Electrochimica Acta 56 (2011) 50605070

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Removal of arsenic from drinking water by the electrocoagulation using Fe and Al electrodes
M. Kobya a, , U. Gebologlu a , F. Ulu a , S. Oncel a , E. Demirbas b
a b

Gebze Institute of Technology, Department of Environmental Engineering, 41400 Gebze, Turkey Gebze Institute of Technology, Department of Chemistry, 41400 Gebze, Turkey

a r t i c l e

i n f o

a b s t r a c t
A novel technique of electrocoagulation (EC) was attempted in the present investigation to remove arsenic from drinking waters. Experiments were carried out in a batch electrochemical reactor using Al and Fe electrodes with monopolar parallel electrode connection mode to assess their efciency. The effects of several operating parameters on arsenic removal such as pH (49), current density (2.57.5 A m2 ), initial concentration (75500 g L1 ) and operating time (015 min) were examined. Optimum operating conditions were determined as an operating time of 12.5 min and pH 6.5 for Fe electrode (93.5%) and 15 min and pH 7 for Al electrode (95.7%) at 2.5 A m2 , respectively. Arsenic removal obtained was highest with Al electrodes. Operating costs at the optimum conditions were calculated as 0.020 D m3 for Fe and 0.017 D m3 for Al electrodes. EC was able to bring down aqueous phase arsenic concentration to less than 10 g L1 with Fe and Al electrodes. The adsorption of arsenic over electrochemically produced hydroxides and metal oxide complexes was found to follow pseudo second-order adsorption model. Scanning electron microscopy was also used to analyze surface topography of the solid particles at Fe/Al electrodes during the EC process. 2011 Elsevier Ltd. All rights reserved.

Article history: Received 3 December 2010 Received in revised form 21 March 2011 Accepted 22 March 2011 Available online 30 March 2011 Keywords: Arsenic Electrocoagulation Drinking water Iron electrode Aluminum electrode

1. Introduction The presence of arsenic in ground and surface waters is one of the major environmental problems as many people are exposed to excessive arsenic amounts through contaminated drinking water [1,2]. The most serious problems being encountered in many regions of the world such as Argentina, Bangladesh, Chile, India, Mexico, Mongolia, Myanmar, Nepal, New Zealand, Thailand, Taiwan, Turkey, and Vietnam when arsenic concentration in ground and surface water exceeds national and international drinking water standards (permissible limit of 10 g L1 ) [1,3]. Natural water sources especially in the west regions of Turkey such as Kutahya, Izmir and Afyon contain much higher levels of arsenic concentrations (10900 g L1 ) than the allowed maximum level of contamination [4,5]. Arsenic contaminated natural waters are a signicant problem since this compound is known as toxic, mutagenic and carcinogenic. Chronic health effects of arsenic include development of various skin lesions such as hyperpigmentation (dark spots), hypopigmentation (white spots), and keratosis of hands and feet. Long-term exposure to arsenic can also cause cancer of the bladder, lungs, skin, kidney, liver and prostate [6,7]. Due to its high

Corresponding author. Tel.: +90 262 6053214; fax: +90 262 6538490. E-mail address: kobya@gyte.edu.tr (M. Kobya). 0013-4686/$ see front matter 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.electacta.2011.03.086

toxic effects on human health, the USEPA and WHO have lowered the maximum contaminant level for arsenic in drinking water from 50 to 10 g L1 [3,8]. The lowering of this maximum contaminant level makes it necessary to nd novel technologies to meet the regulation. The major arsenic species present in natural and ground waters are arsenate ions: H3 AsO4 , H2 AsO4 , HAsO4 2 and AsO4 3 (oxidation state V) and arsenite ions, H3 AsO3 , H2 AsO3 and HAsO3 2 (oxidation state III). However, As(V) ions are most prevalent in oxygenated water while As(III) is found in anaerobic conditions like in well water or in groundwater Fe/Al gets dissolved from the anode generating corresponding metal ions, which almost immediately hydrolyze to polymeric iron or aluminum oxyhydroxides. These polymeric oxyhydroxides are excellent coagulating agents [9]. The task of removing arsenic from water has received extensive attention. Major treatment approaches include treatment with lime, alum or iron coagulation and chemical oxidation [10,11] and adsorption, reverse osmosis, membrane ltration and ion exchange [1214]. These treatment technologies take considerable time; require an extensive set-up and they are not economically applicable in small community systems. Moreover, the entire treatment requires several pH adjustments as well as the addition of acid, coagulants such as alum, ferric sulphate and chloride, lime, caustic or polymeric occulants. These processes generate a considerable quantity of secondary pollutants (chloride, sulphate in the coagulation-precipitation) and large volumes of sludge or waste

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which pose serious environmental problems. Therefore, there is a need for developing, not require chemical additions, a low cost and technically effective arsenic removal technology. In recent years, electrocoagulation (EC) shows the greatest potential for application in the treatment of drinking water and wastewaters [1519]. The advantages of EC over conventional technologies include high removal efciency, compact treatment facility, and possibility of complete automation. The arsenic can be removed successfully from industrial wastewater, surface and ground waters by the EC process and removal efciency could be obtained as high as 99% [2038]. However, most of the studies on arsenic removal by the EC process in literature are in solutions containing high arsenic concentrations prepared by deionised water and industrial wastewater; consequently, their results can differ with respect to those obtained with real water (groundwater and potable water) because a great number of species are present in real water that interfere with the arsenic removal process. Recently, some household lters and micro-alloyed aluminum composite are used for the arsenic removal from aqueous solutions [39] and treatment of metal nishing industry wastewater containing copper and zinc in spontaneous reduction-coagulation process [40]. The ltrates for the arsenic removal do not fulll the recommended guideline value in removing pathogens and other chemicals like uoride present in drinking water, but the EC process is able to reduce arsenic concentration lower than 10 g L1 in drinking and ground waters. The purpose of this work is to achieve lower concentration of arsenic than the permissible level of arsenic using Fe and Al electrodes by the EC process and to reduce the energy and electrode consumption by shortening the treatment time for As removal from drinking water. Inuence of operation parameters that affect the EC process; initial pH, current density, operating time, initial arsenic concentration and electrode type was determined for better removal efciency. Operating costs based on energy and electrode consumptions were also calculated.

When the current is applied, the electrodissolution of the anode is accompanied with the oxidation of water 2H2 O O2 + 4H+ + 4e 2.2. Cathodic reactions for Fe or Al electrodes The second step would take place at the anode. The general cathode reaction takes place at the cathode and results in the liberation of hydrogen. This is represented as: 2H2 O + 2e H2(g) + 2OH (Fe electrode)

(5)

(6) (7)

3H2 O + 3e (3/2)H2(g) + 3OH

(Al electrode)

When introducing air (or oxygen) to the process, Fe2+ is oxidized rapidly: O2(g) + 4Fe2+ + 2H2 O 4Fe3+ + 4OH Al3+ Fe3+ (in bulk solution) (8)

Generally, the or ions released from anode are gradually hydrolyzed and formed the Al(OH)3(s) and Fe(OH)3(s) if there is no other reactive species in solution. For Fe electrodes, the rate of the oxidation depends on the availability of dissolved oxygen. Typically at the cathode the solution becomes alkaline with time. The applied current forces OH ion migration towards the cathode and combine with hydroxide ions (Eqs. (9) and (10)): Fe3+ + 3OH Fe(OH)3(s) Al
3+

(9) (10)

+ 3OH Al(OH)3(s)

2.3. Hydrolysis reactions in the solution At pH 4 < pH < 7, iron undergoes hydrolysis according to reactions (1)(3) [38,41] Fe + 6H2 O Fe(H2 O)4 (OH)2(aq) + 2H+ + 2e Fe + 6H2 O Fe(H2 O)3 (OH)3(aq) + 3H + 3e
+

(11) (12)

2. Arsenic removal mechanism with EC EC consists of an in situ generation of coagulants by an electrical dissolution of Fe or Al electrodes. The generation of metallic cations takes place at the anode, whereas at the cathode, typically a H2 production occurs together with OH release. Ferric or aluminum ions generated by electrochemical oxidation of Fe/Al electrode may form monomeric species and polymeric hydroxyl metallic complexes depending on the pH of the aqueous medium, which have strong afnity for dispersed particles as well as counter ions to cause coagulation [1519]. In an EC process with Fe or Al electrode; the main anode (Eqs. (1)(5)), cathode (Eqs. (6) and (7)), hydrolysis (Eqs. (11)(20)), co-precipitation and adsorption reactions (Eqs. (21)(25)) are shown in the following equations:

Fe3+ hydroxide begins to precipitate oc with yellowish color Fe(H2 O)3 (OH)3(aq) Fe(H2 O)3 (OH)3(s) (13)

Fe causes the evolution of H2 from cathodic reaction (Eq. (6)). Rust may also be formed. 2Fe(H2 O)3 (OH)3(s) Fe2 O3 (H2 O)6 (14)

At pH 6 < pH < 9, precipitation of Fe3+ hydroxide (Eq. (14)) continues. The minimum soluble iron concentration Fe(OH)3 solubility occurs over the pH range of 710 and Fe2+ hydroxide precipitation also occurs presenting a dark green oc 2Fe(H2 O)4 (OH)2(aq) Fe(H2 O)4 (OH)2(s) (15)

2.1. Anodic reactions for Fe or Al electrodes In two-step process where iron is rstly oxidized to ferrous ion which depending on anode potential, then oxidizes to ferric ion [2038]: Fe(s) Fe
2+

The pH for the minimum solubility of Fe(OH)n is in the range of 78. EC oc is formed due to the polymerization of iron oxyhydroxides. Formation of rust occurs as shown in the following reactions [41,42]: 2Fe(OH)3 Fe2 O3 + 3H2 O Fe(OH)2 FeO + H2 O 2Fe(OH)3 Fe(OH)2 + Fe3 O4 + 4H2 O Fe(OH)3 FeO(OH) + H2 O (magnetite) (hematite, maghemite) (16) (17) (18) (19)

+ 2e

(1) (2) (3) (4)

(goethite, lepidocrocite)

Fe2+ Fe3+ + e Fe(s) Fe3+ + 3e Al(s) Al3+ + 3e

Hematite, maghemite, rust, magnetite (Fe3 O4 ), lepidocrocite and goehite were identied by XRD in the literature [9,38,41,42]. The compositon of pollutants in water or wastewater affects the generation and the type of green rust. The oxidation of Fe2+ ions in green rust results in the formation of goethite, lepidocrocite, hematite, maghemite or magnetite in oxygen depleted systems. As

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removal with EC using Fe electrodes was formation of a dark green oc. In general, hydrogen gas and green rust were formed at the cathode as shown in Eq. (15) [41,42] 6Fe + (12 + x)H2 O (1/2)(12 x)H2 (g) + xFe(OH)3 (6 x)Fe(OH)2 (s) (20)

3.3. Experimental procedure In each run, 560 mL arsenic solution (75500 g L1 ) was placed into the EC reactor. The anodes and cathodes were connected to the positive and negative outlets of a DC power supply. Organic impurities and oxide layer on electrode surfaces were removed by dipping for 2 min in a solution freshly prepared by mixing HCl solution (35%) and hexamethylenetetramine aqueous solution (2.80%) [16,19]. Current and cell potential were held constant at desired values for each run and the experiment was started. The samples at the different operating times taken from the EC reactor were ltered using a 45 m Millipore membrane and arsenic concentration was measured. At the end of the run, the electrodes were washed thoroughly with water to remove any solid residues on the surfaces, dried and reweighed. In addition, sludge after the EC experiment was dried at 105 C temperature for sludge analysis. 3.4. Analytical procedure

2.4. Co-precipitation and adsorption reactions The arsenic removal occurs by ligand exchange, arsenate displaces a hydroxyl group of FeOOH giving rise to an insoluble surface complex [22,23]: 2FeOOH(s) + H2 AsO4 (FeO)2 HAsO4 + H2 O + OH 3FeOOH(s) + HAsO4 2 (FeO)3 AsO4(s) + H2 O + 2OH mAl(aq) 3+ + (3m n)OH + nHAsO4(aq) 2 Alm (OH)(3mn) (HAsO4 )n(s) (23) (21) (22)

AlOH(s) + HAsO4(aq) 2 AlOAs(O)2 (OH)(s) + OH(aq) (24)

Al(OH)3(s) + AsO4(aq) 3 [Al(OH)3 AsO4 3 ](s)

(25)

where the surface symbols is used to denote the bonds of the cations with the surface of the solid [9,37]. 3. Experimental 3.1. Materials Stock arsenic solutions of 1000 mg As L1 were prepared according to the EPA standard method by dissolving As2 O3 in drinking water containing 20% (v/v) KOH and then neutralizing by 20% (v/v) H2 SO4 to a phenolphthalein end point and then diluting to 1000 mL with 1% (v/v) H2 SO4 and was stored at 4 C in the refrigerator. The test solutions containing of 75500 g L1 of arsenic were prepared by diluting of stock solution with drinking water before use. 3.2. Experimental set-up The EC experiments were carried out in a batch mode using a 750 mL Plexiglas reactor (81 mm 81 mm 126 mm in dimension) using vertically positioned iron electrodes spaced by 13 mm and dipped in the arsenic solution. Two anodes and two cathodes with dimensions of 50 mm 73 mm 2 mm made of iron and aluminum plate (Fe: 99.5% purity, Al: 99.3% purity), were connected to a digital DC power supply (Agilent 6675A model; 120 V, 18 A) in monopolar parallel connection mode and equipped with galvanostatic operational options [16,19]. The total effective electrode area was 219 cm2 and the constant current was adjusted according to a desirable value (1.757.5 A m2 ). pH and conductivity of solutions before and after the EC were measured by a pH meter (Mettler Toledo 2050e) and a conductivity meter (Mettler Toledo 7100e). pH of the solutions was adjusted by adding either 0.1 N NaOH or 0.1 N H2 SO4 . The solution was constantly stirred at 200 rpm (Heidolp 3600) to reduce the mass transport over potential of the EC reactor.

Based on the standard method suggested by APHA et al. [43], an atomic absorption spectrometer (PerkinElmer SIMAA 6000 AAS) equipped with a manual hydride generator at 188.9 nm wavelength was employed to determine the arsenic concentration in the samples. The detection limit for this study was 0.1 g L1 of arsenic and analysis of the duplicates was within 2% of errors. Laboratory scale experiments were carried out at room temperature. All the chemical reagents used were of analytical grade. The chemical analysis of the drinking water (pH, alkalinity, and presence of arsenic, iron, sulphate and phosphate) was carried out according to Standard methods [43]. It was found that pH of water, bicarbonate alkalinity were varied in the range 7.17.8 and 4550 mg L1 CaCO3 , respectively. The dissolved iron, manganese, magnesium, phosphate and arsenic concentration were not in detectable range in drinking water. Characterizations of drinking water were 85 mg L1 of Cl , 18 mg L1 of SO4 2 , 85 mg L1 of HCO3 , conductivity of 1.7 mS cm1 , 10 mg L1 of NO3 , pH 7.6, 6.2 mg L1 of dissolved O2 and 20 mg CaCO3 L1 of total hardness before the EC process, and 75 mg L1 of Cl , 10 mg L1 of SO4 2 , 60 mg L1 of HCO3 , conductivity of 1.2 mS cm1 , 8 mg L1 of NO3 , pH 6.58.2, 4.6 mg L1 of dissolved O2 and 12 mg CaCO3 L1 of total hardness after the EC process, respectively. 4. Results and discussion 4.1. Effect of initial pH on arsenic removal pH of the medium changes generally during the EC process which depends on type of the electrode material and initial pH. The variation of arsenic concentration with operating time at different initial pH for Fe and Al electrodes is shown in Fig. 1. The rate of arsenic removal was sharp at the beginning of the process and later approached a constant value. This could be explained by the fact that the arsenic ions were more abundant at the beginning of the EC; hence the rate of reaction was high, while on the other hand there was reduced concentration of arsenic ions at the end of the process, resulting in a slower reaction rate. For Fe electrodes, removal of arsenic was increased as initial pHi was changed from 4.5 to 8.5 with respect to operating time. As seen in Fig. 1(a), the allowed permissible limit, 10 g L1 , for arsenic removal was obtained in the pHi range 4.58.5 as 9.5 g L1 in 15 min for pHi 4.5, 8.1 g L1 in 10 min for pHi 5.5, 4.9 g L1 in 10 min for pHi 6.5, 6.5 g L1 in 8 min for pHi 7.5 and 6.1 g L1 in 8 min for pHi 8.5, respectively. As pHi was 6.5, the operating time was decreased which led to increase effectively in arsenic removal. The oxidation of Fe2+ was slow at pHi 6.5 and hydroxides

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Fig. 1. Effect of initial pH for (a) Fe electrode and (b) Al electrode on the residual arsenic concentration as a function of the EC treatment time from drinking water (CD = 2.5 A m2 ). Fig. 2. Changes of pH before and after the EC treatment of arsenic from drinking water for (a) Fe electrode and (b) Al electrode (Ci = 150 g L1 , CD = 2.5 A m2 ).

produced at the cathode were not used up which resulted in an increase in pHi . At 6.5 pH 8.5, Fe(OH)3(s) led to a pH decrease. The Fe2+ produced during the EC underwent complete oxidation to form Fe(OH)3(s) at pHi 6.5. Therefore, removal rate of arsenic was better as pHi 6.5. Lakshmanan et al. [22,28] indicated that at pH 8.5, Fe2+ was completely oxidized and resulted in Fe(OH)3(s) . As Fe(OH)3(s) is amphoteric, some Fe(OH)4 formation was likely at pH 8.5 since OH ions were consumed to form iron hydroxide complexes. For Al electrodes, removal of arsenic was increased as initial pHi was changed from 5.0 to 9.0 with respect to operating time. As seen in Fig. 1(b), the allowed permissible limit for arsenic removal was obtained in the pHi range 5.09.0 as 9.5 g L1 for pHi 5.0, 4.7 g L1 for pHi 6.0, 6.5 g L1 for pHi 7.0 and, 8.8 g L1 for pHi 8.0 in 15 min, respectively. Removal efciencies of 93.5% for Fe and 95.7% for Al electrodes were achieved with a residual arsenic concentration of 10 g L1 or less for drinking water in the EC process. A slight increase in the pH was observed with operating time during the EC process (Fig. 2). The efuent pHn were changed from 6.4 to 9.5 for Fe electrodes and from 6.8 to 9.8 Al electrodes when the experiment was operated at pHi in the range 4.59.0. This slight increase of pH value was associated to the formation of hydrogen gas at the cathode [19,37] and hydroxyl ions (OH ) produced at the cathode electrode according to Eqs. (5) and (6)

in the EC process. Thus, the electrolytic reactor was capable of producing enough OH ions to compensate the acid-buffer and make the solution alkaline. These ions were also mainly consumed in the ferric/aluminum oxyhydroxides formation which explained the slight pH increase after the EC treatment [44,45]. The Fe3+ ions may undergo hydration and depending on the pH of solution, Fe(OH)2+ , Fe(OH)2 + , Fe(OH)3 , Fe(OH)6 , Fe(OH)4 species may also be formed. The following aluminum species were also found in aqueous solution with respect to pH: Al3+ , Al(OH)2 + , Al(OH)3 , Al(OH)4 , Al13 (OH)34 5+ and Al13 (OH)32 7+ [16,18,19,42]. In the EC process, a slight increase observed with time in the pH was within the regulatory drinking water standards. Kobya et al. [19] observed the same effect during the EC process and also reported that EC can act as pH neutralization step (Table 1). 4.2. Effects of current density on arsenic removal It is well known that current density determines coagulant dosage rate and bubble production rate, size and growth of ocs which can inuence removal efciency of the pollutions in the EC process. Results in Fig. 3 showed an important drop in the arsenic concentration with an increase of the operating time for both elec-

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Table 1 The effect of pH on the removal of arsenic by Fe and Al electrodes and operating cost parameters in the EC process. Electrode pHi 4.5 5.5 6.5 7.5 8.5 5.0 6.0 7.0 8.0 9.0 Ci ( g L1 ) 500 500 500 500 500 150 150 150 150 150 CEC ( g L1 ) 9.5 8.1 4.9 6.5 6.1 9.5 4.7 3.5 8.8 48.5 Re (%) 98.1 98.4 99.0 98.7 98.8 93.7 96.9 97.7 94.1 67.6 tEC (min) 15 10 10 8 8 15 15 15 15 >15 Cenergy (kWh m3 ) 0.0148 0.0164 0.0140 0.0131 0.0131 0.0324 0.0324 0.0324 0.0324 0.0324 Celec, exp (kg m3 ) 0.0168 0.0155 0.0153 0.0148 0.0135 0.0077 0.0083 0.0087 0.0085 0.0061 Wsludge (kg m3 ) 0.012 0.014 0.015 0.018 0.013 0.018 0.017 0.020 0.020 0.013 OC (D m3 ) 0.0155 0.0152 0.0146 0.0127 0.0115 0.0154 0.0165 0.0172 0.0167 0.0125

Fe

Al

trodes at Ci = 150 g L1 , pHi 6.5 for Fe and 7.0 for Al electrodes as current density varied in the range 2.57.5 A m2 . The rate of reduction in the arsenic concentration was almost sharp in the early stages of the process and decreased to gradual reduction in later part of electrolysis (Fig. 3). The arsenic removal efciencies were changed in the range 93.594.1% for Fe and 93.796.5% Al electrodes at current density of 2.57.5 A m2 (Table 2). In addition, the results satised for all cases where arsenic concentration permissible level in drinking water was obtained lower than 10 g L1 and this concentration was marked in blue in Fig. 3. An important decrease of the arsenic concentration appeared in the treated drinking water solution just after 5 min for Fe and 2.5 min of operation for Al electrodes, respectively. This can be attributed at high current densities; the extent of anodic dissolution (Faradays law, Eq. (26)) increased which increased the hydroxide cationic complexes resulting in increased arsenic removal [16,19,21]. Celec,theo = itEC Mw zF v (26)

where Celec, theo (kg Al or Fe electrode m3 treated drinking water) is the theoretical amount of ion produced by current i (A) passed for a duration of operating time tEC (s), z is the number of electrons involved in the oxidation/reduction reaction; for Fe, zFe = 2 and for Al, zAl = 3. Mw is the atomic weight of anode material (Mw,Fe = 55.85 g mol1 , Mw,Al = 26.98 g mol1 ), F is the Faradays

constant (96,485 C mol1 ) and v is the volume (m3 ) of the drinking water in the EC reactor. According to Faradays law, the charge passed to the solution was directly proportional to amount of electrode (Fe or Al) dissolved. This implied that the arsenic removal by EC may be governed by the formation of metal-hydrous ferric or aluminum oxide complexes [9,33]. An operating time of 12.5 min for Fe and 15 min for Al electrodes at 2.5 A m2 was selected to achieve a residual arsenic concentration of 10 g L1 or less for drinking water in the EC process which resulted in removal efciencies of 93.5% for Fe and 95.7% for Al electrodes and reducing of the operating cost (Table 2). This was associated with the higher dissolution of Fe2+ or Al3+ ions when current density was increased (anode and cathode reaction Eqs. (1)(10)), and the arsenic removal increased consequently. This was consistent with the results reported by several authors [24,25]. More sludge was also produced from Fe and Al electrodes at higher current density due to elevated dissolution rate of anode. Arsenic species removed by metal hydroxide ocs were formed in the vicinity of the anode surface either by surface complexation or electrostatic attraction. Therefore, when high current densities were applied, the coagulation and removal time of arsenic improved. However, these parameters should be kept at low level to achieve a low-cost treatment. For that a compromise of the current density and electrolysis time was necessary to optimize the treatment efciency with the lowest cost. Considering this operat-

Table 2 The effect of current density on the removal of arsenic by Fe and Al electrodes and results of detailed experimental parameters in the EC process. Parameters Current density (A m2 ) Fe electrode Current density, j (A m2 ) Current intensity imposed, i (A) Operating time, tEC (min)a Initial arsenic concentration, Ci ( g L1 ) Efuent arsenic concentration, CEC ( g L1 )b Arsenic removal efciency, Re (%) Average voltage between electrodes, U (V) Initial pHi Final pHf Coulomb passed (C) Charge loading (Faradays m3 ) Theoretically produced metal (mol) Arsenic removed (mol) Metal/arsenic ratio, Me/As (mol/mol) Removal arsenic/Coulomb passed (mg C1 ) Energy consumption, Cenergy (kWh m3 ) Electrode consumption, Celec, exp (kg m3 )c Electrode consumption, Celec, theo (kg m3 )d Current efciency, CE (%) Sludge production, Wsludge (kg m3 ) Operating cost, OC (D m3 )
a b c d

Al electrode 5.0 0.11 7.5 150 8.9 94.1 1.2 6.5 7.8 49.5 0.9161 2.57 104 1.87 106 137.4 0.0029 0.0276 0.0272 0.0257 106 0.034 0.0255 7.5 0.16 5 150 9.2 93.9 1.6 6.5 8.1 48.0 0.9161 2.49 104 1.88 106 132.5 0.0029 0.0375 0.0268 0.0249 108 0.058 0.0261 2.5 0.05 15 150 6.5 95.7 1.5 7.0 7.5 45.0 0.833 1.55 104 1.90 106 81.3 0.0032 0.0324 0.0087 0.0075 116 0.020 0.0172 5.0 0.11 10 150 9.5 93.7 1.9 7.0 7.5 66.0 1.22 2.28 104 1.90 106 121.7 0.0021 0.0635 0.012 0.011 109 0.019 0.0252 7.5 0.16 4 150 5.2 96.5 2.3 7.0 7.6 38.4 0.711 1.33 104 1.90 106 68.7 0.0038 0.0472 0.0069 0.0064 108 0.0135 0.1485

2.5 0.05 12.5 150 9.8 93.5 0.8 6.5 7.3 37.5 0.694 1.94 104 1.57 106 123.8 0.0038 0.0149 0.0211 0.0194 109 0.031 0.0196

Minimum operating time for WHO recommended level of maximum arsenic concentration (10 g L1 ) in the drinking water. Data show values of arsenic concentrations under WHO recommended as 10 g L1 . Experimental calculations. Theoretical calculations.

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Fig. 3. Effect of current density for (a) Fe electrode and (b) Al electrode on the residual arsenic concentration as a function of the EC treatment time from drinking water (150 g L1 , pHi 6.5 for Fe and 7.0 for Al electrodes).

ing cost factor, all further experiments were carried out at current density values of 2.5 A m2 for both electrodes. In the EC process, the coagulant Al3+ or Fe2+ were produced by electrochemical sacrice of the aluminum or iron anodes. Its dosages were determined by charge loading. The quality of EC efuent depended on the amount of coagulant produced (mg) or applied charge loading. Theoretically, according to Faradays law, whenever 1 Faraday of charge passes through the circuit, 9.0 g of aluminum or 28 g of iron are dissolved at each anode of a different connection mode EC unit. When the charge loading of the EC was low, the coagulant dosages (Al3+ of Fe2+ ) were not sufcient to removal all arsenic ions, and thus the arsenic removal efciency was not high. Fig. 4a showed the arsenic removal as a function of charge loading. The charge loading (Q = i tEC /F v) was calculated as the applied current multiplied by the residence time per unit of volume [34,45]. The arsenic removal was proportional to the charge loading in range of 0.10.9 F m3 (Fig. 4a). The curve for the arsenic removal attened above approximately 0.69 and 0.83 F m3 charge loading values for Fe and Al electrodes. This was as expected since less amount of arsenic was remaining. So, relatively more Fe3+ or Al3+ had to be added at this low concentration to remove rest of the arsenic. Mass transfer could be the limiting step for this concentration and it could be hindered by the increased gas production when applying higher current. Another reason could be that the

Fig. 4. Effects of (a) charge loading and (b) energy consumption on removal of arsenic from drinking water in the EC process.

stress on the lower edges of two electrodes together with relative much higher electric eld around them would make them corrode much faster than other parts of the electrodes. When considering that the only reaction at the anodes were Fe2+ and Al3+ , then the theoretical amount of produced Fe2+ and Al3+ could be calculated by the total electrical charge passed through the EC system (Eq. (26)). The overall arsenic removal as a function of applied electrical charge in Table 2 also showed that the EC process was working at an acceptable level. The arsenic removal rates for Fe for Al electrodes at 2.5 A m2 were 0.0038 and 0.0032 mg Coulomb1 , respectively. It was clear that a technically efcient process must also be feasible economically. The major operating cost of EC was associated with electrical energy consumption during process [16,21,27]. The electrical energy required to arsenic removal for Al and Fe electrodes was calculated in terms of kWh m3 using the equation given as follows: Cenergy = UitEC

(27)

where U is cell potential (V) in the EC reactor. Energy consumption versus operating time for both electrodes in the EC process was shown in Fig. 4b and linear dependences were observed. The

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energy consumptions for both electrodes were required 0.8 V for Fe and 1.5 V for Al electrodes (Table 2). Therefore, longer operating times may be used to obtain higher arsenic removal efciencies using less electric energy. The energy consumptions for Fe electrode (0.015 kWh m3 ) were found to be lower than that for Al electrode (0.032 kWh m3 ). This result was probably due to the higher potential required to achieve a certain current density. According to Faradays law, it was clear that Al3+ or Fe2+ dose released from anode depended on the electrolysis time and current. So in the EC process, current density and operating time were the most important parameters affecting the arsenic removal efciency and controlling the reaction rate in the EC reactor. As seen in Table 2, experimental electrode consumption values at the 2.5 A m2 were 0.021 kg m3 for Fe and 0.0087 kg m3 for Al electrodes while the theoretical electrode consumption reached its highest value of 0.019 kg m3 for Fe and 0.0075 kg m3 for Al electrodes as minimum operating time needed to meet the WHO recommended level of maximum arsenic concentration in the drinking water. It was clear that electrode consumptions were higher with Fe electrode material based on a molecular weight. By considering atomic weights of Al and Fe, the consumptions on molar basis were very different; the calculated values were 0.074 mol g m3 for Fe and 0.093 mol g m3 for Al electrodes at a given current density of 2.5 A m2 . It was also an important parameter for the EC process because it affected lifetime of the electrode [46]. The Faradic yield or current efciency (CE ) is dened as the ratio of the actual electrode consumption to the theoretical value. The CE calculation was based on the comparison of experimental weight loss of aluminum or iron electrodes (Celec, exp ) during the EC process with theoretical amount of aluminum or iron dissolution (Celec, theo ) according to Eq. (28) by the electrode consumption difference before and after the EC process. The current efciency of the arsenic removal experiments with electrode connection modes was calculated using the following equation: CE (%) = Celec,exp Celec,theo 100 (28)

In Table 2, the results showed that the current efciencies for both electrodes were in the range 106116%. This difference in mass may be explained by the corrosion pitting phenomenon which caused holes and led practically to a metallic metal (Fe or Al) loss on the electrode surface [47]. This mass was erroneously calculated as the metal dissolved by the EC process. Amount of electrochemically dissolved Fe or Al electrodes for arsenic removal methods in the EC are a major cost item that is directly proportional to removed arsenic concentration in the drinking water. However, effectiveness of the EC process in the different process conditions was very sensitive to the Me (Fe or Al):As ratio, and this parameter can vary by several orders of magnitude. The ratio metal (Me:Fe or Al; theoretically produced metal) to arsenic (removed from the EC process) at 10 mg L1 in mol mol1 was calculated and shown in Table 2. It was seen from the table that the lowest ratio was obtained for 123.8 mol Fe mol1 arsenic and 68.7 mol Al mol1 arsenic at the 2.5 A m2 . This meant less metal necessary to dissolve in order to adsorb or co-precipitate arsenic ions for both electrodes. In addition, this low ratio assured only a small amount of nal solid waste product in comparison to conventional treatment methods. Furthermore, it could be seen that no residual iron or aluminum was present in the outlet solution, insuring a high arsenic removal efciency of the produced ferric or aluminum ions. This could indicate that OH ions was produced at the cathode and was promoting the arsenic, hydrolysis, precipitation or co-precipitation (Eqs. (11)(25)). These rations was also compared to the literature values, where Me:As ratios for conventional precipitation with FeCl3 /Al(OH)3 addition uctuate was

Fig. 5. Effects of initial concentration on the residual arsenic concentration as a function of the EC treatment time from drinking water (a) Fe electrode and (b) Al electrode (CD = 2.5 A m2 , pHi 6.5 for Fe and 7.0 for Al electrodes).

between 5 and 191 [34,37]. The Fe:As ratio had to be high to reduce the concentration of arsenic below 10 mg L1 around 2028 using a batch EC process [9,21], while the airlift reactor carrying out EC on a 100 mg L1 solution was around 14 mol mol1 . The higher Me:As ratio with 100 mg L1 could be due to mass transfer being the limiting step. For the efcient removal of arsenic from drinking water, the ratio typically was larger than 10 [23,37]. Our results were in agreement with the literature values (Table 2). 4.3. Effects of arsenic concentration on arsenic removal The effect of initial arsenic concentration from 75 to 500 mg L1 was examined with drinking water at 2.5 A m2 , pH 6.5 for Fe and pH 7.0 Al electrodes. Fig. 5a and b illustrated the effect of the initial arsenic concentration as a function of operating time. As can be seen in Fig. 5a and b, the initial arsenic concentration increased from 75 to 500 mg L1 , the operating time and removal efciency for achieving the arsenic concentration of 10 mg L1 increased from 7.5 to 15 min and from 88.5 to 98.1% for Fe and from 4.0 to 15.0 min and from 86.9 to 98.7% for Al electrodes, respectively. In the EC process,

M. Kobya et al. / Electrochimica Acta 56 (2011) 50605070 Table 3 The effect of initial concentration on the removal of arsenic by Fe and Al electrodes and operating cost parameters in the EC process. Electrode Fe Ci ( g L1 ) 75 150 500 75 150 500 CEC ( g L1 ) 8.6 9.8 9.5 9.8 9.5 6.5 Re (%) 88.5 93.5 98.1 86.9 93.7 98.7 tEC (min) 7.5 12.5 15.0 4.0 15.0 15.0 Cenergy (kWh m3 ) 0.0076 0.0149 0.0206 0.0090 0.0324 0.0308 Celec, exp (kg m3 ) 0.0415 0.0211 0.1055 0.0056 0.0087 0.0246 Wsludge (kg m3 ) 0.013 0.031 0.075 0.013 0.020 0.025

5067

OC (D m3 ) 0.0358 0.0196 0.0912 0.0096 0.0172 0.0416

Al

the rate of arsenic removal was proportional to the initial arsenic concentration. Higher arsenic removal efciency at higher initial arsenic concentration can be achieved by a proportionate increase in current density and electrode surface area. This can potentially be explained by three reasons. First, at higher arsenic concentrations arsenic ions readily electrocoagulated in the vicinity of Fe or Al electrodes; however, with progress of the removal, increased diffusional resistance to movement to the surface of the anode acted to reduce the rate of EC. Second, one of the most important pathways of arsenic removal by the EC process was adsorption onto metallic hydroxide ocs, and the adsorption capacity of ocs was limited [37]. Third, since our experiments were all performed under the same operating conditions, the release rate of the hydroxyl ions was almost constant. It was found that the amount of sludge produced was nearly same for all the experiments performed in initial arsenic concentrations range studied (Table 3). As expected, operating cost increased with increasing of operating time. 4.4. Characteristics of EC sludge The sludge production was another important parameter in characterizing the EC process. The EC sludge production was pro-

portional to characteristics of wastewater, settable solids and matter destabilized by coagulation and concentration occulent and was also proportional to current density and residence time [9,36,38]. Sludge contained arsenic and metals (Al or Fe) ions in the EC reactor. In the EC process, arsenic was separated from and oated on the surface of the wastewater in the form of sludge. When values of sludge for each electrode were compared with respect molar electrode consumptions based on a molar basis, it was seen that aluminum hydroxide ocs bound more water, chemically or physically, than iron hydroxide ocs did. Values of the sludge in the initial pH and initial arsenic concentration in the EC process at 10 mg L1 were 0.0120.018 kg m3 and 0.0130.075 kg m3 for Fe and 0.0130.020 kg m3 and 0.0130.025 kg m3 for Al electrodes

Fig. 6. (a) SEM micrograph and (b) EDS spectra of sludge and imaged magnied 2000.

Fig. 7. Pseudo second-order plot for arsenic adsorption (a) Fe electrode and (b) Al electrode at different current densities in the EC process.

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Table 4 The effect of current density and initial concentration on the adsorption kinetics of arsenic by Fe and Al electrodes in the EC process. Parameters Fe electrode k2 (g mg CD (A m2 ) 2.5 5.0 7.5 Ci ( g L1 ) 75 150 500 0.1431 0.1322 0.1810 0.2608 0.1431 0.0790
1

Al electrode
1

min

qe (mg g 5.2 2.6 1.7 3.4 5.2 12.8

k2 (g mg1 min1 ) 0.0232 0.0447 0.0584 0.0242 0.0223 0.0026

qe (mg g1 ) 17.5 7.9 5.5 12.8 17.5 46.2

r2 0.95 0.94 0.93 0.98 0.95 0.94

0.99 0.94 0.95 0.96 0.99 0.95

(Tables 1 and 3). The sludge values at the optimum conditions were 0.031 kg m3 for Fe and 0.020 kg m3 for Al electrodes (Table 2). Generally, more amount of sludge was formed when Fe electrode was used. From operating cost point of view, Al electrode was clearly more economic material type than Fe electrode. Surface

topography of the sludge was analyzed using SEM (SEM, Philips XL30S-FEG). The SEM image in Fig. 6a indicated the presence of mostly amorphous structure which had an aggregate size of 2050 m. The sludge at 2000 magnication appeared to be a relatively uniform cake (showing cracks due to drying). Energy dis-

Table 5 Comparisons of arsenic removals with different electrodes and operating conditions in the EC process. As content and water type Drinking water (C0 = 150 g L1 As(III), pHi = 6.5) Drinking water (C0 = 150 g L1 As (III), pHi = 7.0) Potable water (C0 = 1001000 g L1 As(III) and As(V) pHi = 58.0) Synthetic solution (C0 = 50 g L1 As(V), pHi = 7.5 and 6.5c ) Synthetic solution (C0 = 500 g L1 As(V), pHi = 7.0) Model water (C0 = 190 g L1 As(V), pHi = 8.07) Ground water (C0 = 133 g L1 (122.5 g L1 As(V) and 10.5 g L1 As(III)) pHi = 8.06) Synthetic solution (C0 = 100 mg L1 As(V), pHi = 7.0) Ground water (Mexico) (C0 = 131 g L1 As, pHi = 7.2) Synthetic solution (C0 = 100 mg L1 As(V), pHi = 7.0) Synthetic solution (C0 = 100 mg L1 As(V), pHi = 7.0) Synthetic solution (C0 = 100 mg L1 As(V)) Groundwater (Mexico) (C0 = 40 g L1 Astotal , pHi = 7.0) Synthetic solution (C0 = 2 mg L1 As(III) and As (V), pHi = 68) Type of electrode Fe plate Type of EC reactor Batch Re (%) 93.5 Current density (A m2 ) 2.50 tEC (min) 12.5 OC ($ m3 ) 0.020 Reference This study

Al plate

Batch

95.7

2.50

15

0.017

This study

Rod-shaped Fe

Batch air fed

>9099

0.19

3045a 545b

[22]

Rod-shaped Fe

Al plate

Continuous (0.245 L min1 ) and batch Batch

>7585

0.25

[24]

98.4

20.00

30

[25]

Carbon steel plate AISI 1018

Continuous air fed (3 L min1 )

>95

45.00

0.08

[27]

Carbon steel plate: AISI Continuous air fed 1018 (0.875 L min1 )

99

45.00

0.75

[33]

Mild steel plate

Batch

94

150.00

50

[32]

Low carbon steel plate ASTM 1018 Fe cylinder

Bipolar batch air fed

>93

3.00

0.34

[29]

Batch airlift

>98

120.00

60

[34]

Fe cylinder

Continuous airlift (0.060.24 L min1 )

8850

180.00

16.74.2

[34]

Steel plate: A37-24ES Carbon steel plate

Continuous air fed >98 (3 L h1 ) Lamar Mobil Pilot Plant >99 (30 L min1 ) Batch >99

120.00 4.60

9d (90e ) 1.5

0.002f

[37] [39]

Fe plate

1.53

[40]

OC: operating cost (including costs of energy and electrode consumption), Re : As removal efciency, tEC : operating time, j: current density. a 1001000 g L1 for As(III). b 1001000 g L1 for As(V). c Initial pH for batch process. d The steady state operation mode, the residence time. e Steady state time. f Energy cost only.

M. Kobya et al. / Electrochimica Acta 56 (2011) 50605070 Table 6 Comparison of the conventional processes with EC process for As removal [38,48]. Process type Precipitation with alum Process conditions pH 6.5, ERS = lower as well as higher As0 , AEAC 20 g L1 , Re = 2090%, OC = medium pH 68, ERS = lower as well as higher As0 , AEAC 20 g L1 , Re = 6090%, OC = medium pH > 7, ERS = lower as well as higher As0 , AEAC 10 g L1 ,Re = 4090%, OC = medium pH 10.5, ERS = lower As0 , AEAC 10 g L1 , Re = 8090%, OC = high ERS = lower As0 , AEAC 2 g L1 , Re 90%, OC = high Advantages Well established; suitable for home use Disadvantages

5069

Precipitation with iron

Proven and reliable

Precipitation with Fe/Mn

Proven and reliable

Lime softening

Proven and reliable; reduces corrosion Highest water quality; treats wide range of dissolved salts, minerals; turbidity Pure quality water

Reverse osmosis

Electro dialysis

Ion exchanges

pH 79, ERS = lower As0 , AEAC 3 g L1 , Re 95%, OC = high pH 7.5, ERS = lower As0 , AEAC 2 g L1 , Re 90%, OC = high pH 5.56.0, ERS = lower As0 , AEAC 1 g L1 , Re 90%, OC = low

Use of chemicals; high arsenic contaminated sludge; dose of oxidizing chemicals highly inuence on the removal efciency Use of chemical; high arsenic contaminated sludge; dose of oxidizing chemicals highly inuence on the removal efciency Higher and lower pH reduces efciency; use of chemical; high arsenic contaminated sludge; dose of oxidizing chemicals highly inuence on the removal efciency Sulphate ions inuence efciency; secondary treatment is required; use of chemicals Expensive to install and operation; frequent membrane monitoring; pH, temperature and pressure control to meet membrane tolerance Less proven; costly; needs oxidizing agents Efciency affected by sulphate, nitrates, uorides ions, TDS, selenium, etc. Careful monitoring; effectiveness is based on contaminant type; concentration and rate of water usage; bacteria may grow on alumina surface Efciency depends on the ash content in the carbon and on the metal concentration; not proven

Can produce treated water with As concentration less than 2 g L1 Well established; suitable for home use; typically inexpensive with simple Replacement requirements; improves test and odour Typically inexpensive with simple replacement requirements; improves test and odour

Adsorption in activated alumina

Adsorption on activated carbon

pH 29, ERS = lower As0 , AEAC 7 g L1 , Re = 3090%, OC = low

AEAC: attainable efuent As concentration; Re : removal efciency; ERS: effective range of separation; OC: operating cost.

persive spectrum (EDS) of the sludge at the optimum conditions for both electrodes in Fig. 6b showed the presence of As removed (0.8 at%) from the sample solution. Other elements detected in the sludge were Au, iron and aluminum corresponding to the gold coating used for the SEM process and electrodes, respectively. 4.5. Adsorption kinetics of EC-arsenic removal The kinetics give information about the arsenic adsorption on the solid adsorbent phase [30,37]. The adsorption kinetics of arsenic on amount of electrochemically dissolved metal (ferric or aluminum oxyhydroxides) were determined from the pseudo second-order kinetic model equation. The linearized pseudo second-order kinetic model was expressed as [20,28]: qt = t qt (Ci Cf )v Ci 1 = + t qe k2 q2 e 1 (29)

proportional to the amount of coagulant generated. The amount of both dissolved electrodes was increased 3.2 times more with increasing of the current density. In this case, values of qt would be decreased as the amount of dissolved electrode increased. It can also be observed that the adsorbent capacity also increased with the increase in the initial arsenic concentration (Table 4). The adsorbent capacities and rate constants at 2.57.5 A m2 and 75500 g L1 in the EC were obtained in the range 5.21.7 mg g1 , 3.412.8 mg g1 and 0.14310.1810 g mg1 min1 , 0.26080.0790 g mg1 min1 for Fe and 17.55.5 mg g1 , 12.646.2 mg g1 and 0.02320.0584 g mg1 min1 , 0.02420.0026 g mg1 min1 for Al electrodes, respectively (Table 4). The error limits for the kinetic values were 0.1. Similar kinetic results in the literature were observed in arsenic removal by the EC process from underground and drinking water [20,28,37]. 4.6. Operating cost of arsenic removal

(30)

The slope and intercept were determined from the plot of (t/qt ) versus t. In the equation, qt (mg g1 ) is the amount of arsenic species adsorbed at time t (min), Ci and Cf are arsenic concentrations before and after the EC, k2 (g mg1 min1 ) is the rate constant of the pseudo second-order adsorption, qe is the amount of arsenic adsorbed at equilibrium (the adsorption capacity), and hi = k2 q2 (mg g1 min1 ) is the initial arsenic e adsorption rate, respectively. This kinetic model could provide a good t to the experimental data for the treatment times investigated and the correlation coefcients (r2 ) for the linear plots were higher than 0.92 for all the experimental data (Table 4 and Fig. 7). The arsenic removal depended on the amount of coagulant generated in the EC since the applied charge was directly

One of the most important parameters that affect the application of any method of water and wastewater treatment greatly is the operating cost (OC). The operating cost included material (mainly electrodes) cost, utility (mainly electrical energy) cost, as well as labor, maintenance and other xed costs. The latter costs items were largely independent of the type of the electrode material. Thus; energy, electrode material and chemicals costs were taken into account as major cost items, in the calculation of the operating cost as D m3 of the drinking water treated [16,21]: operating cost (OC, D m3 ) = aCenergy + bCelectrode + cCchemicals (31) where Cenergy (Eq. (27), consumption kWh m3 ), Celectrode (Eq. (26), consumption kg electrode m3 ) and Cchemicals (consumption

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kg chemicals m3 ) of water treated. Unit prices, a, b and c given for the Turkish Market, November 2010 were as follows: a is electrical energy prices (0.072 D kWh1 ), b is electrode material price for Al (1.65 D kg1 ) and Fe (0.85 D kg1 ), c is chemical prices for NaOH and H2 SO4 (0.40 D kg1 and 0.15 D kg1 ). The operating costs were calculated for the removal of arsenic from drinking water at 10 mg L1 or lower. The operating costs at pH 49 and 75500 mg L1 were 0.0120.016 D m3 and 0.040.09 D m3 for Fe and 0.0150.017 D m3 and 0.010.04 D m3 for Al electrodes (Tables 1 and 3). The lower initial arsenic concentration yielded lower operating cost for removal efciency of arsenic under the present experimental conditions. On the other hand, the operating cost was increased for both electrodes as the current density was increased (Table 2). As a result, the operating costs at optimum operating conditions (pH 6.50 for Fe and 7.0 for Al, CD = 2.5 A m2 and Ci = 150 mg L1 ) were calculated 0.020 D m3 at 12.5 min for Fe and 0.017 D m3 at 15.0 min for Al electrodes. Unit cost of the process for Al (0.0012 D m3 min) was found to be cheaper than that of Fe (0.0016 D m3 min1 ). Comparisons of arsenic removals with different electrode materials and operating conditions in the EC process were illustrated in Table 5 [48]. As removal efciencies in EC process with current densities of 0.19180 A/m2 and operating time 0.0890 min were obtained in the range of 50>99%. It was difcult to compare the operating costs of EC process since some of cost items were not given with details in most of the published reports in the literature such as energy, electrode, chemicals, etc. In this study, it was obtained for better rate of As removal efciency of 93.5% for Fe electrode and 95.7% for Al electrode, respectively (Table 5). Table 6 was produced to show comparison of conventional techniques with EC process including process conditions, advantages and disadvantages. As seen in Table 6, the EC process was superior to the other techniques since conventional techniques had some limitations such as use of chemical, large volume of high arsenic contaminated sludge, need of secondary treatment in some cases, longer operating time, difculty in monitoring, high installation and operating cost and lower efciency in many cases. 5. Conclusions Batch EC studies were performed to evaluate the inuence of various experimental parameters such as initial pH, electrolysis time, initial concentration and current density on the removal of arsenic in drinking water. The EC process was able to decrease the residual arsenic concentration to less than 10 g L1 (below the limit set by the WHO). Optimum values of pH and current density for arsenic removal were found to be 6.5 for Fe and 7.0 for Al and 2.5 A m2 , respectively. The optimum operating time for arsenic removal was 12.5 min for Fe and 15 min for Al electrodes. The operating costs at the optimum operating conditions were calculated as 0.020 D m3 for Fe and 0.017 D m3 for Al electrodes. The surface of sludge was analyzed by SEM and the image was mainly composed of irregular and porous particles having amorphous structure. The adsorption kinetics of arsenic on amount of electrochemically dissolved metal (ferric or aluminum hydroxides) based on Faradays laws was followed to the pseudo second-order adsorption kinetic model. The arsenic adsorption capacities at 2.57.5 Am2 and 75500 gL1 for the treatment arsenic from the drinking water in the EC process were in the range 5.21.7 mg g1 and 3.412.8 mg g1 for Fe and 17.55.5mg g1 and 12.846.2 mg g1 for Al electrodes. The removal mechanism of

arsenic by the EC process might be co-precipitation and adsorption with metal hydroxides generated in the process. References
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