Desalination 263 (2010) 8996

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Desalination
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / d e s a l

Removal of nitrobenzene from aqueous solution by adsorption on nanocrystalline hydroxyapatite

Wei Wei a,b, Rong Sun b, Jing Cui a, Zhenggui Wei a,b,
a b

Department of Environmental Science and Engineering, Nanjing Normal University, Nanjing 210097, PR China College of Resources and Environmental Sciences, Nanjing Agricultural University, Nanjing 210095, PR China

a r t i c l e

i n f o

a b s t r a c t
In this study, the nanocrystalline hydroxyapatite (HAP) prepared by thermal decomposition of precursors was used as the adsorbent, and the potential of nanocrystalline HAP for nitrobenzene removal from aqueous solution was evaluated. Results indicated that nitrobenzene adsorption was initially rapid and the adsorption process reached a steady state after 1 min. The adsorption isotherms were well described by the Langmuir and the Freundlich models, the latter being found to provide the better t with the experimental data. The nitrobenzene adsorption capability of the nanocrystalline HAP was investigated as a function of temperature, pH, ionic strength, fulvic acid, and the presence of solvent. According to the experimental results, decrease in pH and temperature resulted in increase in nitrobenzene adsorption capacity; Increasing ionic strength and the presence of fulvic acid decreased the adsorption of nitrobenzene by nanocrystalline HAP; Acetone appeared to inhibit nitrobenzene adsorption to an extent greater than the presence of methanol. Thermodynamics studied revealed that the adsorption of nitrobenzene by nanocrystalline HAP was physisorption, spontaneous and endothermic in nature. This study showed that nanocrystalline HAP could be used as an efcient adsorbent material for the removal of nitrobenzene from aqueous solution. 2010 Elsevier B.V. All rights reserved.

Article history: Received 4 February 2010 Received in revised form 20 June 2010 Accepted 21 June 2010 Available online 14 July 2010 Keywords: Nitrobenzene Adsorption Nanocrystalline hydroxyapatite Isotherm Biocompatible adsorbent

1. Introduction Nitrobenzene, a carcinogenic pollutant, is widely used in the production of different types of products, such as dyes, explosives and pesticides [1]. It is frequently released in the efuent from explosives manufacture as well as in the manufacture of organic chemicals and plastics [2]. Even at low concentrations, nitrobenzene may present high risks to ecological and human health [3]. Because of its toxicity, nitrobenzene is listed as a priority pollutant by the U.S. Environmental Protection Agency [3,4]. Therefore, more and more attention is given to the removal of nitrobenzene from aqueous environment. Conventional methods for the removal of nitrobenzene from aqueous solutions can be divided into three main categories: physical, chemical and biological treatments [58]. Among them, physical adsorption method is generally considered to be the best, effective, low-cost and most frequently used method for the removal of organic pollutants [9,10]. Particularly, adsorption with activated carbon is considered to be one of the most economical and efcient methods for controlling the nitrobenzene in water [1113]. However, the high initial cost and the need for a costly regeneration system make the activated carbon less economically feasible as excellent adsorbent [5,14]. Therefore, the search for low-cost and easily available adsorbents has
Corresponding author. Department of Environmental Science and Engineering, Nanjing Normal University, Nanjing 210097, PR China. Tel./fax: + 86 8439 5014. E-mail addresses: weizhenggui@gmail.com, zgwei@njau.edu.cn (Z. Wei). 0011-9164/$ see front matter 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.desal.2010.06.043

led many researchers to explore more economic and efcient techniques of using the natural and synthetic materials as adsorbents [1518]. Recently, the natural and synthetic inorganic materials have gained importance for their special properties. A signicant aspect of the inorganic adsorbents is that the bonding forces between the adsorbent and the adsorbate are usually weaker than those encountered in activated carbon or polymer adsorbents [9]. On the other hand, the inorganic adsorbents also possess excellent thermal stability. Therefore, the regeneration of the inorganic adsorbents can be achieved by simple and non-destructive methods, such as solvent washing or calcining, which provides the potential approaches to recover these adsorbents. However, the adsorption ability of the traditional natural inorganic adsorbents is low due to their low surface area. Currently, nanocrystalline materials represent a promising application in a variety of elds due to their high surface area and reactivity and their ability to become dispersed in aqueous solution [1921]. Nanocrystalline materials usually display higher surface area and adsorption ability than the traditional materials. In these regards, nanocrystalline materials are one of the most widely used candidates for adsorbents to remove the pollutants from aqueous solutions. Nanocrystalline hydroxyapatite [Ca10(PO4)6(OH)2, HAP] exhibits excellent biocompatibility and adsorption properties, and has been widely used as adsorbents for the adsorption and separation of biomolecules [2224], and for the removal of heavy metals and phenol from contaminated soil and water [9,2527]. The environmental risk of nanocrystalline HAP itself can be neglected because it has displayed

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good cytocompatibility [28]. Moreover, nanocrystalline HAP has also been used for the adsorption of oxalic acid and uoride in our previous work [19,20,22]. However, as to our knowledge, the adsorption and removal of nitrobenzene by HAP has not been reported. The objective of this study was to investigate the possibility of using nanocrystalline HAP as a new biocompatible adsorbent for the adsorption of nitrobenzene from aqueous solution. The effects of contact time, pH, ionic strength, fulvic acid, and the presence of solvent on adsorption processes on the nitrobenzene adsorption, and the adsorption equilibrium and thermodynamic parameters at various temperatures and concentrations were investigated. 2. Materials and methods 2.1. Materials Nitrobenzene (98%, without further purication) was purchased from Shanghai Chemical Reagent Company. Ca(NO3)24H2O, (NH4)2EDTA, NH4H2PO4 were obtained from Nanjing Chemical Reagent Company. Methanol used here was HPLC grade solvents. Deionized water was puried by Millipore Milli-Q system. Unless otherwise stated, all reagents used in this study were analytical grade. 2.2. Preparation and characterization of adsorbent The nanocrystalline HAP adsorbents used in this study were prepared by the thermal decomposition of precursors, this method was described in detail in our previous work [19,22]. Briey, appropriate amounts of Ca(NO3)24H2O, (NH4)2-EDTA, and NH4H2PO4 aqueous solutions were mixed together at a molar ratio of EDTA: Ca: P = 2.667: 1.667: 1, and stirred until a homogeneous solution was formed approximately for 5 min. The nal pH of the solution was controlled to 56 by the addition of ammonia solution. After slowly evaporating the solvent, the precursors were obtained and then were dried at 80 C. The dried precursors were calcined at 800 C for 4 h in air to obtain nanocrystalline HAP. The nal products were used as the adsorbents for the nitrobenzene. The phase purity and crystallinity of the as-prepared HAP were determined by powder X-ray diffraction (XRD) using Cu K ( = 1.5405 ) radiation on a Rigaku D/max-IIIB X-ray powder diffractometer. The morphology and size of the synthetic nanocrystalline HAP were characterized by a Hitachi Model H-7650 transmission electron microscope (TEM). The as-prepared HAP was dissolved in nitric acid and analyzed by inductively coupled plasma-atomic emission spectroscopy (ICP-AES, Pekin Elmer Optimal 2100DV) to determine the Ca/P molar ratio. The specic surface area of nanocrystalline HAP was determined by nitrogen adsorption at 77 K (Micromeritics ASAP 2010). Surface area was calculated from adsorption data using BET equation. And batch equilibration technique [29] was applied to determine pHPZC (point of zero charge) of nanocrystalline HAP. 2.3. Adsorption experiments The effect of contact time on nitrobenzene adsorption on nanocrystalline HAP was studied based on the nitrobenzene concentration in the range from 5 to 50 mg/L. The adsorption experiments were carried out by mixing 1.25 g HAP samples with a 250 ml aqueous solution in a 500 mL stirred ask at temperature of 298 K. Samples were taken out and ltrated by a glass ber with 0.45-m pore size at different times. Then the residual concentration of nitrobenzene was determined. For the optimization of adsorbent dosage, a 10 mL nitrobenzene solution was contacted with different quantities of nanocrystalline HAP adsorbent (210 g/L) till equilibrium was attained and it was found to be 5 g/L.

The adsorption isotherm experiments of nitrobenzene on nanocrystalline HAP, as well as the inuences of pH, ionic strength, fulvic acid, and the presence of solvent on the adsorption of nitrobenzene were performed on the basis of a batch experiment. A given amount of adsorbent (0.05 g) was placed in a 50 mL glass centrifuge tube, into which 10 mL of a nitrobenzene solution with varying concentrations was added. The experiments were performed in a temperaturecontrolled water bath shaker for 4 h at a mixing speed of 200 rpm. The remaining concentration of nitrobenzene was no longer changed with contact time when the adsorption process reached equilibrium, after which the solutions were ltered and analyzed for the remaining concentration of nitrobenzene. The removal efciency of nitrobenzene was calculated from the equation below: C0 Ce 100: C0 1

% Removal =

The adsorption capacity of nitrobenzene was calculated from the following mass balance equation: C0 Ce V m 2

qe =

where qe (mg/g) is the equilibrium adsorption capacity; C0 and Ce (mg/L) are the initial and equilibrium concentrations of nitrobenzene in solution; V (L) is the volume of aqueous solution containing nitrobenzene; and m (g) is the weight of HAP adsorbent. The experiments were performed in triplicate and mean values were taken into account. The relative deviations met with the requirement of less than 5%. 2.4. Analytical method The concentration of nitrobenzene was determined by reversedphase high performance chromatography (RP-HPLC). The chromatographic analyses were performed on a Shimadzu LC-20AT liquid chromatograph equipped with a reversed-phase C18 (Shim-pack VPODS 250 4.6 mm, 5 m particle size) column connected to an SPD-20A Shimadzu UVVis detector. The mobile phase was a mixture of methanolwater (70/30, V/V) at a ow rate of 0.7 mL/min. The injection volume was 20 L and nitrobenzene was detected at a wavelength of 269 nm. Under these conditions, the retention time for nitrobenzene in the column was 9.8 min. 3. Results and discussions 3.1. Characterization of nanocrystalline HAP The XRD pattern of as-prepared HAP was shown in Fig. 1, the synthetic samples were in good agreement with the reference pattern of pure hydroxyapatite (JCPDS no. 09-0432), and no characteristic peaks of impurities, such as calcium hydroxide and calcium phosphates, were observed, meaning that phase pure HAP samples were obtained under the present experimental conditions. Moreover, the sharp diffraction peaks suggested that HAP with high crystallinity was obtained after calcination at 800 C. From XRD data, the crystallinity degree (Xc) of HAP, corresponding to the fraction of crystalline phase present in the examined volume could be determined as: Xc = 1 (V112/300/I300), where V112/300 represented the intensity of the hollow between diffraction peaks (112) and (300), and I300 was the intensity of (300) diffraction peak [30]. The crystallinity degree of the synthetic nanocrystalline HAP was 0.86. By applying the Scherrer formula to the full width at half maximum of the diffraction peaks [31], we could calculate the average particle size of nanocrystalline HAP as 57.4 nm.

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Fig. 1. XRD patterns of the as-prepared HAP and the reference pattern of pure hydroxyapatite (JCPDS no. 09-0432).

Fig. 3. Effect of contact time on nitrobenzene adsorption by nanocrystalline HAP (adsorption conditions: adsorbent dosage = 5 g/L, pH 4.0, and temperature = 298 K).

Fig. 2 showed the morphology of nanocrystalline HAP samples by TEM observation. It indicated that the synthetic HAP samples are sphere-like particles with almost no amorphous constituents and weakly aggregated. The particle size of the synthetic HAP was distributed in the range of 4060 nm, which was in consistent with the XRD data. The Ca/P molar ratio analyzed by ICP-AES was determined to be 1.657, since the HAP had a stoichiometric Ca/P ratio of 1.667, the synthetic HAP was slightly calcium-decient, which was known to be a typical characteristic of HAP being prepared by the wet method. The surface area of the HAP adsorbents, measured by a BET method, was determined to be 42.32 m2/g, and the pHPZC of nanocrystalline HAP was 7.9. 3.2. Effect of contact time and adsorbent dosage on nitrobenzene adsorption Fig. 3 showed the effect of contact time on the adsorption of the nitrobenzene on nanocrystalline HAP. The adsorption equilibrium of nitrobenzene was obtained within 1 min for the initial nitrobenzene concentration of 5, 10, and 50 mg/L, respectively. Thereafter, no detectable concentration changes occurred after adsorption equilibrium (1 min) and the average removal efciency of nitrobenzene

reached about 80.4% (0.804 mg/g adsorption capacity), 70.9% (1.418 mg/g adsorption capacity), and 56.6% (5.661 mg/g adsorption capacity) when the initial concentrations of nitrobenzene were 5, 10, and 50 mg/L, respectively. It was considered that a hydrophobic interaction between adsorbent and organic compounds might be attributed to the rapid adsorption rate [32]. The rapid adsorption of nitrobenzene on nanocrystalline HAP ensured that sufcient time was available for adsorption equilibration to get at the usual operator condition of the adsorption. The equilibrium time of different initial nitrobenzene concentrations was also conducted and the results showed that the initial nitrobenzene concentrations had little effect on the adsorption equilibrium time. Moreover, Fig. 3 also showed that the removal of nitrobenzene at adsorption equilibrium decreased with increasing initial nitrobenzene concentration. The reason was the limited number of adsorption sites available for the uptake of nitrobenzene at a xed adsorbent dosage. The effect of adsorbent dosage was studied with different adsorbent dosages (210 g/L) and 10 mL of 10 mg/L nitrobenzene solutions at equilibrium time. Increase in adsorbent dosage increased the percent removal for nitrobenzene. With the increase in nanocrystalline HAP dosage from 2 to 5 g/L, the nitrobenzene removal efciency increased rapidly from 66.2 to 70.9%. This was attributed to an increase in the adsorbent concentration, which increased the available surface area and adsorption sites [27]. With a further increase in nanocrystalline HAP dosage to 10 g/L, the nitrobenzene removal efciency increased slightly to 72.6%. It is readily understood that the number of available adsorption sites increases with the increase in the adsorbent dosage and it, therefore, leads to the increase in the amount of adsorbed nitrobenzene molecular. The results also indicated that it was possible to remove nitrobenzene completely when there was sufcient nanocrystalline HAP surface area in solution. In this study, the optimized adsorbent dosage was xed at 5 g/L for further experiments. On the other hand, adsorption capacity was decreased with an increase in adsorbent dosage. As the adsorbent dose was increased from 2.0 to 10 g/L, the adsorption capacity for nitrobenzene decreased from 3.31 to 0.726 mg/g. The decrease in adsorption capacity with the increase in the adsorbent dosage was mainly attributed to the unsaturation of adsorption sites during the adsorption process [9]. 3.3. Adsorption isotherms Adsorption equilibrium data, expressed by the mass of adsorbate adsorbed per unit weight of adsorbent and liquid phase equilibrium

Fig. 2. The TEM micrograph of the synthetic nanocrystalline HAP.

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most popular isotherm models due to its simplicity and its good agreement with experimental data. The Langmuir isotherm equation is expressed in the linear form as: 1 1 1 = + qe Q0 Q 0 KL Ce 3

Fig. 4. Adsorption isotherm of nitrobenzene on nanocrystalline HAP at different temperatures (adsorption conditions: adsorbent dosage = 5 g/L and pH 4.0).

where qe (mg/g) is the amount adsorbed at equilibrium; Ce (mg/L) is the equilibrium concentration of nitrobenzene in solution; Q0 (mg/g) is the maximum monolayer adsorption capacity; and KL (L/mg) is the constant related to the free energy of adsorption. The Freundlich [34] isotherm model is an empirical equation and the model is valid for heterogeneous surfaces. It assumes that the adsorption process occurs on the heterogeneous surfaces and the adsorption capacity is related to the concentration of nitrobenzene at equilibrium. The Freundlich model is generally expressed in linear form as: ln qe = ln KF + 1 ln Ce n 4

concentration of adsorbate, were usually represented by adsorption isotherms, which is of importance in the design of adsorption systems. The adsorption isotherms of nitrobenzene on nanocrystalline HAP at temperatures of 282, 290, and 298 K were shown in Fig. 4. The adsorption of nitrobenzene on nanocrystalline HAP decreased from 13.82 mg/g (69.1% removal) to 9.24 mg/g (46.2% removal) when temperature was increased from 282 to 298 K at an initial concentration of 100 mg/L. The decrease in the equilibrium adsorption of nitrobenzene with temperature demonstrated that nitrobenzene removal by adsorption on nanocrystalline HAP favored a low temperature. Adsorption equilibrium data have been tested by using Langmuir and Freundlich isotherms at various temperatures. The Langmuir [33] theory is valid for monolayer adsorption onto a surface containing a nite number of identical sites, and is one of the

where qe (mg/g) is the amount adsorbed at equilibrium; KF [mg/g(L/ mg)1/n] is the empirical constant of Freundlich isotherm; and Ce (mg/L) is the equilibrium concentration of the nitrobenzene in solution. The constant n is the empirical parameter related to the intensity of adsorption, which varies with the heterogeneity of the material. When 1/n values are in the range 0.1 b 1/n b 1, the adsorption process is favorable. Fig. 5 showed the tting plots of Langmuir and Freundlich adsorption isotherms of nitrobenzene on nanocrystalline HAP at 298 K, (plots at 282 and 290 K were not shown), respectively. Table 1 summarized the constants of the Freundlich and Langmuir isotherms obtained from the slope and intercept of the plots of each isotherm at different temperatures. Most of the R2 values exceed 0.95 for both the

Fig. 5. The Langmuir (left) and Freundlich (right) isotherms plot for nitrobenzene adsorption on nanocrystalline HAP at the temperature of 298 K (adsorption conditions: adsorbent dosage = 5 g/L and pH 4.0).

W. Wei et al. / Desalination 263 (2010) 8996 Table 1 Parameters of adsorption isotherms of nitrobenzene on nanocrystalline HAP at different temperatures. Temperature (K) Freundlich isotherm KF [mg/g (L/mg)1/n] 0.8619 0.8529 0.8269 1/n 0.7924 0.6920 0.6090 R2 0.9934 0.9962 0.9962 Langmuir isotherm Q 0 (mg/g) 8.993 7.174 5.754 KL (L/mg) 0.1161 0.1449 0.1757 R2 0.9606 0.9563 0.9449

93

282 290 298

The values of H0 can be obtained from the slope of the plots of ln 1/C e versus 1/T . The negative value of H 0 ( 16.91 kJ/mol, qe = 2.0 mg/g) suggested the process to be exothermic. The values of G0 were calculated as from 2.96 to 4.07 kJ/mol. It was noted that the G0 values were all negative, which indicated the feasibility and spontaneous adsorption of nitrobenzene on nanocrystalline HAP. The negative value of S0 ( 43.09 J/(mol K), qe = 2.0 mg/g, 298 K) showed the decreased randomness at the solidsolution interface during the adsorption of nitrobenzene on nanocrystalline HAP. 3.5. Effect of pH on nitrobenzene adsorption

Freundlich and Langmuir models, suggesting that both models closely tted the experimental results. However, the Freundlich model was more suitable than the Langmuir model to describe the adsorption isotherm, as reected with correlation coefcients. The values of KF were 0.8619, 0.8529 and 0.8269 [mg/g(L/mg)1/n] at 282, 290 and 298 K, respectively. KF decreased with the increase in the temperatures, revealing that the adsorption capacity of nitrobenzene on nanocrystalline HAP decreased with the increase in the temperatures. Moreover, when the interaction is exothermic, the adsorbate has a tendency to escape from the solid phase to the solution. Thus, rise in temperature and excess energy supply will promote desorption. The Freundlich exponent of 1/n gave information about surface heterogeneity and surface afnity for the solute. The values of 1/n between 0.6090 and 0.7924 indicated favorable adsorption and a high afnity of nanocrystalline HAP for nitrobenzene. If the n is below one, then the adsorption is chemical process; otherwise, the adsorption is physical process [9,35]. All values of n exceed one, suggesting the adsorption of nitrobenzene on nanocrystalline HAP was physical process. In summary, this section study showed that the adsorption of nitrobenzene on the nanocrystalline HAP was correlated well with the Freundlich equation as compared to Langmuir equation under the concentration range studied, according to the R2 values shown in Table 1. Then the following equations use Freundlich constants to calculate the thermodynamic parameters. 3.4. Thermodynamic analyses In any adsorption process and engineering practice, both energy and entropy factors should be considered in order to determine what processes will occur spontaneously. Values of thermodynamic parameters are the actual indicators for practical application of a process. Generally, the standard free energy change (G0) of adsorption, standard enthalpy change (H0) and standard entropy change (S0) were calculated from data interpolated using the best tting isotherm. The values obtained were dependent upon the extent of surface coverage of the adsorbent. While the estimated heats of adsorption are probably not accurate because of the assumptions involved in their calculation, they are considered to be the correct order of magnitude [36]. In this study, the Freundlich isotherm was used to calculate the thermodynamic parameters using the following equations [36,37]: 1 H 0 = ln K0 Ce RT
0

It is well known that the most critical parameter affecting the adsorption process in the removal of nitrobenzene by the adsorption method is the pH of the adsorption medium. This is due to the charge of the adsorbate and the adsorbent often depending on the pH of the solution. In order to determine the effect of pH on adsorption capacity of nanocrystalline HAP, solutions were prepared at different pH values ranging from 2.0 to 11.0. The pH before and after adsorption was also measured and the results showed that the difference between the two pH values was less than 0.2. The dependence of pH on the adsorption of nitrobenzene at an initial concentration of 10.0 mg/L on nanocrystalline HAP was showed in Fig. 6. It was clear to see that the adsorption capacity decreases sharply when the pH was higher than 6.0. The maximal adsorption capacity of nitrobenzene on nanocrystalline HAP was at pH 2.0, and the adsorption capacity was 1.428 mg/g (71.4% removal), while at pH 11.0, the adsorption capacity of nitrobenzene was 0.681 mg/g (34.1% removal). At low pH, neutralization of the negative charge at the surface of the adsorbents increased the protonation and resulted in higher adsorption of nitrobenzene on HAP. This facilitated diffusion and resulted in a larger number of active sites on the surfaces of the adsorbents thereby enhancing adsorption at the surface. On the other hand, with increasing pH deprotonation of nitrobenzene took place, which hindered diffusion and a constant decrease in the amount of nitrobenzene adsorbed was observed. Moreover, based on the conclusions of Lu et al. [38] and Qin et al. [5], the maximum extent of nitrobenzene adsorption was at a pH value close to pHPZC of adsorbent, if hydrogen bond interaction was the dominant mechanism for nitrobenzene adsorption. However, it was clear that the maximum extent of adsorption (Fig. 6) was not at a pH value around nanocrystalline HAP pHPZC (7.9) in this study. Thus, it could be inferred that a specic interaction like hydrophobic interaction at the interface occurred between the unionizable nitrobenzene and nanocrystalline HAP.

ln

5 6

G = nRT
0

S =

H G T

where Ce (mg/L) is the equilibrium nitrobenzene concentration in the solution; n is the tting constant of Freundlich exponent; R is the universal gas constant (8.314 J/(mol K)); T is the temperature in Kelvin, and K0 is the empirical constant of Freundlich.

Fig. 6. Effect of solution pH on the adsorption of nitrobenzene on nanocrystalline HAP (adsorption conditions: adsorbent dosage = 5 g/L, temperature = 298 K, initial nitrobenzene concentration = 10 mg/L).

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Fig. 7. Effect of ionic strength on the adsorption of nitrobenzene on nanocrystalline HAP (adsorption conditions: adsorbent dosage = 5 g/L, pH 4.0, and temperature = 298 K).

Fig. 9. Effect of solvent on the adsorption of nitrobenzene on nanocrystalline HAP (adsorption conditions: adsorbent dosage = 5 g/L, pH 4.0, and temperature = 298 K).

3.6. Effect of ionic strength and fulvic acid on nitrobenzene adsorption Because NaCl is often used as a stimulator in adsorption processes, the effect of ionic strength (adjusted by NaCl) on nitrobenzene adsorption has been determined and the results are showed in Fig. 7. It indicated that the amount of adsorbed nitrobenzene on nanocrystalline HAP decreased with the increase of NaCl concentration of the solution. As nitrobenzene is a nonpolar hydrophobic chemical, increasing ionic strength will lead to a decrease of the solubility of nitrobenzene in water. However, the amount of adsorbed nitrobenzene on nanocrystalline HAP decreased with the increase of ionic strength. It was considered that the additive (NaCl) preferred to compete with nitrobenzene for space in HAP, which resulted in the decrease in the amount of nitrobenzene adsorption. Previous studies have indicated that the interactions of dissolved organic carbon (DOC) with organic pollutant could enhance water solubility and thus mobility. [39,40] In this work, the effect of fulvic acid on nitrobenzene adsorption was studied and the results were showed in Fig. 8. The results suggested that the adsorption of nitrobenzene on nanocrystalline HAP decreased from 1.418 mg/g (70.9% removal) to 0.898 mg/g (44.9% removal) when the concentration of fulvic acid was increased from 0 to 100 mg/L at an initial nitrobenzene concentration of 10 mg/L. This could be explained as the existence of fulvic acid partially blocked nanocrystalline HAP adsorption sites and inhibited nitrobenzene corrosion. However,

further increase of FA after 100 mg/L did not produce signicant changes in nitrobenzene adsorption. 3.7. Adsorption of nitrobenzene from solventwater solutions Adsorption of nitrobenzene from aqueous solutions containing 10% methanol or 10% acetone was studied. Fig. 9 showed the adsorption isotherm of nitrobenzene from solventwater solutions. The adsorption of nitrobenzene on nanocrystalline HAP decreased from 1.418 mg/g (70.9% removal) in water solution, to 1.16 mg/g (57.9% removal) in methanolwater solution and 0.661 mg/g (33.1% removal) in acetonewater solution, respectively, when the initial concentration of nitrobenzene was 10 mg/L. The addition of organic solvents to water led to a decrease in adsorption on nanocrystalline HAP. Similar results were obtained by Qin et al. [5], who investigated the adsorption of nitrobenzene by synthetic mesoporous molecular sieves, and indicated that the addition of organic solvents to water enhanced the interaction between the nitrobenzene and the solvents, resulting in a decrease in adsorption capacity. However, it was shown that acetone appeared to inhibit nitrobenzene adsorption to an extent greater than the presence of methanol. That was because acetone was less polar and could interact with nitrobenzene more strongly than methanol. The inhibitory effect in less polar solution for nitrobenzene adsorption was greater than that in polar solution which suggested that hydrophobic driving force was the dominant mechanism for nitrobenzene adsorption on nanocrystalline HAP. 3.8. Comparison of results with related studies In order to assess the performance of nanocrystalline HAP as an adsorbent for nitrobenzene, a comparison with other adsorbents was given in Table 2. In previous studies, batch adsorption of nitrobenzene on synthetic MCM-41 was performed by Qin et al. [5] and the equilibrium nitrobenzene adsorption capacity was 1.8413.705 mol/g. Zhao et al.

Table 2 Comparison of the adsorption capacities of nitrobenzene for various adsorbents. Adsorbent nanocrystalline HAP (MCM-41) Marine sediment Faujasite Activated carbon Oxidized C1 C1 Q 0 (mg/g) 8.993 3.705 mol/g 6.035 267.2 263 158 238 References This study [5] [41] [14] [42] [42] [42]

Fig. 8. Effect of fulvic acid on the adsorption of nitrobenzene on nanocrystalline HAP (adsorption conditions: adsorbent dosage = 5 g/L, pH 4.0, temperature = 298 K, and initial nitrobenzene concentration = 10 mg/L).

W. Wei et al. / Desalination 263 (2010) 8996 Table 3 Characteristics of nitrobenzene-containing wastewater. Parameter pH Turbidity (NTU) Suspended solids (mg/L) Nitrobenzene (mg/L) Aniline (mg/L) CODCr (mg/L) TOC (mg/L) Value 5.2 21.2 102.7 78.1 4.8 626.5 216.4

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4. Conclusions Synthetic nanocrystalline HAP was demonstrated to have considerable potential for the removal of nitrobenzene from aqueous solutions over a wide range of concentration. The results showed that nitrobenzene could be adsorbed on nanocrystalline HAP quickly. The adsorption followed both Langmuir and Freundlich isotherms but better tted to Freundlich isotherm. The removal of nitrobenzene from aqueous solution strongly depended on the pH of the solution and temperature. Decrease in pH and temperature resulted in increase in nitrobenzene adsorption capacity. Increasing ionic strength and the presence of fulvic acid decreased the adsorption of nitrobenzene by nanocrystalline HAP. Thermodynamic calculations showed that the nitrobenzene adsorption process by nanocrystalline HAP was physisorption, spontaneous and exothermic in nature. The main advantages of nanocrystalline HAP were biocompatible, lowcost, easy to prepare in large scale, and could be effectively utilized as promising adsorbent for the removal of nitrobenzene from aqueous solutions. Acknowledgments This work is supported by the National Programs for High Technology Research and Development of China (no. 2007AA10Z406), the Research Fund for the Doctoral Program of Higher Education (no. 20070307051), SRF for ROCS, SEM, the Foundation for Talent Recommendation Program of Nanjing Normal University, and the Leading Academic Discipline Program, 211 Project for Nanjing Normal University (the 3rd phase). References
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[41] investigated the adsorption of nitrobenzene on marine sediments; the equilibrium uptake of nitrobenzene in natural seawater was nitrobenzene was 1.6056.035 mg/g. The studies of Reungoat et al. [14] showed that the nitrobenzene adsorption capacity on faujasite was about 267.2 mg/g. The adsorption capacity of nitrobenzene on activated carbon and other carbon materials was 158263 mg/g determined by Dai et al. [42]. In the present study, the adsorption capacity of nitrobenzene on nanocrystalline HAP was obtained as 5.7548.993 mg/g at 282298 K. This result conrmed that the adsorption capacity of nanocrystalline HAP for nitrobenzene was similar or higher than these natural or synthetic inorganic adsorbents. However, the adsorption capacity of nitrobenzene on nanocrystalline HAP was low compared to the usual adsorption capacities observed with activated carbons (100300 mg/g) [14,42]. This was most probably due to the small surface area of nanocrystalline HAP (42.32 m2/g) compared to those usually associated with activated carbons (around 1000 m2/g) [9,42]. However, when normalized for the surface area, the adsorption capacity for nanocrystalline HAP (approximately 0.21 mg/m2) was similar to that generally observed with activated carbons (0.26 mg/m2) [42]. However, the nanocrystalline HAP materials are low-cost and easy to prepare in large scale, and the environmental risk of nanocrystalline HAP itself can be neglected because it has displayed good cytocompatibility [28]. Therefore, nanocrystalline HAP exhibits potential as a new biocompatible adsorbent for the removal of nitrobenzene from aqueous solution.

3.9. Adsorption of nitrobenzene from wastewater The wastewater obtained from a nitrobenzene manufacturing plant in Nanjing was used for the adsorption experiment. The characteristics of wastewater were shown in Table 3. Since the pH of the wastewater was acidic, the adsorption experiments were done without any pH correction. It was found that a removal of 52.4% nitrobenzene was achieved at an adsorbent dosage of 5 g/L, on further increasing the adsorbent dosage to 20 g/L, a removal efciency of 95% could be achieved.

3.10. Cost evaluation The adsorption of nitrobenzene on nanocrystalline HAP adsorbent obtained by thermal decomposition of precursors is quite comparable to other commercially available adsorbents, of which activated carbon is widely used for the removal of contaminant form aqueous solution. In China, the commercially available activated carbon costs U.S. $ 1857 per tonne. The HAP adsorbent is available for U.S. $ 2048 per tonne, which is a little costly than activated carbon, however, nanocrystalline HAP has signicant advantages over the conventional adsorbents; it could be conveniently regenerated by high-temperature heat treatment due to its excellent thermal stability, and the environmental risk of nanocrystalline HAP itself can be neglected because it has displayed good cytocompatibility. Hence the developed adsorbent has great potential in the removal of nitrobenzene from aqueous solution.

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