Chromium(VI) Removal by Bone Char–ZnO
Composite: Parameters Optimization by Response
Surface Methodology and Modeling
Neda Ranjbar, Seyedenayat Hashemi , Bahman Ramavandi, and Masomeh Ravanipour
Environmental Health Engineering Department, Faculty of Health, Bushehr University of Medical Sciences, Bushehr, Iran;
seyedenayat_hashemi@yahoo.com (for correspondence)
Published online 00 Month 2018 in Wiley Online Library (wileyonlinelibrary.com). DOI 10.1002/ep.12854
This study presents the efficiency of bone char- –ZnO for
eliminating chromium(VI) from aqueous solutions. The bone
char- –ZnO composite was provided using sol-–gel method.
The elemental, morphology, surface analysis of bone char- –
ZnO were fully studied. The prepared composite was mostly
composed of Ca5(PO4)3OH and had a specific surface area
of 28.09 m2/g. Results indicated that central composite
design (CCD) has a desirable ability (R2 > 0.87) to predict
chromium(VI) removal by bone char- –ZnO. Furthermore,
the results suggest that the removal efficiency increased with
the elevation of adsorbent dose, shaking rate, temperature,
and contact time. Isotherm and kinetics investigation indi-
cated that chromium adsorption process follows Langmuir
model (R2 > 0.97 and Qm5 84.03 mg/g) and second- order
kinetic model (R2 > 0.999). The values of DH8 and DS8 of the
chromium adsorption reaction by bone char- –ZnO were
obtained as 580 kJ/mol and 5.5 kJ/mol K, respectively, sug-
gesting spontaneity and endothermicity of the reaction.
Desorption study was also performed by two desorbent
agents of distilled water and nitric acid. Overall, it can be
concluded that the bone char- –ZnO composite is an effi-
cient and potential adsorbent to be used in water and waste-
water treatment plants. V C 2018 American Institute of Chemical
Engineers Environ Prog, 00: 000–000, 2018
Keywords: adsorption isotherm, bone char–ZnO, central
composite design, chromium desorption, kinetics
INTRODUCTION
Heavy metals are among the serious contaminants of the
environment, which belong to the class of priority pollutants,
as they are not degradable in environments and are harmful
to the human health [1,2]. As a hazardous contaminant, chro-
mium is found in many industrial activities including water
plating, leather making and wood processing factories, alloy
and steel production factories, plating, tannery, dyeing, and
welding [3]. Essentially, chromium is found in two states: tri-
valent (Cr(III)) and hexavalent (Cr(VI)). Hexavalent chro-
mium is mainly found in groundwater as hydro chromate
(HCrO2 2 22
4 ), chromate (CrO4 ), and dichromate (Cr2O7 ) ions
[4]. Trivalent chromium has less toxicity and mobility than
hexavalent chromium due to high absorptivity toward soil
particles and formation of water insoluble chromium
C 2018 American Institute of Chemical Engineers
V ous bone char modifiers including cerium [20], iron and
Environmental Progress & Sustainable Energy (Vol.00, No.00) DOI 10.1002/ep
hydroxide. Hexavalent chromium anion has attracted a great
deal of attention in recent years due to its high mobility in
groundwater and its carcinogenic and harmful properties for
living organisms [5]. The maximum allowable level for chro-
mium(VI), as defined by American Environmental Protection
Agency, is 0.1 mg/L to be discharged into water bodies and
0.05 mg/L in drinking water. Considering its toxic nature,
chromium(VI) removal methods from groundwater and
industrial wastewaters are developing [5].
The most important methods for removing hexavalent
chromium from aqueous environments are adsorption [6],
chemical precipitation [7], ion exchange [4], and membrane
processes [8]. Most of these methods have various disadvan-
tages including high cost, large volume of materials, and
incomplete removal of chromium [9]. Comparing the above
methods, the adsorption process can be employed as a prac-
tical process for removing chromium(VI) from wastewater
due to low costs, needing less energy, and not producing
active toxic products [10]. For this reason, adsorption is one
of the major methods of interest to researchers. So far, many
types of the adsorbents were used for removing hexavalent
chromium such as biochar [5], chitosan [11], graphene oxide
[12], multiwall carbon nanotubes [13], and bone char [14].
Bone char plays an important role in controlling water
pollution due to its suitable physiochemical properties,
cheapness, availability, easy preparation, and presence of
strong functional groups in the structure [14]. Another suit-
able characteristics of bone char adsorbents are the meso-
porosity structure and specific surface area of 80–120 m2/g,
which has been obtained through heating bone wastes
[5,14]. As most of the adsorbents like the activated carbon
require the use of high temperature to increase the specific
surface area, bone char is no exception. In recent years, vari-
ous studies have been conducted for removing different
organic and inorganic compounds such as drugs [15], dye
[16], and heavy metals [17] by the bone char adsorbent.
Some researchers have reached the conclusion that the
adsorption efficiency of bone char is higher than that of
active carbon for removal of metals [18]. For example, Choy
et al. [19] reported that the efficiency of bone char in adsorb-
ing ion of metals is around 15% greater than that of active
carbon (Merck Co.) under the same experimental conditions.
Research for enhancing the efficiency of bone char
adsorption is under developing. For this purpose, so far vari-
Month 2018 1
Table 1. Range of independent variables used in the modeling processes.

Levels
Variables Symbol 22 21 0 1 12
pH X1 2 3 6 9 10
Chromium(VI) concentration (mg/L) X2 5 44 131 181 220
Time (min) X3 15 56 128 199 240
Bone char–ZnO dosages (g) X4 0.5 0.56 0.75 0.91 1
Shaking rate (rpm) X5 50 68 100 132 150
Temperature (8C) X6 35 40 48 55 60

aluminum salts [21], and CO2 [22] have been used for
enhancing removal of different contaminants. Given to the
best of authors’ knowledge, no research was found regarding
application of ZnO for modifying the bone char for chro-
mium removal. In a study conducted on ZnO crystals for
removing hexavalent chromium, ZnO was introduced as a
strong adsorbent [23]. Furthermore, the ZnO–yeast composite
has been used successfully for removal of Pb(II) [24]. The
only concern about activating bone char with zinc oxide is
energy consumption, which can be managed by shortening
the activation time and using lower temperatures.
Therefore, the aim of this study is to investigate the perfor-
mance of bone char modified with ZnO in removing chro-
mium(VI) from aqueous solutions. Optimization of the
parameters influencing the adsorption process including pH,
adsorbent dose, contaminant, contact time, solution tempera-
ture, and shaking rate was studied by response surface meth-
odology (RSM). Furthermore, physiochemical properties of the
prepared adsorbent, kinetics, and thermodynamics of the reac-
tion and the desorption process have also been discussed.
MATERIALS AND METHODS
Materials
By dissolving 1.4141 mg of potassium dichromate
(K2Cr2O7) powder in 1000 mL double distilled water, the stock
solution of hexavalent chromium (500 mg/L) was prepared.
The working solutions required were prepared by diluting the
stock solution. The pH of the samples was adjusted using
0.1 M HCl and NaOH solutions. All the chemicals used in this
study were purchased from Merck Co. with analytical grade.
Synthesis of Bone Char–ZnO Composite
After collecting femur bone of cow from butcheries across
Bushehr City, Iran, first their wastes were removed and boiled in
808C water for 3 h, to completely separate fat content (H137153
Precision Laboratory Water Bath 51221073, Gilroy, California,
United States). Next, using an electric furnace (Carbolite,
England) at 10008C within 8 h, bone char was prepared [25].
To modify bone char with ZnO, 2 g of bone char was
added to 50 mL zinc nitrate 0.1 M solution, and stirred at
room temperature. Next, 5 mL of ammonium hydroxide
(25%–28%) was gradually added to the mixture and stirred
by a Heater Stirrer (Model L-81, Labinco BV) for 5 h and
eventually heated for 1 h at 5008C in the electric furnace.
The obtained white solid powder was born char–ZnO com-
posite, which was used as adsorbent in the experiments.
Analytical Methods
The pH-zero point of charge (pHzpc) parameter was cal-
culated by pH drift method [26]. For this purpose, 0.1 M
NaCl solution (1 double distilled water) was used and the
initial solution pH was adjusted between 2 and 12. After that,
2 g/L adsorbent was added to solutions and placed on a
shaker incubator (Parsazma, Iran) at 120 rpm at temperature
of 258C for 24 h. To characterize the adsorbent morphology,
scanning electron microscopy (SEM, JSM-7100FA) and X-ray
diffraction (XRD) (ED2000, Oxford Co., England) were
employed. To determine the specific surface area of the
adsorbent, Broouner–Emmet–Teller (BET) and Barret–Joy-
ner–Helanda (BJH) (ASAP2020, micromeritics Co.) were
applied. The functional groups of the bone char–ZnO were
determined using a Fourier-transform infrared spectroscopy
(FTIR) instrument (Speetram T50, Perkin Elmar Co.). For ele-
mental and compound analysis, X-ray fluorescence (XRF, X
pert pro, Panolytical Co.) was used. The pH of the solution
was measured by a digital pH meter (462, Iran). For weigh-
ing the materials, a digital balance HR-200 (Japan) with an
accuracy of 0.0001 g was employed. Chromium(IV) measure-
ment was performed by atomic adsorption device (AA240,
VARIAN, Australia) at the wavelength of 357.9 nm.
Adsorption Experiment
Before beginning the experiments, all containers and glass-
ware were acid washed in 1 M HNO3. All experiments were per-
formed in 250-mL flask containing 100 mL of different
concentrations of hexavalent chromium and adsorbent dose at
different pHs and contact times. The samples were put in the
shaker incubator for a given mixing rate and then the contents
of the flask were passed through Whatman filter No. 42. The fil-
trates were kept in glass containers at 48C in refrigerator at pH
below 2 according to standard method until measurement [27].
The removal percentage and adsorption capacity of chro-
mium(VI) were calculated by Eqs. (1) and (2), respectively
[28,29].
ðC0 2Ce Þ
Removalð%Þ5 3100 (1)
Ce
ðCi 2Ce Þ
qe 5 3V (2)
W
where qe is the adsorption capacity of the bone char–ZnO
(mg/g), Ci is the metal concentration in the liquid phase at
the beginning (mg/L), Ce represents equilibrium concentra-
tion of the metal at the equilibrium status (mg/L), V is the
liquid volume in the flask (mL), and W is the mass of the
bone char–ZnO (mg).
Parameters Optimization
Given the disadvantages of “one variable at the time” method
including being time-consuming, costly, and high error [30], in
this study, RSM based on central composite design (CCD) was
used for evaluation the effect of variables influencing the
response performance (i.e., chromium removal efficiency) and
prediction of the best response value. To demonstrate the feature
of the response surface in the experimental region and illustrate
the optimal conditions of the most significant independent varia-
bles, the CCD under RSM was employed [31].
As shown in Table 1, six studied parameters include X1,
X2, X3, X4, X5, X6, which are in five levels with codes 12,
11, 0, 21, 22 for high, medium, and low levels.

2 Month 2018 Environmental Progress & Sustainable Energy (Vol.00, No.00) DOI 10.1002/ep
Figure 1. XRD spectrum of (a) fresh and (b) used bone char–ZnO. [Color figure can be viewed at wileyonlinelibrary.com]

To determine the number of experiments, Eq. (3) was used. solution temperature 5 448C. After filtering the samples, the
residual value of the hexavalent chromium was analyzed.
N 5 k 2 12k1CP (3) The models of Langmuir and Freundlich were used for eval-
uation the adsorption isotherm.
where k is the number of factors and Cp represents the num- Linear Langmuir model describes the monolayer adsorp-
ber of repetition of central point [30]. tion on continuous surface of the adsorbent. This model can
In this study, six variables were examined at five levels be used for calculation of the maximum adsorption capacity
and by considering repetition for each level, 86 samples (Qm) for the formation of monolayer. The main Langmuir
equation is as follows [33]:
were designed and studied. The final response was calcu-
lated by Eq. (4) [25,32]. Qm KL Ce
qe 5 (5)
11KL Ce
X
k X
k X
k X
k
y5 b0 1 b1 x1 1 bii xi 2 1 bij xi xj 1 ‹ (4)
i51 i51 i51 j51
where Qm is the adsorbent capacity (mg/g) and KL is the
adsorption energy (L/g).
Freundlich equation is the description of multilayer, uni-
where y is the response, b0, b1, bii, and bij are the regression
form, and heterogeneous adsorption of the adsorbate on the
coefficients, E is the error value, and Xj is coded variables of
adsorbent. The Freundlich model is [34]
the system.
Calculation of the predicted responses was analyzed by
qe 5Kf Ce 1=n (6)
Statistical Software Design Expert 7.00 through RSM. The
data obtained from the response have been calculated by
analysis of variance method. where Kf is the adsorption capacity (mg/g) and 1/n is the
adsorption intensity.

Adsorption Isotherm Adsorption Kinetics

The conditions for performing the isotherm tests were To better understand the extent of chromium adsorption
chromium concentration 5 55 mg/L, adsorbent dose 5 0.1– over time, adsorption kinetics was examined. In this study,
5 mg/L, pH 5 3, time 5 160 min, shaking rate 5 132 rpm, and all experiments were performed under optimal conditions

Environmental Progress & Sustainable Energy (Vol.00, No.00) DOI 10.1002/ep Month 2018 3

Figure 2. SEM image of (a) raw bone char, (b) fresh bone
char–ZnO, and (c) used bone char–ZnO.
determined by RSM (chromium concentration: 55 mg/L,
adsorbent dose: 0.91 g/L, pH 5 3, shaking rate: 132 rpm, and
temperature: 448C). After filtering the samples at the deter-
mined contact times (10, 20, 40, 60, 90, 120, 180, and 240
min), the residual value of hexavalent chromium was mea-
sured. Pseudo-first-order and pseudo-second-order kinetics
were investigated by the following formula [35]:
dqt
Pseudo-first-order : 5k1 ðqe 2qt Þ (7)
dt
where k1 is the constant of pseudo-first-order reaction
(min21), qe and qt are the adsorption capacity at equilibrium
and at time t. If the initial concentration of the adsorbate is
low, the second-order kinetics is mostly appropriated. The
equation of this kinetics is as follows [35]:
4 Month 2018 Environmental Progress & Sustainable Energy (Vol.00, No.00) DOI 10.1002/ep
dqt
Pseudo-second-order : 5k2 ðqe 2qt Þ2 (8)
dt
where k2 is the constant of pseudo-second-order kinetics (g/
mg min).
Adsorption Thermodynamics
The adsorption thermodynamics of chromium was exam-
ined by adsorption experiments under optimal conditions
(chromium concentration: 55 mg/L, adsorbent dose: 0.91 g/L,
pH 5 3, shaking rate: 132 rpm, time: 160 min) and at 27, 35,
44, 55, and 628C. The thermodynamic parameters such as
changes in enthalpy (DH8), entropy (DS8), and Gibbs free
energy (DG8) are obtained by Eqs. (9) and (10) [5].
ln kd 5DS  =R 2 DH  =RT (9)
DG o 5 DH o 2 T  DS  (10)
The DH8 and DS8 parameters are obtained from line slope
and intercept of ln kd versus 1/T plotting.
Desorption Experiments
To investigate desorption of bone char–ZnO, first, the
employed adsorbent in the adsorption process under optimal
conditions obtained by RSM was dried in an oven at 1058C for
2 h. Then, the amount of 0.91 g/L dried mass was added to
desorbent solution. The desorption was performed in double
distilled water with an initial pH of around 6.5 and nitric acid
(0.1 M) with initial pH of around 2 across six times intervals of
30, 60, 90, 160, 240, and 300 min and shaker rate of 132 rpm.
RESULTS AND DISCUSSION
Adsorbent Properties
Based on calculations done by Belsorp software and BET
isotherm and extent of absorption of nitrogen gas, the specific
surface area of the raw bone char was 8.795 m2/g. For the
modified bone char before and after being exposed to chro-
mium, the values were determined as 28.09 and 2.580 m2/g,
respectively. The volume and diameter of pores for the bone
char modified with zinc oxide before adsorption were 8.47 nm
and 0.003118 cm3/g, respectively, while for postadsorption,
they were 0.98 nm and 0.005334 cm3/g, respectively. The
results indicate that treating the bone char with ZnO causes
increased specific surface area, which suggests suitable cover-
age of raw bone char with zinc oxide. However, chromium
adsorption has caused reduction of the specific surface area of
the adsorbent and volume of the pores, which is a reason for
occupation and filling of pores by chromium ions. These
results are in line with the results obtained by Z un~ iga-Muro
et al. [20] who have dealt with investigation of specific surface
area properties of raw and modified bone char.
Analysis of the structure of bone char–zinc oxide using
XRD at angle 100 > 2h > 0 and interpretation of standard
cards indicated that the major compound present in the
structure of studied adsorbent is calcium hydroxyapatite with
the chemical formula of Ca5(PO4)3OH. According to Figure
1, the existence of hydroxyl radicals in the structure of this
adsorbent is one of the most important properties of bone
char and can have an important effect on the extent and
conditions of adsorption of chromium contaminant. Further-
more, this structure shows that bone char adsorbent is classi-
fied as mineral adsorbents group. Choy et al. [19], Abe et al.
[36], and Czerniczyniec et al. [37] reported similar results
regarding the structure of bone char used in their research.
Figure 2a–c represents the morphological properties of the
raw bone char and bone char–zinc oxide adsorbent. Based on
Figure 3. FTIR spectrum of (a) fresh and (b) used bone char–ZnO. [Color figure can be viewed at wileyonlinelibrary.com]

Table 2. Results of XRF elemental analysis of bone char– adsorption using FTIR was detected within 400–4000 cm21.
ZnO. Adsorption bands 1384, 1460, and 1461 cm21 in both adsorb-
ents are related to CAO band in CO22 3 , where both bands
Fresh bone Used bone are attributed to CaCO3 present in the structure of the bone
Element char–ZnO char ZnO char [37]. Bands 1090, 1051, 1460, 1049, 603, and 571 are
associated with PO32
4 groups of hydroxyapatite in bone char
CaO 42.89 41.08 and bands 603 and 571 cm21 are related to stretching vibra-
P2O5 37.08 40.76 tion and bending vibration. The intensity of bands PO32 4
MgO 2.24 1.04 diminishes when Cr is adsorbed by the char. This reduction
Na2O 1.43 1.98 may be attributed to combination of chromium with PO4 or32
ZnO 11.73 11.45 interaction between bone char–ZnO and aqueous solution.
Al2O3 0.82 0.73 Band 3371 cm21, which is observed in both fresh and used
SO3 2.57 2.12
adsorbent is related to OAH stretched groups in crystals of
SrO 0.18 0.15
calcium hydroxyapatite, where a wide range of frequencies
Other material 1.06 0.6
are developed in response to presence of hydroxyl free
Total 100 100
groups linked to OAH bands of carboxylic acid
group [39,40].
Table 2 reveals the XRF results, where bone char modi-
Figure 2a, the raw bone chare is made up particles with different fied with zinc oxide has had 11.73% zinc oxide before being
sizes. Figure 2b shows that smaller particles stick to the bone char exposed to chromium and this value changed to 11.45% fol-
surface, which probably represents the presence of zinc oxide. lowing exposure to chromium.
In the image after adsorption (Figure 2c), the accumulation of
particles on the adsorbent surface is visible, which probably rep-
resents the reaction of chromium and adsorbent [38]. Optimal Conditions
According to Figure 3a,b, determination of functional Regarding chromium(VI) adsorption, RMS predicted that
groups on the adsorbent surface before and after chromium to achieve the maximum efficiency, the optimal values for

Environmental Progress & Sustainable Energy (Vol.00, No.00) DOI 10.1002/ep Month 2018 5
Table 3. ANOVA for response surface quadratic model.

Source Sum of square df Mean square F value P value

Model 16332.92 27 604.59 14.41 <0.0001
Chromium concentration 376.20 1 376.20 8.96 0.0040
pH 7052.26 1 7052.26 168.01 0.0001>
Contact time 169.85 1 169.85 4.05 0.0489
Shaking rate 282.75 1 282.75 6.74 0.0119
Temperature 729.14 1 729.14 17.37 0.0001
Adsorbent dose 274.71 1 274.71 6.54 0.0132

Table 4. Statistical values for obtained removal percentage.

Std dev Mean CV (%) Press R2 Adj. R-Square Pred. R-Square Adeq. R-Square
6.48 62.09 10.43 5937.17 0.8703 0.8099 0.6338 18.45

where T is the temperature, C is the initial chromium con-

centration, t is the time, D is the adsorbent dose, and Sh is
the shaking rate.
To confirm the model prediction, confirmatory experi-
ment was performed under optimal conditions obtained by
the software. Following the confirmatory experiment, chro-
mium removal efficiency (85%) was shown to lie within the
prediction range of the software (87%). Thus, optimal condi-
tions predicted by the model were also confirmed by model
with experiment.

Figure 4. The actual and predicted plot of chromium(VI)
adsorption. [Color figure can be viewed at wileyonlineli-
brary.com]
pH, initial concentration of chromium, contact time, adsor-
bent value, shaking rate, and temperature are 3, 55 mg/L,
160 min, 0.9 g/L, 132 rpm, and 448C. A multiformula second-
order equation (Eq. (11)) was extracted for predicting the
efficiency as a function of different variables.
Removal 5 2 229:82753 1 0:181173C2 15:5118723pH
1 0:864963t 1 0:985313Sh 1 10:444193T 257:188263D
1 0:0253183C3pH 23:90874E20043C3 t 2 3:61371E2004
3 C3sh 11:94677E20033C3T 2 0:292643 C3D 2 6:10416E
20033pH3t 1 4:29235E20033pH3sh 5 0:0374853pH3T
24:857263pH3 D 1 1:66497E20043t3sh 2 9:96207E2003
3t3T 2 0:0934483t3D 2 0:0138413sh 3 T2 0:226553sh
3 D 1 0:338893 T3 D 2 6:84958E20043C2 1 0:910283pH2
2 1:09634E20033t2 25:04218E20043sh2 2 0:0850563T2
1 100:151283 D2
(11)
Statistical Analysis
Design-Expert program (DX7) offers rotatable 3D plots
for visualization of response surfaces. This software pro-
vides highly efficient design of experiments (DOE) for:
Find the ideal process settings and achieve optimal perfor-
mance. For statistical analysis of the results, Experiment
design Software has used analysis of variance (ANOVA)
analysis of variance (Table 3). In this table, the main fac-
tors, their interactions, and P value and F value numbers
can be seen. A summary of the statistical results of chro-
mium(VI) removal model including correlation, mean, var-
iations factor, and other values are provided in Table 4.
The results of this analysis indicate that the model pro-
posed by the software is of second order and significant.
Statistically, regarding the P values obtained in the table,
the model introduced for removal of chromium is signifi-
cant (0.0001 < 0.05) and confidence coefficient 95% has
been provided by the chromium removal model. It sug-
gests that the information obtained from the experiments
has a very good correspondence with the proposed model.
Lower P values mean that there is a greater interaction
between two factors. F value of the proposed model is
14.41, suggesting significance of the second-order model
and satisfactoriness of evaluation of the experiments. Corre-
lation of the models by regression coefficient R2 has been
presented in Table 4. The large value of correlation coeffi-
cient suggests that the obtained model is able to describe
the behavior of chromium removal under these conditions
(R2 5 0.8703). It also signifies the significance of the
response prediction. The regression coefficient proposed
by the model (Pred. R2 5 0.6338) has a considerable corre-
spondence with the regression coefficient of experiments
(Adj. R2 5 0.8099).
The real and proposed removal percentage of chro-
mium(VI) has been shown in Figure 4. Real values are
responses measured from the results of experiments, while
the proposed values are the values that have been evaluated
through estimation of functions obtained for the model.

6 Month 2018 Environmental Progress & Sustainable Energy (Vol.00, No.00) DOI 10.1002/ep
Figure 5. Response surface plots of chromium removal by bone char–ZnO. [Color figure can be viewed at wileyonlineli-
brary.com]

Figure 6. Isotherm modeling of (a) Langmuir and (b) Freundlich (pH: 3, temperature 448C, chromium concentration: 55 mg/L,
shaking rate: 132 rpm, contact time: 160 min). [Color figure can be viewed at wileyonlinelibrary.com]

Environmental Progress & Sustainable Energy (Vol.00, No.00) DOI 10.1002/ep Month 2018 7
Proximity of points to the 458 line indicates that it is suitable
for prediction of response and also suggests that there is a
correlation between proposed values by the model and real
values obtained from the experiments.
Effect of Solution pH
One of the important factors which influence adsorption
process through affecting the superficial charge of the
adsorbent is solution pH. To investigate the effect of pH,
five ranges between 3 and 9 were chosen. Figure 5 dem-
onstrates that adsorption of chromium(VI) by bone char–
zinc oxide is heavily dependent on the environmental pH,
such that with elevation of pH from 3 to 9, the extent of
adsorption decreases from 84% to 63%. This is due to the
effect of pH on superficial charge of the adsorbent and
adsorbate pollutant. The number calculated for pHZPC is
around 8, which was similar to the number calculated by
Rezaee et al. [41]. It suggests negativity of superficial
charge at pHs above 8 and positivity of superficial charge
at pHs below 8. As hexavalent chromium has a negative
electric charge, thus its high adsorption at low pHs of the
environment could be due to presence of ions with oppo-
site electric charge on the surface of chromium adsorbent
and the effect of electrocolomb force, which has resulted
in further adsorption of chromium on the surface of the
adsorbent. The reason of low adsorption of chromium at
pHs above pHZPC by this adsorbent can be attributed to
encirclement of the adsorbent surface by hydroxyl ion,
which prevents from suitable adsorption of chromium.
Another reason lower tendency of Cr(VI) adsorption at
higher pHs is intense competition between OH- and chro-
mate anions for adsorption sites [5]. Similar results are
observed in the study by Hu et al. [42], where the maxi-
mum chromium removal was obtained at acidic pH of 2.5.
In another research conducted by Ahmadi et al. [5] for
removal of chromium, the results indicated that the maxi-
mum chromium(VI) removal efficiency occurred at acidic
pHs.
Table 5. Findings of isotherm modeling.
Isotherm Parameter Value
Langmuir Qm 84.03
kL 5.44
R2 0.9754
RL 0.008–0.04
Freundlich K 34.02
n 0.215
R2 0.936
Figure 7. Kinetic models of (a) pseudo-first order and (b) pseudo-second order (adsorbent dose: 0.9 g/L, pH: 3, temperature
448C, chromium concentration: 55 mg/L, shaking rate: 132 rpm). [Color figure can be viewed at wileyonlinelibrary.com]
8 Month 2018 Environmental Progress & Sustainable Energy (Vol.00, No.00) DOI 10.1002/ep
Effect of Initial Chromium(VI) Concentration
To investigate the effect of initial concentration of chro-
mium(VI) on the removal efficiency, five concentrations
were considered within the range of 5–220 mg/L. The
depicted results in Figure 5 indicated that the extent of chro-
mium(VI) adsorption is a function of initial concentration of
chromium(VI). The extent of adsorption is greater at higher
initial concentrations, which can be attributed to diminished
resistance to adsorption or withdrawal of chromium(VI) in
response to elevated mass transfer force. Higher initial con-
centrations develop a considerable driving force, overcoming
mass transfer resistance. Elevation of initial concentration
also causes increased interactive effect between the adsor-
bent and chromium(VI). Other studies on bone char as
adsorbent of heavy metals [18,43] have been obtained similar
results.
Effect of Bone Char–ZnO Dosage
Based on Figure 5, with elevation of the adsorbent level
from 0.5 to 1 g/L, the chromium(VI) removal increases,
which is due to the large number of available sites of adsor-
bent to be occupied by the adsorbate. This is also due to
active surface of the adsorbent and dynamic factors such as
increased extent of collision and free bands on the adsorbent
surface [42]. Overall, adsorption of metal ions from aqueous
solutions using adsorbent is generally attributed to two types
of interaction: electrostatic and van der Waals. Electrostatic
interaction is associated with superficial charge is developed
on the surface of the adsorbent, while van der Waals interac-
tion is related to coordination of functional groups with
metal ions [42]. Development of superficial charges makes
electrostatic interaction possible. Similar results have been
obtained in other studies where bone char has been used for
chromium removal [14,44]. With elevation of the adsorbent
dose due to increased active sites of adsorption, the adsorp-
tion efficiency increases, but as some active points present
on the adsorbent surface remain unsaturated and its full
Table 6. Results of kinetic study.
Parameter Value
Pseudo-first order
k1 0.1031
qe 2.7175
R2 0.6505
Pseudo-second order
k2 0.0013
qe 57.8034
R2 0.9997

Figure 8. Thermodynamic plot of ln Kd versus 1/T (adsor-
bent dose: 0.9 g/L, pH: 3, temperature 448C, chromium con-
centration: 55 mg/L, shaking rate: 132 rpm).
Table 7. Thermodynamic parameters for adsorption of
Cr(VI) on bone char–ZnO.
Temperature DGo DHo DSo
(oK) (KJ/mol) (KJ/mol) (kJ/mol.K) R2
300 219504 580 5.5 0.954
308 219973
317 220135
328 221243
335 221724
capacity is not used, extent of adsorption per unit of mass
decreases [14].
Effect of Temperature
In this study, the temperature factor and chromium(VI)
removal efficiency were directly related, and the maximum
removal efficiency was seen at 488C (Figure 5). This may be
due to increase in the mobility of adsorbent particles in
response to the temperature elevation, suggesting that
adsorption is endothermic process in nature [35]. Another
reason for elevation of efficiency with rising the temperature
is decreased boundary layer thickness around the adsorbent
[45]. Murant Dandar et al. [46] has been performed bioad-
sorption of chromium ions by using Lepidoptera leaves,
which is supported the results of this study. In this research,
448C was specified as the optimal temperature for
equilibrium.
Effect of Contact Time
As can be seen from Figure 5, with prolongation of the
time of contact, the chromium removal efficiency has
increased, such that at 160 min, it reaches to maximum
amount, and after that the slope of the removal efficiency
starts to diminish. The prolongation of contact time increased
the opportunity and chance of collision of metal ions with
solid particles and thus the extent of adsorption increased.
This means that the removal percentage of metal ions
increases with prolongation of contact time and after 160
min the extent of adsorption of metal ions by the adsorbent
is constant. In other words, after 160 min, the equilibrium is
developed between chromium ions adsorbed by the solid
phase (adsorbent) and the solution. The exposure of the
adsorbate (chromium) and the adsorbent after the equilib-
rium time will not have a significant effect on the extent of
adsorption. The extent of slow chromium(VI) adsorption
after the equilibrium can be due to electrostatic delay devel-
oped by different genera of soluble chromium and slow dif-
fusion of ions into the pores of the adsorbent [46]. In other
words, after some time when superficial sites are occupied
Environmental Progress & Sustainable Energy (Vol.00, No.00) DOI 10.1002/ep
Table 8. Desorption of chromium ions from bone char–
ZnO.
Desorption Initial Time
agent pH (min) Desorption
HNO3 (0.1 M) 2 30 31.46
60 35.16
90 38.53
160 53.93
240 50.68
300 51.24
Distilled water 6.5 30 4.57
60 .6.49
90 8.11
160 11.04
240 10.73
300 10.64
by chromium ions, repulsive forces are developed among
the molecules of the adsorbate on the surface of the solid
and fluid, thereby decreasing the extent of adsorption. Many
studies are consistent with our findings [5,46,47]. Further-
more, in the research by Mekonnen et al. [48], the equilib-
rium time was considered as 160 min.
Effect of Shaking
To investigate the effect of shaking rate on the chro-
mium(VI) removal, the value of stirring was considered as
50–150 rpm. Figure 5 suggests that with elevation of the
shaking rate, the removal efficiency increases up to 69%.
Studies conducted by Hu et al. [42] showed that with eleva-
tion of the stirring rate, the removal efficiency of heavy met-
als increases as well. Increasing the shaking rate causes the
reduction of boundary layer and eventually leads to acceler-
ate the mass transfer [46]. Furthermore, at low shaking rates,
mixing does not occur well and thus dispersion of particles
does not occur uniformly in the liquid. Consequently, parts
of the surface of the adsorbent do not get into contact with
chromium and the removal efficiency diminishes [4].
Adsorption Isotherm
Determination of the adsorption isotherm parameters will
be useful for designing the adsorbent in full-scale pollutant
removal. In this study, Freundlich and Langmuir isotherm
models were examined. As can be seen in Figure 6a,b and
Table 5, adsorption of chromium(VI) follows Langmuir
model, based on the correlation coefficient (R2 5 0.9754).
According to the findings, it can be concluded that the
potential of chromium(VI) adsorption by modified bone char
is 84.03 mg/g. Another important parameter that should be
determined in the adsorption isotherm study is dimensionless
coefficient of RL, representing conditions of contaminant
adsorption across the adsorbent surface. Attaining the value
of RL between 0 and 1 (Table 5), representing suitable
adsorption of chromium ions on the surface of the adsor-
bent. Similar results reported by Hyder et al. [14] study on
adsorption of chromium(VI) by bone char.
Adsorption Kinetics
Kinetic study was performed to predict rate of adsorption
for the design and modeling of the process. The results of
pseudo-first-order and pseudo-second-order kinetic models
are shown in Figure 7 and Table 6. Based on the obtained
results, correlation coefficients in pseudo-first-order and
pseudo-second-order kinetics are 0.6505 and 0.9997, respec-
tively, suggesting that chromium adsorption process follows
pseudo-second-order kinetics. In studies conducted by Asgari
Month 2018 9
 pH 5 6.5 and nitric acid solution with pH 5 2). As can be
seen in Table 8, desorption percentage under relatively neu-
tral conditions is low, and the maximum desorption was
around 10%. It is probable that the released chromium did
not form a bond with the adsorbent and only had an adhe-
sion state [50]. However, in the acidic environment, with the
prolongation of time, the desorption efficiency increased and
a maximum desorption of 53% was achieved at 160th min of
contact time and after that it had a constant trend. Low
desorption values in both agents of desorption suggest that
chromium adsorption process from bone char is irreversible,
which may be due to superficial sequestration of chromium
as Cr(OH)23. The difference between the desorption values
of the both desorption agents can be attributed to the fact
Figure 9. Comparison of the adsorption of chromium(VI) that adsorption of chromium has occurred by different acidic
onto raw and modified bone char (concentration chromium: and alkaline groups and with different chemical bonds to the
55 mg/L, temperature: 448C, shaking rate: 132 rpm, contact adsorbent surface. In addition, the structure of the studied
time: 160 min). adsorbent such as its relatively low surface area (28.09 m2/g)
can be considered as the responsible for lack of complete
desorption of the contaminant. Such interpretations have
been reported by Tytlak et al. [51] for desorption of chro-
mium from wheat straw biochar. Furthermore, in a research
Table 9. Comparison chromium adsorbents with bone char– conducted by Guedes [50], similar desorption results were
ZnO. obtained. He pointed out the reason of precipitation of some
of the adsorbed chromium with residuals of carbonates
Qm resulting from bone char to explain the low desorption rate
Adsorbent (mg/g) Reference of chromium.
Agricultural waste maize bran 312.25 52
Surface modified tannery waste 215 53 Comparison Study
Activated Syzygium jambolanumnut 100 54 To compare the efficiency of chromium(VI) removal by
carbon raw and modified bone char, study was performed on five
Bone char–ZnO 84.03 This work adsorbents doses of 0.5–1 g/L of Figure 9. Based on the
Pomegranate husk carbon 35.2 55 obtained results, 20%–30% increase was observed in removal
Wheat straw 28.1 51 percentages by the bone char modified with zinc oxide, in
Bone char 8.41 14 comparison with the raw one. Furthermore, in this study, the
Oak-bark wood char 4.62 56 capacity of chromium(VI) adsorption of the bone char–ZnO
Surfactant-modified Iranian zeolite 4.4 4 was compared with different adsorbents employed in others’
Coconut tree sawdust derived activated 3.5 57 studies (Table 9), showing the appropriateness of the adsor-
carbon bent for chromium removal among other adsorbents.

et al. [4] and Hyder et al. [14], the adsorption of chro-
mium(VI) followed pseudo-second-order model.
Adsorption Thermodynamics
To investigate the possibility and spontaneity of the
adsorption process and to see whether the process is endo-
thermic or exothermic, thermodynamic factors of DG8, DH8,
and DS8 were determined. The thermodynamic parameters
results are provided in Figure 8 and Table 7.
Negative DG8 values show spontaneity of the reaction. A
positive DH8 also represents endothermicity of the process.
Positive DS8 signifies the increased entropy during the
adsorption and development of structural changes in the
adsorbent and adsorbate and tendency of the adsorbent to
the adsorbate. This means that adsorption is irreversible
[4,49]. R2 values show that entropy and enthalpy values for
bone char–zinc oxide adsorbent are reliable for removal of
chromium(VI). Such results have also been reported in the
research by Mekonnen in adsorption of chromium(VI) [48].
Desorption Study
One of the important parameters in adsorption studies is
the extent of desorption of the adsorbate on the adsorbent.
Indeed, the degree of stability of the adsorbate on the sur-
face of adsorbent was examined, to understand reversibility
or irreversibility of the contaminant. For this purpose,
desorption tests were performed across six times within 30–
300 min with two desorption agents (distilled water with
CONCLUSIONS
In this study, modified adsorbent of bone char–ZnO was
tested for removal of chromium(VI) from aqueous solutions.
Optimal conditions for adsorption of chromium(VI) by the
adsorbent were specified (pH 5 3, adsorbent dose 5 0.9 g/L,
initial concentration of chromium(VI) 5 55 mg/L, temper-
ature 5 448C, shaking rate 5 130 rpm, and contact time 5 160
min). Langmuir isotherm model (with the maximum adsorp-
tion capacity of 84 mg/g) and pseudo-second-order kinetic
model (R2 > 0.999) were suitable for describing the adsorp-
tion data. Thermodynamic findings suggested endothermicity
and spontaneity of the adsorption reaction. Overall, bone
char–ZnO composite had a suitable efficiency and capacity
for adsorption of chromium contaminant from aqueous solu-
tions, and can be developed for the full-scale usages.
ACKNOWLEDGMENT
This article is extracted from the M.Sc. thesis of the first
author. The authors would like to thank Bushehr University
of Medical Sciences, Bushehr, Iran for financial support
(Grant number: BPUMS-95H-313) providing to conduct this
research.
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