Environmental Science and Pollution Research

https://doi.org/10.1007/s11356-021-14150-8

RESEARCH ARTICLE

Synergistic effect of the activated carbon addition

from leather wastes in chitosan/alginate-based composites
Flávia Melara 1 & Thaís Strieder Machado 1 & Ingridy Alessandretti 2 & Christian Manera 3 & Daniele Perondi 3 &
Marcelo Godinho 3 & Jeferson Steffanello Piccin 1

Received: 14 January 2021 / Accepted: 22 April 2021

# The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature 2021

Abstract
In this work, chitosan/alginate composites were developed by the gelation method with the addition of different amounts of
activated carbon produced from tannery waste (ACTW). The performance of these composites was verified through the adsorp-
tion of the textile dye Remazol Brilliant Blue R (RBBR). A synergistic effect was observed by the addition of ACTW; with a
specific surface area up to 45.584 m2/g, the maximum adsorption capacity was 300.96 mg/g. The synergy was due to the
reduction in steric hindrance, with the adsorption capacity 1.2 times higher than expected. The material was regenerated with
sodium hydroxide for 10 cycles. The composite containing 30% ACTW (AC30) was applied in the treatment of real textile
effluent, with 30% reductions in the biochemical oxygen demand (BOD), 39% in the chemical oxygen demand (COD), 78% in
turbidity, and 67% in color.

Keywords Remazol Brilliant Blue R . Textile dye . Textile effluent . Adsorbent synthesis . Adsorption isotherms . Adsorption
kinetics

Introduction metabolized by the present microorganisms and generate

The textile industry demands about 80 to 200 L of water
for each kilogram of fabric produced (Ghaly et al. 2014).
In dyeing, between 10 and 15% of dyes do not stick to
textile fibers and result in color wastewater (Gita et al.
2017). Dyes, when present in water bodies, can be
Responsible editor: Tito Roberto Cadaval Jr
* Flávia Melara
flaviamelara@gmail.com
* Jeferson Steffanello Piccin
jefersonpiccin@upf.br
1
Faculty of Engineering and Architecture (FEAR), Postgraduate
Program in Civil and Environmental Engineering (PPGEng),
University of Passo Fundo (UPF), Passo Fundo, RS, Brazil
2
Faculty of Engineering and Architecture (FEAR), Chemical
Engineering Course, University of Passo Fundo (UPF), Passo
Fundo, RS, Brazil
3 followed by activation, results in an activated carbon with
Postgraduate Program in Process Engineering and Technologies,
University of Caxias do Sul (UCS), Caxias do Sul, Rio Grande do
Sul, Brazil
toxic by-products (Rawat et al. 2018), causing damage to
fish development (De Oliveira et al. 2016) and the death
of other aquatic organisms (Darsana et al. 2015). Since
most dyes are resistant to biodegradation (Bilal et al.
2018), advanced treatment methods can be used to re-
move these pollutants, such as membrane filtration
(Homem et al. 2019), electrolysis (Liu et al. 2020), ad-
vanced oxidative processes (Machado et al. 2020), and
adsorption (De Rossi et al. 2020).
In the treatment of water and wastewater by adsorption,
the most widely used adsorbent is activated carbon
(Bonilla-Petriciolet et al. 2019) that can be produced from
several sources of biomass, with lignocellulosic materials
being the most common (Heinonen et al. 2017). In addi-
tion, activated carbon can also be produced from industri-
al waste. The direct use of tannery shaving waste for
adsorption purposes has been reported in the literature
(Piccin et al. 2017a). Additionally, the thermochemical
conversion of leather shaving waste, through pyrolysis,
adequate adsorbent characteristics, as observed by Manera
et al. (2018).
 Environ Sci Pollut Res

Chitosan is a natural biopolymer obtained by alkaline

deacetylation of chitin. The acetyl groups are hydrolyzed in
the process and result in free amines that, together with hy-
droxyls, have a high potential for adsorption (Piccin et al.
2009; Zhang et al. 2020). Despite the high adsorption capac-
ity, chitosan has undesirable characteristics for an adsorbent,
such as low specific surface area and solubility in acid medi-
um, which causes low mass transfer, steric hindrance of ad-
sorption sites, difficulty in regeneration and it cannot be used
in fixed bed systems (Dotto et al. 2015; Gama et al. 2017;
Kasiri 2019).
In this context, chitosan-based adsorbent materials have
been developed by process such as immobilization on sup-
ports (Vieira et al. 2014), chemical modification with
crosslinkers (Vakili et al. 2018) and surfactants (Pal and Pal
2017), scaffold (Alves et al. 2019), chitosan composites with
silica (Blachnio et al. 2018), sodium alginate (Gokila et al.
2017), and bentonite (Dotto et al. 2016).
Sodium alginate is a linear water-soluble polysaccharide
extracted from algae, composed of alternating blocks of linked
-l-guluronic and -d-manuronic acid residues (Gokila et al.
2017), which forms a gel when in contact with cations
(Bedade et al. 2019), such as calcium or chitosan. This bio-
polymer has a structural function in the formation of compos-
ites, allowing the materials that are the most suitable format
for use in adsorption systems (Abou el Fadl 2014). The
crosslink between the chitosan amine groups and the sodium
alginate carboxyl groups is one of the alternatives for the
chitosan composite production (Tang et al. 2020).
Nevertheless, this composite may have a surface area lower Fig. 1 Experimental setup of the composites development (a) and
adsorption assays (b)
than the chitosan itself (Ngah and Fatinathan 2008 ).
Therefore, the addition of a porous component can improve
the textural characteristics of chitosan composites based in Materials
sodium alginate.
In this work, the development of chitosan/alginate Powdered activated carbon was produced from tannery shav-
adsorbent composites by the gelation technique with ing wastes according to Manera et al. (2016): leather shavings
the addition of different concentrations of activated car- were pyrolyzed in a semi-continuous pilot screw reactor at
bon for application in the adsorption of Remazol 450 °C. Afterward, the char produced was demineralized with
Brilliant Blue R textile dye was realized. Isotherms HCl (3 mol/L), washed and dried. Subsequently, the char was
and kinetics of adsorption in aqueous solution were car- activated with CO2 in a fixed-bed tubular reactor at 900 °C
ried out in order to define the adsorption capacity and and a holding time of 6h.
the mechanisms of mass transfer. The life cycle of the Chitosan was produced from shrimp shells by the proce-
adsorbent was evaluated through assays of desorption of dure described by Weska et al. (2007), according to the adap-
the material for dye adsorption in aqueous solution. The tations suggested by Moura et al. (2015). The shrimp shells
adsorbents were analyzed for their physical and chemi- were demineralized with 2.5% HCl (v/v), deproteinized with
cal properties. Finally, the efficiency of the developed 5% NaOH (w/v,) and deodorized with 0.36% (v/v) NaCl
adsorbent was evaluated when treating a real effluent obtaining chitin. The thermochemical deacetylation of chitin
from a textile industry. was performed with a 45% NaOH solution (m/v) at boiling
temperature for 4 h.
After deacetylation, the material was washed until pH close
Material and methods to neutral (between 7.5 and 8.0), obtaining the unpurified chi-
tosan. Chitosan was subsequently purified by solubilization in
The experimental development happen as shown in Fig. 1. a 2% (v/v) acetic acid solution, followed by centrifugation.
Environ Sci Pollut Res
From the supernatant, chitosan was precipitated by adjusting
to pH 12 with 2 mol/L NaOH, followed by neutralization to
pH 7.5 with 1 mol/L HCl and collected by centrifugation, and
then frozen in an ultra-freezer. Finally, the purified chitosan
was lyophilized (Terroni/LS 3000) with temperature ranging
from −40 to −70 °C, under vacuum. The characteristics of
chitosan and activated carbon used in this study are presented
in supplementary material. Three batches of chitosan produc-
tion were carried out, and a yield of 13.8 to 20.5% was ob-
served about shrimp shells, and 75.4 to 79.2% of chitosan
yield was about chitin. These observed variations depend on
the characteristics of the raw material (shrimp shells), and are
in line with what was observed by Hossain and Iqbal (2014)
and Nouri et al. (2016).
The Remazol Brilliant Blue R (RBBR) dye of the anthra-
quinone class (Sigma Aldrich, CAS N° 2580-78-1 and analyt-
ical grade) was used in adsorption assays.
Development of the composites
The chitosan/alginate composite was developed using the ex-
ternal gelation method. For this, 2 g of sodium alginate were
dissolved in 100 mL of distilled water and kept under agitation
for 4 h at 90 °C. In parallel, a solution containing 1 g of
chitosan and 0.624 g of calcium chloride was dissolved in
100 mL of 2% acetic acid (v/v). The solutions were mixed
using a mechanical stirrer (Fisatom/713D) and crushed in a
multipurpose mixer (Britania/063202012). Afterward, the
solids obtained in this step were dried by parallel air convec-
tion at 1.5 m/s at 50 °C for 12 h. The material was washed with
distilled water to remove excess calcium and dried again un-
der the same conditions for 6 hours. The material was crushed
in a hammer mill (Tecnal/TE-631/3) and milled between the
standard screens mesh 24 to 42 (0.71–0.355 mm). The mate-
rial obtained by this procedure was named AC00.
The variation of this method occurred by the addition of
powdered activated carbon (AC) in the proportions of 10%
(w/w, named AC10), 20% (w/w, named AC20), and 30%
(w/w, named AC30) in relation to the chitosan mass. The
activated carbon was homogenized with the sodium alginate
solution and then mixed with the chitosan solution, following
the same procedure described previously.
Adsorption assays
The assays were performed in duplicate on an orbital shaker at
100 rpm (Tecnal/TE-421) in two steps, with all assays con-
ducted at pH 2.5 using McIlvaine buffer solution, being the
ideal pH for adsorption determined in preliminary studies. The
initial and final RBBR dye concentrations in all experiments
were determined by spectrophotometry at 595 nm (Tecnal/
ESPEC-UV-5100), standard curve ([C, in mg/L] = absor-
bance*132.72+0.4777, R2 = 0.999).
The equilibrium curves were obtained at temperatures of
25 °C, with initial dye concentration of 50 to 400 mg/L. To
this, 50 mL of dye solution were added to 50 mg of adsorbent
and kept under agitation until equilibrium was observed (av-
erage relative error less than 5% in three consecutive measure-
ments at 1 h intervals in the concentration of the supernatant)
(Piccin et al. 2017b). Under common conditions for the com-
posite with the best adsorptive performance, equilibrium
curves were observed at temperatures of 15°C and 35°C.
The adsorption capacity was determined according to Eq. (1):
ðC 0 −C e Þ  V
q¼ ð1Þ
m
where q is the adsorption capacity at equilibrium (mg/g), C0
and Ce are the initial concentrations of the dye and the con-
centration of the dye at equilibrium (mg/L), V is the volume of
the solution (L), and m is the mass of the adsorbent (g).
The adsorption kinetics were obtained at 25 °C, adding 1.2 g/L
of adsorbent to 250 mL of 100 mg/L dye solution, and kept under
agitation. Aliquots were removed in the range of 0 to 300 min.
Adsorption isotherms and kinetic models were used to cor-
relate experimental data. Adjustments of the parameters of the
isotherm and adsorption kinetics models to the experimental
data were performed using MATLAB® software. The algo-
rithms used in the modeling are available at https://www.
dropbox.com/sh/elq2br3319ccbds/AAB2CTE2Hgb8bG_
0Ue48tfLfa?dl=0.
Desorption
The life cycle of the adsorbent was evaluated by subjecting the
composite to ten consecutive cycles of adsorption. The ad-
sorption step was performed by adding 20 mg of adsorbent
in 30 mL of aqueous solution of the RBBR dye at 200 mg/L,
at pH 2.5, at 25 °C, under agitation of 100 rpm, for 3 hours.
After this time, the material was centrifuged and the adsorbent
loaded with the dye was subjected to a desorption step, per-
formed with the addition of 5 mL of 0.05 mol/L NaOH solu-
tion under agitation, at 25 °C, for 10 min. The eluent solution
was completely separated by centrifugation and the material
was washed with 10 mL of distilled water, followed by a new
centrifugation. The removal and regeneration of the adsorbent
was calculated according to Eqs. (2) and (3):
C 0 −C ads
Removal ¼  100 ð2Þ
C0
mdes  100
Regeneration ¼ ð3Þ
mads
which C0 is the initial concentration (mg/L), Cads is the final
concentration corresponding to each adsorption cycle (mg/L),
mdes is the desorbed mass in each desorption cycle (mg), and
mads is the adsorbed mass in each adsorption cycle (mg).

Real textile wastewater treatment
Real textile wastewater was collected in a jeans processing
industry located in the state of Rio Grande do Sul, Brazil. It
was collected after going through the conventional stages of
treatment of equalization, coagulation, and flocculation. The
assay was conducted at a concentration of 1.2 g/L of the ad-
sorbent, wich has presented the highest adsorption capacity in
the equilibrium assays. The pH was adjusted to 2.5 using 1
mol/L HCl. The assay was carried out at 25 °C, under agita-
tion of 100 rpm for 4 h. Wastewater was characterized before
and after adsorption by biochemical oxygen demand (BOD)
(Method 5210B), chemical oxygen demand (COD) (Method
5210D), total phosphorus (Method 4500P E), total nitrogen
(Method 4500-NH3 B), suspended solids (Method 2540D),
Hazen color (Method 2120-B), and turbidity (Method 2130-
B), according to APHA (2017).
Characterization of adsorbents
The morphological characterization of the adsorbent surface
was verified by Scanning Electron Microscopy (SEM)
(Tescan/Vega3 model), using composite particles classified
with size less than 0.074 mm. The specific surface area was
determined by the BET method (Brunauer et al. 1938))
through N2 adsorption isotherm at −196.15 °C, while the pore
size distribution was obtained by the DFT method
(Quantachrome Instruments/Nova 1200e model), using com-
posite particles classified with size less than 0.074 mm. The
samples were initially degassed under N2 flow at 110 °C for
72 h. The characterization of the surface chemical groups was
carried out by Fourier transform infrared spectroscopy
(FT.IR) through attenuated total reflectance (ATR) (Agilent
Technologies/Cary 630 FT.IR), using composite particles
classified with size less than 0.074 mm. The point of zero
charge (pHPZC) was determined by the pH drift method,
adapted from Newcombe et al. (1993), with 50 mg of adsor-
bent (particle size between 0.71 and 0.355 mm) mixed with 20
mL of 0.05 mol/L NaCl solution, in the pH range of 2 to 9
(adjusted with 0.1 mol/L NaOH and 0.1 mol/L HCl) and kept
under agitation of 100 rpm, at a temperature of 25 °C, for 24 h.
After this period, the final pH of the samples was compared to
the initial, with pHPZC being the final pH that most closely
matches the initial.
Results and discussion
Synthesis and characterization of adsorbents
Figure 2 shows photographs of the composites produced.
Composites containing activated charcoal showed a character-
istic color of charcoal, and the chitosan/alginate material
Environ Sci Pollut Res
showed a typical chitosan color. The granulometry shown in
Fig. 2 was obtained on purpose for the adsorption assays.
In Fig. 3, the N2 adsorption isotherms are presented, as well
as the morphology of the different composites. It is possible to
observe that the N2 adsorption capacity (Fig. 3a) increases
with the addition of CA in the composite. According to Fig.
3b, the pores of the composites are mostly micropores (<20 Å)
and mesoporous (20–500 Å). According to Ngah and
Fathinathan (2008), chitosan and alginate composites result
in mesoporous materials; therefore, the interaction between
these components with activated carbon resulted in compos-
ites with micropores. Micropores are desirable since the size
of the pores has an influence on the adsorption process; the
increase in the size of the pores can lead to a reduction in the
specific surface area; on the other hand, very small pores can
prevent the transfer of material (dye) to the particle
adsorbent.As shown in Fig. 3 c and d, it is observed that the
composite AC00 has a smooth surface while with a magnifi-
cation of ×120k a rougher surface can be verified. The com-
posite AC30 (Fig. 3 e and 3f), magnification of ×120k, has a
rougher surface compared to the AC00. According to Dubey
et al. (2016), a rough and irregular surface in chitosan nano-
particles improved the adsorption of mercury (Hg). As noted
by Abou El Fadl (2014) and Nasrullah et al. (2008), the higher
the alginate content in the composite, the lower the observed
roughness. In preliminary studies of this work, in supplemen-
tary material (Table 2A), it was observed that pure sodium
alginate has a low adsorption capacity (40 mg/g in C0 of 450
mg/L). The roughness influences, since it gives to the material
surface irregularities with different strengths, depth and inter-
connection, which are favorable to diffusion (Nasrullah et al.
2018). Therefore, in composites with alginate, it can be in-
ferred that an increase in roughness may represent an increase
in the adsorption capacity.
Table 1 presents the textural properties of composites in
different proportions of activated carbon in relation to chitosan
(from 0 to 30%). The ratio of chitosan and activated carbon
was determined by a mass balance, considering the mass
added at the beginning of the process and the mass yield of
each composite at the end of the process.The specific surface
area of the AC30 is 144% greater than AC20. It is possible to
observe that the addition of CA also caused an increase in the
total pore volume of the composites (from 0.0045 cc/g for
AC00 to 0.0404 cc/g for AC30).
The interaction between chitosan and sodium alginate gen-
erally results in mesoporous materials, as reported by Ngah
and Fatinathan (2008), justifying the mesoporous classifica-
tion of the composites produced in this work.
According to Fig. 4a, the pHPZC for AC00 and AC30 were
5.7 and 6.6, respectively. Thus, it can be inferred that the
addition of CA provided an increase in the pHPZC value, since
the pure CA used in this study has a pHPZC of 7.7 (Manera
et al. 2018). The chitosan used in this work has a pHPZC of 6.7
Environ Sci Pollut Res
Fig. 2 Photographs of the
developed adsorbent composites
(Subramani and Thinkaran 2017). This shown that in an acid
medium, the surface of the composites assumes a positive
charge, with the ability to adsorb anionic materials such as
RBBR dye (Piccin et al. 2009).
Figure 4b shown the FT.IR spectra of the adsorbent com-
posites. The 3246 cm−1 broadband corresponds to OH hy-
droxyl groups (Piccin et al. 2011a). At 2922 cm−1, there is a
more prominent band for AC00, which suggests the elonga-
tion of the NH chitosan group (Dotto et al. 2015). The bands at
1576 cm−1 and 1550 cm−1 are related to deformation of the
chitosan amino groups (Piccin et al. 2011a). The bands at
1405 cm−1 and 1399 cm−1 are the O-H grup formed by inter-
molecular interaction, such as the hydrogen bond between
sodium alginate and chitosan (Smitha et al. 2005). Bands
found by Manera et al. (2018) in this same region (1628,
1575 and 1385 cm−1) of wavenumbers indicate an asymmetric
vibration of the C=O group, present in activated carbon. The
band at 1034 cm−1 and 1021 cm−1 corresponds to a stretching
C=O, which can be found in chitosan molecules (Dotto et al.
2015), sodium alginate, and also on activated carbon (Manera
et al. 2018). The presence of amine groups on the surface is
also suggested by the observed pHPZC values.
Adsorption isotherms
The adsorption isotherms of the RBBR dye are shown in Fig.
5. Composite isotherms can be classified, according to Giles
et al. (1960), as follows: L1 for AC00 and AC10 and L2 for
AC20 and AC30. Class L1 indicates that the adsorption sites
have not been completely occupied and the monolayer is not
saturated. The L2 class indicates that there was complete sat-
uration of the monolayer, and for a new adsorption to happen,
it is necessary to overcome a high repulsion energy barrier
between the adsorbed molecules and those present in the me-
dium (Piccin et al. 2017b; Giles et al. 1960). This demon-
strates that the addition of activated carbon in the chitosan/
alginate composites causes an organization of the availability
of the adsorption sites, facilitating the monolayer formation.
It’s observed in Fig. 5 that in higher equilibrium concentra-
tions, the composites have greater adsorption capacities; this is
due to the formation of a gradient that provides motive force
for the solute to be adsorbed on the surface of the adsorbent
particle (Hoseyni et al. 2013).
For adsorption isotherms classified as L1 and L2, the most
used models in the literature are Langmuir (1918), Freundlich
(1906), Redlich and Peterson (1959), and Liu et al. (2003),
according to Eqs. (4), (5), (6), and (7), respectively:
K L  qm  C e
qe ¼ ð4Þ
1 þ K L  Ce
qe ¼ K F  C 1=n ð5Þ
e
k R  Ce
qe ¼ ð6Þ
1 þ aR  C βe

nL
K g  Ce
qe ¼ qm 
nL ð7Þ
1 þ K g  Ce
where qm is the maximum adsorption capacity (mg/g), KL is
the Langmuir constant (L/mg), KF is the Freundlich constant
((mg/g) (L/mg) n), n is the heterogeneity factor, kR (L/mg) and
aR are the Redlich and Peterson constant ((g/mg) (L/mg)1/b)
and β is an exponent that can vary from 0 to 1, Kg is the Liu
equilibrium constant (L/mg), and nL is dimensionless expo-
nent of the Liu equation. Table 2 shows the adjustment of the
isotherm models to the experimental data.

Fig. 3 Characterization of
composites: N2 adsorption
isotherm by the BET method (a),
pore size distribution (b), SEM
micrographs of AC00 (c and d)
and AC30 (e and f)
In Table 2, the adjusted R2 values indicate the fit of the
models to the experimental data. The data for composites
AC00 and AC10 are best explained by the Freundlich
model (adjusted R2 of 0.906 and 0.959, respectively).
The Liu model presented a better fit to the composite
AC20 data (adjusted R2 of 0.988), and these data are also
represented by the Langmuir model (adjusted R 2 of
0.987). For the composite AC30 data, two models showed
satisfactory fit, the Freundlich model (adjusted R 2 of
0.989) and Liu (adjusted R2 of 0.990).
Langmuir’s model suggests that adsorption occurs homo-
geneously, with constant enthalpies and adsorption energies,
Environ Sci Pollut Res
all sites have the same affinity for adsorbate, and each site can
only adsorb one molecule, forming a monolayer. Freundlich’s
model represents a heterogeneous adsorption to Henry’s law,
suggesting that adsorption does not happen with constant ad-
sorption energies and equal affinity between the sites and the
adsorbate. The Redlich and Peterson isotherm has a linear
concentration dependence in the numerator and an exponen-
tial dependence in the denominator to represent equilibria over
wide concentration ranges in homogeneous and heteroge-
neous adsorption systems. When β approaches to zero, it
tends to the Freundlich model, and when it approaches to 1,
it tends to the Langmuir model (Foo and Hameed 2010). The
Environ Sci Pollut Res

Liu model incorporates parameters from the Langmuir and
Freundlich models, but dismisses the assumption of
Langmuir monolayer formation and Freundlich infinite ad-
sorption. This model suggests that the active sites may present
energetic differences, which may cause a preference for the
adsorbate molecules at the time of occupying the sites (Liu
2003).
It can also be observed that the qm predicted by the Liu
model is higher for all composites. This difference is due to
the fact that the Liu model considers that the adsorbent surface
is saturated in higher concentrations of adsorbate than those
used in this study.
The dotted lines in Fig. 5 represent the “expected” adsorp-
tion capacity for composites developed as a function of the
equilibrium concentration. This value was calculated accord-
ing to Eq. (8):



 ference between the composites is noticeable, and the density
qexpected ¼ xQ  qe;Q þ xA  qe;A þ xAC  qe;AC ð8Þ
where xQ, xA, and xAC are the mass fraction (%) of chitosan,
sodium alginate, and activated carbon, respectively, and qe,Q,
qe,A, and qe,AC, are the equilibrium adsorption capacity (mg/g)
of chitosan, sodium alginate, and activated carbon, respective-
ly, predicted by the Langmuir at different equilibrium
concentration.
According to Fig. 5, for AC00, the experimental qe was
only greater than that expected at equilibrium concentrations
below 80 mg/L. While AC10 presented an experimental qe
above the expected in Ce below 280 mg/L. However, AC20
and AC30 showed an experimental qe above expected in all
equilibrium concentrations, showing that there was a syner-
gistic effect between chitosan and activated carbon improving
the adsorption capacity. This is due to the exposure of the
amine and hydroxyl groups (chitosan and activated carbon).
In addition, the porous structure of activated carbon may have
acted as a support for the polymeric network of sodium algi-
nate, causing the overlap of electronic clouds to decrease. This
leads to a reduction in the steric hindrance of the adsorption
sites. In the adsorption of methyl orange by a chitosan and
maghemite composite, Obeid et al. (2013) observed that in
higher dye concentrations, the steric hindrance made it diffi-
cult to access the adsorption sites. Shariatzadeh and Moradi
(2014) evaluating the surface functionalization of multiwalled
carbon nanotubes with chitosan and magnesium oxide nano-
particles also observed a synergistic effect. In this case, the
synergy occurred because the chitosan NH2 and OH groups
acted in the assembly of MgO nanoparticles through electro-
static interactions and hydrogen bonds.
Adsorption kinetics
The adsorption kinetics presents the mechanisms involved in
the adsorption process and the physico-chemical interactions
between adsorbate and adsorbent (Enayatpour et al. 2018).
Figure 6 shows the adsorption kinetics of the RBBR dye in
composites. It is observed that at the beginning of the adsorp-
tion the composites do not seem to shown a difference in
adsorption density. Though with the evolution of time, a dif-
of adsorption increases in materials with activated carbon.
During the 180-min period, no adsorption equilibrium was
observed.
The kinetic data were compared to the pseudo-first order
(Lagergren 1898), pseudo-second order (Ho and Mckay
2000), and Elovich (Elovich and Larinov 1962) models, ac-
cording to Equations (9), (10), and (11).


qt ¼ qe;1 1−exp−K 1 t ð9Þ
t
qt ¼ ! ! ð10Þ
1 t
þ
K 2 qe;2 2 qe;2
1
qt ¼  lnð1 þ abt Þ ð11Þ
a
where qe and qt the adsorption capacity (mg/g) at equilibrium
and at a given time t (min), K1 (min−1) and K2 (g/mg/min) are
the kinetic rate constant of the pseudo-first and pseudo-second
order models, α is the initial adsorption rate (mg/g/min) and β
is related to the extent of surface coverage and the energy
involved in chemisorption (g/mg). The parameters of the ki-
netic models are shown in Table 3.

Table 1 Composition and

textural characterization of the Material Chitosan Activated carbon Specific surface Total pore Average pore
chitosan/alginate composites content (%) content (%) area (m2/g) volume (cm3/g) radius (Å)
added by the activated carbon
AC00 35.21 0 2.6 0.0045 35.9334
AC10 28.13 2.81 9.5 0.0079 17.4168
AC20 30.70 6.14 19.9 0.0123 12.8740
AC30 32.21 9.66 48.56 0.0404 17.3207

Fig. 4 Chemical characterizations of adsorbents composites. pHPZC (a) and FT.IR spectrum (b)
In Table 3, it is possible to verify that both models
have satisfactory adjusted determination coefficients (R2
adjusted>0.95). However, pseudo-first order model un-
derestimates the adsorption capacity calculated by the
Langmuir isotherm model for the experimental condition
(qe,experimental). The pseudo-second order model was able
to predict the adsorption capacity with a closer approx-
imation to the real values. Considering R2, the model
that best explains the experimental data of the AC00,
AC10, and AC30 composites was the Elovich model,
and the data of the AC20 composite, the pseudo-first
order model.
Fig. 5 Adsorption isotherms of RBBR dye at 25°C and pH 2.5 by
chitosan/alginate composites with different concentrations of activated
carbon: AC00 (a), AC10 (b), AC20 (c), and AC30 (d). Solid lines
Environ Sci Pollut Res
The pseudo-first order model represents the adsorption that
occurs due to a driving force generated by a difference in
concentration of the external mass transfer coefficient
(Piccin et al. 2011a). The Elovich model suggests that the
adsorbent surface is heterogeneous (Lima et al. 2015),
disregarding the desorption mechanisms, and the adsorption
rate decreases over time due to an occupation of the active
sites on the adsorbent surface (Teng and Hsieh 1998).
Similarly, the expected adsorption capacity of the compos-
ite over time (qt,expected) was determined according to Eq. (8).
Comparing the expected adsorption capacity with that verified
experimentally, it was observed that when the amount of
represents the Langmuir isotherm model adjust. Dashed lines represent
the expected capacity
Environ Sci Pollut Res

Table 2 Isothermal parameters of the RBBR dye adsorption by the Adsorption thermodynamics
chitosan/alginate composites with different activated carbon additions at
25 °C and pH 2.5
The effect of temperature in the adsorption of RBBR dye by
Parameter AC00 AC10 AC20 AC30 the AC30 composite is shown in Fig. 8. The adsorption ca-
pacity in equilibrium increased with the increase in tempera-
Langmuir
ture. In addition to the increase in the adsorption capacity, the
KL (L/mg) 0.185 0.030 0.096 0.078
temperature had an effect on the adsorption affinity, observed
qm (mg/g) 70.748 123.632 210.257 231.182
by the decrease in KL values.
R2 0.543 0.816 0.988 0.963
The effect of increasing the temperature results in the in-
R2 adjusted 0.502 0.801 0.987 0.960
crease in kinetic energy and the intraparticle diffusion of the
Freundlich
adsorbate, may cause a pore unblocking, allowing larger mol-
KF (mg/L) 30.137 16.718 49.646 47.918 ecules to be adsorbed (Açikyildiz et al. 2015). Isotherms are
1/n 6.257 2.850 3.637 3.314 classified as L2 (Giles et al. 1960), which are well represented
R2 0.914 0.962 0.913 0.962 by the Langmuir model, as shown previously.
R2 adjusted 0.906 0.959 0.906 0.954 The adsorption thermodynamics was determined using the
Redlich and Peterson thermodynamic equilibrium coefficients at different tempera-
kR (L/g) 1 0.624 1.0 0.833 tures and concentrations. The adsorption characteristics of a
aR 28 14.818 1.751 97.718 material can be expressed in terms of thermodynamic param-
β 2.911 2.974 0.128 0.346 eters, such as ΔG° (Gibbs free energy change), which can be
R2 0.911 0.953 0.992 0.991 calculated by Eq. (13):
R2 adjusted 0.893 0.945 0.990 0.989
Liu ΔG∘ ¼ RT lnðK d Þ ð13Þ
Kg (L/mg) 1.915·10-6 4.382·10 -6
0.0904 0.0309
qm (mg/g) 380.884 153.664 214.750 300.962 where ΔG° is Gibbs free energy, R is the universal gas con-
nL 0.1880 0.3681 0.9313 0.6238 stant (8,314 J/Kmol), T is the temperature (K), and Kd is the
R2 0.908 0.961 0.990 0.991
thermodynamic equilibrium constant calculated according
R2 adjusted 0.890 0.954 0.988 0.990
Lima et al. (2019).
Gibbs free energy is the difference between the adsorption
enthalpy (ΔH°) and the adsorption entropy (ΔS°) multiplied
by the temperature. Thus, applying this concept to Eq. (13),
activated carbon increases in the composites, there was a de- the parameters ΔH° and ΔS° can be calculated using the
crease in the time required for the experimental qt to exceed Van't Hoff plot (Liu 2009), according to Equation (14):
the qt,expected. This suggests an increase in the adsorption rate,
related to the greater porosity and surface area and less steric
ΔG∘ ¼ ΔH ∘ −T ΔS ∘ ð14Þ
hindrance of composites with a greater amount of activated
carbon. Figure 9 shows the Van't Hoff plot and Table 4 shows the
To evaluate the adsorption mechanism of the composites, thermodynamic parameters of adsorption. In Table 4, the neg-
the Weber and Morris (1963) model was used, according to ative values of ΔG° indicate that the adsorption, at tempera-
Eq. (12): tures above 288 K, occurs spontaneously and favorably. The
decrease in the values of values ΔG° with the increase in
qt ¼ K t  t 1=2 þ C ð12Þ
temperature showed that there was an increase in the driving
force of adsorption, being more favorable in these conditions.
where Kt is intraparticle diffusion rate constant (mg/g½)), t ΔH° negative indicates that the adsorption process is exother-
time (min) and C the intercept of the intraparticle diffusion mic. In addition, the magnitude of ΔH° in the range of −4 kJ/
equation (mg/g). mol and −40 kJ/mol suggests physical adsorption, due to Van
The mass transfer mechanisms in the adsorption were der Waals forces (Piccin et al. 2017b; Crini and Badot 2008).
verified through the graph of Weber and Morris as shown Positive values of ΔS° indicate that the system disorder
in Fig. 7. The model adequately describes the entire range increases with the adsorption of the RBBR dye (Crini and
investigated, which indicates rapid external diffusion Badot 2008). Therefore, this shown that it is the high affinity
through the boundary layer (Crini and Badot 2008). If between the dye molecules and the surface of the adsorbent
the regression is linear and passes through the origin, caused by the driving force of the process (dG) that causes
the rate limiter is intraparticle diffusion (Crini and Badot adsorption. Similar values of ΔG.° and ΔH° were observed by
2008; Moradi et al. 2013). Piccin et al. (2011b) in the adsorption of FD&C Red dye n° 40
 Environ Sci Pollut Res

Fig. 6 Adsorption kinetics of the RBBR dye by chitosan/alginate com- second order kinetic model adjust. Dashed lines represent the expected
posites with different concentrations of activated carbon: AC00 (a), capacity (C0=100 mg/L, 100 rpm, 25°C and pH=2.5)
AC10 (b), AC20 (c) and AC30 (d). Solid lines represents the pseudo-

in chitosan, found as a spontaneous and exothermic process,
but with chemical adsorption being observed, due to greater
interaction forces. In the adsorption of Acid Black 210 and
Table 3 Kinetic parameters of the RBBR dye adsorption by the
chitosan/alginate composite with different activated carbon additions (in
C0=100 mg/L, 100 rpm, 25°C, and pH=2.5)
Acid Red 357 dyes onto activated carbon produced from
leather shavings, similar values of ΔG° and ΔS° was found
to that used in the development of the materials in this work
(Manera et al. 2018). This suggests that the activated carbon
added to the chitosan/alginate composite contributes to the
affinity between the dye and the adsorbent material.

Parameters AC00 AC10 AC20 AC30

Desorption process
Pseudo-first order
K1 0.084266 0.062255 0.011554 0.007068 Figure 10 shows the adsorption and desorption assays of the
qe,1 31.954 49.249 61.089 85.336 AC30 material submitted to 10 cycles in order to verify the
R2 0.991 0.990 0.978 0.984
2
R adjusted 0.990 0.989 0.977 0.983
Pseudo-second order
K2 1.413·10-4 6.424·10-5 1.281·10-4 4.668·10-5
qe,2 45.840 71.995 80.567 120.469
R2 0.992 0.993 0.976 0.989
R2 adjusted 0.992 0.992 0.975 0.989
Elovich
α (g/mg) 0.067708 0.040511 0.040741 0.025790
β (mg/g/min) 0.345 0.369 0.995 0.791
qt (mg/g) 58.46 61.33 91.24 90.79
R2 0.993 0.995 0.972 0.993
R2 adjusted 0.993 0.994 0.970 0.993 Fig. 7 Weber and Morris graph of adsorption of RBBR dye by the
composites developed
Environ Sci Pollut Res
Fig. 8 Effect of temperature on the adsorption capacity of the RBBR dye
by the AC30 composite (pH 2.5)
potential for reuse. The regeneration was carried out with 0.05
mol/L NaOH.
As seen in Fig. 10, after the second cycle, the removal and
regeneration gradually decrease. However, even in the tenth
adsorption cycle, it was observed that the removal of the
RBBR dye was greater than 50% of the first adsorption cycle,
indicating that the adsorbent still had potential for reuse.
Vieira et al. (2018) tested the reuse of glass beads coated with
chitosan for adsorption/desorption of the Tartrazine Yellow
dye. They observed that from the first to the third regenera-
tion, the potential dropped from 92.6 to 82.3%, and the re-
moval of dye from 36.3 to 33.8%, from the first to the fourth
cycle. In this study, the potential for regeneration was 79%
and dropped to 71% in the tenth cycle. The dye removal was
initially 42% and dropped to 26% in the tenth cycle. Rêgo
et al. (2013) evaluating the desorption of Tartrazine and
Amaranth dyes in chitosan films using NaOH and NaCl ob-
served NaOH as being more effective because it breaks the
bonds between the chitosan amine groups and the sulfonated
groups of the dyes. However, the use of NaOH causes the
amine, hydroxyl, and carbonyl groups to be deprotonated
(Kumar and Jiang 2016) cycle after cycle, which explains
the gradual reduction in dye removal even with the mainte-
nance of regeneration. The effluent obtained during regenera-
tion can be treated by conventional methods, such as chemical
precipitation, or oxidative methods, due to the lower volume
and higher concentration of the dye.
Table 4 Thermodynamic parameters of the RBBR dye adsorption by
the AC30 composite
T (K) Kd (g/L) ΔG° (kJ/mol) ΔH° (kJ/mol) ΔS° (kJ/mol)
288 55386.12 −59.082628 −17.8704 0.143098
298 40757.66 −60.513607
308 34157.1 −61.944587
Fig. 9 Van't Hoff plot of RBBR dye adsorption by the AC30 composite
Real textile wastewater treatment
Table 5 presents the characterization results of a real effluent
from a textile industry previously treated by conventional
methods. The effluent was submitted to the treatment by ad-
sorption with 1.2 g/L and the material AC30 for 4 h. The
analyzed parameters were compared to the standard
established in Europe for dyeing and washing as shown by
Vajnhandl and Valh (2014).
Table 5 shows that all the parameters analyzed presented a
reduction in values after treatment with adsorption. There was
also a considerable removal of color and turbidity, and after
adsorption, it complies with Brazil’s drinking standard
(Ordinance No. 2914/2011, from the Ministry of Health).
This indicates that despite the presence of residues from other
additives, such as bleach, softener, anti-migration, sodium hy-
pochlorite, sodium metabisulfite, detergents, and degreaser,
the developed adsorbent was able to remove, even if not en-
tirely, the residual dye. The composites development in this
work do not replace the conventional treatments applied to
industrial effluents but are applied as a complementary treat-
ment to remove polluting effluents that conventional treat-
ments are not able to remove as dyes, pesticides, and drugs.
The wastewater treated by adsorption can be reused in the
Fig. 10 Adsorption and desorption cycles of RBBR dye by composite
AC30 using NaOH 0.05 mol/L
 Environ Sci Pollut Res

Table 5 Real textile wastewater treated by adsorption using 1.2 g/L of the AC30 composite per 4 h (in pH 2.5, 25°C, and 100 rpm)

Parameter Wastewater treated Wastewater treated Removal Water quality for Water quality for
in industry by adsorption efficiency dyeing* washing*

BOD 128.9 91 29.40% 0–20 -

COD 376.6 240.6 36.12% 0–160 200–500
Phosphor 0.41 0.3 26.83% - -
Kjeldahl nitrogen 2.8 2.5 10.71% - -
Total suspended solids 16 10 37.50% 0-50 -
Color 10.5 3.5 66.67% Non visible Non visible
Turbidity 14.2 3.1 78.17% 1
pH 9.77 5.32 - 6.5–8.0 6.5–8.0

*According Vajnhandl and Valh (2014)

textile industry process, as their quality parameters meet the
standard for reuse as wash water.
Kyzas et al. (2011) used chitosan spheres to treat a synthet-
ic textile effluent containing the Remazol Red (197 mg/L),
Remazol Yellow (223 mg/L), and Remazol Blue (280 mg/L)
dyes, observing adsorption capacities up to 1300 mg/g.
However, it is necessary to emphasize that the concentrations
of dyes used in the work of Kyzas et al. (2011) for the man-
ufacture of a synthetic effluent are much higher than those of
an effluent subjected to a conventional pre-treatment, such as
in this work. In addition, when comparing the adsorption ca-
pacities of an aqueous solution and a real effluent, a reduction
was observed. This is due to the competition between the dye
and the other compounds for the active sites (Piccin et al.
2016). Finally, an even smaller capacity would be expected
when submitting the adsorbent to a real effluent previously
treated, as in the case of this work, and therefore, a low ad-
sorption capacity would not be an indication of inefficient
adsorption.
Ahmad and Hameed (2010) verified 3 g/L of a bamboo-
activated carbon in the removal of BOD and color in real
textile effluents, and observed removals of 93.08% for color
and 73.98% for BOD. Therefore, it appears that the material
developed behaves satisfactorily in the advanced treatment of
real effluents from the textile industry, contributing not only in
the reduction of color but also in the reduction of COD, BOD,
nitrogen, and phosphorus.
from chitosan, increasing its exposure, thus decreasing the
steric hindrance.
The chemical characterization of the developed composites
demonstrated the presence of chitosan chemical groups.
However, the addition of activated carbon increased the spe-
cific surface area of the adsorbent, leading to the exposure of a
greater number of chitosan adsorption sites.
The adsorption equilibrium data were correlated to the
Freundlich, Langmuir, and Liu models. The maximum ad-
sorption capacity of the AC30 composite was 300.96 mg/g
according to the Liu model; this value being 1.2 times higher
than expected for the composite. The adsorption thermody-
namics was characterized as spontaneous, favorable, and exo-
thermic. The adsorption kinetics was represented by the
Elovich model.
The AC30 composite was subjected to adsorption and de-
sorption for ten cycles, demonstrating its satisfactory life cy-
cle. In addition, this composite performed satisfactorily in the
post-treatment of textile effluents, reducing 30% BOD5, 39%
COD, 78% turbidity, and 67% color.
Abbreviations ACTW, activated carbon of tannery waste; RBBR,
Remazol Brilliant Blue R; BOD, biochemical oxygen demand; COD,
chemical oxygen demand
Supplementary Information The online version contains supplementary
material available at https://doi.org/10.1007/s11356-021-14150-8.

Conclusions Acknowledgements The authors would like to acknowledge the

In this work, adsorbent composites were developed with char-
acteristics that combine the adsorption capacity of chitosan
with the porosity and surface area of activated carbon. In ad-
dition, the synergistic effect between chitosan, alginate, and
activated carbon in the developed composites caused an in-
crease in the capacity and in the adsorption rate. The syner-
gistic effect occurred due to the removal of chemical groups
Coordination for the Improvement of Higher Education Personnel
(CAPES - Finance Code 001), the National Council for Scientific and
Technological Development (CNPq - Proc.405311/2016–8), and the
Foundation University of Passo Fundo for their financial support in this
research.
Author contribution Flávia Melara: investigation, data curation, writing-
original draft preparation, and writing-reviewing; Thaís Strieder
Machado: writing-original draft preparation; Ingridy Alessandretti: vali-
dation; Christian Manera: investigation; Daniele Perondi: Investigation;
Environ Sci Pollut Res
Marcelo Godinho: writing-original draft preparation and editing; Jeferson
Steffanello Piccin: project administration, supervision, and writing-
reviewing and editing.
Data availability Not applicable.
Declarations
Ethics approval and consent to participate Not applicable.
Consent for publication Not applicable.
Competing interests The authors declare no competing interests.
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