Journal of Environmental Chemical Engineering 7 (2019) 103317

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Journal of Environmental Chemical Engineering

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Adsorption performance and mechanism of a low-cost biosorbent from spent T

seedcake of Calophyllum inophyllum in simultaneous cleanup of potentially
toxic metals from industrial wastewater
⁎
Adeniyi Abiodun Adenuga , Olufemi David Amos, John Adekunle Oyedele Oyekunle,
Eseoghene Helen Umukoro
Department of Chemistry, Obafemi Awolowo University, Ile Ife, 220005, Nigeria

A R T I C LE I N FO A B S T R A C T

Keywords: Among the contaminants that are frequently associated with industrial wastewaters, potentially toxic metals are
Wastewater of great health concern because they are non-biodegradable and can be transformed by biochemical processes to
Agricultural waste more poisonous metal-organic complexes. Thus, safe and adequate disposal of wastewater containing these
Potentially toxic metals metals into the environment remains a front-burner challenge. This study investigated metal ions removal from
Kinetics
wastewaters using adsorbents generated from the Spent Seedcake of Calophyllum inophyllum (SSCI) as an al-
Adsorption isotherms
Thermodynamics
ternative low-cost adsorbent. Batch adsorption process was employed to demonstrate the adsorption capacity for
the multi-component removal of Pb(II), Cd(II) and Zn(II) at optimized experimental conditions. Carbonization
and microwaving of the biosorbent produced an optimal performance for the uptake of the metals at solution pH
of 9, temperature of 30 °C, dosage, 10 g/L and 60 min equilibrium time. The maximum adsorption capacities of
the biosorbent were 52.63, 51.28 and 17.99 mg/g for Pb2+, Cd2+and Zn2+ respectively. The adsorption kinetics
of the metals unto the biosorbent was adequately described by a pseudo-second-order kinetic model with po-
sitive enthalpy (ΔH) indicating the endothermic nature of the adsorption process while the negative values of the
Gibbs free energy (ΔG) confirmed the spontaneity of the adsorption process for all the metals studied.The ef-
fectiveness of the biosorbent was tested with real wastewater samples and a removal of the metals between
55–71% was achieved.

1. Introduction biochemical processes to more poisonous metal-organic complexes

Industrialization is one of the major marks of development in any
nation. However, there is no industrial activity without peculiar direct
or indirect impact on the environment. Among the major issues of in-
dustrial development is the generation of wastewaters, which always
contain harmful chemicals such as potentially toxic metals (e.g., Pb, Cd,
Zn, Cu, Co,As, Hg, etc.), organic pollutants, and microbial pollutants,
among others. The existence of potentially toxic metals at elevated le-
vels in most environmental media is consequently a fall out of in-
creasing advancement in technology, industrialization, agricultural
practices and urbanization [1–,2,3]. It is therefore important to proffer
effective, cheap and practicable solutions, capable of removing these
metals from the environment.
Among all the contaminants that may be associated with industrial
wastewaters, potentially toxic metals are of great health concern be-
cause they are non-biodegradable and they can be transformed by
[4,5]. Thus, safe and adequate disposal of wastewater containing these
metals into the environment remains a front-burner challenge that has
attracted the interest of manufacturers, government agencies and en-
vironmentalists and calls for continuous research.Wastewaters from
many industries such as electroplating, mining, metal smelting, dyes,
wood processing (pulp and paper), tanneries, radiator manufacturing,
alloy production, paints, storage batteries, printed circuit board man-
ufacturing, and petroleum refining, usually contain high amount of
potentially toxic metals and therefore require extensive waste treat-
ment. For example, the wood processing industries employ the use of
chromated copper-arsenate in the process of wood treatment leading to
high levels of arsenic-containing wastes; petroleum refining industries
employ metal catalysts for conversion processes, leading to high con-
centration of metals such as nickel, vanadium, and chromium within
the vicinity of petroleum processing factories and dye industries pro-
ducing pigments usually generate high levels of various metal

⁎
Corresponding author.
E-mail address: adenugaa@oauife.edu.ng (A.A. Adenuga).

https://doi.org/10.1016/j.jece.2019.103317
Received 6 June 2019; Received in revised form 20 July 2019; Accepted 23 July 2019
Available online 26 July 2019
2213-3437/ © 2019 Elsevier Ltd. All rights reserved.
A.A. Adenuga, et al.
compounds like chromium and cadmium compounds [6].
Over the years, the unethical discharge of high volumes of waste-
water laden with large amounts of potentially toxic metals into water
bodies has generated austere health and environmental concerns with
the outcry on possible epidemic outcomes across the globe [1]. Yet,
total stoppage of such illicit activities by industries is far from being
achieved. The problem of discharge of untreated or inadequately
treated wastewater into the environment is even more pronounced in
most developing nations of the world in spite of existing environmental
regulations, demanding an improved quality of industrial effluents. This
is partly because of the high cost of conventional treatment techniques
[7–9] and low or no enforcement of the existing environmental laws.
Complete ignorance or low awareness of the adverse impact of
wastewaters enriched in potentially toxic metals, in many communities,
is a major obstacle to curbing the exposure of humans and animals.
Several farmers depend on water bodies into which untreated industrial
effluents are being discharged for their farming activities, such as irri-
gation, fish farming and a source of water for their animals. Most of the
toxic metals, for example, cadmium, arsenic, lead, and mercury, do not
perform any physiological and metabolic functions in man and animals;
rather they cause major adverse health effects. Certainly, few of the
metals are essential and serve as nutrients to plants and animals by
virtue of their physiological and metabolic functions, such metals in-
clude selenium, zinc, iron, and copper. However, they are needed in
trace amounts and will always constitute a danger to man and en-
vironment at elevated concentrations especially when their permissible
limits are exceeded [10–,11,12]. The impact of ingested or contacted
potentially toxic metals on humans can be classified as toxic (acute,
chronic or sub-chronic), carcinogenic, neurotoxic, mutagenic or ter-
atogenic [13]. The ionic forms of these metals constitute the most dif-
ficult environmental menace since they do not succumb to natural de-
gradation or transformation to less harmful form but are easily
absorbed by plants and aquatic animals for reason of their high solu-
bility. Humans are subjected to the higher dose of these metals by
means of biomagnifications as we move up the food chain and due to
their bioaccumulation ability, they are accumulated in the human body
leading to diverse health hazards.
A variety of conventional technologies for wastewater treatment are
available with different degrees of success to control and minimize the
amount of pollutants being released into the environment, especially
water bodies; such as ion exchange, chemical precipitation, electro-
dialysis, membrane filtration, oxidation, reverse osmosis, flocculation,
solvent extraction, evaporation, phytoremediation and activated carbon
adsorption [14–19]. Nevertheless, the inadequacies of the majority of
these techniques are high running and maintenance costs, production of
toxic sludge and complex processes involved in the treatment [20].
Relatively, adsorption process has demonstrated to be a better sub-
stitute in water and wastewater treatment because of handiness, ease of
the process and simplicity of design design ([20–23]. The high ad-
sorption capacity of the low-cost by-products from agricultural sector as
adsorbents have been tested and found preferable and very attractive
alternative adsorption materials [24,9,25,4,26,17]. Therefore, utiliza-
tion of agricultural wastes as adsorbent proffers exceedingly valuable
technological means of handling potentially toxic metals pollution and
at the same time contributes to waste minimization and management,
with minimum investment required [27,28,17]. This field is therefore, a
means to the end of lingering wastewater problems in the developing
countries to alleviate or at least, reduce the impacts of industrial was-
tewater pollution. For the well-being of man and his environment, it is
very important that more agricultural wastes as low-cost materials are
sourced to help industries in the treatment of their wastewaters for
appropriate control of heavy metal releases into the environment. This
study explores the possibility of the use of SSCI, an industrial waste, as a
viable and sustainable low-cost biosorbent for simultaneous adsorption
of Pb(II), Cd(II) and Zn(II) from wastewaters.
2
Journal of Environmental Chemical Engineering 7 (2019) 103317
2. Material and methods
2.1. Reagents used, biosorbent preparation and characterization
The analytical grade chemicals and reagents used were obtained
from Sigma-Aldrich and BDH and were used without further purifica-
tion. The SSCI was obtained as waste, after oil extraction from a re-
search laboratory at the Obafemi Awolowo University, Ile-Ife, Nigeria.
The spent cake was washed with hot water, filtered and thoroughly
rinsed with warm distilled water to remove residual oil. It was then
oven dried at 105 °C until constant weight of 207.23 ± 0.47 g was
attained. A portion of the oven-dried spent seedcake was crushed and
sieved through a mesh of 500 μm. This served as the unmodified ad-
sorbent. Other portions of the spent cake were carbonized in a muffle
furnace (50 Hz, 9 Amps, 220/240 V, England). Carbonization was car-
ried out by heating at 20 °C /min from room temperature until 500 °C
and then held for 45 min. The samples were then left to cool to room
temperature in a desiccator. The carbonized samples were then crushed
and sieved through a pore size of 500 μm and stored in an airtight
plastic container pending further treatments or usage. Portions of the
raw and charred samples were subjected to further modification by
either one method or a combination of methods. A portion of each of
raw and charred spent seedcake samples was soaked in 0.2 M sulphuric
acid for 48 h for acid modification. The samples were filtered, thor-
oughly washed with distilled water until the pH was neutral and dried
overnight at 105 °C. The acid-modified biosorbent materials were
stored in an airtight plastic container pending further use. The micro-
wave modification was carried out by placing dry samples in a micro-
wave oven with an input power of 400 W and 4 min irradiation time.
These were done to investigate the modification(s) best suited for op-
timum performance of the biosorbent. For characterization, the surface
morphologies of the unmodified, the selected modified adsorbents
(before and after adsorption process) were determined with Scanning
Electron Microscopy (SEM) (TESCAN, Vega 3 XMU, Czech Republic)
and the surface elemental compositions determined with Energy-
Disperse X-ray Spectrometer (EDS) (TESCAN, Czech Republic) that is
attached to the SEM. Fourier Transform Infra Red spectroscopic ana-
lyses were performed using Shimadzu FTIR (Model IR 8400S, USA)
2.2. Preparation of adsorbates and analysis
Lead, Cadmium and Zinc solutions of desired concentrations were
prepared by dilution of a stock solution containing the mixture of the
metal ions at a concentration of 1000 mg/L each. The stock solution
was prepared by dissolving calculated amounts of the nitrate salt of the
metals (Cd(NO3)2, Pb(NO3)2 and Zn(NO3)2) in distilled water. The in-
itial concentration of the metal ions in solution and the residual metals
in solution after adsorption equilibrium was analyzed using Flame
Atomic Absorption Spectrophotometer (FAAS) (AA990 F, PG
Instrument Ltd, United Kingdom). Air–acetylene system was used for all
determinations. ISO 17,025 certified metal reference standards used
were obtained from MRS Scientific Ltd, Wickford, Essex, UK.
2.3. Experimental design
Batch adsorption process was employed throughout the study. The
first stage of the study dealt with the optimization of the conditions
under which the adsorbent will demonstrate the best adsorption capa-
city for the removal of the metals. Biosorbent was allowed to interact
with the solution of the selected metals, Pb, Cd, and Zn, simultaneously
while conditions; pH, initial concentration of adsorbates, dosage of the
biosorbent, temperature and contact time were varied. The combina-
tion of the optimum of each condition evaluated was chosen for further
work. The biosorbent was then applied to two types of real water
samples: (1), Effluents from a metal smelting company - representing
industrial wastewater and (2), domestic waste contaminated stream.
A.A. Adenuga, et al.
2.4. Influence of operating parameters and equilibrium studies
Initial screening of the adsorbents was conducted by contacting
0.5 g of the biosorbent types with 50 mL of metal ions solution at a
concentration of 25 mg/L per metal and agitated by sonication
(Ultrawave, 100 W, 50–60 Hz) for 120 min. Then biosorbent was se-
parated from the solution by filtration, and the filtrate analyzed with
FAAS. Results obtained were used as a guide in the selection of the most
appropriate modification for the biosorbent, based on effectiveness. The
effect of pH on the adsorption capacity was studied in the pH range of
3.0–9.0, which is the range found in most industries discharged was-
tewaters depending on the type of industry [7]. The dosage dependence
of the metal uptake was studied in the range of 2–22 mg/L while the
influence of initial metal ion concentration was studied in the con-
centration range of 0–200 mg/L. The dependency of the adsorption
process on temperature was evaluated at different temperatures of 20,
30, 40 and 50 °C. Langmuir and Freundlich's isotherms were used to
verify the results of these equilibrium studies. The equilibrium ad-
sorption capacity of the biosorbent, qe, representing the amount of
metal ions adsorbed by the biosorbent (mg/g) at equilibrium was cal-
culated using Eq. 1
( C0 − Ce )
qe = V
M (1)
where Co = initial concentration of metal ion in solution (mg/L);
Ce = concentration of the metal ion in solution at equilibrium (mg/
L);
V = volume of solution (L);
M = mass of adsorbent (g).
2.5. Kinetic and thermodynamicstudies of the biosorption process
Using different models that includes pseudo-first order, pseudo-
second order and intraparticle diffusion the dependence of the ad-
sorption data on time was evaluated.
The first order parameters were obtained using the linearized
Lagergren’s first order rate equation [29], given as:
ln (qe − qt ) = ln qe − k1 t (2)
In which qt and qe are the quantities (mg/g) of metal ion adsorbed at
a specified time, t, and equilibrium time respectively, and k1in min−1 is
the rate constant, which can be obtained from the slope of the plot of ln
(qe – qt) against t.
The linearized form of pseudo-second order equation [30] was used
to obtain the second order parameters, given as:
t 1 t
= +
qt k2 qe2 qe (3)
The equilibrium constant of the process k2 (g mg−1 min−1),can be
calculated from the intercept of the linear plot of t/qt against t.
Intra-particle diffusion model as given by Furusawa and Smith [31]
is as follows:
1
qt = kp t 2 + I (4)
−1 -1/2
Where kp(mgg min ) represents the intra-particle diffusion rate
constant which can be calculate from the slope of a plot of qt against t1/
2
,and I, the intercept (mg g−1)
For the kinetic studies, 50 mL each of simulated wastewater solution
containing the mixture of the metals at concentrations of 50, 100, 150
and 200 mg/L for each metal ion was contacted with 0.5 g of the ad-
sorbent at 30 °C. The mixture was shaken continuously and monitored
at a time interval of 20 min over a period of 120 min. The solution was
then filtered and the residual metal ion concentration in the super-
natant solution was analysed using FAAS. The Lagergren’s pseudo-first-
order rate constant, k1, Ho’s pseudo-second-order rate constant, k2, and
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Journal of Environmental Chemical Engineering 7 (2019) 103317
intra-particle diffusion rate constant kp. were calculated from the data
obtained.
Thermodynamic studies help us to understand the feasibility and
spontaneous nature of the biosorption. The Changes in Gibbs free en-
ergy (ΔG), enthalpy (ΔH) and entropy (ΔS), are used in the evaluating
the thermodynamic properties of biosorption process. These parameters
were calculated using the following expressions:
CA
KC =
CS (5)
ΔS ΔH
ln K C = −
R RT (6)
ΔG = ΔH − TΔS (7)
KC represents the distribution coefficient, CA, the quantity of ad-
sorbates adsorbed, CS, concentration of adsorbates in solution at equi-
librium, R, the gas constant with a value of 8.314 J/mol K and T,
temperature in kelvin [32,33]. The effect of temperature on the bio-
sorption process was studiedby varying temperature from 20 to 50 °C,
with time, keeping other parameters such as biosorbentdosage, ad-
sorbates concentration, and pH, constant.
2.6. Adsorption isotherms
To understand the mechanism of the biosorption process and de-
termine the maximum biosorption capacity of the biosorbent, the
Langmuir [34] and Freundlich [35] isotherms, which are the most
commonly used models, were applied on the equilibrium data obtained
experimentally. The linearized form of the Langmuir equation is re-
presented as:
Ce 1 C
= + e
qe KL Q0 Q0 (8)
where qe = quantity ofheavy metal adsorbed on the biosorbent (mg/g);
Ce = equilibrium concentration of metal (mg/L) in the solution;
Q0= maximum adsorption capacity of the biosorbent (mg/g);
KL= equilibrium constant related to the energy of biosorption,
which reflects quantitatively the affinity of the binding sites for the
metals (L/mg) (Mahmoodi [36]. When Ce/qe is plotted against Ce a
straight line is obtained whose slope equals 1/Q0 and intercept equals
KL.
The linearized form of the Freundlich isotherm model is given as:
1
log qe = log kf + log Ce
n (9)
kf and1/n are Freundlich isotherm constants related to adsorption ca-
pacity of the biosorbent (L/g) and intensity of adsorption, respectively.
The plots of log qe against log Ce gives a straight line whose slope equals
1/n with an intercept corresponding to log kf
3. Results and discussion
3.1. Influence of modification on the performance of biosorbent
Table 1 shows the results of the percent of metals adsorbed (%) by
the various biosorbent types evaluated. From the results, there is a clear
indication that modification did enhance the performance of the bio-
sorbent at different degree depending on the modification type. Al-
though, charring only marginally performed best for the uptake of Zn, a
combination of charring and microwaving performed best for the up-
take of Cd(II), Pb(II) and Zn(II), and performed excellently well with Zn
(II) when the metals were adsorbed concurrently in solution. Thus, a
combination of charring and microwaving of the biosorbent was
adopted as the appropriate modification for this work.
A.A. Adenuga, et al.
Table 1
Summary of the influence of modification on the performance of the biosorbent,
presented as percent uptake (%): initial concentration of each metal
ion = 25 mg/L; temperature = 30 °C; biosorbent dosage = 10 g/L; time
=120 min.
Treatment Cd Uptake (%) Pb Uptake (%) Zn Uptake (%)
Untreated 46.99 ± 0.23 89.24 ± 0.32 62.93 ± 0.12
Charred 91.32 ± 0.37 97.97 ± 0.41 96.22 ± 0.24
Chemical 74.35 ± 0.27 49.72 ± 0.32 46.46 ± 0.33
MW 94.49 ± 0.16 95.98 ± 0.12 72.39 ± 0.24
Charred & Chemical 89.75 ± 0.28 58.43 ± 0.25 73.95 ± 0.18
Charred & MW 98.34 ± 0.45 99.06 ± 0.14 95.45 ± 0.37
Chemical & MW 82.13 ± 0.24 63.75 ± 0.29 59.33 ± 0.26
Charred, Chemical & MW 72.82 ± 0.11 71.89 ± 0.36 77.32 ± 0.22
MW = microwaved.
3.2. Characterization of the biosorbents (SEM, EDX and FTIR analyses)
The Scanning Electron Microscopy (SEM) micrographs of the nat-
ural biosorbent, char and microwave modified biosorbents, before and
after biosorption of the metal ions are as shown in Fig. 1 (a–c). The
change in the surface morphology of the biosorbent is evident after the
modification with modified biosorbent showing wider pores which is
suggested to be among the features that made the modified biosorbent
to perform better. The evidence of adsorption of metal ions to the
surface of the biosorbent is clearly demonstrated with the SEM of the
biosorbent after the adsorption process with tiny irregular patches of
particles shown on the surfaces of the biosorbent. The EnergyDispersive
X-ray (EDX) results (Fig. 1d-f)corroborated the SEM results with no
change in the surface elemental compositions (C, N, O, Mg, S, K, P, Ca,
Si and Al) of the unmodified and the modified biosorbents but there
were differences in the percentage elemental compositions as a result of
the modifications. For example, percent carbon increased from 60.75%
in the natural to 84.33% in the modified, percent oxygen and nitrogen
atoms reduced from 38.74% and 2.24% in the natural to 12.07% and
1.54%, respectively. The evidence of adsorption is shown in the EDX of
the modified biosorbent after the adsorption process with the appear-
ance of the adsorbates (Cd, Pb and Zn) in addition to those elements
present naturally.
The mechanism and pattern of metal ions adsorption unto the bio-
sorbentcould be attributed to the type of functional groups available on
the biosorbent surface [37,38]). The FTIR spectra showed the major
functional groups in the natural SSCI, with its modified form and the
loaded biosorbent (Fig. 1g). A careful scrutiny of the three IR spectra
patterns showed distinct absorption band at 3352 cm−1 in the natural
biosorbent and appeared at 3373 in the modified biosorbent which was
observed to shift to 3379 cm-1 after adsorption, as a result ofO–H
stretching vibrations signifying the existence of free hydroxyl groups
and bonded OeH bands of carboxylic acids [38,39].The peak appearing
at 2924 cm−1 for both natural and the modified biosorbents with a
slight decrease to 2922 cm−1 after adsorption of metals while the peak
at 2854 cm−1 in both natural and modified biosorbents which got
slightly shifted down to 2850 cm−1 after metals adsorption was at-
tributed to symmetric stretching vibration of CH2 as a result of CeH
bonds of aliphatic acids [40]. Bands at 1541 cm−1 in natural that
shifted to 1574 cm−1 and 1572 cm−1 in the modified and loaded re-
spectively are attributable to NeH bending while the band observed at
1411 cm−1 in the natural adsorbent but appeared at 1377 cm−1 and
1373 cm−1 respectively in the modified and loaded biosorbents could
be apportioned to symmetric stretching of −COO- [41]. The band at
1035 cm−1 in the natural that shifted to 1045 cm−1 and 1043 cm−1
respectively in the modified and loaded adsorbents accounts for
stretching vibration of CeOH of alcoholic groups and carboxylic acids
[40]. New bands were observed to have been formed at 3179 cm−1 as a
results of the modification which was observed shifted to 3200 cm−1 as
4
Journal of Environmental Chemical Engineering 7 (2019) 103317
a result of the metal adsorption unto the biomass. The results show that
chemical interactions took place on the adsorbent surface between the
−OH/-NH group and the metal ions [42,43].
3.3. Influence of pH on biosorption process
Adsorption of metal ions in solution is fundamentally a function of
the pH of the solution because the state and the mobility of all ions is
affected by pH [24].The variation in the pH of the solution leads to an
increase or a decrease in the competition between hydrogen ions and
the cations (adsorbates) for the limited active sites of the biosorbent
[44]. The influenceof pH on the adsorption of the adsorbates (Pb(II), Cd
(II) and Zn(II)) was studied in the pH range of 3–9. The resultsrevealed
asteady increase in the metals removal efficiency by the biosorbent
with increasing pH of the solution until optimum pH of 9 is attained
(Fig. 2a). This maybe attributed to a gradual reduction in the number of
hydrogen ions in solution competing with the adsorbates for the active
sites of biosorbent. It can also be due to a decrease in positive surface
charge on the biosorbent leading to the lowering of the electrostatic
repulsive force between the biosorbent surface and the metal species,
hence, an increase in uptake of metal ions [25]. The lower adsorption of
metal ions at lower pH may also be as a result of high solubility and
ionisation of the adsorbates in acidic medium. All the three metals, Pb
(II), Cd(II) and Zn(II), were most adsorbed at pH 9 and attempts to
study the effect of the pH beyond 9 were futile because of precipitation
of the metal ions at higher pH values.
3.4. Influenceof biosorbentdosage on biosorption efficiency
The impact of the quantity of the biosorbent per volume of ad-
sorbates solution on the adsorption efficiency was investigated with
biosorbent dosage varied from 2 to 22 g/L. Other parameters such as
pH, adsorbate concentration, temperature and contacttime were kept
constant.The results show a general increase in metal ions uptake as the
biosorbent dose increased from 2 to 10 g/L with increase in percentage
adsorption from 13.07, 14.58 and 13.51% at a dose of 2 g/L to 96.80,
99.42 and 99.09% at a dose of 10 g/L for Cd, Pb and Zn respectively
(Fig. 2b). This is attributed to increased available binding sites as do-
sage increased. Beyond 10 g/L dosage, the mass of adsorbates taken up
per unit mass of the biosorbent decreased progressively leading to re-
duction in effectiveness of the biosorbent. The maximum uptake was
recorded at 10 g/L adsorbent dose and was therefore chosen as the
working dosage for further work.
3.5. Influence oftemperature on the biosorption efficiency
Temperature plays a significant role in the kinetic and equilibrium
studies of every adsorption process leading to increase or decrease in
the biosorption efficiency of biosorbent. Results showed a measurable
increase in the uptake of all the metal ions from 20 to 30 °C, suggesting
an endothermic nature for the process, after which the performance of
the biosorbent remained fairly constant on further increase in tem-
perature (Fig. 2c). This may be explained with the fact that increase in
temperature will increase entropy and at moderately high temperature
faster migration of adsorbates to the biosorbent occurred but at higher
temperature there was an increase in the thermal energy of the metal
ions which may induce desorption back into the solution phase. The
decreasing performance with rising temperature is suggestive of a
process that is largely physisorption, suggesting a weak van der Waal
interaction between the biosorbent and the adsorbates [45,46]. The
optimum temperature of 30 °C was therefore adopted for further stu-
dies.
A.A. Adenuga, et al. Journal of Environmental Chemical Engineering 7 (2019) 103317

Fig. 1. Scanning electron micrographs (SEM) (a–c) and Energy dispersive X-ray (EDX) (d–f) of the biosorbent (a & d) unmodified, (b & e) modified (charred and
microwaved), (c & f) modified and loaded with adsorbates, and (g) FT-IR spectra of unmodified, unloaded modified and loaded modified biosorbents.

3.6. Influence of contact time and the initial concentration of adsorbates on
biosorption efficiency
The impact of contact time of biosorbent with the adsorbates on the
biosorption efficiency
for varied initial concentration of the adsorbates (Pb(II), Cd(II) and
Zn(II)) is shownin Fig. 3a & b, temperature: 30 °C; pH 9; biosorbent
dosage of 10 g/L. The results showed the adsorption capacity increasing
rapidly with contact time, up to 40 min, for all the different initial
concentrations of all the three metals with only slight increase after
40 min and reaching maximum at 60 min. There were no significant
change in equilibrium state after 60 min hence, the optimum time for
adsorption to reach equilibrium was set at 60 min for further work. The
adsorption capacities of the biosorbentat 50, 100, 150 and 200 mg L−1
initial concentrations for each metal ion were found to be 4.96, 8.22,
10.07 and 10.86 mg g-1 respectively for Pb(II); 4.97, 8.06, 9.71 and
10.38 mg g-1 respectively for Cd(II); 4.96, 7.93, 8.90, and 9.25 mg g-1
respectively for Zn(II). The general increase in adsorption capacity
observed at higher concentration of metal ions is associated to a more
effective interaction between sorbent active sites and adsorbates which

5
A.A. Adenuga, et al.
Fig. 2. Effects of pH (a): time =120 min, dosage = 10 g/L, conc. = 100 mg/L,
temp. = 30 °C; Adsorbent dosage (b): pH = 9, time =120 min,
conc. = 100 mg/L, temp. = 30 °C; Temperature (c):pH = 9, dosage = 10 g/L,
time =60 min, conc. = 100 mg/L on the adsorption of Pb(II), Cd(II) and Zn(II)
onto spent seedcake of C. inophyllum biochar.
Fig. 3. Effect of initial concentration on the adsorption of Pb(II) and Cd(II) and
Zn(II) onto spent seedcake of C. inophyllum biochar, pH = 9, dosage = 10 g/L,
temp. = 30 °C.
leads the usage of all active sorbent sites available [47].
The quantity of metal ions adsorbed by SSCI followed the order: Pb
> Cd > Zn, which follows the order of their ionic radii (0.118, 0.097
and 0.074 nm for Pb, Cd and Zn respectively). Generally, displacement
of cations with smaller ionic radii by cations with larger ionic radii is
favoured in adsorption process ([48–50]). It can also be attributed to
their order of ectronegativity and ionization energy [51].
3.7. Adsorption kinetics
Table 2a shows kinetic parameters; the experimental q (qexp), cal-
culated q (qcal), k1, k2, kp, I and the correlation coefficients (R2) of the
6
Journal of Environmental Chemical Engineering 7 (2019) 103317
adsorption of Pb(II), Cd(II) and Zn(II) onto SSCI biochar at 30 °C as
extracted from Figures S1-S3. A comparison of the correlation coeffi-
cient values revealed that pseudo-second order kinetic equation, with
better R2values, gave better fits for the bisorption data of the adsorbates
than pseudo-first order kinetics. Also closeness of the qcal of the pseudo-
second order kinetic to qexp affirmed the biosorption process to be
controlled by the pseudo-second order and suggesting chemisorption
mechanism. The thickness of the boundary layer, revealed by the large
values of the intercept, as explained by I values in the intra-particle
diffusion model indicate a greater boundary layer effect [52]. The plots
for intra-particle diffusion model for Pb(II), Cd(II) and Zn(II) (Figure
S3) did not pass through the origin, indicating that intra-particle dif-
fusion is not the only rate controlling step for the sorption of the metals
and showing the possibility of a simultaneous operation of kinetic
processes in the control of the adsorption rate [36].
3.8. Adsorption isotherms
From the results obtained from fitting the experimental data of the
biosorption process into Langmuir and Freundlich isotherm models,
Figures S4& S5, respectively, it can be inferred by the virtue of the
values of correlation coefficients(Table 2b), that both models explained
the biosorption process adequately, but the Freundlich model better
explained the mechanism for the biosorption of Pb(II) and Cd(II) ions,
indicating a heterogeneous biosorptive process,while Langmuir model
better explained the mechanism for Zn(II) ion, indicating a homogenous
monolayer biosorptive process [53,54].Igwe &Abia, [55], showed that
the isotherm that best describes an adsorption process depends on
thepH of the solution and is specific for different fordifferent metals
Based on the Q0 values of the Langmuir model, the maximum
seedcake biosorption capacity (mg/g) for the metals followed the order:
Pb > Cd > Zn. Comparing the maximum adsorption capacity of the
modified spent seedcake of C. inophyllum biochar studied in this work
with some other biosorbents that have been reported in the literature
(Table 3), it is a testimony that the modified spent seedcake of C. in-
ophyllum biochar performed well for simultaneous adsorption of toxic
metal with little influence of the solution matrix.
3.9. Thermodynamics
The thermodynamic parameters as deduced from the plots of ln KC
against 1/T(Figure S6) are presented in Table 2c. The positive enthalpy,
ΔH, values, for all the metal ions (ΔH = 341.40, 238.67, and 311.75 J/
mol for Pb, Cd, Zn, respectively), depict the overall adsorption process
to be endothermic in nature [64] which is corroborated by the increase
observed in the amount of adsorbates adsorbed with increased tem-
perature. The positive values of the entropy, ΔS, indicates a rising
disorderliness at the adsorbent-solution interface which may be due to
redistribution of energy between biosorbent and the adsorbates [47].
The negative values of Gibb’s free energy, ΔG, indicated that the ad-
sorption process was feasible and occurred spontaneously for the three
metal ions and the negative change with increased temperature implied
that the degree of spontaneity of the reaction increased with tempera-
ture [36].
3.10. Application to real samples
The ability of the biosorbentfor simultaneous removal of toxic me-
tals from wastewater was tested with both industrial wastewater and
surface water contaminated with domestic wastes.Industrial waste-
water was collected from the effluent of a metal smelting company in
Osun state, Nigeria while a stream located around a major dumpsite in
Obafemi Awolowo University, Ile-Ife, Osun state, Nigeria was sampled
for surface water. The stream water sample was collected at the point of
the entry of the dumpsite's leachate into the stream representing sam-
ples with high organic constituents in their matrix. The initial
A.A. Adenuga, et al. Journal of Environmental Chemical Engineering 7 (2019) 103317

Table 2
Kinetics, adsorption isotherms and thermodynamics data for the adsorption process.
(a). Pseudo-first order, Pseudo-second order and Intra-particle diffusion parameters for the adsorption of Pb(II), Cd(II), and Zn(II) onto spent seedcake of C. inophyllumbiochar at 30 °C

Metal Pseudo-first order Pseudo-second order Intra-particle diffusion

qexp qcal k1 R2 qcal k2 R2 Kp I R2

Pb 7.54 25.57 −0.1010 0.7462 7.87 0.0299 1.0000 0.2531 5.3445 0.9321
Cd 7.63 20.71 −0.0864 0.8888 8.30 0.0147 0.9930 0.4240 3.4708 0.8710
Zn 7.42 28.95 −0.0912 0.9256 8.58 0.0085 0.9962 0.2481 5.2945 0.8496

(b). summary of isotherm parameters for the sorption of Pb (II), Cd (II) and Zn (II) on the spent seedcake of C. inophyllum (biochar)

Langmuir Freundlich

2
Metal Q0(mg/g) KL (L/g) R kf 1/n R2

Pb 52.63 0.0062 0.9991 0.446 0.8504 0.9992

Cd 51.28 0.0066 0.9746 0.474 0.842 0.9920
Zn 17.99 0.0280 0.9766 1.096 0.5722 0.9661

(c). Thermodynamic parameters for biosorption of Pb(II), Cd(II) and Zn(II) onto the spent seedcake of C. inophyllum

Metal ΔH°/kJ mol–1 ΔS°/kJ mol–1 K–1 ΔG°/kJ mol–1

293K 303K 313K 323K

Pb 0.3414 0.0930 −26.905 −27.835 −28.765 −29.695

Cd 0.2387 0.0671 −19.417 −20.087 −20.758 −21.429
Zn 0.3118 0.0919 −26.626 −27.545 −28.464 −29.384

Table 3 saturation of the biosorbent active surface and also to matrix effect,
Comparison of the Maximum Adsorption Capacities of some Adsorbents with resulting in co-adsorption of interferences present in the wastewater
spent seedcake of C. inophyllum (biochar). [65]. The results revealed that the biosorbent is capable of remediating
Q0 (mg/g) metals in wastewater to permissible levels when the concentration is
within ≤ 25 mg/L and will also do well at higher concentrations.
Adsorbent material Pb Cd Zn Reference

Streptomyces nourse 36.50 3.40 1.60 [56]

4. Conclusion
Coal ash 101.00 8.40 7.50 [66]
Fly ash 23.20 2.940 7.87 [57]
Banana peel 7.79 5.80 [58] The capacity of SSCI to simultaneously clean-up Lead, Cadmium and
Oil Palm frond 13.00 [59] Zinc from wastewaters was investigated. The results showed a depen-
Oil Palm bark 6.40 [59] dence of the biosorptive process on pH, adsorbent dosage, adsorbate
Oil Palm fruit fibre (OPFB) (unmodified) 4.87 7.20 [60].
Chemically modified OPFB 5.58 7.98 [60].
concentration, time and temperature. The optimum pH for the process
Calophyllum inophyllum seed husk 34.50 [24] was 9, resulting in over 98% removal efficiency. Carbonization of the
Rice husk 0.62 19.62 [61] adsorbent only marginally increased the uptake of Zn, while a combi-
Olive stone 112.1 59.88 [62] nation of carbonization and microwaving performed optimally for the
Plantain peel 4.57 [9]
uptake of Cd(II), Pb(II), and Zn(II). The most effective temperature for
Coconut tree sawdust 25.00 23.81 [63]
Sugarcane bagasse 21.28 40.00 [63] the uptake of all the metal ions from the solution was at 30 °C. The
Rogers mushroom 3.89 [43] quantity of metal ions adsorbed by the spent seedcake of C. inophyllum
Calophyllum inophyllum seedcake 52.63 51.28 17.99 This study followed the order: Pb > Cd > Zn. Also, the application of the bio-
sorbent to wastewater samples showed a performance of between
55–71% for different matrices. This implies that spent seedcake of C.
concentrations of Pb, Cd and Zn in the samples were determined using inophyllum is considerably effective for the simultaneous clean-up of
Flame Atomic Absorption Spectrophotometer, then aliquots of the Lead, Cadmium and Zinc from wastewaters.
samples were subjected to biosorption process using the already es-
tablished optimal conditions and the water samples obtained were
analysed for the level of metals. To study the matrix effects at higher Declaration of Competing Interest
concentration of metals, samples were doped with mixture of the metals
Pb(II), Cd(II) and Zn(II)) at a level of 100 mg/L. Blank determination On behalf of all authors, the corresponding author states that there
was done to evaluate the background effect of solvents and materials is no conflict of interest.
used in the experiment.
Results showed that at the levels of the initial concentration of
metals in the samples, the biosorbent gave over 98% performance with Acknowledgement
the industrial wastewater and over 99% with the receiving stream
water. With higher concentration of metals at 100 mg/L, the perfor- The authors acknowledge Chemistry Department of Obafemi
mance of biosorbent ranged from 54.52% for Zn to 68.14% for Pb in the Awolowo University (OAU) Ile-Ife, Nigeria, for providing the research
industrial wastewater sampleand from 61.82% for Zn to 71.30% for Cd, platform for this study. This research did not receive any specific grant
in the stream water sample (Table S1). The lower performance of the from funding agencies in the public, commercial, or not-for-profit sec-
biosorbent at very high concentration of metals could be linked to faster tors

7
A.A. Adenuga, et al.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.jece.2019.103317.
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