Trace metals biogeochemistry of Kumaun Himalayan Lakes, Uttarakhand, India

Environ Monit Assess (2012) 184:2947–2965DOI 10.1007/s10661-011-2163-y

Trace metals biogeochemistry of Kumaun HimalayanLakes, Uttarakhand, India

P. Purushothaman · G. J. Chakrapani

Received: 25 September 2010 / Accepted: 3 June 2011 / Published online: 29 June 2011© Springer Science+Business Media B.V. 2011

Abstract The increasing urbanization, along withtourism, has posed a major threat to the KumaunHimalayan Lakes, Uttarakhand, India. The totalmetal concentration in the water, interstitial wa-ter, and sediments along with the metal fraction-ation studies were carried out to understand theremobilization of the trace metals from the sedi-ments of the lakes. The high concentration of themetals in the water column of the lakes generallydecreases with depth and the metals release fromthe sediment is mainly due to the prevalence ofanoxic condition at the sediment–water interfaceand sediment column. The sediment shows thatmetals Fe and Cr are derived from detrital source,whereas Co, Ni, and Zn are derived mainly fromthe organic matter dissolution. The sparse corre-lation of the trace metals with Ti shows most ofthe metals have chiefly re-precipitated from thewater column. The metals speciation studies alsosupports that metals experience a high rate ofanoxic dissolution and their precipitation onto thesediments are determined by the sediment compo-

P. Purushothaman (B)National Institute of Hydrology, Roorkee,247 667, Indiae-mail: [email protected]

G. J.ChakrapaniIndian Institute of Technology, Roorkee,247 667, India

sition and organic matter content. The high con-centration of manganese in the interstitial water inthe lakes indicates dissolution of organic matter.The released manganese is adsorbed/precipitatedas carbonate phase (Nainital Lake) and oxidepahse (in other lakes). The study shows that thetrace metals are regenerated from the sedimentsdue to oxyhydroxide dissolution and organic mat-ter decomposition.

Keywords Trace metals · Metal fractionation ·Sediment–water interaction · Lakes ·Kumaun Himalaya

Introduction

During the last few decades, industrialization hasled to an increased mobilization of contaminantslike nutrients and trace metals either as a directaction (e.g., mining and smelting operations) oras an indirect consequence (e.g., acidification ofthe rain resulting in an increase in the weatheringproducts; Tessier et al. 1996). In surface water,trace metals are adsorbed onto the Fe–Mn hy-droxides, carbonates, organic matters, and clayparticles and settles down along with sediments(Stumm and Morgan 1996). The permanent accu-mulation of contaminants poses problems becausethe sediments act as a source of pollutants evenafter abation of pollution from waterways.

2948 Environ Monit Assess (2012) 184:2947–2965

The remobilization and sedimentation of themetals mainly depend on the oxic conditionprevailing at the sediment–water interface. Theprevalence of the oxic/anoxic condition dependson the circulation of O2, which at deeper depthsdepends on the degradation of the organic matter.The degradation of the organic matter consumesthe dissolved O2 and enhances the dissolution ofthe secondary oxygen sources like nitrate, man-ganese oxides, iron oxyhydroxides and sulfates areused (Boyle 2001; Tribovillard et al. 2006 and ref-erences therein). This biological/chemical processresults in the release of trace metals from the sed-iment (suspended) particles and causes remobi-lization. The remobilized metals are precipitatedor adsorbed onto the sediment particles. Hence,to understand the geochemical reactions, paleo-productivity, paleoredox conditions in the lakeecosystem, it is necessary to know the chemicalspecies of the elements along with the total con-centration of the sediments and water (Forstnerand Wittmann 1983; Tack and Verloo 1995;Warren and Haack 2001; Wang et al. 2003;Callender 2004; Sparks 2005).

The Kumaun Himalayan Lakes in India, oneof the frequent stopover places during vacation inthe northern part of the country, have been expe-riencing vigorous urbanization. Different sourceslike soil erosion, illegal construction activities, au-tomobile exhausts and painting of boat in touristseason every year pose serious problem of eu-trophication and deterioration of water qualityof these lakes (Singh and Gopal 2002; Choudharyet al. 2009). Nainital one among the four lakes hasbeen intensively affected by the tourism and in-creasing population. The other three lakes, Bhim-tal, Sattal, and Naukuchiatal are relatively unpol-luted and less affected by population growth. Thelakes Nainital and Bhimtal, in the newly devel-oping industrial area, are experiencing increasedinput of toxic metals, organic and inorganic pol-lutants (Singh and Gopal 2002). The other twolakes, Sattal and Naukuchiatal are relatively virginlakes receiving materials mainly from the catch-ment area as plant debris, landslides, and domesticrun-off.

The diversified nature of these lakes locatedvery near to each other has attracted many re-searchers towards them. The posing problem of

water deterioration and increasing populationhave made Lake Nainital as one of the most ex-tensively studied lakes out of these. The eutroph-ication of lake Nainital is found to be increasing(Pant et al. 1980) due to its very high productivity(>8; Singh and Gopal 2002). Ali et al. (1999)observed that this lake water is rich in nutrientsand metals and found that the macrophytes act asgood removers of metals. Nachiappan et al. (2000)studied the hydrodynamics using numerical mod-eling and stable isotopes. Gupta and Pant (1989)on Nainital Lake, Das et al. (1995), Chakrapani(2002) and Das (2005) studied the major ionchemistry of the Kumaun Lakes. Das et al. (1995)estimated the rate of sedimentation and observedthat the Nainital Lake has higher sedimentationrate as compared to the other lakes in the region.Kotlia et al. (2000) studied the paleoclimate inthe Bhimtal and Naukuchiatal region. The speci-ation of metals (Jain et al. 2007) and phosphorus(Purushothaman et al. 2008) in sediments alsohave been carried out in the lake Nainital.Choudhary (2008) have carried out the paleo-environmental and paleo-productivity in theKumaun Himalayan Lakes using the hydrocarbonand stable isotope studies. Despite various studiescarried out in these lakes, the regeneration andsource of the trace metals are yet to be addressedwhich is the focus of the present study.

Study Area

The Kumaun Himalayan Lakes, Nainital, Bhim-tal, Sattal, and Naukuchiatal, are located (29◦24′Nand 79◦28′E, 29◦20′N; 79◦36′E, 29◦21′N; 79◦32′Eand 29◦19′N; 79◦35′E, respectively) in the Nainitaldistrict of Uttarakhand state of India (Fig. 1).Lake Nainital, a tectonically formed, crescent-shaped lake lying at an altitude of 1,938 m,has two different sub-basins, Mallital and Tal-lital, divided in the middle with a ridge. Thelake receives water from two springs, paradharaand siphadara. The other lakes Bhimtal, Sattal,and Naukuchiatal are at an altitude 1,331, 1,370,and 1,320 m, respectively. The formation of theBhimtal–Naukuchiatal Lake system is related toa WNW–ESE trending strike-slip fault traversingthe area. It is believed that Bhimtal Lake had

Environ Monit Assess (2012) 184:2947–2965 2949

Fig. 1 Location map of the study area (the black dots in the lakes indicate sediment core sampling position)

been part of a bigger lake, which was about 7–10 km long and 1 km wide and later dried inHolocene times. The formation of Sattal Lake isbelieved to be due to the blockade of ravinesdue to debris flow. The drainage patterns of thelakes are of trellis type and structurally con-trolled by the faults and fractures (Valdiya 1988;Purushothaman 2009).

Among these lakes, Nainital is highly populatedwith almost 40,000 inhabitants. Other lakes aresparsely populated with the Bhimtal facing anincreasing population due to newly formed indus-trial area. The lithology of the lakes in Naini hillsranges from paleoproterozoic to terminal protero-zoic. The detailed description of the study areais discussed elsewhere (Valdiya 1988; Das et al.1995; Nachiappan et al. 2000; Chakrapani 2002;Das 2005; Purushothaman 2009). The rocks in theNainital Lake catchment consists mainly of car-bonate rocks such as limestone, dolomite, gypsum,calcareous slates, ferruginous shales, greywackes,etc. (Fig. 1; Das et al. 1995; Ali-etal 1999;Chakrapani 2002; Das 2005; Choudhary et al.2009). The northwestern part is made exclusivelyof argillaceous limestone and marlites, whereas

the southwestern part comprises of dolomite withlimestone and black carbonaceous slates (Valdiya1988). The Bhimtal and Naukuchiatal consistof Bhimtal Volcanics (amygdaloidal–vesicularbasalt, chlorite schist) and Bhowali Quartzite(Fig. 1). The Sattal catchment rocks include Jant-waliagaon Limestone along with the Bhimtal vol-canic and Bhowali Quartzite (Valdiya 1988).

Methods and methodology

Sample collection

Water samples were collected from the surface ofthe lake in 2006 and both surface and deep-watersamples at three depth intervals during 2008 in themonth of January. The interstitial water sampleswere extracted by centrifuging the sediments at7,500 rpm for 1 h. The water samples for the metalanalysis were filtered immediately in the fieldusing 0.45-μm membrane filter paper by a hand-powered vacuum of 250 ml volume filter unit andwere acidified to <2.0 pH by adding a few drops ofsupra pure nitric acid. The sediment samples were


collected from the deepest part of the lakes usinga gravity corer (Fig. 1). The collected cores weresegmented into sub-samples of 2 and 5 cm (forextracting interstitial water) interval in the fieldimmediately. The samples were stored in refrig-erated condition in clean and airtight polythenebags.

Sample analysis

Water and sediment analysis

The initial measurements of pH, Eh, and tem-perature were carried out in the water and sed-iment samples immediately after sample collec-tion in the field. The core sediment samples wereair-dried and powdered. Organic matter in thesediments was removed by treatment with H2O2

and digested using tri-acid (HCl + HNO3 + HF)method. Dissolved trace metals in the water anddigested sediments like iron (Fe), aluminum (Al),manganese (Mn), cobalt (Co), chromium (Cr),copper (Cu), nickel (Ni), lead (Pb), and zinc (Zn)were analyzed using DRC 3000 Elan, Perkin-Elmer ICP-MS. Calibration of the instrument forwater sampling analysis was done using laboratorystandards procured from Perkin-Elmer and USGSstandard SCO-1 was used for sediment analysis.

Metal fractionation

Fractionation of metals (Fe, Mn, Co, Cr, Cu,Ni, Pb, and Zn) associated with different chem-ical fractions was carried out using the seven-step procedure (Table 1) developed by Leleyter

and Probst (1999). The seven-step procedure ex-tracts the water soluble, exchangeable, carbonatebound, manganese oxide bound, amorphous ironoxy hydroxide bound, crystalline oxide bound,and organic matter bound. The residue was di-gested using tri-acid method to determine theresidual phase.

Results

The pH value of water in the lakes differs widely.Nainital is alkaline (∼8) in comparison with theother lakes showing lesser pH (7.8–7.3) in thewater column. The pH of water at sediment–waterinterface and interstitial water shows near neutral(∼7) nature in Nainital Lake and slightly acidicnature in other lakes (6.0–6.5). The redox poten-tial of the lakes show that the water column isoxic in nature except Naukuchiatal Lake, whichshows anoxic condition in the deeper water col-umn and at the sediment–water interface (−60,−140, 88, and −120 mV in Nainital, Bhimtal,Sattal, Naukuchiatal, respectively). Nainital Lakeshows high anoxic condition with Eh reduced to−274 mV in the interstitial water and the otherlakes show sub-oxic condition or low anoxic con-dition with the Eh values less than −130 mV.

Dissolved metals

The trace metal concentration in the lake watercolumn and interstitial water is given in Table 2.Trace metal concentration in Nainital is different

Table 1 Metal fractionation procedure (from Leleyter and Probst 1999)

Fraction Reagent Reaction time Temp◦ C

Dissolved with water Water 30 min + shaking 20Really exchangeable 1 M magnesium nitrate 2 h + shaking 20Bound to carbonates Sodium acetate at pH-4.5 (HoAc) 5 h + shaking 20Bound to Mn oxides 0.1 M hydroxyl ammonium chloride 30 min + shaking 20Bound to amorphous 0.2 M ammonium oxalate– 4 h (in dark) + shaking 20

Fe oxides 0.2 M oxalic acidBound to crystalline 0.2 M ammonium oxalate–0.2 M oxalic acid– 30 min + shaking 80

Fe oxides 0.1 M ascorbic, acidBound to organic 0.02 M HNO3, 35% H2O2 3.2 M Ammonium Acetate 30 min + shaking 85

matter (pH 2 with HNO3)Residual Aqua regia + HF (digestion) 89


Table 2 Water chemistry of the lakes—dissolved trace metals

Sample ID Fe (μM) Mn (μM) Al (μM) Co (nM) Cr (nM) Ni (nM) Cu (nM) Pb (nM) Zn (nM)

NainitalSurface (Mallital) 7.0 0.5 3.4 4.2 113.8 57.7 18.2 18.8 198.114 m 6.5 0.4 3.0 3.7 113.2 59.8 15.1 4.5 119.3Surface (Tallital) 6.2 0.4 3.3 3.2 49.8 53.2 15.8 7.6 94.414 m 6.1 0.4 2.8 3.0 127.5 53.5 19.4 5.3 79.3Above sediment 10.1 2.0 25.4 7.0 102.3 63.5 30.7 17.6 312.2PW 0–5 cm 28.7 0.1 0.2 13.5 186.2 276.8 33.2 0.1 54.6PW 5–10 cm 29.7 0.5 0.5 13.9 189.7 285.8 32.8 0.0 58.8PW 15–20 cm 23.0 0.1 0.8 10.9 167.6 229.3 41.8 0.1 124.6PW 25–30 cm 27.6 0.1 0.7 15.9 148.3 281.7 45.1 0.1 52.7

BhimtalSurface 4.1 0.6 1.7 1.8 44.2 27.0 16.1 2.9 132.610 m 4.0 0.6 1.6 1.8 42.0 24.9 9.1 1.7 63.3Above sediment 7.7 1.0 17.9 3.9 13.2 37.9 29.6 5.9 225.9PW 0–5 cm 9.9 3.7 3.0 15.8 148.0 132.2 95.4 0.6 55.1PW 5–10 cm 13.1 30.9 1.6 69.3 41.2 122.5 52.3 0.5 200.9PW 15–20 cm 5.0 21.2 1.9 63.6 13.0 80.7 63.8 0.2 400.5

SattalSurface 2.0 0.8 7.6 2.4 50.0 18.9 30.9 8.0 438.86 m 2.5 0.8 3.6 1.9 22.1 18.1 30.9 13.6 475.4Above sediment 5.4 1.5 10.0 3.1 13.0 25.9 34.0 9.2 615.3PW 0–5 cm 5.2 79.9 7.5 250.4 10.0 153.8 84.0 5.7 1800.6PW 5–10 cm 3.9 33.8 0.7 40.9 23.4 93.2 50.9 0.2 949.6PW 15–20 cm 3.7 41.4 1.3 62.3 23.4 88.7 21.4 0.3 728.8

NaukuchiatalSurface 4.0 1.3 4.1 1.8 5.9 23.0 12.0 6.5 119.320 m 15.8 5.1 0.9 5.5 5.4 28.3 11.0 2.3 102.2Above sediment 50.1 9.2 5.6 8.1 83.6 34.0 15.9 7.7 346.8PW 0–5 cm 8.0 3.8 1.1 13.5 35.3 114.8 66.2 0.1 765.9PW 5–10 cm 3.7 0.3 0.6 4.1 32.0 75.1 89.6 0.1 204.2PW 15–20 cm 4.3 0.2 36.5 9.3 48.8 49.7 143.0 1.6 173.4PW 20–25 cm 1.9 0.6 6.0 4.5 20.5 29.3 84.4 0.2 64.0

NA data not available/below detection limit, PW interstitial (pore) water, T Tallital; M Mallital

in the sub-basins with Tallital (north) having highconcentration than that of Mallital in the south.The metal concentration of this lake increases

up core in the water column (Fig. 2; Table 2),whereas, a decreasing trend is observed in Bhim-tal and Naukuchiatal Lakes. Sattal Lake shows

Fig. 2 Metals (Fe, Mn, and Al) in the water and interstitial water in the lakes (the letters in the parentheses refer to Bhimtal(B), Nainital (N), Naukuchiatal (NK), and Sattal (S) Lakes)


high iron (Fig. 2; Table 2), lead and zinc (Fig. 3)concentration in the water column showing de-creasing trend up core. Metal concentration in thelakes at the sediment–water interface and the top

10 cm of the interstitial water increases many folds(Figs. 2 and 3), the concentration of the metaldecreases with depth thereafter in the interstitialwater column.

Fig. 3 Metals in the water column and interstitial water in the lakes


Metals in sediments

Total metal concentration

The concentration of aluminum is uniform inall the lakes ranging between 4–7%. Metal ironconcentration, dominates the trace metal con-centration in all the lakes (3–12%) highest inBhimtal (10–12%) and lowest in the Nainital(∼3%). Manganese is the next abundant metalwith concentration ranging from 600 mg/kg(Bhimtal) to 1100 mg/kg (Naukuchiatal). Con-centration of cobalt is high in Naukuchiataland Sattal (>50 mg/kg) and low in the NainitalLake (<15 mg/kg; Fig. 4). Chromium is domi-nant in Bhimtal followed by Nainital ranging be-tween 11–70 mg/kg, whereas it is 15–25 mg/kgin Naukuchiatal and Sattal. Nainital and Sattalhave high concentration of nickel of 30–63 mg/kgand 50–80 mg/kg, respectively (Fig. 4). Thesemetals show increasing up core trend in all the

lakes. Concentration of copper is higher inNaukuchiatal (>80 mg/kg) and lesser in Naini-tal (>40 mg/kg). Lead with higher concentrationin Bhimtal and lowest in Nainital (Fig. 4) ex-hibits no significant change in concentration withdepth, zinc is the dominant metal in Nainital andNaukuchiatal Lakes with concentration greaterthan 70 mg/kg.

Heavy metal fractionation

Iron Iron constituting >50% of total iron inresidual fraction is dominant among all other frac-tions in all the lakes. The lakes exhibit diversifiedbehavior with Nainital (Fig. 5a) showing high con-centration in the carbonate and amorphous phasesand Bhimtal (Fig. 6a) showing high concentrationin the amorphous iron oxides and the organicphase. Sattal (Fig. 7a) and Naukuchiatal (Fig. 8a)show high concentration of iron in organic-bound

Fig. 4 Metals in the lake sediments


Fig. 5 Metal fractionation at Nainital Lake sediments

phase. The crystalline iron oxide bound fractionalso contains significant amounts of iron in all thelakes.

Manganese The carbonate phase contains highermanganese in Nainital (Fig. 5b) and Bhimtal(Fig. 6b), whereas the water dissolvable and easily


Fig. 6 Metal fractionation at Bhimtal Lake sediments

exchangeable phases have high percentage ofmanganese in Sattal (Fig. 7b) and Naukuchiatal(Fig. 8b). Manganese oxide bound fraction contains

high concentration of manganese in Nainital. The or-ganic matter bound and crystalline fraction show highconcentration of manganese in all the other lakes.


Fig. 7 Metal fractionation at Sattal Lake sediments


Fig. 8 Metal fractionation at Naukuchiatal Lake sediments

Cobalt The carbonate phase shows high concen-tration of cobalt in the Nainital (Fig. 5d) lakesediments followed by manganese and iron ox-

ide phases, where as the other three (Figs. 6,7 and 8d) lakes show high concentration ofcobalt in the iron oxide fraction (amorphous and


crystalline) and organic matter fraction. The otherfractions show very low cobalt concentration.

Chromium The residual fraction contains con-siderable amounts of chromium in all the lakes.The crystalline iron oxide bound fraction domi-nates Nainital (Fig. 5c) and Sattal Lakes (Fig. 7c)sediments and the amorphous iron oxide frac-tion dominates Bhimtal Lake (Fig. 6c). The or-ganic fraction also contains considerable amountof chromium in all the lakes especially in the Sattal(Fig. 7c) and Naukuchiatal Lakes (Fig. 8c).

Nickel The residual fraction contains consider-able amount of nickel in all the lakes. The carbon-ate bound fraction dominates Nainital (Fig. 5e)Lake sediments and the organic matter frac-tion dominates Bhimtal, Sattal and NaukuchiatalLakes (Figs. 6, 7 and 8e) after residual fraction.The crystalline iron oxide and amorphous iron ox-ide bound fractions are the other fractions, whichhave considerable concentrations of nickel.

Copper Copper is predominant in the carbon-ate fraction in Nainital (Fig. 5f), Naukuchiatal(Fig. 8f) and Bhimtal Lake (Fig. 6f) sedimentsfollowed by the amorphous iron oxide fraction inNainital and Bhimtal and by the organic matterbound fraction in Naukuchiatal. Sediments of Sat-tal (Fig. 7f) shows high concentration of copperin organic-bound fraction followed by residualfraction. The other fractions show considerableamount of copper in all the lakes.

Lead Lead is dominant in the carbonate fractionin Nainital Lake (Fig. 5g) sediments followed bythe amorphous iron oxide fraction. The residualand crystalline iron oxide fractions have consider-able amounts of lead in this lake. The other lakeshave high concentration of lead in the exchange-able fraction. Bhimtal Lake (Fig. 6g) contains con-siderable lead in the amorphous iron oxide and or-ganic fractions, where as Sattal and NaukuchiatalLakes have lead only in the easily exchangeablefraction.

Zinc A sizeable amount of zinc is present inthe amorphous iron oxide fraction in Nainital(Fig. 5h) and Bhimtal Lakes. The sediments in

these lakes have high amounts of zinc in the car-bonate (Nainital) and organic (Bhimtal) fractionsas well. The other fractions also contain consid-erable amounts of zinc in these lakes. Sattal andNaukuchiatal (Figs. 7 and 8g) have high concen-tration of zinc in the organic fraction followed bythe crystalline iron oxide fractions

Discussions

Dissolved metals

The trace metals concentrations in the KumaunHimalayan Lakes differ widely. The metal con-centration in the water column of Nainital Lake(Figs. 2 and 3) varies within the sub-basins, Tallitalshows high concentration compared to Mallital,may be due to the presence of a bus station caus-ing high vehicular pollution. Higher concentrationof zinc (Fig. 3) in the water column is due tothe sewage, vehicular, and the scrapheap wastagesdrained into the lake system (Sparks 2005). Otherlakes generally do not show much variation in thetrace metal concentration in the water column,high concentration of metals such as chromium(Fig. 3) may be due to the influence of weath-ering of catchment rocks, which have high con-centration of chromium (Bhat and Ahmad 1987).Higher concentration of metals is found at thesediment–water interface (SWI) and at the top10 cm of the interstitial water in all the lakes.This may be due to the release of metals frommetal oxides, because of changes in the oxic con-dition, i.e., from oxic to anoxic condition (Guoet al. 1997; Boyle 2001). The concentration ofmanganese is very high in the interstitial water ofthe Sattal and Naukuchiatal (Fig. 3), which is dueto the release of manganese in the anoxic layerdue to the presence of organic matter (Davison1993). The dissolution of oxyhydroxide particlesat sediment–water interface releases manganesewhich may diffuse upward and downward the sed-iment, as the manganese does not adsorb ontoorganic or sulfide phase (Tribovillard et al. 2006and the references therein). A plausible reasonfor low manganese concentration in the interstitialwater of Nainital Lake (Fig. 3) could be due tothe sequestration of manganese, released during


reduction of manganese oxide, by the dominantcarbonate phase. The metals cobalt, chromium,and nickel (Fig. 3) show increased concentrationindicating the dissolution of oxyhydroxide andoxide minerals. The metals aluminum (Fig. 2),copper, lead, and zinc (Fig. 3) show decrease inconcentration, may be precipitating with carbon-ate minerals or might be sequestered by the or-ganic matters since the presence of organic matterenhances the adsorption of these metals into thesurface sites (Calvert and Pederson 1993; Brulandand Lohan 2003; Morel and Price 2003).

Metals in sediments

Total metals

Trace metal composition of lake sediments is com-pared with some of the lakes in various parts ofthe world, average shale, carbonates and crustalcomposition (Table 3). The metals enter the lakethrough the weathering of the catchment rocks(Forstner and Wittmann 1983). Manganese con-centration at Nainital is almost similar to thatof the average carbonate rock (Purushothaman

Table 3 A comparison of metals in sediments (mg/kg) of Kumaun Himalayan Lakes with some of the world lakes and rivers

Country Co Cr Ni Cu Pb Zn

Lake Wielkiea Poland 2.3 1.15 1.6 2.05 9.7 571Lake Bosekowoa Poland 4.2 1.85 2.95 2.95 13.4 1100Lake Dominickea Poland 2.25 1.3 2.05 2.65 12.9 475Blue Mountain Lakeb USA – – – – 64–80 235–287Catfish Pondb USA – – – – 132–177 106–182Crater Lakeb USA – – – – 150–167 129–165Lake Successb USA – – – – 165–179 159–186Long Pine Pondb USA – – – – 114–134 71–30Sunfish Pondb USA – – – – 36–12 57–77Chilika Lakec India 4–74 52–143 10–101 28–59 21–63Clear water Laked Ontario, Canada – – 1133 800 190 95Fairbank Laked Ontario, Canada – – 45 21 16 88Joe Laked Ontario, Canada – – 85 56 34 59Agricultural soile Spain 14 115 35 230 69 500Ell-Ren riverf China – – 11–215 15–1200 32–460 45–1600Oka riverg Spain 15–50 20–180 25–130 40–150 25–110 100–360Seaplane lagoonh USA 14–48 100–1730 108–150 19–240 73–1270 108–580Severn estuaryi Britain – – – < 1.5 < 0.5 2–6Nainitalj India 7–33 11–59 30–64 18–40 6–21 31–105Bhimtalj India 13–20 47–71 26–42 34–60 45–178 42–73Sattalj India 48–80 9–28 57–80 20–101 62–80 26–47Naukuchiatalj India 41–87 12–47 26–51 80–120 48–73 66–159Crustal averagek 25 100 75 55 12.5 70Upper crustk 10 35 20 25 20 71Carbonate rocksl 0.1 11 20 4 9 20Average shalel 19 90 68 45 20 95avan Griethuysen et al. 2005bSzymanowska et al. 1999cYu et al. 2001dSprenger and McIntosh 1989eIrabien and Velasco 1999fCarroll et al. 2002gMortimer and Rae 2000hPanda et al. 1995iTessier et al. 1985jPresent studykTaylor and Mclennan 1985lForstner and Wittmann 1983


2009). The trace metal (Fig. 4) concentration ofNainital Lake is much higher than the averagecarbonate rocks, which indicates some other ad-ditional source for the metals. The presence of abus station near the lake and the draining of thedomestic wastes into the lake are the major iden-tified anthropogenic sources. Decreasing concen-tration of the metals cobalt, chromium, and nickel(Fig. 4) is due to reduction of iron and manganeseoxides and simultaneous release of these metalsinto the interstitial water (Gambrell et al. 1991;Carroll et al. 2002; Davison 1993; Koretsky et al.2006). Almost uniform concentration of the met-als, copper, lead, and zinc exhibits their inertnessfor the redox condition and are retained in thesediments by the carbonate or sulfide minerals(Davison 1993; Boyle 2001). The concentrationof the trace metals in the Bhimtal Lake is muchless than the average shale concentration, exceptfor copper and lead (Fig. 4), which are added tolake systems through vehicular pollution (Sparks2005).

The depletion in potassium content in the sedi-ments can be used as an index of the chemical ma-turity of sediments and consequently a proxy forthe intensity of chemical weathering (Schneideret al. 1997; Zabel et al. 2001). Al2O3/K2O ratio,used to know the influence of the soil erosionin the catchment area shows dominance of soilerosion (Purushothaman 2009). To assess the pa-leoenvironmental and paleoredox conditions pre-vailing in the lake system, it is necessary to un-derstand/estimate the sediment input from thecatchment area. The sediments and sedimentaryrocks usually contain various proportions of min-eral phases, like biogenic phases, which dilute themetal concentration in the sediment. The cross-plot study of metals over aluminum and titaniumwere used to infer the influence of catchment areain the lake sediments. The metal aluminum some-times is scavenged as hydroxide coatings overbiogenic particles (Tribovillard et al. 2006 andreferences therein), hence, the use of titaniumis preferred as it is immobile during diagenesis(Calvert and Pederson 1993; Tribovillard et al.2006). A good correlation is observed if the metalsare derived from detrital mineral fractions. Thepresent study shows that the metals have very

bad correlation with titanium indicating less inputfrom the catchment area. The metals chromium,zinc, and iron show good correlation and leadand nickel show least correlation with titaniumin Nainital Lake. Metals copper and cobalt showgood correlation with titanium and chromium andcobalt show least correlation with titanium inBhimtal & Sattal respectively. These metals donot show any significant correlation with titaniumin Naukuchiatal Lake.

Hence, to understand the influence of anthro-pogenic activity, the geo-accumulation index pro-posed by Muller (1979) was used in the lake sedi-ments. It is determined by the following equation,

Igeo = ln[Cn

/(1.5 × Bn)

]

Where, Cn is the concentration of the metal inthe sediment, Bn is the back ground value ofthe metal; generally the value of average shaleproposed by Turekian and Wedepohl (1961) isused. The pollution state of the lake sediments aredetermined by the Igeo value, which varies from0–6, where, 0 denotes uncontaminated sediments,3 denotes, moderately polluted, and 6 denoteshighly/strongly polluted sediments.

The Igeo value of Nainital Lake shows thatthe metals are uncontaminated–moderately pol-luted in nature. The metal lead shows anuncontaminated–moderately contaminated na-ture throughout the core indicating vehicular pol-lution. The metals chromium and nickel withmoderately contaminated (Table 4) character inthe up core shows increasing pollution in recentpast. The metals, copper and zinc with moder-ately polluted to moderately–strongly pollutedcharacter shows the influence of pesticides andsewage sludge (Sparks 2005). The metal, cobaltshows very highly polluted (Table 4) nature ofthe sediments. All other lakes show uncontami-nated nature for almost all metals except, cobaltin Sattal and Naukuchiatal, showing uncontami-nated to moderately polluted (Table 4) characterand Lead in Bhimtal and Naukuchiatal showinguncontaminated–moderately polluted to moder-ately polluted nature.


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Metal speciation

Nainital Lake shows different speciation charac-teristics with that of the other lakes. This might bedue to the presence of high anoxic condition andcarbonate lithology in the catchment region. Jainet al. (2007) on their study on metal speciation inNainital Lake have observed that the metals Feand Cr is present mostly in the residual fractionand Ni, Pb, and Mn are present in the first threefractions. Our study also exhibits similar charac-teristics with high concentration in the carbonatefraction followed by iron oxide fractions (sum ofall iron oxide fractions). The variation of percent-age of fractions in Nainital Lake with that of ear-lier reported study (Jain et al. 2007) might be dueto the difference in fractionation procedure used.Leleyter and Probst (1999) method is used in thepresent study to precisely understand the natureof chemical forms present in the lake sediment.Speciation of various trace metals in the sedimentsof the lakes are discussed below:

Iron Iron and manganese are the two metalswhose biogeochemical cycle in the aquatic envi-ronment determines the fate of almost all met-als. Iron is one of the most abundant metalsin the Earth’s crust and dominates in the la-custrine sediments (Davison 1993). Iron presentin the aquatic environment settles down as theamorphous iron oxyhydroxides, and dissolutiontakes place at the anoxic sediment–water inter-face. Amorphous iron oxide with aging, trans-forms to the stable crystalline iron oxides (Tessieret al. 1996). Although the reduction of the pre-cipitated iron oxyhydroxides is dominant at thesediment–water interface where organic decom-position dominates, not all the iron oxyhydroxidesare released (Davison 1993). Higher concentra-tion of iron in the oxide fractions (amorphous,crystalline and manganese bound fractions) inthe Kumaun Himalayan Lakes may be due tothe above discussed processes. In the presence ofsulfides, the dissolution of these oxides enhancesthe formation of iron sulfides, mostly of macki-nawite (Schwientek et al. 2008).

Manganese Manganese occurs as carbonate atlower anoxic/sub-oxic condition and sulfides at


higher anoxic condition (Davison 1993). Domi-nance of carbonate fraction may be due to theprecipitation of manganese as rhodochrosite oralong with calcite (Koretsky et al. 2006). Verylow concentration of manganese in the oxide frac-tions is due to the characteristic of manganese todissolve faster than iron in the anoxic condition(Davison 1993). In the presence of organic matter,manganese dissolution is enhanced resulting inits release into the water column. The releasedmanganese gets adsorbed onto the settling clayparticles and mineral surfaces and also gets ad-sorbed onto the carbonates. The manganese ox-ides that have escaped dissolution might havetransformed to the most stable forms with aging atdepth.

Chromium, Nickel, and Cobalt Chromium,cobalt, and nickel show similar characteristics inchemical forms. They prefer manganese and ironoxyhydroxide forms, over the other forms (Scholzand Newmann 2007). All the three metals showhigh concentration in carbonate fraction showingincreasing trend up core; chromium and cobaltshow drastic increase compared to nickel. Thisis because nickel has an affinity to form sulfides(Jacobs et al. 1985). These metals are found to beassociated with the carbonates and organic matterat high anoxic condition (Yu et al. 2001).

(A) Cobalt

Higher amount of cobalt in the carbonate fractionin Nainital Lake may be due to the presenceof high concentration of carbonates and due tothe prevalence of high anoxic condition in thelake. In general, cobalt shows high concentra-tion in crystalline iron oxide, followed by the or-ganic fractions (Koretsky et al. 2006). At lowerEh, cobalt prefers to associate with the sulfidesand organic matters. Cobalt adsorbed on to theamorphous iron oxides on aging gets convertedinto crystalline iron oxides. Cobalt bounded tothe manganese oxides, gets released into solu-tion during the reduction of manganese oxides athigh anoxic condition. The released cobalt in thepresence of organic matter complexes with themineral surfaces forms mono-sulfides and settlesdown (Davison 1993).

(B) Chromium

Chromium may enter an aquatic system anthro-pogenically through the landfills, scrapheap in theform of oxides and organic and inorganic ligands.Chromium, generally, is sorbed by iron oxideminerals than any other phases and settles downon the sediments. Decreasing trend up core ofthe crystalline iron oxide phase compared to theamorphous iron oxide phase may be due to thetransformation/aging of the amorphous iron oxideto crystalline iron oxides. Reduction of these ox-ides may liberate chromium from the sediments(Gambrell et al. 1991; Carroll et al. 2002; Davison1993; Koretsky et al. 2006). In the presence oforganic matter, chromium binds with humic sub-stances (Guo et al. 1997; Koretsky et al. 2006).

(C) Nickel

In general, nickel is found to be present in theorganic and residual fraction (Panda et al. 1995;Staelens et al. 2000; Zhai et al. 2003). This is dueto the adsorption of nickel by the formation ofligands in the presence of high organic content(Jacobs et al. 1985). It has been found that nickelat high anoxic condition binds with the oxidesto undergo reduction and gets released to thewater column. Higher concentration of chromiumin the exchangeable and water dissolvable fractionis also due to the release of chromium by thedissolution of iron and manganese oxides. The re-leased nickel gets adsorbed or co-precipitated bythe carbonates (Yu et al. 2001) in the presence ofhigh carbonate content as in the case of Nainital.

Copper, lead, and zinc These metals are chal-cophilic in nature; copper and zinc are micronu-trients and is settled along with the readily oxidiz-able organic matter. These metals at high anoxicconditions generally are associated with the car-bonate and organic matter and are not affected bythe redox conditions (Yu et al. 2001).

(A) Copper and (B) zinc

Copper may enter an aquatic system throughbrake linings, metal finishing, manure, pesti-cides, wood treatment; lead through automo-bile refineries sewage sludge, pesticides and zincthrough sewage sludge, pesticides (Sparks 2005).


Under high anoxic conditions, these metals arebound to the carbonate and sulfides (Davison1993). This is a major reason for the dominanceof the carbonate fraction in the highly anoxicNainital Lake sediments compared to the otherlakes, where they are relatively less anoxic. Thesemetals generally show high concentration in theorganic and oxides phases. Higher concentrationof copper and zinc in the organic fraction may bedue to their affinity towards the organic substanceand their ability to form complexes (Guo et al.1997; Koretsky et al. 2006). As these metals areless affected by the redox changes they also occurin higher concentrations in the oxide fractions.

(B) Lead

Lead behaves similar to copper and zinc in theNainital Lake sediments, and generally occurs ascarbonates in aquatic systems. Higher concentra-tion of lead in residual fraction shows its naturalorigin. Dominance of carbonates and oxides inthe sediments shows precipitation of lead from theoverlying water column.

Conclusion

The metals in the Kumaun Himalayan behavedifferent with respect to the lithology of the catch-ment area. The presence of high organic mat-ter in the lake sediments and its decompositioncauses anoxic condition in the sediment–waterinterface. The metals in the lakes generally areprecipitated as oxides in the water column andas organic chelates. Iron and manganese play animportant role in sequestration of metals in thewater column and release in the sediment–waterinterface. Dissolution of the oxides and decompo-sition of the organic matter in the anoxic conditionis evidenced by high metal concentration at thesediment–water interface and interstitial water.The carbonate phase derived from the carbon-ate lithology of the Nainital Lake act as majorsequester of the metals in this lake. Whereasthe other lakes show high concentration of met-als in exchangeable and manganese and amor-phous iron oxides indicate their adsorption orre-precipitation with oxide phases. The bad cor-relation of the metals with the titanium indicates

that these metals are re-precipitated to large ex-tent than of detrital origin.

Acknowledgements We thank MoEF, India for fund-ing the project. P.P specially acknowledges MoEF, CSIRIndia for support through fellowship. We also thank Ravi,Yadav, and Vijay for their help in the field and lab.

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Trace metals biogeochemistry of Kumaun Himalayan Lakes, Uttarakhand, India