Progress in Biophysics and Molecular Biology 141 (2019) 60e71

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Progress in Biophysics and Molecular Biology

journal homepage: www.elsevier.com/locate/pbiomolbio

Adsorption of methylene blue on agroindustrial wastes: Experimental

investigation and phenomenological modelling
L. Meili a, P.V.S. Lins a, M.T. Costa b, R.L. Almeida b, A.K.S. Abud c, J.I. Soletti b, G.L. Dotto d,
E.H. Tanabe g, L. Sellaoui e, *, S.H.V. Carvalho b, A. Erto f
a
Laborato
rio de Processos, Centro de Tecnologia, Universidade Federal de Alagoas, Avenida Lorival Melo Mota, Tabuleiro Dos Martins, Maceio
, AL, 57072-
970, Brazil
b
Laborato
rio de Sistemas de Separaça~o e Otimizaça
~o de Processos, Centro de Tecnologia, Universidade Federal de Alagoas, Avenida Lorival Melo Mota,
Tabuleiro Dos Martins, Maceio
, AL, 57072-970, Brazil
c
Departamento de Tecnologia de Alimentos, Centro de Ci^ encias Exatas e Tecnologia, Universidade Federal de Sergipe, Av. Marechal Rondon, Jardim Rosa
Elze, Sa~o Cristo ~o, SE, 49100-000, Brazil

va
d
Departamento de Engenharia Química, Centro de Tecnologia, Universidade Federal de Santa Maria, Avenida Roraima, 1000, Santa Maria, RS, 97105-900,
Brazil
e
Unit
e de Recherche de Physique Quantique, UR 11 ES 54, Universit
e de Monastir, Facult
e des Sciences de, Monastir, Tunisie
f
Dipartimento di Ingegneria Chimica, Dei Materiali e Della Produzione Industriale, Universita di Napoli Federico II, P.leTecchio, 80, 80125, Napoli, Italy
g
Environmental Processes Laboratory (LAPAM), Chemical Engineering Department, Federal University of Santa Maria, UFSM, Roraima Avenue, 1000, 97105-
900, Santa Maria, RS, 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, agro-wastes coming from soursop (peel, seeds and pulp fiber) and sugarcane (bagasse) are
Received 15 May 2018 used as low-cost biosorbents to remove methylene blue (MB) from aqueous media. Batch experiments
Received in revised form are performed under different experimental conditions investigating the effects of biosorbent amount,
13 July 2018
dye concentration and stirring rate. The best results were found using soursop wastes for a MB con-
Accepted 18 July 2018
centration of 100 mg L
1, using 0.75 g of residue and a stirring rate of 110 rpm, removing a percentage
Available online 25 July 2018
above 90%. Theoretically, adsorption kinetic can be successfully described by the pseudo-second order
model. Redlich-Peterson and Sips models are adopted to interpret the equilibrium adsorption of MB on
Keywords:
Agro-wastes
sugarcane bagasse and soursop residue, respectively. Interestingly, the monolayer model with single
Biosorption energy derived by statistical physics theory is also applied for a deeper explanation of the adsorption
Dyes removal mechanism of MB on both the adsorbents. The application of this model allows defining the adsorption
Methylene blue geometry of the investigated adsorbate and provides important information about the interactions be-
Statistical physics tween the adsorbate and sorbents. In particular, the modelling analysis by statistical physics allows
defining that the dye molecules are adsorbed in vertical position and the adsorption process is multi-
molecular (i.e. n > 1). Finally, the estimation of adsorption energy suggested that MB adsorption on
biosorbent is a physisorption process.
© 2018 Elsevier Ltd. All rights reserved.

1. Introduction
Nowadays, the use of synthetic dyes in textile industry has
become extensive. However, the real amount of dyes employed that
adhere on the textile substrate during processing can significantly
vary, to the point that the total losses can account for until the 50%
(e.g. on cotton) of the reactive dyes used (Ali and Aboul-Enein,
* Corresponding author.
E-mail address: sellaouilotfi@yahoo.fr (L. Sellaoui).
2006; Ali et al., 2009; Gupta and Ali, 2012; Ma et al., 2012;
Basheer, 2017; Sellaoui et al., 2017b). Consequently, considerable
amounts of dyes are discharged into the environment, mainly in
liquid media (Ali and Jain, 2004; Sharma et al., 2010; Ali et al. 2012a,
2018; Dehghani et al., 2016; Burakova et al., 2018). In general, dyes
represent a serious problem to human health and environmental
safety; they can be toxic and carcinogenic and are recalcitrant
molecules, making their removal difficult. Their presence in water,
even at low concentrations, is toxic to living species and can cause
inhibition of photosynthesis of aquatic species, reduction of dis-
solved oxygen and, therefore, poor overall oxygenation (Crini,

https://doi.org/10.1016/j.pbiomolbio.2018.07.011
0079-6107/© 2018 Elsevier Ltd. All rights reserved.
 L. Meili et al. / Progress in Biophysics and Molecular Biology 141 (2019) 60e71
2006; Bello et al., 2011; Khan et al., 2011; Moussavi and Khosravi,
2011; Ali et al. 2012b, 2014, 2016a, 2017a, 2017b; Silva et al., 2017).
Dyes are classified according to their chemical structure and are
composed of groups of atoms responsible for the color, called
“chromophores”. Examples of chromophores groups are anthra-
quinone, metinic group, carbonyl group and others. The chemical
structure of most of the existing dyes is rather complex and this
makes them resistant to aerobic digestion and, in many cases, they
remain as stable when exposed to light, heat and oxidizing agents.
Among the basic dyes, methylene blue (MB) is the most common
water-soluble dye, widely used for dying cotton, wood and leather.
It is also widely used for medicinal purposes in its purified zinc-free
form. MB is not highly toxic to human beings and animals. Despite
of this, it can cause heart rate increasing, nausea and vomiting,
when inhaled, and eye/skin irritation and systemic effects by
accidental contact, including, cyanosis (Gupta et al., 2004; Tsai
et al., 2009; Fernandez et al., 2010; Deng et al., 2011; Ali et al.
2015, 2016b, 2016c, 2016d, 2016e, 2016f; Devi and Sarma, 2016).
For all these reasons, dye removal from wastewaters is an
important task to protect humans and the ecosystems, which as it is
an imperative commitment in terms of industrial waste manage-
ment and environmental protection. Decolorizing by photocatalytic
oxidation, microbiological or enzymatic decomposition and
adsorption on inorganic or organic matrices are the processes that
have been more often suggested to remove synthetic dyes from
wastewaters and potable waters (Robinson et al., 2002; Mondal,
2008; Apurva et al., 2018). Among the numerous dye removal
techniques currently available in the literature, adsorption is an
inexpensive operation compared with the others. Adsorption is
superior in terms of initial cost, flexibility and simplicity of design,
ease of operation and insensitivity to toxicity of pollutants. Other
important characteristic of adsorption is the absence of harmful
substances deriving from operational activities (Rafatullah et al.,
2010; Chen et al., 2012; Bhatti et al., 2015). The most commonly
used adsorbent is largely the activated carbon. However, the use of
this material has limited applications on large scale due the relative
high production and regeneration costs (Al-Degs et al., 2001;
Robinson et al., 2002; Pavan et al., 2008a,b; Moussavi and Khosravi,
2011; Di Natale et al., 2013; Paz et al., 2013).
According to Moussavi and Khosravi (2011), the availability of
effective and low cost adsorbents for dyes is the main research
challenge in this field. The use of biological materials for dyes
removal from aqueous solutions is commonly referred as bio-
sorption and, today, it has attracted a great interest in the scientific
community as sustainable and environmental-friendly materials
for the production of alternative sorbents (Crini, 2006; Rafatullah
et al., 2010; Boudechiche et al., 2016). Many studies in the litera-
ture have demonstrated that biosorbents can be considered as valid
and low-cost alternatives to classical adsorbents as they can reduce
dye concentration in water to ppb levels. According to Raftullah
et al. (Rafatullah et al., 2010), the capacity of low cost adsorbents to
remove MB can vary from 1.17 mg g
1 to 869.6 mg g
1 that is
equivalent to commercial activated carbons. In this scenario,
numerous and different biosorbents can be used on purpose. As an
example, sugarcane bagasse is a by-product of alcohol and sugar
production, generated in the sugarcane milling process, and it is
mainly composed of fiber and water (Lopes Silva et al., 2014).
Currently, Brazil is the largest world producer and exporter of sugar,
the biggest exporter of ethanol and the second largest producer of
ethanol (Duarte et al., 2013). Similarly, Soursop (Annona muricata
L.), known in Brazil as “graviola”, is a popular fruit in all the tropical
regions. It is highly appreciated due to its unique flavor and juicy
flesh. The soursop pulp is widely used for manufacturing various
food products as mixtures of juices, nectars, syrups, shakes, jams,
jellies and ice creams (Telis-Romero et al., 2007). Based on the best
61
of our knowledge, there are no studies regarding the application of
soursop wastes as dye biosorbent. However, modified (Amin, 2008;
Saad et al., 2010; Silva et al., 2011; Fideles et al., 2018) and no-
modified (Zhang et al., 2013; Noreen and Bhatti, 2014) sugarcane
bagasse has been used as biosorbent for several substances.
Adsorption techniques are already well known and the litera-
ture is replete with studies focused on the phenomenological
analysis of the effect of the main process parameters. However, due
to the large application of adsorption technology, the research of
new and unexplored sources for the synthesis of adsorbent mate-
rials, the accurate tuning of operative parameters for a low-cost
preparation and the effective removal of specific contaminant are
still topics attracting the researchers. Therefore, the present work
aims to investigate the possible use of two regional agricultural
wastes (i.e. solid residues of soursop and sugarcane), after very mild
and energy saving activation processes, as new adsorbent materials
for the treatment of polluted effluents. The literature often suggests
the use of expensive activation processes for agro-wastes materials,
which is a manifest non-sense for a low-cost sorbent. The very
important aspect of the work is the use of a very low energy and
time-consuming with the solid preparation, which represents a
mandatory property of a true low-cost material. The effects of
biosorbent amount, dye concentration and stirring rate were
investigated for a kinetic study of MB removal and pseudo first-
order and pseudo second-order models were chosen for data
interpretation. Simultaneously, a thermodynamic study was car-
ried out to define the application limits of each of the tested sor-
bents. For a better explanation of the adsorption results, the
classical models were tested in this paper (e.g. Langmuir, Freund-
lich). In addition, a monolayer model with one energy derived by
statistical physics was also used to attribute steric and energetic
interpretations to the observed phenomena. Based on the scientific
literature, these models are able to explain the adsorption mech-
anism by the interpretation of their regression parameters, e.g.
providing info about the adsorption geometry. The final object is a
deeper insight into the investigated adsorption systems in order to
provide additional interpretative keys of the observed adsorption
phenomena.
2. Materials and methods
2.1. Biosorbents and dye
The dye used for adsorption runs was methylene blue (MB), a
cationic organic dye, whose molecular formula is C16H18N3SCl
(color index 52015). MB is used in different kinds of industries, in
particular, textile, paper and polyesters. MB has maximum ab-
sorption peak at a wave length of 665 nm, a molecular weight of
319.8 g mol
1 and a pKa about 5.6 (Paz et al., 2013).
The sorbents used were derived from two different agro-wastes,
i.e. soursop (peel, seeds and pulp fiber) and sugarcane (bagasse).
The raw wastes were cut and sanitized with 100 mg L
1 of sodium
hypochlorite solution for 15 min and oven dried with forced air
circulation at 50  C until a constant weight was reached. The wastes
were all ground in a knife mill and sieved. The fraction used had a
particle diameter lower than 0.60 mm. All residues were stored in
hermetic plastic packages at room temperature (Silva et al., 2016).
2.2. Characterizations techniques
The physicochemical characterization of the sorbents was car-
ried out by evaluating moisture content, ash content, bulk density,
scanning electron microscopy and point of zero charge pH. The
analysis of moisture content was made by heating a defined
amount of each waste sample in an oven at 105  C, until a constant
62 L. Meili et al. / Progress in Biophysics and Molecular Biology 141 (2019) 60e71
weight was obtained (approximately after 8 h). The evaluation of
solution pH was carried out on a sample containing 2.0 g of residue
in 50 mL of distilled water, kept under agitation for 10 min. After,
the pH was measured by a pHmeter (Marconi/MA PA200). The ash
content was evaluated by direct incineration, which was carried out
by heating the dry sample in an electric muffle at 500  C during 4 h.
The bulk density was evaluated by measuring the volume occupied
by a defined mass quantity of each sorbent. The morphology of the
waste surfaces was observed by means of SEM analysis, using a
Shimadzu SSX-550 equipment. The point of zero charge of each
biosorbent was determined by adding 20 mL of 0.050 mol L
1 of
NaCl solution to water sample with a defined initial pH (varied from
2.0 to 10.0 by adding 0.10 mol L
1 of either HCl or NaOH) in several
flasks containing 50 mg of the tested biosorbent. The suspensions
were kept at 298 K in a temperature-controlled shaker and allowed
to equilibrate for 48 h. The pH of the solutions was measured using
the pHmeter. The value of the point of zero charge is the point
where the curve of pHf-pHi versus pHi crosses a line equal to zero
(Calvete et al., 2009).
2.3. Biosorption tests
The biosorption studies were performed in batch mode.
Different experimental runs were carried out in order to investigate
different aspects of biosorption phenomena, both thermodynamic
and kinetic. Three different kinetic tests were carried out. 1) In a
first run, the biosorbent mass was varied (0.1/0.25/0.5/0.75 g),
keeping constants the MB concentration (100 mg L
1) and the
stirring rate (110 rpm). 2) In a second run, the stirring rate was
varied (60/110/160 rpm), keeping constants the MB concentration
(100 mg L
1) and the biosorbent mass (0.5 g). 3) Finally, in a third
run, the MB concentration was varied (50/100/150/200 mg L
1),
keeping constants the stirring rate (110 rpm) and the biosorbent
mass (0.5 g). In all the experimental runs, the biosorbent was put in
contact with 100 mL of dye solution and the system was agitated in
an incubator shaker Solab, at constant temperature (25  C). All the
experiments were performed at constant pH, around 5.5. The
samples were collected in time intervals of 5/10/30/60/120/180/
300 min. The MB adsorbed amount at any time was calculated ac-
cording to Eq. (1):
ðC0
Ct Þ
qt ¼ V (1)
m
in which qt (mg g
1) is the quantity of MB biosorbed per gram of
biosorbent at any time, Ct [mg L
1] is the MB concentration in the
liquid phase at any time, C0 [mg L
1] is the initial dye concentration,
V is the volume of solution [L] and m is the biosorbent amount [g].
Equilibrium studies were performed in batch mode. To this aim,
0.5 g of sorbent were added to different MB solutions (at concen-
tration equal to 100, 150, 200 and 250 mg L
1 for tests carried out
with soursop residues and 50, 100, 150 and 200 mg L
1 for tests
with sugarcane bagasse) and put in contact for 200 min under
constant agitation of 110 rpm in a shaker incubator. After the time
required for equilibration, aliquots of liquid were sampled for the
analysis of MB residual concentration.
In all the tests, the spectrophotometer Shimadzu UV-mini 1240
was used to quantify the dye content in solution at a wavelength of
665 nm, correspondent to the blue color (Paz et al., 2013). The
biosorption capacity and the MB removal percentage at equilibrium
were calculated using the following Eqs. (2) and (3):
ðC0
Ce Þ
R¼ 100 (2)
C0
ðC0
Ce Þ
qe ¼ V (3)
m
where, qe [mg g
1] is the quantity of MB biosorbed per gram of
biosorbent at equilibrium, and Ce [mg L
1] is the MB concentration
in the liquid phase at equilibrium.
2.4. Kinetic and equilibrium models
Pseudo first-order (Albadarin and Mangwandi, 2015) and
pseudo second-order (Ho and Mckay, 1998) models (Eq. (4) and (5),
respectively), were fitted to the experimental data in order to
investigate the kinetic aspects of MB biosorption on agro-wastes.
q1 ¼ q1 ð1
expð
k1 tÞÞ (4)
t
q1 ¼
 (5)
1=k2 q22 þ ðt=q2 Þ
where, k1 [min
1] and k2 [g mg
1 min
1] are the rate constants of
pseudo first-order and pseudo second-order models, respectively,
and q1 and q2 [mg g
1] are the theoretical values of biosorption
capacity at any time.
In order to fit the experimental equilibrium data, Langmuir,
(1918), Freundlich, (1906), Redlich-Peterson (Redlich and
Peterson, 1959) and Sips, (1948) isotherm models were applied,
reported in Eqs. (6)e(9), respectively.
qm kL Ce
qe ¼ (6)
1 þ ðkL Ce Þ
qe ¼ kF Ce
1=nF
(7)
Ce :krp
qe ¼   (8)
b
1 þ arp :Ce rp
qmax :ks cms
qe ¼
e 
(9)
1 þ ks cms
e
where, qm [mg g
1] is the maximum biosorption capacity, kL [L
mg
1] is the Langmuir constant, kF [(mg g
1) (mg L
1)
1/nF] is the
Freundlich constant, 1/nF [-] is the heterogeneity factor, krp is the
constant of equilibrium for Redlich-Peterson model (L.mg
1), arp is
the constant of equilibrium for Redlich-Peterson model (L.mg
1)brp
and brp is the exponent of Redlich-Peterson model, ks is the equi-
librium constant of Sips model (L.mg
1) and ms is the Sips model
exponent. The regression analysis of experimental data was carried
out with statistic software and the accuracy of data fitting analysis
was measured by evaluation of the coefficient of determination (R2)
and the average relative error (ARE).
3. Results and discussion
3.1. Biosorbents characteristics
The main physicochemical properties of the investigated bio-
sorbents are presented in Table 1. The moisture content results
show that the residues have low water contents, which can facili-
tate the biosorption process. It was found that the soursop residue
presented a significantly lower ash content than sugarcane bagasse.
This indicates that the sugarcane bagasse is mainly formed by
organic material. Regarding to the pH, it is know that methylene
 L. Meili et al. / Progress in Biophysics and Molecular Biology 141 (2019) 60e71
Table 1
Physicochemical properties of the sorbents deriving from agro-industrial residues.
Biosorbent Moisture content (%) Ash content (%)
Sugarcane bagasse 10.45 18.85
Soursop residue 10.90 1.60
blue has pH about 5.5 (Weber et al., 2014) and, coherently, all the
aqueous solutions containing both the residues presented an acid
pH.
The SEM images of (a) sugarcane bagasse and (b) soursop resi-
dues are shown in Fig. 1. The sugarcane bagasse material presented
a heterogeneous surface with protuberances, cracks and cavities
and these characteristics may provide an increase in the surface
available to adsorption (Meili et al., 2017). Observing the soursop is
possible to infer that the surface is even more heterogeneous,
rougher and with more uneven surfaces than sugarcane bagasse,
which can favor the MB adsorption (Weber et al., 2013). It can be
concluded that, at a different extent, the heterogeneous cavities of
these residues at microporous and macroporous scale can favor the
diffusion and adsorption of the dye molecules.
Finally, the point of zero charge (pHpzc) of sugarcane bagasse
and soursop residues resulted to be 1.48 and 5.43, respectively. As it
know in the pertinent literature, for pH values lower than pHpzc, the
biosorbents present a positive surface charge, while for pH values
higher than pHzpc the biosorbents become negatively charged
(Calvete et al., 2009). This result shows that sugarcane bagasse is
more accessible to acquire negative charges. The contents of cel-
lulose, hemicellulose, lignin and pectin in both materials can
explain the differences observed in the pHpzc (Dotto et al., 2016;
Pavan et al., 2008a,b; Aloma
et al., 2012; Ahmad et al., 2016).
3.2. Biosorption results
In Fig. 2, the MB removal percentage as a function of time, and
parametric with MB initial concentration, is presented for both
sugarcane bagasse (Fig. 2a) and soursop residues (Fig. 2b).
In general, MB adsorption on sugarcane bagasse is initially more
rapid than on soursop residue, likely due to the different surface
structure. However, the equilibrium value is reached at higher time,
probably due to a higher contribution of micropores in the sorbent
structure.
The soursop residue showed high values of MB removal,
reaching about 80% at a dye concentration of 150 mg L
1,
Fig. 1. SEM images of (a) sugarcane bagasse and (b) soursop residues.
63
pH Density (g cm
3) Average particle size (mm)
5.16 0.070 0.60
4.03 0.383 0.60
biosorbent amount of 0.5 g and stirring rate of 110 rpm. The lower is
MB concentration, the higher resulted the MB removal percentage.
Regarding the sugarcane bagasse, this residue presented higher
values of MB removal (about 90%) in two experiments (at
50 mg L
1). However, in general, soursop residue was superior with
respect to sugarcane bagasse for MB removal, compared at same
MB concentration and time.
The MB percentage removal is higher when MB concentration is
high, but a non-monothonic trend was observed. In particular, MB
percentage removal increased and reached the highest value for
150 mg L
1 MB concentration, likely due to the properties of sor-
bent surface, which can accept more molecules distributed in the
available space, allowing the establishing of more adsorption bonds
on the surface (Leal et al., 2011). On contrary, the efficiency de-
creases when the MB concentration reached the concentration of
200 mg L
1, probably due to the excess of solute, which generated
competition effects (Magriotis et al., 2010; Perez et al., 2011), or for
the possible aggregation of dye molecules and/or the exhaustion of
the accessible activated sites on the biosorbent surface (Gaffar et al.,
2004).
In Fig. 3, it is possible to observe the effect of biosorbent amount
on MB percentage removal for both the investigated sorbents, at
constant MB concentration. Also, MB seems to be adsorbed more
rapidly on sugarcane bagasse. It was found that an increase in the
biosorbent amount determined an increase in the MB removal
percentage, indicative of a favorable adsorption of MB on both the
sorbents. However, the soursop residue presented an exception to
this behavior passing from 0.5 to 0.25 g.
In Fig. 4, the effect of stirring rate on the MB biosorption is
presented. For both the biosorbents, the MB removal was higher at
160 rpm. The stirring rate effect can be explained by the highest
power dissipation in the system at 160 rpm, which in turn could
determine a local temperature increase. This stirring rate increase
also led to a decrease in the external mass transfer resistance,
facilitating the migration of the dye molecules to the biosorbent
surface and increasing the biosorption capacity in the early steps
(Dotto and Pinto, 2012).
64 L. Meili et al. / Progress in Biophysics and Molecular Biology 141 (2019) 60e71

Fig. 2. Initial MB concentration effect on the biosorption of MB by (a) sugarcane bagasse and (b) soursop residues (biosorbent amount of 0.5 g and stirring rate of 110 rpm).

3.3. Analysis of kinetic and equilibrium experimental data
In general, the kinetic studies have the main objective to predict
the rate at which the pollutants are removed by a solid, which is an
important factor to be considered in the operation design (Plazinski
et al., 2009). The kinetic results of the pseudo first-order and
pseudo second-order models for sugarcane bagasse are presented
in Table 2. For both the models, the R2 values were above to 0.90. In
addition, ARE values varied from 8.3% to 19.15% for pseudo first-
order model and from 4.60% to 15.30% for the pseudo second-
order model. The high values of the determination coefficient and
the low values of ARE demonstrated that the pseudo-second order
model was the more suitable to describe the adsorption kinetic of
MB on sugarcane bagasse in comparison with pseudo first-order.
Moreover, the calculated q1 values obtained from the pseudo first
order model resulted in lower values than the experimental qe
values and than the corresponding experimental figures in all the
cases, confirming that the pseudo-second order model predicted
very well the experimental equilibrium biosorption capacity
(experimental qe). The pseudo second-order model predicts a
chemisorption mechanism and suggests that the boundary layer
resistance was not limiting the MB adsorption (Barka et al., 2013;
Silveira et al., 2014; Mitrogiannis et al., 2015).
Similar results were obtained for the soursop residue. The cor-
responding results in terms of kinetic parameters are shown in
Table 3. It is possible observing that, for both the models, the R2
 L. Meili et al. / Progress in Biophysics and Molecular Biology 141 (2019) 60e71 65

Fig. 3. Effect of biosorbent amount on the biosorption of MB by (a) sugarcane bagasse and (b) soursop residues (Initial MB concentration of 100 mg L
1 and stirring rate of 110 rpm).

values were above to 0.89. However, the ARE values vary from
2.27% to 25.24% for Pseudo first-order model and from 0.87% to
23.87% for the Pseudo second-order model. Moreover, it is clear
that in many cases the difference between the qe experimental and
the estimated q2 is very high. Despite this, the pseudo-second order
model resulted as the more adequate to represent the biosorption
of MB on soursop residue in comparison with the Pseudo-first order
model. For kinetic evaluations, similar results were obtained by
(Mitrogiannis et al., 2015) for the bioadsorption of methylene blue
onto Arthrospira platensis biomass and by (Barka et al., 2013) using
dried prickly pear cactus to adsorb the same dye, where for both
studies the pseudo-second order was the more adequate model to
represent kinetic results (Table 4).
Another crucial analysis for a thorough design and operation of
adsorption processes is the determination of the equilibrium con-
ditions between solute concentration in solution and in the
adsorbed phase [28]. Moreover, a correct modelling analysis is a
fundamental tool for the management of an adsorption device, as it
allows determining the performances of the system in any set of the
possible (and potentially infinitive) operating conditions.
In this work, the Langmuir, Freundlich, Redlich-Peterson and
Sips isotherm models were initially considered to describe the
biosorption of MB on sugarcane bagasse and soursop residues
(Fig. 5). The Langmuir model considers that the adsorption energy
is constant and does not depend on the degree of adsorbent sites
occupation. Other important hypothesis is that the sites are
66 L. Meili et al. / Progress in Biophysics and Molecular Biology 141 (2019) 60e71

Fig. 4. Stirring rate effect on the biosorption of MB by (a) sugarcane bagasse and (b) soursop residues (Initial MB concentration of 100 mg L
1 and biosorbent amount of 0.5 g).

Table 2
Kinetic parameters for the biosorption of MB on sugarcane bagasse.

Parameters 50 mg L
1 0.5 g 100 mg L
1 0.5 g 150 mg L
1 0.5 g 200 mg L
1 0.5 g 100 mg L
1 0.1 g 100 mg L
1 100 mg L
1 100 mg L
1 100 mg L
1 0.5 g
110 rpm 110 rpm 110 rpm 110 rpm 110 rpm 0.25 g 110 rpm 0.75 g 110 rpm 0.5 g 60 rpm 160 rpm

qe (mg g
1) 7.8 13.4 13.4 18.1 24.9 20.2 11.8 15.6 15.9
Pseudo first-order
q1 (mg g
1) 6.87 11.42 13.51 14.36 18.60 16.59 10.94 15.28 13.75
k1 (min
1) 0.165 0.120 0.037 0.119 0.155 0.086 0.151 0.013 0.142
R2 0.96 0.94 0.89 0.94 0.91 0.95 0.97 0.99 0.95
ARE (%) 5.62 7.35 7.47 6.10 8.03 6.30 4.71 2.15 5.72
Pseudo second-order
q2 (mg g
1) 7.27 12.35 14.87 15.55 20.01 18.28 11.61 19.21 14.83
k2 (g mg
1 0.035 0.013 0.004 0.010 0.010 0.006 0.019 0.001 0.009
min
1)
R2 0.982 0.97 0.92 0.97 0.93 0.97 0.99 0.99 0.970
ARE (%) 3.85 4.80 7.67 4.56 6.11 4.11 2.53 2.04 3.90
 L. Meili et al. / Progress in Biophysics and Molecular Biology 141 (2019) 60e71 67

Table 3
Kinetic parameters for the biosorption of MB on soursop residues.

Parameters 50 mg L
1 0.5 g 100 mg L
1 0.5 g 150 mg L
1 0.5 g 200 mg L
1 0.5 g 100 mg L
1 0.1 g 100 mg L
1 100 mg L
1 100 mg L
1 100 mg L
1 0.5 g
110 rpm 110 rpm 110 rpm 110 rpm 110 rpm 0.25 g 110 rpm 0.75 g 110 rpm 0.5 g 60 rpm 160 rpm

qe (mg g
1) 5.1 13.9 19.7 26.5 43.6 29.9 10.9 17.1 17.9
Pseudo first-order
q1 (mg g
1) 12.71 4.18 22.13 20.16 25.13 9.90 49.39 15.37 17.57
k1 (min
1) 0.048 0.319 0.027 0.142 0.054 0.152 0.012 0.04 0.123
R2 0.95 0.89 0.93 0.96 0.95 0.97 0.92 0.95 0.99
ARE (%) 5.24 9.33 6.60 4.30 5.91 2.83 7.34 5.91 6.12
Pseudo second-order
q2 (mg g
1) 13.95 4.44 24.50 21.30 28.03 10.50 60.61 16.99 18.159
k2 (g mg
1 0.005 0.101 0.003 0.010 0.002 0.022 0.000 0.003 0.024
min
1)
R2 0.98 0.93 0.96 0.972 0.98 0.99 0.92 0.97 0.99
ARE (%) 3.74 8.28 4.56 4.13 3.84 1.71 8.67 4.60 0.30

Table 4 represents a significant computational advantage, due to the

Equilibrium parameters for the biosorption of MB on soursop and sugarcane simplified base hypotheses of the model. However, as previously
bagasse. demonstrated, this model was not the best performing for the
Models Parameters Soursop Bagasse description of equilibrium data of both the investigated sorbents.
Langmuir qm
ax (mg/g) 55.3973 17.4345
Hence, a deeper analysis of the applicability of Langmuir model, in
KL (L/mg) 0.0546 0.1711 its generalized form deriving from Statistical Physics, was carried
ARE 7.3008 6.7490 out in the following.
R2 0.9786 0.9612
Freundlich N 2.2185 3.7730
KF [(mg.L
1) (L.g
1)1/n] 7.0277 5.4748
ARE 10.3483 4.7778 3.4. Interpretation of the adsorption equilibrium through the
R2 0.9564 0.9815
monolayer model
Redlich-Peterson KR 2.1398 48.0474
aR (L/mg)b 0.0031 8.3444
b 1.6048 0.0745 The monolayer model represents the general case of Langmuir
ARE 5.6337 4.6629 model and it was applied for the description of the entire set of
R2 0.9873 0.9816 experimental data. The derivation of the model and its base hy-
Sips qm
ax(mg/g) 42.1417 1272.19
potheses were, previously published (Sellaoui et al. 2017a, 2017c).
Ks(L/mg) 0.0098 0.0043
mS 1.9105 0.2676 The monolayer model with single energy model supposes that a
ARE 3.8051 4.7702 receptor site can accept n molecule dyes. The expression of this
R2 0.9929 0.9815 model is given by:

identical, energetically equivalent and there is no interaction be-
tween the molecules adsorbed on the neighboring sites (Gimbert
et al., 2008). The Freundlich model hypothesizes a multilayer
adsorption with non-uniform site energy distribution and a het-
erogeneous surface (El Haddad et al., 2014). The Sips isotherm is
also known as the Langmuir-Freundlich isotherm because com-
bines the Langmuir and Freundlich models. This model bypass the
limitation of the potentially infinitive adsorbate concentration
associated with the Freundlich isotherm model (Foo and Hameed,
2010). At low concentrations of adsorbate, this model behaves as
the Freundlich isotherm, while at high concentrations it behaves as
the Langmuir one (Hamdaoui and Naffrechoux, 2007). Redlich and
Peterson (1959) proposed an empirical equation that could be used
to represent the adsorption equilibrium over a large range of con-
centrations, and it can be applied in either homogeneous or het-
erogeneous systems (Gimbert et al., 2008). This model combines
elements of the Langmuir and Freundlich equations and the
adsorption mechanism is a hybrid, following a non-ideal mono-
layer adsorption (Hamdaoui and Naffrechoux, 2007). For both the
investigated adsorbents, all the models suitably fitted the experi-
mental data. However, for sugarcane bagasse Redlich-Peterson
presented higher value of R2 (0.9816) and lower value of ARE
(4.6629) indicating that this model is more adequate to represent
the equilibrium data. On contrary, Sips model was the more suit-
able for soursop equilibrium data interpretation, having the highest
value of R2 (0.9929) and the lowest value of ARE (3,8051).
The description of equilibrium adsorption by Langmuir model
nNM
Q¼  n (10)
1þ
c1=2
c
In this expression, n is the number of dye molecules captured
per adsorbent surface, c1/2 the concentration at half saturation, NM
is the receptor sites effectively occupied. This model was applied to
the equilibrium adsorption isotherms and the fitting results are
reported in Fig. 6.
According to Sellaoui et al. (2018), if the number of dye mole-
cules is n < 1, this evidence indicated that the investigated
adsorption is a multi-anchorage process reflecting a parallel posi-
tion of dye molecules on adsorbent surface. In this case, the dye
molecules can simultaneously interact with several functional
groups of the adsorbent surface. On contrary, if n > 1, adsorption is
multi-molecular process and the molecules can interact by vertical
position with the surface of the investigated adsorbent.
The fitting results demonstrated that the number of dye mole-
cules is 1.22 and 2.18 on Soursop residue and Sugarcane bagasse,
respectively. Hence, the adsorption is a multi-molecular process,
which can be also described by a monolayer model. In addition, the
adsorption geometry of dye molecules is vertical in all the inves-
tigated systems. Finally, it was noticed that the number of dye
molecules linked per adsorbing site is higher on Soursop probably
due to its surface properties, as already previously observed. Based
on the monolayer model, it is possible to further characterize the
interactions between the dye molecules and the adsorbent surface
by the calculation of the adsorption energy. The expression of the
energetic parameter is reported in Sellaoui et al. (2017a) as:
68 L. Meili et al. / Progress in Biophysics and Molecular Biology 141 (2019) 60e71

Fig. 5. Fitting of adsorption isotherms through Langmuir, Freundlich, Redlich-Peterson and Sips models for (a) soursop and (b) sugarcane bagasse.

 .  respectively, suggesting that the adsorption is exothermic and a

DE ¼ RT ln cs c1=2 (11) physisorption process.

in which cs is the solubility of the investigated dye and c1/2 is the 4. Conclusions
concentration at half saturation provided by fitting method. The
adsorption energy values derived from the model were
13.44 kJ/ In this work, sugarcane bagasse and soursop residues were
mol and
22.18 kJ/mol on Soursop residue and Sugarcane bagasse, tested as biosorbents to remove MB from aqueous solutions, under
 L. Meili et al. / Progress in Biophysics and Molecular Biology 141 (2019) 60e71
Fig. 6. Fitting of adsorption isotherms through monolayer model.
different experimental conditions. The results showed that, with
sugarcane bagasse, a maximum removal of 90.4% can be obtained,
with a dye concentration of 50 mg L
1, biosorbent amount of 0.5 g
and stirring rate of 110 rpm. For the soursop residue, the maximum
removal capacity was 91.6% at 110 rpm, dye concentration of
100 mg L
1 and biosorbent amount of 0.75 g.
The kinetic experiments of adsorption of MB onto both sugar-
cane bagasse and soursop residue were successfully interpreted by
the pseudo-second order model, presenting high values of the co-
efficient of determination (R2) and low average relative error (ARE).
The equilibrium experiments showed that for sugarcane bagasse,
higher values of R2 and lower values of ARE indicate the Redlich-
Peterson isotherm as the more adequate model, while, for sour-
sop residue the biosorption followed the Sips model. Moreover, in
order to keep the advantages deriving from Langmuir model
application, the entire set of experimental data was successfully
interpreted by a monolayer model derived from statistical physics,
which allowed determining that MB adsorption is a multi-
molecular process based on physisorption. The results presented
in this work revealed that both sugarcane bagasse and soursop
residue are valid alternative biosorbents for the removal of MB from
aqueous media, as they are characterized by low-cost production
for activation processes and simultaneously offer high removal
performances.
Acknowledgement
The authors thank to CNPq, CAPES and FAPEAL.
Appendix A. Supplementary data
Supplementary data related to this article can be found at
https://doi.org/10.1016/j.pbiomolbio.2018.07.011.
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