Chemosphere 144 (2016) 2113e2120

Contents lists available at ScienceDirect

Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

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

http://dx.doi.org/10.1016/j.chemosphere.2015.10.108
0045-6535/© 2015 Elsevier Ltd. All rights reserved.
2114
n et al. / Chemosphere 144 (2016) 2113e2120
A. Guzma
osmosis, electrodialysis and distillation (Mo
lgora et al., 2013; Cui
et al., 2014). For arsenic removal, adsorption (Kumar et al., 2014)
and coagulation-flocculation procedures are the most common.
They involve the addition of aluminum sulfate, ferric sulfate, cal-
cium hydroxide or polymeric flocculants. However, due to low
concentrations of dissolved As, these processes yield large amounts
of sludge, because SO24 anions consume 50% of the coagulant (Tang
et al., 2014). The arsenic species in water from deep wells (at
pH ~ 7.5) are innocuous arsenite, HAsO2 and H3AsO3 (oxidation
state III) and arsenate anion, HAsO2
4 (oxidation state V) (Pourbaix,
1974). The second species at neutral pH is more susceptible to
removal by EC (Hansen et al., 2006; Balasubramanian et al., 2009;
Wan et al., 2011). We have previously discussed that arsenic
removal is more efficient when arsenite is oxidized to arsenate,
after the addition of a typical amount of sodium hypochlorite used
for disinfection purposes (1 mg L1) (Flores et al., 2013). Moreover,
it is well known that arsenite oxidizes to arsenate on the anode
during the EC process (Wan et al., 2011).
For removing fluoride from groundwater, the most widespread
method is the coagulation-flocculation procedure by calcium and
aluminum salt. Nevertheless, this process causes an increase in pH,
which provokes the appearance of soluble aluminum species,
which are toxic to human health. Besides, for large volumes of
water this process yields large amounts of sludge, resulting in waste
management problems (Singh et al., 2013). For this reason, EC was
selected in this work, where aluminum, when dissolved electro-
lytically, supports the coagulation process and diminishes the
amount of sludge produced. EC is an effective process to destabilize
dispersed fine particles and anions contained in water (Hu et al.,
2007; Essadki et al., 2009). Electro-dissolution of aluminum gen-
erates bulk aluminum hydroxides (Al(OH)3(s)) and aluminum ox-
ides (Al2O3(s)), which are believed to adsorb arsenic, and remove
fluoride by substitution reaction on the surface of the aluminum
hydroxides (Flores et al., 2013; Sandoval et al., 2014). These findings
have been observed in solutions that only contain As or F sepa-
rately, and in some cases, each of them are studied showing the
influence of other ions such as phosphates, sulfates, hydrated silica,
carbonates, humic acids, and calcium, magnesium, among others
(Wan et al., 2011; Kumar et al., 2014).
Few studies have examined simultaneous removal of arsenic
and fluoride (Ingallinella et al., 2011), where iron and aluminum
binary oxide (FeAlOxHy) (Zhao et al., 2011; Liu et al., 2015) and
freshly-prepared aluminum hydroxide (Liu et al., 2015) are
employed as adsorbent materials. It is important to mention that
the main interference observed during the simultaneous removal
of arsenic and fluorine on freshly-prepared aluminum hydroxide is
the formation of soluble complexes of AleF, which solubilize
aluminum oxyhydroxides (AlOxHy), increasing the concentration of
residual aluminum (Liu et al., 2015).
Zhao et al. (2011) reports the efficient removal of both arsenic
and fluoride simultaneously (from synthetic solutions) using a
combination of electro-oxidation and EC processes. However, the
simultaneous removal of arsenic and fluoride from actual samples
of groundwater and the possible interferences of other ions by EC
have not yet been published.
Groundwater may also contain co-existing anions such as SO2 4 ,
PO3 2þ
4 , cations as Mg , Ca
2þ
and hydrated species of silica
(SiO2,xH2O). These co-existing anions compete with F and
HAsO2 4 with aluminum flocs (Sandolval et al., 2014). The presence
1
of SO2 3
4 and PO4 in concentrations higher than 50 mg L and
1
4 mg L , respectively, inhibits arsenic and fluoride removal (Wan
et al., 2011). Dissolved hydrated species of silica, contained in nat-
ural water generally between 20 and 60 mg L1, or in higher con-
centrations, also obstruct the removal of As and F. These species
have a similar function to hydrated acids such as H2SiO3, H4SiO4,
H6SiO7, H8Si3O and H10SiO13 (Pourbaix, 1974). According to
Lakshmanan et al. (2010) the monovalent state of H3SiO4 , which
sparingly appears at hydrated silica concentrations greater than
20 mg L1 and at pH > 8, competes with arsenate for adsorption
sites. Lartiges et al. (1997) investigated the flocculation of colloidal
silica with hydrolyzed aluminum. These authors discuss the for-
mation of aluminum complexes with silica anions (aluminum-sil-
icates). These have potential active sites for aluminum aggregate
growing. Likewise, Tokoro et al. (2014) suggest that hydrated silica
could be removed during kaolinite (amorphous aluminum silicate)
formation by co-precipitation and adsorption processes.
On the other hand, the presence of Ca2þ enhances defluor-
idation owing to the ability of fluoride to form CaF2(s) (Zuo et al.,
2008). In the same way, the ion Mg2þ improved fluoride removal,
because Mg2þ is a good coagulant (MgF2) and is frequently used as
co-coagulant with aluminum salt (Montero and Villafan ~ e, 2010).
The aim of this study was to decrease the arsenic and fluoride
concentrations in groundwater from the Bajío region by EC using
aluminum as the sacrificial anode in a continuous filter-press
reactor. We analyzed the influence of current density and mean
linear flow velocity on the efficiency of arsenic and fluoride
removal. Aluminum flocs were characterized by SEM-EDAX, XRD
and FTIR. The energy consumption for electrolysis was also
estimated.
2. Electrocoagulation process
EC consists of an in situ generation of coagulants by electro-
dissolution of aluminum electrodes. At the anode, aluminum ions
are produced first (Al3þ); afterwards, the aluminum ions are
transformed to aluminum hydroxides (Al(OH)3(s)) and aluminum
oxides (Al2O3(s)) in volume:
Al(s) / Al3þ þ 3e (1)
Al3þ þ 3H2O / Al(OH)3(s) þ 3Hþ (2)
2Al3þ þ 3H2O / Al2O3(s) þ 6Hþ (3)
At the aluminum cathode, hydrogen gas is released:
3H2O þ 3e / 1.5H2 þ 3OH (4)
Typically, at the cathode interface the solution becomes alkaline
with time. The OH migrates and diffuses away from the cathode to
the anode, thus favoring water formation, hydroxyl ions reacts with
protons of Eqs. (2) and (3), making the remaining solution neutral:
OH þ Hþ / H2O (5)
The major problem of the aluminum anode is its passivation,
due to Al2O3(s) precipitation, giving high anode and cell potential,
increasing the energy consumption and cost of EC (Kobya et al.,
2011; Mohora et al., 2012). Passivation can be controlled at low
current densities in combination with turbulent flow conditions,
which favors Al3þ ions transport away from the surface to the bulk
solution. In addition, the use of cathodes of the same material are
recommended to electro-dissolve Al2O3(s) by periodic current
reversal (Mohora et al., 2012), which allows an even consumption
of aluminum electrodes during the process.
As we mentioned above, our group had previously discussed
that arsenic removal is more efficient when arsenite is oxidized to
arsenate, after the addition of a typical amount of sodium hypo-
chlorite used for disinfection purposes (1 mg L1) (Flores et al.,
2013). The Al(OH)3(s) and Al2O3(s) flocs are believed to adsorb

n et al. / Chemosphere 144 (2016) 2113e2120
A. Guzma
HAsO2
4 (Kobya et al., 2011):
h i
AlðOHÞ3ðsÞ þ HAsO2
4 / AlðOHÞ3 HAsO2
4 s (6)
h i
Al2 ðOHÞ3ðsÞ þ HAsO2 2
4 / Al2 ðOHÞ3 HAsO4 s (7)
The mechanism of fluoride removal by EC is carried out using a
chemical substitution, in which F replaces OH group from
Al(OH)3 flocs according to equation (8), (Zhu et al., 2007).
Al(OH)3 þ xF / Al(OH)3xFx þ xOH (8)
Groundwater contains high concentrations of co-existing ions
which affect arsenic and fluoride removal (Bennajah et al., 2010);
hence, the influence of co-existing ions on the As and F removal
efficiency are examined.
3. Materials and methods
3.1. Solutions
Groundwater samples were collected from deep wells (320 m)
located in the Bajío region of Guanajuato, Mexico (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, alkalinity
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-
dium hypochlorite used for disinfection.
3.2. Filter press reactor
The experimental setup and the dimensions of the filter-press
electrochemical reactor were described in Flores et al. (2013). The
system consists of a continuous pre-pilot scale filter-press-type cell,
where the coagulant is produced. The resulting solution (a mixture
of water and coagulant) is passed to a jar test to induce the floc-
culation and adsorption of arsenic on the aluminum flocs and re-
action between fluoride and aluminum aggregates. The arsenic and
fluoride are then precipitated, and the clarified solution is analyzed.
3.3. Methodology
EC was performed at different mean linear flow rates between
0.91  u  3.82 cm s1 and current densities of 4, 5 and 6 mA cm2.
Immediately, each resulting solution was passed to test jar equip-
ment, mixing at slow speed (45 rpm), for a duration of 15 min,
causing the growth of aggregates; then, aggregates are precipitated
in the static solution, for approximately three hours. The arsenic,
fluoride, phosphate, sulfate, hydrated silica, calcium and magne-
sium in the clarified solution were analyzed. After dissolution of the
flocs, the aluminum contained was also analyzed.
3.4. Analytical procedure
3.4.1. Groundwater characterization
Based on the standard method suggested by APHA (1998), an
atomic absorption spectrometer (Perkin Elmer AAnalist 200),
equipped with a manual hydride generator at 188.9 nm wavelength
was employed to determine the arsenic concentrations (detection
limit of 0.1 mg L1). Fluoride concentrations were measured using
an ion selective electrode of fluoride, model 27502-19, from Cole
Palmer (detection limit of 0.02 mg L1). The aluminum concen-
tration was determined by Atomic Absorption (AA) with a detection
limit of 0.15 mg L1. The analysis of phosphate was carried out by kit
2115
HI 93717 Phosphate High Range, ISM, while silica determination
was performed by Heteropoly Blue Method using the kit HI 93705.
Both analyses employed a multi-parameter photometer C99 by
Hanna Instruments. Sulfate was quantified using the turbidimetry
technique (APHA, 1998) using the spectrophotometer Perkin Elmer
Lambda 35 UV/VIS. The detection limit of sulfates, phosphates and
hydrated silica was 0.2 mg L1. Carbonates and hardness tests were
carried out by titration according to standard methods (APHA,
1998). Ca and Mg (which give hardness) were also determined by
AA with detection limits of 0.02 and 0.03 mg L1, respectively.
Conductivity and pH measurements were carried out using a water
proof instrument, model HI 991300 from Hanna Instruments. All
chemical reagents were of analytical grade. Each individual
experiment was performed at least three times, and then the re-
sults were averaged.
3.4.2. Scanning electron microscopy and energy dispersive X-ray
analysis
The Scanning Electron Microscopy (SEM) analysis was carried
out in using a Jeol JSM-6610LV. The Energy Dispersive Analysis of X-
rays (EDAX) was carried out in an Oxford X-Max detector integrated
in the microscope.
3.4.3. X-ray diffraction analysis (XRD)
XRD were performed on a diffractometer Rigaku, model DMAX
220, with nickel filter and radiation of CuK a.
3.4.4. Fourier transform infrared spectroscopy (FTIR)
The FTIR analysis in the flocs was carried out in a Perkin Elmer
Spectrum GX FTIR Spectrometer using an EasiDiff diffuse reflec-
tance accessory. The flocs samples were prepared using potassium
bromide (sample:KBr, 1:14). The diffuse reflectance accessory
allowed conducting the FTIR analysis.
3.4.5. Zeta potential
The zeta potential was measured using an electrokinetic solids
analyzer (Anton Paar SurPass) with the remaining water from EC.
4. Results and discussion
4.1. Simultaneous As and F removal by EC
Fig. 1aec shows the influence of mean linear flow velocity on the
residual concentration of arsenic (CAs) at constant current density
of 4, 5 and 6 mA cm2, respectively. The experimental CAl(III) and
theoretical CAl(III) (N) aluminum doses (Eq. (9)) are also included. At
4 mA cm2 the CAs displayed an abatement at
0.91  u  1.82 cm s1, with experimental aluminum doses be-
tween 20.6  CAl(III)  12.7 mg L1. At u > 1.82 cm s1 CAs increases
up to 37.9 mg L1 with CAl(III) ¼ 7.9 mg L1, indicating that arsenic
removal is not favored with mean linear flow velocity owing to
depletion of CAl(III). It is important to mention that the CAl(III), is
lower than the theoretical value.
 
jLMW  
CAlðIIIÞðNÞ ¼ 1  106 ðNÞ (9)
zFSu
where CAl(III)(N) is the theoretical concentration of aluminum dose
(mg L1), j is the current density (A cm2), L is the length of one
channel (cm), MW is the molecular weight of aluminum
(26.98 g mol1), n is the number of exchanged electrons, 3, F is the
Faraday constant (96485C mol1), S is the channel width (cm), u is
the mean linear flow velocity (cm s1), N is the number of channels,
and 1  106 is a conversion factor to obtain units of concentration of
aluminum in mg L1.
2116
A. Guzma
Fig. 1. Influence of the mean linear flow rate on the residual arsenic concentration and
aluminum dose for groundwater. Applied current density: (a) 4 mA cm2, (b)
5 mA cm2 and (c) 6 mA cm2.
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
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
accumulated in earlier electrolysis. Afterwards, at u > 1.82 cm s1

n et al. / Chemosphere 144 (2016) 2113e2120
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
decrease of Ca2þ (initially 2 mg L1 Ca2þ) and Mg2þ (initially
1.5 mg L1 Mg2þ) with j and remained almost constant with u. The
slightly removal of Ca2þ and Mg2þ suggests that they might
(10)
Fig. 2. Influence of the mean linear flow rate on the residual fluoride concentration,
evaluated from the EC tests similar to those from Fig. 1.

n et al. / Chemosphere 144 (2016) 2113e2120
A. Guzma
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.
precipitate in the flocs. On the other hand, the hydrated silica
depletion was 0.15 mg L1, from its initial value of 112.4 mg L1,
which suggests that silica species were removed by co-
precipitation and/or by the formation of aluminum silicates with
divalent cations such as Ca2þ and Mg2þ; the latter is validated by
XRD analysis shown below.
4.2. Flocs characterization
4.2.1. SEM/EDAX
Fig. 5a shows a SEM image of aluminum flocs obtained either
from the EC process at 4 mA cm2 and 0.91 cm s1, and Fig. 5b at
5 mA cm2 and 0.91 cm s1. These micrographs show particles with
irregular shape and size of up to around 150 mm, Fig. 5a, and up to
around 200 mm in Fig. 5b. Fig. 5ced shows a SEM image of
aluminum flocs obtained from the EC process at 6 mA cm2 and
0.91 cm s1 and 1.82 cm s1, respectively. Particles are also of
irregular shape, whit size of up to around 500 mm. From Fig. 5 it can
be observed that maximum particle size increases with current
density.
Table 1 shows the composition of the flocs, determined by
EDAX. Areas of around 800 mm  800 mm were analyzed. The low
standard deviations imply that the samples are homogeneous. Six
areas were analyzed for flocs produced using currents of 4 mA cm2
and 5 mA cm2, and twelve areas for flocs produced using
6 mA cm2. In flocs corresponding to 4 mA cm2, Mg was not
2117
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.
detected. At 5 mA cm2 and 6 mA cm2, the six elements were
present. Oxygen and aluminum were always present. The presence
of Si on the aluminum flocs can produce hydro-aluminum-silicates
(Tokoro et al., 2014); this last was confirmed by FTIR as shown
below.
It has been reported that arsenic is removed by an adsorption
process on the flocs followed by precipitation (Mo
lgora et al., 2013;
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
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
measured by point analyses.
On the other hand, zeta potential measurements on the flocs
gave negative values (Table 2), except for those obtained at
5 mA cm2 and 1.82 cm s1, which indicates that fluoride, sulfates,
carbonates, and phosphates are removed and form a coordinate
complex with hydrated silica species. The above may be performed
by precipitation with aluminum flocs, likely through an adsorption
process and/or ionic interchange reaction. In addition, the negative
zeta potential is also provoked by the slight increase in pH after EC
tests (see Table 2). This change in pH also increases the electrical
conductivity.
4.2.2. X-ray diffraction analysis (XRD)
In Fig. 6a XRD spectrum shows very broad and shallow
diffraction peaks, the first from 5 to 18 and the second from 25 to
38 . Bragg reflections possessing very broad humps and low in-
tensities indicate that the analyzed sample has a short range order,
2118
n et al. / Chemosphere 144 (2016) 2113e2120
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
could be expected that the broad peaks could be assigned to
amorphous silica or amorphous alumina. However, these peaks do
not match with those previously reported for amorphous silica
(Abis et al., 2001; Musi

c et al., 2011) or amorphous alumina (Wu,
2001; Li and Huang, 2007; Wang et al., 2009). After 38 the XRD
pattern shows a continuous series of narrow peaks. Then, it is
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.

n et al. / Chemosphere 144 (2016) 2113e2120
A. Guzma
Fig. 6. Typical XRD (a) and FTIR (b) spectra of the dried flocs obtained at 4 mA cm2
and 1.82 cm s1.
superposition of a high number of narrow peaks. Peaks corre-
sponding to merwinite (Ca3Mg(SiO4)2), anorthite (CaAl2Si2O8),
albite (NaAlSi3O8), boggsite (NaCa2(Al5Si19O48),H2O), cordierite
(Mg2Al4Si5O18), tremolite (Ca2Mg5(Si8O22)(OH)2) and rosenhahnite
(Ca3SiO8(OH)2) were identified. If a-Al2O3 and g- Al2O3 phases are
present in the samples their content might be below 5 wt. %, owing
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
low content of these elements in the groundwater, Arsenic,
43 mg L1 and fluoride 2.5 mg L1.
4.2.3. FT-IR characterization
FTIR analysis ranged from wave numbers between 4000 and
450 cm1 was performed to analyze the chemical bonds of the
elements present in the flocs (obtained at j of 4 mA cm2 and u of
1.82 cm s1), Fig. 6b. The infrared spectrum analysis showed a wide
band at 3550e3200 cm1, which most likely corresponds to OeH
stretching vibrations (Socrates, 2004). The peak located at
1750 cm1 is likely attributed to the NaeF bounding. AleO bending
is represented by the band at 1500 cm1. The peak at 1300 is likely
attributed to AleOeSi. SieO bond is represented at 1100 cm1. The
band at 705e690 cm1 may be ascribed to the stretching of AleF
(Lartiges et al., 1997; Kobya et al., 2011). The band at 850e800 cm1
is characteristic of AseO bending. The FTIR analysis confirms once
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
at flow rates between 0.91 and 1.82 cm s1, corresponding to
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
with mean linear flow rate owing to aluminum ions are transported
away from the surface to the bulk solution under such turbulent
flow conditions, decreasing Al2O3 precipitation on the anode. The
energy consumption (Econs) was evaluated for the EC test shown in
Table 2. The energy consumption during electrolysis was deter-
mined by:
Ecell I
Econs ¼ (12)
ð3:6ÞSBu
where Ecell is given in units of V, I is the current intensity during
electrolysis (C s1), B is the channel height (cm), S is the channel
width (cm) and the value 3.6, is a conversion factor that allows to
obtain Econs in units of kWh m3. The cost of aluminum doses
evaluated as $Al(III)](CAl(III)  ($1.55 USD kg1)  0.001) is also
included in Table 2. The cost of aluminum considered for this cal-
culations was $1.55 USD kg1 and the value of 0.001 is a conversion
factor to obtain $Al(III) in units of $ USD m3.
The best EC in terms of energy consumption (Econs) and cost of
aluminum dosed was obtained at 4 mA cm2 with u ¼ 1.82 cm s1,
giving Econs of 0.34 KWh m3, and $Al(III) of 0.020 USD m3. It is
important to mention that in this paper we did not included an
estimate of the overall EC process due to electricity fee variance
between countries.
2120
n et al. / Chemosphere 144 (2016) 2113e2120
A. Guzma
5. Conclusions
The decrease of arsenic and fluoride concentrations from
groundwater after EC using aluminum as anode in a continuous
filter press reactor met the WHO standard (CAs  10 mg L1,
CF  1.5 mg L1) at current densities of 4, 5 and 6 mA cm2 and flow
velocities of 0.91 and 1.82 cm s1, highlighting that arsenate was
abated.
XRD, FTIR and SEM-EDAX analyses performed to aluminum flocs
revealed that these were composed by aluminum silicates. Arse-
nate, sulfate and phosphate are adsorbed on aluminum flocs.
Fluoride might replace hydroxyl groups from flocs. The best EC in
terms of energy consumption (0.34 KWh m3) and cost of
aluminum dosed ($ 0.020 USD m3) was obtained at 4 mA cm2
and 1.82 cm s1.
Acknowledgments
Authors thank the Universidad de Guanajuato for financial
support. We are grateful to National Laboratory UG-CONACYT
(project No. 123732) for analytical and technical assistance.
References
Abis, L., Armelao, L., Dell'Amico, D.B., Calderazzo, F., Garbassi, F., Merigo, A.,
Quadrelli, E.A., 2001. Gold molecular precursors and goldesilica interactions.
J. Chem. Soc. Dalton Trans. 18, 2704e2709.
American Public Health Association/American Water Works Association/Water
Pollution Control Federation, 1998. Standard Methods for the Examination of
Water and Wastewater, twentieth ed. (Washington DC).
Balasubramanian, N., Kojima, T., Basha, C.A., Srinivasakannan, C., 2009. Removal of
arsenic from aqueous solution using electrocoagulation. J. Hazard. Mater 167,
966e969.
Basu, A., Saha, D., Saha, R., Ghosh, T., Saha, B., 2014. A review on sources, toxicity and
remediation technologies for removing arsenic from drinking water. Res. Chem.
Intermed. 40, 447e485.
Bennajah, M., Maalmi, M., Darmane, Y., Touhami, M.E., 2010. Defluoridation of
drinking water by electrocoagulation/electroflotation: kinetic study. J. Urban
Environ. Eng. 4, 37e45.
Brahman, K.D., Kazi, T.G., Afridi, H.I., Naseem, S., Arain, S.S., Wadhwa, S.K., Shah, F.,
2013. Simultaneously evaluate the toxic levels of fluoride and arsenic species in
underground water of Tharparkar and possible contaminant sources: a multi-
variate study. Ecotoxicol. Environ. Saf. 89, 95e107.
Cui, M., Jang, M., Ibrahim, S., Park, B., Cho, E., Khim, J., 2014. Arsenite removal using a
pilot system of ultrasound and ultraviolet followed by microfiltration. Ultrason.
Sonochem. 21, 1527e1534.
Essadki, A.H., Gourich, B., Vial, Ch, Delmas, H., Bennajah, M., 2009. Defluoridation of
drinking water by electrocoagulation/electroflotation in a stirred tank reactor
with a comparative performance to an external-loop airlift reactor. J. Hazard.
Mater 168, 1325e1333.
~ o, G., Elorza, E., Martínez, F., 2013. Arsenic removal from
Flores, O.J., Nava, J.L., Carren
groundwater by electrocoagulation in a pre-pilot-scale continuous filter press
reactor. Chem. Eng. Sci. 97, 1e6.
Hansen, H.K., Nún ~ ez, P., Grandon, R., 2006. Electrocoagulation as a remediation tool
for wastewaters containing arsenic. Min. Eng. 19, 521e524.
Hu, C.Y., Lo, S.L., Kuan, W.H., 2007. Simulation the kinetics of fluoride removal by
electrocoagulation (EC) process using aluminum electrodes. J. Hazard. Mater.
145, 180e185.
Ingallinella, A.M., Pacini, V.A., Fern
andez, R.G., Vidoni, R.M., Sanguinetti, G., 2011.
Simultaneous removal of arsenic and fluoride from groundwater by
coagulation-adsorption with polyaluminum chloride. J. Env. Sci. Health. Part A
46, 1288e1296.
Kobya, M., Gebologlu, U., Ulu, F., Oncel, S., Demirbas, E., 2011. Removal of arsenic
from drinking water by the electrocoagulation using Fe and Al electrodes.
Electrochim. Acta 56, 5060e5070.
Kumar, E., Bhatnagar, A., Hogland, W., Marques, M., Sillanpa €€a, M., 2014. Interaction
of anionic pollutants with Al-based adsorbents in aqueous mediaea review.
Chem. Eng. J. 241, 443e456.
Lakshmanan, D., Clifford, D.A., Samanta, G., 2010. Comparative study of arsenic
removal by iron using electrocoagulation and chemical coagulation. Water Res.
44, 5641e5652.
Lartiges, B., Bottero, J., Derrendinger, L., Humbert, B., Tekely, P., Suty, H., 1997.
Flocculation of colloidal silica with hydrolyzed aluminum: an 27 Al solid state
NMR investigation. Langmuir 13, 147e152.
Li, Z.J., Huang, K.L., 2007. Electrochemical fabrication of sandwich nanostructures
based on anodic alumina. J. Braz. Chem. Soc. 18, 406e409.
Liu, R., Zhu, L., Lan, H., Liu, H., Qu, J., 2015. Simultaneous removal of arsenic and
fluoride by freshly-prepared aluminum hydroxide. Colloids Surf. A 486,
147e153.
Mo
lgora, C.C., Domínguez, A.M., Avila, E.M., Drogui, P., Buelna, G., 2013. Removal of
arsenic from drinking water: a comparative study between electrocoagulation-
microfiltration and chemical coagulation-microfiltration processes. Sep. Purif.
Technol. 118, 645e651.
Mohora, E., Ron cevi

c, S., Dalmacija, B., Agbaba, J., Watson, M., Karlovi
c, E.,
Dalmacija, M., 2012. Removal of natural organic matter and arsenic from water
by electrocoagulation/flotation continuous flow reactor. J. Hazard. Mater. 235,
257e264.
Montero, O.C., Villafan ~ e, J.M., 2010. Effect of dissolved species on the fluoride
electro-removal from groundwater. ECS Trans. 28, 57e65.
Musi
c, S., Filipovi

c-Vincekovi
c, N., Sekovani

c, L., 2011. Precipitation of amorphous
SiO2 particles and their properties. Braz. J. Chem. Eng. 28, 89e94.
Pourbaix, M., 1974. Atlas of Electrochemical Equilibria in Aqueous Solutions, second
ed. Texas, Houston.
Sandoval, M.A., Fuentes, R., Nava, J.L., Rodríguez, I., 2014. Fluoride removal from
drinking water by electrocoagulation in a continuous filter press reactor
coupled to a flocculator and clarifier. Sep. Purif. Technol. 134, 163e170.
Singh, K., Lataye, D.H., Wasewar, K.L., Yoo, C.K., 2013. Removal of fluoride from
aqueous solution: status and techniques. Desalination Water Treat. 51,
3233e3247.
Smedley, P., Kinniburgh, D.G., 2013. Arsenic in Groundwater and the Environment.
In: Selinus, O. (Ed.), Essentials of Medical Geology. Springer, New York,
pp. 283e286.
Socrates, G., 2004. Infrared and Raman Characteristic Group Frequencies:
Tables and Charts, third ed. Wiley, United Kingdom.
Tang, X., Zheng, H., Teng, H., Sun, Y., Guo, J., Xie, W., Yang, Q., Chen, W., 2014.
Chemical coagulation process for the removal of heavy metals from water: a
review. Desalination Water Treat. 1e16.
Tokoro, C., Suzuki, S., Haraguchi, D., Izawa, S., 2014. Silicate removal in aluminum
hydroxide co-precipitation process. Mater 7, 1084e1096.
Wan, W., Pepping, T.J., Banerji, T., Chaudhari, S., Giammar, D.E., 2011. Effects of water
chemistry on arsenic removal from drinking water by electrocoagulation. Water
Res. 45, 384e392.
Wang, S.G., Ma, Y., Shi, Y.J., Gong, W.X., 2009. Defluoridation performance and
mechanism of nano-scale aluminum oxide hydroxide in aqueous solution.
J. Chem. Technol. Biotechnol. 84, 1043e1050.
Wu, J., 2001. Nano-sized amorphous alumina particles obtained by ball milling ZnO
and Al powder mixture. Mater. Lett. 48, 324e330.
Zhao, X., Zhang, B., Liu, H., Qu, J., 2011. Simultaneous removal of arsenite and
fluoride via an integrated electro-oxidation and electrocoagulation process.
Chemosphere 83, 726e729.
Zhu, J., Zhao, H., Ni, J., 2007. Fluoride distribution in electrocoagulation defluor-
idation process. Sep. Pur. Technol. 56, 184e191.
Zuo, Q., Chen, X., Li, W., Chen, G., 2008. Combined electrocoagulation and electro-
flotation for removal of fluoride from drinking water. J. Hazard. Mater. 159,
452e457.