sustainability

Article
Kinetic and Isotherm Studies of Ni2+ and Pb2+ Adsorption from
Synthetic Wastewater Using Eucalyptus
camdulensis—Derived Biochar
Muhammad Shafiq 1 , Abdulrahman Ali Alazba 1,2 and Muhammad Tahir Amin 1,3, *

1 Alamoudi Water Research Chair, King Saud University, P.O. Box 2460, Riyadh 11451, Saudi Arabia;
msrana@ksu.edu.sa (M.S.); alazba@ksu.edu.sa (A.A.A.)
2 Agricultural Engineering Department, King Saud University, P.O. Box 2460, Riyadh 11451, Saudi Arabia
3 Department of Environmental Sciences, Abbottabad Campus, COMSATS University, Islamabad,
Abbottabad 22060, Pakistan
* Correspondence: mtamin@ksu.edu.sa; Tel.: +966-11-467-3737

Abstract: The production of biosorbents by waste biomass has attracted considerable attention
due to the low cost and abundance of the raw materials. Here biochar produced from Eucalyptus
camdulensis sawdust (EU-biochar) via pyrolysis at 600 ◦ C was used as a potential biosorbent for
Ni2+ and Pb2+ metal ions from wastewater. Characterization experiments indicated the formation
of C- and O-bearing functional groups on the EU-biochar surface, while shifts and changes in the
shape of C–H bands suggested the adsorption of Ni2+ and Pb2+ onto EU-biochar by interacting
with surface carboxylic groups. Pb2+ was adsorbed more quickly than Ni2+ , indicating a faster and
stronger interaction of Pb2+ with EU-biochar compared to Ni2+ . As the initial concentrations of both
metal ions increased, the percentage removal decreased, whereas increasing the EU-biochar dose





 improved the percentage removal but impaired the adsorption capacity for Ni2+ and Pb2+ . The
Citation: Shafiq, M.; Alazba, A.A.; adsorption capacity could only be improved without affecting the percentage removal of both ions
Amin, M.T. Kinetic and Isotherm by increasing the pH of the metal solutions. The sorption efficiency of EU-biochar and the removal
Studies of Ni2+ and Pb2+ Adsorption mechanism of Ni2+ and Pb2+ were further explored using non-linear and linear forms of kinetic and
from Synthetic Wastewater Using isotherm models.
Eucalyptus camdulensis—Derived
Biochar. Sustainability 2021, 13, 3785. Keywords: adsorption capacity; biochar; Eucalyptus camdulensis; removal mechanism; heavy metals;
https://doi.org/10.3390/su13073785 removal efficiency; kinetic model; isotherm model

Academic Editor: Franco Marsan

Received: 18 February 2021

1. Introduction
Accepted: 24 March 2021
Published: 29 March 2021
Rapid industrialization and urbanization in the last century have increased the con-
sumption of global freshwater by six times [1], leading to a shortage of fresh drinking
Publisher’s Note: MDPI stays neutral
water for the majority of the world’s population [2]. It is estimated that almost 3.9 billion
with regard to jurisdictional claims in
people will suffer from water scarcity by 2050 [3]. Anthropogenic activities have also
published maps and institutional affil- increased the levels of unwanted contaminants in freshwater resources worldwide [4]. For
iations. instance, industrial effluents carrying various organic and inorganic pollutants contribute
significantly to the contamination and depletion of freshwater reservoirs [5]. In particular,
metal and metalloids, such as nickel (Ni2+ ) and lead (Pb2+ ), are critical ecological threats,
as they are widely used in plating and tanning, mineral, machinery, battery manufacturing,
Copyright: © 2021 by the authors.
and other industries [6], while the Ni2+ - and Pb2+ -rich industrial effluents are discharged
Licensee MDPI, Basel, Switzerland.
into adjacent water resources, posing a serious threat to human and animal health. In order
This article is an open access article
to address the current challenges of increasing freshwater needs, depletion of available
distributed under the terms and freshwater supplies, and deterioration of clean water resources due to contamination, nu-
conditions of the Creative Commons merous studies have focused on developing novel technologies for removing threatening
Attribution (CC BY) license (https:// pollutants from wastewater streams.
creativecommons.org/licenses/by/ Specifically, several methods have been developed for the removal of metal and met-
4.0/). alloids from wastewater streams, but most of them are ineffective or expensive. Even

Sustainability 2021, 13, 3785. https://doi.org/10.3390/su13073785 https://www.mdpi.com/journal/sustainability

Sustainability 2021, 13, 3785 2 of 16

advanced methods, such as catalytic degradation, oxidation, solvent extraction, mem-

brane filtration, steam stripping, ion exchange, chemical precipitation, electrocoagulation,
microbial degradation, and electrocoagulation, proved to be ineffective in completely
removing contaminants from water [7–12]. In contrast, adsorption is a widely accepted
technology for the removal of metal and metalloids from contaminated wastewater, as
it is a cost-effective, highly efficient, and easy-to-use method that generates little residue
and allows the recovery and recycling of the adsorbent unlike most traditional wastewater
treatment methods [13,14]. Therefore, great effort has been made to develop effective,
inexpensive, and environmentally friendly adsorbents that are suitable for each type of
contaminant [15–18]. To date, several adsorbents, including clay, biomass, nanomateri-
als, layered double hydroxide, graphene, activated carbon, chitosan, and fly ash, have
been successfully used for the removal of metal/metalloids from contaminated wastew-
ater [19–27]. Furthermore, the production of biosorbents by reusing or recycling waste
biomass and feedstock, such as agricultural waste and wood sawdust, has attracted consid-
erable attention due to the low cost, abundance, and environmental friendliness of the raw
materials [28–31]. Similarly, biochar has been produced from agricultural waste and used
as an efficient adsorbent.
Biochar is a solid, black, and stable porous carbonaceous material produced by the
pyrolysis of waste materials, such as wood, grass, manure, sludge, etc. [32], with little or
no air at 300–800 ◦ C [33,34]. Several studies have shown that biochar is one of the most
effective adsorbents for the removal of metal or metalloids from industrial effluents due to
its large specific surface area, water insolubility, richness in carbon, abundant pore structure,
and active functional groups on its surface [35]. Moreover, the use of agricultural or fruit
waste as the raw material not only reduces the overall costs, but also limits the pollution of
surface water through the reuse of solid waste. To date, various waste materials, such as
rice husk, wheat straw, wood waste biomass, and fruit waste, have been used to produce
biochar to remove metals or metalloids from contaminated wastewater [29,36–40].
Based on the existing data, we considered that Eucalyptus camdulensis (EU) wood
biomass could serve as a low-cost raw material for the production of biochar, as its extensive
use in the manufacture of furniture and other purposes generates a large amount of sawdust
waste. Therefore, in this study, we used EU sawdust to produce biochar via pyrolysis
(EU-biochar), which was further evaluated as a potential adsorbent of Ni2+ and Pb2+ in
synthetic contaminated water. In addition, we applied a series of kinetic and isotherm
models to study the adsorption efficiency of EU-biochar and to elucidate the removal
mechanism of Ni2+ and Pb2+ from water.

2. Materials and Methods

2.1. Preparation and Characterization of Eucalyptus camdulensis (EU)-Biochar
EU-biochar was prepared from EU sawdust collected from different places in Riyadh,
Saudi Arabia. The collected sawdust was first washed with tap water to remove dirt
particles, followed by pre-drying under sunlight for a few days, and final drying in an
ordinary oven at 60 ◦ C for 6 h. Small pieces of the oven-dried sawdust was then crushed to
achieve an average particle size of about 0.5 mm. The very small pieces of EU sawdust were
finally pyrolyzed in a box furnace (Nabertherm, B−150, Lilienthal, Germany) at 600 ◦ C for
3 h to obtain EU-biochar with an average particle size of 50 µm. The specific surface area
of EU-biochar was measured by Brunauer—Emmett—Teller analysis, while the carbon and
volatile contents were estimated by proximate and ultimate analysis using an elemental
analyzer (Thermo Fisher Scientific, Berlin, Germany). The morphology and chemical
composition of the EU-biochar surface were analyzed by scanning electron microscopy
(SEM), energy-dispersive X-ray (EDX), and Fourier-transform infrared (FTIR) spectroscopy.

2.2. Materials
The stock solutions (1.0 g L−1 ) of Ni2+ and Pb2+ were prepared by dissolving 1.0 g of
Ni(NO3 )2 ·6H2 O (analytical grade, Tianjin Benchmark Chemical Reagent Co., Ltd., Tianjin,
Sustainability 2021, 13, 3785 3 of 16

China) or Pb(NO3 )2 (analytical grade, Tianjin Benchmark Chemical Reagent Co.), respec-
tively, in 1 L double distilled water. The stock solutions were further diluted with double
distilled water to prepare metal solutions with known initial concentrations. Depending
on the requirements of each batch experiment, the initial pH of the metal solutions was
adjusted using sodium hydroxide (0.1 M) or hydrochloric acid (0.1 M).

2.3. Batch Experiments and Adsorption Performance

For the batch experiments, each metal solution (50 mL) was homogeneously mixed
with the required amount of EU-biochar for a predetermined time in 100 mL glass funnels
in a temperature and humidity controlled shaker. The samples were then filtered, and the
residual metal concentration (Ct , mg L−1 ) was measured using an ultraviolet–visible (UV–
Vis) spectrophotometer, while the amount of metal uptake (qt , mg g−1 ) and the percentage
removal (R, %) by EU-biochar were estimated using the following equations:

V
qt = (C − Ct ) (1)
M in
(Cin − Ct )
% Removal = × 100 (2)
Cin
where Cin (mg L−1 ) is the initial metal concentration in the solution with volume V (L) and
M (g) is the mass of EU-biochar. Equation (1) was also used to measure the equilibrium ad-
sorption capacity (qe , mg g−1 ) against the equilibrium metal concentration (Ce ; mg L−1 ) in
the solution. Each batch test was repeated in triplicate to reduce any potential experimental
error (Figures 3 and 4). The efficiency of the batch process was optimized using a contact
time in the range of 1–300 min, an adsorbent dose in the range of 0.05–0.8 g, a solution pH
in the range of 2.0–10.0, and an initial metal concentration in the range of 5–100 mg L−1
(Figures 3 and 4).

2.4. Adsorption Kinetic and Equilibrium Isotherm Models

The pseudo-first-order (PFO), pseudo-second-order (PSO), Elovich, and intraparticle
diffusion of Weber and Morris (ID-WM) kinetic models and the Langmuir, Freundlich, Temkin,
Halsey, Dubinin—Radushkevich (D-R), Harkins—Jura (H-J), and Jovanovic isotherm models
were used in their linear and non-linear forms to elucidate the adsorption properties and
adsorption mechanism of EU-biochar (Table 1). The values obtained for the corresponding
parameters in each model using linear and non-linear regression analysis (Figures 5 and 6)
are presented in Tables 2 and 3.
The adsorption data of both metal ions were analyzed using the non-linear and linear
forms of four different kinetic models (Table 1), and the correlation coefficient (R2 ) of each
model was determined to compare their suitability in fitting the adsorption data. The
parameters of the non-linear form were calculated in the OriginPro 8.5 software, while
straight-line curve fitting in Microsoft Excel was used for the linear form. In order to model
the adsorption data, four different initial concentrations of each metal ion with an interval
of 10 mg L−1 were selected (Ni2+ : 10–40 mg L−1 and Pb2+ : 20–50 mg L−1 ). Table 3 presents
the variables calculated for each kinetic model for the selected metal ion concentrations,
i.e., 20 and 40 mg L−1 . The EU-biochar dose used for the adsorption of Ni2+ and Pb2+ was
kept at 0.4 and 0.2 g, respectively, while the pH of all metal solutions was maintained at
6.0 ± 0.2.
Sustainability 2021, 13, 3785 4 of 16

Table 1. Linear and non-linear equations of kinetic and isotherm models.

Model Non-Linear Form Linear Form

Kinetic
PFO k1 qt = qe (1 − exp(−k1 t))
log(qe − qt ) = log qe − 2.303 t
PSO t 1 1 qe 2 k2 t
q t = k q2 + q e t
2 e
qt = q e k 2 t +1
Elovich qt = β ln(t) + β ln(α) 1
qt = β ln(1 + αβt)
ID–WM qt = Kip t1/2 +C
Isotherm  
1 1 1 1 q K C
Langmuir qe = qm +
qm K L Ce q e = (1+ m L e
K L Ce )
1 1
Freundlich logqe = logK F + n logCe qe = K F ce n
Temkin qe = RT RT
bT ln A T + bT ln Ce qe = HRT ads
ln(KT Ce )
 
Halsey ln qe= n H ln k H − n1H ln Ce
1
qe = exp ln k H −ln Ce
n
 H
  2   2 
D–R ln qe = ln qm − K DR ( RT ln 1 + C1e qe = qm exp −K DR RT ln 1 + C1e

BH J
    1
H–J 1 1 A J
q 2 = AH J − A H J logCe qe = BH J −HlogC
2
e
 e 
Jovanovic ln qe = ln qm − k j Ce qe = qm 1 − exp k j Ce

3. Results and Discussion

3.1. Characteristics of EU-Biochar
3.1.1. Scanning Electron Microscopy (SEM) and Energy-Dispersive X-ray (EDX)
Spectroscopy Analysis
SEM analysis revealed that the outer surface of EU-biochar was rough and consisted
of abundant pore structures, which may favor the adsorption of Ni2+ and Pb2+ (Figure 1a).
In contrast, very small particles and some brighter zones were observed onto the adsorbent
surface after the metal ion adsorption (Figure 1b,c), which could be assigned to Pb2+ and
Ni2+ particles [41]. The variations in the elemental compositions of EU-biochar before
and after the adsorption of Ni2+ and Pb2+ were further observed by EDX spectroscopy
(Figure 1).

Figure 1. Scanning electron microscopy (SEM) micrographs and energy-dispersive X-ray (EDX) spectra of (a) Eucalyptus
camdulensis (EU)-biochar, (b) Ni2+ -loaded EU-biochar, and (c) Pb2+ -loaded EU-biochar.
Sustainability 2021, 13, 3785 5 of 16

The C content of EU-biochar increased from 63.05% to 88.14% and 73.51% after the
adsorption of Ni2+ and Pb2+ , respectively, whereas its O content decreased from 12.85%
to 10.76% and 3.54%, respectively. Additionally, the adsorption of Ni2+ and Pb2+ onto the
adsorbent was confirmed by the presence of 0.78% Ni2+ and 19.71% Pb2+ . These results
suggested that complexes bearing C- and O-containing functional groups were generated
on the biochar surface, successfully contributing to the sorption of Ni2+ and Pb2+ .

3.1.2. Fourier Transform Infrared (FTIR) Spectroscopy Analysis

The functional groups and the chemical composition of the free EU-biochar surface
were investigated by FTIR spectroscopy. The FTIR spectra of Ni2+ - and Pb2+ -loaded EU-
biochar were also recorded to further investigate the binding interactions between the
adsorbent and the metal ions (Figure 2).

Figure 2. Fourier transform infrared (FTIR) spectra of EU-biochar before and after the adsorption of
Ni2+ and Pb2+ .

Interestingly, no noticeable and sharp bands were observed in the recorded FTIR
spectra, probably due to the high pyrolysis temperature used for the production of EU-
biochar (600 ◦ C). It has been previously reported that pyrolytic temperatures ≥500 ◦ C
can destroy most functional groups of the biochar surface due to thermalization [42].
Nevertheless, a vibrational band with very low intensity was identified at 877 cm−1 in the
FTIR spectrum of free EU-biochar, which was attributed to aromatic C–H bonds. After Ni2+
adsorption, a slight shift from 877 to 876 cm−1 was observed, whereas no similar bands
were detected in the spectrum of Pb2+ -loaded EU-biochar, suggesting that the surface
carboxylic groups were involved in the adsorption of Ni2+ and Pb2+ . Moreover, after the
adsorption of Ni2+ and Pb2+ , very weak stretching vibration bands appeared at 1534 and
1403/683 cm−1 , respectively, which corresponded to carboxylate and aromatic C–H groups.
A weak stretching vibration peak was also detected in the spectrum of free EU-biochar at
2355 cm−1 corresponding to C=N (or CO2 impurity), which shifted to 2353 cm−1 after Pb2+
adsorption, but remained at the same position after Ni2+ adsorption. Taken together, the
adsorption of Ni2+ and Pb2+ onto EU-biochar was achieved through their complexation
with the carboxylic groups of the biochar surface.

3.2. Adsorption Equilibrium and Optimization of Contact Time, Initial Metal Ion Concentrations,
EU-Biochar Dose, and Solution pH
The changes in the uptake of both metal ions (for selected initial concentrations)
and the removal efficiency of EU-biochar were investigated in relation to the contact
Sustainability 2021, 13, 3785 6 of 16

time (0–300 min) using samples with four different initial metal concentrations that were
collected at regular intervals. During these experiments, the solution pH was kept constant
at 6.0 and the EU-biochar dose for the adsorption of Ni2+ and Pb2+ was set at 0.4 and
0.2 g, respectively.
Upon immediate contact of the sample solutions with EU-biochar, the percentage
removal and metal uptake increased rapidly due to the abundant active sites on the EU-
biochar surface that allowed the development of numerous interactions [43], while a
gradual increase was observed in both parameters as the contact time increased from 10 to
30 min (Figure 3). At this point and when the initial metal concentration was 20 mg L−1 ,
the percentage removal for Ni2+ and Pb2+ was 73% and 95%, respectively, corresponding
to an adsorption capacity of 36 and 129 mg g−1 . However, after 30 min, the adsorption
performance remained stable with insignificant (p = 0.01) or no changes in the percentage
removal or the metal ion uptake by EU-biochar due to the increasing interference of solute–
solute interactions. Therefore, we considered that the adsorption equilibrium was reached
at 30 min. Similar changes were also observed when other initial metal concentrations
were used (Figure 3). For instance, when the metal ion concentration was 40 mg L−1 , the
percentage removal for Ni2+ and Pb2+ reached 48% and 73%, respectively, corresponding
to adsorption capacities of 47 and 183 mg g−1 . Although the half dose of EU-biochar (0.2 g)
was used for the adsorption of Pb2+ compared to Ni2+ (0.4 g), the percentage removal of
Pb2+ was higher and more uptake points were identified, suggesting a faster interaction
between Pb2+ and the biochar surface, as well as a stronger deposition of Pb2+ on the
adsorbent surface compared to the interactions between Ni2+ and EU-biochar.

Figure 3. Optimization of the contact time with respect to the adsorption capacity and removal
efficiency of EU-biochar for (a) Ni2+ and (b) Pb2+ .

At the adsorption equilibrium (contact time, 30 min) and a constant solution pH of

6.0, the percentage removal decreased linearly from 92% to 27% for Ni2+ and from 95%
Sustainability 2021, 13, 3785 7 of 16

to 37% for Pb2+ as the initial metal ion concentrations increased from 5 to 80 mg L−1 and
from 20 to 100 mg L−1 , respectively (Figure 4a). This reduction could be attributed to the
unavailability or saturation of the active sites of EU-biochar with increasing metal ion
concentration and to the reduction in the ratio of fixed number of active sites to initial
number of metal ions [44–47]. Moreover, the adsorption capacities showed an increasing
trend with increasing initial concentrations and reached a maximum of 54 and 200 mg g−1
for Ni2+ and Pb2+ , respectively, at an initial concentration of 80 mg L−1 . This change was
attributed to the increased metal ion uptake, which resulted from the high mass transfer
and the reduced ionic strength of the solution at high initial concentrations. However,
the uptake of metal ions started to decrease after Ni2+ and Pb2+ concentrations of 70 and
80 mg L−1 , respectively, suggesting that these values were the optimal concentrations for
efficient adsorption performance of EU-biochar.

Figure 4. Optimization of (a) initial metal ion concentrations, (b) EU-biochar dose, and (c) initial solution pH in relation to
metal ion uptake and removal efficiency of EU-biochar.

Due to its direct impact on the adsorption performance, the EU-biochar dose for
the batch experiments was optimized using ranges of 0.1–0.8 g for Ni2+ and 0.05–0.3 g
for Pb2+ to enhance its removal efficiency (Figure 4b). In addition, the solution pH was
set at 6.0, and the initial concentrations of Ni2+ and Pb2+ were set at 20 and 40 mg L−1 ,
respectively, and the samples were shaken for 30 min. Our results indicated that, with
increasing EU-biochar dose from 0.1 to 0.8 g, the adsorption capacity of 20 mg L−1 Ni2+
decreased by 59% (from 59 to 24 mg g−1 ), while the percentage removal increased from
30% to 100%. In contrast, the adsorption capacity of EU-biochar for 40 mg L−1 Pb2+ was
reduced by about 64% (from 364 to 132 mg g−1 ) as the EU-biochar dose increased from
0.05 to 0.3 g, while the percentage removal increased from 46% to 100%. Therefore, 0.6 g
and 0.15 g were the optimal EU-biochar doses to achieve the optimal percentage removal
and adsorption capacity for Ni2+ and Pb2+ , respectively. We also reasoned that a high
amount of EU-biochar would provide a larger surface area and a higher number of active
sites for the selected metal ion concentrations, resulting in less significant changes in the
percentage removal.
A pH range of 2.0–10.0 and 2.0–8.0 was also selected to determine its effect on the
adsorption performance after mixing 20 and 40 mg L−1 Ni2+ and Pb2+ with 0.4 and
0.2 g EU-biochar, respectively, for 30 min. In particular, as the pH of the Ni2+ solution
increased from 2.0 to 10.0, the adsorption capacity of EU-biochar for Ni2+ increased from
9 to 48 mg g−1 and the percentage removal increased from 17% to 99% (Figure 4c). The low
initial adsorption capacity and percentage removal were attributed to the excess amount of
positively charged H+ (at low pH values), which competed with the positively charged
metal ions for adsorption on the negatively charged biochar surface [48,49]. Similarly,
the adsorption capacity of EU-biochar for Pb2+ increased from 34 to 196 mg g−1 with
increasing pH, while the percentage removal showed the same trend as that of Ni2+ due to
the improved electrostatic interactions between the negatively charged biochar surface at
high pH values and the positively charged Pb2+ (Figure 4c) [49–51]. A comparison of the
Sustainability 2021, 13, 3785 8 of 16

adsorption capacities of EU-biochar with that of other adsorbents for the studied metal
ions is presented in Table 2.

Table 2. Performance comparison of EU-biochar with other previously reported biochar used for the removal of Pb2+ and
Ni2+ ions.

Pyrolysis Holding Kinetic

Biomass Pollutants Qmax (mg g−1 ) Isotherm Reference
Temp (◦ C) Time Models
EU-biochar 600 6h Ni2+ 54 Langmuir PSO This work
EU-biochar 600 6h Pb2+ 200 Langmuir PSO This work
Rice husk
300 20 min Pb2+ 1.84 Langmuir PSO [52]
biochar
Pine wood
300 20 min Pb2+ 3.89 Langmuir PSO [52]
biochar
Hickory
600 2h Pb2+ 11.2 Langmuir PSO [31]
wood biochar
Date seed Freundlich,
550 3h Pb2+ 74.60 PSO [53]
biochar Langmuir
Buffalo weed
700 4h Pb2+ 333.3 Langmuir PSO [54]
biochar
Corn cob Elovich
600 2h Ni2+ 15.40 Langmuir [55]
biochar model
Sugar cane
Redlich-
bagasse 600 2h Ni2+ 38.15 PFO [56]
Peterson
biochar

3.3. Evaluation of the Adsorption Data through Kinetic Fitting Models

Very low R2 values (0.2–0.36) in the linearized PFO kinetic model reflected a poor
fitting of the model to the adsorption data of both metal ions, confirming its applicability
only for the initial stage (contact time) of adsorption [57,58]. The non-linear form of the PFO
model showed a better fitting to the adsorption of Ni2+ than that of Pb2+ , especially at high
initial concentrations (30 and 40 mg L−1 ). Moreover, the estimated adsorption capacities
(qe cal ) were considerably lower than the experimental values in the linear PFO model,
whereas the qe cal values in the non-linear form were slightly lower than the experimental
values except for the adsorption of Pb2+ at 40 mg L−1 . In addition, the rate constant k1 was
significantly lower in the linear than in the non-linear form of the PFO model with the Pb2+
adsorption showing higher values than Ni2+ (Table 3).
The adsorption data of all tested Ni2+ and Pb2+ concentrations were perfectly fitted
to the linear form of the PSO kinetic model with R2 values of ~1.0 (Figure 5a). Similar
results were obtained for the adsorption of Ni2+ (R2 = 0.94–0.99) using the non-linear form
of the PSO model, while the adsorption data of Pb2+ were good fitted (R2 = 0.81–0.88),
confirming the chemisorption of both metal ions onto EU-biochar, consistent with previous
studies [59–61]. The rate constant k2 in the PSO kinetic model decreased with increasing
initial concentrations of both metal ions, but a reverse trend was observed for the linearized
fitting to the adsorption data of Pb2+ . However, the correlation of the initial adsorption rate
(h) with the initial metal ion concentrations could not be predicted easily. In particular, the
h value was higher for 20 mg L−1 Ni2+ than for 40 mg L−1 Ni2+ , but an opposite trend was
observed for Pb2+ using both forms of the PSO kinetic model (Table 3). Moreover, the qe cal
value was closer to the experimental value only in the non-linear PSO model, but deviated
from the experimental value by about 7% for 40 mg L−1 Pb2+ in both model forms.
Sustainability 2021, 13, 3785 9 of 16

Table 3. Calculated variables in the linear and non-linear forms of the kinetic models used to model the adsorption of 20
and 40 mg L−1 Ni2+ and Pb2+ onto EU-biochar.

Linear Form Non-Linear Form

Kinetic Parameter Ni2+ (mg L−1 ) Pb2+ (mg L−1 ) Ni2+ (mg L−1 ) Pb2+ (mg L−1 )
Model
20 40 20 40 20 40 20 40
qe exp (mg g−1 ) 36.19 46.60 91.95 179.61 36.19 46.60 91.95 179.61
qe cal (mg g−1 ) 2.90 5.39 5.27 34.15 34.98 46.79 89 159.84
PFO k1 (min−1 ) 0.007 0.009 0.009 0.005 0.53 0.26 0.54 0.43
R2 0.24 0.36 0.2 0.32 0.76 0.92 0.46 0.64
qe cal (mg g−1 ) 36.63 49.75 96.15 166.67 36.23 49.1 92.67 166.05
k2 (g mg−1 min−1 ) 0.019 0.007 0.0049 0.0082 0.027 0.009 0.0100 0.0047
PSO
h (mg g−1 min−1 ) 24.88 17.39 45.66 227.27 34.98 21.24 86.22 128.21
R2 0.9999 0.9998 0.9999 0.9998 0.96 0.99 0.81 0.88
α (mg g−1 min−1 ) 5151.96 67.51 2160.36 1154.38 14,247.5 374.38 16,459.4 16,489
Elovich β (g mg−1 ) 2.76 5.48 7.62 14.26 0.36 0.18 0.13 0.07
R2 0.82 0.87 0.9 0.85 0.8 0.86 0.89 0.83
Kip (mg g−1 min1/2 ) 0.75 1.53 2.21 3.91 0.75 1.53 2.21 3.9
ID–WM C (mg g−1 ) 27.48 30.46 68.08 120.09 27.48 30.46 68.1 120.1
R2 0.5 0.57 0.63 0.54 0.5 0.57 0.63 0.54

Figure 5. Examples of the linearized and non-linear fitting of the (a) PSO and (b) Elovich kinetic models to the adsorption
data of Ni2+ and Pb2+ at 20 and 40 mg L−1 .
Sustainability 2021, 13, 3785 10 of 16

Both the linear and non-linear forms of the Elovich kinetic model yielded good R2
values (0.80–0.90) for all tested initial concentrations of Ni2+ and Pb2+ , suggesting that
both metal ions were adsorbed via activated chemical adsorption without desorption
(Figure 5b) [43]. However, in most cases, the relationship of the initial adsorption rate
constant (α) with the initial concentrations could not be established by estimating its
highest values at low initial concentrations. Moreover, based on the calculated β values
in linearized fitting, the number of sites available for adsorption [62] and the activation
energy of chemisorption [63] increased with increasing initial metal ion concentrations,
whereas non-linear fitting showed an opposite trend corresponding to the decreasing β
values (Table 3).
Furthermore, the ID–WM kinetic model yielded high values of parameter C, an
indicator of the boundary layer thickness, suggesting a greater boundary layer effect on
the adsorption process at high initial metal ion concentrations. The model rate constant
Kip also increased as the initial metal ion concentrations increased in both model forms.
However, the R2 values ranged between 0.50–0.63 (Table 3) and did not allow the prediction
of multilayer adsorption of Ni2+ and Pb2+ onto EU-biochar.

3.4. Evaluation of the Adsorption Data through Isotherm Fitting Models

Several two-parameter isotherm models were also applied to the adsorption data of
Ni2+ and Pb2+ (Table 1), and the adsorption performance of Ni2+ (5–80 mg L−1 ) and Pb2+
(20–100 mg L−1 ) onto 0.4 and 0.2 g EU-biochar, respectively, at a solution pH of 6.0 ± 0.2
was assessed using both the linearized and non-linear forms of the models (Table 4). The
regressions of the linear and non-linear forms of isotherms were solved using the OriginPro
8.5 and Curve Expert Professional software, respectively. Based on the experimental data,
the maximum adsorption capacities were achieved when the initial concentrations of Ni2+
and Pb2+ were 80 and 100 mg L−1 , respectively. Therefore, the maximum adsorption
capacities at 80 mg L−1 were selected to compare the theoretical calculated values of both
metal ions in each model.
The Langmuir model proved to be promising in explaining the monolayer adsorption
of both metal ions due to the high R2 values (0.96–0.99) and nearly perfect fitting using
both regression forms (Figure 6a). The estimated maximum adsorption capacity of the
model (qm ) was close to the experimental values for both metal ions (54 mg g−1 for Ni2+
and 200 mg g−1 for Pb2+ ) with a slightly better agreement of the non-linear form (Table 4).
Lower values of the Langmuir constant (KL ) were also found in the non-linear form for
both metal ions (Table 4), while KL was almost double for Pb2+ (0.81 L mg−1 ) than for
Ni2+ (0.41 L mg−1 ), implying a higher affinity of Pb2+ for EU-biochar compared to Ni2+ . In
addition, the dimensionless separation factor, RL [(1 + KL C0 )−1 ], had almost the same value
for both the linearized and non-linear Langmuir model, suggesting a similar isotherm
shape for both model forms [64]. This similarity was, however, not observed for the
adsorption of Ni2+ onto EU-biochar.
The qm values of the non-linear and linear Freundlich isotherm model were by 4% and
8% higher than the experimental values for the adsorption of Pb2+ , respectively, while an
overestimation of 17% and 10% was observed for Ni2+ (Table 4). However, the adsorption
data of Ni2+ were well fitted to the model with R2 values ranging between 0.94–0.95
(Figure 6b), while a reasonable fit to the data of Pb2+ was also achieved with R2 of 0.85 and
0.81 for the linear and non-linear form, respectively. The suitability of the model was
further confirmed by the dimensionless factor (n), which was >1.0 for both metal ions,
suggesting the surface heterogeneity of EU-biochar (1/n = 0–1.0) [65]. Moreover, the model
constant KF was higher in the non-linear form for both metal ions, but deviated significantly
from the favorable range [1–20 (mg g−1 ) (L mg−1 )1/n ], except for the adsorption of Ni2+ in
the linear form (Table 4), suggesting that the Freundlich isotherm model could not be used
to predict metal ion adsorption.
Sustainability 2021, 13, 3785 11 of 16

Table 4. Calculated values of the variables in the linear and non-linear forms of the isotherm models used to model the
adsorption of Ni2+ and Pb2+ (80 mg L−1 ) onto EU-biochar.

Ni2+ Pb2+
Isotherm Model Parameter
Linear Non-Linear Linear Non-Linear
qe exp , mg g−1 54 200
qm, mg g−1 50.51 55.21 192.31 193.95
KL , L mg−1 0.68 0.41 0.91 0.81
Langmuir RL 0.018 0.029 0.014 0.015
R2 0.99 0.98 0.98 0.96
qm , mg g−1 59.46 63.35 215.02 207.79
KF , (mg g−1 ) (L
15.54 21.48 106.28 114.00
Freundlich mg−1 )1/n
1/n 0.306 0.247 0.161 0.137
R2 0.95 0.94 0.85 0.81
KT, L mg−1 8.70 8.70 106.16 106.15
Temkin Hads , kJ mol−1 277.50 277.5 110.75 110.75
R2 0.99 0.99 0.88 0.87
qe cal , mg g−1 61.01 58.78 245.36 195.00
nH −3.27 −4.05 −6.22 −7.30
Halsey KH 0.323 0.000 0.264 0.000
R2 0.95 0.94 0.85 0.81
qm, mg g−1 45.95 49.31 179.68 181.64
KDR , (mol kJ−1 )2 2.0 × 10−7 4.0 × 10−7 2.0 × 10−7 2.6 × 10−7
D–R E, kJ mol−1 1.58 1.12 1.58 1.39
R2 0.85 0.82 0.86 0.81
AHJ , mg g−1 357.14 147.39 25000 1076.7
H–J BHJ 1.5357 3 2.25 4.47
R2 0.72 0.86 0.76 0.76
qm, mg g−1 23.89 50.9 134.05 184.39
Jovanovic Kj , L g − 1 −0.019 −0.28 −0.007 −0.49
R2 0.55 0.91 0.46 0.87

Compared to the Freundlich isotherm model, the Temkin model provided a better
fit to the adsorption data of both metal ions with a perfect fit to the adsorption of Ni2+
(R2 = 0.99), reflecting the heterogeneous adsorption of Ni2+ onto EU-biochar with uniform
distribution of binding energies [66]. In addition, a considerably lower binding constant at
equilibrium (KT ) and a higher heat of adsorption (Hads ) were observed for the adsorption
of Ni2+ compared to the adsorption of Pb2+ (Table 4).
The Halsey model yielded exactly the same R2 values as the Freundlich model with
higher R2 for the adsorption of Ni2+ than Pb2+ and slightly better results in the linear than
the non-linear form. The qe cal values of the non-linear form were closer to the experimental
values compared to the linear form. In addition, the model constant and exponent (KH and
nH , respectively) were higher for the adsorption of Ni2+ than for the adsorption of Pb2+ ,
while the linearized fitting yielded higher KH values than the non-linear fitting (KH = 0) for
both metal ions (Table 4).
The D–R isotherm provided good R2 values (0.81–0.86) for both metal ions, while
linear fitting yielded slightly higher R2 values than the non-linear fitting. However, the
theoretical qe cal of the non-linear form agreed more with the experimental values compared
to that of the linear form for both metal ions (Table 4). Considering also the calculated
values of the mean free energy of adsorption [E = (2KDR )−1/2 , <8 kJ mol−1 ] resulting
from the significantly low values of the model constant (KDR ~ 0, Table 4), the D–R model
suggested that both metal ions were physisorbed onto EU-biochar.
Sustainability 2021, 13, 3785 12 of 16

Figure 6. Examples of the non-linear and linear fitting of the (a) Langmuir and (b) Freundlich
isotherm models to the adsorption data of Ni2+ and Pb2+ at 20 and 40 mg L−1 .

A reasonable fit to the adsorption data of Ni2+ was also estimated by the non-linear
H–J isotherm with R2 = 0.86 (Table 4), supporting its multilayer adsorption onto EU-biochar
with heterogeneous pore distribution, similar to the Freundlich and Halsey models. The
model constant AHJ was much higher in the linear than in the non-linear form for both
metal ions, while AHJ and BHJ (model constant) were significantly higher for the adsorption
of Pb2+ than for the adsorption of Ni2+ . In addition, the BHJ values in the non-linear H–J
isotherm were almost double the values in the linear isotherm for both metal ions.
The linear form of the Jovanovic isotherm was not satisfactory due to the very low
R2 values (0.55 and 0.46 for Ni2+ and Pb2+ , respectively) and the great deviation of the
theoretical from the experimental qm values. The model constant Kj was higher for the
adsorption of Ni2+ than for the adsorption of Pb2+ in the linear form of the model, while a
reverse trend was observed in the non-linear form (Table 4). In addition, the non-linear
Jovanovic model provided satisfactory results with R2 values of 0.91 and 0.87 and slightly
underestimated theoretical qm values of about 6% and 8% compared to the experimental
values for Ni2+ and Pb2+ , respectively. Thus, similar to the Langmuir model, the non-
linear Jovanovic model supported the localized monolayer adsorption of both metal ions
onto EU-biochar without lateral interactions, suggesting the development of mechanical
interactions between the adsorbed and desorbed molecules [67,68].

4. Conclusions
EU-biochar produced via thermal degradation from EU sawdust was used as a po-
tential adsorbent for Ni2+ and Pb2+ contaminants in synthetic wastewater. EDX and FTIR
spectroscopy demonstrated that the metal ions were successfully adsorbed by interacting
with the carboxylic groups on the biochar surface. Further experiments on the uptake of
both metal ions and the removal efficiency of EU-biochar indicated that the adsorption
equilibrium was reached at 30 min, while Pb2+ was removed faster than Ni2+ , suggesting
the development of stronger and faster interactions between Pb2+ and the EU-biochar
surface. Additional studies by varying the initial metal ion concentration, the adsorbent
dose, and the pH of the metal solutions indicated that the simultaneous improvement of
Sustainability 2021, 13, 3785 13 of 16

the adsorption capacity of EU-biochar and the corresponding percentage removal for Ni2+
and Pb2+ could only be achieved by increasing the pH of the metal solutions from 2.0 to
10.0 and from 2.0 to 8.0, respectively.
A series of kinetic and isotherm fitting models were further employed to study the
removal mechanism of Ni2+ and Pb2+ . The adsorption data fitted well to the linear and non-
linear forms of the PSO and Elovich kinetic models, suggesting activated chemisorption
as the removal mechanism of both metal ions. Among the applied isotherm models,
the Langmuir model could adequately explain the monolayer adsorption of both metal
ions, while the Temkin model fitted perfectly the adsorption data of Ni2+ , suggesting its
heterogeneous adsorption onto EU-biochar. The non-linear D–R isotherm also suggested
that both metal ions are adsorbed onto EU-biochar via physisorption, while the non-
linear H–J isotherm supported the multilayer adsorption of Ni2+ with heterogeneous pore
distribution. Finally, the non-linear Jovanovic model supported the localized monolayer
adsorption of both metal ions onto EU-biochar without lateral interactions.

Author Contributions: Conceptualization, M.T.A. and M.S.; methodology, M.S.; software, M.T.A.
and A.A.A.; validation, M.T.A. and M.S.; formal analysis, M.S.; investigation, M.T.A. and A.A.A.;
resources, A.A.A.; data curation, M.T.A. and M.S.; writing—original draft preparation, M.T.A.;
writing—review and editing, M.T.A. and M.S.; visualization, M.S.; supervision, M.T.A.; project
administration, A.A.A. and M.S.; funding acquisition, A.A.A. All authors have read and agreed to
the published version of the manuscript.
Funding: This project was funded by the National Plan for Science, Technology and Innovation
(MAARIFAH), King Abdulaziz City for Science and Technology, Kingdom of Saudi Arabia, Award
Number (12-WAT2623-02).
Acknowledgments: The authors appreciate the Deanship of Scientific Research and RSSU at King
Saud University for their technical support (manuscript editing services).
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Zhang, P.; Yang, D.; Zhang, Y.; Li, Y.; Liu, Y.; Cen, Y.; Zhang, W.; Geng, W.; Rong, T.; Liu, Y.; et al. Re-Examining the Drive Forces
of China’s Industrial Wastewater Pollution Based on GWR Model at Provincial Level. J. Clean. Prod. 2020, 262, 121309. [CrossRef]
2. Shafiq, M.; Alazba, A.A.; Amin, M.T. Removal of Heavy Metals from Wastewater Using Date Palm as a Biosorbent: A Comparative
Review. Sains Malays. 2018, 47, 35–49. [CrossRef]
3. Saritas, O.; Proskuryakova, L.N. Water Resources—an Analysis of Trends, Weak Signals and Wild Cards with Implications for
Russia. Foresight 2017, 19, 152–173. [CrossRef]
4. Qi, M.; Yang, Y.; Zhang, X.; Zhang, X.; Wang, M.; Zhang, W.; Lu, X.; Tong, Y. Pollution Reduction and Operating Cost Analysis of
Municipal Wastewater Treatment in China and Implication for Future Wastewater Management. J. Clean. Prod. 2020, 253, 120003.
[CrossRef]
5. Mohan, D.; Sarswat, A.; Ok, Y.S.; Pittman, C.U. Organic and Inorganic Contaminants Removal from Water with Biochar, a
Renewable, Low Cost and Sustainable Adsorbent—A Critical Review. Bioresour. Technol. 2014, 160, 191–202. [CrossRef]
6. Islam, M.A.; Awual, M.R.; Angove, M.J. A Review on Nickel(II) Adsorption in Single and Binary Component Systems and Future
Path. J. Environ. Chem. Eng. 2019, 7, 103–305. [CrossRef]
7. Hua, M.; Zhang, S.; Pan, B.; Zhang, W.; Lv, L.; Zhang, Q. Heavy Metal Removal from Water/Wastewater by Nanosized Metal
Oxides: A Review. J. Hazard. Mater. 2012, 211–212, 317–331. [CrossRef]
8. Cerná, M. Use of Solvent Extraction for the Removal of Heavy Metals from Liquid Wastes. Environ. Monit. Assess. 1995, 34,
151–162. [CrossRef] [PubMed]
9. Bashir, A.; Malik, L.A.; Ahad, S.; Manzoor, T.; Bhat, M.A.; Dar, G.N.; Pandith, A.H. Removal of Heavy Metal Ions from Aqueous
System by Ion-Exchange and Biosorption Methods. Environ. Chem. Lett. 2019, 17, 729–754. [CrossRef]
10. Barakat, M.A. New Trends in Removing Heavy Metals from Industrial Wastewater. Arab. J. Chem. 2011, 4, 361–377. [CrossRef]
11. Oncel, M.S.; Muhcu, A.; Demirbas, E.; Kobya, M. A Comparative Study of Chemical Precipitation and Electrocoagulation for
Treatment of Coal Acid Drainage Wastewater. J. Environ. Chem. Eng. 2013, 1, 989–995. [CrossRef]
12. Ahmad, J.; Naeem, S.; Ahmad, M.; Usman, A.R.A.; Al-Wabel, M.I. A Critical Review on Organic Micropollutants Contamination
in Wastewater and Removal through Carbon Nanotubes. J. Environ. Manag. 2019, 246, 214–228. [CrossRef] [PubMed]
13. Wang, X.S.; Miao, H.H.; He, W.; Shen, H.L. Competitive Adsorption of Pb(II), Cu(II), and Cd(II) Ions on Wheat-Residue Derived
Black Carbon. J. Chem. Eng. Data 2011, 56, 444–449. [CrossRef]
Sustainability 2021, 13, 3785 14 of 16

14. Yu, J.-X.; Wang, L.-Y.; Chi, R.-A.; Zhang, Y.-F.; Xu, Z.-G.; Guo, J. Competitive Adsorption of Pb2+ and Cd2+ on Magnetic Modified
Sugarcane Bagasse Prepared by Two Simple Steps. Appl. Surf. Sci. 2013, 268, 163–170. [CrossRef]
15. Reddy, N.; Yang, Y. Biofibers from Agricultural Byproducts for Industrial Applications. Trends Biotechnol. 2005, 23, 22–27.
[CrossRef] [PubMed]
16. Oh, T.K.; Choi, B.; Shinogi, Y.; Chikushi, J. Characterization of Biochar Derived from Three Types of Biomass. J. Fac. Agric. Kyushu
Univ. 2012, 57, 61–66. [CrossRef]
17. Sciban, M.; Radetic, B.; Kevresan, Z.; Klasnja, M. Adsorption of Heavy Metals from Electroplating Wastewater by Wood Sawdust.
Bioresour. Technol. 2007, 98, 402–409. [CrossRef]
18. Sud, D.; Mahajan, G.; Kaur, M. Agricultural Waste Material as Potential Adsorbent for Sequestering Heavy Metal Ions from
Aqueous Solutions—A Review. Bioresour. Technol. 2008, 99, 6017–6027. [CrossRef]
19. Muramatsu, H.; Kim, Y.A.; Yang, K.-S.; Cruz-Silva, R.; Toda, I.; Yamada, T.; Terrones, M.; Endo, M.; Hayashi, T.; Saitoh, H. Rice
Husk-Derived Graphene with Nano-Sized Domains and Clean Edges. Small 2014, 10, 2766–2770. [CrossRef]
20. Suman; Kardam, A.; Gera, M.; Jain, V.K. A Novel Reusable Nanocomposite for Complete Removal of Dyes, Heavy Metals and
Microbial Load from Water Based on Nanocellulose and Silver Nano-Embedded Pebbles. Environ. Technol. 2015, 36, 706–714.
[CrossRef]
21. Inyang, M.; Gao, B.; Yao, Y.; Xue, Y.; Zimmerman, A.; Mosa, A.; Pullammanappallil, P.; Ok, Y.S.; Cao, X. A Review of Biochar as a
Low-Cost Adsorbent for Aqueous Heavy Metal Removal. Crit. Rev. Environ. Sci. Technol. 2016, 46, 406–433. [CrossRef]
22. Huang, G.; Wang, D.; Ma, S.; Chen, J.; Jiang, L.; Wang, P. A New, Low-Cost Adsorbent: Preparation, Characterization, and
Adsorption Behavior of Pb(II) and Cu(II). J. Colloid Interface Sci. 2015, 445, 294–302. [CrossRef]
23. Xie, Y.; Yuan, X.; Wu, Z.; Zeng, G.; Jiang, L.; Peng, X.; Li, H. Adsorption Behavior and Mechanism of Mg/Fe Layered Double
Hydroxide with Fe3O4-Carbon Spheres on the Removal of Pb(II) and Cu(II). J. Colloid Interface Sci. 2019, 536, 440–455. [CrossRef]
24. Bouhamed, F.; Elouear, Z.; Bouzid, J.; Ouddane, B. Batch Sorption of Pb(II) Ions from Aqueous Solutions Using Activated Carbon
Prepared from Date Stones: Equilibrium, Kinetic, and Thermodynamic Studies. Desalination Water Treat. 2014, 52, 2261–2271.
[CrossRef]
25. Yang, R.; Li, H.; Huang, M.; Yang, H.; Li, A. A Review on Chitosan-Based Flocculants and Their Applications in Water Treatment.
Water Res. 2016, 95, 59–89. [CrossRef]
26. Hegazi, H.A. Removal of Heavy Metals from Wastewater Using Agricultural and Industrial Wastes as Adsorbents. HBRC J. 2013,
9, 276–282. [CrossRef]
27. Sočo, E.; Kalembkiewicz, J. Adsorption of Nickel(II) and Copper(II) Ions from Aqueous Solution by Coal Fly Ash. J. Environ.
Chem. Eng. 2013, 1, 581–588. [CrossRef]
28. Song, M.; Wei, Y.; Cai, S.; Yu, L.; Zhong, Z.; Jin, B. Study on Adsorption Properties and Mechanism of Pb2+ with Different Carbon
Based Adsorbents. Sci. Total Environ. 2018, 618, 1416–1422. [CrossRef] [PubMed]
29. Jindo, K.; Mizumoto, H.; Sawada, Y.; Sanchez-Monedero, M.A.; Sonoki, T. Physical and Chemical Characterization of Biochars
Derived from Different Agricultural Residues. Biogeosciences 2014, 11, 6613–6621. [CrossRef]
30. Zhao, J.; Shen, X.-J.; Domene, X.; Alcañiz, J.-M.; Liao, X.; Palet, C. Comparison of Biochars Derived from Different Types of
Feedstock and Their Potential for Heavy Metal Removal in Multiple-Metal Solutions. Sci. Rep. 2019, 9, 9869. [CrossRef]
31. Ding, Z.; Hu, X.; Wan, Y.; Wang, S.; Gao, B. Removal of Lead, Copper, Cadmium, Zinc, and Nickel from Aqueous Solutions by
Alkali-Modified Biochar: Batch and Column Tests. J. Ind. Eng. Chem. 2016, 33, 239–245. [CrossRef]
32. Ahmad, M.; Ahmad, M.; Usman, A.R.A.; Al-Faraj, A.S.; Ok, Y.S.; Hussain, Q.; Abduljabbar, A.S.; Al-Wabel, M.I. An Efficient
Phosphorus Scavenging from Aqueous Solution Using Magnesiothermally Modified Bio-Calcite. Environ. Technol. 2017, 1–12.
[CrossRef]
33. Wang, L.; Wang, Y.; Ma, F.; Tankpa, V.; Bai, S.; Guo, X.; Wang, X. Mechanisms and Reutilization of Modified Biochar Used for
Removal of Heavy Metals from Wastewater: A Review. Sci. Total Environ. 2019, 668, 1298–1309. [CrossRef]
34. Ahmad, M.; Rajapaksha, A.U.; Lim, J.E.; Zhang, M.; Bolan, N.; Mohan, D.; Vithanage, M.; Lee, S.S.; Ok, Y.S. Biochar as a Sorbent
for Contaminant Management in Soil and Water: A Review. Chemosphere 2014, 99, 19–33. [CrossRef]
35. Li, H.; Dong, X.; da Silva, E.B.; de Oliveira, L.M.; Chen, Y.; Ma, L.Q. Mechanisms of Metal Sorption by Biochars: Biochar
Characteristics and Modifications. Chemosphere 2017, 178, 466–478. [CrossRef]
36. Xu, X.; Cao, X.; Zhao, L. Comparison of Rice Husk- and Dairy Manure-Derived Biochars for Simultaneously Removing Heavy
Metals from Aqueous Solutions: Role of Mineral Components in Biochars. Chemosphere 2013, 92, 955–961. [CrossRef]
37. Kloss, S.; Zehetner, F.; Dellantonio, A.; Hamid, R.; Ottner, F.; Liedtke, V.; Schwanninger, M.; Gerzabek, M.H.; Soja, G. Characteriza-
tion of Slow Pyrolysis Biochars: Effects of Feedstocks and Pyrolysis Temperature on Biochar Properties. J. Environ. Qual. 2012, 41,
990–1000. [CrossRef]
38. Suliman, W.; Harsh, J.B.; Abu-Lail, N.I.; Fortuna, A.-M.; Dallmeyer, I.; Garcia-Perez, M. Influence of Feedstock Source and
Pyrolysis Temperature on Biochar Bulk and Surface Properties. Biomass Bioenergy 2016, 84, 37–48. [CrossRef]
39. Amin, M.T.; Alazba, A.A.; Shafiq, M. Removal of Copper and Lead Using Banana Biochar in Batch Adsorption Systems: Isotherms
and Kinetic Studies. Arab. J. Sci. Eng. 2017, 1–12. [CrossRef]
40. Rajput, M.S.; Sharma, A.; Sharma, S.; Verma, S. Removal of Lead (II) from Aqueous Solutions by Orange Peel. Int. J. Appl. Res.
2015, 1, 411–413.
Sustainability 2021, 13, 3785 15 of 16

41. Ahmad, M.; Ahmad, M.; Usman, A.R.A.; Al-Faraj, A.S.; Abduljabbar, A.S.; Al-Wabel, M.I. Biochar Composites with Nano
Zerovalent Iron and Eggshell Powder for Nitrate Removal from Aqueous Solution with Coexisting Chloride Ions. Environ. Sci.
Pollut. Res. Int. 2017. [CrossRef]
42. Usman, A.R.A.; Abduljabbar, A.; Vithanage, M.; Ok, Y.S.; Ahmad, M.; Ahmad, M.; Elfaki, J.; Abdulazeem, S.S.; Al-Wabel, M.I.
Biochar Production from Date Palm Waste: Charring Temperature Induced Changes in Composition and Surface Chemistry. J.
Anal. Appl. Pyrolysis 2015, 115, 392–400. [CrossRef]
43. Doğan, M.; Alkan, M.; Demirbaş, Ö.; Özdemir, Y.; Özmetin, C. Adsorption Kinetics of Maxilon Blue GRL onto Sepiolite from
Aqueous Solutions. Chem. Eng. J. 2006, 124, 89–101. [CrossRef]
44. Gunay, A. Application of Nonlinear Regression Analysis for Ammonium Exchange by Natural (Bigadiç) Clinoptilolite. J. Hazard.
Mater. 2007, 148, 708–713. [CrossRef]
45. Manohar, D.M.; Noeline, B.F.; Anirudhan, T.S. Adsorption Performance of Al-Pillared Bentonite Clay for the Removal of Cobalt(II)
from Aqueous Phase. Appl. Clay Sci. 2006, 31, 194–206. [CrossRef]
46. Zaghouane-Boudiaf, H.; Boutahala, M.; Arab, L. Removal of Methyl Orange from Aqueous Solution by Uncalcined and Calcined
MgNiAl Layered Double Hydroxides (LDHs). Chem. Eng. J. 2012, 187, 142–149. [CrossRef]
47. Rajoriya, R.K.; Prasad, B.; Mishra, I.M.; Wasewar, K.L. Adsorption of Benzaldehyde on Granular Activated Carbon: Kinetics,
Equilibrium, and Thermodynamic. Chem. Biochem. Eng. Q. 2007, 21, 219–226.
48. Tang, H.; Zhou, W.; Zhang, L. Adsorption Isotherms and Kinetics Studies of Malachite Green on Chitin Hydrogels. J. Hazard.
Mater. 2012, 209–210, 218–225. [CrossRef] [PubMed]
49. Chowdhury, S.; Mishra, R.; Saha, P.; Kushwaha, P. Adsorption Thermodynamics, Kinetics and Isosteric Heat of Adsorption of
Malachite Green onto Chemically Modified Rice Husk. Desalination 2011, 265, 159–168. [CrossRef]
50. Taty-Costodes, V.C.; Fauduet, H.; Porte, C.; Delacroix, A. Removal of Cd(II) and Pb(II) Ions, from Aqueous Solutions, by
Adsorption onto Sawdust of Pinus Sylvestris. J. Hazard. Mater. 2003, 105, 121–142. [CrossRef] [PubMed]
51. Hamdaoui, O. Dynamic Sorption of Methylene Blue by Cedar Sawdust and Crushed Brick in Fixed Bed Columns. J. Hazard.
Mater. 2006, 138, 293–303. [CrossRef]
52. Liu, Z.; Zhang, F.-S. Removal of Lead from Water Using Biochars Prepared from Hydrothermal Liquefaction of Biomass. J. Hazard.
Mater. 2009, 167, 933–939. [CrossRef]
53. Mahdi, Z.; Yu, Q.J.; El Hanandeh, A. Removal of Lead(II) from Aqueous Solution Using Date Seed-Derived Biochar: Batch and
Column Studies. Appl. Water Sci. 2018, 8, 181. [CrossRef]
54. Yakkala, K.; Yu, M.-R.; Roh, H.; Yang, J.-K.; Chang, Y.-Y. Buffalo Weed (Ambrosia Trifida L. Var. Trifida) Biochar for Cadmium (II)
and Lead (II) Adsorption in Single and Mixed System. Desalination Water Treat. 2013, 51, 7732–7745. [CrossRef]
55. Hu, X.; Xue, Y.; Liu, L.; Zeng, Y.; Long, L. Preparation and Characterization of Na2S-Modified Biochar for Nickel Removal.
Environ. Sci. Pollut. Res. 2018, 25, 9887–9895. [CrossRef] [PubMed]
56. Lyu, H.; Gao, B.; He, F.; Zimmerman, A.R.; Ding, C.; Huang, H.; Tang, J. Effects of Ball Milling on the Physicochemical and
Sorptive Properties of Biochar: Experimental Observations and Governing Mechanisms. Environ. Pollut. 2018, 233, 54–63.
[CrossRef]
57. Aksu, Z.; Tezer, S. Exploited Application of Bacillus Sp. ETL-A & Pseudomonas Sp. ETL-B in Microbial Degradation of Orange 16
Dye. Process. Biochem. 2001, 36, 431–439.
58. Chiou, M.S.; Li, H.Y. Equilibrium and Kinetic Modeling of Adsorption of Reactive Dye on Cross-Linked Chitosan Beads. J. Hazard.
Mater. 2002, 93, 233–248. [CrossRef]
59. Mestre, A.S.; Pires, J.; Nogueira, J.M.F.; Carvalho, A.P. Activated Carbons for the Adsorption of Ibuprofen. Carbon 2007, 45,
1979–1988. [CrossRef]
60. Önal, Y.; Akmil-Başar, C.; Sarıcı-Özdemir, Ç. Elucidation of the Naproxen Sodium Adsorption onto Activated Carbon Prepared
from Waste Apricot: Kinetic, Equilibrium and Thermodynamic Characterization. J. Hazard. Mater. 2007, 148, 727–734. [CrossRef]
61. Hamdaoui, O.; Naffrechoux, E. Modeling of Adsorption Isotherms of Phenol and Chlorophenols onto Granular Activated Carbon:
Part I. Two-Parameter Models and Equations Allowing Determination of Thermodynamic Parameters. J. Hazard. Mater. 2007, 147,
381–394. [CrossRef]
62. Baccar, R.; Sarrà, M.; Bouzid, J.; Feki, M.; Blánquez, P. Removal of Pharmaceutical Compounds by Activated Carbon Prepared
from Agricultural By-Product. Chem. Eng. J. 2012, 211–212, 310–317. [CrossRef]
63. Tan, I.A.W.; Ahmad, A.L.; Hameed, B.H. Adsorption Isotherms, Kinetics, Thermodynamics and Desorption Studies of 2,4,6-
Trichlorophenol on Oil Palm Empty Fruit Bunch-Based Activated Carbon. J. Hazard. Mater. 2009, 164, 473–482. [CrossRef]
64. Foo, K.Y.; Hameed, B.H. Preparation, Characterization and Evaluation of Adsorptive Properties of Orange Peel Based Activated
Carbon via Microwave Induced K2 CO3 Activation. Bioresour. Technol. 2012, 104, 679–686. [CrossRef]
65. Malik, P.K. Use of Activated Carbons Prepared from Sawdust and Rice-Husk for Adsorption of Acid Dyes: A Case Study of Acid
Yellow 36. Dyes Pigment. 2003, 56, 239–249. [CrossRef]
66. Kumar, P.S.; Ramakrishnan, K.; Gayathri, R. Removal of Nickel(II) from Aqueous Solutions by Ceralite IR 120 Cationic Exchange
Resins. J. Eng. Sci. Technol. 2010, 5, 232–243.
Sustainability 2021, 13, 3785 16 of 16

67. Ramadoss, R.; Subramaniam, D. Removal of Divalent Nickel from Aqueous Solution Using Blue-Green Marine Algae: Adsorption
Modeling and Applicability of Various Isotherm Models. Sep. Sci. Technol. 2019, 54, 943–961. [CrossRef]
68. Saadi, R.; Saadi, Z.; Fazaeli, R. Determination of Axial Dispersion and Overall Mass Transfer Coefficients for Ni (II) Adsorption
on Nanostructured γ-Alumina in a Fixed Bed Column: Experimental and Modeling Studies. Desalination Water Treat. 2015, 53,
2193–2203. [CrossRef]