Chemical Engineering Journal 209 (2012) 577–588

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Chemical Engineering Journal

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Application of Mangifera indica (mango) seeds as a biosorbent for removal of

Victazol Orange 3R dye from aqueous solution and study of the biosorption
mechanism
Wagner S. Alencar a, Elie Acayanka b, Eder C. Lima b,⇑, Betina Royer b, Felipe E. de Souza b,
Jerônimo Lameira a, Cláudio N. Alves a
a
Institute of Exact and Natural Sciences, Federal University of Pará (UFPA), R. Augusto Corrêa S/N, 66075-900 Belém, PA, Brazil
b
Institute of Chemistry, Federal University of Rio Grande do Sul (UFRGS), Av. Bento Gonçalves 9500, Postal Box 15003, 91501-970 Porto Alegre, RS, Brazil

h i g h l i g h t s g r a p h i c a l a b s t r a c t

" Mango seed used in its natural and

protonated form as biosorbents.
" Characterization of biosorbents by
FTIR, SEM, BET and BJH techniques.
" A new general order kinetic equation
developed to fit the experimental
results.
" Mechanism of adsorption evaluated
using computational simulation.
" Water plays important role in the
interaction between dye and
biosorbent.

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

Article history: Mango seed, an abundant residue of the food industry, was used in its natural form (MS) and protonated
Received 3 June 2012 form (AMS) as a biosorbent for the removal of Victazol Orange 3R (VO-3R) dye from its aqueous solutions.
Received in revised form 19 August 2012 These biosorbents were characterized by infrared spectroscopy (FTIR), scanning electron microscopy
Accepted 20 August 2012
(SEM), and by nitrogen adsorption/desorption curves. Optimization of the effects of the initial pH of
Available online 27 August 2012
the dye solution, biosorbent dosage and contact time between the dye and the biosorbents on the
biosorption capacities of the biosorbents was studied. Based on an error function (Ferror), the general order
Keywords:
kinetic model provided the best fit to the experimental data when compared to the pseudo-first order and
General order kinetic equation
Mango seed
pseudo-second order kinetic biosorption models. The equilibrium data were fitted to Langmuir, Freund-
Biosorption lich and Liu isotherm models. For both biosorbents, the equilibrium data were best fitted to the Liu
Nonlinear isotherm fitting isotherm model. Finally, the mechanism of biosorption involving VO-3R and lignin–cellulose was evalu-
Thermodynamics ated using the hybrid quantum mechanical/molecular mechanical (QM/MM) approach and molecular
Computational simulation dynamic (MD) simulations. The results suggest that water molecules play a key role in the biosorption
process.
Ó 2012 Elsevier B.V. All rights reserved.

1. Introduction
Many industries use dyes to color their final products. It has
been estimated that about 10,000 different synthetic dyes and
pigments exist and that over 7  105 tonnes are produced annually
⇑ Corresponding author. Tel.: +55 51 3308 7175; fax: +55 51 3308 7304.
E-mail addresses: eder.lima@ufrgs.br, profederlima@gmail.com (E.C. Lima).
worldwide [1]. Approximately 10–60% of the reactive dyes are lost
during the manufacturing process, producing large quantities of
colored wastewater [2]. The dye-containing wastewater dis-
charged from industry can adversely affect the aquatic environ-
ment by impeding light penetration and, as a consequence,
precluding photosynthesis of aquatic flora [3,4]. Moreover, most
of the dyes can cause allergy, dermatitis, skin irritation and can
also provoke cancer and cell mutation in humans [5,6]. Therefore,

1385-8947/$ - see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cej.2012.08.053
578 W.S. Alencar et al. / Chemical Engineering Journal 209 (2012) 577–588
effluents containing dyes require treatment before being released
into the environment [1–4].
It is rather difficult to treat dye effluent because of its complex
aromatic molecular structure that can impart a bright and strong
color to other materials. However, the molecular structure of dyes
make them more stable and non-biodegradable [7–9]. One of the
methods most often employed for the removal of synthetic dyes
from aqueous effluents is the adsorption procedure [10,11], due
to its simplicity and high efficiency, as well as the availability of
a wide range of adsorbents [8–11]. This process transfers the dyes
from the aqueous effluent to a solid phase, significantly decreasing
bioavailability of the dye to living organisms [8–14]. The decon-
taminated effluent can then be released to the environment, or
the water can be reutilized in the industrial process [15]. Subse-
quently, the adsorbent can be regenerated or stored in a dry place
with no direct contact with the environment [15].
Activated carbon is one of the most employed adsorbents for
dye removal from aqueous solution because of its excellent adsorp-
tion properties [11,12]. However, the extensive use of activated
carbon for dye removal from industrial effluents is expensive
[16,17], due to its high initial and regeneration costs [10], thus
limiting more extensive application in wastewater treatment.
There is therefore a growing interest in finding alternative low cost
adsorbents for removal of dyes from aqueous solution. Among
these alternative adsorbents can be cited: aqai stalk [14]; jackfruit
leaf powder [15]; cupuassu shell [16]; Brazilian pine-fruit shell
[17]; pineapple leaf [18]; rice husk [19]; babassu coconut [20];
macauba palm [21]; and mango seeds [22,23].
Mango seed is an abundant residue discarded by the mango
juice industry, and is increasing due to the expansion of fruit pro-
duction [24]. Brazil produces 1.3 million metric tonnes of mangoes
per year, making it the third largest producer of mangoes in the
world, most of which are as juice. The seeds correspond to
30–45% of each mango’s weight, depending on the variety, and re-
main as a residue which is usually burned or discarded [24]. The
disposal of large amounts of mango seed (MS) directly into the soil
can contaminate the environment in an uncontrolled way, because
decomposition of this waste material generates various chemical
compounds and microorganisms. In this context, using MS as a bio-
sorbent for the removal of dyes from industrial effluents imparts a
good economic and environmental advantage to developing coun-
tries such as Brazil, as it also reduces costs of commercial adsor-
bents. Mango seed as a biosorbent for dye removal has been only
reported for methylene blue removal [22], and also as a carbon
precursor for the preparation of activated carbon used for the
adsorption of acid dyes [23]. Mango seeds have not however been
used to biosorb reactive dyes.
In this work, use of mango seed in both its natural (MS) and
acidified (AMS) form is being proposed for the first time as poten-
tial biosorbents for removal of Victazol Orange 3R (VO-3R) reactive
dye from aqueous solutions. This dye is largely used for textile dy-
ing in the Brazilian cloth industries. A new kinetic biosorption
model was developed for studying the biosorption of the dye by
the MS and AMS biosorbents. Additionally, a theoretical investiga-
tion of the molecular mechanism of biosorption was performed
through a hybrid quantum mechanical/molecular mechanical
(QM/MM) approach and molecular dynamic (MD) simulations.
2. Materials and methods
2.1. Solutions and reagents
De-ionized water was used throughout the experiments for
solution preparations.
The textile dye Victazol Orange 3R, also known as Reactive Or-
ange 16 (VO-3R; C.I. 17757; CAS 20262-58-2; C20H17N3O11S3Na2,
617.54 g mol1, kmax = 489 nm, see Supplementary Fig. 1) at 50%
purity, was furnished by Dynasty Colourants Co., Ltd. (China) (see
Supplementary Fig. 1). The dye was used without further purifica-
tion. VO-3R has one sulphatoethylsulphone group and one sulfo-
nate group. These groups present negative charges even in highly
acidic solutions due to their pKa values being lower than zero
[25]. The stock solution was prepared by dissolving the dye in dis-
tilled water to a concentration of 5.00 g L1. Working solutions
were obtained by diluting the dye stock solutions to the required
concentrations. To adjust the pH solutions, 0.50 mol L1 sodium
hydroxide and hydrochloric acid solutions were used. The pH of
the solutions was measured using a Schott Lab 850 set pH meter.
2.2. Biosorbent preparation and characterization
The mango seeds (MS) utilized in this work belong to the family
Mangifera indica L., Tommy Atkins variety. MS was provided by a
juice producer in Ubá-MG, Brazil. MS is mainly composed of cellu-
lose, lignin and hemicelluloses [24,26]. MS was washed with tap
water to remove dust, and then with de-ionized water. It was then
dried at 70 °C in an air-supplied oven for 8 h [14]. Following this,
the MS was ground in a disk-mill and subsequently sieved. That
part of the biosorbent which presented particles of diame-
ter 6 106 lm was used. This mango seed was assigned as MS.
In order to increase the amount of VO-3R dye adsorbed by the
MS biosorbent, the biomaterial was protonated as described below
[14]. An amount of 5.0 g of MS was added to 200.0 mL of 3 mol L1
of HCl, and the slurry was magnetically stirred for 24 h at 70 °C.
Subsequently, the slurry was filtered in a sintered glass funnel,
and its solid phase was thoroughly washed with water, until the
filtrate reached the pH of distilled water. Subsequently, the mate-
rial was dried at 70 °C in an air-supplied oven for 8 h, yielding the
acidified mango seed (AMS).
The MS and AMS biosorbents were characterized by vibrational
spectroscopy in the infrared region with Fourier Transform (FTIR)
using a Varian spectrometer (Australia, model 640-IR). The spectra
were obtained with a resolution of 4 cm1 using 100 cumulative
scans.
The surface analyses and porosity were carried out with a volu-
metric adsorption analyzer, Nova 1000 (Quantachrome Instru-
ments, United States of America), at 77 K (the boiling point of
nitrogen). The samples were pre-treated at 473 K for 24 h under
a nitrogen atmosphere in order to eliminate the moisture adsorbed
on the surface of the solid sample. The samples were then submit-
ted to conditions of 298 K in a vacuum, reaching the residual pres-
sure of 104 Pa. For area and pore calculations, the multi-point BET
(Brunauer, Emmett and Teller) [27] and BJH (Barret, Joyner and
Halenda) [28] methods were used.
The biosorbent samples were also analyzed with scanning elec-
tron microscopy (SEM; Jeol microscope, model JSM 6060) using an
acceleration voltage of 10 kV and magnification ranging from 200
to 5000 [29].
The point of zero charge (pHpzc) of the biosorbent was deter-
mined by adding 20.00 mL of 0.050 mol L1 NaCl with a previously
adjusted initial pH (the initial pH (pHi) values of the solutions were
adjusted from 2.0 to 10.0 by adding 0.10 mol L1 of HCl and NaOH)
to several 50.0 mL cylindrical high-density polystyrene flasks
(height 117 mm and diameter 30 mm) containing 50.0 mg of the
biosorbent, which were immediately securely capped. The suspen-
sions were shaken in an acclimatized shaker at 298 K and allowed
to equilibrate for 48 h. The suspensions were then centrifuged at
14,000 rpm for 10 min to separate the biosorbent from the aqueous
solution. The pHi of the solutions were accurately measured using
the solutions that had no contact with the solid biosorbent; the
final pH (pHf) values of the supernatant after contact with the solid
 W.S. Alencar et al. / Chemical Engineering Journal 209 (2012) 577–588 579

were recorded. The value of pHpzc is the point where the curve of of the software Microcal Origin 7.0. In addition, the models were
DpH (pHf  pHi) versus pHi crosses a line equal to zero [30]. evaluated by a determination coefficient (R2), an adjusted determi-
nation coefficient (R2adj ), as well as by an error function (Ferror) [10],
2.3. Batch biosorption studies which measured the differences in the amount of dye taken up by
the biosorbent as predicted by the models and the actual q mea-
The batch biosorption studies for evaluation of the ability of MS sured experimentally. R2, R2adj and Ferror are given below, in Eqs.
and AMS biosorbents to remove VO-3R dye from aqueous solutions (3)–(5) respectively:
were carried out in triplicate, using the batch contact biosorption Pn   P   !
i;exp 2  ni qi;exp  qi;model 2
qi;exp  q
method. For these experiments, 50.0 mg of biosorbent were placed 2
R ¼ i
ð3Þ
Pn  2
in 50 mL cylindrical polypropylene flasks (117 mm height and 
i qi;exp  qi;exp
30 mm diameter) containing 20.0 mL of dye solution (20.00–
300.0 mg L1), which were agitated for an appropriate time   n  1
(0.0833–24.00 h) using an acclimatized shaker at temperatures R2adj ¼ 1  1  R2  ð4Þ
np
ranging from 298 to 323 K. The pH of the dye solutions ranged
from 2.0 to 10.0. Subsequently, in order to separate the biosorbent
vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
u  X n
u 1  2
from the aqueous solutions, the flasks were centrifuged at F error ¼t  qi;exp  qi;model ð5Þ
14,000 rpm for 5 min using a Unicen M Herolab centrifuge (Stutt- np i
gart, Germany), and aliquots of 1–10 mL of the supernatant were
properly diluted with an aqueous solution fixed at pH 2.0. where qi,model is each value of q predicted by the fitted model, qi,exp is
The final concentrations of the dyes remaining in the solution each value of q measured experimentally, q exp is the average of q
were determined by visible spectrophotometry using a T90 + UV– experimentally measured, n is the number of experiments per-
VIS spectrophotometer (PG Instruments, London, England) fitted formed, and p is the number of parameters of the fitted model [10].
with quartz optical cells. Absorbance measurements were made
at 489 nm: the maximum wavelength of VO-3R dye. 2.5. Kinetic biosorption models
The amount of dye taken up and the percentage of the dye re-
moved by the biosorbents were calculated by applying Eqs. (1) See Supplementary material.
and (2), respectively:
2.6. Equilibrium models
ðC o  C f Þ
q¼ V ð1Þ
m See Supplementary material.

ðC o  C f Þ
%Remov al ¼ 100 
Co
in which q is the amount of dye adsorbed by the biosorbent
(mg g1), Co is the initial dye concentration placed in contact with
the biosorbent (mg L1), Cf is the dye concentration (mg L1) after
the batch biosorption procedure, m is the mass of biosorbent (g)
and V is the volume of dye solution (L).
2.4. Quality assurance and statistical evaluation of the kinetic and
isotherm parameters
To establish the accuracy, reliability and reproducibility of the
collected data, all the batch biosorption measurements were per-
formed in triplicate and the relative standard deviation of all mea-
surements was lower than 5% [16]. Blank tests were run in parallel
and were corrected when necessary.
All dye solutions were stored in glass flasks, which were cleaned
by soaking in 1.4 mol L1 HNO3 for 24 h [16], rinsing five times
with de-ionized water, drying and storing them in a flow hood.
For analytical calibration, standard solutions with concentra-
tions ranging from 5.00 to 150.0 mg L1 of the dyes were used, in
parallel with a blank solution of water adjusted to pH 2.0. The
linear analytical calibration of the curve was furnished by the UV-
Win software of the T90 + PG Instruments spectrophotometer. The
detection limit of the method, obtained with a signal/noise ratio of
3 [16], was 0.12 mg L1 of VO-3R. All the analytical measurements
were performed in triplicate, and the precision of the standards
was better than 3% (n = 3). In order to verify the accuracy of the
VO-3R dye sample solutions during spectrophotometric measure-
ments, standards containing dyes at 50.0 mg L1 were employed
as a quality control every five determinations [16].
The kinetic and equilibrium models were fitted by employing a
nonlinear method, with successive interactions calculated by the
Levenberg–Marquardt method; interactions were also calculated
using the Simplex method, based on the nonlinear fitting facilities
ð2Þ 2.7. Computational chemistry
In this study, we undertook a theoretical investigation of possi-
ble interaction mechanisms between VO-3R and lignin–cellulose
(LC) using the hybrid quantum mechanical/molecular mechanical
(QM/MM) approach and molecular dynamic (MD) simulations.
The initial structure of VO-3R was obtained from pubchem [31],
while the LC structure was constructed using Molden [32]. In order
to study the protonation state of LC based on the experimental
study of pH (ranging from 2.0 to 10.0), we considered two models:
(A) the deprotonated LC; and (B) the LC protonating the guaiacyl
and siringyl groups. The molecules were pre-optimized in vacuum
and were then placed in a cubic box of pre-equilibrated water
(20 Å side). Finally, 300 ps of hybrid QM/MM Langevin–Verlet
molecular dynamics (NVT) at 300 K were used to equilibrate the
models. During MD, atoms of VO-3R and LC were selected to be
treated by QM, using a semi-empirical AM1 Hamiltonian [33,34],
while the water molecules were described using a TIP3P force field
[35,36] implemented in f-Dynamo. Lastly, the molecular electro-
static potential (MEP) surface was generated from the B3LYP/6-
31G(d,p) using the PC Spartan PRO molecular package [37]. This
surface corresponds to an isodensity value of 0.002 au, and it is
interesting to highlight potential non-covalent interactions that
can occur at the molecular level.
3. Results and discussion
3.1. Characterization of biosorbents
FTIR technique was used to examine the surface groups of MS
and AMS biosorbents and to identify the groups responsible for
biosorption of the dye. Infrared spectra of the biosorbents were re-
corded in the range 4000–400 cm1. Supplementary Fig. 2 presents
the FTIR spectra of MS and AMS biosorbents before biosorption
(MS: Supplementary Fig. 2A; AMS: Supplementary Fig. 2C) and
580 W.S. Alencar et al. / Chemical Engineering Journal 209 (2012) 577–588
when loaded with the VO-3R dye (AS + VO-3R: Supplementary
Fig. 2B; AMS + VO-3R: Supplementary Fig. 2D). It was observed
that the vibrational bands for AS, AS + VO-3R, AMS and AMS +
VO-3R appeared at practically the same wavenumber (differ-
ences 6 4 cm1, within the error of the equipment) for the four
situations described above. As previously observed for lignin–
cellulosic materials [14], protonation of the biomass did not signif-
icantly alter the FTIR bands of the biomaterials. It was additionally
observed that the vibrational bands did not alter significantly
when compared before and after the biosorption process, indicat-
ing that the strength of the interaction between the dye and the
biosorbent is a physical interaction and not a chemical bond.
The intense absorption bands at 3384 and 3385 cm1 were as-
signed to OAH bond stretching for AS and AMS, respectively
[14,16,38]. The CH2 stretching band observed at 2919 cm1 was as-
signed to asymmetric stretching of CH2 groups [38]. Bands at 1722
and 1718 cm1, for MS and AMS, respectively, were assigned to
carbonyl groups of carboxylic acid [14,16]. FTIR vibrational bands
at 1603 and 1601 cm1 were assigned to stretching of carboxylate
[38]. Several small bands at 1517, 1457, 1379 and 1325 cm1 for
MS, and 1517, 1457, 1376 and 1379 cm1 for AMS, were assigned
to ring modes of the aromatic rings [38]. The bands at 1160 and
1162 cm1 for MS and AMS, respectively, were assigned to a
CAOAC asymmetric stretch of ether groups of lignin [14,16,38].
The intense FTIR band at 1029 and 1028 cm1 for MS and AMS,
respectively, was assigned to a CAO stretch of primary alcohol of
lignin [38]. Based on these FTIR results, it was expected that the
interaction of VO-3R dye with the MS and AMS biosorbents should
occur with the OH, C@O, COOH and at the aromatic present in the
lignin–cellulosic materials, as previously reported in the literature
[14,16,38].
The textural properties of MS and AMS obtained by nitrogen
adsorption/desorption curves were: superficial area (SBET), 8.52
Fig. 1. SEM of (A) MS with magnification 1000; (B) MS with magnification 1500; (C) AMS with magnification 1000; and (D) AMS with magnification 1500. Accelerating
voltage 10 kV.
and 11.5 m2 g1; average pore diameter (BJH), 4.31 and 5.78 nm;
and total pore volume, 0.00918 and 0.0121 cm3 g1, for MS and
AMS, respectively. These textural properties obtained for MS and
AMS are consistent with values of lignin–cellulosic materials re-
ported in the literature [16,39,40]. The maximum diagonal length
of VO-3R is 1.68 nm (see Supplementary Fig. 1; the dimensions
of the chemical molecule were calculated using ChemBio 3D Ultra
version 11.0.). The ratios of average pore diameter of the biosor-
bents to the maximum diagonal length of dye were 2.56 (£MS/
£VO-3R) and 3.44 (£AMS/£VO-3R). Therefore, the mesopores
of MS could accommodate up to two molecules of VO-3R dye,
and the mesopores of AMS could accommodate up to three mole-
cules of VO-3R dye.
SEM images of the MS and AMS biosorbents are shown in Fig. 1,
revealing that MS biosorbent is a more compact fibrous material
(see Fig. 1A and B), with only a low number of macropores (pore
with £ > 50 nm). AMS biosorbent presents a greater number of
cavities in the fibrous materials (see Fig. 1C and D) when compared
to unmodified MS biosorbent.
From analysis of the textural properties of MS and AMS biosor-
bents, it could be inferred that these biosorbent materials predom-
inantly contain a mixture of mesopores (pores with diameter
ranging from 2 to 50 nm, see textural results described above)
and macropores (pore with diameter >50 nm).
3.2. Effects of pH of dye solution on biosorption
One of the most important factors influencing the biosorption of
dye on a biosorbent is the pH of the adsorbate solution [3,12]. Dif-
ferent dyes present different ranges of suitable pH depending on
which biosorbent is used. The effects of initial pH on percentage
of removal of VO-3R dye solution (40 mg L1) using MS and AMS
biosorbents were evaluated within a pH range between 2 and 10
 W.S. Alencar et al. / Chemical Engineering Journal 209 (2012) 577–588
Fig. 2. Effect of pH on the biosorption of: VO-3R dye, using (A) MS biosorbent; (B) AMS biosorbent. Conditions: Co = 40.0 mg L1 of dye solution; the temperature was fixed at
298 K; mass of biosorbent 50.0 mg.
(Fig. 2). A considerable difference was observed for the effect of pH
solution on the dye using the biosorbents. For MS biosorbent, the
percentage of dye removed decreased markedly from 48.1% of
dye removed at pH 2.0 to less than 0.4% removed at pH 7.0. For
AMS biosorbent, the percentage of dye removed also decreased
from 78.5% at pH 2.0 to 13.5% at pH 7.0.
The point of zero charge (pHPZC) of MS and AMS biosorbents are
5.45 and 2.15, respectively. For pH values lower than pHPZC, the
biosorbent presents a positive surface charge [11,30]. The
dissolved VO-3R dye is negatively charged in water solutions, be-
cause it presents one sulfonate and one sulphatoethylsulphone
group [25]. The biosorption of this dye occurs when the biosorbent
presents a positive surface charge [30]. For MS, electrostatic inter-
action occurs at pH < 5.45, whereas for AMS this interaction occurs
at pH < 2.15. Based on these results, it is clear that the best pH for
VO-3R dye biosorption would be pH 2.0 for both biosorbents.
3.3. Effect of the mass of biosorbent
The study of biosorbent masses in the removal of VO-3R dye
from aqueous solution was carried out using MS and AMS masses
ranging from 20.0 to 200.0 mg, with the initial dye concentration
fixed at 50.0 mg L1. The highest amount of dye removal was at-
tained for biosorbent masses of at least 50 mg, corresponding to
biosorbent dosages of 2.5 g L1 (see Supplementary Fig. 3). For
biosorbent dosages higher than this value, the percentage of dye
removed remained almost constant. Increases in the percentage
of the dye removed with adsorbent masses up to 50.0 mg
(2.5 g L1) could be attributed to increases in the adsorbent surface
area, augmenting the number of adsorption sites available for
adsorption, as has already been reported in several papers
[3,7,8,11,12,30]. Conversely, the increase in the adsorbent masses
promoted a remarkable decrease in the amount of dye uptake
per gramme of adsorbent (q), (Supplementary Fig. 3). This could
be due to two factors. Firstly, the increase in adsorbent mass at a
fixed dye concentration and volume could lead to unsaturation of
adsorption sites through the adsorption process; and, secondly,
the reduction in adsorbent capacity may have been due to particle
aggregation, resulting from a high adsorbent mass. Such an aggre-
gation would lead to a decrease in the total surface area of the
adsorbent and an increase in diffusional path length [28]. There-
fore, the MS and AMS biosorbent masses must be fixed at
50.0 mg, these being the biosorbent masses that corresponded to
the minimum amount of biosorbent that facilitated consistent
dye removal.
581
3.4. Kinetic studies
Nonlinear pseudo-first order, pseudo-second order and general
order kinetic biosorption models were used to evaluate the kinetics
of biosorption of VO-3R dye by using the MS and AMS biosorbents,
as shown in Figs. 3 and 4. The kinetic parameters for the three
kinetic models are listed in Table 1. Taking into account that the
experimental data were fitted to nonlinear kinetic models, an error
function (Ferror) was used to evaluate the fit of the experimental
data. The lower the Ferror, the lower the difference in the q calcu-
lated by the model from the experimentally measured q
[3,4,7,8,10–12,14,16,17] (see Eq. (5)). It should be pointed out that
the Ferror utilized in this work takes into account the number of fit-
ted parameters (p term of Eq. (5)), since it is reported in the liter-
ature [41,42] that the best fit of the results depends on the number
of parameters a nonlinear equation presents. For this reason, the
number of fitted parameters should be considered in the calcula-
tion of Ferror.
The pseudo-first order kinetic model presented Ferror values of
at least 609% and 592% higher than the values obtained for the gen-
eral order biosorption model, using MS and AMS biosorbents,
respectively. Additionally, the pseudo-second order kinetic model
presented Ferror values that were at least 108% and 92% higher than
the values obtained for the general order biosorption model, using
MS and AMS biosorbents, respectively. These results clearly indi-
cate that the experimental kinetic data were not suitably fitted
by the pseudo-first-order and pseudo-second order kinetic models
[43]. On the other hand, the general order kinetic model better
explains the biosorption process of VO-3R dye using the MS and
AMS biosorbents.
Taking into account that the general order kinetic equation pre-
sents different orders (n) when the concentration of the adsorbate
is changed (see Table 1), it is difficult to compare the kinetic
parameters of the model. Therefore, it is useful to use the initial
sorption rate h0 [44] to evaluate the kinetics of a given model,
using the following equation:
h0 ¼ kn  qne ð6Þ
in which, h0 is the initial sorption rate (mg g1 h1), kn is the rate
constant [h1 (g mg1)n  1] [45], qe is the amount adsorbed at the
equilibrium (mg g1), and n is the order of the kinetic model. It
should be stressed that when n = 2, this equation is the same initial
sorption rate as first introduced by Ho and Mckay [44]. It was ob-
served that by increasing the initial dye concentration, the initial
sorption rate was increased for all kinetic models, as expected,
582 W.S. Alencar et al. / Chemical Engineering Journal 209 (2012) 577–588
Fig. 3. Kinetic biosorption curves of VO-3R dye using MS biosorbent. (A) Co 50 mg L1; (B) Co 100.0; (C) Co 50.0 mg L1; (D) Co 100.0 mg L1. Conditions: pH was fixed at 2.0;
the MS biosorbent mass was fixed at 50.0 mg; and the temperature was fixed at 298 K.
indicating that there is coherence with the experimental data [45].
Taking into account that the kinetic data were better fitted by the
general order kinetic model, meaning that the order of a biosorption
process should follow the same logic as a chemical reaction and
where the order is experimentally measured [45,46], instead of
being previously stipulated by a given model, the more confident
initial sorption rates (h0) were obtained by the general order kinetic
model.
It was observed that the kinetics of biosorption of VO-3R dye on
AMS biosorbent were faster than those obtained using MS biosor-
bent. Considering the initial sorption rate (h0) of VO-3R dye taken
up by MS and AMS biosorbents (see Table 1), as obtained by the
general order kinetic model, it was observed that h on AMS biosor-
bent was increased by 120–150% when compared with h0 obtained
for MS biosorbent. It can be concluded that acid treatment of man-
go seed promoted an increase in the macropore structure on the
biomaterial (see Fig. 1), as already reported for other biosorbents
[14,45], contributing to a faster diffusion of the VO-3R dye through
the pores of the biosorbent, and also allowing higher amounts of
the VO-3R dye to be adsorbed by the AMS biosorbent.
The intra-particle diffusion model [45] was also used to verify
the influence of mass transfer resistance on the binding of VO-3R
dye to the biosorbents (Table 1 and Figs. 3C and D and 4C and
D). The intra-particle diffusion constant, kid (mg g1 h0.5), can be
obtained from the slope of the plot of qt versus the square root of
the time. These figures give plots of qt versus t1/2, with three linear
sections for the VO-3R dye using the MS and AMS biosorbents.
These results imply that the biosorption processes involved more
than one sorption rate [45]. For both biosorbents, the biosorption
process exhibited three stages, which can be attributed to each
linear section as shown in Figs. 3C and D and 4C and D. The first
linear section was attributed to the process of the dye diffusing
to the biosorbent surface [45]; hence, it was the fastest sorption
stage. The second section, ascribed to intra-particle diffusion, was
a delayed process [45]. The third stage may be regarded as diffu-
sion through smaller pores, followed by the establishment of equi-
librium [45]. The kid values for biosorption of VO-3R on AMS
biosorbent were 48.9% (50.00 mg L1) and 42.2% (100.00 mg L1)
higher than the value for kid obtained for the biosorption of VO-
3R dye on MS biosorbent, given the same initial dye concentration.
This difference in kid values is related to differences in the textural
properties of the biosorbents after treatment with acid, as already
reported in the literature [14,45], and also in agreement with the
results discussed above in the characterization of the biosorbents.
The increase in the macropore structure of AMS biosorbent should
facilitate the diffusion of VO-3R dye molecules through the mac-
ropores [27,28]. As the adsorbate diffuses through the pores of
the biosorbent, the dye could be adsorbed at the internal sites of
the AMS biomaterial; therefore both a fast kinetics of biosorption
(increasing the intra-particle diffusion) and higher sorption capac-
ity of AMS biosorbent were expected in relation to MS biosorbent.
On the other hand, for the MS biosorbent, with a lower number of
macropores, the biosorption is limited to the external surface of
the biosorbent, decreasing the total amount adsorbed [14,45],
 W.S. Alencar et al. / Chemical Engineering Journal 209 (2012) 577–588 583

Fig. 4. Kinetic biosorption curves of VO-3R dye using AMS biosorbent. (A) Co 50 mg L1; (B) Co 100.0; (C) Co 50.0 mg L1; (D) Co 100.0 mg L1. Conditions: pH was fixed at 2.0;
the AMS biosorbent mass was fixed at 50.0 mg; and the temperature was fixed at 298 K.

Table 1
Kinetic parameters for VO-3R removal using MS and AMS biosorbent. Conditions: temperature of 298 K; pH 2.0; mass of biosorbent 50.0 mg.

MS AMS
Pseudo-first order 50.00 mg L1 100.00 mg L1 50.00 mg L1 100.00 mg L1
k1 (h1) 2.57 2.57 2.55 2.71
qe (mg g1) 9.46 18.4 16.5 30.8
h0 (mg g1 h1) 24.3 47.2 42.0 83.2
R2adj 0.9874 0.9900 0.9693 0.9648
Ferror 0.3218 0.5594 0.8737 1.712
Pseudo-second order
k2 (g mg1 h1) 0.386 0.199 0.215 0.125
qe (mg g1) 9.89 19.2 17.3 32.1
h0 (mg g1 h1) 37.7 73.2 63.9 129.3
R2adj 0.9993 0.9985 0.9976 0.9970
Ferror 0.0767 0.2167 0.2420 0.4977
General order
kN [h1 (g mg1)n1] 0.586 0.452 0.0628 0.0181
qe (mg g1) 9.75 18.8 17.9 33.7
n 1.79 1.69 2.46 2.58
h0 (mg g1 h1) 34.7 64.5 75.2 160.1
R2adj 0.9998 0.9998 0.9994 0.9998
Ferror 0.0369 0.0789 0.1262 0.1424
Intra-particle
kid (mg g1 h0.5)a 1.39 2.63 2.07 3.74
R2 0.9879 0.9854 0.9835 0.9868
a
Second stage.
584 W.S. Alencar et al. / Chemical Engineering Journal 209 (2012) 577–588

Table 2
Isotherm parameters for VO-3R biosorption, using MS and AMS biosorbents. Conditions: biosorbent mass 50.0 mg; pH fixed at 2.0, contact time 6 h.

MS AMS
298 K 303 K 308 K 313 K 318 K 323 K 298 K 303 K 308 K 313 K 318 K 323 K
Langmuir
Qmax (mg g1) 44.8 47.4 51.7 45.9 47.9 51.2 71.6 64.9 62.2 64.9 66.9 68.7
KL (L mg1) 0.0131 0.0135 0.0134 0.0178 0.0184 0.0208 0.0499 0.0626 0.0849 0.0901 0.100 0.116
R2adj 0.9872 0.9797 0.9593 0.9823 0.9776 0.9241 0.9067 0.9761 0.9848 0.9766 0.9755 0.9892
Ferror 1.121 1.515 2.398 1.441 1.881 3.595 5.359 2.697 2.043 2.970 3.2420 2.121
Freudlich
KF (mg g1 (mg L1)1/nF) 2.05 2.27 2.39 3.21 3.10 4.43 10.8 12.0 18.0 17.3 18.7 19.7
nF 1.86 1.88 1.86 2.11 2.04 2.28 2.58 2.87 4.04 3.76 3.90 3.81
R2adj 0.9466 0.9354 0.9041 0.9329 0.9213 0.8396 0.9991 0.8923 0.8982 0.8587 0.8601 0.8967
Ferror 2.292 2.701 3.683 2.809 3.529 5.225 7.330 5.725 5.282 7.295 7.745 6.565
Liu
Qmax (mg g1) 33.4 34.1 34.8 35.5 36.3 36.9 53.3 54.6 56.3 58.3 60.6 63.3
Kg (L mg1) 0.0226 0.0245 0.0264 0.0283 0.0307 0.0333 0.0741 0.0830 0.0931 0.105 0.1169 0.130
nL 1.54 1.73 2.12 1.64 1.77 2.69 2.94 1.69 1.53 1.63 1.676 1.44
R2adj 0.9998 0.9999 0.9998 0.9997 0.9998 0.9998 0.9991 0.9996 0.9997 0.9998 0.9995 0.9997
Ferror 0.1176 0.1279 0.1486 0.1766 0.1610 0.1909 0.5200 0.3444 0.2827 0.2545 0.4602 0.3683

and also leading to slower biosorption kinetics of VO-3R dye. The

cavities generated in the AMS biomaterial can be attributed to its
treatment with 3.0 mol L1 HCl solution.
Figs. 3 and 4 reveal that the minimum contact time of VO-3R
dye with the MS and AMS biosorbents needed to reach equilibrium
was about 5 h for both biosorbents. In order to continue this work,
the contact time between the MS and AMS biosorbents with VO-3R
dye was fixed at 6 h, using the MS and AMS biosorbents. The in-
creased contact time utilized in this work guaranteed that equilib-
rium would be attained for the VO-3R dye even at higher adsorbate
concentrations [14].

3.5. Equilibrium studies

A biosorption isotherm describes the relationship between the

amount of adsorbate adsorbed by the biosorbent (qe) and the
adsorbate concentration remaining in solution after the system
attained equilibrium (Ce), maintaining the process at a constant
temperature. The biosorption parameters of the equilibrium mod-
els often provide some insight into the biosorption mechanism,
surface properties and affinity of the biosorbent with the adsor-
bate. We tested the Langmuir, Freundlich and Liu isotherm models
[10].
The isotherms of biosorption were carried out at 298 to 323 K
with VO-3R dye on the two biosorbents (MS and AMS), and were
performed using the optimum experimental conditions previously
described above (see Table 2, and Fig. 5). Fig. 5 shows the biosorp-
tion isotherms of VO-3R dye using MS and AMS biosorbents at
298 K. Based on the Ferror (see Table 2), the Liu model was found
to be the best isotherm model for both biosorbents at all six pf
the temperatures studied. The Liu model showed (Table 2) the low-
est Ferror values, meaning that the q fit by the isotherm model was
close to the q measured experimentally. The Freundlich isotherm
model was not suitably fitted, presenting Ferror values ranging from
1490% to 2640% and from 1310% to 2770% higher than the Ferror
values obtained for the Liu isotherm model, using MS and AMS Fig. 5. Isotherms of biosorption of VO-3R dye at 298 K. (A) MS; (B) AMS. Conditions:
as biosorbents, respectively. The Langmuir isotherm model was pH was fixed at 2.0; the AMS biosorbent mass was fixed at 50.0 mg; time of contact
6.0 h.
also not suitably fitted, presenting values of Ferror ranging from
850% to 1780%, and from 470% to 1070% higher than the Ferror
values obtained for the Liu isotherm model, using MS and AMS bio-
sorbents, respectively. well-defined sites; each site can only hold one adsorbate species;
The Langmuir isotherm model is based on the following princi- all sites are energetically equivalent; and there are no interactions
ples [45]: adsorbates are chemically adsorbed at a fixed number of between the adsorbate species. The Freundlich isotherm model
 W.S. Alencar et al. / Chemical Engineering Journal 209 (2012) 577–588 585

Table 3
Thermodynamic parameters of the biosorption of VO-3R dye on MS and AMS biosorbents. Conditions: mass of biosorbent 50.0 mg, pH fixed at 2.0; contact time of 6 h.

Temperature (K)
298 303 308 313 318 323
MS
Kg (L mol1) 1.36  104 1.47  104 1.59  104 1.70  104 1.85  104 2.00  104
DG (kJ mol1) 23.58 24.18 24.76 25.36 25.97 26.60
DH° (kJ mol1) 12.3 – – – – –
DS° (J K1 mol1) 120.4 – – – – –
R2 0.9985 – – – – –
AMS
Kg (L mol1) 4.46  104 5.00  104 5.60  104 6.29  104 7.03  104 7.79  104
DG (kJ mol1) 26.52 27.25 28.00 28.75 29.51 30.25
DH° (kJ mol1) 18.0 – – – – –
DS° (J K1 mol1) 149.4 – – – – –
R2 0.9998 – – – – –

assumes that the concentration of adsorbate on the adsorbent sur-

Table 4
face increases with adsorbate concentration. Theoretically, using Comparison of maxima adsorption capacities for Victazol Orange 3R (VO-3R) dye, also
this expression, an infinite amount of adsorption can occur [45]. known as Reactive Orange 16. The values were obtained at the best experimental
The Liu isotherm model is a combination of the Langmuir and Fre- conditions of each work.
undlich isotherm models, and therefore the monolayer of the Lang- Adsorbent Qmax (mg g1) Ref.
muir model is excluded, as is the infinite adsorption of the
Aqai stalk 61.3 [14]
Freundlich model. The Liu model [45] predicts that the active sites Acidified Aqai Stalk 156 [14]
of the adsorbent could not present the same energy; therefore, the Sewage sludge 47.0 [47]
adsorbent may present active sites that are preferentially occupied Chitosan cross-linked (beads) 30 [48]
Chitosan cross-linked (beads) 5.6 [48]
by the adsorbate molecules [45]. However, saturation of the active
Chitosan 30.4 [49]
sites should occur, unlike the Freundlich isotherm model. Humin immobilized on silica 10.2 [50]
The maximum amounts of VO-3R biosorbed were 36.9 and Mango seed (MS) 36.9 This work
63.3 mg g1, respectively, using MS and AMS as the biosorbent, Acidified mango seed (MAS) 63.3 This work
respectively, at 323 K. It should be highlighted that the maximum
amount (Qmax) of the VO-3R dye adsorbed by the AMS biosorbent
was 60–72% higher when compared with the MS biosorbent. These fident. In addition, the magnitude of enthalpy was consistent with
values indicate that MS and AMS are fairly good biosorbents for the a physical sorption for both biosorbents [55]. The type of interac-
removal of this dye from aqueous solutions (see Table 3) [14,47– tion can be classified, to a certain extent, by the magnitude of
50]. Of eight different adsorbents, AMS presents an adsorption enthalpy change. Physical sorption, such as hydrogen bonding, is
capacity higher than seven. On the other hand, of eight different usually lower than 25 kJ mol1 [55]. Enthalpy changes (DH°) indi-
adsorbents, MS presents an adsorption capacity higher than four. cate that the biosorption followed endothermic processes. Nega-
tive values of DG indicate that the VO-3R dye biosorption by MS
3.6. Thermodynamics of biosorption and AMS biosorbents was a spontaneous and favorable process at
all the studied temperatures. The positive values of DS° confirmed
Thermodynamic parameters related to the biosorption process, a high preference of VO-3R molecules for the surface of MS and
i.e., Gibb’s free energy change (DG°, kJ mol1), enthalpy change AMS, and also suggested the possibility of some structural changes
(DH°, kJ mol1) and entropy change (DS°, J mol1 K1) were deter- or readjustments in the dye–carbon biosorption complex [56].
mined by the following equations:
DG ¼ DH  T DS ð7Þ 3.7. Mechanism of biosorption based on computational calculations

DG ¼ RTLnðKÞ ð8Þ
Hybrid QM/MM MD simulations of 300 ps for VO-3R and lig-
The combination of Eqs. (7) and (8) gives: nin–cellulose (LC) were performed. Representative snapshots of
the averaged structures of VO-3R and lignin–cellulose obtained
DS DH 1
LnðKÞ ¼  x ð9Þ from the 300 ps MD simulations are shown in Fig. 6. As can be
R R T observed in this figure, the water molecules play a key role in
where R is the universal gas constant (8.314 J K1 mol1), T is the dye–lignin–cellulose interactions in both the A and B models,
absolute temperature (Kelvin) and K represents the equilibrium bio- where VO-3R dye interacts with LC through chains of H-bonds
sorption constants of the isotherm fits. It has been reported in the formed by water molecules (Fig. 6).
literature that different biosorption equilibrium constants (K) were In model A, the H-bond linkages are formed in two ways: 1, 2, 3
obtained from different isotherm models [10–12,30,41,45,51–54]. and 4, 5, 6, where the distances correspond to 2.93, 3.72, 3.57 and
Thermodynamic parameters of biosorption can be estimated from 1.88, 4.66, 2.22 Å, respectively. In model B, H-bond linkages are
Kg (Liu equilibrium constant), as already reported in the literature also formed in two ways: 1, 2, 3, 4 and 5, 6, 7, where the distances
[10,41]. observed correspond to 1.66, 1.90, 2.92, 2.92 and 1.87, 1.85, 3.16 Å,
The DH° and DS° values can be calculated from the slope and respectively. The H-bond distances obtained from QM/MM MD are
intercept of the linear plot of Ln(K) versus 1/T. in agreement with the literature [57], which suggests that VO-3R
The thermodynamic results are depicted in Table 4. The R2 dye may be interacting with the biosorbent through chains of
values of the linear fit were at least 0.99, indicating that the values water molecules. As the water molecule chain is located between
of enthalpy and entropy calculated for both biosorbents were con- the siringyl group (see Supplementary Fig. 4) of LC and sulfonic
586 W.S. Alencar et al. / Chemical Engineering Journal 209 (2012) 577–588

Fig. 6. Representative snapshots of the averaged structures of VO-3R dye and lignin–cellulose obtained from the 300 ps of QM/MM MD simulations.

groups of VO-3R, we can conclude that the process of diffusion of
the siringyl group is better than in the guaiacyl group. Curiously,
Fourier transform infrared spectroscopy (FTIR) spectra for the
absorbent before and after the contact with VO-3R dye were sim-
ilar (see Supplementary Fig. 2), suggesting the existence of a phys-
ical rather than a chemical reaction [14].
The water molecules form H-bonding links between the VO-3R
dye and lignin–cellulose (Fig. 7), in agreement with the FTIR spec-
tra of the biosorbent obtained before and after biosorption of the
dye, in which no chemical reaction is observed (Supplementary
Fig. 2). Therefore, water molecules play an important role in the
biosorption process. This new proposed interaction mechanism
(Fig. 7) of lignin–cellulose and dye might improve understanding
of the previous mechanism proposed for the biosorption of dyes
using lignin–cellulosic biosorbents [14,16,45].
Fig. 8 shows the molecular electrostatic potential (MEP) for
the VO-3R (Fig. 8A), LC (Fig. 8B) and protonated LC (Fig. 8C).
MEP surfaces were generated using the Spartan program [37].
These surfaces correspond to an isodensity value of 0.002 au.
The most nucleophilic regions (negative electronic potential)
are shown in red, while the most electrophilic regions (positive
electrostatic potential) are shown in blue. In Fig. 8 we can
observe a much more intense region of negative electrostatic
potential around the sulfonate group of the VO-3R (Fig. 8A),
and a more intense region of positive electrostatic potential
around the siringyl group of lignin–cellulose material (Fig. 8B
and C). When the lignin–cellulose material was protonated, the
interactions with the siringyl group were more intense, yielding
a better biosorption.
The computer simulation results reveal that model B better ex-
plains the experimental observations than model A. In fact, we can
observe that the siringyl group and the sulfonate group are close to
each other, as demonstrated by the average distance between then,
which is 8.50 Å and 7.90 Å for model A and B, respectively. This
favorable interaction is reflected in Fig. 8 (MEP) and may explain
the experimental results. Thus, model B is in agreement with

Fig. 7. Mechanism of biosorption process.

 W.S. Alencar et al. / Chemical Engineering Journal 209 (2012) 577–588
Fig. 8. Maps of molecular electrostatic potential (MEP) surfaces derived from
B3LYP/6-31G(d,p)calculations for (A) VO-3R dye; (B) siringyl group of LC and (C)
siringyl group of LC protonated. The increase of negative charges goes from the blue
(positive) to red (negative). (For interpretation of the references to color in this
figure legend, the reader is referred to the web version of this article.)
experimental observations suggesting that the acid pH is a critical
factor in the biosorption process.
Finally, the experimental and theoretical results reported in this
work reveal that water molecules have a key role in the biosorp-
tion process: H-bonds are formed between the VO-3R and
ligno-cellulose (LC) through water molecules which are essential
for biosorption of dye on the biosorbent. In accordance with FTIR
spectra, there is no chemical reaction (Supplementary Fig. 2). In
addition, the magnitude of enthalpy of biosorption obtained in this
work (see Table 3) is consistent with the energy of a hydrogen
bond formation [55]. The formation of acidic sites in the substrate
have not been reported in previous works [14,16,45]. On the other
hand, our results suggest that the formation of acidic sites in the
substrate is crucial to biosorption processes involving water mole-
cule chains.
4. Conclusion
Mango (M. indica L.) seeds in natural form (MS), as well as a pro-
tonated form (AMS), are good alternative biosorbents for removal
of the textile dye Victazol Orange 3R (VO-3R) from aqueous solu-
tions. MS and AMS were characterized by FTIR spectroscopy, SEM
and nitrogen adsorption/desorption curves. The VO-3R dye
interacts with the biosorbents at the solid/liquid interface when
suspended in water. The best conditions were established, with re-
spect to both pH and contact time, to saturate the available sites
located on the biosorbent surface. Four kinetic models were used
to adjust the biosorption, and the best fit was obtained by the
587
general order kinetic model. However, the intra-particle diffusion
model gave multiple linear regions, which suggested that biosorp-
tion may also be followed by multiple sorption rates. The
minimum equilibration time of the dye was obtained after 5 h of
contact between VO-3R dye and the MS and AMS biosorbents.
The equilibrium isotherm of these dyes was obtained, which was
best fitted to the Liu isotherm model. The maximum amounts of
VO-3R adsorbed were 51.2 (323 K) and 71.6 (298 K) mg g1, using
MS and AMS as biosorbents, respectively. The thermodynamic
parameters of biosorption (DH°; DS° and DG) were calculated. Fi-
nally, we investigated the interaction mechanism of biosorbent
and VO-3R using QM/MM MD simulation. The results suggest that
water molecules play a key role in interactions between the biosor-
bent and VO-3R, where a chain of H-bonds formed by water mol-
ecules may be a link to the siringyl group (see Supplementary
Fig. 4) of lignin–cellulosic material to sulfonic groups of VO-3R
dye. Herein, we have proposed a new mechanism of biosorption
of VO-3R on the surface of biosorbents, combining experimental
data (FTIR spectra and pH studies) and theoretical calculations,
that might improve our understanding of biosorption processes.
Acknowledgements
We thank to Professor Guimes Rodrigues-Filho from Institute of
Chemistry, Federal University of Uberlandia for donating the man-
go seeds. The authors are grateful to the National Council for Scien-
tific and Technological Development (CNPq, Brazil), and to the
Foundation for Research Support in the State of Rio Grande do
Sul (FAPERGS, Brazil) for financial support and fellowships. We
are also grateful to Center of Electron Microscopy (CME-UFRGS)
for the use of the SEM microscope. We thank to Herolab (Wiesloch,
Germany) for donating the sealing o-ring of the rotor of the Unicem
M centrifuge.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.cej.2012.08.053.
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