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NBT 911 No. of Pages 15

New Biotechnology xxx (2016) xxx–xxx

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New Biotechnology
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Full length article

Biosorption of lead ions from aqueous effluents by rapeseed biomass


Irina Morosanu, Carmen Teodosiu* , Carmen Paduraru, Dumitrita Ibanescu, Lavinia Tofan
Department of Environmental Engineering and Management, Faculty of Chemical Engineering and Environmental Protection, “Gheorghe Asachi” Technical University of Iasi, 73 Prof.
Dr. D. Mangeron Street, 700050, Iasi, Romania

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

Article history:
Received 27 February 2016 Lead, as well as other heavy metals, is regarded as priority pollutant due to its non-biodegradability,
Received in revised form 26 July 2016 toxicity and persistence in the environment. In this study, rapeseed biomass was used in the biosorption
Accepted 23 August 2016 of Pb(II) ions in batch and dynamic conditions, as well as with tests for industrial wastewater. The
Available online xxx influence of initial concentration (5–250 mg/L), pH and contact time (0.5–6 h) was investigated. The
kinetic data modeling resulted in good correlations with the pseudo-second order and intraparticle
Keywords: diffusion models. The maximum sorption capacities of Pb(II) were 18.35, 21.29 and 22.7 mg/L at 4, 20 and
Biosorption 50 C, respectively. Thermodynamic parameters indicated the spontaneity and endothermic nature of
Lead
lead biosorption on rapeseed biomass. The biosorption mechanism involves both physical and chemical
Rapeseed
interactions. The breakthrough curves at 50 and 100 mg/L were determined and evaluated under
Batch conditions
Fixed-bed column dynamic conditions. The breakthrough time lowered with increasing the influent Pb(II) concentration.
Wastewater The experimental data obtained from fixed-bed column tests were well fitted by Thomas and
Yoon-Nelson models. The calculated sorption capacities were in good agreement with the uptake
capacity of Langmuir model. The applicability of rapeseed to be used as a sorbent for Pb(II) ions from real
wastewater was tested, and Pb(II) removal efficiency of 94.47% was obtained.
ã 2016 Elsevier B.V. All rights reserved.

1. Introduction neurodevelopmental problems even at low concentrations. Pb


(II) ions present high affinity for thio ( SH), oxo (¼O) and
Human activities, through industrial and agricultural processes, phosphate (PO43) groups that are found in some enzymes, and
causes surface water quality degradation, leading to problems also ligands and biomolecules from the human organism and affect
related to supply of drinking water or recycling of wastewater. the membrane permeability of organs and haemoglobin synthesis
Among the multitude of pollutants found in wastewater dis- [5]. Lead bioaccumulates in bones (half-time over 20 years), and
charges, heavy metals generate serious environmental and health affects the nervous and reproductive systems, red blood cells and
concerns. These compounds are known for their ability to migrate kidney, and due to its enzyme inhibitor effects, is a probable
between environmental compartments (e.g. from sediments into carcinogenic [3,6]. Lead is listed as a priority pollutant by the US
water) and to accumulate in living organisms [1,2]. Heavy metals Environmental Protection Agency [7]. In drinking water, World
present toxic and non-biodegradable features, which is why once Health Organization has set up as maximum allowable concentra-
they reach the aquatic environment, they produce impacts on the tion for Pb(II) the limit value of 0.01 mg/L. In another classification
aquatic biota, as well as to the crops near the water body, and then [8], Pb is a metal of high priority for both removal and recovery
arrive in the human body in a more concentrated form than that of from water and wastewater before discharge into the environment.
the lower food chain segments. A number of processes are applied to minimize lead concen-
From the heavy metals category, lead has raised multiple tration in wastewater and they involve chemical precipitation,
concerns due to its frequent occurrence in wastewaters and its reduction, electrochemical methods, ion exchange, adsorption,
significant impacts on human health. Lead is present in effluents flotation [9–13]. These methods have several disadvantages that
coming from smelters and refineries, battery manufacturing, steel influence their applicability, including significant capital and
industry, printing, glass manufacturing [3,4]. In humans, lead operational costs, addition of chemical reagents and generation of
poisoning readily affects young children, causing hazardous wastes, energy demand, low efficiency for diluted
wastewaters [14–16]. In this context, biosorption, a subcategory of
adsorption, has gain interest in recent years due to its efficiency in
* Corresponding author.
E-mail address: cteo@ch.tuiasi.ro (C. Teodosiu).

http://dx.doi.org/10.1016/j.nbt.2016.08.002
1871-6784/ã 2016 Elsevier B.V. All rights reserved.

Please cite this article in press as: I. Morosanu, et al., Biosorption of lead ions from aqueous effluents by rapeseed biomass, New Biotechnol.
(2016), http://dx.doi.org/10.1016/j.nbt.2016.08.002
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mitigating heavy metals pollution of aqueous effluents, in operation is more practical at industrial scale, because of its
particularly of low concentration [13]. simplicity and lower costs, while it can be more easily scaled-up
Biosorption is based on the potential of any biological material from laboratory to the pilot and industrial scale [40].
(i.e. biomolecules or different biomass) to sequester metals and The main objective of this study is to evaluate the potential of
other pollutants from aqueous solutions in a metabolically-free rapeseed biomass to remove lead ions from synthetic aqueous
manner [17]. In this way, biosorption is regarded as a passive solution both in batch as well as continuous systems. The surface of
process based on the affinity between the sorbate and the biomass, the sorbent was studied by infrared (IR) spectroscopy and high
as opposed to bioaccumulation, which involves an active metabolic resolution microscopy. The influence of initial concentration and
process [18]. The main advantages and disadvantages of bio- contact time, related isotherm and kinetic models, and thermody-
sorption are illustrated in Fig. 1 [8,19]. namic parameters were investigated in batch mode for a better
A wide variety of biological materials have been explored for understanding of the biosorption process. Column studies were
heavy metal removal. Such biosorbents include low-cost, available done at different initial metal concentrations and several models
and renewable materials, like: macroalgae, agricultural residues, were applied to analyse the breakthrough curves. In addition, the
industrial waste, animal materials, raw plants, sludge etc. [9,19– applicability of the biosorbent to remove Pb(II) ions from more
22]. Among the agricultural and forestry originating sorbents, complex matrices in a fixed bed column was verified by using a real
Phytolacca americana biomass [23], olive tree pruning [24], Marula industrial wastewater. To our best knowledge, this type of
seed husk [16], cedar leaf [25], maize stover [26], peanut shells experiments used to test the biosorption affinity of rapeseed
[27], cork waste [28] have been used in recent years for treating biomass have not been reported so far.
lead-containing wastewaters. Rapeseed is a member of the family
Brassicaceae and has become a major crop harvested mainly for its
animal feed and oil production potential. The major producers are 2. Materials and methods
European Union (20 Mt/yr), Canada (15 Mt/yr) and China
(12 Mt/yr) [29]. In Romania, the total production of rapeseed 2.1. Biosorbent preparation and characterization
has increased threefold between 2007 and 2014 [30]. To obtain one
tone of biodiesel, 3.3 tons of rapeseed are needed, whereas Rapeseed (RS) originating from agricultural units around Iasi
approximately 2.1 tons is rapeseed meal [31]. Such high quantity of (Romania) was used in the present investigation. The biological
by-products and wastes needs to be handled in an environmentally material was prepared according to [36]. In short, the rapeseed was
safe way. An interesting alternative is its utilization as a low-cost washed several times with Grade I water (Adrona Crystal E), dried
biosorbent of pollutants from aqueous solutions [22,32–36]. at 40  C for 24 h and crushed to obtain particle sizes between 0.1
Rapeseed is rich in specific macromolecules such as fatty acids and 0.2 mm.
and proteins [34], but also has lignin, cellulose and hemicellulose Attenuated total reflection Fourier transform infrared
as major constituents. Such components offer a large variety and (ATR-FTIR) spectroscopy (Platinum ATR ALPHA Bruker, Germany)
abundance of functional groups that can act as active sites on the was used to determine the major functional groups on the surface
surface of the biomaterial. of sorbent. Spectra before and after biosorption were recorded
Over the years, biosorption experiments were carried out with a resolution of 2 cm1 in the range 400–4000 cm1, with 128
intensively in batch mode of operation [25–28,37]. Several papers acquisition scans.
reported lead biosorption by agricultural or vegetable biomass in The surface morphological features of loaded and unloaded
dynamic conditions [24,38,39]. The use of a column in continuous rapeseed biomass were analysed using Scanning Electron

Fig. 1. Advantages and disadvantages of biosorption.

Please cite this article in press as: I. Morosanu, et al., Biosorption of lead ions from aqueous effluents by rapeseed biomass, New Biotechnol.
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Microscopy coupled with Energy Dispersive X-ray Spectroscopy 2.4. Kinetic models
(SEM/EDX). The images were executed using FEI Nova NanoSEM
230, operating at an accelerating voltage of 3 kV. Kinetics investigation provides information on the rapidity of
the biosorption. In this study, pseudo-first-order, pseudo-second-
2.2. Reagents order and intraparticle diffusion kinetic models in linearized form
have been used to determine the rate-controlling steps in Pb(II)
All chemicals used were analytical grade. Stock solution of 1 g/L biosorption on rapeseed (Table 1).
Pb(II) was prepared from Pb(NO3)2 dissolution in deionized water
(Adrona Crystal E, Grade I). The working solutions were obtained 2.5. Equilibrium isotherm models
by diluting the stock solution in deionized water.
Two empirical isotherm models, i.e. Langmuir and Freundlich,
2.3. Batch sorption experiments were used to analyse the equilibrium data obtained from the study.
The Langmuir isotherm describes a homogenous monolayer
Biosorption experiments in the batch mode of operation were adsorption, where all the active sites (identical and in a fixed
performed by using 0.5 g of rapeseed and 50 mL of Pb(II) test number) have an equal affinity for the sorbate, with no interaction
solutions, under intermittent agitation and at 20 C, unless between the sorbate molecules in the plane of the surface [42]. The
otherwise mentioned. The influence of initial pH of the solution Freundlich model was developed for adsorption at lower concen-
was studied in the range 2–6 (0.1), at 20 C and a contact time of trations on heterogeneous surfaces and assumes the adsorbed
24 h. The initial pH was adjusted with 0.1 M HNO3, except of the pH molecules interact with their adjacent neighbours [43]. The model
value around 5. The pH was not controlled during the experiments. equation states that the adsorption energy is reduced exponen-
The initial and final pH of the solutions was measured with Consort tially with the decreasing in the number of active sites of an
C863 multi parameter analyzer. The effect of initial sorbate adsorbent [44]. Linear Langmuir and Freundlich isotherm equa-
concentration was done by varying the Pb(II) initial concentrations tions are presented in Table 2.
from 5 to 125 mg/L, at a contact time of 24 h. In all cases, the initial A dimensionless coefficient, usually named as separation factor
pH of the Pb(II) solution was around 5.2 (unmodified pH of the or equilibrium parameter (RL), can be derived based on the
solution) and no further adjustments were made during the tests. Langmuir constant [44] and can be determined with Eq. (3):
Kinetics measurements were done at two initial concentrations
1
(50 and 100 mg/L) and aliquots were taken at different time RL ¼ ð3Þ
1 þ K L C0
intervals (0.5–6 h) to determine Pb(II) concentration. The initial pH
of the solution was approximately 5.2. The effect of the
temperature was studied at three different temperatures (4, 20 2.6. Thermodynamic parameters
and 50 C) by modifying the initial Pb(II) concentration for the test
solutions between 5 and 125 mg/L, at pH around 5.2 and a contact The thermodynamic parameters determination is in close
time of 3 h. The biosorption isotherms were obtained from these correlation with the effect of temperature on biosorption and the
data. Langmuir constant. In order to assess the thermodynamic nature of
The metal solution was separated from the sorbent by the process and its feasibility, the changes in enthalpy (DH),
centrifugation (Hettich Universal 320) at 4000 rpm for 15 min. entropy (DS) and Gibbs free energy (DG) were calculated
All tests were realised in duplicate and the average values were according to Eqs. (4)–(6) [34,46]:
reported. The equilibrium concentrations (Ce) were determined by
4(2-pyridylazo)-resorcinol at l = 530 nm, using Jasco V-530 UV–
DG ¼ RTlnð55:5K L Þ ð4Þ
Vis spectrophotometer. The amount of metal ion retained at
equilibrium (qe) and the Pb(II) removal efficiency (R) were
calculated with the following equations: DH
lnK L ¼  þY ð5Þ
RT
C 0 C e
qe ðmg=gÞ ¼ V ð1Þ
G
DH  DG
DS ¼ ð6Þ
T
C  Ce
Rð%Þ ¼ 0  100 ð2Þ where R is the gas constant (8.31 J/mol K), T is the temperature (K),
C0
KL(L/mol) is the Langmuir equilibrium constant, 55.5 (mol/L) is the
where C0 is the initial Pb(II) concentration (mg/L), G is the weight of solvent (water) concentration and Y is a constant. Zhou and Zhou
rapeseed (g) and V is the volume of solution (mL). [47] proposed Eq. (3) to calculate DG for sorption systems

Table 1
Kinetic models used for Pb(II) biosorption on RS.

Kinetic model Linear equation Parameters Plot


representation
Pseudo-first k1
logðqe  qt Þ¼ logðqe Þ  2:303t qe (mg/g) and qt (mg/g) are the adsorption capacity at equilibrium and time t (min), respectively, k1 (1/ log(qe-qt) vs t
order [14] min) and k2 (g/mg min) are the pseudo-first- and pseudo-second-order rate constants, respectively, Kid
(mg/g min0.5) is the intraparticle diffusion rate constant. t/qt vs t
Pseudo-second t
qt ¼ 12 þ t
k2 qe qe
order [16]
Intraparticle qt ¼ K id t0:5 qt vs t0.5
diffusion [41]

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(2016), http://dx.doi.org/10.1016/j.nbt.2016.08.002
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Table 2
Isotherm models used for Pb(II) biosorption on RS.

Isotherm Linear equation Parameters Plot


model representation
Langmuir Ce
¼ qCe þ K L1q qe – sorption capacity at equilibrium (mg/g), qm – maximum sorption capacity (mg/g), Ce (mg/L)– equilibrium Ce/qe vs Ce
qe
[42]
m m
concentration, KL – Langmuir constant (L/mg), KF and n are the Freundlich constants
Freundlich log qe ¼ log K F þ 1nlog C e log qe vs logCe
[45]

Table 3
Dynamic characterization models used for Pb(II) biosorption on RS-packed column.

Model Linear equation Parameters Plot


representation
  K q m C0 is the initial metal ion concentration (mg/L), Ct is the equilibrium concentration (mg/L) at time t (min), KT ln(C / C  1) vs
Thomas ln CC0t  1 ¼ T 0ðTÞ
K C
 T F0ðTÞ V 0 t
[50]
F is the Thomas constant (L/min/mg), F is the volumetric flow rate (L/min), q0(T) is the maximum column V
  capacity (mg/g) determined by the Thomas model, m is the mass of sorbent (g) and V is the volume (L), kYN is ln(Ct/ C0-Ct) vs t
Yoon- ln C0CC
t
¼ kYN t  t kYN
Nelson
t the Yoon-Nelson constant (1/min), t is the time required for 50% adsorbate breakthrough.
[51]

considering an exchange mechanism. The plot of lnKL against 1/T lead/rapeseed system investigated. The Thomas and Yoon-Nelson
gives the enthalpy change value. models are presented in the linearized form as depicted in Table 3.
The uptake capacity, q0(YN), can be calculated with Eq. (8) [49]:
2.7. Fixed-bed column experiments
C0 Q t
q0ðYNÞ ¼ ð8Þ
1000w
Fixed-bed column experiments were realised in order to assess
the capacity of lead removal of rapeseed in dynamic conditions. where C0 is the inlet metal ion concentration (mg/L), Q is the flow
The experimental set-up included a down flow glass column of rate (mL/min) and w is the weight of sorbent (g).
1.5 cm inner diameter and 15 cm in length. A 0.7 g of rapeseed was
mixed with a commercially available resin (Purolite MN200) in a 2.10. Experiments with industrial wastewater
ratio 1:2 to avoid column clogging. To ensure that no adsorption
phenomena occurs on the used polymer, tests with Pb(II) solutions Industrial wastewaters contain a large variety of organic and
(50 and 100 mg/L) were done. There was no significant change in inorganic contaminants, constituting a complex matrix of inter-
lead concentration after the experiments. Therefore, the men- acting species. In order to observe the behaviour of RS biosorbent
tioned resin can be considered an inert material for the studied in the retention of Pb(II) from such a matrix, while other
process. The bed height of the mixture rapeseed/resin achieved compounds may interfere and/or compete for the sorption sites,
was 6 cm. A layer of wadding glass was fitted at the bottom of the a column experiment using real wastewater spiked with Pb(II) was
column to support the sorbent during studies. The influent feed performed. The wastewater sample was obtained from a factory
flow was established at 2.5 mL/min. The initial Pb(II) concen- located near Iasi, Romania. A volume of 200 mL of industrial
trations in test solutions were 50 and 100 mg/L. The working effluent was treated through the column at a bed height of 6 cm
temperature was 20 C. The initial pH of the solution was around and a flow rate of 2.5 mL/min. The physico-chemical characteristics
5.2 and it wasn’t controlled during the experiment. Effluent of the wastewater used in the experiment were analysed before
samples were collected at the bottom of the column at certain time and after the column by standard methods and the concentration
intervals and analysed for Pb(II) ions content. of lead ions was determined by spectroscopy, as previously
mentioned. The initial wastewater characteristics are presented in
2.8. Breakthrough curve parameters Table 4.

The breakthrough curve is plotted as the effluent concentration


at a certain time (Ct) against effluent volume. The sorption
capacity, qdyn (mg/g), in fixed-bed studies can be determined by
Eq. (7) [48]:

ZV t  
C0 Ct
qdyn ¼ 1 dV ð7Þ
m C0
0
Table 4
where m is the bed mass (g), C0 is the initial influent concentration Water characteristics before biosorption.
(mg/L), Ct is the effluent concentration at any time t (mg/L), V is the Quality indicator (units) Raw wastewater
volume (L). pH 7.78
TSS (mg/L) 69
2.9. Theoretical models COD (mg/L) 515.65
Pb2+ (mg/L) 4.88
Cl (mg/L) 150
In order to process the breakthrough data, two widely used
Total hardness ( G) 12.4
models have been used and evaluated for their applicability to the

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Fig. 2. Influence of initial pH and pH changes during Pb(II) biosorption on RS (C0 = 50 mg/L, biosorbent dose = 10 g/L, pH = 5.2, T = 20 C, t = 24 h).

3. Results and discussions biosorption has increased over the pHPZC. The deprotonation of
biosorbent’s surface determines higher removal efficiencies. Other
3.1. Batch sorption experiments authors have noticed a similar trend in the variation of pHf when
studying removal of Cu(II) and Ni(II) on grape stalks [54] or Cd(II)
3.1.1. Effect of solution pH biosorption on chemically modified maize straw [55].
Functionalization of biosorbent surface and metal speciation At the natural pH of the Pb(II) solution (around 5.2), biosorption
are influenced by the pH of the solution. At pH under 6, lead can be by electrostatic forces and ion exchange mechanism could be
found predominantly in its divalent cationic form (Pb2+). At more responsible for the large quantity of metal ions removed from
basic pH, hydrolyzed species of lead are starting to be formed, such aqueous phase. Hence, the pH of the Pb(II) solutions in the
as Pb(OH)+, Pb(OH)2 and Pb(OH)3 [52,53]. Accordingly, to avoid following sorption experiments will not be adjusted. By working at
the sorption of other species of lead and Pb(OH)2 precipitation, the the natural pH of the solution, addition of foreign ions in the
effect of solution acidity on lead biosorption on RS was studied for system is avoided, while reducing the costs for pH adjustments
initial pH (pHi) values between 2 and 6. In Fig. 2, the variation of Pb before and after the biosorption.
(II) removal efficiency and final solution pH with initial acidity of
medium is illustrated. The initial pH profile shows an increase in 3.1.2. Effect of initial concentration
the removal efficiency of Pb(II) ions from 46.25% at initial pH 2 to a In order to see the correlation between the initial amount of
maximum of 94.04% at initial pH around 5. At initial pH of 6, the metal ions in aqueous phase and the metal-binding capacity of the
removal efficiency is still high (91.13%). In very acidic conditions, a rapeseed biomass, the initial concentration of lead was varied
competing effect for the sorption sites between the protons and between 5 and 250 mg/L. As shown in Fig. 3, the lead uptake of
Pb2+ ions existing in solution can cause lower removal rates rapeseed is dependent on the initial concentration and is
[26,52]. As the pH increases, the repulsive forces between the H+ increasing with the increase of metal ions availability in test
and metal ions decrease and the access to the sorption sites is solutions. The observed results may be explained by the
easier. enhancement in the motivating gradient force dependent on the
Another explanation regarding the removal efficiency (R%)-pHi initial metal concentration. In a specific amount of sorbent, an
profile is linked to the pH at zero point of charge (pHPZC) of the increase of the quantity of metal ions entails a greater driving force
solid. Paduraru et al. [36] have determined the pHPZC of rapeseed to transport the ions from the aqueous phase to the surface of the
biomass to be 5. Therefore, the surface of the biosorbent will be sorbent, and therefore the possibility of interaction between the
positively charged at pH < 5. Consequently, the metal ions from metal ions and the active binding sites increases [15,36,56].
solution could replace the H+ of the active centers of the sorbent.
This could be the reason for the small change in the final solution 3.1.3. Effect of contact time
pH (from 2.1 to 2.78). In contrast, at higher values of pH, the The results obtained from the influence of the contact time on
sorption sites having negative charge will predominate. In this the biosorption of Pb(II) solutions of 50 and 100 mg/L concentra-
case, Pb2+ ions will be electrostatically attracted to the solid tion at 20 C and natural solution pH are depicted in Fig. 4. In the
surface. first 60 min, an abrupt increase in the retained amount of lead ions
In order to investigate the mechanism of biosorption, the final can be observed. This may be explained by the large availability of
pH (pHf) was measured. As shown in Fig. 2 for pHi  4, the pH after the active sites that can be easily accessed. As they are occupied by

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Fig. 3. Influence of initial Pb(II) concentration on the biosorption on rapeseed (biosorbent dose = 10 g/L, pH = 5.2, T = 20 C, t = 24 h).

the metallic ions, the rapeseed surface becomes saturated and a higher temperature induces more mobility in the particles and
competition for the remaining sites will take place by the reduces liquid viscosity and that the affinity of sorbate on the solid
remaining metal ions in the aqueous phase [16,39,57]. At this is higher at high temperatures [60,61].
point, a diffusion barrier occurs as the lead ions are migrating to
the active sites found in the inner pores. At the same time, the 3.1.5. Biosorption isotherms
gradient concentration of lead ions decreases. Therefore, the An adsorption isotherm describes the dependence between the
process rate decreases until equilibrium is reached. This can be metal ions adsorbed and those in aqueous phase in conditions of
recognized in Fig. 4 by the slower increase in the sorption capacity equilibrium and constant temperature. The adsorption isotherms
until a plateau was reached and the sorption capacity was cvasi- is very important for the design of a sorption system, as these
constant. According to these results, a time of 3 h was considered to graphic representations provide information about the sorption
be sufficient for ensuring the liquid-solid equilibrium. capacity [27]. The experimental data was evaluated by the
Langmuir and Freundlich isotherm models and the biosorption
3.1.4. Effect of temperature equilibrium at different temperatures is well described by these
Temperature is an important parameter that influences the models, as illustrated in Fig. 6. The Langmuir constants, KL and qe,
biosorption process. The effect of temperature on lead uptake by were calculated from the slope and intercept of the linear plot Ce/qe
rapeseed was investigated and this dependence is described by against Ce (Fig. 6a). Fig. 6b presents the plot log qe versus log Ce
Fig. 5. The obtained isotherms of “L”-type (concave curve) indicate from which the Freundlich parameters, KF and n, were determined
a progressive saturation of the biomass, as the ratio between the Pb from the slope and intercept of the line. The models’ parameters
(II) ions in solution and adsorbed decreases as the initial and the correlation coefficients are presented in Table 5.
concentration increases [58]. Comparing the three isotherms, it In the case of Langmuir isotherm model, very good correlation
can easily be observed that the amount of metal ions adsorbed per with the sorption data was observed based on coefficients
unit of sorbent mass increases with rise of temperature, indicating R2 > 0.99. The maximum biosorption capacities by monolayer
the endothermic nature of the process, this feature being typical adsorption hypothesis are 18.35, 21.29 and 22.7 mg/g at 4, 20 and
for a chemical reaction. A reason may be that a higher temperature 50  C, respectively (Table 5).
could strengthen the bonds between the Pb(II) ions and active sites The separation factor RL was calculated for the three isotherms
of the biomass and between adjacent sorbate species of the and all the values were obtained between 0.01 and 0.43, indicating
adsorbed phase [59]. Another explanation may be the fact that a a favourable biosorption of Pb(II) onto rapeseed. The maximum
capacity of Pb(II) retention obtained on rapeseed biomass is
comparable with other lignocellulosic biomaterials used for
removal of lead from aqueous solutions (Table 6). The ability of
rapeseed to remove lead ions from aqueous solutions is compara-
ble with Marula seed husk [16], maize stover [26], olive tree
pruning waste [62], cashew nut shell [63] and porous lignin-based
sphere [39]. This proves the feasibility of agricultural wastes and
vegetable biomass for decontamination of wastewater containing
lead ions.

3.1.6. Biosorption kinetics


The rate at which a sorption process takes place is of practical
importance being helpful also for the process design. It is well
known that there are several rate-controlling steps in the sorption
process, including transport of the sorbate in the bulk solution to
Fig. 4. Effect of contact time for the biosorption of lead(II) onto RS biomass the sorbent surface, diffusion through the boundary layer
(biosorbent dose = 10 g/L, pH = 5.2, T = 20 C). surrounding the sorbent particles, transport from surface to the

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Fig. 5. Influence of temperature on Pb(II) removal on rapeseed sorbent (biosorbent dose = 10 g/L, pH = 5.2, t = 3 h).

interior active sites, and sorption via physical interactions or data corresponding to the first 60 min, when rapid sorption occurs,
chemical bonding [65–67]. whereas afterwards it deviates, resulting in lower R2 coefficients.
In order to investigate the mechanism and rate-controlling Conversely, the pseudo-second order kinetic model plots
steps of the lead biosorption on rapeseed, the kinetic data was shown in Fig. 7b were found to fit the experimental data for the
modeled by using the pseudo-first-order, pseudo-second-order entire study period. Consequently, higher correlation factors
and intraparticle models. The value of the sorption capacity at (R2 > 0.99) were obtained and the predicted equilibrium sorption
equilibrium and the rate constant can be determined from the capacity was closer to the experimental uptake, as can be seen
slope and intercept of the linear plots corresponding to the from Table 7. According to the pseudo-second-order kinetic model,
pseudo-first and pseudo-second order kinetic models, which are the biosorption of lead ions onto RS is based on chemical reaction,
presented in Fig. 7(a and b). Table 7 shows the kinetic parameters involving sharing or exchange of electrons between sorbent and
obtained from the analysis of experimental data. The information sorbate [36,56,60]. Literature review reveals the same kinetic trend
deducted from applying the mentioned kinetic models indicates for lead biosorption on Marula seed husk [16], Cyclosorus
that biosorption of Pb(II) on rapeseed corresponds better to the interruptus [21], lentil husk [45], rice husk [59] and peanut shells
pseudo-second-order kinetic model. In many cases, it was reported [27]. Furthermore, the rate of biosorption depends on the initial
that the Lagergren pseudo-first order equation is not suitable for concentration (Table 7).
the whole range of the considered contact times for biosorbents In order to observe the influence of the diffusion mechanism on
[68]. According to the plot in Fig. 7a, the model describes well the the rate of the sorption process, the intraparticle model was tested.
The linear plots of qt versus t0.5 for the two concentrations
considered are presented in Fig. 7c. If the plot is a line that passes
through the origin, then the intraparticle diffusion is the sole rate-
controlling step. It can be easily observed that in both cases the
result is not a straight line and that it also doesn’t pass through the
origin. This indicates that other mechanisms besides diffusion
from the solid-liquid interface are occurring. In this study, the plots
are presented as curves with three linear portions. They corre-
spond to the stages of metal sorption by sorbents. The first portion,
with a higher slope, depicts the rapid uptake of lead ions on the
exterior surface of rapeseed biomass (diffusion from bulk
solution). Then follows the gradual sorption stage, in which the
metal ions enter the biosorbent pores. As the pores become
crowded with sorbate, the diffusion rate decreases and is the rate-
controlling step. This could be attributed to diffusion into the
mesopores. In the final region (region III), the intraparticle
diffusion into micropores slows down considerable, while the
equilibrium between the metal ions in the solution and on the
sorbent surface is being reached. Table 8 presents the diffusion
rates for each stage. The correlation coefficients R2 were between
0.93 and 1. The low values of Kid,III implied that the intraparticle
diffusion into micropores was the rate-limiting step in the
biosorption process. Other authors have reported similar multi-
linearity of intraparticle diffusion plot regarding biosorption of
lead onto mansonia wood sawdust [66], Phytolacca americana L.
biomass [23] and activated carbon derived from Mangostana
Garcinia shell [69] removal of Cu(II), Co(II) and Fe(III) by rice husk,
palm leaf and water hyacinth [41] and of Cu(II) by Tamarindus
Fig. 6. Biosorption isotherm models of Pb(II)-rapeseed system: a. Langmuir model,
b. Freundlich model. indica seed powder [60].

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Table 5 bands of the native RS and Pb-loaded RS with the respective


Quantitative description of Pb(II)-rapeseed biomass system on the basis of
assignments are indicated in Table 10. By comparing the two
Langmuir and Freundlich isotherm models.
spectra from Fig. 8, one can observe distinctive changes on the
Model Langmuir Freundlich biosorbent surface, as result of sorption process on the RS. The
Parameters qe(mg/g) KL(L/mg) R2 KF n R2 broad peak at 3292 cm1 corresponding to the deformation of
Temperature 
4 C 18.35 0.266 0.997 1.70 0.81 0.958
O H and NH groups present in alcohols, phenols, primary and
20 C 21.29 0.400 0.997 3.02 0.94 0.989 secondary amides has sharply decreased and slightly shifted to
50 C 22.70 0.508 0.991 4.92 1.09 0.985 3274 cm1. A similar trend may be observed for the next pair of
high intensity peaks (from 2923 and 2854 cm1 to 2917 and
2848 cm1) that can be attributed to CH2 group vibration of the
3.1.7. Biosorption thermodynamics
lipid moiety of rapeseed [18]. Several overlapping bands appearing
The results of the thermodynamic parameters calculation are
at 1710 and 1651 cm1 indicate that carbonyl moiety of aldehydes,
reported in Table 9. The negative values for the Gibbs free energy
ketones, carboxylic acids, esters or amides have disappeared or
change show the spontaneity of lead biosorption. It can be
shifted to lower wavenumbers. A reduction of peak also occurred at
observed that DG values decrease with increasing temperature,
1535 cm1, which marks the presence of proteins. The peak at
affirming once again the favourability of the process at higher
1241 cm1, related to P- and S-containing compounds, has shifted
temperatures. Literature reports that values of the free energy
to 1174 cm1. The region 1200–1000 cm1 is believed to be
change in the range 20 to 0 kJ/mol are typical for physical
characteristic of C O stretching [25]. A high intensity peak at
adsorption and for chemical sorption are between 80 and
1037 cm1 characteristic to C OC stretching of polysaccharides
400 kJ/mol [70,71]. As it may be observed in Table 9, the values
or CO P stretching of phosphodiesters is reduced and shifted to
obtained in this study are between the two intervals mentioned. It
a lower band. The infrared spectrum of lead loaded rapeseed shows
may be concluded that retention of Pb(II) ions by RS is rather a
the appearance of two peaks at 1090 and 960 cm1, respectively,
combination of physical and chemical sorption processes rather
that in the native RS might be hidden by the more intense ether
than a pure physical or chemical sorption process.
features. The peak at 1090 cm1 is characteristic to SiO deforma-
The enthalpy change value DH was estimated from the slope of
tion [72], while the band at 960 cm1 corresponds to the C¼C
the line obtained from the plot lnKL versus 1/T (figure not shown). A
stretching of alkenes [73]. The disappearance, reduction and/or
positive value was obtained, that shows that the biosorption
shifting of the peaks in the FTIR diagram of Pb-loaded rapeseed
reaction is endothermic. The endothermic nature of the process
suggest the implication of hydroxyl, carboxyl, amine, C¼O, CO,
may be explained by the fact that more than one molecule of water
C¼S and P¼C groups in the biosorption process. A shift to lower
had to be displaced from the surface of biosorbent so that the metal
wavenumbers indicates the weakening of the bond, while a shift to
ions can reach it [60,71]. Because the heat consumed in the
higher frequencies denotes a stronger bond [23].
diffusion step is higher than the heat produced by adsorption, the
FTIR spectroscopy results proved that, beside electrostatic
overall enthalpy change becomes positive.
attraction, other mechanism based on chemical interactions is
The positive value of entropy, DS, indicates the existence of
involved in the removal of lead from the aqueous phase. These
randomness of the process at the liquid/solid interface, caused by
interactions may be ion-exchange or complexation, or even both.
the affinity of the metal ions towards the sorbent [34,51] and the
In the case of ion-exchange, one Pb2+ ion will take the place of two
translational entropy of the displaced water molecules [71].
monovalent anions (e.g. H+) or one divalent anion existing on the
According to Eq. (5), a negative value for DG, while DS > 0,
biosorbent surface. Biosorption of Pb(II) based on an ion-exchange
corresponds of a reaction to be feasible, indicating the chemisorp-
mechanism has been reported by many researchers [57,78]. A
tion involved.
complexation reaction implicates four electron donor atoms (i.e. N,
O, S, P) and one divalent lead ion. Torres-Blanca et al. [79]
3.2. Biosorbent characterization
considered that lead biosorption by de-oiled allspice husk involves
complexation and proposed a complex formation mechanism
In order to understand the biosorption mechanism, ATR-FTIR
between Pb(II) ions and cellulose molecules of the biosorbent. In
spectroscopy was employed to identify the functional groups that
the present study, the disappearance of the peak at 1710 cm1
may be involved in the studied process. The FTIR spectra were
characteristic of C¼O stretching indicated surface complexion
recorded before and after biosorption, in the range of 4000–
through Cp-cation interactions [80,81]. Based on the Hard Soft
400 cm1. Fig. 8 illustrates the complex nature of this material, by
Acid Base Theory, lead is considered a soft acid or at the limit
revealing a plethora of characteristic peaks. The most important
between soft and hard acid and will interact with soft donors, like
S, P or N of the rapeseed constituents [82]. According to the FTIR
Table 6 spectra (Fig. 8 and Table 10), functionalities containing these
Comparison of Pb(II) Langmuir sorption capacity (mg/g) of RS with various elements appear modified between 1700–1000 cm1, indicating
biosorbents from literature (at room temperature). their involvement in the binding of Pb(II) ions. In another study,
Biosorbent qmax(mg/g) Ref.
Paduraru et al. [36] argued that biosorption onto rapeseed waste
was determined by the cross linking as function of Zn(II) ions
Sugarcane bagasse untreated 6.36 [64]
Sugarcane bagasse treated with H2SO4 7.297
intermolecular complexation.
Moringa olifera bark 34.6 [53] SEM images in Fig. 9 reveal the morphological changes after
Olive tree pruning waste 26.24 [62] metal sorption. Initially, the native RS surface (Fig. 9a) was
Cashew nut shell 28.65 [63] characterized by irregularity, increased roughness and heteroge-
Raw maize stover 19.65 [26]
neous pore distribution. Some distortions present on the surface
Treated maize stover 27.1
Cedar leaf ash 8.04 [25] can offer the favourable conditions for metal ions retention
Porous lignin-based sphere 27.1 [39] between the interstices. After metal binding, the material exhibits
Marula seed husk 20 [16] smoother, with lesser porosity features (Fig. 9b). EDX analysis
Phytolacca americana 10.83 [23] indicates the elements present on the sorbent. As Fig. 9c shows, the
HNO3-modified P.americana 12.66
Rapeseed 21.29 Present study
unloaded biomass contains elements like C, O, Mg, P, S, K, Ca.
Among the constituents of rapeseed are included phytic acid, rich

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Fig. 7. Biosorption kinetics representations of Pb(II) onto rapeseed: a. pseudo-first order model, b. pseudo-second-order model. c. intraparticle diffusion model.

in phosphate groups and with affinities to Ca, K, Mg, sinapine (a The good correlation with the pseudo-second-order kinetic
choline ester of sinapic acid), and glucosinolates, containing sulfur model accompanied by the results obtained from FTIR spectrosco-
and nitrogen. The EDX diagram of RS after biosorption (Fig. 9d) py and EDX analysis demonstrate the complexity of the biosorption
shows the presence of an additional evident peak characteristic to process. The high affinity of rapeseed for lead ions most likely due
Pb. This clearly indicates lead retention on rapeseed. The to various mechanisms operating simultaneously: (i) electrostatic
disappearance of some peaks of Mg, K, Ca may suggest an ion- interactions and (ii) chemical interactions, including ion exchange
exchange mechanism for Pb(II) uptake. reactions (with K+, Ca2+, Mg2+ or H+ of the carboxyl and hydroxyl

Table 7
Kinetic description of Pb(II) biosorption on rapeseed biomass by pseudo-first and pseudo-second order models.

C0(mg/g) Pseudo-first order model Pseudo-second order model qexp(mg/g)

k1 103(1/min) qe(mg/g) R2 k2103(mg/g min) qe(mg/g) R2


50 11.28 2.43 0.973 8.81 6.79 0.999 6.52
100 7.6 3.82 0.919 5.41 13.24 0.999 13.08

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Table 8 process under study. However, at larger scale where continuous


Intraparticle diffusion model rates for RS.
operation is preferred and the contact time is limited, this data is
C0(mg/ Intraparticle diffusion model not sufficient [38].
g)
Kid,I(mg/g min0.5) Kid,II(mg/ Kid,III(mg/g min0.5)
g min0.5) 3.3.1. Breakthrough curve parameters
50 0.7052 0.1247 0.0608
Under dynamic conditions, a breakthrough curve is a requisite
100 1.0799 0.2338 0.1100 in order to better evaluate and understand the biosorption
behaviour and the limited capacity of the sorbent to upload metal
ions. As depicted in Fig. 11, the breakthrough curve obtained for Pb
(II) biosorption on rapeseed has a characteristic “S” shape and is
Table 9
Thermodynamic parameters for the biosorption of Pb(II) on rapeseed.
dependent on the inlet concentration. At lower lead concentration,
the curve is more lengthened and the breakthrough point occurs
Temperature ( C) DG(kJ/mol) DH(kJ/mol) DS(kJ/mol) later. This behaviour can be explained by the fact that at higher
4 34.39 10.05 0.160 initial concentration the active sorption sites are more rapidly
20 35.33 0.155 covered by the metal ions [48].
50 35.88 0.142
From the breakthrough curve, the experimental time and
volume at breakthrough and saturation point, respectively, and the
total dynamic uptake capacity (qdyn) were determined. The results
are shown in Table 11. An increase in the feed concentration is
associated with a higher amount of metal ions for the same
quantity of sorbent and as result a smaller volume of treated water
was obtained before the sorption bed became saturated. An
increase in the Pb(II) sorption capacity is observed at elevated
concentrations. This fact could be explained by the greater driving
mass transfer force caused by a larger metal concentration gradient
between the surface of the biomass and the solution [83,84].

3.3.2. Thomas and Yoon-Nelson models


The experimental data of Pb(II) biosorption on RS was
correlated with Thomas and Yoon-Nelson models (Fig. 12). Table 12
reports the findings regarding to the model parameters and the
correlation coefficient.
From Fig. 12 it can be observed that the Thomas model fitted
well the data obtained in laboratory. The correlation values for this
model were 0.930 and 0.947 for the two concentrations, also
Fig. 8. IR spectra for unloaded and metal loaded rapeseed. showing good fitting with the experimental data. Thomas model
implies monolayer adsorption and describes sorption processes
where external and internal diffusion limitations are not present
[85]. This is in good agreement with the previous batch studies.
The rate constant, KT, was lower at smaller initial concentration,
groups) and/or complexation reactions. Based on the FTIR spectra while an opposite trend was observed in the case of the maximum
and EDX diagrams, the possible interactions that occur between solid phase concentration, q0(T), which increased at a higher inlet
lead ions and the active sites at the surface of rapeseed biomass can concentration.
be schematized according to Fig. 10. Another widely used model for predicting breakthrough curves
is the Yoon-Nelson model. According to Table 12 the correlation
3.3. Fixed-bed column experiments coefficient values obtained were comparable with the case of the
previous model. It can be affirmed that the experimental data is
Biosorption investigations in batch mode of operation provided verified by both models. As shown in Table 12, the time required to
important information about the equilibrium and kinetics of the accomplish 50% retention decreases with the inlet Pb(II)

Table 10
Location of relevant IR bands and their possible assignment.

Transmission band (cm1) Vibration Ref.

Unloaded Loaded

3292 3274 OH and NH stretching [45,74]


2923 and 2854 2917 and 2848 H CH asymmetrical and symmetrical stretching [36,75]
1710 – C¼O stretching [4,16,73]
1651 and 1535 1647 and 1535 C¼O, C N and NH stretching [18,74]
1241 1174 CO, C¼S, P¼O stretching [25,45,76]
1037 1017 COC or COP stretching [72,77]
529 520 Si or sulphate stretching [67]

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Fig. 9. SEM images of rapeseed before (a) and after (b) biosorption and EDX spectra of rapeseed before (c) and after (d) biosorption.

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Fig. 10. Schematic representation of possible interactions involved in the Pb(II)/RS sorption process.

Fig. 11. Breakthrough curves for biosorption of Pb(II) on rapeseed at different influent concentrations.

Table 11
Experimental parameters of the breakthrough curves for Pb(II) biosorption.

C0(mg/L) tb(min) Vb(L) ts(min) Vs(L) qt(mg/g)


50 100.78 0.25 188.48 0.47 20.37
100 89.91 0.22 181.63 0.45 40.04

C0 (mg/L) – influent concentration, tb (min)– breakthrough time (Ct/C0 = 0.1), Vb (L) – breakthrough volume, ts (min) – saturation time (Ct/C0 = 0.9), Vs (L) – saturation volume,
qdyn (mg/g) – total dynamic uptake capacity.

concentration of tested solutions, implying a faster column 3.4. Experiments with industrial wastewater
saturation at higher concentration.
Thomas model, as well as Yoon-Nelson model, has given The physico-chemical characteristics of the industrial waste-
sorption capacities which are higher than the one provided by water before and after column treatment are presented in Table 13.
Langmuir equation, i.e. 21.29 mg/g at room temperature. This After 200 mL of the water has passed through the rapeseed-packed
implies that the rapeseed biomass has preference for diffusion in column, the content of Pb(II) was reduced with over 94%. This fact
fixed bed column mode rather than in batch conditions [83]. clearly indicates the affinity of rapeseed biomass for lead ions even

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Fig. 12. Representations of Thomas (a) and Yoon-Nelson (b) models for lead(II) biosorption on RS-packed column.

Table 12
Thomas and Yoon-Nelson models parameters for the sorption of Pb(II) in fixed bed column.

C0(mg/L) Thomas model Yoon-Nelson model

KT103(L/min/mg) q0(T)(mg/g) R2 kYN(1/min) t (min) q0(YN)(mg/g) R2


50 1.55 23.98 0.930 0.0367 197.47 35.17 0.916
100 0.58 48.81 0.947 0.0479 143.11 51.11 0.927

in the presence of other compounds. In addition, the other quality 4. Conclusions


indicators considered in this experiment, like chemical oxygen
demand (COD), total suspended solids (TSS), chloride and water The present study investigated Pb(II) biosorption on rapeseed
hardness showed a significant improvement (Table 13). In biomass in batch conditions and fixed bed columns. The use of this
conclusion, these results reflect the ability of rapeseed to remove biosorbent can help alleviate two environmental problems –
Pb(II) ions and organic compounds from real wastewater. wastewater contamination and agricultural waste disposal.
Equilibrium studies in batch conditions have shown that lead
biosorption is strongly influenced by the initial metal concentration,
contact time and temperature, as higher uptake capacities are
obtained by increasing each of these operating parameters. Kinetic
Table 13 modeling indicated the applicability of pseudo-second-order model
Treated water characteristics. to better describe the Pb(II)/RS system, but the intraparticle diffusion
Quality indicator (units) Treated water Removal efficiency* (RE,%)
also played an important role in the biosorption process. Langmuir
isotherm model describes very well the experimental data, with high
pH 7.01 9.89
TSS (mg/L) 48 30.43
correlation coefficients for all the studied temperatures. The
COD (mg/L) 256 50.35 negative value of DG and the positive values for DH and DS
Pb2+ (mg/L) 0.27 94.47 indicated the spontaneity, endothermic nature and randomness of
Cl (mg/L) 124 17.33 the process under study. FTIR analysis suggested that the hydroxyl,
Total hardness ( G) 3.52 71.61
carboxyl, amine groups as well as C¼O, C O, C¼S and P¼C groups
*
Calculated as RE (%) = (Cinitial–Cfinal)*100/Cinitial. may interact with Pb(II), while SEM/EDX analysis confirmed the

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