Journal of Geochemical Exploration 147 (2014) 151–158

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Journal of Geochemical Exploration

journal homepage: www.elsevier.com/locate/jgeoexp

Optimization of heavy metal removal from aqueous solutions by

maghemite (γ-Fe2O3) nanoparticles using response
surface methodology
Ali Ahmadi a,b,⁎, Shahriar Heidarzadeh a, Ahmad Reza Mokhtari a,
Emaeel Darezereshki c, Houshang Asadi Harouni a
a
Department of Mining Engineering, Isfahan University of Technology, Isfahan, Iran
b
Mineral Bioprocessing Research Group (MBRG), Biotechnology and Bioengineering Research Institute, Isfahan University of Technology, Isfahan, Iran
c
Energy & Environmental Engineering Research Center, Shahid Bahonar University of Kerman, Kerman, Iran

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

Article history: The presence of heavy metals in the wastewaters is a serious threat to the environment. In this research, the re-
Received 6 February 2014 moval of some heavy metal ions, including Pb(II), Zn(II) and Cd(II) using maghemite (γ-Fe2O3) nanoparticles as
Received in revised form 13 October 2014 adsorbent was studied in an aqueous system. Experiments were carried out at a laboratory scale in 100 mL
Accepted 18 October 2014
Erlenmeyer flasks at 150 rpm for 120 min. A response surface methodology (RSM) with a Box–Behnken Design
Available online 27 October 2014
was employed to evaluate the effects of solution pH, temperature, initial heavy metal concentration and adsor-
Keywords:
bent dosage on the removal efficiency of the heavy metals. Results of analysis of variance (ANOVA) showed
Heavy metal removal that the initial metal concentration and pH were the most significant parameters for Cd(II) ion removal. Adsor-
Maghemite nanoparticles bent dosage, pH and their interaction effect had significant influences on the removal efficiency of Pb(II) ions. The
Optimization interaction effect of pH and initial concentration of metals had the most significant influences on the removal ef-
Adsorption ficiency of Zn(II) ions. The optimum pH, temperature, initial concentration of metals and adsorbent dosage were
found to be 7.5, 45 °C, 50 mg/L, and 4.74 g/L, respectively. The observed selectivity order was as follows: Pb(II)
(10.55 mg/g) N Zn(II) (4.79 mg/g) N (1.75 mg/g) Cd(II). It was confirmed from SEM-EDAX analyses that heavy
metal ions were present on the surface of nanoparticles after adsorption. Results indicated that maghemite nano-
particles can be used as an effective adsorbent for effluent decontamination especially in Pb–Zn bearing
wastewaters.
© 2014 Elsevier B.V. All rights reserved.

1. Introduction Several conventional techniques have been employed to remove

Heavy metals are toxic and unlike most organic contaminants, they
are not biodegradable in the environment (Feng et al., 2010; Fu and
Wang, 2011; Shen et al., 2009). They have a tendency to accumulate
in living organisms and may cause serious harms and fatal health
problems to plants, animals and human beings through food chain
transfers (Feng et al., 2010; Fu and Wang, 2011; Shen et al., 2009;
Song et al., 2011).
With the rapid development of industrial activities, especially in de-
veloping countries, wastewaters contaminated with toxic heavy metals
are discharged directly or indirectly into the environment (Dhakal et al.,
2005; Fu and Wang, 2011; Shen et al., 2009). Cadmium (Cd) and lead
(Pb) have been considered as the most hazardous pollutant elements.
Excess amounts of Zn in the body can also cause major health problems.
These heavy metals are released from the Pb–Zn mine sites.
⁎ Corresponding author at: Department of Mining Engineering, Isfahan University of
Technology, Isfahan PO Box. 84156-83111, Iran. Tel.: +98 311 391 5113; fax: +98 311
391 5176.
E-mail address: a.ahmadi@cc.iut.ac.ir (A. Ahmadi).
heavy metal ions from wastewater effluents including but not limited
to ion exchange, chemical precipitation, membrane processes, electro-
dialysis, reverse osmosis, electrochemical treatment and adsorption
(Feng et al., 2010; Nassar, 2010; Shen et al., 2009; Song et al., 2011).
Most of these methods suffer from some disadvantages such as high
capital and operational costs for the treatment process and sludge
disposal (Nassar, 2010; Tuutijärvi et al., 2009). Among all of these ap-
proaches, the adsorption process is considered more efficient and eco-
nomical because of its flexibility in design, simplicity of operation,
facile handling, and in many cases generation of high-quality treated ef-
fluent (Han et al., 2013; Hua et al., 2012). Therefore, many efforts have
been made for the development of low-cost and ample metal sorbents,
such as activated carbon (Kobya et al., 2005), zeolite (Erdem et al., 2004;
Shawabkeh et al., 2004), chitosan (Juang and Shao, 2002), sawdust
(Shukla and Pai, 2005), functionalized silica (Bois et al., 2003), live bio-
mass (Yan and Viraraghavan, 2003) and agricultural byproducts
(Inbaraj and Sulochana, 2004; Nasiruddin Khan and Farooq Wahab,
2007). These methods, however, have some drawbacks; including the
generation of a large amount of waste sludge, the high regeneration
cost, low adsorption rate and available capacity because of the existence

http://dx.doi.org/10.1016/j.gexplo.2014.10.005
0375-6742/© 2014 Elsevier B.V. All rights reserved.
152 A. Ahmadi et al. / Journal of Geochemical Exploration 147 (2014) 151–158

of intra-particle diffusion in highly porous adsorbents (Hu et al., 2006;

Shen et al., 2009). An effective adsorbent should generally possess a
high surface area, small diffusion resistance and short adsorption
equilibrium time, so that it can be used to remove larger amounts of
contaminants in a shorter time. In addition, it should generate a
minimum amount of sludge (Hu et al., 2006).
In recent years with the development of nanotechnology, numerous
types of magnetic nanoparticles have been successfully synthesized and
applied for the removal of heavy metals from aqueous solutions
(Afkhami and Moosavi, 2010; Hakami et al., 2012; Tang and Lo, 2013).
The magnetic nanoparticles possess the merits of large surface area
with a high number of surface active sites which result in increasing
both the rate and extent of heavy metal adsorption (Afkhami and
Moosavi, 2010; Hakami et al., 2012; Tang and Lo, 2013). The separation
of the adsorbent from solution would be so facile via magnetic field (Hu
et al., 2006). Maghemite nanoparticle as a novel adsorbent is expected
to offer an attractive and inexpensive option for the removal of heavy
metals (Hu et al., 2006). The main advantages of using maghemite
nanoparticles are: high adsorption capacity due to its large surface
area, simple and fast separation of metal-loaded adsorbent from
aqueous solutions using an external magnetic field, non-production of
contaminants, and easy synthesis by different methods (Hu et al.,
Fig. 1. TEM image of γ-Fe2O3 magnetic nanoparticles.
2006; Srinivasan and Viraraghavan, 2010).
Response surface methodology (RSM) is a set of mathematical and
statistical approaches used for designing, improving and optimizing
processes (Anderson and Whitcomb, 2005; Wantala et al., 2012). This 2.2. Adsorption experiments
method can be utilized for evaluating the effects of individual parame-
ters, their relative significance and the interaction of two or more The adsorption of heavy metals on maghemite nanoparticles was
variables and determining the optimum conditions for desired re- studied by a batch technique. A certain amount of adsorbent was equil-
sponses (Demim et al., 2014; Wantala et al., 2012). The main objective ibrated with 50 mL of the heavy metals solution of known concentration
of RSM is to determine the optimum operating conditions for the sys- in 100 mL Erlenmeyer flasks. The flasks were agitated in an incubator
tem or to determine a region that satisfies the operating specifications shaker at 150 rpm for 120 min. After that, the suspension of the adsor-
(Hammari et al., 2004; Mourabet et al., 2012; Myers et al., 2009). The bent was separated from the solution by a 0.22 μm cellulosic filter. The
RSM approach usually includes the following two steps: the first step concentration of heavy metal ions remaining in solution was measured
is the model formulation to determine which factors and their interac- by AAS (Perkin-Elmer 700) using the flame method. The effect of several
tions significantly affect the response, and the second step is the optimi- parameters, such as pH, temperature, contaminant concentration and
zation of the factors that influence the performance of the response adsorbent dose on the adsorption was investigated. The pH of the
(Stekelenburg et al., 2008). adsorptive solutions was adjusted using nitric acid (1 M) and sodium
In this study, the effects of some physicochemical parameters, i.e. hydroxide (1 M) when needed.
pH, temperature, initial heavy metal concentration and adsorbent
dosage on the adsorption efficiency of Pb(II), Cd(II) and Zn(II) ions 2.3. Design of experiments
on maghemite (γ-Fe2O3) nanoparticles were investigated. Using a
Box–Behnken Design, statistically designed experiments were used to Response surface methodology (RSM) was used to evaluate the ef-
determine variables that affect the heavy metal removal efficiency fects of different operating parameters on the removal efficiency of
more significantly. Attempts have also been made to optimize the re- Pb(II), Zn(II) and Cd(II) ions. It not only shows the optimum conditions,
moval process by using response surface optimization techniques. but it also proposes fitted regression models. A 3-level, 4-factor Box–
Behnken Design (BBD) was used to evaluate the effect of the selected

2. Materials and methods

2.1. Materials

Maghemite nanoparticles with a Fe3O4 content in excess of 99.5%

were prepared by a wet chemical method previously described
(Darezereshki et al., 2010). The average particle size of the maghemite
was estimated by transmission electron microscope (TEM) to be around
14 nm. Fig. 1 shows the TEM image of the particles and Fig. 2 shows
the FTIR wave numbers for maghemite to be 454.6, 587.55, and
632.83 cm−1.
Pb(II), Zn(II) and Cd(II) stock solutions were prepared by dissolv-
ing a specified weight of the related metal salts in 500 mL of deion-
ized water, and the working solutions with a desired concentration
were prepared by appropriate dilutions of the stock solution
immediately prior to their use. Pb(NO 3) 2 , Zn(NO 3) 2 ·4H2O and
Cd(NO 3) 2 ·4H2O were of analytical grade and supplied by Merck Fig. 2. FTIR-Spectra of γ-Fe2O3 magnetic nanoparticles performed by 200 (a), 250 (b) and
company (Germany). 300 (c) mg KBr.
 A. Ahmadi et al. / Journal of Geochemical Exploration 147 (2014) 151–158 153

Table 1 The experimental results were analyzed using Design Expert 7.0 and
Actual and coded values of the test variables. a regression quadratic polynomial model was proposed as follows:
Factors Coded values −1 0 +1 X X X
2
pH 4.5 6 7.5
Yð%Þ ¼ α0 þ αi Xi þ αii Xi þ αi j Xi X j þ ε
Temperature (°C) 25 35 45
Contaminant concentration (mg/L) 10 30 50 where, α0 is the constant coefficient, αi, αii and αij are the regression co-
Adsorbent dose (g/L) 1 3 5
efficient and Xi, Xj indicate the independent variables. ε represents the
random error.

parameters on the removal efficiency of Pb(II), Cd(II) and Zn(II) ions
from aqueous solutions by maghemite nanoparticles. The four parame-
ters affecting heavy metal removal, namely solution pH (X1), tempera-
ture (X2), initial contaminant concentration (X3) and adsorbent dosage
(X4) were selected as independent variables, and the removal efficien-
cies (Y) of Pb(II), Zn(II) and Cd(II) were considered as the dependent
variables (responses). Variables were coded in accordance with the
following equation:
2.4. Analyses
Atomic absorption spectrophotometry was used for the analysis
of heavy metals in solution. Scanning electron microscopy (SEM)
equipped with an energy dispersive X-ray microanalyzer (EDAX)
(Cam-Scan MV 2300) was used to study the surface of solid residues
after the adsorption process. Prior to the SEM studies, the samples
were coated with a thin layer of gold.

X i −X 0 3. Results and discussion

xi ¼
ΔX i
where xi is the coded value of an independent variable, Xi is the real
value of an independent variable, X0 is the real value of an independent
variable at the center point and ΔXi is the step change value (Zheng and
Wang, 2010). The removal efficiency of each contaminant (Yi) was
calculated according to the following equation:
C0 −Ct
Y¼  100
C0
where, Y is the heavy metal removal efficiency (%), and C0 and Ct are the
initial and residual (after 120 min) concentrations of metal in solution
(mg/L). The experimental range and levels of independent variables
for metal ion removal were given in Table 1. A set of 29 experimental
runs, including duplicates were designed using BBD (Table 2).
ð1Þ
Statistical analysis by response surface methodology (RSM) was
used to determine a well-fitted regression model of adsorption process.
The experimental data of each adsorbate (Pb(II), Zn(II) and Cd(II)) were
fitted with linear, interactive, quadratic and cubic models to get the re-
gression equations. The significance of suggested regression models for
each adsorbate could be determined through the ANOVA. The final em-
pirical equations obtained from experimental data which demonstrate
the relationship between contaminant removal efficiency and indepen-
dent variables are given in Eqs. (4), (5) and (6) for Cd(II), Pb(II) and
ð2Þ Zn(II), respectively.
2
YCdðIIÞ ¼ 11:82 þ 2:45  A þ 4:84  C−2:56  C ð4Þ
YPbðIIÞ ¼ 76:20 þ 0:59  A−1:07  B þ 12:28  D−7:37  AD
2 2
þ 5:68  A þ 6:51  B ð5Þ

Table 2
Box–Behnken Design matrix for four variables and response values.

Experimental run pH (A) Temperature (B) Metal concentration in solution (C) Adsorbent dosage (D) Cd removal (%) Pb removal (%) Zn removal (%)

1 1.00 0.00 0.00 1.00 20.77 99.33 52.10

2 −1.00 0.00 −1.00 0.00 1.00 69.90 0.50
3 1.00 1.00 0.00 0.00 11.63 95.27 22.10
4 1.00 0.00 −1.00 0.00 2.50 88.40 34.40
5 −1.00 0.00 1.00 0.00 12.84 69.70 76.42
6 1.00 0.00 1.00 0.00 22.76 95.92 36.50
7 0.00 1.00 0.00 1.00 17.30 94.33 14.67
8 0.00 0.00 0.00 0.00 12.43 65.63 1.37
9 0.00 −1.00 −1.00 0.00 14.30 95.80 37.30
10 0.00 0.00 0.00 0.00 13.40 71.70 7.83
11 0.00 1.00 1.00 0.00 10.24 83.00 16.94
12 0.00 0.00 0.00 0.00 11.00 76.77 8.03
13 −1.00 −1.00 0.00 0.00 9.07 78.80 11.50
14 0.00 −1.00 0.00 1.00 8.97 97.30 18.53
15 0.00 0.00 0.00 0.00 9.07 74.27 6.033
16 0.00 −1.00 1.00 0.00 13.76 84.42 18.22
17 1.00 −1.00 0.00 0.00 13.60 98.87 44.03
18 0.00 0.00 −1.00 −1.00 5.00 91.30 2.00
19 0.00 −1.00 0.00 −1.00 12.73 57.83 7.87
20 0.00 0.00 0.00 0.00 10.00 74.43 6.60
21 0.00 0.00 −1.00 1.00 4.30 91.00 2.00
22 −1.00 1.00 0.00 0.00 13.50 92.63 14.30
23 1.00 0.00 0.00 −1.00 17.80 90.03 56.10
24 0.00 0.00 1.00 −1.00 11.76 73.14 17.40
25 0.00 1.00 −1.00 0.00 3.00 81.30 1.00
26 0.00 1.00 0.00 −1.00 11.53 56.67 1.90
27 0.00 0.00 1.00 1.00 14.94 89.58 18.28
28 −1.00 0.00 0.00 −1.00 11.13 48.47 2.43
29 −1.00 0.00 0.00 1.00 7.27 87.27 6.57
154 A. Ahmadi et al. / Journal of Geochemical Exploration 147 (2014) 151–158

Table 3 Table 5
ANOVA results of the regression model for optimization of Cd adsorption (determination ANOVA results of the regression model for optimization of Zn adsorption (determination
coefficient (R2) = 0.82; adjusted determination coefficient (R2adj) = 0.80). coefficient (R2) = 0.84; adjusted determination coefficient (R2adj) = 0.79).

Source Coefficient Sum of Degree of Mean F-value p-Value Source Coefficient Sum of Degree of Mean F-value p-Value
estimate squares freedom square (prob N F) estimate squares freedom square (prob N F)

Model 11.82 399.35 3 133.12 38.81 b0.0001 Model 0.86 7.04 6 1.17 18.14 b0.0001
A 2.45 71.80 1 71.8 20.93 0.0001 A 0.39 1.80 1 1.80 27.89 b0.0001
C 4.84 281.49 1 281.49 82.06 b0.0001 B −0.21 0.53 1 0.53 8.20 0.0090
C2 −2.56 46.06 1 46.06 13.43 0.0012 C 0.43 2.20 1 2.20 33.94 b0.0001
Residual 85.76 25 3.43 AC −0.54 1.16 1 1.16 18.00 0.0003
Lack-of-fit 77.51 21 3.69 1.79 0.3049 BC 0.36 0.51 1 0.51 7.96 0.0099
Pure error 8.25 4 2.06 A2 0.34 0.83 1 0.83 12.84 0.0017
Cor totala 485.11 28 Residual 1.42 22 0.065
a Lack-of-fit 1.35 18 0.075 3.95 0.0962
Total sum of squares corrected for the mean.
Pure error 0.076 4 0.019
Cor total 8.46 28

YZnðIIÞ ¼ 0:86 þ 0:39  A−0:21  B þ 0:43  C−0:54  AC þ 0:36

2
 BC þ 0:34  A ð6Þ
of the data is determined by its p-value being closer to zero (Srinivasan
where, YCd(II), YPb(II) and YZn(II) are the predicted responses for the re- and Viraraghavan, 2010). The main effect of each factor and the interac-
moval efficiency of Cd(II), Pb(II) and Zn(II) ions, respectively, and A, B, tion effects are statistically significant when p-value is less than 0.05
C and D are the coded values of pH, temperature, initial contaminant (Demim et al., 2014). As can be seen from Table 3, all the p-values of
concentration and adsorbent dosage, respectively. A, C and C2 are less than 0.05, which indicates that these variables are
Results of ANOVA for the removal of Cd(II), Pb(II) and Zn(II) were significant on the removal of Cd(II). Based on this hypothesis, A, D, AD,
tabulated in Tables 3, 4 and 5, respectively. The Fisher variation ratio A2 and B2 are the significant variables on the removal of Pb(II) and A,
(F-value) is a statistically valid measure of how well the factors describe B, C, AC, BC and A2 are the significant variables on the removal of Zn(II).
the variation in the data about its mean. The regression models were Response surface plots were used to determine the individual and
statistically significant with a confidence level of 95% at an calculated interaction effects of the input variables on the target responses. They
F-value of 38.8 for Cd(II), 19.5 for Pb(II) and 18.1 for Zn(II) with a very analyze the geometric nature of the surface, the maxima and minima
low probability value (p-value ≤ 0.0001) for all three heavy metal of the response and the significance of the coefficients of the equation
ions. The tabulated F-value for Cd(II) (F0.05, 3, 27), Pb(II) (F0.05, 3, 27) (Prakash et al., 2008).
and Zn(II) (F0.05, 3, 27) were found to be 2.29, 2.34 and 2.34, respectively.
Since, the calculated F-values for all the three models were higher than
3.1. Cadmium removal
the related tabulated F-values (38.8 N 2.29; 19.5 N 2.34; 18.1 N 2.34),
they have statistical significance. “Adequate Precision” ratios were
The response surface plots were obtained by varying two factors
21.19, 17.2 and 15.63 for Cd(II), Pb(II) and Zn(II) removal models re-
while keeping the other constant. Fig. 3 represents the effect of initial
spectively, which were far greater than the minimum desirable amount
concentration of metals and pH on Cd(II) removal. It shows that the ini-
of 4.0 which indicate the presence of adequate signal to noise for all
tial Cd(II) concentration had a positive effect on the removal efficiency
models.
of Cd(II) ions (the coefficient of C in Eq. (4) = 4.84), in which by in-
The value of determination coefficient (R2) determines the
creasing the initial concentration of Cd(II) from 10.0 to 50.0 mg/L, the
goodness-of-fit of the models. The adjusted R2 (R2adj) and predicted R2
Cd(II) removal efficiency increased from 4.4% to 14.1%; however, ac-
should be within approximately 0.20 of each other to be in reasonable
cording to Eq. (4), increasing the initial concentration of Cd(II) too
agreement. The close correspondence between R2adj and R2 indicates
much, had a negative effect on the removal efficiency (the coefficient
that unnecessary variables have not been included.
of C2 in Eq. (4) = − 2.56). This behavior could be related to the
As shown in Tables 3 to 5, the R2 values of 0.82, 0.85 and 0.84 respec-
tively, for Cd(II), Pb(II) and Zn(II) removal models showed the well
fitness of regression models for predicting the removal results.
The regression coefficient values of independent variables of
Eqs. (4) to (6) were listed in Tables 3 to 5. p-Value is used to determine
the effects in the model that are statistically significant. The significance

Table 4
ANOVA results of the regression model for optimization of Pb adsorption (determination
coefficient (R2) = 0.85; adjusted determination coefficient (R2adj) = 0.8).

Source Coefficient Sum of Degree of Mean F-value p-Value

estimate squares freedom square (prob N F)

Model 76.2 3839.89 6 639.98 19.5 b0.0001

A 10.59 1345.21 1 1345.21 40.99 b0.0001
B −1.07 13.72 1 13.72 0.42 0.5246
D 12.28 1809.91 1 1809.91 55.16 b0.0001
AD −7.37 217.56 1 217.56 6.63 0.0173
A2 5.68 222.56 1 222.56 6.78 0.0162
B2 6.51 292.42 1 292.42 8.91 0.0068
Residual 594.12 22 32.81
Lack-of-fit 521.29 18 36.06 1.98 0.2674
Pure error 72.84 4 18.21
Fig. 3. 3D plots for interactive effect of pH and initial Cd(II) concentration on the removal
Cor total 4561.81 28
efficiency of Cd(II) at temperature = 35 °C and adsorbent dosage = 3 g/L.
 A. Ahmadi et al. / Journal of Geochemical Exploration 147 (2014) 151–158 155

complexity of competitive adsorption of the metal ions at different con-

centrations on the surface of the nanoparticles. In the higher range of
adsorbate concentration, the surface of adsorbent began to get saturated
and results in decreasing the adsorption efficiency of Cd(II) ions. As
shown in Fig. 3, solution pH was the other significant factor and showed
a positive effect (the coefficient of A in Eq. (4) = 2.45). The removal ef-
ficiency of Cd(II) increased from 9.37% to 14.26% by increasing the pH
from 4.5 to 7.5. The pH of the zero point of charge (pHzpc) value for
maghemite is about 6.1. Electrostatic attraction is considered as the
main adsorption mechanism at pH values higher than the pHzpc. Metal
ions can also adsorb on the surface of iron oxides through the ion ex-
change process at pH values less than the pHzpc (the exchange of proton
with cation) (Tang and Lo, 2013).
The low removal efficiency of Cd(II) at pH values below the pHzpc is
attributed to the positively charged of the maghemite surface. The re-
moval of Cd(II) at the pH values lower than the pHzpc, is justified by
the exchange of adsorbed proton with Cd(II) ions.

3.2. Lead removal
Figs. 4 and 5 show the effects of significant variables on the removal
efficiency of Pb(II) ions. The removal efficiency of Pb(II) on maghemite
nanoparticles was very sensitive to the changes in solution pH (Coeffi-
cient = 10.59 in Eq. (6)). It shows that increasing in pH value from
4.5 to 7.5 resulted in enhancing the removal efficiency of Pb(II) ions
from 71.29% to 92.47% (Fig. 4). It can also be pointed out that at the
pH values lower than the pHzpc, some Pb(II) ions can be adsorbed on
the surface of maghemite nanoparticles through the ion exchange pro-
cess. It was reported (Lodeiro et al., 2006; Naiya et al., 2008) that the
precipitation of lead hydroxide can play a leading role during heavy
metal removal process at pH above 6. The effect of temperature and
pH on the removal efficiency of Pb(II) ions is represented in Fig. 4. As
can be seen, increasing temperature too much, had a significant positive
effect on the removal efficiency of Pb(II) ions (coefficient = 6.51 in
Eq. (6)). The increased removal of Pb(II) ions with increasing tempera-
ture may be a result of the faster chemical precipitation rate of lead hy-
droxide at the higher temperatures. The interactive effects of pH and
adsorbent dosage were shown in Fig. 5. They show that increasing in ad-
sorbent dosage has the highest effect on the adsorption of Pb(II) ions
(coefficient = 12.28 in Eq. (6)). By increasing the adsorbent dosage
from 1.0 (g/L) to 5.0 (g/L), the removal efficiency of Pb(II) ions rose
from 63.92% to 88.48%. This behavior could be ascribed to a greater sur-
face area and the more availability of adsorption sites at the higher ad-
sorbent dosage. Although the increase in each of pH and adsorbent
Fig. 5. 3D plots for interactive effect of pH and adsorbent dosage at initial Pb(II) concentra-
tion = 30 mg/L and temperature = 35 °C on the adsorption efficiency of Pb(II).
dosage parameters individually had a positive effect on the removal ef-
ficiency of Pb(II) ions, the simultaneous increase of these parameters
showed a negative synergistic effect on the removal.
3.3. Zinc removal
Fig. 6 shows a response surface plot where Zn(II) removal was
represented by varying simultaneously pH from 4.5 to 7.5 and Zn con-
centration from 10 to 50 mg/L. From this plot, it can be found that
about 58% Zn removal can be achieved at the pH value of 4.5 and the
Zn concentration of 50 mg/L. The removal was sensitive to the interac-
tion effect of pH and the initial concentration of Zn(II) which had a neg-
ative synergistic effect on the target variable (Figs. 6 and 7). However,
increasing pH from 4.5 to 7.5 and initial Zn(II) concentration from
10.0 to 50.0 mg/L increased the removal efficiency of Zn(II) ions from
6.6% to 39.1% and from 2.7% to 19.1%, respectively. At the higher level
of pH, the removal efficiency of Zn(II) was increased mainly as a result
of electrostatic attraction. The removal of Zn(II) at pH values less than
the pHzpc is related to the cation exchange mechanism. This assumption
was supported by the decreasing of the solution pH during the process
which could be a result of releasing protons into the solution. Fig. 7

Fig. 4. 3D plots for interactive effect of pH and temperature at initial Pb(II) concentration = Fig. 6. 3D plots for interactive effect of pH and initial Zn concentration at temperature =
30 mg/L and adsorbent dosage = 3 g/L. 35 °C and adsorbent dosage = 3 g/L on the removal efficiency of Zn(II).
156 A. Ahmadi et al. / Journal of Geochemical Exploration 147 (2014) 151–158
Fig. 7. 3D plots for interactive effect of temperature and initial Zn concentration in solution
at pH = 6 and adsorbent dosage = 3 g/L on the adsorption efficiency of Zn(II).
showed the positive effects of temperature and initial Zn(II) concentra-
tion on the heavy metal removal efficiency. It shows that the initial con-
centration of the metal is more significant than temperature under the
high concentration of Zn(II) ions.
3.4. Optimization
Maximum removal efficiency for each adsorbate and the corre-
sponding optimal conditions of variables were determined and the
models were confirmed by some further experimental runs. Numerical
optimization was done to find a maximum point for the desirability
function (Mourabet et al., 2012) by setting the values of pH, tempera-
ture, concentration of initial ions and adsorbent dosage within their
ranges and maximizing the removal efficiencies of Cd(II), Pb(II) and
Zn(II) ions. As can be seen in Fig. 8, the best local maximum value was
Fig. 8. Desirability ramp for numerical optimization of four independent variables and the responses.
found to be at the initial solution pH of 7.5, the temperature of 45 °C,
the initial ion concentration of 50 mg/L and the adsorbent (dosage of
4.74 g/L). In this condition the removal efficiencies of Cd(II), Pb(II) and
Zn(II) ions were 16.6%, 100.0% and 42.5%, respectively and the desirabil-
ity value was found to be 0.90. This optimum condition was checked ex-
perimentally. The results showed the removal efficiency of 16.2%,
100.0% and 42.1% for Cd(II), Pb(II) and Zn(II) ions, respectively. The
high degree of agreement between the predicted optimum conditions
and the repeated experimental results indicated that the Box–Behnken
Design could be employed as an effective and reliable tool for evaluation
and optimization of the effects of adsorption parameters on the removal
efficiency of heavy metals using maghemite nanoparticles.
SEM-EDAX analysis was used to characterize the chemical proper-
ties and morphology of the adsorbent. The results were presented in
Fig. 9. It was confirmed from this analysis that the heavy metal ions
were present on the surface of nanoparticles after the adsorption
process.
4. Conclusion
In this research, maghemite nanoparticles were used to remove
some heavy metal ions, i.e. Pb(II), Zn(II) and Cd(II), from aqueous solu-
tions. Response surface methodology was used to find a maximum loca-
tion in the design space. A Box–Behnken Design was employed to
evaluate the effects of pH, temperature, initial contaminant concentra-
tion and adsorbent dosage on the removal efficiency of Pb(II), Zn(II)
and Cd(II) ions on maghemite (γ-Fe2O3) nanoparticles under competi-
tive conditions. Quadratic models were well fitted to the experimental
data and second-order polynomial equations (regression models)
were described the relationship between the responses and the vari-
ables accurately. Results showed that the initial concentration of
Cd(II) and pH were the most significant parameters on the removal
efficiency of Cd(II) ions. Adsorbent dosage, pH and their interaction ef-
fects had the most significant influences on the removal efficiency of
Pb(II) ions. Moreover, the interaction effect of pH and the initial concen-
tration Pb(II) had the most significant influences on the removal
 A. Ahmadi et al. / Journal of Geochemical Exploration 147 (2014) 151–158
Fig. 9. SEM/EDAX photomicrographs of maghemite nanoparticles after adsorption process at the optimum conditions.
efficiency of Zn(II). The predicted maximum adsorption capacities were
10.55, 4.49 and 1.75 mg/g for Pb(II), Zn(II) and Cd(II), respectively. The
corresponding optimal conditions of variables of adsorption process
were determined to be at the pH of 7.5, the temperature of 45 °C, the
initial metal concentration of 50 mg/L (each metal ion) and the adsor-
bent dosage of 4.74 g/L. The removal efficiency of heavy metal ions by
the nanoparticles was found to follow the order of Pb N Zn N Cd.
SEM-EDAX analysis confirmed that the heavy metal ions were
present on the surface of nanoparticles after adsorption process.
The results of this study suggested that maghemite nanoparticles
could be used as a potential and appealing adsorbent for the removal
of heavy metals from aqueous solutions.
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