Journal of Environmental Chemical Engineering 6 (2018) 1201–1208

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Journal of Environmental Chemical Engineering

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Biosorbent from tomato waste and apple juice residue for lead removal T
a,b,⁎ a,b a a
Eddy Heraldy , Witri Wahyu Lestari , Diah Permatasari , Devita Dwi Arimurti
a
Department of Chemistry, Faculty of Mathematics and Natural Sciences, Sebelas Maret University, Jl. Ir. A. Sutami 36A, Kentingan, Surakarta 57126, Indonesia
b
Porous Materials Reseach Group, Chemistry Department, Sebelas Maret University, Jl. Ir. A. Sutami 36A, Kentingan, Surakarta 57126, Indonesia

A R T I C L E I N F O A B S T R A C T

Keywords: The biosorbents from different fruit waste such as tomato waste and apple juice residue were prepared and had
Biosorbents been investigated in removing of Pb(II) ion from the aqueous solution under optimized conditions. All fruit waste
Apple materials were activated by NaOH in room temperature. The synthesized biosorbents were characterized by FT-
Tomato IR, SEM, and surface area analyzer. Effects of contact time, the pH of the solution, and sorbent dosage on the Pb
Lead
(II) removal process had been optimized. Freundlich isotherm matched the experimental data than Langmuir
isotherm model. A kinetic study presented that Pb(II) sorption follows the pseudo-second-order kinetics. The Pb
(II) removal capacity of tomato waste and apple juice residue biosorbents are 152 and 108 mg/g, respectively.
The results showed that biosorbents have the potential capacity to remove the lead, which further strongly
increases after its activation.

1. Introduction
The heavy metal ions removal from wastewater such as Pb(II) is
imperative due to their bioaccumulation tendency, toxicity, persistence,
and non–biodegradability in nature [1,2]. Lead accumulation in the
human body also causes reproductive problems, central nervous system
damage [3], retard in the physical and mental activities, mainly in the
childhood age. Besides, its potential carcinogenic and neurological ef-
fects [4]; it could even cause death. Therefore, an increased interest had
been focused on effective studies of Pb(II) ion removal. In wastewater,
Pb(II) mainly come from metal plating and finishing manufacturing,
battery manufacturing, soldering material, printing and pigment, glass
industries and ceramic, ammunition, steel and iron manufacturing units
[5]. In literature, numerous treatment methods of Pb(II) wastewater
have been reported. These methods include membrane separation, ion
exchange, chemical precipitation and adsorption [6]. For example,
adsorption was regarded as the superior technique method related with
low lead concentrations in wastewater. Various adsorbents, for in-
stance, activated carbon, montmorillonite, zeolite, wheat straw, waste
biomass, hydrotalcite [7–9] were used. The present study aimed to
investigate the possibility of apple juice residue and tomato waste as an
effective and low-cost sorbent for Pb(II) ion removal. The variables
operation effect such as initial lead ion concentration, adsorbent dose,
solution pH, contact time was investigated. Biosorbents could be in-
creasing their adsorption capacity through chemical modification.
Treatment with acid or alkali was the common modification methods
[10,11]. The equilibrium sorption was modeled using the Freundlich
and Langmuir isotherm. The behavior of sorption with the passage of
time was investigated using kinetic studies.
2. Materials and methods
2.1. Materials
All chemicals and reagents are used in analytical grade without
further purification. The pH of solutions was adjusted by addition of
either HCl or NaOH 0.1 M solution. The fruit waste material required as
starting material for this work was collected locally. Mainly, the apple
juice residue (AR) was obtained from the destruction of locally apple
(“manalagi”) [12]; while the biomass tomato wastes (TW) was collected
from “Pasar Gede Surakarta” market [13].
Initially, for the preparation of biosorbents, the fruit wastes were
crushed, washed several times with distilled water, and dried in the
oven at 70 °C, respectively. Then, they were washed properly using
distilled water and dried at 70 °C for 48 h until the biosorbent constant
weight is obtained. Dried-fruit wastes were crushed and sieved to
100 mesh sizes.
2.2. Procedure
2.2.1. Preparation and modification of biosorbents
NaOH reagent was used to increase the proportion of active

⁎
Corresponding author at: Department of Chemistry, Faculty of Mathematics and Natural Sciences, Sebelas Maret University, Jl. Ir. A. Sutami 36A, Kentingan, Surakarta 57126,
Indonesia.
E-mail address: eheraldy@mipa.uns.ac.id (E. Heraldy).

https://doi.org/10.1016/j.jece.2017.12.026
Received 18 August 2017; Received in revised form 31 October 2017; Accepted 13 December 2017
Available online 09 January 2018
2213-3437/ © 2018 Elsevier Ltd. All rights reserved.
E. Heraldy et al.
Fig. 1. FTIR spectra of AR biosorbent (A) and TW biosorbent (B) before and after activation and Pb(II) loaded.
surfaces. For samples activation, 10 g biosorbents was poured in dif-
ferent beakers containing 100 mL NaOH, 1:10 (m/v) and stirred thor-
oughly for 24 h at room temperature. Then, the solution was filtered,
and the activated samples were taken and washed several times using
distilled water until the washing solution pH becomes neutral. Then the
biosorbents was oven dried at 70 °C for 24 h. The final product was
sieved through 100 mesh sieve again to ensure uniform particle size.
2.2.2. Batch sorption experiments design
The batch sorption experiment was carried out in a set 250 mL
conical flask containing 25 mL of Pb(NO3)2 solution to investigate the
effect of biosorbent dosage (0.0125, 0,0250, 0.0500, 0.0750, 0,1000
and 0.1250 g); pH (2, 4, 6, 8 and 10), contact time (15, 30, 45, 60 and
75 min) and initial Pb(II) concentration (20, 40, 60, 80 and 100 ppm) at
constant agitation speed at 120 rpm and at the finish of pre-determined
time period the reaction mixtures were filtered out. The concentration
of Pb(II) on supernatant was analyzed by atomic absorption spectro-
photometer (AAS). Finally, Pb(II) removal efficiency was calculated
using the follows equation [14]:
C − Ce ⎫
Removal efficiency(%) = ⎧ i × 100
⎩ Ci ⎬
⎨ ⎭
where Ci and Ce are the initial at t = 0 and equilibrium concentration of
Pb(II) (mg/L) in the aqueous solution, respectively. The sorption ca-
pacity was determined using the weight balance equation for the bio-
sorbent by the follows equation:
(Ci − Ce ) V
q=
W (2)
where q is the sorption capacity (mg/g), V is the volume of Pb(II) so-
lution (L), and W is the weight of the sorbent (g).
2.2.2.1. Effect of initial pH. Initial pH effect on Pb(II) removal was
investigated at different pH values (2, 4, 6, 8 and 10). The initial
concentration of Pb(II) was 20 ppm. The samples were stirred for 1 h at
room temperature.
2.2.2.2. Effect contact time. At the optimisation of contact time,
adsorption process was performed in different shaking times (15, 30,
45, 60 and 75 min) at an optimum pH value obtained from the previous
section. The initial Pb(II) concentration was 20 ppm.
2.2.2.3. Determine the optimum biosorbent dosage. Amount of biosorbent
was varied with a range of concentration (0.0250, 0.0500, 0.0750,
0.1000 and 0.1250 mg/L) in 25 mL of Pb(II).
2.2.3. Batch kinetic studies
The processes of the batch kinetic studies were fundamental to those
of equilibrium experiments. The aqueous solutions were chosen at
Journal of Environmental Chemical Engineering 6 (2018) 1201–1208
certain time intervals, and the concentration of Pb(II) was similarly
measured. The quantity of sorption at time t, was computed using the
equation:
(Ci − Ct ) V
qt =
W (3)
where Ct (mg/L) is the concentration of Pb(II) at any time.
2.2.4. Biosorbents characterization
To detect the functional groups present in the prepared biosorbent
and interaction between lead and the active functional group on the
biosorbent surface were analyzed by Fourier transform IR (FTIR)
spectrometry. FTIR spectra were recorded using Shimadzu FTIR model
8201. The sample of dried biosorbents was grinded sufficiently with
KBr by pallet method. The spectra were recorded in the range of
4000–400 cm−1. The surface morphologies were observed with the aid
of field-emission scanning electron microscopy (FE-SEM). SEM images
were taken using the FEI type INSPECT-s50 at an accelerating voltage of
6 kV. The specific surface area (SBET) measurements of the materials
were calculated by Brunauer-Emmett-Teller (BET) method and pore
size distribution were performed by nitrogen (N2) adsorption-deso-
(1) rption isotherms method through a Monosorb direct reading specific
surface analyzer (Nova Win 1200e).
3. Results and discussion
3.1. Characterization of biosorbents
3.1.1. FTIR analysis
FTIR spectra determination was carried out to analyze the potential
changes in vibration frequency resulting in the functional groups of the
prepared biosorbents and after biosorption. The FTIR spectra of bio-
sorbents before and after activating by NaOH and after Pb(II) sorption
are displayed in Fig. 1. In two biosorbent (before activating), the
spectra are similar which is the band observed around 3440 cm−1 due
to OH stretching. The peaks around 2926 and 1746 cm−1 are relating to
CeH symmetrical stretching and C]O stretching that main character of
hemicellulose, respectively. Absorption bands appeared around 1514
and 1016–1163 cm−1 are assigned to C]C aromatic stretching from
lignin and CeO. While in biosorbents after activated, the peaks appear
around 1504 and 1727 cm−1 are corresponding to C]C and C]O bond
that indicated delignification process [15]. The bands shifting to lower
frequencies showed bond weakening, while conversely, a shift to higher
frequencies suggests an increase in bond strength [16]. It is shown that
the decreasing in the bond strength of lignin and hemicellulose in cel-
lulose due to the reaction of delignification by NaOH in the biosorbent.
Hence, delignification by NaOH is able to break the lignin in cellulose
and may solve other substances. In Fig. 1, the intensity of absorption
bands OeH, CeH and C]O group in FTIR spectra of biosorbent before
and after biosorption of Pb(II) decreased due to the interaction of Pb(II)
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with the functional groups [17]. It was seen that the band at 3435 cm−1
shifted to 3492 cm−1 (for AR) and at 3399 cm−1–3463 cm−1 (for TW)
related to OH functional was shifted after sorption, indicating the in-
volvement of OH group with sorption of Pb(II) [18,19].
3.1.2. SEM analysis
SEM analysis is a helpful tool for portraying the surface morphology
of the biosorbents. The SEM was performed to analyze the surface
modifications of biosorbents before and after NaOH activation. As could
be seen in Fig. 2 that a biosorbent before NaOH activation has a dense
and rigid morphology, revealing homogeneous without any porous
structure and a little-damaged surface, caused by liberation of volatile
substances in carbonization process. The SEM images of biosorbents
after NaOH activation obviously indicate surface modifications during
the activation process. The NaOH-activated biosorbents appearance an
irregular surface with cavities of several sizes, demonstrating more
porous with a well-built porous structure, affecting from the vaporiza-
tion of impregnated NaOH and derivative compounds. It is clear that
biosorbents possesses different and a rough surface morphology, where
there is a good possibility for sorbates be adsorbed. The cavities on
biosorbents surface proper canals for diffusion of sorbates into the
biosorbents, make available access to its micro and mesopores, wherein
they can interact with the surface of functional groups [20].
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Journal of Environmental Chemical Engineering 6 (2018) 1201–1208
Fig. 2. SEM images of biosorbent (for instance AR) before (A)
and after activation (B) at 2000×. Similar behaviour was
observed for TW.
The SEM images of biosorbents before and after Pb(II) ions sorption
are displayed in Fig. 3. SEM analyses were carried out with the purpose
to confirm the sorption of Pb(II) onto NaOH-activated biosorbents.
There is a definite difference in the surface morphology of biosorbents
before and after Pb(II) loaded. It is clear from SEM images that bio-
sorbents (Fig. 3A and C) have a rough and varied morphology of surface
with small granules and many holes, wherein there is a good chance for
Pb(II) ions to sorb. The Pb(II) loaded images (Fig. 3B and D) demon-
strate the secondary solids appearance on the surface that knowingly
different from unloaded biosorbent, representing that precipitation of
surface took place during sorption. The surface of Pb(II) loaded bio-
sorbents had various particle sizes; the morphology of surface had al-
tered with no other existing space. It is nothing surface spaces, and the
particles were surfaces closely packed. The result was in agreement
with the FT-IR analysis (Fig. 1).
3.1.3. Surface area analysis
The specific surface area and pore volume of biosorbents were de-
termined by the Brunauer-Emmett-Teller (BET) methods were pre-
sented in Table 1. The BET surface areas of biosorbents before and after
activation were found to be 7.04 and 11.13 m2/g (for AR) as well as
8.83 and 45.00 m2/g (for TW), respectively. Activation of biosorbent
using NaOH cause delignification process, increasing in total pore
Fig. 3. SEM images of biosorbent before (A = AR; C = TW)
and after Pb(II) loaded (B = AR; D = TW) at 2000×.
E. Heraldy et al.
Table 1
BET Surface Area of Biosorbents.
Biosorbent Surface area (m2/g) Pore volume (cc/g)
AR 7.04 6.44 × 10−3
ARac 11.13 8.34 × 10−3
TW 8.83 8.13 × 10−3
TWac 45.00 4.47 × 10−2
volume and surface area. The activation method by NaOH providing the
growth of various pores with different sizes and high surface area. The
pore size founds by BJH method was typical of mesoporous materials.
The TW biosorbent has a good surface area compared with other sor-
bent, for instance, activated phosphate (22.22 m2/g) [21], raw clin-
optilolite (15.36 m2/g) [22], non-activated charcoal (21.0 m2/g) [23]
used for Pb(II) removal.
3.2. Biosorption parameter studies
3.2.1. Effect of pH
The aqueous solution pH containing the sorbate is an essential
parameter in the sorption process [24]. The significant role of pH is
very well documented in the literature because it may affect not merely
the appearance of the compounds dispersed in water but also the
group’s dissociation on the surface of the biosorbents [3]. Besides that,
the efficiency of sorption activity greatly depends on solution pH, due
to the variation of pH could further changes in the charges and states of
the functional groups of biosorbent materials as well as sorbate mole-
cules. Therefore, optimizing of sorbent capacity in Pb(II) removal needs
between other determination of pH value favorable for contact and
interaction among sorbent and sorbate. Influence of initial solution pH
on Pb(II) adsorption onto NaOH-activated biosorbents was evaluated in
the pH value of pH 2–10. Fig. 4 demonstrations the pH effect on the
percentage of Pb(II) removal. As shown in Fig. 4 at pH 2.0 (low pH), Pb
(II) sorbed a low amount of Pb(II). However, when the initial pH of Pb
(II) solution was raised, the sorption capacity was raised as well. As can
be seen, NaOH-activated biosorbents demonstrated a percentage of Pb
(II) removal rises gradually from pH 2.0, reached a maximum nearly
97% at pH 4.0 (for TW biosorbents), and around 99% (for AR biosor-
bents) and then decreases that match of previous research. Thus, the
sorption experiments for Pb(II) removal using biosorbent fruit waste
were not conducted at pH > 4. Hence, the optimum pH for sorption of
Pb(II) was observed at pH 4.0. At the pH 4.0, there are other functional
groups could be revealed and effectively release their protons into the
solution to transport negative charges to increase the binding capacity
for Pb(II). Other investigators who showed that sorption efficiency of
Fig. 4. Effect of solution pH on Pb(II) removal (%).
Journal of Environmental Chemical Engineering 6 (2018) 1201–1208
Pore size (Å)
1.827
1.499
1.841
1.985
Fig. 5. Effect of sorbent dosage on sorption capacity (mg/g) (thin line) and Pb(II) removal
(%) (thick line).
sorbents was low at lower pH and increases at higher pH values [25]
had stated same results. It might be justified by the fact that at acidic
pH (mainly in pH 2), the H+ concentration is higher and most of the
active site of the biosorbent might be occupied by H+ [26], making the
biosorbents surface becomes more positively charged. In such a situa-
tion, thereby being electrostatic repulsion forces for binding of Pb(II)
ions occurs. However, when the pH value increased (from pH 2 to 4),
the concentration of H+ ions decreases and negatively charged on
biosorbents surface is exposed due to deprotonated of sites which could
interact with Pb(II) ions [19,27–29]. At the pH > 6, the Pb(II) ions in
solution might undergo hydrolysis and precipitation as lead hydroxides
[19,30,31].
3.2.2. Effect of biosorbents dosage
Biosorbents dosage had a substantial impact on the sorption of the
Pb(II) at a certain initial concentration. Sorption process is related to
mass transfer phenomenon. Sorption capacity rises with increasing
contact among sorbent and sorbate. Nevertheless, excessive usage of
sorbent adds the expense of sorption process, making contact less at-
tractive. The biosorbents dosage dependency used up on the sorption of
Pb(II) was examined, and the results are presented in Fig. 5. As can be
seen in Fig. 5 that the sorption of Pb(II) rose with the increase of sor-
bent dosage from 0.025 mg to 0.100 mg/25 mL and reached a max-
imum at 95.6% removal (for TW biosorbents) and 90.8% (for AR bio-
sorbents). The increase in sorption was due to the availability of more
amount of sorption active sites and functional groups for the sorption of
Pb(II) ions [27]. Subsequently, with the increase of sorbent dosage from
0.100 to 0.125 mg/25 mL, the amount of Pb(II) removal was found to
diminished caused by the overlying or aggregation of active sites at
higher dosage [32]. Consequently, an optimum sorbent dosage of
0.100 mg/25 mL was chosen for further experiments.
However, the amount sorbed per unit mass of sorbent reduces
considerably. This is caused by the increase in some sorption active sites
on the sorbents surface. The results are predictable due to by increasing
the sorbents dosage, the number of sorption sites accessible for sor-
bent–sorbate interaction is increased as well and consequently be-
coming easier penetration of the Pb(II) ions to the sorption sites. The
increase of biosorbents dosage is parallel with the accessibility of other
active sites for the joining of Pb(II) in solution, which justifies the re-
lation of removal rate with biosorbents dosage increasing.
3.2.3. Effect of contact time
One of the critical parameters that affecting sorption is contact time.
The effect of contact time for Pb(II) ions removal onto AR and TW
biosorbents is presented in Fig. 6. In the beginning, the plot reveals that
the sorption of Pb(II) removal by all biosorbents is rapid very quickly.
Thereafter, the sorption reaction becomes slower. It gradually slows
down a slight change in Pb(II) removal efficiency until it gets the re-
mains constant (equilibrium). In all case of biosorbents, about 94% of
the sorption capacity for Pb(II) removal was reached within the first
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E. Heraldy et al.
Fig. 6. Effect of contact time on Pb(II) removal (%).
15 min of contact for a Pb(II) solution of 20 ppm. It could be seen that in
all circumstance no desorption occur. When the equilibrium is attained,
it remains constant.
It might be explained by initial sorption step, which involved the Pb
(II) sorption onto the free external surface sites of sorbents are available
for sorption. The biosorption is relatively rapid in the initial 15 min due
to the active site of biosorbents were unoccupied, and Pb(II) ions could
easily interact with free active surface sites. After an interval of time,
the next step is slower due to much of the surface sites are occupied
[33]. In addition, it is difficult to occupy the remaining free surface sites
are due to repulsive forces between the molecules of solute on the solid
and bulk phases. Therefore, the equilibrium contact time is regarded as
60 min (AR biosorbents) and 75 min (TW biosorbents) for all furthest
experiments to confirm that the equilibrium was attained.
3.3. Isotherm analysis studies
To measure the sorption capacity of biosorbent for Pb(II) removal
ions, the Freundlich and Langmuir isotherm models were used.
Freundlich and Langmuir’s isotherm is the most common isotherms
describing solid-liquid sorption system. As two-parameter models,
Freundlich and Langmuir isotherms, which give facts on the sorption,
capacity and constants associated with the activation energy. The
maximum sorption capacity (qm) values, correlation coefficient (R2),
and other constants can be determined from experimental data.
The Langmuir model is possibly the largely widely employed to
sorption isotherms. Langmuir sorption isotherm assumes that the
sorption takes place at the surface of sorbent, which is specific homo-
geneous sites, has only one-type sites binding, where the molecules
form a monolayer of sorbate, saturating the pores and avoiding the
migration. No further sorption could take place at this site. It considers
the sorption energy of each molecule is same, independent of the sur-
face of the material. The non-linearized and linearized form of
Langmuir isotherm could be expressed as follow [34].
Ce C 1 k1
= e +
qe qm KL. qm (4)
where qe (mg/g) is the amount of Pb(II) ion sorbed per specified
amount of sorbent; Ce (mg/L) is the equilibrium concentration of Pb(II)
ions; qm is the amount of sorbate required to form a monolayer (mg/g)
and KL (L/mg) is the Langmuir equilibrium constant, respectively. From
the linear plots, Ce/qe vs. Ce of Langmuir model (Fig. 7) can obtain the
value of qm and KL from the slope (1/qm) and the intercept [1/(qm KL)].
The results for sorption of Pb(II) ions onto both AR and TW biosorbents
were 4.00 and 1.51 × 10−1 mg/g, respectively. The linearity (R2) of the
plot was 0.986 and 0.973, respectively. The Langmuir type sorption
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Journal of Environmental Chemical Engineering 6 (2018) 1201–1208
isotherm shows surface sameness of the sorbent and suggestion to the
conclusions that the surface of sorbent is built up of minor sorption
spots, which are energetically same to other, is respect to sorption oc-
currence. It is assumed that the sorption of Pb(II) ions onto biosorbents
is good and the Langmuir isotherms are related to the sorption process.
The Freundlich isotherm model can be considered as one of the
initial empirical equations and is displayed to be reliable with an ex-
ponential distribution of the active centres [35]. The Freundlich iso-
therm model supposes that the multilayers sorption of Pb(II) ions took
place on heterogeneous surface sites. The well-known linear equation of
Freundlich sorption isotherm can be expressed as follows [34]:
ln qe = ln KF + 1/n ln Ce (5)
where KF and 1/n are the Freundlich isotherm constant for Pb(II) ion
sorption. Hence, a plot of ln qe against ln Ce should be a linear line with
a slope 1/n and the intercept of ln KF as shown in Fig. 8. The corre-
sponding parameters of two isotherm models found in the current study
as shown in Table 2.
From the two isotherm models evaluated, the data matched with
Freundlich isotherm with a high-value correlation coefficient (R2) for
AR (R2 = 0.992) and TW biosorbent (R2 = 0.985), compared to
Langmuir isotherm (R2 = 0.980 and R2 = 0.973), respectively. The
sorption capacity found by Langmuir isotherm is 108 mg/g (for AR) and
152 mg/g (for TW). The best match of equilibrium data with Freundlich
isotherm indicates that heterogeneous biosorption performs a key part
in Pb(II) removal ions. In addition, the KF value shows the sorption
capacity of sorbent and the value of 1/n < 1 or n (dimensionless
constant) higher than one shows easy separation and favorable multi-
layer sorption of Pb(II) ion from aqueous medium [36,37]. The smaller
value of 1/n obtained (0.474–0.543) shows better sorption and for-
mation of a relatively stronger bond between biosorbents and Pb(II)
ions.
Table 3 presents many others material used for Pb(II) removal from
aqueous solution. When the comparison of sorption capacity in re-
moving Pb(II) ions of AR and TW sorbent with other sorbents in the
literature, it is be seen that biosorbents in this studied had a good ad-
sorptive character. These results indicate that biosorbent might be well
used as a sorbent of Pb(II) removal from aqueous solution even without
any modifications.
3.4. Sorption kinetic studies
The sorption kinetics might give valuable understanding into the
reaction ways and sorption courses mechanisms. To explain the sorp-
tion kinetic of Pb(II) ion onto biosorbents was studied by two of the
most commonly used models, namely, pseudo-first-order model and
pseudo-second-order model. The compliance between experimental
data and the model expected values was stated by the correlation
coefficient (R2).
3.4.1. Pseudo-first-order model
The pseudo-first order rate model of Lagergren [30,34] is based on
solid capacity and expresses as follows
log(qe − qt ) = log qe − t
2,303 (6)
where qe is the quantity of solute sorbed at equilibrium per weight unit
of biosorbent (mg/g), qt is the quantity of solute sorbed at any time
(mg/g), and k1 is the sorption constant. It is the very well-known form
of the pseudo-first-order kinetic model. The worth of k1 at various times
was determined from the plots of log (qe-qt) versus t (Fig. 9) for Pb(II)
removal. Constant k1 and correlation coefficient (R2) had been com-
puted and presented in Table 4. The correlation coefficient (R2) values
found were quite small. It indicated that the pseudo-first order rate
extremely bad correlation coefficient (R2) for best fits data.
E. Heraldy et al. Journal of Environmental Chemical Engineering 6 (2018) 1201–1208

Fig. 7. Langmuir isotherm plots of Pb(II) ion onto AR biosorbent (A) and TW biosorbent (B).

Fig. 8. Freundlich isotherm plots of Pb(II) ion onto AR biosorbent (A) and TW biosorbent (B).

Table 2 3.4.2. Pseudo-second-order model

Isotherm constants and regression data for sorption of Pb(II) onto biosorbents. For the pseudo-second-order model, the kinetic data were examined
using a formula, which could express as below [34,38]:
Biosorbents Sorption parameters
t 1 1
Langmuir Freundlich
= + t
qt k2 qe2 qe (7)
qm (mg/g) KL (L/mg) R2 KF (mg/g) n R2
where k2 (g/(mg.min)) is the pseudo-second-order rate constant; t (min)
AR 108 0.130 0.980 13.00 1.84 0.992 is the sorption time; qe (mg/g) is the equilibrium Pb(II) sorption ca-
TW 152 0.496 0.973 13.81 2.11 0.985 pacity of biosorbent, and qt (mg/g) is the sorption capacity at a time t.
The k2 and qe could be obtained from the slope (1/qe) and intercept (1/
k2.qe2)) of the linear plot of t/qt versus t (Fig. 10). The k2 and qe, which
Table 3 is computed from the model, are displayed in Table 4. It could be shown
Comparison of sorption capacity (mg/g) of Pb(II) ions removal on some sorbent.
that the sorption of Pb(II) ions follow the pseudo-second-order rate
Sorbent Sorption capacity of Pb(II) References model, with a correlation coefficient (R2) of 0.999 for all biosorbent.
(mg/g) These results indicate that Pb(II) removal on biosorbent follows me-
chanism of a pseudo-second-order, and the sorption process is mostly
Anadara inaequivalvis shell 621.1 Bozbas and Boz [42]
governed by chemisorption.
Orange peel xanthate 204.5 Jiang et al. [40]
Tomato waste 152 This study
Citrus maxima peel 126 Chao et al. [41] 3.5. Desorption studies
Apple residue 15.8 Lee et al. [44]
Apple residue 108 This study
One of the fundamental considering for sorbents usage is the
Ponkan peel 112.1 Pavan et al. [43]
Palm shell activated carbon 95.2 Issabayeva et al. [31] probability of their regeneration, where allows the materials to be re-
Magnetic Litchi peel 78.74 Liang et al. [39] used. It is the main factor in supporting the use of a sorption process as
Passion fruit shell 51.3 Chao et al. [41] a cost-effective and highly effective method of Pb(II) removal ions from
Sugarcane bagasse 27.1 Chao et al. [41] aqueous systems. Due to this fact, in this work the desorbing agents
Cedar leaf ash 8.0 Hafshejani et al. [28]
used were water (for capturing mechanism), ammonium acetate 0.1 M
(for ion exchange mechanism), hydrochloric acid 0.1 M (for acid-base

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E. Heraldy et al. Journal of Environmental Chemical Engineering 6 (2018) 1201–1208

Fig. 9. Pseudo-first-order kinetics models plot of Pb(II) ion onto AR biosorbent (A) and TW biosorbent (B).

Table 4 Table 5
Pseudo-first and pseudo-second-order models for sorption of Pb(II) ions onto biosorbents. Desorption efficiency (%) of Pb(II) ions from biosorbent depending on the sorbing agent
used.
Biosorbent Pseudo-first-order model Pseudo-double-order model
Biosorbent Desorption efficiency (%)
k1 (1/min) qe (mg/g) R2 k2 (g/mg.min) qe (mg/g) R2
H2O NH4-acetate HCl Na2-EDTA
AR 0.041 0.435 0.754 0.184 5.000 0.999
TW 0.040 0.365 0.873 0.259 4.958 0.999 AR 0.000 0.073 59.647 99.809
TW 0.000 8.118 53.473 94.247

reaction mechanism) and sodium EDTA (Na2-EDTA) 0.1 M (for complex

forming reaction mechanism). The results obtained are presented in
Table 5.
As it can be shown when a desorbing agent is a water, the Pb(II) ions
were not eluted. It might demonstrate a strong bond between the sor-
bent and sorbate. However, when Na2-EDTA and hydrochloric acid
were used, the desorption results gave satisfactorily. It showed that the
biosorbent was obtained highly stable and then it can be reused. Hence,
from the desorption results it might be assumed that it is possible to use
the biosorbent in further sorption process, which is significant im-
portance for economic development and ‘green’ technologies in Pb(II)
ions removal from aqueous solution.
4. Conclusions
The following conclusions are arrived at based on the results of the
present study:
• Pre-treatment with NaOH causes the increasing of biosorbents ac-
tivation.
• The optimum conditions for maximum removal percentage of Pb(II)
by biosorbents were found to be at pH 4.0 with 0.1 g of sorbent and
60 min contact time for AR and 90 min for TW.
• The kinetics of Pb(II) ions removal on biosorbents followed a
pseudo-second-order model, which shows that the process was
controlled by chemisorption.
• The equilibrium data can best describe by the Freundlich isotherm
than Langmuir isotherm.
• The sorption capacity of AR and TW were 108 and 152 mg/g, re-
spectively. These values were higher than those of biosorbent, which
had been considered as excellent biosorbent by several researchers.
It can be concluded that the AR and TW were a strong candidate, an
effective and efficient biosorbents for the Pb(II) removal from the
aqueous system.

Fig. 10. Pseudo-second-order kinetics models plot of Pb(II) ion onto AR biosorbent (A) and TW biosorbent (B).

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E. Heraldy et al. Journal of Environmental Chemical Engineering 6 (2018) 1201–1208

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