ABSTRACT

The presence of arsenic in waters, especially groundwater, has become a worldwide problem in the past decades. High arsenic concentrations have been reported recently from the USA, China, Chile, Bangladesh, Taiwan, Mexico, Argentina, Poland, Canada, Hungary, Japan and India. Among 21 countries in different parts of the world affected by groundwater arsenic contamination, the largest population at risk is in Bangladesh followed by West Bengal in India. This report provide a brief review on various arsenic removal methods, which include coagulation followed by precipitation, membrane separation, anion exchange, etc. The use of low-cost biosorbent obtained from an environmentally friendly materials, has been investigated as a replacement for the current expensive methods of removing arsenic from solution. Desorption of arsenic followed by regeneration of sorbents has also been discussed. Key words: Arsenic speciation, methods of arsenic removal, low-cost biosorbents, desorption.

ARSENIC IN AQUEOUS SOLUTION: Arsenic exists in both organic and inorganic forms in nature.Inorganic arsenic is mostly found in natural water systems. Inorganic arsenic is more toxic than organic arsenic. Generally, inorganic arsenic has two different oxidation states, that is, trivalent and pentavalent, in natural aqueous systems (Elizalde3 3 Gonzalez et al., 2001; Chutia et al., 2009).These two forms are: arsenite (AsO3 ) and arsenate (AsO4 ). 3 2 Pentavalent (+5) or arsenate species are: AsO4 , HAsO4 , H2AsO4 , 3 while trivalent (+3) arsenates include: As(OH)3, As(OH)4 , AsO2(OH)2 and AsO3 . Pentavalent species predominate and are stable in oxygen rich aerobic environments. Trivalent arsenites predominate in moderately reducing anaerobic environments such as groundwater. Here is a chart showing various forms and species of arsenic :-

ARSENIC

INORGANIC
(MORE ABUNDANT IN NATURAL WATER SYSTEM)

ORGANIC
(LESS TOXIC)

ARSENITES
DOMINANT FORMS IN AQUEOUS MEDIUM.

(TRIVALENT)

PREDOMINAT IN REDUCING ENVIRONMENT

ARSENATES (PENTAVALENT)

PREDOMINANT IN OXIDISING ENVIRONMENT

ARSHINE GAS

ELEMENTAL ARSENIC

TABLE 1: Deprotonation of arsenic species in solution (Cherry et al.,1979 ; Wee, 2003). SPECIES As(V)

+ +

pKa = 2.2

pKa = 6.96
pKa = 11.5 pKa = 9.32 pKa = 12.1 pKa = 13.41

As(III)

+ + + +

Where: the dissociation constant (pKa) is an equilibrium constant and logarithmic measure of the strength of an acid in solution.

FACTORS AFFECTING ARSENIC SPECIFICATIONS: Redox potential (Eh) and pH are the most important factors controlling speciation of arsenic . Influence of pH: Under oxidizing conditions at pH less than 6.9, H2AsO4 is the dominant species, and at higher pH, 2 HAsO4 becomes dominant. Under reducing conditions at pH less than 9.2, the uncharged arsenite species is dominant. (Chiban et al. ,2011). Figure 1 a:

Figure 1 b:

Influence of Eh: Eh measures the reducing potential of a given chemical species. The combined effect of Eh and pH can be studied from the Pourbaix diagram, as shown below: Figure 2 :

CONVENTIONAL METHODS OF ARSENIC REMOVAL: Some of the methods of arsenic removal from aqueous solution is as follows : Coagulation:

In arsenic removal processes, coagulation and flocculation are among the most common method. Although the terms coagulation and flocculation are often used interchangeably , they are, in fact, two distinct processes. Coagulation is the destabilization of colloids by neutralizing the forces that keep them apart. Cationic coagulants provide positive electric charges to reduce the negative charge of the colloids. As a result, the particles collide to form larger particles. Rapid mixing is required to disperse the coagulant throughout the liquid. Flocculation is the action of polymers to form bridges between the larger mass particles or flocs and bind the particles into large agglomerates or clumps. Bridging occurs when segments of the polymer chain adsorb on different particles and help particles aggregate. An anionic flocculant will react against a positively charged suspension, adsorbing on the particles and causing destabilization either by bridging or charge neutralization (Choong et al., 2007). Pre-oxidation of arsenite to arsenate is required in all coagulation process as precipitated As(V) is more stable than As(III).(Fetter, 1999; Leist et al., 2000; Selvin et al., 2002). Two types of coagulants are generally used: I. Aluminium based (alum) II. Iron based Aluminium-based coagulation with disinfection by chlorination is one of the commonly used treatment methods (McNeill and Edwards ,1995). In case of iron, many coagulants have been reported.Some Iron based coagulants which already have been studied are :

TABLE 2:

Coagulants Ferric sulphate Ferric chloride and lime-polyferric sulphate. Ferric chloride and ferric sulphate.

Reference Yuan et al. (2003) Karcher et al. (1999) and Guo et al. (2000) Han et al. (2002)

Remarks Method is economical and effective.

Removal is mostly by adsorption mechanism onto ferric complexes.

Ferric salts have been found to be more effective in removing arsenic than alum on a weight basis and it is effective over a wider pH range (Cheng et al., 1994; Hering et al., 1997).

Lime softening : Lime softening is used to reduce hardness from the water systems. The same process can be enhanced for arsenic removal. To remove As(V), additional lime is added to increase the pH value above 10.5 units. In this range magnesium hydroxide precipitates and As(V) is removed by co-precipitation with it. As(V) removal by co-precipitation with calcium carbonate (i.e., below a pH of 10.5) is poor (less than 10%).(Fields et al., 2000), (Jain and Singh , 2012). Oxidation: Oxidation followed by filtration is generally used for the removal of iron and manganese from water. The processes involve the oxidation of soluble forms of iron and manganese to their insoluble forms and then removal by filtration. If arsenic is present in the water, it can be removed via two primary mechanisms: I. II. adsorption and co-precipitation

In case of co-precipitation with iron:

Oxidation of iron and As(III).

Adsorbtion of As(V) onto iron hydroxide precipitate.

Removal by filtration.

The arsenic removal efficiency is strongly dependent on: I. II. the initial iron concentration and the ratio of iron to arsenic.

In general, the Fe:As mass ratio should be at least 20:1. These conditions customarily result in an arsenic removal efficiency of 80 to 95%.The effectiveness of arsenic co-precipitation with iron is relatively independent of source water if pH is in the range 5.5 to 8.5.(Fields et al., 2000), (Jain and Singh , 2012).

Numerous authors have also described removal of arsenic by chemical oxidation and sorption onto manganese oxides (Edwards,1994; Driehaus et al., 1995; Bajpai and Chaudhuri, 1999; Oscarson et al., 1983; Moore et al., 1990; Scott and Morgan, 1995; Nesbitt et al., 1998; Manning et al., 2002; Tournassat et al., 2002). Since, manganese dioxides are capable of oxidizing As(III), it has been successfully used for removal of arsenic by chemical oxidation and sorption onto manganese oxides.

Ion exchange Ion exchange is a physical-chemical process in which ions are swapped between a solution phase and solid resin phase. The solid resin is typically an elastic three-dimensional hydrocarbon network containing a large number of ionizable groups electrostatically bound to the resin. These groups are exchanged for ions of similar charge in solution that have a stronger exchange affinity for the resin. In drinking water treatment, this technology is commonly used for softening and nitrate removal. The technology typically can reduce arsenic concentrations to less than 50 mg L_1 and in some cases to below 10 mg L_1. Its effectiveness is sensitive to a variety of untreated water contaminants and characteristics. (Jain and Singh , 2012).

Flowchart Membrane filtration Some synthetic membranes are permeable to certain dissolved compounds but exclude others. Because of their selective permeability for different compounds, such membranes can act as a molecular filter to remove dissolved arsenic, along with many other dissolved and particulate compounds. High pressures are required to cause water to pass across the membrane from a concentrated to dilute solution. For this reason membrane separation is addressed as a pressure driven process. (Chiban et al. ,2011).

Pressure driven processes are commonly divided into four overlapping categories: I. II. III. IV. microfiltration (MF) ultrafiltration (UF) nanofiltration (NF) and hyperfiltration or reverse osmosis (RO).

A brief summary of all the four processes has been described below:TABLE 3: PROCESS USED FOR PARTICLES OF PORE SIZE 0.1 to 1 micron 0.003 to 0.1 micron 0.001 to 0.003 micron REQUIRED PRESSURE 5-100 psi 5-100 psi 50-150 psi REMARKS

Microfiltration(MF) Ultrafiltration(UF) Nanofiltration (NF)

Reverse osmosis(RO)

About 0.005

50-150 psi

used to remove bacteria and suspended solids. remove colloids, viruses and certain proteins . relies on physical rejection based on molecular size and charge. can be used for desalination.

(Chiban et al. ,2011),(Jain and Singh , 2012). Flowchart Oh et al. (2000) applied reverse osmosis and nanofiltration membrane processes for the treatment of arsenic contaminated water applying low pressure by bicycle pump. A nanofiltration membrane process coupled with a bicycle pump could be operated under condition of low recovery and low-pressure range from 0.2 to 0.7 MPa.

DISADVANTAGES OF CONVENTIONAL METHODS OF ARSENIC REMOVAL

TABLE 4: METHODS Coagulation DISADVANTAGES The safe separation, filtration, and the handling and disposal of the contaminated coagulant sludge is difficult . Lowering of arsenic to acceptable level is difficult in many cases. Low efficiency in removal of arsenic as compare to the total sludge generated. Process are significantly affected by the pH and the presence (or absence) of chlorine. High levels of organic mater, orthophosphates and silicates weaken arsenic removal efficiency by competing for sorption sites on iron hydroxide precipitates Efficiency of the process depends strongly on the solution pH and the concentration of other anions, most notably sulfates and nitrates. High levels of total dissolved solids (TDS) can also adversely affect the performance of an Ion Exchange system. Higher treatment cost compare to other treatment technologies. The systems are more costly than other treatment methods. Produces a larger volume of residuals. Consume large amounts of water REFERENCES Chiban et al , 2011

I.

II.

Lime softening

I.

Jain and Singh , 2012

II.

Oxidation

Fields et al., 2000

Ion exchange

I.

Jain and Singh , 2012

II.

III.

I. Membrane filtration II. III.

Jain and Singh , 2012 and Choong et al., 2007.

Adsorption of Arsenic: Adsorption is a process that uses solids for removing substances from either gaseous or liquid solutions. Such phenomena are operative in most natural physical, biological, and chemical systems. A related term is absorption which differs from adsorption by being a bulk phenomenon, where as adsorption is a surface phenomenon. Both the term adsorption and absorption is together known as sorption. Most of the processes are in general sorption in nature, i.e , adsorption and absorption both occurs simultaneously. The process of adsorption involves separation of a substance from one phase accompanied by its accumulation or concentration at the surface of another. Physical adsorption is caused mainly by van der Waals forces and electrostatic forces between adsorbate molecules and the atoms which compose the adsorbent surface. The effectiveness of adsorption depend upon presence of various untreated contaminants in water. As the contaminated water is passed through the column containing adsorbents, contaminants are adsorbed. When adsorption sites become filled, the column must be regenerated or disposed of and replaced with new media. (Mohan and Pittman , 2007 ), (Chiban et al. ,2011),(Jain and Singh , 2012). Various kinds of adsorbents like commercial activated carbons, clays, zeolites, ion exchange , chelating resins, and biosorbents are in use. All these adsorbents can be broadly divided into two classes : I. II. High cost adsorbents Low cost adsorbents.

High cost adsorbents High cost adsorbents includes Commercial and synthetic activated carbons. Activated carbon is also commonly used as the material in arsenic treatment (Wennrich and Weiss, 2004; Huang and Fu, 1984; Gimbel and Hobby, 2000).Activated carbon is a crude form of graphite with a random or amorphous highly porpus structure with a broad range of pore sizes,from visible cracks and crevices, to crevices of molecular dimensions .(Hamerlinck and Mertens 1994). Adsorption capacity depends on : I. activated carbon properties, II. adsorbate chemical properties, III. temperature, IV. pH etc. (Chiban et al. ,2011), (Mohan and Pittman , 2007 ), Activated carbon can be produced by two process: I. Physical reactivation: This is generally done by using one or a combination of the following processes: a. Carbonization: Material with carbon content is pyrolyzed at temperatures in the range 600900 C, in absence of oxygen (usually in inert atmosphere with gases like argon or nitrogen) b. Activation/Oxidation: Raw material or carbonized material is exposed to oxidizing atmospheres (carbon dioxide, oxygen, or steam) at temperatures above 250 C, usually in the temperature range of 6001200 C.

II.

Chemical activation: Prior to carbonization, the raw material is impregnated with certain chemicals. The chemical is typically an acid, strong base, or a salt(phosphoric acid, potassium hydroxide, sodium hydroxide, calcium chloride, and zinc chloride 25%). Then, the raw material is carbonized at lower temperatures (450900 C). It is believed that the carbonization / activation step proceeds simultaneously with the chemical activation. Chemical activation is preferred over physical activation owing to the lower temperatures and shorter time needed for activating material.

Different methods of using activated charcoal for arsenic removal has been studied. These are as follows: Lorenzen et al. ,1995 concluded that Carbon pretreatment with Cu(II) improves the arsenic removal capacity of activated carbon. Arsenic formed insoluble metal arsenates with the impregnated copper. Arsenic is also simultaneously adsorbed by carbon independently. Activated carbon impregnated with metallic silver and copper shows better arsenic removal efficiencies. Jubinka et al. , 1992 A combination of granular activated carbon and carbon steel wool removed arsenic from water. The adsorption ability of the steel wool was due to ironarsenic electrochemical reactions. Campos, 2002 Gu et al., 2005 developed iron-containing granular activated carbon adsorbents (As-GAC) for arsenic removal from drinking water. Granular activated carbon (GAC) was a support for ferric ions that were impregnated using aqueous ferrous chloride (FeCl2) followed by NaClO chemical oxidation. Chuang et al.,2005 studied the efficiency of As(V) adsorption by activated carbon (AC) produced from oat hulls. Adsorption capacity decreased from 3.09 to 1.57 mg As g1 when the initial pH increased from 5 to 8. Daus et al., 2004 studied As(III) and As(V) adsorption onto five different sorbents [activated carbon (AC), zirconium-loaded activated carbon (Zr-AC), a sorption medium with the tradename Absorptionsmittel 3 (AM3), zero-valent iron (Fe), and granulated iron hydroxide (GIH)]. The sorption of arsenate followed the sequence : Zr-AC>>GIH=AM3>Fe >AC. A different order was found for arsenite: AC>>Zr-AC=AM3= GIH = Fe. Peraniemi et al. , 1994 used zirconium-loaded activated carbon and successfully removed arsenic, selenium, and mercury. Arsenic(III) was also removed from aqueous solution (concentration range of 520 mg/L) by activated carbons developed from olive stones and solvent-extracted olive pulp. Budinova et al. , 2006.

Low cost adsorbents: In the adsorption process activated carbon is most popular and widely used adsorbent in wastewater treatment throughout the world, but the high prices and regeneration cost of activated carbon limits their large-scale use for the removal of arssenic, and has encouraged researchers to look for low cost adsorbing materials (Bailey et al., 1999). Numerous low-cost adsorbents have so far been studied for the removal of arsenic from water and wastewater. Dry plants, red mud, fly ash, zeolites, hydroxides and various bioadsorbents are few to mention. Removal of heavy metals by these materials might be attributed to their protein, carbohydrates and phenolic compound contents, which have metal-binding functional groups such as carboxyl, hydroxyl, sulfate, arsenate and amino groups. (Chiban et al. ,2011), (Mohan and Pittman , 2007 ).

Below shows several of natural materials that have been used as adsorbents for arsenic removal: 1) Industrial by-products/wastes Red mud : Red mud is a waste material formed during the production of alumina when bauxite ore is subjected to caustic leaching. A typical Bayer process plant generates a 12 tonnes of red mud per ton of alumina produced. (Mohan and Chander , 2006). Mineralogically, red mud consists mainly of different forms of iron and aluminum oxide minerals, calcium and sodium aluminum silicates, various titanium compounds, etc. Oxidic constituents are undissolved part of bauxite whereas silicates are formed from dissolved silica and alumina during desilication of aluminate liquors. (Altundogan et al., 2000). In a test carried out by Altundogan et al., 2000 following results were obtained: An alkaline aqueous medium (pH 9.5) favored As(III) removal, whereas the acidic pH range (1.13.2) was effective for As(V) removal. The capacities were 4.31 mol g1 at the pH of 9.5 for As(III) and 5.07 mol g1 at the pH of 3.2 for As(V).

Seawater-neutralized red muds (Bauxol) : Seawater-neutralized red mud (not activated) was prepared by suspending the red mud in the seawater solution and stirring until equilibrium pH was achieved. The following results were obtained during adsorption on Bauxol: Adsorption increased with decreasing pH, higher adsorbent dosages, and lower initial arsenate concentrations. The sorption capacity of this Bauxsol was 14.43 mol g1.(McConchie et al. , 2004).

Blast furnace slag : Steel plants generate a large volume of granular blast furnace slag. It has been used as a effective and economical adsorbent for the removal of aqueous arsenic. Zhang and Itoh , 2005 synthesized an adsorbent for aqueous arsenic removal by loading iron(III) oxide onto melted municipal solid waste incinerator slag. The simultaneous generation of amorphous hydrous ferric oxide sol and a silica sol in situ eventually led to the formation of FeSi surface complexes which tightly bonded the iron oxide to the slag. For comparison, amorphous hydrous ferric oxide was also prepared. The results shows that: This adsorbent effectively removed both arsenate and arsenite, exhibiting removal capacities for As(V) and As(III) 2.5 and 3 times of those of amorphous hydrous ferric oxide, respectively. Zhang and Itoh , 2005 also used photocatalytic oxidation of arsenite and removal using slag iron oxideTiO2 adsorbent. The oxidation of arsenite was rapid, but the adsorption of the generated arsenate was slow.A concentration of 100 mg/L arsenite was oxidized to arsenate within 3 h in the presence of adsorbent and under UV-light, but the reaction rate was approximately 1/3rd of the photocatalyzed reaction. The optimum application pH for the adsorbent for oxidation and adsorption was ~ 3.0. (Mohan and Pittman , 2007 ).

Waste cast iron : Choi et al. ,2012 investigated the removal of As(III) and As(V) from aqueous solution by using waste cast iron, which is a byproduct of the iron casting process in foundries. Two types of waste cast iron were used in the experiment: grind precipitate dust (GPD) and cast iron shot (CIS). GPD is a major form of waste generated from grinding and polishing cast iron products, while CIS is a byproduct of cast steel shot which is a ballast material used in the iron casting process. Results showed that in the adsorption of both As(III) and As(V), the adsorption capacity of GPD was greater than CIS, mainly due to the fact that GPD had higher surface area and weight percent

of Fe than CIS. Results also indicated the removal of As(III) and As(V) by GPD and CIS was influenced by the initial solution pH, generally decreasing with increasing pH from 3.0 to 10.5. Fe(III)/Cr(III) hydroxide waste: Chromium(VI) compounds are used as corrosion inhibitors in cooling water systems in industries. Fe(II), generated electrolytically, reduces chromium(VI) in the wastewater to Cr(III) under acidic conditions.The Fe(III)/Cr(III) ions produced in solution are precipitated as Fe(III)/Cr(III) hydroxide by the use of lime.The resultant sludge is discarded as waste. Namasivayam and Senthilkumar , 1998 adsorbed As(V) from water onto a Fe(III)/Cr(III) hydroxide waste generated electrolytically in the treatment of Cr(VI)-containing wastewaters from fertilizer production. (Mohan and Pittman , 2007 ). Chrome sludge, a waste material from electroplating, was tested to adsorb As(V) from aqueous solutions. The maximum sorption capacity of chrome sludge for As(V) was 21 mg/g. (Lee and Lee, 1995). Fly ash: Fly ash is one of the residues generated in the combustion of coal. It is generally captured from the chimneys of power generation facilities. The availability of fly ash is so high that at many places its disposal is a problem. Since the major chemical compounds contained in fly ash are aluminosilicate, intensive efforts have been made to utilize this material as an adsorbent. Removal of arsenate at pH 4 was reported higher than that at pH 7 or 10 by using fly ash collected from coal power stations (Diamaddopoulos et al., 1993). Maple wood ash without any chemical treatment was also utilized to remediate As(III) and As(V) from contaminated aqueous streams in low concentrations. (Rahman et al., 2004). The removal of arsenate from synthetic wastewater by adsorption onto a coal combustion fly ash (CCA) was experimentally studied by Balsamo et al., 2010. Arsenate adsorption on raw CCA at constant temperature (20 C) was carried out in two synthetic arsenic aqueous solutions: a distilled water and a mineral water simulating a groundwater. In both the experimental conditions, CCA showed almost the same arsenate adsorption capacities. In order to increase CCA adsorption capacity and to simultaneously remove the arsenic originally present on CCA, a HCl treatment was performed; the treated sample showed a higher adsorption capacity, likely related to a surface oxidation. 2) Soils and constituents: Soil : Studies made on using soil as an adsorbent for arsenic treatment includes: As(V) adsorptiondesorption kinetics were reported on Olivier loam, Sharkey clay, and Windsor Sand by Zang and Selim , 2005 . As(III) and As(V) adsorption on three arid-zone soils from California (Wasco, Fallbrook, and Wyo) was examined at varying As concentrations, pHs, and ionic strengths . (Manning and Golberg , 1997). The soil with the highest Fe levels and clay (Wyo) had the highest affinity for both As(III) and As(V). This soil displayed adsorption behavior similar to pure ferric oxide. As(V) was adsorbed more strongly than As(III) under most conditions. Sand: A variety of treated and coated sands has been employed for arsenic remediation. Sand coated with iron oxide had more pores and a high specific surface area. Some of the methods of using sand in arsenic remediation has been described below:

Nguyen et al. , 2006 synthesized iron-oxide coated sponge (IOCSp) for As(III) and As(V) removal. Each gram of IOCSp adsorbed about 160 g of arsenic within 9 h. Viraraghavan et al., 1999 examined manganese greensand andiron oxide-coated sand for arsenic remediation from drinking water. Manganese greensand was effective for removing arsenic to <25 g/L . Iron addition was necessary to achieve an effluent arsenic level of 25 g/L in the manganese greensand filtration system. Viraraghavan et al., 2001 achieved 285 g/g of arsenic removal on iron oxide-coated sand. Sulfate modified iron oxide coated sand (SMIOCS) was also used for As(III) and As(V) removal (Vaishya and Gupta , 2002 ). SMIOCS was prepared by coating BaSO4 and Fe on quartz sand. The maximum As(V) removal was obtained in acidic pH while maximum As(III) removal was obtained at pH 79. Aluminum-loaded coral limestones were used for the removal of As(III) and As(V) from aqueous solution (Ohki et al. , 1996). As(III) and As(V) adsorption was almost independent of the initial pH over a wide range (211). The adsorption capacity of this treated coral limestone was 150 g/g for As(V).

Clay minerals. Clay minerals are hydrous aluminum silicates, sometimes with minor amounts of iron, magnesium and other cations . Typical clay minerals are kaolinite, illite and montmorillionite). Finely divided clay minerals and oxides exhibit large surface areas. Clay minerals and oxides adsorb the cationic, anionic, and neutral metal species. They can also take part in the cation- and anion-exchange processes. (Mohan and Pittman , 2007 ). Studies of arsenate and arsenite removal from water by oxides and clay minerals have appeared. Some of them are as follows: Arsenic remediation by clay-rich limestone from the Soyatal formation in Zimapan, Mexico was studied and compared with other rocks from the region. The experimentally contaminated water (0.6 mg As/L) was reacted with various rocks from the Zimapan region. All rocks decreased the aqueous arsenic concentration below detection limits (<0.030 mg/L) in any contaminated waters that had been reacted with the Soyatal Formation. The calcareous shale of the Soyatal formation contains kaolinite and illite. Both minerals adsorbed arsenic. (Ongley et al. , 2001). Adsorption of arsenate on kaolinite, montmorillonite and illite and arsenite on kaolinite, illite, montmorillonite, and amorphous aluminum hydroxide were investigated as a function of pH, and competing anions. The As(V) concentration (6.7107 M), the amount of suspended clay (2.5 g/L) and the ionic strength (0.1M NaCl) were held constant . Distinct As(V) adsorption maxima (0.150.22 mmol As(V) kg1) occurred at approx. pH 5.0 for kaolinite, 6.0 for montmorillonite and 6.5 for illite. When both As(V) and phosphate were present at equimolar concentrations (6.7107 M), As(V) adsorption decreased slightly. In contrast, As(V) adsorption substantially decreased in binary As(V)/phosphate systems when the phosphate concentration was 10 times greater than As(V) (e.g., 6.7106 M). The presence of Mo at 6.7107M (10 times greater concentration than As(V)) caused only slight decreases in As(V) adsorption because theMo adsorption maxima occurred at pH < 4. (Manning and Goldberg , 1997) ,(Manning and Goldberg , 1996).

Amorphous Al and Fe oxides, kaolinite, montmorillonite, and illite were studied as a function of pH for As(III) and As(V) removal.(Goldberg and Johnston , 2001). Arsenate adsorption on these oxides and clays was maximum at low pH and decreased at pH > 9 for Al oxide, pH > 7 for Fe oxide and pH > 5 for the clays. Arsenite adsorption exhibited parabolic

behavior with adsorption maxima at pH 8.5 for all these materials. There was no competitive effect of the presence of equimolar arsenite on arsenate adsorption while a competitive effect of equimolar arsenate on arsenite adsorption was obtained only on kaolinite and illite in the pH range 6.59.

Zeolites: Zeolites are crystalline, hydrated alluminosilicates of alkali and alkaline earth cations. They can lose and gain water reversibly and exchange constituent cations without change in structure. (Mohan and Pittman , 2007 ). At present, there are 191 unique zeolite frameworks identified, and over 40 naturally occurring zeolite frameworks are known (Baerlocher et al., 2007). Both ion exchange and adsorption properties of zeolites have been used for the selective separation of cations from aqueous solution. Xu et al. (2002) studied adsorption and removal of As(V) from drinking water by aluminum-loaded shirasu-zeolite and found its effectiveness over a wide range of pH (3 to 10). Common competing anions such as arsenite, chloride, nitrate, sulfate, chromate, and acetate ions had little effect on As(V) adsorption but phosphate greatly interfered with the adsorption. (Chiban et al. , 2011) ,(Mohan and Pittman , 2007 ).

Biosorption: Biosorption is defined as the process of concentration of sorbate on the sorbent. A prefix bio means that the sorbent is of biological origin, a surface of biological matrix. In general term it is a simple physicochemical process resembling conventional adsorption or ion exchange. The difference lies in the nature of sorbent which in this case is the material of biological origin. The concept of biosorption includes concentrating a sorbent in the biomass. The process involves a solid phase (sorbent or biosorbent; biological material) and a liquid phase (solvent, normally water) containing a dissolved species to be sorbed (sorbate, metal ions). Due to higher affinity of the sorbent for the sorbate species, the latter is attracted and bound there by different mechanisms. The process continues till equilibrium is established between the amount of solid-bound sorbate species and its portion remaining in the solution. (Ahalya et al. , 2003) (Chojnacka , 2010) The biosorbents used in this process are derived from three sources as follows (Apiratikul and Pavasant, 2008): (1) non-living biomass such as bark, lignin, shrimp, krill, squid, crab shell, etc.; (2) algae biomass; (3)microbial biomass, e.g. bacteria, fungi and yeast. A related term often used along with Biosorption is Bioaccumulation. Biosorption and bioaccumulation differ in that in the first process pollutants are bound to the surface of cell wall and in the second, they also become accumulated inside the cell. Also, Biosorption is metabolically passive process and is performed by material of biological origin, not by living biomass whereas Bioaccumulation is metabolically active and is performed by living cells. While in biosorption there is no danger of passing toxicity from sorbate to sorbent, in bioaccumulation such danger exists . A table below shows the various differences between this two process. (Chojnacka, 2010). TABLE 5:

Biosorption
Passive process Biomass is not alive Metals are bound with surface

Bioaccumulation
Active process Biomass is alive Metals are bound with Cellular surface and interior

Adsorption Reversible process Nutrients are not required Single Stage process Rate is quick Not controlled by metabolism No danger of toxic No cellular growth

Absorption Partially reversible process Nutrients are required Double stage process Rate is slow Controlled by metabolism Danger of toxic caused by contaminants Cellular growth occurs

Advantages of Biosorption over other methods includes: 1. Cheap as it is generally made from waste materials. 2. Low sludge generation. 3. Regeneration of biosorbents are possible and easy. 4. Possibilty of metal recovery from the solutions.

Factors affecting biosorption: The factors which influence biosorption performance includes: 1. type of the biomass (and resulting the composition of cell wall) 2. pH, 3. temperature, 4. presence of other competing ions (both cations and anions) (Naja et al., 2010) Generally, increase of pH causes deprotonation of metal ions binding sites exposed by cellular surfaces. Decreasing pH causes competition between protons and positively charged metal ions. However these rules concern only cations (Naja et al., 2010). Since biosorption is reversible process, decreasing pH would result in deprotonation. This property is used in regeneration of biosorbents. Another explanation is that with increased pH, solubility of complexes of metals decreases (Naja et al., 2010). Biosorption properties of a biomass are dependent on the chemical composition of cellwall . Seaweeds are presented as very good sorbents, because the cell wall of green and brown algae contains alginate with its carboxyl and hydroxyl groups. (Davis et al., 2003; Vieira and Volesky, 2000). Worse sorptive properties are possessed by red algae which contain carrageen, exposing hydroxyl and sulfonate groups (Vieira and Volesky, 2000). The biomass of yeasts and other fungi contains chitin and chitosan and thus amino, amido and hydroxyl groups are found on the cellular surfaces. For this reason fungi have a unique properties of binding both cations and anions to their cell wall. Among the group of bacteria we can distinguish gram positive and gram negative. Cell wall of gram negative bacteria contains peptidoglycan and of gram positive also teichoic acids containing phosphoryl and hydroxyl groups and thus the latter are better biosorbents . Temperature seems not to influence the biosorption performances in the range of 20-35 c (Aksu et al. , 1992). Biosorption mechanisms: Several different processes which were thought to contribute to biosorption are: 1. surface complexation 2. precipitation, 3. physical adsorption 4. ion exchange
0

Recently the dominating role of the latter process has been confirmed. The reaction order is related with the mechanism of biosorption, which is the most frequently ion exchange or surface precipitation (metal hydroxide, sulfide or carbonate). (Chojnacka, 2010; Chojnacka et al., 2005). Generally the process of biosorption can be described as biological ion exchange with binding groups present on the surface of cell wall: carboxyl, sulfonate, phosphoryl, amido, amino, imidazole (Volesky and Schiewer, 2000). The groups have distinguishable pKa responsible for the binding properties of a given group (Volesky, 2007). Below are the description of various binding groups and its pKa: TABLE 5: (Volesky, 2007)

Binding Group

Hydroxyl Carbonyl Carboxyl Thiol Sulphonate Thioether Amine Secondary amine Amide Imine Imidazole Phosphonate Phosphodiester

Occurrence in selected molecule PS, UA, SPS, AA Peptide bond UA, AA AA SPS AA AA,Cti Cti,PG,peptide bond AA AA AA PL TA,LPS

pKa 9.5-13

1.7-4.7 8.3-10.8 1.3 8-11 13

11.6-12.6 6.0 0.9-2.1 6.1-6.8 1.5

PS :polysaccharides; UA : uronic acids; SPS : sulphated PS; Cti: chitosan; PG :peptidoglycan; AA: amino acids; TA : teichoic acid; PL : phospholipids; LPS : lipoPS.

Biosorbents for arsenic: Bone char : Bone char derived from the carbonization of the crushed animal bones by heating them to 500700 C in an airtight iron retort for 46 h. The crushed bone, after the heating process, will form the bone charcoal which is composed of calcium hydroxylapatite (CaHAP) (7076 wt%), carbon content (9 11wt%), calcium carbonate (79 wt%), etc. was studied as a biosorbent for arsenic (V). Results obtained were as follows: Effect of pH The optimum adsorption was achieved in the pH range between 9 and 13 for initial As(V) concentration of 0.5, 1.0 and 1.5mg/l. High adsorption percentagewas observed at higher pH value. One reason for the change of pH may be ion exchange. And the reason for the higher adsorption efficiency at higher pH maybe the formation of hydroxyl groups and the co-precipitation between calcium hydrogen arsenate and hydroxylapatite in the aqueous solution on the surface of the bone char.

Effect of adsorbent dose Adsorption efficiency of As(V) increased very rapidly with an increase in dosage of bone char from 0.1 to 0.6 g/l; a marginal increased was observed on further increase in the adsorbent dose. At 0.8mg/l bone char, maximum removal efficiencies of 98.54% were observed at temperature of 28 C (301 K). The increase in the efficiency of removal may be attributed to the fact that with an increase in the adsorbent dose, more adsorbent surface, or more adsorption spotswere available for the solute to be adsorbed. And with the increase of temperature from 28 C (301K) to 48 C (321 K), the adsorption efficiency of As(V) decreased a little. The results also suggested that the removal of As(V) on bone char was complex mechanism where both co-precipitation between calcium hydrogen arsenate and hydroxylapatite in the aqueous solution and ions exchange between calcium hydrogen arsenate and hydroxyl ion occurred.

Wheat straw : As an agricultural waste, wheat straw has a high yield every year. However, most of the wheat straw has been burnt for cooking or heating, or been left directly to decompose. These treatments will not only waste natural resources, but also cause environmental pollutions. Therefore, it is necessary to make the best use of wheat straw. A comprehensive study for the component, structure and morphology of wheat straw was made. Wheat straw has a vascular bundle structure, which will provide additional surface for chemical modification. It also has complicated components including lignin, hemicellulose, cellulose, pectin, protein and fatty acid. The wheat straw is abundant in hydroxyl groups. The hydroxyl groups can provide chemical reaction sites and adsorb iron ions to grow Fe3O4 crystal. In this study, agricultural waste wheat straw was used as template to grow Fe3O4 nano- or micro-particles on its surface, and then its potential application in arsenic adsorption was investigated. The synthesized magnetic wheat straw samples were coded as MWS1, MWS2 and MWS5, the total iron ion concentrations in the reaction system of which were 0.1 mol/ L, 0.2 mol /L and 0.5 mol/ L, respectively. Results obtained were as follows: Comparing the MWSs with different Fe3O4 content, the adsorption capacity was in the order of MWS5 > MWS2 > MWS1. That means Fe3O4 is an effective component of arsenic adsorption. The wheat straw itself does not have the capacity to adsorb arsenic. Its main function is to provide a template with high specific area for Fe3O4 loading. Adsorption capacity of MWSs with pure wheat straw and the synthesized bare magnetite was compared. The adsorption capacities of Fe3O4 loading onto the wheat straw was much higher than the bare ones. Therefore the introduction of wheat straw template can effectively enhance the adsorption capacity. The reason may be that the template can prevent Fe3O4 particles from aggregating in adsorption process, and increase the effective adsorption area, resulting in the highly enhancement of adsorption capacity.