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Ecotoxicology and Environmental Safety 112 (2015) 247–270

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Ecotoxicology and Environmental Safety

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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
Ranjan Plant Physiology and Biochemistry Laboratory, Department of Botany, University of Allahabad, Allahabad 211002, India
Department of Environmental Science, University of Lucknow, Lucknow 226025, India
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


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

Corresponding authors.
E-mail addresses: (V.P. Singh), (S.M. Prasad).
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

(III) 4As(III) 4As(V) 4DMA(V) 4MMA(V), where the MMA(III)
Recently, the environmental fate and behavior of arsenic (As) is metabolite is the most toxic compound and some researchers
receiving increased attention due to the arsenic (As) pollution in considered it to be the central As mode of action (EFSA, 2009; Kile
South-East Asia. Although As contamination in the environment et al., 2011; Wen et al., 2011). In this review, we have summarized
has been reported worldwide (Sohel et al., 2009; Li et al., 2011), As contamination and its remediation techniques in water and soil.
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- 2. Sources of arsenic in the environment
gions, Sonora (Mexico), Pamplonian Plain (Argentina), West Ben-
gal (India), Northern Chile, and Bangladesh (Argos et al., 2010). The The primary source of As in the environment (hydrosphere,
World Health Organization (WHO) deemed the As in Bangladeshi pedosphere, biosphere and atmosphere) is the release of As from
groundwater to be “the largest mass poisoning of a population in As-enriched minerals. The sources of As includes both natural i.e.
history” (Argos et al., 2010). through dissolution of As compounds adsorbed onto pyrite ores
Arsenic is ubiquitous in the environment and highly toxic to all into the water by geochemical factors and anthropogenic i.e.
forms of the life. It is a crystalline “metalloid”, a natural element through use of insecticides, herbicides and phosphate fertilizers,
with features intermediate between metals and non-metals, oc- semi-conductor industries, mining and smelting, industrial pro-
curs naturally as an element, ranks as the 20th most occurring cesses, coal combustion, timber preservatives etc. (Mondal et al.,
trace element in the earth's crust, 14th in seawater, and 12th in the 2006; Bundschuh et al., 2011). A survey of occurrence of As in
human body (Mandal and Suzuki, 2002). Arsenic exists mainly in groundwater/drinking water, fresh waters, marine waters, soil and
four oxidation states – arsenate (AsV), arsenite (AsIII), arsenic (As0), food stuffs is given below.
and arsine (As  III) and its solubility depends on the pH and ionic
environment. Among them, the AsV being the most stable form 2.1. Groundwater/drinking water
(Sharma and Sohn, 2009; Zhao et al., 2010; Gupta et al., 2011). AsV
is thermodynamically stable state in aerobic water, while AsIII is According to the WHO guidelines, the recommended limit of
predominant in reduced redox environment. Arsenic can be pre- arsenic in drinking water is 0.01 mg L  1. However, the levels of As
sent in the environment in various chemical forms such as in unpolluted surface water and groundwater vary typically from
monomethylarsonic acid [MMA; CH3AsO(OH)2], dimethylarsinic 1–10 μg L  1. Groundwater concentrations of As is reported to be
acid [DMA; (CH3)2AsOOH], trimethylarsine oxide [TMAO; very large range from less than 0.5–5000 mg L  1 covering natural
(CH3)3AsO], arsenobetaine [AsB; (CH3)3As þCH2COOH], arseno- As contamination found in more than 70 countries (Ravenscroft
choline [AsC], arsenosugars [AsS], arsenolipids etc. (Tangahu et al., et al., 2009). The As contamination in groundwater in different
2011). In general, inorganic arsenicals are more toxic than organic parts of the world is summarized in Table 1. Large areas of Ban-
ones (Meharg and Hartley-Whitaker, 2002). AsIII is usually more gladesh, West Bengal and other states of India and Vietnam rely on
toxic than AsV (Abedin et al., 2002a, 2002b; Schat et al., 2002), and As contaminated groundwater for irrigation of staple crops such as
dimethylarsinous acid (DMAAIII) and monomethylarsonous acid rice (Nickson et al., 1998; Berg et al., 2001; Abedin et al., 2002a,
(MMAAIII) are more toxic than their parent compounds (Petrick 2002b). On applying the WHO provisional guideline for drinking
et al., 2000; Mass et al., 2001). Methylated As compounds, such as water of 10 μg L  1 of As, a worldwide population of more than 100
MMA, DMA and TMAO are found sometimes as a minor compo- millions people are at risk, and out of these more than 45 millions
nent in the soil (Huang and Matzner, 2006), but can reach high people mainly in developing countries from Asia are at risk of
concentrations (Abedin et al., 2002a, 2002b). Both MMA and DMA being exposed to more than 50 μg L  1 of As, which is the max-
(also known as cacodylic acid) have been widely used as pesticides imum concentration limit in drinking water in most of the coun-
and herbicides, the DMA also as a cotton defoliant. Arsenobetaine, tries in Asia (Ravenscroft et al., 2009). Contamination of drinking
the dominant As species in marine animals, was found to be water is the main source of As for human being but for the po-
present in an acidic fen soil with unclear origin (Huang and pulation not exposed to elevated As in drinking water, consump-
Matzner, 2006). Arsenolipid, a lipid-soluble As compound, main- tion of food grown in As-contaminated soil or irrigated with As-
ly found in the marine organism, and its concentration may reach contaminated water represents the main sources of As intake for
upto 16 mg As/kg fish oil (Sele et al., 2012). Recent findings 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 and geochemistry of the catchments (Smedley and Kinniburgh,
inorganic As exposure drawn attention through food, since some 2002). Basic As concentrations in the water of various con-
food items especially rice and vegetables were reported to contain taminated rivers range between 0.1 to 2.1 mg L  1 with an average
high inorganic As concentrations in areas with elevated As in soil of 0.8 mg L  1 (Table 2), which might be due to the source of con-
and irrigation water (EFSA, 2009; Mondal et al., 2010; Zhao et al., tamination, surface recharge, base flow, and the bedrock lithology.
2010; Fu et al., 2011; Rahman and Hasegawa, 2011a, 2011b; WHO, The geothermal inputs, evaporation, and groundwater con-
2011; and Bhattacharya et al., 2012). tamination are the main cause of high concentrations of As in
rivers. For example, in Lao River of Northern Chile the extremely
2.2. Freshwaters 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
In freshwater systems (rivers and lakes), the variation in As contribute in the occurrence of high As concentrations in river
concentration is in the range of 0.15–0.45 μg L  1 (Bissen and waters. For example, water of Mole River, New South Wales,
Frimmel, 2003a, 2003b) depending on the source, availability, 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

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
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 waters of southern Australia (Maher, 1985) (Table 2). Arsenic
ores (Ashley and Lottermoser, 1999). However, according to the concentrations in estuarine waters are more uniform than those of
WHO guidelines for irrigation purpose the permissible limit of open marine waters. Smedley and Kinniburgh (2002) reported
arsenic in water is 0.10 mg L  1. that As concentrations in the estuarine waters may be affected by
As concentrations in lake waters are close to or lower than that industrial and mining effluents and geothermal water. The physi-
reported for river waters (Table 2). Azcue et al. (1994) and Azcue cal mixing of the fresh and seawater masses and salinity may in-
and Nriagu (1995) studied that the As concentrations in lakes fluence the concentration of dissolved As in estuaries and con-
around British Columbia and Canada ranged between 0.2 and tinental shelves. For example, a linear increase in total As con-
2.08 mg L  1, has been transported from the abandoned Cariboo centrations, ranging from 0.13 mg L  1 in freshwaters to 1.8 mg L  1
Gold Quartz mine tailings of that area, and gets accumulated in in offshore waters, with increase in the salinity has been reported
high concentration (upto 1104 mg g  1) in the bottom sediments of in Krka Estuary, Yugoslavia (Seyler and Martin, 1991).
the lakes. Geothermal sources and mining activities have also in-
creased the concentrations of As in lake waters (Smedley and
2.4. Arsenic concentration in soil
Kinniburgh, 2002). In mine affected lake waters, the As con-
centrations are relatively low because of its adsorption onto Fe-
According to the U.S. Environmental Protection Agency, the
oxides under neutral pH (Smedley and Kinniburgh, 2002), and also
permissible limit of arsenic in soil is 24 mg kg  1. In the case of soil,
due to its accumulation in bottom sediments (Azcue and Nriagu,
there are also numerous pathways for propagating the con-
tamination of As. The major sources of its contamination in soil are
Several studies have reported thermal stratification of As con-
identified to include many man-made activities e.g. the use of
centrations in lake waters (Azcue and Nriagu, 1995; Hasegawa,
insecticides, herbicides and phosphate fertilizers, semi-conductor
1996; Hasegawa et al., 2010). Azcue and Nriagu (1995) studied that
industries, mining and smelting, industrial processes, coal com-
the dissolved As concentration was highest during summer in the
bustion, timber preservatives etc. (Mondal et al., 2006; Bundschuh
Moira Lake, Ontario, Canada with an average concentration of
et al., 2011). Average arsenic concentration in European topsoil is
47 mg L  1 in surface water, compared to 22 mg L  1 in winter.
estimated at 7.0 mg kg  1 (Stafilov et al., 2010) but the background
Hasegawa et al. (2009) have also reported similar trends in the
concentration can significantly differ depending on soil conditions.
occurrence of As concentrations in lake waters. Smedley and
Arsenic contamination in soil in different parts of the world is
Kinniburgh (2002) and Hasegawa et al. (2010) reported that
summarized in Table 3. In lower Silesia, Southwestern Poland upto
thermal stratification in lake water also causes the release of As
18,100 mg kg-1 of As was reported in soil of Au-enriched me-
into the water column from bottom sediments due to depletion of
tallogenic zones (Karczewska et al., 2007).
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 2.5. Arsenic concentration in food stuffs
and along major rivers emerging from the Himalayas with the
Bengal delta being the worst affected area where 4 88% of the 45 The interest in rice as a potential source of exposure to arsenic
millions inhabitants are at high risk of exposure to As concentra- is very recent. Rice is a staple food for more than half the world's
tions 450 mg L  1 (Acharyya and Shah, 2007; Ravenscroft et al., population beacuse it is a good source of carbohydrates, thiamin,
2009; Uddin et al., 2011). The other affected river deltas and river vitamin B6, and some essential elements like magnesium, zinc and
basins in South and South-East Asia are the Red River Delta and copper. The world's total production of rice in 2009 was estimated
the Mekong Delta (4 10 millions exposed) (Berg et al., 2007; to be 682 million metric tons (FAO, 2010). Interestingly, many of
Buschmann et al., 2008) and river basins of Chindwin-Irrawady, the rice-producing countries suffer from arsenic contamination in
Salween; Brahmaputra, Ganges, Indus, Chenab (Chakraborti et al., their groundwater or soil (Rahman and Hasegawa, 2011a, 2011b).
2003; Nickson et al., 2005, 2007; Stanger, 2005; Thakur et al., However, rice may accumulate hazardous levels of toxic elements
2011). such as arsenic. Due to its large daily consumption, it accumulates
in human body and poses serious threat (Meharg et al., 2008;
2.3. Marine waters Shraim, 2014). Besides rice, other cereals such as wheat, corn, oat,
buckwheat are also source of arsenic exposure. Vegetables and
In seawater, the As concentration is usually less than 2 μg L  1 meat products have also been reported a good source of arsenic
(Ng, 2005), and its concentrations in Atlantic and deep Pacific exposure to human beings (EFSA, 2014). The amount of arsenic
waters are between 1.0–1.8 mg L  1 (Cullen and Reimer, 1989), ingested daily by humans via food is greatly influenced by the
3.1 μg L  1 in marine waters of the Pacific coast near Nakaminato amount of food in the diet. The amount of arsenic in various food
(Ibaraki, Japan) (Ishikawa et al., 1987), and 1.1–1.6 mg L  1 in coastal stuffs and its safe limit is summarized in Table 4.

Table 3
Concentrations of arsenic in soil of the arsenic-affected countries.

Country Region Soil As concentration in mg/kg References

Bangladesh Noakhali 3.6–26 mg/kg (Meghna River) Nriagu et al., 2007

Brazil Minas Gerais (Southeastern Brazil) 200–860 mg/kg Bundschuh et al., 2012
Chile Esquiña Up to 489 mg/kg (Río Caritaya region) Bundschuh et al., 2012; Nriagu et al., 2007
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) Nriagu et al., 2007
Poland Lower Silesia, (Southwestern Poland) Up to 18,100 mg/kg (Highly polluted area) Karczewska et al., 2007
Spain Duero Cenozoic Basin 23 mg/kg (Mean) Gómez et al., 2006
Turkey Simav plain (Kutahya) Up to 660 mg/kg (Highly polluted area) Gunduz et al., 2010
United Kingdom Cornwall 2–17 mg/kg (Bioaccessible) Palumbo-Roe et al., 2005
USA Tulare lake average 280 mg/kg (Hawaii) 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.,
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 recognized to be one of the world's greatest environmental ha-
et al., 2010). The accumulation of As is also important in wetland zards (Sohel et al., 2009; Chakraborti et al., 2010; Bundschuh et al.,
species, where there is a potential for reducing conditions to re- 2012; Naujokas et al., 2013). The major arsenicosis regions are
lease As into the soil solution (Ha et al., 2009; Rahman and presently found in large deltas and/or along major rivers emerging
Hasegawa, 2011a, 2011b), or for co-deposition of As with Fe hy- from the Himalayas (Fendorf et al., 2010) such as in the Bengal
droxides adsorbed to the plant's surface (Zhao et al., 2002). In delta (Chakraborti et al., 2010), other parts of India (Saha, 2009;
West Bengal (India) and Bangladesh, most of the crop fields are Shukla et al., 2010), Nepal (Thakur et al., 2011), Pakistan (Malik
contaminated with As (Roychowdhury et al., 2002; Alam et al., et al., 2009), Myanmar, Vietnam, Cambodia (Berg et al., 2007;
2003). Polya et al., 2008) and China (He and Charlet, 2013). A recent study
The various effects of As poisoning on human health are mel- has shown that nutritional deficiency is an important promoter of
anosis, leuco-melanosis, keratosis, hyperkeratosis, dorsum, non- arsenicosis especially for women (Deb et al., 2013).
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-
4. Remediation of arsenic contamination
atosis have been found in many cases. Few cases of skin cancer
have also been identified among the patients seriously affected by
Arsenic contaminated drinking water is a major threat to
arsenite and arsenate (Hsueh et al., 1995). Chronic exposure to
mankind. Although in small quantities it is necessary, however, it
inorganic As causes several disorders upon different biological
is known to be highly toxic if ingested in large dose. Its elevated
systems like digestive system, respiratory system, cardiovascular
system, hematopoietic system, endocrine system, renal system, concentrations are found in groundwater in some areas of India,
neurological system, and reproductive system which ultimately Bangladesh, Chile, China, Argentina, Mexico, Hungary, Taiwan,
lead to cancer (Mandal et al., 1996; Maharjan et al., 2005). Vietnam, Japan, New Zealand, Germany and the United States due
Excessive and long-term (such as 5–10 years) human intake of to naturally occurring arsenic in the aquifer sediment (Bang et al.,
toxic inorganic As having concentration above 0.05 mg L  1 leads 2005a). Thus, in order to reduce the health risk arising due to the
to arsenicosis, which is a common term used for As related health direct consumption of As contaminated drinking water or due to
effects including skin problems, skin cancers, internal cancers the consumption of food/vegetables, grown in soil irrigated with
(bladder, kidney, lung), diseases of the blood vessels of the legs As contaminated water, there is need to develop strategies that
and feet, and possibly diabetes, high blood pressure and re- could alleviate toxicity and availability of As from soil to edible
productive disorders (WHO, 2011). The global extent and severity portions of food/vegetables. Removal of As highly depends on the
of appearing arsenicosis is probably not yet fully revealed. Over- chemistry and composition of the As contaminated water. In most
whelming evidence of non-occupational chronic As exposure is of the major reported incidences As occurs as AsIII and oxidation of
through ingestion of drinking water including food and beverages AsIII to AsV is deemed necessary to achieve the satisfactory results
prepared from drinking water. Inhaled amounts of As may be high of As removal. Here dealing with the presently available technol-
and important in poorly ventilated huts where As rich coal or cow ogies, especially oxidation, phytoremediation, coagulation–floc-
dung is used as a fuel (Lin et al., 2010) with high As concentrations culation, adsorption, ion exchange, electrokinetics and membrane
has been reported over the last two decades and is now technologies will be discussed (Fig. 2).

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.
R. Singh et al. / Ecotoxicology and Environmental Safety 112 (2015) 247–270 253

4.1. Arsenic revomal by oxidation techniques preoxidation of surface water (Gates, 1998). Removal of As using
H2O2 and NH2Cl oxidants would take hours as they oxidizes AsIII
These techniques use various processes and are discussed very slowly whereas Cl2, O3, and FeO42  would react with AsIII in
below. millisecond time scale. The scavenger substances present in water
will affect the fast kinetics of AsIII oxidation with Cl2, O3, and
4.1.1. Oxidation and filtration FeO42  . However, specific selection of oxidants can reduce the
The main purpose of oxidation is to convert the soluble AsIII to effect of scavengers on effectiveness of oxidant. For example, in
AsV, which is then followed by precipitation of AsV. This is es- order to remove As from water that contains excess ammonia, it is
sential for anaerobic groundwater because AsIII is the predominant
better to use ozonation rather than chlorination because O3 reacts
form of As at neutral pH (Masscheleyn et al., 1991). Generally,
slowly with ammonia. FeO42  can be related to the use of other
oxidation and filtration refer to the processes which are designed
chemical oxidants for removing As (Sharma, 2007a). FeO42  does
to remove the naturally occurring iron and manganese from water.
not react with bromide ion and thus carcinogenic bromate ion
The process involves the oxidation of the soluble forms of iron and
would not be produced in the treatment of bromide-containing
manganese to their insoluble forms and then removal by filtration.
Firstly, soluble AsIII is oxidized. Arsenic is mainly present as AsV water (Sharma, 2007a). Moreover, FeIII, a by-product of FeVI is non-
and, as such, is likely to be in the solid phase. Therefore, in such toxic, and acts as a powerful coagulant (Sharma, 2002, 2004;
soils, As in groundwater used for irrigation is quickly adsorbed by Sharma et al., 2005a, 2005b; Yngard et al., 2008) which is suitable
iron hydroxides and becomes largely unavailable to plants. In for the removal of AsV in water (Lee et al., 2003; Sharma et al.,
anaerobic soil conditions such as in flooded paddy fields, As is 2007). Thus, FeVI acts as multifunctional chemical oxidant, disin-
mainly present as AsIII and is easily dissolved in the soil-pore water fectant, and coagulant in a single mixing (Sharma, 2007b). Re-
(the soil solution) (Xu et al., 2008). It is thus more readily available cently, it has been demonstrated that the oxidation of AsIII by
to plant roots. Arsenite has a low affinity to mineral surfaces, while MnO2 coated PEEC-WC nanostructured capsules and demon-
arsenate adsorbs easily to solid surfaces. Thus, for the removal of strated that when water contains a low concentration of As, they
As from water, oxidation/precipitation technology is very effective have a higher efficiency than conventional oxidation methods
(Ghurye et al. 2004; Leupin and Hug, 2005). The oxidation of AsIII (Criscuoli et al., 2012).
into AsV is carried out by traditional chemical oxidants (Ox) such
as chlorine (Cl2), chlorine dioxide (ClO2), ozone (O3), hydrogen 4.1.2. Photochemical oxidation
peroxide (H2O2), chloroamine (NH2Cl), permanganate (MnO4  ), The most widely tested chemical oxidant in presence of natu-
and ferrate (FeO42  ) and have been published in many studies rally occurring iron in the field is UV-light assisted oxidation of AsIII
(Emett and Khoe, 2001; Johnston et al., 2001; Bissen and Frimmel, (Ryu et al., 2013). The oxidation rate of AsIII in the water can be
2003b; Lee et al., 2003; Ghurye et al., 2004; Vasudevan et al., increased by UV irradiation in the presence of oxygen. UV/solar
2006; Dodd et al., 2006; Sharma et al., 2007; Mondal et al., 2013). light helps to generate hydroxyl radicals through the photolysis of
Following equations expresses the stoichiometries of the oxi- FeIII species: (FeOH2 þ ) and in the presence of both hydroxyl radicals
dation reactions:
and O2, the oxidation rate becomes faster (Yoon and Lee, 2005;
Cl2: As(OH)3 þHOCl-AsO43  þ Clþ 4H þ (1) Sharma et al., 2007). Several studies have investigated the photo-
chemical oxidation of AsIII using UV light irradiation. In perchlorate/
ClO2: As(OH)3 þ 2ClO2 þ H2O-AsO43  þ 2ClO2 þ 5H þ (2) perchloric solution at pH 0.5–2.5, addition of FeIII to As-con-
O3: As(OH)3 þO3-AsO43  þO2 þ3H þ (3) taminated water followed by exposure to UV/solar light enhanced
the removal of As (Emett and Khoe, 2001). In this study, FeIII-hy-
3 þ
H2O2: As(OH)3 þH2O2-AsO4 þ3H þH2O (4) droxide and chloride species absorb photons to give highly oxidiz-
NH2Cl: As(OH)3 þNH2Cl þH2O-AsO43  þNH4 þ 
þCl þ3H þ
(5) ing hydroxyl and dichloro radicals which converts AsIII to AsV
(Emett and Khoe, 2001). Although, this system was also found to be
MnO4  : 3As(OH)3 þ2MnO4--3AsO43- þ2MnO2 þ 7H þ þ H2O (6) useful under natural water conditions (Hug et al., 2001). An oxi-
2 2 3 dation of AsIII solution containing 0.06–5 mg L  1 FeII and FeIII using
FeO4 : 3As(OH)3 þ2FeO4 þ H2O-3AsO4 þ2Fe(OH)3 þ
5H þ (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-
When used for oxidation of AsIII to AsV, the reaction is very fast celerated the oxidation of iAsIII (inorganic arsenite) (Hug et al.,
for Cl2, O3 and MnO4  compared to the H2O2 and NH2Cl (Lee et al., 2001). Instead of UV-light, solar-light can also remove As from
2003; Ghurye et al., 2004; Dodd et al., 2006). By using air and pure natural water upon addition of iron and citrate (Lara et al., 2006).
oxygen, about 54–57% of AsIII can be oxidized to AsV in con- Addition of a few drops of lime or lemon juice (citrate) in water may
taminated groundwater (Kim and Nriagu, 2000) whereas, com- also be helpful for the enhancement of photochemical oxidation of
plete oxidation of AsIII can be achieved with O3. The NH2Cl and
AsIII to the less harmful AsV (Hug et al., 2001; Kocar and Inskeep,
H2O2 are sluggish in reacting with AsIII while Cl2 and O3 react very
2003; Lara et al., 2006). The cyclic reaction of lemon juice (citrate)
rapidly. Free Cl2 or hypochlorite is effective for the oxidation of
with strongly oxidizing radicals gives rise to further radicals due to
AsIII, but chlorination creates and leaves disinfectant by-products
which the removal rate was higher but excessive concentration of
(DBPs) in treated water. Reduction in the levels of trihalo me-
citrate has a negative impact due to the formation of acid com-
thanes (THMs) and halo acetic acids (HAAs) was seen with O3, but
it can form the potent carcinogenic bromate ion by reacting with plexants (Bissen and Frimmel, 2003b). Recently, oxidation of AsIII
bromide present in the water (Gunten, 2003; Richardson, 2006). It was accomplished by using vacuum-UV lamp irradiation at 185 and
is suggested that treatment with NH2Cl produces N-ni- 254 nm wavelengths (Yoon et al., 2008). In this study, the effects of
trosodimethylamine (NDMA) which is a suspected human carci- FeIII, H2O2, and humic acids (HA) were examined. Both FeIII and
nogen (Mitch and Sedlak, 2002). For the treatment of high quality H2O2 increased oxidation efficiency but humic acid did not show
water such as surface water, the use of ClO2 is restricted and any influence on the oxidation. In order to achieve effective oxi-
dosing of ClO2 must be kept low. For example, in the United States, dation of AsIII, intense UV light source was used with the potassium
dosages ranging from 1 to 1.4 mg L  1 are used mainly for the 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 adsorbed in FeIII resulting in overall As removal of up to 95% even
The efficient oxidation of AsIII to AsV can be achieved by pho- at high initial As concentrations of 200 mg L  1. The kinetics of
tocatalytic oxidation (PCO) (Bissen et al., 2001). The PCO of AsIII to bacterial AsIII oxidation and subsequent removal of AsV by sorption
AsV followed by adsorption of As on TiO2 was investigated (Dutta onto biogenic manganese oxides during ground water treatment
et al., 2004, 2005; Miller et al., 2011). The PCO of AsIII in suspen- was studied by Katsoyiannis et al. (2004). Their findings suggested
sions with low TiO2 loadings followed by subsequent adsorption of that the rate of oxidation of AsIII was comparatively higher than
AsV onto TiO2 surfaces in slightly acidic media reduced As con- the rates reported for abiotic AsIII oxidation by manganese oxides,
centrations below the WHO drinking water limit of 10 μg L  1 in supporting that bacteria play an important role in both the oxi-
water (initial [As] ¼66.7 μM) (Dutta et al., 2005). Miller and dation of AsIII and the generation of reactive manganese oxide
Zimmer-man (2010) synthesized a TiO2-impregnated chitosan surfaces for the removal of AsIII and AsV from solution. Thus,
bead (TICB) and it was used for oxidation as well as removal of As bacteria play an important role in both the AsIII oxidation and the
from aqueous solution. The adsorption of AsV onto TiO2 is influ- generation of reactive manganese oxide surfaces for the removal of
enced by pH, initial concentration of As, type of TiO2, presence of
dissolved AsIII and AsV. Later, Katsoyiannis and Zouboulis (2006)
anions (e.g. CO32  and PO43  ) and NOM (natural organic matter)
reviewed the use of iron and manganese oxidizing bacteria for the
(Dutta et al., 2004; Bang et al. 2005b; Ferguson and Hering, 2006;
combined removal of iron, manganese and As from contaminated
Pena et al., 2005, 2006; Liu et al., 2008; Miller et al., 2011). They
ground water. According to report, iron oxidizing bacteria remove
observed a higher amount of adsorption of As [6400 mg AsIII g  1
As more efficiently than those of manganese oxidizing bacteria.
TICB and 4925 mg AsV g  1] followed by UV radiation compared to
The rates of oxidation of iron, manganese and As are faster than
the solution that was not exposed to UV light [2198 mg AsIII g  1
those reported for physicochemical oxidation, indicating the cat-
TICB and 2050 mg AsV g  1]. A nanocrystalline Al2O3 and TiO2 im-
pregnated chitosan for As removal was prepared by Yamani et al. alytic role of bacteria in As removal. Leupin and Hug (2005) passed
(2012) and their study proposed a mechanism where AsIII is photo- aerated artificial ground water with high As and iron concentra-
oxidized to AsV by TiO2, then adsorbed by Al2O3. When a very low tion through a mixture of 1.5 g iron fillings and 3–4 g quartz sand
amount of TiO2 is present, the TiO2/UV system has an inefficient in a vertical glass column. By using dissolved oxygen, FeII was
removal of As due to incomplete oxidation of AsIII to AsV (Guan oxidized to hydrous ferric oxides (HFO) while AsIII was partially
et al., 2012). The effect of competitive anions and organic matter oxidized and AsV adsorbed on the HFO. This principle was suc-
that are commonly found in the groundwater are an important cessfully applied in the field by Sen Gupta et al. (2009), where
disadvantage of using UV/TiO2. Bicarbonate and humic acid affect without using any chemical they reversed the bacterial As reduc-
the PCO of AsIII, while the adsorption of As on to the TiO2 based tion process, by recharging calculated volume of aerated water
adsorbent was affected by silicate, fluoride, phosphate and humic (DO44 mg L  1) in the aquifer to create an oxidized zone. This
acid (Guan et al., 2012). The PCO increases in the presence of NOM boosted the growth of iron oxidizing bacteria and suppressed the
but at higher concentration of NOM (2–15 mg L  1), the adsorption growth of As reducing anaerobic bacteria and promoted the
of AsV on the surface of TiO2 decreases (Dodd et al., 2006; Liu et al., growth of chemoautotrophic As oxidizing bacteria (CAOs) over a
2008). Sharma and Sohn (2009) recently reviewed the possible period of six to eight weeks. Saalfield and Bostick (2009) de-
reasons for the decreased adsorption of AsV on TiO2, that are the monstrated a process in the laboratory, where the mobility of As
competitions between NOM and AsV for available binding sites was affected by biologically mediated redox processes by binding
on TiO2 surface and/or the adsorption of NOM, which modifies it to iron oxide through dissimilatory sulphate reduction and
the surface charge of TiO2. Recently, it has been demonstrated that secondary iron reduction processes, in reducing aquifers. Incuba-
the PCO of pentavalent MMAV (monomethylarsonic acid) and tion experiments were conducted using AsIII/V-bearing ferrihydrite
DMAV (dimethylarsinic acid) using Degussa P25 and nanocrystal- in carbonate-buffered artificial groundwater enriched with sul-
line TiO2 (Xu et al., 2007, 2008). In the use of Degussa P25 TiO2, phate (0.08–10 mM) and lactate (10 mM) and inoculated with
both MMAV and DMAV were readily mineralized to iAsV (Xu et al., Desulfovibrio vulgaris (ATCC 7757), which reduces only sulphate
2007). The MMAV was formed as an intermediate of the PCO of but not Fe or As. The end product formed through sulphidization
DMAV, which was subsequently oxidized to iAsV.
of ferrihydrite was magnetite, elemental sulfur and trace Fe sul-
phides. It was suggested that only AsIII species got released under
4.1.4. Biological oxidation
reducing conditions and bacterial reduction of AsV was necessary
It is relatively a new method of oxidation of iron and manga-
for As sequestration in sulphides.
nese as a treatment method for As removal. Biological treatment
methods exploit natural biological processes that allow certain
4.1.5. In-situ oxidation
plants and micro-organisms to help in the remediation of metals
This method is mostly popular for removal of Fe from
in soil and groundwater. This process is based upon the fact that As
groundwater (Appelo et al., 1999). In-situ oxidation can be
contaminated groundwater is usually reducing and containing
achieved by pumping the oxygenated water into the groundwater
iron and manganese concentrations. In the treatment system, the
aquifer to reduce the As content in the pumped groundwater. Its
following sequence of reactions have been found to occur:
(i) oxidation of MnII to MnIV and FeII to FeIII, (ii) oxidation of AsIII to potential for removal of As is investigated in very few studies al-
AsV, (iii) precipitation of manganese oxides, (iv) abiotic oxidation though the results show that As concentrations can be reduced in
of AsIII by manganese oxides, and (v) AsV sorption by manganese the groundwater zone before water extraction (Sen Gupta et al.,
oxides, where steps (i) and (ii) are biotic and steps (iii) to (v) are 2009; van Halem et al., 2010). In-situ oxidation of As and iron in
abiotic. Katsoyiannis and Zouboulis (2004) reported that the mi- the aquifer has been tried under Danida Arsenic Mitigation Pilot
croorganisms Gallionella ferruginea and Leptothrix ochracea were Project (DPHE, 2001). The aerated tube well water is stored in a
found to support biotic oxidation of iron. They performed some tank and released back into the aquifers through the tube well by
experiments in the laboratory where iron oxides and above given opening a valve in a pipe connecting the water tank to the tube
microorganisms were deposited in the filter medium, offering a well pipe under the pump head. The dissolved oxygen content in
favorable environment for the adsorption of As because As in the water oxidizes AsIII to less mobile AsV and also the ferrous iron to
form of AsIII cannot be efficiently sorbed onto iron oxides. Prob- ferric iron in the aquifer causing the reduction in As content of
ably, these microorganisms oxidized AsIII to AsV, which got tube well water.
R. Singh et al. / Ecotoxicology and Environmental Safety 112 (2015) 247–270 255

4.2. Phytoremediation (Eichhornia crassipes), lesser duckweed (Lemna minor) (Alvarado

et al., 2008), dried algae (Lessonia nigrescens) (Hansen et al., 2004)
Phytoremediation is the plant based environmental-friendly and dried macro-algae (Spyrogira spp.) (Bundschuh et al., 2007).
technology, for the remediation of As contaminated sites, using Recently, use of native biomasses (powdered) was reported to
plants and microbes to clean up contaminated air, soil and water remove As from surface water. For example, biomass from the
(Lasat, 2002; Cherian and Oliveira, 2005; Dickinson et al., 2009; stem of a thorny Acacia nilotica was used for the removal of As
Behera, 2014). The Pteris vittata (Chinese brake fern) was found to from As contaminated water bodies (Baig et al., 2010). Earlier,
be resistant to As, having the capability of hyperaccumulating other biomasses derived from fish scales, coconut fiber, dried roots
large amounts of As in its fronds (Ma et al., 2001) by area con- of water hyacinth plant, seed powder of Moringa oleifera, Mo-
taminants are picked up by the roots of plants and transported to mordica charantia, powdered eggshell, human hair, rice husk, rice
their overground parts, and then removed together with the crops polish; without chemical treatment have been reported
(phytostabilization, phytoextraction and phytovolatilization). The (Wasiuddin et al., 2002; Al-Rmalli et al., 2005; Kumari et al., 2006;
brake fern can accumulate between 1442–7526 mg kg  1 As in Nurul-Amin et al., 2006; Oke et al., 2008; Rahaman et al., 2008;
fronds from contaminated soils, and up to 27,000 mg kg  1 As in its Pandey et al., 2009; Ranjan et al., 2009). However, there is still a
fronds in hydroponics culture. The As hyperaccumulation capacity strong challenge in developing economical and commonly avail-
has also been demonstrated in other plants (Meharg, 2003; Du able biosorbents for the As removal.
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- 4.3. Coagulation–flocculation
accumulation is associated with the interaction of As with high-
affinity chelating molecules present in the cytoplasm of the plant. In As removal processes, coagulation and flocculation are
For example, an arsenate activated glutaredoxin from the fern P. among the most common method ever employed. The addition of
vittata L. regulates intracellular arsenite (Sundaram et al., 2008). a coagulant followed by the formation of a floc is a potential way
The molecular studies have shown that many gene products are for the removal of As from groundwater. Coagulants change the
involved in the process of As hyperaccumulation (Dhankar et al., surface charge properties of solids to allow the agglomeration or
2002), hence single gene and multigenic engineering approaches enmeshment of particles into a flocculated precipitate. The final
may be applicable to enhance the efficiency of phytoremediation products are larger particles or floc, which settle under the influ-
(Padmavathiamma and Li, 2007; Tripathi et al., 2007). Besides ence of gravity or filtered more readily. The destabilization of
phytoremediation, phytostabilization methods using plants can colloids by neutralizing the forces that keep them apart, is the
also be applied for long-term remediation of As. This method purpose of coagulation. Positively charged cationic coagulants
limits uptake and excludes mobilization of As. The major benefit of provide positive electric charges to reduce the negative charge
phytostabilization is that the vegetative biomass above ground is (zeta potential) of the colloids and as a result, larger particles are
not contaminated with As, thus reduces the risk of As transfer formed due to the aggregation of particles (Choong et al., 2007).
through food chains (Madejon et al., 2002). Flocculation is the action of polymers to form the bridges between
Furthermore, the bioremediation techniques, including a vari- the larger mass particles or flocs and bind the particles into the
ety of sulfate reducing bacteria and other species such as large agglomerates or clumps (Choong et al., 2007). In this tech-
Paenibacillus, Pseudomonas, Haemophilus, Micrococcus, and Bacillus nique, commonly used chemicals are aluminum salts such as
may be involved to remediate As from contaminated environ- aluminum sulfate [Al2(SO4)3  18H2O], and ferric salts such as ferric
ments (Yamamura et al., 2003, Kirk et al., 2004, Ike et al., 2008). chloride [FeCl3] or ferric sulfate [Fe2(SO4)3  7H2O] because of their
The basic principle of bioremediation is change in the redox re- low cost and relative ease of handling. In As removal by this pro-
actions, increasing/decreasing the solubility using different com- cess, chemicals transform As (dissolved) into solid (insoluble)
plexation reactions, pH changing and adsorption/uptake of a which is precipitated later. Dissolved As may also be adsorbed on
substance from the environment (Smith et al., 1994). Still, the the solid hydroxide surface site and be coprecipitated with other
current bioremediation techniques fail mainly because of the precipitating species (Mondal et al., 2006). The solids can be re-
limitations of phytoremediation in arid area, re-release of im- moved through sedimentation and/or filtration. Removal of As
mobilized or adsorbed heavy metals by some bacteria in the en- from water by coagulation using ferric or aluminum salts have
vironment, microbial sensitivity to redox potential change and been reported in several studies (Zouboulis and Katsoyiannis,
changes into the valence state of particular toxic metal. 2002; Yuan et al., 2003; Wickramasinghe et al., 2004; Song
During the last two decades, phytofiltration, a very en- et al., 2006; Andrianisa et al., 2008; Lakshmanan et al., 2010;
vironmentally friendly and low-cost alternative technique, is a Lacasa et al., 2011). Coagulants such as alum [Al2(SO4)3.18H2O],
promising emerging alternative to conventional cleanup. After the ferric chloride [FeCl3] and ferric sulfate [Fe2(SO4)3  7H2O] are
discovery of As hyperaccumulating and tolerating plants, it is found to be effective in removing As from water (Edwards, 1994).
possible to phytoremediate the As contaminated substrates. Phy- Ferric salts have been found to be more effective than alum in
tofiltration involves several steps, (i) the selection of the most removing As on a weight basis and effective over a wider pH range
promising plants capable of removing the contaminant from water (Cheng et al., 1994; Hering et al., 1997). At pH 7.6 or lower, iron and
and retaining it in their roots, and (ii) plants are then transplanted aluminum coagulants are of equal effectiveness in removing AsV.
into a constructed wetland, where As from the polluted water will However, iron coagulants are advantageous if pH is above 7.6, if
be removed. These plants mainly absorb and concentrate the As in soluble coagulant metal residuals are problematic, or if AsIII is
their roots, but can also translocate low quantities to their shoots present in the raw water. Generally, with increasing coagulant
(Dushenkov et al., 1995; Salt et al., 1998). In recent years, only dosages higher As removal efficiencies can be achieved. The ef-
plants which are able to hyperaccumulate As were discovered, like fectiveness of iron coagulants in removing AsIII diminishes at pH
P. vittata (Ma et al., 2001) and other ferns (Francesconi et al., 2002; 6.0. Wickramasinghe et al. (2004) used ferric chloride and ferric
Zhao et al., 2002; Srivastava et al., 2005). Aquatic macrophytes sulfate as a coagulant and their study suggested that the rate of As
have been particularly considered for As removal from con- removal was dependent on the raw water quality and pH adjust-
taminated surface water bodies. Several studies were performed ment before coagulation. On the other hand, studies investigating
for the removal of As from contaminated surface water bodies the effects of cationic (Wickramasinghe et al., 2004; Zouboulis and
using different species of aquatic macrophytes: water hyacinth 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- reached below 5 μg L  1. Strong oxidants produces during the
ited in numbers. Pallier et al. (2010) used kaolinite and FeCl3 as a Fenton-type reactions were found to oxidize AsIII to AsV (Li et al.,
coagulant/flocculent and they observed over 90% and 77% re- 2012). This is a key reaction for high effectiveness in the Bengal
movals of AsV and AsIII, respectively, using 9.2 mg L  1 of Fe3 þ . In a region because AsIII does not adsorb as strongly as AsV to FeIII
recent study, Hu et al. (2012) used three aluminum based coagu- oxyhydroxide surfaces in natural water at neutral pH (Dixit and
lants (aluminum chloride and two types of polyaluminium chlor- Hering, 2003), and both AsIII and AsV are present in the ground-
ide) and all of them were able to reduce the concentration of As water (Kinniburgh and Smedley, 2001). Although the initial as-
below the MCL (Maximum Contaminant Level) with an initial AsV sessments of reliability, robustness, consumables cost, and sludge
concentration of 280 mg L  1. Further their study suggests that the production from 100 L reactor field trials were promising (Amrose
aluminum species regulates the removal of As and therefore, the et al., 2013), however, is very limited in scope due to the small
efficiency of As removal can be improved by adjusting the pH. The system size and short duration.
presence of sulfates significantly decreases AsIII removal, but only
slightly affects AsV removal. At pH higher than 7.0, removal of AsV 4.6. Adsorption
increases in the presence of calcium. The major limitation of the
coagulation/flocculation process is the production of a large Adsorption is a process that uses solids for removing sub-
amount of sludge with a considerable concentration of As. stances from either gaseous or liquid solutions. Adsorption process
Recently, instead of conventional Al and Fe salts, titanium tet- has been used most widely because of its high removal efficiency,
rachloride (TiCl4) was used (Shon et al., 2007) to remove the easy operation and handling, low cost and sludge-free. Recently,
particulate and dissolved organic matter from wastewater in several studies have focused in the development of novel materials
sewage treatment plants. TiCl4 successfully achieved high organic based on alumina (Han et al., 2013), activated carbon (Zhang et al.,
matter removal to the same extent as Al and Fe salts and the re- 2007; Oliveira et al., 2008), iron oxides (Giménez et al., 2010; Sun
sulting flocs are with better settleability. The most significant ad- et al., 2013), zeolites (Swarnkar and Tomar, 2012), clays (Anjum
vantage of using TiCl4 as a coagulant is that sludge recovery pro- et al., 2011) etc. to adsorb As from water. Adsorption has attracted
duces a valuable by-product, namely titanium dioxide (TiO2) (Shon much attention due to the following advantages: (i) it usually does
et al., 2007; Lee et al., 2009), which is the most widely used metal not need a large volume and additional chemicals, (ii) it is easier to
oxide, whose applications include cosmetics, electronic paper, set up as a POE/POU (point of entry/point of use) As removal
paints, photocatalysts, and solar cells (Hoffmann et al., 1995; Obee process (Jang et al., 2008), and (iii) it does not produce harmful
and Brown., 1995). Furthermore, the residual Ti salt concentration byproducts (Genc et al., 2004, Zhang et al., 2005) and can be more
in the treated water satisfied the requirement of the World Health cost effective (Zhang et al., 2007). Generally, the removal of As by
Organization's (WHO) guidelines (0.5–15 mg L  1) for drinking adsorption techniques depends on pH and the speciation of AsV
water (Ravenscroft et al., 2009). Therefore, TiCl4 is expected to be a thus, at pH lower than 7 showing better AsV removals compared to
promising alternative coagulant for conventional Al and Fe salts. the AsIII (Zhu et al., 2013). The capacity and adsorption rate further
depends on the presence of other ions like phosphate, silicate,
4.4. Electrocoagulation (EC) HCO3- and Ca2 þ competing for the adsorption sites (Giles et al.,
2011, Zhu et al., 2013). There are some common adsorption tech-
It is an alternative process to CF (coagulation/flocculation). In- niques used for the efficient As removal from water are discussed
stead of adding a chemical reagent as ferric chloride, metallic ca- below.
tions are directly generated in the effluent to be treated by ap-
plying a current between iron electrodes to dissolve soluble an- 4.6.1. Activated alumina
odes. In EC, electrolytic oxidation of a sacrificial iron anode pro- Activated alumina (AA) is a physical/chemical process by which
duces FeIII oxyhydroxides/precipitates in As contaminated water. ions in the feed water are sorbed to the oxidized AA surface. It is
With FeIII precipitates As forms binuclear, inner-sphere complexes the most widely tested aluminium oxide (Lin and Wu, 2001; Singh
(van Genuchten et al., 2012), which aggregate to form a floc. Me- and Pant, 2004; Giles et al., 2011). AA was the first adsorptive
tallic cations and hydroxides formed neutralize negatively charged medium to be successfully applied for the removal of As from
colloids allowing them to coagulate (Matteson et al., 1995). During water supplies (EPA, 2000a, 2000b). It is prepared by the thermal
EC with iron electrodes, the amount of iron cations experimentally dehydration of aluminium hydroxide Al(OH)3 at high temperature.
dissolved from the anode corresponds to the value predicted by It is a porous, granular material having typical diameter of 0.3–
the second Faraday's law (Vik et al., 1984; Pretorius et al., 1991) 0.6 mm and a high surface area for good sorption properties. The
which is used to calculate the treatment dose to apply. AA is used in packed beds to remove contaminants such as As,
fluoride, NOM, selenium and silica. Under pressure, feed water is
4.5. Electro-chemical arsenic remediation (ECAR) continuously passed through the beds to remove the con-
taminants. The contaminant ions are exchanged with the surface
The ECAR is a form of electrocoagulation (EC) that has been hydroxides on the alumina. When adsorption sites on the AA
developed to support a community scale micro-utility business surface become filled, the bed must be regenerated.
model (Amrose et al., 2013). In ECAR, the high capacity adsorbent The As removal capacity of activated alumina is pH sensitive
media are generated in-situ, removing the need for a central ad- thus requires pre-and post-pH adjustment using caustic soda and
sorbent manufacturing plant or importing media from abroad. In sulfuric acid. AsV is strongly adsorbed on AA at pH 5–6 whereas
ECAR, the As-laden flocs are separated from clean water through AsIII is best adsorbed at pH 7–8 (Singh and Pant, 2004). The ad-
gravitational settling aided by a small amount of alum as a coa- sorption capacity of AA ranges from 0.003 to 0.112 g of As g  1 of
gulant. The effectiveness of ECAR has been demonstrated by AA. The factors which have significant effects on the As removal
Amrose et al. (2013), using synthetic groundwater in lab studies, achieved with AA are pH, As oxidation state, competing ions,
real contaminated groundwater from Bangladesh and Cambodia, empty bed contact time (EBCT), and regeneration. Other factors
and in short-duration field trials of two 100 L batch reactors in include spent regenerant disposal, alumina disposal, and second-
West Bengal. ary water quality.
The ECAR was found to lower initial As concentrations as high The AA media can either be regenerated on-site or disposed of
as 3000 μg L  1 to below the WHO-MCL of 10 μg L  1, and easily and replaced with fresh media. Regeneration is achieved through a
R. Singh et al. / Ecotoxicology and Environmental Safety 112 (2015) 247–270 257

sequence of rinsing with regenerant, flushing with water, and by Banerjee et al. (2008) and they showed that overall adsorption
neutralizing with acid. The regenerant is a strong base, typically reaction rate constant values for both AsV and AsIII increased with
sodium hydroxide (NaOH) and the neutralizer is a strong acid, increase in the temperature. The thermodynamic parameters ex-
typically sulfuric acid (H2SO4). The regeneration of saturated alu- amination revealed that the adsorption of AsV and AsIII by GFH was
mina is carried out by exposing the medium to 4% NaOH, either in a spontaneous endothermic process.
batch or by flow through the column resulting in high As con- Polymorphs of iron (III) hydroxy-oxide mineral [FeO(OH)] such
taminated caustic wastewater. Onsite regeneration of AA media as goethite (a-FeOOH), akaganèite (b-FeOOH) and lepidocrocite (c-
typically produces 37–47 bed volumes of caustic soda waste (EPA, FeOOH) have been described as good adsorbents for AsV. Pure
2000a, 2000b). The caustic soda residue is then washed out and goethite was synthesized by Mohapatra et al. (2007) with different
the medium is neutralized with 2% solution of H2SO4 rinse. It has dopant cations (Cu, Ni and Co) for adsorption of AsV. With
been reported that at pH range 2.8–11.5, alum-impregnated AA is 330 m2 g  1 surface area, akaganèite exhibited adsorption capacity
much better adsorbent for AsV than untreated AA and when em- as high as 120 mg g  1 (Deliyanni et al., 2003). The adsorption
ployed in batch mode AsV concentration could be brought down capacity of akaganèite (b-FeOOH) can be enhanced by isomorphic
from 10 mg L  1 (10,000 ppb) to 40 ppb (Tripathy and Raichur, substitution of Fe3 þ by Zr4 þ on its structure (Sun et al., 2013). At
2008). pH 7.0, the maximum adsorption capacity for AsV by akaganèite
The adsorption capacity and rate of conventional activated was 60 mg g  1. Adsorption capacities for lepidocrocite have been
alumina (CAA) for As removal is relatively low and slow, which has reported 25.17 mg g-1 with specific area of 103.9 m2 g  1 (Repo
been attributed to its ill-defined pore structure along with small et al., 2012). Another less known polymorph constitutes d-FeOOH,
surface area as it is reported that the maximum AsV adsorption having similar crystallographic structure as CdI2. Crystalline d-
capacity of granular AA with a surface area of 118 m2 g  1 (Ma- FeOOH can be easily prepared in the laboratory by a simple
cherey-Nagel, Germany) is 15.9 mg g  1 (Lin and Wu, 2001). On the method, with small particle size, high specific area and narrow
other hand, mesoporous materials have attracted much attention pore size distribution. The uniqueness of this FeOOH polymorph is
in the field of chemical engineering, optics, electromagnetics, that it is ferrimagnetic, thus after use in catalysis or adsorption
biomedicine, industrial catalysis and adsorption, environmental process it can be easily recovered by using a simple magnet (Pinto
protection, and fabrication of novel nano-object materials due to et al., 2012). These characteristics make d-FeOOH a suitable can-
the high surface area, well-defined and adjustable pore diameter
didate for use as an adsorbent for heavy metals in aqueous med-
of 2–50 nm (Ying et al., 1999; De Vos et al., 2002). Therefore, it
ium. Among the natural minerals, Fe containing natural magnetite
could be concluded that mesoporous alumina (MA) should be an
(Fe3O4), siderite and hematite have given much attention (Dixit
ideal adsorbent for removing As. Recently, efforts have been made
and Hering, 2003; Giménez et al., 2007; Jönsson and Sherman,
to synthesize appropriate mesoporous alumina for removing AsV,
2008). Guo et al. (2007a, 2007b) found that natural siderite and
which included high-temperature crystallization (Patra et al.,
hematite removed As through electrostatic attraction and surface
2012) or the use of expensive aluminum alkoxide (e.g. aluminum
complexation with the Fe hydroxides in the minerals. However,
tri-sec-butoxide) and organic solvent (2-butanol) (Yu et al., 2008).
the rate of reaction was slow and common anions such as bi-
carbonate and phosphate decreased the adsorption capacity of As.
4.6.2. Iron based sorbents (IBS)
In recent years, Fe3O4 (magnetite), a magnetic nanoparticles of
Adsorption on IBS is an emerging treatment technique for As
iron oxide nature and c-Fe2O3 (i.e., maghemite) have been found
removal. Removal has been attributed to ion exchange, specific
applicable in many practical branches of human activity. Based on
adsorption to surface hydroxyl groups or coprecipitation. Cur-
these, a promising technique was devised by mixing magnetite
rently, IBS products available in the market are granular ferric
and maghemite nanoparticles which can adsorb As from aqueous
hydroxide (GFH), iron coated sand, modified iron and iron oxide
solution and fit to use for the groundwater treatment. Under acidic
based adsorbents. Selvin et al. (2000) have described the sorption
pH conditions, 96–99% As uptake was recorded. The maximum
process as chemisorption, which is typically considered to be ir-
reversible. It has been reported that AsV adsorption on hydrous adsorption occurred at 2.0 pH with values of 3.69 and 3.71 mg g  1
iron (III) oxide strongly depended on the system's and pH (Ranjan of adsorbent for AsIII and AsV, respectively at the initial con-
et al., 2003), while AsIII adsorption was pH insensitive. The AsIII centration of 1.5 mg L  1 solution of both species. However, in
required less contact time to attain equilibrium and sulphate; presence of phosphate in the solution, the efficiency of the ad-
phosphate and hydrogen carbonate did not compete strongly with sorption process suffered. Less than 60% As uptake was achieved
the AsIII adsorption. At acidic to neutral pH, adsorption of AsV is from the natural groundwater containing more than 5 mg L  1
generally more effective than the adsorption of AsIII (Arienzo et al., phosphate and 1.13 mg L  1 of As. This is a practical problem to be
2005; Dixit and Hering, 2003; Leupin et al., 2005; Singh et al., faced in the field application of the technology (Chowdhury and
2007; Sharma et al., 2007; Su and Puls, 2008; Abdallah and Yanful, 2010).
Gagnon, 2009; Burton et al., 2009). On the basis of chemistry of Highly stable amorphous mesoporous iron oxides, prepared by
the remediation process, iron based technologies can be divided thermal decomposition of ferric nitrate-oxalic acid complex, showed
into two overlapping groups; first is when iron acts as sorbent, co- to be promising for the adsorption of AsV (Muruganandham et al.,
precipitant or contaminant immobilizing agent and the second is 2010). To increase the adsorption capacity of iron oxides, iron oxides
when iron behaves as a reductant (convert contaminants into composites and carbonaceous materials have been used as a strategy.
lower oxidizing state or used as an electron donor). Two important For example, composites of Fe3O4-reduced graphite oxide-MnO2 re-
iron based materials are hydrous ferric oxide (HFO) and goethite moved 12.22 mg AsV per gram of catalyst (Luo et al., 2012) while in the
(a-FeOOH) which are used as sorbent but goethite is less reactive presence of Fe3O4/graphene composite, a high adsorption capacity
than HFO due to the lack of sufficient surface area (Smedley and (180.3 mg g  1) for AsV was achieved (Mishra and Ramaprabhu, 2012).
Kinniburgh, 2002). The mechanism of AsV adsorption on GFH was Composites of iron oxides and TiO2 or Al2O3 presented adsorption
studied in detail by Guan et al. (2008), and they proposed that at capacity for AsV of 7.8 and 54.55 mg g  1, respectively (D'Arcy et al.,
7.4 pH, bidentate binuclear complexes with GFH are formed as 2011; Basu et al., 2012)). On the other hand, natural iron oxides
evidenced by an average Fe–AsV bond distance of 3.32 Å by EXAFS showed very low adsorption capacity (0.02–0.4 mg g  1) because of its
analyses. The impacts of temperature on adsorption kinetics and low specific surface area (Zhang et al., 2004; Guo et al. 2007a, 2007b;
equilibrium capacities for AsIII and AsV on GFH have been reported 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- Mak et al. (2009) had reported that the removal rate of As by
noparticles are frequently employed for the removal of As due to ZVI increased with increasing concentrations of Ca2 þ or HCO3 
their high surface area. Recently, Sabbatini et al. (2010) have de- because CaCO3 can form and acts as a nucleation seed for the
veloped tubular ceramic adsorbers based on iron oxide nano- growth of iron hydroxides. In the co-existence of Ca2 þ , HCO3  and
particles that have been deposited on porous alumina tubes. Iron humic acid, the presence of HA diminished the positive role of
oxide nanoparticles with combined ozonization-reactive ceramic Ca2 þ due to the formation of Fe-humate complexes in solution
membranes have been proved a good candidate for AsIII removal and delaying of the formation of CaCO3. The effects of HA on AsV
(Park and Choi, 2011). In a study, Pan et al. (2010) have reported removal by ZVI from groundwater was investigated by Rao et al.
that on using iron-oxide-coated diatomite, a granular adsorbent, (2009) and they observed that the removal rate of As was inhibited
for adsorption of AsV from aqueous solution, effectively working at in the presence of HA probably because of the formation of soluble
pH very close to the neutral value; here an industrial grade dia- Fe-humate in the groundwater which hindered the production of
tomite served as the iron oxide support. Recently, Chen et al. iron precipitates. When Fe-humate (complexation of HA with
(2011) have suggested ferric-impregnated volcanic ash as a re- dissolved Fe) was saturated, further corrosion of ZVI accelerated
presentative of low-cost adsorbent for removal of AsV from an the removal of As from groundwater via adsorption and co-pre-
aqueous medium. cipitation. The AsIII is more mobile and more toxic than AsV,
however, the removal of AsIII is more difficult than the removal of
4.6.3. Zero valent iron AsV. To remove high AsIII concentration of 10 mg L–1, Wan et al.
Over the last decade, a great deal of research has been focused (2010) conducted the combined processes of biological oxidation
on the removal of contaminants by zero valent iron (ZVI) because of AsIII, the removal of AsIII and AsV by ZVI obtained a very high As
ZVI is non-toxic, abundant, cheap, easy to produce, and little removal capacity (more than 70 mg As g  1 Fe). The kinetics and
maintenance is required by its reduction process. The method is mechanism of AsIII oxidation and removal by ZVI at pH 3–11 in
based on the principle is when the oxygenated water comes in aerated water was investigated by Katsoyiannis et al. (2008) and
contact with ZVI, it results in corrosion of ZVI and formation of found that AsIII was oxidized by the Fenton reaction and removed
various byproducts like FeII and FeIII hydroxides, that can oxidize by the sorption on newly formed hydrous ferric oxides and hy-
and remove As (Farrell et al., 2001; Manning et al., 2002). Many droxyl radicals were the main oxidant for AsIII at low pH.
groups have extensively investigated the removal of As by using Recently nZVI, a nanoparticle, is effective and extensively used
for the removal of As from contaminated water (Ludwig et al.,
ZVI in the laboratory (Leupin and Hug, 2005; Katsoyiannis et al.,
2009; Morgada et al., 2009; Tanboonchuy et al., 2011, 2012). For
2008; Klas and Kirk, 2013) as well as in the field (Hussam and
example, a novel process, air and/or CO2 bubbling nZVI was tested
Munir, 2007; Chiew et al., 2009; Neumann et al., 2013). Based on
for the removal of high concentration of AsV (3000 mg L  1) and
this technology, approximately 350,000 filters are in use in India,
demonstrated outstanding performances. Tanboonchuy et al.
Bangladesh, Pakistan, Nepal and Egypt with better results of As
(2012) investigated the influence of background species on the
removals in field (Hussam and Munir, 2007, 2013; Neumann et al.,
removal of AsIII and AsV in the groundwater by nZVI process. They
2013). It is desirable to analyze the effect of key variables, such as
found that Ca2 þ plays a promoting role while PO43  and HA play
pH, dissolved oxygen (DO), hardness, and humic acid (HA) on As
an inhibiting role on removal of As. As for Cl  and HCO3  , the
removal. Generally it is accepted that the mechanism of As re-
former enhances AsIII removal, whereas the later inhibits AsIII re-
moval by ZVI involves adsorption, reduction, surface precipitation,
moval; AsV removal was affected slightly in the presence of Cl 
and co-precipitation with various iron corrosion products such as
and HCO3  . Although nZVI is effective for the removal of As from
ferrous/ferric hydroxides (Mak et al., 2009). The removal rates of
contaminated water, but transformations and translocation of As
AsIII were investigated in the presence of various ions and under
at and within the nanoparticles are not clearly understood.
different pH values and results indicated that most of these
parameters affected negatively the removal of AsIII (Biterna et al.,
4.6.4. Indigenous filters and cartridges
2010). Sun et al. (2011) reported that in anaerobic conditions when Presently, several indigenous materials are available that are
AsV reacted with commercial ZVI or acid-treated ZVI both ad- used as filters for As adsorbent. Red soil rich in oxidized iron, iron
sorption and reduction of AsV were fast; commercial ZVI reduced ore, clay minerals, iron scrap or fillings and processed cellulose
AsV to AsIII while acid-treated ZVI reduced AsV to As0. materials are known to have the capacity for As adsorption. The
The DO plays an important role in As removal by ZVI. The re- typical clay minerals such as kaolinite, montmorill ionite and illite
action of ZVI with DO leads to the formation of reactive inter- are used for the As adsorption (Lin and Puls, 2000; Goldberg,
mediates (e.g. HO2/–O2  , H2O2, –OH) and Fe(II). Fe(II) is oxidized 2002; Mohapatra et al., 2007). Manning and Goldberg (1996, 1997)
to Fe(III) and forms hydrous ferric oxides with large sorption ca- and Mohapatra et al. (2007) reported that As is adsorbed on the
pacities (Joo et al., 2004), such that there is a potential for the surface of clay through inner sphere surface complexation. To
transformation and removal of a range of inorganic and organic enhance the adsorption of As on clay, Li et al. (2007) and Su et al.
contaminants. It was found that low pH and high DO would favor (2011) prepared surfactant-modified clay to remove As from
the As removal (Tanboonchuy et al., 2011). In aerobic condition, aqueous solution. Su et al. (2011) in a study used octadecyl tri-
Bang et al. (2005b) observed a rapid rate of As removal from methylammonium chloride, octadecyl benzyl dimethylammonium
aqueous solution via precipitation/co-precipitation on iron hy- chloride and dioctadecyl dimethyl ammonium chloride as cationic
droxide precipitation product and at pH 7.0 the uptake of AsV was surfactants for the modification of bentonite. The charge on the
faster than AsIII. However, in anaerobic conditions, the rate of re- clay surface get reversed i.e. from negative to positive by the re-
action was considerably slower as compared to the aerobic en- placement of exchangeable Na þ and Ca2 þ cations on clays with
vironment and at pH 4.0 and 7.0 the removal rate of AsIII was faster the cationic surfactants and resulting organoclay becomes a po-
than AsV. Furthermore, their study also demonstrated that in ab- tential adsorbent to adsorb the oxy-anions of As from aqueous
sence of O2, reduction of AsV to AsIII and AsIII to metallic As takes solution (Li and Bowman, 2001).
place upon reaction with ZVI. Thus, different reaction mechanisms Zeolites are tectosilicate minerals with 3D aluminosilicate
of As with ZVI predominate in aerobic and anaerobic environ- structure containing water molecules, alkali and alkaline earth
ments. In the absence of O2, ZVI is able to act as a reductant and to metals in their structural framework. Due to high ion exchange,
reduce AsV and AsIII. adsorbing, catalytic and molecular sieving capacities these have
R. Singh et al. / Ecotoxicology and Environmental Safety 112 (2015) 247–270 259

potentials to be used as treatment mineral in the permeable re- aqueous solutions. Furthermore, in China, over 60% of rural
active barriers (PRBs) (ITRC, 2005; Roehl et al., 2005). Removal of households are directly depends on coal honeycomb briquette for
As from different type of water having varying mineralization cooking and heating (Sinton et al., 2004), that ultimately produce
degree can also occur through natural zeolitic rocks such as cha- massive cinders.
bazite–phillipsite, clinoptilolite, and volcanic glass. The As removal
efficiency for chabazite–phillipsite was 60–80% and for clin- 4.6.5. Miscellaneous adsorbents
optilolite-bearing rocks was 40–60%. Removal of As is influnced by In last years, a wide variety of adsorbent systems have been
three key factors first, mineralogy of the zeolites occurring in the developed for the removal of As. Activated carbon (Huang and Fu,
volcanic rock, second, zeolite content of the zeolitic rock and lastly, 1984), fly ash (Diamadopoulos et al., 1993), aluminum-loaded coral
the degree of water mineralization (Ruggieri et al., 2008). limestone (Ohki et al., 1996), modified fly ash (Goswami and Das,
By using above mentioned materials, some of the filters are 2000), iron oxide minerals (Suvasis and Janet, 2003), activated
manufactured including Sono 3-Kolshi Filter, Granet Home-made neutralized red mud (Hulya et al., 2004), chitosan (Chen and
Filter, Chari Filter, Adarsha Filter, Shafi Filter, and Bijoypur Clay/ Chung, 2006), chitosan derivatives (Laurent et al., 2002), iron hy-
Processed Cellulose filters. The Garnet home-made filter contains droxide-coated alumina (Hlavay and Polyak, 2005), modified fun-
relatively inert materials like brick chips and sand as filtering gal biomass (Pokhrel and Viraraghavan, 2006), iron containing
media without added any chemical to the system. Air oxidation mesoporous carbon (Zhimang and Baolin, 2007), iron oxide-im-
and adsorption on iron-rich brick chips and flocs of naturally pregnated activated carbon (Ronald et al., 2007), nanoparticles of
present iron in ground water could be the possible reason for As hydrous iron oxide (Sylvester et al., 2007) etc. were used as ad-
removal from ground water. The study demonstrates that three- sorbents for the removal of As from aqueous environments. Chit-
pitcher filters are an effective option as a short-term measure for osan is transformed polysaccharide obtained from the de-acet-
As removal. However, the three-pitcher filters that are not effec- ylation of chitin, which makes the shells of crustaceans such as
tive option for long duration. The Chari filter also uses brick chips crabs and shrimps. It is biodegradable, biocompatible, and non-
and inert aggregates in different Charis as filter media. The Shafi toxic, making it environment friendly. Guibal (2004) reported
and Adarshs filters use clay material as filter media in the form of chitosan as an efficient heavy metal scavenger due to the presence
candle. Although the Shafi filter was reported to have better As of hydroxyl and amino group with high activity as adsorption site.
removal capacity but clogging of filter media is still a problem. Although, chitin/chitosan have been used for the removal of AsV
Khair (2000) found that Bijoypur clay and treated cellulose were from water but capacity was found to be very low
also able to adsorb As from water. These units/filters remove As (0.13 mmol g  1). Recently, a novel composite chitosan bioadsor-
like any other dissolved ions present in the water but are not bent (CCB) have been developed (Boddu et al., 2008) for the re-
suitable for water having high impurities and iron content in moval of AsIII and AsV from aqueous solutions by coating natural
water. In early 90s, the development of Bio-Sand Filter (BSF) for biopolymer, chitosan, on ceramic alumina, using a dip-coating
homebased drinking water treatment has received much attention process. Their study reported a very high adsorption capacity at
because of its high pollutants removal, technical simplicity, cost pH 4.0 (56.50 and 96.46 mg g  1 for AsIII and AsV, respectively).
effectiveness and least maintenances (Bajpai and Chaudhuri, 1999; Chen et al. (2008) used the chitosan impregnated with molybdate
Gene-Fuhrman et al., 2005; Ngai et al., 2006; Guo et al., 2007a, to remove AsIII and AsV from contaminated water.
2007b; Mahmood et al., 2011). Later Ngai et al. (2006), Ahammed A high As sorption capacity (2860 mg g  1) was observed on
and Davra (2011) and Noubactep et al. (2012) made certain mod- activated carbon by Rajakovic (1992). Rajakovic (1992) found that
ifications to BSF design and filter media for improving its perfor- carbon pretreated with Ag þ or Cu2 þ ions improved the AsIII ad-
mance. In a recent study, Noubactep et al. (2012) employed three sorption but reduced the AsV adsorption. In order to improve the
compartment model of BSF having extended reactive layer of ZVI As adsorption carbon was impregnated with different metal ions
and reported the significant pollutants removal for safe drinking such as iron oxide. For example, Gu et al. (2005) prepared the iron
water production. Kanchan arsenic filter (KAF), a saturated sand containing granular activated carbon (GAC) adsorbents for As ad-
filter was designed by Ngai et al. (2006), and found to successfully sorption from drinking water. Factors such as solution pH, carbon
remove As and pathogens from drinking water. Sand is considered type and carbon pretreatment and elution of the As from loaded
as a non-reactive material and only removed suspended particles carbon that affect the mechanism of the adsorption of As species
during filtrations (Noubactep, 2010). on activated carbons were studied (Lorenzen et al., 1995). They
Metal oxides/hydroxides coated adsorbents such as iron oxide observed that AsV is more effectively removed from solution by
coated sand, manganese-coated sand, Fe3 þ impregnated activated using activated carbon with high ash content and pre-treatment of
carbon, siderite-coated quartz and hematite coated quartz have the carbon with Cu(II) solutions also improved its As removal ca-
been extensively used to improve the filter efficiency (Jessen et al., pacity. Gu and Deng (2006) prepared iron containing mesoporous
2005; Leupin et al., 2005; Guo et al., 2007a, 2007b; Chang et al., carbon (IMC) from a silica template (MCM-48) and used for the
2008; Mondal et al., 2008; Chiew et al., 2009; Noubactep, 2010; removal of As from drinking water. The maximum adsorption ca-
Noubactep and Care, 2010; Maji et al., 2011; Noubactep et al., pacities were 5.96 mg As g  1 for AsIII and 5.15 mg As g  1 for AsV.
2012). Recently, Rahman et al. (2011) employed sub-surface wet- Focusing the morphology and size of adsorbents it is aimed to
land and soil filter systems for As removal. Many emergent ad- generate high surface areas and high density of adsorptive sites.
sorbents being used in filter-based treatments are not sufficient to For example, three-dimensional flower-like, urchin-like and hier-
remove total As (AsIII þ AsV) from water (Xu et al., 2007; Guan archical superstructure adsorbents have been found to well suit
et al., 2012). Therefore, in order to provide As free drinking water the adsorption application (Zhong et al., 2006; Wang et al., 2012;
on sustainable basis, pre-oxidation process is essential to convert Zhang et al., 2012). Pore structure also influences the adsorption
AsIII into better adsorbable AsV (Chang et al., 2008). In many de- behavior of an adsorbent (Drisko et al., 2009; Kimling et al., 2012).
veloping countries, cinders generated from the combustion of coal Hierarchically porous materials, possessing macro-and/or meso-
honey comb briquette (HBC) in decentralized cylindrical stoves porous networks, facilitate rapid As species diffusion as well as
have mostly been used for the civil applications. Recently, Yue promote access to the active sites, resulting in a high As uptake
et al. (2011) and Sheng et al. (2014) experimentally proved HBC to and kinetics (Zhang et al., 2010a, 2010b; Wu et al., 2012). Chemical
be useful for the pollutants removal. Sheng et al. (2014) confirmed composition variation can change the properties of adsorbent
that iron-amended HBC efficiently removed AsV (961.5 mg g  1) in 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 for example, sulfate ions may displace previously sorbed AsV ions,
and the surface charge of the adsorbents are related strongly to the the resulting levels of As in the effluent is greater than the As level
water pH value. Thus, pH effect plays a great role in the As ad- in the influent. In general, ion exchange for As removal is only
sorption process (Sofia Tresintsi et al., 2012). applicable for low-TDS, low-sulfate source waters. Removal of As
In the past few years, ceria (Ce) and zirconia (Zr), highly re- can also be affected by the presence of iron, FeIII, in feed water. In
active rare-earth metal oxides, are found incorporated into the the presence of FeIII, As may form complexes with iron. These
adsorbents that significantly can improve the adsorption capacity complexes are not removed by ion exchange resins and therefore
of As because they have a unique selectivity for polyoxy anions As is not removed.
(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 4.8. Electrokinetics
oxide (Deng et al., 2010), Zr (IV)-loaded ligand exchange fiber
(Rabiul Awual et al., 2012), Zr (IV)-loaded orange waste gel (Biswas Electrokinetic (EK) remediation is a technique that already had
et al., 2008), etc. showed enhanced As adsorption performance proven its value, especially in contaminated fine-grain soils.
because of their increased surface areas, surface hydroxyl group, Virkutyte et al. (2002) reported three phenomena occurs during
and pore accessibility. In aqueous solutions, Ce and Zr can form electrokinesis are electro-osmosis, electromigration and electro-
tetranuclear or octanuclear species, which have abundant hydro- phoresis. This method uses a low-level direct current as the
xyl groups and water molecules to be involved in ligand sub- “cleaning agent”, several transport mechanisms (electroosmosis,
stitution with As species (Zhong et al., 2007; Biswas et al., 2008; Li electromigration and electrophoresis) and electrochemical reac-
et al., 2010). Thus, composites combined CeO2 and ZrO2 might be tions (electrolysis and electrodeposition) are induced (Acar and
an ideal candidate for the removal of As. Alshawabkeh, 1993). When a direct electrical field is applied across
a wet mass of contaminated soil, the migration of non-ionic pore
4.7. Ion exchange fluids by electro-osmosis and the ionic migration of dissolved ions
take place towards the electrodes. This technique has certain ad-
In the past, ion exchange has been used for removal of con- vantages over the conventional methods: (1) it is efficient in low
taminants from water (Oehmen et al., 2006). Ion exchange is a permeability soil, which is difficult to treat by using other meth-
physical/chemical process by which an ion on the solid resin phase ods; (2) is possible to set-up in situ for sites that are impossible to
is exchanged for an ion in the feed water. The solid resin is typi- excavate, such as residential areas and railway soil and (3) it can
cally an elastic three-dimensional hydrocarbon network contain- remove organic and inorganic pollutants from soil simultaneously.
ing a large number of ionizable groups electrostatically bound to The electro-remediation is considered to be the most effective
the resin. These groups are exchanged for ions of similar charge in in treating near saturated, clay soils polluted with metals, whereby
solution that have a stronger exchange affinity (i.e. selectivity) for removal is 4 90% (Virkutyte et al., 2002). Sims (1990) and
the resin. Typically, strong-base anion exchange resins are com- Cauwenberghe (1997) reported that in sub-surface the electro-
monly used for the removal of As where the oxy-anionic species of migration rate is dependent upon the density of water current, soil
AsV (such as H2AsO4  , HAsO4  2 and AsO4  3) are effectively ex- pore, ionic mobility, grain size, concentration of contaminant and
changed with the anionic charged functional group of the resin, total ionic concentration. In turn, it is governed by advection
thus produces effluents with low concentration of AsV (Choong which is generated by electroosmotic flow and externally applied
et al., 2007). Over a larger range of pH, strong-base anion resins hydraulic gradients, diffusion of the acid front to the cathode and
tend to be more effective than weak-base resins. The order of the migration of anions and cations towards the respective elec-
exchange for most strong-base resins is given below: trodes (Zelina and Rusling, 1999).
HCrO4  4CrO42  4 ClO4  4SeO42  4SO42  4NO3  4Br  4 During the EK process, the dominant electron transfer reaction
(HPO42  , HAsO42  , SeO32  , CO32  )4CN  4NO2  4Cl  4 i.e. electrolysis of water occurs at electrodes is as follow:
(H2PO4  , H2AsO4  , HCO3  )4 OH  4CH3COO  4F
This technology in drinking water treatment is commonly used H2O-2H þ þ ½ O2(g) þ 2e  (8)
for the softening and nitrate removal. Before passing the As con- 2H2O þ2e  -
-2OH þ H2(g) (9)
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 The hydrogen ions produced in the above given process de-
exchanged with As. The AsV can be easily removed through the use creases the pH near the anode causing desorption of metallic
of strong-base anion exchange resin either in the form of chloride contaminants from the soil solid phases. The dissolved metallic
or hydroxide. Sarkar et al. (2007), Wan et al. (2010) and Donia et al. ions are then removed from the soil solution by ionic migration
(2011) have reported As removal by using strong base anion ex- and precipitation at the cathode (Acar and Alshawabkeh, 1993). On
change resins. The efficiency of ion exchange process is improved the other hand, when hydroxide ion concentration increases the
by pre-oxidation of AsIII to AsV but before the ion exchange, the pH near the cathode also increases. Electro-kinetic remediation
excess of oxidant often needs to be removed in order to avoid the techniques demonstrated 85–95% As removal efficiency, from low-
damage of sensitive resins. Therefore, the efficiency of the ion permeability soils such as clay, peat, kaolinite, high-purity fine
exchange process for AsV removal strongly depends on the solu- quartz, Na and sand montmorillonite mixtures, as well as from
tion pH and the concentration of competing ions most notably argillaceous sand (Yeung et al., 1997). However, kaolinite showed
sulfates and nitrates, resin type, alkalinity, and influent. Other more than 90% removal efficiencies of heavy metals (Pamukcu and
factors include the affinity of the resin for the contaminant, spent Wittle, 1992).
regenerant and resin disposal requirements, secondary water During EK remediation process, various chemicals such as
quality effects, and design operating parameters. The performance chelating agents, surfactants, etc. have been investigated to facil-
of an ion exchange system can be adversely affected by high levels itate the mobility of pollutants in soil. To remediate the soil con-
of total dissolved solids (TDS). Nitrate, sulfate and phosphate, taminated with gasoline Bhattacharya (1996) applied surfactant
common competitive anions, play a significant role for the removal effectively using EK system. To restore the diesel-contaminated
of As via ion exchange. When an ion is preferred over AsV, higher sandy soil, Kim and Lee (1999) adopted an anionic surfactant,
As level in the product water than exist in the feed water can be sodium dodecyl sulfate (SDS), in the EK process. In their experi-
produced. Höll (2010) suggested if a resin prefers sulfate over AsV, ments, the effects of electrophoretic transportation of SDS fed into
R. Singh et al. / Ecotoxicology and Environmental Safety 112 (2015) 247–270 261

a catholyte chamber, showed the dominant mechanism for the four aluminium sheets of 0.15 m  0.05 m  0.002 m, were continued
removal of diesel and compared them to those of electroosmotic upto 45 minutes with a current density of 625 A m  2.
flow. Yang et al. (2005) tested surfactants that had anionic or non-
ionic characteristics and observed the effects of their ionic char- 4.9.2. As removal using ultrafiltration
acteristics and concentrations during the EK process. On the other Ultrafiltration (UF) is a size exclusion-based low pressure-dri-
hand, to increase removal of heavy metals from the soil, Yeung ven membrane separation process having pore sizes in the range
et al. (1996) and Wong et al. (1997) tested a chelating agent, EDTA, from 10 to 1000 Å and is capable of retaining species in the mo-
in EK remediation system. lecular weight ranging from 300 to 5,00,000 Da. The rejection of
As by charged membrane explored the influence of co-occurring
4.9. Membrane technology divalent ions and natural organic matter (NOM). In presence of
divalent cations such as Ca2 þ , Mg2 þ , AsV rejection reduced almost
Membranes are typically synthetic materials with billions of upto zero. This reduction in AsV rejection probably due to the
pores or microscopic holes that act as a selective barrier; the formation of ion pairs between counter ions and the fixed charge
structure of the membrane allows some constituents to pass group in the membrane matrix locally neutralizes the membrane
through, while others are excluded or rejected. The movement of charges. Brandhuber and Amy (2001) investigated the effect of
molecules across the membrane needs a driving force, such as charge on the UF membranes and reported that mechanism of As
pressure difference between the two sides of the membrane. This removal was mainly due to the electrostatic interaction between
the As ions and the negatively charged membrane surface, con-
technology can reduce As concentrations to less than 50 mg L  1
sistent with the Donnan theory. In their study they found a
and in some cases to below 10 mg L  1. It produces large residual
moderate rejection of 53% and 65% for AsIII and AsV, respectively.
volumes and is more expensive than other As treatment technol-
Thus, alone UF is not able to remove the As species directly due to
ogies. Researchers have explored various types of pressure driven
the pore size, which easily passes the dissolved As through the
membrane such as microfiltration (MF), ultra-filtration (UF), nano-
filtration (NF) and reverse osmosis (RO) for the removal of As from
The presence of NOM improved AsV rejection in presence of
contaminated water. The separation by these processes depends
divalent cations. This might be due to the complexion of divalent
on the pore size of the membrane; for MF and UF membranes,
ions whose presence in the solution reduces AsV rejection. Another
mechanical sieving is responsible for separation while for NF and
possibility might be due to the adsorption of NOM onto the
RO membranes, separation is achieved via capillary flow or solu-
membrane surface to form a negatively charged layer. Solution
tion diffusion (Shih, 2005; Choong et al., 2007).
with higher concentration of NOM led to higher charge density in
the adjacent membrane layer causing more rejection of the ne-
4.9.1. As removal using microfiltration
gatively charged As species.
The MF is a low pressure driven membrane process for separ-
Iqbal et al. (2007) studied the effect of co-occurring inorganic
ating colloidal and suspended particles in the range 0.1–10 μm.
solutes (such as HCO3-, HPO42-, H4SiO4 and SO42-) on the removal
The MF alone cannot remove the dissolved AsV and AsIII species
of AsV in feed water and permeate flux were investigated by using
from As contaminated water. The As removal by MF membrane
a cationic surfactant cetlylpyridinium chloride (CPC) and a flat
can only be achieved by increasing particle size of As bearing
sheet hydrophilic polyethersulfone (PES) ultrafiltration membrane
species therefore prior to MF, coagulation and flocculation pro-
(Millipore, Bedford, MA). The PES membrane without surfactant
cesses could be effective to increase the particle size of As bearing micelles was found to be ineffective for the removal of As while
species and were found to remove As species from As con- the addition of surfactant significantly increased the efficiency of
taminated water (Meng et al., 2000; Han et al., 2002; Chwirka As removal. Removal of As with surfactant was found to be 78–
et al., 2004; Ghurye et al., 2004). For example, Han et al. (2002) 100% while As removal in the presence of inorganic solutes was
used FeCl3 and Fe2(SO4)3 as flocculants and studied the removal only 25%.
rate, which was dependent on the adsorption of As on to the FeIII- The removal characteristics of As with ground water was in-
complex and their subsequent removal from the solution. Their vestigated by using micellar-enhanced ultrafiltration (MEUF)
results showed that by the combination of flocculation and MF (Iqbal et al., 2007). The different cationic surfactants used by them
technique, the As removal efficiency are higher than MF alone and were benzalkonium chloride (BC), hexadecylpyridinium chloride
depends on the effectiveness of As adsorption onto the FeIII- (CPC), hexadecyltrimethyl ammonium bromide (CTAB) and octa-
complex present and also on the rejection of the As containing decylamine acetate (ODA). Among these four cationic surfactants
flocs formed by the MF membrane. In turn, adsorption of As on the used during MEUF, the highest As removal efficiency was obtained
FeIII complex was found to be affected by the pH of the solution as in case of CPC i.e. 96%, with CTAB was 94% and the removal effi-
well as the presence of other ions in the solution. ciency with ODA was over 80% while the As removal efficiency
Shih (2005) reported that in the pH range 4.0–10.0, negatively with BC was the lowest i.e. 57% due to the higher critical micelle
charged AsV anions got effectively adsorbed by forming surface concentration (CMC) of BC compared to those of other surfactants.
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- 4.9.3. As removal using Nanofiltrations
sorbed. Therefore, complete removal of As from water could have Nanofiltrations (NFs), high pressure techniques and are able to
been achieved by completely oxidizing AsIII to AsV prior to coa- remove the dissolved As from the contaminated water to an ap-
gulation–microfiltration process. The size of As containing parti- preciable level provided that the feed water contains a very low
cles increases via coagulation–flocculation process and thus makes amount of suspended solids (Figoli et al., 2010). The nominal pore
it possible to remove As species using low-pressure membrane size of the membrane is about 1 nm and molecular weight is ty-
technology like MF. pically less than 1000 Da.
Recently, Ghosh et al. (2011) studied the electrocoagulation (EC) Generally, NF membranes are applied for the separation of
followed by MF by using a ceramic membrane was found to be ef- multivalent ions from the monovalent ions. These membranes
fective in the removal of As from feed solution having concentration have slightly charged surfaces and charge interaction plays a
of 200 μg L  1 in presence of fluoride and iron contaminant to a As dominant role in separation of molecules. The NF membranes are
content of 8.7 μg L  1. The EC experiment, consisted of a bath with 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- less than 50%. Therefore, where AsIII is the dominant species RO
ported that both dissolved AsV and AsIII can be effectively removed seems to be ineffective for As contaminated natural water espe-
(up to 99%) from water due to the size exclusion. However, Urase cially for reducing conditions.
et al. (1998) demonstrated that charged membranes generally
have a higher rejection for charged solutes than for uncharged 4.10. As removal by advanced hybrid and integrated technologies
solutes and concluded that the pore size of the membrane does
not have a significant effect on As rejection, but rather charge 4.10.1. As removal using membrane distillation
exclusion is predominant over the size exclusion mechanism. Presently, As remediation is taking place with better under-
Seidel et al. (2001) and Velizarov et al. (2004) demonstrated standing of complex chemical processes due to the recent advance-
that separation of As is caused due to the electrostatic repulsion ment in science and technology. Among the different kinds of
between anionic As species and the charge of membrane (Donnan membrane distillation (MD), direct contact membrane distillation
exclusion) as well as the small sized pores of the membrane. Al- (DCMD) is the most simple, economical and efficient technique
though the charges of the NF membranes are not fixed but may where the hot feed and the cold permeate are directly separated by
change due to adsorption of anions onto the membrane, and the membrane. The MD is a non-isothermal membrane separation
therefore are dependent on the bulk anion concentration process that employs a microporous hydrophobic membrane with
(Velizarov et al., 2004 ). Moreover, at the isoelectric point of the pore size ranging from 0.01 μm to 1 μm. The main requirements for
membrane, the charge of the membrane is zero, which changes to MD process are that the membrane should not be wetted and only
positive values for a lower pH. Thus, pH selection is important vapor and non-condensable gases should be present within its pores.
with respect to the target ions are to be separated. The perfor- Based on these requirements hydrophobic, microporous membranes
mances of two commercially available NF membranes (NF90 and made of polytetrafluoroethylene (PTFE), polyethylene (PE), poly-
NF200) were studied by Uddin et al. (2007) for removal of both propylene (PP), and polyvinylidenefluoride (PVDF) are now com-
AsIII and AsV from contaminated water. They demonstrated that mercially available. Recently, there have been studies to remove As
the rejection of AsV was better than AsIII and even when the feed using DCMD (Islam, 2004; Manna et al., 2010; Yarlagadda et al.,
solutions contain 50 mg L  1, AsIII could not be reduced to MCL and 2011). In one such study, Manna et al. (2010) had performed ex-
they concluded that oxidation of AsIII to AsV is an essential pre- periments by using three different types of hydrophobic membranes
treatment step. Figoli et al. (2010) demonstrated that the AsV re- for solar driven MD and studied the removal of AsIII and AsV from
moval efficiency was increased with increasing of solution pH groundwater. Their study demonstrated that nearly 100% of the As
along with decrease of operating temperature and the feed As removal from the contaminated groundwater with high flux of
concentration, while the transmembrane pressure had little/no 49.80 kg m  2 h  1. Recently, AsV and AsIII removal studied by Qu
effect. Sato et al. (2002) and Uddin et al. (2007) reported that et al. (2009) using self-made polyvinylidene fluoride (PVDF) mem-
without oxidative pretreatment, NF is not sufficient for the re- brane in a DCMD unit and the experimental results indicated that the
moval of total As from aqueous solution and therefore is not able permeate AsIII and AsV were under the maximum contaminant limit
to provide water quality below the MCL. (10 μg L  1) until the feed AsIII and AsV concentration achieved 40 and
In a recent study, As removal by employing self-made PMIA 2000 mg L  1, respectively. Macedonio and Drioli (2008) tested the
(poly m-phenylene isophthalamide) nanofiltration membrane was performance of an integrated RO and MD system. This integrated
investigated with aqueous solution of As salt (Na2HAsO4.7H2O) process (RO followed by MD) removes total As from water and leaves
and more than 90% AsV rejection was reported (Zhao et al., 2012). less environmental hazardous waste on comparing to oxidation fol-
Furthermore, AsV rejection increased from 83% at pH 3 to 99% at lowed by the RO and thus is very promising for contaminated water
pH 9. In presence of NaCl, AsV rejection increased in the feed range purification.
studied and was reported to be 99% when feed concentration was
100 μg L-1. 4.10.2. As removal using forward osmosis
Forward osmosis (FO) is another membrane process that has
4.9.4. As removal using reverse osmosis been used for treatment of industrial waste, concentrate landfill
Reverse osmosis (RO) is the oldest and identified as the best leachate, liquid food in food industry and desalination of seawater
available technology for the small water treatment systems to (Cath et al., 2006). Water is filtered due to the osmotic pressure
remove As from water. The RO membrane contains extremely difference, which is the driving force for FO separation. Cath et al.
small pores ( o0.001 μm) (Schneiter and Middlebrooks, 1983) and (2006) had determined several advantages of the use of FO: (i) it is
a very high (often close to 100%) rejection of low-molecular mass a simple equipment set-up (ii) there is low or no requirement of
compounds and ions can be achieved (Velizarov et al., 2004). hydraulic pressure, (iii) the membrane have a high rejection, and
Moreover, the process can easily be automated and controlled. In (iv) the probability of lower membrane fouling than other con-
the 1980s, with the invention of cellulose acetate RO membrane, ventional membrane processes. Recently, Jin et al. (2012) in-
AsV removal efficiency have been achieved of above 90% with the vestigated the removal of As using FO and also studied the influ-
RO system operated at high-pressure around 400 psi (Clifford ence of membrane orientation and membrane fouling. The As from
et al., 1986; Fox, 1989) while, AsIII removal efficiency was less solution was successfully removed by the FO and the removal/
than 70%. The operational parameters for As removal by RO rejection was better when the surface active membrane side faced
membranes was investigated by Akin et al. (2011) and found that the feed water compared to the draw water due to more severe
although the feed water concentration had no effect on the re- concentrative internal concentration polarization. In addition, they
jection rate, the rejection of As was largely affected by the pH of also found that for FO, the AsIII rejection from solution was greater
the feed water and operating pressure. Yoon et al. (2009) studied than that of RO; the rejection increased by increasing water flux.
the effect of charged membranes on the As removal and their Further, they concluded that the lower rejection by RO was due to
study concluded that there was a considerable rejection of the the deformation of the fabric supported membrane followed by
oxy-anionic AsV while below pH 10 AsIII removal was low due to expansion of membrane pores by hydraulic pressure, which en-
the existence of uncharged AsIII species in solution. Thus, the abled As and other solute particles to pass through the membrane.
presence of AsIII plays an important role for removal of As. Ac- Although in DCMD and FO, the waste water with an increased As
cording to the Walker et al. (2008) when AsIII was the dominant As concentration after separation may be re-treated, the As con-
species in the groundwater, the As removal efficiency decreased to centration significantly increases in the feed water. As a result, the
R. Singh et al. / Ecotoxicology and Environmental Safety 112 (2015) 247–270 263

risk for membrane damage increases along with the cost of Al-Rmalli, S.W., Harrington, C.F., Ayub, M., Haris, P.I., 2005. A biomaterial based
treatment. Therefore, this concentrate then can be treated with approach for arsenic removal from water. J. Environ. Monit. 7, 279–282.
Alvarado, S., Guédez, M., Lué-Merú, M.P., Nelson, G., Alvaro, A., Jesús, A.C., Gyula, Z.,
ZVI under an inert atmosphere so as to reduce the soluble As to 2008. Arsenic removal from water by bioremediation with the aquatic plants
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