JRRAS146_proof ■ 18 March 2015 ■ 1/9

J o u r n a l o f R a d i a t i o n R e s e a r c h a n d A p p l i e d S c i e n c e s x x x ( 2 0 1 5 ) 1 e9

H O S T E D BY Available online at www.sciencedirect.com

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1
ScienceDirect 66
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2 Journal of Radiation Research and Applied 68
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4 Sciences
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journal homepage: http://www.elsevier.com/locate/jrras
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9 Application of biopolymer composites in arsenic 75
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11 removal from aqueous medium: A review 77
12 78
13 Arsenic removal from aqueous medium using 79
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15 Q1 polymeric biocomposites 81
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Q5 Muhammad Rahim*, Mas Rosemal Hakim Mas Haris 84
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20 School of Chemical Sciences, Universiti Sains Malaysia, 11800 Minden, Pulau Pinang, Malaysia 86
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23 article info abstract 89
24 90
25 Article history: Various sorbents have been used to remove arsenic from contaminated water which is one 91
26 92
Received 20 December 2014 of the most toxic elements for mankind. In this review, concentration has been focused on
27 93
Received in revised form the removal of arsenic from aqueous medium using natural, non-toxic, biodegradable and
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26 February 2015 eco-friendly polymeric materials. Therefore, chitosan has been selected one of the most
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30 Accepted 6 March 2015 appropriate biopolymer to remove heavy metals form contaminated water particularly
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31 Available online xxx arsenic. Therefore, chitosan grafting, blending, doping and biocomposite formulations
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32 with polymeric and/or activated inorganic materials have gained much attention. This
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33 Keywords: review provides the relevant literature on the applications of polymeric biocomposites for 99
34 Arsenic contamination removal of arsenic from aqueous medium. However, the literature survey reveals that very 100
35 Sorption limited attention has been focused on the applications of biocomposites for the removal of 101
36 Polymeric sorbents and arsenic in the past. The sorption capacities of sorbents and LD50 of the arsenic compounds 102
37 103
biocomposites have been compiled.
38 104
Copyright © 2015, The Egyptian Society of Radiation Sciences and Applications. Production
39 105
and hosting by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
40 106
41 (http://creativecommons.org/licenses/by-nc-nd/4.0/).
107
42 108
43 109
44 110
45 111
46 of all poisons (Thakur & Semil, 2013). In natural environment 112
47 1. Introduction 113
arsenic appears in trivalent and pentavalent oxidation states.
48 114
Naturally, arsenic occurs in the Earth's crust (about 0.00005%
49 Arsenic is a steel-gray, brittle, toxic, non-degradable heavy 115
of the earth's crust) which is a major source of water
50 metal, exists in nature in different oxidation states, the most 116
51 contamination. Arsenic leaches to ground water in the form of
frequent oxidation states are
III (arsines), zero (arsenic), þIII 117
52 arsenite (III) and arsenate (V) through weathering of rocks,
(arsenite) and þV (arsenate) (Oremland & Stolz, 2003). Arsenic 118
53 volcanic emissions, biological activities and geochemical re-
119
is a solid crystalline metal with atomic number 33; specific actions (Kanel, Manning, Charlet, & Choi, 2005). Anthropo-
54 120
55 gravity 5.73, and vapor pressure 1 mm-Hg at 372  C (Mohan & genic sources of arsenic contaminations are burning of fossil 121
56 Pittman, 2007). The word arsenic has been derived from the fuels, smelting of metals and massive utilization of arsenical 122
57 Greek word arsenikon, meaning potent which is known as king pesticides (Xie & Huang, 1998). 123
58 124
59 125
60 * Corresponding author. Tel./fax: þ60 104625195. Q2 126
61 E-mail address: kpk566@gmail.com (M. Rahim). 127
62 Peer review under responsibility of The Egyptian Society of Radiation Sciences and Applications. 128
63 http://dx.doi.org/10.1016/j.jrras.2015.03.001
129
64 1687-8507/Copyright © 2015, The Egyptian Society of Radiation Sciences and Applications. Production and hosting by Elsevier B.V. This is an
open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Please cite this article in press as: Rahim, M., & Mas Haris, M. R. H., Application of biopolymer composites in arsenic removal
from aqueous medium: A review, Journal of Radiation Research and Applied Sciences (2015), http://dx.doi.org/10.1016/
j.jrras.2015.03.001
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2 J o u r n a l o f R a d i a t i o n R e s e a r c h a n d A p p l i e d S c i e n c e s x x x ( 2 0 1 5 ) 1 e9

1 During the past two decades arsenic poisoning is of great Bhongsuwan, & Bhongsuwan, 2013). Composites materials 66
2 concern due to its widespread problems (Kapaj, Peterson, consist of matrix and activated component, composites are 67
3 Liber, & Bhattacharya, 2006). Arsenic ground water contami- the superior sorbents due to chemical stability and high me- 68
4 nation has been reported from numerous countries all around chanical properties. Biopolymers such as attapulgit, bentonit 69
5 70
the world. Higher level of arsenic is a big thread for safe and chitosan are the attractive materials for composite sor-
6 71
drinking water and food safety. Long-term exposure to arsenic bents (Porschova & Parschova , 2013).
7 72
may cause lungs, kidneys, urinary tract, liver, skin, buccal The review has been focused on the removal of arsenic
8 73
9 cavity, large intestine, bone and rectum cancers (Guan et al., from aqueous medium via polymeric biocomposites. The 74
10 2012). Non-carcinogenic diseases associated to arsenic over suitability of green, biodegradable, eco-friendly and cost 75
11 exposure are hypertension, diabetes mellitus, hepatomegaly effective sorbents has been reviewed. Our research team has 76
12 and the diseases of peripheral vascular, cerebrovascular and been working to prepare suitable biocomposite materials for 77
13 cardiovascular systems, dysfunction of respiratory system the removal of heavy metals from aqueous medium. 78
14 and injury to central nervous system (Thomas, Styblo, & Lin, 79
15 2001). Drinking water has been considered as a main source 1.1. Arsenic acute toxicity 80
16 to arsenic exposure (Dopp, von Recklinghausen, Diaz-Bone, 81
17 82
Hirner, & Rettenmeier, 2010). Therefore, statutory arsenic Arsenic acute toxicity can significantly increase Glutathione
18 83
permissible limit in drinking water has been reduced from Peroxidase and mitochondrial SOD activities of liver and lungs
19 84
20 0.05 to 0.01 mg/L (Kapaj et al., 2006). The LD50 of the most in rates. The toxic effects have been observed exactly 6 h later 85
21 common arsenic compounds has been summarized in Table the oral dose administration (Shi, Shi, & Liu, 2004). The 86
22 1. increased lactate level, decreased hepatic pyruvate level in the 87
23 Development of treatment technologies for the removal of serum and livers of arsenic exposed rates have been observed. 88
24 arsenic is one of the most important area of wastewater Liver injury along with chlorfenvinphos was found during the 89
25 treatment (Ko
, Furac
sutic
, Sipos, & Kunst, 2005). Various acute intoxication of rates (Leukaszewicz-Hussain & 90
26 techniques have been reported for the removal of arsenic Moniuszko-Jakoniuk, 2004). The acute arsenic LD50 poisoning 91
27 from contaminated water such as ultrafiltration, ion ex- 92
has been reported in the concentration range of 100e300 mg/
28 93
change, coagulation and adsorption (Xu, Nakajima, & Ohki, kg/day. However, the inorganic acute most probable LD50
29 94
2002). The adsorption process is the most suitable technol- amount for humans per day has been estimated 0.6 mg/kg of
30 95
ogy due to simplicity, environment friendliness and cost the body weight. Oral administration of 8 g of arsenic can
31 96
32 effectiveness (Zhang, Yang, & Huang, 2003). Similarly, cause death within eight days (Ratnaike, 2003). 97
33 removal of sorbent is very easy from aqueous media after 98
34 treatment (Xu et al., 2002). Numerous adsorbents have been 1.2. Chronic toxicity and arsenic metabolism 99
35 used such as activated carbon (Chuang et al., 2005), activated 100
36 alumina (Kunzru & Chaudhuri, 2005), sandy soils (Kuhlmeier, Chronic arsenic toxicity can cause cardiovascular diseases, 101
37 1997), hydrous zirconium oxide (Bortun, Bortun, Pardini, 102
hypertension and affects vascular system. Similarly, long
38 Khainakov, & Garcı́a, 2010), lanthanum-loaded silica gel (Xu 103
term arsenic over exposure may cause lungs, kidneys, skin
39 et al., 2002), hematite (Mamindy-Pajany, Hurel, Marmier, & 104
and rectum cancers (Guan et al., 2012), gastrointestinal prob-
40  o, 2009), magnetite, goethite (Gimenez, Martı́nez, de 105
Rome lems, peripheral neuropathy and increased levels of liver en-
41 106
Pablo, Rovira, & Duro, 2007), feldspar and metal-loaded coral zymes (Jomova et al., 2011). Arsenic is one of the most
42 107
43 limestone (Ohki, Nakayachigo, Naka, & Maeda, 1996). How- carcinogenic and genotoxic metal, can cause DNA damage 108
44 ever, biocomposites are the most appropriate materials for and induce hypomethylation and hyper (Vahter & Concha, 109
45 removal of arsenic from aqueous medium (Chomchoey, 2001). Arsenic metabolism is significantly associated with 110
46 111
47 112
48 113
49 Table 1 e Arsenic compounds along with their LD50. 114
50 115
Type of arsenic compounds Rout of administration Species applied Dose/LD50 (mg/kg) References
51 116
52 Arsenic trioxide In vivo Mice 350 (Verstovsek et al., 2006) 117
53 Arsenic trioxide Oral Mice 34.5 (Kaise et al., 1989) 118
54 Indium arsenide Intraperitoneal Mice and Rats 15000 (Flora, 2000) 119
55 Aarsenite Intraperitoneal Hamsters 15 (Hughes et al., 2005) 120
56 Sodium arsenite Intramuscular Mice 9.75 (Kumar, 2007) 121
Sodium arsenite Injection Mice 14.5 (Liu, Liu, Powell, Waalkes, & Klaassen, 2002)
57 122
Sodium arsenite Intraperitoneal Hamsters 15 (Petrick, Jagadish, Mash, & Aposhian, 2001)
58 123
Monomethylarsonic acid Oral Mice 1800 (Hughes et al., 2005)
59 124
Monomethylarsonic acid Intraperitoneal Hamsters 4.10 (Hughes et al., 2005)
60 125
Monomethylarsonous acid Intraperitoneal Hamsters 4.10 (Petrick et al., 2001)
61 126
Methylarsonic acid Oral Mice 1800 (Kaise et al., 1989)
62 Dimethylarsininc acid Oral Mice 1200 (Kaise et al., 1989)
127
63 Dimethylarsinic acid Oral Rat and Mouse 644e1800 (Hughes et al., 2005) 128
64 Trimethylarsine oxide Oral Mice 10,600 (Kaise et al., 1989) 129
65 130

Please cite this article in press as: Rahim, M., & Mas Haris, M. R. H., Application of biopolymer composites in arsenic removal
from aqueous medium: A review, Journal of Radiation Research and Applied Sciences (2015), http://dx.doi.org/10.1016/
j.jrras.2015.03.001
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J o u r n a l o f R a d i a t i o n R e s e a r c h a n d A p p l i e d S c i e n c e s x x x ( 2 0 1 5 ) 1 e9 3

1 the transformation of the toxic-form to less toxic form. The 66

2 conversion of one form to the other has been followed by 67
3 excretion and/or accumulation by the cells (Roy & Saha, 2002). 68
4 Ratnaike (2003) reported that the absorbed arsenic un- 69
5 70
dergoes biomethylation to form dimethylarsinic acid and
6 71
monomethylarsonic acid. The respective acids are compara-
7 72
tively much less toxic and excrete about 50% through urine.
8 73
9 However, dimethylarsinic acid is one of the most dominant 74
10 metabolite excreted via urine along with small quantity of 75
11 unchanged inorganic arsenic. The literature also claimed that 76
12 high concentration has been observed in kidneys and liver 77
13 after acute poisoning. In case of chronic toxicity, the arsenic 78
14 accumulation has been found in kidneys, heart, liver and 79
15 lungs (Ratnaike, 2003). 80
16 81
17 82
18 83
19
2. Biocomposite sorbents 84
20 85
21 Recently, biosorption has becoming an emerging and effective 86
22 wastewater treatment technique (Zhang, Xia, Teng, Liu, & 87
23 Zhang, 2013). The study of biocomposites is one of the most 88
24 attractive research field due to biodegradability and eco- 89
25 friendliness (Wang, Zhu, Yao, & Wilkie, 2002). Biopolymers 90
26 are the basic constituent of biocomposites. Some of bio- 91
27 polymers such as alginate, microalgal, chitin and chitosan 92
28 93
have been studied for the removal of heavy metals. The ad-
29 94
vantages of such materials are their natural abundance, non- Fig. 1 e Structure of chitosan, chitin and cellulose.
30 95
toxicity, environment friendliness and cost effectiveness
31 96
32 (Zhang et al., 2013). 97
oxalic can also form ionic and hydrogen bonding with the
33 reactive functional groups on the skeletal backbone of chito- 98
34 2.1. Chitosan 99
san. Therefore, the uptake of metal ions can be due to ion-
35 100
exchange, sorption and/or chelation processes. The adsorp-
36 Chitosan is a natural, the most abundant, non-toxic and 101
tion of As3þ and As5þ metal ions were conducted at 25  C in
37 biodegradable linear copolymer (Aider, 2010). Chitosan has 102
38 aqueous medium. The sorption capacity of the composite was 103
been derived from chitin which is the main constituent of the
39 found to be 79.4 and 74.6 mg/g of chitosan, respectively for 104
exoskeleton of crustaceans (Raju, Haris, Azura, Baharin, &
40 As5þ and As3þ (Boddu, Smith, & Nano, 2001). 105
Kartini, 2013). Chitin is a natural, second most abundant
41 Veera et al. (2008) studied the effect of pH on the sorption of 106
polymer after cellulose. Chitin, chitosan and cellulose having
42 As5þ and As3þ using the above chitosan/a-alumina bio- 107
43 the same chemical structure the only difference is the N- 108
composite. The sorption of arsenic (V) was found higher than
44 acetyl, amino and hydroxyl functional groups at C-2 position, 109
arsenic (III) at pH 4.0, which was considered as speciation of
45 as shown in Fig. 1 (de Alvarenga, 2011). Chitosan is composed 110
arsenic. Bed volume of 40e120 has completely removed
46 of b(1 / 4)-linked D-glucopyranosamine repeating units. 111
arsenic (As5þ and As3þ) at the concentration of 100 ppm. The
47 Chitosan is one of the eco-friendly natural polymer, recom- 112
column bed can be regenerated using 0.1 M sodium hydroxide
48 mended for biomedical and agricultural applications (Mas 113
solution (Boddu, Abburi, Talbott, et al., 2008). Veera et al. (2008) Q3
49 Haris & Raju, 2014). Chitosan is a biodegradable and non- 114
50 prepared the same composite for the removal of copper (II) 115
toxic biopolymer with LD50  16 g/kg in mice
51 and nickel (II) ions. Although, the present review is concerning 116
(Mukhopadhyay, Mishra, Rana, & Kundu, 2012).
52 with the removal of arsenic from contaminated water (Boddu, 117
53 Abburi, Randolph, et al., 2008). 118
2.2. Chitosan/a-alumina composite
54 119
55 120
56 The adsorption properties of alumina have been widely 2.3. Manganese copper ferrite/polymer (AA, MA, VA) 121
57 recognized due to acidebase dissociation which leads to sorb composite 122
58 positive as well as negative ions dependent on pH of the me- 123
59 dium (Wan Ngah, Teong, & Hanafiah, 2011). Limited work has Polymers, acrylic acid (AA), methylacrylate (MA) and vinyl 124
60 been carried out on this composite to remove metal ions from acetate (VA) have been used widespread for numerous appli- 125
61 contaminated water (Boddu, Abburi, Talbott, et al., 2008). cations. However, the introduction of AA into the polymeric 126
62 Veera et al. (2001) prepared chitosan/a-alumina biocomposite, biocomposites at the time of preparation provides an anionic 127
63 128
partial size 100e150 mm, surface area 105.2 m2/g, pore volume character to the composite materials (Martinez-Rubio,
64 129
0.187 cm3/g and pore diameter about 71.2 Å. The process is Ireland, Fern, Silver, & Snowden, 2001). Malana, Qureshi, and
65 130
based on the crosslinking of chitosan via oxalic acid however, Ashiq (2011) prepared aluminum doped manganese copper

Please cite this article in press as: Rahim, M., & Mas Haris, M. R. H., Application of biopolymer composites in arsenic removal
from aqueous medium: A review, Journal of Radiation Research and Applied Sciences (2015), http://dx.doi.org/10.1016/
j.jrras.2015.03.001
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4 J o u r n a l o f R a d i a t i o n R e s e a r c h a n d A p p l i e d S c i e n c e s x x x ( 2 0 1 5 ) 1 e9

1 ferrite/AAeMAeVA composite by chemical co-precipitation. characterized for composition and morphology by FTIR and 66
2 The composites were used for the removal of arsenic from SEM. Point of zero charge (PZC) and nitrogen adsorption at 67
3 aqueous medium. The sorption capacity of the composite was
196  C were investigated in order to determine the suitable 68
4 found to be 0.053 mg/g of the composite. The sorption energy pH range for the sorption of cations (As5þ and As3þ). The effect 69
5 70
was found to be 40.98 kJ/mol which was greater than standard of arsenic initial concentration, contact time, temperature
6 71
value (16 kJ/mol), confirms chemisorption phenomenon and pH were studied and optimized finally. The maximum
7 72
(Malana et al., 2011). However, chloroform was used in the sorption capacity was found to be 66.7 mg/g of the composite
8 73
9 preparation process as porogen which is toxic and causes at 30  C (Hassan et al., 2014). 74
10 numerous environmental and health complications (Lilly, 75
11 Ross, & Pegramt, 1997). 76
12 3. Discussions and future challenges 77
13 2.4. Thiol functionalised polyacrylamide based cryogel 78
14 composite Biopolymers are the most attractive natural materials, re- 79
15 searchers have been encouraged due to non-toxicity, biode- 80
16 Polyacrylamide (PAA) is a homopolymer of acrylamide gradability and environment friendliness. From the literature, 81
17 82
repeating units. PAA is a water soluble polymer, has been used it has been concluded that natural polymer should be used for
18 83
to improve soil stabilization. The formulation of PAA with a the removal of heavy metals particularly arsenic. The litera-
19 84
20 copolymer can produces specific charges which gives PAA ture summarized in Table 2, indicates that arsenic (III) sorp- 85
21 several characteristics (Green & Stott, 1999). Onnby, Pakade, tion capacity of Chitosan zerovalent Iron Nanoparticles 86
22 Mattiasson, and Kirsebom (2012) prepared thiol functional- (Gupta, Yunus, & Sankararamakrishnan, 2012) have been 87
23 ised cryogel composite by polymerization of polyacrylamide found to be 99.98% greater than Clinoptilolite-rich tuff, 99.97 88
24 based cryogel followed by coupling of SH-groups to the poly- (Waste materials; Atlantic Cod fish scale), 99.97 (Slag-iron 89
25 merized cryogel skeletal backbone. Polymerization was taken oxideeTiO2), 99.97 (Iron oxide-coated sand), 99.81 (Laterite 90
26 place at
12  C in a LAUDA thermostat for 24 h. The maximum soil), 99.80 (Scoria), 99.79 (Hematite), 99.71 (Acidithiobacillus 91
27 sorption capacity of the composite was found to be ferrooxidans BY-3), 99.30 (Red mud), 99.27 (Iron oxide coated 92
28 93
20.3 ± 0.8 mg/g of the sorbent in the pH range of 2e8 (Onnby cement), 99.21 (Polymetallic sea nodule), 99.06 (Biomass;
29 94
et al., 2012). Momordica charantia), 98.92 (Activated carbon), 98.72 (Activated
30 95
bauxite), 96.91 (Polymer/inorganic fibrous sorbent), 96.07
31 96
32 2.5. Fe3O4/HBC composite (Magnetiteemaghemite nanoparticles), 84.36 (Natural Fe and 97
33 Mn enriched sample), 82.82 (Ironechitosan composites), 80.64 98
34 Baig et al. (2014) reported the successful preparation of Fe3O4/ (Nano zero-valent Fe), 77.12 (PVDF/zirconia blend), 65.53 99
35 HBC (honeycomb briquette cinders) composite for the removal (TiO2), 44.78 (Fungus biomass; Inonotus hispidus) and 9.57% 100
36 of arsenic from contaminated water. The in situ chemical co- greater than Ironetitanium binary mixed oxide. 101
37 precipitation method was used for composite preparation at The sorption arsenic (V) capacity of Chitosan derivatives 102
38 temperature range of 400e1000  C in the presence of air ni- (Gupta, Chauhan, & Sankararamakrishnan, 2009) has been 103
39 trogen. The effect of pH, temperature, contact time and initial found to be 99.98% greater than Waste materials (Atlantic Cod 104
40 105
concentration of arsenic on the sorption capacity of the fish scale), 99.91 (Hematite), 99.85 (A. ferrooxidans BY-3), 99.82
41 106
composite was investigated. Characterizations such as FTIR, (Natural iron ores), 99.78 (Clinoptilolite-rich tuff), 99.77 (Red
42 107
43 BET, SEM, XRD and HT-XRD were performed for the composite mud), 99.77 (Illite), 99.72 (Montmorillonite), 99.67 (Polymetallic 108
44 in order to determine the structure and morphology of the sea nodule), 99.62 (Kaolinite), 99.52 (Granular ferric hydrox- 109
45 synthesized composite. The maximum sorption capacity of ide), 98.38 (Magnetiteemaghemite nanoparticles), 98.30 (He- 110
46 the composite was found to be and 3.07 mg/g and 3.35 mg/g, matite), 97.81 (Activated bauxite), 96.30 (Natural Fe and Mn 111
47 respectively of As (III) and As (V) in the pH range of 4e10. enriched sample), 95.97 (Modified sawdust of spruce), 94.78 112
48 However, high temperature treatment discourages method of (Nano zero-valent Fe), 94.74 (Metal oxide nanomaterials), 93.78 113
49 biocomposite preparation (Baig et al., 2014). (Ironetitanium binary mixed oxide), 87.92 (Activated carbon), 114
50 84.86 (Synthetic zeolites H-MFI-90), 84.43 (Synthetic zeolites 115
51 116
2.6. Calcium alginate/activated carbon composite H-MFI-24), 82.00 (TiO2), 79.56 (Ultrafine a-Fe2O3 nanoparticles),
52 117
74.84 (Modified fungal biomass), 74.08 (Fungus biomass; I.
53 118
Alginate, a polysaccharide, derived from brown algae, intra- hispidus), 69.39 (Ce(IV)-doped iron oxide), 61.73 (Zr(IV)-loaded
54 119
55 cellular matrix and some bacteria (Gombotz & Wee, 2012), is a orange waste gel), 47.82 (Akaganeite-type nanocrystals) and 120
56 linear polymer of b(1 / 4)-linked D-mannuronic acid (M) and 11.21% greater than Fe3O4-loaded activated carbon. The above 121
57 a-L-guluronic acid (G) residues (Rowley, Madlambayan, & discussions clearly indicate that encapsulation and/or 122
58 Mooney, 1999). Aqueous solution of sodium-alginate can impregnation of active inorganic materials by biopolymers are 123
59 form insoluble calcium-alginate by the addition of Ca2þ (Kim the most appropriate materials towards adsorption and 124
60 & Lee, 1992). Alginate is an environment friendly polymer, removal of heavy metals including arsenic. 125
61 used for the encapsulation and entrapment techniques The literature comparison of polymeric sorbents with the 126
62 (Smidsrød, 1990). most commonly used materials such as activated carbon 127
63 128
Hassan, Abdel-Mohsen, and Elhadidy (2014) used Calcium (Budinova et al., 2009) and TiO2 (Bang, Patel, Lippincott, &
64 129
alginate/activated carbon composite beads for the sorption Meng, 2005) have been indicated that Chitosan zerovalent
65 130
and removal of arsenic (V). The composite materials were Iron Nanoparticle (Gupta et al., 2012) has 98.92 and 65.53%

Please cite this article in press as: Rahim, M., & Mas Haris, M. R. H., Application of biopolymer composites in arsenic removal
from aqueous medium: A review, Journal of Radiation Research and Applied Sciences (2015), http://dx.doi.org/10.1016/
j.jrras.2015.03.001
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1 66
Table 2 e Sorption capacity of different sorbents.
2 67
3 Type of compounds Initial Surface area pH Sorption Sorption References 68
4 conc: (m2/g) capacity As capacity As 69
5 mg/L (III) mg/g (V) mg/g 70
6 Chitosan-coated biosorbent 100 125.24 4.0 56.50 96.46 (Boddu, Abburi, Talbott, Smith, & 71
7 Haasch, 2008) 72
8 Ironechitosan composites 0.5 7 16.15 22.47 (Gupta et al., 2009) 73
9 Chitosan derivatives 20 2e3 70 230 (Dambies et al., 2002) 74
10 Chitosan zerovalent iron 1 69 7 94 119 (Gupta et al., 2012) 75
11 nanoparticle 76
12 Polymer/inorganic fibrous 0.01 7.7 2.9 (Vatutsina et al., 2007) 77
13 sorbent 78
14 Zr(IV)-loaded orange waste gel 20 7.25 9e10 130 88 (Biswas et al., 2008) 79
15 Biomass (Momordica charantia) 0.5 2e11 0.88 (Pandey, Choubey, Verma, Pandey, 80
16 & Chandrashekhar, 2009) 81
17 Modified sawdust of spruce 20e500 8 9.259 (Urik, Littera, & Kolen, 2009) 82
(Picea abies)
18 83
Fungus (Inonotus hispidus) 10e500 6 51.9 (Sarı & Tuzen, 2009)
19 84
biomass
20 85
Fungus (Inonotus hispidus) 10e500 2 59.6 (Sarı & Tuzen, 2009)
21 86
biomass
22 87
Modified fungal biomass 1e300 3 57.85 (Loukidou, Matis, Zouboulis, &
23 Liakopoulou-Kyriakidou, 2003)
88
24 Waste materials (Atlantic 0.2e1 4.0 0.02475 0.02667 (Rahaman, Basu, & Islam, 2008) 89
25 Cod fish scale) 90
26 Clinoptilolite-rich tuff 0.1e4 4 0.014 0.5 (Elizalde-Gonza  lez, Mattusch, 91
27 Wennrich, & Morgenstern, 2001) 92
28 Akaganeite-type nanocrystals 20 330 7.5 120 (Deliyanni, Bakoyannakis, 93
29 Zouboulis, & Matis, 2003) 94
30 PVDF/zirconia blend 1 3e8 21.5 (Zheng, Zou, Nanayakkara, 95
31 Matsuura, & Chen, 2011) 96
32 TiO2 0.4e80 250.7 7 32.4 41.4 (Bang et al., 2005) 97
33 TiO2 44.95 330 7 37.46 (Pena, Korfiatis, Patel, Lippincott, & 98
34 Meng, 2005) 99
35 Slag-iron oxideeTiO2 100 163 3 0.0256 (Zhang & Itoh, 2006) 100
36 Activated carbon 5 26e1313 7 27.78 (Yürüm et al., 2014) 101
37 Activated carbon 5e20 258 10.7 1.01 (Budinova et al., 2009) 102
Fe3O4-loaded activated carbon 40 349 8.0 204.2 (Liu, Zhang, & Sasai, 2010)
38 103
Activated bauxite 1.20 5.02 (Soner Altundog  an, Altundog  an,
39 104
Tümen, & Bildik, 2000)
40 105
Hematite 0.20 3.90 (Soner Altundog  an et al., 2000)
41 106
Hematite 1 3e10 0.202 (Guo, Stüben, & Berner, 2007)
42 107
Laterite soil 0.33 7.2 0.18 (Maji, Pal, & Pal, 2008)
43 Kaolinite 10 33 2e5 0.86 (Mohapatra, Mishra, Chaudhury, &
108
44 Das, 2007) 109
45 Montmorillonite 10 58 2e5 0.64 (Mohapatra et al., 2007) 110
46 Illite 10 28 2e5 0.52 (Mohapatra et al., 2007) 111
47 Synthetic zeolites H-MFI-24 0.5e2 450 6.35 35.8 (Chutia, Kato, Kojima, & Satokawa, 112
48 (H24) 2009) 113
49 Synthetic zeolites H-MFI-90 0.5e2 400 3.15 34.8 (Chutia et al., 2009) 114
50 (H90) 115
51 Iron oxide coated cement 0.7e13.5 3.2e12 0.73 (Kundu & Gupta, 2006) 116
52 (IOCC) 117
53 Iron oxide coated cement 1 7 0.69 (Kundu & Gupta, 2007) 118
54 (IOCC) 119
55 Granular ferric hydroxide (GFH) 240e300 6.5e7.5 1.1 (Banerjee et al., 2008) 120
56 Ironetitanium binary mixed 5e10 7.0 85 14.3 (Gupta & Ghosh, 2009) 121
57 oxide 122
Natural iron ores (RM 12318) 1 30 4.5e6.5 0.4 (Zhang, Singh, Paling, & Delides,
58 123
2004)
59 124
Iron oxide-coated sand 0.1 7.5 0.02857 (Gupta, Saini, & Jain, 2005)
60 125
Nano zero-valent Fe 2 69.4 6.5 18.2 12.0 (Zhu, Jia, Wu, & Wang, 2009)
61 126
Natural Fe and Mn enriched 0.1 40.8e17.1 3 14.7 8.5 (Deschamps, Ciminelli, & Ho € ll,
62 127
sample 2005)
63 Ultrafine a-Fe2O3 nanoparticles 162 95 47 (Tang, Li, Gao, & Shang, 2011)
128
64 129
65 (continued on next page) 130

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1 66
Table 2 e (continued )
2 67
3 Type of compounds Initial Surface area pH Sorption Sorption References 68
4 conc: (m2/g) capacity As capacity As 69
5 mg/L (III) mg/g (V) mg/g 70
6 Ce(IV)-doped iron oxide 1 90 5.0 70.4 (Zhang et al., 2003) 71
7 Magnetiteemaghemite 1.5 49 2 3.69 3.71 (Chowdhury & Yanful, 2010) 72
8 nanoparticles 73
9 Acidithiobacillus ferrooxidans BY- 0.5e3 2.0e8.0 0.27722 0.32385 (Yan et al., 2010) 74
10 3 75
11 Metal oxide nanomaterials 0.1 50e150 6.7e8.4 1.3e12.09 (Hristovski, Baumgardner, & 76
12 Westerhoff, 2007) 77
13 Scoria 7.49e74.92 5.0 0.19 (Kwon, Yun, Lee, Kim, & Jo, 2010) 78
14 Polymetallic sea nodule 0.34 5.9e6.1 0.74 (Maity, Chakravarty, 79
15 Bhattacharjee, & Roy, 2005) 80
16 Polymetallic sea nodule 0.78 2.0e2.2 0.74 (Maity et al., 2005) 81
Red mud 1.103 9.5 0.66 (Soner Altundog  an et al., 2000)
17 82
Red mud 12.833 3.2 0.51 (Soner Altundog  an et al., 2000)
18 83
19 84
greater sorption capacity towards arsenic (III), respectively. Academy of Sciences) for TWAS-USM fellowship, {TWAS-FR.
20 85
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Arsenic removal from aqueous solutions using Fe3O4eHBC
34 terials. Our research group has been looking for the prepara- composite: effect of calcination on adsorbents performance. 99
35 tion of polymeric biocomposites and its applications in PLoS One, 9, e100704. 100
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44 promising alternative of the conventional sorbents. Ohto, K., et al. (2008). Adsorptive removal of As(V) and As(III) 109
45 from water by a Zr(IV)-loaded orange waste gel. Journal of 110
Numerous polymers can be used for this purpose. However,
Hazardous Materials, 154, 1066e1074.
46 chitosan has been considered as one of the most appropriate 111
Boddu, V. M., Abburi, K., Randolph, A. J., & Smith, E. D. (2008).
47 biopolymer due to non-toxic, biodegradable and environment 112
Removal of copper (II) and nickel (II) ions from aqueous
48 113
friendly properties. Chitosan biocomposites can be formu- solutions by a composite chitosan biosorbent. Separation
49 114
lated with other polymeric and/or activated inorganic mate- Science and Technology, 43, 1365e1381.
50 115
rials via impregnation, encapsulation, coating and/or Boddu, V. M., Abburi, K., Talbott, J. L., Smith, E. D., & Haasch, R. (2008).
51 Removal of arsenic (III) and arsenic (V) from aqueous medium 116
52 polymerization techniques. The first protonation of amino 117
using chitosan-coated biosorbent. Water Research, 42, 633e642.
53 group (present at the polymer backbone) undergoes followed 118
Boddu, V. M., Smith, E. D., & Nano, G. (2001). Adsorption of arsenic
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55 static interactions. The review suggests that this field of biosorbent. Bridges, 10, 418. 120
56 research has enough space which should be covered in the Bortun, A., Bortun, M., Pardini, J., Khainakov, S. A., & Garcı́a, J. R. 121
57 near future and hopefully the laboratory scale research should (2010). Effect of competitive ions on the arsenic removal by 122
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62 Acknowledgment
carbon for the removal of arsenic and manganese ions from 127
63 aqueous solutions. Applied Surface Science, 255, 4650e4657. 128
64 Chomchoey, N., Bhongsuwan, D., & Bhongsuwan, T. (2013). 129
Q4 The author would like to acknowledge Universiti Sains Arsenic removal from synthetic wastewater by activated
65 130
Malaysia, Pulau Penang, Malaysia and TWAS (The World carbonemagnetic nanoparticles composite.

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Please cite this article in press as: Rahim, M., & Mas Haris, M. R. H., Application of biopolymer composites in arsenic removal
from aqueous medium: A review, Journal of Radiation Research and Applied Sciences (2015), http://dx.doi.org/10.1016/
j.jrras.2015.03.001