Journal of Cleaner Production 198 (2018) 1302e1310

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Journal of Cleaner Production

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

Biosorption of rhodamine B dye from dyeing stones effluents using the

green microalgae Chlorella pyrenoidosa
Ana Lúcia Denardin da Rosa a, *, Elvis Carissimi a, Guilherme Luiz Dotto b, Hedda Sander c,
Liliana Amaral Feris d
a
Department of Sanitation and Environmental Engineering, Federal University of Santa Maria, UFSM, Roraima Avenue, 1000, 97105-900 Santa Maria, RS,
Brazil
b
Department of Environmental Processes Laboratory, Chemical Engineering, Federal University of Santa Maria, Roraima Avenue, 1000, 97105-900 Santa
Maria, RS, Brazil
c
Department of Supply Engineering: Environmental Engineering, Ostfalia University of Applied Sciences, Salzdahlumer Str. 46/48, 38302, Wolfenbüttel,
Germany
d
Department of Chemical Engineering, Federal University of Rio Grande do Sul, Engenheiro Luis Englert Str, 90040e040, Porto Alegre, RS, Brazil

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

Article history: Rhodamine B has been widely used in dyeing of semiprecious stones (agate), which are exported from
Received 8 February 2018 the Southern Brazil, and in this dyeing process, colored effluents are generated. So, the objective of this
Received in revised form study was the use green microalgae Chlorella pyrenoidosa for the removal of rhodamine B dye from
23 May 2018
dyeing stones effluents. Biosorption was carried out in order to evaluate effects of pH, contact time and
Accepted 12 July 2018
Available online 17 July 2018
temperature. Biosorption kinetics was studied for the dye concentration range of 20e500 mg L
1 using
pseudoefirst order, pseudoesecond order and Elovich models. Equilibrium isotherms were analyzed by
the Langmuir, Freundlich, Sips and Temkin models. Results showed that when the initial dye concen-
Keywords:
Dye removal
tration was 100 mg L
1, the microalgae biomass presented the highest biosorption capacity, at pH 8.0 and
Biosorption temperature of 25  C. The time required to reach the equilibrium was 120 min. The kinetic model that
Dye better fitted the experimental data was pseudoesecond order, with an average relative error lesser than
Rhodamine B 2.4%. The Sips isotherm presented the best performance, being the calculated values of biosorption ca-
Chlorella pyrenoidosa pacities of 63.14; 53.46 and 54.20 mg g
1 for the temperatures of 25, 35 and 45  C respectively,
demonstrating that a temperature increase has a negative effect on the biosorption capacity. Results
indicated that the biosorption using Chlorella pyrenoidosa has a great potential for rhodamine B removal
from dyeing stones effluents.
© 2018 Elsevier Ltd. All rights reserved.

1. Introduction Sul, organic rhodamine B dye is used for dyeing agate, since the
state is the largest producer and exporter of this material world-
Dyes are substances with high potential for application in the wide. To prepare the geode for export, several processing proced-
most diverse areas. These compounds are used to color final ures are used, among them dyeing, which are performed to obtain
products of textile, precious stones, leather, paper, plastics and food different shades of products, making them more attractive to the
industries. It is estimated that there are more than 100,000 syn- market. However, colored effluents are generated, with concen-
thetic dyes on the market, with an annual output of more than trations of dyes ranging from 20 to 500 mg L
1 (Carissimi et al.,
700,000 tons worldwide (AleFawwaz and Abdullah, 2016). 2000).
Rhodamine B (RhB) is a water soluble dye of the xanthene class and It is known that colored effluents are one of the most prob-
is widely used in biological, analytical, optical sciences (Hou et al., lematic ones to be treated, not only because of their high
2011). In Brazil, more specifically in the state of Rio Grande do amounts of chemical and biochemical oxygen demand or
amounts of suspended solids and toxic compounds, but also
because of the color, which is the first parameter to be recog-
nized by human beings, causing aesthetic repugnance. In addi-
* Corresponding author. tion, these dyes can significantly affect photosynthetic activity in
E-mail address: eng.analucia@yahoo.com.br (A.L.D. da Rosa).

https://doi.org/10.1016/j.jclepro.2018.07.128
0959-6526/© 2018 Elsevier Ltd. All rights reserved.
 A.L.D. da Rosa et al. / Journal of Cleaner Production 198 (2018) 1302e1310 1303

aquatic life, reduce light penetration and may also be toxic due to 2.3. Biosorption experiments
the presence of complex aromatic compounds, making their
biodegradation difficult (Aksu and Tezer, 2005). Barros et al. The discontinuous experiments were carried out in triplicates
(2006) and Pizzolato et al. (2002) emphasize that techniques using 250 mL glass beakers with 100 mL of rhodamine B solution, in
such as photochemical degradation, chemical oxidation and which, to maintain stirring uniformity, the DBO BODTRAK II
advanced oxidative treatment processes have already been equipment agitator table was used at a speed of 100 rpm. After the
tested to mitigate the problems caused by agate dyeing. How- biosorption operation, samples were filtered using an AP40 filter,
ever, they have generated byproducts that are as harmful to which did not show iteration with the dye, and the dye concen-
human health as the dyes themselves. tration was determined by a spectrophotometer (V1600 Spectro-
Some authors (Crini, 2006; Gupta and Suhas, 2009; Srinivasan photometer) at a 554 nm wavelength.
and Viraraghavan, 2010; Sharma et al., 2011; Solís et al., 2012) Dye removal percentage (R%) and biosorption capacity of the
point out that adsorption is an acceptable technique for treatment biosorbent (qt) were determined by Eqs. (1) and (2), respectively.
of colored effluents and that several adsorbents have been studied
in order to reduce the process cost, among them residual materials ðC0
Ct Þ
Rð%Þ ¼ 100 (1)
from agriculture and industry such as carbons activated from C0
residues of wood, sawdust, rice husks, fly ash, as well as natural
materials such as clays, zeolites, chitosan, microalgae biomass, ðC0
Ct Þvol
bacteria and fungi. Biosorption, as the adsorption is called when
qt ¼ (2)
m
using biological materials such as microalgae, has presented
excellent results for dye removal (Dogar et al., 2010; Ergene et al., where, C0 is the initial dye concentration (mg L
1); Ct is the dye
2009; Kousha et al., 2014, 2015; Pathak et al., 2015; Tsai and Chen, concentration at time t in (mg L
1); vol represents the solution
2010). Therefore, the main goal of this work was to use the volume (L); m is the mass of biosorbent used (g).
microalgal species Chlorella pyrenoidosa belonging to the Chlor-
ophyta divison as a biosorbent for the removal of rhodamine B 2.3.1. Effect of biosorbent amount
from dyeing stones effluents. The species was used because it is Initially, a test was carried out to evaluate biomass amount ef-
widely cultivated worldwide (Pathak et al., 2015) and has been fect on color removal efficiency and biosorption capacity. Thus the
successfully employed to remove heavy metals (Zhou et al., 2012) amount of microalgae dry biomass ranged from 0.5 to 2.0 g, in the
and food dyes (Hornik et al., 2013; Sinha et al., 2016) from aqueous normal pH of the dye solution (pH 4.5) at room temperature
solutions. (25 ± 2  C) and dye concentration of 100 mg L
1. After 4 h aliquots
were removed to measure the final concentration of the dye
2. Methodology solution.

2.1. Materials 2.3.2. pH effect

The pH evaluated were 2, 4, 6, 8 and 10, using NaOH or HCl
The Chlorella pyrenoidosa powder biomass was produced by (0.5 mol L
1) solutions in a solution of 100 mg L
1 of dye, keeping
Green Gen company, UK; the rhodamine B dye was supplied by the temperature at 25  C where at the end of the 4-h test the dye
MERCK™; the AP40 0.45emm fiberglass filters were produced by concentration was measured by means of previous filtration of the
MiliporeTMand the NaOH and HCl solution used for pH adjustment microalgae.
were from Vetec™.
2.3.3. Contact time e biosorption kinetics
2.2. Characterization Upon obtaining optimum mass (0.1 g) and pH (8), found in
previous studies, tests were carried out to determine the kinetic
The biomass of Chlorella pyrenoidosa was characterized in rela- profile. At room temperature, dye concentration ranged from 20 to
tion to moisture, ashes, protein and lipids, according to standards 500 mg L
1, that are the same range concentrations found in the
by (AOAC, 2005). Moisture and ash content were determined by the effluents of the agate dyeing industries according to Pizzolato et al.
gravimetric method (AOAC 950.46 and AOAC 920.153). Carbohy- (2002). Aliquots were taken at times of 5, 15, 30, 45, 60, 75, 90, 120,
drate content was obtained by difference. Protein percentage was 150, 180 and 240 min.
obtained by the Kjeldhal method using 6.25 (AOAC 928.08) con- The experimental data were fitted to the models of pseudoefirst
version factor. Ethereal extract was quantified, which is a method order (Eq. (3)) (Lagergren, 1898), pseudoesecond order (Eq. (4))
applicable in lipid content determination using the Soxhlet method (Ho and Mckay, 1998) and Elovich (Eq. (5)) (Elovich, 1957) models.
(AOAC 960.39). The point of zero charge was also performed (pHpzc)

according to the methodology presented by Park and Regalbuto qt ¼ q1 1
e
ðk1 tÞ (3)
(1995).
The materials were also analyzed before and after biosorption
t
by Fourier transform infrared spectrometry (FTIR), and the qt ¼ 1
(4)
morphology was verified by scanning electron microscopy (SEM). k2 q22
þ qt2
FTIR analyzes were (Shimadzu, IR Prestige 21) in the range of
450e4000 cm
1 to identify the surface functional groups. SEM was 1
carried out with an electron microscope (VEGA 3, Tescan), in which qt ¼ lnð1 þ abtÞ (5)
a
the samples were metalized with gold and used voltage accelera-
tion of 5 kV and magnification range from 250 to 1000 times when where q1 and q2are the theoretical values of the biosorption ca-
using secondary electron detector (SE). In order to determine the pacity (mg g
1) determined by the models of pseudoefirst and
elemental composition on the biosorbent surface, Xeray energy pseudoesecond orders, respectively; k1 is the biosorption rate
dispersion detector (EDXeOxford) was used. All the analyses were constant (min
1) of pseudoefirst order; k2 is the rate constant (g
carried out in triplicates. mg
1min
1) of pseudoesecond order; b the initial biosorption rate
1304 A.L.D. da Rosa et al. / Journal of Cleaner Production 198 (2018) 1302e1310

(mg g
1min
1) and a the desorption constant of the Elovich model 3. Results and discussion
(g mg
1).
3.1. Microalgae characterization
2.3.4. Biosorption isotherms
Using the same optimum values of mass and pH, at tempera- The microalgae biomass composition is shown in Table 1. The
tures of 25, 35 and 45  C, the aliquots were sampled for determi- composition obtained for the Chlorella pyrenoidosa biomass
nation of isotherms after 4 h of test at initial dye concentrations of (Table 1) was similar to the one obtained by (Um and Kim, 2009) in
20, 100, 200, 300, 400 and 500 mg L
1. With the experimental data which the dry biomass consisted on average of 57% of proteins, 26%
obtained, the Langmuir (Eq. (6)) (Langmuir, 1918), Freundlich (Eq. of carbohydrates and 2% of lipids. The biomass is composed mainly
(7)) (Freundlich, 1906), Sips (Eq. (8)) (Sips, 1948) and Temkin (Eq. by proteins and carbohydrates. The biomolecules contains a series
(9)) (Piccin et al., 2011) models were adjusted which are frequently of functional groups that can be potential binding sites for the
used in modeling dye removal when using biosorbents (Crini and rhodamine B dye.
Badot, 2008; Ergene et al., 2009; Foo and Hameed, 2010; Saeed The FTeIR spectra of biomass before and after dye biosorption
et al., 2010; Sinha et al., 2016). are shown in Fig. 1. Both show a similar pattern, in which no abrupt
changes or new bands were observed after dye biosorption. It
qm kL Ce suggests little likelihood of any biodegradation of the dye during
qe ¼ (6) the biosorption process, also indicating that the interaction of the
1 þ kL Ce
dye with the biosorbent is physical and presented low energy.
However some changes in some peaks were observed, the broad
qe ¼ kF Cen
1
(7) peak at 3410.29 shifting to 3425.72 cm
1, suggests overlap of OeH
and NeH stretching vibrations, indicating the presence hydroxyl
groups (Mona et al., 2011a; Wang et al., 2017). The bands of 2960.17
qms ðks Ce ÞmT and 2927.10 cm
1 were intensified after biosorption, indicating a
qe ¼ (8)
1 þ ðks Ce ÞmT stretching of the methylene (eCH2) and methyl (eCH3) groups. A
C]O stretching of amines was observed in 1724.44 to
RT 1643.42 cm
1. At 1547.94 to 1454.39 cm
1 were attributed to C]C
qe ¼ lnðkT Ce Þ (9) stretching of aromatic rings (Cardoso et al., 2012; Dotto et al., 2012).
b
The bands 1401.00 to 1245.10 cm
1 were assigned to the aromatic
where qe represents the amount of dye adsorbed (mg g
1); qm the ethers CeO stretching, and the bands observed at 1079.22 to
maximum biosorption capacity in the monolayer (mg g
1); qmS the 1057.04 cm
1 represented the PeO stretching (Daneshvar et al.,
maximum biosorption capacity of Sips (mg g
1); kL the Langmuir 2017; Li et al., 2015; Marzbali et al., 2017). In addition it can be
constant (L mg
1); kF the Freundlich constant (mg g
1) (L mg
1)1/ seen that the transmittance values were lower for the algae when
n
); kS the Sips constant (L mg
1); kT the equilibrium constant cor- there was no presence of the dye, consequently, more energy was
responding to the maximum binding energy (L mg
1); Ce repre- required to generate the bands, this confirms that microalgae prior
sents the equilibrium concentration (mg L
1); when n presumes to biosorption had more available sites for dye binding. This
values higher than 1, it represents favorable biosorption conditions, composition shows the potential of using microalgae as a bio-
mT the fractional exponent related to the biosorption mechanism, R sorbent, since they contain many functional groups such as amino,
the universal gas constant (8.31  10
3 kJ K
1mol
1); T the tem- carboxyl, hydroxyl, sulfates, phosphates that shall associate with
perature (K) and b the biosorption heat. dyes (Aksu and Tezer, 2005; Ergene et al., 2009; Mona et al., 2011b).
As shown in Fig. 2 (a, b and c), the microalgae are of the cocoid
type, a typical form of Chlorella (Tsai and Chen, 2010), with different
2.4. Adjustment of kinetic and isotherm models
particle sizes, thus being unformed, presenting a rigid and homo-
geneous morphological structure, besides a rough and irregular
The kinetic and isotherms parameters were determined by
surface with the presence of some grooves and protuberances. The
nonlinear regression using the Statistic 10.0 software, in which
SEM images after biosorption are shown in Fig. 2 (d, e and f). The
adjustment quality was measured according to the coefficient of
microalgae were grouped into large agglomerates; however, it was
determination (R2) (Eq. (10)), adjusted coefficient of determination
clear that there was a persistence of the cocoid form and integrity of
(R2adj) (Eq. (11)) and average relative error (ARE) (Eq. (12)).
the cell walls.
P
2 P
2 The elemental composition of the microalgae has been exam-
qexp
qexp
qexp
qcal ined by SEMeEDX analysis in which it was possible to verify ele-
2
R ¼ (10)
P
2 ments present on the surface. The microalga was composed by
qexp
qexp carbon 67.77%, oxygen 30.48%, phosphorus 0.69%, potassium 0.36%
and sulfur 0.28%. Magnesium, calcium, iron and copper present in

N
1 the analysis were less than 0.15% each. This composition of Chlor-
R2adj ¼ 1
1
R2 (11) ella is similar to those found other studies of (Shen et al., 2013;
N
P
 
100 Xqexp
qcal  Table 1
ARE ¼   (12) Composition of Chlorella pyrenoidosa powder biomass.
N  qexp 
Composition Average values (%) Standard deviation

Moisture 3.758 0.0372

where qexp are the experimental data (mg g
1); qexp is the mean of Ash 6.274 0.0263
the experimental data (mg g
1); qcal are values predicted by the Protein 58.463 0.3278
models (mg g
1); N is the sample size and P is the number of the Ethereal extract 0.694 0.0850
Carbohydrates 29.837 0.3536
model parameters.
 A.L.D. da Rosa et al. / Journal of Cleaner Production 198 (2018) 1302e1310 1305

valueseinitial pH is presented in relation to initial pH of the bio-

sorbent suspension. As shown in Fig. 3, point of zero charge (pHpzc)
of the microalga was 6.94 (±0.03), which is consistent with the
study of Hornik et al. (2013), who found pHpzc of 6.79 for Chlorella
pyrenoidosa. Thus, it can be stated that at pH values lower than 6.94,
the microalgae are positively charged, whereas at pH values higher
than 6.94 the adsorbent has a negative surface charge (Hao et al.,
2004).

3.2. Effect of biosorbent amount

Fig. 1. FTIR spectra of the microalgae before and after biosorption. Fig. 4 shows the biosorbent amount effect on the biosorption of
rhodamine B in the dye initial concentration of 100 mg L
1, tem-
perature 25 ± 2  C, solution pH of 4.5, 100 rpm and contact time of
Singhal et al., 2013). The elemental composition is in agreement 4 h. It was possible to verify that the biosorbent amount increase
with the composition presented in Table 1. caused a decrease in biosorption capacity from around 20.0 to
The point of zero charge is important information to understand 3.6 mg g
1. This occurred because some biosorption sites can be
the biosorption mechanism, since it is possible to verify the bio- overlapped, decreasing the amount biosorbed per unit of mass. The
sorbent samples surface charges. In Fig. 3, the final pH removal percentage in turn increased with the biosorbent dosage,

(a) (b) (c)

(d) (e) (f)

Fig. 2. SEM images of the microalgae: (a) before biosorption and magnification 250; (b) before biosorption and magnification 500; (c) before biosorption and magnification
1000; (d) after biosorption and magnification 250; (e) after biosorption and magnification 500; (f) after biosorption and magnification 1000.
1306 A.L.D. da Rosa et al. / Journal of Cleaner Production 198 (2018) 1302e1310

2 50

1
40
Final pH - Initial pH

0
30

qe (mg.g-1)
-1
20
-2

10
-3

-4 0
1 2 3 4 5 6 7 8 9 10 11 12 2 4 6 8 10 12
Initial pH pH

Fig. 3. Point of zero charge of the microalgae (n ¼ 3 repetitions). Conditions: Tem- Fig. 5. Effect of pH of the dye solution on the biosorption of rhodamine B dye (n ¼ 3
perature 25  C; adsorbent mass 0.25 g; agitation 100 rpm; time 24 h. repetitions). Conditions: Temperature 25  C; adsorbent mass 0.1 g; agitation 100 rpm;
time 4 h.

attaining 89.0%. Thus, it was chosen to use the mass of 0.1 g of dye and there is a decrease in the amount biosorbed. The presence
microalgae for the next tests, since provides high biosorption of excess ions Hþ in pH lower than pHpzc can decrease the car-
capacity. boxylic group ionization by decreasing the biosorption capacity of
rhodamine B. On the other hand, when the solution pH is increased,
the surface becomes negatively charged due to OH
biosorption
3.3. Influence of pH and biosorption mechanism and there is deprotonation, thus improving biosorption by elec-
trostatic attraction (Ahmad and Kumar, 2010). However, according
Fig. 5 shows the pH effect on the biosorption of rhodamine B at to Lacerda et al. (2015), biosorption reduction when the solution pH
the initial concentration of 100 mg L
1, using 0.1 g of the biosorbent was higher than 8 may be due to formation of hydrated ions of
under temperature conditions of 25 ± 2  C and 4 h. It was observed rhodamine B, which leads to a larger molecular structure (dimer)
that, when the pH increased from 2 to 8, an increase in the dye that hinders dye entry into the biosorbent pores. This same
biosorption capacity from 9.41 to 26.29 mg g
1 occurred. A new behavior was reported by (Fernandez et al., 2014), who studied the
increase from 8 to 10 led to a decrease in biosorption capacity. removal of rhodamine B dye by activated carbons developed from
Evidently, the best values were found at pH of 8. The biosorption orange peels, and in a study by (Santhi et al., 2011) who analyzed
behavior shown in Fig. 5 can be explained by the point of zero the removal of the same dye, but using activated carbon produced
charge of the biosorbent as well as by the molecular nature of the by the leaves of Acacia nilotica. Based on these results, pH 8 was
rhodamine B dye. Thus, when the dye solution pH is lower than the chosen for the development of the other tests.
biosorbent pHpzc, i.e., less than 6.94, the biosorbent surface is
positively charged. Therefore, the rhodamine B biosorption, which
is a cationic dye, tended to be smaller due to the repulsive forces 3.4. Influence of time and dye concentration e biosorption kinetics
between the biosorbent surface and the cationic molecule. In
addition, at low pH values, the Hþ ions compete with the cationic Biosorption is a time dependent operation. Therefore, by means
of a kinetic model it is possible to know the mass transfer resistance
110 110 in the biosorbent particle, describing the speed with which the dye
molecules are biosorbed. In addition, from these models it is
100 100
possible obtain information about factors that affect these reactions
90 90 (Ho and Mckay, 1998). Thus, biosorption kinetics was analyzed by
80 80 using the pseudoefirst and pseudoesecond orders models and
70 70 Elovich. In Fig. 6 the models studied and the experimental data are
qe (mg.g-1)

plotted.
60 60
R (%)

Results on Fig. 6 show that the initial dye concentration is an

50 50 important factor in the biosorption operation. The increase in initial
40 40 dye concentration led to an increase in biosorption capacity. This is
30 30 due to the fact that the increase of the initial dye concentration
20 20 increases the likelihood of contact between dye molecules and the
biosorbent (Yagub et al., 2014). In addition, it was observed that for
10 10
all concentrations studied, biosorption was a fast operation. It was
0 0 verified that 82e95% of saturation was attained within the first
0,1 0,3 0,5 1,0 1,5 2,0
30 min. After 30 min, the biosorption rate gradually decreases until
Mass (g) reaching equilibrium. This fact can be explained because, initially,
qe (mg.g-1) R (%) all active sites on the biosorbent surface are free, resulting in a fast
Fig. 4. Effect of microalgae biosorbent mass on the biosorption of rhodamine B dye
biosorption. As they are being occupied by rhodamine B, free sites
(n ¼ 3 repetitions). Conditions: Temperature 25  C; pH normal of the dye solution; tend to decrease, leading to the process equilibrium point. It was
agitation 100 rpm; time 4 h. also possible to identify in Fig. 6 that equilibrium was reached at
 A.L.D. da Rosa et al. / Journal of Cleaner Production 198 (2018) 1302e1310 1307

60 70

50 60

40 50
qt (mg.g-1 )

qe(mg.g-1 )
30 40

20 30
10 20
0 10
5 15 30 45 60 75 90 120 150 180 240
Time (min) 0
-1 -1 0 50 100 150 200 250 300 350 400 450 500
20 mg.L 100 mg.L 200 mg.L-1 300 mg.L-1 400 mg.L-1
-1)
500 mg.L-1 Ce (mg.L
__ 25 °C 35°C 45 °C
Pseudo-first order -- Pseudo second order .... Elovich
Fig. 6. Biosorption kinetics (n ¼ 3 repetitions). Conditions: Temperature 25  C; Fig. 7. Biosorption equilibrium isotherms (n ¼ 3 repetitions). Conditions: adsorbent
adsorbent mass 0.1 g; pH of 8; agitation 100 rpm; time 4 h. mass 0.1 g; pH of 8; agitation 100 rpm; time 4 h.

Table 2
minutes of the biosorption process (Ho and Mckay, 2000). In gen-
Analysis of variance (ANOVA) applied for the biosorption capacities at times of
120 min, 150 min and 180 min for all studied concentrations. eral, this model does not satisfactorily describe the biosorption
kinetics of rhodamine B dye as shown by authors (Khamparia and
Initial dye concentration (mg L
1) ANOVA pevalue
Jaspal, 2016; Lacerda et al., 2015; Wang et al., 2017). The model
20 0.772 that best simulated the biosorption kinetics was the
100 0.051
pseudoesecond order model, since the values of R2 and R2adj were
200 0.708
300 0.912 above 0.98 in all concentrations studied and the ARE values were
400 0.807 below 2.4%. In addition, the equilibrium biosorption capacity
500 0.553 calculated by the pseudoesecond order model for concentrations
of 20, 100, 200, 300, 400 and 500 mg L
1 were 7.52, 25.54, 36.62,
48.07, 51.94 and 55.89. These values were very close with the
120 min of the test for all concentrations, when applying the experimental data (qexp), confirming the good fit of this model. The
ANOVA test with a significance level of 5% for three consecutive q2 values increased with the initial rhodamine concentration,
times, 120 min, 150 min and 180 min, and no difference was found, confirming that the biosorption capacity is favored at higher dye
as shown in Table 2. concentrations. The h values presented the same trend, indicating
Table 3 shows the kinetic parameter values for each model, that at the initial stages, biosorption was faster at higher dye
coefficient of determination (R2) values, adjusted coefficient of concentrations.
determination (R2adj) and average relative errors (ARE) values for all
concentrations studied. Comparing with all the models tested, the 3.5. Biosorption isotherm
pseudoefirst order was the one that obtained the lowest values of
R2 and R2adj and the highest values for ARE (%). This result was By plotting the concentration in solid phase (qe, mg g
1) against
already expected, since the model typically only fits the initial the concentration of the liquid phase (Ce, mg L
1) under the

Table 3
Kinetic parameters for the biosorption of rhodamine B dye on the microalga (pH ¼ 8; temperature 25  C; adsorbent mass 0.1 g; agitation 100 rpm).

C0 (mg L
1) 20 100 200 300 400 500

qexp (mg g
1) 7.59 26.79 37.02 48.89 52.02 57.79
Pseudoefirst order
k1 (min
1) 0.284 0.284 0.227 0.182 0.254 0.448
q1 (mg g
1) 7.38 24.75 35.24 45.00 50.14 55.00
R2 0.9964 0.9799 0.9844 0.9624 0.9835 0.9862
R2adj 0.9956 0.9754 0.9809 0.9540 0.9799 0.9832
ARE (%) 1.12 3.12 2.92 5.03 3.06 2.73
Pseudoesecond order
k2 (g.mg
1 min
1) 0.125 0.022 0.011 0.005 0.009 0.023
q2 (mg g
1) 7.52 25.54 36.62 48.07 51.94 55.89
h (mg g
1 min
1) 7.07 14.06 14.91 11.53 24.42 72.21
R2 0.9995 0.9935 0.9922 0.9906 0.9971 0.9925
R2adj 0.9993 0.9921 0.9904 0.9885 0.9965 0.9908
ARE (%) 0.44 1.70 1.99 2.31 1.26 0.49
Elovich
a (mg g
1 min
1) 3.37 0.58 0.35 0.21 0.27 0.45
b (g mg
1) 2.17108 3.77104 7.34103 6.65102 3.47104 1.71109
R2 0.9940 0.9963 0.9826 0.9931 0.9919 0.9989
R2adj 0.9927 0.9955 0.9787 0.9916 0.9901 0.9987
ARE (%) 1.74 1.40 2.66 2.27 2.16 0.70
1308 A.L.D. da Rosa et al. / Journal of Cleaner Production 198 (2018) 1302e1310

Table 4 Fig. 7 shows the equilibrium isotherms for the considered bio-
Equilibrium parameters for the biosorption of rhodamine B dye on the microalga sorption system, at temperatures of 25, 35 and 45  C. Table 4 shows
(pH ¼ 8; biosorbent mass 0.1 g; agitation 100 rpm).
the values of the isotherm parameters and of the statistical ana-
Temperature 25  C 35  C 45  C lyzes. Observing the shape of the isotherms obtained with the
Langmuir experimental data of Fig. 7 and according to Bl
azquez et al. (2010),
qm (mg g
1) 74.83 55.02 50.78 these are associated to formation of a monomolecular layer on the
kL (L mg
1) 0.0070 0.0110 0.0104 biosorbent surface. In addition, they indicate that the biosorption
R2 0.9905 0.9984 0.9947
operation is favorable, that is, it is possible to obtain a relatively
R2adj 0.9841 0.9973 0.9912
ARE (%) 6.78 1.59 3.17 high biosorption capacity, even under conditions of low dye con-
Freundlich centration in the solution. It is also concluded that the most suitable
kF ((mg g
1) (L mg
1)1/n) 3.35 4.14 3.63 temperature for biosorption of rhodamine B is 25  C, since the
n 2.12 2.48 2.44
biosorption capacity decreased with increasing temperature. Such
R2 0.9836 0.9497 0.9658
R2adj 0.9727 0.9161 0.9431
behavior may be related both to changes in the dye and those in the
ARE (%) 10.32 17.13 14.04 biosorbent due to increase in temperature. Authors (Crini and
Sips Badot, 2008; Feng et al., 2013; Salleh et al., 2011) explain that,
qms (mg g
1) 63.13 53.46 54.19 with increasing temperature, dye solubility also increases, and thus
kS (L mg
1) 0.0122 0.0117 0.0089
the interaction forces between the water and the dye become
mT 1.08 1.05 0.90
R2 0.9692 0.9986 0.9956 stronger than the forces between the dye and the biosorbent and
R2adj 0.9230 0.9966 0.9890 consequently it is more difficult for the dye to be adsorbed. Another
ARE (%) 6.39 1.35 2.97 explanation is the fact that temperatures above 35  C can damage
Tenkim the microalgae cell wall, thus affecting the biosorption sites and
kT (L mg
1) 0.1167 0.1330 0.1351
B 0.1775 0.2264 0.2579
consequently reducing biosorption capacity, (Aksu and Tezer, 2005;
R2 0.9754 0.9942 0.9947 Cardoso et al., 2012; Dotto et al., 2012). Another observation, which
R2adj 0.9590 0.9903 0.9912 can be carried out with the inverse relationship between the
ARE (%) 10.62 2.91 3.33 microalgae biosorption capacity and the increase in temperature, is
that this is indicative of the exothermic nature of the rhodamine B
biosorption operation by microalgae. Other authors (Aravindhan
equilibrium conditions, graphically it is possible to describe equi- et al., 2007; Guler et al., 2016; Ozer and Turabik, 2005) have also
librium biosorption isotherms, which are fundamentally important observed this behavior in removal of dyes using green and blue
in the design of the sorption system. There are many models that microalgae.
are used to analyze experimental biosorption data at equilibrium Among the isotherms models adjusted, it was possible to verify,
and these models equation parameters generally suggest the bio- from Table 4, that the Sips model was the best fit to the experi-
sorption mechanics and biosorbent surface properties (Cardoso mental data, since it presented values of R2 higher than 0.96 and the
et al., 2011). lowest values of ARE for all temperatures tested. Other authors,

Table 5
Comparison between the Chlorella pyrenoidosa and other materials used for the removal of rhodamine B dye from aqueous solutions.

Adsorbent/biosorbent pH T ( C) qmax (mg g
1)a Reference

Chlorella pyrenoidosa 8.0 25 63.14 This work

Beta zeolites (SiO2/Al2O3) 3.0 22 27.97 Cheng et al. (2018)
Activated carbon 5.0 e 162.4 Tuzen et al. (2018)
Activated carbon/Fe 5.0 e 225.2 Tuzen et al. (2018)
Activated carbon/Fe/Ce 5.0 e 324.6 Tuzen et al. (2018)
Xanthium strumarium L. seed 2.0 50 10.39 Khamparia and Jaspal (2017)
Earth worm manure derived biochare400 e e 14.79 Wang et al. (2017)
Earthworm manure derived Biochar
500 e e 17.39 Wang et al. (2017)
Earthworm manure derived Biochar 600 e e 21.60 Wang et al. (2017)
Argemone mexicana seed 3.0 50 17.29 Khamparia and Jaspal (2016)
Activated carbon (CarnaubaeH3PO4) 7.0 45 35.99 Lacerda et al. (2015)
Activated carbon (Carnaubae CaCl2) 7.0 45 39.98 Lacerda et al. (2015)
Activated carbon (MacaubaeH3PO4) 7.0 45 33.69 Lacerda et al. (2015)
Activated carbon (MacaubaeCaCl2) 7.0 45 34.22 Lacerda et al. (2015)
Activated carbon (Pine nut shelleH3PO4) 7.0 45 33.08 Lacerda et al. (2015)
Activated carbon (Pine nut shelle CaCl2) 7.0 45 33.97 Lacerda et al. (2015)
Kaolinite 6.9 30 21.65 Bhattacharyya et al. (2014)
Kaolinite (0.25 M H2SO4) 6.9 30 23.15 Bhattacharyya et al. (2014)
Kaolinite (0.50 M H2SO4) 6.9 30 23.70 Bhattacharyya et al. (2014)
Montmorillonite 6.9 30 181.81 Bhattacharyya et al. (2014)
Montmorillonite (0.25 M H2SO4) 6.9 30 185.18 Bhattacharyya et al. (2014)
Montmorillonite (0.25 M H2SO4) 6.9 30 188.67 Bhattacharyya et al. (2014)

tica (Microwave treated)
Acacia nilo 7.0 27 24.39 Santhi et al. (2014)

tica (Chemicallyetreated)
Acacia nilo 7.0 27 22.37 Santhi et al. (2014)
Milled sugarcane bagasse e e 51.50 Zhang et al. (2013)
Kaolinite 7.0 30 46.08 Khan et al. (2012)
Ironepillared bentonite 5.0 25 98.62 Hou et al. (2011)
Fly ash e e 10.00 Chang et al. (2009)
Rice husk 2.1 60 42.05 Jain et al. (2007)
Activated carbon (Industrial solid) 5.7 30 16.12 Kadirvelu et al. (2005)
a
Maximum adsorption capacity.
 A.L.D. da Rosa et al. / Journal of Cleaner Production 198 (2018) 1302e1310 1309

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