Desalination 263 (2010) 89–96

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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
Department of Environmental Science and Engineering, Nanjing Normal University, Nanjing 210097, PR China
b
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

Article history: In this study, the nanocrystalline hydroxyapatite (HAP) prepared by thermal decomposition of precursors
Received 4 February 2010 was used as the adsorbent, and the potential of nanocrystalline HAP for nitrobenzene removal from aqueous
Received in revised form 20 June 2010 solution was evaluated. Results indicated that nitrobenzene adsorption was initially rapid and the adsorption
Accepted 21 June 2010
process reached a steady state after 1 min. The adsorption isotherms were well described by the Langmuir
Available online 14 July 2010
and the Freundlich models, the latter being found to provide the better fit with the experimental data. The
Keywords:
nitrobenzene adsorption capability of the nanocrystalline HAP was investigated as a function of temperature,
Nitrobenzene pH, ionic strength, fulvic acid, and the presence of solvent. According to the experimental results, decrease in
Adsorption pH and temperature resulted in increase in nitrobenzene adsorption capacity; Increasing ionic strength and
Nanocrystalline hydroxyapatite the presence of fulvic acid decreased the adsorption of nitrobenzene by nanocrystalline HAP; Acetone
Isotherm appeared to inhibit nitrobenzene adsorption to an extent greater than the presence of methanol.
Biocompatible adsorbent 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 efficient adsorbent material for the removal of nitrobenzene from aqueous solution.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction led many researchers to explore more economic and efficient

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 effluent 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 [5–8]. 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 efficient methods for
controlling the nitrobenzene in water [11–13]. 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).
techniques of using the natural and synthetic materials as adsorbents
[15–18]. Recently, the natural and synthetic inorganic materials have
gained importance for their special properties. A significant 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, nanocrystal-
line materials represent a promising application in a variety of fields due
to their high surface area and reactivity and their ability to become
dispersed in aqueous solution [19–21]. 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 [22–24], and for the removal of heavy metals and phenol
from contaminated soil and water [9,25–27]. The environmental risk of
nanocrystalline HAP itself can be neglected because it has displayed

0011-9164/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2010.06.043
90 W. Wei et al. / Desalination 263 (2010) 89–96
good cytocompatibility [28]. Moreover, nanocrystalline HAP has also
been used for the adsorption of oxalic acid and fluoride 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 purification) was purchased
from Shanghai Chemical Reagent Company. Ca(NO3)2·4H2O, (NH4)2-
EDTA, NH4H2PO4 were obtained from Nanjing Chemical Reagent
Company. Methanol used here was HPLC grade solvents. Deionized
water was purified 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]. Briefly, appropriate
amounts of Ca(NO3)2·4H2O, (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 final pH of the solution was controlled to
5–6 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 final 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 Kα (λ =
1.5405 Å) radiation on a Rigaku D/max-IIIB X-ray powder diffractom-
eter. 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
specific 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 concen-
tration 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 flask at temperature of 298 K. Samples
were taken out and filtrated by a glass fiber with 0.45-μm 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 (2–10 g/L) till equilibrium was
attained and it was found to be 5 g/L.
The adsorption isotherm experiments of nitrobenzene on nano-
crystalline HAP, as well as the influences 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 temperature-
controlled 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 filtered and analyzed for the remaining
concentration of nitrobenzene.
The removal efficiency of nitrobenzene was calculated from the
equation below:
ðC0 −Ce Þ
% Removal = × 100: ð1Þ
C0
The adsorption capacity of nitrobenzene was calculated from the
following mass balance equation:
ðC0 −Ce ÞV
qe = ð2Þ
m
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 nitroben-
zene; 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 reversed-
phase high performance chromatography (RP-HPLC). The chromato-
graphic analyses were performed on a Shimadzu LC-20AT liquid
chromatograph equipped with a reversed-phase C18 (Shim-pack VP-
ODS 250× 4.6 mm, 5 μm particle size) column connected to an SPD-20A
Shimadzu UV–Vis detector. The mobile phase was a mixture of
methanol–water (70/30, V/V) at a flow rate of 0.7 mL/min. The injection
volume was 20 μL 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 deter-
mined 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.
 W. Wei et al. / Desalination 263 (2010) 89–96
Fig. 1. XRD patterns of the as-prepared HAP and the reference pattern of pure
hydroxyapatite (JCPDS no. 09-0432).
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 40–60 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-deficient, 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 equilib-
rium (1 min) and the average removal efficiency of nitrobenzene
Fig. 2. The TEM micrograph of the synthetic nanocrystalline HAP.
91
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).
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 sufficient 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 fixed adsorbent dosage.
The effect of adsorbent dosage was studied with different
adsorbent dosages (2–10 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 nano-
crystalline HAP dosage from 2 to 5 g/L, the nitrobenzene removal
efficiency 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 efficiency 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 sufficient nanocrystalline HAP surface
area in solution. In this study, the optimized adsorbent dosage was
fixed 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
92 W. Wei et al. / Desalination 263 (2010) 89–96
Fig. 4. Adsorption isotherm of nitrobenzene on nanocrystalline HAP at different
temperatures (adsorption conditions: adsorbent dosage = 5 g/L and pH 4.0).
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 concen-
tration 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 finite number of identical sites, and is one of 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).
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
= + ð3Þ
qe Q0 Q 0 KL Ce
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:
1
ln qe = ln KF + ln Ce ð4Þ
n
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 fitting 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
 W. Wei et al. / Desalination 263 (2010) 89–96 93

Table 1 The values of ΔH0 can be obtained from the slope of the plots of ln
Parameters of adsorption isotherms of nitrobenzene on nanocrystalline HAP at different 1/C e versus 1/T. The negative value of ΔH 0 (− 16.91 kJ/mol,
temperatures.
qe = 2.0 mg/g) suggested the process to be exothermic. The values
Temperature Freundlich isotherm Langmuir isotherm of ΔG0 were calculated as from −2.96 to −4.07 kJ/mol. It was noted
(K)
KF [mg/g 1/n R2 Q 0 (mg/g) KL (L/mg) R2 that the ΔG0 values were all negative, which indicated the feasibility
(L/mg)1/n] and spontaneous adsorption of nitrobenzene on nanocrystalline HAP.
282 0.8619 0.7924 0.9934 8.993 0.1161 0.9606 The negative value of ΔS0 (− 43.09 J/(mol K), qe = 2.0 mg/g, 298 K)
290 0.8529 0.6920 0.9962 7.174 0.1449 0.9563 showed the decreased randomness at the solid–solution interface
298 0.8269 0.6090 0.9962 5.754 0.1757 0.9449 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
fitted the experimental results. However, the Freundlich model was
more suitable than the Langmuir model to describe the adsorption
isotherm, as reflected with correlation coefficients. 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 tempera-
tures, 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 hetero-
geneity and surface affinity for the solute. The values of 1/n between
0.6090 and 0.7924 indicated favorable adsorption and a high affinity
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 para-
meters are the actual indicators for practical application of a process.
Generally, the standard free energy change (ΔG0) of adsorption,
standard enthalpy change (ΔH0) and standard entropy change (ΔS0)
were calculated from data interpolated using the best fitting 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 equa-
tions [36,37]:
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 nanocrys-
talline 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 nanocrystal-
line 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, neutral-
ization 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 mecha-
nism 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 specific interaction like hydrophobic interaction at the
interface occurred between the unionizable nitrobenzene and
nanocrystalline HAP.

1 ΔH 0
ln = ln K0 − ð5Þ
Ce RT

0
ΔG = −nRT ð6Þ

0 0
0 ΔH −ΔG
ΔS = ð7Þ
T

where Ce (mg/L) is the equilibrium nitrobenzene concentration in the

solution; n is the fitting constant of Freundlich exponent; R is the Fig. 6. Effect of solution pH on the adsorption of nitrobenzene on nanocrystalline HAP
universal gas constant (8.314 J/(mol K)); T is the temperature in (adsorption conditions: adsorbent dosage = 5 g/L, temperature = 298 K, initial nitro-
Kelvin, and K0 is the empirical constant of Freundlich. benzene concentration = 10 mg/L).
94 W. Wei et al. / Desalination 263 (2010) 89–96
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).
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 nanocrys-
talline 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 nitroben-
zene 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 concen-
tration 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,
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).
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).
further increase of FA after 100 mg/L did not produce significant
changes in nitrobenzene adsorption.
3.7. Adsorption of nitrobenzene from solvent–water solutions
Adsorption of nitrobenzene from aqueous solutions containing
10% methanol or 10% acetone was studied. Fig. 9 showed the
adsorption isotherm of nitrobenzene from solvent–water 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 methanol–water solution and 0.661 mg/g (33.1%
removal) in acetone–water 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 1.841–3.705 μmol/g. Zhao et al.
Table 2
Comparison of the adsorption capacities of nitrobenzene for various adsorbents.
Adsorbent Q 0 (mg/g) References
nanocrystalline HAP 8.993 This study
(MCM-41) 3.705 μmol/g [5]
Marine sediment 6.035 [41]
Faujasite 267.2 [14]
Activated carbon 263 [42]
Oxidized C1 158 [42]
C1 238 [42]
 W. Wei et al. / Desalination 263 (2010) 89–96
Table 3
Characteristics of nitrobenzene-containing wastewater.
Parameter Value
pH 5.2
Turbidity (NTU) 21.2
Suspended solids (mg/L) 102.7
Nitrobenzene (mg/L) 78.1
Aniline (mg/L) 4.8
CODCr (mg/L) 626.5
TOC (mg/L) 216.4
[41] investigated the adsorption of nitrobenzene on marine sediments;
the equilibrium uptake of nitrobenzene in natural seawater was
nitrobenzene was 1.605–6.035 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 158–263 mg/g
determined by Dai et al. [42]. In the present study, the adsorption
capacity of nitrobenzene on nanocrystalline HAP was obtained as
5.754–8.993 mg/g at 282–298 K. This result confirmed that the
adsorption capacity of nanocrystalline HAP for nitrobenzene was
similar or higher than these natural or synthetic inorganic adsor-
bents. However, the adsorption capacity of nitrobenzene on nano-
crystalline HAP was low compared to the usual adsorption capacities
observed with activated carbons (100–300 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 nanocrystal-
line 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 biocom-
patible 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 efficiency 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 significant advantages over the conventional adsorbents; it
could be conveniently regenerated by high-temperature heat treat-
ment 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.
95
4. Conclusions
Synthetic nanocrystalline HAP was demonstrated to have consid-
erable 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 fitted 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, low-
cost, 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 Recom-
mendation Program of Nanjing Normal University, and the Leading
Academic Discipline Program, 211 Project for Nanjing Normal Univer-
sity (the 3rd phase).
References
[1] M.C. He, Y. Li, X.R. Sun, Z.F. Yang, Distribution patterns of nitrobenzene and
polychlorinated biphenyls in water, suspended particulate matter and sediment
from mid- and down-stream of the Yellow River (China), Chemosphere 65 (2006)
365–374.
[2] M. Ikeda, A. Kita, Excretion of p-nitrophenol and p-aminophenol in the urine of a
patient exposed to nitrobenzene, Br. J. Ind. Med. 21 (1964) 210–213.
[3] X.L. Wang, Y. Li, Y.Z. Wang, T. Wang, Q. Gao, X.Y. Du, New evidence for the
importance of Mn oxides contributed to nitrobenzene adsorption onto the
surficial sediments in Songhua River, China, J. Hazard. Mater. 172 (2009)
755–762.
[4] S.F. Nishino, J.C. Spain, Degradation of Nitrobenzene by a Pseudomonas
pseudoalcaligenes, Appl. Environ. Microbiol. 59 (1993) 2520–2525.
[5] Q.D. Qin, J. Ma, K. Liu, Adsorption of nitrobenzene from aqueous solution by MCM-
41, J. Colloid Interface Sci. 315 (2007) 80–86.
[6] M. Koh, T. Nakajima, Adsorption of aromatic compounds on CxN-coated activated
carbon, Carbon 38 (2000) 1947–1954.
[7] Y.X. Yang, J. Ma, Q.D. Qin, X.D. Zhai, Degradation of nitrobenzene by nano-TiO2
catalyzed ozonation, J. Mol. Catal. A: Chem. 267 (2007) 41–48.
[8] S.F. Nishino, J.C. Spain, Oxidative pathway for the biodegradation of nitrobenzene
by Comamonas sp. strain JS765, Appl. Environ. Microbiol. 61 (1995) 2308–2313.
[9] K.L. Lin, J.Y. Pan, Y.W. Chen, R.M. Cheng, X.C. Xu, Study the adsorption of phenol
from aqueous solution on hydroxyapatite nanopowders, J. Hazard. Mater. 161
(2009) 231–240.
[10] O.J. Hao, H. Kim, P.C. Chiang, Decolorization of wastewater, Crit. Rev. Environ. Sci.
Technol. 30 (2000) 449–505.
[11] M. Franz, H.A. Arafat, N.G. Pinto, Effect of chemical surface heterogeneity on the
adsorption mechanism of dissolved aromatics on activated carbon, Carbon 38
(2000) 1807–1819.
[12] M. Miyahara, M. Okazaki, Concentration dependence of surface diffusivity of
nitrobenzene and benzonitrile in the liquid phase adsorption onto activated
carbon, J. Chem. Eng. Jpn 25 (1992) 408–414.
[13] L. Li, P.A. Quinlivan, D.R.U. Knappe, Effects of activated carbon surface chemistry
and pore structure on the adsorption of organic contaminants from aqueous
solution, Carbon 40 (2002) 2085–2100.
[14] J. Reungoat, J.S. Pic, M.H. Manéro, H. Debellefontaine, Adsorption of nitrobenzene
from water onto high silica zeolites and regeneration by ozone, Separat. Sci.
Technol. 42 (2007) 1447–1463.
[15] I. Dékámy, A. Farkas, I. Regdon, E. Klumpp, H.D. Narres, M.J. Schwuger, Adsorption
of nitrobenzene and n-pentanol from aqueous solution on hydrophilic and
hydrophobic clay minerals, Colloid Polym. Sci. 274 (1996) 981–988.
[16] A. Zlatkis, L. Ghaoui, S. Weisner, H. Shanfield, A new adsorbent for trace level
organic contaminants, Chromatographia 20 (1985) 343–346.
[17] S. Wang, H. Wu, Environmental-benign utilisation of fly ash as low-cost
adsorbents, J. Hazard. Mater. 136 (2006) 482–501.
96 W. Wei et al. / Desalination 263 (2010) 89–96
[18] M.Z. Othman, F.A. Roddick, R. Snow, Removal of dissolved organic compounds in
fixed-bed columns: evaluation of low-rank coal adsorbents, Water Res. 35 (2001)
2943–2949.
[19] S. Gao, R. Sun, Z.G. Wei, H.Y. Zhao, H.X. Li, F. Hu, Size-dependent defluoridation
properties of synthetic hydroxyapatite, J. Fluorine Chem. 130 (2009) 550–556.
[20] S. Gao, J. Cui, Z.G. Wei, Study on the fluoride adsorption of various apatite
materials in aqueous solution, J. Fluorine Chem. 130 (2009) 1035–1041.
[21] Z.Z. Zhang, M.Y. Li, W. Chen, S.Z. Zhu, N.N. Liu, L.Y. Zhu, Immobilization of lead and
cadmium from aqueous solution and contaminated sediment using nano-
hydroxyapatite, Environ. Pollut. 158 (2010) 514–519.
[22] W. Wei, R. Sun, Z.G. Wei, H.Y. Zhao, H.X. Li, F. Hu, Elimination of the interference
from nitrate ions on oxalic acid in RP-HPLC by solid-phase extraction with
nanosized hydroxyapatite, J. Liq. Chrom. Rel. Technol. 32 (2009) 106–124.
[23] G.M.S. El Shafei, N.A. Moussa, Adsorption of some essential amino acids on
hydroxyapatite, J. Colloid Interface Sci. 238 (2001) 160–168.
[24] O. Takagi, N. Kuramoto, M. Ozawa, S. Suzuki, Adsorption/desorption of acidic and
basic proteins on needle-like hydroxyapatite filter prepared by slip casting,
Ceram. Int. 30 (2004) 139–143.
[25] Y. Xu, F.W. Schwartz, S.J. Traina, Sorption of Zn2+ and Cd2+ on hydroxyapatite-
surfaces, Environ. Sci. Technol. 28 (1994) 1472–1480.
[26] Q.Y. Ma, T.J. Logan, S.J. Traina, J.A. Ryan, Effects of aqueous Al, Cd, Cu, Fe(II), Ni, and
Zn on Pb immobilization by hydroxyapatite, Environ. Sci. Technol. 28 (1994)
408–418.
[27] X.L. Pan, J.L. Wang, D.Y. Zhang, Sorption of cobalt to bone char: kinetics,
competitive sorption and mechanism, Desalination 249 (2009) 609–614.
[28] X.Y. Lin, H.S. Fan, X.D. Li, M. Tang, X.D. Zhang, Evaluation of bioactivity and
cytocompatibility of nano hydroxyapatite/collagen composite in vitro, Key Eng.
Mater. 284 (2005) 553–556.
[29] I.D. Smičiklas, S.K. Milonjić, P. Pfendt, S. Raičević, The point of zero charge and
sorption of cadmium (II) and strontium (II) ions on synthetic hydroxyapatite,
Separ. Purifi. Technol. 18 (2000) 185–194.
[30] C. Stötzel, F.A. Müller, F. Reinert, F. Niederdraenk, J.E. Barralet, U. Gbureck, Ion
adsorption behaviour of hydroxyapatite with different crystallinities, Colloids
Surf. B Biointerfaces 74 (2009) 91–95.
[31] C.F. Li, F.T. Meng, Nano-crystallinite hydroxyapatite synthesized by neutralization
with the assist of citric acid, Mater. Lett. 62 (2008) 932–934.
[32] M. Khalid, G. Joly, A. Renaud, P. Magnoux, Removal of phenol from water by
adsorption using zeolites, Ind. Eng. Chem. Res. 43 (2004) 5275–5280.
[33] I. Langmuir, The adsorption of gasses on plane surface of glass, mica and platinum,
J. Am. Chem. Soc. 40 (1916) 1361–1368.
[34] H.M.F. Freundlich, Über die adsorption in lösungen, Z. Phys. Chem. 57 (1906)
385–470.
[35] J.Q. Jiang, C. Cooper, S. Ouki, Comparison of modified montmorillonite adsorbents:
Part I. Preparation, characterization and phenol adsorption, Chemosphere 47
(2002) 711–716.
[36] R.A. Garcia-Delgado, L.M. Cotouelo-Minguez, J.J. Rodriguez, Equilibrium study of
single-solution adsorption of anionic surfactants with polymeric XAD resins,
Sep. Sci. Technol. 27 (1992) 975–987.
[37] M. Aoyama, Removal of Cr (VI) from aqueous solution by London plane leaves,
J. Chem. Technol. Biotechnol. 78 (2003) 601–604.
[38] M.C. Lu, G.D. Roam, J.N. Chen, C.P. Huang, Adsorption characteristics of dichlorvos
onto hydrous titanium dioxide surface, Water Res. 30 (1996) 1670–1676.
[39] A. Torrents, S. Jayasundera, The sorption of nonionic pesticides onto clays and the
influence of natural organic carbon, Chemosphere 35 (1997) 1549–1565.
[40] C. Maqueda, E. Morillo, F. Martin, T. Undabeytia, Interactions of pesticides with the
soluble fraction of natural and artificial humic substances, J. Eniron. Sci. Technol. B
28 (1993) 655–670.
[41] X.K. Zhao, G.P. Yang, X.C. Gao, Studies on the sorption behaviors of nitrobenzene
on marine sediments, Chemosphere 52 (2003) 917–925.
[42] Y. Dai, Y. Miharaa, S. Tanaka, K. Watanabe, N. Terui, Nitrobenzene-adsorption
capacity of carbon materials released during the combustion of woody biomass,
J. Hazard. Mater. 174 (2010) 776–781.