Journal of Environmental Management 92 (2011) 2666e2674

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Journal of Environmental Management

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Sorption and desorption of Cd, Cu and Pb using biomass from an eutrophized

habitat in monometallic and bimetallic systems
J.M. Lezcano*, F. González, A. Ballester, M.L. Blázquez, J.A. Muñoz, C. García-Balboa
Departamento de Ciencia de los Materiales e Ingeniería Metalúrgica, Facultad de Ciencias Químicas, Universidad Complutense, Madrid, Spain

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

Article history: This work examines the sorption capacity of a natural biomass collected from an irrigation pond. The
Received 12 July 2010 biomass mainly consisted of a mixture of chlorophyte algae with caducipholic plants. Biosorption
Received in revised form experiments were performed in monometallic and bimetallic solutions containing different metals
12 May 2011
commonly found in industrial effluents (Cd, Cu and Pb). The biosorption process was slightly slower in
Accepted 3 June 2011
the binary system comparing with monometallic system which was related to competition phenomena
Available online 1 July 2011
between metal cations in solution. The biosorbent behaviour was quantified by the sorption isotherms
fitting the experimental data to mathematical models. In monometallic systems, the Langmuir model
Keywords:
Biosorption
showed a better fit with the following sorption order: Cu w Pb > Cd; and biomass-metal affinity order:
Desorption Pb > Cd w Cu. In bimetallic systems, the binary-type Langmuir model was used and the sorption order
Heavy metals obtained was: Pb w Cu > Cd. In addition, the effectiveness of the biomass was investigated in several
Isotherms sorptionedesorption cycles using HCl and NaHCO3. The recovery of metal was higher with HCl than with
Residual biomass NaHCO3, though the sorption uptake of the biomass was sensitively affected by the former desorption
agent in subsequent sorption cycles.
Ó 2011 Elsevier Ltd. All rights reserved.

1. Introduction
The fast development experienced by industry in the last
century has had a dramatic effect on the natural environment.
Pollutants change the natural quality of the environment in phys-
ical, chemical, or biological characteristics (Gupta et al., 2009).
Certainly that is the case of pollution of aquatic systems by heavy
metals (Capó Martí, 2002).
Separation methods based on physical or chemical properties of
solutions have been usually applied in the treatment of industrial
effluents contaminated with heavy metals. The main drawbacks of
those methods are the generation of large amounts of sludges and
the fact that they cannot lower metal concentrations below
100 mg/L, despite that some metals are still extremely toxic at such
concentration.
The potential use of biological materials (biomass) for the
treatment of contaminated sites has been proposed, since several
decades ago, as a substitute to physicochemical decontamination
methods. Among biological methods, biosorption has the unique
advantage that can be performed in the absence of microbial
* Corresponding author.
E-mail address: fgonzalezg@quim.ucm.es (J.M. Lezcano).
metabolism which allows the use of dead biomass with the
subsequent economic savings.
In recent years, there has been an increasing interest in devel-
oping the sorption uptake of many industrial by-products such as:
fertilizers, used for the treatment of hexavalent chromium solu-
tions (Gupta et al., 2010); sugar, for the treatment of heavy metals
including lead, nickel and copper (Gupta and Ali, 2004; Gupta and
Ali, 2000; Gupta et al., 2003); and even different kind of residues
such as red mud, an aluminium industry waste, for the sorption of
cadmium and zinc (Gupta and Sharma, 2002). In addition, algae
have shown good sorbent properties (Gupta and Rastogi, 2008a,b,c;
Gupta et al., 2006) and, in general, low cost adsorbents (Ali and
Gupta, 2007).
However, the feasibility of biosorption versus traditional
methods has been questioned on the base of a series of limitations:
the relatively low metal uptake, the high brittleness of the biomass
and the inherent poor reproducibility. Those limitations may be
overcome, at least in part, whether recovering the metal biosorbed
or reusing the biomass in a new process. In this way, the scale up of
bisorption technology involves studies to minimize both costs and
the environmental impact caused by waste generation (Lister and
Line, 2001; Jalai-Rad et al., 2004; Vijayaraghavan et al., 2005a,b).
On the other hand, in an attempt to approach to actual condi-
tions of water pollution by heavy metals, where is very improbable

0301-4797/$ e see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jenvman.2011.06.004
 J.M. Lezcano et al. / Journal of Environmental Management 92 (2011) 2666e2674 2667

to have just one metal species in solution, research studies have (37.65%) and, in less extent, photosynthetic bacteria (0.31%) and
been extended to systems concerning two or more metals (Chong protistes (0.63%).
and Volesky, 1996; Yu and Kaewsarn, 1999; Gardea-Torresdey Previous to biosorption experiments, the as-received biomass
et al., 2004; Pagnanelli et al., 2004a,b; Mehta and Gaur, 2005). was dried to a constant weight in a stove at 60
C then ground in
Those studies have focused on the effect of a given metal on the a Fritsch Pulverisette grinding mill model 6 and screened to
sorption uptake of another one by a certain biomass and on the a particle size of <0.1 mm.
relative affinity of the biomass for each metal. Nevertheless, the
number of biosorption studies published on multimetallic systems 2.2. Metal solutions
is comparatively less than those related to monometallic systems
(Yu and Kaewsarn, 1999; Romera et al., 2006). In this way, the Metal solutions were prepared from stock solutions of 1000 mg/
evaluation, interpretation and representation of multimetallic L of Cd2þ, Cu2þ and Pb2þ, using the following chemical reagents of
systems is more complex than for monometallic systems because of analytical grade (Panreac): CdSO4$8/3 H2O, CuSO4$5H2O and
competition phenomena between metals in solution for the Pb(NO3)2, respectively. In bimetallic systems with lead, all metal
biomass active sites (Lee and Volesky, 1999; Hammaini et al., 2003; solutions were prepared from the corresponding nitrate salts, also
Volesky, 2003). These competition phenomena, in turn, depend on of analytical grade, in order to avoid metal precipitation.
factors such as metal speciation, solution pH, nature of bond sites, The initial pH in monometallic systems was set at 4 for Cd and
metal concentration or selectivity of the biomass to metal species. Cu and at 5 for Pb (Lezcano et al., 2010). All tests were done in
This work examines the metal sorption uptake of a biomass duplicate. In bimetallic systems, the pH values selected were: 4 for
collected in an eutrophized habitat, both in monometallic and CueCd and 4.5 for CuePb and PbeCd. pH was adjusted with dilute
bimetallic systems. The recovery of the adsorbed metals using H2SO4 (0.1% v/v) for metal solutions prepared from sulphate salts
NaHCO3 and HCl as eluents and the reuse of the biomass in and with dilute HNO3 (0.3% v/v) for those prepared from nitrate
subsequent biosorption cycles. The use of residual biomass salts. In all cases, NaOH at a concentration of (0.001% w/w) was
provides two important advantages: low cost of the biosorbent used as alkaline reagent.
material and recycling of a natural residue with an environmental The experiments were controlled measuring metal concentra-
impact. Metal biosorption was evaluated for three different metals tion over time by atomic absorption spectrometry in a Perkin Elmer
(Cd, Cu and Pb) frequently found in industrial effluents and with 1100B spectrophotometer (detection limits (micrograms/liter): Cd:
a high level of toxicity. The study was performed both in mono- 0.8, Cu: 1.5 and Pb: 15).
metallic and in bimetallic systems and the biomass sorption uptake
was quantified from the isotherms plot and the fit of experimental 2.3. Kinetic study: biosorption tests
data to different mathematical models.
The biosorption tests were performed at constant temperature
and magnetic stirring in 100 mL flasks containing 0.5 g/L of dry
biomass and 40 mL of the corresponding metal solution. After
2. Materials and methods
120 min, pH and metal concentration were measured.
The sorption kinetics was evaluated in several biosorption tests
2.1. Biomass
at different metal concentrations: from 10 mg/L (0.16, 0.09 and
0.05 mmol/L for copper, cadmium and lead, respectively) up to
The residual biomass tested was collected from an eutrophized
150 mg/L (2.36, 1.33 and 0.72 mmol/L for copper, cadmium and
ecosystem, an irrigation pond located at the Forestry Research
lead, respectively) in monometallic systems. Identical concentra-
Centre of Madrid, Spain (CIFOR). The composition of the biomass,
tions of both metals were used in bimetallic systems. During the
shown in Table 1, indicates a wide compositional variety of several
biosorption tests, 5 mL of liquid sample were removed at different
species of clorophite algae (61.41%) and caducipholic plants
times and, after sample centrifugation (at 3000 rpm for 5 min), pH
and metal concentration were measured.
Table 1
Composition of the biomass collected at CIFOR. 2.4. Sorption isotherms
Species Amount (g) in 100 g of biomass
Oedogonium sp.a 26.93
Metal sorption in monometallic systems was quantified from
Eichhornia crassipesb 25.00 the isotherms plot by fitting the experimental data to two mathe-
Cladophora sp.a 20.18 matical models. The sorption isotherms were plotted from several
Spirogyra sp.a 13.52 biosorption tests at different metal concentrations ranged between
Aesculus hippocastanumb 6.94
10 and 150 mg/L.
Platanus orientalisb 3.80
Acer negundob 1.27 The linear Langmuir equation (that provides two parameters:
Diatomeac 0.47 qmax, the maximum metal uptake by the biomass, and K constant,
Scenedesmus sp.a 0.47 which is inversely proportional to the affinity between metal and
Cyanobacteriad 0.31 biomass) and the linear expression of the Freundlich model (that
Micrasterias sp.a 0.31
Hedera elixb 0.20
also provides two parameters: Ke, a constant which is related to the
Euglena sp.c 0.16 biomass sorption uptake, and (1/n) which is an indicative of the
Ulmus sp.b 0.12 sorption degree and gives the exponential relationship between the
Ligustrum sp.b 0.11 sorption uptake by the biomass and the equilibrium metal
Vinca sp.b 0.10
concentration) have been used (Volesky, 2003).
Bambusia sp.b 0.08
Ilex sp.b 0.03 In addition, the sorption uptake, qe, was determined in bio-
a
sorption tests as follows:
Chlorophyta algae.
b
Deciduous plants.
VðC0  Ce Þ
qe ¼
c
Protistes. (1)
d
Photosynthetic bacteria. B
2668 J.M. Lezcano et al. / Journal of Environmental Management 92 (2011) 2666e2674

where V is the liquid volume (L), C0 the initial metal concentration C0=10 mg/L
(mg or mmol/L), Ce the metal concentration at equilibrium (mg or
mmol/L) and B the biomass concentration (g/L).
For bimetallic systems, the sorption isotherms plot was obtained 0,16
by contacting the biomass with metallic solutions of different Cd Cu Pb
concentration (0, 10, 25, 50, 100 and 150 mg/L). In these tests, the

Ce(mm/L)
concentration of the first metal was set while the concentration of
the second metal varied within such range. 0,08
The competition between metals for the sorption sites of the
biomass was quantified by fitting the experimental data to the
binary-type Langmuir model. This model assumes the equilibrium
between two metals in solution (M1 and M2) with the species
resulting from their sorption (BM1 and BM2) by the biomass (B) 0,00
(Sánchez et al., 1999; Hammaini et al., 2003; Volesky, 2003): 0 20 40 60 80 100 120

k1 ½B½M1  1 Time (min.)

B þ M1 %BM1 ; K1 ¼ ¼ ;b ¼ (2)
k1 ½BM1  1 K1 Fig. 1. Metal concentration versus time in monometallic systems.

k2 ½B½M2  1
B þ M2 %BM2 ; K2 ¼ ¼ ;b ¼ (3) Furthermore, the sorption rate of the process will determine the
k2 ½BM2  2 K2
type of reactor to be used and contribute final costs. In general, the
The binary Langmuir model as a function of parameter K, or the sorption rate depends on several factors (Veglio et al., 2002; Jalai-
inverse of the equilibrium constant, is given by the following Rad et al., 2004; Rangsayatorn et al., 2004; Diniz and Volesky,
expressions: 2005): 1) the biosorbent or type of biomass (chemical composition
and number of active sites) and its physiological state (active or
qmax
CeðM1 Þ inactive, free or immobilized) and structural properties (surface
K1
qe ðM1 Þ ¼ (4) area, morphology); 2) the metal, its diffusion in the biosorbent,
1 1 concentration, and competition with other metal ions by active
1 þ CeðM1 Þ þ CeðM2 Þ
K1 K2 sites; and 3) experimental conditions, especially stirring.
Fig. 1 depicts the evolution of metal concentration versus time in
qmax monometallic systems for an initial concentration of 10 mg/L. The
CeðM2 Þ
K2 biosorption process was very fast and around 80% of metal was
qe ðM2 Þ ¼ (5)
1 1 recovered in the first 8 min while equilibrium was reached at
1 þ CeðM1 Þ þ CeðM2 Þ
K1 K2 30 min. Similar results were obtained for the rest of initial metal
concentrations tested in agreement with other studies that have
Thus, parameter K is inversely proportional to the affinity of the
established biosorption times shorter than 15 min after bio-
biomass for one of the two metals in solution. Then, a high value of
massemetal solution contact (Reddad et al., 2002; Deng and Bai,
K for metal M2 (K2) versus M1 (K1) means that the biosorbent
2004; Martins et al., 2004; Chojnacka et al., 2005; Goksungur
presents a higher affinity for the latter than for the former metal
et al., 2005; Seki et al., 2005).
since a high value of K is associated to a high metal desorbed/metal
Fig. 2 shows the variation of pH versus time for tests at
adsorbed ratio. Those constants together with the maximum
different initial Pb concentrations. pH values increased with
biomass sorption uptake were determined with the MATLABÒ 5.1
decreasing the concentration of this metal in solution. This was
software (MATLAB, 1997).
expected since the binding mechanism of protons to active
centres of the biomass is similar to that of metal cations in
2.5. Recovery of the metal adsorbed solution (Matheickal et al., 1999; Yu and Kaewsarn, 1999; Yu
et al., 2001; Gulnaz et al., 2005; Han et al., 2005; Lin and Lin,
The reuse of the biomass was considered in consecutive sorp- 2005; Saeed et al., 2005). For biomass with free active sites,
tionedesorption cycles. After sorption, the biomass was recovered
by filtration and dried in a stove at 60
C for 12 h. In that way,
desorption tests were performed using the same biomass concen- Pb
tration as in sorption tests. Then, the biomass loaded with metal 7
10 mg/L 25 mg/L 50 mg/L
was treated with an eluent (HCl at pH 3 or 0.1 N NaHCO3) and
100 mg/L 150 mg/L
samples of 5 mL were removed at different times to evaluate
desorption kinetics. After 120 min, tests were centrifuged and pH
6
and metal concentration determined in the supernatant solution.
pH

This process was repeated two times.

3. Results and discussion 5

3.1. Sorption kinetics

4
There is a double interest in sorption kinetics: 1) to gather
0 50 100 150
information on the biosorption process at different pH and metal
Time (min.)
concentrations and 2) to estimate the time required to complete
the process. Fig. 2. pH versus time in monometallic systems at different initial Pb concentrations.
 J.M. Lezcano et al. / Journal of Environmental Management 92 (2011) 2666e2674 2669

the simultaneous uptake of metal cations and protons increased 3.3. Sorption isotherms in bimetallic systems
the solution pH.
The fast biosorption rate would be related to two facts: the The analysis of bimetallic systems is based on competition
process takes place mainly on the biosorbent surface (Herrero et al., between metal species in solution and can be treated in three
2005; Kamala et al., 2005) and metal binding is accomplished by different ways (Chong and Volesky, 1995; Loaec et al., 1997; Lee and
fast reversible reactions independent of metabolism (Cruz et al., Volesky, 1999; Hammaini et al., 2002; Volesky, 2003; Mehta and
2004; Pagnanelli et al., 2004a,b). Gaur, 2005):
In general, biosorption in bimetallic systems was slightly slower
than for monometallic systems, and this is in agreement with other (i) Fitting experimental data to bidimensional isotherms, as for
experimental studies (Ozdemir et al., 2005). Those differences monometallic systems. Thus, each isotherm represents the
could be due to the absence of competition phenomena in mono- different sorption uptakes of the first metal, as a function of its
metallic systems. equilibrium concentration, for each given concentration of the
second metal. This method allows a qualitative but not
quantitative analysis of the sorption influence of one metal
over the other one.
(ii) Fitting experimental data to 3-D surfaces, using three axes: X
3.2. Sorption isotherms in monometallic systems
and Y axes represent the equilibrium concentrations of both
metals and Z axis the sorption uptake of one of the two metals
The sorption process was quantified from the equilibrium
or the sum of both. This method is a better plot than the
parameters obtained by fitting the experimental data to the two
former but, as main drawback, sometimes shows irregular
mathematical models usually employed in literature: Langmuir
surfaces that are far from being the real behaviour of the
and Freundlich (Chojnacka, 2005; Goksungur et al., 2005; Gulnaz
bimetallic system. In addition, it only provides qualitative
et al., 2005; Han et al., 2005; Herrero et al., 2005; Kamala et al.,
information.
2005; Lodeiro et al., 2005; Mehta and Gaur, 2005; Saeed et al.,
(iii) Fitting experimental data to a mathematical model. This
2005).
method, unlike the others, provides quantitative information
Table 2 collects the values of the relative constants for both
of the biosorption process in bimetallic systems. Among the
models and the linear regression coefficient (R2). The latter values
mathematical models described in the literature for bimetallic
indicate a better fitting of experimental data to the Langmuir than
systems, the binary-type Langmuir model has been the most
to the Freundlich model. According to the former model, the bio-
applied since, besides being the most simple, it allows the
sorption process: 1) takes place in a monolayer; 2) there is homo-
determination of the equilibrium constant of the bio-
geneity with respect to the type and affinity of metal by the active
massemetal interaction given whether by the value of b or by
sites; 3) the adsorbed ions do not affect the sorption of other ions
its inverse (K). This method was adopted in the present work.
by neighbour active centres; and 4) metal can saturate the biomass
(Puranik and Paknikar, 1997; Satiroglu et al., 2002; Goksungur et al.,
The values of the Langmuir constants corresponding to the three
2005; Saeed et al., 2005).
systems studied and obtained using the MATLAB 5.1 software are
A similar conclusion can be reached from the analysis of
given in Table 3. The maximum sorption uptake of the biomass,
constants for each metal derived from both models: values of qmax
qmax, remained practically constant for all systems around
for the Langmuir model and Ke for the Freundlich model gave the
0.5 mmol of cation adsorbed/g of biomass. That would be an indi-
following sorption order: Pb w Cu > Cd. This sequence is in
cation that the number of active sites in the biomass available for
agreement with the electronegativity values of the different metal
metal binding is fixed and independent of the working solution
cations tested (Sheng et al., 2007): the higher the electronegativity
(Romera et al., 2008).
of the ion the stronger is the attraction for the negatively charged
Considering the values of the affinity parameters, K1 and K2, for
ligands on the biomass. Of the three metals tested, Pb and Cu, with
the CueCd and PbeCd bimetallic systems, the affinity of the
the highest electronegativity (2.33 and 1.91, respectively), were
biomass was five times higher for Cu or Pb than for Cd. In contrast,
adsorbed in a greater extent. Cadmium, with a lower electronega-
the biomass presented a high and similar affinity for both metals for
tivity (1.69) and a larger volume, presented the lowest metal
the PbeCu system.
uptake.
Similar results were obtained by Sheng et al. (2007), in binary
The metal ion affinity order of the biomass, deduced from the
systems and using the marine alga Sargassum sp. Moreover, our
values of K from the Langmuir model, was: Pb > Cd w Cu. In spite
results agree with those recorded in monometallic systems, espe-
that the affinity for cadmium was high, the metal uptake was low as
cially for Pb, the metal with the lowest value of K (Table 2).
indicated by the value of qmax. This behaviour could be related to
However, unlike monometallic systems, the biomass presented
the presence of few active sites, but with low activation energy, on
a different affinity for Cu and Cd in bimetallic systems. A similar
the cell wall to bind this metal. In such case, Cd would be easily
biosorption behaviour was observed using Fucus spiralis as bio-
bioadsorbed at low concentrations but saturation is rapidly reached
sorbent (Romera et al., 2008). In this case, the different electro-
(Hashim and Chu, 2004).
negativity of both ions (higher for Cu) and the different ion radius
(bigger for Cd) could be responsible for such results.

Table 2
Langmuir and Freundlich constants.
Table 3
Metal Langmuir Freundlich
Values of Langmuir constants for the three bimetallic systems studied.
qmax (mmol/g K (mmol/L) R2 Ke (mmol/g 1/n R2
System K1 (mmol/L) K2 (mmol/L) qmax (mmol/g)
biomass) biomass)
CudCd Cu: 0.066 Cd: 0.340 0.474
Cd 0.290 0.055 0.993 0.576 0.188 0.955
PbdCu Pb: 0.001 Cu: 0.004 0.452
Cu 0.508 0.067 0.996 0.719 0.196 0.897
CdePb Cd: 0.340 Pb: 0.066 0.474
Pb 0.388 0.003 1.000 0.707 0.125 0.986
2670 J.M. Lezcano et al. / Journal of Environmental Management 92 (2011) 2666e2674
Let us consider each bimetallic system separately:
3.3.1. CdeCu system
The competition between Cd and Cu for the active sites of the
biomass is depicted in Fig. 3. The surface isotherms show a decrease
of cadmium uptake in the presence of increasing amounts of Cu
(Fig. 3b). In contrast, Cu uptake was kept high even at high Cd
concentrations (Fig. 3a). The higher affinity of the biomass for Cu
agrees with the previous values of K. The sorption for the simul-
taneous uptake of both metals reached a constant value
Fig. 3. Sorption isotherms for the CueCd system.
independently of each metal concentration, as expected from the
values of qmax obtained (Fig. 3c).
3.3.2. CuePb system
The isotherm for this system (Fig. 4) shows that the influence of
Pb on the Cu sorption uptake was similar to its reciprocal, in
agreement with the low values of K obtained for both metals. In this
bimetallic system, the biomass reached saturation faster than in the
previous system which is a clear indication of the high affinity of
the biomass for both metals (Fig. 4c).
Fig. 4. Sorption isotherms for the CuePb system.
 J.M. Lezcano et al. / Journal of Environmental Management 92 (2011) 2666e2674
3.3.3. PbeCd system
Fig. 5 shows that Pb had a negative effect on the uptake of Cd,
especially at high concentrations of the former metal. Conversely,
the effect of Cd on the Pb sorption uptake was practically negligible
(Fig. 5a). This behaviour is in agreement with the previous quan-
titative analysis according to which the affinity of biomass is pref-
erentially towards Pb than Cd. Also, the simultaneous sorption
uptake of both metals reached a constant value independently of
metal concentration (Fig. 5c).
Let us consider all bimetallic systems globally:
In all cases, an increase of concentration of a given metal led to
a lower sorption uptake of the other metal present in solution since
Fig. 5. Sorption isotherms for the PbeCd system.
2671
both metals compete for the same active centres of the bio-
adsorbent (Chong and Volesky, 1995; Loaec et al., 1997).
The affinity order of the biomass agrees with that obtained for
monometallic systems: Pb w Cu > Cd. A higher affinity of a given
metal with respect to the other one can be due whether to lower
activation energy, to a stronger binding strength towards the active
centre, or to a different binding mechanism. Some authors have
pointed out that the affinity can be related to specific properties of
each metal, such as (Chong and Volesky, 1996): ionic radius (the
smaller the radius the higher the affinity) or cation charge density
(the higher the charge density the higher the affinity because
a higher electrostatic attraction).
In the three cases studied, the total amount of metal adsorbed,
obtained from the sorption uptakes of both metals in solution,
tends to a maximum and constant value around 0.5 mmol/g. This
would be in agreement with Langmuir’s hypothesis that the
number of active centres available on the biomass is fixed and
remains constant over the whole surface and that each metal ion
could bind any of them (Chong and Volesky, 1995; Loaec et al.,
1997).
3.4. Recovery of the metal adsorbed
The desorption process for the recovery of metals is based on
several mechanisms. Basically, there are three desorption mecha-
nisms (Huang et al., 1998; Kapoor et al., 1999; Gardea-Torresdey
et al., 2004):
(i) Precipitation of the metal adsorbed by formation of insoluble
compounds with the desorbent agent, e.g. H2S.
(ii) Complexation of the metal adsorbed by reaction with
compounds which have pairs of electrons available to share
with the metal cation. Desorbent agents such as NaHCO3,
Na2CO3 and EDTA follow this mechanism.
(iii) Ion exchange. This mechanism gives good yields by
exchanging a cation from the desorbent agent for the metal
adsorbed. The most common desorbent agents in this category
are: HCl, H2SO4 and NaOH.
There is a large number of desorbent agents that can be used but
acids, inorganic or organic, have the highest metal desorption
capacity (Huang et al., 1998; Davis et al., 2000). The desorbent agent
should fulfil four basic requirements: 1) a high elution efficiency; 2)
low damage of the biomass in order to be reused in subsequent
cycles; 3) low degree of contamination; and 4) low cost (Davis et al.,
2000; Gardea-Torresdey et al., 2004; Chojnacka et al., 2005; Mehta
and Gaur, 2005).
In the present study, two different eluent agents were selected:
one acidic (HCl) and another complexing (NaHCO3), both with
a relatively low cost.
3.4.1. HCl as desorbent
Fig. 6 shows the elution kinetics with HCl quantified as a func-
tion of the amount of metal release. Like biosorption, the desorp-
tion process took place rapidly and more than 80% of metal retained
on the biomass was released within the first 5 min. In addition, the
increase of pH during desorption (Fig. 6) would indicate an
exchange between metal cations adsorbed and protons supplied by
the desorbent agent, in agreement with other authors (Huang et al.,
1998; Gardea-Torresdey et al., 2004; Mehta and Gaur, 2005).
Fig. 7 shows the amount of metal retained by the biomass after
each biosorption or desorption step. HCl was markedly efficient as
desorbent agent (Desorption I) with metal recoveries of 85.7% for
Cd, 66.7% for Cu and 63.2% for Pb. Thus, the desorption sequence
was inverse to the sorption order recorded. These results agree with
2672 J.M. Lezcano et al. / Journal of Environmental Management 92 (2011) 2666e2674

0,20 4 0,15 9

Metal released (mmol/L)

Metal released (mmol/L)

3,8 8,5
0,15
0,10
3,6

pH
8

pH
0,10
3,4 0,05
7,5
0,05
3,2
0,00 7
0,00 3
0 20 40 60 80 100 120 140
0 20 40 60 80 100 120 140
Time (min.)
Time (min.)
Cd released Cu released Pb released
Cd released Cu released Pb released Cd pH Cu pH Pb pH
Cd pH Cu pH Pb pH
Fig. 8. Desorption kinetics using NaHCO3.
Fig. 6. Desorption kinetics using HCl.

NaHCO3 %Naþ þ HCO

those obtained by several authors (Mattuschka et al., 1993; Puranik
and Paknikar, 1997; Davis et al., 2000; Lin and Lin, 2005; Saeed
et al., 2005).
However, once the biomass was reused in a new biosorption test
(Biosorption II) its efficiency significantly decreased with respect to
the first sorption cycle (Biosorption I).
This could be due to several factors, such as: structural damages
of the active centres provoked by the desorbent agent, or blockage
of those sites due to the inefficiency of the eluant leaving less active
sites available for the a new sorption cycle (Puranik and Paknikar,
1997; Davis et al., 2000; Rangsayatorn et al., 2004; Sekhar et al.,
2004; Lin and Lin, 2005; Vijayaraghavan et al., 2005a,b).
3.4.2. NaHCO3 as desorbent
The desorption kinetics with NaHCO3 (Fig. 8) showed that
despite being a process relatively fast, recoveries higher than 80%
can be reached in the first 30 min, had a worse performance than
HCl. The desorption mechanism can be explained by the existence
of bicarbonate anions with pairs of electrons available that can
remove by complexation the metal cations uptaked by the biomass
(Puranik and Paknikar, 1997; Gardea-Torresdey et al., 2004).
As in the previous case, an increase of solution pH took place
simultaneously to metal desorption (Fig. 8). In this case, however, it
should not be due to ion exchange since it is a weak acid salt and its
dissociation in the aqueous medium provides alkalinity due to the
following equilibria:
3 (6)
HCO
3 þ H2 O%H2 CO3 þ OH

(7)
Thus, this would explain the slight increase of pH shown in
Fig. 8.
Fig. 9 depicts the amount of metal at the end of each sorption or
desorption step. The efficiency of NaHCO3 as desorbent agent was
relatively low, except for Cu, with a recovery of 76.7%, the recovery
for the rest of metals was: 11.4% for Pb and 1.4% for Cd.
In spite that in the first desorption process (Desorption I) metal
recovery was low, the reuse of the remaining biomass (Biosorption
II) in a second biosorption cycle improved significantly both its
sorption uptake and metal recovery that was even higher than in
the first cycle (Biosorption I). This would be related to chemical
changes in the biomass produced by NaHCO3. Yan and
Viraraghavan (2000) have reported similar effects of NaHCO3,
after a second cycle under identical conditions, on Mucor rouxii and
the increase of the sorption uptake observed was attributed to
several facts: removal of impurities on the biomass surface,
breakdown of the cell wall or generation of new sorption active
centres.
After a second desorption (Desorption II) in identical conditions
to the first one, the desorption yield was even lower than that
recorded in the first cycle (Fig. 9). The percentages of metal des-
orbed, with respect to the total amount of biomass, after the second
biosorption cycle, were: 53.8% for Cu, 3.0% for Pb and 0.3% for Cd.

0,6
0,8
Cd Cu Pb
Amount of metal retained

0,5 0,7 Cd Cu Pb
(mmol/g of biomass)

Amount of metal retained

0,6
(mmol/g of biomass)

0,4
0,5
0,3 0,4

0,3
0,2
0,2
0,1
0,1

0 0
Biosorption I Desorption I Biosorption II Biosorption I Desorption I Biosorption II Desorption II

Fig. 7. Metal uptake by the biomass after different sorptionedesoprtion cycles with Fig. 9. Metal uptake by the biomass after different sorptionedesorption cycles with
HCl. NaHCO3.
 J.M. Lezcano et al. / Journal of Environmental Management 92 (2011) 2666e2674
Clearly, metal desorption after the first cycle was higher using
HCl than NaHCO3. A plausible explanation is the different
performance mechanism of each eluant: ion exchange for HCl
and complexation for NaHCO3 (Gardea-Torresdey et al., 2004).
Nevertheless, HCl, a strong acid, could provoke a serious damage
on the biomass affecting its sorption capacity. On the contrary,
NaHCO3 significantly improved the sorption uptake of the
biomass.
Therefore, the significant increase of sorption of the biomass
treated with NaHCO3 is an indication that this reagent is able to
improve its metal sorption uptake.
4. Conclusions
- The eutrophized biomass can be used effectively for decon-
taminating effluents contaminated with heavy metals.
- The sorption kinetics in monometallic systems was very fast
and equilibrium was reached after 30 min. The pH values
increased with decreasing metal concentration because of
competence phenomena between protons and metal cations
for the same active sites of the biomass.
- The sorption kinetics in bimetallic systems was slower than in
monometallic systems and the equilibrium was reached after
120 min. That was related to the strong competence between
metal cations for the same active sites of the biomass.
- The sorption order in monometallic systems was: Cu w Pb > Cd
and the biomass-metal affinity: Pb > Cd w Cu.
- The affinity order in bimetallic systems was: Pb w Cu > Cd. In
addition, the maximum total amount of metal adsorbed for the
three systems studied was around 0.5 mmol/g.
- The desorption process was fast and released more than 80% of
the metal adsorbed within the first 5 min with HCl and in the
first 30 min with NaHCO3.
- The percentages of metal recovery obtained with HCl in the
first cycle ranged between 63 and 100%. The lower sorption
metal uptake with reused biomass was related to damage or
blockage of its active centres.
- The percentages of metal recovery obtained with NaHCO3 in
the first cycle ranged between 1 and 77%. The sorption metal
uptake increased for the reused biomass but the yield of the
second desorption cycle was lower than for the first one.
Acknowledgements
The authors wish to express their gratitude to the Spanish
Ministry of Science and Technology for funding this work.
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