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Modification of Pomegranate Waste With Iron Ions A

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Salmani et al.

AMB Expr (2017) 7:225


https://doi.org/10.1186/s13568-017-0520-0

ORIGINAL ARTICLE Open Access

Modification of pomegranate waste


with iron ions a green composite for removal
of Pb from aqueous solution: equilibrium,
thermodynamic and kinetic studies
Mohammad Hossein Salmani1*, Mohammad Abedi2, Sayed Ahmad Mozaffari2 and Hossien Ali Sadeghian3

Abstract
Pomegranate waste modified with ­Fe2+ and ­Fe3+ ions followed with carbonization were used as an adsorbent to
remove the ­Pb2+ ions from aqueous solution. To optimum the highest adsorption efficiency, adsorption experiments
were conducted on iron modified carbons by batch technique. The characteristic of composite was studied by scan-
ning electron microscope (SEM) and Fourier transform infrared spectrometer (FT-IR). The best pH for control of chemi-
cal adsorption was selected within pH of 6.0–6.5. It was observed that the contact time of 90 min, initial concentration
50.0 ppm, and adsorbent dose, 1.0 g/100 ml solution was found to be optimum conditions. On this condition, the
maximum adsorption capacity was obtained 27.5 and 22.5 mg/g for ­Fe2+ and ­Fe3+ impregnated pomegranate peel
carbons (PPC), respectively. The value of ­Cid, 1.584 for ­Fe2+-PPC and 0.552 for ­Fe3+-PPC, indicates that the effect of
the boundary layer is more important in adsorption of ­Pb2+ by ­Fe2+-PPC and the pore diffusion is the rate limiting
mechanism after 30 min. Thermodynamic parameters of Gibbs free energy, enthalpy, and entropy of P ­ b2+ adsorp-
tion on iron-modified carbons suggest that the adsorption process is favorable and spontaneous under the optimum
condition.
Keywords: Iron modified carbon, Pomegranate peels, Composite, Thermodynamic, Kinetic

Introduction such as ion exchange, coagulation, electrochemical pro-


Lead is known as the heavy metals, which is strongly cess, reverse osmosis, and ion flotation (Ehrampoush
toxic to humans, animals, and plants. Inter of lead to et al. 2015). These methods are costly and produce the
the human body even at low concentrations causes seri- secondary wastes. One of the high-performance and
ous problems to the nervous and reproductive system, low-cost methods for removing of ionic pollutants from
kidney, liver, brain and bony tissues (Grant 2008; Ren- aqueous solutions is adsorption. However, the cost of
ner 2010; Andrade et al. 2015). Environmental Protection used adsorbents and their separation from suspension
Agency (EPA) approved the maximum threshold limit of after adsorption are the important restricting factors in
0.015 ppm for lead in drinking water. The removal of lead perspective on the applicability of adsorption process.
from wastewaters, before discharging to aquatic environ- Recently, considerable notation has been given to the
ment, in high concentration is accomplished by common development of substitutes from readily available and
processes, including precipitation with hydroxide ion or cheaper materials such as agricultural wastes for prepara-
lime and in low concentration by advanced processes tion of activated carbon to remove pollutants to approach
the standard levels (Babel and Kurniawan 2003). Until
now, using of low-cost agricultural sorbents, including
*Correspondence: mhsn06@yahoo.com
1
Ponkan peel (Pavan et al. 2008), waste tea leaves (Cher-
Department of Environmental Health, School of Public Health, Shahid
Sadoughi University of Medical Science, Yazd, Islamic Republic of Iran
aghi et al. 2015), potato peel (Taha et al. 2011), modi-
Full list of author information is available at the end of the article fied onion skins (Saka et al. 2011), the activate carbon

© The Author(s) 2017. This article is distributed under the terms of the Creative Commons Attribution 4.0 International License
(http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium,
provided you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license,
and indicate if changes were made.

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Salmani et al. AMB Expr (2017) 7:225 Page 2 of 8

of peanut shell (Wilson et al. 2006), pistachio shell, and and ­Fe2+ solutions for 12 h, separately. The impregnated
apricot stone (Kazemipour et al. 2008), have been exam- granules were dried and then carbonized at 400 °C for
ined for removing of P­ b2+ ions from aqueous solutions. 3 h into a programmable furnace in the absence of air.
Pomegranate wastes as a by-product of juice, jams, The residual was washed 3 times with distilled water to
syrup, and sauce manufacturing industries, which pro- eject excess ions from the modified carbons. Eventually,
duced in large amounts in Iran. The peels include about the iron modified carbons were heated at 105 °C, named
45–50% of the total weight of fruit. The fruit peels have ­Fe2+-PPC and ­Fe3+-PPC and maintain for further uses.
a strong affinity and high selection towards heavy metals
because of the various functional groups on the surface Calibration
of it. Hence, the idea to change the by-product of pome- The ranges of the calibration curves (0–50 ppm) for P­ b2+
granate fruit to iron impregnation carbon for cleaning of the samples were selected for calibration of AAS. For
the environment and removing of heavy metal is valu- this purpose, the absorbance of standard solutions was
able. Abedi et al. impregnated of ­Fe2+ and ­Fe3+ ions to constructed versus concentration at a maximum wave-
the PPC were studied to remove Cd(II) ions (Abedi et al. length of 283.3 nm. Detection and quantification limits
2016). were defined as the lowest concentrations of a compo-
Considering the above descriptions, we used as an nent that produces a signal equal to three and ten times
adsorbent the iron modification of PPCs for removing of the standard deviation for a series of the blank solu-
of ­Pb2+ from aqueous solution by one factor at a time tion. The following equations were used for calculation of
methodology. The main objective of this work is to obtain the detection (DL) and quantification (QL) limit:
the adsorption kinetic and thermodynamic parameters
3.3 ∗ σ A
for the adsorption reaction of ­Pb2+ ions with prepared D.L. = (1)
composite. m
The adsorption process depends on many factors
10 ∗ σ A
including pH, temperature, adsorbent mass, concentra- Q.L. = (2)
tion of pollutant, adsorbent type, contact time and agita- m
tion time. In the present study, the effect of initial lead DL and QL are the detection and quantification limit, σA
concentration, adsorbent dose, and temperature was is the standard deviation of the intercept, and m is the
screened for removing of ­Pb2+ ions by ­Fe2+ and ­Fe3+ slope of the calibration of linear equation.
impregnated into PPC adsorbents. The experiments were
performed in batch technique and adsorption capacity Experiments
was calculated in the each step. Then, the plot of adsorp- To obtain optimal conditions, the effect of contact time,
tion capacity via parameter changes was used to choose initial ­Pb2+ concentration, and adsorbent dose were
the optimum amount of each factor. determined at laboratory temperature (27 °C) based on
the following experiments:
Materials and methods The effect of initial P ­ b2+ concentration was studied
Reagents using 0.2 g of adsorbents and 50 ml of different concen-
All of the chemicals used in this work were of analytical trations of ­Pb2+ solution in the range of 10, 25, 50, 75 and
grade. The 100 ppm stock solution of P ­ b2+ was prepared 100 ppm in the screw-capped containers. The influence
by dissolving of Pb(NO3)2 in distilled water. The ­FeCl3 of composite dose on P ­ b2+ adsorption was examined by
and ­FeCl2 solutions were used for modification of pome- taking 50 ml of 50 ppm of ­Pb2+ solutions and shaking
granate peels. Five standard solutions of 0.0, 5.0, 10.0, with varying amounts of adsorbents in ranging from 0.1
25.0, 50.0 ppm were made from a solution of 100 ppm to 1.5 g. The similar solutions without adsorbents as con-
by dilution with 1% (v/v) ­HNO3 for calibration of atomic trol samples were examined in parallel. All of the batch
absorption spectrometer (AAS). The working solutions experiments were performed at solution pH of 6.5 in the
with desired P­ b2+ concentration were daily made by dilu- 150 ml closed containers and constant shaker 180 RPM
tion of the stock solution. using a shaker equipped with an electrical heater. At the
end of all the experiments, the suspension was filtered
Preparation of composites and the concentration of P ­ b2+ in the filtered solution
Pomegranate wastes were collected from Agro Indus- was measured by AAS that it was calibrated, previously.
tries Co in Fars province, Iran. They were dried at labo- According to the obtained data, the adsorption capacity
ratory temperature in the absence of sunlight and sized (q) of adsorbents (mg/g) was determined by the differ-
in mesh 40–100 by standard sieves. To modify them, ence of initial and equilibrium concentration using the
10 g of the granules were mixed with 10 ml of 0.1 M ­Fe3+ mass balance equation, as follows:

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Salmani et al. AMB Expr (2017) 7:225 Page 3 of 8

programmable orbital shaker. The experimental data


V
qt = (C0 − Ce) × (3) were applied to determination of thermodynamic distri-
m bution constant as follows:
Where ­C0 and C ­ b2+ in
­ e are ion concentrations (mg/l) of P
Cs
solution at initial and equilibrium time, respectively, m is K = (5)
the mass of adsorbent (g) and V is the volume of solution Ce
(ml). The Gibbs free energy (ΔG), entropy (ΔS) and enthalpy
(ΔH) were obtained from the Eqs. 6 and 7:
Adsorption kinetic
For evaluation of information the kinetic adsorption G = −RT ln K (6)
mechanism, a satisfactory selection of model is required.  
S H 1
Different adsorption models are available for designing lnk = + (7)
of the adsorption rate a system. In the present study, five R R T
batch adsorption experiments were conducted by varia- where K and R are the equilibrium and the universal
tion of contact time from 10 min up to 120 min related to gas constant (8.314 J/mol °K), C ­ s and C
­ e are ion con-
kinetic studies. The obtained data were fitted to intrapar- centrations adsorbed on the solid phase (mol/g) and
ticle diffusion model in order to consider the adsorption in equilibrium liquid phase (mol/l), and T is the abso-
mechanism and rate limiting step in the adsorption pro- lute temperature °K. According to Eq. 7, enthalpy func-
cess which expressed by Weber–Morris as follows: tion was calculated from the slope and entropy from the
intercept of the line of lnK against 1/T.
qt = kid t 1/2 + Cid (4)
Where ­qt is the adsorption capacity (mg/g), ­kid (mg/g/ Results
min) is the intraparticle rate constant and intercept of ­Cid SEM
(mg/g) related to the thickness of the boundary layer. SEM is a powerful magnification tool that produces
images of a sample by scanning the surface with a focused
Adsorption thermodynamic beam of electrons to obtain information. The electrons
For investigation of thermodynamic parameters, the interact with the atoms in a sample, producing various
equilibrium adsorption experiments were performed signals that contain information about the topology of
by taking 50 ppm ­Pb2+ solution using 0.1 g of adsor- sample surface. Figure 1a, b shows the SEM photographs
bents at temperatures 25, 55 and 85 °C on a temperature of the PPCs without and with impregnation of iron ions.

Fig. 1 SEM images of adsorbents prepared for adsorption of Pb. SEMs were recorded in the acceleration voltage 15.00 kV and magnitude ×100.00
for focusing on surface porous. a SEM image of pomegranate peel carbon and b iron modified pomegranate peel carbon. There was a significant
difference of porous between two image corresponding modifications

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Salmani et al. AMB Expr (2017) 7:225 Page 4 of 8

FT‑IR Table 1 The results of AA calibration for measurement


FT-IR instrument is a good tool to identify the character- of ­Pb2+
istic of functional groups in a compound. The main func- Concentration No. of replicates Mean value SD
tional groups found in ­Fe2+-PPC by adsorption spectra in of ­Pb2+ (ppm) of signal
the infrared region, which illustrated in Fig. 2.
0.0 20 0.0037 0.01108
5.0 5 0.1718 0.00227
Analytical sensitivity and detection limit
10.0 5 0.3312 0.00368
A calibration of absorbance versus concentration was
25.0 5 0.8526 0.00225
constructed using 5 points of varying concentration. The
50.0 5 1.7070 0.00574
following replicate data are presented in Table 1.
Linearity of methods was checked within the
0–50 ppm. An analysis of the calibration data for the optimum of the effective parameters on the adsorption
determination of ­Pb2+ based upon its AAS yielded the capacity of ­Fe2+ and ­Fe3+ impregnation to pomegranate
following equation: peel carbons for adsorption of P­ b2+ ions from equation
solution.
S = 0.0037 (± 0.0111) × C + 0.03463 (± 0.000434)
(8)
Effect of time
R2 = 0.9996 SE = 0.0132 F = 6349.17 P-value = 0.0001. The results of experiments (Fig. 3) conducted to obtain
The statistical parameters show that the analytical the equilibrium time required for the uptake of ­Pb2+
method for determination of P ­ b2+ had suitable calibration. ­ e2+-PPC and F
ions by two adsorbents. For F ­ e3+-PPC, 8.8
Sensitivity is the response of the instrument to changes in and 8.6 mg of lead were adsorbed in the unit of adsor-
analyte concentration or a measure of the ability of method bent mass at the 90 min, respectively. The uptake of
to distinguish between small differences in concentration ­ e2+-PPC and F
metal ions for F ­ e3+-PPC decreased to 8.6
in different samples. The sensitivity was obtained from and 7.9 mg/g after 120 min. In general, the total capac-
the slope of the calibration curve. The detection limit is ity adsorption of ­Fe2+-PPC and ­Fe3+-PPC was achieved
defined as the lowest concentration of the component, constant in the 90 min. Therefore, in subsequent experi-
which will generate a signal/noise ratio of 3. The detection ments, 90 min was selected for contact times.
and quantification limit value were obtained from Eqs. 1
and 2. The results are represented in Table 2. Effect of initial concentration
Preliminary experiments showed that iron modified Pb2+ con-
Figure 4 represents the effect of initial ­
pomegranate peel carbonized at 400 °C gives the high- centrations on the adsorption capacity of ­Fe2+-PPC
est adsorption for P ­ b2+ ions in aqueous solution. There- 3+
and ­Fe -PPC at pH of 6.5. The finding showed that
fore, several batch experiments were done to find out the ­b2+ increased from 3.2
the adsorption capacity of P

Fig. 2 FT-IR spectrum of ­Fe2+ modified pomegranate peel carbon

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Salmani et al. AMB Expr (2017) 7:225 Page 5 of 8

Table 2 Linearity, limit of detection and quantification


for the AA
Parameters Value

Linearity range 1–50 ppm


Intercept 0.0037 ± 0.0111
Slop 0.0346 ± 0.00043
Correlation coefficient (­ R2) 0.9996
Probability (P) < 0.0001
Detection limit (D.L.) 1.050 mg/l
Quantification limit (Q.L.) 3.200 mg/l
Fig. 5 The effect of composite dose on adsorption capacity. The
change of adsorption capacity in removal of the ­Pb2+ vs amount
of adsorbents in solution for ­Fe2+-PPC is depicted in red and for
­Fe3+-PPC is depicted in blue

shows the plot of adsorption capacity of ­Fe2+-PPC and


­Fe3+-PPC to uptake of ­Pb2+ versus adsorbent doses. The
adsorption of ­Pb2+ increased from 25.1 and 24.2 to 26.7
and 25.4 mg/g with an increase in adsorbent dose from
0.10 to 1.0 w/v% for ­Fe2+-PPC and F
­ e3+-PPC respectively.
With increasing of the adsorbent dose to 1.5 w/v%, the
adsorption capacity decreased from 26.7 and 25.4 to 14.6
and 13.0 mg/g further.
Fig. 3 The effect of contact time on adsorption capacity. The
change of adsorption capacity in removal of ­Pb2+ vs contact time for
­Fe2+-PPC is depicted in red and for ­Fe3+-PPC is depicted in blue Kinetic
In this work, the experimental data were fitted to the
intraparticle diffusion equation that was given by Weber
and Morris equation as Eq. 3. Figure 6 represents the plot
of ­qt versus ­t1/2 for ­Fe2+-PPC.
The ­kid, ­Cid, and ­R2 values were obtained from the plot
of ­qt versus ­t1/2 (Fig. 6) are summarized in Table 3.

Thermodynamic
The equilibrium constant, adsorption free energy,
enthalpy, and entropy changes of reaction were estimated
by Eqs. 6 and 7. The corresponding values of thermody-
namic functions are summarized in Table 4.
Fig. 4 The effect of initial concentration on adsorption capacity. The
change of adsorption capacity in removal of ­Pb2+ vs initial concen- Discussion
tration of ­Pb2+ for ­Fe2+-PPC is depicted in red and for ­Fe3+-PPC is Comparison of two images in Fig. 1 revealed that the PPC
depicted in blue
had low porosity and regular surfaces, whereas iron mod-
ified composite showed the development in their poros-
ity and hence an increasing of the number of sites on the
to 20.6 mg/g for ­ Fe2+-PPC and 3.1 to 19.4 mg/g for surface, consequently the modification with iron have
3+
­Fe -PPC until 50 ppm, but it had a little increasing to been enhanced the active surface of composite.
27.5 and 22.5 mg/g by increasing duplicate of the initial The functional groups on the surface adsorbent are
concentration of ­Pb2+ from 50 to 100 ppm. important for understanding of the adsorption process.
The Fig. 2 shows a broadband about 3400 and 2900/cm
Effect of dose which denote the presence of hydrogen-bonded OH
The influence of the adsorbent dose on the adsorption groups on the surface of adsorbent, originally bonded
process at a constant initial concentration of ­Pb2+ was to an organic polymeric structure. The IR spectra indi-
examined to obtain the right adsorbent mass. Figure 5 cates a strong peaks about 1600/cm band is related to

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Salmani et al. AMB Expr (2017) 7:225 Page 6 of 8

species in solution. In aqueous solution, the general


­ b2+ ions at different pH ranges
hydrolysis reaction of P
can be written as follows:
pH < 2 H3 O+ + Pb2+ = no reaction (9)

pH = 2−6.5 6H3 O+ + Pb2+ = Pb(H2 O)2+


6 + 6H
+

(10)

pH = 6.5−7 6H2 O + Pb2+ = Pb(H2 O)5 (OH)+


(aq) + H
+

(11)
2+
Fig. 6 Diffusion kinetic models for ­Pb adsorption. The Morris Weber pH = 7−8 2HO− + Pb2+ = Pb(OH)2(aq.) (12)
model kinetic were don’t in various times. This model for ­Fe2+-PPC is
depicted in blue. The Morris Weber model in the range of 0–30 min
for ­Fe3+-PPC is depicted in red and in the range of 30–60 min is pH > 8 2HO− + Pb2+ = Pb(OH)2(s) and then
depicted in green
HO− + Pb(OH)2(s) = Pb(OH)−
3 (aq) (13)
Based on the above equations, dissolved Pb species
Table 3 The intraparticle diffusion kinetic data for adsorp-
which are present in the solution, depend on pH and
tion of ­Pb2+ ions on iron modified pomegranate peel car-
bons are in different forms such as ­Pb2+, ­PbOH+, Pb(OH)2,
and Pb(OH)3−. The Eqs. 9 and 10 indicate that P ­ b2+
Adsorbent Parameters ions are the predominant species to pH of 6.5, and are
Kid Cid R2 responsible for maximum adsorption. Another pH con-
ditions for the formation lead hydroxide species like
Up to 30 min
­PbOH+, Pb(OH)2, and Pb(OH)− 3 occur after pH of 6.5,
Fe2+ PPC 0.228 1.584 0.998
which causes a decrease in the adsorption yield. It is
Total of time
clear that precipitation of ­Pb2+ in the form of Pb(OH)2
Fe3+ PPC 0.299 0.552 0.986
at pH > 7 can be decreased the adsorption of ­Pb2+ ions,
which cause a decrease in the adsorption yield. The
precipitation did not occur at the pH lower than 6.5,
the vibration of –C=O group stretching from aldehydes, but the adsorption yield of metal ions may be very low
ketones, and carboxylic acids (Palin et al. 2016). The at acidic pH values. This situation is explained based
peaks of 500–900/cm regions indicate the loading of ­Fe2+ on electrostatic repulsion forces between surface posi-
ions into functional groups of granola surface. tive charges and Pb species. The ­Pb2+ ions adsorption
The pH value not only has an impact on the charge of occurred on the adsorbent surface by exchange with
the adsorbent surface, but also the ionization degree of ­H+ at pH of 6.5.
particles and the existence of adsorbate species in solu- Regards to the above, it is concluded that the pH for
tion (Zhan and Zhao 2003). In the case of P ­ b2+ ions, adsorbents must be selected higher than the pHzpc
the relative hydrolysis and precipitation of Pb species of adsorbate that it was obtained for F ­e2+-PPC (4.3)
3+
at different pH, have an effect on the adsorption pro- and ­Fe -PPC (6.0) in our previous work (Abedi et al.
cess with changing of the form and number of Pb ion 2016). In this state, most of the sorption sites on the two

Table 4 Thermodynamic parameters for Pb(II) adsorption on iron modified pomegranate peel carbons (­Fe2+-PPC
and ­Fe3+-PPC)
Temp (°C) Fe2+-PPC Fe3+-PPC
ΔG* ΔH* ΔS* ΔG* ΔH* ΔS*

25 − 0.17 50.0
55 − 3.87 40. 6 0.136 − 2.51 27.5 0.092
85 − 8.35 − 5.45
* kJ/mol

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Salmani et al. AMB Expr (2017) 7:225 Page 7 of 8

composites are negatively charged in the solution. In are governed by the adsorption mechanism (Weber and
contrast, the pH for formation of ­Pb2+ must be selected Morris 1963). Figure 6 is not linear at all times, but have
lower than pH of 6.5. According to the above description, two regions linear. The first stage (until 30 min) indicates
it is concluded that the adsorption process for ­Pb2+ ions intraparticle diffusion or pore diffusion and the second
will be electrically favorable at pH of 6.0–6.5. So, this pH region (up to 30 min) related to the adsorption on the
was selected for other adsorption experiments. Under interior of the adsorbent. It also indicates that the pore
this condition, biosorption of P ­ b2+ on the F
­ e2+-PPC and diffusion is not only the rate limiting mechanism and
3+
­Fe -PPC was expected to be favorable by electrostatic other mechanisms are involved in the adsorption of P ­ b2+
2+
forces. by ­Fe -PPC. Similar results were obtained in the study
The effect of time data was studied to investigate the of (Jiménez-Cedillo et al. 2013). In addition, The result
adsorption mechanism of P ­ b2+ ions on the iron-modified shows that the linearity q ­ t vs t­ 1/2 plots for a total of con-
carbons. A time required for the adsorbate concentration tact time between the ­Pb2+ ions and F ­ e3+-PPC did not
to reach a constant value during the adsorption process pass through the origin. This show that the intraparticle
was defined as adsorption equilibrium time. Figure 3 diffusion was only the rate-controlling step, but also the
shows the rate of ­Pb2+ adsorption was fast in the initial one portion linearity of the plot for ­Fe3+-PPC shows that
times proportional to the enough available surface area the one stage is involved in adsorption mechanism and
on the adsorbent. Until time increased, more amount of the boundary layer effect on the adsorption is limiting
­Pb2+ adsorbed on the active sites on the adsorbent sur- control of mechanism. According to Table 3, The value
face by attraction forces and caused a decrease in avail- of ­Cid gives information about the boundary layer, so the
able surface areas on adsorbent (Onundi et al. 2011). value of C ­ e2+-PPC and 0.552 for F
­ id, 1.584 for F ­ e3+-PPC,
According to Fig. 4, the two states of adsorption of indicates that the effect of the boundary layer is more
­Pb2+ indicated that from 0 to 50 ppm the adsorption important in adsorption of ­ Pb2+ by ­ Fe2+-PPC after
capacity increased proportional to the existence of unoc- 30 min. These deviations from the origin may be due
cupied adsorption sites on both biosorbents, but from to the difference in the initial and the final rate of mass
50 to 100 ppm the adsorption sites gradually saturated transfer.
and the additional concentration of ­Pb2+ remained in Thermodynamic studies are used to predict the possi-
the solution, therefore the adsorption capacity remained bility of doing reaction in a better way and performed by
nearly constant. changing temperature against the yield of P ­ b2+ adsorp-
The Fig. 5 showed, at a constant concentration of ­Pb2+, tion (Huang et al. 2007). Adsorption of ­Pb2+ ions on
the adsorption capacity F ­e2+-PPC and F ­e3+-PPC to the two composites increased by rising of the tempera-
2+
adsorb of ­Pb ions increased by increasing of the adsor- ture from 25 to 85 °C. It is clear, increasing temperature
bent dose. It is related to the presence of more sites on the enhances the chemical affinity and mobility of the Pb
surface of biosorbents at higher doses and the fact that cations toward the active sites on the biosorbent surface
certain adsorption sites are unsaturated during the batch leading to the occurrence of chemical interaction during
adsorption process (Mehrasbi et al. 2009). The adsorption the adsorption process. The same conclusion reported by
capacity of ­Fe2+-PPC and ­Fe3+-PPC was about marginal Garcia-Rosales and Colin- Cruz in adsorption of Pb(II)
to 25 mg/g for two studied adsorbents when adsorbent and Cd(II) on the stalk sponge of Zea mays (García-
dose increased from 0.1 to 1.0% w/v. This fall in the P ­ b2+ Rosales and Colín-Cruz 2010).
adsorbed amount per unit mass of biosorbent is a usual The positive value of enthalpy changes (40.6 and
manner which has also been reported by Acharya et al. 27.5 kJ/mol) indicates the endothermic nature of adsorp-
(2009). Hence, other experiments were conducted at the tion of P­ b2+ on Fe-PPC. A possible interpretation is that
2+
optimum value of 1.0% w/v of adsorbent dose. the ­Pb ions are hydrated in the solution. This reaction
Obtaining of the kinetic data is necessary to extend requires high energy, is endothermic, and supersedes the
an equation for designing of the rate system and under- exothermic attraction of Pb ions toward active sites on
standing the process mechanism that evaluated by the composite surface. The similar observation has been
matching the experimental data to kinetic models. Vari- previously found in the removal of lead onto prepared
ous kinetic models are used for evaluation of the rate activated carbon from coconut shell (Sekar et al. 2004).
adsorption process. The intraparticle diffusion model is The positive value of entropy changes (136 and 92.0 J/
an equation to survey the rate and mechanism of adsorp- mol) also indicates the affinity of ­Pb2+ ions toward active
tion process (Srihari and Das 2008). According to them, sites of adsorbents and suggests an increasing degree of
If the line of ­qt via ­t1/2 goes through the origin, then the freedom during the metal ions adsorption on an adsor-
limiting rate of reaction is intraparticle diffusion; as well bent (Arshadi, et al. 2014). The negative values of Gibbs
as, if the plot forms multi-linearity, more than one stage free energy changing (ΔG), except for adsorption in the

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Salmani et al. AMB Expr (2017) 7:225 Page 8 of 8

25 °C for ­Fe3+-PPC, showed that the process is favorable References


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Abbreviations
from aqueous solution by green synthesis iron oxide nanoparticles with
SEM: scanning electron microscope; FT-IR: Fourier transform infrared spec-
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read and approved the final manuscript.
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Author details
1 Kazemipour M, Ansari M, Tajrobehkar S, Majdzadeh M, Kermani HR (2008)
Department of Environmental Health, School of Public Health, Shahid Sad-
Removal of lead, cadmium, zinc, and copper from industrial wastewater
oughi University of Medical Science, Yazd, Islamic Republic of Iran. 2 Depart-
by carbon developed from walnut, hazelnut, almond, pistachio shell, and
ment of Chemical Technologies, Iranian Research Organization for Science
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and Technology (IROST), Tehran, Islamic Republic of Iran. 3 Department
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of Environmental Health Education and Health Promotion, School of Public
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Health, Shahid Sadoughi University of Medical Sciences, Yazd, Islamic Republic
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ski D (2016) Evaluation of Pb(II) biosorption utilizing sugarcane bagasse
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lead. Environ Health Pers 118:A68–A72
Availability of data and materials
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The dataset supporting the conclusions of this article is included within the
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a new adsorbent. Sep Sci Technol 46(3):507–517
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Consent for publication
of lead(II) onto activated carbon prepared from coconut shell. J Colloid
All authors gave their consent and agree to publish the article.
Interface Sci 279(2):307–313
Srihari V, Das A (2008) The kinetic and thermodynamic studies of phenol-sorp-
Ethics approval and consent to participate
tion onto three agro-based carbons. Desalination 225(1):220–234
No human participants were involved in the study.
Taha G, Arifien A, El-Nahas S (2011) Removal efficiency of potato peels as a
new biosorbent material for uptake of Pb(II) Cd(II) and Zn(II) from their
Funding
aqueous solutions. J Solid Waste Technol Manage 37(2):128–140
This work has been supported by the Iranian Research Organization for Sci-
Weber WJ, Morris JC (1963) Kinetics of adsorption on carbon from solution. J
ence and Technology (IROST).
Sanitary Eng Division 89(2):31–60
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Publisher’s Note by activated carbon made from peanut shells. Bioresour Technol
Springer Nature remains neutral with regard to jurisdictional claims in pub- 97(18):2266–2270
lished maps and institutional affiliations. Zhan X-M, Zhao X (2003) Mechanism of lead adsorption from aqueous solu-
tions using an adsorbent synthesized from natural condensed tannin.
Received: 5 October 2017 Accepted: 5 December 2017 Water Res 37(16):3905–3912

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