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REMEDIATION OF CONTAMINATED SOIL USING SYNTHETIC
AND NATURAL SURFACTANT SOLUTION AND COLLOIDALGAS APHRONS
Soumyadeep Mukhopadhyay
Candidature Level
Doctor of Philosophy (PhD)
Department of Chemical EngineeringFaculty of Engineering
12th Feb 2014,
ISO Meeting Room, Engg Tower, UM
Supervisors
Prof Mohd Ali Hashim
Dr Jaya Narayan Sahu
Dr Bhaskar Sen Gupta (QUB)
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Soil contamination
Soil is the most important resource available to man
Soil pollution causes loss of productivity.
In USA and Europe, there are more than 1.5 million contaminated sites that
needs to be treated.
I am concentrating on removal of arsenic, cadmium and zinc from soil. All of
them are highly toxic.
Introduction
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High concentrations of cobult, nickel, lead, zinc, arsenic, cadmiumand copper has been found in
Malaysian soil, originating from fertilisers, mining activities and industrial spills (Zarcinas et al.
(2004)).
Arsenicis an extremely toxic metalloid. Mining, smelting, coal burning, wood preservation, fertiliser,
pesticide and illegal waste dumping activities result in arsenic pollution in the environment
Cadmium has toxicity 2 to 20 times higher than many other heavy metals and is a common toxic metal
found as pollutant. It represents the heavy metals of period V.
Zinc phytotoxicity has been demonstrated in soils contaminated by smelters and mining waste,
incinerators, excessive applications of fertilizers and pesticides, burned rubber residues, galvanized
materials, livestock manures and biosolid sewage sludge. It represents the heavy metals of period IV.
Zarcinas, B., Ishak, C., McLaughlin, M., & Cozens, G. (2004). Heavy metals in soils and crops in Southeast Asia.
Environmental Geochemistry and Health, 26(4), 343-357.
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Why Arsenic, Zinc and Cadmium ?
Introduction
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Ex-situ soil washing
Introduction
In-situ soil flushing by micro bubbles
Soil washing is the best option to reduce the environmental risk from soil contamination.
Soil washing can be ex-situ and in-situ process.
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Natural surfactants for soil washing
Soil washing by acids, alkalis, chelates and solvents corrode the soil.
So it is important to identify a natural washing agent that does not affect soil
productivity.
Soapnut, a natural surfactant is such an environment friendly agent.
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Introduction
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Sapindus mukorossior soapnut is a common tree in
sub-tropical regions. The fruit pericarp contains
saponin, a natural surfactant.
Earlier, soapnut has been used for removing
hexachlorobenzene and organic pollutants from soil.
Some researchers used soapnut for removing
cadmium and zinc from soil. Soapnut has never beenused for arsenic removal from soil.
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Sapindus mukorossi
Introduction
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The performance of soapnut has been compared with acommonly used inorganic surfactant Sodium Dodecyl
Sulphate (SDS) under different conditions, e.g.
Soil pHFlow modes
Surfactant concentrations
Soil: solution ratio
Effects of additives (phosphate and EDTA)
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Introduction
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Colloidal gas aphrons (CGAs)
CGAs is a system of microfoam, having some colloidal
properties. Bubbles are above 25 m diameter. They were
first described by Sebba (1987).
CGAs can be pumped and they are very stable under
constant stirring condition. Schematic diagram of structure of CGAs
(Sebba, 1987)
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Introduction
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1. CGAs: Characterization and propagation through soil column.
2. Arsenic removal by solution and CGAs of soapnut and SDS. Effect of phosphate.
3. Zinc and Cadmium removal by solution of soapnut and SDS. Effect of EDTA on
the process.
4. Mechanism and kinetics of the soil washing process by soapnut and SDS.
5. Environmental friendliness of the process: damage to soil, recovery and reuse of
wash effluent.
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Objectives
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Soil sampling and spiking: Sampled from 1stlayer aquiferof Hulu Langat Basin
Soil characterization : XRD, pH, density, classification,
metal content
Extraction of saponin from soapnut: Fruit pericarp
dissolved in water, filtered and evaporated.
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Research Methodology
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Research Methodology
Scheme of research
R h M h d l
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Effect of Surfactant concentrations
Standard conditions
Soil/Solution ratio: wt:vol = 1:20 (1 g soil : 20 mL solution)
Temperature = 25oC
Shaking time 4 hrs
100 mM Phosphate
Variable conditions:Soapnut (0.5%, 0.75%, 1%, 1.25%, 1.5%)
SDS (10 mM, 15 mM, 20 mM, 25 mM, 30 mM)
Mixture of Phosphate and Soapnut
(100 mM Ph + 0.5% SN, 100 mM Ph + 0.75% SN, 100 mM Ph + 1% SN, 100
mM Ph + 1.25% SN, 100 mM Ph + 1.5% SN)
Effect of Phosphate concentrations
Standard conditions
Soil/Solution ratio: wt:vol = 1:20 (1 g soil : 20 mL solution)
Temperature = 25o
CShaking time 4 hrs
Surfactants= 1% Soapnut and 20 mM SDS
Variable conditions:
Phosphate (50mM, 75mM, 100mM, 125mM, 150mM)
Mixture of Phosphate and Soapnut
(50 mM Ph + 1% SN, 75 mM Ph + 1% SN, 100 mM Ph + 1% SN, 125 mM Ph +
1% SN, 150 mM Ph + 1% SN)
Effect of Soil:Solution ratio
Standard conditions:
Temperature = 25oC
Composition of aqueous solution:
20mM SDS
Wash solutions= 1% Soapnut, 100mM Phosphate, 1% Soapnut + 100mM
Phosphate
Shaking time 4 hrs
Variable conditions:
S/S ratios: w/V = (1/10, 1/20, 1/30), (1g soil : 10ml, 20ml, and 30ml solution)
Experimental conditions and
variables for arsenic removal
Research Methodology
Batch Experiments
Shake Flask Study
R h M th d l
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Experimental conditions and variables for zinc removal
Research Methodology
Batch ExperimentsShake Flask Study
Effect of Surfactant concentrations
Standard conditions
Soil/Solution ratio: wt:vol = 1:20 (1 g soil : 20 mL solution)
Temperature = 25oC
Shaking time 4 hrs
Unadjusted pH
Variable conditions:
Soapnut (0.5%, 1%, 1.5%, 2%, 2.5%)
SDS (10 mM, 20 mM, 30 mM)
Effect of pH
Standard conditions
Soil/Solution ratio: wt:vol = 1:20 (1 g soil : 20 mL solution)
Temperature = 25oC
Shaking time 4 hrs
Surfactants= 1% Soapnut and 20 mM SDS
Variable conditions:
pH = 4,5,6,7
Effect of Soil:Solution ratio
Standard conditions:
Temperature = 25oC
Composition of aqueous solution:Surfactants= 1% Soapnut and 20 mM SDS
Shaking time 4 hrs
Unadjusted pH
Variable conditions:
Soil: Solution ratios: w/V = 1:10, 1:20, 1:30
Effect of Surfactant concentrationsStandard conditions
Soil/Solution ratio: wt:vol = 1:20 (1 g soil : 20 mL solution)
Temperature = 25oC
Shaking time 4 hrs
Unadjusted pH
No EDTA
Variable conditions:
Soapnut (0.5%, 1%, 1.5%, 2%, 2.5%)
SDS (10 mM, 20 mM, 30 mM)
Effect of EDTA
Standard conditions
Soil/Solution ratio: wt:vol = 1:20 (1 g soil : 20 mL solution)
Temperature = 25oC
Shaking time 4 hrs
Surfactants= 1% Soapnut and 20 mM SDS
Variable conditions:
EDTA concentration = None, 0.05M, 0.1M
Effect of Soil:Solution ratio
Standard conditions:
Temperature = 25oC
Composition of aqueous solution:Surfactants= 1% Soapnut and 20 mM SDS
Shaking time 4 hrs
Unadjusted pH
No EDTA
Variable conditions:
Soil: Solution ratios: w/V = 1:10, 1:20, 1:30
Experimental conditions and variables for cadmium removal
R h M th d l
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Generation of CGAs
CGAs were generated by a using a
homogenizer IKA Ultra-Turrax T25 at 6000
rpm for 5 minutes.
To maintain the homogeneity of the CGA
solution, it was continuously stirred by a
magnetic stirrer at 1000 rpm.
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Research Methodology
Research Methodolog
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Characterization of CGAs
Liquid drainage of CGA
Stability of CGA
Air holdup
Average hydraulic conductivity
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Research Methodology
Research Methodology
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Research Methodology
Soil column washing experiment by CGA and surfactant solutions
Research Methodology
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Column Washing Experimental Setup
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Research Methodology
Research Methodology
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Parameter Level 1 Level 2 Level 3
Type of washing agent SDS Soapnut Soapnut + Phosphate
Physical state of wash agent Solution CGAs ---
Concentrationof washing
agent
SDS (mM) 10 mM 20 mM ---
Soapnut (%) 0.5% 1% ---
Soapnut (%) +
Phosphate (mM)
0.5% + 50
mM1% + 100 mM ---
Soil pH 5 6 ---
Flow mode Down flow Up flow ---
Control factors and their levels for column experiments
Research Methodology
Research Methodology
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Standard conditions
Soil/Solution ratio: wt:vol = 1:20 (10 g soil : 200 mL solution)
Temperature = 25oC
Shaking time= 4 hrs
Shaking speed= 135 rpm
Unadjusted pHSampling times= 5, 10, 15, 20, 25, 30, 45, 60, 120 mins, 4, 6, 10, 15, 24, 48 hours
Sampling volume= 5 mL
Variable conditions
Wash solutions for arsenic= 1% soapnut, 1% soapnut+ 100 mM phosphate, 20 mM SDS
Wash solutions for zinc= 1% soapnut, 20 mM SDS
Wash solutions for cadmium= 1% soapnut, 1% soapnut+0.05M EDTA
Experimental conditions and variables for kinetic experiments
Research Methodology
Research Methodology
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Mechanism of As(V) desorption
FT-IR spectra.
Zeta potential measurement.
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Research Methodology
The wash solutions were analyzed for Ca, Mg, Si, Fe, Al to check for any structural
damage of soil.
Scanning Electron Microscope.
Damage to soil
Recovery of wash solution
Jar test were performed with 200 mL of 0.5, 1 and 1.5% soapnut solutions containing 10 mg/L As
in 500 mL beakers by adding different doses of FeCl3 using the standard jar test apparatus. ThepH of soapnut solutions are adjusted by HCl or NaOH.
1 min of rapid mixing at 120 rpm, 30 min of slow mixing at 40 rpm, followed by 30 min of
settling.
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Soil Characterization
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a. Characterization of natural soil sample
Soil properties Value Method
pH 4.5 USEPA SW-846 Method 9045D
Specific Gravity 2.64 ASTM D 854 - Water Pycnometer method
CEC (Meq) 5 Ammonium acetate method for acidic soil (Chapman, 1965)
Organic matter content 0.14 % Loss of weight on ignition (Storer, 1984)
Bulk Density (gm cc-1) 2.348
Total porosity (%) 39 (Di Palma et al., 2003)
Total arsenic (mg kg-1) 3
USEPA 3050B
Total iron (mg kg-1) 3719Total silicon (mg kg-1) ~390,000
Aluminium (mg kg-1) 2400
Total manganese (mg kg-1) 185
Magnesium (mg kg-1) 635
Lead (mg kg-1) 11
Zinc (mg kg-1) 18
Soil particle size distribution
Sand (< 50 m) 92.66 %
Sandy soil according to USDA Soil ClassificationSilt (50-2 m) 5.2 %
Clay (> 2 m) 2 %
Research Findings
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Arsenic(V) content of soil = 83 mg Kg-1
Zinc content of soil = 540 mg Kg-1
Cadmium content of soil = 47.5 mg Kg-1
Research Findings
Level of contaminant in spiked soil
Research Findings
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Surfactant Characterization
Research Findings
Extractants Empirical Formula/
Chemical name
Mol Wt Concentrations
used
CMC at 25OC Surface Tension
(mN m-1)
pH
Water H2O 18 - 71.2 7
Soapnut (SN) C52H84O21.2H2O 1081.24 0.5% 0.1% 41 4.63
1% 40 4.44
1.5% 39.5 4.35
SDS NaC12H25SO4 288.38 10 mM 8.2 mM 34 9.6620 mM 32 10.06
30 mM 31 10.25
Triton X-100 t-octylphenoxy
polyethoxyethanol
625 1 mM 0.24 mM 35 7
Phosphate KH2PO4 136.086 50 mM --- --- 4.78
100 mM 4.66
150 mM 4.67
Soapnut +Phosphate
--- --- 0.5%+50 mM 0.1% 4.791%+100mM 4.69
1.5%+150 mM 4.62
Comparison of CGAs characteristics
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Comparison of CGAs characteristics
CGAs stability
Rise of CGA-liquid front with time for SDS
and soapnut (SN) at different concentrations
Half-life of CGAs produced from Soapnut and SDS solutions of
different concentrations (Soapnut: L-0.5%, LM-1%, M-1.5%, MH-2%,
H-2.5%; SDS: L-10mM, LM-15mM, M-20mM, MH-25mM, H-30mM;
Soapnut-phosphate: L-0.5%-50mM, LM-1%-100mM, M-1.5%-
150mM, MH-2%-200mM, H-2.5%-250mM)
300
400
500
600
700
800
900
1000
1100
1200
1300
L LM M MH H
Soapnut
SDS
Soapnut-Phosphate
Time(sec)
10
11
12
13
14
15
16
0 500 1000 1500
SN 0.5%
SDS 30mM
SN0.5-Ph50
Height of
CGA
time (sec)
H
eightofCGA
(cm)
Propagation of CGA through soil column
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Propagation of CGA through soil column
The experimental results showed that pressure gradient depended on flow rates,
viscosity of fluids and flow modes.
The flow rates were maintained at 10 mL/min for the remaining experiments.
0
10
20
30
40
50
60
SN 0.5% SN 1% SN 1.5% SN 0.5% SN 1% SN 1.5%
Up flow Down flow
Flow rate 10 (ml/min)
Flow rate 15 (ml/min)
Flow rate 20 (ml/min)
Pressuregradient(kPa/cm)
Column experiments : Overall performances
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pH5 pH6 pH5 pH6 pH5 pH6 pH5 pH6 pH5 pH6 pH5 pH6 pH5 pH6 pH5 pH6 pH5 pH6
Water 1% Soapnut CGA1% Soapnut SolutionSN1-Phosphate100 CGASN1-Phosphate100 Solution20 mM SDS CGA20 mM SDS Solution1 mM Triton CGA1 mM Triton solution
Downflow 15.66 13.44 45.42 38.60 60.00 59.46 63.44 72.82 81.88 79.16 29.93 31.09 46.53 47.42 48.76 35.43 55.62 51.22
Upflow 23.44 21.86 70.96 65.46 62.90 71.23 71.43 86.9 88.79 82.91 44.68 35.39 33.87 42.2 51.82 38.49 52.45 53.88
0
10
20
30
40
50
60
70
80
90
100
CumulativeAsremovalin6PV(%)
Column experiments : Overall performances
Zinc removal by batch experiments
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Zinc removal by batch experiments
Water SDS 20 mM Soapnut 1%
Zn extracted (%) 6 30.11 68.33
0
10
20
30
40
50
60
70
80
Znex
tracted(%)
Zinc extraction with water, SDS and soapnut at unadjusted pH
Cadmium removal by batch experiments
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Cadmium removal by batch experiments
Water SDS 30 mMSDS 30 mM + 0.1
M EDTASoapnut 1%
Soapnut 1%+ 0.1M EDTA
Cd removal (%) 12 63 68 71 80
0
10
20
30
40
50
60
70
80
90
Cdremoval(%)
Performance of different washing agents at soil: solution ratio of 1:30
The kinetic models for desorption
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The kinetic models for desorption
Arsenic(V) desorption kinetics follow Elovich equation
Zinc desorption kinetics follow Two-constant rate equation
Cadmium desorption kinetics follow Elovich equation
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FT-IR Analysis
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No shifting of peaks in FT-IR spectra was
observed in the soapnut solution in presence
of arsenic.
Therefore, it can be suggested that no
chemical interaction was involved in the
arsenic removal by soapnut solution.
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Mechanism of contaminant
removal from soil by non-ionic
surfactant solution
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Dissolution of soil mineral components such as Ca, Mg, Al, Si and Fe
was evaluated.
The extractants were not strong enough to dissolve Al and Si. Among the
soil components, Ca, Fe, and Al contribute to sorption of As by soils,
whereas, Si and other components contribute little.
1.5% Soapnut resulted in more Ca and Fe dissolution than others, and
concurrently was found to remove most arsenic.
Damage to soil
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Dissolution of metal from soil (% of total content)
Extractant Concentration Ca Mg Fe Al Si
SN 1.5% 1.97 2.05 0.42 0.46 0.00
SDS 30mM 0.33 1.02 0.14 0.18 0.00
Phosphate 150 mM 1.87 2.83 0.75 0.70 0.01
SN+Ph 1.5%+150mM 3.51 4.09 1.02 1.11 0.02
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Damage to soil
SEM image
Recovery of wash solution
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y
Arsenic removal from effluent by ferric chloride
Arsenic removal efficiency with FeCl3is maximum in the pH range of 7-8. At pH of 8 with
15 mg/L of ferric chloride, up to 87% of the As is removed from the soapnut. However, after
8-10 mg/L dose of ferric chloride, the improvement in As removal does not increase too
much.
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CONCLUSIONS
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Objective 1: CGAs: Characterization and propagation through soil column.
Soapnut CGAs : More stable, more homogenous than SDS
Up flow experienced higher pressure gradient than down flow modes.
CONCLUSIONS
Objective 2: Arsenic removal by solution and CGAs of soapnut and SDS. Effect of phosphate.
Solutions and CGAs of soapnut removed up to 88% of arsenic, compared to SDS (up to only 46%).
CGAs and solutions showed comparable results. CGAs comprises of up to 35% of its volume of air
and is more economical.
Arsenic removal is highest in up flow mode for both CGAs and solutions.
High concentration soapnut CGAs performed better due to higher air hold-up which exposes more
interfacial area, facilitating mass transfer.
Cumulative As removal increased linearly in subsequent pore volumes.
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Objective 3: Zinc and Cadmium removal by solution of soapnut and SDS. Effect of EDTA on the process.
Soapnut solution removed higher amount of Zn (74%) and Cd (73%) due to higher acidity than SDS.
With addition of EDTA, Cd desorption increased to 82%.
Objective 4: Mechanism and kinetics of the soil washing process by soapnut and SDS.
As and Cd desorption followed Elovich equation. Zn desorption followed two-constant rate equation.
Micellar solubilization,
Physical association of contaminants with CGAs
Low pH
Objective 5: Environmental friendliness of the process: damage to soil, recovery and reuse of washeffluent.
Soil corrosion was negligible as proved by minimal metal dissolution and SEM image.
Soapnut wash effluent can be recovered by 8-10 mg/L of ferric chloride at the pH of 8 by coagulation-
flocculation-precipitation process.
CONCLUSIONS
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Material cost for washing 1 ton of soil by 1% soapnut ~ USD 28.57
Material cost for washing 1 ton of soil by 20 mM SDS ~ USD 27.7
Material handling, structural installation and operational cost being similar, both the natural and
synthetic surfactants have comparable cost factors, with the added advantage of environmentally
safe and biodegradability in favor of soapnut
41Cost of application
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Scope of application
In Europe and USA, there are more than 1.5 million industrial andmining sites contaminated with heavy metals. The developing
nations do not have any reliable statistics.
ETCS. (1998). Topic report : Contaminated sites. Copenhagen, Denmark: European Topic Centre
Soil, European Environment Agency.
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Novelty
My thesis addresses the fundamental problem of soil pollution which questions the
very existence of human race on the earth and it is also associated with other
problems such as desertification, poverty, famine and other related economic and
societal issues.
My research recommends a simple solution which is completely safe, financially
viable, compatible to the existing facilities, biodegradable, natural, plant based,
does not corrode the soil, has high scope of application around the globe and
carries no environmental risk.
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Future scope of work
Mixed metal systems as contaminants.
Mixed surfactant systems can be used to address anionic, cationic and organic contaminants all
together.
Mixed contaminants such as heavy metals and organics should be treated with soapnut and mixed
surfactant systems.
Field testing for further understanding of the process.
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PUBLICATIONS
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Published
1. Hashim, M. A., Mukhopadhyay, S.,Sahu, J. N., & Sengupta, B. (2011). Remediation technologies for heavy metal contaminated
groundwater. [doi: 10.1016/j.jenvman.2011.06.009].Journal of Environmental Management, 92(10), 2355-2388. (ISI, Q1)
2. Hashim, M. A., Mukhopadhyay, S.,Gupta, B. S., & Sahu, J. N. (2012). Application of colloidal gas aphrons for pollution remediation.
Journal of Chemical Technology and Biotechnology, 87(3), 305-324. doi: 10.1002/jctb.3691(ISI, Q1)
3. Mukhopadhyay, S., Hashim, M. A., Sahu, J. N., & Sengupta, B. (2013). Comparison of a plant based natural surfactant with SDS for
washing of As(V) from Fe rich soil.Journal of Environmental Science-China, 25(11), 1-11. doi: 10.1016/S1001-0742(12)60295-2 (ISI,
Q2)
4. Mukhopadhyay, S., Hashim, M. A., Allen. M., & Sengupta, B. (2013). As removal from soil with high iron content using a natural
surfactants and phosphate. (IJEST, ISI, Q2) Accepted
Under review
1. Mukhopadhyay, S., Hashim, M. A., Yusoff, I., & Sengupta, B. (2013). Removal of cadmium from contaminated soil by Sapindus
mukorossiand EDTA. Submitted toEnvironmental Earth Sciences. (ISI, Q2)
2. Mukhopadhyay, S., Hashim, M. A., Yusoff, I., & Sengupta, B. (2013). Zinc removal from soil containing high iron by washing with
Sapindus mukorossi, a natural surfactant. Submitted to Chemical Engineering Research and Design. (ISI, Q2)
3. Mukhopadhyay, S., Hashim, M. A., Yusoff, I., & Sengupta, B. (2013). Application of colloidal gas aphron suspensions produced from
Sapindus mukorossi for arsenic removal from contaminated soil. Submitted toEnvironmental Science and Technology. (ISI, Q1)
Under Preparation
1. Mukhopadhyay, S., Hashim, M. A., Yusoff, I., & Sengupta, B. (2013). Effect of phosphate on arsenic removal from contaminated soil
using colloidal gas aphron suspensions produced from Sapindus mukorossi.
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Award
Awarded 1st place in University of Malaya
Three-Minute Thesis Competition at Faculty
of Engineering, 2013
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Conference papers
Conference papers:
1. Mukhopadhyay, S., Hashim, M.A., Sen Gupta, B. Remediation of contaminated soil using synthetic and natural surfactant
solution and colloidal gas aphrons, 2013. University Of Malaya Researchers' Conference 2013 (Special Session 3: FutureResearch Leaders), 19-20 November 2013, University of Malaya, Kuala Lumpur, Malaysia.
2. Soumyadeep Mukhopadhyay, Mohd Ali Hashim, Bhaskar Sen Gupta. Application of colloidal gas aphrons produced
from soapnut fruitfor arsenic removal from contaminated soil, 2013 Asia-Oceania Top University League on Engineering
(AOTULE) Student Conference, Chulalongkorn University, Bangkok, 16-19th October, 2013.
3. Mukhopadhyay, S., Hashim, M. A., Sahu, J. N., Ismail, Y., & Sengupta, B. (2011).A comparative study of heavy metal
removal by acid, chelant and natural surfactant washing from alluvium soil with high iron content obtained from Klang
Valley, Malaysia. Paper presented at the Third International Congress on Green Process Engineering.
4. Mukhopadhyay, S., Hashim, M. A., Sahu, J. N., & Sengupta, B. (2012).Performance of a biosurfactant in comparison tocommercial synthetic surfactants in removing heavy metal from soil. Paper presented at the 14th Asia Pacific
Confederation of Chemical Engineering (APCChE 2012).
5. Sengupta, B., Mukhopadhyay, S.,& Hashim, M. A. (2011a).In-situ treatment of heavy metal contaminated groundwater -
special emphasis on arsenic pollution. Paper presented at the UK - Malaysia - Ireland Engineering Science Conference.
6. Sengupta, B., Mukhopadhyay, S.,& Hashim, M. A. (2011b).Innovative Technologies for Heavy Metal Contaminated
Groundwater Remediation. Paper presented at the International Conference on Chemical Innovation, (ICCI2011).
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Research outputs
in other fields
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Publications in other research areas
Published
1. Nosrati, S., Jayakumar, N. S., Hashim, M. A., & Mukhopadhyay, S.(2013). Performance
evaluation of vanadium (iv) transport through supported ionic liquid membrane.Journal of the
Taiwan Institute of Chemical Engineers, 44(3), 337-342.
2. Mukherjee, S., Mukhopadhyay, S., Hashim, M. A., Sahu J.N. & Sen Gupta, B. (2013).
Contemporary environmental issues associated with landfill leachate: Plume monitoring, impact
assessment & remedial measures. Critical Reviews in Environmental Science and Technology (ISI
Q1)
3. Sumona Mukherjee, Soumyadeep Mukhopadhyay, Agamuthu Pariatamby, Mohd. Ali Hashim,
Bhaskar Sen Gupta. (2013). A comparative study of biopolymers and alum in the separation and
recovery of pulp fibres from paper mill effluent by flocculation. Journal of Environmental
Sciences (ISI, Q2)
Under preparation
1. Zamri, W. M., Sengupta, B., Mukhopadhyay, S.,Yusoff, I., & Hashim, M. A. (2013). In-situ iron
removal from aquifer by recharging oxidized groundwater. To be submitted in ISI Q1 journal.
2. Sengupta, B., Bandopadhyay, A., Mukhopadhyay, S.,Yusoff, I., & Hashim, M. A. (2013).
Sustainable in-situ treatment of arsenic contaminated groundwater - long term performance of achemical free technology in rural community. To be submitted in ISI Q1 journal.
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Conference papers on other research fields
1. Wan Mohd Zamri, S. Mukhopadhyay,M.A. Hashim, I. Yusoff , B. Sen Gupta; 2014. Sustainable in-situ treatment process
for groundwater iron removal suitable for urban water management; Workshop on Arsenic Pollution and Health in Rural
Bengal as a part of the UKIERI Project: Assessment of effects of arsenic pollution on health in rural Bengal and development
and implementation of sustainable technology solution Organized by Department of Civil Engineering, Bengal Engineering
and Science University, Shibpur, Howrah in association with Queen's University, Belfast, UK; 13.01.2014, BESU, Howrah,
India.
2. Wan Mohd Zamri, M.A. Hashim, S. Mukhopadhyay, I. Yusoff, B. Sen Gupta. Sustainable in-situ treatment process for
groundwater iron removal suitable for urban water management, 2013. Myanmar Water, 24 - 26 October 2013, Tatmadaw
Hall Yangon, Myanmar
3. B. Sen Gupta , A. Bandopadhyay , S. Mukhopadhyay. Subterranean Arsenic Removal (SAR) Technology for Groundwater
Remediation, 2013. Myanmar Water, 24 - 26 October 2013, Tatmadaw Hall Yangon, Myanmar
4. Soumyadeep Mukhopadhyay, Mohd Ali Hashim, Ismail Yusoff, Bhaskar Sen Gupta. Sustainable In-situ Treatment Process
for Groundwater Iron Removal Suitable for Urban Water Management, 2nd Water Research Conference, 2013, Singapore, 20-
23rd January, 2013.
5. Soumyadeep Mukhopadhyay, Mohd Ali Hashim, Ismail Yusoff, Bhaskar Sen Gupta. In-situ iron removal from aquifer by
recharging oxidized groundwater, 5th International Conference on Water Resources and Arid Environments 2012, Riyadh, 2-
5th Dec, 2012.
6. Soumyadeep Mukhopadhyay, Mohd Ali Hashim, Ismail Yusoff, Bhaskar Sen Gupta. In-situ iron removal from aquifer by
recharging oxidized groundwater, 2012 Asia-Oceania Top University League on Engineering (AOTULE) Student Conference,
Kuala Lumpur, 23-25th November, 2012.
7. B. Sen Gupta, A. Bandopadhyay, N. K. Nag, S. Mukhopadhyay, A. Mazumdar. Subterranean Arsenic Removal - A journey
to the future, International Conference on Water Quality with special reference to Arsenic ,18th - 20th February, 2012,
Kolkata, India
8. B. Sen Gupta, S. Mukhopadhyay, M.A. Hashim. Innovative Technologies for Heavy Metal Contaminated Groundwater
Remediation, International Conference on Chemical Innovation, (ICCI2011), TATi College, Terrenganu, Malaysia 2011
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Acknowledgements
University of Malaya for giving me an opportunity and funding to carry out research.
My supervisors Prof Mohd Ali Hashim, Dr Jaya Narayan Sahu and Dr Bhaskar Sen Gupta(Queen's University Belfast)
The Head of the Dept Dr Rozita, external and internal examiners and all academic staff of
Dept of Chemical Engg, UM
Lab technicians Ms Fazizah, En Jalaluddin, En Kamaruddin, En Azaruddin and En Kamalrul
Office staff of Dept of Chemical Engg and Faculty of EnggMs Laila, Ms Amy, Ms Meena,
En Norhafizal
My family and friends
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REMEDIATION OF CONTAMINATED SOIL USING SYNTHETIC
AND NATURAL SURFACTANT SOLUTION AND COLLOIDAL
GAS APHRONS
53
Soumyadeep Mukhopadhyay
Candidature Level
Doctor of Philosophy (PhD)
Department of Chemical EngineeringFaculty of Engineering
Feb 2014
Supervisors
Prof Mohd Ali Hashim
Dr Jaya Narayan Sahu
Dr Bhaskar Sen Gupta (QUB)
Research Methodology
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Soil Characterization
Soil sampling
XRD for minerals present in soil
ICP-OES for Heavy metal content
Bulk density & specific gravity
pH, Conductivity
Soil Classification
Organic Matter Content
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Research Methodology
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The soil was sampled from 1st layer aquifer in Hulu Langat area, Selangor,Malaysia
The soil was spiked by 200 mgL-1sodium arsenate solutions, 100 mgL-1solution of Cd(NO3)2, 1000 mgL
-1solution of Zn(NO3)2at room
temperature by mixing it for 7 days at weight: volume ratio of 3:2
As/Cd/Zn-spiked soil samples were leached with 2 pore volumes ofartificial rainwater of pH 5.9 following the method proposed by Oorts etal. (2007)
The dried soils were digested following USEPA method 3050B tomeasure metal contents by ICP-OES
Soil sampling and spiking
Research Methodology
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Extraction of surfactant from soapnut fruit
56A 10% natural surfactant solution was prepared by extracting
10 g of fruit pericarp powder in 100 mL of deionized water.
Drying of fruit pericarps at 50C for 2 days
The pericarps were ground and sieved through U.S. Standard No. 20sieve (840m).
The powder was added to deionized water and stirred for 3 h at room
temperature
The mixture was centrifuged at 4,000 rpm for 10 min, and thesupernatant was filtered through a normal filter paper. The filtrate wasallowed to evaporate on a water bath at 70 C.
The dry paste obtained was re-dissolved in water and used as stock
solution.
Research Methodology
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Characterization of CGAs
Liquid drainage of CGA
The liquid drainage rates are measured by reading the volume of the liquid drained as a
function of time. Tests are conducted by transferring 300 mL of CGAs suspension into a
500mL measuring cylinder at room temperature.
Stability of CGA
The stability of CGAs, measured in terms of half-life (tdh), is defined as the time taken by
the CGAs dispersionbulk liquid interface to reach half its final height. The aphrons
phase separates easily from the bulk-liquid phase because of its buoyancy.
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Air Holdup
Air holdup is defined as the volume percentage of entrapped air in the CGA
dispersion.
Average hydraulic conductivity
The average hydraulic conductivity of the CGAs was also calculated for all surfactant
concentrations based on Darcy's equation for the various pressure readings and flow
rates.
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Characterization of CGAs
Research Methodology
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Sequential extraction for soil fractionation
Hall's sequential extraction of arsenic from soil Tessier's sequential extraction of zinc and cadmium from soil
Arsenic sorption in soil
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The unspiked soil has a pH value of 4.5
and Eh value of 260 mV. According to therevised EhpH diagrams for the AsOH
system at 25OC and 1 bar (Lu and Zhu,
2011), arsenic is expected to exist in +5
state under these conditions in aqueous
matrices.
Soil spiked with 200 mgL-1As solution is
found to retain 85.63 mg kg-1of As after
washing with artificial rain water of pH
5.9. Arsenic is retained in the soil matrix
mostly by hydrous oxides of Fe(III) and
Al(III)
Shake Flask Experiments
Overall performance
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0
10
20
30
40
50
60
70
80
90
0
2
4
6
8
10
12
water SDS 20 mM SN 1% SN+Ph
As removal
pH
pHofwashsolution
Asremoval(%)
Performance of different extractants for arsenic
removal from soil in shake flask study
Arsenic desorption increased with
surfactant concentration.
There was not much improvement of
performance above 100 mM phosphate
concentration.
Arsenic desorption increases with an
increase in the soil: solution ratio.
3-factor 3-level Box
Behnken (BB) experimental design
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Response surfaces for combined effect of (a) surfactant and
phosphate concentration at constant soil: solution ratio of 1:20; (b)
soil: solution ratio and surfactant concentration at constant
phosphate concentration of 75.03 mM; and (c) soil: solution ratio
and phosphate concentration at constant soapnut concentration of
0.76% on desorption of As(V) from soil
Phosphate
conc (mM)
Soapnut
conc (%)
Soil:Solutio
n (w/v)
Desirability
Value
Arsenic desorption (%)
Predicted
Experim
ental
Error
(%)75.73 1.5 1:30 1 79.82 76.77 3.97
101.29 1.46 1:30 1 80.53 77.63 3.73
Model validation
The kinetic models for desorption
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Two-constant rate equation Elovich equation Parabolic diffusion equation First order kinetics
lnS = A + kdlnt S = A + Blnt S/Smax= A + kdt1/2 ln(S0S) =A + kdt
A kd R2 SE A B R2 SE
(mg/(g
min))
(g/mg) A kd R2 SE A kd R
2 SE
Arsenic(V)
Soapnut 1% -2.962 0.327 0.985 0.108 -0.034 0.060 0.991 0.013 0.034 16.67 0.302 0.015 0.888 0.103
-
0.342 0.000 0.753 0.118
Soapnut
1%+Phosphate
100mM -2.027 0.174 0.829 0.107 0.117 0.037 0.959 0.017 0.874 27.03 0.567 0.010 0.799 0.097
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0.441 0.000 0.560 0.118
SDS -2.588 0.222 0.940 0.079 0.017 0.043 0.965 0.018 0.064 23.26 0.349 0.012 0.911 0.076
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0.324 0.000 0.762 0.084
Mean 0.918 0.098 0.972 0.016 0.866 0.092 0.692 0.107
Zinc(II)
Soapnut 1% 3.232 0.076 0.942 0.052 11.450 9.112 0.948 2.957 32.014 0.11 86.230 7.000 0.950 9.064 6.899 0.000 0.845 0.005
SDS 20mM 2.856 0.079 0.969 0.040 7.558 6.518 0.967 1.665 20.783 0.15 48.510 4.006 0.950 5.150 6.910 0.000 0.837 0.004
Mean 0.956 0.046 0.958 2.311 0.950 7.107 0.841 0.005
Cadmium
(II) Soapnut 1% -2.175 0.177 0.938 0.063 0.071 0.041 0.923 0.017 0.232 24.39 0.571 0.024 0.818 0.042
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1.227
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0.002 0.900 0.085
Soapnut1% +EDTA0.05M -1.747 0.145 0.849 0.085 0.146 0.042 0.918 0.018 1.358 23.81 0.449 0.032 0.949 0.066
-1.558
-0.003 0.872 0.140
Mean 0.894 0.074 0.921 0.017 0.884 0.054 0.886 0.112
Sequential extraction of As(V) following Hall et al. (1996)
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640
10
20
30
40
50
60
70
80
90
100
Spiked soil SDS 20 mM Soapnut 1% Soapnut 1%+Phosphate 100mm
Chart Title
Extracted by wash agent
Residual fraction
Sulphides & Organics
Cry-Fe ox bound
Am-Fe ox bound
AEC fraction
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Mechanism of contaminant
removal from soil by anionic
surfactant solution