PHD VIVA presentation.pptx

8/10/2019 PHD VIVA presentation.pptx

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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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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


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


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


Batch Experiments

Shake Flask Study

R h M th d l


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Experimental conditions and variables for zinc removal


Batch ExperimentsShake Flask Study

Effect of Surfactant concentrations

Standard conditions


Temperature = 25oC

Shaking time 4 hrs

Unadjusted pH


Soapnut (0.5%, 1%, 1.5%, 2%, 2.5%)

SDS (10 mM, 20 mM, 30 mM)

Effect of pH

Standard conditions


Temperature = 25oC

Shaking time 4 hrs



pH = 4,5,6,7



Temperature = 25oC

Composition of aqueous solution:Surfactants= 1% Soapnut and 20 mM SDS

Shaking time 4 hrs

Unadjusted pH


Soil: Solution ratios: w/V = 1:10, 1:20, 1:30

Effect of Surfactant concentrationsStandard conditions


Temperature = 25oC

Shaking time 4 hrs

Unadjusted pH

No EDTA


Soapnut (0.5%, 1%, 1.5%, 2%, 2.5%)

SDS (10 mM, 20 mM, 30 mM)

Effect of EDTA

Standard conditions


Temperature = 25oC

Shaking time 4 hrs



EDTA concentration = None, 0.05M, 0.1M



Temperature = 25oC

Composition of aqueous solution:Surfactants= 1% Soapnut and 20 mM SDS

Shaking time 4 hrs

Unadjusted pH

No EDTA


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 Methodolog


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Characterization of CGAs

Liquid drainage of CGA

Stability of CGA

Air holdup

Average hydraulic conductivity

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Soil column washing experiment by CGA and surfactant solutions



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Column Washing Experimental Setup

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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




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Standard conditions


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




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Mechanism of As(V) desorption

FT-IR spectra.

Zeta potential measurement.

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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)



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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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)



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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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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



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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.



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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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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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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



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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

-

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

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

-

1.227

-

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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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

PHD VIVA presentation.pptx

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