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Journal of Environmental Management 190 (2017) 102e112

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Journal of Environmental Management


journal homepage: www.elsevier.com/locate/jenvman

Research article

Simultaneous arsenic and fluoride removal from synthetic and real


groundwater by electrocoagulation process: Parametric and cost
evaluation
Lokendra Singh Thakur, Prasenjit Mondal*
Department of Chemical Engineering, Indian Institute of Technology Roorkee, Uttarakhand, India

a r t i c l e i n f o a b s t r a c t

Article history: Co-existence of arsenic and fluoride in groundwater has raised severe health issues to living being. Thus,
Received 12 May 2016 the present research has been conducted for simultaneous removal of arsenic and fluoride from synthetic
Received in revised form groundwater by using electrocoagulation process with aluminum electrode. Effects of initial pH, current
16 December 2016
density, run time, inter electrode distance and NaCl concentration over percentage removal of arsenic
Accepted 21 December 2016
and fluoride as well as operating cost have been studied. The optimum experimental conditions are
found to be initial pH: 7, current density: 10 A/m2, run time: 95 min, inter electrode distance: 1 cm, NaCl
concentration: 0.71 g/l for removal of 98.51% arsenic (initial concentration: 550 mg/l) and 88.33% fluoride
Keywords:
Electrocoagulation
(initial concentration: 12 mg/l). The concentration of arsenic and fluoride in treated water are found to be
Synthetic groundwater 8.19 mg/l and 1.4 mg/l, respectively, with an operating cost of 0.357 USD/m3 treated water. Pseudo first
Real groundwater and second order kinetic model of individual and simultaneous arsenic and fluoride removal in elec-
Arsenic removal trocoagulation have also been studied. Produced sludge characterization studies also confirm the pres-
Fluoride removal ence of arsenic in As(III) form, and fluoride in sludge. The present electrocoagulation process is able to
Operating cost reduce the arsenic and fluoride concentration of synthetic as well as real groundwater to below 10 mg/l
and 1.5 mg/l, respectively, which are maximum contaminant level of these elements in drinking water
according to WHO guidelines.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction carcinogenic nature, which appears in human body in the form


skin, lung, liver and kidney cancer (Karim, 2000; Morales et al.,
Co-existence of arsenic and fluoride in natural water has raised a 2000). It is reported that co-exposure of arsenic and fluoride can
severe health issue for many countries worldwide in recent years. A have more impact on the integrity of the genetic material of cells
large populations in India, Bangladesh, Pakistan, Mexico, Mongolia, than the individual exposure (Rao and Tiwari, 2006). Co-exposure
Argentina, etc. (Farooqi et al., 2007a, 2007b; He et al., 2009; Kumar of these can also lead to both endemic fluorosis and arsenicosis
et al., 2010; Chaurasia et al., 2012; Dutta, 2013; Reyes-Go mez et al., (Alarco  n-Herrera et al., 2013). Arsenic and fluoride are introduced
2015; Gomez et al., 2009) are affecting due to various type of dis- in groundwater mainly through oxidative weathering and
eases related to arsenic and fluoride. Excess fluoride intake in body geochemical reactions (Banerjee et al., 2008; Meenakshi and
causes many diseases such as skeleton fluorosis, teeth disintegra- Maheshwari, 2006). Anthropogenic sources, such as liquid waste
tion etc. (Nell and Livanos, 1988; Brown et al., 1977). However, the of glass, metal, semiconductor, pesticides, mining etc. industries
fluoride concentration less than 1.5 mg/l (WHO, 2011) in drinking can also deep percolate inside the earth, and subsequently
water is essential for strengthen of bone and teeth. In addition to contaminate the groundwater (Lacasa et al., 2011; Ayoob and
that, arsenic concentration greater than 10 mg/l (WHO, 2011); is Gupta, 2006; Meenakshi and Maheshwari, 2006). Arsenic and
more severe threat to humans due to its inherent toxic and fluoride both exist in the form of anion in water. In natural water,
arsenic is predominantly present in the form of arsenite (As(III))
and arsenate (As(V)), the ratio of these arsenic species depends on
the pH and redox potential (Luukkonen et al., 2016; Ungureanu
* Corresponding author. Department of Chemical Engineering, Indian Institute of
Technology Roorkee, Roorkee 247667, Uttarakhand, India. et al., 2015). As(V) occurs in oxygenated water, while in anaerobic
E-mail address: mondal2001@gmail.com (P. Mondal). groundwater As(III) is normally available. As(III) species is much

http://dx.doi.org/10.1016/j.jenvman.2016.12.053
0301-4797/© 2016 Elsevier Ltd. All rights reserved.
L.S. Thakur, P. Mondal / Journal of Environmental Management 190 (2017) 102e112 103

more toxic than As(V) (Kobya et al., 2011). Very recently in 2015, h i
high arsenic and fluoride concentration has been reported in the AlðOHÞ3ðsÞ þ HAsO2 2
4 / AlðOHÞ3 HAsO4 (4)
s
groundwater of Rajnandgaon district of Chhattisgarh in India (Patel
et al., 2015). Hence, it is an urgent need to find a technology which The mechanism of fluoride removal in electrocoagulation is still
can efficiently remove arsenite and fluoride both from not fully understood. This stems mainly from the fact that at least
groundwater. three mechanisms may compete (Zhu et al., 2007):
From literature it is revealed that many approaches such as
adsorption, chemical coagulation, membrane filtration, electrodi- (a) Adsorption on aluminum hydroxide particles
alysis, oxidation, biological methods etc. are applied for removal of
arsenic and fluoride from contaminated water (Liu et al., 2012; AlðOHÞ3 þ xF /AlðOHÞ3x Fx þ xOH (5)
Mohan and Pittman, 2007; Amor et al., 2001; Castel et al., 2000).
All these technologies mentioned above suffer from various dis-
(b) Coprecipitation
advantages; for examples the adsorption process is pH dependent,
it requires pre-treatment step, high treatment time, and its nAl þ ð3n  mÞOH þ mF / Aln Fm ðOHÞ3nm (6)
contamination removal efficiency reduces after each regeneration
cycle (Kobya et al., 2011; Mohan and Pittman, 2007). Coagulation
method requires a large amount of chemical, large area for treat- (c) Fluoride attachment to electrodes.
ment and produces a secondary sludge (Kobya et al., 2011;
Balasubramanian et al., 2009). High membrane and operating Many studies are available on removal of arsenic and fluoride
cost, skilled labour requirement, and concentrated sludge genera- from aqueous solution by applying electrocoagulation process (Ali
tion are major drawbacks associated with the membrane filtration et al., 2012; Flores et al., 2013; Lacasa et al., 2011; Song et al.,
technologies (Balasubramanian et al., 2009; Lacasa et al., 2011). 2014a; Ghosh et al., 2008; Zhu et al., 2007; Zuo et al., 2008; Zhao
Whereas, biological processes, are mainly used for treatment of et al., 2009; Un et al., 2013). All these studies were conducted for
industrial waste water and not for drinking water, as the processes removal of arsenic or fluoride separately. While, Zhao et al. (2011)
require several types of pathogenic and non-pathogenic microor- had designed and used an integrated electro-oxidation and elec-
ganisms like algae, yeast, fungi, bacteria etc. Moreover, their trocoagulation process for simultaneous removal of arsenite and
selectivity depends on type of contaminants which has to be fluoride. Titanium based dimensionally stable anode with different
removed (Veglio and Beolchini, 1997). High treatment time, large combination of Fe and Al electrode were used in their research
land area requirement, less design flexibility are additional draw- work. Cost of any treatment process is a significant factor associated
backs of biological processes (Veglio and Beolchini, 1997; Yadav with their implementation. Since, titanium based electrode was
et al., 2012). used, hence their cost of treatment was high. Although, no cost
In comparison to above conventional treatment methods, elec- estimation study was performed by them. Moreover, initial con-
trocoagulation process has drawn attention of researchers due to its centrations of arsenite and fluoride were 1 mg/l and 4.5 mg/l,
high removal efficiency, easy to operate, cost effectiveness and respectively. However, in real groundwater, the concentration of
possibility of complete automation of process (Rajeshwar et al., arsenic is found less (<500 mg/l) and fluoride concentration is found
1994; Chen, 2004; Mollah et al., 2004; Emamjomeh and higher (>10 mg/l) (Neva rez et al., 2011; Aiuppa et al., 2000; Jadhav
Sivakumar 2009). In electrocoagulation process insitu generated et al., 2015). Patel et al. (2015) also reported the presence of arsenic
metal hydroxides act as coagulant in aqueous solution, which and fluoride in groundwater of Rajnandgaon district of Chhattis-
provides the active sites for adsorption of polluting species. Apart garh, India, in which most of the sample contains arsenic concen-
from adsorption, sweep coagulation, bridge coagulation, copreci- tration <575 mg/l and fluoride concentration >10 mg/l. According to
pitation etc. also play a role for the removal of pollutants in elec- the information available, no study has been performed for
trocoagulation process. The electrochemical reactions using Al as simultaneous removal of arsenic and fluoride in these range by
electrode materials may be summarized as follows (Kobya et al., electrocoagulation along with cost estimation.
2011): In the present study, the lab experiments in batch mode have
Reaction at anode been performed at constant initial arsenic and fluoride concentra-
tion, to investigate the effects of initial pH, current density, run
Al/Al3þ þ 3e (1) time, inter electrode distance and NaCl concentration on percent-
age removal of arsenic and fluoride as well as operating cost of
Reaction at cathode
treatment. Removal of arsenic and fluoride mainly depends on their
initial concentration. Hence, variation of initial concentration on
2H2 O þ 2e /H2 þ 2OH (2)
their removal efficiency has also been studied. Furthermore, the
Reaction in aqueous solution kinetic studies for individual and simultaneous arsenic and fluoride
removal in electrocoagulation have also been performed to eval-
Al3þ þ 3OH /AlðOHÞ3ðsÞ (3) uate the reaction rate constants as well as interactions. To explore
the mechanism of removal of arsenic and fluoride, produced sludge
In electrocoagulation aluminum and hydroxides ion generated characterization has been conducted by Field emission scanning
by reactions (1) and (2), react together and form various species of electron microscopy (FESEM), X-ray diffraction (XRD) and Fourier
monomeric such as AlðOHÞþ 4þ 2þ
2 , Al2 ðOHÞ2 , AlðOHÞ , AlðOHÞ4 and

transform infrared spectroscopy (FTIR).
polymeric species viz. Al6 ðOHÞ3þ 15 , Al7 ðOHÞ 4þ
17 , Al 8 ðOHÞ4þ
20 ,
5þ 7þ
Al13 ðOHÞ34 , Al13 O4 ðOHÞ24 (Ghosh et al., 2008; Rinco  n and La
Motta, 2014). This species are further transformed into amor- 2. Materials and methods
phous AlðOHÞ3ðsÞ according to complex precipitation kinetics
(Behbahani et al., 2011). Furthermore, this AlðOHÞ3 complex is 2.1. Materials
believed to adsorb arsenic (Kobya et al., 2011; Flores et al., 2013)
and fluoride (Hu et al., 2003). All chemicals used in the present experiment were of analytical
104 L.S. Thakur, P. Mondal / Journal of Environmental Management 190 (2017) 102e112

grade. Stock solutions of arsenite (As(III)) and fluoride (1000 mg/l) water, while a and b are coefficient for Indian market in year 2015,
were prepared from sodium arsenite (NaAsO2) and sodium fluoride respectively.
(NaF) salt, respectively. Desired concentration of arsenite and Coefficient a: Wholesale electrode material price ¼ 1.77 USD/kg
fluoride were made from the dilution of stock solution in distilled Al (Web link 1).
water. Initial pH of solution was adjusted by using 1 N NaOH and Coefficient b: Industrial electricity price ¼ 0.08 USD/kwh1
1 N HCl solution. (Web link 2).
Energy consumption in electrocoagulation process was calcu-
2.2. Experiment setup lated by Eq. (9).
 
Experiments were carried out in a Perspex made batch reactor kwh voltage  current  runtime
Energy consumption ¼
having dimension of 0.15 m  0.10 m  0.12 m with working vol- m3 working volume of reactor
ume of 1.4 l (Behbahani et al., 2011). Four Al electrodes (97.4% pu- (9)
rity) were fitted in monopolar mode with total effective surface
area of 512 cm2. DC power supply of range 0e30 V and 0e10 A was Cost of electrode material was considered in term of material
used to conduct electrocoagulation. loss in electrocoagulation process by subtracting the initial weight
and final weight of anode electrode before and after electro-
coagulation process.
2.3. Procedure
To evaluate the removal rate constant, which depends on the
initial arsenic and fluoride concentration, further experiments were
Aluminum electrodes were rubbed with sand paper and then
performed in single and bi-component solution at the optimized
dipped in dilute nitric acid solution and distilled water for surface
conditions. The removal kinetics of arsenic and/or fluoride on the
cleaning. After cleaning, electrodes were dried at 105  C and then
amount of electrochemically dissolved aluminum oxyhydroxides
weighted. Working solution composed of fix concentration of
were described by pseudo-kinetic models. The rate of removal of
550 mg/l arsenite and 12 mg/l fluoride was treated in batch elec-
arsenic and fluoride can be represented by the following nth order
trocoagulation at 500 rpm by using magnetic stirrer. The effects of
mechanism:
initial pH, current density, run time, inter electrode distance and
NaCl concentration were studied at different conditions as listed in
dC
Table 1. At the end of electrocoagulation, the solution was filtered ¼ kCn (10)
dt
through 0.45 m filter and analyzed for arsenic and fluoride detec-
tion. All experiments were performed thrice and the average values where, C represents the arsenic/fluoride concentration, k is the rate
are reported. In addition, after the electrocoagulation experiment constant, n is the order of reaction, and t is the run time. For a
produced sludge was dried at 105  C temperature for sludge pseudo first order reaction, the integration of above Eq. (10) yields;
analysis.
 
The percentage removal of contaminant was calculated from Eq. Ct
ln ¼  k1 t (11)
(7) Ci
 
Ci  Co A slope of graph of ln CCti versus run time (t) gives the value of
Removal ð%Þ ¼  100 (7) 1
rate constant k1 (min ). Here, Ci is the initial arsenic/fluoride
Ci
concentration, Ct is the concentration values at run time t.
where, Ci and Co are initial and final concentration of contaminants Furthermore, for the pseudo second order reaction, above Eq. (10)
in solution. becomes;
Visual MINTEQ simulation program was used for single
component speciation of As(III), fluoride and aluminum at different 1 1
 ¼ k2 t (12)
initial pH (1e14) putting the fixed temperature value of 25  C. Ct Ci
Implementation feasibility of any treatment process in large A slope of graph between C1t versus run time (t) gives the value of
scale depends mainly on cost of treatment process. Operating cost rate constant k2 (l/(mg min)).
of electrocoagulation process includes cost of electrode, chemical,
electricity, sludge disposal, fixed cost etc. In the present study,
electrode material cost and electricity charges were taken in ac- 2.4. Analysis
count for preliminary economic evaluation (Daneshvar et al., 2006)
2.4.1. Inductively coupled plasma mass spectrometry and ion
Operating cost ¼ a  CElectrode þ b  CEnergy (8) selective electrode
Arsenic analysis was carried out by Inductively Coupled Plasma
where, CElectrode (kg Al/m3) and CEnergy (kwh/m3) are consumption Mass Spectrometer (ICP-MS, Perkin Elmer, model ELAN-DRC-e)
of quantities for the treatment of arsenic and fluoride contaminant according to standard method USEPA 200.8 (Creed et al., 1994).

Table 1
Range of operating parameters for arsenic and fluoride removal by electrocoagulation.

Type of experiments Initial Current density Run time Inter electrode NaCl Initial As(III) Initial F
pH (A/m2) (min) distance concentration concentration concentration
(cm) (g/l) in mg/l in mg/l

Effect of initial pH 3e11 30 60 1 0.71 550 12


Effect of current density (A/m2) 7 10e60 60 1 0.71 550 12
Effect of run time (min) 7 10 0e120 1 0.71 550 12
Effect of inter electrode distance (cm) 7 10 95 0.5e2 0.71 550 12
Effect of NaCl concentration (g/l) 7 10 95 1 0.5e1.5 550 12
L.S. Thakur, P. Mondal / Journal of Environmental Management 190 (2017) 102e112 105

While, fluoride analysis was carried out by Ion meter (Orlab India,
model-OR930) coupled with compatible fluoride ion selective
electrode. To prevent the interference of other ions in fluoride
detection, TISAB buffer was added to each aliquot with the volume
ratio of 1:1. This is a solution containing sodium chloride, acetic
acid, sodium hydroxide and 1,2-cyclohexylene diamine tetra acetic
acid (Thakur and Mondal, 2016).

2.4.2. Field emission scanning electron microscopy


The sludge produced in electrocoagulation was analyzed by
Field Emission Scanning Electron Microscopy (FE-SEM, FEI, model-
Quanta 200 FEG). For sample preparation, the dried sludge sample
was coated with gold in presence of argon. Energy dispersive X-ray
analysis was an integrated feature of the scanning electron
microscope.

2.4.3. Fourier transform infrared spectroscopy


An infrared spectrum of produced sludge was taken by Thermo Fig. 1. Effect of initial pH on removal of arsenic and fluoride, operating cost (Initial As
FTIR (model- Nicolet 6700). Around 10 mg of dried sludge was concentration: 550 mg/l, F concentration: 12 mg/l, NaCl concentration: 0.71 g/l, current
density: 30 A/m2, run time: 60 min, inter electrode distance: 1 cm); Initial pH and final
dispersed in 100 mg of spectroscopic grade KBr to record IR spectra
pH of solution (inset).
in the wavenumber range of 500e4000 cm1.
pH 7, while no significant improvement is observed beyond the
2.4.4. X-ray diffraction initial pH 7. High removal of arsenic in acidic pH proposes that apart
The produced sludge crystal structure was studied by X-ray from adsorption, sweep coagulation and coprecipitation are also
diffractometer (XRD, BRUKER D8 advance, with Cu Ka, l ¼ 1.54 Å, liable for removal. During aluminum electrocoagulation, several
scanning rate is 1 min1) and the data was analyzed through monomeric and polymeric species such as AlðH2 OÞ4 ðOHÞ2þ ,
þ
PANalytical X'Pert HighScore software version 1.0e using database AlðH2 OÞ5 ðOHÞ2þ , AlðH2 OÞ3þ 2þ
6 , AlðOHÞ , AlðOHÞ2 , Al2 ðOHÞ2 ,

of X-ray powder diffraction patterns maintained by the Interna- AlðOHÞ 4 , Al6 ðOHÞ 3þ
15 , Al7 ðOHÞ 4þ
17 , Al8 ðOHÞ 4þ
20 , Al 13 ðOHÞ 5þ
34 ,
tional Centre for Diffraction Data (ICDD) as well as published Al13 O4 ðOHÞ7þ24 etc. can be formed in aqueous solution (Rebhun and
literature. Lurie, 1993). These species may further transform into amorphous
AlðOHÞ3ðsÞ according to complex precipitation kinetics (Behbahani
2.4.5. Statistical analysis et al., 2011). Freshly formed amorphous AlðOHÞ3 has minimum
Experimental data were subjected to statistical analysis. solubility and is finally polymerized to Aln ðOHÞ3n , which results
into dense flocs formation (Kobya et al., 2006, 2011; Behbahani
3. Results and discussion et al., 2011). The presence of common ions in the solution may
slightly influence the formation of these intermediates (Mouedhen
The effects of initial pH, current density, run time, inter elec- et al., 2008), thus, further investigation is required for better un-
trode distance, and NaCl concentration on percentage removal of derstanding of the process and to determine the intermediates
arsenic and fluoride as well as operating cost are discussed below. under common ion effects. The dense floc has large surface area,
The standard deviations of experimental data are found in range of which provides entrapment of colloidal arsenic particles and thus,
0 to 1.5. the arsenic removal occurs (Ouaissa et al., 2014). Hence, at initial
acidic pH range, entrapment of arsenic in flocs and elevation in
3.1. Effect of initial pH solution pH are accountable for high arsenic removal. It is ascer-
tained from Fig. 2a that as the pH increases to 7, neutral form of
The pH of a solution is one of the most significant parameter arsenite H3 AsO3 decreases slightly, as well as negatively charged
that governs the removal of arsenic and fluoride in electro- H2 AsO 3 increases. Although, at these pH positive charged AlðOHÞ3
coagulation. To investigate this effect, a series of experiments are moiety (Fig. 2b) dominates in bulk solution, hence removal in-
performed according to the parameters mentioned in Table 1. It is a creases due to charge neutralization and is found maximum at
highlighted fact that pH of the solution increases during electro- initial pH 7. As initial pH increases to above 7, amount of negative
coagulation (Fig. 1) for the formation of OH ions and H2 (Vik et al., charge of arsenite and AlðOHÞ3 increases. Therefore, percentage
1984; Chen et al., 2000) gas at the cathode according to Eq. (2). arsenic removal decreases due to charge repulsion. It is also note-
Fig. 1 shows the effects of initial pH on percentage removal of worthy to mention that for initial pH of 11 the solution pH reduces
arsenic and fluoride as well as also depicts the plot of initial pH and to 9.5 which is attributed to amphoteric aluminum hydroxide
final pH of solution before and after electrocoagulation. Final pH of behavior (Eq. (13)), leading to decline in pH (Song et al., 2014b). Due
solution is found to 8.4 for all the initial pH values (3e11). Arsenic to this reason high As(III) removal is observed even at initial pH
and fluoride removal depends on both initial pH and elevation of of 11.
pH during electrocoagulation. In aqueous solution arsenite (As(III))
species are present in the form of H3 AsO3 , H2 AsO 2
3 , HAsO3 , while AlðOHÞ3 ðsÞ þ ðOHÞ ðaqÞ/AlðOHÞ
4 ðaqÞ (13)
fluoride is present in HF and F form. Speciation of arsenic and
fluoride changes with pH of solution and redox potential. Similarly, The FTIR spectra (Fig. 8e) also confirms the presence of As(III) in
the aluminum ion speciation also changes with the solution pH. the produced sludge. In case of fluoride, percentage removal is
Thus, in electrocoagulation process arsenic and fluoride removal found maximum (95.83%) at initial pH 3 and then decreases
changes with solution pH. continuously with increase in pH. It is revealed from Fig. 2c that
It is evident from Fig. 1 that percentage arsenic removal in- negative charge fluoride and positive charge AlðOHÞ3 are domi-
creases from 93.61% at acidic initial pH 3 to 98.43% at neutral initial nated at pH 3. Hence, maximum removal of fluoride is observed
106 L.S. Thakur, P. Mondal / Journal of Environmental Management 190 (2017) 102e112

Fig. 2. Distribution of species as a function of pH, a) Arsenite, b) Aluminum, c) Fluoride in solution simulated by Visual MINTEQ version 3.1. (Song et al., 2014b).

due to charge neutralization. The drop in percentage removal of current I (A) passed for a period of time t (s), M is molecular mass of
fluoride occurs with the increment in initial pH, it is attributed due Al (26.98 g/mol), Z is number of electron transferred (Z ¼ 3 for Al), F
to reduction in positive charged AlðOHÞ3 colloidal particles. As is Faradays constant (96,485 C/mol), V is volume (m3). It is ascer-
initial pH increases to above 8, the removal decreases further due to tained from Eq. (14) that as more current passes through process,
presence of negative charge fluoride and AlðOHÞ 4 species in solu- more amount of coagulant and bubble generate, which increase
tion. No significant effect of pH is observed on operating cost, as for mixing intensity inside electrocoagulation process. Thus, increasing
cost calculations only anode mass loss and electricity consumption current density would accelerate the liberation rate of Al3þ and
were considered (Eq. (8)). FTIR and XRD spectra (Fig. 8e and f) also OH ions, which further help to accelerate the removal efficiency.
prove the presence of fluoride in the produced sludge. To understand the effect of current density on operating cost,
percentage removal of arsenic and fluoride, several lab experiments
have been performed at different current densities in the range of
3.2. Effect of current density 10e60 A/m2. Fig. 3 represents the effect of current density on
operating cost and percentage removal of arsenic and fluoride. It
Current density plays an important role for removal of arsenic could be seen from Fig. 3 that at current density 10 A/m2 operating
and fluoride in electrocoagulation process, as it determines rate of cost, percentage removal of arsenic and fluoride are found
coagulant dosage, bubble production, size and growth of flocs, 0.269 USD, 96.11% and 83.33%, respectively. Incremental increased
which influence the removal efficiency of electrocoagulation. Cur- in operating cost, percentage removal of arsenic and fluoride are
rent density is a measure of amount of current passed through unit observed with increased in current density. At current density 40 A/
cross section area. According to Faraday law (Eq. (14)), loss in m2 and above the residual concentration of arsenic and fluoride
weight of material is proportional to quantity of electricity passed reduce to 10 mg/l and 1.5 mg/l, respectively, which comes under
in solution during electrocoagulation. the safe drinking water according to WHO guidelines. Maximum
percentage removal of arsenic (99.47%) and fluoride (91.66%) are
MIt
Celec thero ¼ (14) found at current density 60 A/m2. It is mainly attributed due to the
ZFV generation of high amount of Al3þ and OH ions at anode and
where Celect is theoretical amount of aluminum produced by cathode, respectively, and combination of these to form AlðOHÞ3 ,
thero
L.S. Thakur, P. Mondal / Journal of Environmental Management 190 (2017) 102e112 107

fluoride according to WHO guidelines. Initially up to 45 min, fluo-


ride removal is found higher as compared to arsenic removal as the
initial fluoride concentration is twenty one times more than the
initial arsenic concentration. Hence more fluoride removal as
compared to arsenic is observed. As time reaches to 120 min, per-
centage fluoride removal increases to 91.75%. The operating cost is
found to be 0.521 USD/m3. As described in section 3.2. and from Eq.
(14) it could be clearly understood that run time increases the
operating cost of process. As the time increases more amount of
metal dissolution occurs due to anodic oxidation, consequently, it
consumes more energy according to Eq. (9). Therefore, operating
cost increases linearly with the run time. Since, the removal of
arsenic and fluoride is achieved to 97.46% and 87.5%, respectively in
90 min, the arsenic removal does not come to below WHO drinking
water guidelines. Hence according to Fig. 4, for the removal of
Fig. 3. Effect of current density on removal of arsenic and fluoride, operating cost 98.18% arsenic (residual concentration-  10 mg/l) 95 min of run
(Initial As concentration: 550 mg/l, F concentration: 12 mg/l, NaCl concentration:
time is considered. To find out the operating cost for 95 min run
0.71 g/l, initial pH: 7, run time: 60 min, inter electrode distance: 1 cm).
time another experiment has been performed at optimum condi-
tions (pH: 7, current density: 10 A/m2), at which final concentration
when high current density is applied. Furthermore, these accu-
of arsenic and fluoride in treated water is found to be 8.19 mg/l
mulated aluminum hydroxides adequately remove arsenic and
(98.51%) and 1.4 mg/l (88.33%), respectively while the operating
fluoride in bulk solution. Hence, when high current densities are
cost is found as 0.357 USD/m3.
applied, the removal of both arsenic and fluoride increases. How-
ever, more sludge is also produced at higher current densities due
to elevated dissolution rate of aluminum anode electrode. 3.4. Effect of inter electrode distance
Furthermore, it would increase the cost of treatment process. For an
economically feasible process it is necessary to optimize the cost of The results of various inter electrode distance on removal of
treatment process (due to current density) in such a way that high arsenic and fluoride as well as operating cost are presented in Fig. 5.
percentage removal achieves with lowest treatment cost. Consid- With the increase in electrode distance from 0.5 to 1 cm, percent-
ering this factor, all further experiments were performed at current age removal of arsenic and fluoride increases from 92.47 to 98.51%
density of 10 A/m2. and 86.67 to 88.33%, respectively and decreases thereafter from 1.5
to 2 cm. Very less inter electrode distance (0.5 cm) makes it difficult
3.3. Effect of run time to circulate the solution between the electrodes, hence removal is
less, it increases gradually with the increase in inter electrode
It is elucidated from Fig. 4 that removal of both arsenic and distance up to 1 cm. Removal of both arsenic and fluoride reduces
fluoride increases with increase in run time. Removal of 45.22% with the increase in electrode distance from 1.5 to 2 cm due to less
arsenic is achieved in first 15 min operation and it enhances further interaction of arsenic and fluoride with the hydroxyl polymers. In
to 97.46% at 90 min and thereafter no appreciable increase in other words, the decreases in local concentration and electrostatic
removal is observed (99.06% at 105 min and 99.26% at 120 min). As attraction are the reasons for the decrease in removal. Operating
the time progresses, more amount of coagulant is accumulated cost increases slightly with increase in inter electrode distance
inside the reactor, which is accountable for high arsenic removal. It from 0.5 to 1 cm afterward it increases linearly with inter electrode
is also found that 70% fluoride removal is achieved in first 15 min of distance. As the distance between electrodes increases, current
process and then increases gradually with run time. It is attributed reduces, thus to maintain a constant current density the voltage has
due to high adsorption capacity of insitu generated aluminum to be raised, which further enhances the operating cost. From the
coagulant for fluoride ion (Hu et al., 2003). At run time 90 min, above discussion, the most suitable electrode distance is found to
87.5% of fluoride removal is achieved i.e. residual fluoride concen- be 1 cm.
tration of 1.5 mg/l, which is a maximum contaminant level for

Fig. 4. Effect of run time on removal of arsenic and fluoride, operating cost (Initial As Fig. 5. Effect of inter electrode distance on removal of arsenic and fluoride, operating
concentration: 550 mg/l, F concentration: 12 mg/l, NaCl concentration: 0.71 g/l, initial cost (Initial As concentration: 550 mg/l, F concentration: 12 mg/l, NaCl concentration:
pH: 7, current density: 10 A/m2, inter electrode distance: 1 cm). 0.71 g/l, initial pH: 7, current density: 10 A/m2).
108 L.S. Thakur, P. Mondal / Journal of Environmental Management 190 (2017) 102e112

3.5. Effect of NaCl concentration

The effect of various NaCl concentration on removal of arsenic


and fluoride as well as operating cost is shown in Fig. 6. Removal of
arsenic and fluoride also depends upon the specific conductivity of
the solution. In present study, NaCl has been selected as a sup-
portive electrolyte due to its cheap price and low toxicity. The
percentage removal of both arsenic and fluoride increases to 98.51
and 88.33%, respectively, with the increase in NaCl concentration
up to 0.71 g/l; which satisfy the WHO drinking water guidelines.
This demonstrates that the removal of both arsenic and fluoride
takes place rapidly due to the ionic conductivity of the solution
which enhances with the different dose of NaCl. Addition of chlo-
ride ions facilitate the passage of electric current by increasing in
solution conductivity, and also rupture the passive films of
aluminum electrodes (Behbahani et al., 2011; Hu et al., 2003). It
permits more dissolution of aluminum anode in solution, therefore
the removal of both arsenic and fluoride increases. In case of high
NaCl concentration (1 and 1.5 g/l), removal of both arsenic and
fluoride reduces slightly. It can be attributed due to competitive
adsorption effect (Zuo et al., 2008). When the NaCl concentration
increases from 0.5 to 0.71 g/l operating cost reduces due to less
consumption of electrical energy. Although, further increase in
NaCl concentration beyond 0.71 g/l has less effect on energy con-
sumption and subsequently on operating cost. Maximum per-
centage removal of arsenic and fluoride is achieved at 0.71 g/l NaCl
concentration.

3.6. Effect of variation of initial arsenic and fluoride concentration Fig. 7. Effect on removal of a) arsenic in presence of fluoride. b) fluoride in presence of
on their removal arsenic (Initial As concentration: 300e1250 mg/l, F concentration: 5e20 mg/l, NaCl
concentration: 0.71 g/l, initial pH: 7, current density: 10 A/m2, inter electrode distance:
1 cm).
It is revealed from Fig. 7a that removal of arsenic (initial con-
centration: 550 mg/l) decreases from 99.05, 98.65, 95.39 and 94.15%
with the increase in initial fluoride concentration from 5, 10, 15 and
20 mg/l, respectively. Similarly, removal of fluoride (initial con- 3.7. Real groundwater study
centration: 15 mg/l) also decreases from 87.33, 85.33, 84.66 and
84% with the increase in initial arsenic concentration from 300, The performance of electrocoagulation process was also evalu-
550, 900, 1250 mg/l. Similar trends of decrease in percentage ated for the removal of arsenic and fluoride from real groundwater
removal are also observed with the other initial arsenic and fluoride sample collected from Kaudikasa village, Rajnandgaon district,
concentration as shown in Fig. 7a and b. It is due to the preferential Chhattisgarh, India. The initial characteristics of groundwater was
adsorption of high amount of available ions in the solution as pH: 6.8, D.O.: 4 mg/l, turbidity: 17 NTU. Other parameters are
compared to less amount ion as the dose of coagulant remains same mentioned in Table 2. At optimum conditions (Initial pH: 7, current
in electrocoagulation. It is also evident from Fig. 7a and b, that density: 10 A/m2, run time: 95 min), electrocoagulation process
removal of both arsenic and fluoride is responsive to alteration of successfully reduced the arsenic and fluoride concentration to
their initial concentration. below maximum contaminant level according to WHO drinking
water guidelines (removal As: 98.41%, F: 96.69%) along with
reduction of nitrate, iron, phosphate and total hardness as shown in
Table 2.
Evaluation of present process with some reported literature on
the removal of arsenic and fluoride individually or simultaneously
from water through electrocoagulation process are listed in Table 3.
There is only one literature for the simultaneous removal of As and
F through electrocoagulation in which no economic evaluation is
reported. Further, the precise comparison of the performance and
operating cost of present process with the other are difficult, since
the initial concentration, electrode material, operating conditions
etc. are not similar in these studies. From Table 3 it seems that the
operating cost of the present process with F concentration 12 mg/l
and As(III) concentration 550 mg/l, is lower than the operating cost
of the process reported by Ghosh et al., 2008 with 10 mg/l F con-
centration. Most of the studies have not provided cost comparison.
Fig. 6. Effect of NaCl concentration on removal of arsenic and fluoride, operating cost From this it is evident that the present process is highly competitive
(Initial As concentration: 550 mg/l, F concentration: 12 mg/l, initial pH: 7, current
to others.
density: 10 A/m2, inter electrode distance: 1 cm).
L.S. Thakur, P. Mondal / Journal of Environmental Management 190 (2017) 102e112 109

Table 2 Table 4
Initial characteristics of real groundwater and their removal. Kinetic rate constants with pseudo first order and pseudo second order models for
arsenic and/or fluoride removal.
Initial concentration (mg/l) Removal (%)
Pseudo first order model Pseudo second order model
As 512a 98.41
F 6.3 96.69 k1 (min1) R2 K2 ((l/(mg min)) R2
Iron 3.5 97.14
Individual
Nitrate 42 30.95
As 0.064 0.899 4.747 0.949
Phosphate 3 82.12
F 0.018 0.887 0.014 0.981
Total hardness 105 73.33
Simultaneous
a
mg/l. As 0.046 0.948 1.004 0.922
F 0.009 0.895 0.006 0.958

3.8. Studies on arsenic and fluoride removal kinetics of


electrocoagulation management as well as to explore the mechanism for the removal
of arsenic and fluoride through electrocoagulation. The surface
2
Table 4 shows the computed rate constants and R values ob- morphology of produced sludge is shown through SEM image
tained from pseudo first order and pseudo second order kinetic (Fig. 8a). The existence of adsorbed arsenic and fluoride in
models for arsenic and fluoride removal individually and simulta- aluminum sludge can be seen in Fig. 8b and c, respectively, which
neously. These results indicate that reaction rate of individual represent the mapping of arsenic and fluoride over the sludge.
arsenic and fluoride adsorption system follows pseudo second or- Moreover, the EDX analysis as shown in Fig. 8d also confirms the
der kinetic model. Similar kinetic results of arsenic and fluoride presence of arsenic and fluoride in sludge with other elements such
removal also obtained by other authors (Kobya et al., 2011; as oxygen and aluminum, and it can be explored for aluminum
Vasudevan et al., 2011). However, in simultaneous arsenic and recovery. Cementation and brick formation can also be a suitable
fluoride removal system, arsenic removal follows both pseudo first option for the management of this sludge (Chen et al., 2009). To
and second order kinetics and fluoride follows pseudo second order understand the leaching of arsenic and fluoride from the brick TCLP
kinetics. In case of arsenic, rate constant values for individual and test can be performed. As per the EPA guideline the permissible
simultaneous removal as per pseudo second order kinetic model limits of arsenic and fluoride concentrations in the solution after
are 4.747 and 1.004 l/(mg min), respectively. Similarly, in case of leaching test should be below 5 mg/l and 140 mg/l, respectively
fluoride, rate constant value for individual removal as obtained (The EPA TCLP; Jing et al., 2005; MoEF, 2016). The FTIR spectrum is
from pseudo second order kinetic model is found as 0.014 min1, presented in Fig. 8e showing peaks at 3550 and 3468 cm1 are
which reduces to 0.006 min1 for simultaneous removal. It can be likely attributed to the presence of OeH stretching (Gomes et al.,
ascertained that the rate constant decreases with increase in the 2007). The peaks located at 1640 and 1020 cm1 indicate the
initial concentration (Balasubramanian et al., 2009). It could be due presence of OeH bending and AleO bond stretching, respectively
to the decrease in ratio of aluminum oxyhydroxides to the initial (Gomes et al., 2007; Ghosh et al., 2008). The peaks at 604 and
contaminant concentration, which eventually reduces the rate of 646 cm1 are characteristics of As(III)eO and AleF stretching,
arsenic and/or fluoride removal, and subsequently the rate respectively (Gomes et al., 2007; Gross et al., 2007). The XRD
constant. spectrum of produced aluminum sludge as presented in Fig. 8f
show a shallow diffraction peaks which reveals that the sludge is
amorphous or poor crystalline in nature. The peaks at 2q ¼ 26, 28,
3.9. Characteristics of sludge
36, 40 and 45 are due to the presence of AlðOHÞ3 whereas, the peaks
at 2q ¼ 22, 60, 68, and 73 indicate the presence of AlF3 3H2 O (ICDD
Produced sludge characterization has been conducted to put
data base). The presence of AlAsO4 can be anticipated by the peak
insight on its properties required to assess its further utilization/

Table 3
Evaluation of the performance of some electrocoagulation processes along with operating cost for the individual and simultaneous removal of arsenic and fluoride (Thakur and
Mondal, 2016).

Type of electrode Parameters Initial concentration Removal (%) Operating cost (USD/m3) Reference

Simultaneous
Al pH: 7, Current density: 10 A/m2, run time: 95 min, As(III): 550 mg/l As: 98.51 0.357 This study
Electrode distance: 1 cm F: 12 mg/l F: 88.33
DSAa pH: 7, Current density: 40 A/m2, run time: 40 min, As(III): 1000 mg/l As: 99 e Zhao et al. (2011)
Fe Electrode distance: 0.02 cm F: 4.5 mg/l F: 77.7
Al
Individual
AleFe pH: 4, Current density: 300 A/m2, run time: 60 min, As(III): 13,400 mg/l As: >99.6 e Gomes et al., 2007
Electrode distance: 3 cm
AleAl pH: 4, Current density: 300 A/m2, run time: 60 min, As(III): 13,400 mg/l As: 97.8 e Gomes et al., 2007
Electrode distance: 3 cm
FeeFe pH: 2.4, Current density: 300 A/m2, run time: 60 min, As(III): 13,400 mg/l As: 97.2 e Gomes et al., 2007
Electrode distance: 3 cm
Fe pH: 6.5, Current density: 2.5 A/m2, run time: 12.5 min, As(III): 150 mg/l As: 93.5 0.022 Kobya et al., 2011
Electrode distance: 1.3 cm
Al pH: 7, Current density: 2.5 A/m2, run time: 15 min, As(III): 150 mg/l As: 95.7 0.019 Kobya et al., 2011
Electrode distance: 1.3 cm
Al pH: 8, Current density: 625 A/m2, run time: 45 min, F: 10 mg/l F: >90 For monopolar connection- 0.38 Ghosh et al., 2008
Electrode distance: 5 cm For bipolar connection- 0.62
a
DSA- Dimensionally stable electrode.
110 L.S. Thakur, P. Mondal / Journal of Environmental Management 190 (2017) 102e112

Fig. 8. a) SEM image b) existence of arsenic c) existence of fluoride d) EDX image e) FTIR spectra f) XRD pattern of produced sludge.

at 2q ¼ 67, 76 and 81 (ICDD data base). The FTIR and XRD analysis of pH: 7, current density: 10 A/m2, run time: 95 min, inter electrode
sludge confirm once again that arsenic and fluoride are linked with distance: 1 cm, NaCl concentration: 0.71 g/l at initial arsenic and
aluminum hydroxide complexes. fluoride concentration 550 mg/l and 12 mg/l, respectively. Under the
optimized condition, the concentration of arsenic and fluoride in
4. Conclusion treated water are found to be 8.19 mg/l (% removal: 98.51%) and
1.4 mg/l (% removal: 88.33%), respectively, with an operating cost of
Arsenic and fluoride contaminated groundwater can be effec- 0.357 USD/m3 treated water. Removal of both arsenic and fluoride is
tively treated by using electrocoagulation process. The optimum found responsive to the alteration of their initial concentration.
condition for arsenic and fluoride removal are found to be initial Reaction rate of individual arsenic and fluoride removal in
L.S. Thakur, P. Mondal / Journal of Environmental Management 190 (2017) 102e112 111

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