Chemical Engineering Journal 200–202 (2012) 471–479

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Chemical Engineering Journal

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Lead sorption properties of nanohydroxyapatite–alginate composite adsorbents

Fahimeh Googerdchian a, Ahmad Moheb a,⇑, Rahmatollah Emadi b
a
Department of Chemical Engineering, Isfahan University of Technology, Isfahan 8415683111, Iran
b
Department of Materials Engineering, Isfahan University of Technology, Isfahan 8415683111, Iran

h i g h l i g h t s

" Composite adsorbents were prepared from natural hydroxyapatite and alginate.
+2
" The adsorbents were used for Pb removal from aqueous solutions.
" Film type adsorbents had better performance than bead shape adsorbents.
" Removal performance improved by increasing nHAP content of adsorbent films.
" Adsorption capacity of the adsorbents was higher than other composite adsorbents made by other researchers.

a r t i c l e i n f o a b s t r a c t

Article history: In the present work bio-composite adsorbents were prepared by incorporating natural nano-sized
Received 13 March 2012 hydroxyapatite (nHAp) into alginate polymer. Bead and film form composite adsorbents with two differ-
Received in revised form 19 June 2012 ent compositions were used for the Pb2+ removal from aqueous solutions. The adsorption results were
Accepted 20 June 2012
compared with the results obtained by using pure alginate films and beads as well as pure nHAp particles.
Available online 28 June 2012
In case of bead form adsorbents, incorporating nHAp particles into alginate decreased the adsorption
capacity. SEM and EDX analysis proved that it was due to agglomeration of nHAP particles on the bead sur-
Keywords:
face and reduction in Pb2+ diffusion in the beads. However, composite films had greater sorption capacities
Pb2+ removal
Hydroxyapatite
than pure alginate film and nHAp powder. Maximum equilibrium capacity of 270.3 mg g1 was obtained
Composite adsorbent after 6 h for composite film from adsorbent containing 50 wt% of nHAp. Kinetics studies showed that the
Alginate pseudo-second-order kinetic model was able to describe the dynamic behavior of the adsorption process
Adsorption capacity by composite adsorbents used in this work. Also the Langmuir isotherm model is very well fitted to the
equilibrium data. The mechanism of Pb2+ adsorption by the composite adsorbents was described. Finally,
the film type nHAp–alginate composite adsorbents were found to be promising for lead ions removal from
aqueous solutions.
Ó 2012 Published by Elsevier B.V.

1. Introduction Conventional methods for removal of heavy metal ions from

Heavy metal containing pollutants are released to environment
by different industrial activities such as tanneries, electronics, min-
ing, electroplating and petrochemical industrial processes. Heavy
metals are not biodegradable and usually tend to accumulate in
organisms, causing numerous diseases and disorders. Therefore
even low levels of heavy metals in contaminated soils and waters
pose a threat to humans, animals and plants. Lead is a toxic heavy
metal which is extensively used in different industries and is
widely spread in the environment due to careless disposal methods
used by the industries. This results in lead contamination of soils
and waters, makes lead removal from contaminated natural
resources an important issue [1,2].
⇑ Corresponding author. Tel.: +98 3113915618; fax: +98 3113912677.
E-mail address: ahmad@cc.iut.ac.ir (A. Moheb).
contaminated waters include filtration, adsorption by activated
carbon, reverse osmosis, solvent extraction, chemical precipitation
and membrane separation techniques. Most of these methods have
limitations such as high capital and operational cost, low efficiency,
sensitive operating conditions and production of secondary
sludges. Activated carbon is the most common used adsorbent for
heavy metals removal, however it is relatively expensive because
of its high production costs [3,4].
Adsorption by a low-cost adsorbent is known as an economic
and efficient method for heavy metal decontamination of the
aqueous solutions. Thus many researchers have focused their
research work on the preparation of new efficient and cost-effective
adsorbents from natural or biological materials or industrial
wastes. One of the promising materials, which can fulfill the desired
properties for this purpose, is natural or biogenic hydroxyapatite
which is prepared from animal bones wastes. Hydroxyapatite

1385-8947/$ - see front matter Ó 2012 Published by Elsevier B.V.

http://dx.doi.org/10.1016/j.cej.2012.06.084
472 F. Googerdchian et al. / Chemical Engineering Journal 200–202 (2012) 471–479
[Ca10(PO4)6(OH)2, HAp] is a major inorganic component of bones
and teeth; thus animal bones represent a natural source of biogenic
apatite. For many years HAp has been of interest by bio-material
scientists and it is one of the most widely used bio-materials for
dental and orthopedic applications [5]. Also, HAp has shown high
sorption capacity for heavy metal ions and radionuclides [6–8].
HAp is produced either by normal calcinations of bio-wastes
such as fish bones, bovine bones, and pig bones as natural sources
or by synthesis processes. Synthesis processes might be either
complicated or expensive due to using high purity reagents. As a
result, recent production of hydroxyapatite from natural sources
has gained much attention by the researchers [9–11].
Sorption of heavy metals on HAp has been extensively studied.
It has previously shown by researchers that HAp had the greatest
sorption capacity for Pb compared to other heavy metals and it
could effectively immobilize Pb ions existing in the contaminated
soils and waters [7,8,12,13]. High sorption capacity of HAp for Pb
is due to the different dominant sorption mechanism for Pb, disso-
lution–precipitation, whose driving force is rapid dissolution of
HAp followed by precipitation of less soluble hydroxypyromorph-
ite (HPy) [12,14–17].
HAp is mostly prepared in powder form, which limits its
applications under aqueous conditions. Insufficient strength and
relatively weak mechanical properties of prepared granulated
HAp make its applications in adsorption columns almost impossi-
ble; thus, there is a necessity to immobilize HAp powders into a
certain form. Making HAp- polymer composite adsorbents is an
emerging method.
Recently different polymers such as polyurethane, poly(acryl-
amide), chitin/chitosan, cellulose and poly(vinyl alcohol) have
been used to immobilize HAp powders and adsorption capabilities
of HAp-polymer composites for heavy metals removal from aque-
ous solutions have been evaluated by researchers [18–25]. More-
over, biocomposites made from both organic and inorganic
components, have been introduced as immobilizing agents due
to their improved mechanical, thermal, optical or chemical proper-
ties as well as their biocompatibility and biodegradability. Among
these, alginate is a biopolymer with special properties such as non-
toxicity, biocompatibility and biodegradability, which make it
appropriate to be employed as an adsorbent. Alginate is a linear
copolymer of a-l-guluronate (G) and a-dmannuronate (M), which
is extracted mainly from brown seaweeds and various bacteria
(e.g. Pseudomonas spp. and Azotobacter spp.). This biopolymer
has been widely used both as an immobilization material and as
a biosorbent for several heavy metals and some radionuclides.
Sorption capability of alginate is due to its carboxyl groups which
are capable of binding with heavy metal cations. Depending on the
type of the algal species used for the extraction of alginic acid, both
molecular weight and M/G ratio of alginate have wide variations.
The capability of this copolymer to form stable biodegradable gels
in the presence of divalent cations can be attributed to the simul-
taneous binding of the divalent cations such as Ca2+ to different
chains of a-l-guluronate blocks (G-blocks) as an ‘‘egg box’’ model.
According to this model Ca2+ ions are localized into electronegative
cavities, like eggs in an egg box [26,27].
Due to its gelation property, cross-linked alginate has been
mostly used as a matrix for the immobilization of microbial cells
and several enzymes via entrapment. Recently Ca–alginate has
been utilized for immobilization of some other materials such as
activated carbon, chitosan, goethite and zeolite for waste water
treatment applications. Entrapment of microbial cells or inorganic
materials in an alginate support improves microbial cell perfor-
mance, increases adsorptive capacity of the biosorbent for heavy
metals removal, and makes it possible to simultaneously remove
heavy metal ions and organic compounds from wastewaters
[28–35].
HAp–alginate composite has been extensively investigated by
scientists as a promising material for biomedical applications such
as the fabrication of tissue scaffolds and controlled drug-release,
due to its unique properties [36–40].
The work of Mavropoulos et al. is the only published report on
the application of HAp–alginate composite for water treatment. In
their work, they briefly investigate capability of the HAp–alginate
composite bead form adsorbents for removal of lead and cadmium
ions existing in simulated gastric fluid [41]. It seems that more pre-
cise and comprehensive investigations are required to inspect
application of HAp–alginate composite as an adsorbent for heavy
metals removal. Hence, the subject of this study was preparation
of nHAp–alginate composite adsorbents and investigation on their
sorption properties for Pb2+ removal from aqueous solutions. The
adsorbents were made with two different values of nHAp content
each in two different forms of bead and film. The effects of compo-
sition and shape of nHAp–alginate composite adsorbents on Pb2+
removal capacity of the adsorbents were investigated.
The results were compared with the results obtained by using
pure alginate film and bead as well as nHAp powder adsorbents.
Also, governing kinetics and isotherm models were investigated.
2. Experimental procedures
2.1. Materials
Natural nano HAp powder (nHAp) was prepared from bovine
bones by heating the bone at 750 °C for 4 h followed by 2 h ball mill-
ing using a high energy planetary ball mill. The prepared nHAp pow-
der was characterized by XRD analysis method and TEM imaging.
The results are presented in Section 3.1. Reagent grade sodium algi-
nate and calcium chloride were purchased from Acros and Merck
companies, respectively. Lead nitrate [Pb(NO3)2] was supplied by
Riedel-de Haen company. It was used for preparing aqueous Pb2+
solutions. Also, potassium hydroxide and nitric acid solutions were
used for adjusting the initial pH of lead nitrate solutions.
2.2. Preparation of nHAp–alginate composite adsorbents
nHAp–alginate composite adsorbents were prepared in two
forms of bead and film with two nHAp contents of 20 and 50 wt%.
2.2.1. Preparation of nHAp–alginate composite beads
For preparing 50 wt% nHAp–alginate composite, 0.6 g of nHAp
powder was dispersed in 60 mL deionized water. Due to nano-size
of the nHAp powder, the particles extremely tended to agglomer-
ate, especially when dispersed in water; therefore, dispersion pro-
cess was facilitated by employing mechanical stirring at 1200 rpm
and sonication. At first the solution was stirred with mechanical
stirrer for 75 min, then it was sonicated for 15 min to break the
agglomerates. This cycle was repeated once more to obtain a
homogeneous and fine dispersion of the nHAp powder in water.
Next, a measured amount of sodium alginate powder was
added to the nHAp solution to obtain 1% (w/v) alginate solution.
The resulting nHAp/alginate solution was vigorously stirred by
mechanical stirrer for 6 h to have a homogeneous mixture. The fi-
nal nHAp–alginate mixture was then extruded by needle injection
syringe into 0.1 mol L1 CaCl2 solution and left to ion exchange for
2 h while the CaCl2 solution was stirred slowly by a magnetic stir-
rer. The resulting beads were washed with deionized water to re-
move excess CaCl2 remaining on the composite surface. Finally
the beads were dried overnight in an oven at 55–60 °C.
The procedure for preparing 20 wt% nHAp–alginate composite
beads was exactly the same except that in the first step 0.15 g of
nHAp powder was dispersed in 60 mL deionized water.
 F. Googerdchian et al. / Chemical Engineering Journal 200–202 (2012) 471–479
2.2.2. Preparation of nHAp–alginate composite films
The method used for the preparation of 20 and 50 wt% nHAp–
alginate solutions were exactly the same as described for the bead
preparation. To make the composite films, filter papers (Filterak)
with the dimension of 3  4 cm2 were cut and immersed in the
nHAp–alginate solutions. By this mean the solution was absorbed
on the filter paper surface. Next, the papers were transferred into
0.1 mol L1 CaCl2 solution and left there for 10 min. Then the com-
posite films were washed with deionized water; and finally they
were dried in an oven at 55–60 °C for 3 h. The amount of composite
adsorbent coated on the filter papers was simply determined from
the weight difference between the dried adsorbent-coated filter
paper and the plain filter paper without coating.
2.3. Pb2+ removal adsorption experiments
Batch sorption experiments for Pb2+ ions removal from aqueous
solutions were performed by using four different adsorbents: the
composite beads, the composite films, the alginate beads and nHAp
powder. The last two adsorbents were used to compare their re-
sults with the adsorption data obtained for the composite. To run
each experiment, 0.075 g of the desired adsorbent was added to
30 mL of lead solution with an initial concentration of 900 mg L1
for Pb2+. Prior to each experiment the pH of the solutions were ad-
justed at five by adding proper amounts of 0.1 M HNO3 or 0.3 M
KOH solutions. It is worth mentioning that the zero point charge
of the adsorbents were determined by batch equilibration tech-
nique [42] using 0.1 mol dm3 KNO3 solution as an inert electro-
lyte. To measure the pHpzc the initial pH of KNO3 solutions were
adjusted at a predetermined value varying from 2 to 10 by adding
proper amount of 0.1 mol dm3 HNO3 or KOH solution. Then
adsorbent was added to the solution and it was left for 24 h to
reach equilibrium. The final pH of the solution at equilibrium
was measured and pHPZC was determined from the plots of pHfinal
vs pHinitial. The pHpzc values were found to be 6.2, 6.5, and 7.1 for
pure alginate film, 50 wt% nHAp–alginate film, and nHAp powder,
respectively.
At solution pH values lower than the pHpzc the total surface
charge of adsorbents is on average positive, whereas at pH values
above pHpzc, the surface is negatively charged. Generally speaking
negatively charged surface promotes the sorption of Pb2+.
Since the PHpzc for all adsorbents were higher than six, it
seemed that the working pH should have been higher than six.
But, reviewing the works done by other researchers in the same
field showed that the Pb2+ is efficiently adsorbed by calcium algi-
nate at pH values higher than four and especially in the pH range
of 4–5. At lower pH values, H+ ions would compete with Pb2+ ions
for the exchangeable sites on the calcium alginate which results in
reduction of lead removal [27,43,44].
Another reason for working at pH of five was to avoid hydrolysis
of Pb2+ cations which occurs at pH higher than five [13].Further-
more, lead removal experiments with pure HAp and HAp compos-
ites were mostly done at pH of five by other researchers
[13,20,23,45–47]. Therefore, by selecting the pH of five for the
adsorption experiments made it possible to compare the results
of this work with the works done by others.
All sorption experiments were performed at ambient tempera-
ture on a shaker working at 140 rpm. After 1 and 6 h of contact
time, a specific volume of the solution was withdrawn and diluted
by adding deionized water. Next, the diluted samples were ana-
lyzed by atomic absorption spectroscopy method to determine
the remaining metal concentration. Since the nHAp powder could
not properly be dispersed in the lead solution by only using the
shaker, mechanical stirrer was used for the nHAp powder adsorp-
tion experiments with the same adsorption conditions mentioned
above.
473
The amount of Pb2+ ions removed by the adsorbent, qt (mg g1),
was calculated according to the following equation:
C0  Ct
Qt ¼ V ð1Þ
mads
where C0 and Ct are the metal concentrations in liquid phase in ppm
(mg L1) at the initial and any arbitrary time t (s), respectively. The
adsorbent mass (g) is represented by mads and V is the volume of the
solution (L). Adsorption isotherm and adsorption capacity of 50 wt%
nHAp–alginate composite adsorbent film were obtained from equi-
librium batch tests. For this purpose 0.075 g of the adsorbent was
added to 30 mL of the lead solution and left for 24 h to reach the
equilibrium. The initial pH was adjusted to five before the experi-
ments and the initial concentrations of the solution varied from
300 to 1500 mg L1.
Kinetic batch studies were also conducted to evaluate sorption
capacity of adsorbents for lead ions removal. To this aim 0.2 g of
adsorbent was added to several beakers each containing 80 mL of
the lead solutions with initial Pb2+ concentration of 900 mg L1
and sorption kinetic data were collected by sampling from each
beaker at different time intervals varying from 5 to 360 min.
3. Results and discussion
3.1. Characterization of nHAp powder
X-ray diffraction analysis (XRD) was carried out on the prepared
nHAp powder by a Philips diffractometer (Philips X’PERT), using
Ni-filtered Cu Ka radiation (k = 0.154056 nm at 20 kV and 30 mA)
over the 2h range of 10–55° and scanning step size of 0.04°. The
XRD patterns of the nHAp powders are shown in Fig. 1.
Crystallite size of the powders was determined from broaden-
ing XRD peaks by using the Williamson–Hall equation [48]:
k
Cosh ¼ 0:9 þ 2eSinh ð2Þ
d
where k is wavelength of the X-ray (nm), h is the diffraction angle, e
is lattice strain and b is the diffraction peak (rad) width in the mid-
dle of its height. b was estimated after computer-fitting of X-ray
data using the Gaussian line shape. The average crystallite size
was found equal to 37 nm.
TEM micrograph of nHAp is shown in Fig. 2. This image reveals
that plate-shaped particles with an average size of 42 nm were
formed after milling the raw materials for 2 h. Therefore the parti-
cles were shown to be nano-sized.
3.2. Morphology of nHAp–alginate composites
SEM images of the beads made of pure alginate and nHAp–algi-
nate composite with two different nHAp contents of 20 and 50 wt%
Fig. 1. XRD patterns of the ball milled nHAp powder.
474 F. Googerdchian et al. / Chemical Engineering Journal 200–202 (2012) 471–479
Fig. 2. TEM image of nHAp powder.
are shown in Fig. 3. The SEM images show that the surface of the
beads made of pure alginate was nonporous and without wrinkles.
However, adding nHAp to alginate wrinkled the surface of beads
and some superficial grooves appeared on the beads. These effects
were more significant when more nHAp was added to alginate. In
addition, by adding nHAp to alginate, the average diameter of the
beads increased. It was 1240, 1405, and 1472 lm for pure alginate,
20 wt%, and 50 wt% nHAp–alginate beads, respectively.
SEM images of composite films are shown in Fig. 4. Comparing
the images for two types of the composite films containing 20 and
50 wt% nHAp, it was seen that in both cases some of nHAp particles
Fig. 3. SEM images of different adsorbent beads: (a) pure alginate, (b) 20 wt% nHAp–alginate composite, and (c) 50 wt% nHAp–alginate composite.
had accumulated on the surface of the films. Although, nHAp par-
ticles were dispersed more uniformly and less agglomerated in the
film with 20 wt% of nHAP.
3.3. Pb2+ adsorption by composite beads
The composition and shape of the adsorbents are two important
parameters strongly affecting the Pb2+ removal capacity by the
adsorbents. The adsorption experiments were carried out using
solutions initially containing 900 mg L1 of Pb2+ at pH adjusted
to five.
Three different adsorbent beads explained previously in Section
3.2 were used for this purpose.
The amounts of Pb2+ ions removed per unit mass of adsorbent
(q) were determined for 1 and 6 h of contact time for each adsor-
bent separately. The results are shown in Fig. 5. These results re-
vealed that adding nHAp powder to alginate beads had negative
effect on the adsorption capacity of the polymer, even though
the negative effect increased by increasing the amount of nHAp
in the composite beads. To explain this finding one can consider
the size of beads and the diffusion path length through the adsor-
bent beads. Generally speaking nHAp particles have less adsorp-
tion capacity for Pb2+ removal than alginate. This is shown in
Fig. 6. By adding nHAp particles to alginate and making bead shape
composite adsorbent, the size of beads increased and the diffusion
length through the adsorbent structure increased. In addition,
most of nHAp particles agglomerated on the beads’ surface. These
 F. Googerdchian et al. / Chemical Engineering Journal 200–202 (2012) 471–479
Fig. 4. SEM images of composite adsorbent films: (a) 20 wt% nHAp–alginate composite and (b) 50 wt% nHAp–alginate composite.
Fig. 5. Amount of Pb2+ ions removed per unit mass of adsorbent for nHAp–alginate
composite beads with different nHAp contents.
two effects decreased the adsorption capacity of the composite
adsorbents in comparison with the beads made of pure alginate.
Due to these undesirable results further studies were focused on
using film shape composite adsorbents.
3.4. Pb2+ adsorption by composite films
Adsorption experiments were conducted by using three differ-
ent film shape adsorbents. One film was made from pure alginate
whereas the two others were composite films containing 20 wt%
and 50 wt% of nHAp powder. To have a better judgment on the ef-
fect of adding alginate and nHAp to each other, some experiments
were done by using only pure nHAp powder as adsorbent. The ini-
tial conditions of the Pb2+ solutions were exactly the same as the
experiments with the composite beads. The dynamic data for
Pb2+ removal by all four types of adsorbents are presented in
Fig. 6. By comparing the amounts of Pb2+ removed after 6 h of oper-
ation for the composite adsorbents in two different forms (Figs. 5
and 6) it is understood that adsorption capacity of the composite
475
Fig. 6. Amount of Pb2+ ions removed per unit mass of adsorbent vs contact time for
different adsorbents.
adsorbents increased significantly when the adsorbents were made
in the film form. According to data graphed in this figure most of
Pb2+ adsorption took place in the first 15 min of experiments for
all of the adsorbents. However, the adsorption process with the
adsorbents made of pure alginate and 20 wt% nHAp composite
films reached to its final equilibrium only after one hour – it took
about 6 h for the two other adsorbents. In addition, this figure re-
vealed that despite pure nHAp being in the powder form and thus
having larger contact surface area with the solution, its adsorption
capacity was lower than that of pure alginate in the film form.
Most interestingly when nHAp particles were added to alginate
to make composite adsorbent the adsorption capacity increased.
This can be explained by considering the mechanism of adsorption
which will be discussed in the next section.
3.5. Mechanism of Pb2+ removal by composite adsorbents
According to the literature, two main mechanisms have been
proposed for Pb2+removal from aqueous solutions by nHAp. The
476 F. Googerdchian et al. / Chemical Engineering Journal 200–202 (2012) 471–479
first mechanism, which recently has been more considered by the
researchers, is dissolution–precipitation mechanism. In this mech-
anism at first nHAp is dissolved in the solution and then it is pre-
cipitated as hydroxypyromorphite (Pb10(PO4)6(OH)2) [14,49]. This
mechanism is expressed as:
Dissolution : Ca10 ðPO4 Þ6 ðOHÞ2 þ 14Hþ
! 10Ca2þ þ 6H2 PO4 þ 2H2 O
2þ
Precipitation : 10Pb þ 6H2 PO4 þ 2H2 O
þ
! 14H þ Pb10 ðPO4 Þ6 ðOHÞ2
The second main mechanism is ion exchange reaction in which the
Ca2+ ions of the nHAp lattice are partially replaced by the Pb2+ ions
from the solution, which results in the formation of more stable
lead apatites shown as Ca(10x)Pbx(PO4)6(OH)2 [50]. The following
reaction presents this mechanism:
2þ
Ca10 ðPO4 Þ6 ðOHÞ2 þ xPb ! xCa2þ þ Cað10xÞ Pbx ðPO4 Þ6 ðOHÞ2
Beside these two main mechanisms, metal complexation on the
nHAp surface also occurs as a secondary mechanism [14,47].
The dominate mechanism of divalent metal ions sorption on the
alginate adsorbent is ion exchange involving mainly the carboxyl
groups present in the alginate molecule, with hydroxyl groups
playing a secondary role [43,44,51].
In order to investigate the mechanism of Pb2+ removal by the
composite adsorbents, SEM images were obtained for 50 wt%
nHAp–alginate composite film before and after 6 h adsorption pro-
cess on the 900 mg L1 Pb2+ solution. As seen in Fig. 7, small parti-
cles appeared on the surface of the composite adsorbent after
adsorption process, probably due to dissolution–precipitation
mechanism domination for Pb2+ removal. To validate this hypoth-
esis, the composition of these particles was determined by EDX
Fig. 7. SEM images of 50 wt% nHAp–alginate composite film (a) before and (b) after adsorption experiment (900 mg L1 initial Pb2+ concentration and pH = 5).
Fig. 8. EDX spectra of 50 wt% nHAp–alginate composite film (a) before and (b) after adsorption experiment (900 mg L1 initial Pb2+ concentration and pH = 5).
analysis. Fig. 8 shows the EDX spectra for the adsorbent before
and after adsorption process.
The EDX results presented in Fig. 8 proved that the bright
particles on the surface of the composite adsorbent belonged to
nHAp agglomerates. Besides the peaks relating to nHAp, there
was a weak peak for Cl atoms which came from composite film
production method in which the film was immersed in CaCl2
ð3:1Þ solution.
The EDX spectra of the used adsorbent showed strong absorp-
tion peaks of Pb atoms as well as weekend peaks of Ca atoms, while
the intensity of the peaks relating to P atoms remained unchanged.
ð3:2Þ Jang et al. investigated the mechanism of Pb2+ removal by HAp–
polyurethane and HAp–polyacrylamide composite adsorbents.
They suggested that since the overall morphology of the composite
adsorbents remained unchanged after adsorption process, ion-ex-
change was the dominant mechanism. In this case, weak Ca peaks
together with strong Pb peaks were found in the EDX spectra of the
adsorbents after adsorption experiments [20,23].
In the present work, despite weak Ca peaks and strong Pb peaks
ð4Þ
being detected in the EDX spectra of the adsorbent after adsorption
process, the overall morphology of the adsorbent changed. It is sug-
gested that weak Ca peaks were related to the Ca presenting in the
alginate polymer lattice on which HPy particles were precipitated.
Therefore, when the adsorbent was immersed into the Pb2+ solution,
the nHAp particles which were placed on the surface of the alginate
were released and dissolved in the solution. Dissolution of nHAp
particles led to formation and participation of HPy on the surface
of the composite adsorbent resulting in Pb2+ ions removal. On the
other hand, by releasing the nHAp particles from the composite sur-
face, more alginate polymer was accessible to the Pb2+ solution; thus
at the same time while nHAp particles dissolved to remove Pb2+ ions,
alginate also removed some Pb2+ ions leading to improved sorption
capacity of the nHAp–alginate composite compared to the pure algi-
nate and nHAp powder adsorbents.
 F. Googerdchian et al. / Chemical Engineering Journal 200–202 (2012) 471–479
3.6. Kinetics studies
The kinetic behavior of the metal ion removal by different
adsorbents used in this work was investigated by using the dy-
namic data presented in Fig. 6. Among different kinetic models,
pseudo-second order kinetic model has been shown to be able to
be more appropriate for many cases of metal ion removal by
adsorption process. This model is usually expressed as [52]:
t 1 t moval by different adsorbents. In the Langmuir model it is
¼ þ
qt k2 q2e qe
where qt and qe are amounts of Pb2+ ions removed per unit mass of
adsorbent in mg g1 at an arbitrary contact time t (s) and at equilib-
rium stage, respectively. Also k2 is the pseudo-second-order rate
constant expressed in g.mg1 min1. Once t/qt is plotted vs t, if a lin-
ear graph is obtained, the rate constant and qe can be determined
from the intercept and slope of the line, respectively [53]. The re-
sults for linear curve fitting to the dynamic data for four different
types of adsorbent are shown in Fig. 9. In addition, the kinetic model
parameters as well as regression coefficient (R2) for each adsorbent
are reported in Table 1. In this table h is the initial rate of metal re-
moval. The R2 values very close to one reveal that pseudo-second-
order kinetic model can describe very well the dynamic behavior
of adsorption process for all the film form adsorbents prepared
and used in this work.
Comparing the k2 values obtained for different adsorbents
shows that 20 wt% nHAp–alginate composite had the fastest kinet-
ics whereas the slowest kinetics belonged to 50 wt% nHAp–algi-
nate composite. However, the latter had the highest adsorption
capacity at equilibrium (236 mg g1). The equilibrium time ob-
tained in this work is much less than those obtained by using dif-
ferent adsorbents for Pb2+ removal [20,23,24]. Therefore, despite
having the slowest kinetics the 50 wt% nHAp–alginate composite
adsorbent can be considered as the most preferred adsorbent pre-
pared in this work due to its highest adsorption capacity.
Fig. 9. Variation of t/qt with time for different adsorbents.
Table 1
Experimental equilibrium capacity and pseudo-second order kinetic model parameters for lead adsorption by various adsorbents.
Adsorbent type qe,exp (mg g1) Parameters of pseudo-second order model
k2  103 (g mg1 min1)
nHAp powder 193 1.22
Alginate film 204 3.16
20 wt% nHAp–alginate film 226 2.69
50 wt% nHAp–alginate film 236 1.07
477
3.7. Adsorption isotherm study
Since 50 wt% nHAp–alginate composite film was recognized as
the most preferred adsorbent among the ones prepared in this
work, the adsorption isotherm studies were done only for this
adsorbent for Pb2+ removal at pH of 5. Different isotherm models
are considered to describe the equilibrium behavior of adsorption
systems. Among different adsorption isotherm models, the Lang-
muir model is the most widely used model for heavy metal re-
ð5Þ
assumed that adsorbent has sites which have uniform energy for
adsorption of the adsorbate, resulting in monolayer homogeneous
adsorption [43]. The linear form of Langmuir isotherm is presented
as [54]:
Ce 1 Ce
¼ þ ð6Þ
qe K e qmax qmax
where qe (mg g1) and Ce (mg L1) are the amounts of adsorbed spe-
cies per unit mass of adsorbent and concentration of Pb2+ in the
solution, respectively, both at equilibrium stage. In this equation,
qmax (mg g1) is the maximum sorption capacity which is the re-
quired amount of adsorbed component per unit mass of adsorbent
to form a complete monolayer on the actual surface of the adsor-
bent. In addition, Ke (L mg1) denotes the Langmuir constant related
to the energy of adsorption. Once the equilibrium adsorption
behavior of an adsorbent obeys the Langmuir isotherm model, then
plotting Ce/qe vs Ce gives a fairly good linear curve and the values of
qmax and Ke can be obtained from the slope and intercept of the lin-
ear plot, respectively.
Two other isotherm models investigated in this work were Fre-
undlich and Tempkin models. According to the Freundlich model,
at equilibrium the amount of a substance adsorbed (qe) is related
to the concentration of the solute Ce by the following equation:
qe ¼ K F C eð1=nÞ ð7Þ
where KF and n are the Freundlich constants characteristic of the
system which are indications of the adsorption capacity and
adsorption intensity, respectively, of the system [27]. The linear
form of the Freundlich isotherm model is obtained by taking loga-
rithm from Eq. (7):
lnðqe Þ ¼ lnðK F Þ þ 1=n lnðC e Þ ð8Þ
By plotting ln(qe) vs ln(Ce), KF and n are obtained from the intercept
and slope of the linear plot, respectively.
Another isotherm model investigated in this work was Tempkin
isotherm. This model assumes that the heat of adsorption de-
creases linearly with the coverage due to adsorbent–adsorbate
interaction [55]. The Tempkin isotherm is generally applied in
the following linear form:
qe ¼ B ln A þ B ln C e
ð9Þ
B ¼ RT=b
where A (L g1) is Tempkin isotherm constant and b (J mol1) repre-
sents a constant related to heat of sorption. R is the gas constant
(8.314 J mol1 K1) and T stands for the absolute temperature (K).
qe,cal (mg g1) h (mg g1 min1) R2
192.3 45.12 0.9997
204.1 131.61 1.0000
227.3 138.89 1.0000
238.1 60.66 0.999
478 F. Googerdchian et al. / Chemical Engineering Journal 200–202 (2012) 471–479
Fig. 10. Linear plot of Langmuir isotherm for 50 wt% nHAp–alginate composite film.
Fig. 11. Linear plot of Freundlich isotherm for 50 wt% nHAp–alginate composite
film.
Fig. 12. Linear plot of Tempkin isotherm for 50 wt% nHAp–alginate composite film.
A plot of qe vs ln(Ce) enables the determination of the isotherm con-
stants b and A from the slope and intercept, respectively.
The isotherm studies were carried out by using the experimen-
tal data obtained for adsorption of Pb2+ by 50 wt% nHAp–alginate
composite film. Fig. 10 shows the graph of Ce/qe vs Ce for Langmuir
isotherm. Also, Figs. 11 and 12 present the linear curve fitting for
the two other models, Freundlich and Tempkin, using the same
experimental data. The models’ parameters are summarized in Ta-
ble 2. Comparing the regression coefficient (R2) values shows that
the Langmuir isotherm with R2 higher than 0.99 was the most
proper model to describe the equilibrium behavior of the
adsorbent.
From the model parameters for Langmuir isotherm, it is
noticeable that the maximum Pb2+ sorption capacity of 270.3
Table 2
Isotherm models’ parameters for 50 wt% nHAp–alginate composite adsorbent.
Model Isotherm parameters Regression
coefficient (R2)
Langmuir qmax (mg g1) Ke (L mg1) 0.9972
270.3 0.088
Freundlich Kf (mg g1) (mg L1)n n 0.8983
121.2 8.16
Tempkin A b 0.9491
128.6 104.9
mg g1 for 50 wt% nHAp–alginate composite film was much larger
than maximum lead sorption capacities of other composite
adsorbents used by other researchers. qmax was reported to be
16.32, 150, and 178 mg g1 for hydroxyapatite/cellulose composite,
50 wt% hydroxyapatite/polyurethane composite foam, and 50 wt%
hydroxyapatite/polyacrylamide composite hydrogels, respectively.
In addition very short equilibrium time for the adsorbent used
in this work (6 h) in comparison with 48 and 120 h for 50 wt%
hydroxyapatite/polyurethane composite foam and 50 wt%
hydroxyapatite/polyacrylamide composite hydrogels makes our
adsorbent contradistinctive for possible industrial applications
[20,23,24].
4. Conclusions
Nano-sized natural hydroxyapatite particles were prepared by
mechanical activation of bovine bone. The particles were used to
make nHAp–alginate composite adsorbents containing 20 and
50 wt% of nHAp. The composite adsorbents were formed in two
different shapes of beads and films. The adsorbents were used to
investigate their capability for removing contaminating Pb2+ ions
from aqueous solutions at initial concentration of 900 mg L1 and
pH = 5. The results for bead form adsorbents showed that incorpo-
rating nHAp particles into alginate not only did not have positive
effect on adsorption capacity but also reduced it to lower values
less than that of pure alginate. But when the film type composite
adsorbents were formed and used with the same composition as
the beads, different results were obtained. The adsorption capaci-
ties of 20 and 50 wt% composite films were higher than those for
pure alginate film and pure nHAp powder. Increasing nHAp con-
tent of the composite films from 20 to 50 wt% led to enhancement
of adsorption capacity, but it had negative effect on the adsorption
rate. Kinetics studies proved that the dynamic behavior of Pb2+
adsorption by all of the film type adsorbent used in this work could
be described by pseudo-second order kinetic model. Also, isotherm
equilibrium data fitted very well to the Langmuir model. Finally, in
comparison with other hydroxyapatite–polymer composite adsor-
bents with lower adsorption capacities and longer equilibrium
times, 50 wt% nHAp–alginate film type composite adsorbent with
maximum adsorption capacity equal to 270.3 mg g1 and equilib-
rium time of 6 h can be considered as a promising candidate for
Pb2+ removal from aqueous solutions.
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