Accepted Manuscript

Title: Influence of alginate fixation on the adsorption capacity

of hydroxyapatite nanocrystals to Cu2+ ions

Authors: Jiali Guo, Yingchao Han, Yuting Mao, M. Nirmali

Wickramaratne

PII: S0927-7757(17)30637-4
DOI: http://dx.doi.org/doi:10.1016/j.colsurfa.2017.06.075
Reference: COLSUA 21762

To appear in: Colloids and Surfaces A: Physicochem. Eng. Aspects

Received date: 25-4-2017

Revised date: 26-6-2017
Accepted date: 28-6-2017

Please cite this article as: Jiali Guo, Yingchao Han, Yuting Mao, M.Nirmali
Wickramaratne, Influence of alginate fixation on the adsorption capacity of
hydroxyapatite nanocrystals to Cu2+ ions, Colloids and Surfaces A: Physicochemical
and Engineering Aspectshttp://dx.doi.org/10.1016/j.colsurfa.2017.06.075

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 Influence of alginate fixation on the adsorption capacity of

hydroxyapatite nanocrystals to Cu2+ ions

Jiali Guoa, Yingchao Hana*, Yuting Maoa, M. Nirmali Wickramaratneb

a
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing,

Biomedical Materials and Engineering Research Center of Hubei, Wuhan University of

Technology, Wuhan 430070, Hubei, P.R. China

b
Faculty of Applied Sciences, Sabaragamuwa University of Sri Lanka, 70140 Belihuloya, Sri

Lanka

Correspondence to: Y.C. Han (E-mail: hanyingchao@whut.edu.cn); Tel:86-27-87651852; Fax:

86-27-87880734

Graphical abstarct

ABSTRACT

Nano-hydroxyapatite (HAP) can be used as an environmentally friendly adsorbent of heavy

metal ions. However, the agglomeration and precipitation of nano-HAP will result in the loss of

adsorption capacity to heavy metal ions. Herein, the stable nano-HAP suspension was

synthesized with the stabilization effect of polyacrylic acid and further fixed by alginate to form
nano-HAP-alginate composite. The effect of alginate fixation on the adsorption capacity of

nano-HAP to Cu2+ ions was studied. Results showed that the adsorption capacity to Cu2+ ions of

alginate fixed nano-HAP was depended on the mass ratio of nano-HAP to alginate. With the

increase of mass ratio of nano-HAP to alginate from 5:95 to 95:5, the displayed adsorption

capacity of nano-HAP to Cu2+ ions was gradually decreased due to the increasing agglomeration

of nano-HAP. Especially, while the mass ratio of nano-HAP to alginate was at 5:95-10:90, the

nano-HAP was fixed in alginate with single-particle distribution, showing adsorption capacity

comparable to that of nano-HAP suspension (60.99 mgg-1). The adsorption of Cu2+ on nano-HAP

was attributed to Langmuir isotherm model (monolayer sorption). After fixation by alginate, the

resulting nano-HAP-alginate (50:50) composite showed the adsorption to Cu2+ followed both the

Langmuir and Freundlich isotherm models, indicating the multilayer sorption of Cu2+ on

heterogeneous surface. Accordingly, the alginate fixation is an alternative way for nano-HAP as

adsorbent of heavy metal ions.

Keywords: Nano hydroxyapatite; Alginate fixation; Composite; Heavy metal ions; Adsorption

1. Introduction

Growing industrial activities, such as tanning, mining, electronics, electroplating and

petrochemical industrial emissions, can cause serious pollution to the environment. In particular,

heavy metal ions causing water pollution will lead to long-term toxicity effects in plants, animals

and humans if the heavy metal ions are not effectively treated and removed from water.

Therefore, it is very important to seek effective methods for removing heavy metal ions in

industrial wastewater. Chemical precipitation, adsorption, filtration, reverse osmosis, solvent

extraction and membrane separation are commonly used methods for removing heavy metal ions
[1-6]. Due to its low cost, high efficiency and ease of use, the adsorption method is becoming a

promising technology for wastewater treatment [7-10].

The removal capacity of the adsorbent is a vital factor influencing the removal effect of heavy

metal ions. In addition, the adsorbent should be environmentally friendly and causes no

secondary pollution. Hydroxyapatite (HAP) is the main mineral constituent of teeth and bones of

mammals and has been widely used as biomaterials. HAP can also be utilized as an inorganic

adsorbent with good adsorption ability to a variety of heavy metal ions [11-15]. The adsorption

takes place through dissolution-precipitation, ionic exchange reaction and/or surface

complexation with phosphate, calcium and hydroxyl groups. Due to a higher specific surface area,

nano-HAP has a higher adsorption capacity [16,17]. However, the aggregation of nano-HAP in

aqueous solutions without stabilizers will result in the loss of removal capacity; moreover, well

dispersed and highly stable nano-HAP is not easy to be isolated from aqueous solutions after

adsorption of heavy metal ions. An alternative is to disperse and fix nano-HAP in polymer, to

inhibit agglomeration of nano-HAP and to easily separate the material from the aqueous solution

after adsorption of heavy metal ions [7]. Sodium alginate (SA) is a biocompatible and

biodegradable material that can easily exchange its Na+ ion with heavy metal ions to form gels

and has a great application prospect in the adsorption of heavy metal ions [18, 19]. It can be used

to fix HAP particles and the resulting HAP-alginate composite shows good adsorption capacity

and removal efficiency due to the integrated function of different components [20].

In this paper, the stable nano-HAP suspension was synthesized with the stabilization effect of

polyacrylic acid and further fixed by alginate to form nano-HAP-alginate composite. The effect

of alginate fixation on the adsorption capacity of nano-HAP to Cu2+ ions was studied with varied

mass ratio of nano-HAP to alginate.

2. Experimental

2.1 Preparation of nano-HAP

Nano-HAP was prepared by a chemical precipitation method as follows. First, according to

the Ca/P molar ratio of 1.67, 100 mL of Ca(NO3)2 aqueous solution (Ca2+: 0.0334 M) was mixed

quickly with 100 mL of (NH4)2HPO4 aqueous solution (PO43-: 0.02 M) to obtain precipitation at

80 °C under strong stirring. Then, ammonium hydroxide was added to adjust the pH value to

approximately 10, and the reaction was maintained at 80 °C for 1 h. Next, the precipitate was

separated by centrifugation and washed three times using deionized water. Finally, the obtained

precipitate was ultrasonically re-dispersed in water to form a stable suspension by adding

polyacrylic acid (PAA, 0.3 mgmL-1) as the stabilizer and using a high intensity ultrasound probe

(6 min).

2.2 Preparation of HAP-alginate nanocomposite

Under stirring, alginate was dissolved in the above nano-HAP suspension, and the mixture

was heated at 80 °C. After evaporation of water, gels were formed. The concentration of mixture

(nano-HAP and alginate) was controlled at 0.067 gmL-1. Next, the gels were shaped in a cylinder

mold and frozen at -20 °C. After the freeze drying process, a dried composite was obtained. The

mass ratio of nano-HAP to alginate was controlled from 5:95 to 95:5, corresponding to the

weight percentage of nano-HAP in composite from 5 % to 95 %. Finally, the composite was

immersed into the mixture of alcohol and 10% CaCl2 aqueous solution (volume ratio of 5:1) for

the gelation process of 1 h. After washing and drying, the nano-HAP was fixed by alginate and

the composite adsorbent was obtained.

2.3 Characterization of materials

 Samples were analyzed by Fourier transform infrared spectroscopy (FTIR, Nicolet6700,

Thermo Nicolet, USA). X-ray diffraction analysis (XRD, D8 Advance, Germany) was utilized to

analyze HAP. Crystallite size of the powders was calculated by using the equation: X hkl = k λ/

(β1/2cosθ). Transmission electron microscope (TEM, JEM2100F, Japan) and scanning electron

microscope (SEM, ULTRA PLUS-43-13, Germany) were used to observe the morphology and

microstructure of nano-HAP and HAP-alginate nanocomposites, respectively. Dynamic light

scattering (DLS, ZetaSizer 3000HS, UK) was used to determine the size distribution of the

nano-HAP suspension. The concentration of heavy metal ions were determined by Atomic

absorption spectroscopy (AAS, GBC AVANTA M, Australian).

2.4 Adsorption experiment for the removal of heavy metal ions

2.4.1 Cu2+ removal experiment on nano-HAP

Cu2+ aqueous solution was added into nano-HAP suspension with resulting concentrations

from 20 mgL-1 to 500 mgL-1. Under stirring, the adsorption of Cu2+ on HAP was carried out for 1

h. After centrifugation, the concentration of Cu2+ in the supernatant was measured using the

atomic absorption spectroscopy (AAS) method.

2.4.2 Cu2+ removal experiment on nano-HAP-alginate composite

The adsorption property of nano-HAP-alginate for Cu2+ was studied in detail. First, the

saturated adsorption time was determined. Adsorption time was set at 10 min, 20 min, 30 min, 40

min, 50 min, 60 min, 120 min, 180 min, 240 min, 360 min. For each time point, an independent

adsorption experiment was carried out as the following. The obtained nano-HAP-alginate (20 mg)

was immersed in 4 mL of Cu2+ aqueous solution (500 mgL-1). The concentration of Cu2+ in the

supernatant was measured by the AAS method at the setting time point. Next, for determining

the saturated adsorption capacity, the obtained nano-HAP-alginate (20 mg) was immersed in 4
mL of Cu2+ aqueous solution with increasing concentration from 20 mgL-1 to 500 mgL-1. After 1

h, the concentration of Cu2+ in the supernatant was measured by the AAS method.

All adsorption experiments were carried out at ambient temperature on a shaker working at

110 rpm. The removal capacity (Qt, mgg-1) was calculated according to the following equation:

Qt = (C0-Ct) Vm-1, where C0 and Ct are the metal ion concentrations at the initial time and an

arbitrary time, respectively, V is the volume of the solution, and m is the mass of the adsorbent.

3. Results and discussion

3.1 Characterization of HAP

The XRD pattern in Figure 1(a) shows that the sample was crystalline HAP. The calculated

crystallite sizes of HAP in the (002) and (310) crystallographic planes were 28.2 nm and 15.2 nm,

which corresponded to the sizes in the long axis and cross section directions, respectively. This

indicated that the HAP nanoparticles should be short rod-like. The FT-IR spectrum of the sample

(Figure 1(b)) also showed the characteristic vibrations assigned to HAP. The vibration bands of

PO43- were detected at 1048 cm-1, 890 cm-1, 605 cm-1 and 958 cm-1; the broad band centered at

3437 cm-1 was due to the adsorption of -OH groups in water, and the band at 3570 cm-1 was due

to the adsorption of -OH groups in HAP. As shown in the SEM micrograph (Figure 2(a)), the

obtained HAP nanoparticles were needle-like with sizes of 18.7±1.2 nm in diameter and

196.0±31.3 nm in length. The HAP nanopowders could be well dispersed in water to form a

stable suspension with PAA (0.3 mgmL-1) by ultrasound treatment. The size distribution (Figure

2(c)) of the HAP suspension was from 40 nm to 400 nm, and the intensity-averaged particle size

was 122.7 nm. The polydispersity index was 0.131, showing a narrow size distribution in the

HAP suspension. The good stability of HAP suspension is mainly attributed to the steric effect of

PAA. The TEM micrograph (Figure 2(b)) shows that HAP was needle-like nanoparticles with
sizes of 7.3-15.6 nm × 68.0-105.0 nm. The smaller value of the length from TEM compared with

that from SEM demonstrated that HAP nanoparticles were well dispersed in a stable suspension,

and severe aggregation was avoided.

3.2 Characterization of nano-HAP-alginate composite

Nano-HAP-alginate composites with different mass ratio of nano-HAP to alginate (from 5:95

to 75:25), corresponding to HAP contents from 5 wt% to 75 wt%, were obtained. SEM images of

Nano-HAP-alginate composites are shown in Figure 3. It can be seen here that for the

composites with 5-10 wt% HAP, HAP nanoparticles were fixed and dispersed uniformly in the

alginate matrix with single-particle distribution. However, when the content of HAP was 20-50

wt%, the fixed nano-HAP showed some agglomeration. With a further increase of the HAP

content to 75 wt%, the agglomeration of nano-HAP became more severe.

FT-IR spectra of nano-HAP-alginate composites (without CaCl2 cross-linking), SA and

nano-HAP are shown in Figure 4. The results showed that the intensity of the vibration bands of

HAP was gradually enhanced, demonstrating the increasing content of HAP in the composite. In

particular, the bands assigned to the asymmetric and symmetric stretching of the –COO- group of

alginate in the composite were moved to 1617-1628 cm-1 and 1416-1420 cm-1, respectively,

compared to those in pure SA (1609 cm-1 and 1431 cm-1). However, the positions of the –COO-

group of alginate in the composite were close to those in CaCl2 treated SA. In addition, the

intensity of the symmetric stretching of the –COO- group was lower than that of the asymmetric

stretching of the –COO- group in the composite, which is consistent with the change in

CaCl2-treated SA. The changes of bands in the position and intensity can be attributed to the

interaction between the –COO- group in alginate and Ca2+ on the surface of HAP via an
electrostatic attraction force. It can be concluded that the nano-HAP was integrated with alginate

in chemical bonds.

3.3 Cu2+ adsorption by nano-HAP

Adsorption experiments were conducted to observe the characteristic of Cu2+ adsorption on

nano-HAP without alginate fixation. The adsorption capacity and removal efficiency of

nano-HAP for Cu2+ are shown in Figure 5. With increasing concentration of Cu2+ in the solution

to 250 mgL-1, the adsorption capacity of nano-HAP rapidly increased at a high removal

efficiency of 97-99 %. With a further increase of the Cu2+ concentration from 250 mgL-1 to 500

mgL-1, the removal rate gradually decreased. However, the adsorption capacity was still

increased and reached the highest value of 60.98 mgg-1 at a Cu2+ concentration of 350 mgL-1.

3.4 Cu2+ adsorption by nano-HAP-alginate composite

First, the adsorption equilibrium time of the nano-HAP-alginate composite (50 wt% of

nano-HAP) was studied at a Cu2+ concentration of 500 mgL-1. As shown in Figure 6, when the

adsorption time was below 60 min, the adsorption capacity was rapidly elevated. With the further

increase of adsorption time, the increase of adsorption capacity plateaued. Therefore, an

adsorption time of 60 min was selected as the best adsorption time and was adopted for all other

experiments. It was also observed that the adsorption efficiency decreased gradually with the

increase of Cu2+ concentration (20-500 mgL-1), and the highest adsorption capacity was 48.27

mgg-1 at a Cu2+ concentration of 400 mgL-1, as shown in Figure 7.

The effect of the mass ratio of nano-HAP to alginate on the adsorption capacity of the

composite was examined. As shown in Figure 8, the adsorption capacity of the

nano-HAP-alginate composite for Cu2+ decreased gradually from 71.03 mgg-1 (0 wt% of
nano-HAP) to 40.48 mgg-1 (95 wt% of nano-HAP) with increasing content of nano-HAP due to

an increase of agglomeration of alginate fixed nano-HAP particles.

On the basis of the obtained experimental values of adsorption capacity of pure alginate

(EValginate) and pure nano-HAP (EVnano-HAP), the calculated value of adsorption capacity of

composite (CVcomposite) was obtained using equation: CVcomposite = EValginate × (1- HAP wt%) +

EVnano-HAP × HAP wt%, where EValginate was 71.0 mgg-1 (the value at 0 of HAP wt%); EVnano-HAP

was 61.0 mgg-1 (deriving from Figure 5). The calculated values were denoted by symbol ( ) in

Figure 8. In addition, the calculated value of alginate fixed nano-HAP (CVfixed nano-HAP) was

obtained based on the experimental values of adsorption capacity of pure alginate (EValginate) and

composite (EVcomposite) using equation: CVfixed nano-HAP = [EVcomposite - EValginate × (1- HAP wt%)] /

HAP wt%, where EValginate was 71.0 mgg-1 (the value at 0 of HAP wt%); EVcomposite was the

obtained experimental value. The calculated values were denoted by symbol (○) in Figure 8.

Results showed that while the mass ratio of nano-HAP to alginate was from 5:95 to 20:80, the

experimental adsorption capacity of composite was very close to the calculated adsorption

capacity; moreover, the calculated adsorption capacity of alginate fixed nano-HAP was very

close to the adsorption capacity of nano-HAP (61.0 mgg-1). These indicate that after being fixed

by alginate fixation, nano-HAP can maintain its adsorption capacity to Cu2+ with the mass ratio

of 5:95-20:80 (nano-HAP:alginate). This is because that nano-HAP is uniformly fixed in alginate

with single-particle distribution. However, with the further increase of mass ratio of nano-HAP

to alginate, the experimental adsorption capacity of composite was becoming smaller than the

calculated adsorption capacity with an increasing disparity; moreover, the alginate fixed

nano-HAP showed many loss in adsorption capacity. This is due to the increasing agglomeration

of nano-HAP in alginate fixation.

 For nano-HAP, there are three main mechanisms for removing heavy metal ions from aqueous

solution, which are dissolution-precipitation, ionic exchange reaction and surface complexation

[21, 22]. First, nano-HAP has a higher solubility than bulk HAP and can be dissolved in solution

to form H2PO4- groups which can react with heavy metal ions (M2+) to form precipitation, i.e.,

(M10(PO4)6(OH)2). Second, the Ca2+ ions in the HAP lattice can be exchanged with heavy metal

ions, resulting in the removal of heavy metal ions from the aqueous solution by forming heavy

metal ions partially substituted with HAP (Ca(10-x )Mx(PO4)6(OH)2. Finally, the phosphate and

hydroxyl groups on the surface of HAP crystals can adsorb heavy metal ions by complexation.

For alginate, the abundant carboxyl groups can interact with divalent heavy metal ions by ion

exchange, facilitating the removal of heavy metal ions [23, 24]. Nano-HAP suspension is in a

high dispersity situtation and nano-HAP can provide large contact areas with heavy metal ions,

leading to a high removal capacity. After being fixed by alginate, the solubility and crystal nature

of nano-HAP are not be changed. Therefore, the removal capacity of nano-HAP to heavy metal

ions, which is based on dissolution-precipitation and ionic exchange reaction, should not be

significantly influenced. However, the agglomeration of nano-HAP results in many unexposed

adsorption sites (phosphate and hydroxyl groups) and decrease the contact areas with heavy

metal ions. Accordingly, the adsorption capacity of nano-HAP based on surface complexation is

declined.

3.5 Adsorption kinetics and isotherm studies

The kinetic behavior of the metal ion removal by nano-HAP-alginate composite adsorbent was

investigated by using the dynamic data presented in Figure 6. The pseudo-first order kinetic

model, pseudo-second order kinetic model and intraparticle diffusion model were proposed to

clarify the adsorption kinetics (Figure 9) [7]. The results for the kinetic model parameters as well
as regression coefficient (R2) are shown in Table S1. The higher R2 value of 0.998 of

pseudo-second order kinetic model than other two models (0.943 and 0.824) as well as a close

calculated Qe to experimental Qe revealed that the pseudo-second order kinetic model was more

appropriate to describe the dynamic behavior of the metal ion removal by nano-HAP-alginate

composite. Also, the removal of metal ion by nano-HAP-alginate composite was mainly

attributed to the chemisorption.

The adsorption isotherm studies were done for nano-HAP and 50% nano-HAP-alginate

composite for Cu2+ removal by using the data presented in Figure 5 and Figure 7 respectively.

Langmuir model, Freundlich model and Tempkin model were considered to describe the

equilibrium behavior of nano-HAP (Figure 10) and 50% nano-HAP-alginate composite (Figure

11) and the results are shown in Table S2 [20]. For nano HAP, the higher R2 value of 0.999 and

the very close calculated Qmax to experimntal value indicated the Langmuir isotherm model was

more suitable to describe the adsorption of Cu2+ ions. For 50% nano-HAP-alginate composite,

the both higher R2 values of 0.998 and 0.993 show that the adsorption of Cu2+ onto composite

followed both the Langmuir and Freundlich isotherm models. That is to say, nano-HAP-alginate

composite may occur the multilayer sorption of Cu2+ on heterogeneous surface of adsorbent

compared to the monolayer sorption of Cu2+ onto nano HAP.

4. Conclusions

PAA stabilized nano-HAP was successfully prepared and further fixed by alginate as

adsorbent for removing heavy metal ions. The mass ratio of nano-HAP to alginate influenced the

adsorption capacity to Cu2+ ions. With the mass ratio of nano-HAP to alginate from 5:95 to

20:80, the adsorption capacity of composite close to the calculated value was obtained and the

alginate fixed nano-HAP showed the adsorption capacity comparable to that of nano-HAP in
suspension (61.0 mgg-1). This is because that nano-HAP is uniformly fixed in alginate with

single-particle distribution. However, the further increasing mass ratio resulted in the loss of

adsorption capacity due to the increasing agglomeration of nano-HAP in alginate fixation.

Nano-HAP showed monolayer sorption of Cu2+ (Langmuir isotherm model). After alginate

fixation of nano-HAP, the resulting composite displayed multilayer sorption of Cu2+ on

heterogeneous surface (Langmuir and Freundlich isotherm models). So, nano-HAP can be used

as adsorbent for removing heavy metal ions in the form of alginate fixation, leading to easy

separation from aqueous solution.

Acknowledgements

This work was supported by the Science and Technology Partnership Program, Ministry of

Science and Technology of China (KY201602002), the National Key Research and Development

Program of China (2016YFB1101302), the Wuhan International Science and Technology

Cooperation Project (2016030409020217), the Fundamental Research Funds for the Central

Universities (WUT: 2017II44GX).

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Figure Captions

Figure 1. XRD pattern and FT-IR spectrum of nano-HAP.

Figure 2. SEM image of nano-HAP(a), TEM image (b) and size distribution (c) of PAA

stabilized nano-HAP.

Figure 3. SEM images of nano-HAP-alginate composites with different contents of nano-HAP.

(a): 5 %; (b): 10 %; (c): 20 %; (d): 40%; (e): 50 %; (f): 75 %.

Figure 4. FT-IR spectra of CaCl2 treated SA (a), pure SA (b), CaCl2 untreated

nano-HAP-alginate composites with 5% (c), 10% (d), 20% (e), 40% (f), 50% (g), 75% (h) HAP,

and pure HAP (i).

Figure 5. Adsorption capacity and removal efficiency of nano-HAP to Cu2+ at 1 h of adsorption

time.

Figure 6. Adsorption equilibrium time (Cu2+) of 50 % nano-HAP-alginate composite.

Figure 7. Adsorption property (Cu2+) of 50 % nano-HAP-alginate composite.

Figure 8. Experimental adsorption capacity of nano-HAP-alginate composites with different

nano-HAP content for Cu2+ and the corresponding calculated values of nano-HAP-alginate

composites and alginate fixed nano-HAP.

Figure 9. Pseudo-first order kinetic model fitting (a), pseudo-second order kinetic model fitting

(b) and intraparticle diffusion model fitting (c) for Cu2+ adsorption onto 50% nano-HAP-alginate

composite.

Figure 10. Langmuir model, Freundlich model and Tempkin model fittings for Cu2+ adsorption

onto nano-HAP

Figure 11. Langmuir model, Freundlich model and Tempkin model fittings for Cu2+ adsorption

onto 50% nano-HAP-alginate composite.

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