EFFICACY EVALUATION OF AZADIRACHTA INDICA (NEEM) AND

MORINGA OLEIFERA (DRUM STICK) SEED SHELL BLENDED

CLAY SOIL AS LINER MATERIAL IN CHROMIUM (VI) LADEN
WASTE CONTAINMENT STRUCTURES

Thesis Submitted to National Institute of Technology Durgapur for the Award of

Doctor of Philosophy (Engineering) Degree

By
Chandrima Bhadra
Department of Civil Engineering,
National Institute of Technology, Durgapur

Under the guidance of

Dr. Supriya Pal
Associate Professor
Civil Engineering Department
National Institute of Technology, Durgapur
Durgapur-713209, West Bengal, INDIA

And

Dr. Kalyan Adhikari

Professor
Department of Earth & Environmental studies
National Institute of Technology, Durgapur
Durgapur-713209, West Bengal, INDIA
2021
 CERTIFICATE FROM THE SUPERVISORS
CERTIFICATE

It is certified that the work contained in the thesis entitled "Efficacy Evaluation Of

Azadirachta Indica (Neem) And Moringa Oleifera (Drum Stick) Seed Shell Blended Clay

Soil As Liner Material In Chromium(VI) Laden Waste Containment Structures " has been

carried out by me Chandrima Bhadra , Roll No. 15/CE/1505 & Registration No.

NITD/PhD/CE/2017/00885 , under the guidance of Dr. Supriya Pal & Dr. Kalyan Adhikari

in Civil Engineering Department Of National Institute of Technology Durgapur . The

data reported herein is original and that this work has not been submitted elsewhere for any

other Degree or Diploma.

-----------------------------------------

(Signature of Candidate)

CHANDRIMA BHADRA

Place………………………….:

Date…………………………..:

This is to certify that the above declaration is true.

--------------------------------------------- -------------------------------------------
Dr. Supriya Pal Dr. Kalyan Adhikari
Associate Professor Professor
Department of Civil Engineering Department of Earth & Environmental studies
NIT, Durgapur NIT, Durgapur
 ABSTRACT

Now-a- days, environmental pollution due to indiscriminate release of several toxic

compounds, generated mainly from various industries viz. tanneries, coke ovens, fertilizers etc.

raises a global concern, as these have toxic impacts on living organisms, causing different

health disorders such as skin problem, kidney disease, cancer, anemia, etc. in human beings

when the concentration levels of these candidates exceed the permissible limits (Mohan et al.

2005). These industries mainly discharge huge quantities of Cr (VI) in different form like solid,

liquid and gaseous wastes into the surrounding site causes major adverse biological and

ecological effects. Chromium is more toxic when it exists in hexavalent state. Hence, habitants

residing near a landfill site or any industrial area face colossal health effects due to exposure of

toxic contaminants viz. Cr (VI) etc. than other populations residing away from the disposal

sources. Furthermore the crop quality and agricultural production are also drastically affected in

these areas due to severe lithospheric (soil and groundwater) pollutions. Hence, the lateral and

sub-surface migration of pollutants from any waste disposal site can be protected through

confinement of the pollutants in the engineered containment structures in which low permeable,

chemically compatible and possessing good contaminants adsorption potential liner materials

play vital role in restricting the aforesaid migration.

So, proper selection of liner material is very much important for attenuation of

lateral and vertical migratory movement of contaminants in the sub-surface environment due to

leaching of pollutants from waste disposal sites to prevent groundwater pollution (Pu and Fox

2015). The migration of contaminants through subsurface soil is dependent on hydraulic

conductivity, tortuosity and adsorption capacity of the soil (Sharma and Reddy 2004; Vaishya et

al. 2008). The prediction of contaminant transport through soil is urged to protect
 groundwater from sources of pollutants. Using field simulation through horizontal tank

experiments and numerical modeling like HYDRUS-3D assessment of soil resilience and

movement of contaminants (in the present case Cr (VI) pollutants in aqueous medium) through

the subsurface to reach aquifers can be predicted. If experimental results match with a model

derived results then the model can be used to work out techniques to resist and remediate the

contaminated site.

Several authors of different parts of the world have studied the transport of contaminants

like heavy metals, organics (mainly pesticides) through subsurface using HYDRUS-1D model.

Abdel- Nasser et al. (2011) successfully applied HYDRUS model to predict the transport

behavior of Atrazine and Malathion pesticides in soil. HYDRUS-1D model was found

reasonably simulating the fate and transport of Cr (VI) in an anaerobic and fully saturated waste

column in which biodegradation and sorption are the prevailing fate processes (Adhikari et al.

2014; Rakshit et al. 2019).

The current research work was undertaken to explore the potentiality of Cr (VI)

attenuating capacity of locally available fine grained amended clayey soil with an aim for using

the soil as low cost liner material in engineered waste containment structures. The physico

chemical properties of soil were carried out conforming to Bureau of Indian Standard (BIS)

specifications. The soil was found with high clay content of about 56 %. The soil was black in

color and basic in nature (pH 7.7). The Atterberg limits of the soil were found as liquid

limit-47.12%, plastic limit-29.33%, plasticity index-17.79%. The saturated hydraulic

conductivity (Ks=6.5 x 10-7cm/s) of the soil was extremely low. Hence, the soil can be

considered as a good candidate for using as liner material in waste containment structures

(Ghosh et al. 2007).

According to Güler and Avci (1993), any soil material which is to be used as the primary liner

for containment of waste should have low hydraulic conductivity (<1.0×10-7cm/s).

 Cr(VI) adsorption by using locally available natural soils were experimentally explored

earlier using laboratory batch adsorption and Horizontal tank test . However, the study on

modeling of fate Cr (VI) through subsurface soil media including evaluation of reaction

parameters and validating the data using numerical model HYDRUS-3D etc. is not well

documented in literature.

In the present work, Laboratory scale batch and Horizontal tank experiments

were conducted to investigate the attenuative capacity of the studied soil for removal of Cr (VI).

The soil was found with reasonable Cr (VI) uptake capacity (65.789 mg/Kg). Laboratory batch

test results were found well fitted with nonlinear Langmuir isotherm model (coefficient of

determination, R2= 0.987.

In this present study, an attempt was made to blend AI seed shell and MO seed

shell dusts with the clay soil independently to enhance its Cr (VI) adsorptive capacity. Separate

batch adsorption studies were performed using synthetically prepared Cr (VI) solution as

adsorbate and AI and MO amended clayey soil as adsorbent, respectively. The pH of the

solution was maintained at 6.5 < pHzpc of the amended clay soil. It is observed that maximum

removal was achieved at 12 h contact time in both the cases and the Cr(VI) removal percentage

was found more than 90 % and 83% when 20% (by weight) AI and 20%( by weight) of MO

were blended with the clay soil, respectively. Desorption study was performed and only 5 %

desorption of Cr(VI) was observed . Hence to reinforce the statement of chemi-sorption SEM

Analysis was performed to examine the changes in microstructure of the soil for both raw soils

and soil after the desorption study . It can be seen that many irregular surface structure of soil as

well as pores are present on the surface prior to adsorption. Moreover, it can also be seen that

lots of crystals adhere on the soil surface ever after performance of desorption study. This

phenomena clearly indicates the chemi-sorption of the Cr(VI) on the AI blended soil surface.

XRD test was performed to examine the changes in the crystalline phases of the AI blended soil

before and after the adsorption study with synthetic solution of Cr(VI). A strong peak as seen at
2θ=44.16° which indicates the presence of Chromium adsorption in the soil. Plane (210) of

Chromium shows the evidence of presence of chromium in the sample.

The physical modelling studies were conducted in a laboratory scale tank made of perspex sheet

to assess the three dimensional migratory extent of Cr6+ from a source point in the AI amended

clay soil. As well as Numerical modelling of Cr6+ migration through soil were carried out using

HYDRUS 3D solute transport software. The nonlinear Langmuir isotherm coefficients were

used as input parameters in the HYDRUS 3D model to estimate the Cr6+ breakthrough curves

(BTCs) considering soil tortuosity value as 0.5. The breakthrough curve predicted by the

HYDRUS 3D model showed that the liner bed exhaustion is happening after a period of 38

years. The outcome of the present study is clearly indicating that the AI amended clay soil has

high potential in restricting the subsurface spreading of contaminants emanating from

chromium laden wastes disposed to open land or water bodies and thereby, the same may be

considered as an excellent candidate as liner material in waste containment structures.

 ORGANIZATION OF THESIS

Following chapters are structured in the thesis for presentation of entire work. Chapter

1 contains of introduction of the studied work, drawback of the previous studies and

justification of the contributory work. Scope and objective of the work in the present

investigation are given in Chapter 2. Broad review of literature relating to soil characterization

and groundwater pollution due to landfill and disposal of untreated or partially treated industrial

wastewater from tannery industry containing chromium and other contaminants, adsorptive

potential of clayey soils by using numerical model HYDRUS 1D are presented in Chapter 3.

Justification of the present investigation work is given in Chapter 4. Theoretical thoughts in

related to the present research work and various standard models used in the present research

work are presented in Chapter 5. Details experimental investigations highlighting the

experimental set up, experimental scheme adopted are presented as Materials and Methods in

Chapter 6. Chapter 7 exhibits the experimental results, data, analysis of results, model

validations and discussions with different graphs and tables. The concluding remarks on the

present investigation are described point-wise in Chapter 8. Future prospect of the work is

highlighted in Chapter 9. Lastly the references as cited in the thesis are all listed at the end of

the thesis as References. Abstract and front pages of the published papers pertaining to the

research work also enclosed as appendices.

 ACKNOWLEDGEMENTS

This thesis is the end of my journey in obtaining my Ph.D. I have not traveled in a vacuum in
this journey. This thesis has been kept on track and been seen through to completion with the
support and encouragement of numerous people including my well-wishers, my friends and
technical staff members of this department. At the end of my thesis I would like to thank all
those people who contributed in many ways to the success of this study and made this journey
possible and an unforgettable for me.

I am extremely indebted to my guide Dr. Supriya Pal of Civil Engineering Department and Dr.
Kalyan Adhikari from Departmentof Earth & Environmental Studies , National Institute of
Technology, Durgapur, for providing their invaluable guidance, support and encouragement
along with the necessary infrastructure and resources to accomplish my research work which
otherwise would have been an very uphill task. Under their guidance I successfully overcame
many difficulties and learned a lot. Despite of their extremely busy academic schedule, they
constantly used to review my thesis progress, give their valuable suggestions and made
corrections. Their unflinching courage and conviction will always inspire me, and I hope to
continue to work with them in future also. I can only say a proper thanks to them through my
future work.

I take this opportunity to sincerely acknowledge the Director, National Institute of Technology
(NIT) Durgapur, West Bengal, India, for providing financial support in the form of procurement
of laboratory equipments which buttressed me to perform my work comfortably.

I gratefully acknowledge Mr. Pallab Biswas, Technical Assistant, Soil Mechanics & Foundation
Engineering Laboratory, Civil Engg Dept., NIT Durgapur, for his endless support and
encouragement to carry out the Experimental work in this Laboratory. I am thankful to Mr.
Avishek Adhikary and Mr. Sumonto Rakshit for their support during my computational work.
My special thanks to all the members of Doctoral committee of my dissertation work for
providing necessary advice and suggestions.
I cannot find any words to express my gratitude to my parents, my father Shri. Mrinal Kanti
Bhadra who is there with me in every step of my life and my mother Smt. Sikha Bhadra who
always supports and strengthens me, My Husband Mr. Shatadru Guha , whose immense
support and inspiration made my work successful. I owe my encompassing debt and my
heartfelt gratitude to all my friends and relatives whose silent blessing and best wishes were
source of strength of my work.

Date:
Name of the student : Chandrima Bhadra
Regn. No.: NITD/PhD/CE/2017/00885
Department: Civil Engineering
National Institute of Technology Durgapur
West Bengal, 713209, India
 Civil Engineering Department
National Institute of Technology, Durgapur
Durgapur-713209

1. Title of the Thesis: Efficacy Evaluation Of Azadirachta Indica (Neem)

And Moringa Oleifera (Drum Stick) Seed Shell
Blended Clay Soil As Liner Material In Chromium(VI)
Laden Waste Containment Structures
2. Name, Designation & i) Dr. Supriya Pal
Institution of the Supervisors: Associate Professor, Civil Engineering Department
National Institute of Technology, Durgapur
Durgapur -713209.
ii) Dr. Kalyan Adhikari
Professor, Department of Earth & Environmental studies
National Institute of Technology, Durgapur
Durgapur -713209.
3. List of Publications:
● Bhadra C, Pal S, Adhikari K (2018) Use of compacted clay liner for the attenuation of
landfill leachate migration from a MSW site in Durgapur , West Bengal .
Journal of Indian Chemical Society, Vol. 95, March 2018, pp. 1-8, Elsevier Publication
(SCI INDEX Expanded) .
● Bhadra C, Pal S, Adhikari K (2019) Efficacy evaluation of chromium(VI) adsorption on
clay soil blended with Azadirachta indica (Neem) and Moringa oleifera (Drum stick)
seed shell . Journal of Indian chemical society , Vol. 96, April 2019, pp. 1-5, Elsevier
Publication , (SCI INDEX Expanded) .
● Bhadra C, Pal S, Adhikari K (2020) Assement of the migratory behaviour of
contaminant originating from tannery waste water through amended clay liner using
HYDRUS-3D solute transport model . Journal of Indian chemical society , Vol. 97, No.
12b, December 2020, pp. 1-9 , Elsevier Publication , (SCI INDEX Expanded)

● Bhadra C, Adhikary A , Pal S, Adhikari K(2020), Assessment of migratory behaviour of

Chromium(VI) contaminant through clay liner using Hydrus-3D solute transport model.
Journal of Environmental engineering & Landscape Management . SCI INDEX,(Under
Review )
● 4. List of Patents: Nil

5. List of Presentations in National and International:

● Bhadra C, Pal S, Adhikari K 2020 , Assessment of migratory behaviour of
Chromium(VI) contaminant through clay liner using Hydrus-3D solute transport model .
International Conference on Water, Energy, and Environmental Sustainability 2020
(WEES 2020)
● Bhadra C, Pal S, Adhikari K 2020 , Assesment Of The Migratory Behaviour Of
Contaminant Originating From Tannery Waste Water Through Amended Clay Liner
Using Hydrus-3D Solute Transport Model . 2nd International Conference on Advanced
Technologies for Industrial Pollution Control (ATIPC-2020).
 TABLE OF CONTENTS
Chapte Title Page
r No. No.
CERTIFICATE i
ABSTRACT ii-v
ORGANIZATION OF THESIS vi
ACKNOWLEDGEMENT vii-vii
i
PUBLICATION DETAILS ix
LIST OF TABLES x
LIST OF FIGURES xi
LIST OF SYMBOLS AND ABBREVIATIONS xii

1.0 INTRODUCTION 1-4

2.0 OBJECTIVE AND SCOPE OF RESEARCH

2.1 Objective of the study 5
2.2 Scope of the study 5

3.0 LITERATURE REVIEW

3.1 Properties of chromium 7
3.2 Uses of chromium 7
3.3 Permissible limits of chromium 7
3.4 Presence of chromium in industrial wastewater 7
3.5 Abatement technologies for chromium in wastewater 8
3.6 Characterization of lithosphere pollution surrounding the solid waste 9
disposal sites and wastewater outlet pool containing chromium and other
pollutants
3.7 Removal of chromium compounds in aqueous medium by soils and other 10
adsorbents
3.8 Factors affecting the adsorption of chromium in soils 11
3.9 Modeling aspect of chromium adsorption phenomena
3.9.1 Fixed-bed adsorption 12
3.9.2 Numerical modeling of solute transport mechanism using 14
HYDRUS-1D and application of CXTFIT model

4.0 JUSTIFICATION OF THE PROPOSED INVESTIGATION WORK 19

5.0 THEORETICAL CONSIDERATION OF FATE OF CHROMIUM 20

THROUGH AMENDED CLAY SOIL
5.1 Adsorption isotherm 20
5.2 Theoretical models
5.2.1 Isotherm model
5.2.1.1 Linear isotherm model 21
5.2.1.2 Langmuir isotherm model 21
5.2.1.3 Freundlich isotherm model 21
5.3 Quantitative Data Analysis 22
5.3.1 Statistical Analysis 22
 5.4 Transport models 22

6.0 TEST PROGRAM AND EXPERIMENTAL PROCEDURE

6.1 Study Area 23
6.1.1 Study Area 1 23
6.1.2 Study Area 2 24
6.2.1 Sampling procedures 25
6.3 Collection of samples near tannery waste disposal site 25
6.3.1 Soil Sample Preparation 26
6.3.2 Leachate generation 26
6.3.3 Preparation of sample for heavy metal analysis 27
6.4 Experimental Methods
6.4.1 Test for physical properties of soil samples
6.4.2 Test for chemical properties of soil samples
6.4.3 Experimental procedures 28
6.4.3.1 Determination of physical properties of soil
samples
6.4.3.1.1 Natural moisture content test
6.4.3.1.2 Field bulk unit weight test
6.4.3.1.3 Particle size analysis
6.4.3.1.4 Specific gravity test
29
6.4.3.1.5 Liquid limit & Plastic limit test
6.4.3.1.6 Light compaction test
6.4.3.1.7 Total Porosity
6.4.3.1.8 Saturated hydraulic conductivity
6.4.3.1.9 Organic carbon content 30
6.4.3.2 Test for chemical analysis
6.4.3.2.1 Determination of soil pH value 31
6.4.3.2.2 Determination of Chromium(VI)
concentration by colorimetric Method
6.5 Collection of adsorbents and characterization
6.6 Adsorbate preparation 32
6.7 Zero Point charge test for clayey soil
6.8 Batch adsorption test for the unadulterated clay soil
6.9 Preparation of the natural adsorbent 33
6.10 Batch adsorption test for the amended clay soil 34
6.11 Kinetic studies 34
6.12 Horizontal Tank test 35

7.0 Research Findings and Discussion of Results

7.1 Subsurface soil quality characteristics in the study area 1 37
7.2 Subsurface groundwater characteristics in the study area 1 43
7.3 Descriptive statistics of groundwater contaminants 44
7.4 Physical properties of soil at the waste disposal site at Durgapur 45

7.5 Groundwater quality characteristics in the study area 2 45

 7.6 Soil Characteristics in the tannery waste disposal site at Kolkata 47
7.7 Batch Adsorption Study for Cr (VI) removal by the landfill soil of site 1 47
(Durgapur)
7.8 Efficacy of amended clay soil as liner material for attenuation of Cr (VI) 49
in waste disposal site
7.8.1 Test results on clay soil quality 49
7.8.2 Batch Adsorption test for the clayey soil used for liner material 50

7.8.2.1 Effect of pH on chromium (VI) adsorption in aqueous media 51

7.8.2.2 Effect of adsorbent dosage and contact time on chromium (VI) 52
adsorption in aqueous media.
7.8.2.3 Study of Adsorption Isotherm 54
7.8.2.4 Desorption Study 57
7.8.3 Scanning Electron Microscopy (SEM) 58
7.8.4 XRD Studies 59
7.9 Modelling of Cr6+ migration through amended clay soil 60

8.0 CONCLUSIONS 64-66

9.0 FUTURE SCOPE OF WORK 67

REFERENCES 68-77
 LIST OF TABLES

Table Title Page

No. No
3.1 Industrial sources and concentrations of Cr (VI) 8
3.2 Comparison of Cr (VI) uptake capacity on various low-cost adsorbents 11
7.1 Descriptive Statistics of soil samples collected from landfill 38
7.2 Correlation coefficient matrix of soil quality parameters. 40
7.3 Initial eigenvalues of soil quality data 41
7.4 Varimax rotated factor loading matrix for landfill soil data (Kaiser 42
Normalization)
7.5 Well Parameters 43
7.6 Descriptive Statistics for ground water samples (” =Permissible limit) 44
7.7 Physico-chemical characteristics of the test soils 45
7.8 Descriptive statistics of groundwater samples collected near the leather 46
industrial zone
7.9 The physical and chemical characteristics of the test soils 47
7.10 Batch adsorption test results of Cr (VI) using landfill soil as adsorbent 48
7.11 Physico-chemical properties of the clay soil 49
7.12 Freundlich and Langmuir isotherm constants, R2 values for Cr(VI) 56
adsorption on amended clay soil.
7.13 Comparative study of Cr (VI) adsorption capacities of different adsorbents 57
along with AI & MO blended clay soil.
 LIST OF FIGURES

Fig. Title Page

No No
6.1 Study Area, West Bengal Map Extract 1:50,000 Topo sheet No. 73 M/6 23

6.2 Major soil patterns in the study area 24

6.3 Study Area 2 , West Bengal Map Extract 25
6.4 Leachate Generation Procedures 26
6.5 Vacuum Filtration 27
6.6 Acid Digestion- Laboratory Setup 27
6.7 Standard Calibration Curve of Cr(VI) 31
6.8 Experimental setup used for the Cr6+ migration test. 36
7.1 Illustration of DTW, WTD and Height above msl 43
7.2 Graphical representation of batch adsorption test results of Cr (VI) on 50
naturally available clay soil.
7.3 Graphical representation of pHZPC test results on amended clay soil 51
7.4 Graphical representation of effect of pH on absorption of Chromium (VI) 52
with natural adsorbent as Azadirachta indica .
7.5 Graphical representation of effect of pH on absorption of Chromium (VI) 52
with natural adsorbent as Moringa oleifera.
7.6 Plot of batch adsorption test result of AI amended clay soil as adsorbent 53
and Cr6+ solution as adsorbate .
7.7 Plot of batch adsorption test result of MO amended clay soil as adsorbent 54
and Cr6+ solution as adsorbate .
7.8 Plot of Langmuir isotherm model for the adsorption of Cr 6+ by AI 55
blended clay soil
7.9 Plot of Langmuir isotherm model for the adsorption of Cr 6+ by MO 55
blended clay soil.
7.10 Plot of Freundlich isotherm model for the adsorption of Cr 6+ by AI 55
blended clay soil
7.11 Plot of Freundlich isotherm model for the adsorption of Cr 6+ by MO 56
blended clay soil.
7.12 Desorption percentage of hexavalnt chromium 57
7.13 SEM Images (a) Raw Clay soil (b) clay soil blended with AI (20% by 58
weight of soil) prior to Cr (VI) adsorption, (c) Cr (VI) adsorbed AI
blended clay soil after desorption study .
 7.14 Graphical representation of the XRD of raw soil and soil composition 59
after adsorption (a) Amended clay soil after adsorption (b) Amended clay
soil.
7.15 Pictorial representation of the HYDRUS 3D generated model of the 60
horizontal tank test for the prediction of the solute transport of hexavalent
chromium through amended clay liner .
7.16 Experimental and Hydrus-3D predicted Cr (VI) breakthrough curves in 61-62
AI amended clay soil (a) 1st observation point of tank test (b) 2nd
observation point of tank test.
7.17 HYDRUS- 3D predicted Cr (VI) breakthrough curve in 1m thick 62
amended clay liner.

LIST OF SYMBOLS AND ABBREVIATIONS

Symbols and Significance
abbreviations
k hydraulic conductivity
BTC breakthrough curve
AI Azadirachta indica
RMSE Root mean square error
MO Moringa oleifera
CME co-efficient of model efficiency
Kd distribution coefficient
BDST bed depth service time
R retardation factor
Kd partitioning coefficient in linear isotherm
tb breakthrough times
te bed exhaustion times
Z soil bed height (cm)
C concentration of solute in liquid phase (mg/L)
t time (day)
Vx average pore water velocity (cm/day)
DL longitudinal dispersion coefficient (cm2/day)
qe solute concentration in solid phase at equilibrium (mg/Kg)
Qmax maximum adsorption capacity at monolayer (mg/Kg)
b constant related to free energy of adsorption (l/mg)
kf adsorbent capacity (mg/Kg)
n adsorbent intensity (l/mg)
ρd dry density of soil
γb bulk density of soil
Ks saturated hydraulic conductivity
NMC natural moisture content (%)
LL liquid limit
PL plastic limit
PI plasticity index
G specific gravity
n porosity
foc organic carbon content
pHzpc pH point of zero charge
SEM scanning electron microscopy
XRD X-Ray Diffraction
α dispersivity
df degree of freedom
SS Sum of squares
MS Mean square
C0 initial concentration of solute
Ce Equilibrium/effluent concentration of solute
R2 coefficient of determination
R percentage removal of chromium

Chapter 1 : INTRODUCTION
INTRODUCTION
Waste containment structures and tailing ponds are employed in many parts of the world
including India for disposal of hazardous materials either in liquid or slurry form. Toxic
substances laden wastewater emanating from industrial establishments are indiscriminately
discharged in wetland area elsewhere simply onto land surfaces . All these sites are known to be
contaminant releasing sources for migration of various toxic and xenobiotic pollutants through
soil resulting in groundwater and lithospheric pollution. The pollutants when released to the
subsurface soil layers with fine grained texture, migrates in the direction of groundwater flow
causing a serious depletion of groundwater quality (Lee et al. 2012). For prevention of
movement of such pollutants, various kinds of materials are being used as a containment barrier
such as clay, amended clay, organoclay, geosynthetic clay, geomembrane, high density
polyvinyl chloride (HDPC) etc. considering their aspects of low hydraulic conductivity (kp) and
reasonable adsorption capacity of the candidate materials (Ghosh et al. 2012; Pal et. al 2017).
But most of the synthetic materials being used for the said purpose are expensive and
sometimes don’t support the economics of the pollution control measures considering their
application in the vast extent of the area. Clay liners of low kP value and good adsorption
capacity are considered to be low cost and proved to be economical in underdeveloped countries
(Güler and Avci 1993; Kalkan and Akbulut 2004; Adhikari et. al. 2014). Moreover, in order to
assess the migratory plume dispersion of pollutants into the surrounding soil pathways,
estimation of the adsorption behavior of soil is very much important in congruence with
retardation of the transport of pollutants if the same is to be used as a liner material.
Chromium is considered one of the priority pollutant (119th out of 126 priority
pollutants) in USEPA (United States Environmental Protection Agency) list and highly toxic
when exists in its hexavalent state. Chronic inhalation and consumption of Cr (VI) either from
air or groundwater may cause different health disorders such as skin problem, cancer, anemia,
infertility etc. in human beings when the concentration levels of these candidates exceed the
permissible limits (Mohan et al. 2005). Cr (VI) has been utilized on a big scale in several
industries like electroplating, metallurgy, tanning, chemical production, wood preservation and
paper production (Dakiky et al. 2002). These industries discharge huge quantities of Cr (VI)
compounds in different form like solid, liquid and gaseous wastes into the surrounding site
causes major adverse biological and ecological effects. The maximum permissible limit as par
WHO (World Health Organization) for Cr (III) & Cr (VI) in effluents are 5 and 0.05 mg/L
respectively.
 Various methods and researches have been conducted for the removal of excess amounts
of different forms of Chromium from waste water, preferably the hexavalent Chromium since it
is having a carcinogenic effect on the living organism. Such adverse effects are encountered
when chromium laden wastes are disposed from the above industries into containment
structures or simple disposal to a land either after partial treatment of effluents or without any
treatment. Chromium compounds trickles down through different strata and migrate along with
groundwater flow due to tortuosity effect and favorable hydraulic conductivity in soil. In some
literatures it has been recommended that some specified types of soil of low hydraulic
conductivity would be useful as primary liner materials for retarding or imbibing some toxic
compounds (Mohamedzein et al. 2005; Ghosh et al. 2007; Pal et. al. 2017). Adsorptive capacity
of soil depends upon clay content and type of clay minerals present in the soil . Soil with low
clay content usually posses low adsorptive capacity . However it is very important to explore
surrounding soils of waste disposal site for assessment of the extent of pollution and uptake and
accumulation of such compounds in soil. Moreover, additive inclusions in such soil sometimes
elevates its contaminant adsorption capacities and thereby extends the life of the containment
structures if the amended soil is used as liner material. The uptake capacity of soils of
contaminant particularly cations from industrial wastewater is largely dependent on surface area
of the clay particles , background pH and clay content of the soils (Djebbar et al. 2012; Park et
al. 2011). Ghosh et. al (2014) investigated distribution coefficients and mobility characteristics
of hexavalent Chromium in clayey soils. They found that clay mineral content was the most
important soil component controlling adsorption potential of soils. The specific surface area
(SSA) of soil increases with the increment of fine grained particles (clay and silt content). The
larger SSA is beneficial to sorption by offering more adsorption sites to be utilized by adsorbate
(Liang et al. 2010).

A number of mathematical models are developed till date to study the nature of the
adsorption process namely Langmuir, Freundlich, Redlich-Peterson etc. for adsorption isotherm
study along with various reaction order models such as pseudo- first- order,
pseudo-second-order, inter particle diffusion models for kinetics studies (Ho and Macay, 1998;
Adhikari et. al. 2014). The linear least square regression method is frequently used in fitting the
equillibrium experimental adsorption data with the above models to estimate the coefficients of
the model equations. In case of design of liner thickness in waste landfill site and to generate
breakthrough curves, the continuous fixed-bed column studies are to be performed in the
laboratory. However, the requisite experiments are complex, time dependent and necessitate
close surveillance. The significance of the present investigation is to incorporate batch, fixed
bed adsorption experimental data of chromium-soil system in various adsorption- isotherm
model to investigate the attenuation behavior of fine grained clayey soil to mitigate chromium
pollution in the on-site disposal of the waste soil environment. Limited literatures and research
reports are available in this context, using all kind of batch scale and fixed bed adsorption
models for examining soil as a material for attenuation of chromium transmission through soil
particularly having low hydraulic conductivity. Moreover, novel natural additives are also
blended with the soil to explore its enhancement of adsorptive attenuation capacity so that the
same can be used as primary liner material in waste containment structures containing
chromium laden wastes.

Published literature on experimental researches on chromium adsorption by natural soil

using laboratory batch adsorption and fixed bed column studies is very limited (Khalid et al.
2017; Falciglia et al. 2018). However, the study on modeling of chromium adsorption processes,
migration phenomena through soil media and validating the data using solute transport
modelling tool is very much less documented in the available literature.

It is therefore felt the urge of exploring the application of fine grained clay soil blended
with natural adsorbents viz. neem (Azadirachta indica) and drumstick (Moringa oleifera) seed
dusts for attenuation of chromium pollutants from a typical real life waste disposal site. In the
present investigation two sites have been undertaken: (i) the effluent disposal site (22° 33' 18'' N
and 88° 22' 47" E) of a tannery industry located in Kolkata, West Bengal, India and (ii) Waste
dump sites (23° 33' 05'' N and 87° 19' 03" E) located in the industrial city Durgapur, West
Bengal, India. Both the sites exhibit a high chromium pollution in sub-surface soil and
groundwater due to discharge of tannery wastewater (Site 1) and prolong dumping of mixed
(municipal and Industrial) solid wastes (Site 2). Hence, selection of suitable soil material is
necessary as a primary liner for controlling subsurface movement of toxic Chromium for the
sites.
Most of the subsurface pollution problems start from activities involving the
unsaturated/vadose zone between the soil surface and groundwater table. The vadose zone
hence provides better opportunities to limit or prevent groundwater pollution. Once the
contaminant enters the groundwater system, pollution is essentially irreversible or can be
remediated only with high costs and depleting the natural resources.
 Furthermore, in order to predict the fate and transport of solute in clayey soil more
accurately, the reliable hydrodynamic parameters of solutes in soil are needed to evaluate
(Chotpantarat et al. 2012). For this purpose, the non-linear least square curve fitting program
was used by many researchers (Saquing et al. 2012; Pal et. al. 2017) using nonreactive tracer
breakthrough curves (BTCs) analysis.
The application of complex mathematical modeling based on numerical solution, is an
attracting important tool for analyzing subsurface flow and contaminant transport problems. In
this context, the application of Windows based HYDRUS-3D software package is extremely
useful for prediction of data selection of preventive materials for retarding solute transportation
on soils (Zhi 2013). The contaminant fate and transport model HYDRUS-3D Version has been
widely used to simulate reactive solute transport in soils with the help of estimated
hydrodynamic parameters and linear, non-linear isotherm parameters (Bahaminyakamwe et al.
2006; Ngoc et al. 2009).
However, no such literature is found on the application of HYDRUS-3D model to
simulate the fate and transport of chromium contaminants particularly through soil media in
both vertical and horizontal directions after performing necessary vertical and horizontal
migration tests.
In view of the above, a research study was undertaken to examine the efficacy of natural
additive blended fine grained clay soil for assessing its fitness to use as liner material by
conducting necessary adsorption experiments and to validate the experimental data with the
HYDRUS-3D model as a prediction of migratory movement of chromium from waste disposal
site.
The present investigation is expected to provide an important contribution and
guidelines for assessment and determination of attenuation capacity of soil for removal of toxic
pollutants released from any disposal site or containment structures.
Though the study was conducted looking in a live waste disposal site releasing
chromium in the subsurface, the methodology can also be applied for toxicants other than
chromium as leaching out from similar type of waste disposal site containing other than
chromium also.
Chapter 2 : Objective & Scope
 OBJECTIVE AND SCOPE OF RESEARCH
2.1 Objective of the Study
The objective of the present research was
● To assess the impact of leachate generated from chromium laden waste disposal sites
to the subsurface soil and groundwater quality and thereby to ascertain the extent of
threat to the hydrogeology in close proximities of the disposal sites.
● To examine the adsorptive efficacy of naturally available fine grained clay soil
blended with Azadirachta indica seed and Moringa oliefera seed shell dust as natural
adsorbents in removing hexavalent chromium from aqueous solution with an aim to
use same as liner material in chromium laden waste containment structures.
● To assess the migratory behaviour of Cr (VI) contaminants through the amended
clay liner using Hydrus 3D solute transport model in order to evaluate the optimum
design thickness of the liner.

2.2 Scope of the Study

Following scopes were considered for achieving the objective of the present research
investigation.
1. Reconnaissance study of chromium contaminated source and surroundings.
2. Selection of sampling points for soil characterization and groundwater characterization.
3. Analysis of soil and groundwater samples for different physico-chemical parameters
including concentration of Cr (VI) in both the samples.
4. Preliminary investigation on assessing the extent of pollutants in the contaminated sites
5. Statistical analysis (correlation analysis, factor analysis, principal component analysis
etc.) for characterization groundwater pollution and soil pollution in the sites.
6. Laboratory study of chromium (VI) adsorption capacity by soil samples
(uncontaminated soil samples) collected from the adjoining areas of contaminated sites.
7. Laboratory study for determination of chromium (VI) adsorption capacity by locally
available fine grained clay soil samples as well as amended (Azadirachta indica and
Moringa oliefera seed shell dust) clayey soil samples.
8. Conducting adsorption experiment program through laboratory scale batch and
horizontal migration studies.
9. Determination of adsorption isotherm coefficients.
10. Validation of three dimensional pollutant transport model by available experimental data
and with test performance data.
11. To explore and assess the horizontal migratory extent of chromium pollution in soil and
groundwater environment and also to test the experimental results with standard
software package HYDRUS-3D.
12. The model simulation with respect to the depth and time variant for estimating Cr (VI)
transport mechanism in three dimensional saturated soil media surrounding the real life
chromium contaminated site.
Chapter 3: LITERATURE REVIEW
 LITERATURE REVIEW
3.1 Properties of chromium
Louis-Nicolas Vauquelin, a French pharmacist and chemist extracted contaminated
chromium by reduction of Cr2O3 with charcoal in 1798. Normally, the existences of chromium
in aqueous media have been found as Cr (III) and Cr (VI) under natural conditions. As per
toxicological reports, Cr (VI) is significantly 500 times more toxic than Cr (III) (Kowalski
1994). The basic properties of Cr (VI) are as follows (Lunk 2015):

(i) Crystal structure

(ii) Molar mass : 51.9961 g/mol
(iii) Melting point :1,907 °C
(iv) Density :7.19 g/cc
3.2 Uses of chromium
● Cr (VI) is used for wood preservation, tanning of leather, metal polish, titrating agent
etc.

3.3 Permissible limits of chromium

Cr (VI) is considered as a priority pollutant and emanated mainly from the wastewater
discharge of several industries like tannery, electroplating, textile dyeing etc. The contaminant
has toxic impacts on living organisms, causing different health disorders such as kidney disease,
cancer, anemia, etc. in human beings when the concentration level of this candidate exceed the
permissible limit (Mohan et al. 2005). As par WHO (World Health Organization), the alarming
level of chromium in trivalent state and hexavalent state in wastewater are 5 mg/L and 0.05
mg/L, respectively.

3.4 Presence of chromium in industrial wastewater

Different industries, such as refineries, manufacture of petrochemicals leather tanning,
aluminum conversion and coal processing discharging wastewater containing Cr (VI)
compounds. The concentration of Cr (VI) in industrial waste water were found within the range
of 0.20-53 mg/L (Baral et al. 2009). The concentrations of Cr (VI) compound detected in the
effluents of various industries are presented in Table 3.1.
Table 3.1: Industrial sources and concentrations of Cr (VI) (Owlad et al. 2009)
Cr(VI)
Industry Concentration References
(mg/L)
Hardware factory 60 Xu et al. 2005
Chrome tanning plant 3.7 Gupta et al. 1999
Tannery plant 3950.0 Esmaeili et al. 2005
Electroplating plant 75.4 Tukaram Bai et al.2005

3.5 Abatement technologies for chromium in wastewater

Various procedures used for eliminating Cr (VI) from the industrial effluents. These
procedures can be classified into three categories: physical, biological and chemical procedures.
In actual practice, a grouping of different procedures is used to treat Cr (VI) bearing wastewater
because of the complex nature of the industrial effluents. The natural arrangements are also used
to treat industrial effluents using land based applications.
The selection of methods depends upon several factors like initial concentration of
effluent pollutants, effectiveness of the process, reasonable aspects, volume of effluent to be
treated, simplicity of operation and maintenance etc. Adsorption is an active and useful method
to eliminate low concentration effluents specially containing a dissolved solid (Ahmaruzzaman
and Sharma, 2005) which resolves the difficulty of sludge disposal and also make the system
more economically viable, particularly if low-cost adsorbents are used. The factors affecting
adsorption are:
● Characterization of the adsorbent by finding out surface area, chemical composition,
pore size etc.).
● Characterization of the adsorbate by finding out molecular size, molecular polarity,
chemical composition etc.
● The initial concentration of the adsorbate in the aqueous phase (solution).
● The characteristics of aqueous phase (pH, temperature).
● The adsorbate and adsorbent reaction time in the system.
3.6 Characterization of lithosphere pollution surrounding the solid waste disposal sites
and wastewater outlet pool containing chromium and other pollutants
Recently, investigators observed that soil and groundwater contaminated by various types of
pollutants around waste disposal sites for disposing/discharging of untreated municipal and
several industrial wastes (Singh et al. 2004; Alexakis 2011; Lu et al. 2012; Nosrati and
Eeckhaut, 2012) and some of the investigators have carried out statistical analysis to study the
influence of various kinds of wastes coming from several waste disposal sites on surrounding
soil and groundwater (lithosphere) quality (Srivastava and Ramanathan, 2008; Lu et al. 2012;
Zamani et al. 2012; Han et al. 2013). Adhikari et al (2012) assess the heavy metal
contamination of native soil by mining activities in the two hundred years old Raniganj coal
field area. Samples were collected from mine wastes and analysed for heavy metals Fe, Mn, Zn,
Cu, Cr, Ni, Pb and Cd. Average concentration of heavy metals in shale has been considered as
background value. Average concentrations of Fe, Ni, and Cd in both native soil and mine spoil
lie above the average concentration of world soil. Augustin Jr. and Viero (2011) investigated the
ecological effect and geochemical conduct of soil toxins from a municipal solid waste landfill in
southern Brazil. The outcomes indicated far and wide pollution of soil in the encompassing
regions of the landfill. Cr, Cl-, and NH4-had the most elevated toxin levels, mirroring their high
substance in the landfill leachate. Pal et al. (2011) carried out characterization of subsurface
water near an industrial waste water disposal site in Durgapur, West Bengal, India. Water
quality assessment was carried out for parameters like TDS, TH, TA, pH, EC, Cl-, SO42-, NO3-,
Ca2+, Mg2+, Na+, K+, Phenol, As, Cr6+ and CN-. Each parameter was then compared with
standard limits as specified by WHO to assess the groundwater quality. Pearsons’ multivariate
correlation analysis was exercised to find out the relationship between various sampling data
and factor analysis was carried out to the datasets which resulted in three factors explaining
80.92% of the total variance of the respective datasets.
Most of the industries in developing countries like India discharges their untreated or
partially treated wastewater directly on depression land or containment structures outside their
boundary premises and subsequently channeling them to nearby surface water bodies viz. pond,
lake, river, sea etc. This industrial wastewater most of the cases contains very high
concentrations of toxic contaminants such as Cr, Co, Zn, Cd, Ni, Cu, Ag (Shackelford 1991).
Among of this toxic heavy metals, Cr (VI) resulting from landfill sites in many waste disposal
sites or waste containment structures causing serious lithospheric (soil and ground water)
pollution (Vaishya et al. 2008) and great anxiety to local authorities and experts, since
agricultural activities in many cases are carried out surrounding these sites and groundwater is a
major supply of both irrigation and domestic water (Han et al. 2013).
3.7 Removal of chromium compounds in aqueous medium by soils and other adsorbents
Various techniques were used for eliminating Cr (VI) from industrial wastewater as described
earlier. However, low cost physical adsorption process is most popular techniques worldwide to
eliminate Cr (VI) which resolves the difficulty of sludge disposal and also make the system
more economically viable. Some remarkable investigations were examined for removal of Cr
(VI) from aqueous solutions by various types of low cost adsorbents such as agricultural waste
material (Dubey and Gopal 2007), neem saw dust (Vinodhini and Das 2010), tea residue
(Dizadji and Anaraki 2011), corn stalk (Chen at el. 2012), pcc beads (Zuo and Balasubramanian
2013). All above mentioned researchers have stated a significant amount of Cr (VI) could be
removed by using each of these adsorbent.
Dubey and Gopal (2007) investigated the performance of agricultural waste material for
removal of chromium (VI). In their investigation they observed the effects of various variable
parameters like dosage, pH, contact time and agitation rate. Maximum removal of hexavalent
chromium was achieved (97%) at pH 3 and contact time at 5 h. The batch test data were fitted
best with Freundlich adsorption isotherm model.
Garg et al. (2007) examined the performance of agricultural waste biomass for removal of
chromium (VI). They used various types of agricultural wastes as an adsorbent like sugarcane
bagasse, maize corncob and Jatropha oil cake. Optimum condition of the adsorption system was
found in the acidic medium at pH 2 with a contact time of 60 min at 250 rpm stirring speed.
Langmuir and Freundlich adsorption isotherms were reasonably fitted with the experimental
data and the performance of Jatropha oil cake had found better comparison to other adsorbent
under optimal conditions.
Jain et al. (2009) investigated the performance of helianthus annuus (sunflower) stem
waste for removal of Cr (VI) from aqueous system. Two adsorbents were used to study the
performance of adsorbent. Adsorbent one was prepared by boiling stem waste of sun flower
and second adsorbent was modified by using formaldehyde. The maximum metal removal
efficiencies of boiled sunflower stem absorbent and formaldehyde-treated sunflower stem
absorbent were 81.7 and 76.5%, respectively at pH 2.0 and at adsorbent dose 4.0 g/L.
Ghosh et al. (2014) carried out the performance of a clayey soil as liner material for
removal of Cr (VI) . From experimental test results they observed that studied soil can resist
maximum overburden pressure of 3.0 kN/m2 from dumping waste materials if the clayey soil is
to be used as a liner material and Cr6+ attenuating capacity from 80-90%. This investigation also
showed that the compacted clay soil with a thickness of 600mm is suitable for arresting the
migration of a leachable hexavalent chromium with an initial concentration of 7.5 mg/L.
Performance of some low cost adsorbents for removal of Cr (VI) as reported by some
research investigations has been presented in Table 3.2.
Table 3.2: Comparison of Cr (VI) uptake capacity on various low-cost adsorbents (Dubey and
Gopal 2007)
Capacity
Adsorbents References
(mg/g)
Red mud 1.60 Pradhan et al. (1999)
Namasivayam and Yamuna
Biogas residual slurry 2.40
(1995)
Pine needles 5.87 Dakiky et al. (2002)
Fly-ash wollastonite 2.92 Pandey et al. (1984)
Sawdust 3.30 Srivastav et al. (1986)
Coconut tree sawdust 3.46 Selvi et al. (2001)
Wool 8.66 Dakiky et al. (2002)
Sugar cane bagasse 13.4 Sharma and Forster (1994)
Coconut husk fibers 29.0 Tan et al. (1993)
Bagasse fly-ash 260.0 Gupta et al. (1999)

3.8 Factors affecting the adsorption of chromium in soils

Factors effecting adsorption of Cr (VI) in soils were initial concentration of Cr (VI),
adsorbent dosage, solution pH and reaction time as referred by Sahu et al. (2009). It was
obvious that the Cr (VI) removal efficiency by adsorbent (soils) increases with the increment of
adsorption dosage up to a certain limit and then negligible effect observed. With increase in
adsorbent dosage in solution, surface area of the adsorbent increased and as a result higher
amount adsorbate [Cr (VI)] gets adsorbed on the surface of the adsorbent. After certain period
of time the system reaching in equilibrium condition, an overlapping of active places prevailed
and the surface area of the adsorbent decreased, resulting in the conglomeration of exchanger
elements (Gupta and Balomajumdar 2017). With increase in initial concentration of Cr (VI),
higher amount of adsorbate adsorbed on the surface of adsorbent because of the higher
concentration gradient. The large amount of adsorbed Cr (VI) is thought to have an inhibitory
effect on further adsorption on the adsorbent surface (Amin et al. 2012; Mitra et al. 2015).
The solution pH is a significant factor that affects in adsorption process. It was observed that
with the increase of solution pH, the adsorption of Cr (VI) were increased up to a certain limit
and then decreased with further increase of solution pH. (Mitra et al. 2015) examined that the
maximum Cr (VI) removal in laterite soils was observed at pH 6. At lower pH values the soil
surfaces become positively charged due to strong protonation. The Cr (VI) adsorption increased
due to electrostatic forces between the positively charged of the soil surface and the negatively
charged Cr2O72− , HCrO4− ions in the interlayer region but at higher pH values (pH>pHzpc), the
soil surfaces become negatively charged due to de-protonation of the functional group (Eba et
al. 2010). The chromium removal efficiency of the soil decreased due to electrostatic repulsion
between chromate ions and negatively charged soil surfaces. A similar observation was reported
by (Plaska et al. 2012).
3.9 Modeling aspect of chromium adsorption phenomena
3.9.1 Fixed-bed adsorption
Continuous fixed-bed column or tank studies are important tool for the design of soil
liner for containment of pollutants in engineered landfill site and to also generate breakthrough
curves (BTCs) which includes certain complex and time dependent experiments which requires
close surveillance. This BTCs can be generated by plotting the dimensionless concentration
Ct/C0 ratio (where Ct is the effluent solute concentration and C0 is the influent solute
concentration) versus time.
The contaminant attenuation systems are designed on the basis of accurate predictions of
breakthrough curves for particular conditions. Fixed-bed adsorption studies are influenced by
kinetic (diffusion and convention coefficients), equilibrium (isotherm and capacity) and
hydraulic (liquid retention and geometric analysis) factors (Cavas et al. 2011; Chowdhury and
Saha 2013) as well as in designing liner in waste containment structures.
Batch adsorption studies are conducted to examine the efficacy of an adsorbent to adsorb
contaminants from aqueous phase as well as determining the adsorption capacity of the
adsorbent material (Jain et al. 2009). In most cases batch experimental test data limited to
laboratory scale and for this data cannot be accurately applied in industrial systems. On the
other hand, fixed bed adsorption experiment facilitates to replicate the field scale systems in real
life scenario (Ghosh et al. (2014).
Vinodhini and Das (2010) performed fixed bed column studies by using neem saw dust
as adsorbent for up taking of Cr (VI) from tannery waste water. From the test result they
observed that adsorption efficiency was higher (72.13%) at bed height 15cm and flow rate
5ml/min. The adsorption capacity of neem saw dust was 33.009 mg/g estimated from the BDST
model.
Karimi et al. (2012) conducted fixed bed column experiment to assess the removal of Cr
(VI) onto modified silica-polyacrylamide microspheres composite. The effect of various
parameters viz. initial solute concentration (50-200 mg/L), solute flow rate (3-10 ml/min) and
adsorbent bed height (0.5-1.5 cm) on the breakthrough characteristics of the adsorption system
were investigated. They observed that the percentage of Cr (VI) removal decreased from 76.69
to 66.29 with varying initial concentration of Cr (VI) from 50 to 200 mg/L. The breakthrough
time decreased from 79 to 14 min with the increase of flow rates from 3 to 10 ml/min. The
adsorption capacity as well as removal percentage increased from 44.79 to 56.33 mg/g, 64.31 to
82.82 % respectively with increased bed height from 0.5 to 1.5 cm.
Chen at el. (2012) carried out the fixed-bed column study for removal of hexavalent
chromium from aqueous solution by using modified corn stalk as adsorbent. The effect of
various parameters viz. bed depths (1.4, 2.2 & 2.9 cm), initial concentrations (100,200 and 300
mg/L), flow rate (5, 10 and 15 ml/min) and pH of influent solution (2.66, 4.91 & 5.66) etc. on
removal of hexavalent chromium were examined. Fixed bed column test results showed that
removal percentage of chromium was increased from 83.02-93.78% with increasing bed depth
from 1.4-2.9cm, but at higher influent concentration and flow rate removal percentage
decreased. It was also observed that metal uptake capacity increased from 372 to 420 mg/g at
acidic condition with the increase of pH from 2.66 to 4.91. The Thomas and Yoon–Nelson
models were used to predict the breakthrough curves, indicating that both models were closely
fitted for MCS column design.
Through literature review revealed that chromium removal studies carried out by using
different adsorbents (other than clayey/amended clayey soils) are mostly confined to batch
studies. Batch studies only imply the viability of sorption behavior of an adsorbent and
conclude its adsorption capacity through best-fitting isotherms and several kinetic models under
equilibrium state. As the pivotal elements in sorption are presence of coexisting ions and
characteristics of water under consideration for treatment, the adsorption capacity of natural
ground water derived from column studies, proves to be a more effective indicator for its field
application. The natural unsteady condition prevailing in the fixed bed makes a difficult task for
accurate prediction of the dynamic sorption responses (Baral et al. 2009), yet simple
mathematical models like Yoon–Nelson, Thomson, Adams–Bohart etc could be used to predict
the dynamic behavior of adsorption columns as well as for chromium sorption. The field
application of adsorbents (clayey soil) as a primary liner in the containment of chromium rich
waste waters, with its sorption profile described through fixed bed column studies are very less
reported in the literature.
3.9.2 Numerical modeling of solute transport mechanism using HYDRUS-1D and
application of CXTFIT model
Lithosphere pollution in India is a major geo-environmental problem due to
indiscriminate discharge of industrial effluent as well as disposal of hazardous and
nonhazardous solid waste in open land and thereby subsurface migration of contaminants
through soil media and subsequent mixing with groundwater cause subsurface environmental
pollution. Hence, habitants residing near a waste disposal site face colossal health effects due to
exposure of toxic contaminants susceptible to risk. So, proper selection of landfill liner material
is very much important for attenuation of lateral and vertical migratory movement of
contaminants within the ground and also to prevent groundwater pollution (Pu and Fox 2015).
Keeping in view of the gravity of the problem compacted clay soils of low saturated hydraulic
conductivity (kP< 1.0 x 10-07 cm/s) value and good contaminants adsorption capability are
considered to be cost-effective liner material in waste containment structures (Kalkan and
Akbulut 2004). However, laboratory scale column and batch experiments are performed to
assess the contaminants adsorption capacity and attenuative potential of pollutants migratory
movement through sub-surface soil media to prevent lithospheric pollution. Moreover, solute
transport numerical models help in predicting the migration of contaminants through soil media
and evaluating the optimum liner thickness in engineered contaminant structure. However,
several important parameters viz. adsorption isotherm co-efficient, hydraulic conductivity,
tortuosity of soils are required to evaluate for providing as input parameters in such model
(Saquing et al. 2012; Pal et al. 2014).
In addition, contaminant transport model HYDRUS-1D/2D/3D was also widely used to
simulate reactive solute transport in soils by putting the hydrodynamic parameters, best fitted
isotherm parameters (Ngoc et al. 2009; Adhikari et al. 2014). It is very significant to predict
accurately the fate and transport of toxic leachate through the subsurface soil. If the laboratory
scale experimental results fit with the HYDRUS model derived results then the model can be
used a tool to predict the optimized liner thickness in designing the waste containment
structures.
Inoue et al. (2000) carried out study to estimate hydro-dynamic and solute transport
parameters of soil from transient infiltration experiments. The combination of HYDRUS-1D
code and Levenberg marquardt optimization algorithm were used to simulate the experimental
results. From the experimental results, they observed maximum hydraulic conductivity (0.00862
cm/s), dispersivity (0.304 cm), and dispersion coefficient (0.0116 cm2/s) of the soil at
infiltration rate 0.00869 cm /s and pore water velocity 0.0382 cm/sec.
Li (2006) investigated the laboratory scale adsorption study to determine the transport
and adsorption parameters of mercury through different soil samples collected from different
sites in the western suburb of Beijing, China. A nonlinear least-square parameters optimization
method CXTFIT model was used to estimate the hydrodynamic dispersion co-efficient (D) in
vertical direction by providing bromide tracer data as input. Two solute transport models viz.
two-side non equilibrium model (TSN) and CDE were also used in his study to establish
mercury transport in saturated soil media. It was found that retardation factor (R) obtained from
TSN model was fitted well with experimental derived results as compared to CDE model.
Dousset et al. (2007) performed column study by considering bromide and isoproturon
solute transported through disturbed and undisturbed silty clay loam soil. The transport
parameters were estimated from bromide experimental breakthrough curves (BTCs) and by
using convective-dispersive and dual-permeability (DP) models in HYDRUS-1D. Then
isoproturon transport process parameters were determined by inverse analysis of the
experimental isoproturon BTCs using chemical equilibrium and non-equilibrium DP model in
HYDRUS-1D and inserting the previously estimated hydro-dynamic transport parameters in the
model. The chemical non-equilibrium DP model in HYDRUS-1D was found to be best
describing the isoproturon BTCs in both disturbed and undisturbed soils. Higher preferential
flow and a lower fraction of equilibrium sorption sites caused a faster movement of isoproturon
in undisturbed soil column.
Peng. S (2009) carried out column experiment by using boron as a tracer to estimate the
hydrodynamic parameters at two different soil bulk densities (1.92 and 1.62 g/cm³) under two
different flow rates (2 and 5 L/m².hˉ¹). He also used nonlinear least-square parameters
optimization method CXTFIT model to estimate the hydrodynamic dispersion co-efficient (D)
and mass transfer coefficient (ω). The model derived parameters was then used to predict the
solute BTCs of a 18m high leaching heap.
Disli E (2010) conducted laboratory scale batch and column experiments to investigate
the fate and transport mechanisms of reactive heavy metals (Cu, Zn and Mn) through
heterogeneous alluvial soils (clay, silty clay loam, sandy loam, loamy sand, silty loam and sand)
found in the region between Mogan Lake and Eymir Lake, Ankara, Turkey. Batch adsorption
results showed that the sorption process of Zn and Mn onto the surface of different size soils
was better described by Langmuir and Freundlich isotherm models and the sorption of Cu were
best described by the linear isotherm model. On the basis of the distribution coefficient (Kd) the
sequence of metal adsorption was found as follows: Cu>Zn>Mn. The Kd value for Cu was
found in the range between 18170.76 to 32550.35 L/kg. The one dimensional CDE was also
applied to the model. The experimental BTCs using saline solution NaCl for six (6) soil
columns selected by him and nonlinear least square optimization code “CXTFIT” (Toride et
al.,1995) were applied to estimate the dispersivity (α) of the soil samples. The highest
dispersivity (α=3.70cm) and lowest dispersivity (α=1.37cm) were found for clayey and sandy
soil respectively.
Leju et al. (2011) conducted column study for assessing BTC of atrazine through soil
and also to estimate the hydro-dynamic parameters by using HYDRUS-1D model. The test
result showed that the dispersivity values (3.09) slightly lower in disturbed column in
comparision to dispersity values (3.11) of undisturb column, which indicate that if the soil is
more heterogeneous then dispersity will be more. The average pulse duration for undisturb
column was five times more than in disturb columns. The simulation of observed BTC for
disturb and undisturb soil columns with predicted BTC by using HYDRUS-1D model were
showed symmetrical in nature.
Chotpantarat et al. (2011) performed vertical column experiment to investigate of
selective heavy metals such as Pb2+, Zn2+, Mn2+ and Ni2+ through lateritic soil at acidic
condition (pH 4 and 5). The breakthrough curves obtained from the experimental results showed
that Pb2+ has the highest retardation factor (33.3 and 38.7) and uptake capacity (0.091 and 0.134
mmol/g soil) at pH 4 and 5 respectively. The hydrodynamic dispersion co-efficient (D) in
lateritic soil was estimated by using the CXTFIT model and provided as a input in
HYDRUS-1D model to predict the migratory behavior of heavy metals in soil. The two-sites
chemical non equilibrium model (TSN) in HYDRUS-1D was found to be favorable to predict
the heavy metal transport in soil than equilibrium model using conventional isotherm equations.
Merdun (2012) examined the effects of different factors on water flow and solute
transport in sandy clay loam field soil. The experimental results showed that the applied CaCl2
solution move faster in the undisturbed, wet initial soil water content. Modelling results also
showed that performance of HYDRUS-1D model is better than VS2DTI model to predict
electrical conductivity and specially soil water content.
Chotpantarat et al. (2012) studied the migration of heavy metals under single, binary
and multi-metal systems(Pb 2+,Ni 2+
,Mn2+ ,Zn2+ ) through lateritic soil columns experimentally
and then modelled using CDE & TSM codes of HYDRUS 1D. They observed that the BTCs
were better described by TSM model than CDE model in both binary and multi-metal systems.
It was also observed that the equilibrium sites of all metals, particularly for secondary metals
increased with the increment of metal concentrations in the system which suggest the diffusion
dominated sorption and transport of heavy metal in the system.
Elmi et al. (2012) studied the transport of phosphate (PO43-) ion in reconstructed soil
columns using the HYDRUS-1D model. They found that the simulated results of the
HYDRUS-1D model were in close agreement to the observed results of the effluent PO43-
concentration during first 10 h of the experiment but the model over predicted towards the end
of the experiment. The poor goodness of fit in the aforesaid model was indicated by the value of
co-efficient of model efficiency (CME) i.e. 0.211<<1. The discrepancy of the simulated and
observed results was found due to the preferential flow within the soil column and inaccurate
estimation of reaction parameters using non-linear Freundlich isotherm equation as stated by the
investigators.
Saquing et al. (2012) used HYDRUS-1D model to simulate the transport process of
phenol in an anaerobic and fully saturated degraded newsprint (DNP) waste column in which
biodegradation and sorption were two prevailing driving forces for the attenuation of phenolic
compounds. The input parameters such as dispersivity and porosity factors as used in the
HYDRUS- 1D model were inversely estimated using CXTFIT code from bromide tracer BTCs.
The dispersivity and initial porosity in the soil columns were varied between 0.32 to 0.44 cm
and 0.51 to 0.58 respectively. The HYDRUS-1D model predicted results for various soil column
depths (20 to 60 cm) were found in close agreement with the observed results.
Pal et al. (2014) investigated the phenol-soil adsorption dynamics using HYDRUS- 1D model.
Batch adsorption data showed that the Freundlich isotherm model fitted well with regression
coefficient R2=0.94 for sorption of phenol on locally available fine grained clayey soil.
Laboratory scale vertical column test with different bed height as well as horizontal migration
test was performed to explore the movement of solute in both directions. The hydrodynamic
dispersion coefficients (D) in both direction (vertical and horizontal) were estimated using
CXTFIT program. HYDRUS- 1D model also applied to simulate the fate and transport of
phenol in both direction using Freundlich isotherm constants and estimated hydrodynamic
parameters as input parameters in the model.
Adhikari et al. (2014) performed column experiment and HYDRUS-1D modelling for
assessment of migration of phenolic compounds through the subsurface soil media. They
observed that with the increase of soil bed heights, the phenol uptake capacity and the length of
the mass transfer zone increased. The phenol BTC predicted for 1.2 m soil depth using
HYDRUS-1D model, indicated that the exhaustion point was reached within 12 days of elapsed
time and thus it clearly demonstrated poor efficacy of the soil to retard migration of phenol to
the groundwater. It was also suggested that suitable liner system should be designed to prevent
subsurface transport of phenol for protecting precious groundwater from pollution.
Though studies have been carried out by researchers earlier for application of
HYDRUS-1D model for analyzing the fate and transport of contaminants through subsurface
soil media, however, very limited studies are available on the application of the above model
and more particularly HYDRUS 3D model to simulate the migration of chromium compound
through clayey soil which is required for predicting the liner thickness in retarding the
sub-surface spreading of the contaminants in waste containment structures and inhibiting
lithosphere pollution.
Chapter 4 : JUSTIFICATION
OF
WORK
JUSTIFICATION OF THE PROPOSED INVESTIGATION WORK
● Since Azadirachta indica seed and Moringa oliefera seed shell dust amended clay
material to be used in the proposed research study and its adsorptive attenuation capacity
against Cr (VI) movements are to be examined which previously not much carried out in
detail by other investigators.
● Research work regarding modeling of fate of Cr (VI) through saturated soil media is
very much limited.
● Though the literature indicated the availability of simulation models for water and solute
transport in field soils in general, but not much work has been reported under Indian soil
conditions for fate of contaminants particularly with chromium compound contaminant.
● After thorough literature review, it was found that Cr (VI) migration from a waste
disposal site to the underground water using three dimensional software model like
HYDRUS-3D software package has not yet been applied using fixed bed adsorption
experimental data.
Chapter 5 : THEORETICAL
CONSIDERATION
 THEORETICAL CONSIDERATION OF FATE OF CHROMIUM (VI) THROUGH
AMENDED CLAY SOIL

The assessment of contaminant’s attenuative potential of sub-surface soil surrounding the

pollutant disposal sites as well as contaminants retardation potential of compacted clay liner in
waste containment structures require the knowledge of sorption behavior of soil inclusive of
evaluation of kinetic parameters, isotherm parameters, breakthrough times etc. of the pollutants
through batch adsorption and column studies using the chosen soil material and also
determination of physic-chemical characteristics of the particular soil. The design parameters
are obtained from a series of experimental observations and also using soft computing tools and
solute transport models (Aghav et al. 2011; Yilmaz and Kaynar, 2011).
In addition to the physico-chemical aspects of the chemical itself, the adsorption
phenomenon of a contaminant on a natural solid is a very complex method which includes
many sorbent properties. These characteristics are mainly the relative quantity and composition
of the mineral present in the soil / sediment, together with associated physical characteristics,
including pore characteristics and surface phenomena. Adsorption is a two dimensional
accumulation of matter at the solid / water interface and is described primarily in terms of
intermolecular interaction between solute and solid phases.
An adsorbent's adsorption capacity depends on various properties, viz. Distribution of particle
size, particular surface area, pH, organic matter, and constituents of minerals. Depending on the
chemical characteristics of the adsorbate, these properties influence the sorption behaviour more
or less. In the present study, special concentration of interest is Cr (VI) adsorption by
Azadirachta indica seed and Moringa oliefera seed shell dust blended fine grained clayey soils
with a view to explore its efficiency as primary liner material in waste containment structures
containing Cr (VI) laden waste.

5.1 Adsorption isotherm

The convergence of the solute on the strong surface includes adsorption from aqueous solutions.
The adsorption isotherm is the connection between the measure of solute adsorbed per unit
weight of the adsorbent and the balance fixation in the mass arrangement at a consistent
temperature.
5.2 Theoretical models

5.2.1 Isotherm model

The adsorption isotherm study is useful to determine the adsorptive capacity of an adsorbent for
removal of contaminant from wastewater. The Linear, Freundlich and Langmuir isotherm
models were studied for fitting with kinetic equilibrium experimental results by various
researchers earlier (Froehner et al. 2009; Djebbar et al. 2012).

5.2.1.1 Linear isotherm model

Linear isotherm is expressed as :
qe=KdCe (5.1)
Where Kd is the partition coefficient equal to the ratio of the concentration of solute
(sorbate) at equilibrium in the solid phase, qe, mg/Kg (also indicated as x/m, where 'x' is the
quantity of compound sorbed at sorbent mass m), to the concentration of the solute at the
equilibrium Ce (mg/L) in the aqueous phase. Typical units for Kd is cm3/Kg. Higher or lower
values of Kd entails lower or higher adsorption capacity of the sorbent respectively.

5.2.1.2 Langmuir isotherm model

Langmuir model (1918) is based on the assumption that the adsorption energy is
constant and independent of surface coverage. Adsorption occurs on a finite number of identical
sites and maximum adsorption takes place when the surface is covered by a monolayer of
adsorbate. The Langmuir isotherm equation is expressed as:

(5.2)

Where Qmax= Maximum adsorption capacity at monolayer (mg/Kg); b= Constant related

to the free energy of adsorption and a measure of affinity of binding sites (L/mg).

5.2.1.3 Freundlich isotherm model

The Freundlich model (1926) is based on the assumption that adsorption occurs on a
heterogeneous surface. The isotherm equation is expressed as follows:

(5.3)
Where, kf =Adsorbent capacity (mg/Kg) and n= adsorbent intensity (L/mg) respectively.
5.3 Quantitative Data Analysis

5.3.1 Statistical Analysis

The descriptive statistics of soil samples viz. mean, standard deviation, maximum and minimum
concentrations of pollutants as exhibited in the results and discussions section of this thesis were
evaluated using SPSS 17.0 statistical software package and correlations between the parameters
were assessed by using Pearson’s correlation method . Correlation examination is a starter
descriptive technique to appraise the level of relationship of factors in order to determine the
degree of association between two variables, while Pearson's correlation analysis was used in
the current study to determine the relationship between different sampling data. Factor analysis
was applied to datasets to explain the total variance of respective datasets. Most parameters
have been found to be significantly correlated with each other, indicating that these parameters
are closely associated with each other, so a single parameter could provide a reasonably good
indication of a number of parameters (Vasil Simeonov, 2005). Factor loading was utilized to
quantify the relationship among variables and factors after acquiring the connection matrix and
Eigen values, and afterward, the factors were turned by varimax rotation techniques to obtain a
fresh set of variables that are uncorrelated and arranged in decreasing order of importance.

5.4 Transport models

HYDRUS 3D model was applied in the present study for modeling the fate and transport
of Cr(VI) through amended clay soil. HYDRUS-3D is a numerical model that uses the finite
element method to solve the flow equation and the advection-dispersion-reaction equation
(ARDE) for transport of solutes in variably saturated porous media (Lee et al. 2012).
The HYDRUS-3D solute transport model also includes Marquardt-Lavenberg parameter
optimization algorithm for inverse estimation of soil hydraulics, solute transport and reaction
parameters from measured transient or steady state flow and transport data.
The governing differential equations are solved using the Galenkin-type linear finite element
technique for integration in space, and the backward finite difference scheme for integration in
time. HYDRUS-3D model can solve the solute transport equation under either the first
(Dirichlet) or third (Cauchy) boundary conditions and also provides a good simulation interface
between saturated and unsaturated conditions.
Chapter 6 : EXPERIMENTAL
PROCEDURE
 TEST PROGRAM AND EXPERIMENTAL PROCEDURE
6.1 Study Area

In this present study, two waste disposal sites were selected based on the possibility of
chromium pollution in sub-surface soil and groundwater due to migration of leachate through
sub-surface media from the sites.

6.1.1 Study Area 1 : A mixed (Municipal and Industrial) solid waste dump sites located at the
city Durgapur, West Bengal, India was operative for 10-12 years and presently abandoned due
to closure for the past 8 years was selected as study area. The boundaries of the study area are
defined through coordinate system by using hand held GPS instrument as shown in Figure 6.1 .
The landfill area was subdivided into 5 grids and subsurface soil samples collected from the
middle points of each grid.
 Fig 6.2 : Major soil
patterns in the study area

6.1.2 Study Area 2:

The study area is located in
the Leather Industrial zone
near Tangra region, situated at
the South Eastern part of
Kolkata, West Bengal,
India. Many small scale leather
industries have been
operating adjacent to that area for more than 50 years. Almost all the leather industries dispose
their tannery effluent directly to the nearby surface water bodies or on the land without any
pre-treatment. People residing nearby these waste disposal points are consuming the surface
water for their household purposes. Moreover, most of the houses have tube wells to withdraw
the groundwater for using as drinking as well as cooking purposes. The study area lies between
22° 33' 18'' to 22° 32' 59'' North latitudes 88° 22' 47” to 88° 22' 59” East longitudes.
6.3. Collection of samples from waste disposal sites
6.2.1 Sampling procedures
The soil samples were collected from the waste disposal sites by augur boring upto
predetermined depths below the subsurface. Groundwater samples were collected from 12
unlined dug wells in close proximity of the solid waste dump sites at Durgapur, West Bengal,
India. A total number of 11 soil samples were collected from a depth in between 20-50 cm and
stored in polyethylene bags and were immediately transported to the laboratory of Department
of Earth and Environmental Studies of NIT Durgapur, India.

6.3 Collection of samples near tannery waste disposal site

Groundwater as well as surface water samples were collected from deep tube wells and unlined
hand dug wells located in the nearby slum areas beside the leather industries . The surface water
samples were collected from the nearby ponds which are being used by the local dwellers for
household activities. One sample was collected from the effluent discharge point itself .
The soil sample was collected from the nearby area of the tannery effluent disposal site by
augur boring upto specific depth below the subsurface .
6.3.1 Soil Sample Preparation
A substantial amount (500 grams) of each soil sample was oven dried for three days at a
temperature of 60oC keeping in mind that temperatures above this would destroy biomass and
minimize volatilization of some analytes (US EPA 2002, Puget sound). The oven dried soils
were then pulverized using a wooden mallet and sieved through 425µm sieve to obtain a
homogenized sample. 20 grams from each oven dried sieved samples were taken into 100 ml of
distilled water to make a ratio of 1:5 in polyethylene bottles and placed on a rotary shaker with a
speed of 160 rpm (Yang et. al. 2018) for 2 hours and it was allowed to settle and then sieved
through 0.45µm filter paper. The filtrate was tested for pH, EC, TDS using a conductivity meter
made of LMPH-10 from Lab man scientific Instruments.

Figure 6.4: Leachate Generation Procedures

6.3.2 Leachate generation

To analyze the contaminant levels in the soil samples, 5 grams of the oven dried sieved sample
added to 100 grams of double distilled water to make a ratio of 1:20 in polyethylene bottles and
placed on a shaker at 160rpm (Francisco et. al. 2017) for 24 hours while maintaining a pH of
5.05 (range 5.0-5.2) using acid buffer. The resultant was then filtered through 0.22 µm filter
paper to ensure removal of organic impurities to prevent interference during analysis. The acid
buffer was prepared by adding 3ml of H2SO4 and 3ml of HNO3 to 100ml of distilled water and
added to ensure the pH was maintained within the required range.
 Figure 6.5 Vacuum Filtration
6.3.3 Preparation of sample for heavy metal analysis

To generate samples for heavy metal analysis, 100 grams of oven dried sieved soil was mixed
with 100 ml of 0.1N HCl, 100 ml of (1:9 v/v) H3PO4, 100 ml (0.1N HNO3) and 200 ml double
distilled water and digested for about 2 hours. 50 ml of HNO3 was then added in the mixture
and digested for further 30 minutes and thereafter boric acid solution was used to absorb the
fumes that are generated during the digestion process. The suspension was then allowed to cool
and transferred into 200 ml of distilled water and filtered through 0.47µm Whatman filter paper
and filtrate was analyzed for respective heavy metals as described in APHA 22nd Edition:
2012-3120B.

Figure 6.6 Acid Digestion- Laboratory Setup

6.4 Experimental Methods

 Following experimental procedures were followed in the present investigation in order
to achieve the desired objective in pursuance of the scope of work.
6.4.1 Test for physical properties of soil samples:
▪ Natural moisture content (IS 2720: Part 2:1973)
▪ Field bulk unit weight
▪ Particle size analysis (IS 2720: Part IV:1985)
▪ Specific gravity (IS 2720: Part III:Sec 2:1980)
▪ Atterberg limits:
Liquid Limit (IS 2720: Part V:1985)
Plastic Limit (IS 2720: Part V:1985)
▪ Light Compaction Test (IS 2720: Part 7:1980) (Reaffirmed 1997)
▪ Total porosity
▪ Saturated hydraulic conductivity (IS 2720: Part 17:1986) (Reaffirmed 1997)
▪ Organic carbon content (IS 2720: Part XXII:1972) (Reaffirmed 2010)
6.4.2 Test for chemical properties of soil samples:
▪ pH of Soil (IS 2720: Part 26:1987) (Reaffirmed 1997)
▪ Batch Adsorption Studies
▪ Isotherm studies
▪ Vertical Column Test
▪ Chemical properties of soil samples

6.4.3 Experimental procedures

6.4.3.1 Determination of physical properties of soil samples
6.4.3.1.1 Natural moisture content test
Natural moisture content of soil was determined by collecting the soil samples in a container
from the field and tested in the laboratory using a digital moisture meter (Model M-3A, make
Advance Research Instrument Co., India).

Calculation:
(100×𝑅)
𝑁𝑎𝑡𝑢𝑟𝑎𝑙 𝑚𝑜𝑖𝑠𝑡𝑢𝑟𝑒 𝑐𝑜𝑛𝑡𝑒𝑛𝑡 = 100−𝑅
(%) ( 6.1)

Where, R=Moisture meter reading of the collected soil sample

.
6.4.3.1.2 Field bulk unit weight test
The field bulk unit weight of the soil was determined by inserting sampling tubes (38
mm inner dia and 76 mm high) in the ground to collect the sample. The tubes were than sealed
with molten wax at top and bottom to preserve the natural moisture and transported to the
geotechnical laboratory, NIT Durgapur for testing. The bulk unit weight was then calculated by
dividing mass of sample to its volume.
6.4.3.1.3 Particle size analysis (combined mechanical and wet analysis)
Mechanical analysis was carried out by using a set of Indian Standard sieves to find
the grain size distributions of the soil particles up to dia 75μ. The size distributions of finer
particles (˂75μ) were determined by sedimentation analysis using hydrometer.
6.4.3.1.4 Specific gravity test
Specific gravity is the ratio of the mass/weight in air of a given volume of dry samples
to the mass/ weight of equal volume of distilled water at 4ºC. This test has been conducted on
the basis of IS 2720: Part III: Sec 2:1980. Specific gravity of the soil sample was determined by
using pycnometer.

6.4.3.1.5 Liquid limit & Plastic limit test

Casagrande apparatus was used for this test. Atterberg’s limits (Liquid limit & Plastic
limit) of the oven dried soil samples were determined according to IS-2720(Part V)-1985.
6.4.3.1.6 Light compaction test
Standard Proctor Tests were performed in the laboratory in order to achieve maximum
dry density (MDD) corresponding to optimum moisture content (OMC) of soil following the
guidelines depicted in the Bureau of Indian Standard (IS 2720: 1997).
6.4.3.1.7 Total Porosity
The total porosity of the soil was calculated using the following equation:

(
𝑛(%) = 1 −
γ𝑏
𝐺 ) × 100 (6.2)

Where, n= porosity of the soil sample; γb= Bulk density of undisturbed soil sample in
g/cc and G= specific gravity of the soil.
6.4.3.1.8 Saturated hydraulic conductivity
Falling head hydraulic conductivity test was performed for determining the permeability of
clayey soil. For falling head permeability test, the soil sample of length (L) was kept in a
vertical cylinder of cross sectional area (A) and the specimen was connected through the top
inlet to a stand pipe of cross sectional area (a). The test the soil sample was then saturated by
allowing water to pass through the sample from the stand pipe. After the completion of
saturation of soil sample, the stand pipe was again filled with water up to a height(H1).The
bottom outlet was opened and the time (t) required for the water level to fall down from a
known initial head(H1) to final head (H2) was measured above the center of the outlet. Three
successive observations were taken for determination of the permeability.
The permeability was calculated as
𝑎𝐿 𝐻1
𝑘 = 2. 303 𝐴𝑡
𝑙𝑜𝑔10 𝐻2

(6.3)
Where, k is the saturated hydraulic conductivity (cm/s), H1 and H2 are the head of water
in the stand pipe at two chosen time intervals t1 and t2.
6.4.3.1.9 Organic carbon content
Organic carbon content in soil was determined as per IS: 2720 (Part XXII) - 1972. (Reaffirmed
2010). Potassium dichromate (K2Cr2O7) and concentrated H2SO4 are added to between 0.5 g and
1 g of soil or sediment. The solution is mixed properly and allowed to cool (the solution must be
cooled because of the exothermic reaction when the potassium dichromate and sulfuric acids are
mixed) prior to adding water to pause the reaction. After the sample has cooled the addition of
H3PO4 to the digestive mix has been used to eliminate interferences from the ferric (Fe 3+) iron
that may be present in the sample although in most cases, this step is not necessary (Tiessen and
Moir, 1993)

Calculation:

( )= ( )
𝑤 𝑉𝑏𝑙𝑎𝑛𝑘−𝑉𝑠𝑎𝑚𝑝𝑙𝑒 ×0.3×𝑀
% 𝑜𝑓 𝑜𝑥𝑖𝑑𝑖𝑧𝑎𝑏𝑙𝑒 𝑐𝑎𝑟𝑏𝑜𝑛 𝑤 𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑠𝑜𝑖𝑙
(6.4)

% 𝑜𝑓 𝑡𝑜𝑡𝑎𝑙 𝑜𝑟𝑔𝑎𝑛𝑖𝑐 𝑐𝑎𝑟𝑏𝑜𝑛( ) = 1. 334 × % 𝑜𝑓 𝑜𝑥𝑖𝑑𝑖𝑧𝑎𝑏𝑙𝑒 𝑐𝑎𝑟𝑏𝑜𝑛

𝑤
𝑤
(6.5)

% 𝑜𝑓 𝑜𝑟𝑔𝑎𝑛𝑖𝑐 𝑚𝑎𝑡𝑡𝑒𝑟 = 1. 724 × % 𝑜𝑓 𝑡𝑜𝑡𝑎𝑙 𝑜𝑟𝑔𝑎𝑛𝑖𝑐 𝑐𝑎𝑟𝑏𝑜𝑛 (6.6)

M= molarity of ferrous ammonium sulphate (FAS)

0.3 = 3 X 10-3 X 100, where 3 is the equivalent weight of carbon

6.4.3.2 Test for chemical analysis

6.4.3.2.1 Determination of soil pH value
Electrometric method was used to measure pH of a given soil sample using a digital pH
meter (Model-pH 1100, make- EUTECH, Singapore). The instrument was calibrated first by
using standard buffer solution of known pH. The buffer solutions of pH 4.0, 7.0, 9.20 were used
to calibrate the instrument. The soil was mixed in the ratio of 1:5 with distilled water. Then it
was shaken in the rotary shaker so that the soil gets completely mixed with water. Then it was
filtered through whattmann filter paper 42 and the solution was collected and pH of the soil was
measured by pH meter.
6.4.3.2.2 Determination of Chromium(VI) concentration by colorimetric Method
Stock solution of Chromium was prepared by dissolving 141.4 mg K2Cr2O7 in distilled water
and dilute up to 1 L. (1ml=50mg/l).
Procedure:
Colour Development:
Adjust pH of solution to 1.0 ± 0.3 with 0.2N H2SO4.Transfer to 100ml volumetric flask, dilute
to 100ml and mix. Add 2.0ml of diphenylcarbazide solution mix and let the mixture to stand for
5-10 mins for full colour development. Measure absorbance at 540 nm .
Calculation :
μg Cr+6 ( in 102 ml final volume)
Cr+6 (mg/l) = X 100……...............................(6.7)
AXB
Where,
A = ml of original volume
B = ml portion from 1oo ml digested sample .
Standard curve for Chromium(VI)

Figure 6.7 : Standard Calibration Curve of Cr(VI)

6.5 Collection of adsorbents and characterization
The clayey soil samples to be used as liner material were collected from a soil quarry situated at
Andal, West Bengal, India. The samples were brought to the Soil Mechanics and Foundation
Engineering laboratory, NIT Durgapur for determining various physico-chemical properties.
Firstly, the soils were oven dried at 100 ±20 C temperatures for 24 hours and stored in a
desiccator until use. The physico-chemical properties viz. natural moisture content, liquid &
plastic limit, particle size distribution, organic matter, pH, Permeability of the collected soil
samples were determined following the guidelines depicted in the Bureau of Indian Standard (IS
2720).

6.6 Adsorbate preparation

The stock solution of Chromium (VI) was produced by dissolving Potassium dichromate
(K2Cr2O7) in 1.0 L of deionized water (50 mg/L). The desired concentration of Cr (VI) solutions
were prepared by diluting the stock solution with deionized water. The water used for preparing
chromium solution did not exhibit any background chromium concentrations. During all kinds
of laboratory analysis necessary quality assurance (QA) / quality control (QC) techniques as per
EPA (Environmental Protection Agency) guidelines were followed. The initial solution pH was
adjusted using 0.1 (N) HCl and 0.1 (N) NaOH solutions. The pH measurement was done with a
digital pH meter (Model-pH 1100, make-EUTECH, Singapore). UV-VIS Spectrophotometer
(Agilent 8453) was used to determine the concentration of Cr(VI) in the test solution, at a
wavelength of 540 nm for the maximum absorbance of Cr (VI) (APHA, 1995).
6.7 Zero Point charge test for clayey soil
This test was performed to determine zero-point charge of the soil. 0.1M NaNO3 was first
prepared. For each 100 mL of 0.1M NaNO3 solution taken, 1 g of the soil sample was added and
the pH was set accordingly using HCl and NaOH solutions. The pH range was kept between 2
to 12. The solutions were kept at a BOD shaker for 48 hours having a temperature of 27±1˚C
and a rotational speed of 150 rpm. After 48 hours, the samples were filtered and pH was
measured again. The point of zero charge pH was obtained by plotting a graph of initial pH vs
final pH measured.
6.8 Batch adsorption test for the unadulterated clay soil:
Batch adsorption tests were performed to examine the adsorption behavior of solid waste dump
site soils for Cr6+. Oven dried soil samples collected from the dumpsite area from depth of
below 50cm and passing through 600µm IS sieve was used in the study. 1000 ppm of Cr6+
solution was prepared by dissolving 2.8289g of potassium dichromate, (K2Cr2O7) in deionized
water and volume made to the 1000ml mark before carrying out a batch study to measure the
adsorptive capabilities. For batch studies, initial chromium concentration of (1.0, 2.0, 4.0, 5.0,
and 10 mg/L) were taken respectively in a series of 100-mL capacity conical flasks along with
soil as adsorbent doze of 30 g/L. In each batch a total of 6 samples including 1 blank were
prepared alternately in series and shaken at room temperature 25oC for varying contact times of
30mins, 90mins, 180mins and 360mins respectively at 160 rpm. The solutions were then filtered
through 0.22µm filter paper and residual Cr6+ concentrations in the filtrate were measured using
a UV-spectrophotometer at a wave length of 540nm. Although the adsorptive affinity of Cr6+ to
soil surfaces notably increase in acidic environments (pH˂7), (Al-Hamdan and Reddy, 2005), in
our case a pH of 6.5 was maintained in the solutions to ensure natural onsite conditions of our
soil samples as the average pH of the dumpsite soils was found to be 6.72. The pH of the
solution was adjusted using the buffer solutions. The percentage of Cr6+ removed was then
calculated from [(Co-Ce)/Co] x100 (Mohanty et al. 2005; Aroua et al. 2007; Owlad et al. 2008).

The percentage Cr (VI)removed by the adsorbent was then calculated by the following
equation (6.8).

𝑅= ( )
𝐶𝑖−𝐶𝑓
𝐶𝑖
× 100 ………………………………………………..( 6.8 )

Where, Where R is the percentage of Cr (VI) removal by the adsorbent, Ci and Cf are the initial
and final solution concentration at the end of the sorption process (mg/L) respectively.
6.9 Preparation of the natural adsorbent
The seed shells of the natural adsorbents were collected and cleaned. It was then broken into
pieces and cleaned by distilled water again and air dried for grinding into required sizes. These
grinded materials were then oven dried at a temperature up to 105±5ºC for 24 h. The adsorbent
was then blended with the clay soil in various percentages by weight of the soil mass. The
locally available clay soil of about 200 g was oven dried for 3 days at 60ºC keeping in mind that
temperature above this would destroy biomass and maximizes the volatilization of some
analytes (USEPA 2002). The oven dried soil samples were then pulverized by using a wooden
mallet and sieved through a 425-micron sieve . These adsorbents ( AI and MO) were mixed
with soil in (10%, 15% and 20%) by the weight of the clay soil taken respectively.
6.10 Batch adsorption test for the amended clay soil :
In the batch adsorption test, a pre-determined amount of adsorbent (amended clay soil) was
added with the synthetically prepared aqueous Cr (VI) solution of different concentrations in a
100 ml polyethylene bottle. The solution was stirred on a rotary shaker at a speed of 120 rpm
for a fixed reaction time. The solution pH was maintained to the desired value of 6.5 using 0.1
mol/L HCl or 0.1 mol/L NaOH. The supernatants of the agitated samples were subsequently
filtered through 0.45 µm filter paper by vacuum filtration process. The pH of the solution is
maintained at 6.5 because pHzpc of clay soil was found to be 6.75. The residual chromium (VI)
concentration was determined by using UV-Vis spectrometer at a wavelength of 540 nm with
the use of diphenylcarbazide complexing agent. All the readings were noted after 5–10 min of
waiting to allow the full colour development with respect to the blank sample. The absorbance
were noted and the concentration of chromium(VI) were calculated from the standard
calibration curve. The contact time (t) was maintained as 2 , 6, 8, 12 , 16 and 24 h. The initial
concentration (C0) of chromium (VI) was kept as 0.5, 1, 2, 4 and 5 ppm and the adsorbent dose
(W) was considered as 0.1, 0.15 and 0.20 g/100 ml of the solution. The percentage of
chromium(VI) removal (R%) and the solute adsorption capacity (qe) of the amended soil was
estimated based on eq. (6.9) and eq. (6.10), respectively.

𝐶0−𝐶𝑒
( )𝑅 =
0
0 𝐶0
× 100 …………………………………….............................. (6.9)

−1 (𝐶0−𝐶𝑒 )𝑣
𝑞𝑒(𝑚𝑔 𝑔 )= 𝑀
..........................................................................................(6.10)

where Ce and Co are the equilibrium and initial concentrations of the solute, respectively. All
the experiments were repeated in triplicate and the average values were considered.

6.11 Kinetic studies

Known amount of adsorbent was taken into conical flasks containing 100 ml synthetic
solution with initial chromium concentration ranging from 2 to 10 mg/L. The conical flasks
were then placed in an orbital rotary shaker and agitated at a speed of 150 RPM for different
predetermined time intervals (0.5,1, 2, 4, 6, 8, 12 and 24 h). The flasks were taken out serially at
different predetermined time intervals one after another from the shaker, and the treated
solutions were then filtered through filter paper (Whatman 42 grade). The residual
concentration of chromium (VI) at specified time interval was determined using UV-Visible
spectrophotometer.
The amount of chromium adsorption with time, qt (mg/Kg), was calculated by the
following equation (6.9).

𝑞𝑡 = ( )× 𝑣
𝐶𝑖−𝐶𝑟
𝑚
(6.11)

Where, Cr= Residual concentration of chromium (VI) with time.

6.12 Horizontal Tank test

Continuous adsorption test in tank was performed with 3 nos. perforated column with 3
cm internal diameter and 30 cm height as shown in Fig: 6.8. The amended clayey soil after
passing through 600 μm IS sieve was considered for preparing compacted soil bed in the
horizontal tank. The soil bed of desired height was made by compacting with rammer in three
layers with addition of water in such a way that the compacted density should be 90% of the
standard proctor’s density (Daniel, 1994). The water content in the soil should be 2% more than
the OMC as determined from soil compaction test. Glass wools and glass beads were placed at
the bottom of the column , the perforated surface of the column was surrounded with fine wire
mesh for resisting the perforations from getting clogged so that to maintain the uniform flow of
solution though the soil media and also to protect the same from the impact of water pressure. A
freshly prepared double distilled water was applied through the injection well in the form of
column under down flow mode at a flow rate of 6 mL/hr for about 24 h to saturate the soil prior
to start the solute transport process (Karimi et al. 2012). As the bed soil got saturated, chromium
solutions of predetermined initial concentrations were passed through to the top of the soil bed
at a specific flow rate and the effluent samples were obtained at predefined time intervals from
the bottom outlet of the column to analyze the effluent concentration of chromium by using
UV-VIS Spectrophotometer. The solute breakthrough curves of chromium migration through
the soil media were obtained by plotting the dimensionless concentrations (Cf/Ci) ratio versus
the number of days elapsed where, Cf and Ci are effluent and influent concentration of solutes in
mg/L. Blank test (soil having distilled water in absence of any chromium content) was also
performed in order to confirm the pre-existence of chromium in the studied soil as described by
Hanna et al. (2012).
Figure 6.8: Experimental setup used for the Cr6+ migration test.
1 - Synthetic Cr6+ solution; 2- Injection well; 3- Observation well no. 1; 4- Observation well no.
2; 5- compacted amended clay soil; 6-effluent of the Cr6+ solution from Observation well no. 2; 7-
effluent of the Cr6+ solution from Observation well no. 1; 8-Adjustable valve.
Chapter 7 : RESULT
&
DISCUSSION
Research Findings and Discussion of Results
7.1 Subsurface soil quality characteristics in the study area 1 (Solid waste dump site at
Durgapur, West Bengal, India)
The descriptive statistics of background pollutant concentrations in soil samples are presented
in Table 7.1. A wide variation of concentration ranges of heavy metals pollutants were observed
in the subsurface soil samples such as As: 1.05-0.48, Cd: 0.48-0.23, Pb: 2.33- 8.65, Fe: 4733 -
11413, Hg: 0.09 - 0.24, Cr: 6.43 - 12.5, Cu: 2.18 - 10.93, Al: 4657 - 13333, Ni : 3.80 - 7.90 and
Zn : 2.35 - 50.70 mgkg-1, respectivey. The heavy metal pollutant concentrations were compared
to the Canadian Council of Ministers of The Environment (CCME 2005) soil quality standards
to determine the extent of enrichment of heavy metals in the studied site. The arithmetic mean
concentrations of Fe, Al, Zn, Cu, Ni, Pb, Cd, As except Cr were observed below the threshold
value. The average concentartion of Cr was found close to 7 times higher its permissible value
which clearly indicated that the subsurface soil in the study area possessed alarming level of Cr
pollution. The presence of heavy metals could provide important information on the sources and
pathways of heavy metals at the study region. The high avarage concentration level of Fe (8010
mgkg-1) in the soil samples indicated that Iron and steel residue had been deposited at the site.
The presence of Zn at an average value of 18.29 mgkg-1 showed that the landfill received waste
from industries and moreover, the mean concentration level of Pb (4.63 mgkg-1) was indicative
of disposal of waste lead batteries, lead base varnishes and scrapes at the landfill. The high
average concentration level of Cr (10.16 mgkg-1), Cu (5.8 mgkg-1), Ni (5.02 mgkg-1) in soil
samples were also reinforced the anthropogenic deposition of industrial wastes in the landfill
alongwith municipal solid wastes. The average pH value (6.72) with a range in between 6.13
to7.75 also indicates the alkaline nature of the soil in the study area.
Table 7.1 Descriptive Statistics of soil samples collected from landfill
%TOC pH EC TDS NO3- SO42- Ca2+ Mg2+ Zn
(µs/cm)
(mg/kg) (mg/kg) (mg/kg) (mg/kg) (mg/kg) (mg/kg)

Mean

SD

Max

Min

Threshold

Table 7.1(continued) : Descriptive Statistics of soil samples collected from landfill

TH As Cd Pb Fe Hg Cr Cu Al Ni

(mg/k (mg/k (mg/k (mg/k (mg/k (mg/k (mg/k (mg/k (mg/k (mg/k
g) g) g) g) g) g) g) g) g) g)

Mean

SD

Max

Min

Thresh
old
Multivariate Pearson correlation analysis was applied to identify the possible statistical
relationship between different soil quality parameters. The correlation coefficients (r) among
various soil quality parameters are shown in Table 7.2. Correlation being a statistical measure
of the realationships between two parameters that ranges from -1 and +1. -1 being considered
perfectively –ve correlation and thus the two parameters would have completely no chance of
occuring together at the same time while +1 is considered perfectly +ve correlation to imply that
the two parameters would occur togehther at the same time and 0 (Zero) meant the two
parameters had no relation whatsoever. Significant positive correlations existed between Al-Ni,
Cu-Zn, Hg-Ni, Fe-Al, Pb-Zn, Cd-Cu and As-Cr pairs stating probable common source of the
dual in the study area.
Table 7.2: Correlation coefficient matrix of soil quality parameters.
TO P E TD NO3 SO42 Ca2 Mg2 T A C P F H C C A N Z
- - + +
C h C S H s d b e g r u l i n

TO
C
pH
EC
TDS
NO3-
SO42
-

Ca2+
Mg2
+

TH
As
Cd
Pb
Fe
Hg
Cr
Cu
Al
Ni
Zn
Factor analysis of the study area considering 18 such parameters extracted 3 factors as shown in
Table 7.3, where the Eigen value 11.827 associated with factor 1 explains 62.247% variance and
remaining two factors with Eigen values 4.856 and 1.52 explain 25.56% and 7.99% variance
respectively. Cumulative variance explained by these factors is 95.79%. The rotated factor
matrix presents loading of each parameter onto each factor as shown in Table 7.4. According to
the criteria of Liu et al. (2003), the factor loadings were termed as strong, moderate and weak
corresponding to absolute loading values of >0.75, 0.75-0.50 and 0.50-0.30 respectively. Factor
1 is characterized by strong positive loadings (>0.75) of TDS, TH, EC, SO42-, Ca2+, Pb, Cr and
Ni. Factor 2 had strong positive loading of Hg. The two factors cumulatively explain 87.80% of
total variance. Factor 1 explains the ionic pollution of the soil in the study area. The sources of
this ionic pollution were due to geogenic characteristics and partly due to disposal of industrial
waste. The physicochemical meaning of factor 1 also agrees with the correlation coefficient
between these variables. The high loading of Pb and Cr on factor 1 confirms that the occurrence
of the soil pollution in the study area was due to industrial waste disposal. The high loading of
Hg on factor 2 may be due to mercury laden waste disposal in the area in the past.
Table 7.3: Initial eigenvalues of soil quality data
Comp. Initial Eigenvalues

Total % of Cumulative
Variance %

1
2
3
4
5
6
7+
8
9
10
11
12
13
 14
15
16
17
18

Table 7.4: Varimax rotated factor loading matrix for landfill soil data (Kaiser
Normalization)
Variables Factor 1 Factor 2 Factor 3

%TOC
pH
EC
TDS
NO3-
SO42-
Ca2+
Mg2+
TH
As
Cd
Pb
Fe
Hg
Cr
Cu
 Al
Ni

7.2 Groundwater quality characteristics in the study area 1

Groundwater samples were collected from different wells in and around the study area as
exhibited in Table 7.5. The illustration of well parameters is shown in Fig. 7.1. The water table
depth (WTD) was determined by subtracting the depth of water table from ground level to RL
of ground level.
Table 7.5: Well Parameters
Well Well Depth DTW Height Latitudes Longitudes WTD
(feet) (m) above msl (N) (E) (m)
(m)

L1* 20 1.80 114 87.303 23.560 112.20

L2* 07 0.91 104 87.304 23.568 103.09

D1** 25 4.22 96 87.313 23.574 91.78

L3* 12 1.23 103 87.306 23.562 101.77

D2** 30 3.95 98 87.318 23.578 94.05

L4*** 33 5.92 87 87.329 23.539 81.08

L5*** 25 3.44 93 87.333 23.554 89.56

L6* 25 1.80 78 87.335 23.554 76.20

L7** 15 1.23 76 87.347 23.548 74.77

L8** 05 2.57 76 87.340 23.542 73.43

L9** 12 1.81 76 87.338 23.535 74.19

L10** 50 1.24 89 87.329 23.541 87.76

L11* 24 4.84 97 87.328 23.545 92.16

L12* 24 3.40 100 87.322 23.545 96.00

*Never Dries up **Dries up in summers ***Level Reduces in summers

 Figure 7.1: Illustration of DTW, WTD and Height above msl
7.3 Descriptive statistics of groundwater contaminants
Table 7.6: Descriptive Statistics for ground water samples (” =Permissible limit)
  pH TDS EC Ca2+ Mg2+ TH NO3- SO42+ Cu Cr Pb Fe Zn

                           

Mean

SD

Min

Max

WHO
”

Except pH and EC (μS/cm) all unit are in mg/L where applicable

The contaminations concentration levels were observed notably higher ( 0.09 mg/l of
hexavalent chromium) in the wells nearer to the landfill and the same were observed reducing
with increasing distance away from the landfill site. Fe concentration varied from 0.05 to 0.33
which may have been due to leachate percolation and its presence in groundwater usually
causes change in color of groundwater. The maximum Fe concentration was found to be above
permissible limit as per WHO standards portraying effect of leachate on groundwater. High EC
values obtained nearer to the landfill site was indicative of the effect of leachate on groundwater
quality.
The presence of metals like Pb, Cr are characterized as toxic for drinking water and subsurface
migration of these metals are usually dependent on parameters like soil sorption capacity, their
reaction rate and primary concentration and even if there may be migration of contaminants into
groundwater, however, the level was found below the threat value indicating that these metals
may be absorbed by the soil strata or by the organic matter in the soil.

7.4 Physical properties of soil at the waste disposal site at Durgapur

The physico-chemical characteristics of the soil samples collected from the study area
are exhibited in Table 7.7. The results showed that the percentage of fines (silt and clay) of the
soil was 57%. The soil is classified as silt with low compressibility (ML) according to the
Indian Standard Classification System (IS: 1498-1970). The soil was marginally alkaline (pH).
The saturated hydraulic conductivity (Ks= cm/s) of the soil was high and not fit as primary
liner material for containment of waste where industrial wastewater is discharged to land.
According to Güler and Avci (1993), the soil material used as the primary liner for containment
waste should have low hydraulic conductivity (<1.0×10-7cm/s).

Table 7.7: Physico-chemical characteristics of the test soils

Grain size NMCa LLb PLc Gd ne Ksf(cm/s) pH focg
distribution (%) (%) (%) (%)
San Silt Cla
d (%) y
(%) (%)

a
Natural moisture content; bLiquid limit; cPlastic limit; dSp. Gravity; ePorosity; fSaturated
hydraulic conductivity; g Organic carbon content.

7.5 Groundwater quality characteristics in the study area 2 (Leather industrial zone at
Kolkata, West Bengal, India
Descriptive statistical analysis of pollutant concentrations in groundwater samples collected
from the leather industrial zone at Kolkata, West Bengal, India are presented in Table 7.8, which
indicate a wide variation of pH, TH, COD, BOD and Cr (VI) (0.04 - 5.6 mg/l) in the studied
water. Most of the parameters with large standard deviation indicate their existence or randomly
fluctuating concentration levels in the groundwater. The mean concentration values of total
hardness (TH), SO42-, calcium (Ca2+), Mg2+, Cl-, and Cr (VI) were found exceeding to the
desirable level of both WHO and Indian Standards (IS 10500:2012).
 Table 7.8 : Descriptive statistics of groundwater samples collected near the leather
industrial zone
pH EC Turbidity Ca2+ Mg2+ COD TH TS BO Cl-
D
Mean

SD

Max

Min

WHO
standards
BIS

Except pH and EC (μS/cm) all unit are in mg/L where applicable

Table 7.8 (Continued) : Descriptive statistics of groundwater samples collected near the
leather industrial zone
TDS NO3- SO4- Cd Cr(VI) Pb Fe Zn Temp.°C

Mean

SD

Max

Min
WHO
standards
BIS
Except pH and EC (μS/cm) all unit are in mg/L where applicable
7.6 Soil Characteristics in the tannery waste disposal site at Kolkata

The physico-chemical properties of the soil at the tannery waste discharge site is shown in
Table 7.9. The soil was found with high silt content of about 41 %, which states the fact that
it was basically cohesive by nature. The soil was dark gray in color and acidic in nature (pH
4.88). The Atterberg limits of the soil were found as liquid limit-35.24%, plastic
limit-21.04%, plasticity index-14.20%. The soil can be categorized as MI (silt of medium
plastic) or OI (organic silt and clays of medium plastic) type (IS 1498). The saturated
hydraulic conductivity (Ks=6.37 x 10-5cm/s) of the soil was found out to be high. Based on
physical properties, the soil is considered as poor candidate for using as a primary liner
material for waste containment structures. According to Güler and Avci (1993), any soil
material which is to be used as the primary liner for containment of waste should have low
hydraulic conductivity (<1.0×10-7cm/s).
Table 7.9: The physical and chemical characteristics of the test soils
Sand (%)
Silt (%)
Grain Size Clay (%)
distribution
NMCa (%)
LLb (%)
PLc (%)
Gd
ne
Ksf (cm/s)
pH
focg
Cr ( mg/kg)
a
Natural moisture content; bLiquid limit; cPlastic limit; dSp. Gravity; ePorosity; fSaturated
hydraulic conductivity; gOrganic carbon content

7.7 Batch Adsorption Study for Cr (VI) removal by the landfill soil of site 1 (Durgapur)
In the present study, Cr (VI) was considered as test contaminant as it was observed as prime
pollutant in the groundwater as well as subsurface soil samples collected from both the sites.
The chromium (VI) adsorption studies were carried out using landfill soil as adsorbent to
examine its adsorptive potential as shown in Table 7.10. The outcome of the laboratory scale
batch adsorption test results indicate that the soil has reasonable Cr (VI) adsorption capability
at slightly acidic pH conditions. It was observed from Table 7.10 that the Cr (VI) removal
percent increases mostly with the increase in initial Cr (VI) concentration up to 4 mg/L and
then found to be decreased with further increase of initial Cr (VI) concentration. The reasons
behind this may be after reaching limiting equilibrium i.e. initial Cr (VI) concentration of 4
mg/L, the adsorbed Cr (VI) on surface of soil particles inhibits the direct contact of Cr (VI)
with the adsorbent surface and consequently Cr (VI) removal efficiency decreases with a
further increment of initial Cr (VI) concentration. Higher percent of Cr (VI) removal at initial
stage was due to formation of high degree of concentration gradient between the solute and
adsorbent phase. But with the increase of reaction time, the concentration gradient descended
and subsequently resulted in less Cr (VI) removal. The maximum Cr (VI) uptake capacity of
the studied soil was found to be 282.9 mg/kg at fixed adsorbent dosage (20 g/L), initial Cr
(VI) concentration (10 mg/L) for a constant time of 90 min at solution pH of 6.5.
Table 7.10: Batch adsorption test results of Cr (VI) using landfill soil as adsorbent
Contact Time (minutes)

30 90 180 360

Ce % qe Ce % qe Ce % qe Ce % qe
rem. rem. rem. rem.

Ce and Co are the equilibrium and initial Cr6+ concentration in (mg/L); % rem= Percentage Cr
(VI) removal; qe = Adsorption capacity in mg/kg

In spite of reasonable Cr (VI) adsorption capacity of the landfill soil, the same could not be
treated as a candidate for using as primary liner material in chromium laden waste
containment structures due to its high value of hydraulic conductivity as shown in Table 7.7.
There is a high probability of subsurface percolation of Cr (VI) laden leachate through the
studied soil and therefore, the groundwater quality in the surrounding area of the waste
disposal site may be severely degraded which in turn may cause colossal health effects to the
inhabitants.
7.8 Efficacy of amended clay soil as liner material for attenuation of Cr (VI) in waste
disposal site
7.8.1 Test results on clay soil quality
An attempt was made in the present study to use naturally available clayey soil as primary
liner material in the engineered landfill structure to impede the sub-surface migration of the
contaminants from the waste disposal site. The physico-chemical properties of the clay soil to
be used as liner material is depicted in Table 7.11.
The type of the soil was found predominantly cohesive in nature with high clay content
(56%). The color of the soil was dark gray. The Atterberg limits of the soil were: liquid
limit-47.12%, plastic limit-29.33%, plasticity index-17.79%. The soil can be classified as silts
and clays of medium compressibility (MI) or organic silts and clays of high compressibility
(OI) type (IS-1498:1970). The soil was alkaline in nature (pH 7.70). The saturated hydraulic
conductivity (Ks=6.5 x 10-7 cm/s) of the soil was very low. Hence the soil possesses good
resistance against transport of leachate to surrounding groundwater (Ghosh et al. 2007) and
can be used as effective liner material with reasonable adsorptive properties. The background
Cr (VI) concentration in the studied soil were also tested and no preexistence was observed.
Table7.11 : Physico-chemical properties of the clay soil
Properties Clay soil
Specific gravity
Maximum Dry density
Optimum moisture
content
Grain size distribution
Liquid limit(%)
Plastic limit(%)
Plasticity index (%)
pH
Cr6+ (mg/l)
Permeability (cm/sec)
7.8.2 Batch Adsorption test for the clayey soil used for liner material:
An attempt was made in the present study to use naturally available clayey soil as primary
liner material in the engineered landfill structure to impede the sub-surface migration of the
contaminants from the waste disposal site. The physico-chemical properties of the clay soil to
be used as liner material is depicted in Table 7.11. Laboratory scale batch adsorption studies
(Figure 7.2) were carried out with synthetically prepared Cr (VI) solution as test contaminant
and clay soil as adsorbent. The contact time (t) was maintained as 2, 6, 12 and 24 hours. The
initial concentration (C0) of chromium (VI) was kept as 0.5, 1, 2, 4 and 5 ppm and the
adsorbent dose was considered as 1g/100 ml of the solution. The study revealed that
maximum Cr (VI) removal efficacy of 74% was achieved by the clay soil as shown in Figure
7.2. Though the hydraulic conductivity of the clay soil is very low (6.5 x 10-7 cm/sec), the
poor contaminant (Cr6+) adsorption capacity of the same doesn’t make it suitable candidate of
using as liner material in waste containment structures.
Figure 7.2: Graphical representation of batch adsorption test results of Cr (VI) on
naturally available clay soil.
An attempt was made in the present study to examine the possibility of enhancement of Cr
(VI) adsorption capacity of the clay soil with the addition of two different natural adsorbents
(Azadirachta indica and Moringa oleifera) in various proportions. Effect studies were carried
out to ascertain the maximum possible removal of hexavalent chromium from the aqueous
medium at optimum values of process parameters.

7.8.2.1 Effect of pH on chromium (VI) adsorption in aqueous media

The effect of pH on Cr (VI) removal by amended clayey soil was investigated by varying pH
of the solution in between 2 and 14 as shown in Fig. 7.4 and 7.5. The experimental results
indicated that the removal of Cr (VI) at pH lower than 2.0 is found to be negligible. The
removal efficiency increased with the increase of pH from 2 to 7 and then decreased with
further increase of pH in the solution. The sudden fall in chromate adsorption at higher pH
values due to the existence of various forms of Cr (VI) anions in the aqueous phase which
caused repulsion with the negatively charged clay surface. The dominant forms of Cr (VI)
were Cr2O72− and HCrO4− ions at higher pH values (Li and Bowman 2000). At a low pH, the
surface of clay become positively charged due to strong protonation. The electrostatic forces
2−
between the positively charged surface and the negatively charged Cr2O7 and HCrO4− ions
in the interfacial region enhanced Cr (VI) adsorption. Therefore, a larger amount of Cr (VI)
was adsorbed by the clayey soil at a low pH of the solution. The surface charge of the soil as
well as the ionization of organic contaminants was influenced by the solution pH (Kermani et
al. 2006). At lower pH value (pH< pHzpc), the soil surface was found highly protonated (H+).
The pHzpc value of the amended clay soil was observed as 6.75 as shown in Fig.7.3.
Therefore, maximum Cr (VI) adsorption took place at solution pH less than 6.75. A similar
observation was reported by (Plaska et al. 2012) in their study on Cr (VI) adsorption in soil
media. Hence, further batch adsorption studies using amended clay soil as adsorbent were
conducted at a pH of 6.5.

Figure 7.3: Graphical representation of pHZPC test results on amended clay soil

Fig.7.4:Graphical representation of effect of pH on absorption of Chromium (VI) with

natural adsorbent as Azadirachta indica .
Fig. 7.5:.Graphical representation of effect of pH on absorption of Chromium (VI) with
natural adsorbent as Moringa oleifera.
 Chapter 8 : CONCLUSION

8.1 Conclusions
 The transportation of foreign substances through soil media enhances geo-ecological
issues, leading to lithospheric contamination. Close surface aquifers are frequently vulnerable
to pollution from surface sources, if overlying soil has a poor pollutant constriction limit.
Utilizing laboratory scale batch adsorption and pollutants migration study through tank test as
well as validation through numerical modeling using solute transport software like
HYDRUS-3D considering soil versatility, the development of impurities through the
subsurface up to the aquifers can be anticipated. The efficacy of fine grained amended clayey
soils was assessed in the present study for using the same as liner material in engineered
waste containment structures for attenuation of Cr (VI) migration to the sub surface soil and
aquifer and thereby protecting the precious lithospheric environment. Based on present study
and fitting of experimental data on various models, the following conclusions are drawn:

• The mean concentration level of hexavalent chromium was found to exceed almost 7
times the threshold value in the solid waste disposal site as well as the groundwater
near the leather industry.
• The higher value of hexavalent chromium in the subsurface soil of the solid waste
disposal site at Durgapur is a major cause of concern to the people residing nearby the
area. However, the concentration of Cr (VI) in the groundwater samples was found is
still less and which happened may be due to higher Cr (VI) adsorption potential of the
sub-surface soil and leachate containing Cr (VI) might not still percolate to the
groundwater.
• Statistical analysis of soil samples at solid waste disposal site at Durgapur
demonstrated that two major group of pollutants namely ionic and chromium
compound exist in the study area. The sources of this ionic pollution were due to
geo-genic characteristics and partly due to disposal of industrial waste. The
physicochemical meaning of factor 1 also agrees with the correlation coefficient
between these variables. The high loading of Pb and Cr on factor 1 confirms that the
occurrence of the soil pollution in the study area was due to industrial waste disposal.
• Near surface aquifer (1.23 m) and higher saturated hydraulic conductivity (4.27 x10-4
cm/s) of subsurface soil in the study area increases the possibility of groundwater
contamination from surface source.
• A higher value of chromium concentration (5.92 mg/kg) was observed by analysing
the sub-surface soil data in the nearby areas of the leather industrial zone at Kolkata.
• Due to the higher saturated hydraulic conductivity (6.37 x 10-5 cm/sec) of the
sub-surface soil near the leather industries, it increases the chances of groundwater
contamination from surface source.
• Batch adsorption study results showed poor chromium resilience of the subsurface
soil in the study areas.
• The uptake potential of locally available fine grained clayey soil as adsorbent were
also examined for design of suitable liner system to retard the migration of hexavalent
chromium in the surrounding area of the chromium laden waste disposal sites.
• Physico-chemical characterization revealed a good fit of the naturally available clay
soil as a liner material, due to its lower value of saturated hydraulic conductivity (6.5
x 107 cm/sec).
• The clayey soil showed a reasonable hexavalent chromium uptake capacity (65.78
mg/Kg).
• Batch study results showed maximum 74% chromium removal for the unadulterated
clay soil dose of 1 g with an initial chromium concentration of 0.5 mg/L varying up to
5 mg/L at an equilibrium time of 12 hours and optimum pH level of 6.5.
• The pH level obtained from zero-point charge test for the liner clayey soil was 6.75.
Therefore, further studies were carried out by considering pH 6.5.
• The Cr (VI) adsorption efficiency was found enhanced remarkably when AI/MO seed
shell dusts amended clayey soil was introduced as adsorbent. The Cr (VI) removal
efficiencies of 91 and 80 % were achieved when clayey soil was blended with 20 %
by weight of AI and MO, respectively.
• Desorption study result of Cr (VI) adsorbed AI blended clay soil showed very less (5
%) desorption of Cr (VI) in the solution. SEM Analysis results shows a distinct
change in the soil microstructure leading to a possibility of chemisorption.
• To reinforce the statement of chemisorption, XRD analysis result showed a sharp
peak at 2θ=44.6° which indicated the presence of chromium in AI blended clay soil
according to the data obtained from PCPDF WIN software.
• BTCs for hexavalent chromium generated from laboratory scale horizontal tank test
as well as numerical modelling through HYDRUS -3D are symmetrical in nature
which reinforces equilibrium condition of solute transport in the saturated soil media.
• The HYDRUS 3D predicted results were found reasonably corroborating with the
laboratory test results on fate and transport of chromium in the saturated soil media.
• Up scaling the hydrodynamic parameters, the HYDRUS 3D model can be applied in
real life situation for designing a landfill liner system.
• The HYDRUS 3D model was further extended to predict the migration of the Cr (VI)
contaminant in amended clay soil of 1m thick for the purpose of using the same as
bottom liner material in waste containment structure. The breakthrough curve
predicted by the HYDRUS 3D model showed that the liner bed exhaustion is
happening after a period of 38 years. The outcome of the present study is clearly
indicating that the AI amended clay soil has high potential in restricting the
subsurface spreading of contaminants emanating from chromium laden wastes
disposed to open land or water bodies and thereby, the same may be considered as an
excellent candidate as liner material in chromium laden waste containment structures.
• Though the study was conducted looking in front of a real life waste disposal site
containing chromium, the methodology can also be extended for other toxicants as
leach out from similar type of site containing other than chromium also.
Chapter 9 : FUTURE SCOPE OF
WORK

FUTURE SCOPE OF WORK

Following components are proposed as future scope of the works and congruence with
current investigation of transportation of Cr (VI) from industrial wastewater as well as
solid waste disposal site in sub-surface soil media.
• In the present investigation, the laboratory batch and horizontal migration study were
conducted using synthetically prepared Cr (VI) solutions. Testing with real life Cr
(VI) aqueous solutions is to be carried out further to examine the efficacy of the AI
amended clay soil as adsorbent.
• Field scale studies are to be conducted for verification of the physical as well as
numerical modelling on Cr (VI) transport in soil media.
• The study should also be conducted for higher concentration range of hexavalent
Chromium.
• MOD-FLOW and other solute transport models are to be applied to explain the
mechanism in a better way.
• Other kinetic models on isotherm studies including temperature variations should also
be done.
• Test for achieving higher efficiency of uptake composite liner system with clay plus
synthetic material, amended soil with different admixtures to be examined in the
future.

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