Thesis entitled

Adsorptive Remediation of Pb(II) and Cd(II)

from Simulated Wastewater using
Low Cost Agro-Waste Materials
Submitted for the Degree of

By

Under the supervision of

Professor
Department of Chemistry, BHU
(Supervisor)

&

Chief Scientist & Head

Analytical Chemistry Section, CSIR-IITR
(Co-Supervisor)

DEPARTMENT OF CHEMISTRY
FACULTY OF SCIENCE
BANARAS HINDU UNIVERSITY
VARANASI- 221005
INDIA
Enrolment No. 330047 2014
Copyright @ Faculty of Science, Department of Chemistry,
Banaras Hindu University, Varanasi, India (2014),
All right are reserved.
 Undertaking from the Candidate

I, Ruchi Pandey present the thesis entitled “Adsorptive Remediation of Pb(II) and
Cd(II) from Simulated Wastewater using Low Cost Agro-Waste Materials”. The
thesis mainly deals with the Pb(II) and Cd(II) adsorption study using unexplored economic
agro-waste/plant waste. The analysis of the heavy metals in the aqueous solution before
and after adsorption study has been performed by Atomic Absorption Spectrophotometer
and the biosorbents have been characterized by using analytical techniques (FTIR and
SEM). To compile the thesis, I have taken proper care to ensure that no mistake is
committed in the data included therein. I would be extremely sorry if any wrong
information or method tends to occur in my work.
I would like to thank my Supervisor (BHU), Co-Supervisor (CSIR- IITR) and Head
of the Department of Chemistry (BHU) for his continuous help, co–operation and valuable
suggestion.
I am especially thankful to my friends who always suggested me to do hard work.

2014 Ruchi Pandey

Place: Varanasi
 ANNEXURE – E
(see Clause XIII.2 (b) (iii))

CANDIDATE’S DECLARATION
I, Ruchi Pandey, certify that the work embodied in this Ph. D. thesis is my own bonafide
work carried out by me under the supervision of Prof. R.L. Prasad and co-supervision of
Dr. R.C. Murthy for a period of 4 years 3 months from September 2010 to December 2014
at Banaras Hindu University, Varanasi and CSIR-Indian Institute of Toxicology Research,
Lucknow. The matter embodied in this Ph. D. thesis has not been submitted anywhere for
the award of any other degree/diploma.
I declare that I have faithfully acknowledged, given credit to and referred to the research
workers wherever their work has been cited in the text and the body of the thesis. I further
certify that I have not willfully lifted up some other’s work, para, text, data, results, etc.
reported in the journals, books, magazines, reports, dissertations, theses, etc., or available
at web-sites and included them in this Ph. D. thesis and cited as my own work.

Date:
Place: Varanasi Ruchi Pandey

Certificate from the Supervisor/Co-Supervisor

This is to certify that the above statement made by the candidate is correct to the best of
my/our knowledge.

(Dr. R.C. Murthy) (Dr. R.L. Prasad)

Chief Scientist & Head Professor
Analytical Chemistry Section Department of Chemistry
CSIR-IITR Faculty of Sciences
Co-Supervisor BHU
Supervisor

Head
(Department of Chemistry, BHU)
 ANNEXURE – F
(see Clause XIII.1 (c) and XIII.2 (b) (iv))

COURSE/COMPREHENSIVE EXAMINATION COMPLETION

CERTIFICATE

This is to certify that Smt. Ruchi Pandey, a bonafide research scholar of this department
of Chemistry, has satisfactorily completed the course work / comprehensive examination
requirement which is a part of her Ph. D. programme.

Date:

Place: Varanasi (Head)

Department of Chemistry
 ANNEXURE – F
(see Clause XIII.1 (c) and XIII.2 (b) (iv))

PRE-SUBMISSION SEMINAR COMPLETION CERTIFICATE

This is to certify that Smt. Ruchi Pandey (Registration No. Chem.10-11/Res/Sept.10

Sem.30/890), a bonafide research scholar of this department of Chemistry, has
satisfactorily completed the pre-submission seminar (Dated 12.09.2014) as a requirement
which is a part of her Ph. D. programme.

Date:

Place: Varanasi (Head)

Department of Chemistry
 ANNEXURE – G
(see Clause XIII.2 (b) (v))

COPYRIGHT TRANSFER CERTIFICATE

Title of the Thesis: Adsorptive Remediation of Pb(II) and Cd(II) from Simulated
Wastewater using Low Cost Agro-Waste Materials

Candidate’s Name: Ruchi Pandey

COPYRIGHT TRANSFER

The undersigned hereby assigns to the Banaras Hindu University all rights under copyright
that may exist in and for the above thesis submitted for the award of Ph. D. degree.

(Ruchi Pandey)
 ACKNOWLEDGEMENT
First and foremost, I wish to express my gratitude to The Almighty God who
bestowed me with his blessings and all the favorable circumstances to go through this
crucial juncture.
At this moment of accomplishment, I must offer my profoundest gratitude to my
supervisor Prof. R.L. Prasad for his scientific advice and for providing me many
insightful and valuable suggestions regarding my thesis work. He has a deep knowledge
and great command on the subject. Whenever I needed help, he was always with me to
resolve at its simplest. He was always available for my question and he was positive
and gave generously his time and vast knowledge. A thorough background check and
a rigorous interrogation for my thesis by him was very much helpful to me. He exactly
taught me that how to write an impactful article in a precise way. I also have to thank
for his helpful career advice and suggestions in general. He has been very supportive
throughout this period. He always pushed me to do my best and stand by me in my good
and bad times.
I also feel very obliged to my Co-supervisor, Dr. R.C. Murthy, for supporting
me during these past five years, whenever I needed, he was just beside me. He remains
my best role model as a scientist, mentor, and more importantly as a human being. He’s
the genuine advisor and one of the smartest and simplest people I know. I hope that I
could be as lively, enthusiastic, and energetic as he is and to someday be able to
command an audience as he does. He has been supportive and always gave me the
freedom to plan the experiment and write the projects without any objection. He is my
primary resource for getting my science questions answered and was instrumental in
helping me crank out this thesis, all in one month.
I would like to extend my sincere gratitude towards Head Prof. L. Mishra,
Department of Chemistry, Faculty of Science, BHU, former Heads Prof. T. R. Rao and
Prof. B. Singh, for providing the infrastructure at the University. I am also feel obliged
for the affirmative suggestions given by the DRC members of Chemistry department
Prof. N. Singh, Prof. D.S. Pandey, Department of Chemistry and Prof. R.A. Yadav of
Department of Physics, BHU which made my study a successful and flawless venture.
I am also extremely indebted to The Director, Indian Institute of Toxicology
Research, for providing necessary infrastructure and resources to accomplish my
research work. My Special thanks go to Dr. V.P. Sharma, IITR as an in-charge of our
 Acknowledgement

campus and creating a healthy environment for the work. I also want to thank Dr.
Nasreen G Ansari, IITR for her support and care in different phases of my thesis, and
I greatly benefited from the scientific discussions with her. I am particularly thankful
to Dr. Jyotsana Singh, IITR as it was a great chance to meet and interact with her in
the last phase of my thesis. She guided me about very minute and important essentials
in the research field. I want to thank, Dr. P.N. Saxena, Dr. R.K Kanojia, Dr. Kewal
Lal and Dr. U.Mani all technical officers of the lab for their help during the course of
this work. I would also like to thank the helping staff of my lab Mr. Sitaram and Mr.
Chedi Lal for their untiring help during my PhD work.

My special thanks are due to Dr. DDS Yadav, Chemistry Department, Christian
College, Lucknow. Without his motivation I would not have been able to come up to
this stage. I also want to thank to Dr. Padma Vankar, Principal Research Scientist,
Indian Institute of Toxicology Research for providing me the facilities like FTIR and
SEM for my thesis work. I would also like to thank Uttar Pradesh Council of Science
and Technology for providing me financial assistance for my thesis work.

I am indebted to my colleagues for providing a stimulating and fun filled

environment. My thanks go in particular to Deepshikha, Bhanu Pratap, Shweta,
Roopshikha, Shraddha, Neeraj, Uzra at BHU with whom I shared a good environment
in the work place and I admire their distinguished helping nature. I’m also glad to have
friends like Mamta, Jasmeet, Vani, Vartika, Uday, Madhu, Priya and Prashant from
IITR for a couple of years. I value their friendship and support as well. My special
appreciation goes to my best friends, Aarti and Parul, for their love, care and moral
support.
I also thank people who were not part of my lab but helped me out, like Vishal,
Rajani, Vikas, Neelima, Rama Shankar and Aditi who kept motivating me throughout
the phase of my thesis writing.
I specially thank my Maa Smt. Rajeshwari Pandey and papa Shri D.N. Pandey,
my hard-working parents who have sacrificed their lives for their children and provided
unconditional love and care. Their spiritual support is also indispensable to sustain me
to complete this thesis. I love them so much, and I would not have made it this far
without them. I owe everything to them. My elder brothers Prashant and Prakash had
been my mentors right from my childhood. Their guidance throughout my academic
career helped me to come up to this stage. I love and thank to both of my brothers for
 Acknowledgement

all their advice and support. I also want to thank my both bhabhi, Suchita and Neha,
for their love and support.
Special thanks to my mother-in law Smt Mamta Shukla and father-in law Mr.
Rajesh K. Shukla, who treated me like my parents, after my marriage and always stood
by me in my good and bad times. A good support system is important in surviving and
staying sane during Ph.D. phase. I also thank to all my in-laws for their constant love,
care and support.
The best outcome even more precisely the real earning from these past five years
is finding my life, my love, best friend, my soul mate.. Shiv. I feel greatly blessed, to be
with him. I find it difficult to express my gratitude to him because it is so boundless.
Indeed, he is my strength, my anchor. No matter how many times I have done wrong,
sooner or later he appreciated me and always, believed in me. Without his care, love
and support, I would have been lost in the crowd. I am grateful to him not just because
he has given up so much to make my career a priority in our lives, but because he has
seen me through the ups and downs of the entire Ph.D. process. He has shared this
entire journey with me. At last I just want to say Thanks a lot for always listening to
me, supporting me and encouraging me, so it only seems right that I dedicate this thesis
to him.
 Table of Contents
Acknowledgement
Abbreviations I
Preface II-IV
Chapter 1 Introduction 1-6
Chapter 2 Review of Literature 7-27
Chapter 3 Removal of Pb(II) ions from simulated wastewater
using Cucumis sativus (Cucumber) peel 28-50
Chapter 4 Removal of Cd(II) ions from simulated wastewater using
Cucumis sativus Peel 51-64
Chapter 5 Removal of Pb(II) and Cd(II) ions from simulated
wastewater using Citrullus lanatus Rind 65-84
Chapter 6 Removal of Cd(II) ions from simulated wastewater
using NaOH modified Desmostachya bipinnata
& Bambusa arundinacea Leaves 85-105
References 106-141
Summary 142-147
List of Publication
Resume
 Abbreviations
CSP Cucumis sativus Peel
DBL Desmostachya bipinnata (Kush grass) Leaves
BAL Bambusa arundinacea (Bamboo) Leaves
MDBL Modified Desmostachya bipinnata Leaves
MBAL Modified Bambusa arundinacea Leaves
CLR Citrullus lanatus Rind
BIS Bureau of Indian Standard
m/V Mass/Volume Ratio
WHO World Health Organization
EPA Environmental Protection Agency
AAS Atomic absorption Spectrometry
EDL Electrode-less discharge lamp
FTIR Fourier Transform Infrared spectroscopy
SEM Scanning Electron Microscopy
rpm Rotation per minute
RT Room Temperature
g Gram
cm Centimeter
J Joule
µg Microgram
L Liter
V Volume
T Temperature in Kelvin
w Weight
DW Deionized water
ΔGo Change in Gibbs free energy
ΔHo Change in Enthalpy
ΔSo Change in Entropy
R Universal Gas constant
MSW Municipal Solid Waste

I
 Preface of Thesis

The thesis entitled “Adsorptive remediation of Pb(II) and Cd(II) from simulated
wastewater using low cost agro-waste materials” is divided into 6 chapters. The first
introductory chapter, is an attempt to provide a precise and brief information about the
heavy metals pollution in environment specifically about Lead and Cadmium pollution,
their source of pollution, remediation techniques and the objectives of the thesis. The
presence of these heavy metals in water is due to both natural and anthropogenic sources.
Lead and Cadmium stand out among other heavy metals due to their severe toxic nature
even at very low concentration and due to their abundant presence in environment. Their
removal even from their dilute contaminated and large volumes of aqueous solution can be
technically challenging and expensive. Conventional treatment technologies such as ion
exchange process, reverse osmosis, precipitation, electro chemical treatment etc. for the
removal of these toxic heavy metals are not economical, and further generate huge quantity
of toxic chemical sludge. Therefore the main focus of this chapter is on biosorption, as it
is emerging as a potential alternative to the existing conventional technologies for the
removal of these metal ions from aqueous solutions. Hence it has led to the investigation
of unexplored and economic agro-waste materials as potential metal biosorbents for the
removal of heavy metals. In this direction the present thesis deals with the adsorptive
removal of Pb(II) and Cd(II) from simulated wastewater using selected agro-waste
materials as biosorbent i.e.. Cucumis sativus (Cucumber) peel, Citrullus lanatus
(Watermelon) Rind, Desmostachya bipinnata (Kush grass) & Bambusa arundinacea
(Bamboo) leaves, in the continuation with work done by other authors earlier.
The second chapter i.e. Review of Literature, includes the review on studies
performed in the direction of heavy metal toxicity, their source of pollution and especially
on their remediation techniques i.e. conventional techniques and biosorption treatment of
aqueous solution as an alternative. There has been provided a comparative details of merit
and demerits of conventional techniques. In this chapter it has been discussed that why the
researchers have moved their track for heavy metal removal using the conventional
remediation method to biosorption. In this chapter, the work done for the heavy metal
removal using low cost agro-waste material in the recent past have been summarized for

II
 Preface of Thesis

the Pb(II) and Cd(II) removal. The adsorption capacity obtained using several different
biosorbents have also been reviewed for lead and cadmium removal.
Thus to proceed in this direction , in third & fourth chapter Cucumis sativus peel
an unexplored and low cost biosorbent alternative was utilized for the removal of Lead and
Cadmium from simulated wastewater, respectively. The effect of several parameter has
been discussed in detail such as pH, contact time, adsorbent dosage, initial ion
concentration, presence of other ions and temperature on the biosorption process. Classical
equilibrium models i.e. Freundlich and Langmuir adsorption isotherm models were applied
to describe the interaction between the biosorbent and the metal ions at equilibrium. These
isotherms are critical for optimization of the adsorption mechanism and for the loading
capacity of the adsorbent. The adsorption capacity using CSP as biosorbent were also
compared with some earlier used biosorbent for the Pb(II) and Cd(II) removal.
Thermodynamic study was also performed to predict the feasibility and the nature of
adsorption process. The experimental data were examined using pseudo first order and
pseudo second order kinetics and Intraparticle diffusion model to provide valuable insights
about the adsorption mechanism. Desorption studies were also performed to evaluate the
reuse of exhausted adsorbent for further cycles.
The chapter five describes the removal of Pb(II) and Cd(II) using citric acid
modified Citrullus lanatus (Watermelon) Rind as biosorbent. The modification process
was performed to enhance the adsorption capacity of raw Citrullus lanatus Rind for both
Pb(II) and Cd(II) ion uptake. Same as in the chapter third & fourth, here also the effect of
affecting parameters have been evaluated to optimize the experimental condition for the
removal of Lead and Cadmium from simulated wastewater. Isothermal, kinetic and
thermodynamic studies were performed using the equilibrium experimental data. Effect of
presence of some salts in the aqueous solution on the biosorption process was also
evaluated in order to correlate the findings with the real wastewater.
Chapter 6 describes the removal of Cd(II) ion using two agro-waste materials i.e.
Desmostachya bipinnata (Kush grass) & Bambusa arundinacea (Bamboo) as biosorbents.
They both belong to the same family: Poaceae. These both have been choosen as the
precursor to prepare biosorbent due to their abundant availability throughout the year, and
both of them can provide a comparable data as they both belongs to same family. A very

III
 Preface of Thesis

little work has been done using lawny grass but not with this particular species i.e
Desmostachya bipinnata which is known as Kush grass in India and grows abundantly,
everywhere and available freely and the same conditions are with Bambusa arundinacea
i.e. Bamboo leaves. Their modification was performed using NaOH to enhance their metal
uptake capacity. Physicochemical characterization was also done for the modified
adsorbents. Isothermal, kinetic, and thermodynamic studies were performed to the
experimental data in order to get insight about the adsorption behavior of these biosorbents
for Cd(II) removal from aqueous solution. Same as in the previous chapter 3 & 4, in this
chapter also to check the reusability of the exhausted biosorbents, desorption experiments
were also performed with all the materials using HNO3.
In all the chapters, the effect of interfering ions was studied in the simulated
wastewater to correlate the findings with real wastewater. The characterization of
biosorbents was done before and after the adsorption process through Fourier transform
Infrared (FTIR) spectroscopy to show the presence of several functional groups which are
involved/responsible for metal binding on adsorbent surface and Scanning Electron
Microscopy (SEM) to show the morphological changes in the surface of adsorbent.
Important findings of the present investigation are as, all the selected adsorbents i.e
Cucumis sativvus peel, Citrullus lanatus Rind, Desmostachya bipinnata (Kush grass) &
Bambusa arundinacea (Bamboo) leaves can be used as cost effective, efficient and green
alternatives for Pb(II) and Cd(II) removal from aqueous solution showing excellent
adsorption capacities as compared to previously studied other biosorbents by other
researchers. All these biosorbents can be used for number of further adsorption-desorption
cycles after desorption of adsorbed metal ions from the adsorbent surface without
significant loss of adsorption capacities. Even in presence of other ions they showed
effective adsorption capacities. Therefore, all these agro-waste precursors could be
considered efficient novel biosorbents for Pb(II) and Cd(II) ion removal from aqueous
solution.

IV
 1
Introduction
Since present thesis deals with the, adsorption studies for the removal of Pb(II)
and Cd(II) ions from the aqueous solution using low cost agro-waste materials,
therefore, it will be worthwhile to discuss about the heavy metal presence in the
environment, their toxicity, remediation techniques, and merit of using agro-waste
materials for heavy metal removal from the aqueous solution.

Earth's surface embraces 70% water that is the most treasured natural resource
existing on our planet. The life on Earth would not exist without water. Due to rapid
industrialization and contamination of the environment, water pollution emerges as the
main concern for the researchers these days and the fact is widely accepted. Lakes,
rivers and oceans are being overwhelmed with many toxic contaminants most
importantly heavy metals [1] and their presence in wastewater is of great concern
because of their known toxic effects. On the other hand, the treatment of wastewater in
terms of metal remediation is also of great importance to minimize the quantity of heavy
metals discharged into aqueous bodies. Heavy metals enter the environment through
natural ways such as leaching/weathering of rocks, forest fires, and volcanic eruptions
and besides this, almost all anthropogenic activities are potential contributors to heavy
metal pollution [2]. Heavy metals present in many industrial wastewaters such as
automobile, metal finishing, leather tanning, electroplating, petroleum and textile dying
industries are known to have toxic effects to the environment [3-5]. Direct discharge of
heavy metal containing wastewaters cause detrimental effects on all forms of life [6-8].
1.1 Heavy Metals
Heavy metals are elements having atomic weights between 63.5 and 200.6, and
a specific gravity greater than 5.0 [3, 9]. The special characteristics nature of heavy
metals are described [10] below:
 Toxicity that can last for a long time in nature.

1
 Chapter 1

 Bioaccumulation and bio-augmentation of heavy metals by food chain that

could damage normal physiological activity and endanger human life.
Some of the heavy metals are essential and useful for living beings while some
are very toxic even at very low concentration (1µg/l). They cannot be degraded even
by bio-treatment. Copper, zinc, lead, mercury, chromium, cadmium, iron, nickel and
cobalt are the most frequently found heavy metals in industrial wastewaters. Trace
amounts of some metal ions such as copper, zinc, cobalt, iron, manganese, and nickel
are required by some organisms as cofactors for their enzymatic activities [11]. Heavy
metals are taken into the body via inhalation, ingestion, and skin absorption [12]. The
toxicity of the heavy metals even at very low concentration to the organisms is due to
their reversible inhibition of many enzymes [13]. Amongst the heavy metals, Pb
(Lead) and Cd (Cadmium) have no advantageous biological function and are severely
toxic even in very small amount, that’s why both of them are regarded as the most
toxic heavy metals. Cadmium is mainly used in various industrial applications like
electroplating industry, Ni-Cd batteries, pigments, plastics, pesticides, dyes and textile
operation etc. [14]. However, Cadmium is known to possess nephrotoxic and
neurotoxic potential for human beings [15-17]. Pb is known to damage the kidney,
liver and reproductive system, basic cellular processes and brain functions [18, 19].
The main sources of human exposure to Pb is from lead accumulator batteries, leaded
gasoline, industrial sources such as lead mining, smelting and coal combustion, the
use of lead-based paint and very commonly lead containing pipes in old water supply
systems. Permissible limits of Pb and Cd in drinking water as per Bureau of Indian
Standard (IS 10500:1991) is 0.01mg/l and 0.003mg/l [20], respectively. In developing
countries like India, many industries are operated in a small and medium scale which
can pollute the environment considerably as they do not treat the effluents using an
appropriate treatment plant for removal of Lead and Cadmium. This situation demands
monitoring of the wastewater in a systematic manner and strict legislation for the
effluents from the industries and safe disposal of the effluent, so that the water is
safeguarded against elevated level of toxic metals.

1.2 Remediation of Heavy Metals Pollution

Conventional treatment technologies for the Pb(II) and Cd(II) ion removal are
not economical, and it further generate huge quantity of toxic chemical sludge. Till
date, different methods have been developed for the removal of heavy metal ions from
2
 Chapter 1

wastewater, some of which are coagulation, precipitation, ion exchange, electrolysis,

reverse osmosis, solvent extraction, adsorption and membrane filtration [21-23]. In
addition to being expensive, above methods suffer from other shortcomings such as
incomplete metal removal, large amount of reagents and energy requirements. Further
they generate toxic waste products, which need proper disposal as they are not eco-
friendly. The cost of precipitation-filtration method is comparatively low, but the
treatment procedure is complicated. On the other hand, the operation of ion exchange
method, reverse osmosis, membrane separation are simple for the removal of heavy
metals but the cost of resins and membranes are comparatively very high [24].
Therefore, the search for efficient, eco-friendly and cost effective remedies for
wastewater treatment is utmost important. It was only in the 1990s that a new scientific
area called bioremediation was developed to recover heavy metal ions from the
wastewater [25]. Bioremediation is a waste management technique that involves the
use of organisms to remove pollutants from a contaminated sites. According to the
Environmental Protection Agency (EPA), bioremediation is a “treatment that uses
naturally occurring organisms to break down hazardous substances into less toxic/non
toxic substances”.
Now these days, adsorption has become an alternate option to conventional
methods for the removal of heavy metal pollutants from contaminated aqueous solution
and this is also called as adsorptive remediation. Basically, adsorption is a mass transfer
process by which a substance is transferred from the liquid phase to the surface of a
solid. The main advantage of adsorption method for the removal of pollutants is that it
can be carried out in situ at the contaminated site and is usually environmentally benign
(no secondary pollution). The adsorbate are bound to the adsorbent by physical and/ or
chemical interactions [26]. Recent years have witnessed remarkable interest in
development of new adsorbents and to modify the performance of existing ones. The
activated carbon is being widely used to treat heavy metal polluted wastewater because
of their large specific surface area, high adsorption capacity and special surface
chemical properties [27]. Commercially available adsorbents such as silica gel,
activated alumina, zeolite etc. are quite expensive, therefore it is of interest to use agro-
waste materials as adsorbents to reduce the cost. Thus, use of low-cost, naturally and
easily available biological/agro-waste materials as biosorbents emerges as an effective
and affordable technological solution for adsorptive remediation of heavy metal ions

3
 Chapter 1

from aqueous solution. Due to use of these biomaterials as adsorbent the process is
known as biosorption.
Biosorption has been demonstrated [6, 28] to have a good potential to replace
the conventional methods for the heavy metal removal. Metal biosorption onto
agricultural wastes is very promising field but rather complex process affected by
several factors such as contact time, solution volume to mass of plant particles ratio
(m/V), particle size, solution pH and metal concentration [29]. Several mechanisms are
known to be involved in the biosorption process like chemisorption, complexation,
adsorption–complexation on surface and pores, ion exchange, micro-precipitation,
heavy metal hydroxide condensation onto the biosurface, and surface adsorption [30].
Ion exchange is recognized as the principal mechanism of biosorption for heavy metal
uptake. The polymeric structure of biomass surfaces consists of proteins, carbohydrates
and lipids, which contain negatively charged organic functional groups attached on side
chains of the polymeric structure. The functional groups of cell wall constituents
including proteins contain carboxyl, amino, phosphoryl, sulfonate groups etc. which
are the probable sites for ion exchange [31]. The use of waste biomass in biosorption is
more advantageous as compared to bioremediation for water treatment, since waste
biomass is not affected by toxic wastes and does not require a continuous supply of
nutrients as in case live biomass. Use of biosorption have additional advantage that used
biosorbent can be regenerated and reused for many cycles [32]. Therefore, it is
worthwhile to develop economical biosorbents for removal of heavy metals, which can
be utilized in developing countries in general. The major advantages of biosorption
process using agro waste adsorbents are their low cost, high efficiency, minimization
of sludge production, regeneration and possibility of metals recovery, therefore
contributing to environmental protection [33]. Agro-waste adsorbents consist of large
amount of dry biomass to extract toxic heavy metals from industrial effluents. The
biomass can be shredded or ground to yield stable biosorbent particles. Alternatively,
it can be immobilized by a synthetic polymer or fixed onto an inorganic support
material. A packed column can also be prepared using biosorbent particles and can be
used as the most effective devices for continuous removal of heavy metals. When the
metal binding reaches saturation, the biomass can be regenerated using dil. acid and/or
hydroxide solutions, which discharges small volumes of concentrated mixture of heavy
metals. Its advantages constitute the primary incentives for developing full-scale

4
 Chapter 1

biosorption processes for the removal of heavy metals from contaminated solutions
[34]. As is evident from the survey of published studies, numerous low cost raw natural
materials have been proposed as prospective biosorbents, including peat moss, algae,
leaf mould, sea weeds, coconut husk, sago waste, peanut hull, hazelnut, bagasse, rice
hull, sugarbeet pulp, plants biomass and bituminous coal [26, 35-40]. Most importantly,
the sorption capacities may also vary, depending on the characteristics of the distinct
adsorbents, the degree of surface modification and the initial concentration of the
adsorbate.
In view of effective utilization of the agro-waste materials for the removal of
heavy metals reported in literature, it is worth to study the potential of some unexplored
and/ or little explored agro-wastes as novel adsorbents for the removal of Pb(II) and
Cd(II) ions from wastewater with following objectives.

1.3 Objectives of This Study

1. Selection of different agro-waste materials based on their easy availability

and cost effectiveness and preparation of adsorbents.
2. To study the effect of various parameters such as pH, contact time, initial
concentration adsorbent dose and temperature on adsorption efficiency.
Evaluation of cadmium and lead removal performance of by conducting
batch experiments for agro-waste adsorbents composite.
3. Characterization of metal free adsorbents and metal loaded adsorbents i.e.
after conducting removal experiments and elucidation of the findings after
applying different kinetic and equilibrium isotherm models.

1.3.1 Selection of Agro-Waste Materials as Biosorbents

The selection of agro-waste material was based on their easy avalibility, cost
effectiveness and their easy processing. The selected agro-wasre materials are;
Cucumis sativus (Cucumber) peel, Desmostachya bipinnata (Kush grass) Leaves
(MDBL) and Bambusa arundinacea (Bamboo) Leaves. All these materials are
unexplored for the removal of heavy metals especially for Pb(II) and Cd(II) ions from
aqueous solution, however few reports are available regarding the use of Citrullus
lanatus (Watermelon) Rind for the removal of. Cr , Ni and Co [41]. These agro-wastes
are originated mainly in India, however, now a days they are also produced/used all

5
 Chapter 1

over the world. In addition to that, these agro-waste products are freely available, easy
to process and are eco-friendly. Further they possess convenient adaptability as
biosorbents and these type of materials ensure high swelling capacities with an
excellent mechanical strength [42]. Consequently, it is imperative to explore their
constructive use to minimize the waste generation. Therefore, in the present thesis we
choose these four different agro-waste material i.e. Cucumis sativus (Cucumber) peel,
Desmostachya bipinnata (Kush grass) Leaves (MDBL), Bambusa arundinacea
(Bamboo) Leaves and Citrullus lanatus (Watermelon) Rind to conduct the batch
adsorption studies for the removal of Pb(II) and Cd(II) ions from the simulated
wastewater.

********************

6
 2
Review of Literature
Rapid industrialization over the past few decades has inevitably resulted in
increased flux of environmental waste containing heavy metals and persistent organic
pollutants, such as high production volume chemicals, polychlorinated biphenyls,
dioxins and furans. The wastes may be infectious, toxic or radioactive [43]. Among
these pollutants, the heavy metals ions are stable and persistent environmental
contaminants since they cannot be degraded or destroyed [3]. These metal ions can be
harmful to aquatic life and as well as causes severe health effect on humans due to their
entrance in the food chain through drinking water and crop irrigation. This is a major
and a well-known problem particularly in poorer countries [44]. Lead, and Cadmium
stand out among these toxic metals, because of their hazardous nature and
omnipresence [45-47]. Industrial waste of many industries, such as metal plating
facilities, mining operations, battery industries, phosphate fertilizers, pigments,
stabilizers alloys, and tanneries constitutes etc. are the major source of Cd and Pb
pollution in natural water. Thus remediation of these heavy metals are of special
concern due to their persistent nature in the environment as they are non-biodegradable
and tend to accumulate in living organisms, causing various diseases and disorders [4,
5, 48]. As the present thesis is mainly focused on the removal of Pb(II) and Cd(II) ions
from water bodies/environment, therefore this review is based on the work done in this
area in the recent past.

2.1 Concerned Heavy Metals: Source & Toxicity

2.1.1 Cadmium (Cd)
Cadmium occurs naturally in the environment by the gradual process of erosion and
abrasion of rocks and soils, and from singular events such as forest fires and volcanic
eruptions. It is therefore naturally present everywhere in air, water, soils and foodstuffs.
Apart from their natural presence, Cd(II) ion polluted wastewaters/effluents are being
produced either by anthropogenic activities for Cd production or through secondary

7
 Chapter 2

sources such as smelting alloy manufacturing, electroplating, cadmium-nickel

batteries, in plastic, fertilizers, pesticides, mining, textile operations, pigments dyes,
and refining all over the world, [46, 49-59]. Through these industrial operations Cd(II)
ions that are being added to the water stream at a, much higher concentration than that
of the prescribed limits for industries. This leads to the health hazards and
environmental degradation. Taking this as a severe health issue, various regulatory
bodies have set the maximum limits for the discharge of toxic heavy metals in the
aquatic systems [27]. According to WHO’s recommendation Cd(II) limit in drinking
water is 0.003 mg/l [60].
Epidemiological and experimental studies have associated the occupational
exposure of Cd with neuro and nephrotoxic effect, lung cancer and other cancers such
as the prostate, renal, liver, hematopoietic system, urinary bladder, pancreatic, and
stomach [61, 62]. Specially the function of the nervous system gets severely affected
by the Cd exposure [15-17, 63], including Parkinson’s like symptoms, olfactory
dysfunction, headache and vertigo, slowing of vasomotor functioning, decreased
equilibrium, peripheral neuropathy, learning disabilities, and decreased ability to
concentrate [64-66]. The famous disaster ‘Itai-Itai’ due to contamination of cadmium
in Jintsu river of Japan is well known [67].

2.1.2 Lead (Pb)

Lead is released from lead treatment and recovery industries and its
concentration approach 200–500 mg/l in the industrial effluent [43], such as metal
plating tanneries, oil refining, pigment industries and mining [46, 58]. This value is
very high in relation to the water quality standards and it should be reduced to a range
of 0.1mg/l [60, 68-70]. Lead poisoning can cause hypertension, nephritis, abdominal
pain, constipation, cramps, nausea, vomiting, behavioral changes, learning disabilities,
reading problems, development defects, speech and language difficulties [71-75].
Acute toxicity is related to occupational exposure and is quite uncommon, however,
chronic toxicity on the other hand is much more common and may result when blood
Pb levels exceeds about 40–60 ug/dl or even more in some cases [19]. The situation can
become more adverse by causing persistent vomiting, encephalopathy, lethargy,
delirium, convulsions and coma, if not treated in time [19, 76]. Lead affects the
hematopoietic system directly through restraining the synthesis of hemoglobin by
inhibiting various important key enzymes that involved in the pathway of heme

8
 Chapter 2

synthesis and thus leading to anemia [77]. At higher level, it can cause permanent brain
damage and even death [78], hypertension and cardiovascular disease, infertility,
miscarriage [19], convulsions, paralysis, coma and ataxia [19] etc.

2.2 Heavy Metal Remediation

As discussed above, the enormous damage caused by water pollution specially
due to heavy metal accumulation in aqueous bodies have led to numerous investigations
as their objective to protect the threatened environment and living beings through
several methods/physico-chemical treatments [79-81]. The methods have been
critically reviewed by Fenglian et al. [3] for the removal of heavy metals contaminated
waste streams like chemical precipitation including hydroxide precipitation [82, 83]
and sulfide precipitation [84], ion exchange [85] , membrane filtration [86], zeolite
adsorption [87], carbon adsorption [88-90], co-precipitation, foam floatation [91-93],
coagulation [94, 95], advanced oxidation process [96] etc. However, these conventional
treatment processes have shortcomings like secondary pollution, high cost, high energy
input, large amount of chemical reagents, metallic sludge that make metal removal
difficult from aqueous solution. The sludge also needs further disposal in a safe manner
so as not to contaminate the environment. In addition, effluent even after such treatment
has unacceptably high total dissolved solids.

Table 2.1: Assessment of heavy metals removal processes as given in the literature.
Method Advantage Disadvantage Ref
Chemical Simple process, Low capital cost, Huge amount of sludge [97]
Precipitation Most of the metal can be removed and disposal its problem
Ion Exchange High regeneration of material, Metal High cost, Less no of metal ion [98]
selective, Recovery of precious metal removed
Electro No consumption of metal, Pure metal High capital cost/ running cost, [99]
Chemical can be achieved and Metal selective Initial solution pH and current
Treatment density
Membrane Less solid waste produced, Less High initial & running cost, Low [97]
Process & chemical consumption, High flow rate, and Removal decreases
Ultrafiltration efficiency and Small space required in presence of other metal ions.
No of metal can be removed Waste generation and [40]
High efficiency using inexpensive Comparatively low recovery of [100]
precursor adsorbents
Adsorption Less solid waste produced
High metal binding capacity, wide
range pH
Effective even on very low
concentration
No additional nutrient requirement

9
 Chapter 2

Usually, these processes are proficient for metal removal from bulk solution at
high or moderate concentrations or this can be said that these methods are inadequate
by technical and economic barriers especially at dilute heavy metal wastewater/lower
metal concentration in wastewater [24, 101] specially below <100 ppm [102]. In
addition to these restrictions, these processes are not cost-effective and even require
high level of expertise; hence they are not applied by many end-users [103-105]. Table
2.1 summarizes the main advantages and disadvantages of the various physico-
chemical treatments.

2.2.1 Adsorptive Remediation: An Emerging Trend!!

Keeping all the above fact i.e. shortcomings of the conventional methods in
mind, researchers looked for an alternative treatment for the removal of heavy metal
from polluted water. Therefore in present scenario, there is utmost need to work out for
adsorptive remediation of wastewater because in contrast to conventional methods it
can efficiently remove metal ions even from their low concentrated aqueous solution
with the use of economic and green alternative such as agro-waste based adsorbent
including plants waste, leaves, stems, shells, hulls husks, fruit peels etc. Therefore the
search and development of an efficient and low-cost metal removal processes is of
utmost importance. For these reasons, adsorption technology has emerged as a preferred
technique with wider applications due to its inherent low cost, simplicity, versatility
robustness and its effectiveness in reducing the of heavy metal concentration to very
low levels even from their lower concentration in aqueous solution. Basically,
adsorption is a mass transfer process by which a substance is transferred from the liquid
phase to the surface of a solid, and becomes bound by physical and/or chemical
interactions [26]. A number of materials have been extensively investigated as
adsorbents in water pollution control. Some of the important ones include silica gel
[106-108], activated alumina [109, 110], zeolites [111-113] and activated carbon [26,
88, 114-117], etc. due to their large surface area, high adsorption capacity and surface
reactivity. In spite of abundant uses of activated carbon, its applications are sometime
restricted due to its higher cost.
In recent years, the search for low-cost adsorbents that have metal-binding
capacities has intensified. Large quantities of locally available materials such as natural
materials, agricultural waste or industrial byproducts can be utilized as low-cost
adsorbents. Some of these materials can be used as adsorbents for water purification

10
 Chapter 2

with little processing i.e. conversion of these materials into activated carbon, modified
adsorbents etc., which would improve economic value, helping industries in reduce the
waste disposal cost and providing a potential alternative to activated carbon [97].

2.2.1.1 Biosorption: A Solution to Pollution

2.2.1.1.2 Use of Low-Cost Agro-Wastes Alternatives
The selection of the adsorbent should be based on the concentration of waste
and the cost effectiveness, easy availability and their easy processing [118]. In spite of
using commercial adsorbents, activated carbons, zeolites, activated alumina etc. for the
heavy metal removal from the aqueous solution, cost effective alternative adsorbents
proposes a new line of research in this direction and being economic they are acceptable
to the society in general, therefore their use should be promoted. Natural materials,
industrial waste materials, forest and agricultural products are the most abundant
renewable resources available worldwide. It is stated that an adsorbent can be termed
as a low-cost adsorbent if it requires little processing, is abundant in nature, or is a by-
product or waste material from some selected industries [43] and if the adsorbents go
under modification/treatment process, the expense involved for the treatment of
individual sorbents may vary due to their required degree of processing and local
availability of that particular material [103]. Thus, there is an exigency to explore all
possible sources of agro-based inexpensive adsorbents and their feasibility for the
removal of heavy metals should also be studied in detail [30, 39, 43, 71, 119].
Agriculture is one of the richest sources for low-cost adsorbents [120] and the use of
agriculture and forest waste for adsorption shows great promise. They are available in
large quantities, and may have potential as inexpensive sorbents [39, 121]. As the cost
is an important parameter for comparing the sorbent materials, low cost of agricultural
wastes make them preferable over several other sorbents [122] therefore option of using
these materials as biosorbents for wastewater treatment would help in reducing the
overall cost and to overcome the problem of waste disposal. Earlier studies enumerated
less expensive materials for Pb and Cd removal from water including algae [34, 123],
carbon cloth [124], peat [125, 126], agricultural byproducts [125, 127, 128], lignin [129,
130], biomaterials [131], bagasse fly ash [132, 133] etc. The technical feasibility of
various low-cost adsorbents for heavy metal removal from contaminated water has been
thoroughly reviewed earlier [26, 30, 39, 40, 134]. The schematic representation of agro-
waste based adsorption process is shown in Figure 2.1.

11
 Chapter 2

Figure 2.1: Schematic representation of overall adsorption using agro-waste

biosorbents (adsorption-desorption) cycle.

2.2.1.2 Biosorption Mechanism

The basic components of the agricultural waste materials include cellulose,
hemicellulose, lignin [135-137] (Figure 2.2), lipids, proteins, simple sugars, water,
hydrocarbons and starch, containing variety of functional groups (alcoholic, carbonyl,
phenolic, amido, amino, sulphydryl group [5, 138, 139].

Figure 2.2: Basic composition of agro-waste/plant waste adsorbents (Adopted From

[135]

12
 Chapter 2

These groups have the ability to bind heavy metal ions to some extent by
hydrogen ions replacement in solution or by the donation of an electron pair from these
groups to form complexes with the metal ions in solution [140]. Some biosorbents are
non-selective and adsorb a wide range of heavy metals with no specific priority,
whereas some others are specific for certain metals depending upon their chemical
composition. Presence of various functional groups and their complexation with heavy
metals during biosorption process have been confirmed by spectroscopic techniques
[4]. The functional groups present in agricultural waste biomass have the affinity for
heavy metal ions to form metal complexes or chelates that immobilize the contaminants
through reactions of chemisorption, complexation, adsorption on surface, entrapment
of adsorbate in inter and intrafibrillar capillaries and spaces of the polysaccharides
network as a result of the concentration gradient and diffusion through cell wall and
membrane [4, 141-143]. Sud et.al presented a very good schematic representation of
overall possible mechanism of adsorption using agro-waste biosorbents (Figure 2.3)

Figure 2.3: Plausible mechanism of biosorption [4]

13
 Chapter 2

Depending on the basis of site of adsorption/physicochemical interaction

between the metal and functional groups of the cell surface also, the biosorption process
is classified in the same manner [144] (Figure 2.4).

Figure 2.4: Classified according to the location where the metal removal is found.

The occurrence of complexion of functional groups with heavy metals during

adsorption process has been reported earlier [145]. A number of reviews have
appeared highlighting the potential of low-cost adsorbents prepared from agricultural
waste materials [4, 26, 39, 45, 97]. Apart from using raw/unmodified biosorbents for
the metal removal from aqueous solution, now these days modification process has also
been tried effectively to enhance the adsorption capacity of natural adsorbents/ plant
bio-sorbents, [146-151].

2.2.1.3 Modification of Raw Biosorbents

In general, modification of raw lignocellulosic biosorbents are performed to
increase their sorption capacities with physical or chemical treatments [137-139, 149,
152-157]. It is believed that lignocellulosic material contain functional groups as their
building blocks and these chemical functional groups are involved in metal-ion binding
[30]. Different physical and chemical treatments for modification of the surface of
adsorbents have been tested to increase the metal removal capacity of biomasses, and
for desorption of bound metals. Sometime modification of surface of adsorbents for the
enhancement of functional groups such as –OH, -COOH, -NH3, -NH2+ and -C=O etc.
was done by pretreatment/oxidation of biosorbents with activation agents like HNO3,
NaOH, CH3COOH, Chitosan, EDTA etc. [158-160]. Apart from these pretreatment

14
 Chapter 2

methods, activation is also a well-known process, used to activate the surface of

adsorbent and it increases their surface area. Activated carbon is one of well-known and
the most abundantly used adsorbents for heavy metal removal which is prepared by
using one of the two basic activation methods, namely physical activation and chemical
activation [43, 161].
Physical activation is a process in which the precursor is developed into
activated carbons using gases [162]. In the first phase, the precursor is carbonized by
pyrolyzation in the 600–900°C temperature range in an inert atmosphere. Second phase
is activation process, in which the material is exposed to oxidizing atmospheres (carbon
dioxide, oxygen or steam) usually in the temperature range 600–1,200°C [163], and as
a result an adsorbent is obtained with a high surface area and as well as formation of a
well-developed porous structure is also achieved by the removal of the more
disorganized carbon from their structural matrix.
Chemical modification became popular and many researchers devised elaborate
modification procedures [164]. Predominantly, chemical modifications include
delignification, esterification of carboxyl and phosphate groups, methylation of amino
groups, and hydrolysis of carboxylate groups. So many researcher have been followed
the chemical activation method to enhance the biosorption capacity of the biosorbents
used in their study for Pb(II) and Cd(II) ion removal [123, 146, 148, 150, 155, 156, 160,
165, 166]. Chemicals used in the chemical activation process are H3PO4, KOH, ZnCl2
or NaOH, HCl, Citric acid, followed by heating under nitrogen gas flow in the 450–
900°C temperature range [71, 72, 119, 156, 167]. The output of different studies varied
greatly and showed dependency on the biomass treatment [168, 169]. Weight loss of
biomass has been observed because of the treatments using heat, acids, bases, EDTA,
and different organic solvents [168, 170]. Reduced metal binding capacity is associated
with the weight loss of biomass when binding sites are destroyed [170], and when new
binding sites are generated as a result of partial cell wall degradation, the metal binding
capacity gets increased [168]. Chemical activation have advantage over physical
activation, that it’s lower temperature at which the process is accomplished. Maximum
Pb and Cd binding capacities have been reported to vary between different types of
agro/plant waste, with values ranging from a few milligrams to a few hundred
milligrams per gram of dry biomass. Thus, a number of biosorbents have been
investigated with or without treatment as adsorbents for the removal of Pb(II) and
Cd(II) ions from wastewaters.
15
 Chapter 2

2.3 Adsorption Study

2.3.1 Adsorption Isotherms
Isotherm adsorption models have been used in water treatment to predict the
ability of a certain adsorbent to remove a contaminant [85, 114, 118, 168, 171]. Under
the same environmental conditions (e.g. pH, temperature, rpm etc.), obtained
equilibrium isotherm plot provides best inference for the comparison of single-sorbate
sorption system. The plot of the sorption uptake (q) versus the final equilibrium
concentration of the residual metal remaining in the solution (Ce) is known as the
equilibrium adsorption isotherm. Adsorption isotherm are characterized by values of
isothermal constants that express the surface properties and affinity of the sorbent to
the sorbate at equilibrium of adsorption process [172, 173]. When a mass of adsorbent
and a contaminated aqueous solution are in interaction for an adequately long time,
equilibrium develops between the amount of adsorbed contaminant and the amount of
adsorbate remaining in solution For any system under equilibrium conditions, the
amount of material adsorbed onto the media can be calculated using the mass balance
of Eq.1
C0 −Ce
qe = ( )V [1]
m

where Co & Ce are initial concentration and final equilibrium concentration of

adsorbate (mg/l), qe is adsorption capacity at equilibrium (mg adsorbate/g adsorbent) ,
V is the volume of liquid (l) and m is the mass of adsorbent (g). Adsorption data for
wide range of adsorbate concentrations are most conveniently described by adsorption
isotherms, such as the classical isotherm model i.e. Freundlich [174] or Langmuir [175]
or isotherms.
In 1909 Freundlich [174] proposes an expression representing the isothermal
variation of adsorption of a quantity of gas adsorbed by unit mass of solid adsorbent
with pressure and generally expressed as:
1
log q e = log K F + n log Ce [2]

where Ce (mg/l) is the metal concentration in the aqueous phase at equilibrium;

KF and n are the Freundlich coefficients. KF provides an indication of the adsorption
capacity and n is related to the intensity of adsorption. If, the numerical value of n is
greater than 1, it suggests favorability of adsorption process. This isotherm does not
predict occurrence of saturation of the adsorbent by the sorbate, thus infinite surface
coverage is predicted mathematically, indicating multilayer adsorption on the surface

16
 Chapter 2

as shown in Figure 2.5. At present, Freundlich isotherm is widely applied in

heterogeneous systems especially for organic compounds or highly interactive moiety
on activated carbon and molecular sieves [176, 177].

Figure 2.5: Adapted Schematic representation [178] of Langmuir (Monolayer) and

Freundlich (Multilayer adsorption) Isotherm

In 1916, Irving Langmuir published [175] an isotherm for gases adsorbed on

solids, which retained his name i.e. Langmuir isotherm model. The Langmuir isotherm
is based on the assumption that a fixed number of adsorption sites are available on
adsorbent surface, and also indicates that the adsorption process is reversible. The
Langmuir isotherm may be used when the adsorbent surface is homogeneous and
expressed as
Ce 1 Ce
= + [3]
qe qm KL qm

where KL is the Langmuir constant and qm (mg/g) is adsorption capacity i.e. the
amount adsorbed to form a complete monolayer on the adsorbent surface. It is an
empirical isotherm derived from a proposed kinetic mechanism and based on four
hypotheses:
 The adsorbent surface is uniform, and all the adsorption sites are equal.
 Adsorbed molecules do not interact.
 All adsorption occurs through the same mechanism.
 Monolayer formation: molecules of adsorbate do not deposit on other,
already adsorbed, molecules of adsorbate, only on the free surface of the
adsorbent.
17
 Chapter 2

Langmuir isotherm provides the maximum adsorption capacity qmax/ qm that

defines a better sorbent with higher adsorption capacity. The comparison of sorbents
based on “% Removal” is also often encountered in the literature [4]. However, it is so
approximate that it could lead to outright misleading conclusions on the relative
sorption performance [7, 117]. It can only serve the purpose of crude orientation,
perhaps only for quick and approximate screening of biosorbent materials.
The Langmuir and Freundlich isotherm models are applicable to batch adsorber
systems where sufficient time is provided to allow equilibrium between the pollutant in
solution and the pollutant adsorbed on the media to occur [179]. Langmuir and
Freundlich isotherm models are frequently used isotherm models for describing short
term and mono component adsorption process of metal ions by different adsorbents
[180]. Several researcher applied their experimental data of adsorption study to both of
these isotherm models. Adsorption studies for the contaminants removal such as
adsorption of chromium(VI) using iron oxide nanoparticles [181], divalent heavy metal
ions removal from water using carbon nanotube sheets [182], removal of lead from
aqueous solution by activated carbon prepared from Enteromorpha prolifera [183]
followed Freundlich isotherm model, whereas Langmuir adsorption isotherm model
was followed by several adsorption studies such as Cd(II) ion removal by adsorption
onto nano zerovalent iron particles [184], biosorption of Pb(II) and Cd(II) from aqueous
solution by macrofungus [185], removal of Cd(II) and Pb(II) ions using Turkish illitic
clay [186], Cd ion removal from wastewater using rice polish [187], Cd ion removal
from aqueous solutions by chitin [188], cadmium (II) and Pb(II) ions removal using
sawdust [189] [190], cadmium adsorption onto oxidized granular activated carbon
[191], utilization of neem leaf powder for Pb(II) removal [192], and for Cu(II) ions
removal [193].
Several studies have been performed for Pb(II) and Cd(II) ion removal using
agro-waste biosorbents. Pb(II) ion removal from aqueous solution were studied by
numerous unmodified/modified agrowaste biosorbents such as banapeels [136], ficus
caracia leaves [194], leaf, stem and root phytomass of holly oak [127], crop milling
waste of black gram husk [195], rice husk [149, 157, 196-198], coffee residue activated
with zinc chloride [199], corncobs chemically modified hydrolyzed [160], modified
lawny grass [153], lignin modified from alkali glycerol [139], orange peel
formaldehyde treated [200] palm shell polyethyleneimine-impregnated [201], peanut
shells modified [202], pomegranate peel chemically treated [203], rose petals
18
 Chapter 2

chemically modified [159] and sugarcane bagasse chemically modified [165], wheat
bran acid treated [204] have been investigated in recent past.
Whereas Cd(II) ion removal has also been studied using a number of
modified/unmodified agro-waste materials such as rice husk [118, 149, 205], crop
milling waste black gram husk [195], neem, maize and ficus religiosa leaves [14, 206,
207], Scolymus hispanicus [208], modified cassava waste [146], nitric and citric acid
modified corncob [209], sodium hydroxide modified juniper fiber and rice husk [205,
210], sodium bicarbonate modified sugarcane bagasse [211], acidified wheat bran [212]
etc. The maximum adsorption capacity obtained applying Langmuir isotherm model
using these natural adsorbents, commercial adsorbents, bio-organism,
unmodified/modified plant wastes for the removal of Pb(II) ions and Cd(II) ions are
shown in Table 2.2 and Table 2.3, respectively.

Table 2.2: Adsorption capacities of different adsorbents for the removal of Pb(II) ions
from water.

Agro-waste qm/% Removal References

Algae, marine, nonliving biomass 126.5 [213]
Biomass, Mucor rouxil, dead 53.75
Biomass, Mucor rouxil, live 35.69 [214]
Banana Peel 2.18 mg/g [171]
Barley straw 23.2 mg/g [133]
Bengal Gram Husk 49.97 mg/g [195]
Charcoal natural 150 [215]
Charcoal activated 53.76mg/g
Charcoal raw (bamboo) 10.66mg/g [216]
Chitin natural 264mg/g [151]
Coconut shell granular activated carbon 21.88mg/g [217]
Coffee Residue 63.3mg/g [218]
Coir 15.2 mg/g [219]
Coir fiber 52mg/g [72, 220]
Eucalyptus Bark 0.89 mmol/g [221]
Ficus carcia leaves 32-38mg/g [194]
Fly ash, bagasse 2.50mg/g [220]
Grape stalk waste 0.241 mmol /g [222]
Grape bagaase 0.428 mmol/g [133]
Groundnut husk 0.19 mmol/g [154]
Hazelnut Shell 28.18 mg/g [223]
Almond Shell 8.08mg/g
Holy oak leaves 39.5mg/g [127]
Mapple sawdust >90% [224]
Pinus sylvestris 22.22 mg/g [225]
Orange Peel 476.1 mg/g [150]
Mango peel 99.05 mg/g [226]
19
 Chapter 2

Pomegranate peel 13.87 mg/g [227]

Ponkan peel 112.1 mg/g [228]
Peanut hull 0.18 mmol/g [229]
Palm Shell 95.2 mg/g [230]
Peepal Leaves 127.34 mg/g [71, 72]
Rice Husk 5.69mg/g [231]
Rice husk 31.13mg/g [71, 72]
Rice husk ash 10.86mg/g [197]
Soyabean oil cake activated carbon 476 mg/g [88]
Sunflower waste 33.2 mg/g [232]
Teak saw dust 40.70mg/g [71, 72]
Tree fern 38mg/g [233]
Walnut sawdust 4.48-15.90 mg/g [190]

Table 2.3: Adsorption capacities of different adsorbents for the removal of Cd(II)
ions from water.

Agro-waste qm/% Removal References

Algae, marine, dead biomass 80 [234]
Aspergillus niger, living 15.50 [235]
Ascophyllum nodosum 38 [236]
Aluminosilicates 42.7–57.9 [237]
Banana Peel 4.75 mg/g [136]
Banana Peel 32.52 mg/g [238]
Banana Pee 5.71 mg/g [171]
Bengal Gram Husk 39.99 mg/g [195]
Black Teawaste 13.77 mg/g [239]
Calcite 18.52 [240]
Cassava tubar bark waste 45.61 mg/g [156]
Modified casaava waste 18.05 mg/g
Coconut copra meal 4.99 mg/g [241]
Coconut Shell 45-60mg/g [147]
Coconut coir pith 99.9% [242]
Corncobs 8.89 mg/g [156]
Corncob oxidised 19.3-5.2mg/g [209]
Corncob 6.43 mg/g [243]
Eucalyptus Bark 14.53 mg/g [244]
Pinus pinaster bark 8 mg/g
Ficus religiosa leaf 27.14 mg/g [14]
Ficus carcia leaves 29-34mg/g [194]
Grape stalk waste 0.25mmol/g [222]
Grape bagasse 0.774 mmol/g [133]
Groundnut husk 0.36 mmol/g [154]
Holly oak leaves 53.2mg/g [127]
3.65 mg/g [136]
Orange Peel 293.3 mg/g [150]
4.96 mg/g [245]
Mango peel 68.92 mg/g [226]
20
 Chapter 2

Jackfruit peel 52.08 mg/g [246]

Pea Nut Hulls 5.96 mg/g [247]
Pine Bark 5 mg/g [248]
Pinus sylvestris 9.29 mg/g [225]
Rice husk (Epichlorohydrin treated) 11.12 mg/g
Rice husk (NaOH treated) 20.24 mg/g [158]
Rice husk (NaHCO3) 16.18 mg/g
Teawaste 16.87 mg/g [249]
Sawdust Cedrus deodar NaOH treated 73.62mg/g [189]
Sugarcane bagasse pith 24.70 mg/g [132]
Syzygium cumini L leaf 34.54 mg/g [250]
Walnut sawdust 5.76 mg/g [190]
Wheat Bran 15.71 mg/g [251]
Wheat Bran 0.70 mmol/g [252]

2.3.2. Thermodynamic parameters

Analysis of thermodynamic parameters of equilibrium sorption can give
noteworthy information about adsorption process i.e. whether it is spontaneous or not.
Free energy change (ΔGo) is a fundamental criterion of process spontaneity which is
related to the equilibrium constant by the following relationship [184, 253].

ΔGo= -RT ln Kc (4)

The spontaneity of the adsorption process is also affected by the thermodynamic

parameters ΔH◦ (heat of adsorption) and ΔS◦ (entropy change). The relation of ΔG◦
with ΔH◦ and ΔS◦ is generally expressed as

∆Go = ∆H o − T∆S o (5)

∆So ∆Ho
ln K c = − (6)
T RT

The correlation between free energy change, enthalpy change (ΔHo) and entropy
change (ΔSo) is given by the above equations. R is the universal gas constant (8.314
J/mol K), T is the absolute temperature and K is equilibrium constant. The apparent
equilibrium constant of the biosorption, ln kc is obtained from multiplying Langmuir
constant KL and qm [254-256]. Thermodynamic parameters i.e. ΔGo, ΔHo, and ΔSo
defines the spontaneity, endo/exothermic nature of adsorption process and feasibility
of adsorption process, respectively. ΔG◦ will always be negative according to Eq. (5)
at any given temperature for adsorption system with negative values of ΔH◦ and
positive values of ΔS◦. Thus, it is very important to have the knowledge of the signs of

21
 Chapter 2

various thermodynamic parameters in determining the spontaneity of a given process

[257].

2.3.3 Adsorption Kinetics

A simple introductory sorption kinetics test will establish the contact time
necessary for the given adsorbent to reach up to the equilibrium state characterized by
the unchanging adsorbate concentration in the solution [7] that is determined by time-
based analyses. The rate prediction for a given adsorption system at which adsorption
takes place is probably the most important factor in adsorption system design [258].
Basically, adsorption kinetics depends on the adsorbate–adsorbent interaction and
system condition and has been investigated for their suitability for their application to
control the water pollution problem [259]. The adsorption mechanism and the reaction
rate are the two dynamic evaluation factors for an adsorption process unit. Solute uptake
rate determines the residence time necessary for completing the adsorption process and
can be computed from kinetic analysis [259]. Numerous attempts were made in
formulating a general expression to describe the kinetics of adsorption on solid surfaces
for the liquid–solid adsorption system [259]. The adsorption rate is an important factor
for a better choice of material to be used as an adsorbent; where the adsorbent should
have a large adsorption capacity and a fast adsorption rate. In past decades, several
mathematical models have been proposed to describe the adsorption data, which can
generally be classified as adsorption reaction (i.e rate order equations) and adsorption
diffusion (i.e. intraparticle diffusion model).
Most of adsorption studies used pseudo-first-order and pseudo second-order
models to study the adsorption kinetics [153, 243, 260-263]. The first order kinetics
model was presented by Lagergren in 1898 [264] presented a first-order rate equation
to describe the kinetic process of liquid–solid phase adsorption of oxalic acid and
malonic acid onto charcoal, which is believed to be the earliest model pertaining to the
adsorption rate based on the adsorption capacity [265]. To distinguish kinetic equations
based on adsorption capacity from solution concentration, Lagergren’s first order rate
equation has been called pseudo-first-order [266]. The pseudo-first-order equation is
generally expressed as:
𝐾 1𝑎𝑑
log(q e − q t ) = logq e− 2.303 t [7]

where qe, qt are the adsorption capacities (mg/g) at equilibrium and at time t,
respectively. K1ad is the rate constant of pseudo-first-order adsorption. The values of

22
 Chapter 2

log (qe-qt) were linearly correlated with time (t). The plot of log (qe - qt) versus t should
give a linear relationship from which K1ad and qe can be determined from the slope and
intercept of the plot, respectively.
The second-order Lagergren equation was given by Ho and Mckay [266]. It is
expressed as:
t 1 t
= + [8]
qt K2ad q2e qe

where, K2ad is the rate constant of pseudo-second-order adsorption (g mg-1 min-

1
). The plot of (t/qt) and t should give a linear relationship from which qe and K2ad can
be determined from the slope and intercept of the plot, respectively. Pseudo second
order kinetics suggests the occurrence of chemisorption process [44, 158, 184, 267,
268]
The pseudo-first-order and pseudo-second-order kinetic models could not
identify the diffusion mechanism and the kinetic results can be then analyzed by using
adsorption diffusion model. The adsorption diffusion models are mainly constructed to
describe the process of film diffusion and/ or intraparticle diffusion [265]. According
to this model, if a linear trend obtained using the plot of solute uptake (qt) vs the square
root of time then it can be said that intraparticle diffusion is involved in the adsorption
process. If the obtained lines pass through the origin then intraparticle diffusion is the
rate controlling step [182, 183, 269], whereas deviation of lines/plots from origin
indicates that intraparticle diffusion is not the only rate-limiting step, but also other
processes may control the rate of adsorption, all of which may be operating
simultaneously with some extent of boundary layer control.
The mechanism of adsorption of a sorbate on a sorbent follows a series of steps
in which the slowest step control the overall rate of the process [270]. Generally, pore
and intraparticle diffusion are often rate limiting in a batch reactor while, for a
continuous flow system, film diffusion is more likely the rate-limiting step [271]. This
possibility was tested in terms of a graphical relationship between qt and the square root
of time, t1/2, according to the intraparticle diffusion model proposed by Weber and
Morris [272]. The intraparticle diffusion model is expressed as,
q t = K i t 0.5 + I [9]
where qt is the amount of Cd(II) ion adsorbed at time t, I is the intercept and Ki
is the intraparticle diffusion rate constant. The value of I provides an insight about the
thickness of the boundary layer.

23
 Chapter 2

So many researchers have analyzed their experimental data applying these

kinetic models to provide insightful details regarding adsorption process. It is reported
in literatures by authors in most of the cases, the pseudo-first-order equation of
Lagergren does not fit well for the whole range of contact time and is generally
applicable over the initial duration of contact time of the adsorption process [130, 190,
194, 273]. Whereas experimental data follows pseudo second order kinetic model for
entire range of contact time. Pseudo second order kinetics was followed by adsorption
studies for metal uptake by number of investigation such as modified distillation sludge
of rose (Rosa centifolia) petals for Pb(II) removal [159], removal of Cd(II) ion from
aqueous solution by living Aspergillus niger [235], Cd(II) removal by unmodified rice
straw [101], sorption Pb (II) from wastewater by green algae Cladophora fascicularis
[274], Removal of lead from aqueous solution by activated carbon prepared from
Enteromorpha prolifera [183], Cd(II) ion removal from the aqueous solutions by
activated carbon derived from Ceiba pentandra hulls [275], biosorption of Pb(II) and
Cd(II) from aqueous solution by macrofungus (Amanita rubescens) biomass [185],
Cd(II) ion removal using by chitin etc.

2.3.4 Parameters Affecting Biosorption

Removal using biomass is a rapid process in which the bulk of the removal
occurs during the first few minutes of contact between the metal solution and the
biomass. The removal is mainly influenced by pH and very low removal is typically
observed at pH below 2-3, whereas at pH above 3 a sharp increase in removal occurs
and maximum removal is often reached at pH 4-6 [146, 245, 276]. The effect of pH is
a result of competition for negatively charged binding sites between cationic metals and
protons. It has been generally reported that in highly acidic medium (pH~2) the removal
of metal ions is almost negligible and it increases by increasing the solution pH up to a
certain limit.
Several studies have shown that the pH has been very imperative factor,
affecting the metal adsorption on biomass [277]. Not only do different metals have
different pH optima for their sorption, these may also differ from one type of sorbent
to the other [278]. Reviewing the Pb(II) and Cd(II) ions predominant species as function
of the solution pH, it can be inferred that .free cadmium (II) and lead (II) ions are the
predominant species formed at pH between 3.5 and 6 [279]. At pH values higher than
8 for cadmium, or higher than 5 for lead, several hydroxyl low-soluble species can be

24
 Chapter 2

formed, i.e. Cd(OH)2, Cd(OH)3− or Pb(OH)2 [280] (Figure 2.6). According to several
reports, [171, 274, 281] at low pH the, minimum biosorption is due to the fact that H+
ions start competing with metal ions due to their high concentration and high mobility.
Thus making H+ ions preferential over metal ions for the adsorption to occur on surface
of adsorbent and therefore percentage metal adsorption/removal is less at lower pH.
Whereas, the number of H+ ions decrease and simultaneously greater number of ligands
with negatives charges results in greater metal ion uptake at higher pH [150]. FTIR
analysis of biomasses have revealed that carboxyl, phosphoryl, sulfonate, and amino
groups are the main functional groups responsible for heavy metal binding onto
biomass [282].

Figure 2.6: Aqueous speciation of Cd and Pb as a function of pH in the single-element

system (Cited from [280]).

The effect of pH on the biosorption process may also be explained in terms of

pH of the point of zero charge, (pHpzc) at which the adsorbent surface is neutral. When
the biomass is kept in a solution having pH less than pHpzc of biomass, the protonation
of certain functional groups occur and the biomass behaves as a positively charged
matrix [134]. An increase in pH above this point makes the functional groups on the
biomass type deprotonate and act as negative species [134].
Another important parameter, which affects biosorption is the initial ion
concentration of heavy metal ions. As a rule, the biosorption capacity increases with
increasing initial metal concentration as it provides a driving force to overcome mass
transfer resistance between the biosorption medium and adsorbent [152, 283, 284]. At
lower ions concentration in the solution, the ions would interact with almost all
available active binding sites and thus facilitate almost higher percentage adsorption
25
 Chapter 2

whereas at higher concentrations, more ions are left un-adsorbed in the solution due to
the saturation of the binding sites [285] [198] and therefore facilitate low percentage
removal.
The effect of biomass dosage on metal ions adsorption was also investigated by
many workers [171, 210, 262, 286, 287]. For a fixed metal initial concentration,
increasing the adsorbent dose provides greater surface area and availability of more
active sites, thus leading to the enhancement of percentage metal removal [288]. In
other words, at higher adsorbent dosage, number of ions adsorbed at overall surface
area are higher due to the availability of more empty binding sites as compared to lower
dosage which has less binding sites to adsorb the same amount of metal ions in the
adsorbate solution [283]. Whereas by increasing the adsorbent dosage adsorption
density/adsorption capacity decreases. In other words it can be understood as, the
amount of ions adsorbed per unit adsorbent weight is high at low adsorbent dosage.
When the adsorbent dosage increases, the adsorption capacity/unit weight (adsorbate
mg/ adsorbent g) is reduced due to a decrease in adsorbate (i.e. metal ions) to binding
site ratio distribution onto larger amount of biomass binding sites.
In batch biosorption experiments, the determination of the optimum contact
time required to achieve the highest removal of metal ions is one of the key factors
usually assessed [171]. Equilibrium time is one of the important parameters for
selecting a wastewater treatment process [79, 287]. With increase in contact time
between interaction of adsorbate and adsorbent, researcher observed metal rapid
removal rate initially, but it gradually decreases with time until it reaches equilibrium.
The rate of percent metal removal is higher in the beginning due to availability of larger
surface area of the adsorbent for the adsorption of the metal ions [183, 289].

2.3.5 Scope of Reusability of Adsorbents

Desorption experiments have established the reversibility of cadmium and lead
removal by several biomasses. Dilute mineral acids (HCl, HNO3, H2SO4), salt solutions
(CaCl2, NaCl, KCl, KI) and EDTA have been tested for desorption. The best results,
i.e. recovery close to 100%, have been obtained with dilute acids [267, 274, 290-293].
The resorption capacity of different biomasses after desorption of bound metal is
generally lower than that of the fresh biomass. The degree of reduction in percentage
removal depends on the biomass and desorbent/eluent used, and has been reported to

26
 Chapter 2

vary from 1 to 63 % for dilute acids, and from 6.5 to 30 % for EDTA [213, 267, 293,
294].
In a precise way it can be said that in present scenario biosorption emerges as a
relatively new and efficient process that has shown significant contribution for the
removal of contaminants from aqueous effluents. Being highly efficient, low cost and
renewable source of biomass, agro waste material should be exploited for heavy metal
remediation and these materials could prove to be better substitutes for the expensive
adsorbents as well as expensive treatments. Some of the important issues can be
summarized as below:
• Selection and identification of an efficient and economic low-cost adsorbent
is an important key to achieve the maximum removal of precise contaminant
depending upon the adsorbent–adsorbate characteristics.
• Further these agro waste materials can be modified for better efficiency and
multiple reuses to enhance their applicability at industrial scale [4].
• Low production/processing cost for adsorbent production.
• Regeneration studies plays important role to recover the adsorbate as well
as adsorbent.
Overall this review focuses on the potential of a wide variety of low cost
sorbents for heavy metal ions biosorption on inexpensive and efficient biosorbents from
agricultural waste materials as replacement strategy for existing conventional systems.
The use of low cost agro-waste materials is still not very common, in general, however
they present a very good adsorption capacity [39, 295]. [4] and very less work has been
carried out in this direction. Although the amount of available literature data on the use
of low-cost adsorbents in water and wastewater treatment is increasing at a tremendous
pace, there are still an utmost need to search other unexplored biorsbents over currently
available expensive commercially activated carbons to use them for water treatment
system specially in case of heavy metal pollution in aqueous solution

*******************

27
 Removal of Pb(II) ions from simulated wastewater
3
using Cucumis sativus (Cucumber) peel
3.1 Introduction
Heavy metal ions present in the environment especially from the transition
series are of foremost concern due to their toxicity to several life forms. Besides their
toxic and harmful effects to living organisms of water, heavy metals also accumulate
throughout the food chain and may affect/harm human beings [296]. Beyond
permissible levels they can cause grave health disorders/toxicity; therefore,
considerable attention has been paid to wastewater treatment prior to its discharge in
the environment. Among these heavy metals, lead ions are significant environmental,
hazards because they are widely used in a variety of industrial processes such as battery
manufacture, electronics, petroleum refining, and metal mining etc. [297].
When ingested/absorbed by humans, it can cause severe health issues such as semi-
permanent brain/nervous system damage, kidney diseases and many other symptoms
[16, 19]. Therefore, the removal of lead from aqueous solution is still the focus of
extensive research [125, 185]. Many surface chemistry processes for wastewater
treatment such as precipitation, adsorption, membrane processes, ionic exchange,
floatation, and others [298, 299] have been investigated in detail. However, these
technologies suffer from some disadvantages such as high cost, sensitive operating
conditions and production of secondary sludge [4, 24]. These methods use huge
amounts of chemicals and are partially or non-effective at low concentrations of metals
[263]. Adsorption is by far the most versatile and widely used process, and activated
carbon is the furthermost commonly used adsorbent [300], conversely the use of
activated carbon is also very expensive. Therefore, the concern over the problem of
heavy metal pollution has led to develop alternative technologies for effective removal
of pollutants from aqueous effluents and advocating the use of several agro waste
materials and by-products of cellulosic origin for sorption of heavy metals [301, 302].
It has been reported that the low-cost agro-waste adsorbents have demonstrated
outstanding performance for removal of certain metal ions as compared to activated

28
 Chapter 3

carbon [30]. In recent years, agricultural by-products have been widely considered for
metal sorption studies including peat, banana pith, pine bark, peanut, shells, hazelnut
shell, rice husk, wood, sawdust, wool, soybean and cottonseed hulls, orange peel,
leaves and compost [26, 39, 40, 44, 72, 134].
In view of above, this chapter describes the use of a novel adsorbent dried
Cucumber peel (Cucumis sativus peel, CSP) for the removal of Pb(II) ions from
simulated aqueous solution through batch experiments. Cucumber peel is produced as
a waste product of the food processing, and has no significant industrial and commercial
use. CSP is fibrous material, mostly composed of cellulose, hemi-cellulose, lignin, and
chlorophyll pigments [303], which contain carboxyl and hydroxyl functional groups,
that is capable to potentially adsorb several metals through ion–exchange and/or
complexation mechanism. The main objective of this study was to investigate the
effects of various parameters such as solution pH, adsorbent dosage, and contact time
on the adsorption efficiency of Pb(II) ions on CSP. In most of the batch studies, effect
of individual parameter of the adsorption process has been investigated maintaining
other parameter constant at specified levels [304]. Equilibrium, kinetics and
thermodynamic studies were also performed to determine the potential application of
CSP for effective removal of Pb(II) ion.

3.2 Material and Method

3.2.1 Chemicals
All reagents used including Standard Pb(II) 1000 mg/l solution were of
analytical grade purchased from Merck, India. The experimental stock solution of
Pb(II) (1000mg/l) was prepared from Lead Nitrate [Pb(NO3)2] and further dilutions
were prepared from this stock solution with the use of deionized water (DW) produced
by a pure hyper filtration water system (Millipore, Water purification system, USA).
For the pH study, pH of the solutions was maintained by using 0.1N HNO3/0.1N NaOH.
Standard labware and glassware were cleaned with HNO3 and rinsed with DW.

3.2.2 Adsorbent Preparation

CSP was collected in bulk from the individual users/commercial users. It was
thoroughly rinsed with DW to remove dust and soluble material and allowed to dry at
100°C for 24 hours in the oven. The dried CSP were crushed, ground using a domestic
mixer. The ground materials were then sieved to constant particle sizes of 0.250mm

29
 Chapter 3

using analytical sieve (Sethi Standard Test Sieve, Delhi, India ) [305] stored in a
desiccator for further use.

3.2.3 Batch Adsorption Studies

Batch adsorption experiments were carried out in order to evaluate the use of
CSP as biosorbent for the removal of Pb(II) ions from aqueous solutions. For these
experiments, pre-weighed amount of the CSP and a measured volume of Pb(II) ion
solution were taken in 100ml Erlenmeyer flask and stirred in an incubator shaker at a
constant temperature (25±2oC) for 240 min to ensure equilibrium. After shaking the
flasks for regular intervals, samples were withdrawn and filtered. The filtrates were
analyzed for the concentration of Pb(II) ions by flame Atomic Absorption
Spectrophotometer; AAS (Perkin- Elmer, AAnalyst 300, USA) using Electrode less
Discharge Lamp (EDL) with characteristic wavelength of 283.3 nm of Pb(II). A first
series of sorption experiment was carried out with an initial concentration of 25mg/l to
optimize the most favorable pH for further biosorption studies. Thereafter, the
influences of adsorbent dose, contact time, initial ion concentration were also evaluated.
Percentage metal removal was calculated using the following formula,
C0 −Ce
%R= × 100 [1]
C0

where C0 and Ce (mg/l) are initial and equilibrium concentration, respectively.

Isotherm studies were recorded by varying the initial concentration of Pb(II) ion from
5- 150 mg/l with CSP. A known and same amount of adsorbent was added into the
solutions of Pb(II) ions in different flasks followed by agitating them at 160 rpm till
equilibrium is reached (~ 90 min). The adsorption capacities qe (mg/g) were calculated
by mass balance relationship equation:
(Co −Ct )
qe = V [2]
W

Where, Co, Ct (mg/l) are initial concentration and concentration at time t, V is the
volume (l) of Pb(II) ion solution and w is the mass of adsorbate (g). Adsorption isotherm
experiments, thermodynamic and kinetic experiments were performed in duplicates.

3.2.4 Analytical/ Physico-Chemical Characterization

The prepared adsorbent was characterized for its physic-chemical parameters
as in relation to the knowledge of the adsorptive behavior of CSP. It is often desirable

30
 Chapter 3

to have information about the basic properties of adsorbent which determines their
utility in adsorption process (Table 3.1).

3.2.4.1 Determination of Bulk Density, Particle Density and Porosity

The CSP was characterized for bulk density, particle density and porosity using
the method described by Ekpete et al. [306]. Regarding the analysis of bulk density of
CSP, the CSP was dried at a temperature of 105oC for one hour until its weight become
constant. A known quantity of ground CSP was passed into a dry graduated cylinder
(readable to 2ml). The level of adsorbent particles was carefully managed without
compacting and the unsettled apparent volume (V) was noted to the nearest graduated
unit. The bulk density (Table 3.1) was calculated in g/ml (or g/cm3) by the formula:

Mass of adsorbent,m (g)

Bulk Density = (3)
Volume of adsorbent,V (ml)

For particle density measurement the, the known mass of the adsorbent was
transferred in a dry graduated cylinder same as in bulk density, but here the cylinder
was stirred/ or the particles were tapped to remove the trapped air between the particles.
The particle density was calculated using formula:

Mass of adsorbent,m (g)

Particle Density = Volume of dry airfree adsorbent,V (ml) (4)

Simultaneously percentage porosity was determined using formula:

Bulk Density
% Porosity = 1 − Particle density × 100 (5)

3.2.4.2 Moisture Content Determination

Moisture content was determined according to ASTM 2867-99 [307]. A known

amount of CSP (2g) sample was weighed and dried in a furnace continuously. The
drying sample was constantly reweighed at a 10 min interval until a constant weight
(wp) was obtained. The crucible and its content was retrieved and cooled in desiccators.
The % Moisture content was calculated from equation (6)

(2−wp)
% Moisture Content = × 100 (6)
wo

Where wp and wo are the weight of CSP retrieved from the furnace and initial
dry weight of the CSP, respectively.

31
 Chapter 3

3.2.4.3 Ash Content Determination

Ash content determination was done according to the ASTM D2866-94 method
[308]. Dry CSP sample (1g) was placed into crucible and transferred into a preheated
muffle furnace set at a temperature of 1000°C. The furnace was left on for one hour
after which the crucible and its content was transferred to desiccators and allowed to
cool. The crucible and content was reweighed and the weight of the ash content of the
CSP sample (wash) was recorded. Then the percentage ash content (Table 3.1) was
calculated from the equation 7:
wash
% Ash Concent = × 100 (7)
wo

3.2.4.4 FTIR and SEM Analysis

Fourier Transform Infrared (FTIR) spectrophotometer (Spectrum RX-1 FTIR,

Perkin Elmer, USA) was used to analyse the presence of various functional groups on
the surface of adsorbent. The morphological changes of CSP was observed before and
after adsorption studies, using Scanning Electron Microscope SEM (Carl Zeiss
EVO18 Special Edition Model, Germany).

3.2.5 Effect of Other Ions in Aqueous Solution on Adsorption

To compare the removal efficiency of Pb(II) ions with CSP with the real
wastewater, the effect of presence of other ions on Pb(II) ion removal was also
evaluated. To study the effect of anions and cations on Pb(II) ion removal, a simulated
solution containing different anions such as Sulfate (SO4-), carbonate (CO32-), chloride
(Cl-), nitrate (NO32-) and cations like Na+, K+, Ca2+, Mg2+ of concentration 2,5,15, and
20mg/l have been chosen. To facilitate the comparison of results, all the solutions of
cations were prepared in present study with their nitrate salts, whereas, studied anions
solutions were prepared using their sodium salts. The different concentrations of anions
and cations were added individually along with 25 mg/l Pb(II) ion solution in different
flasks and were shaken for a time period of 2h. Subsequently, the solutions were filtered
and the filtrate were analysed for the remaining Pb(II) ion concentration. For the
evaluation of the effect of presence of other heavy metal ions such as Cd(II), Cu(II) and
Ni(II) ions on the removal of Pb(II) ions, experiments were also performed similarly.
For this study, only one concentration (25mg/l) of Cd(II), Cu(II) and/or Ni(II) ions were
taken to form binary metal as well as multi-metal ions solution. Rest procedure was
same as illustrated above.
32
 Chapter 3

3.2.5 Desorption and Regeneration

Desorption procedure described by Sari et al. was adopted [185] to study the
reusability of the exhausted CSP. For this experiment, a sample volume of 25ml
containing 25 mg/l of Pb(II) ions, was transferred into a beaker and 25mg of CSP
(according to 1 g/l CSP dosage) was added to the system. The mixture was shaken again
for 60 min at 160 rpm and filtered with Whatman filter paper. The filter paper and Pb(II)
loaded CSP were washed with DW. In order to desorb the adsorbed Pb(II) ions from
CSP, it was washed with sequential addition of 1-1ml of 1M HNO3 up to 8-10 times
and filtrate were collected. The filtrate was determined by AAS for the Pb(II) ions
concentration. In order to reuse CSP for further set of experiments, it was washed with
optimized amount of 1M HNO3 and distilled water, successively followed by drying of
CSP in oven at 100°C for 1h. The same procedure was applied to the blank solution for
comparison purpose.

3.3 Results and Discussion

3.3.1 Characterization of CSP
The physico-chemical parameters of CSP such as percentage ash content,
moisture content, particle density, bulk density, and porosity were analysed to provide
the detail idea about their behavioral characteristic regarding adsorption (Table 3.1).

Table 3.1: Physical Characteristics of CSP

Parameters
Moisture content (%) 13.5
Ash content (%) 8.5
Particle density 0.235
Bulk density (gcm3) 0.127
Porosity (%) 15

The analysis of percentage moisture and percentage ash content were high
suggested high organic content which may be due to its plant origin. Factors which
influence the overall density measurements include; organic matter content, the
porosity of the adsorbent, and the adsorbent structure. These factors will intern control
hydraulic conductivity [309] that describes the ease with which water contain adsorbate
ions/metal ions can move through groves, pores, spaces or fractures and therefore high
values of these parameters supports/enhance their metal uptake capacity. Porosity is
directly related to the adsorptive properties of adsorbent as the highly porous material
can adsorb high quantity of adsorbate [310].

33
 Chapter 3

3.3.2 Effect of pH
The pH plays a significant role on the sorption of adsorbates on the surface of
adsorbents. The pH level affects the network of negative charge on the surface of the
adsorbent, as well as hydrolysis of the metal ions [155]. Therefore, the preliminary
experiments were performed to determine the optimum pH value. In this experiment,
the pH of solution was varied from 3.0-8.0 of Pb(II) ions vs pH (Figure 3.1). A plot of
percentage removal shows a trend of increasing metal ion binding with increasing pH
from 3.0 to 5.0 [311] and the optimum Pb(II) ion sorption obtained at pH 5.0. However,
a plateau is obtained with slight decrease in Pb(II) sorption beyond pH 5.0. Under
highly acidic conditions (pH ≈ 3.0), the metal sorption efficiency was very small, and
this lower efficiency is due to the presence of high concentration of H+ ions (hydronium,
H3O+) and also partly because of the chemical speciation of Pb(II) [312]. At higher pH
value, fewer H+ ions exist, and consequently, Pb(II) ions have a better chance to bind
on the freely available binding sites. The adsorption experiments was not performed in
high basic conditions i.e. beyond pH 8 due to formation of lead hydroxide Pb(OH)2
(Eq. 8 & 9),
Pb2+ + H2O Pb(OH)+ + H+ (8)
Pb2+ + 2H2O Pb(OH)2 + 2H+ (9)

Figure 3.1: Effect of pH on Pb(II) sorption by CSP at 25°C (Condition: 25mg/l Pb(II),
160 rpm, 1g/l Adsorbent dosage, 60 min)

3.3.3 Effect of Adsorbent Dosage

The adsorption of Pb(II) on different adsorbent dosage (0.5–10.0 g/l) was
studied keeping other experimental conditions such as Pb(II) concentration (25 mg/l),
stirring speed (160 rpm), pH (5.0) and contact time (60 min) constant. The outcome

34
 Chapter 3

indicates (Figure 3.2) that percentage removal of Pb(II) increases with increasing CSP
dose from 0.5 to 5g/l to a maximum, however percentage removal of Pb(II) decreases
slightly on higher dose of CSP beyond 5g/l. The increase of percentage removal of
Pb(II) with increasing dose of CSP may be ascribed to increase of surface area of
adsorbent consequently increase in number of adsorption sites on surface of CSP.

Figure 3.2: Effect of adsorbent dosage for Pb(II) sorption by CSP at 25°C (Condition:
25mg/l Pb(II), 160 rpm, 60 min)
Maximum removal of ~ 82 % was observed with an adsorbent dosage of 5 g/l,
whereas, beyond this the removal capacity of CSP was lesser. Lowering of adsorption
capacity of CSP at higher dosage may be attributed to overlying or aggregation of
available binding sites ensuing in decrease in total available adsorbent surface area to
metal ions and an increase in diffusion path length [313].

3.3.4 Effect of Contact Time

The retention of heavy metals on the surface of adsorbent was found to be
increased with increasing contact time for a fixed concentration of Pb(II) ions (25mg/l)
and a fixed adsorbent mass (5g/l) and optimum pH 5.0 [314] (Figure 3.3). The Pb(II)
ions sorption increased steeply with time up to 90 min and thereafter showed steady
adsorption rate. The maximum uptake of Pb(II) ions was ~ 87 % at 90 min. The gradual
increase of percentage removal of Pb(II) ions with time on the surface of CSP may be
attributed to the binding of those Pb(II) ions which are very close to the free
coordinating/adsorption sites on the surface of CSP.

35
 Chapter 3

Figure 3.3: Effect of contact time on Pb(II) sorption by CSP, at 25°C (Condition:
25mg/l Pb(II), 160 rpm, 5g/l Adsorbent dosage)

Subsequently the metal ion which are away from CSP, diffuse gradually near to
CSP therefore the percentage removal increases with time. Further, the conformation
of CSP may change on initial binding of Pb(II), making some binding sites less
accessible/accessible with difficulty therefore some binding may take time
consequently maximum adsorption occurs around 90 min rather than instantaneous
adsorption. In addition to above, at initial phase the large number of sites are available
for sorption [183], however, few minutes later the remaining free surface sites are hard
to be occupied due to repulsive forces between the Pb(II) on the solid and the aqueous
phases [315, 316]. For further experiments, optimal contact time (90 min) was used to
make sure that equilibrium was properly attained.

3.3.5 Equilibrium Studies

The equilibrium study is the most important informative parameter to
understand the adsorption process. It indicate how metal ions are partitioned between
the adsorbent and liquid phases at equilibrium as a function of metal ion concentration.
When an adsorbent comes into contact with a metal ion solution, the concentration of
metal ions on the adsorbent surface increases until a dynamic equilibrium is reached;
at this point, there is a clearly defined distribution of metal ions between the solid
adsorbent and liquid mobile phases [314]. The equilibrium relationship between
adsorbent and adsorbate is described by isotherms.

36
 Chapter 3

Figure 3.4: Effect of Initial Pb(II) concentration on sorption process by CSP

(Condition: 25°C, 160 rpm, 5g/l Adsorbent dosage, 90 min).

The effect of equilibrium concentration was measured using the heavy metal
ion initial concentrations ranging from 5 to 150 mg/l with a fixed adsorbent mass
(according dosage 5g/l) and pH 5 (Figure 3.4). It is apparent from the plot of percentage
removal vs initial metal ion concentration, that the percentage removal efficiency
increases from ~75 to ~86% on increasing metal ion concentration from 5- 25 mg/l and
decreases on increasing the concentration of metal ion 25-150 mg/l to 65%. The
maximum adsorption was obtained at the initial concentration of Pb(II) ions, 25mg/l
for a given adsorbent mass, and thereafter, adding more metal ions does not increase
adsorption due to non-availability of more binding sites for the same adsorbent dose
i.e. all the sites on the adsorbent surface are occupied. The decreased percentage Pb(II)
ion removal with increasing initial metal ion concentration can be accredited to the
increased amount of Pb(II) ions to the static number of available active sites on the
CSP. Hence, more metal ions were left in solution [285]. Whereas, adsorption capacity
increases from 0.75-19 mg/g on increasing initial metal ion concentration from 5-150
mg/l.
The isothermal studies were performed at varying initial Cd(II) ion
concentration (from 5mg/l-150 mg/l) at three different temperatures (i.e. 298 K, 308 K
and 318 K) using the optimized CSP dosage (5 g/l), optimized contact time (90 min)
at 160 rpm. The heavy metal adsorption capacities were calculated by means of least-
squares regression using linear expression of Freundlich Isotherm [317] Eq.(10) and
Langmuir Isotherm [317] Eq.(11).

37
 Chapter 3

Frendlich Isotherm
1
log q e = log K F + n log Ce (10)

where Ce the equilibrium metal ion concentration (mg/l), KF and n are the
Freundlich coefficients. KF provides an indication of the adsorption capacity and n is
related to the intensity of adsorption [184, 318]. The value of the parameters KF and n
was obtained using linear fit of the plot log qe vs log Ce as shown in Figure 3.5(a).
Langmuir Isotherm,
𝐶𝑒 1 𝐶𝑒
= + (11)
qe qm KL qm

where qe, qm are equilibrium adsorption capacity under given condition and
maximum adsorption capacity, respectively. Ce is the equilibrium concentration. KL is
the Langmuir constant which is related to the energy of adsorption [184]. Maximum
adsorption capacity, qm were obtained from slope of the graph plotted between Ce/qe
versus Ce (Figure 3.5b).
One of the essential characteristics of the Langmuir isotherm is separation factor
i.e. dimensionless equilibrium parameter ‘‘RL’’ as shown in Eq.5. It provides
significant information about the nature of adsorption. The value of RL indicates the
type of adsorption [319] i.e. irreversible (RL=0), favorable (0<RL< 1), linear (RL=1) or
unfavorable (RL>1).
1
R L = 1+K (12)
L Co

where Co, is the initial concentration (mg/l). The RL values for adsorption of
Pb(II) ions on CSP are in the range of 0 < RL< 1, at all three temperatures (298, 308
and 318K) indicates the favorable adsorption (Table 3.2). The resulting adsorption
isotherms parameters for Pb(II) ions adsorption study are summarized in Table 3.2. The
value of regression coefficient in case of Langmuir isotherm (R2 ≥ 0.985) is closer to 1
as compared to that of Freundlich isotherm (R2 ~ 0.960), indicating that the equilibrium
data are best fitted to Langmuir isotherm at all the three temperatures. This implies
occurrence of monolayer adsorption of Pb(II) ions on the surface of CSP under present
experimental conditions [181]. Increasing values of KL for Pb(II) ions sorption onto
CSP with increasing temperature suggests stronger binding affinity as a consequence
of increased energy of adsorption [320]. The maximum adsorption capacity (qm)
obtained at 25°C (i.e 298 K) is 28.25 mg/g, and going towards higher temperature 308K
& 318K, adsorption capacity decreases as shown in table 3.2. The reason for the

38
 Chapter 3

obtained trend may be attributed to the fact that at high temperature the thickness of the
boundary layer decreases due to increased tendency of the metal ions to escape from
adsorbent surface to the solution phase [321]. As the difference in adsorption capacities
at studied temperature range is very small, therefore, monitored temperature range
between 298-318 K can be used for effective removal of Pb(II) ions from aqueous
solutions efficiently.

Figure 3.5: Freundlich (a) and Langmuir (b) adsorption isotherm for Pb(II) ion removal
using CSP.
Table 3.2: Equilibrium Parameters for the adsorption of Pb(II) ions on CSP at different
temperatures
Temp Langmuir Isotherm Langmuir Isotherm
R2 n KF R2 qm KL RL
(mg1−1/n g−1 l1/n) (mg/g) (l/mg)
298K 0.963 1.31±0.25 1.34±0.32 0.987 28.25±1.25 0.05±0.005 0.45±0.002
308K 0.964 1.35±0.20 1.57±0.37 0.985 27.40±1.25 0.06±0.002 0.40±0.002
318K 0.961 1.37±0.22 1.67±0.30 0.986 26.74±1.78 0.07±0.003 0.38±0.003

The maximum adsorption capacity qm (28.25 mg/g) obtained under present study
using CSP by Langmuir isotherm model is quite higher than those obtained by previous
workers using other adsorbents such as walnut sawdust (qm = 15.90 mg/g) [190] , Pinus
sylvestris (qm = 9.78 mg/g) [225], banana peel (qm = 2.18 mg/g) [171], pomegranate
peel (qm = 13.87 mg/g) [227], hazelnut and almond shell (qm = 28 and 8.08 mg/g,
respectively) [322] and barley straw (qm = 23.2 mg/g) [133].

39
 Chapter 3

3.3.6 Thermodynamic Studies

Analysis of thermodynamic parameters of equilibrium sorption can give
noteworthy information about adsorption process. Thermodynamic parameter can be
determined from following equations [184, 253].
ΔGo= -RT ln Kc (13)
∆Go = ∆H o − T∆S o (14)
∆So ∆Ho
ln K c = − (15)
T RT

where Kc is the equilibrium/distribution constant, obtained by multiplying

Langmuir constant KL and maximum adsorption capacity qm(mg/g) [254-256]. R is the
universal gas constant (8.314×10-3 kJ/mol K) and T is the absolute temperature (K).
The values of ΔHo and ΔSo (Table 3.3) were dogged from the slope and the intercept
from the plot of ln kc vs 1/T, respectively, (Figure 3.6).
The negative values of Gibbs free energy (ΔGo) (Table 3.3) indicates feasibility
and the spontaneous nature of Pb(II) sorption on CSP [323]. More negative ΔG◦ value
with increasing temperature suggests easier adsorption at higher temperature. Further,
positive value of ΔHo indicates the endothermic nature of the biosorption of Pb(II) ions
onto CSP [193, 274, 324]. The positive value of ΔSo indicates increased randomness
and the affinity of CSP for Pb(II) ions at the adsorbent/solution interface during the
adsorption of Pb(II) ions onto CSP [183, 325]. Further, positive value of ΔSo also
contributes the adsorption process to become spontaneous and indicates that the process
is irreversible which again the characteristic of chemisorption [326]. In addition to
above, the positive value of ΔSo suggests a few structural changes in the adsorbent,
favored complexion and sorption constancy [105, 327]. Overall, both contributing
thermodynamic parameters to free energy change (ΔGo) i.e. enthalpy (ΔHo) and entropy
(ΔSo) favors the removal of Pb(II) ions by biosorption on CSP.

Table 3.3: Thermodynamic parameters at different temperatures

Temp Thermodynamic Parameters
ΔGo
ΔHo ΔSo
(kJ/mol) (kJ/mol) (kJ/mol K)
298K -0.81
308K -1.19 10.43 0.038
318K -1.58

40
 Chapter 3

0.6
0.5
0.4

ln kc
0.3
0.2
0.1
0.0
0.0032 0.0033 0.0034 0.0035
1/T
Figure 3.6: Plot of ln kc versus 1/T for Pb(II) sorption onto CSP

3.3.7 Biosorption Kinetics

Kinetic investigation have been carried out using pseudo-first order, pseudo-
second-order and intraparticle diffusion kinetic models to investigate the sorption of
Pb(II) ion from 25 mg/l of metal ion concentration onto CSP at varying temperatures
(298 K, 308 K and 318 K). The integral form of the pseudo-first-order kinetic model
[328] is generally expressed as follows:
𝐾1𝑎𝑑
log(q e − q t ) = logq e − t (16)
2.303

where, qe and qt are the adsorption capacities (mg/g) at equilibrium and time t
(min), respectively. The pseudo-first-order rate constant K1ad (min-1) was determined
experimentally by plotting log (qe-qt) versus t (Figure 3.7a).
The pseudo-second-order kinetic model, proposed by Ho and McKay [329], is
based on the assumption that the adsorption follows chemisorption and the linear form
of equation can be written as:
t 1 1
=K 2 +q t (17)
qt 2ad qe e

where, K2ad (g/mg min) is the second order rate constant and was evaluated by
plotting a curve of t/qt vs t, qe (Figure 3.7b). The pseudo first and second order kinetic
parameters are summarized in the Table 4.
Amongst both kinetic models i.e. pseudo first order and pseudo second order
kinetic model, the results confirm the applicability of the Pseudo second-order kinetic
model with higher correlation coefficient (R2 = 0.99) as compared to that of pseudo first
order kinetic model (R2 ~0.85) (Table 3.4).

41
 Chapter 3

Figure 3.7: Pseudo First Order (a) and Pseudo second Order (b) rate kinetics for Pb(II)
ion removal using CSP.

In case of pseudo first order kinetic model the experimental data does not fit
well to the entire range of contact time and which in apparent from figure 3.7a. The
data showed a linear fit only to the initial phase of contact time and that too only up to
60 min and after 60 min of contact time deviated from the linear fit [190, 273]. It is
apparent that the rate constant for pseudo-second-order kinetic model i.e. K2ad,
increases as temperature rises for Pb(II) ion adsorption on to CSP, thereby implying
that the biosorption system reached equilibrium faster at higher temperatures.
Additionally, the rate of sorption processes could be enhanced by an increment in
temperature, which again suggests an endothermic nature of the biosorption process
[324]. Pseudo second order kinetic model also suggests that the rate-limiting step may
be the chemisorption.

3.3.8 Adsorption Mechanism

The evaluation of rate controlling steps is very advantageous to understand the
mechanism involve in the adsorption phenomenon. The overall adsorption process can
be divided into four steps [330]:
Ist Step: Transport of metal ion from the bulk to the boundary layer.
IInd Step: The film diffusion, i.e. transport of metal ions from the boundary
layer to the external surface of the adsorbent.
IIIrd Step: Transfer of ions from the surface to the intra-particular spaces
present in adsorbent as active sites and this step is known as particle diffusion.

42
 Chapter 3

IVth Step: Metal ions interaction at the available adsorption sites on the internal
surfaces of the adsorbent.

It is apparent from the above description, that there is no involvement of

adsorbent in first step and the fourth step is a very rapid process so both of these steps
do not belong to the rate controlling steps. Consequently, the rate controlling step
depends on either film diffusion or particle diffusion step [183]. In order to provide
insightful description of mechanism involved in biosorption process, the intraparticle
diffusion model [331] is of major consideration. Therefore, the kinetic data were
analyzed by an intraparticle diffusion model to elucidate the diffusion mechanism.
Weber and Morris model is a widely used intraparticle diffusion model to predict the
rate controlling step [332, 333]. The rate constant of intraparticle diffusion (Ki) was
determined using the following equation:

q t = K i t 0.5 + I (18)

where qt (mg/g) is the adsorbed metal amount at time t. Ki is the intraparticle diffusion
rate constant (mg/g min1/2) and I is the intercept which is related to the thickness of
boundary layer [183] (Table 3.4). According to this model, the plot of uptake (qt) versus
the square root of time (t0.5) should be linear if only intraparticle diffusion is involved
in the adsorption process [332]. If line of plot passes through the origin, intraparticle
diffusion becomes the sole rate-controlling step [334]. In intraparticle diffusion plot
(Figure 3.8) the data points are related to two straight lines, which predicts two or more
steps influence the adsorption process such as external diffusion, intraparticle diffusion
etc. [335]. In the beginning, magnitude of qt increases sharply with increase of time due
to the immediate availability of active adsorption sites on large surface area of CSP that
signifies the external surface adsorption. The second subdued portion of the plot
represents the steady adsorption capacity, where rate-controlling step is the intraparticle
diffusion [335]. The intraparticle diffusion is not the only rate controlling step for the
adsorption of Pb(II) ions onto CSP, which is confirmed by the deviation of plot from
the origin [183].

43
 Chapter 3

Figure 3.8: Intra particle diffusion model of Pb(II) sorption by CSP

Table 3.4: Pseudo first order, pseudo second order kinetics and intraparticle diffusion
parameters for Pb(II)ions removal using CSP
Temp Pseudo First Order Pseudo Second Order
R2 qe k1ad×10-2 R2 qe k2ad×10-2
(mg/g) (min-1) (mg/g) (g/mg min)
298K 0.976 2.43±0.02 1.8±0.004 0.999 4.44±0.35 2.8±0.004
308K 0.984 2.46±0.18 4.63±0.07 0.999 4.52±0.76 3.0±0.005
318K 0.973 3.90±0.07 1.8±0.002 0.999 4.56±1.04 3.2±0.002
Intra Particle Diffusion
2
R Kid (mg/g min0.5) I
298K 0.971 0.281±0.06 1.73±0.02
308K 0.954 0.286±0.005 1.81±0.03
318K 0.953 0.293±0.003 1.85±0.04

Table 3.5: Competitive adsorption data in binary and multi-metal systems for the
adsorption capacity of Pb(II) ions onto CSP from aqueous solution.
(Experimental Condition: 25mg/l conc. of other metal ions + 25 mg/l of
Pb(II) ion conc., CSP dosage 5g/l, contact time 90 min, agitation speed 160
rpm, temperature 25±1°C)

Sorption System qe (mg/g) % decrease of qe

Pb(II) 4.30 -
Pb(II)-Cu(II) 3.98 7.36
Pb(II)-Ni(II) 4.06 5.49
Pb(II)-Cd(II) 4.14 3.63
Pb(II)-Cd(II)-Ni(II)-Cu(II) 3.82 11.08

3.3.9 Effect of Multi Metallic (Heavy Metals) Solution on Pb(II) Removal/Uptake

Real wastewater contains a number of different ions as well as other organic
and inorganic pollutants which could obstruct the concerned metal uptake due to
44
 Chapter 3

competitive sorption among other ions. To understand the removal of Pb(II) ion in the
presence of other ions, an experiment was conducted for removal of Pb(II) ions
accompanied with other ions in the aqueous solution. From table 3.5, it is apparent that
in case of single metal solution the adsorption capacity (qe) was greater in comparison
to binary or multi-metal solution. The reason may be due to absence of competitive
adsorbate of Pb(II) ions in the single metal solution [336]. However, in case of binary
and multi-metal system the adsorption capacity (qe) of CSP for Pb(II) ions decreases
(Table 3.5). Thus, a considerable reduction in metal sequestering ability of adsorbents
was found in binary and multi-metal systems in comparison to single metal system.
From Pb(II) ions removal efficiency it can be concluded that the combined action of
multiple ions was antagonistic [337, 338]. The most possible reason for the antagonistic
effect is the competition for active binding sites or the screening effect by the competing
metal ions on the surfaces of biosorbent (CSP) [339].
The data from binary metal system (Table 3.5) shows that Cu(II) ions exerted
the most inhibitory effect on the of Pb(II) ion uptake and causes drop of adsorption
capacity by 7.36%, followed by Ni(II) and Cd(II) ions. It can be explained on the basis
of differences of their ionic radius, the small ionic radius of Cu(II) (0.73Ǻ and Ni(II)
ions (0.72Ǻ) as compared to those of Cd(II) (0.95 Ǻ) and Pb(II) (1.19 Ǻ) ions [340]
induces a rapid saturation of binding sites i.e. preferential adsorption of Cu(II) and
Ni(II) over Pb(II) ions. However, greater inhibitory effect of Cu(II) on adsorption of
Pb(II) ions as compared to Ni(II) may be explained on the basis of higher complexing
ability of former due to John-Teller distortion. Thus, in multi-metal system larger no of
Cu(II) and Ni(II) ions occupied on same available surface of CSP as compared to that
of Cd(II) and Pb(II) ions. Thus the decrease in adsorption capacity in case of binary
metal solution of different metal ions followed the trend Cu(II) > Ni(II) > Cd(II) [341].

3.3.10 Effect of Anions & Cations (Alkali & Alkaline Earth Metals) on Biosorption
The effect of anions such as sulfate (SO4-), carbonate (CO32-), chloride (Cl-),
nitrate (NO32-) and cations such as Na+, K+, Ca2+, Mg2+ on Pb(II) ion removal was
investigated using different concentrations of them and results are presented in Figure
3.9. It is apparent from the result of above studies that the presence of anions reduces
the Pb(II) ion removal to a very small extent maximum up to ~5-7%, whereas, the
presence of cations reduces the Pb(II) removal significantly ( maximum up to ~ 30-
40%). The decreased efficiency was observed with increasing concentration of cations.
45
 Chapter 3

The influence of Na+ and K+, on the adsorption of Pb(II) ions is very small in
comparison to Mg2+ and Ca2+ due to lower complexing ability of former metal ions as
compared to later. The presence of Ca2+ and Mg2+ at 20 mg/l caused percentage removal
to drop by ~40 & ~30 %, respectively, due to competition for the available binding sites
on the surface of CSP with Pb(II) ions [274].

Figure 3.9: Effect of Anions (a) and Cations (b) on Pb(II)ion removal using CSP

3.3.11 Desorption of Adsorbed Pb(II) Ions from Exhausted CSP

Desorption of adsorbed Pb(II) ions from CSP was also studied by using dil.
HNO3. For these studies, 10 ml of HNO3 was used as eluant. The effect of volume of
1M HNO3 as eluent was also investigated in the range of 3.0–10.0 ml. The recovery for
Pb(II) ions was found to be ~93% even when only 6.0mL of 1M HNO3 was consumed.
Subsequent elution with higher amounts of dil. HNO3 does not remove any additional
amount of Pb(II) ions from CSP [185]. In addition, as it can be seen from Figure 3.10,
the high stability of CSP permitted five times of adsorption–desorption process along
the studies without a decrease of ~7% in recovery of Pb(II) ions was observed [185].

46
 Chapter 3

96
94

% Desorption
92
90
88
86
84
C-1 C-2 C-3 C-4 C-5
Cycles
Figure 3.10: Desorption efficiency of CSP with cycle number

3.3.12 FTIR and SEM Analysis

To identify the type of possible Pb(II) binding sites of CSP, FTIR spectra and
to observe changes in surface morphology SEM images were recorded before and after
the adsorption (Figure 3.11 & 3.12). The FTIR spectrum of CSP was complex due to
the existence of various functional groups on the surface of the biomass. When CSP got
to interact with Pb(II) of aqueous phase, the bond energy of C=O, -COO- and C-O-C
functional groups present at the surface of adsorbent were impacted by chemical action
generated in adsorption process, consequently, resulting in the shift on the characteristic
peaks. There are several distinct peaks that were observed from the spectrum as shown
in table 3.6. As shown in Fig.3.11, a broad and strong band stretch was observed from
3000 to 3600 cm−1, indicating the presence of free or hydrogen bonded –OH groups
present on the adsorbent surface [223]. The peak present at ~3452 cm-1 before
adsorption broadens and shifts towards ~3465 cm-1 after adsorption which may be due
to replacement of OH bonded H+ ion with Pb(II) ion. The peaks located ~2270 cm-1 and
1724 cm-1 may arise due to –N-C=O (isocyanate) [342] and –C=O (carbonyl) group,
respectively present on cyclic ring on CSP. The Peak regarding carbonyl functional
group shifted towards higher wavelength i.e. 1730 cm-1, indicating the involvement of
carbonyl functional group for the binding/adsorption of Pb(II) ions on the surface of
CSP. The band at 1659 cm-1 corresponds to the C=O stretching frequency of primary
amide [343]. Shifting of ~1103cm-1 band to higher wavenumber i.e. ~1219 cm-1 shows
the participation of C-O-C group of cellulose in metal binding [344, 345]. The peak at
1593 cm-1 arising due to C=C stretching frequency may be ascribed to the aromatic ring
present on CSP is shifted to ~1627 cm-1 after Pb(II) interaction. Very large number of
bands are observed below 1000-400 cm−1 due to complex interacting vibration systems
47
 Chapter 3

which do not corresponds to the “fingerprint region” therefore these absorption bands
cannot be clearly assigned to any particular functional group [346]. Although according
to Jahn et al. [347] peaks in range of 950-700cm-1 shows side group deformation region
for COH, CCH and OCH of cellulose and hemicelluloses.

Figure 3.11: FTIR spectra of CSP before and after Pb(II) ion adsorption

Table 3.6: Functional groups & mode of vibration from FTIR spectrum of CSP
FTIR Peaks (cm–1) Assignment of bonds Mode of Vibration
3692.2,
3655.1, Free O-H & H-bonded OH on Stretching
3629.9 & Surface
3451.9
2369.2 & 2270.3 - NCO group Stretching
1813.5 Carbonyl C=O Strong stretching
1723.7 6-membered cyclic ketone Strong stretching
1659.1 C=O of amide Strong stretching
1593.7 C=C present in aromatic rings Stretching
1102.6 C-O-C of phenol, cellulose Symmetrical stretching

48
 Chapter 3

The scanning electron micrographs (SEM at 800X) enable the direct

observation of the surface microstructures of the adsorbent. Figure 3.12a illustrates the
SEM images of native adsorbent which possesses irregular grooves and porous
structure. The above characteristics favor easy accessibility of Pb(II) ions to the
adsorbent surface [304] SEM images of exhausted/metal loaded adsorbent CSP clearly
indicates the presence of shiny bulky particles and metal loaded layer over the surface
of adsorbent and groves/pores present in native adsorbent disappeared (Figure 3.12b).
Above morphological changes are in conformity with adsorption of Pb(II) ions on the
surface of CSP i.e. there is a significant change in morphology of CSP after loading
Pb(II) ions as compared to that of native adsorbent.

Figure 3.12: Scanning Electron Micrograph showing morphology of virgin CSP (a)
and (b) Pb(II) loaded CSP

3.4 Conclusion
The results obtained by batch experiments shows that Pb(II) ion sorption on
CSP was significantly affected by experimental parameters i.e. pH of solution,
adsorbent dosage contact time and initial metal ion concentration. The optimum pH
obtained for the Pb(II) ions removal from aqueous solution is pH 5, whereas, optimum
adsorbent dose is 5g/l. Maximum removal of Pb(II) ions is obtained by keeping the
adsorbent CSP for an optimum contact time of 90 min. Adsorption capacity increases
with increasing initial metal ion concentration even up to 150 mg/l, whereas, percentage
removal increases up to 25mg/l Pb(II) ion but decreases beyond that. The equilibrium
data presented a better fit to the Langmuir isotherm model with a maximum adsorption
capacity of 28.25 mg/g at 25°C, indicating a monolayer sorption process. The
maximum adsorption capacity qm (28.25 mg/g) obtained under present study on CSP
by Langmuir isotherm model is quite higher than those obtained by previous workers
49
 Chapter 3

using other bio-adsorbents. Thermodynamic parameters indicated the feasibility,

spontaneity and endothermic nature of adsorption process. Kinetic study of Pb(II)
adsorption on to CSP surface showed a better agreement with the pseudo-second order
kinetics. This result confirms the occurrence of chemisorption process. Alteration of
vibrational frequencies of functional groups such as –OH, –C=O, –C–O–C–, –COOH,
and –COO– present on surface of CSP after adsorption of Pb(II) ions as compared to
the vibrational frequencies that of native CSP indicated the active participation of these
functional group in the adsorption of Pb(II) ions onto CSP and also confirmed the
occurrence of chemisorption along with pseudo second order kinetic model. Study of
removal of Pb(II) ions in the presence other heavy metal was affected in order of
Cu(II>Ni(II)>Cd(II) ion due same order of decreased ionic radii. Percentage Pb(II) ion
removal was also affected by the presence of alkali and alkaline earth metals especially
due to of Ca2+ ions whereas presence of anions did not significantly affected the
adsorption of Pb(II) ion. The recovery for Pb(II) ions was found to be very effective
using 1M HNO3 as a desorbing agent. As CSP has no commercial value and is readily
available inexpensive source of biomaterial and in light of its most effectiveness in
removing Pb(II) ions as compared to other reported biosorbents, it can be successfully
used as a low-cost environment friendly adsorbent for the removal of heavy metals from
an aqueous solution of Pb(II) ions.

*******************

50
 Removal of Cd(II) ions from simulated wastewater using
4
Cucumis sativus Peel

4.1 Introduction
In previous chapter we studied Removal of Pb(II) ions from aqueous solution
by Cucumis sativus (Cucumber) peel. In wastewater/ industrial effluent other heavy
metals are also present such as cadmium, chromium, copper, nickel, silver, tin and zinc.
Amongst these, Cadmium is a non-essential element and is one of the most hazardous
elements, classified as a “priority metal” from the stance of potential toxicological
effects to human health and plants [348]. Cadmium is frequently used in industrial
processes such as electroplating, metallurgical processes, batteries production, mining,
smelting, and alloy industries [14, 49-52]. Cadmium may be present in high
concentrations in industrial wastes and is often deposited directly in the environment
without any pre-treatment. Physicochemical methods conventionally used for the
treatment of industrial wastewaters include coagulation [349], membrane separation
[350], electrochemical treatment [351], flotation [352], softening and reverse osmosis
[353]. All these methods suffer from one or the other limitation; even none of these are
successful in removing the metal from wastewater completely and also generate
enormous quantity of toxic chemical sludge [100]. Adsorption systems are rapidly
gaining prominence as treatment processes for dissolved metals. The ability of
biomaterials to remove heavy metals, through biosorption has been projected as an
attractive alternative. Various adsorbents have been tried for removal of Cd(II) ion from
wastewater stream [90, 275] including plant materials, such as apple residues, sawdust,
papaya wood, rice polish, tea-waste, sugarcane bagasse, rice husk, pine bark, hazel-nut
shell, coconut husk, petiolar-felt sheath of palm, black gram husk, and wheat bran
[277]. However, none of the reported biosorbents are satisfactory on economical level
as well as not having efficient removal capacity. Therefore, there is a need to find other
more economically feasible, viable, eco-friendly biosorbents for the remediation of
wastewater containing toxic metals. No work has been reported for the removal of any
pollutant especially Cd(II) ions using cucumber peel as adsorbent except one study

51
 Chapter 4

where activated carbon prepared from Cucumis sativus was used for the removal of a
cationic dye from wastewater [354], Therefore, in the present study, an effort was made
to explore the feasibility of utilizing C. sativus peels (CSP) as biosorbent for the
removal of Cd(II) ion from simulated wastewater. The effects of pH, adsorbent dose,
contact time and initial cadmium concentration were studied. The isotherm models and
adsorption kinetic were studied by using experimental data at equilibrium. FTIR and
SEM were employed to evaluate the involvement of functional groups and surface
morphology of the biomass before and adsorption.

4.2 Materials and Methods

4.2.1 Chemical
The experimental stock solution of Cd(II) ion (1000±2mg/l) was prepared by
dissolving cadmium nitrate in DW and further dilutions were prepared from the stock
solution same as discussed in chapter 3.

4.2.2 Adsorbent Preparation

The same adsorbent i.e. CSP is used in this present study, therefore the
procedure for its preparation was also the same as described in chapter 3.

4.2.3 Batch Adsorption Studies

Batch experiments were followed same as used in chapter 3 for Cd(II) ions
removal from aqueous solution at 160 rpm throughout the experiments. The stock
solution, diluted solution or filtrates of Cd(II) ion resulting from the experiments were
analyzed on AAS using Electrodeless Discharge Lamp (EDL) at characteristic
wavelength 228.8 nm for Cd(II) ions.

4.2.4 Analytical/ Physic-Chemical Characterization

The same biosorbent is used here for the removal of Cd(II) ions from the
simulated wastewater. Therefore, the analytical/ physic-chemical characterization
parameter of CSP were same as described in chapter 3. FTIR and SEM analysis of CSP
before and after Cd(II) removal was performed same as described in chapter 3.

4.2.5 Effect of Other Ions in Aqueous Solution on Adsorption

To study the effect of presence of other anions such as Sulfate (SO4-), carbonate
(CO32-), chloride (Cl-), nitrate (NO32-) and cations like Na+, K+, Ca2+, Mg2+ and some
heavy metal ions such as Pb(II), Cu(II) and Ni(II) ions on Cd(II) ion removal was
52
 Chapter 4

studied using 25mg/l of initial Cd(II) ion concentration following the same procedure
as described in chapter 3.

4.2.6 Desorption and Regeneration

The experiment was followed same as described in chapter 3 using 25 mg/l of
initial Cd(II) ions concentration.

4.3 Result and Discussion

4.3.1 Characterization of CSP
The analysis of physico-chemical parameter of adsorbent (Percent moisture
content, Percent ash content, particle density, bulk density and percent porosity) are
summarized in Table 3.1 (chapter 3).

4.3.2 Influence of pH and Contact Time

Several studies have shown that pH has been very imperative factor, affecting
the metal adsorption on the surface of biomass [277]. Not only do different metals have
different pH optima for their sorption, these may also differ from one type of sorbent
to the other [278]. Since CSP is being reported as a new sorbent material, the effect of
pH on the sorption of 25mg/l of Cd(II) ion concentration at 1g/l dose was studied in
the pH range of 2-9 at RT and 160 rpm (Fig.4.1a). It was noted that percent Cd(II)
sorption at pH 2 was ~71% and increased with the increasing pH from 2-5. The low
metal sorption at pH 2 may be explained on the basis of protonation of active sites such
as hydroxyl, carboxylate, and amino groups on the surface of CSP resulting in
hindrance of Cd(II) ion to occupy the binding sites [355]. As the pH increased, the
biosorbent surface gets deprotonated, which favors the adsorption of Cd(II) ion. The
percentage removal of Cd(II) ion continues with increasing pH up to 5 until the
maximum percentage removal of ~77% was achieved using normal experimental
condition as stated above. At pH higher that 5 the competition between H+ ion and
Cd(II) ion become less due to obvious low concentration of H+ ions at higher pH. At
pH > 9, adsorption studies could not be carried out due to precipitation of feebly soluble
hydroxide of Cd(II) ion such as Cd(OH)+ and Cd(OH)2 [356] .

53
 Chapter 4

Figure 4.1 Effect of pH on adsorption of Cd(II) (a) and effect of contact time on
adsorption of Cd(II) onto CSP (b).

Fig.4.1 b shows percentage removal as a function of time for 25mg/l Cd(II) ion
concentration by 1g/l dose of CSP (pH 5, 160 rpm at RT). The result revealed initial
rapid sorption up to 120 min of contact time and then became maximum (~82 %) near
the equilibrium at 150 min and after this equilibrium it showed steady removal of Cd(II)
ions from aqueous solution. The fast adsorption of Cd(II) ions in initial phase reason
may be due to the availability of uncovered surface area and freely available binding
sites for the uptake of metal ions [183]. Further, the higher initial driving force of metal
ions towards biosorbent and the higher difference of concentration between the bulk
solution and the solid-liquid interface also resulted in a faster adsorption rate in initial
phase of contact time [357]. However, after 150 min of contact time, percentage
removal showed a constant/steady trend and this may be due to the slower diffusion of
solute into the interior of the biosorbent [358].

4.3.2 Effect of Biosorbent Dose and Initial Ion Concentration

CSP dosage of 1-15g/l was employed to evaluate the optimum removal of metal
from 25mg/l concentration of Cd(II) ion for optimized contact time (i.e. 150 min) at pH
5. The optimum percentage removal was found to be ~ 88% at a biomass level of 5 g/l
(Fig.4.2a), however, above this dose percentage removal did not seem to increase
significantly due to equilibrium limitation i.e. for a given initial Cd(II) ion
concentration, further increase of the adsorbent dosage did not showed any effect on
the adsorption rate of Cadmium [359]. On the other hand adsorption capacity decreased
from 41-1.67 mg/g when the biomass dosage increased from 1-20g/l. Similar
observations have been documented earlier with varying biomass dosage [360, 361].
54
 Chapter 4

Figure 4.2: Effect of adsorbent dose (a) and effect of initial ion concentration (b) on
Cd(II) sorption onto CSP.

Figure 4.2b shows maximum removal efficiency of ~83% as a function of initial

Cd(II) ion concentration using 5g/l of CSP dosage for 150 min of contact time. For
CSP, the percentage Cd(II) ion removal increased quickly over increasing initial Cd(II)
concentration from 2 to 25 mg/l. However, as the initial Cd(II) concentration increased
continuously above 25 mg/l the percentage Cd(II) ion removal decreases due to the
release of more Cd(II) ions in the solution because of the saturation of binding sites i.e.
at a fixed adsorbent dose, biosorbent has a limited number of active sites, which become
saturated at a certain concentration [361].

4.3.3 Adsorption Equilibrium Study

Freundlich and Langmuir isotherm models were applied to analyses the
equilibrium data at varying initial Cd(II) ion concentration from 5mg/l-150mg/l..
Freundlich parameters, i.e. n (heterogeneity factor) and KF (Freundlich Constant) were
determined same as discussed in chapter 3 i.e. from the slope and intercept of the plot
between log qe versus log Ce (Figure 4.3a and Table 4.1). The parameters n and KF
provides an indication of the adsorption capacity of biosorbent and intensity of
adsorption, respectively. Values of Langmuir constant qm and KL (l/g) were also
determined same as described in chapter 3, i.e. from slope and intercept of plots
between Ce/qe versus Ce (Figure 4.3b) which indicates monolayer sorption capacity and
indicative of binding energy for Cd(II) ion adsorption onto CSP, respectively
(Table4.1).

55
 Chapter 4

Figure 4.3: Freundlich Isotherms (a) and (b) Langmuir Isotherms model for Cd(II)
ion removal using CSP.
Table 4.1: Adsorption Isotherm parameters for Cd(II) ion removal using CSP

Temp Freundlich Isotherm Langmuir Isotherm

R2 n Kf R2 qm KL
(mg1−1/n g−1 l1/n) (mg/g) (l/mg)
298K 0.975 1.29 1.50 0.765 37.45 0.038
308K 0.985 1.42 2.24 0.902 33.33 0.070
318K 0.993 1.49 2.62 0.935 30.86 0.092

From the correlation coefficient values of the tested isotherm models, it was
concluded that experimental data for the adsorption of Cd(II) ions by CSP fits better in
Freundlich isotherm model. The Freundlich isotherm is valid to both monolayer
(chemisorption) and multilayer adsorption (physisorption) [184] and is based on the
hypothesis that the adsorbate adsorbs onto the heterogeneous surface with different
energetic distribution of active sites of an adsorbent [184, 362]. The freundlich isotherm
parameter n obtained here is greater than unity which indicates the favourable
chemisorption of the Cd(II) ions on CSP [184, 362]. The Freundlich isotherm model is
indicative of surface heterogeneity of the adsorbent, i.e. the adsorptive sites are made
of small heterogeneous adsorption patches that are homogenous in themselves [363].

4.3.4 Thermodynamic Study

Langmuir isotherm constant KL and qm were used for the analysis of
thermodynamic parameters i.e. free energy (∆Go), enthalpy (∆Ho) and entropy change
(∆So) using thermodynamic equations same as described in Chapter 3. The plot of ln kc
(obtained by multiplying Langmuir constant KL and qm [256] ) versus 1/T yields a

56
 Chapter 4

straight line (Fig. 4.4) from which ΔHo and ΔSo were calculated from the slope and
intercept, respectively. The negative values of ΔG° indicates thermodynamically
feasible and spontaneous behavior of adsorption (Table 4.2). The value of ΔG° becomes
more negative with an increase in temperature, which indicates that a higher adsorption
is actually occurred at higher temperatures [193]. The positive ΔHo and ∆So value as
shown in Table 4.2, indicates endothermic process and increasing randomness at the
solid/liquid interface, respectively [184].

Figure 4.4: Plot of ln kc versus 1/T for determining thermodynamic parameters for
Cd(II) ions removal using CSP

Table 4.2: Thermodynamic Parameters for Cd(II) ion removal using CSP

Temp Thermodynamic Parameters

ΔG (kJ/mol)
o
ΔHo(kJ/mol) ΔSo(kJ/mol K)
298K -1.00
308K -1.94 27.19 0.094
318K -2.89

4.3.5 Kinetics Study

The prediction of kinetics is necessary for the design of sorption systems.
Kinetics explains the dynamic of rate of reaction and factors affecting the reaction rates
[190]. The pseudo-first-order rate constant K1ad and qe obtained from the plot of log (qe-
qt) vs t [264] (Fig.4.5a) and pseudo-second-order parameters i.e. qe (mg/g) and K2ad
(g/mg min) were obtained from the slope and intercept of linear plots between t/q t
against t (Fig. 4.5b) for the metal ion sorption same as described in chapter 3 [305, 329].
Pseudo second order model suggests that the adsorption rate is proportional to the
square of the number of unoccupied sites [364]. The validity of each model was
estimated by comparing the R2 values. The experimental data (Table 4.3) shows a linear
57
 Chapter 4

fit to the pseudo-second-order kinetic model for entire range of contact time with a very
high correlation coefficient (R2 ~ 0.99) as compared to that of pseudo first order kinetic
model (R2 ~ 0.80-0.90) for explaining the kinetics of the adsorption process. Pseudo
first order kinetic model fits only to the initial phase of contact time up to 120min,
similar observations were reported by other authors also [130, 190, 194]. Hence, the
adsorption process follows the pseudo-second order kinetic model which considers
chemisorption as the rate limiting step [268]. It also shows that the rate of Cd(II) ion
uptake by CSP increases on going from 25oC -35oC (i.e. from 298 K–308 K) that may
be due to increased kinetic energy at higher temperature which causes rapid uptake of
Cd(II) ions on the CSP surface, whereas beyond 35oC (i.e. above 308K and up to 318
K) the adsorption rate decreases may be due to increased tendency of metal ion to
escape from biomass surface to the solution phase at higher temperature.

Figure 4.5: Plots for Pseudo-first-order (a), Pseudo-second-order (b) Kinetic models
for adsorption of Cd(II )ions onto CSP.

4.3.6 Adsorption Mechanism

The intraparticle diffusion rate constant Ki and the parameter I were obtained
by slope and intercept of a plot of qt vs t0.5, respectively [272] (described in detail with
equation in Chapter 3). A relationship between intercept (i.e. I), and the thickness of
boundary layer implies the contribution of surface adsorption in the rate controlling step
[365]. In addition, the intraparticle model was studied to understand the mechanisms
and rate controlling steps that affects the kinetics of adsorption by fitting the
experimental results into this model. It can be seen that the obtained curves can be
subdivided into linear part and non-linear part indicating more than one process such
as external diffusion, intraparticle diffusion etc. are involved in the adsorption of Cd(II)
58
 Chapter 4

ions onto CSP (Figure 4.6). The linear plot deviated from origin, indicating intraparticle
diffusion is not the sole rate-controlling step. The value of Ki and I (Table 4.3) are in
accordance with the observations of other similar studies [366]. .

Figure 4.6: Intraparticle diffusion model for adsorption of Cd(II) onto CSP

Table 4.3: Kinetic Parameters for the adsorption of Cd(II)ions onto CSP at different
temperatures
Temp Pseudo First Order Reaction Pseudo Second Order Reaction

R2 qe K1ad×10-2 R2 qe K2ad×10-2
(mg/g) (min-1) (mg/g) (g mg-1min-1)

298K 0.983 1.57 2.4 0.999 4.65 3.3

308K 0.995 1.47 2.1 0.999 4.94 2.3
318K 0.997 1.40 2.2 0.999 4.80 3.5
Temp Intraparticle Diffusion

R2 Kid I
(mg/g min0.5)
298K 0.877 0.093 3.26
308K 0.883 0.090 3.38
318K 0.892 0.088 3.49

4.3.7 Effect of Multi Metallic Solution on Cd(II) Uptake

The results indicated as in table 4.4 demonstrate that the presence of other
cations reduced the Cd(II) ion uptake capacity of CSP with the competitive binding of
Pb(II), Cu(II) and Ni(II) ions in binary metal system as well as in the multi-metal
solution system. The observed reduction in the sorption capacity of Cd(II) ions in the
presence of other could be attributed to the competition between metal ion for the
available binding sites on the adsorbent. The highest inhibition effect was observed in
the presence of Cu(II) ions with a 8.56% decrease in adsorption capacity, followed by
Ni(II) and Pb(II) ions. This could be explained by the same reason as discussed in

59
 Chapter 4

chapter 3 i.e. smaller their ionic radii of Cu(II) ion [341] and due to John Teller
distortion effect caused by Cu(II) ion as discussed in chapter 3.

Table 4.4: Competitive adsorption data in binary and multi-metal systems for the sorption
capacity of Cd(II) ions onto CSP from aqueous solution
(Experimental Condition: 25mg/l conc. of other metal ions + 25 mg/l of
Cd(II) ion conc., CSP dosage 5g/l, contact time 150 min, agitation speed 160
rpm, temperature 25±1°C)
Sorption System qe (mg/g) % decrease in qe
Cd(II) 4.44 -
Cd(II)-Cu(II) 4.06 8.56
Cd(II)-Ni(II) 4.20 5.36
Cd(II)-Pb(II) 4.23 4.78
Cd(II)-Pb(II)-Ni(II)-Cu(II) 3.77 14.96

4.3.8 Effect of Anions and Cations on Biosorption

The effect of anions and cations on Cd(II) ion removal was studied, and the
results are illustrated in Figure 4.7a. The result shows that Cd(II) ion percentage
removal decreases with increase in anions concentration, especially in case of carbonate
and sulfate as compared to that of chloride and nitrate ions. The Cd (II) ion percentage
removal decreases significantly from ~73 to 54%, and from ~75 to 59% with increasing
concentration (from 1-25mg/l) of carbonate and sulfate ions, respectively. The reason
for this trend may be attributed to the fact that the complex forming ability of the these
anions with Cd(II) is in the order of carbonate > sulfate > chloride > nitrate ion [367]
and this is the justified cause for the substantial inhibition of Cd(II) sorption in the
presence of carbonate and sulfate ions the most.

Figure 4.7: Effect of Anions (a) and Cations (b) on Cd(II) ion removal using CSP

60
 Chapter 4

The effect of cations was also found to be very informative as shown in Figure
4.7b. The presence of Ca2+ ions affected the Cd(II) ions removal the most, causing drop
of 30% of percentage removal, followed by Mg+2 ions that causes 23% drop of Cd(II)
ion percentage removal. Whereas Na+ and K+ ions causes moderate effect on Cd(II) ion
removal [274]. The probable reason for this trend may be due to competition between
Cd(II) ions and cations for the adsorption sites of binding on the surface of CSP.

4.3.9 Desorption of Adsorbed Cd(II) Ions from Exhausted CSP

Desorption of adsorbed Cd(II) ions onto CSP was studied same as described in
chapter 3 by using HNO3. For these studies, 10 ml of HNO3 was used as eluent. The
effect of volume of eluent was also investigated using sequential addition of 2-2 ml of
1M HNO3 up to10 ml. The recovery for Cd(II) ions was found to be ~ 91% using 8 ml
of 1M HNO3 (Figure 4.8a). Subsequent elution with higher amounts of HNO3 did not
showed any significant effect on further desorption of adsorbed metals ions. In addition,
it can be seen from Figure 4.8b, that the high stability of desorption experiment was up
to second cycle with ~90% efficiency, whereas efficiency decreased in subsequent
cycle.

Figure 4.8: Desorption efficiency as a function of HNO3 (a) & Number of cycles (b).

4.3.10 FTIR and SEM Studies

To identify the type of possible Cd(II) binding sites on CSP, FTIR spectra
(Perkin–Elmer1760X) was performed in spectral range of 4000-400 cm-1 before and
after adsorption (Fig. 4.9). The spectrum of CSP was complex due to the existence of
various functional groups on the surface of the biomass. The region between 2600 and
3600 cm−1 shows two major band stretches. A broad and strong band stretch was
observed from ~ 3000 to 3600 cm−1, indicating the presence of free or hydrogen bonded
–H groups (alcohols and carboxylic acids) on the surface of the adsorbent (Iqbal, Saeed
61
 Chapter 4

& Zafar, 2009). A shift of alcoholic group (–OH) at 3452 cm-1 to 3433 cm-1 was
observed in the FTIR spectrum of Cd(II) ion loaded CSP.

Figure 4.9: FTIR spectra of (A) biomass of CSP and (B) Cd(II) ion loaded biomass of
CSP
The region between ~ 2250 and ~ 2700cm−1 showed the presence of R-NH3+
groups (=NH+2, ≡NH+, =NH+). A band at ~1647 cm−1 indicated C=O stretching in
carboxyl groups [368], which shifted to ~1651 cm−1 after Cd(II) adsorption. The
presence of carbonyl group on the CSP surface was indicated by the occurrence of
characteristic peak for C=O at ~1724 cm-1, however there is no significant change
observed after Cd(II) ion adsorption. The peak at 1593 cm−1 showed the bending of N–

62
 Chapter 4

H which shifted to higher wavelength 1625 cm−1 after Cd(II) adsorption which indicates
participation of amino group as an active site for Cd(II) removal. The C-O stretching
of lignin structure shifted from ~1102 to higher wavelength to 1110 cm-1, respectively
after adsorption. The changes in FTIR spectrum of CSP after the adsorption of Cd(II)
suggest the involvement of –OH, C-O of lignin structure and –NH groups in the
adsorption process [369]. Although there are very minor change in FTIR spectrum of
Cd(II) loaded CSP after adsorption, but presence of these functional group of CSP
surface suggests their probability of participation in Cd(II) uptake from the aqueous
solution.
The surface morphology of biomass was analyzed by Scanning Electron
Microscope (SEM) (ZEISS, JSM-840A) before & after adsorption. The SEM of the
biomass showed the irregular pattern at 20µm indicating huge irregular surface with
porous structure available for adsorption and after sorption of Cd(II) ion, the adsorbent
surface became abnormal and a great deal of substance adhered to the surface showing
agglomeration on it as shown in Fig.4.10. These alternations in surface morphology are
one of the evidence of Cd(II) ion sorption onto biomass.

a b

Figure 4.10: SEM micrograph images of CSP (a) before adsorption and (b) after
adsorption of Cd(II)ions onto CSP

4.4 Conclusion
In the present investigation, performance of unmodified and unexplored
biosorbent CSP was evaluated for the removal of Cd(II) ions from aqueous solution.
The maximum Cd(II) ion sorption was obtained at pH 5. The contact time, initial
concentration and temperature were also determining factor for the biosorption. The
removal efficiency of ~82% was achieved in 150 min of contact time with initial ion
concentration of 25 mg/l. Batch studies displayed that the equilibrium experimental
63
 Chapter 4

data follows Freundlich isotherm model (R2 ≥ 0.975) as compared to that of Langmuir
isotherm model. At RT, pseudo second-order model shows a good correlation
coefficient value (R2 ~0.999 ) closer to 1 as compared to that of pseudo-first order,
indicated that Pseudo second order kinetic model shows best fit to experimental data
and therefore confirming the occurrence of chemisorption. Thermodynamic parameter
shows that the process was spontaneously feasible and endothermic in nature for all the
temperature range evaluated. Due to smaller size and higher affinity of Cu(II)/Ni(II)
ions as compared to Cd(II) and Pb(II) ions, they reduced the maximum adsorption
capacity of Cd(II) ions on the surface of CSP from bimetallic or multi-metallic solution.
However, Cu(II) ions being a bit larger in size to Ni(II) ion reduced the Cd(II)
adsorption capacity more than Ni(II) ion due to its probable john teller distortion effect.
Maximum desorption of Cd(II) ions from CSP surface showed the ~91% using a
minimum volume of 8 ml of 1 M HNO3 as eluent. The probable interaction of Cd(II)
ion and biosorbent were displayed by FTIR and SEM studies. It can be concluded that
the removal capacity of CSP was at par with other commercially adsorbents or other
adsorbents prepared with other agro waste materials. Utilization of biomass in
unmodified form will not only reduce the cost, but also lower the energy requirement
in modifying the biomass, thereby presenting a green chemistry option.

*******************

64
 Removal of Pb(II) and Cd(II) ions from simulated
5
wastewater using Citrullus lanatus Rind
5.1 Introduction
In previous chapters the removal of Pb(II) and Cd(II) using CSP as biosorbent
have been described where it was found that CSP is very effective in removing Pb(II)
and Cd(II) ion from aqueous solution. CSP in-spite of being almost free of cost was
found to be much better adsorbent as compared to other biosorbents reported in the
literature [133, 171, 190, 225, 227, 322]. In view of above, encouraging results it was
decided to determine the effectiveness of peel of other bio-materials specially Citullus
lanatus rind (CLR) in present chapter. The reason for selecting CLR is mentioned
below.
CLR are normally thrown away without any gain as waste and they are known
to have a relatively high carbon and possess a porous structure [370]. CLR is an
inexpensive and abundantly available agro-waste product, which can be used as a
substitute to the prevailing adsorbents such as activated carbon because it not only
substitutes the waste into a productive material but also prevents environmental
pollution due to its on-site burning and/ or rottening and saving its disposal cost [371].
It is consists of a variety of polymers such as cellulose, hemicelluloses, pectin, lignin
and proteins whose structural backbone possess side chain having functional groups
such as hydroxyl, carboxyl and amines and citrulline and carotenoids [372, 373]. It is
consists of a variety of polymers such as cellulose, hemicelluloses, pectin, Due to the
presence of active functional groups in constituents of CLR, it is capable to bind with
metal ions. In light of immense potential of CLR to bind with metal ions, it was decided
to use CLR as a biosorbent for the removal of theses heavy metal ions. Here in the study
citric acid modified CLR was used as an adsorbent to enhance the adsorption capacity
of CLR, because in pilot experiment using unmodified CLR, it did not showed
significant/impressive adsorption capacity for Pb(II) and Cd(II) ions from aqueous
solution. In the present chapter the batch experiments were used to evaluate the
adsorption behavior of the CLR for Pb(II) and Cd(II) with respect to pH, adsorbent

65
 Chapter 5

dose, contact time, and initial ion concentration Sorption experiments using multi-metal
solution as a model for industrial effluent/wastewater and desorption experiments for
heavy metal ions were performed also to investigate the reusability of the CLR.

5.2 Materials and Methods

5.2.1 Chemicals
The stock solutions of Pb(II) and Cd(II) and all other working solutions were
prepared and used by same method as described in chapter 3.

5.2.2 Adsorbent
The CLR was obtained from the local market (Lucknow, India) washed several
times with DW and dried under sunlight for 5 days followed by grinding and drying at
100o C for 24 hours as described in chapter 3. It was screened to get the average particle
diameter of 0.5 mm based on analytical mesh sieve size 30. The CLR was stored in
airtight container for further usage.

5.2.3 Pre-Treatment of Adsorbent (CLR)

A solution containing 40 g CLR and 200 ml of 1M citric acid (CA) was heated
at 60°C for 2 hours and resulting solution was allowed to cool to room temperature
(RT) and filtered. Residual CLR was washed 2-3 times and dried in an oven at 50°C
for 24 h followed by heating at 120°C for 3 h and cooling to RT [209]. The physical
characteristic analysis of CLR for the determination of particle density, bulk density,
porosity, moisture content and ash content, were carried out by the methods as
described in chapter 3. The results are summarized in Table 5.1.

5.2.4 Point of Zero Charge Determination using Solid Addition Method

For the determination of zero point of charge (pHzpc), 40 ml of NaNO3 solution
(0.01 mol/l) was taken in eight polyethylene bottles (125 ml) [374, 375]. 1M HCl /
NaOH were used to obtain pH in increasing order from 2–10 for NaNO3 solution. Final
volume in each bottle was made up to 50 ml by 0.01 mol/l NaNO3. The pH values of
each bottles were recorded and considered as initial pH (pHi). Subsequently, an equal
known amount of the CLR was added in each bottle, stoppered and placed on a rotatory
shaker at room temperature for 24 h. The pH of the supernatant liquid of each bottle
was recorded and designated as final pH (pHf). The pHzpc was obtained by plotting a
graph of pHf vs pHi (Figure 5.1).

66
 Chapter 5

5.2.5 Batch Adsorption Studies

Batch adsorption experiments for the removal of Pb(II) and Cd(II) ions using
their initial concentration of 20mg/l with CLR as a biosorbent was performed by
applying the same method as described in chapter 3.
Isotherm studies were recorded by varying the initial concentration of Pb(II)
and Cd(II) ion from 10- 150 mg/l with CLR following the method as described in
chapter 3. Thermodynamic studies were performed at different temperatures as
described in chapter 3. Similarly, the kinetic experiments were performed for the
removal of Pb(II) and Cd(II) ions from aqueous solution following the method
described in chapter 3.

5.2.6 Effect of Ionic Strength

The electrolytes such as NaCl, KCl, NaNO3, and Na2HPO4 salts, may present
in industrial effluents/wastewaters besides heavy metal ions. These may also interfere
with the removal of heavy metal ions by an adsorbent. Therefore these electrolytes were
chosen to study their effect on Pb(II) and Cd(II) ions adsorption onto CLR. For this
purpose different concentrations of electrolyte/salts solutions (in the range of 0.01-0.5
M) were treated with initial concentration of 20 mg/l of Pb(II) and Cd(II) ion
individually and shaken with 1g/l CLR dose for 60 min.

5.2.7 Desorption Procedure

Desorption and regeneration experiments were performed following the
procedure as described in chapter 3.

5.2.8 Analytical/ Physico-Chemical Characterization

All the analytical/ physico-chemical characterization method were followed as
described in chapter 3 except, FTIR spectra were recorded on spectrophotometer
(Bruker model Vertex-70)

5.3 Results and Discussion

5.3.1 Characterization of CLR
The physical properties of the adsorbent was analyzed to get the detail idea
about the behavioral characteristic of adsorbent CLR regarding adsorption. The
obtained pHzpc for the modified CLR is represented in figure 5.1. The physical

67
 Chapter 5

characteristics data of CLR such as percentage ash content, moisture content, particle
density, bulk density, and porosity is summarized in Table 6.1

Figure 5.1: pHzpc determination of CLR

Table 5.1: Physical Characteristics of CLR

Parameter CLR
Particle density 0.207
Bulk density (g/ml) 0.176
Porosity (%) 15
Moisture content (%) 11.50
Ash content (%) 16
pHzpc 4.9

5.3.2 Effect of pH and Biosorbent Dosage

The pH of the solution is documented [171, 194] as a significant parameter that
affects the adsorption capacity of adsorbents. It affects the surface property of the
adsorbent in relations of surface charge and dissociation of functional groups [376].
Fig. 5.2 shows remarkable effect of pH on % uptake of the Pb(II) and Cd(II) metal ions
using 20 mg/l aqueous solution of these metal ions for a period of 60 min. Percent
removal increases sharply in the pH range 3-6 for both metal ions. The optimum
removal of both the metal ions was observed at pH 6. Beyond pH 6 % removal of metal
ions neither increases nor decreases i.e. a plateau was obtained probably due to
saturation of all active sites present on the adsorbent surface on or beyond pH 6. This
behavior can be explained by taking into account the CLR’s pHzpc value [377]. At pHzpc
value the charge of the whole surface is zero because the absorbent do not promptly
release H+ and/or OH- ion in solution via acid-base dissociation. The pHzpc of the CLR
(4.9), indicates that the carboxyl and phenolic groups are deprotonated above pH 4.9,
making them capable to bind effectively with positively charged metal ions. The least
68
 Chapter 5

adsorption observed at pH ≤ 3 is obvious due to competition between heavy metal ions

and the H+ ions at active sites of the adsorbent leads to protonation of adsorbent surface
depletion of metal ions adsorption. At the pH ≥ 8, the precipitate of hydroxy complexes
of heavy metals is formed due to increase of OH- ions concentration [378], therefore
the experiments were carried out at pH 6.

Figure 5.2 Effect of pH on Pb(II) and Cd(II) removal (Condition: 20mg/l Pb(II) and
Cd(II) ion conc., 1g/l CLR dosage, 60 min, 250rpm, 25±1°C)
Adsorbent dose affects the adsorption capacity of an adsorbent for a given initial
metal ion concentration as discussed in previous chapters, therefore, optimum
adsorbent dose was determined (Fig. 5.3).

Figure 5.3 Effect of CLR dosage on Pb(II) and Cd(II) removal (Condition: 20mg/l
Pb(II) and Cd(II) ion conc., pH 6, 60 min, 250rpm, 25±1°C)

69
 Chapter 5

The percentage metal adsorption increases with increasing adsorbent dose up to

2.5 and 1.5 mg/l for Pb(II) and Cd(II) ions, respectively. However, above this, a plateau
is obtained due to the formation of aggregates. Formation of aggregates may block the
pores and/or active sites of adsorbent, consequently causing unavailability of a fraction
of the binding sites of adsorbent to metal ions in the solution. The reason for this may
also be attributed to the fact that the binding sites endure saturation for the same and
fixed initial metal ion concentration during the adsorption process, although the number
of available sites for adsorption increased by increasing the biosorbent dose [379].

5.3.3 Effect of Initial Ion Concentration and Contact Time

The Pb(II) and Cd(II) ion uptake is significantly reliant on the initial ion
concentration. At the lower range of initial metal ion concentration, Pb(II) and Cd(II)
ion are adsorbed by active sites effectively, while at higher range of concentration the
% adsorption decreases due to saturation of adsorption sites/ lack of sufficient surface
area to accommodate further metal ions. The influence of the initial Pb(II) and Cd(II)
ion concentration on their removal with CLR (Fig. 5.4) shows a decrease in percent
removal from ~72-30% and ~96-40% with increasing initial concentration from10-150
mg/l, respectively.

Figure 5.4 Effect of initial ion concentration on Pb(II) and Cd(II) removal (Condition:
pH 6, 1g/l CLR dosage, 60 min, 250rpm, 25±1°C)
The effect of contact time on adsorption study (Fig. 5.5) shows that the metal
uptake is very rapid up to 180 and 120 min of contact time for Pb(II) and Cd(II) ion
removal, respectively, whereas beyond above time a plateau is obtained. The reason

70
 Chapter 5

ascribed for this trend may be due to the saturation of available active sites on the
surface of adsorbent CLR as discussed in previous chapters.

Figure 5.5 Effect of contact time on Pb(II) and Cd(II) removal (Condition: 20mg/l
Pb(II) and Cd(II) ion conc., 1g/l CLR dosage, pH 6, 250rpm, 25±1°C)

5.3.4 Effect of Ionic Strength of Solution on Adsorption of Pb(II) and Cd(II) Ions
on CLR
Besides heavy metal ions, some other salts, which interferes with heavy metal
ion uptake by adsorbents in real wastewater [186]. With increasing electrolyte
concentration (0.01-0.5 M), adsorption capacities of CLR for removal of Pb(II) and
Cd(II) ions was found to decrease for both metal ions (Figure 5.6 a, b).

Figure 5.6 Effect of ionic strength on Pb(II) ions (a) and Cd(II) ions (b) removal

71
 Chapter 5

It is apparent that CaCl2 and Na2HPO4 exert greater influence on adsorption

capacity of CLR for the removal of both metal ions than that of NaCl. Decrease of q e
value of CLR may be attributed to competition between Pb(II) or Cd(II) ions and
cations of the salts at the active adsorption sites of CLR [380, 381].

5.3.5 Adsorption isotherms

The adsorption process was investigated using following three equilibrium
isotherms; Freundlich, Langmuir isotherm and Dubinin-Radushkevich (D-R) isotherm
models where former two models were described in Chapter 3 and last model is
summarized as below. Dubinin-Radushkevich (D-R) isotherm model was applied to
determine the nature of biosorption processes i.e. physical or chemical process [185].
The D–R sorption isotherm is more generalized than Langmuir isotherm, as its
derivation does not depend on ideal assumptions, such as equipotent of the binding
sites, absence of steric hindrance between incoming and adsorbed metal ions and
surface consistency [382]. The linear presentation of the D–R isotherm equation is
expressed by:
ln q e = lnq m − βε2 [1]

where qe and qm (mg/g), are the equilibrium and maximum biosorption capacity
of adsorbent (CLR), β (mol2/kJ2) is the activity coefficient related to adsorption mean
free energy and ε is the Polanyi potential which can be calculated using Equation 2.
1
ε = RT ln(1 + c ) [2]
e

The biosorption mean free energy (E; kJ/mol) can be calculated using the
following equation;
E = 1/(−2β)1/2 [3]

If the value of E lies in the range 8 -16 kJ/mol, the chemical adsorption process
takes place whereas, when E < 8 kJ/mol, the physical adsorption process occurs [383].
Mean biosorption energy E for adsorption of Pb(II) and Cd(II) ions on surface of CLR
lies (11.18 kJ/mol) within the range of chemisorption (Table 5.2).
The equilibrium data were fitted in the Freundlich, Langmuir and D-R isotherm
models and all of the isotherm parameters were calculated from their concerned linear
equations as described in chapter 3, and are provided in Table 5.2. Experimental data
(Figure 5.7 and Table 5.2) shows a better agreement with Langmuir adsorption isotherm
72
 Chapter 5

model (R2~0.99) as compared to that of the Freundlich isotherm model for removal of
both metal ions Pb(II) and Cd(II) using CLR indicating monolayer formation of metal
ions on the surface of adsorbent. The value of Freundlich constant n > 1, indicates that
the biosorption of Pb(II) and Cd(II) ions onto CLR was favorable process [384]. The
Langmuir maximum biosorption capacity (qm) of CLR was found to be 43.67 mg/g for
Pb(II) and 55.56 mg/g for Cd(II) ions. The maximum adsorption capacity of CLR is
significantly higher as compared to those of many other biosorbent studied earlier
(Table 5.3). Due to higher adsorption capacity of CLR for removal of Pb(II) and Cd(II)
ion, it might be used as a promising adsorbent for removal these metals from aqueous
solutions.

Figure 5.7 Adsorption isotherm of Pb(II) (a) & Cd(II) ion (b) removal using CLR at
25±1°C.

73
 Chapter 5

Table 5.2: Adsorption equilibrium parameters of Pb(II) and Cd(II) ions on the surface of CLR.
Freundlich Isotherm Langmuir Isotherm D-R Isotherm
kF N R2 kL qm R2 β qm E R

(mg1−1/n g−1 l1/n) (l/mg) (mg/g) (mol2kJ−2) (mg/g) (kJ/mol)

Pb 6.11±0.001 1.79 ± .014 0.980 0.135 ± .0002 43.67 ± .190 0.993 4×10-7 ± .001 22.5±.31 11.18 ± 0.001 0.840

Cd 12.19 ±0.856 2.14 ± .070 0.983 0.305 ± 0.036 55.56 ± .309 0.990 4×10-7± .001 24±0.27 11.18 ± 0.003 0.830

Table 5.3: Adsorption capacities of Pb(II) and Cd(II) ions by various adsorbents.

Metal Agro-waste Metal uptake Reference

(mg/g)
Pb(II) Maize Tassel Activated Carbon 37.31 [285]
ZnCl2 activated Coffee residue 62.57 [199]
Granular activated coconut shell 21.28 [217]
Alkali glycerol modified Lignin 8.2-9.0 [139]
Wheat bran acid treated 79.37 [204]
Citric acid modified CLR 43.67 Present study
Cd(II) NaOH treated Rice husk 20.20 [158]
Jack fruit peel 52.08 [246]
Thioglycolic acid treated cassava waste 18.05 [146]
Pyrolised coffee residue 39.50 [385]
Citric acid modified corncob 55.20 [386]
NaOH treated Cedrus deodar sawdust 73.62 [189]
Citric acid modified CLR 55.56 Present Study

74
 Chapter 5

5.3.6 Thermodynamic study

The thermodynamic parameters (ΔGº, ΔHo, and ΔSo) were determined by the
method as described in chapter 3 (Figure 5.8). Negative ΔGº values (Table 5.4) indicate
the spontaneity and feasibility of the adsorption process of Pb(II) and Cd(II) ions on
CLR surface. The value of free energy change ΔGº for the adsorption of Pb(II) ions on
CLR surface increases from 15-35oC and decreases in going from 35 to 45oC, however,
in Cd(II) ion adsorption study, there is a continuous increase of ΔGº in above
temperature range.

3.5
3.0 Pb
2.5 Cd

2.0
ln kc

1.5
1.0
0.5
0.0
0.0031 0.0032 0.0033 0.0034 0.0035
1/T

Figure 5.8: Plot of ln kc versus 1/T for the estimation of thermodynamic parameters
for biosorption of Pb(II) and Cd(II) onto CLR

The higher negative value of ΔGº with increasing temperature indicates that
bonding between metal ions and adsorbent CLR is stronger at higher temperature [387].
With increasing temperature, the kinetic and vibrational motion of adsorbent as well as
adsorbate molecules will increase, therefore, the physio-sorption of heavy metal ions
on the surface of adsorbent should decrease and result in decrease of ΔGº. Magnitude
of experimental ΔGº value increases with increasing temperature, therefore, it may be
concluded that adsorption process between heavy metal ion on CLR surface is of mixed
type and magnitude of chemisorption is increasing with increasing temperature to result
higher ΔGº value. The magnitude of free energy change ΔGº for the adsorption of Cd(II)
ion is greater than that for the Pb(II) ions (Table 5.4) indicating stronger bonding
between Cd(II) and CLR than that between Pb(II) ions and CLR. Change in enthalpy,
ΔH◦ is also negative for the adsorption of both metal ions like similar to ΔG◦. The
positive value of ΔH◦ shows the endothermic nature of adsorption process. Magnitude
of ΔH◦ for Cd(II) adsorption is higher than that of Pb(II) ions adsorption corroborating
75
 Chapter 5

the conclusion drawn earlier that the bonding between Cd and adsorbent CLR is
stronger than that between Pb(II) ions and CLR. Positive ΔSº value corresponds to
increase of randomness at the solid/liquid interface during the adsorption process,
which suggests the replacement of some previously adsorbed water molecules on the
surface of adsorbent by Pb(II) and Cd(II) ions [388].

Table 5.4: Thermodynamic parameters of Pb(II) and Cd(II) adsorption onto CLR
Metal ion T (°C) ΔG° ΔH° ΔS°
(kJ/mol) (kJ/mol) (kJ/mol K)
15 -2.47±0.04
25 -3.67±0.02 30.70±0.46(a) 0.115±0.001(a)
Pb(II) 35 -4.77±0.01
45 -5.92±0.005
15 -3.07±0.02
25 -4.82±0.03 47.28±1.0(a) 0.174±0.001(a)
Cd(II) 35 -6.57±0.05
45 -8.32±0.06
(a)
Calculated between 15-45°C (i.e. between 288K-318K)

5.3.7 Kinetic study

Kinetic models i.e. Pseudo first order and pseudo second order models were
applied to the experimental data and the kinetic parameters for both models were
evaluated using the same method as discussed in chapter 3, to get the information about
the mechanism of the adsorption process. The plots of log (qe−qt) vs t for the pseudo-
first-order model were not shown as figure because this plot deviated considerably from
the theoretical data after a short period. Therefore pseudo first order model will not be
applicable to the Pb(II) and Cd(II) ion adsorption onto CLR. In most cases, the pseudo
first order equation did not apply well throughout the entire range of contact time and
is generally applicable over the initial duration of contact time of the adsorption process
[190]. Moreover, It can be seen that the experimental values of adsorption capacity,
qe(exp) is not in good agreement with the pseudo first order theoretical values qe(theoretical)
(Table 5.5). In addition to above the R2 value of pseudo first order also deviates
significantly, therefore, it is concluded that the pseudo-first-order model is not suitable
for the biosorption of Pb(II) and Cd(II) onto CLR. However, the R2 values on the basis
of pseudo second order kinetic model have been found to be in better agreement for the
biosorption of Pb(II) and Cd(II) ions onto CLR. In addition to R2 value, the qe,(theoretical)
value of pseudo second order kinetics are very close to qe,(exp) values for Pb(II) and
Cd(II) ion sorption onto CLR, thereby reinforcing the applicability of pseudo second
order kinetics (Figure 5.9). As the Pb(II) adsorption kinetics on modified CLR followed
76
 Chapter 5

a pseudo-second order kinetics, therefore, it may be concluded that chemisorption is

the dominant mechanism of adsorption.

Figure 5.9: Pseudo second order kinetics for Pb(II) and Cd(II) ion removal from
aqueous solution using CLR at 25±1°C
The plots of qt vs. t0.5 (Fig. 5.6) indicates multi-linearity i.e. the occurrence of a
two-step adsorption process [389] for both, Pb(II) and Cd(II) metal ions. The first
segment is the external surface adsorption [390]. The second segment defines the
gradual adsorption and attainment of equilibrium of metal ions sorption process, where
the intraparticle diffusion is rate-controlled. On the basis of this data it is obvious that
intraparticle diffusion is involved in the Pb(II) and Cd(II) adsorption onto CLR, but it
is not the sole rate-controlling-step as the initial kinetic data do not pass through the
origin [391]. So the overall mechanism involves both the adsorption and intraparticle
diffusion.

77
 Chapter 5

Table 5.5: Adsorption kinetic parameters of Pb(II) and Cd(II) ions on CLR

Pseudo First Order Pseudo Second Order Intraparticle Diffusion

qe(exp) k1ad×10-2 qe1 (theoretical) R2 k2ad×10-3 qe1 (theoretical) h R2 I ki R2
(mg/g) (min-1) (mg/g) (g/mg min) (mg/g) (mg/g min0.5)

Pb(II) 8.44 2.2±0.002 7.73±0.323 0.980 3 ± 0.001 9.10 ± 0.110 0.276 ± .009 0.990 1.22 ± .076 0.49± .005 0.875

Cd(II) 8.99 1.7±0.0002 6.158 ± .110 0.927 8± 0.001 9.40± 0.018 0.737 ±0.040 0.997 1.40 ± .108 0.34± 0.006 0.829

10
9
8
7
6
qe (mg/g)

5
4 Pb Cd
3
2
1
0
0 2 4 6 8 10 12 14 16 18 20
t0.5
Figure 5.10: Intraparticle diffusion plot for Pb(II) and Cd(II) ion removal from aqueous solution using CLR at 25±1°C

78
 Chapter 5

5.3.8 FTIR and SEM Analysis of CLR

The FTIR spectrum of the CLR was complex due to the existence of various
functional groups on the surface of the CLR. When CLR interacted with Pb(II) and
Cd(II) ions of the aqueous phase, bond energy of various functional groups such as OH,
C=O, -COO- and C-O-C present at the surface of CLR were altered, consequently, the
characteristic vibrational peaks of these functional groups were shifted (Figures 5.11
and Table 5.6). An envelope of broadband observed ~ 3390 cm−1 covering combined
hydrogen-bonded –OH and –NH stretching frequency of CLR was shifted to higher
wavenumber ~ 3411 in Pb(II) and ~ 3420 cm−1 in Cd(II) loaded CLR indicating mild
interaction between functional groups present on CLR to respective metal ions. The
peaks ~ 2921 cm−1 due to the C–H stretching vibrations in CLR does not exhibit
significant change on adsorption of heavy metal ions. The C=O stretching vibrations of
CLR is observed as shoulder ~ 1732cm-1 which is shifted to lower wavenumber ~ 1728
cm-1 indicating interaction of carbonyl oxygen to the metal ions on adsorption. A very
small magnitude of shifting indicates a weak interaction. It is worth to be mention that
C=O stretching frequency is observed as distinct band in metal ion loaded CLR unlike
metal free CLR where it is merged with NH and OH bending vibrations ~1646 cm−1
and is observed as shoulder (Figure 5.8a). Presence of only one strong intensity
absorption band at ~ 1646 cm−1 in metal free CLR in the range of 1550- 1700 cm-1
indicate that NH and OH bending and C=C stretching vibration merged into one
envelope. However, Pb(II) loaded CLR exhibit three distinct peaks in the above region
at 1652, 1640 and 1632 cm-1 indicates that NH and OH bending and C=C stretching
vibrational mode are observed at distinct position unlike metal free CLR. Almost
similar trend of vibrational modes are observed in case of Cd(II) loaded CLR. These
observation may be attributed to different magnitude of interaction of OH and NH
functional groups to the Pb(II) ion. C-H stretching frequency is observed at 1427 cm−1
[392] in CLR was shifted to lower wavenumber ~1378 cm−1 for both metal ion sorption
on CLR surface. C-OH bending vibration of carboxylic acid group observed at ~1318
cm−1 [393] was shifted to 1300 cm−1 in Pb(II) and 1252 cm−1 for Cd(II) loaded CLR
indicating strong interaction between heavy metal ion and carboxylic group present on
CLR surface. Peak at ~1036 cm−1 present in IR spectrum of CLR is assigned to
stretching vibration of C-O of lignin structure [394] indicating presence of lignin in
CLR. The corresponding peak was shifted towards higher wavenumber ~1074 cm−1 on

79
 Chapter 5

metal loaded CLR. On the basis of FTIR analysis it has been found that there are
significant changes in vibrational modes of OH group particularly carboxylic group,
NH, phenolic OH and minor change in C=O stretching frequency. Based on these
observation it may be concluded that carboxylic, phenolic and amino groups are the
prominent donor sites present on surface of CLR which are responsible for adsorption
of heavy metal ions, however, ketonic group (C=O) also weakly coordinate to the metal
ions.
SEM images of metal free CLR (Figure 5.12a) shows a rough heterogeneous
surface with groves/ cavities and pores on its surface, whereas, Pb(II) loaded CLR
(Figure 5.12b) shows completely blocked/filled pores and smaller cavities, however
bigger cavities appears to be partially filled. In case of Cd(II) loaded CLR (Figure
5.12c), the SEM images shows almost complete blockage of all the groves/cavities and
pores. Partial blockage of cavities on surface of Pb(II) loaded CLR and completely
blockage of cavities on the surface of Cd(II) loaded CLR is consistent with higher
adsorption capacity of Cd(II) ions as compared to that of Pb(II) ions discussed earlier.

Table 5.6: Wave numbers (cm−1) of main characteristic FTIR peaks of native CLR,
Pb(II) & Cd(II) ion Loaded CLR
Functional group CLR Pb (II) Cd (II)
(cm-1) loaded loaded
CLR CLR
(cm-1) (cm-1)
Stretching vibration of the - OH group from alcohol and 3390 3411 3420
phenols of the surface and also dominated by –NH stretching
Asymmetrical stretching vibration of –C-H 2921 2920 2920 &
2851
Stretching vibration absorption band of carbonyl group 1732 1729 1728
Strong stretching vibration of C-O from carboxylic acid in 1646 1641 1642
presence of intermolecular H bonding
C-H stretching of aromatic rings 1427 1377 1378
C-OH bending vibration of carboxylic acid 1318 1300 1252
Bending vibration of OH and stretching vibration of C-O in 1036 1073 1074
lignin structure

80
 Chapter 5

Figure 5.11: FTIR spectra of different (a) Control CLR, and (b) Pb(II) ions & (c) Cd(II)
ions Loaded CLR samples
81
 Chapter 5

Figure 5.12: Scanning Electron Micrograph of (a) control CLR (b) Pb(II) loaded (c)
Cd(II) loaded CLR

5.3.9 Effect of Multi Metallic Solution on Pb(II) and Cd(II) Uptake

To understand the effect of other ions on the sorption capacity of Pb(II) and
Cd(II), an experiment was conducted by the method described in chapter 3. Bimetallic
solution of Pb(II) ion and one of the metal ions among Cu(II), Ni(II) and Cd(II) and
similarly Cd(II) with one of the metal ions among Cu(II), Ni(II) and Pb(II) were used
for adsorption study. It was found that all the metal ions used in the present study
decreases the uptake of Pb(II) as well as Cd(II) ions. Decrease in adsorption capacities
of Pb(II) and Cd(II) ions were found to be affected by the presence of other metal ions
in the solution in the order Ni(II) > Cu(II) > Pb(II) / Cd(II) [340] (Table 5.7). Thus,
Ni(II) ions most adversely affected the adsorption of respective metal ions. The reason
for this trend may be attributed to competitive adsorption capability and greater affinity
of the metal ions for adsorption on adsorbent surface. Higher affinity of Ni(II) for
adsorption on CLR surface may be responsible for decrease of adsorption capacity of
Pb(II)/Cd(II) metal ions probably due to smaller ionic radius of Ni(II) ions (0.72Ǻ) as
compared to those of Cu(II) (0.73Ǻ) and Pb(II) (1.19 Ǻ) /Cd(II) (0.95 Ǻ) ions. Their
higher complexing/binding ability of Ni(II), it binds to the surface of CLR more
strongly than those of Pb(II) and Cd(II), therefore, Ni(II) ions may occupy the major
portion of the surface and thereby reduces the Pb(II) and Cd(II) uptake. Similarly,
Cu(II) ions are also adsorbed on the CLR surface in preference to Pb(II) and Cd(II)
ions. Due to above reason the adsorption capacity of CLR for Pb(II)/Cd(II) was
decreased to significant extent in multi-metal solution.

82
 Chapter 5

Table 5.7: Effect of multi-metal systems on the adsorption capacity of Pb(II) and
Cd(II) ions onto CLR from aqueous solution on Pb(II) and Cd(II) removal
(Condition: Pb(II) and Cd(II) ion conc. 20mg/l, CLR dosage 2.5g/l, contact
time 60 min, agitation speed 250 rpm, temperature 25±1°C)
Sorption System qe (mg/g) Sorption System qe (mg/g)
Pb(II) 9.08 ± 0.03 Cd(II) 9.47 ± 0.06
Pb(II)-Cd(II) 8.13 ± 0.04 Cd(II)-Pb(II) 7.95 ± 0.05
Pb(II)-Cu(II) 8.09 ± 0.04 Cd(II)-Ni(II) 8.48 ± 0.01
Pb(II)-Ni(II) 7.03 ± 0.01 Cd(II)-Cu(II) 7.45 ± 0.01
Pb(II)-Cd(II)-Ni(II)-Cu(II) 6.20 ± 0.10 Cd(II)-Pb(II)-Ni(II)-Cu(II) 6.61 ± 0.03

5.3.10 Desorption Study

The adsorbed metal ion on the CLR surface was desorbed using 1M HNO3 as
per details described in chapter 3. The percentage desorption was studied by progressive
increase of volume of eluent (1M HNO3) from 3.0–10.0 ml. Maximum percentage
desorption for Pb(II) and Cd(II) ions was found to be 97% and 92% using 7 and 9 ml
of 1 M HNO3 as eluent, respectively (Fig. 5.13a). Higher amount of eluent required to
desorb maximum amount of Cd(II) ion from CLR as compared to that of Pb(II) indicate
that Cd(II) ion is adsorbed on CLR surface more tenaciously than Pb(II). Repeatedly
using regenerated CLR by adsorption followed by desorption shows that maximum
percentage desorption decreases 16 and 9% for Pb(II) and Cd(II) ions, respectively (Fig.
5.13b) after ten cycles of adsorption – desorption process. This indicates that CLR can
be used for removal of Cd(II) ions repeatedly more times with good efficiency than that
of Pb(II) ions removal.

Figure 5.13: Desorption efficiency of CLR with respect to eluent volume (a) and cycle
number (b).
83
 Chapter 5

5.4 Conclusion
The highest present removal of Pb(II) and Cd(II) ions by CLR was found at pH
6. The experimental data for the adsorption of Pb(II) and Cd(II) on CLR showed a better
agreement with Langmuir isotherm model as compared to that of Freundlich isotherm
model. For the sorption of Pb(II) and Cd(II) ions onto CLR both Langmuir and D–R
isotherms adsorption models was used for interpretation of the equilibrium data.
Langmuir isotherm model indicated monolayer formation of metal ions on the CLR
surface, whereas using D-R isotherm mean biosorption energy E exhibited the value
(11.18 kJ/mol) within the range of chemisorption for the adsorption of Pb(II) and Cd(II)
ions on the surface of CLR, suggesting the occurrence of chemisorption. The
thermodynamic parameters i.e ΔG°, ΔS° and ΔH° indicated endothermic nature of the
adsorption process i.e. spontaneously feasible adsorption of Pb(II) and Cd(II) ions on
CLR surface. Kinetic studies showed a better fit of pseudo-second order kinetics to the
experimental data with a higher correlation coefficient value (R2= 0.990) as compared
to pseudo first order kinetics, further confirmed the occurrence of chemisorption of
Pb(II) and Cd(II) ions onto modified CLR surface. Higher affinity of Ni(II) due to its
smaller size, it reduced the maximum adsorption capacity of Pb(II) and Cd(II) ions on
the surface of CLR from bimetallic or multi-metallic solution as compared to those of
other metal ions such as Cu and Cd/Pb. Maximum desorption of Pb(II) and Cd(II) ions
from CLR surface showed the ~97% and ~92%, respectively of above metal ions using
a minimum volume of 7 and 9 ml of 1 M HNO3 as eluent. Higher amount of eluent
required to desorb maximum amount of Cd(II) ion from CLR surface as compared to
that of Pb(II) indicated that Cd(II) ion is adsorbed on CLR surface more tenaciously
than Pb(II). Higher adsorption capacity of CLR (qm for Pb(II) = 47 mg/g and qm for
Cd(II) =55.56 mg/g) and multiple repeated reusability with good efficiency as
determined from desorption study showed that CLR has a significant potential as an
adsorbent for the removal of Pb(II) and Cd(II) ions from aqueous solutions/industrial
wastewater. Heavy metal removal with the CLR would be technically feasible with high
efficiency, its recyclability without much loss of efficiency, cost effective and
ecofriendly, therefore, the CLR can be adopted and widely used for the remediation
process of heavy metals.

*******************
84
 Removal of Cd(II) ions from simulated wastewater using
6
NaOH modified Desmostachya bipinnata (Kush grass)
Leaves & Bambusa arundinacea (Bamboo) Leaves
6.1 Introduction
In previous chapters we studied the removal of Cd(II) ions using Cucumis
sativus peel (CSP) and watermelon rind (CLR). These biosorbents are seasonal and are
available only for a short period of time, therefore, it was decided to study the removal
of Cd(II) ions by a suitable cheap biosorbent which are available throughout the year.
In view of above it was decided to study, Cd(II) ion sorption using Desmostachya
bipinnata (Kush grass) Leaves (DBL) and Bambusa arundinacea (Bamboo) Leaves
(BAL), both members of true grass family: Poaceae. As both the adsorbents correspond
to the same family, their major constituents are almost the same. These materials are
the major organic components of the solid waste, comprising about 14.6% of total
municipal solid waste (MSW) and about 50% of the organic fraction of the MSW [395].
However, in the entire world, India has a vast rate of biomass production, including
organic wastes, such as grass, leaves and flowers. Therefore, it is better to use these
abundant agricultural wastes for remediation of heavy metal from contaminated
aqueous solutions. These materials contain lignin and cellulose which possess
numerous polar functional groups including phenolic and carboxylic acid groups,
therefore, they can exhibit strong potential for removal of heavy metal ions such as
Cd(II) [396] [397, 398]. In addition to above these materials are of low cost, therefore,
DBL and BAL are an attractive option for the adsorption of Cd(II) ion from the aqueous
solution. Further it was observed that several biosorbents exhibit increased adsorption
capacity when treated with NaOH [399]. Therefore, it was decided to use NaOH treated
DBL and BAL adsorbents for removal of Cd(II) ion in present chapter. In study of
present chapter same parameters were applied as in previous chapters.

85
 Chapter 6

6.2 Materials and Methods

6.2.1 Chemicals
The stock solution of Cd(II) ion (1000 mg/l) was prepared in DW using
Cadmium nitrate salt (Merck) and all working solutions were prepared using the same
method as described in chapter 3.

6.2.2 Adsorbent Preparation

DBL and BAL were obtained from the open fields of Indian Institute of Toxicology
Research, Gheru Campus (Lucknow, India). Both were dried under the sunlight for two
days, ground, washed several times with DW. These samples were modified using 0.5
M NaOH solution with 1:20 for 30 min (solid-liquid ratio) [400]. After 30 min both the
materials were filtered. The MDBL and MBAL were again dried at 100oC for 24 h and
afterwards screened to obtain approx. 0.250 mm sized particles (mesh sieve, 60), and
then stored in an airtight container.

6.2.3 Analytical/ Physico-Chemical Characterization

Analytical/ physico-chemical characterization parameter i.e. bulk density,
particle density, percentage porosity, percentage moisture content and percentage ash
content were determined using the procedure as discussed in Chapter 3 (Table 5.1).
The pHZPC determination was performed in the same way as described in chapter 4.
All the solutions were analyzed for Cadmium using AAS with characteristic
wavelength of 228.8 nm for Cd(II). FTIR and SEM analysis of MDBL and MBAL
before and after Cd(II) removal was performed same as described in chapter 3.

6.2.4 Batch Adsorption Studies

Batch experiments were executed following the same method as described in
Chapter 3 with an initial concentration of Cd(II) ions at 20mg/l for 240 min to ensure
equilibrium at a steady temperature (25±2oC) and agitating speed (250 rpm). Percentage
metal removal (% removal) and the adsorption capacities q (mg/g) were calculated by
mass balance relationship equation as described in detail in Chapter 3.
Isotherm studies were recorded by varying the initial Cd(II) ion concentration
from 10-150 mg/l using MDBL and MBAL separately following the same method as
described in chapter 3. Thermodynamic study was performed at three temperatures (i.e.
25°C, 35°C and 45°C) and the thermodynamic parameters were determined using the
same method as discussed in chapter 3. Equilibrium data were also evaluated after

86
 Chapter 6

applying pseudo first order and pseudo second order kinetic model same as described
in chapter 3. Here it’s worth to mention that kinetic study was performed at RT for three
varying concentration of Cd(II) ion i.e. 20, 30 and 50mg/l.

6.2.5 Effect of Other Ions in Aqueous Solution on Adsorption

The effect of presence of other anions such as Sulfate (SO4-), carbonate (CO32-
), chloride (Cl-), nitrate (NO32-) and cations like Na+, K+, Ca2+, Mg2+ and heavy metal
ions such as, Cu(II), Ni(II) and Pb(II) ions on Cd(II) ion removal was studied using 20
mg/l of initial Cd(II) ion concentration at optimized conditions following the same
procedure as described in Chapter 3.

6.2.6 Desorption and Regeneration

Desorption experiments were performed to consider the practical usefulness of
the biosorbents. After the biosorption experiments using 20mg/l of Cd(II) metal
concentration, 0.2g of metal loaded sorbent were agitated in 100 ml of 0.1 M HCl and
0.1 M HNO3. [401]. After 60 min of contact time the metal concentration in the solution
was determined. To check the applicability as the best eluent the sorption desorption
steps were repeated five times.

6.3 Results and Discussion

6.3.1 Characterization of MDBL and MBAL

Physical characteristics of both the modified adsorbents i.e MDBL and MBAL are
summarized in table 6.1.
Table 6.1: Physical characteristic of MDBL & MBAL
Parameter MDBL MBAL
Particle density 0.144 0.196
Bulk density (g/ml) 0.127 0.166
Porosity (%) 11.3 15
Moisture content (%) 10.93 8.30
Ash content (%) 2.57 1.42
pHzpc 5.50 5

6.3.2 Effect of pH
The effects of initial pH of the solution on the Cd(II) ion removal efficiency was
studied at varying pH range from 3.5 to 8.5. With increasing pH from 3.5 to 6.5, a sharp
increase in the percentage Cd(II) ion removal was observed from ~56 to ~72% for
MDBL and ~51 to ~69% for MBAL (Figure 6.1). The Cd(II) ion removal efficiency is
little below pH 4.5 and reason may be attributed to the presence of higher proton
87
 Chapter 6

concentration in the solution that compete with the Cd(II) ions for the adsorption sites
of the adsorbents at lower pH. As the pH increases above 4.5, the H+ concentration
decreases, leading to enhanced Cd(II) ion uptake up to pH 6.5. Whereas, beyond pH
6.5 the Cd(II) ion percentage removal become static due to saturation of active sites on
the surface of both the adsorbents. It is apparent that optimum percentage removal was
obtained at pH 6.5, therefore pH 6.5 was selected as the best pH to study the overall
adsorption process for both the adsorbents. Batch experiment could not performed
beyond pH 8.5 due to precipitation of Cd(II) ions [209, 402].

Figure 6.1: Effect of pH on Cd(II) ion adsorption by MDBL and MBAL at 25°C
(Condition: 20mg/l of Cd(II) ion solution, 250 rpm, 5g/l adsorbent dosage, 60 min).
The effect of pH can also be explained in terms of pHzpc of the adsorbent. As it
is described in chapter 5 that above pHzpc the adsorbent surface become negatively
charged and this may be due to deprotonation of carboxyl and hydroxyl groups present
on the adsorbent surface. Cd(II) ion may most likely be bound on the MDBL and
MBAL surface via an ion exchange mechanism as following equation:
2(-RCOOH) + Cd+2 = (RCOO)2 Cd + 2H+ [3]
(where -R represents the matrix of the adsorbents)

Whereas above pHzpc value i.e. 5.5 for MDBL and 5 for MBAL, as a rule of
interaction, the positively charged Cd(II) species (soft acids i.e. Cd2+ and Cd (OH)+)
present in the aqueous solution will interact with the negatively charged adsorbent
surface, thereafter a sudden increase in percentage removal of Cd(II) ions from aqueous

88
 Chapter 6

solution was observed above pH 5.5 for both adsorbents up to pH 6.5. Therefore the
optimum percentage removal was obtained at pH 6.5 [191].

6.3.3 Effect of Initial Ion Concentration

The Cd(II) ion uptake is particularly reliant on the initial metal ion
concentration. At the lower range of initial metal ion concentration, Cd(II) ion is
adsorbed by available binding sites, while at higher range decreased adsorption is due
to the saturation of adsorption sites and also due to lack of sufficient surface area to
accumulate further available ions. It is observed that with increasing initial The
percentage Cd(II) ion removal using MDBL decreases from ~74-66% on increasing
initial Cd(II) ion concentration from 10-150 mg/l. Whereas, using MBAL percentage
Cd(II) ion removal decreases from ~69-56% on increasing Cd(II) concentration from
same in the above range (Figure 6.2).

Figure 6.2: Effect of initial Cd(II) ion concentration for adsorption process by MDBL
and MBAL at 25°C (Condition: 5g/l adsorbent dosage, 250 rpm, 60 min)

6.3.4 Effect of Biosorbent Dosage

Figure 6.3 shows the effect of adsorbent dosage on percent Cd(II) ion removal
and as well as on the adsorption capacity of MDBL and MBAL. It was observed that
the percent removal of heavy metals increases rapidly with an increasing adsorbents
dosage in case of both the adsorbents i.e. MDBL and MBAL. It is apparent from figure
6.3, that for the initial Cd(II) ion concentration of 20 mg/l, the percentage Cd(II)
removal increases from ~64 to 86% with increasing MDBL dosage from 2 to 10 g/l,
whereas in case of MBAL, percentage Cd(II) removal increases from ~66 to 82 % with

89
 Chapter 6

the increasing dosage from 2 to 8 g/l. This may be due to the fact that high adsorbent
dosage provides availability of free binding sites on entirely exposed [275] larger
adsorbent surface area and also due to higher pore volume [403]. Beyond the 10g/l
dosage of MDBL and 8g/l dosage of MBAL there is no significant change in percentage
Cd(II) ion removal.

Figure 6.3: Effect of adsorbent dosage for Cd(II) ion adsorption by MDBL and
MBAL at 25°C (Condition: 20mg/l of Cd(II) ion solution, 250 rpm, 60 min, pH 6.5).
Whereas, adsorption capacity (i.e. the amount adsorbed per unit mass) decreases
on increasing adsorbent dosage because only a part of active binding sites are exposed
[404] which is occupied by Cd(II) ions and also due to unsaturation of adsorption sites
on higher dosage through the adsorption reaction for the fixed initial metal ion
concentration [356] thus leading to a lower adsorption capacity. Therefore the obtained
optimum dose for MDBL is 10 g/l and for MBAL is 8 g/l for the removal of Cd(II) ions
using initial Cd(II) ion concentration of 20 mg/l.

6.3.5 Effect of Contact Time

The effect of contact time on Cd(II) ions removal by MDBL and MBAL was
studied and shown in Figure 6.4. It can be seen that on increasing contact time from 10-
120 min, it shows a rapid increase in the Cd(II) ions percentage removal from ~37% to
87%, whereas in case of MBAL the percentage Cd(II) ion removal increases from ~30%
to 87% and after 120 shows a gradual uptake of Cd(II) ions. Further increasing contact
time beyond 180 min for MDBL and 150 min for MBAL, the percentage Cd(II) ion
removal did not changed significantly and may be due to attainment of equilibrium.

90
 Chapter 6

The rapid uptake of Cd(II) ions at the initial stage may be due to the higher driving
force that make fast transfer of metal ions to the surface of adsorbent and also due to
the accessibility of the free surface area and the binding sites on the adsorbent [183].
With further increasing time, there is no significant change is observed and this may be
due to unavailability of the free surface area/freely available binding sites.
Simultaneously with increasing contact time driving force also decreases and, therefore,
metal ions slowly diffuse into the intra-particle pores of the adsorbent and thus it take
some time to reach equilibrium [405]. Therefore it is apparent that it takes about 180
and 150 min to reach adsorption equilibrium for MDBL and MBAL, respectively.

Figure 6.4: Effect of contact time on Cd(II) ion adsorption by MDBL and MBAL, at
25°C, (Condition: 20 mg/l of Cd(II) ion solution, 250 rpm, 5g/l adsorbent dosage)

6.3.6 Adsorption Isotherms

The adsorption data were analyzed using Freundlich (1906) and Langmuir
(1918) isotherm models. Freundlich and Langmuir equations have their own limitations
in describing the equilibrium data adequately. Both are based on utterly unlike
principles, and the fact that the experimental [406] fallouts fit one or another equation,
imitates a purely mathematical apt. The values of Freundlich isotherm parameters (KF
and n) and Langmuir adsorption isotherms parameters (qm and KL) for Cd(II) ion
removal using MDBL (Figure 6.5) and MBAL (Figure 6.6) were determined using the
same method as described in chapter 3 on the basis of linear correlation between the
values of :

 log qe vs log Ce (Freundlich Isotherm)

 Ce/qe vs Ce (Langmuir Isotherm)
91
 Chapter 6

Figure 6.5: Freundlich (a) and Langmuir (b) isotherm for Cd(II) ion removal using
MDBL at varying temperature.

Figure 6.6: Freundlich (a) and Langmuir (b) isotherm for Cd(II) ion removal using
MBAL at varying temperature.

In the present study at increasing temperature, higher k F values and value of n

>1 (Table 6.2) indicating a high affinity between adsorbent and Cd(II) ions thus shows
favorable adsorption of Cd(II) ions onto MDBL and MBAL. The experimental data
shows a better agreement to Langmuir isotherm model higher with a high correlation
coefficients value (R2 > 0.990 for MDBL and R2 > 0.985 for MBAL) as compared to
that of Freundlich isotherm model for both the adsorbents at varying temperatures
(Table 6.2).

92
 Chapter 6

Initially, on increasing the temperature from 298 to 308K adsorption capacity

increases for MDBL and decreasing values were noticed from 308-318 K. Whereas,
continuous decrease in adsorption capacity was observed for MBAL up to 318 K, which
might be due to either the damage of active binding sites of adsorbent [407] or
increasing propensity of desorption of Cd(II) ions from the interface to the solution at
higher temperature [408]. This is because at higher temperature the thickness of the
boundary layer decreases and thus tendency of the metal ion to escape from the biomass
surface to the solution phase increases [409]. From the admirable values of adsorption
capacity (qm) (Table 6.2), it is obvious that MDBL and MBAL exhibited a high number
of favorable accessible adsorption sites, and evidenced excellent promising adsorbents
for Cd(II) ions from aqueous solution.

Table 6.2: Adsorption Isotherm parameters at different temperatures

Temp Freundlich Isotherm Langmuir Isotherm
kF n R2 qm kL R2
(mg1−1/n g−1 l1/n) (mg/ g) (l/mg)
MDBL
298 1.251±0.057 1.505±0.002 0.977 15.222±0.162 0.077±0.006 0.997
308 1.460±0.067 1.522±0.045 0.979 19.843±0.570 0.090±0.006 0.992
318 1.552±0.028 1.501±0.006 0.955 15.540±0.085 0.104±0.003 0.995
MBAL
298 1.424±0.025 1.472±0.016 0.977 19.705±0.097 0.064±0.001 0.987
308 1.961±0.020 1.596±0.011 0.949 18.483±0.151 0.107±0.001 0.986
318 2.024±0.061 1.602±0.018 0.933 17.331±0.425 0.135±0.008 0.993

6.3.7 Thermodynamic Study

Thermodynamic parameters i.e. entropy (ΔSo) and enthalpy (ΔHo) change were
obtained from the slope and intercept of the plot of log kc vs 1/T, respectively using the
same method as described in chapter 3. (Figure 6.7). kc is the equilibrium constant
obtained using Lagmurian parameters. ΔGo is also calculated using the same equation
as discussed in chapter 3. The negative ΔGº (Table 6.3) value indicates feasibility and
spontaneity of the adsorption process. The higher negative value of ΔGº with increasing
temperature regardless the nature of adsorbent, indicate that a better adsorption is
actually obtained at the higher temperature [387]. Positive value of ΔH◦ shows the
endothermic nature of reaction [388], whereas the positive ΔSº value corresponds to
the increased randomness at the solid/liquid interface during the adsorption process
[325], which suggests the displacement of previously adsorbed some water molecules
from the surface of adsorbent with coming Cd(II) ions from the solution [190]. All the

93
 Chapter 6

displaced molecules gain more translation entropy than lost by the adsorbate ions, hence
permitting the prevalence of randomness in the system [190, 388].

Figure 6.7: Plot of ln kc versus 1/T for the estimation of thermodynamic parameters for
Cd(II)ion sorption onto MDBL and MBAL
Table 6.3: Thermodynamic parameters at different temperatures for Cd(II) ion
adsorption using MDBL and MBAL.

Temp Thermodynamic Parameters

(K) ΔGo ΔHo ΔSo
(kJ/mole) (kJ/mol) (kJ/ mol K)
MDBL
298 -0.40
308 -0.93 15.21 0.052
318 -1.45
MBAL
298 -0.75
308 -1.46 20.68 0.072
318 -2.18

6.3.8 Kinetic Study

In the present study, to evaluate the kinetics of adsorption of Cd(II) ions using
the MDBL and MBAL as adsorbents, the pseudo-first-order [259] and pseudo-second-
order kinetics models [329, 410] were tested. The pseudo first and pseudo second order
kinetics parameters have been evaluated using the same method as described in chapter
3. It should be pointed out that, in the present study all the kinetic data up to 240 min
were considered at different initial ion Cd(II) concentration for pseudo-second-order
rate model. Whereas, for pseudo-first-order rate model, only initial kinetic data up to
150 min and 120 min for MDBL and MBAL, respectively have been used because
using a whole range of contact time, the calculated values of qe (mg/g) for pseudo-first-

94
 Chapter 6

order rate model is physically unacceptable [411]. The pseudo-first-order rate model
does not fit well to the whole range of contact time in several other cases also and is
generally applicable to the initial phase of the adsorption processes [329, 412].
The equilibrium adsorption capacity and the second-order rate constant were
determined from the slope and intercept of the plot of t/qt vs t (Figure 6.8 a, b). The data
illustrated good compliance with higher correlation coefficients (R2 > 0.990) value for
the pseudo-second order kinetic model as compared to pseudo first order kinetic model
(Table 6.4) for both the adsorbents i.e. MDBL and MBAL. It also suggests the
hypothesis behind the pseudo-second-order kinetics that the metal sorption process is
due to chemisorption [329]. Chemisorption may occur by the polar functional groups
of cellulose, hemicellulose and lignin, which include alcohols, aldehydes, ketones,
acids, and phenolic hydroxides as chemical bonding functional groups [305]. It can also
be perceived that, for both the adsorbents, with an increase in initial metal concentration
from 20 to 50 mg/l, the adsorption capacity increases [411] while the pseudo second
order rate constant of adsorption (k2ad) decreases (Table 6.4) [329]. The observed
decrease in the rate constants (k2ad) with an increase in initial metal ion concentration
may be because at higher concentration, the average distance between the adsorbed ion
is contracted to a point where each ion affect the charge distribution of its adjacent ions.

Figure 6.8: Pseudo Second Order Kinetic Parameters for the adsorption of Cd(II) ion
on MDBL and MBAL at various initial Cd(II) ion concentrations

95
 Chapter 6

Table 6.4: Pseudo-First-Order and Pseudo-Second-Order Kinetics Parameters and

Intraparticle diffusion model Parameters for Cd(II) ion adsorption using
MDBL and MBAL at varying initial Cd(II) ion concentration.

Bio- Metal Pseudo-first order Pseudo-second order

sorbent Conc.
(mg/l) qe, cal k1ad×10-2 R2 qe, cal k2ad×10-2 R2
(mg/g) (min-1) (mg/g) (g /mg min)
MDBL 20 1.09±0.054 1.8±0.0002 0.924 1.88±0.020 5.8±0.004 0.997
30 2.10±0.023 2.7±0.0003 0.985 2.83±0.006 3.0±0.001 0.996
50 3.54±0.014 1.8±0.0012 0.978 4.79±0.001 1.0±0.000 0.991
MBAL 20 1.52±0.014 1.4±0.001 0.920 2.38±0.007 2.8±0.0002 0.991
30 2.88±0.018 3.0±0.006 0.930 3.59±0.025 1.6±0.0004 0.990
50 5.38±0.092 3.2±0.005 0.963 5.95±0.007 1.1±0.0004 0.990
Intra particle diffusion
I kid R2
(mg/g min0.5)
MDBL 20 1.04±0.070 0.033±0.03 0.976
30 1.95±0.021 0.058±0.001 0.987
50 1.95±0.021 0.180±0.002 0.921
MBAL 20 1.27±0.08 0.060±0.010 0.971
30 2.08±0.02 0.093±0.006 0.983
50 3.86±0.24 0.140±0.020 0.976

6.3.9 Sorption Mechanism

The kinetic data were analyzed by intraparticle diffusion model to elucidate the
key steps involved during the adsorption process for a solid liquid adsorption process.
The adsorbate transfer is usually characterized by either external mass transfer
(boundary layer diffusion) or intraparticle diffusion or both as described in previous
chapters. The plots of qt vs. t0.5 at different initial Cd(II) ion concentrations shows the
occurrence of a three-step adsorption process of Cd(II) ions on the surface of MDBL
(Figure 6.9a) and MBAL (Figure 6.9b) [389].
The intra particle diffusion parameters for MDBL and MBAL are shown in
Table 6.4. The intra particle diffusion plot shows three sectioned plots for the Cd(II)
ion removal using MDBL and MBAL. The first sharp section of the plots represent the
external surface adsorption or an instantaneous adsorption stage [184] whereas, the
second section represents a gradual adsorption where intraparticle or pore diffusion
process is rate limiting step [184]. The stable third portion shows stabilization of
process which confirms that the process reached up to equilibrium [390]. Thus, in case
of both the adsorbent MDBL and MBAL, it showed occurrence of three processes that
were controlling the rate of adsorption but only one was rate-limiting in any particular
96
 Chapter 6

time range [184]. The intercept values increased with the increasing initial metal ion
concentration suggesting that the surface diffusion shows more impact at higher metal
concentration [184] due to the larger availability metal ions. The initial kinetic data do
not pass through the origin for both MDBL and MBAL too, so on the basis of these
data it is obvious that intraparticle diffusion is not the sole rate controlling step [391].
Therefore it can be concluded that the overall mechanism involves adsorption and
intraparticle diffusion for the removal of Cd(II) ions using MDBL and MBAL.

Figure 6.9: Intraparticle diffusion model for Cd(II) ion adsorption by MDBL (a) and
MBAL (b) at various initial Cd(II) ion concentrations.

6.3.10 Effect of Anions and Cations on Biosorption

The effect of anions and cations on Cd(II) ion removal was studied using MDBL
and MBAL (Figure 6.10). Some anions can have an affinity towards the metal ions
forming an insoluble/soluble complex, displaced with difficulty in the presence of the
sorbent material [413], for these reasons, we have respectively studied the effect of the
presence of four classic anions: carbonate, sufate, chloride and nitrate. It is apparent
that, for the same Cd(II) ion concentration (i.e. 20 mg/l) in solution, the percentage
Cd(II) ion removal decreases appreciably with increasing concentration of carbonate or
sulfate ions as compared to chloride or nitrate ions using MDBL (Figure 6.10a) and
MBAL (Figure 6.10b) as biosorbent. This observation can be attributed to the
formation of various stable complexes of Cd2+ with carbonate/sulfate ligands [367]. The
stability constants of Cd(II) ion with carbonate, sulfate and chloride ions are 4.02, 2.4,
and 1.98, respectively [414, 415].

97
 Chapter 6

Figure 6.10 Effect of presence of anions on Cd(II) ion removal using MDBL (a) and
MBAL (b).
The effect of cation on Cd(II) ion removal using MDBL (Figure 6.11a) and
MBAL (Figure 6.11 b) shows that the presence of Na+ or K+ at their different initial
concentrations, do not disturb the sorption of Cd(II) ions significantly. Whereas
increasing concentration of Ca2+ and Mg+2 ions (from 2mg/l - 20mg/l), the Cd(II) ion
uptake decreases considerably from ~90 to 58% and ~90 to 68%, respectively for
MDBL. Using MBAL the percentage Cd(II) ion removal decreases from ~92 to 60%
and ~ 92 to 70 % for Ca2+ and Mg2+, respectively indicating that the maximum decrease
in percentage Cd(II) ion removal is obtained in presence of Ca2+ ions. The phenomenon
of competition between Cd(II) and Ca2+ ions for the binding sites on adsorbent surface
are in agreement with results those observed by many authors [416, 417].

Figure 6.11 Effect of presence of cations on Cd(II) ion removal using MDBL (a) and
MBAL (b).

98
 Chapter 6

6.3.11 Effect of Bi/Multi-Metallic Solution on Cd(II) Ion Uptake

Table 6.5 demonstrates that the presence of other heavy metals reduced the Cd(II) ion
uptake capacity of MDBL and MBAL with the competitive binding of Pb(II), Cu(II) and Ni(II)
in binary metal system as well as in the multi-metal solution system. The observed reduction in
the sorption capacity of Cd(II) ions in the presence of other could be attributed to the
competition between metal ion for the available binding sites on the adsorbent. In case of Cd(II)
ion removal using MDBL, the highest inhibition effect was observed in the presence of Cu(II)
ions with 11.29% decrease in adsorption capacity followed by Ni(II) and Pb(II) using MDBL
(Table 6.5). Same in case of, Cd(II) ion removal using MBAL, Cu(II) ion causes decreases in
adsorption capacity by 10.70% followed by Ni(II) and Pb(II) ion. The reason is the same as
described in previous chapters i.e. the smaller ionic radius of Cu(II) (0.73 Ǻ) /Ni(II) (0.72 Ǻ)
[340] compared to that of Pb(II) ) (1.19 Ǻ) and Cd(II) (0.95 Ǻ), ions which induces a rapid
saturation of binding sites on to MDBL and MBAL. The findings are similar with previous
chapters and some outcome of authors too.

Table 6.5: Competitive adsorption data in binary and multi-metal systems for the
sorption capacity of Cd(II) ions onto MDBL & MBAL from aqueous
solution
Sorption System MDBL MBAL
(Bimetallic & multi- qe (mg/g) % decrease qe % decrease
metallic system) in qe (mg/g) in qe
Cd(II) 3.60 - 3.80 -
Cd(II)-Pb(II) 3.58 0.56 3.76 0.95
Cd(II)-Ni(II) 3.26 9.45 3.49 8.06
Cd(II)-Cu(II) 3.19 11.29 3.39 10.70
Cd(II)-Pb(II)-Ni(II)-Cu(II) 2.60 27.70 3.17 16.44

6.3.12 Desorption Study

Apart from adsorption, desorption also plays an important role to define the
versatility of an adsorbent as it allows reuse of adsorbent and recovery of valuable
heavy metals. Desorption studies were carried using 0.1M HNO3 and result shows that
~ 80% and ~ 91% efficiency was achieved for desorption of Cd(II) ions from exhausted
MDBL and MBAL, respectively. After the desorption of Cd(II) ions, both sorbents
were washed thoroughly with DW. Five cycles of successive sorption-desorption were
carried out to test the reusability of MDBL and MBAL using 0.1N HNO3 and the
outcome indicated that the adsorption capacity decreases in the range of ~80-71% and
~91-74% for HNO3 regenerated MDBL and MBAL, respectively (Figure 6.11).

99
 Chapter 6

100 MDBL
MBAL
80

60

40

20

0
C-1 C-2 C-3 C-4 C-5

Figure 6.11: Successive use of exhausted MDBL and MBAL for five cycles

6.3.12 FTIR and SEM Analysis of MDBL & MBAL

Occurrences of diverse type of functional groups on MDBL before adsorption
(Figure 6.12a) and & MBAL before adsorption (Figure 6.13a) are confirmed by FTIR,
and their detailed illustration is shown in Table 6.6. Alteration in stretching and bending
vibrations of functional groups after adsorption of Cd(II) ion was visible in FTIR
spectrum of Cd(II) loaded MDBL (Figure 6.12b) and Cd(II) loaded MBAL (Figure
6.13b). Mainly, metal ions were bonded by functional groups such as carboxylic groups
(pectin, hemicellulose and lignin), phenolic groups (lignin and extractives) and a little
amount may also adsorbed by hydroxyl (cellulose, lignin, extractives, and pectin) and
carbonyl groups (lignin) [418]. An envelope of broadband observed at ~3418 cm−1
covering combined hydrogen bonded –OH and –NH stretching frequency of virgin
MDBL was shifted to ~ 3415 cm−1 for Cd(II) ion loaded MDBL. Whereas in case of
MBAL peak at ~3402 cm−1 before adsorption shifted to 3431 cm-1 after Cd(II)
adsorption. The peaks present at ~ 2923 cm−1 due to the C–H stretching vibrations in
both MDBL and MBAL does not exhibit significant change on adsorption of Cd(II)
ions. Before adsorption of Cd(II) ion the peak at ~ 1631 and ~ 1634 cm-1 in MDBL and
MBAL, respectively is due to the strong stretching vibration of C-O from carboxylic
acid in presence of intermolecular H bonding. This peak shifted from ~1634 to 1640
cm-1 in case of Cd(II) ion loaded MBAL, whereas there is no change observed for Cd(II)
ion loaded MDBL. In the region of 1800-1500 cm-1 number of overlapping bands are
observed. The carbonyl component i.e. C=O stretching can be observed in the FTIR
spectra as small peaks, and the shoulders forming part of the main band that appears at
~ 1631 and ~ 1634cm-1 in MDBL and MBAL. In MDBL, the peak due to stretching of

100
 Chapter 6

aromatic ring observed at ~1508 cm-1 [145] before Cd(II) ion adsorption and shifted to
~1516 cm-1 after Cd(II) ion adsorption, however after adsorption peak become broad
and intensified (Figure 6.12 a). Whereas in case on MBAL, before Cd(II) adsorption
peak was observed at ~1540 cm-1 and was shifted to lower wavelength ~1514 cm-1 after
uptake of Cd(II) ion. The C-O symmetric stretching of carboxylic acid group observed
at ~1380 cm−1 before Cd(II) ion adsorption in MDBL was shifted to 1377 cm−1 in Cd(II)
loaded MDBL whereas in MBAL this peak was observed at ~1378cm-1 before
adsorption whereas after adsorption of Cd(II) this peak was shifted to lower wavelength
~1356cm-1. Peak at ~ 1049 and 1069 cm−1 present in FTIR spectra of MDBL and
MBAL before adsorption are assigned to stretching vibration of C-O of lignin which
indicates presence of lignin in both the adsorbents. The corresponding peak was shifted
towards higher wavenumber ~1073 cm−1 on metal loaded MDBL, whereas in MBAL
peak was shifted to 1103cm-1. On the basis of FTIR analysis it has been found that there
are significant changes in vibrational modes of OH group particularly carboxylic group,
and phenolic OH stretching frequency. Based on these observation it may be concluded
that carboxylic, phenolic and amino groups are the prominent active functional groups
which had their position altered and thus confirming the active participation of these
bonded OH groups, secondary amine group, carboxyl groups, C–O stretching of ether
groups and –C–C– group [275, 419] present on surface of CLR which are responsible
for adsorption of Cd(II) ions. Hence, the good sorption properties of both MDBL and
MBAL towards Cd(II) ions can be ascribed to the presence of these functional groups
on their surfaces.
Figure 6.14 (a) and (b) shows SEM images for MDBL and MBAL before and
after the adsorption process, respectively. It is clearly visible that before adsorption
surface of MDBL have rough heterogeneous surface with a large number of steps and
kinks on the adsorbent surface and after adsorption a layer of sorbed metal appear
confirming the Cd(II) adsorption on to MDBL. Whereas, in case of MBAL before
adsorption surface is heterogeneous with pore and groves and after adsorption the
change in the morphology of the adsorbent surface with wrecked edges after adsorption
indicates good possibility for Cd(II) ions to be trapped and adsorbed onto the surface.

101
 Chapter 6

Table 6.6: Functional groups and mode of vibration from the FTIR spectrum of MDBL
and MBAL before and after Cd(II) ion adsorption.

Functional group MDBL Cd (II) MBAL Cd (II)

(cm-1) loaded (cm-1) loaded
MDBL MDBL
(cm-1) (cm-1)
Stretching vibration of bonded -OH group on ~3418 ~3415 ~3402 ~3421
surface
Asymmetrical stretching vibration of –CH3 ~2923 ~2920 ~2923 ~2923
Strong stretching vibration of C-O from ~1634 ~1640 ~1631 ~1640
carboxylic acid in presence of intermolecular H
bonding
Stretching of aromatic ring observed ~1508 ~1516 ~1539 1514
C-C stretching of aromatic ring 1380 1377 1378 1356
C-O stretching of carboxylic acid 1249 1252 - -
Bending vibration of OH and stretching 1049 1064 1059 1103
vibration of C-O-C in lignin
Fingerprint region: Adsorption can’t be clearly 605.21 664.60 563.42 602.96
assigned to any particular vibration because they 610.27 466.37 469.10
correspond to complex interacting vibration
systems

Figure 6.12: FTIR spectra of MDBL before adsorption (a) and Cd(II) ion loaded
MDBL (b).

102
 Chapter 6

Figure 6.13: FTIR spectra of MBAL before adsorption (a) and Cd(II) ion loaded
MBAL (b).

Figure 6.14: Scanning Electron Micrograph showing morphology of MDBL (a) and
MBAL (b) before and after Cd(II) ion adsorption.

103
 Chapter 6

6.3.14 Comparison of MDBL & MBAL with Other Adsorbents

The adsorption capacity of Cd(II) ion onto MDBL & MBAL was noticeable as
compared with other NaOH treated adsorbents reported in literature as sawdust (73.62
mg/g-) [189], Juniper fiber (29.54 mg/g) [210], Rice husk (20.24 mg/g) [158], Coconut
bagasse (17.51 mg/g) [420] and spent grains (17.3 mg/g) [421]. It can be observed that
a pH near 6.0 was found to be an optimum in nearly all the cases with the same
modification method. The adsorption capacity differences of metal uptake are due to
the properties of each adsorbent such as structure, functional groups and surface area.
Thus the capacities found in this work with MDBL (19.84 mg/g) and MBAL (19.71
mg/g) are significant related to other.

6.4 Conclusion
In the present study, NaOH modified DBL and BAL (i.e. MDBL & MBAL)
were characterized and used successfully for the remediation of Cd(II) ions from
simulated wastewater. All the operational parameters such as the pH, adsorbent dosage,
contact time and initial metal ion concentrations evidently affected the removal
efficiency. The Langmuir adsorption isotherm agrees well to the equilibrium adsorption
data with higher correlation coefficient values for MDBL (R2 ~0.99) and MBAL (R2 ≥
0.98) suggesting the occurrence of monolayer formation of Cd(II) ion onto surface of
adsorbent. The obtained maximum adsorption capacity for MDBL (qm = 15.22 mg/g)
and MBAL (qm = 19.70 mg/g) was significantly higher than the adsorption capacities of
lots previously studied adsorbents for the Cd(II) ion removal specialy compared with
NaOH treated biosorbents. The adsorption process follows a pseudo-second-order
kinetics rate model with a higher correlation coefficient value (R2 ≥ 0.99) compared to
than that of pseudo first order kinetic model confirming the existence of chemisorption.
The intra particle diffusion model suggested that more that the overall mechanism
involved both the processes i.e. adsorption and intraparticle diffusion. Thermodynamic
parameters indicated that the adsorption process was spontaneous, feasible and
endothermic under normal conditions. In the bi/multi metallic adsorption system, the
highest inhibition effect was observed in the presence of Cu(II) followed by Ni(II) using
MDBL and MBAL probably due to their smaller ionic radii as compared to Pb(II) and
Cd(II) ions. Desorption study suggested that the regeneration of exhausted MDBL and
MBAL could be performed efficiently using 0.1M HNO3 as an eluting agent
successively up to five adsorption-desorption cycles without any significant loss in

104
 Chapter 6

adsorption capacities at RT. FTIR suggested the involvement of -COOH, -OH, -NH, C-
O functional groups present on MDBL and MBAL surface for the interaction with
Cd(II) ions from the aqueous solution. The high adsorption capacity and which is also
significantly higher than numerous previously studied biosorbents and effective
regeneration of exhausted adsorbents after desorption study strongly recommends its
use as Cd(II) ion removal from aqueous solution. Therefore it can be concluded that
MDBL and MBAL demonstrated a remarkable potential as the low-cost substitutes for
Cd(II) ion removal from aqueous solution.

*******************

105
References
[1] Vieira, R.H., Volesky, B. Biosorption: a solution to pollution? Int. Microbiol.
2000, 3, 17-24.

[2] Armah, F.A., Obiri, S., Yawson, D.O., Onumah, E.E., Yengoh, G.T., Afrifa,
E.K., et al. Anthropogenic sources and environmentally relevant
concentrations of heavy metals in surface water of a mining district in Ghana:
a multivariate statistical approach. J. Environ. Sci. Health A Tox. Hazard.
Subst. Environ. Eng. 2010, 45, 1804-13.

[3] Fu, F., Wang, Q. Removal of heavy metal ions from wastewaters: A review. J.
Environ. Manag. 2011, 92, 407-18.

[4] Sud, D., Mahajan, G., Kaur, M.P. Agricultural waste material as potential
adsorbent for sequestering heavy metal ions from aqueous solutions – A
review. Bioresour. Technol. 2008, 99, 6017-27.

[5] Celik, A., Demirbaş, A. Removal of Heavy Metal Ions from Aqueous
Solutions via Adsorption onto Modified Lignin from Pulping Wastes. Energy
Sources. 2005, 27, 1167-77.

[6] Volesky, B., Holan, Z.R. Biosorption of heavy metals. Biotechnol. Prog. 1995,
11, 235-50.

[7] Kratochvil, D., Volesky, B. Advances in the biosorption of heavy metals.

Trends Biotechnol. 1998, 16, 291-300.

[8] Aksu, Z. Application of biosorption for the removal of organic pollutants: a

review. Process Biochem. 2005, 40, 997-1026.

[9] Srivastava, N.K., Majumder, C.B. Novel biofiltration methods for the
treatment of heavy metals from industrial wastewater. J. Hazard. Mater. 2008,
151, 1-8.

[10] Wang, J., Chen, C. Biosorbents for heavy metals removal and their future.
Biotechnol. Adv. 2009, 27, 195-226.

[11] Remy, L., Carriere, M., Derre-Bobillot, A., Martini, C., Sanguinetti, M.,
Borezee-Durant, E. The Staphylococcus aureus Opp1 ABC transporter imports
nickel and cobalt in zinc-depleted conditions and contributes to virulence.
Mol. Microbiol. 2013, 87, 730-43.

[12] Athar, M., Vohora, S. Heavy metals and environment, New Age International,
1995

106
 References

[13] Ercal, N., Gurer-Orhan, H., Aykin-Burns, N. Toxic metals and oxidative stress
part I: mechanisms involved in metal-induced oxidative damage. Cur. Top.
Med. Chem. 2001, 1, 529-39.

[14] Rao, K.S., Anand, S., Venkateswarlu, P. Adsorption of Cadmium from

Aqueous Solution by Ficus religiosa Leaf Powder and Characterization of
Loaded Biosorbent. CLEAN – Soil, Air, Water. 2011, 39, 384-91.

[15] de Burbure, C., Buchet, J.P., Leroyer, A., Nisse, C., Haguenoer, J.M., Mutti,
A., et al. Renal and neurologic effects of cadmium, lead, mercury, and arsenic
in children: evidence of early effects and multiple interactions at
environmental exposure levels. Environ. Health Perspect. 2006, 114, 584-90.

[16] Flora, S.J., Mittal, M., Mehta, A. Heavy metal induced oxidative stress & its
possible reversal by chelation therapy. Indian J. Med. Res. 2008, 128, 501-23.

[17] Wang, B., Du, Y. Cadmium and its neurotoxic effects. Oxid. Med. Cell
Longev. 2013, 2013, 898034.

[18] Adekunle, A.S., Oyekunle, J.A.O., Baruwa, S.O., Ogunfowokan, A.O.,

Ebenso, E.E. Speciation study of the heavy metals in commercially available
recharge cards coatings in Nigeria and the health implication. Toxicol.
Reports. 2014, 1, 243-51.

[19] Flora, G., Gupta, D., Tiwari, A. Toxicity of lead: A review with recent
updates. Interdiscip. Toxicol. 2012, 5, 47-58.

[20] BIS. Drinking water specifications IS: 10500: 1991, First revision, Bureau of
Indian Standards. India. 1992.

[21] Ahalya, N., Ramachandra, T., Kanamadi, R. Biosorption of heavy metals. Res.
J. Chem. Environ. 2003, 7, 71-9.

[22] Polat, H., Erdogan, D. Heavy metal removal from waste waters by ion
flotation. J. Hazard. Mater. 2007, 148, 267-73.

[23] Qdais, H.A., Moussa, H. Removal of heavy metals from wastewater by

membrane processes: a comparative study. Desal. 2004, 164, 105-10.

[24] Ahluwalia, S.S., Goyal, D. Microbial and plant derived biomass for removal
of heavy metals from wastewater. Bioresour. Technol. 2007, 98, 2243-57.

[25] Tarangini, K. Biosorption of heavy metals using individual and mixed cultures
of Pseudomonas aeruginosa and Bacillus subtilis National Institute of
Technology, Rourkela, 2009.

107
 References

[26] Babel, S., Kurniawan, T.A. Low-cost adsorbents for heavy metals uptake from
contaminated water: a review. J. Hazard. Mater. 2003, 97, 219-43.

[27] Rao, K., Mohapatra, M., Anand, S., Venkateswarlu, P. Review on cadmium
removal from aqueous solutions. Int. J. Eng. Sci. Technol. 2010, 2.

[28] Malik, A. Metal bioremediation through growing cells. Environ. Int. 2004, 30,
261-78.

[29] Benhima, H., Chiban, M., Sinan, F., Seta, P., Persin, M. Removal of lead and
cadmium ions from aqueous solution by adsorption onto micro-particles of dry
plants. Colloids Surf. B Biointerfaces. 2008, 61, 10-6.

[30] Demirbas, A. Heavy metal adsorption onto agro-based waste materials: a

review. J Hazard Mater. 2008, 157, 220-9.

[31] Bux, F., Kasan, H. Comparison of selected methods for relative assessment of
surface charge on waste sludge biomass. Water S. A. 1994, 20, 73-6.

[32] Zouboulis, A.I., Matis, K.A., Hancock, I.C. Biosorption of Metals from Dilute
Aqueous Solutions. Sep. Purif. Rev. 1997, 26, 255-95.

[33] Bhatnagar, A., Sillanpää, M. Utilization of agro-industrial and municipal

waste materials as potential adsorbents for water treatment—A review. Chem.
Eng. J. 2010, 157, 277-96.

[34] Klimmek, S., Stan, H.J., Wilke, A., Bunke, G., Buchholz, R. Comparative
analysis of the biosorption of cadmium, lead, nickel, and zinc by algae.
Environ. Sci.Technol. 2001, 35, 4283-8.

[35] Brown, P., Atly Jefcoat, I., Parrish, D., Gill, S., Graham, E. Evaluation of the
adsorptive capacity of peanut hull pellets for heavy metals in solution. Adv.
Environ. Res. 2000, 4, 19-29.

[36] Manassra, A., Khamis, M., El-Dakiky, M., Abdel-Qader, Z., Al-Rimawi, F.
Simultaneous HPLC analysis of pseudophedrine hydrochloride, codeine
phosphate, and triprolidine hydrochloride in liquid dosage forms. J. Pharm.
Biomed. Anal. 2010, 51, 991-3.

[37] Johnson, P.D., Watson, M.A., Brown, J., Jefcoat, I.A. Peanut hull pellets as a
single use sorbent for the capture of Cu(II) from wastewater. Waste Manag.
2002, 22, 471-80.

[38] Chong, K.H., Volesky, B. Description of two-metal biosorption equilibria by

Langmuir-type models. Biotechnol. Bioeng. 1995, 47, 451-60.

108
 References

[39] Bailey, S.E., Olin, T.J., Bricka, R.M., Adrian, D.D. A review of potentially
low-cost sorbents for heavy metals. Water Res. 1999, 33, 2469-79.

[40] Bhatnagar, A., Sillanpää, M. Utilization of agro-industrial and municipal

waste materials as potential adsorbents for water treatment—A review. Chem.
Eng. J. 2010, 157, 277-96.

[41] Reddy, N.A., Lakshmipathy, R., Sarada, N.C. Application of Citrullus lanatus
rind as biosorbent for removal of trivalent chromium from aqueous solution.
Alexandria Eng J.

[42] Annadural, G., Juang, R.S., Lee, D.J. Adsorption of heavy metals from water
using banana and orange peels. Water Sci. Technol. 2003, 47, 185-90.

[43] Saka, C., Şahin, Ö., Küçük, M. Applications on agricultural and forest waste
adsorbents for the removal of lead (II) from contaminated waters. Int. J.
Environ. Sci. Technol. 2012, 9, 379-94.

[44] Demirbas, A. Heavy metal adsorption onto agro-based waste materials: a

review. J. Hazard. Mater. 2008, 157, 220-9.

[45] Yadanaparthi, S.K.R., Graybill, D., von Wandruszka, R. Adsorbents for the
removal of arsenic, cadmium, and lead from contaminated waters. J. Hazard.
Mater. 2009, 171, 1-15.

[46] Jarup, L. Hazards of heavy metal contamination. Br. Med. Bull. 2003, 68, 167-
82.

[47] Patra, R.C., Rautray, A.K., Swarup, D. Oxidative stress in lead and cadmium
toxicity and its amelioration. Vet. Med. Int. 2011, 457327.

[48] Wang, Y.-H., Lin, S.-H., Juang, R.-S. Removal of heavy metal ions from
aqueous solutions using various low-cost adsorbents. J. Hazard. Mater. 2003,
102, 291-302.

[49] Staessen, J.A., Amery, A., Lauwerys, R.R., Roels, H.A., Ide, G., Vyncke, G.
Renal function and historical environmental cadmium pollution from zinc
smelters. The Lancet. 1994, 343, 1523-7.

[50] Cheung, C.W., Porter, J.F., McKay, G. Elovich equation and modified second-
order equation for sorption of cadmium ions onto bone char. J. Chem.
Technol. Biotechnol. 2000, 75, 963-70.

[51] Wu, J., Lu, J., Chen, T., He, Z., Su, Y., Jin, X., et al. In situ biotreatment of
acidic mine drainage using straw as sole substrate. Environ. Earth. Sci. 2010,
60, 421-9.

109
 References

[52] Islamoglu, S., Yilmaz, L., Ozbelge, H.O. Development of a Precipitation

Based Separation Scheme for Selective Removal and Recovery of Heavy
Metals from Cadmium Rich Electroplating Industry Effluents. Sep. Sci.
Technol. 2006, 41, 3367-85.

[53] Lin, X., Burns, R., Lawrance, G. Heavy Metals in Wastewater: The Effect of
Electrolyte Composition on the Precipitation of Cadmium(II) Using Lime and
Magnesia. Water Air Soil Pollut. 2005, 165, 131-52.

[54] Nogueira, C.A., Margarido, F. Nickel-cadmium batteries: effect of electrode

phase composition on acid leaching process. Environ. Technol. 2012, 33, 359-
66.

[55] Page, A.L., Bingham, F.T. Cadmium residues in the environment. In: Residue
Reviews, Springer New York, 1973, Vol. 48, 1-44.

[56] Pinot, F., Kreps Sarah, E., Bachelet, M., Hainaut, P., Bakonyi, M., Polla
Barbara, S. Cadmium in the Environment: Sources, Mechanisms of
Biotoxicity, and Biomarkers. In: Rev. Environ. Health, 2000, Vol. 15, 299.

[57] Wilson, D.C., Young, P.J., Hudson, B.C., Baldwin, G. Leaching of cadmium
from pigmented plastics in a landfill site. Environ. Sci. Technol. 1982, 16,
560-6.

[58] Garrett, R.G. Natural Sources of Metals to the Environment. Hum. Ecol. Risk
Assess. 2000, 6, 945-63.

[59] Williams, C.H., David, D.J. The Accumulation in Soil of Cadmium Residues
from Phosphate Fertilizers and Their Effect on the Cadmium Content of
Plants. Soil Sci. 1976, 121, 86-93.

[60] WHO. International year of fresh water. General Assembly Resolution

A/RES/55/196. 2003.

[61] Waalkes, M.P. Cadmium carcinogenesis in review. J. Inorg. Biochem. 2000,

79, 241-4.

[62] Lopez, E., Figueroa, S., Oset-Gasque, M.J., Gonzalez, M.P. Apoptosis and
necrosis: two distinct events induced by cadmium in cortical neurons in
culture. Br. J. Pharmacol. 2003, 138, 901-11.

[63] Cao, Y., Chen, A., Radcliffe, J., Dietrich, K.N., Jones, R.L., Caldwell, K., et
al. Postnatal cadmium exposure, neurodevelopment, and blood pressure in
children at 2, 5, and 7 years of age. Environ. Health Perspect. 2009, 117,
1580-6.

110
 References

[64] Kim, S.D., Moon, C.K., Eun, S.-Y., Ryu, P.D., Jo, S.A. Identification of
ASK1, MKK4, JNK, c-Jun, and caspase-3 as a signaling cascade involved in
cadmium-induced neuronal cell apoptosis. Biochem. Biophys. Res. Commun.
2005, 328, 326-34.

[65] Monroe, R.K., Halvorsen, S.W. Cadmium blocks receptor-mediated Jak/STAT

signaling in neurons by oxidative stress. Free Radical Bio. Med. 2006, 41,
493-502.

[66] Pihl, R.O., Parkes, M. Hair element content in learning disabled children.
Science. 1977, 198, 204-6.

[67] Yoshida, F., Hata, A., Tonegawa, H. Itai-Itai disease and the countermeasures
against cadmium pollution by the Kamioka mine. Environ. Econ. Policy Stud.
1999, 2, 215-29.

[68] Ucun, H., Bayhana, Y.K., Kaya, Y., Cakici, A., Algur, O.F. Biosorption of
lead (II) from aqueous solution by cone biomass of Pinus sylvestris. Desal.
2003, 154, 233-8.

[69] Vilar, V.J.P., Botelho, C.M.S., Boaventura, R.A.R. Influence of pH, ionic
strength and temperature on lead biosorption by Gelidium and agar extraction
algal waste. Process Biochem. 2005, 40, 3267-75.

[70] Özacar, M., Şengil, İ.A., Türkmenler, H. Equilibrium and kinetic data, and
adsorption mechanism for adsorption of lead onto valonia tannin resin. Chem.
Eng. J. 2008, 143, 32-42.

[71] Gupta, S., Kumar, D., Gaur, J.P. Kinetic and isotherm modeling of lead(II)
sorption onto some waste plant materials. Chem. Eng. J. 2009, 148, 226-33.

[72] Gupta, V.K., Carrott, P.J.M., Ribeiro Carrott, M.M.L., Suhas. Low-Cost
Adsorbents: Growing Approach to Wastewater Treatment—a Review. Crit.
Rev. Environ. Sci. Technol. 2009, 39, 783-842.

[73] Ake, C.L., Mayura, K., Huebner, H., Bratton, G.R., Phillips, T.D.
Development of porous clay-based composites for the sorption of lead from
water. J. Toxicol. Environ. Health A. 2001, 63, 459-75.

[74] Tunali, S., Akar, T., Özcan, A.S., Kiran, I., Özcan, A. Equilibrium and
kinetics of biosorption of lead(II) from aqueous solutions by Cephalosporium
aphidicola. Sep. Purif. Technol. 2006, 47, 105-12.

[75] Kalia, K., Flora, S.J. Strategies for safe and effective therapeutic measures for
chronic arsenic and lead poisoning. J. Occupat. Health. 2005, 47, 1-21.

[76] Pearce, J.M. Burton's line in lead poisoning. Eur. Neurol. 2007, 57, 118-9.
111
 References

[77] Guidotti, T.L., McNamara, J., Moses, M.S. The interpretation of trace element
analysis in body fluids. Ind. J. Med. Res. 2008, 128, 524-32.

[78] Cleveland, L.M., Minter, M.L., Cobb, K.A., Scott, A.A., German, V.F. Lead
hazards for pregnant women and children: part 1: immigrants and the poor
shoulder most of the burden of lead exposure in this country. Part 1 of a two-
part article details how exposure happens, whom it affects, and the harm it can
do. Am. J Nur. 2008, 108, 40-9.

[79] Kadirvelu, K., Thamaraiselvi, K., Namasivayam, C. Removal of heavy metals

from industrial wastewaters by adsorption onto activated carbon prepared
from an agricultural solid waste. Bioresour. Technol. 2001, 76, 63-5.

[80] Frisbie, S.H., Ortega, R., Maynard, D.M., Sarkar, B. The concentrations of
arsenic and other toxic elements in Bangladesh's drinking water. Environ.
Health Perspect. 2002, 110, 1147-53.

[81] Iqbal, M., Saeed, A., Akhtar, N. Petiolar felt-sheath of palm: a new biosorbent
for the removal of heavy metals from contaminated water. Bioresour. Technol.
2002, 81, 151-3.

[82] Huisman, J.L., Schouten, G., Schultz, C. Biologically produced sulphide for
purification of process streams, effluent treatment and recovery of metals in
the metal and mining industry. Hydrometallurgy. 2006, 83, 106-13.

[83] Chen, Q., Luo, Z., Hills, C., Xue, G., Tyrer, M. Precipitation of heavy metals
from wastewater using simulated flue gas: Sequent additions of fly ash, lime
and carbon dioxide. Water Res. 2009, 43, 2605-14.

[84] Özverdi, A., Erdem, M. Cu2+, Cd2+ and Pb2+ adsorption from aqueous
solutions by pyrite and synthetic iron sulphide. J. Hazard. Mater. 2006, 137,
626-32.

[85] Alyüz, B., Veli, S. Kinetics and equilibrium studies for the removal of nickel
and zinc from aqueous solutions by ion exchange resins. J. Hazard. Mater.
2009, 167, 482-8.

[86] Blöcher, C., Dorda, J., Mavrov, V., Chmiel, H., Lazaridis, N.K., Matis, K.A.
Hybrid flotation—membrane filtration process for the removal of heavy metal
ions from wastewater. Water Res. 2003, 37, 4018-26.

[87] Motsi, T., Rowson, N.A., Simmons, M.J.H. Adsorption of heavy metals from
acid mine drainage by natural zeolite. Int. J. Mineral Process. 2009, 92, 42-8.

112
 References

[88] Erdem, M., Ucar, S., Karagoz, S., Tay, T. Removal of lead (II) ions from
aqueous solutions onto activated carbon derived from waste biomass.
Scientific World J. 2013, 146092.

[89] Guo, M., Qiu, G., Song, W. Poultry litter-based activated carbon for removing
heavy metal ions in water. Waste Manag. 2010, 30, 308-15.

[90] Jusoh, A., Su Shiung, L., Ali, N.a., Noor, M.J.M.M. A simulation study of the
removal efficiency of granular activated carbon on cadmium and lead. Desal.
2007, 206, 9-16.

[91] Mavros, P., Daniilidou, A.C., Lazaridis, N.K., Stergiou, L. Colour removal
from aqueous solutions. Part I. Flotation. Environ. Technol. 1994, 15, 601-16.

[92] McIntyre, G., Rodriguez, J.J., Thackston, E.L., Wilson, D.J. Inexpensive
heavy metal removal by foam flotation. Res. J. Water Pollut. C. 1983, 1144-9.

[93] Zouboulis, A., Matis, K. Removal of metal ions from dilute solutions by
sorptive flotation. Crit. Rev. Environ. Sci. Technol. 1997, 27, 195-235.

[94] Tan, B.H., Teng, T.T., Omar, A.K.M. Removal of dyes and industrial dye
wastes by magnesium chloride. Water Res. 2000, 34, 597-601.

[95] Johnson, P.D., Girinathannair, P., Ohlinger, K.N., Ritchie, S., Teuber, L.,
Kirby, J. Enhanced removal of heavy metals in primary treatment using
coagulation and flocculation. Water Environ. Res. 2008, 80, 472-9.

[96] Esplugas, S., Giménez, J., Contreras, S., Pascual, E., Rodrı́guez, M.
Comparison of different advanced oxidation processes for phenol degradation.
Water Res. 2002, 36, 1034-42.

[97] Kurniawan, T.A., Chan, G.Y.S., Lo, W.-H., Babel, S. Physico–chemical

treatment techniques for wastewater laden with heavy metals. Chem. Eng. J.
2006, 118, 83-98.

[98] Da̧browski, A., Hubicki, Z., Podkościelny, P., Robens, E. Selective removal of
the heavy metal ions from waters and industrial wastewaters by ion-exchange
method. Chemosphere. 2004, 56, 91-106.

[99] Keerthi, Vinduja, V., Balasubramanian, N. Removal of heavy metals by

hybrid electrocoagulation and microfiltration processes. Environ. Technol.
2013, 34, 2897-902.

[100] Barakat, M.A. New trends in removing heavy metals from industrial
wastewater. Arab. J. Chem. 2011, 4, 361-77.

113
 References

[101] Ding, Y., Jing, D., Gong, H., Zhou, L., Yang, X. Biosorption of aquatic
cadmium(II) by unmodified rice straw. Bioresour. Technol. 2012, 114, 20-5.

[102] Witek-Krowiak, A., Szafran, R.G., Modelski, S. Biosorption of heavy metals

from aqueous solutions onto peanut shell as a low-cost biosorbent. Desal.
2011, 265, 126-34.

[103] Hegazi, H.A. Removal of heavy metals from wastewater using agricultural
and industrial wastes as adsorbents. HBRC Journal. 2013, 9, 276-82.

[104] Ravikumar, K., Deebika, B., Balu, K. Decolourization of aqueous dye

solutions by a novel adsorbent: Application of statistical designs and surface
plots for the optimization and regression analysis. J. Hazard. Mater. 2005,
122, 75-83.

[105] Mittal, A., Krishnan, L., Gupta, V.K. Removal and recovery of malachite
green from wastewater using an agricultural waste material, de-oiled soya.
Sep. Purif. Technol. 2005, 43, 125-33.

[106] Wang, H., Kang, J., Liu, H., Qu, J. Preparation of organically functionalized
silica gel as adsorbent for copper ion adsorption. J. Environ. Sci. (China).
2009, 21, 1473-9.

[107] Bowe, C.A., Poore, D.D., Benson, R.F., Martin, D.F. Extraction of heavy
metals by amines adsorbed onto silica gel. J. Environ. Sci. Health A Tox.
Hazard. Subst. Environ. Eng. 2003, 38, 2653-60.

[108] Bowe, C.A., Benson, R.F., Martin, D.F. Extraction of heavy metals by
mercaptans attached to silica gel by a corkscrew mechanism. J. Environ. Sci.
Health A Tox. Hazard. Subst. Environ. Eng. 2002, 37, 1391-1398.

[109] Naiya, T.K., Bhattacharya, A.K., Das, S.K. Adsorption of Cd(II) and Pb(II)
from aqueous solutions on activated alumina. J. Colloid Interf. Sci. 2009, 333,
14-26.

[110] Mahmoud, M.E., Osman, M.M., Hafez, O.F., Hegazi, A.H., Elmelegy, E.
Removal and preconcentration of lead (II) and other heavy metals from water
by alumina adsorbents developed by surface-adsorbed-dithizone. Desal. 2010,
251, 123-30.

[111] Wang, S., Peng, Y. Natural zeolites as effective adsorbents in water and
wastewater treatment. Chem. Eng. J. 2010, 156, 11-24.

[112] Erdem, E., Karapinar, N., Donat, R. The removal of heavy metal cations by
natural zeolites. J. Colloid Interf. Sci. 2004, 280, 309-14.

114
 References

[113] Ackley, M.W., Rege, S.U., Saxena, H. Application of natural zeolites in the
purification and separation of gases. Micropor. Mesopor. Mater. 2003, 61, 25-
42.

[114] Alslaibi, T.M., Abustan, I., Ahmad, M.A., Foul, A.A. Kinetics and equilibrium
adsorption of iron (II), lead (II), and copper (II) onto activated carbon prepared
from olive stone waste. Desal. Water Treat. 2013, 1-11.

[115] Figueiredo, J., Pereira, M., Freitas, M., Orfao, J. Modification of the surface
chemistry of activated carbons. Carbon. 1999, 37, 1379 - 89.

[116] Han, Y., Quan, X., Chen, S., Zhao, H., Cui, C., Zhao, Y. Electrochemically
enhanced adsorption of aniline on activated carbon fibers. Sep. Purif. Technol.
2006, 50, 365 - 72.

[117] Kumar, A., Prasad, B., Mishra, I.M. Adsorptive removal of acrylonitrile by
commercial grade activated carbon: Kinetics, equilibrium and
thermodynamics. J. Hazard. Mater. 2008, 152, 589-600.

[118] Ajmal, M., Ali Khan Rao, R., Anwar, S., Ahmad, J., Ahmad, R. Adsorption
studies on rice husk: removal and recovery of Cd(II) from wastewater.
Bioresour. Technol. 2003, 86, 147-9.

[119] Gupta, A., Chauhan, V.S., Sankararamakrishnan, N. Preparation and

evaluation of iron–chitosan composites for removal of As(III) and As(V) from
arsenic contaminated real life groundwater. Water Res. 2009, 43, 3862-70.

[120] Abdel Salam, O.E., Reiad, N.A., ElShafei, M.M. A study of the removal
characteristics of heavy metals from wastewater by low-cost adsorbents. J.
Adv. Res. 2011, 2, 297-303.

[121] Say, R., Yılmaz, N., Denizli, A. Biosorption of Cadmium, Lead, Mercury, and
Arsenic Ions by the Fungus Penicillium purpurogenum. Sep. Sci. Technol.
2003, 38, 2039-53.

[122] Torosyan, G., Matevosyan, G., Harutyunyan, S. Use of Natural Materials for
Wastewater Treatment & Improvement of Water Quality. In: Advanced Water
Supply and Wastewater Treatment: A Road to Safer Society and Environment,
Springer Netherlands, 2011, 171-80.

[123] Luo, F., Liu, Y., Li, X., Xuan, Z., Ma, J. Biosorption of lead ion by
chemically-modified biomass of marine brown algae Laminaria japonica.
Chemosphere. 2006, 64, 1122-7.

115
 References

[124] Kadirvelu, K., Faur-Brasquet, C., Cloirec, P.L. Removal of Cu(II), Pb(II), and
Ni(II) by Adsorption onto Activated Carbon Cloths. Langmuir. 2000, 16,
8404-9.

[125] Reddad, Z., Gerente, C., Andres, Y., Le Cloirec, P. Adsorption of Several
Metal Ions onto a Low-Cost Biosorbent:  Kinetic and Equilibrium Studies.
Environ. Sci. Technol. 2002, 36, 2067-73.

[126] Lee, S.-J., Lee, M.-E., Chung, J.W., Park, J.H., Huh, K.Y., Jun, G.-I.
Immobilization of Lead from Pb-Contaminated Soil Amended with Peat Moss.
Journal of Chemistry. 2013, 2013, 6.

[127] Prasad, M.N.V., Freitas, H. Removal of toxic metals from solution by leaf,
stem and root phytomass of Quercus ilex L. (holly oak). Environ. Pollut. 2000,
110, 277-83.

[128] Sousa, F., Sousa, M., Isadora, R., Oliveira, I., Oliveira, A., Cavalcante, R., et
al. Evaluation of a low-cost adsorbent for removal of toxic metal ions from
wastewater of an electroplating factory. J. Environ. Manag. 2009, 90, 3340 -
4.

[129] Verma, K.V.R., Swaminathan, T., Subrahmanyam, P.V.R. Heavy metal

removal with lignin. J. Environ. Sci. Health A Environ. Sci. Eng. Toxicol.
1990, 25, 243-65.

[130] Mohan, D., Pittman Jr, C.U., Steele, P.H. Single, binary and multi-component
adsorption of copper and cadmium from aqueous solutions on Kraft lignin—a
biosorbent. J. Colloid Interf. Sci. 2006, 297, 489-504.

[131] Minamisawa, M., Minamisawa, H., Yoshida, S., Takai, N. Adsorption

behavior of heavy metals on biomaterials. J. Agric. Food Chem. 2004, 52,
5606-11.

[132] Anoop Krishnan, K., Anirudhan, T.S. Removal of mercury(II) from aqueous
solutions and chlor-alkali industry effluent by steam activated and sulphurised
activated carbons prepared from bagasse pith: kinetics and equilibrium studies.
J. Hazard. Mater. 2002, 92, 161-83.

[133] Farinella, N.V., Matos, G.D., Lehmann, E.L., Arruda, M.A. Grape bagasse as
an alternative natural adsorbent of cadmium and lead for effluent treatment. J.
Hazard. Mater. 2008, 154, 1007-12.

[134] Farooq, U., Kozinski, J.A., Khan, M.A., Athar, M. Biosorption of heavy metal
ions using wheat based biosorbents – A review of the recent literature.
Bioresour. Technol. 2010, 101, 5043-53.

116
 References

[135] Alonso, D.M., Wettstein, S.G., Dumesic, J.A. Bimetallic catalysts for
upgrading of biomass to fuels and chemicals. Chem. Soc. Rev. 2012, 41, 8075-
98.

[136] Annadural, G., Juang, R.S., Lee, D.J. Adsorption of heavy metals from water
using banana and orange peels. Water Sci. Technol. 2003, 47, 185-90.

[137] Lü, L., Lu, D., Chen, L., Luo, F. Removal of Cd(II) by modified lawny grass
cellulose adsorbent. Desal. 2010, 259, 120-30.

[138] Mahajan, G., Sud, D. Modified agricultural waste biomass with enhanced
responsive properties for metal-ion remediation: a green approach. Appl.
Water Sci. 2012, 2, 299-308.

[139] Demirbas, A. Adsorption of lead and cadmium ions in aqueous solutions onto
modified lignin from alkali glycerol delignication. J. Hazard. Mater. 2004,
109, 221-6.

[140] Ofomaja, A.E., Ho, Y.S. Effect of pH on cadmium biosorption by coconut

copra meal. J. Hazard. Mater. 2007, 139, 356-62.

[141] Mohee, R., Mudhoo, A. Bioremediation and Sustainability: Research and

Applications, John Wiley & Sons, 2012.

[142] Basso, M.C., Cerrella, E.G., Cukierman, A.L. Lignocellulosic Materials as

Potential Biosorbents of Trace Toxic Metals from Wastewater. Indust. Eng.
Chem. Res. 2002, 41, 3580-5.

[143] Erdtman, H. Lignins: Occurrence, formation, structure and reactions, K. V.

Sarkanen and C. H. Ludwig, Eds., John Wiley & Sons, Inc., New York, J.
Polym. Sci. B: Polymer Lett. 1972, 10, 228-30.

[144] Sag, Y., Kutsal, T. Recent trends in the biosorption of heavy metals: A review.
Biotechnol. Biopro. Eng. 2001, 6, 376-85.

[145] Tarley, C.R., Arruda, M.A. Biosorption of heavy metals using rice milling by-
products. Characterisation and application for removal of metals from aqueous
effluents. Chemosphere. 2004, 54, 987-95.

[146] Abia, A.A., Horsfall, M., Jr., Didi, O. The use of chemically modified and
unmodified cassava waste for the removal of Cd, Cu and Zn ions from
aqueous solution. Bioresour. Technol. 2003, 90, 345-8.

[147] Amuda, O.S., Giwa, A.A., Bello, I.A. Removal of heavy metal from industrial
wastewater using modified activated coconut shell carbon. Biochem. Eng. J.
2007, 36, 174-81.

117
 References

[148] Chen, L., Lü, L., Shao, W., Luo, F. Kinetics and Equilibria of Cd(II)
Adsorption onto a Chemically Modified Lawny Grass with H[BTMPP]. J.
Chem. Eng. Data. 2011, 56, 1059-68.

[149] Dada, A., Ojediran, J., Olalekan, A.P. Sorption of from Aqueous Solution unto
Modified Rice Husk: Isotherms Studies. Adv. Phys. Chem. 2013, Article ID
842425.

[150] Feng, N., Guo, X., Liang, S., Zhu, Y., Liu, J. Biosorption of heavy metals
from aqueous solutions by chemically modified orange peel. J. Hazard. Mater.
2011, 185, 49-54.

[151] Kim, S.-H., Song, H., Nisola, G.M., Ahn, J., Galera, M.M., hee Lee, C., et al.
Adsorption of lead (II) ions using surface-modified chitins. J. Indus. Eng.
Chem. 2006, 12, 469-75.

[152] Jiang, Y., Pang, H., Liao, B. Removal of copper(II) ions from aqueous
solution by modified bagasse. J. Hazard. Mater. 2009, 164, 1-9.

[153] Lu, D., Cao, Q., Cao, X., Luo, F. Removal of Pb(II) using the modified lawny
grass: mechanism, kinetics, equilibrium and thermodynamic studies. J.
Hazard. Mater. 2009, 166, 239-47.

[154] Okieimen, F.E., Okundia, E.U., Ogbeifun, D.E. Sorption of cadmium and lead
ions on modified groundnut (Arachis hypogea) husks. J. Chem. Technol.
Biotechnol. 1991, 51, 97-103.

[155] Reddy, D., Harinath, Y., Seshaiah, K., Reddy, A. Biosorption of Pb(II) from
aqueous solutions using chemically modified Moringa oleifera tree leaves.
Chem. Eng. J. 2010, 162, 626 - 34.

[156] Vaughan, T., Seo, C.W., Marshall, W.E. Removal of selected metal ions from
aqueous solution using modified corncobs. Bioresour. Technol. 2001, 78, 133-
9.

[157] Wong, K.K., Lee, C.K., Low, K.S., Haron, M.J. Removal of Cu and Pb by
tartaric acid modified rice husk from aqueous solutions. Chemosphere. 2003,
50, 23-8.

[158] Kumar, U., Bandyopadhyay, M. Sorption of cadmium from aqueous solution

using pretreated rice husk. Bioresour. Technol. 2006, 97, 104-9.

[159] Nasir, M.H., Nadeem, R., Akhtar, K., Hanif, M.A., Khalid, A.M. Efficacy of
modified distillation sludge of rose (Rosa centifolia) petals for lead(II) and
zinc(II) removal from aqueous solutions. J. Hazard. Mater. 2007, 147, 1006-
14.
118
 References

[160] Tan, G., Yuan, H., Liu, Y., Xiao, D. Removal of lead from aqueous solution
with native and chemically modified corncobs. J. Hazard. Mater. 2010, 174,
740-5.

[161] Ioannidou, O., Zabaniotou, A. Agricultural residues as precursors for activated

carbon production—A review. Renew. Sust. Energy Rev. 2007, 11, 1966-2005.

[162] Suresh, S., Srivastava, V.C., Mishra, I. M. Adsorption of catechol, resorcinol,

hydroquinone, and their derivatives: a review. Int. J. Energy Environ. Eng.
2012, 3, 32.

[163] Pradhan, S. Production and characterization of Activated Carbon produced

from a suitable Industrial sludge 2011.

[164] Morita, M., Higuchi, M., Sakata, I. Binding of heavy metal ions by chemically
modified woods. J. App. Poly. Sci. 1987, 34, 1013-23.

[165] Karnitz Jr, O., Gurgel, L.V.A., de Melo, J.C.P., Botaro, V.R., Melo, T.M.S.,
de Freitas Gil, R.P., et al. Adsorption of heavy metal ion from aqueous single
metal solution by chemically modified sugarcane bagasse. Bioresour. Technol.
2007, 98, 1291-7.

[166] Leon-Gonzalez, M., Perez-Arribas, L. Chemically modified polymeric

sorbents for sample preconcentration. J. Chromatogr. A. 2003, 902, 3 - 16.

[167] Boudrahem, F., Aissani-Benissad, F., Aït-Amar, H. Batch sorption dynamics

and equilibrium for the removal of lead ions from aqueous phase using
activated carbon developed from coffee residue activated with zinc chloride. J.
Environ. Manag. 2009, 90, 3031-9.

[168] Akar, T., Tunali, S. Biosorption characteristics of Aspergillus flavus biomass

for removal of Pb(II) and Cu(II) ions from an aqueous solution. Bioresour.
Technol. 2006, 97, 1780-7.

[169] Kiran, I., Akar, T., Tunali, S. Biosorption of Pb(II) and Cu(II) from aqueous
solutions by pretreated biomass of Neurospora crassa. Process Biochem. 2005,
40, 3550-8.

[170] Lodeiro, P., Herrero, R., Sastre de Vicente, M.E. Thermodynamic and Kinetic
Aspects on the Biosorption of Cadmium by Low Cost Materials: A Review.
Environ. Chem. 2006, 3, 400-18.

[171] Anwar, J., Shafique, U., Waheed uz, Z., Salman, M., Dar, A., Anwar, S.
Removal of Pb(II) and Cd(II) from water by adsorption on peels of banana.
Bioresour. Technol. 2010, 101, 1752-5.

119
 References

[172] Oladoja, N., Aboluwoye, C., Oladimeji, Y. Kinetics and isotherm studies on
methylene blue adsorption onto ground palm kernel coat. Turkish J. Eng. Env.
Sci. 2008, 32, 303-12.

[173] Bharathi, K.S., Ramesh, S.T. Removal of dyes using agricultural waste as low-
cost adsorbents: a review. Appl. Water Sci. 2013, 3, 773-90.

[174] Freundlish, H. Over the adsorption in solution. J. Phys. Chem. B. 1906, 57,
385-470.

[175] Langmuir, I. The constitution and fundamental properties of solids and liquids.
Am. Chem. Soc., 1916, 38, 2221-2295

[176] El Harti, M., Hannache, H., Khouya, E., Oumam, M., Fakhi, S., Djafari, D., et
al. Removal of lead (II) by adsorption onto moroccan oil shale of timahdit:
Effect of pH, contact time and equilibrium isotherm analyses. Der. Pharmacia
Lett. 2013, 5, 132-9.

[177] Shahbeig, H., Bagheri, N., Ghorbanian, S.A., Hallajisani, A., Poorkarimi, S. A
new adsorption isotherm model of aqueous solutions on granular activated
carbon. World J. Modell. Simulat. 2013, 9, 243-54.

[178] Lyubchik, S., Lyubchik, A., Lygina, O., Lyubchik, S., Fonseca, I. Comparison
of the thermodynamic parameters estimation for the adsorption process of the
metals from liquid phase on activated carbons. 2011.

[179] Crini, G., Badot, P.-M. Sorption processes and pollution: Conventional and
non-conventional sorbents for pollutant removal from wastemasters, Presses
Univ. Franche-Comté, 2010.

[180] Aksu, Z., AÇIkel, U., Kutsal, T. Investigation of Simultaneous Biosorption of

Copper(II) and Chromium(VI) on Dried Chlorella Vulgaris from Binary Metal
Mixtures: Application of Multicomponent Adsorption Isotherms. Sep. Sci.
Technol. 1999, 34, 501-24.

[181] Burks, T., Avila, M., Akhtar, F., Gothelid, M., Lansaker, P.C., Toprak, M.S.,
et al. Studies on the adsorption of chromium(VI) onto 3-Mercaptopropionic
acid coated superparamagnetic iron oxide nanoparticles. J. Colloid Interf. Sci.
2014, 425, 36-43.

[182] Tofighy, M.A., Mohammadi, T. Adsorption of divalent heavy metal ions from
water using carbon nanotube sheets. J. Hazard. Mater. 2011, 185, 140-7.

[183] Li, Y., Du, Q., Wang, X., Zhang, P., Wang, D., Wang, Z., et al. Removal of
lead from aqueous solution by activated carbon prepared from Enteromorpha
prolifera by zinc chloride activation. J. Hazard. Mater. 2010, 183, 583-9.

120
 References

[184] Boparai, H.K., Joseph, M., O'Carroll, D.M. Kinetics and thermodynamics of
cadmium ion removal by adsorption onto nano zerovalent iron particles. J.
Hazard. Mater. 2011, 186, 458-65.

[185] Sari, A., Tuzen, M. Kinetic and equilibrium studies of biosorption of Pb(II)
and Cd(II) from aqueous solution by macrofungus (Amanita rubescens)
biomass. J. Hazard. Mater. 2009, 164, 1004-11.

[186] Ozdes, D., Duran, C., Senturk, H.B. Adsorptive removal of Cd(II) and Pb(II)
ions from aqueous solutions by using Turkish illitic clay. J. Environ. Manag.
2011, 92, 3082-90.

[187] Singh, K.K., Rastogi, R., Hasan, S.H. Removal of cadmium from wastewater
using agricultural waste ‘rice polish’. J. Hazard. Mater. 2005, 121, 51-8.

[188] Benguella, B., Benaissa, H. Cadmium removal from aqueous solutions by

chitin: kinetic and equilibrium studies. Water Res. 2002, 36, 2463-74.

[189] Memon, S.Q., Memon, N., Shah, S.W., Khuhawar, M.Y., Bhanger, M.I.
Sawdust—A green and economical sorbent for the removal of cadmium (II)
ions. J. Hazard. Mater. 2007, 139, 116-21.

[190] 90] Bulut, Y., Tez, Z. Removal of heavy metals from aqueous solution by
sawdust adsorption. J. Environ. Sci. 2007, 19, 160-6.

[191] Huang, X., Gao, N.-y., Zhang, Q.-l. Thermodynamics and kinetics of cadmium
adsorption onto oxidized granular activated carbon. J. Environ. Sci. (China).
2007, 19, 1287-92.

[192] Bhattacharyya, K.G., Sharma, A. Adsorption of Pb(II) from aqueous solution

by Azadirachta indica (Neem) leaf powder. J. Hazard. Mater. 2004, 113, 97-
109.

[193] Febriana, N., Lesmana, S.O., Soetaredjo, F.E., Sunarso, J., Ismadji, S. Neem
leaf utilization for copper ions removal from aqueous solution. J. Taiwan Inst.
Chem. Eng. 2010, 41, 111-4.

[194] Farhan, A., Al-Dujaili, A., Awwad, A. Equilibrium and kinetic studies of
cadmium(II) and lead(II) ions biosorption onto Ficus carcia leaves. Int. J.
Indus. Chem. 2013, 4, 24.

[195] Saeed, A., Iqbal, M., Akhtar, M.W. Removal and recovery of lead(II) from
single and multimetal (Cd, Cu, Ni, Zn) solutions by crop milling waste (black
gram husk). J. Hazard. Mater. 2005, 117, 65-73.

121
 References

[196] Asrari, E., Tavallali, H., Hagshenas, M. Removal of Zn(II) and Pb(II) ions
using rice husk in food industrial wastewater. J. App. Sci. Manag. 2010, 14,
159 - 62.

[197] Feng, Q., Lin, Q., Gong, F., Sugita, S., Shoya, M. Adsorption of lead and
mercury by rice husk ash. J. Colloid Interf. Sci. 2004, 278, 1-8.

[198] Naiya, T.K., Bhattacharya, A.K., Mandal, S., Das, S.K. The sorption of
lead(II) ions on rice husk ash. J. Hazard. Mater. 2009, 163, 1254-64.

[199] Boudrahem, F., Aissani-Benissad, F., Ait-Amar, H. Batch sorption dynamics

and equilibrium for the removal of lead ions from aqueous phase using
activated carbon developed from coffee residue activated with zinc chloride. J
Environ Manage. 2009, 90, 3031-9.

[200] Lugo-Lugo, V., Hernandez-Lopez, S., Barrera-Diaz, C., Urena-Nunez, F.,

Bilyeu, B. A comparative study of natural, formaldehyde-treated and
copolymer-grated orange peel for Pb(II) adsorption under batch and
continuous mode. J. Hazard. Mater. 2009, 161, 1255-64.

[201] Yin, C., Aroua, M., Daud, W. Enhanced Adsorption of Metal Ions Onto
Polyethyleneimine-Impregnated Palm Shell Activated Carbon: Equilibrium
Studies. Water Air Soil Pollut. 2008, 192, 337-48.

[202] Chamarthy, S., Seo, C.W., Marshall, W.E. Adsorption of selected toxic metals
by modified peanut shells. J. Chem. Technol. Biotechnol. 2001, 76, 593-7.

[203] El-Ashtoukhy, E.S.Z., Amin, N.K., Abdelwahab, O. Removal of lead (II) and
copper (II) from aqueous solution using pomegranate peel as a new adsorbent.
Desal. 2008, 223, 162-73.

[204] Özer, A. Removal of Pb(II) ions from aqueous solutions by sulphuric acid-
treated wheat bran. J. Hazard. Mater. 2007, 141, 753-61.

[205] Kumar, U., Bandyopadhyay, M. Fixed bed column study for Cd(II) removal
from wastewater using treated rice husk. J. Hazard. Mater. 2006, 129, 253-9.

[206] Babarinde, N. Kinetic, equilibrium and thermodynamic of the biosorption of

Pb(II), Cd(II) and Cr(III) by neem leaf. J. Innovative Res. Eng. Sci. 2011, 2,
291 - 306.

[207] Babarinde, N., Babalola, J., Sanni, S. Isotherm and thermodynamic studies of
the biosorption of Cd(II) from solution by maize leaf. Int. J. Phys. Sci. 2007,
2, 207 - 11.

122
 References

[208] Barka, N., Abdennouri, M., Boussaoud, A., El Makhfouk, M. Biosorption

characteristics of cadmium(II) onto Scolymus hispanicus L. as low-cost
natural biosorbent. Desal. 2010, 258, 66 - 71.

[209] Leyva-Ramos, R., Bernal-Jacome, L.A., Acosta-Rodriguez, I. Adsorption of

cadmium(II) from aqueous solution on natural and oxidized corncob. Sep.
Purif. Technol. 2005, 45, 41-9.

[210] Min, S.H., Han, J.S., Shin, E.W., Park, J.K. Improvement of cadmium ion
removal by base treatment of juniper fiber. Water Res. 2004, 38, 1289-95.

[211] Gurgel, L.V.A., Gil, L.F. Adsorption of Cu(II), Cd(II) and Pb(II) from
aqueous single metal solutions by succinylated twice-mercerized sugarcane
bagasse functionalized with triethylenetetramine. Water Res. 2009, 43, 4479-
88.

[212] Özer, A., Pirinççi, H.B. The adsorption of Cd(II) ions on sulphuric acid-
treated wheat bran. J. Hazard. Mater. 2006, 137, 849-55.

[213] Jalali, R., Ghafourian, H., Asef, Y., Davarpanah, S.J., Sepehr, S. Removal and
recovery of lead using nonliving biomass of marine algae. J. Hazard. Mater.
2002, 92, 253-62.

[214] Yan, G., Viraraghavan, T. Heavy-metal removal from aqueous solution by

fungus Mucor rouxii. Water Res. 2003, 37, 4486-96.

[215] Wilson, J., Pulford, I., Thomas, S. Adsorption of heavy metals by natural
charcoal (bone charcoal): its potential as a water treatment cleanup. In:
Breeding of the 11th Annual International Conference on Heavy Metals in the
Environment, Contribution, 2000.

[216] Lalhruaitluanga, H., Jayaram, K., Prasad, M.N.V., Kumar, K.K. Lead(II)
adsorption from aqueous solutions by raw and activated charcoals of
Melocanna baccifera Roxburgh (bamboo)—A comparative study. J. Hazard.
Mater. 2010, 175, 311-8.

[217] Goel, J., Kadirvelu, K., Rajagopal, C., Garg, V.K. Removal of Lead(II) from
Aqueous Solution by Adsorption on Carbon Aerogel Using a Response
Surface Methodological Approach. Indust. Eng. Chem. Res. 2005, 44, 1987-
94.

[218] Boudrahem, F., Aissani-Benissad, F., Aït-Amar, H. Batch sorption dynamics

and equilibrium for the removal of lead ions from aqueous phase using
activated carbon developed from coffee residue activated with zinc chloride. J.
Environ. Manag. 2009, 90, 3031-9.

123
 References

[219] Conrad, K., Bruun Hansen, H.C. Sorption of zinc and lead on coir. Bioresour.
Technol. 2007, 98, 89-97.

[220] Gupta, V.K., Ali, I. Removal of lead and chromium from wastewater using
bagasse fly ash—a sugar industry waste. J. Colloid Interf. Sci. 2004, 271, 321-
8.

[221] Patnukao, P., Kongsuwan, A., Pavasant, P. Batch studies of adsorption of

copper and lead on activated carbon from Eucalyptus camaldulensis dehn.
bark. J. Environ. Sci. (China). 2008, 20, 1028-34.

[222] Martínez, M., Miralles, N., Hidalgo, S., Fiol, N., Villaescusa, I., Poch, J.
Removal of lead(II) and cadmium(II) from aqueous solutions using grape stalk
waste. J. Hazard. Mater. 2006, 133, 203-11.

[223] Pehlivan, E., Altun, T., Cetin, S., Iqbal Bhanger, M. Lead sorption by waste
biomass of hazelnut and almond shell. J. Hazard. Mater. 2009, 167, 1203-8.

[224] Yu, B., Zhang, Y., Shukla, A., Shukla, S.S., Dorris, K.L. The removal of
heavy metals from aqueous solutions by sawdust adsorption--removal of lead
and comparison of its adsorption with copper. J. Hazard. Mater. 2001, 84, 83-
94.

[225] Taty-Costodes, V.C., Fauduet, H., Porte, C., Delacroix, A. Removal of Cd(II)
and Pb(II) ions, from aqueous solutions, by adsorption onto sawdust of Pinus
sylvestris. J. Hazard. Mater. 2003, 105, 121-42.

[226] Iqbal, M., Saeed, A., Zafar, S.I. FTIR spectrophotometry, kinetics and
adsorption isotherms modeling, ion exchange, and EDX analysis for
understanding the mechanism of Cd2+ and Pb2+ removal by mango peel waste.
J. Hazard. Mater. 2009, 164, 161-71.

[227] El-Ashtoukhy, E.S.Z., Amin, N.K., Abdelwahab, O. Removal of lead (II) and
copper (II) from aqueous solution using pomegranate peel as a new adsorbent.
Desal. 2008, 223, 162-73.

[228] Pavan, F.A., Mazzocato, A.C., Jacques, R.A., Dias, S.L.P. Ponkan peel: A
potential biosorbent for removal of Pb(II) ions from aqueous solution.
Biochem. Eng. J. 2008, 40, 357-62.

[229] Xu, T., Liu, X. Peanut Shell Activated Carbon: Characterization, Surface
Modification and Adsorption of Pb2+ from Aqueous Solution. Chinese J.
Chem. Eng. 2008, 16, 401-6.

124
 References

[230] Issabayeva, G., Aroua, M.K., Sulaiman, N.M.N. Removal of lead from
aqueous solutions on palm shell activated carbon. Bioresour. Technol. 2006,
97, 2350-5.

[231] Zulkali, M.M.D., Ahmad, A.L., Norulakmal, N.H., Sharifah, N.S.

Comparative studies of Oryza sativa L. husk and chitosan as lead adsorbent. J.
Chem. Technol. Biotechnol. 2006, 81, 1324-7.

[232] Zhang, Y., Banks, C. A comparison of the properties of polyurethane

immobilised Sphagnum moss, seaweed, sunflower waste and maize for the
biosorption of Cu, Pb, Zn and Ni in continuous flow packed columns. Water
Res. 2006, 40, 788-98.

[233] Ho, Y.-S. Effect of pH on lead removal from water using tree fern as the
sorbent. Bioresour. Technol. 2005, 96, 1292-6.

[234] Herrero, R., Lodeiro, P., Rojo, R., Ciorba, A., Rodríguez, P., Sastre de
Vicente, M.E. The efficiency of the red alga Mastocarpus stellatus for
remediation of cadmium pollution. Bioresour. Technol. 2008, 99, 4138-46.

[235] Liu, Y.G., Fan, T., Zeng, G.M., Li, X., Tong, Q., Ye, F., et al. Removal of
cadmium and zinc ions from aqueous solution by living Aspergillus niger.
Trans. Nonferrous Met. Soc. China. 2006, 16, 681-6.

[236] Lodeiro, P., Cordero, B., Barriada, J.L., Herrero, R., Sastre de Vicente, M.E.
Biosorption of cadmium by biomass of brown marine macroalgae. Bioresour.
Technol. 2005, 96, 1796-803.

[237] Davila-Rangel, J.I., Solache-Ríos, M., Badillo-Almaraz, V.E. Comparison of

three Mexican aluminosilicates for the sorption of cadmium. J. Radioanal.
Nucl. Chem. 2005, 267, 139-45.

[238] Memon, J.R., Memon, S.Q., Bhanger, M.I., Memon, G.Z., El-Turki, A., Allen,
G.C. Characterization of banana peel by scanning electron microscopy and
FT-IR spectroscopy and its use for cadmium removal. Colloids Surf. B. 2008,
66, 260-5.

[239] Mohammed, R. Removal of Heavy Metals from Waste Water Using Black
Teawaste. Arab. J. Sci. Eng. 2012, 37, 1505-20.

[240] Yavuz, O., Guzel, R., Aydin, F., Tegin, I., Ziyadanogullari, R. Removal of
cadmium and lead from aqueous solution by calcite. Pol. J. Environ. Stud.
2007, 16, 467.

125
 References

[241] Anirudhan, T.S., Rijith, S., Divya, L. Preparation and Application of a Novel
Functionalized Coconut Coir Pith as a Recyclable Adsorbent for Phosphate
Removal. Sep. Sci. Technol. 2009, 44, 2774-96.

[242] Anirudhan, T.S., Divya, L., Rijith, S. Adsorption characteristics of

cadmium(II) onto functionalized poly(hydroxyethylmethacrylate)-grafted
coconut coir pith. Bull. Environ. Contamin. Toxicol. 2010, 85, 42-7.

[243] Shen, J., Duvnjak, Z. Adsorption kinetics of cupric and cadmium ions on
corncob particles. Process Biochem. 2005, 40, 3446-54.

[244] Ghodbane, I., Nouri, L., Hamdaoui, O., Chiha, M. Kinetic and equilibrium
study for the sorption of cadmium(II) ions from aqueous phase by eucalyptus
bark. J. Hazard. Mater. 2008, 152, 148-58.

[245] Meunier, N., Laroulandie, J., Blais, J.F., Tyagi, R.D. Cocoa shells for heavy
metal removal from acidic solutions. Bioresour. Technol. 2003, 90, 255-63.

[246] Inbaraj, B.S., Sulochana, N. Carbonised jackfruit peel as an adsorbent for the
removal of Cd(II) from aqueous solution. Bioresour. Technol. 2004, 94, 49-52.

[247] Brown, P., Atly Jefcoat, I., Parrish, D., Gill, S., Graham, E. Evaluation of the
adsorptive capacity of peanut hull pellets for heavy metals in solution. Adv.
Environ. Res. 2000, 4, 19-29.

[248] Hanzlik, P., Jehlicka, J., Weishauptova, Z., Sebek, O. Adsorption of copper,
cadmium and silver from aqueous solutions onto natural carbonaceous
materials. Plants Soil Environ. 2004, 50, 257-64.

[249] Wan, S., Ma, Z., Xue, Y., Ma, M., Xu, S., Qian, L., et al. Sorption of Lead(II),
Cadmium(II), and Copper(II) Ions from Aqueous Solutions Using Tea Waste.
Indus. Eng. Chem. Res. 2014, 53, 3629-35.

[250] Rao, K., Anand, S., Venkateswarlu, P. Cadmium removal from aqueous
solutions using biosorbent Syzygium cumini leaf powder: Kinetic and
equilibrium studies. Korean J. Chem. Eng. 2010, 27, 1547-54.

[251] Nouri, L., Ghodbane, I., Hamdaoui, O., Chiha, M. Batch sorption dynamics
and equilibrium for the removal of cadmium ions from aqueous phase using
wheat bran. J. Hazard. Mater. 2007, 149, 115-25.

[252] Singh, K.K., Singh, A.K., Hasan, S.H. Low cost bio-sorbent 'wheat bran' for
the removal of cadmium from wastewater: kinetic and equilibrium studies.
Bioresour. Technol. 2006, 97, 994-1001.

126
 References

[253] Al-Anber, Z.A., Matouq, M.A. Batch adsorption of cadmium ions from
aqueous solution by means of olive cake. J. Hazard. Mater. 2008, 151, 194-
201.

[254] Yao, Z.Y., Qi, J.H., Wang, L.H. Equilibrium, kinetic and thermodynamic
studies on the biosorption of Cu(II) onto chestnut shell. J. Hazard. Mater.
2010, 174, 137-43.

[255] Ghaedi, M., Nasab, A.G., Khodadoust, S., Sahraei, R., Daneshfar, A.
Characterization of zinc oxide nanorods loaded on activated carbon as cheap
and efficient adsorbent for removal of methylene blue. J. Indust. Eng. Chem.
2014.

[256] Djeribi, R., Hamdaoui, O. Sorption of copper(II) from aqueous solutions by

cedar sawdust and crushed brick. Desal. 2008, 225, 95-112.

[257] Khan, A.S.A. Evaluation of thermodynamic parameters of cadmium

adsorption on sand from Temkin adsorption isotherm. Turkish J. Chem. 2012,
36, 437-43.

[258] Chabani, M., Amrane, A., Bensmaili, A. Kinetics of nitrates adsorption on

Amberlite IRA 400 resin. Desal. 2007, 206, 560-7.

[259] Yuh-Shan, H. Citation review of Lagergren kinetic rate equation on adsorption

reactions. Scientometrics. 2004, 59, 171-7.

[260] Salleh, M.A.M., Mahmoud, D.K., Karim, W.A.W.A., Idris, A. Cationic and
anionic dye adsorption by agricultural solid wastes: A comprehensive review.
Desal. 2011, 280, 1-13.

[261] Blazquez, G., Martin-Lara, M., Tenorio, G., Calero, M. Batch biosorption of
lead(II) from aqueous solution by olive tree pruning waste: equilibrium,
kinetics and thermodynamic study. Chem. Eng. J. 2011, 168, 170 - 7.

[262] Gueu, S., Yao, B., Adouby, K., Ado, G. Kinetics and thermodynamics study
of lead adsorption on to activated carbons from coconut and seed hull of the
palm tree. Int. J. Environ. Sci. Technol. 2007, 4, 11-7.

[263] Vázquez, G., González-Álvarez, J., Freire, S., López-Lorenzo, M., Antorrena,
G. Removal of cadmium and mercury ions from aqueous solution by sorption
on treated Pinus pinaster bark: kinetics and isotherms. Bioresour. Technol.
2002, 82, 247-51.

[264] Lagergren, S. About the theory of so-called adsorption of soluble substances.

K. Handlingar PA Norstedt & söner, 1898.

127
 References

[265] Qiu, H., Lv, L., Pan, B.-c., Zhang, Q.-j., Zhang, W.-m., Zhang, Q.-x. Critical
review in adsorption kinetic models. J. Zhejiang University Sci. A. 2009, 10,
716-24.

[266] Ho, Y.S., McKay, G. A Comparison of Chemisorption Kinetic Models

Applied to Pollutant Removal on Various Sorbents. Process Saf. Environ.
Protec. 1998, 76, 332-40.

[267] Chojnacka, K., Chojnacki, A., Gorecka, H. Biosorption of Cr3+, Cd2+ and Cu2+
ions by blue-green algae Spirulina sp.: kinetics, equilibrium and the
mechanism of the process. Chemosphere. 2005, 59, 75-84.

[268] Ho, Y.-S. Review of second-order models for adsorption systems. J. Hazard.
Mater. 2006, 136, 681-9.

[269] Wu, F.-C., Tseng, R.-L., Juang, R.-S. Initial behavior of intraparticle diffusion
model used in the description of adsorption kinetics. Chem. Eng. J. 2009, 153,
1 - 8.

[270] Faust, S.D., Aly, O.M. Chemistry of water treatment, CRC Press, 1998.

[271] Goswami, S., Ghosh, U.C. Studies on adsorption behaviour of Cr (VI) onto
synthetic hydrous stannic oxide. Water SA. 2006, 31, 597-602.

[272] Weber, W., Morris, J. Kinetics of adsorption on carbon from solution. J. Sanit.
Eng. Div. Am. Soc. Civ. Eng. 1963, 89, 31-60.

[273] Pan, X., Wang, J., Zhang, D. Sorption of cobalt to bone char: Kinetics,
competitive sorption and mechanism. Desal. 2009, 249, 609-14.

[274] Deng, L., Su, Y., Su, H., Wang, X., Zhu, X. Sorption and desorption of lead
(II) from wastewater by green algae Cladophora fascicularis. J. Hazard.
Mater. 2007, 143, 220-5.

[275] Madhava Rao, M., Ramesh, A., Purna Chandra Rao, G., Seshaiah, K. Removal
of copper and cadmium from the aqueous solutions by activated carbon
derived from Ceiba pentandra hulls. J. Hazard. Mater. 2006, 129, 123-9.

[276] Kulczycki, E., Ferris, F.G., Fortin, D. Impact of Cell Wall Structure on the
Behavior of Bacterial Cells as Sorbents of Cadmium and Lead. Geomicrobiol.
J. 2002, 19, 553-65.

[277] Kurniawan, T.A., Chan, G.Y.S., Lo, W.-h., Babel, S. Comparisons of low-cost
adsorbents for treating wastewaters laden with heavy metals. Sci. Total
Environ. 2006, 366, 409-26.

128
 References

[278] Saeed, A., Iqbal, M. Bioremoval of cadmium from aqueous solution by black
gram husk (Cicer arientinum). Water Res. 2003, 37, 3472-80.

[279] Olu-owolabi, B., Pputu, O., Adebowale, K., Ogunsolu, O., Olujimi, O.
Biosorption of Cd2+ and Pb2+ ions onto mango stone and cocoa pod waste:
kinetic and equilibrium studies. Sci. Res. Essays. 2012, 7, 1614-29.

[280] Xue, Y., Hou, H., Zhu, S. Competitive adsorption of copper(II), cadmium(II),
lead(II) and zinc(II) onto basic oxygen furnace slag. J. Hazard. Mater. 2009,
162, 391-401.

[281] Miretzky, P., Muñoz, C., Carrillo-Chávez, A. Experimental binding of lead to

a low cost on biosorbent: Nopal (Opuntia streptacantha). Bioresour. Technol.
2008, 99, 1211-7.

[282] Raize, O., Argaman, Y., Yannai, S. Mechanisms of biosorption of different

heavy metals by brown marine macroalgae. Biotechnol. Bioeng. 2004, 87,
451-8.

[283] Chong, H.L., Chia, P.S., Ahmad, M.N. The adsorption of heavy metal by
Bornean oil palm shell and its potential application as constructed wetland
media. Bioresour. Technol. 2013, 130, 181-6.

[284] Pahlavanzadeh, H., Keshtkar, A.R., Safdari, J., Abadi, Z. Biosorption of

nickel(II) from aqueous solution by brown algae: equilibrium, dynamic and
thermodynamic studies. J. Hazard. Mater. 2010, 175, 304-10.

[285] Moyo, M., Chikazaza, L., Nyamunda, B.C., Guyo, U. Adsorption Batch
Studies on the Removal of Pb(II) Using Maize Tassel Based Activated
Carbon. Journal of Chemistry. 2013, 2013, 8.

[286] Ayyappan, R., Sophia, A.C., Swaminathan, K., Sandhya, S. Removal of Pb(II)
from aqueous solution using carbon derived from agricultural wastes. Process
Biochem. 2005, 40, 1293-9.

[287] Abdel-Ghani, N.T., Hefny, M., El-Chaghaby, G.A.F. Removal of lead from
aqueous solution using low cost abundantly available adsorbents. Int. J.
Environ. Sci. Technol. 2007, 4, 67-73.

[288] Kumar, D., Gaur, J.P. Metal biosorption by two cyanobacterial mats in
relation to pH, biomass concentration, pretreatment and reuse. Bioresour.
Technol. 2011, 102, 2529-35.

[289] Abdel-Ghani, N.T., Hegazy, A.K., El-Chaghaby, G.A. Typha domingensis

leaf powder for decontamination of aluminium, iron, zinc and lead:

129
 References

Biosorption kinetics and equilibrium modeling. Int. J. Environ. Sci. Technol.

2009, 6, 243-8.

[290] Lodeiro, P., Herrero, R., Sastre de Vicente, M.E. Batch desorption studies and
multiple sorption-regeneration cycles in a fixed-bed column for Cd(II)
elimination by protonated Sargassum muticum. J. Hazard. Mater. 2006, 137,
1649-55.

[291] ] Lu, W.B., Shi, J.J., Wang, C.H., Chang, J.S. Biosorption of lead, copper and
cadmium by an indigenous isolate Enterobacter sp. J1 possessing high heavy-
metal resistance. J. Hazard. Mater. 2006, 134, 80-6.

[292] Tuzen, M., Uluozlu, O.D., Usta, C., Soylak, M. Biosorption of copper(II),
lead(II), iron(III) and cobalt(II) on Bacillus sphaericus-loaded Diaion SP-850
resin. Anal. Chim. Acta. 2007, 581, 241-6.

[293] Senthilkumar, R., Vijayaraghavan, K., Thilakavathi, M., Iyer, P.V.R., Velan,
M. Application of seaweeds for the removal of lead from aqueous solution.
Biochem. Eng. J. 2007, 33, 211-6.

[294] Arica, M.Y., Bayramoglu, G., Yilmaz, M., Bektas, S., Genc, O. Biosorption of
Hg2+, Cd2+, and Zn2+ by Ca-alginate and immobilized wood-rotting fungus
Funalia trogii. J. Hazard. Mater. 2004, 109, 191-9.

[295] Dushenkov, V., Kumar, P.B., Motto, H., Raskin, I. Rhizofiltration: the use of
plants to remove heavy metals from aqueous streams. Environ. Sci. Technol.
1995, 29, 1239-45.

[296] Martins, R.J.E., Pardo, R., Boaventura, R.A.R. Cadmium(II) and zinc(II)
adsorption by the aquatic moss Fontinalis antipyretica: effect of temperature,
pH and water hardness. Water Res. 2004, 38, 693-9.

[297] Freitas, O.M.M., Martins, R.J.E., Delerue-Matos, C.M., Boaventura, R.A.R.

Removal of Cd(II), Zn(II) and Pb(II) from aqueous solutions by brown marine
macro algae: Kinetic modelling. J. Hazard. Mater. 2008, 153, 493-501.

[298] Kocaoba, S., Akcin, G. Removal of chromium (III) and cadmium (II) from
aqueous solutions. Desalination. 2005, 180, 151-6.

[299] Govindasamy, V., Rengasamy, T., Mahendra Das, D.K. Removal of Cd 2+

ions from aqueous solution using live and dead Bacillus Subtilis 2011.

[300] Starvin, A.M., Rao, T.P. Removal and recovery of mercury(II) from hazardous
wastes using 1-(2-thiazolylazo)-2-naphthol functionalized activated carbon as
solid phase extractant. J. Hazard. Mater. 2004, 113, 75-9.

130
 References

[301] Ng, J.C., Cheung, W.H., McKay, G. Equilibrium studies for the sorption of
lead from effluents using chitosan. Chemosphere. 2003, 52, 1021-30.

[302] Ho, Y.S., Wang, C.C. Pseudo-isotherms for the sorption of cadmium ion onto
tree fern. Process Biochem. 2004, 39, 761-5.

[303] Rodriguez, M.D., Redondo, A., Villanueva, M.J. Study of dietary fibre content
in cucumber by gravimetric and spectrophotometric methods. Food Chem.
1992, 43, 295-8.

[304] Bansal, M., Garg, U., Singh, D., Garg, V.K. Removal of Cr(VI) from aqueous
solutions using pre-consumer processing agricultural waste: a case study of
rice husk. J Hazard Mater. 2009, 162, 312-20.

[305] Vadivelan, V., Kumar, K.V. Equilibrium, kinetics, mechanism, and process
design for the sorption of methylene blue onto rice husk. J. Colloid Interf. Sci.
2005, 286, 90-100.

[306] Ekpete, O., Harcourt, P. Preparation and characterization of activated carbon

derived from fluted pumpkin stem waste (Telfairia occidentalis Hook F). Res.
J. Chem. Sci. 2011, 1, 10-7.

[307] International, A. Test Methods for Moisture in Activated Carbon. 1999.

[308] International, A. Test Method for Total Ash Content of Activated Carbon.
2004.

[309] Jamshidi, A., Tayari, E., Neisy, A. Comparision of Two Earth Surface
Machine Oil on Soil Compaction, Water Consumption and Wheat Yield in
Shoushter Region. Indian J. Sci. Res. 2014, 7, 1162-6.

[310] Malik, R., Ramteke, D., Wate, S. Physico-chemical and surface

characterization of adsorbent prepared from groundnut shell by ZnCl2
activation and its ability to absorb colour. Indian J. Chem. Technol. 2006, 13,
319.

[311] Gardea-Torresdey, J.L., Gonzalez, J.H., Tiemann, K.J., Rodriguez, O., Gamez,
G. Phytofiltration of hazardous cadmium, chromium, lead and zinc ions by
biomass of Medicago sativa (Alfalfa). J Hazard Mater. 1998, 57, 29-39.

[312] Wang, X.J., Xia, S.Q., Chen, L., Zhao, J.F., Chovelon, J.M., Nicole, J.R.
Biosorption of cadmium(II) and lead(II) ions from aqueous solutions onto
dried activated sludge. J Environ Sci (China). 2006, 18, 840-4.

[313] Namasivayam, C., Prabha, D., Kumutha, M. Removal of direct red and acid
brilliant blue by adsorption on to banana pith. Bioresour. Technol. 1998, 64,
77-9.
131
 References

[314] Argun, M.E., Dursun, S., Ozdemir, C., Karatas, M. Heavy metal adsorption by
modified oak sawdust: thermodynamics and kinetics. J Hazard Mater. 2007,
141, 77-85.

[315] Mehrizad, A., Aghaie, M., Gharbani, P., Dastmalchi, S., Monajjemi, M., Zare,
K. Comparison of 4-chloro-2-nitrophenol adsorption on single-walled and
multi-walled carbon nanotubes. Iranian J. Environ. Health Sci. Eng. 2012, 9,
5.

[316] Anbia, M., Ghaffari, A. Adsorption of phenolic compounds from aqueous

solutions using carbon nanoporous adsorbent coated with polymer. Appl.
Surface Sci. 2009, 255, 9487-92.

[317] Altın, O., Özbelge, H.Ö., Doğu, T. Use of General Purpose Adsorption
Isotherms for Heavy Metal–Clay Mineral Interactions. J. Colloid Interf. Sci.
1998, 198, 130-40.

[318] Aksu, Z., Isoglu, I.A. Use of agricultural waste sugar beet pulp for the removal
of Gemazol turquoise blue-G reactive dye from aqueous solution. J. Hazard.
Mater. 2006, 137, 418-30.

[319] ] Adeogun, A., Idowu, M., Ofudje, A., Kareem, S., Ahmed, S. Comparative
biosorption of Mn(II) and Pb(II) ions on raw and oxalic acid modified maize
husk: kinetic, thermodynamic and isothermal studies. Appl. Water Sci. 2013,
3, 167-79.

[320] ] Vazquez, G., Gonzalez-Alvarez, J., Freire, S., Lopez-Lorenzo, M.,

Antorrena, G. Removal of cadmium and mercury ions from aqueous solution
by sorption on treated Pinus pinaster bark: kinetics and isotherms. Bioresour.
Technol. 2002, 82, 247-51.

[321] Elaigwu, S., Usman, L., Awolola, G., Adebayo, G., Ajayi, R. Adsorption of Pb
(II) from aqueous solution by activated carbon prepared from cow dung. Adv.
Natural Appl. Sci. 2009, 3, 442-6.

[322] Pehlivan, E., Altun, T., Parlayici, S. Utilization of barley straws as biosorbents
for Cu2+ and Pb2+ ions. J. Hazard. Mater. 2009, 164, 982-6.

[323] Ho, Y.-S., Ofomaja, A.E. Biosorption thermodynamics of cadmium on

coconut copra meal as biosorbent. Biochem. Eng. J. 2006, 30, 117-23.

[324] Alfaro-Cuevas-Villanueva, R., Hidalgo-Vazquez, A.R., Cortes Penagos Cde,

J., Cortes-Martinez, R. Thermodynamic, kinetic, and equilibrium parameters
for the removal of lead and cadmium from aqueous solutions with calcium
alginate beads. Scientific World Journal. 2014, 647512.

132
 References

[325] Nuhoglu, Y., Malkoc, E. Thermodynamic and kinetic studies for

environmentaly friendly Ni(II) biosorption using waste pomace of olive oil
factory. Bioresour. Technol. 2009, 100, 2375-80.

[326] Aksu, Z., Tunç, Ö. Application of biosorption for penicillin G removal:

comparison with activated carbon. Process Biochem. 2005, 40, 831-47.

[327] Donat, R., Akdogan, A., Erdem, E., Cetisli, H. Thermodynamics of Pb2+ and
Ni2+ adsorption onto natural bentonite from aqueous solutions. J. Colloid
Interf. Sci. 2005, 286, 43-52.

[328] Namasivayam, C., Yamuna, R. T. Adsorption of chromium (VI) by a low-cost

adsorbent: Biogas residual slurry. Chemosphere. 1995, 30, 561-78.

[329] Ho, Y.S., McKay, G. The kinetics of sorption of divalent metal ions onto
sphagnum moss peat. Water Res. 2000, 34, 735-42.

[330] Özer, A., Gürbüz, G., Çalimli, A., Körbahti, B.K. Biosorption of copper (II)
ions on Enteromorpha prolifera: Application of response surface methodology
(RSM). Chem. Eng. J. 2009, 146, 377-87.

[331] McKay, G. The Adsorption of basic dye onto silica from aqueous solution-
solid diffusion model. Chem. Eng. Sci. 1984, 39, 129-38.

[332] ] Weber, W., Morris, J. Kinetics of adsorption on carbon from solution. J.

Sanit. Eng. Div. Am. Soc. Civ. Eng. 1963, 89, 31-60.

[333] Wang, L., Zhang, J., Zhao, R., Li, Y., Li, C., Zhang, C. Adsorption of Pb(II)
on activated carbon prepared from Polygonum orientale Linn.: kinetics,
isotherms, pH, and ionic strength studies. Bioresour. Technol. 2010, 101,
5808-14.

[334] Chen, J.P., Wu, S., Chong, K.-H. Surface modification of a granular activated
carbon by citric acid for enhancement of copper adsorption. Carbon. 2003, 41,
1979-86.

[335] Figaro, S., Avril, J.P., Brouers, F., Ouensanga, A., Gaspard, S. Adsorption
studies of molasse's wastewaters on activated carbon: modelling with a new
fractal kinetic equation and evaluation of kinetic models. J. Hazard. Mater.
2009, 161, 649-56.

[336] Filipovic-Kovacevic, Z., Sipos, L., Briski, F. Biosorption of chromium,

copper, nickel and zinc ions onto fungal pellets of Aspergillus niger 405 from
aqueous solutions. Food Technol. Biotechnol. 2000, 38.

[337] Sharma, S.K., Sanghi, R. Advances in water treatment and pollution

prevention, Springer, 2012.
133
 References

[338] Shouaib, A., Badar, T., Aslam, N. Removal of Pb (II), Cu (II) and Cd (II) from
aqueous solution by some fungi and natural adsorbents in single and multiple
metal systems. Pakistan J. Botany. 2011, 43, 2997-3000.

[339] Sheng, P.X., Ting, Y.-P., Chen, J.P. Biosorption of heavy metal ions (Pb, Cu,
and Cd) from aqueous solutions by the marine alga Sargassum sp. in single-
and multiple-metal systems. Indust. Eng. Chem. Res. 2007, 46, 2438-44.

[340] Kayestha, R., Sumati, Hajela, K. ESR studies on the effect of ionic radii on
displacement of Mn2+ bound to a soluble beta-galactoside binding hepatic
lectin. FEBS Lett. 1995, 368, 285-8.

[341] Faur-Brasquet, C., Reddad, Z., Kadirvelu, K., Le Cloirec, P. Modeling the
adsorption of metal ions (Cu2+, Ni2+, Pb2+) onto ACCs using surface
complexation models. App. Surf. Sci. 2002, 196, 356-65.

[342] Thomson, M.A., Melling, P.J., Slepski, A.M. Real-time monitoring of

isocyanate chemistry using a fiber-optic FTIR probe. Polymer Preprints-
America. 2001, 42, 310-1.

[343] Senda, T., He, Y., Inoue, Y. Biodegradable blends of poly(ε-caprolactone)

with α-chitin and chitosan: specific interactions, thermal properties and
crystallization behavior. Polymer Int. 2002, 51, 33-9.

[344] Braovac, S., Kutzke, H. The presence of sulfuric acid in alum-conserved

wood–Origin and consequences. J. Cultural Heritage. 2012, 13, S203-S8.

[345] Garside, P., Wyeth, P. Identification of Cellulosic Fibres by FTIR

Spectroscopy-Thread and Single Fibre Analysis by Attenuated Total
Reflectance. Studies in Conservation. 2003, 48, 269-75.

[346] Kamal, M.H., Azira, W.M., Kasmawati, M., Haslizaidi, Z., Saime, W.N.
Sequestration of toxic Pb(II) ions by chemically treated rubber (Hevea
brasiliensis) leaf powder. J. Environ. Sci. (China). 2010, 22, 248-56.

[347] Jahn, A., Schroder, M.W., Futing, M., Schenzel, K., Diepenbrock, W.
Characterization of alkali treated flax fibres by means of FT Raman
spectroscopy and environmental scanning electron microscopy. Spectrochim.
Acta A Mol. Biomol. Spectrosc. 2002, 58, 2271-9.

[348] Zvinowanda, C., Okonkwo, J., Shabalala, P., Agyei, N. A novel adsorbent for
heavy metal remediation in aqueous environments. Int. J. Environ. Sci.
Technol. 2009, 6, 425-34.

[349] Huang, C.-H., Chen, L., Yang, C.-L. Effect of anions on electrochemical
coagulation for cadmium removal. Sep. Purif. Technol. 2009, 65, 137-46.

134
 References

[350] Choi, D., Kim, Y. Cadmium removal using hollow fiber membrane with
organic extradant. Korean J. Chem. Eng. 2003, 20, 768-71.

[351] Bayar, S., Yilmaz, A.E., Boncukcuoğlu, R., Fìl, B.A., Kocakerìm, M.M.
Effects of operational parameters on cadmium removal from aqueous
solutions by electrochemical coagulation. Desal. Water Treat. 2013, 51, 2635-
43.

[352] Salmani, M.H., Davoodi, M., Ehrampoush, M.H., Ghaneian, M.T.,

Fallahzadah, M.H. Removal of cadmium (II) from simulated wastewater by
ion flotation technique. Iranian J. Environ. Health Sci. Eng. 2013, 10, 16.

[353] Saeed, A., Iqbal, M., Höll, W.H. Kinetics, equilibrium and mechanism of Cd 2+
removal from aqueous solution by mungbean husk. J. Hazard. Mater. 2009,
168, 1467-75.

[354] Senthilkumar, T., Raghuraman, R., Miranda, L.R. Parameter Optimization of

Activated Carbon Production from Agave sisalana and Punica granatum Peel:
Adsorbents for CI Reactive Orange 4 Removal from Aqueous Solution.
CLEAN–Soil, Air, Water. 2013, 41, 797-807.

[355] Saeed, A., Iqbal, M., Akhtar, M.W. Removal and recovery of lead(II) from
single and multimetal (Cd, Cu, Ni, Zn) solutions by crop milling waste (black
gram husk). J. Hazard. Mater. 2005, 117, 65-73.

[356] Chen, G., Zeng, G., Tang, L., Du, C., Jiang, X., Huang, G., et al. Cadmium
removal from simulated wastewater to biomass byproduct of Lentinus edodes.
Bioresour. Technol. 2008, 99, 7034-40.

[357] Aroua, M.K., Leong, S.P.P., Teo, L.Y., Yin, C.Y., Daud, W.M.A.W. Real-
time determination of kinetics of adsorption of lead(II) onto palm shell-based
activated carbon using ion selective electrode. Bioresour. Technol. 2008, 99,
5786-92.

[358] Zhu, B., Fan, T., Zhang, D. Adsorption of copper ions from aqueous solution
by citric acid modified soybean straw. J. Hazard. Mater. 2008, 153, 300-8.

[359] Azouaoua, N., Belmedanib, M., Mokaddema, H., Sadaoui, Z. Adsorption of

Lead from Aqueous Solution onto Untreated Orange Barks. Chem. Eng. 2013,
32, 55-60.

[360] Shukla, A., Zhang, Y.-H., Dubey, P., Margrave, J.L., Shukla, S.S. The role of
sawdust in the removal of unwanted materials from water. J. Hazard. Mater.
2002, 95, 137-52.

135
 References

[361] Mouni, L., Merabet, D., Bouzaza, A., Belkhiri, L. Adsorption of Pb(II) from
aqueous solutions using activated carbon developed from Apricot stone.
Desal. 2011, 276, 148-53.

[362] Yang, C. Statistical Mechanical Study on the Freundlich Isotherm Equation. J.

Colloid Interf. Sci. 1998, 208, 379-87.

[363] Okafor, P., Okon, P., Daniel, E., Ebenso, E. Adsorption capacity of coconut
(Cocos nucifera L.) shell for lead, copper, cadmium and arsenic from aqueous
solutions. Int J. Electrochem. Sci. 2012, 7, 12354-69.

[364] Zafar, M.N., Nadeem, R., Hanif, M.A. Biosorption of nickel from protonated
rice bran. J. Hazard. Mater. 2007, 143, 478-85.

[365] Jiang, W., Pelaez, M., Dionysiou, D.D., Entezari, M.H., Tsoutsou, D., O’Shea,
K. Chromium(VI) removal by maghemite nanoparticles. Chem. Eng. J. 2013,
222, 527-33.

[366] Demirbas, E., Kobya, M., Senturk, E., Ozkan, T. Adsorption kinetics for the
removal of chromium (VI) from aqueous solutions on the activated carbons
prepared from agricultural wastes. Water SA. 2004, 30, p. 533-9.

[367] Benaissa, H., Benguella, B. Effect of anions and cations on cadmium sorption
kinetics from aqueous solutions by chitin: experimental studies and modeling.
Environ. Pollut. 2004, 130, 157-63.

[368] Arslanoglu, H., Soner Altundogan, H., Tumen, F. Preparation of cation

exchanger from lemon and sorption of divalent heavy metals. Bioresour.
Technol. 2008, 99, 2699-705.

[369] Doshi, H., Ray, A., Kothari, I. L. Biosorption of cadmium by live and dead
Spirulina: IR spectroscopic, kinetics, and SEM studies. Curr. Microbiol. 2007,
54, 213-8.

[370] Lakshmipathy, R., Sarada, N.C. Application of watermelon rind as sorbent for
removal of nickel and cobalt from aqueous solution. Int. J. Mineral Process.
2013, 122, 63-5.

[371] Weng, C.-H., Lin, Y.-T., Tzeng, T.-W. Removal of methylene blue from
aqueous solution by adsorption onto pineapple leaf powder. J. Hazard. Mater.
2009, 170, 417-24.

[372] Jayaprakasha, G.K., Chidambara Murthy, K.N., Patil, B.S. Rapid HPLC-UV
method for quantification of l-citrulline in watermelon and its potential role on
smooth muscle relaxation markers. Food Chem. 2011, 127, 240-8.

136
 References

[373] Mort, A., Zheng, Y., Qiu, F., Nimtz, M., Bell-Eunice, G. Structure of
xylogalacturonan fragments from watermelon cell-wall pectin.
Endopolygalacturonase can accommodate a xylosyl residue on the
galacturonic acid just following the hydrolysis site. Carb. Res. 2008, 343,
1212-21.

[374] Zhu, Z.L., Ma, H.M., Zhang, R.H., Ge, Y.X., Zhao, J.F. Removal of cadmium
using MnO2 loaded D301 resin. J. Environ. Sci. 2007, 19, 652-6.

[375] Tripathy, S.S., Kanungo, S.B. Adsorption of Co2+, Ni2+, Cu2+ and Zn2+ from
0.5 M NaCl and major ion sea water on a mixture of delta-MnO2 and
amorphous FeOOH. J. Colloid Interf. Sci. 2005, 284, 30-8.

[376] Kazemipour, M., Ansari, M., Tajrobehkar, S., Majdz, M., Kermani, H.
Removal of lead, cadmium, zinc and copper from industrial carbon developed
from walnut, hazelnut, almond, pistachio and apricot stone. J. Hazard. Mater.
2008, 150, 322 - 7.

[377] Wan Ngah, W.S., Hanafiah, M.A.K.M. Removal of heavy metal ions from
wastewater by chemically modified plant wastes as adsorbents: A review.
Bioresour. Technol. 2008, 99, 3935-48.

[378] Baes, C.F., Mesmer, R.E. Hydrolysis of cations. 1976.

[379] Vasudevan, P., Padmavathy, V., Dhingra, S.C. Biosorption of monovalent and
divalent ions on baker's yeast. Bioresour. Technol. 2002, 82, 285-9.

[380] Jiang, M.-q., Jin, X.-y., Lu, X.-Q., Chen, Z.-l. Adsorption of Pb(II), Cd(II),
Ni(II) and Cu(II) onto natural kaolinite clay. Desal. 2010, 252, 33-9.

[381] Arief, V.O., Trilestari, K., Sunarso, J., Indraswati, N., Ismadji, S. Recent
Progress on Biosorption of Heavy Metals from Liquids Using Low Cost
Biosorbents: Characterization, Biosorption Parameters and Mechanism
Studies. CLEAN – Soil, Air, Water. 2008, 36, 937-62.

[382] Malik, U.R., Hasany, S.M., Subhani, M.S. Sorptive potential of sunflower
stem for Cr(III) ions from aqueous solutions and its kinetic and
thermodynamic profile. Talanta. 2005, 66, 166-73.

[383] Walton, H.F. Ion Exchange. F. G. Helfferich. McGraw-Hill, New York,

Science. 1962.

[384] Hameed, B.H. Spent tea leaves: A new non-conventional and low-cost
adsorbent for removal of basic dye from aqueous solutions. J. Hazard. Mater.
2009, 161, 753-9.

137
 References

[385] Boonamnuayvitaya, V., Chaiya, C., Tanthapanichakoon, W., Jarudilokkul, S.

Removal of heavy metals by adsorbent prepared from pyrolyzed coffee
residues and clay. Sep. Purif. Technol. 2004, 35, 11-22.

[386] Leyva-Ramos, R., Landin-Rodriguez, L.E., Leyva-Ramos, S., Medellin-

Castillo, N.A. Modification of corncob with citric acid to enhance its capacity
for adsorbing cadmium(II) from water solution. Chem. Eng. J. 2012, 180, 113-
20.

[387] Zaki, A.B., El-Sheikh, M.Y., Evans, J., El-Safty, S.A. Kinetics and
Mechanism of the Sorption of Some Aromatic Amines onto Amberlite IRA-
904 Anion-Exchange Resin. J. Colloid Interf. Sci. 2000, 221, 58-63.

[388] Malkoc, E., Nuhoglu, Y. Determination of kinetic and equilibrium parameters

of the batch adsorption of Cr(VI) onto waste acorn of Quercus ithaburensis.
Chem. Eng. Processing: Process Intensification. 2007, 46, 1020-9.

[389] Wu, F.C., Tseng, R.L., Juang, R.S. Comparisons of porous and adsorption
properties of carbons activated by steam and KOH. J. Colloid Interf. Sci.
2005, 283, 49-56.

[390] Cheung, W.H., Szeto, Y.S., McKay, G. Intraparticle diffusion processes

during acid dye adsorption onto chitosan. Bioresour. Technol. 2007, 98, 2897-
904.

[391] Gerçel, Ö., Gerçel, H.F. Adsorption of lead(II) ions from aqueous solutions by
activated carbon prepared from biomass plant material of Euphorbia rigida.
Chem. Eng. J. 2007, 132, 289-97.

[392] Bregg, R.K. Current Topics in Polymer Research, Nova Publishers, 2005.

[393] Yan, W., Yuan, P., Chen, M., Wang, L., Liu, D. Infrared spectroscopic
evidence of a direct addition reaction between palygorskite and pyromellitic
dianhydride. App. Surf. Sci. 2013, 265, 585-90.

[394] Williams, D., Fleming, I., Pretsch, E. Spectroscopic Methods. Organic

Chemistry. 1989.

[395] Hameed, B.H. Grass waste: a novel sorbent for the removal of basic dye from
aqueous solution. J. Hazard. Mater. 2009, 166, 233-8.

[396] David, G.J.M., Nicole, L., Robert, W.S., Kristen, G., Lindsey, K., Isabella,
M.S., et al. Rapid Assessment of Lignin Content and Structure in Switchgrass
(Panicum virgatum L.) Grown Under Different Environmental Conditions.
Bioenerg. Res. 2009, 2-245-256.

138
 References

[397] Matheickal, J.T., Yu, Q., Woodburn, G.M. Biosorption of cadmium(II) from
aqueous solutions by pre-treated biomass of marine alga DurvillAea
potatorum. Water Res. 1999, 33, 335-42.

[398] Ting, Y.P., Prince, I.G., Lawson, F. Uptake of cadmium and zinc by the alga
Chlorella vulgaris: II. Multi-ion situation. Biotechnol. Bioeng. 1991, 37, 445-
55.

[399] Ghali, L., Msahli, S., Zidi, M., Sakli, F. Effect of pre-treatment of Luffa fibres
on the structural properties. Mater. Lett. 2009, 63, 61-3.

[400] Carvalho, M.L., Sousa Jr., R., Rodríguez-Zúñiga, U.F., Suarez, C.A.G.,
Rodrigues, D.S., Giordano, R.C., et al. Kinetic study of the enzymatic
hydrolysis of sugarcane bagasse. Brazilian J. Chem. Eng. 2013, 30, 437-47.

[401] Witek-Krowiak, A. Application of beech sawdust for removal of heavy metals

from water: biosorption and desorption studies. Euro J. Wood and Wood
Products. 2013, 71, 227-36.

[402] Raji, C., Manju, G.N., Anirudhan, T.S. Removal of heavy metal ions from
water using sawdust-based activated carbon. Indian J. Eng. Mater. S. 1997, 4,
254-60.

[403] Li, Y.-H., Luan, Z., Xiao, X., Zhou, X., Xu, C., Wu, D., et al. Removal of
Cu2+ Ions from Aqueous Solutions by Carbon Nanotubes. Adsorpt. Sci.
Technol. 2003, 21, 475-85.

[404] Gupta, V.K., Rastogi, A. Biosorption of lead from aqueous solutions by green
algae Spirogyra species: Kinetics and equilibrium studies. J. Hazard. Mater.
2008, 152, 407-14.

[405] Wu, Y., Zhang, S., Guo, X., Huang, H. Adsorption of chromium (III) on
lignin. Bioresour. Technol. 2008, 99, 7709-15.

[406] Vassileva, P., Detcheva, A., Uzunov, I., Uzunova, S. Removal of metal ions
from aqueous solutions using pyrolyzed rice husks: adsorption kinetics and
equilibria. Chem. Eng. Commun. 2013, 200, 1578-99.

[407] Ozer, A., Ozer, D. Comparative study of the biosorption of Pb(II), Ni(II) and
Cr(VI) ions onto S. cerevisiae: determination of biosorption heats. J. Hazard.
Mater. 2003, 100, 219-29.

[408] Saltali, K., Sari, A., Aydin, M. Removal of ammonium ion from aqueous
solution by natural Turkish (Yildizeli) zeolite for environmental quality. J.
Hazard. Mater. 2007, 141, 258-63.

139
 References

[409] Horsfall, M., Jr., Spiff, A.I. Sorption of lead, cadmium, and zinc on sulfur-
containing chemically modified wastes of fluted pumpkin (Telfairia
occidentalis Hook f.). Chemistry & Biodiversity. 2005, 2, 373-85.

[410] Ho, Y., McKay, G. Pseudo-second order model for sorption processes.
Process Biochem. 1999, 34, 451 - 65.

[411] Chatterjee, S., Woo, S.H. The removal of nitrate from aqueous solutions by
chitosan hydrogel beads. J. Hazard. Mater. 2009, 164, 1012-8.

[412] [412] Ho, Y.S., McKay, G. The sorption of lead(II) ions on peat. Water Res.
1999, 33, 578-84.

[413] Fourest, E. Etude des mécanismes de biosorption des métaux lourds par des
biomasses fongigues industrielles en vue d'un procédé d'éputation des
effluents aqueux contaminés 1993.

[414] Lodeiro, P., Barriada, J.L., Herrero, R., Sastre de Vicente, M.E. The marine
macroalga Cystoseira baccata as biosorbent for cadmium(II) and lead(II)
removal: Kinetic and equilibrium studies. Environ. Pollut. 2006, 142, 264-73.

[415] Sankararamakrishnan, N., Sharma, A.K., Sanghi, R. Novel chitosan derivative

for the removal of cadmium in the presence of cyanide from electroplating
wastewater. J. Hazard. Mater. 2007, 148, 353-9.

[416] Muzzarelli, R.A., Tubertini, O. Chitin and chitosan as chromatographic

supports and adsorbents for collection of metal ions from organic and aqueous
solutions and sea-water. Talanta. 1969, 16, 1571-7.

[417] Tobin, J.M., Cooper, D.G., Neufeld, R.J. Uptake of Metal Ions by Rhizopus
arrhizus Biomass. Appl. Environ. Microbiol. 1984, 47, 821-4.

[418] Prasanna Kumar, Y., King, P., Prasad, V.S.R.K. Adsorption of zinc from
aqueous solution using marine green algae—Ulva fasciata sp. Chem. Eng. J.
2007, 129, 161-6.

[419] Sheng, P.X., Ting, Y.-P., Chen, J.P., Hong, L. Sorption of lead, copper,
cadmium, zinc, and nickel by marine algal biomass: characterization of
biosorptive capacity and investigation of mechanisms. J. Colloid Interf. Sci.
2004, 275, 131-41.

[420] Sousa, F.W., Oliveira, A.G., Ribeiro, J.P., De Keukeleire, D., Sousa, A.F.,
Nascimento, R.F. Single and multielementary isotherms of toxic metals in
aqueous solution using treated coconut shell powder. Desalin. Water Treat.
2011, 36, 289-96.

140
 References

[421] Low, K.S., Lee, C.K., Liew, S.C. Sorption of cadmium and lead from aqueous
solutions by spent grain. Process Biochem. 2000, 36, 59-64.

*******************

141
 Summary

The presence of heavy metals in environment has become a major issue due to
their toxicity for living beings. Among the most toxic heavy metals, the Lead and
Cadmium are most abundantly found in natural water bodies and are also released into
the environment as a result of electroplating industries, metallurgical processes, metal
finishing, tannery, battery manufacture, and fertilizer industries etc. They enter into the
living organisms via inhalation, ingestion, and skin adsorption and cause severe toxic
effects. Hence, the development of efficient techniques for the removal of Cd(II) and
Pb(II) ions from waters and wastewaters is an important task in terms of public health
and environment protection.
So many conventional methods have been used for treatment of wastewater such
as, chemical oxidation, precipitation, solvent extraction, ion exchange, membrane
processes, reverse osmosis and adsorption. Adsorption among them is the most
effective treatment process with selection of a proper adsorbent. The most significant
features of the adsorption process is high metal removal efficiency even from very
dilute metal contaminated solutions. On the other hand, this process possess additional
advantage such as easy handling, high selectivity, lower operating cost, minimization
of chemical or biological sludge, and regeneration of adsorbent. A wide range of
adsorbents have been used for heavy metal removal including activated carbon and
which is recognized as an effective adsorbent due to its large surface area and high
adsorption capacity. However, its high cost limit its use as an adsorbent like other
conventional methods.
The new biosorption technology for metal removal offers as an alternative for
potentially economic and attractive treatment particularly suited for dilute metal
contaminants. In recent years, the search for low-cost agro-based adsorbents having
high metal-binding capacities have attracted the attention of environmentalists to a great
extent with main focus on the natural materials that are locally available in large
quantities such as agricultural waste or industrial byproducts to utilize them as low-cost
adsorbents.
In concern of the above, four unexplored agro-waste material i.e. Cucumis
sativus (cucumber) peel, Desmostachya bipinnata (Kush grass), Bambusa arundinacea
(Bamboo) leaves and Citrullus lanatus (Watermelon) rind have been

142
 Summary

selected because they are inexpensive and easily available in bulk at various locations
around the world and are ecofriendly. Particularly, the cost considerations and excellent
performance of these materials make them expedient to use as biosorbents for removal
of these heavy metals.
In present thesis the whole work is summarized in six main chapters, the first
chapter is introduction, second one deals with literature review and the rest of the four
chapters describe experimental studies done under present thesis. In the third chapter,
Cucumis sativus (Cucumber) peel (CSP) was explored for the removal of Pb(II) ions
from simulated wastewater by batch experiments by optimizing the experimental
conditions one by one. The optimum pH, adsorbent dose and contact time for the
removal Pb(II) ions from 25 mg/l initial concentration of Pb(II) was found to be 5, 5g/l
and 90 min, respectively. The equilibrium data presented a better fit to the Langmuir
isotherm model (Figure 1a) with a maximum adsorption capacity of 28.25 mg/g at
25°C, indicating a monolayer sorption process. The high value of adsorption capacity
of CSP indicates its significant utility as biosorbent. Kinetic study of Pb(II) adsorption
on CSP surface showed a better agreement with the pseudo-second order kinetics
(Figure 1b) thereby confirming the occurrence of chemisorption. Intra-particle
diffusion also played a significant role at the initial stage of the adsorption process.
Thermodynamic parameters i.e. ΔG°, ΔS° and ΔH° indicated the spontaneous
feasibility and endothermic nature of adsorption process.

Figure 1: Best fit of Langmuir isotherm model (a) and Pseudo second order kinetic
model (b) for Pb(II) ions removal using CSP from simulated wastewater.
In the fourth chapter, the removal of Cd(II) ions from simulated wastewater
was performed using Cucumis sativus (Cucumber) peel as adsorbent. The maximum
143
 Summary

Cd(II) ion sorption was obtained at pH 5. The maximum removal efficiency ~82% was
achieved in contact time 150 min with initial Cd(II) ion concentration 25 mg/l. Batch
studies displayed that the equilibrium experimental data follows Freundlich isotherm
model (R2 ≥ 0.975) (Figure 2a) as compared to that of the Langmuir isotherm model.
Experimental data shows the best fit to pseudo second-order model with a high
correlation coefficient value (R2 ~0.999) closer to 1(Figure 2b) as compared to that of
pseudo-first order. These results are in conformity with the occurrence of
chemisorption. Thermodynamic parameters indicated that the process was spontaneous,
feasible and endothermic in nature.

Figure 2: Best fit of Freundlich isotherm model (a) and Pseudo second order kinetic
model (b) for Cd(II) ions removal using CSP from simulated wastewater.
In chapter five, Citrullus lanatus (Watermelon) Rind (CLR) modified by citric
acid was used for the removal of Pb(II) and Cd(II) ions from simulated wastewater
through batch experiments. The optimum pH was found to be 6. Freundlich, Langmuir
and D-R isotherm models were applied to explain adsorption behavior for the removal
of Pb(II) and Cd(II) ions with CLR. The q(theoretical) values obtained by Langmuir and D-
R isotherm model are in better agreement with q(experimental) values as compared to that
of Freundlich isotherm model for this set of experiment (Figure 3). Therefore both the
adsorption isotherms models i.e. Langmuir and D–R model were used to interpret the
equilibrium data for the sorption of Pb(II) and Cd(II) ions onto CLR. Mean biosorption
energy E (11.18 kJ/mol) calculated from D-R isotherm model for the adsorption of
Pb(II) and Cd(II) ions on surface of CLR suggests the existence of chemisorption in
this process. Thus Langmuir isotherm model indicated monolayer formation of metal
ions on the surface of CLR, whereas the occurrence of chemisorption was confirmed
144
 Summary

by the D-R isotherm model. Kinetic studies showed a better fit of the experimental data
to the pseudo-second order kinetics with a higher correlation coefficient value (R2=
0.990) as compared to that of pseudo first order kinetic model (R2 ≤ 0.980). The intra
particle diffusion model suggested involvement of more than one process i.e. adsorption
and intraparticle diffusion in the overall adsorption mechanism. The thermodynamic
parameters indicated spontaneous feasibility and endothermic nature of the adsorption
process of Pb(II) and Cd(II) ions on the surface of CLR. High adsorption capacity of
CLR for Pb(II) qm=47 mg/g and Cd(II) qm=55.56 mg/g showed that CLR has a
significant potential as efficient biosorbent for the removal of Pb(II) and Cd(II) ions
from aqueous solutions/industrial wastewater.

Figure 3: Adsorption isotherm of Pb(II) (a) & Cd(II) ion (b) removal using CLR at
25±1°C.

In the sixth chapter, NaOH modified Desmostachya bipinnata (MDBL) &

Bambusa arundinacea Leaves (MBAL) were characterized and used for the
remediation of Cd(II) ions from simulated wastewater. All the operational parameters
such as the pH, adsorbent dosage, contact time and initial metal ion concentrations
evidently influenced the removal efficiency. The optimum pH was found to be 6.5 for
both the adsorbents for Cd(II) ion removal from simulated aqueous solution. Langmuir
and Freundlich isotherm models were applied to the adsorption equilibrium data.
Langmuir adsorption isotherm agreed well to the adsorption equilibrium data with
correlation coefficient value for MDBL (R2 ~0.99) and MBAL (R2 ≥ 0.98) suggesting
monolayer formation of Cd(II) ion on the surface of adsorbents. The maximum
adsorption capacity for MDBL was found to be (qm = 15.22 mg/g) and for MBAL (qm =
19.70 mg/g), which was significantly higher than the adsorption capacities of numerous

145
 Summary

adsorbents previously studied for the removal of Cd(II) ion. The adsorption process
follows pseudo-second-order kinetics rate model with a higher correlation coefficient
value (R2 ≥ 0.99) compared to than that of pseudo first order kinetic model, confirming
the existence of chemisorption. On application of intraparticle diffusion model the
results showed that it was not the only rate-limiting step i.e. there were more than one
processes controlling the adsorption rate like surface adsorption and intraparticle
diffusion. Thermodynamic parameters indicated that the adsorption process was
spontaneously feasible and endothermic in nature.

Figure 4: Langmuir isotherm model for Cd(II) ion removal from aqueous solution
using MDBL (a) and MBAL (b).

Figure 4: Pseudo second order kinetic model for Cd(II) ion removal from aqueous
solution using MDBL (a) and MBAL (b).

To correlate the observations with the real wastewater, sets of batch experiments
were performed in the presence of other heavy metal ions such as Cu(II), Ni(II) and
Cd(II)/Pb(II). The outcomes of these studies showed that the most inhibitory effect was

146
 Summary

caused by Cu(II) ion for the adsorption of Pb(II)/ Cd(II) ions with all the adsorbents
used in this thesis work. The effect of commonly cations such as Na+, K+, Ca2+ and
Mg2+ and anions like sulfate, carbonate, chloride and nitrate on the uptake of
Pb(II)/Cd(II) ions using different adsorbents was also studied. Involvement of
functional groups present on the adsorbent surface on adsorption phenomenon were
studied by recording Fourier Transform Infrared Spectra (FTIR) of adsorbents before
and after adsorption. FTIR study confirmed the involvement of various functional
group such as -COOH, phenolic OH, -NH, C-O-C of lignin structure and carbonyl
group i.e. C=O. Similarly, Scanning Electron Microscopy (SEM) images of adsorbents
were taken before and after adsorption to observe the morphological changes on the
surface of adsorbents.

In all the chapters desorption study was successfully performed using small
amount of dil. HNO3 as an eluent. Regenerated adsorbents by desorption of adsorbed
metal ions exhibited effective adsorption of metal ions even after successive desorption.
Therefore, the reuse of exhausted adsorbents after desorption of previously adsorb
metal ions for the further sets of adsorption studies is recommended.
Present study showed that all the biosorbents exhibited an excellent adsorption
capacities for the removal of Pb(II) and Cd(II) ions from aqueous solutions as compared
to those of earlier studied biosorbents. Adsorption capacity of these adsorbents are at
par with other commercial adsorbents / numerous previously studied other biosorbents
prepared with agro-waste materials. Therefore, all these selected biosorbents can be
successfully used as a low-cost, environment friendly adsorbent for the efficient
removal of Pb(II)/Cd(II) ions from aqueous solution. Utilization of these freely and
abundantly available biomass will not only reduce the cost, but also lower the energy
requirement in modifying the biomass.

*****************

147
 Publications

Related to Ph.D. Work

1. Utilization of NaOH modified Desmostachya bipinnata (Kush grass) Leaves &

Bambusa arundinacea (Bamboo) Leaves for Cd(II) removal from aqueous
solution.
Ruchi Pandey, R. L. Prasad, N. G. Ansari, R. C. Murthy, Journal of
Environmental Chemical Engineering, DOI: 10.1016/j.jece.2014.06.015, 2014.

2. Pb(II) Removal from Aqueous Solution by Cucumis sativus (Cucumber) Peel:

Kinetic, Equilibrium & Thermodynamic Study.
Ruchi Pandey, N. G. Ansari, R. L. Prasad, R. C. Murthy, American Journal of
Environmental Protection, 2 (3), 51-58. DOI: 10.12691/env-2-3-1, 2014.

3. Cd(II) adsorption from aqueous solution onto cucumis sativus peel: Equilibrium,
Thermodynamics and Kinetic study.
Ruchi Pandey, N.G. Ansari, R.C.Murthy and R.L. Prasad, Journal of
Ecophysiology and Occupational Health, 3 & 4, 75-84, 2013.
Other:
 Multiple approaches to evaluate the toxicity of the biomass fuel cow dung
(kanda) smoke.
Kewal Lal, U. Mani, Ruchi Pandey, N. Singh, A K. Singh, D.K. Patel, M. P.
Singh & R.C. Murthy, Journal of Ecotoxicology & Environmental Saftey,
DOI: 10.1016/j.ecoenv.2011.06.006, 2011.

Communicated Manuscripts
 Utilization of NaOH modified Citrullus lanatus Rind for Pb(II) and Cd(II)
removal from aqueous solution.
Ruchi Pandey, R. L. Prasad, N. G. Ansari, R. C. Murthy, 2014
 G Model
JECE 376 1–10

Journal of Environmental Chemical Engineering xxx (2014) xxx–xxx

Contents lists available at ScienceDirect

Journal of Environmental Chemical Engineering

journal homepage: www.elsevier.com/locate/jece

1 Utilization of NaOH modified Desmostachya bipinnata (Kush grass)

2 leaves and Bambusa arundinacea (bamboo) leaves for Cd(II) removal
3 from aqueous solution
b a
4 Ruchi Pandey a,b , Ram Lakhan Prasad , Nasreen Ghazi Ansari ,
5 Ramesh Chandra Murthy a, *
6 a
Analytical Chemistry Section, CSIR-Indian Institute of Toxicology Research, M.G. Marg, Post Box 80, Lucknow 226001, India
7 b
Department of Chemistry, Faculty of Science, Banaras Hindu University, Varanasi 221005, India

A R T I C L E I N F O A B S T R A C T

Article history: A fundamental investigation for the Cd(II) ions removal from aqueous solutions by NaOH modified
Received 6 March 2014 Desmostachya bipinnata (Kush grass) leaves (MDBL) and Bambusa arundinacea (bamboo) leaves (MBAL)
Received in revised form 11 June 2014 was conducted in batch experiments. The influence of different experimental parameters such as pH,
Accepted 12 June 2014
contact time, initial Cd(II) ion concentration, adsorbent dosage, on the Cd(II) adsorption was studied.
The Cd(II) uptake by MDBL and MBAL was quantitatively evaluated using sorption isotherms. Freundlich
Keywords: and Langmuir isotherm models were used to fit the equilibria data, of which Langmuir model is
Desmostachya bipinnata leaves
considered better in correlation and the maximum adsorption capacity was found to be 15.22 mg g
1 for
Kush grass
Bambusa arundinacea leaves
MDBL and 19.70 mg g
1 for MBAL at room temperature. The kinetic data were found to follow closely the
Bamboo leaves pseudo second order kinetic model by both adsorbents. FTIR and SEM were recorded, before and after
Isotherm adsorption, to explore number and position of the functional groups available for Cd(II) binding on to
Kinetics studied adsorbents and changes in surface morphology of adsorbent. Desorption studies show 94.18%
and 92.08% recovery for adsorbed Cd(II) ions from MDBL and MBAL, respectively using 0.1 N HNO3.
Thermodynamic studies indicated that the adsorption reaction was a spontaneous and exothermic
process. It can be concluded that MDBL and MBAL are low-cost biosorbent alternatives for wastewater
treatment, since both have a considerable high adsorption capacity.
ã 2014 Published by Elsevier Ltd.

8 Introduction because of its low permissible limit (0.005 mg L
1) in drinking 22

water [3]. So many surface chemistry practices for wastewater 23

9 An increased flux of heavy metals in the aquatic environment treatment such as precipitation, adsorption, membrane processes, 24
10 due to their swift use [1] in industries, has led severe threat to ionic exchange, floatation, and others [4,5] have been studied. 25
11 human being. Beyond permitted concentration, they can cause However, because of inherent limitation of such techniques as less 26
12 grave health disorders; therefore, considerable attention has been competent, perceptive operating settings, and production of 27
13 paid to wastewater treatment prior to its discharge in the sludge, they further require costly disposal [6], whereas, adsorp- 28
14 environment. Among these metallic pollutants, Cd(II), an extreme- tion is by far the most versatile and widely used method, and 29
15 ly toxic heavy metal causes a potential risk to environmental and activated carbon is the furthermost commonly used adsorbent [7]. 30
16 human health because it is incorporated into the food chain, Conversely, the use of activated carbon is expensive, so consider- 31
17 mainly by plant uptake [2]. The main anthropogenic pathway able interest has been shown towards the use of other efficient 32
18 through which Cd(II) enters the water bodies is via wastes from sorbent materials, particularly biosorbents [8]. In recent years, 33
19 industrial processes such as electroplating, plastic manufacturing, agricultural by-products have been widely considered for metal 34
20 metallurgical processes, and Cd/Ni batteries. Over exposures may sorption studies including peat, banana pith, pine bark, peanut, 35
21 befall even in conditions where a little amount of Cd(II) found shells, hazelnut shell, rice husk, wood, sawdust, wool, soybean and 36

cottonseed hulls, orange peel, leaves and compost [9–13]. In a 37

previous study we have carried out Cd(II) removal using cucumber 38

* Corresponding author. Tel.: +91 522 223222; fax: +91 522 223222. peel and obtained a maximum adsorption capacity of 7.142 mg g
1 39

[14]. In the adsorption process, various metal-binding mechanisms 40

E-mail address: murthyrc729@gmail.com (R.C. Murthy).

http://dx.doi.org/10.1016/j.jece.2014.06.015
2213-3437/ ã 2014 Published by Elsevier Ltd.

Please cite this article in press as: R. Pandey, et al., Utilization of NaOH modified Desmostachya bipinnata (Kush grass) leaves and Bambusa
arundinacea (bamboo) leaves for Cd(II) removal from aqueous solution, J. Environ. Chem. Eng. (2014), http://dx.doi.org/10.1016/j.
jece.2014.06.015
 G Model
JECE 376 1–10

2 R. Pandey et al. / Journal of Environmental Chemical Engineering xxx (2014) xxx–xxx

41 are thought to be involved, including ion exchange, surface a steady temperature (25  2  C), for 240 min to ensure equilibri- 93
102
101
100
99
98
97
96
95
94
42 adsorption, chemisorption, complexation, and adsorption–com- um. After shaking the flasks for regular intervals, samples were 103
43 plexation [15–18]. withdrawn, filtered and the filtrates were analyzed by atomic 104
44 In the present study, Cd(II) sorption using Desmostachya absorption spectrophotometer (PerkinElmer AAnalyst 300, USA) 105
45 bipinnata (Kush grass) leaves (DBL) and Bambusa arundinacea for the concentration of Cd(II). A first series of sorption experi- 106
46 (bamboo) leaves (BAL), members of true grass family: Poaceae, had ments was carried out with an initial concentration of 20 mg L
1. In 107
47 been studied and as both adsorbents correspond to same family, these experiments the most favorable pH of biosorption was 108
48 their major constituents must be same. These materials are the determined. Subsequently, the influence of adsorbent dosage, 109
49 major organic components of the solid waste, comprising about contact time, initial ion concentration was also evaluated. 110
50 14.6% of total municipal solid waste (MSW) and about 50% of the Percentage metal removal was calculated using the following 111
51 organic fraction of the MSW [19]. However, in the entire world, formula: 112
52 India has the huge rate of biomass production, including organic
53 C0
Ct
wastes, such as grass, leaves and flowers. Therefore, it is essential %R ¼  100 (1)
54 C0
to search for a better use of these abundant agricultural wastes
55 such as, remediation of heavy metal from contaminated aqueous where C0 is initial and Ct is the final concentration of Cd(II). The 113
56 solutions. Both materials found abundantly throughout the year, morphological characteristics of adsorbents were evaluated by 114
57 and these kinds of materials exhibit strong potential due to their using a scanning electron microscope (SEM) and disposition of the 115
58 high content of lignin and cellulose [20] that abide numerous polar functional group present on the adsorbent surface were studied 116
59 functional groups, including phenolic and carboxylic acid groups, before and after biosorption using Fourier transform infrared 117
60 which may be involved in metal binding [21,22]. Due to the low (FTIR) spectrophotometer. 118
61 cost, DBL and BAL are an attractive and inexpensive option for the
62 adsorption of Cd(II) ion from aqueous solution. Further NaOH was Adsorption isotherms studies 119
63 used in the modification process because it can enhance surface
64 characteristics of DBL and BAL with increased adsorption capacity Isotherm studies were recorded by varying the initial concen- 120
65 [23]. The adsorption capacity of modified DBL and BAL (MDBL and tration of Cd(II) solutions from 10 to 150 mg L
1 with MDBL and 121
66 MBAL, respectively) was investigated by batch experiments. The MBAL separately. A known amount of adsorbents was then added 122
67 influences of parameters such as pH, adsorbent dosage, contact into solutions in different flasks followed by agitating them at 123
68 time, initial ion concentration were investigated and the experi- 250 rpm till equilibrium. The metal ion concentrations, retained in 124
69 mental data obtained were evaluated and fitted using adsorption the adsorbent phase qe (mg g
1) which is defined as adsorption 125
70 equilibrium and kinetic models. capacity, was calculated by using the following mass balance 126

equation for the process at equilibrium condition: 127

71 Materials and methods
ðC 0
C t Þ
qe ¼ V (2)
72 W
Adsorbent and chemicals
where V is the volume of solution (L) and W is the mass of 128
73 adsorbate (g). 129
DBL and BAL were obtained from the Indian Institute of
74 Toxicology Research, Gheru Campus (Lucknow, India). Both were
75 Desorption study 130
dried under the sunlight for 2 days then, ground, washed several
76 times with double distilled water (DDW) and afterwards screened
131
77 to obtain 80 mm sized particles. These samples were modified Desorption experiments were performed to consider the
78 practical usefulness of the biosorbents. After the biosorption 132
using 0.5 M NaOH solution with 1:20 for 30 min (solid–liquid ratio)
133
79 [24]. The MDBL and MBAL were again dried at 100  C for 24 h and studies, 0.2 g of metal loaded sorbent were agitated in 100 mL of
80 0.1 M HCl and 0.1 M HNO3 same as described by Witek–Krowiak 134
stored in an airtight container. The physical characteristics of the
81 [25]. After 60 min of contact time the metal concentration in the 135
MDBL and MBAL are presented in Table 1.
136
82 The stock solution of Cd(II) (1000 mg L
1) was prepared in DDW solution was determined. To check the applicability as the best
137
83 using Cd (NO3)24H2O salt (Merck); all working solutions were eluent the sorption desorption steps were repeated five times.
84 prepared by diluting the stock solution with DDW.
Results and discussion 138
85 Biosorption experiments
Characteristic of MDBL and MBAL before and after adsorption 139
86 Batch experiments were executed for adsorption studies. A pre-
87 Presence of functional groups on MDBL and MBAL powder were 140
weighted sample of the adsorbents (MDBL and MBAL) with a
88 analyzed using FTIR, as shown in Fig. 1(A) and (B). Occurrences of 141
measured volume of Cd(II) solution were taken in 100 mL
89 diverse type of functional groups are confirmed by the peaks, and 142
Erlenmeyer flask and stirred in an incubator shaker (250 rpm) at
their detailed illustration is shown in Table 2. Mainly, metal ions 143

were bonded by functional groups such as carboxylic groups 144

(pectin, hemicellulose, and lignin), phenolic groups (lignin and 145

Table 1 146
Physical characteristic of MDBL and MBAL. extractives) and a little amount may also be adsorbed by hydroxyl
(cellulose, lignin, extractives, and pectin) and carbonyl groups 147
Parameter MDBL MBAL 148
(lignin) [26]. After sorption, several functional groups which were
Particle size (mm) 80 80 initially present, disappeared, while some other had their position 149
Particle density 0.144 0.196 150
altered and thus confirming the active participation of bonded OH
Bulk density (g mL
1) 0.127 0.166 151
Porosity (%) 0.113 0.15 groups, secondary amine group, carboxyl groups, C

O stretching
90 Moisture content (%) 10.93 8.30 of ether groups and

C

C

group [3,27] as shown in Fig. 1(A) 152
91 Ash content (%) 2.57 1.42 and (B) and Table 2. Hence, the good sorption properties of both 153
92 Phzpc 5.50 5 MDBL and MBAL towards Cd(II) ions can be ascribed to the 154

Please cite this article in press as: R. Pandey, et al., Utilization of NaOH modified Desmostachya bipinnata (Kush grass) leaves and Bambusa
arundinacea (bamboo) leaves for Cd(II) removal from aqueous solution, J. Environ. Chem. Eng. (2014), http://dx.doi.org/10.1016/j.
jece.2014.06.015
 G Model
JECE 376 1–10

R. Pandey et al. / Journal of Environmental Chemical Engineering xxx (2014) xxx–xxx 3

Fig. 1. FTIR spectra of MDBL (A) and MBAL (B) before and after Cd(II) adsorption.

155 presence of these functional groups on their surfaces. Fig. 2(A) and pH of the solution on the Cd(II) removal efficiency were studied at 168
156 (B) shows SEM images for MDBL and MBAL before and after the different pH ranging from 3.5 to 8.5. A sharp increase in the Cd(II) 169
157 adsorption process, respectively. From Fig. 2(A and B), it is clearly removal was observed from 64.4% to 77.6% and 60.88% to 75.2% at 170
158 visible that before adsorption, both the adsorbents have rough pH 6.5 (Fig. 3) for MDBL and MBAL, respectively and after that with 171
159 heterogeneous porous surface and a large number of steps and a slight decrease, the value became constant because of the 172
160 kinks on the adsorbent surface, with wrecked edges [28]. The saturation of active sites on the adsorbents surface. So the pH 6.5 173
161 change in the morphology of the adsorbent after adsorption was selected as the best pH to study the overall adsorption process. 174
162 indicates that there is a good possibility for Cd(II) ions to be Precipitation of Cd(II) ions was observed at pH 8 [29]. At low pH, 175
163 trapped and adsorbed onto the surface. the little removal efficiency is due to occurrence of higher 176

concentration of protons in the solution which compete with 177

164 Effect of pH the Cd(II) ions for the adsorption sites of the adsorbents. As the pH 178

increases, the H+ concentration decreases, leading to enhanced Cd 179

165 The pH plays a very significant role in the sorption of heavy (II) uptake. The effect of pH can be explained in terms of pHzpc of 180
166 metals by affecting the surface charge of adsorbent, the degree of the adsorbent. The pH at, which the charge of the whole surface is 181
167 ionization, and speciation of adsorbate. Thus, the effects of initial zero is referred as the zero point of charge (pHzpc) and above which 182

Table 2
Functional groups and mode of vibration from the FTIR spectrum of MDBL and MBAL before and after adsorption.

Functional group MDBL Cd(II) loaded MBAL Cd(II) loaded

(cm
1) MDBL (cm
1) MDBL
(cm
1) (cm
1)
Stretching vibration of bonded

OH group on surface 3418.35 3415.14 3402.93 3431.08
Asymmetrical stretching vibration of

CH3 2922.73 2920.52 2922.59 2923.30
Strong stretching vibration of C

O from carboxylic acid in presence of intermolecular H bonding 1631.46 1639.24 1634.58 1644.39
Generation of this peak after adsorption is outcome of an overlapped band of bending vibration of N

Hand – 1516.20 – –
stretching vibration of C

N
C

C stretching of aromatic ring 1380.35 1377.07 1376.61 1514.93
Bending vibration oh OH and stretching vibration of C

O

C in lignin structure 1059.02 1103.39
C

O stretching of carboxylic acid 1246.16 1252.85 – –
Bending vibration of OH and stretching vibration of C

O

C in lignin structure 1049.61 1073.96 – –
Fingerprint region: adsorption cannot be clearly assigned to any particular vibration because they correspond 605.21 664.60 563.42 602.96
to complex interacting vibration systems 466.37 469.10

Please cite this article in press as: R. Pandey, et al., Utilization of NaOH modified Desmostachya bipinnata (Kush grass) leaves and Bambusa
arundinacea (bamboo) leaves for Cd(II) removal from aqueous solution, J. Environ. Chem. Eng. (2014), http://dx.doi.org/10.1016/j.
jece.2014.06.015
 G Model
JECE 376 1–10

4 R. Pandey et al. / Journal of Environmental Chemical Engineering xxx (2014) xxx–xxx

Fig. 2. Scanning electron micrograph showing morphology of MDBL (A) and MBAL (B) before and after Cd(II) adsorption.

183 the surface become negatively charged. The obtained pHzpc of Effect of biosorbent dosage 203
184 MDBL and MBAL is 5 and 5.5, respectively by using the batch
185 equilibration technique [30]. Positively charged Cd(II) species are One of another important parameter that strongly affects the 204
186 soft acids and as a rule the interaction of Cd2+ and Cd(OH)+ with the sorption capacity is the biosorbent dosage. As shown in Fig. 4 with 205
187 negatively charged adsorbent surface containing carboxyl and the increasing adsorbent dosage from 2 to 12 g L
1, it can easily be 206
188 hydroxyl groups are responsible for the sorption of Cd(II) ions and inferred that the percent removal of metal ions boosts from 63.95% 207
189 also supported by FTIR studies. At low pH, particularly below pHzpc to 85.50% and 65.50% to 82.05% for MDBL and MBAL, respectively, 208
190 the Cd2+ and Cd(OH)+ species present in the solution may exchange whereas the amount adsorbed per unit mass decreases. It is 209
191 with H+ from peripheral. Apparently, at very low pH (3), the apparent that the percent removal of heavy metals increases 210
192 presence of higher concentrations of H+ ions in the mixture, owes rapidly with an increase in the dosage of the adsorbents due to the 211
193 electrostatic repulsion between both positively charged adsorbent greater availability of the exchangeable sites or surface area [3], 212
194 surface and metal ion. A decreasing trend in adsorption was also whereas the decrease in Cd(II) uptake with increasing adsorbent 213
195 observed at very high pH also, and this may be due to the formation dosage is mainly due to unsaturation of adsorption sites through 214
196 of soluble hydroxy complexes [31]. Dissociation of the

COOH the adsorption reaction and the similar results were obtained in a 215
197 groups (pKa = 3.8–5.0) is the plausible reason for becoming the study performed by Chen et al. [33]. 216
198 surface of MDBL and MBAL negatively charged at optimum pH 6.5
199 and thus, favorable to the adsorption of Cd(II) at this pH [32]. Cd(II)
Effect of initial ion concentration 217
200 may most likely be bound on the MDBL and MBAL surface via an
201 ion exchange mechanism as following equation:
The Cd(II) ion uptake is particularly reliant on the initial Cd(II) 218
2þ þ concentration. At the lower range, Cd(II) is adsorbed by specific 219
2ð
RCOOHÞ þ Cd ¼ ðRCOOÞ2 Cd þ 2H (3)
active sites, while at higher sides; decreased adsorption is due to 220
202 where


R represents the matrix of the adsorbents. the saturation of adsorption sites and also because of lack of 221

Please cite this article in press as: R. Pandey, et al., Utilization of NaOH modified Desmostachya bipinnata (Kush grass) leaves and Bambusa
arundinacea (bamboo) leaves for Cd(II) removal from aqueous solution, J. Environ. Chem. Eng. (2014), http://dx.doi.org/10.1016/j.
jece.2014.06.015
 G Model
JECE 376 1–10

R. Pandey et al. / Journal of Environmental Chemical Engineering xxx (2014) xxx–xxx 5

Fig. 3. Effect of pH on Cd(II) adsorption by MDBL and MBAL at 25  C (condition:

20 mg L
1 of Cd(II) solution, 250 rpm, 1 g L
1 adsorbent dosage, 60 min). Fig. 5. Effect of initial Cd(II) ion concentration for adsorption process by MDBL and
MBAL at 25  C (condition: 1 g L
1 adsorbent dosage, 250 rpm, 60 min).
222 sufficient surface area to accumulate further available ions. This is
223 due to the competition for the available active sites on the surface. 239
points (Fig. 6). The subsequent increase in contact time had no
224 The influence of the initial Cd(II) concentration on its removal with 240
effect on Cd(II) adsorption.
225 MDBL and MBAL shown in Fig. 5, where a decrease in removal
226 percent from 74.2% to 66.60% and 77.90% to 62.61% (for C0 = 10– 241
Adsorption isotherms
227 150 mg L
1) could be observed, respectively.
The equilibrium isotherm study is very essential for designing 242
228 Effect of contact time 243
adsorption systems and also facilitate the comprehensive of the
interaction involved between adsorbate and adsorbent. The 244
229 The effect of contact time on adsorption was studied up to 245
adsorption data were analyzed Freundlich (1906) and Langmuir
230 240 min. It appeared from Fig. 6 that the metal uptake is very rapid 246
(1918) isotherm models. The linearized forms of the Freundlich
231 up to 90 and 180 min of equilibrium for MBAL and MDBL, 247
isotherm can be expressed as in Eq. (4) [35] and of Langmuir
232 respectively, after that Cd(II) uptake does not significantly change 248
isotherm as in Eq. (5) [35] below:
233 with time. Therefore, 240 min of contact time is chosen to achieve
1
234 the equilibrium [34]. For 20 mg L
1 of Cd(II) concentration with an log qe ¼ log kF þ log C e (4)
235 n
increase in contact time from 10 to 180 min for MDBL and 10 to
236 150 min for MBAL, the percentage Cd(II) sorption increased from
237 36.80% to 89.55% and 29.15% to 90.05%, respectively, and after Ce 1 Ce
¼ þ (5)
238 which a plateau is obtained, which showed saturation of the active qe qmax kL qmax

Fig. 6. Effect of contact time on Cd(II) adsorption by MDBL and MBAL, at 25  C,

Fig. 4. Effect of adsorbent dosage for Cd(II) adsorption by MDBL and MBAL at 25  C
(condition: 20 mg L
1 of Cd(II) solution, 250 rpm, 1 g L
1 adsorbent dosage).
(condition: 20 mg L
1 of Cd(II) solution, 250 rpm, 60 min).

Please cite this article in press as: R. Pandey, et al., Utilization of NaOH modified Desmostachya bipinnata (Kush grass) leaves and Bambusa
arundinacea (bamboo) leaves for Cd(II) removal from aqueous solution, J. Environ. Chem. Eng. (2014), http://dx.doi.org/10.1016/j.
jece.2014.06.015
 G Model
JECE 376 1–10

6 R. Pandey et al. / Journal of Environmental Chemical Engineering xxx (2014) xxx–xxx

Fig. 7. Langmuir isotherm for MDBL and MBAL at 25  C.

249 where Ce (mg L
1) is the equilibrium Cd(II) concentration in admirable qmax data as shown in the Table 3, it is obvious that 284
250 solution, qe and qmax (mg g
1) are the equilibrium and maximum MDBL and MBAL exhibited a favorable combination of a high 285
251 adsorption capacities (mg g
1), 1/n is the heterogeneity factor, number of accessible adsorption sites, and evidenced excellent 286
252 kF (L g
1) and kL(L g
1) are Freundlich and Langmuir constant, promising adsorbents for Cd(II) ions from aqueous solution. 287
253 respectively. The values of Freundlich and Langmuir parameters Freundlich and Langmuir equations have their own limitations 288
254 were obtained based on the linear correlation between the values in describing the equilibrium data adequately. Both are based on 289
255 of (i) log qe vs. log Ce and (ii) (Ce/qe) vs. Ce, respectively. utterly unlike principles, and the fact that the experimental 290
256 Fig. 7(a) and (b) shows the adsorption isotherms of Cd(II) using fallouts fit one or another equation, imitates a purely mathematical 291
257 MDBL and MBAL, respectively. Freundlich isotherm is the most apt [13]. So here it may be concluded from Table 3, that the Cd(II) 292
258 basic relationship describing non-ideal and reversible adsorption, adsorption isotherm exhibit Langmuir behavior with comparative 293
259 valid for heterogeneous surface having non uniform energy high coefficients of determination (R2 > 0.980) than Freundlich 294
260 distribution and is not restricted to monolayer formation [36]. isotherm. 295
261 In the present study (Table 3) at increasing temperature, higher kF
262 values and n > 1 indicated, favorable process [37] and are classified Thermodynamic study 296
263 as L type isotherm reflecting a high affinity between adsorbent and
264 adsorbate thus shows beneficial adsorption for MDBL and MBAL, Langmuir isotherm constant kL for varying temperatures, i.e. 297
265 and is indicative of chemisorption [38]. 298, 308, and 318 K has been used to evaluate the thermodynamic 298
266 The Langmuir model is based on the hypothesis that all binding parameters, the change in Gibbs free energy (DG ), enthalpy (DH ), 299
267 sites are, likewise, active on the energetically homogeneous and entropy (DS ) for the adsorption process [38], and the 300
268 surface, and monolayer surface formation takes place without following equations are used for the calculations for these 301
269 any interaction between the adsorbed molecules [12]. As it can be parameter: 302
270 seen from Table 3, the coefficients of determination (R2 > 0.980) at 
271 varying temperatures proved that the linear fit of the Langmuir DG ¼
RT log kL (6)
272 model agrees well for both the adsorbents.   
273 Initially, on increasing temperature from 298 to 308 K adsorp- DG DS DH
log kL ¼
¼ ¼ (7)
274 tion capacity increases for MDBL and decreasing values were RT R RT
275 noticed from 308 to 318 K. On the other side continuous decrease in where R is the universal gas constant (1.987 cal mol
1) and T is the 303
276 adsorption capacity is observed for MBAL up to 318 K, and it may be temperature (K). The entropy (DS ) and enthalpy (DH ) change 304
277 due to either the damage of adsorbent’s active binding sites [39] or 305
were obtained from the slope and intercept of the plot of log kL
278 increasing propensity of desorption of Cd(II) ions from the against 1 T
1 (Fig. 8), respectively. All the thermodynamic 306
279 interface to the solution [40]. This is because at the higher 307
parameters of the adsorption process are shown in Table 4. As
280 temperature the thickness of the boundary layer decreases and expected, the negative DG value indicates feasibility and 308
281 thus tendency of the metal ion to escape from the biomass surface 309
spontaneity of the adsorption process. The change of the standard
282 to the solution phase increases [41]. This trend in the result 310
free energy decreases with increasing temperature regardless the
283 indicates the exothermic nature of Cd(II) adsorption. The 311
nature of adsorbent, indicate that a better adsorption is actually

Table 3
Adsorption isotherm parameters at different temperatures.

Freundlich Langmuir
2
Temp. kF n R qmax kL R2
(K) (mg1
1/n g
1 L1/n) (mg g
1) (min
1)
MDBL 298 1.251  0.057 1.505  0.002 0.977 15.222  0.162 0.077  0.006 0.997
308 1.460  0.067 1.522  0.045 0.979 19.843  0.570 0.090  0.006 0.992
318 1.552  0.028 1.501  0.006 0.955 15.540  0.085 0.104  0.003 0.995

MBAL 298 1.424  0.025 1.472  0.016 0.977 19.705  0.097 0.064  0.001 0.987
308 1.961  0.020 1.596  0.011 0.949 18.483  0.151 0.107  0.001 0.986
318 2.024  0.061 1.602  0.018 0.933 17.331  0.425 0.135  0.008 0.993

Please cite this article in press as: R. Pandey, et al., Utilization of NaOH modified Desmostachya bipinnata (Kush grass) leaves and Bambusa
arundinacea (bamboo) leaves for Cd(II) removal from aqueous solution, J. Environ. Chem. Eng. (2014), http://dx.doi.org/10.1016/j.
jece.2014.06.015
 G Model
JECE 376 1–10

R. Pandey et al. / Journal of Environmental Chemical Engineering xxx (2014) xxx–xxx 7

Table 4
Thermodynamic parameters at different temperatures for Cd(II) adsorption using
MDBL and MBAL.

Thermodynamic parameters

Temp. DG DH DS

(K) (kJ mol
1) (kJ mol
1) (J mol
1 K
1)
MDBL 298
0.389  0.143
308
1.506  0.174 5.50  0.916 1.58  0.089
318
1.112  0.053

MBAL 298
0.661  0.064

308
1.731  0.031 9.283  6.564 2.673  1.890
318
2.051  0.085

capacity and solid phase sorption has been evaluated, respectively. 332

log ðqe
qt Þ ¼ log qe
k1ad t (8)

t 1 1
¼ þ t (9)
qt kq2e qe
Fig. 8. Plot of log kL vs. 1/T for Cd(II) sorption onto MDBL and MBAL.
qe and qt are adsorption capacities (mg g
1) at equilibrium and at 333

time t, respectively. k1ad is the first order rate constant (L min
1) 334

312 obtained at the higher temperature [42]. Moreover, the standard and k2ad is the rate equilibrium constant (g mg
1 min
1) for pseudo 335

second order kinetics. 336

313 free energy change for multilayer adsorption was more than
314
20 kJ mol
1 and less than zero. It should be noted that the h ¼ k2ad q2e (10)
315 magnitude of DG values is in the range of multilayer adsorption
316 [43]. Each metal ion has to displace more than one ion of the where h is the initial sorption rate (mg g
1 min
1) [49]. 337
317 In the present study, at different initial ion Cd(II) concentration, 338
solvent. The net result corresponds to the endothermic process
339
318 [44]. Moreover, the positive DS value corresponds to the increased all the kinetic data were considered up to 240 min for pseudo-
319 second-order rate model, but for pseudo-first-order rate model, 340
randomness at the solid/liquid interface during the adsorption
320 only initial kinetic data up to 150 and 120 min for MDBL and MBAL, 341
process, which suggests that Cd(II) ions replace some water
321 respectively have been used, because using a whole range of 342
molecules from the solution previously adsorbed on the surface of
322 adsorbent. Positive value of DH shows the endothermic nature of contact time, the calculated values of qe (mg g
1) from pseudo- 343

first-order rate model is physically unacceptable. The pseudo-first- 344

323 reaction [45]. The values of adsorption (DH ) obtained in this study
order rate model does not fit well to the whole range of contact 345
324 (<20 kJ mol
1) are consistent with hydrogen bond and dipole bond
325 time in several other cases also and is generally applicable to the 346
forces for both adsorbents [46].
initial phase of the adsorption processes [49,50]. 347
326 The equilibrium adsorption capacity and the second-order rate 348
Kinetic study
constant were calculated from the slope and the intercept of the 349
327 plot t/qt against t (Fig. 9a and b). A competitively high adsorption 350
Adsorption kinetic studies are important as they provide
328 capacity (qe) was obtained for MBAL than MDBL. The data 351
valuable information about the mechanism of the adsorption
329 illustrated good compliance with the pseudo-second order rate 352
process [47] such as mass transfer and chemical reaction. In the
330 law based on sorption capacity because the coefficients of 353
present study, applicability of the pseudo-first-order (Eq. (8)) [48]
331 determination, R2 from Table 5 were higher than 0.990 for both 354
and pseudo-second-order kinetics (Eq. (9)) [37] based on solid

Fig. 9. Kinetic parameters for the adsorption of Cd(II) on MDBL and MBAL at various initial Cd(II) ion concentrations.

Please cite this article in press as: R. Pandey, et al., Utilization of NaOH modified Desmostachya bipinnata (Kush grass) leaves and Bambusa
arundinacea (bamboo) leaves for Cd(II) removal from aqueous solution, J. Environ. Chem. Eng. (2014), http://dx.doi.org/10.1016/j.
jece.2014.06.015
 G Model
JECE 376 1–10

8 R. Pandey et al. / Journal of Environmental Chemical Engineering xxx (2014) xxx–xxx

Table 5
Parameters of pseudo-first-order and pseudo-second-order kinetics for Cd(II) adsorption using MDBL and MBAL at various initial Cd(II) ion concentration.

Pseudo-first order Pseudo-second order

C0 qe,cal k1ad R2 qe,cal k2ad h R2

(mg L
1) (mg g
1) (min
1) (mg g
1) (g mg1 min
1)
MDBL 20 1.097  0.054 0.008  0.001 0.924 1.882  0.020 0.058  0.004 0.194  0.009 0.997
30 2.105  0.023 0.012  0.001 0.985 2.828  0.006 0.030  0.001 0.236  0.002 0.996
50 3.546  0.014 0.008  0.001 0.978 4.785  0.001 0.010  0.000 0.233  0.001 0.991

MBAL 20 1.528  0.014 0.007  0.001 0.920 2.384  0.007 0.028  0.0002 0.157  0.001 0.991
30 2.880  0.018 0.013  0.001 0.930 3.586  0.025 0.016  0.0004 0.213  0.003 0.990
50 5.389  0.092 0.014  0.001 0.963 5.950  0.007 0.011  0.0004 0.396  0.002 0.990

Table 6
Intra-particle diffusion parameters for Cd(II) adsorption using MDBL and MBAL at various initial Cd(II) ion concentration.

Intra particle diffusion

C0 I ki1 R2 I ki2 R2 I ki3 R2

(mg L
1) (mg g
1) (mg g
1 min
1/2) (mg g
1) (mg g
1 min
1/2) (mg g
1) (mg g
1 min
1/2)
MDBL 20
0.239  0.061 0.308  0.016 0.996 1.049  0.070 0.057  0.007 0.927 2.009  0.029
0.018  0.005 0.794
30 0.050  0.111 0.316  0.026 0.9967 2.092  0.154 0.046  0.013 0.9841 2.399  0.361
0.007  0.002 0.456
50 0.244  0.551 0.301  0.238 0.962 2.830  0.010 0.009  0.0002 0.999 4.456  0.021
0.0002  0.001 0.865

MBAL 20 0.660  0.127 0.566  0.075 0.985 1.125  0.010 0.160  0.101 0.965 2.44  0.075
0.010  0.009 0.927
30
1.286  0.658 0.172  0.029 0.989 1.432  1.155 0.040  0.008 0.735 3.486  0.127 0.049  0.006 0.921
50 0.742  0.198 0.485  0.043 0.985 2.718  1.143 0.247  0.110 0.913 5.725  0.180
0.012  0.011 0.657

355 MDBL and MBAL. It can also be perceived by values of Table 5 that, Sorption mechanism 372
356 for both the adsorbents, with an increase in initial metal
357 concentration, the adsorption capacity increases while the rate The kinetic data were analyzed by intraparticle diffusion model 373
358 constant of adsorption (k2ad) decreases. A similar observation was (Eq. (11)) to elucidate the key steps involved during the adsorption 374
359 also reported by some earlier researchers [49]. The observed process. 375
360 decrease in the rate constants with an increase in initial metal ion
361 concentration may be because, at higher concentration, the qt ¼ ki t0:5 þ I (11)
362 average distance between the adsorbed ion is contracted to a
363 point where each affect the charge distribution of its adjacent ions. ki is the intra-particle diffusion rate constant (mg g
1 min0.5). 376

364 In this direction, the kinetic data obtained by plotting qt vs. t0.5 377
The second-order rate constant decreases with an increase in
365 plays a significant role to understand the mechanism of adsorp- 378
initial Cd(II) concentration, while the initial sorption rate, h,
366 tion: as migration of metal species from the solution to adsorbent, 379
generally increases with an increasing initial Cd(II) concentration
367 diffusion, intraparticle diffusion through boundary layer and 380
at all temperatures. This interaction can alter the ability of the ions
368 adsorption to the internal sorbent surface. Table 6 shows that 381
to adsorb onto adsorbent, hence higher concentration of metal ions
369 with an increase in the initial Cd(II) concentration, the intra- 382
may limit the ability of the biomass to adsorb metal ions and
370 particle diffusion rate constant (ki) also increases because ki is 383
consequently sorption process may require several cycles in order
371 directly related to qe and intra-particle diffusivity (I). 384
to meet regulatory standards [31].

Fig. 10. Intra particle diffusion model for Cd(II) adsorption by MDBL and MBAL at various initial Cd(II) ion concentrations.

Please cite this article in press as: R. Pandey, et al., Utilization of NaOH modified Desmostachya bipinnata (Kush grass) leaves and Bambusa
arundinacea (bamboo) leaves for Cd(II) removal from aqueous solution, J. Environ. Chem. Eng. (2014), http://dx.doi.org/10.1016/j.
jece.2014.06.015
 G Model
JECE 376 1–10

R. Pandey et al. / Journal of Environmental Chemical Engineering xxx (2014) xxx–xxx 9

385 The plots of qt vs. t0.5 at different initial Cd(II) ion concentrations Acknowledgments 445
386 (Fig. 10a and b) show multi-linearity characterizations for both the
387 adsorbents, indicates the occurrence of a three step adsorption The authors would like to acknowledge and extend their 446
388 process [51]. For all three stages, the intra particle diffusion heartfelt gratitude to the Director, CSIR-Indian Institute of 447
389 constant (ki1, ki2, and ki3) for MDBL and MBAL are shown in Toxicology Research, Lucknow, and to, the HOD, Department of 448
390 Table 6, that shows first sharp section is the external surface Chemistry, Faculty of Science, BHU, Varanasi for taking interest in 449
391 adsorption or an instantaneous adsorption stage, then intraparticle the study. The authors thank the Council of Science and 450
392 diffusion decelerated down and stabilized [52]. The initial kinetic Technology, Uttar Pradesh, India (Project code, GAP-271) for 451
393 data do not pass through the origin for both the absorbents, so on providing their financial support for this research work. 452
394 the basis of these data it is obvious that, intra-particle diffusion is
395 not the sole rate controlling step [53]. So here the overall
References 453
396 mechanism involves adsorption and intra-particle diffusion.
[1] B. Volesky, Z.R. Holan, Biosorption of heavy metals, Biotechnol. Progress 11
397 Desorption 454
(1995) 235–250, doi:http://dx.doi.org/10.1021/bp00033a001. 7619394.
[2] E.A. Ayuso, Cadmium in soil-plant systems: an overview, Int. J. Environ. Poll. 33
(2008) 275–291, doi:http://dx.doi.org/10.1504/IJEP.2008.019399. 455
398 Apart from adsorption, desorption also plays an important role [3] M.M. Rao, A. Ramesh, G.P. Rao, K. Seshaiah, Removal of copper and cadmium
399 to define the versatility of an adsorbent as it allows reuse of 456
from the aqueous solutions by activated carbon derived from Ceiba pentandra
400 457
adsorbent and recovering of valuable heavy metals. Desorption hulls, J. Hazard. Mater. 129 (2006) 123–129, doi:http://dx.doi.org/10.1016/j.
jhazmat.2005.08.018. 16191464. 458
401 studies were carried using 0.1 N HNO3 and 0.1 N HCl. Results
402 [4] S. Kocaoba, G. Akcin, Removal of chromium (III) and cadmium (II) from
showed that MDBL achieved 94.18% and 93.65% desorption of aqueous solutions, Desalination 180 (2005) 151–156, doi:http://dx.doi.org/ 459
403 460
adsorbed Cd(II) ions using HNO3 and HCl, whereas for MBAL, 10.1016/j.desal.2004.12.034.
404 attained desorption is 92.08% using HNO3 and 91.60% using HCl, [5] V. Govindasamy, T. Rengasamy, D.K. Mahendra Das, Removal of Cd2+ ions from
aqueous solution using live and dead Bacillus subtilis, Chem. Eng. Res. Bull. 15 461
405 respectively. It indicates that HNO3 acts as a better eluting agent for 462
(2011) 18–24.
406 Cd(II) ions from the used biosorbent than HCl. After the desorption [6] S.S. Ahluwalia, D. Goyal, Microbial and plant derived biomass for removal of
407 heavy metals from wastewater, Bioresour. Technol. 98 (2007) 2243–2257, doi: 463
of Cd(II) ions, both sorbents were washed thoroughly with DDW. 464
408 http://dx.doi.org/10.1016/j.biortech.2005.12.006. 16427277.
Five cycles of successive sorption–desorption were carried out to [7] A.M. Starvin, T.P. Rao, Removal and recovery of mercury(II) from hazardous
409 test the reusability of MDBL and MBAL using 0.1 N HNO3 and the 465
wastes using 1-(2-thiazolylazo)-2-naphthol functionalized activated carbon
410 as solid phase extractant, J. Hazard. Mater. 113 (2004) 75–79, doi:http://dx.doi. 466
outcome indicated that the adsorption capacity decreases in the 467
411 org/10.1016/j.jhazmat.2004.04.021. 15363516.
range of 93.75–80% and 91.13–73.80% of HNO3 regenerated MDBL [8] J.C. Ng, W.H. Cheung, G. McKay, Equilibrium studies for the sorption of lead
412 and MBAL, respectively. 468
from effluents using chitosan, Chemosphere 52 (2003) 1021–1030, doi:http://
dx.doi.org/10.1016/S0045-6535(03)00223-6. 12781235. 469
413 [9] B. Nagy, A. Ma ica
neanu, C. Indolean, S. Burca
, L. Silaghi-Dumitrescu, C. Majdik,
Comparison of MDBL and MBAL with other adsorbents Cadmium(II) ions removal from aqueous solutions using Romanian untreated fir 470
tree sawdust a green biosorbent, Acta Chim. Slov. 60 (2013) 263–273. 23878929. 471
414 The adsorption capacity of Cd(II) onto MDBL and MBAL was [10] A. Saeed, M. Iqbal, W.H. Höll, Kinetics, equilibrium and mechanism of CD2+
removal from aqueous solution by mungbean husk, J. Hazard. Mater. 168 (2009) 472
415 noticeable as compared with other NaOH treated adsorbents
1467–1475, doi:http://dx.doi.org/10.1016/j.jhazmat.2009.03.062. 19386413. 473
416 reported in literature as sawdust (73.62 mg g
1) [54], Juniper fiber [11] S.M. Shaheen, F.I. Eissa, K.M. Ghanem, H.M. Gamal El-Din, F.S. Al Anany, Heavy
417 (29.54 mg g
1) [55], rice husk (20.24 mg g
1) [56], coconut bagasse metals removal from aqueous solutions and wastewaters by using various 474
475
418 (17.51 mg g
1) [57] and spent grains (17.3 mg g
1) [58]. It can be byproducts, J. Environ. Manage. 128 (2013) 514–521, doi:http://dx.doi.org/
476
419 10.1016/j.jenvman.2013.05.061. 23831673.
observed that a pH near about 6.0 was found to be an optimum in [12] N.-c. Feng, X.-y. Guo, S. Liang, Kinetic and thermodynamic studies on
420 nearly all cases with the same modification method. The biosorption of Cu(II) by chemically modified orange peel, Trans. Nonferrous 477
421 Met. Soc. China 19 (2009) 1365–1370, doi:http://dx.doi.org/10.1016/S1003- 478
adsorption capacity differences of metal uptake are due to the 479
422 6326(08)60451-3.
properties of each adsorbent such as structure, functional groups [13] P. Vassileva, A. Detcheva, I. Uzunov, S. Uzunova, Removal of metal ions from
423 and surface area. Thus, the capacities found in this work with 480
aqueous solutions using pyrolyzed rice husks: adsorption kinetics and
481
424 MDBL (19.84 mg g
1) and MBAL (19.71 mg g
1) are significantly equilibria, Chem. Eng. Commun. 200 (2013) 1578–1599, doi:http://dx.doi.
482
425 org/10.1080/00986445.2012.755519.
related to other. [14] R. Pandey, N.G. Ansari, R.C. Murthy, R.L. Prasad, Cd(II) adsorption from aqueous
solution onto Cucumis sativus peel: equilibrium, thermodynamic and kinetic 483
426 study, J. Ecophysiol. Occup. Health 13 (2013) 75–84. 484
Conclusion
[15] B. Alyüz, S. Veli, Kinetics and equilibrium studies for the removal of nickel and
zinc from aqueous solutions by ion exchange resins, J. Hazard. Mater. 167 (2009) 485
427 In this detailed study, the NaOH modified DBL and BAL have 486
482–488, doi:http://dx.doi.org/10.1016/j.jhazmat.2009.01.006. 19201087.
428 been found to be very effective biosorbents for Cd(II) ions removal [16] A. Kumar, N.N. Rao, S.N. Kaul, Alkali-treated straw and insoluble straw
xanthate as low cost adsorbents for heavy metal removal – preparation, 487
429 from aqueous solution. The data of the present study is
characterization and application, Bioresour. Technol. 71 (2000) 133–142, doi: 488
430 comparable, as the both materials represent same family. All the 489
http://dx.doi.org/10.1016/S0960-8524(99)00064-4.
431 operational parameters such as the pH, adsorbent dosage, contact [17] X. Gu, L.J. Evans, Surface complexation modelling of Cd(II), Cu(II), Ni(II), Pb(II)
432 and Zn(II) adsorption onto kaolinite, Geochim. Cosmochim. Acta 72 (2008) 490
time and initial metal ion concentrations evidently affected the 491
433 267–276, doi:http://dx.doi.org/10.1016/j.gca.2007.09.032.
removal efficiency. The Langmuir adsorption isotherm fits well to [18] I.A.H. Schneider, J. Rubio, R.W. Smith, Biosorption of metals onto plant
434 the equilibrium adsorption data and suggest that the monolayer biomass: exchange adsorption or surface precipitation? Int. J. Miner. Process. 492
435 62 (2001) 111–120, doi:http://dx.doi.org/10.1016/S0301-7516(00)00047-8. 493
and homogeneous adsorption process take place. The adsorption
436 [19] B.H. Hameed, Grass waste: a novel sorbent for the removal of basic dye from
process follows a pseudo-second-order kinetics rate model. The aqueous solution, J. Hazard. Mater. 166 (2009) 233–238, doi:http://dx.doi.org/ 494
437 overall mechanism involves adsorption and intra-particle diffu- 495
10.1016/j.jhazmat.2008.11.019. 19111987.
438 sion. Regeneration of used MDBL and MBAL can be performed [20] D.G.J. Mann, N. Labbé, R.W. Sykes, K. Gracom, L. Kline, I.M. Swamidoss, J.N.
Burris, M. Davis, C.N. Stewart, Rapid assessment of lignin content and structure 496
439 efficiently using 0.1 N HNO3 as an eluting agent. The adsorption in switchgrass (Panicum virgatum L.) grown under different environmental 497
440 process was spontaneous and exothermic under natural con- 498
conditions, BioEnergy Res. 2 (2009) 246–256, doi:http://dx.doi.org/10.1007/
441 s12155-009-9054-x. 499
ditions. These results demonstrate the remarkable potential of
442 [21] J.T. Matheickal, Q. Yu, G.M. Woodburn, Biosorption of cadmium(II) from
MDBL and MBAL as the low-cost substitutes with a considerable 500
aqueous solutions by pre-treated biomass of marine alga Durvillaea potatorum,
443 high adsorption capacity of 15.22 mg g
1 and 19.70 mg g
1, Water Res. 33 (1999) 335–342, doi:http://dx.doi.org/10.1016/S0043-1354(98) 501
444 502
respectively at room temperature. 00237-1.

Please cite this article in press as: R. Pandey, et al., Utilization of NaOH modified Desmostachya bipinnata (Kush grass) leaves and Bambusa
arundinacea (bamboo) leaves for Cd(II) removal from aqueous solution, J. Environ. Chem. Eng. (2014), http://dx.doi.org/10.1016/j.
jece.2014.06.015
 G Model
JECE 376 1–10

10 R. Pandey et al. / Journal of Environmental Chemical Engineering xxx (2014) xxx–xxx

[22] Y.P. Ting, I.G. Prince, F. Lawson, Uptake of cadmium and zinc by the alga Mater. 141 (2007) 258–263, doi:http://dx.doi.org/10.1016/j.jhaz- 547
503 chlorella vulgaris: II. Multi-ion situation, Biotechnol. Bioeng. 37 (1991) 445– mat.2006.06.124. 16930832. 548
504 455, doi:http://dx.doi.org/10.1002/bit.260370506. 18597390. [41] M. Horsfall Jr., A.I. Spiff, Sorption of lead, cadmium, and zinc on sulfur-
[23] L. Ghali, S. Msahli, M. Zidi, F. Sakli, Effect of pre-treatment of luffa fibres on the containing chemically modified wastes of fluted pumpkin (Telfairia occiden- 549
505 structural properties, Mater. Lett. 63 (2009) 61–63, doi:http://dx.doi.org/ talis Hook f.), Chem. Biodivers. 2 (2005) 373–385, doi:http://dx.doi.org/ 550
506 10.1016/j.matlet.2008.09.008. 10.1002/cbdv.200590017. 551
[24] M.L. Carvalho, R. Jr. Sousa Jr, U.F. Rodríguez-Zúñiga, C.A.G. Suarez, D.S. [42] A.B. Zaki, M.Y. El-Sheikh, J. Evans, S.A. El-Safty, Kinetics and mechanism of the
507 Rodrigues, R.C. Giordano, R.L.C. Giordano, Kinetic study of the enzymatic sorption of some aromatic amines onto Amberlite IRA-904 anion-exchange 552
508 hydrolysis of sugarcane bagasse, Braz. J. Chem. Eng. 30 (2013) 437–447, doi: resin, J. Colloid Interface Sci. 221 (2000) 58–63, doi:http://dx.doi.org/10.1006/ 553
509 http://dx.doi.org/10.1590/S0104-66322013000300002. jcis.1999.6553. 10623452. 554
[25] A. Witek-Krowiak, Application of beech sawdust for removal of heavy metals [43] Z. Bekçi, Y. Seki, M.K. Yurdakoç, Equilibrium studies for trimethoprim
510 from water: biosorption and desorption studies, Eur. J. Wood Wood Prod. 71 adsorption on montmorillonite KSF, J. Hazard. Mater. 133 (2006) 233–242, 555
511 (2013) 227–236, doi:http://dx.doi.org/10.1007/s00107-013-0673-8. doi:http://dx.doi.org/10.1016/j.jhazmat.2005.10.029. 16310307. 556
[26] Y.P. Prasanna Kumar, P. King, V.S.R.K. Prasad, Adsorption of zinc from aqueous [44] B.K. Singh, N.S. Rawat, Comparative sorption equilibrium studies of toxic
512 solution using marine green algae – Ulva fasciata sp, Chem. Eng. J. 129 (2007) phenols on fly ash and impregnated fly ash, J. Chem. Technol. Biotechnol. 61 557
513 161–166, doi:http://dx.doi.org/10.1016/j.cej.2006.10.023. (1994) 307–317, doi:http://dx.doi.org/10.1002/jctb.280610405. 558
[27] P.X. Sheng, Y.-P. Ting, J.P. Chen, L. Hong, Sorption of lead, copper, cadmium, [45] E. Malkoc, Y. Nuhoglu, Determination of kinetic and equilibrium parameters of
514 zinc, and nickel by marine algal biomass: characterization of biosorptive the batch adsorption of Cr(VI) onto waste acorn of Quercus ithaburensis, Chem. 559
515 capacity and investigation of mechanisms, J. Colloid Interface Sci. 275 (2004) Eng. Process. 46 (2007) 1020–1029, doi:http://dx.doi.org/10.1016/j. 560
516 131–141, doi:http://dx.doi.org/10.1016/j.jcis.2004.01.036. 15158390. cep.2007.05.007. 561
[28] K.G. Bhattacharyya, A. Sharma, Adsorption of Pb(II) from aqueous solution by [46] N.F. Cardoso, E.C. Lima, B. Royer, M.V. Bach, G.L. Dotto, L.A.A. Pinto, T. Calvete,
517 Azadirachta indica (Neem) leaf powder, J. Hazard. Mater. 113 (2004) 97–109, Comparison of Spirulina platensis microalgae and commercial activated carbon 562
518 doi:http://dx.doi.org/10.1016/j.jhazmat.2004.05.034. 15363519. as adsorbents for the removal of reactive Red 120 dye from aqueous effluents, J. 563
[29] R. Leyvaramos, L.A. Bernaljacome, I. Acostarodriguez, Adsorption of cadmium Hazard. Mater. 241–242 (2012) 146–153, doi:http://dx.doi.org/10.1016/j. 564
519 (II) from aqueous solution on natural and oxidized corncob, Sep. Purif. Technol. jhazmat.2012.09.026. 23040660. 565
520 45 (2005) 41–49, doi:http://dx.doi.org/10.1016/j.seppur.2005.02.005. [47] M.I. El-Khaiary, G.F. Malash, Y.-S. Ho, On the use of linearized pseudo-second-
[30] J.B. Stankovic, S.K. Milonjic, S.P. Zec, The influence of chemical and thermal order kinetic equations for modeling adsorption systems, Desalination 257 566
521 treatment on the point of zero charge of hydrous zirconium oxide, J. Serbian (2010) 93–101, doi:http://dx.doi.org/10.1016/j.desal.2010.02.041. 567
522 Chem. Soc. 78 (2013) 987–995, doi:http://dx.doi.org/10.2298/JSC121010149S. [48] H. Yuh-Shan, Citation review of Lagergren kinetic rate equation on adsorption
[31] C. Raji, G.N. Manju, T.S. Anirudhan, Removal of heavy metal ions from water reactions, Scientometrics 59 (2004) 171–177, doi:http://dx.doi.org/10.1023/B: 568
523 using sawdust-based activated carbon, Indian J. Eng. Mater. Sci. 4 (1997) SCIE.0000013305.99473.cf. 569
524 254–260. [49] Y.S. Ho, G. McKay, The sorption of lead(II) ions on peat, Water Res. 33 (1999)
[32] X. Huang, N.Y. Gao, Q.L. Zhang, Thermodynamics and kinetics of cadmium 578–584, doi:http://dx.doi.org/10.1016/S0043-1354(98)00207-3. 570
525 adsorption onto oxidized granular activated carbon, J. Environ. Sci. (China) 19 [50] S. Chatterjee, S.H. Woo, The removal of nitrate from aqueous solutions by
526 (2007) 1287–1292, doi:http://dx.doi.org/10.1016/S1001-0742(07)60210-1. chitosan hydrogel beads, J. Hazard. Mater. 164 (2009) 1012–1018, doi:http:// 571
527 18232220. dx.doi.org/10.1016/j.jhazmat.2008.09.001. 18977085. 572
[33] G. Chen, G. Zeng, L. Tang, C. Du, X. Jiang, G. Huang, H. Liu, G. Shen, Cadmium [51] F.C. Wu, R.L. Tseng, R.S. Juang, Comparisons of porous and adsorption
528 removal from simulated wastewater to biomass byproduct of Lentinus edodes, properties of carbons activated by steam and KOH, J. Colloid Interface Sci. 283 573
529 Bioresour. Technol. 99 (2008) 7034–7040, doi:http://dx.doi.org/10.1016/j. (2005) 49–56, doi:http://dx.doi.org/10.1016/j.jcis.2004.08.037. 15694423. 574
530 biortech.2008.01.020. 18313919. [52] W.H. Cheung, Y.S. Szeto, G. McKay, Intraparticle diffusion processes during acid
[34] N.-c. Feng, X.-y. Guo, Characterization of adsorptive capacity and mechanisms dye adsorption onto chitosan, Bioresour. Technol. 98 (2007) 2897–2904, doi: 575
531 on adsorption of copper, lead and zinc by modified orange peel, Trans. http://dx.doi.org/10.1016/j.biortech.2006.09.045. 17110098. 576
532 Nonferrous Met. Soc. China 22 (2012) 1224–1231, doi:http://dx.doi.org/ [53] Ö. Gerçel, H.F. Gerçel, Adsorption of lead(II) ions from aqueous solutions by
533 10.1016/S1003-6326(11)61309-5. activated carbon prepared from biomass plant material of Euphorbia rigida, 577
[35] M.A. Tofighy, T. Mohammadi, Adsorption of divalent heavy metal ions from Chem. Eng. J. 132 (2007) 289–297, doi:http://dx.doi.org/10.1016/j. 578
534 water using carbon nanotube sheets, J. Hazard. Mater. 185 (2011) 140–147, doi: cej.2007.01.010. 579
535 http://dx.doi.org/10.1016/j.jhazmat.2010.09.008. 20926186. [54] S.Q. Memon, N. Memon, S.W. Shah, M.Y. Khuhawar, M.I. Bhanger, Sawdust – a
[36] K.Y. Foo, B.H. Hameed, Insights into the modeling of adsorption isotherm green and economical sorbent for the removal of cadmium(II) ions, J. Hazard. 580
536 systems, Chem. Eng. J. 156 (2010) 2–10, doi:http://dx.doi.org/10.1016/j. Mater. 139 (2007) 116–121, doi:http://dx.doi.org/10.1016/j.jhaz- 581
537 cej.2009.09.013. mat.2006.06.013. 16844287. 582
[37] Y.S. Ho, G. McKay, The kinetics of sorption of divalent metal ions onto [55] S.H. Min, J.S. Han, E.W. Shin, J.K. Park, Improvement of cadmium ion removal by
538 sphagnum moss peat, Water Res. 34 (2000) 735–742, doi:http://dx.doi.org/ base treatment of juniper fiber, Water Res. 38 (2004) 1289–1295, doi:http:// 583
539 10.1016/S0043-1354(99)00232-8. dx.doi.org/10.1016/j.watres.2003.11.016. 14975662. 584
[38] H.K. Boparai, M. Joseph, D.M. O'Carroll, Kinetics and thermodynamics of [56] U. Kumar, M. Bandyopadhyay, Sorption of cadmium from aqueous solution
540 cadmium ion removal by adsorption onto nano zerovalent iron particles, J. using pretreated rice husk, Bioresour. Technol. 97 (2006) 104–109, doi:http:// 585
541 Hazard. Mater. 186 (2011) 458–465, doi:http://dx.doi.org/10.1016/j.jhaz- dx.doi.org/10.1016/j.biortech.2005.02.027. 15936939. 586
542 mat.2010.11.029. 21130566. [57] F.W. Sousa, A.G. Oliveira, J.P. Ribeiro, D. De Keukeleire, A.F. Sousa, R.F.
[39] A. Ozer, D. Ozer, Comparative study of the biosorption of Pb(II), Ni(II) and Cr Nascimento, Single and multielementary isotherms of toxic metals in aqueous 587
543 (VI) ions onto S. cerevisiae: determination of biosorption heats, J. Hazard. solution using treated coconut shell powder, Desalin. Water Treat. 36 (2011) 588
544 Mater. 100 (2003) 219–229, doi:http://dx.doi.org/10.1016/S0304-3894(03) 289–296, doi:http://dx.doi.org/10.5004/dwt.2011.2597. 589
545 00109-2. 12835024. [58] K.S. Low, C.K. Lee, S.C. Liew, Sorption of cadmium and lead from aqueous
[40] K. Saltali, A. Sari, M. Aydin, Removal of ammonium ion from aqueous solution solutions by spent grain, Process Biochem. 36 (2000) 59–64, doi:http://dx.doi. 590
546 by natural Turkish (Yildizeli) zeolite for environmental quality, J. Hazard. org/10.1016/S0032-9592(00)00177-1. 591

Please cite this article in press as: R. Pandey, et al., Utilization of NaOH modified Desmostachya bipinnata (Kush grass) leaves and Bambusa
arundinacea (bamboo) leaves for Cd(II) removal from aqueous solution, J. Environ. Chem. Eng. (2014), http://dx.doi.org/10.1016/j.
jece.2014.06.015
American Journal of Environmental Protection, 2014, Vol. 2, No. 3, 51-58
Available online at http://pubs.sciepub.com/env/2/3/1
© Science and Education Publishing
DOI:10.12691/env-2-3-1

Pb(II) Removal from Aqueous Solution by

Cucumissativus (Cucumber) Peel: Kinetic, Equilibrium
& Thermodynamic Study
Ruchi Pandey1,2, Nasreen Ghazi Ansari1, Ram Lakhan Prasad2, Ramesh Chandra Murthy1,*
1
Analytical Chemistry Section, CSIR-Indian Institute of Toxicology Research, 80- M.G. Road, Lucknow, India
2
Department of Chemistry, Faculty of Science, Banaras Hindu University, Varanasi, India
*Corresponding author: murthyrc729@gmail.com
Received June 03, 2014; Revised June 14, 2014; Accepted June 23, 2014
Abstract Cucumissativus peel (CSP), was investigated as a new adsorbent for Pb(II) removal from aqueous
solution under several varying conditions such as pH, adsorbent dosage, and contact time. Maximum metal sorption
was found to occur at initial pH 5.0. The adsorption capacity of CSP was found to be 28.25mg/g for initial Pb(II)
concentration of 25 mg/l at 25°C. The equilibrium data best fitted to the Langmuir adsorption isotherm model. Batch
adsorption models, based on the assumption of the pseudo first-order and pseudo second order mechanism were
applied to examine the kinetics of the adsorption. The results showed that kinetic data were followed pseudo second-
order model than the pseudo first-order equation. With no loss in the Pb(II) ion removal efficiency, CSP could be
regenerated using 1M HNO3 during repeated sorption–desorption cycles and showed recovery of 93.5% for 25mg/l
of Pb(II) ion concentration. Comprehensive characterization parameters using FTIR, and SEM were recorded before
and after adsorption to explore the number and position of the functional groups available for Pb(II) binding onto
adsorbent and changes in surface morphology of the adsorbent.
Keywords: Cucumis sativus, adsorption, equilibrium, kinetic, sorption-desorption, recovery, FTIR, SEM
Cite This Article: Ruchi Pandey, Nasreen Ghazi Ansari, Ram Lakhan Prasad, and Ramesh Chandra Murthy,
“Pb(II) Removal from Aqueous Solution by Cucumissativus (Cucumber) Peel: Kinetic, Equilibrium &
Thermodynamic Study.” American Journal of Environmental Protection, vol. 2, no. 3 (2014): 51-58. doi:
10.12691/env-2-3-1.

amounts of chemicals and at low concentrations of metals,

are incompetent [5].
1. Introduction This paper describes the use of a novel adsorbent, dried
Cucumber peel (Cucumissativus peel, CSP) for the
Heavy metal ions present in the environment especially removal of Pb(II) ions from aqueous solution through
from the transition series are of foremost concern due to batch experiments. Cucumber peel is generated as a
their toxicity to several life forms. Amongst them Lead is residue of the food processing, and has no significant
a non-essential metal for human consumption and due to industrial and commercial use. CSP is Fibrous material,
its widespread existence in natural systems and the mostly composed of cellulose, hemi-cellulose, lignin, and
propensity to accumulate as it moves up in the food chain, chlorophyll pigments [6]. In our previous study [7], it is
represent imperative environmental and occupational also found that it contain carboxyl and hydroxyl functional
hazards. Concern over the problem of heavy metal groups, thus making it a potential adsorbent material for
pollution has led to develop alternative technologies for several metals through ion–exchange and/or complexation
effective removal of pollutants from aqueous effluents mechanism. The main objective of this study was to
explaining the use of several agro waste materials and by- investigate the effects of various parameters such as
products of cellulosic origin for sorption of heavy metals solution pH, adsorbent dosage, and contact time on the
[1]. It is evident that low-cost adsorbents have adsorption efficiency of Pb(II) ions on CSP.In most of the
demonstrated outstanding removal capabilities for certain batch studies, effect of individual parameter of the
metal ions as compared to activated carbon [2]. On the adsorption process has been investigated maintaining
other hand, conventional methods can be used such as ion other parameter constant at unspecified levels [8].
exchange, chemical oxidation and chemical precipitation Equilibrium, kinetics and thermodynamic studies were
for eradicating heavy metal ions from aqueous solution. performed to determine potential application of CSP for
However, some disadvantages of these technologies, such metal ion removal.
as high cost, sensitive operating conditions and production
of secondary sludge [3,4]. These methods use huge
2. Methodology
52 American Journal of Environmental Protection

2.1. Chemicals to determine the optimum pH value and for this, pH of the
solution was varied from 3±0.1 to 8±0.1. A trend of
All reagents used including Standard Pb(II) 1000mg/l increasing metal ion binding with increasing pH from 3.0
solution were of analytical grade purchased from Merck, to 5.0 could be observed that is similar to results of some
India. The experimental stock (1000mg/l) solution was researcher [11]. Under highly acidic conditions (pH ≈ 3.0)
prepared from Lead Nitrate Pb(NO3)2 and further dilutions the metal sorption efficiency was very small, and this
were prepared from this stock solution with the use of lower efficiency is due to the presence of high
deionized distilled water produced by a pure hyper concentration of H+ ions/hydronium ions (H3O+) and also
filtration water system (Millipore, Water purification partly because of the chemical speciation of Pb(II) [12].
system, USA). For the pH study, pH of the solutions was Besides, at higher pH value, fewer H+ ions exist, and
maintained by using 0.1N HNO3/0.1N NaOH. Standard consequently, Pb(II) ions have a better chance to bind free
lab ware and glassware cleaned with HNO3 and rinsed binding sites. Later, when the pH enters basic conditions
with double distilled water (DDW) were used all over. All beyond pH 8 (Eq.1&2), lead hydroxide formation takes
the solutions were analyzed for Lead on a flame atomic place due to the dissolution of Pb(OH)2 and as a result, the
absorption spectrophotometer (AAS; Perkin-Elmer, adsorption rate decreases.
Analyst 300, USA), using Electrodeless discharge lamp.
+
Pb 2+ + H 2 O  Pb ( OH ) + H + (1)
2.2. Adsorbent Preparation
CSP was collected in bulk from local market. It was Pb 2+ + 2H 2 O  Pb ( OH )2 + 2H + (2)
thoroughly rinsed with DDW to remove dust and soluble
As shown in Figure 1, results revealed that the optimum
material and allowed to dry at 100°C for 24 hours. The
biosorption pH value for Pb(II) removal is pH 5.0. After
dried CSP were crushed, ground using a domestic mixer.
pH 5.0, a plateau was obtained with slight decrease in
The ground materials were then sieved to constant particle
Pb(II) sorption.
sizes of +60 to −85 mesh [9] stored in a desiccator for
further use. Characterization of CSP including percent ash
content, moisture content, particle density, bulk density,
and porosity was summarized in Table 1.

Table 1. Physical Characteristics of CSP

Parameters
Particle density 0.235
Bulk density (gml−1) 0.127
Porosity (%) 0.15
Moisture content (%) 13.5
Ash content (%) 8.5

2.3. Desorption and Regeneration

Desorption procedure was followed as described by
[10]. A sample volume of 25mL, containing 25 mg/l of
Pb(II) ions, was transferred into a beaker; 10mL of buffer
Figure 1. Effect of pH on Pb(II) sorption by CSP at 25°C (Condition:
solution was added. After a fast shaking, 1 g/l of CSP was
25mg/l Pb(II), 160 rpm, 1g/l Adsorbent dosage, 60 min)
added and the mixture was shaken again for 60 min at 160
rpm. The system was filtered with What man filter paper. 3.1.2. Effect of Adsorbent Dosage
The filter and constituents were washed with DDW. In
order to elute the adsorbed analytes onto CSP, 8–10mL of
1M HNO3 was used. The final volume was completed to
25 ml with 1M HNO3. Pb(II) in the final solution were
determined by flame atomic absorption spectrometry. The
same procedure was applied to the blank solution. In order
to reuse CSP for next set of experiment, it was washed
with excess of 1M HNO3 and distilled water, successively.

3. Results and Discussion

3.1. Batch Studies
3.1.1. Effect of pH and Adsorbent Dosage
pH plays a significant role on the sorption of adsorbates
on adsorbents. The pH level affects the network of
negative charge on the surface of the adsorbent cell walls,
as well as the physic chemistry and hydrolysis of the Figure 2. Effect of adsorbent dosage for Pb(II) sorption by CSP at 25°C
metal ions. Preliminary experiments have been performed (Condition: 25mg/l Pb(II), 160 rpm, 60 min)
 American Journal of Environmental Protection 53

The sorption of Pb(II) with different adsorbent dosage and pH, the removal decreased from 75.4 to 65.1% while
(0.5–10.0 g/l) was studied keeping other experimental the adsorption density increased from 0.754- 19.622 mg/g
condition constant,Pb(II) concentration(25 mg/l), stirring (Figure 4). The apparent behavior can be accredited to the
speed (160 rpm), pH (5.0) and contact time (60 min). The increase in the amount of Pb(II) ions to the static number
outcome indicates (Figure 2) that increases in adsorbent of available active sites on the CSP. Hence, more metal
dosage resulted in a higher removal of Pb(II). This may be ions were left in solution [15]. This also indicates that,
due to the increase in the number of adsorption sites on there is some metal concentration that produces the
surface of CSP. Maximum removal of 87.12% was maximum adsorption for a given adsorbent mass, and
observed with an adsorbent dosage of 5.0 g/l and beyond thereafter, adding more metal cannot increase adsorption
this, the removal capacity was lesser, may be attributed to because no more sites are available: all are occupied. A
overlying or aggregation of available binding sites [13], progressive decrease in the proportion of covalent
ensuing in decrease in total available adsorbent surface interactions and an increase in the proportion of
area to metal ions and an increase in diffusion path length. electrostatic interactions at sites with a lower affinity for
heavy metals can also be attributed as another reason for
3.1.3. Effect of Contact time decreased percentage removal.
The retention of heavy metals on adsorbent increased
with increasing contact time for a fixed concentration of
heavy metal and a fixed adsorbent mass [14]. The effect of
contact time can be seen in Figure 3 for the adsorption of
Pb(II) ions on CSP. The Pb(II) ions sorption increased
hastily with time up to 90 min and thereafter shows steady
adsorption rate. The uptake of Pb(II) ions was 85.92% at
90 min. This is apparent by the fact that a large number of
sites are available for sorption during the initial stage, and
few minutes later, the remaining vacant surface sites are
hard to be occupied due to repulsive forces between the
Pb(II) on the solid and the aqueous phases. According to
the results, the equilibrium reached at 90 min and was
taken as the optimal contact time for the succeeding
experiments to make sure that equilibrium is properly
attained. Figure 4. Effect of Initial Pb(II) concentration on sorption process by
CSP (Condition: 25°C, 160 rpm, 5g/l Adsorbent dosage, 60 min)

The heavy metal adsorption capacities were calculated

by means of least-squares regression using linear
expression of Freundlich Isotherm [16] Eq. (3) and
Langmuir Isotherm [16] Eq. (4).
1
=
log q e log K F + log Ce (3)
n
where Ce (mg/l) the metal concentration in the aqueous
phase; KF and n are the Freundlich coefficients. KF
provides an indication of the adsorption capacity and n is
related to the intensity of adsorption.
1 1 1
= + (4)
q e q m K L Ce q m
Figure 3. Effect of contact time on Pb(II) sorption by CSP, at 25°C,
where qe, qm are equilibrium adsorption capacity and
(Condition: 25mg/l Pb(II), 160 rpm, 5g/l Adsorbent dosage:)
maximum adsorption capacity, Co, Ce are initial and
equilibrium concentration. The Langmuir constant KL
3.2. Equilibrium Studies related to the energy of adsorption. One of the essential
The analysis and design of the process entail the characteristics of the Langmuir isotherm is separation
relevant equilibrium sorption, which is the most important factor or dimensionless equilibrium parameter ‘‘RL’’ as
informative parameter to understand the adsorption since shown in Eq. 5 provides significant information about the
they indicate how metal ions are partitioned between the nature of adsorption. The value of RL indicates the type of
adsorbent and liquid phases at equilibrium as a function of the Langmuir isotherm [17] to be irreversible (RL=0),
metal concentration. When an adsorbent comes into favorable (0<RL< 1), linear (RL=1) or unfavorable (RL>1).
contact with a metal ion solution, the concentration of The RL values as shown in Table 2, at different
metal ions on the adsorbent surface will increase until a temperatures (298, 308 and 318K) indicates the favorable
dynamic equilibrium is reached; at this point, there is a biosorption.
clearly defined distribution of metal ions between the solid
1
and liquid phases [14]. For heavy metal ion concentrations RL = (5)
ranged from 5 to 150 mg/l with a fixed adsorbent mass 1 + (1 + K L Co )
54 American Journal of Environmental Protection

The resulting adsorption isotherms parameters for adsorption capacity obtained by some other researcher are
heavy metals used in this study are summarized in Table 2, quite higher [18-23]. The adsorption capacity is quite high
indicate that the data best fitted to Langmuir isotherm at with the finding of our previous studies for removal of
all three temperatures, which implies the occurrence of Cd(II) ion using Cucumissativus (qmax, 3.597 mg/g) [7]
monolayer adsorption onto homogeneous surface for the and NaOH modified Desmostachyabipinnata Leaves(qmax,
experimental conditions used. With respect to the 19.84 mg/g) & Bambusaarundinacea Leaves (qmax, 19.71
coefficients of the Langmuir model, KL increases with the mg/g) [24] at room temperature i.e. 298K.A little
temperature, indicating that the adsorption capacity difference in adsorption capacity was observed i.e. at temp
increases with the temperature and the higher values of KL 298 K compared to 308K & 318K. This means that any
confirm the stronger binding affinity [5] of dried CSP to temperature can be used for removing Pb(II) effectively
Pb(II) ions. The qm values compared to maximum from aqueous solutions.

Table 2. Equilibrium Parameters for the adsorption of Pb(II) on CSP at different temperatures
Freundlich Isotherm Langmuir Isotherm
Temp
R2 N KF(mg1−1/n g−1 l1/n) R2 qm(mgg-1) KL(l mg-1) RL

298K 0.963 1.31 1.34 0.987 28.25 0.049 0.312

308K 0.964 1.35 1.57 0.985 27.40 0.060 0.266

318K 0.961 1.37 1.67 0.986 26.74 0.067 0.273

randomness, irreversible process and the affinity of
3.3. Thermodynamic Studies biosorbent at the solid aqueous interface during the
Analysis of thermodynamics of equilibrium sorption adsorption process. In addition, the positive value of ΔSo
data can give noteworthy information about sorption suggests a few structural changes in the adsorbent, favored
process. Thermodynamic parameter can be determined complexion and sorption constancy [29,30]. The
from following equations [25,26]. thermodynamic parameters indicated favored biosorption
for the removal of Pb(II) ions by CSP.
∆G  =− RT ln K c (6)
Table 3. Thermodynamic parameters at different temperatures
∆G  =∆H − T∆S (7) Thermodynamic Parameters
Temp ΔGo ΔHo ΔSo
where Kc is the distribution constant, obtained by (kJmol-1) (kJ mol-1) (J mol-1 K-1)
multiplying Langmuir constant KL and maximum
298K -0.774 -1255 4.54
adsorption capacity qm(mg/g) [27]. R is the universal gas
constant (8.314×10-3 kJ/mol/K) and T is the absolute 308K -1.230
temperature (K). The values of ΔHo and ΔSo were dogged 318K -1.427
from the slope and the intercept from the plot of ln Kc
versus 1/T as shown in Figure 5. 3.4. Biosorption Kinetics and Mechanism
A further kinetic investigation with pseudo-first order,
pseudo-second-order and intra-particle diffusion kinetic
models have been used to investigate the Pb(II) ion
sorption mechanism onto CSP and the mechanism of rate-
controlling steps. The integral form of the pseudo-first-
order kinetic model [31] is generally expressed as follows:
log(q e − q t =
) log q e − K1ad t (8)
where, qe and qt are the adsorption capacities (mg/g) at
equilibrium and time t (min), respectively. The pseudo-
first-order rate constant K1ad (min-1) was determined
experimentally by plotting log (qe-qt) versus t.
The pseudo-second-order kinetic model, proposed by
Ho and McKay [32], is based on the assumption that the
Figure 5. Plot of ln Kc versus 1/T for Pb(II) sorption onto CSP
adsorption follows chemisorption. The linear form can be
written as:
The enthalpy change (ΔHo) and the entropy change
(ΔSo) recorded from the study were shown in Table 3. The =
t 1 1
+ t (9)
negative values of Gibbs free energy (ΔGo) indicate 2
q t K 2ad q e q e
feasibility and the spontaneous nature of Pb(II) sorption.
The ΔG◦ value is more negative with increasing where, qe (mg/g), qt (mg/g) are the adsorption capacity at
temperature, which suggests that higher temperature equilibrium and time t(min), whereas, K2ad (g/mg/min) is
makes the adsorption easier. The negative value of ΔHo the rate constant of adsorption. By plotting a curve of t/qt
indicates the exothermic nature of the biosorption of Pb(II) against t, qe and K2ad can be evaluated. The pseudo first
onto CSP [28]. The positive ΔSo value shows increase in
 American Journal of Environmental Protection 55

and second order kinetic parameters were summarized in adsorption and shows that, in the beginning higher rate of
the Table 4. metal removal is due to the immediate availability of large
The evaluation of rate controlling steps such as surface area and active adsorption sites. The second
chemical reaction and mass transport is very advantageous portion represents the gradual adsorption, where rate-
to understand the mechanism involve in the adsorption controlling step is the intra-particle diffusion. The intra-
phenomenon. The overall adsorption process can be particle diffusion is not the only rate controlling step for
divided into four steps [33]: the adsorption of Pb(II) ions onto CSP, which is
Ist Step: The transport of metal ion from the bulk to the confirmed by the deviation of plot from the origin.
boundary layer takes place. All three kinetic models applied at different
IInd Step: The film diffusion, i.e. transport of metal ions temperatures, confirms the applicability of the Pseudo
from the boundary layer to the external surface of the second-order kinetic model, with a straight line obtained
adsorbent. through a plot of t/qt against t with a higher correlation
IIIrd Step: Transfer of ions from the surface to the coefficient (Table 4) compared to Pseudo first order and
intra-particular spaces present in adsorbent as active sites intra particle diffusion model. This suggests that the rate-
and this step is known as particle diffusion. limiting step may be the chemisorption instead of mass
IVth & Final Step: Metal ions interaction at the transport promoted through sharing of electrons between
available adsorption sites on the internal surfaces of the the sorbate and biosorbent, or covalent bond formation,
adsorbent. through the interchange of electrons between the parties
The second and third steps are slow, therefore, due to involved [32] .Figure6 present multi-linear plots, that
their slow rate, the rate controlling steps mainly depend on predicts, two or more steps influence the adsorption
either film diffusion or particle diffusion. process such as external diffusion, intra-particle diffusion
Therefore, to provide insightful description of etc [35].
mechanism involved in biosorption process, the intra-
particle diffusion model [34], is of major consideration.
The Eq.10 is a common representation of intra-particle
diffusion model, where the intercept is associated with the
mass transfer across the boundary layer and the expected
value of the exponent is 0.5.

=
q t K i t 0.5 + I (10)
where qt (mg/g) is the adsorbed metal amount and Ki is the
intra- particle diffusion rate constant (mg/g/min1/2).
According to this model, the plot of uptake (q) versus the
square root of time should be linear if intra-particle
diffusion is involved in the adsorption process and if these
lines pass through the origin then intra-particle diffusion is
the sole rate-controlling step. As shown in the Figure 6,
the first sharp section signifies the external surface Figure 6. Intra particle diffusion model of Pb(II) sorption by CSP

Table 4. Kinetic Parameters for the adsorption of Pb(II) on CSP at different temperatures
Pseudo First Order Pseudo Second Order Intra Particle Diffusion
Temp
qe qe k2 Kid
R2 k1 (min-1) R2 R2 I
(mgg-1) (mgg-1) (g mg-1min-1) (mgg-1min1/2)
298K 0.854 1.58 0.018 0.999 4.44 0.028 0.758 0.125 2.64

308K 0.856 3.90 0.463 0.999 4.52 0.030 0.735 0.126 2.76

318K 0.844 1.40 0.018 0.999 4.56 0.032 0.706 0.125 2.76

3.5. Desorption of the Adsorbed Pb(II) ions

Desorption of adsorbed Pb(II) ions onto CSP also
studied by using HNO3. For this studies, 10mL of HNO3
was used. The effects of volume of 1M HNO3 as eluent
were also investigated in the range of 5.0–10.0 ml The
recovery for Pb(II) ions was found to be 93.5% even
using only 6.0mL of 1M HNO3. Subsequent elution with
high amount of HNO3 readily strips the Pb(II) ions from
CSP. In addition, as it can be seen from Figure 7, the high
stability of permitted five times of adsorption–desorption
process along the studies without a decrease about 5% in
recovery of Pb(II) ions was observed.
Figure 7. Desorption efficiency of CSP with cycle number
56 American Journal of Environmental Protection

3.6. FTIR and SEM Analysis broaden and shifted towards 3464.9 cm-1 after adsorption
may be due to replacement of OH bonded H ion with
To identify the type of possible Pb(II) binding sites of Pb(II) ion. The peaks located at 2270.3 cm-1, 1723.7 cm-1
CSP, FTIR spectra and to observe changes in surface may be of isocyanate and –C=O present on cyclic ring
morphology SEM images were recorded before and after respectively shifted to 2148.1cm-1 and 1729.9cm-1 shows
the adsorption (Figure8&9). The FTIR spectrum of CSP their contact with the Pb(II). The band at 1659 cm-1
was complex due to the existence of various functional correspond to stretching of C=O of primary amide.
groups on the surface of the biomass. When CSP got to Shifting of 1102.6cm-1 towards 1218.6cm-1 shows the
interact with Pb(II) of aqueous phase, the bond energy of participation of C-O-C group of cellulose in metal binding.
C=O, -COO- and C-O-C functional groups present at the The peak at 1593 cm-1 of C=C may be of the aromatic ring
surface of adsorbent were impacted by chemical action of CSP shifted to 1627.1 cm-1 after metal interaction.
generated in adsorption process, consequently, resulting in Below 1000 cm−1the region which exist known as
the shift on the characteristic peaks. There are several “fingerprint region” and the adsorption cannot be clearly
distinct peaks that were observed from the spectrum as assigned to any particular vibration because they
shown in Table 5. A broad and strong band stretch was correspond to complex interacting vibration systems [37].
observed from 3000 to 3600 cm−1, indicating the presence Although according to Jahn et al. [38] peaks in range of
of free or hydrogen bonded –OH groups present on the 950-700cm-1 shows side group deformation region for
adsorbent surface [36] (alcohols and carboxylic acids). COH, CCH and OCH of cellulose and hemicelluloses.
The peak present at 3451.9 cm-1 before adsorption

Figure 8. FTIR spectra of CSP before and after Pb(II) adsorption

adsorbent. Figure 9a illustrates the SEM of native

Table 5. Functional groups and mode of vibration from the FTIR adsorbent at 800X that shows irregular grooves and
spectrum of CSP porous structure that might favor accessibility of Pb(II) to
Mode of
FTIR Peaks (cm–1) Assignment of bonds the adsorbent surface [8]. Figure 9b shows SEM of
Vibration
3879.9 Unknown exhausted adsorbent clearly indicates the presence of new
3777.8 - shiny bulky particles and layer over the surface of metal
3692.2, 3655.1, Free O-H and H-bonded OH loaded adsorbent those are absent from the native
Stretching
3629.9 and 3451.9 on Surface respectively adsorbent before metal loading, and thus observed
2369.2 & 2270.3 - NCO group Stretching significant visible changes in the morphology of CSP
1813.5 Carbonyl C=O Strong stretching before and after Pb(II) sorption.
1723.7 6-membered cyclic ketone Strong stretching
1659.1 C=O of amide Strong stretching
C=C present in aromatic
1593.7 Stretching
rings
Symmetrical
1102.6 C-O-C of phenol, cellulose
stretching
In addition, the surface structure of the CSP was
analyzed by scanning electron microscopy (SEM Zeiss,
Germany). The scanning electron micrographs enable the
direct observation of the surface microstructures of the Figure 9. Scanning Electron Micrograph showing morphology of virgin
CSP (a) and (b) Pb(II) loaded CSP
 American Journal of Environmental Protection 57

(Amanita rubescens) biomass, Journal of hazardous materials, 164

4. Conclusion (2009) 1004-1011.
[11] J.L. Gardea-Torresdey, J.H. Gonzalez, K.J. Tiemann, O.
Pb(II) ion sorption on CSP were found to be dependent Rodriguez, G. Gamez, Phytofiltration of hazardous cadmium,
on experimental conditions, particularly on pH and initial chromium, lead and zinc ions by biomass of Medicago sativa
concentration of Pb(II) ions in solution. Adsorption (Alfalfa), Journal of hazardous materials, 57 (1998) 29-39.
[12] X.J. Wang, S.Q. Xia, L. Chen, J.F. Zhao, J.M. Chovelon, J.R.
capacity was affected at low pH but increased with Nicole, Biosorption of cadmium(II) and lead(II) ions from
increase in concentration, adsorbent dosage and contact aqueous solutions onto dried activated sludge, Journal of
time. The equilibrium data presented a better fit to the environmental sciences, 18 (2006) 840-844.
Langmuir isotherm model indicating monolayer sorption [13] C. Namasivayam, D. Prabha, M. Kumutha, Removal of direct red
and acid brilliant blue by adsorption on to banana pith,
while following kinetics of pseudo-second order. The Bioresource technology, 64 (1998) 77-79.
FTIR analysis revealed –OH, –C=O, –C–O–C–, –COOH, [14] M.E. Argun, S. Dursun, C. Ozdemir, M. Karatas, Heavy metal
and –COO– as the major functional groups that act as adsorption by modified oak sawdust: thermodynamics and kinetics,
adsorption sites for Pb(II). Chemical adsorption was the Journal of hazardous materials, 141 (2007) 77-85.
main adsorption mechanism involved as indicated by [15] M. Moyo, L. Chikazaza, B.C. Nyamunda, U. Guyo, Adsorption
Batch Studies on the Removal of Pb(II) Using Maize Tassel Based
Langmuir isotherm, pseudo second order kinetics and Activated Carbon, Journal of Chemistry, 2013 (2013) 8.
FTIR. As CSP has no commercial value and is a good, [16] O. Altın, H.Ö. Özbelge, T. Doğu, Use of General Purpose
inexpensive source of readily available biomaterial so Adsorption Isotherms for Heavy Metal–Clay Mineral Interactions,
from the reported observations it can be concluded that Journal of Colloid and Interface Science, 198 (1998) 130-140.
this can be successfully used as a low-cost environment- [17] A. Adeogun, M. Idowu, A. Ofudje, S. Kareem, S. Ahmed,
Comparative biosorption of Mn(II) and Pb(II) ions on raw and
friendly adsorbent for the removal of heavy metals from oxalic acid modified maize husk: kinetic, thermodynamic and
aqueous solution. isothermal studies, Appl Water Sci, 3 (2013) 167-179.
[18] V.K. Gupta, I. Ali, Removal of lead and chromium from
wastewater using bagasse fly ash--a sugar industry waste, J
Acknowledgement [19]
Colloid Interface Sci, 271 (2004) 321-328.
T.G. Chuah, A. Jumasiah, I. Azni, S. Katayon, S.Y. Thomas
Choong, Rice husk as a potentially low-cost biosorbent for heavy
The authors would like to acknowledge and extend their metal and dye removal: an overview, Desalination, 175 (2005)
heartfelt gratitude to The Director, CSIR-Indian Institute 305-316.
of Toxicology Research, Lucknow, for taking interest in [20] S.S. Ahluwalia, D. Goyal, Removal of Heavy Metals by Waste
the study. The authors also express their gratefulness to all Tea Leaves from Aqueous Solution, Engineering in Life Sciences,
5 (2005) 158-162.
the technical staff for their help. The authors thank the
[21] M.M. Rao, D.K. Ramana, K. Seshaiah, M.C. Wang, S.W. Chien,
Council of Science and Technology, Uttar Pradesh, India Removal of some metal ions by activated carbon prepared from
(Project Code, GAP-271) for providing their financial Phaseolus aureus hulls, Journal of hazardous materials, 166 (2009)
support for this research work. 1006-1013.
[22] E. Pehlivan, T. Altun, S. Parlayici, Utilization of barley straws as
biosorbents for Cu2+ and Pb2+ ions, Journal of hazardous
materials, 164 (2009) 982-986.
Reference [23] H.Z. Mousavi, A. Hosseynifar, V. Jahed, S.A.M. Dehghani,
Removal of lead from aqueous solution using waste tire rubber ash
[1] Y.S. Ho, C.C. Wang, Pseudo-isotherms for the sorption of as an adsorbent, Brazilian Journal of Chemical Engineering, 27
cadmium ion onto tree fern, Process Biochemistry, 39 (2004) 761- (2010) 79-87.
765. [24] R. Pandey, R.L. Prasad, N.G. Ansari, R.C. Murthy, Utilization of
[2] A. Demirbas, Heavy metal adsorption onto agro-based waste NaOH modified Desmostachya bipinnata (Kush grass) leaves and
materials: a review, Journal of hazardous materials, 157 (2008) Bambusa arundinacea (bamboo) leaves for Cd(II) removal from
220-229. aqueous solution, Journal of Environmental Chemical Engineering.
[3] D. Sud, G. Mahajan, M.P. Kaur, Agricultural waste material as [25] H.K. Boparai, M. Joseph, D.M. O'Carroll, Kinetics and
potential adsorbent for sequestering heavy metal ions from thermodynamics of cadmium ion removal by adsorption onto nano
aqueous solutions - a review, Bioresource technology, 99 (2008) zerovalent iron particles, Journal of hazardous materials, 186
6017-6027. (2011) 458-465.
[4] S.S. Ahluwalia, D. Goyal, Microbial and plant derived biomass for [26] Z.A. Al-Anber, M.A. Matouq, Batch adsorption of cadmium ions
removal of heavy metals from wastewater, Bioresource from aqueous solution by means of olive cake, Journal of
technology, 98 (2007) 2243-2257. hazardous materials, 151 (2008) 194-201.
[5] G. Vazquez, J. Gonzalez-Alvarez, S. Freire, M. Lopez-Lorenzo, G. [27] Z. Aksu, İ.A. İşoğlu, Removal of copper(II) ions from aqueous
Antorrena, Removal of cadmium and mercury ions from aqueous solution by biosorption onto agricultural waste sugar beet pulp,
solution by sorption on treated Pinus pinaster bark: kinetics and Process Biochemistry, 40 (2005) 3031-3044.
isotherms, Bioresource technology, 82 (2002) 247-251. [28] Z.Y. Yao, J.H. Qi, L.H. Wang, Equilibrium, kinetic and
[6] M.D. Rodriguez, A. Redondo, M.J. Villanueva, Study of dietary thermodynamic studies on the biosorption of Cu(II) onto chestnut
fibre content in cucumber by gravimetric and spectrophotometric shell, Journal of hazardous materials, 174 (2010) 137-143.
methods, Food Chemistry, 43 (1992) 295-298. [29] R. Donat, A. Akdogan, E. Erdem, H. Cetisli, Thermodynamics of
[7] R. Pandey, N.G. Ansari, R.C. Murthy, R.L. Prasad, Cd(II) Pb2+ and Ni2+ adsorption onto natural bentonite from aqueous
Adsorption from Aqueous Solution onto Cucumis sativus Peel: solutions, J Colloid Interface Sci, 286 (2005) 43-52.
Equilibrium, Thermodynamic and Kinetic Study, Journal of [30] A. Mittal, L. Krishnan, V.K. Gupta, Removal and recovery of
Ecophysiology & Occupational Health, 13 (2013), 75-84. malachite green from wastewater using an agricultural waste
[8] M. Bansal, U. Garg, D. Singh, V.K. Garg, Removal of Cr(VI) material, de-oiled soya, Separation and Purification Technology,
from aqueous solutions using pre-consumer processing 43 (2005) 125-133.
agricultural waste: a case study of rice husk, Journal of hazardous [31] C. Namasivayam, R.T. Yamuna, Adsorption of chromium (VI) by
materials, 162 (2009) 312-320. a low-cost adsorbent: Biogas residual slurry, Chemosphere, 30
[9] V. Vadivelan, K.V. Kumar, Equilibrium, kinetics, mechanism, and (1995) 561-578.
process design for the sorption of methylene blue onto rice husk, [32] Y.S. Ho, G. McKay, Pseudo-second order model for sorption
Journal of Colloid and Interface Science, 286 (2005) 90-100. processes, Process Biochemistry, 34 (1999) 451-465.
[10] A. Sari, M. Tuzen, Kinetic and equilibrium studies of biosorption [33] A. Özer, G. Gürbüz, A. Çalimli, B.K. Körbahti, Biosorption of
of Pb(II) and Cd(II) from aqueous solution by macrofungus copper(II) ions on Enteromorpha prolifera: Application of
58 American Journal of Environmental Protection

response surface methodology (RSM), Chemical Engineering [37] M.H. Kamal, W.M. Azira, M. Kasmawati, Z. Haslizaidi, W.N.
Journal, 146 (2009) 377-387. Saime, Sequestration of toxic Pb(II) ions by chemically treated
[34] G. McKay, The Adsorption of basic dye onto silica from aqueous rubber (Hevea brasiliensis) leaf powder, Journal of environmental
solution-solid diffusion model, Chemical Engineering Science, 39 sciences, 22 (2010) 248-256.
(1984) 129-138. [38] A. Jahn, M.W. Schroder, M. Futing, K. Schenzel, W. Diepenbrock,
[35] S. Figaro, J.P. Avril, F. Brouers, A. Ouensanga, S. Gaspard, Characterization of alkali treated flax fibres by means of FT
Adsorption studies of molasse's wastewaters on activated carbon: Raman spectroscopy and environmental scanning electron
modelling with a new fractal kinetic equation and evaluation of microscopy, Spectrochimica acta. Part A, Molecular and
kinetic models, Journal of hazardous materials, 161 (2009) 649- biomolecular spectroscopy, 58 (2002) 2271-2279.
656.
[36] E. Pehlivan, T. Altun, S. Cetin, M. Iqbal Bhanger, Lead sorption
by waste biomass of hazelnut and almond shell, Journal of
hazardous materials, 167 (2009) 1203-1208.
RUCHI PANDEY
Ph.D. Scholar
BHU/CSIR-Indian Institute of Toxicology Research
Lucknow, Uttar Pradesh, India
ruchipandey3@gmail.com
+919307335008
(CURRICULUM VITAE)

Academic Credentials
 PhD on topic entitled “Adsorptive remediation of Pb(II) and Cd(II) from simulated wastewater
using low cost agro-waste materials.”
 Post-Graduation (M.Sc.) in Chemistry, Lucknow University, 2007.
 Graduation (B.Sc.) with Zoology, Botany, and Chemistry, Lucknow University, 2005.
 12th (C.B.S.E Board), 2002.
 10th (C.B.S.E Board), 2000.

Award
 Snehlata Banerjee Gold Medal (2014) by the Academy of Environmental Biologist (AEB),
India.
 Senior Research Scholar award from UP-Council of Science and Technology for project
proposal on “Cost-effective method development for enhanced Arsenic removal from ground
water using Magnetic Activated Carbon prepared by impregnation of Magnetite
Nanoparticles.”

Publications
1. Pb(II) Removal from Aqueous Solution by Cucumis sativus(Cucumber) Peel: Kinetic,
Equilibrium & Thermodynamic Study.
Ruchi Pandey, N. G. Ansari, R. L. Prasad, R. C. Murthy, American Journal of Environmental
Protection, 2 (3), 51-58. DOI: 10.12691/env-2-3-1, 2014.

2. Utilization of NaOH modified Desmostachya bipinnata (Kush grass) Leaves & Bambusa
arundinacea (Bamboo) Leaves for Cd(II) removal from aqueous solution.
Ruchi Pandey, R. L. Prasad, N. G. Ansari, R. C. Murthy, Journal of Environmental Chemical
Engineering, DOI: 10.1016/j.jece.2014.06.015, 2014.

3. Cd(II) adsorption from aqueous solution onto cucumis sativus peel:

Equilibrium.thermodynamics and Kinetic study.
Ruchi Pandey, N.G. Ansari, R.C.Murthy and R.L. Prasad, Journal of Ecophysiology and
Occupational Health, 3 & 4, 75-84, 2013.

4. Multiple approaches to evaluate the toxicity of the biomass fuel cow dung (kanda) smoke.
Kewal Lal, U. Mani, Ruchi Pandey, N. Singh, A K. Singh, D.K. Patel, M. P. Singh & R.C.
Murthy Journal of Ecotoxicology & Environmental Saftey, DOI: 10.1016/j.ecoenv.2011.06.006,
2011.
Manuscripts Communicated
 Utilization of NaOH modified Citrullus lanatus Rind for Pb(II) and Cd(II) removal from
aqueous solution

Personal Details
Name: Ruchi Pandey
Father’s name: Shri. D. N. Pandey
Date of birth: 3-11-86
Birthplace: Lucknow
Country: India
Marital Status: Married

Place-Lucknow
Date- 12-12-2014 Ruchi Pandey