REMEDIATION OF CONTAMINATED SOIL USING SYNTHETIC

AND NATURAL SURFACTANT SOLUTION AND COLLOIDAL

GAS APHRONS

Soumyadeep Mukhopadhyay
Candidature Level
Doctor of Philosophy (PhD)
Department of Chemical Engineering
Faculty 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)

Introduction

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

Why Arsenic, Zinc and Cadmium ?

High concentrations of cobult, nickel, lead, zinc, arsenic, cadmium and copper has been found in
Malaysian soil, originating from fertilisers, mining activities and industrial spills (Zarcinas et al.
(2004)).

Arsenic is 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.

Introduction

Soil washing is the best option to reduce the environmental risk from soil contamination.
Soil washing can be ex-situ and in-situ process.

Ex-situ soil washing

In-situ soil flushing by micro bubbles

Introduction

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.

Introduction
Sapindus mukorossi

Sapindus mukorossi or 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 been
used for arsenic removal from soil.

Introduction

The performance of soapnut has been compared with a

commonly used inorganic surfactant Sodium Dodecyl
Sulphate (SDS) under different conditions, e.g.
Soil pH
Flow modes
Surfactant concentrations
Soil: solution ratio
Effects of additives (phosphate and EDTA)

Introduction

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)

Objectives

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.

10

11

Research Methodology

Soil sampling and spiking: Sampled from 1st layer aquifer

of Hulu Langat Basin

Soil characterization : XRD, pH, density, classification,

metal content

Extraction of saponin from soapnut: Fruit pericarp

dissolved in water, filtered and evaporated.

12

Research Methodology

Scheme of research

13

Research Methodology
Effect of Surfactant concentrations

Batch Experiments
Shake Flask Study

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

Experimental conditions and

variables for arsenic removal

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:
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)

14

Research Methodology
Batch Experiments Shake Flask Study
Experimental conditions and variables for zinc removal
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

Experimental conditions and variables for cadmium removal

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
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

15

Research Methodology

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.

16

Research Methodology

Characterization of CGAs

Liquid drainage of CGA

Stability of CGA
Air holdup
Average hydraulic conductivity

17

Research Methodology

Soil column washing experiment by CGA and surfactant solutions

18

Research Methodology

Column Washing Experimental Setup

19

Research Methodology

Control factors and their levels for column experiments

Parameter

Level 1

Level 2

Level 3

Type of washing agent

SDS

Soapnut

Soapnut + Phosphate

Physical state of wash agent

Solution

CGAs

---

SDS (mM)

10 mM

20 mM

---

Soapnut (%)

0.5%

1%

---

Soapnut (%) +
Phosphate (mM)

0.5% + 50
mM

1% + 100 mM

---

Soil pH

---

Flow mode

Down flow

Up flow

---

Concentration
of washing
agent

20

Research Methodology

Experimental conditions and variables for kinetic experiments

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 pH
Sampling 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

21

Research Methodology
Mechanism of As(V) desorption

FT-IR spectra.
Zeta potential measurement.

Damage to soil

The wash solutions were analyzed for Ca, Mg, Si, Fe, Al to check for any structural
damage of soil.
Scanning Electron Microscope.

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. The
pH 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.

22

23

Soil Characterization
a. Characterization of natural soil sample
Soil properties
pH
Specific Gravity
CEC (Meq)
Organic matter content

Value
4.5
2.64
5
0.14 %

Bulk Density (gm cc-1)

2.348

Total porosity (%)

Total arsenic (mg kg-1)
Total iron (mg kg-1)
Total silicon (mg kg-1)
Aluminium (mg kg-1)
Total manganese (mg kg-1)
Magnesium (mg kg-1)
Lead (mg kg-1)
Zinc (mg kg-1)
Soil particle size distribution
Sand (< 50 m)
Silt (50-2 m)
Clay (> 2 m)

39
3
3719
~390,000
2400
185
635
11
18

92.66 %
5.2 %
2%

Method
USEPA SW-846 Method 9045D
ASTM D 854 - Water Pycnometer method
Ammonium acetate method for acidic soil (Chapman, 1965)
Loss of weight on ignition (Storer, 1984)
(Di Palma et al., 2003)

USEPA 3050B

Sandy soil according to USDA Soil Classification

24

Research Findings

Level of contaminant in spiked soil

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

25

Research Findings

Surfactant Characterization
Extractants

Empirical Formula/
Chemical name

Mol Wt

Water

H2O

18

Soapnut (SN)

C52H84O21.2H2O

1081.24

Concentrations CMC at 25OC

used

0.5%

SDS

NaC12H25SO4

288.38

Triton X-100

t-octylphenoxy
polyethoxyethanol
KH2PO4

625

1%
1.5%
10 mM
20 mM
30 mM
1 mM

136.086

50 mM

Phosphate

Soapnut +
Phosphate

---

---

Surface Tension
(mN m-1)

pH

71.2

0.1%

41

4.63

0.24 mM

40
39.5
34
32
31
35

4.44
4.35
9.66
10.06
10.25
7

---

---

4.78

8.2 mM

100 mM

4.66

150 mM
0.5%+50 mM
1%+100mM
1.5%+150 mM

4.67
4.79
4.69
4.62

0.1%

26

Comparison of CGAs characteristics

CGAs stability
1300

Soapnut

16

Height of
CGA

1200

SDS
Soapnut-Phosphate

1100

15

Height of CGA (cm)

1000
900

14

Time (sec)

800

13

12

700
600
500

11

SN 0.5%

400

SDS 30mM

300
L

SN0.5-Ph50

LM

MH

10
0

500

1000

1500

time (sec)

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)

27

Propagation of CGA through soil column

60
Flow rate 10 (ml/min)

Pressure gradient (kPa/cm)

50

Flow rate 15 (ml/min)

Flow rate 20 (ml/min)

40

30

20

10

0
SN 0.5%

SN 1%
Up flow

SN 1.5%

SN 0.5%

SN 1%

SN 1.5%

Down flow

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.

28

Column experiments : Overall performances

100

90

80

70

Cumulative As removal in 6 PV (%)

60

50

40

30

20

10

Downflow

pH5
pH6
Water
15.66
13.44

Upflow

23.44

21.86

pH5
pH6
pH5
pH6
pH5
pH6
pH5
pH6
pH5
pH6
pH5
pH6
pH5
pH6
pH5
pH6
1% Soapnut CGA1% Soapnut Solution
SN1-Phosphate100
SN1-Phosphate100
CGA
Solution
20 mM SDS CGA20 mM SDS Solution1 mM Triton CGA1 mM Triton solution
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
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

29

53.88

Zinc removal by batch experiments

80

70

Zn extracted (%)

60
50
40

30
20
10
0

Zn extracted (%)

Water
6

SDS 20 mM
30.11

Soapnut 1%
68.33

Zinc extraction with water, SDS and soapnut at unadjusted pH

30

Cadmium removal by batch experiments

90

80

70

Cd removal (%)

60

50

40

30

20

10

0
Cd removal (%)

Water

SDS 30 mM

12

63

SDS 30 mM + 0.1
M EDTA
68

Soapnut 1%
71

Soapnut 1%+ 0.1

M EDTA
80

Performance of different washing agents at soil: solution ratio of 1:30

31

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

32

FT-IR Analysis

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.

33

Mechanism of contaminant
removal from soil by non-ionic
surfactant solution

34

Damage to soil

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.

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

35

Damage to soil
SEM image

36

Recovery of wash solution

Arsenic removal from effluent by ferric chloride

Arsenic removal efficiency with FeCl3 is 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.

37

38

CONCLUSIONS

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.

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.

39

CONCLUSIONS

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 wash
effluent.
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 coagulationflocculation-precipitation process.

40

 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

Cost of application

41

 In Europe and USA, there are more than 1.5 million industrial and
mining 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.

Scope of application

42

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.

Novelty

43

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.

Future scope of work

44

PUBLICATIONS

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
mukorossi and EDTA. Submitted to Environmental 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 to Environmental 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.

45

Awarded 1st place in University of Malaya

Three-Minute Thesis Competition at Faculty
of Engineering, 2013

Award

46

Conference papers:
1.

2.

3.

4.

5.
6.

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: Future
Research Leaders), 19-20 November 2013, University of Malaya, Kuala Lumpur, Malaysia.
Soumyadeep Mukhopadhyay, Mohd Ali Hashim, Bhaskar Sen Gupta. Application of colloidal gas aphrons produced
from soapnut fruit for arsenic removal from contaminated soil, 2013 Asia-Oceania Top University League on Engineering
(AOTULE) Student Conference, Chulalongkorn University, Bangkok, 16-19th October, 2013.
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.
Mukhopadhyay, S., Hashim, M. A., Sahu, J. N., & Sengupta, B. (2012). Performance of a biosurfactant in comparison to
commercial synthetic surfactants in removing heavy metal from soil. Paper presented at the 14th Asia Pacific
Confederation of Chemical Engineering (APCChE 2012).
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.
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).

Conference papers

47

Research outputs
in other fields

48

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 a
chemical free technology in rural community. To be submitted in ISI Q1 journal.

Publications in other research areas

49

1.

2.

3.
4.

5.

6.

7.

8.

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.
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
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
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, 2023rd January, 2013.
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, 25th Dec, 2012.
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.
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
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

Conference papers on other research fields

50

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 Engg Ms Laila, Ms Amy, Ms Meena,
En Norhafizal
My family and friends

Acknowledgements

51

52

REMEDIATION OF CONTAMINATED SOIL USING SYNTHETIC

AND NATURAL SURFACTANT SOLUTION AND COLLOIDAL
GAS APHRONS

Soumyadeep Mukhopadhyay
Candidature Level
Doctor of Philosophy (PhD)
Department of Chemical Engineering
Faculty of Engineering
Feb 2014

Supervisors
Prof Mohd Ali Hashim
Dr Jaya Narayan Sahu
Dr Bhaskar Sen Gupta (QUB)

53

Research Methodology

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

54

Research Methodology

Soil sampling and spiking

The soil was sampled from 1st layer aquifer in Hulu Langat area, Selangor,
Malaysia

The soil was spiked by 200 mgL-1 sodium arsenate solutions, 100 mgL-1
solution of Cd(NO3)2 , 1000 mgL-1 solution of Zn(NO3)2 at 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 of

artificial rainwater of pH 5.9 following the method proposed by Oorts et
al. (2007)

The dried soils were digested following USEPA method 3050B to

measure metal contents by ICP-OES

55

Research Methodology

Extraction of surfactant from soapnut fruit

Drying of fruit pericarps at 50C for 2 days

The pericarps were ground and sieved through U.S. Standard No. 20
sieve (840 m).

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 the
supernatant was filtered through a normal filter paper. The filtrate was
allowed to evaporate on a water bath at 70 C.

The dry paste obtained was re-dissolved in water and used as stock
solution.

A 10% natural surfactant solution was prepared by extracting

10 g of fruit pericarp powder in 100 mL of deionized water.

56

Research Methodology

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 dispersion bulk liquid interface to reach half its final height. The aphrons

phase separates easily from the bulk-liquid phase because of its buoyancy.

57

Characterization of CGAs
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.

58

Research Methodology

Sequential extraction for soil fractionation

Hall's sequential extraction of arsenic from soil

Tessier's sequential extraction of zinc and cadmium from soil

59

Arsenic sorption in soil

Soil spiked with 200 mgL-1As solution is

found to retain 85.63 mg kg-1 of 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)

The unspiked soil has a pH value of 4.5

and Eh value of 260 mV. According to the
revised 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.

60

Shake Flask Experiments Overall performance

12

90
As removal

10

80

pH

60
50

6
40
4

30
20

As removal (%)

pH of wash solution

70

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.

10
0

0
water

SDS 20 mM

SN 1%

SN+Ph

Performance of different extractants for arsenic

removal from soil in shake flask study

61

3-factor 3-level BoxBehnken (BB) experimental design

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

Model validation

Phosphate
conc (mM)
75.73
101.29

Soapnut
conc (%)
1.5
1.46

Soil:Solutio
n (w/v)
1:30
1:30

Arsenic desorption (%)

Desirability
Experim
Value
Predicted
ental
1
79.82
76.77
1
80.53
77.63

Error
(%)
3.97
3.73

62

The kinetic models for desorption

Two-constant rate equation

lnS = A + kd lnt

Cadmium (II)

Zinc (II)

Arsenic (V)

kd

Elovich equation

Parabolic diffusion equation

S = A + Blnt

R2

SE

S/Smax = A + kd

R2

SE

(mg/(g
min))

(g/mg)

kd

R2

First order kinetics

ln(S0S) = A + kd t

t1/2

SE

kd

R2

SE

Soapnut 1%
Soapnut
1%+Phosphate
100mM

-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

-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 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 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

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

20.783 0.15

48.510 4.006 0.950 5.150 6.910 0.000 0.837 0.004

Mean
Soapnut 1%
Soapnut1% +EDTA
0.05M
Mean

0.956 0.046
-2.175
-1.747

0.177 0.938 0.063

0.145 0.849 0.085
0.894 0.074

6.518 0.967 1.665

0.958 2.311

0.071
0.146

0.041 0.923 0.017

0.042 0.918 0.018
0.921 0.017

0.950 7.107
0.232
1.358

24.39
23.81

0.841 0.005

0.571

0.024 0.818 0.042 1.227 0.002 0.900 0.085

0.449

0.032 0.949 0.066 1.558 0.003 0.872 0.140

0.884 0.054

0.886 0.112

63

Sequential extraction of As(V) following Hall et al. (1996)

Chart Title
100

90

80

70

60
Extracted by wash agent
Residual fraction
50

Sulphides & Organics

Cry-Fe ox bound
Am-Fe ox bound

40

AEC fraction

30

20

10

64

Spiked soil

SDS 20 mM

Soapnut 1%

Soapnut 1%+
Phosphate 100mm

Mechanism of contaminant
removal from soil by anionic
surfactant solution

65