REMOVAL OF ARSENIC FROM WATER BY USING IRON-COPPER BINARY

OXIDE AS ADSORBENT

A Dissertation Submitted to

KHWOPA COLLEGE

DEPARTMENT OF ENVIRONMENTAL SCIENCE

Tribhuvan University
Dekocha, Bhaktapur, Nepal

In Partial Fulfillment of the Requirements for the Award of

Degree of
M.Sc. in Environmental Science

By
Menuka Prajapati

February, 2023
REMOVAL OF ARSENIC FROM WATER BY USING
IRON-COPPER BINARY OXIDE AS ADSORBENT

A Dissertation Submitted to

KHWOPA COLLEGE

DEPARTMENT OF ENVIRONMENTAL SCIENCE

Tribhuvan University
Dekocha, Bhaktapur, Nepal

In Partial Fulfillment of the Requirements for the Award of Degree of

M.Sc. in Environmental Science

By
Menuka Prajapati
T.U. Registration No. : 5-2-0408-0327-2013
Symbol No.: 945

February, 2023

i
 LETTER OF DECLARATION

I hereby declare that the work presented in this dissertation is a genuine work done
originally by me and has not been submitted anywhere for the award of any degree. All
the sources of information have been specifically acknowledged by reference to the
author(s) or institutions(s).

…………………

Menuka Prajapati

February, 2023

ii
 LETTER OF RECOMMENDATION

This is to certify that Ms. Menuka Prajapati has completed this dissertation work
entitled "Removal of Arsenic from water by using Iron-Copper binary oxide as
Adsorbent" as a partial fulfillment of the requirements of M.Sc. in Environmental
Science under my supervision and guidance. To my knowledge, this research has not
been submitted for any other degree, anywhere else.

I therefore, recommend the dissertation for acceptance and approval.

…..........................

Supervisor
Dr. Tista Prasai Joshi
Scientific Officer
Nepal Academy of Science and Technology

iii
 LETTER OF APPROVAL

On the recommendation of supervisor “Dr. Tista Prasai Joshi” this dissertation

submitted by Ms. Menuka Prajapati entitled “Removal of Arsenic from water by
using Iron-Copper binary oxide as Adsorbent” has been approved for the examination
and submitted to the Tribhuvan University in partial fulfillment of the requirements of
M.Sc. in Environmental Science.

..............................

Ms. Meera Prajapati

Incharge, B.Sc. and M.Sc.
Khwopa College

iv
 CERTIFICATE OF ACCEPTANCE

This dissertation entitled “Removal of Arsenic from water by using Iron-Copper

binary oxide as Adsorbent” submitted by “Ms. Menuka Prajapati” has been examined
and accepted as a partial fulfillment of the requirements of M.Sc. in Environmental
Science.

Evaluation Committee

…………………… ………………………

Mr. Roopak Joshi Ms. Meera Prajapati

Principal In-charge, Environmental Science
Khwopa college Khwopa College

……………………… …………………………….

Dr. Tista Prasai Joshi

Supervisor External examiner
Scientific Officer
Nepal Academy of Science and Technology

…………………………. ………………………….
Prof. Dr. Siddhi Bir Karmacharya
Chairman Research Committee
Khwopa College

v
 ACKNOWLEDGEMENTS
First and foremost, I would like to express my utmost gratitude to my supervisor Dr.
Tista Prasai Joshi, Scientific Officer, Nepal Academy of Science and Technology
(NAST), Khumaltar, Lalitpur for providing me with her professional guidance, constant
encouragement, valuable support, and motivation. I am grateful to have worked under
her guidance and supervision.

I acknowledge the help, advice and guidance rendered my co-supervisor Ms. Meera
Prajapati, Incharge, Department of Environmental Science, Khwopa College, Dekocha,
Bhaktapur for her recommendation for my enrollment at NAST and also for her
suggestions and motivation throughout my research is unforgettable.

I would like to express my deepest gratitude to the Environment and Climate Study
Laboratory, Faculty of Science, Nepal Academy of Science and Technology (NAST),
Khumaltar, Satdobato, Lalitpur for providing laboratory facilities. I am equally thankful
to UNESCO and the International Development Research Center (IDRC), Ottawa,
Canada for providing the grant to conduct this research.

Also, I would like to thank Ms. Naina Byanjankar and Mr. Agni Dhakal for guiding me
throughout my study and for helping in completing my research work without whom this
research work could not have been completed. I am equally indebted to all the staffs of
NAST who helped me in completing my work.

Lastly, I would like to pay my gratitude to my parents for being so patient and supportive,
my sister for motivating me to work harder, my friends who encouraged and helped me in
completing my thesis, and all those people who directly and indirectly helped me in
completing my research work.

Date: Menuka
Prajapati

vi
 ABSTRACT

Groundwater pollution by arsenic is one of the serious problems worldwide and is considered
with high toxicity and carcinogenicity. To remove the arsenic concentration from drinking water,
nanostructured iron-copper binary oxide (Fe-Cu), copper oxide (CuO), and ferric hydroxide
(FeOOH) were synthesized in the laboratory via the co-precipitation method. Characterization of
the prepared adsorbents was done by Zeta Potential (ζ-potential), Particle Size, X-Ray
Diffractometer (XRD), and Fourier Transform Infrared Spectroscopy (FTIR). Batch experiments
like Effect of pH, Adsorption Isotherm, and Adsorption kinetics were performed to evaluate
adsorption of arsenite (As III) and arsenate (As V). Furthermore, the regeneration capacity of
adsorbents was analyzed to understand the reusability properties of adsorbents. Results exhibited
that Fe-Cu shows a higher removal capacity towards As (III) and As s(V) than FeOOH and CuO.
Adsorption of As (III) and As (V) onto Fe-Cu, FeOOH, and CuO was more favorable at pH 4.0,
adsorption decreased with an increase in pH. To understand the adsorption kinetics, two models
pseudo-first-order and pseudo-second-order models were fitted to the kinetic data. By comparing
the correlation coefficient R2, adsorption onto Fe-Cu can be best described with a pseudo-
second-order model on As (III) and As (V). Similarly, the obtained experimental data were fitted
by Langmuir and Freundlich isotherm models. Langmuir model was better fitted to describe the
adsorption of As (III) and As (V) on Fe-Cu in comparison to the Freundlich model. The
recyclability result showed that Fe-Cu could be easily regenerated and has a good potential for
the long-term stabilities of the adsorbent. Hence, Fe-Cu showed good adsorption performance
towards As (III) and As (V).

Keywords: Arsenic, Adsorption, Arsenite, Arsenate, nanoparticles

vii
 ABBREVIATIONS AND ACRONYMS
FTIR : Fourier Transform Infrared Spectroscopy

AAS : Atomic Absorption Spectrophotometer

Fe-Cu : Ferric copper binary oxide

FeOOH : Ferric hydroxide

CuO : Copper Oxide

XRD : X-ray Diffraction

ζ-potential : Zeta Potential

As (III) : Arsenite

As (V) : Arsenate

mM : milli molar

mmolL-1 : milli molar per litre

mL : milli Litre

μm : micro metre

rpm : rotation per minute

mgL-1 : milli gram per litre

mV : milliVolt

nm : Nanometer

μg/L : microgram per litre

pH : Potential of Hydrogen

WHO : World Health Organization

USEPA : United States Environmental Protection Agency

viii
MCL : Maximum Concentration Limit

TABLE OF CONTENTS

Contents
LETTER OF DECLARATION...........................................................................................ii

LETTER OF RECOMMENDATION................................................................................iii

LETTER OF APPROVAL.................................................................................................iv

CERTIFICATE OF ACCEPTANCE..................................................................................v

ACKNOWLEDGEMENTS................................................................................................vi

ABSTRACT......................................................................................................................vii

ABBREVIATIONS AND ACRONYMS........................................................................viii

LIST OF FIGURES...........................................................................................................xii

LIST OF TABLES............................................................................................................xii

CHAPTER 1 INTRODUCTION.....................................................................................1

1.1 Background...........................................................................................................1

1.2 Rationale of the Study...........................................................................................3

1.3 Objectives of the study..........................................................................................3

1.3.1 General Objective........................................................................................3

1.3.2 Specific Objectives.......................................................................................3

1.4 Limitations............................................................................................................3

1.5 Overview of Research Process..............................................................................4

CHAPTER 2 LITERATURE REVIEW.................................................................................5

2.1 Arsenic Contamination.........................................................................................5

2.2 Arsenic in the Environment..................................................................................6

2.3 Health Impacts of Arsenic.....................................................................................6

2.4 Treatment Process for arsenic removal.................................................................7

ix
CHAPTER 3 MATERIALS AND METHODS.............................................................12

3.1 Materials..............................................................................................................12

3.2 Preparation of adsorbents....................................................................................12

3.3 Structural Characterization of Adsorbents..........................................................13

3.3.1 Zeta Potential (ζ- potential):.....................................................................13

3.3.2 Particle Size:...............................................................................................13

3.3.3 X-Ray Diffraction (XRD):.........................................................................13

3.4 Batch Experiments..............................................................................................14

3.4.1 Effect of pH................................................................................................14

3.4.2 Adsorption Isotherm.................................................................................14

3.4.3 Adsorption Kinetics...................................................................................15

3.5 Regeneration of adsorbents.................................................................................16

3.6 Analytical methods.............................................................................................16

3.6.1 Fourier Transform Infrared Spectroscopy (FTIR)................................16

3.6.2 Atomic Absorption Spectroscopy (AAS).................................................16

CHAPTER 4 RESULTS AND DISCUSSIONS............................................................17

4.1 Structural Characterization of adsorbents...........................................................17

4.1.1 Zeta Potential (ζ- potential)......................................................................17

4.1.2 Particle Size:...............................................................................................18

4.1.3 X-Ray Diffraction (XRD)..........................................................................19

4.2 Batch Experiments..............................................................................................20

4.2.1 Effect of pH................................................................................................20

4.2.2 Adsorption Isotherm.................................................................................21

4.2.3 Adsorption Kinetics...................................................................................23

4.2.4 Fourier Transform Infrared Spectroscopy (FTIR)................................26

x
 4.3 Regeneration of Adsorbents................................................................................26

CHAPTER 5 CONCLUSIONS......................................................................................28

CHAPTER 7 RECOMMENDATION...........................................................................29

REFERENCES.................................................................................................................30

PLATES.............................................................................................................................31

xi
 LIST OF FIGURES
Figure 1: Overview of Research Process...........................................................................18
Figure 2: ζ- Potential measurement of Fe-Cu, CuO and FeOOH nano-particles over a
wide pH range....................................................................................................................32
Figure 3: Particle size of Fe-Cu, CuO and FeOOH nano-particles...................................33
Figure 4: X-Ray pattern of Fe-Cu, CuO and FeOOH nano-particles................................34
Figure 5: Effect of pH on adsorption of As (III) and As (V) onto Fe-Cu, CuO and
FeOOH...............................................................................................................................35
Figure 6: Adsorption isotherms for the adsorption of As (III) and As (V) onto Fe-Cu, Cuo
and FeOOH surfaces..........................................................................................................36
Figure 7: Adsorption kinetics as a function of time of As (III) and As (V) onto Fe-Cu,
Cuo and FeOOH surfaces..................................................................................................38
Figure 8: FTIR spectra of Fe-Cu, CuO and FeOOH.........................................................40
Figure 9: Removal rate of As (III) and As (V) onto Fe-Cu and FeOOH...........................41

LIST OF TABLES
Table 1: Langmuir and Freundlich isotherm constants for the adsorption of As(III) and
As(V) onto Fe-Cu, CuO and FeOOH at pH 7.5 ± 0.1.......................................................37
Table 2: Adsorption kinetic models for the adsorption of As (III) and As (V) onto Fe-Cu,
CuO and FeOOH at pH 7.5 ± 0.1......................................................................................38

xii
 1.1INTRODUCTION
1.2 Background
Water is necessary for all human life and economic activity. It is employed in home, commercial, and
agricultural settings. Maintaining health involves drinking enough water, both in quantity and quality. To
reduce sickness and enhance quality of life, it is crucial to have access to clean water. As human activity
and population grew, so did the need for water (Sudani 2018).

Al-Sudani, H.I.Z. 2018. Hydrochemical Evaluation and Utilization of Groundwater in Khanaqin Area,
Diyala Governorate - East of Iraq. Iraqi Journal of Science, 59 (4C): 2279-2288.

One of the most important natural resources in the globe is groundwater. Due to its availability,
consistency in quality, and low cost of extraction, groundwater is the primary source of water for many
major small towns and cities around the world (Morris et al., 2003). Groundwater is the underground
water that exists below the water table in fully saturated soils and geologic formations (Freeze & Cherry,
1979).

In 2003, it was estimated that groundwater holds nearly 50% of the drinking water supply, 40% of the
demand for industrial water, and 20% of the water used for irrigation (Foster et al., 2003). Globally, more
than a third of water used by humans comes from groundwater. In rural areas, the ratio is higher: more
than half of all drinking water worldwide is supplied from groundwater (Harter 2015; Sudani 2018).

Ref: Al-Sudani, H.I.Z. 2018. Hydrogeological Properties of Groundwater in Karbala’a Governorate –

Iraq. Journal of University of Babylon, Engineering Sciences. 26 (4):70-84

Groundwater contaminants are often tasteless and colorless. Additionally, contaminated groundwater has
long-lasting and highly challenging to detect effects on human health (Chakraborti et al. 2015). Since
groundwater is present in underground geological layers and dwellings durations are lengthy, cleanup
after contamination is difficult and expensive (Wang et al. 2020; Su et al. 2020). Even if the source of
pollution is eliminated, the natural cleansing methods for treating contaminated groundwater might
hundreds of years or even decades (Tatti et al. 2019). Ground water contamination can result in low-
quality drinking water, a lack of water supply, the degradation of surface water systems, high cleaning
expenses, rising prices of alternative water supplies, and/or serious health problems (U.S. Environmental
Protection Agency 1993).

The production of highly effective and affordable adsorbents for the removal of arsenic has received a lot
of focus over the last decades; examples of these adsorbents include metal oxides (Aredes et. al, 2013;
Zhang et. al, 2004; Mohan et. al., 2007; Chakravarty et al, 2002), activated carbons (Chen et al 2007) and
modified minerals (Li et al, 2007; Ramesh et al 2007). For instance, comparing to water for drinking with
13
arsenic, 0.5 lgl-1, a lifetime exposure to arsenic, 50 lgl-1 raises the danger of developing cancer by 100
times (NAS 1999). The revised suggested value was determined based on the ability to assess As's
toxicity, notably its carcinogenicity, and on growing public awareness of its toxicity (WHO, 1993).

The removal of arsenic has been treated more recently via adsorption on iron-based (IB) media, and it is
regarded to be one of the most promising solution. Numerous products, comprising iron oxide-based
adsorbents, iron-coated sand, zero valent iron, modified iron, and granular ferric hydroxide, have been
developed as a result of this (Jain and Singh, 2012). The most efficient and reliable technology is the
adsorption method since it is low-cost, easy to use, and extremely effective (Zhang et. al., 2007).

In this study, synthesized ferric copper binary oxide adsorbent was used due to its simple synthesis
process, low cost, and ease of regeneration for the removal of arsenic from drinking water. (Zhang et. al,
2013). Hence, our study's objective was to prepare ferric copper binary oxide (Fe-Cu binary oxide),
FeOOH, and CuO and characterize their properties using X-ray diffractometer (XRD), Fourier Transform
Infrared Spectroscopy (FTIR) and Zeta potential (ζ-potential). Several techniques were employed to
characterize the morphology of adsorbents, which has provided structural insights into the properties of
adsorbents. After that, adsorptive behaviors was examined on the absorbents via batch experiments such
as effect of pH, adsorption isotherms and adsorption kinetics. This study provides information for
understanding the adsorption mechanism and the results shows functional insights into the application of
the adsorbents for water purification.

Arsenic Distribution in Nepal

In 1999, arsenic presence in groundwater in the Terai district was brought to light for the first time
during the survey conducted by WHO [42]. Figure 3 indicates the number of samples containing
various concentration of arsenic in groundwater samples in 25 districts of Nepal which were studied by
different organizations and individuals. In general maximum numbers of samples are having the
arsenic concentration below 10 µg/L. Few samples were also reported arsenic concentration in
the range of 10–50 µg/L. The southwestern to southeastern regions, located along the Indian
border, proved to be severely affected arsenic, with concentration larger than 50 µg/L. Thus, this study
reflects that there is alarming situation in a few areas which needs the analysis, mitigation and removal
of the low level arsenic concentration from the groundwater.

Figure 3. Groundwater arsenic map of Nepal showing proportion of arsenic contaminated

samples found in various districts of Nepal.

14
 The district Iiam, Jhapa, Morang, Udayapur, Mahottari, Parsa, Kathmandu, Lalitpur, Chitwan, Palpa,
Dang, and Bardiya had reported the low level of arsenic concentrations hence arsenic pollution level is
low (Figure 4).

15
 Figure 4. Arsenic (total) concentration in the samples of groundwater of different districts

in Nepal.
Number of groundwater samples (in Thousands)

90

80
Total no.

70 of tests

60 0-10 ppb

50 >10-50

40 ppb
> 50 ppb
30

20

10

Districts of Nepal

The district such as Sunsari, Saptari, Siraha, Dhanusha, Sariahi, Rautahat, Bara, Nawalparasi,
Rupandehi, Kapilbastu, Banke, Kailali and Kanchanpur had reported the varying from the degree of

10–50 µg/L and even higher than the 50

µg/L.

16
 The districts showing the minimum arsenic pollution and concentration are in Ilam, Palpa and

Chitwan, where the maximum values of As concentration in the tested samples lie in the range of

10–50 µg/L, which is higer than the WHO 1993 threshold (Figure 5). The highest arsenic
concentration, >50 µg/L As, was reported at Nawalparasi but over all arsenic concentration level was
less than the Morang which had 46% tested sample having 10–50 µg/L As and 2% samples
having

>50 µg/L As. Udaypur and Jhapa have reported around 10–50 µg/L arsenic concentrations. Other
districts of Nepal had reported both types of arsenic concentration that is 10–50 µg/L As and >50
µg/L As in their tested sample.

In summary, the 89.8% of the samples of groundwater contamination by arsenic in Nepal has shown
a concentration lower than 10 µg/L, 7.9% in the range 10–50 µg/L and 2.3% higher than 50 µg/L of
As (Figure 6). Nevertheless, long term changes in land use practices, urbanization, industrialization,
population increment and other developmental activities foreseen in the near future could easily lead to
arsenic related problems. For this reason, the studied areas, which are not monitored regularly, will
require a continuous and regular monitoring of the arsenic pollution to find out eventual trends. Of
course, the 10.2% of tested samples showing already concentration values larger than the
internationally established threshold will require critical observation procedures and more sustainable
approaches for the mitigation and management of arsenic related problems.

17
 Figure 5. Percentage of arsenic contaminated samples in various districts of Nepal.

Kanchanpur
Kailali
Bardiya
Banke
Dang
Palpa
Kapilbastu

Rupandehi
Nawalparasi
Chitwan
Lalitpur
Kathm andu
Districts of Nepal

Parsa

Bara
Rautahat
Sarlahi % o f samp
les with <10 p
Mahottari p b As
Dhanusha
Udayapur
% o f samp les
Siraha with 10-50 p p
Saptari b As

Sunsari
Morang % o f samp
les with >50 p
Jhapa
p b As

Ilam

0% 50% 100%

Percentage of samples

18
 Figure 6. Overall arsenic concentration in the groundwater of Nepal.

>10–50 µg/L

7.91%

89.75%

0–10 µg/L

The statistical summary subdivided per institution or group, as well as the relative total, is reported in
Table 2. The results suggest that the samples having arsenic concentration in the range 10–50 µg/L
or greater than 50 µg/L require more attention for their management.

Table 2. Statistical summary of relative total groundwater arsenic contamination samples

subdivided per institution or group [43].

Total no.
of tests

Rural Water Supply and Sanitation Support

Programme (RWSSSP)/Finnish International

Rural Water Supply and Sanitation Fund

Japan International Cooperation Agency

(JICA)/Environment and Public Health Organization

19
 1.3 Rationale of the Study
 In the Terai region of Nepal, arsenic contamination is a major issue.
 Many research related to removal of arsenic has been carried out but only few
research has been carried out for the removal using Iron based adsorbents.
 Iron based adsorbents has been considered as an effective strategy for the removal of
arsenic due to its simplicity and regeneration potential.

1.4 Objectives of the study

Based on the factors discussed above, the overall objective of this study was to develop
an effective adsorbent using cellulose and iron hydroxide through a simple modification
process. Then the adsorbent was applied in batch and column experiments to investigate
the adsorption removal of As(III) and As(V) from water.

1.3.1 General Objective

 The primary objective of this study is to remove arsenic from water by using Iron-
Copper binary oxide as adsorbent.

1.3.2 Specific Objectives

 To characterize the structural properties of the adsorbents by different techniques.
 To investigate their removal efficiency towards arsenic under different condition.
 To analyze the regeneration and reuse of used adsorbent.
 To determine adsorption kinetics and adsorption isotherms of As(III) and As(V) by
the prepared adsorbents.
 To investigate the effect of iron contents on adsorption capacity of the adsorbents for
As(III) and As(V).

1.5 Limitations
 This research work is a preliminary work and in-depth study has not been
conducted.

1
2
1.6 Overview of Research Process

Literature Review

Preparation of adsorbents
(Fe-Cu, CuO, FeOOH)

Structural Characterization of Adsorbents

(ζ-potential, XRD, Particle Size, FTIR)

Batch experiments
Effect of pH, Adsorption Isotherm, and
Adsorption kinetics

Data Analysis and Interpretation

Results

Figure 1: Overview of Research Process

3
 1.7 LITERATURE REVIEW

2.1 Introduction
The name Arsenic is derived from the Greek word arsenikon, which means yellow
orpiment. Arsenic compound have been mined and used since ancient times. The
extraction of the element from arsenic compound was first reported by Albertus
th th th
Magnus in 1250 A.D. Arsenic ranks 20 in earth's crust, 14 in sea water and 12 in
human body. Arsenic exhibit metallic as well as non-metallic characteristics and
corresponding chemical properties. Hence, it is called metalloid.

Arsenic is one of the oldest human poisons known to mankind. It has six specific
characteristics (Azcui & Nriagu, 1994):
- It is a virulent poison on acute ingestion.
- It is extremely toxic on long term exposure to very low concentrations.
- It is not visible in water and food.
- It has no taste.
- It has no smell.
- It is difficult to analysis, even when occurring in concentration twice as high as
WHO guidelines.

2.2 Properties of Arsenic

Arsenic is a chemical element in the Nitrogen family, existing in both yellow and
grey crystalline forms. Although some forms of the Arsenic are metal-like, it
is best classified as metalloid and non metal. Some of the significant properties
of Arsenic are listed in Table 2.2.

Table 2.2 Properties of

arsenic

Parameter Value
Atomic Number 33
Atomic Weight 74.92158
0
Melting point 814 C at 36 atm
0
Boiling point 616 C

4
 Density: Gray form 5.73 g/cm3 at 14 0 C
Yellow form 2.03 g/cm3 at 18 0 C

Specific gravity (a, b, g ) 2.026,4.7,5.727

Latent heat of fusion 27,740 J/(mol-K)

Oxidation number -3, 0, +3, +5
Electronic configuration 2-8-18-5
Covalent radius 121 pm
Ionic radius 69 pm
Metallic radius 139 pm
Hard ness (Moh's scale) 3.5

2.3 Sources of Arsenic

There are mainly two sources of Arsenic, which are as follow:
a) Natural Sources
In nature, the Arsenic is distribute in variety of minerals, commonly as arsenide
of iron, copper, lead, silver and gold or as sulfide minerals, for example
arsenopyrite. The geochemical cycling of arsenic in the environment is through
interaction of natural water with bedrock, sediments and soils, together with the
local atmospheric deposition. The weathering of different geologic formation
such as volcanic rock, as well as mining waste consequently results in high
level of arsenic in surface and ground water.
b) Anthropogenic Sources
Anthropogenic processes such as industrial activities are great sources of arsenic
emissions. Arsenic based compounds have been used in pesticides, herbicides,
insecticides, fungicides, rhodenticides, algaecides, dye-stuff, dipping agent for
sheep, and vine killer. However, most developed countries have replaced such
inorganic compounds by organic arsenicals in agriculture. Arsenic-based
chemicals such as CCA (copper-chrome-arsenate) have been used in wood
preservation industries and there by caused widespread contamination of soil and
water. Other anthropogenic activities resulting high arsenic level in
the environment are mining, smelting and ore benefaction.

5
 2.4 Arsenic Contamination
Arsenic (As) is a toxic metalloid element which is ubiquitously found throughout the
earth’s crust (Chakraborti et. al 2010). It’s the twelfth most prevalent component in the
human body, the 14th most abundant element in the sea, and the twentieth most common
component in the earth's crust (Shih, 2005). Arsenic is a recognized carcinogen and is
one of the most toxic compounds in the world (USEPA 2001).

For many parts of the world, groundwater poisoning with arsenic poses a serious health
risk. 13 million Americans and 45 million to 57 million individuals in Bangladesh are
thought to be exposed to levels of arsenic greater than 10 µg/L (WHO, 2006). In Texas,
the Ogallala and Gulf coast aquifers frequently include groundwater sources with arsenic
values above 50 µg/L (Regner et al., 2004).

Many south and south-east Asian regions as well as the USA, Canada, China, Argentina,
and Chile have reported finding high quantities of as in their groundwater (Chen et al.,
1985; Welch and Lico, 1988; BGS and DPHE, 2001; Smedley and Kinniburgh, 2002;
Bhattacharyya et al., 2003a; Chatterjee et al., 2005; Nath et al., 2005, 2008a; Charlet and
Polya, 2006).

The 21 nations with proven groundwater arsenic pollution have the biggest population at
risk in Bangladesh, followed by West Bengal in India (Das et. al., 1995; Jain and Ali
2000; Rahman et. al., 2002, Chatterjee et. al., 1995, Robertson et. al., 1989).

Arsenic exists in both organic and inorganic forms in nature. In natural water systems,
inorganic arsenic is usually present. Inorganic arsenic often appears in trivalent and
pentavalent oxidation states in natural aqueous systems (Chang et al, 2008). The
solution's pH has a significant effect on arsenic speciation. Pentavalent arsenic (As (V),
arsenate) can only exist in an oxidizing surrounding, in contrast to trivalent arsenic (As
(III), arsenite), which is steady in reductive environments (Mohana et. al, 2007). In
general, inorganic arsenic poses a greater threat compared to organic arsenic and As (III)
is more hazardous than As (V) (Guo et. al, 2007). Arsenic cannot be removed by
controlling pH in an aqueous environment, even though heavy metals can be quickly
eliminated by a pH change or adsorption. In order to reduce these dangers, the United

6
States Environmental Protection Agency (USEPA) and World Health Organization
(WHO) enacted more strict arsenic rules (Jiang, 2001).

2.5 Arsenic in the Environment

There is a release of arsenic into the water and groundwater by a number of human-made
actions like mining, agriculture, and manufacturing as well as natural processes like
weathering reactions, mineral dissolution, and biological process (Cullen and Reimer,
1989; Smedley and Kinniburgh, 2002).

The main anthropogenic sources of arsenic are industrial effluents from the
metalworking, glass, ceramic, dye, and pesticide production, rare earth, gasoline
refinement, and other inorganic and organic chemical industries. Various industries that
release arsenic into the environment include those that produce phosphate detergent
builder, lead shot, wood and hide preservative, and use of in variety of fertilizers
(Banerjee et al., 1999; Viraraghavan et al., 1999). Another anthropogenic source of
arsenic is the burning of fossil fuels in homes and power plants. Arsenic-containing coals
or ores are also exposed during mining, and smelters release arsenic waste into natural
waterways (Bissen and Frimmel, 2003a).

2.6 Health Impacts of Arsenic

Drinking water poisoning with arsenic now poses a serious concern to the public's health
and has impacted millions of people worldwide (Mudhoo, 2011). Additionally, due to
processes of urbanization and the expansion of the global economy, abrupt anthropogenic
water contamination catastrophes happen regularly (Hu et al, 2014).

Intake of harmful inorganic substances by people over an extended period of time (like
5–10 years) causes arsenicosis, a term used to describe As-related health issues such as
skin conditions, internal cancers (urethra, kidneys, and lungs), skin conditions, conditions
that affect the blood arteries in the feet and legs perhaps diabetes, hypertension, and
reproductive problems, may all be brought on by consuming As contaminated food and
water (WHO 2011; USEPA 2013; Santra et al., 2013). Concern over arsenic in drinking
water has spread around the world because of its toxicity (Viet et al. 2003). Arsenic is
often strongly linked with naturally occurring minerals and so forth (Jay et al, 2005;
Karim, 2000). Because As (III) has a poorer affinity for soils and sediments than As (V),

7
research has shown that it is more mobile than As (V) (Smedley and Kinniburgh, 2002;
Tufano and Fendorf, 2008).

The United States Environmental Protection Agency has suggested decreasing the
maximum contamination limit (MCL) for arsenic in drinking water from 50 micrograms
per liter (µg/L) to 10 (µg/L) in order to protect humans from the effects of long-term
chronic exposure to arsenic. (U.S. Environmental Protection Agency, 2001). The World
Health Organization (WHO) suggested a maximum arsenic contamination level in
drinking water of 10 µg/L to avoid environmental dangers (World Health Organization,
2011).

2.7 Effects of Arsenic on Health

Arsenic called the king of all poison. The fatal dose, the dose which is sufficient for the
death of person, is 125 mg. The arsenic is 4 times stronger than mercury. Arsenic enters
the human body either from respiration or from mouth. The effects of arsenic after it
enters by breathing or meals and drinks depend on the amount and physico-chemical
states.

Arsenic has been identified as cause of cancer by the International Agency for Research
on Cancer (IARC). Many people died due to the cancer caused by arsenic.

According to the consumption of arsenic in human body, its toxicity can be

divided in three categories.

1. Acute toxicity

2. Sub acute toxicity

3. Chronic toxicity

Chronic arsenic poisoning, which occurs after long-term exposure through drinking-
water is very different to acute poisoning. Immediate symptoms on an acute poisoning
typically include vomiting, esophageal and abdominal pain, and bloody "rice water"
diarrhoea. Chelation therapy may be effective in acute poisoning but should not be used
against long-term poisoning.

8
The symptoms and signs that arsenic causes appear to differ between individuals,
population groups and geographic areas. There is no universal definition of the disease
caused by arsenic. This complicates the assessment of the burden on health of
arsenic. Similarly, there is no method to identify those cases of internal cancer that were
caused by arsenic from cancers induced by other factors.

Long-term exposure to arsenic via drinking water may causes cancer of the skin, lungs,
urinary bladder, and kidney, as well as other skin changes such as pigmentation changes
and thickening (hyperkeratosis). Increased risks of lung and bladder cancer and of arsenic
associated skin lesions have been observed at drinking water arsenic concentrations of
more than 0.05 mg/l.

Absorption of arsenic through the skin is minimal and thus hand-washing, bathing,
laundry, etc. with water containing arsenic do not pose human health risk.

Following long-term exposure, the first changes are usually observed in the skin:
pigmentation changes, and then hyperkeratosis. Cancer is a late phenomenon, and
usually takes more than 10 years to develop. The relationship between arsenic exposure
and other health effects is not clear-cut. For example, some studies have reported
hypertensive and cardiovascular disease, diabetes and reproductive effects.

2.8 Drinking Water Criteria for Arsenic

Arsenic in drinking water affects human health and is considered one of the most significant
environmental causes of cancer in the world. Keeping in view, the toxic effects of inorganic
arsenic on human and other living organism. It is necessary to understand the level of
arsenic in drinking water, and its chemical speculation, to establish regulatory
standards. The Food and Agriculture Organization(FAO) health limit for As in
groundwater was 50mg/l, but in view of recent incidences of arsenic poisoning in
Bangladesh and India, a decrease in groundwater as concentration to 5-10 mg/l is being
considered by a number of regulatory bodies throughout the world. The provisional WHO
guideline value adopted for arsenic in drinking water is 10 mg/l, which is based on a 6x10-4
excess skin cancer risk. WHO states that the health based drinking water guideline for
arsenic should be 0.17mg/l. However, the detection limit for most laboratories is 10 mg/l,
which is why the less protective guideline was adopted.

9
The United State Environmental Protection Agency (USEPA) drinking water standard for
arsenic (50 mg/l) was set in 1975. On the basis of the investigations initiated by national
Academy of Science, It was concluded that the previous standard did not eliminate the risk
of long term exposure from low arsenic concentrations in drinking water causing skin,
bladder, lungs and prostate cancer. To achieve the Environmental Protection Agency's
goal of protecting public health, recommendations were made to lower the safe drinking
water limit to 5 mg/l. Recently the USEPA has established a health based non forceable
maximum contaminant level goal of zero arsenic and an enforceable maximum contaminant
level (MCL) of 10 mg/l in all drinking water systems as against the previous MCL of 50
mg/l set by the USEPA in 1975. However, the current drinking water guideline for
arsenic of 10 mg/l, adopted by WHO and USEPA, is higher than the Canadian and
Australian MCL of 5 and 7 mg/l respectively. The national limit in India and Bangladesh is
50 mg/l (WHO, 1999). Nepal has also set 50 mg/l, as interim National standard for Arsenic.

In Nepal, guideline value for national drinking water quality standard has not been
finalized. Many organizations are working in this direction. The water quality
standard for Nepal, as suggested by Department of Water Supply and Sewerage is
tabulated in Table 2.4.

Table 2.4 Drinking water quality standard of Nepal

(proposed)

Category Parameters Units Desirable Maximum.

General pH - 6.5-8.5 9.2

Calcium mg/l <75 200
TDS mg/l <1000 1500
Aesthetic Turbidity NTU 5 20
Color TCU <5 15
Ammonia, NH3 mg/l <1.5 5
Chloride mg/l 250
Sulphate,SO4 mg/l <250
Total Hardness mg/l 150 300
Manganese, Mn mg/l 0.1 0.5
Iron, Fe mg/l 0.3 1.5
Copper, Cu mg/l <1 2.0
Chloride, Cl mg/l 250

10
 Chemical Cyanide, CN mg/l <0.07 0.2
Cadmium, Cd mg/l <0.003 0.01
(Inorganic)
Fluoride, F mg/l 0.5 1.5
Nitrate, NO3 mg/l <50
Arsenic, As mg/l <0.01 0.05
Lead, Pb mg/l <0.05 0.1
Chromium mg/l 0.05 0.05

Source: (IDI/DWSS, 2004)

2.9 Prevention and Control of Arsenic Contamination

The most important remedial action is prevention of further exposure by providing safe
drinking water. The cost and difficulty of reducing arsenic in drinking water increases as
the targeted concentration lowers. It varies with the arsenic concentration in the source
water, the chemical matrix of the water including interfering solutes, availability of
alternative sources of low arsenic water, mitigation technologies, amount of water to be
treated, etc.

Control of arsenic is more complex where drinking water is obtained from many
individual sources (such as hand pumps and wells), which is common in rural areas. Low
arsenic water is only needed for drinking and cooking. Arsenic rich water can be used
safely for laundry and bathing. Discrimination between high- arsenic and low-arsenic
sources by painting the hand pumps (e.g. red and green) can be an effective and low cost
measure to reduce exposure to arsenic when accompanied by effective health education.

Alternative low arsenic sources such as rain water and treated surface water may be
available and appropriate in some circumstances. Where low arsenic water is not
available, it is necessary to remove arsenic from drinking water. The technology for
arsenic removal for piped water supply is moderately costly and requires technical
expertise. It is inapplicable in some urban areas of developing countries like Nepal, and in
most rural areas world wide.

New types of treatment technologies, including co-precipitation, ion exchange and

activated alumina filtration are being field-tested. Until now, there are no proven
technologies for the removal of arsenic at water collection points such as wells, hand

11
pumps and springs. Simple technologies for household removal of arsenic from water
are few and have to be adapted to, and proven sustainable in each different setting.

2.10 Treatment Process for arsenic removal (Arsenic Removal

Technologies)
For the past decades, various methods have been developed and employed to remove
arsenic from water. Generally, the most studied technologies include oxidation,
coagulation and precipitation, lime softening, ion exchange, membrane filtration and
adsorption (Mondal et al. 2006, Sarkar and Paul 2016, Singh et al. 2015). To meet the
requirements of safe drinking water supply, any developed technology to be used in
arsenic polluted areas, especially in rural areas of developing countries, should consider
the factors such as simplicity in operation, cost -effectiveness, versatility and use
environmentally friendly resources. It is important to consider the accessibility of such
technologies to local communities and if these technologies can fit well with the rural
circumstances (Chwirka et al. 2000, Hsiao-Wen et al. 1999). So, this section is to make an
overview of these treatment processes for arsenic removal from water and to
compare advantage and disadvantage for each technology.

According to the literature, arsenic oxide cannot simply be destroyed; instead, it can only
be changed into other forms or into compounds that are soluble (Choong et. al 2007).
Therefore, it is a crucial and urgent task to create the materials and technologies needed
to effectively remove As (III) and As (V) from water (Abedin et. al, 2002). Both physico-
chemical or biological elimination techniques can be used to remove arsenic from
contaminated water (Mondal et al. 2006).

2.10.1. Oxidation
Under the near neutral pH and slightly reducing conditions in groundwater, arsenic is mainly
present as As(III), which is in the form of uncharged molecules. However, many techniques are
effective to remove the negatively charged As(V). Thus, oxidation has been applied as a pre-
treatment process to transform As(III) to As(V) before the treatment such as filtration,
coagulation and adsorption (Baig et al. 2013, Bissen and Frimmel 2003b). The general redox
transformation between As(III) and As(V) can be described as:

 
H3AsO4  2H  2e  H3AsO3  H2O E0  0.56 V

12
Although oxidation is a simple process and can be easily applied to the treatment of
large volumes of water, it can produce unwanted toxic by-products which need further
treatments.

2.10.2. Coagulation and Flocculation

The coagulation reaction between arsenic and coagulants can transform soluble arsenic
into floc which is easier to be separated from water by sedimentation or filtration.
Floc or large aggregates are formed due to the reduction of negative charge of arsenic
colloids by the positively charged coagulants (Choong et al. 2007b).

Coagulation is generally followed by filtration to remove the flocs, which is an

effective combination and widely used for arsenic removal. Because As(III) is
uncharged, it needs to be oxidized to As(V) for better removal by coagulation.

Coagulation combined with precipitation and filtration is an efficient method to remove

arsenic from water. However, the problems such as low removal efficiency for As(III)
and disposal of produced coagulation sludge have limited the applicability of this
technology.

2.10.3 Ion Exchange

Ion exchange method has been widely used for arsenic removal from water. It utilizes a
physicochemical process in which arsenic exchange with ions on the solid phases, which
are in most cases the synthetic resins. The surface of synthetic resins can be modified
using charged functional groups including strongly and weakly acidic groups or
strong and weakly basic groups by covalent bonds (Clifford 1999).

However, it requires the uncharged As(III) to be oxidized to As(V) before passing

through the resin column and the oxidant should be removed in case the chemicals
cause damage to the resins (Whitacre et al. 2012).

2.10.4 Membrane Filtration

Arsenic species can be separated from water by passing through a semi permeable
membrane under the pressure as driving force. Membrane has been regarded as one of the
most promising technologies for deep treatment of water. There are four types of
membrane filtration processes that are most widely studied for arsenic removal. They are

13
microfiltration (MF), ultrafiltration (UF), nanofiltration (NF), and reverse osmosis
(RO), of which MF is the low-pressure membrane process while the other three need high
pressure to provide driving force (Mondal et al. 2013).

The advantage of membrane filtration processes for arsenic removal is independence of

pH. In addition, there is no toxic by-product generated from the process. But the
processes can be affected by the presence of specific colloids which foul the back wash.
So, pretreatment is need for water containing high level of colloids. Another
disadvantage for membrane method i s the high cost and high energy
consumption, which may not be acceptable for people in rural areas in developing
countries (Mondal et al. 2013).

2.10.5 Absorption

Adsorption for arsenic removal is the process of accumulating arsenic species onto the
solid surface by physical as well as chemical forces. Numerous adsorbents have been
developed and applied for arsenic removal in the past decades. To better under the
development of ideas for the design of arsenic adsorbents, Mohan and Pittman critically
evaluated the performances of numerous adsorbents including the conventional
activated carbon, natural constituents, industrial by-products, metal oxides, and
composite materials (Mohan and Pittman Jr 2007). In this section, a brief review is made
based on some of the most commonly used adsorbents.

The most well-known adsorbent is activated carbon due to its high specific surface area,
which could be up to 2000 m2/g based on different activation methods. It has been reported
that the adsorption capacity of activated carbon for arsenic was only a few milligrams
arsenic per gram activated carbon. For example, arsenic adsorption by a set of 28 activated
carbons with the surface areas ranging from 388 to 1747 m2/g was studied. It showed that
the largest adsorption capacity was 2.0 mg/g. Sometimes the adsorption rate is not
sufficient to reach drinking water quality. However, a huge adsorption capacity (2860
mg/g) was reported with a coal-derived commercial activated carbon (Mohan and Pittman
Jr 2007). The adsorption of arsenic using activated carbon is dependent on the pH of the
water. The carbon-based nanomaterials such as graphene and carbon nanotubes are also
used for arsenic removal with the surface being functionalized by hydroxyl (-OH) or
carboxyl (-COOH) (Kuila et al. 2012). The granular activated carbon has been modified

14
using impregnation of metallic silver and copper to improve the adsorption capacity
(Rajaković 1992). Extensive reviews have been conducted on the metal based materials, the
most extensively studied are activated alumina, granular ferric hydroxide, iron oxide
coated carbon materials, and metal - metal composites (Adeleye et al. 2016, Lata and
Samadder 2016, Mehta et al. 2015, Ray and Shipley 2015). Adsorption of As(III) onto
activated aluminum has was investigated in terms of kinetics and isotherms. The
adsorption equilibrium was achieved within 6 hours and was dependent on initial
concentrations. The Langmuir isotherm showed the highest adsorption capacity was
2.29 mg/g. The intraparticle modeling showed that the mechanisms for arsenic to be
adsorbed included surface adsorption and intraparticle diffusion (Singh and Pant 2004).
For As(V), the adsorption removal using activated aluminum showed a Langmuir
behavior and the adsorption capacity reached 36.6 mg/g (Han et al. 2013). This suggests
that activated aluminum is more effective for adsorption of As(V) than As(III). Various
adsorption models have been used to fit the adsorption data of As(III) and As(V) by
activated aluminum grains. The adsorption can be described using both Freundlich and
Langmuir adsorption model (Lin and Wu 2001). A mesoporous alumina was used for
arsenic adsorption and the adsorption capacity reached 121 mg/g for As(V) and 47
mg/g for As(III) (Kim et al.2004).

Iron based adsorbents have been most widely studied and applied for arsenic adsorption
in recent years. Due to the high affinity to arsenic species, iron oxides and hydroxides
have attracted great attention. The adsorption capacity of iron oxides for arsenic was
reviewed to be higher than 100 mg/g. Studies have shown that the high affinity was
attributed to the formation of surface complex between iron hydroxide and arsenic
species. (Appelo et al. 2002, Farquhar et al. 2002, Sherman and Randall 2003) This
indicated that iron oxides are ideal materials for selective adsorption of arsenic from
water. However, if the iron hydroxides are applied alone, disadvantages of iron oxides
for arsenic removal include slow adsorption kinetics, narrow applicable pH range and
difficulty in disposal after adsorption. Also, because of its small particle size, iron oxide
nanoparticle cannot be used in continuous flow system. To overcome these difficulties,
novel materials were developed by combining iron oxides with other traditional
adsorbents. In the modification process, the traditional adsorbents serve a s supporting

15
matrix while iron oxides selectively remove arsenic from water (Adeleye et al. 2016, Lata
and Samadder 2016, Mehta et al. 2015, Mohan and Pittman 2007). The most frequently
used method is the modification of activated carbon by impregnating iron oxides on
the activated carbon surface. This kind of materials could take advantages of both
activated carbon as an ideal supporting media and iron oxides offering high affinity
with arsenic species (Chen et al. 2007). Studies have shown that in the adsorption
process, arsenate oxyanions could exchange with hydroxyl groups from iron hydroxides
and form inner-sphere monodentate or bidentate surface complex, represented as Fe-O-
AsO(OH)-O-Fe. Comparative studies showed that the impregnation of iron oxides with
activated carbon increased the adsorption capa city by more than ten times. Javier et
al. studied the influencing factors affecting arsenic adsorption by iron modified
activated carbon. It was proposed that the most important factor was the pH pzc value,
followed by iron content of the iron doped activated carbon. An iron content of about 1
wt.% was most favorable for arsenic adsorption. Mechanism study demonstrated that
arsenic was removed by both ligand exchange with hydroxyl groups and electrostatic
attraction with surface groups (Arcibar-Orozco et al. 2014). Muniz et al. compared
arsenic adsorption performance by activated carbon impregnated with Fe(III) and Fe(II).

However, most adsorbents obtained so far are not adaptive to packed bed filters due to
their nanometer level particle sizes. This is a major limitation for these adsorbents
to be applied in practical water purification projects. Also, for the iron based composite
adsorbents, the iron loading is a key factor affecting arsenic adsorption behavior. It
can be concluded that, to increase the adsorption capacity and adsorption rate of iron-
based adsorbents for arsenic, it is generally necessary to increase the loading
contents of iron and at the same time make the effective adsorption sites more accessible
to arsenic species (Yang et al. 2014). However, there is a lack of sufficient study on the
relations of iron loading contents and the adsorption capacity and kinetics for arsenic.
Therefore, in the present study, an iron hydroxide loaded cellulose bead adsorbent was
synthesized using a simple hydrolysis loading process. The potential of the obtained
adsorbent in application of arsenic adsorption was investigated through batch and
column study. The effects of iron hydroxide loading amount on arsenic adsorption
capacity and kinetics were studied.

16
 Ion exchange, chemical reduction, reverse osmosis, electrochemical means, modified
coagulation/filtration, and adsorption are just a few of the many approaches that
researchers with an emphasis on separation techniques have employed to remove arsenic
(Aredes et. al., 2013). However, these traditional methods have a number of problems,
including low efficiency, the need for chemicals, high energy use, and considerable
sludge formation (Mateen et. al., 2020).

Anion exchange resins were used in ion exchange technology, which was thought to be
an effective way to remove arsenic from water (Laatikainen et al, 2016). However, it is
ineffective for the uncharged As (III) species in water and only effective for the removal
of As (V). Additionally, the high-tech water filtration systems and the development of ion
exchange resin are typically expensive. The interference from the competing adsorption
of other co-existing anions reduced the adsorption capacity. Sludge disposal issues were
also brought up by the adsorbent regeneration process. Arsenic removal from water using
membrane techniques, including reverse osmosis and nanofiltration, has increased in
recent years (Bahmani et al, 2017). These methods have the benefits of high removal
effectiveness, simplicity of use, and minimal production of harmful sludge (Mezzenga et
al, 2017). However, the original cost and ongoing expenses are rather substantial, and
tremendous pressure is frequently required to push the contaminated water through the
membranes. Additionally, in the membrane process, the discharge of the concentrate,
membrane fouling, and flux reduction are typically unavoidable (Hao et al, 2018).
Arsenic and other pollutants could be removed using electro-dialysis, but significant
amounts of insoluble coagulants were also left behind on the cathode (Song et al, 2017).

Numerous nanoparticles have been created as a result of recent developments in

nanoscience and nanotechnology for the environmental remediation of different
pollutants from groundwater (Zhang, 2003). Nanoparticles are thought to be a good
alternative for quickly removing pollutants from aqueous solutions due to their high
specific surface area and reactivity (Huber, 2005). Researchers have become interested in
nanostructured metal oxides because of their excellent ability to remove arsenic, such as
mesoporous alumina, titanium oxide, nanocomposites made of aluminum oxide
nanoparticles (AluNPs) incorporated in macroporous polyacrylamide-based cryogels,

17
iron oxide, and hydrous cerium oxide. However there is a lot of interest in researching
alternative nanomaterials (Tsynedov et al., 2014).

Due to their simplicity of use, increased efficiency, and cost-effectiveness, adsorption-

based techniques are more often accepted when dealing with such restrictions (USEPA
2001; WHO 2011). Since nano-sized adsorbents have a large surface area and a lot of
active binding sites, ongoing research on them has received a lot of attention (USEPA
2013). The available surface area increases with decreasing size, boosting adsorption
over their surface (Santra et al., 2013).

Arsenic has been successfully adsorbable by a number of sorbents, with metal oxide
based sorbents including titanium [13], aluminum(14), zirconium(15), iron(16), and so
forth receiving the majority of attention.

Adsorbate and adsorbent are terms used to describe contaminants that are adhered to the
surface of solid surfaces (Ali 2012). Adsorption is one of the spontaneous methods used
in separation science and technology. It is also referred to as a physicochemical process
that involves the mass transfer of solutes from the liquid phase to the adsorbent surface
62, 63 without further formation of harmful by-products. Adsorption can be used to
recover valuable trace chemical elements, and adsorbents can be recycled 64, 65, 66.

Temperature, pH, the adsorbents' surface characteristics, and the characteristics of the
adsorbate are some of the factors that affect an adsorbent's ability to adsorb. 61, 67, 68.
Adsorption has historically been considered a crucial step in the process of treating
drinking water to remove organic waste that has been contaminated by heavy metals,
industrial wastes, colors, minerals, pesticides, fertilizers, and other pollutants 69.

The chemistry and composition of the As-contaminated water are the key determinants of
As removal. Most of the main reported cases of As involve As III, and oxidizing AsIII to
AsV is thought to be necessary to provide satisfactory As removals. (Shankar et al 2014).

Among the various metal oxides, copper oxide (CuO) and CuO-based nanomaterials,
important materials that are largely employed in energy, medical applications, have
gained significant attention for the removal of heavy metals from polluted water for
environmental remediation due to their high efficiency and low cost. Besides, the large

18
surface area and abundance of active sites on the surface of CuO makes it a reliable
adsorbent material for heavy metals, particularly As(V). This is clearly reflected in
various earlier studies. For instance, Pillewan reported that more than 95% of As(III) and
As(V) was successfully removed by copper oxide fused mesoporous alumina-based
material (Pillewan et. al., 2011). In another study, Zhang et al. applied Fe-Cu binary
oxide, a low-cost material prepared using a facile method as an effective adsorbent for
the exclusion of both As(V) and As(III) from water and has displayed excellent
performance (Zhang et. al., 2013). Moreover, CuO-based materials are also regard as
proficient adsorbents for water purification due to their low toxicity and negligible
solubility in the water.

Babaee et. al., 2017 conducted a study on using iron-copper bimetallic nanoparticles to
remove arsenic from synthetic contaminated waterways. From the study, he found that
maximum adsorption capacities for As(III) and As(V) to be 19.68 mg/g and 21.32 mg/g,
respectively and Adsorption isotherms fitted well into the Langmuir equation, and
sorption followed pseudo-second-order kinetics.

The research conducted by Shabani et. al., 2018 on the removal of arsenic and copper
from water by nanoparticles of magnetic iron bentonite showed that by enhancing the
contact time, temperature, and adsorbent dosage of the solution, the capacity for ions to
be adsorb was increased.

Koju et al 2020 conducted research on Adsorption of inorganic as(iii) from aqueous

solutions by iron-manganese oxide and studied As (III) adsorption under batch
experiments as an adsorption kinetics, isotherms, and effect of pH and prepared Iron-
Manganese oxides by oxidation and co-precipitation. Found that prepared adsorbents
were highly efficient in the removal of As(III). Adsorption of As (III) increases with
increase in the adsorbent dosage.

CuO is an effective arsenic adsorbent because it does not require pH adjustments or

oxidation of As (III) to As (V) and it performs well in the presence of competing anions
(Chen et. al., 2014). Cao et al. developed a hierarchically nanostructured CuO with high
specific surface area through a facile two-step process [85].

19
Martinson and Reddy synthesized CuO nanoparticles with a surface area of 85 m2 /g
[86], and the nanoparticles could effectively remove As(III) and As(V) at pH 6–10, with
a Langmuir monolayer capacity was ca. 9.4 mg g−1. Zheng et al. prepared a zirconium-
based magnetic sorbent with a surface area of 151 m 2 /g, showing a maximum As
adsorption capacity of 45.6 mg/g, which was much higher than many reported sorbents
[94]. It was proposed that the –OH groups played an important role in the uptake. Some
of the arsenate was reduced to arsenite after its adsorption onto the magnetic sorbent.

Cupric oxide (CuO) was found as an effective arsenic removal nano adsorbent, because it
did not require pH adjustments or oxidation of As (III) into As (V) and it performed well
in the presence of competing anions (Reddy, 2007; Reddy and Attili, 2005). These
nanoparticles are easy to regenerate and can be reused to remove arsenic from water. In a
study, cupric oxide nanoparticles was used in polypropylene centrifuge tubes for batch
study while sand was used as supporting material of nanoparticles for column study
(Reddy et al., 2013).

A nanostructured Fe-Cu binary oxide was synthesized via a facile co-precipitation

method as a facile, efficient, and low-cost adsorbent for arsenic removal from water
[106]. The Fe-Cu binary oxide with a Cu/Fe molar ratio of 1/2 displayed excellent
performance in removing both As(V) and As(III) from water, with the maximal
adsorption capacities for As(V) and As(III) of 82.7 and 122.3 mg/g at pH 7.0,
respectively. The presence of sulfate and carbonate showed no significant effect on
arsenic removal, but the phosphate obviously inhibited the arsenic disposal, especially at
high concentrations. Furthermore, the Fe-Cu binary oxide could be used repeatedly after
regeneration with NaOH solution.

Recent studies have demonstrated that nanoscale CuO can be used to prepare various
organic–inorganic nanocomposites with high thermal conductivity, high electrical
conductivity, high mechanical strength, high-temperature durability, and so on
[32,33,49,50]. CuO is more stable than Cu2O because Cu(II) ions are much more stable
in ambience, which makes it more important in practical applications.

20
 1.8MATERIALS AND METHODS
3.1 Materials
All the chemicals was of analytical quality and were used without additional purification.
Each month, the stock solutions were prepared and to prevent oxidation, it was stored in
the dark. As(V) stock solution of 1.5 mM was prepared with deionized water using
Sodium Arsenate (NaHAsO4.7H2O) and As(III) stock solution of 1.5 mM was prepared
with deionized water using Sodium Arsenite (NaAs2O3) and required solutions thereof
was prepared using the stock solution, which were then diluted with distilled water to
achieve predetermined concentration. All glass wares required for the study were soaked
in 15% nitric acid for 24 hours prior to before being used and was rinsed with distilled
water and dried at 160oC for 2 hours.

3.2 Preparation of adsorbents

The adsorbents Fe-Cu binary oxides, FeOOH and CuO were prepared following the
methods as described in previous studies with slight modifications (Gaosheng et.al.,
2013). To prepare Fe-Cu binary oxide, 20g of ferric chloride hexahydrate (FeCl 3.6H2O)
and 31.12g of copper(II) sulfate pentahydrate (CuSO4.5H2O) were dissolved in 250 mL
deionized water. The Cu:Fe molar ratio was adjusted to the predetermined value via
changing the amount of CuSO4.5H2O or FeCl3.6H2O added. Then, Sodium hydroxide
solution (5 mol L-1) was added drop wise under vigorous magnetic-stirring, to raise the
solution pH to around 7.5 ± 0.1. After pH was maintained, the prepared solutions was
continuously mixed under magnetic stirring for 1 hour and the suspension was kept at
room temperature for 3-4 hours. The formed supernatant was decanted, settled residue
was washed and the same volume of distilled water was added. The washing process was
continued until the clear solution appeared. After obtaining a clear solution, the mixture
was transferred in 50 mL polypropylene tubes to centrifuge at 7000 rpm for 4 minutes.
After this, the samples was placed in petridish and dried at 40°C for 3-4 hours and the
formed dried particles was crushed and sieved to obtain fine particles of size less than
100 μm. The sieved particles was then stored in a dessicator for the further use. A similar
process was used for the preparation of FeOOH (mixing Ferric Chloride hexahydrate

21
(FeCl3.6H2O) and NaOH), and CuO (mixing Cupric Chloride dihydrate (CuCl 2.2H2O)
and NaOH) .

3.3 Structural Characterization of Adsorbents

The adsorbents were characterized to know the structural properties and surface
morphology of the adsorbents. Fe-Cu Binary oxide, FeOOH and CuO were characterized
by the methods like Zeta potential (ζ-potential), Particle Size and X-ray diffraction
patterns (XRD).

3.3.1 Zeta Potential (ζ- potential):

The zeta (ζ-) potential of the adsorbents at different pH was analysed. Firstly, 10mg
(0.01g) of adsorbent was weighted and kept in polypropylene tube and 40ml distilled
water was added in it. By adding 0.1N NaOH and 0.1N HNO 3, pH of the solutions was
adjusted in a wide range of 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0 and 10.0 respectively. The
zeta potential was measured using Horiba Scientific Nano-Particle Analyzer SZ-100V2.
A minimum of three readings were recorded and the average value was measured under
different pH values.

3.3.2 Particle Size:

10 mg (0.01g) of adsorbent was weighted and kept in polypropylene tube and 40ml
distilled water was added in it. By adding 0.1N NaOH and 0.1N HNO3, pH of the
solutions was adjusted in a wide range of 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0 and 10.0
respectively. The prepared sample solution was filtered using 0.22 μm syringe filter and
particle size was analysed using Horiba Scientific Nano - Particle Analyzer SZ-100V2.

3.3.3 X-Ray Diffraction (XRD):

XRD was performed to know the crystalline structure of the adsorbents and X-ray
diffractometer (D2 phase Bruker) by using Cu ka radiation was for it. Data were collected
at 30 KV using a graphite curved crystal monochromator in the range of 10° to 90° (2θ).
The prepared adsorbents i.e. Fe-Cu, CuO and FeOOH were analysed to know their
structures.

22
 3.4 Batch Experiments
3.4.1 Effect of pH
pH of the solution is one of the important parameters in adsorption mechanism. The
experiment was carried out in 50 mL polypropylene tubes in room temperature. 40 mL
arsenic solution of 0.03 mM concentration was taken in the polypropylene tubes. With
the addition of 0.1 M NaOH and 0.1 M HNO 3, pH of the solutions was adjusted in a wide
range of 4.0, 5.0, 6.0, 7.0, 8.0 & 9.0 respectively. After the adjustment of pH about 5.0
mL solutions was syringed out from each solution before the addition of the adsorbents.
Then the adsorbents (Fe-Cu binary oxide, FeOOH and CuO) with a dosage 250 mgL -1
was added to the solution. After the addition of the adsorbents, pH was further
maintained and polypropylene tubes were kept on an end over end shaker set at 40 rpm
for 24 hours at room temperature. The pH was adjusted continuously throughout the
process at different intervals of time. After 24 hours reaction time, about 5.0 mL of the
solutions was drawn out with the help of syringe and filtered through 0.45 μm syringe
filter into polypropylene tube.

3.4.2 Adsorption Isotherm

In this study, all the adsorption isotherm experiments was conducted in 50 mL
polypropylene tubes with 40 mL of wide range of concentrations of arsenic
(0.002,0.004,0.006,0.008,0.011,0.015,0.022,0.03,0.045 and 0.06mM). The pH of the
solution was adjusted to 7.5±0.1 with the addition of 0.1 M NaOH and 0.1 M HNO 3.
After the adjustment of pH about 5.0 mL of solutions was drawn out as initial
concentration adding the adsorbents. Then, the adsorbents (Fe-Cu binary oxide, FeOOH
& CuO) with a dosage of 250 mgL -1 was added into the solutions. After the addition of
the adsorbents in the solution, the pH was maintained and the polypropylene tubes were
kept on an end over end shaker set at 40 rpm for 24 hours at room temperature. The pH
was adjusted in the solution throughout the reaction process in different intervals of time.
After 24 hours, approximately 5.0 mL of the solutions was drawn out with the help of
syringe and filtered through 0.45 μm syringe filter into the polypropylene tube. The
adsorption isotherm data was characterized using Langmuir and Freundlich model.

23
The equilibrium uptake qe,( mg g-1) of an adsorbent was calculated using the equation
(III).

[
q e= ( Co−Ce ) ×V (III)
M ]
Where,‘C0’is the initial concentration of adsorbate, ‘Ce’ is the equilibrium concentration
of the adsorbate, ‘V’ is the volume of the adsorbate and ‘M’ is the weight of the
adsorbents used in the study.

3.4.3 Adsorption Kinetics

In this study, the adsorption kinetics was performed in a glass beaker at room temperature
at initial arsenic concentration containing 0.0015 mmolL-1. The pH value of the solution
was maintained at 7.5±0.1 with the drop wise addition of 0.1 M NaOH and 0.1 M HNO 3.
After pH was maintained, approximately 5.0 mL of the solutions was drawn out with the
help of syringe and filtered through 0.45 μm syringe filter into the polypropylene tube
and was labelled as 0 min. Then, the dose of the adsorbents 200 mgL -1 was added into the
solutions. The solution was continuously stirred in a magnetic stirrer. The pH 7.5±0.1
was maintained throughout the process. After that, about 5.0 mL solutions was drawn
from the suspension with the help of syringe and filtered through 0.45 μm syringe filter
into the polypropylene tube at different interval of time 5min, 10min, 15min, 20min,
30min, 1 hour, 2hour, 3 hour and 24 hours.

The adsorption capacity (qt) of an adsorbent was calculated using the Equation (I) as
follows:

{ ( Co−Ct ) V } (I)
qt=
m

Where, qt is adsorption capacity in (mg g-1), CO& Ct are the concentrations of arsenic
before and after adsorption, m is the amount of the adsorbent used (g) and V is the
volume of the suspension (L). Similarly, removal efficiency of arsenic was calculated
according to equation (II).

Co−Ce
Removal %= × 100 (II)
Co

24
Where, Co is the initial concentration of arsenic solution and C e is the final concentration
of arsenic solution respectively.

3.5 Regeneration of adsorbents

The regeneration study is essential for reducing the operation cost in practical
application. The reusability of adsorbent was carried out by conducting five continuous
cycles of adsorption and desorption. For adsorption process, 0.25 g of each adsorbent was
taken in 100 mL distilled water with 0.0075mmL -1 arsenic solution and kept in a beaker.
It was continuously stirred in a magnetic stirrer by maintaining pH at 4.0 with the drop
wise addition of 0.1 M NaOH and 0.1 M HNO 3. After 5h, it was taken out and filtered in
a vaccum filter after completing the reaction cycle. The adsorbent was taken out and it
was air dried at room temperature. For desorption process, the adsorbents containing
arsenic were desorbed in 100 mL of 0.5M NaOH allowed to stir for 4 hours and filtered
in a vaccum filter. After filtration, the remaining adsorbent was washed thoroughly with
distilled water and it was air dried. Then again similar process was repeated. The
concentration of arsenic was determined by AAS.

3.6 Analytical methods (Analytical Procedures)

3.6.1 Fourier Transform Infrared Spectroscopy (FTIR)
For FTIR, 100 mL of 0.6 Mm arsenite and arsenate solution was taken in a beaker. Then, pH
7.5 ± 0.1 and pH 4 ± 0.1 was maintained separately. After maintaining pH, 0.2g (200mg)
of adsorbent was added. Then, the solution was left for mixing on magnetic stirring for
24 hours by maintaining pH throughout the reaction time. After 24 hour, the solution was
filtered using Rocker 300 Vacuum filter. The filtrate was dried at room temperature. The
FTIR spectra of each adsorbent were measured on Shimadzu IR Tracer -100.

3.6.2 Atomic Absorption Spectroscopy (AAS)

The concentrations of arsenic species were measured by Graphite Furnace AAS (GTA
120 graphite tube atomizer, Agilent Technologies 200 series AA).

25
 1.9RESULTS AND DISCUSSIONS
4.1 Structural Characterization of adsorbents
4.1.1 Zeta Potential (ζ- potential)
Results showed that ζ- potential of Fe-Cu decreased from 38.02 mV to -39.57 mV as pH
increased from 2.0 to 10.0. The iso-electric point (pH where the zeta potential is zero) of
Fe-Cu was found to be at pH 7.0. Similarly, ζ- potential of CuO decreased from 10 mV to
-58.1mV as pH increased from 2.0 to 10.0. The iso-electric point of CuO was at pH 3.0.
Likewise, the ζ- potential of FeOOH decreased from 28.00 mV to -75.90 mV as pH
increased from 2.0 to 10.0. The iso-electric point of FeOOH was pH 5.0. The higher the
value of Zeta potential, higher the stability state of the colloidal systems and potential
values (Sun et al., 2016).

It can be seen that the zeta potential of Fe-Cu nanoparticles gradually changes from
positive at a low pH value to negative at a high pH value. For Fe-Cu, below the pH 8, the
adsorbent surface is positively charged, and anion adsorption favored. With the increase
in pH, uptake of Fe-Cu ions decreased apparently because of the higher concentration of
OH– ions present in the reaction mixture. These OH– ions compete with Fe-Cu species for
the adsorption sites. Therefore, in the pH range of 2–6, nanoparticles could adsorb
negatively charged arsenic(III) and arsenic(V), while in the pH range of 7–10 they are not
favorable adsorbed since they are negatively charged. This result is similar with that
reported by Feng et. al. 2012.

Specific adsorption of anions makes the surface of oxides more negatively charged,
which results in a shift of the isoelectric point of adsorbent to a lower pH value ( Ren et.
al., 2011; Zhang et. al., 2009).

26
Figure 2: ζ- Potential measurement of Fe-Cu, CuO and FeOOH nano-particles over
a wide pH range

4.1.2 Particle Size:

The particle size of adsorbents was measured by application of dynamic light scattering
using Horiba scientific Nano-Particle Analyzer SZ-100V2. The particle size of Fe-Cu
ranges from 31.01 nm to 134.16 nm with mean particle size of 71.43 nm. The particle
size of CuO ranges from 3205.35 nm to 9615.42 nm with mean particle size of 5899 nm.
Similarly, the particle size of FeOOH ranges from 402.44 nm to 837.07 nm with mean
particles size of 597.85 nm.

It is important to note that the adsorption of Mn on the surface of GAC-Fe is more

influenced by its particle size than the other elements. By the decrease in the particle size
the outer surface of GAC-Fe increase, hence more % removal of Mn is obtained with
smaller particle size of GAC-Fe (Mondal et. al, 2008).

The adsorbent particle size also influences the adsorption capacity because fine particles
tend to have more adsorption surface area per unit mass (Schulze-Makuch et al. 2003). It
is found that particle size significantly influences both the adsorption capacity and

27
adsorption rate constant (Canales R.M. and Guan H., 2013). In this context, adsorbents
with particle sizes at nanometer scales have recently been found improving arsenic
removal from water, due to the different physical and chemical properties from that of
regular sizes are exposed at the nanoparticle surfaces (Yean et al. 2005).

Figure 3: Particle size of Fe-Cu, CuO and FeOOH nano-particles

4.1.3 X-Ray Diffraction (XRD)

The XRD patterns of Fe-Cu, CuO and FeOOH with 2θ degree ranging from 10° to 90°
are shown in Figure 4. Results showed that FeOOH was amorphous in nature having a
high surface area and a large number of active sites for adsorption as no obvious
crystalline peak were detected. The XRD pattern of Fe-Cu showed 3 slightly crystalline
peaks at 2θ values in the range of 16.30° to 39.87° and that of CuO showed 5 crystalline
peaks at 2θ values in the range of 16.54° to 53.94°. Out of 5 peaks, 3 peaks showed
intensity values of 7762, 6607 and 5360 at 2θ values of 16.54°, 32.59° and 39.99°
respectively. The observed XRD pattern showed few crystalline peaks indicating the
adsorbents to be slightly crystalline in nature (Hong, Farooq et al. 2010).

28
 Figure 4: X-Ray pattern of Fe-Cu, CuO and FeOOH nano-particles

4.2 Batch Experiments

4.2.1 Effect of pH
The pH of the solution determines the concentration distribution of the ionic forms of the
arsenic (III) and arsenic (V) (Chowdhury and Yanful 2010). The pH is an important
factor affecting the dissociation degree of adsorbate and surface charge of sorbent (Zhao
L. et. al., 2020). pH is one of the major influencing factors that affect the adsorptive
interaction on the adsorbents. So, it is essential to study the influence of pH value of the
solutions during adsorption process. To gain more insight into the adsorption process, the
effects of initial pH on adsorption capacity of arsenic (III) and arsenic (V) on adsorbents
were examined over a wide range of pH (4.0-9.0), respectively as demonstrated in Fig 5.

The adsorption of As (III) and As (V) was most significant at pH 4.0 and the elevated pH
inhibited their adsorption on any adsorbent. In this study, the maximum adsorption
capacity of As (III) onto Fe-Cu, CuO and FeOOH at pH 4.0 was determined to be 8.35
mg/g, 6.03 mg/g and 6.55 mg/g respectively.

Similarly, the maximum adsorption capacity of As (V) onto Fe-Cu, CuO and FeOOH at
pH 4.0 was determined to be 7.88 mg/g, 5.35mg/g and 9.21 mg/g respectively.
respectively. It was observed that the adsorption of As (III) and As (V) on adsorbents
increased quickly at pH …….. and then slowed at pH………….The removal rate showed
the same tendency as the maximum adsorption capacity was found at pH 4.0, which is
similar to the result of arsenic removal by Fe3O4 nanoparticles (Feng 2012). This result
indicates that the nanoparticles can remove the As(III) and As(V) more readily in an
acidic pH range. The amount of arsenic(III) and arsenic(V) uptake both decreased with

29
increasing pH, which may be attributed to zeta potential change of the nanoparticles
solution at different pH values. The decrease in As(III) sorption may be due to the
coulombic repulsion between As(III) species and the negative surfaces of Ce-Mn binary
oxide (pHpzc = 6.5) (Chen et al 2018).

pHpzc is a pH in which the net charge of chemical substances in the aqueous solution is
zero. At pH < pHpzc the adsorbent’s surface will positively charge, while at pH > pHpzc
the surface charge will be negative (Hylander, LD et al 2006). The pH zpc values suggest
the surface of the mixed oxide material should be predominantly positive and negative,
respectively, at below and above the pH 6.0 (±0.05). The surface charge density of the
material should increase or decrease with decreasing or increasing pH from the pH ZPC
(Gupta and Ghosh, 2008).

Figure 5: Effect of pH on adsorption of As (III) and As (V) onto Fe-Cu, CuO and
FeOOH
4.2.2 Adsorption Isotherm
Adsorption isotherms are used to describe the adsorbed mass as a function of the
equilibrium concentration of the adsorbing molecule at a constant temperature and pH
(Foo and Hameed 2010). Adsorption isotherms describe the adsorbate distribution
between adsorbed on sorbent and in aqueous solution, when adsorption equilibrium is
approached at a constant temperature.

In this study, the adsorption isotherms of As (III) and As (V) onto Fe-Cu, CuO and
FeOOH at pH 7.5±0.1 are exhibited in Figure 6. The maximum adsorption capacity
(Qmax) of Fe-Cu towards As (III) and As (V) was determined to be 12.08 and 9.40 mg g-1
respectively. Similarly, CuO and FeOOH showed lower adsorption capability, and their

30
corresponsive Qmax, As(III) was determined to be 2.40 and 14.94 mg g-1.and Qmax, As(V) was
found to be 7.43

and 9.62 mg g-1 respectively.

Figure 6: Adsorption isotherms for the adsorption of As (III) and As (V) onto Fe-
Cu, Cuo and FeOOH surfaces

The obtained experimental data of As (III) and As (V) were fitted by two adsorption
isotherm models i.e. Langmuir and Freundlich isotherm models as shown in Table 1. The
best fit between the two models was determined according to the favorable R 2 value and
the results showed that the Langmuir model was better fitted than the Freundlich model
to describe the adsorption of As(III) and As(V) onto the adsorbents Fe-Cu, CuO and
FeOOH with coefficient of regression (R2) value of ………………..
respectively.

The parameters were well fitted to Langmuir isotherm refers to the adsorption on
homogeneous surfaces within the adsorbents and monolayer coverage of arsenite and
arsenate at its outer surface (Liang et al., 2020).

31
Table 1: Langmuir and Freundlich isotherm constants for the adsorption of As(III)
and As(V) onto Fe-Cu, CuO and FeOOH at pH 7.5 ± 0.1

Adsorb Adsorbe Langmuir Freundlich Isotherm

ate nts Isotherm
qmax
(mg/ n
kL R2 kF R2
g)
As(III) 64.6 4.179 0.9 166.069 1.1 0.962
Fe-Cu
45 65 0
23.8 1.931 0.9 37.395 1.0 0.972
CuO
51 73 4
6230 0.003 0.9 266.256 0.9 0.999
FeOOH 5.53 98 8
1
40.1 5.080 0.9 113.553 1.1 0.993
Fe-Cu
98 95 3
As(V) 11.3 30.674 0.9 42.086 1.6 0.884
CuO
99 35 6
32.7 6.909 0.9 105.896 1.1 0.991
FeOOH
95 95 8

4.2.3 Adsorption Kinetics

The adsorption kinetics of As (III) and As (V) onto Fe-Cu, CuO and FeOOH were
determined through the curves of adsorption capacity as a function of time. Fig. 7 shows
that the adsorption of As (III) on these adsorbents was fast during the initial stage in 30
minutes and gradually slowed with increasing reaction time. The optimum time to attain
the equilibrium was 3 hours. The maximum adsorption capacity of As (III) i.e qt. max of
Fe-Cu, CuO and FeOOH were observed to be μg/g

Similarly, the adsorption of As (V) on Fe-Cu, CuO and FeOOH was fast during the initial
stage in 30 minutes and gradually slowed with increasing reaction time. This may be due

32
to the fine particles of Ce-Mn binary oxide powder. The smaller particle size is favorable
for the diffusion of arsenite molecules from bulk solution onto the active sites of the
adsorbent (Chen et. al., 2017)

To understand the adsorption mechanisms of arsenic onto adsorbents, two kinetic models
pseudo-first-order and pseudo-second-order models were fitted to the kinetic data. By
comparing the correlation coefficient R2, adsorption onto Fe-Cu can be best described
with a pseudo-second-order model on As(III) and As(V). Pseudo-second order model
best represented the adsorption kinetics characteristic indicating that adsorption process is
mainly driven by chemical reaction (chemisorption) (Fransiscus Y., 2018).

Generally, when adsorption involved a surface reaction process, the initial adsorption was
observed to be rapid because of a large number of available adsorption sites presenting on
the sorbent. Then, slower adsorption was expected as the number of available adsorption
sites gradually decreased (Zhao et. al., 2020).

Figure 7: Adsorption kinetics as a function of time of As (III) and As (V) onto Fe-
Cu, Cuo and FeOOH surfaces

33
Table 2: Adsorption kinetic models for the adsorption of As (III) and As (V) onto
Fe-Cu, CuO and FeOOH at pH 7.5 ± 0.1

Pseudo-first-order Pseudo-second-order

Adsorbate Adsorbents
Qmax K1 R2 Qmax K2 R2

mg/g 1/h mg/g 1/h

As(III) Fe-Cu 0.163 14.617 0.995 0.169 198.310 0.869
CuO 0.008 0.200 0.795 0.010 19.609 0.992

FeOOH 0.025 24.399 0.959 0.025 3309.482 0.872

As(V) Fe-Cu 0.021 60.649 0.514 0.021 66008.286 0.875

CuO 0.021 26.726 0.816 0.021 4383.289 0.872
FeOOH 0.021 35.836 0.886 0.021 10350.343 0.909

34
 4.2.4 Fourier Transform Infrared Spectroscopy (FTIR)
FTIR was performed to know the functional group of adsorbents before and after
adsorption. Fourier Transform Infrared Spectroscopy has been considered as a kind of
direct means for investigating mechanisms of arsenic adsorption on iron oxide minerals.
The specific adsorption of arsenic on the mineral surfaces involves ligand exchange
reactions where the anions displace OH- and=or H2O from the surface and therefore
changes in intensity of bands after and before the adsorption, which could be determined
through FTIR spectroscopy (Zhang et al. 2003).

Figure 8: FTIR spectra of Fe-Cu, CuO and FeOOH

4.3 Regeneration of Adsorbents

The regeneration capacity of adsorbents was analyzed to understand the reusability properties
of adsorbents. The adsorption and desorption cycles were performed for 5 consecutive cycles.
The adsorption capacity of Fe-Cu was retained above 90% during 5-cyclic successive runs.
The adsorption capacity of FeOOH slightly decreased after second cycle and remained
constant with the increasing cycles. The decrease in the adsorption rate could be ascribed to
the loss of certain portion of adsorbents during the operation. The recyclability result showed
that Fe-Cu could be easily regenerated and has a good potential for the long-term stabilities of
the adsorbent. Hence, Fe-Cu showed good adsorption performance towards As (III) and As
(V).

35
Figure 9: Removal rate of As (III) and As (V) onto Fe-Cu and FeOOH

36
 1.10 CONCLUSIONS
In this study, nanostructured Fe-Cu, Cuo and FeOOH were synthesized using co-
precipitation method. Adsorbents were characterized by Zeta-Potential, XRD, Particle
size and FTIR. Batch experiments like Effect of pH, Adsorption isotherm, adsorption
kinetics and Regeneration was performed. Results showed that Fe-Cu and FeOOH was
amorphous whereas FeOOH was crystalline in nature. The adsorption of adsorbents was
dependent on pH. The adsorption increased as pH value decreases and vice-versa.
Adsorption was more favourable under acidic conditions. The adsorption isotherm was
better fitted to Langmuir isotherm model with R2 value…….. referring to the
adsorption with monolayer on homogenous surface. Similarly, adsorption kinetics was
better fitted to the Pseudo-second-order model referring the adsoprtion to be
chemisorption. Also, Fe-Cu showed higher removal capacity towards As(III) and As(V)
than FeOOH. Fe-Cu can be easily regenerated, so it can be a promising adsorbent for
removing arsenic from water.

1.11

37
 1.12 RECOMMENDATION
Based on the finding of study following recommendation are made:

38
REFERENCES

39
PLATES

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