Separation and Purification Technology 56 (2007) 184–191

Fluoride distribution in electrocoagulation defluoridation process

Jun Zhu, Huazhang Zhao, Jinren Ni ∗
Department of Environmental Engineering, Peking University, The Key Laboratory of Water and Sediment Sciences,
Ministry of Education, Beijing 100871, PR China
Received 20 September 2006; received in revised form 24 December 2006; accepted 31 January 2007

Abstract
Electrocoagulation (EC) is an effective process to remove fluoride from water, but few of scientific literatures explore its inside mechanism.
A new approach was used in this study to investigate fluoride distribution in the EC defluoridation process, which divided the fluoride into three
parts: remained in water, removed by electrodes, and adsorbed on hydroxide aluminum flocs. The fluoride distribution was investigated in terms
of several critical parameters such as pH, charge loading, current density and initial fluoride concentration. The experimental results showed that
the removal by electrodes was primarily responsible for the high defluoridation efficiency, and the adsorption by hydroxide aluminum flocs gave
a secondary effect. The parameters affected the efficiencies of defluoridation in a way of changing the fluoride distribution in the EC process.
A chemical complex of Aln (OH)m Fk 3n−m−k was formulated to explain the mechanism inside the EC defluoridation process. The new approach
provides a detailed insight of the electrocondensation effect, which helps to gain more scientific comprehension about the cooperation between
electrochemical and chemical ways occurring inside the EC process.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Fluoride; Electrocoagulation; Chemical coagulation; Electrocondensation

1. Introduction The electrocoagulation (EC) is the process utilizing “sacri-

Fluoride is recognized as an essential constituent in the
human diet. Low fluoride concentration (<1 mg/L) could prevent
dental problem, but higher fluoride concentration (>1.5 mg/L)
will cause dental and skeletal fluorosis [1]. Many countries,
such as China, Egypt, India, Kenya, etc., have areas where
fluorosis is endemic [1]. Fluoride pollution in environment
occurs through two different channels: natural sources and
anthropogenic sources. Fluoride is frequently encountered in
minerals and in geochemical deposits. Because of the erosion
and weathering of fluoride-bearing minerals, it becomes a
surface species. The discharge of industrial wastewater, such
as semiconductor industries, aluminum industries, and glass
manufacturing industries, also contributes fluoride in water
pollution, especially in groundwater.
Many methods have been developed to remove excessive flu-
oride from drinking water. These methods can be categorized
into four categories: adsorption [2,3], chemical precipita-
tion [4,5], membrane separation [6,7], and electrocoagulation
[8–10].
∗ Corresponding author. Tel.: +86 1 62751185; fax: +86 1 62756526.
E-mail address: nijinren@iee.pku.edu.cn (J.R. Ni).
ficed” anodes to form active coagulant which is used to remove
pollutant by precipitation and flotation in situ. Compared with
traditional chemical coagulation (CC), EC process reportedly
requires less space and does not require chemical storage, dilu-
tion, and pH adjustment [11]. It is proven to be effective in
water treatment such as drinking water supply for small or
medium sized community [12]. EC process has been widely
studied in water and wastewater treatment to remove heavy met-
als [13,14], organics [15,16], bacteria [17], turbidity [18] and
inorganic anions [19–21]. Because of its proven ability to effec-
tively remove wide range of pollutants, together with its inherent
simplicity of design and operation, EC is being re-examined as
potential treatment technology [22].
Some researchers [8–10,23,24] have demonstrated that EC
using aluminum electrodes is effective in defluoridation. They
focused on investigating the effects of critical operating param-
eters, such as inter-electrode distance, influent pH, charge
loading, current density, electrode area/volume ratio, and ini-
tial F− concentration. The kinetics of EC defluoridation process
was reported to follow the exponential function with time [9,25].
Emamjomeh [10] developed an empirical model using critical
parameters to evaluate the rate constant (K) for fluoride removal
by a monopolar EC-flotation process.

1383-5866/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.seppur.2007.01.030
 J. Zhu et al. / Separation and Purification Technology 56 (2007) 184–191
The mechanism of fluoride removal process was a chemi-
cal adsorption process with F− replacing the –OH group from
the Aln (OH)3n flocs [26]. Fluoride ions and hydroxide ions can
clearly coprecipitate with Al3+ ions to form Aln Fm (OH)3n−m
[27]:
− −
nAl3+
(aq) + 3n − mOH(aq) + mF(aq) → Aln Fm (OH)3n−m(s)
However, the fluoride ions in the precipitate are very easily
substituted for hydroxide ions:
Aln Fm (OH)3n−m(s) + OH−
(aq)
→ Aln Fm−1 (OH)3n−m+1(s) + F−
(aq)
It was reported that EC system performed better than CC
system in defluoridation efficiency [24,25,27]. However, only
simple explanation was offered about the electrocondensation
effect near the surface of electrode without directly experimental
proof.
EC is a complex electrochemical process, which comprises
chemical and physical processes involving many surface and
interfacial phenomena. The technology lies at the intersection of
three more fundamental technologies—electrochemistry, coag-
ulation and flotation [22]. When a potential is applied to form
an external power source, the anode material undergoes oxi-
dation, while the cathode will be subjected to reduction or
reductive deposition of elemental metals. If aluminum electrodes
are used, the generated Al3+ (aq) ions will immediately undergo
further spontaneous reactions to produce corresponding hydrox-
ides and/or polyhydroxides. These hydroxides compounds have
strong affinity for dispersed particles as well as counter ions
to cause coagulation. The gases evolved at the electrodes may
impinge on and cause flotation of the coagulated materials.
However, fundamental researches on physical, chemical and
electrochemical interactions are still needed for successful engi-
neering design of EC reactor [28].
A new approach to investigate the fluoride distribution could
provide more detailed information on the defluoridation in EC
process. The fluoride in the EC process was divided into three
parts: (1) remain in water; (2) adsorbed by flocs generated and
formed in situ; and (3) removed by the gelatinous layer attached
on the electrodes which were immediately taken out of the reac-
tor after the electrolysis reaction. The fluoride attaching on the
electrodes resulted from the electrophoresis and/or electrocon-
densation effects in the electric field.
The objective of this study is to explore the electrochemi-
cal and the chemical interaction in EC defluoridation process.
The membrane filtration was used after the coagulation pro-
cesses to eliminate the removal effects from precipitation or
flotation. The effects of the influent pH, charge loading, current
density and initial fluoride concentration on the fluoride distri-
bution were further investigated. From the experimental results,
a mechanism of fluoride removal by EC was proposed and
described. The defluoridation performance of EC and CC was
also compared.
185
2. Experimental
2.1. Materials
Deionized water with 3.0 mM NaHCO3 and 2.0 mM NaCl
was used to simulate natural water with a certain degree of alka-
linity and ionic strength. Desired concentrations of F− solution
(1) were made by adding proper amount of sodium fluoride into
the water. The conductivities of the sample water in all the
experiments are between 500 and 750 ␮S/cm.
2.2. Analytical methods
The pH was measured by a pH meter (Hanna, PH201), which
(2) was freshly calibrated by 2 points (6.86, 9.18) before each test.
The fluoride concentration was determined by an ion chromato-
graph (Dionex, ICS 2500).
2.3. Electrocoagulation test
A 300-mL of sample solution was placed into a batch reac-
tor for each test run. Two monopolar aluminum electrodes,
both having a purity of 99.999%, were used as the anode and
cathode, respectively. The dimensions of the electrodes were
90 mm × 60 mm and the A/V is 18 m2 /m3 . Before each test,
organic impurities on electrode surfaces were removed by wash-
ing with acetone and follow-up HCl solution (10% wt) prior to
use. The two electrodes were placed at a distance of 10 mm. The
current density was maintained constant by using a potentiostat
in intensiostat mode.
According to conventional mixing mode, the rapid mixing by
a magnetic stirrer was used to enhance full contact between the
solution and the coagulant produced in situ. After electrolysis,
the electrodes were taken out and the solution was flocculated for
10 min by gentle mixing. Samples taken from the reactor were
directly filtered by syringe filter (0.22 um, PSE membrane). The
residual fluoride in the filtrate was then measured. At the end of
each run, the electrodes were washed thoroughly with water to
remove any solid residues on the surfaces, and then dried and
re-weighted. The calculated current efficiency in this study was
around 111%.
2.4. Coagulation test
A proper amount coagulant of Al(NO3 )3 was added to the
sample water containing fluoride, and then the water was mixed
rapidly for 1 min. During the mixing, the pH of the water was
adjusted to the desired value with dilute acid (HCl) or base
(NaOH) solution. After mixing, the solution was flocculated for
10 min by gently mixing. The samples taken from coagulation
test were also directly filtered by syringe filter.
2.5. Fluoride distribution experiment
The ion chromatograph method has been used in several
studies [24,27] to measure fluoride concentration, which is not
limited by pH and coexisting cations. Thus, the fluoride adsorbed
186 J. Zhu et al. / Separation and Purification Technology 56 (2007) 184–191

Fig. 1. Selected area energy dispersive X-ray spectra of the electrodes: (a) anode and (b) cathode.

on the flocs can be measured by adjusting the sample pH with 3.2. Fluoride distribution in the EC process
1 M NaOH to exceed 13, then completely dissolving aluminum
hydroxide particles and releasing the F− ions adsorbed on the 3.2.1. Effect of influent pH
flocs. The eluents used in the ion chromatograph is NaOH and The influent pH is one of the important factors affecting the
high purity water, so the high pH will not affect the result. Each performance of electrochemical process [15]. In the EC sys-
test was run more than three times to eliminate the experimental tem, the fluoride removal efficiency is solely determined by the
errors. The experimental procedure was as follows: fluoride on electrodes and flocs. The fluoride distribution was
shown in Fig. 2, from which the variation of overall removal
(1) Add 300 mL of test water with initial F− concentration efficiency of fluoride with the influent pH could be clearly identi-
([F− ]initial ) into the EC reactor. fied. The optimal pH range was 5.5–6.5, at which higher fluoride
(2) Take out the electrodes immediately when the electrolysis removal efficiency could be reached. Similar results have also
reaction is finished. been reported by other investigators [26].
(3) Flocculate the solution for 10 min by gentle mixing. The adsorption on flocs is of primary importance to under-
(4) Take samples from the flocculated solution; filtrate the sam- standing of the fluoride distribution. Based on the chemical Eqs.
ple by 0.22 ␮m filter for fluoride analysis and express the (1) and (2), lower pH is favorable for fluoride removal. In the EC
result as [F− ]remain (F− in water). process, however, the pH could be increased not only because
(5) Mix the residual flocculated solution rapidly; take samples
for pH adjustment (pH > 13) with 1 M NaOH. Take sample Table 1
for fluoride analysis and express the result as [F− ]floc+remain The surface composition of the electrodes analyzed by XPS
(F− in water and flocs) until the flocs is completely dis- Atomic concentration (%) C O F Na Al Cl
solved. Anode 28.44 48.60 1.93 0.58 19.19 1.25
Cathode 24.26 46.69 0.56 4.03 23.89 0.56
Based on the aforementioned experiments, the distribution
of fluoride concentration including [F− ]remain , [F− ]flocs and
[F− ]electrodes could be obtained, of which [F− ]flocs (fluoride
adsorbed on flocs) = [F− ]flocs+remain − [F− ]remain ; [F− ]electrodes
(fluoride removal by electrodes) = [F− ]initial − [F− ]flocs+remain .
Furthermore, the efficiency of fluoride removal can be defined
as εF = 1 − [F− ]remain /[F− ]initial .

3. Results and discussion

3.1. Characteristics of Al electrodes

The Al electrodes after EC defluoridation was analyzed by

using EDX and XPS to prove the existence of fluoride ions in the
surface layer of electrodes. The results were given in Fig. 1 and
Table 1, respectively (operation: [F− ] initial = 1 mmol/L, pH 6.5,
charge loading = 2.07 F/m3 ), which showed that the fluoride ions
exist on both the anode and the cathode after EC defluoridation Fig. 2. Fluoride distribution at various pH values; initial [F− ] = 5 mg/L, charge
process. loading = 1.55 F/m3 , t = 10 min.
 J. Zhu et al. / Separation and Purification Technology 56 (2007) 184–191 187

of the hydrogen generation at the EC cathodes [29], but also

the liberation of hydroxide ions from aluminum hydroxide due
to the substitution of fluoride ions. Therefore, further increase
of the influent pH would decrease the defluoridation capabil-
ity. In Fig. 2, the adsorbed fluoride on flocs declined quickly
to be neglected as the influent pH was getting over 7.5. Since
aluminum hydroxide is an amphoteric hydroxide, high pH will
lead to the formation of Al(OH)− 4 , which is soluble and useless
for defluoridation.
The defluoridation by electrodes is a major contributor to
overall removal efficiency in an EC system. Higher removal
efficiency of electrodes was corresponding to the influent pH
range of 6.0–7.0, but the efficiency would decrease as the influ-
ent becoming acidic or basic. However, the removal efficiency of
electrodes would become dominant even under basic conditions
(pH ≥ 7.5). The variation of defluoridation with the influent pH
implied that different interactions might exist around the elec-
trodes, such as electrophoresis, adsorption and precipitation of
hydrofluoroaluminum complexes. It is the complexes formed on
electrodes that vary with the influent pH, which in turn lead to
the change of fluoride removed by electrodes.
3.2.2. Effect of charge loading
The quality of EC effluent depends on the amount of coag-
ulant produced (mg) or applied charge loading [12]. In this
study, charge loading was obtained at the same reaction time
by changing current density. The fluoride distribution with dif-
ferent charge loading was illustrated in Fig. 3. Initial sharp
increase of overall removal efficiency could be clearly seen. As
charge loading was over 1.55 F/m3 , the overall removal effi-
ciency approached a plateau at 91%. The same tendency was
also observed by other investigators [15]. The optimal charge
loading appeared at the end of the sharp increasing stage.
Similar trends were found between variations of removal effi-
ciency of electrodes and those of the overall removal efficiency,
whereas removal efficiency of the hydro-aluminum flocs tended
to decrease with increasing charge loading. The applied poten-
tial increased with the current densities rising, which enhanced
the electrophoresis effect. The higher Al3+ concentration on the
Fig. 4. γ e/f at various charge loadings.
surface of anode could also help to capture the fluoride ions
by complexation, adsorption and coprecipitation. Consequently,
fluoride ions were attracted to the electrodes and the fluoride
concentration near the electrodes exceeded that in bulk solu-
tion. Lower fluoride concentration in bulk solution reduced the
possibility of removal by flocs adsorption, although the amount
of hydro-aluminum flocs was increased. This indicated that fluo-
ride ions were apt to be removed by the electrodes, which proved
the occurrence of the electrocondensation effect [24,25,27].
Therefore, greater defluoridation efficiency by electrodes could
be expected than hydroxide aluminum flocs.
In order to compare the removal effects of electrodes and
flocs, we calculated the ratio (re/f ) of removal efficiency of elec-
trodes (εelectrodes ) to that of flocs (εflocs ). As results, the rise of re/f
with increasing charge loading as shown in Fig. 4 implied that
electrochemical effect was enhanced significantly with chemical
effect weakened relatively.
3.2.3. Effect of current density
Many researchers studied the influence of current density
based on varying charge loading [9,20]. In this study, the effect
of current density was investigated based on a constant applied
charge loading by varying reaction time. It was found that current
density has little effect on defluoridation by flocs (Fig. 5). The
reason is that the principal factors influencing adsorption of flu-
oride by flocs are coagulant dosage and solution pH. Moreover,
the experimental results showed that (Table 2) the current effi-
ciency changed little with varying current density for the same
charge loading.
Hence, change of the overall removal efficiency should be
primarily attributed to the variation of defluoridation efficiency
of the electrodes. The overall removal efficiency would decrease
as current density exceeds 9.26 A/m2 as shown in Fig. 5. Current

Table 2
Aluminum electrodes behavior during the EC test at various current densities
1 2 3 4 5

Current density (A/m2 ) 4.63 9.26 18.52 37.04 92.59

[Al3+ ] (mg/L) (theoretical) 9.33 9.33 9.33 9.33 9.33
[Al3+ ] (mg/L) 9.77 9.77 9.93 10.50 10.03
Fig. 3. Fluoride distribution at various charge loadings; initial [F− ] = 5 mg/L, Current efficiency (%) 104 104 106 112 107
pH 6.5, t = 10 min.
188 J. Zhu et al. / Separation and Purification Technology 56 (2007) 184–191
Fig. 5. Fluoride distribution at various current densities; initial [F− ] = 5 mg/L,
charge loading = 1.04 F/m3 , pH 6.5.
density directly affected coagulant dosage and bubble genera-
tion rate, as well as the mixing intensity and mass transfer near
electrodes [22], so increasing current density would accelerate
the liberation rate of Al3+ and OH− ions. Furthermore, the run
time was varied to keep the same charge loading, of which the
biggest and smallest run times differed by a factor of about 20,
e.g. the run time was only 1 min when the current density was
applied at 92.59 A/m2 . Thus, both rapid liberation and short run
time would lead to incomplete reaction around the electrodes due
to insufficient time to reach dynamic equilibrium. In addition,
the rapid liberation of Al3+ and OH− ions from the surface of
electrode would make the solution around the anode and cathode
extremely acidic or basic respectively, which would decrease the
removal efficiency of electrodes as discussed in Section 3.2.1.
Experiments on defluoridation under different applied current
densities revealed that operating current was of less significance
to removal efficiency of electrode as current density was below
9.26 A/m2 (Fig. 5). Furthermore, long reaction time was unde-
sirable from the engineering viewpoint. For the current density
of 9.26 A/m2 , 10-min reaction time was enough to equilibrate
solution pH and form hydrofluoroaluminum complexes. Thus,
Fig. 6. Fluoride distribution at various initial F− concentrations (a) defluoridation efficiency (b) defluoridation capacity; charge loading = 2.07 F/m3 , pH 6.5, t = 10 min.
Fig. 7. γ e/f at various initial fluoride concentrations.
there should be an optimal current density at a certain applied
charge loading for the EC system.
3.2.4. Effect of initial F− concentration
Fig. 6 showed the general relation between the overall deflu-
oridation efficiency and initial F− concentration, from which
we could see that the former gradually decreased from 92 to
80% as the latter increased from 3 to 15 mg/L. Moreover, deflu-
oridation efficiency and capacity were also shown in Fig. 6a
and b, respectively. It was observed that the defluoridation effi-
ciency of electrodes tended to decrease although defluoridation
capacity increased relatively with the initial F− concentration
rising. However, both removal efficiency and capacity of flocs
increased when the initial F− concentration went up. The rela-
tionship between re/f and initial F− concentration as shown in
Fig. 7 revealed that the increase of initial F− concentration would
improve the chemical effect by increasing fluoride concentration
in bulk solution.
Adsorption isotherm of the EC process was drawn by the
mass of fluoride adsorption and the equilibrium concentration
of fluoride remained in the water. Both Freundlich and Lang-
muir equations were used to specify the data, and a better fit was
found for the latter as shown in Fig. 8. Although the EC deflu-
oridation process could be well described by the conventional
Langmuir equation as also reported in other similar studies [30],
the fluoride distribution provided more detailed information on
 J. Zhu et al. / Separation and Purification Technology 56 (2007) 184–191
Fig. 8. Equilibrium isothems.
the removal mechanisms inside EC process under different oper-
ating conditions.
3.3. Proposed mechanism of fluoride removal by EC
From above discussions, it is found that the removal by
electrodes was primarily responsible for the high defluorida-
tion efficiency, and the adsorption by hydroxide aluminum flocs
gave a secondary effect. In order to have a deeper under-
standing of the EC process, hydro-fluoro-aluminum complex
Aln (OH)m Fk 3n−m−k was used to describe various chemical
species containing fluoride, hydroxide and Al3+ , such as Al–F
complexes, Al–OH complexes and the hydro-fluoro- aluminum
colloid flocs.
An schematic of Aln (OH)m Fk 3n−m−k complex based on ion
structure was shown in Fig. 9. At 3n = m + k, Aln (OH)m Fk 3n−m−k
complexes were likely to exist in the form of colloid species,
which could be removed by the follow-up membrane filtration.
At 3n < m + k, the negatively charged Aln (OH)m Fk 3n−m−k com-
plexes would move towards the anode by electric migration.
In the immediate region around the anode, there was a locally
higher concentration of hydro-fluoro-aluminum complexes. The
Aln (OH)m Fk 3n−m−k complexes could integrate with dense Al3+
ions on the surface of anode to form colloid flocs precipitated
or adsorbed on the anode surface. At 3n > m + k, the positively
charged Aln (OH)m Fk 3n−m−k complex would also be attracted to
the adjacent area of the cathode by the electrophoretic effect.
The liberated hydroxide ions near the cathode could neutralize
Fig. 9. Scheme of proposed defluoridation process in EC.
189
Fig. 10. Enhancement in fluoride removal from 2 to 40 times at higher Al3+ and
F− concentrations. Final Al3+ = 10 mg/L, final F− = 5 mg/L, pH 6.5.
the charge of the Aln (OH)m Fk 3n−m−k complexes to form colloid
flocs precipitated or adsorbed on the cathode surface. Both kinds
of Aln (OH)m Fk 3n−m−k would be removed when electrodes were
taken out of the reactor. It was electrical field that encouraged
Aln (OH)m Fk 3n−m−k to be condensed near the electrodes, which
made the fluoride adsorbed mostly on the electrodes so that the
EC process had a higher defluoridation efficiency.
According to the previous studies [31], the F− /Al3+ ratio
of hydro-fluoro-aluminum precipitated at a high concentration
of fluoride exceeded that at a low concentration of fluoride. A
CC process with manually concentrating Al3+ and fluoride was
designed to simulate the EC process for local condensation in
the area near the electrodes [17]. Fig. 10 summarized the defluo-
ridation efficiency for various Al3+ and F− concentration. From
Fig. 10, it could be seen that locally high concentration of Al3+
and F− ions significantly improved F− removal.
3.4. Comparison of EC and CC
Tests were conducted to compare EC and CC under vari-
ous Al3+ dosages and pH values at an initial F− concentration
of 5 mg/L. Samples obtained from CC and EC effluent were
filtrated with micro-membrane (0.22 ␮m) to eliminate precip-
itation or flotation. The experimental results are summarized
in Fig. 11, in which the pH range of CC process was referred
to other studies [32]. Fig. 11 showed that EC process signif-
icantly outperformed CC process for fluoridation removal for
all the Al3+ concentrations tested in the pH range of 6.0–7.0,
especially for low Al3+ dosages. For example, 80% reduction
of fluoride was achieved by EC process at an Al3+ dosage of
10–20 mg/L, whereas the same reduction achieved by CC pro-
cess required Al3+ dosage of 30–40 mg/L. It is well understood
that it was electrocondensation that made EC outperform CC in
the low coagulant dosage, which was essentially absent in the
CC process.
Although the present study indicated the contribution of
electrodes to defluoridation in the EC process by investigat-
ing fluoride distribution, efforts are still needed to understand
the fluoride removal mechanism with particular attention to the
potential applications, such as removal by flotation and by pre-
190 J. Zhu et al. / Separation and Purification Technology 56 (2007) 184–191
Fig. 11. Comparison of defluoridation efficiency between the EC process and CC process.
cipitation. The removal by electrodes is the dominant contributor
to the defluoridation of EC process, but the complexes near the
electrode would more or less passivate the electrodes. From the
engineering viewpoint, more practical issues should be consid-
ered before the final purpose of designing a fluoride removal
system would be achieved.
4. Conclusion
The fluoride in the EC process could be distributed into three
parts, i.e. remained in water, adsorbed by flocs generated and
formed in situ, and removed by the gelatinous layer attached
on the electrodes. In this study, the existence of the fluoride on
the electrodes was proved experimentally with help of EDX and
XPS analysis. The overall defluoridation efficiency varies with
fluoride distribution that is altered by operating parameters such
as pH, charge loading, current density and initial fluoride con-
centration. The removal efficiency of electrodes was compared
with that of flocs, and the ratio between them (re/f ) was found
to be increased with the rise of charge loading but decreased
with increasing initial F− concentration. The existence of elec-
tric field would enhance the concentration of the Al3+ and F−
around the surface of electrode, and thus significantly improve
F− removal in EC process. As far as the fluoridation removal
is concerned, the EC process has obvious advantages over the
CC process at various Al3+ concentrations (especially low Al3+
dosages) with pH of 6.0–7.0. The approach proposed in this
study could provide not only insight into electrocondensation
around the surface of electrode but also more detailed infor-
mation on electrochemical and chemical interactions in the EC
process.
Acknowledgements
The authors are thankful to Professor Alistair Borthwick in
University of Oxford and Professor C.F. Chiang in China Med-
ical University for their valuable help in English editing during
the preparation of the paper. Thanks are also to J.L Xie and
W.W. Zhou, College of Chemistry and Molecular Engineering in
Peking University, for their assistance in XPS and EDX analysis.
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