 2014
[77] G Aloisi K Wallmann M Drews and G BohrmannldquoEvidence for the submarine weathering of silicate minerals inBlack Sea sediments possible implications for the marine Liand B cyclesrdquo Geochemistry Geophysics Geosystems vol 5no 4 pp 1ndash22 2004
[78] C Degueldre and V Cloet ldquoPore water colloid properties inargillaceous sedimentary rocksrdquo Science of e Total Envi-ronment vol 569-570 pp 423ndash433 2016
Journal of Chemistry 19
[79] J A Higgins and D P Schrag ldquoRecords of Neogene seawaterchemistry and diagenesis in deep-sea carbonate sedimentsand pore fluidsrdquo Earth and Planetary Science Letters vol 357-358 pp 386ndash396 2012
[80] H Schroeder A-L Fabricius D Ecker T A Ternes andL Duester ldquoMetal(loid) speciation and size fractionation insediment pore water depth profiles examined with a newmesoprofiling systemrdquo Chemosphere vol 179 pp 185ndash193 2017
[81] Y Song and G Muller ldquoFreshwater sediments sinks andsources of brominerdquo Naturwissenschaften vol 80 no 12pp 558ndash560 1993
[82] M E Goher H I Farhat M H Abdo and S G Salem ldquoMetalpollution assessment in the surface sediment of Lake NasserEgyptrdquo Egyptian Journal of Aquatic Research vol 40 no 3pp 213ndash224 2014
[83] G F El-Said M M El-Sadawy and A A Moneer ldquoIncor-poration of fluoride and boron into surface sediments alongthe Egyptian Mediterranean coastrdquo Egyptian Journal ofAquatic Research vol 36 no 4 pp 569ndash583 2010
[84] B Gilfedder G M Petri M Wessels and H Biester ldquoAniodine mass-balance for Lake Constance Germany insightsinto iodine speciation changes and fluxesrdquo Geochimica etCosmochimica Acta vol 74 no 11 pp 3090ndash3111 2010
[85] E Korobova L Kolmykova B Ryzhenko et al ldquoDistributionand speciation of iodine in drinking waters from geochem-ically different areas of Bryansk region contaminated after theChernobyl accident in relation to health and remediationaspectsrdquo Journal of Geochemical Exploration vol 184pp 311ndash317 2018
[86] V Zic V W Truesdale and N Cukrov ldquo-e distribution ofiodide and iodate in anchialine cave watersmdashevidence forsustained localised oxidation of iodide to iodate in marinewaterrdquoMarine Chemistry vol 112 no 3-4 pp 168ndash178 2008
[87] M B Heeb J Criquet S G Zimmermann-Steffens andU Von Gunten ldquoOxidative treatment of bromide-containingwaters formation of bromine and its reactions with inorganicand organic compoundsmdasha critical reviewrdquo Water Researchvol 48 pp 15ndash42 2014
[88] V Sivasankar A K Darchen and R Omine SakthivelldquoChapter 2 ldquofluoride a world ubiquitous compound itschemistry and ways of contaminationrdquo in Surface ModifiedCarbons as Scavengers for Fluoride fromWater V SivasankarEd pp 5ndash32 copy Springer International Publishing Switzer-land Cham Switzerland 2016
[89] O Cabestrero P Del Buey and M E Sanz-Montero ldquoBio-sedimentary and geochemical constraints on the precipitationof mineral crusts in shallow sulphate lakesrdquo SedimentaryGeology vol 366 pp 32ndash46 2018
[90] M A Hassaan O A El-Rayis and E I Hemada ldquoEstimationof the redox potential of lake mariut drainage system (Qalaaand Umum drains)rdquoHydrology vol 5 no 6 pp 82ndash85 2017
20 Journal of Chemistry
indicates the possible transfer of Na between pore water andsediment partitions
34 Interactions of Precipitated Halogenated Compounds inSurface and Pore Waters -e Saturation Index (SI) [23 60]of twenty-three and fifteen structures in surface water andpore water samples respectively are listed (Table 1) -ecorrelation matrix of the calculated Saturation Indices withthe presented data shows the different factors affecting theinteraction of the halogenated compound with other pre-cipitated salts and minerals Table 1 explores the precipitationof the phosphate minerals and salts are most abundantfollowed by the hydroxidesrsquo salts iodate salts sulfate andcarbonate minerals and salts in surface waters Amongst thehalogens precipitated salts fluoride minerals especiallyfluorapatites and carbonate-fluorapatite (FAP and CFAP)have high SI values in surface water (4277ndash5195 and1604ndash6089 respectively) and in pore water (5126ndash5460 and1752ndash7833 respectively) Bromide and chloride are mainlyfound in the soluble forms in surface and pore waters Iodidesalts (Ca(IO3)2 and Ca(IO3)26H2O) moderately precipitatein surface and pore Iron salts precipitate in surface waterwhile in pore water they are not formed -us SI contentreflects that halogens especially fluoride and iodide play avital role in reducing lake pollution
In addition Table 1 shows that the precipitation com-pounds that may be formed in surface water are relativelydifferent from those in sediment pore water For examplefluorite (CaF2) and sellaıte (MgF2) may be only formed inpore water while calcite and aragonite may be deposited insurface water However the formation of fluorite in surfacewater is related to Naw (r 0778 ple 0003) Kw (r 0704ple 0011) CO3w (r minus0718 ple 0009) Fw (r 0770ple 0003) and Ip (r minus0785 ple 0003) (SupplementaryTable 1)
-e formation of calcium sulfate hemihydrate calciumsulfate and anhydrite in water is related to the increase in theamounts of Caw Mgw SO4w Nap Fp Sip Cls and Mns andthe decrease in porosity values On the other hand pre-cipitation of calcium phosphate is related to Brw (r 0751ple 0005) Znw (r 0668 ple 0018) Pw (r 0881ple 0001) and Ks (r 0881 ple 0001) ie it is affected bythe discharged water composition (Supplementary Table 1)
-e formation of calcite and aragonite in surface water isrelated to the formation of CO3w (r 0753 ple 0005) anddissociation of HCO3w (r minus0660 ple 0020) pHw values(r minus0654 ple 0021) and their dissolution in sediment(r minus0620 ple 0032) (Supplementary Table 1)
-e dolomite formation in water may be affected by theincrease of CO3w (r 0817 ple 0001) and the decrease ofHCO3w (r minus0658 ple 0020) increase in TDSw (r 0599ple 0040) and increase in pHw (r minus0656 ple 0021)besides the possible release of CO3s from abundant sediment(r minus0624 ple 0030) and the precipitation of calcite(r 0984 ple 0000) and aragonite (r 0984 ple 0000) intosediment fraction (Supplementary Table 1)
Generally in the current study the possible formedhalogenated minerals and salts are affected by their
abundance in different components of the lake besides theirpossible dissolution or formation on the sediment texturesgeochemistry of the sediments and physicochemical vari-ables of water in addition to the components of the dis-charged waters
35 Interactions of Dissolved Halogenated Compounds inSurface and PoreWaters -e utilization of dissolved salts insurface and pore waters by utilizing Palmerrsquos method andpiper ternary diagram [50] indicates that Na is the richestcation in surface water followed by Mg Ca and K At thesame time Mg is the most predominate one in the porewater (Figures 3 and 4) Obviously Cl is the most importantanion in surface water and pore waters samples Howeverthe piper ternary diagrams of surface water and pore waterclearly shows that NaCl is the most dominant in surfacewater while MgCl2 is the most abundant in pore waterCoincidently Palmerrsquos method also reflects that NaCl(574) is the most existent species in surface water fol-lowed by MgCl2 (304) CaCl2 (71) CaSO4 (29)Ca(HCO3)2 (14) and KCl (12) (Figure 3) At the sametime MgCl2 (760) is the most present species in porewater followed by NaCl (73)asympMg(HCO3)2 (73)Ca(HCO3)2 (52) and MgSO4 (31) (Figure 4)
36 Multivariate Analysis
361 Principal Component (PCA) By applying Varimaxrotation and Kaiser normalization to 98 variables in the PCAfor halogens and tested variables and calculated parametervalues 7 extracted PCs with eigenvalues higher than 1 areobtained However it is important that the eigenvalue mustbe greater than 1 Its seven PCs explain 8558 of the totalvariance
-e first principle component (PC1) is 1473 of thetotal variance and shows positive coefficient factor loadingsfor CO3w TDSw Kp calcite aragonite dolomite FeCO3MgCO3 ZnCO3 and ZnCO3H2O (0804 0547 05320938 0938 0947 0741 0940 0866 and 0866 respec-tively) In addition it provides negative factor loadings forHCO3w pHw Bw Nap and CO3s (minus0782 minus0610 minus0595minus0532 and minus0572 respectively) PC1 is related to thefactors affecting the carbonate compounds that may beformed in the area under consideration
PC2 accounts to 1458 of the total variance and alsoshows positive and negative coefficient factor loadingsrepresenting the different interactions between the CawMgw Liw SO4wMgp Nap pHp Cls SO4s Brs and porosityin water pore water and sediment that are responsible forthe composition of sulfate magnesium and phosphateprecipitates besides the effect of the discharged waters onwater-pore water-sediment componentsrsquo cycles
PC3 typically shows 1377 of the total variance withpositive and negative loadings which can properly explorethe effect of the principal sources of local pollution on thedissolving of heavy metals B and P from sediment into thewater column and the probable formation of Fe(OH)2Fe(OH)3) and FePO4
Journal of Chemistry 13
Similarly the coefficient factor loadings of PC4 with1355 are related to the influence of the polluted dischargewater and sediment texture on the formation of F Cl and Isalt besides the precipitation of halogenated compounds(FeF2 Mn(IO3)2 KIO4 and KCIO4) besides their minerals(CaF2 MgF2 FAP and CFAP)
Simultaneously PC5 gives 1092 of the total variancewith positive and negative loadings which explains therelations between the physicochemical limits of the surfacewater pore water and sediment components and theprecipitation of minerals and salts (OCP HAP CuBrZn(OH)2 and Zn(IO3)22H2O) -is is also associated tothe influence of the sedimentary material on the release ofMn Fe and P from sediment into pore water and watercolumn and formation of Ca3(PO4)2 OCP and HAPminerals
However PC6 associates with 100 of the total variancegiving positive and negative coefficient factor loadingswhich explain that the sediments (minerals andor organic-iodine compounds) are only the acting sink for iodine andiodine species (Iminus and IOminus
3 ) in the water as previously re-ported [84] PC6 also reflects the precipitation of severalhalogenated compounds such as calcium iodate (Ca(IO3)2and Ca(IO3)26H2O) and copper iodate (CuI andCuIO3H2O) besides Cu3(PO4)2 species in the lake watercolumn
-e loadings of PC7 contribute by 804 and show thatthe release of calcium in pore water into the water column isresponsible for the precipitation of halogenated compounds(CuCl and Zn(IO3)22H2O) as well as copper and Zn salts(Cu3(PO4)2 and Zn(OH)2)
362 Cluster Analysis On the other hand cluster analysisshows that the similarity of sites 1amp4 5amp8 6amp9 2amp10 and11amp13 is due to the texture of sediment
363 Multiple Regression Multiple regression equations ofhalogens as dependent variables and the other determinedand calculated parameters as independent variables insurface water pore water and sediment partitions are listed(Table 5)-e amount of fluoride in water samples is affectedby the discharged watersrsquo fundamental components espe-cially Zn and Cu besides its surface water-pore water in-teractions Its content in pore water seems to be stronglyaffected by its substitution competition with other halogensin surface water-spore water-sediment cycle due to its highelectronegativity Generally in the affected area the type ofpollutant in the discharged water plays an important role inthe dissolution andor precipitation of fluoride and otherhalogens in the surface water-pore water-sediment cycle
574
147129
300
12
Ca(HCO3)2CaSO4CaCl2
MgCl2KClNaCl
(a)
SO4
2 + CIndash Ca 2+ + Mg 2+
CO32ndash + HCO3
ndashNa+ + K+
Mg2+ SO42ndash
Ca2+ CIndash
(b)
Figure 3 (a) distribution and (b) piper ternary diagram of the formed dissolved salts in surface water of Lake Mariout
Ca(HCO3)2Mg(HCO3)2MgSO4
NaClMgCI2KCl
760 1052
7373 31
(a)
SO4
2ndash + C
Indash
Ca 2+ + Mg 2+
CO32ndash + HCO3
ndashNa+ + K+
Mg2+ SO42ndash
CIndashCa2+
(b)
Figure 4 (a) distribution and (b) piper ternary diagram of the formed dissolved salts in pore water of Lake Mariout
14 Journal of Chemistry
Table 5 -e multiple regression analyses of each halogen as dependent variable and other tested variables in the surface water pore waterand sediment partitions besides the precipitated salts in surface water along Lake Mariout
Dependentvariable Multiple regression equation R2
FluorideLake water FW 3162 + 092 Zn F2 minus 033 SiP + 021 CuIminus 017 SpermilP 09911
Pore water Fp minus2567minus117 SiW minus 033 LiP minus 062 CuClminus 028 IS + 023 TDSW+ 017 KIO4 minus 012 BrW minus 004porosity + 004 PW
10000
Sediment FS 088 CAPminus 049 MgS minus 046 DOW+039MgW+ 027 Mn(IO3)2 + 015 Cu3(PO4)2 + 004 HAP+ 002 pHP 10000ChlorideLake water No relation 00000Pore water No relation 00000Sediment ClS minus116 + 046 MgP + 077 Kp minus 049 dolomite + 017 TDSW minus 011 CuI + 005 NaS + 002 BS + 001 FeF2 10000Bromide
Lake water BrW 1563 + 110 CuBrminus 057 CuClminus 021 KS minus 014 pHP minus 011 TPS + 014 FeW+ 007 ZnSminus 002 PP + 001turbidity 10000
Pore water BrP minus1516minus 055 FeS minus 073 BS + 061 MnW+ 083 SiP + 049 NaS minus 031MnS minus 015 CuBr + 011 pHW minus 001CaW
10000
Sediment BrS 015 SiP + 195 CFAP+ 002 FP minus 045 IS + 192 sand+ 037 MnW minus 029 MgS minus 012 LiP + 005Ca3(PO4)2 minus 002 ZnF2
10000
IodideLake water IW 099 Ca(IO3)6H2O 09999
Pore water IP minus097 ZnF2 minus 057 Li3PO4 minus 053 BP + 034 FAP+ 015 Ca(IO3)2 +MnW+ 005 KS minus 009 turbidity + 055CaS
09999
Sediment IS minus072 + 135 SO4P + 023 Mn(IO3)2 + 063 FeW+ 031 TPS minus 035 MgP minus 012 Zn(CO3)22H2O 09993
40E + 0135E + 0130E + 0125E + 0120E + 0115E + 0110E + 0150E + 0000E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
12345
678910
111213
(a)
10E + 0090E ndash 0180E ndash 0170E ndash 0160E ndash 0150E ndash 0140E ndash 0130E ndash 0120E ndash 0110E ndash 0100E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
12345
678910
111213
(b)
12345
678910
111213
40E ndash 0235E ndash 0230E ndash 0225E ndash 0220E ndash 0215E ndash 0210E ndash 0250E ndash 0300E ndash 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
(c)
12345
678910
111213
80E ndash 0670E ndash 0660E ndash 0650E ndash 0640E ndash 0630E ndash 0620E ndash 0610E ndash 0600E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
(d)
Figure 5 Hazard quotient of ingestion and dermal contact of surface water and sediment of LakeMariout (a) ingestion of water (b) dermalcontact of water (c) ingestion of sediment and (d) dermal contact of sediment
Journal of Chemistry 15
Minerals and precipitated salts in the different partitions(surface water pore water and sediment) play an importantrole in the deposition and release of halogens in sedimentsAdditionally the texture and the porosity of the sedimentsplay a key role in the distribution of halogens in the threepartitions Interestingly chloride is the only halogen that hasnegligible interactions along the surface water and porewater partitions because it is present in large quantities inthe form of soluble salts (NaCl and MgCl2)
37 Pollution Status
371 Enrichment Factor (EF) Twowell-knownmethods areused to assess environmental pollution public health sig-nificance of ingestion and dermal contact with water andsediment components and sediment enrichment factor (EF)[59 60]
-e average EF values of the determined elements CaMg Na K Li B P Cu Zn Mn Fe F Cl Br and I are alllower than the value that is less than the minimum en-richment value (EFlt 2)-us the area under investigation isstill ecologically considered as an unpolluted region
372 Human Health Risk Assessment -e EDI HQ and HIshow the variable values of all pollutants in the surface waterand sediments along the lake region and in drains (sites11ndash13) under study Among all the calculated variables ofsurface water ingestion (EDIIngw) and dermal contact(EDIDermw) Cl is still the only variable that shows high levels(average 1551 and 43mg kgminus1 dayminus1 respectively) -eestimation daily intake of sediment ingestion (EDIIngs) anddermal contact (EDIDerms) of Mg Ca and Na give maximumaverage amounts of 841Eminus 02 513E ndash 02 and167Eminus 03mg kgminus1 dayminus1 respectively
Among the HQ of the calculated detection variables thecontent of HQB of ingestion and dermal contact with waterand sediment is the highest However 70 of sites have HQBvalues more than 10 (Figure 5) Comparing the HQ values ofall the determined variables HQB of the ingestion of surfacewater shows values higher (gt10) However due to the impactof drainage the HQB values of stations 1ndash4 8ndash10 12 and 13
are higher than 10 -erefore these sites can be consideredas the area with the most serious boron pollution caused byuntreated discharged water disposal In addition the HIIngwlevel of water ingestion for the studied variables in all sites ismuch higher than 10 (Figure 6) Except for boron it isusually concluded that the study area does not pose any riskto the population due to halogens or other variables Ac-cordingly this information may help the official authoritiesoptimize management plans and strengthen their pollutioncontrol actions in Lake Mariout
4 Conclusions
-e effects of halogen salts and minerals on the pollution ofLake Mariout were studied Halogens and some physico-chemical variables in three partitions surface water porewater and sediment in Lake Mariout were evaluated -ehalogen content was variable between different sites andchloride was the main halogen in surface water and porewater but it was very rare in the lakersquos sediment partitionPiper ternary diagram and Palmerrsquos method reflected thatNaCl was the dominant salt in surface water while MgCl2was the main dissolve salt in pore water-e chlorinity ratiosof halogens and tested variables were directly matched to thefeeding drain sources
Moreover the Saturation Index (SI) reveals that 23 and 15precipitated salts and minerals are formed in surface water andpore water respectively -e SI value indicated the formationof phosphate minerals in surface water and pore water es-pecially octacalcium phosphate (OCP Ca4H(PO4)325H2O)and hydroxyapatite (HAP Ca5(PO4)3OH) In addition tofluoride minerals especially fluorapatite (FAP) and carbonate-fluorapatite (CFAP) were obviously precipitated from surfacewater and pore water Soluble salts of bromide and chloridewere formed in surface water and pore water Iodide salts(Ca(IO3)2 and Ca(IO3)26H2O) were moderately precipitatedin the surface water and pore water
Moreover the multivariate analysis including the cor-relation matrix multiple stepwise linear regression treeclustering and principle component (PCA) of all the de-termined and calculated variables was applied to estimatethe proposed interaction between halogens and other tested
10E + 02
16E + 0214E + 0212E + 02
80E + 0160E + 0140E + 0120E + 0100E + 00
1 2 3 4 5 6 7 8 9 10 11 12 13
HIIngHIDerm
(a)
1 2 3 4 5 6 7 8 9 10 11 12 13
HIIngHIDerm
40E ndash 0235E ndash 0230E ndash 0225E ndash 0220E ndash 0215E ndash 0210E ndash 0250E ndash 0300E + 01
(b)
Figure 6 Hazard index of ingestion and dermal contact of the studied variables in surface water and sediment of Lake Mariout (a) waterand (b) sediment
16 Journal of Chemistry
variables in the polluted area under study -e multivariateanalysis showed that there were many interactions betweenhalogens and tested variables High levels of fluoride bro-mide and chloride in surface water were related to thecomposition of drainage waters -e enrichment factor (EF)showed that Lake Mariout was not polluted However thehuman health adverse effects calculated for surface waterand sediment did not reflect any possible likelihood hazardeffects from halogens
Interestingly the current study concluded that halogencompounds especially fluorides are most likely to be de-posited from surface lakes in the form of many minerals andprecipitation thereby reducing the adverse pollution effectson human health -e results obtained through this workhelp to find the correlations between the sampling sites andthe variables obtained by physical and chemical measure-ments which can be used to construct a fast decision modelfor separating different water quality samples -is infor-mation may help the official authorities optimize manage-ment plans and strengthen their pollution control measuresin Lake Mariout
Data Availability
-e data used to support the findings of this research areincluded within the paper
Conflicts of Interest
-e authors declare that there are no conflicts of interestregarding the publication of this manuscript
Supplementary Materials
Supplementary Table 1 correlation matrix of variable insurface water pore water and sediment partitions besidesthe precipitated salts in surface water along Lake Mariout(Supplementary Materials)
References
[1] M S Masoud T O Said G El-Zokm and M A ShreadahldquoAssesment of heavy metals contamination in surface sedi-ments of the Egyptian Red Sea Coastsrdquo Australian Journal ofBasic and Applied Sciences vol 6 pp 44ndash58 2012
[2] M A Shreadah M I Abdel Moneim T O SaidE M I Fathallah and M E Mahmoud ldquoPAHs in seawater ofthe semi-closed areas along the Alexandria coast of EgyptianMediterranean seardquo Journal of Environmental Protectionvol 4 no 11 p 11 Article ID 40298 2013
[3] S Abdel Ghani G El Zokm A Shobier T Othman andM Shreadah ldquoMetal pollution in surface sediments of Abu-Qir bay and Eastern harbour of Alexandria Egyptrdquo EgyptianJournal of Aquatic Research vol 39 no 1 pp 1ndash12 2013
[4] G F El-Said ldquoBioaccumulation of key metals and othercontaminants by seaweeds from the Egyptian MediterraneanSea Coast in relation to human health riskrdquo Human andEcological Risk Assessment An International Journal vol 19no 5 pp 1285ndash1305 2013
[5] M A Shreadah A H Shobier S Abdel Ghani G M El-Zokm and T O Said ldquoMajor ions anomalies and
contamination status by trace metals in sediments from twohot spots along the Mediterranean Coast of Egyptrdquo Envi-ronmental Monitoring and Assessment vol 187 no 280pp 1ndash18 2015
[6] A El Nemr G F El-Said A Khaled and S Ragab ldquoDis-tribution and ecological risk assessment of some heavy metalsin coastal surface sediments along the Red Sea Egyptrdquo In-ternational Journal of Sediment Research vol 31 no 2pp 164ndash172 2016
[7] A El Nemr G F El-Said S Ragab A Khaled and A El-Sikaily ldquo-e distribution contamination and risk assessmentof heavy metals in sediment and shellfish from the Red Seacoast Egyptrdquo Chemosphere vol 165 pp 369ndash380 2016
[8] A El Nemr and G F El-Said ldquoAssessment and ecological riskof heavy metals in sediment and molluscs from the Medi-terranean coastrdquo Water Environment Research vol 89 no 3pp 195ndash210 2017
[9] M A Sheradah A A El-Sikaily N M Abd El MoneamN E Abd El Maguid and M G Zaki ldquoChemical and bio-chemical evaluation of marine pollution by polychlorinatedbiphenyls and pesticides in two regions along the EgyptianMediterranean Seardquo International Journal of EnvironmentalMonitoring and Analysis vol 6 no 3 pp 95ndash109 2018
[10] M A Shreadah A A-M M El-Sayed A A S TahaA-M M Ahmed and H H Abdel Rahman ldquoEvaluation ofdifferent anthropogenic effluents impacts on the water qualityusing principal component analysis a case study of Abu-QirBay-Alexandria-Egyptrdquo International Journal of Environ-mental Monitoring and Analysis vol 7 no 3 pp 56ndash67 2019
[11] G F El-Said M M El-Sadaawy A H Shobier andS E Ramadan ldquoHuman health implication of major and traceelements present in commercial crustaceans of a traditionalseafood marketing region Egyptrdquo Biological Trace ElementResearch vol 199 pp 315ndash328 2020
[12] M A Shreadah S A A Ghani H B I HawashA A E Samie and A E M M Ahmed ldquoOrganotin com-pounds in sediments of northern lakes Egyptrdquo Journal ofEnvironmental Protection vol 05 no 17 pp 1654ndash1666 2014
[13] A M Younis G M El-Zokm and M A Okbah ldquoSpatialvariation of acid-volatile sulfide and simultaneously extractedmetals in Egyptian Mediterranean Sea lagoon sedimentsrdquoEnvironmental Monitoring and Assessment vol 186 no 6pp 3567ndash3579 2014
[14] G F El-Said S E O Draz M M El-Sadaawy andA A Moneer ldquoSedimentology geochemistry pollution statusand ecological risk assessment of some heavy metals insurficial sediments of an Egyptian lagoon connecting to theMediterranean Seardquo Journal of Environmental Science andHealth Part A vol 49 no 9 pp 1029ndash1044 2014
[15] G M El Zokm M A Okbah and A M Younis ldquoAssessmentof heavy metals pollution using AVS-SEM and fractionationtechniques in Edku Lagoon sediments Mediterranean SeaEgyptrdquo Journal of Environmental Science and Health PartAvol 50 no 6 pp 571ndash584 2015
[16] G M El Zokm H R Z Tadros M A Okbah andG H Ibrahim ldquoldquoEutrophication assessment using TRIX andCarlsonrsquos indices in Lake Mariout water Egyptrdquo EgyptianJournal of Aquatic Biology and Fisheries vol 22 no 5pp 331ndash349 2018
[17] N Donia ldquoLake Maryut monitoring using remote sensingrdquo inProceedings of the gypt Eighteenth International WaterTechnology Conference IWTC18 Sharm El Sheikh Abu DhabiUAE March 2015
Journal of Chemistry 17
[18] M A Khairy ldquoAssessment of priority phenolic compounds insediments from an extremely polluted coastal wetland (LakeMaryut Egypt)rdquo Environmental Monitoring and Assessmentvol 185 no 1 pp 441ndash455 2013
[19] N A El-Naggar and E A Rifaat ldquoEgyptian coastal lakes andwetlands part Imdashcharacteristics and hydrodynamicsrdquo in eHandbook of Environmental Chemistry A M Negm EdSpringer International Publishing AG Berlin Germany 2017
[20] J J Hanley and K T Koga ldquoChapter 2 ldquohalogens in terrestrialand cosmic geochemical systems abundances Geochemicalbehaviors and analytical methodsrdquordquo in e Role of Halogensin Terrestrial and Extraterrestrial Geochemical ProcessesD E Harlov and L Aranovich Eds Springer InternationalPublishing AG Berlin Germany pp 21ndash121 2018
[21] A Ghosh K Mukherjee S K Ghosh and B Saha ldquoSourcesand toxicity of fluoride in the environmentrdquo Research onChemical Intermediates vol 39 no 7 pp 2881ndash2915 2013
[22] M M Naim A A Moneer and G F El-Said ldquoPredictiveequations for the defluoridation by electrocoagulation tech-nique using bipolar aluminum electrodes in the absence andpresence of additives a multivariate studyrdquo Desalination andWater Treatment vol 57 no 14 pp 6320ndash6332 2016
[23] G F El-Said N A Shaltout M M El-Sadaawy andA M H Morsy ldquo-e precipitation of fluoride calcium andmagnesium minerals from Egyptian Mediterranean Sea coastin relation to discharged watersrdquo Desalination and WaterTreatment vol 57 no 5 pp 2113ndash2124 2016
[24] H Bureau ldquoIodine encyclopedia of geochemistry A com-prehensive reference source on the chemistry of the earthrdquo inEncyclopedia of Earth Sciences Series W M White Ed copySpringer International Publishing AG 2016
[25] F C Kupper and C J Carrano ldquoKey aspects of the iodinemetabolism in brown algae a brief critical reviewrdquo Metal-lomics vol 11 pp 756ndash764 2019
[26] R Liteplo R Gomes P Howe and H Malcolm Fluorides-Environmental Health Criteria 227 p 290 World HealthOrganization (WHO) Geneva Switzerland 2002
[27] G F El-Said and M M El-Sadaawy ldquoSeasonal variation ofboron and fluoride in Tilapia nilotica from an Egyptian fishfarm in relation to Human health hazard assessmentrdquoHumanand Ecological Risk Assessment An International Journalvol 19 no 4 pp 930ndash943 2013
[28] WHO (World Health Organization) Bromide in Drinking-Water Background Document for Development of WHOGuidelines for Drinking-Water Quality WHO Press WorldHealth Organization Geneva Switzerland 2009
[29] G F El-Said and N A Sallam ldquo-e uptake of fluorideconcentration and its effects on the growth rate of shrimps(Palaemon elegans Rathke)rdquo Chemistry and Ecology vol 24no 3 pp 191ndash205 2008
[30] X Zhang J He B He and J Sun ldquoAssessment formationmechanism and different source contributions of dissolvedsalt pollution in the shallow groundwater of Hutuo Riveralluvial-pluvial fan in the North China Plainrdquo EnvironmentalScience and Pollution Research vol 26 no 35 pp 35742ndash35756 2019
[31] Y Zhu B Huang Z Zhu et al ldquoldquoCharacterization disso-lution and solubility of the hydroxypyromorphitendashhydroxyapatite solid solution [(PbxCa1minusx)5(PO4)3OH] at25 degC and pH 2ndash9rdquo Geochemical Transactions vol 17 no 2pp 1ndash18 2016
[32] G F El-Said M M El-Sadaawy A A Moneer andN A Shaltout ldquo-e effect of fluoride on the distribution ofsome minerals in the surface water of an Egyptian lagoon at
the Mediterranean Seardquo Egyptian Journal of Aquatic Researchvol 41 no 1 pp 31ndash39 2015
[33] Y Zhu Z Zhu X Zhao Y Liang and Y Huang ldquoChar-acterization dissolution and solubility of lead hydroxypyr-omorphite [Pb5(PO4)3OH] at 25ndash45degCrdquo Journal ofChemistry vol 2015 Article ID 269387 10 pages 2015
[34] M A Z Chahouki ldquoMultivariate analysis techniques inenvironmental sciencerdquo in Earth and Environmental SciencesDr Imran Ahmad Dar Ed InTech Open London UK 2011httpwwwintechopencombooksearth-and-environmental-sciencesmultivariate-analysis-techniques-inenvironmental-science
[35] J V Klump and C S Martens ldquoBiogeochemical cycling in anorganic-rich coastal marine basin 5 Sedimentary nitrogenand phosphorus budgets based upon kinetic models massbalances and the stoichiometry of nutrient regenerationrdquoGeochimica et Cosmochimica Acta vol 51 no 5 pp 1161ndash1173 1987
[36] R L Folk Petrology of Sedimentary Rocks University of TexasAustin TX USA 1974
[37] P Saenger ldquoA rapid spectrophotometric method for thedetermination of bromine in seawater and in the ash ofmarine algaerdquo Helgolander Wissenschaftliche Meer-esuntersuchungen vol 23 no 1 pp 32ndash37 1972
[38] P G Jeffery Chemical Methods of Rock Analysis PergamonPress New York NY USA 2nd edition 1975
[39] J D H Strickland and T R Parsons ldquoA practical handbook ofseawater analysisrdquo in Fisheries Research Board of CanadaBulletin 167p 311 Second edition Wiley Ottawa Canada1972
[40] B Horvath O Opara-Nadi and F Beese ldquoA simple methodfor measuring the carbonate content of soilsrdquo Soil ScienceSociety of America Journal vol 69 no 4 pp 1066ndash1068 2005
[41] K Grasshoff Methods of Seawater Analysis p 317 VerlagChemie Weinkeim Germany 1976
[42] R Danovaro D Marrale N Della Croce P Parodi andM Fabiano ldquoBiochemical composition of sedimentary or-ganic matter and bacterial distribution in the Aegean Seatrophic state and pelagic-benthic couplingrdquo Journal of SeaResearch vol 42 no 2 pp 117ndash129 1999
[43] APHA-AWWA-WPCF (American Public Health Associa-tion) Standard Methods for the Examination of Water andWaste Water American Public Health Association Wash-ington DC USA 20th edition 1999
[44] K I Aspila H Agemian and A S Y Chau ldquoA semi-auto-mated method for the determination of inorganic organicand total phosphate in sedimentsrdquo e Analyst vol 101no 1200 pp 187ndash197 1976
[45] J P Riley and D Taylor ldquoChelating resins for the concen-tration of trace elements from sea water and their analyticaluse in conjunction with atomic absorption spectrophotom-etryrdquo Analytica Chimica Acta vol 40 pp 479ndash485 1968
[46] G F El-Said and A El-Sikaily ldquoChemical composition ofsome seaweed from Mediterranean Sea coast Egyptrdquo Envi-ronmental Monitoring and Assessment vol 185 no 7pp 6089ndash6099 2013
[47] Directorate General of Health Services Ministry of Health andFamilyWelfare Government of India ldquoManual of methods ofanalysis of foodsrdquo in Fruit and Vegetable Productsp 57Directorate General of Health Services Ministry of Health andFamily Welfare Government of India New Delhi India2005
[48] A Gunnars S Blomqvist and C Martinsson ldquoInorganicformation of apatite in brackish seawater from the Baltic Sea
18 Journal of Chemistry
an experimental approachrdquo Marine Chemistry vol 91 no 1-4 pp 15ndash26 2004
[49] W M Haynes D R Lide and T J Bruno CRC Handbook ofChemistry and Physics A Ready Reference Book of Chemicaland Physical Data CRC Press Taylor amp Frances Group BocaRaton FL USA 97th edition 2017
[50] M S Masoud M I El-Samra and M M El-Sadawy ldquoWaterchemistry of el-mex bay west of Alexandria Egyptrdquo eEgypian Science Magazine vol 2 pp 70ndash78 2005
[51] F J Millero R Feistel D G Wright and T J McDougallldquo-e composition of standard seawater and the definition ofthe reference-composition salinity scalerdquo Deep Sea ResearchPart I Oceanographic Research Papers vol 55 no 1pp 50ndash72 2008
[52] S K El-Wakeel S A Morcos and A M Mahlis ldquo-e majorcations in Lake Maryut watersrdquo Hydrobiologia vol 36 no 2pp 253ndash274 1970
[53] A M Mahlis S A Morcos and S K El-Wakeel ldquo-e majoranions in Lake Maryut watersrdquo Hydrobiologia vol 36 no 2pp 275ndash294 1970
[54] A S Saad M A Massoud R A Amer and M A GhorabldquoAssessment of the physico-chemical characteristics andwater quality analysis of Mariout Lake southern of Alexan-dria Egyptrdquo Journal of Environmental and Analytical Toxi-cology vol 7 no 1 p 421 2017
[55] R Rumuri ldquoDataset on hydrogeochemical characteristics ofgroundwater and surface water in Kattumannarkoil TalukIndiardquo Data in Brief vol 32 Article ID 106058 2020
[56] P Szefer S W Fowler K Ikuta et al ldquoA comparative as-sessment of heavy metal accumulation in soft parts and byssusof mussels from subarctic temperate subtropical and tropicalmarine environmentsrdquo Environmental Pollution vol 139no 1 pp 70ndash78 2006
[57] N F Soliman G M El Zokm and M A Okbah ldquoRisk as-sessment and chemical fractionation of selected elements insurface sediments from Lake Qarun Egypt using modifiedBCR techniquerdquo Chemosphere vol 191 pp 262ndash271 2018
[58] G M El Zokm M I A Ibrahim L A Mohamed and M El-Mamoney ldquoCritical geochemical insight into Alexandria coastwith special reference to diagnostic ratios (TOCTN amp SrCa)and heavy metals ecotoxicological hazardsrdquo Egyptian Journalof Aquatic Research vol 46 no 1 pp 27ndash33 2020
[59] A S Likuku K B Mmolawa and G K GaboutloeloeldquoAssessment of heavy metal enrichment and degree of con-tamination around the copper-nickel mine in the SelebiPhikwe Region Eastern Botswanardquo Environment and EcologyResearch vol 1 no 2 pp 32ndash40 2013
[60] M K Khalil S E O Draz G M El Zokm and G F El-SaidldquoApportionment of geochemistry texturersquos properties and riskassessment of some elements in surface sediments from Bar-dawil Lagoon Egyptrdquo Human and Ecological Risk AssessmentAn International Journal vol 22 no 3 pp 775ndash791 2016
[61] M M El-Sadaawy and G F El-Said ldquoAssessment of fluoridein three selected polluted environments along the EgyptianMediterranean Sea effects on local populationsrdquo Human andEcological Risk Assessment An International Journal vol 20no 6 pp 1643ndash1658 2014
[62] USEPA ldquoSuperfund exposure assessment manualrdquo inOSWER Directive 92855-1EPA540l-88001Office of Emer-gency and Remedial Response Washington DC USA 1988
[63] USEPA ldquoExposure factors handbookrdquo in EPA6008-89043Office of Health and Environmental Assessment Wash-ington DC USA 1989
[64] Health Canada ldquoFederal Contaminated Site Risk Assessmentin Canadardquo Part II Health Canada Toxicological ReferenceValues (TRVs) Cat H46-204-368E Calgary Health CanadaOttawa Canada 2007
[65] J Iqbal S A Tirmizi and M H Shah ldquoStatistical appor-tionment and risk assessment of selected metals in sedimentsfrom Rawal Lake (Pakistan)rdquo Environmental Monitoring andAssessment vol 185 no 1 pp 729ndash743 2013
[66] USEPA (US Environmental Protection Agency) Region 6USAEPA ldquoMultimedia Planning and Permitting DivisionrdquoOffice of Solid Waste Center for Combustion Science andEngineering Washington DC USA 2005
[67] P Jeschke ldquoLatest generation of halogen-containing pesti-cidesrdquo Pest Management Science vol 73 no 6 pp 1053ndash10662017
[68] M A Shreadah O A El-Rayis N A Shaaban andA M Hamdan ldquoWater quality assessment and phosphorusbudget of a lake (Mariut Egypt) after diversion of wastewaterseffluentsrdquo Environmental Science and Pollution Researchvol 27 no 21 pp 26786ndash26799 2020
[69] J P Riley and M Tongudai ldquo-e major cationchlorinityratios in sea waterrdquo Chemical Geology vol 2 pp 263ndash2691967
[70] R B McCleskey D K Nordstrom D D Susong J W Balland J M Holloway ldquoSource and fate of inorganic solutes inthe gibbon river yellowstone national park Wyoming USArdquoJournal of Volcanology and Geothermal Research vol 193no 3-4 pp 189ndash202 2010
[71] G T F Wong and K-Y Li ldquoWinklerrsquos method overestimatesdissolved oxygen in seawater iodate interference and itsoceanographic implicationsrdquo Marine Chemistry vol 115no 1-2 pp 86ndash91 2009
[72] B S R V Prasad P D N Srinivasu P S VarmaA V Raman and S Ray ldquoDynamics of dissolved oxygen inrelation to saturation and health of an aquatic body a case forChilka Lagoon Indiardquo Journal of Ecosystems vol 2014 Ar-ticle ID 526245 17 pages 2014
[73] China Environmental Protection Agency EnvironmentalQuality Standards for Surface Water (GB3838ndash2002) NationalEnvironmental Protection Agency of China Beijing China2002
[74] Y Jia L Wang Z Qu and Z Yang ldquoDistribution con-tamination and accumulation of heavy metals in watersediments and freshwater shellfish from Liuyang RiverSouthern Chinardquo Environmental Science and Pollution Re-search vol 25 no 7 pp 7012ndash7020 2018
[75] A Moneer M El-Sadawy G El-Said and A Radwan ldquoBoronhuman health risk assessment relative to the environmentalpollution of Lake Edku Egyptrdquo Journal of King AbdulazizUniversity vol 23 no 2 pp 41ndash55 2012
[76] C B Tabelin T Igarashi T Arima D Sato T Tatsuhara andS Tamoto ldquoCharacterization and evaluation of arsenic andboron adsorption onto natural geologic materials and theirapplication in the disposal of excavated altered rockrdquo Geo-derma vol 213 pp 163ndash172 2014
[77] G Aloisi K Wallmann M Drews and G BohrmannldquoEvidence for the submarine weathering of silicate minerals inBlack Sea sediments possible implications for the marine Liand B cyclesrdquo Geochemistry Geophysics Geosystems vol 5no 4 pp 1ndash22 2004
[78] C Degueldre and V Cloet ldquoPore water colloid properties inargillaceous sedimentary rocksrdquo Science of e Total Envi-ronment vol 569-570 pp 423ndash433 2016
Journal of Chemistry 19
[79] J A Higgins and D P Schrag ldquoRecords of Neogene seawaterchemistry and diagenesis in deep-sea carbonate sedimentsand pore fluidsrdquo Earth and Planetary Science Letters vol 357-358 pp 386ndash396 2012
[80] H Schroeder A-L Fabricius D Ecker T A Ternes andL Duester ldquoMetal(loid) speciation and size fractionation insediment pore water depth profiles examined with a newmesoprofiling systemrdquo Chemosphere vol 179 pp 185ndash193 2017
[81] Y Song and G Muller ldquoFreshwater sediments sinks andsources of brominerdquo Naturwissenschaften vol 80 no 12pp 558ndash560 1993
[82] M E Goher H I Farhat M H Abdo and S G Salem ldquoMetalpollution assessment in the surface sediment of Lake NasserEgyptrdquo Egyptian Journal of Aquatic Research vol 40 no 3pp 213ndash224 2014
[83] G F El-Said M M El-Sadawy and A A Moneer ldquoIncor-poration of fluoride and boron into surface sediments alongthe Egyptian Mediterranean coastrdquo Egyptian Journal ofAquatic Research vol 36 no 4 pp 569ndash583 2010
[84] B Gilfedder G M Petri M Wessels and H Biester ldquoAniodine mass-balance for Lake Constance Germany insightsinto iodine speciation changes and fluxesrdquo Geochimica etCosmochimica Acta vol 74 no 11 pp 3090ndash3111 2010
[85] E Korobova L Kolmykova B Ryzhenko et al ldquoDistributionand speciation of iodine in drinking waters from geochem-ically different areas of Bryansk region contaminated after theChernobyl accident in relation to health and remediationaspectsrdquo Journal of Geochemical Exploration vol 184pp 311ndash317 2018
[86] V Zic V W Truesdale and N Cukrov ldquo-e distribution ofiodide and iodate in anchialine cave watersmdashevidence forsustained localised oxidation of iodide to iodate in marinewaterrdquoMarine Chemistry vol 112 no 3-4 pp 168ndash178 2008
[87] M B Heeb J Criquet S G Zimmermann-Steffens andU Von Gunten ldquoOxidative treatment of bromide-containingwaters formation of bromine and its reactions with inorganicand organic compoundsmdasha critical reviewrdquo Water Researchvol 48 pp 15ndash42 2014
[88] V Sivasankar A K Darchen and R Omine SakthivelldquoChapter 2 ldquofluoride a world ubiquitous compound itschemistry and ways of contaminationrdquo in Surface ModifiedCarbons as Scavengers for Fluoride fromWater V SivasankarEd pp 5ndash32 copy Springer International Publishing Switzer-land Cham Switzerland 2016
[89] O Cabestrero P Del Buey and M E Sanz-Montero ldquoBio-sedimentary and geochemical constraints on the precipitationof mineral crusts in shallow sulphate lakesrdquo SedimentaryGeology vol 366 pp 32ndash46 2018
[90] M A Hassaan O A El-Rayis and E I Hemada ldquoEstimationof the redox potential of lake mariut drainage system (Qalaaand Umum drains)rdquoHydrology vol 5 no 6 pp 82ndash85 2017
20 Journal of Chemistry
Similarly the coefficient factor loadings of PC4 with1355 are related to the influence of the polluted dischargewater and sediment texture on the formation of F Cl and Isalt besides the precipitation of halogenated compounds(FeF2 Mn(IO3)2 KIO4 and KCIO4) besides their minerals(CaF2 MgF2 FAP and CFAP)
Simultaneously PC5 gives 1092 of the total variancewith positive and negative loadings which explains therelations between the physicochemical limits of the surfacewater pore water and sediment components and theprecipitation of minerals and salts (OCP HAP CuBrZn(OH)2 and Zn(IO3)22H2O) -is is also associated tothe influence of the sedimentary material on the release ofMn Fe and P from sediment into pore water and watercolumn and formation of Ca3(PO4)2 OCP and HAPminerals
However PC6 associates with 100 of the total variancegiving positive and negative coefficient factor loadingswhich explain that the sediments (minerals andor organic-iodine compounds) are only the acting sink for iodine andiodine species (Iminus and IOminus
3 ) in the water as previously re-ported [84] PC6 also reflects the precipitation of severalhalogenated compounds such as calcium iodate (Ca(IO3)2and Ca(IO3)26H2O) and copper iodate (CuI andCuIO3H2O) besides Cu3(PO4)2 species in the lake watercolumn
-e loadings of PC7 contribute by 804 and show thatthe release of calcium in pore water into the water column isresponsible for the precipitation of halogenated compounds(CuCl and Zn(IO3)22H2O) as well as copper and Zn salts(Cu3(PO4)2 and Zn(OH)2)
362 Cluster Analysis On the other hand cluster analysisshows that the similarity of sites 1amp4 5amp8 6amp9 2amp10 and11amp13 is due to the texture of sediment
363 Multiple Regression Multiple regression equations ofhalogens as dependent variables and the other determinedand calculated parameters as independent variables insurface water pore water and sediment partitions are listed(Table 5)-e amount of fluoride in water samples is affectedby the discharged watersrsquo fundamental components espe-cially Zn and Cu besides its surface water-pore water in-teractions Its content in pore water seems to be stronglyaffected by its substitution competition with other halogensin surface water-spore water-sediment cycle due to its highelectronegativity Generally in the affected area the type ofpollutant in the discharged water plays an important role inthe dissolution andor precipitation of fluoride and otherhalogens in the surface water-pore water-sediment cycle
574
147129
300
12
Ca(HCO3)2CaSO4CaCl2
MgCl2KClNaCl
(a)
SO4
2 + CIndash Ca 2+ + Mg 2+
CO32ndash + HCO3
ndashNa+ + K+
Mg2+ SO42ndash
Ca2+ CIndash
(b)
Figure 3 (a) distribution and (b) piper ternary diagram of the formed dissolved salts in surface water of Lake Mariout
Ca(HCO3)2Mg(HCO3)2MgSO4
NaClMgCI2KCl
760 1052
7373 31
(a)
SO4
2ndash + C
Indash
Ca 2+ + Mg 2+
CO32ndash + HCO3
ndashNa+ + K+
Mg2+ SO42ndash
CIndashCa2+
(b)
Figure 4 (a) distribution and (b) piper ternary diagram of the formed dissolved salts in pore water of Lake Mariout
14 Journal of Chemistry
Table 5 -e multiple regression analyses of each halogen as dependent variable and other tested variables in the surface water pore waterand sediment partitions besides the precipitated salts in surface water along Lake Mariout
Dependentvariable Multiple regression equation R2
FluorideLake water FW 3162 + 092 Zn F2 minus 033 SiP + 021 CuIminus 017 SpermilP 09911
Pore water Fp minus2567minus117 SiW minus 033 LiP minus 062 CuClminus 028 IS + 023 TDSW+ 017 KIO4 minus 012 BrW minus 004porosity + 004 PW
10000
Sediment FS 088 CAPminus 049 MgS minus 046 DOW+039MgW+ 027 Mn(IO3)2 + 015 Cu3(PO4)2 + 004 HAP+ 002 pHP 10000ChlorideLake water No relation 00000Pore water No relation 00000Sediment ClS minus116 + 046 MgP + 077 Kp minus 049 dolomite + 017 TDSW minus 011 CuI + 005 NaS + 002 BS + 001 FeF2 10000Bromide
Lake water BrW 1563 + 110 CuBrminus 057 CuClminus 021 KS minus 014 pHP minus 011 TPS + 014 FeW+ 007 ZnSminus 002 PP + 001turbidity 10000
Pore water BrP minus1516minus 055 FeS minus 073 BS + 061 MnW+ 083 SiP + 049 NaS minus 031MnS minus 015 CuBr + 011 pHW minus 001CaW
10000
Sediment BrS 015 SiP + 195 CFAP+ 002 FP minus 045 IS + 192 sand+ 037 MnW minus 029 MgS minus 012 LiP + 005Ca3(PO4)2 minus 002 ZnF2
10000
IodideLake water IW 099 Ca(IO3)6H2O 09999
Pore water IP minus097 ZnF2 minus 057 Li3PO4 minus 053 BP + 034 FAP+ 015 Ca(IO3)2 +MnW+ 005 KS minus 009 turbidity + 055CaS
09999
Sediment IS minus072 + 135 SO4P + 023 Mn(IO3)2 + 063 FeW+ 031 TPS minus 035 MgP minus 012 Zn(CO3)22H2O 09993
40E + 0135E + 0130E + 0125E + 0120E + 0115E + 0110E + 0150E + 0000E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
12345
678910
111213
(a)
10E + 0090E ndash 0180E ndash 0170E ndash 0160E ndash 0150E ndash 0140E ndash 0130E ndash 0120E ndash 0110E ndash 0100E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
12345
678910
111213
(b)
12345
678910
111213
40E ndash 0235E ndash 0230E ndash 0225E ndash 0220E ndash 0215E ndash 0210E ndash 0250E ndash 0300E ndash 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
(c)
12345
678910
111213
80E ndash 0670E ndash 0660E ndash 0650E ndash 0640E ndash 0630E ndash 0620E ndash 0610E ndash 0600E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
(d)
Figure 5 Hazard quotient of ingestion and dermal contact of surface water and sediment of LakeMariout (a) ingestion of water (b) dermalcontact of water (c) ingestion of sediment and (d) dermal contact of sediment
Journal of Chemistry 15
Minerals and precipitated salts in the different partitions(surface water pore water and sediment) play an importantrole in the deposition and release of halogens in sedimentsAdditionally the texture and the porosity of the sedimentsplay a key role in the distribution of halogens in the threepartitions Interestingly chloride is the only halogen that hasnegligible interactions along the surface water and porewater partitions because it is present in large quantities inthe form of soluble salts (NaCl and MgCl2)
37 Pollution Status
371 Enrichment Factor (EF) Twowell-knownmethods areused to assess environmental pollution public health sig-nificance of ingestion and dermal contact with water andsediment components and sediment enrichment factor (EF)[59 60]
-e average EF values of the determined elements CaMg Na K Li B P Cu Zn Mn Fe F Cl Br and I are alllower than the value that is less than the minimum en-richment value (EFlt 2)-us the area under investigation isstill ecologically considered as an unpolluted region
372 Human Health Risk Assessment -e EDI HQ and HIshow the variable values of all pollutants in the surface waterand sediments along the lake region and in drains (sites11ndash13) under study Among all the calculated variables ofsurface water ingestion (EDIIngw) and dermal contact(EDIDermw) Cl is still the only variable that shows high levels(average 1551 and 43mg kgminus1 dayminus1 respectively) -eestimation daily intake of sediment ingestion (EDIIngs) anddermal contact (EDIDerms) of Mg Ca and Na give maximumaverage amounts of 841Eminus 02 513E ndash 02 and167Eminus 03mg kgminus1 dayminus1 respectively
Among the HQ of the calculated detection variables thecontent of HQB of ingestion and dermal contact with waterand sediment is the highest However 70 of sites have HQBvalues more than 10 (Figure 5) Comparing the HQ values ofall the determined variables HQB of the ingestion of surfacewater shows values higher (gt10) However due to the impactof drainage the HQB values of stations 1ndash4 8ndash10 12 and 13
are higher than 10 -erefore these sites can be consideredas the area with the most serious boron pollution caused byuntreated discharged water disposal In addition the HIIngwlevel of water ingestion for the studied variables in all sites ismuch higher than 10 (Figure 6) Except for boron it isusually concluded that the study area does not pose any riskto the population due to halogens or other variables Ac-cordingly this information may help the official authoritiesoptimize management plans and strengthen their pollutioncontrol actions in Lake Mariout
4 Conclusions
-e effects of halogen salts and minerals on the pollution ofLake Mariout were studied Halogens and some physico-chemical variables in three partitions surface water porewater and sediment in Lake Mariout were evaluated -ehalogen content was variable between different sites andchloride was the main halogen in surface water and porewater but it was very rare in the lakersquos sediment partitionPiper ternary diagram and Palmerrsquos method reflected thatNaCl was the dominant salt in surface water while MgCl2was the main dissolve salt in pore water-e chlorinity ratiosof halogens and tested variables were directly matched to thefeeding drain sources
Moreover the Saturation Index (SI) reveals that 23 and 15precipitated salts and minerals are formed in surface water andpore water respectively -e SI value indicated the formationof phosphate minerals in surface water and pore water es-pecially octacalcium phosphate (OCP Ca4H(PO4)325H2O)and hydroxyapatite (HAP Ca5(PO4)3OH) In addition tofluoride minerals especially fluorapatite (FAP) and carbonate-fluorapatite (CFAP) were obviously precipitated from surfacewater and pore water Soluble salts of bromide and chloridewere formed in surface water and pore water Iodide salts(Ca(IO3)2 and Ca(IO3)26H2O) were moderately precipitatedin the surface water and pore water
Moreover the multivariate analysis including the cor-relation matrix multiple stepwise linear regression treeclustering and principle component (PCA) of all the de-termined and calculated variables was applied to estimatethe proposed interaction between halogens and other tested
10E + 02
16E + 0214E + 0212E + 02
80E + 0160E + 0140E + 0120E + 0100E + 00
1 2 3 4 5 6 7 8 9 10 11 12 13
HIIngHIDerm
(a)
1 2 3 4 5 6 7 8 9 10 11 12 13
HIIngHIDerm
40E ndash 0235E ndash 0230E ndash 0225E ndash 0220E ndash 0215E ndash 0210E ndash 0250E ndash 0300E + 01
(b)
Figure 6 Hazard index of ingestion and dermal contact of the studied variables in surface water and sediment of Lake Mariout (a) waterand (b) sediment
16 Journal of Chemistry
variables in the polluted area under study -e multivariateanalysis showed that there were many interactions betweenhalogens and tested variables High levels of fluoride bro-mide and chloride in surface water were related to thecomposition of drainage waters -e enrichment factor (EF)showed that Lake Mariout was not polluted However thehuman health adverse effects calculated for surface waterand sediment did not reflect any possible likelihood hazardeffects from halogens
Interestingly the current study concluded that halogencompounds especially fluorides are most likely to be de-posited from surface lakes in the form of many minerals andprecipitation thereby reducing the adverse pollution effectson human health -e results obtained through this workhelp to find the correlations between the sampling sites andthe variables obtained by physical and chemical measure-ments which can be used to construct a fast decision modelfor separating different water quality samples -is infor-mation may help the official authorities optimize manage-ment plans and strengthen their pollution control measuresin Lake Mariout
Data Availability
-e data used to support the findings of this research areincluded within the paper
Conflicts of Interest
-e authors declare that there are no conflicts of interestregarding the publication of this manuscript
Supplementary Materials
Supplementary Table 1 correlation matrix of variable insurface water pore water and sediment partitions besidesthe precipitated salts in surface water along Lake Mariout(Supplementary Materials)
References
[1] M S Masoud T O Said G El-Zokm and M A ShreadahldquoAssesment of heavy metals contamination in surface sedi-ments of the Egyptian Red Sea Coastsrdquo Australian Journal ofBasic and Applied Sciences vol 6 pp 44ndash58 2012
[2] M A Shreadah M I Abdel Moneim T O SaidE M I Fathallah and M E Mahmoud ldquoPAHs in seawater ofthe semi-closed areas along the Alexandria coast of EgyptianMediterranean seardquo Journal of Environmental Protectionvol 4 no 11 p 11 Article ID 40298 2013
[3] S Abdel Ghani G El Zokm A Shobier T Othman andM Shreadah ldquoMetal pollution in surface sediments of Abu-Qir bay and Eastern harbour of Alexandria Egyptrdquo EgyptianJournal of Aquatic Research vol 39 no 1 pp 1ndash12 2013
[4] G F El-Said ldquoBioaccumulation of key metals and othercontaminants by seaweeds from the Egyptian MediterraneanSea Coast in relation to human health riskrdquo Human andEcological Risk Assessment An International Journal vol 19no 5 pp 1285ndash1305 2013
[5] M A Shreadah A H Shobier S Abdel Ghani G M El-Zokm and T O Said ldquoMajor ions anomalies and
contamination status by trace metals in sediments from twohot spots along the Mediterranean Coast of Egyptrdquo Envi-ronmental Monitoring and Assessment vol 187 no 280pp 1ndash18 2015
[6] A El Nemr G F El-Said A Khaled and S Ragab ldquoDis-tribution and ecological risk assessment of some heavy metalsin coastal surface sediments along the Red Sea Egyptrdquo In-ternational Journal of Sediment Research vol 31 no 2pp 164ndash172 2016
[7] A El Nemr G F El-Said S Ragab A Khaled and A El-Sikaily ldquo-e distribution contamination and risk assessmentof heavy metals in sediment and shellfish from the Red Seacoast Egyptrdquo Chemosphere vol 165 pp 369ndash380 2016
[8] A El Nemr and G F El-Said ldquoAssessment and ecological riskof heavy metals in sediment and molluscs from the Medi-terranean coastrdquo Water Environment Research vol 89 no 3pp 195ndash210 2017
[9] M A Sheradah A A El-Sikaily N M Abd El MoneamN E Abd El Maguid and M G Zaki ldquoChemical and bio-chemical evaluation of marine pollution by polychlorinatedbiphenyls and pesticides in two regions along the EgyptianMediterranean Seardquo International Journal of EnvironmentalMonitoring and Analysis vol 6 no 3 pp 95ndash109 2018
[10] M A Shreadah A A-M M El-Sayed A A S TahaA-M M Ahmed and H H Abdel Rahman ldquoEvaluation ofdifferent anthropogenic effluents impacts on the water qualityusing principal component analysis a case study of Abu-QirBay-Alexandria-Egyptrdquo International Journal of Environ-mental Monitoring and Analysis vol 7 no 3 pp 56ndash67 2019
[11] G F El-Said M M El-Sadaawy A H Shobier andS E Ramadan ldquoHuman health implication of major and traceelements present in commercial crustaceans of a traditionalseafood marketing region Egyptrdquo Biological Trace ElementResearch vol 199 pp 315ndash328 2020
[12] M A Shreadah S A A Ghani H B I HawashA A E Samie and A E M M Ahmed ldquoOrganotin com-pounds in sediments of northern lakes Egyptrdquo Journal ofEnvironmental Protection vol 05 no 17 pp 1654ndash1666 2014
[13] A M Younis G M El-Zokm and M A Okbah ldquoSpatialvariation of acid-volatile sulfide and simultaneously extractedmetals in Egyptian Mediterranean Sea lagoon sedimentsrdquoEnvironmental Monitoring and Assessment vol 186 no 6pp 3567ndash3579 2014
[14] G F El-Said S E O Draz M M El-Sadaawy andA A Moneer ldquoSedimentology geochemistry pollution statusand ecological risk assessment of some heavy metals insurficial sediments of an Egyptian lagoon connecting to theMediterranean Seardquo Journal of Environmental Science andHealth Part A vol 49 no 9 pp 1029ndash1044 2014
[15] G M El Zokm M A Okbah and A M Younis ldquoAssessmentof heavy metals pollution using AVS-SEM and fractionationtechniques in Edku Lagoon sediments Mediterranean SeaEgyptrdquo Journal of Environmental Science and Health PartAvol 50 no 6 pp 571ndash584 2015
[16] G M El Zokm H R Z Tadros M A Okbah andG H Ibrahim ldquoldquoEutrophication assessment using TRIX andCarlsonrsquos indices in Lake Mariout water Egyptrdquo EgyptianJournal of Aquatic Biology and Fisheries vol 22 no 5pp 331ndash349 2018
[17] N Donia ldquoLake Maryut monitoring using remote sensingrdquo inProceedings of the gypt Eighteenth International WaterTechnology Conference IWTC18 Sharm El Sheikh Abu DhabiUAE March 2015
Journal of Chemistry 17
[18] M A Khairy ldquoAssessment of priority phenolic compounds insediments from an extremely polluted coastal wetland (LakeMaryut Egypt)rdquo Environmental Monitoring and Assessmentvol 185 no 1 pp 441ndash455 2013
[19] N A El-Naggar and E A Rifaat ldquoEgyptian coastal lakes andwetlands part Imdashcharacteristics and hydrodynamicsrdquo in eHandbook of Environmental Chemistry A M Negm EdSpringer International Publishing AG Berlin Germany 2017
[20] J J Hanley and K T Koga ldquoChapter 2 ldquohalogens in terrestrialand cosmic geochemical systems abundances Geochemicalbehaviors and analytical methodsrdquordquo in e Role of Halogensin Terrestrial and Extraterrestrial Geochemical ProcessesD E Harlov and L Aranovich Eds Springer InternationalPublishing AG Berlin Germany pp 21ndash121 2018
[21] A Ghosh K Mukherjee S K Ghosh and B Saha ldquoSourcesand toxicity of fluoride in the environmentrdquo Research onChemical Intermediates vol 39 no 7 pp 2881ndash2915 2013
[22] M M Naim A A Moneer and G F El-Said ldquoPredictiveequations for the defluoridation by electrocoagulation tech-nique using bipolar aluminum electrodes in the absence andpresence of additives a multivariate studyrdquo Desalination andWater Treatment vol 57 no 14 pp 6320ndash6332 2016
[23] G F El-Said N A Shaltout M M El-Sadaawy andA M H Morsy ldquo-e precipitation of fluoride calcium andmagnesium minerals from Egyptian Mediterranean Sea coastin relation to discharged watersrdquo Desalination and WaterTreatment vol 57 no 5 pp 2113ndash2124 2016
[24] H Bureau ldquoIodine encyclopedia of geochemistry A com-prehensive reference source on the chemistry of the earthrdquo inEncyclopedia of Earth Sciences Series W M White Ed copySpringer International Publishing AG 2016
[25] F C Kupper and C J Carrano ldquoKey aspects of the iodinemetabolism in brown algae a brief critical reviewrdquo Metal-lomics vol 11 pp 756ndash764 2019
[26] R Liteplo R Gomes P Howe and H Malcolm Fluorides-Environmental Health Criteria 227 p 290 World HealthOrganization (WHO) Geneva Switzerland 2002
[27] G F El-Said and M M El-Sadaawy ldquoSeasonal variation ofboron and fluoride in Tilapia nilotica from an Egyptian fishfarm in relation to Human health hazard assessmentrdquoHumanand Ecological Risk Assessment An International Journalvol 19 no 4 pp 930ndash943 2013
[28] WHO (World Health Organization) Bromide in Drinking-Water Background Document for Development of WHOGuidelines for Drinking-Water Quality WHO Press WorldHealth Organization Geneva Switzerland 2009
[29] G F El-Said and N A Sallam ldquo-e uptake of fluorideconcentration and its effects on the growth rate of shrimps(Palaemon elegans Rathke)rdquo Chemistry and Ecology vol 24no 3 pp 191ndash205 2008
[30] X Zhang J He B He and J Sun ldquoAssessment formationmechanism and different source contributions of dissolvedsalt pollution in the shallow groundwater of Hutuo Riveralluvial-pluvial fan in the North China Plainrdquo EnvironmentalScience and Pollution Research vol 26 no 35 pp 35742ndash35756 2019
[31] Y Zhu B Huang Z Zhu et al ldquoldquoCharacterization disso-lution and solubility of the hydroxypyromorphitendashhydroxyapatite solid solution [(PbxCa1minusx)5(PO4)3OH] at25 degC and pH 2ndash9rdquo Geochemical Transactions vol 17 no 2pp 1ndash18 2016
[32] G F El-Said M M El-Sadaawy A A Moneer andN A Shaltout ldquo-e effect of fluoride on the distribution ofsome minerals in the surface water of an Egyptian lagoon at
the Mediterranean Seardquo Egyptian Journal of Aquatic Researchvol 41 no 1 pp 31ndash39 2015
[33] Y Zhu Z Zhu X Zhao Y Liang and Y Huang ldquoChar-acterization dissolution and solubility of lead hydroxypyr-omorphite [Pb5(PO4)3OH] at 25ndash45degCrdquo Journal ofChemistry vol 2015 Article ID 269387 10 pages 2015
[34] M A Z Chahouki ldquoMultivariate analysis techniques inenvironmental sciencerdquo in Earth and Environmental SciencesDr Imran Ahmad Dar Ed InTech Open London UK 2011httpwwwintechopencombooksearth-and-environmental-sciencesmultivariate-analysis-techniques-inenvironmental-science
[35] J V Klump and C S Martens ldquoBiogeochemical cycling in anorganic-rich coastal marine basin 5 Sedimentary nitrogenand phosphorus budgets based upon kinetic models massbalances and the stoichiometry of nutrient regenerationrdquoGeochimica et Cosmochimica Acta vol 51 no 5 pp 1161ndash1173 1987
[36] R L Folk Petrology of Sedimentary Rocks University of TexasAustin TX USA 1974
[37] P Saenger ldquoA rapid spectrophotometric method for thedetermination of bromine in seawater and in the ash ofmarine algaerdquo Helgolander Wissenschaftliche Meer-esuntersuchungen vol 23 no 1 pp 32ndash37 1972
[38] P G Jeffery Chemical Methods of Rock Analysis PergamonPress New York NY USA 2nd edition 1975
[39] J D H Strickland and T R Parsons ldquoA practical handbook ofseawater analysisrdquo in Fisheries Research Board of CanadaBulletin 167p 311 Second edition Wiley Ottawa Canada1972
[40] B Horvath O Opara-Nadi and F Beese ldquoA simple methodfor measuring the carbonate content of soilsrdquo Soil ScienceSociety of America Journal vol 69 no 4 pp 1066ndash1068 2005
[41] K Grasshoff Methods of Seawater Analysis p 317 VerlagChemie Weinkeim Germany 1976
[42] R Danovaro D Marrale N Della Croce P Parodi andM Fabiano ldquoBiochemical composition of sedimentary or-ganic matter and bacterial distribution in the Aegean Seatrophic state and pelagic-benthic couplingrdquo Journal of SeaResearch vol 42 no 2 pp 117ndash129 1999
[43] APHA-AWWA-WPCF (American Public Health Associa-tion) Standard Methods for the Examination of Water andWaste Water American Public Health Association Wash-ington DC USA 20th edition 1999
[44] K I Aspila H Agemian and A S Y Chau ldquoA semi-auto-mated method for the determination of inorganic organicand total phosphate in sedimentsrdquo e Analyst vol 101no 1200 pp 187ndash197 1976
[45] J P Riley and D Taylor ldquoChelating resins for the concen-tration of trace elements from sea water and their analyticaluse in conjunction with atomic absorption spectrophotom-etryrdquo Analytica Chimica Acta vol 40 pp 479ndash485 1968
[46] G F El-Said and A El-Sikaily ldquoChemical composition ofsome seaweed from Mediterranean Sea coast Egyptrdquo Envi-ronmental Monitoring and Assessment vol 185 no 7pp 6089ndash6099 2013
[47] Directorate General of Health Services Ministry of Health andFamilyWelfare Government of India ldquoManual of methods ofanalysis of foodsrdquo in Fruit and Vegetable Productsp 57Directorate General of Health Services Ministry of Health andFamily Welfare Government of India New Delhi India2005
[48] A Gunnars S Blomqvist and C Martinsson ldquoInorganicformation of apatite in brackish seawater from the Baltic Sea
18 Journal of Chemistry
an experimental approachrdquo Marine Chemistry vol 91 no 1-4 pp 15ndash26 2004
[49] W M Haynes D R Lide and T J Bruno CRC Handbook ofChemistry and Physics A Ready Reference Book of Chemicaland Physical Data CRC Press Taylor amp Frances Group BocaRaton FL USA 97th edition 2017
[50] M S Masoud M I El-Samra and M M El-Sadawy ldquoWaterchemistry of el-mex bay west of Alexandria Egyptrdquo eEgypian Science Magazine vol 2 pp 70ndash78 2005
[51] F J Millero R Feistel D G Wright and T J McDougallldquo-e composition of standard seawater and the definition ofthe reference-composition salinity scalerdquo Deep Sea ResearchPart I Oceanographic Research Papers vol 55 no 1pp 50ndash72 2008
[52] S K El-Wakeel S A Morcos and A M Mahlis ldquo-e majorcations in Lake Maryut watersrdquo Hydrobiologia vol 36 no 2pp 253ndash274 1970
[53] A M Mahlis S A Morcos and S K El-Wakeel ldquo-e majoranions in Lake Maryut watersrdquo Hydrobiologia vol 36 no 2pp 275ndash294 1970
[54] A S Saad M A Massoud R A Amer and M A GhorabldquoAssessment of the physico-chemical characteristics andwater quality analysis of Mariout Lake southern of Alexan-dria Egyptrdquo Journal of Environmental and Analytical Toxi-cology vol 7 no 1 p 421 2017
[55] R Rumuri ldquoDataset on hydrogeochemical characteristics ofgroundwater and surface water in Kattumannarkoil TalukIndiardquo Data in Brief vol 32 Article ID 106058 2020
[56] P Szefer S W Fowler K Ikuta et al ldquoA comparative as-sessment of heavy metal accumulation in soft parts and byssusof mussels from subarctic temperate subtropical and tropicalmarine environmentsrdquo Environmental Pollution vol 139no 1 pp 70ndash78 2006
[57] N F Soliman G M El Zokm and M A Okbah ldquoRisk as-sessment and chemical fractionation of selected elements insurface sediments from Lake Qarun Egypt using modifiedBCR techniquerdquo Chemosphere vol 191 pp 262ndash271 2018
[58] G M El Zokm M I A Ibrahim L A Mohamed and M El-Mamoney ldquoCritical geochemical insight into Alexandria coastwith special reference to diagnostic ratios (TOCTN amp SrCa)and heavy metals ecotoxicological hazardsrdquo Egyptian Journalof Aquatic Research vol 46 no 1 pp 27ndash33 2020
[59] A S Likuku K B Mmolawa and G K GaboutloeloeldquoAssessment of heavy metal enrichment and degree of con-tamination around the copper-nickel mine in the SelebiPhikwe Region Eastern Botswanardquo Environment and EcologyResearch vol 1 no 2 pp 32ndash40 2013
[60] M K Khalil S E O Draz G M El Zokm and G F El-SaidldquoApportionment of geochemistry texturersquos properties and riskassessment of some elements in surface sediments from Bar-dawil Lagoon Egyptrdquo Human and Ecological Risk AssessmentAn International Journal vol 22 no 3 pp 775ndash791 2016
[61] M M El-Sadaawy and G F El-Said ldquoAssessment of fluoridein three selected polluted environments along the EgyptianMediterranean Sea effects on local populationsrdquo Human andEcological Risk Assessment An International Journal vol 20no 6 pp 1643ndash1658 2014
[62] USEPA ldquoSuperfund exposure assessment manualrdquo inOSWER Directive 92855-1EPA540l-88001Office of Emer-gency and Remedial Response Washington DC USA 1988
[63] USEPA ldquoExposure factors handbookrdquo in EPA6008-89043Office of Health and Environmental Assessment Wash-ington DC USA 1989
[64] Health Canada ldquoFederal Contaminated Site Risk Assessmentin Canadardquo Part II Health Canada Toxicological ReferenceValues (TRVs) Cat H46-204-368E Calgary Health CanadaOttawa Canada 2007
[65] J Iqbal S A Tirmizi and M H Shah ldquoStatistical appor-tionment and risk assessment of selected metals in sedimentsfrom Rawal Lake (Pakistan)rdquo Environmental Monitoring andAssessment vol 185 no 1 pp 729ndash743 2013
[66] USEPA (US Environmental Protection Agency) Region 6USAEPA ldquoMultimedia Planning and Permitting DivisionrdquoOffice of Solid Waste Center for Combustion Science andEngineering Washington DC USA 2005
[67] P Jeschke ldquoLatest generation of halogen-containing pesti-cidesrdquo Pest Management Science vol 73 no 6 pp 1053ndash10662017
[68] M A Shreadah O A El-Rayis N A Shaaban andA M Hamdan ldquoWater quality assessment and phosphorusbudget of a lake (Mariut Egypt) after diversion of wastewaterseffluentsrdquo Environmental Science and Pollution Researchvol 27 no 21 pp 26786ndash26799 2020
[69] J P Riley and M Tongudai ldquo-e major cationchlorinityratios in sea waterrdquo Chemical Geology vol 2 pp 263ndash2691967
[70] R B McCleskey D K Nordstrom D D Susong J W Balland J M Holloway ldquoSource and fate of inorganic solutes inthe gibbon river yellowstone national park Wyoming USArdquoJournal of Volcanology and Geothermal Research vol 193no 3-4 pp 189ndash202 2010
[71] G T F Wong and K-Y Li ldquoWinklerrsquos method overestimatesdissolved oxygen in seawater iodate interference and itsoceanographic implicationsrdquo Marine Chemistry vol 115no 1-2 pp 86ndash91 2009
[72] B S R V Prasad P D N Srinivasu P S VarmaA V Raman and S Ray ldquoDynamics of dissolved oxygen inrelation to saturation and health of an aquatic body a case forChilka Lagoon Indiardquo Journal of Ecosystems vol 2014 Ar-ticle ID 526245 17 pages 2014
[73] China Environmental Protection Agency EnvironmentalQuality Standards for Surface Water (GB3838ndash2002) NationalEnvironmental Protection Agency of China Beijing China2002
[74] Y Jia L Wang Z Qu and Z Yang ldquoDistribution con-tamination and accumulation of heavy metals in watersediments and freshwater shellfish from Liuyang RiverSouthern Chinardquo Environmental Science and Pollution Re-search vol 25 no 7 pp 7012ndash7020 2018
[75] A Moneer M El-Sadawy G El-Said and A Radwan ldquoBoronhuman health risk assessment relative to the environmentalpollution of Lake Edku Egyptrdquo Journal of King AbdulazizUniversity vol 23 no 2 pp 41ndash55 2012
[76] C B Tabelin T Igarashi T Arima D Sato T Tatsuhara andS Tamoto ldquoCharacterization and evaluation of arsenic andboron adsorption onto natural geologic materials and theirapplication in the disposal of excavated altered rockrdquo Geo-derma vol 213 pp 163ndash172 2014
[77] G Aloisi K Wallmann M Drews and G BohrmannldquoEvidence for the submarine weathering of silicate minerals inBlack Sea sediments possible implications for the marine Liand B cyclesrdquo Geochemistry Geophysics Geosystems vol 5no 4 pp 1ndash22 2004
[78] C Degueldre and V Cloet ldquoPore water colloid properties inargillaceous sedimentary rocksrdquo Science of e Total Envi-ronment vol 569-570 pp 423ndash433 2016
Journal of Chemistry 19
[79] J A Higgins and D P Schrag ldquoRecords of Neogene seawaterchemistry and diagenesis in deep-sea carbonate sedimentsand pore fluidsrdquo Earth and Planetary Science Letters vol 357-358 pp 386ndash396 2012
[80] H Schroeder A-L Fabricius D Ecker T A Ternes andL Duester ldquoMetal(loid) speciation and size fractionation insediment pore water depth profiles examined with a newmesoprofiling systemrdquo Chemosphere vol 179 pp 185ndash193 2017
[81] Y Song and G Muller ldquoFreshwater sediments sinks andsources of brominerdquo Naturwissenschaften vol 80 no 12pp 558ndash560 1993
[82] M E Goher H I Farhat M H Abdo and S G Salem ldquoMetalpollution assessment in the surface sediment of Lake NasserEgyptrdquo Egyptian Journal of Aquatic Research vol 40 no 3pp 213ndash224 2014
[83] G F El-Said M M El-Sadawy and A A Moneer ldquoIncor-poration of fluoride and boron into surface sediments alongthe Egyptian Mediterranean coastrdquo Egyptian Journal ofAquatic Research vol 36 no 4 pp 569ndash583 2010
[84] B Gilfedder G M Petri M Wessels and H Biester ldquoAniodine mass-balance for Lake Constance Germany insightsinto iodine speciation changes and fluxesrdquo Geochimica etCosmochimica Acta vol 74 no 11 pp 3090ndash3111 2010
[85] E Korobova L Kolmykova B Ryzhenko et al ldquoDistributionand speciation of iodine in drinking waters from geochem-ically different areas of Bryansk region contaminated after theChernobyl accident in relation to health and remediationaspectsrdquo Journal of Geochemical Exploration vol 184pp 311ndash317 2018
[86] V Zic V W Truesdale and N Cukrov ldquo-e distribution ofiodide and iodate in anchialine cave watersmdashevidence forsustained localised oxidation of iodide to iodate in marinewaterrdquoMarine Chemistry vol 112 no 3-4 pp 168ndash178 2008
[87] M B Heeb J Criquet S G Zimmermann-Steffens andU Von Gunten ldquoOxidative treatment of bromide-containingwaters formation of bromine and its reactions with inorganicand organic compoundsmdasha critical reviewrdquo Water Researchvol 48 pp 15ndash42 2014
[88] V Sivasankar A K Darchen and R Omine SakthivelldquoChapter 2 ldquofluoride a world ubiquitous compound itschemistry and ways of contaminationrdquo in Surface ModifiedCarbons as Scavengers for Fluoride fromWater V SivasankarEd pp 5ndash32 copy Springer International Publishing Switzer-land Cham Switzerland 2016
[89] O Cabestrero P Del Buey and M E Sanz-Montero ldquoBio-sedimentary and geochemical constraints on the precipitationof mineral crusts in shallow sulphate lakesrdquo SedimentaryGeology vol 366 pp 32ndash46 2018
[90] M A Hassaan O A El-Rayis and E I Hemada ldquoEstimationof the redox potential of lake mariut drainage system (Qalaaand Umum drains)rdquoHydrology vol 5 no 6 pp 82ndash85 2017
20 Journal of Chemistry
Table 5 -e multiple regression analyses of each halogen as dependent variable and other tested variables in the surface water pore waterand sediment partitions besides the precipitated salts in surface water along Lake Mariout
Dependentvariable Multiple regression equation R2
FluorideLake water FW 3162 + 092 Zn F2 minus 033 SiP + 021 CuIminus 017 SpermilP 09911
Pore water Fp minus2567minus117 SiW minus 033 LiP minus 062 CuClminus 028 IS + 023 TDSW+ 017 KIO4 minus 012 BrW minus 004porosity + 004 PW
10000
Sediment FS 088 CAPminus 049 MgS minus 046 DOW+039MgW+ 027 Mn(IO3)2 + 015 Cu3(PO4)2 + 004 HAP+ 002 pHP 10000ChlorideLake water No relation 00000Pore water No relation 00000Sediment ClS minus116 + 046 MgP + 077 Kp minus 049 dolomite + 017 TDSW minus 011 CuI + 005 NaS + 002 BS + 001 FeF2 10000Bromide
Lake water BrW 1563 + 110 CuBrminus 057 CuClminus 021 KS minus 014 pHP minus 011 TPS + 014 FeW+ 007 ZnSminus 002 PP + 001turbidity 10000
Pore water BrP minus1516minus 055 FeS minus 073 BS + 061 MnW+ 083 SiP + 049 NaS minus 031MnS minus 015 CuBr + 011 pHW minus 001CaW
10000
Sediment BrS 015 SiP + 195 CFAP+ 002 FP minus 045 IS + 192 sand+ 037 MnW minus 029 MgS minus 012 LiP + 005Ca3(PO4)2 minus 002 ZnF2
10000
IodideLake water IW 099 Ca(IO3)6H2O 09999
Pore water IP minus097 ZnF2 minus 057 Li3PO4 minus 053 BP + 034 FAP+ 015 Ca(IO3)2 +MnW+ 005 KS minus 009 turbidity + 055CaS
09999
Sediment IS minus072 + 135 SO4P + 023 Mn(IO3)2 + 063 FeW+ 031 TPS minus 035 MgP minus 012 Zn(CO3)22H2O 09993
40E + 0135E + 0130E + 0125E + 0120E + 0115E + 0110E + 0150E + 0000E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
12345
678910
111213
(a)
10E + 0090E ndash 0180E ndash 0170E ndash 0160E ndash 0150E ndash 0140E ndash 0130E ndash 0120E ndash 0110E ndash 0100E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
12345
678910
111213
(b)
12345
678910
111213
40E ndash 0235E ndash 0230E ndash 0225E ndash 0220E ndash 0215E ndash 0210E ndash 0250E ndash 0300E ndash 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
(c)
12345
678910
111213
80E ndash 0670E ndash 0660E ndash 0650E ndash 0640E ndash 0630E ndash 0620E ndash 0610E ndash 0600E + 00
HQ
CaH
QM
gH
QN
aH
QK
HQ
LiH
QB
HQ
PH
QCI
HQ
FH
QBr
HQ
IH
QCu
HQ
Mn
HQ
ZnH
QFe
(d)
Figure 5 Hazard quotient of ingestion and dermal contact of surface water and sediment of LakeMariout (a) ingestion of water (b) dermalcontact of water (c) ingestion of sediment and (d) dermal contact of sediment
Journal of Chemistry 15
Minerals and precipitated salts in the different partitions(surface water pore water and sediment) play an importantrole in the deposition and release of halogens in sedimentsAdditionally the texture and the porosity of the sedimentsplay a key role in the distribution of halogens in the threepartitions Interestingly chloride is the only halogen that hasnegligible interactions along the surface water and porewater partitions because it is present in large quantities inthe form of soluble salts (NaCl and MgCl2)
37 Pollution Status
371 Enrichment Factor (EF) Twowell-knownmethods areused to assess environmental pollution public health sig-nificance of ingestion and dermal contact with water andsediment components and sediment enrichment factor (EF)[59 60]
-e average EF values of the determined elements CaMg Na K Li B P Cu Zn Mn Fe F Cl Br and I are alllower than the value that is less than the minimum en-richment value (EFlt 2)-us the area under investigation isstill ecologically considered as an unpolluted region
372 Human Health Risk Assessment -e EDI HQ and HIshow the variable values of all pollutants in the surface waterand sediments along the lake region and in drains (sites11ndash13) under study Among all the calculated variables ofsurface water ingestion (EDIIngw) and dermal contact(EDIDermw) Cl is still the only variable that shows high levels(average 1551 and 43mg kgminus1 dayminus1 respectively) -eestimation daily intake of sediment ingestion (EDIIngs) anddermal contact (EDIDerms) of Mg Ca and Na give maximumaverage amounts of 841Eminus 02 513E ndash 02 and167Eminus 03mg kgminus1 dayminus1 respectively
Among the HQ of the calculated detection variables thecontent of HQB of ingestion and dermal contact with waterand sediment is the highest However 70 of sites have HQBvalues more than 10 (Figure 5) Comparing the HQ values ofall the determined variables HQB of the ingestion of surfacewater shows values higher (gt10) However due to the impactof drainage the HQB values of stations 1ndash4 8ndash10 12 and 13
are higher than 10 -erefore these sites can be consideredas the area with the most serious boron pollution caused byuntreated discharged water disposal In addition the HIIngwlevel of water ingestion for the studied variables in all sites ismuch higher than 10 (Figure 6) Except for boron it isusually concluded that the study area does not pose any riskto the population due to halogens or other variables Ac-cordingly this information may help the official authoritiesoptimize management plans and strengthen their pollutioncontrol actions in Lake Mariout
4 Conclusions
-e effects of halogen salts and minerals on the pollution ofLake Mariout were studied Halogens and some physico-chemical variables in three partitions surface water porewater and sediment in Lake Mariout were evaluated -ehalogen content was variable between different sites andchloride was the main halogen in surface water and porewater but it was very rare in the lakersquos sediment partitionPiper ternary diagram and Palmerrsquos method reflected thatNaCl was the dominant salt in surface water while MgCl2was the main dissolve salt in pore water-e chlorinity ratiosof halogens and tested variables were directly matched to thefeeding drain sources
Moreover the Saturation Index (SI) reveals that 23 and 15precipitated salts and minerals are formed in surface water andpore water respectively -e SI value indicated the formationof phosphate minerals in surface water and pore water es-pecially octacalcium phosphate (OCP Ca4H(PO4)325H2O)and hydroxyapatite (HAP Ca5(PO4)3OH) In addition tofluoride minerals especially fluorapatite (FAP) and carbonate-fluorapatite (CFAP) were obviously precipitated from surfacewater and pore water Soluble salts of bromide and chloridewere formed in surface water and pore water Iodide salts(Ca(IO3)2 and Ca(IO3)26H2O) were moderately precipitatedin the surface water and pore water
Moreover the multivariate analysis including the cor-relation matrix multiple stepwise linear regression treeclustering and principle component (PCA) of all the de-termined and calculated variables was applied to estimatethe proposed interaction between halogens and other tested
10E + 02
16E + 0214E + 0212E + 02
80E + 0160E + 0140E + 0120E + 0100E + 00
1 2 3 4 5 6 7 8 9 10 11 12 13
HIIngHIDerm
(a)
1 2 3 4 5 6 7 8 9 10 11 12 13
HIIngHIDerm
40E ndash 0235E ndash 0230E ndash 0225E ndash 0220E ndash 0215E ndash 0210E ndash 0250E ndash 0300E + 01
(b)
Figure 6 Hazard index of ingestion and dermal contact of the studied variables in surface water and sediment of Lake Mariout (a) waterand (b) sediment
16 Journal of Chemistry
variables in the polluted area under study -e multivariateanalysis showed that there were many interactions betweenhalogens and tested variables High levels of fluoride bro-mide and chloride in surface water were related to thecomposition of drainage waters -e enrichment factor (EF)showed that Lake Mariout was not polluted However thehuman health adverse effects calculated for surface waterand sediment did not reflect any possible likelihood hazardeffects from halogens
Interestingly the current study concluded that halogencompounds especially fluorides are most likely to be de-posited from surface lakes in the form of many minerals andprecipitation thereby reducing the adverse pollution effectson human health -e results obtained through this workhelp to find the correlations between the sampling sites andthe variables obtained by physical and chemical measure-ments which can be used to construct a fast decision modelfor separating different water quality samples -is infor-mation may help the official authorities optimize manage-ment plans and strengthen their pollution control measuresin Lake Mariout
Data Availability
-e data used to support the findings of this research areincluded within the paper
Conflicts of Interest
-e authors declare that there are no conflicts of interestregarding the publication of this manuscript
Supplementary Materials
Supplementary Table 1 correlation matrix of variable insurface water pore water and sediment partitions besidesthe precipitated salts in surface water along Lake Mariout(Supplementary Materials)
References
[1] M S Masoud T O Said G El-Zokm and M A ShreadahldquoAssesment of heavy metals contamination in surface sedi-ments of the Egyptian Red Sea Coastsrdquo Australian Journal ofBasic and Applied Sciences vol 6 pp 44ndash58 2012
[2] M A Shreadah M I Abdel Moneim T O SaidE M I Fathallah and M E Mahmoud ldquoPAHs in seawater ofthe semi-closed areas along the Alexandria coast of EgyptianMediterranean seardquo Journal of Environmental Protectionvol 4 no 11 p 11 Article ID 40298 2013
[3] S Abdel Ghani G El Zokm A Shobier T Othman andM Shreadah ldquoMetal pollution in surface sediments of Abu-Qir bay and Eastern harbour of Alexandria Egyptrdquo EgyptianJournal of Aquatic Research vol 39 no 1 pp 1ndash12 2013
[4] G F El-Said ldquoBioaccumulation of key metals and othercontaminants by seaweeds from the Egyptian MediterraneanSea Coast in relation to human health riskrdquo Human andEcological Risk Assessment An International Journal vol 19no 5 pp 1285ndash1305 2013
[5] M A Shreadah A H Shobier S Abdel Ghani G M El-Zokm and T O Said ldquoMajor ions anomalies and
contamination status by trace metals in sediments from twohot spots along the Mediterranean Coast of Egyptrdquo Envi-ronmental Monitoring and Assessment vol 187 no 280pp 1ndash18 2015
[6] A El Nemr G F El-Said A Khaled and S Ragab ldquoDis-tribution and ecological risk assessment of some heavy metalsin coastal surface sediments along the Red Sea Egyptrdquo In-ternational Journal of Sediment Research vol 31 no 2pp 164ndash172 2016
[7] A El Nemr G F El-Said S Ragab A Khaled and A El-Sikaily ldquo-e distribution contamination and risk assessmentof heavy metals in sediment and shellfish from the Red Seacoast Egyptrdquo Chemosphere vol 165 pp 369ndash380 2016
[8] A El Nemr and G F El-Said ldquoAssessment and ecological riskof heavy metals in sediment and molluscs from the Medi-terranean coastrdquo Water Environment Research vol 89 no 3pp 195ndash210 2017
[9] M A Sheradah A A El-Sikaily N M Abd El MoneamN E Abd El Maguid and M G Zaki ldquoChemical and bio-chemical evaluation of marine pollution by polychlorinatedbiphenyls and pesticides in two regions along the EgyptianMediterranean Seardquo International Journal of EnvironmentalMonitoring and Analysis vol 6 no 3 pp 95ndash109 2018
[10] M A Shreadah A A-M M El-Sayed A A S TahaA-M M Ahmed and H H Abdel Rahman ldquoEvaluation ofdifferent anthropogenic effluents impacts on the water qualityusing principal component analysis a case study of Abu-QirBay-Alexandria-Egyptrdquo International Journal of Environ-mental Monitoring and Analysis vol 7 no 3 pp 56ndash67 2019
[11] G F El-Said M M El-Sadaawy A H Shobier andS E Ramadan ldquoHuman health implication of major and traceelements present in commercial crustaceans of a traditionalseafood marketing region Egyptrdquo Biological Trace ElementResearch vol 199 pp 315ndash328 2020
[12] M A Shreadah S A A Ghani H B I HawashA A E Samie and A E M M Ahmed ldquoOrganotin com-pounds in sediments of northern lakes Egyptrdquo Journal ofEnvironmental Protection vol 05 no 17 pp 1654ndash1666 2014
[13] A M Younis G M El-Zokm and M A Okbah ldquoSpatialvariation of acid-volatile sulfide and simultaneously extractedmetals in Egyptian Mediterranean Sea lagoon sedimentsrdquoEnvironmental Monitoring and Assessment vol 186 no 6pp 3567ndash3579 2014
[14] G F El-Said S E O Draz M M El-Sadaawy andA A Moneer ldquoSedimentology geochemistry pollution statusand ecological risk assessment of some heavy metals insurficial sediments of an Egyptian lagoon connecting to theMediterranean Seardquo Journal of Environmental Science andHealth Part A vol 49 no 9 pp 1029ndash1044 2014
[15] G M El Zokm M A Okbah and A M Younis ldquoAssessmentof heavy metals pollution using AVS-SEM and fractionationtechniques in Edku Lagoon sediments Mediterranean SeaEgyptrdquo Journal of Environmental Science and Health PartAvol 50 no 6 pp 571ndash584 2015
[16] G M El Zokm H R Z Tadros M A Okbah andG H Ibrahim ldquoldquoEutrophication assessment using TRIX andCarlsonrsquos indices in Lake Mariout water Egyptrdquo EgyptianJournal of Aquatic Biology and Fisheries vol 22 no 5pp 331ndash349 2018
[17] N Donia ldquoLake Maryut monitoring using remote sensingrdquo inProceedings of the gypt Eighteenth International WaterTechnology Conference IWTC18 Sharm El Sheikh Abu DhabiUAE March 2015
Journal of Chemistry 17
[18] M A Khairy ldquoAssessment of priority phenolic compounds insediments from an extremely polluted coastal wetland (LakeMaryut Egypt)rdquo Environmental Monitoring and Assessmentvol 185 no 1 pp 441ndash455 2013
[19] N A El-Naggar and E A Rifaat ldquoEgyptian coastal lakes andwetlands part Imdashcharacteristics and hydrodynamicsrdquo in eHandbook of Environmental Chemistry A M Negm EdSpringer International Publishing AG Berlin Germany 2017
[20] J J Hanley and K T Koga ldquoChapter 2 ldquohalogens in terrestrialand cosmic geochemical systems abundances Geochemicalbehaviors and analytical methodsrdquordquo in e Role of Halogensin Terrestrial and Extraterrestrial Geochemical ProcessesD E Harlov and L Aranovich Eds Springer InternationalPublishing AG Berlin Germany pp 21ndash121 2018
[21] A Ghosh K Mukherjee S K Ghosh and B Saha ldquoSourcesand toxicity of fluoride in the environmentrdquo Research onChemical Intermediates vol 39 no 7 pp 2881ndash2915 2013
[22] M M Naim A A Moneer and G F El-Said ldquoPredictiveequations for the defluoridation by electrocoagulation tech-nique using bipolar aluminum electrodes in the absence andpresence of additives a multivariate studyrdquo Desalination andWater Treatment vol 57 no 14 pp 6320ndash6332 2016
[23] G F El-Said N A Shaltout M M El-Sadaawy andA M H Morsy ldquo-e precipitation of fluoride calcium andmagnesium minerals from Egyptian Mediterranean Sea coastin relation to discharged watersrdquo Desalination and WaterTreatment vol 57 no 5 pp 2113ndash2124 2016
[24] H Bureau ldquoIodine encyclopedia of geochemistry A com-prehensive reference source on the chemistry of the earthrdquo inEncyclopedia of Earth Sciences Series W M White Ed copySpringer International Publishing AG 2016
[25] F C Kupper and C J Carrano ldquoKey aspects of the iodinemetabolism in brown algae a brief critical reviewrdquo Metal-lomics vol 11 pp 756ndash764 2019
[26] R Liteplo R Gomes P Howe and H Malcolm Fluorides-Environmental Health Criteria 227 p 290 World HealthOrganization (WHO) Geneva Switzerland 2002
[27] G F El-Said and M M El-Sadaawy ldquoSeasonal variation ofboron and fluoride in Tilapia nilotica from an Egyptian fishfarm in relation to Human health hazard assessmentrdquoHumanand Ecological Risk Assessment An International Journalvol 19 no 4 pp 930ndash943 2013
[28] WHO (World Health Organization) Bromide in Drinking-Water Background Document for Development of WHOGuidelines for Drinking-Water Quality WHO Press WorldHealth Organization Geneva Switzerland 2009
[29] G F El-Said and N A Sallam ldquo-e uptake of fluorideconcentration and its effects on the growth rate of shrimps(Palaemon elegans Rathke)rdquo Chemistry and Ecology vol 24no 3 pp 191ndash205 2008
[30] X Zhang J He B He and J Sun ldquoAssessment formationmechanism and different source contributions of dissolvedsalt pollution in the shallow groundwater of Hutuo Riveralluvial-pluvial fan in the North China Plainrdquo EnvironmentalScience and Pollution Research vol 26 no 35 pp 35742ndash35756 2019
[31] Y Zhu B Huang Z Zhu et al ldquoldquoCharacterization disso-lution and solubility of the hydroxypyromorphitendashhydroxyapatite solid solution [(PbxCa1minusx)5(PO4)3OH] at25 degC and pH 2ndash9rdquo Geochemical Transactions vol 17 no 2pp 1ndash18 2016
[32] G F El-Said M M El-Sadaawy A A Moneer andN A Shaltout ldquo-e effect of fluoride on the distribution ofsome minerals in the surface water of an Egyptian lagoon at
the Mediterranean Seardquo Egyptian Journal of Aquatic Researchvol 41 no 1 pp 31ndash39 2015
[33] Y Zhu Z Zhu X Zhao Y Liang and Y Huang ldquoChar-acterization dissolution and solubility of lead hydroxypyr-omorphite [Pb5(PO4)3OH] at 25ndash45degCrdquo Journal ofChemistry vol 2015 Article ID 269387 10 pages 2015
[34] M A Z Chahouki ldquoMultivariate analysis techniques inenvironmental sciencerdquo in Earth and Environmental SciencesDr Imran Ahmad Dar Ed InTech Open London UK 2011httpwwwintechopencombooksearth-and-environmental-sciencesmultivariate-analysis-techniques-inenvironmental-science
[35] J V Klump and C S Martens ldquoBiogeochemical cycling in anorganic-rich coastal marine basin 5 Sedimentary nitrogenand phosphorus budgets based upon kinetic models massbalances and the stoichiometry of nutrient regenerationrdquoGeochimica et Cosmochimica Acta vol 51 no 5 pp 1161ndash1173 1987
[36] R L Folk Petrology of Sedimentary Rocks University of TexasAustin TX USA 1974
[37] P Saenger ldquoA rapid spectrophotometric method for thedetermination of bromine in seawater and in the ash ofmarine algaerdquo Helgolander Wissenschaftliche Meer-esuntersuchungen vol 23 no 1 pp 32ndash37 1972
[38] P G Jeffery Chemical Methods of Rock Analysis PergamonPress New York NY USA 2nd edition 1975
[39] J D H Strickland and T R Parsons ldquoA practical handbook ofseawater analysisrdquo in Fisheries Research Board of CanadaBulletin 167p 311 Second edition Wiley Ottawa Canada1972
[40] B Horvath O Opara-Nadi and F Beese ldquoA simple methodfor measuring the carbonate content of soilsrdquo Soil ScienceSociety of America Journal vol 69 no 4 pp 1066ndash1068 2005
[41] K Grasshoff Methods of Seawater Analysis p 317 VerlagChemie Weinkeim Germany 1976
[42] R Danovaro D Marrale N Della Croce P Parodi andM Fabiano ldquoBiochemical composition of sedimentary or-ganic matter and bacterial distribution in the Aegean Seatrophic state and pelagic-benthic couplingrdquo Journal of SeaResearch vol 42 no 2 pp 117ndash129 1999
[43] APHA-AWWA-WPCF (American Public Health Associa-tion) Standard Methods for the Examination of Water andWaste Water American Public Health Association Wash-ington DC USA 20th edition 1999
[44] K I Aspila H Agemian and A S Y Chau ldquoA semi-auto-mated method for the determination of inorganic organicand total phosphate in sedimentsrdquo e Analyst vol 101no 1200 pp 187ndash197 1976
[45] J P Riley and D Taylor ldquoChelating resins for the concen-tration of trace elements from sea water and their analyticaluse in conjunction with atomic absorption spectrophotom-etryrdquo Analytica Chimica Acta vol 40 pp 479ndash485 1968
[46] G F El-Said and A El-Sikaily ldquoChemical composition ofsome seaweed from Mediterranean Sea coast Egyptrdquo Envi-ronmental Monitoring and Assessment vol 185 no 7pp 6089ndash6099 2013
[47] Directorate General of Health Services Ministry of Health andFamilyWelfare Government of India ldquoManual of methods ofanalysis of foodsrdquo in Fruit and Vegetable Productsp 57Directorate General of Health Services Ministry of Health andFamily Welfare Government of India New Delhi India2005
[48] A Gunnars S Blomqvist and C Martinsson ldquoInorganicformation of apatite in brackish seawater from the Baltic Sea
18 Journal of Chemistry
an experimental approachrdquo Marine Chemistry vol 91 no 1-4 pp 15ndash26 2004
[49] W M Haynes D R Lide and T J Bruno CRC Handbook ofChemistry and Physics A Ready Reference Book of Chemicaland Physical Data CRC Press Taylor amp Frances Group BocaRaton FL USA 97th edition 2017
[50] M S Masoud M I El-Samra and M M El-Sadawy ldquoWaterchemistry of el-mex bay west of Alexandria Egyptrdquo eEgypian Science Magazine vol 2 pp 70ndash78 2005
[51] F J Millero R Feistel D G Wright and T J McDougallldquo-e composition of standard seawater and the definition ofthe reference-composition salinity scalerdquo Deep Sea ResearchPart I Oceanographic Research Papers vol 55 no 1pp 50ndash72 2008
[52] S K El-Wakeel S A Morcos and A M Mahlis ldquo-e majorcations in Lake Maryut watersrdquo Hydrobiologia vol 36 no 2pp 253ndash274 1970
[53] A M Mahlis S A Morcos and S K El-Wakeel ldquo-e majoranions in Lake Maryut watersrdquo Hydrobiologia vol 36 no 2pp 275ndash294 1970
[54] A S Saad M A Massoud R A Amer and M A GhorabldquoAssessment of the physico-chemical characteristics andwater quality analysis of Mariout Lake southern of Alexan-dria Egyptrdquo Journal of Environmental and Analytical Toxi-cology vol 7 no 1 p 421 2017
[55] R Rumuri ldquoDataset on hydrogeochemical characteristics ofgroundwater and surface water in Kattumannarkoil TalukIndiardquo Data in Brief vol 32 Article ID 106058 2020
[56] P Szefer S W Fowler K Ikuta et al ldquoA comparative as-sessment of heavy metal accumulation in soft parts and byssusof mussels from subarctic temperate subtropical and tropicalmarine environmentsrdquo Environmental Pollution vol 139no 1 pp 70ndash78 2006
[57] N F Soliman G M El Zokm and M A Okbah ldquoRisk as-sessment and chemical fractionation of selected elements insurface sediments from Lake Qarun Egypt using modifiedBCR techniquerdquo Chemosphere vol 191 pp 262ndash271 2018
[58] G M El Zokm M I A Ibrahim L A Mohamed and M El-Mamoney ldquoCritical geochemical insight into Alexandria coastwith special reference to diagnostic ratios (TOCTN amp SrCa)and heavy metals ecotoxicological hazardsrdquo Egyptian Journalof Aquatic Research vol 46 no 1 pp 27ndash33 2020
[59] A S Likuku K B Mmolawa and G K GaboutloeloeldquoAssessment of heavy metal enrichment and degree of con-tamination around the copper-nickel mine in the SelebiPhikwe Region Eastern Botswanardquo Environment and EcologyResearch vol 1 no 2 pp 32ndash40 2013
[60] M K Khalil S E O Draz G M El Zokm and G F El-SaidldquoApportionment of geochemistry texturersquos properties and riskassessment of some elements in surface sediments from Bar-dawil Lagoon Egyptrdquo Human and Ecological Risk AssessmentAn International Journal vol 22 no 3 pp 775ndash791 2016
[61] M M El-Sadaawy and G F El-Said ldquoAssessment of fluoridein three selected polluted environments along the EgyptianMediterranean Sea effects on local populationsrdquo Human andEcological Risk Assessment An International Journal vol 20no 6 pp 1643ndash1658 2014
[62] USEPA ldquoSuperfund exposure assessment manualrdquo inOSWER Directive 92855-1EPA540l-88001Office of Emer-gency and Remedial Response Washington DC USA 1988
[63] USEPA ldquoExposure factors handbookrdquo in EPA6008-89043Office of Health and Environmental Assessment Wash-ington DC USA 1989
[64] Health Canada ldquoFederal Contaminated Site Risk Assessmentin Canadardquo Part II Health Canada Toxicological ReferenceValues (TRVs) Cat H46-204-368E Calgary Health CanadaOttawa Canada 2007
[65] J Iqbal S A Tirmizi and M H Shah ldquoStatistical appor-tionment and risk assessment of selected metals in sedimentsfrom Rawal Lake (Pakistan)rdquo Environmental Monitoring andAssessment vol 185 no 1 pp 729ndash743 2013
[66] USEPA (US Environmental Protection Agency) Region 6USAEPA ldquoMultimedia Planning and Permitting DivisionrdquoOffice of Solid Waste Center for Combustion Science andEngineering Washington DC USA 2005
[67] P Jeschke ldquoLatest generation of halogen-containing pesti-cidesrdquo Pest Management Science vol 73 no 6 pp 1053ndash10662017
[68] M A Shreadah O A El-Rayis N A Shaaban andA M Hamdan ldquoWater quality assessment and phosphorusbudget of a lake (Mariut Egypt) after diversion of wastewaterseffluentsrdquo Environmental Science and Pollution Researchvol 27 no 21 pp 26786ndash26799 2020
[69] J P Riley and M Tongudai ldquo-e major cationchlorinityratios in sea waterrdquo Chemical Geology vol 2 pp 263ndash2691967
[70] R B McCleskey D K Nordstrom D D Susong J W Balland J M Holloway ldquoSource and fate of inorganic solutes inthe gibbon river yellowstone national park Wyoming USArdquoJournal of Volcanology and Geothermal Research vol 193no 3-4 pp 189ndash202 2010
[71] G T F Wong and K-Y Li ldquoWinklerrsquos method overestimatesdissolved oxygen in seawater iodate interference and itsoceanographic implicationsrdquo Marine Chemistry vol 115no 1-2 pp 86ndash91 2009
[72] B S R V Prasad P D N Srinivasu P S VarmaA V Raman and S Ray ldquoDynamics of dissolved oxygen inrelation to saturation and health of an aquatic body a case forChilka Lagoon Indiardquo Journal of Ecosystems vol 2014 Ar-ticle ID 526245 17 pages 2014
[73] China Environmental Protection Agency EnvironmentalQuality Standards for Surface Water (GB3838ndash2002) NationalEnvironmental Protection Agency of China Beijing China2002
[74] Y Jia L Wang Z Qu and Z Yang ldquoDistribution con-tamination and accumulation of heavy metals in watersediments and freshwater shellfish from Liuyang RiverSouthern Chinardquo Environmental Science and Pollution Re-search vol 25 no 7 pp 7012ndash7020 2018
[75] A Moneer M El-Sadawy G El-Said and A Radwan ldquoBoronhuman health risk assessment relative to the environmentalpollution of Lake Edku Egyptrdquo Journal of King AbdulazizUniversity vol 23 no 2 pp 41ndash55 2012
[76] C B Tabelin T Igarashi T Arima D Sato T Tatsuhara andS Tamoto ldquoCharacterization and evaluation of arsenic andboron adsorption onto natural geologic materials and theirapplication in the disposal of excavated altered rockrdquo Geo-derma vol 213 pp 163ndash172 2014
[77] G Aloisi K Wallmann M Drews and G BohrmannldquoEvidence for the submarine weathering of silicate minerals inBlack Sea sediments possible implications for the marine Liand B cyclesrdquo Geochemistry Geophysics Geosystems vol 5no 4 pp 1ndash22 2004
[78] C Degueldre and V Cloet ldquoPore water colloid properties inargillaceous sedimentary rocksrdquo Science of e Total Envi-ronment vol 569-570 pp 423ndash433 2016
Journal of Chemistry 19
[79] J A Higgins and D P Schrag ldquoRecords of Neogene seawaterchemistry and diagenesis in deep-sea carbonate sedimentsand pore fluidsrdquo Earth and Planetary Science Letters vol 357-358 pp 386ndash396 2012
[80] H Schroeder A-L Fabricius D Ecker T A Ternes andL Duester ldquoMetal(loid) speciation and size fractionation insediment pore water depth profiles examined with a newmesoprofiling systemrdquo Chemosphere vol 179 pp 185ndash193 2017
[81] Y Song and G Muller ldquoFreshwater sediments sinks andsources of brominerdquo Naturwissenschaften vol 80 no 12pp 558ndash560 1993
[82] M E Goher H I Farhat M H Abdo and S G Salem ldquoMetalpollution assessment in the surface sediment of Lake NasserEgyptrdquo Egyptian Journal of Aquatic Research vol 40 no 3pp 213ndash224 2014
[83] G F El-Said M M El-Sadawy and A A Moneer ldquoIncor-poration of fluoride and boron into surface sediments alongthe Egyptian Mediterranean coastrdquo Egyptian Journal ofAquatic Research vol 36 no 4 pp 569ndash583 2010
[84] B Gilfedder G M Petri M Wessels and H Biester ldquoAniodine mass-balance for Lake Constance Germany insightsinto iodine speciation changes and fluxesrdquo Geochimica etCosmochimica Acta vol 74 no 11 pp 3090ndash3111 2010
[85] E Korobova L Kolmykova B Ryzhenko et al ldquoDistributionand speciation of iodine in drinking waters from geochem-ically different areas of Bryansk region contaminated after theChernobyl accident in relation to health and remediationaspectsrdquo Journal of Geochemical Exploration vol 184pp 311ndash317 2018
[86] V Zic V W Truesdale and N Cukrov ldquo-e distribution ofiodide and iodate in anchialine cave watersmdashevidence forsustained localised oxidation of iodide to iodate in marinewaterrdquoMarine Chemistry vol 112 no 3-4 pp 168ndash178 2008
[87] M B Heeb J Criquet S G Zimmermann-Steffens andU Von Gunten ldquoOxidative treatment of bromide-containingwaters formation of bromine and its reactions with inorganicand organic compoundsmdasha critical reviewrdquo Water Researchvol 48 pp 15ndash42 2014
[88] V Sivasankar A K Darchen and R Omine SakthivelldquoChapter 2 ldquofluoride a world ubiquitous compound itschemistry and ways of contaminationrdquo in Surface ModifiedCarbons as Scavengers for Fluoride fromWater V SivasankarEd pp 5ndash32 copy Springer International Publishing Switzer-land Cham Switzerland 2016
[89] O Cabestrero P Del Buey and M E Sanz-Montero ldquoBio-sedimentary and geochemical constraints on the precipitationof mineral crusts in shallow sulphate lakesrdquo SedimentaryGeology vol 366 pp 32ndash46 2018
[90] M A Hassaan O A El-Rayis and E I Hemada ldquoEstimationof the redox potential of lake mariut drainage system (Qalaaand Umum drains)rdquoHydrology vol 5 no 6 pp 82ndash85 2017
20 Journal of Chemistry
Minerals and precipitated salts in the different partitions(surface water pore water and sediment) play an importantrole in the deposition and release of halogens in sedimentsAdditionally the texture and the porosity of the sedimentsplay a key role in the distribution of halogens in the threepartitions Interestingly chloride is the only halogen that hasnegligible interactions along the surface water and porewater partitions because it is present in large quantities inthe form of soluble salts (NaCl and MgCl2)
37 Pollution Status
371 Enrichment Factor (EF) Twowell-knownmethods areused to assess environmental pollution public health sig-nificance of ingestion and dermal contact with water andsediment components and sediment enrichment factor (EF)[59 60]
-e average EF values of the determined elements CaMg Na K Li B P Cu Zn Mn Fe F Cl Br and I are alllower than the value that is less than the minimum en-richment value (EFlt 2)-us the area under investigation isstill ecologically considered as an unpolluted region
372 Human Health Risk Assessment -e EDI HQ and HIshow the variable values of all pollutants in the surface waterand sediments along the lake region and in drains (sites11ndash13) under study Among all the calculated variables ofsurface water ingestion (EDIIngw) and dermal contact(EDIDermw) Cl is still the only variable that shows high levels(average 1551 and 43mg kgminus1 dayminus1 respectively) -eestimation daily intake of sediment ingestion (EDIIngs) anddermal contact (EDIDerms) of Mg Ca and Na give maximumaverage amounts of 841Eminus 02 513E ndash 02 and167Eminus 03mg kgminus1 dayminus1 respectively
Among the HQ of the calculated detection variables thecontent of HQB of ingestion and dermal contact with waterand sediment is the highest However 70 of sites have HQBvalues more than 10 (Figure 5) Comparing the HQ values ofall the determined variables HQB of the ingestion of surfacewater shows values higher (gt10) However due to the impactof drainage the HQB values of stations 1ndash4 8ndash10 12 and 13
are higher than 10 -erefore these sites can be consideredas the area with the most serious boron pollution caused byuntreated discharged water disposal In addition the HIIngwlevel of water ingestion for the studied variables in all sites ismuch higher than 10 (Figure 6) Except for boron it isusually concluded that the study area does not pose any riskto the population due to halogens or other variables Ac-cordingly this information may help the official authoritiesoptimize management plans and strengthen their pollutioncontrol actions in Lake Mariout
4 Conclusions
-e effects of halogen salts and minerals on the pollution ofLake Mariout were studied Halogens and some physico-chemical variables in three partitions surface water porewater and sediment in Lake Mariout were evaluated -ehalogen content was variable between different sites andchloride was the main halogen in surface water and porewater but it was very rare in the lakersquos sediment partitionPiper ternary diagram and Palmerrsquos method reflected thatNaCl was the dominant salt in surface water while MgCl2was the main dissolve salt in pore water-e chlorinity ratiosof halogens and tested variables were directly matched to thefeeding drain sources
Moreover the Saturation Index (SI) reveals that 23 and 15precipitated salts and minerals are formed in surface water andpore water respectively -e SI value indicated the formationof phosphate minerals in surface water and pore water es-pecially octacalcium phosphate (OCP Ca4H(PO4)325H2O)and hydroxyapatite (HAP Ca5(PO4)3OH) In addition tofluoride minerals especially fluorapatite (FAP) and carbonate-fluorapatite (CFAP) were obviously precipitated from surfacewater and pore water Soluble salts of bromide and chloridewere formed in surface water and pore water Iodide salts(Ca(IO3)2 and Ca(IO3)26H2O) were moderately precipitatedin the surface water and pore water
Moreover the multivariate analysis including the cor-relation matrix multiple stepwise linear regression treeclustering and principle component (PCA) of all the de-termined and calculated variables was applied to estimatethe proposed interaction between halogens and other tested
10E + 02
16E + 0214E + 0212E + 02
80E + 0160E + 0140E + 0120E + 0100E + 00
1 2 3 4 5 6 7 8 9 10 11 12 13
HIIngHIDerm
(a)
1 2 3 4 5 6 7 8 9 10 11 12 13
HIIngHIDerm
40E ndash 0235E ndash 0230E ndash 0225E ndash 0220E ndash 0215E ndash 0210E ndash 0250E ndash 0300E + 01
(b)
Figure 6 Hazard index of ingestion and dermal contact of the studied variables in surface water and sediment of Lake Mariout (a) waterand (b) sediment
16 Journal of Chemistry
variables in the polluted area under study -e multivariateanalysis showed that there were many interactions betweenhalogens and tested variables High levels of fluoride bro-mide and chloride in surface water were related to thecomposition of drainage waters -e enrichment factor (EF)showed that Lake Mariout was not polluted However thehuman health adverse effects calculated for surface waterand sediment did not reflect any possible likelihood hazardeffects from halogens
Interestingly the current study concluded that halogencompounds especially fluorides are most likely to be de-posited from surface lakes in the form of many minerals andprecipitation thereby reducing the adverse pollution effectson human health -e results obtained through this workhelp to find the correlations between the sampling sites andthe variables obtained by physical and chemical measure-ments which can be used to construct a fast decision modelfor separating different water quality samples -is infor-mation may help the official authorities optimize manage-ment plans and strengthen their pollution control measuresin Lake Mariout
Data Availability
-e data used to support the findings of this research areincluded within the paper
Conflicts of Interest
-e authors declare that there are no conflicts of interestregarding the publication of this manuscript
Supplementary Materials
Supplementary Table 1 correlation matrix of variable insurface water pore water and sediment partitions besidesthe precipitated salts in surface water along Lake Mariout(Supplementary Materials)
References
[1] M S Masoud T O Said G El-Zokm and M A ShreadahldquoAssesment of heavy metals contamination in surface sedi-ments of the Egyptian Red Sea Coastsrdquo Australian Journal ofBasic and Applied Sciences vol 6 pp 44ndash58 2012
[2] M A Shreadah M I Abdel Moneim T O SaidE M I Fathallah and M E Mahmoud ldquoPAHs in seawater ofthe semi-closed areas along the Alexandria coast of EgyptianMediterranean seardquo Journal of Environmental Protectionvol 4 no 11 p 11 Article ID 40298 2013
[3] S Abdel Ghani G El Zokm A Shobier T Othman andM Shreadah ldquoMetal pollution in surface sediments of Abu-Qir bay and Eastern harbour of Alexandria Egyptrdquo EgyptianJournal of Aquatic Research vol 39 no 1 pp 1ndash12 2013
[4] G F El-Said ldquoBioaccumulation of key metals and othercontaminants by seaweeds from the Egyptian MediterraneanSea Coast in relation to human health riskrdquo Human andEcological Risk Assessment An International Journal vol 19no 5 pp 1285ndash1305 2013
[5] M A Shreadah A H Shobier S Abdel Ghani G M El-Zokm and T O Said ldquoMajor ions anomalies and
contamination status by trace metals in sediments from twohot spots along the Mediterranean Coast of Egyptrdquo Envi-ronmental Monitoring and Assessment vol 187 no 280pp 1ndash18 2015
[6] A El Nemr G F El-Said A Khaled and S Ragab ldquoDis-tribution and ecological risk assessment of some heavy metalsin coastal surface sediments along the Red Sea Egyptrdquo In-ternational Journal of Sediment Research vol 31 no 2pp 164ndash172 2016
[7] A El Nemr G F El-Said S Ragab A Khaled and A El-Sikaily ldquo-e distribution contamination and risk assessmentof heavy metals in sediment and shellfish from the Red Seacoast Egyptrdquo Chemosphere vol 165 pp 369ndash380 2016
[8] A El Nemr and G F El-Said ldquoAssessment and ecological riskof heavy metals in sediment and molluscs from the Medi-terranean coastrdquo Water Environment Research vol 89 no 3pp 195ndash210 2017
[9] M A Sheradah A A El-Sikaily N M Abd El MoneamN E Abd El Maguid and M G Zaki ldquoChemical and bio-chemical evaluation of marine pollution by polychlorinatedbiphenyls and pesticides in two regions along the EgyptianMediterranean Seardquo International Journal of EnvironmentalMonitoring and Analysis vol 6 no 3 pp 95ndash109 2018
[10] M A Shreadah A A-M M El-Sayed A A S TahaA-M M Ahmed and H H Abdel Rahman ldquoEvaluation ofdifferent anthropogenic effluents impacts on the water qualityusing principal component analysis a case study of Abu-QirBay-Alexandria-Egyptrdquo International Journal of Environ-mental Monitoring and Analysis vol 7 no 3 pp 56ndash67 2019
[11] G F El-Said M M El-Sadaawy A H Shobier andS E Ramadan ldquoHuman health implication of major and traceelements present in commercial crustaceans of a traditionalseafood marketing region Egyptrdquo Biological Trace ElementResearch vol 199 pp 315ndash328 2020
[12] M A Shreadah S A A Ghani H B I HawashA A E Samie and A E M M Ahmed ldquoOrganotin com-pounds in sediments of northern lakes Egyptrdquo Journal ofEnvironmental Protection vol 05 no 17 pp 1654ndash1666 2014
[13] A M Younis G M El-Zokm and M A Okbah ldquoSpatialvariation of acid-volatile sulfide and simultaneously extractedmetals in Egyptian Mediterranean Sea lagoon sedimentsrdquoEnvironmental Monitoring and Assessment vol 186 no 6pp 3567ndash3579 2014
[14] G F El-Said S E O Draz M M El-Sadaawy andA A Moneer ldquoSedimentology geochemistry pollution statusand ecological risk assessment of some heavy metals insurficial sediments of an Egyptian lagoon connecting to theMediterranean Seardquo Journal of Environmental Science andHealth Part A vol 49 no 9 pp 1029ndash1044 2014
[15] G M El Zokm M A Okbah and A M Younis ldquoAssessmentof heavy metals pollution using AVS-SEM and fractionationtechniques in Edku Lagoon sediments Mediterranean SeaEgyptrdquo Journal of Environmental Science and Health PartAvol 50 no 6 pp 571ndash584 2015
[16] G M El Zokm H R Z Tadros M A Okbah andG H Ibrahim ldquoldquoEutrophication assessment using TRIX andCarlsonrsquos indices in Lake Mariout water Egyptrdquo EgyptianJournal of Aquatic Biology and Fisheries vol 22 no 5pp 331ndash349 2018
[17] N Donia ldquoLake Maryut monitoring using remote sensingrdquo inProceedings of the gypt Eighteenth International WaterTechnology Conference IWTC18 Sharm El Sheikh Abu DhabiUAE March 2015
Journal of Chemistry 17
[18] M A Khairy ldquoAssessment of priority phenolic compounds insediments from an extremely polluted coastal wetland (LakeMaryut Egypt)rdquo Environmental Monitoring and Assessmentvol 185 no 1 pp 441ndash455 2013
[19] N A El-Naggar and E A Rifaat ldquoEgyptian coastal lakes andwetlands part Imdashcharacteristics and hydrodynamicsrdquo in eHandbook of Environmental Chemistry A M Negm EdSpringer International Publishing AG Berlin Germany 2017
[20] J J Hanley and K T Koga ldquoChapter 2 ldquohalogens in terrestrialand cosmic geochemical systems abundances Geochemicalbehaviors and analytical methodsrdquordquo in e Role of Halogensin Terrestrial and Extraterrestrial Geochemical ProcessesD E Harlov and L Aranovich Eds Springer InternationalPublishing AG Berlin Germany pp 21ndash121 2018
[21] A Ghosh K Mukherjee S K Ghosh and B Saha ldquoSourcesand toxicity of fluoride in the environmentrdquo Research onChemical Intermediates vol 39 no 7 pp 2881ndash2915 2013
[22] M M Naim A A Moneer and G F El-Said ldquoPredictiveequations for the defluoridation by electrocoagulation tech-nique using bipolar aluminum electrodes in the absence andpresence of additives a multivariate studyrdquo Desalination andWater Treatment vol 57 no 14 pp 6320ndash6332 2016
[23] G F El-Said N A Shaltout M M El-Sadaawy andA M H Morsy ldquo-e precipitation of fluoride calcium andmagnesium minerals from Egyptian Mediterranean Sea coastin relation to discharged watersrdquo Desalination and WaterTreatment vol 57 no 5 pp 2113ndash2124 2016
[24] H Bureau ldquoIodine encyclopedia of geochemistry A com-prehensive reference source on the chemistry of the earthrdquo inEncyclopedia of Earth Sciences Series W M White Ed copySpringer International Publishing AG 2016
[25] F C Kupper and C J Carrano ldquoKey aspects of the iodinemetabolism in brown algae a brief critical reviewrdquo Metal-lomics vol 11 pp 756ndash764 2019
[26] R Liteplo R Gomes P Howe and H Malcolm Fluorides-Environmental Health Criteria 227 p 290 World HealthOrganization (WHO) Geneva Switzerland 2002
[27] G F El-Said and M M El-Sadaawy ldquoSeasonal variation ofboron and fluoride in Tilapia nilotica from an Egyptian fishfarm in relation to Human health hazard assessmentrdquoHumanand Ecological Risk Assessment An International Journalvol 19 no 4 pp 930ndash943 2013
[28] WHO (World Health Organization) Bromide in Drinking-Water Background Document for Development of WHOGuidelines for Drinking-Water Quality WHO Press WorldHealth Organization Geneva Switzerland 2009
[29] G F El-Said and N A Sallam ldquo-e uptake of fluorideconcentration and its effects on the growth rate of shrimps(Palaemon elegans Rathke)rdquo Chemistry and Ecology vol 24no 3 pp 191ndash205 2008
[30] X Zhang J He B He and J Sun ldquoAssessment formationmechanism and different source contributions of dissolvedsalt pollution in the shallow groundwater of Hutuo Riveralluvial-pluvial fan in the North China Plainrdquo EnvironmentalScience and Pollution Research vol 26 no 35 pp 35742ndash35756 2019
[31] Y Zhu B Huang Z Zhu et al ldquoldquoCharacterization disso-lution and solubility of the hydroxypyromorphitendashhydroxyapatite solid solution [(PbxCa1minusx)5(PO4)3OH] at25 degC and pH 2ndash9rdquo Geochemical Transactions vol 17 no 2pp 1ndash18 2016
[32] G F El-Said M M El-Sadaawy A A Moneer andN A Shaltout ldquo-e effect of fluoride on the distribution ofsome minerals in the surface water of an Egyptian lagoon at
the Mediterranean Seardquo Egyptian Journal of Aquatic Researchvol 41 no 1 pp 31ndash39 2015
[33] Y Zhu Z Zhu X Zhao Y Liang and Y Huang ldquoChar-acterization dissolution and solubility of lead hydroxypyr-omorphite [Pb5(PO4)3OH] at 25ndash45degCrdquo Journal ofChemistry vol 2015 Article ID 269387 10 pages 2015
[34] M A Z Chahouki ldquoMultivariate analysis techniques inenvironmental sciencerdquo in Earth and Environmental SciencesDr Imran Ahmad Dar Ed InTech Open London UK 2011httpwwwintechopencombooksearth-and-environmental-sciencesmultivariate-analysis-techniques-inenvironmental-science
[35] J V Klump and C S Martens ldquoBiogeochemical cycling in anorganic-rich coastal marine basin 5 Sedimentary nitrogenand phosphorus budgets based upon kinetic models massbalances and the stoichiometry of nutrient regenerationrdquoGeochimica et Cosmochimica Acta vol 51 no 5 pp 1161ndash1173 1987
[36] R L Folk Petrology of Sedimentary Rocks University of TexasAustin TX USA 1974
[37] P Saenger ldquoA rapid spectrophotometric method for thedetermination of bromine in seawater and in the ash ofmarine algaerdquo Helgolander Wissenschaftliche Meer-esuntersuchungen vol 23 no 1 pp 32ndash37 1972
[38] P G Jeffery Chemical Methods of Rock Analysis PergamonPress New York NY USA 2nd edition 1975
[39] J D H Strickland and T R Parsons ldquoA practical handbook ofseawater analysisrdquo in Fisheries Research Board of CanadaBulletin 167p 311 Second edition Wiley Ottawa Canada1972
[40] B Horvath O Opara-Nadi and F Beese ldquoA simple methodfor measuring the carbonate content of soilsrdquo Soil ScienceSociety of America Journal vol 69 no 4 pp 1066ndash1068 2005
[41] K Grasshoff Methods of Seawater Analysis p 317 VerlagChemie Weinkeim Germany 1976
[42] R Danovaro D Marrale N Della Croce P Parodi andM Fabiano ldquoBiochemical composition of sedimentary or-ganic matter and bacterial distribution in the Aegean Seatrophic state and pelagic-benthic couplingrdquo Journal of SeaResearch vol 42 no 2 pp 117ndash129 1999
[43] APHA-AWWA-WPCF (American Public Health Associa-tion) Standard Methods for the Examination of Water andWaste Water American Public Health Association Wash-ington DC USA 20th edition 1999
[44] K I Aspila H Agemian and A S Y Chau ldquoA semi-auto-mated method for the determination of inorganic organicand total phosphate in sedimentsrdquo e Analyst vol 101no 1200 pp 187ndash197 1976
[45] J P Riley and D Taylor ldquoChelating resins for the concen-tration of trace elements from sea water and their analyticaluse in conjunction with atomic absorption spectrophotom-etryrdquo Analytica Chimica Acta vol 40 pp 479ndash485 1968
[46] G F El-Said and A El-Sikaily ldquoChemical composition ofsome seaweed from Mediterranean Sea coast Egyptrdquo Envi-ronmental Monitoring and Assessment vol 185 no 7pp 6089ndash6099 2013
[47] Directorate General of Health Services Ministry of Health andFamilyWelfare Government of India ldquoManual of methods ofanalysis of foodsrdquo in Fruit and Vegetable Productsp 57Directorate General of Health Services Ministry of Health andFamily Welfare Government of India New Delhi India2005
[48] A Gunnars S Blomqvist and C Martinsson ldquoInorganicformation of apatite in brackish seawater from the Baltic Sea
18 Journal of Chemistry
an experimental approachrdquo Marine Chemistry vol 91 no 1-4 pp 15ndash26 2004
[49] W M Haynes D R Lide and T J Bruno CRC Handbook ofChemistry and Physics A Ready Reference Book of Chemicaland Physical Data CRC Press Taylor amp Frances Group BocaRaton FL USA 97th edition 2017
[50] M S Masoud M I El-Samra and M M El-Sadawy ldquoWaterchemistry of el-mex bay west of Alexandria Egyptrdquo eEgypian Science Magazine vol 2 pp 70ndash78 2005
[51] F J Millero R Feistel D G Wright and T J McDougallldquo-e composition of standard seawater and the definition ofthe reference-composition salinity scalerdquo Deep Sea ResearchPart I Oceanographic Research Papers vol 55 no 1pp 50ndash72 2008
[52] S K El-Wakeel S A Morcos and A M Mahlis ldquo-e majorcations in Lake Maryut watersrdquo Hydrobiologia vol 36 no 2pp 253ndash274 1970
[53] A M Mahlis S A Morcos and S K El-Wakeel ldquo-e majoranions in Lake Maryut watersrdquo Hydrobiologia vol 36 no 2pp 275ndash294 1970
[54] A S Saad M A Massoud R A Amer and M A GhorabldquoAssessment of the physico-chemical characteristics andwater quality analysis of Mariout Lake southern of Alexan-dria Egyptrdquo Journal of Environmental and Analytical Toxi-cology vol 7 no 1 p 421 2017
[55] R Rumuri ldquoDataset on hydrogeochemical characteristics ofgroundwater and surface water in Kattumannarkoil TalukIndiardquo Data in Brief vol 32 Article ID 106058 2020
[56] P Szefer S W Fowler K Ikuta et al ldquoA comparative as-sessment of heavy metal accumulation in soft parts and byssusof mussels from subarctic temperate subtropical and tropicalmarine environmentsrdquo Environmental Pollution vol 139no 1 pp 70ndash78 2006
[57] N F Soliman G M El Zokm and M A Okbah ldquoRisk as-sessment and chemical fractionation of selected elements insurface sediments from Lake Qarun Egypt using modifiedBCR techniquerdquo Chemosphere vol 191 pp 262ndash271 2018
[58] G M El Zokm M I A Ibrahim L A Mohamed and M El-Mamoney ldquoCritical geochemical insight into Alexandria coastwith special reference to diagnostic ratios (TOCTN amp SrCa)and heavy metals ecotoxicological hazardsrdquo Egyptian Journalof Aquatic Research vol 46 no 1 pp 27ndash33 2020
[59] A S Likuku K B Mmolawa and G K GaboutloeloeldquoAssessment of heavy metal enrichment and degree of con-tamination around the copper-nickel mine in the SelebiPhikwe Region Eastern Botswanardquo Environment and EcologyResearch vol 1 no 2 pp 32ndash40 2013
[60] M K Khalil S E O Draz G M El Zokm and G F El-SaidldquoApportionment of geochemistry texturersquos properties and riskassessment of some elements in surface sediments from Bar-dawil Lagoon Egyptrdquo Human and Ecological Risk AssessmentAn International Journal vol 22 no 3 pp 775ndash791 2016
[61] M M El-Sadaawy and G F El-Said ldquoAssessment of fluoridein three selected polluted environments along the EgyptianMediterranean Sea effects on local populationsrdquo Human andEcological Risk Assessment An International Journal vol 20no 6 pp 1643ndash1658 2014
[62] USEPA ldquoSuperfund exposure assessment manualrdquo inOSWER Directive 92855-1EPA540l-88001Office of Emer-gency and Remedial Response Washington DC USA 1988
[63] USEPA ldquoExposure factors handbookrdquo in EPA6008-89043Office of Health and Environmental Assessment Wash-ington DC USA 1989
[64] Health Canada ldquoFederal Contaminated Site Risk Assessmentin Canadardquo Part II Health Canada Toxicological ReferenceValues (TRVs) Cat H46-204-368E Calgary Health CanadaOttawa Canada 2007
[65] J Iqbal S A Tirmizi and M H Shah ldquoStatistical appor-tionment and risk assessment of selected metals in sedimentsfrom Rawal Lake (Pakistan)rdquo Environmental Monitoring andAssessment vol 185 no 1 pp 729ndash743 2013
[66] USEPA (US Environmental Protection Agency) Region 6USAEPA ldquoMultimedia Planning and Permitting DivisionrdquoOffice of Solid Waste Center for Combustion Science andEngineering Washington DC USA 2005
[67] P Jeschke ldquoLatest generation of halogen-containing pesti-cidesrdquo Pest Management Science vol 73 no 6 pp 1053ndash10662017
[68] M A Shreadah O A El-Rayis N A Shaaban andA M Hamdan ldquoWater quality assessment and phosphorusbudget of a lake (Mariut Egypt) after diversion of wastewaterseffluentsrdquo Environmental Science and Pollution Researchvol 27 no 21 pp 26786ndash26799 2020
[69] J P Riley and M Tongudai ldquo-e major cationchlorinityratios in sea waterrdquo Chemical Geology vol 2 pp 263ndash2691967
[70] R B McCleskey D K Nordstrom D D Susong J W Balland J M Holloway ldquoSource and fate of inorganic solutes inthe gibbon river yellowstone national park Wyoming USArdquoJournal of Volcanology and Geothermal Research vol 193no 3-4 pp 189ndash202 2010
[71] G T F Wong and K-Y Li ldquoWinklerrsquos method overestimatesdissolved oxygen in seawater iodate interference and itsoceanographic implicationsrdquo Marine Chemistry vol 115no 1-2 pp 86ndash91 2009
[72] B S R V Prasad P D N Srinivasu P S VarmaA V Raman and S Ray ldquoDynamics of dissolved oxygen inrelation to saturation and health of an aquatic body a case forChilka Lagoon Indiardquo Journal of Ecosystems vol 2014 Ar-ticle ID 526245 17 pages 2014
[73] China Environmental Protection Agency EnvironmentalQuality Standards for Surface Water (GB3838ndash2002) NationalEnvironmental Protection Agency of China Beijing China2002
[74] Y Jia L Wang Z Qu and Z Yang ldquoDistribution con-tamination and accumulation of heavy metals in watersediments and freshwater shellfish from Liuyang RiverSouthern Chinardquo Environmental Science and Pollution Re-search vol 25 no 7 pp 7012ndash7020 2018
[75] A Moneer M El-Sadawy G El-Said and A Radwan ldquoBoronhuman health risk assessment relative to the environmentalpollution of Lake Edku Egyptrdquo Journal of King AbdulazizUniversity vol 23 no 2 pp 41ndash55 2012
[76] C B Tabelin T Igarashi T Arima D Sato T Tatsuhara andS Tamoto ldquoCharacterization and evaluation of arsenic andboron adsorption onto natural geologic materials and theirapplication in the disposal of excavated altered rockrdquo Geo-derma vol 213 pp 163ndash172 2014
[77] G Aloisi K Wallmann M Drews and G BohrmannldquoEvidence for the submarine weathering of silicate minerals inBlack Sea sediments possible implications for the marine Liand B cyclesrdquo Geochemistry Geophysics Geosystems vol 5no 4 pp 1ndash22 2004
[78] C Degueldre and V Cloet ldquoPore water colloid properties inargillaceous sedimentary rocksrdquo Science of e Total Envi-ronment vol 569-570 pp 423ndash433 2016
Journal of Chemistry 19
[79] J A Higgins and D P Schrag ldquoRecords of Neogene seawaterchemistry and diagenesis in deep-sea carbonate sedimentsand pore fluidsrdquo Earth and Planetary Science Letters vol 357-358 pp 386ndash396 2012
[80] H Schroeder A-L Fabricius D Ecker T A Ternes andL Duester ldquoMetal(loid) speciation and size fractionation insediment pore water depth profiles examined with a newmesoprofiling systemrdquo Chemosphere vol 179 pp 185ndash193 2017
[81] Y Song and G Muller ldquoFreshwater sediments sinks andsources of brominerdquo Naturwissenschaften vol 80 no 12pp 558ndash560 1993
[82] M E Goher H I Farhat M H Abdo and S G Salem ldquoMetalpollution assessment in the surface sediment of Lake NasserEgyptrdquo Egyptian Journal of Aquatic Research vol 40 no 3pp 213ndash224 2014
[83] G F El-Said M M El-Sadawy and A A Moneer ldquoIncor-poration of fluoride and boron into surface sediments alongthe Egyptian Mediterranean coastrdquo Egyptian Journal ofAquatic Research vol 36 no 4 pp 569ndash583 2010
[84] B Gilfedder G M Petri M Wessels and H Biester ldquoAniodine mass-balance for Lake Constance Germany insightsinto iodine speciation changes and fluxesrdquo Geochimica etCosmochimica Acta vol 74 no 11 pp 3090ndash3111 2010
[85] E Korobova L Kolmykova B Ryzhenko et al ldquoDistributionand speciation of iodine in drinking waters from geochem-ically different areas of Bryansk region contaminated after theChernobyl accident in relation to health and remediationaspectsrdquo Journal of Geochemical Exploration vol 184pp 311ndash317 2018
[86] V Zic V W Truesdale and N Cukrov ldquo-e distribution ofiodide and iodate in anchialine cave watersmdashevidence forsustained localised oxidation of iodide to iodate in marinewaterrdquoMarine Chemistry vol 112 no 3-4 pp 168ndash178 2008
[87] M B Heeb J Criquet S G Zimmermann-Steffens andU Von Gunten ldquoOxidative treatment of bromide-containingwaters formation of bromine and its reactions with inorganicand organic compoundsmdasha critical reviewrdquo Water Researchvol 48 pp 15ndash42 2014
[88] V Sivasankar A K Darchen and R Omine SakthivelldquoChapter 2 ldquofluoride a world ubiquitous compound itschemistry and ways of contaminationrdquo in Surface ModifiedCarbons as Scavengers for Fluoride fromWater V SivasankarEd pp 5ndash32 copy Springer International Publishing Switzer-land Cham Switzerland 2016
[89] O Cabestrero P Del Buey and M E Sanz-Montero ldquoBio-sedimentary and geochemical constraints on the precipitationof mineral crusts in shallow sulphate lakesrdquo SedimentaryGeology vol 366 pp 32ndash46 2018
[90] M A Hassaan O A El-Rayis and E I Hemada ldquoEstimationof the redox potential of lake mariut drainage system (Qalaaand Umum drains)rdquoHydrology vol 5 no 6 pp 82ndash85 2017
20 Journal of Chemistry
variables in the polluted area under study -e multivariateanalysis showed that there were many interactions betweenhalogens and tested variables High levels of fluoride bro-mide and chloride in surface water were related to thecomposition of drainage waters -e enrichment factor (EF)showed that Lake Mariout was not polluted However thehuman health adverse effects calculated for surface waterand sediment did not reflect any possible likelihood hazardeffects from halogens
Interestingly the current study concluded that halogencompounds especially fluorides are most likely to be de-posited from surface lakes in the form of many minerals andprecipitation thereby reducing the adverse pollution effectson human health -e results obtained through this workhelp to find the correlations between the sampling sites andthe variables obtained by physical and chemical measure-ments which can be used to construct a fast decision modelfor separating different water quality samples -is infor-mation may help the official authorities optimize manage-ment plans and strengthen their pollution control measuresin Lake Mariout
Data Availability
-e data used to support the findings of this research areincluded within the paper
Conflicts of Interest
-e authors declare that there are no conflicts of interestregarding the publication of this manuscript
Supplementary Materials
Supplementary Table 1 correlation matrix of variable insurface water pore water and sediment partitions besidesthe precipitated salts in surface water along Lake Mariout(Supplementary Materials)
References
[1] M S Masoud T O Said G El-Zokm and M A ShreadahldquoAssesment of heavy metals contamination in surface sedi-ments of the Egyptian Red Sea Coastsrdquo Australian Journal ofBasic and Applied Sciences vol 6 pp 44ndash58 2012
[2] M A Shreadah M I Abdel Moneim T O SaidE M I Fathallah and M E Mahmoud ldquoPAHs in seawater ofthe semi-closed areas along the Alexandria coast of EgyptianMediterranean seardquo Journal of Environmental Protectionvol 4 no 11 p 11 Article ID 40298 2013
[3] S Abdel Ghani G El Zokm A Shobier T Othman andM Shreadah ldquoMetal pollution in surface sediments of Abu-Qir bay and Eastern harbour of Alexandria Egyptrdquo EgyptianJournal of Aquatic Research vol 39 no 1 pp 1ndash12 2013
[4] G F El-Said ldquoBioaccumulation of key metals and othercontaminants by seaweeds from the Egyptian MediterraneanSea Coast in relation to human health riskrdquo Human andEcological Risk Assessment An International Journal vol 19no 5 pp 1285ndash1305 2013
[5] M A Shreadah A H Shobier S Abdel Ghani G M El-Zokm and T O Said ldquoMajor ions anomalies and
contamination status by trace metals in sediments from twohot spots along the Mediterranean Coast of Egyptrdquo Envi-ronmental Monitoring and Assessment vol 187 no 280pp 1ndash18 2015
[6] A El Nemr G F El-Said A Khaled and S Ragab ldquoDis-tribution and ecological risk assessment of some heavy metalsin coastal surface sediments along the Red Sea Egyptrdquo In-ternational Journal of Sediment Research vol 31 no 2pp 164ndash172 2016
[7] A El Nemr G F El-Said S Ragab A Khaled and A El-Sikaily ldquo-e distribution contamination and risk assessmentof heavy metals in sediment and shellfish from the Red Seacoast Egyptrdquo Chemosphere vol 165 pp 369ndash380 2016
[8] A El Nemr and G F El-Said ldquoAssessment and ecological riskof heavy metals in sediment and molluscs from the Medi-terranean coastrdquo Water Environment Research vol 89 no 3pp 195ndash210 2017
[9] M A Sheradah A A El-Sikaily N M Abd El MoneamN E Abd El Maguid and M G Zaki ldquoChemical and bio-chemical evaluation of marine pollution by polychlorinatedbiphenyls and pesticides in two regions along the EgyptianMediterranean Seardquo International Journal of EnvironmentalMonitoring and Analysis vol 6 no 3 pp 95ndash109 2018
[10] M A Shreadah A A-M M El-Sayed A A S TahaA-M M Ahmed and H H Abdel Rahman ldquoEvaluation ofdifferent anthropogenic effluents impacts on the water qualityusing principal component analysis a case study of Abu-QirBay-Alexandria-Egyptrdquo International Journal of Environ-mental Monitoring and Analysis vol 7 no 3 pp 56ndash67 2019
[11] G F El-Said M M El-Sadaawy A H Shobier andS E Ramadan ldquoHuman health implication of major and traceelements present in commercial crustaceans of a traditionalseafood marketing region Egyptrdquo Biological Trace ElementResearch vol 199 pp 315ndash328 2020
[12] M A Shreadah S A A Ghani H B I HawashA A E Samie and A E M M Ahmed ldquoOrganotin com-pounds in sediments of northern lakes Egyptrdquo Journal ofEnvironmental Protection vol 05 no 17 pp 1654ndash1666 2014
[13] A M Younis G M El-Zokm and M A Okbah ldquoSpatialvariation of acid-volatile sulfide and simultaneously extractedmetals in Egyptian Mediterranean Sea lagoon sedimentsrdquoEnvironmental Monitoring and Assessment vol 186 no 6pp 3567ndash3579 2014
[14] G F El-Said S E O Draz M M El-Sadaawy andA A Moneer ldquoSedimentology geochemistry pollution statusand ecological risk assessment of some heavy metals insurficial sediments of an Egyptian lagoon connecting to theMediterranean Seardquo Journal of Environmental Science andHealth Part A vol 49 no 9 pp 1029ndash1044 2014
[15] G M El Zokm M A Okbah and A M Younis ldquoAssessmentof heavy metals pollution using AVS-SEM and fractionationtechniques in Edku Lagoon sediments Mediterranean SeaEgyptrdquo Journal of Environmental Science and Health PartAvol 50 no 6 pp 571ndash584 2015
[16] G M El Zokm H R Z Tadros M A Okbah andG H Ibrahim ldquoldquoEutrophication assessment using TRIX andCarlsonrsquos indices in Lake Mariout water Egyptrdquo EgyptianJournal of Aquatic Biology and Fisheries vol 22 no 5pp 331ndash349 2018
[17] N Donia ldquoLake Maryut monitoring using remote sensingrdquo inProceedings of the gypt Eighteenth International WaterTechnology Conference IWTC18 Sharm El Sheikh Abu DhabiUAE March 2015
Journal of Chemistry 17
[18] M A Khairy ldquoAssessment of priority phenolic compounds insediments from an extremely polluted coastal wetland (LakeMaryut Egypt)rdquo Environmental Monitoring and Assessmentvol 185 no 1 pp 441ndash455 2013
[19] N A El-Naggar and E A Rifaat ldquoEgyptian coastal lakes andwetlands part Imdashcharacteristics and hydrodynamicsrdquo in eHandbook of Environmental Chemistry A M Negm EdSpringer International Publishing AG Berlin Germany 2017
[20] J J Hanley and K T Koga ldquoChapter 2 ldquohalogens in terrestrialand cosmic geochemical systems abundances Geochemicalbehaviors and analytical methodsrdquordquo in e Role of Halogensin Terrestrial and Extraterrestrial Geochemical ProcessesD E Harlov and L Aranovich Eds Springer InternationalPublishing AG Berlin Germany pp 21ndash121 2018
[21] A Ghosh K Mukherjee S K Ghosh and B Saha ldquoSourcesand toxicity of fluoride in the environmentrdquo Research onChemical Intermediates vol 39 no 7 pp 2881ndash2915 2013
[22] M M Naim A A Moneer and G F El-Said ldquoPredictiveequations for the defluoridation by electrocoagulation tech-nique using bipolar aluminum electrodes in the absence andpresence of additives a multivariate studyrdquo Desalination andWater Treatment vol 57 no 14 pp 6320ndash6332 2016
[23] G F El-Said N A Shaltout M M El-Sadaawy andA M H Morsy ldquo-e precipitation of fluoride calcium andmagnesium minerals from Egyptian Mediterranean Sea coastin relation to discharged watersrdquo Desalination and WaterTreatment vol 57 no 5 pp 2113ndash2124 2016
[24] H Bureau ldquoIodine encyclopedia of geochemistry A com-prehensive reference source on the chemistry of the earthrdquo inEncyclopedia of Earth Sciences Series W M White Ed copySpringer International Publishing AG 2016
[25] F C Kupper and C J Carrano ldquoKey aspects of the iodinemetabolism in brown algae a brief critical reviewrdquo Metal-lomics vol 11 pp 756ndash764 2019
[26] R Liteplo R Gomes P Howe and H Malcolm Fluorides-Environmental Health Criteria 227 p 290 World HealthOrganization (WHO) Geneva Switzerland 2002
[27] G F El-Said and M M El-Sadaawy ldquoSeasonal variation ofboron and fluoride in Tilapia nilotica from an Egyptian fishfarm in relation to Human health hazard assessmentrdquoHumanand Ecological Risk Assessment An International Journalvol 19 no 4 pp 930ndash943 2013
[28] WHO (World Health Organization) Bromide in Drinking-Water Background Document for Development of WHOGuidelines for Drinking-Water Quality WHO Press WorldHealth Organization Geneva Switzerland 2009
[29] G F El-Said and N A Sallam ldquo-e uptake of fluorideconcentration and its effects on the growth rate of shrimps(Palaemon elegans Rathke)rdquo Chemistry and Ecology vol 24no 3 pp 191ndash205 2008
[30] X Zhang J He B He and J Sun ldquoAssessment formationmechanism and different source contributions of dissolvedsalt pollution in the shallow groundwater of Hutuo Riveralluvial-pluvial fan in the North China Plainrdquo EnvironmentalScience and Pollution Research vol 26 no 35 pp 35742ndash35756 2019
[31] Y Zhu B Huang Z Zhu et al ldquoldquoCharacterization disso-lution and solubility of the hydroxypyromorphitendashhydroxyapatite solid solution [(PbxCa1minusx)5(PO4)3OH] at25 degC and pH 2ndash9rdquo Geochemical Transactions vol 17 no 2pp 1ndash18 2016
[32] G F El-Said M M El-Sadaawy A A Moneer andN A Shaltout ldquo-e effect of fluoride on the distribution ofsome minerals in the surface water of an Egyptian lagoon at
the Mediterranean Seardquo Egyptian Journal of Aquatic Researchvol 41 no 1 pp 31ndash39 2015
[33] Y Zhu Z Zhu X Zhao Y Liang and Y Huang ldquoChar-acterization dissolution and solubility of lead hydroxypyr-omorphite [Pb5(PO4)3OH] at 25ndash45degCrdquo Journal ofChemistry vol 2015 Article ID 269387 10 pages 2015
[34] M A Z Chahouki ldquoMultivariate analysis techniques inenvironmental sciencerdquo in Earth and Environmental SciencesDr Imran Ahmad Dar Ed InTech Open London UK 2011httpwwwintechopencombooksearth-and-environmental-sciencesmultivariate-analysis-techniques-inenvironmental-science
[35] J V Klump and C S Martens ldquoBiogeochemical cycling in anorganic-rich coastal marine basin 5 Sedimentary nitrogenand phosphorus budgets based upon kinetic models massbalances and the stoichiometry of nutrient regenerationrdquoGeochimica et Cosmochimica Acta vol 51 no 5 pp 1161ndash1173 1987
[36] R L Folk Petrology of Sedimentary Rocks University of TexasAustin TX USA 1974
[37] P Saenger ldquoA rapid spectrophotometric method for thedetermination of bromine in seawater and in the ash ofmarine algaerdquo Helgolander Wissenschaftliche Meer-esuntersuchungen vol 23 no 1 pp 32ndash37 1972
[38] P G Jeffery Chemical Methods of Rock Analysis PergamonPress New York NY USA 2nd edition 1975
[39] J D H Strickland and T R Parsons ldquoA practical handbook ofseawater analysisrdquo in Fisheries Research Board of CanadaBulletin 167p 311 Second edition Wiley Ottawa Canada1972
[40] B Horvath O Opara-Nadi and F Beese ldquoA simple methodfor measuring the carbonate content of soilsrdquo Soil ScienceSociety of America Journal vol 69 no 4 pp 1066ndash1068 2005
[41] K Grasshoff Methods of Seawater Analysis p 317 VerlagChemie Weinkeim Germany 1976
[42] R Danovaro D Marrale N Della Croce P Parodi andM Fabiano ldquoBiochemical composition of sedimentary or-ganic matter and bacterial distribution in the Aegean Seatrophic state and pelagic-benthic couplingrdquo Journal of SeaResearch vol 42 no 2 pp 117ndash129 1999
[43] APHA-AWWA-WPCF (American Public Health Associa-tion) Standard Methods for the Examination of Water andWaste Water American Public Health Association Wash-ington DC USA 20th edition 1999
[44] K I Aspila H Agemian and A S Y Chau ldquoA semi-auto-mated method for the determination of inorganic organicand total phosphate in sedimentsrdquo e Analyst vol 101no 1200 pp 187ndash197 1976
[45] J P Riley and D Taylor ldquoChelating resins for the concen-tration of trace elements from sea water and their analyticaluse in conjunction with atomic absorption spectrophotom-etryrdquo Analytica Chimica Acta vol 40 pp 479ndash485 1968
[46] G F El-Said and A El-Sikaily ldquoChemical composition ofsome seaweed from Mediterranean Sea coast Egyptrdquo Envi-ronmental Monitoring and Assessment vol 185 no 7pp 6089ndash6099 2013
[47] Directorate General of Health Services Ministry of Health andFamilyWelfare Government of India ldquoManual of methods ofanalysis of foodsrdquo in Fruit and Vegetable Productsp 57Directorate General of Health Services Ministry of Health andFamily Welfare Government of India New Delhi India2005
[48] A Gunnars S Blomqvist and C Martinsson ldquoInorganicformation of apatite in brackish seawater from the Baltic Sea
18 Journal of Chemistry
an experimental approachrdquo Marine Chemistry vol 91 no 1-4 pp 15ndash26 2004
[49] W M Haynes D R Lide and T J Bruno CRC Handbook ofChemistry and Physics A Ready Reference Book of Chemicaland Physical Data CRC Press Taylor amp Frances Group BocaRaton FL USA 97th edition 2017
[50] M S Masoud M I El-Samra and M M El-Sadawy ldquoWaterchemistry of el-mex bay west of Alexandria Egyptrdquo eEgypian Science Magazine vol 2 pp 70ndash78 2005
[51] F J Millero R Feistel D G Wright and T J McDougallldquo-e composition of standard seawater and the definition ofthe reference-composition salinity scalerdquo Deep Sea ResearchPart I Oceanographic Research Papers vol 55 no 1pp 50ndash72 2008
[52] S K El-Wakeel S A Morcos and A M Mahlis ldquo-e majorcations in Lake Maryut watersrdquo Hydrobiologia vol 36 no 2pp 253ndash274 1970
[53] A M Mahlis S A Morcos and S K El-Wakeel ldquo-e majoranions in Lake Maryut watersrdquo Hydrobiologia vol 36 no 2pp 275ndash294 1970
[54] A S Saad M A Massoud R A Amer and M A GhorabldquoAssessment of the physico-chemical characteristics andwater quality analysis of Mariout Lake southern of Alexan-dria Egyptrdquo Journal of Environmental and Analytical Toxi-cology vol 7 no 1 p 421 2017
[55] R Rumuri ldquoDataset on hydrogeochemical characteristics ofgroundwater and surface water in Kattumannarkoil TalukIndiardquo Data in Brief vol 32 Article ID 106058 2020
[56] P Szefer S W Fowler K Ikuta et al ldquoA comparative as-sessment of heavy metal accumulation in soft parts and byssusof mussels from subarctic temperate subtropical and tropicalmarine environmentsrdquo Environmental Pollution vol 139no 1 pp 70ndash78 2006
[57] N F Soliman G M El Zokm and M A Okbah ldquoRisk as-sessment and chemical fractionation of selected elements insurface sediments from Lake Qarun Egypt using modifiedBCR techniquerdquo Chemosphere vol 191 pp 262ndash271 2018
[58] G M El Zokm M I A Ibrahim L A Mohamed and M El-Mamoney ldquoCritical geochemical insight into Alexandria coastwith special reference to diagnostic ratios (TOCTN amp SrCa)and heavy metals ecotoxicological hazardsrdquo Egyptian Journalof Aquatic Research vol 46 no 1 pp 27ndash33 2020
[59] A S Likuku K B Mmolawa and G K GaboutloeloeldquoAssessment of heavy metal enrichment and degree of con-tamination around the copper-nickel mine in the SelebiPhikwe Region Eastern Botswanardquo Environment and EcologyResearch vol 1 no 2 pp 32ndash40 2013
[60] M K Khalil S E O Draz G M El Zokm and G F El-SaidldquoApportionment of geochemistry texturersquos properties and riskassessment of some elements in surface sediments from Bar-dawil Lagoon Egyptrdquo Human and Ecological Risk AssessmentAn International Journal vol 22 no 3 pp 775ndash791 2016
[61] M M El-Sadaawy and G F El-Said ldquoAssessment of fluoridein three selected polluted environments along the EgyptianMediterranean Sea effects on local populationsrdquo Human andEcological Risk Assessment An International Journal vol 20no 6 pp 1643ndash1658 2014
[62] USEPA ldquoSuperfund exposure assessment manualrdquo inOSWER Directive 92855-1EPA540l-88001Office of Emer-gency and Remedial Response Washington DC USA 1988
[63] USEPA ldquoExposure factors handbookrdquo in EPA6008-89043Office of Health and Environmental Assessment Wash-ington DC USA 1989
[64] Health Canada ldquoFederal Contaminated Site Risk Assessmentin Canadardquo Part II Health Canada Toxicological ReferenceValues (TRVs) Cat H46-204-368E Calgary Health CanadaOttawa Canada 2007
[65] J Iqbal S A Tirmizi and M H Shah ldquoStatistical appor-tionment and risk assessment of selected metals in sedimentsfrom Rawal Lake (Pakistan)rdquo Environmental Monitoring andAssessment vol 185 no 1 pp 729ndash743 2013
[66] USEPA (US Environmental Protection Agency) Region 6USAEPA ldquoMultimedia Planning and Permitting DivisionrdquoOffice of Solid Waste Center for Combustion Science andEngineering Washington DC USA 2005
[67] P Jeschke ldquoLatest generation of halogen-containing pesti-cidesrdquo Pest Management Science vol 73 no 6 pp 1053ndash10662017
[68] M A Shreadah O A El-Rayis N A Shaaban andA M Hamdan ldquoWater quality assessment and phosphorusbudget of a lake (Mariut Egypt) after diversion of wastewaterseffluentsrdquo Environmental Science and Pollution Researchvol 27 no 21 pp 26786ndash26799 2020
[69] J P Riley and M Tongudai ldquo-e major cationchlorinityratios in sea waterrdquo Chemical Geology vol 2 pp 263ndash2691967
[70] R B McCleskey D K Nordstrom D D Susong J W Balland J M Holloway ldquoSource and fate of inorganic solutes inthe gibbon river yellowstone national park Wyoming USArdquoJournal of Volcanology and Geothermal Research vol 193no 3-4 pp 189ndash202 2010
[71] G T F Wong and K-Y Li ldquoWinklerrsquos method overestimatesdissolved oxygen in seawater iodate interference and itsoceanographic implicationsrdquo Marine Chemistry vol 115no 1-2 pp 86ndash91 2009
[72] B S R V Prasad P D N Srinivasu P S VarmaA V Raman and S Ray ldquoDynamics of dissolved oxygen inrelation to saturation and health of an aquatic body a case forChilka Lagoon Indiardquo Journal of Ecosystems vol 2014 Ar-ticle ID 526245 17 pages 2014
[73] China Environmental Protection Agency EnvironmentalQuality Standards for Surface Water (GB3838ndash2002) NationalEnvironmental Protection Agency of China Beijing China2002
[74] Y Jia L Wang Z Qu and Z Yang ldquoDistribution con-tamination and accumulation of heavy metals in watersediments and freshwater shellfish from Liuyang RiverSouthern Chinardquo Environmental Science and Pollution Re-search vol 25 no 7 pp 7012ndash7020 2018
[75] A Moneer M El-Sadawy G El-Said and A Radwan ldquoBoronhuman health risk assessment relative to the environmentalpollution of Lake Edku Egyptrdquo Journal of King AbdulazizUniversity vol 23 no 2 pp 41ndash55 2012
[76] C B Tabelin T Igarashi T Arima D Sato T Tatsuhara andS Tamoto ldquoCharacterization and evaluation of arsenic andboron adsorption onto natural geologic materials and theirapplication in the disposal of excavated altered rockrdquo Geo-derma vol 213 pp 163ndash172 2014
[77] G Aloisi K Wallmann M Drews and G BohrmannldquoEvidence for the submarine weathering of silicate minerals inBlack Sea sediments possible implications for the marine Liand B cyclesrdquo Geochemistry Geophysics Geosystems vol 5no 4 pp 1ndash22 2004
[78] C Degueldre and V Cloet ldquoPore water colloid properties inargillaceous sedimentary rocksrdquo Science of e Total Envi-ronment vol 569-570 pp 423ndash433 2016
Journal of Chemistry 19
[79] J A Higgins and D P Schrag ldquoRecords of Neogene seawaterchemistry and diagenesis in deep-sea carbonate sedimentsand pore fluidsrdquo Earth and Planetary Science Letters vol 357-358 pp 386ndash396 2012
[80] H Schroeder A-L Fabricius D Ecker T A Ternes andL Duester ldquoMetal(loid) speciation and size fractionation insediment pore water depth profiles examined with a newmesoprofiling systemrdquo Chemosphere vol 179 pp 185ndash193 2017
[81] Y Song and G Muller ldquoFreshwater sediments sinks andsources of brominerdquo Naturwissenschaften vol 80 no 12pp 558ndash560 1993
[82] M E Goher H I Farhat M H Abdo and S G Salem ldquoMetalpollution assessment in the surface sediment of Lake NasserEgyptrdquo Egyptian Journal of Aquatic Research vol 40 no 3pp 213ndash224 2014
[83] G F El-Said M M El-Sadawy and A A Moneer ldquoIncor-poration of fluoride and boron into surface sediments alongthe Egyptian Mediterranean coastrdquo Egyptian Journal ofAquatic Research vol 36 no 4 pp 569ndash583 2010
[84] B Gilfedder G M Petri M Wessels and H Biester ldquoAniodine mass-balance for Lake Constance Germany insightsinto iodine speciation changes and fluxesrdquo Geochimica etCosmochimica Acta vol 74 no 11 pp 3090ndash3111 2010
[85] E Korobova L Kolmykova B Ryzhenko et al ldquoDistributionand speciation of iodine in drinking waters from geochem-ically different areas of Bryansk region contaminated after theChernobyl accident in relation to health and remediationaspectsrdquo Journal of Geochemical Exploration vol 184pp 311ndash317 2018
[86] V Zic V W Truesdale and N Cukrov ldquo-e distribution ofiodide and iodate in anchialine cave watersmdashevidence forsustained localised oxidation of iodide to iodate in marinewaterrdquoMarine Chemistry vol 112 no 3-4 pp 168ndash178 2008
[87] M B Heeb J Criquet S G Zimmermann-Steffens andU Von Gunten ldquoOxidative treatment of bromide-containingwaters formation of bromine and its reactions with inorganicand organic compoundsmdasha critical reviewrdquo Water Researchvol 48 pp 15ndash42 2014
[88] V Sivasankar A K Darchen and R Omine SakthivelldquoChapter 2 ldquofluoride a world ubiquitous compound itschemistry and ways of contaminationrdquo in Surface ModifiedCarbons as Scavengers for Fluoride fromWater V SivasankarEd pp 5ndash32 copy Springer International Publishing Switzer-land Cham Switzerland 2016
[89] O Cabestrero P Del Buey and M E Sanz-Montero ldquoBio-sedimentary and geochemical constraints on the precipitationof mineral crusts in shallow sulphate lakesrdquo SedimentaryGeology vol 366 pp 32ndash46 2018
[90] M A Hassaan O A El-Rayis and E I Hemada ldquoEstimationof the redox potential of lake mariut drainage system (Qalaaand Umum drains)rdquoHydrology vol 5 no 6 pp 82ndash85 2017
20 Journal of Chemistry
[18] M A Khairy ldquoAssessment of priority phenolic compounds insediments from an extremely polluted coastal wetland (LakeMaryut Egypt)rdquo Environmental Monitoring and Assessmentvol 185 no 1 pp 441ndash455 2013
[19] N A El-Naggar and E A Rifaat ldquoEgyptian coastal lakes andwetlands part Imdashcharacteristics and hydrodynamicsrdquo in eHandbook of Environmental Chemistry A M Negm EdSpringer International Publishing AG Berlin Germany 2017
[20] J J Hanley and K T Koga ldquoChapter 2 ldquohalogens in terrestrialand cosmic geochemical systems abundances Geochemicalbehaviors and analytical methodsrdquordquo in e Role of Halogensin Terrestrial and Extraterrestrial Geochemical ProcessesD E Harlov and L Aranovich Eds Springer InternationalPublishing AG Berlin Germany pp 21ndash121 2018
[21] A Ghosh K Mukherjee S K Ghosh and B Saha ldquoSourcesand toxicity of fluoride in the environmentrdquo Research onChemical Intermediates vol 39 no 7 pp 2881ndash2915 2013
[22] M M Naim A A Moneer and G F El-Said ldquoPredictiveequations for the defluoridation by electrocoagulation tech-nique using bipolar aluminum electrodes in the absence andpresence of additives a multivariate studyrdquo Desalination andWater Treatment vol 57 no 14 pp 6320ndash6332 2016
[23] G F El-Said N A Shaltout M M El-Sadaawy andA M H Morsy ldquo-e precipitation of fluoride calcium andmagnesium minerals from Egyptian Mediterranean Sea coastin relation to discharged watersrdquo Desalination and WaterTreatment vol 57 no 5 pp 2113ndash2124 2016
[24] H Bureau ldquoIodine encyclopedia of geochemistry A com-prehensive reference source on the chemistry of the earthrdquo inEncyclopedia of Earth Sciences Series W M White Ed copySpringer International Publishing AG 2016
[25] F C Kupper and C J Carrano ldquoKey aspects of the iodinemetabolism in brown algae a brief critical reviewrdquo Metal-lomics vol 11 pp 756ndash764 2019
[26] R Liteplo R Gomes P Howe and H Malcolm Fluorides-Environmental Health Criteria 227 p 290 World HealthOrganization (WHO) Geneva Switzerland 2002
[27] G F El-Said and M M El-Sadaawy ldquoSeasonal variation ofboron and fluoride in Tilapia nilotica from an Egyptian fishfarm in relation to Human health hazard assessmentrdquoHumanand Ecological Risk Assessment An International Journalvol 19 no 4 pp 930ndash943 2013
[28] WHO (World Health Organization) Bromide in Drinking-Water Background Document for Development of WHOGuidelines for Drinking-Water Quality WHO Press WorldHealth Organization Geneva Switzerland 2009
[29] G F El-Said and N A Sallam ldquo-e uptake of fluorideconcentration and its effects on the growth rate of shrimps(Palaemon elegans Rathke)rdquo Chemistry and Ecology vol 24no 3 pp 191ndash205 2008
[30] X Zhang J He B He and J Sun ldquoAssessment formationmechanism and different source contributions of dissolvedsalt pollution in the shallow groundwater of Hutuo Riveralluvial-pluvial fan in the North China Plainrdquo EnvironmentalScience and Pollution Research vol 26 no 35 pp 35742ndash35756 2019
[31] Y Zhu B Huang Z Zhu et al ldquoldquoCharacterization disso-lution and solubility of the hydroxypyromorphitendashhydroxyapatite solid solution [(PbxCa1minusx)5(PO4)3OH] at25 degC and pH 2ndash9rdquo Geochemical Transactions vol 17 no 2pp 1ndash18 2016
[32] G F El-Said M M El-Sadaawy A A Moneer andN A Shaltout ldquo-e effect of fluoride on the distribution ofsome minerals in the surface water of an Egyptian lagoon at
the Mediterranean Seardquo Egyptian Journal of Aquatic Researchvol 41 no 1 pp 31ndash39 2015
[33] Y Zhu Z Zhu X Zhao Y Liang and Y Huang ldquoChar-acterization dissolution and solubility of lead hydroxypyr-omorphite [Pb5(PO4)3OH] at 25ndash45degCrdquo Journal ofChemistry vol 2015 Article ID 269387 10 pages 2015
[34] M A Z Chahouki ldquoMultivariate analysis techniques inenvironmental sciencerdquo in Earth and Environmental SciencesDr Imran Ahmad Dar Ed InTech Open London UK 2011httpwwwintechopencombooksearth-and-environmental-sciencesmultivariate-analysis-techniques-inenvironmental-science
[35] J V Klump and C S Martens ldquoBiogeochemical cycling in anorganic-rich coastal marine basin 5 Sedimentary nitrogenand phosphorus budgets based upon kinetic models massbalances and the stoichiometry of nutrient regenerationrdquoGeochimica et Cosmochimica Acta vol 51 no 5 pp 1161ndash1173 1987
[36] R L Folk Petrology of Sedimentary Rocks University of TexasAustin TX USA 1974
[37] P Saenger ldquoA rapid spectrophotometric method for thedetermination of bromine in seawater and in the ash ofmarine algaerdquo Helgolander Wissenschaftliche Meer-esuntersuchungen vol 23 no 1 pp 32ndash37 1972
[38] P G Jeffery Chemical Methods of Rock Analysis PergamonPress New York NY USA 2nd edition 1975
[39] J D H Strickland and T R Parsons ldquoA practical handbook ofseawater analysisrdquo in Fisheries Research Board of CanadaBulletin 167p 311 Second edition Wiley Ottawa Canada1972
[40] B Horvath O Opara-Nadi and F Beese ldquoA simple methodfor measuring the carbonate content of soilsrdquo Soil ScienceSociety of America Journal vol 69 no 4 pp 1066ndash1068 2005
[41] K Grasshoff Methods of Seawater Analysis p 317 VerlagChemie Weinkeim Germany 1976
[42] R Danovaro D Marrale N Della Croce P Parodi andM Fabiano ldquoBiochemical composition of sedimentary or-ganic matter and bacterial distribution in the Aegean Seatrophic state and pelagic-benthic couplingrdquo Journal of SeaResearch vol 42 no 2 pp 117ndash129 1999
[43] APHA-AWWA-WPCF (American Public Health Associa-tion) Standard Methods for the Examination of Water andWaste Water American Public Health Association Wash-ington DC USA 20th edition 1999
[44] K I Aspila H Agemian and A S Y Chau ldquoA semi-auto-mated method for the determination of inorganic organicand total phosphate in sedimentsrdquo e Analyst vol 101no 1200 pp 187ndash197 1976
[45] J P Riley and D Taylor ldquoChelating resins for the concen-tration of trace elements from sea water and their analyticaluse in conjunction with atomic absorption spectrophotom-etryrdquo Analytica Chimica Acta vol 40 pp 479ndash485 1968
[46] G F El-Said and A El-Sikaily ldquoChemical composition ofsome seaweed from Mediterranean Sea coast Egyptrdquo Envi-ronmental Monitoring and Assessment vol 185 no 7pp 6089ndash6099 2013
[47] Directorate General of Health Services Ministry of Health andFamilyWelfare Government of India ldquoManual of methods ofanalysis of foodsrdquo in Fruit and Vegetable Productsp 57Directorate General of Health Services Ministry of Health andFamily Welfare Government of India New Delhi India2005
[48] A Gunnars S Blomqvist and C Martinsson ldquoInorganicformation of apatite in brackish seawater from the Baltic Sea
18 Journal of Chemistry
an experimental approachrdquo Marine Chemistry vol 91 no 1-4 pp 15ndash26 2004
[49] W M Haynes D R Lide and T J Bruno CRC Handbook ofChemistry and Physics A Ready Reference Book of Chemicaland Physical Data CRC Press Taylor amp Frances Group BocaRaton FL USA 97th edition 2017
[50] M S Masoud M I El-Samra and M M El-Sadawy ldquoWaterchemistry of el-mex bay west of Alexandria Egyptrdquo eEgypian Science Magazine vol 2 pp 70ndash78 2005
[51] F J Millero R Feistel D G Wright and T J McDougallldquo-e composition of standard seawater and the definition ofthe reference-composition salinity scalerdquo Deep Sea ResearchPart I Oceanographic Research Papers vol 55 no 1pp 50ndash72 2008
[52] S K El-Wakeel S A Morcos and A M Mahlis ldquo-e majorcations in Lake Maryut watersrdquo Hydrobiologia vol 36 no 2pp 253ndash274 1970
[53] A M Mahlis S A Morcos and S K El-Wakeel ldquo-e majoranions in Lake Maryut watersrdquo Hydrobiologia vol 36 no 2pp 275ndash294 1970
[54] A S Saad M A Massoud R A Amer and M A GhorabldquoAssessment of the physico-chemical characteristics andwater quality analysis of Mariout Lake southern of Alexan-dria Egyptrdquo Journal of Environmental and Analytical Toxi-cology vol 7 no 1 p 421 2017
[55] R Rumuri ldquoDataset on hydrogeochemical characteristics ofgroundwater and surface water in Kattumannarkoil TalukIndiardquo Data in Brief vol 32 Article ID 106058 2020
[56] P Szefer S W Fowler K Ikuta et al ldquoA comparative as-sessment of heavy metal accumulation in soft parts and byssusof mussels from subarctic temperate subtropical and tropicalmarine environmentsrdquo Environmental Pollution vol 139no 1 pp 70ndash78 2006
[57] N F Soliman G M El Zokm and M A Okbah ldquoRisk as-sessment and chemical fractionation of selected elements insurface sediments from Lake Qarun Egypt using modifiedBCR techniquerdquo Chemosphere vol 191 pp 262ndash271 2018
[58] G M El Zokm M I A Ibrahim L A Mohamed and M El-Mamoney ldquoCritical geochemical insight into Alexandria coastwith special reference to diagnostic ratios (TOCTN amp SrCa)and heavy metals ecotoxicological hazardsrdquo Egyptian Journalof Aquatic Research vol 46 no 1 pp 27ndash33 2020
[59] A S Likuku K B Mmolawa and G K GaboutloeloeldquoAssessment of heavy metal enrichment and degree of con-tamination around the copper-nickel mine in the SelebiPhikwe Region Eastern Botswanardquo Environment and EcologyResearch vol 1 no 2 pp 32ndash40 2013
[60] M K Khalil S E O Draz G M El Zokm and G F El-SaidldquoApportionment of geochemistry texturersquos properties and riskassessment of some elements in surface sediments from Bar-dawil Lagoon Egyptrdquo Human and Ecological Risk AssessmentAn International Journal vol 22 no 3 pp 775ndash791 2016
[61] M M El-Sadaawy and G F El-Said ldquoAssessment of fluoridein three selected polluted environments along the EgyptianMediterranean Sea effects on local populationsrdquo Human andEcological Risk Assessment An International Journal vol 20no 6 pp 1643ndash1658 2014
[62] USEPA ldquoSuperfund exposure assessment manualrdquo inOSWER Directive 92855-1EPA540l-88001Office of Emer-gency and Remedial Response Washington DC USA 1988
[63] USEPA ldquoExposure factors handbookrdquo in EPA6008-89043Office of Health and Environmental Assessment Wash-ington DC USA 1989
[64] Health Canada ldquoFederal Contaminated Site Risk Assessmentin Canadardquo Part II Health Canada Toxicological ReferenceValues (TRVs) Cat H46-204-368E Calgary Health CanadaOttawa Canada 2007
[65] J Iqbal S A Tirmizi and M H Shah ldquoStatistical appor-tionment and risk assessment of selected metals in sedimentsfrom Rawal Lake (Pakistan)rdquo Environmental Monitoring andAssessment vol 185 no 1 pp 729ndash743 2013
[66] USEPA (US Environmental Protection Agency) Region 6USAEPA ldquoMultimedia Planning and Permitting DivisionrdquoOffice of Solid Waste Center for Combustion Science andEngineering Washington DC USA 2005
[67] P Jeschke ldquoLatest generation of halogen-containing pesti-cidesrdquo Pest Management Science vol 73 no 6 pp 1053ndash10662017
[68] M A Shreadah O A El-Rayis N A Shaaban andA M Hamdan ldquoWater quality assessment and phosphorusbudget of a lake (Mariut Egypt) after diversion of wastewaterseffluentsrdquo Environmental Science and Pollution Researchvol 27 no 21 pp 26786ndash26799 2020
[69] J P Riley and M Tongudai ldquo-e major cationchlorinityratios in sea waterrdquo Chemical Geology vol 2 pp 263ndash2691967
[70] R B McCleskey D K Nordstrom D D Susong J W Balland J M Holloway ldquoSource and fate of inorganic solutes inthe gibbon river yellowstone national park Wyoming USArdquoJournal of Volcanology and Geothermal Research vol 193no 3-4 pp 189ndash202 2010
[71] G T F Wong and K-Y Li ldquoWinklerrsquos method overestimatesdissolved oxygen in seawater iodate interference and itsoceanographic implicationsrdquo Marine Chemistry vol 115no 1-2 pp 86ndash91 2009
[72] B S R V Prasad P D N Srinivasu P S VarmaA V Raman and S Ray ldquoDynamics of dissolved oxygen inrelation to saturation and health of an aquatic body a case forChilka Lagoon Indiardquo Journal of Ecosystems vol 2014 Ar-ticle ID 526245 17 pages 2014
[73] China Environmental Protection Agency EnvironmentalQuality Standards for Surface Water (GB3838ndash2002) NationalEnvironmental Protection Agency of China Beijing China2002
[74] Y Jia L Wang Z Qu and Z Yang ldquoDistribution con-tamination and accumulation of heavy metals in watersediments and freshwater shellfish from Liuyang RiverSouthern Chinardquo Environmental Science and Pollution Re-search vol 25 no 7 pp 7012ndash7020 2018
[75] A Moneer M El-Sadawy G El-Said and A Radwan ldquoBoronhuman health risk assessment relative to the environmentalpollution of Lake Edku Egyptrdquo Journal of King AbdulazizUniversity vol 23 no 2 pp 41ndash55 2012
[76] C B Tabelin T Igarashi T Arima D Sato T Tatsuhara andS Tamoto ldquoCharacterization and evaluation of arsenic andboron adsorption onto natural geologic materials and theirapplication in the disposal of excavated altered rockrdquo Geo-derma vol 213 pp 163ndash172 2014
[77] G Aloisi K Wallmann M Drews and G BohrmannldquoEvidence for the submarine weathering of silicate minerals inBlack Sea sediments possible implications for the marine Liand B cyclesrdquo Geochemistry Geophysics Geosystems vol 5no 4 pp 1ndash22 2004
[78] C Degueldre and V Cloet ldquoPore water colloid properties inargillaceous sedimentary rocksrdquo Science of e Total Envi-ronment vol 569-570 pp 423ndash433 2016
Journal of Chemistry 19
[79] J A Higgins and D P Schrag ldquoRecords of Neogene seawaterchemistry and diagenesis in deep-sea carbonate sedimentsand pore fluidsrdquo Earth and Planetary Science Letters vol 357-358 pp 386ndash396 2012
[80] H Schroeder A-L Fabricius D Ecker T A Ternes andL Duester ldquoMetal(loid) speciation and size fractionation insediment pore water depth profiles examined with a newmesoprofiling systemrdquo Chemosphere vol 179 pp 185ndash193 2017
[81] Y Song and G Muller ldquoFreshwater sediments sinks andsources of brominerdquo Naturwissenschaften vol 80 no 12pp 558ndash560 1993
[82] M E Goher H I Farhat M H Abdo and S G Salem ldquoMetalpollution assessment in the surface sediment of Lake NasserEgyptrdquo Egyptian Journal of Aquatic Research vol 40 no 3pp 213ndash224 2014
[83] G F El-Said M M El-Sadawy and A A Moneer ldquoIncor-poration of fluoride and boron into surface sediments alongthe Egyptian Mediterranean coastrdquo Egyptian Journal ofAquatic Research vol 36 no 4 pp 569ndash583 2010
[84] B Gilfedder G M Petri M Wessels and H Biester ldquoAniodine mass-balance for Lake Constance Germany insightsinto iodine speciation changes and fluxesrdquo Geochimica etCosmochimica Acta vol 74 no 11 pp 3090ndash3111 2010
[85] E Korobova L Kolmykova B Ryzhenko et al ldquoDistributionand speciation of iodine in drinking waters from geochem-ically different areas of Bryansk region contaminated after theChernobyl accident in relation to health and remediationaspectsrdquo Journal of Geochemical Exploration vol 184pp 311ndash317 2018
[86] V Zic V W Truesdale and N Cukrov ldquo-e distribution ofiodide and iodate in anchialine cave watersmdashevidence forsustained localised oxidation of iodide to iodate in marinewaterrdquoMarine Chemistry vol 112 no 3-4 pp 168ndash178 2008
[87] M B Heeb J Criquet S G Zimmermann-Steffens andU Von Gunten ldquoOxidative treatment of bromide-containingwaters formation of bromine and its reactions with inorganicand organic compoundsmdasha critical reviewrdquo Water Researchvol 48 pp 15ndash42 2014
[88] V Sivasankar A K Darchen and R Omine SakthivelldquoChapter 2 ldquofluoride a world ubiquitous compound itschemistry and ways of contaminationrdquo in Surface ModifiedCarbons as Scavengers for Fluoride fromWater V SivasankarEd pp 5ndash32 copy Springer International Publishing Switzer-land Cham Switzerland 2016
[89] O Cabestrero P Del Buey and M E Sanz-Montero ldquoBio-sedimentary and geochemical constraints on the precipitationof mineral crusts in shallow sulphate lakesrdquo SedimentaryGeology vol 366 pp 32ndash46 2018
[90] M A Hassaan O A El-Rayis and E I Hemada ldquoEstimationof the redox potential of lake mariut drainage system (Qalaaand Umum drains)rdquoHydrology vol 5 no 6 pp 82ndash85 2017
20 Journal of Chemistry
an experimental approachrdquo Marine Chemistry vol 91 no 1-4 pp 15ndash26 2004
[49] W M Haynes D R Lide and T J Bruno CRC Handbook ofChemistry and Physics A Ready Reference Book of Chemicaland Physical Data CRC Press Taylor amp Frances Group BocaRaton FL USA 97th edition 2017
[50] M S Masoud M I El-Samra and M M El-Sadawy ldquoWaterchemistry of el-mex bay west of Alexandria Egyptrdquo eEgypian Science Magazine vol 2 pp 70ndash78 2005
[51] F J Millero R Feistel D G Wright and T J McDougallldquo-e composition of standard seawater and the definition ofthe reference-composition salinity scalerdquo Deep Sea ResearchPart I Oceanographic Research Papers vol 55 no 1pp 50ndash72 2008
[52] S K El-Wakeel S A Morcos and A M Mahlis ldquo-e majorcations in Lake Maryut watersrdquo Hydrobiologia vol 36 no 2pp 253ndash274 1970
[53] A M Mahlis S A Morcos and S K El-Wakeel ldquo-e majoranions in Lake Maryut watersrdquo Hydrobiologia vol 36 no 2pp 275ndash294 1970
[54] A S Saad M A Massoud R A Amer and M A GhorabldquoAssessment of the physico-chemical characteristics andwater quality analysis of Mariout Lake southern of Alexan-dria Egyptrdquo Journal of Environmental and Analytical Toxi-cology vol 7 no 1 p 421 2017
[55] R Rumuri ldquoDataset on hydrogeochemical characteristics ofgroundwater and surface water in Kattumannarkoil TalukIndiardquo Data in Brief vol 32 Article ID 106058 2020
[56] P Szefer S W Fowler K Ikuta et al ldquoA comparative as-sessment of heavy metal accumulation in soft parts and byssusof mussels from subarctic temperate subtropical and tropicalmarine environmentsrdquo Environmental Pollution vol 139no 1 pp 70ndash78 2006
[57] N F Soliman G M El Zokm and M A Okbah ldquoRisk as-sessment and chemical fractionation of selected elements insurface sediments from Lake Qarun Egypt using modifiedBCR techniquerdquo Chemosphere vol 191 pp 262ndash271 2018
[58] G M El Zokm M I A Ibrahim L A Mohamed and M El-Mamoney ldquoCritical geochemical insight into Alexandria coastwith special reference to diagnostic ratios (TOCTN amp SrCa)and heavy metals ecotoxicological hazardsrdquo Egyptian Journalof Aquatic Research vol 46 no 1 pp 27ndash33 2020
[59] A S Likuku K B Mmolawa and G K GaboutloeloeldquoAssessment of heavy metal enrichment and degree of con-tamination around the copper-nickel mine in the SelebiPhikwe Region Eastern Botswanardquo Environment and EcologyResearch vol 1 no 2 pp 32ndash40 2013
[60] M K Khalil S E O Draz G M El Zokm and G F El-SaidldquoApportionment of geochemistry texturersquos properties and riskassessment of some elements in surface sediments from Bar-dawil Lagoon Egyptrdquo Human and Ecological Risk AssessmentAn International Journal vol 22 no 3 pp 775ndash791 2016
[61] M M El-Sadaawy and G F El-Said ldquoAssessment of fluoridein three selected polluted environments along the EgyptianMediterranean Sea effects on local populationsrdquo Human andEcological Risk Assessment An International Journal vol 20no 6 pp 1643ndash1658 2014
[62] USEPA ldquoSuperfund exposure assessment manualrdquo inOSWER Directive 92855-1EPA540l-88001Office of Emer-gency and Remedial Response Washington DC USA 1988
[63] USEPA ldquoExposure factors handbookrdquo in EPA6008-89043Office of Health and Environmental Assessment Wash-ington DC USA 1989
[64] Health Canada ldquoFederal Contaminated Site Risk Assessmentin Canadardquo Part II Health Canada Toxicological ReferenceValues (TRVs) Cat H46-204-368E Calgary Health CanadaOttawa Canada 2007
[65] J Iqbal S A Tirmizi and M H Shah ldquoStatistical appor-tionment and risk assessment of selected metals in sedimentsfrom Rawal Lake (Pakistan)rdquo Environmental Monitoring andAssessment vol 185 no 1 pp 729ndash743 2013
[66] USEPA (US Environmental Protection Agency) Region 6USAEPA ldquoMultimedia Planning and Permitting DivisionrdquoOffice of Solid Waste Center for Combustion Science andEngineering Washington DC USA 2005
[67] P Jeschke ldquoLatest generation of halogen-containing pesti-cidesrdquo Pest Management Science vol 73 no 6 pp 1053ndash10662017
[68] M A Shreadah O A El-Rayis N A Shaaban andA M Hamdan ldquoWater quality assessment and phosphorusbudget of a lake (Mariut Egypt) after diversion of wastewaterseffluentsrdquo Environmental Science and Pollution Researchvol 27 no 21 pp 26786ndash26799 2020
[69] J P Riley and M Tongudai ldquo-e major cationchlorinityratios in sea waterrdquo Chemical Geology vol 2 pp 263ndash2691967
[70] R B McCleskey D K Nordstrom D D Susong J W Balland J M Holloway ldquoSource and fate of inorganic solutes inthe gibbon river yellowstone national park Wyoming USArdquoJournal of Volcanology and Geothermal Research vol 193no 3-4 pp 189ndash202 2010
[71] G T F Wong and K-Y Li ldquoWinklerrsquos method overestimatesdissolved oxygen in seawater iodate interference and itsoceanographic implicationsrdquo Marine Chemistry vol 115no 1-2 pp 86ndash91 2009
[72] B S R V Prasad P D N Srinivasu P S VarmaA V Raman and S Ray ldquoDynamics of dissolved oxygen inrelation to saturation and health of an aquatic body a case forChilka Lagoon Indiardquo Journal of Ecosystems vol 2014 Ar-ticle ID 526245 17 pages 2014
[73] China Environmental Protection Agency EnvironmentalQuality Standards for Surface Water (GB3838ndash2002) NationalEnvironmental Protection Agency of China Beijing China2002
[74] Y Jia L Wang Z Qu and Z Yang ldquoDistribution con-tamination and accumulation of heavy metals in watersediments and freshwater shellfish from Liuyang RiverSouthern Chinardquo Environmental Science and Pollution Re-search vol 25 no 7 pp 7012ndash7020 2018
[75] A Moneer M El-Sadawy G El-Said and A Radwan ldquoBoronhuman health risk assessment relative to the environmentalpollution of Lake Edku Egyptrdquo Journal of King AbdulazizUniversity vol 23 no 2 pp 41ndash55 2012
[76] C B Tabelin T Igarashi T Arima D Sato T Tatsuhara andS Tamoto ldquoCharacterization and evaluation of arsenic andboron adsorption onto natural geologic materials and theirapplication in the disposal of excavated altered rockrdquo Geo-derma vol 213 pp 163ndash172 2014
[77] G Aloisi K Wallmann M Drews and G BohrmannldquoEvidence for the submarine weathering of silicate minerals inBlack Sea sediments possible implications for the marine Liand B cyclesrdquo Geochemistry Geophysics Geosystems vol 5no 4 pp 1ndash22 2004
[78] C Degueldre and V Cloet ldquoPore water colloid properties inargillaceous sedimentary rocksrdquo Science of e Total Envi-ronment vol 569-570 pp 423ndash433 2016
Journal of Chemistry 19
[79] J A Higgins and D P Schrag ldquoRecords of Neogene seawaterchemistry and diagenesis in deep-sea carbonate sedimentsand pore fluidsrdquo Earth and Planetary Science Letters vol 357-358 pp 386ndash396 2012
[80] H Schroeder A-L Fabricius D Ecker T A Ternes andL Duester ldquoMetal(loid) speciation and size fractionation insediment pore water depth profiles examined with a newmesoprofiling systemrdquo Chemosphere vol 179 pp 185ndash193 2017
[81] Y Song and G Muller ldquoFreshwater sediments sinks andsources of brominerdquo Naturwissenschaften vol 80 no 12pp 558ndash560 1993
[82] M E Goher H I Farhat M H Abdo and S G Salem ldquoMetalpollution assessment in the surface sediment of Lake NasserEgyptrdquo Egyptian Journal of Aquatic Research vol 40 no 3pp 213ndash224 2014
[83] G F El-Said M M El-Sadawy and A A Moneer ldquoIncor-poration of fluoride and boron into surface sediments alongthe Egyptian Mediterranean coastrdquo Egyptian Journal ofAquatic Research vol 36 no 4 pp 569ndash583 2010
[84] B Gilfedder G M Petri M Wessels and H Biester ldquoAniodine mass-balance for Lake Constance Germany insightsinto iodine speciation changes and fluxesrdquo Geochimica etCosmochimica Acta vol 74 no 11 pp 3090ndash3111 2010
[85] E Korobova L Kolmykova B Ryzhenko et al ldquoDistributionand speciation of iodine in drinking waters from geochem-ically different areas of Bryansk region contaminated after theChernobyl accident in relation to health and remediationaspectsrdquo Journal of Geochemical Exploration vol 184pp 311ndash317 2018
[86] V Zic V W Truesdale and N Cukrov ldquo-e distribution ofiodide and iodate in anchialine cave watersmdashevidence forsustained localised oxidation of iodide to iodate in marinewaterrdquoMarine Chemistry vol 112 no 3-4 pp 168ndash178 2008
[87] M B Heeb J Criquet S G Zimmermann-Steffens andU Von Gunten ldquoOxidative treatment of bromide-containingwaters formation of bromine and its reactions with inorganicand organic compoundsmdasha critical reviewrdquo Water Researchvol 48 pp 15ndash42 2014
[88] V Sivasankar A K Darchen and R Omine SakthivelldquoChapter 2 ldquofluoride a world ubiquitous compound itschemistry and ways of contaminationrdquo in Surface ModifiedCarbons as Scavengers for Fluoride fromWater V SivasankarEd pp 5ndash32 copy Springer International Publishing Switzer-land Cham Switzerland 2016
[89] O Cabestrero P Del Buey and M E Sanz-Montero ldquoBio-sedimentary and geochemical constraints on the precipitationof mineral crusts in shallow sulphate lakesrdquo SedimentaryGeology vol 366 pp 32ndash46 2018
[90] M A Hassaan O A El-Rayis and E I Hemada ldquoEstimationof the redox potential of lake mariut drainage system (Qalaaand Umum drains)rdquoHydrology vol 5 no 6 pp 82ndash85 2017
20 Journal of Chemistry
[79] J A Higgins and D P Schrag ldquoRecords of Neogene seawaterchemistry and diagenesis in deep-sea carbonate sedimentsand pore fluidsrdquo Earth and Planetary Science Letters vol 357-358 pp 386ndash396 2012
[80] H Schroeder A-L Fabricius D Ecker T A Ternes andL Duester ldquoMetal(loid) speciation and size fractionation insediment pore water depth profiles examined with a newmesoprofiling systemrdquo Chemosphere vol 179 pp 185ndash193 2017
[81] Y Song and G Muller ldquoFreshwater sediments sinks andsources of brominerdquo Naturwissenschaften vol 80 no 12pp 558ndash560 1993
[82] M E Goher H I Farhat M H Abdo and S G Salem ldquoMetalpollution assessment in the surface sediment of Lake NasserEgyptrdquo Egyptian Journal of Aquatic Research vol 40 no 3pp 213ndash224 2014
[83] G F El-Said M M El-Sadawy and A A Moneer ldquoIncor-poration of fluoride and boron into surface sediments alongthe Egyptian Mediterranean coastrdquo Egyptian Journal ofAquatic Research vol 36 no 4 pp 569ndash583 2010
[84] B Gilfedder G M Petri M Wessels and H Biester ldquoAniodine mass-balance for Lake Constance Germany insightsinto iodine speciation changes and fluxesrdquo Geochimica etCosmochimica Acta vol 74 no 11 pp 3090ndash3111 2010
[85] E Korobova L Kolmykova B Ryzhenko et al ldquoDistributionand speciation of iodine in drinking waters from geochem-ically different areas of Bryansk region contaminated after theChernobyl accident in relation to health and remediationaspectsrdquo Journal of Geochemical Exploration vol 184pp 311ndash317 2018
[86] V Zic V W Truesdale and N Cukrov ldquo-e distribution ofiodide and iodate in anchialine cave watersmdashevidence forsustained localised oxidation of iodide to iodate in marinewaterrdquoMarine Chemistry vol 112 no 3-4 pp 168ndash178 2008
[87] M B Heeb J Criquet S G Zimmermann-Steffens andU Von Gunten ldquoOxidative treatment of bromide-containingwaters formation of bromine and its reactions with inorganicand organic compoundsmdasha critical reviewrdquo Water Researchvol 48 pp 15ndash42 2014
[88] V Sivasankar A K Darchen and R Omine SakthivelldquoChapter 2 ldquofluoride a world ubiquitous compound itschemistry and ways of contaminationrdquo in Surface ModifiedCarbons as Scavengers for Fluoride fromWater V SivasankarEd pp 5ndash32 copy Springer International Publishing Switzer-land Cham Switzerland 2016
[89] O Cabestrero P Del Buey and M E Sanz-Montero ldquoBio-sedimentary and geochemical constraints on the precipitationof mineral crusts in shallow sulphate lakesrdquo SedimentaryGeology vol 366 pp 32ndash46 2018
[90] M A Hassaan O A El-Rayis and E I Hemada ldquoEstimationof the redox potential of lake mariut drainage system (Qalaaand Umum drains)rdquoHydrology vol 5 no 6 pp 82ndash85 2017
20 Journal of Chemistry