PhD-Migration of Leachate Solutin Through Clay Soil

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MIGRATJON OF LEACHATE SOLUT,ION THROUGH CLAY SOIL
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by
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MOSTAF A ABDEL JlARITH
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A Thesis submitted to the Facutty of Graduate Studies
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and Research in partial fulfi.llmen\ 0: the, requirements '
for th.e degree of Doct~r of Philosophy
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Department of Civil Engineering and Applied, Mech'llic:;s
McGi11, University
Montreal, Quebec, Canada

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1987 ,
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MIGRATION OF ...LEACHATE SOlUTION THROUGH CLAY SOIL
, by
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MOST~ACDFJ. WARl:
ABSTRACT
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The problem of domeseic solid was~es buried in landfill sites ls
viewed from the aspect of i~achate contamination and migratio? in' the
sub~trate . Generally, this occurs through the penetration of the
contaminant into the liner mater~al. In,this study, the use of na~ural
clay ~barriers as, an expedient ~co~omJ.c 'Uning material has led, to t~e
assessment of the efficiency of the liner and the resultant migration"of

the ~leachat! -
To evalua~e the potential of the use of natural cray as a barrieF

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~ to contaïn the domestic solid waste, an actual wast~ cont~inment site at
Lachenaie (35 km east of Montreal) was studied. Th~ , various chemical

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constituents Qf the landfili

, leachate
. were determined 'from samples taken
from bas ins which were designe;d to collect the leachate fr~'m the
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landfill .
.rn companion laboratory tests, thesé leachate samples wer.e
permeated through laboratory columns that9_ contained the natural clay

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compacted at the optimum water content. 'The col~s were constructed 50

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as to permit simulation pf slow, saturated, anaerob~c flow of leachate
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through the clay lining surrounding the landfill and leachate basins.
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Leachates were permeated through the soil columns 'for periods of four to
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five months, during which effluents were collected per,iodically and
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analyzed for different chemical species and physical parameters. These
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c f. chemical analysis meaqured ?hanges in the concentration of:
(Na; K, Ca, and Mg), (b) anions (Cl, Heo, , and CO,),
(a) cations 1
(c) total!
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~c me~als
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c.,bon, (TOC), and (d) he.vy (Fe, Zn, Pb, and Cu), The; .\
J'>3: physical parameters meas~!red inc;:lud~d: (~~ pH, and (b) specifi
condue tivi ty .
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Subsequent to the leaching tests, the column contents were cut "nto
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six sections and ,analyzed ta de termine the distribution profiles f(thb.-, '4'
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,a4orbed .nd retained contaminants at v.rious Ume 'durations, /

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'ft Predictiohs, using a dispersion-convection mOGel for Icentration,
profile development for either adsorbed or retained co~t~inants, were
.- compared'vith the e~~e_ent~llY determin~d

columns and lan~fill laboratory model).
Another se: of experiments vas al~o

profiles
conducte
1'(ï~h
to evaluaté the
in 'leaching
.,
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~~fect . of some, org~.~ic f\lUidS on the geoteChlcal properties of
different clay soils (natural clay and two referenc clay so~ls: illite
and kaolinite) .
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The result~ from this study have demonstrated that the natural clay
.
,'. soil cau be llsed to adequately contain the different contaminant species
usually present in the leachate solutions. Furthermore, the data
suggest.ed that under favourable soil cpnditions, lJndfill leachates
containing low levels of trace metals will not pose a substantial
contamination threat to the subsurface environment, provided that a
propsF thickness of barrier is used. /

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MIGRATION DEûL:txIVIATS DANS Dm SOLS D'ARGILE •
,, par
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, MOSTAFA ABDEL WARITH
Le problème de déc:het$ solides' domestiques, enterrés dans des 81 tes

d'enfoui,!3sement est-étudié du point" de vue de la contamïnation et de la
migration des lixiviats dans les argiles. En général, celà" se décrit par
•
une pénétration du
- contaminant daps le matériel constituant.. )a membrane\
protectriée. L'utilisation de barrières d'~gile comme étant des matériaux

économiques et convénients; iénére des questions sur l' éff;icaci té de ces
argiles comme matériel de recouv.rement et sur' la migration des lixivla~s
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dans l'arcEile.
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Danè le but d' é,?aluer le potentiel et la nature de l' argil~ utilisé

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comme membrane pour contenit des déchets solides domestiques, un site

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d'ehfouissement situé à Lachenaie (35 km de Montréal) fut étudié. Les
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différents consti tuents chimiques du. lixiviat provenant de, ce site ont
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été déterminés à partir q'échantillons pris dans +es bassins col~ecteurs.
Des tests de laooratoire ·parallèles ont été menés sur la percolation

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de lixi viats provenant -de Lachenaie à travers des colonnes d'argile
naturelles, compactées à leur tenêur en eau optimale. Les cellules de

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lessi vage ont été déssinées pour fermettre la simulation d'une
percolation lente et saturée d'un lixiviat anaerobe à travers une

épaisseur d'argile de la membrane entourant le si te d'enfouissement et
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les bassins collecteurs. Les llxiviats ont percolé à travers les colonnes
d "argile perdant des périodes variant de 4 à 5 mois, durée pendant
laquelle l'effluent a été collècté et amlysé pé~ement pour son

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contenu en espèces chimiques et ses paramètres physiques. LI analyse

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chimique visait à étudier les variations de condentration des: a)
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~ations (Na, K, Ca et Mg), b) anions' (Cl, HC0
et C0 ) , c) carb9ne
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organique total (car) et deS' métaux lourds (Fe, Zn, Pb et Cu). 'Les
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paramètres physiques analysés ,étaient le pH et la ~o~tuctiVité Spéc~fiqUe.
, du lixi viat .
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Apr:es
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pé rl\.JUe Il t'10p,
percola les colonnefj! dl argile ont. été
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'~t r~-'3ées p~ur

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sectionnées en 6 déterminer les profils de ~istri bution
Ir '\,
des contaminants adsorbés et" retenus à. des tlps ~ percol~tian
spécifiqL1:es.
Des prédictions faites à partir dl un modèle de dispersion-
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. cOJ1v~ctibn,'" furent utilisées pour développer les profils de concen-
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t!tions des contaminants adsorbés ou retenus. Ces' prédictjons furent
( ensuite comparées aux profils dérivés des
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résultats
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experimentaux
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(provenant des colonnes de lixiviation et des modèles de lâboratoire) •
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DI autres expériences furent également menées pour évaltler 11 influence
de quelques fluLdes organiques sur. les propriétés géotechnique~ de

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plUsieurs, sols d' argile (~rgiles naturelles, et deux argiles de
référence: illite et kaolin).
Les résultats de cette étudè ont démontrés que les sols dl argile
naturelles peuvent être lltilîsés pour contenir adéquatement les espèces
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. différentes de contaminants généralement c,orttenues dans les lixi viats. En
plus, les r.ésultats ont suggéré que sous des condi ti ons favorables, des
lixiviats contenant des faibles concentrations de métaux ne poseront pas
de problèmes importants de contamination des env~.

r nnements souterrains,
pourvu qu'une épaisseur d'argile suffisante soit dispon'ble.
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o , ACKNOWLEDGEMENTS
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The authbr wishes to express his sincere ~ppreciadon and "gratitude '
to:
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- Professor R: N. Yong, William Scott Professor of Ci:vil Engineering and-
" Applied Mechanies, and Dirèctor of the Geoteehnical Rese'areh c:enter at
M6G!ll University. for his invaluable guidance' an'd continued

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e~couragement throughout this study;
...
Dr. P. Boonsinsuk, for his hèlpful advice and discussions;
- Mr. Gerald Girouard: Environment Canada, Dept. of Emergeney and Waste,
for his suppor~ and help" in providi-ng the access", to the' different
làndfflls 'in Montreal'area and supplying the useful information;

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• Dr,'C. S. Kim
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~or helpful diseussion~;
Mr: F. " Caporusc id, Mp§'. P. •

Lytle and their labor'atory staff for
their technical assistapce;

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- Quebee Department of Education for supportîng this study;
- . Speci..al apP7'eèiation is extended to my father a~d mot:her for their
encouragement and und~rstanding,
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TABLE OF CONTENTS
ABSTRACT
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ACKNOYLEDGEMENTS
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CHAPTER 1 INTRODUCTION
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1.1 Statement of the Prob~em
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l. 2 Scope anq. Obj ,ectivé'S'I of,

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1.3 Organizat.i0Il of the Thesis 5
CHAPTER 2 MATERIAL SAND., METHODS
f 2.1 General 8
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2.4 Soil -Properties and Characterist1cs 10

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2.3- Chemical Analysis oft the Leachate Solution 21
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2.4 Physico-C~emical Properties of Organic:Leachate
F1uids • 21
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( 2.5 Laboratory Investigation of Contaminant
Migration. .;
2.5.1 Soil preparation

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2.,5.2 Test Procedure • 26
2.5.3 The Experimental Series Invest~gated 29
2':'6 Labor:atory Investigation of Change in Hydraùlic 04.

Condûativity and Strength -of Clay Soils 29
2.7 Laboratory Landfill Model ,33

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2.8 Field Study
.' 34
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CHAfTER 3 EXPERIMENTAL RESUL TS AND ANALYSES
3.1 -General
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3.2 Migration of Diff~rent Contaminant ~pecies 41

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3 . 2 . 1 Heavy Me taIs 41
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c ' 3.2 . 2 Cations 44
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3 . 2 . 3 Ani,ons 55
() 3.2.4 Organic Substances (TOC)' 61
3.3 Analyses and Discussion on the Contaminant

Spe~ies Migration • 66
3.3.1 Attenuation of Heavy Metals 66

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3.3.2. Attenuation of Cations 69
3.3.2.1 Water Content and Attenuation Number 70 .<
3.3.2.2 Mass Balance and the Relation between

Eluted and Reta~ned Cations 71
3.3.2.3 The Relation between Soluble and Adsorbed

• Cations 78
3.3.2.4 Desorption of Cation Species 87
3.3.2.5 Calculation of Selectivity Coefficients 92
3.3.2.6 Mathematical Ana1ysis of

Cation Migration 93
3.3.3 Migration of Ch10ride Ions, 101

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3.3. ~ Comparison between Cati.on and Anion
Behaviour along the Migration Profiles 104
3'.3.5 Migration of Organic Substances (TOC) 106
3.3.5.1 Mathematical Analysis of Chloride and

Organic Migration 109
3.4. Summary 115
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. CHAPT ER 4 COMPARISONS AND PREDICTIONS OF CONTAMINANT
MIGRATION THROUGH"CLAY SOILS
4.1 General 117

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4.2 Formulation of the Mathematical Mode1 119
4.2 . 1 Boundary and Inî tial CO,ndi tions 123

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4.3 Comparisons and Predictions of Contaminant Species
Migrating through Clay Soil Columns 124
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4.4 Compa~isons bet~een Experimental and PredicCed
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.~~ Results in a Landfill Model 136
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4.4.1 Pore F1uid Analysis 136
4.4.2 Predictions and Compar,isons 137
4.5 Summary 141
CHAPTER 5 FIELD INVESTIGATION (CASE STUDY)
5.1 General
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5.2 Description of the Study Area
5.3 Variation in Leachate Quality 144
5.3.1 Changes in pH Value 144 0
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5.3.2 Changes in Specifie Conductivi ty Value 146
5.3.3 Chan~es in Heavy Metal co~entrations 146
5.3,.4 Changes in Alka1i and A1kaline Earth

Metal Concentrations 148
5 . 3 . 5 Change in Chloride Çlnd Organics

Concentrations 151
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5.3.6 Other Cont;,aminant Species 154-
5.4 Summary 155

5.5 Prediction of Contaminant Migration
in. the Field 156
~.5.1 Average Dispersion Coefficient 156

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5.5.2 Predic'êion with Variable Dispersion

Values 161
5.5.3 Pre~id?ed Moving Front of Contaminant

Species 1b2
CHAPTER 6 SUMMARY, CONCtUDING REMARKS', AND SUGGESTIONS

FOR FURTHER STUDIES .rt..
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6.1 Summc3J:Y and Conc1uding Remarks 167 0
6.2 Suggestions ;or Further Stuàies 170
( REFERENCES 171
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ÀPPENDIK A: CLAY SOIL 'PROPERTIES AND CO~INÀNT INTERACTIONS
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A.l Gen~ral 1.83
A.2 Cray Soil ~roperties 184
A. 2.1 Chemistry and Mineralogy of Clay 185
A.2.2 Soil Attenuation Properties 189-

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A.3 permeability 'Of Compacted Clay 192
A.4 The Effect of Waste L~quids on Clay Soils 198

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~A.4.4. The Effects of Exchangeable Cations on the

Permeability of Clay 198
A.4.2 The Effects of Organics on the Permeal?ility

of Clay Soils 201
A.4.3 The Effect of Contaminant Mi'gration on

Other Geotechnieal Properties 207
.A:-4.4 Vo~ume Changes 209

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~.4.4.1 Soil Gharacteristics Affecting Swelling
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and Shrinking 209
A.4.5 Dissolution of Clay 212
A.4.6 Piping 213
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APP~IX B: PHYSIGO-CHEMIGAL AND ANALYTICAL CONCEPT OF LEACHATE
MIGRATH>N
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B.l General 216
B.2 Hydrodynamie Dispersion 217
B•. 3 Reaction Proeesses 224 ;
B.4 Adsorption 226·
B.5 Ion Exchange 232
B.6 Microbial Degl:adation of Organic\ Waste 235

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B.6 . l Anaerobie Degradation 236 \
B. 6 2 Microbial Mass Transport in Soil M<edia

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B.6.3 Biodegradation Kinetics 237
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( a.7 Precipl tation 238
APPENDIX C: ONE DIMENSIONAL MATHEMATICAL MODELS FOR

PREDICTING ~CTIONS AND MIGRATION OF
LEACHATE THROUGH CLAY SOILS
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C.1" General 241
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Cl
C.2 The Governing Equation of the Convective-
Dispe~sive Transport Reactive Solution 242
c.3 Mathematical Models that Assume Ghemlcal

Equilibrium 244 1
C.3.1 Retardation Functions 245
C.3.2 Transport Models that Assume Local

Equilibrium Reactions (Instantaneous) 247
C.,k Mathemat'ical Models that Assume Chemical

Non-Equilibrium Reactions 249
C.4.. l Mathematical- Models Assuming Irreversible

Kinetid Reactions 250
l C.4.2 Sorption Model~ Assuming both Reversible

and Irreversible Kinetic Reactions 251
C.5 Mathematical Models Assuming Biodegradation

Reactions 252
APP~IX D: EXPERIMENTAL RESULTS CONCERNING MIGRATION OF'

CONTAMINANTS THROUGH CLAY SOILS "
SECTION l Experimental Results 255
,D.l Mass Balance Calculations of Different Ions

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Permeated through Clay Columns 1 282
D.l.1 Definitio~s 282
D.l.2 Sample of Calc~iattons 282
SECTION 2 : Comput~r Programs 284
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0, APPENDIX E: THE, EFFJWT OF THE MIGRATION OF' ORGANIC CONTAMINANTS
., ON THE GEOTEC~ICAL PROPERTIES OF DIFFERENT CLAY SOILS
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E.1 Gener~l 295
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E.2 Variation of the Hydrau1ic Conductivity
of Clay SoUs 298
E.2.1 The Effect of the Different Forces

between the Clay Particl,es on the
Hydrau1ic Conductivity 306
&.2.2 The Effect of the'Organic Solutions Intrusion /
on the ~ydrau1ic Conductivity Behàvio~r 318
E.2.3 The Effect of Organic Adsorption on the

Hydraulic Conductivity
1 .323
E.2.4 The Effect'of the Dielectric Constant on the
Hydraulic Conductivity 329
E. 2.5 Summary 33!

1 E.3 Change ih the Strength of ~lay Soi1s pèrmeated
) with Organic F1uids 332
\ E.3.1 General 332
E.3.2 Shear Strength,Results 332
E.4 Summary 337
APPEND]x F: ,GEN~ CONSIDERATIONS 338
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LIST OF FIGURES
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Figure {No.) Contents Page (No).
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1.1 Schematic Representation
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of the Present Study 6
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2.1 General Landfil1 Scheme used in Actual Landfill Site 9
2.2 Par~icle Size Analysès for Different SQils." 12

,. 2. 3a - X-Ray Diffra tion Ana1ysis for Natural Soil 15
1
2.3b X-Ray Diffraction Analysis for Illite Soil 16
2.3c X-Ray Diffràction Analysis for Kaolinite Soil 17

2.4a \ Dry Unit Weight-Water Content Relationship for
Natural and Illite Soils 19
2.4b Dry Unit Weight-Water Conte~.Relationship for
Kaolini te Soil 20
2.5 Schema tic Represent~tion of Laboratory Leaching

Cel} Used in this Study 25
è 2.6
2.7
Test Scheme Used in the Study
Test Spheme Used in the Organic Permeation St~dy

27
31
2.8 Schematic Representation of the ,Landfill Moâel
2.9 General Layout of the Landfill Area 37
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3.1 Relative Cdncentrations of Heavy Metals (studies) in ! // ;'
Solution Collected after teaching- as a Result of
Pore Volume Passage of Leachate \ 42 !
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~ Heavy Metal Migration Profiles aiter the Displacement
of 5 Pore Volumes 43
3.3 Relationship Between Fe Ion Concentration and

Different Types of Clay: Soils
3.4 ~nd-CI-Breakthrough Curves 46

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3.5- Relative Concentration of Different Cations in
Solution Collected after Lèaching- as a Result
'~o:É Pore Volume Passage of Leachate 48
c- 3.;6a Cation Migration Profiles in Natural Soil 49
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o 3.6b Cation Migration Profiles in Illite Soil"

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50
3.6e Cation Migration Profiles in Kaolinite Soil 51
3.7 Relative Concentrations of Diffe~ent Cations in

Solution Collect~d after Leaching- as a Result
of Pore Volume Passage of Leachate 52
3.8a Na Concentration Profile Distribution in NaturaI

Soil Colwnns , 53
3.8b Ca Concentration Profile Distribution in Natural
Soil Colwnns 54
3.9' cl Relative Conc~ntrations in Solution Coilected

after Leaching- as a Result of Pore Volume Passage
of Leachate 56
3.10 Cl Profile Distribut10ns in Naturai SQil Columns 58
3.11 HC0 3 Migration Profiles after 3 and 5 Pore Volume ," ..... JI ,
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Displacement 60
3.12 Ratios of Chioride to Bicarbonate along the Natural

Clay Co~wnn Depth 62
3.13 TOC Relative Concentrations in Solution Col1ected

after Leaching- as a Result of Por~ Volume Passage
of Leachate 63
3.~4 TOC Profile Distributions in Natural Soil Columns 65 ~
3.15 'Schematic Flow-Sheet of Mass Balance Calculations 75 / ' -w
3,16 Schematic Diagram of a. Typical Migration Profile 77
3.17 RelationsQip('between Soluble and Adsorbed Ca Ions

Series II (Natural Soil) 82
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Relationship between Soluble and-Adsorbed Mg Ions

Series II, (natural Soil) _ #" 83
,r-\ 3.19 Retationship between Soluble and Adsorbed K Ions

3.20 Relationship between Soluble and Adsorbed C~ 10ns-

(lUite Soil) 88
3.21 Relationship between Soluble and Adsorbed Ca Ions

(Kaolinitè Soil) 89
o 3.22 Relationship between Soluble and Desorbed Na Ions

Series III (Natural.Soil) 91
XIV
c 3.23 Schematic Diagram Illustrat~s the Typical Behaviour

of the A, B, and CC Constants ~ 96
3.24 Comparison of Predicted and Measured Mg Ion Profiles
in Series III 99
3.25 Comparison of Predicted and Measured K Ion Profiles
in Series III . 100
3.26 Typical Nomograpb to Determine the Ratio between A,

B, and CC for Natural Soi1 102
3.27 Ratios of,," Cl ta ather Species along the Migration

Profiles after 1 and 5 Pore Volumes' 103
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3.28a Equivalence Ratios of Major Cations ta the Total ,1
Cation Equivalents (E Cations) 105

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3.28b Equivalence Ratios of Cl ,and HC03 ta the Total
Cation Equivalents (E Cations) 107
3.29a Comparison of Predicted and Measured Cl Ion Profiles 110
3.29b Comparison of Predict~d and Measured TOC Ion Profiles 111

3.30 Comparison BeQween COD Removal Data (Soypak, 1979)
( and ~he pr~ic~ed Value from Equation (3.7) 113
3.31 Comparison Between Chloride Migration Prpfiles
(Crooks and Quigley, 1984) and the Predicted
.Profiles from Equation (3.7) • 114
4.1 Schematic F10w-Sheet for the M6de1ling Technique 120

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4.2a Dispersion Coefficients (D), Calculated from

Laboratory Tests as a Function of Pbre Volume
Passage and Depth (Cl and K) ,
4.2b Dispersion coefficients (D), Calculated from

\ Laboratory Tests as a Function of Pore Volume
Passage and ~epth (Ca and Mg) 126
4.3a Cl Profile Distributions in_Natural Sail Columns
Together with Predicted Profiles Using Conv~ction
Dispersion Model 128
4.3b K Profile Distr,ibutio1(ls in Natural Soil ColÙtnns

Together with Predicted Profiles Uping Conveétion
4.3c Ca Profile Distributions in Natural Sail Columns
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( Together with Predicted Profiles Using Convection
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Dispersion Model 13 9
o 4.3d
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Mg Profile Distributions in Natural Soil Columns
Togethêr witb Predicted Profiles Using Convection
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4.4 Procedure for Model Calibration Using Trial and
Error Approach 135
4.5 Schematic Representation of the Prediction Procedure 139
4.6 Migration Profiles from Laboratory Landfi~l Kodel

Together with Predicted Results at One Pore Volume 140
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5.1 cKange in pH Values in ITifferent Monitoring Wells - 145
5.1 Change in Specifie Conductivity in Different

Monitoring Wells 147
5.3a Changes in Cation Concentration in Weil No. 2 149

5.3b Changes in Cation Concentration in Weil No. 5 150
5.4a Changes in Concentration of TOC a9d Cl Ions in o

Well No. 2 152
5.4b Changes in Concentration pf TOC and Cl Ions in
Well No. (/5 153
5.5
, Finite Differenc~ Scheme 158
5.6 Concentration of Ca with Depth and Time

at WeIl No. 2 159
5.7 Concentration of Cl with Depth and Time

at We1l No. l
5.8 Prediction of Ca Migration through Clay Soil of •

20 m Depth 163
5.9 Prediction of Cl Migration through Clay Soil o'f

20 m Depth ~ 164'
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5.10 Nomograph for Solution of Time, Dis~nce, and
Concentration for Cl Ions ~ 165
A.l Permeabil i ty 'of Kaolini te as Function of e 3 /1+e

(After Michaels and Lin. 1954) 195
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The Effect of Activity on Hydraulic ~onductivity
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(After Acar and Seal, 1984) 197
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A.3 Relative Permeabi1ity Values for Three C1ays with

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Variable'Percentages of Calcium and Sodium on Exchange

( Sites (After Yong and Warkentin, 1975) ~99
A.4 Relationship between Dispersibility (Susceptibility

to Colloidal Erosion) and Dissolved Pore-Water Salts
on Pinho+e Test and Experience whth Erosion in Nature
ÇAfter Sherard et al., 1976) • 214
B.l Relative Tracer Concentration in Outflow from Column

of Soil (After Freeze and Cherry, 1979) 218
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B.2 Hydrodyn~ic Dispersion Coefficient Determined from
a Brea~throug~ Curve" 223
B.3 Advance of Adsorbed and Nonadsorbed Solutes through
a Column of Soil (After Freeze and Cherry, 1979) 227
D.l Relationship be~een Soluble and Adsorbed Ca Ions

Series I (Natural Soil) 259
D.2 Re1ationship between Soluble and Adsorbed Mg Ions
Series I (Natural SoU) 260
D.3 Relationship 'between Soluble and Adsorbed K Ions

Series l (Natural Soil) 261
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( D.4a Relationship between Soluble and,Adsorbed Mg Ions

(IlUte Soil) 262
, D.4b. Relationship. between.Soluble and Adsorbéd Na Ions
(!lUte Soil) 263
D.Sa R~lationship between Soluble and Adsorbed K Ions

(Kaolinite Soil) 264
D.Sb Relationship between Soluble and Adsorbed Mg Ions
(Kaolinite Soil) 26S
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D.Sc Relationship between Soluble and Adsorbed Na Ions
(Kaolinite Soil) ~66
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D.6a Relationship between Soluble and Desorbed Na Ions
t D.6b Rè~ationshipbetween Soluble and Desorbed Na Ions
Ô.6e Relationship bet*ee~oluble and Desorbed K Ions

Series II (Illite Soil) 269
D.7a Comparison of Predicted and Measured Mg Ions

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XVII
D.7b Comparison of Predicted and Measured Mg Ions

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0'. Series II (Natural Soil) ) 271
D.Sa Comparison of Predicted and Measured K Ions
Series l (Natural Soil) 272-
D.8b 'Comparison of Predicted and Measured K Ions \,
D.9 COmParison of Predicted and Measured Cl Ions

Series l (Natural Soil)
. 274.
D.lOa rlispersion Coefficients (D), Calculated from

Laboratory Tests as a Function of Pore Volume
Passage and Depth (Na and K) for Illite Soil 27~
/
Dispersion Coefficients tD), Calculated fram
Passage and Depth (Mg and Ca) fQr-Illite Sail 276
D.lla Dispersion Coefficients (0), Calculated from

Passage and Depth (Na and KI) for Kaoiinxte Soil 277
D.llb Dispersion Coefficients (0) " Clilculated from '

Laboratory Tests as a Function of Pore Volum~
Passag: and Depth (Mg and Ca) for Kaolinite Soil 278
- D.12 Cation Distribution along the Landfill Physical

Model after thePassa~e of 0.30 Pore Volume of
Leachate Solutibn 297
D.iSa C0ncentration with Depth and Time at WeIl No. 4 280
D.13b Concentration with Depth and Time at WeIl No. 9 281

\\
E.1 Organic Leaching Solutions Used in this Study 297
E.2 Hydraulic Conductivity of Kaolinite to Different
Organic Solution~
E.3 Hydraulic Conductivity of Iliite Sail to Different
~
Organic So~utions ,,300
E.4 Hydraulic Conductivity of Natural Soil ta Different
.Organic Solutions 301
;.-
E.5 Relative Hydraulic Conductivity of Kaolinite ". 302
E.6 Relative Hydraulic Conductivity of Illite 303
E.7 Relative Hydraulic Conductivity of Natural Sail. 304
'.
E.8a Distribution of Cations before and afu~r Leach~ng
;J"""',
j f Natural Sail with Heptane
, .{ Ir
... ,.t.li~<f
. ",
XVIII
1[, ( .1
E.8b Distribution of Cations before and after Leaching
Illite Sail with Heptane -, 309
~- E.9 Pore Pressure" Distribution along the Clay Sail

(Landfill Madel) 322
E.IO The Effect of Molecular Weight on the,Hydraulic ['
Conduc tivi ty 325

J-
E.ll Typical -Temperature - Loss Weight Relationships 328

. ,
1 ,
E.12 The Effect of Dielectric Constant on the Hydraulic 1
-\
Conductivity of Different Soils 3~0
E.13 Shear Strength-Normal Pressure Relationship for

, Natural Soil ,333
i·
'i
~
E.l4 N~rmalized She~r~trength Behaviour at Different \: \
\
Dielectric Constants 337>
,~-'
F.l Generalized Flow Diagram for Leachate Migration \

~
Prediction 340
;
(
... l'
'. '
(
\"
/ \ l
\
1
..r '
\
o Table (No.)
\
LIST OF TABLES
Contents Page (No.)
2.1 Properties of Clay Sa ils Used in the Present Study 11
2.2 Gfain Size Analysis and Mineralogy 13
2 .. 3 Sail Por~ Fluid Analysis

'2.4 Analysis of Leaehate Colleeted at Landfill Site for
Use in Controlled Laboratory Leaching Tests 22
"
2.5 Physical and Chemical Properties ~f Test P~rpeants 23 ;,
,
2.6 Initial ànd Boundary ConditVons of Series under
Investigation 30
3.L Mean
, Attenuation Number (ATN) 72
3.2 Rank of Chemical Constituents in the Leachate According

to their Relative Mobility tnrough Natural Soil 73 ..
3.3 ,Summary of the G Constant in Equation 3.1 for
"Different Cations 85
~.
3.4 Results of Sorne Selectivity Coefficient Calculations.
If Sorne Leached Samples 94
3.5 Summary of Different Constants (Ai B, and CC) in

). .Equation 5.7 for Different Contaminant Species
During Permeation in Natural Soil 98
.
A.l Common Clay MineraIs and Charge Characteristics 190
A.2 Interlayer Spacing of Calcium Smectite Immersed in

ILiquids of Various Dielectrie Constants 205
A.3 Interlayer Spaeing ~f Calcium Smectite as a Funct!on

of Dieleetric Constant and Dipole Moment 206
'"
B.l' Molecular Diffusion, Mechanieal Dispersion and
Hydrodynamie Dispersion Coefficients 222
B.2· Value of ~ available in Li terature 239
o
xx
-c C.l Models for Describing th~ Movement, Adsorption and

Storage of Chemicals in Clay Liner 253
D.l Summary of Different Constànts (A, B, and CC) in

EqUation 5.7 for Different Contaminant Species
, During Permeation in Illite Soil 256
D.2 Summary of Different Constants (A, B, and CC) in,

"
Equation 5,.7 for Different Contaminant Species
During Permeation in Kaolinite Soil ·257
~.3 Results -of the Chemical Analys~s of the Pore F1uid 258
"
E.la Water Soluble and Exchangeable Ions for Soils Leached

with Different Organic Solutions (after the Passage of
TItree Pore Volumes) 311
E.lb Water Soluble and Exchangeable Ions .for Soils Leached

with Heptane (after th~ Passage of Three Pore Volumes) 314
E.2 Values of VR Calculated after Leaching of Three

Pore VolUIIfes 317
( / \
E.3 Zeta Potential in mV for Different Soils Leached
with Organic Solutions 319
-E.4 Water Content and Surface Area Re~ults,for Some of

the.Cases Studied 321
E.5 o
Direct Shear Test Result~ For D~fferent Permeant
'Fluids 324
'. ,
;' . .. ~
( .
J
J
\ 1
,
g
~
-:,4 ~ CHAPTER 1
:V
INTRODUCTION
,
LI STATEMENT OF THE PROBLEM
~e disposal of ~or~ than one million kilograms of solid wastes in

(, }~.
the United States an"t ,s~nad.a each day is a major problem. This waste
disposal in turn often leads to serious _ health, es thetic, and
\ environmental problems. ~ong these is the poll~tion of vital subsurface
and groundwater resources.
Classically, solid wastes have long been dis.p0,sed of in ways that
have appeared to be the cheapest and the least repulsive to the public.
Very often the method of disposaI has simply involved land ~plication;
....
~
an open d~ and/or sanitary l~ndfills. With the expansion of industry

i ...no_
\., :. and the migration of a large portion of the population ta suburban and
" '
rural areas, the ability of land to adsorb such wastes with no apparent
consequence has diminished. The basic problem with these methods of

:1 sol id wasre disposaI stems from the movement of the leachate solution,
1
"
originating fr6m the infiltration of rain water, into and through the
buried waste at the disposal.site. The dissolution of waste materials
results in species being transported from the waste site ta

co~taminant
,
larger regions of the subsoil zone and underlying aquifers In many
o instances, contamination of water resources is not detected until .years
after land disposaI of the sol id waste has begun, owing primarily to the
slow movement of the contaminants and the conveying groundwater There
are many recorded cases in which the migrating leachate has eaused
, ...
.j:
groundwater con1:amination, ranging from a slight degradation of water
quality ta the presence of toxie concentrations of heavy metllls

"
la
1 2
( (Morrison, 1981), organic compounds, and radioactive materials (EPA,
1977) . ,Sorne of these cases occurred in (Wood, 1984):' "
(1) The Love Canal, Niagara Falls, N.Y. (1978);
(2) Toope, Tennessee, (1978); and
(3)" Sarnia, Ontario, (1977).

'" .
\
Many of these disposa1 cfacilities ,which caused groundwater
contamination were unlined'and relied virtually on the natural geology
to reduce \he impact of the migrating pollutants. The extent of the
pollution from the migration of this leachate solution~ is mainly
dependent upon the geologic '~nvironrnent in which the solid waste is

1
J
deposited. Pollution potential is highest in permeable areas with a
shallow watertable wnere the wastes are in direct contact ;"ith the
groun<;lwater. In relative1y impermeable areas, 'the pollution is
-/ generally confin:d 10CallY' to the vicinity of the waste disp'osal site. '
Site selection for disposaI of solid waste must bè based on two
basic criteria: (1) adequate in~orrnation on water resources. This will

~
require regional and localized hydrogeological data on the surface and
subsurface water systems of the selected area, and (2) the disposaI site
must be located on clay strata of adequate depth. The value of clay
soils in modern environmental technology has been clearly recognized. In
particular, the low hydr~ulic conductivity and the high adsorption
... capacity (attè~uation capacity) of clays have led to their use as
physical and chemical barri ers ànd/or buffers against tre migration of
leachates frQm disposal sites. This attenuation capacity of the clay

, . ~j
soils arises from: (1) the presence of net charg*) on the clay ,/'
c surfaces favouring the adsorption of other ionic species, which are

3
usually present in th~ leadbate solution, and (2) precipitation and
filtration mechanisms. The United Stqtes EnvirQnmentat Protection ~gency
(EPA) and the Environmental Protection Service of Canada (EPS) have made
( ,
the pre-use of this forrn ~f clay barrier a fundamental criteria for (ibs
definition of) a secure làndfill site.
The knowledge of physical, chemical, and biological interactions
that take place between clay barriers and l~achate solutions, is yet
limited due ta a myriad of constituents and mechanisms involved. The

·f
rate of interac~i01 and the domin~nce of one reaction over another are
controlled by specific soil constituents and their associated buffering
capability.
1:2 SCOPE AND OBJECTIVES OF THE PRESENT STUDY

)
Although clay soils have long been used in earthfill dams and dykes
- as a seepage control material, the total criteria which lead to the
prediction of long term stability, and non-degradability of the soil

.
mass, have not been clearly defined. This lack of understanding is due
ta the limited consideration that has been given ta the interaction
between clay soils and different chemical constituents. (Appendices A,
B, and C p'resent extensive technical revicws on this ~ubj ec t.) Flux of

o
• ~ontaminant speèies from the was te impoundrr.ènts changes the pore fluid
chemistry which is closely related ta sail properties (e g.

/
permeability, shear strength, buffering capacity,.. etc.) Any change
in the Rare fluid chemistry may lead ta a removal of the existing bonds,
and/or a change in the interlayer spacing between particles, and hence
an alteration of the internaI equllibrium stab il i ty and membrane
capp.bility. For example, a change in the composition of the existing

..... ";.~ u..;.wy~· ;~/,·7··
" .
1 . 4·
\
• -
cations, either in .valêncy or concentration leads to a change in pore
.,
'C , >
dimensions, as a result of changes, in the interparticle forces witq.in
the clay, matrix. Interlayer spacing incrfoases with cation sequence K <
Na < C:, (Yong and Warkéntin, 1975), Also, exposure of, the clay soil to
(
organic br inorganic acids or, bases may dissolve portion's of the clay'
,,' ! . , t) 1
" '" ~ 4 \.
structure, Solubility ~f clay mineraIs in acids varies with the ~ture

:) F .... "
of acid, acid concentration, acid to c'lay ratio, and duration of

.~
•
-exposure (Grlm, 1968),
As a result of these reactions, whlch may take place in the soil
matrix due 'to the, flux of pollutants from the disposa1 faci.1ities,
changes in the soi1 properties and the rate of pol1utant mi~ation may
l"
o~cur. Investigations concerned with the influence of f1uids on soil
interaction mechanisms and behaviour have been carried out at the
Geotechnical Research Center (GRC) since 1968 by Yong and his coworkers.
\'"
The present study is another phase of the ove raIl program. The main
objecti~s of this research are:
(1) To evaluate the capabilit~ of different cla~ soi1s to contain'
various types of pollutants usually present in landfil·l
leachate; and
,
(2) To establish fi rational approach for designing the clay liner
based dn the quality of' the effluent a~d the retained po11utant
1
profile,s.
o
In conjunction with the above-mentioned objectives, the follow~ng
\ questions àre asked:

: \ 1\ " '
, J )
i •
(1) How are,. the contaminant species retarded, adsorbed, and

v
J
transmitted througb.. the sqi1?
o
(2) How can one predict the amount of each specif~c contaminant
, .
, "
.J
"
'5
o that
far?
~ill be transmitted through the soil? How fast, and how
.\
(3) Is the laboratory model Adequate ln the slmu~ation of an accual.
sanitary landfill lirfer and how does lt compare to sma11 scale
tests?
(4) Is the naturar clay soi1 sui~able.to'function as a line~? Will

aIl the cqntaminant species be adsorbed/retained?
(5) What are the effects of the migration of contaminants through

\
the ~lay upon certain geotechnical properties?
To answer chese questi9ns, the physics and ché~istry ?f interaction
between specifie (individual) eontaminants and clay need to be examLnpd.
Laboratory investigation and field measurements are an important filet of
environmental studies, sinee they serve to verify' existing theorLes and
-- highli~t new considerations.
s tudy is gi ven in Figure 1.. 1.

A schernatic repre'sentfition of ,the overall
1 . .3 ORGANIZATION OF THE. THESIS
The thesis consists of 'six chapters .and six appendices TIlt>
contents of the six ehapters are as follo .... :
Chapter 1: is an i~troductory chapter prescnting the problf!m and tha
purpose of chis study.
Chapter 2: provides Il description of the experimcntlll methodu. w4teri31u
and techniques employed in the study
Chapt(!r 3: presents.., the resul t'a of the laboratory studio. coneurnlng
the migration ~f contaminant spoc1cs throup,h difforont clny
solls; and a discussion of t~e5e result$.

/ .
Chapter 4: presents the I1I4thematical model used tor th. prod1ctlon o'f
>
~ ~
«'il'
'"
....
Migration of Contaminant Species Through Clay Soils
.,;
\- --~ -_.~ -~--- .-- .~.~._--

1- ' ._.--
---- _. - T---· -~ - T~ . ~I
'Literature Review Laboratory Study Mathematical Field Study
Predictions
-r- .,- - 1 1
. 1 1
")
.
Clay
Soils-Contaminants
-
Mechanisms
'Controlling
,
-
.
:4;
Interaction Contaminants Migration.
,<
"-
Migration Profiles, Break through Carrying Capacity Hydraufic
C,urves Conductivity Change.s

-",-
Fiq. 1.1. Schernatic Representation of the Present study.
v"\
0\
7
O·
" . ' . "
contaminant migration and the moving ft;1ont; .comparlsons
between the laboratory determined data and the predlcted

1
\
results.
Chapter 5: describes the case\study and the field predictions.
Chapter 6: contains Othe summary, concluding r~marks and suggdstions for !

further studies.
,?'l
The contents of
~
the appendices are as follows:
Appendix A: presents the different aspects of the properties of c-lay
soils with special attention to the fon-' sieving or

\.
'filtering capabili ty. Also, this appendi-x highli'ghts the "

effeet of sorne eontaminantOspeeies on clay soil properties,
Appendix B: concentra tes on the physico~chemieal processes which
govern the earrying capacity of the various clay soils.
Ap~endix C: summarizes the avai lable ma thernat'ical models for

~,
, .
predieting the reaetions and migration a·f· eon'taminant
species through clay sail media.
Appendi}t 0: presents sorne of the experimental results .concerning the
migration of contaminants through the clay soil colwnns.
Appendix E: concentrates on the effeet of orgllniç p'ollutants on the
g~oteehnical properties of clty sbils . The Seotechl.11 ça l

- y ; \
properties studied include; hydraul ie C ondue t 1vii ty and
... 1
-
shear strength. 1
Appendix F: presents sorne general e.onsidératlons
.;
.\ ~
,l' 8
...
CHAPTER 2
HATERIALS AND METHODS
2.1 GENERAL
An operative landfill site located near Montreal (35 km east) was

, -
'selected for the study of:' (a) the effectiveness or usefulness of the
, '
natural clay sail as a containment material, and (b) the influence of
the Ieachate, which is genèrated from the disposaI of solid 'waste, on

r'
Q
the different natural clay sail properties. Figure 2.1 shows the
general landfiii scheme used in the containment of municipal solid waste
(MSW). materiais. ~
In order ta fuifii the ,'above obj ectives, a research program was
designed for both field and laboratory study. This program included the
( following:
(1) The evaluation of the characteristics of the natural clay sail
used to Une the disposaI facilities at the landfHI site,
(2) Characterization of the Ieachate solution generated from the

.
buried solrd waste,
(3) A leaching test program conducted ta aetermine the adsorbing

J
capability of the natural clay and tt.TO other laboratory
controlled soi1s for various chemic~l constituents present in

,
the, Iandfiii 1eachate solution, determination of"the migration
profiles of different côntaminant species in, the laboratory
tests~ ,and comparison of these results with the field results,
(4) A le'aching t~st

o
'program conducted ta evaluate changes in
1
1
different soi1 properties (e.g: shear strength and hydraulic
1
( conductivity) due
"
~o permeation of different organic solutions,
1
\1, f
1
1
J
\
,
\
,-"
\ , 1
.. .....
,,) , -.. 1
. "
,
"
,
1 .
slope 2~~
---..
. 1
--.L·T.70...l1.2a;. protection cover
1 m l '1
. "
~~
1"
clay barrier
~3.0' -:.....}
m
. solid waste __n_a_tu_r_a_I_C__
la_Y____
Fig. 2.. 1. General Landfill Schene Used 1J':l'Actual LtVldfill Site 1
·0.
-
\
10
(5) lns-tallation of samp1ing points (monit<:.>ring welis) for 1
monitoring the ear1y migration of contaminants into the

\ ~--!
subsurface environment at the 1andfil1 sÜe (located near
Montreal) and collection of data from these monitoring points
ta be used in examining the prediction mode1, and
(6) The eva1uation of the sca1e-up ef:tect on the migration of
contaminant species, by comparing thé leaching co1umn results
with the laboratory 1andfill model resu1ts.
, .1 t \
2.2 SOI~P~UPERTIES AND CHARACTERISTICS
Three types of clay soils were selected Tor this investigation.
They were: (1) natural clay, representing Quebec clay soil, '(2) i11ite,
and (3)'kaolinite. The latter two were used as controlled laborat?ry
s~ils for comparative purposes. The natural clay soil samples were
obtained from the landfi11 area, at a point sufficient1y remote from the
actual disposaI site to ensure purity. lUite (Domtar Sea1bond) was
obtained from Domtar Construction Materials, Ltd .• and the kaolinite
(Hydrite PX) from' the Georgia Kaolin Company.

\
,
The selected soil samples were subjected.to a variety of physical
and chemical tests. The various physical properties of the different
soifs a~e pre~ented in Table 2.1. The particle-size gradation curves
are shown in Figure 2.2. The avelt"age particle size (D50 ), the
effec ti ve si ze (D 10 ) ' uniformi ty coefficient (C ), and the

u
coefficient of curvature (Cc) are summarized in Table 2.2.
The X-ray diffraction analysis was performed on an oriented sample
mount, which was prepared by pipeting 4 ml of a 1% clay suspension op to

l' ",/
114
\ f ...
'r,'
.J
TABLE 2.1 Propérties of Clay Soils Used in thè Present Study,
0 Properties AS'IM Natural ~llit:e

1 '
Kaolinite
Test No. Soil (PX) •
(1984 )
, ,
LiquiSi Li(ni t ' D-423:"~4 65% 32.8% 66%

\~
v
Plastic Lirnit 0-424-54 26% 19.6% 40%

• rj
'./.,\
Natural Water Conten~ 02216 <62% 0.80% 0.3%
Specifie Gravit y 0854-52 2.67 ' 2.68 2.59
Void Ratio 0.90

, "
Dry Density Mg/m

.
3
071 1. 39 .'
3
, Wet Density Mg/m D71 ,'" 2.17 i· ~
!
" Specifiê Surface
2
80 81 12
Area m /g
tJ
--
d
•
t
j
fat ion Exchange .
Capacity meq/100 9
Permeability Coeff.
"(D. Water as penœate
,)
D2434-68
60
7xlO
,1.9
50
.9x10
1
_9
10
3xlO
_8
solution) rn/sec
~
1. I-llite = Domtar
•
Sealbond
,1
,r
\
0-
( _.- '1
.
, \
\
12
(
la 0
!l0
v--' ~
~
_. -- ~
p
110
f,
/ V
........
"
.A"
~
- l----1--
10
~ V
\ ./ ./ (
60
-;7
~
,
~
ID ~
• "'ite
C:' 50
~ .
-
I..L.
c:
ID
0
~
411
lU
.-------- ~
/ ... Natural S oU- ~
ID
a.
:l0
,
-
la -
"
0
~ 1ft ..... _ .. 0 o Q 0 0 00000
N n • an .,
..... ~ 0
Diameter (micron)
,-
100 .
....1
lia , ..---
, .. " ,/
~
~U
70
/
,
...ID ,60
v
/ !,
C
/
-
I..L.
c:
ID
0
!.o
40 >V • KaoJinit!e
.
~
ID
./ -'
a. 30
2U
/ -
./'
/ ,
10
~' .
,/
0
N
n . tI'I.~· . o
( Diameter (micron)
• Fiq. 2.2. Particle Size Analyses for the Different Sails.

1·
\
,,
13
TABLE 2.2 G.rain Size Analysis and Mineralogy
0 ..
Properties Naturel SOil Illite l<Ao linite .
1
• ~ 1
..... L .(
"
Gr~: .~.ize Analysis ( 1 )':
D$O J..IITI 0.80 . 5.0 / 0.78

!J , I?'1 O. lJITl 0.10 0.10 0.18
(2) 13.0
Cu a 86.0 6.11
c (3)
0.78 1.16
,t
0.71
c
.~neralogy: feldspar. illite kaolinite

illite chlorite mica
quartz rrontnorillonite
kaqlinite quartz
homeblende feldspar
chlorite'
- Organic conten\ . ,
dolomite
0.4% (w/w) 0.0 ·0.0
(1 ) AS'IM. Test No. (D422-54) (1970)

, (
\( 2) c' = Unifonnity Coefficient (0 ID )

u 60 10
( 3) C = Coefficient ~f Cw:vature (0 )2~/D X0
o C ~ ,~o . 10 60
o
. .
,
"," ,"-
14
c a ,glass s liele and allowing it to air .dry.
given in Figures 2.3 a, b, and c. 'A list 'of mineraIs prese~t, based on
\
X- rflY diffractograms are
the X-ray di ffractograms, a~e arranged in order of decreasing abundance
in Table 2.2.
The results of _-,the chemical atllllyses of the pore fluid obtained
from the natural and'ill~te c1ays are ,sunurrh:ed,in Table 2.3. Pore
fluid was obtai~ed (from the soil samples employing the pore fluid
remova1 method (EPS Laboratory Manua1, 1979),' This pr~cedure required
the preparation of a 1:10 susp~nsion of soil in disti\led water. The
fluid was then separated from the solid by centrifugation and chemical
. -
analyses were then subsequently performed. The tests gave the amount of
soluble ions per 100 grams of soil. The chemical analyses included the
f
d~termination of'pH, e1ectrica1 conductivity, cations (Na, K, Ca, a.nd
c' Mg, ,
Fe) .
anions (C0 3 , HC0 3 , and Cl), and heavy metals (Zn',
The analysis .of the heavy metais was carrie4 out using an Atomic
Cu, Pb, and
,~bsorption Spectrophotometry. The resu1ts showe~ that the conçentrations
of the heavy metals in aIl pore fluids, obtained from three soil
samp1es, were be10w the.detection limits .
. The relat:ionships between optimu\ll water content; and the maximum
dry,density for the three types of soi1s wère determined fol1owing ASTM
Standard No) (698-70). 'Figures 2.4 a)rtd b display th~~e re1ationships,

•
! •
, as well as 'the lines of the relative air content, which indicate the
effectiveness of èompaction~
(>
4'>
.... ,.. ..
".
·C· "
"
,~
..
~,
:-
.. ' .'
.,. V
p
J
.::> "
.f
t::~,
'....... c o
\
~I
, ~
~
I"zj
..... ,,,
""
Ll
"->
2. 90 ~ Do1ollli Le
,-",0-
0
W 0
tII
J R Ilorneb 1enlie
X
t-J
l.D'-
3.] 4
3.2LJ ft rel<.lsf)[ll' ,
"
1
S.2S Jt Feldspal"
"
tII
-< ~,
0'>
J._
3.3 i l ft Quar Lz
0
..... .L ~6 ft Kaol i rllle
Hl
Hl 1-,,).- 3. (,9 R Do 101111 Le
t-1
\OJ
'-' ....
()
rt"
,...- '....)1- 4006 ft reldspar '11,
0 hl
::l
/1.27 ft Quartz
5" hl
0
....
tII
r,J
ll.72 RCfllorlle
• 'V1
1-'-
<D
~
.....-
CD
Ul n. ft Illile
>-t}
0
rtI
<.0
..., ....
a,
t-1 ln
10
Z
01
L~
....
Ë '-'
Rfelllspar
t-1
tII
.....
~
>-
L..J
1 - R~hloriLe/Kaoijnll6 -
....
1-'-
L'
-:: =-0.51 R lIornb 1el1de 1O.0~ H' [Il Ile
ru
a- 14.,5 R C'''oriLe
I::-
,J t-
)::.
o
-u
\Il
\ft
1-'
V1
a .Cl
~ a a , -0
6' n o '-
" ~
"
" -
--'
•
<>
16
(
.-' '.
:l4
.'
, .
30 S.0276 A ° CAL.CITE
•
28 3.1965 ,,0 FELOSP"R :a.S3ge ,,0
QUARTZ
S.
26 - 8.5339 ,,0 CHL.OR.ITE:.
", II..L!TE:
" 4.4839 R QUARTZ
.. W 20
"
~ W
Il:
"
UJ
C
18
v
...
4) 16
ru ... ,
14
O
, 7. aS1 A CHLORtTS
,
...
/
0
l.Q. C ... A tL.l..ITE
~
1.4.caa AO CHL.ORITE
(
Fiq. 2 .3b. ~X-Ray Diffraction An~lysis ,for Illite Soil.
.:> o
'<i'
!~\
~~f f
..
"
" (
l'%j ~
1-'- g
.Q
N '"
QI
W '?6.~· (3_351~)MiCa
a
r '"
al
. X
-:1, N
~
24;7·(3.6073JQ Kaolinite·
) ~
_-dl
....,-
...,
bl
o :p .
HI 21'(4.23 K ) Kaolinite
HI
20.19(4.3959/\ ) Kaolinite 1
1.. ~
n ",-
'"
0
19.7 (4.5063 Â ) Ka 0 linite
rT- o',
...... .....
g, QI
. S-Pl '
I\)
,0 ...
. al
,"'"
0
1-'
~
CfI
(Q
...
1-'- , ..,.
""
tIl
~
CIl
CIl
..
~,
Po.)
(
12.2'( 7.254 SA') !5aolini te

1t1
... \' "
~
1-'
0
, \ 8,1" ('O".3Â1 Mica
~
....
$
-QI
"
'CIl
,0
nt
......
1-'
•
al
""
-\,---.-_--- "'. \'" ~
" ~
N'
,- .
/f'
1
f
\ ./
1
1-'
......
If
1·
.~ .;~
: 1':;~
-~.... • j~ r ,'.-; -
' ' ' "

""'- \
\
1
. "
\
18
1"
TABLE 0 2.3 Soil Ppre Fluid Analysis
C
1. > •
c
Pararreter Concent=ation mg/1OO 9 soil AS'lM

•
Nat'...tral Soil Test No •
.1
Illite ( 1984')
He0
3
180 79r~0
'~"?I '
o 513
/'
~' ~
. co 0.0 0.0 o 513 i,
3 1
" \
. Cl. 170 70.0 01253
Na 130 42.0 04191
/'iO
of! "
"
K. 14 2.0 04192
~
~, '"
/ - ca 22 36 0511
Mg 29 2.0 D 511
Fe ;> 0.1 <0.10 01691
pH (pH units) 7.5 7.9 01293

1
\t ,
Specifie Conductivity 38 15 D1125
J.l mho/an
C 'lœ 50 <la' 02579
c
, .
~~--~---
, . ..,." '
' 1'" ~ -, 4~ > -'" ;;.~ 'f"
\-
19
"j
0 1.6"
Natural Sail
-
CO)
E
......
155
1.S-
0
1
--
0)
::2 1.45
t.
,~
.r:.
0)
Q)
1.4
--
.'
~
1
-C
:::;)
1.35
13
»
'- 125
Cl Air Content
12
0 5 10 15 20 25 30 35 40 45 50
0 Water Content (%)
185
Illite
18
-
CO)
E
......
0)
..
...
1.7'5
-~
~/
0)
CI)
3:
1.7
5%
\0% \ ,,
-
~
c
'.65 - -
\\ \
>-
'-
Cl Air Content ,
1,8 ---:---l
5 7- 9 11 13 15 17 19 21 23 25
Water Content (%)
o· ,
Fiq.'· 2:4a. Dry U~it Weiqht:_Water Content Pel,at1onsh1p for MaturaI
&nl and Illlte.
.
l •
l, -;y
: - \',
, 1
20
. '
c- i
1 4
-
C'l
-f . 1.35
Kaolinlte'
"Cl
-..
~
.t::.
Cl
1.3
, <I>
..
~
c
r
::>
1.2
>.
~-
/ Q
/
1.15 Air Content
-c 1. 1
10
)
15 20 25 30
Wa ter Content (%).

35 40 45 50
Fiq. 2.4b. t Unit weiqht' - Water content Relati~hiP for Kaolinite.
(
21
AHE~ICAL ,ANALYSIS OF THE ~CilATE SOLUTION
The 1eachate solution used in the 1aboratory study as a control

-
permeant solution was collected directly from the basi-ns designed to
gather t~e leachate solution generated at the landfi11 site (due to rain'
, -
- water infiltration and/or interception of the subsurface 'Water with the
•buried waste). Samples of the leactrate solution were taken from a
number ,of locations within the leachate basins, and were pooled
,
together. To ensure that the composition of the leachate solution used
in aIl laboratory tests remained constant, a large quantity of this
solution was collected. These samples 'Were stored in polyethylene
containers and were kept at a constant temperature of -10°C, in order

1)
to minimize chemica1 changes due to microbial action. The results' of
chemical analyses performed on the leachate solution are provided in
Table 2.4. The selected chemical analyses were conducted on three
- different samples and the average values 'Were reported,
were conducted according to procedures described by the Envlronmentlll

The analyses
Protection Service (EPS) (1979), and ASTM Standards (1984).
2.4 PHYSICO-CHEMICAL PROPERTIES OF ORGANIC LEACHATE FLUIDS,
Hydrau1ic conductivity and shear strength tests were carried out on
the three types of cl,ay soils permeated by five organic - liquida,
se1ected from four classes of organic compoundt;i~ and water (as -
c,Pntrol). The four classes of organic compounds were: (1) ac1dlc, (2)
basic, (3) neutral polar, and (4) neutral non-polar. Table 2. S lists the
\
organ1.c solutions (Heptane. Xylene. Aniline. Acetic Ac1d. Acetone. and

.
water), along with their relevant physical and cheiidcal propertles.
These _organic solutions were selected to represent li range of dieléctr1c
eonst~ts froID 7\8.5 (polar wliter) to 1.90 (ne'utrai non-polar heptane),

-.. " f
22
Analysi~
c
TABLE 2. 4 of Leachate Collected at Landfil1 Site for Use
in Control1ed Laboratory Leaehing Tests
\
~arameter AS'lM Concen tration Standard for'Drinking
Test No. Water '
(1984) mg/1 mg/1*
BOD o 888 450 40

COD 01252 860 100
'!OC D2579 190
TC 02579 289
oil & grease 04281 24 15
phenol D1783 0.04 0.02
total iron 01068 5.0 17
Mg D511 35 150
Ca o SIr 180 1 200
+K D4192 16
Na D4191 140 270
NH 01426 20.0 0.5
3
Cl D1253 190 250
C0 D 513. 0.0
3
He0 D513 303
3
pH D1:29-3 6.8 (pH units)
Spec. Electrical
Conductivi ty D1125 • 2.7x10 3 ,umho/cm 23.0 ,u.ml)o/cm
,
Zn D1691 2.5_ 5.0
Pb D3551 1.0 0.05
CU D1688 r 1.7 1.0
...
: . * (Envirorurent ~anada, 1979)
, j
1
j
J
o f.:o,l
y
.0
f
,
TABLE 2.5 Physical and Ch~cal Properties of Test Permeants
<li U 1
~
~
a. b'-
III 'r-!
c:
.!If
+J .r-! H+J -ô 'r-!
Organ:':: Chenù.Cé!l >tu CV) 'r-! U 8. +J~U
° ~ 2h'O ~ I-I..QN~oo
U +J''!:i
Tenperature" 'r-! III
III 8
IIlO .
;!:i°o E U +JO
~c:'O
00""" <li +'~ •
Range c:
,~ ~
<li ;:)
IIlN
""'-
UN+'
c:
r-iIllN ~ :;: eJ Sc: 1
~~,
Group Type Name C' Cl III <li C:' H +Jr-i+J
~10 ~
'r-i +' ~
> co
r-!O+,
Cl U co ~ :x::
COOCO
::: Cf) -
• "
Meltmg BOl.lmg
'
> Cl '0
.Acid Aliphatic Acetic 1.O~J1.20 .6.20 60.05 20.0 CX)

17 118 0.875 1.04-
Acid
Base Aromatic Aniline 1.02 4.50 6.90 93.13 18.10 " 34.0 -6 184 0.226 1.55
amine
",
Neutral Ketone Acetone 0.79 0.33 20.70 58.08 9.7!)" coi -95 56 2.39 2.74
Polar \'
~
Neutral Alkane Heptane 0.68 0.41 1.'90 100.20 100.21 0.003 -91 98· 1.6& 0:00
rbnpolar
"-
0
,
Neutral Alkyl Xylene 0.87 O..{31 2.60 106.16 O.~ 0.20 -47 139 1.074 0~40
Nonpolar Benzene
Trlater ' 1.0 1.0 78.50 18.00 ' 39.00 CX)

0 100 LOO" 1.83
."
-r
'.
't
..,
. ~<
.
~... ~
l\l
W
,',
1
-t!o.
24
c
2.5 LABORATORY,~NVESTIGATION OF CO~AMINANT MI~RATION
In this investigation, laboratory leaching éells we're designed to
simulate slow, saturated, ana~robic flow of leachate through clay liners
'surrounding the landfill and the leachkte basins. Each cell consisted
of a hollow plexiglass cylinder 3 mm thick, with an oul:side diameter of
106 lIl1ll, and a total length of 100 1lIl'fi. ~lexiglass top cap, and botto~
.
plate were :screwed to the top and bottom of each aylinder, and fitt'ed
with rubber O·rings to 'prevent leakage. The permeant solution and a

-,
pressure head were applied to the top of thE' soil and the effluent· was
drained from the bottom at atmospheric pressure. A hydraulic head of
2.5 m was applied ~ simulate the pressure hea.d in the leachate basins
1 •
by applying an air pressure equivalent' to 2.5 m of water head, as shown

/
in Figure 2. 5 .
( Leachate lolution was allowed to permeate through the clay cores
for periods ranging from 1 to 6 months.' During this time, effluent was
1-
collected'periodically i? polyethyl~ne bottles at 2 week intervals and
analY7ed for different chemical parameters.
The soil thickness was kept at 100 mm. A 3,& mm 'thick porous stone
was placed on top of th~soi1 fore to ensure uniform distribution of
the hydraulic pressu~e on the soil' surface. Another, similar pQrous stone
was used at the column base to collect and channel the effluent to
the drainage outlet (Fig. 2.5).-
( !
25
o
,
ln~et for air pressure
"-
M 1 ______ :.- V~ _.
)
-:::::F" -.:.;...---
- reservoir
,
... permeant solution,
3 ; i 100mm . 3.
,
1
- L
o
r-
" Il Il Il Il Il Il Il Il Il /1 Il ~
~
/
,
Q
6 i . ~
-
J
3mm porou13 stone
compacted soir _-
E
E 'plexiglass ~ylind,~r
"'0 3' ~ 100 mm 3
...
d
o ~ ,
il'
,
,
, /
-3 mm porous sone
'"
1 ~
H
, " 0
0
lU
\
effl uent • l , outlet
Fiq.' 2.5. Schematic Representation of Laboratory Leachinq CeU

tJsed' in This ~tudy.
0,
1
.
c 2.5.1 Soil Preparation

The so il, used in the leaching columns was prepared in the
following manner.
A 1,500-2,000 g soil sample of'welf ground, (to pass through a ASTM
1 No. 4 sieve), afr-dried clay soil was weighed anp transferr~d to a mixing
pan. An amount of distillQd water equivalent to the optimum moisture
content was added. After it had been mixed, the sample was wrapped with
parafilm, and stored overnight for equilibration (Green et al., 1981).
With the mould and collar clamped to the base of the compaction·
/
, apparatus, about ~me half of the mixed clay soil was placed in the,
mo}lld. The samp l~ was compac ted wi th a 2.5 kg (5.5 lb) standard hanuner .1
c
to conform with the Standard Proctor compaction test procedures, (i.e.

1
1
1
5.9 x lOs J/m3 of compàcted energy). The actual moisture content
c was then determined.
carefully leveled.
'The excess clay in the mould was' Iscraped and
After this preparation, the moulded clay soil cores
were placed in the leaching cells and the test permeant solutions were
introduced. Wax and grease poured in layers were used to fill in the
gaps between the soil core and th~ plexiglass 'cylinder, in order ~
prevent any s ide leakage. . Introduction of the leachate solution took
place only after the hydrauliq conductivity value was stabilized (us'ing
d~stilled water)', 1. e after a hydraulic conductivi ty value in the order
of 10-8 tQ 10- 9 m/sec 'was obtained.
2.5.2'Test Procedure
Each series studied consisted of four replicate samples, and were
structured for testing, using the test scheme s~own in Figure 2.6. In
1
the first cell, after completion of the passage of one ~\pore volume (PV)
C
\
\ . 27
o Naturar Permeant Solution

,
~
constant- concentration (Co)
hydraulic head (2.5 m)
Kaolinite
1 t
Illite Natural Soil
L 1
::.. : :.~::::. ;;.;~::~

.' SOu.;:·::::::
:;~·~,\t:,;\l:~
C1 ~
1 pv
1
\
1- !=ff)uent Analysis (Breakthrough ,cl,1rve)
2-Hydraulic Conductivity
... ...
Soil Content Taken Out
,
\ .'
A- Pore Fluid AnaJysis B-Soil Analysis
Soluble ions C Exchangeable ions 5

.: 4='" ..•:~ •.:: .:...••:. <.. . . ...
3-Migration Profiles
o 4-Adsorption Isotherms
Fiq. 2.6. Test Scheme Used ir1 This Study.
\.
28
of the assigned permeant solution, the test sample was removed and
( sectioned into six layers for analysis. In each of the other three
cells, selected po~e volumes of permeant solution were also leached
through the soil cores. The values of the selected pore volumes were;
one, two, three, and five, respe\tively. Each single pore volume of
effluent was colrected in a period of approximately 30-35 days.
Following the~ the specified le.ching test, the test
sample was sectioned into six layers and the soil pore solution in each
layer analyzed for extrô;ctable and soluble ions. The extractable
cations (Na, K, Ca, and Mg) were determined using the si1ver thiourea
'method described by Chabbra (1975). The soluble cations, anions (Cl,
C03 , and HC03 ), and heavy metals ÇFe, Zn, Ca" and Pb) were measured
,
on p,ulverized samples using the pore fluid extraction method (EPS
( Laboratory Manual, -1979). Finally, the exchangeable cations were
determined by subtracting the extractab1e cations from the soluble
cations.
,
The, analyses- for cations and heavy metals -were conducted using
Atomic Absorption Spèctrophotometry (902 Double Bearn). The anions were

" determined by the titration mèthod (EPS Laboratory Mânual, 1979) .
"
.
'
The organic load was measured in the column effluents and pore
fluids as total organic carbon (TOC). TOC measurements are considered
in the pre-sent study because of the advantage over chemical oxygen
demand (COD) and bi01ogica1 oxygen demand (BOD) , as the latter
methodo10gies ,.may be significantly biased by the presence of reducing
agents, refractory compounds or toxic materia1s (Barcelona, 1984). The
concentration of the total organic carbon (TOC), of aIl samples was-

(
,-
29
\.
o determined using a Beckman
this method,
~odel 91SA Total Organic Carbon Analyzer.
the difference bet:We,an the total carbon and the total

In
inorganic carbon represents the total organic content of the sample .

•
The pH and the specifie electrical conductivity were determined in
all samples using a pH' meter (Beckman Century TM 55-1) _and
Electrophoretic ~ass-transport analyzer (Model 1202), respectively .
.0;-
2.5.3 l'he Experimental se'rOtè-s-Invest~gated

~ 1 1
·The initial and boundary conditions of each series are sununarized
in Table 2.6. In Series l, the natural soil was compacted wet of
Proctor optimum m?isture content, to allow for easier handl1ng and to
simulate possible field liner implementation practices. In Series II,
the natural clay was cOippacted at a high~r compaction effort: to generate
a lower hydraulic conductivity, in order to test this method as a
potent~al liner implementation technique. Series III to VI were used as

.:,1
contrdl models for eornparison purposes.
,
2.6 LABORATORY INVESTIGATION OF CHANGES IN HYDRAULIC CONDUCTIVITY
AND STRENGTH OF CLAY SQILS
. In this part of the study, the chan~es in different clay soil
properties such as hydraulic conductivi ty, shear strength, surface

"
0'
are~, and zeta potential due to the permeation of various organic
solutions were studied. Three test series 'were structured for testing,
using the test scheme shown in Figure 2.7. The three test series are
p~ovided as follows:
o
,," ~ ~~
.. l',
,
"
~
0 .. " " 'l

~
~
..
.
""
". "
.
TABLE 2.6 Initia~ and Boundary Conditions' 0(' Series under Investigation
,
Series ,No:, Soil Type Water Content Degree of Carpaction Perrreant
"-
Sa tur.a tion Effort r Solution
l
. ,natural ,clay 35%
(wet of optim.tm)
94%
(average)
,25 (standard) natûral leachate
- II na tural clay 30% 96% 35 '.

, (optirrum) (average)
natural leachate
/
\
III natural clay 30% 94% 25 (standard) natural Ieachate
( opt.i.num) (average)
oC
--
IV ~oliJlit~ ""33% 95%,
L
(optinunf ",
(average)
V iIIite 17% 94% natural leachate

( opÜnum) (average)
,\ .'
.'
~
w
., ,-, ", o
""?
f'
"
" . ..
31
, .
Permeant Solution
Initial
t Acetlc
t
Distilled water Xylene rd Heptane A n III n e Ace ton e 'L e a cha t e
1 1
.. , :
ac
, 1 1 , 1
,~' . -K -:': ~:' .K
• :,..- 1 ~
, .,' 'K" ,., -
1'\',1, 'r
,:', 'K' :' ,

, . -
':i
-,
; -, L. " 'L , J ,'" ,L. , : ,1.
:-L:,: "
1 ~~
,. ~ .- -
: ' ,,- N ,,' :..:
1
J
>: jjr,':: j ;! '~,
~,
No: , :" N. '-,' .- - ;- . :- ',-' ,~:,'.' ::,~,
, ,1
. . \
r f · t t t
.:
1-,Effluent Analysls
- -
Experimental Data {
2- Permeabliity Measurements
After 3 Pore Volumes Passage'
\ SolJ Content Taken Out

1
t
f f f t
Pore Fluld Soli Analysls Sh'ear Strength / Vlscoslty
Analysls
, Direct Shear
Note: K: Kaolinite 1= mite W= Natural Seil
Fiq. 2'.7. Test Scheme Used in ~e 9rganic Permeation Study.
", "
,
O
~
1
1
. /
1
'.
l
Series Clay Type Optimum Max.Dry ~ Compaction* Degree 'of
/ Water Density \.Effort Saturation
Content Mg/m3
.
A Kaolinite 33% 1.37 25 blows/layer 9~%
'.
, " ,
B .lllite 1 17% 1.80 25 blows/layer 94%
C Natural Clay 30% 1.47 2'5 blows/lay~r 94%
* Standard Proctor Compaction Test (
-' -
11:e detailed leaching test proced~re was describëd in Section 2,5.
The soils were moulded with distilled water and coIiipacted- 'by following
the StanDard Proctor c@mpaction test procedure (A~ N~. 698-70). After
. ihis, prep.aration, the mou1ded clay was placed in the lElaching ceIIs.
"
Such samples,would simulate water-wê~ clay barriers.
After the passa~e of three ',~9tre volumes of different organic

(
.permeate solutions through the assigned clay samples, the soil samples
~ .
,
were removed and examined for changes in physico-chemical and
/
mechanical properties ~ As previouslj mentioned, each sôil samp'le was

• .t
sectioned into six equal
, (horizontal) parts, and the resident pore fluid
was 'a,nalyzed. Exchangeable and extractable ions, as well as the ?rganic
cOQtent (meÇlsuréd as TOC) were "determined.
The mechanical properties of the leached 50 il samples were ex~ined

1
using the direct shear test. This test was carried out in a conventional
~ ~
~, .
she~r box apparatus of 40 x 40 x 15 mm. Porous stones and filter paper
.
"', were used on bath the to.P and the bottom of the sam~les. Normal
"
pressures
.
of 35, 70, 140 kPa were 'used .
4
The vi~cosity of the samples was measur_ed with a rotating cylinder
~ ~ c ~
, 1 :
, \, . ,
1.
j
33
viscometer (Contraves Rheomate 15), capable of 15 different shear rates,.
increasing in geometric progression. By measur.i'ng the torque required
to ms.intain a given ~hear rate, the shear stress can be' calculated and
the flow· behaviour of the suspens~on can be deduced accordlng1y. The
solid concentrat~on was 8,% by weight ~.or aIl. s~ples examined in this
study.
.•. The ethylene glycol monoethyl ether (EGME) retentlon 'method was
employed to de termine the surface area of the 1eached soils.
The zeta potentials of the tested soils were determlned with the
aid of a. 'zetameter and the application of the Helmholtz-Smoluchowski
equation. The zeta "potential test procedure required a minute quantity
of the soil.
. .
Suspension of 1% sQlid concentration by weight 8{ test
'
c
-\
'.
:..j.
soils were prepared
which contains partièles less

,
.lf;#~':lbsequently
~~~
than 2 J.'m in size, was
.
centrifuged. Only the supernatant,
used for the

,
"
electrophoretic mobility measurements. The values were corrected using
';f
the Helmho1tz-Smoluchowski relationship as fo1lows (Hie~enz, 1977):
Ç'- v t 4 ~l t (Ka,ç' ) (2.1)
r n whic~ Ç'.... zeta potential in esu; v~ '- electrophoretic mobility in
cm/sec/vo 1 t/cm; Vl viscos i ty of suspension in po ise; E
dielectric constant of suspension; and Ka - inverse of double lay.er
thickness multiplied by the particle radius.
2.7 LABORATORY LANDFILL MaDEL·

.
A laboratory landfill model was structured to ~1low for comparisop
of the different parameters (such as 'diffusivity coefficients, sorption

'-
. "
. '
f •
"
(
, ,
34
isotherms, etc.) relating ta the soil c~lumn and' actua1 landfi11 site.
( ,
\ This provided a reference point in the subsequent scalé-u~ procedure.
The model is described in detail by Lex (1986), ana a schematic
representation is given in Figure 2.8. It was designed to be 100'.!1times
greater than the leaching column. The model consisted of upper and lower
plexiglass tanks. The upper tank was designed to con~p.in the prescribed
leachate solution, while the lower\ one, was designed to hold the ,natural
compacted clay soi1. The exterio'r dimensions' of the upper and lower
tanks were 851 x 178 x 95 mm apd 953 x·635 x 133 mm, respectiv~ly .
./
The model was equipped hth 45 monitoring outlets arranged in 9
row.!!à and 5 columns (Fig . . 2.8). The first and four th columns were
des igned for pore pressure measurements which reflected the change in
hydraulic conductivity; the second and fifth co1umns were designed to

..
co11ect pore flui'ds from different levels during leachate permeation,
, -;;-
without disturbing the soil body; and finâlly the third column was
designeq for the measurement of temperature and *

electrical
conductivity .
2. S FIELD STUDY
In this part of the investigation, the effec~iveness of a natural
clay (in-situ clay) as an expedient economic liner material was

\ '
observed. The actual working landfill site studied, was located 'near
Montreal (35 knt east). lt' began operation as a dump site in ear1y: 1981.
At this site, the natural clay in- the excavated site was CJ)mpacted and
"-
used as lining maté rial. Compact ion in place was designed to achieve
lOO%- Standard Proctor density. In February 1984, ten 'sampling points
( (monitoring wells) were installed for monitoring the ear1y migrati?n of

/)
."
o
t~ t:: ~ ~ ;«.- CI
\.
.. J.o..-- 810 mm ... ; 95 -.r- '

J.- 2 13- ) 213 ' l' , 2 13 Je 213 r
'. 1
1
".!T
1
1 l'
-
" 1
1
1 \ l
1 Upper tank 1 "'-!
l ' '. 1
1 1
l ,
1 l
: ,0 0 0 0 0 -1
1
: 6 0 0 0 0 1 ï
0
1
1
1
-1
.0
0
0
0
' •
0
0
0
0
0
0
,
1
1
1
r
:E
CD
""'1
.....
" -0
~ Il
1 0 0 0 0 0 1 Dl
t , 1 ::J
l ' 1 7'
"~
1 0 0 0 0 0 1
1 • 1
t- 0 0 0 0 '0 1
1 · 1
l 0 0 ,0 0 0 1
1 1
1 0 0 0 0 0 1
l , . 1
1 . _ 1 1
~--------rh- - -~----~1--- -- - ---CC-------- L
----
•
f' 229 . « 248 k 248- ;. -229- t.
_lL -
....
---_...-
...L ...... ...
953 mm ..,40 mn1.
IN
,, U1
"
Fia. 2.R. SChernatlC Renresentation of the Land fi Il, t-bdel.
"
'\
36
. ,
.C ~ontaminants in the subsurface environment. Each mon~toring weIl was
made of a PVC tube with an outside diameter of 0,1 m and a depth of 4.0
m. This allowed the bottom of the weIl to penetrate about_one meter-
into the eiay substrate. The bottom 1.0 ID of eaeh weIl was perforated
to allow the seepage of the gr~und water into the standing weIl. Sand
was 'poured in -the annular spaee around the bottom p~rt of the well
followed by cement grouting up to the ground surface.
Of the three wells located inside the clay barrier (F~g. 2.9, Wells
..
No. 5, 6, and 7) one was located directly in the fill itself (WeIl No.
7) , ,while the other t~o were on the periphery of the fill. The
remaining seven wells were located just o~tside th~ciay barrier at

.
various locations surrounding the fill. Figure 2.9 is a general layout "
of the refuse disposaI site showing the location of the sampling wells,
the ponds (leachate basins) and the fill area.
-Fluid samples were taken from the monitoring wells at intervals of

3-4 weeks from February. 1984 unt{l January 1986. The leachate samples
were co11ected using a suction pump. Each monitoring we1l was pumped
'for 5-10 min. before, sampling to ensure that the ent~re ,sample was from
the clay substrate and did not include any water accumulated from other
sources. The samples were pumped into plastic bottles, for subsequent
chemica1- analys is in the lab?ratory. Care waS taken to maintain the
fi~ld samples at or below the in-situ water temperature to minimize r
chemica1 and biochemical changes, durihg the time taken to transport and
store them in the laboratory. "

1
Chemieai ~nalysis was limited to the determination of pH, specifie
c ,
\
eondûetivity, Na, K, Ca, Mg, Cl, HC03 , C03 • ,and TOC,> A11 analytical
J. .;.
t::> 1,' ,,' 1,
~-lo... " \.
"
o
c
-.
• 2 "
3
• 1
•
(
Flll ARE A
Natural Area Groundwat'er Flow
Control WeU - !.
'.
, . • MONITORING WELLS .:
,..
"
~
•
lliâ
BASINS OF LEACHATE
INACTIVE A~EA
(fully filled) , lN
.....
Fiq. 2.9. \~eral Layout of the Landfill Area. ..

....., '- ' , .• ~ '", - . c~· ~,~~. r :; .... - -
" "4
"
,'"
•
38
<0
( procedur,es conformed to Standard Methods (1980).
To determine the field p~rmeability of the in-si~u clay::: fhld

! ,a, "
permeability tests wer,e performed, during February a~a Ma"rch: 1984,
.,
using PVC tubes which were installed in the field at locations delected
randomly in both the oid barrier (thr~e ye_ars 6ld) and the recently
built ones. The permeant l solutlon used in these permeability'tests' was

'\\
the leacha.te collected from the ieachate basins.
/
,u
" ..
1
','
. ,
, .
"
" /
.
"
."
• J ..~
c ~ ..
" ~"
. .J
39
CHAPTER 3
EXPERIMENTAL RESULTS AND ANALYSES
3.1 GENERAL
,
The fol1owing results and analyses are based on the data obtained
from the soil columns leached with,different leaching solutions for the
J
different series described in the previous chapter. This chapter
includes .the following:
._,
(1) The effluent concentration analyses and the· breakthrough
curves, which define the characteristic saturation capacity
of each clay soil type with respect to var,ious contaminant
species.
(2) The depth distribution profiles of different contaminants
during the migration of the leachate solution through the
-
,
t
"
'
clay s~il, whiclp illustrate the attenuation câpacity o~ the
soil, and
(3) The plausible reaction and interaction' mechanisms between clay

" ,
s~il particles and/or fabric units and the contaminnnts.
Due to the complex natj.1re and the various chemical species which
J
can be generated ,from \he dissolution of the soUd waste, it is neither
facile nor feasible to detail all compositionnl fentures and
characteristics of such products. In chis study, the various contaminant
species were divided into four main c,ategories: (1) heavy metais. (2)
\ ,
major cations. (3) maj-or anions. and -(4) orgnnic matter measured ~s
total organic carbon (TOC). Because of the 'multitude of contaminant

1'1'
speci( 5,' only sorne individual contam1nants were trace,d for tntrusion anJ!
n"- '
. ,
retention in the soil columns. The ~election of these contaminants was
. ' ....,'?
40
c baseq. on two main ,.fundamental cri te~ia:
cont~inants, in the leacha~e

,
solution generated a
(1) availability of these
T the landfill sites,

1
and (2) potential hazardous effect.expected in the case .of contaminant
breakthrough t~ the subsurface ,environment. The ele~erits analy~ed in
this study 'wer~:
,(1) heavy metals: ;Fe, Zn, Cu, and Pb;
(2) cations: ,Na, K, Ca, and Mg;
(3) anions: Cl, HC03, 9°3' and, S04 ; and
(4) organic content (TOC).
\ The results and analyses are presented in two'sections:
section (Sec. 3.2) describes the l<;1boratory results and the second
the first
section (Sec. 3.3) provides analyses and discussion on the various
c attenuation mechanisms of the contaminant species.
The results were plotted in the manner of relative concentration

" '1
versu~ pore volume fraction. Relative concentration is the ~atio of the
column effluËmt concentrat~on (Ce) to the influent corlcentration
Thus the "breakthrough" point for a given element occurs when

1
. the 'coliunn effluent concentration equals the influent concentration
(Ce-Co) and has a relative concenttation value of onel. A pore
volume (PV) of effluent ;, defi~ed as the vol';"e necessary _ ~o d,l-splace
the volume of interstitial li"quid in the pore space withi~ the soil
i
column. The pore fraction 1s then given as the cUIJlulative\ volume of,
column effluent divided by the pore volume of the individual ~Qlumn.

1
c \
\
'\ .
.( \
,
A 41
o 3.2 MIGRATION OF DIFFERENT CONTAMINANT SFECIES
3.2.1 lIeavy Metals

It was observed during the characterization of 1eachate sa~p1es
that the municipal landfql 1eachate contained relatively low trace

\
elements including heavy metals. Results from leach~~g ,tests confirmed
that these smal1 amounts do not migrate in a significant way through the
different types of clay soils examined. Figure 3.1 displays the effluent
relative concentration prof,Hes for the heavy metals of Zn, Pb, Cu, and
Fe as a function of five pore volume displacements obtained from the
natural c~ay soil (Series III). The other constituents such as Ni, Cr,
and As were found to be be10w the detection limits. There was no

o
,recognized significant differenCe in, the migration_ of the ~eavy metais
through the three ser~es of natura1 soi1s. Comparing. the attenuation

\.
resul ts obtainéd from the three types of solls, heavy meta1s in
kaolinite sail ~ere observed ta be more mobile th an in bath illit~ and
natural soils. These data indicate that the exchange capacity and the
chemical characteristics of sail aL~ the dominant fe~tures controlling
the attenuation of,heavy metafs.
Results obtained from the chemical ;,analysis of the pore fluid
extracted from the sectioned clay cores were consiftent with the sail
'eolumn éff1uent concentration ~Figs. 3.1 and 3.2). The results showed
that significant amounts of the heavy metais were retained in the top
portions of the soil samples, aS seen in the concentration depth
prof,iles depicted in Figure 3.2, ' Fe ions appeared ta be more mobile
than Che other heavy metals found in the leachate solution, especially
in the case of kaol,inite clay wher, a more ~cidlc environmenç. prevalled

o 4.
J
, .....
. < ,
.,
~
"
'
0
1
42
'C , .
1 .
(j.
,
,.:....
0
ü Natural Soil
..... 4)
ü
..., 0.15
,e: '" Zn
.-.....0 0.10
\ t • Cu
tU
.....
~ 0, Pb
e:
Cl)
c
0.05
,,
• Fe
c:
0 0.0
ü
Cl)
-0
-
,',
>
4 5 6
tU 0,0 1 2 1
3
Cl)
CI: Pore Volume
- î
~
..
( l î
<1;"
\
Fiq. 3.1. Relative Concentrations of Heavy Metals (Studies) in Solution

fi> Collected after Leaching - as a Resul t of Pore Volume Passaqe
of Leachate. (Co re~ers ta initial. concentration in the
leachate) ..
1
, \.), 1
c -'
1
• 0 ' .
)
'0 I,:"~
J.,..... (
<
-----
o
,
'II>
, .
-.." 1
\.u Concentration (mg/l)
,-
QO 2.0 4.0 0.0 - 4.0
'"
2.0 40 0.0 20 6.0
0.0
-
E
,20
--
E
or:
0.
40
60 "
Cl>
0 80
, ~
too 1- .
KabtiAite lllite Natural Soil
F~ 00 5.0 mgll C.1 = 0.1 mgll

"
• • . =-
... ----~
Zn Co == 2.5 - mg Il ' Ci = 0.1 mg/l
0--. _.-<> Pb Co = 2.0 mg/l CI = 0.5 mgll

;'
r
"' 1
J..--.- - - . Cü Co = 32 mg/l Ci = 0.1 mgll
Co Ipput Concentra1ion
Ci Background Concentration
.z:,.
l w
\
Fiq. 3.2. Heavv f.~tals Miqration profiles after the DisplacetTl€:nt of 5 Pore Volumes.'
-,
~ r ~'?.~
44
~Fig. 3.35._
(
In order to>confirm these results, and examine the effect of the
high concentration of heavy metals J two additional leaching tests were
conducted, ,using two laboratory prepared permeant solutions: O.l"N

.-/.*(t 'i( ,
CUCIz and 0.1 N Pb(N03 }2' These two solutions, which were leached
through the compacted natur.aI clay soil, were sele,cted to study 4l1e
behaviour of two extreme situations: (1) the migration of highly mobile,
contaminants,' primarily Cl ions and to a lesser e~tent N0 3 , and, (2)

. .
the migration of heavy metais with l~w mobility. Also, these two'series
~ere conducted to investigate the eft'e'c,t of ~he interference of the
other contaminant species on ,the migration of heavy metàls. The results
shown ip Figure 3.4 indicate the attenuation of the heavy metal (Cu) and
the high mobility of Cl ions. Similar results were obtained for pb.
(
3.2.2 tations
6_-'}(f....; ;
The dQminant intru'ding cations at the municipal solid'-..waste
disposaI sites are the alkali ,metals' (Group lA) and the alka.~e. eart~
(f _
metais (Group lIA) 1 e:g. Na and K, Ca, and Mg, respectively. 'Analysis of
the po're fluid chemistry of the natural' clay soil used in the present
.....
study showed that the pore fluid was rich in Na ions while other cations
J
such as K, Ca, and Mg were present only in low concentrations, as shown 1

in Table 2.3. On the other hand, the cation concentrations initially
'"
present in the laboratory-prepared soUs (illite and kaoliriite) were
extremely low. These maj or cations present in the leachate solution
0Figinate from the refuse, as well· as dissolution; of minerals in the
soil top cover at the landfill. Sorne of the typical experimental results
o
of the effluent cation concentrations (breakthrough curves) for th~
.C "
, . ,.. ~
4S
o ,••____ Natural Sail
-_.-e Illite
.Â---.Â Kaolinite
pl
c: Fe ion initial concentration

.-....0
,
(Ij
....c:'"' 0.2 =5 mg/l
<1>
0
c: "
0
':ü ..... - -. .
O,1
-.....
Ja---~-
----
Q) ........
~ >
....al Â"-
_--- e...-..e-.-.- . .J..-.-e
Q)
0: 0. 0 ...---
-__e.--.
-~-
c:
•
-u.
0
Q) o 2 4 5 6
J
Pore Volume'
,Fiq. 3.3. RelationsDip between F~ Ion Relative conce~tration'and D~fferent

Types of Clay Soils. ...
"
,
..
-0
,
o
.
. '
- .,
46
c
\
\
1,0
--
0°
09
.
,
1
-
<Il
0
c: .'
-0
,,0.8 11---.... CI
-
/
as
~
c:
Q)
(,)
• • Cu
c: 0,7'
o'
0
Il)
->
as 0.1
-c
Il)
0::
0.05
0,0
0.0 1,0 2.0 3,0 4.0 5.0 60
...
/ Pore Volume
, Fiq. 3.4, cu and Cl Breakthrouqh CUrves.
--... ,
f.
.. \
-,
~.
)
47
different ,clay soUs used are presented in Figures 3.5 and 3.7,, while
the corresponding migration profiles are shawn in , Figures

, 3.9 a, b, and
c; and Figures 3.8 a and b.

, .
Figures 3.5 and 3.6 illustrate' tne wide range of attenuation
j
observed from differerit cations such as K, Ca, and Mg, which were
~ontained in the leachat~ as they permeated through the columns of

- ,
different clay soils .•The leachate solution, was subj ected to physical as
well as chemical procesl:!es as it moved along the flow path withi~ th;t'
soil column. The major cations attenuated mainly through cation, exch?nge
replaceability, e1ectrostatic ~dsorption (physical sorption), and.(or

------
incorporation
. in ta the structure
,
lattice (chemisorption). The amount of
éy\
reduction observed in the concentration of a given eleme,nt as it passed

,
through the column was reflected by: (1) the shift of the breakthrough
curve towards higher pore volumes, and (2) the extent to which the
relative cO,ncentration remained below unity (Ce/Co - 1).
Figure 3.5 illustrates the effects of the difference in so.il types
on the breakt1!rough rof d1fferent cations (Na, K, Mg, and Ca). - Weak
retentio,!! was ~demonstrated by ké\olinÏ:te clay, however, a large sorption
capacity was found for both natural and i1lite soils.
,Figures 3.5 and 3.7 disp1ay the resul ts for the negati:re
! •
at:!tenuation or elution of Na from the natural soil colu,mns, after the
.
passage of two "por~, volumes of the leaching solution. The relative
f
c~oncentration ,;'f greater than 1.0 indicates that Na e.1uted from the \
f
sail column, at a higher con~entration than that of the effluent )
l~achate. Similar results, but, to a lesser extent, weré observed for the
K ions, in the case of i11itic clay system (Fig. 3.5). The comparison of
~ ..
i, .
,1 ".",
0
48
-l'
50 [,
40 Na
30 Natural Soil
20
•
10
.. llIite
-- '00
a
0 Kao'linite
1
0 1 2 3' 4 5 6
~~
,
'"
K ..
-
20
' ·T
0
1.5
Ü
-
......4) 0
Ü 1.Q /
--
c:
0 05,
«S
( -'-
c
Q)
0
c: 0 1 2 3 4 5 6
0
0
Q)
-
>
«S
Q)
1.0
1.5 Ca
/
0::
0.5
op
0 1 3 4 .~ 6 ,
2
"-
1.5 ",
0 Mg ,
ft
, o 1 2 3
Pote' Volume
4 5
"
" Fiq. 3.5. Rel~tive CQI1centration 'of Different éations in Solution

Collected after Leachinq - as a Resul t of Pore Volume
Passage of Leachate. . )
o i";;"'''4
,,,,,,,, f " el
Natural Soil
Concentration (mg/!)
O.~ 50 100 150 200 0.0 5 10 15 20 00 60 120 180 240 0.0 10 20 30 40 50
0.0
1 J,l1 _II /:lL',{66 1.

20"
-
E
40
--
E
..c
c.
60
80 • bJ.l ta yà l '/r r r '. 1..- J. U ..

"
Q)
C.
100
Na L K Ca Mg
.
,
Co ~ Ci
mgl! ,. mgll A 1 pore volume
Na 150 130 ~ Co . Input Concentration
... 2 pore volumes
K 16 16
o 3 pore volûmes C. Background Concentrafion .
1
Ca 180 22
• 5 pore volumes
"'9 35 16 .
-
~~ ~
Fig. 3~6a. Cation Miqration Profiles in Natural Soil. \0
"
i "
-'" ~ .r-
"
C lUite
\, Goncentration (mgll)
00 .. 50 11)0 -150 200 0.0 5 lO 15 20 0.0 60 120 180 240 0.0 10 20 30 40 50
0.0
1.'- 'A
\.- -
-E
E
20
40"
~., f
~
/"
~
• 1
Li.
f{ 1
""'--':
......s:: A
.'
, a.
(])
Cl
60
80
l,
t 9 t~ (â
\
, , 100
Na K Ca Mg
• -:',
,;
. Co C;
mg/l mg}1
Â 1 pore volume
'-
~a 150 42
f.'
., 2 pore volumes
~ 16 20 '"
0 3 pore" volume s
Ca 180 36 ""
Mg 3'5 20
• 5 pore volumes
,-
~JfJ
1 -
Fig. 3.6b. Cation Miqration Profiles in Illite Soil. U1

o
'\.
~
,
~ .=- ~
l! >.,>, .~
''1''1 Ct
,. \
p
Kaolinite
Concentration- (mg"~
0.0 50 100 150 200 0.0 5 la 15 20 9.0 60
1
' 1'20 180 240 0.0 10 20 30 .. 0 50
0.0
, E - 20
--
'E
.c
0.
40
60
<1>
(:)
80
h~ ~~ + b'.
~
~
~ ~
i ly
l ~b 'a
100 l Na K- ~ ·Ca
-h
Mg .,-)
l.~'"
Co Ci
mg/l mg/l
-
i:. 1 pore volume
Na ,150 0.1
" K 16 0.1
• 2 pore volumes
./
o 3 pore volumes
Ca 1 180 0.1
'. • 5 pore volumes
Mg_ 35 0.1
",
V1
1-'
Fig. 3. 6c. Cation Mi9"rati~n Profiles in Kaolini te Soil.-

52'
c Natural Soil
,..
0
(J
5
.....Q)
(J
Na' o series
...... 4
c: • series Il
--...
0
e:!
3 T series III
-c:
0 2
0
c:
0
(J 1
al
:>
== 0.0
le:!
al
,0,0 1 2 3 4 5 6
cr:
Pore Volume
Nafural Soil
,.... Ca
0
(J
......Q)
(J
'"c:: o series
0 1.0 ~ serie~ 1/
t>:S
"- T series III
c:, ~.5
al
0
c;: o,q,
'0
(J
al
--
>
\tJ
0.0 1 2 , 3' 1
4 -5 '5
al
cr: pore Volume
-'"
. ,
" 1
. Fig. 3.7. Relative Concentration of Different Cations in . Solution
,
/'
Collected after LeachiÏ'lg - as a Resul t of pore Volume

, Passag-è of Leachate.
"
.'
"!..I J
o "
.._."!f",~
V-~t f
o
: 1
N'atural Soil
, Na , Concentration (mg!!)
0.0 50 100 150 0,0 50 100 150 0,0 50 100 150

o0 1 :::> 55>T AJ :;;;w
Series 1 Sorles Il S,èrles
20
,......
E 40
E
'-'
-'=
.- 60
C-
m ....
o
80
100
j
o • 1- pore volume 0, 3 pore volumes C,:::130 mgll

.....
• 2 porc "olumes • • 5 porc volumes Co::: 150 mgll
Fiq. 3.8a.Na Concentration Profile Distribution in Soil Columns.

"
U1
W
"
~.
~' f":-
• '-
,..
...
:>
Natural Soil' - .~ ..
~-: ...... ;
_Ca Concentration (mg/l)
• 0,0 59 too 150 0.0 50 100 150 0.0 50 100 150

0.0
20
,...,.
E 40
E
.......
-
oC
Cl
0.
Q)
60
'.
80
series III
100
,.
'--
• 1 pore volume o 3 pore volumes CI = 22 mg/'
o 2 pore volumes ~~5 pore vQlumes' Co := 180 mglt
-'
Fig. 3.8b. Ca Concentration Profile Distribution in Soil Çolumns.
f"'
~
.,
VI
.~
1····'-
1 ..
I~ 55
o FigUres 3.5 to 3.8 shows that the elution of Na in the natural clay
system and K ions in ,the illitic system ~ere followed by an increase in
/ the Ca and Mg co~centration within ,the pore space. The plausible
explanation of 'these resul ts rests wi th the cation exchange
process(es), i.e. the replacement of the Na ions in the exchangeable
sites by Ca and Mg.
,
The charge balance was maintained by the migration of Ca and Mg
ions originally contained in th~ .lea~hate solution. Crooks and Quigley

-
(1984) have shown similar results indicating that Ca. and Mg migration
balances the charge deficit due to the elution of Na and Cl ions. The
)
progression of the Ca and .Mg 'ion front ais known in literature as a
"hardness halo" which is conunonly observed in the vicinity of landfill
sites based on clay soils (~riffin et al., 1976). ,,
3.2.3 Anions
~e behaviour of chloride ions was ~tudied mainly to separate the
effects of dispersion and éhemical processes operating in the soil
system. The chloride ion a~tenuation that was observed was relatively
low, as depicted in Figure 3.9 .. This low attenuation is not surprising,

( ,,
because: (1) Cl i~ considered to be a mobile and non-interact1ng anion
(cons:rat~ve contaminant) 1 and (2) chloride ions are gener~lly

J
considered to be· non-specifie ions, (i.e. 'existing ,only in the outer
coati'ng of the double layer; Sposito, 1984): ~his observed attenuation·
is gener~lly not a function of thè type or amount of clay mineraIs ,.

'p,resent in ~e soil .-system, as illustrated in Figure 3.10.
10
. : ,
analys is \ of thé sectioned cO,lumns rèvealed low
f/f
/
..
56
c· - O' .
,
p'
, -C,)
G»
-.
/
\ Natural Soil
-C,)
c 1.0
CI ions
- 0 ~
- t1l
100
c:
Cl>
()
c
0.5
0.0
0
•
y
series
series JI
series
0
C,)
0.0 1 2
'"
3 4 5 6
Q)
- ::>
t1l
Pore Volume
"
"
.
. .~~
-
--C,)0
C,)G»
( ~ c
ta
- 0
co
.......
c:
0.5
•
Cl> 0.0 Â l/lite
()
c:
0
C,)
0.0 2 3 4 5 6
o Cl>
....co::> Pore Volume

-Cl>
0:
Fiq. 3.9 ~ Cl Relative Concentration in Solution Collected after

• f
teachinq - as a Resul t of Pore Vo~ume Passaqe .of Leachq.te.
"
'. i
- ,
.. - -.1 .. ,~""I" ~; ....
57
o accumulation and retention of the Cl ion, as seen iri the concentration-

~
depth profiles shown in Figure 3.10. This can be attributed mainly to
"
physical dispersion in the soil column, with perhaps a sma~l amount of
\ interaction at anion exchange 'si tes on the clay edges;' or to ~t&er
chemical reactions. The exchange between chioride ions an~ other ions
with negative charges, which are part of the 1a~tice, is not feasib1e
because the chloride ion is about two and half times the size of the
,ft '!
"
oxygen ion, i.e. it is too large to r~place or coordinate with oxygen
/'
and hydroxyl ions.
The breakthrough point of chloride ions in Series III was observed

,
at about 1 ~5 pore volumes. However, for Series land II the'
breakthrough points were at 'about 2.5 and 3 pore volumes, respective~y

, ,
(Fig. 3.9). This can be attributed to the change in moisture content
which influenc~s the diffus-ion in the clay water system. Yong and
Warkentin (l~75) pointed out that with increasing water cC!lntent, the
hydraulic conductivity as well as the diffusivity will increase. It was
.. also ,indicated il'!; Figure 3.9, that the effluent reached 20% chloride
concentration at only 0.4 pore volumes in the

, :>
case of kaolinite soil, and to a 1esser extent in the' case of ilUte
,sotl, 'where the breakthrough point was reached at about 2.0 pore
volumes.
The resu1ts shown in ~igure 3',.9 (for 'the -nitural soil) suggest
that migration progressed furtq.er in Series l and II than "in Series

1
rir. The chloride profiles indicate a Larger concentration of chloride
than sodium. for example, at each depth. The charge balance was
maihtained by migration of natural Ca and,Mg, originally contained in
the 1eachate solution. This observation is supported by the profiles of

~,-",.
;.:(~
' .,
'~
"
11
t/
f""t: .., r\ -~~
<fi
.,'
Natural Soit ...

"
. '
.
\,
CI Concentration (mg/Il '"

" 0.0
.
50 100 150 0.0 50 100 150 0.0 50 100 150
C"
0.0 1
series series
20
~
'"'
E' 40
E
'-'"
-
..C
o
0.
Q)
60 .,
series III
,.
80 .- "
~ 100 ~------------------L---____~__~____-l________~~__~~~
•
Â
,';
'. o
•
Fiq. 3.10. Cl Migration Profile Distribution in Natural Sail Colurnns.
J>
111
00
•
'-
.... J
59
o Ca and Mg, which
above the~r ~nitial éoncentr~tions.

ind~cate lar~e
~
increas
,-,
in Ca and Mg concentratiobs
Exactly the same pattern of results

\ • 1
\ was obtalned
J
for illite ana kaolinite s~ils.
\\
•
. The thr~e other anions examined. during the course of
,
th~s
. study
were
G
5°4 , and ,RC03 •

.
It was observed in, the preliminary
-1 1"
investi!ation carriéd out on the c~lect~d leachate s6lution, samp1ed
f"m the leachate. basins J that the concentrations of S04 and COl
w~re belpw the detection limits<of the experimental procedures. There

•
are two phenomena whicli can contribute to these findings: (11 the redox
éonditions t.1ithin the land'fiU and/or the 1eachat~ basi~s 'were

J
sufficiently' reducing. and this in turn preveI)ted' the formfl'tion of $04

o •
from any sulphur compounds possibly present in the solid waste. . (The
. .
~tendency in the geochemical system, however, is towards oxygen depletion
. , l
and reducing ~onditiong). And (2), the pH range of the gene~ated leachate
solution wa~ in the range of 6.8 to 7:1, which usually favours the
\ " , -
"
formation, of RCD 3 compounds rather than C03 . ,
v • "
ReO l , which represent.s most of the dissolved inorganic carbon, _
was thé dominant anionic species found in both the leachate solution and
• 4
the pore fluid extracted from the leached clay soii columns. Figure
3-,11 illustrates the migration profÜes of HCD 3 in the natural clay,

"
·,illite,' and kaolinite soils. No definite trend was,observed, ·however, an
incre~se in the He0 3 concentration in the int.errnediate ;;ections was

a
recognized in the natura1 and illite 50 il co1umns. Furthermore, in the
~
case of'kao1inite clay, litt1e.HCOl was detected in the extracted pqre

. \" , ~ t ... "t
f1uid, aftet leachate migration. (tt shôuld be noted that the pH vaiues
"
for the leachate s.olution were .in the range of 6.9 to 7.1 wi th an'
-/
"o
" '" 1
"
,.. J ~ ". r'\
')
(
<;
...... "-
"
')
"-
\
.
Je
,: Conéentration (mgll)
0.0 100
-
200 300 100 200 300 100 - 200 300
0
.r
·20
/'
"'40 =
_
e'
-....
E
. c 60
a.
"
(])
..0
"
80 f
j
1
100L,~~~__~~~~~~JL~______________~__-L__________~____~__~
\
'-- Natural.Soii Itli~e . Kaolinite
o 3" pore volumes
" , ,
• 5 pore volume's (l> .,,;~
.,~
.',
Fig. 3 .11. ReD Miqrat~on .prof~les after 3 and 5 Pore' Vol,.ume Displacement •
3
.. m
-->----- ,
.
. o
"
.....î
'-
'ï·
,61
o average value of 6.9" while the pH of the soil co1wnn effluents ,were in
the range of 8.0 to 8.5.)
The trend of Cl/HC03 (disso1ved inorganic carbon, DrC) ratios_
calculated along the migration profi~,es for both three and five pore l
volumes, suggested a loss of bictirbonate within the soil system (both'

, '
aq";:eou~ and soUd phases). Figure 3.12 shows a comparison with J the
béhaviour of the chloride ions. lt was observed that the balance
between Cl and HC0 3 was maintained a1most' consta~t, although sorne

'111"
minor differences were observed.
/
3.2.4 Organic Substances (TOC) /
Leachate solution. generated from the- dissolùtion of the, buried

,
""solid waste at sanitary 1andfills, is usually- characterized- by the
prese~ce of a '-high con~entratitm of organic compounds. The organic
content in most ~ cases accoùnts for about 40 to 60% of thé t9ta1
constituents. In the case at hand (Lachenaie Landfil1) , however, the
organic fraction was re1ative~y 10w: on1y l{) ,to 15%. These organic
compounds usually consisted of the rell!ains of biologièally-produced
compounds of low molecu1ar weight, principa1ly fulvic acid, in addition
"
to a variety of synthe tic organiè contruninants (Appendix B, Sec. B.6).
Such organic substances were found to be high1y mobile in a clay-water
system and,presented a veritable thréat to groundwat€r ~u~li~y even a~
very low concentrations.

JIÎIIt>'
figure 3.13 shows the attenuation 'observee} in the organic load
containeo in the leachate solutlon as it passed through the columns

,""
1
containing the natural clay (Series .1_, II and. III) as well as kaolinite
,
and illite. Little attenuation was found' for the organic 10ad meàsured
)
"
- -~.
(-
20 • 1 pore vblume
o t
• 5 pore volumes
o-
_ 1.0
00
, 00 20 40 60 80 100
Depth (mm)
(
li'"
2.0 ' .'
•
CO) Background Concènfration t
--
0
( :c 1.0
,r
0 '" o • '1
00
00 20 40 60 80 100
\ Depth (mm)
,
~iq. 3.12,. Ratios If Chlo~ide to Bicarbonate along the' Natural ;lay
. Column Depth, -
1.
'.
«" (
"
..
....
J
63
-§ TO,C
Natural Soil
~" 1.0
-~
r::
(])
(,)
0.5
o series
c
o 0.0 • series Il
(.).
... series III
0)
-
>
CO
03
0:
0.0 1
/,
2 3
1
Por'e Volume
4 5 6
•
/
,r
J
.' \
• I\lite
KaolinJte
c
-ë
o
'CO
~
1.0
0.5
-0)
(,)
c:: 0.0
o
,J' (.)
, 2 3 5 6
Pore Volum~
Fiq. 3.13. 'Iœ Relative Concetltration in Solution Collected after

/ . Leachiri'q - as a Resul t of Pore Volume Passaqe of Leachate.'
•
.'
• •
1 .
64
/
as total organic carbon (TOC). The breakth~oùgh point for TOC was
\
observed at an average valué of 2.5 pore volumes. This result was i~

1
agreement with the results of of Zanoni (1973), who reported pbor
removal of ehemical oxygen demand (COD) wh en leaehate was pondeçl on
soUs.
• ,1 •
Fi.,gure 3.14 shows tl1e TOC mlgraUon profiles in the' natural sail
(S~ries l, ,II, and III). In these leaehing co luron experiments, the ",,'
. , 1 \
landfill leachate, w~th an in~tial TOC value of 190 mg/l, together with
othe:.:: ionie species, was passed through the cl,fly, columns under a low
hydrau1ie gradient of 21' From 20 to 30% of, TaO removal was observed
after six months of l~achate solution displaeement (5 pore volumes). The

.,
~inor differenee~ observed in Series' l, II, and III co~ld be due to the
c var,iations in the individual samples.

,.
obtained for i1lite sail and to a lesser extent for

.. 1
Exact:ly the same results were
k~olinite soil (Fig.
3.13). This removal of TOC could be-attributed t6 the complex formation

... '. \ ,
of",organi~-metallic ions,' sinee organic, matter adsorbs metfy i<?ns
'better than clays. This ,can, in turn, expl!in the high remo~al of heavy
metal ions found in the present study (as previ~usly pointed out in
Section 3.2.1). . In general, adsorption was found to proceed 'ln the
following order: organic matter> il1ite > natural soil > kao1inite.
't
\ . \
•, \
,
~ ,/
/
.,
1
1 /
1
\ \
'
(
1
!
.... _. __ -::-_ 1
f;t
....
t·_~
_'fi
0\
t ~
o
"
v
.. c
Natural Soil
TOC' Concentra lIon' (m'gl/)
0.0 50 100. 150 0.0 50 100 150 0.0 50 100 150

00
1
'Series 1 Sef'os JI ---= Series 111
o
20 .,.
......
E 40
t (/! 1 ~ .-
E
......, D • • .,#
.c
...... 60
a.
Q) ....
0
80 . .' \.
-.. lpO
--- , • 1 pore=---volUlne ~ o 3 pore volumes Co-= 190 mgll ~
t'
Q ·2 pore volumes ·t~. 5 porc volumes CI =50 mgl)
. ...
.~Fig. 3.14. TOC Profile·Distributions in N~~.~~_S9jl Columns.-
Jo
~
..
':$,
./
0\
,.
111
l!>
"
,''- '" J _ ,
66
c 3.3 ANALYSES AND DISCUSSION ON THE CONTAMINANT SPECIES MIGRATION
3.3.1 Attenuation of Heavy Metals
The retention or removal of heavy metals in clay soils depends on
their types and concentrations, and the carrying capacity_ of the sail.
The mechanisms should,thus include:~ (1) association with the surface of
clay soil constituents (due to the. cation exchange processfijl and

IQ • \ l .. ,
-adsorption), (2) precipitation and/or filtration, and (3) incorporation
with organic compounds and/or hydro,us oxides. These mechanisms are
interrelated and operate together for the ret~ntion of heavy metais.

-
'"
Chemical and analytical analyses on the soUd and aqueous phases ~ere ,
cond~cted to determine the more dominant méchan:î.~m givi~? the. 'observed

results.
The,removal or atcenuation of heavy metals could be attributed to

( the~cation exchan~e
.'
processes due to the high replacement ~apacity of-
-'
Zn, Cu, and Pb \ ov~r the o'ther cation species. In natural soil, the
calculation of the chemical equilibr.ium, which Is based" on the mass
\ \
\
, ~ctit)n' and mass ba1.ance equations: revealed that 'the solid phase (clay
soil)
an associated
o~ the top layer of the leaching column had a rnass of 184 g and
C~C of·l09' milliequivi~lent (meq) , which wa; capable of

,
'âcçommodating the" lotor input of the heavy metais (0.70 meq) on the
1',
charged igntc sites located'on the surfaces of clay particles .
.
Nevertheless, in the landfili site ~nd simulated models (leaching.
l ,
Ic~lumns
, - and tphysical model)' r pre~ipitation' and/or filtration mechanisms
c
appeared to be the more plausible cause, based on the increase of pH
1
1
values (generated by the reduction reactions of organic matter): The
, ,
\
~ /precipitation which occurred in this s tudy could play a role· in the
,1
. 'r
., i
,\
1 j !
)
... :~
67
o formation 'of heavy. metal oxides 'or carbonates, brought about by the
, ,
,relatively nigh pH conditions found in, the column effluents.
'
The pH
1
values for the leachate solution were in t_he range of 6.8 to 7.1; with,
, .
an average yalue of 6.9, while the pH of the effluent columns was in
~ 1
the range of 8.0 to 8.5. The increase of pH and the development of the
oxidizing conditions could result in precipitation and/or complexation

1
'of heavy metais with the soil constituents, which would be in

, . . )
~
accordance wi th ~ong et ~l. (1986) ~ho observed that increasing pH
values caused precipitation ofr insoluble ferrous compounds, or the
oxidation of ferrous ions whiéh precipitate as fer~ic compounds. Also,
at this relative-ly high pH vâlue of 8.0, the concentration of these
heavy metals was so low (due to the low solubili ty) that very Uttle
would be re,tained on the cation exc:hange complex. This is supported by'
the finding that most of the h~avy metals were detected in the extracted
,-
p<;lre fluids. The other factor controlling thla relative dominance dt .
precipitation over the surface sorption react{ons was the presence of
carbonate. In this stu,dy a relatively high carbonate' concentration of
85 mg/l (in average) was found.
(
~
~ t .
Filtration of heavy metals from the leachate solution by clay soils
1• tJ '"
~s another.possible attenuation mechanism. Nevertheless, experiments, in
which the natural leacha te wa} ._fll tered thr~~h a O. 45pm pore size
,
~embrane, indicated that only relatively small amounts of these metals
were :J:"etained on the membrane'. It was therefore concluded that
filtration was n~t an important attenuation mechanism for the removal of
"t;he heavy metals in the present ·study. .

Similar ,resul.ts were also
,~
observed by Gr~fin and Shimp (1978).
., <- J
, - ,
, " " f.,~ ..
\
68
C: \
Orga~ic matter
lI- r .." )
is often regarded las a, maj or activator in the

J
sorption of heavy meta1s. This is,based on the che1ating abi1ity of sail
\ o
\ organic consti~ents. The total organic carbon in the pore fluid an~ the
întruding leachate solution was in the range of 150 mg/1,which could

.
contribute to the reducti'on in heavy me'toii concentratio,n. The
interaction of organic-metal~ proc'eeds in one or more of the following

" /
forms : (1) ion E!xchange, (2) elec.trostatic attraction, and (3) ion- /
E
dipole interaction and coordination. The interaction can occur directly
between the metai and the giv~ organic molecules or indirectly thro~gh
\
a "water bridge Il •
-'
The sorption of heavy, metals
1
in soils is based to sorne degree on
the characteristics of hydrous metal oxides. These oxides'are common in
soils, e.g. the natura1' soil used in the p~esent study contained 12-1~~
c of meta1 oxidés. Many of these hydrous oxides have an ill-defined
structure ,runorphous) and·composition. They usually(have high surface
v areas in relation to their weight (speoific surface area) , and are
highly reactive. The presence of these h{drous m~tals in the natur~l
soi1 co1umns can contribute to the removal of the heavy metals on the
). ~
\ top J.ayers o~ the soil, during the mi'gration of leachate solutions. '
With the Increase of the pH values, a complexation of multivalent cation
with hydr~us oxides will occur main1y due ta proton-exchange reaction,
with the <protons derived from weak1y aci~ic surfa~e-OH groups (Yang and
Ohtsubo, .1986),
/
_Adsorption of heavy metals 1s more pronounced in the presence of
anions such as Cl and S04' as 9-epicted in Ffigure 3.4. The raIe of

~
c: anions in the adsorption of heavy metai ions can, be delineated by

r , .....
.. .' .. ,
\ , ::~
69
o "
~ considerin& th~ followi;ng:-(l) anions accumulated in thé double layer of
a p~sitively charged particle, accompanied by, Ji compensation o.f the
double layer potential, (2) the approach of metal ~ons to the soil
~
sur fàce, faci1itated?y the accumula~ionoof anions (Hodgson, 1963), and'
(3) complexes formed getween heavy metal ions and the already adsorbed.
aqueous,anionic l~gands.
In summary, the main factors. responsible for removal of heavy

,/ i ,
metals are: (1) an increase in the pH value of the pore fluid'a~d column
\
effluent, (2) the'presence of a relatively sufficient amount'of organic
carbon, and (~) the presence of anions and hydrous oxides .. The findings
from this' study suggest that the low teve~. 'of heavy metals in the
municipal landfill leachate studied will not "pose a substantia1 \
~,' .
contamination threat to the subsurface envirorunent; provided a ~ow
.Jf
- acidic envirottment is maintained. It should be emphasized that care must
b~ 'given ta minimiz~ the disposaI of acidiç wÇiste in these landfill

sites, since these c9uld increase bath the mobility of trace metals, and
those contaminants ,already retained in the sail pores.

/'
"'
3.3.2 Attenuation of Cations
\
There are many factors, such as (1) properties of. the ,sail, (2)
, .
~ characteris~ics of the solutioh transpor~ system, and (3) reactions"of
.
the specific polluta~t, that determine t~e shape of the b~ea~through
-/
curve of the cation species. Ideally J only a few of t.hes~

)
characteristics are primarily responsible for the rate of movement that

.. ~
determines the final shape and the breakthrough.point. The present study
\ .
examines the ~ffects ~f
,
water con\ent and
,
sail' cation,exchange ~apacity
cations species attenuation~roperties. Cation exchange results
"
\
i :~, ,v ~ "
70
in the storage of some cations on the exchange sites on the clay
surfaces, and the r,elease of other cations to the pore fluid solution.
The quantities of cations exchanged along the flow path cAn be estimatçd
by determining: (1) the cation-exchange capacity of the clay soil mat~ix
in the leaching' co11lllIlIl, an~ (2) the chemica~ equil~-brium between the"
~nput cations anQ exchangeable ones. The ~hanges in the net storage of
cations on exchange sit,es in the sail columns' can be estimated using

~ r
the standard mass balance and mass -action relations, as weIl as
selectivity coefficients. These approaches will be explained in the

, ' . l ,
subsequent sections. .-
3.3.2.1 Water Content and Attenu~tion Number
~r a given catron spec'1es, where the initial soil conditions

..
varied, the reduction in the relative concentration of the pore volume
.
c 'displacement changed with the water content at which the clay soil was
compac'ted. This phenomenon is illustrated in Figures 3.7 and 3.8 a and

\
, b as a comparison betwêÈm S~r,ies l, II, and III .(which included the same
.)
natu):'al soil but compacted at different initial water contents). The,

"-
.. higher the water content,. the. faster th( relative concentratiQn of a
\ .
specific contaminant app~ached unity , as demonstrated in'Series 1. ~e
nat::ural clay soil compacted at 'a higher compact ion effort (35
\
blpwsjlayer of soil) was associated with substantial deS[e"ases in the
hydraulic conductivi ty, ,which influenced the behaviour of the migrating 1

contaminant species (Series II). The test results of the natural clay
system indicated that the breakthrough point~, for different cations

1
studied were obtained after the passage of an avèrage value of about 3.0
pore volume (Series II

and IJ' For Series l, however, the "
..
breakthrough point shifted towards he value of 3.5 pore volume, due to
\
,.
71
o the re~ction observed in the soil
contents slightly ab ove optimum.

co~es.permeability compacted at wft~~
\
\
\
\
To quant ify the attenuation observed, ,the relative attenuation
number (ATN) was used~ The ATN was calculated by integrating the area '
i •
~der the breakthrough cUrVes, between pore volumes 1.0 and 5.0. The (
,
, "
area between 0.0 and 1. 0 pore volumes was eX,?lude,d because it

;. 4 " ..
represented the displacem~nt of the distilled water initially present in

•
the soil columns. Thus, the total area was that area bounded' by four
pore volumes ~.O to 5 pore volumes) and relative -concentrations
(Ce/Oo ) between 0.0 and 1. O. The relative attenuation number (ATN)
was t,hen obtained by s,:btr:acting the area under the curve from' the'
total area and was then expressed as a percentà:ge. .Th~\. ATN numbers
express the relative mooilities for each element through each particular
_ :- f' 1
clay system. The attenuatlon number was computed for aIl soil columns
and each chemical èonstituent studied. ,The attenuation number for each
'chemical cons,tituent wa~ used to ;rank the constituents according to

1 , /
their relative mobility through the clay columns. The resu1ts, given in
, .
Tabies 3.1 and 3.2, demonstrate the low attenation
. and the high mobili~y
of TOC and the other ionic - species such as' K, Mg, and Cl. On the other
Î band, t~e results .. l'tighlight ~he high attenuation and low dl'obili"ty of
the boar .metals (Pb, Zn, Cu, a"" Fe) ..
3.3.2.2 Mass Balance an,d ~he Relation between C:luted 'and Retained
(
Cations
,Figures 3.5 to 3.8 show that the tbtal amount of each element
eluted'(leached out) can be calculated using the mass balance concept.
·0
",.,.
In arder ta apply 'this concept, it 15 necessary to consider: ,( 1) the
- .- ., .. -.,.. .,. -_ ... _- .. .. -:" .. ~ -, ~ .. -J "i-".~" Ii; 1-~·"'·"\ ..,... ", ..
~ ~ l '
;'
,
1
72
• ,1
.. ,
.c" TABLE 3'-. l ,Mean Attenuatio~ Number (ATN)*.
r
Cbemical ATN
Cons t ituent Natural Clay Soil lUite 'Kaolinil:e
Series l Series Il Series III
.' .
"
". "
'.
c
. .', ,
"
i 1 1
r
. 9 ; 1 ,.
1""·
", {
f
,. !
~
1
73
o TABLE 3 .. 2
.
/. '
1
1
Rank of ChemLcal Constituents in the Leachate.
According to Their Relat,ive Mobility Through

, ,
}
1 Natural,Soil
e
....
'\
.
: 74 .,.
p
.
input concentratibns (C) (2) t;he total amou~ts ,of each element,
o '
... retained, soluble .and adsorbed (Cs, and CA)' and, (3), the measured
ft "
cation exchange capacity (CEC) ~f the sail system.
The amount of the retained ions ,was estimated from tl're effluent
analysis and breakthrough curves. This wa"s compared ",ith t.he amount> of
i0!1s measured in the" pore fluid (both exchangeable and sQluble !pns)
which were determined on the sect'ioned soi.l cores by means of.,. migratioh
. profiles and adsorption isotherms. A sample calcula,tion is de~cribed' in
Appendix D. The different elements considered in the mass balance
c,alcul,ations were determinid as, follows: (1) thf: area under the
breakthrough curves gave the total amount of eluted tons (CE)' (2) the
. \
area bounded by the initial and five pore volumes m:i!gration pJ;ofiles
-. - gave the total retained ions (Cs), ~nd (3) the amount of adsorbed ions
was .established from the relatdonship between sorbed and soluble ions
"
(CA)' The estimation of these retained ions by mass balance .procedures

~ ,
is of grea!; s ignificance when calculating the required depth and volume
of the clay soil:-'wHich would be required to perforÏn effectively as a r
barrier system in the l~ndfill site (Yong et al., ,19~6). For

II'
aonve~ie~e~ the method used in the mass balance calculation is divided
,. 75
into steps, as schematically dtagramea in Figu~e 3~?r-
...
Th~ results of the mass balance determination agree fairly !"ell,
within the range of ±lO-20%, for most of the ions studied

1
(Append i'f, D) . The descrepancies between the input: ion concentration

.,
(Co) and: the summation of the eluted, soluble and adsorbed ions (CE
1 • ,
+ ~A) could be attributed ta the following mechanisms; q

1 -, ~ •
1
(1): The effect of the bottom boundary condition,. in the.. migration
} ,
1
1
j
-;1
~
1
~ .:
, J
i ~ 'fI\
" .
Con~.
Il '
.--
",'
( Input CCI
-.,
'\
-'-
,. ",'
~
"
•
Eluted Ions \, Retained Ions ..".
-
Effluent (CE) (Cs) 1~ ~
"il
00
conc Co \ ads
00 f t
o
1,0 q
J:
'j
oC
1"
/ )
o 1
+-'
a.
+-'
-a.
0, 0,5 • ,', ", .. 1 a> 05 'a> 05
:::;: GI?:Z: ~~ ,!.

-0
'f c.o, -0 1 C
."" '.. :.~:
, ~. ,
<2
00
2 3 4 5 1 a ~. -.;~~.~.~ ~~ 1
10·l
L'" A
\
--' -----
tpv 5pv
t!
AV "of
." l
1 .... ..
, T
-"'-
, .~ ,\
c. 0-- C + C + C ±. sink&1 or source
E SA,
1
,
" .,
- 1
r e.g ,Microbial Action e.g Elution of Ions ~
,
~
ln
F1Q. 3.1~ Schema,iC Flow Sheet of Mass Balance Calculatio5.
,.
t
, ... 76
,,/
p~fi1es shown in Figures 3. 6 and 3.8; and more pronounced _~lJ,

\'>
Figure 3.16 (layer 6). Th; profiles in Fi~re 3.~6 have been
deliberate1y drawn to highlight the problem which can arfse

,."
(Yong, 19~5; Yong et al., 1985)' due to: (a) void p1ugging
"
effects at the bottom bpundary, when fine particle sieving
occu~, and (b) a much, less permeabl~ayer encountered at the

\
• bottom boundary '. lt should be noted that fine particle sieving
or void plugging can occur either because of the high hydr~uli~ fi

~ ,/ :;
grad:itents used in 1aboratory experiments or because oi self-
dislocation of the soil particles in, the' fac-a of changes il(),
po~e
"
fluid chemistry.
(2) The'reverse movement of the leached constituents due to the
osmotic gradiènt' built. up between the top -and bottom of the
soil co~e. Thi~ gradient arises due to the inorease in water
cbntent in the bottom end ef the core as a result of the

•
migration o,f leachpte solution and tlfe retention of the
different ionie species,
, '(3) The presence of miero- and mac.ro-pores within the sail

,
The experimenta1 observations indicate th~t the
\
strv-c.ture.
cont{iminant speciés passed' through the interconnectèd
macropores in the cbmpac ted clay cores; re~ul ting in
breakthrough curves -close to unit y (C./Co '" 1) in 'most

.. 1
of the cases studied; however, the migration profiles did no,t

, , -
reach the saturation ~tate (Figs, 3.6, and 3.8), and
,(4) The effects of biomass' interference,

, (
which would èonsume some
of the nutrients such as K, Ca and other lons lin the soil

'!!
- "
- ,
" .'
1
,
.' 77
c \ . ,(
'-
_ '",or' !',/
Migration profiles ~ - '.

of éifferent contaminants
C (mg!.!) ;0
Layer
. ,..... 1
E
f
E -+-_ _ _2_ _ < Saturation Lirie
-
.c.
o
0.
--~.~ '-,. ~I-:+--I--I--!--"':"-_
3#
6
C b \ l' \ \ 0... ;pv d
1 pvd
, ~, 1 3 pv d
) 2 pvd -
J
C -;:: Baëkground Concentration
b
c=
o
(input) influent Concentration
,
-, Fiq. a.16. Schernatj,c Diaqrarn of a Typica.l Miqration Profile.
~
, .
,
\'
/
..
',,-
78
o
, 1
system. 'For example, sorne of the a1kali me'tal,s; particu1arly

\
i,
K,P~an be' attenu'ated by inc'~rporation in the mierobial biomass,
,
-"
as "estab1ished previous1y by many inve~tigators ,Campbell et '"
, . ..
(.
ai., 1983).\. AU the conditions required Ifor the growth and
reproduction of microorganisms wer~ pr~sent (such as low
leachate migration veloctties, ~equired ~onutrients, and the"

1
existerice of fine grained soil media). No attempt, however, was \
\~
made to de termine these effeçts, and ~nly this assumption ls
based.. ~m qualitative observations only.
, 3.3.2.3 The Relation between Soluble and Adsorbed Cations
:; In the -claY soil systems,
removal of ionie species from the pore fluid.

adsorption processes result in the
~
An incréase in the
~ .... concentration of these ions at th~ clay surfaces .wil1 occur, unti1
--
~~~
~
il
E~
dynamic equilibrium is obtained between the species remaining in the
~ote fluid solution,and those at the sail surface. ~nowing the relation
betwëen soluble
"
anr ~dsorbed
.
cations 'for a specifie system (i.e. 'for a
certain type of ~il and contaminant)'adds ano~~er ~erspective to the

. \
1
mo~eJ.1ing procedures of the system. The adsorption isotherm can be
utilize~ ta ~xpre~p the equi1ibrium,distribùtion of Sand C, where S is
the amount of solute addorbed at equi1ibrium per unit weight of-so1id
'ads~rbent (clay ~on), and C is the concentra~ion of solute remaining in
the pore f1uid €lt equilibrium. By means of the adsorption isotherm

. , ,.
reiati~nships, the re~a~~ation function R(C) - (1 + pla B(C)}, as weIl
as th~ ~bufferi:g capacity,\ B (C)-(aSla~Ould' be fairly wel{'
." èstimated,·where p and a "

are the density and porosity, respectively.
Thèse ads~tion isotherms have long been used and described by a number
t. -
'-
,, ,,
, J" ~ A
.' '.'
79 "
, , ..
of inve~tigators (SpQsito, 1979; Horford, 1978; Parker et ;à1:, ~984;
:
, .' ."
and,~~ickhoff'et al., 1979). Somè of tHese adsorption lsotherms are
reviewed in more detai~ in Appendix Band AppendÛK C.

;'
t
[ ..... J." ...
...
, The mo'~t' popular adsorfl'tfon eisotherm model usuallly used in ~ ,
~? 1 ., 6'
a#'sorption #udies of soil is the Langmuir model. Even. with its
. '
, ,
"1
,
,.fil
d'eficienci~s and
z
limitations,
1
this model provides informat,ion concerning
the mechanism by which some contaminant species are retained on soiL-

,
surfaces. Theo\etical~y,
1,
t6 the
~J
the Langmuir model is n~t a!~L:able
r 4
\, ,
mechanisms contr~tling the retent~Qn of sorne ions, such as those in
1 ~
soi1, even though ex~erimental data for many. so11s have bean shoWn to be'
, '. the quàntitative form o'f, the Langmuir equatio}l (Mansell and \Selim, ....
"
.'
19SÏ). , '
~
The 'Langmuir adsorption isotherm model is based on the fo11owing
.
"
assumptions:
(1) Constant energy of sorption,
'(2) The adsorbed ions covering aIl the .adsorption sites 'at a1l
times and forming no more than a mono layer on' these sites,
•
(3) Uniform and localized adsorptiQn sites, i.e. the adsorb~d ions,
1
regardless of species, must not ~nter~ct with one another, ~nd

..,
(4) The ion exchange process involving t~e replacement 9f a single
ion by an~thèr single ion.
~
l
The validit:Y-'of these asswnptipns is questionable especi,ally tif the
Il
assumptions are applie,d .~o the natural soil "System in contact with a .f.
•
".
.. .. t
nat~ral leachate, ·solution. F'Or example, sorption. of different

•,
"
1 ) ,-
-
contaminant species lS frequen~ly observed t proceed to an ~tent that
tl. ! , ' $ ~
'" . capacity 'of the so 1 sut.face (Adams on , 1963').

exceeds the monolaye,r
,~
, . ..
\ '
......
"
• 1
J. \. .
•Î
.
}
80
Manse11 and Selim (1981) have' stated that physical sorption which may
I;a,..
form mU'ltilay~s of adsorbate, i5 not ioc~1ized, and undergoes weak and
,
(non~peci~ic bon~ing. These observations contradict assumption numb,er
(2). 'Holford (19't8) in~licated that

. observed curvilinearity of the- linear
,
\
, ,
transformation of the Langmuir isotherm is simply caused by the fact
- - ' .
.
• that Langmuir' s assumption of uniform sorption e.nergy over the entire
,
s6rption surface d6es not.hold. Thus, one must consider the occurrence
\
of a nonuI1iform sorption energy in a naturaL soil system. In these
". - circumstances the Langmuir tra~sformation of the lsotherm to linear form
will produce' a curve .ather than a s't7raight lil1e, because the

f'
~dsorption of contaminant species occurs s~multaneously on aIl surfaces,
in addit.fôn to the interferènce caused by the desorbed ions. The
attempt by Harter (1968) a1jld others to -resolve the curve into two
Jtraight lines ls not

, valid, bec~usé this procedure asSumes, t:hat
, "
"
adsorption on the iow energy sites occurs after the ,adsorption on high
energy sites isocompleted.
Having mentioned t h df!

e ; t ency a~d limitations of the Langmuir
model it is clear that the PI~cation of this model, or any similar
exist~ng m~dds on the be iour of the natural system, will give
predicted adsorption 'values with sorne shortcomings. These shortcomings

,
can ce attributed ~o the complexity of the natural sys~~ and the,chang~
in soi~ properties and its response behaviour due to the interac~ns

~f
establishec1 during the, le:achate migration through the so~l system. It
could be more signiflcant to come up with\an adsorption model

. fo~ . each
"
, individual system using the sarne adsorbent and adsorbate as weIl as in
the presence of other competing ions. Th~ procedure cou1d allow for
the effect~ of the forward and backwarq reactions (Le. adsorption and
l .
j " .
, ,
.,
.,
81
deSO~tiOn proce.~es), "
An attempt J1s made .Ï-Il: this research. to describe mathematically
the reiationship'i between the s~luble and exchangeable cations

• 1
1
experimentally. delrmined in natural clay. illite. and kaoîinit~ so11s,
Figures 3.17, 3.!ld and 3.19 display the relations between the soluble
(C) and exchangeabl Â (8) for Ca, 11g, and K. A mathematicai functicm of
.. {\.
the form: , . ~
8 - G - B ex~ (a C) ...
(3.1)
,
was feund to describe the behaviour and the response of the natural ~
. \ ~
system fairly well; where, Sand C are the exchangeable and soluble
cations, respectively; ç, B, and Q are constants. This fUnction seems

.,
to overcome the disadvaqtage of the-previous modeis.
J
( The constant G depends mainly on both the type and characteristic
of. thè compacted soil medium, as weIl as on the nature Qf th~ solute
(contaminartt species). This _c~nstant takes into account th~1ffect of
the e"change capadty of Ilhe soil system, It should be noted that the
value' of the constant G changes with each type of soil, as well as wi,th
each tyPe of in terac ting lions. For example, the natur~l clay soil used
in tbe pres,eut study was found to have GCa - 0.01. Table 3.3
summarizes some of the G values detepmined in the adso~ption study.
The B constant depends mainly on the i'nitial conditions of the
system:
At C - 0 , G-B .. 80 (3.2)
.
~her~o is l' the initial adsorbed concentration contaminant
J
\
.:; "'---- l
t ?:';
.)
1
,et
"<> ,
, \~
.. 010
Fig .. 3.17. Relationship between Soluble and Adsorbed Ca Ions. '" .",
,
,
<
z
0\.
0.000
, '0 40 80 120 160' 200
SOLUBLE Ca lIONS (mg/I) <Xl

I\J
j.
~
'---,
~- ~ fI\'
o
• - 1
_J
,1
r l'
Fid'~ ~.18. ~elation'ship betw~ren 'Soluble and Adsorbed Mg Ions .

. 010
~
e
f'
~)
.008 ,
-~
...J
Predicted' (3
(1) SERrEs' II (NATURAl SOIl) r}

:z ,.006 1- ~ .-
0
H
.; B .:nO .005
Cl
:E r.
œ,'" ca-O.U29 l(m9.
53
-al
" 1
~
,
'\
...
CI:
0 , .004
Langmuir G 1. = 0.007-
en ,<'5' ,r .--------- -~
a
<1: "- il
Smax ::; 0.004 ...
1/K ca 1.465 mg/,l'
""'- 1,
1·
.002 ,
....'"
~
-:
""ü-
"
... '" a
:l'- L ,. _t __
0.000
o 20 40 60 80 -. ~ -100
(Xl
\il 'e~
'J w
• SOLUBLE Mg IONS (mg/I)
",'
...
. ,1
/
... l,
f
t::t t: ~ ,
~
If'-'i
_,.l.
'"
-'-
--
. 1 ~
Fig. 3.19'-RelatJonship betllleen Soluble and Adsorbed K Ions .

- ~
. 010 ~(
0-
/'
" -
,,-
.OOB .,
~
SERIES II (NATURAL SOIl)
]'
1. a 4 0.002:
'"
-00
:z .006 '$ ct =-0.050 l/mg
o
H G = 0.003
~ '\
'l'
a Smax = 0.006
w
ID
oc
o
CI) .004 "
~ ,
."
1/K = 2.BBBS mg/l il
~o 1
4:
...l *C . . li
~=K
'\.
\. ,
.002 ., Predicted ~
~
'.
Langmuir
"
.' <i> l
o <i>
o. 000 ..,.....-- JE l ' 1 • ~-
{
o 10' 20 30 40 50
---- (XI
SOLUBLE-K IONS (mg/I) • 1 ~
) ~
..;..
1 ,1
,.
~
'.
r-
"
,
85
/
"
TABLE 3.3 Summary of G Val~es for Bifferent
.. Clay Soils (Equation 3 ..1)
"
\ '" ,
G
Contami nant :
Species _ Natural r,11 ite Kao lin i te
Soil
-'"
?O.O~016 .
6 , \
Ca 0.0\ O. 00025
"
l' Mg " 0.00016 O. 00008'

r-
K 0.001*, O. 000015, ,
J ~ , "
Na 0.0002 .\ O. 000010
\ Q
.
1 _.
* Desor pt ion occurs during 'leaching

.,.. .'
C, \
'.
..
-
",
c >,
/
.,
86
."
species (i.e. the concentration of the con~inant on soil before the
leachate migration). The constants Band. Gare dim'ens ionles s, i. e.,

, ,~~"\ .. . 1
. .t% exchangeab1e. ions

(l' •
simi1é!.r (MjM). Furthermore. "'as C -increases, S
.
approaches the value of G (S""G). ,lt is pertinent to note that the
summàtion of different G values (i.e.' for all cations invoLved),should

.
~ \
~
be equivalent to the cat10n exchan~e capacity (i . e.

•
+ ~ ... - CEC). ~ \ ,
The constant Cl i5 def~ed ~s· an affinLty constant Qf the sorption
sites for certain 'contaminant species. lt ls a II!easure--; of the intensity

4'
and .strength ~f the sorption. lt 'increases wi.th ~he increase in the
aétivi ty and, concentration of cel{tain ions.
related' to the buffering capacity of the soil

..
- e
o
à S
B(C). - - -
ac ~
- B Cl exp (a C.) (3.3)'~ , .
The value of aS/8C >0 in aIl -che adsorption process.
,
Nevertheless, dn the cas'e' of desorption, aSj8C < 0, SA that, as Cl
increases the bufferirig capacity ~(C) increases as weIl. The affinity

.' \
constant a has dimensiôns of [L 3 lM] or, ~s it is· shown in equation
'
(. 1
,
(3}), it'has similar dimensions to !=he sorption bufïering,capacity
B(C) .
,The comparison between the developed model, designated as predicted

f
values, and 'the I:.angmuir model are shown in Figures 3.17,3.18, and
o
3:19. The Langmuir mode1 in mos't of the cases \studied noticeably

\
overestimated the adsorption values in the \vicinity of low
~
concent~ations .
A linear adsorption relationship was also illustrated in Figures

,
87
(. 3.17, 3.18, and 3.Ü (S - KC·), together with the other two- models
(Langmuir model and the developed model). This linear adsorption
isotherm hB;s been used extensively by many researchers. in the study of
co~taminant migration (Soyupak-, 1979). This model expresses an infini te

~
sink; as the concentrqtion increases, the adsorption component

• J
• C' increases. However, the concentration should approach a éertain m~imum
value due ta the limited adsorption c4pacity (CEC) of the sail medium.
Figures 3.20. , and 3.21 display the relationships between adsorbed
and soluble cations for iUite and kaolini te, together wi th the
•
predicted profiles by the Langmuir model and the ::th/matical
relationship presented by equation (3 1). The Langmuir adsorption model
has been shawn ta be an adequate model for the laboratory' prepàred
soi1:s. Nevertheles-s, the model described in this study has also shawn a
(~ good agreement with the- experimentally determined data. This model has
the advantagè of considering most of tbe cases studied.
,3.3.2.4 Desorption of Cation Species
The' preference of the natural clay soil for Ca and Mg readHy
present in the leachate solution was pron~~nced throughout theQcourse of
the migration of the contaminant

" st:udy, as weIl as 'during Na ion
"-
desorption. In general, desorption and s'electivity of the clay soil is
dependent upon several factors, which can be summarized as follows:

l '
(1) The magnitude of the charge of the ion .
.-
(2) The relative hydrated sizes or the relative energies of
hydration of the various cations.
(3) The ionie size, and
(4) The exclusion of ions by sereening"or- sieving action, e.g.

(
"-
.'
)
~
~,
/1:~#"1
J.
1r
1\
(
./
éf
"-
'l
...
3.2~. Relationship between Soluble and Adsorbed Ca Ions:
.00020 r Fig:
lb ~ \0
" .
-
-t
~ ~ -, '-
~:: .. .:: ~11
.00016 ~ :r.-..- .. "
,
o.l_ ..1..1I:
..a.J..'I"--=....... ,>--... :-..z.
l
U.....,l..J.., ..... JI. b
'
~--~lJ :lof))
.IllITE SOIl
B = 0.00014 .....
CI)
-Z .00012
ct =-0.006 l/mg ~,
c
H
10
G = 0.00016
c..J
Cl
Smax = 0.00003
W
al
cr
o' .00008 1/K = 0.992 mg/l
CI) ,
Cl
<t
~
Predicted
("
~
"
.00004 (> () 0 Langmuir
~ " .'
o
______ ~O____ <>
. . -- 0
ô
~ <Z <l>
0.00000 0 40 Ba 120 160 200
SOLUBLE Ca IONS (mg/l) - 00

co
":f. "~/>- " .. "" .. ,.--",.,.·~"J<:!.r""f"~~~_
~.
,"""
f f""\
.0005
Fig. 3.21. Relationship between Soluble and Adsorbed
~ Ca ID\",
KAOLINITE SOIl
B = 0 ~_0002~
œ =-0.006 l/mg
-8 >= 0.00025
c Predicted Smax = 0.0002

<.> 1/K = 2.195 mg/l -.-/
o
Langmuir < J
, '0°
"
) ...
\
0.0000 r , -, 1
0 , 10' 20 30 40 50 0
l .r
SOLUBLE Ca IONS (mg/I) (X)
\0
~ ---------
~
-----
~ f
L
.t'
-----------_ _---_ -
... .. .... -
90
organic ions and i~organic comp.lexes are oft~n t~o large to

.---.
penetrate the soiL matrix.
Often the specifie' rate of desorption ...i~ difficu1t to deterllline
'"
because the adsorption proceeds at a rate whieh comp1icates the accurate
determinatlon of the desorption rate (Gri~fin and J.u,Finak, 1973).
Therefore', it is necessary to deve'lop an adsorption-desorpti.o,n model for

Q
the natural soil using the natural leachate solution.

, This proc~dure
presents an opportunity to take into account the presence of other

\
competing ions and their relative concentrations at,if possible, similar
environmental conditions.
Figure 3.22 displays the Na desorption behaviour obtained ,during

\
- .
the migration of the -natural leachate solution. A simila..r. pattern, but
-
: .
to a lesser extent, was also observed for illite soil, where K ions were
~"
desorbed (Fig .. D.6 c), i .. e. t~e concentration of K ions in the effluent
increased over that of the influent). The mathematical relationship
whîch was, found to express the desorption data is of the form:
S G - B exp (~ C) (3.1)
which is the sarne form~la used to express the adsorption data. This
adds another perspective to the use of Equation (3.1). The constants G,

\ (
R, and~, which were'previously defined in Se.,ction 3.3.2.3, can be
optained by using the least square fitting technique.

c
,.., ~
\
~ "... 1
...
"
,.
Fig. 3,22.~Relationship between Soluble and Adsorbed Na ions . "
l
•
. 004
*
.OO~ r Co
NATURAL SOEL lSERIES III}
B :;: CLOO18
s
CI) ~
ct' =,-0.002 l/mg
z
0
H
G" = 0.0002
10
z
Cl
w
oOO2l ~
.
en
. a:
Cl
"- "
CI)
Cl
4:
.001
\ ~ ,.
~ ~ .ç
~
~ ,,
\/
~I ~ Predicted
~
~ ~
~ ~ ~ J
0.000 1
0 40 80 '120 ,160 200
t
SOLUBLE Na IONS (mg/!)' \0
• 1-'
., ~
~
, 1
~>
92 - ..
",'
3.3.2.~ Calculation of Selectivity Coefficients
o When setting a model for contaminant migration, an account must bè
tà.ken for the selec~ive p~eference of the clay soil foi sorne contaminant
,
... species.
fi ,
Thi~ is reflected by the selectivi~ coefficient vatues. ln
this subsection, the calculated Belectivity co~fficients were based on

~':
the assumption that- .the cation exchange c,apacity governing t'he
exchange processes is fixed, i.e. the subsequertt changes in the clay
exchang.e capacity due to the contaminant migration through the clay
matrix are inevitable. (It wa'S observed that cation exchange capacity
~hanged within ±' 8% after the passage of the leachate ,solution, Table
3.4. )
b
The selectivity coefficients were calculated from the relationship
given by Rawart and Singh (1981). This can be eKpressed in a general
form as: t
-
"(
,
il
(3.4)
,
w~ere ~'and ~ . are- the eqtiivalent fractions of i})'ns m and n in
the exchanger phase, resp,ectively; ~ and ~ are mo~ "'fractions of 1I1
and n in- the sO'lution phase, respective ly; and 1"III- and "Y .. are
n
1
activity coefficients of ions in solution. The activity coefficient of
,
cations in the solution phase is calculated using "'the Debye-Huckel
equation:
(3.5)
•
where Land F are constants, ai 18 the ion size par'ameter, and Jo' is
1()
...,.... • the ionic strength. The values of L a~d F were taJ<en from the tablè,
, ~- 93
o
1
given by Manov et al. (1943) and the ion 'size, a, from that given by
Fieiser an9 Fernando (1966).
Because a complete' chemica1 analysis was not conducted on the pore
!luid, the ionic strength'(~), was estimated using the analy~ed cation
concentrations and the relation,
(3.6)
where the' parentheses represent meta1 concentration (Rearder et al .. ,
1983; Freeze and Cherry, 1979). Table 3.4 gives the concentrations of
catipns both soluble and exchangeable together with the sèlectivi ty
coefficients and CEC calculations. The data. shows that calcium
dominates the exchange site population. The selectivity coefficients

./
( indicate that Ca was preferred over Na and less preferred over K and Mg,
1
respectively, and this phenomenon was more pronounc~d in the case of the
laboratory prepared illite ànd kaolinite soils.
3.3.2.6 Mathematical Analysis of Cation Migration
lt was d~emed important and significant ,to find a...."mathematica1
relat~onship(s) which could conveniently express and exp1ain the
behaviour of sorne contaminant species during their movement throu~h th"
clay 'soil cores. The mathematic!11 function should take into
consideration two main criteria: (1) the nature of the soil system, and
.
(2) the concentration of the permeate solution (lea\::hate solution). The
essence ·of such a function cen~ers a~ound the ability of predicting the
l,
decrease an~/o~increase in pore fluid cation concentration ca'Used by
,
the infi1trating 1eachate solution. Such a simple application allows a
.
1
<;:
f,:;> t~~-" ,
e·
TABLE 3 .4 Results of Sorne Selectivity Càefficient Calculations* '9
7 1
v
No. CEe AdS .... Cations_ Tôtal Soluble Cations Sensitivity Coefficient -'Type of Soil
me /100 (meqJ 100 g) Soluble (meq.Ll) ,
q g lOg log log
+ ,+ 2+ 2+ + 2+
Na K Ca Mg meqJl Na K Ca Ca-Na Ca-K Ca-Mg
85 4.13 4.30 37.05 25.57 6.44 4.34'0.30 1.12 0.68 0.941 -0.238 -0.055 natural soil
2 79 1.24 2. 7 1 29.20 28.37 5.43 3.910.35 '0.80 .0.37 1.45 0.710 0.322 Il
3 75 4.11.3027.102,2.0 4.552.520.301.230.5 0.53 0.104 '-0.3tJO "
4 63 2.02 2.64 45.09 23.15 5.82 3.(i5 0.30 "1.21 0.6 1.20 -0.003. -0.036
. ~-
11
5 66 ,4.1 0.77 23.63.21.12 4.94 2.260.331.63 0.72 0.33 0.191 -0.306 "
6 69--_- 5.211.4519.8 18.0 6.26.'4.0 0.411.31 0.54 0.46 0.002 -0.343 ri
7 58 1.39 1.64 2'0.0 5;50- 3.16 1.03 0.58 1.29 0.26 0.80 0.137 -0.134 Hlite
<;-
8 61 J-;-l(6 1.89 12.8 5.0 3.11 1.39 0.58 G.91 0.23 0.52 0.003 -0.189 11
-'
9 64 1.46 1.94 14.0 5.60 3.13 1.54 0.48 0.88 0.23 0.62 -0.007 -0./86 "
,,-
4! 10. 13 .0.113 0.12 9.72 2.0 1.02 0.52 0.12 0.24 ...
0.14- 1.66 1.005 0.452 kaolinite
Il 13 Û.I070.1335.68 1.83 0 .. 970.530.080.230.13 1.48 0.585 0.244 '" ~

12 14 0.194 0.143 5.52 2.16 2\ 0.97 0.19 0.63 0~l3 1.04' 0.468 0.126 "
~~
- , ~'
r'
* The results shown in this table are so~~:cted results of the chemical analysis
of tbe sectioned columns of different soils. ~
~
-,J
",' ..
95
c fai~ly good approximatidn for the prediction of the contaminant species
migration profiles.
A mathematical relationship of
. ~he form:
(3.7)
Jo
was found to describe the experimentally determined ion concentration
with both time and space (migration profiles). The physical meanings of
- '
this mathematical func tion and the associated constants, the
relationship between the pore volume and the constants A, B and CC, of
equation 3.7 is sc~ematically drawn in Figure 3.23 to further elaborate,
illustrate and hi~light the behaviour of these constants.
c~~k is defined as the attenuation constant, w,h:Lch
correspoGs. to a certain type of soil' as weIL as to a certain
( contaminant, 1'. e. 1 i ts value changes from one ion to another and aiso
. '
changes with respect to the soil type. Constant A depends mainly on the
ion adsorption capaci ty of the soi"l system which will be used as a
barrier. lt was observed that the general trend of constant A MaS to
decrea'se wi th the numbt of the pore volume displacement ,of the input
solution. This ~ehaviour of con~ant A paralleled the change in the
soil attenuation capacity whi'ch decreased' with the progression of the
time of its use as a barrier system. Constant A has a dimension of
(L- 1 ) which can relate the soil ,surface' area to the total volume
of the clay barrier (L 2/L 3 ) •
Constant B is influenced ~.y the 'initial concentration of the··..\
contaminant species in the generated leachate solution, while constant
CC is affected by the base c.oncentration in the drainage layer

C·.
j
';'-",
.
{
rJ • t~
, "
~
96
t
~..0-
0 >
AX
35 ,C =CC +8 e
~ - 30
-~
CD
06
25
B
20
Q Yi
Q ,.
15
CC
10 't<,.
0
2 3 4 5 6
R,t . , 0.1
.,.... ~re Volume
~ p
~ 0:2
-
... 0.3
-~
«
0.4
A
0.5
tIi
0.6
..
lh....
'r .
Fiq~ 3.23. Schematic Diagram Illustrates the Typical ~haviour of'
, '
A, B and CC.
Note: The dat~ points are given in Table 3.5
o
97
c-
• 1 •
(aquifer). Both B and CC have units of concentration (MjL3 ). At
deptlj X o (at the interface between ~he leachate and the clay soi~
surJ;ce)
/ ,
, B + cc where Co is the initial concentration. lt
1 \ ~
was l ob.served <::hat after 3 to--4 pore volumes displacement, B - CC for
1
1
most of the cases studied. At X - L, (Le. at the top of the'drainage
1
Ifyer) ,. the concentration C - CC (the base concentration). Some of
1
'hese const~nts ~re summarized in Table 3.5. Figures 3.24 and 3.25
the comparison between the predie-t:ed and experimental ,data for
clay systems leached with natural leacning solution (Series
III). Other comparisons are provided in Appendix D (Series l and II

-
natural soil).
As the number of pore volume disI\lacements incr~ase, constant~'îfY-'\, -.

\
decreases, and lt can reach zero after the passage of a significant
numb~r of pore volumes, i.e. the &ffect of the initial concentration is
not any ~r~ vital with the increase in, time. Nevertheless, (the
importance of constant CC (the base concentration) becomes more •
! pronounced with the increasing number of pore volume displacements.
o
lt is pertinent ta note that thëse calculated constants are based,
upon a certain type of leachate sol~tion with a certain strength and
under ~aboratory conditions, however. it is important to know the
behaviour of-such constants, in arder ta fac~litate the design and the
estimation ôf the required clay barr~er depth; and to obtain an effluent

,a.
with a reasonab.le quality, which meets the standard stated by the
vf-rious environmental agencies (e.g. 'Environment Canada). These
constants (A , B, and CC) in practice should. be given in the forro of a_
nomograph for the various contaminant species. ~is can produce a quick
( estimation of. the migration profiles in similar landfill sites. A
, .
.:> 1
1
rt>';
'-- ·0. '
.:
OI-
t-,
1
1
0
,C,- •
, ~4 ..
TABLE 3.5 Surnmary of Different Constant·s '(A, B, ~CC) in Equation 3.7 for
•
Different Contaminant Species During Permeation in Natural
sonO) >
'to.
Pore Ca Mg R Cl TOC
A(J) B(2) Cc(2) -A ' B
B CC 'A B CC A CC A B CC
'"
-0.53 30
• t. 1
ISO -0.47 28 7 -0.21 11 5 -0.64 136 54 -0.63 130 60
~. , 1
2 -0.49 135 45 ,J -0.45 26 "9 -0.22 9 7 -0.33 130 60 -0.65 124 68
. "
J
3 -0.51, 105 75 -0.47 24 10 -0.2\ 8 8 -0.41 107 ' 83
~1
• • '!I
111 ·79
4 -0.34 89 90 -0.35 21 14 -0.24 7 9 -0.26 80 110 -0.55 95 95

5 -0.20, 70 110 -0.41 18 17 -0.28 6 10 -0.42 61 129 -0.35 58 131 ,
'"
!IL_~~ _.-
--~_.~- --~_ ..
l
"
1. A [l/L]
.3 ,
2. B and CC [M/L ]
. . 3• Similar tables for Blite and kaolinite sail ar~. providea in Appendix 0 ...
Tables D.l and 0.2
, .
-
\C
CD
" ~
"
~
..
--~----------~----------------------
~ - ~
".1
~
i
....... ~
J "
Mg CONCENJRATION (mg/l)
•
"
10: 15 20 25 30 35 40 45 . 58
/ j
. -,
Naturel Soil (SeriQ~ III)
"
.' "Exper i mel1ta 1 Detq
-
Ê
E
::t:
l-
(L
.40
- Predicted
~
UJ
o
60 ..
"JI,
1 PV A ~-0.559 B = 26.5 CC = 8.~
'- 2 PV A =-0.593 B = 25.1 CC = 9;9
80 'r 3 PV A =-0.357 B = 22 CC = 13
• ... . 4 ,FlV A =-0.354 ~= 21 cc = 14

J
,
5 PV, A =-0.499 B = 16.6 /CC = 18.4
100 .>-
JI.
"\
,
Fiq. 3.24. Comparison of Predicted and, Measured Mq Ion Profiles in Series III.
\0
\0
\
..
~!
. ~.
- ,. ..-!! \
-1::, o "
dJ
.' ,
K CONCENTRÀTIO~ (mg/l)
4 -;-
o 5· 10 15 20 , ~5 @ 30
o ~
. .. "
<>
20
~
-.
Natura1 5011 (Series III)
y o
'èE 40
...,
I r r jfltl ,.- 1r
.
-'"
" ,
* Experimental pat~ "-'"""
...
:::z::
0..
'- ..---
~ Predicted
~. 1 __ __ 1
60 . ~ ,_. _"-.L
1
1 PV ~ A ~-d.246 8 =t 7 CC = 9
1 .' li'
80 l , , l ,..'
A =-0. 159 CC = 7 =9
:2 PV 8 1
3 PV A =-0.217 B ='S CC = S
l' 11 1 1
1 *'* * 4 PV A =-0.241 B =7 CC = 9
l '
100 5 PV ) A ~-O. 288 8 =, 6 CC = 10

,
1 J
"
)
120
Fiq. 3.25. COMparison of pre?i6ted and Measured ~ Ion Profiles in Series III .
.;! 1-'
.... '" o
o
...
101
( typical example of a nomogr~ph is given in Figure 3.26.
3.3.3 Migration of Chloride Ions
To investigate the effect of the hydrodynamic disp~rsion and the
chemical processes in ehe clay soil system, chloride migration 'and
attenuation behaviour were used as bases for comparison with ~her

, , . ~,~
cont~inant species. The ratios of chloride to other ionic species in
the migrated leachate solution (migrat'ion profiles) were used to
indicate relative changes in the concentration of contaminants
- 1 -
indeperident of the - di spe,rs ion effec t. An increase in the
chloride/contaminants ratios can suggest 'that the species is being

~ ~
chemically attenuated by,othef mechanisfs (adsorption, precipitation,
etc.). The Cl/contaminants species rattos is cons,tant 'with time, only
(~ when one neglects the effect of the other attenuation mechanisms.
The ratios 'of the chloride ions to the different cations studied
show trends expected from cation-exchange processes. The Cl/Na, CIl
Ca, and Cl/K ratios indicate chat thê chloride concentration along the
flow path increase,d with the successive intrusion of the leachate
solution; as illustrat'ed in Figure. 3.27. The attenuation of K, Ca, and

,
Mg ions was more pronounced at the upper layer of the clay columns, and
attenuation decreased towards the low~r p~rtLon.

.
Cl/Na, Ca, and K ratios
1
were relatively cons~ant at this lower part of the clay co#uffins, and the
Cl/Mg ratio was in the range of 2~5 ta 5.0, with no odistinct trend, The
values, of the ratio ïncreased and then decreased towards the lower
\ ...
i \ por'1!ion of the c-lay column.
These results are~strongly §upported by the dispersion coef~icients

.f
J'
'1.
t. r:/ 12 a
102
r
100
0 C:: CC. 8e AX
80
C-a
,....
CO)
LI
-
60
~
co Ca
~
40
<()
()
Mg
B
20
Mg K
k
00
... 2 3 4 5 6
.... ,. r
Pore Volume
""""
02
K
A
04
,....
- A
-
I..J
«
06 , Co
mgll
K 16 0
1 2 _
08
C-,-a-+--'-8-0--'~
Mg 1 3S-[~--
1.0
"
t ~1-" •
103
20
( ,.. Na
ct1
z...... 1.0 Â 1 pore volume _
ü
• 5 pore volumes
00
oq 20 40 60 ao 100
~,.. 20
~
......
.....
0--.
1.0
()
• • • .
~
~......"
0.0
00 20 40 80 100
1
20
Ca
( ()
co
......
-ü 10
.- ... ...
0.0
00 20 40 60 ao 100
10
Mg
OJ
~
1
-......
U
5
;à' ... Â
•
0.0
0.0 - 20 40 60 80 100
Depth (mm)
Fiq. 3.27. Ratios of Cl to-C>ther Species along the Miqration Profiles

(. after 1 and 5 Pore Volumes .
.,
J
r
back-calculated from the migration profiles. Chloride dispersion
coefficients were 3.0 to 4.0 times greater than for other lonic,species
(Ca. Mg. K•... ). Also an asymptotic behaviour was'observed towards the
lower end of the clay columns, These results will be give~ in more
detail in Chapter 4.
One can predict from the preceding' discussion' on the attenu'ation of
chloride ions that it is not important ta consider an adsorption u'nn
(sink term) while modelling the migration of chlol'fde 10ns throllgh Lhe
sail systems The only two main parameters which control ,tlU' trtm:-ipot't
of chloride ions amj. the response of the sail media ta chase ion1>, an'
(1) the seepage velocity of the migrating leùchatc solution, . llld (1)'01 tl\('
dispersion coefficient (where the seep.1~e yelocity tl1kes into ilCCOUllt
the porosity and hydraulic conductivity of the sail_system, as w{'ll ,'W
the hydraulic gradient) The dispersion coefficient t.lk(·s lnto
consideration the physico-chemical aspects of the sail )nedin Ilnd tlw
nature of the contaminant species .... ..
the Mixration Profiles
Figure 3 28 a displays the equivlIlcncc (lnNl/l) r.1lior, of tlw major
cations (Na, K, Ca, and Mg) to the tolal holllbio ('o'll1()nt. '0; clIt10nul
alang t~migration profiles, tlft(~r th(. di:.:plllc,(.IU(·nl of flotll ()tw :1I1d
five pore volumes. The advantagc .of usin& tlw r>qulvlÎlel1t w.,l/l,ht in th .. ",.,
comparisons is té>. eliminate, to l'iom<> cxtcnt. tho (>fff1(:t ot th ... v.,lPll('Y
The shaded area in the L cationr.·Jep:h rl1.1gratn r"l'r"'1~ ... nt~ the."
\
total aJllaunt of cation inc:rease lin m<''1/l) in' th~ t'xtr.1ctt'd PQ,I" tbl1lt,
due ta the intrusion of leachlltc 'iolution

j
)
105
2'0
~
l Cations
• 1 pore volume/
( .....
5 pore volumes
15
\ Ct
~
E
10
5
1) Background Con'centration
00
en
c
0 06
.....
(1j
. 0 04
~
" r....:.,
(1j 02
'Z
00
.-
en
c
0
..... -
'0
(1j
0.03
002
~
• • •
•
•
•
•
•
• ' .
• .
"-
~ 001
( ....
~
0,0
en 075
c
.-0
..... 05 -"
~. . .----==--: : :.
(1j
ü
~
025
....
(1j
Ü 00
en
c
.-.....
0
(1j,
03
~.
ü 02 - a
~
• • • • • • "
.....0) -
~
01
00
-----a • • • • ,.,
..00 20 40 60 80 100, ~
,
,Oepth (mm)
( -Fig. 3.28a. Equivalence Ratios of Maior Cations to the Total Cation' .

~, Equivalents 0': Cations), -
,-
.J
-106
be in the range of 40 tO' '50% (3.5 ta 5.0 meq/l). Comparison of the
,equivale,nts of each cation to 'the tot~l equivalent sturunation in the pore
fluid along the flow path showed that the relative amounts of both Ca
and Mg increased with an increase of the number of pore volutue
displacements, while the concentrations of the other cations (Na and K)
decreased.
The summÇition of Cl and HC0 3 species repres1nts about: 30% of the
total cations after one pore volume displacement After five porc
I s the ratio increased to a value of about 40% (Fig. 3 28 b)
I
io
ese: chan.ges were due mainly to the relatively high mobni ty of
c species (as explained in the previous section). The high mobility
of the Cl ions can result" in an increase in the positive dharges. within

th!!~l'
the sail pores, wren compared ta that in the collected effluent..
- Althdugh sorne of the charge balance could be maintaihed by ather aniant-.
present in the pore fluid, this, difference in positlva llnd n(~gativc
charges eould add another driving potential (streaming potentlal) to thp
co~taminants migration system. This potentinl could nccelerl'lte the
migration 9.f the ,positiv.e ionie spacies tu &ati!ify the es!:>(>ntinl
symmetry l:!etween posltlve and negative,charges These resul, ts Wera .

observed when comparisons wp.re made between the "different migratioll
profiles with respect to the differen't pore voltune,s.

.
' 1 -
3.3.5 Migration of Organic Substances (TOC)
The attenuation of 't"h~e or&atlic cornpounds_ observee.! CMl bl'
attributed mainly to t'he adsorption of oqymic molccules on tht· (',lay
. surfaces. The forces involved are tho~c .1cting in .d1 '1nst'llncps wlwr~
,
atoms and molecules are in close proximity
"-
/'
107
C
~
1/)
• 1 pore volume
-
c::
0
.....
~
0.8 • 5 pore Volumes
Ü
-
H
oC:
0.6
•.-=--- •• ••
04
••
Ü
~-
J:
±. 02 • t!
Ü
H
0,0
CI}.
c:: ...
.-.....0 0.3
-\
~
-
Ü
H 02
0
M
0,1 :======: 1=>"4 1 1
Ü
:r:
( 00
1/)
c:: 0.3
.-.....
0
~
~:====:;---I -: :
.'
0.2
ü
~
J,
..... 0.1 -
Ü
00
00/ 20 40 60 ' 80 100
, . Depth ~mm)
Fiq. 3.2ab. Equivalence Ratios of Cl and HC0 to the 'rotal Cation

3
"EoÙivalents (r pa tionê.,) .
......
~
i
!
( --\
"
)
108
o organlc molecule approach~s the surface of the clay sail, clay organic
complexes are formed, primarily due to: (a) major interactions between
specifie groups of the organic molecules and the charged,sites on clay
surfaces, and (b) , minor interactions between different parts of the clay
,
surfaces and other molecules (Yong, 1985). In fact, therè often llppears
ta be a s tro~g preference of the clay for organic cations and anions
(Van Olphen, 1977). The basic mechanisms responsible for formation of

,!
clay-organic complexes can include: .( 1) ion exchange, (2) hydrogen
bonding, (3) Pi bonding, (4) covalent bonding, (5) ion-dipole and
coordination, and (6) Van der Waals forces.
Lt is strongly felt that bio1ogical degradatton 15 one of the major
mechanisms contributing to organic substance attenuation observed in

<'1
the soi1 c01umns. This, however, has bèen based on qualitative racher
........ than quantitative assessment. The conditions nœcessnry for microbial
processes taO develop are present. TI1ese include both the 10'10' leach.1.tl>
migration -...œlocity. and, the presence of various nutrients r(!quircd for
..
the microbial growth .
The fact that the collectcd leachate is re 1atively oid (i, e setting
in the leachate ,basins for 2 years), probab1y llccounts for the 10"'"
"'\
1 reduction in TOC. This aho might be attributed to scver,1.! factors. ~uch
as the type of organic compound present in the leachate solution, nnd
the stage of degradation (Appendix B, Sec. B 6), due to the <'Xlt'IWlvf;' \
time required for the comp1etion 'l.of the biodegrad..ttlon of the reml1lnl.ng.
orgAnic compounds.
l'h~ observe'd results imply that adsorption of orglinH mat.ter m1ght
not be important as an attenWltion mechanism dùr1ng lenchl.ttê mOvOlllent-
(
109
_through the
- soil columns. The results appear to agree, with the
( observations reported by Griff~n and Shimp (1977) and Farquhar (~9J~
.,.
who found almost no COD red~ction after passing. lysimeter leachate
_.
through a series of soil columns . However, flow veloéities and
.
hydraulic gradients, encountered under the field conditions, are usually
m~ch smaller than those u~ed in laboratory soil colwnn experiments.
Thus, as thè ~\contact times between the - organic matter and the soi1
t'
surfaces (sorptlon sites) are inareased, the possibility ~f adsorption
and/or transformation ls increased.
In summary, the high~ mob ili ty of organic compounds has two main
effects: (1) thé,'deterioration ,of the groundwater quality, and (2) the
alteration of the soil characteristics and behaviour (shear strength,
hydraulic conductivity ... etc.) and these are discussed in more detail
in Appendix E.
3.3.5.1 Mathematical Analysis of Chloride'and Organic Migration
The normalized chloride ion co"ncentratlons and normalized TOC
cOncen'trations for t~e soil column effluents followed essentially the
samè breakthrough curve pattern (Figs. 3.9 and 3.13). , Such an
observation supports the TOC results, which indicated'the lowadsorption
capaci ty of the clay for the organics. Figures , 3.29 a and b,display the
'
typical behaviour of TOC and Cl ions in -the natural clay soil (il lite
and kaolinite soil are given in Appendix D). The samé mathematical
function presented in Section 3.3.2.6 XEqu~tion 3.7) was used to predict
the migration profiles of Cl ions and TOC. T~e comparison of the
predicied data and the measured one are presented in ~igures 3.29 a and
c b.
)
_ _ _ _ _ _ _ _ c _ _ _ _ _ _ _ _ _ _ _ _ _ __
---
(~ ·c '") ..... o·
~
Cl CONCENTRATION (mg/l)
o 50 100 150 200 250

o r----------------r---------------,~----~·~~~------;---~I-~---~~~~·~~---------------,
.\ ..
, 20
.. Natural Soi 1 (Series ! 1D

..... 40 ....
E
...,
E
. .. Experimental Data
~ Predicted
fl:;
Cl 60 .,
~
1
IPV A =-0.'65B = 136 CC =
.... ".-~
2PV A =-0.33 8 = 130 CC =: 0
80 3PV A =-0.41 8 = ·107 CC = 83
,
1
Î
4PV A =-0.26 B = 80 CC = 110
5PV A =-0.42 8 := 61 CC = 129
--------
100 ::>
. 120 1
'~ ~
" F10. 3.2 Q a. Ccrrrparison 0: Precllcted and Measured Cl Ion Profiles in Series III.
....
t-
o
,.,. ..
........
~
,...
....-
,
TOC CONCENTRATION (mg/l) i;:;
.'
~
\,-
o 25 50 75 100 '125 150 175 200 225 250

"---t" a1 1 :;dl ,
1 *
20 1
1
Natural 5011 (Sarlas III)
'EE 40
.....,
:r:
* * Exparimantal Data
1-
a.. ... Predicted
w
Cl
- 60 ï
" IPV A =-0.M.1 8 = 130.5 CC ~ 59.5

'--1
80 2PV A =-0. ·654 8 = 122 CC = 68

3PV A =-0.490 8 = 111 . CC = 19
.;
.,.
~
*
4PV A =-0.552 8 = 95 CC = 95
100
•
\ .- 5PV fi =-0.353 8 = 58 ·cc = 131
~
"
(,
-. .
Fig. 3. 29b. Canparison of Predicted and Measured 'Iœ Ion Profiles in S~ries III.
120
"
f--'
~ &
""'"
""'"
~.
,
112
The different constants A, B, and CC were obtained and the aver~ge
o values are sÙInmarized in Table '3.5. The overall behaviour of these
constants 1s similar to the cation behaviour whieh is schematically

.~.
visualized in Fi~re 3.23. Tqe Cl ions and TOC attenuation factors
Ac~ and Âroc were found to range from -0.65 to -0.42 and
-0.63 to -0.35 re~pectively.
To examine the sensitivi ty of the adopted mathematical ,function
(-Equation 3.7) in' predicting organic migration in sorne Ôther·
environments, the COD removal oata obtained by Soyupak (1979) were vsed
for comparison purposes. These COD data were obtained from the
laboratory sand soil columns during the permeation of the natural
leaching solution collected from the CFB Borden landfill in Ontario.
The constants B and CC appearing in equation 3.7 were estimated ba~ed on

- - " # '
the initial COD concentration of the leach-a,te, while the proportion
-. .<
between B and CC was selected from the values already determined in the
present study. The attenuation factor A., which depends niainly on the
CEG of the soil, was taken as ~O.05 (less tha~ the attenuation factor
found for -kaolinite with respect to the organic compounds). Figure 3.30
d~splays the cqmparison between Soyupak's oata (1979) and the predicted
results; the correspondence bètween predicted and measured values was
highly acceptable.
Figure 3.31 presepts 'another comparison between the experimentally
measure~ migration profiles of Cl ions obtained by Grooks and Quigley
(1984), _ (lusing NaCl solution of concentration pf 15 gm/l permeated
through .silty clay àoil obtained from an f open excavation site near
Sarnia, 'lntario), and the predicted profiles ohtained from equation 3.7.
fi- measur~d
'-
Poor correspondence between computed and actuai profileS-Wss
r •
...
113
.
(- '
T,ime • ____ • ",Soyupak (1979)

A, 8 CC
dqys (,
0
-'- Predicted using

3 -0.05 245 105
,- -
~
6 ... 0,05 31'0 40

. -
15 _0,05 ,'325 25
,
1
) J
100 _0,05 340 10
c Fiq. 3.30.~· Canparison Be~en COD Removal"Data (Soyupak 1979) 'and- the
predi~ted value fran Equa~on (3.7). .
..
1
~.
114
• r
o î_
.[ -
T'me
1
days
A . B CC " - 4--l:!- -~S & QLHgley
-
( 1984)
58 . -0.5 8600
.
,
800 .. , 1
. Predicted' using
154 .,...0.45 3600, .$800
.
. -
319 ~Q4 1900, 7500
,-
. "'1
Piq. 3,31. Ccrnoarison Between Chloride Miaration Profiles (Cfooks and

~ OuiQ1ey, 1984) and the Predicted Profiles fran
o. Equ~tion (3.7).
J
115
c ~ found for thé e~rly migration p:çofile
volume) .
"
Nevertheless,
~
(slightly greater than 1 pore
acceptable agreement was found for pro;files
after 154 days and 319 days of Na~l permeation. By and large, equation
3 .. 7 seems to be reasonàb1e for preliminary studies of liifferent
contaminant species migra-tion and with tbe he1p of the nomograph

'1
. presented in Figure 3.20 (or simila'r nomographs), the different
coefficieri'ts (B, cc, and. A) can be estimated.
3.4 SUMMARY·
The leaching test results obtained, during this investigation have

1>
-demonstrated the potential of the natural clay soil in the attenuation
of different cont~inant species. The experimental results indicate the
following:
(1) Heavy metals are strong1y attenuated by the natural clay soil"
"-
lt appears that precipitation is the primary mechanism
caus iI'!g the removal,
(2) Sodium ions are eluted more than those applied, implying the
po~ibility'of replacing sodium with ca~~urn-and magnesium in
the exchangeable sites on clay surfaces.

o
(9) The chloride migration curves show. the 'characteristics of the
non-r:eactive ions, whichc are not readily altered by chemieal

/ .
and biological prooesses. Chloride ions migrate faster than
other cations and anions: "
(4) The organic compounds .• measured as .

Tot, show a low degree of
attenu~tion and r:elatively high mobi}it'y th~ou&h aIl three

(
.\
\
1
al
di·fferent types of clay soils.
\
(5) Sulfate and carbonate concentrations are found to be ext:remely
low ( below the detection limits).
(6) A mathematical relationship of the form (S -1 G ~ B exp(o C) 1

!
1
is found to describe the behaviour and the respot;lse of the .

natural systém fairly well.:> (wher: Sand C are !the excJ~angelible
and soluble cations respectivel~, C, B, and Q are constants)
This funetion seems ta overcome the previous models
._.fleficieneles .'
This study has demonstrated that the natural clay soil used to
contain the solid waste can be used ta adequa te 1y conta in d i.f fe'rent
Cc
contamina~t species (excluding the TOC). Furthermore, the results
suggest that under favourabîë sail conditions, landfill lcaehatos,
containing low levels ,\f heavy metals, will not pose li substantial
threat to the subsurface envirorunent Similarly, ~he data obtaincd hnv~
demonstrated that the clay it-self can release potential contaminanls
under permeation 0 f the leacha te solut ions, and 'have rev"lll cd the
"">
importance of adsorption-desorption mechanisms. l t should be not('d th,tl
the clay soil buffering capacity 1s not infinite. As noted 1"n th; tost
results, care should be given ta the disposa! of acidlc and/or
concentrated organic wJs te in the se- landE i 11 sites
..
-.
117
c CHAPTER 4
COMPARISONS ANp PREDICTIONS OF CONTAMINANT
MIGRATION THROUGH CLAY SOILS
4.1 GENERAL
This chapter centers exclusively-on the mo~lling and application
of data derived from the soil columns in order to predict the movement
of the contaminabts through clay soils. Mathematical models whi~
describe the reactions and transport of different èontaminant species
through clay soils have been reviewed and are summarized in Appendix C.
These models have been used in the literature to simulate the movement
and interaction of certain ions in soils. Convective~dispersive models
for ,contaminant transport in soils are classified into two broad
categories, base~ upon whether sorption-desorption processes occur under

(~ local equilibrium or nonequilibrium conditions. These two categories are
~ther divided into subgroups depending on whether ~orption-desorp~on
~ceeds with linear or nonlinear equilibrium, and on whether the

'1 reactions occur reversibly or irreversib~y (Appendix B).
. In aH models, the different ionie species are considered to be
Î mobile and to move through the clay soil pore spaces with the flowing
"
intruding solution (i.e. leachate solution). As the solute moves through
the pores, the ionic species come into contact with the sorption sites
associated with'clay'minerals. Forward sorption reactions at t~se sites

, .
• result in a transfer of certain ionic species from the mobile solution
phase to the immobile sorbed phase. The reverse process can occur, as in
the case of backward desorption reactions. ,Under local equilibrium
- . conditions, all forward and backward reactions arè considered to occur

.C 4!1
)
j
118
instantaneously, and are thus independent of the pore fluid velocity.
For the assumption,of local nonequilibrium conditions, the forward and
back~ard reactions occur as kinetic or time-dependent"processes, and
th~s they depend on pore fluid,veloci~y. Since the pore fluid velocity
determines the residence time for contaminant species within the pore
space. an increase in the pore fluid vel0,iity tends ta decrease the

"
possibiiity of the adsorption and removal of contaminant species from
the liquid 'phase (leachate solution),
In practice, there are a number of other factors that do not appear
to have been considered in the existing mode11ing techniques, and they
can be summarized as fa llows :

o
(1) The effect of the presence of other competing ions for free
charged sites on the clay surfaces, and the rep1acing pawer of
-
- sorne .ions over other ions,
(2) The exehange capacity of the soi1 medium and the existence of,
the e1ectrostatie environment,
(3), Ion exchange pracesses, sorpt ion- desorption, and forward-
backward reactions "
(4) Changes in subsurfaee envi ronment al cond i tions due to
reaetions and interactions with various contaminant specles as
a function of time,
(5) The presence of a biomass in the natural system, the nutrlcnt

, requirements, as weIl as the byproduct gencratlon tvolatile
fatty ac ids, CH~"., etc. ) ,
(6) The heterogent:!ty of the solid waste, und, ln tur!l, the
generated leachate. which' causes shock loadlng on th~ clay
"0'"
~ -'
barrier system,
119
(7) The osmotic effect, generated due. to the increase in water \

o
( content in the output encl of the flow (bottom of leaching
\
• ceU) in order 'to fulfill the equilibriwn requirements,
(8) The cross effect of different fluxes causing water movement due \
\
to the solute gradient and vice versa, and
(9) The effect of concentration and ch"emical activities on
'diffuSivity o~ contaminants. .'
The objective of this chapter is to examine-the ability of the
convective-dispersive mathematical model to describe the buffering

.
capabili ty of the different clay' soils. This has been do ne with respect
to various groups of contaminant species. Furthermore 1 this chapter
highlights the importance of considering sorne of the above-mentioned
factors which are usually neglected in modelling the migration of the
contaminants. Figure 4.1 schematically illuFtrates the method selected
as a rational approach for predicting the migration of various
contaminant species through the suhsurface environment.

\
4.2 FORMULATION OF TH~ MATHEMATICAL MODEL

•
The deri va'tion of the solu~- transport equation is based on the
J
principle of the conservation of mass. The basic assumptions are:
(1) The porous medium is homogeneous and isotropic,

{
(2) The porous medium is fully saturated,

.. (3) Steady state flow conditions are in effect, and
(4) Darcy's law is valid.
It ls also assumed that the molecular diffusion and mechanical
dispersion can both be treated as a Fickian type spreading mechanism .
. The two mechanisms can be combined together in terms of a single

.~
Infiltration
't~ ,
J;
o < 1
,1
L» H Clay
__-----/.... SOIl~- wast-;--- ~

L= 500m
1Ir
-WJ "
7 t ~
\
Leachate
STEP 1
~
Clay 5011 .-
. 1-D
H clay
20m -9
K=10 m/aec
Aqulfer
,'" -4
H aqu-Ifer
~ .~~ ~
K::-10 m/aec
/f//// ~
r STEP IV "
'.
1 l
5011 éolùmns
STEP Il
Co STEP III , - ---- ~

--T- Co
, Co Co C.. 0 ,
Hf
t:>
Laboratory
H2
HI -, 50,iI soil soit soif
Land.lI. Moder
H = H clay C1 C2 C3 Cs
1 20,0 1 1 1 1
~
H =6H 1
.1
2
D=f(x,t)_ S= f(C)
.....
fi.)
o
fllJ -II ')\ ht-'llIdtl'_ 1 )"w-Sht"eI for tht" f..1otlt.·llm'J 1t:'Lhn)'lu~
, J
J
.. :
121
....
c hydrodynamic dispersion coefficiént (0) (Yong et al.
dimenS~Onal tran~port
"
1985).
in the Z-direct1o, the flux (Fz)~ is given by:

For o~-
(4.1)
where the first and the second terrils. on the right-ha~d side of the
equation (4.1) represent the convective and dispersive transport
mechanisms, respectively: 8 being the volume tric water content or t~e
effective porosity; C the concentration (mass ~er \,lnit volume of fluid);

\
and Vz the seepage ve1dcity. The negative sign before the dispersive
term indicates that transport of the contaminant is in the direction of

L
the decreasing conceI1tration gradient, whose z is the distance from the
contaminant source (i .ri. from the top surf~ce of, the clay barrier
dOWnward) .
\
( Considering the masa balance condition:
aaFzz _ (9 ac +
• p as) (4.2)
at at
where p
as represents the source/sini< term describing
at
the geochemical reac~ion, p being the bulk density of the soil
matrix, and S repreHmting the adsorption term (wei~t/weight). A
positive sign denotes a source and< a negative sign. denotes a sink.
Combining equations (4.1) and (4.2) gives: -
ae a2e ac p as
at - Dz az2 V-z az - ë at -
\
This is known as the convective-dispersive equation for solute-
transport in one dimension.
)
'7 - • t, 122.
The sink term in equation (4.3) is a function of the concentration,
and using the Chain rule yields:
(4.4)
The re1ationship be;ween the adsorbed contaminant (S) and the

,
concentration
, in the pore fluid (C) can be approximated by aither an
e~onentiar function or by a linear re1ationship (Chapter 3). Hence,
sUbstituting equation (4.4) into equation (4.3) gives:
\ ,
ae '(1+ !!.. as) (4.5)

at ,9 ae
1
• '1
where ( 1+\P.
e as).
BC '
is usually known as the re tardation term (R) and
as as the, buffering cap a c i t Y" 4B ( C ) , which can be

ae
,.'
determined experimentally for a given type Qf sail and) any solute
"
species, as described in,qChapter'3. The reciprocal of the retllrdation
factor (R) i5' referred to as the relative velocity (R) - Vs/Vc
Substituting (R) into equation ~~.5) gives:
(4.6)
Ana.ther ·factor which should be taken into considerlltion in

~
calcu1ating the retardation factor (R) is the selectivity coefftc lent.

, "
This 15 to account for the preference of clay soU for certain l~lS. duc
to ~evera1 factors such as concentration, activity, and hydrated radius
(Ch~p""er 3).
.\
123
( \
4,.2.1 Boundary and Initial Conditions
A standard set ~f bOUndary and initial conditions were '\.!.Sed in this
study:
)
t >u z- 0 C - Co (a)
t - 0 0 <z < L C - Ci (b)
BC _ 0
t > 0 z- L Bz
(c)
\
Since the landfill is constructed on a deep clay laye~ of about 20
'm thickness, the time required for the leachate solution to reach a peak
concentration at the bottom 1s often very small. On the other hand, a
considerable longer time is required for the migration of contaminant
species through the clay matrix, due to the low hydraulic conductivity .
.
Thus, it can be assumed that the contaminant has a maximum concentration
( (Co) shortly after construction
()
(t - 0), and that this concentration
will then decrease with time, as leachate is percolated through the clay
soil matrix, leading to condition (a). Condition (b) takes into account
the initial chemical concentration of certain contaminants in the pore
fluid of the clay sail. Finally, flux con~inulty leads to condition (c),
which expresses the condition that there is no change in the
concentration of the contaminant species' at the drainage layer

\ .
(neglecting the dilution effect due to groundwater movement).
124
4.3 COMPARISONS AND PREDICTIONS OF CONTAMINANT SPE~IES MIGRATING

TRaOUGH CLAY SOIL COt.UMNS
To test the method of prediction, one -can work with _the dispersion
coefficients. c~lculated from the test results obtained after leaching
with one or more pore volumes of the leachate. Instead of assuming that
_ 0
the dispersion coefficients represent average values throughout the test
samples for the various individual contamina~t components, the procedure
followed recognizes that interac tions es tab lished between the
contaminant and the soil will cause continuous alterations in the
bransmissibility characteristics of the soil. Thus, the dispersion
coefficients should be ca1culated for individuar layers in the soil

"-
samples, and for each pore volume passage of the contaminant, by using
test Series III as the control test samples and the finite difference
scheme as follows:
• \
D C{tl - 2 cj1 + Ct-l V CI+l-CI-l
il - il (4.7)
I:.z 2 2 toz
where i is the depth factor and j the time factor.
The back-calculated dispersion coefficients for Cl, K, Mg, and Ca

. ~
are displayed in Figures 4.2 a and b. This procedure permi ts the
determination of the variation of the dispersion coefficient ~ith depth
"and increased passage of the leachate solution. A computer pro gram
written in Fortran was developed to compute the dispersion coefficient
\ from the experimental data. A copy of this program is given in Appendix
D (S~ction 2). ather results of dispersion coefficients back-calcu1âted
_ for differi!nt contaminant species and other types of so11s (lUité and
kaolinite), are a1so presented in Appendix D.

05 125
CI -,
0 =MZ N
C 0.4 0
'ot
~
'0...
N
-
"0
X
~
~
.....
0.3_
t:. 1 pv
...
M
0.039 0.609
N
0
r
0.959
2
E
-
Cl
0.2 Y
0 3pV
2pV 0.057 0.601 0.927
0054 0564 0.825

...
0.1 • 5pv- Q079 0552 0.974
0.0
0.0 20 40 80 80 100
Depth (mm)
.-
C tO K '"
N
""
D MZ
2
M N r
Q.8
A 1 pv 0.146' 0.754 095
'Of
'0... 2pv
" 0.927
-
0.092 0.692
X 0.6
.~
, 0 ap,v 0..067 0.865 0.885
~
"0
N.....
_ E
...
04 • 5 pv 0062 0.817 0.907
Cl
0.2
"c
0,0
0.0 20 40 60 80 100
Depth (mm)
Fig. 4.2a. Dispersion Coefficients (D), Calculated fr::rn Laboratory"Tests as
a Function of Pore Volume Passage and Depth of Soil Column.
. ) ~
126
Ca '-
0 .
. 16
.a- M N r
2
N
c:i~ MZ .a. 1 pv 0.040 0,555 0959
•
v
"-
b....
. 2 pv 0.036 0.534
--
0977
- )(
>.
a:s
,12
0 3pV
- ,
0.036 0.531 0~80
--
N
"C
E f .08
• 5pv 0.034 0520 0983
- 0
.04
J ,
.00
qo 20 40 60 80 100
Depth (mm)
-...
--
J
Mg
M N r
2
.16
N
0 = MZ .a. 1 pv 0.039 0554 0 60
.0037
"
v ... 2pv 0534 0974
-
'0
.... 12 1
)(
0 3pv 0.036' 0533 0918
>.
-
a:s
"Q.
N
E
.08
• • 5 pv 0038 0.531 0974
-
0
04
.00
0.0 20 ~o 80 , 100
Depth (mm)
(
Fiq. 4.2b. Dispersion Coefficients (0), Calculated' frcrn Laboratory Tests
as a Functlon of Pore Volume Passaqe-1and
. ' 'Depth of S011 Colurons .
127
c lt was observed that the dispersion coefficients underwent a slight
decrease as thé number of pore volume displacements of the leachate
solution increased. Also, the dispersion coefficients increased' when
determined further from _the source of the inflow; 'fhey approached an
"asymptotic value as the distance..from the source increased (Figs. 4.2 a'
and b) .
•
The variable dispersion c~efficient functiooO, "detepnined from a
curve fitting technique, can be expressed as:
D- M zN (4.8)
... where z is the depth,. and M and N are ,constant's determined from the
Least Squares technique. These two constants are given in the tables
accompanying Figures 4 ~ a and b.
( Usi~g these values of D computed from the test results of >Series

~
III, and taking into account that these values vary throughout the
"
length of' the test sample and wi th the number of. pore volumes' of
- leachate passed, predict;.ion of contaminant profiles obtained from Series
:r and I I was attempted. These profiles can

Q Q)~
be' compared with the actual
measured values as shown in Figures 4.3 a, b, c, and d.
Comparison between predicted' and measured 'profiies' for various
contaminant species can be made in addition to the cnes shown in Figures ~
4.3 a, b ,. c, and d by using th~ constant dispersion qoefficients (taken

f
as an average value of the calculated dispersion coefficients at each
layer). The agreement between ptedicted and measured values for Series
l and I I was observed to be highly acceptable while uS,lng the variable
c dispersion coefficienss. o
NeverthÉdess, in the normal procedure for'
~
.J
o
1
o· .:~,
'~~'-f
,- - . fil
'-
'.
"
'.
Natural Soil
CI Concentration (mgll)
}
0.0 50 100 150 0.0 '50 100 150 00 ,':;0 100 150
0.0
4 >-
series series
l '
20
"......
E 40
E
---:
.c
..- 60 ._
.)0
0. series III
(1)
·0
80
. . •
100
=
C o 190 mgll
• 1 pore volume
Ci = 170 mgll
0 2 pore voltJm~s - ,e~perimental'
lf/It1J . ''7
0 3 pore volumes -r- predicted from series Ifr(eg. 2,3 and 5 pv)
/
(Oavg :: 0,18 cm 2 /day) 3,5 pore volumes
• 5 porc volumes predicted
1
.,
/
Fiq. 4.3a. CI Profile Distributlqlsin Natural Soi! Columns 1'oqether with Predicted Profiles.
\
t-'
~
....
•
~ f"'. ,~
• " ..
Natural Soil
.... K Concentration (mg/!)

,
. 0 4 8 12 16 20 o 4 8 12 16 20 o •
•
4 8 12 16, 20
00
, . 20
~
...... 40 L"
E
'E
....... 60
..c
......
a.
(]) 80
0
100
series series II series III
12'0
"" o 1 pore volume

co = 16 mgll
'-
o 2 pore vowmes c. = 16 mgll
1
q,
., 3 pore volumes
e xp'erimen~al
A 5 pore vqlumes - - - - - predicted from series 11\
-~icted (D avg = 0.26" ~m?/day) 3,5 pore volumes
Fiq. 4.3b. K Profile Distrlbutl0ns ln Natural Soil Columns Toqether with Predicted Profiles.
./
'" !..,
1-"
.. ~
IV
\tl
\
!t
/
•____ •. _____ r_'_ _ •
~
_
...
't'J t• l'~ t
~~ t'.;~ ~,
C ?
~
... Natural Se..i.l ~

u
'\
\ Ca Concentr'ation (mg!!)
00 50 100 150 00 50 100 150 0.0 50 100 _ 150
..p
20
.......
E .
E 40
'-"
.r:
..-
\
Cl.
1
60
a>
0
, 80'
" . 100
seri~s series" series III i
r
c o = ~80 mg/l
-(
• 1 pore volume CI = 22 mgll
J
0 2 pore volumes 4
experimentaA
• 3 pore volumes
,[ predicted fram series III
6. 5 pore volumes predicted (Davg :; 0093 cm 2 /day) 3,5 pore volumes

1
Fiq. 4 ~ 3e. Ca Proüle DIstrIhutIons ln Natural SolI ColUJT1TlS Toqether vhth Predicted Profiles.
~
1-'
W
0'
~ j
J
~
,.., fi'
"
Natural Soil
'"
Mg Concentration (mg/!)
1
0 8 116 24 32 40 o 8 16 24 032 40 o 8 16 ~4 32 40 0
00
20
....... 40
E-,
E
......... 60
"
0
-
..c
Q.
ID 80
100
<:)
" series series III
series Il
120
=
'"\...
• 1 pore volume !
experimental
C o 35 mgll
C j ='16 mgll
0 2 pore volumes , 0
1
--- -- predlcted from seriès III
.... 3 pore vofumes ----- predicted (D avg =0.089 cm 2 /day)
, 3.5 pore volumès
6. 5, pore volumes
Fig. 4.3d. Mq Profile Distributions in Natural Soil Columns Together with ?redicted Profiles.
1
'" ~
w
~
/- p
,.
-'
132
,,
computed profiles, poor corresponaence between the computed and
actually measured pro~+~e was found.) The apparent difference in the
predicted migration profiles, u~

/'
the two methods. reffects the
influence of the factors which were taken into cons ideration, while
calculating the variable dispersion coefficients.
lt should be noted that the dis.persion coefficient values of the
di'fferent contaminant species in the experimental ~ticomponent)
system, back-calculated from the migration profiles (Chapter 3), w~re
(
less than those values given in the literature for single component
systems in both water and/or nonreactive soil media. (The calcul ated
dispersion coefficients values were lesser by a fac tor of 5 to 7.) Thes('
discrepancies arise from the fact that the driving force for contmnin.wl
species migration in a clay' soil system is affected not only by tlll'
chemical potential gradient, but also by the electrostatic potcntial.
gradient resulting from. (1) different migration rate~ of th('
contaminants. and (2) the ch,3.rged surface of clay sail consritut'nts:

"-
Nevertheless, the single component bas 1.<- ca lcul a ted di spl:'r sion
coefficients can be adjusted for the presence of other ionie spcei(!s by
consid~ring the selectivity coeffieien~s given in Chapter 3
Sorne problems were experienced in applying the above-mentlon"d
method in the calculation' of disper'iion coefficients (D). TheHI'
included the appearance of sorne negative values, as weIl liS soml'
relatively large values for the disperslon coefficients TIlt' plllusibl(' ,.
reasons for such inconsistencies cah be swrunarized as follows'
(1) Because ~ the hig.hly eomplex natural system, it 19 very
difficult to simulate, matk-ematical1y, II fIIodel that will

- 133
)
provide a 'completè understanding of the actual system (i.e.
( experimentally-obtained results).
(2) Because of the interference in the last layers, as
observed in the migration profiles (Chapter 3). The last layer
showed an increase in the concentration of approximately 5%,
instead of the expected decre.ase in the concentration with
depth. This could be attributed to a possible upward migration
of the contaminant species arising from the osmotic effect

"\
built up due to an increase in water content at the bottom of
the sample.
In arder to avoid thèse inconsistencies, a calibration trial and
error ~ethod was used to select the dispersion coefficient that.insured
a fairly good agreement with the concentration profile~ obtained
experimentally. This was used in conjunction with the convective-

( \
dispersive model to increase the reliability of the prediction. This
technique had two general components: the first part was used, to
\
calculate the best fit dispersion coefficients and the second part'was
used to evaluate the stati~ti9al properties of the best fit.
The part of dispersion coefficient estimation ~hat involved the
best fit was relatively straightforward in concep~. The objective of
this was to obtain the estimates of the dispersion coefficients that~
\
gave the "best fit" between the observed data and model calculations.
This required the selection of a "trust model" which could adequately
and easily find the best dispersion coefficients. The trust model chosen
\'1n this research program w<jS the analytical sol':1t.ion for the ~ne
dimensional contamina:t transport equation. 1s given by oga'ta' (1970). A
computer program written in Basic was developed to facilitate the

(
)
134
estimation of the/dispersion coefficient based on the experimental data.

,
A copy of this program is given in Al\pendh. D, and a flow diagrrun
describing the computation steps is depicted in Figure 4.4.
The statistical analysis of curve fitting was basad an the Least
Squares method to find the regression, co~fficients and the variance.
The least squares criterion may be written as:
Minimize ~.l (C(z, t)obsarved-C(z, t)calcutated 12 •
where i - l, ... , ~ n being th~number of observed,.yalues, which are,
in this case, 6 equal layers.
" 0
I~ summary, the input parameters (or the prediction of contaminant
migration through the clay 50 il columns were:
- (
(1) The input concentration (Co),
(2) The initial concentration along the soil column (Cl)'

..
(3) The relevant dispersion coefficient (0), for specifie time
and depth intervals,
(4) The se~page velocity (V z ) which can be estimated from
the hydraulic ,conductivity results using Darcy's Law, and
(5) The sink or source funetion corresponding to a certain

contaminant species.
These parameters were then used to predict the contentrl1t1on
profiles both in the landfUl model and in-situ. .

This will be describcd
in the next section .
....
,
1
135
Start
Initial Parameter Estimates
Model
Specification ~
en
""
(J)
+'"
(J)
-_.~... __ Run Model
E
tU
""
tU
a..
::
(J)
z Calculate
(J)
+'" No Criteria
( -tU
:::::1
-0
tU
()
Yes Convergence?
No
î Are results
acceptable?
Yes
8
Fiq. 4.4. proceduré for Model Calibration Usinq Trial and Error Approach.
. ) ,.
136
4.4 COMPARISONS BETWEEN EXPERIMENTAL AND PREDICTED RESULTS IN

A LANDFILL MODEL
In this section the reliability of the prediction method \Jas
investigated through the use of a laboratory landfill model (phys1cal

,
mo'd~l) which was about 100 times larger than the leaching colwnn. The
landfill model was fille,d with the same natural soil used in the
leaching colurnns (Chapter 2). The soil was compacted at the optimum
water content and maximum dry density (30% s,nd 1.47 Mg/m.3,
respectively), in order to fac i l i tate compar 1son with those resul ts
obtained previously using test Seri~s No. III (Chapter 3 and Appcndix
D) . Also, the same hydraul ic head used for the permeat ion of th"
1
leachate solution in .the leaching columns .... as applied for the landfi Il
'0
mode 1 in order ta minimi.ze 85 many sources of errors as poss ib le. TIl(>
...,...,.
variable dispersion coefficient function, as well as the sourCE> or sink
"funetions previously obtained in Chapter 3, Were used for the predict ion
of the migration profiles
-
The leachate solution was allowed to perrne~te through the land!i11
model for a period of la months: which was equivalent to the pa&sa&~ 01
about one pore volume During this period, effluent and pore flu'id
,
-
samples were periodically collected at every 100 mm of th", clllY-
matrix, every 3 to 4 weeks. The pore prl'S5Ure, conduct1v1ty, and,
temperature ..... ere also measured along the clay depth of th~ landf i Il
model.
4.4.1 Pore Fluid Analy~ls
f'
An ~xamit:'ation of the eluted effluent and the 8011 pore fluld,
especially in the first 20 veeks of t.h~ land!1ll mod.l op.ration.

137
-( revealed that the contaminant species originally presented in the
compa~ted natural clay were washed out mainly due to: (1) "the initial
passage of distilled ~ater to stabilize the hydraulic coWu~tivit~!. of
the clay matrix, and (2) the mild nature of the leachate solution used
in the present study. This observation can highlight the problem of
elution or negative attenuation associated with the clay barrier,'
especially in the beginning of the landfill operation. The adsorption-
desorption and diffusi.on processes operate in a soil medium in such a
way, depending on the concentration of the ionic species in both the

1
pore fluid and adSorbed phase. The concentration of different cations
(Na, K, Ca, and Mg) was reduced st the upper clay soil levels and
increased at the lower levels. Nevertheless, following this initial
period, the migration profiles took the normal shape. Two relevant
contributing factors were: (1) tbe successive permeation of the leachate
solution through the clay matrix, and (2) the' increase in the ion
species concentration in both the pore fluid and the exchangeable
sites on the clay particle surfaces. Some of these results are given in
Appendix D.
Before proceeding further, it is pertinent to note that the
temperature did not vary with depth. Therefore, no flow occurred by
virtue of a thermal gradient. In fact, the effect of a thermal gradient
on seepage rate was insign.ificant when compared with the hydraul~c
gradient (R~udkivi and Nguyen, 1976).°
1 4.4.2 Predictions and Comparisons
To'predict the migration profile~ in the landfill model. the fini te
difference method explained previously'in Section 4.3 was applied. The

..
r
)
138
o variable dispersion coefficient functio~ was divided into six steps, and
the clay soil depth was treated in a similar manner (six layers, each
~ayer 100 mm in 1;teight). In estimating the concentration of the
contaminant species at a certain depth, the corresponding value of the
dispersion coefficient was used (Yong et al., 1985). The comparison in
predictions, using variable and constan,t dispersion coefficients for the 0
prediction of contaminant migra.tion, showed that better agreement \was
obtained between measured and predicted values when variable dispersion
coefficients were used. This was not unexpected, in view. of the fact
.
that the transmissibility properties of the soil changed with the time
of exposure to the contaminant load. For convenience, the method used in
the calculations was divided into steps, as schematically depictei in
Figure 4.5.
-- The agreement between'the

,
observe~ and predicted profiles after the
passage of one pore volume was fairly good (Fig. 4.6), since the method
was generally underpredicted, Le. predicted a lesser rate of movement
than occurred under natural conditions. The observed differences can be
attributed main~y' to: (1) the scale:up effects and the generlllization of
the back-calculated dispersion coefficient and sorption-dcsorption
functions determined using the laborftory leaching co lumns, (2) the
neglected retardation mechanisms (e.g. the biological upt~ke or fixation
of the different contaminant spec'ies, the backflow due to the osmotic
~radie~.f' and the boundary effects), (3) the efféct of the m~cro -tnl1cro
pores within the soil structure, and (4) many natural unknown phenomena
such as dehydration, co-precipitation reactions that cannot be fully
identi=ied or evaluated.
/
,~
139
permeant solutlcn (natural leachate)
'- !
c ;
«1
l-
CI
c:
:au
ca
CI
same
denslty
-l
pvd 5 pvd
~ 1 1
CD
:; (pvd::: pore volume displaced)
. '0
CI
U
0
I!lfluent analysis
J
$011 analysis performed for 6 layers as shown
è:
,,', iü
'ECI
t
.. J
layer 1
:§ layer 2 b - sOli analysis - 6 layers
Ci a - sOli pore fluld analysis
(exchangeable i ons and
c. layer 3
>< - 61ay ers (soluble Ions)
1 layer 4 extractable ions
ut
-. - layer 5
layer 6
t
mÎgra tion profiles

t t
calculatlon ot 0
of different contamlOants Ci ln each layer
;;_NC"'I.", ID
layer
.-.
- 1
1
E
.....E
2 l ~
.....
• 0-
ut
1-
CI)
)(
3
4
5
- "e
0
Il
Depth (mm)
Input Concentration C Hydrauhc Head = 25 m
L °1 l
1 1
li Initiai Concentration
J
c;' i:
1
1
layer,
i1
,I--~---------------------------l1
: z 1
:
,
:
1
= : 3 J
0-
ut 1 1
l- : .. 1
CI) l ,
1 1
:1 5 "
1 1
1~-------~",-- ______ J _____ - ___ l,..-------1
~ + ~ /
~nvectlon-Disperslon EQuation
1 1 1 1 1
0- 1+' Cl + Q.,o.1 C I " 1 -2CI ... Cl _, +~AI C,+rCI_t
ut CI = i 2. 2A Z
l-
CI) ~ Al ... R
c ::
0-
ut
l-
CI)
Predictions
, ·of
1
C
I~I
1
Fig. 4.5. Schernapic Representation of the Prediction
. Procedure,
o C ~.:')
,i/
"
el
< \
'1
Concentration (mgll) -~
o 5 15 20 25 o 5 10 15' 20 25' 0 8 16 24 ~ 32 40
0.0
1 1
,1 1
g ! 1
0.1
,f.
1 1
1
j, .1
1
"il
1 1 '.
1
,..... 10.2 1 1
1,--
--
E
,1
1 1
1
1
oC. 1
Q.
1 1
---03 1
Il) 1
0 1 1
1
1 1
1 1
0'4 1 1
r 1
•1
1 1
f
1 \
05
1
K 1\ Mg Ca
!
0.6 ~
Co C·
mg!l mgh predlcted Co Input Concentration
K 23 "8 \,..
., C. Background Concentration
"
~ 1
Ca 35 15-
j'
,....
Mg 8 .
Fla. 4.6. r-!iqration Profiles fran Laboratory 'Land.fi Il Model
"'o"'
.
"
16
'T'oaether wlth P're:hcted Resul ts at One Pore VOlumé .
.
.. r:'
. r ~,
-.
141
4.5,SUHHARY
The prediction df contaminant migration
..
4ivided into four steps, namely: '
(1) Quantitative measurements of the influence of s~ll and ieaçhate

., ,
."
,(
"
parameters on the attenuation of those contaminant speciés.
(2) Comparison of the theoretical curve~ obtained from- the

/
computer model wi~? the actual data obtained exp~rimentally.
(3) Translation of .J;kese parameters blto migration r~tes (through
the use" of a dispersion co~fficient function) fOl?' a parti,cular
contaminant, us ing the migration, profil~~ deteimined from'
measured sQil-Ieachate pararneters:

o
(4) Use of these bacK-calculated functions to predict tha mi~ation
of contaminant species under field conditions.
( The convection-dispersion mathematical mOQel offets a promising

"..
~pp~oach for assessing contaminant migration arôund a solid waste land
disposai system. Through simu~ation, the model can describe the system
in its' present state to a reasonable accuracy, or it, can be used to,'

.
evaluate its future behaviour ,-or status: Neverthele-ss, .the results of
. "
these prediction techniques must not be allowed to' takce "precedence over
field inv~stigations, data
landfill si te.
, ,
'( ,1
~... \'
(. \(
Tf) .,1: \'
, " . 1'0', "
.(\
c:
"':,L " '. ~,
.~
"1
) \ r .. "':;,!,
142
o CHAPTER 5
FIELD INVESTIGATION (CASE z;;STUDY)

".
'.
5.1 GENERAL
""The groundwate,r pollution poténtial of the active sanitary
v·
1àndf\ll s~te located near Montreal was investigate~ in the period of
.
January 1984 to January 1986. The purposes of the study were:
(1) To examfpe the qualit~of the 1eachate produced in the landfill
site,
. (2) To determine the attenuation 'of the contaminant species in the
landfill site,
/
(3) To evaluat~ the possible extent ~f groundwater pollution by
,. ;..
"
1andfill leachate at the site, and ~
-
\-~ ;.
(4) ToJp~ediçt contaminant species migration in the field.
This Chapter presents the results of a two~year investigation

,
concerning groundwater quality at the actual landfill site.
..
J 5.2. DESCRIPTION OF THE STUDY AREA
t " "-
. 'Ote .landfill site investigated is loc.sted at Lschenaie (35 km east
of Montreal). lt serves a population.o'f- about 270,000 and receives
225,000 tons of muniéipal and industrial solid· waste annually, The

1 •
landfill began op~ration

.., as a dump site in early 1981. ~xcavation was
made for waste containment,

, and patural clay sail in the excavated area .
was compacted alGmg the slopes to ,serve as lining material (Fig. 2.1).
Compaè'tion in plaçe wa"S specified ta achieve 100% st"andard Proctor
dens-ity.
{)
" ,
-
•
.-
,
·1
143
The soils underlying the site consist of. sands, silt clays and
. '
tills of Quaternary ~ge. The upper-mo.:;t lay~r.)ls formed by sands of 2
to 4 m in thickness. The sand layer is underlain by approximately 20 m
thick '$ilty clays deposited'during the Champlain sea episodes, and
tills dating to the Wisconsin glaçial period. The groundwater level in'
the al1ea is located. about 0.4 m below the ground surface level during
the spring, but it descended tp 0.8 m below the ground surface during
the months o~ July and Augu~t, and groundw-at-er "Was" àlso detected in
~
the till layer. The hydraulic gradients measur!,'!d frore "the monitori~g
. ~
system indlcate that, the groundwater flows from the north side of the
landfill ta the §outh side.
The Iandfill is operated by the trench method (ASCE, 1959).
Individual refuse cells are about 15 m wide, 7 m deep, and range from 70
.,. .
to 400 m in length. Re.fuse cells are covered with a final layer of
compact;ed soil ranging from a few mni to' 600 mm in thickness (Fig. 2.1).
Final re~toration of the site involves planting evergreen seedlings,
although natural', grass and vegetation predomina te about 5 yea'rs after
the solid waste is buried.
,
Refuse cells usually become~ predominantly anaerobic shortly after
,
empl.acement. In.general, conditions are relatively perobip near the
~face of a refuse cell and become increasingly anaerobic towards the

'"
bottom. Leachatê quality is primarily influenced by the composition and
amount of refuse in the landfill cell, and secondarily by its sorting
and degree of compaction, the amount of water in contact with the solid
" .
waste, and the seasonal temperature. Solid waste.constituents ,which
aff ect leachate quality include biodegradablè organic matter, soluble
inorganic materials, and redox-sensitive substal)ces, such as mast of: the
• ..
•
144'
o metals.
The chemical analysi~ of the leachate' solution samples was limited
to the determination of specific conductivity, pH, major cations (Na, 1<,
Ca, and Mg), maj or ~nions (Cl, C03 , HC0 3 , and 804 ) , heavy me tals
(Zn, Cu, Pb, and total Fe), and total organic carbon (TOC).
Well No. 4, which was located at the' upstream end o_f the disposai
",
,
site (Fig. 2.9), was selected as a reference well to reflect the
"
chemical quality of the uncontaminated. water entering the landfill
vicinity, The concentrations of different contaminant species in Well
No. 7, which was located directly in the fill,e were used as tRe initial
concentration CC o ) for field predictions.
5,3 VARIA'fIONS IN LEACHATE QUALITY AT THE LANDFILL SITE
- 5,3.1 Changes in pH Value

\
As shown in Figure 5.1, the samples from Weil No. 5, located in the
immediate downstream Emd of the inactive dumping area, indicated an
increàse in pH value wh en - compared to those of Wells No. 2 and 3
located near the active area. The p~ value increased to 7,5 from an
.
average value of 6.1, probably reflec~ing the phase ~hanges of' the
.-
was.te
•
decomposition
.fi
from an ace tic• production phase to a methane
production phase. This could be associated with the fact that the
earlier arriva1 of leachate -containing ~ganic cOp1pounds of a few mg/l

~
initi,ated the anaeropic conditions and the bacterial reduc.tion of
nitrate and nitrite to ~onia, ensued by reactions such as:
•
NO; + éH2 0 + 5H+ 1'" 4e- - NH4 0H + HCO; + H2 0 (5.1)
0.
"
145
),
o
• WELL 5
e WELL 2
4 WELL 3
8 0 WELL 4
7 0- 0
C
~
-'
• •
J:
0.
6
_tE~
_./ e--::;::::::. ====-. • t ..
• •
5
,
1
!
4
March June Sep Dec March June Sep Dec

1984 1985
Fiq. 5.1. Change in pH Values in Different Monitorinq Wells.
\
..,
)
146
where ~H20 represents - the or ganlc matter. The reduction reaetion

/
illustra ted in equation (5 .1) raise~ the pH value and probably accounts
for the maximum pH values of 7.5 observed in the field. Quasim and
Burchinai (1971) have observed similar results in their simulated
lancUhll model. lt is also pertinent to note that -pH values in the

-' "-
control WeIl No. 4 were slight1l higher'than in the other wells.
"
5.3.2 Changes in the Specifie Conduetivity Value

"
Figure 5.~ illustrates the variations in_the specifie electrical

"
conductiviy as an indirect indication of the. total so lubIe ions. WeIl ,
No. 5 showed signifieantly high coneentratio-ns of excess ions as
compared to the reference WeIl No. 4, while WeIl No. 3 sho~~d relatively
stable specifie conductivity values. Nevertheless, after 6 months of
- sampling, the specifie conductivity values at WeIl No. 2 showed a sharp
- increase, while the other wells (e. g. We1ls No. 1 and 8) did not show
any detectab1e change, indicating that the distance of the wells from
the source of potential contamination was sufficiently far.
5.3.3 Changes in Heavy Metal Concentrations
Migration of heavy metais is essentially limi ted due to their
attenuation by more stable fractions, sueh as coprecipitation with Iron
hydroxides and incorporation in silicate lattices. The laboratory
results cçnfirm this tendeney. These heavy metais did not occur 'at
leveis above the drinking-water limits even at the monitoring wel~s
close to the dumping area (Wells No. 4 and 5). From the consideration of
sôlubility and observe4 pH values, it is expected that solid~phase
solubility should severely limit the appearance of'most heavy metals in
-,
--,
-.
147
( t
WELt 5
•
• WELL 2
... ,
- E
0
........
WELL 3
0 o WELL 4
~
E 1000
:::t. ...
1 ......
.....>-
.....>
(,)
:::::J
800
600
---- ~~.~--~.~
_--_---e
~~ .
'"0
c: 400 ---4.----.- ..-/.:_______ .- .. ,
0
() ~-=t-o- - +=-- '<:::.....,~":.::.":.::.===*~----~.----. .~o.
..
<. .-- (,)
( ,)
(l)
200
00
Co
Cf) June Sep Dec
March June Sep, Dec" March
1984 1985
Fig. 5.2. Change in Specifie Conductivity in Different Monitorinq Wells.,
,.
.C
( ,
. \
148
t
\
o the migrating leachate solution. It is aiso-expected chat adsorption
would be an important mechanism in limiting the mobility of some heavy

"\
m'etals, based on the concentration and selectivity coefficient
constraints. Thus, heavy metais were effectively removed from the
leachate solution which migrated through the subsoil below and around
the lanifill such' that heavy metals did not occur at concentrations
.'
reaching the hazardous levels. Nevertheless, the chemical analysis of
the well water samples showed a s ignificant amount of iron, 1. e. in the
,~ ___ ord~r of 5.0 to 8.0 mg/l. This could be attributeo to the isolation of
solid waste materials in the landfill celis which in turn could preven\
contact with atmospheric oxygen or oxygen-rich fresh recharge water'and
biodegradable organics in the refuse. Under such environmental
conditions, dissolved oxygen in the water and soil moisture is rapidly

,
-
depleted by aerobic bacteria, and anaerobic decomposition then
predominates. In the anaerobic environment, iron can exist in its highly.
soluble and mobile divalent form (Apgar and Lagmuir, 1971; Full,er and
Korte, 1976).
o
5.3.4 Changes in ~~kali and Alkaline Eart~ Metal Concentrations
Figure ·5.3 (Wells No. 2 and 5) displays the changes in alkali and
alkaline e&rth metals. The concentration of Na is seen to increase with
time, after a slight. decrease observed in the beginning of the sampling
period. No sïgnificant change in K ion concentration is mted, while. 'a
.
dec}:'ease in Ca concentration is observed, followed by a somewhat
steady state of the concentration. Thesè variations of concéntration are
ascribed Co: (1) che result-of'increasing pH values, suff~cient enough
tQ precipit~te calcium carbonate, and (2) the adsorption of Ca ions on

/
/.
1.
1
r
J
/
149
(
,
• <:.
Wè~1 2
200
• Na Ca
o K Mg
"'"'
.....
Ol 150
-E
c:
·C . -
0
- ,,
-
CV 100 \
'-
k-------~__~--~------Â Â
-
c:
Q)
C,)
c:
0
Ü 50
.-
. • v--~-- V
.-__ ~ 1 -Or-----V~o,--- 0
<1>-0--0--<>--0 -c---o--- o~
.. ~ V
~-v-,,-v . "~ y ~\
00
March June Sep Dec March June Sep D~c

~
1984 1985 ~
Fiq. S.3a. Chanqesin Cation ConC'entration in WeIl No. 2.
, - (
,, . ,
,) .
150
o·
Weil 5
200
• Na
0 K
"'......"" ....
Cl 150 .... Ca
", - E
c: ! Mg
., .... --°
co 100
• •
.~7'. •
~
} c: t- Â A
....... Cl)
()
c:
\...-- .......
",0
Ü 50 ~.-e-.---e----A------ 'V" t7 V
7-11~fl----
fl
o~
......... 0 0
o----c--o
..:...
00
) March June Sep Dec March June. Sep De'c

1984 1985.
Fiq. 5.3b. Chanqes in Cation Concentration in Well No .. 5.
o·
\
. '
the charged sites on the clay surfaces. Nevertheless, Mg concentration

( in the control and other wells did no~ show any definite tr!,!nd. A
comparison of typical cation concentratibns in the· pore fluid of soil_
samples close to the site and remote from the dump area is given below: "_
"
Cation· ,- Uncontaminated C6ntaminated
--
pore :fluid (mg/l) pore,fluid (mg/l)
--------------------------------------------------------~----------.-----
Ca 22 ./ 40
.... --~
Mg 29 38
K 14 21
Na 130 156
* Samples were collected from the landfill area in Jan. 1984.
o
5.3.5 Changes ~n Chloride and Organic Substance Concentrations
The Cl ion concentration was the parameter most indic~tive of the
extent of the contaminant migration. Wells downstream from the refuse
area showed an increase of 50 mg/l more than the chloride concen~rat~?n
detected in the control ,Well No.4 (Fig. 5.4). Thus, the chloride ion
could be considered to be the most suitable indicator of 1eaching

,-
migratio~n from a refuse dump because:' (1) it can,be easily mea~ured and
detected _(both at site and laboratdry), (2) it 15 not readily adsorbed

-..!
by the soil, (3) it is not altered by biological processes, and (4) it
is present in the leachate solution in s~fficient quantities.
The concentration-time plots (Figs. 5.1 ta 5.4) show that maximum
( specifie e1e'ètrical conductivity and Cl concentration were obtained
"
)
152
WELL 2
(,
200
• Cl
-
......
O'l
0 TOC
-Ë
__ c:
150
....
0
......
.----------.
-
~I .'
"li (-
~
<'il
1....
......
c:
ID
()
§
100
/
• •
ü
50 ...-.............
.-.-o-~o--O---D- -0 0 0 0 0
00
March June Sep Dec March June Sep Dec

1984 1985
(
l?ig. 5. 4a. Changes in Cl and '!'CC Concentra tj:on in Well No. 2.
.
153
C'
o
WELL 5
200
-
.....
Cl
E
.....,
• CI
150 o TOC
c::
.
-
.2
-C'J
Loo
c::
(])
()
100
c::
0
()
50
00 ~'------~------~I~.----~L-------L---~~~----~------~
Mareh Junes ·Sep Dec Mareh June Sep" \ pee
1984 1985
- .
Fig. 5.4b. Changesin Cl and'Iœ Concentration in Well No. 5.'
. 1
·c
...
154
o aImos t simul taneous ly at each monitoring we 11.
The behaviour of rédox-sensitive species including organics and
ammonia is' complex and less systema~~c. The total ~rganic carbon (TOC) o
concentration in Well No. 5' underwent a significant increase over the
concentration in the cc;>ntro1 well, especia11y in the first 6 months of
the fnvestigation. ' This increase was in the order of 100 mgll.
N~vertheless, --.the :roc concentration at 'wells No.< 2 and 3 were almost

.
.cons tant (Fig. 5. li). These results for dissolved organic carbon
iÏldicate that organic compounds are very mobile. '
5.3.6 Other Contaminant Species
Sulfate compounds were found to be extremely low. Sulfate was
present in the leaching solutions from inorganic matter and organic '\
sul fur produced by microbial d~composition of amino acids: The pa-et:ern

"
of S04 concent~ations suggested, that S04 was removed from the
leachate eithe~ py adsorption on the 'positi.ve edge charges of the clay

... minera1s, . or by transformation into othér éompo~nds due to the redox
conditions within the landfill.
:t'he bicarbonate (HC0 3 ) concentration increased significantly at
Well No. 3 which· is !jIufficiently distant frpm the source of potential
contamination. The incre-ase was of the order of 50 mgll.,
o
\
\ \
\,
\ - --~
- -~--
. "" ~ " ... "~ "" """ ;" ~
, .'
10
l,' , (
1
'-' ,:::.
" (j ~-
îss
.
c 5.4 SUMMARY
During the 1984 to 1985 p,eriod of

, c
investigati~~b no
c "
-,
mae,~J'
,t
r
,
,~
"-
varlàtions in water quality of the reference wé11 wet'e noted. 1Any ~
, ,
~,
1 ~
,
()
chemica1 changes that were observed in the reference well could be j
1
influenced by the location of the well, and by the~climatic vari~tions \
, 7
• 0 ,
that occurred during the two years" of 'samp1ing period. As 1eachate moved
•
slowly through the subsurfacè, ~ts compositi01'l.. gradually changed,
ref1ecting the increase of sorne contaminant species or the various
~ 1eachate-soil interactions. The results from the field study and the
-
associated laboratory experiment suggest that the clay soi1 is fairly.
efficient in containing the various contaminant specie~ generated at the
landfill site. The findings from the field study can be summarized as
follows:
.
C ( 1) 't'he migration of heavy metals was found to be limited,
with no significant concentx:ations detected.

')
(2) Geoc!1emically, the most important p+,ocess is ~he acid/base
reaction, which tends to increase 'the pore fluid pH, thereby
favouring the precipitation of contaminants spéh aS heavy,

•
metals, and increasing the q~se exchange cap~city of the soil
system.
(3) Both chloride and dissolved organic carbon compounds ,were

"
. found to be very mobile in the' natural soil.
Q
(4) ather contaminants such as sulfate, bicarbonate, and nitrate

'l
were not present at hazardous 1eve1~, as observed in all.the
monitoring wells. \
....
..
,,-
... ,(J
o '
156
..
,0 5.5oPRED~CTION,OF CONTAMINANT ~IGRATION
The >,field monitoring results presented in Section 5.3 indicate

IN THE FIELD
the infl~n~ of the dumping site on the qua1ity of the water collected
in.the wells located at different di~tances from the site. Dispersion,

" '
in addition to convection flow, can be tbe driving mechanism for the

~ t; ~... ~ ,
.
,l 1 1 0 . .
, ,
migration of different contamin~t species. The two principal mechanisms
( ~
contr~llin~co~taminant transport are..rnsid;ted i~ arder to predict
the ettent of contaminan~ migrâtion oyer a period bf time, as weIl as
the required'clay thickness for retention of v~rious contaminants. The
analytical model selected for predic~ion purposes is the convective-
dispersive mas~ transport, using the sarne Jnput pararneters as explained
previously in Chapter 4.
, .
5.5.1 Average Dispersion Coefficient
...
" ~ .
A s~mplified> case ustng an ave~age dispersion coefficient and a
linear relation~ip between S a~d C:

<> -
.'
(5.2)
, ,
was used ta 'prediet the migration of 'calcium ions in the field as an
example of ionic migra~ion (other examples are shown in Ap-pen.çix ~).

~..(
An average dispersièn value of O.OOOO~ mZ/day was used and by the t
method of least squares, Kl and ~ were found ta be 81.40 {ind 0.004, '"
_ , 0
~espectively. The tintte difference method was employedqto solve the
partial c;lifferential equation of the convect'iv~-d,isper.sive model.
Central difference as an approximation to detivatives was "',,!sed, and Q
sinee the prop:,"sation Is fOI;Ward ";"ith tespèet to -the time scale, a
forward time difference was a1so used. "

Tnerefore, an approximation"to
...
.
.'.
o
" .
157
c
_ - - - ---- - ------ 1)
the differential equa~ion by the fini~e differencé equation is:
j 1
Ci + cj Cj 2 cj Cj
- i D -=.i+""'1:..-_---,~1....+_-'1:..-..;1 (4.7)
At - R .llz2
Figure 5.5 shows the relative positions of the mesh values of the
concentrat,ions involved. The fact that there is only one value at the
~
further fo~ward time level (j+l) indfcates that this is an explicit

..
scheme. The schemè is valid for mesh points in the interior of the
.
domain of the solution; the values on the boundary are specified.
Rearranging the scheme gives explicitly a formula for CJ +1

1
f-
I ~
~
T
j
CJ + Q At C1+1 .. 2 C + CI-l - y. At Ci+1- ci-l
J
CJ +1 _ 1
(5.3)
1 1 R Az 2 • R 2 'Az
The time Increment chosen was 90 days and the depth Increment was
0.25 m. A constant concentration Co was taken as the average value
obtained at Well No. 7 beèause it was located in the fill itself. The
seepage velocity calculations were based on the piezomet~r levels

" ,
observed in the field, and the hydraulic conductivity was measured from
,
the laboratory tests and by'the application of Darcy's Law, Using these
input data, a computer program was developed to predict the ion ~Yement
in the field 'for periods of 25, 50, 75, and 100 years. A copy of the
•
computer program is given in Appendix D (Section 2) and the results are
shown in Figure 5.6 and 5.7. Additional results are given in Appendix D.
t
Since the dispersion coefficients were ~btai~ed from th~ migràtion
,
.profiles at laboratory tempetature (20 OC), these values ·were
correc'ted for the field temperature us ing the relati~nship given by

(
\
\
\
,
'.,.
1
".\ ("
158'
1>
o .c.
j
0 ~ ./ ./" ./" /' ./' ./'" ,../"
/'
. .
/' -
./"
k
...
...- • <
1'"
i -1
-
-
.. ./'
.!III i
-
.
i +1
./
.' "" ~
. ,
./ ,
h "
/'
"
~
./"
\,
~
-
x= L
.......
Fig. 5.5. Finite Difference Sch~è.
",
. .~
\
.~
159
/- -----
~
Concentration (mg/!)
120 150 180 210 240 270 300 310
o ;------r------~~~-----r------ïï------,-----=-~----~
8
,...... Weil No. 2
E
....,
a>
'u
liJ
">-
l-
:::J
1
I
1
• ~5-years
l
~(
Cf)
12 '"'- 'il 50-years
....
1J
c
C'Ü~
• 75-years
....J a "
"0 100-years
~
0
t, a> ~
CO 16
.c
....
0.
Q)
Cl
\
20
..
, >
.'
24
c Fiq. 5.6. Concentration of Ca with Depth and Time at Well No, 2.
i
J
;
,J
'~
'(f -
160
r- -
ConcentraJion (mgll)
100 130 . 160 190 220 250 280 310

( "
('
"..
c'
4
b
~,
"
..-. 'J
\\
- E
C)
ü
8
Weil No. 1
:
,i
\
"
' ...."-
Cil
'::l
~
Cf)
.....-
• 25-years
::it 1l -0\ "V 50-years
.........
..
C\
Cil 12 ...
~ ,
-l
$
0
• 75-years\1 ,
~
Qjt ...
0 10Q-yea.rs
• m
0
-
.c.
0.
(!)
16
< ~
, e
20
24 •
Fiq. 5.7. Concentration of Cl with Depth and 'rime at WeIl No;' 1., ".
161
c Mangelsdorf et al. (1969) ..
~
(5.4)
-,
5.5.2 Prediction with Variable Dispersion Values

'.
As seen from the experimental results, the dispe'rsion coefficient
,
values were constantly changi~g with ~ime and depth. In o(der to depict
migration profiles for. different contaminant species comparable to the
actual situation, variable dispersion functions obtained from the
experimental data,of the leaching columns were used. An,exponential
relationship between adsorbed (S) and soluble (C) contaminant species
was used. This mathematical relationship was as follows:
S - G - B exp (QC) (5.5)
where B, and G are constants det~rmined by the least square method.

( Q,-
This atlsorption functiOn together with the convection-dispersion model
was used: (1) to pred~ct the contaminant migration profiles at different
~ time intervals , and (2) to estimate the moving front of the di~ferent
/"
contamin~nts under field conditions. This mov~~g front represen~s the
location of the contaminant which reaches the influent concentration,
i.e. Ci - C (ft pore fluid).

".
For the
.-
prediction o'f the calcium migration profile in the field,'
(\
the different constants Q, B, and G: Wére found to be -0.002 I/mg,
0.006, and O~Ol. re'spectively. Befor~ applying the finite~difference

- -\
technique, the following conditions we~e imposed: - "\
~ ,
(l') The prediction periods of 25, to lOD yeats were assumed to fan
within the first stage of the ç~ntam~nant migration through the

/ ~ /~//
c clay'so,i1 depth, i.e the functr'ion -concerning the passage of one
1
(
, <
1r
162
pore volume was the one employed in the prediction.
(2) Si;nce the monitoring wells penetrated to a depth of 4 m,
each layer in the prediction was assumed to be 4 m deep with
an illcrement of 4 m as weIl, i. e the prediction of the
concentration~ was made at, every 4 m.
. (3) The contaminant concentrations at every 0.25 m "'lere estimated.
by extrapolation.
The finite difference method was used with the ~receding to solve
the equation of the convective-dispersive model. Typical res lt.:S are
given in Figures 5.8 and 5.9. The results showed th'at there
1 -
significant increase in concentration from the depth of 8 m do
Therefore, one can conclude that the' compacted clay is effici
contai~ing the .leachate and thus im preventing it from polluti the

~
" '-
l:;i
\
:;,~
groundwater system, at least for a period of
that the clay is sufficiently thick.

~p
5.5~3 Predicted Moving Front 0 Contaminant Species

'"\ "
It is ·Qften necessary 10 e ,ma~e the potentifll! travel distance or

length ~of time required \for aJontaminant to' migrate through the
{
subsoil. ,The analytical' solution of the convective-d~spersive mas's
...
transport equation was used to deveiop a.graphical solu\ion (nomograph)
ff
for providing a simple cornput~tional tool to prediét leachate' rnoveme~
and i'ts corresponding C4!I"Ocentration. A typi't:al exarnple of these
nornographs predicting the movement of Cl at different concentrations is
dèpicted in Figure 5.10. As mentioned earlier, Cl is very mobile and can
serv~ as an indicator for the extent of the migration of a, landfill
leachate solution.
, '
,. .
.. ~
163
c <"
\\
(
~
Ca Concentration (mg//)
+250
C;.- Landfill
-
0.0 ,40 120 160 1200 240
0.0
\- 80
--'-- - --
---.~ .. -- -
::::::;;---.:- ,.
000
«>
--
E
2.0
/
.'
~
.-.--'
/",/
-"
..
.....
,.."
.....
<1> 4.0
.. /r ./ ""
-
()
CCl
/ 25-years
~
6.0
:::7
Cf)
-.--
"0
C
CCl
8.0
10.0
, 50-yeats
75-years
...J
;:
'(l.-\ 0
<1>
120 100-years
CC
-
14.0
.t:
C.
<1> 1 6,0
Cl
Natural Soil
18.0
"20.0 _ 20.00 .
G.r:oundwater
" ,
Fiq. 5.8. Prediction of Ca Miqratio~,Th~qh.ClaYSOil of 40 m Depth.
... 1
1
/- ,
( )
,
.'
'-.
J
164
.()
,.
CI Concentration (mg/I) -
"1
+2 50
- 1
, Landfill
0.0 40 80 120 160 200 240
0.0 000,
~----
- -- 1
.,
.......
1=
(J.)
2.0
4.0
,/
/
~'~/--' ,
.
/
./
/'
\
Ü ;
co
.... 1
~
:::l
60 25-y~arS
(J)
80 _.- 50-year~
....
-..-~:::
v 'Ilf
c:
-
-~}
~
~
, $
(\l
...J
100
120
e
- _.-
-------
75-years
100-,years
0
(J.)
..
.1,
C!)
=
- (rllg/I)
N.O
-C C o 50
!f
Q.
(J.) 16.0
0
Natural Soil ,/
18.0
200 _ 20.00
Groundwater
.
sa
F1U '5 9. Predll::llOll or
'P
Cl ~lgratlon Throua h Clay S'lll of 20 m Dt"pt h. '"
i ~.
/
~n
'1, _ ~ 1 0
• ..... ,
"
J
,, '\' ~
1
1
1
'1 \0,
# ....
r
1"!tt4
/
~
, . ~ ,... J
4.0
Natural Clay: Water Content ~3'2 %' & ·Initial Dry Density = 1.67 Mg/m
3
tiydraulic Head = 2.5 m

. . .' .9 .9,
3.5 Hydrauhc'Conductlvity = 7~10 to 7.5X10 rn/sec
Diffusion Coèfficient = ~ zN
30
0.5 pv M= 0.186 & N=0.736·

l)
25 1 pv M= 0.226 & N= 0.739
...... ,
'-'
E 3 pv M= 0.298 & N= 0.583
.,C.
-
0.
(])
2.0
5 pv M= 0.149
..,
0
15 Lv /
1.0
'""-
05 .'
0.0
o 5 1p 15 20 25 30 35 40 ~5 50 55 ~
Time (.year)
/'
.... "
• ' 0.5 N NaCI A2.0_N NaCl • 5.C} N NaCI
'" o 1.0 N NaCI • 3.0' N NaCI .....
0-.
\J1
*.e:
Fig. 510. N@mograJ?h for Solution of Tlme, Distance. and Concenlration
for Cl Ions.
.. " ... ,.
a66
Such a relationship can-be used to predict the following: (l} the
maximum distance of the contaminant migration for a given
concentration, which might be that established as a standard for)safe
drinking water, and (2) the maximum leachate concentration that Gould be
tio
reached at a specifie distance from t~ landfill. The prediction is not
absplute because of, the simplifying assumptions and estimatep-made for
- the parameters required in the solùtion of the mathematical model.
Nevertheless, the predicti~ns are useful for better understanding of the

, \
.
hydrological setting and contaminant behavioûr at a~ existing or
'\
proposed landfill site.
---~
"
"
•
o "
,
.
, ',~
__ -- - ~~--r--l-
167
- -,
SUMMARY, CONCLUDING REMARKS AND
SUGGESTIONS FOR FURTHER STUDIES
6.1 S~Y AND CONCLUDING REMARKS
This study is focused mainly on the attenuation of contaminant
sp~c;Les which are usually pr~sent ,in landfill. leachate solution by
natural clay soil, This research program is also centered on the
modelling and application of data derived from the soil! columns for ~.
'pre~ieting contaminant spec~es migration through clay soils, both under
laboratory and field conditions. The following observations and
conclusions were drawn:
:1 A. Laboratory investigation: "
(1) The migr~tion~f heavy metals (Pb, Cu, Zn, and Fe) appears t~
"be limited through' attenuation by the natural clay soil.> The
experimental data suggest that the low level of heavy metals
in the municipal landfill leachate is unlikely to pose
a contamination threat to the ~ubsurface environment, provided ",

-
trat a low< acidie {Vironment is maintained. It shouid be
emph~sized that ~ar must be given to minimize the disposaI of
acidic waste, sine it can increase the mobility of 4eavy

1,1
,/
metals. ;{I
"""'-
l '\
," .(2) The ratios of chloride to different cations stud,ed showed
trends expected from the cation-exchange prdcesses. ~e CI/Na,
K, and Ca ratios i~dicate that chloride concentration along the
flow path significa~tly increased with the successive intrusion

-- ----~~~
~~--~---~ - - - - - - - - -- - --- - ---~~~------
168
of the leachate solution, as seen in the di the
one and five por~ volume profiles. tions of K, . Ca,
and Mg ions were more pronounced ,at the 'upper la er of the" clay
column, and attenuation de~reased toward the lowe porti~n of,
the clay column.
(3) The organics were found to be relatively h the
olay soil.
(4) It was observed that the exiSting "'models

- 1
- 1"_-
desorption did not, fit the behaviour of the multicomponen
natural system. Nevertheless, a mathematical relationship of
the form (S - G - B exp(a C)} was found to describe the
behaviQUr and the response of the ~atural system fairly._well
(where Sand C are the exchangeable and soluble cations,
respectively; G 1 B, and a are constants). This funct;ion
~eemed to overcome deficiencies of the previous models.
-
eS) The point of interest in maki~g predictions ,of contaminant
migrayion capability in a particular soil system centers-around
the dispersion coefficients. Clearly, d,ispersj,on coefficient
(D) values changed with continued intrusion of the
contaminant. as seen from .the experimeptal resul ts. Thus, a
- fixed ~alue for D for a paitic~lar ion, and for a specifie

-,
type of soil, is fictitious. A generalized function of D
.
values in terms of time and space is needed and
. (
~less
o
this 1s\
• \
established, an âccur~te pr~diction of contaminant migration
can not be re.asonably m'ade.
(6) The
1
convection-dispersion mathematical.model offers a promising
~ ,\.
169
c- approach for a~sessing a s01id waste disposaI system to a

"
reasonab1e accuracy in its present state or it may be us~d to
1
1
_ evaluate its future behaviour or status. _Nevertheless, the
results of these prediction techniques must not be allowed to
take p~ecedence ov~r fièld measur~me~ts and investigations,
dal:a collection, as weIl as inte1l;>retation at t;he landfill

• ~.. ,. ~ 1 ..
\'
site.
B. Field Study:
"-
The quality of the groundwater and leachate solution generated'at ~
the landfill site reflected the composition of the soUd waste

1
with
•
which rain-wa~r and/or subsurface water was in -~ontact. The Iresu~ts. of
the field and a'ssociated experimental analy,ses suggest that the clay
soil is fairly adequate in containing .the various contaminant species

.
ge?erated at the landfil1 site. The .find~~m t~is field study can
be summarized as follows: l,
,~
-
~~ ..... -..""""
~
/
(1) The mig r a t ' 9 heavy metals was found to be 'Umited, with no
significant concentrations being oetected.
(2) Bo.t\ chlor~de, and dissolved organic carbon compounds were

'\
found to be very mobilè in the natural soil.
(3) Other cont~inant species, sud} as 5ulfat.e apd bicarbonate,' did
not exist at hazardous levels.
\ , ,
\ \
\
\ \
•\ r.
1
n-
.~
1:;70
l
6.2 SUGGESTIONS FOR FURTHER STUDIES

~
Further
•
work shoul~
•
be concentrated
<
on:
\
(1) Develo~ing a more comprehen~ive mathematical model ?.for

/"
t
predictive purposes, which could include more environmental
variables, and better s~mulatio~ of~e natutt~~ ~ystem,

(2) The effects of the initial and bcundary conditio~s; as weIl a~
,
the shock loads of the contaminants on the clay barrier system. >
tl '.
(3) Exercising more attention to the physical moAels (laboratory
landfi,ll model). despi te the high cos·t and the time- required
Go
.-
~
for thé analyses.
; 0 . -
(4) Th~,mechanisms evolved in ~he attenuation ~ different' organic r
-";=
- --
- '\
groups,' especially the total o~ganic halogen (TOX) which is an
.!"-.; - ..
.'
1.
, indication of syn~~etic chemical contamination, anrr~-
(5) The microbial degradation and fixàtioh 9f t~~'~ifferen~ organic"

\ 1 1
species "present in the landiill leachate solutions.
. -/
1
.~ .....
".
\
\
" . '
o...
. , ..
1
/
C'
ln "
•
i"
REFERENCES
-
Acar, Y.B. and Sea1, R.K. ,(1984). "Clay Barrier Techno1ogy for Shallow
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( Interscience, John Wiley and Sons, Inc., New York. 747p.
~ , '
Alexander, G. B., Heston, W M. and 11er, R.K (1954). "The Solubility of

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~
American Society for Testing and Materials (1970). "Special Procedures'

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"
Anderson, D.C. (1981). "Organic Leachate Effects on the Permeability of
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/
Apgar, M.A.. and Langmuir, D. (1971). "Ground Water Pollution Potenti~l.
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\
Aru1anandan, K., Bausu, Rand Schar1in, R. J (1973) " Significanoe of
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\
.
172
"
( ". -
Sei. Soc. Amer. Proc., 16:176-182.
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f'
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~ ,
, 0
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p
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l '
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(~
Cogauan, B.G , Green, R. E. and Uehara G. (1968). "Solute Dispersion in
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f
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•
"Complexes of Halloysitr with Organic
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J-
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\
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-~ # " "
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1 •
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- . Lindsay (Ed.), Mieronutrients in Agriculture. Soil Sei. Amer.
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Their Effect on Ground Water," Report No. EPA 570-9/77-002,
Washinton, DC.
,r~,
Environmental Protection Agancy (1983). "Lining of Waste Impoundment and
.......
,,
\
Disposa'l Facilities," SW-870, Office of SoUd Waste and Eme~gency
~
174
-
Response Washington DC. 20460.
. "
Environmenta1 Protection Service (1979). }" Laboratory
. Manua1,"
....
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Colloidal
(
183
AP~ENDIX A
CLAY SOIL PROPERTIES AND CONTAMINANT IN~ERACTIONS
A.l GENERAL •
Lining the sanitary landfills an~waste containment po~ds with man-
made materials of low .

permeabili~y has been demonstrated as a feasible ~
method for preventing leachate and waste liquid components from leaving
the waste storage site and polluting the subsurface environment and/or
the surface water system near the site. A wide range of materials are
available as candidates for specifie impoundments,' one of these being
the compacted clay, or clay liner

\
A clay liner is defined as the èlay mate rial at or near the waste
dispos al sitè that has been properly treated, remoulded and/or compacted
sa that a flow-impeding layer of low permeability is obtained. Due to
their general availability, clayey soils must be considered as the first

\
possibility for lining tne waste containment ponds Alternatives
should be consldered only after a negative analysis is made on the
native soil, based on engineering, environmental, and economic criteria
(Landreth, 1980)
Liners can function in two ways: .

\
a) They can imped~ the flow of contaminant species\ into the
\
subsurf~ce environment, and/or
b) They can adsorb or attenuate .suspended or dissolved
contaminants, sa that effluent from the landfi l1s an~ waste

/
containment ponds will fall within the quality ranges set by
the environmental agencies

\
-..
/
184
(~
Most liners function tn bath ways but ta different degrees.
. .
r
Membrane liners are the most impermeable, but they have lit~le capacity
for adsorbing materials from the waste. In contrast, clay lilners have a
large capacity for adsorbing and/or retaining contaminant species, but
they are more permeable than membrane liners (geomembi-anes)
. .
Nevértheless, their greater thickness can.result in low hydraulic flux
through the liner The clay lining system must be confined mechanically
under pressure great enough to reduce the porosity to a point where the
claj matrix can retard the potential waste migration.
A.2 CLAY SOI1 PROPERTIES
The sail types to be used as lining material for waste disposaI

,
fac~lities must contain a relatively large proportion of fine particles
smallel:' than 2 ~m. The minimum amount of clay size particles requireÇl
for soil to yield a good lining system is in the range of 25% to 28% by
weight (Landreth, 1980; EPA, 1983)
The ability of clay soils to function as lining system& arises from
their relatively low permeability and the presence of net charges on the
surfaces and edges of the clay particles, which allow the retention of
qther ionic speci~_s commonly present in the leachate genenfted from
landfills Ta better appreciate the io~-sieving or filtering capability
of clay soi1s, it is first necessary to recall the various aspects of
clay constituent interaction, mineralogy, and its characteristics
These will establish the basic mechanisms which produce ~he capability
of the clay soils to act as a buffer, and in effect attenuate the
contaminants.
(
185.
A.2.1 Chemistry and Mineralogy of Clays
Clay mineraIs are composed of plate-like structures of Si0 4
tetrahedral and A13 octahedral lattice sheets. !WO basic combin~ons

of these lat~ice sheets are 2:1 clays, which consist of one octahedral
sheet sandwiched between two tetrahedral sheets; and 1.1 clays, which
.
consist of one octahedral and one tetrahe~r'sheet
,
Clay mineraIs with 2 1 lattice conflgurations include both ,
montmorliionite and illite clays. These clays have identical structures
except for the bonding mechanisms between adjacent unlt layers.
Montmorillonite layers are 1005ely ~ounded, resulting in a clay wlth
1 a large capacity for vOtume changes.
by interlayer potassi~ ions, resulting in

Ulite layers are tightly bounded
~ clay with little potential
for volume changes Recent reviews of these common clay mineraIs in

~
t) l'.r"'P
- sail ha~
, been edited by Yong and Warkentin (1975) and Mitchell (1975)
Montmorillonite clays have a la'rge cation exchange capacity (100-
150 meq/lOO g soil), a spècific surface)trea (800 m2/g) , and a

.
potenti.:il for volume change (200%). Montrnorillonite has the ability of "
having the lowest PQrmeability values of clay minera)~ due ta small unit
particle size and a large capacity for swelling with water adsorption
,
Grim (1968) stated that the extraction of interlayer water from
montmorillonité has 'been the cause of

and cracking.shrinkage
~ .
Shrinkage due ta the removal of interlayer water is ascribed to a
decrease in. the thickness of the water film surrou~Jng individual
montmorillonite particles. In a study conduc~ed by Green-Kelly (1~74) on

•
the shrinkage characteristics for various clay soils at high wat.er
content, however, the deformation of pores was considered to be

- 186
responsible for the shrinkage of clay soils, based upon the assumption
( that the water film thickness in montmorilloni te has a constant
thickness at suction values between zero and 1. 36 x 10 5 mm Hg. Since
clay liners are usually

,
kept moist'(if not saturated) in the landfill
and waste ponds, any significant degree of shrinkage would be attributed
to the compaction and repacking of soil particles, accompanied by
changes in pore size distribution

\
Surface-bound layers of wa,.ter are held strongly to the clay
particles, while water layers further aw~.., from the clay surface are
belà-~ess strongly in place by hydrogen bonding. These outer layers of
water can be displaced more easily by an intruding fluid. Theng (1974)
showed that these oU,ter layers interacted with different organic
substances, such as nitriles,"alcohols, ketones and others.
(~ Yong and Warkentin (1975) found that the thickness of the water
film between adjacent montmorillonite layers affects sail properties
such as· plasticity, interparticle bonding, compaction, and water
movement within pore spaces It is wigely believed that the water
layer irnrnediately adjacent ta montmorillonite clay surfaces is held more'
stronglf than water layers further away from the surface. The thickness
of these water layers varies, depending on the adsorbed cation.
Montmorillonite has an adsorbed water layer thickness of 1.0 nm or 4
water layers per clay surface when calcium i5 the adsorbed cation.
Sodium montmorillonite has a water thickness of 0.75 nm or 3 water
layers on its surfaces (Grim and Cuthbert, 1945). Also, Glaeser (1949)
found that the distance between dehydrated montmorillonite layers, upon
being exposed to acetone, increases to 1.25 and 1.51 nm when sodium and
calcium, respectively, were the adsorbed cations.
c'
b -
186
responsib1e
- .
for the shrinkage of clay soi1s, based upon the assumption
that the witer film thickness in montmori11onite has a constant
thickness at suction values between zero and 1.36 x 10 5 mm Hg. Since
clay liners are usually kept moist (if not sattiratAd) in thé landfill
-and waste ponds, any significant degrée of shrinkage would be attributed
ta the compaction and repacking of ~oil particles, ac"Companied by
changes in pore size distribution
Surface-bound layers of water are held strong1j to the clay
particles, while water layers further away from the clay surface are
held less strongly in place by hydrogen bonding These outer 1ayers of
water can be displaced more easily by an intruding fluid Theng (1974)
showed that these outer layers interacted with different organic
substances, such as nitrites, alcohols, ketones and others.
Yong and Wa\kentin (1975) found that the thickness ,of the water
film between adjacent montmori1lonite layers affects soil properties
such as: plasticity, interparticle bonding, compaction, and water
movement within pore spaces. lt is widely believed that the water

o
layer immediately adjacent to montmorillonite clay surfaces is held more

#"
strong1y than water layers further a~y from the surface. The thickness
of these water layers var.les, depending on the adsorbed cation.
Montmori11onite has an adsorbed water layer thickness of 1 0 nm or 4
water layers per clay surface when calcium is the adsorbed cation.
Il
Sodium montmori110nite has a water thickness of 0.75 nm or 3 water
layers on its surf~es (Grim and Cuthbert, 1945). Also, Glaeser (1949)
found that the distance between dehydrated montmori11onite layers, upon
being exposed ta acetone, increases ta 1.25 and 1.51 nm when sodium and
calcium, respectively, were the adsorbed cations.

18?
Qther fac tors whic~ increase the inter layer spac ing in
montmorillonite are the increase of the "dielectric constant and the
dipole moment of the adsorbed fluid (Grim, 1968). Since water has both
a very high dielectric constant and dipole moment, its rep'lacement in

- .
clay interlayer spaces by polar organic compounds wou-ld cause a
significant decrease in inter layer spacing. Interlayer shrinkage could

. cause a significant increase\in hydraulic conductivity of a clay liner
(Appendix E).
lUite has a specific surface area of 80 m2 /g, cation exchange
capacity of 10-40 meq/100 g, and the potential for a volume change of
10%, being intermediate between montmori 110ni te and kaolinite. Many
illitic soils are actually adrnixtures of interstratified structures of
illit~, montmorillonite, and vermiculite (Theng, 1979). Hence, there is

( a wide variation in composition and physico-chemical properties
associated with this clay miner~l.
As mentioned previously. illite l,,-yers are tightly bounded,
compared to montmorilloni te, by interlayer potassium cations fixed
between repeating 2: 1 1ayars. Consequent1y,. this non-expandable clay
will be '~ncapable of adsorbing water or polar organic fluids~ on
interlayer surfaces. Nonetheless, MacIntosh et al. (1971) found that an
or.ganic cation which closely approximates the size and charge of
potassium (such as dodecylammonium), could replace potassium ions in the
interlayer. Otherwise, adsorption of contaminant species would largely
be confined to the external unit particle surfaces.
Hardcastle and Mitchell (1974), using a mixture of illite and·silt,

" o
c' found that the permeability ls positively correlated with electrolyte
\
188
4.
concentratio~ in the _mixture, and the increase in pèrmeability resu1ts

......
'"
from a slight d~erease in clay swelling. Recent reviews whieh summarize
the literature dealingt with iUite. interactions with low m01ecu1ar
weight organics (Theng, 1974~ and orianic po1ytners (Theng, 1979) are
availab1e.
Kaolinite is t'he 1: 1 layer elay mineraI, which has a 10\.1 cation
exchange eapacity (5-14 meq/lOO g), and a low specifie surface area (8-
9- J.,
with on1y a sma1l potentia1 for volume change. Adjacent 1: 1
layers are tightly bounded by a network of hy~rogen bonds, which usually
prevent interlayer penetration of fluids (Grim, 1968). The 1.1 layers
are stacked into hexagonal plates ranging from 0 05 ta 2 0 nm in
thickness. Except where, the inter1ayer spaee has been expanqed by
certain inorganic salts, organic fluids can only be adsorbed to the

,
externa1 surfaces of the hexagonal plate1ets.
Michaels and Lin (1954) found that the permeability of compacted \

kaolinite was significantly increased,' as the permeant solution was
\ .~
changed,from water ta a non-polar organic fluid. ~urthermore, kaolinite
has been shawn ta interac t with ordganic base (Grim et al" 1947) and
"..
organic acid (E\Tans and Russell, 1954).
-\
Another member of the 1'1 clay is halloysite, which has hydrated
interlayers, and is shaped like hollow tubes. Hydrated halloysite has a
large specific surface area (40 m2 /g) compared to kaolinite, and a
cation exchange capacity of 12 meq/lOO g. Halloysite has als~ been
sho~~ to interact with a variety of organic compounds (Carr and Chih,
1971), ~uch as a1coho1s, amines, ketones, ~nd others. While kao1inite
genèrally opposes interlayer penetrati~n of water or organic fluid~,

189
•
c halloysite adsorbs polar and basic organic fluids on 'the interlayer
surface (MacEwan, 1948). Table' A. 1 summarizes the properties ,and
characteristics of the different clay soils.
A.2.2 Sail Attenuation ~roperties
Attenuation can be described as the pennanen~ or 'temporary decrease
in the maximum concentration of a solute in transport, due ta various

,
physÎ\cal, chemical, and bio10gical processes (Folkes, 1982). The
attenuating characteristic of clay 50 ils may also bè 'categorizeçl as the
carrying capacity, which describes the capability of the soil material
in buffering intrusrve contaminants (Yang, 1985). The carrying capacity
of the' clay sail is defined as the ability of the soil ta filter,
attenuate, adsorb, and essentially retain or neutrali 4 e the contaminant
species which intrude into the soil matrix.
The development, of' the carrying capaci ty in soi 15 can be

,.
attributed ta the followipg items: bonding
,
forces, cation exchange
capacity, the presence of'functional groups, specifie surface ar~a, iso-

.
electrical point (lEP) or zero point'of charge (ZPC), . and surface
activity or the particles. It is pertinent ta note that the

l1'
transmissibility characteristics of the soil is indeed governed by the
preceding items.
Clay mi'nerals exhibit cationfexchange phenomenon owirig ta a net
negative charge on. the surface of most clay particles. This charge
deficiency arises from imperfections or isomorphous substitutions within
the crystal
_ lattice,
.. ~nd chemical dissociati~n reactions
t, at the particle
\
surface. Surface hydroxides have a charge which is dependent upon the
degree of association or d1sassociation. In this case, the nature of the

t"~~) J ( , Ct
~
Tahle A.l Common Clay t1inerals and Charl]e CharaclerÎsllcs

~'!l
.~
LATTICE C.E.C. SURfACE . SOlJlHT'" Of CI/AnGE

CLA y t1INŒAI. DESCRIPT ION (meq/lOOl] ) AREA CI/ARGE CIIARACTŒJSTICS '"
(m 2 jl])
'.
kaol.lnJ tes 1:1, strong 5 - lS 1S edl]es, hroken varjable charge

1/ - bonds bonds (hycfroxyl-
B sted ed!]es) .,
il} ) tes 1:2, strol)g 25 DO isomorpholls most) y fixed.
1< - bonds suhslllllti on, char(]e
§ sorne brol<en
honds at eelges
~ chlorltes 2:2 J slront) 10 - 40 00· )somorphoL/s fIxed char(]e
bonds .. subsll tutinn
5\
vermiculiles 1:2; weal< 1O'!;- 150 n.d. ~ isomorp~olls fixed charlJe
MI] - bonds " subslll Illon
S'
montmorillonltes 1:2, very . BO - 100 000 IsnrnofphollS mostl y fixecl
Tek honds slIhslllulIon, charge
§ Il
~
sorne, broken
hol1tJs al edlJes
~ ~
,/
= SILICA :: c..:J :: J\L1JtH NA = r=:::J

J~ • '_
......
\0
0
....
191
( surface charge ls a functibn of pH. At a low pH, the association of
protons dominate and a posltive1y charged surface prevails; while at a

J-
high pH, disassociation of protons and a negatively charged -surface is
predominant. At an intermediate pH, a zero charge will exist. This

'Ii
condition is termed the zero point of charge. The hydrous oxide type
surfaces occur at the broken edge of clay particles, and on aIl
surfaces of crystall ine and am~rphous o~ides, oxyhydroxides and

/
hydroxides occurring in soils (Yong, 1985). Kaolinites.and chlorites
might be expected to have both hydrous oxide and siloxane basal surfaces
(Gr'eenland an~ Mott, 1978).
Exchange adsorption resulting from: (1) e1ectrostatic attractions
to charged clay surfaces, (2) physical adsorption resu1t~ng from van der
Waals bonding forces, (3) and chemical adsorption are principal types of
(~ processes that may serve to remove contaminating ions from leacQate
solut'ion 'and tie them 1to soil surfaces (Weber, 19!?). The diffusion of
ions into the solid phase may be associated with chemical adsorption,
...
(Yong, 1985) .
. Ion exchange occurs in the environment of the double lay~r or the
solution surrounding the surface Q(a clay platelet. According to the
Gouy-Chapman-Stern theory! the thickness of the double 'layer is a
function of charge density on the mineraI surface, the valence of
e1ectrolyte, and the concentration of e1ectro1yte in contact with the
clay, as well as the temperature.
The attenuation capacity of a clay soi1 increases with surface area
and cation exchange capacity, i.e. montmorillonite is most effective,
(
~
fol1owed by illite, and then kao1inite (Griffin and Shimp,'1978).
(
l~
o A.3. PERMEABILITY OF COMPACTED CLAY

'Hydràhlic conductivity or permeability i5 the primary laboratory
measurement made on compacted clay soi15 to a55e5S their suitability for
'use in constructing compacted clay liners for sanitary landfills and
waste contaminant pond~ The va~ue obtained for permeability i5 usua\ly
used to judge whether a compacted clay soil liner will prevent the
\
movement of leachate into the subsurface environment.
Darcy (1856) was first to study the relationships between the flux
,) '" of liquid through a porous matrix J (L 3 /L2. t), volumetrie Üquid
flow Q (L 3 /t), the hydraulic gradient H (L/L) , cross-sectional area of

,.
liquid flow A~L2), and tha permeability coefficient for a given porous
matr"ix K(L/t). These parameters are related through Darcy' s law as:
(1..1).
- To normalize the permeability constant (K) for the flow of fluids
" various viscosities (,.,.) expressed in (MIL. t) ,. and densities (p)
with .,
(M/L 3"), the intrinsic permeability constant k of P?rous matrix is
•
defined as follows:
k_K,.,. (A.2)
p g
where g l's the gravitational constant. The viscosity parameter-,
normalizes the resistance to flow of a fluid due ta cohesiveness, while
the density parameter normalizes the effect of gravity.
The distinct feature of this relationship is the linearity between
gradient and flux. The validity

....
of Darcy' 5 law has been questioned for
some clay SOi+5. In highly compacted and very fine clays, the physical
/
'"
t.!
193
( properties of a large proportion of the pore fluid may be altered due to

...
the int~raction between the liquid and clay particles, which affect the
/
overall viscosity. The result is a soil structure displaying either
lower or higher hydra~lic conductivity.

..
-A more drastic effect in changing the permeability is obtained with
sorne clay soils when the hydraulic gradient is increased. Yang and
~arkentin (1975) found that the thickness of immobilized fluid films on
soil particles would be substantial1y decreased at high hydraulic
gradients. This would increase the effective pore diameter availab1e for
\
fluid, thus increasing permeability. On the other hand, 1arg~ hydraulic
/ gradients can increase soil partie le migration, causing sail clogging
and resulting decrease in permeabi1ity (Olsen, and Daniel, 1979) Zimmie
et al. (1981) suggested the use of hydraulic gradients between 6 and 20
for laboratory studies attempting to duplicate field conditions
o
As mentioned earlier, the physico-chemical behaviour of a clay soii
has a great effect upon soil permeabi1ity. The mechanic,al and
engineering properties, as weil, affect the permeability to a certain
degree. Lambe (1958) showed that the permeability of clay compacted dry
of optimum was much greater than that compacted on the wet side of the
optimum. He also found that the higher the compactive effort, the
smaller the differences between the ranges of permeabilitie~ obtained on
both sides of the optimum .. tlay compacted'dry-of-optimum was found to
have an open flocculated structure, while the wet-of-optimum clay tended
. to have a disper~ed structure. Acar and Seal (1984) noted that while
the total cumula~ive porosity ~f both samples is the same, the frequency
distribution for the two samples is different. The sample at the wet-
1-
194
v
-
of-optimum water content is uni-modal, while the sample st the dry-of-
optimum water content is bi-modal .

..... "'"1
\)~ • 4'
( ~ r :
Mitchell et al. (1965) ~ho~ed that samples compacted by kneading
,- '
'
compaction' have. lower permeabilities than those prepared by static
compaction because of the more\dis.persed structure induce~ by the larger

110 •
shear strain associated with kneading compaction. Sherard et al. (1976)
concluded that compact ion at efforts greater than the standard Proctor
.energy resul ts fn excessive cracking in the clay matrix. This is
attributed ta the brittle behaviour of soils compacted at high
compactive efforts, together with their failure at a very 10w strain
under tensUe forces (Acar and Seal, 1984). co~sequent1y, it i5 not
1
advisab1e to compact
Proctor.
fine-gra~ned
- soils at'efforts greater th an standard
Furthermore, the compacted sail should be protected against

,
possible ~endency to shrink, by using loose soil covers at high water
content.
The permeability of compacted clay a1so seems to be affected by the ~_.
degree of saturation.
in the degree of
-Mit~hell
satu~ation
et al. (1965)" indicated that an increase
leads ta an increase in permeability The
saturation, but correlates equa1ly as weIl in terms of a di rect
variation~ith saturation.
Michaels and Lin (1954) noted that the coefficie~t of permeability

~ la
increased as the coefficient (e 3 /l+e) of the Kozeny-Carman equat~on
increased (K 2
e3 ), as presented in Figure A.l A similar model
KoS (l+e)
developed recently by Bengochea and Lovell, (1981) telates the
...
permeability coefficient ta the hydraulic radius calculated from the
195
( \
N.
E
o"
'0
>- o
~ "0
::i )(
c:: ~
ct
~ O.Ir---~---+--~----~~;-~~--~--~~~·~~~~-+--~
:!
c::
\1.1
~
( o 0.2 0.4 06 '~4 1.6 la z..g 2.Z Z.04
Fiq. A.l. Penneability of Kaolinite as Function of e 3 /l+e After

Michaels and Lill (1954). j
(Where e is the void ratio, S specifie surfa~e Area, and Ko constant

depends on pore shape 'and the ratlo of the lenqth of actual flow path
to the bed thickness) .
.
(
196
u- •
pore size distribution. This model is given as:
K - Cs ~ n
• (A.3)
where, R - l
H 4
ti
f(dt>
di
where di - pore diameter,
f(di) - vo!umetric f~equ1ncy,
'n -_ porosity,
Cs - shape factor, and
K - absolute permeability.
1 _
Another factor which influences the permeability of certain soil is

./
)
the activity, which is ~efined as the ratio of p1asticity index to the
percen~ passing 2~m fraction in a soi1 deposit. This is an index of
clay ~inera1 types iresent in a soil. Minerals with a high surface
- charge denpity per unit dry weight have higher activities (Acar and
,- Sed,, ,1984). Figure A.2 disp1ays the effect of activity on the
hydraulic conductivitY'f.ùf sons prepared at the same dry density. lt is
observed that high active soi1s have lo~er permeabi1ities. Thi& ls
main1y<attributed to the fact that the fully deve10ped diffus~ double
1ayers around the active clay minera1s anq theîr interactions, resu1t in
a more oriented and dispersed fabric leading to lower hydraul ie

'.
conductivities (Yong and Warkentin, 1975). As a consequence, it is a
standard practice to choose soUs with high activities in lining
disposal faeilities (EPA, 1983) The faprie' of a 5011 wi th a fine-
grained fraction is sensitive not ~n1y to composition, but a1so to the
.
interactions between the pore f1uid and the clay surfaces .
••
."
/
197
.(
10. 4 ~----~~~~~~~~---------------,
• H - K~OLINITE:
C.O-I(ACLINITE
:
(.J
Cl
en
......
CE
~
(J
. K - KAOLI NITE
r-
>
r-
u
~ ::::l
0
Z
0
C,)
U
...1
::::l
<!
0: NATURAL
(~ 0
~
::r:
ATTAPULGITE
• H- MONTMO~ILLONITE
No.-
MONTMCRILLONITE
8
10- ~--------~--------~~~--------~
CI la 100
ACTIV1TY
Fiq. A.2. The Effect of Activity on Hydraullc Conductivïtv

(After Acar and Sea1, '1984). Q
..
(
198
A.4 THE
,
EFFECT OF WASTE LIQU1DS ON CLAY 501L5
The durabil,ity and service life of a given liner in a san! tary
landfill or waste containment pond depend upon the spec Hic 1 iquids
which contac t the liner. The liqu!ds emanating from wastes clin he
/
highly complex, and can vary from highly polar sol vents such as waler to
highly non-polar materials such as. Iubricating oils and hydrocllrhon
..
solvents .
carrier,
Most of the-wastes probably contain wntpr as
al though wastes of high organic compounds

th. prinrlpAl
can ~11 ~o ht'
encountered, and aIl compounds either inorganic or organic lIrt' solllhl.·
to a certain degree in water The éomplexity of wa'it(>s C.1I1 rt'~ult III
combined effects on the clay liner In the followinp, <,ub!:ol'ct Ion'" t 1\1'
\.
general properties and characteristics of clay soi 1 s wi Il Ill' dl.,c\l·.·.t·d
considering the Iiquid in contact with so11s
......
A 4 1 The Effects of Exchangeable Cat iOTl_~n __~_l'le
Permeability of Clay
The permeability of clay 15 a funct!on of thr" i!XtllJlll,L',f·.dd.·
positively charged cations which are n'ver5ibly ildsorhl'Ci tn 11I'~·•• lf IVI'I':-
charged 'surfaces. The exchangeable calcium and .. odlum will r.lf·IIII·,
affect the permeabllity of a compacte'd l'Illy ~.oll, lit<. vl·.II.a1Lt.,,, III
Figure A 3. In generai. a clay saturat (·d .... 1 t h r11 v(ll ('!lt S'1l t lollr. '>'Il Il .'1'..
"---
calcitun ls more permeable th.1n one !:olltUl"llf('(\ wl'Ih monovll!"111 '1\11"11"
such as sodildJD (Yong and Wlirkent1n. 19/)
In anottier studYI Qulrk n Q 6'J) tO\lTId that th" p .. nllllllhl11d of
sodium-saturated montmorl 110n1 te decreand when t hr (.on('plIl r Af 11111 nf
sodium ch10rlde (NaCl) ln th .. pt"rmflant 50111110n ""u d"cI"Pllru'll ""

~ )
.' \ simllar clay saturated w1 th ca le i '.ml "ho'W.d nt;) ApprfO<" l"b l tI (ifrc r.~IICS 1n
\ 199
%Nâ· 100
o
-
100
o
Exchangeable Cation
\
Fig. A.3. Relative per.meability Values for Three Clays with Va~iable
Percentages of Calcium and sodium on Exchange Sites
(Yang and Warkentin, 1975l.
(
,
l'
\
200
1
4
the permeability with percolating calcium solution. Backmore and
\
Marshal (1965) found that increasing sodium chloride concentration in a
.
liquid passing through sodium-saturated montmor,illonites suppressed the'
double layer: The decrease in the double layer then inhibtts swelling
and decreases interlayer spacing and permeability
Sodium has a large hydrated radius which results in large
inter.layer ,spacing, and hence disperses the clay. The dispersC'd clay
'ô
particles are free to migrate with the percolating leacha~e, eventually
n
lodging in and clogging the pores, which effectively ,reduces (1)(>
permeqbility of the sail. Calcium has a. relatively small hydraled

radius and two charges per at,om These characteristics combine ta m,/kt'
calcium-saturated clay more resistant ta dispersion and ge m''r Il 11 y mnrl·.~

1 '" ....
permeable than sodium-saturated clay soUs (Yong and WlIrkpntin, 1<)7'J)
Theng (1979) mentioned thllt sodium-saturatt'd montmorillolllt('
adsorbs interlayer water to yield a basal sp<lcing from 1 lun (or lin ()vf'I)-
dried sample ta 5 run for a fully sa turdtNj DIli', wh Il Il l-(lpr~!ll'II t" .1
thickness of 4 nm of water on each surface In C],1Y J 11)('r appllcllt 10[1'.,
this appear""to, be advantageous for reducinp, the P{' rmt'l1b 1 1 1 t y, IHn lh!'
expansion is reversible and hence sodium-montm~rl11oni Ft' 15 'lUlU'('pt'llIlc'
to shrinkage or internaI erosion
As for calcium-saturated montmorl11onire, llwng (979) t"und thot
it adsorbs interlayer water to yt~ld an inCr~IlH" in th(' hAIIAI lipndnt;
f;:om l run to about 2 nm, which corresponds ta a l 't1m t hlckll1!'1U or wnl pr
With some dlvalent cations, Ruch as calclllm of may,n("slUl1l, lIc1sorhc.. l (m
Surtacès, the clay 15 more "

resist~nt to swplling IInd dlDp .. ralon
..
201
Hughes (1975) examined the effect of a concentrated salt solution
on the permeability of a clay liner constructed f,:-om a mixture

.,..-..,.
of sandy.
sail and sodium-saturated montmorillonite. With a four-foot hydraulic
head, permeability of the clay liner incr~ased 100 fold (from 1.0 x
10E-'S to 1. 0 x 10E-6 rn/sec) in seven days. This phenomenon, as

'J
1 explained by Anderson (\981), is attributed to a decrease in the
effective hydrated radius of sodium and the presence of a higher salt
concentration in the clay than in the free water. Thus, sodium-saturated
clays which generally have a low permeability, might not disperse if t~e
concentration of salts ion the soil is high enough. Therefore, the
permeability of a soil May depend on the total salt concentration more
than on the compositiO\ of exchangeable cations.
McNeal and Coleman (1966) examined the effect of the salt
( concentration and sodiwn adsorption ratio (SAR) of the percolating
solution on seven soils of. varying clay mineralogy. The authors found
that the decrease in permeability was particularly pronounced for soils
rich in 2:1 layer-clay minerals, with the most unstable in those soils
consisting mainly of montmorillo?ite. A sail containing considerable
amounts of
.
amorphous material was much more stable than the average, and
a sail rich in kaolinite was virtually insensitive to variations in salt
. concentration. Soils with predominantly illitic clays showed moderate
decreases in permeability with ~ncreaslng salt concentration.
A.4.ÂThe Effects of Organics on the Permeability of

, .
Clay SoUs
Lutz and Kemper (1959) stated that large non-polar organic
Molecules pass through a clay membrane 10 5 10 6 times faster than

( -
....
,- .
202
- .... the polar watèr molecules do, while Mokaday and Low (1968) reported t~t.
.,
the flux of 'water 15 about 500 times faster than the flux of NaCl.
-
These resu1ts indieate the e~feet of the electrical charge on the clby
membrane.
Interaction~ of uncharged polar organics with the clay soils were
studied'extensively by many authôrs such as MacEwan (1948), Hoffman and

,
Brindley (1960) and, more recently, Theng (1974) Their observations+
indicate( that a number of organ1c layers interactlng with
mon~moril~ are related ta the ratio of d1pole moment to molecular
size. Hoffman and Brindley (1960) subsequently' showed that, nt lenst
for adsorption from aqueous solution, lt is the CH activity rather than
the polarit~ of the appropriate organ,ic molecule that 'inf.luence~ thf'
interaction process. The CH activity arises fr'om. the activation of

..-.
- methylene group~
as G. .. 0 and C
by neighbouring electron - withdrawing strUctures,
~ N. Molecules possessing many carbonyl or nitrile

Su~}
groups adjacent 'Co methylene groups clearly have greater CH actlvlty lInù
\
accordingly would be more strongly adsorbed than those compounùs ln
which such groups are few or absent (Theng, 1974)
'\
Neutral non-polar organiçs are probably the larg~st elass of non-
aqueous waste liquids Most waste oils and a largf' part of dlscarded
industrial solvents can be characterized as non· polar, 1 p xylt'nf' /lnd
benzene The rep,lacement of a polar permeant, such as water, by n non-

\
polar one was found to be a cause of permeabll1ty IncrPRSP of b~tw~~n
10% and 30% in compacted kaolinite clay (Mich"Jf.ls~llnd Lin, 195 1,> Il
,\
was cone luded tha t the most important f'llc tor cont ro lIin& th~
permeability was the degree of dispersion or dlaaggregal10n .xl.ting ln
- the original permeant.'

203
(- The results of permeability obtained by Anderson et al. (1982) for
four clay soils permeated by xylene showed an initial rapid increase in
permeability followed by a nearly constant permeability. Since the
permeability increased an average of 10,000%, mechanisms other than

.,
viscosity and density such as changes in clay mâss structure, were
involved. Green et al~

.
(1981) suggested that the large change in the
'.
permeability may be due to the formation of shri~ge cracks.
A recent study by Anderson (1981) on the effect of different
organic acids, namely acetic acid which is usually present in a leachate
from sanitary landfills, on four types of clay soils showed initial
deereases in permeability. The decrease in permeability was attributed
to partial dissolution and subsequent migration of soil particles.
Migrating particle fragments could lodge in the fluid-conduéting pores,
thus decreasing permeabili ty by reducing the cross-sec tional area
available for fluid flow Two of the soils treated with acetic tCid
(montmorillonite and kaolinite) decreased continuously in permeability
throughout the test. The density and viscosity ratio of aeetic acid
(0.82) implied that permeability should decrease approximately 18% from
the value obtained with a standard permeant. Nevertheless, the
substantial decrease and subsequent inerease ~n permeability in both of
the soils indicated that soil piping was the predominant influence
responsible for permeability changes.
A study by Green et al. (1981), on clay soil exposed to organic
hazardous waste, showed that the hydrophobie or hydrophilic nature of
the solvent (as measured by the dielectric constant) is more important
than lts density or viscosity in predicting the solvent' s rate of flow
( through clay soils.
\
\
Green et al. (1~81) developed an empiric~l equation for estlmating

l'
the permeabllity (cm/sec):
(A.5)
where E ls the dielectric constant and d, is the packed bulk clay
densi ty (g/cm 3 ) Moreover, their study showed ~hat a11 clay ;;0115 were
more permeable to water than to organic solv~nts. which i5 çontrnry to

1
_ the results of Anderson et al. (1982) The dielectric constant of a
liquid i~ its ability to transmi~ an electricàl charge W}wn the
original water solution of the soil 1s replace! by an' organic compound
with a lower dielectric constant. lhe fluid film surround1ng and present. t
inside the clay particles must be thinner for the r,'egative surface
charge to be neutralized by the cations Thus, the lower the dielectric
- constant of the rèplacing liquid, thQ smaller the interlayer spacing
(EPA, 1983). Accofding to the double layer theory. the "half - distance" .
which is a measure of thl'! interlayer spacing, ts propo'rtional to
dielectric constant raised ta power 0.5
Barashed (1952) presented sorne results which 1l1tistrated

,
the ('f[l'ct
of dielectric constant on the interlayer spac ing.
presented in Table A. 2. Furthermore. Barashed (195:7) showed. that not
only does the dielectric constant of the organic c.ompollnds affec t thp
.
interlayer s,pacing, but sorne other factors do too, ,,.. uch as the 'cHpoh
mOUlent and the nature of adsorbed clay Table A. 3 summar1ze$ Sarshed' 5
(195~) results ln that respect.
(
205
(
TABLE A.2 Interlaye'r Spacing of Calclum Srnectlte 3
Immersed ln LlqUlds of Varlous'
Dlelectrlc Constants b
".
Imme~SlDn llquld Dlelectrlc Interlayer

Constant Spaclng
(25°C) (nm)
(
\
100:0 Water:propanol • 78.5 1.92
70:30 IrJater: propanol 57.7 1.88
40:60 IrJater :propano1 36.4 1.84
30:'70 IrJélter: propanol 30.7 1.77

~
"
20:80 IrJater: propanol 26.1 1. 77
10:90 IrJater: propanol 22.7 1. 52

(. 0:100 L-Jater: propanol 20.1 1.44
100:0 IrJater: glycero1 78.5 1.92

.t-
40:60 Wat~r:glycerol 59.4 1. 79 \
0:100 W~ter:glycerol 39.2 1.68
~Dehydrated at 250°C prlor to lmmerSlon in liqu~d.
b EPA (1983).
..
( t
..
206
f) J
TABLE A.3 Interlayer Spac~ng of Calclum Smectite as a

tunctlon of Olelectrlc Constant and
OlPoÏe Homent a
Interlayer Sorbed Dlpole Dielectflc

Spaclng Fluld Moment Constant
"
nm
0.99 Benzene 4 0 2.3
0.99 ParaFFln - 0 2. l
1.45
1. 70
BU:(
. Ethan
-
1.6
1.7
17. 7
25.0
~
1. 71 Methanol 1.6 32.4

4"'"
-
~
1.73 Methy1 'ethy1 2.7 18.9

ketone
"
78.5
1.92 Water 1.8
[PA (1983)
'"
/ Source:
1
1 ln the
aAlI samples ~ere dehydrated at 2)OoC prl0f ta ImmerSIon
test flUId.
1
1
(
\
/'
207
.~
A.4.3 The Effect of Contaminant Migration on other Geotechnical
Properties
Since the fabric of clay soils is sensitive to changes in the
sy.s tem vary?ili le~ which affec t the thickness of the 1ffu~e double layer,
other geotechnical properties such as shear strengt~ and compressibility
are also \ affected by post-cotilstruction alteration in P\~e fluid
chemistry The resu1tant interaction~ deve10ped by the cortaminant
species, in terms of dominant repulsion or attraction betw~en soil

l
particles and fabric units, become particularly significant in the
control of the mechanical properties of the soi1. In a natural clay soil

,
system, increases in the net repu1sion will (a) weaken the capability of
the natural bonds to function, because the increased repulsive forces
will serve to lower the pot~ntial energy barrier needed to di~rupt the
,
( bonds (Warkentin and Yong, 1962, Yong, 1985), and (b) provide gr~ater
resistance to mutual di~placement of adjacent soil units under shear.
Increased net repulsion can either increase or decrease the strength of
1 the clay-soil, depending on whether the natural bond strength is -,
considerab1y la!ger than the increase in net repulsion. In either case,
the resu1tant strain at maximum strength development will always be

'"
larger (Yong et al., 1985a).
Increase in the net attraction, because of changes in interaction

,
between soil constituents and contaminant species, will (a) increase the
capability of natural bonds to function, and (b) decrease resi.,stance to
tqe mutual displacement of adjacent soil units. As in the case of net
repulsion, increasing net attraction can either increase or decrease
soil strength depending ta a great degree on the initial bond strength.
c In ~ither case, the resultant strains at maximum strength development

208
1
,
will always be smaller in comparison to the uncontaminated sail (rong et
al.. 1985).
There are many factors responsible for the net attractive and
repulsive forces between the c~ay particles. The primary factor which
is responsible for repulsion between two clay particles results from the
interaction of diffuse double layers between the particles.
Furthermore, when all other' factors including the distance between the
particles remain constant, this repulsive force is proportional to the
dielectric constant of the pore medium (Sridharan and Rao, 1979).

"
-#
There are a number of phenomena responsible for attractive forces
among the clay particles and fabric units. They can be grouped into
primary valence bonds, hydrogen bonds and secondary valence forces The
CouJ..ombic attraction and other possible' attractions, such as the ion-
dipole, or induced dipole interaction, or dipole-dipole interaction are
inversely proportional to the dielectric constant of the medium and the
distance between the units (Lambe, 1958).
The secondary valence forces,are of more concern to the engineering
applications, since the y are greatly influenced by applieF stress and by
the changes in the -nature of the clay-water system, and in addition
they can act over relative1y large distances (Sridharan and Rao, 1979).
Accor,ding ,to London' s {=heory, these forces are universal between aU
pairs of atoms or molecules and vary inversely as the seventh power of
the distance between them.
>
The above discussion serves to illustrate the complexity of
r:,
~ ~
mechanisms which provide the natura! Boil wi th its mechanical and
..
\
c physica.l behaviour. Adsorption, desorption, attenuation, complexation,
and transformations aIl contribute to the development of changes in net

\
repulsion/attraction and natural bonding. In the following subsections

c
the failure mechanisms in clay soil liners will be discussed. The major
fai1ure mechanisms inc1ude voHune change, dissolution of clay and
plping .
. A.4.4 Volume Changes
Volume changes in clay liners occur when the water content is

\ .
changed. When clay soi1s are dried, shrinkage and cracking occur. If
.
'-;-- rewetting occurs subsequent to drying, swe1ling occurs. Large volume
changes will resu1t from a climate with a1ternate wet and dry seasons,
whi1e s~al1er changes a)e associated with a1ternating preci~itating and
drying periods. For a given change in water cOI1tent, the magnitude- of ....
( volume change is dependent
, upon clay minera1
. type, arrangement of clay
partic1es, surface area per unit weight of clay, and the species and
propdrtion of cations adsorbed in clay (Landreth, 1980). A1so, volume

\
changes of a- soil liner may occur when the soi1 water is replaced by a
leachate soJution or if an organic contaminant extracts water from tb~
clay, liner.' Extraction of the inter1ayer liquid could cause ,shrinkage
and cracks, as weIl. Yong and Warkentin (1975) stated that cracking'is
a resu1t of the clay undergoing three-dimensional shrinkage.
A.4.4.1 Soi! Characteristics Affecting Swelling and Shrinkage Behaviour
Swelling behaviour of compacted clay soils has been found to be
related to tpe clay minera1s present (Yong and Warkentin, 1975) and
their orientation, the presehce of organic compoùnd~ adsorbed 'on clay.

"
surfaces (Hughes, 1975), exchangeable cations p'resent, and the fabric or
(
,
/ ~ 1
r
- 210
.\
structural arrangement of clay particles (Lambe, 1958). \.
Bath kaolinite and il1ite have substantially less ~ap~city to swell
than montmoril10nite clays. Hallosite has a swel1ing potential between
tha t 0 f kao lini te and i 11i te . Montmorillonite's large shrink-swell
oapacity is'due to a combination of tts large cation exchange capacity,
moderate surfac;:e charge density, octahedral layer: isomorphous
substitution, and large surface area to volume ratio (Gast, 1979).
<>
Yong and Wa~kentin (1975) found that the presence of monovalent
~
exchangeable ions, such as sodium, causes greater sweIling th an diva1ent
c~lcium ions, wh~ch is exp1ained by the greater extension of the diffuse
ion layer. Swelling and-dispersion of so11s ,ith ?xchangeable s~~ium
are reduced at a higher salt concentration due ta the compressipn of the
-- availab1e water surrounding the clay surfaces (Hughes, 1975).
Cementation between partic1es ~ a major ~actor in 1imiting volume
increase of clays on swelling. Iron hydroxides, carbonates and various

, ~
.
organic molecules act as the cementing materia1s . The decrease in
swelling .'4:'s more pr0rt0unced in weath~re4 c1ays which have undergone
cycles~.of wetting and drying.

- Most of the mechanisms for cementation
. ~
depend upon the dehydr~tionof colloidal material ta forro bonds between

....
particles (Buclonan and Brady, 1969) .
•
Watson (1968) found that ce;;tain concentrations of surfactan~s
stabilize soils against dispersion and swel1ing. Hughes (19~5) stated

~
that one reason for the hindrance of swelling in·montmori11onite was the ~
adsorption of organics on clay surfaces. He a1so sugges ted that'

1
adsorbed organics interfered with the interactions between the

J
interlayer water and clay surface.

o
211
•
( Grim et al. (1947) noted that the water adsorption capacity of
kao1inite c1ays was reduced fo110wing 'treatments with organic cations.
, .
That decre'Àse in water adsorption of kao1inite was 1ess"
. th~n the
decrease exh'ibited by mo~tmorillonite c1ays. This reduction in
adsorption ~apacity was due to the coating of the interlayer spaces by
organic cations.
.- r•
The influence of particle arrangement on swelling seems

,
to be of
great effect. There are two extremes of possible arrangements of clay
particles The firs't is an edge to face structure which forms the
flocculated structure... ,Clay soils with a dispersed (face to face
arrangements) structure will tend to undergo more vol~etric shrinkage
with changes in water content (Lambe, 1958) Mitchell (1975) concluded

.
that compacted clay returns to a more flQcculated structure after
placement and hence may exhibit an increase in the permeability with
time.
In investigating the mechanisms controlling the volume change

,
behaviour of clays having 100% degree of saturation, Sridharan and Roa
(1973) conducted tests using .different organic f1uids A crit:;,ical
'evaluation of their results indicates that the compressibility of

~
kaolinite is governed by the shearing resistance at the near particle

• contact points, while montmori.l1onite is governed by th.e--"long range
repulsive forces.
Another' factor 'which influences clay soi1s' swel1ing and shrinkage

< ,
potentia1 is ovetburden pressure (Anderson, 1982). Swel1ing pressure 'in
clay will determinc the extent to which it is capable of swelling·under
{ 'a given overburden pressure. Davidson aQd Pag~ (1956) determined that
u-
212
swelling pressure exhibited by sodium-saturated mineraI samples of
montmorillonite was substantial, while kaolinite and illite exhihited
negligible swelling pressure.
A.4.5 Dissolution of Clay
Dissolution 'of clay liners can he 1nvestigated by uslng lin
infiltùting chemical s·olution that dissolves soil-exposE'd surfncl's
Either organic or inorganic acids or bases may dissolve portions of th~
clay struc ture The solubility of the clay mlnerals in ac1ds varh·!.
with the nature of the acid, aeid concentration, Ilcid to clay ratio.
tempe rature , and duration of exposure (Grim. 1968)
Acids and strongly alk,line solut!ons have been reporte'cI to
dissolve siliea (EPA, 1983) Since clay mineraIs eontain both sllic.l
and aluminum in large quantities, they are SuscE'ptible to part illl
dissolution by either aeids or bases Grim (1968) r('port(l(j thnt tlll'
r
alkaline earth metals are removed more rapidly than tlH' il lwnlm1ln or lIon
in ,the attack of acid on ma'ntmorillonite and pl'obably nl~o on' ttllt
illite. lt appears that the aeid attaek begins around th€' pdg.'" of tlw
particles'and works inward
~
SUica ls also more soluble in the presence of orp,.'1nlc nc 1 d~ IlliCh
as those present in waste impoundments and landff Il S liS .... nllf.rold.
décomposition by-products (Bartels, 196 /.) nases hav .. 311le) 1>" ... " "110 ....11
to ;:!xtract silica from clay lattice structurl:ls. SolIJb111 ty 01 A11in\ lu
pH dependent and greatly lncreases above pH 9 0 (Alttxl1ml .. r ~t III . l 'l'J',.
Sbumm lnd Morgen, 1970)
, ,
" 213 .
( A.4.6 Piping
Piping is the active erosion,. of soil constituents due to fluid
pressurè and the concentration of seepage in 10ca1ized channels (Mansur
and Kaufman, 1956). Gustomari1y piping and dissolution are considered
to be physical and chemical phenomena respectively, and often occur
together. Disperse soi1s are most susceptible to piping (Grouch, 1978).
Mitchell (1975) found that quick clays were often associated with
the présence of organic compounds possessing strong dispersing
characteristics These clays act as viscous fluids with no structural
strength and are thus susceptible to erosion caused by seepage Also,
changes in chemistry of the pore fluid have been reported to result in
the formation of channels an~avities. Sherard et al. (1976) stated
that the percent of sOdium_~~: saturation extract from the soil is a
( reliable indicator oI probable dispersion performance. The study of the
performance of many dams led to the correlation between the above
parame ters (Fig. ft.4), which can be used às a guideline for the
(-
"
estimaFion of a tendency for spontaneous dispersion. A reactive fluid
may enlarge the surface are as of the pores by dissolution of the soil
matrix between two pores. While reactivity in a fluid is reduced by its
action on the pore wall, the size increase in the pore will increase~the
rate of delivery of the fluid to the pore Soi1 piping also results in
the, shifts of pore size distribution toward macropores with no
corresponding change in total porosity.
Piping involves slaking partfcles. Slaking 15 defined as the
disintegration of unconfined soil samples when submerged in a ~j.d.
Hardcastle and Mitchell (1974) investigated dispersive slaking of sodium
( and calcium-saturated kaolinite, illite, and montmorillonite. AlI the

214
u-
Na
S~n.
,.,
80
E
:l
"0
0 60
Vl
-
c 040
..
G
U
G
a.. 20
0 j
O. J o~ /.0 ~.O 10 ~ 100
Tarai CÜlolvtd Salt~ in SaturatIOn Extroct
'\ (m.q/lit ... )
:'
Fiq. A.4. Relationship betwecn Disoersibility (SllSC::0rtlbil Uy tn

Colloidal Erosion) anrl 01ss01 vcd Porp-Watpr Sa 1 t"s on
, Pinho1e Tests anrl Exerience Wl th Eros lon in Na turp
(After Sherarrl ct al., 1Q76l.
\ .
,
CI
215
c c1ays were slaked by dispersion when saturated with sodium; the process
proceeds faster with sodium-kao1inite and sodium-i11ite .
.
It is pertinent to note that piping -initiates on the underside of
a clay liner where clay partic1es can migrate into a substrate with
1arger pore diameters (EPA, 1983). The piping cou1d further progress
upward through the clay liner unti1 it makes an opening into the waste
impoundment. Clay partic1es have been shown to migrate through porous
media having 1ess than 15% clay (Hardcast1e and Mitche1, 1974).
Consequent1y, a clay liner under1ain by soi1s containing 1ess than 15%
c1ay,may be susceptible to soi1 piping. ~
" .
, (
(
"
216,'
APPENDIX B
PHYSICO-CHEMICAL AND ANALYTICAL'CONCEPTS OF
LEACHING MIGRATION
B.l-GENERAL
Changes in the composition and concentrations of 1eachate migrating
from waste containment ponds and sanitary landfills for indus trial and
domestic wastes, result from the occurrence of one or more of the
following processés:
(a) Convective and/or dispersive mass,transport of contaminants
through the soil system,
(b) Interactions and reactions which occur within the soil system,
(c) Adsorption of contaminants onto surfaces of soi1 constituents,

1
(d) Ion-exchange,
-... -
(e) Biodegradation and generation of varlous by-products due to
,
microbial interaction and activity, and
(f) Dissolution and precipitation.
Depending on the nature and composition of the contam~nt, these
processes may be of varying importance and signi ficance in the
consideration of leachate migration through clay soils used e ither as
liner material and/or containment substrate. In general, however, the
a~lysis of a given leachate transport necessitates the analysis of more

J
than just convective and dispersive mass tran,sport. Other processes
must be.... considered and, for most systems, included. This inclusion
complicates the analysis, as the effects of non-transport processes
become superimposed on the transport processes, or in ather words,
creates a retardation mechanism which affects the transport of

C>
\
217
( contaminants through clay soils. As a resul t, in the analys is and

\
description of the behaviour of 1eachate migration, the separation of
the effects of the participating processes "

may become extremely
difficult (Sykes, 1975).
In this Appendix, the physico-chemical processes and theoretical
concepts of leachate migration are introduced. In addition to the
aforementioned processes, a process such as filtration, which i5 often
operatiye in porous media, influencing the transport of contaminants to

..y
varying degrees. However, it is assumed that this filtration mechanism
is of less impact on inorganic and organic\migration. A subsequent
assessment of the literatt,lre provides support for this expectation
(Sykes. 1975; Soyupak • ...l979; and Griffin and Shimp, 1978).
( B.2 HYDRODYNAMIC DISPERSION

/
In fluid flow through porous media. dispersion or hydrodynamic
dispersion is the occurrence and development of a transition zone
between the domains of the f~uid

• composition (Fried.
phases of different
1975). With the introductio'n of a fluid containing a

• f- •
cert~n mass
solute of concentration Cl into a clay soil system wi th a moisture
content containing solute concentration Cz • and assuming a neg1igible
density effect. the transition zone is defined as the zone where the
tracer concentration varies from Cl to C2 , In the absence of
dispersion. the shape of a step function will occur between the phases,
with a zero width to the transi tion zone, With the 'development of a
transition zone. however. the width genera11y increases with time (Fig.
B.l) ,
(
218
v Breakthrougth t 2
t.- 1.0
Effect of
dispersion
First
appearance
t1
o
Time
- Fiq. B.l. Relat~ve

•
Tracer Concentration in outflaw tram
Column of Soi l (After Freeze and Cherry,
1979 >.
\
219
( The mass transport mechanism of hydrodynamic dispersion is the
result of two separate phenomena, Le. molecular diffusion and
mechanical dispersion. The former is a phenomenon of the microscopie
scale, Le. the scale of the pore size. The other, mechanical
dispersion, results from convection flow, and is a phenomenon of the
macroscopic scale (Sykes, 1975r. While molecular diffusion is a physico-
chemical phenomenon, mechanical dispersion is 'a purely mechanical
phenomenon. lt is not generally possible to distinguish between their
individual effects on contaminant migration through clay sail systems.
Within the pore spaces, the contaminant species are subJected to
motions and collisions resul ting from the random movement known as
fi
Brownian motion . In the presence of a concentration gradient or

••
inequilibrium within the soil system, Brownian motion will result in a
l contaminant species migration from zones of high concentration to zones
of lower concentration .. The molecular diffusion phenomenon can also
occur as a result of temperature gradients. Molecular diffusion in clay
sail systems is a time-dependent process independent of pore fluid
velocities.
Mechanical dispersion is a function of convective mass transport,
and its intensity is determined by (Fried and Comparnous, 1971): (1)
veloci ty gradients developed within the soin pores during 1iquid
movement, (2) variations in pore dimensions and direction, creating
v{!.ri ations in the maximum velocities along the pore axis, and (3)
veloci ty flucyuations about the mean value. Mechanical dispersion
't'esults in bo~h a lougi tudinal effect due ta differences, between
velocity compobents in the mean velocity directio~, and a transverse
( effect due to differences bktween the velocity components or~ogonal to

,
220
mean direction (Sykes, 1975). ln most of the field s.ituations.
mechanical ~ispersion
.
predomina tes over molecular diffusion (Bredehoeft
and Pinder, 1973).
The physical processes of both molecular diffusion and mechanical
dispersion can be treated as a Fickian type sprea~ng mech~nism. The
two meehanisms can be treated together in terms of a single hydrodynamic
dispersion coefficient (D). The mass flux (F) is given by:

\
F - 9 VC - 9 D ô C
-a-x (B.l)
where C concentration of the contaminant species,
V average pore water velocity, and •

9 - pore fraction (effèctive porosity)
(
or the volumetric
-
water content
The first term on the right-hand'side of equation (B.l) refers to
convection transport and the second term refers to disp~rsive transport .
The negative sign of the •dispersive term indicates that transport of
the contaminant species occurs in the direction of a decreasing the

'"
concentration gradient. and x represents the distance from the
contaminan~ source.
Considering the mass balance condition:
Bec ôF (B.2)
ôt -- ôx
Combining equation (B.l) and (B.2) gives:
(B.3)
i
221
Equation (B.3) is the dispersion-cbnvection equation in its one-
dimensiona! form without c~nsidering the adsorption-desorption mechanism\
(i.e. the geochemical reactions). In the present study, the numerical
solution of equation (B. 3) was performed b~..............1I<, the finite difference
technique, similar to the one used Lai and Jurinak (1971),

".
as described in more detail in Chapter 4.
Many empirical relationships have been described to assess

, . -"
mole~ular diffusion coefficients, mechanieal dispersion, and
hydrodynamic dispersion coefficients. Some of these formulations are
given i~ Table B.l and Figure B.2.
To describe the relative importance of molecular " diffusion and
mechanical dispersion, the Peclet ~umber is often used:

.'
( (B.4)
,. where, ,p. is the Peclet num~er, d is the mean grain size or any other
characteristic length of the medium, v is the average iT.ltersti tial
ve1ocity, and Dd is the molecular diffusion.
When the interstitial velocity is zero, the hydrodynamic dispersion
coefficient (0 - Dd + Dm) i5" equal to that for molecular diffusion
(Dd ) through the clay soil system. Similarly, when the intèrstitial
.............
veloclty 15 high, mechanical dispersion (Dm) can be considered as the
predomi~an~ dispersion mechanism.
(
r
222
•
0 Equation Source
0 = 0
m + °d Bear 1972, Fried 1975
D = Cl v Scheidegger 1957
m
°d = 0 w
n e<P€ Olsen and Kemper 1968
2
Dd = 0 W € Desaulneirs et al. 1981
o = hydrodynarruc dispers~on coeff~cient
om = mechanical d~sperslon coeff~cient

0d = molecular dlffuslon coefficient
Cl = geametrlc dlsperslvlty
o ~ molécular diffusion coefflcient for speciflC

W . contamlnant in water
= volumetrie
--
€ water content
n & cp = constant
v = average velocity
r
TABLE B.1. t-blecular DiffuslOn, Mechanica1 Dlspersion, and
Hydrodynamic Dlspersion Coefficients tWar1,h 1984).
\
'0
-
r
223
1.0 - - - - - - - - - - -____ .::_;..:::;00_ _1,,_
o
-
Ü
Ü 05
- o. 0 "'"------.L.---.:~_ _ _ _ ____J
Volume of 'Effluent
D = V L ~
471' y--
)
"
S~
0
L = length of the sOli column ,

V,)= effluent volume at the contamlna~t concentrat Ion
C/Co = OS
( Co~ Influent solute concentration
S ,= .. Iope of the breakthrough cur:v~ at C/C') =.S
C = solute concentration
v= the average veloclty
.'
Fiq. B.2. Hydrodynamic Dispersion Coefficient Deténnîned

f ran a Breakthrough Curve'
...
..~ ~
(Rifai ~t al., 1956),
./
--,
(
.' .
224
B.3 REACTION PROCESSES

During the migration of pollutants th.ough clay soil systems,
dispersion will occur simultaneously with sorne reaction process(es).
The ...
inve stigation of reaction processes requires two princ ipal
considerations: firstly, the energetic or thermodynamic feasibility for'
reac'tion, and second1,y, the kinetics or rate at whicl1 the reaction will
proceed
, (Weber, 1972). With respect to the former, the present study
considered only the concept of equilibrium. According ta Sykes (1975),
equilibrium refers to a specifie state of a reacting system and
represents that state in which the system is most stable and in which no
net changes occur in the compositi,on of the system. A closed system
subj ect to internaI reactions only, and at any state other than
equilibrium, will undergo spontaneous reaction and internaI changes will
- subject ta addition
;
take place until the system reaches equilibrium.
anà'subtrac~ion
For open systems
of different components as weil as

./
internaI reactions, as in the case of landfill and leachate migration, a
time-inyariant condition i9 a steady state rather th an an eq;uilibrium
one. With a balance in the input of reactants and output of products, 'a
system will maintain a non-equilibrium steady state situation (Weber,
1972) .
Considering'the equllibrium state, changes occurring in a syst~m
can be classified into three types: (1) a natl,1ral change, (2) an
unnatural change ~ and (3) a revers ible change. A natural change
results from a reac~ion which tends ta bring the system closer to its
equilibrium state. On the other hand, an·unn~tural c~ange i5 caused by a
reactian which tends ta drive the system fu~ther from the equilibrium
state. 'Reversible changes represent a limiting case between natural and
'.
.
-
225
unnatura1 processes (Stumm and 'Morgan, 1970).
The fundamental basis for reac tion kinetics is the 1aw of mass
actio~ which states that the rate of an e1ementarY,homogeneous chemica1

.
reaction is direct1y proportiona1 to the product of the concentrations
1
of the reaction species (Weber, 1972). For an irreversib1e, homogeneous
reaction be"t:Meen two species A and B combining to form a compound AB,
the.stoichiometric equation may be written as:
(B 5)
The 1aw of mass action gives the time ~ependent forward ve10city or
rate of reaction a~ rf whe re CA and CB are
concentrations of A and B respective1y, and K is the time inde pendent
rate constant (Stumm and Morgan, 1970) A detai1ed discussion of

(~ different types of reactions is given ty Weber (1972) and Stumm and
Mctrgan ,(1970) .
According to Yong (1985) and Yong et al. (1985b), the mechanisms
q.nd reaction rates pertaining to the interactions between sévera1
, , contaminants and clay soi1 system depend on:

1
(1) Clay species and conyents,
(2) Amorphous mater,ia1s (composition and contents),

~ 1
(3) Organic content in soil, \.

~ .
(4) Exchangeable"cati~ns and anions~
(5) The pH of the syst~m, and
(6) Solute compo~ition and concentration.
Yang (1985) has also described the ~rob1em of mu1ti-contaminants
and has referred' th'e prob~em to the compositions of spécifie
•
1
226
con~aminants during their reactioos and interactions with ~he various

,f'
soil constituents. This is due primarily to the fact that these actions
are not indepsndent and cannot be simply superimposed by conside~ing the
individual réacti~s and interactions. The coupling and ~nterdependent
actions, wnich arise in the complex natural system of multi-contaminartts
and mixed constituent clay soil, have yet to be fully studied and
understood.
B.4 ADSORPTION
Basically, it is the" presence of adsorption and ion exchange
mechanisms in clay soil systems that allows the subsurface environment
to-be used for-waste disposaI. With the occurrence of these processes,
the movement of multi-eontaminants throul!;h clay soil mf~dill can be
effeetively re"tarded as illustrated in Figure B 3 For sorne
contaminants e.g. heavy metals, adsorption and ion exehange operpte in
such a manner that a complete removal from the solution can be
;:.smsidered.
/Aa:;orptioI\ i~ a surface phen?menon, in which contaminant spec ies

(. f\
are extraéted from One phase and Goncentrated at the surface of a
second phase (Weber, 1972) The primary driving force for adsorption
may be a consequence of the solvent-disliking (hydrophobie) character of
the solute relative t~"a partieular solvent, and a high affinity of the
solute for the solid. The more a matter likes the pore fluid solution
(solve,nt), the less hydrophobie, the less likely it is to move toward
thL solid phase to be adsorbed Conversely, a hydrophobie pore 'fluid

...
..
disliking matter will be more adsorbed The rat io of soluble and
......
\
adsorbed species' is know'h -as a distribution- t:oeffic lent Kd : For mast

\
227
-0
('J
0°
-~
C
ID
0'
10
C
0
() ,
ID
", ..N onretarded species
species
-
>
('J
ID
00
\
cr: a b
Distance
(
Fiq. B.3. Advan'ce of AdsorbOO and Nonadsorbed Solutes Throuqh a Co1urnn
of Porous Materials (After Freeze and Cherry, 1979) .
( \
22R
• contaminant-sail systems, adsorption resu1ts from the combined action of
the two forces.
Three principal types of adsorption are: (1) physical adsorption
res~lting from van der Yaa1s attraction, (2) chemical adsorption, and
'(3) exchange adsorption ,;esulting from electro-static attractions ta
charged surface sites on the solid phase (Weber, 1972),
The factors affecting adsorption of a contaminant on to a soil
surface include: specific surface area, concentration and nature of the
adsorbate (contaminants), pH, tempe rature , concentration, and nature of
the competing ions present in the intruding solution (leachatt>

~
solution); and the nature of the absorbent (soil system) (Stwnm and
Morgan, 1970, Weber, 1972)
I~ clay sail systems, adsorption results in the removal of certain

- species from pore fluid, causing an increase in their concentration nt
the surface of the clay soil wilJ. occur, until the concentration of rhp
species remaining in pore fluid solution is in a dynl\mic equilibriwn
with that at the soil surface The adsorption isotherm can be utiliz~d
to express the equilibrium distribution of Sand C S is defined as tht>
amount of solute adsorbed at equilibrium per unit weight of solid

1
}
adsorbent (clay soil) , and C as the concentration of solute rel!l~inlngin
the pore fluid solution at equilibriwn Th us , the ~orPtion lsotherm, S
- f(C). is a functional expression for the variation of adsorption wl th
concentration of adsorbate in the solution at a constant tempcrllture
(Ye1:-~r, 1972). In the literature, three isotherma 1 adsorption modeÀs
are g~nerally cited These inc1ude
.",. (1) The Langmuir Moie1

229
s _ Q~C
(B.6)
(l+bC)
where b 1s a constant and QO is the number of moles of solute
(contaminant) adsorbed per unit weight of adsorbent to form a complete
mon01ayer at the soil particle surface.
(2) The Brunauè'r, Emmett, T~l1er (BET) Model
S - BCQO/(Cs-C) [l+(B-l)(g)] (B.7)

s
where B is a constant and Cs is the saturation concentration of the
solute.
(3) The Freundlich Model
S - K C- 1 / n • (B.B)
;;
~here K and n are constants.
In the analysis and application of adsorption in a clay soil
system, the rate at which dissolved contaminants are removed from the
solution is highly significant. Within the soil media, the rate of
adsorption can be limited by either the rate of the transfer of solute
through the pores (micro-macropores), or by the actual adsorption of the
solute on the surfaces of the soil particles and/or fabric units. With
solute dispersion and convection being rate-limiting, f~ can be assumed
th'at instantaneous point-wise equilibrium is establ.ished between/ the
adsorbed and desorbed concentration

, (S and C) of a given solute or
contaminant Considering this assumption, equilibrium type isotherms _
given by the equations of B.6, B.7, and B.B can be used to describe the
...
adsorption of contaminants during leachate migration through the clay
t soil,systems. The assumption of equilibrium implies either the slow
...
i1
230
o movement of dissolved solute past an active sorbing site on the pore
wall, such that sufficient solute molecules are adsorbed ta produce
equi1ibrium, or the existence of active sorbing sites of sufficient
strength, far-ranging enough to yield the point-wise equilibrium.

~
For some contaminants and soils, the assumption of the
establishment of an instantaneous equi1ibrium is not valid. In such non-
equi1ibrium systems, time variant kinetic type models must be used
(Lapidus and Amundson, 1952) .

."
Equi1ibrium or non-equilibrium adsorption models combined with
solute transport have been analyzed by many authors. Lapidus and
Amundson (1952) analyzed adsorption in a one-diménsional diffusion
column using an equilibrium condition given as:

..
(B 9)
where Kl and IS are constants. The autho~s, and most recently
Mansell and Selim (1981), used a first-order kinetic reaction isotherm
given as:
a pS
(B 10)
Tt
to analyze the non-equilibrium case.
In the study of Lindstromtand Boersma (1970), a one·dimensional'
finite difference solution technique was Iilsed to analyze a Freundl1ch
type equilibrium model where
(B.11)
o
which gives
as _ a .. c~-l ac
n r Tt ..
(8.12)
1
231
,...
( where p - lin; 0 is the ratio of chemically active surface area of
,
the soil to the total surface area; and 1 is a partition coefficient.
A similar analysis was also used by Van Genuchten and Wierenga (1976)
and Selim et al. (1977) .' In the anatysis of non-equilibrium models,

''\
Lindstrom and Boersma (1970) used a first-order kinetic reaction type of
adsorption similar ~o that of Lapidus and Amundson (1952). Their
equation is of the form:
aC-
a-t K (0 1 C - S) (B.l3)
An analysis of adsorption using a second-order kinet!c equation is
presented by Weber (1972).
Exchange adsorption, assuming equilibrium conditions, has been
analyzed by Lai and Jurinak (1971, 1972a, and 1972b). Using a one-
( dimensional
,
finite difference solution technique, the authors
investigated both linear and non-linear exchange functions in the •
transport of cations through a saturated soi1 column. The exchange
functions were of the forms:
S .f..+ (B.14)
Q- Kl
Co IS
and
"
...
S·
-Q -- C' C
[ - + (1
Co Co
C
- -Co
-) aAr 1
(B.1S)
where Q is the cation exchange capacity per unit weight of exchanger;
Co is the total concentration of cations in solution; 0 is a function
of CI,C o which is known as the separation factor; and Kl and IS

are constants. The effects of dispersion and convection, both constant
( in time and space, were included in the developed model. The model
" .
......
232
,
,
presented by Lai and Jurinak can be adapted to model both equilibriwn
,
exchange adsorption conditions and special cases of ion exchange. A
similar model was considered in the present study 1 to express the
re~ationship between the concentration of contaminant in pore 'fluid
solution and that on the solid phase.
In sununary 1 sorne mode ls of adsorption processes in clay sa il
systems have been presented in this section. The correct modelling of a

1
solute undergoing bath transport and adsorption through a clay soil
system necessitates the selection of an adsorption model that best sults
the given system The use of an improper adsorption equation w1 II
greatly affect the transport model, and will possibly give rise to
erroneous conclusions regarding the nature and description of both
parameters and processes of the system analyzed
B. 5 ION EXCHANGE \: l
Ion exchange i5 a process in which ions held 'by electrostatlc

,
forces ta charged functional groups on the surface of a solid, 111"('
. \
exchanged for ions of similar charge in a solution ln which the solld l5
in contact with (Weber, 1972) Ion exchange resembles adsorption ln a

/
manner that, in both c~se5. contaminant speci ..,s arc takE'n up at tlw
~
interface between the two phases in con tac t The hllsic diffel'"l>!H'('
between the two phenomena is that ion exchang~. in contrllst to
adsorption, i5 à stoichiometrlc process (Helfferlch, 1'167, IInd Syk(!s,
1973) . For examp1e, every Ion which 15 remuved from the p~rmt'lltl.'
... solution is rep!aced by an equlv~1ent amount of another lonie speci~s of
the sanie sign. While the distinction' between 10n exchsnge and
233
adsorption seems to be clear-cut, it is often difficult to separate the
two phenomena in field observations (Helfferich, 1962).

\
Ion exchangers, by definition, are insoluble solid materials which
carry exchangeable cations or anions. In the case of contaminant
transport, they ·are represented by clay soil aQd soil constituents.·
They consist of a,framework held together by chemical bonds or lattice
energy, and carry either a positive or negative charge. This surplus
charge is compensated by ions of opposite signs, which are called
counter-ions (Helfferich, 1962).
Clay minerals exhibit cation-exchange phenomena owing to a net
negative charge on the surface of, most clay soils. This charge
deficiency may be caused in a number of ways such as: (1) broken bonds
at surfa.ces and particle edges, (2) i:io,omorphous substitution of a
counter-ion of lower valence, and (3) ionization of structural
functional groups (OH-, COOH-, etc.) (Buckman and Brady, 1969; and
Yong, 1975). Exchange capacity due to isomorphous substitution is
constant over a wide range of pH, while the exchange capacity due to
J
ionization is highly dependent on the pH of the clay soil-pore fluid
system and the counter ion concentration. Be low pH 7, li ttle
ionization occurs, while above pH 7, ex change capacity increases with
increasing pH. In comparison, ionization could account for approximately
1..
50% of the ex change capacity of kaolinite, and, to a 1esser éxtent,
iUite and montmorillonite (5% only).
The cation exchange equilibrium of soils has been adequately
described by the mass action law (Wahlberg and Dewar, 1965). This 1aw
( and the resulting equation assume that the exchanger (clay soil) has a
\ 234
--
V homogeneous charge distribution and that exchange takes place throughout
the volume of the soil exchanger. In contrast, the double-layer theory
and the Donnan equi1ibrium model more correctly assume that charges are
distributed at the surface of the exchange materia1s (Sykes, 1975), For

•
claY,soils, for example montmorillonite as compared to kaolinite, the
difference between assuming that the charge resides on the partie le
surface or throughout, is not too great (Weber, 1972).
The ion ex change reaction can be described as
(B.16)
where a and b are the valence of the counter 10ns A and B, respectivè1y;
\.
and (R-) represents art imm~bi1e functlona1 group attracted to the ion
exchanger. According ta the law of mass action, the equilibrium
-
•• relationship is:
(B.17)
where ~ i5 the mo1ar 5e1ectlvity coefficient; CA and Cs are
the concentration of A and B, respec~ively, in solution (meq/cm 3 ); and
and the adsorbed concentrations (meq!s of
exchanger), The selectivity coefficient is not constant but is rather

/
dependent on the equilibrium conditions. According ta Nicholson et al.
(1983), the changes ln the net storage of the 10ns on the exchanger
sites available in the aquifer can be estimated using mass-a.ction
relations and.selectivity coefficients.
The kinetic processes involved in ion-exchange in the clay soi1
system are very simi1ar to those involved in the adsorption of solutes

1
235
( from solutions. The ion ~Change reactions treated in the present study
are assumed to be governed by the local chemical equilibrium. The

t
appropriate transport equations and numerical solution techniques for
\ .
these types of reactions have been treated extensively by Rubin and
James (1973).
,
~.
B.6 HICROBIAL DEGRADATION OF ORGANIC WASTE
5ecause of large amoun~s of deC;lmpos ible organic material present
in most sol id wastes, the tendency is towards partial decomposition and
production of volatile fatty acid formation within the landfill. This
results in the release of soluble organic matter ta , the generated
leachate solution, producing chemical oxygen demand (COD) as hign as
40,000 mgll in the extreme cases (Rovers and Farquhar, 1973), in
contrast to a COD value for, domestic sewage in the order of 100 ta 200
mg/l (Metcalf and Eddy, 1972).
The mechanisms working to reduce organic matter concentrations in

1
leachate, during migration through,clay soil, can involve both physico-
chemical and biochemical processes. The most active physico-chemical
processes are likely to be dispersion, diffusion, and ionic exchange and
adsorption, whith have been discussed in the preceding sections, as weIl
as a filtration mechanism which could operate for'particulate matter.
The biochemical processes involve microbial degradation, either aerobic
or anaerobic, with the latter expected to be most active, since oxygen
supply at depths within the subsurface environment can be expected to be
limited (Farquhar and Rovers, 1973).

1
(
\"
236
B.6.1 Anaerobie Degradation
The anaerobic deco~position of organic matter involves seViraI
seqUent~al and parallel \omplex biochemical reaction5. The first major
step of degradation i5 the conversion of complex organics such as fats,
proteins, and carbohydrates into simple forms, usually volatile fatty
acids, through fermentative processes (Chian and DeWalle, 1976)" The
simpler volatile fatty acid intermediates include formlc, acetlc,
propionic, butyric, and carbonic acids (McCarty, 1964). Subsequent
reactions mainly involve the production of CH 4 as a result of volatile
fatty acid utilization. lt is weIl established that the first s tep ls
rapid relative to the second step. As a result, the volatile fatty acid
utilization step is taken as the rate limiting step
-- Chian and DeWalle (1976, 1977) introduced two addi tional phases
over and above the two phases described by McCarty (1964)

1
One phase
invo1ves the assimilation of catabo1ites such as amino acids accumulated
in the firs~ twa phases. During the other, the humic carbohydrate-lik~
materials with molecular weights greater than 50,000, accumulated in the
third phases, are removed. CMan and DeWalle (1976) also found that
refractory organics consisting ~ainly of fulvic materials remained as a
non-biodegradable residual at the end of the anaerobic processes.
ri)
In summary, four distinct biodegradatlon steps were identified:
1. The removal of humic, carbohydrate-like substances,

2. The removal of volatile fatty ~cids,
/' \
. ~f
3. The removal of,inte~ediates teased during the second stage,
4. The removal of refractory organics.
The biodegradation rates are reported to decrease as the system
progresses from (1) to (4) (Chian and DeWalle, 1977).
,
237
B.6.2 Microbial Hàss Transport in Soi1 Media
Soyupak (1979) observed that soUd retention Ume in an anaerobic.
filter ranges from 84 to 665 days, ar:d the liqu1d detention time ~nge~-
from 4.5 to 72 hours. Thus the microbial mass transport within the
anaerobic fil ter was slow. . Consequently, in the case of leachate
migration and accompanying biodegradation in soil, microbial, transport
is likely to be small. ' This observation Is also supp~rted by several

..
sour~es. Dazzo et al. (1972) reported that 90% of fecal coliforms were
removed in the
; ,
top 13 cm of soil when liquid manure was allowed to
percolate through soil. Bitton et al. (1974) observed an increase in
the retention of microorganisms by soils with increasing clay contents
of the soil. Wollumn and Cassel (1978) investigated the transport of
microorganisms in sand columns and reported that most of the organisms
( introduced to the fil ter were retained and trapped within the first 1 cm
."
of a 20 cm 10ngocolumn. A1so, the ratio of measured effluent microbial
concentration to the influent feed- concentration introduced as stock
loading was less than 0.05%, indicating a limited transport.

1
1
B.6.3 Biodegradation Kinetics
In the case of organic matter with a poor biodegradation rate, a
decay function can be considered to be due to the biodégradation by
anaerobic bacteria. The decay function can be expressed as a function
of solute concentration (C) as follows:
(B.18) ,.
where (t-~) the first order desradation coefficient 1s.
c A simUar sink te~ wu utilized ~USly by Van Ceunchten et al.·

238
o (1977) as a genera1 biodegradation term and a1so by Soyupak (1979).
Table B~2 summarizes the value of ~ available in ~iterature.
El
Fulvie acid-1ike materia1s, with mo1ecular weights predominantly
between 5,000-10,000 were considered to be non-biodegradab1e refractory
J, organics (Chian and DeWa11e, 1976). Consequently, no biodegradation
term shou1d be included in the mass transport equations, i.e.
ac _ 0
(S.19)
at
/
Soyupak (1979) concluded that the very slow rate of organic removal
'"
was attributed to either: (1) a space limitation for growth such ~hat
the microstructure of the soil was unable to s~pport microbial growth

r
beyond a maximum level, and/or (2) the presence of the leachate solution
- of poor1y degraded organie matter.
-- '1
B.7 PRECIPITATION
.
.'
Precipitation involves the fortnation of insoluble salts of
multivalent metailie ions, The major anions involved include carbonate
(C03 ) , bi,carbonate (HC0 3 ) , hydroxide (OH), silicate (S~04)' and
phosphate (P0 lt ) ' The- advantages of precipitation as a inechanism for
co~taminant removal are its,high capacity and its low reversibility.

u
Similarly, there is no equivalent cohtaminant released as in the case
of the ion exchange process (Farquhar and Sykes, 1980).
kt
Griffen et al. (1977), Fuller ;nd Korte (1976), and Farquhar (1977) ,
studied' the precipitation Dt metals during contact ~etween landfill
lea~hate and so11s of various types o• Their results indicate that most
multivalent metallie ions, except calcium (Ca) and Magnesium (Mg), are
..
"
?
( TABLE B. 2 'J.alue of K3 Available in Literature
The Avai1able The Source The Conditions Untler Which K3

Literature
Value was Estimated
-1
K3 (day )
0.131 Chian & DeWa11e' Aerobic biodegradation of leachate

(1977) organ~cs for TOC levels between
100-900 mg/1 for biodegradatlOn .
phases (1) through (4) as def~ned
byauthors
0.209 " AerobJ.c b~odegradat1on of 1eachate

organics for 'l'CX: l~vels between
100 to 290 mg/l for biodegradat~on
phase (4) def~ned byauthors.
Batch reacotrs were ut11ized
1 - 3 . Ganon (1966)
Eckenf1eder & '
1 Settling and/or high
existed for n.vers.
ox~datJ.on
O'Connor (1961)
0.6 - 0.8 Ganon (1966) 1 Settll ng and b1ooxidat~on "Normal

Eckenfelder & B~ochemit:al Ox1dat~on Rate"
O'Connor (1961), for streams .
• & Camp (1965)
0~092 - 0.14 Schroepter BOD bottle rate for a river

(1960 )
( ..
. (
240
kept in low concentrations through precipitate formation.

~- \ j
The most important factors affecting precipitation appear to ...ge-t>H,
PC0 2 , leachate composition, and the free lime content in the soil.
The data presented in the literature demonstrate precipitation as a
required contaminant- attenuation process in soil. Unfortunate1y, it
functions for only a limi ted number of the contaminants present in
leachate (Farquhar and Sykes, 1980).
r
241
( APPENDIX' C
ONE DIHENSIONAL MATHEHATICAL MODELS FOR PREDICTING REACTIONS
AND MIGRATION OF LEACHATE THROUGH CLAY SOILS
o
C.l GENERAL
Differ~nt approaGhes for the modelling and simulation of leachate
interactions and migration through various clay soils can be divided
into two broad categories: (1) those approaches ~t are based on
thermodynamü.s, and (2) those that are based on lhemica1 kinetics

• • 1
assuming equilibrium and/or non-equilibrium conditions. The kinetic or
dynamic approach attempts to provide insight into both the rate and the
mechanism of interactions and transport processes. According to Wilson
(1967), the interaction mechanism of the app1ied phosphorus (P) with
soil can more appropriately be described via the kinetic approach rather
{ than the thermodynamic approach. The rates of adsorption (forward
reactions), which remove ions from the pore f1uid solution, and
desorption (backward reactions), which increases ions in the solution,
are general1y more important than equilibria concentràtions of ions in
the soil solution.
A basic principle underlying the thermodyna!llic treatmen-t of any
physical or chemical reaction is that the process must be comp1etely
reversible (Mansel1 and Selim, 1981). Leachate migration through clay
soils, however, undergoes a cQmplex series of reactions that common1y
exhibit some degree of irreversibility. Thus an ion-exchange reaction
for different contaminants which exhibit incomplete reversibility cannot
be analyzed (Lee, 1973) using a thermodynamic or static approach.
( In the following subsections a review of the mathematical models

J
242
used for predicting the reaction$ and the bransport of various cations
andjor anions applied to elay soil during the migration of the ieaehate
solution will be presented.
C.2 THE GOVERNING EQUATION OF THE CONV~TIVE-DISPERSIVE ~RANSPORT OF
REACTIVE SOLUTION
The common starting point in the development of a differential
equation ta dElscribe the transport of contaminants into clay soil 1s to
consider the flux of solute into and out of a fixed elernental volume
within the flow domain. A conservation of mass staternent for this
elernental volumè is:
net rate of flux of flux of loss or gain
-
"
char:ge of solute out
Jnass of solute - of the

, .
solute into
the
of solute mass
± due ta
within the element e1ement reactions
element
The ge nera1 mathematical equation that describes the one
dimensional form of the convection-dispersion equation for reactive
constituents in saturated, homogeneous, isotropie media under 5teady
state, uniform f10w is:
a a ac a a
at(9 C)- az(9 D az) - az(9 v C) - aE(p S)-Q (C .1.)
where C is the ~oncentration of the excha~ging solute (MjL 3 ), S i5 the
amount of solute ~sorbed per unit we1ght of the exch~nger (M~), z 1s
the depth of the sail column along the direction of flow (L), t i5 time
(t), 0 is the fluid dispersion coefficient (L 2 jt), v is the average.

243
c pore water velocity (L/t) ,
pore fraction (-effective -porosity)

p is the bulk density. (M/L 3 ) ,
or the volumetrie water content

e is the
(L 3 /L 3 ) , and Q is the rate of an -irreversible reaction (M/L 3 .t)
which removes solute from the solution phase.
The first term on the right-hand side of equation C.1 refers to
dispersion or mixi-\1g, and represents the combined influence of molecular
diffusion and hydrodynamie dispersion (Appendix B). The second term
refers to the transport by convection. Reversible sorption is given by
the third term and Irreversible 50rption is given by the sink term, Q.
The accompanying differential equation that describes water flow in

~ ~
the 50il may be expressed as (Wong, 1972):
(C.2)
( where q k(h) ah is the Darey flow veloc i ty and k(h) i5

az
the hydraulic conductivity of the soil. expressed as a function of soil
water pressure head (m of water) 1 h. The pore water velocity i5 defined
as V ~
e
When the 1each~te flows through the clay lin.~r is steady, such that
the pore-water velocity remains constant, the solute transport equation
becomes: .
(C.3)
If the reversible sorption oceurs as an instantaneous (loealized

1
equilibrium) p'rcreess, as leachate moves through the clay soil pore
space~ then this equation may be rewritten'as:

144
(C.4)
where R(C)-l+~ 1s a retardation function resulting from
reversible sorption, B(C) -~ is the sorption buffering
capacity 3
(L /M) of the soil under equilibrium
.
conditions,
-
DR(C)-Rfc) is the retarded dispersion coefficient, VR
v is
if(ë) the average veloci ty of the so lute or retarded pore
water velocity, 1/9 ~ is the retarded sink

R(C)
term.
If the sorptio~ isotherm, which is a plot of S versus C for
equilibrium conditions, can be described by an ana1ytic equation, then
the 5 lo~e at any concentration becomes the

-
sorption buffering capacity B(C).
- C.3 MATHEMATICAL MODEL~ THAT ASSUME CHEMICAL EQUILIBRIUM

"
AlI' the contaminant species in the pore fluid may be considered as
being in either the mobile solution phase or in the immobile sorbed
phase,
[9 Cl ..... ~! [p S 1 (C.S)
where r! and rb are the forward and backward rate coefficients
(t 1 ). ,frransformation of contaminant .species between' the two phases may
be assumed to be instantaneous for equilibrium mode1s with the rate of
reversible sorption in Eq. (C.I) expressed as:
a(pS) _ B(C) a(ec) (C.6)

at at
where the shape of the sorption isotherm will dete~1ne the buffering
..
245
capacity B(C). For kinetic models 1 the tran~formation of different
species between the two phases is assumed to occur at a Tnet rate
represented as the difference between finite forward and backward rates
(c.7)
where n - 1 if the equilibrium adsorption isotherm ~s linear 1 and n < 1
if the isotherm follows the convex shape of the Freundlich isotherm.
After sufficient contact time between the soil constituents and the pore
fluid solution, the left side of Eq. (C. 7) becomes -zero and the
equilibrium distribution coefficient can be given as a function of t~e
'ratio of the forwa·rd and backward rate coefficients r f and r b .
c. 3.1 Retardation FunctiQns
For a linear sorpt'ion isothenn where
/ (C.B)
and K1 is the distribution coefficient (L 3 !M) (Freeze and Cherry 1
1979; Higgins, 1959), the sorption buffering capacity has a constant
value B - K1 . The resulting retardation function
R-l+!:K
8 1 (C.9)
is independent of the e51uilibrium- solution concentration, so that
transport of the solute through the clay liner is neither enhanced nor
st.\ppressed by a considerable change of concentration in the soil
·solution'. Of course, for the simple case of a non-reactive solute that
does not undergo sorption with clay soil components, the retardation
function is unity and the pore-water velocity approximates t;:he solute
velocity :
1
;
/
/ 246
For nonlinear sorption models such as the Fre~dlich and Langmuir

/
û equations, both B(C) and R(C) functions vary with ~olute concentration
!
in the solution phase. For the Freundlich equation:
• n
(C.lO)
where n>l, the sorption buffering capacity is expressed as:
B(C) - n IS Cn - 1
and the retardation function as
R(C) - 1 + ~ n IS n 1
C- (C.l2)
Therefore, the buffering capacity predicted by the Freundlich
equation decreases with an increase in solute concentration, i.e. there

,
is a decrease in the effect of retardation on contaminant transport
through the clay soil.
Solutes that obey a Freundlich sorption isotherm would be expected
to move rapidly through tne ~oil when the concentration in the leachate
solution is relatively hig~. Thus, during the migration of leachate
through clay soil, the most rapid velocities for cbntaminant
concentration are near the surface and should decrease with the depth
and time as sorption reactions remov'e those contaminants from the
downward- flowing solution phase. Also, pol lutant migration through
coarse-;textured sandy soils which have small values of the distribution
coefficient ~ tUld be expected ta undergo less retardation' than
through clay soi s with large values of IS.

,
equation:
(C.l3)
247
where S~x is tte maximum content of the sorbed solute

( (contaminant species) in the solid phase, and t~e parameter K4 is a
measure of the affinity of sorpt~on si tes on clay surfaces. The
" sorption buffering capacity is expressed as:
1 (C.14)
B(C) - Smn'
and the retardation functrion as:
(C .15)
Since Smax represents the maximum solute sorption when aIl the
f
sorption sites are occupied, the buffering capacity defined by the
Langmuir equation, and thus the retardation function R(C), will be
sma1lest for soils having the smallest value of Smax' Solutes that
( obey a Langmuir sorption isotherm are expected to move through the clay
soil with decreasing retardation as the solute concentration in the
. leachate solution is increased to higher values. For solute
concentrations that exceed saturation of the sorption sites, the solute
can be predicted to move as rapidly,through the soil media as if
sorption did not occur.
C.3.2 Transport Models that Assume Local Equilibrium Reactions.
(Instantaneous)
This model was developed and used by Cogaun et al. (1968) while
studying the miscible displacement of sorne anions, such as Cl and P, in
two H~waiian soi1s. They used an existing ana1ytica1 solution for a
step change of the influent concentration Co of a nonreactive solute
c as follows:
248
Cco - 0.5 (erfe (~~) + exp(VoZ) + erfe (~~» (C.16)

~4Dt ~40t
where C is the solute concentration, 0 is the hydrodynamié dispersion
coefficient, and V i5 the average pore ve10city of the soil water. To
adapt the mode1 to account for the a5sumptions of: (1) instantaneous
sorption, (2) rèversible reaction, and (3) linear adsorption isotherm,
Eq. (C.l6) was modified as:
(C .17)
)
by omitting the second term in Eq. (C.l6), i.e. CIC o - 0.5 when z - Vt
which implies that CIC o - 0.5 after l pore volume of cumulative
leachate f10w The second modification in Eq. (C.l6) used the volume
of cumulative flow Va"" that occurred with the arrival of CIC o - 0.5.
In Eq. (C.l7), '7 - OjVz, for nonreactive solute: Vt - (V/Vo)z.
- Equation (C.16) can also be expressed as
C z-V t
-C - 0.5 erfc {__o_.} CC .18)
() ~4Dot
( V
where Vo -11+ (9Ip) K]
is the retarded solute" velocity and'
o is the retarded dispersion coefficient.

[1+ (9Ip) K]
Thus, the use of the parame ter Va as used by Cagauan et al.
(1968) only applies if contaminant sorption occurs linear1y and
instantaneously. In genera1, these two assumptions severe1y restrict the
use of. the Va concept. Also, if these two assumptions hold, then the
retardation factor shou1d not vary with a change in the pore f1uid
ve10city. Nonethe1ess, some researchers (Selim et al., 1975) found that
by inereasing the pore f1uid ve10city from 292 to 1050 m/hr, a resulting
1:
1
249 (\
( decrease in the re~ardation function (R) occurred.
C.4 HATHEHATICAL MODELS THAT ASSUME CHEMICAL NON-EQUILIBRIUM
REACTIONS
Sorption of certain cations and/or anions pres'ent in th~. leaching
solution are characterized by an initial rapid rate of removal followed
by a slower rate, which may not reach equi1ibrium even after a contact
time of several weeks (Parfitt, 1978). The slower rate appears to be
dependent upon the concentration of that solute in the leachate
solution, and has been attributed to a slow decomposition, precipitation
process, and/or diffusion into the sorbing surface (solid phase). Thus,
for modelling this process a kinetic model s~ould be considered. An
empirical sorption-rate equation of the form:
( (C.19)
is usually used in similar conditions, where a, b, ana d are constants.
Equation (C.19) was reported to provide a better description of the
experimental data than did an equation of the form (Enfield, 1968):
~~ - cr (!S C - S) (C.20,
where cr is the rate coefficient for desorption ,and !S is the

distribution coefficient for a linear Freundlich adsorption isotherm.
Kua and Lotse (1974) proposed an empirical equation based on the
Freundlich isotherm equation. They altered the Freundlich equation by
arbitrarily inserting the time-dependent expression
c
(C.21)
"
250'
to give the following equa~on for the time dependency of sorption:
(C.22)
where the Freundlich superscript n - NjM, K is a constant, and t is the
reaction time:
C.4.1 Mathematical Models Assuming Irreversible Kinetic Reactions
Giddings (1965) reported that removal of solute from the solution
by chemisorption to a solid surface is usually very slow compar~d to
removal by physical sorption. The author also stated that physical
sorption May often occur as a first step to chemisorption. In the

~
second step, the physically sorbed molecules undergo a slow
rearrangement and strengthen the bond to the surface of the clay soil.
- Once a Molecule bec.omes chemisorbed to the
slowly.
su~face, desorption occurs
Thns, chemisorption May account for irreversible sorption of

solutes.
Irreversible precipitatiçm or chemical inunobilization processes
represented by the sink terro Q in equation C.1 have been considered by
Many investigators (Cho et al., 1970; Panda et al., 1978; Mansell and
Selim, 1981) in two wàys. Firstly, the sink term was given ~s a first
order reaction with respect to C
(C.23)
where Kc 1s , the rate

'
(t- 1 ) fur precipitation and/or
chemisorption of solute from the sail solution. Secondly, the sink terro
Q 1s expressed as a first order with respect to'g

',- J 251
/
( (C.24)
where K. is considered to be the rat;e coefficient for chemical
• immobili~ation of physically sorbed solute to irreversib1e forms.

)
,_ 1
C.4.2 So~ption Models Assuming both Reversible and Irreversible
Kinet1c Reactions
Overman and Chu (1977) developed a reversib1e sorption-desorption
reaction followed by an irreversible sorption (~ical) reaction. This
model can be illustrated by:
(C.25)
where C represents the concentration of the contaminant species in
1eachate solution (solute); S1' the sorbed solute; S2' the content
of immobile solute attached to the solid phase; 5 - S1 + 52' the

(
total solute on the solid phase; and M, the concentration of the
sorption sites (positive and/or negative) unoccupied on the sOI,id °ph~se.
The chemical reaction ~1aS assumed to "fix" the contaminant species,
which had previously undergone reversible physica1 adsorption to
sorption sites present in the soil. The fixation processes cO,uld
involve the production of new compounds.

.Mathematically this model May
'... ( ,\
be ex-pressed as:
(C.26) ,
and
(C.26)
, where -K S1 is the sink term.

r
( .'
252
C.S MATHEMATICA~ MODELS ASSUHING BIODEGRADATION REACTIONS
:Jt •
~ Van Genuchten et al.(1977) and Soyupak (1979) suggested a first
•
order decay funetion for the biodegradatiQn ~f,o~ganic material due to
the microbial activity in the form of
(C.28)
"
where Ka ~s the first order biodegradation- coefficient (t- 1 ).
This model 15 s~mil~r to that of the Langmuir adsorption lsotherm model.
at infinite dilution., Soyupak (1979) used equition (C.28) based pn the
assumption that a~raction of the origi~l organic load presented in the
leachate solution is non-biodegradable, either in its o~iginal form or

1
as consumed oy microb1al processes. Furthermore, in the case of non-
biodegradab1e organic loads, Soyupak (1979) considered only the
convection and dispersion term in the migration of leachate through clay
- soil, 1. e.
(C.29)
"
F~nally, Lindstrom et al. (1967) introduce to the·one-dimensional
form of the convèctive-dispersive equation a factor that takes into

.'
account the rat:io of the surface area of the chemically active sites' to
"
the total particle surface area. The mathematical,model can be given as:
ac 2
a- e- - Vae (C.30)
3t - Daz 2 az-
G
,The above-mentioned prediction models are summarized in Table C.l.

,. ·r
o
• •
.' .
tJ
253
TABLE C.l Models for Describinq the Movernent, Adsorption, anà
Storaqe of Chemicals in Clay Liner
(
Phenomenon M:>del Equation
(1) Transport of buildup = +convergence

nonsorbin~ nonreactive or
solutes - divergence
Movement
-{a) rnolecuJ..ar diffusion Fick's law Jz =- D ac
az
and hydrodynamic
dispersl.on
Jb l convection plston flow , ~ •. Jz = VC
ac= Da-
c - vac 2
- -
dt az2 - az
(2) Transport of bUl.ldup = +converqence d(C+ pS)

at
= ~v D
az2
dC
az
reactive solutes or
- diverqence
storaqe
adsorption
(i) eqlll.libnum linear
nonlinear
(ii) non-equllibrlUffi linear

2
a(c + pS) - D ~
(3) Transport of buildup = +convergence at - az2
reacti ve wi th or - divergence
irreversible reaction + source - v ~
é)z
=Q
or - sink
source or Slnk Q=K7

Q = K8C
(4) Transport of Quildup = '+convergence t==~

at
a2c
. az2
biodegradable organic or - diverqence '
materials - Q
+ sink
sink Q = ~C
113 = tl:le first order
. biodêqradation
coefficient "
(
\
... 1
r' 254
o APPENDIX D
EXPERIMENTAL RESULTS CONCERNING MIGRATION OF
CONTAMINANTS THROUGH CLAY SOILS
- .)
i-
l
\ '
1
255l
c , SECTION 1
~XPERIMENTAL RESULTS
( \
~, .
, /
1
(
. ,,::;~ .A;
, .~
C·
, ,
'1'
N
• 1.11
0\
,1
-, ~ -
,.. ....
lA.,
(
,...
"-
;
----
TABLE 0.2 Summary of Different Constants (A,B,CC) in Equation 5.7
for Dlfferent Contamlnant Species During the Permeation in Kaolinlte Sail
.
.-
Pore Ca Mg Na Cl TOC
Volume CC B CC A . B CC A B CC A B
A B A CC
1 -0.49 166 14 -0.74 33.{) 1 -0.87 1140.8 9.2 -0.23 130 60 -0.66 185 5
2 -0.98 178.1 1.9 -0.68 32.7 1.3 -0.66 140 10 -0.33 94.99 90 -0.73 182 8
3 -0.98 177.7'23 -0.87 32.25 1.75 -0.56 138 12 -0.44 91.0 99 -0.78 179- 11
4 -0.35 173.2 6.8 -0.55 31. 5 2.5 -0.66 128 22 -0.43 71.0 Hg -0.70 178 12
r
• ,
5 -0.58 170 10 -0.44 30.50 3.5 -0.49

<
114.5 35.5 -0.38 52.0 138 -0 . . 66 176 13.5
O"""\~
.-
J
h- I
t.
N
U1
~
-/ "
)
..
..,
_•.J ( ~
C·
ÀtL
--1 •
• TABLED.3 'Results of the Chemical Analys~s of the Pore Fluid ~
'" of Sorne Leached Samples

,. n
Sample pH E.C. Water Soluble Ions (mg/IOO g soil) ....

~
Soil Type ,
No. f.l mho lem Na+ K+ Cà2 + Mg 2+ HCO; C0 2 - Cl "
3
..
7.4 2 7 .22 55.0 9.5 40.0 ~-O:-O-35:75 natural soil
2 7.3 26.1l9-_-6'3"':O- ------

~4.5 ~---100.0
--" p.O l
88.45 '~ 0.0 33.25 Il
-..J
3 7.3 26.50 70.0 8.25 46.0 6.6 . 76.25 0.0 33.20 Il
4 8.4 21.78 40 25 10 .4 2.2 51.85 0.0 70.0 illite

">-
.
5 8.7 21.78 50 21.2 12.7 2.60 76.25 0.0 70.0 "
0
6 7.2 32.67 50.0 36.0 11.0 2.,0 J8.25 0.0 52.5 kaolinite
7 6.6 7.53 12.0 3.25 > 6.6 1.8 3.05 0.0 0.0 " ~ -......
\ .' '\.
..,
, t
,
.
~:-~-
-"
IV
1 lJ1
00
'"
6
-.,
" t..
/k
J, ~' ,..
. 010 Fig. 0.1. Aelationship between Soluble ,and Adsorbed Ca Ions . ~
~
~
;
.008 o
Predicted
J <> "-
o o
al Langmuir
z
0
.006 0
H
ca 0
u
Cl 0 <> NATURAl SaIL (SERIES I)
w 0
al 0-
a:
0
al
.004 B - 0.006
Cl
ct
.. a- ..-o. 183 l/mg Kt
_6 ... 0.010
.002 .Smax - 0.662 "-
..If'""
l/K = 0.557 mg/1
0.000
o 20 40 60 80 100
'" •
1'.)
U1
SOLUBLE Ca IONS (mg/l) 1.0
l'
".
o
,1. /
Ct 1',"""'- •
~~~ .. f
.
. 010 Fig. 0.2.' Relationship betweer:a' Soluble and Adsorbed Mg~ons .
.-... predicted\
.008 ~
, ,~ Langmuir
en
z
0
H-
.006
-,
V~
f -- -----::;:;
/.
--' (>
--,"-...,..,-
'-
~/
C)
:E
1
c:J NATURAL SOIL (SERIES Il
tLI
ID
f5~
en
Cl
, / '"
ro
œ
B = 0.005
< =-0.007 l/mg

/ ~~
G ... 0.007
~
~
Smax :or 0.008
!
l/K la 21.94 mg/l

,:
....
Cl
.,
o~ooo
o 20 40 60 BD 100
4..
~ SOLUBLE Mg ~ONS (mg/l)

l'V
0\
o
.,
/
r
,..
"
':'
"1'
"
..J
~~ -
. 010 Fig. 0.3. Relationshlp bè~een Soluble and Adsorbed K Ions .
.
1
NATURAL SOIL (SERIES I)
,il
.OOB B = 0.002
Ct" --0.002 l/mg
,
'" s = 0.003
.,
~ .006 Sniax D 0.015
o
H
/,l/K =-382.1 mg/l
~
Cl
UJ
ID
a:
o " 0
en .004
Cl
/
0/
-<
<> /"
4
o ~Predicted
.002
O~/'
p7 o ~---- 1 '-.
Langmuir
'
0.000 - .:::
~'~~--------~----------~---- ________L -__________~________~
1 r o 10 20 30 J 40 50 ~,
SOLUBLE K IONS (mg/I) 1\.)

O't
f--'
.:.
.,Ir --
o c) o
\ . 00020 Fig. 0.4a. Relationship between Soluble and Adsorbed Mg Ions .
.. ILlITE SaIL
.00016 B .. 0.00014
... œ --0: 002, l/mg
G • 0.0001
~ .00012 Smax 0.00007
c
..... .. sa
Q)
l/K = 0.004 mg/l
:E
Predicted
ffi-
~. __ ~
. J tl
~rJl Langmuir ~
cr
c .00008
en ~~.-r ~.,
'----
c
ct /' ~ ~ ~
<:>
l'
.00004
,1 "
~
0.00000 I~------ __~~__________-L__________~__~________L-________- - J

o 20 40 60 80 100
rv
SOLUBLE Mg IONS (mg/I) '"
rv
.;>
./
" ~
~
.
"
'" ,..
. 00025 Fig. D.4b. Relationship between Soluble and Adsorbed Na Ions .
IllITE SaIL
.00020 B ... 0.00017
œ
>~
"'-0.005 l/mg
G - 0.0002
al
z .000lS
0
H
• SlJlax .. 0.00011
lU l/K - 70.07 mg/l

Z
Cl
UJ
al
a: o
~ .00010 ~
Cl
< Pred1cted
o o. _----7.':------
-
.....
) 0
- é> Langmuir
,/ .00005
~
-- -- o
o
-0
(
~
o "
~ ~
,..---
.--)
------ 1 80 .
0.00000 ~ ------~~'~
---- 20 40 60 '~
----:-:100 \
a 1
)
I\J
SOLUBLE Na IONS (mg/I) 0\
W
~
/
o
•.
"
::.
t!)
~
)
,
'~
t:': ) o
. 000015 Fig. Ô.5a. Ae~at1onshlp between Soluble and Adsorbed K Ions .
~
v r
,
KADLINIT~ SOIL .
.ooatH2 B = 0.00001
- ------------ œ --0.007 Itmg
.. 6 - 0.ObOO15 6
~.000009 Smax - 0.00002

o
t-t
"'-191,. B mg!1
::.::
~
..
filal
a:
" $ ~
/----:;:,~/_~T -
~.000006
Cl
<
// 1
~ /'
.000003 ~ ~ /'
Langmuir - ~.
~,~
o. 000000 ~V=~ ____ ~ _ _ _ _ _--1._ _ _ _ _----1_ _ _ _ _--..JL-_ _ _ _---.J
o 10 20 30 40 50
1\)
SOLUBLE K IONS (mg/I) 0'1
A
"
,.. f"". ,..~
"
,
•00010 .
Fig. O.5b.· Relatlonshlp
. between Soluble and Adsorbed Mg Ions .
~
KAOLINITE SaIL ~ l'
~ __,; .00008 B - 0.00006
ct --0.152 l/mg
G - 0.00008
~ .00006 0- Smax - 0.00000

H
l/K - 1. 353 mg/1 ~
.C»
2:,
•
1.00004 (
al
~ . ~ J' Langmuir
_~0='-j-
~
f '.>
.00002
J
~,
0.00000 ~
1
10 20 30 40. 50
1\)
0\
SOLUBLE Mg IONS (mg/I) Ln
. ..".~,
........ -
~~
~.~,~ . %
.000010
',,-
~
KAOLINITE SOIl:
.J ). •
B ... O.OOOQOS
.000008 ,
Ct =-0.009 l/mg
,
S - O.OOOOi
CI) - Smax .. 0.000003
z.000006
o
t-t 1/K - 4.004 mg/I .'
ca
Z
Cl
UJ
CD • •
a:: ~ 0
~.000004 o 0<> Predicted
c:(
o 00<> ° 0
Langmuir . . J
,.000002 ~. ------. -----:- - ~'._----
.,.
/ .. <:>
•
<> • " '- ..
0.0.00000 ; c -- 10 20 30 40 ,,' 50
,.
.., f"
1'1.)
0\
SOLUBLE Na'IONS (mg/Il. D
0'1
r
"'. . I!! ,
J
.~ ~
t~ "', è"~.
..,.
'~-
~
"
-1
~
l'V
0\
SOLUBLE Na IONS (mg/I) -.J
1
_.Ji
~ ~ - . fAt t
-
. 004 r Fig. D. 6b. Aelat~onship between Soluble and Adsorbed Na Ions.
.J
'\
{.
NATURAL SOIL (SERIES II)
B - 0.0018
.003 f- a ...-0.109 l/mg ..,J.
~ G ~.0002
.r ,
"-
~
CIl
:z
•
0
t-f
.. ca
:z .002
'- !
cUJ
m
a:
O'
• CIl
C
< .~
~'
~ ~
~
~ .001 ~ ~~ ... ~
Predtcted
~
.
~
o. 000 " /' , 1 1

o ·20 40 ~60 80 100
SOLUBLE Na IONS (mg/I)
,
ru
0\
(X)
(.
'.-!1 e, ~ f
"" Ct
....
~
"
~ fi"+: '~
,
,...
.. , Mg CONCENTRATION (mg/l)
~
,{ o 5 10 15 20 25 30 35 40 45 50
o
* ---..,.,.
20 1 -..
'eE 40
'"
" * ~ Natural Soi l <Series D
::z::
l-
lL.
W
CJ
60 ** *
* Experimental Data
Predicted
~
* 1 PV A =-0.473 B = 28 CC = 7
80,
2 PV A =-0.459 8.= 26 CC =9
"
3 PV A =-0.479 8 = 24 CC =10.9
4 PV
-
100 ~
A =-0.354 8 = 21 CC =14
5 PV A =-0.415 B = 18 CC =17
\
120 Fig D7(1.C()mp<~rlson of Pl'edlded allo t.1ed<;lIred Ma Pr()flle~ b~l'les Il
N
'-l
Cl
f:!)
.....
C-.' ~
il e·
of'
J
Mg CONCENTRATION (mg/})
o 5 10 15 20 25 30 35 40 45 50
o
...,.
,\
\;-
20
..
"E 40
E
'" ... Natural Soil (Series II)
:::r:
t-
0...
Lü
Cl
60 r '* / ... /'* 11- / '* / '* ,
1" '* Experimental Data
"
Predicted
'*
8'0 ~. 1 / // / 1 PV
-'-
A =-O.~5 8 = 28 CC = 7
2 PV A =-0. 7 8 = 25 CC = 9.9
~
3·PV A =-0.436 = 22 CC = -13

B
1001-
4 PV A ';'-0.354 8 = 21 CC =, 14
5 PV A =-0.424 B = 17 CC = 18 .
--
120 L
l'lU D 7b. Compar ISCln of Predlcted and Mea~ul'ed Mg Profiles (Series II)
r-v
...J
1-'
~
~ ,- ,.... ~
"
K CONCENTRATtON (mg/l)
~
o 5 10 15 • 20 25 ao
0'1 :1 1
II"
20
1 -Natural Soil (Series !)
120
FIU Il Ha (ulllpdrl'.>lI11 of Predlcted and Mea:=.ured K PrllfIlv::> (Sf'J'le~ Il
" . N
-...J
N
• ,~,1 r- ,.
"
~
"
. r~- ,
.'
K CONCENTRATION (mg/l)
•
..>
... "
0 5 10 15 20 25 30
o1 7 1 ...
".
~\
- - - - -
20
1 //1// Natural 5011 (5e~ies'II) ..,.'
.:-
"E 40
1 1// /1 •
E
'"
:J: 1
~
17 I TIT
j: • Experimental Data
~
Cl..
llJ
0
\' / / / 1 1 Predicted
60
l
11/-/ 1
~
, .. '-.l,
~
'\ 1/ J 1 PV A =-0.264 ·8 =9 CC= 7
•
80 r l '1 1
2 'PV A --o. 159 8
-
=9 CC= 7 .
3 PV A =-0.217 8 = 8 CC= 8
~ '4 PVA =-0.241 8 = 7 cc: 9
100 .... 5 PV A =-0.288 8 = 6 CC= 10
'-'
'"
...
- 120 ..... , rlu Il Hb. C()IÙp~r1.,nll Cil' Pre(l!( led,and ~1ed~ed K Proflif'''i (St>rle's II)
t- -J
N
--.J
i W
~ " ,
""" ./'- " ,
."
,~ Cl CONCENTRATION (mg/})
o 50 100 150 200 250

o
* *
2é} .. .
.* * Natural Soil (Series I)
"E.("
E 40 ~~
-------
-... ----.. -
.....---
.....,
'"
:J:
*
'- * Experimental Data
1-
a... predicted
LU
Cl
60 .,
* 1 PV A =-0.64 B = 136 CC = 54
2 PV A =-0.33 8 = 130 CC = 60
80 3.PV . A =-0.41 '8
~
= 107 CC =,83
. 4 PV A =-0. 26 B = 80 CC = 110 - - 1 •
5 PV A =-0:42 8 = 61 CC = 129 " '0
100 .i'.
."
120
FI!]
\
D9. COmpJI-I'iOI1 of Prt>dlcted and Mea'511red CJ Profilf'~
.-
(St-Mfles Il
e
1\)
-...J
A
--
"-
'r
2,0" Illite
Na
'0 .. .
N
1.6 o_ MZ
. .,.
'0
,..
-
"0
~
»
cu,
,
1.2
M N r
~
2'
N
......
t. 1 PV q.389 Q.840 0981
'E ,
'1
--
a
O,B.
"
2pv 0.233 0776 0.983
0 3pv 0.191 0.741 0981

04
• 5pv 0,113 0.660 0939
00
o 20 40 60 80 100
Depth (mm.)
"r;
-
''\
,1
0.25
, '
K
\ 2
N M N r
.,. 0.20 D = MZ
b... A '1 pv 0,088 043 068
-
~
x
»
015
.. 0.059 0.517 0784
......
N o 3pV 0055 0.5 6 3 0980
E
• Spv 0048 0586 0994
a 0.10
\
\ \
0.05 \
"
a 20 40 60 Ba 100
Depth (mm)
,
Fiq. D.IOa. Dispersion Coeffici€!lt (0) Calculaterl fran Laboratory Tesbs
.
as a Function of Pore Volume Passaqe and OOpth of
. Soil Columfi', .
..
Mg
.
0.75
\Ilite
276 \ .
N
0 = Mz
( ~o
... 060
--
ct!
"0
X
>.
1 pv
M
0.175
N
0737
r
0980
2
........ A
~5
N
E .
-
,
0
• 2pv , ,.
0111 0669 0985
0 3pv 0,097 0651 1 0979

Q.30
o 641
• "5 pv 0088 0994
0;15 '
0.0
0.0 20 40 .. 60 80 100 '
Depth (mm)
"
Ca
( 20
N
0 = MZ'
M N 2
r
16 1
1 p" 0.971 ~o 971
., .
A. 0265
...
10
,....X
>- 1.2
• 2p" 0209 0752 0938
-"0
-
N
co
E
0
•
3 pW
Spv
0177
0169
o 716
0700
0848
084
-
Cl
08
0.4
op
0.0 20 40 60 80 100 •
(
Depth (mm)
F~g. mo .b: Dispersion Coefficient (D) Calculated fran LaboIÇltory TestS
as a Function Qf Pore Volume Passaqe and Depth of Sail Column . ..."
, Na
1.25
Kaolinite
'"
277
N
.., ... 0 MZ
~
} 1.00
....... ~
1
0
XC?
........
>.
al 0.75
"0
N...... M N r2
E
'-' .0. 1 pV 0.289 . 0765 0994
050
Cl
• 2pV 0283 0740 0966
0 3PV 0142 0729 0,947

025
• SpV
"
0180 0700 0956
00
0.0 20 40 60 80 100
Depth (mm)
-"" 2.0 K
9-
.. ,
0 = M ZN
~ 1.6
1
...
0
X
6-
1 •
M N r2
'"'
>. 1 l'V o 216 o 897
--,
-.0. 0827
ü
~
. 1 ~
--
."..
N
E • 2pv 0067 0,626 o 981
0 3pv 0051 0671 o 983

a 0.8
• 5 pv 0051 0560 0,.885

'\,
/,
04
0,0
00 20 40 60 80 100 -
Depth (mm)
F{g. D.l,a. Dispersion Coefficient (0) Calculated fran 'Laboratory Tests
as a F\mction of Pore Volume P*saqe and Depth of Soil
Column.
.
05
~
Mg 278
Kaolinite
.C 0.4 D'= MZ
N
~b
...
-
,2
x
>-
03 • M N
• 1 pV 0106 0673 0993
-
~
"0 ""
N
y 2pv 0067 0639 0;862
E
...., 02
0 0, 3pV 0063 0630 0962
01
• 5 pV 0,060 0622 0920
00
00 20 40 60 80 100
\
Depth (mm)
(~ 1,2'5
Ca
D , -_ MZ N
100
~
M ,2
'0 ~
x 075
,......
>- • 1 pV 0.273 0777 0.947
-
~
"0
N
... 2 pv 0260 0750 0950
,E 0,5
...., 0 3pV 0257 0.741 0930
Cl
0,25
• 5pV 0187 0739 0,990
0,0
00 20 40 60 80 100
( /
Depth (mm)
Fig. D.llb, Dispersion Coeffieient (0) Calculated fran Laboratory Tests
as a ~.c ion of Pore Volume Passage and Depth of Sail
{ . Colunm. (~'-_
~ ~ ,
~
el
Concentration (mgll) -:
o
o
.. 150 300 450 600 0
,.
20 40 60 80
1.
0 150 300 450 600 0
. 20 40. 60 80
t "
~.
100
2(JO
'"'
E 1 \ ~
E
'-'
-
.c
Cl.
<D
300
0
400
500
K Ca Mg
Na
600 ... .-
-.- ""
j
.,,-
,Fiq. D.12. Catlon Distrlbution Alonq the Landfill Physical Model after the passag~
<' of 0.30 Pore Volume of Leachate Solution. ~
IV
-....J
'1 \Q
~
, "
280
( Concentration (mgll)
140 170 2'00 230 260 290 320

o r-------,--------r-------.-------,r-----~~------~
,1
,....
E
.......
• "
<!)
ü Weil No. 4
-co
~
::J
(J)
8
• 25-years
-
"'0
c:
CO
v 50-years
(. ...J
~
12 , • 75-years
0
~ o 10Q-years
-
-=
0.
Q.)
Cl
16
c
,... ,
20 . 1
1.
/
24
Fiq. D.l3a. Concentration of ca'with Depth at Weil No. 4.

281
Copcentration (mg/j,
65 95 125 155 185 215 245 275 305

o ;------r------r------r-----;r------r--~--r------r--~~
Weil No .. 8 10-
....... 8
E
'-'
0
ü
• 25-years
- ~
~
:J "V 50-years
~~ (
Cf)
- -
'-
ü
c:
Cil
--'
12 •
0
75-years
10Q-years
~
0
.. ~
0)
en
..!::
..... 16
..
~)
'"
a.
0) "-
Cl<
~
""'!' )
20
"
1
24 1
Fiq. D. l3b. Concentration of Ca with Dept!:l at Well NQ. 8.

282
0.1 HASS BALANCE CALCULATIONS OF DIFFERENT IONS
PERMEATED THROUGH CLAY COLUHNS

.
0.1.1 DEFINITIONS
Co ... The input concentration of certain ions present in the
leachate solution,
CE"'" The amount of eluted ions, i.e.

'.
ions measured in the
effluent collected at the bottom o~ the soil column,
Cs - The ions ret8cined in the resident pore fluid which
designated as soluble io~s, and
CA - The adsorbed ions on the clay surfaces.
0.1.2 SAMPLE OF CALCULATION
The mass balance calculations given below is provided for Ca ions
( in series 1.
Co ... No. of pore volumes x volume of soil column x porosity
x influent concentration.
332.10 mg
CE ~ tne area unqer the breakthrough curve between zero and 5
pore volumes .
... Volume of the effl-uent x Relative concentration (C/Co )
x Initial concentration (Co)

.'
108.6 mg
Cs ... The area bounded by the initial and 5 pore volumes
migration profile curve
69.0 mg
, CA ... The area bounded by the initial and the adsorbed ion-
depth profiles, and/or the established relationship

\
283
o ) -
between sorbed and adsorbed ions.
170 mg ,
The fo110wing are sorne of the mass balance r~sults of contaminant
species migrated through natura1 clay soil.
________________________________ :~ ___________________ l ___________________ _
(1) (2) (3) (4) (5) (6) (6)/(1)%
Element ~(2)+(3)+(4) (lj-5)

--------------------.--------------------------------------------------------
Ca 332 106 69 112 287 45 13.3
Mg 64 19 12 23 54 10 15.6
K 28 12 3 7 22 6 22.2
-------------------------------1--------------------------------------------
......
.., .;
(After Yong et al., 1986)
o
284
c' l'
,<
SECTION 2
,
COMPUTER PROGRAHS
.
.
f]
. '
c
tI
ç' , l
l' ;: r:1 . . rl!:l~11 IJ~ 2às
1'1 ',.,. U It; I~,' i_,::-H'~ T :;Ç)I)Hl~F: 1'1,:' p.j( 'Ci
:::- TIl
ü 1h C
[,
ri
r: (î .
1 HI:, T I s e H CC, E 11 ] F "~- 8 t ~'I-\ 1- [)
ï ~ THI:: ~'-':,n'IPTOTI'~ ',1ALUE IJF llŒ ';UI',\:'-:=i,lrFI~1 Tlltl,
IJULf, BE Uf,T~IN[cli:':=rL,M '[3(lUNlI(U<r ',ClI'Hl_ r 1 UIJ'~ ,,," .' , f I
,- l , ,... HI-\ '; 6 Ffi',1 fj~j T f-H I~) 8 1 -'11 ri U-ll 'J 1 l'It, r :'i1-= L, r !., T hl' le t. ";l,.jUH ,,'}-
.! 1 l'TrJI
l, r.~.J ~C.ll)) ;1(: 1 LeJ J I:C, ..Jl,I~1
! r
,311 l'f.I_''' = it-J/t.;

'" 1"1 .... , ,,'C'!)
1 1 "-' ,-'I~I~ [.:1 fil ;-
JI') r-rll) "'~_f-,} Tf, "(li STEi-1 c,n ('
L' \', p.:: ,..;
I~ L 1 l ,J' 1 1
; :', "JE" T N : 1~E .. r l

1.11 1 CI"frlr d:-JNtf:Nrr;I-\TTUI'I~:;
":,/1 1- ()f·' 1: l rD -;
!..-".1 f!"r:'h' [',1:,-:.1 ro ")1)1 '':;TfP <':10
."1' p:nrlr UJrl\I(~ 11lHHttt l:iUU
•1 H (i " ; r " [ r J,' .
l ,:i() r,It:::, 1\1 - f~1::. ,1 l
1 l" .) \ ~, E F.: '1 .2 . l' E 'lOF F :' L:':;
, 'l" l, l f lE' ,..;Ct • 20) - \ SdU , ;:,)) : L if~E" 60 ,2t) ) -11:;(' , l -1') )
: l" [:.'.'_llf' fîfJ\ E:.1'lrprirIOrl~, PO[IJT-:' Ol~ '.qUIWIfÜ·~TF,.'::; '.'1 , ': r1
1) r'Ji-' ,J~l TD .::') :1.,HIC:(~3t)+JI2S,~'2}"(o31)+Jt.:::.L:" : '1:' 1 r
- ~'.' For·' .1-1 rCI H' :LIh'EI8:::'.:':U+,rtL:"}-, '::l,.:'(/I-,.fIJ'=,J,1 r 1
Il' f: tOI P f': ,-:, l r fî :3') L ' :; 1 E P r:, ( ,
':,) fUr,' f-\ TO 7
~ '"j 1" \ : , . ;j", j- C (L ~ j ) / ,'1 {..; J ,>( ~ '::, \ 'II )
, ' , r - . l ,-'- ( l - J ),' ..- 1 l 5lJ

,-,(' . f,· L [ TH[f.J L.IN!::,,< {" l ' r ' I / ' -1>( (, 'r'()
"1' J '\, ' , ' : T Tl· i 1
"r~, '=1':: TI ,>< ( , , \, ) • 1. T j:'(~I_E 1 ;( ' ( , ,.) 4

) 'JL',' T l 'I~f:" T 1\1 •
'.:;urlJ o'LS
.l
,l, :- r JI.
,"
1J - " J Hi -':-,1 J]
, :-- J ) : \ 1 ~,Î J "
C, r f LI ,-:, (,
\
.' " t ':,II-',r.1 J:'(-, 1_(:,',..;1 :J1)11t-.1'::;' t-1f:.IHu-[l
~ .• ,( • L 1 _ 1)
flli-' [:['T") -;
" ",1 riJoI' llJel !...,I~ 1 .1'4 l , (1 f', T ),11 t: f J... 1 : '- 1 1 l' l) .. !: '
,'1 ,1 1 l, 1:- ( ( J \ l' 1 1 - ,- 1-, ri J
lI" , , ' [ 1 f j / :. UX:' l I~ 1 J r' 1 i )

,-11(' I~':::'" T l : l'~E:\ T 1'1
'\, 1 ) -::)
,,
:=- Il h' i: [ r ':1 :.'
't , t- l " '1 r , 1" 1 FL '
: 1:'~ 1 If: < r. l
lt'",l J:.(,:r_iJ ,f-
./ '1 L JI It 1 ~II ~'I' r-l <:',8 ), .?I) 1 : L J l'je 1 -,1', :":' 1- ( ',1) 1 Ir, l ,
~ ,( ,1 1 : t -, r. T - f } Tl") : J_ f; JI: 1 ., 1 ) t~ j t _ ~, 4: 1. ) - t 1',1 +- \ j ; _~. t ,1 1 - , '1 1'
l ' ;,
" 1 J
l' t', l~'
:.',r; - -1'-1r-i
1.:'
r 1 1
r C'
..j
11 J : ,_ J" H. 1 " ,1- 1 y ::-' ) . 1 ~ -;,
. '() j- 1, l' If
_ 1';' I,C" -, r,::: J,~ ·:"l!~rrJr· ~I'D:~' 1 ('fj:'JI! ~lr~J:-1rLtJf'11 f'11,

..., :..: ): l ,-_
r( :;1Lr-' l', ;','., • ..,r.:. '., T :1-" 'hl ~'·l:~ ~, :'1'; Cil l' 1 1 l"," ~I n; !I
'-,' 1. :.' ,"\ .:. 1 ~ ..... 1 -1 :~' 11 l r

,~_ : /-' :.' ! 11r 1. ' ) .'
1
J.
-
' :~i'lrlr l ,-_ i -' r l-~ 1 "" l '
1_ [-,1 riT '-: ... _J t -i : ,J 1" r ,~ ; ". \ J:':! !:1 1'1" ,1 j-l".' .. rI
•
,-i/J ~ ,- l '
,'11 ~ ~~l 1 t 1.,.......1 r,\,J (1:
," .:.' )
: l" 1 ;:"
- I} , ... , ti! ,,: 1)
c ,,:"':
J' " :=tlP
),1-=:'·[[
[;: L rrJ .J.J
286
" :-,~)t·I .... :.SIJf'11+)(J)

,:, - 1 •.: 1JI 1:.. :',1 1r'i ~- +.: 1 IN)
'. '\' '1'1'=; + .. ( 1 f ::
'. 1 1f'l:::; " ,j i
, (, lJf1..1 =,"
lM...). j-'\, f )1' Cl [ ~I j
- 1" :~t'T l
, . 'l 1 P;. l ~ 1 ï" : 1 l . 1'1 ) = ". '1 l ,l'~ J
-, :u J:.' r 1 1 ,1 f)
- t" :; 1 f, l..l - R r ': 1 It 11)
1-\: 1 ': l 'f1 3
~ ':-' 1 l 1 JT "r HE t: Id \),.; T J Oi' 1
~lf.
.. ," '1-1:; Tf J r .. ~ , l i t ~ . t • l , t , ., , t ...
7" -, " f :. E;- P" t= \ 1
':-~I, 'F,~r:'lr';: ::;.[,\PI11Z)+,:C" .
- '1-' P;: fil j "h: "1-1 'p,: 'F: , '\~{: = "G::I N J
".'1) J~t}iJt) '1::-:;..),
-lU/·:, r'H) :PPI,'jf"I'lI)-= '80
,J', ~'!J'T FITrE[f !:l'T LEr;:..;T -;QII(-\RF;
IIIF"iE f'lE1H(1I
.: 1 l ': n~ 1 T - 1 l f) l ~ 1
-~o-" F_f-"L_'Plh" T-)I, IS)t-r'-tfl,
:, ~() ~ '" ;j..f' t = }'1;'-1 ' \ t t"ltJ\) 1
co' L. 1" f Î - _ nt i - 1 J \
H-i1"::/,1 1.[:11::\ ,'c'. 1 (f )-, ;\", Il

-'/ : ' (~I lI;)( =- 1( • T '( Y - T'Y
~::.\) fI~' r
c 'i,
l'
"
1 r .T
1: ,Ir
/1
-1
, .
,
(
Il' l' r "Il,: ",. . , r", i' 1IJ
f ,, IHI_ "I-",P,~',("I I}::',EI' F'):) l:iE LoI::TC.:f'IIÎI,~FIIJrJ ,;;:0 :he- r,I'::'::'; ,=-[l 287
· ~l , r-." L1( ,j ~ ,,.' 1--: 011 ~I/,-).Ir::~, Il ,l!~" Tf,E r'I"J~'(j-El) j'IO(';-_'-. -I.I' ,-t'. 1.loil'J ,j':I;1
f' l '1 , 1 ~ ~ ~ 'J \ _l) 1 \ 1 ~t,.}

' 1
,
~ 1i"'..:t ,{. •• 11 rl 1 • '/"'{-. l'P... .;
0
: 1 :
_01 1
, , ;:' 311 r 1 ! "
,,', L
"
:~Jr,'
J'IF'
f=L
'-r '.' l,) il; l'
~ I,.~ , 1 1 L 1.. 1 l 1 11 r
Il \) l , l. 1 :t"", r J ~ .'''''()l}(){)L : '.) \ f :(t)t.lJul ,
1- t 1 l , - 1 ( TI: :}~;', [ ) ..
f ,:'" l
l j
\'1 'I~ , -,_ r'lf4 (.. (,JU(tU!) 1
J .. ~ '. 1 ::,r',','Et:N
:' l'Œ( OfF :'.L:,
"'), , '.T"It:, ' J ( I . L 711 ' , - ( SSt). 17t)
"," 1 JI'IEI ~d",17""-''::''',:2U)
l',' ,=-'J\-;' l - l F) LtJ·I_HIt::(S"+II<.':,I.,~'l)'-I·"'.,)-rf':,U lr:.. :1,1::.,,1
f" l ,', l F CI P ï -: J h) LL : LIN Et"', u. 1 ; ~ ,- J 1 l ~ -,~.':' ! . , , - l 1 l ~=. 1 • nt, 1
..
L "1) FOI~ [:: i TI] r~
."tJ ".":;1)+(.' ])/I'f"II-, ..<I';.,(,,-, ;
,: l" (: ~ (L-,), l ),' ~r'I,~,\ 1 L ':)1)
_ J':'" I~ 1 : ri)" '1 .;:: ( ;., • ( ) • ~',
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290
PRO GRAM No. 4
TH'IS PROGRA~f DETER.\fINES THE DISPERSION COEFFICIENTS AT

DIFFERENT DEPTH AND PORE VOLUMES USING THE FINITE DIFFERE~CE
/' SWATF IV ,r-.CEXT •

1 I~PLICrl REAL*8 (A.2'
2 CIMEN~ICN ({4,7',OC(3,7J,OCf.3,fOJ,00CIEO,E',CC(180,7)
3 l''TEGER 1 • .,J.1<
4 0)=1 C.OOI6.00
5 CT=30 .00/60 .00
of \/=0.0100
7 CC=190.00'-
E! '( (1 ,1 , :90. co
Ci C(2" '=120.00
10 ( 3 . 1 )~ 130.00
Il
12
=
C (4 ,1 , 1 40 • co
C(1.2'=5B.OC
13 (2.2J=85.CO
14 C(3,2'=lCB.DO
15 ( 4 .. 2 '=124.00
If ( (1 ,3 , =58 • CO
17 C(2.3'=E2.o0
lE! ( (3.3 , =96 • co
ICi C(4,':'=107.00-
~} C(1.4.=52.CO
C(2.4)=58.00
22 ( ( 3 ,4 )= e 8 • CO
23 C(4,4.=c;l8.CO
24 / C(l.~'=5tl.00
l 2S
~6
27
C(2.5'=62.CO
C(:~.S)=e4.00
(4.5'=92.00
2E! (Cl,6.=50.CO
~C; C(2,6,=78.o0
JO (3,6'=84.1:0
31 (4.6'=<;0.CO
~2 DO 1 0 1= 1.4
33 ( 1.7 )=( (1.6' -0 .95CO
"
';4 10 CCNlI IIIUE
35 CO 20 J= 1.7
3l: CC 20 '1=1.3
~7 DC( I ••H=(C (1+ l ,J,-C( I.J •• /60.CO
3€ 20 CCr-.T[r-.UE
~C; OC JO 1=1.3
, .40 CO 30 J=I. fO
41 A=oC{ I.II/CT
4~ 8= '01* ( CO- (C ( 1 • .:, Hec ( 1 . 2 ' . ( J-l , • »
12.00. ex. ( -1 1
43 1 E = CCC ( ( 1,j , + ( C ( ( 1 • 1 »~C J -1 , , I-C 0 ,- CCC ( 1, ~ H ( CC (1 .. 2' • ( J- 1 l ) )-
M(C(loll+(OC(I,I'.(J-l'»)J •• ( - l t - ~
44 F=(OX",ox'/E
45 o (1 • l • J , -= F. ( A .e ,
46 30 C.CNTINUE
( .'"
47 CC 40 1<=2.f
4€
4Ç
OC 40 =
1 1• ~
CC40 J=l.EO
50 AA=oCCI.I<"oT .
el E E= '01* ( ( C ( 1. K- 1 , + ( OC ( l ,K-l f* (J- 1) » , - ( C ( 1 • K H , + (OC ( l , K+ 1 , * ( J-l » ) ) 1
E E -= 8 E.* ( - 1 , / 2 • CO'" 0 x "
..
52
"" EE =( ( (C ( l , 1< ) + (OC ( l , 1< , . ( J- 1 , ) , -- ( ( ( 1 • K - 1 » • (C C ( J • K -1 ) . ( J -1 , 1 1 ) -
II ( ( C ('1 • K + 1 , •• (C C ( l , 1< • l ). ( J- 1 , , , - ( C ( 1. K , • ( CC ( l ,K " • ( J - 1 ) ) , , ) .. (- 1 )
~4 FF=(o>c*ox, IEE
S5 (I<,1,JI=FF>t(""+EE)
et: 40 CCfI,U"UE '
C •
291
c
57 ·cc K=l.E
-.... g
~e
SC; 60
50
.,.r; ITE (6,60)t(
FCRMAT(I/3S)C,'K = , .12/,1//'
.
\.J 60
El
CC 70 1= 1. ~
~ ~ 1 TE (6 .80 )( 0 (le, 1 • J ) • J= 1 .15 )
~PITE(~.eO)(D(K.I.~).J=16,301
62
E3 WJ:; 1 TE' 6 • 80 ) (0 (K , 1 •. .J , • J= 3 1 • 4 5 1
64 "'PITE (6.80) (D( 1<, 1 ... » .J=46 .60)
65 80 FORM A T ( S X. 15 ( F 7.4 , 1 )C. t 1
66 70 CCNTlf\UE
67 50 (CNTI f\UE
(
~ of. .: "'t- l
Ee \/2=0.C1CO \ ... .,,1
6<; (co= 1 S 0.00 ~ 1.
70 (( ( 1 • 1 , =90 • CO ' 1
71 (((1,2'=58.00 \"y
"
72 (C( 1.3 )=56 .00
73 C«1.4'=52.CO.
74 (((1,5'=51.00
7S CC ( l ,6 , -= 4 9 • CO
1E C«1,7)=CC(1.6'*0.9500
77 ~ 1= CT /( ox*OX )
7e A2=OT.V2/(2.00*OX)
7e;
C
CO
'*
100 K= l ,4s
fa cc 100 J-=l .60
a1 CO ( J , 1< »= 0 ( 1< • 1.., J ,
E~ 100 CC~TIf\UE
c
e3 CO 200 K= 1 .f
E4
e~
86 .200
CC 200 J-= 1 .60
oO(J+fQ,K.)=o(I<.2.J.
CON,TINUE
\
C
87 oc 300 1<=I,f
ea CC 300 J-= l ,fO
eq DOeJ+120.1<)=D(I<.3,.J)
<,;0 300 CONTINUE
(
<,; 1 CD 40 C 1 =1 ,7
<,;2 CO400 J=2.18Cl
Cj3 C ( ( J, 1 , =0
<;4 400 CCNTI/l.UE
(
95 CC 500 J=2,180
c; 6 (C ( J • 1 ) =CC ( -J .. 1 ) .. Al. 0 D (J , 1 , • ( « (C - C ( ( J, 1 ) ) -( (.oC (J • 1 J-C C (J , 2 ) ) 1
11-12* «(C (J. 2 I-(CO)
<;7 cc 500 T=2.6
<; e ( ( ( J , 1 '-=CC ( J. 1 1+ Al" DO ( J • 1 1 ... ( (C C ( J - l, 1 - 1 1 - CC ( J -1 , 1 1 1 - ( CC' ( J -1 • l ,-
Nec ( J - 1 .r +1 1 ) ) - A2. ( C C (J- 1, ( • 1 ) - « ( J - l, 1- 1 , ,
sc; SOO CCNTIf\UE
C
100 CC 600 1= l ,6 -
10 l 'ftP ( TE ( 6 .10 0 ) ( ,CC ( 1 • ~ ) ,C C (30 • ( ) , ( C (60. 1'. CC ( <i O. 1 .. Cc ( 1 2n , r ) •
,«(1S0, !t.c(nao. 1)
102 700 FC~MA'(1/5),I2.3X,7(Flp.4,3X)//)
103 600 CCNTIN~E
104 () ST CP
lOS Ef\D
-
292
c PRO GRAM No 5
liWATFIV 4IC'FXT. \
CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCccccccrCCCCCCCCCCCCCCCCCCCr.
C . r.
·c PQOGPAM TO CALCULAT~ C0NCENTqATIO~ AT nrFFEAENT OFPTH C
CA'" 0 ft T 1) l F FER E~J T T 1 M~ ~J f.: ft.. q 1-1 F L L 2. ( C 1\ ) C
C C
CCCCCCCr.CccccccrccccccccccrccccccccccrccccccCCCCCC~CCC ccc
1 l'~PLICIT Rt;AL*~ (I\-H,O-l)
2 [) l r.., E N <; ION C ( 9 Q , 0 ') )
3 PHf:IjER I,J
CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCGCCCCCCC~r.CCCCcc
C C
C ~ ASSIGN '10IH'I)A~Y CONDITlc1N A'\J/) ItIITIAL CONf)ITION C
C r.
cccccr.rcr.ccCCCCccccccr~ccr.CCCCCCr.CCCCCCCCCCCCCCCCCCCr.Ccc
4 00 1.0 1=1,00
5 CC1,f)=?Q"r-n,c,
6 11) Cf)NTINIIF
7 Of) 11 I=?,ln
R C ( 1 , , ) = 1 (1 3D -0 fl
Q . 11 CONTf/JUE
CCCCCCCCCCCCCCCCCCCCr.CCCCCCCCCCCCCCCCCCCCr.r.CCccccccrccr
C _ r
C' AS,)IIj~ CONSTANT VALU!'S <-C
C C
CCCCCCCCCCCCCCCCCccccccrcccrcccCCCCCCCCCccccccrccccccr.c
10 V:2.SD-O~
11 DT=Q()
1? DX=25
13 ~1=DT/DX
14 ~2:DT/DX~D~
15 0=1).t',
cccccrccccccCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCcc
c c
C CALCULATE PI;:T4QDATION FACTOR FOq T~E SURFACE AT C
C DIFFERENT TIM~ C
C C
CCCCCCCCCCCCccccccrcrCCCCCCCCCCCCCCCCCCC€CCCCCCcrccccccc
16 R=l +«1. '510.47>.>31.413)
CCr.ccr.ccrCCCCCCCC(Cr.CCCCCCr.CCCCCCCCCCCCCCCCCCCCCCCCC~CC
à C
C CALCUL~TE CON(CNTRATI0N AT ~IFF~R~NT ~~PTH ANn AT C
C D 1 F FER ~ r~ T T 1 \1:· C
r. , C
CCCCCrCCCCCCCCCCCCCCCCccccccrrcccccCCCCCCCCCCCCCCCCCCCC
17 ' DO i.e; J-=1,O~
13 C(07,J)=r(()6,J)
1° DO =ir. I=1,QS
2 1) C ( l • 1 , J + 1 ) = ( ( COI Il ) ,. '<.? ) ... ( C cr, J ) - ;> ... t: ( 1 + 1 , J ) + C ( T .. 2 , J ) ) )
If - CC (If 1 R ) +1(' /2) + ( C <r + .., , J ) -f ( r , J ) ) )
fi +(CP1,J)
21 S [1 CI) "J T P.J 1) F ~
, 22 40 C0NTINUF
?3 ~qITE(A,1n~l)
24 /)0 sron J=1,??
2S '01 RIT E ( ., , 2 0 r) n ) ( C( 1 , J ) , l " 1 , 0" , 1 ') )
Z 1) 5 a 0 0 C1) N T 1 ~J Uf
27 1 (j nn F 1) P '1 A T ( , 1 ')
2p 2 non F Il R ~1 fi T ( <; X , 1 ( D1 J • ~ , 1 '( ) )
29 STOP
(
'.
-- ,
" 293
,
.
~ 1 o0 '5 ( ,
1 = ? rI') q
L? , n
R ( [ , J ) .,. 1 ~ ( ( 1 • \ •• , Cl • 1. 7 ) ~ ( 1 f') 'i R ~ f-. ? ... n •n 1 ..
/1 ( ;: '( p ( - 1 ~ J 'ï ~ • ') 7 .. 1 2 fJ F - n l, ) ) ) ) ;
fa Cf'lNTINIJF
q CONT {NIJf
01) 10,1 1=1,17
OCr,l)=(l.nnr;
1() 0 r. 1) '" :,,10
00
T 1 ~/" r
[=1~,\~
fl(I,1)=t,.{.14
? nn r. 0NT1IJ l' F
01) 3nn 1=14,/),
I)(J,1)=::?""1
~O(l cnNTINUr
00 400 l=fI"", ~1
"CI,1)=?3."71
4(lO r MIT [ NU 1'"
JOO son I='P,Q? "'
/ I)CI,1)=f).1\9
'5 0 n c 1) t'Il l '1 LI F
cccccccccccccccccccccccccccr.cccccccccccrcccccccccccr.cccr.
c ~
c C .\ t. CUL AT E 0 1 R F 0 ~ 0 r ~ FF. RE N T L AY1: ri A, ND A TOI r FF RS ~I T, r
c' TIME' r.
r. , r
cccccccrccrccccccrccccrcccccccccccccccr.ccccccccccccccrcr
1)0 T(l)=O
1) 1 DO 6 r n ,,= 1 , 14
- 5?
Cj~
54
5S
;6
57
I)O·7nn 1=1,17
T(H1)=T (JH1r
T l Mt:: ( T ( J .. 1 ) , ",~ 'i 1)
r>Cl,J+l) =().O[)"*Exrcn • .779*TIMFl
700 CONTINUE
00 RIlO [=13,:.n
.. 1
5~ D(ld+1 )=6.414*EXP(-O.564*TIME)
59 800 CONTINUF
,60 DO 900 1=34,65
61 D( [,j+l )=2.120 .... EXP(-0.677*TI'10
62 900 CONTINUE
63 DO "3000 [=I,.s,Rl
64 oc l,j+1 )=23.571*EXP(-1.Së6*TlME)
t',5 "'\ 3000 CONTINUJ:
66 DO 4000 I=~2,97
67 o ( 1, i+ 1 ) =0 • 1 3 t"} *,E X P (0.53 * TI MF)
68 4000 CONTINU~ .
69 600 CONTINUE
ccccccccccccccccccccccccccccccccccccccccccccccccccccccC
C C
C CAL CULA T f CON C E NT RAT 1 O_N AT D1FF E REtif 0EPT" AN 0 AT C
C DIFFERENT TIME C
C C
CCC CCC ccc CCC CCC CCC ['C CCC Cr. CCC CCC CCC C( CCr. ccc ccc CCC ccc Ccre
7n 00 4n J=1,14
71 r ( 0 7, J) =r.~ ( Q !, , j )
7? /')o,r;n 1=1,Q5
73 C ( 1 +1, J .. 1 ) :: CC" ( , t 1 , J ). l('). (r ( 1 , 1) - ] . r ( f .. 1 , J \ .. r ( 1" ','J ) ) )
- ( C v, ~ ( 1 .. 1, J) • V.1 ). (C ( 1 . ' , J ) -r ( [ .. 1 , J) ) )
l' HC"",J)
74 C (PI f r ~/I 1 ~
75 r. ,1 t 1 T t ~III r
7,.. I./qITF{.'),1O"r> )
...., ,77" on 5noo J =1, ''l
... 7~
7"1
~o
1\1
~onn
WqITÇ(h,2~0~)(C(I,J),1=1,n~,1")
CO"lTI~tJf
1('100 F0 Q '1ATC'l')
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:~ .? STOD
ln [NO
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SDATA
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c' f' f 1:)I:>OI,I,'1-4fl ni=.: Ti::i" U'I-~ THE ill")l,' H 1(; F Prj~~ T ')-1 ;-c-:= t--l~cr 1r
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1. l 1 J l ( 1 () ,
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1 Il r
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11-1 . :.;',c.:. )( 1
,;;
,., ~, 1 5(' .l( J l Il) ,1 ..lI ,II
'-" j 1 \ ' _1 ( l \ 1r' , 11 rJ, :: 1 J r ,~,- ri' 1I~ JI J 111:. 1_ L l'· r' ·,1'\' , ),
,-' ; ': l! : t t ~ • • t 1_ t 1 ~ • t t 1 1 1 1 • , t 1 1 , 1 1 1 Il' 1 • ; 1 1 ; l '
,- ,llf'
,' \
j : If-
• ,1 J ,
"
.' i' r 11 r lIt· t
( l' .
,=
\,
1 _ ;~
~ t ,
Jo' loi
.
-.1 1 ; Il:=. :J - l ,
T
c. _ .- 1 1 1 ~ r; jl 1
~"
.. t" ~t '1 t:l !t tt "\tt 't i' !!.! t!.!
11 • 1( 1" Il , " , '
., - 1 1 1; liT 1. _ . : t.
.'
Il
295
APPENDIX E
,
THE EFFECT OF THE HIGRATI~ OF ORGANIC
CONTAMINANTS ON THE ,GEOTECHNICAL PROPERTIES
OF DIFFERENT CLAY SOILS
E.I GENERAL
The question of t~ possf1>le detrimental alteration in geote<;hnlcill
properties (i. e bydraulic conductivity, strength. etc) of clnyey soil
,used as a naturai bcrrrier in Iandfills or wilste conta inmC'nl IJolld'i
continually ar ises in the evaluation of such ,fac il i t ies Changl's in tilt'
stability characteristics, which coul<i occur because of the 1IItt>r.lt iOll~,
in the resident pore f~uid c~emistry via changes in tht' overllll 1 (HlI,'
species and concentration, will influence the balance b<>twN'n tilt'
-
elec.trical attractive and repulsive forces, Ilt> weil Il'> t~l!' hondllll'.
established between clay particles and/or sail fabric units
This appendix presents an extension to Chapter l to tovlllullt (> tll!'
eHect of the migration of sorne organic compounds on the • p,('otl'dm!"111
properties of clay sail barriers, such a'S (1) hydrauli; cond\lctivltv.
and (2) shear streT}gth of differe,nt clay soils, Includlnp. nillurlll cillY.
and two reference clay soUs I<nolini te and 1111 tf',
The organic solutions used to permeate thf" Cl~ly 80th wc>rp' huptllfH>.
xylane, aniline. acetic acid. acetone, nllturnl lcachlltl! s<)lutlol1. lUul
distilled water as a control peorTDcant solution ThtHH! p"rml,1ant lIo1utfOllri

'---
weI"! 'selected to coyer a range of diel!!ctr1c constants from 711 ')0 (polar
• water) to l 90 (neutral non polar heplane)
properties of the test permeant solutions are prutmtl'd'ln T4b1 .. (2 ~),
f
•
296
c and schematically grouped in Figure E.1.
discussion Qll each of the following:

This appendix includes a
(1) The effect; of different organic solutions on the change of
hydraulic conductivity of clay soUs', together with the
plausible mechanisms which could be responsible for -this
alteration, and
(2) The effect of leaching organic solutions on the strength and
integri ty of different clay soUs. The changes in cohesion
intercept .!lnd angle of internaI friction were used as indices
__ ~o~valuate the change in soil strength. '
.
(
t!) _ p'
t--~ e.
Organic Leachate Solutions V'
. AFidic Basic Neutral Polar Neutral Nonpo(ar
1 . ,
..
'- Acetic Acid Aniline Acetone
~,
, ,
CH 3 COOH CH3 CHNH COOH CH 3 COCH 3
2
Aliphatic Aromatic
il Heptane Xylene
'-
C H C6 H.. (CH3 )2
'6
"
Flq. Ll. Ora.'l:"llC ~3,~r.L'10' 501~tlOns lised in Tbi..§ Study.

~
.....a
. .
~. J
, ~l ~4".
t
298
c o
E.2 THE VARIATION OF THE HYDRAULIC CONDUCTIVITY OF CLAY SOILS
Hydrau1ic conductivity values for clay soils were plotted against
the cumulative pore volumes of test solutions that passed through the
compacted soil columns. The vertical dashed line on each graph indicates
the point at which distilled water was replaced by the orglJ.nic-~permeant
solutions . Hydraulic conductivity values of kaolinite (Hydrite PX),
ilIite (Domtar Seal Bond), and natural clay are depicted in Figures E.2,
E.3, and E.4, respectively. The normalized hydraulic conductivity
({) V,s. pore volume displacement is a1so illustrated in
Figures E.5, E.6, and E.7, where Ka and K are the initial hydraulic
1
conductivities ana those at any time (pore volume), re~p~~tively.
The hydraulic conductivity of kaolinite clay (Figs. 'E.2 and E.5)
was constant during the passage of 4 pore volumes of distilled water .
.( Nevertheless, there was a s light decrease in the hydraulic conductivity
(less than one order of magnitude) in the kaolini te columns permeated
with low dielectric constant non-polar hydrocarbons (heptane and
xylene), and a notieeable increase in the hydraulie conduetivity in the
case of acetie acid solutio~.
The variation in the hydraulic conductivity values of illite clay
(Figs. E.3 and E.6) was more pronounced than kaolinite clay. Samples
permeated with distil~ed water exh~bited stable hydraulic conductivities
during the passage of 4 pore volumes, however, the hydraulic
.conductivity· value elimbed up ta 2xlO- s m/sec in the illite sample
leached with aeetic acid, in partieular. Polar acetone yielded a gradual
deerease in i11i te hydraulic ebnductivity

.J
~rom 9xlO-
g "" ta
m/see~ Furthermore, the immiscible _ non-polar organic fluids such as
xylene and heptane eaused a decrease in the hydraulic conductivity by
J
\
- ~ -- - ------ - - ~--- - - ----
\
~
299
K AOLI N ITE,
0 l;). ~NILINE
, .
• DISTILLED WATER
'"
ACETIC AC ID
~ XYLENE 0 ACET ONE
• HEPTA~E \.0 LEACHATE

(-
10.7 DfSTllLED
WATER
. Permeant Solutions ~
1
7 , ,
-0
Q)
CI)
5
-...
.....
E
>.
.-...>
4
- .. .
0
2
•
-
~ .$ \-
"'0 10
c:
0
U 7
" • Â Â Â
0
- ~ 5
"0
~
r- .. ,
>- ,. .
J: 3 1
1 •
1
2 1
1
1
~ 1 '\
1
10.9
0 2- 3 ..
Pore. V,alume
F1.q. E.2. Hydrau 11 c coonuctivi ty 0 f Kao 1 in i tp to nif fe n:-n t

Orqanic Solutions,
......
2
300
c ILLITE • 'ANILINE
ACETIC ACIO
• DISTILLED WATER ...
.... XYLENE o ACETONE
• HEP'TAN E o LEACHATE
.,
1
1 ....
DISTILLED 1
7 W A TER ---t~-""III~I------ Perme ant Solut ion s.S~-------IIoI~
1
_ 5 1
1
o
a> 4 .1
(/J 1
-
......
e 3
\ 1
1
1
1
.... 2 1
.-....> 1
1
g 10~~~~~~~~~~~~1r-A~~~~~~-â~-.~~~~~~
'0
c:: 1
o 7 1
() 1
1 \
.-o 5 1
1
1
1
1
1
1
1
1
1 1
1
1
1
1
o 2 4
Pore Volume
"
Fiq. E.3. Hydraulic Conductivity of Illite t Different Orqanic,

Solutions.
(
1
1
1
.- 301
o NATURAL SOIL \
o ANILINE
• DISTllLED WATER T ACETIC A CID ,

XYLENE
, a ACETONE
. 10.7
• HEPTANE LÈACHATE
1
1
1
DISTILLED 1
7 14-- W AT E R~.~I4---- Permeant Soluti,ons
1
1
1
-o )5
1
Q)
1
th 4
..... 1
-...
E
>- 3
1
1
l, .~
t
J'i 10
.8
...... "0,
c: \
- 0
()
.--
t
()
::::1
as
~
""
4
5 1
l '-'
1
1
"'0 \ 1
>- 3 1
::r:
1
2 1
1 o
-' 1
1
1
1
1
1
• t~ ______ _
l '
- 5 ~__----------~___~______~--~--------~--------------
o , 2 3 ..
Pore Volume
,-
Fiq. E.4. Hydraulic Conductivity of Natllral So11 ta OiffN'r.>pt
Orqanic Solutions,
o
--
(
302
KAOLINITE
t:.. ANIL~/'/
. ACETIC ACIO
0 LEACHATE
'" //
Â XYLENE ~' ACETONE "
• HEPTAY
~
\ '1
\
-~
0
2.5
-.-
~
.......
>-
.- ,
(
--
-
.~
'0
0
:::J
c:
~.o
0
1 5
U
.-0
:::J
...'0CO 1.0
>.
J:
.. ,
-
Cl)
.-> 0.5
CO
Cl)
ex:
o
o ~2 3
1 4
Pore Volume', "
Fig. E.5. Relative HydraD:lic CondUctivity cf Kaolinite.
t
, '"
~
,'1 303
-0 ILLtTE
"-
A ANILINE
~
ACETIC ACID
0 LEACt;1ATE
\
XYLENE' 0 ACETONE
'Â
• HEPTANE
-
:
.(
. 2.5
0
~
.....
-.-
~"
-~
..... 20
.-.....:>
(,)
:J
"0 1.5
c:
0 F,
U
............... ~
(,). .---- .....
t' Â A A Â ta 0. t' A .'
1.0
"0
...
CU
0 0 0 0 0 0 0 Q
~
J:
::;;
Q)
:> 0.5
.....
CU
Q)
"f
0
CC
0
0
.. .. Pore Volume
2 3 .
,; "" ~~.
'
'.' " ~;')

-\i-
•
. .
. . '
Fiq. E.6. Relat1ye Hydraulic Conductivity of rl11té.
·r 1
~I
o
•
304
~,
( NATURAl SOll
0 ANILINE
tJ. LEACHATE T ACETIC ACIO

,
1
" , -
.... XYLENE 0 ACETONE
• HEPTANE ,
3.0
.....0 T
~
.....
--
~
>-
2.5
->
()
:::J
"0
2.0
C
"1 0
C,.)
..-
()
1.5
::J
C Cd
~
"C
>- ./
.., /
/
.., "
:z:: //
./
.... ...-
1.0
CD ..
->
1,52
Cl)
0: 0.5
o
o 1 2 3 4
... 1
Pore Volume
Fig. E.7. Relative Conductivit:y of Natura~ Soil. \.

\ .
...
/
- -----~-------------~--
305
o· less than one arder of magnitude during the test peridd.
In the case of the natural (lay soil (Figs. E • 4 and E-. 7,), the 1
permeated samples exhiblted .stable hydraulic conductivities during the
pa~sage of 0.5 pore volume (15 -20 days). By the end of this period,
however. hydraulJc conductivities ehanged ta values above or below the
values given by distilled water. For example. in the case of aeetie
acid, the hydraulic conduetivity underwent a dramaticedecrease. The
aniline -permeated core showed a signifieant inerease in hydraul ie
conduetivity, despite the fac~ that aniline.has a higher viscosity th an
the distilled wster, and this can be attributed ta the nature of aniline
as an organie base.
#
By and large, based on the previous resul ts, i t was not iced that
......... equilibrium hydraulic conductivity value~ of the different clay cores
- were smaller than that of distilled water in most of the cases
usually by one arder of magnitude or less ..

~tudied,
The hydraulic conductivi ty variations are usually explained by
physical variables such as size, shape, and geometrical arrangement of
clay partiel es , whiçh in turn describe the geometrieal configuration of/
the pore sys~em. For exarnple, Terzaghi (1925) emphasized the importance
of the nènuniformity of the voids and the void ratio on the hydraul ie
conduetivity coefficients. Lamb (1932) showed that the coefficient of
hydraulic eonductivity is directly propoi'tional ta the second power of··
the diameter of the pore channel The ge~metry "

of the f10w channel 1.5 a
funClion of the shape aAd orientation of the clay particles. This
partic;e orientation is signif1.cant for particles with à larger d1.ameter
ta thickness ratio. The d1.améter ta thickness ratio 1.ncrease& frOID

•
306
c kaolinite to i11ite to montmoril1onite (Mesri and OIson, 1971).

\
According ta the intrinsic perm'eability equation: '.
(E.1)
lt is clear that the hydrau1ic conductivity of the organic permeant
solution should be dependent on tFe ratio between solution density and
viscosity (Table 2,5) , ~md shou1d have permeated more
rapidly through the clay soil cores than disti11ed water would have.
N~verthe1ess, the absence of an inc,rease in the hydrau1ic conductivity
coefficients wi th low die1ec tric constant perrllea ted so lutions

1
~dicts the previous explanation, and gives rise ta ~he importance

l
of ather mechanisms and 'variab1es that m~ght influence the hydrau1ic
conductivity m~re than the physical properties of the soil matrix do.
"
Cons idering the nature of these organic solutions, and the
mechanisms causing the migration through the clay matrix, it is
therefore more convenient to separate the factors which may contribute
to th~ change in the hydraulic conducti vit y . The four 'important factors
affecting the data presented in Figures E,2 to E.7 are discussed in the
following sections,
E.2.1 The Effect o;f thet Different Forces Acting between the
Clay Particles on the Hydraulic Conductivity
The fiJ,'st factor believed to affect the hydraulic conductivity of

~ 0
the clay coPès is the decrease in the pore fluid cation ;JPlIcentration,
or the overall va1ency, which is caused by the intrusion of the organic

•
-
fluids. This 4ecrease in cation distribution' might advance the thickness
~~
t
(
307
of the clay particle diffuse double layers by increasing the repulsive
forces between tpe particles. This effect might cause a tendency towards
dispersion,and a decrease in hJdraulic conductivity. On the other hand,
an. increase in cation concentrations or valency might cause

1 •
flocculation, shrinkage, and/or fissuring, .
In arder to investigate the vali,dity of the above-mentioned
hypotheses, ,the chemical analysis of, the pore fluid extracted' from the
~
/-
leached clay cores, as weIl as the,anarysis of the retained ions on the
solid phase, were conducted to de termine the change in the different
soluble and exchangeable ion. dis tribut ions. Typical results of the
'chemical analyses for the various cases studied are summarlzed in Table
(E.l). Typical examples are given in Figures E.8 a and b.
The results showed a dramatic change in tlae distribution of the

-~
various soluble and exchangeable ions within the pore fluid anr on the
clay ~urfaces (adsorbed ions). In the cas.e of natural sail, the

,
concentration of the soluble afid exchangeable cations decreased by 45% J
1-
compared to the ini tial concentra tian (before leaching) This result
can be attributed to the organic molecules displacement of the resident
ions, which 'eventually can cause a disturbance in the diffuse ion
balance (ions in the pore f1u!ds) This effec t may be respons ib le for
changing the clay structure within the cores
The elution of the resLdent cations, and the pro~ounced increase in
their concentration in the periodically collected effluent santples was

•
J '-
another indication of the sarne phenomena
-.>
In the case of il l i te clay. however 1 the distribution of the
cations substantially differs from that of the natural clay. In the pore
"",
~
""\
..
..
li> 308 ~
(
G
Natural Soil
0
' -
..
-
.0-
CI)
5 Soluble Ca tions
0)
4
·0
0
'f"'"
...... 3 'L
C'
C>
2
~E
c
-...
0
r
-C
~
Cl)
()
c'
O·
,
Na. K Ca Mg
0
Ü
..
(~
0
CI)
0)
50
Exchangeable Cations
'-
•
0
After Leach~ng
aefore Leaching
40
0
,...
0
...... 30
-C'
Cl)
"e 20
c:
--...
.-
0
C't1
c:
Q)
10
0
t: Na K Ca Mg
0
C,)
~'I,
Fiq. E.8a. Distribution of Cations before and after LeachiFlq

Natural Clay with Heptane. .
(
309
Illite \
20
Soluble Cations
10
-.-
0
CI)
Cl
0
-0
0 Mg
,- Na K Ca
......
0-
C,)
E 30
c:
0 Exchangeable Cations
.....
C'i3
.....
L..
20
c:
....
1;,
C,)
()
• After Leaching
c:
a \
()
10 o Before Leaching
-Na K Ca Mg
\
F.:.q. E.8b. nistrihution of Catio!îs bf·forr. ;11\r! afh'r ~'ll(;hlnq IlIH,'
Soil wi th Hr>ot...'1!1P.
- 1
\
310
( fluid, the trend was an increase ~n K and Mg ions, and the concurrent
decrease in Na ions. On the other hand, the concentrations of the
eX<7hangeable cations Na, K, and Mg decreased, and only Ca ions

fi..
significantly increased, i.e. the charge balance was maintained,by the
migration of Ca ions from the liquid to the solid phase. These resulcs
suggest the ability of the intruding organic solutions to eliminate the
monovalent cations and, less successfully, the divalent cations from
the solid phase. One can attribute these results also to the great
replacing power of Ca over the other cations (Yong, 1985). lt is
pertinent to note that the anion concentrations, especially Cl and
,HC0 3 , .increased substantially in the intermediate cl~ soil cores
(Table E.I). furthermore, C0 3 ions were below detectable limits
Kaolinite clay permeated with different organic solutions showed no
sign{ficant change in the cation distributions already present in the
pore fluid in a '~~ concentration. For example, in the case of a
kaolinite clay ~olumn leached with heptane, Ca ions were the only
detectable exchangeable cations. lt is important to note that the
Georgia kaolinite is water-processed commercial soil, to reduce soluble

r/
salt contents to e~remely low levels.
The pH values did not show any significant changes, especially in
the cases of natural and illite clay. The pH villues ,wete in the range of
6.5 to 8.0. This observation highlights the buffering capability of t~e
natural and illite clay soils, and the fact that there was no
contribution of pH to the hydraulic conductivity behaviour observed in
the course of this study; or, i~ other words, the pH effect was minimal .
.IIJ
( Cl Therefore, the only two factors which can affect tha repulsive
f-
t,,~} "" •
't
Ir"- ..
~ ....,::! f
...
'\
• Note: each value recorded ln thlS table 15 an average value a10ng the sail co1umn
.r---
/.
W
,. ....
r-
-,
" TABLE E.1a Cont'd
fi":
.
Water Soluble and Exchangeab1e Ions for 50;15 Leached
~,
With Difference Organic Solutions (After the Passage of

Three Pore Volumes}
2. Il 1ite +
Exchangeable Cations
Le. Water Soluble Ions meq/100 9 S011 (meq/lOO ..9) ESp·
!l mho/
1
. C~q/ SAR TOC
?ample pH + Ca 2+ Ml+ HCO; CO;2 Cl- 0.5
cm Na K+ Na+ K+ Ca+ Mg 2+ 100 9 % (meq/I) mg/l
Distilled "
7.8 21. 78 1. 74 0.64 0.12 0.45 0.60 0.0 2.0 1. 55 2.26 30.38 1.36 56 2.76 0.55 80
Water
,
tleptane 7.9 14.74 1.04 0.13 0.55 0.06 1. 36 0.0 2.16 0.55 1.44 24.69.0.85 48 1.15 2.05 171
Xylene 7.8 16.67 1.26 1. 53 0.29 0.05 1. 65 0.0 1.17 0.68 0.06 22.00 0.86 47. 1.44 7.27 133
An il i ne 7.8 41.61 3.26 0.50 0.30 0.05 1.60 0.0 2.10 1.60 1.09 22.10 0.91 55 2.90 0.66 450
Acetic
Acid 6.1 56.32 3.47 2.05' 0.40 0.15 1.80 0.0 1.15 1.85 1. 58 18.20 0.99 54 3.41 0.84 410
"-
Acetone 7.8 22.98 1. 54 0.72 0.38 0.10 1. 53 0.0 1.75 0.73 1.33 18.10 0.71 55 1.35 8.73 110
~
"'-- Leachate 8.6, 44.34 2.87 0.85 0.28 0.61 0.96 0.0 2.15 2.05 1.64 32.70 0.52 60 3.49 13.60 100
13
)1' W
1-'
~
o
'-
e ! o
TABLE E.la Cont d 1 Water Soluble and Exchangeable Ions for Soi15 Leached
'" With Difference Organic Solutions (After the -Passage of
Three Pore Volumes)

3. Kaolio~te
Exchangeable Catlons
Le. _Water Soluble Ions ~eq/lOO 9 Soil (meq/lOO g)
CEC ESP SAR TOC
~Imho/
Sample pH + 2+ rœq/ 0.5
cm Na K+ Ca 2+ Ml+ HCO; CO;2 Cl- N/ K+ C/ Mg 100 g % (meq/I) mg/l
Dlstilled 6.7 23.33 0;56 0.19 0.25 0.52 0.60 0.0 0.0 0.99 0.22 3.58 0.130 12 8.25 1.02 40
Water
Heptane 4.3 3.83 0.32 0.071 0.48 0.089 0.41 0.0 0.55 0.0 0.0 0.220 0.0 - 14 0.0 0.0 111
Xylene 4.3 3.28 0.19 0.076 0.36 0.078 0.56 0.0 2.5 0.00 0.01 0.17 0.0 16 0.00 3.76 86
Aniline 6.9 17 .69 0.66 0.04 0.44 0.06 0.50 0.0 0.50 0.50 0.20 3.80 0.120 12 4.13 5.05 150
AceUc 3.8 7.65 0.95 0.07 0.53 0.70 0.58 0.0 0.0 0.10 0.0 0.70 0.20 12 0.83 0.21 380
Acid
Acetone 5.0 13.49 0.365 0.055 0.178 0.047,.9.18 0.0 0.0 0.84 0.25 1. 33 0.25 17 5.10 2.93 60
Leachat"E 6.8 27.42 0.94 0.22 ,0.26 0.54 0.95 O.C 2.08 2.3 0.29 2.12 0.130 15 2.17 4.52 63
"" \>0.
-",\,J
'Il
w
.....
w
~
--------------------------..............
~ ~ ~
(Natural SOlI + Heptane)

Sarrple pH E.C. Water Soluble Ions rœq/100 9 soil Exchangeable Cations CEC ESP SAR '!OC
I-l mho/ (t.req / lO Qg) 2+ meql (meq/ rrg/l
an Na+ K+ ca2 + Mg2 + HC03 co- 2 Cl
- Na+ K Ca' Mg 100g %
3 1) 0':5 -
NIl 7.2 35.9 2.96 1.28 0.85 0.26 2.75 0.0 2.50 2.43 0.7 6.65 3.32 _ 46 14.4 3.97 150
N
12
7.5 34.3 2.78 0.89- 0.5 0.23 3.29 0.0 3.50 3.13 1.07 19.5 4.10 46 18.0 4.60 125
N 7.9 29.7 2.44 0.74 0.75 0.18 2.00 0.0 3.0 3.38 1.16 16.75 3.48 46 20.1 3.57 130
l3
N 7.7 36.3 2.91 0.35 0.37 0.11 2.63 0.0 2.0 2.55 1. 45 17.23 4.22 42 19.0 5.94 150
N{5
14
7.9 34.3 2.48 0.33 0.26 0.11
•
2.27 0.0 1.95 3.43 1.63 27.24 3.97 42 21.0 5.76 135
~ ,
N 7.7 33.8 3.30 0.64 0.40 0.15 3.00 0.0 2.0 2.79 1.26 17 .10 3.55 46 17.0 6.29 130
15 ,-
--~----- - - ~
(Ill1te + Heptane)
III 7.9 15.17 0.87 0.13 0.21 0.066 1.50 0.0 2.0 0.69 1.55 24.69 0.76 49 1.30 2.0 200
1 7.9 15.56 1.04 0.13 0.38 0.066 1.30 0.0 2.70 0.41 1.42 20.61 0.93 49 0.8~20 140
12
"-
lU 7.9 13 .90 0.95 0.13 1.25 0.062 1. 70 0.0 2.40 0.54 ,1.37 24.75 0.81 50 1.08 1.17 230
'1
I 7.9 14.70 1.08 0.13 Ô.20 0.047 1".50 0.0 4.40 0.47 1.47 25.30 0.91 50 0.94 3.07 140
14
'7.9 14.70 1.13 0.15 0.88 0.056 1.20 0.0 1.0 0.61 1.44 26.11 0.89 55 1.09 1.65 140
115
I 7.8 14.40 0.95 0.13 0.30 0.066 1.0 0.0 0.50 0.61 -1.43 26.70 0.8 36 1.69 2.22 180
16
/
TABLE E.lb Water Soluble and Exchangeable Ions for Sail Leached with Heptane After the
Passage of 3 Pore Volumes 0
w
......
"'"
o . ""~
t .- f
o
CKaolinite + Heptane)
SaIJtlle pH E.C. \later Soluble Ions meq/lOO g sm.l Exchangeable Cations CEC ESP SAR 'Iœ
mho/ (~q/lO~)
~
,Il
an Na
+ K+ ci+ Ml+ HC0 3 CO'-2
3
Cl
- Na+ K Ca Mg
2+ neq/
100g %
(meq/ rrg/I
1)°·5
5.1 3.20 0.208 0.051 0.325 0.104 0.49 0.0 1.50 0.0 0.0 0.225 0.0 16 0.0 0.45 120
• KU -
K 4.4 3.60 0.24 0.051 0.537 0.068 0.60 0.0 0.20 0.0 0.0 0.225 0.0 8 0.0 0.43 120
12
KU 4.3 4.20 0.24 0.089 0.273 0.183 0.60 0.0 0.30 0.0 0.0 0.195 0.0 8 0.0 0.50 120
1<14 4.3 4.10 0.65 0.089 1.25 0.072 0.29 0.0 0.,30 0.0 0.0 0.195 0.0 15 0.0 0.80 140
K15 4.2 4.00 0.13 0.097 0.250 0.0-75 0.2 0.0 0.50 0.0 0.0 0.13 0.0 20 0.0 0.28 100
K 4.3 3.90 0.22 0.051 0.150 0.037 0.4 0.0 0.50 0.0 0.039 0.35 0.029 16 0.0 0.72 70
16
..
5 TABLE E.lb Cont'd
Cc
....
IN
lJ1
5 ,
.,
316
forces in these cases are: a; (1) the decrease in the ion concentrations in
\
th~ pore fluid, and (2) the decrease in the dielectric constant, caused
by the permeation of organic fluids through the clay soil columns. An

attempt was made to calculate the repulsion energy between clay
particles before and after the leaching processes, based on the
equations and assumptions of the double layer theory, and taking into
account the changes in both the dielec tric cons tant and. ion
distribution. The results of the repulsion energy are summarized i~
Table E,2. The calculated repulsion energies were not surprising; they
showed a significant increase after the leaching of three pore volumes
of the organic solutions, in spite of the simplified assumptions
èonsidered in the ealculations of the ion concentrations and valency.
To further support these results; and their effect on the hydraulic
l ••
condue ti vi ty behaviour, another two variables were examined: (1)
dispersibility, and (2) the zeta potential, which can be related to the
net energy of interaction between clay particles and/or fabric units.
The relationship between the dispersibility of elay and both
soluble and exchangeable cations was investigated, using the method
suggested by Sherard et al. (1976) by calcu1ating both SAR (sodium
adsorption ratio) and ESP (exchangeable sodium percentage) (Table E .1) ."
The results generally indicated the existence of nondispersive clay,
whieh was confirmed by the zeta potential measurements using the
clasc;ification technique given by Yong and Sethi (1977). The zeta
potftials wt::rp in the average of -22 mV for the three types_ of clay
soi scons idereâ in this study, except for a few cases due to the
int rference of the nonpolar organic molecules (which in turn can

(
317
TABLE E. 2 Values of VR Cêtlculated after Leaching

of Three Pore VO+urTeS
LeaShing Solution V J/m 2

R
Kaolinite Illite N. Clay
5 9 9
D. Water O.24xlO 6.75xlO 1l.34xlO
5 9 9
Heptane 1l.26xl0 3.80xlO 5.68xl0
5 9
Xylene 18.5xlO 5.94~9 4 6.44xl0
5 \, 9
~ . Aniline 14.84xl0 4.05x'109 6.31xlO
5 9 9
Acetic Acid \ O.68xl0 O.69xl0 4.6xl0
9 • 9
Acetone .1 14.58xl0 S 2.4xl0 4.98xl0
• 9 9
Leachate Solution O.58xl0 S 43.5xl0 4.6xlO
o
.:
!.
318
( explain the observed low zeta potential result~). Nevertheless, these
results indicated a slight to moderate dispersion, in the case of
heptane, xylene, acetone, and 1eachate.so1ution, due to the desorption
of different ions from clay particles surfaces. The results of the zeta
potential are summa~E.3.
E.2.2 The Effect of the Organic Solutions Intrusion on the
Hydraulic Conductivity Behavior
The second factor considered. to affect the hydraulic conductivity
is related to the change in the size of the individual clay particles,
due t;o the intrus ion of organic per!llea~sol~ions (non-kaolinite
clay). The factors which might contribute to~effect are: (1) the
decrease in ~lectrolyte concentration and valency, and (2) the increase
in the dielectric constant, size of hydrated ion" pH, and anion

( adsorption. If the interlayer spacing decreases, an additional pore
space will become available for the clay particles to 'reorient
themselves, abiowing for flocculation. , This reorientation of clay
particles may result in a decreasing void ratio, but more significant~y
,. can pr:oduce a pore size distribution with a larger average pore, which
may lead to an increase in the hydraulic conductivity of the soil mass.
~To examine this hypothesis twb variables were controlled(~~ring the
leaching process: (1) water content, and (2) surface area. Th1? average
water content of the clay co~s showed no significant changes after the
passage of three pore volumes of the above-mentioned organiç fluids,

-......
except in the cases' of acetic acid and aniline (Table E. 4).
Nevertheless, in the ~pper sect~on of the clay column (Section 1 and 2),
the water content sli.ghtly increased, probably due to the direct

(
.J
319
TABLE E.3 Zeta Potential in mV for Different Soils Leached

f , - - ~
•
With.Organic Solutions
Permeant Kaolinite Il lite Natura 1, Sail

Fluid
\
Di st; 11 ed
Water -17 .10 . -23.0 -17.10
Heptane -24.0 -21. 50 0.0
,>
Xylene -17.20 . -15.5 -24.0
Ani 1ine 0.0 -26.5 -26.0
Acetic Acid +40.0 -27.0 -12.50
Acetone
, -16.0 -20.8 -25.50
Leachate -23.50 -18.5 -20.0
(J.
/
o·
,
1
\
320
contac:t with the leaching solution on the leachate reservoir (Fig.
2.5), and the relatively high hydraulic gradient employed in the
laboratory experiments.
'Al though there might be some Interference in the surface area
detetmination employed (EGME, Chapter 2), nevertheless, there was a

\
)
, noticeable decrease of 15% (on the, average) in the surface area, i~
the case of natural clay permeated with xylene, heptane, and acetone.
Illitic clay showed a 1esser degree of change, only 8% (on the
average); and no significant changes in the case of kaolinitic clay solI
were observed. The surface area changes mostly on the upper portion of
the clay columns (Table E.4). Me anwh i le , the middle and lower parts of
the soil co1umns showed si,nificantl Y less changes in surface area.
These results can be attributed to the high hydraulic head applied on
c the top layer of the clay cores (equivalent to 2.50 m of water), which
reight c reate macro pores and/or a hydraulic frac ture, which
consequently would increase the hydraulic conductivity, especia1ly in
the upper layer of the clay matrix. These results had already been
investigated by the use of a careful set of experiments, in which the
pore pressure was measured along the clay core during leaching (using a
large leaching ce1l) (Lex, 1986). The pore pressure distribution showed
insignificant éhange in the first layer and chen dropped linearly
following a Darcian behaviour (Fig. E.9). Theie results indicated the
presence of an extremely high hydraulic conductivi ty on the upper

1
portion of the cell as compared to the rest of the clay soil matrix.
Another factor which was believed to affect the hydraulic
cO,nductivity of the compacte,d clay soil was the mo1ecular weight of the
( organic compounds used in the permeation of the clay soil columns. The
, 321
o TA~LE E.4 , Wat~r

Content and Surface Area Results
for Sorne of the Cases Studied
Perrneated Kaolinite I1lite '-- Natural Clay

Fluid Water Surface Water Surface Water ' SU'rf ace
Content Area Content Area Content Area
.... 2
% rn /g' % rn 2/g % m?/g
D. Water 33 . ~ 12 17 29 33 60
38 8 23 18 37 66
Xylene 39 " 9 22 21 34 <5

Acetone 35 10 19 19 35 66
o •
u'
322
(
•
Pore Pressure (kPa)
o 5 -.., 10 15 20
0.0 25
010
0.20
030 ..
-
--
0
E
(~. ~
Cl.
0.40
..
J
Q)
0
050
"
0.60
.
0.70
1
,}
Fiq. E.9. Pore pr~ssure Dis~~ption alona the Clay Soil

(Landfill Model).
. ,
( 1
"
•
•
323
mol,ecular weight was substantially Increased from 18 for polar water to
100 and 106 for t'lon-polar heptane and xylene, respectlvely (Table 2 .5).
Figure E.I0 displays the relationship between the hydraulic conductJvity

and molecular weight of the permeant organic solutions. This
.....
observation was to sorne extent consistent iri aIl three types of soils
examined. lt was observed that hydraulic conductivity slightly
decreased with increasing mo1ecu1ar weight unti1 the range 9f moleeular
weight of about 90. This was followed by a sharp deerease in hydraulic
eonductivity as the molecu1ar weight increased ta 100 or greater
E.2.3 The Effect of Organic Adsorpt ion on the Hydraul le
Conductivity
The third factor c(l)nside~ed to affect the hydraulic eonduètivity

..
.,. . ( was tbe adsorption of organie molecules on the clay surfaces. Organic
'\,olecules, whieh are weak1y adsorbed by soil partie1es, tend to move
quiek1y through the pore channe1s However, hydrophobie substanee~j sueh
as heptane, xylene, and aniline, that are highly partioned at any
instant into the soi1 phase and liquid pha~e, will be expeeted to have
hYd~lie conduétivity values mueh 10wer than ~hose of acetone (Gre~n et
al., 1981) Both non-polar and non-Ionie organie compounds have
extre~;low so\ubility -in water and this generally limits the
possibility of an appreciable migration of large quantities
Organie cations or anions may be adsorbed on negative clay surfaces

<
,- and positive edges ManYoorganie eompounds with a dipole character are
adsorbed on clay surfaces, analogous to the behaviour of water. The
adsorption energy of many of these compounds mus t be of a magnitude
comparable with that of water to cause adsorbed water displacement (Van'

.
.,
324
,
C' TABLE E.5 Direct Shear Test Results for Different
Permeant Fluids
Kaollnlte III ite Natura1 S011

Permeant
Fluid c c
C {Il III 0
(kPa) (deg) ( kPa) (deg) (kPa) ( deg)
Dl st 111 ed
Water 12 20 4 - 24 22 18
Heptane 22 20 5 7 32 10
,0
Xy1ene 7 26 7 9 17 7
..J
Anlllne "3 28 8 40 19 26
Acetlç Acid Il '23 19 24 18 27
(. Acetone
-
12 23 23 37 28 3
Leachate 12 19 15 - 21 17 8
,;
"
')
325
-....
,; ....
- ()
10.7
)
Q)
UJ
......
- E
10. 8
.. •
Kaolfnlte
~
~
10. 9
0 20 40 60 80 100 120
Molecular Wt (GMW)
"'" 10 ·7
- ()
Q)
lIIite
UJ
...... /
- E 10. 8
10.9 t : •
~•
..... J
0 20 40 60 80 100 120
Molecular Wt (GMW)
10.7 • Natural Soli
4
-u.
Q)
UJ
-
...... 10. 8
E
~
"
10. 9
0 20 40 60 80 100 120
MOlecu;lr Wt (GMW)
•
Fiq. E.10. The Effect of Mo10cular Wt>iqht on t.h(! Hyrlraulic C:ondllî.'ti vity.
) 326
( 01phen, 1977).
When expanding 1c1ay is treated with polar organic compounds, such
as alcohols, glycols or amines. the organic molecules May penetrate
between the unit 1ayers and disp1ace inter1ayer water (Van Olphen,
1977). The driving force for sorption is apparently an increase in

,
entropy coming from the displacement of a single large organic molecule
on a Surface, which releases a number of water molecules bound on the
surface, increasing the overall randomness (Schwarzenbench and Westall,
1981).
The total organic carbon (TOC) of the extracted pore flui~ at
different sections along the leached clay cores with low dielectric
,
constant organic solutions (heptane and xylene,) showed insignificant
l accumulation of TOC on the pore fluid.
organics were retained on the pore fluid,

Only 4 to 10% of the permeant
in the case of natural and
illite clay. However, in the case of kaolinite , the percentage dropped
to a value between 1 to 2% Furthermore, Fernandez and Quigley (1984)
using Leda clay found that only 6% by weight of the pore fluid consisted
of benzene, the rest being water. The results agreed fairly weIl with
the findings from the present study, for both heptane and xylene. These
can be attributed to the hydrophobie

,
nature of the low dielectric
constant solutions, and their ability to be partioned between the liquid
and solid phase.

"
In the case of natura1 soil, and illitic clay pe4:-meated with
acetone, the TOC percentages were in the range of 10-12% of the value in
the leaching solution. In pore fluid extracted from kaolinite, the TOC
( values correspdhding to acetone were on1y 5%. Acetone can displace

327
adsorbed water from clay surfaces, due to its higher dlpole moment but
it cannot form multiadsorbed 1ayers as water does, beca~se of'its higher
molecular weight (Anderson, 1981). Furthermore, aeetone ean inerease the
interlayer spacing between adj aeent clay partieles, as eomp~ with
water.
An attempt was made in the present investiga~ion to measure the
ad~orbed organies, i. e the organic content associated wi th the solid
phase. The thermal gravemetric analysis (TGA) was employed This tE'!.t
was accomplished by a combustion procedure, in which organic matter was
",converted ta carbon dioxide and wa ter, whi le the temperature wa!.
contro11ed to prevent decomposition and vo1atilization of inorganic
substances The sail samples were heated up ,to 600 oC, which i8
.
be1ieved to be the lowest temperature at which organic matter 'can hl'
oxidized at a reasonable speed. Also, at 600 oC, decomposition of
inorganic salts is minimized (Sawyer and McCarty, 1978) Figures E Il a
and b disp1ay a typica1 loss of weight-temperature re1atlonship TIl(>
loss of weight was in the arder of 3 to 5% (on the average), which

.indicated the amount of organic carbon associated with the solid phase
(EPA, 1983) It i5 pertinent to note} that this observation i5
qualitative rather than quantitative, and this is beclluse of tilt'
possibility of losing sorne of the adsorbed water layers dU' ta the
elevation of the temperature.

/
328
100.5
a
1~.0 JLLITE + HEPTANE
.,
99.5
99.0
"
'"
H ~
.,
oJ
98.5
-a,
...
fi
:.
98.0
97.5
97.0
"
96.5
a 100 200 300 400 500 600 700
l TempQratura (OC)
100.5
b
100.0
99.5
JLLITE + LEACHATE
99.0
,..
H 98.5
v
.,
1:.
....m- 98.0
IJ
:.
97.5
1-
97.0
,
98.S
96.0
a 100 200 300 400 500 600 700
TempQraturQ C·C)
Fiq. E.ll. Typical Temperature - Loss of Weiqht Relationshios.
.-J\
329
E.2.4 The Effect' of the D1electr1c Conatant on th. Hydrau11c

"
G· Conduct1vity
In general, organic fluids consist of miscible and imm1s1cble
chemicals which have 8 wide range of dielectric constant values. In the
case of f~l~y miscible chemicals, equation (E 2) (Gouy-Chapman theoty):
(E 2)
Indi,cates that a decrea,se ~n the dielectr1c constant «() of the port'
fluid results in a decrease in the thickness of the diffuse double lnvrl
(H), which eventually leads to an increase in thp at tract1v(' forcf\<; nnd
to flocculation, as weIl as an'increase Jn hvdraul{c conductivity (T l~
the absolute temperature, no 15 the number of ions, and v 15 ttH'
valency )
The resul ts of a recent study by Acar et al (19Bt.) conf i nnNI thb
conclusion, while the study of Green et al (198]) contrlldicl.(·d th~
above-ment1oned trend There was a relat10nshlp bptwef'Tl th .. hvdl/lul1t
conductivity of the clay 5011 and the organic fluid dif']('ctric COfl!.!.1Il!,
su ch that the greater the dielectric constant, tht' ~rp8t('r Wf'n' tlu'
values of hydraulic conductivity coefficients A suh .. tlmc(· with Il hlp,h
dielectric constant. such as water, tends to b(· hydrophl1Il and '(,lITl
therefore be expected to move morl' quiçkly thlough th(' port' chann .. l!. ..
in the clay cores Low dielE'ctric substl1nc('<, 8urh Il'' XVlPTH'. h .. ptllflr
have the tendency to be adsorbt'd. and thu!. Il rl'tllrdcd mov~m('pt
Figure E 12 illustrates thl' relationship b .. tw(,l'Tl th" equJ I1brhm
hydraulic conductivity (k valu .. after 3 poa volumes p ... m"ar ion) of"
kaolinit.-, 1111te, and natural soil and th .. dlel .. nrit" conatant. fot th ..
different permeant solutions vh1ch vert' uled in thh study

330
Kaolinite
10. 7
C - ()
Q)
•
-"E
en
10. 8 .y
•
~
10. 9
0 20 40 60 80
. 0
Dielectric Constant (at 20 C)
10. 7 Illite
- ()
. .....en
Q)
10. 8
-~
E
10· Q
0 20 40 60 80
Dieleétric Constant (at 20°c)
,....
0
10-7 Natural Soil
,
(l)
(/)
.....
40. 8 , -
1
-E
::s:::
10. 9 •
0 20 .• 40 60 80
Dielectric Constant (at 2'OOC)
, Fig. E.12. The Effect of Dielectric Constant on the Hydraulic

Conductivity of Different Soils.
, '
3~n
•trend was towards ~slight decrease in the hydraulic conductivity wieh
decreasing the diele~ric constant. This trend was followed by a sharp
decrease in hydraulic conductivity at the range of dielectric between 2
and 7. Nonetheless, these resules did not ·follow the straight line
relationship previously presented by Green et al. (1981) This can
indicate that the change in the dielectric constant is not the· sole
fac~or affecting the hydraulic conductivity of the different clay soi1s,
but that there is also the change in valency, ion concentration, and
the other .fac tors discussed in the previous sections.
E.2.5 Summary
Hydraulic conductivity values are the primary criterion for
evaluating the suitability of clay soUs for lining landfill sites.
Neverthe1ess, the present study revealed t\at the hydrau1ic conductivity
....... values of clay soil cou1d be significantly affected by the interaction
with the intruding organic fluids. The re sul ts indicated a s light
decrease and/or in sorne cases increase of less than one order of
magnitude. Clay soils permeated with low dielectric constant non-polar
organics, such as xylene, heptane, and aniline, showed a decrease in
hydraulic conductivi ty . Furthermore, kaolinite and illite clay l~ached
with acetic acid and acetone u~derwent an increase in hYd)aUlic
conductivi ty t and only in the case of.a natura1 clay sail leached with
acetic acid did hydraulic cQnductivity decrease dramatically
The hydrau1ic gradient used in the present study was in the range
.
of 25, which may have influenced the obtained resul ts, and lncreased
the ·possibility of the hydraulic fracture, fine partic1es migration
and/or the shear of water layer around the clay particlss.

l'
.
332
o
E.3 CHANGE IN THE STRENG~H OF CLAY S01LS PERHEA~ED W1TH
ORGANIC FLU1DS
E.3.1 General
- ,~/
Change in shear strength of clay soils used as a barrier in waste

j"1,-
containment ponds and/or landfills i5 a factor, that must be considered

t
in the design of the clay barrier system. The consolidation of the solid
\ )
waste or evaporation of the liquid waste during à storage per~od can
result in ~n uncovering of the slopes, relief of lateral pressure, and
'possibly uns table conditions caused by the change in shear strength
characteristics due to the intrusion of leachate solution. In the
following subsection, the change ;f t~ ,trength due ta permeation of
organic fluids is discussed.
E.3.2 Shear Strength Resu~ts
c The results obtained fram the direct shear test -fo~ the nadu{al
clay soil are shown in Figure E .13. They illustrate the relationship
~
between the applied normal pressure and the ultimate shear strength, and
both are given in kPa, each line r~ferring to a particular pore fluid.
Similar results were abtained for illite and kaolinite soils.
Two regions were clearly distinguishable: regian (A), which

"
includ~d non-polar low dielectric co~stant organic fluids (heptane and
xylene), acetone, and leachate solution. This regian was characterized
by a law strength and low cahes ion intercept; while region (B), which
included aniline and a<?etic acid, as weIl as distilled water, was
characterized by an increase in the angle of internal friction (~), and
the high'strength. The values of the cohesion intercept and angle of

;'
----
\ internal friction (~) for the three types of so11s have -been tabulated
-'
\ ~
in Table (E.5). (
..
333
o
NATURAl SOll
120
• DISTllLED WATER
Â XYLENE'
_
~
100
• HEPTANE
0..
A'N Il:.J NE
-:r:
~ A
80 ... ArC E TIC A CID

t-
e!' a ACETONE
Z
.---
w
Cl: 60 0 LEACHATE
•
.
' t-
(JJ
~
tJ:.
_.
0
Cl:
« 40
'
w
:r:
(JJ
:.------- - .".,. ,
... ~
---:= ~
,~~
___ -~?~ 0 ~ ~_-:..-----
..,.,. .".,. _~~/
."." -"" _ 0-- ________ Â
-_..- - -
- ---
20 ~
~
~~ ~
- ~... ,
-..;-~----
00
00 20' 40 60 80 100 120 140
NORMAL PRESSURE (KPa)
F;,q. E.l3. Shear Strenqt1l - Normal Pressure Relationshfp for

Natural 5011.
o
334
.
~ The lower shear strength observed in region (A) (heptane and
xylene). w~s attributed te, the deerease in repul~ion forces. The
reduetion was in the range ot 4.6 to 6.4 X 10 9 J 1m2 , as

~ "
calculated from th~ double layer theory (compared to the value given by
distilled water) (Table E. 2). These results are probably due t~he
decrease in the dielectric constant of the permeant solution, as well as
by the associated changes in pore fluid ion concentration, caused by
the desorption of different cations (Table E.l). Ion desorption occurred
due ta the hydrophobie behaviour of the nonpo lar org~nies, and i ts
tendeney to be divided at any instant into the soil phase and the pore
fluid phase. According to Yong et al. (1985), these decreases in the

~
interparticle repulsion forces allow easier particle readjustment, and
result in a deereq,se of shear strength. Furthermore, this behaviour in
( region (A) can be attributed to the formation of brittle bonds due to

o
precipitation of a limited amount ot organie compounds. In the case of
iUite leached with xylet;e and heptâ.ne, the organic content measûred in
the resident pore fluid as TOC increased by an average value of 150 and~~
120 mg TOC/IOO g soil, respectively. This hypothesis was also supported
by the sharp slope of the stress-strain curves obtained from the direct
shear test.
As mentioned previously region (B) was mostly el1,aracterized by

)
the substantial increase in the shear strength and 'the angle of internaI
friction. "'
The increase in the angle of internaI friction indicated the
presence of highly cemented soil (Lambe, 1960; Arulanandan îmd Smith,
1973; Arulanandan et al., 1973). The increase in shear streng-th was
probably caused by the following two meehanisms:
c (1) The slight deerease in the water content, assoéiated with

335
leaching the different types of soi1s with aniline and ace tic
~
< acid. The average change in water content beforè and after the
lea~hing process (passage of 3 pore volumes) ~as 3 to 4%. As
more organic fluid permeated through the soil cores, more

()
wa:ter layers were removed from clay surfaces; and
(2) The precipitation of bondiIJS materia1s. The TOC content greatl,y
increased in the case of illite soil 1eached wi th anil ine and
acetic acid. This increase was in the order of 300 mg TOC/IOO g
soil. These organic materials can cause the forma tian of
cemen~ing bonds and reinforcement of fa~ic units.
Figure E.14 disp1ays the relationship between thè permeant fl.uids
dielectric constant, and the normalized shear strength for the three
l'
tJpes of soil studied (shear strength/normal pressure applied) In
- examining these overall performance, it was apparent that there was a
tendency towards a o
decrease in shear strèngth, in comparison with
disti lled water, except in the cas~ of aniline and ace tic ae id which
showed an increase in shear strength, compared to the behaYiour of
distilled water. These results agreed with those given by Sridharan and
Rao (1979); l100re and Mitchell (1974); Mitchell and Aru1anandan (1968);
and Waildelich (1958).
In summary, the shear strength behaviour" of the clay so"ils was.

~
governed mostly by:

, Cp a decrease' in repulsion forces due tola decrease
.
in the dielectric constant, and a subsequent increase in pore fluid ion
concentration, (2) a slight decrease in water content due to the organic

, '"
..
displacement of adsorbed water layers, and (3) the prec1pf.t:at.lo,# of
n o
organic materials and the strengthening of the
'
interparticle bonds .
. .
336
( 0..8
0.7 0 Kaolinite
0,)
"-
:J
rJ)
• lIIite
• Natural Soil
.'
rJ) 06
0,)
."-
0...
ct!
.E
"-
0
OS
Z
.......
-
-<:;
0)
c:
- OA
.0,)
"-
( j)
"-
ct!
0,)
~ 03
(j) 0
(,~
•
02
01
Â
•
\
1 II m
'00
00 10 20 30 40 50 60 70 80
0
DieJectric Cqnstant (at 20 C)
v>
Fig. E.14. Nonnal1zed Shear strength Behaviour at Different

Dielectric Constants.
.
(
..
337
1 Other factors which can have an influence- on the observed results are:
(1) the dipo1e moment, and (2) the size and structure of ,the permeant
mo1ecu1es.
E.4 SUMMARY
b-: The resu1ts of this appendix indicate ,the e,ffects of the decreàse
in the dielectric constant of the resident pore f1uids, and of the
displacement of ionie species adsorbed on clay surfaces, resu1ting from

\
organic solution p~rmeation, on the geotechnica1 prop~rties (hydrau1ic
.
conductivity and the strength) and behavi.ouI;" of different· clay .soils.
In genera1, the hydraulic conductivity in ,'most of the cases studied

()
underwent a decrease (less than one arder of magnitude), while the
strength alsé decreased with the increase of the die1ectric constant of
- the permeant fluid. The combined effect of the changes in the pore fluid
dielectric constant and ion concentration, exercises an important
infll,lence on bath the hydraulic conductivi ty and the strength behaviour
of the soil. The. various relationships described in this appendix can
~ serve as a guide to sofving questions pertaining ta the possible
detrimenta1 alteration of certain geotechnicai properties of such types
of clay, soils.
_.
~
,. f
.; ".
338
c APPENDIX F
GENERAL CONSIDERATIONS
The starting point of the analysis for the design of a sanitary
landfill site should be the limiting seepage and the permissible flux of
leachate between the soil liner and the subsurface soil. The level of
tolerable flux should be determined by considering the following
factors:
(1) An estimation of the volume of the leachate solution generated
at the landfill si te, which will require some information
about the infiltra;ion and evaporation rate7nd the surface
runoff coefficients,
. '(2) The concentration of the contaminant species n excess of the
drinking water standard,
(3) The carrying capacity (exchange capaclty) of both the clay
liner and the subsurface soil, which identifies, to a great
extent, the amount of contaminants which could be held within
the pore space and on the surface of the soil particles,
(4) The hydraulic gradients and the dispersion coefficients, \
(5) Groundwater characteristics' including: depth, flow rate, and
flow direction, and
(6) The sink-source distance, i. e. the distance between the
contamination point (the landfill site) and the usage point
(the well depleting the aquifer).'
Once the permissible flux (Qp) is obtain'ed: its value should be
incorporated into the analysis of the soil hydraulic conductivity (K)
for certain geometrical_characteristics and clay soil properties. The
sail attenuation properties and the dispersion coefficient (D) must be
,l.
1 (
339
..
... determined experimentally using the soil-column leaching test technique
described in Chapter 2.
The convective-dispersive equation aids the estimation of the time
for a leachate solution with a given strength or concentration to reach
a certain depth. lt can also be used to calculate the concentration of

.
soil pore fluid at a given time and depthoabove the groundwater table,
if the initial concentration of ~he leachate solution permea~ng through
the soil profile is estimated to a reasonable dègree of accuracy.
Depending on the size of the aquifer and the rate of groundwater flow,
f the concentration of hazardous elements in water may or may not reach a
dangerous level in a short time. If the aquifer ls large and the
horizontal movement of water is appreciab le, the le,vel of the
contaminant species might not exceed the permissible limi ts of the

1
- drinking water for a long period of time.
In summary, the principal requirements that a clay soil must meet
for use as a barrier in l~ndfill,sites are as follows:
(1) Law hydraulic conductivity to water and waste fluid,
(2) Little or no interaction with the contaminant species which
might affect the impermeability of the barrier system,
(3) Carrying capacity for different contaminant species, and
(~) The strength, initially and after contact with waste' fluid to
maintain slope stability.
A generalized flow diagram for the contaminant species migration
predictions using the concept investigated in this research program 15 •
shown in Figure F.l.
'.
340
( Phase ,1
Site Selection
1
Initial Hydrogeologie Urdisturbed Su.r:rouOOing • Precipitation,Evaporation
Field Data Soil Characteristics and Surface Runaff Coefficients
.'
Phase II
Waste Fluid (Ieachate Solution)
, 1
1
Es tirnation of Leachate Est.irnation of Leachate
Volune Quality
Phase III
1
Soil-Leachate
Int7='= 1
I.aboratory Sttrly \ Field Investigation
(~ical ~els) Mcnitoring Wells
. ~I----------------r-------------------~
Soil carrying ,. TransmissibilltY Characteristics
Capacity
i
Phase IV
Mathanatical PredictionS'
1
Graphical Carputer Modelling
Solution
The conceAtration (C) Tœ distance (x) where The 't.iJœ (t)

at a selected distance (x) a selected concentration (C) when the Concentration
am tiIœ (t) will ~ at a qgiven will mach a selected
t.i.rie (t) Concentration· (C) at a
prEHietennined location '
(.
'-~
Fi9_. F .1. Generalized Flow Diagram for Leachate Migration Prediction.

PhD-Migration of Leachate Solutin Through Clay Soil

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, ... ....

for th.e degree of Doct~r of Philosophy

Department of Civil Engineering and Applied, Mech'llic:;s

Montreal, Quebec, Canada

MIGRATION OF ...LEACHATE SOlUTION THROUGH CLAY SOIL

sub~trate . Generally, this occurs through the penetration of the

assessment of the efficiency of the liner and the resultant migration"of

To evalua~e the potential of the use of natural cray as a barrieF

Lachenaie (35 km east of Montreal) was studied. Th~ , various chemical

constituents Qf the landfili

.rn companion laboratory tests, thesé leachate samples wer.e

permeated through laboratory columns that9_ contained the natural clay

compacted at the optimum water content. 'The col~s were constructed 50

c f. chemical analysis meaqured ?hanges in the concentration of:

,a4orbed .nd retained contaminants at v.rious Ume 'durations, /

'ft Predictiohs, using a dispersion-convection mOGel for Icentration,

profile development for either adsorbed or retained co~t~inants, were

.- compared'vith the e~~e_ent~llY determin~d

Another se: of experiments vas al~o

usually present in the leachate solutions. Furthermore, the data

suggest.ed that under favourable soil cpnditions, lJndfill leachates

containing low levels of trace metals will not pose a substantial

contamination threat to the subsurface environment, provided that a

propsF thickness of barrier is used. /

, MOSTAFA ABDEL WARITH

Le problème de déc:het$ solides' domestiques, enterrés dans des 81 tes

protectriée. L'utilisation de barrières d'~gile comme étant des matériaux

Danè le but d' é,?aluer le potentiel et la nature de l' argil~ utilisé

comme membrane pour contenit des déchets solides domestiques, un site

été déterminés à partir q'échantillons pris dans +es bassins col~ecteurs.

Des tests de laooratoire ·parallèles ont été menés sur la percolation

de lixi viats provenant -de Lachenaie à travers des colonnes d'argile

naturelles, compactées à leur tenêur en eau optimale. Les cellules de

percolation lente et saturée d'un lixiviat anaerobe à travers une

laquelle l'effluent a été collècté et amlysé pé~ement pour son

contenu en espèces chimiques et ses paramètres physiques. LI analyse

'~t r~-'3ées p~ur

de quelques fluLdes organiques sur. les propriétés géotechnique~ de

de problèmes importants de contamination des env~.

" Applied Mechanies, and Dirèctor of the Geoteehnical Rese'areh c:enter at

M6G!ll University. for his invaluable guidance' an'd continued

- Mr. Gerald Girouard: Environment Canada, Dept. of Emergeney and Waste,

làndfflls 'in Montreal'area and supplying the useful information;

Mr: F. " Caporusc id, Mp§'. P. •

their technical assistapce;

- . Speci..al apP7'eèiation is extended to my father a~d mot:her for their

encouragement and und~rstanding,

l. 2 Scope anq. Obj ,ectivé'S'I of,

1.3 Organizat.i0Il of the Thesis 5

CHAPTER 2 MATERIAL SAND., METHODS

2.4 Soil -Properties and Characterist1cs 10

2.5.1 Soil preparation

2.,5.2 Test Procedure • 26

2.5.3 The Experimental Series Invest~gated 29

2':'6 Labor:atory Investigation of Change in Hydraùlic 04.

2.7 Laboratory Landfill Model ,33

3.2 Migration of Diff~rent Contaminant ~pecies 41

3.3 Analyses and Discussion on the Contaminant

3.3.1 Attenuation of Heavy Metals 66

3.3.2.1 Water Content and Attenuation Number 70 .<

3.3.2.2 Mass Balance and the Relation between

3.3.2.3 The Relation between Soluble and Adsorbed

3.3.2.4 Desorption of Cation Species 87

3.3.2.5 Calculation of Selectivity Coefficients 92