Electrochimica Acta 56 (2011) 5060–5070

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

Article history: A novel technique of electrocoagulation (EC) was attempted in the present investigation to remove arsenic
Received 3 December 2010 from drinking waters. Experiments were carried out in a batch electrochemical reactor using Al and Fe
Received in revised form 21 March 2011 electrodes with monopolar parallel electrode connection mode to assess their efficiency. The effects
Accepted 22 March 2011
of several operating parameters on arsenic removal such as pH (4–9), current density (2.5–7.5 A m−2 ),
Available online 30 March 2011
initial concentration (75–500 ␮g L−1 ) and operating time (0–15 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
Keywords:
15 min and pH 7 for Al electrode (95.7%) at 2.5 A m−2 , respectively. Arsenic removal obtained was highest
Arsenic
Electrocoagulation
with Al electrodes. Operating costs at the optimum conditions were calculated as 0.020 D m−3 for Fe
Drinking water and 0.017 D m−3 for Al electrodes. EC was able to bring down aqueous phase arsenic concentration to
Iron electrode less than 10 ␮g L−1 with Fe and Al electrodes. The adsorption of arsenic over electrochemically produced
Aluminum electrode 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.

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 L−1 ) [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 (10–900 ␮g L−1 ) than the allowed maximum level
of contamination [4,5].
Arsenic contaminated natural waters are a significant problem
since this compound is known as toxic, mutagenic and car-
cinogenic. 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 blad-
der, 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).
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 L−1 [3,8]. The lowering of this maximum contaminant
level makes it necessary to find 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− (oxi-
dation state V) and arsenite ions, H3 AsO3 , H2 AsO3 − and HAsO3 2−
(oxidation state III). However, As(V) ions are most prevalent in oxy-
genated 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 exten-
sive attention. Major treatment approaches include treatment with
lime, alum or iron coagulation and chemical oxidation [10,11] and
adsorption, reverse osmosis, membrane filtration and ion exchange
[12–14]. These treatment technologies take considerable time;
require an extensive set-up and they are not economically appli-
cable 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 flocculants. These processes generate a consider-
able quantity of secondary pollutants (chloride, sulphate in the
coagulation-precipitation) and large volumes of sludge or waste

0013-4686/$ – see front matter © 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2011.03.086
 M. Kobya et al. / Electrochimica Acta 56 (2011) 5060–5070 5061

which pose serious environmental problems. Therefore, there is a When the current is applied, the electrodissolution of the anode
need for developing, not require chemical additions, a low cost and is accompanied with the oxidation of water
technically effective arsenic removal technology.
2H2 O → O2 + 4H+ + 4e− (5)
In recent years, electrocoagulation (EC) shows the greatest
potential for application in the treatment of drinking water and
2.2. Cathodic reactions for Fe or Al electrodes
wastewaters [15–19]. The advantages of EC over conventional
technologies include high removal efficiency, compact treatment
The second step would take place at the anode. The general cath-
facility, and possibility of complete automation. The arsenic can
ode reaction takes place at the cathode and results in the liberation
be removed successfully from industrial wastewater, surface and
of hydrogen. This is represented as:
ground waters by the EC process and removal efficiency could be
obtained as high as 99% [20–38]. However, most of the studies on 2H2 O + 2e− → H2(g) + 2OH− (Fe electrode) (6)
arsenic removal by the EC process in literature are in solutions con- − −
3H2 O + 3e → (3/2)H2(g) + 3OH (Al electrode) (7)
taining high arsenic concentrations prepared by deionised water
and industrial wastewater; consequently, their results can differ When introducing air (or oxygen) to the process, Fe2+ is oxidized
with respect to those obtained with real water (groundwater and rapidly:
potable water) because a great number of species are present in
real water that interfere with the arsenic removal process. O2(g) + 4Fe2+ + 2H2 O → 4Fe3+ + 4OH− (in bulk solution) (8)
Recently, some household filters and micro-alloyed aluminum Generally, the Al3+
or Fe3+
ions released from anode are grad-
composite are used for the arsenic removal from aqueous solu- ually hydrolyzed and formed the Al(OH)3(s) and Fe(OH)3(s) if there
tions [39] and treatment of metal finishing industry wastewater is no other reactive species in solution. For Fe electrodes, the rate
containing copper and zinc in spontaneous reduction-coagulation of the oxidation depends on the availability of dissolved oxygen.
process [40]. The filtrates for the arsenic removal do not fulfill the Typically at the cathode the solution becomes alkaline with time.
recommended guideline value in removing pathogens and other The applied current forces OH− ion migration towards the cathode
chemicals like fluoride present in drinking water, but the EC pro- and combine with hydroxide ions (Eqs. (9) and (10)):
cess is able to reduce arsenic concentration lower than 10 ␮g L−1 in
drinking and ground waters. Fe3+ + 3OH− → Fe(OH)3(s) (9)
The purpose of this work is to achieve lower concentration of 3+ −
Al + 3OH → Al(OH)3(s) (10)
arsenic than the permissible level of arsenic using Fe and Al elec-
trodes by the EC process and to reduce the energy and electrode
2.3. Hydrolysis reactions in the solution
consumption by shortening the treatment time for As removal
from drinking water. Influence of operation parameters that affect
At pH 4 < pH < 7, iron undergoes hydrolysis according to reac-
the EC process; initial pH, current density, operating time, initial
tions (1)–(3) [38,41]
arsenic concentration and electrode type was determined for better
removal efficiency. Operating costs based on energy and electrode Fe + 6H2 O → Fe(H2 O)4 (OH)2(aq) + 2H+ + 2e (11)
consumptions were also calculated. +
Fe + 6H2 O → Fe(H2 O)3 (OH)3(aq) + 3H + 3e (12)

Fe3+ hydroxide begins to precipitate floc with yellowish color

2. Arsenic removal mechanism with EC
Fe(H2 O)3 (OH)3(aq) → Fe(H2 O)3 (OH)3(s) (13)
EC consists of an in situ generation of coagulants by an electrical
Fe causes the evolution of H2 from cathodic reaction (Eq. (6)).
dissolution of Fe or Al electrodes. The generation of metallic cations
Rust may also be formed.
takes place at the anode, whereas at the cathode, typically a H2
production occurs together with OH− release. Ferric or aluminum 2Fe(H2 O)3 (OH)3(s) → Fe2 O3 (H2 O)6 (14)
ions generated by electrochemical oxidation of Fe/Al electrode may
At pH 6 < pH < 9, precipitation of Fe3+ hydroxide (Eq. (14)) con-
form monomeric species and polymeric hydroxyl metallic com-
tinues. The minimum soluble iron concentration Fe(OH)3 solubility
plexes depending on the pH of the aqueous medium, which have
occurs over the pH range of 7–10 and Fe2+ hydroxide precipitation
strong affinity for dispersed particles as well as counter ions to
also occurs presenting a dark green floc
cause coagulation [15–19]. In an EC process with Fe or Al electrode;
the main anode (Eqs. (1)–(5)), cathode (Eqs. (6) and (7)), hydroly- 2Fe(H2 O)4 (OH)2(aq) → Fe(H2 O)4 (OH)2(s) (15)
sis (Eqs. (11)–(20)), co-precipitation and adsorption reactions (Eqs.
(21)–(25)) are shown in the following equations: The pH for the minimum solubility of Fe(OH)n is in the range of
7–8. EC floc is formed due to the polymerization of iron oxyhydrox-
ides. Formation of rust occurs as shown in the following reactions
2.1. Anodic reactions for Fe or Al electrodes [41,42]:

2Fe(OH)3 → Fe2 O3 + 3H2 O (hematite, maghemite) (16)

In two-step process where iron is firstly oxidized to ferrous ion
which depending on anode potential, then oxidizes to ferric ion Fe(OH)2 → FeO + H2 O (17)
[20–38]:
2Fe(OH)3 → Fe(OH)2 + Fe3 O4 + 4H2 O (magnetite) (18)
2+ −
Fe(s) → Fe + 2e (1) Fe(OH)3 → FeO(OH) + H2 O (goethite, lepidocrocite) (19)

Hematite, maghemite, rust, magnetite (Fe3 O4 ), lepidocrocite

Fe2+ → Fe3+ + e− (2)
and goehite were identified by XRD in the literature [9,38,41,42].
The compositon of pollutants in water or wastewater affects the
Fe(s) → Fe3+ + 3e− (3)
generation and the type of green rust. The oxidation of Fe2+ ions
in green rust results in the formation of goethite, lepidocrocite,
Al(s) → Al3+ + 3e− (4) hematite, maghemite or magnetite in oxygen depleted systems. As
5062 M. Kobya et al. / Electrochimica Acta 56 (2011) 5060–5070
removal with EC using Fe electrodes was formation of a dark green
floc. 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)
2.4. Co-precipitation and adsorption reactions
The arsenic removal occurs by ligand exchange, arsenate dis-
places 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)(3m−n) (HAsO4 )n(s)
≡ Al–OH(s) + HAsO4(aq) 2− → ≡ Al–OAs(O)2 (OH)(s) −
+ OH(aq) −
Al(OH)3(s) + AsO4(aq) 3− → [Al(OH)3 ∗ AsO4 3− ](s)
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 L−1 were prepared accord-
ing 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 75–500 ␮g L−1 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 dimen-
sion) 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 alu-
minum 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 galvanos-
tatic operational options [16,19]. The total effective electrode area
was 219 cm2 and the constant current was adjusted according to a
desirable value (1.75–7.5 A m−2 ).
pH and conductivity of solutions before and after the EC were
measured by a pH meter (Mettler Toledo 2050e) and a conductiv-
ity 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.
3.3. Experimental procedure
In each run, 560 mL arsenic solution (75–500 ␮g L−1 ) was placed
into the EC reactor. The anodes and cathodes were connected to
the positive and negative outlets of a DC power supply. Organic
(20) impurities and oxide layer on electrode surfaces were removed by
dipping for 2 min in a solution freshly prepared by mixing HCl solu-
tion (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 fil-
tered 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,
(21) dried and reweighed. In addition, sludge after the EC experiment
was dried at 105 ◦ C temperature for sludge analysis.
(22)
3.4. Analytical procedure
Based on the standard method suggested by APHA et al. [43],
(23) 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 sam-
ples. The detection limit for this study was 0.1 ␮g L−1 of arsenic and
analysis of the duplicates was within 2% of errors.
(24) Laboratory scale experiments were carried out at room tem-
perature. 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
(25) out according to Standard methods [43]. It was found that pH
of water, bicarbonate alkalinity were varied in the range 7.1–7.8
and 45–50 mg L−1 CaCO3 , respectively. The dissolved iron, man-
ganese, magnesium, phosphate and arsenic concentration were not
in detectable range in drinking water. Characterizations of drink-
ing water were 85 mg L−1 of Cl− , 18 mg L−1 of SO4 2− , 85 mg L−1 of
HCO3 − , conductivity of 1.7 mS cm−1 , 10 mg L−1 of NO3 − , pH 7.6,
6.2 mg L−1 of dissolved O2 and 20 mg CaCO3 L−1 of total hardness
before the EC process, and 75 mg L−1 of Cl− , 10 mg L−1 of SO4 2− ,
60 mg L−1 of HCO3 − , conductivity of 1.2 mS cm−1 , 8 mg L−1 of NO3 − ,
pH 6.5–8.2, 4.6 mg L−1 of dissolved O2 and 12 mg CaCO3 L−1 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 dif-
ferent 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 L−1 , for
arsenic removal was obtained in the pHi range 4.5–8.5 as 9.5 ␮g L−1
in 15 min for pHi 4.5, 8.1 ␮g L−1 in 10 min for pHi 5.5, 4.9 ␮g L−1 in
10 min for pHi 6.5, 6.5 ␮g L−1 in 8 min for pHi 7.5 and 6.1 ␮g L−1
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
 M. Kobya et al. / Electrochimica Acta 56 (2011) 5060–5070 5063

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 m−2 ).

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 L−1 , CD = 2.5 A m−2 ).
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.
in the EC process. Thus, the electrolytic reactor was capable of
The Fe2+ produced during the EC underwent complete oxidation
producing enough OH− ions to compensate the acid-buffer and
to form Fe(OH)3(s) at pHi ≥ 6.5. Therefore, removal rate of arsenic
make the solution alkaline. These ions were also mainly consumed
was better as pHi ≥ 6.5. Lakshmanan et al. [22,28] indicated that at
in the ferric/aluminum oxyhydroxides formation which explained
pH 8.5, Fe2+ was completely oxidized and resulted in Fe(OH)3(s) .
the slight pH increase after the EC treatment [44,45]. The Fe3+
As Fe(OH)3(s) is amphoteric, some Fe(OH)4 − formation was likely
ions may undergo hydration and depending on the pH of solu-
at pH 8.5 since OH− ions were consumed to form iron hydroxide
tion, Fe(OH)2+ , Fe(OH)2 + , Fe(OH)3 , Fe(OH)6 − , Fe(OH)4 − species may
complexes.
also be formed. The following aluminum species were also found
For Al electrodes, removal of arsenic was increased as initial pHi
in aqueous solution with respect to pH: Al3+ , Al(OH)2 + , Al(OH)3 ,
was changed from 5.0 to 9.0 with respect to operating time. As
Al(OH)4 − , Al13 (OH)34 5+ and Al13 (OH)32 7+ [16,18,19,42]. In the EC
seen in Fig. 1(b), the allowed permissible limit for arsenic removal
process, a slight increase observed with time in the pH was within
was obtained in the pHi range 5.0–9.0 as 9.5 ␮g L−1 for pHi 5.0,
the regulatory drinking water standards. Kobya et al. [19] observed
4.7 ␮g L−1 for pHi 6.0, 6.5 ␮g L−1 for pHi 7.0 and, 8.8 ␮g L−1 for pHi
the same effect during the EC process and also reported that EC can
8.0 in 15 min, respectively. Removal efficiencies of 93.5% for Fe and
act as pH neutralization step (Table 1).
95.7% for Al electrodes were achieved with a residual arsenic con-
centration of 10 ␮g L−1 or less for drinking water in the EC process.
A slight increase in the pH was observed with operating time 4.2. Effects of current density on arsenic removal
during the EC process (Fig. 2). The effluent pHfin were changed
from 6.4 to 9.5 for Fe electrodes and from 6.8 to 9.8 Al electrodes It is well known that current density determines coagulant
when the experiment was operated at pHi in the range 4.5–9.0. dosage rate and bubble production rate, size and growth of flocs
This slight increase of pH value was associated to the formation which can influence removal efficiency of the pollutions in the EC
of hydrogen gas at the cathode [19,37] and hydroxyl ions (OH− ) process. Results in Fig. 3 showed an important drop in the arsenic
produced at the cathode electrode according to Eqs. (5) and (6) concentration with an increase of the operating time for both elec-
5064 M. Kobya et al. / Electrochimica Acta 56 (2011) 5060–5070

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 Ci (␮g L−1 ) CEC (␮g L−1 ) Re (%) tEC (min) Cenergy (kWh m−3 ) Celec, exp (kg m−3 ) Wsludge (kg m−3 ) OC (D m−3 )

4.5 500 9.5 98.1 15 0.0148 0.0168 0.012 0.0155

5.5 500 8.1 98.4 10 0.0164 0.0155 0.014 0.0152
Fe 6.5 500 4.9 99.0 10 0.0140 0.0153 0.015 0.0146
7.5 500 6.5 98.7 8 0.0131 0.0148 0.018 0.0127
8.5 500 6.1 98.8 8 0.0131 0.0135 0.013 0.0115

5.0 150 9.5 93.7 15 0.0324 0.0077 0.018 0.0154

6.0 150 4.7 96.9 15 0.0324 0.0083 0.017 0.0165
Al 7.0 150 3.5 97.7 15 0.0324 0.0087 0.020 0.0172
8.0 150 8.8 94.1 15 0.0324 0.0085 0.020 0.0167
9.0 150 48.5 67.6 >15 0.0324 0.0061 0.013 0.0125

trodes at Ci = 150 ␮g L−1 , pHi 6.5 for Fe and 7.0 for Al electrodes as
current density varied in the range 2.5–7.5 A m−2 . The rate of reduc-
tion 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 efficiencies were
changed in the range 93.5–94.1% for Fe and 93.7–96.5% Al elec-
trodes at current density of 2.5–7.5 A m−2 (Table 2). In addition,
the results satisfied for all cases where arsenic concentration per-
missible level in drinking water was obtained lower than 10 ␮g L−1
and this concentration was marked in blue in Fig. 3. An important
decrease of the arsenic concentration appeared in the treated drink-
ing water solution just after 5 min for Fe and 2.5 min of operation
for Al electrodes, respectively. This can be attributed at high cur-
rent densities; the extent of anodic dissolution (Faraday’s law, Eq.
(26)) increased which increased the hydroxide cationic complexes
resulting in increased arsenic removal [16,19,21].
itEC Mw
Celec,theo =
zF v
where Celec, theo (kg Al or Fe electrode m−3 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 elec-
trons 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 mol−1 , Mw,Al = 26.98 g mol−1 ), F is the Faraday’s
constant (96,485 C mol−1 ) and v is the volume (m3 ) of the drink-
ing water in the EC reactor. According to Faraday’s law, the charge
passed to the solution was directly proportional to amount of elec-
trode (Fe or Al) dissolved. This implied that the arsenic removal
by EC may be governed by the formation of metal-hydrous fer-
ric 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 m−2 was
selected to achieve a residual arsenic concentration of 10 ␮g L−1
or less for drinking water in the EC process which resulted in
removal efficiencies 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.
(26) Arsenic species removed by metal hydroxide flocs were formed in
the vicinity of the anode surface either by surface complexation
or electrostatic attraction. Therefore, when high current densi-
ties 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 cur-
rent density and electrolysis time was necessary to optimize the
treatment efficiency 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 m−2 )

Fe electrode Al electrode

Current density, j (A m−2 ) 2.5 5.0 7.5 2.5 5.0 7.5

Current intensity imposed, i (A) 0.05 0.11 0.16 0.05 0.11 0.16
Operating time, tEC (min)a 12.5 7.5 5 15 10 4
Initial arsenic concentration, Ci (␮g L−1 ) 150 150 150 150 150 150
Effluent arsenic concentration, CEC (␮g L−1 )b 9.8 8.9 9.2 6.5 9.5 5.2
Arsenic removal efficiency, Re (%) 93.5 94.1 93.9 95.7 93.7 96.5
Average voltage between electrodes, U (V) 0.8 1.2 1.6 1.5 1.9 2.3
Initial pHi 6.5 6.5 6.5 7.0 7.0 7.0
Final pHf 7.3 7.8 8.1 7.5 7.5 7.6
Coulomb passed (C) 37.5 49.5 48.0 45.0 66.0 38.4
Charge loading (Faradays m−3 ) 0.694 0.9161 0.9161 0.833 1.22 0.711
Theoretically produced metal (mol) 1.94 × 10−4 2.57 × 10−4 2.49 × 10−4 1.55 × 10−4 2.28 × 10−4 1.33 × 10−4
Arsenic removed (mol) 1.57 × 10−6 1.87 × 10−6 1.88 × 10−6 1.90 × 10−6 1.90 × 10−6 1.90 × 10−6
Metal/arsenic ratio, Me/As (mol/mol) 123.8 137.4 132.5 81.3 121.7 68.7
Removal arsenic/Coulomb passed (mg C−1 ) 0.0038 0.0029 0.0029 0.0032 0.0021 0.0038
Energy consumption, Cenergy (kWh m−3 ) 0.0149 0.0276 0.0375 0.0324 0.0635 0.0472
Electrode consumption, Celec, exp (kg m−3 )c 0.0211 0.0272 0.0268 0.0087 0.012 0.0069
Electrode consumption, Celec, theo (kg m−3 )d 0.0194 0.0257 0.0249 0.0075 0.011 0.0064
Current efficiency, CE (%) 109 106 108 116 109 108
Sludge production, Wsludge (kg m−3 ) 0.031 0.034 0.058 0.020 0.019 0.0135
Operating cost, OC (D m−3 ) 0.0196 0.0255 0.0261 0.0172 0.0252 0.1485
a
Minimum operating time for WHO recommended level of maximum arsenic concentration (10 ␮g L−1 ) in the drinking water.
b
Data show values of arsenic concentrations under WHO recommended as 10 ␮g L−1 .
c
Experimental calculations.
d
Theoretical calculations.
 M. Kobya et al. / Electrochimica Acta 56 (2011) 5060–5070
Fig. 3. Effect of current density for (a) Fe electrode and (b) Al electrode on the resid-
ual arsenic concentration as a function of the EC treatment time from drinking water
(150 ␮g L−1 , 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 m−2 for both electrodes.
In the EC process, the coagulant Al3+ or Fe2+ were produced
by electrochemical sacrifice of the aluminum or iron anodes. Its
dosages were determined by charge loading. The quality of EC efflu-
ent depended on the amount of coagulant produced (mg) or applied
charge loading. Theoretically, according to Faraday’s 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 connec-
tion mode EC unit. When the charge loading of the EC was low,
the coagulant dosages (Al3+ of Fe2+ ) were not sufficient to removal
all arsenic ions, and thus the arsenic removal efficiency 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 vol-
ume [34,45]. The arsenic removal was proportional to the charge
loading in range of 0.1–0.9 F m−3 (Fig. 4a). The curve for the arsenic
removal flattened above approximately 0.69 and 0.83 F m−3 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 concen-
tration and it could be hindered by the increased gas production
when applying higher current. Another reason could be that the
5065
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 field 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 m−2 were 0.0038 and 0.0032 mg Coulomb−1 , respectively.
It was clear that a technically efficient process must also be fea-
sible 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 elec-
trodes was calculated in terms of kWh m−3 using the equation given
as follows:
UitEC
Cenergy = (27)
v
where U is cell potential (V) in the EC reactor. Energy consump-
tion versus operating time for both electrodes in the EC process
was shown in Fig. 4b and linear dependences were observed. The
5066 M. Kobya et al. / Electrochimica Acta 56 (2011) 5060–5070

energy consumptions for both electrodes were required 0.8 V for

Fe and 1.5 V for Al electrodes (Table 2). Therefore, longer operat-
ing times may be used to obtain higher arsenic removal efficiencies
using less electric energy. The energy consumptions for Fe elec-
trode (0.015 kWh m−3 ) were found to be lower than that for Al
electrode (0.032 kWh m−3 ). This result was probably due to the
higher potential required to achieve a certain current density.
According to Faraday’s 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 efficiency
and controlling the reaction rate in the EC reactor. As seen in Table 2,
experimental electrode consumption values at the 2.5 A m−2 were
0.021 kg m−3 for Fe and 0.0087 kg m−3 for Al electrodes while the
theoretical electrode consumption reached its highest value of
0.019 kg m−3 for Fe and 0.0075 kg m−3 for Al electrodes as min-
imum 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 elec-
trode 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 m−3 for Fe and
0.093 mol g m−3 for Al electrodes at a given current density of
2.5 A m−2 .
It was also an important parameter for the EC process because
it affected lifetime of the electrode [46]. The Faradic yield or cur-
rent efficiency (CE ) is defined 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 efficiency of the arsenic removal exper-
iments with electrode connection modes was calculated using the
following equation:
Celec,exp
CE (%) = × 100 (28)
Celec,theo
In Table 2, the results showed that the current efficiencies for
both electrodes were in the range 106–116%. 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 Fig. 5. Effects of initial concentration on the residual arsenic concentration as a
as the metal dissolved by the EC process. function of the EC treatment time from drinking water (a) Fe electrode and (b) Al
electrode (CD = 2.5 A m−2 , pHi 6.5 for Fe and 7.0 for Al electrodes).
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 between 5 and 191 [34,37]. The Fe:As ratio had to be high to reduce
drinking water. However, effectiveness of the EC process in the the concentration of arsenic below 10 mg L−1 around 20–28 using a
different process conditions was very sensitive to the Me (Fe or batch EC process [9,21], while the airlift reactor carrying out EC on
Al):As ratio, and this parameter can vary by several orders of mag- a 100 mg L−1 solution was around 14 mol mol−1 . The higher Me:As
nitude. The ratio metal (Me:Fe or Al; theoretically produced metal) ratio with 100 mg L−1 could be due to mass transfer being the lim-
to arsenic (removed from the EC process) at 10 mg L−1 in mol mol−1 iting step. For the efficient removal of arsenic from drinking water,
was calculated and shown in Table 2. It was seen from the table that the ratio typically was larger than 10 [23,37]. Our results were in
the lowest ratio was obtained for 123.8 mol Fe mol−1 arsenic and agreement with the literature values (Table 2).
68.7 mol Al mol−1 arsenic at the 2.5 A m−2 . This meant less metal
necessary to dissolve in order to adsorb or co-precipitate arsenic 4.3. Effects of arsenic concentration on arsenic removal
ions for both electrodes. In addition, this low ratio assured only a
small amount of final solid waste product in comparison to con- The effect of initial arsenic concentration from 75 to 500 mg L−1
ventional treatment methods. Furthermore, it could be seen that was examined with drinking water at 2.5 A m−2 , pH 6.5 for Fe and
no residual iron or aluminum was present in the outlet solution, pH 7.0 Al electrodes. Fig. 5a and b illustrated the effect of the initial
insuring a high arsenic removal efficiency of the produced ferric or arsenic concentration as a function of operating time. As can be seen
aluminum ions. This could indicate that OH− ions was produced in Fig. 5a and b, the initial arsenic concentration increased from 75
at the cathode and was promoting the arsenic, hydrolysis, pre- to 500 mg L−1 , the operating time and removal efficiency for achiev-
cipitation or co-precipitation (Eqs. (11)–(25)). These rations was ing the arsenic concentration of 10 mg L−1 increased from 7.5 to
also compared to the literature values, where Me:As ratios for con- 15 min and from 88.5 to 98.1% for Fe and from 4.0 to 15.0 min and
ventional precipitation with FeCl3 /Al(OH)3 addition fluctuate was from 86.9 to 98.7% for Al electrodes, respectively. In the EC process,
 M. Kobya et al. / Electrochimica Acta 56 (2011) 5060–5070 5067

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 Ci (␮g L−1 ) CEC (␮g L−1 ) Re (%) tEC (min) Cenergy (kWh m−3 ) Celec, exp (kg m−3 ) Wsludge (kg m−3 ) OC (D m−3 )

75 8.6 88.5 7.5 0.0076 0.0415 0.013 0.0358

Fe 150 9.8 93.5 12.5 0.0149 0.0211 0.031 0.0196
500 9.5 98.1 15.0 0.0206 0.1055 0.075 0.0912
75 9.8 86.9 4.0 0.0090 0.0056 0.013 0.0096
Al 150 9.5 93.7 15.0 0.0324 0.0087 0.020 0.0172
500 6.5 98.7 15.0 0.0308 0.0246 0.025 0.0416

the rate of arsenic removal was proportional to the initial arsenic
concentration. Higher arsenic removal efficiency 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 concentra-
tions arsenic ions readily electrocoagulated in the vicinity of Fe or
Al electrodes; however, with progress of the removal, increased dif-
fusional 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 flocs, and the adsorption capacity of flocs 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.
portional to characteristics of wastewater, settable solids and
matter destabilized by coagulation and concentration flocculent
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
floated 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 flocs bound more water, chemically or
physically, than iron hydroxide flocs did. Values of the sludge in
the initial pH and initial arsenic concentration in the EC process at
10 mg L−1 were 0.012–0.018 kg m−3 and 0.013–0.075 kg m−3 for Fe
and 0.013–0.020 kg m−3 and 0.013–0.025 kg m−3 for Al electrodes

4.4. Characteristics of EC sludge

The sludge production was another important parameter in

characterizing the EC process. The EC sludge production was pro-

Fig. 6. (a) SEM micrograph and (b) EDS spectra of sludge and imaged magnified Fig. 7. Pseudo second-order plot for arsenic adsorption (a) Fe electrode and (b) Al
2000×. electrode at different current densities in the EC process.
5068 M. Kobya et al. / Electrochimica Acta 56 (2011) 5060–5070

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 Al electrode

k2 (g mg−1 min−1 ) qe (mg g−1 ) r2 k2 (g mg−1 min−1 ) qe (mg g−1 ) r2

CD (A m−2 )
2.5 0.1431 5.2 0.99 0.0232 17.5 0.95
5.0 0.1322 2.6 0.94 0.0447 7.9 0.94
7.5 0.1810 1.7 0.95 0.0584 5.5 0.93
Ci (␮g L−1 )
75 0.2608 3.4 0.96 0.0242 12.8 0.98
150 0.1431 5.2 0.99 0.0223 17.5 0.95
500 0.0790 12.8 0.95 0.0026 46.2 0.94

(Tables 1 and 3). The sludge values at the optimum conditions were
0.031 kg m−3 for Fe and 0.020 kg m−3 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
20–50 ␮m. The sludge at 2000× magnification 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 Type of electrode Type of EC reactor Re (%) Current density tEC (min) OC ($ m−3 ) Reference
(A m−2 )

Drinking water Fe plate Batch 93.5 2.50 12.5 0.020 This study
(C0 = 150 ␮g L−1 As(III),
pHi = 6.5)
Drinking water Al plate Batch 95.7 2.50 15 0.017 This study
(C0 = 150 ␮g L−1 As (III),
pHi = 7.0)
Potable water Rod-shaped Fe Batch air fed >90–99 0.19 30–45a 5–45b – [22]
(C0 = 100–1000 ␮g L−1
As(III) and As(V)
pHi = 5–8.0)
Synthetic solution Rod-shaped Fe Continuous >75–85 0.25 2 – [24]
(C0 = 50 ␮g L−1 As(V), (0.245 L min−1 ) and
pHi = 7.5 and 6.5c ) batch
Synthetic solution Al plate Batch 98.4 20.00 30 – [25]
(C0 = 500 ␮g L−1 As(V),
pHi = 7.0)
Model water Carbon steel plate AISI Continuous air fed >95 45.00 0.08 – [27]
(C0 = ∼190 ␮g L−1 As(V), 1018 (3 L min−1 )
pHi = 8.07)
Ground water Carbon steel plate: AISI Continuous air fed 99 45.00 0.75 – [33]
(C0 = 133 ␮g L−1 1018 (0.875 L min−1 )
(122.5 ␮g L−1 As(V) and
10.5 ␮g L−1 As(III))
pHi = 8.06)
Synthetic solution Mild steel plate Batch 94 150.00 50 – [32]
(C0 = 100 mg L−1 As(V),
pHi = 7.0)
Ground water (Mexico) Low carbon steel plate Bipolar batch air fed >93 3.00 0.34 – [29]
(C0 = 131 ␮g L−1 As, ASTM 1018
pHi = 7.2)
Synthetic solution Fe cylinder Batch airlift >98 120.00 60 – [34]
(C0 = 100 mg L−1 As(V),
pHi = 7.0)
Synthetic solution Fe cylinder Continuous airlift 88–50 180.00 16.7–4.2 – [34]
(C0 = 100 mg L−1 As(V), (0.06–0.24 L min−1 )
pHi = 7.0)
Synthetic solution Steel plate: A37-24ES Continuous air fed >98 120.00 9d (90e ) – [37]
(C0 = 100 mg L−1 As(V)) (3 L h−1 )
Groundwater (Mexico) Carbon steel plate Lamar Mobil Pilot Plant >99 4.60 1.5 0.002f [39]
(C0 = 40 ␮g L−1 Astotal , (30 L min−1 )
pHi = 7.0)
Synthetic solution Fe plate Batch >99 1.53 5 – [40]
(C0 = 2 mg L−1 As(III) and
As (V), pHi = 6–8)

OC: operating cost (including costs of energy and electrode consumption), Re : As removal efficiency, tEC : operating time, j: current density.
a
100–1000 ␮g L−1 for As(III).
b
100–1000 ␮g L−1 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) 5060–5070 5069

Table 6
Comparison of the conventional processes with EC process for As removal [38,48].

Process type Process conditions Advantages Disadvantages

Precipitation with alum pH ≤ 6.5, ERS = lower as well as
higher As0 , AEAC ≤ 20 ␮g L−1 ,
Re = 20–90%, OC = medium
Precipitation with iron pH 6–8, ERS = lower as well as
higher As0 , AEAC ≤ 20 ␮g L−1 ,
Re = 60–90%, OC = medium
Precipitation with Fe/Mn pH > 7, ERS = lower as well as
higher As0 ,
AEAC ≤ 10 ␮g L−1 ,Re = 40–90%,
OC = medium
Lime softening pH ≥ 10.5, ERS = lower As0 ,
AEAC ≤ 10 ␮g L−1 , Re = 80–90%,
OC = high
Reverse osmosis ERS = lower As0 , AEAC ≤ 2␮g L−1 ,
Re ≥ 90%, OC = high
Electro dialysis pH 7–9, ERS = lower As0 ,
AEAC ≤ 3 ␮g L−1 , Re ≥ 95%,
OC = high
Ion exchanges pH 7.5, ERS = lower As0 ,
AEAC ≤ 2 ␮g L−1 , Re ≥ 90%, OC = high
Adsorption in activated pH 5.5–6.0, ERS = lower As0 ,
alumina AEAC ≤ 1 ␮g L−1 , Re ≥ 90%, OC = low
Adsorption on activated carbon pH 2–9, ERS = lower As0 ,
AEAC ≤ 7 ␮g L−1 , Re = 30–90%,
OC = low
Well established; suitable for
home use
Proven and reliable
Proven and reliable
Proven and reliable; reduces
corrosion
Highest water quality; treats wide
range of dissolved salts, minerals;
turbidity
Pure quality water
Can produce treated water with As
concentration less than 2 ␮g L−1
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
Use of chemicals; high arsenic
contaminated sludge; dose of oxidizing
chemicals highly influence on the
removal efficiency
Use of chemical; high arsenic
contaminated sludge; dose of oxidizing
chemicals highly influence on the
removal efficiency
Higher and lower pH reduces
efficiency; use of chemical; high
arsenic contaminated sludge; dose of
oxidizing chemicals highly influence
on the removal efficiency
Sulphate ions influence efficiency;
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
Efficiency affected by sulphate,
nitrates, fluorides ions, TDS, selenium,
etc.
Careful monitoring; effectiveness is
based on contaminant type;
concentration and rate of water usage;
bacteria may grow on alumina surface
Efficiency depends on the ash content
in the carbon and on the metal
concentration; not proven

AEAC: attainable effluent As concentration; Re : removal efficiency; 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 coat-
ing 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]:
(Ci − Cf )v
qt =
Ci
t 1 1
= + t (30)
qt k2 q2e qe
The slope and intercept were determined from the plot of
(t/qt ) versus t. In the equation, qt (mg g−1 ) is the amount of
arsenic species adsorbed at time t (min), Ci and Cf are arsenic
concentrations before and after the EC, k2 (g mg−1 min−1 ) 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 q2e (mg g−1 min−1 ) is the initial arsenic
adsorption rate, respectively. This kinetic model could provide a
good fit to the experimental data for the treatment times inves-
tigated and the correlation coefficients (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 coag-
ulant generated in the EC since the applied charge was directly
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 2.5–7.5 A m−2
and 75–500 ␮g L−1 in the EC were obtained in the range
5.2–1.7 mg g−1 , 3.4–12.8 mg g−1 and 0.1431–0.1810 g mg−1 min−1 ,
0.2608–0.0790 g mg−1 min−1 for Fe and 17.5–5.5 mg g−1 ,
12.6–46.2 mg g−1 and 0.0232–0.0584 g mg−1 min−1 ,
0.0242–0.0026 g mg−1 min−1 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].
(29)
4.6. Operating cost of arsenic removal
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 fixed 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 m−3 of the drinking water treated [16,21]:
operating cost (OC, D m−3 ) = aCenergy + bCelectrode + cCchemicals
(31)
where Cenergy (Eq. (27), consumption kWh m−3 ), Celectrode (Eq.
(26), consumption kg electrode m−3 ) and Cchemicals (consumption
5070 M. Kobya et al. / Electrochimica Acta 56 (2011) 5060–5070
kg chemicals m−3 ) 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 kWh−1 ),
b is electrode material price for Al (1.65 D kg−1 ) and Fe
(0.85 D kg−1 ),
c is chemical prices for NaOH and H2 SO4 (0.40 D kg−1 and
0.15 D kg−1 ).
The operating costs were calculated for the removal of arsenic
from drinking water at 10 mg L−1 or lower. The operating costs
at pH 4–9 and 75–500 mg L−1 were 0.012–0.016 D m−3 and
0.04–0.09 D m−3 for Fe and 0.015–0.017 D m−3 and 0.01–0.04 D m−3
for Al electrodes (Tables 1 and 3). The lower initial arsenic con-
centration yielded lower operating cost for removal efficiency 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 m−2 and Ci = 150 mg L−1 ) were calculated 0.020 D m−3
at 12.5 min for Fe and 0.017 D m−3 at 15.0 min for Al electrodes.
Unit cost of the process for Al (0.0012 D m−3 min) was found to be
cheaper than that of Fe (0.0016 D m−3 min−1 ).
Comparisons of arsenic removals with different electrode mate-
rials and operating conditions in the EC process were illustrated
in Table 5 [48]. As removal efficiencies in EC process with current
densities of 0.19–180 A/m2 and operating time 0.08–90 min were
obtained in the range of 50–>99%. It was difficult 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 litera-
ture such as energy, electrode, chemicals, etc. In this study, it was
obtained for better rate of As removal efficiency of 93.5% for Fe
electrode and 95.7% for Al electrode, respectively (Table 5).
Table 6 was produced to show comparison of conventional tech-
niques 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, difficulty in monitoring, high installation
and operating cost and lower efficiency in many cases.
5. Conclusions
Batch EC studies were performed to evaluate the influence 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 L−1 (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 m−2 , respectively. The optimum operating time
for arsenic removal was 12.5 min for Fe and 15 min for Al elec-
trodes. The operating costs at the optimum operating conditions
were calculated as 0.020 D m−3 for Fe and 0.017 D m−3 for Al
electrodes. The surface of sludge was analyzed by SEM and the
image was mainly composed of irregular and porous particles hav-
ing amorphous structure. The adsorption kinetics of arsenic on
amount of electrochemically dissolved metal (ferric or aluminum
hydroxides) based on Faraday’s laws was followed to the pseudo
second-order adsorption kinetic model. The arsenic adsorption
capacities at 2.5–7.5 Am−2 and 75–500 ␮gL−1 for the treatment
arsenic from the drinking water in the EC process were in the range
5.2–1.7 mg g−1 and 3.4–12.8 mg g−1 for Fe and 17.5–5.5–mg g−1
and 12.8–46.2 mg g−1 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.
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