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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.
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
2.1. Materials
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 2.4. Analyses
from aqueous solutions by maghemite nanoparticles. The four parame-
ters affecting heavy metal removal, namely solution pH (X1), tempera- Atomic absorption spectrophotometry was used for the analysis
ture (X2), initial contaminant concentration (X3) and adsorbent dosage of heavy metals in solution. Scanning electron microscopy (SEM)
(X4) were selected as independent variables, and the removal efficien- equipped with an energy dispersive X-ray microanalyzer (EDAX)
cies (Y) of Pb(II), Zn(II) and Cd(II) were considered as the dependent (Cam-Scan MV 2300) was used to study the surface of solid residues
variables (responses). Variables were coded in accordance with the after the adsorption process. Prior to the SEM studies, the samples
following equation: were coated with a thin layer of gold.
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 (%)
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
Table 4
ANOVA results of the regression model for optimization of Pb adsorption (determination
coefficient (R2) = 0.85; adjusted determination coefficient (R2adj) = 0.8).
3.2. Lead removal 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).
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-
dosage parameters individually had a positive effect on the removal ef-
cient = 10.59 in Eq. (6)). It shows that increasing in pH value from
ficiency of Pb(II) ions, the simultaneous increase of these parameters
4.5 to 7.5 resulted in enhancing the removal efficiency of Pb(II) ions
showed a negative synergistic effect on the removal.
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- 3.3. Zinc removal
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 Fig. 6 shows a response surface plot where Zn(II) removal was
metal removal process at pH above 6. The effect of temperature and represented by varying simultaneously pH from 4.5 to 7.5 and Zn con-
pH on the removal efficiency of Pb(II) ions is represented in Fig. 4. As centration from 10 to 50 mg/L. From this plot, it can be found that
can be seen, increasing temperature too much, had a significant positive about 58% Zn removal can be achieved at the pH value of 4.5 and the
effect on the removal efficiency of Pb(II) ions (coefficient = 6.51 in Zn concentration of 50 mg/L. The removal was sensitive to the interac-
Eq. (6)). The increased removal of Pb(II) ions with increasing tempera- tion effect of pH and the initial concentration of Zn(II) which had a neg-
ture may be a result of the faster chemical precipitation rate of lead hy- ative synergistic effect on the target variable (Figs. 6 and 7). However,
droxide at the higher temperatures. The interactive effects of pH and increasing pH from 4.5 to 7.5 and initial Zn(II) concentration from
adsorbent dosage were shown in Fig. 5. They show that increasing in ad- 10.0 to 50.0 mg/L increased the removal efficiency of Zn(II) ions from
sorbent dosage has the highest effect on the adsorption of Pb(II) ions 6.6% to 39.1% and from 2.7% to 19.1%, respectively. At the higher level
(coefficient = 12.28 in Eq. (6)). By increasing the adsorbent dosage of pH, the removal efficiency of Zn(II) was increased mainly as a result
from 1.0 (g/L) to 5.0 (g/L), the removal efficiency of Pb(II) ions rose of electrostatic attraction. The removal of Zn(II) at pH values less than
from 63.92% to 88.48%. This behavior could be ascribed to a greater sur- the pHzpc is related to the cation exchange mechanism. This assumption
face area and the more availability of adsorption sites at the higher ad- was supported by the decreasing of the solution pH during the process
sorbent dosage. Although the increase in each of pH and adsorbent 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). 4. Conclusion
showed the positive effects of temperature and initial Zn(II) concentra- In this research, maghemite nanoparticles were used to remove
tion on the heavy metal removal efficiency. It shows that the initial con- some heavy metal ions, i.e. Pb(II), Zn(II) and Cd(II), from aqueous solu-
centration of the metal is more significant than temperature under the tions. Response surface methodology was used to find a maximum loca-
high concentration of Zn(II) ions. 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)
3.4. Optimization and Cd(II) ions on maghemite (γ-Fe2O3) nanoparticles under competi-
tive conditions. Quadratic models were well fitted to the experimental
Maximum removal efficiency for each adsorbate and the corre- data and second-order polynomial equations (regression models)
sponding optimal conditions of variables were determined and the were described the relationship between the responses and the vari-
models were confirmed by some further experimental runs. Numerical ables accurately. Results showed that the initial concentration of
optimization was done to find a maximum point for the desirability Cd(II) and pH were the most significant parameters on the removal
function (Mourabet et al., 2012) by setting the values of pH, tempera- efficiency of Cd(II) ions. Adsorbent dosage, pH and their interaction ef-
ture, concentration of initial ions and adsorbent dosage within their fects had the most significant influences on the removal efficiency of
ranges and maximizing the removal efficiencies of Cd(II), Pb(II) and Pb(II) ions. Moreover, the interaction effect of pH and the initial concen-
Zn(II) ions. As can be seen in Fig. 8, the best local maximum value was tration Pb(II) had the most significant influences on the removal
Fig. 8. Desirability ramp for numerical optimization of four independent variables and the responses.
A. Ahmadi et al. / Journal of Geochemical Exploration 147 (2014) 151–158 157
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 Demim, S., Drouiche, N., Aouabed, A., Benayad, T., Couderchet, M., Semsari, S., 2014. Study
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