MINI PROJECT REPORT

ON

“ARSENIC REDUCTION FROM WATER”

SUBMITTED IN PARTIAL FULFILLMENT FOR THE COURSE OF

BACHELOR OF ENGINEERING
IN
CHEMICAL ENGINEERING

SEMESTER IV
SUBMITTED BY :
Rutika Patil
Mayur Sawant
Smitesh Shirke
Parag Ganagaram Juvatkar

UNDER THE GUIDANCE OF

Dr.S.R.DHOKPANDE

DEPARTMENT OF CHEMICAL ENGINEERING

DATTAMEGHE COLLEGE OF ENGINEERING
AIROLI, NAVI MUMBAI-400708.
(2021-2022)
 Program Out comes as defined by NBA (PO)

Engineering Graduates will be able to:

1. Engineering knowledge: Apply the knowledge of mathematics, science, engineering
fundamentals, and an engineering specialization to the solution of complex
engineering problems.
2. Problem analysis: Identify, formulate, review research literature, and analyse complex
engineering problems reaching substantiated conclusions using first principles of
mathematics, natural sciences, and engineering sciences.

3. Design/development of solutions: Design solutions for complex engineering problems

and design system components or processes that meet the specified needs with
appropriate consideration for the public health and safety, and the cultural, societal, and
environmentalconsiderations.
4. Conduct investigations of complex problems: Use research-based knowledge and
research methods including design of experiments, analysis and interpretation of data, and
synthesis of the information to provide valid conclusions.

5. Modern tool usage: Create, select, and apply appropriate techniques, resources, and
modern engineering and IT tools including prediction and modelling to complex
engineering activities with an understanding of the limitations.
6. The engineer and society: Apply reasoning informed by the contextual knowledge to
assess societal, health, safety, legal and cultural issues and the consequent responsibilities
relevant to the professional engineering practice.

7. Environment and sustainability: Understand the impact of the professional

engineering solutions in societal and environmental contexts, and demonstrate the
knowledge of, and need for sustainable development.

8. Ethics: Apply ethical principles and commit to professional ethics and responsibilities
andnorms of the engineering practice.
9. Individual and team work: Function effectively as an individual, and as a member or
leader indiverse teams, and in multidisciplinary settings.
10. Communication: Communicate effectively on complex engineering activities with
the engineering community and with society at large, such as, being able to comprehend
and write effective reports and design documentation, make effective presentations, and
give and receiveclear instructions.
11. Project management and finance: Demonstrate knowledge and understanding of the
engineering and management principles and apply these to one’s own work, as a
member and leader in a team, to manage projects and in multidisciplinary environments.
12. Life-long learning: Recognize the need for, and have the preparation and ability to engage
inindependent and life-long learning in the broadest context of technological change.
 Datta Meghe College of Engineering, Airoli, Navi Mumbai

DEPARTMENT OF CHEMICAL ENGINEERING

Institute Vision : To create value - based technocrats to fit in the world of

work and research

Institute Mission : To adapt the best practices for creating competent human
beings to work in the world of technology and research.

Department Vision : To provide enabling environment to nurture critical and

creative minds and to propel them together heights of
excellence in their pursuit of acquire knowledge in
chemical engineering in particular and life skills in general.

Department Mission:

M1: To focus on Chemical Engineering solution for sustainable development

M2: To develop skills to become technically competent professionals

M3: To understand the impact of Chemical Engineering solutions in a global,

environment, social context.

M4: To incorporate knowledge related to Chemical Engineering, sciences and

humanities’ for the overall development of the student
Program Educational Objectives (PEOs)

PEO1 - To be effective in applying Chemical Engineering principles in

practice or for advanced study in Chemical Engineering.
PEO2 – To have productive career in many diversified fields of Chemical
Engineering such as biotechnology, energy, environment etc.
PEO3 - To function effectively in the complex modern work environment with the
ability to assume professional leader roles.
PEO4 - To pursue higher study and or continuously upgrade the knowledge with
personal and professional growth.
PEO5 - The graduating students will be capable of identifying, formulating and
solving Chemical Engineering problems by using multidisciplinary tools
and techniques.

Program Specific Outcome (PSO)

PSO1 - An ability to grasp and apply Chemical Engineering fundamentals

considering the impact of environment, safety, economics and sustainability.
PSO2- Ability to identify, analyse, develop, design unit processes,
operation energy networking and equipment suitable to the contemporary
needs of the chemical industry.
PSO3 - Ability to work in Chemical and allied industries giving emphasis on
process control, simulation and to develop soft skill, managerial skill
and leadership attitude for addressing future challenges faced by society
and Industry.
 Datta Meghe College of Engineering, Airoli

Department of Chemical Engineering

Course Name: Mini Project 1B

Course Code: CHM401

Year of Study: S.E Semester: IV

Course Outcomes
CHM401.1 Identify problems based on societal / research needs.
CHM401.2 Apply Knowledge and skill to solve societal problems in a group.
& Develop interpersonal skills to work as member of a group or
leader.
CHM401.3 Draw the proper inferences from available results through
theoretical/ experimental/simulations.
CHM401.4 Analyse the impact of solutions in societal and environmental
context for sustainable development
CHM401.5 Excel in written and oral communication.

CHM401.6 Demonstrate project management principles during project work.

 UNIVERSITY OF MUMBAI
DATTA MEGHE COLLEGE OF ENGINEERING
PLOT NO-98, SEC-3, AIROLI, NAVI MUMBAI-400 708
DEPARTMENT OFCHEMICAL ENGINEERING

CERTIFICATE
This is to certify that:

Rutika patil

Mayur Umesh Sawant

Smitesh Shirke

Parag Ganagaram Juvatkar

has successfully carried out a Mini project 1B
On

ARSENIC REDUCTION FROM WATER

and submitted the work in Second Year Semester IV of Chemical Engineering of
University of
Mumbai during academic year 2021-2022.

Dr.S.R.DHOKPANDE
(Internal Project Guide) (External Examiner)

Dr. Mrs. K. S. DESHMUKH Dr. S. D. SAWARKAR

(H.O.D) (PRINCIPAL)
 ACKNOWLEDGEMENT

I am gratified to the Chemical Engineering Department, Datta Meghe College of

Engineering for giving me the opportunity for presenting a seminar on
“ARSENIC REDUCTION FROM WATER” in the final year as per the
curriculum of degree course of chemical engineering.
I am thankful to, Dr.S.R.Dhokpande my project guide for mentoring me
throughout the course and for sharing her valuable knowledge and time. She has
been a constant source of motivation, never expecting anything less than the best
efforts. Without her concern, advice and motivation it would have been difficult to
complete the seminar.
I would like to further extend my gratitude to Dr. Mrs. K. S. Deshmukh, the head
of department for chemical engineering and all the staff members of Chemical
Engineering Department. I would also like to thank all our faculty members and
librarians for their kind co-operation and support.
Last but not the least I would like to thank all our friends and family for their
unconditional support and help.
 INDEX
SR.NO. TOPICS PAGE NO.

1) ABSTRACT 5
2) INTRODUCTION 5
3) ARSENIC 7
4) HEALTH EFFECTS OF ARSENIC 7
6) Conventional Techniques 11
7) Oxidation Techniques 11
8) Coagulation-Flocculation 15
9) Membrane Technologies 18

10) Adsorption and Ion Exchange 20

11) Application of Nanoparticles 26
12) Conclusions 33

4|Page
 Abstract
This review paper presents an overview of the available technologies used nowadays for the
removal of arsenic species from water. Conventionally applied techniques to remove arsenic
species include oxidation, coagulation-flocculation, and membrane techniques. Besides, progress
has recently been made on the utility of various nanoparticles for the remediation of contaminated
water. A critical analysis of the most widely investigated nanoparticles is presented and promising
future research on novel porous materials, such as metal organic frameworks, is suggested.
Even at high concentrations, arsenic-contaminated water is translucent, tasteless, and odorless.
Yet almost every day, studies report a continually increasing plethora of toxic effects that have
manifested in exposed populations throughout the world. In this article we focus on recent
findings, in particular those associated with major contributions since 2006. Early life exposure,
both in utero and in childhood, has been receiving increased attention, and remarkable increases
in consequent mortality in young adults have been reported. New studies address the dose-
response relationship between drinking-water arsenic concentrations and skin lesions, and new
findings have emerged concerning arsenic and cardiovascular disease. We also review the
increasing epidemiological evidence that the first step of methylation of inorganic arsenic to
monomethylated arsenic (MMA) is actually an activation step rather than the first step in
detoxification, as once thought. Hexavalent chromium differs from arsenic in that it discolors
water, turning the water yellow at high concentrations. A controversial issue is whether chromium
causes cancer when ingested. A recent publication supports the original findings in China of
increased cancer mortality in a population where well water turned yellow with chromium.
Keywords: arsenic, pollution, water purification technology, engineered nanoparticles,
adsorption, metal organic framework

INTRODUCTION:
Being the 20th most abundant trace element in the earth’s crust, arsenic (As) is a constituent in
approximately 245 mineral species, which are predominantly ores containing sulfide, copper,
nickel, lead, cobalt, or other metals [1,2]. Arsenic is widely used in various fields such as
electronics, agriculture, wood preservation, metallurgy, and medicine [3]. These anthropogenic
sources contribute to the release of arsenic to the environment in addition to its release from
natural geological sources, for instance, by weathering of arsenic-containing rocks and volcanic
activities.
Arsenic is a naturally occurring metalloid that is very mobile in the environment. Its mobility
largely depends on the parent mineral form, oxidation state, and mobilization mechanisms [4]. In
terms of oxidation state, arsenic can exist in four forms, which are arsenite (As(III)), arsenate
(As(V)), arsenic (As(0)), and arsine (As(III)). Among these four arsenic species, the most
prevalent forms, which are commonly found in water, are the inorganic arsenite and arsenate [5].
Because of slow redox transformations, arsenite and arsenate are present in both reduced and
oxidized environments [4]. However, under anoxic reducing conditions (e.g., subsurface waters,
reduced sediments), arsenic primarily exists as arsenite, whereas arsenate is prevalent in aerobic
oxidizing environments, such as surface waters [6]. The pH also plays an important role in
determining the state of arsenic [7]. Figure 1 shows the Eh-pH diagram of arsenic species in the
system As-O2-H2O at a temperature of 25 ºC and total pressure of 101.3 kPa. Given a particular
pH and redox potential, the speciation of arsenic, including its oxidation state, can be determined
through this diagram [8]. This information is particularly useful in the determination of arsenic
5|Page
toxicity, taking the fact that the different arsenic oxidation states possess different toxicities into
account [9]. Moreover, considering the fact that negatively charged arsenate (i.e., H2AsO4− and
HAsO42−) is generally much easier to remove compared to uncharged arsenite (i.e., H3AsO3), this
Eh-pH diagram can assist in the selection of optimum environmental conditions for arsenic
removal [10].
Arsenic is known to be highly toxic to all life forms [11]. This element has been classified by the
World Health Organization as a group 1 human carcinogenic substance [12]. Recently, many
studies have been conducted regarding the environmental fate and behavior of arsenic due to
several arsenic pollution cases worldwide and the hazards associated with these. Upon chronic
intake of inorganic arsenic being present in concentrations above 50 μg/L in drinking water,
different kinds of skin lesions (e.g., hyperpigmentation, hyperkeratosis) and cancers (e.g., skin,
lung, kidney, bladder) can develop, which are collectively termed as arsenicosis [11]. In literature,
it is well reported that inorganic arsenic species are more toxic than the organic species mono-
methylarsenate (MMA) and dimethylarsinate (DMA). The toxicity of these species increases in
the order: DMA–MMA–arsenate–arsenite [13]. As(III) is more harmful for human health than
As(V) as it is more cytotoxic, genotoxic, mobile, and soluble [5,11,14]. With the accumulation of
trivalent intermediates in the human body, there is a higher possibility of developing arsenic-
induced diseases [15,16].
Exposure to arsenic can be through ingestion of arsenic-contaminated water or food and contact
with arsenic-contaminated air. Reports have shown that elevated levels of arsenic in drinking
water primarily contribute to human arsenic toxicity in the world [14,18,19]. Based on World
Health Organization (WHO) guidelines, arsenic concentrations in drinking water should be
strictly limited to 10 μg/L [6]. As groundwater is generally the main source of drinking water,
levels exceeding this standard can often be linked to the contamination of groundwater by
geothermal processes, mineral dissolution (e.g., pyrite oxidation), mining activities, desorption in
oxidizing environments, and reductive desorption and dissolution [20]. In regions where
contaminated drinking water is not the main source of arsenic for inhabitants, intake of food grown
in areas with elevated arsenic concentrations in soils and irrigation water represents the primary
cause of arsenic toxicity [11,21].
In 2012, it was estimated that about 202 million people worldwide are exposed to arsenic
concentrations in drinking water above 50 μg/L [18]. Comparing this to an estimate of 130 million
people in 2001, it can be inferred that there was a substantial increase in the number of people
affected [12].
Worldwide, groundwater arsenic contamination is worst in Asian countries, especially in
Bangladesh and West Bengal, India [22,23]. In both areas, the majority of the population depends
on tube wells for water supply. Since the arsenic source is geogenic in nature, it has been reported
that 79.9 million and 42.7 million people in Bangladesh and India, respectively, are exposed to
contaminated groundwater having concentrations above 50 µg/L [19,24]. In Bangladesh, the
arsenic concentration in some tube wells is as high as 4730 µg/L [22].
For the past three decades, several studies have shown that drinking arsenic-contaminated water
should be one of the major concerns for the health of mankind [25,26]. Thus, strategies to avoid
arsenic contamination of the groundwater and/or to alleviate the impact of such contamination
need to be developed in an attempt to reduce the health risks associated with the intake of arsenic-
contaminated water. In the following, a comprehensive overview is presented of the conventional
techniques used for the removal of As species from water. Moreover, besides the use of
nanoparticles for the treatment of arsenic-contaminated water, some novel porous adsorbents will
be presented in this work which could act as superior adsorbent materials in the near future due to
their outstanding characteristics, e.g., high pore volume and surface area.

6|Page
ARSENIC:

Arsenic is a chemical element with the symbol As and atomic number 33. Arsenic occurs in
many minerals, usually in combination with sulfur and metals, but also as a pure
elemental crystal. Arsenic is a metalloid. It has various allotropes, but only the gray form, which
has a metallic appearance, is important to industry.
The primary use of arsenic is in alloys of lead (for example, in car batteries and ammunition).
Arsenic is a common n-type dopant in semiconductor electronic devices. It is also a component
of the III-V compound semiconductor gallium arsenide. Arsenic and its compounds, especially
the trioxide, are used in the production of pesticides, treated wood products, herbicides,
and insecticides. These applications are declining with the increasing recognition of the toxicity
of arsenic and its compounds.
A few species of bacteria are able to use arsenic compounds as respiratory metabolites. Trace
quantities of arsenic are an essential dietary element in rats, hamsters, goats, chickens, and
presumably other species. A role in human metabolism is not known. However, arsenic
poisoning occurs in multicellular life if quantities are larger than needed. Arsenic contamination
of groundwater is a problem that affects millions of people across the world.
The United States' Environmental Protection Agency states that all forms of arsenic are a serious
risk to human health. The United States' Agency for Toxic Substances and Disease Registry
ranked arsenic as number 1 in its 2001 Priority List of Hazardous Substances at
Superfund sites. Arsenic is classified as a Group-A carcinogen.

HEALTH EFFECTS OF ARSENIC:

Carcinogenicity
Arsenic is the only carcinogen known to cause cancer through respiratory exposure and
gastrointestinal exposure. In the 1980s, arsenic was officially recognized as a carcinogenic
substance and registered with the International Agency for Research on Cancer (IARC) . Afterthe
association between arsenic exposure and carcinogenicity was revealed, studies were conducted
in the United States, Taiwan, Bangladesh, India, Argentina, and Chile to further examine this
association, and these results supported those of previous reports. Results from animal and
epidemiological studies have shown that inorganic arsenic compounds can be categorized as
clear carcinogens (group 1) or potential carcinogens (group 2B) such as DMA andMMA, while
arsenobetaine and other organoarsenicals have not been categorized as carcinogens (group 3).
Several hypotheses regarding the carcinogenicity of inorganic arsenic compounds have been
suggested; nevertheless, the biomolecular mechanisms are poorly understood. Nine different
hypotheses regarding the toxic mechanism behind arsenic have been suggested, including induced
chromosome abnormalities, oxidative stress, altered DNA repair, altered DNA methylation
patterns, altered growth factors, enhanced cell proliferation, promotion/progression, suppression
of p53, and gene amplification. To date, the IARC has confirmed the association of arsenic
exposure with cancers of the skin, lungs, and bladder, while reports on the relationship with the
7|Page
liver, kidney, and prostate cancer remain limited. Key epidemiological evidence regarding the
carcinogenicity of arsenic stems from studies from those in Taiwan, Bangladesh, Chile, and
Argentina, who consume drinking water containing high concentrations of arsenic (150 μg/L).
However, despite the well-established toxicity of arsenic, studies regarding the association
between chronic exposure to low concentrations of arsenic and the development of cancer are
lacking; further study is needed to support effective public health management.

Skin cancer
Several studies have reported an association between arsenic exposure and skin cancer.
Specifically, exposure to trivalent arsenite was found to be associated with the occurrence of UV-
induced skin cancers. In multiple regions, skin cancers associated with arsenic are often basalcell
carcinomas or squamous cell carcinomas caused by keratinization. For example, a cohort study
on 654 Taiwanese residents showed that the observed incidence rate of skin cancer was 14.7per
1000 person-years. In addition, skin cancer incidence increased significantly with the length of
stay in a black foot disease-infected region, length of drinking water usage, arsenic
concentration in the drinking water, and accumulated exposure to arsenic. Moreover, a recent
study has reported an association between skin cancer and vascular diseases. In a recent
epidemiological study conducted on residents of Hungary, Romania, and Slovakia that assessed
the carcinogenic risk of long-term low concentrations of arsenic in drinking water (the Arsenic
Health Risk Assessment and Molecular Epidemiology Study), low concentrations of arsenic
(≤100 μg/L inorganic arsenic) were significantly associated with the risk for developing basal cell
carcinoma.

Lung cancer
Hopenhayn-Rich et al. [22] observed a significant increase in lung cancer-related deaths with
arsenic intake. Moreover, numerous studies have investigated the dose-dependent relationship
between arsenic intake and lung cancer incidence, making lung cancer the most well-known
cancer associated with arsenic exposure [27,28]. Epidemiological studies have shown that the
incidence of lung cancer is consistently higher in groups exposed to arsenic than it is among the
general population or a control group [29]. In a recent study conducted in Taiwan, a high mortality
rate and standardized mortality ratio of lung cancer was observed among patients who consumed
high-arsenic concentrated drinking water for the past 50 years [30]. Moreover, reductions in the
arsenic concentration of tap water also decreased lung cancer mortality rates [30]. In the majority
of epidemiological studies, the relative risk of lung cancer is between 2 to 3. However, tobacco
smoking combined with and arsenic exposure increases the risk of lung cancer, and decreasing
arsenic exposure was also found to decrease lung cancer risk in smokers [31].
Until now, research has focused on the association between lung cancer and exposure to high
levels of arsenic studies of the association between lung cancer and low-level arsenic exposure
are lacking. A cohort study on 3932 Native Americans aged between 45 to 74 years investigated
the association between cancer mortality and low to medium arsenic concentrations was
conducted (average inorganic and methylated arsenic in the urine was 9.7 μg/g creatinine) [32].
They reported a hazard ratio was 1.56 (95% confidence interval [CI], 1.02 to 2.39), indicating a
significant, but relatively minor risk level. Given the potential relevance of low level arsenic
exposure, this paucity of data necessitates additional investigation.

Bladder cancer
Incident bladder cancer and arsenic exposure through drinking water has been verified by studies
in Taiwan and Bangladesh [33]. However, these studies have only verified the association after
exposure to high concentrations of arsenic; however, there is thought to be no association with
low exposures to arsenic (100 to 200 μg/L). Recent studies have debated whether, exposure to low
8|Page
concentrations of arsenic is related to bladder cancer because of potentially insufficient statistical
power and errors in the classification of exposure status in the previous studies. Thus, studies
accurately address these issues are needed. Under exposure to high concentrations of arsenic,
smoking interacts synergistically with arsenic to increase the risk of bladder cancer. During this
process, there is also a high possibility that the arsenic detoxification process is inhibited because
of DNA repair inhibition and reduced levels of essential nutrients [34,35]. In 2010, Meliker et al.
[36] reported no association with bladder cancer incidence after low concentrations of arsenic
exposure and smoking, but further confirmation is needed. One major limitation of these previous
studies might be an inability to a accurately measure of smoking and arsenic exposure levels,
which are needed future studies.

Liver cancer
Although previous studies conducted in Argentina, Chile, Denmark, and other regions have
reported a relationship with liver cancer, no consensus has been made on this relationship mostly
because of a limited availability to representative data [37,38]. Recently, the results of a 20-year
retrospective cohort study on liver cancer patients (802 male and 301 female) from 138
communities in Taiwan found a significant increase in liver cancer incidence in both genders at a
arsenic concentration above 0.64 mg/L, but no association was found at exposure levels lower
than lower 0.64 mg/L [39].

Prostate cancer
The association between exposure to high concentrations of arsenic and prostate cancer was
reported in Taiwan [5]. However, the association between exposure to low concentrations of
arsenic and prostate cancer is unclear, and epidemiological research is lacking. In a recent study
investigating low to medium inorganic arsenic exposure (via urine collection) and cancer
mortality in 3932 Native Americans (45 to 74 years of age), a high prostate cancer mortality
hazard ratio was observed (3.30; 95% CI, 1.28 to 8.48), which was even higher than that for liver
cancer (1.56; 95% CI, 1.02 to 2.39) [32].

Leukemia
Very few studies have investigated the association between arsenic exposure and leukemia. One
report observed that the number of leukemia patients (n=28) in Woburn, Massachusetts between
1966 and 1986 was more than 4 times greater than the average incidence rate of the US, and the
drinking water in this region was found to be contaminated with heavy metals such as arsenic (70
μg/L) and chromium (240 μg/L) at levels greater than the limit permitted by the state government
[40]. Furthermore, in a recent population-based case-control study on 69 pediatric leukemia
patients in California, a significant association between arsenic exposure and leukemia was
reported in most pregnant mothers (OR, 1.33; 95% CI, 1.02 to 1.73) [41].

Non-carcinogenic Effects

Neurological effects, memory, and intellectual function

Arsenic accumulated in the body during childhood may induce neurobehavioral abnormalities
during puberty, and neurobehavioral changes as an adult [42]. In addition, increased effects may
result after lead exposure; thus, caution is required. Neuritis caused by arsenic is a recognized
complication of arsenic toxicity, and is known to affect the sensory functions of the peripheral
nerves. Research on Mexican children has indicated an association between arsenic exposure and
deficits in verbal intelligence quotient and long-term memory. Furthermore, the effect was
proportional to the dose; therefore, a child exposed to 50 μg/L of arsenic performed significantly

9|Page
lower than a child exposed to 5.5 μg/L of arsenic did [43]. However, the effects of toxicity may
vary with the length of arsenic exposure, dose, and other nutritional factors.

Diabetes
Recently, the possibility of arsenic exposure affecting the incidence of diabetes has been
suggested. In particular, an association has been reported between type 2 diabetes occurring in
obese individuals aged 40 years or older and inorganic arsenic exposure. Studies conducted in
Taiwan reported that the incidence rate of diabetes for residents in a region with a high arsenic
drinking water level was 2 to 5 times higher than it was in unexposed subjects, which suggests
arsenic may influence diabetes incidence [44,45]. However, another study reported no association
[46]. It has been predicted that inorganic arsenic may be diabetogenic in humans, but additional
research is needed to elucidate the potential mechanism.

Effects on the skin

Several studies have examined the incidence of various skin disorders because of arsenic
exposure. According to a study conducted in Bangladesh, melanosis and keratosis occurred in 36
of 167 residents (13.9%) exposed to drinking water with low concentrations of 10 μg/L or less
arsenic [47]. Another recent study on 11 746 residents of Bangladesh exposed to arsenic in the
drinking water at concentrations of 8.1 to 40.0, 40.1 to 91.0, 91.1 to 175.0, and 175.1 to 864.0
μg/L reported ORs of 1.91, 3.03, 3.71, and 5.39, respectively [48]. These results suggest that
exposure to various concentrations of arsenic might affect skin cancer risk, and is related to
disorders in the prodromal phases of skin cancer.

Effects on cardiovascular disorders

Lee et al. [49] reported that arsenic might affect thrombocytes, which play an important role in
cardiovascular diseases. In the presence of thrombin, trivalent arsenite increases the agglutination
of thrombocytes. In animal studies, arsenic in drinking water was observed to increase arterial
thrombus formation. The study by Lee et al. [49] also reported that long-term intake of drinking
water with arsenic can increase thrombocyte agglutination and induce cardiovascular diseases.
However, additional studies are required to determine the relevance of these results in humans
[18].

Effects on the reproductive system

Pregnancy complications because of arsenic exposure from drinking water have been reported
[50]. In particular, fetal mortality and preterm birth increased as exposure to arsenic increased. It
was also found that exposure to arsenic during pregnancy affects urine excretion and the
distribution of metabolites, it affect the development of the fetus. Moreover these effects are
thought to manifest in various ways depending on the stage of pregnancy [51]. Animal studies
have suggest that these effects may be caused by necrosis, apoptosis, and loss of the fertilized egg
due to arsenic exposure [52]. While Hopenhayn et al. [53] suggested the possibility that chronic
exposure to low concentrations of arsenic (<50 μg/L ) may cause low birth weight and impair the
growth of the placenta in the uterus [53], additional research in this area is needed.

Conventional Techniques for Removal of as from Water

10 | P a g e
The chemistry and composition of arsenic-contaminated water are the major factors determining
the removal of arsenic [11]. Most of the available removal technologies are more efficient for
arsenate given that arsenite is predominantly non-charged at pH below 9.2 [27]. This makes the
trivalent form of arsenic less available for precipitation, adsorption, or ion exchange. Accordingly,
treatment technologies are believed to be more effective by using a two-step approach consisting
of an initial oxidation from arsenite to arsenate followed by a technique for the removal of arsenate
[5]. Figure 2 summarizes the presently available technologies that can be used for the removal of
arsenic from water

Arsenic Removal by Oxidation Techniques

Oxidation involves the conversion of soluble arsenite to arsenate. This alone does not remove
arsenic from the solution, thus, a removal technique, such as adsorption, coagulation, or ion
exchange, must follow [27]. For anoxic groundwater, oxidation is an important step since arsenite
is the prevalent form of arsenic at near neutral pH [11]. Aside from atmospheric oxygen, many
chemicals, as well as bacteria, have already been used to directly oxidize arsenite in water and
these are enumerated in Table 1.

Table 1
Different oxidants used to oxidize arsenite to arsenate, their operating conditions, properties, and
efficiencies.

11 | P a g e
 Operating Initial as Type of
Oxidants Remarks Reference
pH Concentration Water

Oxidation of As(III) by
ozone is faster than by
pure oxygen or air. In
less than 20 minutes,
complete oxidation was
Oxygen and ozone 7.6–8.5 46–62 µg/L Groundwater obtained using ozone, [28]
whereas five days were
needed to oxidize 57%
and 54% of As(III) using
pure oxygen and air,
respectively.

As(III) was completely

oxidized to As(V) by
active chlorine when its
Deionized
Chlorine 8.3 300 µg/L initial concentration was [29]
water
greater than 300 µg/L.
Stoichiometric rate was
0.99 mg Cl2/mg As(III).

After one hour contact

time, 86% oxidation
yield was achieved. This
relatively high value is
Chlorine dioxide 8.12 50 µg/L Groundwater mainly due to the [30]
presence of some metals
in water that could assist
the catalysis of As(III)
oxidation.

12 | P a g e
 Operating Initial as Type of
Oxidants Remarks Reference
pH Concentration Water

Very long contact time is

needed to obtain
effective As(III)
Monochloroamine 8.12 50 µg/L Groundwater [30]
oxidation. An oxidation
yield of only 60% was
achieved after 18 h.

Given a hypochlorite
concentration of 500
Hypochlorite 7 500 µg/L Groundwater µg/L, there was a [31]
complete oxidation of
As(III) to As(V).

The efficiency of As(III)

Freshwater oxidation improved as
Hydrogen peroxide 7.5–10.3 50 µg/L [32]
and seawater pH was increased from
7.5 to 10.3

Oxidation was
Potassium
8.12 50 µg/L Groundwater completed after one [30]
permanganate
minute.

Combining hydrogen
peroxide (H2O2) with
Photocatalytic
8 100 µg/L Groundwater ultraviolet (UV) [33]
oxidation (UV/H2O2)
radiation resulted in an
efficient As(III)
oxidation. As UV dose

13 | P a g e
 Operating Initial as Type of
Oxidants Remarks Reference
pH Concentration Water

increases, oxidation
efficiency also increases.
85% of As(III) was
oxidized to As(V) at a
UV dose of 2000
mJ/cm2.

CAOs can participate in

the oxidation of arsenite
Biological
to arsenate through the
Oxidation (e.g.,
use of oxygen (or nitrate)
chemoautotrophic - - - [34]
as terminal electron
arsenite-oxidizing
acceptors during the
bacteria (CAOs))
fixation of inorganic
carbon into cell material.

Oxygenated water is
pumped into the
In situ oxidation - - Groundwater groundwater aquifer to [35]
reduce As concentrations
to <10 µg/L.

In developing countries, atmospheric oxygen, hypochlorite, and permanganate are the most
commonly used oxidants. Oxidation of arsenite with oxygen is a very slow process, which can
take hours or weeks to complete [36]. On the other hand, chemicals, such as chlorine, ozone, and
permanganate, can rapidly oxidize As(III) to As(V) as presented in Table 1. However, despite this
enhanced oxidation, interfering substances present in water need to be considered in selecting the
proper oxidant as these substances can greatly affect and dictate the kinetics of As(III) oxidation
[11]. For instance, the oxidation rate of arsenite by ozone can be greatly reduced if S2− and TOC
are present in water [37]. Also, in another study, it was shown that competing anions and organic
matter in groundwater greatly affect the use of UV/titanium dioxide (TiO2) in arsenic oxidation
[38]. Furthermore, this involves a complex treatment, which produces an As-bearing residue that
is difficult to dispose. Thus, to efficiently remove arsenic from a solution by oxidation, oxidants

14 | P a g e
should be selected carefully. Moreover, all cited disadvantages of oxidation alone make it a less
competent method for arsenic removal.

Coagulation-Flocculation
Coagulation and flocculation are among the most employed and documented techniques for
arsenic removal from water [27,39]. In coagulation, positively charged coagulants (e.g., aluminum
sulphate (Al2(SO4)3), ferric chloride (FeCl3)) reduce the negative charge of colloids, thereby
making the particles collide and get larger. Flocculation, on the other hand, involves the addition
of an anionic flocculant that causes bridging or charge neutralization between the formed larger
particles leading to the formation of flocs. During these processes, dissolved arsenic is
transformed by the chemicals into an insoluble solid, which undergoes precipitation later [40].
Alternatively, soluble arsenic species can be incorporated into a metal hydroxide phase and be co-
precipitated [27]. Either way, solids can be removed afterwards through sedimentation and/or
filtration.
Arsenic removal efficiency of different coagulants varies as a function of pH. Below pH 7.6,
Al2(SO4)3, and FeCl3 are equally effective in removing arsenic from water [41]. Between the two
inorganic arsenic species, most researchers suggested that arsenate is more efficiently removed
compared to arsenite and that FeCl3 is a better coagulant than Al2(SO4)3 at pH higher than 7.6
[41,42,43,44,45]. However, despite their reported inferior performance compared to ferric
chloride, aluminum-based coagulants were still able to reduce arsenic concentrations to below the
maximum concentration level (MCL) of 10 μg/L given that the initial concentration is 280 µg/L
[29]. Table 2 shows a list of the coagulants used in arsenic removal, together with their operating
conditions, properties, and efficiencies.

Table 2
Different coagulants used to remove arsenic, their operating conditions, properties, and
efficiencies.

Operating Initial as Type of

Coagulant Remarks Reference
pH Concentration Water

At an optimum FeCl3 dosage of 30

mg/L, As(III) and As(V) removal

Distilled efficiencies were approximately 45%

Ferric Chloride 7.0 2 mg/L [46]
water and 75%, respectively. Arsenic
removal was enhanced at higher
FeCl3 concentrations, however,
residual iron after coagulation

15 | P a g e
 Operating Initial as Type of
Coagulant Remarks Reference
pH Concentration Water

exceeded MCL of iron in drinking

water.

About 90% of initial As(V)

concentration was removed from the
River solution using 40 mg/L
Alum 7.0 20 µg/L [47]
water Al2(SO4)3 ·18 H2O. As(III) removal
with alum was negligible even at
higher alum doses.

The percentage removal of As(V)

with 2 mg/L ZrCl4 dosage was

approximately 55%. This value

Zirconium(IV) Distilled
7.5 50 µg/L increased at pH 6.5 and decreased at [48]
Chloride water
pH 8.5. In contrast to that of As(V),
the removal efficiency of As(III) was
approximately 8% regardless of pH.

With 2 mg/L TiCl3, As(III) and

As(V) removal efficiencies of 32%

Titanium(III) Distilled
7.5 50 µg/L and 75% were achieved, [48]
Chloride water
respectively. Both As(III) and As(V)
removal were highly pH dependent.

As(V) removal was highly pH

Titanium(IV) Distilled
7.5 50 µg/L dependent, whereas As(III) removal [48]
Chloride water
was independent of pH. With 2 mg/L
TiCl4 dosage, approximately 55% of

16 | P a g e
 Operating Initial as Type of
Coagulant Remarks Reference
pH Concentration Water

As(V) was removed, while As(III)

removal was 26%.

Both As(V) and As(III) removal

were pH dependent. The percent
Titanium(IV) Distilled removal of As(V) with 2 mg/L
7.5 50 µg/L [48]
Oxychloride water TiOCl2 dosage was 37%. Given the
same conditions, As(III) removal
was about 20%.

With 2 mg/L ZrOCl2 dosage,

approximately 8% and 59% of
As(III) and As(V) were removed,
Zirconium(IV) Distilled
7.5 50 µg/L respectively. As(V) removal was [48]
Oxychloride water
highly pH dependent, whereas
As(III) removal was independent of
pH.

Double As(III) removal efficiency of 80%

Ferric Sulfate 7.0 1 mg/L distilled was achieved with 25 mg/L [49]
water Fe2(SO4)3 dosage.

Ti(SO4)2 was employed for enhanced

Double
Titanium(IV) As(III) removal. The removal
7.0 1 mg/L distilled [49]
Sulfate efficiency of As(III) was 90% at a
water
coagulant dose of 25 mg/L.

Open in a separate window

17 | P a g e
The major drawback of coagulation-flocculation is the production of high amounts of arsenic-
concentrated sludge [11]. The management of this sludge is necessary so as to prevent the
consequence of secondary pollution of the environment. Moreover, treatment of sludge is costly.
These limitations make this process less feasible, especially in field conditions [40].

Membrane Technologies
In view of drinking water production, membrane filtration is a technique that can be used for the
removal of arsenic and other contaminants from water. Typically, membranes are synthetic
materials with billions of pores acting as selective barriers, which do not allow some constituents
of the water to pass through [50]. A driving force, such as pressure difference between the feed
and the permeate sides, is needed to transport the water through the membrane [51]. Generally,
there are two categories of pressure-driven membrane filtrations: (i) low-pressure membrane
processes, such as microfiltration (MF) and ultrafiltration (UF); and (ii) high-pressure membrane
processes, such as reverse osmosis (RO) and nanofiltration (NF) [40,50]. The characteristics of
these four processes are summarized in Table 3.

Table 3
Overview of pressure-driven membrane processes and their characteristics [51,52].

Reverse
Microfiltration
Parameter Ultrafiltration (UF) Nanofiltration (NF) Osmosis
(MF)
(RO)

Permeability
> 1000 10–1000 1.5–30 0.05–1.5
(l/h.m2·bar)

Pressure (bar) 0.1–2 0.1–5 3–20 5–120

Pore size (nm) 100–10,000 2–100 0.5–2 < 0.5

Rejection
− − − +
Monovalent ions

Multivalent ions − −/+ + +

18 | P a g e
 Reverse
Microfiltration
Parameter Ultrafiltration (UF) Nanofiltration (NF) Osmosis
(MF)
(RO)

Small organic
− − −/+ +
compounds

Macromolecules − + + +

Particles + + + +

Separation Solution-
Sieving Sieving Sieving Charge effects
mechanism Diffusion

Clarification; Removal of Removal of organic

Removal of
Applications Pretreatment; macromolecules, compounds and some
salts
Sterilization bacteria, viruses dissolved salts

Using membranes with pore sizes between 0.1 and 10 µm, MF alone cannot be used to remove
dissolved arsenic species from arsenic-contaminated water. Thus, the particle size of arsenic-
bearing species must be increased prior to MF; the most popular processes for this being
coagulation and flocculation [11]. In a study conducted by Han et al. [53], arsenic removal from
drinking water was investigated through flocculation and MF wherein ferric chloride (FeCl3) and
ferric sulphate (Fe2(SO4)3) were used as flocculants. Results showed that flocculation before MF
leads to effective arsenic binding onto the ferric complexes present and subsequent arsenic
removal in the permeate. However, the pH of the water and the presence of other ions are major
factors affecting the efficiency of this arsenic immobilization. This can be a disadvantage of this
technique especially when dealing with arsenite removal as this arsenic form has a neutral charge
in the pH range of 4–10 [50]. Since arsenate is negatively charged in this pH range, it can bind by
surface complexation resulting in efficient arsenate removal. Thus, for this technique to be
effective, complete oxidation of arsenite to arsenate is needed.
In the same way as MF, UF alone is not an effective technique for the treatment of arsenic-
contaminated water due to large membrane pores [54]. To make use of this technique in arsenic
removal, surfactant-based separation processes such as micellar-enhanced ultrafiltration (MEUF)
can be utilized [55,56]. For instance, adding cationic surfactant to contaminated drinking water at

19 | P a g e
a concentration above the critical micelle concentration (CMC) of the water will lead to formation
of micelles, which can bind to negatively charged arsenic species. In effect, there will be arsenic
removal in the permeate as the surfactant aggregates are large enough to pass through the
membrane pores. Several studies have already focused on arsenic removal using MEUF. In one
such study, the arsenate removal efficiency of different cationic surfactants was investigated [57].
Among the tested surfactants, hexadecylpyridinium chloride (CPC) showed the highest removal
efficiency, i.e., 96%. However, arsenic removal was also reported to decrease with decreasing pH.
Moreover, despite the effective removal of arsenic, the concentration of the surfactant in the
effluent is so high that it needs to be further treated with powdered activated carbon (PAC) before
being discharged to the environment.
Both NF and RO are suitable for the removal from water of dissolved compounds with a molecular
weight above 300 g/mol [51]. These techniques can significantly reduce the dissolved arsenic
level in water given that the feed is free from suspended solids and that arsenic is preferably
present as arsenate [58]. In a study conducted by Sato et al. [59], it was shown that the removal
efficiency for As(V) exceeded 85% for all investigated NF membranes, while that of As(III) was
far too low. This is supported by the findings of Uddin et al. [60], who indicated that without
oxidation of arsenite to arsenate, NF cannot comply with the MCL of arsenic in water. The same
is the case for RO, as shown in several studies [50,61].
Although technically not a membrane system, diatomaceous earth (DE) filtration is a process that
works very similar to that of membrane filters [62]. DE is a chalky sedimentary material
containing fossil-like skeletons of microscopic water plants known as diatoms [63]. The size of
diatoms ranges from 5–100 micrometers and are characterized by a porous structure having small
openings of about 0.1 micrometer in diameter. The combined effect of small pore sizes and high
porosity makes DE one of the most effective filters used to remove small particles at high water
filtration rates [62,63]. Furthermore, this type of filter is odorless, tasteless, and chemically inert
making it safe for filtering drinking water. Misra and Lenz [64] developed a method for removing
arsenic and heavy metals from water using precipitated mixed hydroxides followed by DE
filtration. In one of the laboratory-scale tests performed, an initial arsenic concentration of 100
µg/L was reduced by 90% using a reagent dose of 1000 mg/L. However, several drawbacks should
also be considered, such as the need for pH adjustment, reagents, and a long conditioning time
[64].

Adsorption and Ion Exchange

Adsorption is a process that uses solids as medium for the removal of substances from gaseous or
liquid solutions [11]. Basically, substances are separated from one phase followed by their
accumulation at the surface of another. This process is driven mainly by van der Waals forces and
electrostatic forces between the adsorbate molecules and the adsorbent surface atoms. This makes
it important to characterize first the adsorbent surface properties (e.g., surface area, polarity)
before being used for adsorption [39].
A wide variety of sorbents has already been studied in several research areas as shown in Table
4. These include activated carbon, coal, red mud, fly ash, chicken feathers, kaolinite,
montmorillonite, goethite, zeolites, activated alumina, titanium dioxide, iron hydroxide, zero-
valent iron, chitosan, and cation-exchange resins. The table illustrates that iron-based adsorption
is an emerging technique for the treatment of arsenic-contaminated water. This can be explained
by the fact that there exists a high affinity between inorganic arsenic species and iron [65]. Iron
can remove arsenic from water either by acting as a sorbent, co-precipitant or contaminant-
immobilizing agent, or by behaving as a reductant [40].

20 | P a g e
 Table 4
Comparative evaluation of different sorptive media previously used for arsenic removal.

Sorption
Capacity
Adsorben Surfac (mg/g)
Type of Optimu Temperatur Reference
Adsorbent t Dosage e Area
Water m pH e (°C) s
(g/L) (m2/g)
As(III As(V
) )

Coconut-shell Distilled
5.0 5 1200 25 - 2.40 [74]
carbon water

Coconut-shell
carbon Distilled
5.0 10 - 25 - 4.53 [74]
pretreated with water
Fe(III)

Coal-based Distilled
5.0 5 1125 25 - 4.09 [74]
carbon water

Copper-
impregnated Distilled
6.5 2 206 30 20.35 - [75]
coconut husk water
carbon

Deionized
double-
Rice polish 7.0 20 452 20 0.14 0.15 [76]
distilled
water

21 | P a g e
 Sorption
Capacity
Adsorben Surfac (mg/g)
Type of Optimu Temperatur Reference
Adsorbent t Dosage e Area
Water m pH e (°C) s
(g/L) (m2/g)
As(III As(V
) )

Sorghum Deionized
5.0 10 - - 3.6 - [77]
biomass water

Distilled
Fly ash 4.0 1 0.8 * 20 - 30 [78]
water

Activated Drinking
7.6 1–13 370 25 0.18 - [66]
alumina water

Modified
Synthetic
chicken 4.0 10 - 20 0.13 - [79]
water
feathers

Allyl alcohol-
Synthetic
treated chicken 7.0 10 - 25 0.115 - [80]
water
feathers

Eggshell Distilled
7.0 8 - 30 - 24.2 [81,82]
membrane water

22 | P a g e
 Sorption
Capacity
Adsorben Surfac (mg/g)
Type of Optimu Temperatur Reference
Adsorbent t Dosage e Area
Water m pH e (°C) s
(g/L) (m2/g)
As(III As(V
) )

Synthetic
Deionized
zeolite H-MFI- 6.5 2 450 20 - 35.8 [83]
water
24

Granular
Groundwate
titanium 7.0 1 250.7 13.4 32.4 41.4 [84]
r
dioxide

Granular ferric Deionized-

240–
hydroxide distilled 6.5 0.25 20 - 1.1 [85]
300
(GFH) water

Double-
Iron oxide-
distilled 7.0 30 - 15 0.73 - [86]
coated cement
water

Iron oxide- Distilled

7.5 20 - 27 0.029 - [87]
coated sand water

Deionized
Iron-oxide- 7.0 5 9.18 * 25 2.216 5.452 [88]
water
coated

23 | P a g e
 Sorption
Capacity
Adsorben Surfac (mg/g)
Type of Optimu Temperatur Reference
Adsorbent t Dosage e Area
Water m pH e (°C) s
(g/L) (m2/g)
As(III As(V
) )

manganese
sand (IOCMS)

Iron-modified Deionized-
activated distilled 7.6–8.0 0.1–20 723 20-23 38.8 51.3 [89]
carbon water

Amorphous Deionized
6.0–8.0 1.6 - - 28.0 7.0 [70]
iron hydroxide water

Zero-valent Groundwate
10.0 5 1.8 * 25 - 1.92 [90]
iron r

Deionized
Goethite 6.0–8.0 1.6 - - 22.0 4.0 [70]
water

Fex(OH)y-
Deionized
Montmorillonit 6.0–8.0 1.6 165 - 13.0 4.0 [70]
water
e

24 | P a g e
 Sorption
Capacity
Adsorben Surfac (mg/g)
Type of Optimu Temperatur Reference
Adsorbent t Dosage e Area
Water m pH e (°C) s
(g/L) (m2/g)
As(III As(V
) )

TixHy-
Deionized
Montmorillonit 6.0–8.0 1.6 249 - 13.0 3.0 [70]
water
e

Natural siderite Tap water 7.31 2 - 20 1.04 0.52 [91]

Kaolinite - 5.0 100 33 * 25 - 0.86 [92]

Modified Double-
calcined distilled 7.0 5 - 30 - 1.566 [93]
bauxite water

Activated red Distilled

7.25/3.50 20 - 25 0.884 0.941 [94]
mud water

Deionized
Chitosan resin distilled 6.0 2 - 40 4.45 - [95]
water

25 | P a g e
 Sorption
Capacity
Adsorben Surfac (mg/g)
Type of Optimu Temperatur Reference
Adsorbent t Dosage e Area
Water m pH e (°C) s
(g/L) (m2/g)
As(III As(V
) )

Cerium-loaded
Deionized
cation 5.0–6.0 10 - 25 2.5 1.03 [96]
water
exchange resin

Surface-
Artificial 50–
modified 7.0 - 25 - 8.0 [97]
wastewater 55 *
diatomite

Adsorption has been reported as the most widely used technique for arsenic removal due to its
several advantages including relatively high arsenic removal efficiencies [66,67], easy operation,
and handling [68], cost-effectiveness [69], and no sludge production [11]. However, adsorption
of arsenic strongly depends on the system’s concentration and pH. At low pH, arsenate adsorption
is favored, whereas for arsenite, maximum adsorption can be obtained between pH 4 and 9 [70].
Moreover, contaminated water does not only contain arsenic; it is always accompanied by other
ions, such as phosphate and silicate, competing for the adsorption sites [71]. Aside from the
system’s conditions, the effectiveness of adsorption in arsenic removal can also be hindered by
the type of adsorbent itself. As shown in Table 4, a number of adsorbents have already been
studied for the removal of arsenic from water. However, most conventional adsorbents have
irregular pore structures and low specific surface areas, leading to low adsorption capacities. Lack
of selectivity, relatively weak interactions with metallic ions, and regeneration difficulties can also
confine the ability of these sorbents in lowering arsenic concentrations to levels below MCL
[72,73].

Application of Nanoparticles

Recently, advances in nanoscience and nanotechnology have paved the way to the development
of various nanomaterials for the remediation of contaminated water [40]. Due to their high specific
surface area, high reactivity, and high specificity, nanoparticles have been given considerable
environmental attention as novel adsorbents of contaminants, such as heavy metals and arsenic,
26 | P a g e
from aqueous solutions [98]. Carbon nanotubes and nanocomposites, titanium-based
nanoparticles, iron-based nanoparticles, and other metal-based nanoparticles are among the most
widely used and investigated nanoparticles for the treatment of arsenic-contaminated water
[72,99,100,101]. Table 5 presents a summary of the comparative evaluation of some nano-
adsorbents used for arsenic removal.

Table 5
Comparative evaluation of various nano-adsorbents for arsenic removal.

Sorption
Properties Capacity
(mg/g)

Adsorben
Operatin Temperatur Reference
Nano-Adsorbent t Dosage
Averag g pH e (°C) s
(mg/L)
e Surfac
As(III As(V
Particl e Area
) )
e Size (m2/g)
(nm)

Multiwall carbon
nanotubes
functionalized
17.4 22.5 4.0 0.1 25 - 13.0 [93]
with polyethylene
glycol (PEG-
MWCNTs)

Hydrous titanium
4.8 312 7.0 500 25 83.0 - [95]
dioxide

Iron-doped TiO2 108.0 - 7.0 4000 - - 20.4 [108]

27 | P a g e
 Sorption
Properties Capacity
(mg/g)

Adsorben
Operatin Temperatur Reference
Nano-Adsorbent t Dosage
Averag g pH e (°C) s
(mg/L)
e Surfac
As(III As(V
Particl e Area
) )
e Size (m2/g)
(nm)

Ti-loaded basic
10.0–
yttrium carbonate 82.0 7.0 1000 25 - 348.5 [109]
30.0
(Ti-BYC)

α-
Fe2O3 nanoparticl 5.0 162.0 7.0 100 25 95.0 47.0 [104]
es

γ-
7.0–
Fe2O3 nanoparticl 168.73 - - - 67.02 - [110]
12.0
es

Fe2O3 nanoparticl
12.3 - 6.0 100 - 20.0 4.9 [111]
es

Magnetite
20.0 69.4 6.5 400 25 8.0 8.8 [105]
nanoparticles

28 | P a g e
 Sorption
Properties Capacity
(mg/g)

Adsorben
Operatin Temperatur Reference
Nano-Adsorbent t Dosage
Averag g pH e (°C) s
(mg/L)
e Surfac
As(III As(V
Particl e Area
) )
e Size (m2/g)
(nm)

Fe3O4 nanoparticl
5.0 178.48 7.0 60 - 46.06 16.56 [112]
es

Ceria
6.6 86.85 - 5000 30 18.02 * [107]
nanoparticles

CeO2–CNT - 189.0 7.0 25 - - 81.9 [113]

Zirconium oxide
10.8 98.0 7.0 100 - 5.2 6.0 [108]
nanoparticles

Zirconium oxide
- 327.1 7.0 100 25 83.0 32.4 [109]
nanoparticles

Carbon Nanotubes (CNTs)

CNTs have been reported to be effective in the adsorption of various organic chemicals and metal
ions after treatment with oxidants [102,103,104]. In a study conducted by Choudhury et al. [105],
As(III) adsorption efficiency of Multiwall CNTs was approximately 34.22% after 30 min, given
an initial As(III) concentration of 542 µg/L and a sorbent concentration of 1 g/L. Furthermore, the

29 | P a g e
results revealed that Multiwall CNTs are able to remove arsenic to safe limits, but only for a low
initial arsenic concentration.
CNTs can also be functionalized in order to increase removal efficiency for metal ions.
Velickovic et al. [106] synthesized CNTs functionalized with polyethylene glycol (PEG) for the
removal of As(V) and other metal ions from wastewater. It has been shown that the adsorption of
these metal ions on PEG-CNTs is strongly pH dependent. Moreover, for an initial concentration
of 10 mg/L and pH equal to 4, the maximum adsorption capacity of As(V) on this functionalized
CNT was found to be 13.0 mg/g.
However, in general, CNTs may not be a better alternative for activated carbon as all-
encompassing adsorbents. Nevertheless, CNTs still show potential in some applications wherein
only small amounts of materials are required, which implies less material cost. These applications
include polishing steps to remove recalcitrant compounds or pre-concentration of trace organic
contaminants for analytical purposes [100].

Titanium-Based Nanoparticles
Pena et al. [107] evaluated the effectiveness of nanocrystalline titanium dioxide (TiO2) in arsenic
removal and in photocatalytic oxidation of As(III). Adsorption of arsenite and arsenate by
nanocrystalline TiO2 reached equilibrium within four hours, whereas with commercial nonporous
TiO2 particles, it was already reached in an hour. Furthermore, higher adsorption capacity was
obtained using nanocrystalline TiO2, which can be due to its higher specific surface area than the
nonporous TiO2 particles. At an equilibrium arsenic concentration of 45 g/L, more than 80% of
both arsenic species was adsorbed by this nano-adsorbent. In terms of oxidation, nanocrystalline
TiO2 was also shown as an efficient photocatalyst considering that arsenite was completely
converted to arsenate within 25 min in the presence of sunlight and dissolved oxygen.
Another titanium-based nano-adsorbent being used in arsenic removal is hydrous titanium dioxide
nanoparticles (TiO2·x H2O). These offer the advantage of being effective adsorbents for As(III)
without the need for oxidation to As(V) or any pH adjustment before and after the adsorption
process [38]. Xu et al. [114] synthesized hydrous TiO2 nanoparticles, which were tested for
As(III) removal from laboratory-prepared and natural water samples. With a maximum adsorption
capacity of 83 mg/g at near neutral pH and 96 mg/g at pH 9, application of TiO2·x H2O proved to
be an effective, low-cost, and single-step process for the treatment of arsenic-contaminated water.
However, because of their size, dispersion of these nanoparticles into the environment is to be
expected. Thus, granulation of these nanoparticles into micron-sized particles or loading onto very
porous host materials is needed.
A recent study conducted by Lee et al. [109] showed an enhanced arsenate removal in aqueous
solution using Ti-loaded basic yttrium carbonate (BYC). The maximum adsorption capacity of
Ti-loaded BYC at pH 7 was reported to be 348.5 mg/g, which is 25% higher than either BYC or
yttrium hydroxide. This can be attributed to its increased specific surface area (82 m2/g) and
surface charge (PZC:8.4). Moreover, Ti-loaded BYC also displayed high adsorption capacities in
a wider pH range (pH 3–11). This adsorbent also performed well even in the presence of
coexisting anionic species (e.g., phosphate, silicate, bicarbonate). However, this study did not
report on the potential of Ti-loaded BYC to adsorb arsenite.

Iron-Based Nanoparticles
Among the most important nanomaterials studied for the treatment of arsenic-contaminated water
are iron-based nanoparticles, which include zero-valent iron nanoparticles (nZVI) and iron oxide
nanoparticles (i.e., Fe3O4, and γ-Fe2O3). The oxidation state of iron in these particles has a major

30 | P a g e
influence on their capability to remove contaminants [101]. Several mechanisms are involved in
these removal processes (Figure 3).

Open in a separate window

Figure 3
Schematic model of the removal mechanisms of nZVI, Fe3O4, and γ-Fe2O3 (Adapted with permission
from [101]).

Zero-Valent Iron Nanoparticles (nZVI)

Several laboratory studies have demonstrated that the application of nZVI is an effective
technology for transforming pollutants into their nontoxic form [115]. For instance, dyeing
reagents can be adsorbed effectively to functionalized nZVI, which exhibited a maximum
adsorption capacity of 191.5 mg/g for one type of dye studied [116]. In this case, adsorption was
the result of donor-acceptor bonds formed in the reaction between the functional group –NH2 on
the nZVI surface and the –OH group on the target compound. As for heavy metals, adsorption
and co-precipitation are generally accepted mechanisms involved in removal by nZVI [72]. As
schematically shown in Figure 3, these mechanisms occur because an iron oxide shell is formed

31 | P a g e
once nZVI is brought in contact with air or water. Removal of arsenic is a widely studied example
[117,118].
Using high resolution X-ray photoelectronic spectroscopy (HR-XPS), Ramos et al. [119] studied
the arsenic immobilization mechanism using nZVI. Primarily due to the core-shell structure of
nZVI, it was shown that both reductive and oxidative mechanisms take place upon application of
nZVI. This structure is characterized by a highly reducing metal core and a thin layer of
amorphous iron (oxy)hydroxide that helps in the coordination and oxidation of As(III). However,
despite this reported advantage of nZVI being a versatile technology for arsenic remediation, other
studies also indicated that this nano-adsorbent is disadvantageous when it comes to synthesis
[120].

3.3.2. Iron Oxide Nanoparticles

Iron oxide nanomaterials are increasingly becoming prevalent in the field of arsenic removal
because of their ability to remove arsenic five to ten times more effectively than their micron-
sized counterparts [72]. This enhanced uptake capacity for metals, in general, can be attributed to
their high surface-to-volume ratios [121]. In addition to this, iron oxide nanoparticles possess
magnetic properties, which allow them to be conveniently separated from aqueous solutions [122].
Tang et al. [123] synthesized ultrafine α-Fe2O3 nanoparticles using a solvent thermal process to
treat laboratory-prepared and natural water samples contaminated by arsenic. Studying the
kinetics revealed that As(III) and As(V) removal by α-Fe2O3 nanoparticles can be achieved very
rapidly. Within the first 30 minutes of contact, around 74% of As(III) was already removed with
an α-Fe2O3 loading of 0.04 g/L and an initial As(III) concentration of 0.115 mg/L. For a solution
containing 0.095 mg/L of As(V), 100% removal was achieved when the α-Fe2O3 loading was only
half of that used for As(III). The synthesized nanomaterial, with a BET specific surface area of
162 m2/g and an average particle diameter of 5.0 nm, showed high arsenic adsorption capacities
at around neutral pH conditions. Adsorption capacities for As(III) and As(V) were determined to
be 95 mg/g and 47 mg/g, respectively. Moreover, this study showed that the presence of Cl−, NO3−,
and SO42− in the water has only a minimal negative effect on arsenic adsorption. Only HPO42− and
SiO32− could lower the arsenic adsorption substantially, especially the adsorption of As(V), when
the concentrations of these two anions were high.
The performance of magnetite (Fe3O4) nanoparticles in treating arsenic-contaminated water was
investigated by Chowdhury and Yanful [124]. This nano-adsorbent has a BET surface area of 69.4
m2/g and a mean particle diameter of 20 nm. Results showed that arsenic adsorption by
Fe3O4 nanoparticles is largely dependent on the pH of the solution, contact time, initial arsenic
concentration, PO43− concentration in the solution, and the adsorbent concentration. At an initial
arsenic concentration of 2 mg/L, maximum adsorption of both arsenic species was achieved at pH
2. Arsenate adsorption decreased rapidly when pH was above 7, whereas for arsenite, adsorption
was more or less constant in the pH range 2–9. Furthermore, maximum arsenic adsorption
capacities were calculated to be 8.0 mg/g and 8.8 mg/g for As(III) and As(V), respectively, using
the Langmuir isotherm. The effect of phosphate on arsenic removal was also studied and results
showed that removal percentages decreased with increasing phosphate concentration. This result
is in accordance with the study conducted by Roy et al. [105] wherein the presence of phosphate
at a concentration of 0.5 mg/L decreased As(III) and As(V) removal percentages by 13% and
25%, respectively.
Mayo et al. [125] also studied As(III) and As(V) removal using nanocrystalline magnetite
particles. Their results confirmed that the size of the nanoparticles has a significant effect on their
adsorption behavior. Adsorption capacities for both arsenic species increased about 200 times
when the particle size was decreased from 300 nm to 12 nm. Hristovski et al. [98] investigated
the removal of arsenate through batch experiments carried out using 16 commercially available
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nanoparticles of metal oxides. Most of these nanoparticles removed >90% of arsenate from almost
all water matrices, with TiO2, Fe2O3, ZrO2, and NiO nanopowders performing best. These
nanoparticles showed the highest removal efficiencies, exceeding 98%, except for ZrO2 in
groundwater.

Other Metal-Based Nanoparticles

Ceria Nanoparticles
Feng et al. [126] conducted batch experiments to study the adsorption of arsenic on ceria
nanoparticles. Results showed that arsenic removal by this nanomaterial is pH-dependent. For
arsenate, adsorption increased when the pH increased from 1 to 6, and then decreased as pH
continued to increase beyond 6. Similar trends were observed for arsenite, although arsenite
adsorption was observed to continuously increase in the pH range from 1 to 8. Moreover,
Langmuir adsorption isotherms revealed that the adsorption capacities of these nanoparticles
were 17.08 mg/g, 18.02 mg/g, and 18.15 mg/g at 10, 30, and 50 °C, respectively, indicating that
arsenic adsorption is favored at higher temperatures.

Zirconium Oxide Nanoparticles

Being chemically stable, non-toxic, and insoluble, zirconium-based oxides could also be an
option for drinking water purification [127]. One of the few studies regarding this group of
nanoparticles was conducted by Cui et al. [128]. They synthesized amorphous zirconium oxide
(am-ZrO2) nanoparticles by a hydrothermal process for arsenic removal from water. Through
kinetics studies, it was shown that by using only a relatively low dosage of am-
ZrO2 nanoparticles (i.e., 0.10 g/L), arsenic concentrations in water can be reduced to levels
below MCL within 12 h for As(V) and 24 h for As(III). Moreover, the adsorption process was
observed to be effective under near neutral pH conditions and does not need any pretreatment or
post-treatment. Maximum adsorption capacities of these am-ZrO2 nanoparticles were found to
be 83.2 mg/g and 32.5 mg/g for As(III) and As(V), respectively.

Conclusions and Perspectives

Arsenic is recognized as a persistent contaminant in groundwater with severe impact on human
health when exposed through, amongst other sources, drinking water. Arsenic emissions from
natural sources, including not in the least certain Asian countries, and anthropogenic emissions
urge for on-site remediation to reduce the toxicity risks. Conventional techniques generally focus
on arsenate removal after an initial oxidation of arsenite by either atmospheric oxygen, bacterial
activity, or chemical reagents. Increasing the particle size of soluble species is possible by a
coagulation/flocculation process and allows removal by precipitation or membrane filtration in a
consecutive step. Ion-exchange resins alternatively are capable of directly immobilizing As ions,
but this process is subject to pH influences and competition from co-occurring ions such as
phosphate or silicate. Nevertheless, practical use of these conventional and non-conventional
techniques is still limited due to the fact that their adsorption capacities are still too low and there
is a lack of potential to regenerate and reuse the adsorbents.

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Nanomaterials made of carbon, titanium, iron, ceria, or zirconium are an emerging class of
adsorbents due to their high specific surface areas, high reactivity and high specificity.
Nevertheless, the nanoparticles’ high surface energies mean they tend to aggregate in aqueous
media, which results in a drastic decrease in surface area and therefore in a reduced capacity and
selectivity, reducing the process lifetime and potential for real life application.
However, despite the number of studies conducted regarding nanoparticle stabilization for
adsorption, little or no attention was given to a novel class of porous materials that was recently
gaining considerable attention in other fields of research because of their outstanding properties.
These are Metal Organic Frameworks (MOFs), which possess high surface areas, tunable pore
sizes and shape, high thermal stability, and a relatively simple synthesis. Moreover, they have the
advantages that they can be easily pre- or post-modified on the organic moieties for target specific
compounds. MOFs now became subject of exploration for removing hazardous substances such
as arsenic or fluoride from contaminated water streams. Their excellent adsorption capacities
encourage further development of adsorption technologies towards reaching acceptable arsenic
levels.

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