Chemosphere 144 (2016) 2113e2120

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Chemosphere
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Arsenic and fluoride removal from groundwater by electrocoagulation

using a continuous filter-press reactor
Athziri Guzma
L. Nava b, *, Oscar Coren

n a, Jose ~ o c, Israel Rodríguez d, Silvia Gutie

rrez a
a
Universidad de Guanajuato, Departamento de Química, Cerro de la Venada s/n, Pueblito de Rocha, 36040 Guanajuato, Guanajuato, Mexico
b
Universidad de Guanajuato, Departamento de Ingeniería Geoma
tica e Hidra
ulica, Av. Jua

rez 77, Zona Centro, 36000 Guanajuato, Guanajuato, Mexico
c
rez 77, Zona Centro, 36000 Guanajuato, Guanajuato, Mexico
Universidad de Guanajuato, Departamento de Ingeniería Civil, Av. Jua
d
noma de San Luis Potosí, Facultad de Ingeniería-Instituto de Metalurgia, Av. Sierra Leona 550, 78210 San Luis Potosí, San Luis Potosí,
Universidad Auto
Mexico

h i g h l i g h t s

Arsenic and fluoride removal from real groundwater by electrocoagulation.

Aluminum as sacrificial anodes.

Electrolyzes at different flow velocities and current densities.

Electrocoagulation led to 100% arsenic removal (43 mg L1) with 0.34 KWh m3.

Fluoride depletion from 2.5 to 0.15 mg L1 meet the WHO standard (<1.5 mg L1).

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

Article history: We investigated simultaneous arsenic and fluoride removal from ground water by electrocoagulation
Received 4 May 2015 (EC) using aluminum as the sacrificial anode in a continuous filter-press reactor. The groundwater was
Received in revised form collected at a depth of 320 m in the Bajío region in Guanajuato Mexico (arsenic 43 mg L1, fluoride
17 October 2015
2.5 mg L1, sulfate 89.6 mg L1, phosphate 1.8 mg L1, hydrated silica 112.4 mg L1, hardness 9.8 mg L1,
Accepted 25 October 2015
alkalinity 31.3 mg L1, pH 7.6 and conductivity 993 mS cm1). EC was performed after arsenite was
Available online xxx
oxidized to arsenate by addition of 1 mg L1 hypochlorite. The EC tests revealed that at current densities
of 4, 5 and 6 mA cm2 and flow velocities of 0.91 and 1.82 cm s1, arsenate was abated and residual
Keywords:
Arsenic removal
fluoride concentration satisfies the WHO standard (CF < 1.5 mg L1). Spectrometric analyses performed
Fluoride removal on aluminum flocs indicated that these are mainly composed of aluminum-silicates of calcium and
Sulfate removal magnesium. Arsenate removal by EC involves adsorption on aluminum flocs, while fluoride replaces a
Aluminum sacrificial anode hydroxyl group from aluminum aggregates. The best EC was obtained at 4 mA cm2 and 1.82 cm s1 with
Electrocoagulation electrolytic energy consumption of 0.34 KWh m3.
Groundwater treatment © 2015 Elsevier Ltd. All rights reserved.

1. Introduction polluted water with arsenic and fluoride creates chronic health
problems such as hyperpigmentation, and keratosis of hands and
Groundwater represents one of the mean drinking water sour- feet. It also causes bladder, lung, skin, kidney, liver, and prostate
ces for most people around the world (Basu et al., 2014). However, cancer (Smedley and Kinniburgh, 2013); furthermore, it can lead to
uncontrolled consumption of drinking water has led to the drilling fluorosis of the teeth and may stunt child growth (Brahman et al.,
of deeper wells (>150 m). At these depths, elements such as arsenic 2013). Considering the toxicity of arsenic, the World Health Orga-
(As) and fluoride (F) are typically found in the Bajío area in Gua- nization (WHO) and the U.S. Environmental Protection Agency have
najuato, Mexico at concentrations that exceeds the Mexican stan- set the maximum acceptable level of arsenic in drinking water at
dard (CAs < 25 mg L1, CF < 1.5 mg L1). Long-term exposure to 10 mg L1. For fluoride, the maximum acceptable level is 1.5 mg L1
for both the WHO and Mexican standard.
Different technologies have been developed to decrease the
* Corresponding author. arsenic and fluoride concentrations in groundwater, such as inverse
E-mail address: [email protected] (J.L. Nava).

http://dx.doi.org/10.1016/j.chemosphere.2015.10.108
0045-6535/© 2015 Elsevier Ltd. All rights reserved.
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osmosis, electrodialysis and distillation (Mo
lgora et al., 2013; Cui H6SiO7, H8Si3O and H10SiO13 (Pourbaix, 1974). According to
et al., 2014). For arsenic removal, adsorption (Kumar et al., 2014) Lakshmanan et al. (2010) the monovalent state of H3SiO4 , which
and coagulation-flocculation procedures are the most common. sparingly appears at hydrated silica concentrations greater than
They involve the addition of aluminum sulfate, ferric sulfate, cal- 20 mg L1 and at pH > 8, competes with arsenate for adsorption
cium hydroxide or polymeric flocculants. However, due to low sites. Lartiges et al. (1997) investigated the flocculation of colloidal
concentrations of dissolved As, these processes yield large amounts silica with hydrolyzed aluminum. These authors discuss the for-
of sludge, because SO24 anions consume 50% of the coagulant (Tang mation of aluminum complexes with silica anions (aluminum-sil-
et al., 2014). The arsenic species in water from deep wells (at icates). These have potential active sites for aluminum aggregate
pH ~ 7.5) are innocuous arsenite, HAsO2 and H3AsO3 (oxidation growing. Likewise, Tokoro et al. (2014) suggest that hydrated silica
state III) and arsenate anion, HAsO2
4 (oxidation state V) (Pourbaix, could be removed during kaolinite (amorphous aluminum silicate)
1974). The second species at neutral pH is more susceptible to formation by co-precipitation and adsorption processes.
removal by EC (Hansen et al., 2006; Balasubramanian et al., 2009; On the other hand, the presence of Ca2þ enhances defluor-
Wan et al., 2011). We have previously discussed that arsenic idation owing to the ability of fluoride to form CaF2(s) (Zuo et al.,
removal is more efficient when arsenite is oxidized to arsenate, 2008). In the same way, the ion Mg2þ improved fluoride removal,
after the addition of a typical amount of sodium hypochlorite used because Mg2þ is a good coagulant (MgF2) and is frequently used as
for disinfection purposes (1 mg L1) (Flores et al., 2013). Moreover, co-coagulant with aluminum salt (Montero and Villafan ~ e, 2010).
it is well known that arsenite oxidizes to arsenate on the anode The aim of this study was to decrease the arsenic and fluoride
during the EC process (Wan et al., 2011). concentrations in groundwater from the Bajío region by EC using
For removing fluoride from groundwater, the most widespread aluminum as the sacrificial anode in a continuous filter-press
method is the coagulation-flocculation procedure by calcium and reactor. We analyzed the influence of current density and mean
aluminum salt. Nevertheless, this process causes an increase in pH, linear flow velocity on the efficiency of arsenic and fluoride
which provokes the appearance of soluble aluminum species, removal. Aluminum flocs were characterized by SEM-EDAX, XRD
which are toxic to human health. Besides, for large volumes of and FTIR. The energy consumption for electrolysis was also
water this process yields large amounts of sludge, resulting in waste estimated.
management problems (Singh et al., 2013). For this reason, EC was
selected in this work, where aluminum, when dissolved electro- 2. Electrocoagulation process
lytically, supports the coagulation process and diminishes the
amount of sludge produced. EC is an effective process to destabilize EC consists of an in situ generation of coagulants by electro-
dispersed fine particles and anions contained in water (Hu et al., dissolution of aluminum electrodes. At the anode, aluminum ions
2007; Essadki et al., 2009). Electro-dissolution of aluminum gen- are produced first (Al3þ); afterwards, the aluminum ions are
erates bulk aluminum hydroxides (Al(OH)3(s)) and aluminum ox- transformed to aluminum hydroxides (Al(OH)3(s)) and aluminum
ides (Al2O3(s)), which are believed to adsorb arsenic, and remove oxides (Al2O3(s)) in volume:
fluoride by substitution reaction on the surface of the aluminum
hydroxides (Flores et al., 2013; Sandoval et al., 2014). These findings Al(s) / Al3þ þ 3e (1)
have been observed in solutions that only contain As or F sepa-
rately, and in some cases, each of them are studied showing the Al3þ þ 3H2O / Al(OH)3(s) þ 3Hþ (2)
influence of other ions such as phosphates, sulfates, hydrated silica,
carbonates, humic acids, and calcium, magnesium, among others 2Al3þ þ 3H2O / Al2O3(s) þ 6Hþ (3)
(Wan et al., 2011; Kumar et al., 2014).
Few studies have examined simultaneous removal of arsenic At the aluminum cathode, hydrogen gas is released:
and fluoride (Ingallinella et al., 2011), where iron and aluminum
binary oxide (FeAlOxHy) (Zhao et al., 2011; Liu et al., 2015) and 3H2O þ 3e / 1.5H2 þ 3OH (4)
freshly-prepared aluminum hydroxide (Liu et al., 2015) are
employed as adsorbent materials. It is important to mention that Typically, at the cathode interface the solution becomes alkaline
the main interference observed during the simultaneous removal with time. The OH migrates and diffuses away from the cathode to
of arsenic and fluorine on freshly-prepared aluminum hydroxide is the anode, thus favoring water formation, hydroxyl ions reacts with
the formation of soluble complexes of AleF, which solubilize protons of Eqs. (2) and (3), making the remaining solution neutral:
aluminum oxyhydroxides (AlOxHy), increasing the concentration of
residual aluminum (Liu et al., 2015). OH þ Hþ / H2O (5)
Zhao et al. (2011) reports the efficient removal of both arsenic
and fluoride simultaneously (from synthetic solutions) using a The major problem of the aluminum anode is its passivation,
combination of electro-oxidation and EC processes. However, the due to Al2O3(s) precipitation, giving high anode and cell potential,
simultaneous removal of arsenic and fluoride from actual samples increasing the energy consumption and cost of EC (Kobya et al.,
of groundwater and the possible interferences of other ions by EC 2011; Mohora et al., 2012). Passivation can be controlled at low
have not yet been published. current densities in combination with turbulent flow conditions,
Groundwater may also contain co-existing anions such as SO2 4 , which favors Al3þ ions transport away from the surface to the bulk
PO3 2þ
4 , cations as Mg , Ca
2þ
and hydrated species of silica solution. In addition, the use of cathodes of the same material are
(SiO2,xH2O). These co-existing anions compete with F and recommended to electro-dissolve Al2O3(s) by periodic current
HAsO2 4 with aluminum flocs (Sandolval et al., 2014). The presence reversal (Mohora et al., 2012), which allows an even consumption
1
of SO2 3
4 and PO4 in concentrations higher than 50 mg L and of aluminum electrodes during the process.
1
4 mg L , respectively, inhibits arsenic and fluoride removal (Wan As we mentioned above, our group had previously discussed
et al., 2011). Dissolved hydrated species of silica, contained in nat- that arsenic removal is more efficient when arsenite is oxidized to
ural water generally between 20 and 60 mg L1, or in higher con- arsenate, after the addition of a typical amount of sodium hypo-
centrations, also obstruct the removal of As and F. These species chlorite used for disinfection purposes (1 mg L1) (Flores et al.,
have a similar function to hydrated acids such as H2SiO3, H4SiO4, 2013). The Al(OH)3(s) and Al2O3(s) flocs are believed to adsorb

n et al. / Chemosphere 144 (2016) 2113e2120
A. Guzma 2115

HAsO2
4 (Kobya et al., 2011): HI 93717 Phosphate High Range, ISM, while silica determination
h i was performed by Heteropoly Blue Method using the kit HI 93705.
AlðOHÞ3ðsÞ þ HAsO2
4 / AlðOHÞ3 HAsO2
4 s (6) Both analyses employed a multi-parameter photometer C99 by
Hanna Instruments. Sulfate was quantified using the turbidimetry
h i technique (APHA, 1998) using the spectrophotometer Perkin Elmer
Al2 ðOHÞ3ðsÞ þ HAsO2 2
4 / Al2 ðOHÞ3 HAsO4 s (7) Lambda 35 UV/VIS. The detection limit of sulfates, phosphates and
hydrated silica was 0.2 mg L1. Carbonates and hardness tests were
The mechanism of fluoride removal by EC is carried out using a carried out by titration according to standard methods (APHA,
chemical substitution, in which F replaces OH group from 1998). Ca and Mg (which give hardness) were also determined by
Al(OH)3 flocs according to equation (8), (Zhu et al., 2007). AA with detection limits of 0.02 and 0.03 mg L1, respectively.
Conductivity and pH measurements were carried out using a water
Al(OH)3 þ xF / Al(OH)3xFx þ xOH (8) proof instrument, model HI 991300 from Hanna Instruments. All
chemical reagents were of analytical grade. Each individual
Groundwater contains high concentrations of co-existing ions experiment was performed at least three times, and then the re-
which affect arsenic and fluoride removal (Bennajah et al., 2010); sults were averaged.
hence, the influence of co-existing ions on the As and F removal
efficiency are examined. 3.4.2. Scanning electron microscopy and energy dispersive X-ray
analysis
3. Materials and methods The Scanning Electron Microscopy (SEM) analysis was carried
out in using a Jeol JSM-6610LV. The Energy Dispersive Analysis of X-
3.1. Solutions rays (EDAX) was carried out in an Oxford X-Max detector integrated
in the microscope.
Groundwater samples were collected from deep wells (320 m)
located in the Bajío region of Guanajuato, Mexico (arsenic 43 mg L1, 3.4.3. X-ray diffraction analysis (XRD)
fluoride 2.5 mg L1, sulfate 89.6 mg L1, phosphate 1.8 mg L1, XRD were performed on a diffractometer Rigaku, model DMAX
hydrated silica 112.4 mg L1, hardness 9.8 mg L1, alkalinity 220, with nickel filter and radiation of CuK a.
31.3 mg L1, pH 7.6 and conductivity 993 mS cm1). Water samples
were collected from the wells after the addition of 1.0 mg L1 so- 3.4.4. Fourier transform infrared spectroscopy (FTIR)
dium hypochlorite used for disinfection. The FTIR analysis in the flocs was carried out in a Perkin Elmer
Spectrum GX FTIR Spectrometer using an EasiDiff diffuse reflec-
3.2. Filter press reactor tance accessory. The flocs samples were prepared using potassium
bromide (sample:KBr, 1:14). The diffuse reflectance accessory
The experimental setup and the dimensions of the filter-press allowed conducting the FTIR analysis.
electrochemical reactor were described in Flores et al. (2013). The
system consists of a continuous pre-pilot scale filter-press-type cell, 3.4.5. Zeta potential
where the coagulant is produced. The resulting solution (a mixture The zeta potential was measured using an electrokinetic solids
of water and coagulant) is passed to a jar test to induce the floc- analyzer (Anton Paar SurPass) with the remaining water from EC.
culation and adsorption of arsenic on the aluminum flocs and re-
action between fluoride and aluminum aggregates. The arsenic and 4. Results and discussion
fluoride are then precipitated, and the clarified solution is analyzed.
4.1. Simultaneous As and F removal by EC
3.3. Methodology
Fig. 1aec shows the influence of mean linear flow velocity on the
EC was performed at different mean linear flow rates between residual concentration of arsenic (CAs) at constant current density
0.91  u  3.82 cm s1 and current densities of 4, 5 and 6 mA cm2. of 4, 5 and 6 mA cm2, respectively. The experimental CAl(III) and
Immediately, each resulting solution was passed to test jar equip- theoretical CAl(III) (N) aluminum doses (Eq. (9)) are also included. At
ment, mixing at slow speed (45 rpm), for a duration of 15 min, 4 mA cm2 the CAs displayed an abatement at
causing the growth of aggregates; then, aggregates are precipitated 0.91  u  1.82 cm s1, with experimental aluminum doses be-
in the static solution, for approximately three hours. The arsenic, tween 20.6  CAl(III)  12.7 mg L1. At u > 1.82 cm s1 CAs increases
fluoride, phosphate, sulfate, hydrated silica, calcium and magne- up to 37.9 mg L1 with CAl(III) ¼ 7.9 mg L1, indicating that arsenic
sium in the clarified solution were analyzed. After dissolution of the removal is not favored with mean linear flow velocity owing to
flocs, the aluminum contained was also analyzed. depletion of CAl(III). It is important to mention that the CAl(III), is
lower than the theoretical value.
3.4. Analytical procedure
 
jLMW  
CAlðIIIÞðNÞ ¼ 1  106 ðNÞ (9)
3.4.1. Groundwater characterization zFSu
Based on the standard method suggested by APHA (1998), an
atomic absorption spectrometer (Perkin Elmer AAnalist 200), where CAl(III)(N) is the theoretical concentration of aluminum dose
equipped with a manual hydride generator at 188.9 nm wavelength (mg L1), j is the current density (A cm2), L is the length of one
was employed to determine the arsenic concentrations (detection channel (cm), MW is the molecular weight of aluminum
limit of 0.1 mg L1). Fluoride concentrations were measured using (26.98 g mol1), n is the number of exchanged electrons, 3, F is the
an ion selective electrode of fluoride, model 27502-19, from Cole Faraday constant (96485C mol1), S is the channel width (cm), u is
Palmer (detection limit of 0.02 mg L1). The aluminum concen- the mean linear flow velocity (cm s1), N is the number of channels,
tration was determined by Atomic Absorption (AA) with a detection and 1  106 is a conversion factor to obtain units of concentration of
limit of 0.15 mg L1. The analysis of phosphate was carried out by kit aluminum in mg L1.
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A. Guzma

the current efficiency values are close to 100%.

Even when the aluminum dose is imposed by j and u, the arsenic
abatement is independent of j at 0.91  u  1.82 cm s1. It can be
associated on the one hand, with the concentration of aluminum
CAl(III) (between 12.72 and 72.46 mg L1), which might favor the EC,
and on the other hand, with the effective flocculation performed at
such low flow rates. At u > 1.82 cm s1 CAs increases owing to hy-
drodynamics might promote the breaking of the flocs. Microfilm
analysis of the flocs growing during EC processes can be helpful to
elucidate the influence of current density and mean linear flow rate
on the floc size; although this analysis was beyond of the scope of
this paper.
During the same EC trials the fluoride residual concentration
(CF) was followed, Fig. 2. For the experiment assessed at
4 mA cm2 and at u ¼ 0.91 cm s1, CF decreases to 0.6 mg L1 from
the initial concentration (2.5 mg L1), with a CAl(III) of 20.6 mg L1.
The major defluoridation, CF ¼ 0.39 mg L1, was obtained at
u ¼ 1.82 cm s1, with CAl(III) ¼ 12.70 mg L1. Finally, u > 1.82 cm s1 CF
achieves an increased concentration of 0.91 mg L1 at 3.64 cm s1
with CAl(III) ¼ 7.9 mg L1; CF increased due to CAl(III) depletion in
addition to the breaking of the flocs.
EC tests at 5 and 6 mA cm2 presented a similar behavior to that
obtained at 4 mA cm2. The final pH of the groundwater after EC
tests slightly increased to 8.5, likely due to F interchanges with
OH. It is important to point out that all EC experiments meet
Mexican standard (CF  1.5 mg L1).
During the same electrolyzes the residual concentration of SO2 4
and PO3 4 (Fig. 3aeb) was determined to analyze their interaction
during the EC process. The average residual concentrations of sul-
fate and phosphate did not present a trend with j and u, possibly
due to interferences from the analytical method employed here.
However, the average residual concentration after EC tests were
around 30 mg L1 SO2 4 from the initial value of 89.6 mg L
1
SO2
4 ,
1 3 1 3
and 1.1 mg L PO4 from initial value of 1.8 mg L PO4 . The
depletion of SO2 3
4 and PO4 suggests that these anions are adsorbed
on the flocs and compete with arsenic and fluoride for the flocs
active sites (Wan et al., 2011; Flores et al., 2013; Sandoval et al.,
2014). Fig. 4aeb showed a slightly residual concentration
Fig. 1. Influence of the mean linear flow rate on the residual arsenic concentration and decrease of Ca2þ (initially 2 mg L1 Ca2þ) and Mg2þ (initially
aluminum dose for groundwater. Applied current density: (a) 4 mA cm2, (b) 1.5 mg L1 Mg2þ) with j and remained almost constant with u. The
5 mA cm2 and (c) 6 mA cm2. slightly removal of Ca2þ and Mg2þ suggests that they might

The current efficiencies of EC (assessed by the ratio between

experimental and theoretical aluminum doses) were comprised
between 63.6 and 85.2%. These values can be a consequence of
oxygen evolution reaction Eq. (10), which typically occurs simul-
taneously with Eq. (1), and on the other hand, the passivation of the
anode due to Al2O3(s) precipitation on the anode.

2H2O / O2 þ 4Hþ þ 4e (10)

At 5 mA cm2 CAs is similar to that obtained at 4 mA cm2. It

shows an abatement of CAs at 0.91  u  1.82 cm s1 with
aluminum doses of 41.4  CAl(III)  18.5 mg L1. Then, at
u > 1.82 cm s1 a linear increase of CAs from 0 to 14.2 mg L1 took
place with an CAl(III) ¼ 8.3 mg L1. The current efficiency approached
100%.
At 6 mA cm2 a similar behavior to that obtained at 4 and
5 mA cm2 was obtained at 0.91  u  1.82 cm s1. However, at
u > 1.82 cm s1 the CAs surpasses the obtained at 5 mA cm2 even
when CAl(III) increases to 6 mA cm2. The current efficiency at this
current density is higher than 100% at 0.91 cm s1, likely a conse-
quence of the aluminum oxides dissolution on the anode that was Fig. 2. Influence of the mean linear flow rate on the residual fluoride concentration,
accumulated in earlier electrolysis. Afterwards, at u > 1.82 cm s1 evaluated from the EC tests similar to those from Fig. 1.

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Fig. 4. Influence of the mean linear flow rate on the residual: (a) calcium concentra-
tion, (b) magnesium concentration, evaluated from the EC tests similar to those from
Fig. 1.
Fig. 3. Influence of the mean linear flow rate on the residual: (a) sulfate concentration,
(b) phosphate concentration, evaluated from the EC tests similar to those from Fig. 1.

detected. At 5 mA cm2 and 6 mA cm2, the six elements were

present. Oxygen and aluminum were always present. The presence
precipitate in the flocs. On the other hand, the hydrated silica
of Si on the aluminum flocs can produce hydro-aluminum-silicates
depletion was 0.15 mg L1, from its initial value of 112.4 mg L1,
(Tokoro et al., 2014); this last was confirmed by FTIR as shown
which suggests that silica species were removed by co-
below.
precipitation and/or by the formation of aluminum silicates with
It has been reported that arsenic is removed by an adsorption
divalent cations such as Ca2þ and Mg2þ; the latter is validated by
process on the flocs followed by precipitation (Mo
lgora et al., 2013;
XRD analysis shown below.
Basu et al., 2014; Cui et al., 2014; Kumar et al., 2014), and it is well
known that fluoride replaces the hydroxide ion of the aluminum
4.2. Flocs characterization flocs (through Eq. (8)). Although, these elements were not detected
in area analysis, contents of up to 1.23 at. % As and 4.61 at. % F were
4.2.1. SEM/EDAX measured by point analyses.
Fig. 5a shows a SEM image of aluminum flocs obtained either On the other hand, zeta potential measurements on the flocs
from the EC process at 4 mA cm2 and 0.91 cm s1, and Fig. 5b at gave negative values (Table 2), except for those obtained at
5 mA cm2 and 0.91 cm s1. These micrographs show particles with 5 mA cm2 and 1.82 cm s1, which indicates that fluoride, sulfates,
irregular shape and size of up to around 150 mm, Fig. 5a, and up to carbonates, and phosphates are removed and form a coordinate
around 200 mm in Fig. 5b. Fig. 5ced shows a SEM image of complex with hydrated silica species. The above may be performed
aluminum flocs obtained from the EC process at 6 mA cm2 and by precipitation with aluminum flocs, likely through an adsorption
0.91 cm s1 and 1.82 cm s1, respectively. Particles are also of process and/or ionic interchange reaction. In addition, the negative
irregular shape, whit size of up to around 500 mm. From Fig. 5 it can zeta potential is also provoked by the slight increase in pH after EC
be observed that maximum particle size increases with current tests (see Table 2). This change in pH also increases the electrical
density. conductivity.
Table 1 shows the composition of the flocs, determined by
EDAX. Areas of around 800 mm  800 mm were analyzed. The low 4.2.2. X-ray diffraction analysis (XRD)
standard deviations imply that the samples are homogeneous. Six In Fig. 6a XRD spectrum shows very broad and shallow
areas were analyzed for flocs produced using currents of 4 mA cm2 diffraction peaks, the first from 5 to 18 and the second from 25 to
and 5 mA cm2, and twelve areas for flocs produced using 38 . Bragg reflections possessing very broad humps and low in-
6 mA cm2. In flocs corresponding to 4 mA cm2, Mg was not tensities indicate that the analyzed sample has a short range order,
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A. Guzma

Fig. 5. SEM images of aluminum flocs obtained from the EC process at 0.91 cm s1 and 4 mA cm2 (a), and 5 mA cm2 (b); SEM images of aluminum flocs obtained from the EC
process at 6 mA cm2 and 0.91 cm s1 (c), and 1.82 cm s1 (d).

Table 1
Composition of the flocs determined by EDAX.

4 mA cm2 5 mA cm2 6 mA cm2

Element Average at. % Standard deviation Average at. % Standard deviation Average at. % Standard deviation

O 54.60 0.76 53.31 0.65 55.22 0.71

Na 7.11 0.26 4.99 0.26 3.12 0.28
Mg 0.00 0.00 1.74 0.13 1.97 0.17
Al 29.29 0.42 32.16 0.26 33.02 0.21
Si 7.19 0.21 6.68 0.27 5.70 0.31
Ca 1.83 0.11 1.13 0.14 0.98 0.10

characteristic of amorphous phases. From the EDAX analyses, it (Abis et al., 2001; Musi

c et al., 2011) or amorphous alumina (Wu,
could be expected that the broad peaks could be assigned to 2001; Li and Huang, 2007; Wang et al., 2009). After 38 the XRD
amorphous silica or amorphous alumina. However, these peaks do pattern shows a continuous series of narrow peaks. Then, it is
not match with those previously reported for amorphous silica possible that the two broad peaks are the result of the

Table 2
Residual arsenic and fluoride concentrations after hypochlorite addition satisfying the WHO standard (CAs10 mg L1, CF  1.5 mg L1), as well as experimental aluminum dose,
experimental aluminum flow rate, cost of aluminum dosed, Z potential, pH, conductivity, cell potential and energy consumption. Initial composition of groundwater: arsenic
43 mg L1, fluoride 2.5 mg L1, sulfate 89.6 mg L1, phosphate 1.8 mg L1, hydrated silica 112.4 mg L1, hardness 9.8 mg L1 (calcium 2 mg L1, magnesium 1.5 mg L1), alkalinity
31.3 mg L1, pH 7.6 and conductivity 993 mS cm1.

J (mA cm2) U (cm s1) CAs (mg L1) CF (mg L1) CAl(III) (mg L1) FAl(III) (mg s1) $Al (USD m3) Z Potential (mV) pH Conductivity (mS cm1) Ecell (V) Econs (kWh m3)

4 0.91 0.0 0.60 20.63 0.034 0.032 10.29 8.65 1324 6.1 0.6
1.82* 0.0 0.39 12.72 0.042 0.020 15.08 8.77 1272 7.0 0.34
5 0.91 0.0 0.44 41.38 0.068 0.064 10.38 8.60 1273 7.7 0.95
1.82 0.0 0.16 18.51 0.062 0.029 0.176 8.64 1351 8.6 0.53
6 0.91 0.0 0.17 72.46 0.12 0.112 2.436 8.87 1228 9.8 1.45
1.82 0.0 0.15 20.45 0.068 0.031 16.99 8.78 1191 10.5 0.78

*Residual concentrations for the best EC in terms of Econs: sulfate 33.1 mg L1, phosphate 1.6 mg L1, calcium 1.2 mg L1, magnesium 1.4 mg L1, hydrated silica 112.25 mg L1.

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A. Guzma 2119

again that arsenic is removed by adsorption according to equations

(6) and (7) and F might replace OH group from the flocs (Zhu
et al., 2007). In addition, the presence of AleOeSi bounding con-
firms the formation of hydrated aluminum silicates as a product of
EC process.
It is important to mention that FTIR spectra did not show bands
corresponding to any Selement bounding, which can be associ-
ated to a weak SO2 4 adsorption on aluminum flocs (Sandoval et al.,
2014).
Zuo et al. in (2008) performed an X-ray photoelectron spec-
troscopy study of aluminum flocs in the presence of SO2 4 and
proposed that SO2 4 has a negative effect on defluoridation, which is
associated with the ion exchange competition between SO2 4 and
F , that is:


AlðOHÞ3x Fx þ ySO2
4 4AlðOHÞ3x Fx2y ðSO4 Þy þ 2yF (11)

However, in this paper the AlðOHÞ3x Fx2y ðSO4 Þy phase was not
detected by the spectroscopy techniques employed here.

4.3. Energy consumption and costs of EC

Table 2 reveals that EC at 4, 5 and 6 mA cm2 satisfied the WHO

standard for arsenic and fluoride at flow rates between 0.91 and
1.82 cm s1 (volumetric flow rates, q, 1.6  103 and
3.3  103 L s1), corresponding to experimental aluminum dose of
12.7 and 72.5 mg L1 and experimental aluminum flow rate of
FAl(III) ¼ 0.042 and 0.12 mg s1, evaluated as FAl(III)]CAl(III)  q.
EC at 4 mA cm2 satisfied the WHO standard at flow rates be-
tween 0.91 and 1.82 cm s1, corresponding to aluminum doses of
20.63 and12.72 mg L1and aluminum flow rates of
0.034e0.042 mg s1. EC at 5 mA cm2 satisfied the WHO standard
at flow rates of 0.91e1.82 cm s1, corresponding to aluminum doses
of 41.38 and 18.51 mg L1 and aluminum flow rates of 0.068 and
0.062 mg s1. Finally, EC at 6 mA cm2 satisfied the WHO standard
Fig. 6. Typical XRD (a) and FTIR (b) spectra of the dried flocs obtained at 4 mA cm2 at flow rates between 0.91 and 1.82 cm s1, corresponding to
and 1.82 cm s1. aluminum doses of 72.4 and 20.45 mg L1and aluminum flow rates
of 0.12e0.068 mg s1. It should be noted that the cell potential, Ecell,
increases with current density according to Ohm law and decreases
superposition of a high number of narrow peaks. Peaks corre- with mean linear flow rate owing to aluminum ions are transported
sponding to merwinite (Ca3Mg(SiO4)2), anorthite (CaAl2Si2O8), away from the surface to the bulk solution under such turbulent
albite (NaAlSi3O8), boggsite (NaCa2(Al5Si19O48),H2O), cordierite flow conditions, decreasing Al2O3 precipitation on the anode. The
(Mg2Al4Si5O18), tremolite (Ca2Mg5(Si8O22)(OH)2) and rosenhahnite energy consumption (Econs) was evaluated for the EC test shown in
(Ca3SiO8(OH)2) were identified. If a-Al2O3 and g- Al2O3 phases are Table 2. The energy consumption during electrolysis was deter-
present in the samples their content might be below 5 wt. %, owing mined by:
to their XRD peaks were not distinguished. In the same way, phases
containing As or F were not detected. This can be explained by the
Ecell I
low content of these elements in the groundwater, Arsenic, Econs ¼ (12)
43 mg L1 and fluoride 2.5 mg L1. ð3:6ÞSBu

where Ecell is given in units of V, I is the current intensity during

4.2.3. FT-IR characterization electrolysis (C s1), B is the channel height (cm), S is the channel
FTIR analysis ranged from wave numbers between 4000 and width (cm) and the value 3.6, is a conversion factor that allows to
450 cm1 was performed to analyze the chemical bonds of the obtain Econs in units of kWh m3. The cost of aluminum doses
elements present in the flocs (obtained at j of 4 mA cm2 and u of evaluated as $Al(III)](CAl(III)  ($1.55 USD kg1)  0.001) is also
1.82 cm s1), Fig. 6b. The infrared spectrum analysis showed a wide included in Table 2. The cost of aluminum considered for this cal-
band at 3550e3200 cm1, which most likely corresponds to OeH culations was $1.55 USD kg1 and the value of 0.001 is a conversion
stretching vibrations (Socrates, 2004). The peak located at factor to obtain $Al(III) in units of $ USD m3.
1750 cm1 is likely attributed to the NaeF bounding. AleO bending The best EC in terms of energy consumption (Econs) and cost of
is represented by the band at 1500 cm1. The peak at 1300 is likely aluminum dosed was obtained at 4 mA cm2 with u ¼ 1.82 cm s1,
attributed to AleOeSi. SieO bond is represented at 1100 cm1. The giving Econs of 0.34 KWh m3, and $Al(III) of 0.020 USD m3. It is
band at 705e690 cm1 may be ascribed to the stretching of AleF important to mention that in this paper we did not included an
(Lartiges et al., 1997; Kobya et al., 2011). The band at 850e800 cm1 estimate of the overall EC process due to electricity fee variance
is characteristic of AseO bending. The FTIR analysis confirms once between countries.
2120
n et al. / Chemosphere 144 (2016) 2113e2120
A. Guzma

5. Conclusions Simultaneous removal of arsenic and fluoride from groundwater by

coagulation-adsorption with polyaluminum chloride. J. Env. Sci. Health. Part A
46, 1288e1296.
The decrease of arsenic and fluoride concentrations from Kobya, M., Gebologlu, U., Ulu, F., Oncel, S., Demirbas, E., 2011. Removal of arsenic
groundwater after EC using aluminum as anode in a continuous from drinking water by the electrocoagulation using Fe and Al electrodes.
filter press reactor met the WHO standard (CAs  10 mg L1, Electrochim. Acta 56, 5060e5070.
Kumar, E., Bhatnagar, A., Hogland, W., Marques, M., Sillanpa €€a, M., 2014. Interaction
CF  1.5 mg L1) at current densities of 4, 5 and 6 mA cm2 and flow of anionic pollutants with Al-based adsorbents in aqueous mediaea review.
velocities of 0.91 and 1.82 cm s1, highlighting that arsenate was Chem. Eng. J. 241, 443e456.
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revealed that these were composed by aluminum silicates. Arse- Lartiges, B., Bottero, J., Derrendinger, L., Humbert, B., Tekely, P., Suty, H., 1997.
nate, sulfate and phosphate are adsorbed on aluminum flocs. Flocculation of colloidal silica with hydrolyzed aluminum: an 27 Al solid state
NMR investigation. Langmuir 13, 147e152.
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terms of energy consumption (0.34 KWh m3) and cost of based on anodic alumina. J. Braz. Chem. Soc. 18, 406e409.
aluminum dosed ($ 0.020 USD m3) was obtained at 4 mA cm2 Liu, R., Zhu, L., Lan, H., Liu, H., Qu, J., 2015. Simultaneous removal of arsenic and
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Acknowledgments arsenic from drinking water: a comparative study between electrocoagulation-
microfiltration and chemical coagulation-microfiltration processes. Sep. Purif.
Technol. 118, 645e651.
Authors thank the Universidad de Guanajuato for financial Mohora, E., Ron cevi

c, S., Dalmacija, B., Agbaba, J., Watson, M., Karlovi
c, E.,
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(project No. 123732) for analytical and technical assistance. by electrocoagulation/flotation continuous flow reactor. J. Hazard. Mater. 235,
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