Journal of Cleaner Production 151 (2017) 603e615

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Journal of Cleaner Production

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Adsorption of Lead on Cucumber Peel

Mousumi Basu a, *, Arun K. Guha b, Lalitagauri Ray a, 1
a
Department of Food Technology & Biochemical Engineering, Jadavpur University, 188, Raja S. C. Mullick Road, Kolkata, 700032, India
b
Department of Biological Chemistry, Indian Association for the Cultivation of Science, 2A & B Raja S.C. Mullick Road, Kolkata, 700032, India

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

Article history: The competency of cucumber peel (CP) was explored for adsorption of lead. Optimum adsorption
Received 10 November 2016 occurred at pH 5.0 and at incubation temperature of 30
C. The process of adsorption was quite fast to be
Received in revised form completed within a time frame of 60 min obeying pseudo second order rate kinetics. 1.0 g sorbent was
5 March 2017
capable enough to adsorb 133.60 mg lead (qmax) with Langmuir isotherm model categorically illustrating
Accepted 5 March 2017
Available online 22 March 2017
the adsorption process. The magnitude of hindrance exerted by cadmium in binary system as a conse-
quence of co-ion effect was found to be rather insignificant. Functional group modification study
confirmed principal role of carboxyl group in metal binding. The biomass was characterized by different
Keywords:
Cucumber peel
instrumental analyses like TGA, SEM, EDAX, XRD, FTIR and zeta potential measurement which addi-
Lead biosorption tionally authenticated the sorption phenomenon. Post adsorption elution of the loaded metal was suc-
Chemical modification cessfully executed using HCl as eluant.
Technological characterization © 2017 Elsevier Ltd. All rights reserved.

1. Introduction lead pollution are metal plating, battery manufacturing units,

Water pollution, a severe environmental concern of the present
world is escalating at an alarming rate despite all mitigating mea-
sures due to ever-increasing industrialization. Release of untreated
industrial effluents contaminated with organic and inorganic pol-
lutants including heavy metals enhance the problem to the utmost
extent. Lead being an indispensible element is widely used in
various industrial applications though the treatment strategy of
lead contaminated effluents depends on the type of industries
concerned. Reddy et al. (2010) emphasized that international au-
thorities like United States Environmental Protection Agency
(USEPA) and United States Agency for Toxic Substances and Disease
Registry (USATSDR) have already acknowledged it as one of the
hazardous and non biodegradable heavy metals posing danger to
human and other life forms. A well documented fact highlighted by
Chen et al. (2016), that vital organs and systems are damaged and
normal metabolic functioning of the body are disrupted upon lead
poisoning. In human beings lead is known to cause neural toxicity,
depression, encephalopathy, mood changes, dizziness, forgetfulness
besides attacking kidney, liver and brain as explained by Ren et al.
(2015). The industrial processes that contribute to anthropogenic
* Corresponding author.
E-mail addresses: mousumi.bio@rediffmail.com (M. Basu), arunkumarguha@
gmail.com (A.K. Guha).
1
Prof. Lalitagauri Ray expired on March 30, 2016.
printing, lead mining and smelting operations along with ceramics
and glass goods productions stated by Liu et al. (2016). In order to
mitigate lead poisoning World Health Organization (WHO) has
restricted its maximum concentration in drinking water to
0.01 mg L1, reported by Sarada et al. (2014) and Environmental
Regulatory Authority of India has directed to lower the concentra-
tion of lead to 1.0 mg L1 in effluents before disposal, informed by
Bairagi et al. (2011). Kong et al. (2014) mentioned that some
chemical treatment procedures like reverse osmosis, coagulation,
chemical precipitation, electro dialysis, ultra filtration are employed
with a view to clean wastewaters. However these techniques are not
at all satisfactory either in the standard of performance or at the cost
of execution. Activated carbon seems to be the only option but it is
also associated with high cost and without any provision for
regeneration. These constraints have made the researchers to adopt
a greener, cleaner and inexpensive technology; the biosorption.
Biosorption as defined by Das et al. (2007) exploits the innate
binding ability of different biomaterials for organic and inorganic
contaminants from their respective solution. The process is desig-
nated as ‘green and clean’ as it promises minimized sludge gener-
ation by repeated use of the same sorbent with a provision for
sorbate recovery. What’s more, it is a ‘cost effective’ method utiliz-
ing local and commonly available biological sorbents like fruit and
vegetable peels, agricultural wastes and other plant materials in
decontamination procedure. Literature review shows extensive use
of different biological adsorbents viz. utilization of pongamia oil

http://dx.doi.org/10.1016/j.jclepro.2017.03.028
0959-6526/© 2017 Elsevier Ltd. All rights reserved.
604 M. Basu et al. / Journal of Cleaner Production 151 (2017) 603e615
cake by Shanmugaprakash and Sivakumar (2015); employment of
chemically treated tomato waste by Yargic et al. (2015); experi-
mentation of pomegranate peel by Ben-Ali et al. (2017): exploration
of lentil husk by Basu et al. (2015): application of Dicerocaryum
eriocarpum plant mucilage by Jones et al. (2016) to adsorb heavy
metals from contaminated water. In analogy with the incessant
search for cheaper, feasible and probable sorbent the efficacy of
cucumber peel (CP) has been explored in this research work to
assess its lead adsorption potential.
Cucumber is a very popular fruit that is consumed in all seasons.
Although being eaten as fruit it is used in various other food items.
Cucumber peel (CP) is generated in massive quantities everyday
and is disposed as garbage creating another source of pollution. CP
is rich in biopolymers like cellulose, hemicellulose and lignin. These
biopolymers possess various functional groups (carboxyl, hydroxyl,
amino, phosphate, carbonyl etc.) that can be the binding sites for
heavy metals. Our investigation aims at detailed characterization of
CP and comprehensive study of the adsorption procedure to eval-
uate the usefulness of this sorbent.
2. Materials and methods
2.1. Chemical reagents
All the chemical reagents used in this research work were of
analytical reagent (AR) grade from E. Merck, Darmstadt, Germany.
2.2. Biosorbents
The biomaterials employed comprised of orange peel, cucumber
peel, mango peel, pea peel, groundnut shell and sweet lemon peel
which were procured from adjacent areas. Thus, these materials
were washed thoroughly first with tap water followed by deionized
water to get rid of dust and other adhering particles. The washed
sorbents were oven dried at 60e70
C until a steady weight was
attained. The biosorbents were grounded into fine particles to pass
through 36-mesh screen and stored in desiccated condition for
experimental purpose.
2.3. Analysis of components of CP
Cellulose, hemicellulose and lignin form essential ingredients of
plant biomass apart from extractives, moisture and ash content. In
this study a thorough analysis of different structural components of
CP was conducted following the procedures of Li et al. (2004).
Moisture and ash contents were analyzed according to Zainuddin
et al. (2014).
2.3.1. Moisture content
2.0 g CP was oven dried at 80
C in porcelain crucible. Initial and
final weights of the sample containing crucibles were measured
and the moisture content was calculated by Equation (1).
ðInitial weight of filled crucibleÞ  ðFinal weight of filled crucibleÞ
ðInitial weight of filled crucibleÞ eðInitial weight of empty crucibleÞ
 100%
(1)
2.3.2. Ash content
The amount of ash present was determined by incinerating 3.0 g
CP in washed porcelain crucible in muffle furnace at 700
C for 8 h.
The cooled ash was weighed and the ash content was calculated by
Equation (2).
Weight of ash
¼ % of ash (2)
Weight ofbiomass
2.3.3. Extractives analysis
Dried and powdered CP (G0, g) was contacted with a mixture of
benzene and ethanol (2:1) for 3 h at 30
C. The residue after being
oven dried at 105e110
C (till constant weight) was cooled to room
temperature and weighed again (G1, g). Weight of extractives was
calculated by Equation (3).
G0  G1
W1 ðwt%Þ ¼  100% (3)
G0
2.3.4. Hemicellulose analysis
The residue G1 after extractive analysis was developed with
150 mL NaOH solution (20 g L1). The mixture was refluxed for
3.5 h. The washed residue was dried to constant weight followed by
cooling to room temperature and weighed again (G2, g). Weight of
hemicellulose was calculated by Equation (4).
G1  G2
W2 ðwt%Þ ¼  100% (4)
G0
2.3.5. Lignin analysis
Following extractive analysis 1.0 g residue was oven dried (till
constant weight), cooled and weighed (G3, g). 30 mL H2SO4 was
added and the mixture was kept at 14
C for 24 h followed by
dilution with 300 mL distilled water and reflux for 1 h. After
filtration the residue was washed thoroughly till no sulfate ion was
present in the filtrate (detected by 10% barium chloride). Finally the
oven dried residue was cooled and weighed (G4, g). Weight of lignin
was calculated by Equation (5).
G4 ð1  W1 Þ
W3 ðwt%Þ ¼  100% (5)
G3
2.3.6. Cellulose analysis
Weight of cellulose was calculated by Equation (6).
W4 ðwt%Þ ¼ 100  ðW1 þ W2 þ W3 þ AshÞ (6)
2.4. Thermo gravimetric analysis
A plant material contains several components which get vola-
tilized by progressive heating of the biomass in thermo gravimetric
analyzer. In this analysis weight loss of the biomass served as an
indicator of degradation of its components as a function of tem-
perature. Thermo gravimetric analysis (TGA) of CP was conducted
in Thermo gravimetric analyzer (Pyris Diamond TG/DTA, Perkin
Elmer, Singapore) in nitrogen atmosphere (150 mL min1) in
platinum crucibles. The heating rate of the biomass was 20
C
min1 with temperature ranging from 30 to 1000
C.
2.5. Zeta potential measurement
Zeta potential measurement was done to inspect the variation of
surface charge of CP corresponding to changing pH values. The
instrument used for the purpose was Malvern Zetasizer (Model No.
Zen 3690 Zetasizer Nano ZS 90). The experiment was executed as
per protocol of Li and Bai (2005) which suggested suspending of
0.1 g powdered biomass in 100 mL deionised water. The resulting
 M. Basu et al. / Journal of Cleaner Production 151 (2017) 603e615
suspension was subjected to sonication for 4 h and stirring in
magnetic stirrer for another 24 h followed by a settlement period of
12 h. The supernatants with micro particles of CP were dispensed
into scintillation vials. The pH (2.0e6.0) of the samples was
adjusted with 0.1 M HCl or 0.1 M NaOH prior to measurement.
2.6. Experimental procedures
1
Stock solution of lead (1000 mg L ) was prepared by dissolving
required amount of lead nitrate in deionized water. Working so-
lutions of desired concentrations were obtained by diluting the
stock solution. The experiments of biosorption were mainly per-
formed with biosorbent dose of 0.1 g and 50 mL metal ion solution
(50 mg L1, pH 5.0) incubating at 30
C in 250-mL Erlenmeyer flask
in a shaker (120 rpm) for 24 h if not otherwise mentioned. Post
incubation separation of sorbent was accomplished by centrifuga-
tion (Remi R8C) at a speed of 5500 rpm for 15 min. The residual
concentration of lead in the supernatant was analyzed by Atomic
Absorption Spectrophotometer (Chemito AA203). The adsorption
capacity of CP for lead was measured using mass balance equation
as stated by Masoumi et al. (2016):
 
Ci Cf
q¼ V (7)
W
in this equation q is the amount of lead uptake (mg g1), Ci and Cf
are initial and final metal ion concentrations (mg L1), W repre-
sents weight of biosorbent (g) and V the volume of solution (L). The
role of pH and temperature on adsorption of lead by CP was
investigated at different pH values from 2.0 to 6.0 and at varied
incubation temperatures ranging from 20e35
C (at the optimized
pH 5.0). Kinetic study determining the rate of adsorption was
executed using three different concentrations of lead (20 mg L1,
50 mg L1 and 100 mg L1). The residual concentration of lead in
the solution was checked from time to time. As individual flask
represented each data point so no rectification regarding with-
drawal of sampling volume was required. The isotherm study
concerning maximum adsorption capacity of CP for lead was
investigated at different initial concentrations of lead from
20 mg L1 to 350 mg L1 at 30
C and pH 5.0.
2.7. Co-ion effect in binary system
Wastewaters are often contaminated with more than one metal.
Under this situation usually one metal exerts a pronounced co-ion
effect upon the adsorption of the other. So an endeavor was un-
dertaken to testify the competence of CP to sequester both lead and
cadmium from bimetallic solution. In our investigation, experi-
ments regarding bimetallic system were conducted using mixed
metal solution (50 mL) of lead and cadmium with a biomass dose of
0.1 g at pH 5.0 and an incubation temperature of 30
C. Firstly, the
co-ion effect was investigated by varying initial concentrations of
lead from 20e300 mg L1 while fixing the concentration of cad-
mium at 50 mg L1. In the second case there was concurrent vari-
ation in the initial concentrations of both lead and cadmium
(20e100 mg L1). Finally to figure out the selectivity of binding sites
amongst the two metals, CP was saturated first either with cadmium
or lead (500 mg L1). Metal saturated CP was subjected to centri-
fugation followed by washing and drying. The saturated biomass
was employed to inspect adsorption of lead or cadmium (50 mg L1,
pH 5.0) obeying the same procedure as described in Section 2.6.
2.8. SEM-EDAX analysis
The morphologies of pristine and lead adsorbed CP were studied
605
using scanning electron microscope (SEM) (JEOL JSM 6360). Energy
dispersive X-ray analysis (EDAX) was recorded in the same
instrument.
2.9. X-ray diffraction (XRD) analysis
The biomass was further characterized using X-ray diffraction
(XRD) analysis. XRD patterns of pristine and lead adsorbed CP were
recorded in X-ray diffractometer (Rigaku, Ultima III, Japan) using
CuKa radiation at the scanning speed of 5
min1 with 2q angle
varying in the range of 5-80
.
2.10. FTIR spectroscopy
Fourier transform infrared (FTIR) spectra of CP before and after
lead adsorption were recorded with SHIMADZU IR Prestige-21,
Japan, FTIR spectrometer (resolution 4 cm1). The samples were
first grounded together with IR grade KBr in an agate mortar in the
ratio of 1:100. Pressed pellets were then prepared which were
finally analyzed in the region of 4000e400 cm1.
2.11. Chemical modification of functional groups of CP
1.0 g dried and powdered CP was pretreated with different
chemicals in order to modify its functional groups as per proced-
ures described below. The pretreated adsorbent was used for lead
adsorption.
Methylation of amino group: CP was subjected to formaldehyde
and formic acid treatment for 6 h at 30
C for methylation of its
amino group as per suggestion of Loudon (1984).
Modification of phosphate group: To modify its phosphate group,
CP was refluxed with a mixture of triethyl phosphite and nitro
methane for 6 h as instructed by Markowska et al. (1975).
Acetylation of hydroxyl group: This was achieved by treating the
biomass with 0.1% acetic anhydride dissolved in ultra dry petro-
leum ether for 3 min as recommended by Curtis et al. (1983).
Esterification of carboxyl group: CP was stirred with a mixture of
anhydrous CH3OH and concentrated HCl at 30
C as suggested by
Gardea-Torresdey et al. (1990) for the esterification reaction to
complete.
2.12. Desorption and reuse of CP
The exhausted sorbent was refreshed and reused for succeeding
lead adsorption by means of desorption. To accomplish the pur-
pose, five eluants (0.1 M) consisting of HCl, HNO3, H2SO4, EDTA and
Na2CO3 were screened for their efficacy. 0.1 g lead adsorbed CP was
added to 20 mL of the suitable eluant and incubated for 3 h at 30
C
under shaking condition (120 rpm).
2.13. Lead adsorption from industrial effluent
CP was finally exposed to actual industrial effluent containing
lead to ensure its capability to be used for practical purpose. The
effluent was collected from battery industry located at North 24-
Parganas of West Bengal, India. The concentration of lead in the
untreated wastewater was 6.35 mg L1. At first pH of the effluent
was optimized to 5.0. Then adsorption experiment was conducted
with 50 mL wastewater with other conditions remaining constant
as stated in Section 2.6.
3. Results and discussion
3.1. Screening of biosorbents
Among the six biosorbents experimented, cucumber peel (CP)
606 M. Basu et al. / Journal of Cleaner Production 151 (2017) 603e615
claimed its suitability exhibiting 96% removal efficiency and hence
selected for further studies (Fig. 1). Other sorbents displayed per-
centage adsorption ranging from 67% to ~94%. The disparity in
adsorption capacities as explained by Panda et al. (2006) may be
accredited to morphological characteristics and nature of binding
sites of the biomaterials.
3.2. Analysis of components of CP
The analysis revealed hemicellulose was the primary constitu-
ent of CP. Cellulose and lignin represented secondary and tertiary
components respectively. A detailed report of this analysis is pre-
sented in Table 1.
3.3. Thermo gravimetric analysis
Thermo gravimetric analysis (TGA) illustrated thermal degra-
dation of different components of CP with rising temperature. TGA
curve as represented in Fig. 2a depicted that the initial weight loss
of about 12% upto the temperature rise of 225
C may be accounted
for evaporation of moisture present in the sample. In the next step,
degradation of hemicellulose occurred at temperature range of
225e330
C. This stage witnessed maximum decline in the sample
mass and residual weight of the biomass after this phase was ~55%.
Cellulose was pyrolysed from 330e480
C after which merely 30%
of sample residue left. A further loss of weight continued until
900
C decomposing lignin. TGA analysis demonstrated that
hemicellulose was the major component of the biomass and was
easily degraded followed by cellulose, the secondary component.
Lignin was found to be the most stable among all three components
and it was the last to degrade. The outcome of this investigation is
in good fit with the results obtained by Yang et al. (2007).
3.4. Zeta potential measurement
Zeta potential measurement revealed that surface charge of CP
exhibited an inverse relation with pH of the suspension. It was
observed that zeta values of CP were lowered from 0.546 mV
Fig. 1. Adsorption of Pb (II) by different biomaterials at 30
C with initial concentration
of 50 mg L1. ±SD shown by error bar.
Table 1
Component analysis of CP.
Component Wt (%)a
Moisture 94.27 ± 0.04
Ash 0.43 ± 0.04
Extractives 12.16 ± 0.07
Hemicelluloseb 61.18 ± 0.06
Ligninb 7.62 ± 0.07
Cellulose 18.59 ± 0.08
a
All data are presented as dry weight per cent.
b
Free of extractive matter.
to 19.70 mV as pH of the suspension elevated from 2.0 to 6.0
(Fig. 2b). An abrupt shift in zeta value from 0.546 mV to 12.40 mV
was observed when pH increased from 2.0 to 3.0 which confirmed
the location of isoelectric point (IEP) somewhere between pH
2.0e3.0. Earlier works of Bismarck et al. (2002) on zeta potential
measurement validate the outcome of this experiment according to
which carboxyl groups present in plant biomass dissociate into
COO (aq) and Hþ (aq) in presence of water generating an overall
negative surface charge. It was due to this reason zeta values of CP
remained primarily negative over the pH range measured.
3.5. pH and temperature
pH is a steering factor that governs sorption phenomenon by
influencing surface charge of the sorbent besides controlling other
factors like metal speciation, sequestration and mobility, elaborated
by Das et al. (2007). Zeta potential analysis of CP demonstrated that
surface charge of the biomass became progressively more negative
as pH of the suspension increased from 2.0. This enhanced surface
negativity of the sorbent at higher pH values influenced adsorption
of the metal to a great extent. The negative surface charge leads to
deprotonation of functional groups of the biomass as Hþ (aq) and
H3Oþ (aq) are released from them. Hence, these deprotonated
functional groups that serve as binding sites become easily acces-
sible to metal ions causing better sorption. This fact was well re-
flected in the experiment where adsorption of lead was favored at
elevated pH reaching an optimum value at pH 5.0 (Fig. 2b). How-
ever, at lower pH Coulombic repulsion between lead ions and
positively charged binding sites in conjunction with contest be-
tween Hþ and H3Oþ deterred successful adsorption, justified by Das
et al. (2007). Stated by Iqbal et al. (2009) MINEQLþ employed by
earlier researchers revealed that free lead ions persist when solu-
tion pH is below 6.0 and on crossing the borderline low soluble
hydroxyls like Pb(OH)2 are formed which are responsible for
declined sorption beyond pH 5.0. Abbaszadeh et al. (2016) noted
similar pattern of lead adsorption at different pH values. As pH 5.0
ensured maximum sorption so this pH value was considered for
further experimental procedures.
Adsorption of lead on CP was almost uniform at different tem-
peratures (20e35
C) studied (Fig. 2c). The experimentation
revealed that incubation temperature played insignificant role in
adsorption process which is in accordance with the results of Riaz
et al. (2009).
3.6. Sorption kinetics
The kinetic study illustrates that rate of lead adsorption on CP
followed the same trend as observed by Nadeem et al. (2016) i.e. a
speedy initial stage accompanied by maximum removal followed
by a sluggish final stage approaching equilibrium. In the present
study over 90% of lead was adsorbed during the first 15 min,
thereafter the rate dwindled and equilibrium was attained at
M. Basu et al. / Journal of Cleaner Production 151 (2017) 603e615 607

60 min for all three metal concentrations (Fig. 3a). Thus the time
frame of 60 min was regarded as the optimum contact time. This
sorption phenomenon as illustrated by Singha and Das (2012) can
be exemplified by the fact that enhanced accessibility to active sites
on the sorbent rendered the early phase of sorption very swift, but
in due course of time saturation of those very sites coupled with
competition among residual metal ions for left over sites delayed
the sorption process afterwards.
The data obtained from kinetic study were analyzed in accor-
dance with Lagergren pseudo first order and pseudo second order
kinetic models to find out the mechanism of adsorption. Explained
by Iqbal et al. (2009) pseudo first order model emphasizes phys-
isorption as the rate limiting step while chemisorption and
involvement of valence forces concerning sharing or exchange of
electrons are hypothesized by pseudo second order model. Panda
et al. (2007) depicted in their literature Lagergren pseudo first or-
der and pseudo second order kinetic models (Eq. (8) and Eq. (9)).

k1
logðqe  qt Þ ¼ logqe  t (8)
2:303

t 1 1
¼ þ :t (9)
qt k2 q2e qe

where uptake of lead per gram of biomass at equilibrium is rep-

resented by qe (mg g1) and uptake at any time t (min) is given by qt
(mg g1), k1 (min1) and k2 (g1 mg1 min) are the first order and
second order rate constants. Plotting of experimental data (t/qt
versus t) for pseudo second order model resulted in straight lines
passing through origin for all three concentrations (Fig. 3c) with
high correlation coefficient values (r2) ranging from 0.999 to 1.0.
The results when plotted for pseudo first order model yielded lower
correlation coefficient values and displayed poor linearity (Fig. 3b).
Higher correlation coefficient values and high degree of linearity
confirmed suitability of pseudo second order kinetic model over
the first one in interpreting adsorption of lead on CP.
To determine whether intra particle diffusion had a crucial role
in adsorption phenomenon, kinetic data were further analyzed by
Weber and Morris intraparticle diffusion model. According to
Weber and Morris (1963) this model accentuates external mass
transfer, diffusion through pores and bulk transportation of solute
molecules. Weber Morris model as expressed in Eq. 10
1
qt ¼ Kp t 2 þ c (10)

where amount of lead adsorbed at time t is given by qt (mg g1),

intraparticle diffusion rate constant is denoted by Kp (mg g1
min1/2) and C is the intercept (mg g1). The experimental data
plots (qt versus t1/2) produced non linear curves and lower corre-
lation coefficient values (Fig. 3d). So it can be concluded that intra
particle diffusion was not the sole rate controlling step for the
present adsorption process. Pseudo first order and pseudo second
order kinetic model constants along with Weber and Morris
intraparticle diffusion model constants are presented in Table 2.

3.7. Adsorption isotherm

Adsorption isotherm denotes the magnitude of affinity a sorbent

displays for a particular sorbate. In the present study CP was

Fig. 2. Thermo gravimetric analysis (TGA) of CP at different temperatures (a); Influ-

ence of pH on zeta potential values of CP and on Pb (II) adsorption at 30
C with initial
concentration of 50 mg L1 (b); Effect of incubation temperature on adsorption (c).
Symbols: (-) Pb (II); (C) zeta potential. ±SD shown by error bar.
608 M. Basu et al. / Journal of Cleaner Production 151 (2017) 603e615

Fig. 3. Role of contact time (a); Pseudo first order kinetic plots (b); Pseudo second order kinetic plots (c); Weber Morris intraparticle diffusion model plots (d) on Pb (II) adsorption
by CP. Symbols: (-) 20 mg L1; (C) 50 mg L1; (:) 100 mg L1. ±SD shown by error bar.

contacted with increasing concentrations of lead (20e350 mg L1) saturation of active sites of CP at higher concentrations according to
at the optimized conditions of pH and temperature (pH 5.0, 30
C). Saeed et al. (2009).
The outcome of the experiment demonstrated that uptake of the The data obtained from isotherm experiment were evaluated by
metal increased consistently with escalating concentrations and Langmuir, Freundlich and Temkin isotherm models. Langmuir
became steady at initial concentration of 300 mg L1 beyond which isotherm model as outlined by Langmuir (1918) focuses on mono-
no significant increment in adsorption was noted (Fig. 4a). layer sorption and homogeneity of adsorption sites. The model is
Explained by Nadeem et al. (2016) at elevated concentrations, suggestive of saturation of binding sites of the sorbent with
concentration gradient serves as the steering force for overcoming negligible interaction among the adsorbed species. Freundlich
mass transfer resistance ensuing enhanced sorption. Although the isotherm model postulated by Freundlich (1906) denotes multi-
equilibrium condition above 300 mg L1 might be due to the layer sorption and heterogeneous distribution of active sites.
Temkin model illustrated by Reddy et al. (2010) opinionates that
heat of adsorption of all molecules comprising a layer decreases in a
Table 2 linear fashion as a result of interaction between sorbate and sor-
Pseudo first order and pseudo second order kinetic constants and intraparticle bent. This model also proposes characterization of adsorption
diffusion rate constant on sorption of Pb (II) by CP. process based on uniform distribution of binding energies upto
Parameters Concentration (mg L1) some maximum binding energy.
Langmuir and Freundlich models are represented in Eqs. (11)
20 50 100
and (12) as mentioned by Panda et al. (2007). Temkin isotherm
qe (exp) (mg g1) 9.12 24.04 49.11 model according to literature of Yadav et al. (2014) is represented in
Pseudo first order model constants
Eq. (13).
qe (mg g1) 1.44 2.37 1.048
k1 (min1) 0.005 0.004 0.021
r2 0.092 0.105 0.504
Ce 1 aL Ce
Pseudo second order model constants
1
¼ þ (11)
qe (mg g ) 9.16 24.04 49.16 qe KL KL
k2 (g mg1min1) 0.146 0.255 0.144
r2 0.9999 1 1
Weber Morris intraparticle diffusion model constants
kp (mg g1 min 1/2)
1
0.103 0.084 0.138 log qe ¼ log KF þ log Ce (12)
C (mg g1) 8.04 23.17 47.67 n
2
r 0.778 0.604 0.735
 M. Basu et al. / Journal of Cleaner Production 151 (2017) 603e615 609

Fig. 4. Adsorption isotherm of Pb (II) with 0.1 g CP at various initial concentrations (20e350 mg L1) at pH 5.0 (a), Separation factor profile (inset); Linearized isotherm plot
represented in terms of Langmuir model (b) Linearized isotherm plot represented in terms Freundlich model (c); Linearized isotherm plot represented in terms of Temkin model (d).
±SD shown by error bar.

isotherm models revealed that Langmuir model appropriately

illustrated the present adsorption process (Fig. 4b) showing higher
qe ¼ B lnA þ B lnCe (13) correlation coefficient (r2) value of 0.999 and high degree of line-
arity, confirming monolayer sorption. The theoretical monolayer
where Ce and qe are the concentrations of lead at equilibrium in
adsorption capacity (qmax) of CP for lead was 133.60 mg g1.
solution (mg L1) and on CP (mg g1). Langmuir constants aL (L g1)
Freundlich and Temkin models with lower correlation coefficient
and KL (L g1) designate adsorbate-adsorbent equilibrium and
(r2) values (0.859 and 0.917) proved unsuitable for interpreting
monolayer capacity. 1/n is the heterogeneity factor and KF is
adsorption of lead on CP (Fig. 4c and 4d). Langmuir, Freundlich and
Freundlich constant related to biosorption capacity (L g1). In
Temkin model constants and correlation coefficient values (r2) are
Temkin isotherm model, B ¼ RT ; A is the equilibrium binding
b presented in Table 3.
constant that corresponds to maximum binding energy (L g1), b is
To substantiate whether the present adsorption process was
Temkin isotherm constant and is related to heat of adsorption (J
favorable or unfavorable a dimensionless constant viz. separation
mol1), T is the absolute temperature (K), R is gas constant
factor or equilibrium parameter (RL) was employed. RL as denoted
(8.314 J mol1 K). Analysis of isotherm data in accordance with the
610 M. Basu et al. / Journal of Cleaner Production 151 (2017) 603e615

by Riaz et al. (2009) is expressed in Eq. (14).

1
RL ¼ (14)
1 þ KL Ci

where KL is Langmuir constant as mentioned before, Ci is the initial

metal concentration (mg L1). The values of RL lying within the
range of 0e1 indicate favorable adsorption. RL values calculated
from Eq. (14) were well within 0e1 range which established a
favorable attribute for adsorption of lead on CP. Graphical illustra-
tion of separation factor on adsorption of lead on CP is presented in
Fig. 4a (inset).

3.8. Co-ion effect in binary system

Adsorption pattern of lead and cadmium in binary system was

unlike that of monometallic one. In this system when CP was
exposed to increasing concentrations of lead (20e300 mg L1) in
presence of a fixed concentration of cadmium (50 mg L1) the
sorbent was found to attain equilibrium at 250 mg L1 contrary to
300 mg L1 in monometallic system (Fig. 5a). Though the adsorp-
tion capacity of CP for lead did not decline significantly, however it
was exactly the opposite in case of cadmium where adsorption
capacity deteriorated even more at increasing concentrations of
lead. The extent of hindrance offered by lead on cadmium sorption
became more apparent when initial concentrations of both the
metals were varied concomitantly to the same extent (Fig. 5b). In
that case adsorption of lead remained almost unaffected though a
substantial decrease in uptake of cadmium was noticed as con-
centrations of both the metals increased in the system. This dif-
ferential adsorption behavior may be due to competition between
lead and cadmium ions for occupancy of active sites. Lead possesses
higher electro negativity value (1.8) as compared to cadmium (1.7)
reported by Sulaymon et al. (2013). Chatterjee and Schiewer (2014)
highlighted that hydrated ionic radius of lead (401 pm) is smaller
than that of cadmium (426 pm). Thus being more electronegative
and smaller lead becomes more competitive with respect to cad-
mium which in turn augments its adsorption over cadmium. Pre-
vious reports of Coelho et al. (2016) substantiate the findings of the
present work. Lastly when CP saturated with 500 mg L1 cadmium
was tested for lead adsorption its performance was found to be
satisfactory adsorbing ~91% lead. Conversely lead saturated
biomass displayed only 18% cadmium uptake. The results of these
three experiments thus conveniently established the preference of
binding sites for lead and insignificant interference caused by
Fig. 5. Adsorption of Pb (II) in absence and presence of 50 mg L1 Cd (II) by CP (a);
cadmium in binary system.
Comparison of binary adsorption of Pb (II) and Cd (II) simultaneously by CP. ±SD shown
by error bar.

Table 3
3.9. SEM-EDAX analysis
Isotherm model constants and the values of linear
regression coefficients.
The alteration that occurs in the surface morphology due to
Isotherm model Value
metal adsorption can be easily categorized by comparing SEM mi-
Langmuir crographs of pristine and metal bonded biomass. The surface
qmax (mg g1) 133.60 structure of pristine biomass as displayed in Fig. 6a showed prev-
KL (L g1) 82.16
r2 0.999
alence of asymmetrical particles of varying shapes and sizes
Freundlich distributed unevenly upon the matrix. Modification occurred as a
KF (L g1) 38.46 result of interaction with lead and morphology of metal adsorbed
n 2.75 biomass assumed a fibrillar arrangement with occurrence of micro
r2 0.859
particles of lead amongst the fibrillar network (Fig. 6b and 6c).
Temkin
A (L g1) 13.35 Energy dispersive X-ray analysis (EDAX) spectrum of pristine
B 20.70 biomass (Fig. 6d) represented peaks of C, O, Ca, Na, Mg, K, S, Si, P
b (J mol1) 121.74 and Cl. In the spectrum of metal laden biomass it was noticed that
r2 0.917 signals of Na and Mg were replaced by signal of Pb which suggested
 M. Basu et al. / Journal of Cleaner Production 151 (2017) 603e615
Fig. 6. SEM micrograph of pristine CP (a); Pb (II) adsorbed CP (b) and (c); EDAX spectrum of pristine CP (d); Pb (II) adsorbed CP (e).
that ion exchange mechanism was involved in adsorption of lead on
CP (Fig. 6e).
3.10. XRD analysis
X-ray diffraction (XRD) pattern of pristine CP was characteris-
tically amorphous in nature owing to the presence of hemicellulose
and lignin in the biomass. Occurrence of crystalline peak at 21.49

(2q, Cuka) signified existence of cellulosic material, explained by
Reddy et al. (2012). X-ray diffractogram of adsorbed biomass dis-
played all the basic attributes of pristine CP along with emergence
of a sharp peak at 30.44
(2q, Cuka) and other small intermittent
peaks which may be accounted for binding of lead on the biomass
(Fig. 7a).
3.11. FTIR spectroscopy
Fourier transform infrared (FTIR) spectroscopy illustrated that
CP is enriched with an array of different functional groups and
active participation of those groups in lead sequestration.
611
Characterization of these functional groups as per literature of
Kemp (1991) demonstrated that the broad and distinguished peak
of the spectrum of pristine biomass (Fig. 7b, curve 1), displayed in
between 3600e3200 cm1 is due to overlapping stretching vibra-
tion of O-H of alcohols and N-H of amines. Stretching vibrations of
enolic O-H and aldehydic C-H were obvious from emergence of
bands at 2944.46 cm1 and 2869.30 cm1. A small peak at
1735.40 cm1 accounted for C¼O stretching of esters. The steep
band placed at 1631.45 cm1 was attributed to C¼O stretching of
carboxylate ion and C¼O stretching and N-H deformation of am-
ides. An incidence of peak at 1405.95 cm1 revealed C-H defor-
mation of aldehydes and alkanes. Both C-O stretching and O-H
deformation of carboxylic acids were evident from the appearance
of peak at 1321.19 cm1. Presence of phenolic C-O and O-H groups
was depicted at position 1241.22 cm1. C¼S stretching of thioacids
was indicated by the band at 1108.48 cm1. Peak position at
1062.10 cm1 was characteristic of S¼O stretching of sulfones. P-O-
C vibration was designated at position 1034.91 cm1.
Involvement of functional groups in adsorption was evident
from alterations in the peak positions in metal loaded spectrum
612 M. Basu et al. / Journal of Cleaner Production 151 (2017) 603e615
Fig. 7. X-ray diffractograms of pristine CP and Pb (II) adsorbed CP (a); FTIR spectra of
pristine CP (curve 1) and Pb (II) adsorbed CP (curve 2) (b).
(Fig. 7b, curve 2). The broad peak in between 3600e3200 cm1 was
reallocated after lead adsorption owing to participation of hydroxyl
and amino groups in the metal sorption process. The bands at
2944.46 cm1 and 2869.30 cm1 symbolizing enolic and aldehydic
groups were shifted to lower positions on metal binding. Wave
number at 1735.40 cm1 denoting ester group was relocated after
adsorption. Shift in the transmittances at 1631.45 cm1 and
1321.19 cm1 to 1642.51 cm1 and 1384.31 cm1 after sorption
established participation of carboxyl and amide groups. Lead
adsorption caused reallocation in the wave number at
1405.95 cm1 indicating involvement of alkanes and aldehydic
groups. Association of phenolic groups was denoted by change in
peak position at 1241.22 cm1. Participation of sulfur and phos-
phorus in the adsorption process was indicated from the shifts in
the wave numbers at 1108.48 cm1, 1062.10 cm1 and
1034.91 cm1.
3.12. Chemical modification of functional groups of CP
CP being a plant biomass possesses functional groups like
carboxyl, hydroxyl, amino etc. As a part of our investigation we
modified these groups to ascertain their roles in the binding
process.
Esterification of carboxyl group: This was done by anhydrous
methanol and hydrochloric acid treatment. Shifting in FTIR peaks
from 1631.45 cm1 and 1321.19 cm1 to 1654.64 cm1 and
1368.36 cm1 (Fig. 8b) confirmed the esterification reaction.
Reduction in adsorption capacity by 42.79% (Fig. 8a) ascertained the
major role of carboxyl group in lead sorption.
Acetylation of hydroxyl group: Acetylation of hydroxyl group
resulted in 12.08% decrease in uptake capacity (Fig. 8a). Successful
acetylation was confirmed by displacement of the broad peak
placed in between 3600e3200 cm1 in FTIR spectrum (Fig. 8c).
Methylation of amino group: Amino group played insignificant
role as its methylation resulted merely 5.19% decline in adsorption
(Fig. 8a). Methylation of primary and secondary amines was
established by relocation of FTIR band located in between
3600e3200 cm1 (Fig. 8d).
Modification of phosphate group: Phosphate group played a sig-
nificant role subsequent to carboxyl group and its modification
hindered lead adsorption by 22.51% (Fig. 8a). Successful modifica-
tion of phosphate group of the biomass was evident from shift in
FTIR peak located at 1034.91 cm1 to 1039.71 cm1 (Fig. 8e).
3.13. Desorption and reuse of the sorbent
Desorption, one of the important aspects of biosorption was
done to rejuvenate metal loaded CP by eluting it with suitable
most eluant. Three acids (HCl, HNO3 and H2SO4), one chelating
agent (EDTA) and one alkaline salt (Na2CO3) each of 0.1 M con-
centration were employed for the purpose. 0.1 M HCl proved its
unsurpassed ability over other eluants tested, desorbing ~97% of
adsorbed lead from the biomass (Fig. 9a) Adsorption-desorption
cycles were implemented successfully for five times (Fig. 9b) af-
ter which the biomass worn out to some extent due to repeated
acid treatment during elution, explained by Saeed and Iqbal
(2003).
3.14. Ability of CP to clean actual industrial effluent
The last part of our investigation dealt with employment of CP
to remove lead from effluent collected from industrial source
(battery industry) located at North 24-Parganas of West Bengal,
India. The concentration of lead in the untreated wastewater was
6.35 mg L1. After treatment with CP concentration of lead in the
effluent was lowered to 0.56 mg L1 (Table 4). The reduced con-
centration of lead in the effluent after treatment with CP proved
its efficiency to clean actual industrial effluent. Metal ions like
copper, chromium, nickel that are usually present in battery in-
dustry wastewater, mentioned by Bahadir et al. (2007) did not
seem to interfere with adsorption of lead in the present study.
Moreover by desorbing the adsorbed metal using 0.1 M HCl as
eluant, the refreshed sorbent could be reused several times for
adsorption. Since the concentration of lead in CP treated effluent
was far below the permissible limit of 1.0 mg L1 as directed by
Environmental Regulatory Authority of India, reported by Bairagi
et al. (2011), it could be safely disposed. As CP successfully
treated industrial effluent so this sorbent can be utilized practi-
cally for abating water pollution caused by lead.
 M. Basu et al. / Journal of Cleaner Production 151 (2017) 603e615 613

Fig. 8. Reduction in adsorption capacity of CP after modification of functional groups (a); FTIR spectra of pristine and carboxyl group modified CP (b); FTIR spectra of pristine and
hydroxyl group modified CP (c); FTIR spectra of pristine and amino group modified CP (d); FTIR spectra of pristine and phosphate group modified CP (e). ±SD shown by error bar.

4. Conclusion amorphous nature of CP with occasional occurrence of crystalline

The present investigation emphasizes adsorption potential of
cucumber peel (CP) towards lead. Zeta potential measurements
reveal that surface charge of the biomass was primarily negative
above pH 2.0 which explains enhanced sorption at higher pH
values, the optimum being 5.0. Kinetic study illustrated that ~90%
of the metal could be removed within first 15 min which ensures its
prospect for practical application. The pattern of lead adsorption on
CP was monolayer as confirmed by fitting of equilibrium data to
Langmuir model. X-ray diffraction (XRD) analysis characterized
cellulosic peak. Carboxyl and phosphate groups of the biomass
played key role in adsorption. Involvement of ion exchange
mechanism in adsorption process was indicated from EDAX study.
Adsorption of lead was favored even in presence of cadmium in
binary system. Desorption was successful and the biomass could be
regenerated using 0.1 M HCl. CP displayed the capability of
decontaminating lead containing industrial effluent by lowering its
concentration within permissible limit. Therefore it can be
concluded that CP fulfills the criteria of a probable adsorbent for
lead adsorption.
614 M. Basu et al. / Journal of Cleaner Production 151 (2017) 603e615

Fig. 9. Desorption efficiencies of different eluants for desorption of Pb (II) from CP (a); Five regenerative cycles using 0.1 M HCl (b). ±SD shown by error bar.
 M. Basu et al. / Journal of Cleaner Production 151 (2017) 603e615
Table 4
Adsorption of Pb (II) by CP from actual industrial effluent.
Concentration of Pb (II) before Concentration of Pb (II) after treatment
treatment with CP (mg L1) with CP (mg L1)
6.35 0.56
Conflict of interest
Authors declare no competing financial interest.
Acknowledgements
Authors express their gratitude to University Grants Commis-
sion (UGC), New Delhi e 110002, Government of India, for
extending financial support (Grant No. F.5-46/2007(BSR)) to
execute this research work.
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