New Biotechnology
journal homepage: www.elsevier.com/locate/nbt
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.
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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NBT 911 No. of Pages 15
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
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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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.
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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Table 2
Isotherm models used for Pb(II) biosorption on RS.
Table 3
Dynamic characterization models used for Pb(II) biosorption on RS-packed column.
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.
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
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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NBT 911 No. of Pages 15
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
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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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.
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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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].
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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NBT 911 No. of Pages 15
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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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.
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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Table 10
Location of relevant IR bands and their possible assignment.
Unloaded Loaded
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(2016), http://dx.doi.org/10.1016/j.nbt.2016.08.002
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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.
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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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) – 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
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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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.
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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NBT 911 No. of Pages 15
presence of lead on RS surface and indicated that an ion-exchange [14] Gundogdu A, Ozdes D, Duran C, Bulut VN, Soylak M, Senturk HB. Biosorption of
mechanism would be involved in addition to electrostatic Pb(II) ions from aqueous solution by pine bark (Pinus brutia Ten.). Chem Eng J
2009;153:62–9, doi:http://dx.doi.org/10.1016/j.cej.2009.06.017.
interactions and complexation reactions. [15] Nguyen TAH, Ngo HH, Guo WS, Zhang J, Liang S, Yue QY, et al. Applicability of
Biosorption capacity for 50 mg/L and 100 mg/L feed concentra- agricultural waste and by-products for adsorptive removal of heavy metals
tion of lead ions for dynamic tests were higher than the batch from wastewater. Bioresour Technol 2013;148:574–85, doi:http://dx.doi.org/
10.1016/j.biortech.2013.08.124.
conditions for the same initial concentrations, indicating the [16] Moyo M, Guyo U, Mawenyiyo G, Zinyama NP, Nyamunda BC. Marula seed husk
suitability of the biosorbent in the column mode operation. The (Sclerocarya birrea) biomass as a low cost biosorbent for removal of Pb(II) and
breakthrough curve obtained for Pb(II) biosorption on rapeseed Cu(II) from aqueous solution. J Ind Eng Chem 2015;27:126–32, doi:http://dx.
doi.org/10.1016/j.jiec.2014.12.026.
presented a steeper slope for a higher metal inlet concentration. [17] Altenor S, Gaspard S. Biomass for water treatment: biosorbent, coagulants and
Thomas model successfully predicted breakthrough curves and the flocculants. Biomass Sustain Appl Pollut Remediat Energy R Soc Chem 2014;1–
calculated sorption capacity from this model was in agreement 45, doi:http://dx.doi.org/10.1039/9781849737142-00001.
[18] Araujo CST, Carvalho DC, Rezende HC, Almeida ILS, Coelho LM, Coelho NMM,
with the value of Langmuir isotherm. Column studies with real
et al. Bioremediation of waters contaminated with heavy metals using
industrial wastewater presented a removal efficiency of 94.47% for Moringa oleifera seeds as biosorbent. Appl Biorem Act Passive Approach
Pb(II) and a general improvement of the other quality indicators InTech 2013;227–55, doi:http://dx.doi.org/10.5772/56157.
from the effluent showed the practical utility of the biosorbent. [19] Fomina M, Gadd GM. Biosorption: current perspectives on concept, definition
and application. Bioresour Technol 2014;160:3–14, doi:http://dx.doi.org/
Further research includes more investigations regarding the 10.1016/j.biortech.2013.12.102.
operating parameters of continuous biosorption process, sorbent [20] Hlihor RM, Diaconu M, Leon F, Curteanu S, Tavares T, Gavrilescu M.
regeneration and metal recovery options. Experimental analysis and mathematical prediction of Cd(II) removal by
biosorption using support vector machines and genetic algorithms. N
Biotechnol 2015;32:358–68, doi:http://dx.doi.org/10.1016/j.nbt.2014.08.003.
Acknowledgement [21] Zhou K, Yang Z, Liu Y, Kong X. Kinetics and equilibrium studies on biosorption
of Pb(II) from aqueous solution by a novel biosorbent: cyclosorus interruptus. J
Environ Chem Eng 2015;3:2219–28, doi:http://dx.doi.org/10.1016/j.
This work was supported by a grant of the Romanian National jece.2015.08.002.
Authority for Scientific Research, CNDI–UEFISCDI, project no. 60/ [22] Feizi M, Jalali M. Removal of heavy metals from aqueous solutions using
2012, “Integrated System for Reducing Environmental and Human- sunflower, potato, canola and walnut shell residues. J Taiwan Inst Chem Eng
2015;54:125–36, doi:http://dx.doi.org/10.1016/j.jtice.2015.03.027.
related Impacts and Risks in the Water Use Cycle” (WATUSER).
[23] Wang G, Zhang S, Yao P, Chen Y, Xu X, Li T, et al. Removal of Pb(II) from aqueous
The support of the University of Basel, Switzerland (research solutions by Phytolacca americana L. biomass as a low cost biosorbent. Arab J
group of Prof.dr. Cornelia Palivan) is also gratefully acknowledged Chem 2016;2014:0–11, doi:http://dx.doi.org/10.1016/j.arabjc.2015.06.011.
[24] Ronda A, Calero M, Blázquez G, Pérez A, Martín-Lara MA. Optimization of the
for the contribution to some of the characterization tests.
use of a biosorbent to remove heavy metals: regeneration and reuse of
exhausted biosorbent. J Taiwan Inst Chem Eng 2015;51:109–18, doi:http://dx.
doi.org/10.1016/j.jtice.2015.01.016.
References [25] Hafshejani LD, Nasab SB, Gholami RM, Moradzadeh M, Izadpanah Z, Hafshejani
SB, et al. Removal of zinc and lead from aqueous solution by nanostructured
[1] Jitar O, Teodosiu C, Oros A, Plavan G, Nicoara M. Bioaccumulation of heavy cedar leaf ash as biosorbent. J Mol Liq 2015;211:448–56, doi:http://dx.doi.org/
metals in marine organisms from the Romanian sector of the Black Sea. N 10.1016/j.molliq.2015.07.044.
Biotechnol 2015;32:369–78, doi:http://dx.doi.org/10.1016/j.nbt.2014.11.004. [26] Guyo U, Mhonyera J, Moyo M. Pb(II) adsorption from aqueous solutions by raw
[2] Olguín EJ, Sánchez-Galván G. Heavy metal removal in phytofiltration and and treated biomass of maize stover—a comparative study. Process Saf Environ
phycoremediation: the need to differentiate between bioadsorption and Prot 2015;93:192–200, doi:http://dx.doi.org/10.1016/j.psep.2014.06.009.
bioaccumulation. N Biotechnol 2012;30:3–8, doi:http://dx.doi.org/10.1016/j. [27] Taşar Ş, Kaya F, Özer A. Biosorption of lead(II) ions from aqueous solution by
nbt.2012.05.020. peanut shells: equilibrium, thermodynamic and kinetic studies. J Environ
[3] Largitte L, Lodewyckx P. Modeling the influence of the operating conditions Chem Eng 2014;2:1018–26, doi:http://dx.doi.org/10.1016/j.jece.2014.03.015.
upon the sorption rate and the yield in the adsorption of lead(II). Microporous [28] López-Mesas M, Navarrete ER, Carrillo F, Palet C. Bioseparation of Pb(II) and Cd
Mesoporous Mater 2015;202:147–54, doi:http://dx.doi.org/10.1016/j. (II) from aqueous solution using cork waste biomass. Modeling and
micromeso.2014.09.045. optimization of the parameters of the biosorption step. Chem Eng J
[4] Meitei MD, Prasad MNV. Lead (II) and cadmium (II) biosorption on spirodela 2011;174:9–17, doi:http://dx.doi.org/10.1016/j.cej.2011.07.026.
polyrhiza (L.) schleiden biomass. J Environ Chem Eng 2013;1:200–7, doi: [29] Carré P, Pouzet A. Rapeseed market, worldwide and in Europe. OCL 2014;21:
http://dx.doi.org/10.1016/j.jece.2013.04.016. D102, doi:http://dx.doi.org/10.1051/ocl/2013054.
[5] Pawar RR, Lalhmunsiama PL, Bajaj Lee HCS-M. Activated bentonite as a low- [30] No Title n.d. http://www.madr.ro/culturi-de-camp/plante-tehnice/rapita-
cost adsorbent for the removal of Cu(II) and Pb(II) from aqueous solutions: pentru-ulei.html (accessed 23.02.16).
batch and column studies. J Ind Eng Chem 2016;34:213–23, doi:http://dx.doi. [31] Ga˛siorek E, Wilk M. Possibilities of utilizing the solid by-products of biodiesel
org/10.1016/j.jiec.2015.11.014. production—a review. Polish J Chem Technol 2011;13:58–62, doi:http://dx.doi.
[6] World Health Organization International Agency for Reseach on Cancer. org/10.2478/v10026-011-0012-y.
Inorganic and organic lead compounds, vol. 87. Lyon, France: International [32] Al-Asheh S, Duvnjak Z. Sorption of heavy metals by canola meal. Water Air Soil
Agency for Research on Cancer; 2006. Pollut 1999;114:251–76, doi:http://dx.doi.org/10.1023/A:1005093821620.
[7] USEPA. Code of Federal Regulations 40 EPA Part 423 Appendix A. US EPA; 2014. [33] Németh D, Labidi J, Gubicza L, Bélafi-Bakó K. Comparative study on heavy
[8] Volesky B. Detoxification of metal-bearing effluents: biosorption for the next metal removal from industrial effluents by various separation methods.
century. Hydrometallurgy 2001;59:203–16, doi:http://dx.doi.org/10.1016/ Desalin Water Treat 2011;35:242–6, doi:http://dx.doi.org/10.5004/
S0304-386X(00)00160-2. dwt.2011.2438.
[9] Vijayaraghavan K, Balasubramanian R. Is biosorption suitable for [34] Tofan L, Paduraru C, Volf I, Toma O. Waste of rapeseed from biodiesel
decontamination of metal-bearing wastewaters? A critical review on the production as a potential biosorbent for heavy metal ions. Bioresources
state-of-the-art of biosorption processes and future directions. J Environ 2011;6:3727–41.
Manage 2015;160:283–96, doi:http://dx.doi.org/10.1016/j. [35] Štefušová K, Lovás M, Zubrik A, Matik M, Václavíková M. Removal of Cd2+ and
jenvman.2015.06.030. Pb2+ from aqueous solutions using bio-char residues. Nova Biotechnol Chim
[10] Al-Zoubi H, Ibrahim KA, Abu-Sbeih KA. Removal of heavy metals from 2012;2:139–46, doi:http://dx.doi.org/10.2478/v10296-012-0016-x.
wastewater by economical polymeric collectors using dissolved air flotation [36] Paduraru C, Tofan L, Teodosiu C, Bunia I, Tudorachi N, Toma O. Biosorption of
process. J Water Process Eng 2015;8:19–27, doi:http://dx.doi.org/10.1016/j. zinc(II) on rapeseed waste: equilibrium studies and thermogravimetric
jwpe.2015.08.002. investigations. Process Saf Environ Prot 2015;94:18–28, doi:http://dx.doi.org/
[11] Misra RK, Jain SK, Khatri PK. Iminodiacetic acid functionalized cation exchange 10.1016/j.psep.2014.12.003.
resin for adsorptive removal of Cr(VI), Cd(II), Ni(II) and Pb(II) from their [37] Bhatnagar A, Sillanpää M, Witek-Krowiak A. Agricultural waste peels as
aqueous solutions. J Hazard Mater 2011;185:1508–12, doi:http://dx.doi.org/ versatile biomass for water purification–A review. Chem Eng J 2015;270:244–
10.1016/j.jhazmat.2010.10.077. 71, doi:http://dx.doi.org/10.1016/j.cej.2015.01.135.
[12] Huang Y, Wu D, Wang X, Huang W, Lawless D, Feng X. Removal of heavy metals [38] Cruz-Olivares J, Pérez-Alonso C, Barrera-Díaz C, Ureña-Nuñez F, Chaparro-
from water using polyvinylamine by polymer-enhanced ultrafiltration and Mercado MC, Bilyeu B. Modeling of lead (II) biosorption by residue of allspice
flocculation. Sep Purif Technol 2016;158:124–36, doi:http://dx.doi.org/ in a fixed-bed column. Chem Eng J 2013;228:21–7, doi:http://dx.doi.org/
10.1016/j.seppur.2015.12.008. 10.1016/j.cej.2013.04.101.
[13] Fu F, Wang Q. Removal of heavy metal ions from wastewaters: a review. J [39] Li Z, Ge Y, Wan L. Fabrication of a green porous lignin-based sphere for the
Environ Manage 2011;92:407–18, doi:http://dx.doi.org/10.1016/j. removal of lead ions from aqueous media. J Hazard Mater 2015;285:77–83,
jenvman.2010.11.011. doi:http://dx.doi.org/10.1016/j.jhazmat.2014.11.033.
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
G Model
NBT 911 No. of Pages 15
[40] Long Y, Lei D, Ni J, Ren Z, Chen C, Xu H. Packed bed column studies on lead(II) shell Anacardium occidentale L. Ecol Eng 2014;73:514–25, doi:http://dx.doi.
removal from industrial wastewater by modified Agaricus bisporus. Bioresour org/10.1016/j.ecoleng.2014.09.103.
Technol 2014;152:457–63, doi:http://dx.doi.org/10.1016/j. [64] Martín-Lara MA, Rico ILR, Vicente I de la CA, García GB, de Hoces MC.
biortech.2013.11.039. Modification of the sorptive characteristics of sugarcane bagasse for removing
[41] Sadeek SA, Negm NA, Hefni HHH, Wahab MMA. Metal adsorption by lead from aqueous solutions. Desalination 2010;256:58–63, doi:http://dx.doi.
agricultural biosorbents: adsorption isotherm, kinetic and biosorbents org/10.1016/j.desal.2010.02.015.
chemical structures. Int J Biol Macromol 2015;81:400–9, doi:http://dx.doi.org/ [65] Mushtaq M, Bhatti HN, Iqbal M, Noreen S. Eriobotrya japonica seed
10.1016/j.ijbiomac.2015.08.031. biocomposite efficiency for copper adsorption: isotherms, kinetics,
[42] Foo KY, Hameed BH. Insights into the modeling of adsorption isotherm thermodynamic and desorption studies. J Environ Manage 2016;176:21–33,
systems. Chem Eng J 2010;156:2–10, doi:http://dx.doi.org/10.1016/j. doi:http://dx.doi.org/10.1016/j.jenvman.2016.03.013.
cej.2009.09.013. [66] Ofomaja AE. Intraparticle diffusion process for lead(II) biosorption onto
[43] Gautam RK, Mudhoo A, Lofrano G, Chattopadhyaya MC. Biomass-derived mansonia wood sawdust. Bioresour Technol 2010;101:5868–76, doi:http://dx.
biosorbents for metal ions sequestration: adsorbent modification and doi.org/10.1016/j.biortech.2010.03.033.
activation methods and adsorbent regeneration. J Environ Chem Eng [67] Nadeem R, Manzoor Q, Iqbal M, Nisar J. Biosorption of Pb(II) onto immobilized
2014;2:239–59, doi:http://dx.doi.org/10.1016/j.jece.2013.12.019. and native Mangifera indica waste biomass. J Ind Eng Chem 2015;22–5, doi:
[44] Rangabhashiyam S, Anu N, Giri Nandagopal MS, Selvaraju N. Relevance of http://dx.doi.org/10.1016/j.jiec.2015.12.030.
isotherm models in biosorption of pollutants by agricultural byproducts. J [68] Ho YS, Ng JCY, McKay G. Kinetics of pollutant sorption by biosorbents: review.
Environ Chem Eng 2014;2:398–414, doi:http://dx.doi.org/10.1016/j. Sep Purif Rev 2000;29:189–232, doi:http://dx.doi.org/10.1081/SPM-
jece.2014.01.014. 100100009.
[45] Basu M, Guha AK, Ray L. Biosorptive removal of lead by lentil husk. J Environ [69] Chowdhury ZZ, Zain SM, Khan RA. Studies of lead (II) cations from aqueous
Chem Eng 2015;3:1088–95, doi:http://dx.doi.org/10.1016/j.jece.2015.04.024. solutions onto granular activated carbon derived from mangostana garcinia.
[46] Anastopoulos I, Kyzas GZ. Are the thermodynamic parameters correctly BioResources 2012;7:2895–915, doi:http://dx.doi.org/10.15376/
estimated in liquid-phase adsorption phenomena? J Mol Liq 2016;218:174–85, biores.7.3.2895-2915.
doi:http://dx.doi.org/10.1016/j.molliq.2016.02.059. [70] Liang S, Guo X, Feng N, Tian Q. Isotherms, kinetics and thermodynamic studies
[47] Zhou X, Zhou X. The unit problem in the thermodynamic calculation of of adsorption of Cu2+ from aqueous solutions by Mg2+/K+ type orange peel
adsorption using the langmuir equation. Chem Eng Commun 2014;201:1459– adsorbents. J Hazard Mater 2010;174:756–62, doi:http://dx.doi.org/10.1016/j.
67, doi:http://dx.doi.org/10.1080/00986445.2013.818541. jhazmat.2009.09.116.
[48] Bhaumik M, Setshedi K, Maity A, Onyango MS. Removal from water using fixed [71] Anirudhan TS, Radhakrishnan PG. Thermodynamics and kinetics of adsorption
bed column of polypyrrole/Fe 3O4 nanocomposite. Sep Purif Technol of Cu(II) from aqueous solutions onto a new cation exchanger derived from
2013;110:11–9, doi:http://dx.doi.org/10.1016/j.seppur.2013.02.037. tamarind fruit shell. J Chem Thermodyn 2008;40:702–9, doi:http://dx.doi.org/
[49] Sotelo JL, Rodríguez A, Álvarez S, García J. Removal of caffeine and diclofenac 10.1016/j.jct.2007.10.005.
on activated carbon in fixed bed column. Chem Eng Res Des 2012;90:967–74, [72] Smidt E, Böhm K, Schwanninger M. The application of FT-IR spectroscopy in
doi:http://dx.doi.org/10.1016/j.cherd.2011.10.012. waste management. fourier transform. New Anal Approach FTIR Strateg InTech
[50] Al-Ghouti MA, Khraisheh MAM, Ahmad MN, Allen SJ. Microcolumn studies of 2011;405–30, doi:http://dx.doi.org/10.5772/15998.
dye adsorption onto manganese oxides modified diatomite. J Hazard Mater [73] Kuppusamy S, Thavamani P, Megharaj M, Venkateswarlu K, Lee YB, Naidu R.
2007;146:316–27, doi:http://dx.doi.org/10.1016/j.jhazmat.2006.12.024. Potential of Melaleuca diosmifolia leaf as a low-cost adsorbent for hexavalent
[51] Li Q, Tang X, Sun Y, Wang Y, Long Y, Jiang J, et al. Removal of Rhodamine B from chromium removal from contaminated water bodies. Process Saf Environ Prot
wastewater by modified Volvariella volvacea: batch and column study. RSC 2016;100:173–82, doi:http://dx.doi.org/10.1016/j.psep.2016.01.009.
Adv 2015;5:25337–47, doi:http://dx.doi.org/10.1039/C4RA17319H. [74] Yuvaraja G, Krishnaiah N, Subbaiah MV, Krishnaiah A. Biosorption of Pb(II)
[52] Xu D, Tan X, Chen C, Wang X. Removal of Pb(II) from aqueous solution by from aqueous solution by Solanum melongena leaf powder as a low-cost
oxidized multiwalled carbon nanotubes. J Hazard Mater 2008;154:407–16, biosorbent prepared from agricultural waste. Colloids Surf B Biointerfaces
doi:http://dx.doi.org/10.1016/j.jhazmat.2007.10.059. 2014;114:75–81, doi:http://dx.doi.org/10.1016/j.colsurfb.2013.09.039.
[53] Reddy DHK, Seshaiah K, Reddy AVR, Rao MM, Wang MC. Biosorption of Pb2+ [75] Smidt E, Eckhardt KU, Lechner P, Schulten HR, Leinweber P. Characterization of
from aqueous solutions by Moringa oleifera bark: equilibrium and kinetic different decomposition stages of biowaste using FT-IR spectroscopy and
studies. J Hazard Mater 2010;174:831–8, doi:http://dx.doi.org/10.1016/j. pyrolysis-field ionization mass spectrometry. Biodegradation 2005;16:67–79,
jhazmat.2009.09.128. doi:http://dx.doi.org/10.1007/s10531-004-0430-8.
[54] Villaescusa I, Fiol N, Martı’nez M, Miralles N, Poch J, Serarols J. Removal of [76] Qi W, Zhao Y, Zheng X, Ji M, Zhang Z. Adsorption behavior and mechanism of Cr
copper and nickel ions from aqueous solutions by grape stalks wastes. Water (VI) using Sakura waste from aqueous solution. Appl Surf Sci 2016;360:470–6,
Res 2004;38:992–1002, doi:http://dx.doi.org/10.1016/j.watres.2003.10.040. doi:http://dx.doi.org/10.1016/j.apsusc.2015.10.088.
[55] Guo H, Zhang S, Kou Z, Zhai S, Ma W, Yang Y. Removal of cadmium(II) from [77] Cui X, Hao H, Zhang C, He Z, Yang X. Capacity and mechanisms of ammonium
aqueous solutions by chemically modified maize straw. Carbohydr Polym and cadmium sorption on different wetland-plant derived biochars. Sci Total
2015;115:177–85, doi:http://dx.doi.org/10.1016/j.carbpol.2014.08.041. Environ 2016;539:566–75, doi:http://dx.doi.org/10.1016/j.
[56] Flores-Garnica JG, Morales-Barrera L, Pineda-Camacho G, Cristiani-Urbina E. scitotenv.2015.09.022.
Biosorption of Ni(II) from aqueous solutions by Litchi chinensis seeds. [78] Chojnacka K. Biosorption and bioaccumulation—the prospects for practical
Bioresour Technol 2013;136:635–43, doi:http://dx.doi.org/10.1016/j. applications. Environ Int 2010;36:299–307, doi:http://dx.doi.org/10.1016/j.
biortech.2013.02.059. envint.2009.12.001.
[57] Abdolali A, Ngo HH, Guo W, Lu S, Chen SS, Nguyen NC, et al. A breakthrough [79] Torres-Blancas T, Roa-Morales G, Fall C, Barrera-Díaz C, Ureña-Nuñez F, Pavón
biosorbent in removing heavy metals: equilibrium, kinetic, thermodynamic Silva TB. Improving lead sorption through chemical modification of de-oiled
and mechanism analyses in a lab-scale study. Sci Total Environ 2016;542:603– allspice husk by xanthate. Fuel 2013;110:4–11, doi:http://dx.doi.org/10.1016/j.
11, doi:http://dx.doi.org/10.1016/j.scitotenv.2015.10.095. fuel.2012.11.013.
[58] Limousin G, Gaudet J-P, Charlet L, Szenknect S, Barthès V, Krimissa M. Sorption [80] Xu X, Cao X, Zhao L, Wang H, Yu H, Gao B. Removal of Cu Zn, and Cd from
isotherms: a review on physical bases, modeling and measurement. Appl aqueous solutions by the dairy manure-derived biochar. Environ Sci Pollut Res
Geochem 2007;22:249–75, doi:http://dx.doi.org/10.1016/j. 2013;20:358–68, doi:http://dx.doi.org/10.1007/s11356-012-0873-5.
apgeochem.2006.09.010. [81] Tran HN, You S-J, Chao H-P. Effect of pyrolysis temperatures and times on the
[59] Naiya TK, Bhattacharya AK, Mandal S, Das SK. The sorption of lead(II) ions on adsorption of cadmium onto orange peel derived biochar. Waste Manag Res
rice husk ash. J Hazard Mater 2009;163:1254–64, doi:http://dx.doi.org/ 2016;34:129–38, doi:http://dx.doi.org/10.1177/0734242X15615698.
10.1016/j.jhazmat.2008.07.119. [82] Naja G, Murphy V, Volesky B. Biosorption. Metals. Encycl. Ind. Biotechnol.
[60] Chowdhury S, Das Saha P. Biosorption kinetics, thermodynamics and isosteric 2010;1–29.
heat of sorption of Cu(II) onto Tamarindus indica seed powder. Colloids Surf B [83] Tofan L, Paduraru C, Teodosiu C, Toma O. Fixed bed column study on the
Biointerfaces 2011;88:697–705, doi:http://dx.doi.org/10.1016/j. removal of chromium (III) ions from aqueous solutions by using hemp fibers
colsurfb.2011.08.003. with improved sorption performance. Cell. Chem. Technol. 2015;49:219–29.
[61] Saha P, Chowdhury S. Insight into adsorption thermodynamics. Thermodyn [84] Luo X, Deng Z, Lin X, Zhang C. Fixed-bed column study for Cu2+ removal from
InTech 2011, doi:http://dx.doi.org/10.5772/13474. solution using expanding rice husk. J Hazard Mater 2011;187:182–9, doi:
[62] Blázquez G, Martín-Lara MA, Tenorio G, Calero M. Batch biosorption of lead(II) http://dx.doi.org/10.1016/j.jhazmat.2011.01.019.
from aqueous solutions by olive tree pruning waste: equilibrium, kinetics and [85] Muthusamy S, Venkatachalam S. Competitive biosorption of Cr(VI) and Zn(II)
thermodynamic study. Chem Eng J 2011;168:170–7, doi:http://dx.doi.org/ ions in single- and binary-metal systems onto a biodiesel waste residue using
10.1016/j.cej.2010.12.059. batch and fixed-bed column studies. RSC Adv 2015;5:45817–26, doi:http://dx.
[63] Coelho GF, Gonçalves Jr. AC, Tarley CRT, Casarin J, Nacke H, Francziskowski MA. doi.org/10.1039/C5RA05962C.
Removal of metal ions Cd (II), Pb (II), and Cr (III) from water by the cashew nut
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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