Ecotoxicology and Environmental Safety 112 (2015) 247–270

Contents lists available at ScienceDirect

Ecotoxicology and Environmental Safety

journal homepage: www.elsevier.com/locate/ecoenv

Review

Arsenic contamination, consequences and remediation techniques:

A review
Rachana Singh a, Samiksha Singh b, Parul Parihar a, Vijay Pratap Singh c,n,
Sheo Mohan Prasad a,n
a
Ranjan Plant Physiology and Biochemistry Laboratory, Department of Botany, University of Allahabad, Allahabad 211002, India
b
Department of Environmental Science, University of Lucknow, Lucknow 226025, India
c
Govt. Ramanuj Pratap Singhdev Post Graduate College, Baikunthpur, Korea 497335, Chhattisgarh, India

art ic l e i nf o a b s t r a c t

Article history: The exposure to low or high concentrations of arsenic (As), either due to the direct consumption of As
Received 12 August 2014 contaminated drinking water, or indirectly through daily intake of As contaminated food may be fatal to
Received in revised form the human health. Arsenic contamination in drinking water threatens more than 150 millions peoples all
6 October 2014
over the world. Around 110 millions of those peoples live in 10 countries in South and South-East Asia:
Accepted 6 October 2014
Available online 26 November 2014
Bangladesh, Cambodia, China, India, Laos, Myanmar, Nepal, Pakistan, Taiwan and Vietnam. Therefore,
treatment of As contaminated water and soil could be the only effective option to minimize the health
Keywords: hazard. Therefore, keeping in view the above facts, an attempt has been made in this paper to review As
Arsenic contamination contamination, its effect on human health and various conventional and advance technologies which are
Arsenic sources
being used for the removal of As from soil and water.
Health hazards
& 2014 Elsevier Inc. All rights reserved.
Remediation techniques

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 248
2. Sources of arsenic in the environment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 248
2.1. Groundwater/drinking water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 248
2.2. Freshwaters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 249
2.3. Marine waters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
2.4. Arsenic concentration in soil. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
2.5. Arsenic concentration in food stuffs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
3. Health hazards. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
4. Remediation of arsenic contamination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252
4.1. Arsenic revomal by oxidation techniques. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
4.1.1. Oxidation and filtration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
4.1.2. Photochemical oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
4.1.3. Photocatalytic oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 254
4.1.4. Biological oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 254
4.1.5. In-situ oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 254
4.2. Phytoremediation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255
4.3. Coagulation–flocculation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255
4.4. Electrocoagulation (EC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 256
4.5. Electro-chemical arsenic remediation (ECAR) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 256
4.6. Adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 256
4.6.1. Activated alumina . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 256
4.6.2. Iron based sorbents (IBS). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257
4.6.3. Zero valent iron . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 258

n
Corresponding authors.
E-mail addresses: vijaypratap.au@gmail.com (V.P. Singh), profsmprasad@gmail.com (S.M. Prasad).

http://dx.doi.org/10.1016/j.ecoenv.2014.10.009
0147-6513/& 2014 Elsevier Inc. All rights reserved.
248 R. Singh et al. / Ecotoxicology and Environmental Safety 112 (2015) 247–270

4.6.4. Indigenous filters and cartridges. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 258

4.6.5. Miscellaneous adsorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 259
4.7. Ion exchange . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 260
4.8. Electrokinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 260
4.9. Membrane technology. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261
4.9.1. As removal using microfiltration. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261
4.9.2. As removal using ultrafiltration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261
4.9.3. As removal using Nanofiltrations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 261
4.9.4. As removal using reverse osmosis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262
4.10. As removal by advanced hybrid and integrated technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262
4.10.1. As removal using membrane distillation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262
4.10.2. As removal using forward osmosis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262
4.11. Disposal of As laden sludges and wastes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
5. Conclusion and future perspective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263

1. Introduction suggested the following order in terms of acute As toxicity: MMA

Recently, the environmental fate and behavior of arsenic (As) is
receiving increased attention due to the arsenic (As) pollution in
South-East Asia. Although As contamination in the environment
has been reported worldwide (Sohel et al., 2009; Li et al., 2011),
however, As pollution in groundwater has been a serious health
threat to the human beings in South-East, South-West and North-
East USA, inner Mongolia (China), South-West Taiwan coastal re-
gions, Sonora (Mexico), Pamplonian Plain (Argentina), West Ben-
gal (India), Northern Chile, and Bangladesh (Argos et al., 2010). The
World Health Organization (WHO) deemed the As in Bangladeshi
groundwater to be “the largest mass poisoning of a population in
history” (Argos et al., 2010).
Arsenic is ubiquitous in the environment and highly toxic to all
forms of the life. It is a crystalline “metalloid”, a natural element
with features intermediate between metals and non-metals, oc-
curs naturally as an element, ranks as the 20th most occurring
trace element in the earth's crust, 14th in seawater, and 12th in the
human body (Mandal and Suzuki, 2002). Arsenic exists mainly in
four oxidation states – arsenate (AsV), arsenite (AsIII), arsenic (As0),
and arsine (As
III) and its solubility depends on the pH and ionic
environment. Among them, the AsV being the most stable form
(Sharma and Sohn, 2009; Zhao et al., 2010; Gupta et al., 2011). AsV
is thermodynamically stable state in aerobic water, while AsIII is
predominant in reduced redox environment. Arsenic can be pre-
sent in the environment in various chemical forms such as
monomethylarsonic acid [MMA; CH3AsO(OH)2], dimethylarsinic
acid [DMA; (CH3)2AsOOH], trimethylarsine oxide [TMAO;
(CH3)3AsO], arsenobetaine [AsB; (CH3)3As þCH2COOH], arseno-
choline [AsC], arsenosugars [AsS], arsenolipids etc. (Tangahu et al.,
2011). In general, inorganic arsenicals are more toxic than organic
ones (Meharg and Hartley-Whitaker, 2002). AsIII is usually more
toxic than AsV (Abedin et al., 2002a, 2002b; Schat et al., 2002), and
dimethylarsinous acid (DMAAIII) and monomethylarsonous acid
(MMAAIII) are more toxic than their parent compounds (Petrick
et al., 2000; Mass et al., 2001). Methylated As compounds, such as
MMA, DMA and TMAO are found sometimes as a minor compo-
nent in the soil (Huang and Matzner, 2006), but can reach high
concentrations (Abedin et al., 2002a, 2002b). Both MMA and DMA
(also known as cacodylic acid) have been widely used as pesticides
and herbicides, the DMA also as a cotton defoliant. Arsenobetaine,
the dominant As species in marine animals, was found to be
present in an acidic fen soil with unclear origin (Huang and
Matzner, 2006). Arsenolipid, a lipid-soluble As compound, main-
ly found in the marine organism, and its concentration may reach
upto 16 mg As/kg fish oil (Sele et al., 2012). Recent findings
(III) 4As(III) 4As(V) 4DMA(V) 4MMA(V), where the MMA(III)
metabolite is the most toxic compound and some researchers
considered it to be the central As mode of action (EFSA, 2009; Kile
et al., 2011; Wen et al., 2011). In this review, we have summarized
As contamination and its remediation techniques in water and soil.
2. Sources of arsenic in the environment
The primary source of As in the environment (hydrosphere,
pedosphere, biosphere and atmosphere) is the release of As from
As-enriched minerals. The sources of As includes both natural i.e.
through dissolution of As compounds adsorbed onto pyrite ores
into the water by geochemical factors and anthropogenic i.e.
through use of insecticides, herbicides and phosphate fertilizers,
semi-conductor industries, mining and smelting, industrial pro-
cesses, coal combustion, timber preservatives etc. (Mondal et al.,
2006; Bundschuh et al., 2011). A survey of occurrence of As in
groundwater/drinking water, fresh waters, marine waters, soil and
food stuffs is given below.
2.1. Groundwater/drinking water
According to the WHO guidelines, the recommended limit of
arsenic in drinking water is 0.01 mg L
1. However, the levels of As
in unpolluted surface water and groundwater vary typically from
1–10 μg L
1. Groundwater concentrations of As is reported to be
very large range from less than 0.5–5000 mg L
1 covering natural
As contamination found in more than 70 countries (Ravenscroft
et al., 2009). The As contamination in groundwater in different
parts of the world is summarized in Table 1. Large areas of Ban-
gladesh, West Bengal and other states of India and Vietnam rely on
As contaminated groundwater for irrigation of staple crops such as
rice (Nickson et al., 1998; Berg et al., 2001; Abedin et al., 2002a,
2002b). On applying the WHO provisional guideline for drinking
water of 10 μg L
1 of As, a worldwide population of more than 100
millions people are at risk, and out of these more than 45 millions
people mainly in developing countries from Asia are at risk of
being exposed to more than 50 μg L
1 of As, which is the max-
imum concentration limit in drinking water in most of the coun-
tries in Asia (Ravenscroft et al., 2009). Contamination of drinking
water is the main source of As for human being but for the po-
pulation not exposed to elevated As in drinking water, consump-
tion of food grown in As-contaminated soil or irrigated with As-
contaminated water represents the main sources of As intake for
humans, which causes a life-threatening problem for millions of
 R. Singh et al. / Ecotoxicology and Environmental Safety 112 (2015) 247–270 249

Table 1
Concentrations of arsenic in groundwater of the arsenic-affected countries.

Location (Countries) Concentration in μg L
1 Arsenic sources References

Argentina, Pampa, Cordoba 100–3810 2–15 m, 61°45′–63°W; 32°20′–35°00′S Nicolli et al., 1989
Argentina, Cordoba 4100 Astolfi et al., 1981
Bangladesh o 10– 41000 Well waters Dhar et al., 1997
Calcutta, India o 50–23,080 Arsenic-rich sediments Mandal et al., 1996
Chile 470–770 United Nations, 2001
Fukuoka, Japan 0.001–0.293 Natural origin Kondo et al., 1999
Hanoi, Vietnam 1–3050 Arsenic-rich sediments Berg et al., 2001
Hungary 1–174 Deep groundwater Sancha and Castro, 2001
Inner Mongolia, China 1–2400 Drinking water; bores Guo et al., 2001
Lagunera region, Mexico 8–624 Well waters Razo et al., 1990
Mekong River floodplain, Cambodia 1–1340 Groundwater Buschmann et al., 2007
Nakhon Si Thammarat Province, Thailand 1.25–5114 Shallow (alluvial) groundwater, mining Williams et al., 1996
Nepal 8–2660 Drinking water Shrestha et al., 2003
Northeastern Ohio o 1–100 Natural origin Matisoff et al., 1982
Peru 500 Drinking water Sancha and Castro, 2001
Romania 1–176 Drinking water bores Gurzau and Gurzau, 2001
Ronpibool, Thailand 1–5000 Water contaminated by tin mining waste Choprapwon and Porapakkham, 2001
Shanxi, PR China 0.03–1.41 Well water Yinlong, 2001
South-west Finland 17–980 Well waters; natural origin Kurttio et al., 1998
West Bengal, India 3–3700 Arsenic-rich sediments Mandal et al., 1996
Western USA 1–48,000 Drinking water Welch et al., 1988
Xinjiang, PR China 0.05–850 Well water Yinlong, 2001

people in large areas of South-East Asia. For example, recently
inorganic As exposure drawn attention through food, since some
food items especially rice and vegetables were reported to contain
high inorganic As concentrations in areas with elevated As in soil
and irrigation water (EFSA, 2009; Mondal et al., 2010; Zhao et al.,
2010; Fu et al., 2011; Rahman and Hasegawa, 2011a, 2011b; WHO,
2011; and Bhattacharya et al., 2012).
2.2. Freshwaters
In freshwater systems (rivers and lakes), the variation in As
concentration is in the range of 0.15–0.45 μg L
1 (Bissen and
Frimmel, 2003a, 2003b) depending on the source, availability,
and geochemistry of the catchments (Smedley and Kinniburgh,
2002). Basic As concentrations in the water of various con-
taminated rivers range between 0.1 to 2.1 mg L
1 with an average
of 0.8 mg L
1 (Table 2), which might be due to the source of con-
tamination, surface recharge, base flow, and the bedrock lithology.
The geothermal inputs, evaporation, and groundwater con-
tamination are the main cause of high concentrations of As in
rivers. For example, in Lao River of Northern Chile the extremely
high concentrations of As (upto 21,000 mg L
1) is due to the above-
mentioned processes (Cáceres et al., 1992). Mining activity can also
contribute in the occurrence of high As concentrations in river
waters. For example, water of Mole River, New South Wales,
Australia contains high levels of As (from 110–600 mg L
1 upto

Table 2
Arsenic concentrations in some major aquatic systems (rivers, lakes, estuaries and marine) of the world.

Aquatic systems and location Arsenic concentrations (average/range (mg L
1) References

Lakes
Biwa Lake, Japan 2.2 (0.6–1.7) Hasegawa et al., 2010
Moira Lake, Ontario, Canada 20.4 (22.0–47.0) Azcue and Nriagu, 1995
Mono Lake, California, USA 10,000–20,000 Maest et al., 1992
Marine and Estuaries
Bunnefjord, Norway 0.5–1.9 Abdullah et al., 1995
Coastal Malaysia 1.0 (0.7–1.8) Yusof et al., 1994
Coastal Nakaminato, Japan 3.1 Ishikawa et al., 1987
Deep Pacific and Atlantic 1.0–1.8 Cullen and Reimer, 1989
Krka Estuary, Yugoslavia 0.1–1.8 Seyler and Martin, 1991
Rhone Estuary, France 2.2 (1.1–3.8) Seyler and Martin, 1990
Saanich Inlet, B.C., Canada 1.2–2.5 Peterson and Carpenter, 1983
Schelde Estuary, Belgium 1.8–4.9 Andreae and Andreae, 1989
Southern coast, Australia 1.3 (1.1–1.6) (inorganic) Maher, 1985a
Southeast coast, Spain 1.5 (0.5–3.7) Navarro et al., 1993
Tamar Estuary, UK 2.7–8.8 Howard et al., 1988
Uranouchi Inlet, Japan 22.0–32.0 Hasegawa, 1996
Vestfjord, Norway 0.7–1.0 Abdullah et al., 1995
Rivers
Ashanti, Ghana 284( o 2–7900) Smedley et al., 1996
Cordoba, Argentina 7–114 Lerda and Prosperi, 1996
Dordogne, France 0.7 Seyler and Martin, 1990
Madison and Missouri rivers, USA 44 (19–67), 10–370 Robinson et al., 1995
Mole River, NSW, Australia 110–600 (up to 13900) Ashley and Lottermoser, 1999
Owens River, CA, USA 85–153 Wilkie and Hering, 1998
Po River, Italy 1.3 Pettine et al., 1997
Ron Phibun, Thailand 218 (4.8–583) Williams et al., 1996
Waikato, New Zealand 32 (28–36) McLaren and Kim, 1995
250 R. Singh et al. / Ecotoxicology and Environmental Safety 112 (2015) 247–270
13,900 mg L
1) due to the mining and processing of arsenopyrite
ores (Ashley and Lottermoser, 1999). However, according to the
WHO guidelines for irrigation purpose the permissible limit of
arsenic in water is 0.10 mg L
1.
As concentrations in lake waters are close to or lower than that
reported for river waters (Table 2). Azcue et al. (1994) and Azcue
and Nriagu (1995) studied that the As concentrations in lakes
around British Columbia and Canada ranged between 0.2 and
2.08 mg L
1, has been transported from the abandoned Cariboo
Gold Quartz mine tailings of that area, and gets accumulated in
high concentration (upto 1104 mg g
1) in the bottom sediments of
the lakes. Geothermal sources and mining activities have also in-
creased the concentrations of As in lake waters (Smedley and
Kinniburgh, 2002). In mine affected lake waters, the As con-
centrations are relatively low because of its adsorption onto Fe-
oxides under neutral pH (Smedley and Kinniburgh, 2002), and also
due to its accumulation in bottom sediments (Azcue and Nriagu,
1995).
Several studies have reported thermal stratification of As con-
centrations in lake waters (Azcue and Nriagu, 1995; Hasegawa,
1996; Hasegawa et al., 2010). Azcue and Nriagu (1995) studied that
the dissolved As concentration was highest during summer in the
Moira Lake, Ontario, Canada with an average concentration of
47 mg L
1 in surface water, compared to 22 mg L
1 in winter.
Hasegawa et al. (2009) have also reported similar trends in the
occurrence of As concentrations in lake waters. Smedley and
Kinniburgh (2002) and Hasegawa et al. (2010) reported that
thermal stratification in lake water also causes the release of As
into the water column from bottom sediments due to depletion of
O2 levels in the hypolimnion (due to increased biological activities)
and its subsequent redistribution throughout the lake.
Recently, the major As affected regions are found in large deltas
and along major rivers emerging from the Himalayas with the
Bengal delta being the worst affected area where 4 88% of the 45
millions inhabitants are at high risk of exposure to As concentra-
tions 450 mg L
1 (Acharyya and Shah, 2007; Ravenscroft et al.,
2009; Uddin et al., 2011). The other affected river deltas and river
basins in South and South-East Asia are the Red River Delta and
the Mekong Delta (4 10 millions exposed) (Berg et al., 2007;
Buschmann et al., 2008) and river basins of Chindwin-Irrawady,
Salween; Brahmaputra, Ganges, Indus, Chenab (Chakraborti et al.,
2003; Nickson et al., 2005, 2007; Stanger, 2005; Thakur et al.,
2011).
2.3. Marine waters
In seawater, the As concentration is usually less than 2 μg L
1
(Ng, 2005), and its concentrations in Atlantic and deep Pacific
waters are between 1.0–1.8 mg L
1 (Cullen and Reimer, 1989),
3.1 μg L
1 in marine waters of the Pacific coast near Nakaminato
(Ibaraki, Japan) (Ishikawa et al., 1987), and 1.1–1.6 mg L
1 in coastal
Table 3
Concentrations of arsenic in soil of the arsenic-affected countries.
Country Region Soil As concentration in mg/kg
Bangladesh Noakhali 3.6–26 mg/kg (Meghna River)
Brazil Minas Gerais (Southeastern Brazil) 200–860 mg/kg
Chile Esquiña Up to 489 mg/kg (Río Caritaya region)
India Uttar Pradesh 16–417 mg/kg (Central India) 5.40–15.43 ppm (Uttar Pradesh) Das et al., 2013; Srivastava and Sharma, 2013
Mexico Lagunera 2215–2675 mg/g (Highly polluted area)
Poland Lower Silesia, (Southwestern Poland) Up to 18,100 mg/kg (Highly polluted area)
Spain Duero Cenozoic Basin 23 mg/kg (Mean)
Turkey Simav plain (Kutahya) Up to 660 mg/kg (Highly polluted area)
United Kingdom Cornwall 2–17 mg/kg (Bioaccessible)
USA Tulare lake average 280 mg/kg (Hawaii)
waters of southern Australia (Maher, 1985) (Table 2). Arsenic
concentrations in estuarine waters are more uniform than those of
open marine waters. Smedley and Kinniburgh (2002) reported
that As concentrations in the estuarine waters may be affected by
industrial and mining effluents and geothermal water. The physi-
cal mixing of the fresh and seawater masses and salinity may in-
fluence the concentration of dissolved As in estuaries and con-
tinental shelves. For example, a linear increase in total As con-
centrations, ranging from 0.13 mg L
1 in freshwaters to 1.8 mg L
1
in offshore waters, with increase in the salinity has been reported
in Krka Estuary, Yugoslavia (Seyler and Martin, 1991).
2.4. Arsenic concentration in soil
According to the U.S. Environmental Protection Agency, the
permissible limit of arsenic in soil is 24 mg kg
1. In the case of soil,
there are also numerous pathways for propagating the con-
tamination of As. The major sources of its contamination in soil are
identified to include many man-made activities e.g. the use of
insecticides, herbicides and phosphate fertilizers, semi-conductor
industries, mining and smelting, industrial processes, coal com-
bustion, timber preservatives etc. (Mondal et al., 2006; Bundschuh
et al., 2011). Average arsenic concentration in European topsoil is
estimated at 7.0 mg kg
1 (Stafilov et al., 2010) but the background
concentration can significantly differ depending on soil conditions.
Arsenic contamination in soil in different parts of the world is
summarized in Table 3. In lower Silesia, Southwestern Poland upto
18,100 mg kg-1 of As was reported in soil of Au-enriched me-
tallogenic zones (Karczewska et al., 2007).
2.5. Arsenic concentration in food stuffs
The interest in rice as a potential source of exposure to arsenic
is very recent. Rice is a staple food for more than half the world's
population beacuse it is a good source of carbohydrates, thiamin,
vitamin B6, and some essential elements like magnesium, zinc and
copper. The world's total production of rice in 2009 was estimated
to be 682 million metric tons (FAO, 2010). Interestingly, many of
the rice-producing countries suffer from arsenic contamination in
their groundwater or soil (Rahman and Hasegawa, 2011a, 2011b).
However, rice may accumulate hazardous levels of toxic elements
such as arsenic. Due to its large daily consumption, it accumulates
in human body and poses serious threat (Meharg et al., 2008;
Shraim, 2014). Besides rice, other cereals such as wheat, corn, oat,
buckwheat are also source of arsenic exposure. Vegetables and
meat products have also been reported a good source of arsenic
exposure to human beings (EFSA, 2014). The amount of arsenic
ingested daily by humans via food is greatly influenced by the
amount of food in the diet. The amount of arsenic in various food
stuffs and its safe limit is summarized in Table 4.
References
Nriagu et al., 2007
Bundschuh et al., 2012
Bundschuh et al., 2012; Nriagu et al., 2007
Nriagu et al., 2007
Karczewska et al., 2007
Gómez et al., 2006
Gunduz et al., 2010
Palumbo-Roe et al., 2005
Nriagu et al., 2007
 R. Singh et al. / Ecotoxicology and Environmental Safety 112 (2015) 247–270 251

Table 4 Besides, the organic arsenic compounds have been used as feed
Arsenic concentrations in various food stuffs and its recommended limit. additives for swine disease control and weight improvement (Li
and Chen, 2005). Once the excessive additives are released in the
Food stuff(s) Arsenic concentra- Recommended limit of Reference
tion (mg As kg
1) arsenic in food (FAO) environment, arsenic may compromise food safety and environ-
mental quality as it contains arsenic in range of 0.42–
Rice 153.1 1 mg kg
1 EFSA, 2014 119.0 mg kg
1. Therefore, there is a growing public concern about
Wheat 22.0 do EFSA, 2014
the arsenic residues accumulation in pig manure. Silbergeld and
Oat 27.3 do EFSA, 2014
Corn 49.3 do EFSA, 2014 Nachman (2008) also observed arsenicals in pig manure that may
Vegetables 90–3900 do Das et al., likely increase the burden of global human arsenic exposure and
2004 risk.
Pulses 1300 do Santra et al.,
2013
Chicken meat 286 do Islam et al.,
2013 3. Health hazards
Fish 3000 do Lin and Liao,
2008 Numerous studies have been conducted to assess the toxicity of
As and its effects on human health in various As-contaminated
In poultry, use of arsenic compounds is very common. For in- regions (Kongkea et al., 2010; Maity et al., 2012). Arsenic enters in
stance, arsenic is used in the forms of roxarsone as an additive in human beings through two pathways; first, direct consumption of
As contaminated drinking water and second, for populations not
the feed of conventionally-raised broilers. It is used to control
exposed to elevated As in drinking water, foods represent the main
protozoan parasites known as coccidians and to enhance weight
sources of As intake for humans (Fig. 1). Arsenic accumulation in
gain (Miller et al., 2000) Feeding arsenic to laying hens is pro-
vegetables followed by ingestion may result in a significant con-
hibited. Organic regulations prohibit feeding arsenic to birds
tribution on to the daily human intake of inorganic As
raised for organic certification. It is estimated that roxarsone is
(Fontcuberta et al., 2011). Arsenic contamination in drinking water
added to poultry feed at the rate of 22.7–45.4 g per ton, or 0.0025–
threatens health risk for more than 150 millions people all over
0.005 percent (Miller et al., 2000; Bellows, 2005). Most of the the world (Ravenscroft et al., 2009). Around 110 millions of those
roxarsone passes through the birds and is excreted unchanged people live in 10 countries in South and South-east Asia: Bangla-
(Kpomblekou et al., 2002). Each broiler excretes about 150 mg of desh, Cambodia, China, India, Laos, Myanmar, Nepal, Pakistan,
roxasone during the 42-day growth period in which it is ad- Taiwan and Vietnam (Brammer, 2008). In total 88,750 km² in West
ministered (Sims and Wolf, 1994). Moreover, Rosal et al. (2005) Bengal has been identified as As contaminated zone among which
have also investigated fate of roxarsone and its possible transfor- 38,861 km² area has been identified as highly affected zones, this
mation products (arsenite, arsenate, monomethylarsonate, di- include Nadia, North and South 24 Parganas, Murshidabad and
methylarsinate, 3-amino-4-hydroxyphenylarsonic acid, and 4-hy- Kolkata districts (Chakraborti et al., 2009). Groundwater is used for
droxyphenylarsonic acid) in chicken manure and found that these the irrigation to cultivate a variety of crops and vegetables, and
compounds are responsible for arsenic contamination of chicken. thus irrigation with As-enriched groundwater is the main pathway
Large amount of pig manure is produced all over the world for As to enter the human food chain (Das et al., 2004; Chatterjee
which can be used as organic fertilizers on agricultural lands. et al., 2010; Samal et al., 2011) which is the potential human health

Fig. 1. Schematic diagram is showing transfer of arsenic from soil and water to human beings through food chains. Intake of arsenic by human beings causes several diseases.
252 R. Singh et al. / Ecotoxicology and Environmental Safety 112 (2015) 247–270
risk have recently received attention, especially for rice (Zhao
et al., 2010). The accumulation of As is also important in wetland
species, where there is a potential for reducing conditions to re-
lease As into the soil solution (Ha et al., 2009; Rahman and
Hasegawa, 2011a, 2011b), or for co-deposition of As with Fe hy-
droxides adsorbed to the plant's surface (Zhao et al., 2002). In
West Bengal (India) and Bangladesh, most of the crop fields are
contaminated with As (Roychowdhury et al., 2002; Alam et al.,
2003).
The various effects of As poisoning on human health are mel-
anosis, leuco-melanosis, keratosis, hyperkeratosis, dorsum, non-
petting edema, gangrene and skin cancer (Fig. 1). Melanosis and
keratosis are the most common presentations among the affected
peoples (Karim, 1999). Patients of leuco-melanosis and hyperker-
atosis have been found in many cases. Few cases of skin cancer
have also been identified among the patients seriously affected by
arsenite and arsenate (Hsueh et al., 1995). Chronic exposure to
inorganic As causes several disorders upon different biological
systems like digestive system, respiratory system, cardiovascular
system, hematopoietic system, endocrine system, renal system,
neurological system, and reproductive system which ultimately
lead to cancer (Mandal et al., 1996; Maharjan et al., 2005).
Excessive and long-term (such as 5–10 years) human intake of
toxic inorganic As having concentration above 0.05 mg L
1 leads
to arsenicosis, which is a common term used for As related health
effects including skin problems, skin cancers, internal cancers
(bladder, kidney, lung), diseases of the blood vessels of the legs
and feet, and possibly diabetes, high blood pressure and re-
productive disorders (WHO, 2011). The global extent and severity
of appearing arsenicosis is probably not yet fully revealed. Over-
whelming evidence of non-occupational chronic As exposure is
through ingestion of drinking water including food and beverages
prepared from drinking water. Inhaled amounts of As may be high
and important in poorly ventilated huts where As rich coal or cow
dung is used as a fuel (Lin et al., 2010) with high As concentrations
has been reported over the last two decades and is now
Fig. 2. Schematic diagram is showing various techniques used for removal of arsenic from soil and water. These techniques are discussed in detail in the text.
recognized to be one of the world's greatest environmental ha-
zards (Sohel et al., 2009; Chakraborti et al., 2010; Bundschuh et al.,
2012; Naujokas et al., 2013). The major arsenicosis regions are
presently found in large deltas and/or along major rivers emerging
from the Himalayas (Fendorf et al., 2010) such as in the Bengal
delta (Chakraborti et al., 2010), other parts of India (Saha, 2009;
Shukla et al., 2010), Nepal (Thakur et al., 2011), Pakistan (Malik
et al., 2009), Myanmar, Vietnam, Cambodia (Berg et al., 2007;
Polya et al., 2008) and China (He and Charlet, 2013). A recent study
has shown that nutritional deficiency is an important promoter of
arsenicosis especially for women (Deb et al., 2013).
4. Remediation of arsenic contamination
Arsenic contaminated drinking water is a major threat to
mankind. Although in small quantities it is necessary, however, it
is known to be highly toxic if ingested in large dose. Its elevated
concentrations are found in groundwater in some areas of India,
Bangladesh, Chile, China, Argentina, Mexico, Hungary, Taiwan,
Vietnam, Japan, New Zealand, Germany and the United States due
to naturally occurring arsenic in the aquifer sediment (Bang et al.,
2005a). Thus, in order to reduce the health risk arising due to the
direct consumption of As contaminated drinking water or due to
the consumption of food/vegetables, grown in soil irrigated with
As contaminated water, there is need to develop strategies that
could alleviate toxicity and availability of As from soil to edible
portions of food/vegetables. Removal of As highly depends on the
chemistry and composition of the As contaminated water. In most
of the major reported incidences As occurs as AsIII and oxidation of
AsIII to AsV is deemed necessary to achieve the satisfactory results
of As removal. Here dealing with the presently available technol-
ogies, especially oxidation, phytoremediation, coagulation–floc-
culation, adsorption, ion exchange, electrokinetics and membrane
technologies will be discussed (Fig. 2).
 R. Singh et al. / Ecotoxicology and Environmental Safety 112 (2015) 247–270
4.1. Arsenic revomal by oxidation techniques
These techniques use various processes and are discussed
below.
4.1.1. Oxidation and filtration
The main purpose of oxidation is to convert the soluble AsIII to
AsV, which is then followed by precipitation of AsV. This is es-
sential for anaerobic groundwater because AsIII is the predominant
form of As at neutral pH (Masscheleyn et al., 1991). Generally,
oxidation and filtration refer to the processes which are designed
to remove the naturally occurring iron and manganese from water.
The process involves the oxidation of the soluble forms of iron and
manganese to their insoluble forms and then removal by filtration.
Firstly, soluble AsIII is oxidized. Arsenic is mainly present as AsV
and, as such, is likely to be in the solid phase. Therefore, in such
soils, As in groundwater used for irrigation is quickly adsorbed by
iron hydroxides and becomes largely unavailable to plants. In
anaerobic soil conditions such as in flooded paddy fields, As is
mainly present as AsIII and is easily dissolved in the soil-pore water
(the soil solution) (Xu et al., 2008). It is thus more readily available
to plant roots. Arsenite has a low affinity to mineral surfaces, while
arsenate adsorbs easily to solid surfaces. Thus, for the removal of
As from water, oxidation/precipitation technology is very effective
(Ghurye et al. 2004; Leupin and Hug, 2005). The oxidation of AsIII
into AsV is carried out by traditional chemical oxidants (Ox) such
as chlorine (Cl2), chlorine dioxide (ClO2), ozone (O3), hydrogen
peroxide (H2O2), chloroamine (NH2Cl), permanganate (MnO4
),
and ferrate (FeO42
) and have been published in many studies
(Emett and Khoe, 2001; Johnston et al., 2001; Bissen and Frimmel,
2003b; Lee et al., 2003; Ghurye et al., 2004; Vasudevan et al.,
2006; Dodd et al., 2006; Sharma et al., 2007; Mondal et al., 2013).
Following equations expresses the stoichiometries of the oxi-
dation reactions:
Cl2: As(OH)3 þHOCl-AsO43
þ Clþ 4H þ
ClO2: As(OH)3 þ 2ClO2 þ H2O-AsO43
þ 2ClO2 þ 5H þ
O3: As(OH)3 þO3-AsO43
þO2 þ3H þ
3
þ
H2O2: As(OH)3 þH2O2-AsO4 þ3H þH2O
NH2Cl: As(OH)3 þNH2Cl þH2O-AsO43
þNH4 þ

þCl þ3H
MnO4
: 3As(OH)3 þ2MnO4--3AsO43- þ2MnO2 þ 7H þ þ H2O
2
2
3

FeO4 : 3As(OH)3 þ2FeO4 þ H2O-3AsO4 þ2Fe(OH)3 þ
5H þ
When used for oxidation of AsIII to AsV, the reaction is very fast
for Cl2, O3 and MnO4
compared to the H2O2 and NH2Cl (Lee et al.,
2003; Ghurye et al., 2004; Dodd et al., 2006). By using air and pure
oxygen, about 54–57% of AsIII can be oxidized to AsV in con-
taminated groundwater (Kim and Nriagu, 2000) whereas, com-
plete oxidation of AsIII can be achieved with O3. The NH2Cl and
H2O2 are sluggish in reacting with AsIII while Cl2 and O3 react very
rapidly. Free Cl2 or hypochlorite is effective for the oxidation of
AsIII, but chlorination creates and leaves disinfectant by-products
(DBPs) in treated water. Reduction in the levels of trihalo me-
thanes (THMs) and halo acetic acids (HAAs) was seen with O3, but
it can form the potent carcinogenic bromate ion by reacting with
bromide present in the water (Gunten, 2003; Richardson, 2006). It
is suggested that treatment with NH2Cl produces N-ni-
trosodimethylamine (NDMA) which is a suspected human carci-
nogen (Mitch and Sedlak, 2002). For the treatment of high quality
water such as surface water, the use of ClO2 is restricted and
dosing of ClO2 must be kept low. For example, in the United States,
dosages ranging from 1 to 1.4 mg L
1 are used mainly for the
253
preoxidation of surface water (Gates, 1998). Removal of As using
H2O2 and NH2Cl oxidants would take hours as they oxidizes AsIII
very slowly whereas Cl2, O3, and FeO42
would react with AsIII in
millisecond time scale. The scavenger substances present in water
will affect the fast kinetics of AsIII oxidation with Cl2, O3, and
FeO42
. However, specific selection of oxidants can reduce the
effect of scavengers on effectiveness of oxidant. For example, in
order to remove As from water that contains excess ammonia, it is
better to use ozonation rather than chlorination because O3 reacts
slowly with ammonia. FeO42
can be related to the use of other
chemical oxidants for removing As (Sharma, 2007a). FeO42
does
not react with bromide ion and thus carcinogenic bromate ion
would not be produced in the treatment of bromide-containing
water (Sharma, 2007a). Moreover, FeIII, a by-product of FeVI is non-
toxic, and acts as a powerful coagulant (Sharma, 2002, 2004;
Sharma et al., 2005a, 2005b; Yngard et al., 2008) which is suitable
for the removal of AsV in water (Lee et al., 2003; Sharma et al.,
2007). Thus, FeVI acts as multifunctional chemical oxidant, disin-
fectant, and coagulant in a single mixing (Sharma, 2007b). Re-
cently, it has been demonstrated that the oxidation of AsIII by
MnO2 coated PEEC-WC nanostructured capsules and demon-
strated that when water contains a low concentration of As, they
have a higher efficiency than conventional oxidation methods
(Criscuoli et al., 2012).
4.1.2. Photochemical oxidation
The most widely tested chemical oxidant in presence of natu-
rally occurring iron in the field is UV-light assisted oxidation of AsIII
(Ryu et al., 2013). The oxidation rate of AsIII in the water can be
increased by UV irradiation in the presence of oxygen. UV/solar
light helps to generate hydroxyl radicals through the photolysis of
FeIII species: (FeOH2 þ ) and in the presence of both hydroxyl radicals
and O2, the oxidation rate becomes faster (Yoon and Lee, 2005;
(1) Sharma et al., 2007). Several studies have investigated the photo-
chemical oxidation of AsIII using UV light irradiation. In perchlorate/
(2) perchloric solution at pH 0.5–2.5, addition of FeIII to As-con-
(3) taminated water followed by exposure to UV/solar light enhanced
the removal of As (Emett and Khoe, 2001). In this study, FeIII-hy-
(4) droxide and chloride species absorb photons to give highly oxidiz-
þ
(5) ing hydroxyl and dichloro radicals which converts AsIII to AsV
(Emett and Khoe, 2001). Although, this system was also found to be
(6) useful under natural water conditions (Hug et al., 2001). An oxi-
dation of AsIII solution containing 0.06–5 mg L
1 FeII and FeIII using
(7) 90 W m
2 UV-A light removed more than 90% of the 500 μg L
1
total As in 2–3 h. Addition of citrate to this solution strongly ac-
celerated the oxidation of iAsIII (inorganic arsenite) (Hug et al.,
2001). Instead of UV-light, solar-light can also remove As from
natural water upon addition of iron and citrate (Lara et al., 2006).
Addition of a few drops of lime or lemon juice (citrate) in water may
also be helpful for the enhancement of photochemical oxidation of
AsIII to the less harmful AsV (Hug et al., 2001; Kocar and Inskeep,
2003; Lara et al., 2006). The cyclic reaction of lemon juice (citrate)
with strongly oxidizing radicals gives rise to further radicals due to
which the removal rate was higher but excessive concentration of
citrate has a negative impact due to the formation of acid com-
plexants (Bissen and Frimmel, 2003b). Recently, oxidation of AsIII
was accomplished by using vacuum-UV lamp irradiation at 185 and
254 nm wavelengths (Yoon et al., 2008). In this study, the effects of
FeIII, H2O2, and humic acids (HA) were examined. Both FeIII and
H2O2 increased oxidation efficiency but humic acid did not show
any influence on the oxidation. In order to achieve effective oxi-
dation of AsIII, intense UV light source was used with the potassium
peroxydisulphate (KPS) system (Neppolian et al., 2008).
254 R. Singh et al. / Ecotoxicology and Environmental Safety 112 (2015) 247–270
4.1.3. Photocatalytic oxidation
The efficient oxidation of AsIII to AsV can be achieved by pho-
tocatalytic oxidation (PCO) (Bissen et al., 2001). The PCO of AsIII to
AsV followed by adsorption of As on TiO2 was investigated (Dutta
et al., 2004, 2005; Miller et al., 2011). The PCO of AsIII in suspen-
sions with low TiO2 loadings followed by subsequent adsorption of
AsV onto TiO2 surfaces in slightly acidic media reduced As con-
centrations below the WHO drinking water limit of 10 μg L
1 in
water (initial [As] ¼66.7 μM) (Dutta et al., 2005). Miller and
Zimmer-man (2010) synthesized a TiO2-impregnated chitosan
bead (TICB) and it was used for oxidation as well as removal of As
from aqueous solution. The adsorption of AsV onto TiO2 is influ-
enced by pH, initial concentration of As, type of TiO2, presence of
anions (e.g. CO32
and PO43
) and NOM (natural organic matter)
(Dutta et al., 2004; Bang et al. 2005b; Ferguson and Hering, 2006;
Pena et al., 2005, 2006; Liu et al., 2008; Miller et al., 2011). They
observed a higher amount of adsorption of As [6400 mg AsIII g
1
TICB and 4925 mg AsV g
1] followed by UV radiation compared to
the solution that was not exposed to UV light [2198 mg AsIII g
1
TICB and 2050 mg AsV g
1]. A nanocrystalline Al2O3 and TiO2 im-
pregnated chitosan for As removal was prepared by Yamani et al.
(2012) and their study proposed a mechanism where AsIII is photo-
oxidized to AsV by TiO2, then adsorbed by Al2O3. When a very low
amount of TiO2 is present, the TiO2/UV system has an inefficient
removal of As due to incomplete oxidation of AsIII to AsV (Guan
et al., 2012). The effect of competitive anions and organic matter
that are commonly found in the groundwater are an important
disadvantage of using UV/TiO2. Bicarbonate and humic acid affect
the PCO of AsIII, while the adsorption of As on to the TiO2 based
adsorbent was affected by silicate, fluoride, phosphate and humic
acid (Guan et al., 2012). The PCO increases in the presence of NOM
but at higher concentration of NOM (2–15 mg L
1), the adsorption
of AsV on the surface of TiO2 decreases (Dodd et al., 2006; Liu et al.,
2008). Sharma and Sohn (2009) recently reviewed the possible
reasons for the decreased adsorption of AsV on TiO2, that are the
competitions between NOM and AsV for available binding sites
on TiO2 surface and/or the adsorption of NOM, which modifies
the surface charge of TiO2. Recently, it has been demonstrated that
the PCO of pentavalent MMAV (monomethylarsonic acid) and
DMAV (dimethylarsinic acid) using Degussa P25 and nanocrystal-
line TiO2 (Xu et al., 2007, 2008). In the use of Degussa P25 TiO2,
both MMAV and DMAV were readily mineralized to iAsV (Xu et al.,
2007). The MMAV was formed as an intermediate of the PCO of
DMAV, which was subsequently oxidized to iAsV.
4.1.4. Biological oxidation
It is relatively a new method of oxidation of iron and manga-
nese as a treatment method for As removal. Biological treatment
methods exploit natural biological processes that allow certain
plants and micro-organisms to help in the remediation of metals
in soil and groundwater. This process is based upon the fact that As
contaminated groundwater is usually reducing and containing
iron and manganese concentrations. In the treatment system, the
following sequence of reactions have been found to occur:
(i) oxidation of MnII to MnIV and FeII to FeIII, (ii) oxidation of AsIII to
AsV, (iii) precipitation of manganese oxides, (iv) abiotic oxidation
of AsIII by manganese oxides, and (v) AsV sorption by manganese
oxides, where steps (i) and (ii) are biotic and steps (iii) to (v) are
abiotic. Katsoyiannis and Zouboulis (2004) reported that the mi-
croorganisms Gallionella ferruginea and Leptothrix ochracea were
found to support biotic oxidation of iron. They performed some
experiments in the laboratory where iron oxides and above given
microorganisms were deposited in the filter medium, offering a
favorable environment for the adsorption of As because As in the
form of AsIII cannot be efficiently sorbed onto iron oxides. Prob-
ably, these microorganisms oxidized AsIII to AsV, which got
adsorbed in FeIII resulting in overall As removal of up to 95% even
at high initial As concentrations of 200 mg L
1. The kinetics of
bacterial AsIII oxidation and subsequent removal of AsV by sorption
onto biogenic manganese oxides during ground water treatment
was studied by Katsoyiannis et al. (2004). Their findings suggested
that the rate of oxidation of AsIII was comparatively higher than
the rates reported for abiotic AsIII oxidation by manganese oxides,
supporting that bacteria play an important role in both the oxi-
dation of AsIII and the generation of reactive manganese oxide
surfaces for the removal of AsIII and AsV from solution. Thus,
bacteria play an important role in both the AsIII oxidation and the
generation of reactive manganese oxide surfaces for the removal of
dissolved AsIII and AsV. Later, Katsoyiannis and Zouboulis (2006)
reviewed the use of iron and manganese oxidizing bacteria for the
combined removal of iron, manganese and As from contaminated
ground water. According to report, iron oxidizing bacteria remove
As more efficiently than those of manganese oxidizing bacteria.
The rates of oxidation of iron, manganese and As are faster than
those reported for physicochemical oxidation, indicating the cat-
alytic role of bacteria in As removal. Leupin and Hug (2005) passed
aerated artificial ground water with high As and iron concentra-
tion through a mixture of 1.5 g iron fillings and 3–4 g quartz sand
in a vertical glass column. By using dissolved oxygen, FeII was
oxidized to hydrous ferric oxides (HFO) while AsIII was partially
oxidized and AsV adsorbed on the HFO. This principle was suc-
cessfully applied in the field by Sen Gupta et al. (2009), where
without using any chemical they reversed the bacterial As reduc-
tion process, by recharging calculated volume of aerated water
(DO44 mg L
1) in the aquifer to create an oxidized zone. This
boosted the growth of iron oxidizing bacteria and suppressed the
growth of As reducing anaerobic bacteria and promoted the
growth of chemoautotrophic As oxidizing bacteria (CAOs) over a
period of six to eight weeks. Saalfield and Bostick (2009) de-
monstrated a process in the laboratory, where the mobility of As
was affected by biologically mediated redox processes by binding
it to iron oxide through dissimilatory sulphate reduction and
secondary iron reduction processes, in reducing aquifers. Incuba-
tion experiments were conducted using AsIII/V-bearing ferrihydrite
in carbonate-buffered artificial groundwater enriched with sul-
phate (0.08–10 mM) and lactate (10 mM) and inoculated with
Desulfovibrio vulgaris (ATCC 7757), which reduces only sulphate
but not Fe or As. The end product formed through sulphidization
of ferrihydrite was magnetite, elemental sulfur and trace Fe sul-
phides. It was suggested that only AsIII species got released under
reducing conditions and bacterial reduction of AsV was necessary
for As sequestration in sulphides.
4.1.5. In-situ oxidation
This method is mostly popular for removal of Fe from
groundwater (Appelo et al., 1999). In-situ oxidation can be
achieved by pumping the oxygenated water into the groundwater
aquifer to reduce the As content in the pumped groundwater. Its
potential for removal of As is investigated in very few studies al-
though the results show that As concentrations can be reduced in
the groundwater zone before water extraction (Sen Gupta et al.,
2009; van Halem et al., 2010). In-situ oxidation of As and iron in
the aquifer has been tried under Danida Arsenic Mitigation Pilot
Project (DPHE, 2001). The aerated tube well water is stored in a
tank and released back into the aquifers through the tube well by
opening a valve in a pipe connecting the water tank to the tube
well pipe under the pump head. The dissolved oxygen content in
water oxidizes AsIII to less mobile AsV and also the ferrous iron to
ferric iron in the aquifer causing the reduction in As content of
tube well water.
 R. Singh et al. / Ecotoxicology and Environmental Safety 112 (2015) 247–270
4.2. Phytoremediation
Phytoremediation is the plant based environmental-friendly
technology, for the remediation of As contaminated sites, using
plants and microbes to clean up contaminated air, soil and water
(Lasat, 2002; Cherian and Oliveira, 2005; Dickinson et al., 2009;
Behera, 2014). The Pteris vittata (Chinese brake fern) was found to
be resistant to As, having the capability of hyperaccumulating
large amounts of As in its fronds (Ma et al., 2001) by area con-
taminants are picked up by the roots of plants and transported to
their overground parts, and then removed together with the crops
(phytostabilization, phytoextraction and phytovolatilization). The
brake fern can accumulate between 1442–7526 mg kg
1 As in
fronds from contaminated soils, and up to 27,000 mg kg
1 As in its
fronds in hydroponics culture. The As hyperaccumulation capacity
has also been demonstrated in other plants (Meharg, 2003; Du
et al., 2005; Keller et al., 2007; Tripathi et al., 2007; Gonzaga Maria
et al., 2008; Zhang et al., 2008). It is hypothesized that hyper-
accumulation is associated with the interaction of As with high-
affinity chelating molecules present in the cytoplasm of the plant.
For example, an arsenate activated glutaredoxin from the fern P.
vittata L. regulates intracellular arsenite (Sundaram et al., 2008).
The molecular studies have shown that many gene products are
involved in the process of As hyperaccumulation (Dhankar et al.,
2002), hence single gene and multigenic engineering approaches
may be applicable to enhance the efficiency of phytoremediation
(Padmavathiamma and Li, 2007; Tripathi et al., 2007). Besides
phytoremediation, phytostabilization methods using plants can
also be applied for long-term remediation of As. This method
limits uptake and excludes mobilization of As. The major benefit of
phytostabilization is that the vegetative biomass above ground is
not contaminated with As, thus reduces the risk of As transfer
through food chains (Madejon et al., 2002).
Furthermore, the bioremediation techniques, including a vari-
ety of sulfate reducing bacteria and other species such as
Paenibacillus, Pseudomonas, Haemophilus, Micrococcus, and Bacillus
may be involved to remediate As from contaminated environ-
ments (Yamamura et al., 2003, Kirk et al., 2004, Ike et al., 2008).
The basic principle of bioremediation is change in the redox re-
actions, increasing/decreasing the solubility using different com-
plexation reactions, pH changing and adsorption/uptake of a
substance from the environment (Smith et al., 1994). Still, the
current bioremediation techniques fail mainly because of the
limitations of phytoremediation in arid area, re-release of im-
mobilized or adsorbed heavy metals by some bacteria in the en-
vironment, microbial sensitivity to redox potential change and
changes into the valence state of particular toxic metal.
During the last two decades, phytofiltration, a very en-
vironmentally friendly and low-cost alternative technique, is a
promising emerging alternative to conventional cleanup. After the
discovery of As hyperaccumulating and tolerating plants, it is
possible to phytoremediate the As contaminated substrates. Phy-
tofiltration involves several steps, (i) the selection of the most
promising plants capable of removing the contaminant from water
and retaining it in their roots, and (ii) plants are then transplanted
into a constructed wetland, where As from the polluted water will
be removed. These plants mainly absorb and concentrate the As in
their roots, but can also translocate low quantities to their shoots
(Dushenkov et al., 1995; Salt et al., 1998). In recent years, only
plants which are able to hyperaccumulate As were discovered, like
P. vittata (Ma et al., 2001) and other ferns (Francesconi et al., 2002;
Zhao et al., 2002; Srivastava et al., 2005). Aquatic macrophytes
have been particularly considered for As removal from con-
taminated surface water bodies. Several studies were performed
for the removal of As from contaminated surface water bodies
using different species of aquatic macrophytes: water hyacinth
255
(Eichhornia crassipes), lesser duckweed (Lemna minor) (Alvarado
et al., 2008), dried algae (Lessonia nigrescens) (Hansen et al., 2004)
and dried macro-algae (Spyrogira spp.) (Bundschuh et al., 2007).
Recently, use of native biomasses (powdered) was reported to
remove As from surface water. For example, biomass from the
stem of a thorny Acacia nilotica was used for the removal of As
from As contaminated water bodies (Baig et al., 2010). Earlier,
other biomasses derived from fish scales, coconut fiber, dried roots
of water hyacinth plant, seed powder of Moringa oleifera, Mo-
mordica charantia, powdered eggshell, human hair, rice husk, rice
polish; without chemical treatment have been reported
(Wasiuddin et al., 2002; Al-Rmalli et al., 2005; Kumari et al., 2006;
Nurul-Amin et al., 2006; Oke et al., 2008; Rahaman et al., 2008;
Pandey et al., 2009; Ranjan et al., 2009). However, there is still a
strong challenge in developing economical and commonly avail-
able biosorbents for the As removal.
4.3. Coagulation–flocculation
In As removal processes, coagulation and flocculation are
among the most common method ever employed. The addition of
a coagulant followed by the formation of a floc is a potential way
for the removal of As from groundwater. Coagulants change the
surface charge properties of solids to allow the agglomeration or
enmeshment of particles into a flocculated precipitate. The final
products are larger particles or floc, which settle under the influ-
ence of gravity or filtered more readily. The destabilization of
colloids by neutralizing the forces that keep them apart, is the
purpose of coagulation. Positively charged cationic coagulants
provide positive electric charges to reduce the negative charge
(zeta potential) of the colloids and as a result, larger particles are
formed due to the aggregation of particles (Choong et al., 2007).
Flocculation is the action of polymers to form the bridges between
the larger mass particles or flocs and bind the particles into the
large agglomerates or clumps (Choong et al., 2007). In this tech-
nique, commonly used chemicals are aluminum salts such as
aluminum sulfate [Al2(SO4)3  18H2O], and ferric salts such as ferric
chloride [FeCl3] or ferric sulfate [Fe2(SO4)3  7H2O] because of their
low cost and relative ease of handling. In As removal by this pro-
cess, chemicals transform As (dissolved) into solid (insoluble)
which is precipitated later. Dissolved As may also be adsorbed on
the solid hydroxide surface site and be coprecipitated with other
precipitating species (Mondal et al., 2006). The solids can be re-
moved through sedimentation and/or filtration. Removal of As
from water by coagulation using ferric or aluminum salts have
been reported in several studies (Zouboulis and Katsoyiannis,
2002; Yuan et al., 2003; Wickramasinghe et al., 2004; Song
et al., 2006; Andrianisa et al., 2008; Lakshmanan et al., 2010;
Lacasa et al., 2011). Coagulants such as alum [Al2(SO4)3.18H2O],
ferric chloride [FeCl3] and ferric sulfate [Fe2(SO4)3  7H2O] are
found to be effective in removing As from water (Edwards, 1994).
Ferric salts have been found to be more effective than alum in
removing As on a weight basis and effective over a wider pH range
(Cheng et al., 1994; Hering et al., 1997). At pH 7.6 or lower, iron and
aluminum coagulants are of equal effectiveness in removing AsV.
However, iron coagulants are advantageous if pH is above 7.6, if
soluble coagulant metal residuals are problematic, or if AsIII is
present in the raw water. Generally, with increasing coagulant
dosages higher As removal efficiencies can be achieved. The ef-
fectiveness of iron coagulants in removing AsIII diminishes at pH
6.0. Wickramasinghe et al. (2004) used ferric chloride and ferric
sulfate as a coagulant and their study suggested that the rate of As
removal was dependent on the raw water quality and pH adjust-
ment before coagulation. On the other hand, studies investigating
the effects of cationic (Wickramasinghe et al., 2004; Zouboulis and
Katsoyiannis, 2002; Han et al., 2002) and anionic (Zouboulis and
256 R. Singh et al. / Ecotoxicology and Environmental Safety 112 (2015) 247–270
Katsoyiannis, 2002) polymers for increasing As removal are lim-
ited in numbers. Pallier et al. (2010) used kaolinite and FeCl3 as a
coagulant/flocculent and they observed over 90% and 77% re-
movals of AsV and AsIII, respectively, using 9.2 mg L
1 of Fe3 þ . In a
recent study, Hu et al. (2012) used three aluminum based coagu-
lants (aluminum chloride and two types of polyaluminium chlor-
ide) and all of them were able to reduce the concentration of As
below the MCL (Maximum Contaminant Level) with an initial AsV
concentration of 280 mg L
1. Further their study suggests that the
aluminum species regulates the removal of As and therefore, the
efficiency of As removal can be improved by adjusting the pH. The
presence of sulfates significantly decreases AsIII removal, but only
slightly affects AsV removal. At pH higher than 7.0, removal of AsV
increases in the presence of calcium. The major limitation of the
coagulation/flocculation process is the production of a large
amount of sludge with a considerable concentration of As.
Recently, instead of conventional Al and Fe salts, titanium tet-
rachloride (TiCl4) was used (Shon et al., 2007) to remove the
particulate and dissolved organic matter from wastewater in
sewage treatment plants. TiCl4 successfully achieved high organic
matter removal to the same extent as Al and Fe salts and the re-
sulting flocs are with better settleability. The most significant ad-
vantage of using TiCl4 as a coagulant is that sludge recovery pro-
duces a valuable by-product, namely titanium dioxide (TiO2) (Shon
et al., 2007; Lee et al., 2009), which is the most widely used metal
oxide, whose applications include cosmetics, electronic paper,
paints, photocatalysts, and solar cells (Hoffmann et al., 1995; Obee
and Brown., 1995). Furthermore, the residual Ti salt concentration
in the treated water satisfied the requirement of the World Health
Organization's (WHO) guidelines (0.5–15 mg L
1) for drinking
water (Ravenscroft et al., 2009). Therefore, TiCl4 is expected to be a
promising alternative coagulant for conventional Al and Fe salts.
4.4. Electrocoagulation (EC)
It is an alternative process to CF (coagulation/flocculation). In-
stead of adding a chemical reagent as ferric chloride, metallic ca-
tions are directly generated in the effluent to be treated by ap-
plying a current between iron electrodes to dissolve soluble an-
odes. In EC, electrolytic oxidation of a sacrificial iron anode pro-
duces FeIII oxyhydroxides/precipitates in As contaminated water.
With FeIII precipitates As forms binuclear, inner-sphere complexes
(van Genuchten et al., 2012), which aggregate to form a floc. Me-
tallic cations and hydroxides formed neutralize negatively charged
colloids allowing them to coagulate (Matteson et al., 1995). During
EC with iron electrodes, the amount of iron cations experimentally
dissolved from the anode corresponds to the value predicted by
the second Faraday's law (Vik et al., 1984; Pretorius et al., 1991)
which is used to calculate the treatment dose to apply.
4.5. Electro-chemical arsenic remediation (ECAR)
The ECAR is a form of electrocoagulation (EC) that has been
developed to support a community scale micro-utility business
model (Amrose et al., 2013). In ECAR, the high capacity adsorbent
media are generated in-situ, removing the need for a central ad-
sorbent manufacturing plant or importing media from abroad. In
ECAR, the As-laden flocs are separated from clean water through
gravitational settling aided by a small amount of alum as a coa-
gulant. The effectiveness of ECAR has been demonstrated by
Amrose et al. (2013), using synthetic groundwater in lab studies,
real contaminated groundwater from Bangladesh and Cambodia,
and in short-duration field trials of two 100 L batch reactors in
West Bengal.
The ECAR was found to lower initial As concentrations as high
as 3000 μg L
1 to below the WHO-MCL of 10 μg L
1, and easily
reached below 5 μg L
1. Strong oxidants produces during the
Fenton-type reactions were found to oxidize AsIII to AsV (Li et al.,
2012). This is a key reaction for high effectiveness in the Bengal
region because AsIII does not adsorb as strongly as AsV to FeIII
oxyhydroxide surfaces in natural water at neutral pH (Dixit and
Hering, 2003), and both AsIII and AsV are present in the ground-
water (Kinniburgh and Smedley, 2001). Although the initial as-
sessments of reliability, robustness, consumables cost, and sludge
production from 100 L reactor field trials were promising (Amrose
et al., 2013), however, is very limited in scope due to the small
system size and short duration.
4.6. Adsorption
Adsorption is a process that uses solids for removing sub-
stances from either gaseous or liquid solutions. Adsorption process
has been used most widely because of its high removal efficiency,
easy operation and handling, low cost and sludge-free. Recently,
several studies have focused in the development of novel materials
based on alumina (Han et al., 2013), activated carbon (Zhang et al.,
2007; Oliveira et al., 2008), iron oxides (Giménez et al., 2010; Sun
et al., 2013), zeolites (Swarnkar and Tomar, 2012), clays (Anjum
et al., 2011) etc. to adsorb As from water. Adsorption has attracted
much attention due to the following advantages: (i) it usually does
not need a large volume and additional chemicals, (ii) it is easier to
set up as a POE/POU (point of entry/point of use) As removal
process (Jang et al., 2008), and (iii) it does not produce harmful
byproducts (Genc et al., 2004, Zhang et al., 2005) and can be more
cost effective (Zhang et al., 2007). Generally, the removal of As by
adsorption techniques depends on pH and the speciation of AsV
thus, at pH lower than 7 showing better AsV removals compared to
the AsIII (Zhu et al., 2013). The capacity and adsorption rate further
depends on the presence of other ions like phosphate, silicate,
HCO3- and Ca2 þ competing for the adsorption sites (Giles et al.,
2011, Zhu et al., 2013). There are some common adsorption tech-
niques used for the efficient As removal from water are discussed
below.
4.6.1. Activated alumina
Activated alumina (AA) is a physical/chemical process by which
ions in the feed water are sorbed to the oxidized AA surface. It is
the most widely tested aluminium oxide (Lin and Wu, 2001; Singh
and Pant, 2004; Giles et al., 2011). AA was the first adsorptive
medium to be successfully applied for the removal of As from
water supplies (EPA, 2000a, 2000b). It is prepared by the thermal
dehydration of aluminium hydroxide Al(OH)3 at high temperature.
It is a porous, granular material having typical diameter of 0.3–
0.6 mm and a high surface area for good sorption properties. The
AA is used in packed beds to remove contaminants such as As,
fluoride, NOM, selenium and silica. Under pressure, feed water is
continuously passed through the beds to remove the con-
taminants. The contaminant ions are exchanged with the surface
hydroxides on the alumina. When adsorption sites on the AA
surface become filled, the bed must be regenerated.
The As removal capacity of activated alumina is pH sensitive
thus requires pre-and post-pH adjustment using caustic soda and
sulfuric acid. AsV is strongly adsorbed on AA at pH 5–6 whereas
AsIII is best adsorbed at pH 7–8 (Singh and Pant, 2004). The ad-
sorption capacity of AA ranges from 0.003 to 0.112 g of As g
1 of
AA. The factors which have significant effects on the As removal
achieved with AA are pH, As oxidation state, competing ions,
empty bed contact time (EBCT), and regeneration. Other factors
include spent regenerant disposal, alumina disposal, and second-
ary water quality.
The AA media can either be regenerated on-site or disposed of
and replaced with fresh media. Regeneration is achieved through a
 R. Singh et al. / Ecotoxicology and Environmental Safety 112 (2015) 247–270
sequence of rinsing with regenerant, flushing with water, and
neutralizing with acid. The regenerant is a strong base, typically
sodium hydroxide (NaOH) and the neutralizer is a strong acid,
typically sulfuric acid (H2SO4). The regeneration of saturated alu-
mina is carried out by exposing the medium to 4% NaOH, either in
batch or by flow through the column resulting in high As con-
taminated caustic wastewater. Onsite regeneration of AA media
typically produces 37–47 bed volumes of caustic soda waste (EPA,
2000a, 2000b). The caustic soda residue is then washed out and
the medium is neutralized with 2% solution of H2SO4 rinse. It has
been reported that at pH range 2.8–11.5, alum-impregnated AA is
much better adsorbent for AsV than untreated AA and when em-
ployed in batch mode AsV concentration could be brought down
from 10 mg L
1 (10,000 ppb) to 40 ppb (Tripathy and Raichur,
2008).
The adsorption capacity and rate of conventional activated
alumina (CAA) for As removal is relatively low and slow, which has
been attributed to its ill-defined pore structure along with small
surface area as it is reported that the maximum AsV adsorption
capacity of granular AA with a surface area of 118 m2 g
1 (Ma-
cherey-Nagel, Germany) is 15.9 mg g
1 (Lin and Wu, 2001). On the
other hand, mesoporous materials have attracted much attention
in the field of chemical engineering, optics, electromagnetics,
biomedicine, industrial catalysis and adsorption, environmental
protection, and fabrication of novel nano-object materials due to
the high surface area, well-defined and adjustable pore diameter
of 2–50 nm (Ying et al., 1999; De Vos et al., 2002). Therefore, it
could be concluded that mesoporous alumina (MA) should be an
ideal adsorbent for removing As. Recently, efforts have been made
to synthesize appropriate mesoporous alumina for removing AsV,
which included high-temperature crystallization (Patra et al.,
2012) or the use of expensive aluminum alkoxide (e.g. aluminum
tri-sec-butoxide) and organic solvent (2-butanol) (Yu et al., 2008).
4.6.2. Iron based sorbents (IBS)
Adsorption on IBS is an emerging treatment technique for As
removal. Removal has been attributed to ion exchange, specific
adsorption to surface hydroxyl groups or coprecipitation. Cur-
rently, IBS products available in the market are granular ferric
hydroxide (GFH), iron coated sand, modified iron and iron oxide
based adsorbents. Selvin et al. (2000) have described the sorption
process as chemisorption, which is typically considered to be ir-
reversible. It has been reported that AsV adsorption on hydrous
iron (III) oxide strongly depended on the system's and pH (Ranjan
et al., 2003), while AsIII adsorption was pH insensitive. The AsIII
required less contact time to attain equilibrium and sulphate;
phosphate and hydrogen carbonate did not compete strongly with
the AsIII adsorption. At acidic to neutral pH, adsorption of AsV is
generally more effective than the adsorption of AsIII (Arienzo et al.,
2005; Dixit and Hering, 2003; Leupin et al., 2005; Singh et al.,
2007; Sharma et al., 2007; Su and Puls, 2008; Abdallah and
Gagnon, 2009; Burton et al., 2009). On the basis of chemistry of
the remediation process, iron based technologies can be divided
into two overlapping groups; first is when iron acts as sorbent, co-
precipitant or contaminant immobilizing agent and the second is
when iron behaves as a reductant (convert contaminants into
lower oxidizing state or used as an electron donor). Two important
iron based materials are hydrous ferric oxide (HFO) and goethite
(a-FeOOH) which are used as sorbent but goethite is less reactive
than HFO due to the lack of sufficient surface area (Smedley and
Kinniburgh, 2002). The mechanism of AsV adsorption on GFH was
studied in detail by Guan et al. (2008), and they proposed that at
7.4 pH, bidentate binuclear complexes with GFH are formed as
evidenced by an average Fe–AsV bond distance of 3.32 Å by EXAFS
analyses. The impacts of temperature on adsorption kinetics and
equilibrium capacities for AsIII and AsV on GFH have been reported
257
by Banerjee et al. (2008) and they showed that overall adsorption
reaction rate constant values for both AsV and AsIII increased with
increase in the temperature. The thermodynamic parameters ex-
amination revealed that the adsorption of AsV and AsIII by GFH was
a spontaneous endothermic process.
Polymorphs of iron (III) hydroxy-oxide mineral [FeO(OH)] such
as goethite (a-FeOOH), akaganèite (b-FeOOH) and lepidocrocite (c-
FeOOH) have been described as good adsorbents for AsV. Pure
goethite was synthesized by Mohapatra et al. (2007) with different
dopant cations (Cu, Ni and Co) for adsorption of AsV. With
330 m2 g
1 surface area, akaganèite exhibited adsorption capacity
as high as 120 mg g
1 (Deliyanni et al., 2003). The adsorption
capacity of akaganèite (b-FeOOH) can be enhanced by isomorphic
substitution of Fe3 þ by Zr4 þ on its structure (Sun et al., 2013). At
pH 7.0, the maximum adsorption capacity for AsV by akaganèite
was 60 mg g
1. Adsorption capacities for lepidocrocite have been
reported 25.17 mg g-1 with specific area of 103.9 m2 g
1 (Repo
et al., 2012). Another less known polymorph constitutes d-FeOOH,
having similar crystallographic structure as CdI2. Crystalline d-
FeOOH can be easily prepared in the laboratory by a simple
method, with small particle size, high specific area and narrow
pore size distribution. The uniqueness of this FeOOH polymorph is
that it is ferrimagnetic, thus after use in catalysis or adsorption
process it can be easily recovered by using a simple magnet (Pinto
et al., 2012). These characteristics make d-FeOOH a suitable can-
didate for use as an adsorbent for heavy metals in aqueous med-
ium. Among the natural minerals, Fe containing natural magnetite
(Fe3O4), siderite and hematite have given much attention (Dixit
and Hering, 2003; Giménez et al., 2007; Jönsson and Sherman,
2008). Guo et al. (2007a, 2007b) found that natural siderite and
hematite removed As through electrostatic attraction and surface
complexation with the Fe hydroxides in the minerals. However,
the rate of reaction was slow and common anions such as bi-
carbonate and phosphate decreased the adsorption capacity of As.
In recent years, Fe3O4 (magnetite), a magnetic nanoparticles of
iron oxide nature and c-Fe2O3 (i.e., maghemite) have been found
applicable in many practical branches of human activity. Based on
these, a promising technique was devised by mixing magnetite
and maghemite nanoparticles which can adsorb As from aqueous
solution and fit to use for the groundwater treatment. Under acidic
pH conditions, 96–99% As uptake was recorded. The maximum
adsorption occurred at 2.0 pH with values of 3.69 and 3.71 mg g
1
of adsorbent for AsIII and AsV, respectively at the initial con-
centration of 1.5 mg L
1 solution of both species. However, in
presence of phosphate in the solution, the efficiency of the ad-
sorption process suffered. Less than 60% As uptake was achieved
from the natural groundwater containing more than 5 mg L
1
phosphate and 1.13 mg L
1 of As. This is a practical problem to be
faced in the field application of the technology (Chowdhury and
Yanful, 2010).
Highly stable amorphous mesoporous iron oxides, prepared by
thermal decomposition of ferric nitrate-oxalic acid complex, showed
to be promising for the adsorption of AsV (Muruganandham et al.,
2010). To increase the adsorption capacity of iron oxides, iron oxides
composites and carbonaceous materials have been used as a strategy.
For example, composites of Fe3O4-reduced graphite oxide-MnO2 re-
moved 12.22 mg AsV per gram of catalyst (Luo et al., 2012) while in the
presence of Fe3O4/graphene composite, a high adsorption capacity
(180.3 mg g
1) for AsV was achieved (Mishra and Ramaprabhu, 2012).
Composites of iron oxides and TiO2 or Al2O3 presented adsorption
capacity for AsV of 7.8 and 54.55 mg g
1, respectively (D'Arcy et al.,
2011; Basu et al., 2012)). On the other hand, natural iron oxides
showed very low adsorption capacity (0.02–0.4 mg g
1) because of its
low specific surface area (Zhang et al., 2004; Guo et al. 2007a, 2007b;
Giménez et al., 2010).
258 R. Singh et al. / Ecotoxicology and Environmental Safety 112 (2015) 247–270
Besides micrometer-sized particle assemblies, iron oxide na-
noparticles are frequently employed for the removal of As due to
their high surface area. Recently, Sabbatini et al. (2010) have de-
veloped tubular ceramic adsorbers based on iron oxide nano-
particles that have been deposited on porous alumina tubes. Iron
oxide nanoparticles with combined ozonization-reactive ceramic
membranes have been proved a good candidate for AsIII removal
(Park and Choi, 2011). In a study, Pan et al. (2010) have reported
that on using iron-oxide-coated diatomite, a granular adsorbent,
for adsorption of AsV from aqueous solution, effectively working at
pH very close to the neutral value; here an industrial grade dia-
tomite served as the iron oxide support. Recently, Chen et al.
(2011) have suggested ferric-impregnated volcanic ash as a re-
presentative of low-cost adsorbent for removal of AsV from an
aqueous medium.
4.6.3. Zero valent iron
Over the last decade, a great deal of research has been focused
on the removal of contaminants by zero valent iron (ZVI) because
ZVI is non-toxic, abundant, cheap, easy to produce, and little
maintenance is required by its reduction process. The method is
based on the principle is when the oxygenated water comes in
contact with ZVI, it results in corrosion of ZVI and formation of
various byproducts like FeII and FeIII hydroxides, that can oxidize
and remove As (Farrell et al., 2001; Manning et al., 2002). Many
groups have extensively investigated the removal of As by using
ZVI in the laboratory (Leupin and Hug, 2005; Katsoyiannis et al.,
2008; Klas and Kirk, 2013) as well as in the field (Hussam and
Munir, 2007; Chiew et al., 2009; Neumann et al., 2013). Based on
this technology, approximately 350,000 filters are in use in India,
Bangladesh, Pakistan, Nepal and Egypt with better results of As
removals in field (Hussam and Munir, 2007, 2013; Neumann et al.,
2013). It is desirable to analyze the effect of key variables, such as
pH, dissolved oxygen (DO), hardness, and humic acid (HA) on As
removal. Generally it is accepted that the mechanism of As re-
moval by ZVI involves adsorption, reduction, surface precipitation,
and co-precipitation with various iron corrosion products such as
ferrous/ferric hydroxides (Mak et al., 2009). The removal rates of
AsIII were investigated in the presence of various ions and under
different pH values and results indicated that most of these
parameters affected negatively the removal of AsIII (Biterna et al.,
2010). Sun et al. (2011) reported that in anaerobic conditions when
AsV reacted with commercial ZVI or acid-treated ZVI both ad-
sorption and reduction of AsV were fast; commercial ZVI reduced
AsV to AsIII while acid-treated ZVI reduced AsV to As0.
The DO plays an important role in As removal by ZVI. The re-
action of ZVI with DO leads to the formation of reactive inter-
mediates (e.g. HO2/–O2
, H2O2, –OH) and Fe(II). Fe(II) is oxidized
to Fe(III) and forms hydrous ferric oxides with large sorption ca-
pacities (Joo et al., 2004), such that there is a potential for the
transformation and removal of a range of inorganic and organic
contaminants. It was found that low pH and high DO would favor
the As removal (Tanboonchuy et al., 2011). In aerobic condition,
Bang et al. (2005b) observed a rapid rate of As removal from
aqueous solution via precipitation/co-precipitation on iron hy-
droxide precipitation product and at pH 7.0 the uptake of AsV was
faster than AsIII. However, in anaerobic conditions, the rate of re-
action was considerably slower as compared to the aerobic en-
vironment and at pH 4.0 and 7.0 the removal rate of AsIII was faster
than AsV. Furthermore, their study also demonstrated that in ab-
sence of O2, reduction of AsV to AsIII and AsIII to metallic As takes
place upon reaction with ZVI. Thus, different reaction mechanisms
of As with ZVI predominate in aerobic and anaerobic environ-
ments. In the absence of O2, ZVI is able to act as a reductant and to
reduce AsV and AsIII.
Mak et al. (2009) had reported that the removal rate of As by
ZVI increased with increasing concentrations of Ca2 þ or HCO3

because CaCO3 can form and acts as a nucleation seed for the
growth of iron hydroxides. In the co-existence of Ca2 þ , HCO3
and
humic acid, the presence of HA diminished the positive role of
Ca2 þ due to the formation of Fe-humate complexes in solution
and delaying of the formation of CaCO3. The effects of HA on AsV
removal by ZVI from groundwater was investigated by Rao et al.
(2009) and they observed that the removal rate of As was inhibited
in the presence of HA probably because of the formation of soluble
Fe-humate in the groundwater which hindered the production of
iron precipitates. When Fe-humate (complexation of HA with
dissolved Fe) was saturated, further corrosion of ZVI accelerated
the removal of As from groundwater via adsorption and co-pre-
cipitation. The AsIII is more mobile and more toxic than AsV,
however, the removal of AsIII is more difficult than the removal of
AsV. To remove high AsIII concentration of 10 mg L–1, Wan et al.
(2010) conducted the combined processes of biological oxidation
of AsIII, the removal of AsIII and AsV by ZVI obtained a very high As
removal capacity (more than 70 mg As g
1 Fe). The kinetics and
mechanism of AsIII oxidation and removal by ZVI at pH 3–11 in
aerated water was investigated by Katsoyiannis et al. (2008) and
found that AsIII was oxidized by the Fenton reaction and removed
by the sorption on newly formed hydrous ferric oxides and hy-
droxyl radicals were the main oxidant for AsIII at low pH.
Recently nZVI, a nanoparticle, is effective and extensively used
for the removal of As from contaminated water (Ludwig et al.,
2009; Morgada et al., 2009; Tanboonchuy et al., 2011, 2012). For
example, a novel process, air and/or CO2 bubbling nZVI was tested
for the removal of high concentration of AsV (3000 mg L
1) and
demonstrated outstanding performances. Tanboonchuy et al.
(2012) investigated the influence of background species on the
removal of AsIII and AsV in the groundwater by nZVI process. They
found that Ca2 þ plays a promoting role while PO43
and HA play
an inhibiting role on removal of As. As for Cl
and HCO3
, the
former enhances AsIII removal, whereas the later inhibits AsIII re-
moval; AsV removal was affected slightly in the presence of Cl

and HCO3
. Although nZVI is effective for the removal of As from
contaminated water, but transformations and translocation of As
at and within the nanoparticles are not clearly understood.
4.6.4. Indigenous filters and cartridges
Presently, several indigenous materials are available that are
used as filters for As adsorbent. Red soil rich in oxidized iron, iron
ore, clay minerals, iron scrap or fillings and processed cellulose
materials are known to have the capacity for As adsorption. The
typical clay minerals such as kaolinite, montmorill ionite and illite
are used for the As adsorption (Lin and Puls, 2000; Goldberg,
2002; Mohapatra et al., 2007). Manning and Goldberg (1996, 1997)
and Mohapatra et al. (2007) reported that As is adsorbed on the
surface of clay through inner sphere surface complexation. To
enhance the adsorption of As on clay, Li et al. (2007) and Su et al.
(2011) prepared surfactant-modified clay to remove As from
aqueous solution. Su et al. (2011) in a study used octadecyl tri-
methylammonium chloride, octadecyl benzyl dimethylammonium
chloride and dioctadecyl dimethyl ammonium chloride as cationic
surfactants for the modification of bentonite. The charge on the
clay surface get reversed i.e. from negative to positive by the re-
placement of exchangeable Na þ and Ca2 þ cations on clays with
the cationic surfactants and resulting organoclay becomes a po-
tential adsorbent to adsorb the oxy-anions of As from aqueous
solution (Li and Bowman, 2001).
Zeolites are tectosilicate minerals with 3D aluminosilicate
structure containing water molecules, alkali and alkaline earth
metals in their structural framework. Due to high ion exchange,
adsorbing, catalytic and molecular sieving capacities these have
 R. Singh et al. / Ecotoxicology and Environmental Safety 112 (2015) 247–270
potentials to be used as treatment mineral in the permeable re-
active barriers (PRBs) (ITRC, 2005; Roehl et al., 2005). Removal of
As from different type of water having varying mineralization
degree can also occur through natural zeolitic rocks such as cha-
bazite–phillipsite, clinoptilolite, and volcanic glass. The As removal
efficiency for chabazite–phillipsite was 60–80% and for clin-
optilolite-bearing rocks was 40–60%. Removal of As is influnced by
three key factors first, mineralogy of the zeolites occurring in the
volcanic rock, second, zeolite content of the zeolitic rock and lastly,
the degree of water mineralization (Ruggieri et al., 2008).
By using above mentioned materials, some of the filters are
manufactured including Sono 3-Kolshi Filter, Granet Home-made
Filter, Chari Filter, Adarsha Filter, Shafi Filter, and Bijoypur Clay/
Processed Cellulose filters. The Garnet home-made filter contains
relatively inert materials like brick chips and sand as filtering
media without added any chemical to the system. Air oxidation
and adsorption on iron-rich brick chips and flocs of naturally
present iron in ground water could be the possible reason for As
removal from ground water. The study demonstrates that three-
pitcher filters are an effective option as a short-term measure for
As removal. However, the three-pitcher filters that are not effec-
tive option for long duration. The Chari filter also uses brick chips
and inert aggregates in different Charis as filter media. The Shafi
and Adarshs filters use clay material as filter media in the form of
candle. Although the Shafi filter was reported to have better As
removal capacity but clogging of filter media is still a problem.
Khair (2000) found that Bijoypur clay and treated cellulose were
also able to adsorb As from water. These units/filters remove As
like any other dissolved ions present in the water but are not
suitable for water having high impurities and iron content in
water. In early 90s, the development of Bio-Sand Filter (BSF) for
homebased drinking water treatment has received much attention
because of its high pollutants removal, technical simplicity, cost
effectiveness and least maintenances (Bajpai and Chaudhuri, 1999;
Gene-Fuhrman et al., 2005; Ngai et al., 2006; Guo et al., 2007a,
2007b; Mahmood et al., 2011). Later Ngai et al. (2006), Ahammed
and Davra (2011) and Noubactep et al. (2012) made certain mod-
ifications to BSF design and filter media for improving its perfor-
mance. In a recent study, Noubactep et al. (2012) employed three
compartment model of BSF having extended reactive layer of ZVI
and reported the significant pollutants removal for safe drinking
water production. Kanchan arsenic filter (KAF), a saturated sand
filter was designed by Ngai et al. (2006), and found to successfully
remove As and pathogens from drinking water. Sand is considered
as a non-reactive material and only removed suspended particles
during filtrations (Noubactep, 2010).
Metal oxides/hydroxides coated adsorbents such as iron oxide
coated sand, manganese-coated sand, Fe3 þ impregnated activated
carbon, siderite-coated quartz and hematite coated quartz have
been extensively used to improve the filter efficiency (Jessen et al.,
2005; Leupin et al., 2005; Guo et al., 2007a, 2007b; Chang et al.,
2008; Mondal et al., 2008; Chiew et al., 2009; Noubactep, 2010;
Noubactep and Care, 2010; Maji et al., 2011; Noubactep et al.,
2012). Recently, Rahman et al. (2011) employed sub-surface wet-
land and soil filter systems for As removal. Many emergent ad-
sorbents being used in filter-based treatments are not sufficient to
remove total As (AsIII þ AsV) from water (Xu et al., 2007; Guan
et al., 2012). Therefore, in order to provide As free drinking water
on sustainable basis, pre-oxidation process is essential to convert
AsIII into better adsorbable AsV (Chang et al., 2008). In many de-
veloping countries, cinders generated from the combustion of coal
honey comb briquette (HBC) in decentralized cylindrical stoves
have mostly been used for the civil applications. Recently, Yue
et al. (2011) and Sheng et al. (2014) experimentally proved HBC to
be useful for the pollutants removal. Sheng et al. (2014) confirmed
that iron-amended HBC efficiently removed AsV (961.5 mg g
1) in
259
aqueous solutions. Furthermore, in China, over 60% of rural
households are directly depends on coal honeycomb briquette for
cooking and heating (Sinton et al., 2004), that ultimately produce
massive cinders.
4.6.5. Miscellaneous adsorbents
In last years, a wide variety of adsorbent systems have been
developed for the removal of As. Activated carbon (Huang and Fu,
1984), fly ash (Diamadopoulos et al., 1993), aluminum-loaded coral
limestone (Ohki et al., 1996), modified fly ash (Goswami and Das,
2000), iron oxide minerals (Suvasis and Janet, 2003), activated
neutralized red mud (Hulya et al., 2004), chitosan (Chen and
Chung, 2006), chitosan derivatives (Laurent et al., 2002), iron hy-
droxide-coated alumina (Hlavay and Polyak, 2005), modified fun-
gal biomass (Pokhrel and Viraraghavan, 2006), iron containing
mesoporous carbon (Zhimang and Baolin, 2007), iron oxide-im-
pregnated activated carbon (Ronald et al., 2007), nanoparticles of
hydrous iron oxide (Sylvester et al., 2007) etc. were used as ad-
sorbents for the removal of As from aqueous environments. Chit-
osan is transformed polysaccharide obtained from the de-acet-
ylation of chitin, which makes the shells of crustaceans such as
crabs and shrimps. It is biodegradable, biocompatible, and non-
toxic, making it environment friendly. Guibal (2004) reported
chitosan as an efficient heavy metal scavenger due to the presence
of hydroxyl and amino group with high activity as adsorption site.
Although, chitin/chitosan have been used for the removal of AsV
from water but capacity was found to be very low
(0.13 mmol g
1). Recently, a novel composite chitosan bioadsor-
bent (CCB) have been developed (Boddu et al., 2008) for the re-
moval of AsIII and AsV from aqueous solutions by coating natural
biopolymer, chitosan, on ceramic alumina, using a dip-coating
process. Their study reported a very high adsorption capacity at
pH 4.0 (56.50 and 96.46 mg g
1 for AsIII and AsV, respectively).
Chen et al. (2008) used the chitosan impregnated with molybdate
to remove AsIII and AsV from contaminated water.
A high As sorption capacity (2860 mg g
1) was observed on
activated carbon by Rajakovic (1992). Rajakovic (1992) found that
carbon pretreated with Ag þ or Cu2 þ ions improved the AsIII ad-
sorption but reduced the AsV adsorption. In order to improve the
As adsorption carbon was impregnated with different metal ions
such as iron oxide. For example, Gu et al. (2005) prepared the iron
containing granular activated carbon (GAC) adsorbents for As ad-
sorption from drinking water. Factors such as solution pH, carbon
type and carbon pretreatment and elution of the As from loaded
carbon that affect the mechanism of the adsorption of As species
on activated carbons were studied (Lorenzen et al., 1995). They
observed that AsV is more effectively removed from solution by
using activated carbon with high ash content and pre-treatment of
the carbon with Cu(II) solutions also improved its As removal ca-
pacity. Gu and Deng (2006) prepared iron containing mesoporous
carbon (IMC) from a silica template (MCM-48) and used for the
removal of As from drinking water. The maximum adsorption ca-
pacities were 5.96 mg As g
1 for AsIII and 5.15 mg As g
1 for AsV.
Focusing the morphology and size of adsorbents it is aimed to
generate high surface areas and high density of adsorptive sites.
For example, three-dimensional flower-like, urchin-like and hier-
archical superstructure adsorbents have been found to well suit
the adsorption application (Zhong et al., 2006; Wang et al., 2012;
Zhang et al., 2012). Pore structure also influences the adsorption
behavior of an adsorbent (Drisko et al., 2009; Kimling et al., 2012).
Hierarchically porous materials, possessing macro-and/or meso-
porous networks, facilitate rapid As species diffusion as well as
promote access to the active sites, resulting in a high As uptake
and kinetics (Zhang et al., 2010a, 2010b; Wu et al., 2012). Chemical
composition variation can change the properties of adsorbent
materials; consequently affect the adsorption performance in
260 R. Singh et al. / Ecotoxicology and Environmental Safety 112 (2015) 247–270
applications (Kimling et al., 2012). In addition, the speciation of As
and the surface charge of the adsorbents are related strongly to the
water pH value. Thus, pH effect plays a great role in the As ad-
sorption process (Sofia Tresintsi et al., 2012).
In the past few years, ceria (Ce) and zirconia (Zr), highly re-
active rare-earth metal oxides, are found incorporated into the
adsorbents that significantly can improve the adsorption capacity
of As because they have a unique selectivity for polyoxy anions
(Biswas et al., 2008). For example, granular Fe–Ce oxide (Zhang
et al., 2010a, 2010b), Fe–Zr binary oxides (Ren et al., 2011), Ce–Ti
oxide (Deng et al., 2010), Zr (IV)-loaded ligand exchange fiber
(Rabiul Awual et al., 2012), Zr (IV)-loaded orange waste gel (Biswas
et al., 2008), etc. showed enhanced As adsorption performance
because of their increased surface areas, surface hydroxyl group,
and pore accessibility. In aqueous solutions, Ce and Zr can form
tetranuclear or octanuclear species, which have abundant hydro-
xyl groups and water molecules to be involved in ligand sub-
stitution with As species (Zhong et al., 2007; Biswas et al., 2008; Li
et al., 2010). Thus, composites combined CeO2 and ZrO2 might be
an ideal candidate for the removal of As.
4.7. Ion exchange
In the past, ion exchange has been used for removal of con-
taminants from water (Oehmen et al., 2006). Ion exchange is a
physical/chemical process by which an ion on the solid resin phase
is exchanged for an ion in the feed water. The solid resin is typi-
cally an elastic three-dimensional hydrocarbon network contain-
ing a large number of ionizable groups electrostatically bound to
the resin. These groups are exchanged for ions of similar charge in
solution that have a stronger exchange affinity (i.e. selectivity) for
the resin. Typically, strong-base anion exchange resins are com-
monly used for the removal of As where the oxy-anionic species of
AsV (such as H2AsO4
, HAsO4
2 and AsO4
3) are effectively ex-
changed with the anionic charged functional group of the resin,
thus produces effluents with low concentration of AsV (Choong
et al., 2007). Over a larger range of pH, strong-base anion resins
tend to be more effective than weak-base resins. The order of
exchange for most strong-base resins is given below:
HCrO4
4CrO42
4 ClO4
4SeO42
4SO42
4NO3
4Br
4
(HPO42
, HAsO42
, SeO32
, CO32
)4CN
4NO2
4Cl
4
(H2PO4
, H2AsO4
, HCO3
)4 OH
4CH3COO
4F
This technology in drinking water treatment is commonly used
for the softening and nitrate removal. Before passing the As con-
taminated water, the resin bed are usually flushed with HCl so as
to implant labile Cl
on the surface of the resin, which later easily
exchanged with As. The AsV can be easily removed through the use
of strong-base anion exchange resin either in the form of chloride
or hydroxide. Sarkar et al. (2007), Wan et al. (2010) and Donia et al.
(2011) have reported As removal by using strong base anion ex-
change resins. The efficiency of ion exchange process is improved
by pre-oxidation of AsIII to AsV but before the ion exchange, the
excess of oxidant often needs to be removed in order to avoid the
damage of sensitive resins. Therefore, the efficiency of the ion
exchange process for AsV removal strongly depends on the solu-
tion pH and the concentration of competing ions most notably
sulfates and nitrates, resin type, alkalinity, and influent. Other
factors include the affinity of the resin for the contaminant, spent
regenerant and resin disposal requirements, secondary water
quality effects, and design operating parameters. The performance
of an ion exchange system can be adversely affected by high levels
of total dissolved solids (TDS). Nitrate, sulfate and phosphate,
common competitive anions, play a significant role for the removal
of As via ion exchange. When an ion is preferred over AsV, higher
As level in the product water than exist in the feed water can be
produced. Höll (2010) suggested if a resin prefers sulfate over AsV,
for example, sulfate ions may displace previously sorbed AsV ions,
the resulting levels of As in the effluent is greater than the As level
in the influent. In general, ion exchange for As removal is only
applicable for low-TDS, low-sulfate source waters. Removal of As
can also be affected by the presence of iron, FeIII, in feed water. In
the presence of FeIII, As may form complexes with iron. These
complexes are not removed by ion exchange resins and therefore
As is not removed.
4.8. Electrokinetics
Electrokinetic (EK) remediation is a technique that already had
proven its value, especially in contaminated fine-grain soils.
Virkutyte et al. (2002) reported three phenomena occurs during
electrokinesis are electro-osmosis, electromigration and electro-
phoresis. This method uses a low-level direct current as the
“cleaning agent”, several transport mechanisms (electroosmosis,
electromigration and electrophoresis) and electrochemical reac-
tions (electrolysis and electrodeposition) are induced (Acar and
Alshawabkeh, 1993). When a direct electrical field is applied across
a wet mass of contaminated soil, the migration of non-ionic pore
fluids by electro-osmosis and the ionic migration of dissolved ions
take place towards the electrodes. This technique has certain ad-
vantages over the conventional methods: (1) it is efficient in low
permeability soil, which is difficult to treat by using other meth-
ods; (2) is possible to set-up in situ for sites that are impossible to
excavate, such as residential areas and railway soil and (3) it can
remove organic and inorganic pollutants from soil simultaneously.
The electro-remediation is considered to be the most effective
in treating near saturated, clay soils polluted with metals, whereby
removal is 4 90% (Virkutyte et al., 2002). Sims (1990) and
Cauwenberghe (1997) reported that in sub-surface the electro-
migration rate is dependent upon the density of water current, soil
pore, ionic mobility, grain size, concentration of contaminant and
total ionic concentration. In turn, it is governed by advection
which is generated by electroosmotic flow and externally applied
hydraulic gradients, diffusion of the acid front to the cathode and
the migration of anions and cations towards the respective elec-
trodes (Zelina and Rusling, 1999).
During the EK process, the dominant electron transfer reaction
i.e. electrolysis of water occurs at electrodes is as follow:
H2O-2H þ þ ½ O2(g) þ 2e
(8)
2H2O þ2e
-
-2OH þ H2(g) (9)
The hydrogen ions produced in the above given process de-
creases the pH near the anode causing desorption of metallic
contaminants from the soil solid phases. The dissolved metallic
ions are then removed from the soil solution by ionic migration
and precipitation at the cathode (Acar and Alshawabkeh, 1993). On
the other hand, when hydroxide ion concentration increases the
pH near the cathode also increases. Electro-kinetic remediation
techniques demonstrated 85–95% As removal efficiency, from low-
permeability soils such as clay, peat, kaolinite, high-purity fine
quartz, Na and sand montmorillonite mixtures, as well as from
argillaceous sand (Yeung et al., 1997). However, kaolinite showed
more than 90% removal efficiencies of heavy metals (Pamukcu and
Wittle, 1992).
During EK remediation process, various chemicals such as
chelating agents, surfactants, etc. have been investigated to facil-
itate the mobility of pollutants in soil. To remediate the soil con-
taminated with gasoline Bhattacharya (1996) applied surfactant
effectively using EK system. To restore the diesel-contaminated
sandy soil, Kim and Lee (1999) adopted an anionic surfactant,
sodium dodecyl sulfate (SDS), in the EK process. In their experi-
ments, the effects of electrophoretic transportation of SDS fed into
 R. Singh et al. / Ecotoxicology and Environmental Safety 112 (2015) 247–270
a catholyte chamber, showed the dominant mechanism for the
removal of diesel and compared them to those of electroosmotic
flow. Yang et al. (2005) tested surfactants that had anionic or non-
ionic characteristics and observed the effects of their ionic char-
acteristics and concentrations during the EK process. On the other
hand, to increase removal of heavy metals from the soil, Yeung
et al. (1996) and Wong et al. (1997) tested a chelating agent, EDTA,
in EK remediation system.
4.9. Membrane technology
Membranes are typically synthetic materials with billions of
pores or microscopic holes that act as a selective barrier; the
structure of the membrane allows some constituents to pass
through, while others are excluded or rejected. The movement of
molecules across the membrane needs a driving force, such as
pressure difference between the two sides of the membrane. This
technology can reduce As concentrations to less than 50 mg L
1
and in some cases to below 10 mg L
1. It produces large residual
volumes and is more expensive than other As treatment technol-
ogies. Researchers have explored various types of pressure driven
membrane such as microfiltration (MF), ultra-filtration (UF), nano-
filtration (NF) and reverse osmosis (RO) for the removal of As from
contaminated water. The separation by these processes depends
on the pore size of the membrane; for MF and UF membranes,
mechanical sieving is responsible for separation while for NF and
RO membranes, separation is achieved via capillary flow or solu-
tion diffusion (Shih, 2005; Choong et al., 2007).
4.9.1. As removal using microfiltration
The MF is a low pressure driven membrane process for separ-
ating colloidal and suspended particles in the range 0.1–10 μm.
The MF alone cannot remove the dissolved AsV and AsIII species
from As contaminated water. The As removal by MF membrane
can only be achieved by increasing particle size of As bearing
species therefore prior to MF, coagulation and flocculation pro-
cesses could be effective to increase the particle size of As bearing
species and were found to remove As species from As con-
taminated water (Meng et al., 2000; Han et al., 2002; Chwirka
et al., 2004; Ghurye et al., 2004). For example, Han et al. (2002)
used FeCl3 and Fe2(SO4)3 as flocculants and studied the removal
rate, which was dependent on the adsorption of As on to the FeIII-
complex and their subsequent removal from the solution. Their
results showed that by the combination of flocculation and MF
technique, the As removal efficiency are higher than MF alone and
depends on the effectiveness of As adsorption onto the FeIII-
complex present and also on the rejection of the As containing
flocs formed by the MF membrane. In turn, adsorption of As on the
FeIII complex was found to be affected by the pH of the solution as
well as the presence of other ions in the solution.
Shih (2005) reported that in the pH range 4.0–10.0, negatively
charged AsV anions got effectively adsorbed by forming surface
complex while AsIII removal was poor because in the pH range
4.0–10.0, it remained as neutral species and could not get ad-
sorbed. Therefore, complete removal of As from water could have
been achieved by completely oxidizing AsIII to AsV prior to coa-
gulation–microfiltration process. The size of As containing parti-
cles increases via coagulation–flocculation process and thus makes
it possible to remove As species using low-pressure membrane
technology like MF.
Recently, Ghosh et al. (2011) studied the electrocoagulation (EC)
followed by MF by using a ceramic membrane was found to be ef-
fective in the removal of As from feed solution having concentration
of 200 μg L
1 in presence of fluoride and iron contaminant to a As
content of 8.7 μg L
1. The EC experiment, consisted of a bath with
261
four aluminium sheets of 0.15 m  0.05 m  0.002 m, were continued
upto 45 minutes with a current density of 625 A m
2.
4.9.2. As removal using ultrafiltration
Ultrafiltration (UF) is a size exclusion-based low pressure-dri-
ven membrane separation process having pore sizes in the range
from 10 to 1000 Å and is capable of retaining species in the mo-
lecular weight ranging from 300 to 5,00,000 Da. The rejection of
As by charged membrane explored the influence of co-occurring
divalent ions and natural organic matter (NOM). In presence of
divalent cations such as Ca2 þ , Mg2 þ , AsV rejection reduced almost
upto zero. This reduction in AsV rejection probably due to the
formation of ion pairs between counter ions and the fixed charge
group in the membrane matrix locally neutralizes the membrane
charges. Brandhuber and Amy (2001) investigated the effect of
charge on the UF membranes and reported that mechanism of As
removal was mainly due to the electrostatic interaction between
the As ions and the negatively charged membrane surface, con-
sistent with the Donnan theory. In their study they found a
moderate rejection of 53% and 65% for AsIII and AsV, respectively.
Thus, alone UF is not able to remove the As species directly due to
the pore size, which easily passes the dissolved As through the
membrane.
The presence of NOM improved AsV rejection in presence of
divalent cations. This might be due to the complexion of divalent
ions whose presence in the solution reduces AsV rejection. Another
possibility might be due to the adsorption of NOM onto the
membrane surface to form a negatively charged layer. Solution
with higher concentration of NOM led to higher charge density in
the adjacent membrane layer causing more rejection of the ne-
gatively charged As species.
Iqbal et al. (2007) studied the effect of co-occurring inorganic
solutes (such as HCO3-, HPO42-, H4SiO4 and SO42-) on the removal
of AsV in feed water and permeate flux were investigated by using
a cationic surfactant cetlylpyridinium chloride (CPC) and a flat
sheet hydrophilic polyethersulfone (PES) ultrafiltration membrane
(Millipore, Bedford, MA). The PES membrane without surfactant
micelles was found to be ineffective for the removal of As while
the addition of surfactant significantly increased the efficiency of
As removal. Removal of As with surfactant was found to be 78–
100% while As removal in the presence of inorganic solutes was
only 25%.
The removal characteristics of As with ground water was in-
vestigated by using micellar-enhanced ultrafiltration (MEUF)
(Iqbal et al., 2007). The different cationic surfactants used by them
were benzalkonium chloride (BC), hexadecylpyridinium chloride
(CPC), hexadecyltrimethyl ammonium bromide (CTAB) and octa-
decylamine acetate (ODA). Among these four cationic surfactants
used during MEUF, the highest As removal efficiency was obtained
in case of CPC i.e. 96%, with CTAB was 94% and the removal effi-
ciency with ODA was over 80% while the As removal efficiency
with BC was the lowest i.e. 57% due to the higher critical micelle
concentration (CMC) of BC compared to those of other surfactants.
4.9.3. As removal using Nanofiltrations
Nanofiltrations (NFs), high pressure techniques and are able to
remove the dissolved As from the contaminated water to an ap-
preciable level provided that the feed water contains a very low
amount of suspended solids (Figoli et al., 2010). The nominal pore
size of the membrane is about 1 nm and molecular weight is ty-
pically less than 1000 Da.
Generally, NF membranes are applied for the separation of
multivalent ions from the monovalent ions. These membranes
have slightly charged surfaces and charge interaction plays a
dominant role in separation of molecules. The NF membranes are
usually asymmetric and negatively charged at neutral and alkaline
262 R. Singh et al. / Ecotoxicology and Environmental Safety 112 (2015) 247–270
media but lose their charge in acidic pH. Waypa et al. (1997) re-
ported that both dissolved AsV and AsIII can be effectively removed
(up to 99%) from water due to the size exclusion. However, Urase
et al. (1998) demonstrated that charged membranes generally
have a higher rejection for charged solutes than for uncharged
solutes and concluded that the pore size of the membrane does
not have a significant effect on As rejection, but rather charge
exclusion is predominant over the size exclusion mechanism.
Seidel et al. (2001) and Velizarov et al. (2004) demonstrated
that separation of As is caused due to the electrostatic repulsion
between anionic As species and the charge of membrane (Donnan
exclusion) as well as the small sized pores of the membrane. Al-
though the charges of the NF membranes are not fixed but may
change due to adsorption of anions onto the membrane, and
therefore are dependent on the bulk anion concentration
(Velizarov et al., 2004 ). Moreover, at the isoelectric point of the
membrane, the charge of the membrane is zero, which changes to
positive values for a lower pH. Thus, pH selection is important
with respect to the target ions are to be separated. The perfor-
mances of two commercially available NF membranes (NF90 and
NF200) were studied by Uddin et al. (2007) for removal of both
AsIII and AsV from contaminated water. They demonstrated that
the rejection of AsV was better than AsIII and even when the feed
solutions contain 50 mg L
1, AsIII could not be reduced to MCL and
they concluded that oxidation of AsIII to AsV is an essential pre-
treatment step. Figoli et al. (2010) demonstrated that the AsV re-
moval efficiency was increased with increasing of solution pH
along with decrease of operating temperature and the feed As
concentration, while the transmembrane pressure had little/no
effect. Sato et al. (2002) and Uddin et al. (2007) reported that
without oxidative pretreatment, NF is not sufficient for the re-
moval of total As from aqueous solution and therefore is not able
to provide water quality below the MCL.
In a recent study, As removal by employing self-made PMIA
(poly m-phenylene isophthalamide) nanofiltration membrane was
investigated with aqueous solution of As salt (Na2HAsO4.7H2O)
and more than 90% AsV rejection was reported (Zhao et al., 2012).
Furthermore, AsV rejection increased from 83% at pH 3 to 99% at
pH 9. In presence of NaCl, AsV rejection increased in the feed range
studied and was reported to be 99% when feed concentration was
100 μg L-1.
4.9.4. As removal using reverse osmosis
Reverse osmosis (RO) is the oldest and identified as the best
available technology for the small water treatment systems to
remove As from water. The RO membrane contains extremely
small pores ( o0.001 μm) (Schneiter and Middlebrooks, 1983) and
a very high (often close to 100%) rejection of low-molecular mass
compounds and ions can be achieved (Velizarov et al., 2004).
Moreover, the process can easily be automated and controlled. In
the 1980s, with the invention of cellulose acetate RO membrane,
AsV removal efficiency have been achieved of above 90% with the
RO system operated at high-pressure around 400 psi (Clifford
et al., 1986; Fox, 1989) while, AsIII removal efficiency was less
than 70%. The operational parameters for As removal by RO
membranes was investigated by Akin et al. (2011) and found that
although the feed water concentration had no effect on the re-
jection rate, the rejection of As was largely affected by the pH of
the feed water and operating pressure. Yoon et al. (2009) studied
the effect of charged membranes on the As removal and their
study concluded that there was a considerable rejection of the
oxy-anionic AsV while below pH 10 AsIII removal was low due to
the existence of uncharged AsIII species in solution. Thus, the
presence of AsIII plays an important role for removal of As. Ac-
cording to the Walker et al. (2008) when AsIII was the dominant As
species in the groundwater, the As removal efficiency decreased to
less than 50%. Therefore, where AsIII is the dominant species RO
seems to be ineffective for As contaminated natural water espe-
cially for reducing conditions.
4.10. As removal by advanced hybrid and integrated technologies
4.10.1. As removal using membrane distillation
Presently, As remediation is taking place with better under-
standing of complex chemical processes due to the recent advance-
ment in science and technology. Among the different kinds of
membrane distillation (MD), direct contact membrane distillation
(DCMD) is the most simple, economical and efficient technique
where the hot feed and the cold permeate are directly separated by
the membrane. The MD is a non-isothermal membrane separation
process that employs a microporous hydrophobic membrane with
pore size ranging from 0.01 μm to 1 μm. The main requirements for
MD process are that the membrane should not be wetted and only
vapor and non-condensable gases should be present within its pores.
Based on these requirements hydrophobic, microporous membranes
made of polytetrafluoroethylene (PTFE), polyethylene (PE), poly-
propylene (PP), and polyvinylidenefluoride (PVDF) are now com-
mercially available. Recently, there have been studies to remove As
using DCMD (Islam, 2004; Manna et al., 2010; Yarlagadda et al.,
2011). In one such study, Manna et al. (2010) had performed ex-
periments by using three different types of hydrophobic membranes
for solar driven MD and studied the removal of AsIII and AsV from
groundwater. Their study demonstrated that nearly 100% of the As
removal from the contaminated groundwater with high flux of
49.80 kg m
2 h
1. Recently, AsV and AsIII removal studied by Qu
et al. (2009) using self-made polyvinylidene fluoride (PVDF) mem-
brane in a DCMD unit and the experimental results indicated that the
permeate AsIII and AsV were under the maximum contaminant limit
(10 μg L
1) until the feed AsIII and AsV concentration achieved 40 and
2000 mg L
1, respectively. Macedonio and Drioli (2008) tested the
performance of an integrated RO and MD system. This integrated
process (RO followed by MD) removes total As from water and leaves
less environmental hazardous waste on comparing to oxidation fol-
lowed by the RO and thus is very promising for contaminated water
purification.
4.10.2. As removal using forward osmosis
Forward osmosis (FO) is another membrane process that has
been used for treatment of industrial waste, concentrate landfill
leachate, liquid food in food industry and desalination of seawater
(Cath et al., 2006). Water is filtered due to the osmotic pressure
difference, which is the driving force for FO separation. Cath et al.
(2006) had determined several advantages of the use of FO: (i) it is
a simple equipment set-up (ii) there is low or no requirement of
hydraulic pressure, (iii) the membrane have a high rejection, and
(iv) the probability of lower membrane fouling than other con-
ventional membrane processes. Recently, Jin et al. (2012) in-
vestigated the removal of As using FO and also studied the influ-
ence of membrane orientation and membrane fouling. The As from
solution was successfully removed by the FO and the removal/
rejection was better when the surface active membrane side faced
the feed water compared to the draw water due to more severe
concentrative internal concentration polarization. In addition, they
also found that for FO, the AsIII rejection from solution was greater
than that of RO; the rejection increased by increasing water flux.
Further, they concluded that the lower rejection by RO was due to
the deformation of the fabric supported membrane followed by
expansion of membrane pores by hydraulic pressure, which en-
abled As and other solute particles to pass through the membrane.
Although in DCMD and FO, the waste water with an increased As
concentration after separation may be re-treated, the As con-
centration significantly increases in the feed water. As a result, the
 R. Singh et al. / Ecotoxicology and Environmental Safety 112 (2015) 247–270
risk for membrane damage increases along with the cost of
treatment. Therefore, this concentrate then can be treated with
ZVI under an inert atmosphere so as to reduce the soluble As to
commercially valuable metallic As (Bang et al., 2005a; Sun et al.,
2011).
4.11. Disposal of As laden sludges and wastes
In all the above mentioned methods, sludge is generated as a
result of precipitation of Fe or Al hydroxides depending on the
amount of coagulant present naturally and/or added. This sludge
contains high concentrations of As, therefore, for disposal of this
sludge care should be taken. In a recent study, Sarkar et al. (2010)
addressed to dig holes and bury the sludge away from edible crops
and children's playing area is one of the possible ways of disposing
of the sludge from household removal units, whereas the sludge
from community based removal units can be stored in aerated
coarse sand filters.
5. Conclusion and future perspective
South-East, South-West and North-East USA, Inner Mongolia
(China), South-West Taiwan coastal regions, Sonora (Mexico),
Pamplonian Plain (Argentina), West Bengal (India), Northern Chile,
and Bangladesh are highly As polluted centres. Therefore, treat-
ment of As contaminated water and soil could be the only effective
option to minimize health hazard. To achieve this, various tech-
niques are being used. However, the adopted technologies have
some drawbacks and their by-products can be a further potential
source for secondary As pollution. Therefore, for better clean up of
the environment, new technologies with the options of new hy-
brid technologies are needed to challenge the menace of As.
Among various techniques, membrane technologies, electro-re-
mediation and phytoremediation are seemed to be more suitable
for removal of As from water and soil. However, further research is
needed to develop more efficient techniques without drawbacks
for As free life.
Acknowledgments
Authors are thankful to the University Grants Commission, New
Delhi for providing financial assistance to carry out the work.
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