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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


alumina [11], natural minerals such as laterite, zeolite, and
The impact of uoride concentration in drinking water onto caolinite [1214], nanomaterials [15], carbonaceous materials
human health has been extensively studied and reviewed in [7,16], bone char (BC) and hydroxyapatite (HAP) [5,17,18].
various works [1,2]. A concentration of uoride between 0.5 and BC is manufactured by the carbonization of cattle bones and
1.5 mg/L is essential for the human body, especially in preventing contains around 10% carbon and 90% HAP [19]. The adsorption of
the incidence of dental caries; however, long term ingestion of uoride on BC has been investigated in various works [5,6,18,20].
water with excess amount of uoride, above 2 mg/L, can cause In a previous work [5], it was shown that the capacity of BC for
diseases such as dental and skeletal uorosis, masculine infertility adsorbing uoride was higher than those of activated alumina and
and cancer [2]. activated carbon. Furthermore, the effect of solution pH and
Several treatment processes have been applied to remove temperature on the adsorption capacity of uoride onto BC was
excess uoride from drinking water. Some of the common investigated and it was found that the maximum adsorption took
processes are chemical precipitation [3], ion exchange [4], place at pH 3 and decreased nearly 20 times by increasing the pH
adsorption [5,6], reverse osmosis [4], electrodialysis [7] and from 3 to 12. This behavior was attributed to the electrostatic
nanoltration [8]. Adsorption is the most suitable process for interactions between the surface of BC and uoride ions in
drinking water treatment because it is relatively simple, economic, solution. The adsorption capacity was not inuenced by tempera-
and appropriate for small communities [9,10]. ture in the range from 15 to 35 8C.
During the past 10 years, extensive research has been carried The anions HCO3, CO32, Cl, NO3, NO2, and SO42 are
out to nd both low-cost and high capacity adsorbents for the commonly found in drinking water and these anions can compete
removal of uoride from drinking water. A wide range of 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
* Corresponding author. Tel.: +52 444 826 2440; fax: +52 444 826 2372. been investigated in detail. Due to the high toxicity of As(V), the
E-mail address: rlr@uaslp.mx (R. Leyva-Ramos). 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 4015

solution on BC has been studied because it is well documented that diffractometer, Rigaku, model DMAX 2000. The textural properties
uoride and As(V) may be co-occurring in drinking waters in of both materials (specic area, pore volume and average pore
several countries of Latin America [21]. Mlilo et al. [22] determined diameter) were determined by the N2-BET method using a surface
the adsorption isotherm of uoride on BC with and without As(V) area and porosimetry analyzer, Micromeritics, model ASAP 2010.
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. 2.3. Determination of the concentrations of the anions in water
Calcium hydroxyapatite, Ca10(PO4)6(OH)2, is an important solution
inorganic material in biology and chemistry [2325]. Its structure,
ion exchange capacity, adsorption afnity, and its capacity to bond The uoride concentration in an aqueous solution was
with organic molecules of different sizes, have attracted much determined by a potentiometric method using a potentiometer,
attention in the last two decades. The adsorption of heavy metals, Orion, model SA720, and a selective electrode for uoride ion. This
Pb2+, Cu2+ and Cd2+, from aqueous solutions on HAP has been method allowed the determination of uoride concentrations in
attributed to the ion exchange of Ca2+ on the HAP by the metal the range from 0.1 to 10 mg/L. The uoride calibration curves were
cation in solution [26,27]. Adsorption of uoride on this adsorbent prepared with standard solutions of uoride. Further details of the
has been studied in several works [17,27] and it has been found analytical method can be found elsewhere [28,30].
that the mechanism of uoride adsorption is due to electrostatic The concentrations of bicarbonate (HCO3), carbonate (CO32),
attractions and ion exchange processes. chloride (Cl), nitrate (NO3), nitrite (NO2), phosphate (PO43),
BC is mainly composed of HAP and it is essential to evaluate the and sulfate (SO42) in water solutions were determined using the
contribution of this mineral to the adsorption of uoride on BC. methods recommended by APHA [30].
Thus, the main objective of this research was to evaluate the role of
HAP on the capacity of BC for adsorbing uoride from aqueous 2.4. Adsorption equilibrium data
solution. Furthermore, the mechanism of uoride adsorption on BC
would be elucidated, and the effect of the presence of anions, Experimental adsorption equilibrium data were obtained as
commonly found in natural waters, on the uoride adsorption follows. A portion of 490 mL of an aqueous solution of a known
capacity of BC would be analyzed in detail. initial concentration of uoride or HCO3, CO32, Cl, NO3, NO2,
and SO42 was added to the batch adsorber. A given mass of BC or
2. Materials and methods 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
2.1. Bone char and hydroxyapatite concentrations of uoride varied from 1 to 20 mg/L. The adsorber
was placed in a constant temperature water bath and the solution
In this work, the granular BC used is commercially known as Fija was continuously mixed by a magnetic stirrer located just below
Fluor and is manufactured from cattle bones by APELSA, the water bath. The solution was left in contact with the BC or HAP
Guadalajara, Mexico. The BC was sieved to an average particle until equilibrium was reached, which took between 5 and 7 days.
diameter of 0.79 mm, washed repeatedly with deionized water, The solution pH was measured periodically with a pH-meter and
dried in an oven at 100 8C for 24 h, and stored in plastic containers. kept constant by adding few drops of 0.01 and 0.05 HNO3 or NaOH
Analytical grade hydroxyapatite (purity < 99% according to the solutions as required. The total volume added of HNO3 or NaOH
manufacturer, SigmaAldrich, CAS Number: 1306-06-5) was also solutions was recorded and considered in the mass balance. The
used in this study. solution was sampled at specic time intervals and the concen-
tration of uoride was determined for each sample. Equilibrium
2.2. Characterization of bone char and hydroxyapatite was reached when the concentrations of two consecutive samples
did not change over time. The mass of uoride or HCO3, CO32,
The contents of carbon, hydrogen and nitrogen on BC were Cl, NO3, NO2, and SO42 adsorbed at equilibrium was calculated
determined using an Elemental Analyzer, Fisons Carlo Erba, EA- by performing a mass balance of uoride or other anions.
1108. The phosphorus weight percentage of BC was evaluated by The effect of coexisting or competing anions such as chloride on
Inductively Coupled Plasma (ICP) Atomic Emission Spectroscopy the uoride adsorption capacity of BC was carried out by
using a Thermo Jarrel Ash, model IRIS/AP, instrument. The sample determining the adsorption equilibrium data of uoride at
was prepared for ICP analysis using the method described by pH = 7.0 and T = 25 8C, and varying the initial concentration of
Medellin-Castillo [28]. chloride from 20 to 80 mg/L during the adsorption of uoride.
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 3. Results and discussion
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 3.1. Morphology of BC and HAP
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 As seen in Fig. 1(a), the forms and shapes of the BC particles are
0.1 N HNO3 and NaOH solutions. The BC and acid solution were left very irregular and its surface is fractured, rough and porous. The
in contact for 7 days and periodically mixed in an orbital shaker, distribution of the particle sizes is not uniform. The morphology of
and the nal pH of the acid solution was measured. Moreover, the the HAP particles is shown in Fig. 1(b), and the particles presented
concentration of Ca2+ and PO43 dissolved in the acid solutions a layered shape that is typical of HAP.
were determined by atomic absorption spectroscopy and atomic
emission spectroscopy. 3.2. Chemical composition
The morphology of BC and HAP particles were observed by
means of a scanning electron microscope (SEM), Philips, model XL- The elemental analysis of BC showed that the weight
30. The microscope was equipped with an energy dispersive Si(Li) percentages of nitrogen, hydrogen and carbon were 0.95, 0.52
detector EDAX DX4 for microanalysis. and 6.31%, correspondingly. The carbon content is very similar to
X-ray diffraction (XRD) analysis was used to identify the the value reported by Wilson et al. [31] for a BC manufactured from
crystalline species present in both adsorbents employing an X-ray 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 The surface charge of the BC and HAP are illustrated in Fig. 4.
characteristic of mesoporous solids and corresponded to type IV The pHPZC of the HAP and BC were 7.0 and 8.4, respectively. Similar
isotherm [33]. The average pore diameters of BC and HAP were results have been reported for BC and HAP [3436]. The pHPZC of
11.1 and 16.4 nm, respectively. The pore volume distribution of BC the BC was basic because its concentration of basic sites was higher
and HAP revealed that mesopores (2 nm < pore diame- than that of acid sites [5]. As noted in Fig. 4, the surface charge of
ter < 50 nm) represented approximately 46 and 80% of the total the BC was increased by raising the ionic strength, but the pHPZC of
pore volume of HAP and BC, respectively. BC was not dependent on the ionic strength.
It was shown that the main constituent of BC was HAP and the
3.5. XRD analysis of BC and HAP surface charge of the BC was mainly due to the interactions
between the HAP surface and the ions in the water solution. The
The XRD patterns of the BC and HAP are shown in Fig. 3a and b, functional groups of the HAP surface that affect its surface charge
respectively. The crystalline species of both materials were are the phosphates, BBP-OH, and the hydroxyls, BBCa-OH. The
identied comparing the characteristic peaks shown in the XRD positive charge of the BC surface was due to the following
pattern with the database of the diffractometer (Journal of protonation reactions:
[(Fig._3)TD$IG]Crystallographic Powder Diffraction Spectra). The characteristic
BBP-OH H ! BBPOH2
100 HAP

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: the uoride in aqueous solution is mostly adsorbed on the HAP
contained in the BC and not by the other constituents of BC.
q kC 1=n (1)
3.9. Effect of pH on the capacity of BC for adsorbing uoride
q KC
q m (2) In a previous work [5], it was reported that the capacity of BC for
1 KC
adsorbing uoride was signicantly dependent on the solution pH
aC and decreased considerably while raising the pH from 3 to 11.
q (3) Similar results were found in this work and are displayed in Fig. 5.
1 bC b
This behavior was attributed to the electrostatic interactions
where C (mg/L) is the concentration of uoride at equilibrium and q between uoride ions in water solution and the surface charge of
(mg/g) is the mass of uoride adsorbed per mass of adsorbent. The BC. The surface of BC was positively charged at pH < pHPZC = 8.4
parameters K (L/mg) and qm (mg/g) are the Langmuir constants and the F ions in solution were attracted to the surface of BC. The
related to the energy of adsorption and maximum adsorption mass of uoride adsorbed decreased by reducing the pH from 3 to
capacity, respectively. The parameters k (L1/n mg11/n g1) and n 8.4 because the surface charge of BC decreased by raising the pH,
are the Freundlich constants related to the adsorption capacity and this behavior is depicted in Fig. 4.
b
intensity. The parameters a (L/g), b (L/mg) and b are the Additional experiments were carried out to investigate the
Prausnitz-Radke isotherm constants. variation of the solution pH during the adsorption of uoride on
The isotherm constants were estimated by a least-squares the BC. The experiments consisted on performing adsorption
method based on an optimization algorithm and the values are experiments as already described using a BC mass of 1.0 g, various
shown in Table 2 along with the average absolute percentage initial uoride concentrations (1, 5, 10, and 20 mg/L) and various
deviation, %D, which was computed from the following equation: 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
N  
1X qexp  qcal  along with the mass of uoride adsorbed.
%D    100 (4)
N  qexp  As expected, the results revealed that the uoride adsorption
i1
capacity of BC decreased when the pH increased independently on
where N is the number of experimental data points, qexp (mg/g) is the initial concentration of uoride (Fig. 6a). Additionally, it was
the experimental mass of uoride adsorbed, and qcal (mg/g) is the observed that the solution pH varied during the adsorption of
mass of uoride adsorbed predicted with the adsorption isotherm uoride on BC. The initial pHs of the solutions were approximately
model. 3, 5, 7, 9 and 12 and the nal pH of the solutions presented an
The experimental adsorption equilibrium data were satisfacto- average value of 6.9, 7.9, 7.9, 8.1 and 11.8, respectively. The
rily interpreted by the three isotherm models since the average [(Fig._5)TD$IG]
percentage deviations were less than 10.5, 16.9, and 17.1% for the
Prausnitz-Radke, Langmuir and Freundlich isotherms, correspon- 14
BC, pH = 5
dently. As shown in Table 2, the Prausnitz-Radke isotherm best
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 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
Fig. 6. Effect of initial pH and initial concentration of uoride on the adsorption
reactions:
capacity of BC (a) and the nal pH (b).
BBCa-OH2 F ! BBCa-OH2 F

BBPOH2 F ! BBPOH2 F
variation of the solution pH during adsorption is shown in Fig. 6b,
and the solution pH increased when the experiments were In the above mechanisms, the interaction between the surface
performed at a pH < pHPZC, while it remained almost constant complexes BBCa-OH2+ and BBPOH2+ and the F do not lead to a
when the experiments were carried out at a pH > pHPZC. At the chemical reaction or chemisorption because it has been demon-
initial pH of 3 and 5, the pH increased drastically during the strated that the adsorption of F on BC was reversible [5].
adsorption and the magnitude of the increase was almost the same
without and with uoride in the solution. In other words the 3.11. Effect of competing anions upon the adsorption of uoride on BC
variation of pH was independent on the initial concentration of
uoride. It is important to mention that the amount of uoride In a previous study [5], the BC was tested to remove uoride
adsorbed at the initial pH of 3 and 5 is much greater than that at the from a sample of actual drinking water and the capacity of BC for
other pH values. This implies that the pH variation cannot be removing uoride was slightly reduced due to the presence of
attributed to the adsorption of uoride. Thus, the OH ions on the competing ions in the drinking water. The sample of drinking
BC surface were not exchanged by the F ions from the solution water was from the city of San Luis Potosi, Mexico. It is important
since the nal pH of the solution without uoride was almost the to investigate the competitive adsorption of Cl, NO2, NO3,
same as the nal pH of the solution with uoride. CO32, HCO3, and SO42, which are among the most frequently
The pH variation during the adsorption of uoride can be anions detected in drinking water.
explained recalling that the protons are released from or bound to The individual adsorption equilibrium data of Cl, NO2, NO3,
the BC surface due to the protonation/deprotonation reactions CO32, HCO3, and SO42 on BC are depicted in Fig. 8. Except for the
described previously. Furthermore, the solution pH can be also 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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