4.1 GENERAI.

111 tliis Chapter. {lie cirai.actcristics o f tile tlirce cliosen efflue~its diie to ariiiicinl contariiination of

t\rao coiiirnercinl soils (Itoulinite aritl bentoiiitc) and tiirec iiati~ral soiis (NSI. NS2. US31 in t\xo

modes of'operatioii (hatcll :~nd coritiriiioiis ~iiotles) and soil - poli\i[;~nt ii?icinctioiis :ire critically

assessed and presciilctl. Basctl oil thc i~bovc asscssnieirt, iiie clrect oii tl?e intlcs aiid slre~igrli

c l i a r a c t e r i s : ~ ~ ~ of the commercial soils ( r S I a i d C'S2) aiid ilati~ral soils (WSI. US2. NS3) are

discussed and presented. Results fro111 t!ic atlopreti ~natl:e;:iatica iiiodcl have beer1 coriipared

\\it11 the expcrirnental data and significant observatioiis there froill, arc ~l lso presented.

4.2 SOIL - POLLUTANT INTERACTION: INORGASIC I'OLLUTANTS

4.2.1 B;ttch hlotlc

(A) Kflolbiite Soil (CSI)

.l'lic clinrcicicristics oSiil1: Lllrcc cS!luents tluc Lo arlilic~nl contami~latiori o n com~iierci :~ soil - CS I

, in batch mode. are presented iii Tables 4.1 (a) and (b) and the variatioii of pH and alltalinity;

cl~loritlc and sulpliate; cleclrical concluctivily (KC). lotal ~oli t ls ('1's) mid total ciissolvctl solids

(TDS), \\itIi time (in d a y ) are shown in Figs. 4.1 (a) - (c) to 4.3 (a) - (c), respec,tively. The

iiiteractions between CSI a~ id tile varioi~s inorganic pollutaiits present in the three effli~ents

considered. are explained based on critical analysis of the above results.

(1) ptl and Alkalinity: The pl-i values of arninoacid, surfactant and pliarmaceutical effluents

Irere ill the range of 3 to 4; 6 to 12.1 and 3 to 4 before passing tlirougli the soil colullin (i.e.

before coiitaminatioii). respectively. The pH values were found to vary after contamination on

CSI from 6.2 to 8.3, 6.7 to 8.2 and 6.6 to 8.2, for amino acid, si~rfactant and pharniaceutical

effluents, respectively.

Amino acid and surfactant effluents showed peak pl-i values of 8.3 and 8.2 respectively at the

end of 18"' day, whereas, a peak pI-I value of 8.2 was observed at the end of 14th da) for the

pIia~~iliacciitic:tl c l l l i~c~ i i . SLc~idy sintc contliiiuil was li!~l~iLi to !I;IVC. ~ C C I ~ il[i:~i~?c:I ;it tlic clid 01'00111

day arid 84'" day respectively. for aminoacid and s~irfactziit etili1e:its ant1 pliarmaceutical

eCiliierit was obscrved to attain a steady state coittii1ion at llic ciid of 84''' clay.

pli variation in tliis experiniental study was found to folio\\, a similar trend ~vitli that oi'R~1Ii1 and

Daniel (1997) for tlie experiments conduc!ed by tlieni oil geosyntlietic cla) lii~ers (tested for fly

ash and milnicipal solid waste as leachate) for the periiieatioii of acidic and alkalilie chemical

solutions. Tlie pH of tlie periiieated soliitions (\vitli 0.lM NaOi-i and 0, I hf 1-1CL as i~if l~ient in

tlie above study) were respectivel~ Ibi~iid to vary f'ro111 9.5 to i3 aritl 3 to 95. 'i'hese pH variations

are comparable to the pl-I variations observed in rile present study. for amino acid and

pliarmaceiitical effliients.

Alltalinity of amino acid and phariiiacei~ticai effluents \\.ere zero, ivllereas. it was I000 to 5000

iilg/I, for surfactant effluent, before passing throilgli the soil coluinn. Ilo\vever, tile alkalinity

was found to vary (after contamination on CSI ) from 72 to 725, 72 to 725 and 58 to 871 mg/I,

ibr amino acid, surfactant niid pharmaceutical effluents, respcctivcly.

Alkalinity of amino acid and surfactant effluents (iiitei- contanii~iation), showed peali alltalinit>

\aIiies of 725 11ig;I. at tile elid of 60"' day. Flo\vever, a lpealc alltalinity value of 87 I mgiI, was

observed at tlie end of 25"' day ill the case of pharmacei~ticiil effluent. Steady state conditioli was

found to have been attained at the end of 60"' day for amino acid and 84'" (la) for surfactant and

pliarmaceutical eftlilents.

12) Chloride and Suloliate: Cliloride concentrations of amino acid and pliarmaceii~ical effluents

were zero, whereas, it was 1900 to 2500 ~ n g i L for surfactant effluent, before passing ~lirougli tlie

soil coltimn. Tlie cl~loride concentrations were found to vary froni 21 to 2357. 12 to 2428 and

28 to 5935 1iig1L afier contamination on CSI. for amino acid. surfactant and pharniaceutical

effluents. respectively.

Amino acid and surfactan1 effluents showed peak chloride concentrations o f 2 3 5 7 and 2428

mgiL at the end of 14 and I lib day, respectively. A peak cliloride concentration of 3935 n7glI.

was obsewed at tlie elid of i 1'" da) iil tlie case of pl~arn~aceutical ei l l~~eii t . Steady state conditio~i

\+'as found to have heen readied zt the end of 39"' da!! anrl 74''' dai . respcc~ivel!. f o r aniiilo acid

anti surfactant efllueuts and at the elid of 60''' day. Tor pliariiiacei~ticai ef'fliient.

Stilphate coricentrations of amino acid and surfactant effluents were foir~id to be iri the range of

200 ro 260 and 200 to 4.500 mg!L. wiiereas, it h a s zero for pllarninceutical ef!luent before

passing rliroi~gli tile soil co l i~~nn . tlo\vever, the sulphate concentrations were foli~id to vary after

contaminatio~i on CSI, from 40 to 1640. 20 to 1520 and 20 to 1290 ing/L for a~n ino acid.

surfactant and phamiacei~tical effluents, respectively.

m i l l o acid and surfactarit effluents (after conta~iiination) shoived peak sulpbate concentrations

of 1640 and 1520 ~ng!.L at the end of 32""ay aanti 12:'"aay, respecrively. But. tile peak

concentration of phar~naceutical effluent was observed to be 1290 mgll, at rhe end of 32"' day.

Steady state conditio~i was found to Iiave been reached at tlie end of 52"%aaq for a~n ino acid and

pharmaceutical effluents, ~vliereas. it was at the end of 12""ay, for surfactiiiit eftli~ent.

I t is evitlent li.orn [lie ahove. l l~at tile retcntiori of s~ilpliatc co~icentration undergoes ;I lorgcr

variatioii when compared to tliat o f cllloi.ide, before attaining tlie stead! state condition. Tliis is

due to tlie reason tliat sulphate is reacting at a lhigher rate and assists ill brealcup o r soil intel.stices

leading to pernleation of more sulphate ions than that of chloride ions. Moreover, the variation

in sulpliate conceiitration is comparably less for pllarmacec~tical eini~eri~s. ivllen compared to

the other two effluents considered.

Variation in chloride coricentration observed in the present study is foulid to be Tery close to tlie

valiie reported by Badv and Rowe (1996) for the experimeiital study on silt and clayey silt for

chloride transport uilder unsaturated condition (batch ~liode). 'The reported varia~ion in chloride

concentration ie 800 to 1200 ingIL for tile above study is cornparable to [lie steady state cliloride

concentration of 2250 mg1L for surfactant effluent, under batch mode of operation. Moreover.

the variation in chloride and sulphate concentrations observed in tile present ~ t u d y are found to

be similar as that of the result reported by Das and others (2002) for tlie experimental study

of tile impact of amino acid effluent on the qilality of soil and ground water.

(3) Total Solids ITS). Electrical Conductivity IECj 2nd Total Dissolved Solids ('fDS);

The concerltralion of TS of amino acid. surfacta~lt and phal-rnacet~:icaI effluents were it1 the

range of 18 to 19 x I 0'. 8.1 to 16.4 x 10' and 24.5 to 34.5 x 10' mg/L respectively, before

passing th ro i~g l~ tlie soil column ( i.e. before contaminatioii ). Howeber, after containination on

CSI; tile coi~centrations were fotind to vary froin 0.2 to 9.0 x lo', 0.3 to 12.0 s 10' and 0.5 to

14.0 x 10' mgli, for amino acid. surfactaiit atid pharinaceiltlcal effluents, resnectively.

Aiiiino acid and si~rfactant einue~its slio\ved peak .'TS' coriceiitratio~i oT9.0 s i0' a!;d 12.0 u 10'

rn_e;L. at !he end of and 60th and 67th day. respectivel\;. \\liereas. a pcalc conce~itratiou of 14.0

x i0' ~ n g / L \\as observed at the end of Gith day, for pharniaceu~ical efflilent. Steady state

cond~t io~ i was foillid to reach at the end of 46th day for anilllo acid and 84th day for

sul-faclan: and piiarinaceutical effliienrs.

Tlie above behaviour slioivs tliat 1iiglie:- peak values resull in lower retelitioli time. It can he

o b s e r ~ e d tliat tlie SRT diie to amirio acid and surfactant conramiiiation at1 CS I. is liiglier than

that of' pliariiiaceutical contamination on CSI .

EC value of aminoacid. surfactant and phar~i~aceiltical effluents were 10.00 to I2 38 x 103. 0.02

lo 0.05 1 10' allti 12 to I X x 10' pS/cni. rcspectivcly, bclbre pnssilig tlirougli Llic soil colum~i (

ie before contamination ). I-lowever. values aftel. coiltamination oil CSI. nere foi~nd to vary

fro~ii 1.08 lo 7.32 x 103, 1.02 lo 3.22 s 10' n~itl 1 .(I4 Lo 3.02 x 10' liS/cm for amino acicl.

surfactant atid pharmaceutical effluents. respectively.

Amino acid an3 stirfactant effluents sliowetl peak EC valiies of 7.32 x 10' a:icl 3.22 x 10' 11S1cm

at the end of and 2" day, respectively. A peak EC value of 1.02 s 10' pS,'cni was also observed

at tile end of 2"d day for pl~annace~itical effli~ent. Steady state conditions nlerc found to reach at

the end of 60"' day for amino acid ant1 8lS'day for surfactant and pharmaceutical effluents.

Concentration of 'TDS' in amino acid . surfactant and pharmaceutical effluents, ue re in the

range of 15.50 to 17.80 x lo3, 5.00 to 10.00 x lo3 and 18.50 to 25.00 x 10'1ng/L respectively,

before passing through tlie soil colunui ( i.e. before contarnination ) and they were found to vary

afier co:?iai i i inr . i~o~~ o:i CS1 iio~ii 0.50 :rt 6.00 s 1 0 ' . O.?il to 13 O(l u 10' act1 0.4ii to 8.00 x I 0'

ingil. for aliiiilo acid, si~rfactant arid pl~ar;naceutic;~i c f l l i ~ ~ ~ i i i . respcc:i\ el!

A11ii:io ac~tl afid s~iri'iciant efllc~enls sho\ved peak "i'i1S' co~icciitratio~i oi6.90 x 110' and 13.00 x

10' iiig I . a! tile e ~ i d of 53'" a ~ i d 2"" da? I-erpecii\,el!. I io\vc\er, :I lpc,iii ..l'l)S' i.o~iceii!ra!ioil (il.

11.00 s 10' iiig!l. u a s observcd only a! !lie e~;d (11. 74"' day for ;,!?as~l;acc~~!ic:~~ el'lli~elii. Steady

i t i~ic conditiorl? \&err: l'ouiid lo reach at tile end ot'60'" cia! a~,tl 84"' day, r~speetively h r a~i i ino

licit1 aiid suri'actant effluents. iiliereas. i! \ \as at tlie end o!'tlle 84"' clay. I"<,; pl~a~inaccut icai

esll~lelll.

The cliai-ac!erisrics of tlie illree cfflue~its due to artificial coniiiniinaiioii on CS2 . iii batcl~ ~i iode.

arc p rc~c~ i i c t l in Tahlcs 4.7 (a: and (h) and [tic variation of pll arid allialiilit?; cl~loride a i ~ d

sulpliate: I:(:. 'T'S and I [IS with time (in daqsi are siio~vn ill Figs. 4.8 (a) - (c) to 4.10 (a) - (c).

I-cspcctivcly. 'Tllc il~tcractiolis hetween CS2 and lie variocis inol-ginic poiluia~lts prcscnt in the

three eftlue~irs considered. are explai~ied based on critical analysis of !lie above resi~lts

( L m n d alkalinit): The pf-l values o f amino acid, siirfactant and pl~armaceu~icnl effluents

were in the range of 3 to 4. 6 to 12.1 and 3 to 4 before passing tlirougii tlie soil colu~nn ( ie before

contamination 1, respectively, The pt l values were found to bary after contamiiintioti on CS2,

from 4.5 to 8.9. 6.9 to 8.5 and 6.5 to 9.0 for amino acid, siisfactant and plia~~maceutical

effliients. respectively

Amino acid ant1 surfactalit effluents silowed peak pi-1 values of 8.9 aiid 8.5 a t tlie end o f 36"' day

and 85"' day, wilereas, a peak pH value oS 9.0 was observed at tlie end of 64'" day for Llie

pharinaceutical effluent. Steady state condition was found to Iiavc been reaclied a1 tile end o f 61%'

day. 75"' day and 78"' day for amino acid. surfactant and pharmaceutical emuents.

pl-l variation ill this experimental s t i~dy was found lo rollow n si~iiilar trend ~ i t h that o f Rulil and

Daniel (I 997) for the experiments conducted by them on geosynthetic clay liners (tested for fly

as11 aiid bentonite as lec~cliate) for tiie ~,er!iicatioii oracidic at~tl aii:nli~:e clielnic~l rola:ioris. Tlie

bpi1 oI'!Iie lpct~iieatetl sollition? (\\it11 O . i M NaOi-1 alid 0.1 1\1 I-lC1. as I I ~ : ! ~ I ~ I ? I ill [lie above sti~tly)

ne re respectively io~intl to var. t'l-on] 9.5 to 13 and 3 to 9.5. I'iiese 111 1 \,ariatiotis are coiiiparable

to tlie p l l variatiotis obse r~ed iii tlie prcsent stiidy. for aiiiino acid aiid p l i a r~nacc~~t icd effluents.

Alltaliiiit~ oi'aiiiiiio acid aiid piiarniaccutica! efiluenrs were iwo . \\liereas. i t nas 1000 to 5000

11ig:l.. for s~irfacti~nl effllicnt. !kfore passiiig tlirotigli tlie soii coii11111i. I-ic\\'c\,e:-. the alliali~~ity

was Ibunc! to vary (ailer zontatiiinatioii) from .37 to 552. 172 to 401 niid 93 to 564 ~iigl l . ibr

ainino acid. s~~rfactant and pliarmaceiitical effluents. respecti) ely.

t\miiio acid, s~~rfnctant and pharmaceutical effluetiis (after contarninat i~~t~). sl~oived peak

alltali~iity \,aIi~es of 552, 491 and 564 mglL, at tile e!itl of 50". 2Id day and 19'' day,

respecrivel). Steadp state cotidition was found to liavz been reaciicd at the end of his ' day. 75"'

day ant1 78"' day for amilio acid. surfactant and phai-maceutical e f f l t ~ e ~ ~ t s . respectively.

Variation in pi-l and alkali~iity as observed above were found to be rniniiiil~iil duc to liigli clay

content. 'i.lie variations in l~ydrogen - ion conceiitration were found to be appreciable from 2"' to

84"' day u~id tlien i t gets stabilizeti to a crinsistc~il val~ic lo\wl.ds tlic elid of baicl~ lnocic. The

above plienomenoii is in agreemenr nit11 tlie reportetl physico-chemica! cliai~ges of soil

properties investigated by LVosten aiitl Geni~cliten (1988) and for rlic s tud) I-eportetl by Cliu

(2003) carried out Ibr si~rfactant contaminated soil tirider a two pliase systen? (1.e. gaseous &

liquid phase).

( 2 ) Cliloride and SuInIiate : Cliloride concentratiot~s oramino acid 2nd plial-~iiaceutical effluents

were zero. lier re as. 1900 to 2500 mgiI, for surfactant effluent before passing :Iirougl: the soii

colii~ii~i. Tlie chloride concentratio~is were Ihiinci to vary ai'tcr contamiiiarion o n CS2. from 204

to 2925; I06 to 1728 and 62 to 2180 ingII, for atliino acid. rurfactalit and pl~armacei~tical

effluents. respectively.

Amino acid. siirfactant and phar~nnceiltical effluents, showed peal< cliloriJe concentrations of

2925, 1728 and 3935mglL at tlie end of 2nd , 40"' and 12'" day, respectively. Steady state

co~idition *as found to have been reaclietl at the end of 61" day. 64'" and 50'" day, respectively,

for amino acid. siirfactant and pharniacciitical ef luents .

Suipilate concentraiions of amino acid ano surfactan1 effluents were in tlie range o f 200 to 260

and 200 to 4500 mg/L. \\liereas. it was zero for pliarinacei~tical effluent. before passing tlirough

tlie soil column, l-loc\ze\rer. the concentrations were fount1 to var) after coiitamiiiation on CS2

from 200 to 1850; 400 to 1680 and 200 to 1540 tng/I. for amino acid. surfactaiit and

pharmaceutical effluents. respectively.

Aniino acid, surfactant atid pliarmaceutical effl~ients (after coniaminatioii) slli.\icd ;leak suipliate

concentratioiis of 1880 1iig;L . 1680 riigt1, and 1840 iiig'L at tlie end of 68"' . I."" day and 57"

(la!. respectively. Steady srate condiiion \\as fount1 to 1ia1,e bcen reaclied at tlie eiltl of 50"'. 47'"

antl 40"' da), for aiiiilio acid. s~irfictaiii and pliarmaceiitical eSI1uen:s. respectivel).

It is e ~ i d c n i fso~ii tile above. tliat tlie retenti011 of s~~ lp l i a t e coiiccntration iiiitlergoes a larger

variation \i'lietl compared to that of cliloritle, before attaining the sieady state co~ id i t ion Tliis is

clue to tlie reasoli tliat sulpliate is reacting at a lhiglier rate and assists in b~.cal<iip o f soil

interstices leading to pcr~iieatioci of ~i iore siilpliate ions tlian tliat o fc l~ lo r ide ions. bforeover. !lie

a i a t i o I siilpliate concentration is co~nparahly less for pliarmaceutical effluent, \\lien

compared to tlie other two effluents considered.

Variaiio~i in cliloride colicentration ohserved iii tlie present stutly is found to he close lo

the value repor[etl by Uadv and Rowe (1996) ibr tile experimental sti~d! oil silt antl clayey silt

for cliloride transport ~ ~ i i d e r ilnsaturated conditio~i (batch mode). Tile reported >ariation i.e.

chloride concentration 800 to 1200 mgiL for the above stiidy is comparable to tile steady spate

chloride concelitration of 2250 mg/L for surfactant under batch mode. I r is also seen that the

varia~ioli ill cliloride concentration observed in tlie present study is foillid to he s i~n i l a r to tile

reported results by Ro\ve and Badv (1996) for this experimental study on chloride ~ i~ ip ra t ion

tlirougli clayey silt tlnderlain by fine silt under near saturated coiidition

13) Total Solitis ITS). Electrical Co~tductiiity (EC) attd 'Total Dissolved Solicis (TDS) : The

concet~tration of .TS' of ami~ioacid. surfactant and pharmaceutical eiflueiits it ere it1 the range of

18 to 19 s !0'. 8.1 to 16.4 x 10' and 24.5 to 34.5 s 10' mgl i . respectively, before passing

ihroi~gli the soil coiunill. iionever, the concentratiotls were foi111d to var) aftei- conta:iiitiation on

CS2. from 1.00 to 36.00 x 10'; 2.00 to 23.00 x 10' and 1.00 to 16.00 x 10:'tngil. for amino acid.

surfactatit and pliarn?aceutical effluents, respectively

Alliino acid. surfactant alld pharmaceuticai effluei~ts sho\\ed peak '1's' concr~ltratio~is oC36.00

x 10' : 23.00 x 10' and 16 00 s 10'mg/l, at the end of 54"' , 29"' and 99" daq. respecrively.

Steatl) state conditioti was found to h a w bee11 reached at tlie e11d of 61"' day for hotli ainino acid

and surfactatlt effluents and at tlie etid of 68"' da! for pharniaieiirica! effloenr.

'Tlie abo\e belia\iour slio\vs thdt liiglier pea!( \'slues resitit in lower retention t in~e . It can be

seeti tiiat tile SRT ibr atiiino acid atid stirfactant contamination on CS2 is liiglier ~liat! that of

pliartnnceulical coiitnmination on CS2.

'IT' ~ n l ~ i c of a~iiitio aci t l~ sitrfactant and p11armaccutic:il eflliccnts w r c in tlic range of 10.00 to

12.38 .; 103, 0.02 - 0.05 s 10' and 12 - 18 s 10' pS1cm respectively. before passing tlirougli tlie

soii coluinn aiid tlieq nc rc Ihitnd to \';u.g aftci- contati~itintion oil C S 2 finm 0.36 to 4.45 x 10':

2.07 lo 4.13 r 10' zt~itl 0.23 lo 4.96 s 1 0 ~ 11Slcni. fos a117iiio nsid. siirr,ictailt ailti plinrnlaccuticd

cffluctils. rcspccti~ely.

Amino acid, s~irfactailt and p1,arniaceuticaI eff luc~~ts slio~ved peak EC val~ies o r 1 45 s IO' , 4.13

x 10' and 4.96 s 10' ~tS/cm at the end of 2"" 43r"~id ci8"' da). respectivei). Steady state

condition 1zas ibki~ld to rcacl? al the entl oC61" da!, 51''' ,lntl 57'" day. rcspcctivel>~. Cor amino

acid , surhctant and pllarmaceutical efili~ents.

Concentration of 'TDS' in amino acid. surfactant and plia~maceutical effluents n3ere in the range

of 15.50 to 17.80 s 10'; 5.00 to 10.00 x I @ atid 18.50 to 25.00 x 10'1n@:I,. respectibel~; before

passing tlirough the soil colunln. Tlie co~~centrations \Jete found to vnr) after contaminatioi~

c;ii CS2 from 2.00 to 14.00 x 10'; 1.00 to 10.00 x 10' and I . O O to 18.20 x 10' mglL for amino

acid, s~irfactatit and pharmaceiitical effli~ents, respectively.

.2niino acid, surfactant and pharmaceutical effluents slio\\ed peak 'TDS' concenlrations o f

14.00 s 1 0': 10.00 x 10' atid 18.20 x 10' m d L at rile end of and 26'" , I 2"' day and 2""ay,

respectivel!.. Stcatl> statc conditioii \ \as found to liabe been seaclied at tlie eiid of 50'" da? . 43rd

arid 33"'day. respecti\,ely. Tot. atnillo acid . ?i~r-f'acrai?i anti plial-~naceuticnl efiluei~ts.

Tlie cliaracteristics of tlie atiiino acid effliietit ( E l ) due to artificial contaminarioii oil tlie rhree

natural soils (NSI, US2 and NS3 ) . in batcli niode are presented in I'ables 4.13 (a) - (b) and the

variaiioii of pH and alkaliliity ; TS, TDS, cliioride and siilphate for NSI to NS3 are given in

Figs.4.14 (a) - (c) to Figs 4.16 (a) - (c) respecii~cly.

( I i pH and Alltalinit~ : Variation in pi4 was obserbetl to be in tile range of 6.0 to 7.7 for NSI

and NS2 ; 5.1 to 7.6 for h S 3 , during the batch inode of operatioi-i and pt l attained the steady state

betueen tiic 65"' and 70"'daq. for all tlie natural soils considci-ed.

Variation in alltalinity was obse r~ed to be in tlie range o f321 to 2575 mgll, for S S I and NS2 ;

859 to 2578 mgiL for NS3, diiring tlie batch niode of operation and alkalinity attained tlie steady

state on the 35'" day for all the natural soils coilsidered.

(2) Electrical Conductivitt IEC). Total Solids ITS) and Total Dissolved Solids (TDSL

'EC' values have declined fro111 a higher vailie 1 2 . 7 ~ 1 0 ' )I Sicm for NSl and 15.9 x1 o3 p Slcm

for NS2 to a lower v a h e of about 3.8 slo3 11 S/cm for NS, and NSz and attained steady state

on 52""a\1 o n ~ a r d s . On the other hand: the startiiig valiie of about 14.2 s10 ' ji Slcm for NS3

ilas rcnlnincd iiigii during tile first ISdayq of hatcli ~iiotlc a ~ i d therearicr tlccrcasetl cisastically

ailtl ;~t!niiletl steady state at the ell(! of 50"' da).

1 !, ailti I'LIS \\ere kii~iid to l~iidergo a large variation in the hatch niode. it ill1 ~! ieir co~ icc~~t re t ion

i)iiip in ihe rangc of aboi~t O 2- 8.0 s 10' mgll, for YSI . a n d O 5 -- i7 .9 \ 10' ilig/l, h r 2 S 2 ,

ili~ring tlic firs[ 10 days of opel-ation, lio\$ever . bc>oild 10"' ciay aild till tile (!aq ol'attainii~g tlie

<lead!, state (i.e. iOlh day ). the variation ill 1.5 n n d 7 D S co~icentrations \+ere foai~ti to be less.

SS3 slio\\etl still lhigller variation iii tile conccn~rat ioi~ of TS a~:d TOS . in the range fab bout 0.3

to 19.8 10' mg!l. and within tile first I0days ofopcratii,i> . in the ba~cli ~niocie. NS3 attaii~eci thc

stcad! state on h e 65" day.

'The \ariation in TS and TDS as observed in the present srtidy is tl>1111d to have a similar trend

\iit!i the reported investigations of Filjus et al (1907) foi- h e i r experimental s ~ i r d j ofcontaininant

traiislmrr through an unsari~rated soil layer beneath a laiidfill.

[-ride all(! Sulolia[e: The concentration o f cliloride u a s foiiiid to vary in the range of about

372 to 3722. 388 to 5318 and 399 to 7090 mg/I. for NSl . NS2 atid h S 3 ; ~.espectively during the

I" to 35"' day of batch mode. Steady state for NSI ai~t l NS2 \\as atlaitled from 36"' day o~lwards

aiid for VS3 on 43rd day. Tlie concentrrztioil of sulphate was fo~intl to \ary in tlie range of about

228 to 1616: 228 to 440 and 232 to 2480 mg/L. for NSI , XS2 aiitl NS3, respectitclj. during I " to

32" (lay of hatch mode. Steady state was reached on the 65'' daq for NS I anti NS2. \vliereas . it was on 39" (lay for NS3.

The above variation can be attributed to the shorter interval taltcn by tile pollutant (solitis) to

react with higher clay content available in NS3. Tlie higher clay conten1 is responsible for

sl~orter reteiitiorl time required to attain tlie steady state condition. Variation in the

concentrations of cilloride and sulphate observed in tile present study showed a sirniiar trend

as that of tile reported study, by Peirce et a1 (1987) and Rowe and Badv (1997). respectively,

on tlie effect of inorganic leachate on clay and migration of chloride and siilphate on fine sand I

silt.

(D) Surfflclntif Effluent oft A'S], fiS2 ni~d ,W

?.lie cliaracteristics of tlie s~irfactaiit efflue~lt ( E2) due to artificial contaniinatiotl on tile three

~iatural soils (NSI. NS2 and NS3 ) . in batch mode are presented in Tables 4.1'2 !a) - (b) and tile

variation of pH and alkaliliity : TS. TDS. nit[-ite. cl~loride and sulphate for h S l to US? ar-e given

in Figs.4.21 (a) - ic) to Figs 4.24 (a) - (c). respecti\ely.

( 1 ) p H and Alkaliliitv :- Variation ill ptl was observed to be in the range of 7.0 to 11.0 for NSI

and NS2 : 7.3 to 9.8 for NS3, between l s to 40"' day during the batch i i~ods of operation and pH

attaiiied tlie steady slate bet\veeti the 83'"ad 90"' day. for all the natural soiis considered.

Variation it1 alkalinity was observed to be in tile range of 179 to 4296 for NSl and NS2 : 259 to

3579 for NS:. during the batcli mode of operation and alkalinity attained the stead? state on

57" dab. for all the natural soils considered.

The above behaviour is attributed to the decrease in hydrogen ion concentration due to tile

permeation of salts from the soil. The pH and alkalinity got stabilized between 83.' day and 90"

day. The results obtained in tile present experimental investigations are found to be similar to

tlie esperimental results reported by Sivapuliaiali et al (1996) for the mechanisni and control of

index propelties of black cotton soil.

(2) Electrical conductivity IEC). Total Solids ITS) a~nd Total Dissolved Solids (TDS). 'EC'

values have declined from a lhiglier val~ie 25 slo3 p S!cm for NSI and 30 X I @ ' p S:cm for

KS2, to a lower valrie of about 5 x10' p S!cm for S S I and NS2 and attained stead! state on ~ 3 ' ~

day onwards. On the other harid, the starting value of EC for KS3 nhich 48 xi$ p S/cm,

remained high during tlie first 20 days of batch mode and tliereafter, decreased drastically and

attained steady state at the same time as that of KS 1 and US?.

TS and TDS were found to undergo a large variation in tile batch mode , with their concentration

lying in the range of about 9500 to 1 I5000 mg/L for NSI and 3000 tol5OO00 mg!L for NS2

during tlie first 40 days of operation. However, beyond 40" day and till the day of attaining

steady state ( i t . 77'" day), the variation in TS and TDS concentrations were found to be less.

NS.3 shoiied still liiglier variation in tlie coiicentratinn of TS and TDS. in die range of about

2000- 1?000 ing'L atid \vitii in tlie first 30 days of operation. i ~ : tile batch mode. US; attained the

steady state on the 84"' day.

Tile val.iaiion i n TS 2nd 'TDS as observetl ill tlie present stiiti!~ I S found to Ihave a si~iiiiar trend

wit11 tlie reported investigations of Fithus et al (1997). for [heir experi~ne~ita! study o f

coillamiiiant transport tlirougll an unsatilrated soil layer beneath a landfill.

~ l i l o r i d e and Su!p~te : ' r l i l : ccinceii~l-atioil oi'cliloridc aiit! s~ilpllate wei-c ib~ i~ i t i to Lary in

tlie I-anyc o f ribout 570 to 3540 iiigl. i'or NSi aiitl 570 to 4670 inigil, Sol NS2 11p tc 48d~l!s. \\'ill?

1;irger ~mria~ioii in co~ice~itration up to lI?e first 22 (la!,.. 170r NS3 ~aria:ion ill tile colicenrratiori

ilas in tile raiigc oi'aboul 650 lo 8740 iiig.'I 11pio 22 d:i>s anti tlicicaiici~ :uii!ai~icd coiialaiit.

Steatl! statc was leached 01, tile 48"' day for NS I ;ind '452. nliereas, i t \\,a$ oli 2 2 " ) d,~! i'or NS3.

'Slie n h o ~ c varintio~i c;ln he attributed to the shorter i i i~er\al talte~i by tile lpc~ll~ltaiil (solitis) to

react \\it11 liigher cia! conteiit available in NS3. The liigliei. clay content is responsil?le for tlie

~Iiortcr rctc~itio~i ti~iic reql~ired to attai~i steady state colidition. Varit~tioii 111 tlic conccntlxtic~iis

tis observetl in tile present stud? were coiiiparahle wit11 the reported resi~lts of Semer and Keddq.

(1995) for tile evaliiation of soil \~as l i i~ ig proccus to re~iioue mixecl contaniina~its fi.o~n a sandy

ioani. I.arger vnriatioli in [lie concentration o r chloride and sulphate observed up to tlic tit-st

22 days ivere clue to tile soil washing or dissoiutio~i (repeated adsorption or tlesosption) of

siirface inorganic iiiipurities taking place between the soil matrix and the aqueous pliase.

(E) Pl~nr~noceufical Effluent 012 NSI, !VSZ mzd 1YS.Z

The cliaracterislics of the pharmaceutical effluent ( E3) due to artificial co~itaminatioii on the

three natural soils (NSI. NS2 and NS3 ) , in batch mode are presented in Tables 4.25 (a) - (b)

and the variation of pH and alkalinity ; TS, TDS, cliloride and sulphate for WS I to NS3 are given

in Figs.4.29 (a) - (c) to Figs 4.32 (a) - (c), respectively.

1 I j pi! arid il&alirliti :- Varialion in pH isas observed to be in ilie range of 5.1 to 7.2 for ?dSI

and KS2 : 6.3 to 7.3 for NS3 during the hatch node of operation and p t l attai!led tihe steady state

betneeii tile 52"" and 41" day Cor all tlie iiati~ral soils considered.

Variation it1 alkalinity was observed to be in tlie rarige of 71 8 !o 34367 n ig i i for NS I . KS2 and

NS3 during the batcli inode of operation sild alltalinity attained the steady state 41" day for ail

the natliral soils consitlered.

(2)<lectricaI C o ~ i d ~ i c t i \ i ~ \ (LC). 1 otiil Solii!s (-1 S) ;111d 'I_ott~I 1lissi)lved Solidi ( I'IIS): 'EC'

vaiues 1i:ive dccli~ictl ti-om a Ihiglier value 16.7 ~ 1 0 ' 11 S/crn for NSI ni-itl 20.5 x10' 11 S'cm

NS2 to a Ioj'iei. valiic of iibo~it 4.67 x l0 ; !I S~CI?: YS1 niid NS2 ,ind atraincd stead! srate on

35"' day oiinarcls. On llle otliei- Ihand. tiie starling xal~ie off:(' i'or US3 ~vhich \vzs about 50.2

X I O ' 11 Shrli. rernaincd I?igli during the first 5 dais of hatct: nlode aiid thcreaf'ter, decreased

0r.a~ticalIy and artained steady stntc at llie eilil ol '44" cia!.

TS and TDS \\ere foiind to iirldergo a large \arialion in tile batcl] mode, \hith tlieir colicentration

lying iri the range of about 2.0 to 10.2 x 10' mgiL for KS1 arid 2.5 to 9.1 u 10' nig'l. for KS2

during tlie firsr 5 days of operation. Ho\vever. beyond 5:': day and till tiie da? of attaining stead)

state (i.e. 42"" day ). tlie variatio~i in TS arid TIIS conccntratio~is werc fourld to be less. NS3

slio\veci still higher \ariatioil in tlie coilcentration of TS arid TOS , iri tile t a ~ ~ g e of about 3.20 -

23.9 x 10' mg!L aiid will? in the first 15da);s of operatio11 . it1 the batch rnode. '4S3 ertained tlie

steady state on tlie 41" day.

( 3 ) Chloride and Suiphate: The concentration of cl~loride b a s found to var); in tlie rarige of

about 708 to 2482; 779 to 2836 and 708 to 7090 mgiL for NSI. NS2 and NS3 respectively.

during IS' to 20"' day of batch mode. Steady state for NS1 and NS3 was attained 011 17'' day

oriwards and for NS2 on 28Ih day. The co~icentration of suiphate was found to vary in the range

of about I600 to 5440; 1205 to 9760 and 400 to 7500 mg/L for NS I . NS2 and NS3 respectively,

during 4 ~ : ~ to 52'ld day of batch mode. Steady state was reached on the 57''' clay for NSI and

NS2, whereas, it was on 5 f h day for NS3.

4.2.2 Continoous Mode

As stated in Chapter 3 (Sec. ;.5,3j. tile purpose of tlie continoo~is mode. is !o stud) tlie effect of

\ariztion of tloa. rate (8 and I6 lir IIRT) and concentration (25% and 50 ?') oil soil -pollutant

inieraction. Tlioilgll, the effect of c o i l t i ~ i ~ i o ~ ! ~ ~riode was studied on soil in~eraction will1 various

illorganic pollutants (pll. alltalinity. EC . 1's. 'TDS, chloride and si~lpliate). significatlr variations

were obser\'ed for soil interadion on11 \+it11 pl-I. alkalinity. chloride ancl si~lpliate. tleiice. soil-

iiiteraction on rhese inorganic pollutants a!otie are disciissed belo-.

(A) Ii'flulitri[e Soil (CSIJ

The cliaracteristics of tile three effllleiits diic to artificial colirailii~iation 011 CSI. in col~tinuoils

node, are presentcd in Tables 4.2 (a) - (h ) & 4.2 (di - (e) 8 hr I-IRT. atid 4 . j (a) - (b), 6: 4.3

(ti) -- (e). for 16 lir IIRI' at 25 anti 50 % concc~iirniions. 7'lic intci-ndioils hc[\\ccn ( '$1 aii~i llic

varioiis siyiiificaril inorgniiic polli~tants. u i z . pi], all tali nit^, cliloridc and .;lilpliate arc

explained. hased oil critical aiiaI!sis of tile above results.

Ailiiiio acid, surl:actant and pliarmaceutical ei'llitc~its at~nined tlic steady statc coildilion uithin a

period of 19 da j s for 8 lir HRT and I I (lays for 16 lir HIIT at 25 94 co~iceritratioii, wliercas. tile

ehove el'llue~its attained the steady state condiiioii witlii:l a period of I6 days ibr 8 lir I-1RT anti

I I d:iy~ Tor 16 lir IIRT at 50 ?h conce~itratioii.

( 1 ) p l i and Alltalinitv: pH values were found to var) i'ro~ii 4.7 to 7.8: 5.2 t o 7.6: and 5.3 to 7.9

for 8 hr HRT. and 4.8 to 9.1: 6.1 to 8.6; and 7.0 to 8.0 for 16 Ilr HRT. respecti\,ely. for a~t i ino

acid, surfactant atid pharmacei~tical effllients.

Alkalinit! values were found to tsar) from 290 to 877; 290 to 871; atid 290 to 821 nig:'L for 8 111.

tillT. and 290 to 725; 335 to 759: and 435 to 871 rng.'I. for 16 Ill- HRT. respectively. fol- amino

acid. surhctant and oharmaceutical effluents.

Variation in pH observed in the present stud! was found to follow a siniilar trend with that o f

the reported \slues of Ruhl and Daniel (1997) for tlie esperilnents coiidilcted by tliem on

geosynthetic clay liners (tested for fly ash and ~nunicipal solid waste as leachate) for the

pei-iiieation o f a c ~ d i c and all;aline cliernical sol~itions. Voreo\er . (lie above bei;a\ioilr is same as

that for the case of batch tnodc under identical conditions.

(2) Cllloride arld S u i p ~ . Chloride co~~cciltrations \\ere So~itlti to vary li.o~il 70 to 432: 88 to

793 and 124 to 793 mg/L for 8 !ir HRT, and 35 !o 65 I: 13 1 to 820 and 248 to 900 tng'L for 16

iir I iRT. respectively. fot amir?o acid, susfactnrit and pliar~naceutica efflire~its.

Sulphatc coiiceii!r.arions \\'ere fo~iiid to vary fiotii 60 to 2400: 20 to 1984 and 40 lo 2621 n?g'I. i'or

8 lhr I lill'. anti 20 lo 512. G O to 608 ;rlitI 20 10 701 ~iig'l. li)r 10 !ir I l l < ' / ' . r c ~ p c c l i v ~ I ~ . (br aliii~io

acid. surfactant a n d pl~asniaccuiical eSflucrits.

Be~tlo~ii te Soil (CS2)

'l'lle clia~.actc~.istics of lllc tlwce cflliients tI[lc to artificial ccrntaini~iatio~i on C02. . ! I coiitin~lous

mode are preseiiled ill Tables 4.8 (a) - (b), 4.8 ( d ) - (el fnr 8 lir kIRT and 4.9 (a) - (b). 4.9 (ti) -

(c) Ibs I6 111. I l l l l ' nt 25 anti 50 '% concc~~traiiotis. I'lie iiiterac~io~is h c t ~ c c n CS:! ar:d the \ar ious

significant inorganic pollirtants. biz., pl-I. alltniitiiiy. cliloritlr: and sulpliate ate explai:ied. based

(111 critical atial)sis o f ~ l i e above resiil~s.

Amino acid. surfactant atid phasmace~itical effluents attained tlie stead! state conditiotl \+itliiti a

period of 56 days for 8 Ilr HRT arid 15 days Tor 16 lhr HRT at 25 Oio colicentratioii. \rilereas, the

above effluents attained tlie steady state condition \\.ithin a ]period of 17 days for 8 Iir HRT and

14 days for I6 lis I-IRT at 50 % co~icentsatioti.

(1) pH and .4ll;aii1iitv: pH calues were foutid to vary from 8.0 to 8.9: 7.0 to 7.9 arid 6.5 to 8.1

for 8 hr I-IRT, and 6.0 to 7.5; 7.0 to 7.2 and 6.3 to 8.1 for 16 Ilr HRT: respectively, Tor amino

acid, surfactant and pharmaceutical effluents.

Alkalinity valires ue re foutld to vary from 153 to 183; 122 to 2 14 and 153 to 183 tngiL for 8 lir

HRT, and 123 to 168, 153 to 195 and 153 to 290 1ng1L for 16 lir HRT, respectively. for ariiino

acid, surfactant and pharmaceutical effluents.

(2) Clilol-i(!e and Sulvhate : Cliloride concentrations \sere foi?ii!id to vary from 48 to 525; 3 10 to

990 and I57 to 750 mg~l, for 8 lir HRT and SO to 285; 3 I0 to 889 a~itl 168 lo 467 mg/L for I6

hr I-ll<'i'. respectively. for aniiilo acid, si~rfiictaiit and pharmnccu~ical efiliiciits

Sulphate concentrations here found to vary f ro~n 440 to 2040. 280 to 1472 and 760 ro 3024

mg/L for 8 lir I-IRT and 400 to 884. 240 to 680 arid 640 to 1292 mg,L for 16 hr HRT.

respectively. for amino acid, sul-factant and plial-maceiltical effluents.

it is evident from tile aboi'e results that the retention of sulphate within tlie soil mass (i.e. CS2 j

undergoes a larger variation tviien compared to that of cilloride before attaining the steady state

coiidition. This is due to tile fact that sulpliate is reacting at a lliglier rate and assists in breakup o f

soil interstices leading to per~neatio~i of Inore slilpi?ate ions tvl~eri coinpared lo that of cllloride

ions due to arriiiciai contaminatioii on CS2. The variation in sii!plinte coiiceiitratlon was found

to be coiiipnrably less for pl~armaccutical effluent \ \hen coinpared lo tlint of a~iiino acid and

surfactarit effluents. The permeation of chloride tllroiigli tlie CS2 is in line \tit11 the result

reported by Stern and Sliakelford (1998) for the fortiii~lation of a hjpoihesis relating to tile

change i ~ i tlie liydraulic coilductivit). of sand - bentonite mixtures due to tile rerlileation of CaC12

solution.

Tlie cliaracteristics of a~hiiiio acid efflueiit due to artificial corita~ilination o ~ i \SI . h S 2 and

NS3 . i t ? continliol~s ~ilodc are prcsciitcd in Tnhlcs 4.14 (a) - (h) ; 4, I4 (il) - (c) fbs 8 lir I IRT and

4.15 (a) - (b); 4.15 (d) - (e) for 16 lir HRT at 25 and 50 concentrations. The interactions

between the three natural soils PSI. NS2 atid US3) and tlie ~ a r i o u s significant inorganic

pollutants, viz.. ptl, alkalinity: chloride and s ~ ~ l p h a t e are explaillcd hased 011 cri~icai analysis of

tlie above results.

Amino acid effluent attained the steady state condition w i t l ~ i i ~ a period of 13 days for 8 Ihr I-IRT

and 13 d a ~ s for 16 fir HRT at 25 % coticentration. and it attained rile steady state conditioii

within a period of 18 days for 8 hr HRT and 14 days for 16 hr HRT at 50 % concentiatioil.

( I ) pH aitd Alkalinity: p1-I ba1~1e.s \$ere found to vas) froin 3.7 to 3.5: 3.7 to 4.4: 3 7 to 4.3 for

8 lir HRT. and 3.7 to 4.0; 3.6 to 4.0 and 3.8 to 4.1 for I6 lir IIRT, respecrivel;. for arnina acid

eff l i~e~rt oil h S 1 , KS2 a id NS3.

AlLali~~ity b:1111cs \\,ere SCNII I~ to bar!! !Yo111 321 10 063 ini$/I. l'(ir 8 lhr ;111(i I6 11s llf<'r. for aillil~o

acid. effluent on USI. I S 2 atid YS3.

(2) Clllorides and Sulplia& : Chloride co~icenti-ations \\ere fbi~i:d ro jar) ii-oil? 567 io I I?? . 567

to 1064 arid 567 to 1134nig!I. for 8 hr HRT, and 992 to ! 2 7 6 , 1064 to 1275 ai;d 992 ro 1276

inlgil, for 16 hr I-IRT. respect~vei>. for aini~lo acid ei'fli~eilt on US1 , I S 2 and ZS.3.

Sulpllate colicentl.atio11s \\ere foiind lo vary fioiii 4000 to 5800 . 3800 to 6800 a ~ i d 1400 to SO00

nigiL ibl- 8 lir liR7 ; ~ n d 800 to 4400 , 800 to 4600 and 900 to 4300 1n1g'L for 16 hi HRT.

rcspecti~ely. for amino acid efflileiit on NSI . NS2 and NS?

Variatioil in ptl. cliloritle and sulphate due to a~nirio acid contalninatioii 011 NSI illid h S 2 as

obscr\ed in tlie present stiidy are conlparable to tlie l i n d i n s of Ragllu (20051 i \ ~ !lie study on

q~;anriiicatioil of leacliiiig capacities of poI1111ed Iaiidfill.

(D) Su~~fnctnfrt Efflue~tf on IWI, 1YS2 i7n(ld,'VS.i

The cllaracteristics of surfactant efflile11t due to artificial contan~ination on NSI. US2 anti ZS3 .

in continuous mode are p~.eseiited in Tables 4.20 (a) - (b). 4.20 (dl - (e) for 8 lir HRT and 4.21 (a)

- (b). 1.21 ( d ) - (e) for I6 lhr I IRT at 25 aiid 50 96 coiicentratioi~s. The ii~teractions het\\'eeii KS I ,

NS2 and NS3 and the various sigiiiiicai~t inorganic pollutants, viz., pH. alkalini~y, chloride and

siilpllate are explained, based oil critical ana1)sis of the above results.

Surfactant eflluent attained tlle steady state coiiditioli withi11 a period of 14 days for 8 lhr liRT

and I5 days for 16 iir HRT at 25 % concentration. and it attained the steady state condition

~vitliiri a period of 17 days for 8 hr HRT and 15 days for 16 hr I-IRT at 50 % concentration.

( I ) 911 and Allialinitv: 1114 valucs \vci-e ibi~nd to \,ar!, fi-oiii 6.5 lo 8.2: 5.5 to 7.6 arid 6.4 !o 7.8

ii,r S 11s IIR'i. aiid 7.3 In 8.1. 7.0 to 7.4 ,!lid 7.0 lo 7.7 for I6 !ir HRI'. respectivsl\. fur surfactant

ciiltie!it on US1 . XS2 and VS3.

.4lkalinity valiies \\'ere ib~ind to car); fro111 i?s3 to 2586: 129: to 2596 and 258 to 840 nig/L. for

8 lir HRT. and I354 to 21 13, 2257 to 3168 and 474 to 71 I iiigL. for I6 lhr IHRT, respec!i\ely. for

surfactant et'fliie~it on \ S I . YS2 a~ld XS3.

121 Chloride and Suluhate : Cli101-ide cu~ice~ l t ra~ io ;~s werc iiiund to \.or> Croni 195 to 1133. 71 lo

I063 and 71 to 638 iiig1L for 8 !ir HRT. and 425 to 708. I IS lo 590 and 71 to 554 mg/L. for 16

lir HRT. i-especticely. for surlbc!aiit efflucti~ oli YS 1 . \S2 a:id NS3.

Sulpllate concentrations \\)ere found to var) froni 460 to 3160. 720 to 5100 and 500 to 5940

111~'L for 8 lir HRT. and 1940 to 5266. 5000 to 7300 and 890 to 1600 iil8'1, for 16 hr HRT,

respectivel>. for surfactant effluent oii US1 . \S2 and NS3.

TIie cariations ill pi-!. chloride and sulpliaie co~icentrations as observed in tlie present study are

coinparable to tlie permeation of surfactan! solu:ion, sulpliiiric acid (pH: 2.0) a~td KaOH (8 - 12)

studied foi- the change in ciia~acteristics of polliitants uiidergoing adsorption and desorption

belia\~iour in a laboratory colu!i~n as reported by Su i ibo~i~ i~ Park er a!. (1998) under in-situ

enviroiiment using aqueotis solution extracrioli The cliaiige ill coiicenrratior, of ihe chloride and

sulphate under 25 ?6 and 50 Oib conccutration i n the present stud? \\.ere obseibed to be due to the

chailge in tlie concentration of desorbed liquid pel-meating tile aqueous phase tinder 8 lit and 16

lir HRT.

(E) Plrarn~aceutical Effluent on ,VSI, lVS2 and .\'S3

Tile characteristics of tlie phamaceiiticai effluent dite to artificial con tami~?a i io~~ of NSI . 3 S 2

aiid NS3. in contin~ioiis mode are 111-ese~iied iii Tables 4.26 (a) - (b). 4.26 (d) - (e) for 8 hr HRT

a i d 4.27 (a) - (b), 4.27 (d) - (e) for i G hr HRT at 25 a ~ i d 50 %I co~icentrations. The interactions

between NS I, NS2 and NS3 and the various significant inorganic pollutants, \+., pH. alkalinit),

chloride and sulphate are explained. based on critical aiialysis of the abo \e results.

'!!;e pliarlnaceutical effluent attained the steady state condition within a period of 17 days for 8

lir I-IR?. and 14 days for 16 Iir IiRT at 25 O/o concentration. and ir attained the steady state

condition witllin a period of 17 days Sor 8 lir 1klR.T atid 13 days Ihr I6 lir I-IRT at 50 O/o

coticentrdlio~i.

(1) 01 I itiil Alhaiii~ity: pI I \ ,a!uen\erc Ibi~nd to vriry froiii 7.4 to 10.4: 7.4 to 10.6 and 7.4 10.4

for 8 lir 1-111T, and 7.0 to 8.9: 7.4 to 8.7 n!id 7.4 to 8.7 I G ilr I-IRT. respecti\ely. for

pliarniaceutic~il eftlue~it on hS 1 . NS2 atid NS3.

Alkaliiiity values were i b u n d to vat-y fi-om 129 to 5690: 327 to 5366 atid 5 8 1 10 5172 m;lL for 8

111- IHRT. anti 129 to 2457; 327 to 21 92 and 5 8 1 to 23271i?<L for 16 lir HRT. respectively. Tor

pharmaceatical effluent on NS1 . XS2 and h S 3 .

( 2 ) Chloride and Sulohate : Cl~loride concentrations \<ere founcl to vaty fl-oln 11 2 ro 1699: 344

to 1699 and 424 to I699 mg!L for 8 hr ilRT: and 316 to 757. i l to 779 and I42 to 779 mg'L for

I6 hr IIRT. respecti\ely, for phar~naceutical efiluent on NSI . h S 2 and NS3.

Sulphatc concentrations were found to vary froin 010 3260: 940 to 2940 atid 985 io 3000

mgIL for 8 Iir I-IRT: a~ id 1160 to 31 10, 940 to 31 10 and 985 to 3230 m g L for 16 lir I-1RT.

respcctivel>. for pharlnace~ilical dflileilt on NS I . US2 and NS3

it is evident ftrom tile a b o ~ e data that tlie retention of siilphate coiicentratioli it~idergoes a lat-ger

\ariation \\heti cotiipared to that of cliloride before attaining the steady slalz contlitioii This is

due ro the fact tliat sulpliare is reacting at a faster rate and hence assists In breakup of soil

interstices leading to permeation of more sulpliare ions. wllen compared to that of chloride ions,

due to at-tificial coiitnminatioii on NSI to NS?. Tlic variation ill suipliate concentration \\as foulid

to be coml?nrably less for pliarniace~itical e f i l ~ ~ e n t nlien cornparted to tliat of tlie otlicr tho

effluents. It is found that tlie cliloride and sulphate concentration observed iii tlie present study

is comparable to tlie reported results of Olania et al. (1991) for the study of effect of solid waste

disposal on land.

7.3 SOIL - I'OLLCTANT IKTERACTION: ORGANIC I'OLLCT!INrrS

(A) Knoli~life Soil (CSl)

Tlie clial.acteris!ics of the three efflueiits doe to artificial coiitamiiiatio~: of CSI soil. in batch

node. are presented iii Table 4.1 (c) and tile variation of COD, BOD atid TVS \+it11 time (ill

days) are s l io\~i i ill Figs. 4.4 (a) to (c). respectivel>. Tlie i~iteractions bet+.ee~l CS I and the

variouc organic pollutants are explaiiied. based oii critical analjsis of rile above resi~!ts.

(1) COD Concentration: COD concentrations of' aminoacid, surfactalit and plia~~macetitical

effluents \\ere in the range of 19.00 to 20.00 x 10'. 9.00 to 13.30 u 10' and 10.00 ro 14.5 I x 10'

mglL, respecti\ely. before passing through tile soil column. and the concei?trations Ivere found to

car) after contamination on CSI. from 6.80 to 19.80 x 10'. 3.60 to 20.10 x 10' and 4.60 to

19.20 x 10'mg!L Cor amino acid, surfactant and pliarrnaceutical effloenis, on CS I , respectively.

Allii~io acid. surfaclaiit arid pliartnacci~tical erflucnls s h o ~ e t l peak COD concenvatio~is of 19.80

x 10' . and 20.10 x 10' and 19.20 x 10' mg!L at tlie end of and 11'" 14th and 39th day,

respectibely. Steady state condition was foiind to Iiave been reached at tlie ciid of GO"' d a y . 74"'

and 8 I " day respectively, for aniino acid, si~rfactant and pharmaceutical effluents.

Variation in COD concentration due to contamination on CSI. as observed iii the present

study, is co~nparahie to the permeation of organic cliemicais, viz., methanol, acetic acid and

tricliloro ethylene tlirough ltaolinite soil sample. as reported by Bowder et a1 (1987). Further, tile

resulrs obtained in the present study is in close co~iiparison ni th that of tlie results reported by

Khan et a1 (1999) for the study of mechanisni involved in tlie ruobilization process of certain

amino acids tlirough pesticide amended soils.

121 BOD Concentration: BOD concentrations of amiliaacid, si~rfactarlt and pharmaceutical

effluents were in tlie range of 4.97 to 5.23 x lo3, 4.05 to 8.76 x 10' and 2.46 to 3.47 x 10'11ig/l,

respectively, before passing thsough the soil column. and tlie concentrations \*ere found to vary

$ter contnini~latioil on CSI fro111 1.66 to 4.85 x 10': 0.93 to 5.22 x 10' and 0.88 to 4.90 x 10'

i:igil_ for aril~no acid, s:irfacia~it and p l ~ a r r n ~ c c ~ ~ ~ i c a l clliicnts. on CSl . rcspecr~~cl!

h111ii1o acid. silrfiictant and pl~arinaceutical ef'll~ien~ slloir,ed peal; Boll col?cei!u.ations o f 4.85 X

10' 5.22 s 10' and 4.90 s 10' mg/L at tile elid of and I I".. 14'" slid 39"' day respectiveiy.

Stead) state condi[iolls was found to have been reached at the elid of 60''' day, 74" and 81''

day respec:i\ ely, for amino acid. surfactant. pl~armaceuiical efllilents.

( 3 ) Tolal Volatile Solids (TVSL TVS conccntratiotls of amiiio acid, ~~lrfactal i t atid

pharrnacei~tical effluents were in the range of 14.60 to 16 30 s 10'. 1.20 to 4.80 r 10' and 14.110

to 28.00 x 10' n;g/L rcspectibely, before passing thro:ipl~ tlie soil columii and tile

concentra~ioils were foiind to Yary after contatniiiatio~r oil CSI , froi:~ 0.10 to 5.00 .K 10': 0.20 to

4.00 s 1 0' and 0. 10 Lo 4.00 x 10' mgl l , for ali~itio acid. surhc:ai~t and pl~arrnaceu~ical eff l~~eii ts .

iespecti\'el?.

Aniino acid, surfactant and pl~arliiaceutical emllents slioued peal, TVS concentrations o f5 .00 x

10' . and 4.00 x 10' and 4.00 x 10' mg'L at tile end of 2"" (la). 70''' day a i d 56"' daq.

respectively. Steady state cctiditioiis was foi~nd lo have been reached at the end of 60" day.

74'" day and 81" day, respectively, for alninoacid , siirfcictai~i and pharmaceutical ef'lliients.

(Bj Berttonite Soil (CSZj

The cllaracteristics of the three effluents due to artificial containination of CS2 soil, i i ? barch

mode. are prcseiitcd in Table 4.7 (c) and tlic vat-iatiol~ of COD. BOD aiid TVS i41tli tilne (in

days) are s l iosn i n Figs. 4.1 1 (a) to (c), respectively. The interactions bemeen CS2 and the

various organic polliltants are explained based on critical analysis of the above results.

(1) COD Concentration COD concentrations of aminoacid, surfactant and pliannaceuticai

effluents were in tlie range of 19.00 to 20.00 x 1 03, 9.00 to 13.40 x I 0' and 10.00 to 14.5 1 x 10'

mglL respectively, before passing tlirough tlie soil column, and tlie concentrations were found

to val-y afier contaniiiiaiion on CS2. iioni 3.75 to 22.50 x 10'. 7.00 to 20.00 x 10' and 2.75 to

23.00 1 1 0 ' l i l ~ i ~ for amino acid. surfactaiit and pharmaceutical effluents. respectivcl).

Amino acid . stirf;jctaiit and pl!armaceulical e f f l ~ ~ e ~ i t s slioi\~cd pealc COD concentratio~ls o f 22.50

x 1 0 ' . 20.00 x 10' and 23.00 x l $ m g / ~ at tile end o f and 501", 2""ad 19"' da!. respectibely.

Steady state conditioiis was found to ha\.e bee11 reaciied at the e~ici o f71" daq. 75" and 71" day,

respeclivel). for aniino acid , slirfacranr and pliarinaceiiticdl effluents.

Tlie aho1.e results is i~i close to the reported results of Khan e! a1 (1999) tile siudy o f

~meclianisrii il~volved in tile rnobilimtion process of certai~i amino acids tlirougli pesticide

amended soils. F~I-tiler. it is evident froni the experi~iieiiral in\estigatioii of Sou!e and Burns

(2001) or, organo-bentonites, (for the srudy of the effect or arpatiic-cation Ytruiturc on orgaiio-

belitonire bel~aviour) that tlie exchange of osgaiio-cationic strilcture vir . 8.1cyI chains and

benzyltrietliyianilnonillni (BTEA) chloride drast~call) reduced ~"urtlier accun:ii'ation oforga~iic-

cations and hence. results iri hydrophobic nature of bentonite. Siinilar behnviour \4as observed in

tile present study. as shown by rile niore or less unifor~ii concen~ration o f COD after 61'' day r i l l

tile end of the batch mode (99": daq).

(2) BOD Concentration: ROD concentrations o f amino acid. surfactant alnd pliarniaceutical

effluents were in the range o f 4.97 to 5.23 x lo3: 4.05 to 8.76 x 10' and 2.46 to 3.47 x 10'mgiL

respectively before passing through tlie soil coluin~i, and the colicentrations were found to vary

after contamination on CS2. from 0.37 to 5.52 x lo', 2.21 to 4.91 x 10' and 0.92 to 4.35 x 10'

1ng1. for aniino acid, surfactant and pharlnaceutical efflue~its. respcctivelq.

A~iiino acid, si~rlhctant nntl pl~arniaccuticnl c f l l ~ ~ c ~ i t s sliowctl ipcalc BOD co1icc1i11-atio~is 01'5.52 x

l o 3 , 1.91 x 10' and 4.35 x 10' mg/L at tlie end o f and 47" : 2"" day and 2'" da). respectively.

Sleady state cotidition \yere found to reach at tlie eiid o f 71" clay. 75" day a ~ i d 71" day,

respectively. for amino acid , surfactant and pilarlnacei~tical effluerlts.

(31 Total Volatile Solids (TVSI: TVS co~icentrations o f amino acid, surfactant and

pharmaceutical effluents were in the range of 14.60 to16.30 x 10'; 1.20 to 4.80 x 10' and 14.00

to 28.00 x 10' tng/L respectively, before passing through the soil column and tlie

concentratio~is were found to i3allt after contamination oil CS2, from 0.30 - 18.00 x 10': 0.20 -

24.00 x lo3 and I .OO to 9.00 x I$ m g / ~ for amino acid. surfactant and pharmaceutical effluents,

on CS?. respectively.

Amino acid . surfactant and phsrinaceutical effluents slio\+ed peal; TVS concentrations of 18.00

x 10' , 24.00 x 10' and 9.00 x l !2 'mg/~ at the end of and 61". 8"' and day 5"' day. respectively.

Steady state conditions were found to reacli a: tlie eiid of ~ 8 ' ~ daq , 43rd day and 82"' day.

respectively. for amiiloacid. surfactant and phar~nacei~tical effluents.

The behaiiour of dissolved aromatic benzene and organic solvents were treated ill a ground

water recharge straturn by Drewes and Jekel (1998) to explain the degradation and beha\iour of

aromatic constituents in a soil-laden polliltant s)slen?. Tile rcsults of the above in\-estigation is

comparable to the experimental results and trends obtained for tile present sri~cly.

(C) Ambto Acid E f l u e ~ ~ f on NSI, "S2 nad AS3

( I ) COD & BOD : \'ariation ill the concentration of COD & BOD was foi~iid to be in tile

range of about 3276 to 155 I0 mylL for KSI: and 3 133 to 155 10 111giL for US2 and KS3 . till the end of 22 days and tliei-e21fier they relnaincd fairly constant , till steady state \\,as attained on

tlie 724''' day.

'file results of tile present itorlc is coinparable to result reported by Gowda and I<ottaiah (2000)

for their investigation on percolation of organic solids in soil layers and also found to be in good

agreement -ith the experimental results of Boxvders and Daniel (1957) for tile permeation of

d i l ~ ~ t e organic clie~nicals in cia! lagers.

COD variatioils as observed in the present study nere co~iiparable with tlie results of Semer and

Reddy (1995) for tlie study of ecaluation of soil uashing process to remove mixed contaniinants

from a sandy loam. The minor variation of COD observed closer to the ste a d; I state condition for

NSI lnay be due to the low rate of repeated adsorption or desorptio~i of organic impurities

taking place betaeen the soil matrix and the aqueous phase. The organic content of the

amirioacid cffl~ient (COD) !akes a longer time for tlie bio-transforniatii~~l a~ id bio-degradation of

amino acid and its inter~nediates. as obserbed during tlle ineasurement of COD concentration.

7 . l ~ results as obtained above is comparable to tlie results ireported by Rohcrt et al (1992) for

tlie field stud) of determination of organic water quality changes during ground water recliarges

in tlie Palo Alro-Baylands.

(2) Nitrite : \'ariation in nitrite concetltration due to artificial contamination of al i~ino acid

efiluent on KSI to SS3. are sho\v~i in Figs 4.17Ca) - (cj and in 'Table 4.1 3 (c 1. For all the three

natural soils (KSI. NS2 and NS?), tlie concentratio11 of ~iitrite \\.as found to var) from an iliitial

concentratio~i of about 400 -720 mgiL to about 60 -70 iiigiL. at tile end of 32 days. Beyond 32

days. the concentration \+as foiind to vary \er) mildly ' re~iiaiii constant. I-letice, it can be stated

that for nitrite to attain a steady state. it taltes tiot lcss tlidii 32 dabs, consideri:lg tile beIia\ioiir of

three natural soils (NS I . NS2 and NS3) due ro tlie effect oftlie above effluents.

The ohserved nitrite variation of the present stud) is cornparahie with that of !tie lalid applicatioli

system carried out b) Korolil and Jeppson (1994) for tile nutrient leaching frcm municipal

nastewater irrigated soil. The tl-ansitioiis of an~nionia to ]nitrite atid nitrate nitrogen were

comparable with tlie nitrite concentratio~i o f 6 0 - 70 mgil, (present stud)) transformed at tlie elid

of 32 days.

(3)TotaI Volatile Solids (TVSI : \'ariation ill the concentration of I 'VS are shown i i i Figs .

4.18 ( a) - (c) and presentctl in 'fable 4.13 (c) . Variatioii in tile co~~ceu t ra t io~ i \+as found to be

0.10 to 6.60 1iig1L for S S I . NS2 and NS3 till 9''' day and thereafter tlie concentratio~i was found

to vary less. till the end of batch mode. It can be taken that the stead), state has been attained 011

tlie 6 jLh day for NSland 60"' day forNS2, S S 3 . NS3 ivliicli has a liiglwr silt content ( i s . 96 56)

slio\+ed a variation betueen 100 to 5000 mgiL (betueen I " and 20"' day) steady state o f TVS

concentration before it reached the steady state. The above behaviour of NS3 may be attributed

to the higher void content available during the initial stage and acc~lmulation of TVS with

transformation (at higher SRT), close to tlie steady state condition.

(D) Surj~~cfotlf Ejflr!e~rlo~z .VSi; !VS2 011N';1'S.Z

( I ) COD & BOD :

The \.ariation ill the coricciirratio~? of C O D & BOD was found to \el;L liigll . in the range o f

about I 1 lU0 to I3000 m@L for NSl ; and I I I00 to 12000 111giL for KS2; till the end of 25 d a y

and tliereaficr rerliained fairly constant . t i l l they a t~a i~ ied the stead) state on tile 71'' day.

i-Ioaeber. for KS3 . COD S( BOD concentrations (I I200 -12000 rng/!) \ \as found to be Iligh till

tlie end of 20 days and thereafter there \\.as a drastic reduction and rel-naineci constant till it

attained the stead) slate \+as attained on 84'" day

Tlie variat~on i i i CODjUOD concentrations as obser\,cd ror KSI aiid US2 :\ere pri~icipally duc

to tlie difference i n the rate of adsorptio~i iind d c s ~ ~ . i ) t i o ~ ~ taliing place beti\ccii :lie soil surface

and aqiieotis phase. 71ie nho\e bariatio~i Ilia!: also be attrib~ited to the dii'i'erence iii the

distribittio~i o f organic content in tlie soil mass \\iti1 rcspcct to [!it C O D ' B O D conceiitration of

surfactant effluent. Tlie abobe observed behaviour \\ere co~nparable 10 tlie reported 5nditigs of

Lee et al. (2004) carried oiit for the distribution of organic compounds in the soil solid.'\\ater

syslcm due to wasliing of surfactant soll~tion.

Tile more or less constant C O D co~~centration observed at the outlet of soil col:~mn, a t e r 48'"

da: r i l l tlie end of 89"' day. shows the attainmerit of limiting value of C O D towards bio-

transfortilation and bio-gradation for surfactant effluent considered i l l this stiidg. The above

behaviour is in close agreement with the observation of Allah and Srorr (1998) reported for the

bio - degradability of anionic suri'acta~lts (hexadecaiie and naphtlialene) in tlie presence of other

organic contarninants.

(2) Nitrite : Variation in nitrite concentration for l<SI to hS3 are shown in Figs 4.24 (a) - (c)

and in Table 4.19 (c ). For soil KSI , the variation was initially in tlie range of 100 to 15.000

mglL upto 1 to 20 days and thereafter. remained fairly cotistaiit till it attained steady state at tlie

end of 9 0 ' ~ day.

l'or all tile three natural s o ~ l s (NSI, h S 2 aiid KS3) cotisidered. the co~icentratioil o f nitlire was

fc>ui:d to \ary over n large range ie from an initial concciiiration of about i5000 -17000 1?1g/L to

about 600 - 4200 mgiL . at tile end of 20 days. Beyolid 2 0 d a ~ s . tile concentration \?as found to

18ai.y very iniildly 1 reiliain constant. From tile a b o ~ e . it c a ~ ? be stated [\,at for nirritc to attain a

steady slate. i t takes not less thail 36 days . considering the be1iaviou1- of three natural soils h s l .

NS2 arid NY3.

( 3 ) 'To:al Voi,i~ile Solids ( i VS) . Variation iii tile concentrdlioli o f I'\'S are slioi\n in Figs . 4.26

(a) - (c) and presented ill 'l'nhle 3.19 (c) . I-liglier ~ a r i a t i o ~ i in tlic concentration was fo~ind for

KSI and hS2 , t i l l the 40" day 2nd fur AS3 t i l l tlis 20''' day. 'l'lierealier. 11ic coilccnlrarion h a s

found to bar) less. till tile elid of Satcli mode. It can be talteii tliar tlie steady state lias been

attained on the 40'' day Tor NSI .KS2 aucl 25"' dab . for NS?.

\S1 ivhicli lias a Iiiglier sil coiltent ii.e. 96%) slioaed a \ariation be~ueeii 100 lo SO00 mg/L

(between I " and 20"' da) j of TVS concentration before it reaclied tile stead) stare condition.

Tlie above behaviour of KS3 imaj be attributed to lie higher void content mailable during the

initial stage and accumulatioil of TVS witll transformatioii (ar higher SRT) close to tile stead]

state condition. The above beliavioi~r is comparable to tile reported experime~ital outcome of

.4dams et al (1996) for the bio -degradation of non - ionic si~rfactanrs

( I ) COD & BOD : Tlie iariatioli in tlie concentration of COD & BOD n a s foulid to be in the

range of about 2563 1 to I 19183 mgil, for US!: 25764 to I20272 img/I, for N S 2 , till the elid of

59 d a y , till they attained tile s t e a d state on tlie 60"' day. I-Ioivever, for NS3. the concentl-ations

(26031 to i 14449 mgiL) was found to remain very high till tlie end of 42 da!s and tliereaiter,

there was a drastic reductio~i alld remained constant till steady state was allained 011 tile 52."' d a ) ~

[Table 4.25 ( c ) ; Figs 4.31 (a) - (c) ] .

Variation in COD concentration was found to reach the lo\\est and highest concentration

between 0 - 10 days for NSI and 0- 20 days for NS3. signifying the fact that tlie rate of

permeatio~l \\as faster during initial stages of hatch mode. This behaviour is coniparable to the

stody reported by Ijirata atld Muraoka (1998) for the niigratioil of chlorinated organic

compounds ( tricliloro etliylene) through the unsatiirated zone of tlie porous tiiedium.

12) Nitrite : Variation in nitrite are sho\\n in Figs 4.32 (a) - (c) and in Table 3.25 (c ). For ail

tlie three natural soils (NS I . NS2 and NS3 ), tile concentration of nirrite was found to vary from

all initial concentratio11 of about 650 to 820 mgIL to about 100 ro 230 mg/L , at the end o f 37

da!s. Ueyoiid 27 dais. tile concentrarioli was fouiid to less and vary iery mi!dly ! reniain

consiant. Hencc. it car1 be staled Illat for nitrite to attain a steady state , it takes not less tliaii 40

days . co!lsidering tlie beliaviour of three natural soils.

( 3 ) Total Volatile Solids (TVS'I: Variation iii tlie concetitration of TVS are sliown it! Figs. 4.34

(a) - (c) and presented in Table 4.25 (c). Tile concentration \$as found to be 6 50 to 8.30 m g ~ L

for all tlie natural soils. till 3 ' h a y and thereafter. the variation \+,as found to be very less . till the

end of batcli mode . Hence. it can be taken that the steady state has been attained on the 35" day

for NSi , XS2 and 20" day forNS3.

The belia~iour of NS3 in the present case is found to be similar to that of the behaviour whet? it is

artificially contaminated with the other types of effluents.

Moreover, the results obtained for NS3 is f o ~ ~ t i d to have a similar trend \\it11 that o f Kim et al.

12003) for their experi~iletital study on volatile organic coliipound (VOC) transport through

cotnpacted clay.

4.3.2 Continuous Mode

Though the effect of continuous mode is studied on soil interaction n.it11 various organic

pollutants (COD ,' BOD, Total Volatile Solids and nitrites)? significant ~ariariolis were obserbed

only in the concentration of CODIBOD due to the interaction o f soil with tlie various effluents.

Hence, only the variation in CODIBOD concentration due to the above interaction alone. is

discussed and presented in this section.

(A) Kaolinire Soil (CSI)

The characteristics of the three effluents due to artificial contamination on CSI , in continuous

mode, are presented in Tables 4.2 (c), 4.2 (0 for 8 hr HRT and 4.3 (c), 4.3 (0 for 16 lir HRT at

:j atid 5 0 O/o coiicentraiio~is. :'lie interactions bci\+,ecil CSI and the various significant organic

pollutants. viz..COD and BOD are explaitled bascd oil critical analysis o f the above results.

Aniiiio acid. siii-factant and pliarmaceutical effluents attained steady state condition witllin a

period of 19 days for 8 lir HRT and 1 I days for 16 lir liRT at 25 % concentration. wilereas, the

above effluents attained the stead) state coildition nitliin a period of 16 days for 8 hr HRT and

I l days for 16 iir IiKT at 50 ?lo coiicenlratioli.

[ I ) COD Conceniration. COD concentrations were found to \ary from 500 to 2400. 320 to

2400 and 400 to 2400 nig/L for 8 hr HRT. and 400 to 2400. 600 to 2080 atid 300 to 2240 mgiL

fbr 16 ihr HRT, respectively. for arnino acid. surfactant and pharmaceutical effluents.

(2) BOD Concentration: BOD concentrations he re tb~lnd to fro111 120 to 587. 49 to 587

and 98 lo 587 mg/L for 8 lir HRT, atid 98 to 578. 147 to 5 10 and 73 to 550 mg/L for 16 lir HRT.

respecti~ely. for aillino acid, surfactant and pharmaceutical effluents.

It is found that tlie above variations in orgaiiic concentration (COD) was coliiparable to the

permeation of organic chemicals, viz.. methanol. acetic acid and tl.ichloro ethylene through

kaolinite soil sample. as reported by Boivder and Daniel (1987) and also in close agreement

with tlie reported results of Klian et a1 (1999) for the mechanism i l i~o l \ ed in the niobilization

process of certain amino acids through pesticide aiiiended soils.

(B) Bentortire Soil (CS2)

The characteristics of the tliree efflueiits due to artificial conta~ninatioii on CS2 . in continuous

mode. are presented in Tables 4.8 (c) , 4.8(t) for 8 hr HRT and 4.9 (c), 4 .9 (i) for 16 hr HRT at

25 and 50 % concentrations. The i~iteractions between CS2 and the various significant organic

pollutants, viz.,COD and BOD are explained. based on critical analysis of the above results.

Amino acid, surfactant and pharinaceutical effluents attained steady state condition within a

period on 56 days for 8 hr HRT and 15 days for 16 hr HRT at 25 % concentration, whereas, the

aboie eftluellts nttailied tlie steady state cot!dition \vitiiin a per~od of I7 days for S lir HRT and

14 days for 16 lhr H R T at 50 ?/o conce~~trarioii.

( i ) COD Concentration: COD concentrations a e r e fouild to \ary froln 800 to 363CiO. 900 to

26000 and 1000 to 32000 ~ng iL for 8 lir i iRT, and 5030 to 20000. 8000 to 22000 and 7000 to

I5000 ~nigl i for I6 hr IIRT. respectively. for alilino acid. surfactaiit and piiarmacei~tical

effluents.

(2) BOD Concentra~ion: BOD concentrations \\ere found to vnry fl-0111 172 to 834. 146 to 538

and 172 to 667 nigil for 8 hr HRT, and 123 to 542, I96 to 542 mg!L for I6 llr HRT.

respectively. for amino acid. surfactant and pharmaceiitical eftli~ents.

'Tile longer di~rat ioi~ observed for tile bio - transformation t i~i ie depzndellt bio-transfol.matio11 of

CODtBOD coi?centration in the present study. at 25 and 50 % concentrations :~nder S lir a ~ i d 16

hr I-IRT. is comparable to the rend reportetl by Soule and Burlis (2001) for [lie cxpcrilnental

investigations on organ - bentonites.

(C) A~vbto Acid Effrue~ll 011 IWI, A'S2 and 1\53

The ciiaraacrislics oi' Llic nlilino acid cr i l i~c~it due io arlifici'ii conta~iiillatio~i ol? '4Sl. XS2 and

NS3 soils. in co~iti~iiious mode are presented in Tables 4.14 (c), 4.14 (0 for 8 iir HRT and 4.15

(c) . 4.15 (f) for I6 Iir HRT at 25 and 50 % concentrations. Tile inieraaions bct~vecn US1 to

NS2 and the various significant organic pollutanrs, viz., COD and BOD are explained based on

critical analysis of tlie above results.

Atnino ncid eflli~ent attained tile stead! state condition uitliin a periotl of I3 days To!. 8 hr IdRT

and I3 days for 16 hr I-IRT at 25 % concentralion. whereas. it attained the steady state

condition within a period of 18 days for 8 hr HRT and 14 da l s for 15 lhr HRT at 50 %

concentration.

(1) COD Concentration: COD concentrations were round to var) from 125 17 lo1 3061 mg!L for

8 hr HRT. and 12517 to 14422 ~ngiL for 16 hr HRT, respectively.

(2) BOD Concentration: BOD conceiitrationt wet-e Soi~nd to \dry fiom 3275 to 3418 n?g/L for

R Iir HRT. and 2275 to 3774 ~i?g/l, for 16 lir I-IRT. ~respectively.

(D) Surfuctnilt Effi~ient oil !VSI, iIS.2 und1VS3

Tlie cliaracteristics of tlie surfactant effluent diie to artificial conta~nination o n NS 1, NS2 and

NS3 soils, in continuous inlode. ai-e presented in Tables 4.20 (c). 4.20 (0 for 8 hr I-IRT and 4.21

(c), 4.21 (0 for 16 lir HRT at 25 and 50 % concentrations. The interactions bet~reen NS I to NS3

and the barioi~s significant organic pollutants, viz.. COD and are explained. basecl on critical

analysis of tlie above resiilts.

Surfactant effluent attained the steady state condition \\"itIiin a period oi' I4 days for 8 Iir HRT

and 15 days for I6 lir HR7 at 25 96 co~icentration. bilereas. it attained steadj state condition

witliiil a period of 17 days for 8 lir HRT and 15 days for I6 lhr HRT at 50 % conce~itration.

(1) COD Concentration: COD concentratioils were foiiiid to varj from 130755 to 287074,

10476 !o 386295 a~id 9469 to 13061 mg/l, for 8 Iir HR'T. a~itl 21 7687 to 390623, 264625 to

582321 and I0829 to1 1656 ~ n g / L for 16 lir HRT. respectively.

(21 BOD Concentration: The BOD concentrations were found to \ar! froni 38701 to 61419.

23664 to 82766 and I970 to 2797 ~ng!L for 8 hr HRT, and I8260 to 83543. 78 102 to 12473 1

and 23 I9 to 2495 mglL for 16 Iir HRT. respectively.

Variation ~n CODIBOD concentrations under varyi~ig flow raies (8 and I6 Iir I-IRT) a5 obscrved

in the present study were comparable to the findings of Zhou and Zliu (2005) and Kin? and

otliers (2005) for the study of the anio~iic-nonio~iic 111ixcd sitrfactaiit and non- io~~ic si~rfactant

enhanced reniediation processes. Tlie anionic-nonionic mixed surfactant led to the concept of the

soli~bilisation of polycyclic aromatic hydrocarbons (PAI-Is) which are expected to occur during

bio-trailsformation stage. The non-ionic surfactant enhanced remediation process revealed that

the possible bio-transformation process is limited b) tile ionic strength of contaminatecl liquid

and chemical structure of the constituents of surfactant.

(@ Pl~nrn~aceuticol Effluent on MI, .W ond ,VS3:

Cllaracteristics of the pliar~naceutical effluei~t clue to artificial contaniinatioii 011 h'SI. U S 2 8113

NS3 soils. in co~itinuous mode, are presented iii Tables 4.26 (c). 4.26 (fl for 8 11s HRT and 4.27

(c). 4.27 (f) for 16 hr HRT at 25 a i d 50 $6 concentrations. Tlie inreractions betu>.een CSI and the

varioiis significant organic polliltants. viz..COD and BOD are esplaii~ed based on critical

a~ialysis of tlie above results.

I'Iiarinaccutic:~l cfiluci~t otiaiiicd !lie sic'iriy siatc colid~lioli ui t l i i~l 3 lpc~-i~d or I T clays for 8 lir

I IRT and I4 dnys i'or 16 lii- I l l< ' l a! 25 % concclitratioii. \\liercns. it at~ainetl the stead) stntc

condirioii within a period of 17 days for 8 11s tlR'l' and 13 dabs Tor I 6 11s I-IRT ar 50 ?4

conccn~ration.

W O D Co~icc~itration: T1ie COD concentrations ticre round to vary froni 108299 to 1208 12.

I08843 to 120812 and 108833 to 120812 ingX fbr 8 11s 1-IR'I', and 108843 to 227476. 108843 to

229654 and 10993 I to 228564 mg'L for 16 lir I-IRT, respecti~cly.

321 BOD Co~icciltratioii, i'lie BOD coi~cciitrations wc~.c foulid to v:rr) i'ro~;i 26565 to 2953 1.

2669') to 20769 a ~ ~ r l 20699 to 29635 ~iig'!, li)r j; Iir I IICl, illid 2060'1 to 5590!1. 26OOO !(I 56334

and 26966 to 56601nig1L for I6 lir I-IRT. respectii.el).

Variatioiis in tlie coilce~itratio~i of CODlBOD as ohserved a b o ~ e c o ~ ~ l d be cc~inpared to tile

ieporied resuirs of' 4dams aiid Redd) (1999) & Adams and Reddl (2003) respectively, for. tlie

remediation of tricliloro etliylene (TCE) and benzene biodegradation i ~ i a sauil-ated colu~iin.

4.4 SOIL - POLLLTAhT INTEfL4CTIO\: EFFECT OF RETEhTIOb TILIE

A111 COhCGNTRATiON

The effect of retention time and coiicentratioii of inorganic and organic pollutants present in

amino acid. surfactant and pl~armaceutical efiluents for conimel.cia1 soils (CSI and CS2) and

natural soils (NS I, NS2 aiid NS3) under the continuous mode operation are discussed and only

the salient observations / infereilces drawn, are presented below.

4.4.1 Commercial Soils

(A) Kuolir~ite Soil

l'lic cl'itct of rcteiitioii tiiiic and coticentrarioii of iiiorga~iic aiitl orgsni i l~ollatants presetit in

amino a c ~ d . stirfactant and phar~iiace~irical effliients oil Ikaoliiiite soil (CSI ) are sllown i!! Figs 4.5

( a ) - (c) and J 6 (a) - (c). ~sespeclivelg.

( I ) Inornatiic Poil~itaiits

TIic alnillo acid ciiliicnt slions a \ariati011 in chloridz co!icentrlition fsorli 283 to 301 mg:l at the

end of 8 lir Flll'i at 50 "/o coilce~itration. 'Illis concentration bias roiintl to n i s e Io 381 1rg/1 at the

end of 16 lir HRT. at 50% concentl-ation. The \at-iation in chloride concelltration (n.r . t

retelltioil) was comparatively less at 81ir HRT and at 50 % concentratioil than that o f I 6 hr

HRT at 50 % concentration. This is attributed to the doininat rolc played by tlie amino acid

eff l i~e~it (ie. through adsorption and diffusion process). The above beliaviour is similar to tile

reported study of Rowe and Badv (1996) for chloride diffusion on a clayey silt soil. Surfactant

effluent does inot show marked influence in the retention o f cliloride even at higher HRT and

concentration, considered.

Pharmaceutical effluent shoued low variation o f chloride (i.e. high retention) at 16hr H R T and at

50% concentration. Hoizever retention of cl?loride was found to not appreciable during 8 hr

l iRT for both the concentrations.

Amino acid and pharmaceutical effluents s h o ~ e d variation in the siilphate concentratioti in the

range of 160-310 mg:I. and 400-1640 ing'L,, respectively, at I 6 lir I-IRT anci at 50%

concentration. The above behaviour is attributed due to .the high reactivit:. of sulpliate' and

hence it is responsible for initiation of reaction in terms of the adsorptio~i process. lqo\?eier, rile

variation in concentration (25% 8: 50% ) at 8 lir 1-IICi' be re ib~incl to be less significant.

Surfactant effluent do not serve to accumulate suiphate content in CSI botli at 8 lir and 16 hr

HRT. at 25% and 50% concentrations.

(2) Organic I'oilulants

?.lie reteiition of organic content (COD) is ~i lorc in CSI due to artificial containinntion of

;,liasinaceu~ical effluent t!?aii anlino acid effluent, at I G lhr HRT anti 50% concentrarioii. This is

due to i~n iq i~e cliaracterisiic of pharmaceutical cifiueiit (i.e, due lo tile slrilctilrc of the organic

rnoleci~le present in tlie organic polliltant). On tlie other hand. surfacta~i,~ effl~ient shou,s very

less \ariation in COD conce~itration dire to its a~lique tiatiire of inreraction \\ill1 soil. i.e.

imparting iiiipervio~tsness to tlie soil Inass rcsalti;ig iii !lie pi-e\enlioii of perineatio~l of efiluent

throilgl~ the soil.

(B) Beiilo~iiie Soil

Tlie effect of retention tiine and concentra~ion oF inorga~~ic and organic polluta~lts presznt in

;\mino acid. si~ri'actant a~ id pliarmaceiitical cRluoits arc iliotbn 111 Figs 1.12 fa - (ci and 4.13 (a) -

(c) respectively.

(1) Inorganic Pollutants

A high retention of chloride was observed for soil CS2 due to artiticial contamination of amino

acid and pharmaceutical effluents. .41nirio acid effluent showed a peak cliloride retention of

2681 nig/L at 16 hr HRT. at 50 % concentration when compared to that of pliartnaceutical

effluent. Tlie coticetitration variation (25% arid 50%) at 8 11s HRT did ilot slion liigli retention of'

chloride on soil CS2. Surfactant effluent showed a similar belia\iour (w.r.t retention of chloride)

on CS2, as that of CSI at both 25 % and 50% concentration at I6 hr HRT.

Tlie reteiitioti of sulphate was observed to be high ( 1 11 0 mgiL) for soil CS2 due to artificial

containination of pharmaceutical effluents ar 16 hr HRT, at 50 % conce~itration. Amino acid

rclativelq slioircd a lowcr retention ofsulpliate on CS2 at 16 lir HRT, at 50's concc~itration as

that of pliarniaceutical effluent.

This behaviour is orice again attributed to the 'high reactivity' of sulphate on CS2 uitli respect to

pharmaceutical effluent. Surfactant effluent showed a very low variztioi? (with respect to

sulphate retention) due to artificial concentrations on CS2, at ail HRTs atid concentration,

considered.

12) Oruaiiic I'oll~itaiit

Pliarmacei~ticnl ci.lli~cnt slioiieil a iiig!i rcleiilirii~ o r oreailic contclll (COD) o n soil CS2 (200

ing!L). \vlien coinpared to thai of a~niilo acid erfliient (50 mg!i.) at 50 concentration at 16 hr

tlRT. .rliis is attributed to the unique cliaractcristics of tile eflluent. St~rihct~~ii t ef'fl~ienr was

observed lo sliow a insignificant variation in retention of organic content (COD) oil soil CS2, at

all HRTs and co~icentratlons, considered.

1.4.2 Natural Soils ( NSI , US2 and SS3)

Tile effect of retelltion time and concentl-ation of' inorganic pollutants presents in atnino acid.

surfactaiit arid pliarmaceurical effli~ents on nauiral soils (hS 1. KS2 and hS3) are sIio\v~i ill Figs.

4.19 (a) - (c). 4.27 (a) - (c) a~ id 4.35 (a) - ( c ~ . respectively and rhat of' orgalilc pollutants are

slio\vn in Figs. 4.203a) - (c). 3.28 (a) - (c) and 4.26 (a) - (c), respectivelg.

(C) .Yniiirnl Soil - l\'Sl

(1) Lnoreanic Pollutants

Aiiii~io acid and pharmaceutical effluents slio\+ed less variation of cliloride concentration (i.e.

high retention of chloride 600 to 1100 mg/L due to their anificiai contamii~ation on NS i. at 8 hr

aiid I6 lir HRTs at 50 % conceiitration. Tlie retention of chloride attains a maximum of (1251

miS/l,) on NSI, at 16 lir I-IRT, and nt 50 % concentration. Sucli a bcliaviour is generally

attributed to the time-dependent chloride adsorption and diffusion on soil Inass NSI . Tlie

surfactant effluent showed a less retenti011 of chloride (150-220 mg./L) even at I6 111. I-IRT, at 50

concentration (i.e., 25 O/o and 50 % concentration at 8 lir HRT were not appreciable).

The retenti011 of sulphate tvas found to reacli a high value at the end of 8 hr HRT at 50 %

conccntratioii due to aliiinu acid a~ id pliarmaccutical cITucnts. Tlie retcniioil of sulpliate oli soil

WSI was not found to be influenced by ainino acid and pllarmaceutical effluents at 16 lir HRT

and at 25 D/o and 50 % concentration. Sulphote rctentio~i was foiind to rcacli a maxii i iu~i~ of 628

nlgiL on NS1, due to phar~i~aceutical effluent contamination. The above bel iavio~~r is visualized

on tlie basis of initiation of reaction (i.e. adsorption process) by sulphate on soil S S I . The

surfactaiit effluent do no sliow appreciable retention of sulphate on NSI e~c in at I6 hr HRT and

a; 50% conceiltration. i\hicli ma) he auributed basicaliy due to 10% coilcentraticln of sulpl~ate

colitent ill :lie above effluent a!ld also due to slo\ver rate o f reactioil of sulpiiare in an a l l ~ ~ l i n e

medillin rllat is available ill tile above efflue~lt

m e a n i c Pollutants

1 n i n o acid and pliarinaceutical effli~ents slio\t.icd high variation of COD (i.e. lo\\ ~.etei?tio~? o f

COD) due to artificial contamination o S U S l . at 16 1:r IiRT at 5O0% co~lceil!i.atioil. Tile S lir

HRT at borh 25 % and 50 O/o concentratio11 of amino acid and pharnraceutical efflueiit do not

show appreciable rcteiltion of COD on soil US I.

Surfactant effluent ar both 25 O/o and 50 9.6 corlceiitrations and at 8 lir and 16 lir I-IRT was seen to

show a Iiigh retention of COD. due to artificial containination on soil NSI . icllicli may be

attributed to tlie high clay content in NSI .

(D) hrnfurol Soil - IVSZ

(1) Inorganic Polll~tants

Amino acid and pliarmacei~lical effluents silowed relatively loiv retention of cllloride on U S 2 at

50 % concentration and at 16 hr HRT, when compared to that of N S 2 . Tlle soil NS2 reached a

maximom retention of cllloride (567 mg/L) at 50 % concentration and 16 111. I-IRT due to artificial

contamination of pharmaceutical effluent. The variation in retetition times (8 hr & 16 lhr HRT)

and concelitrations (25% & 50 %) of silrfacta~lt effluent was observeti to be ina affected y

contamination on soil N S 2 , with respect to chloride retentio~i.

The pharinaceutical effluent was found to show a maximum retention of sillpliate on U S 2 (421

mg/L) at tlie end of 16 Ihr HRT and at 50% concelllration. Aiiiino acid erflucnt s l ~ o k e d relativel!,

less retention o f sulpliate even at the end of 16 hr HRT (at 50% concentration) when cornpared to

that of pharmaceutical effluent. Surfactant effluent do not show appreciable variation in

retention o f sulpliate on N S 2 , both at 25 % & 50 % coacentration and at 8 11s and I6 lhr HRTs.

Q) 0rga;iic Poliutants

Amino acid and plianiiaceutica! efflucrits slioi\,ed a reiativelq 10% retclition of COD OI? NS2 (ill

[lie range of 10.000 to 12.000 m g L ) at I6 lhr HRT arid at 50% concentratioli \rile11 coinpared to

that of S S I . Surfactant effluent sliowed iower retetitio~l of COD. on h S 2 (at 50fl/0 concentration

and at I6 hi. HRT) due lo tlie lo~ver cia! cotitelit of NS2 llian that of NS I

(E) ,l;a!~o.(il Soil - FS3

(1) Inorga!iic Pollutarirs

Amino acid and pharmaceutical effluents slioived lower retention of cliloride o r NS3 (300-420

mg'L) at 16 lir HRT and at 50 % concentration \\hen compared to NSI and NS2. The 8 ihr HRT

at both 25 % and 50 % concentrations do not show any appreciable retention of chloride due to

artificial contamination of tlie above effluents on KS3. Tile above beiiaviour was attributed to

the higher voids present in NS3 when compared to h S 1 and S S 2 (96 % silt content).

Surfactant effluelit showed a over all maximum retention of chloride (900-1000 mg/L), NS3 at

50 % concentration and at 16 hr HRT, when compared to that of NSI and NS2. The above

beh~iour is attribiited to the physical interception and subsequellt built LIP of chloride aggregation

on soil NS3 due to advection and adsorption phenomena. Sulphate retention Mas observed to be

very lou (100-155 mg;L) on NS3. due to artificial contamiiiation o i amino acid and

pliar~nace~itical effluents. and is interpreted, due to the low clay content (4?4), which fails to

initiate adsorptioii between the sulpliate in tlie effluent and tlie soil mass.

Surfactant efflueiit (at 25 % and 50% concentration a1 8 lir 16 lir HRTs) does not seen1 to sliow

appreciable variation in retention of sulpliate on soil NS3. due to tlie 10% clay content arid

alkaline nature of effluent.

12) Organic Pollutallts

The retention of COD on soil NS3. was observed to be more (3000-4205 111glL) due to

coilcentration of amino acid than pharmaceutical effluent at all coilcentratio~is and all HRTs

This beliaviour was due to the presence of higher voids in soil KS3 (i.e. allowing effluent to pass

through it). However, the surfactant effluent showed a peak retention of COD (4000-5050 mgiL)

011 YS3 l i a ~ e to artificial coiitamination of pliarn~aceutical effluent. at 50 96 cciicentration and at

16 hr HRT. Loner HRT (8 hr HRT) and concentration 2 j Oh and 50 46 do rior slio\i appreciable

retenrion of CCD on soil NS3. Tile reteiltion of organic content (COD). at 16 lhr tiRT i~ndergoes

a long bio-tra~lsformatio;?. sllo\vn by a more or less constant COD conce!ltralio~l. at rlie oc~tiet of

soil -column.

4.4.3 Coinrnercial Soils Vs Natural Soils

Basetl oil results and inret-pretations presented sections 4.4.1 $ 4.4.2, the fol lou~ii~g salient

inferences are dra~bn:

(i) Based on tlie interaction of inorganic pollutants i.e. chloride present in the chosen

effloents (tliree) and the three natural soils; it is observed that interaction of above effluents

on US2 is found to be critical ~vllen coiiipared to NS1 and NS?. The behaviour of S S 2 ~vith

surfactant effluent is comparable to that of CSI.

(ii) On the basis of interaction of three effluents on the three chose~i soils, it is evident that

atnillo acid effluent is found to play a predoliiiiiant role on sulpliate re~ention. The

interaction of above effluent or? NS2 is found to be comparable to tha tofCSI .

(iiii The retention of organic content was found to be higii on NS2 and YS3 than NSI due to

artificial contamination of pharmaceutical effluent. Tliis behavioi~r was found to be

iilfluenced by tlie limiting clay content presetit in natul-ai soils.

(iv) In view of tlie organic pollutant interaction. dire ro tliree cliose~i soil 9i effluents, it is

evideill that NS I to s l i o ~ ~ s a larger variatiot~ in retention of organic contclit (COD) \vIlcn

compared to XS2 atid NS3. Tile belia~iour of NSI, i.e. interaction of organic pollutant \\it11

tile natural soil - KSI. is colnparablc to tile beliavioi~rof CS2.

4.5 EFFECT O F EFFLUENTS ON T H E INDEX PROPERTIES OF SOILS

4.5.1 Effect of Amino Acid Effluent on Liquid Limit (LL)

Liquid limit with titiie for kaolinite and beiito~iite soils ji.e. CSI; CS2) d ~ i e to artificial

contamination of amino acid effluent upto 160 - 195 days. are given in Tables 4.4 and 4.10,

respectively. For the three chosen naturals soils A'S1 to NS3, liquid litnit (upto about 140 days)

are given in Tables 4.16 to 4.18, respectively. Variation of liquid limit Vs time (in days ) are

shown in Figs. 4.37 (a) arid 4.38 (a) for CSI and CS2 and that for the three natural soils NSI to

NS3, in Fig. 4.39 (a). Discussio~? based oil the above results and on co~npal.ison ~vitli liquid Iinlir

bebre containiiiatio~i (bq tile effluent) and ~nfere:ices drawn are gi\eii belo\\

j/i) Canzr?tei.cic~i Sails (CSI and CS2/

the liquid liniit of ltaolinite soil (CSI) remained almost constant (after artificial contamination )

tip to 100 days, beyond \~Ii ich only slight increase in the valiies were observed, till 175 days.

Hence, for all practical purposes, it can be stated tliat amino acid effluent do not cause significant

changes in tlie liquid liniit of ltaolinite soil. Tliis is due to the fact that ltaolinite has basically a

non-expanding lattice, a non-interactive system and lias a lo~v CEC (carion exchange capacity)

[Rlitchel (1976). Sridharan (1990)]. Due to the above, changes in tlie pore-fiuid characteristics

\voi~id not be reflected on its behaviour.

On the other hand, bento~iite soil (CS2),wIiich has montmorillonite as tlie niajor minerai. exhibit

significant clianges in the liquid limit with respect to tiiile, due to (artificial) co~ltaniiiiation of

amino acid effluerit. The liquid limit increased to a ~naximum value of 173 % i at the end o f

200'baay) fro~m the initial value of 157 % (i.e., at zeroth day). !However, beyond 150 d a ~ s . liquid

limit of CS2, remained almost constant. Significant increase in tlie liquid limit with time. may

he attributed to tlie presence of sulpliate and cliloridc in the abovc effluent. wliich generally

causes particle disassociation and hence, increases the liquid 1i1:lit ( Sivapullaial; and others.

1985).

(B) 1"1'ntlnoiSoils l;VSJ, ;VSZ and NS3)

It is generally observed tliat the liquid limit of all the tliree nati~ral soils P S I , NS2 and h S 3 )

lhave increased continuously with time, LIP to about 140 days of (artificial ) conta~nination.

Highest liquid limit was obtained for NS2, followed by NSI and NS3. at tlie end of 141 days.

Moreover, up to 15-30 days of contamination; the liquid limit remained niore 01. less constant.

but. thereafter lias increased niore or less continuously, up to 90 days. The increase in liquid li~iiit

with duration of contamination can be explained as follows: (i) In the case of amino acid

effluent, the presence of sulpllate and chloride seem to over ride tile effect of monovalent @at)

and divaleiit (cat?) ions, which normallj promote partial aggregatioil, due to suppl-ession o f

double l q c r thickness; (ii) I'lie prescncc of sulphate and cliloritlc in tiic above ci'tli~ent has

induced particle repletion and lience the Iicjiiid has increased.

.I'lie obserbed delayed rcspoiise in the abovc soils. i.e.. iiicrease in tile liquid liinit only after a

considerable period of coiitainiination, (i.e.. 15-30 days) is attributed to tile iiiteractioii o f

sulpliate with the soil. Tile above delayed response is similar to tlie reported beiiaciocr of lime

treated soil (i.c.. shoiving inegative ci'l'c~t 0111) allel- a coiisicler,rblc period. sn) 6-12 ~niontlis) b?

Siiaapulliah arid others (1994).

4.5.2 Effect of Surfactant Effluent 011 Liquid Limit (LL)

LL for kaoli~iite and henotinile soils (CSI and CS2) due to artificial co~itanlinaiion of s~~ri'acraint

effluerll (up to 165-1 75 days) are given in Tables 4.5 and 4.1 I, respectively. Fol tlie liatural soils

(US1 to KS3): LL (up to I65 dais), are given in Tables 4.22 to 4.24, respecti~elp. Variation of

ILL Vs tiilie (in days) are slio\bn in Figs 4.37 (a) and 4.18 (a) for CS I. and C S 2 . Sii~lilarly. for

tlie three iiatural soils. the abobe variation is shobn in Fi_e 4.40(a). Based on tlie above. salient

discussion and inferences draivn are given below.

(A) ComniercinlSoils (CS1 nrld CS2)

'llie LL of ltaolinite soil (CS I) remained allnost constant after (ai-tific~al) co~itainii~iatjo~n. up Lo

160 days. Tlie above behab io~~r (i.e., no significant clla~i_ees in LL ui th respect ro pro!onged

duration o f contanninarioii) is similar to the belnaviour exhibited by CS I due lo contamination of

amino acid effluent. bur For tile same reasons stated earlier [section 4.5. I(A)].

LL of bentonite soil (CS2), due to (artificial) contamination of surfactant effluent and LL of CS2

due to contamination of amino acid effluent, Lvere found to be alinost identical (Tables 4.10 and

4.1 I ) , considering the total period of contamination. Tliis again could be attributed to tlie

presetice of sulpliate and clnloride in the effluent and their interaction with the soil-CS2.

IB) ,Vufarul Soils (ASl, lVS2 and NS3)

The LL of all tlie natural soils(NSI to NS3) were found to increase significantly up to 75 days of

contamination atid after that to a lesser extent till 165 days o f contamination. Trends in the

maximum values of LL due to contamination the above effluent for T S l to NS3, \\ere found to

be siliiilar !o tliet of co~~tamiiiatio~i of amino acid effluent for US1 to NS3, the above behaiio~tr

is once again attributed to tlie Yery high coiicentratio~i of chloride and sulpliate in surfactant

effluent. wllich lias resulted in masking tlie effect of tlie anions it1 tlie soils.

4.5.3 Effect of Pl~armaceutical Effluent on Liquid Limit

Liquid Limit for CSI and CS2 due to (artificiai) co!ita~nination of pharmaceutical effluent (up I@

175-195 daysj are g i x n in Tables 4.6 and 4.i2, respectixely, and ihar for XSi to NS3 are given

Tables 4.28 to 4.30. Variation of liquid limit Vs time are shown in Figs. 4.37 (a) and 4.38 (a) for

CSi and CS2 respectively, and in Fig. 4.41 (a) for h S i to NS3. Based on tlie abo\e. following

inferences are drawn.

(A) Cow~tt~ercinl Soil (CSl ui~d CSZ)

Kaoliliite (CSI) exlnibited similar behaviour ail11 respect to liquid limit, as due to iartific~ali

contamitlation of the other t\+o types effluents considered, 111 other words. hquid liimit of

kaolinite is not significantly affected, due to (artificial) contstninaiion VF three effluents

considered. for the reasons stated earlier[ sectioii 4.5.1 (A)].

Similarly. bentonite (CS2) exhibits identical behaviour with respect to range of liq~tid limit

values attained, due to conlamination of the three ef'fluents considered. I-lowever, the only

distilictive difference betxeen CSI and CS2, being. the Lariation of liquid limit. whicli is

significant in CS2 (during tlie period of contamination).

(B) ~l?lirturol Soils (NSI , RS2 ond iW3)

The LL of a1 rhree natural soils were fourtd to increase gelitly up to 30-45 days of'contami~~ation,

beyond which, LL decreases up to the end of 138 days of contamination. Of tlie three soils. 5 5 2

sllows higher values of liquid limit initially, i.e., up to 45 days, than tlie liquid limit values of

their two natural soils considered. In general, tlie above behaviour is similar to rlie behaviour o f

X i to NS3, with respect to other two effluents considered.

4.5.4 Effect of 4mirlo Acic! Effluent on P l a ~ t i c Limit (PL)

piastic I.imit (PL) for kaolinite and bentonite soils ( i t . . CSI and CS2) due to artificial

conta~ninalion of amino acid up to 165-195 days, are gi\,e~i in Tables 4.4 and 1.10. re~pecti \~ely.

For tile tliree chosen natural soils PL values (up to 140 days). ase giben in Tables 1, ih to 4.18.

respectively. Variation of P L ni th time ale shown in Figs 1.37 (b) and 4.33 (b) for CSI and

CS2. respectively and in Fig. 4.39 (b) for US! to NS3. Based on [lie above. follo\+ing infereilce

are draivn:

(A) Contn~errinl Soils (CSI nnd CSZ)

Plastic li~:iit CSI was found to vary bei\\ee~i 20-23 a~ ld that for CS2 bet\wei: 67-75. in o:lie:

\\ords. CSI i l ioas insig~iifica~it variations. wlieseas, CS2 s'lo\\,i significarit \a~-iation in plastic

limit vaiues. di~riiig the pesiod of coniami~iatio~i considered. The abo\#e heiin\iour is identical

to that o f the hehaviour of CSI and CS2 with lespect to liquid li~nit. due to con:a~iii~lntioii of

a ~ n i ~ i o acid and it is also attributed to the reasons stared earlier.

(B) hbturol Soils (KSI, M.2 nnd jVS3)

PL values for NSI to NS3 are found to be in tlie range of about 30-60: 22-75 and 36-68,

respectively, during the period of contamination. Highest plastic limit was obtained for NS2.

than for LS1 and NS3. bloreover, NSI and NS3 attain nearly equal values of PL, nithin the

period of contamination.

The above bel~aviour is identical to that of XSI to NS3, with respect to LL. due to conlamination

of anii~io acid. for tlie reasons stated earlier.

4.5.5 Effect of Surfactant Effluent on Plastic Liniit (PI,)

Plastic limit for kaolinite and bentonite soils (CS1 and CS2) due to artificial contamination of

surfacraiil effluent (LIP to 165-175 days) are given in Tables 4.5 and 4.1 1, respectively. Tor

natural soils 'SI to NS3), PL (up to 145 days), are given in Tables 4.22 to 4.24, respectively.

Variation in plastic limit Vs time are shown in Fig. 4.37 (b) and 4.38 (b) for CSI and CS2,

respecli\ely aiid in Fig. 4.40(b) for US1 and NS3. Based 011 the above, inferences drab611 are

glven below.

(A) Com~zercialSoils (CSI and CSZ]

PL for CSI and CS2 are found to be in tlie railge of 20 to 25 atid 67 to 75 for CS2 and CS2,

respectively. during tile period of contan~iiiatio~r. The above treiids are identical to ilia1 o f the

trends observed for liquid liiliit for CSI and CS2. due to artificial corrtaniiilatioii of surracmnt

effluent.

(B) n'atural Soils fi\TSI, : W , a n d SS3)

PL for NS1 to TS3 are found to be in tire range of 27 to 43, 29 to 46 and 36 to 47. respectibely,

during tlie period of conla~iri~latioii. In illis case also, idenlic;~l ircntls are eshibitetl b! h S 1 to

h S 3 as in tlie case of contamina~ion by amino acid eff l~~ent . on the natl~ral soils.

4.5.6 Effect of Pharmaceutical Effluent on Plastic Limit

PL for CSI and CS2 due to contamination of plrarnraceutical effluent (i~pto 175 - 195 da)s) are

given in Tables 4.6 and 4.12. respectibely. For NS! to KS3, PL \aiues due to contamination of

phar~nacecitical effluent are giben in Tables 4.28 to 4.30. Val-iation 111 Pi- Vs unre are shown in

Figs. 4.37 (b) and 4.38 (b) for CS! and CS2, respectively, and File. 4.41 (b) for NSI to NS3.

Based on tlie above, following inferences are draan.

(B) ~Vatural Soils fiYS1, lYS2, NS3)

Range of PL values due to coiltarnination of NSI to NS3 are found to 27 to 3 1; 22 to 36 and 29

to 39, respectively, during tile period ofcontamination. I t is seen plastic liniit values are found to

\ary gently and tlie range of variation is slightly lriglrer for NS2 than for the other two natural

soils considered. Tile above beliaviour is fourid to be similar to tliar of [lie beliaviour of rile tliree

liatliral soils, with respect liquid litnit.

4.5.7 Effect of Amino Acid Effluent on Shrirlkage Limit

SL for the two commercial soils due to (artificial ) contaniination of nmirlo 3cid efflucnl are

given in Tables 4.4 and 4.10, respectively and that for the three natural soils are given in Tables

4.16 to 4.18, respec~.ively. Variation in shrinltage Iiniit \\tit11 time for commercial soils and

liatural soils are s h o ~ n in 4.37 (c) & 4,38 (c)and in 4.41 (c), respectivel). Based on tlie above

following inferences are dra\hli.

(A) Conzn~ercialSoils (CSI and CS2)

SL for CSI has sliown very little variatio~l during the period of contaniination which !nay

attributed to a possible completion of ion-exchange process. On the other hand CS2 has showt~

considerable variation ill SL values (i.e.. about 8-25). during tile period of contamination. which

is significant. I-iiglicst shrinkage Iiniit vaiues was found at the end of h e period of

conta~niiiation, whereas. the lowest value at the beginning of contami~iation. Pressrice of

cliioride and sulphate in tlie effluent lias iticreased the particle flocc~ilarion. resulting in liig!ier

values of shrinkage limit. This shows iiiat tire behavio~lr oTCS I lhas 'I-emained u~iclianged' tlue lo

contamination of amino acid, whereas, tlie behal,iour of CS2 has changed form ' ao rse ' to

'good'. wit11 respect to shrinkage limit. In other so rds . there is a 'positive influence' in CS2.

due to containination of amino acid.

(B) hratural Soils ( .MI, KS2 arzd M3)

SI, is Ib[ind ro be ill tlic range of ctbout 15 to 20; I6 to 20; l I to16 for h S l . VS2 ant1 NS3,

respectivelj. Variation in shrinkage litnit vali~es are foiind to be siniilar for NSI and US3.

whereas. for NS2, tlie \ariation is found to be colnparatively higher. Tlie beliaviour of NS2 is

found to be similar to that of CS2, in respect to shrinltage limit. due to contamination of amino

acid ei'ilucnt.

4.5.8 Effect of'Surfactant Effluent on Shrinltage L i n ~ i t (SL)

SL for the commercial soils. due to (artificial) contamination of surfactant eff luen~ are given in

'Tables 4.5 and 4.1 1, and that for natural soils. SL are given in Table 4.22 to 4.24. Variatioli of'

SL with time for CSI and CS2 are sliown in Figs. 4.37 (c) and 4.38 (c ) and that For natural soils

in Fig. 4.40 (c ).

(A) Conmzercial Soils ( CS1 and CS2)

Comparing tlie 'SL' values due to contaniination of surfactant effluent and a~n ino acid effluent ~t

i-. j~iiild ihat actual values o i SI. it1 tlic i'or~nel- arc found to less than the latter. 'The above

bella\iour oi'coiiumercial soils 1s a~tributed to tile highest chloride coiitelit present in surfactant

eflueni. In tile case oi' CS2. 'negative inili~e~lce' due to contaminatio~i of effluent i.e. froin

.betier' to ' \~orse ' is obser\.ed.

(5) nirtrrrnl Soils (.YSI, ,W ortd .VS3)

NSi to NS3 also exhibit loaer v a l ~ ~ e s of SL due to contaminarion of surfactaiit than the case o f

amino actd. This is also attributed to the presence of higher chloride content present in the

ef'lluent. For all tile natural soils, there seems to be a posir i~e influence, due to contaminario:? of'

tlie tfrluent. i.e. fsom 'worse' to 'better'. \\it11 ;espect to tlie actual values oSSL.

4.5.9 Effect of Pharmaceutical Effluent a n Shrinkage Limit (SL)

SL for CSl and CS2 due to (art~ficial) contamiilation of phartnaceutical efililent are given 111

Tables 4.6 and 4.12, respectivelj and that for NS1 to iiS3 are given in Tables 4.28 to 4.30.

Variation of SL Vs tiilie for CS1 to CS2 are shou;n in Figs. 4.37 (c) and 4.38 (c). res?ectivel!,

and that for US1 to NS3, are shown in Fig. 4.41 (c).

(A) Conr~tercinl Soils ( CSI nrld CSZ j

CS1 exhibited a slight increase in SL values i.e. 6-7 ahereas: CS2 has shown considerable

\ariation in SL values (i.e. about 6-26), during the period of contamination. \vInch is sipxtican:.

Highest SL value was found at the elid of tile period of contan~ination. \~ l l i ch shous that the

beha\.ioiir of C S 2 has changed form 'worse' to 'good' wit11 respect to SL. The above behaviour

is sim~lar to that of the beliaviour exhibited h) CS2 due to contaminatio~l of amino acid effluent.

On the orher hand. CSI had rernaiiled unchanged, which is also similar to the behaviour o f CSl

due to contamination amino acid effluent.

(5) Ilintuml Soils (MI, ,VS2 arld R'S3)

The trends in SL values due to contaniination of pharmaceutical effluent are sinlilar to that o f

surfactant effluent. Moreover, similar behaviour in terms of positive influence are also observed

in all the three natural soils.

4.5 EFFECT OF EFFLUENT ON THE SWEAR STRENGTH OF SOILS

4.6.1 Effect of Amino acid Effluent

znconiined compressive strength (UCC) of the two co~n~nercial soils due to (artificial)

colltalnination of a~n ino acid effliielit are gibe11 ill Tables 4.4 arid 4.10 respecti\eI)'. For :lie

~lati~ral soils. I!CC values after contaniination are given in 4.16 to 4.18. respectively. Variation

of I!CC will1 time for CSI and CS2 arc sl10\\.11 in Fig 4.42 and 4.43. respectivel) and for natl~ral

soil? ill Fig 4.44. B o w on ilie aho\.e discucsion i inrcrcnce~ at-c givcn hclo\v.

(A) Conir??ercial & Siitlrrol Soils

UCC valiies geiierallj show a moderate iilcrease ul? to 60 da!s o f contamiiiarioii ant1 thercatier.

decreases gently, for all tile live soils. The a b o ~ e bcliavioiir illy be attributcd to the conibi~led

predominat role of sulpliate and cliloride in flocculating the particles a n d lhence Icading to

increase iii the strength. I4owever. beyond :he above initial period eschalige of ions rnny have

ceased and hence iioula have resulted in dispersion of particles leading to ireduction in strengrh.

The ahove behaviour holds good for all the five soils considered

4.6.2 Effect of Surfactant Effluent

UCC oi'coinmercial soils are giierl in 'l'ablcs 4.5 and 4.1 I. lrespeclivel! For natural soils. U C C

values are given in Tables 4.22 to 4.24, respectikely. Variation of UCC !\~itli time for CSI and

CS2 are slio~vii in Fig. 4.42 and 4.43, respectively and for natural soils in Fig. 4.42 and 4.43,

respectively and for natural soils in Fig 4.45. Discussion ,' inferences based on tile above. are

given below.

(A) Conitiiercial uizd hirtrtral Soils

UCC values generally show a moderate increase up to 30 days and thereafter decreases. gently

for all the five soils. except, CS I (i.e. kaolinite). CS I shows increase in tlie strength for a longer

period, which may be due to prolonged flocculation of particles and hence leads to increase in

strength. However, after tlie above period. immediate dispersion of particles, would have caused

the sudden decrease in the strength. The behaviour of all other soils, is similar to that of the

behaviour due to contamination of amino acid.

4.6.3 Effect of Pharmaceutica? Efflue~lt

UCC of coinlnercial soils are g i ~ e n in tables 4.6 and 4.12, respectively, atid that for \S! to NS3

in Tables 4.28 to 4.30, respectively. Variation of UCC uitl; time for CSI and CS2 are siiown in

Fig. 4.42 and 4.43, respectively, and for natural soils in Fig 4.46. Discussion/infereiices based on

[lie above are given below.

(A) Comnte~cial and Natural Soils

UCC val~ies generally sliow a moderate increase liplo 30 days and tliereafier decreases. for all rile

five soils. The above behavio~ir is due to reasons stated earlier [section 4.6.1 (A)].

4.7.1 Leacliate Contamination Model

.An attelnpt was inade to inodel the variation of concentration of significant inorganic i organic

pollutants, with respect to solid retention times. Literature search ~i iade in this regard. resulted in

the identification of the various 'leachate contamination model' proposed by Nair and others

(1990).

The above leachate contamination model could be used for obtaining the concentratio~i of

cotitamiiiaiit in the aqueous phase or iti gas pliase and in multi-phase. The aqueous phase niodsl

does not include tlie effect of organic transformation that raltes place in tlie soil tiiass v.liicli

would alter tlie liquid and plastic limits of soil. Tlie gas-pliase emission rate nod el is used for tlie

predicrion of rate of transformation and hence per~neatio~i of dilute organics iii the soil. A brief

description of tlie three models based 011 reported lirerature, are given below.

(A) Aqueous Phase Contan~inafion Model

This model is used for tile prediction of cot~servatice and non-conservati~e contaminants

prediction in tlie aqueous-phase (Nair and otliers 1990). It is presuined that tlie rate of

transfortnation of contaminant, especially in tlie gaseoits pliase, is negligible when coinpared to

non-conservative pollutant in tlie aqueous phase. 'Tlie equation used for tlie iniodel is given in

(4.1).

,,here, R~ = I-eaclia~c rate ofco~ita~i i inant to \+ater taiiic ik~no l / 111' d )

I),, = i:rScctive 11iola1 diff i~sio~i cocnicielit

D,,, = Dispersion coefficient

= POI-osity of unsat~~rated zone

S = Mciisture content

, = Aqueous phase velocit! in poi-es

C,, = Aqueous phase coiltaminant concentration

(B] Gas-Plrnse Enfission Rate lModel

TIie model signifies the state o f leachate emission rate during organic traiisfor~nations. It is

assumed in the model that the solids in the pores of saturated zone ~~nc ie r long retentioil tin:e.

undergoes gaseous transformation. and lience a l l o ~ i n g ~ h c soil to periileatc to lhigli concentration

ofcoiltaminants and hence influence liquid limit of soil.

where.

C* = Molar density o f gas phase

D, = Effective ~no la r diffusion coefficiein

Q = Porosity of unsaturated zone

S = Moisture content in unsaturated zone

C, = Gas phase contaminant concentration

V, = Gas phase velocity ill pores

(Cl Multiphose Confanlinnnt Concentrnfion (MCC) dfo~le l

This model predicts the variation of contaminant concentration (both conservative aiid nnn-

collservativc) (LC. iilorganic and orga~iic pollutants) in tlic aqucoils phnse \villi rcspcct iil

gaseous and solid phases (i.e. in the presence o f solid and liquid phases).

The collta~ninant variation i n the aqueous phase would be significant during co~ i t in i~ous inode o f

operation when compared to the batch mode of operation. Continuous mode o f operatioi: is more

sig~iificant, d ~ ~ e to long traiisfor~nation phase involving gaseous and solid phases. resi~ltin_p iii the

nodificetion of soil properties (i.e. liquid, plastic and shrinltage liniits of' soil)

cp s R~ ,,,, = a~az [ D,, I? s ac,, I s z ] t a~ez [ D,,, cp s sc, , 8Zj

- ' r . , , (3SC. , - i~sp ' rC , , /H , ,~s

wliere . Rdu. = Aqueoiis phase retardation factor [It p h / (I-Iws p )]

cp = Porosity of unsaturated zone

S = Moistlire content iii ii~isaturated zone

C = Aqueous phase contaminant concentration

D, = Effective niolar diffusion coefficient of contaminant in tlie liquid phase

D,,, = Dispersion coefficient in the flowing aqueous phase

y = Porosit) of unsaturated zone

, = Aqueous phase velocity in porcs (in 1 d)

D, = Effective molar diffusion coefficieiit in gas pliase

Id,,,, = Water - gas partition coefficient

C* = Moiar deiisity o f gas

Vy = Gas phase velocity in pores

. = Deca) constant for nori- consenative contaniinant in aqueous phase

H,,, = Water - solid partitior coefficient

I , = Decay constant for non- conservative conta~iiinant in gas pliase

= Decal colistant for non- conservative c o ~ i ~ a ~ i i i n a ~ i t in gas pllase

PI, = Bulk density of solids

4.7.2 Selection of ,Model

Tile three ~iiodels proposcd i 11sed hy Nair atid otlieru (1990) \\ere 01-igiilally L~riiiulatctl ibr

iiiodeli~ig leachte contaminant concentration/(si. Of the tliree models 'MCC' is applicable for a

multi-phase system and lhence chosen for tlie preselit study to model tile iiil~l~i-phase.

colita~iiinant concentration (i.e. the concentration of chloride, sulphate, TVS, COD) with respect

to various concentrations of effluent and solid retention times.

4.7.3 \'isuallzatio~s of soil polluta~at ln t e rac t io i~ fo r the Application of 'MCC' Model

.rile trn~isport end traiislbrmat~oi~ phenoniena responsible for soil pollutant interaction. are

vlsualizcd it1 this stud! as detailed in Fig. 4.47 (a) for tlle purpose o f undei-standing and

application o f 'MCC' model to the present study.

4.7.4 Validation of Erpe r i rne~ i t a l Data Usillg 'MCC' Model

(A) Sintuiafiari

For tile present work. tlie system equation [as given in Eqii. (4.3)] is ~iiodified in reiation to the

11on-din~eiisionai para~ileters (i.e, concentrations of chloride sulpliate. COD and TVS. \iritll

~recpeci to concentration at 50 Yo atid solid retention time) to obtain tile (i) solid retention factor

a~ld iii) concentration factor for continuous inode (1.e. 8 hr tIRT and I6 iir HRT).

'rile ~nulti - pliase coiitatiiinant concentl.ation model Iias been applied for the prediction of

aqueous pliase pollutant concentration. ( i.e. both inorganic I organic ) for two of tlie three

industrial efflueiits (i.e. anlino acid and pharmacei~tical). and foi all the ~iatural soils ( NS I to

hS3) considered in this stud!.

The inodel is used to first simulate the concentration factor for various pollutants and solid

rerelition factoi-. using Eqn.. (4.3) and assuming the following parameters :

(i) Kater - gas partition coefficient. H,,, = 2 mg/L

(ii) Molar density of gas (C') = 1.2 gl ~moie

(iii) Gas phase velocity in pores (\i, ) =negligible

(iv)Decay constant for non- conser\,ative contaminant in aqueous phase ( I , , ' ) = 0.72:d

(v) Water - solid partition coefficient (H,,) = 1.34 mg'L

(vi) Decay constant for lion- conservative contaminant in gas phase (1%) = negligible

(vii) Bulk density o f solids = 2.64 g,/://c& The above \slues are substituted to get tlie aqueous phase coiltaminant concenirarion (C\\) as

concentration factor. Tlie simulated co~lcenti-ation factors Ibr the chosen pollutants and for tlie 6

various effluents, are slio\\n in Figs 4.49i4253s

match the experimental &?a. !ii order to evaluate the goodness of fit (between the simulated and the actual concentrat~oii curves). tile staiidard root mean error, was calculated ; considering all data poiiltr , u"11g Eqii. (4.5). Based on the above error analysis. the range of error is found to be 13.18%. colisidering all effluents and pollutants considered for the 'model validation'. The above error can be considered as acceptable and reasonable.

Table 4.1 (a): Characteristics of Pharmaceutical, Amino Acid and Surfactant Effluents due to Artificial Contamination of Kaolinite soil (CSI) - Batch Mode

Xote iii P - Phaniiaceii~ical, A - Amiiio acid, S - Szirfaciaiit (11) l*) - Indicaies readings/resiiils 11 hich are insign(/icani and hence no1 given (fir) Daj's b~dicate tile elid ofperiod a1 ivhicii the parariieiers ivere delermived

Table 4.1. (b): Characteristics of Pharmaceutical, Amino Acid and Surfactant Effluents due to Artificial Contamination of Kaolinite soil (CS1) - Batch Mode

Table 4.1 (c): Characteristics of Pharniaceutical. Amino Acid and Surfactant Effluents due to Artificial Co~~tamination of Kaolinite soil (CSI) - Batch Mode

Table 4.2 (a): Characteristics of Pharmaceutical, Amino Acid and Surfactant Effluents due to .4rtificial Contamination of Kaolinite Soil (CS1) -

(Continuous Mode - 8 hr HRT -25 % Concentration)

Table 1.2 (b): Characteristics of Pharmaceutical. Amino Acid and Surfactant Effluents clue to Artificial Contamination of Kaolinite Soil (CS1) - (Continuous Mode - 8 hr HKT- 25 :h Concentration )

Table 4.2 ( c): Characteristics of Pharmaceutical, Amino Acid ant! Surfactant Effluents due to Artificial Contamination of Kaolinire Soil

(CSZ) -(Continuous Mode - 8 hr HRT- 25 % Concentration)

Table 4.2 (d): Characteristics of Pharmaceutical, Amino Acid and Sur-faetant Effluents due to Artificial Contamination of Kaolinite Soil (CSI) - (Continaous Mode - 8 hr HRT- 50 % Concentration)

Table 4.2 (e): Characteristics of Pharmaceutical, Amino Acid and Surfactant Effluents due to Artificial Contamination of Kaolinite Soil (CS1) - ( Continuous hlode - 8 hr HRT- 50 % Concentration)

Tabiie 4.2 ( f): Characteristics of Pharmaceutical, Amino Acid and Surfactant Effluents due to Artificial Contamination of Kaolinite Soil

(CS1) - (Continuous Mode - 8 hl- HRT - 50 O/o Concentration )

Table 4.3 (a) Characteristics of Pharmaceutical, Amino Acid and Surfactant Effluent Contamination Kaolinite Soil (CS1) - (Continuous Mode - 16 hr HRT - 25 % Concentration)

Table 4.3 (b) Characteristics of Pharmaceutical, Amino Acid and Surfactant Effluent Contamination Kaolinite Soil (CS1) - (Continuous Mode -16 hr HRT - 25 % Concentration)

Table 4.3 (c) Characteristics of Pharmaceutical, Amino Acid and Surfactant Effluent Contamination Kaolinite Soil (CS1) - (Contini~oi~s Mode -16 hr MRT - 25 "/a Concentration)

Table 4.3 (d) : Characteristics of Pharmaceutical, An~ino Acid and Surfactant Effluents due to Artificial Contamination of Kaolinite Soil (CSI) - (Continuous Mode - 10 hr HRT-50 % Concentration)

1

/ Alkalinity ' Conductivity Total Solids pH I ( r n g ~ ~ ) (lo3 r n g ~ ~ )

Table 4.3(e) : Characteristics of Pharrnacetrtical, Amino Acid and Surfactant Effluents due to Artificial Contamination of Kaolinite Soil (CSI) - (Continuous Mode - 16 hr HRT - SO % Concentration )

-- Dissolved Solids 1 Chloride 1 Sulnhatc I ,

( lo3 rng/L) ,

(rngIL) Days

( n l i / ~ )

P A s P A S I> 1 A I I S /

Table 4.3(f) : Characteristics of Pl~armaceutical, Amino Acid and Surfactant Effluents due to Artificial Contamination of Kaolinite Soil (CS1) - (Continuous Mode - 16 hr HRT - 50 % Concentration )

'Table 4. 4: Effect of Artificial Contamination of Amino acid Effluent on the Properties of Kaolinite Soil (CSI) with Tirne

Table 4.7 (a) : Characteristics of Pharmaceutical, An~ino Acid and Surfactant Effluent, due to Artificial Contamination of Bentonite Soil (CS2) - Batch \lode

PW 4lkalinltj (mgIL) Da)s

I Total Solids Conducti\i@ (lo3

( l o 3 mglL) pSIcm)

rable 4.7 (b) : Characteristics of Pharmaceutical, Amino Acid and Surfactant Effluents due to Artificial Contamination of Bentonite Soil (CS2) Batch Mode

Table 4.7 ( c): Characteristics of Pharmaceutical, Amino Acid and Surfactant Effluents due to Artificial Contamination of Bentonite Soil (CS2) - Batch Mode

Day

Table 4.8 (a) : Cha~~acte?istics of Pharmaceuticnl, An~ i r~o Acid and Surfactant Effluents due to Artificial Contamination of Bentonite Soil (CS2) - (Continuous Rlodc -8hr HRT - 25 "/a Concentration)

Electrical Conduct~r t t j *lkaiinlb (n~g iL ) 1

Table 4.8 (b) : Characteristics of Pharmaceutical, Amino Acid and Surfactant Effluents due to Artificial Contan~inatior~ of Bentonite Soil (CS2) - (Continuous niode - 8hr HRT - 25 "A Concentration)

/ Total Dissolved

~ a y r Solids (n~g/L) Chlorides (mg/L)

A ~ P / S

Sulphates (mg1L)

Table 4.8 (b) : Characteristics of Pharmaceutical, Amino Acid and Surfactant Effluents due to Artificial contamination of Bentonite Soil (CS2) - (Continuous Mode -8hr HRT - 25 '/o Concentration)

Chlorides (mg1L) Sulphates (mg/L) 1 5 Solids (rnglL)

rable 4.8 (c) : Characteristics of Pharmaceutical, Amino Acid and Surfactant Effluents due to Artificial Contamination of Bentonite Soil (CS2) (Continuous Mode - 8hr HRT - 25% Concentration)

COD (mg/L) Days1

j , 18 1 15 11

4 16 ' 17 10

5 1 7 11 9

6 13 , 12

7 1 3 1 8 ! 6

S 1 3 1 8 / 7

9 ' 1 2 1 7 ; 8

10 11 I 19 10

1 1 1 0 , 12 11

12 18 , 16 11

Total Volatile Solids BOD (rng/L) (10 3 m g / ~ )

Table 4.8 (c) : Characteristics of Pharmaceutical, Amino Acid and Surfactant Effluer~ts due to Artificial Coritaminatio~~ of Bentonite Soil (CSZ) (Continuous Mode - 8hr HRT - 25% Concel9tration)

Table 4.8 (d) : Characteristics of Pharmaceutical, An~ilio Acid and Surf:~cta~lt Ilf'flueiit I)uc to Artilicial Co~~tarnination of Bentonite Soil - CS2 (Contiliuous ;\lode - 8i1r HRT- 50% Concentration )

-"F- - - F l e c t r i c a l Conductivity 1 Alkalinib (mg/L) ;

I pH , Days, I X ~ O ~ ( ~ S ~ C I I I )

m m m o o o a o o o

- - 1 - --

\

- I r n ;:::?:;:::::;;:;;I 1 7 5 C P I , 2 5 , - W m m N a a N - m m w m N - 0 - N

p m o m m w o - ~ m ~ m o m m m m - " m = - 5

~"~a,:::::::g::::::::::::~:::i

Table 4.9 (I>) : Characteristics of Pharmaceutical, Amino Acid and Surfactant Effluents duc to Artificial Contaniination of B~lliOllite Soil (CS2) - (Cotitinuoas Mode-- 16 hr I3KT -25% Concentration)

'I'ahle 4.9 (d) : Characteristics of Pharmaceutical, Amino Acid and Surfactant Effluents due to Artificial Conta~ni~lation of Bentonite Soil - CS2 - (Continuous Mode - 16hr HRT - 50 % Concentrntio~~ )

j .- L i & i L 2 3 E E G L L L E e 1; o - -5 0 < % % % ~ ~ ~ g ~ ~ g * N N N N N N % * I

5; / ~ ~ ~ ~ o - w r n * m r n ~ r n m ' N N N N N N N N N Nii

Table 1.12: Effcct of Artificial Contamination of I'harmacciitical Effluent on t l ~ c Propertics of Deritooite Soil (CS2) with Time

-

Table 4.13 (b) : Charactel.is1ics of Amino acid Efflucnl Due la Artificial Coatamination of Natural Soils (Batch Mode)

- -. . . -- --

Chloride Sulphate (1ng1L)

Table 4.14 (c) : Characteristics of Amino acid Effluent due ta Artificial Contamination of Natural Soils ( Continuous hlode - 8 Xr HRT-25% Concentration )

COD (mglL)

BOD 1 Ni t ra t e Total Volat i le Solids ! (10' rngiL)

(mgiL) (rng!L)

: i ~ l z / w q q q ; o q q o : q m q j y Z ! m '1 rn r- o n n i- r l n n c

r- i

3 - ? ? f * - r e * IgiE K E K K K K K K E E E E C? '1 <? 0 C? c-, C? 0 C? C1 C1 r-- "-

1 ..I .̂ . 1. . .. C. .. .. .I n. .. r- , q q $ $ $ $ z s $ 2 : $ 3 'i-

I - - - - _ n - 2 4 4 z c * 1 -

Table 4.19(a) : Characteristics of Surfactant EfIluel~t DIIC to Arlificial Co~~tau~inal ion of Natural Soils -Uatch Mode

p~p ~ - ~

Electrical Conductivity 7 Total Solids

Table 4,19(~): Cher:\cterislics of Surfactant Effluest Due to Artilicial (:onlarnisatiao of Natural Soils - Batch Modc

I Days / pH I Alkalinity

( m d l , )

Electrical Conductivity (10' f l l c r n )

-- Nil[: 4.0 5 1 3.8 4.9 2.9 3.6 4.7 5.6 4.5 4.3 5.4 4.4 4.1 5.1 4.8 4.2 5.4 4.5 4.3 5.5 4.6 3.9 5.1 4.6 4.2 5.6 3.9 3.8 4.6 3.9 3 7 5.1 3.8 3.6 4 8

Tolal Solids I (10' mgiL) /

i : - I C O W ~ ~ . . , ~ ~ ~ ~ ~ W . Q W . Q

I , w , * m a - m m a m m m m m m m m N N W N z N N N N N b n r , n v ' 21 - - - - - - N N N N i-q----

Table 4.20(0: Charnctcristics of Surfactant Effluent due to Arlificial Contan~ination of Natural Soils ( Coutiuuous Mode - 8 IIr 1IRT - 50% Concentration )

- ~ -

600

IS 16 17 18

240544 1 236190 228571 ! 244897 234013 243811 243809 , 245238

12190 11700 12190 12180

51525 48960 50126 52224

51592 52457 52221 63240

2611 2506 2611 2609

1440 1280 1400 1440

1510 2420 1250 1750

98 91 100 97

400 200 400 400

200 200 200 200

200 200 400 400

Table 4.25(a) : Characteristics of Pharmaceutical Effluent Due to Artificial Contamination of Naturai Soils -Batch Mode

I pH Days I

.4lkalinitp (n1gIL)

NSl I N S 2 I N S 3 ! -

Electrical Conductivity

Total Solids

NSl US2 N S 3 hS1 NSZ N S 3 =

Table 4.25(a): Characteristics of Pharrnaceutieal EdTlueiit Due to Artificial Contaminatiorr of Natural Soils - Batch Mode

Electrical A1kalini@ / Conductiviw : Total Solids

hS3 NSI ' Y S 2 I \S3 -- =--

I

Table 4.25(b): Characteristics of Pharmaceutical Effluent Due lo Artificial Contamination of Natural Soils -Batch Mode

Total Dissolved Solids

(lo3 mg/L)

2i.O 2482 2836 / 7090 1 3880 1 5160 33920

4.35 / 4.30 4.30 850 850 1 850 1 4260 1 6500 / 5675

3.80 ! 3.60 4.10 850 850 5120 5560 4680 921 1 1

4.30 14.60 4.40 850 921 1 779 3600 1600 5840

3.90 14.70 4.90 708 850 1 779 1 3100 4800 4800

NS1

Ctnloride 1 Sulphate (nlg/L) 1 (mgh)

NS2 / NS3 I

NS3 NS1 NS2 / NS3 / NS1 / NS2 I

i

Table 4.25(b): Characteristics of Pharmaceutical Effluent Due to Artificial contamination of Natural Soils - Batch Mode

Days Total Dissolved Solids

Chloride

Table 4.25(c): Characteristics of PI~armaceutical Emuent Due to Artificial Contamination of Katural Soils - Batch Mode

, Total Volatile COD Nitrate S o l ~ d s

Days I (mglL) ( m g l ~ ) 1 (lo3 rng-/L) 1 I I 1 I I

NS3 NSl KS2

I

Tabie 4.25(c): Characteristics of Pharmaceutical Effluent Due to Artificial Contamination of Natural Soils - Batch Mode

~ 1 I 1 Total Volati le I

I I COD Nitrate 1 Solids I BOD I

I

Daj s I

- NSZ

Table 4.26 (a) : Characteristics of Pllarrnaceutical Effluent due to Artificial Contamiuatior~ of Natural Soils ( Continuous Mode - 8 Hr HRT - 25% Concentratior~ )

I PH Alkalinity Conductivity Days / -

NSI 4138

5 172

4526

4849

4849

4849

4526

5690

NS3 1 NSI 17.6 1.20

18.5 3.00

18.2 3.80

19.9 4.40

19.9 3.60

17.9 i 3.00

18.4 1 3A0

19.1 . 1 60

19.4 1 2100

19.2 1 2.20

19.1 2.60

20.5 1 2.40

20.6 j 2.60

20.3 1 2.60

20.1 i 2.70

20.2 i 2.60

20.4 1 2.40

Table 4.26 (b) : Characteristics of Pharmaceutical Effluent due to Artificial Contamination of Natural Soiis ( Continuous Mode - 8 HI- H R T - 25% Concentration )

Days r-lrotali~issolved I Solids

Chloride Sulphate

Table 4.26 (e) : Cllaracteristics of Pharmaceutical Effluent due to Artificial Contamination of Natural Soils ( Continuous Mode - 8 Hr HRT - 25% Concentration )

Total Volatile BOD Nitrate I

Solids !

(lo3 mg/L) : I

Table 4.26(d): Characteristics of Pharmaceutical Emuent due to Artificial Contamination o f Natural Soils ( Continuous Mode - 8 Hr HRT - Concentration )

7 I ! Electrical 1 Total Solids ~ 1 AlkaliniQ Conductivity

Days 1 1 (n1glL) / (ic+ psicm) ,

Table 4.26(e): Characteristics of Pharmaceutical Emuent due to Artificial Contamination of Natural Soils ( Continuous Mode - 8 Hr HRT - 50% Concentration )

Solids

Table 4.27 (a) : Characteristics oPPharrnaccutical Effluent due to Artificial Contamination of Natural Soils ( Continuous Mode - 16 Hr HRT - 25% Concentration )

Alkalinity 'lectrica' Total So'iids 1

Conductivity (mgfk) (10' P S I C ~ )

I

NS2 / NS3 / NSI NS2 ( NS3 / NS1 / NS? I I I 1 I

Table 4.27 (b) : Charactel-istics of Pharmaceutical Effluent due to Artificial Contamination of Natural Soils ( Continuous Mode - 16 H r HRT - 25% Concentration )

Total Dissolved Solids

Chloride Sulphate I

(mg/L) ,

Table 4.27 ( e ) : Characteristics of Pharmaceutical Effluent due to Artificial contamination of Natural Soils ( Continuous Mode - 16 Hr WRT - 25% Concentration )

I / Total Volatile BOD Nitrate 1 Solids

l Days (mglL) (nlg/L) / (lo3 m g ~ ~ ) 1

Table 4.27 (d) : Characteristics of Pharmaceutical Effluent due to Artificial Contamination of Natural Soils ( Continuous Mode - 16 Hr HRT - 50% Concentration )

' PH Days

Electrical AIhlinity ,-onducti,,iQ

(mg/L) ' (lo3 pS/crn)

Total Solids 1

Table 4.27 (e) : Characteristics of Pharmaceutical Effluent due to Artificial Contamination of Natural Soils ( Continuous Mode - 16 Hr HRT - 50% Concentration )

Total Dissolved Chloride Sulphate Solids (%/L) (mg/L)

(mg/L)

Table 4.27 (fi : Chal.acteristics of Pharmaceutical Effluent due to Artificial Contamination of Natural Soils ( Continuous Mode - 16 Hr HRT - 50% Concent~.ation j

I i

-i COI) BOD Nitrate I Solids 1

Days , (mglL) ( m g i ~ ) ( m g i ~ ) 1 (lo3 m g i ~ j I 1 I

134 e ~ s ~ w : ~ ~ ~ 1 c 1 0 - - g r" C i - r? <^ C? <" r.. r-, (.C r..

+

Fig. 4.1 (a): Variation of pH and AlkalinitJ. due to Artificial Contamination of Amino acid Effluent on Kaolinite Soil(CS1)- Batch Mode

Fig. 4.1 (b): Variation of pH and Alkalinity due to Artificial Contamination of Surfactant Effluent on Kaolinite Soil (CSI) -Batch Mode

Ti~ne I'eriod (Days)

Fig. 4.1 (c): Variation of ])I1 and Alkalinity due to Artificial Contamination of Pharmaceutical Effluent on Kaolinite Soil (CS1) - Batch Mode

2 14 2% 42 57 70 81 98 Time Period (days)

Fig. 4.2 (a): Variation of Chloride and Sulpltate due to Artificial Contamination of Aminoacid Effluent on Kaolinite Soil (CSl) - Batch Mode

14 28 42 57 70 84 98

Time Period (da).si

Fig. 4.2 (h): Variation of Chloride and Sulplkate due to Artificial Contamination of Surfactant Effluent on Kaoliiiile Soil (CS1) - Batch Mode

2 I3 28 42 5 7 70 Time Period (days)

Fig. 4.2 (c): Variation of Chloride and Sulphate due to Artificial Contsmination o f Pharmaceutical EMuent on Kaolinite Soil (CSI) - Batch Mode

Fig. 4.3 (a): Variation of Total Solids, Dissolved Solids and Eiectrical Conductivity due to Artificial Contamination of Arninoacid Effluent on Kaolinitc Soil (CS1) - Batch Mode

i ? 28 42 57 70 84 98 Time Period (days)

Fig. 1.3 (b): Variation of Total Solids, Dissolved Solids and Electrical Conductivity due to Artificial Contamination of Surfactant Efiluent on Kaolinite Soil (CSI) - Batch Mode

Fig. 4.3 (c): Variation of Total Solids, Dissolved Solids and Electrical Conductivity due to Artificial Contamination of Pharmaceutical EfIluent on Kaolinite Soil (CS - Batch Mode

Fig. 4.4 (a): Variation of COD, BOD and Total Volatile Solids due to Artificial Contamination of Arnir~oacid Effluent on Kaolinite Soil (CS1) - Batch 4lodc

Fig. 4.4 (b): Variation of COD, BOD and Total Volatile Solids due to Artificial Contamination of Surfactant Effluent on Kaolinite Soil (CS1) . Batch Mode

Fig. 4.4 (c): Variation of COD, ROD and Total Volatile due to Artificial Contamination of Pharmaceutical Emuent on Kaolinite Soil (CS1) - Batch Mode

2 18 3 5 5 3 128 133 138 143 158 168 178 196 206

Tirne Period (Days)

Fig. 4.5 (a): Variation of Chloride and Sulphate due to Artificial contamination of Aminoacid Effluent on Kaolinite Soil (CSI) - Batch and Colitinuous

Mode (8,16,48hr HRT)

2 18 35 53 70 88 126 131 136 141 154 164 174 192 202 212 'Timc Period (Days)

Fig. 4.5 (b): Variation of Chloride and Sulphate due to Artificical Contamination of Surfactant Emuent on Kaolinite Soil (CS1) -Batch and Continuous Mode (8,16,48hr HRT)

53 126 : + I 174 212 3 '

Time I'er~od (Days)

Fig. 4.5 (c): Variation of Chloride and Suiphate due to Artificial Contarnination of Pharmaccuticai Effluent on Kaolinite Soil (CSI) - Batch and Continuous Mode (8,16,48hr HRT)

I i I 2 4000 k Continuous mode

!2 -A 813r & i 6 H i 4 8 i I 1

2 53 138 168 206 Toe Period (DAYS)

Fig. 1.6 (a): Variation of COD, BOD due to Artificial Contamination of Amiuoacid Effluent on Kaolinite Soil (CS1) - Batch and Continuous Mode (8,16,48hr I i R n

I Continuous inode

3 4 Batc11 \!ode _iA SHr 1 1 6 H . g 3000 1 1 T -1.

2 53 126 131 I74 212 l'ine l'efiod (DAYS)

Fig. 4.6 (b): Variation of COI3,BOD due to Artificial Contamination of Surfactant EMuent on Kaolinite Soil (CS1) - Batch and Continuous Mode (8,16,48hr HRT)

6000 T I

5000 j

i. Continuous Y ! 3 4000 / - cl - Batch .. . . . . . ... ..

$ 3000 /

Fig. 1.6 (e): Variation of COD, BOD due to Artificial Contamination of Pharmaceutical Effluent on Kaolinite Soil (CSI) - Batch and Continuous Mode (8,16,48br HKT)

2 5 3 !26 141 174 212

'fine !'?<id (Day)

Fig. 4.7 (a) - (c): Variation of Total Volatile Solids due to Artificial Contamination of Aminoacid, Surfactant and Pharmaceutical Emuent on Kanlinite Soil (CS1) - Datch and Continuous Mode (8.16,48hr HRT)

I 500 -

- 5 d

- ~ - 300 .g .- - *

i y t zoo <

0 70 4 0 60 SO 100 'I'iiiic pcrind (days)

Fig. 4. 8(a): Variation of pIi and Alkalinity due lo Artificial Contamination of

Aminoarid EMucnt on Bentonite Soil (CSZ) - Uatcl~ Mode

0 2 0 40 60 80 100 1%2 pertod (days)

Fig. 4.8(b): Variation ofpl i and Alkalinity due to Artificial Contamination of

Surfactant Effluent on Bentonite Soil (CSZ) - Batch Mode

Tnnc period (days)

Fig. 4. 8(c): Variation of pliI and Alhlinih; due to Artificial Contamination of

Pharmaceutical Effluent on Bentonite Soil (CS2) - Batch Mode

0 20 40 60 80 100 120 Ti- period ((days)

Fig. 4. 9(a): Variation of Chloride and Sulpllate due to Artificial Contamination of

Arninoacid Efnuent on Bentonite Soil (CS2) - Batch Mode

0 20 40 GO 80 ! 00 Tim.: period (days)

Fig. 4.9(b): Variation of Chloride and Sulpbate due to Artificial Contamination of Surfactant EMuent on Bentonite Soil (CS2) - Batch Mode

0 70 40 60 80 ! 00 i 2 0 Tiine perlod (days)

Fig. 4. Vc): Variatian of Chloride and Sulphate due to Artificial Contamination of

Pharmaceutical Effluent on Bentonite Soil (CS2) - Batch Mode

Fig. 4. 10(a): Variation of Eiertrical Conductivity, Total Solids and Total Dissolved

Solids due to Artificial Contamination of Amino acid Effluent on

Bentonite Soil (CSZ) - Hatch Mode

20 40 60 80 100 120

1"m period (days)

Fig. 4. 10(b): Variation of Electrical Conductivity, Total Solids and Total Dissoll ed

Solids due to Artificial contamination of Surfactant Effluent on

Bentonite Soil (CS2) - Batch Mode

Fig. 4. 10(c): Variation of EIectrical Conductivity, Total Solids and Total Dissolved

Solids due to Artificial Contamination of Pharmaceutical Eflluent on

Bentonite Soil (CS2) - Watch Mode

0 20 40 GO 80 100 ! 20

Time period (days)

Fig. 4. l l(a): Variation o f COD, BOD and Total Volatile Solids due to Artificial

Contamination of Aminoacid Emuent on Bentonite Soit (CSZ) -

Batch Mode

Fig. 4. Il(b): Variation of COD, BOD and Totat Volatile Solids due to Artificial Contamination of Surfactant Efnuent on Bentonite Soil (CS2) - Batch Mode

0 20 40 60 80 100 1 20

'J inie period (days)

Fig. 4. Ilfc): Variation of COD, BOD and Total Volatile Solids due to Anificial Contamination of Pharmaceutical Efnuent on Bentonite Soil (CS2) Batch Mode

T ~ m c period (days!

Fig. 4. 12(a): Variation of Chloride and Sulphate due to Artificial Contamination of Aminoacid Effluent on Bentonite So!! (CSZ) - Batch Mode and Continuous Mode (S,16 hr HRT)

Fig. 4.

Wb): Variation of Chloride and Sulphate due to Artificial contamination of

Surfactant Efiluent on Bentonite SoiI (CS2) - Watch Mode and

Continuous .Mode (%,I6 hr HRT)

0 20 40 GO 80 100 120 140 160 180 200

Time period ( days)

Fig. 4. 12(c): Variation of Chloride and Sulphate due to Artificial Contamination of

Pharmaceutical Effluent o:, Bentonite Soil (CSZ) - Batch Mode and Continuous Mode

8,16 hr HRT)

Fig. 4. 13(a): Variation of COD, BOD and Total Volatile Solids due to Artificial

Contamination of Aminoacid Effluent on Bentonite Soil (CSZ) - Batch Mode and

Cantinous Mode (8,16 hr HRT)

Fig. 4. 13(b): Variation of COD, BOD and Total Volatile Solids due to Artificial

Contamination of Surfactant Effluent on Bentonite Soil (CS2) - Batch Mode and

Continuous Mode ($,I6 h r HKT)

Fig. 4. 13(c): Variation of COD. BOD and Total Volatile Solids due to Artificial

Contamination of Pharn~aceutical Cmuent on Bentonite Soil (CS2) - Batch %lode and

Continuous Mode @,I6 h r WRT)

Time Period (daqsj

Fig. 4 . I4 (a): Variation of pH and Alkalinity due to Artificial Contamination of Aminoacid Effluent on Natural Soil (NS1) - Batch Mode

Time Period (days)

Fig. 4.14(b): Variation of pH and Alkalinity due to Artificial Contamination of Aminoacid Effluent on Natural Soil (NS2) - Batch Mode

0 10 20 30 40 50 60 70 8il

Time Period (days)

Fig. 4 .14 (c): Variation of pH and Alkalinity due to Artificiai Contamination of Aminoacid Effluent on Natural Soil (NS3) - Batch Mode

h I

S ~ 2 12.!

I 0 I - - 9-i + .+ .2 I .- 2 6 :

E ! 0 I ;; 3 j 0 i .- L. L,

4 s 0 - a ' 0

0 10 20 30 40 50 60 70 80

Time I'eriod (days)

Fig. 4.15 (a): Variation of Electrical Conductivity and Total Dissolved Solids due to Artificial Contamination of Aminoacid Effluent on Natural Soil (NSl) - Batch Mode

0 10 20 30 40 50 60 70 80 Lr;

'Time Period (days)

Fig. 4 .I5 (b): Variation of Eiectrical Conductivity and Total Dissolved Solids due to Artificial Contamination of Aminoacid Effluent on Natural Soil (NS2) - Batch Mode

Time Period (days)

FIG. 4 .I5 (c): Variation of Electrical Conductivity and Total Dissolved Solids due to Artificial Contamination of Aminoacid Emuent on Natural Soil (NS3) - Batch Mode

0 10 20 30 40 50 60 70 80 Time Pedod (days)

Fig. 4.16 (a): Variation of Chloride and Sulphate due to Artificial Contamination of Arninoacid Effluent on Natural Soil (351) -Batch Mode

Fig. 4.16 (b): Variation of Chloride and Sulphate due to Artificial Contamination of Aminoacid EMuent on Natural Soil (NS2) -Batch Mode

Time Pei-iod (days)

Fig. 4 .16 (c): Variation of Chloride and Sulphate due to Artificial Contamination of Aminoacid Effluent on IVatural Soil (NS3) -Batch Modc

Time Period (Days)

Fig. 4.17 (a): Variation of COD,BOD and Nitrates due to Artificial Contamillation of Arninoacid Effluent on Natural Soil (NS1) -Batch Mode

Time Period (Days)

Fig. 4.17 (b): Variation of COD,BOD and Nitrates due to Artificial Contamination of Aminoaeid Effluent on Satural Soil (NS2) -Batch Mode

0 20 4 0 6 0 E O 'I'irnc Per iod ( d a y s )

Fig. 4.17 (c): Variation of COD,ROD and Nitrates due to Artificial Contamination of Aminoacid Effluent on Natural Soil (NS3) -Batch Mode

Time Period (days)

Fig. 4.18 (a): Variation of Total Volatile Solids and Total Solids due to Artificial Contamination of Aminoacid Effluent on Naturai Soil (NSI) -Batch Mode

0 10 20 30 40 50 60 70 80

Time Period (days)

Fig. 4 .I8 (b): Varintion of Total Volatile Solids and Total Solids due to Artificial Contamination of Aminoacid Effluent on Natural Soil (NS2) -Batch Mode

0 10 20 30 40 50 60 70 80 Time Period

Fig. 4.18 (c): Variation of Total Volatile Solids and Total Solids due to Artificial Contamination of Aminoacid Effluent on Eatural Soil (NS3) -Batch Mode

0 ?O GO 4 0 120 1 50 T:me period (days)

Fig. 4.19(a): Variation of Chloride and Sulphate due to Artificial Contamination of Aminoacid Emuent on Natural Soils (NS1)-Batch Mode and Continuous Mode (8,16 hr HRT)

I 4 L

1: I. A 9000 50000 1 Batch mode 8 h r l ! R S 16 h r HKT

0 30 60 90 120 !50 Time period (days)

Fig. 4.19(b) : Variation of Chloride and Sulphate due to Artificial Contamination of Aminoacid Effluent on Natural Soil (NSZ) - Batch Mode and Continuous Mode (8,16 hr HRT)

A 4 .Id 7 , - 7 *! 9000 50000 -! Batch mode t t I R T

16 hrT1RTi

0 30 GO 90 120 1 0 Time period (day$)

Fig. 4.19(c) : Variation of Chloride and Sulphate due to Artificial Contamination of Aminoacid Effluent on Natural Soil (NS3) - Batch Mode and Continuous Mode (8,16 hr HRT)

0 .; n 60 90 120 150 .lit!ie pe: ~ o d (d3)s)

Fig. J.?O(n) : \'ariation of Total Solids, Total Volatile Solids arltf COD due to Artificial Cor~tarnirlatior~ of Arninoacid Effluent on Natural Soil (NSI) - I3atch Mode and Contirli~ous Rlode (8, 15 hr HIIT)

Fig. 4.20(b) : Var~at ion of ?'otaI Solids, Total Volatile Solids and COD due to Artificial Conlami~ration af Amrnoacid Effluent on Sa tu ra l Soil (NSZ) - Batch Mode and Continuous Mode ($,I6 h r HIIT)

0 30 GO 90 120 150 Time period (days)

Fig. 4.20(c) : Variation of Total Solids, Total Volatile Solids and COD due to Artificial Contamination of Aminoacid Effluent on Natural Soil (NS3) - Batch Mode and Continuous Mode (8,16 hr HRT)

Fig. 4 .21 (a): Variation of pH anti -\lk;:linity due to ,Artificial Contan?i~i;itii;r! ii:

Surf:.~ctarit l7ffloerit ~ I I I Natur;tl Soil (SSI) - Ratcli I o d c

Fig. 4 .21 (b): Variation of pll and Alkalinity due to Artilicial Cont;anainelil~~: of Surfactant Efflucr~t on Saturai Soil (NSZ) - Batch t11)ilc

Fig. 4 .21 (c): Variation of pH allti Alkalinity due to Artificial Contan~inatio~i of Surfactant Emuent on Natural Soil (NS3) - Batch Mode

Fig. 4 .22 (a): Variation ofElectrica1 Conductivity due to Artificial Coutamination of Surfactant Emuerit on Natural Soil (NSI) - Batch Mode

Fig. 4 .22 (b): Variation of Electrical Conductivity duc to Artificial Contamination of Surfactsnt Effluent on Natural Soil (NS2) - Batch Mode

- 0 - 1 2

I A b 1

-E/ i

'l 'in~e period (days)

- -, 20 - .-

Fig. 4.22 (c): Variation of Electrical Conductivity due to Artificial Contamination of Surfactsnt Emucnt on Natural Soil (NS3) -Batch Mode

i t / i i 1

> .- + s - 2

y'\ I i I

!

B 10 ; - i I I 2 4 I 0 1

I ; ; ! -

0 1

0 30 60 99 I ' i~ne :,cnod (days)

1 E.O? i ! t - O i l

0 7 0 60 90

.ii7. , t L . ~ x r t o d (days)

Fig. 4.23 (a): Variation of Toral Solids and Total Dissolved Solids due to Artificial Contamination of Surfactant Effluent on Natural Soil (NS1) -Batch i\.lotLe

Fig. 4.23 (b): Variation of Total Solids and Total Dissolbed Solids due to Artificial Contamination of Surfactant Effluent on Natural Soil (NS2) - Batch Mode

Fig. 4.23 (c): Variation of Total Solids and Total Dissolved Solids due to Artificial Contan~inafion of Surfactant Effluent on Katural Soil (YS3) - Batch Mode

0 30 6 0 90

'!'i!nc period (days)

Fig. 4.24 (a): Variation of Nitrate, Chloritlr and Sulphate due to Artificial Contamination of Surfactant Effluent on Natural Soil (NSl) - Batch Mode

Fig. 4 .24 (b): Variation of Yitrate. Chloride and Sulphatc due to Artific~al Contamination of Surfactant Effluent on Natural Soil (NS2) - Batch Mode

Fig. 4.24 (c): Variation o f Nitrate, Chloride and Sulpl~atc due to Artificial Contamination o f Surfactant Effluent on Natural Soil (NS3) - Batcl~ Mode

Time pencd (days)

Fig. 4 25 (a): Variation of COD and BOD due to Artificial Contamination of Surfactant Effluent on Naturai Soil (h'S1) - Batch Mode

T ime pcriod (days)

Fig. 4 .25 (b): Variation of COD and BOD due to Artificial Contamination of Surfactant Effluent on Natural Soil (NSZ) - Batch Mode

Fig. 4 .25 (c): Variation of COD and BOD due to Arlificial Contamination of Surfactant Emuent on Natural Soil (NS3) - Batch Mode

0 30 60 40 Time period (days)

j0000

22-0G

3 h E

15000 '

7500

0

i .E- 07

i 1.E105

n

Fig. 4.26 (a): Variation of Total Volatile Solids due to Artificial Contamination of Surfactant Efiluent on Natural Soil (NSl) - Batch Mode

0 3 0 60 90

Time pel iod (days)

rbl 0 0 I

i I

I .E-iO3 I

0 3 0 60 90

Tiine period (days)

Fig. 4 .26 (b): Variation of Total Volatile Solids due lo Artificial Contamination of Surfactant Effluent on Saturai Soil (NS2) - Batch Mode

0 3 0 60 90

Tiine period (days)

Fig. 4 .26 (c): Variation of Total Volatile Solids due to Artificial Contamination of Surfactant Effluent on Natural Soil (NS3) - Batch Mode

0 3 5 70 I05 140 175

Time I'eriod (days)

Fig. 4.27(a) Variation o f Cl~ lor idc and Sulphate due to Artificial Contamination of Surfactant Eflluent on natural Soil (NS1) - Batch Mode nnd Continuous Mode ( & I 6 hr ITRT)

1 I I ; : ~ I'ciiod (da! a)

1 . i ~ . 1.27(1>) \ arial ion o f (:hloride and Sulphatc d u e to Artificinl Contnnlinntinrr o r Siirfnrtant I<fflurnt on n a t u r a l Soil (.VSZ) - Batch h l o d c and Continuous \ l o d e (8. 16 h r IIII'l)

0 50 100 150 'Tune Pe:iod (days)

Fig. 4 .27 (c): Variation of Cl~loride and Sulphate due lo Artificial Contamination of Surfactant Effluent on Natural Soil (XS3) - Batch Mode and Continuous Mocie (8, 16 11r HKT)

(50% 8: 25%) (504' & 25%

0 $0 60 90 120 150 !80

Time Period (days)

Fig 4.28 (a): Variation of Total Solids, Volatile Solids and COX) due to Artificial Contamination of Surfactant Emuent on Natural Soil (NSI) - Batch Motle and Continuous Mode (8.16 hr HRT)

Contaniination of Surfactznt Efilucnl on Natural Soil (NSZ) -Batch Mode and Continuous Mode (8,16 hr IHRT

Fig. 1 .28 (c): Variation of Total Solids, Volatile Solids and COD due to Artificial Contamination of Surfactant Effluent o n Natural Soil (h'S3) - Batch Mode and Continuous Mode (8,16 hr HRT)

0 I0 20 30 40 50 6 0 70

Ti111e period (days)

Fig. 3. 29 (a): Variation of pK and alkalinity due to Artificial Contamination of Pharmaceutical Effluent on Natural Soil (iYS1) - Batch >lotte

0 10 20 30 40 50 60 70

'l'i~ne period (days)

Fig. 4. 29 (b): Variation of pII and alkalinity d% to Artificial Contamination o f Pharmaceutical Effluent on Natural Soil (NS2)-Batch Mode

Fin,. 4. 20 ( c ) : Variation of pI-1 and alkalinit? dur t o .4rtificial Contamination of Pl~armaccutical Effluent on Natural Soil (NS3)

0 I 0 20 -30 30 50 60 70

Tim* period (days)

Fig. 4. 30 (a): Variation of Electrical Conductivity due to Artificial Contamination of I'harmaccutical Effluent on Naturi~i Soil (NSI

0 10 20 30 40 50 60 70 'Erne period (days)

Fig. 4.30 (b): Variation of Electrical Conductivity due to Artificial Contamination of I'11arrnaceuticaI Effluent on Satural Soil (NS2)- Batch Mode

i,() ---- I

- I

I - 1 ; 1 ? . I .- I .? 1 : I $ I :

2 : =, . ! u - .c ! 9 j ! .- , - , i, I 5, 1) h"-- I - a

0 10 20 30 40 50 60 70 'Tirne period (days)

Fig. 4.30 (c): Variation of Electrical Conductivity due to Artifici;iI Contamination of harmaccutical EMuent on h'aturiii Soil (NS3)- Batch Mode

i ! .E-t?O? ! .I<-03

0 10 20 30 40 50 60 70

Tinie period (days)

Fig. 4. 31 (a): Variation of Total Solids and Total Dissolved Solids due to Artificial Contamination of Pharmaceutical Effluent on Natural Soil ( M I ) - Batch Mode

I - 1 4 I i -

9100 i ' j \ 94

I ' - E

1 I

100 .! 1 ' 1800

0 10 20 30 40 50 60 70 Time period (days)

Fig. 4.31 (b): Variation ofTota1 Solids and Total Dissolved Solicfs due to Artificial Contamination of Pharmaceutical Effluent on Natural Soil (NS2) -Batch Mode

0 10 20 30 40 50 GO 70

'Tinie period (days)

Fig. 4. 31 (c): Variation of Total Solids and Total Dissolved Solids due to Artificial Contaminatiori of Pliarmaceutical Effluent on Satural Soil (NS3) -Batch Mode

50 t I I 200

0 I0 70 30 40 50 60 70

Time period (days)

Fig. 4.32 (a): Variation of Nitrite, Chloride and Sulphate due to Artificial Contamination of Pharmaceulieaf Effluent on Natural Soil (NS1) -Batch Mode

0 10 20 30 40 50 60 70 Time period (days)

Fig. 4.32 (b): Variation of Nitrite, Chloride anti Sulphate due to Artificial Contamination of Pharmaceuticai Efflucnt on Natural Soil (NSZ) -Batc!l Mode

0 !O 20 30 40 50 60 70

l'ilne period (days)

Fig. 4. 32 (c): Variation of Nitrite, Chloride and Sulp l~a tc due to Artificial Contaminntion of Pharmaceutical Effluent on Natural Soil (KS3i -Batch Mode

0 10 20 30 10 50 5? 70 Time I'el iod ida>s)

Fig. 4. 33 (a): Variation of COlf and BOD due to r t i f i c ia l Contamination of Pharniaceutical Effluent on Yatu~al Soil (NSI) -Batch Rlode

0 1 2 3 1 5 6 7 Time Period idavs)

Fig. 4.33 (b): Variation of COD and BOD due to Artificial Contamination of Pharmaceutical Effluent on Natural Soil (NS2) -Batch Mode

100000 I- 20000

0 10 20 30 40 SO 60 40 Time Period (days)

Fig. 4. 33 (c):Variation of COD and BOD due to Artificial Contamination of Pharmaceutical Effluent on Zatural Soil (NS3) -Batch Mode

0 10 20 30 40 50 60 70 Time period (days)

Fig. 4.34 (a):Variation o f Total Volatile Solids due to Artificial Contamination of Pharmaceutical Effluent on Natural Soil (NSI) -Batch Mode

Fig. 4. 34 (b):Variation of Total Volatile Solids due to Artificial Contamination of Pharmaceutical Effluent on Natural Soil (NS2) -Batch Mode

0 10 20 30 40 50 60 70 Time period (days)

Fig. 4.34 (c):Variation of Total Volatile Solids due to Artificial Contamination of Pharmaceutical Effluent on Natural Soil (NS3) -Batch Mode

0 20 40 60 80 100 120 140 Time period (days)

Fig. 4. 35 (a):Variation of Chloride and Sulphatc due to Artificial Contamination of Pharmaceutical Effluent on Natural Soil (NS1) -Batch and Continuous YIode(8, l6hr HRT)

- -- --- - .. - - 12000 Batch inode ,Iq X hr 1iRT 1 16 hr HRT

j 10000 I 7

il / I

0 20 40 60 80 100 i20 140 Time period (days)

Fig. 3.35 (b):Variation of Chloride and Sulphate due to Artificiai Contamination of Pharmaceutical Effluent on Natural Soil (NSZ) -Batch and Continuous Mode($, l 6 h r IIKT)

42000 Batch niode .I, 8 llr I

10000 '

- '.

CO yT;

8 , 0 + m

;21000 5 - >

LC

130011

0 20 40 60 SO 100 i20 140 l'inic period (days)

Fig. 4.35 (c):Variation of Chloride and Sulphate due to Artificial Contamination of Pl~arrnaceutical Effluent on Natural Soil (NS3) -Batch and Continuous Mode(& 16hr HRT)

0 20 40 GO 80 100 120 140 Time period (days)

Fig. 4.36 (a):Variation of Total Solids, Total Volatile Solids and C011 due to Artificial Contamination of Pharmaceutical Effluent on Katural Soil (NS1) -Batch and Continuous iClode(8, 16hr HRI')

0 20 40 60 80 100 120 110 Time period (days)

Fig. 4.36 (b):Variation of Total Solids, Total Volatile Solids and COD d u e to Artificial Contamination of Pharniaceutical Effluent on Natural Soil (KS2) -Uatclt and Cootinuous Rlode(8. 16hr HRT)

0 20 40 60 80 100 120 :40 'rime period (days)

Fig. 4.36 (c):Vnrintion ofTotnl Solids. Total Volatilc Solids nnd COD due to Artilicial Contnminrtion of Pharmnceutic~i Emuent on Xatural Soil (NS3) -Batch and

Continuous Modc(8,Ibhr IIKT)

- - < m c I . !

Fig 4.44 UCC Vs Timc duo to Artificial Contarninatlon of Amino Effluont on Natural Soils (NSi, NS2 8 NS3) Fig 4.45 UCC Vs Tlin? duo to Arlif~clal contamination of Surfactant

Effluent on Natural Soils (NSI . NSZ 8 NS3)

I

01- .. . . - - 1

- - 1

0 20 40 so no l o o 120 140 160

iirna (Days) Fig 4.46 UCC Vs rlrno clue to ARlficial Cnrltalninatlon of Pharrrraccuticel

Effluont on Natural So115 (NS1, NSZ 8 NS3)

Soil

t Chc~llical Reactlon

Chemical T ra~~s fo r~ i a t i on

Soil Coiuinn Chemical transport

Soil

Bio!ogical .4 Transformation

- - , Chernical Pet~neation Stage.1

@L Soil Transformed

Organic ' ~ a y e r Con\ ersion

Soil

Fig. 4.47 Visualization of Soil - Pollutant interaction (Phpsio-chemical

hehaviour)

Solid :-etentio~i fact01

Fig. 4.48 Simulated Concentration Factors For Chiorides and Sulphate due to Artificial contamination of Amino acid on all Natural Soils

k I / y c n n I

' 1 /I/ / TVS 2 I

Solid retention factor

Fig. 4.49 Simulated Concentration Factors for COD, TVS due to Artificial Contamination of Amino acid Effluent on all Natural Soils

Note: SS - S3 - Concentration of sulphate for NSS to NS3 C1 - C3 - Concentration of Chloride for NS1 to NS3 Subscripts used (ie., COD1 - COD 3 and TVSl - TVS3) refer to Natural Soil types

A

A A

. . . . . . . . m ..... ... . . . . , .

- I 6

1 Experimeotai (Sulphaq)

I ----Mode (Chloride) l l - - - - - - Model (Sulphate) 1 ; Exper~mental (Chioride) 1:

Fig. 4.50 Comparison of Concentration Profile of Chloride and Sulptlate (Enpt. Vs Model ) for Amino acid Effluent

O Experirnentai (TVS) 1 Model (COD)

A Exper~mental (COD I- / - - - - Model (TVS)

Solid retention factor

Fig. 4.51 Comparison of Concentration Profile of COD, TVS (Expt. Vs Model ) for Atnino acid Effluent

Fig. 4.52 Simulated Concentration Factors For Chlorides and Suiphatr due to Artificial Contamination of Pharmaceutical Eftluent on all Vatural Soils

Solid retention factor

Fig. 4.53 Simulated Concentration Factors for COD, TVS due to Artificial Contamination of Pharmaceutical Effluent on ail Natural Soils

Mcdel (Sulphate)

A Experimental (Chloride)

Solid rerention factor

Fig. 4.54 Comparison of Concentration Profile of Chjoride and Sulphate (Expr. Vs Model ) for Pharmaceutical Effluent

Solid retention factor Fig. 4.55 Comparison of Concentration Profile of COD, TVS (Expt. Vs hlodei ) for

Pharmaceutical Effluent