Chemical Engineering Journal 168 (2011) 44–51

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Chemical Engineering Journal

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Kinetic and equilibrium adsorption of Cu(II) and Cd(II) ions on Eichhornia

crassipes in single and binary systems
Aparecido N. Módenes ∗ , Fernando R. Espinoza-Quiñones, Daniela E.G. Trigueros, Fábio L. Lavarda,
Andreia Colombo, Nora D. Mora
Department of Chemical Engineering, Postgraduate Program, West Parana State University, UNIOESTE, Campus of Toledo, rua da Faculdade 645, Jd. La Salle, 85903-000 Toledo, PR,
Brazil

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

Article history: In this work, the sorption capacity behavior of copper and cadmium divalent ions in single and binary
Received 13 October 2010 systems has been investigated. Batch metal sorption experiments to obtain the kinetic and equilibrium
Received in revised form 8 December 2010 data for the dry biomass of the Eichhornia crassipes species were performed under controlled temperature,
Accepted 9 December 2010
constant shaking and pH 5. An equilibrium time of 60 min was achieved for both Cu(II) and Cd(II) ions
in mono-component system as well as in binary one. It was found that the overall adsorption data were
Keywords:
best described by the pseudo second-order kinetic model. Six adsorption isotherms have been tested
Biosorption surface modeling
to fit the mono-component equilibrium data, obtaining the best description by the Langmuir-type one.
Multi-component
Metal adsorption capacity
A modified extended-to-multi-component Langmuir-type isotherm model was applied to predict the
binary adsorption data and its adjustable parameters were estimated by the PSO method. Finally, the
results have shown that the affinity of each metal ion onto the E. crassipes surface is influenced by the
presence of the other one.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction
The pollution of aquatic ecosystem by heavy metals resulting
from the release of industrial effluents is a matter of great con-
cern. In aquatic environment, heavy metals such as cadmium and
copper are accumulated on biota and bio-magnified in the food
chain, resulting in harmful effects on human physiology and other
biological systems [1,2]. Cadmium is one of the most toxic heavy
metals, even in low concentrations, causing renal dysfunction, bone
degeneration, lung inefficiency, liver damage and hypertension in
humans, while copper can be deposited in the brain, skin, liver,
pancreas and myocardium causing serious toxicological effects on
humans and animals [3,4].
In high metal concentration-contaminated wastewater treat-
ments, several conventional methods such as chemical precip-
itation, membrane filtration, ion exchange and electrochemical
treatment have also been applied [5–9]. However, when the most of
these methodologies are applied in low metal concentration efflu-
ent treatments, they could have high chemical costs or low removal
efficiencies, low selectivities, high-energy requirements, and gen-
eration of secondary toxic slurries [10]. A variety of mechanisms
∗ Corresponding author. Tel.: +55 45 3379 7092; fax: +55 45 3379 7002.
E-mail addresses: modenes@unioeste.br, anmodenes@yahoo.com.br
(A.N. Módenes).
exist for the removal of heavy metals in low concentrations from
aqueous solution by macrophytes [11–16], activated carbon [17],
fungi [18], orange peel [19–21], and higher plants [22], sequestering
and accumulating metallic ions.
Although lot of works have used different biomaterials as low
cost biosorbent for single metal removal, while employing the
biosorption technique, the presence of a large number of metals
in industrial wastewaters has increased the difficulty in studying
the adsorption of multimetal systems [23]. In such systems, the
metal ion biosorption is strongly depending on the solution pH,
initial metal ion concentration, surface properties of the adsor-
bent, the interaction between metal ion species among others
[1]. So far, many biosorption researches have been mainly dedi-
cated to test biomaterials as biosorbent, investigate their selectivity
and adsorption capacity, and explain the interference and com-
petition produced by metals for adsorption sites on the basis of
representative biosorption isotherms and kinetic models. In this
context, literature survey also reveals that the application of dead
biomass of aquatic macrophytes like Eichhornia crassipes [24,25],
Spirodela intermedia, Lemna minor and Pistia stratiotes [26], and Ege-
ria densa [10–12] among others is preferred as efficient biosorbent
for removing heavy metal from aqueous system.
The aim of this work was to evaluate the adsorption capacity of
E. crassipes as well as to investigate on the adsorption equilibrium
and kinetic of copper and cadmium divalent ions in both single and
binary component systems. Preliminary tests were also performed

1385-8947/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2010.12.029
 A.N. Módenes et al. / Chemical Engineering Journal 168 (2011) 44–51
to optimize the conditions, viz. drying temperature and biosorbent
grain size for removal of copper and cadmium ions from single
and bi-metal systems. As the presence of one ion could influence
the maximum capacity or affinity of other ones in a Cu–Cd binary
sorption system, correction parameters to the classical competi-
tive Langmuir equation have been used in order to make the model
capable to depict the complexity of the adsorption process. The
PSO method was used to predict all modified extended Langmuir
isotherm parameters, allowing fitting well the multi-component
adsorption data in a 3-D representation. These studies may be
useful for low cost industrial wastewater treatment, where the
simultaneous removal of several heavy metals is needed.
2. Materials and methods
2.1. Chemicals
The chemicals used were of analytical-reagent grade. Deionized
waters were also used as dilution media. Several stock solutions of
Cu and Cd in deionized waters were prepared, ranging from 4.0 to
8.0 mequiv. L−1 , from their water-soluble metallic salt (CuCl2 ·2H2 O
and CdCl2 ·H2 O, Merck Pro Analysis) and stored in 1-L volumet-
ric flasks for posterior metal adsorption experiments. Solutions of
NaOH (1 M) and HCl (1 M) were also used as a pH adjustment. Based
on Cu and Cd standard solutions (1.0 g L−1 for AAS, Merck), different
diluted-metal concentrations ranging from 0.1 to 1.5 mg L−1 were
also prepared and used to obtain the calibration curve for atomic
absorption spectrometer (AAS).
2.2. Biomass Sampling
For biosorption experiments, aquatic macrophytes E. crassipes
plants were collected from natural shallow ponds near Cascavel
city, which is located in the western region of the Brazilian Paraná
state. After collection, aquatic macrophytes E. crassipes were thor-
oughly cleaned in running tap water, in order to eliminate any
remains of sediment and particles. In the laboratory, the biomasses
were dried using an electrical oven at 30 ◦ C and then grounded
using the steel-knifes electrical mill and sieved into different par-
ticle sizes.
2.3. AAS measurements
For metal concentration measurements, after each test and
biosorption experiment, the liquid phase was separated from
the adsorbent by a vacuum filtration system using 0.45 ␮m-
membranes. An absorption atomic spectrometer, model AA
932-GBC (Analitica) was used. For cadmium analysis, eight diluted
standard solutions ranging from 0.004 to 1.8 mg L−1 were used in
order to calibrate the absorption atomic spectrometer (AAS), while
for copper, the AAS calibration was made by using eight diluted
standard solutions ranging from 0.01 to 4 mg L−1 , respectively. The
calibration coefficients (r2 ) obtained from four calibration stan-
dards for all analyses were 0.995 or better. The wavelengths (nm)
used for the metals were: Cu, 224.7 and Cd, 228.8. After the AAS cal-
ibration, some samples were diluted to fit in the calibration range.
Confidence intervals of 95% were calculated for the results.
2.4. Preliminary tests
In order to improve the biosorption kinetic and experimental
equilibrium conditions, the temperature effect on the drying plant
was tested using a 30–50 ◦ C temperature range, while the sorption
temperature effect was evaluated at four controlled temperatures,
ranging from 25 ◦ C to 45 ◦ C. For these tests, a volume of 50 mL for
45
metal solution was added to 250 mg dry plant in a 125-mL Erlen-
meyer flask. The solution pH was adjusted below the precipitation
threshold for each metal, approximately 5.0 for both metal ions
[12]. The mixtures were shaken on a rotary shaker for 120 min for
each temperature setting, and then, the quantity of metal in each
sample was measured by AAS. The biosorbent grain size effect was
also studied, using three fractional grain sizes between 0.147 and
0.589 mm and their mixture as well. This test was carried out using
the same procedure for the temperature effect test, but in this case,
a 30 ◦ C controlled temperature metal solution and 120 min con-
tact time were used. Then the metallic solution was separated from
the biosorbent by using a vacuum filtration system and the metal
concentrations were measured by AAS. The amount of adsorbed
metal during contact time by E. crassipes biomass was calculated
according to the mass balance expressed by Eq. (1):
V (C0 − Ct )
qt = (1)
m
where qt (in mequiv. g−1 ) is the amount of adsorbed metal by E.
crassipes, C0 and Ct (in mequiv. L−1 ) are the initial and final metal
concentrations in solutions, respectively, V is the solution volume
and m is the adsorbent mass.
2.5. Kinetic test
In order to obtain the equilibrium time, single standard solutions
of Cu and Cd were prepared of approximately 4.0 mequiv. L−1 . For
monocomponent kinetic experiments, a 250 mg dry biomass was
added to a 50 mL metal solution of Cu and Cd, at 5 initial pH, while
for a binary mixture only 25 mL of each metal solution was added
to 250 mg dry biomass. The mixtures were agitated on a shaker at
30 ◦ C constantly controlled temperature. The solution for pH moni-
toring was carried out during the sorption experiments and the pH
adjustment to 5 was made, as required. The adsorption experimen-
tal times were set up at several short contact times, ranging from 0
to 120 min, in order to determine the equilibrium time. In this way,
a whole sample was taken at each setting time and the liquid phase
was separated from the adsorbent using a vacuum filtration system.
Afterwards, initial and final cadmium concentrations in each liquid
phase were determined by AAS and the amount of adsorbed metal
(qt ) during contact time by E. crassipes was calculated by Eq. (1).
2.6. Equilibrium tests
Several batch single metal sorption experiments using the E.
crassipes biomass as biosorbent were carried out using a con-
stant volume of 50 mL metal-supplied solution (4.0 mequiv. L−1 ) in
contact with dry biomass, ranging from 20 to 550 mg. For batch
Cu–Cd sorption experiments, only 25 mL of each metal solution
with the same initial concentrations (4.0 mequiv. L−1 ) was added
to dry biomass, ranging from 20 to 550 mg. All experiments were
performed in duplicates, with constant shaking and controlled tem-
perature of 30 ◦ C, and the pH adjustment to 5 was made, as required,
during the 120 min contact time. Afterwards, the whole sample was
taken at each setting time and the liquid phase was separated from
the adsorbent by using a vacuum filtration system, which deter-
mined the initial and final metal concentrations for each liquid
phase by AAS and the amount of adsorbed metal (qt ) during contact
time by E. crassipes was calculated by Eq. (1).
2.7. Search analysis of kinetic and equilibrium adsorption
parameters
In this work, a stochastically optimized global method, called
a particle swarm optimization (PSO) proposed by Kennedy and
46 A.N. Módenes et al. / Chemical Engineering Journal 168 (2011) 44–51

Table 1
Metal percent removal in preliminary biosorption tests at different values of drying temperature, solution temperature and grain size, using the E. crassipes biomass.

Metal Percent removal

Drying temperature (◦ C) Solution temperature (◦ C) Grain size (mm)

30 50 25 30 35 40 0.147 0.295 0.589 Mixture

Copper 52 ± 2 45 ± 2 41 ± 2 49 ± 2 45 ± 2 40 ± 2 44 ± 2 43 ± 2 44 ± 2 45 ± 2
Cadmium 41 ± 2 35 ± 2 53 ± 2 63 ± 2 56 ± 2 57 ± 2 52 ± 2 51 ± 2 52 ± 2 53 ± 2

Eberhard [27], has been applied to search for the globally opti- previous results, the 30 ◦ C solution temperature was set up for sin-
mized parameter values, which correspond to a set of non-linear gle and binary metal sorption experiments. On the other hand, the
models that represent the kinetic and equilibrium adsorption data. metal-sorption experiments based on fractional biomass grain sizes
The PSO method is similar to the evolutionary algorithms (EAs) (0.147–0.589 mm) have not shown significant differences on the
and is based on a population of individuals, called particle swarm. metal ion removal as compared to their mixture and different grain
However, the only difference between EA and PSO is in the space sizes tested (see Table 1). For practical purpose, the grain size effect
localization of individuals (particles) recognized by the operator might be considered insignificant, and consequently, grains, with-
speed. In genetic algorithms GA, the individuals pass through the out a previous size separation after the grounding process, were
operator reproduction, mutation and election [13]. PSO method has chosen, obtaining thus a 45% and 53% removal rate for copper and
been recently applied in several studies to solve nonconstrained cadmium, respectively.
optimization problems [28–33]. In contrast to the linearization
methods, the search procedure was found to reach convergence 3.2. Kinetic test
in a few iterations for the given numbers of parameters and objec-
tive functions. The obtained results were comparable with those The E. crassipes biomass-based kinetic data using copper and
obtained via an application of a hybrid genetic algorithm. In early cadmium in single and binary biosorption systems, at pH 5 and
works [28–30], the parameter identification procedure based on 30 ◦ C solution temperature are shown in Fig. 1. Logistic-type func-
the PSO method was reported, having empirically estimated the tions are used to fit the adsorption process of single metal (Fig. 1a)
essential PSO parameter values and their influence on the search achieving a good correlation coefficient (r2 = 0.981 for Cu and
space for the estimation of modeling parameters, in order to obtain
a quick and good convergence and reliable results.
The description of the PSO algorithm is basically as follows: sin-
gle particle in a chaotic movement in an N-particles swarm, namely
solution search space, is kinematically described as reported in
previous works [13,28–30], where its position vector and the
corresponding velocity one are iteratively assigned, based on a
few parameters or variables that resemble swarm inertia, chaotic
movement of each particle in the swarm and their geographical
space constraints. For the initialization of the population, the fol-
lowing parameter values are predefined: particle number, number
of iterations, number of parameters, inertia factors, acceleration
constants and the search limit. The fitness of each particle is
measured in accordance with statistical criterion (the last square
method as objective function). When the specified number of iter-
ations is reached, the best search solution is used as information
in the process of restriction of the search space, where the most
sensible parameters are considered. This evaluation of the param-
eter sensitivity is possible in a graphical dialog, by using Maple®
software. The end of the search is determined by the better global
position of the swarm. For the PSO method application to equilib-
rium adsorption data, a swarm of 1000 particles with 30 iterations
was considered and a built-in objective function based on the least
square statistical method was used.

3. Results and discussion

3.1. Preliminary results

Within the drying temperature range tested, a slight difference

on the metal removal performance for copper and cadmium ions
was observed when 30 and 50 ◦ C drying temperatures were used, as
shown in Table 1. Then, a drying temperature of 30 ◦ C was chosen in
order to reduce the preparation cost. In the interval from 25 to 45 ◦ C
controlled temperatures, the highest metal removal percent was
observed to occur at 30 ◦ C solution temperature, corresponding to Fig. 1. Effect of the contact time on (a) single and (b) binary sorption of copper and
cadmium ions for E. crassipes, at pH 5, 120 min and 30 ◦ C. Standard deviations are
a removal rate of 49 and 63% for Cu and Cd, respectively, which were equal or less than the symbol size for all metals. All data were fitted by logistic-type
approximately 12% above the other ones (see Table 1). Based on the functions.
 A.N. Módenes et al. / Chemical Engineering Journal 168 (2011) 44–51 47

r2 = 0.996 for Cd) and 2 (1.889 for Cu and 0.574 for Cd), allowing to
extract further information such as equilibrium time. The biosorp-
tion of each metal has increased sharply at short contact and slowed
gradually as equilibrium was approached around 60 min contact
time and achieving approximately 52% and 58% removal for Cu
and Cd ions, respectively. This kind of behavior is typical for metal
biosorption characterized by no energy exchange reaction, and
thus, the metal removal is governed by a purely physical–chemical
interaction between the biosorbent and the metal-supplied liquid
phase.
For binary adsorption process (Fig. 1b), logistic-type functions
that allow extract further information from kinetic data are also
used, achieving a good correlation coefficient (r2 = 0.984 for Cu and
r2 = 0.994 for Cd) and 2 (0.583 for Cu and 0.142 for Cd). As can be
observed in Fig. 1b the same equilibrium time for binary adsorption
system was also achieved, with removal values of 28 and 25% for
copper and cadmium ions, respectively.
In binary system, the addition of simultaneously observed
removal values for copper and cadmium (approximately 53%)
resembles the 52–58% removal range that was observed in single
adsorption processes. In single adsorption systems, it was observed
that the cadmium removal is higher than copper one, whereas
for a Cu–Cd binary system the preference was inverted, having a
higher copper removal than cadmium one when both metallic ions
are simultaneously being adsorbed onto the E. crassipes biosorbent
surface. This phenomenon might be associated with the different
physical/chemical properties existing between copper and cad-
mium ions in an adsorption process or other ones on the biosorbent
surface.
The kinetic results in the present work were similar in order to
apply this kind of biosorbent in effluent treatment system, when
they are compared with other studied biosorbents in previous
works. Pietrobelli et al. [12], under the same experimental con-
dition, have reported that around 70% uptake of Cu(II) and Cd(II) Fig. 2. The kinetic data of (a) single and (b) binary sorption of copper and cadmium
was observed in single metal adsorption experiments using the ions for E. crassipes, at pH 5, 120 min and 30 ◦ C. Standard deviations are less than the
symbol size for copper and cadmium. All metal adsorption kinetic data were also
E. densa as biosorbent, with equilibrium times around 45–60 min. fitted by linear-type functions, according to the pseudo second order model.
Besides, in another work, Lodeiro et al. [34] have reported that
the cadmium removal and equilibrium time have been found as
tion of the sorption rate constant, namely K2 (g mequiv.−1 min−1 ),
being around 50% and 3 h, respectively, using Bifurcaria bifurcata,
in a simple way.
Saccorhiza polyschides, Pelvetia caniculata, Ascoplyllum nodosum,
Laminaria ochroleuca as biosorbents. Taking into account its low t 1 1
= 2
+ t (3)
equilibrium time, the E. crassipes as biosorbent could reduce the qt K2 qeq qeq
mass transfer zone in a continuous system for lower dimensions
For single and binary metal sorption data, obtained at pH 5 and
than other biosorbents or take the biosorption-based effluent treat-
30 ◦ C solution temperature, the uptake metal concentration in time,
ment systems for a long using time.
labeled as qt , by the E. crassipes biomass was calculated using Eq.
(1). The Ho’s second-order rate equation has fitted better the single
3.3. Adsorption kinetic
metal sorption data as well as the Cu–Cd binary one, according to
the good correlation coefficient values (r2 ≈ 0.999) and as shown in
In order to analyze the metal sorption kinetics in single and
Fig. 2. The sorption rate constant (K2 ) and the uptake metal capac-
binary systems, the pseudo-first order and pseudo-second order
ity at equilibrium (qeq ), which are summarized in Table 2, were
kinetic models were applied to the data. A simple pseudo first-order
estimated from the adjustable straight line parameters, accord-
equation, which was an early proposal by Lagergren, is described
ing to Eq. (3). Fig. 2a shows the single sorption data behavior for
by Eq. (2) [35,36]. From the linearization of the pseudo-first order
copper and cadmium ions and their linear fits, where the slope
kinetic equation, plotted as log(qeq − qt ) versus t, the adsorption
obtained from the linearity of the copper kinetic data is observed
rate constant (K1 ) can be calculated [37]:
 K 
1 Table 2
log (qeq − qt ) = log (qeq ) − t (2)
2303 The equilibrium uptake concentration (qeq ) and sorption rate constant (K2 ) of Cu
and Cd ions for E. crassipes, at pH 5 and 30 ◦ C, obtained from the linearity of the
where K1 is the rate constant of the pseudo first-order adsorp- adsorption kinetic experimental data in single and binary systems, according to the
tion process (min−1 ), qeq and qt (in mequiv. g−1 ) are the adsorption pseudo second-order model.
amounts at equilibrium and in time, respectively.
System Metal qeq (mequiv. g−1 ) K2 (g mequiv−1 min−1 )
On the other hand, the Ho’s second-order rate equation, which
Copper 0.323 ± 0.002 2.344 ± 0.032
has been called a pseudo-second order kinetic expression, has also Single
Cadmium 0.507 ± 0.005 0.717 ± 0.132
been applied widely [38,39] and described by Eq. (3). For this case, it
was convenient to plot the experimental data as t/qt against t, which Copper 0.245 ± 0.007 0.752 ± 0.150
Binary
Cadmium 0.214 ± 0.023 1.558 ± 0.016
shows a linear tendency of the data and allows for the determina-
48 A.N. Módenes et al. / Chemical Engineering Journal 168 (2011) 44–51

to be higher than that of the cadmium one, indicating that E. cras-

sipes exhibits a lower adsorption capacity at equilibrium for Cu
ion (qeq = 0.3229 mequiv. g−1 ) as compared to that for the Cd one
(qeq = 0.5071 mequiv. g−1 ), under the same experimental sorption
condition. From the linear fits of Cu–Cd binary kinetic data in Fig. 2b,
however, the biosorption capacities of the E. crassipes biomass were
0.2445 mequiv. for Cu(II) and 0.2141 mequiv. for Cd(II) per g of dry
biosorbent (see Table 2). In addition, based on the metal biosorption
capacity values, a great part of all the available metal adsorption
sites are preferentially occupied on the E. crassipes surface by the
copper ions instead of cadmium ones.

3.4. Equilibrium adsorption in single and binary systems

In order to optimize the design of biosorption-based effluent

treatment systems to remove metal ions it is important to estab-
lish the most appropriate correlations for the equilibrium curves.
In this context, equilibrium adsorption data for single and binary
systems were obtained at pH 5 and 30 ◦ C temperature, combining
biosorbent dosage values and metal concentration ones.
The experimental data of the single component adsorption
isotherms of Cu(II) and Cd(II) ions have been graphically arranged as
two-dimensional plots and shown in Fig. 3, in which the E. crassipes
biosorbent-based metal uptake is plotted as a function of its corre-
sponding equilibrium metal concentration. To test the fit of data,
most widely known mathematical models of adsorption isotherms,
as summarized in Table 3, have been applied to describe the single
metal uptake by the E. crassipes biosorbent. By employing the min-
imization procedure based on the Levenberg–Marquadt method
that is available in OriginLab Origin 8.0® software, the set of adsorp-
tion fitting parameters corresponding to the each isotherm model
was estimated and summarized in Table 4. It must be noted that
for both metal ions the specific adsorption fitting parameter values,
namely nT , m and g, of the Toth, Sips and Redlich–Peterson isotherm
models, respectively, are equal to one, reducing all of them to the Fig. 3. Sorption isotherm of (a) copper and (b) cadmium for E. crassipes at pH
same Langmuir-type one. The Langmuir, Freundlich and Temkin 5, 120 min equilibrium time and 30 ◦ C. All metal sorption isotherms were fitted
isotherm curves were also drawn in Fig. 3 using their adjustable according to the Langmuir and Freundlich equations.

adsorption parameters (see Table 4). Besides, according to the cor-

relation coefficient values, the Langmuir model has provided the
best fitting of the single component equilibrium data for Cu(II) and
Cd(II) ions in order to characterize the E. crassipes biomass as the
metal adsorbent; followed by the Temkin and Freundlich models.
On the other hand, both Temkin and Freundlich models were not
good isotherms to fit the single component adsorption data since
they exhibit rather higher relative-to-data difference and worse
fitting statistical parameters than the Langmuir one.
In single component adsorption system, the E. crassipes
biosorbent exhibits a higher maximum sorption capacity
(qmax = 0.667 ± 0.036 mequiv. g−1 ) for Cd ion as compared to
that for Cu one (qmax = 0.615 ± 0.037 mequiv. g−1 ), under the same
experimental sorption condition, suggesting the following affin-
ity order Cd(II) > Cu(II). Apart from the obtained metal sorption
capacities, which are lower than those reported by Pietrobelli
et al. [12] for E. densa (1.43 and 1.25 mequiv. g−1 for Cu and Cd,
respectively), the obtained metal sorption ones are comparable to
other types of macrophytes-based sorbents [40], suggesting that
E. crassipes could potentially be used in wastewater treatment
processes involving removal of heavy metals.
On the other hand, the experimental data of Cu–Cd binary
adsorption system can be graphically represented by three-
dimensional plots, namely the metal adsorption surfaces, where the
E. crassipes-based metal uptake responses (z-axis) are plotted as a
function of the equilibrium concentrations of copper and cadmium
ions (x- and y-axis). As the Langmuir isotherm model has shown
the best fitting of the single adsorption data, a multi component
isotherm model based on Langmuir one, namely extended Lang-
muir isotherm model [2], was proposed to describe the adsorption
of metal ions from a binary-metal ion solution on the E. crassipes
biosorbent. However, as reported in the literature [2], in many cases
the adsorption constants of the individual isotherms fail to describe
the interactions between metal ions in a multi-metallic system. For
this reason, further correction parameters to the classical competi-
tive Langmuir equation are introduced, namely modified extended
Langmuir one (Eq. (4)), in order to make the model capable to depict

Table 3
Isotherm models used to fit the single metal adsorption data.

System Isotherm Expression Application Characteristic

Langmuir qeq = qmax [(bL Ceq )/(1 + bL Ceq )] Mono layer Homogeneous surfaces Two theoretical parameters
Freundlich qeq = kF (C)nF Multi layer Heterogeneous surfaces Two empirical parameters
Temkin qeq = B ln(kT Ceq ) Mono layer Chemisorption Two theoretical parameters
Single n 1/n
Toth qeq = qmax (bT Ceq /(1 + (bT Ceq ) T ) T ) Multi layer Heterogeneous surfaces Three empirical parameters
Sips qeq = qmax ((bS Ceq )m )/(1 + (bS Ceq )m ) Combined Langmuir–Freundlich Three semi-empirical parameters
Redlich–Paterson qeq = kRP Ceq /1 + aRP Ceq g Heterogeneous surfaces Three semi-empirical parameters
 A.N. Módenes et al. / Chemical Engineering Journal 168 (2011) 44–51 49

Table 4
Single metal adsorption modeling parameters for Langmuir, Freundlich, Toth, Sips,
Temkin and Redlich–Peterson isotherm models and their respective fitting statistical
parameters, for Cu and Cd adsorption data obtained at pH 5, 30 ◦ C and 120 min
equilibrium time.

Isotherm models Parameters Copper Cadmium

qmax 0.615 ± 0.037 0.667 ± 0.036

Langmuir bL 0.444 ± 0.066 0.566 ± 0.078
r2 0.9688 0.9801

kF 0.207 ± 0.016 0.248 ± 0.017

Freundlich nF 0.425 ± 0.052 0.438 ± 0.052
r2 0.8862 0.9086

kT 0.150 ± 0.011 0.151 ± 0.010

Temkin B 3.369 ± 0.581 5.166 ± 0.851
r2 0.9453 0.9577

qmax 0.615 ± 0.037 0.667 ± 0.036

bT 0.444 ± 0.066 0.566 ± 0.078
Toth
nT 1 1
r2 0.9688 0.9801

qmax 0.615 ± 0.037 0.667 ± 0.036

bS 0.444 ± 0.066 0.566 ± 0.078
Sips
m 1 1
r2 0.9688 0.9801

kRP 0.273 ± 0.026 0.378 ± 0.034

aRP 0.444 ± 0.066 0.566 ± 0.079
Redlich–Peterson
g 1 1
r2 0.9688 0.9801

the complexity of the adsorption process. In the present work, the

modified extended Langmuir equation that is described by Eq. (4)
has been applied to fit the Cu–Cd binary adsorption surfaces:
 
(bLi /nLii )Ceq,i
qeq,i = qmax,i N (4)
1+ j=1
(bLj /nLij )Ceq,j

where qeq,i (mequiv. g−1 ) is the metal uptake of the component i,

N is the number of the components, Ceq,j (mequiv. L−1 ) is the equi-
librium concentration of each component j, while bLi (g mequiv.−1 )
and qmax,i (mequiv. g−1 ) are Langmuir parameters to be determined,
nLi is the correction parameter of species i, which is characteristic
of each species and depends on the concentrations of all the other
components in the solution.
For the PSO method application to equilibrium adsorption data
in Cu–Cd binary system, the performance of each particle is related
Fig. 4. Sorption surfaces of Langmuir-type isotherm fitted to the experimental equi-
to a built-in objective function (OF), determined by the least square
librium data of (a) copper and (b) cadmium in Cu–Cd binary system for E. crassipes at
statistical method, as shown in Eq. (5): pH 5, 120 min equilibrium time and 30 ◦ C. Both binary sorption surfaces modeling
  q∗exp − q∗pred 2 for Cu–Cd system were performed by the PSO method.
OF = (5)
q∗exp

where q∗exp and q∗pred (in mequiv. g−1 ) are the quantities of equi-
librium adsorbed metal by E. crassipes biosorbent, which were
Table 5
experimentally obtained in binary metallic system and predictable Binary metal adsorption modeling parameters for extended modified Langmuir
by modeling, respectively. isotherm model obtained from the Cu–Cd adsorption data (pH 5, 30 ◦ C and 120 min
In the case of a mixture of Cu(II) and Cd(II) ions, it can be seen equilibrium time).
that the modified extended Langmuir model provides adequate Metallic ion Parameters Estimated values by the PSO method
prediction of the binary data, including the single one. Fig. 4 shows
qmax1 0.615
a wide visual perspective of adsorption behavior as a mixture of
bL1 0.444
Cu(II) and Cd(II) ions in different concentration values is consid- Cu(II)
nL1 0.7044
ered. Regarding the modeling of binary adsorption data, the values r2 0.9864
of the maximum adsorption capacities (qmax,i ) and affinity param- qmax2 0.667
eter (bLi ) for Cu(II) and Cd(II) ions were kept the same that those bL2 0.566
obtained from the fits of the single adsorption data by Langmuir Cd(II) nL2 1.3649
isotherm model. Adjustable parameters were estimated by the PSO r2 0.9894
OF 0.062002
method and their values and indicators of the goodness of fit (r2 and
OF) are summarized in Table 5. In Fig. 5, the obtained simulation
results by using the PSO method have been compared to the equi-
50 A.N. Módenes et al. / Chemical Engineering Journal 168 (2011) 44–51
Fig. 5. Linear correlation between the experimental maximum adsorption capacity
values and PSO-adjusted, Langmuir one for (a) copper and (b) cadmium ions in their
mixtures for E. crassipes at pH 5, 120 min equilibrium time and 30 ◦ C.
librium experimental data of the binary system. The quality of the
predicted model results was assessed by the sum of the squared
errors between the equilibrium experimental data points and the
theoretically predicted ones (0.01134 for Cu and 0.01590 for Cd).
According to the modified extended Langmuir sorption model,
the presence of other metals in the solutions affects the shape of the
isotherm curve, due to changes in apparent metal affinity for the
active sites. Regarding the value of correction parameter of species
i (nLi ), if the biosorbent has different affinity between both metal
ions then different nLi values are expected to be predicted by the
proposed model, instead of nLi ones equals to one. In the present
work, the estimated values of correction parameter of species i
were 0.7044 and 1.3649 for Cu and Cd, respectively. Performing the
evaluation of this result (see Table 5), it is observed that the ratio
of affinity to correction parameters (bLi /nLi ) are 0.6303 and 0.4147
for Cu and Cd ions, respectively, indicating that the corrected affin-
ity parameter of Cu(II) by the biosorbent E. crassipes is higher than
Cd(II) in the binary adsorption system.
From the iso-metal concentration plane that was built by cut-
ting the 3D-metal adsorption surface plot by a diagonal plane,
the predicted maximum Cu(II) capacity was estimated to be
0.418 mequiv. g−1 (see Fig. 4a), while the predicted qmax for
Cd(II) was estimated to be 0.207 mequiv. g−1 (see Fig. 4b). In
addition, a sum of these predicted maximum metal capacities
(0.625 mequiv. g−1 ), namely the total metal capacity, is between
those obtained in single metal adsorption systems (0.615 and
0.667 mequiv. g−1 for copper and cadmium, respectively). In addi-
tion, it must be noted that the single metal isotherms of each metal
can be seen in the respective main vertical planes, where the con-
centration of the other metal is zero, predicting thus the single
metal adsorption points and its corresponding maximum capac-
ity. As can be expected from the 3D Cu–Cd adsorption plots (Fig. 4)
and the 2D simple ones, the maximum capacity of one metal ion is
not a parameter depending on the other one in their mixture. How-
ever, the different values of the correction parameter of species i
(nLi ) and the corrected affinity parameter values (bLi /nLi ) suggest that
the affinity of each metal ion onto the E. crassipes surface is influ-
enced by the presence of the other one. Furthermore, the binary
adsorption isotherm data of the E. crassipes biosorbent can effec-
tively be predicted using an extended modified Langmuir model,
which assumes that the Cu(II) and Cd(II) ions in binary compo-
nent mixtures behave dependently of each other, with competition,
interaction, or displacement effects. Its applicability in ternary mix-
tures of divalent metallic ions will be part of a future work. Based on
its heavy metal sorbent characteristics for divalent ions, the E. cras-
sipes is a promising material to be used in wastewater treatment
systems.
4. Conclusion
The results of this study suggest that the dry E. crassipes biosor-
bent shows a significant capacity to absorb of Cu(II) and Cd(II)
ions in single adsorption system as well as in the binary ones.
Batch tests have shown that the best experimental condition to
adsorb metal divalent ions onto sorbent surface has been achieved
by working at pH 5 and 30 ◦ C metallic solution temperature. It
was observed that there is no significant influence on the metal-
lic ion removal performance when a specific grain size range or a
mixture of them was used. From the kinetic tests, a short equilib-
rium time around 60 min was obtained, indicating that the dry E.
crassipes biomass could be used in adsorption-based continuous
treatment systems. In addition, the pseudo-second order model
has fitted better the single metal sorption data as well as the
Cu–Cd binary one. The equilibrium data obtained from single metal
adsorption systems were interpreted on the basis of a set of six
isotherm models, resulting that the best description was assigned
to the Langmuir one. It was found that the maximum uptake of
Cd(II) ions (0.667 mequiv. g−1 ) by the E. crassipes is higher than
that of Cu(II) one (0.615 mequiv. g−1 ), revealing the following metal
affinity order Cd(II) > Cu(II). On the other hand, the equilibrium
data of a mixtures of Cd(II) and Cu(II) ions were graphically rep-
resented by 3D adsorption surface and modeled by an modified
extended-to-multi-component Langmuir-type isotherm, obtaining
good fits. The PSO method has allowed the prediction of all mod-
ified extended Langmuir parameters. Under iso-concentration of
metallic ions in binary solutions, the predicted maximum capacity
of Cu(II) was estimated to be 0.418 mequiv. g−1 , while the pre-
dicted qmax for Cd(II) was estimated to be 0.207 mequiv. g−1 . In
addition, a sum of these predicted maximum metal capacities is
very near to those obtained in single metal adsorption systems.
Finally, the results have shown that the affinity of each metal ion
onto the E. crassipes surface is influenced by the presence of the
other one.
 A.N. Módenes et al. / Chemical Engineering Journal 168 (2011) 44–51
Acknowledgements
We thank the Araucaria Foundation for financial support of this
study. F.L. Lavarda thanks to the PTI-Itaipú research supporting
agency for MSc. Scholarship.
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