Journal of Industrial and Engineering Chemistry 20 (2014) 40144021

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Journal of Industrial and Engineering Chemistry

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Adsorption capacity of bone char for removing uoride from water

solution. Role of hydroxyapatite content, adsorption mechanism and
competing anions
N.A. Medellin-Castillo a, R. Leyva-Ramos b,*, E. Padilla-Ortega b, R. Ocampo Perez b,
J.V. Flores-Cano b, M.S. Berber-Mendoza a
a
Centro de Investigacion y Estudios de Posgrado, Facultad de Ingeniera, Universidad Autonoma de San Luis Potosi, Av. Dr. M. Nava 8, San Luis Potosi, SLP
78290, Mexico
b
Centro de Investigacion y Estudios de Posgrado, Facultad de Ciencias Qumicas, Universidad Autonoma de San Luis Potosi, Av. Dr. M. Nava 6, San Luis Potosi,
SLP 78210, Mexico

A R T I C L E I N F O A B S T R A C T

Article history: The adsorption of uoride from water on bone char (BC) was investigated in this work, and the uoride
Received 21 August 2013 adsorption capacity of BC was compared to that of hydroxyapatite (HAP). The adsorption capacity of BC
Accepted 30 December 2013 and HAP drastically increased while decreasing the pH from 7.0 to 5.0. Furthermore, the uoride
Available online 8 January 2014
adsorption on BC was due to its HAP content and was not considerably affected by the presence of the
anions Cl, HCO3, CO32, SO42, NO3 and NO2. The mechanism of uoride adsorption on BC was
Keywords: attributed to electrostatic interactions between surface charge of BC and uoride ions in solution.
Adsorption
2014 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
Bone char
Fluoride
reserved.
Hydroxyapatite
Water pollution

1. Introduction adsorbents have been developed and tested, including activated

The impact of uoride concentration in drinking water onto
human health has been extensively studied and reviewed in
various works [1,2]. A concentration of uoride between 0.5 and
1.5 mg/L is essential for the human body, especially in preventing
the incidence of dental caries; however, long term ingestion of
water with excess amount of uoride, above 2 mg/L, can cause
diseases such as dental and skeletal uorosis, masculine infertility
and cancer [2].
Several treatment processes have been applied to remove
excess uoride from drinking water. Some of the common
processes are chemical precipitation [3], ion exchange [4],
adsorption [5,6], reverse osmosis [4], electrodialysis [7] and
nanoltration [8]. Adsorption is the most suitable process for
drinking water treatment because it is relatively simple, economic,
and appropriate for small communities [9,10].
During the past 10 years, extensive research has been carried
out to nd both low-cost and high capacity adsorbents for the
removal of uoride from drinking water. A wide range of
* Corresponding author. Tel.: +52 444 826 2440; fax: +52 444 826 2372.
E-mail address: rlr@uaslp.mx (R. Leyva-Ramos).
alumina [11], natural minerals such as laterite, zeolite, and
caolinite [1214], nanomaterials [15], carbonaceous materials
[7,16], bone char (BC) and hydroxyapatite (HAP) [5,17,18].
BC is manufactured by the carbonization of cattle bones and
contains around 10% carbon and 90% HAP [19]. The adsorption of
uoride on BC has been investigated in various works [5,6,18,20].
In a previous work [5], it was shown that the capacity of BC for
adsorbing uoride was higher than those of activated alumina and
activated carbon. Furthermore, the effect of solution pH and
temperature on the adsorption capacity of uoride onto BC was
investigated and it was found that the maximum adsorption took
place at pH 3 and decreased nearly 20 times by increasing the pH
from 3 to 12. This behavior was attributed to the electrostatic
interactions between the surface of BC and uoride ions in
solution. The adsorption capacity was not inuenced by tempera-
ture in the range from 15 to 35 8C.
The anions HCO3, CO32, Cl, NO3, NO2, and SO42 are
commonly found in drinking water and these anions can compete
with the uoride for the adsorption sites of BC, affecting the
adsorption capacity of BC toward uoride. The competing effect of
these anions on the capacity of BC for adsorbing uoride has not
been investigated in detail. Due to the high toxicity of As(V), the
competitive adsorption of As(V) and uoride from aqueous

1226-086X/$ see front matter 2014 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jiec.2013.12.105
 N.A. Medellin-Castillo et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 40144021
solution on BC has been studied because it is well documented that
uoride and As(V) may be co-occurring in drinking waters in
several countries of Latin America [21]. Mlilo et al. [22] determined
the adsorption isotherm of uoride on BC with and without As(V)
and concluded that the As(V) did not affect the uoride adsorption
capacity of BC for an initial concentration of As(V) of 0.250 mg/L.
Calcium hydroxyapatite, Ca10(PO4)6(OH)2, is an important
inorganic material in biology and chemistry [2325]. Its structure,
ion exchange capacity, adsorption afnity, and its capacity to bond
with organic molecules of different sizes, have attracted much
attention in the last two decades. The adsorption of heavy metals,
Pb2+, Cu2+ and Cd2+, from aqueous solutions on HAP has been
attributed to the ion exchange of Ca2+ on the HAP by the metal
cation in solution [26,27]. Adsorption of uoride on this adsorbent
has been studied in several works [17,27] and it has been found
that the mechanism of uoride adsorption is due to electrostatic
attractions and ion exchange processes.
BC is mainly composed of HAP and it is essential to evaluate the
contribution of this mineral to the adsorption of uoride on BC.
Thus, the main objective of this research was to evaluate the role of
HAP on the capacity of BC for adsorbing uoride from aqueous
solution. Furthermore, the mechanism of uoride adsorption on BC
would be elucidated, and the effect of the presence of anions,
commonly found in natural waters, on the uoride adsorption
capacity of BC would be analyzed in detail.
2. Materials and methods
2.1. Bone char and hydroxyapatite
In this work, the granular BC used is commercially known as Fija
Fluor and is manufactured from cattle bones by APELSA,
Guadalajara, Mexico. The BC was sieved to an average particle
diameter of 0.79 mm, washed repeatedly with deionized water,
dried in an oven at 100 8C for 24 h, and stored in plastic containers.
Analytical grade hydroxyapatite (purity < 99% according to the
manufacturer, SigmaAldrich, CAS Number: 1306-06-5) was also
used in this study.
2.2. Characterization of bone char and hydroxyapatite
The contents of carbon, hydrogen and nitrogen on BC were
determined using an Elemental Analyzer, Fisons Carlo Erba, EA-
1108. The phosphorus weight percentage of BC was evaluated by
Inductively Coupled Plasma (ICP) Atomic Emission Spectroscopy
using a Thermo Jarrel Ash, model IRIS/AP, instrument. The sample
was prepared for ICP analysis using the method described by
Medellin-Castillo [28].
The surface charge and point of zero charge (PZC) of BC and HAP
were determined by a titration method [5]. The acid stability of BC
was determined by a procedure similar to that recommended by
Wingenfelder et al. [29]. A BC mass of 0.5 g and 40 mL of solution
with an initial pH varying from 0.8 to 12.0 were added to a plastic
bottle. The solutions were prepared by mixing proper volumes of
0.1 N HNO3 and NaOH solutions. The BC and acid solution were left
in contact for 7 days and periodically mixed in an orbital shaker,
and the nal pH of the acid solution was measured. Moreover, the
concentration of Ca2+ and PO43 dissolved in the acid solutions
were determined by atomic absorption spectroscopy and atomic
emission spectroscopy.
The morphology of BC and HAP particles were observed by
means of a scanning electron microscope (SEM), Philips, model XL-
30. The microscope was equipped with an energy dispersive Si(Li)
detector EDAX DX4 for microanalysis.
X-ray diffraction (XRD) analysis was used to identify the
crystalline species present in both adsorbents employing an X-ray
4015
diffractometer, Rigaku, model DMAX 2000. The textural properties
of both materials (specic area, pore volume and average pore
diameter) were determined by the N2-BET method using a surface
area and porosimetry analyzer, Micromeritics, model ASAP 2010.
2.3. Determination of the concentrations of the anions in water
solution
The uoride concentration in an aqueous solution was
determined by a potentiometric method using a potentiometer,
Orion, model SA720, and a selective electrode for uoride ion. This
method allowed the determination of uoride concentrations in
the range from 0.1 to 10 mg/L. The uoride calibration curves were
prepared with standard solutions of uoride. Further details of the
analytical method can be found elsewhere [28,30].
The concentrations of bicarbonate (HCO3), carbonate (CO32),
chloride (Cl), nitrate (NO3), nitrite (NO2), phosphate (PO43),
and sulfate (SO42) in water solutions were determined using the
methods recommended by APHA [30].
2.4. Adsorption equilibrium data
Experimental adsorption equilibrium data were obtained as
follows. A portion of 490 mL of an aqueous solution of a known
initial concentration of uoride or HCO3, CO32, Cl, NO3, NO2,
and SO42 was added to the batch adsorber. A given mass of BC or
HAP was added to a Nylon basket and placed inside the adsorber.
The mass of BC or HAP was 0.5 or 1.0 g, and the initial
concentrations of uoride varied from 1 to 20 mg/L. The adsorber
was placed in a constant temperature water bath and the solution
was continuously mixed by a magnetic stirrer located just below
the water bath. The solution was left in contact with the BC or HAP
until equilibrium was reached, which took between 5 and 7 days.
The solution pH was measured periodically with a pH-meter and
kept constant by adding few drops of 0.01 and 0.05 HNO3 or NaOH
solutions as required. The total volume added of HNO3 or NaOH
solutions was recorded and considered in the mass balance. The
solution was sampled at specic time intervals and the concen-
tration of uoride was determined for each sample. Equilibrium
was reached when the concentrations of two consecutive samples
did not change over time. The mass of uoride or HCO3, CO32,
Cl, NO3, NO2, and SO42 adsorbed at equilibrium was calculated
by performing a mass balance of uoride or other anions.
The effect of coexisting or competing anions such as chloride on
the uoride adsorption capacity of BC was carried out by
determining the adsorption equilibrium data of uoride at
pH = 7.0 and T = 25 8C, and varying the initial concentration of
chloride from 20 to 80 mg/L during the adsorption of uoride.
3. Results and discussion
3.1. Morphology of BC and HAP
As seen in Fig. 1(a), the forms and shapes of the BC particles are
very irregular and its surface is fractured, rough and porous. The
distribution of the particle sizes is not uniform. The morphology of
the HAP particles is shown in Fig. 1(b), and the particles presented
a layered shape that is typical of HAP.
3.2. Chemical composition
The elemental analysis of BC showed that the weight
percentages of nitrogen, hydrogen and carbon were 0.95, 0.52
and 6.31%, correspondingly. The carbon content is very similar to
the value reported by Wilson et al. [31] for a BC manufactured from
cattle bones.
[(Fig._1)TD$IG]
4016 [(Fig._2)TD$IG]
N.A. Medellin-Castillo et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 40144021

1800

Concentration of calcium, mg/L

1500

1200

900

600

300

0
0 2 4 6 8 10 12
Final pH
a)
80

Concentration of phosphate, mg/L

70
60
50
40
30
20
10
0
0 2 4 6 8 10 12
Final pH
Fig. 1. SEM images of BC particles (a) and HAP particles (b). b)
Fig. 2. Acidbase stability of the BC at T = 25 8C. (a) Concentration of calcium and (b)
concentration of phosphate in solution.
The weight percentage of phosphorus in the BC was found to be
15.0%. Assuming that all the phosphorus belongs only to the HAP
present in the BC, the percentage of HAP in BC can be estimated to
be 84.8%. This value is slightly higher than that reported by Wilson changed by the dissolution of HAP, at any solution pH, the molar
et al. [29], who found a HAP weight percentage in a BC of 76%. The ratio of Ca2+/PO43 would be constant to 5/3, according to the
difference can be attributed to the cattle bone used as raw material chemical formula of HAP, Ca10(PO4)6OH. The molar ratio of Ca2+/
in the manufacture of the BC. PO43 was 43.1, 1.96 and 0.05 at pH 2.0, 7.0 and 12.0, respectively.
This result corroborated that the calcium concentration in aqueous
3.3. Acidbase stability of BC solution was from the dissolution of both HAP and calcium
carbonate contained in the BC.
The chemical stability of BC was studied by contacting this
adsorbent with acid and basic solutions at different pH during 5 3.4. Textural properties of BC and HAP
days and analyzing the Ca2+ and PO43 concentrations in the
solution. The concentrations of calcium and phosphate in the The textural properties of BC and HAP are shown in Table 1. The
aqueous solution vs. the nal pH is plotted in Fig. 2(a) and (b), textural properties of BC have been reported in various works [32],
respectively. In these gures, it can be observed that the Ca2+ and the values are very similar to those presented in this work. The
concentration is less than 28.2 mg/L at pH > 4 and increased results showed that the BC has a greater surface area than that of
drastically at pH < 3. This behavior is due to the dissolution of HAP the HAP. This is probably due to the main components of BC being
and calcium carbonate in the water solution. Moreover, the PO43 the HAP, Ca10(PO4)6(OH)2 and carbon. Therefore, the increase in
concentration varied from 6 to 13 mg/L in a pH range between the surface area of BC is essentially due to its carbon content. The
4 < pH < 12 and increased drastically at pH < 4, which is a result of surface area of HAP has been reported in the literature [17], and the
the dissolution of the BC. If the Ca2+ concentration was exclusively values are in the range from 45 to 54.2 m2/g.
 N.A. Medellin-Castillo et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 40144021 4017

Table 1 peaks of the HAP happen at the 2u values of 25.98, 31.78, 408, 46.78,
Textural properties and pHPZC of BC and HAP.
and 49.58 [32]. Comparing the XRD pattern of BC to that of HAP, it
Adsorbent Surface Pore volume Average pore pHPZC can be noted that BC is mainly composed of HAP, but the relative
area (m2/g) (cm3/g) diameter (nm) intensities of the characteristic peaks for BC are slightly different
BC 104 0.30 11.1 8.4 from those of the HAP due to the content of HAP in BC.
HAP 62.9 0.26 16.4 7.0
3.6. Surface characterization of BC and HAP

The N2 adsorption isotherms on BC and HAP were shown to be
characteristic of mesoporous solids and corresponded to type IV
isotherm [33]. The average pore diameters of BC and HAP were
11.1 and 16.4 nm, respectively. The pore volume distribution of BC
and HAP revealed that mesopores (2 nm < pore diame-
ter < 50 nm) represented approximately 46 and 80% of the total
pore volume of HAP and BC, respectively.
3.5. XRD analysis of BC and HAP
The XRD patterns of the BC and HAP are shown in Fig. 3a and b,
respectively. The crystalline species of both materials were
identied comparing the characteristic peaks shown in the XRD
pattern with the database of the diffractometer (Journal of
[(Fig._3)TD$IG]Crystallographic Powder Diffraction Spectra). The characteristic
100 HAP
The surface charge of the BC and HAP are illustrated in Fig. 4.
The pHPZC of the HAP and BC were 7.0 and 8.4, respectively. Similar
results have been reported for BC and HAP [3436]. The pHPZC of
the BC was basic because its concentration of basic sites was higher
than that of acid sites [5]. As noted in Fig. 4, the surface charge of
the BC was increased by raising the ionic strength, but the pHPZC of
BC was not dependent on the ionic strength.
It was shown that the main constituent of BC was HAP and the
surface charge of the BC was mainly due to the interactions
between the HAP surface and the ions in the water solution. The
functional groups of the HAP surface that affect its surface charge
are the phosphates, BBP-OH, and the hydroxyls, BBCa-OH. The
positive charge of the BC surface was due to the following
protonation reactions:
BBP-OH H ! BBPOH2

BBCa-OH H ! BBCa-OH2

80 Bone Char On the other hand, the negative charge of the BC surface was
originated by the following deprotonation reactions:
Relative Intensity

60 BBP-OH ! BBPO H

HAP BBCa-OH ! BBCa-O H

40
HAP where BB represents the BC surface. Thus, the protonation reactions
HAP HAP
predominated at pH < pHPZC, although the deprotonation reac-
20 tions occurred at pH > pHPZC.

3.7. Adsorption isotherm

0
20 30 40 50 60 70 80 90 The Freundlich, Langmuir, and Prausnitz-Radke isotherm
2 models were tted to the experimental adsorption equilibrium
a) data of uoride on BC and HAP. These isotherm models can be
[(Fig._4)TD$IG]
100 HAP

HAP
80
Relative Intensity

Hydroxyapatite

60

HAP
40
HAP

HAP
20

0
20 30 40 50 60 70 80 90
2
b)
Fig. 3. XRD patterns of the BC (a) and the HAP (b). Fig. 4. Surface charge distribution of BC and HAP.
4018 N.A. Medellin-Castillo et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 40144021

Table 2
Values of the parameters for the Langmuir, Freundlich and Prausnitz-Radke adsorption isotherms.

Adsorbent pH Freundlich Langmuir Prausnitz-Radke

1/n 1/n1 b
k (L /mg g) 1/n %D K (L/mg) qm (mg/g) %D a (L/g) b (L/mg) b %D

BC 5 3.96 0.31 6.86 1.55 7.74 16.4 36.9 7.55 0.79 9.54
7 2.72 0.29 4.39 1.22 5.44 16.0 42.0 3.07 0.76 2.15

HAP 5 5.15 0.35 17.1 1.32 10.9 15.7 64.4 11.0 0.70 10.5
7 2.37 0.48 11.3 0.18 11.1 16.9 56.4 23.0 0.53 7.56

represented by the subsequent mathematical relationships:
q kC 1=n
q KC
q m
1 KC
aC
q (3)
1 bC b
where C (mg/L) is the concentration of uoride at equilibrium and q
(mg/g) is the mass of uoride adsorbed per mass of adsorbent. The
parameters K (L/mg) and qm (mg/g) are the Langmuir constants
related to the energy of adsorption and maximum adsorption
capacity, respectively. The parameters k (L1/n mg11/n g1) and n
are the Freundlich constants related to the adsorption capacity and
b
intensity. The parameters a (L/g), b (L/mg) and b are the
Prausnitz-Radke isotherm constants.
The isotherm constants were estimated by a least-squares
method based on an optimization algorithm and the values are
shown in Table 2 along with the average absolute percentage
deviation, %D, which was computed from the following equation:
 
N  
1X qexp  qcal 
%D    100 (4)
N  qexp 
i1
where N is the number of experimental data points, qexp (mg/g) is
the experimental mass of uoride adsorbed, and qcal (mg/g) is the
mass of uoride adsorbed predicted with the adsorption isotherm
model.
The experimental adsorption equilibrium data were satisfacto-
rily interpreted by the three isotherm models since the average
percentage deviations were less than 10.5, 16.9, and 17.1% for the
Prausnitz-Radke, Langmuir and Freundlich isotherms, correspon-
dently. As shown in Table 2, the Prausnitz-Radke isotherm best
the uoride in aqueous solution is mostly adsorbed on the HAP
contained in the BC and not by the other constituents of BC.
(1)
3.9. Effect of pH on the capacity of BC for adsorbing uoride
(2) In a previous work [5], it was reported that the capacity of BC for
adsorbing uoride was signicantly dependent on the solution pH
and decreased considerably while raising the pH from 3 to 11.
Similar results were found in this work and are displayed in Fig. 5.
This behavior was attributed to the electrostatic interactions
between uoride ions in water solution and the surface charge of
BC. The surface of BC was positively charged at pH < pHPZC = 8.4
and the F ions in solution were attracted to the surface of BC. The
mass of uoride adsorbed decreased by reducing the pH from 3 to
8.4 because the surface charge of BC decreased by raising the pH,
this behavior is depicted in Fig. 4.
Additional experiments were carried out to investigate the
variation of the solution pH during the adsorption of uoride on
the BC. The experiments consisted on performing adsorption
experiments as already described using a BC mass of 1.0 g, various
initial uoride concentrations (1, 5, 10, and 20 mg/L) and various
initial pH values (3, 5, 9, and 12). During these experiments, the pH
of the solution was not kept constant and the nal pH was recorded
along with the mass of uoride adsorbed.
As expected, the results revealed that the uoride adsorption
capacity of BC decreased when the pH increased independently on
the initial concentration of uoride (Fig. 6a). Additionally, it was
observed that the solution pH varied during the adsorption of
uoride on BC. The initial pHs of the solutions were approximately
3, 5, 7, 9 and 12 and the nal pH of the solutions presented an
average value of 6.9, 7.9, 7.9, 8.1 and 11.8, respectively. The
[(Fig._5)TD$IG]
14
BC, pH = 5
BC, pH = 7
Mass of fluoride adsorbed, mg/g

tted the data for BC and HAP since, in the 3 of the 4 isotherm cases 12
HAP, pH = 5
shown in Table 2, the %D of the Prausnitz-Radke isotherm was HAP, pH = 7
lower than the %D of Langmuir and Freundlich isotherms. This can 10
be explained by recalling that the Prausnitz-Radke model is a
three-parameter isotherm whereas the Langmuir and Freundlich
models are two-parameter isotherms. 8

3.8. Effect of the presence of HAP on the adsorption capacity of BC 6

The experimental adsorption equilibrium data of uoride on BC

4
and HAP are shown in Fig. 5 at T = 25 8C and pH = 5.0 and 7.0. It can
be noted that the uoride adsorption on HAP is greater than that of
the BC. At an equilibrium uoride concentration of 1.5 mg/L, the 2
ratio between the mass of uoride adsorbed on the BC and that on
the HAP, qBC/qHAP is 0.77 and 0.95 at pH = 5.0 and 7.0, respectively, 0
and at an equilibrium uoride concentration of 4.0 mg/L, the ratio 0 2 4 6 8 10 12 14
qBC/qHAP is 0.73 and 0.81 at pH = 5.0 and 7.0, correspondingly.
Concentration of fluoride at equilibrium, mg/L
These ratios are very close to the weight fraction of HAP in the BC,
which is 0.848 (see Section 3.2). This reveals that the uoride Fig. 5. Adsorption isotherms of uoride on BC and HAP. T = 25 8C and pH = 5.0
adsorption capacity of BC is mostly due to its content of HAP. Thus, and 7.0.
[(Fig._6)TD$IG] N.A. Medellin-Castillo et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 40144021
Fig. 6. Effect of initial pH and initial concentration of uoride on the adsorption
capacity of BC (a) and the nal pH (b).
variation of the solution pH during adsorption is shown in Fig. 6b,
and the solution pH increased when the experiments were
performed at a pH < pHPZC, while it remained almost constant
when the experiments were carried out at a pH > pHPZC. At the
initial pH of 3 and 5, the pH increased drastically during the
adsorption and the magnitude of the increase was almost the same
without and with uoride in the solution. In other words the
variation of pH was independent on the initial concentration of
uoride. It is important to mention that the amount of uoride
adsorbed at the initial pH of 3 and 5 is much greater than that at the
other pH values. This implies that the pH variation cannot be
attributed to the adsorption of uoride. Thus, the OH ions on the
BC surface were not exchanged by the F ions from the solution
since the nal pH of the solution without uoride was almost the
same as the nal pH of the solution with uoride.
The pH variation during the adsorption of uoride can be
explained recalling that the protons are released from or bound to
the BC surface due to the protonation/deprotonation reactions
described previously. Furthermore, the solution pH can be also
4019
altered by the dissolution of the carbonate and HAP contained in
the BC.
3.10. Adsorption mechanism
Abe et al. [18] assumed that OH and PO43 ions in BC were the
only ionic species that could be exchanged by uoride ions, and
concluded that the ion exchange between uoride ions from the
solution and the OH ions on the BC was not relevant to the
adsorption of uoride. This conclusion is in agreement with the
result argued in the previous section.
Furthermore, Abe et al. [18] proposed that the ion exchange of
uoride ions with the PO43 ions represented between 18 and 42%
of the uoride adsorbed. In order to corroborate this assumption,
the amount of phosphate released from BC during uoride
adsorption and its variation with the nal pH of the solution
and the initial concentration of uoride was investigated and the
results are graphed in Fig. 7a. In this gure, it can be observed that
independently of the nal pH, a certain amount of phosphate was
always released to the solution. The phosphate released from BC
was supposed to be from the dissolution of BC and the uoride ion
exchange. In this last mechanism, the uoride ions were
transferred from the solution to the surface of BC and the
phosphate ions were released from the surface of BC to the
solution. However, in some experiments, the mass of phosphate
released when no uoride was present, was even higher than that
of phosphate released when the uoride was present in the
solution (see Fig. 7a).
The dependence of the milliequivalents of phosphate released,
QP, with respect to the milliequivalents of uoride adsorbed, QF, is
shown in Fig. 7b. If the adsorption of uoride on BC was due to ion
exchange of phosphate, the QF must be equal to QP. This condition
is represented by the straight line (QP = QF) plotted in Fig. 7b. The
QP is greater than the QF when the QF is below 0.07 mequiv., and the
opposite occurs when the QF is above 0.07 mequiv. The data
graphed in Fig. 7b indicated that the ratio of QP/QF ranged from 0.34
to 9.5. There was not relationship between the QF and the QP.
Hence, most of the phosphate ions in the solution were dissolved
from the BC, but it cannot be argued that the amount of phosphate
was exchanged by uoride, as it was previously concluded [18].
The adsorption of uoride can be attributed to electrostatic
interactions between the surface charge of BC and uoride ions in
the aqueous solution and it can be represented with the following
reactions:
BBCa-OH2 F ! BBCa-OH2 F
BBPOH2 F ! BBPOH2 F
In the above mechanisms, the interaction between the surface
complexes BBCa-OH2+ and BBPOH2+ and the F do not lead to a
chemical reaction or chemisorption because it has been demon-
strated that the adsorption of F on BC was reversible [5].
3.11. Effect of competing anions upon the adsorption of uoride on BC
In a previous study [5], the BC was tested to remove uoride
from a sample of actual drinking water and the capacity of BC for
removing uoride was slightly reduced due to the presence of
competing ions in the drinking water. The sample of drinking
water was from the city of San Luis Potosi, Mexico. It is important
to investigate the competitive adsorption of Cl, NO2, NO3,
CO32, HCO3, and SO42, which are among the most frequently
anions detected in drinking water.
The individual adsorption equilibrium data of Cl, NO2, NO3,
CO32, HCO3, and SO42 on BC are depicted in Fig. 8. Except for the
experimental data of CO32, the Freundlich isotherm tted
[(Fig._7)TD$IG]
4020 [(Fig._8)TD$IG]
N.A. Medellin-Castillo et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 40144021

0.24
Initial concentration of F
Amount of phosphate released, meq

0.0 mg/L
0.20 1.0 mg/L
5.0 mg/L
10.0 mg/L
0.16 20.0 mg/L

0.12

0.08

0.04

0.00
6 7 8 9 10 11 12
Final pH
Fig. 8. Individual adsorption isotherms of anions on BC at T = 25 8C and without
a) control of pH.

0.30
Initial concentration of F
Amount of phosphate released, meq

1.0 mg/L
of F in a wide concentration range. In the case of the CO32, the
0.25 5.0 mg/L
uptake of CO32 was dependent on the concentration of F. The
10 mg/L
20 mg/L uptake of CO32 was much less than that of F at concentrations of
0.20 CO32 at equilibrium below 0.2 mequiv./L; however, the uptake of
CO32 was comparable to that of F at concentrations greater than
0.3 mequiv./L. In other words, the CO32 anions did not compete
0.15 with the uoride ions for the active sites of the BC when the
concentration of CO32 at equilibrium was less than 0.2 mequiv./L.
In a previous work, it was reported that the presence of CO32 did
0.10 not affect the uoride adsorption capacity of BC [5] when the BC
was tested in removing uoride from drinking water drawn from a
0.05 well in San Luis Potosi, Mexico, and the concentration of CO32 was
0.03 mequiv./L. The results of this work proved that the CO32 did
not affect the uoride capacity of BC because the concentration of
0.00 CO32 was below 0.2 mequiv./L.
0.00 0.05 0.10 0.15 0.20 0.25 0.30 From the above arguing, the Cl ions could compete against the
Amount of fluoride adsorbed, meq F for the active sites of BC. The competitive adsorption of Cl and


F was investigated by determining the adsorption equilibrium of

b) uoride at various initial concentrations of Cl. The mass of F
adsorbed in the presence of Cl is graphed in Fig. 9, and it can be
Fig. 7. Effect of initial pH and amount of uoride adsorbed on the amount of
phosphate released from BC to the solution.
observed that the capacity of BC for adsorbing F varies slightly
when Cl ions are present in the aqueous solution. Similar result
was found by Medellin-Castillo et al. [5]. Furthermore, the uoride
adsorption capacity of BC does not vary with a trend related to the
plausibly well the experimental adsorption equilibrium data of the initial concentration of Cl since the adsorption capacity of BC
anions from aqueous solution, and the Freundlich constants as well increased or decreased slightly in relation to the uoride
as the average absolute percentage deviation, %D, are given in adsorption isotherm. The reason of this behavior is that the
Table 3. The adsorption equilibrium of CO32 presented a afnity of the F toward BC is much greater than that of the Cl.
sigmoidal shape (Fig. 8), and this unusual behavior could not be Thus, the F ions do not compete against Cl ions for the basic sites
represented by the Freundlich isotherm. of BC.
As seen in Fig. 8, the anions NO2, NO3, and SO42 were slightly As seen in Fig. 6, the anion afnity order toward BC decreased in
adsorbed on BC, whereas the uptake of Cl was very similar to that the following order: F > Cl > CO32 > NO2  NO3  HCO3 
SO42 for the concentrations of anions less than 0.3 mequiv./L.
Several factors inuence the anion afnity order, among the most
Table 3 important are hydrated ionic radius, acid dissociation constant
Freundlich isotherm parameters for the adsorption of Cl, NO2, NO3, and SO42
and ionic charge [37]. In the case of BC, the accessibility of the
from aqueous solution on BC at T = 25 8C and without controlling the solution pH.
anions to the BC pores did not affect the anion afnity because
Anion k (L1/n mequiv.11/n g1) 1/n %D the average pore diameter of BC (11.1 nm) was at least 28 times
Cl 0.60 0.89 6.44 greater than the hydrated ionic radii of the anions, which ranged
NO2 0.042 0.62 14.1 from 0.332 to 0.394 nm [38]. Much more experimental informa-
NO3 0.08 1.25 17.8
tion is required to conduct a detail analysis of the anion afnity
SO42 0.07 0.88 24.2
order.
[(Fig._9)TD$IG] N.A. Medellin-Castillo et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 40144021 4021

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