removal of arsenic (iii) and chromium (vi) from the water using phytoremediation and ...

239 Pages·2013·4.2 MB·English

REMOVAL OF ARSENIC (III) AND CHROMIUM (VI) FROM THE WATER
USING PHYTOREMEDIATION AND BIOREMEDIATION TECHNIQUES

ANIL KUMAR GIRI

Department of Chemistry
National Institute of Technology, Rourkela
Rourkela – 769 008, Odisha, India
JULY, 2012
REMOVAL OF ARSENIC (III) AND CHROMIUM (VI) FROM THE WATER
USING PHYTOREMEDIATION AND BIOREMEDIATION TECHNIQUES
A

Thesis Submitted
in Partial Fulfillment of the Requirements
for the Degree of

DOCTOR OF PHILOSOPHY
IN
CHEMISTRY

BY

ANIL KUMAR GIRI

Under the guidance of

Prof. R. K. PATEL

Department of Chemistry
National Institute of Technology
Rourkela - 769 008
JULY, 2012
i
DEDICATED TO ------------------------

MY BELOVED PARENTS

ii
Prof. Rajkishore Patel, M.Sc. Ph.D.
Department of Chemistry
National Institute of Technology
Rourkela – 769 008
Odisha, India.

CERTIFICATE
This is to certify that the dissertation entitled “ Removal of arsenic (III) and chromium
(VI) from the water using phytoremediation and bioremediation techniques” being
submitted by Sri Anil Kumar Giri for the award of Ph.D. degree is a record of
bonafied research work carried out by him under my supervision. In my opinion, the
work fulfills the requirements for which it is being submitted.
The work incorporated in this thesis has not been submitted elsewhere earlier, in part
or in full, for the award of any other degree or diploma of this or any other Institution
or University.

(Prof. R. K. Patel)
Department of
Chemistry
National Institute of Technology,
Rourkela-769008,
Odisha
INDIA

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ACKNOWLEDGEMENT
First and foremost, I record my deep sense of gratitude and Indebtedness to Prof. R.
K. Patel, Department of Chemistry, National Institute of Technology, and Rourkela
for his meticulous care, constructive criticism, innovative suggestions and unfailing
affection during the entire period of investigation in spite of his busy schedule, which
made this work possible.
I highly appreciate the help extended by Prof. S. S. Mahapatra, Department of
Mechanical Engineering, National Institute of Technology, Rourkela, for their
inspiration and encouragement during the period of work.
I am very much grateful to Prof. K. M. Purohit, Ex. H.O.D., Department of Life
Science, National Institute of Technology, Rourkela, for their timely help and
cooperation.
I express my great depth of gratitude to Prof. B. G. Mishra, H.O.D., Department of
Chemistry, National Institute of Technology, Rourkela, for their inspirations and
encouragement throughout the research work.
I extend my special thanks to other faculty members, all my DSC members and the
supporting staff members of the Department of Chemistry, National Institute of
Technology, Rourkela, for their prompt help and co-operation at various phases of the
experimental work.
I highly appreciate the help extended by Dr. P. C. Mishra, Department of Chemistry,
PIET, Rourkela, and thank him for his friendly and ready help for carrying out some
work.
I thanks to technicians of SEM-EDX, XRD and BET instruments of National Institute
of Technology, Rourkela, for testing the samples of research work.
I wish to place on record my deep sense of gratitude to the Librarians National
Institute of Technology, Rourkela, for permitting me to carry out reference work.
I extend my thanks to my wife Dr. Manimala Behera for their help and support from
time to time.
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I extend my thanks to my dear friends Ramesh, Satish, Sandip, Ashsis and Kishore
babu Ragi for their help and support from time to time.
I acknowledge my heartfelt gratefulness to my family members for their blessings and
affections which made me to move ahead to finish the work.
Thanks to for all his blessings and wish for accomplishing this work.

(Anil Kumar Giri)

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ABSTRACT

Advancement in science and technologies parallel to industrial revolution has opened
new vistas to exploit the inherent traits of natural resources including green plants and
microorganisms to overcome the damage to the environment by pollutants.
The present work was aimed to develop the phytoremediation potential of the aquatic
plant Eichhornia crassipes for arsenic (III) and chromium (VI) from water. The
accumulation, relative growth and bio-concentration factor of plant on treatment with
different concentrations of arsenic(III) and chromium(VI) solution significantly
increased (P<0.05) with the passage of time. Plants treated with 0.100 mg/L arsenic
(III) accumulated the highest concentration of arsenite in roots (7.20 mg kg-1, dry
weight) and shoots (32.1 mg kg-1, dry weight); while those treated with 4.0 mg/L of
chromium (VI) accumulated the highest concentration of hexavalent chromium in
roots (1320 mg/kg, dry weight) and shoots (260 mg/kg, dry weight) after 15 days. The
plant biomass was characterized by SEM, EDX, FTIR and XRD techniques.
Microwave-assisted extraction efficiency is investigated for extraction of arsenic from
plant materials by comparison of the results by three extractant solutions: (i) 10%
(v/v) tetramethylammonium hydroxide (TMAH) (ii) Deionized water and (iii)
Modified protein extracting solution at different temperature and times. Extraction of
chromium ions was carried by same procedure from plant materials using three
extractant solutions: (i) 0.02 M ethylenediaminetetraacetic acid (EDTA), (ii)
Deionized water and (iii) HCl solution at different temperature and times.
Chromatograms are obtained for arsenic and chromium species in plant shoot biomass
by using HPLC-ICP-MS.
The biosorption of arsenic (III) and chromium (VI) from water is studied by living
cells of Bacillus cereus biomass as bioremediation. Bacillus cereus biomass is
characterized, using SEM-EDX, AFM and FTIR. Dependence of biosorption was
studied with variation of various parameters to achieve the optimum condition. The
maximum biosorption capacity of living cells of Bacillus cereus for arsenic (III) and
chromium (VI) was found to be 32.42 mg/g and 39.06 mg/g at pH 7.5, at optimum
conditions of contact time of 30 min, biomass dosage of 6 g/L, and temperature of 30
± 2°C. Biosorption data of arsenic (III) chromium (VI) are fitted to linearly
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transformed Langmuir isotherm and pseudo-second-order model with R2 (correlation
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coefficient) > 0.99. Thermodynamic parameters reveal the endothermic, spontaneous,
and feasible nature of sorption process of arsenic (III) chromium (VI) onto Bacillus
cereus biomass. The arsenic (III) and chromium (VI) ions are desorbed from Bacillus
cereus using both 1M HCl and 1M HNO .
3
The biosorption data of both arsenic (III) and chromium (VI) ions collected from
laboratory scale experimental set up is used to train a back propagation (BP) learning
algorithm having 4-7-1 architecture. The model uses tangent sigmoid transfer function
at input to hidden layer whereas a linear transfer function is used at output layer.
The removal of chromium (VI) from aqueous solutions by activated carbon prepared
from the Eichhornia crassipes root biomass. The maximum removal capacity of
activated carbon was found to be 36.34 mg/g for chromium (VI), at pH 4.5, contact
time of 30 min, biomass dosage of 7 g/L, and temperature of 25 ± 2 °C. The
adsorption mechanisms of chromium (VI) ions onto activated carbon prepared from
the Eichhornia crassipes root biomass are also evaluated in terms of thermodynamics,
equilibrium isotherm and kinetics studies. Column studies are also performed to know
the breakthrough point with an initial concentration of 10 mg/L.

Key words- Eichhornia crassipes ; Phytoremediation ; Arsenic (III); Chromium(VI);
Microwave assisted extraction; Bio-concentration factor; Bacillus cereus;
Biosorption isotherm, Biosorption kinetics; Thermodynamic parameters;
Regeneration and reuse; Atomic force microscopy; HPLC-ICP-MS; SEM-EDX;
XRD, FTIR; HG-AAS; ANN; Activated carbon; Column studies.

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CONTENTS

Chapter Particulars Page
Title i
Dedication ii
Certificate iii
Acknowledgement iv-v
Abstract vi-vii
List of figures xiv-
xix
List of Tables xx-xxi
Abbreviations xxii
Chapter-1 Introduction 1-8
Chapter-2 Aims and Objectives 9-10
Chapter-3 Literature Review 11-35
3.1. Heavy metals/metalloids 11
3.1.1. Arsenic 12
3.1.1.1. Sources of arsenic 12
3.1.1.2. Uses of arsenic 13
3.1.1.3. Toxicity of arsenic in water 14
3.1.2. Chromium 15
3.1.2.1. Sources of chromium 16
3.1.2.2. Uses of chromium 16
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3.1.2.3. Toxicity of chromium in water 17
3.2. Conventional methods for treatment of water 18
3.2.1. Precipitation 18
3.2.2. Chemical reduction 18
3.2.3. Cementation 20
3.2.4. Solvent extraction 20
3.2.5. Electrodeposition 20
3.2.6. Reverse osmosis 21
3.2.7. Electrodialysis 21
3.2.8. Biosorption/Adsorption 22
3.2.8.1. Physical sorption 23
3.2.8.2. Chemical sorption 23
3.2.8.3. Electrostatic sorption (ion exchange) 23
3.2.9. Disadvantages of conventional methods 24
3.3. Water treatment using phytoremediation techniques 24
3.3.1. The role of genetics 25
3.3.2. Mechanisms involved in phytoremediation 26
3.3.3. Advantages and limitations of phytoremediation techniques 28
3.4. Water treatment using bioremediation techniques 29
3.4.1. Mechanism involved in bioremediation 29
3.4.2. Biosorption and Bioaccumulation 31
3.4.2.1. Biosorbent materials 31
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