Environmental Nanotechnology, Monitoring & Management 6 (2016) 176–183

Contents lists available at ScienceDirect

Environmental Nanotechnology, Monitoring &

Management
journal homepage: www.elsevier.com/locate/enmm

Biosorption of heavy metals ions in real industrial wastewater using

peanut husk as efficient and cost effective adsorbent
Ibrahim Abdelfattah a,∗ , Adel A. Ismail b,∗ , Fathy Al Sayed c , Ali Almedolab d ,
K.M. Aboelghait a
a
Water Pollution Research Department, National Research Centre, P.O. Box 12622, 33 El-Bohouth Street, Dokki, Giza, Egypt
b
Nanomaterials and Nanotechnology Department, Central Metallurgical Research and Development Institute (CMRDI), P.O. 87 Helwan, Cairo 11421, Egypt
c
Chemistry Department, Faculty of Science, Menoufia University, Egypt
d
General hospital of Sadat City, Menoufia, Egypt

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

Article history: In this research, the practical feasibility of using a low-cost adsorbent, peanut husk powder (PHP), for
Received 16 July 2016 the removal of different heavy metals ions, Pb2+ , Mn2+ , Cd2+ , Ni2+ and Co2+ from wastewater has been
Received in revised form 16 October 2016 tested and the goal was achieved. The evaluation of PHP ability for bio-sorption of highly concentrated
Accepted 27 October 2016
heavy metal ions (100 mg/L) from real industrial wastewater has been performed. The batch treatment
process was employed to obtain the optimum parameters conditions such as bio-sorbent dose, pH val-
Keywords:
ues, shaking time and metal ions concentrations. The optimal conditions for the removal of metal ions
Bio-sorption
using PHP were approximate pH value of 6, 5 g/L adsorbent dose, and 20 mg/L metals ions concentration,
Removal
Heavy metals
and 3 h shaking time. Thus, it was possible to obtain the highest removal efficiency with the following
Wastewater order Pb2+ > Cd2+ > Mn2+ > Ni2+ > Co2+ . Both adsorption parameters of Langmuir and Freundlich isotherms
Peanut husk were calculated, and better-fitted experimental data to the Langmuir equation were obtained. PHP was
employed to treat a metal finishing for processing industrial wastewater, and indicated the removal effi-
ciency of Pb2+ , Fe3+ , Cr3+ , CN− , Cu2+ , Cd2+ , Mn2+ , Zn2+ , Co2+ and Ni2+ ions of 100%, 95%, 56%, 51%, 45%, 41%,
38%, 30% and 24%, respectively.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction indirectly or directly discharged into the water resources especially

Wastewater remediation is considered to be one of the main
approaches for water recycling that provides the deficiency of
water in different regions in our daily life. To-date, only 10% of the
produced wastewater is remediated and the residual wastewater is
released into water resources such as rivers, seas and diffused into
groundwater (Al-Zoubi et al., 2015). Heavy metals are considered
to be the main contaminants in wastewater especially at high con-
centrations causing health problems in human beings and raising
serious environmental issues (Chowdhury et al., 2016). They pos-
sess a specific gravity greater than 5.0 and having atomic weights
between 63.5 and 200.6 (Fu and Wang, 2011). These metal ions
have toxicity potential, and might cause carcinogenicity in the liv-
ing organisms. The rapid development of industries leads to the
production of huge amount of toxic heavy metals ions. They are
∗ Corresponding authors.
E-mail addresses: iabdelhafiz@yahoo.com (I. Abdelfattah),
adelali141@yahoo.com, aismail@cmrdi.sci.eg (A.A. Ismail).
in developing countries. As a result of their non biodegradability
feature and its tendency to accumulate in living organisms, treat-
ment of industrial wastewaters is a particular concern for removing
toxic heavy metals such as Pb(II), Cd(II), Ni(II), Co(II), Mn(II). . ..etc.
at high and low level concentrations (Fu and Wang, 2011). There
are several techniques employed for removing heavy metal ions
such as chemical precipitation (Huisman et al., 2006; Alvarez et al.,
2007), ion exchange (Alyüz and Veli, 2009; Abo-Farha et al., 2009;
Zewail and Yousef, 2015), adsorption (Ismail et al., 2010, 2008;
Mohamed et al., 2009), membrane filtration (Fu and Wang, 2011;
Rether and Schuster, 2003; Gunatilake, 2015), coagulation and floc-
culation (Johnson et al., 2008; Amuda et al., 2006; Pang et al., 2009),
electrochemical treatment (Hunsom et al., 2005; Chen et al., 2013),
microorganism (Javanbakht et al., 2014; Ozdemira et al., 2009;
Xiong et al., 2008). Unfortunately, all the above techniques have
drawbacks including cost and sludge problems and/or maintenance
problems. Bio-sorption of heavy metal ions is the removal of dis-
solved metal ions from water by certain types of biomass that has
an ability to bind and concentrate metals ions. Bio-sorption is a cost
effective and regenerative metal recovery technology for purifica-

http://dx.doi.org/10.1016/j.enmm.2016.10.007
2215-1532/© 2016 Elsevier B.V. All rights reserved.
 I. Abdelfattah et al. / Environmental Nanotechnology, Monitoring & Management 6 (2016) 176–183 177

Table 1
Biosorption capacities of different biosorbents for removal of heavy metals ions.

Metal ions Biosorbent Maximum Reference

Adsorption (mg/g)

Ni2+ Corn cob 12 Abdelfattah et al. (2016)

Maize cob 18.4 Muthusamy et al. (2012)
Saw dust 35 Adie et al. (2012)
Maize cob 10 Adie et al. (2012)
Corn cob powder 14.6 Arunkumar et al. (2014)
Pb2+ Corn cob 32.4 Abdelfattah et al. (2016)
Sawdust 15.9 Bulut and Tez (2007)
Myriophyllum spicatum 55.1 Yan et al. (2010)
Lichen (Cladonia furcata) 12.3 Sari et al. (2007)
Macro-fungus (Amanita 38.4 Sari et al. (2009)
rubescens) 72.5 Amirnia (2015)
Saccharomyces cerevisiae yeast
Mn2+ Corn cob 12 Abdelfattah et al. (2016)
Leaves of dump palm 3 Jonathan et al. (2011)
Plant biomass 7 Dubey et al. (2014)
Maize stalk 5.5 El-Sayed et al. (2011)
Cd2+ Corn cob 24 Abdelfattah et al. (2016)
Zea maize waste 25 Jamil and Munwar (2009)
Maize cob 20 Ibrahim (2013)
Saw dust 5.2 Ibrahim (2013)
Macro-fungus (Amanita 32.5 Sari et al. (2009)
rubescens)
Co2+ Corn cob 3.2 Abdelfattah et al. (2016)
Pine saw dust 56 Musapatika et al. (2012)
lemon peel 22 Bhatnagar et al. (2010)
Amaranthus hybridus 19.5 Egila et al. (2010)

Table 2 2.2. Preparation of the bio-sorbent

Removal and Adsorption capacity (mg/g) of heavy metal ions by PHP as adsorbent.

No. Metal ions Removal (%) Adsorption capacity (mg/g) Peanut husk was collected from a farm in Delta land, Menoufia,
1 Pb+2
(25–99) (19.7–49.4) Egypt, washed thoroughly to remove dust using tap water, followed
2 Cd+2 (23–62) (12.3–46) by deionized water, dried in an oven at 80 ◦ C for 12 h, grinded using
3 Co+2 (3–30) (6.1–25) a laboratory mill, sieved, then washed with deionized water fol-
4 Mn+2 (9–44) (8.8–18) lowed by washed with both diluted HCl and NaOH, then washed
5 Ni+2 (10–39) (7.9–20)
with by deionized water, and finally dried at 80 ◦ C for 24 h.

2.3. Equipment

tion of wastewater from heavy metal ions (Abdelfattah et al., 2016).
There are significant contributions of various research groups on
removing heavy metals ions through the bio-sorption adsorbents
and technologies as summarized in Table 1.
In the current contribution, we focused on the practical feasi-
bility of using a low-cost adsorbent, peanut husk powder (PHP) for
removing various heavy metals ions, Pb(II), Mn(II), Cd(II), Ni(II) and
Co(II) from contaminated model and real wastewaters. In addition
to studying the reaction kinetics, the goals of determining the opti-
mum conditions to adsorb metal ions and obtaining the highest
adsorption efficiency are achieved.
For shaking the suspension solution, Lab shaker, Wiseshake,
SHO-2D, South Korea was utilized. pH-meter, WTW-inolab,
Germany, was used for adjustment of pH values of the suspension
solutions. The concentrations of heavy metal ions were deter-
mined using atomic absorption spectrometer Varian Spectr-AA
(220), USA. PHP images were taken by scanning Electron micro-
scope (SEM) images at different magnifications using Quanta-250
FEG, USA. FTIR absorption spectra of the PHP were recorded for the
350–4000 cm−1 range using Jasco-FTIR-Spectroscopy, Japan.
2.4. Methodology

For bio-sorption experiments, freshly prepared model solutions

2. Materials and methods
2.1. Chemical and reagents
Pb(NO3 )2 , CdCl2 , CoCl2 ·6H2 O, MnSO4 ·H2 O, NiCl2 ·6H2 O, HCl and
NaOH were purchased from Sigma-Aldrich and used as received
without further purification. Freshly prepared model solutions of
Pb(NO3 )2 , CdCl2 , CoCl2 ·6H2 O, MnSO4 ·H2 O and NiCl2 ·6H2 O, with
desired concentration were used as a source of heavy metal ions
(adsorbate). Real sample of industrial wastewater was collected
from a metal industry at Sadat industrial city and it was chemically
characterized. pH values of the collected samples were adjusted for
desired value via HCl (1 M) and NaOH (1 M).
of Pb+2 , Cd+2 , Co+2 , Mn+2 and Ni+2 ions with known initial concen-
tration and real industrial wastewater were employed. pH values
for all prepared suspension solution were adjusted before con-
ducting the experiments. Different bio-sorbent doses were added
to 100 mL of prepared solution or to a real wastewater sample.
The mixtures were shaken using lab shaker with speed 250 rpm
for 0.5–6 h. The bio-sorbents were separated by filtration through,
Whatman qualitative No. 4, filter paper. The concentration of resid-
ual heavy metal ions was determined using the atomic absorption
spectrometer. All measured parameters of raw and treated wastew-
aters have been analyzed according to procedures given in The
American Standard Methods (APHA, 2012). The treatment of real
wastewater unit, which could be used in removal of heavy metals
from real industrial wastewater, is shown in Scheme 1.
178 I. Abdelfattah et al. / Environmental Nanotechnology, Monitoring & Management 6 (2016) 176–183

Table 3
Langmuir constants for the sorption of Pb+2 , Mn+2 , Cd+2 , Ni+2 and Co+2 ions onto PHP as adsorbent.

Metal ions Slope intercept Qmax (mg/g) KL RL R2

+2
Pb 0.037 0.003 27.03 12.33 (0.0005–0.0040) 0.998
Cd+2 0.088 0.055 11.36 1.60 (0.004–0.030) 0.995
Co+2 0.164 0.761 6.10 0.22 (0.03–0.19) 0.987
Mn+2 0.070 0.077 14.29 0.91 (0.02–0.16) 0.998
Ni+2 0.018 0.15 56.82 0.12 (0.05–0.30) 0.985

Scheme 1. Treatment plant for industrial wastewater.

3. Results and discussions removal efficiency was boosted with the increase of PHP doses from
1 to 5 g. Moreover, the Pb+2 removal efficiency was the highest
Fig. 1 shows SEM images of PHP at different magnifications. It and reached to 100% within 4 h shaking time. However, the other
is clearly seen that at low magnification PHP has different shapes metal ions need longer shaking time and higher PHP dose to reach
and the particle sizes are large (Fig. 1a). However, at higher magni- complete removal efficiency. Furthermore, metal ions adsorption
fication, the PHP exhibited homogenous pore structures along the capacity decreased with boosting of PHP dose. There could be many
surface of the PHP particles (Fig. 1b). Fig. 1c displays the FTIR spec- factors contributing to this result. We suggest that the most impor-
trum of PHP. The two FTIR peaks at 1629 cm−1 and 1632 cm−1 are tant one is the adsorption site remaining unsaturated during the
assigned to C C, while the two peaks at 1718 cm−1 and 1721 cm−1 adsorption reaction, this is attributed to the non-saturation of the
arise from identical C O group. The two signals at 3437 cm−1 adsorption active sites (Han et al., 2006; Achak et al., 2009). The
and 3452 cm−1 belong to OH group, while the broad band from present results regarding PHP as efficient adsorbent confirmed that
1000 cm−1 to 1200 cm−1 indicates the presence of NH. It was the PHP has higher effectiveness with respect to the corncob uti-
reported that all of these binding groups have high efficiency for lized for removal of heavy metal ions (Abdelfattah et al., 2016).
adsorption of heavy metals ions from wastewater. Removal of metal ions at different pH values (3–8) was con-
Generally, the performance of the optimized conditions for ducted at the following conditions: Adsorbent dose 5 g/L, 6 h
removal of metal ions through PHP was crucially affected by the shaking time, 100 mg/L initial heavy metal ions concentration (C0 )
pH values, PHP doses, and the shaking time. Herein, we performed and 250 rpm shaking speed and the results are shown in Fig. 3.
a series of experiments to systematically determine the pH value, Removal efficiency of Pb+2 , Mn+2 , Cd+2 ,Ni+2 and Co+2 ions was grad-
PHP doses, shaking time and heavy metal ions concentration to ually increased with the increase of the pH value from 3 to 6 and
obtain the highest removal efficiency. The optimal doses of PHP then decline at higher pH value owing to the competitive adsorp-
0.5, 1, 2, 3, 4 and 5 g/L to adsorb metal ions Pb+2 , Cd+2 , Co+2 , Mn+2 tion between hydrogen ion and the heavy metal cation at low pH
and Ni+2 were studied by conduction systematic experiments at (Hashem, 2007). Furthermore, the electronegative metal ions pos-
constant conditions: pH value ∼6, for 6 h shaking time, 100 mg/L sess higher charge density and as a result they easily adsorb onto
initial heavy metal ions concentration (C0 ) and 250 rpm shaking the PHP surface. However, at higher pH value, there is a decrease
speed (Fig. 2 and Table 2). The results revealed that the metal ions in removal efficiency of metal ions due to the abundance of − OH
ions that cause hindrance effect on the diffusion of metal ions to the
organic matter (Jimoh et al., 2012). It is clear that adsorption capac-
Table 4
Freundlich constants for the sorption of Pb+2 , Mn+2 , Cd+2 ,Ni+2 and Co+2 ions onto
ity of PHP is based on the pH value and hence the surface charge
peanut husk as adsorbent. and the ionization. The optimum pH value is ∼6 for maximum
adsorption of Pb+2 , Mn+2 , Cd+2 ,Ni+2 and Co+2 ions.
Metal ions Slope Intercept ln KF KF 1/n n R2
Studying effect of shaking time (0.5, 1, 2, 3, 4, 5 and 6 h) on
+2
Pb 0.246 2.7 2.7 14.8 0.246 4.1 0.980 the removal efficiency of Pb+2 , Mn+2 , Cd+2 , Ni+2 and Co+2 ions by
Cd+2 0.23 1.5 1.5 4.5 0.23 4.3 0.712
PHP at constant conditions: pH value ∼6, 5 g/L adsorbent dose,
Co+2 0.206 0.91 0.91 2.5 0.206 4.9 0.764
Mn+2 0.26 1.65 1.65 5.2 0.26 3.9 0.670 100 mg/L initial heavy metal ions concentration (C0 ) and 250 rpm
Ni+2 0.12 1.23 1.23 3.4 0.12 8.5 0.617 shaking speed and the results are shown in Fig. 4. The efficiency
 I. Abdelfattah et al. / Environmental Nanotechnology, Monitoring & Management 6 (2016) 176–183 179

Fig. 1. (a) SEM image of peanut husk at low magnification, (b) SEM image of peanut husk at high magnification, (c) FT-IR spectrum of peanut husk.

of adsorption of metal ions was rapid in the first 30 min, and then
became slower until reaching equilibrium. The removal efficien-
cies of metals ions adsorption were faster at the starting owing to
the accessibility of enormous number of the adsorbent sites. At this
adsorption stage, the metals ions adsorption rate is dominated by
the mass transfer rate of the metal ions at the heterogeneous metal
ions solution-PHP solid interface. These findings are consistent with
those early documented (Dorris et al., 2000; Nouha et al., 2016). At
steady region, the removal efficiency was 99%, 62%, 30%, 45% and
38% for Pb+2 , Cd+2 , Co+2 , Mn+2 and Ni+2 , respectively. The steady
reaction of Pb+2 , Cd+2 , Co+2 , and Ni+2 was reached the maximum
adsorption within 3 h, however Mn+2 needed 4 h.
The behavior of metal ion adsorption by PHP were carried out
at 25 ± 2 ◦ C using different initial metal ion concentrations (20, 40,
60, 80,100 and 120 mg/L) at constant conditions: pH value ∼6, 5 g/L
adsorbent dose, and 250 rpm shaking speed (Fig. 5). The percent-
age removal efficiency of metal ions is reduced with the increase in
initial metal ion concentration from 20 to 100 mg/L. With increas-
ing Pb+2 concentrations, the binding sites were considered to be
more quickly saturated as the amount of PHP dose remained con-
stant. The maximum removal efficiencies of Pb+2 , Cd+2 and Mn+2
using PHP were 100% at 20 mg/L ions concentration, and the max-
imum removals of Co and Ni were 75% and 85%, respectively at
a metal concentration of 20 mg/L. Such results revealed the out-
standing of PHP as efficient adsorbent for removal metal ions at
high concentrations.
3.1. Adsorption isotherms
Adsorption isotherm equation represented the relation between
the amount of solute adsorbed and the concentration of the solute
in the aqueous phase. The adsorption isotherms are evaluated in

Table 5
Industrial wastewater analysis before and after treatment using peanut husk.
a b
Metal ions and Concentration of Concentration of % Removal of metals ions
metals ions in mg/L metals ions in mg/L

CN− 11 5.4 50.9

Pb2+ 0.26 – 100
Zn2+ 11.61 7.2 37.9
Cu2+ 11.55 6.3 45.4
Fe3+ 2.13 0.1 95.3
Ni2+ 30.76 23.5 23.6
Cd2+ 46 27 41.3
Mn2+ 52 32 38.4
Cr3+ 44.69 19.45 56.4
Co2+ 20 14 30
a
Before treatment.
b
After treatment.
180 I. Abdelfattah et al. / Environmental Nanotechnology, Monitoring & Management 6 (2016) 176–183

100
(a) 100
+2
Pd
+2 Pd
+2
Cd
+2 Cd

Removal of metal ions, %

80 +2
Removal of metal ions,%

Co
+2 80 Co
+2
Mn
+2 Mn
+2
60 Ni
+2 Ni
60

40
40

20
20

0
0
0 1 2 3 4 5 3 4 5 6 7 8
Peanut husk dose, g/L pH

Fig. 3. Effect of pH on removal metal ions efficiency over peanut husk as adsorbent
at 25 ± 2 ◦ C (adsorbent dose 5 g/L, 6 h shaking time, 100 mg/L initial heavy metal ions
concentration (C0 ) and 250 rpm shaking speed).

50 100
+2 +2
Pd Pd
45 (b) +2
90
Cd
+2
Cd
Removal of metal ions, mg/g

+2
Co
+2 80 Co
40
Removal of metal ions, %

+2
Mn
+2 Mn
70 +2
35 +2 Ni
Ni
60
30
50
25
40
20
30
15
20
10
10
5
0
0 1 2 3 4 5 0 1 2 3 4 5 6
Peanut husk dose, g/L Shaking time, h

Fig. 2. (a) Effect of peanut husk dose on removal efficiency of Pb+2 , Mn+2 , Cd+2 , Ni+2 Fig. 4. Effect of shaking time on the removal efficiency of Pb+2 , Mn+2 , Cd+2 , Ni+2 and
and Co+2 ions at 25 ± 2 ◦ C, (b) Effect of peanut husk dose on removal of Pb+2 , Mn+2 , Co+2 ions by peanut husk (pH value ∼6, 5 g/L adsorbent dose, 100 mg/L initial heavy
Cd+2 , Ni+2 and Co+2 ions. metal ions concentration (C0 ) and 250 rpm shaking speed at 25 ± 2 ◦ C).

Ce 1 1
order to describe the process (Sari and Tuzen, 2009). The Langmuir = + ∗ Ce (3)
qe q m KL qm
and the Freundlich adsorption isotherms’ equations have been suc-
cessfully applied to many adsorption processes (Abdelfattah et al., where qm and KL are Langmuir constants related to the sorption
2016; Khoufi et al., 2008; Aktas and Cecen, 2007; Ozkaya, 2006; capacity, and sorption energy, respectively, Ce is the equilibrium
Aksu and Yener, 2001) and were adopted in the present study as concentration in mg/L, and qe is the amount of adsorbate adsorbed
follows: per unit weight of adsorbent (mg/g). The essential characteristics of
The Langmuir equation is based on the assumptions that Langmuir dimensionless constant separation factor or equilibrium
maximum adsorption corresponds to a saturated mono-layer of parameter, RL , which is defined by the following equation:
adsorbate molecules on the adsorbent surface with uniform dis- 1
RL = (4)
tribution of energy level, (Langmuir, 1916). The Langmuir isotherm 1 + K1L ∗ C0
is defined as:
From the value of RL calculated using the above expression, the
q K L Ce nature of the adsorption process is determined to be one of the fol-
qe = max (1) lowing: Unfavorable (RL > 1), Linear (RL = 1), Favorable (0 < RL < 1),
1 + KL Ce
Irreversible (RL = 0). The Langmuir isotherm constants and their
and in linearized form is: correlation coefficients R2 for adsorption of heavy metals ions via

1 1
1 1
PHP are listed in Table 3. The plots of Ce /qe against Ce are shown
= + (2) in Fig. 6; the adsorption of Pb+2 , Mn+2 , Cd+2 , Ni+2 and Co+2 ions
qe qm K L Ce qm over PHP adsorbents showed that Langmuir isotherm model best
 I. Abdelfattah et al. / Environmental Nanotechnology, Monitoring & Management 6 (2016) 176–183 181

4.0
100
Pd2+
90 3.5
Removal of metal ions, %

Cd2+
80
3.0 Co2+
70
Mn2+

ln qe
2.5
60
Ni2+
+2
50 Pd
+2
2.0
Cd
+2
40 Co
+2 1.5
Mn
30 +2
Ni
1.0
20
1 2 3 4 5 6

20 40 60 80 100 120 140 ln Ce

Intial metal ions concentration, mg/L
Fig. 7. Freundlich plot of peanut husk as adsorbent for Pb+2 , Mn+2 , Cd+2 , Ni+2 and
Co+2 ions removal at 25 ± 2 ◦ C.
Fig. 5. Effect of initial metal ion concentration on removal% for peanut husk at
25 ± 2 ◦ C (pH value ∼ 6, 5 g/L adsorbent dose, and 250 rpm shaking speed).
Co+2 , Mn+2 , and Ni+2 with PHP possess RL values ranged between 0
Table 6 and 1, which shows that the adsorption process is favorable.
Construction cost for treatment plant of real industrial wastewater.

Construction Price ($) Quantity Total price ($) 3.2. Freundlich isotherm equation
1 m3 basin 100 2 200
Pump 150 1 150
The Freundlich adsorption isotherm, one of the most widely
Stirrer (0.5 hp) 160 1 160 used mathematical descriptions, gives an expression encompass-
Cloth micro-filter 10 1 10 ing the surface heterogeneity and the exponential distribution of
Connections and welding 30 1 30 active sites and their energies (Freundlich, 1906). The Freundlich
Total Price ($) 550
isotherm is defined as:

qe = Ce 1/n (5)
25
and in linearized form it is expressed as:
Pd2+
ln qe = ln KF + (1/n) ln Ce (6)
20
2+
Cd
where Ce is the equilibrium concentration in mg/L, qe = amount of
2+ adsorbate adsorbed per unit weight of adsorbent (mg/g). “kF ” is a
Co
15 parameter related to the temperature and “n” is a characteristic
Mn2+ constant for the adsorption system under study. The Freundlich
Ce/qe

isotherm constants (n) and their correlation coefficients R2 are

10 Ni2+ summarized in Table 4 and the plots of ln qe against ln Ce are shown
in Fig. 7. The Freundlich isotherm model for adsorption of Pb2+ best
fitted with the equilibrium data presented a high R2 value (0.980),
5 while the Freundlich isotherm model for adsorption of Mn+2 , Cd+2 ,
Ni+2 and Co+2 ions fitted less than Pb2+ with equilibrium data, pre-
sented a moderate R2 value (ranged between 0.617 and 0.764)
0 (Table 4). For all ions’ values of “n” between 2 and 10, there is a
0 20 40 60 80 100 120 favorable adsorption behavior.
Ce
3.3. Case study
Fig. 6. Langmuir plot of peanut husk as adsorbent for Pb+2 , Mn+2 , Cd+2 , Ni+2 and Co+2
ions removal at 25 ± 2 ◦ C.
The major disadvantage of the previously published adsorp-
tion researches is that most of the research works are still in the
fitted with the equilibrium data, presented a high R2 values (ranged lab-scale not extended to the pilot-scale or commercialization.
between 0.985 and 0.998) (Table 3). The results in the present work Therefore, there is only limited information available for detailed
indicated that the RL -values for the adsorption process of Pb+2, Cd+2 , economic analyses. (Srinivasan and Viraraghavan, 2010; Kyzas and

Table 7
Running cost for treatment of real industrial wastewater using peanut husk.

Dose of Cost of Cost of Cost of Cost of Total cost of

PHP PHP ($) electricity($) filtration($) Labor ($) ($)/m3

5 kg/m3 0.2 0.1 0.1 0.1 0.5

10 kg/m3 0.4 0.1 0.1 0.1 0.7
50 kg/m3 2.0 0.1 0.1 0.1 2.3
182 I. Abdelfattah et al. / Environmental Nanotechnology, Monitoring & Management 6 (2016) 176–183
Kostoglou, 2014). To apply the treatment method used for remov-
ing different heavy metals from the real industrial wastewater
using PHP, adequate amount (10 L/d) of real industrial wastewa-
ter was collected from a metal industry at Sadat industrial city of
Egypt as a batch form. The metal industry produces 300 m3 /month
of heavy metals-polluted wastewater. The wastewater was chem-
ically analyzed in detail and the results showed the presence of a
numerous types of heavy metals ions in the wastewater; Pb2+ , Fe3+ ,
Cr2+ , Cu2+ , Zn2+ , Cd2+ , Mn2+ , Co2+ , Ni2+ and CN− in concentrations of
0.26, 2.13, 44.69, 11.55, 11.61, 46, 52, 20, 30.76 and 11 mg/L, respec-
tively as summarized in Table 5. The highly loaded wastewater with
heavy metals was experimentally subjected to the bio-sorption
treatment via PHP. The treatment conditions were carried out at
the natural pH value of wastewater ∼6.6. Because the optimal pH
of PHP causes the maximum removal of heavy metals from aque-
ous solutions, it is not needed to adjust the pH. Therefore, PHP
sorbent dose of (5 g/L) for 1 h shaking time and at ambient temper-
ature in 1 L beaker as a batch mode were utilized. After bio-sorption
process was completed using peanut husk, PHP was separated by
filtration and then the filtrate was chemically analyzed and the
results are listed in Table 5. The findings revealed that effective
removal of Pb2+ , Fe3+ , Cr2+ , CN− , Cu2+ , Zn2+ , Cd2+ , Mn2+ , Co2+ and
Ni2+ ions by peanut husk were obtained with the efficiency values
of 100%, 95%, 56%, 51%, 45%, 41%, 38%, 38%, 30% and 24%, respec-
tively. The results revealed that PHP is an effective adsorbent to
remove metals ions within one hour, for removing almost all met-
als ions from the real wastewater. When extended treatment unit
is needed, the PHP could be reused by washing with diluted acid
and then dried at 80 ◦ C for 24 h. Hashim et al., 2000 stated that a
desorbing agent accomplishes complete metal recovery together
with unaltered capacity of the sorbent for removal of heavy met-
als. Mineral acids had a highly efficiency for metal recovery with no
loss in removal efficiency (Jalali et al., 2002; Lau et al., 2003; Bakir
et al., 2010).
A simple schematic diagram of supposed bio-sorption treatment
plant showed in Scheme 1. First, the wastewater was pumped and
the PHP was added to the mixing container for the appropriate con-
tact time. Then, the bottom valve in the mixing tank was opened
to drain on a filtration container, which has upper cloth micro-
filter adequate enough for detaining of the PHP and the attached
residues. After completing the filtration process, the valve at the
bottom of the filtration tank was opened to drain the treated efflu-
ent. The PHP and the adsorbed residues were treated by diluted acid
for removing the heavy metals followed by washing with water for
removing the residual acid. The final stage is drying at 80 ◦ C for 24 h
in order to remove the residual water.
Construction cost for 1 m3 treatment plant for real industrial
wastewater treatment was calculated (Table 6). The calculations
confirmed the low cost evaluation for the construction of the treat-
ment plant, and Table 7 illustrated the calculated running cost for
removal of heavy metals ions from real industrial wastewater using
PHP. The PHP is a cost effective adsorbent, US$ 40 in compari-
son with the adsorbent prepared from waste fruit peel which cost
approximately ≈US$ 100–200/ton and the commercial activated
carbons (generally used for effluent treatment) cost ≈US$ 2000/t.
(Bhatnagar et al., 2010).
4. Conclusions
Low-cost peanut husk powder is an effective bio-sorbent for
the removal of Pb+2 , Mn+2 , Cd+2 , Ni+2 and Co+2 ions from aque-
ous solutions. The removal efficiency increases with the increase of
adsorbent dose, while the adsorption capacity (qe ) decreases with
increasing of adsorbent dose. The optimum pH corresponding to
the maximum adsorption ions removal was pH 6. The efficiency
of adsorption of metal ions was rapid in the first 30 min, and then
turned out to be slower till reaching the equilibrium state. At steady
region, the removal efficiency was 99%, 62%, 30%, 45%, and 38% for
Pb+2 , Cd+2 , Co+2 , Mn+2 and Ni+2 , respectively. The steady reaction
of Pb+2 , Cd+2 , Co+2 , and Ni+2 was reached the maximum adsorption
within 3 h. However, removal of Mn+2 needed 4 h. The removal of
heavy metals decreased with increasing initial metal ions concen-
trations. The essential characteristics of Langmuir dimensionless
constant separation factor or equilibrium parameter, (0 < RL < 1),
and thus adsorption is favorable. The Langmuir isotherm better
fitted the experimental data since the correlation coefficient (R2 )
for the Langmuir isotherm was higher than that of the Freundlich
isotherm for all of the metal ions used in the current contribu-
tion. Applying the treatment method for reality, a metal industry
wastewater is selected as a case study. The polluted wastewater
containing a high concentrations of heavy metals Pb2+ , Fe3+ , Cr2+ ,
CN− , Cu2+ , Zn2+ , Cd2+ , Mn2+ , Co2+ and Ni2+ ions was treated by the
PHP bio-sorption and their removal efficiencies were 100%, 95%,
56%, 51%, 45%, 41%, 38%, 38%, 30%, and 24%, respectively. PHP is
an ideal cost-effective solution for removal of heavy metals from
industrial wastewater.
References
APHA, 2012. AWWA, WEF. Standard Methods for Examination of Water and
Wastewater, 22nd edn. American Public Health Association, Washington, pp.
1360, ISBN 978-087553-013-0.
Abdelfattah, I., Al Sayed, F., Almedolab, A., 2016. Removal of heavy metals from
wastewater using corn cob. Res. J. Pharm. Biol. Chem. Sci. 7, 239–248.
Abo-Farha, S.A., Abdel-Aal, A.Y., Ashourb, I.A., Garamon, S.E., 2009. Removal of
some heavy metal cations by synthetic resin purolite C100. J. Hazard. Mater.
169, 190–194.
Achak, M., Hafidi, A., Ouazzani, N., Sayadi, S., Mandi, L., 2009. Low cost biosorbent
banana peel for the removal of phenolic compounds from olive mill
wastewater: kinetic and equilibrium studies. J. Hazard. Mater. 166, 117–125.
Adie, D.B., Okuofu, C.A., Osakwe, C., 2012. Comparative analysis of the adsorption
of heavy metals in wastewater using borrassus aethiopium and cocos nucifera.
Int. J. Appl. Sci. Technol. 2, 314–322.
Aksu, Z., Yener, J., 2001. A comparative adsorption/biosorption study of
monochlorinated phenols onto various sorbents. Waste Manage. 21, 695–702.
Aktas, O., Cecen, F., 2007. Adsorption, desorption and bioregeneration in the
treatment of 2-chlorophenol with activated carbon. J. Hazard. Mater. 141,
769–777.
Al-Zoubi, H., Ibrahim, K.A., Abu-Sbeih, K.A., 2015. Removal of heavy metals from
wastewater by economical polymericcollectors using dissolved air flotation
process. J. Water Process Eng. 8, 19–27.
Alvarez, M.T., Crespo, C., Mattiasson, B., 2007. Precipitation of Zn(II), Cu(II) and
Pb(II) at bench-scale using biogenic hydrogen sulfide from the utilization of
volatile fatty acids. Chemosphere 66, 1677–1683.
Alyüz, B., Veli, S., 2009. Kinetics and equilibrium studies for the removal of nickel
and zinc from aqueous solutions by ion exchange resins. J. Hazard. Mater. 167,
482–488.
Amirnia, S., (2015) PhD-Thesis, Biosorption processes for removal of toxic metals
from wastewaters, The School of Graduate and Postdoctoral Studies, The
University of Western Ontario, Canada.
Amuda, O.S., Amoo, I.A., Ipinmoroti, K.O.O., Ajayi, O., 2006.
Coagulation/flocculation process in the removal of trace metals present in
industrial wastewater. Appl. Sci. Environ. Mgt. 10, 159–162.
Arunkumar, C., Perumal, R., Lakshmi, S.N., 2014. Use of corn cob powder as low
cost adsorbent for the removal of nickel (II) from aqueous solution. Int. J. Adv.
Biotechnol. Res. 5, 325–330.
Bakir, A., McLoughlin, P., Fitzgerald, E., 2010. Regeneration and reuse of a
seaweed-based biosorbent in single and multi-metal systems clean. Soil Air
Water 38 (3), 257–262.
Bhatnagar, A., Minocha, A.K., Sillanpaa, M., 2010. Adsorptive removal of cobalt
from aqueous solution by utilizing lemon peel as biosorbent. Biochem. Eng. J.
48, 181–186.
Bulut, Y., Tez, Z., 2007. Removal of heavy metals from aqueous solution by sawdust
adsorption. J. Environ. Sci. 19, 160–166.
Chen, X., Huang, G., Wang, J., 2013. Electrochemical reduction/oxidation in the
treatment of heavy metal wastewater. J. Metall. Eng. (ME) 2, 161–164.
Chowdhury, S., Mazumder, M.A.J., Al-Attas, O., Husain, T., 2016. Heavy metals in
drinking water: occurrences, implications, and future needs in developing
countries. Sci. Total Environ. 569–570, 476–488.
Dorris, K.L., Yu, B., Zhang, Y., Shukla, A., Shukla, S.S., 2000. The removal of heavy
metal from aqueous solutions by sawdust adsorption-removal of copper. J.
Hazard. Mater. B 80, 33–42.
 I. Abdelfattah et al. / Environmental Nanotechnology, Monitoring & Management 6 (2016) 176–183
Dubey, A., Mishra, A., Singhal, S., 2014. Application of dried plant biomass as novel
low-cost adsorbent for removal of cadmium from aqueous solution. Int. J.
Environ. Sci. Technol. 11, 1043–1050.
Egila, J.N., Dauda, B.E.N., Jimoh, T., 2010. Biosorptive removal of cobalt (II) ions
from aqueous solution by Amaranthus hydridus L. stalk wastes. Afr. J.
Biotechnol. 9, 8192–8198.
El-Sayed, G.O., Dessouki, H.A., Ibrahim, S.S., 2011. Removal of Zn(II), Cd(II) and
Mn(II) from aqueous solution by adsorption on maize stalks, Malay. J. Anal. Sci.
15, 8–20.
Freundlich, H.M.F., 1906. Über die Adsorption in Lösungen. Z. Phys. Chem.,
57385–57470.
Fu, F., Wang, Q., 2011. Removal of heavy metal ions from wastewaters: a review. J.
Environ. Manage. 92, 407–418.
Gunatilake, S.K., 2015. Methods of removing heavy metals from industrial
wastewater. J. Multidiscip. Eng. Sci. Stud. 1, 12–18.
Han, R.P., Zou, W.H., Zhang, Z.P., Shi, J., Yang, J.J., 2006. Removal of copper(II) and
lead(II) From aqueous solution by manganese oxide coated sand. I.
Characterization and kinetic study. J. Hazard. Mater. 137, 384–395.
Hashem, M.A., 2007. Adsorption of lead ions from aqueous solution by okra
Wastes. Int. J. Phys. Sci. 2, 178–184.
Hashim, M.A., Tan, N.H., Chu, K.H., 2000. Immobilized marine algal biomass for
multiple cycles of copper adsorption and desorption. Sep. Purif. Technol. 19,
39–42.
Huisman, J.L., Schouten, G., Schultz, C., 2006. Biologically produced sulphide for
purification of process streams, effluent treatment and recovery of metals in
the metal and mining industry. Hydrometallurgy 83, 106–113.
Hunsom, M., Pruksathorn, K., Damronglerd, S., Vergnes, H., Duverneuil, P., 2005.
Electrochemical treatment of heavy metals (Cu2+ , Cr6+ , Ni2+ ) from industrial
effluent and modeling of copper reduction. Water Res. 39, 610–616.
Ibrahim, M.B., 2013. Thermodynamics and adsorption efficiencies of maize cob and
sawdust for the remediation of toxic metals from wastewater. J. Geosci.
Environ. Protect. 1, 18–21.
Ismail, A.A., El-Midany, A.A., Ibrahim, I.A., Matsunaga, H., 2008. Heavy metal
removal using TiO2 -SiO2 binary oxide: experimental design. Adsorption 14,
21–29.
Ismail, A.A., Mohamed, R.M., Ibrahim, I.A., Kini, G., Koopman, B., 2010. Synthesis,
optimization and characterization of zeolite A and its ion exchange properties.
Coll. Surf. A 366, 80–87.
Jalali, R., Ghafourian, H., Asef, Y., Davarpanah, S.J., Sepehr, S., 2002. Removal and
recovery of lead using nonliving biomass of marine algae. J. Hazard. Mater. B
92, 253–262.
Jamil, N., Munwar, M.A., 2009. Biosorbtion of Hg(II) and Cd(II) from waste water by
using Zea Mays Waste. J. Chem. Soc. Pak. 31, 3.
Javanbakht, V., Alavi, S.A., Zilouei, H., 2014. Mechanisms of heavy metal removal
using microorganisms as biosorbent. Water Sci. Technol. 69 (9), 1775–1787.
Jimoh, T.O., Iyaka, Y.A., Nubaye, M.M., 2012. Sorption study of Co, Cu and Pb ions
removal from aqueous solution by adsorption on flamboyant flower. J. Chem.
2, 165–170.
Johnson, P.D., Girinathannair, P., Ohlinger, K.N., Ritchie, S., Teuber, L., Kirby, J.,
2008. Enhanced removal of heavy metals in primary treatment using
coagulation and flocculation. Water Environ. Res. 80, 472.
Jonathan, Y., Hussaina, H., Tijani, J.O., 2011. Application of adsorbent from Dum
palm for the removal of Manganese (II), Zinc (II) and Copper (II) ions from
aqueous solution. J. Am. Sci. 7, 10.
183
Khoufi, S., Aloui, F., Sayadi, S., 2008. Extraction of antioxidants fromolive mill
wastewater and electro-coagulation of exhausted fraction to reduce its toxicity
on anaerobic digestion. J. Hazard. Mater. 151, 531–539.
Kyzas, G.Z., Kostoglou, M., 2014. Green adsorbents for wastewaters: a critical
review. Materials 7, 333–364.
Langmuir, I., 1916. The constitution and fundamental properties of solids and
liquids. J. Am. Chem. Soc. 38, 2221–2295.
Lau T. C., Ang P. O., Wong P. K., (2003) Development of seaweed biomass as a
biosorbent for metal ions.
Mohamed, R.M., Ismail, A.A., Kini, G., Ibrahim, I.A., Koopman, B., 2009. Synthesis of
highly ordered cubic zeolite A and its ion-exchange behavior. Coll. Surf. A 348,
87–92.
Musapatika, E.T., Singh, R., Moodley, K., Nzila, C., Onyango, M.S., Ochieng, A., 2012.
Cobalt removal from wastewater using pine sawdust. Afr. J. Biotechnol. 11,
9407–9415.
Muthusamy, P., Murugan, S., Manothi, S., 2012. Removal of nickel ion from
industrial waste water using maize cob. ISCA J. Biol. Sci. 1, 7–11.
Nouha, K., Kumar, R.S., Tyagi, R.D., 2016. Heavy metals removal from wastewater
using extracellular polymeric substances produced by Cloacibacterium
normanense in wastewater sludge supplemented with crude glycerol and
study of extracellular polymeric substances extraction by different methods.
Bioresour. Technol. 212, 120–129.
Ozdemira, S., Kilinc, E., Poli, A., Nicolausc, B., Guvena, K., 2009. Biosorption of Cd,
Cu, Ni, Mn and Zn from aqueous solutions by thermophilic bacteria, Geobacillus
toebii sub.sp. decanicus and Geobacillus thermoleovorans sub.sp. stromboliensis:
equilibrium, kinetic and thermodynamic studies. Chem. Eng. J. 152, 195–206.
Ozkaya, B., 2006. Adsorption and desorption of phenol on activated carbon and a
comparison of isotherm models. J. Hazard. Mater. B 129, 158–163.
Pang, F.M., Teng, S.P., Teng, T.T., Omar, A.K.M., 2009. Heavy metals removal by
hydroxide precipitation and coagulation-flocculation methods from aqueous
solutions. Water Qual. Res. J. Can. 44, 174–182.
Rether, A., Schuster, M., 2003. Selective separation and recovery of heavy metal
ions using water-soluble N-benzoylthiourea modified PAMAM polymers.
React. Funct. Polym. 57, 13–21.
Sari, A., Tuzen, M., 2009. Kinetic and equilibrium studies of biosorption of Pb(II)
and Cd(II) from aqueous solution by macro fungus (Amanita rubescens)
biomass. J. Hazard. Mater. 164, 1004.
Sari, A., Tuzen, M., Uluozlu, O.D., Soylak, M., 2007. Biosorption of Pb(II) and Ni(II)
from aqueous solution by lichen (Cladonia furcata) biomass. Biochem. Eng. J.
37, 151–158.
Srinivasan, A., Viraraghavan, T., 2010. Decolorization of dye wastewaters by
biosorbents: a review. J. Environ. Manag. 91, 1915–1929.
Xiong, J., He, Z., Liu, D., Mahmood, Q., Yang, X., 2008. The role of bacteria in the
heavy metals removal and growth of Sedum alfredii Hance in an aqueous
medium. Chemosphere 70 (3), 489–494.
Yan, C., Yan, G., Xue, P., Wei, Q., Li, Q., 2010. Competitive effect of Cu(II) and Zn(II)
on the biosorption of lead(II) by Myriophyllum spicatum. J. Hazard. Mater. 179,
721–728.
Zewail, T.M., Yousef, N.S., 2015. Kinetic study of heavy metal ions removal by ion
exchange in batch conical air spouted bed. Alex. Eng. J. 54, 83–90.