Separation and Purication Technology 56 (2007) 184191

Fluoride distribution in electrocoagulation deuoridation 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 uoride from water, but few of scientic literatures explore its inside mechanism.
A new approach was used in this study to investigate uoride distribution in the EC deuoridation process, which divided the uoride into three
parts: remained in water, removed by electrodes, and adsorbed on hydroxide aluminum ocs. The uoride distribution was investigated in terms
of several critical parameters such as pH, charge loading, current density and initial uoride concentration. The experimental results showed that
the removal by electrodes was primarily responsible for the high deuoridation efciency, and the adsorption by hydroxide aluminum ocs gave
a secondary effect. The parameters affected the efciencies of deuoridation in a way of changing the uoride distribution in the EC process.
A chemical complex of Al
n
(OH)
m
F
k
3nmk
was formulated to explain the mechanism inside the EC deuoridation process. The new approach
provides a detailed insight of the electrocondensation effect, which helps to gain more scientic 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
Fluoride is recognized as an essential constituent in the
human diet. Lowuoride concentration (<1 mg/L) could prevent
dental problem, but higher uoride concentration (>1.5 mg/L)
will cause dental and skeletal uorosis [1]. Many countries,
such as China, Egypt, India, Kenya, etc., have areas where
uorosis 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 uoride-bearing minerals, it becomes a
surface species. The discharge of industrial wastewater, such
as semiconductor industries, aluminum industries, and glass
manufacturing industries, also contributes uoride in water
pollution, especially in groundwater.
Many methods have been developed to remove excessive u-
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
[810].

Corresponding author. Tel.: +86 1 62751185; fax: +86 1 62756526.

E-mail address: nijinren@iee.pku.edu.cn (J.R. Ni).
The electrocoagulation (EC) is the process utilizing sacri-
ced anodes to form active coagulant which is used to remove
pollutant by precipitation and otation 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 [1921]. 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 [810,23,24] have demonstrated that EC
using aluminum electrodes is effective in deuoridation. They
focused on investigating the effects of critical operating param-
eters, such as inter-electrode distance, inuent pH, charge
loading, current density, electrode area/volume ratio, and ini-
tial F

concentration. The kinetics of EC deuoridation process

was reported to followthe exponential function with time [9,25].
Emamjomeh [10] developed an empirical model using critical
parameters to evaluate the rate constant (K) for uoride removal
by a monopolar EC-otation 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 Purication Technology 56 (2007) 184191 185
The mechanism of uoride removal process was a chemi-
cal adsorption process with F

replacing the OH group from

the Al
n
(OH)
3n
ocs [26]. Fluoride ions and hydroxide ions can
clearly coprecipitate with Al
3+
ions to form Al
n
F
m
(OH)
3nm
[27]:
nAl
3+
(aq)
+3n mOH

(aq)
+mF

(aq)
Al
n
F
m
(OH)
3nm(s)
(1)
However, the uoride ions in the precipitate are very easily
substituted for hydroxide ions:
Al
n
F
m
(OH)
3nm(s)
+OH

(aq)
Al
n
F
m1
(OH)
3nm+1(s)
+F

(aq)
(2)
It was reported that EC system performed better than CC
system in deuoridation efciency [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 technologieselectrochemistry, coag-
ulation and otation [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 depositionof elemental metals. If aluminumelectrodes
are used, the generated Al
3+
(aq)
ions will immediately undergo
further spontaneous reactions to produce corresponding hydrox-
ides and/or polyhydroxides. These hydroxides compounds have
strong afnity for dispersed particles as well as counter ions
to cause coagulation. The gases evolved at the electrodes may
impinge on and cause otation 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 uoride distribution could
provide more detailed information on the deuoridation in EC
process. The uoride in the EC process was divided into three
parts: (1) remain in water; (2) adsorbed by ocs 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 uoride attaching on the
electrodes resulted from the electrophoresis and/or electrocon-
densation effects in the electric eld.
The objective of this study is to explore the electrochemi-
cal and the chemical interaction in EC deuoridation process.
The membrane ltration was used after the coagulation pro-
cesses to eliminate the removal effects from precipitation or
otation. The effects of the inuent pH, charge loading, current
density and initial uoride concentration on the uoride distri-
bution were further investigated. From the experimental results,
a mechanism of uoride removal by EC was proposed and
described. The deuoridation performance of EC and CC was
also compared.
2. Experimental
2.1. Materials
Deionized water with 3.0 mM NaHCO
3
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
were made by adding proper amount of sodium uoride 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 pHwas measured by a pHmeter (Hanna, PH201), which
was freshly calibrated by 2 points (6.86, 9.18) before each test.
The uoride 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 mm60 mm and the A/V is 18 m
2
/m
3
. 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 occulated for
10 min by gentle mixing. Samples taken from the reactor were
directly ltered by syringe lter (0.22 um, PSE membrane). The
residual uoride in the ltrate 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 efciency in this study was
around 111%.
2.4. Coagulation test
A proper amount coagulant of Al(NO
3
)
3
was added to the
sample water containing uoride, 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 occulated for
10 min by gently mixing. The samples taken from coagulation
test were also directly ltered by syringe lter.
2.5. Fluoride distribution experiment
The ion chromatograph method has been used in several
studies [24,27] to measure uoride concentration, which is not
limitedbypHandcoexistingcations. Thus, the uoride adsorbed
186 J. Zhu et al. / Separation and Purication Technology 56 (2007) 184191
Fig. 1. Selected area energy dispersive X-ray spectra of the electrodes: (a) anode and (b) cathode.
on the ocs can be measured by adjusting the sample pH with
1 M NaOH to exceed 13, then completely dissolving aluminum
hydroxide particles and releasing the F

ions adsorbed on the

ocs. The eluents used in the ion chromatograph is NaOH and
high purity water, so the high pH will not affect the result. Each
test was run more than three times to eliminate the experimental
errors. The experimental procedure was as follows:
(1) Add 300 mL of test water with initial F

concentration
([F

]
initial
) into the EC reactor.
(2) Take out the electrodes immediately when the electrolysis
reaction is nished.
(3) Flocculate the solution for 10 min by gentle mixing.
(4) Take samples fromthe occulated solution; ltrate the sam-
ple by 0.22 m lter for uoride analysis and express the
result as [F

]
remain
(F

in water).
(5) Mix the residual occulated solution rapidly; take samples
for pH adjustment (pH>13) with 1 M NaOH. Take sample
for uoride analysis and express the result as [F

]
oc+remain
(F

in water and ocs) until the ocs is completely dis-

solved.
Based on the aforementioned experiments, the distribution
of uoride concentration including [F

]
remain
, [F

]
ocs
and
[F

]
electrodes
could be obtained, of which [F

]
ocs
(uoride
adsorbed on ocs) =[F

]
ocs+remain
[F

]
remain
; [F

]
electrodes
(uoride removal by electrodes) =[F

]
initial
[F

]
ocs+remain
.
Furthermore, the efciency of uoride removal can be dened
as
F
=1 [F

]
remain
/[F

]
initial
.
3. Results and discussion
3.1. Characteristics of Al electrodes
The Al electrodes after EC deuoridation was analyzed by
using EDXand XPS to prove the existence of uoride 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/m
3
), which showed that the uoride ions
exist on both the anode and the cathode after EC deuoridation
process.
3.2. Fluoride distribution in the EC process
3.2.1. Effect of inuent pH
The inuent pH is one of the important factors affecting the
performance of electrochemical process [15]. In the EC sys-
tem, the uoride removal efciency is solely determined by the
uoride on electrodes and ocs. The uoride distribution was
shown in Fig. 2, from which the variation of overall removal
efciency of uoride with the inuent pHcould be clearly identi-
ed. The optimal pHrange was 5.56.5, at which higher uoride
removal efciency could be reached. Similar results have also
been reported by other investigators [26].
The adsorption on ocs is of primary importance to under-
standing of the uoride distribution. Based on the chemical Eqs.
(1) and (2), lower pHis favorable for uoride removal. In the EC
process, however, the pH could be increased not only because
Table 1
The surface composition of the electrodes analyzed by XPS
Atomic concentration (%) C O F Na Al Cl
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
Fig. 2. Fluoride distribution at various pH values; initial [F

] =5 mg/L, charge
loading =1.55 F/m
3
, t =10 min.
J. Zhu et al. / Separation and Purication Technology 56 (2007) 184191 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 uoride ions. Therefore, further increase
of the inuent pH would decrease the deuoridation capabil-
ity. In Fig. 2, the adsorbed uoride on ocs declined quickly
to be neglected as the inuent 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 deuoridation.
The deuoridation by electrodes is a major contributor to
overall removal efciency in an EC system. Higher removal
efciency of electrodes was corresponding to the inuent pH
range of 6.07.0, but the efciency would decrease as the inu-
ent becoming acidic or basic. However, the removal efciency of
electrodes would become dominant even under basic conditions
(pH7.5). The variation of deuoridation with the inuent pH
implied that different interactions might exist around the elec-
trodes, such as electrophoresis, adsorption and precipitation of
hydrouoroaluminumcomplexes. It is the complexes formed on
electrodes that vary with the inuent pH, which in turn lead to
the change of uoride removed by electrodes.
3.2.2. Effect of charge loading
The quality of EC efuent 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 uoride distribution with dif-
ferent charge loading was illustrated in Fig. 3. Initial sharp
increase of overall removal efciency could be clearly seen. As
charge loading was over 1.55 F/m
3
, the overall removal ef-
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 ef-
ciency of electrodes and those of the overall removal efciency,
whereas removal efciency of the hydro-aluminum ocs tended
to decrease with increasing charge loading. The applied poten-
tial increased with the current densities rising, which enhanced
the electrophoresis effect. The higher Al
3+
concentration on the
Fig. 3. Fluoride distribution at various charge loadings; initial [F

] =5 mg/L,
pH 6.5, t =10 min.
Fig. 4.
e/f
at various charge loadings.
surface of anode could also help to capture the uoride ions
by complexation, adsorption and coprecipitation. Consequently,
uoride ions were attracted to the electrodes and the uoride
concentration near the electrodes exceeded that in bulk solu-
tion. Lower uoride concentration in bulk solution reduced the
possibility of removal by ocs adsorption, although the amount
of hydro-aluminumocs was increased. This indicated that uo-
ride ions were apt to be removed by the electrodes, which proved
the occurrence of the electrocondensation effect [24,25,27].
Therefore, greater deuoridation efciency by electrodes could
be expected than hydroxide aluminum ocs.
In order to compare the removal effects of electrodes and
ocs, we calculated the ratio (r
e/f
) of removal efciency of elec-
trodes (
electrodes
) to that of ocs (
ocs
). As results, the rise of r
e/f
with increasing charge loading as shown in Fig. 4 implied that
electrochemical effect was enhanced signicantly with chemical
effect weakened relatively.
3.2.3. Effect of current density
Many researchers studied the inuence 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 loadingbyvaryingreactiontime. It was foundthat current
density has little effect on deuoridation by ocs (Fig. 5). The
reason is that the principal factors inuencing adsorption of u-
oride by ocs are coagulant dosage and solution pH. Moreover,
the experimental results showed that (Table 2) the current ef-
ciency changed little with varying current density for the same
charge loading.
Hence, change of the overall removal efciency should be
primarily attributed to the variation of deuoridation efciency
of the electrodes. The overall removal efciency would decrease
as current density exceeds 9.26 A/m
2
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/m
2
) 4.63 9.26 18.52 37.04 92.59
[Al
3+
] (mg/L) (theoretical) 9.33 9.33 9.33 9.33 9.33
[Al
3+
] (mg/L) 9.77 9.77 9.93 10.50 10.03
Current efciency (%) 104 104 106 112 107
188 J. Zhu et al. / Separation and Purication Technology 56 (2007) 184191
Fig. 5. Fluoride distribution at various current densities; initial [F

] =5 mg/L,
charge loading =1.04 F/m
3
, 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 Al
3+
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/m
2
. Thus, both rapid liberation and short run
time wouldleadtoincomplete reactionaroundthe electrodes due
to insufcient time to reach dynamic equilibrium. In addition,
the rapid liberation of Al
3+
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 efciency of electrodes as discussed in Section 3.2.1.
Experiments ondeuoridationunder different appliedcurrent
densities revealed that operating current was of less signicance
to removal efciency of electrode as current density was below
9.26 A/m
2
(Fig. 5). Furthermore, long reaction time was unde-
sirable from the engineering viewpoint. For the current density
of 9.26 A/m
2
, 10-min reaction time was enough to equilibrate
solution pH and form hydrouoroaluminum complexes. Thus,
Fig. 7.
e/f
at various initial uoride 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 deu-
oridation efciency 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, deu-
oridation efciency and capacity were also shown in Fig. 6a
and b, respectively. It was observed that the deuoridation ef-
ciency of electrodes tended to decrease although deuoridation
capacity increased relatively with the initial F

concentration
rising. However, both removal efciency and capacity of ocs
increased when the initial F

concentration went up. The rela-

tionship between r
e/f
and initial F

concentration as shown in
Fig. 7revealedthat the increase of initial F

concentrationwould
improve the chemical effect by increasing uoride concentration
in bulk solution.
Adsorption isotherm of the EC process was drawn by the
mass of uoride adsorption and the equilibrium concentration
of uoride remained in the water. Both Freundlich and Lang-
muir equations were used to specify the data, and a better t was
found for the latter as shown in Fig. 8. Although the EC deu-
oridation process could be well described by the conventional
Langmuir equation as also reported in other similar studies [30],
the uoride distribution provided more detailed information on
Fig. 6. Fluoride distribution at various initial F

concentrations (a) deuoridation efciency (b) deuoridation capacity; charge loading =2.07 F/m
3
, pH6.5, t =10 min.
J. Zhu et al. / Separation and Purication Technology 56 (2007) 184191 189
Fig. 8. Equilibrium isothems.
the removal mechanisms inside ECprocess under different oper-
ating conditions.
3.3. Proposed mechanism of uoride removal by EC
From above discussions, it is found that the removal by
electrodes was primarily responsible for the high deuorida-
tion efciency, and the adsorption by hydroxide aluminum ocs
gave a secondary effect. In order to have a deeper under-
standing of the EC process, hydro-uoro-aluminum complex
Al
n
(OH)
m
F
k
3nmk
was used to describe various chemical
species containing uoride, hydroxide and Al
3+
, such as AlF
complexes, AlOH complexes and the hydro-uoro- aluminum
colloid ocs.
An schematic of Al
n
(OH)
m
F
k
3nmk
complex based on ion
structure was shown in Fig. 9. At 3n =m+k, Al
n
(OH)
m
F
k
3nmk
complexes were likely to exist in the form of colloid species,
which could be removed by the follow-up membrane ltration.
At 3n <m+k, the negatively charged Al
n
(OH)
m
F
k
3nmk
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-uoro-aluminumcomplexes. The
Al
n
(OH)
m
F
k
3nmk
complexes could integrate with dense Al
3+
ions on the surface of anode to form colloid ocs precipitated
or adsorbed on the anode surface. At 3n >m+k, the positively
charged Al
n
(OH)
m
F
k
3nmk
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 deuoridation process in EC.
Fig. 10. Enhancement in uoride removal from 2 to 40 times at higher Al
3+
and
F

concentrations. Final Al
3+
=10 mg/L, nal F

=5 mg/L, pH 6.5.
the charge of the Al
n
(OH)
m
F
k
3nmk
complexes to formcolloid
ocs precipitated or adsorbed on the cathode surface. Both kinds
of Al
n
(OH)
m
F
k
3nmk
would be removed when electrodes were
taken out of the reactor. It was electrical eld that encouraged
Al
n
(OH)
m
F
k
3nmk
to be condensed near the electrodes, which
made the uoride adsorbed mostly on the electrodes so that the
EC process had a higher deuoridation efciency.
According to the previous studies [31], the F

/Al
3+
ratio
of hydro-uoro-aluminum precipitated at a high concentration
of uoride exceeded that at a low concentration of uoride. A
CC process with manually concentrating Al
3+
and uoride was
designed to simulate the EC process for local condensation in
the area near the electrodes [17]. Fig. 10 summarized the deuo-
ridation efciency for various Al
3+
and F

concentration. From
Fig. 10, it could be seen that locally high concentration of Al
3+
and F

ions signicantly improved F

removal.
3.4. Comparison of EC and CC
Tests were conducted to compare EC and CC under vari-
ous Al
3+
dosages and pH values at an initial F

concentration
of 5 mg/L. Samples obtained from CC and EC efuent were
ltrated with micro-membrane (0.22 m) to eliminate precip-
itation or otation. 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 uoridation removal for
all the Al
3+
concentrations tested in the pH range of 6.07.0,
especially for low Al
3+
dosages. For example, 80% reduction
of uoride was achieved by EC process at an Al
3+
dosage of
1020 mg/L, whereas the same reduction achieved by CC pro-
cess required Al
3+
dosage of 3040 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 deuoridation in the EC process by investigat-
ing uoride distribution, efforts are still needed to understand
the uoride removal mechanism with particular attention to the
potential applications, such as removal by otation and by pre-
190 J. Zhu et al. / Separation and Purication Technology 56 (2007) 184191
Fig. 11. Comparison of deuoridation efciency between the EC process and CC process.
cipitation. The removal by electrodes is the dominant contributor
to the deuoridation 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 nal purpose of designing a uoride removal
system would be achieved.
4. Conclusion
The uoride in the EC process could be distributed into three
parts, i.e. remained in water, adsorbed by ocs generated and
formed in situ, and removed by the gelatinous layer attached
on the electrodes. In this study, the existence of the uoride on
the electrodes was proved experimentally with help of EDX and
XPS analysis. The overall deuoridation efciency varies with
uoride distribution that is altered by operating parameters such
as pH, charge loading, current density and initial uoride con-
centration. The removal efciency of electrodes was compared
with that of ocs, and the ratio between them (r
e/f
) was found
to be increased with the rise of charge loading but decreased
with increasing initial F

concentration. The existence of elec-

tric eld would enhance the concentration of the Al
3+
and F

around the surface of electrode, and thus signicantly improve

F

removal in EC process. As far as the uoridation removal

is concerned, the EC process has obvious advantages over the
CC process at various Al
3+
concentrations (especially low Al
3+
dosages) with pH of 6.07.0. 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 XPSand EDXanalysis.
References
[1] World Health Organization, Fluoride in drinking water, WHO Guidelines
for Drinking Water Quality, 2004. www.who.int/entity/water sanitation
health/dwq/chemicals/uoride.pdf.
[2] H. Lounici, L. Addour, D. Belhocine, H. Grib, S. Nicolas, B. Bariou,
N. Mameri, Study of a new technique for uoride removal from water,
Desalination 114 (1997) 241251.
[3] S. Ghorai, K.K. Pant, Equilibrium, kinetics and breakthrough studies for
adsorption of uoride on activated alumina, Sep. Purif. Technol. 42 (2005)
265271.
[4] G.L. He, S.R. Cao, Assessment of uoride removal from drinking water
by calcium phosphate systems, Fluoride 29 (1996) 212216.
[5] M. Pinon-Miramontes, R.G. Bautista-Margulis, A. Perez-Hernandez,
Removal of arsenic and uoride from drinking water with cake alum and
a polymeric anionic occulent, Fluoride 36 (2003) 122128.
[6] P.I. Ndiayea, P. Moulin, L. Dominguez, J.C. Millet, F. Charbit, Removal
of uoride from electronic industrial efuent by RO membrane separation,
Desalination 173 (2005) 2532.
[7] Z. Amor, B. Bariou, N. Mameri, M. Taky, S. Nicolas, A. Elmidaoui, Flu-
oride removal from brackish water by electrodialysis, Desalination 133
(2001) 215223.
[8] S.C. Li, Electro-chemiclal method to remove uoride from drinking water,
Water Supply 3 (1985) 177186.
[9] N. Mameri, A.R. Yeddou, H. Lounici, D. Belhocine, H. Grib, B. Bariou,
Deuoridation of septentrional Sahara water of north Africa by electro-
coagulation process using bipolar aluminium electrodes, Water Res. 32
(1998) 16041612.
[10] M.M. Emamjomeh, M. Sivakumar, An empirical model for deuoridation
by batch monopolar electrocoagulation/otation (ECF) process, J. Hazard.
Mater. 131 (2006) 118125.
[11] M.Y.A. Mollah, R. Schennach, J.R. Parga, D.L. Cocke, Electrocoagulation
(EC)science and applications, J. Hazard. Mater. 84 (2001) 2941.
[12] G.H. Chen, Electrochemical technologies in wastewater treatment, Sep.
Purif. Technol. 38 (2004) 1141.
[13] N. Adhoum, L. Monser, N. Bellakhal, J.E. Belgaied, Treatment of
electroplating wastewater containing Cu
2+
, Zn
2+
and Cr(VI) by electro-
coagulation, J. Hazard. Mater. 112 (2004) 207213.
[14] P. Gao, X.M. Chen, F. Shen, G.H. Chen, Removal of chromium(VI) from
wastewater bycombinedelectrocoagulationelectrootationwithout a lter,
Sep. Purif. Technol. 43 (2005) 117123.
[15] G.H. Chen, X.M. Chen, P.L. Yue, Electrocoagulation and electrootation
of restaurant wastewater, J. Environ. Eng. -ASCE 126 (2000) 858863.
[16] X.H. Xu, X.F. Zhu, Treatment of refectory oily wastewater by electro-
coagulation process, Chemosphere 56 (2004) 889894.
[17] B.T. Zhu, D.A. Clifford, S. Chellam, Comparison of electrocoagulation
and chemical coagulation pretreatment for enhanced virus removal using
microltration membranes, Water Res. 39 (2005) 30983108.
J. Zhu et al. / Separation and Purication Technology 56 (2007) 184191 191
[18] M.J. Matteson, R.L. Dobson, R.W. Glenn, N.S. Kukunoor, W.H. Waits,
E.J. Clayeld, Electrocoagulation and separation of aqueous suspensions
of ultrane particles, Colloid Surf. A-Physicochem. Eng. Asp. 104 (1995)
101109.
[19] A.S. Koparal, U.B. Ogutveren, Removal of nitrate fromwater by electrore-
duction and electrocoagulation, J. Hazard. Mater. 89 (2002) 8394.
[20] A. Murugananthan, G.B. Raju, S. Prabhakar, Removal of sulde, sulfate
and sulte ions by electro coagulation, J. Hazard. Mater. 109 (2004) 3744.
[21] N. Bektas, H. Akbulut, H. Inan, A. Dimoglo, Removal of phosphate from
aqueous solutions by electro-coagulation, J. Hazard. Mater. 106 (2004)
101105.
[22] P.K. Holt, G.W. Barton, C.A. Mitchell, The future for electrocoagulation as
a localised water treatment technology, Chemosphere 59 (2005) 355367.
[23] N. Mameri, H. Lounici, D. Belhocine, H. Grib, D.L. Piron, Y. Yahiat, Deu-
oridation of Sahara water by small plant electrocoagulation using bipolar
aluminium electrodes, Sep. Purif. Technol. 24 (2001) 113119.
[24] C.Y. Hu, S.L. Lo, W.H. Kuan, Effects of co-existing anions on uoride
removal in electrocoagulation (EC) process using aluminum electrodes,
Water Res. 37 (2003) 45134523.
[25] M. Lui, R.Y. Sun, J.H. Zhang, Y. Bina, L. Wei, Elimination of excess
uoride in potable water with coarcervation by electrolysis using aluminum
anode, Fluoride 20 (1983) 5463.
[26] F. Shen, X.M. Chen, P. Gao, G.H. Chen, Electrochemical removal of u-
oride ions from industrial wastewater, Chem. Eng. Sci. 58 (2003) 987
993.
[27] C.Y. Hu, S.L. Lo, W.H. Kuan, Effects of the molar ratioof hydroxide andu-
oride to Al(III) on uoride removal by coagulation and electrocoagulation,
J. Colloid Interface Sci. 283 (2005) 472476.
[28] M.Y.A. Mollah, P. Morkovsky, J.A.G. Gomes, M. Kesmez, J. Parga, D.L.
Cocke, Fundamentals, present and future perspectives of electrocoagula-
tion, J. Hazard. Mater. 114 (2004) 199210.
[29] E.A. Wik, D.A. Carlson, A.S. Eikum, Electrocoagulation of potable water,
Water Res. 18 (1984) 13551360.
[30] M. Carmona, M. Khemis, J.P. Lecler, F. Lapicque, Asimple model topredict
the removal of oil suspensions from water using the electrocoagulation
technique, Chem. Eng. Sci. 61 (2006) 12371246.
[31] J. Bufe, N. Parthasarathy, W. Haerdi, Importance of speciation
methods in analytical control of water treatment processes with appli-
cation to uoride removal from wastewater, Water Res. 19 (1985) 7
23.
[32] G.H. Zhang, Y. Gao, Y. Zhang, P. Gu, Removal of uoride from drinking
water by a membrane coagulation reactor (MCR), Desalination 177 (2005)
143155.