ORIGIN OF THE PROBLEM

In the process of human evolution, some of the issues confronting todays society are safe guarding the natural environment and maintaining a good quality of life. Access to Safe Drinking Water is essential to health, a basic human right and a component of effective policy for health protection. However, a slight imbalance in any equilibrium in the environment is bound to manifest itself in the form of pollution. Pollution of water is increasing steadily due to rapid population growth, industrial exploitation, urbanization, increasing living standard and wide spheres of human activities. Toxic metals/metalloids are the important member of dirty dozen clubs of pollutants. Arsenic, a metalloid, is found in virtually all the eco-systems of the environment. Due to its high toxicity and discreetness, arsenic has been called The King of Poisons and is classified as a human carcinogenic substance of group 1 by IARC (International Agency for Research on Cancer). Arsenic toxicity causes skin lesions, damage mucous membranes, nervous system, gastrointestinal, cardiovascular, mutagenic etc. Considering the lethal impact of arsenic on human health, environmental authorities have taken a more stringent attitude towards the presence of arsenic in water. The scale of the problem of arsenic poisoning is illustrated by the frequently used term Mass Poisoning. WHO and EPA re-established a guideline of 0.01mg/L as the maximum allowable arsenic content. Arsenic, therefore, is under strict watch, globally. The conventional methods used for abatement of arsenic are often restricted because of technical, economical and environmental constraints. Arsenic has also been removed by means of the various simple methods viz precipitation with lime, alum, lanthanum, sodium sulfide/hydrogen sulfide and co-precipitation with ferric sulfate. These methods involve the use of large amount of chemicals and suffer from a post treatment problem regarding the sludge, containing large amount of water having chances of leaking of arsenic back to environment after exposure to water and air. Further, recent research findings have raised strong doubts about the use of synthetic coagulants for water purification. The speciation of arsenic in environmental materials is of interest because of the differing levels of toxicity exhibited by the various species. The toxicological, physiological and geochemical behaviour depends on its oxidation state. Toxicity is especially due to inorganic arsenic. Inorganic arsenic species, i.e. arsenite and arsenate, predominantly found in natural water, are more toxic than organic species such as monomethylarsonic acid and dimethylarsinic acid. Thus, it is important to determine each of the arsenic species rather than the total arsenic. The speciation of arsenic has been attempted using non degradable inorganic chemical species. Not much attention has been paid towards the use of biomaterials to alleviate current problems of arsenic from water bodies.

To combine technology with environmental safety is one of the key challenges of the new millennium. There is a global trend of bringing technology into harmony with natural environment, thus aiming to achieve the goals of protection of ecosystem from the potentially deleterious effects of human activity and finally improving its quality. The challenges of treating and diagnosing environmental problems require discovery of newer, more potent, specific, safe and cost effective synthetic or natural molecules. The magic plants/products/wastes are around and waiting to be discovered and commercialized. The emerging concept of Clean Production and Process is a new principle guiding the next generation products and processes. Bioremediation: A Green Solution to Pollution, involves processes that reduce overall treatment cost through the application of indigenous agricultural wastes which are particularly attractive as they lessen reliance on expensive water treatment chemicals, negligible transportation requirements and offer genuine, local resources as appropriate solutions to tackle local issues of water quality. Regeneration of the biomaterials increases the cost effectiveness of the process thus, warrants its future success. Use of plant materials with an aim to effectively alleviate the economic aspects allowing, further extension of water supply to rural areas of developing countries. Recently, agricultural wastes exhibiting potential for the decontamination of toxic

metals/metalloids from water bodies have been found to have drawbacks of less sorption efficiency and stability, restricting their commercial use. Current research is oriented towards the Structural Modifications onto the biomaterials leading to the Enhancement of Binding Capacity, Selectivity and Environmental Stability in terms of their Reusability are, therefore, in great demands. A search for low cost easily available adsorbents for abatement and chemical speciation of arsenic has led to the investigation of biomaterial of agricultural origin and becomes an area of current research. Keeping above views in mind, the present work explores the unexploited property of some agricultural wastes [Zea mays corn cob & Leucaena leucocephala seeds] as a bioremedial approach for the abatement of arsenite and arsenate from water bodies and their modifications leading to the formation of Novel Biomaterials with enhanced sorption efficiency and environmental stability reaching to the level of their commercialization.

The implementation of the local environment tactics for achieving the environmental goals in a localized region of environment is Green Environmental Strategy and the need of the day

ARSENIC: ENVIRONMENT TERRORIST

Water is undeniably the most valuable natural resource existing on our planet. Without this invaluable compound, the life on the Earth would be non-existent. The vitality of water is mandatory to all forms of life and fundamental for environmental health and management. However, due to Technological Development, Agricultarization, Urbanization and Industrialization, the levels of pollutants have been steadily rising. So, the pollution problem of industrial waste water is becoming more and more serious in the world. Among all of the pollutants, heavy metals/metalloids have been a major cause of the environmental pollution. Effluents from textile, leather, tannery, electroplating, galvanizing, pigment, dyes, metallurgical, paint industries and other metal processing and refining operations at small and large-scale sector contains considerable amounts of toxicants (Gonzaga et al., 2006; Vahidnia et al., 2007; Malik et al., 2009). Lead, Arsenic, Cadmium, Chromium and Mercury are the examples of heavy metals/ metalloids that have been classified as priority pollutants by the U.S. Environmental Protection Agency (USEPA, 2003). Widespread contamination of drinking water by arsenic has recently come to the forefront of world attention (Bose et al., 2011). Arsenic may change chemical form in the environment, but it does not degrade (Smedly and Kinniburg, 2002). The World Health Organization (WHO) estimated that about 130 million people worldwide are exposed to arsenic concentrations (WHO, 2006). Over 70 million people in Eastern India, Bangladesh, Vietnam, Taiwan and Northern China have been victims of arsenic poisoning (Wang and Wai, 2004; Sohel et al., 2009; Mahmood and Halder, 2011). Therefore, a complete understanding about noxious effects caused by the release of toxic metals/metalloids into the environment and the emergence of more severe environmental protection laws, have encouraged studies about removal/recovery of them from aqueous solutions. Over a few decades, scientific community is developing concentrated efforts for the treatment and removal of arsenic in order to combat this problem.

ARSENIC: GENERAL CHEMISTRY

The name Arsenic is derived from the Greek word arsenikon, which means yellow Orpiment. Arsenic compounds have been mined and used since ancient times. The extraction of the element from arsenic compound was first reported by Albertus Magnus in 1250 AD. Arsenic ranks 47th most abundant element in nature (1.8 mg/kg) and 20th in earths crust (Wikipedia, 2010). It exhibits metallic as well as non-metallic characteristics. In the Victoria era, arsenic was mixed with vinegar and chalk and eaten by women to improve the complexion of their faces, making skin fairer. During the Bronze Age, arsenic was often included in the bronze (mostly as an impurity), which made the alloy harder. Arsenic is one of the oldest human poisons known to mankind.

 Arsenic, a metalloid, has been classified as a human carcinogenic substance of group 1 by IARC (International Agency for Research on Cancer). Ranked first in a list of 20 hazardous substances by the Agency for Toxic Substances and Disease Registry and United States Environmental Protection Agency. Arsenic has been found in at least 784 of the 1,662 National Priority List of hazardous substance identified by the Environmental Protection Agency.

Physical Properties of Arsenic

Arsenic is a semi metallic element. It has an atomic number of 33 and atomic weight of 74.92. It exists in three allotropic forms: yellow (alpha), black (beta) and gray (gamma). Arsenic also exists in black and yellow amorphous forms. The metallic gray form is the stable form of arsenic. Arsenic appears in Group 15 in the periodic table in the 4th Period. Elemental arsenic has a specific gravity of 5.73, sublimes at 613 C and has a very low vapour pressure of 1 mmHg at 373 C. Many of the inorganic arsenic compounds occur as white, odourless solids with a specific gravity ranging from 1.9 to 5. The physical properties of arsenic are summarized in table 1.01.

Table 1.01: Physical properties of arsenic

Name Symbol Atomic no. Electronic shell Electronegativity Chemical series Atomic weight Melting point Boiling point Critical temperature Heat of vaporization Critical pressure Density (at 14C) Isotopes Most stable isotope Covalent Radius Atomic Radius Ionic Radius Vapour Pressure

Arsenic As 33 [Ar] 3d10 4s2 4p3 2.0 Metalloid 74.92 g/mol 817C (1090K, 1503F) 613C 1,400C 11.2 Kcal/g-atm 22.3 Mpa 5.727g/cm3 8
75

As

1.19 A 1.39 A 2.22 A 1mm (375C)

(Source: ATSDR, 2010)

Environmentally Relevant Forms of Arsenic

Arsenic is found in four oxidation states, -3 (arsine), 0 (arsenic) +3 (arsenite) and +5 (arsenate) and in the aquatic environment both the organic and inorganic forms are found (Mandal and Suzuki, 2002). The two dominant oxidation states for inorganic arsenic are the trivalent arsenite at moderately and strongly reduced conditions and the pentavalent arsenate in the aerobic environment. Many of the chemical behaviours of arsenic are linked to the ease of conversion between +3 and +5 valence states (NRC, 1999). The valence state affects the toxicity of arsenic compounds. Arsenic occurs naturally as a constituent of a number of different compounds in both marine and terrestrial environments.

Inorganic Arsenic
Inorganic arsenic with +5 (arsenate) and +3 (arsenite) oxidation states, is more prevalent in water than organic arsenic (Irgolic, 1994). The dominant arsenic species depends on pH and redox conditions. In general +5 predominate under oxidizing conditions and +3 predominate under reducing conditions (Smedley and Kinniburgh, 2005). Inorganic arsenic compounds found in the environment include oxides [As2O3, As2O5, R3(AsO)n, RnAsO(OH)3-n (n=1, 2)] and sulfides [As2S3, AsS, HAsS2, HAsS33-] (Cullen and Reimer, 1989). Inorganic arsenic species which are stable in oxygenated waters include arsenic acid [As (V)] species [H3AsO4 and H2AsO4-, HAsO42- and AsO43-]. Arsenous acid [As (III)] is also stable as H 3AsO3 and H2AsO3- under slightly reducing aqueous conditions.

Organic Arsenic
If carbon is present with the compound it is considered to be an organic arsenic species. Organic arsenic compounds such as Monomethyl arsonic acid (MMAA), Dimethyl arsinic acid (DMAA), Trimethylarsine (TMA) and Trimethylarsine oxide (TMAO) are generally associated with terrestrial settings, however, some are found in water (NRC, 1999). Organic arsenic is produced naturally in the environment in the natural gas (ethyl methyl arsines), shale oil, in water when microorganisms metabolize inorganic arsenic, and in the human body, as a result of enzyme activity in the liver (Berger and Fairlamb, 1994). Table 1.02 includes a summary of both organic and inorganic species of arsenic which may be found in food and water.

Table 1.02: Organic and inorganic species of arsenic

Name Arsenous acid Arsenic acid Monomethylarsonic acid Methylarsonous acid Dimethylarsinic acid Dimethylarsinous acid Trimethylarsine

Abbreviation As (III) As (V) MMA (V) MMA (III) DMA (V) DMA (III) TMA

Chemical Formula H3AsO3 H3AsO4 CH3AsO(OH)2 CH3As(OH)2 (CH3)2AsO(OH) (CH3)2AsOH[((CH3)2As)2O] (CH3)3As

(Source: Mass et al., 2001)

Chemical Properties of Arsenic

Arsenic is stable in dry air but the surface oxidizes slowly in moist air to give a bronze tarnish and finally a black covering to the element. When heated in air, arsenic ignites to form arsenic trioxide actually tetra arsenic hexaoxide (As4O6). When heated in oxygen, arsenic ignites in oxygen to form arsenic pentaoxide actually tetra arsenic decaoxide (As4O10 and As4O6). 4 As (s) + 5 O2 (g) 4 As (s) + 3 O2 (g) As4O10 (s) As4O6 (s)

Arsenic reacts with fluorine (F2) to form penta fluoride arsenic (V) fluoride. 2 As (s) + 5 F2 (g) 2 AsF5 (g) [Colourless] Arsenic reacts under controlled conditions with the halogens fluorine (F2), chlorine (Cl2), bromine (Br2) and iodine (I2), to form the respective trihalides arsenic (III) fluoride (AsF3), arsenic (III) chloride (AsCl3), arsenic (III) bromide (AsBr3) and arsenic (III) iodide (AsI3). 2 As (s) 2 As (s) 2 As (s) 2 As (s) + 3F2 (g) + 3Cl2 (g) + 3Br2 (g) + 3I2 (g) 2 AsF3 (l) [colourless] 2 AsCl3 (l) [colourless] 2 AsBr3 (l) [colourless] 2 AsI3 (l) [colourless]

Occurrence of Arsenic
Arsenic has two sources one of them is natural and the other is manmade. Natural sources include earth crust, sedimentary rocks and weathered volcanic rocks. Fossil fuels, mineral deposits, mining wastes and geothermal are other natural sources through which arsenic can occur in ground water (Smith et al., 1998). Some of the naturally occurring minerals of arsenic are listed in table 1.03. Anthropogenic sources include man-made such as fertilizers, drugs, feed additives, insecticides, wood preservatives and herbicides (Adriano, 2001). Significant anthropogenic sources include combustion of fossil fuels, leaching from mining wastes and landfills,

mineraling, metal production, timber treatment, cattle and sheep dips and arsenical pesticides (Eisler, 2004). Precipitation from the atmosphere and application of a range of agricultural by products such as poultry manure, can also contribute to large quantities of arsenic contamination on land. Some volatile organic compounds (VOCs) in ground water may facilitate the release of arsenic from aquifer materials to ground water (Christen, 2001). Ground water affected by VOCs like petroleum products and other landfill wastes may be sufficiently reduced to result in elevated dissolved iron-oxide concentrations. Under these reducing conditions, aquifer materials may be a source of dissolved arsenic in ground water (Ogden, 1990).

Table 1.03: Naturally occurring minerals of arsenic Name of minerals Arsenopyrite Cobaltite Orpiment Lollingite Realgar Niciolite Chemical Formula FeAsS CoAsS As2S3 FeAs2 As4S4 NiAs
(Source: Yan-Chu, 1994)

Environmental Concentrations
Arsenic is the 20th most abundant element in the earths crust (NAS, 1977). Concentrations of arsenic in the earths crust vary but average concentrations are generally reported to range from 1.5 to 5 mg/Kg (Cullen and Reimer, 1989).

Arsenic in Soil
Arsenic contamination source in soil is the parent rock from where the soil is obtained. Its concentrations in soil were examined in a wide range of soils and reported an average of 5-6 mg/kg (may vary with the geological history of the region) for uncontaminated soils (Mandal and Suzuki, 2002). Sandy soil and granites has the lowest concentration of arsenic. On the other hand alluvial and organic soils have higher concentrations of arsenic (Smedly and Kinniburg, 2002).

Arsenic in Atmosphere
High temperature processes such as coal-fired power generation, smelting, burning vegetation and volcanism results in emission of arsenic into the atmosphere. Naturally occurring low temperature biomethylation of arsenic species and microbial reduction process also release arsenic to the atmosphere. In this process microorganisms forms volatile methylated derivatives of arsenic under both aerobic and anaerobic conditions (Le, 2002). Microorganisms can also reduce these methylated compounds to release arsine gas. Arsenic is released to the atmosphere primarily as As2O3 or less frequently as one of several volatile organic compounds. In air, arsenic exists predominantly absorbed on particulate matters and is usually present as a mixture of arsenite and arsenate, with being of negligible importance except in areas of arsenic pesticide application or biotic activity (Liu et al., 2007).

Arsenic in Water
Arsenic is the 10th most abundant element in sea water with an average value of 2.0 g/L (Vahidnia et al., 2007). In general, concentration of arsenic is relatively stable in sea water but some seasonal variations can occur due to biological uptake of surface sea water. Inorganic As (V) is the major arsenic species because arsenic can be stabilized as a series of pentavalent oxyanions [H3AsO4, H2AsO4-, HAsO42- and AsO43-] at high redox potential conditions. However, under most reducing (acid and mildly alkaline) conditions and lower redox potential, the trivalent arsenite species (H 3AsO3) predominate. As (0) and As (3-) are rare in aquatic environment. As (III), MA and DMA are present at lower levels, usually accounting to 10% of the total arsenic concentration (Le, 2002). In ground water, inorganic arsenic commonly exists as As (V) and As (III), the latter is considered to be more mobile and toxic for living organisms.

Arsenic in Food
Trace elements are important but they are more important in food because they can have adverse health effects. Arsenic, one of the trace elements has no known biological function and human body higher levels may cause cancer. Arsenic, if in its inorganic form, can damage DNA and is carcinogenic. However, arsenic present in food is in less harmful (organic) forms (Edmonds and Francesconi, 1993). Inorganic arsenic species found in food is not more than 1 to 3 percent of the total arsenic presents (Food Standards Agency, 2004). Levels of arsenic are higher in the aquatic

environment than in most areas of land as it is mostly water-soluble. It could be washed out of arsenic bearing rock and sea foods arsenic enters into the daily consumption of human being. Table 1.04 presents a list of arsenic concentrations in environmental media. Arsenic in igneous and sedimentary rocks is listed in table 1.05.

Table 1.04: Arsenic concentrations in environmental media Environmental Media Air from remote and rural areas Air from urban areas Air near industrial areas Rain from terrestrial air Rivers Lakes Ground water Sea water Soil Arsenic Conc. Range 0.02 4.0 3.0 - 200 >1000 0.46 0.20-264 0.38-1,000 <1.0- >1,000 0.15-6.0 0.1-1,000 Units ng/m3 ng/m3 ng/m3 g/L g/L g/L g/L g/L mg/Kg

(Source: ATSDR, 2005)

Table 1.05: Arsenic in igneous and sedimentary rocks Rocks Arsenic Conc. range (mg/kg) Igneous Rocks Ultra basic Basalts, gabbrous Granitic 0.3 16 0.06 113 0.2 - 13.8 Sedimentary Rocks Limestones Sandstones Shales and clays 0.1 20 0.6 120 0.3 490
(Source: Mok and Wai, 1994)

Average

3.0 2.0 1.5

1.7 2.0 14.5

10

Arsenic Toxicity
Inorganic arsenic is more toxic than organic arsenic (Bose et al., 2011). The toxicity of inorganic arsenic compounds depend both on the oxidation state of arsenic. Arsenite [As (III)] and arsenate [As (V)] are considered to be most toxic forms and classified as human carcinogen substances (USEPA, 2005). Moreover, they are the predominant forms found in water. One of the most toxic arsenic compounds is arsine gas, AsH 3, with -3 oxidation state. Trivalent arsenic species are more toxic than inorganic As (V), MA (V) and DMA (V) in vitro (Styblo et al., 2000; Andrew et al., 2003). This may be related to more efficient uptake of trivalent methylated arsenic species than of pentavalent arsenic species by micro vessel endothelial cells and CHO (Chinese Hamster Ovary) cells (Dopp et al., 2004; Hirano et al., 2004). The toxicity of trivalent arsenic is related to its high affinity for the sulfurydyl groups of biomolecules such as glutathione (GSH) and lipoic acid and the cysteinyl residues of many enzymes (Aposhian and Aposhian, 2006). The formation of inorganic As (III)sulfur bonds results in various harmful effects by inhibiting the activities of enzymes such as glutathione reductase, glutathione peroxidases, thioredoxin reductase and thioredoxin peroxidise (Schuliga et al., 2002).

Arsenic Lesions
Arsenic is extremely poisonous. IARC (International Agency for Research on Cancer, 2004) has classified arsenic as a human carcinogenic substance, group 1. Long-term intake of drinking water with elevated arsenic concentrations can cause the development of arsenicosis, the collective term for diseases caused by chronic exposure to arsenic. Arsenic toxicity causes skin lesions, damage mucous membranes, nervous system, gastrointestinal, cardiovascular, genotoxic, mutagenic and carcinogenic effects (Hymer et al., 2004; Tofail et al., 2009; Rivas and Aguirre, 2010; Hamadani et al., 2010; Bose et al., 2011). Hyperpigmentation, an excess of skin pigmentation, is most often the first visible symptom. Considering the lethal impact of arsenic on human health, environmental authorities have taken a more stringent attitude towards the presence of arsenic in water.

Arsenic is under strict watch globally. The European Commission/U.S. Environment Protection Agency has revised the maximum contaminant limit of arsenic from 0.05 mg/L to 0.01 mg/L in drinking water.

11

Arsenic Lesions in Eye

Keratosis on Hand

Remedy for Arsenic Contamination

Arsenic Lesions on Head

Bowen's Disease

Skin Cancer

Blackfoot Disease
Figure 1.01: Arsenic lesion

(Source: Bissen and Frimmel, 2003)

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ARSENIC POISONING: A WORLD WIDE PROBLEM

The most well-known and severe case of arsenic poisoning through drinking water is currently ongoing in Bangladesh. The scale of the problem is illustrated by the frequently used term mass poisoning (Halem et al., 2009). Two-thirds of the tube wells installed over the last three decades, roughly three million in total, have been shown to contain arsenic concentrations above the permissible level set by the WHO (BGS/DPHE, 2001). These wells were installed with the firm conviction that they would contribute a secure and reliable drinking water supply, in order to put an end to various contagious diseases caused by the use of (unsafe) surface water (Figure 1.02). It is therefore, a bitter observation that this approach has led to widespread arsenic poisoning through drinking water. It is estimated that 37 to 100 million people are at risk of drinking arsenic-contaminated drinking water (WHO, 2001; Chowdhury et al., 2006). World Health Organization (WHO) estimated that long-term exposure to arsenic in groundwater, at concentrations over 500 g/L, causes death in 1 in 10 adults in Bangladesh (Smith et al., 2000).

Figure 1.02: Arsenic poisoning in Bangladesh (Source: http://www.banglapedia.org/httpdocs/HT/A_0308.HTM) The problem of arsenic contaminated source water is, however, not confined to the Eastern countries. In China the reducing conditions in the subsurface are the cause of arsenic mobilization. In Vietnam and Cambodia, arsenic concentrations were also observed to be high (up to 1,340 g/L) due to reductive dissolution of young sediments (Buschmann et al., 2007; Buschmann et al., 2008). Arsenic mobilization caused by mineral dissolution has been

13

found in active volcanic areas of Italy (Aiuppa et al., 2003) and inactive volcanic regions in Mexico (Armienta and Segovia, 2008). Volcanism in the Andes has lead to arsenic contamination of ground water in Chile and Argentina (Smedley and Kinniburgh, 2002). Also mining activities have been found to contribute to arsenic contamination in Latin American ground water (Smedley and Kinniburgh, 2002). More recently, ground water in Burkino Faso was found to be contaminated by arsenic with concentrations up to 1,630 g/L, caused by mining activities (Smedley et al., 2007). Furthermore, Gunduz et al. (2009) reported elevated arsenic levels (<560 g/L) due to mining and geothermal influenced ground water in Turkey. In the Netherlands, arsenic concentrations have also been observed in the ground water (including, peaty soil and dune area), but concentrations exceeding the WHO guideline have never been reported in the drinking water (Stuyfzand et al., 2006).

Arsenic Poisoning In India

The first case of arsenic poisoning was revealed in West Bengal in early 1980s, the widespread contamination was not recognized until 1995. Arsenic in ground water above the WHO permissible limit has been found in six districts of West Bengal covering an area of 34,000 km2 with a population of 30 million (Michael and Voss, 2008). At present, 37 administrative blocks by the side of the River Ganga and adjoining areas are affected. More than 8 lakh people from 312 villages are drinking arsenic contaminated water and amongst them at least 1.75 lakh people show arsenical skin lesions (Table 1.06).

Table 1.06: Districts of West Bengal affected by arsenic poisoning

District

No. of blocks affected

No. of villages 229 354 541 472 409 4 18 38 2065

Population of the village 696822 1343866 1743889 1884676 964431 107951 37678 101171 6970484

Malda Murshidabad Nadia North 24 Paraganas South 24 Paraganas Howrah Hooghly Bardhaman Total

7 18 17 19 9 2 1 2 75

(Source: Harvey et al., 2002)

14

Thousands of tube-well in these six districts have been analysed for arsenic species. As such chronic arsenic toxicity in West Bengal due to drinking contaminated water are reported from eight districts from Malda to 24-South Parganas through Murshidabad, Nadia and 24North Paraganas on the eastern bank of Bhagirathi river and Bardhman, Haora and Hugli districts from western bank of river (Hira-Smith et al., 2007). All 75 blocks have been affected by arsenic contamination.

Unfortunately, today similar mistakes are being repeated in UP, Bihar, Jharkhand and Assam, where still the villagers are drinking contaminated water. The Times of India explores the effect of arsenic poisoning on the villagers in Ballia, UP (Figure 1.03). All the 310 villages in Ballia have arsenic above that limit, with 94 having concentrations greater than 100 mg/L. In Gazipur and Varanasi, arsenic concentration was found above 10 mg/L in 100 villages (Dixit, 2011). In June 2002, first arsenic contamination was reported in Bihar in middle Ganga plain (Chakraborti et al., 2004; Acharya and Shah, 2004). Today, on the basis of analyzing 15,000 samples from Bihar, arsenic concentrations was found above 50 g/L in 12 districts, 32 blocks and 201 villages (Mukherjee et al., 2006). The districts, Bhagalpur, Khagaria, Munger, Begusarai, Lakhisarai, Samastipur, Patna, Baishali and Buxar were identified hundreds of subjects with arsenical skin lesions (Chakraborti et al., 2008; Mukherjee et al., 2012). The administration in UP and Bihar is yet to learn from the mistakes committed in a neighboring state of West Bengal.

Figure 1.03: Arsenic poisoning in UP (Source: http://www.indiawaterportal.org/node/10925)

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ARSENIC REMEDIATION TECHNIQUES

The constantly increasing degree of industrialization and rising standards of living are strongly impacting on the use of available water sources. Controlling heavy metal discharges and removing toxic heavy metals from aqueous solutions have become a challenge for the 21st century. The commonly used procedures for removing metal ions from aqueous streams include Oxidation, Ion Exchange, Reverse Osmosis, Nanofiltration, Adsorption and Bucket Treatment. The basic principle, procedural details and commercially available instrumentation based on above phenomenon have been described in brief as below:

Oxidation Process
Arsenic is present in groundwater in As (III) and As (V) forms in different proportions. Most treatment methods are effective in removing arsenic in pentavalent form and hence include an oxidation step as pre-treatment to convert arsenite to arsenate. Arsenite can be oxidized by oxygen, ozone, free chlorine, hypochlorite, permanganate, hydrogen peroxide and Fultons reagent but atmospheric oxygen, hypochloride and permanganate are commonly used for oxidation in developing countries. H3AsO3 H3AsO3 3 H3AsO3 + + + O2 HClO = = H2AsO4HAsO4- + Cl- + 3H+

2 KMnO4 =

3 HAsO4- + 2MnO2+ + 2 K+ + 4 H+ + H2O

Air oxidation of arsenic is very slow and can take weeks for oxidation (Pierce and Moore, 1982) but chemicals like chlorine and permanganate can rapidly oxidize arsenite to arsenate under wide range of conditions.

Solar Oxidation
SORAS are a simple method of solar oxidation of arsenic in transparent bottles to reduce arsenic content of drinking water (Wegelin et al., 2000). Ultraviolet radiation can catalyze the process of oxidation of arsenite in presence of other oxidants like oxygen (Lara et al., 2006). Experiments in Bangladesh show that the process on average can reduce arsenic content of water to about one-third.

Ion Exchange
Ion exchange is an exchange of ions between two electrolytes or between an electrolyte solution and a complex (Figure 1.04).

16

In most cases the term is used to denote the processes containing of of purification, aqueous with and solid separation, other ionpolymeric decontamination

solutions

exchangers. The process is similar to that of activated alumina just the medium is a synthetic resin of more well defined ion exchange capacity. The process is normally used for removal of specific undesirable cation or anion from water. As the resin becomes exhausted, it needs to be regenerated. The arsenic exchange and regeneration equations with common salt solution as regeneration agent are as follows: Figure 1.04: Ion exchange process + 2Cl-

2R-Cl

HAsO4--

R2HAsO4

Arsenic exchange R2HAsO4 + 2Na+ + 2Cl= 2R-Cl + HAsO4-+ 2Na+

Regeneration Where, R stands for ion exchange resin. The ion exchange process is less dependent on pH of water. The efficiency of ion exchange process is radically improved by pre-oxidation of As (III) to As (V) but the excess of oxidant often needs to be removed before the ion exchange in order to avoid the damage of sensitive resins. Development of ion specific resin for exclusive removal of arsenic can make the process very attractive. Tetrahedron ion exchange resin filter tested under rapid assessment program in Bangladesh (BAMWSP, DFID and Water Aid, 2001) showed promising results in arsenic removal. The system needs pre-oxidation of arsenite by sodium hypochloride. The residual chlorine helps to minimize bacterial growth in the media. The saturated resin requires regeneration by recirculating NaCl solution. The liquid wastes rich in salt and arsenic produced during regeneration require special treatment.

Membrane Techniques
Membrane techniques like reverse osmosis, nanofiltration and electro dialysis are capable of removing all kinds of dissolved solids including arsenic from water.

17

Natural osmosis occurs when solutions with two different concentrations are separated by a semi-permeable membrane (Figure 1.05). Pure water is driven and from the concentrated solution collected

downstream of the membrane. Because RO membranes are very restrictive, they yield very slow flow rates. RO also involves an ionic exclusion process, only solvent is allowed to pass through the semi-permeable RO membrane, while virtually all ions and dissolved molecules are retained (including salts and sugars). Figure 1.05: Reverse osmosis process

Ultra Filtration
Ultra Filtration (UF) is a variety of membrane filtration in which hydrostatic pressure forces a liquid weight against are a semipermeable while water membrane. and low the Suspended solids and solutes of high molecular retained molecular weight solutes pass through

membrane (Figure 1.06). This separation process is used in industry and research for purifying and concentrating solutions, macromolecular protein (103-106 solutions. Da) Ultra especially

filtration is not fundamentally different from reverse osmosis, microfiltration or nanofiltration, except in terms of the size of the molecules it retains. Figure 1.06: Ultra filtration process

MRT-1000 and Reid System Ltd.

Jago Corporation Limited promoted a household reverse osmosis water dispenser MRT-1000 manufactured by B & T Science Co. Limited, Taiwan. This system was tested at BUET and showed arsenic (III) removal efficiency more than 80%. A wider spectrum reverse osmosis system named Reid System Limited was also promoted in Bangladesh. Experimental results showed that the system could effectively reduce arsenic content along with other impurities in water. The capital and operational costs of the reverse osmosis system would be relatively high.

18

Low Pressure Nanofiltration

Oh et al., (2000) applied reverse osmosis and nanofiltration treatment applying of membrane arsenic processes contaminated by bicycle for pump. the A water

low pressure

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 (Figure 1.07). Arsenite was found to have lower rejection than arsenate in ionized forms and hence water containing higher arsenite requires pre-oxidation for reduction of total arsenic acceptable level. In tube well water in Bangladesh the average ratio of arsenite to total arsenic was found to be 0.25. Figure 1.07: Nanofiltration process

Adsorption Processes
Water treatment with coagulants such as alum, Al2(SO4)3.18H2O, ferric chloride, FeCl3 and ferric sulfate Fe2(SO4)3.7H2O are effective in removing arsenic from water. Ferric salts have been found to be more effective in removing arsenic than alum on a weight basis and effective over a wider range of pH. In both cases pentavalent arsenic can be more effectively removed than trivalent arsenic. In the coagulation-flocculation process aluminium sulfate, or ferric chloride, or ferric sulfate is added and dissolved in water under efficient stirring for one to few minutes. The water is then gently stirred for few minutes for agglomeration of microflocs into larger easily settable flocs. During this flocculation process all kinds of micro particles and negatively charged ions are attached to the flocs by electrostatic attachment. Arsenic is also adsorbed onto coagulated flocs. As trivalent arsenic occurs in non-ionized form, it is not subject to significant removal. Oxidation of As (III) to As (V) is thus required as a pre-treatment for efficient removal. This can be achieved by addition of bleaching powder (chlorine) or potassium permanganate. The possible chemical equations of alum coagulation are as follows: Al2(SO4)3.18 H2O Alum dissolution 2 Al+++ + 6H2O = 2 Al(OH)3 + 6 H+ = 2 Al+++ + 3 SO4+++ + 18 H2O

Aluminium precipitation (acidic)

19

H2AsO4-

Al(OH)3

Al-As (complex + other products)

Co-precipitation (Non-stoichiometric, non-defined product) Arsenic adsorbed on aluminium hydroxide flocs as Al-As complex is removed by sedimentation. Filtration may be required to ensure complete removal of all flocs. Similar reactions take place in case of ferric chloride and ferric sulfate with the formation of Fe-As complex as end product which is removed by the process of sedimentation and filtration. The possible reactions of arsenate with hydrous iron oxide are shown below where [ FeOH] represents oxide surface site (Mok and Wai, 1989; Hering et al., 1996). Fe(OH)3 (s) + H3AsO4 FeOH + AsO43- + 3 H+ FeOH + AsO43- + 2 H+ FeAsO4. 2H2O + H2O FeH2AsO4 + H2O FeHAsO4- + H2O

Immobilization of arsenic by hydrous iron oxide requires oxidation of arsenic species into As (V) form for higher efficiency. Arsenic removal is dependent on pH. In alum coagulation, the removal is most effective in the pH range 7.2-7.5 and in iron coagulation; efficient removal is achieved in a wider pH range usually between 6.0 and 8.5 (Ahmed and Rahman, 2000).

Bucket Treatment Unit

The Bucket Treatment Unit (BTU), developed by DPHE Danida Project is based on the principles of coagulation, co-precipitation and adsorption processes. It consists of two buckets, each 20 litre capacity, placed one above the other. Chemicals are mixed manually with arsenic contaminated water in the upper red bucket by vigorous stirring for about 90 seconds. The mixed water is then allowed to flow into the lower green bucket via plastic pipe and a sand filter installed in the lower bucket. The flow is initiated by opening a valve fitted slightly above the bottom of the red bucket to avoid inflow of settled sludge in the upper bucket. The lower green bucket is practically a treated water container. The DPHE Danida project in Bangladesh distributed several thousand BTU units in rural areas of Bangladesh. These units are based on chemical doses of 200 mg/L aluminium sulfate and 2 mg/L of potassium permanganate supplied in crushed powder form. The units were reported to have very good performance in arsenic removal in both field and laboratory conditions (Sarkar et al., 2000; Kohnhorst and Paul, 2000). In many cases, the units under rural operating conditions fail to remove arsenic to the desired level of 0.05 mg/L in Bangladesh. Poor mixing and variable water quality particularly pH of ground water in

20

different locations of Bangladesh appeared to be the cause of poor performance in rapid assessment. The method Bucket Treatment Unit used zero-valent iron. This method had between 68% to 100% arsenic removal efficiency with a 36 L/day flow rate of filtrate (Awuah et al., 2010).

Stevens Institute Technology: A Modified Version

This technology also uses two buckets, one to mix chemicals (reported to be iron sulphate and calcium hypochloride) supplied in packets and the other to separate flocs by the process of sedimentation and filtration. The second bucket has a second inner bucket with slits on the sides as shown in the figure 1.08 to help sedimentation and keeping the filter sand bed in place. The chemicals form visible large flocs on mixing by stirring with stick. Rapid assessment showed that the technology was effective in reducing arsenic levels to less than 0.05 mg/L in case of 80 to 95% of the samples tested (BAMWSP, DFID, Wateraid, 2001). The sand bed used for filtration is quickly clogged by flocs and requires washing at least twice a week.

Figure 1.08: Stevens Institute Filtration Technology

21

Sorptive Filtration Media

Several sorptive media have been reported to remove arsenic from water. These are activated alumina, activated carbon, iron and manganese coated sand, kaolinite clay, hydrated ferric oxide, activated bauxite, titanium oxide and many synthetic media. The efficiency of sorptive media depends on the use of oxidizing agent as an aid to sorption of arsenic. Saturation of media by different contaminants and components of water takes place at different times of operation depending on the specific sorption affinity of the medium to the given component. Saturation means that the efficiency in removing the desired impurities becomes zero.

Activated Alumina
Activated alumina, Al2O3, having good sorptive surface is an effective medium for arsenic removal (Kim et al., 2004). When water passes through a packed column of activated alumina, the impurities including arsenic present in water are adsorbed on the surfaces of activated alumina grains. Eventually the column becomes saturated, first at its upstream zone and later the saturated zone moves downstream towards the bottom end and finally the column get totally saturated. Regeneration of saturated alumina is carried out by exposing the medium to 4% caustic soda, either in batch or by flow through the column resulting in high arsenic contaminated caustic waste water. The residual caustic soda is then washed out and the medium is neutralized with a 2% solution of sulfuric acid rinse. During the process about 5-10% alumina is lost and the capacity of the regenerated medium is reduced by 30-40%. The activated alumina needs replacement after 3-4 regeneration. Like coagulation process, pre-chlorination improves the column capacity dramatically. Some of the activated alumina based sorptive media used in Bangladesh include:

BUET Activated Alumina Alcan Enhanced Activated Alumina ARU of Project Earth Industries, Inc., USA Apyron Arsenic Treatment Unit

The BUET and Alcan activated alumina have been extensively tested in field condition in different areas of Bangladesh under rapid assessment and found very effective in arsenic

22

removal (BAMWSP, DFID, WaterAid, 2001). The Arsenic Removal Units (ARUs) of Project Earth Industries Inc. (USA) used hybrid aluminas and composite metal oxides as adsorption media and were able to treat 200-500 Bed Volume (BV) of water containing 550 g/L of arsenic and 14 mg/L of iron (Ahmed et al., 2000).

Granular Ferric Hydroxide

M/S Pal Trockner (P) Ltd, India and Sidko Limited, Bangladesh installed several Granular Ferric Hydroxide based arsenic removal units in India and Bangladesh. The Granular Ferric Hydroxide is arsenic selective adsorbent developed by Technical University, Berlin, Germany. The unit requires iron removal as pre-treatment to avoid clogging of filter bed. The proponents of the unit claim to have very high arsenic removal capacity and produces nontoxic spent granular ferric hydroxide.

Indigenous Filters
There are several filters available in Bangladesh which uses indigenous material as arsenic adsorbent. Red soil rich in oxidized iron, clay minerals, iron ore and iron scrap or fillings are known to have capacity for arsenic adsorption. Some of the filters manufactured using these materials include:

Sono 3-Kolshi Filter Granet Home-made Filter Chari Filter Adsorptive Filter Shafi Filter Bijoypur clay

The Sono 3-Kolshi Filter uses zero valent iron fillings and coarse sand in the top kolshi, wood coke and fine sand in the middle kolshi while the bottom kolshi is the collector of the filtered water (Khan et al., 2000). Earlier Nikoliadis and Lackovic (1998) showed that 97% arsenic can be removed by adsorption on a mixture of zero valent iron fillings & sand and recommended that arsenic species could have been removed through formation of co-

23

precipitates, mixed precipitates and by adsorption onto the ferric hydroxide solids. The Sono 3-Kolshi unit has been found to be very effective in removing arsenic (BAMWSP, DFID and Water Aid, 2001). The one-time use unit becomes quickly clogged, if groundwater contains excessive iron. The Granet home-made filter contains relatively inert materials like brick chips and sand as filtering media. No chemical is added to the system. Air oxidation and adsorption on ironrich brick chips and flocs of naturally present iron in ground water could be the reason for arsenic removal from ground water. The unit produced inadequate quantity of water and did not show reliable results in different areas of Bangladesh and under different operating conditions. The Chari filter also uses brick chips and inert aggregates in different Charis as filter media. The effectiveness of this filter in arsenic removal is not known. The Shafi and Adarsh filters use clay material as filter media in the form of candle. The Shafi filter was reported to have good arsenic removal capacity but suffered from clogging of filter media. The Adarsh filter participated in the rapid assessment program but failed to meet the technical criterion of reducing arsenic to acceptable level (BAMWSP, DFID and WaterAid, 2001). Bijoypur clay was also found to adsorb arsenic from water (Khair, 2000).

Cartridge Filters
Filter units with cartridges filled with sorptive media or ion-exchange resins are readily available in the market. These units remove arsenic like any other dissolved ions present in water. These units are not suitable for water having high impurities and iron in water. Presence of ions having higher affinity than arsenic can quickly saturate the media requiring regeneration or replacement. Two household filters were tested at BUET laboratories. These are:

Chiyoda Arsenic Removal Unit, Japan Cool mart Water Purifier, Korea

The Chiyoda Arsenic Removal Unit could treat 800 BV meeting the WHO guideline value of 0.01 mg/L and 1300 BV meeting the Bangladesh Standard of 0.05 mg/L when the feed water arsenic concentration was 0.30 mg/L. The Coolmart Water Purifier could treat only 20L of water with an effluent arsenic content of 0.025 mg/L (Ahmed et al., 2000). The initial and operation costs of these units are high and beyond the reach of the rural people.

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DRAWBACKS OF THE EXISTING REMEDIATION TECHNIQUES

These currently practiced technologies for removal of pollutants from industrial effluents appear to be inadequate, creating often-secondary problems with metal bearing sludge, which are extremely difficult to dispose off. Further, research findings have clearly raised strong doubts about the advisability of the use of synthetic coagulants used for metal removal. Table 1.07 explains the advantages and disadvantages of the conventional techniques used for arsenic remediation.

Table 1.07: A Comparison of arsenic remediation technologies Technologies Advantages Disadvantages

Oxidation/precipitation Air oxidation Chemical oxidation Relatively simple, low The process remove only a cost but slow process part of arsenic Capital costs and operating Relatively simple and costs are typically high. rapid process Oxidizes other impurities and kills microbes Coagulation co-precipitation Relatively low cost Relatively simple Common Chemicals available Produces toxic sludges Low removal of As(III) Pre-oxidation may be required

Alum Coagulation Iron Coagulation

Sorption Techniques Activated Alumina Iron Coated Sand Ion Exchange Resin Other sorbents Relatively well known and commercially available Well defined technique Development of scope Produces toxic solid waste

Replacement/regeneration required High tech operation and maintenance Relatively high cost

Membrane Techniques Nanofiltration Reverse osmosis Electro dialysis Well defined and high removal efficiency No toxic solid wastes produced Capable of removal of other contaminants Very high capital and running cost High tech operation and maintenance Toxic wastewater produced

(Source: www.freedrinkingwater.com/water-education/quality-water filtration-method.htm)

25

GREEN TECHNOLOGIES
Unfortunately, the Science particularly Chemistry, despite numerous contributions to the well being and progress of humanity, has been blamed for the present ills of the world. In fact, it is not Chemistry or Science or Technology but our past mistakes of increasing the production only without considering the simultaneous generation of large amount of side products or waste which have underlined us as culprit. Basically unscientific and careless rapid urbanization, industrialization and agricultralization are major threat to environment. Chemists, since 1990 have started addressing complicated environmental issues in safe and an economically profitable manner under the various names like Clean Chemistry, Environmentally Benign Chemistry, Sustainable Chemistry, Come Back to Nature, Grey to Green Chemistry, Green Technologies, Eco-friendly Techniques, Green Processes and more popularly as Green Chemistry. Green Chemistry is a special contribution of chemists to the conditions for sustainable development, incorporating an environmentally benign by design approach to all aspects of chemical industry. The word Green Chemistry was jointly coined by Prof. Paul T. Anastas and Prof. John C. Warner, which means The invention, design and application of chemicals products and processes to reduce or to eliminate the use and generation of hazardous substances. To combine technology with environmental safety is one of the key challenges of the new millennium. There is a global trend of bringing technology into harmony with natural environment, thus aiming to achieve the goals of protection of ecosystem from the potentially deleterious effects of human activity and finally improving its quality. The challenges of safe and various treating and diagnosing environmental problems require discovery of newer, more potent, specific, safe and cost effective synthetic or natural molecules. The magic plants are around and waiting to be discovered and commercialized . They are now recognized and accepted as storehouses of infinite and limitless benefits to human beings. These natural systems are often referred to as Green Technologies, as they involve naturally occurring plant materials. Biosorption is one such important phenomenon, which is based on one of the twelve principles of Green Chemistry Use of Renewable Resources. It has garnered a great deal of attention in recent years due to rise in environmental awareness and consequent severity of legislation regarding the abatement of arsenic ions from water bodies.

26

Prof. Paul T. Anastas

Prof. John C. Warner

Prof. Paul T. Anastas (Green Chemistry Institute, American Chemical Society, Washington) and Prof. John C. Warner (University of Massachusetts, Washington) have given twelve principles of Green Chemistry.

DESIGN FOR ENERGY EFFICIENCY

LESS HAZARDOUS CHEMICALS SYNTHESIS SYNTHESIS

USE OF RENEWABLE FEED STOCKS

SAFER SOLVENTS AND AUXILIARIES

ATOM ECONOMY

DESIGNING SAFER CHEMICALS

SAFER CHEMISTRY

GREEN CHEMISTRY
PREVENTION IS BETTER THAN CURE

USE OF SELECTIVE CATALYST

REAL TIME ANALYSIS FOR POLLUTION PREVENTION

REDUCED DERIVATIVES

DESIGN FOR DEGRADATION

Figure 1.09: Twelve principles of Green Chemistry

27

BIOSORPTION: A GREEN SOLUTION

During the 1970s, increasing environmental awareness and concern led to a search for new techniques capable of inexpensive treatment of polluted waste waters with metals/metalloids. The search for new technologies involving the removal of toxic pollutants from waste waters has directed attention towards Biosorption, based on binding capacities of various agricultural waste/biological materials. The assessment of the metal/metalloid binding capacity of biomaterials has gained momentum since 1995 (Volesky and Holan 1995a). Till date, research in the area of biosorption suggests it to be an ideal alternative for abatement of metal/metalloid containing effluents. Biosorption is a rapid phenomenon of passive metal sequestration by the

non-growing biomass/adsorbents. It can be defined as a non-directed physicochemical interaction that may occur between metal/metalloid/radionuclide species and microbial cells. The biosorption process involves a solid phase (sorbent or biomaterial; adsorbent; biological material) and a liquid phase (solvent, normally water) containing a dissolved species to be sorbed (adsorbate, metal/metalloid). Due to the higher affinity of the adsorbent for the adsorbate species, the latter is attracted and bound by different mechanisms. The process continues till equilibrium is established between the amount of solid bound adsorbate species and its portion remaining in the solution. The degree of adsorbent affinity for the adsorbate determines its distribution between the solid and liquid phases.

Biomaterials: A Forecast for the Future

Biomaterials are attractive since naturally occurring biomaterials/adsorbents or spent biomaterial can be effectively reused. Natural materials that are available in large quantities or certain waste from agricultural operations may have potential to be used as low cost adsorbents, as they represent unused resources, widely available and are environment friendly (Hench, 1998; Park et al., 2010; Narukawa et al., 2012). Availability is a major factor to be taken into account to select biomaterial for clean up purposes (Volesky and Holan, 1995b). Some biomaterial can bind and remove a wide range of metals/metalloids with no specific priority, where as other are specific for certain types of metals/metalloid. When choosing the biomaterial for metal biosorption experiments, its origin is a major factor to be taken into account (Keith et al., 1979). In Biosorption, the use of non living biomaterials containing metal binding compounds would have the advantage of not requiring tremendous care and maintenance as well as being useful in remediating toxic high levels of contaminants that would otherwise kill live system (Basso et al., 2002; Narukawa and Chiba, 2010; Egila et al., 2011). However, live biological system work well for low concentration; they cannot survive the high levels that are found in seriously contaminated areas and industrial effluents (Fourest and Roux, 1992).

28

Biomaterials can come from Industrial waste, which should be free of charge. Plants easily available in large amount in nature and of quick growth. Agricultural waste products. Organisms of quick growth, especially cultivated for biosorption process.

Biosorption clearly shows that from most perspectives, plants are ideal for environmental clean up: capital cost is low, ongoing operational costs are minimal, implementation is easy and non-invasive and public acceptance is high (Veglio and Belochini, 2001; Volesky, 1999). All this shows that biosorption is a new and vibrant technology having great potential. To realize this, it will be necessary to understand the various processes that are involved in it. This may require a multidisciplinary approach and diverse fields of plant biology.

Advantages of biosorption process Cost-effectiveness High efficiency Minimization of chemical and or biological sludge Regeneration of biomaterial Possibility of metal/metalloid recovery

Competitive performance
Metal/Metalloid selectivity
(Volesky, 2003)

29

BIOSORPTION: MECHANISTIC ASPECTS

The complex structure of plant materials and microorganisms implies that there are many ways for the metal to be taken by the biomaterial. Numerous chemical groups have been suggested to contribute to biosorption metal binding by either whole organisms or by molecules. These groups comprises hydroxyl, carbonyl, carboxyl, sulphaydryl, thioether, sulphonate, amine, amino, imidazole, phosphonate and phosphodiester etc. The importance of any given group for biosorption of certain metals by plant biomaterial depends on factors such as number of sites in the biomaterial, the accessibility of the sites, the chemical state of the sites (availability) and affinity between site and metal (Volesky et al., 1999). Adsorption and desorption studies invariably yield important information on the mechanism of metal biosorption. This knowledge is essential for understanding of the biosorption process and it serves as a basis for quantitative stoichiometric considerations, which constitute the foundation for mathematical modeling of the process (Yang and Volesky, 2000).

Biosorption Mechanism
Various metal-binding mechanisms have been postulated to be active in biosorption process and presented in figure 1.10.

BIOSORPTION MECHANISMS

INTRACELLULAR ACCUMULATION

CELL SURFACE ADSORPTION AND PRECIPITATION

EXTRACELLULAR
ACCUMULATION PRECIPITATION

TRANSPORT ACROSS CELL MEMBRANES

ION EXCHANGE

COMPLEXATION

PHYSICAL ADSORPTION

PRECIPITATION

Figure 1.10: Mechanism of biosorption Due to the complexity of the biomaterials used, it is possible that at least some of these mechanisms are acting simultaneously to varying degrees, depending on the biomaterial and the solution environment.

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Chemisorption
It is the adsorption in which the forces involved are valence forces of the same kind as those operating in the formation of chemical compounds. Some features, which are useful in recognizing chemisorption, include: The phenomenon is characterized by chemical specificity. Since the adsorbed molecules are linked to the surface by valence bonds, they will usually occupy certain adsorption sites on the surface and only one layer of chemisorbed molecules is formed (monolayer adsorption). The energy of chemisorption is of the same order of magnitude as the energy change in a chemical reaction between a solid and a fluid. Chemisorption is irreversible.

Chemisorption is of three types: Ion Exchange, Chelation and Co-ordination (Complexation).

Ion Exchange
Ion exchange is a reversible chemical reaction wherein an ion in a solution is exchanged for a similarly charged ion attached to an immobile solid particle. These solid ion-exchange particles are either naturally occurring inorganic zeolites or synthetically produced organic resins. Synthetic organic resins are the predominant type used today because their characteristics can be tailored to specific applications. Ion exchange reactions are stoichiometric, reversible and as such they are similar to other solution-phase reactions. For example, in the reaction the nickel ions of the nickel sulfate (NiSO4) are exchanged for the calcium ions of the calcium hydroxide Ca(OH)2 molecule. NiSO4 + Ca (OH)2 Ni(OH)2 + CaSO4

Chelation
The word chelation is derived from the Greek word chele, which means claw and is defined as the firm binding of a metal ion with an organic molecule (ligand) to form a ring structure. The resulting ring structure protects the mineral from entering into unwanted chemical reactions. Examples include the carbonate (CO32) and oxalate (C2O42) ions:

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Coordination (Complex Formation)

A coordination complex is any combination of cations with molecules or anions containing free pairs of electrons. Bonding may be electrostatic, covalent or a combination of both; the metal ion is coordinately bonded to organic molecules. Example of the formation of a coordination compound is: Cu2+ + 4H2O [Cu (H2O)]42+ Cu2+ + 4Cl [CuCl4]2 Where, coordinate covalent bonds are formed by donation of a pair of electrons from H 2O and Cl (Lewis base) to Cu2+ (Lewis acid). In general, biosorption of toxic metals and radionuclide is based on non-enzymatic processes such as adsorption. Adsorption is due to the non-specific binding of ionic species to polysaccharides and proteins on the cell surface or outside the cell. Bacterial cell walls and envelopes, and the walls of fungi, yeasts and algae, are efficient metal biomaterials that bind charged groups. The cell walls of gram-positive bacteria bind larger quantities of toxic metals and radionuclide than the envelopes of gram-negative bacteria. Bacterial sorption of some metals can be described by the linearized Freundlich adsorption equation: log S = log K + n log C where, S is the amount of metal absorbed in mol/g, C is the equilibrium solution concentration in mol/L, K and n are the Freundlich constants. Biomaterial deriving from several industrial fermentations may provide an economical source of biosorptive materials. Many species have cell walls with high concentrations of chitin, a polymer of N-acetyl-glucosamine that is an effective biomaterial. Biosorption uses biomaterial raw materials that are either abundant (e.g., seaweeds) or wastes from other industrial operations (e.g., fermentation wastes). The metal-sorbing performance of certain types of biomaterial can be more or less selective for heavy metals, depending on the type of biomaterial, the mixture in the solution, the type of biomaterial preparation, and the chemical-physical environment.

Physisorption
In physisorption, physisorbed molecules are fairly free to move around the sample. As more molecules are introduced into the system, the adsorbate molecules tend to form a thin layer

32

that covers the entire adsorbent surface. Physiosorption takes place with the help of Vander Waals forces. Some features, which are useful in recognizing physisorption, include: The adsorbate molecules are held by comparatively weaker Vander Waals forces, thus resulting into lower activation energy. The process is, however, reversible as the substance adsorbed can be recovered from the adsorbent easily on lowering the pressure of the system at the same temperature. Physisorption may extend beyond a monolayer also, since the physical forces can operate at any given distances. Physical adsorption is not specific in nature because it involves Vander Waals forces, which exist among the molecules of every two substances.

Factors Affecting Biosorption Temperature seems not to influence the biosorption performances in the range of 20O-35OC. pH seems to be the most important parameter in the biosorption process. It affects the solution chemistry of the metals/metalloids, the activity of the functional groups in the biomaterial and the competition of metallic ions. Biomaterial concentration in solution seems to influence the specific uptake. An increase in biomaterial concentration leads to interference between the binding sites. Biosorption is selective also. This aspect has to be investigated in detail. Biosorption is mainly applied to treat waste water containing metal ions and the removal of one metal may be influenced by the presence of other metals/metalloids. (Fourest and Roux, 1992)

33

BIOSORPTION: APPLICATION STRATEGIES

Over the past few years, intensifying research into metal biosorption elucidated the principles of this effective metal removal phenomenon. Biosorption can be cost effective, particularly in environmental applications where low cost of the metal removal process is most desirable. Some efficient natural biomaterials have been identified that require little modification in their preparation. It is particularly in ecological aspects where biosorption can make a difference due to its anticipated low cost. The application makes the research and development work in this novel area exciting and worthwhile. Biosorption process could be used even with a relatively low degree of understanding of its metal binding mechanisms better understanding will make it more effective and optimized applications. If the biosorption processes were to be used as an alternative in the waste water treatment scheme, the regeneration of the biomaterial may be crucially important for keeping the process cost down and to open the possibility of recovering the metal/metalloid extracted from liquid phase. For this process, it is desirable to desorb the sorbed metals and to regenerate the biomaterial for another cycle of application.

Desorption Involves Yield the metals in a concentrated form Restore the biomaterial to close to the original conditions for effective reuse Undiminished metal uptake No physical change or damage

Extensive desorption work may be necessary for assessing whether this is possible and under what conditions. Desorption and sorbent regeneration studies might require somewhat different methodologies. While the regeneration of the biomaterial may be accomplished by washing the metal laden with an appropriate solution, the type and strength of the solution would depend on just how the deposited metal has been bound. Dilute solutions of mineral acids (hydrochloric acid, nitric acid, sulphuric acid and acetic acid) can be used for metal desorption from the biomaterial (Pagnanelli et al., 2002). Due to different affinities of metal ions for the predominant sorption site (under the solution conditions), there will be a certain degree of metal selectivity by the sorbent on the uptake. Similarly, selectivity may be achieved upon the elution-desorption operation (Jessen et al.,

34

2005). Advantage could be taken of this selectivity on the desorption side of the operation which can contribute to the separation of metals from one another, if desirable. The overall capacity of sorption process is to concentrate the sorbate metals. This is assessed by expressing a simple overall process parameter, the concentration ratio (CR). Obviously, the higher the CR, the better is the overall performance of the sorption process making the eventual recovery of the metal more feasible as it becomes more concentrated in the small volume of the eluent solution. The feasibility of applying the biosorption process into wastewater purification would best be assessed based on a stage-wise approach. A considerable amount of research on biomaterials has developed solid basis of knowledge and indicated their enormous potential. The highest priority at the early stage would be the preliminary and approximate assessment of the commercial potential and practicality of application of the new technology based on the family of new biomaterial products. The preliminary assessments that should be carried out simultaneously as part of a better quantitative estimation of this technology are as follows:

Assessment of the Competiting Technologies

The current costs and market share of the established conventional processes for metal removal/recovery from dilute solutions or waste waters have to be summarized or assessed. As the emission standards tighten the conventional methods for metal detoxification are becoming progressively more inadequate or prohibitively costly for use of water treatment. Better and effective metal removal technologies are invariably more costly and often just not feasible for that purpose. The search is on for efficient and particularly cost effective remedies. Biosorption promises to fulfill the requirements. Its overall performance and process application modes justify a comparison with the other existing techniques.

Assessment of the Market Size

It is known that the environmentally-based market for metal removal /decontamination of metal containing (industrial) effluents is enormous, the actual figure to support this generally prevailing perception would be most convincing for commercialization. A quantitative review of the potential clientele for the biosorption metal-removal process needs to be carried out for different countries where applications of biosorption technology would be considered. Comparison of costs between the traditional and new technology establish the feasibility of biomaterial applications and their competitiveness in the market place. As the application of biosorption proves cheaper, it is anticipated that new applications, otherwise perhaps not feasible, will significantly increase the size of the current market and scope of potential clients for biosorption technology.

35

Assessment of Costs of New Biomaterial

Approximate costs of different types of raw biomaterial need to be ascertained, as well as the costs of processing the biomaterial into applicable biomaterials maintaining their high efficiency. Preliminary technical work needs to be carried out on the processing, necessary for biomaterial formulation into a product suitable for use. Different raw biomaterial would require specific treatment for their optimal formulation into finished ready to use products. This part would entail specifically planned small-scale laboratory work resulting in an efficient biomaterial. The most compelling reasons for using biosorption technology, based on renewable or waste raw materials, are that it is effective and inexpensive. The initial information gathered in preliminary economic feasibility studies, leads to following main conclusions regarding the application of bioremediation technology.

Ideally, all these preliminary assessments should be carried out simultaneously as part of a better quantitative estimation of the venture feasibility. They could also be carried out simultaneously with the technically oriented pilot-plant efforts. These assumptions lead to considering the low cost of the biomaterials as the primary significant difference factor between the biosorption and other processes. For this reason, the study of the biomaterial sources and costs are particularly important and will allow a measurement of the economic performance of the process.

Biosorption can be viewed as Water treatment process Significant cost saving process in comparison with existing competing techniques. Effective in terms of technical performance, operational qualities and chemical properties. Commonly usable having low sensitivity to environmental and impurity factors. Additional cost reducing because of possible recovery of heavy metals. Cost effective, obviously reinforced by a higher market value of recovered metal and lower costs of biomaterial.

36

BIOMATERIALS USED SO FAR

Bioremediation as a variant and Green Technology becomes promising to remediate the environmental pollutants. It has many advantages, i.e., environmental friendly, excellent performance, possible recycling and low cost for remediation of arsenic from contaminated water. A range of microorganisms (Table 1.08) and plant biomaterials (Table 1.09) have been reported for efficient remediation of arsenic from water bodies. However, there is still a strong challenge in developing economical and commonly available biomaterial for arsenic removal.

Table 1.07: List of microorganisms used for arsenic removal

Microorganism Penicillium purpurogenum Brown rot fungi Aspergellus fumigatus Waste tea fungal biomaterial Bacillus subtilis

Arsenic species As (III) As (V) As (III) As (III) & As (V) As (III)

Reference Ridvan et al., 2003 Kartal & Imamura, 2004 SathishKumar et al., 2004 Murugesan et al., 2006 Hossain & Anantharaman, 2006 Cernansky et al., 2007 Urik et al., 2007 Pokhrel 2007 & Viraraghavan,

Heat resistant fungi Aspergillus clavatus Fungal biomass

As (III) As (III) & As (V) As (III) & As (V)

Thiobascillus Algae

As (V) As (V)

Malik et al., 2009 Llorente-Mirandes 2010 et al.,

Lessonia nigrescens Escherichia coli Lactobacillus acidophilus Aspergilus flaves

AS (V) As (III) As (III) As (III)

Ruiz-Chancho et al., 2010 Wu et al., 2010 Singh & Sharma, 2010 Maheshwari 2011 & Murgusen,

Turbinaria conoides

As (V)

Sivaprakash & Rajamohan, 2011

37

Table 1.08: List of plant biomaterials used for arsenic removal

Plant Biomaterial Water lettuce Orange waste Garcinia cambogia Coconut fiber Rice husk Sorghum biomass Jute leaf powder (JLP), sugarcane powder Banana peel Picea abies Pteris vittata Seaweed

Arsenic Species As (V) As (III) & As (V) As (III) As (V) As (III) & As (V) As (V) As (V) As (V) As (V) As (III) & As (V) As (III) & As (V)

Reference Basu et al., 2003 Ghimire et al., 2003 Kamala et al., 2005 Igwe & Abia, 2006 Amin et al., 2006 Haque et al., 2007 Islam et al., 2007 Memon et al., 2008 Urik et al., 2009 Wang et al., 2011 Llorente-Mirandes et al., 2011 Mahamadi, 2011 Rezaitabar et al., 2012

Water hyacinth Farm Rice

As (III) & As (V) Total As

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CHEMICAL SPECIATION OF ARSENIC

The element exists in different oxidation states and in different chemical form in the environment, which is called as species. An element can have different species and these species can have different property and toxicity between each other. The doses of these elements are also important, higher doses cause toxicity and lower doses cause deficiency. As a result, total concentration of an element does not give enough information about its toxicity, biotransformation and other biochemical properties of the element to be analyzed (Jain and Ali, 2000). Speciation is essential to understand the distribution, mobility, toxicity and bioavailability of chemical elements in natural systems. Speciation of arsenic is an important consideration because toxicity is mainly species-dependent and not well correlated with the total arsenic concentration (Kumarasen and Riyazudin, 2001). Determination of total arsenic in a sample is of limited value because the result does not usually reflect the true level of hazard of that element. Hence, speciation of arsenic is highly relevant in providing meaningful risk assessment data to assess the appropriate hazard level (Caumette et al., 2011). Inorganic arsenic is considered to be the most toxic form of the element (Quaghebeur and Rengal, 2004). Inorganic arsenic species, i.e. As (III) and As (V), predominantly found in natural water, are more toxic than organic species (Smith et al., 2009). The speciation of arsenate and arsenite is determined by the pH as both (arsenate and arsenite) protonate/deprotonate depending on the pH of the solution. The trivalent arsenic species exists in a non-ionic form (H3AsO3) in the pH range 27 and in the anionic (H2AsO3-1, HAsO3-2) form in the pH range 710 (Moriarty et al. 2009). The pentavalent arsenic species exists in the monovalent (H3AsO4 1) and divalent anion (H2AsO42) in the pH range 29 as shown in figure 1.11.

Figure 1.11: Speciation of arsenite and arsenate as a function of pH (Source: http://ldambies.free.fr/arsenicchemistry.html)

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TECHNIQUES USED FOR DETECTION AND SPECIATION OF ARSENIC

Several analytical techniques have been used for the detection and speciation of arsenic species in aqueous system like Capillary Zone Electrophoresis (Timerbaev et al., 2000, Timerbaev et al., 2001), Mass Spectroscopy (Mcsheehy et al., 2001), Solvent Extraction (Vela et al., 2001; Galagher et al., 2002), HPLC (Ali et al., 2002), Electrophoresis (Sun et al., 2003), Gas Chromatography (Bednar et al., 2004), HPLC-NAA (Youqing et al 2004), Sonoelectrochemical (Simm et al., 2005), Spectrophotometry (Jain and Ali, 2000; Butcher, 2007), Hydride Generation (Del Razo et al., 2001; Hashemi and Modasser, 2007), Ion Exclusion Chromatography (Yuan and Le, 2009), Atomic Fluorescence Spectroscopy (Liu et al., 2009), Microwave assisted sequential extraction (Jamali et al., 2009; Rahman et al., 2009), HPLC-ICP-MS (Miyashita et al., 2009; Caumette et al., 2011) and Ion Exchange Chromatography (Ammann, 2011; Chavan et al., 2011).

Voltammetric Technique
Voltammetry is an electrochemical method in which current is measured as a function of the applied potential. This technique is based on the principle of measurement of the diffusion controlled current flowing in an electrolysis cell in which one electrode is polarisable (Fifield and Kealey, 2000). A time dependent potential is applied to an electrochemical cell, and the current flowing through the cell is measured as a function of the potential. A plot of current which is directly proportional to the concentration of an electroactive species as a function of applied potential is called a voltammogram. The voltammogram provides quantitative and qualitative information about the species involved in the oxidation or reduction reaction or both at the working electrode. The advantage of this technique include high sensitivity where quantitative and qualitative determination of metals, inorganic and organic compounds at trace levels (Fifield and Kealey, 2000), selectivity towards electro active species (Barek et al., 2001), a wide linear range, portable and low-cost instrumentation, speciation capability and a wide range of electrode that allow assays of many types of samples such as environmental samples (Zhang et al., 2002; Ghoneim et al., 2003; Buffle et al., 2005), pharmaceutical samples (Abdine et al., 2002; Hilali et al., 2003 and Carapuca et al., 2005 ), food samples (Ximenes et al., 2000; Volkov and Mwesigwa, 2001) and forensic samples (Pournaghi-Azar and Dastangoo, 2000; Woolever Dewald, 2001). Various advances during the past few years have pushed the detectability of voltammetric techniques from the submicromolar level for pulse Voltammetric techniques to the subpicomolar level by using an adsorptive catalytic stripping voltammetry (Cavicchioli et al., 2004). Stripping technique is one of the most important and sensitive electrochemical

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techniques for measuring trace metals and organic samples. The term stripping is applied to a group of procedures involving pre-concentration of the determinant onto the working electrode, prior to its direct or indirect determination by means of a potential sweep (Wang, 2000). The pre-concentration (or accumulation) step can be adsorptive, cathodic or anodic. Its remarkable sensitivity is attributed to the addition of an effective pre-concentration step with advanced measurement procedures that generate an extremely favourable signal-tonoise ratio as reported by Blanc et al., (2000). Square Wave Voltammetry (SWV) is a large-amplitude differential technique in which a waveform composed of a symmetrical square wave, superimposed on a base staircase potential, is applied to the working electrode. The current is sampled twice during each square wave cycle, once at the end of forward pulse and another at the end of the reverse pulse. Since, the square-wave modulation amplitude is very large, the reverse pulses cause the reverse reaction of the product of the forward pulse. Among the various voltammetric techniques, Square Wave Anodic Stripping Voltammetry (SWASV) has several advantages like excellent sensitivity, rejection of background currents and speed (Salaun et al., 2007). This speed, coupled with computer control and signal averaging, allows for experiments to be performed repetitively and increases the signal tonoise ratio. Applications of square-wave voltammetry include the study of electrode kinetics with regard to preceding, following, or catalytic homogeneous chemical reactions and determination of some species at trace levels. Electroanalytical techniques particularly square wave stripping voltammetry is highly popular for speciation of metals/metalloids in aqueous system (Brusciotti and Duby 2007; Mays and Hussam, 2009; Bose et al., 2011).

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LACUNA IN THE PRESENT STATE OF KNOWLEDGE

The vigorous survey of the relevant literature indicates the following points: Abatement of arsenic has been largely attempted using inorganic coagulants. Not much attention has been paid on decontamination of arsenic using organic biomaterials. The potential of chemically modified biomaterials for cationic metal species has been explored. Information on the ability of chemically modified biomaterials to remove anionic metal species from waste water is still highly restricted. Little attention has been paid on the physico-chemical interaction of arsenic and plant biomaterial which is strongly required for explaining the mechanistic aspects of arsenic sorption. The methods used for arsenic estimation are sensitive to total arsenic rather than individual arsenic species, while the toxicological, physiological and geochemical behaviour depends on its oxidation state.

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