Kinetics, thermodynamics and equilibrium in Nickel (II) and Lead

(II) biosorption using corn residues

Abstract
Agricultural residues rich in lignocellulosic biomass are low-cost and sustainable renewable adsorbents
widely used in water treatment. In the present research, thermodynamics, kinetics, and equilibrium of
Nickel (II) and Lead (II) ion biosorption were studied using corn cob (Zea mays). The experiments were
done in a batch system evaluating the effect of temperature and dose of adsorbent; Langmuir and
Freundlich's models were used to study the equilibrium, and thermodynamic and kinetic parameters were
determined. Biosorbent characteristics were studied by FTIR, SEM, and EDS analysis. It was found that
the hydroxyl, carboxyl, and phenolic groups are the major contributors to the removal process. Besides, Pb
(II) forms micro-complexes on the surface of the biomaterial while Ni (II) forms bonds with the active
centers. It was obtained that the highest Ni (II) removal yields are achieved with 0.02 g of adsorbent and
70°C, while Pb(II) removal yields are achieved at 0.003 g and 55°C. A maximum Ni (II) adsorption
capacity of 3.52 mg/g (86%) and 13.32 mg/g (94.3%) for Pb (II) was obtained in 250 and 330 min,
respectively. Pseudo-first-order and pseudo-second-order models fit the data tightly, and Langmuir and
Freundlich models describe the isotherm of the process. Thermodynamic parameters (∆H 0, ∆G0, ∆S0)
suggest the adsorption process of both cations is exothermic, irreversible, and not spontaneous.
Keywords: Heavy metals, Zea mays, adsorption capacity.

1. Introduction
Heavy metal pollution is a problem caused by human activities (industry, agriculture, tanneries,
fertilizer manufacturing, batteries, and mining waste disposal); since these are discharged into the
environment reaching concentrations above the permissible values. Rapid industrial and urban
developments have put significant pressure on natural resources. Water is vital to life; therefore, it is a
scarce resource worth fighting for 1.
Water bodies present a significant risk due to the high solubility of heavy metals, their mobility in
water, resistance to degradation, persistence, and tendency to accumulate in living organisms 2 3, 4.
Lead is harmful to vital organs and systems, and its toxicity triggers enzymatic inhibition 5. Moreover,
Nickel can cause dermatitis, genotoxic effect on lungs, liver, kidneys, and brain, inhibition of
enzymatic action, alteration of protein function, calcium deficiency in bones, DNA damage, cancer,
among others 6 7.
Nowadays, several options are available to remove metal ions from wastewater, such as
coagulation-flocculation, membrane filtration, flotation, chemical precipitation, and electrochemical
precipitation 4 8. However, some of these methods produce a large amount of sludge, which increases
the risk of metal ion leaching. Therefore, simple, stable, and safe systems are needed to remove metal
ions 9. Adsorption is one of the proposed strategies to remove heavy metals in solution. There is a
growing interest in the development of adsorbents that meet some requirements such as open-pore
structure for fast kinetics, accessible adsorption sites, surface properties suitable for high adsorption
capacity, simple synthesis, and low cost 10 11. Heavy metals can also be immobilized through
precipitation 12 13.
Thus, from specialized products to commodities, a wide range of bioproducts and biofuels can be
produced from biomass 14 as bioabsorbents. In addition to their potential characteristics, bio-
absorbents contribute to sustainable development, taking into account that the traditional supply chain
has been replaced by a more environmentally friendly chain that ensures economic development as
well as environmental and social improvement 15.
Environmental uses of biosorbents depend mainly on the mechanisms of interaction with heavy
metals; for water treatment, the presence of multiple contaminants in solution and reuse of the
adsorbent is expected 16. Consequently, it is crucial to identify the mechanisms of interaction between
the adsorbent and the heavy metals for their practical applications.
This research was intended to evaluate the use of corn cob as an adsorbent, its thermodynamics,
kinetics, and balance of Ni (II) and Pb (II) adsorption, as well as the study in a competitive system.
The bioadsorbent was characterized by FTIR, SEM, and EDS, identifying the functional groups
involved in metal removal, morphology, composition, and mechanisms of metal removal. Adsorption
tests were performed in a batch system, evaluating the effect of temperature and dose of adsorbent on
the process.
2. Methodology

2.1 Materials and equipment

Lead (II) nitrate (Pb(NO3)2) and Nickel (II) sulfate (NiSO4) from Sigma Aldrich were used for the
experimental development. Shaker incubator IN-666 from Gemmy industrial brand,
Spectrophotometer IR Shimadzu IRAinfinity-1S, Electron Scanning Microscope JEOL Ltd. model
JSM 6490-LV. All reagents used were analytical grade.

2.2 Experimental design

The design of continuous factor experiments on central composite response surface (star) was
used, as shown in Table 1 and developed with Statgraphics Centurion XVI.II.

Table 1.
Experimental Design
Independent Range and Level
Unit
Variables -α -1 0 +1 +α

Adsorbent quantity g 0.0034 0.02 0.06 0.1 0.1166

Temperature °C 33.79 40 55 70 76.21

2.3 Adsorbent preparation and characterization

The corn cob was collected fresh and in perfect condition. The biomass was washed and dried in
an oven at 70 °C for 24 hours to a constant mass. Then, it was reduced in size using a conventional
screw mill and sorted to 0.355mm. The pretreated material was characterized before, and after the
adsorption process by SEM, EDS, and FTIR analysis to determine the morphology, composition, and
functional groups present that could be involved in the removal process 17 18.
2.4 Adsorption testing

For the adsorption tests, synthetic solutions of Lead and Nickel were prepared in concentrations
of 29.35 mg/L, using Lead (II) nitrate and Nickel (II) sulfate as reagents. The Lead solution was
adjusted to pH 5 and the Nickel solution to pH 6, using NaOH and 1 M HCl. Solutions were exposed
to the biomass at 200 rpm for 24 h, following the experimental design in Table 1. Optimal adsorption
conditions were determined from the results obtained 19 20. The final concentration at equilibrium was
determined by Atomic Absorption Spectroscopy (AA) at 232 and 217 nm for Nickel and Lead,
respectively. Adsorption efficiency and capacity were determined by equations 1 and 2:

C0 −Cf
% R= x 1 00(1)
Ci
V ( C0−Cf )
q e= (2)
m
Where C0 is the initial concentration and C f is the final concentration in mg/L, V the volume in L,
m the mass of adsorbent in g, %R the adsorption efficiency and qe the adsorption capacity of the
adsorbent in mg/g.

Data statistical analysis was performed using Statgraphics Centurion XVI.II by analysis of
variance (ANOVA), effect plots, standardized effect Pareto chart, to determine the incidence of the
evaluated variables and the percentage of Lead and Nickel adsorption.

2.5 Kinetics and adsorption isotherms

Under the optimal conditions of temperature, particle size, and adsorbent dose that presented the
highest percentage of removal for each metal and biomass, kinetic studies were performed by taking
eight samples at different time intervals in 24 h. Experimental kinetic data were adjusted to the
Pseudo First Order, Pseudo Second Order and Elovich models (Table 2) using the curve fitting tool of
the Origin Pro 9 program, in order to know the behavior of Lead and Nickel adsorption with lemon
peel and corn cob over time and to determine the mechanism of the adsorption process in each of
these systems.

Table 2.
Kinetic models of adsorption in the batch system
Model Equation Parameters

Pseudo-first order q t=qe∗1+ e−k ∗t 1 qt (mmol/g): it´s the adsorbed amount in a time
named t
qe (mmol/g): it´s the adsorbed amount in the
equilibrium
k1 (min-1): it´s the first-order kinetic constant

Pseudo-second order t k2 (g/mmo.min): kinetic constant of pseudo-second

q t= order and the initial adsorption rate
1 t
+
2
k 2∗qe e q qe: adsorption capacity in equilibrium

Elovich 1 1 α (mmol·g-1·min-1): it´s the initial rate of adsorption

q t= ∗ln ( α∗β ) + ∗ln t
β β β (mmol·g-1): it´s related to the surface area
covered and the activation energy by chemical
 adsorption.

Adsorption isotherms were performed to describe the quantity of Nickel and Lead in the
equilibrium of the separated solute between the solid and liquid phases. The experiments were
conducted using different concentrations of Lead (20, 40, 60, and 80 ppm) and Nickel (5, 10, 15, and
20 ppm), with a single sample taken at the end of 24 hours. Langmuir and Freundlich models were
used to adjust the data (Table 3).

Table 3.
Adsorption isotherm models in the batch system
Model Equation Parameters

Langmuir K Cf qe: it´s the adsorbed metal

q e =q max concentration in the bioadsorbent
1+ K C f
Cf: it´s the residual concentration
of the metal in the solution
qmax: it´s the maximum adsorption
corresponding to the saturation
sites
K: it´s the ratio of the
adsorption/desorption rate

Freundlich 1 q (mg/g): adsorption capacity

q=K C ne
Ce (mg/L): concentratio in the
equilibrium
K (L/mg): parameter related to the
affinity of the bioadsorbent for
metal ions
n: parameter related to
adsorption intensity

2.6 Thermodynamic parameters

A thermodynamic study was conducted to understand the nature of the Ni(II) and Pb(II)
adsorption process on corn cob. For this purpose, the change in Gibbs' standard free energy (ΔG°),
standard enthalpy (ΔH°) and standard entropy (ΔS°) were calculated, according to the expression in
equations 7-10.

∆ G °=RT . ln k c
(3)

−∆ H ∆ S °
ln k c = +
R.T R
(4)

∆ H °=−m. R
(5)
∆ S °=R . b
(6)

qe
k c=
Ce
(7)
Where Kc is the equilibrium constant, q is the equilibrium solid phase concentration (mg/g), Ce is
the equilibrium concentration (mg/g), R is the ideal gas constant (8,314 J/molK), T is the absolute
temperature in K. ΔH° and ΔS° are determined from the slope and the y-axis intercept of lnKc vs. T-
1, respectively, following Van't Hoff's graphical method.
2.7 Competitive system
The study of the competitive system was done under each metal's optimal adsorption conditions,
varying the concentration of the interfering metal. Initially, the Nickel concentration was fixed by
adjusting the Lead concentration, and subsequently, the Lead concentration was fixed by adjusting the
Nickel concentration.
3. Results and discussion
3.1 Adsorbent characterization
Corn cob EDS spectrum (Figure 1a), demonstrated that the predominant element in the biomass
structure is Carbon (59.62%), followed by Oxygen (35.02%), due to the lignocellulosic nature of the
material; the presence of materials in smaller proportion as Si, K and Sn was also found. After
adsorption of Pb (II) and Ni (II) (Figures 1b and 1c), the presence of the metals on the surface of the
adsorbent was evident. Meanwhile, C and O were the materials with the highest presence in the
adsorbent, with a slight increase in their percentages in weight, which can be attributed to the
formation of links between ions and biomass.

(a) (b) (c)

Fig. 1. EDS spectrum of corn cub (a) before and after of removal of (b) Pb (II) and (c) Ni (II)

Figure 2a presents the spectrum of the corn cob before adsorption and exhibits a porous flaky
surface with an irregular surface, which allows better heterogeneous biosorption due to the large
interface 21. From SEM microphotographs obtained after the adsorption process (Figure 2b), it is
observed that Pb(II) was adsorbed on the surface of the material, evidencing the ion agglomeration
that is attributed to the formation of chelates by microcomplexity 22 23; it was found that the removal of
Ni(II) in corn sludge occurs by electrostatic attraction forces between the active centers and the ion 23.

(a) (b) (c)

Fig. 2. SEM images of corn cob (a) before and after of removal of (b) Pb (II) and (c) Ni (II)

Figure 3 illustrates the FTIR spectrum for corn cob before and after the adsorption process. The
complexity of the lignocellulosic material was confirmed due to the various bands identified. Several
peaks were identified at 3200-3500 cm -1 (OH and secondary amines), 2927.94 cm -1 (methoxy group),
2500 cm-1 (COOH), 1650 cm-1 (C=CC), 1000-1200 cm-1 (alcohols), and 950 cm -1 (C-N) 24. After the
metal adsorption process, changes were observed in width and stretching of the bands: 3390 cm -1
(NH), 2361.19 cm-1 (-C≡N), 1650 cm-1 (C = C), 1120.66 cm-1 (OH), and 1156.55 cm-1 (sulfonamides);
this can be explained by the formation of bonds between the Pb(II) and Ni(II) ions with the active
centers of the material 25.

100

90 CC
T r a n s m itta n c e ( % )

Pb (II)
Ni (II)
80

70

60

50

40

30
0 500 1000 1500 2000 2500 3000 3500 4000 4500
-1
Wavelength (cm )

Fig. 3. The infrared spectrum of corn cob before and after the adsorption.

3.2 Effect of temperature and dose of adsorbent

The amount of biosorbent used for adsorption studies is an important parameter, which
determines the potential of the biosorbent to remove metal ions at a given initial concentration 26.
Moreover, the influence of temperature on metal removal processes determines the mechanisms that
define and control the process 27. The relationship between biosorbent dose, temperature, and the
adsorption capacity of Nickel (II) and Lead (II) is shown in Table 1.

Table 4.
Adsortion Capacity of Pb (II) y Ni (II) at differents conditions of adsorbent dosage and temperature
Adsorbent Quantity (g) Temperature (°C) q (mg/g)

Pb (II) Ni (II)

0.06 33.79 15.9298 3.6519

0.1 40 8.4991 1.2926

0.02 40 41.9664 10.7959

0.06 55 17.1369 3.7323

0.003 55 305.5055 61.7968

0.116 55 8.7629 1.9421

0.02 70 44.0669 8.5639

0.1 70 9.9180 1.9409

0.06 76.21 15.5909 3.2783

Figure 5 describes the effect of the adsorbent dose and temperature on the percentage of Nickel
adsorption on corn silage. It is observed that higher temperature results in lower adsorption, which is
expected to be exothermic 28; moreover, higher adsorbent dose results in better Nickel adsorption
because higher adsorbent quantity increases the availability of active sites available for metal removal
29
.

Gráfica de Efectos Principales para Adsorption efficiency

80

78
Adsorption efficiency

76

74

72

70

68
40.0 70.0 0.02 0.1
Temperature Adsorbent dose

.
Fig. 4. Effect of temperature and adsorbent dose on nickel adsorption.

Figure 6 presents the percentage of Lead adsorption concerning temperature and adsorbent dose;
it is observed that the removal efficiency increases gradually with temperature and adsorbent dose,
and the removal is lowest at low temperature and adsorbent dose. However, maximum adsorption
occurs at the intermediate points of temperature and adsorbent dose; that is because temperature
affects adsorption equilibrium. Higher temperatures tend to improve adsorption capacity and facilitate
porous diffusion of the adsorbent materials 4.
 Gráfica de Efectos Principales para Adsorption efficiency

101

99

Adsorption efficiency
97

95

93

91
40.0 70.0 0.02 0.1
Temperature Adsorbent dose

Fig. 5. Effect of temperature and dosage of adsorbent on lead adsorption

Figure 7a presents the Pareto chart for the process of extracting Nickel cobs from corn cobs; it is
observed that temperature had a negative significance for the adsorption capacity of this system, while
the adsorbent dose had a positive effect. Figure 7b illustrates the Pareto diagram of Lead removal; it is
observed that temperature and adsorbent dose, in the ranges evaluated, had no significant effect on
adsorption in this system.

Diagrama de Pareto Estandarizada para Adsorption efficiency Diagrama de Pareto Estandarizada para Adsorption efficiency

+ +
A:Temperature B:Adsorbent dose
- -

B:Adsorbent dose AA

BB BB

A:Temperature
AA

AB
AB

0 1 2 3 4
0 1 2 3 4 Efecto estandarizado
Efecto estandarizado

(a) (b)

Fig. 6. Pareto diagram for the adsorption of (a) Nickel and (b) Lead on corn cob

The analysis of variance (Table 5) indicates the numerical significance of the independent
variables in the ranges evaluated on the Nickel and Lead removal process with a P-value lower than
0.05, corroborating the findings of the Pareto chart in Figure 7.

Table 5.
Analysis of Variance for Lead and Nickel Adsorption
Source Nickel Lead

Sum of Mean F P Sum of Mean F P

Df Df
Squares Square Ratio Value Squares Square Ratio Value

A:Temperatur
180,506 1 180,506 16,70 0,0150 28,2522 1 28,2522 0,85 0,4080
e
B:Adsorbent
124,462 1 124,462 11,51 0,0274 80,219 1 80,219 2,42 0,1946
dosage
AA 49,3199 1 49,3199 4,56 0,0995 142,003 1 142,003 4,29 0,1072
 AB 2,605 1 2,605 0,24 0,6492 23,242 1 23,242 0,70 0,4493
BB 63,3334 1 63,3334 5,86 0,0727 94,8552 1 94,8552 2,86 0,1658
Total Error 43,2385 4 10,8096 132,487 4 33,1218

3.3 Adsorption kinetics

Figure 10 presents the experimental data adjustment to the pseudo-first-order, pseudo-second-
order, and Elovich kinetic models (Table 2), in order to determine the steps that control the process.
Based on the adjustment, it can be established that the first- and second-order models best describe the
Nickel and Lead removal data with R2 d 0.994 and 0.999, respectively.

14

12
Pb (II)
Ni (II)
10
PFO- Pb (II)
PFO- Ni (II)
qt (mg/g)

PSO- Pb (II)
8
PSO- Ni (II)
Elovich- Pb (II)
6 Elovich- Ni (II)

0
0 200 400 600 800 1000 1200 1400 1600
Time (min)

Fig. 1 Adsorption kinetics for Lead-Corn cob System

Figure 10 indicates that the adsorption of both ions was very fast in the initial stages of the
process, and from the 60th minute, it gradually decreases until equilibrium, suggesting that the
availability of active sites in the biomass is reduced 30. The adjustment to the pseudo-first-order model
establishes that the adsorption rate depends on a mechanism operating at an active site on the biomass
surface 31. Moreover, the pseudo-second-order model states that the mechanism that controls
adsorption is chemical, so the rate of adsorption is limited by valence forces given by the exchange of
electrons between the adsorbate and the adsorbent 32.
Table 6 depicts the adjustment parameters of the kinetic models for the adsorption of Nickel (II)
and Lead (II) on corn cob; it is established that the theoretical adsorption capacity (q e) was correlated
with the data obtained experimentally (3.52 mg/g for Nickel and 13.32 mg/g for Lead).

Table 6.
Adjusting parameters of the kinetic models of Ni(II) and Pb(II) adsorption
Model Parameters Nickel (II) Lead (II)

qe (mg/g) 3,5055 13,2091

Pseudo-First
k1 (min-1) 91,64897 0,5408
Order
0,9994 0,9996
R2
Pseudo-Second qe (mg/g) 3,5055 13,2042
Order
k2 (g/mg*min) 3,11E+13 8,5839
 0,9994 0,9996
R2
α (mg/g*min) 3,653544 1,41E+43

Elovich β (g/mg) 31,621 8,04733

0,996 0,997
R2

3.4 Adsorption isotherms

Adsorption isotherms describe the concentration dependence of the degree of adsorption at a
constant temperature, and the nature of the binding forces between the adsorbate and the adsorbent,
such as physical or chemical forces 33. The equilibrium data for Nickel and Lead were fitted to the
Langmuir and Freundlich isotherm models and are presented in Figure 11, at the optimum condition
of temperature, adsorbent dosage, and particle size for each metal; Table 7 shows the adjustment
parameters.

12

1.6
10
1.4

1.2 8

1.0
qe (mg/g)

6
qe (mg/g)

0.8
4
0.6

0.4 Experimental 2 Datos experimentales

Langmuir Langmuir
0.2 Freundlich
0 Freundlich
0.0
0 2 4 6 8 -0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
Ce (mg/L) Ce (mg/L)

(a) (b)
Fig. 7. Adsorption isotherms of (a) Ni (II) and (b) Pb (II) on corn cob obtained by non-linear regression

As shown in Figure 8 and the parameters in Table 4, both models showed good correlation;
however, Freundlich's model describes better the data behavior for the two metals evaluated at the
concentrations, considering the adjustment shown in the graphs and the correlation parameters (R 2).
This suggests that both physical and chemical mechanisms have an effect on the adsorption process
and that this process occurs on the heterogeneous outer surface of the biomass 31.

Table 7.
Adjusting parameters of Ni(II) and Pb(II) adsorption isothermal models
Model Parameter Ni (II) Pb (II)

qmax (mg/g) 1.5941 4.9944

Langmuir b (L/g) 1248.6 14700.5
 R2 0.9481 0.935

Freundlich kf (mg/g)(L/mg)1.0821 0.162 7.240

n 0.899 0.821

1/n 1.1123 1.2180

R2 0.9532 0.9489

3.5 Adsorption thermodynamic

The thermodynamic consideration of the adsorption process is essential to assume that the process
is feasible or not, whether exothermic or endothermic. The Van't Hoff equation was used to calculate
the values of ΔH°, ΔG°, and ΔS°, using equations 3 to 7. The thermodynamic absorption parameters
of Ni(II) and Pb(II) are reported in Table 8; enthalpy was found to have negative values for the
removal of both metals, indicating the exothermic character of the system 31. This is consistent with
the increased removal of Pb(II) and Ni(II) as temperature increases (Table 1). Furthermore, the
negative value of the adsorption entropy shows that the process presents a modification in the surface
of the adsorbent, so there is a low possibility of reversibility 34. The positive values of Gibbs' energy
prove that the system is not spontaneous, so it is necessary to provide energy to the system 35.

Table 8.
Thermodynamic parameters
Temperature Ni (II) Pb (II)
(ºC)
ΔHº (KJ/mol) ΔSº (KJ/ ΔGº (KJ/mol) ΔHº ΔSº (KJ/ ΔGº
mol*K) (KJ/mol) mol*K) (KJ/mol)

306,9 -7.4995 -0.05312 8.7995 -4.0653 -0.0259 3.8912

328,2 - - 9.9309 - - 4.4435
349,4 - - 11.0570 - - 4.9932

4. Conclusions
It was found that the hydroxyl, carboxyl, and phenolic groups are the major contributors to the
removal process and that Pb (II) forms coordination micro-complexes on the surface of the
biomaterial while Ni (II) forms bonds with the active centers. It was obtained that the best Ni (II)
removal yields are achieved with 0.02 g of adsorbent and 70°C, while Pb (II) at 0.003 g and 55°C. A
maximum Ni (II) adsorption capacity of 3.52 mg/g (86%) and 13.32 mg/g (94.3%) for Pb (II) was
achieved at 250 and 330 min, respectively. Pseudo-first-order and pseudo-second-order models fit the
data best, and Langmuir's and Freundlich's models describe the isotherm of the process.
Thermodynamic parameters (∆H0, ∆G0, ∆S0) suggest that the adsorption process of both cations is
exothermic, irreversible, and not spontaneous.
References
1. Liu, Z.; Deng, X.; Wang, M.; et al. BSA-modified polyethersulfone membrane: Preparation,
characterization and biocompatibility. J Biomater Sci Polym Ed. 2009.
https://doi.org/10.1163/156856209X412227.
2. Raval, N. P.; Shah, P. U.; Shah, N. K. Adsorptive removal of nickel (II) ions from aqueous
environment: A review. J Environ Manage. 2016, 179:1–20.
https://doi.org/10.1016/j.jenvman.2016.04.045.
3. Neris, J. B.; Luzardo, F. H. M.; da Silva, E. G. P.; Velasco, F. G. Evaluation of adsorption processes of
metal ions in multi-element aqueous systems by lignocellulosic adsorbents applying different isotherms:
A critical review. Chem Eng J. 2019, 357:404–20. https://doi.org/10.1016/j.cej.2018.09.125.
4. Hernández Rodiguez, M.; Yperman, J.; Carleer, R.; et al. Adsorption of Ni(II) on spent coffee and
coffee husk based activated carbon. J Environ Chem Eng. 2018, 6(1):1161–70.
https://doi.org/10.1016/j.jece.2017.12.045.
5. Basu, M.; Guha, A. K.; Ray, L. Adsorption of Lead on Lentil Husk in Fixed Bed Column Bioreactor.
Bioresour Technol. 2019, 283(December 2018):86–95. https://doi.org/10.1016/j.biortech.2019.02.133.
6. Song, X.; Fiati Kenston, S. S.; Kong, L.; Zhao, J. Molecular mechanisms of nickel induced
neurotoxicity and chemoprevention. Toxicology. 2017, 392:47–54.
https://doi.org/10.1016/j.tox.2017.10.006.
7. Singh, S.; Shukla, S. R. Theoretical studies on adsorption of Ni(II) from aqueous solution using Citrus
limetta peels. Environ Prog Sustain Energy. 2017. https://doi.org/10.1002/ep.12526.
8. Bhanvase, B. A.; Ugwekar, R. P.; Mankar, R. B. Novel Water Treatment and Separation Methods :
Simulation of Chemical Processes. n.d.
9. Yi, Y.; Lv, J.; Liu, Y.; Wu, G. Synthesis and application of modified Litchi peel for removal of
hexavalent chromium from aqueous solutions. J Mol Liq. 2017, 225:28–33.
https://doi.org/10.1016/j.molliq.2016.10.140.
10. Dai, Y.; Sun, Q.; Wang, W.; et al. Utilizations of agricultural waste as adsorbent for the removal of
contaminants: A review. Chemosphere. 2018, 211:235–53.
https://doi.org/10.1016/j.chemosphere.2018.06.179.
11. De Gisi, S.; Lofrano, G.; Grassi, M.; Notarnicola, M. Characteristics and adsorption capacities of low-
cost sorbents for wastewater treatment: A review. Sustain Mater Technol. 2016, 9:10–40.
https://doi.org/10.1016/J.SUSMAT.2016.06.002.
12. Shi, J.; Fan, X.; Tsang, D. C. W.; et al. Removal of lead by rice husk biochars produced at different
temperatures and implications for their environmental utilizations. Chemosphere. 2019, 235:825–31.
https://doi.org/10.1016/j.chemosphere.2019.06.237.
13. Shen, Z.; Hou, D.; Jin, F.; et al. Effect of production temperature on lead removal mechanisms by rice
straw biochars. Sci Total Environ. 2019. https://doi.org/10.1016/j.scitotenv.2018.11.282.
14. Ouhimmou, M.; Rönnqvist, M.; Lapointe, L.-A. Assessment of sustainable integration of new products
into value chain through a generic decision support model: An application to the forest value chain.
Omega. 2019:102173. https://doi.org/10.1016/J.OMEGA.2019.102173.
15. Babazadeh, R.; Razmi, J.; Pishvaee, M. S.; Rabbani, M. A sustainable second-generation biodiesel
supply chain network design problem under risk. Omega. 2017, 66:258–77.
https://doi.org/10.1016/J.OMEGA.2015.12.010.
16. Shen, Z.; Zhang, Y.; McMillan, O.; Jin, F.; Al-Tabbaa, A. Characteristics and mechanisms of nickel
adsorption on biochars produced from wheat straw pellets and rice husk. Environ Sci Pollut Res. 2017,
24(14):12809–19. https://doi.org/https://doi.org/10.1007/s11356-017-8847-2.
17. Mondal, S.; Aikat, K.; Halder, G. Biosorptive uptake of ibuprofen by chemically modified Parthenium
hysterophorus derived biochar: Equilibrium, kinetics, thermodynamics and modeling. Ecol Eng. 2016,
92:158–72. https://doi.org/10.1016/j.ecoleng.2016.03.022.
18. Manirethan, V.; Gupta, N.; Balakrishnan, R. M.; Raval, K. Batch and continuous studies on the removal
of heavy metals from aqueous solution using biosynthesised melanin-coated PVDF membranes.
Environ Sci Pollut Res. 2019:1–15. https://doi.org/10.1007/s11356-019-06310-8.
19. Allahdin, O.; Mabingui, J.; Wartel, M.; Boughriet, A. Removal of Pb 2+ ions from aqueous solutions by
fixed-BED column using a modified brick: (Micro)structural, electrokinetic and mechanistic aspects.
Appl Clay Sci. 2017, 148(July):56–67. https://doi.org/10.1016/j.clay.2017.08.002.
20. Manjuladevi, M.; Anitha, R.; Manonmani, S. Kinetic study on adsorption of Cr (VI), Ni (II), Cd (II) and
Pb (II) ions from aqueous solutions using activated carbon prepared from Cucumis melo peel. Appl
Water Sci. 2018, 8(1):36. https://doi.org/10.1007/s13201-018-0674-1.
21. Pradhan, P.; Arora, A.; Mahajani, S. M. Pilot scale evaluation of fuel pellets production from garden
 waste biomass. Energy Sustain Dev. 2018, 43:1–14. https://doi.org/10.1016/j.esd.2017.11.005.
22. Medellín-Castillo, N. A.; Hernández-Ramírez, M. G.; Salazar-Rábago, J. J.; Labrada-Delgado, G. J.;
Aragón-Piña, A. Bioadsorción de Plomo (II) presente en solución acuosa sobre residuos de fibras
naturales procedentes de la industria ixtlera (Agave lechuguilla Torr.Y Yucca carnerosana (Trel.)
McKelvey). Rev Int Contam Ambient. 2017, 33(2):269–80.
https://doi.org/10.20937/RICA.2017.33.02.08.
23. Tejada-Tovar, C.; Gonzalez-Delgado, A.; Villabona-Ortiz, A. Characterization of Residual Biomasses
and Its Application for the Removal of Lead Ions from Aqueous Solution. Appl Sci. 2019, 9(21):4486.
https://doi.org/10.3390/app9214486.
24. Johari, K.; Saman, N.; Song, S. T.; Chin, C. S.; Kong, H.; Mat, H. Adsorption enhancement of elemental
mercury by various surface modified coconut husk as eco-friendly low-cost adsorbents. Int Biodeterior
Biodegrad. 2016, 109:45–52. https://doi.org/10.1016/j.ibiod.2016.01.004.
25. Tejada-Tovar, C.; Villabona-Ortíz, A.; González-Delgado, Á. D.; Granados-Conde, C.; Jiménez-
Villadiego, M. Kinetics of Mercury and Nickel adsorption using chemically pretrated cocoa
(Theobroma cacao) husk. Trans ASABE. 2019, 62(2):461–6. https://doi.org/10.13031/trans.13133.
26. Burevska, K. A.; Memedi, H.; Lisichkov, K.; et al. Biosorption of nickel ions from aqueous solutions by
natural and modified peanut husks: equilibrium and kinetics 2017, 00(2011):1–9.
https://doi.org/10.1111/wej.12325.
27. Yin, W.; Zhao, C.; Xu, J.; Zhang, J.; Guo, Z.; Shao, Y. Removal of Cd(II) and Ni(II) from aqueous
solutions using activated carbon developed from powder-hydrolyzed-feathers and Trapa natans husks.
Colloids Surfaces A Physicochem Eng Asp. 2019, 560:426–33.
https://doi.org/10.1016/j.colsurfa.2018.10.031.
28. Cherik, D.; Louhab, K. A kinetics, isotherms, and thermodynamic study of diclofenac adsorption using
activated carbon prepared from olive stones. J Dispers Sci Technol. 2018, 39(6):814–25.
https://doi.org/10.1080/01932691.2017.1395346.
29. Ibisi, N.; Asoluka, C. Use of agro-waste (Musa paradisiaca peels) as a sustainable biosorbent for toxic
metal ions removal from contaminated water. Chem Int. 2018, 4(1):52–9.
30. De Luna, M. D. G.; Murniati; Budianta, W.; Rivera, K. K. P.; Arazo, R. O. Removal of sodium
diclofenac from aqueous solution by adsorbents derived from cocoa pod husks. J Environ Chem Eng.
2017, 5(2):1465–74.
31. Da’Na, E.; Awad, A. Regeneration of spent activated carbon obtained from home filtration system and
applying it for heavy metals adsorption. J Environ Chem Eng. 2017, 5(4):3091–9.
https://doi.org/10.1016/j.jece.2017.06.022.
32. Chen, Y.; Wang, H.; Zhao, W.; Huang, S. Four different kinds of peels as adsorbents for the removal of
Cd (II) from aqueous solution: Kinetics, isotherm and mechanism. J Taiwan Inst Chem Eng. 2018.
https://doi.org/10.1016/j.jtice.2018.03.046.
33. Naseem, K.; Huma, R.; Shahbaz, A.; et al. Extraction of Heavy Metals from Aqueous Medium by Husk
Biomass: Adsorption Isotherm, Kinetic and Thermodynamic study. Zeitschrift Fur Phys Chemie. 2019,
233(2):201–23. https://doi.org/10.1515/zpch-2018-1182.
34. Dobrosz-Gómez, I.; Gómez, M.; Santa, C. Optimización del Proceso de Adsorción de Cr (VI) sobre
Carbón Activado de Origen Bituminoso. Inf Tecnológica. 2018, 29(Vi):43–56.
35. Haroon, H.; Ashfaq, T.; Gardazi, S. M. H.; et al. Equilibrium kinetic and thermodynamic studies of
Cr(VI) adsorption onto a novel adsorbent of Eucalyptus camaldulensis waste: Batch and column
reactors. Korean J Chem Eng. 2016, 33(10):2898–907. https://doi.org/10.1007/s11814-016-0160-0.