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Journal of Environmental Management 204 (2017) 23e30

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Journal of Environmental Management


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Research article

Wood (Bagassa guianensis Aubl) and green coconut mesocarp (cocos


nucifera) residues as textile dye removers (Remazol Red and Remazol
Brilliant Violet)
Mo^ nica S. Monteiro a, Robson F. de Farias b, Jose
 Alberto Pestana Chaves a,
Sirlane A. Santana , Hildo A.S. Silva , Cícero W.B. Bezerra a, *
a a

a
Departamento de Química, Universidade Federal do Maranha ~o, Av. dos Portugueses s/n, 65080-040 Sa
~o Luis, MA, Brazil
b
Universidade Federal do Rio Grande do Norte, Cx. Postal 1664, 59078-970 Natal, RN, Brazil

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

Article history: In this work the efficiency of two lignocellulosic waste materials, wood residues and coconut mesocarp,
Received 7 March 2017 were investigated as adsorbents towards two representative textile dyes (Remazol Red, RR and Remazol
Received in revised form Brilliant Violet, RBV). The moisture, carbohydrate, protein, lipid, ash and fiber contents of both natural
17 August 2017
matrices were characterized. The materials were also characterized by infrared spectroscopy, X-ray
Accepted 22 August 2017
diffractometry, scanning electron microscopy, specific surface area analysis and thermogravimetry. The
Available online 29 August 2017
adsorption of dyes was monitored by using UVeVis spectrophotometry. It was verified that both, coconut
mesocarp (CM) and wood residues can act as effective adsorbents towards the investigated dyes. It is
Keywords:
Adsorption
verified that the maximum adsorption capacity GM (mg g1) for RBV and RR are 7.28 and 3.97 towards
Agricultural waste CM and 0.64 and 0.71 towrads SD. Furthermore, it was verified that the adsorption is strongly pH
Textile dyes dependent and, as a general behavior, an increase in the pH value is associated with a decrease of the
total amount of adsorbed dye. The adsorption of violet dye onto coconut mesocarp is well described by
the Langmuir model, while all the remazol red fitted better with the Freundlich equation.
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction colorants in the effluent and loss of resources by the industry. More
than 10 thousand kinds of dyes are used annually by industries,
The environmental impacts caused by industrial effluents, equivalent to about 700,000 tons/year (Kharat, 2015; Dallago et al.,
agricultural and urban solid waste discharges in water bodies and 2005). In Brazil, this figure is about 26,500 tons/year (Dallago et al.,
open dumpsters have worsened in recent years, drawing the 2005). In water bodies, the vast majority of dyes remain stable, with
attention of all segments of society (Pinto et al., 2016; Bharathi and negative effects on the photosynthetic activity and the amount of
Ramesh, 2013). In this connection, several research have been oxygen available, due to reduced penetration of sunlight, besides
conducted, dealing with the production of water filters (Btatkeu-K. making the water unsuitable due to the natural toxicity of these
et al., 2016). compounds (Silva, 2014; Dallago et al., 2005; Zanoni and Carneiro,
It is estimated that only in Brazil every year are discharged up to 2001).
7 million tons of coconut shell (Silva, 2014). Without a reuse or Among the several techniques available for industrial effluents
proper disposal, this stuff becomes a serious environmental treatment or the recovery of impacted areas, adsorption stands out
obstacle just by its simple but alarming accumulation. Many other for its simplicity, low cost, efficiency and practicality. In general, the
lignocellulosic wastes, such as rice husk and sawdust, have the adsorbent can be reused and the adsorbed materials can be
same polluting potential. recovered and reused (Santos et al., 2008).
On the other hand, textiles are characterized by low efficiency in It was shown (Kabir et al., 2014) that chitosan can be an excellent
the fibers' fixing and dyeing process, leading to high charge of substrate to the adsorption of Remazol Red, RR. However, chitosan is
a relatively expensive compound, making it unsuitable in large
amount (thousands of tons) for industrial wastewater treatment.
* Corresponding author. As another example of expensive and non-large scale applicable
E-mail address: cwb.bezerra@ufma.br (C.W.B. Bezerra).

http://dx.doi.org/10.1016/j.jenvman.2017.08.033
0301-4797/© 2017 Elsevier Ltd. All rights reserved.
24 M.S. Monteiro et al. / Journal of Environmental Management 204 (2017) 23e30

matrix, it was investigated the removal of Remazol Red dye by HMS at a heating rate of 10  C min1, under argon inert atmosphere. For
ordered mesoporous silica, aminopropyl modified HMS (HMSNH) the analyzes, masses of 10.0 mg of material were used.
and bcyclodextrin modified HMS (HMSCD) materials (Asouhidou The vibrational spectra in the infrared region were obtained
et al., 2009). using a Bomem-Hartmann & Braun spectrometer, model MB-series,
On the other hand, the search for cheap matrix to adsorb (cap- with the Fourier transform at 400-4000 cm1 spectral range, in KBr
ture) dyes is a promising field, with works dedicated to the study of tablet with 4 cm1 resolution.
matrices such as activated carbon obtained from seed of various The X-ray analyzes were performed in a Shimadzu X-ray
plants (Hameed et al., 2017), waste materials of Daucus carota plant diffractometer, model XRD-7000 using 40 kV and 30 mA, with
(Kushwaha et al., 2014) and Cucumis sativus (Smitha et al., 2017), as CuKa radiation source (1.5406 Å), at 2q ranging from 5 to 50 .
recent examples. Scanning Electron Microscopy (SEM) was used for materials
In this context, the main objective of this study was to establish morphological analysis. Samples were conveniently deposited on
the adsorption capacity of two abundant (and cheap or even free of carbon ribbons and next analyzed in a JEOL Scanning Electron
charges) lignocellulosic residues that require a better use or final Microscope, model JSD-6360 LS.
disposal: coconut (cocos nucifera) mesocarp (CM) and wood resi- The pHzpc values were estimated by direct measurement of the
dues (sawdust, SD, from Bagassa guianensis Aubl). Due to the pH standard solutions (1e12, HCl/0.10 mol L1 KCl and NaOH/
severity and the polluting potential of the textile dyes (Carr, 1995), 0.10 mol L1 KCl), before and after contact with the solids (Vieira
two representative members of this class of compounds, Remazol et al., 2009).
Red (Remazol Red 5R, C27H22ClN7Na4O16S5) and Remazol Brilliant The Remazol Brilliant Violet (RBV) and Remazol Red (RR) dyes
Violet (Remazol Brilliant Violet 5R, C20H16N2Na3O15S4), were used (Guaratini and Zanoni, 2000; Pelosi et al., 2014) were initially
as adsorbate. These two dyes were chose taking into account their characterized by UVeVis spectrophotometry, under various pH
large use in Brazilian textile industry and so, their potentiality as an conditions. Analytical curves were constructed for all pH values of
environmental threat. interest and checked their linearity, as predicted by the Lambert-
Beer equation (0,9996  R2  1,0000).
2. Materials and methods

2.1. Collection and preparation of adsorbents 2.4. Adsorption studies

The lignocellulosic of interest in this study, green coconut (cocos The sorption experiments (contact times, kinetic and equilib-
nucifera) mesocarp (CM) and sawdust (SD), were collected in local rium) were conducted by the batch technique, under orbital
trade, as residuals. The employed SD were from “Tabajara” three agitation of flaks containing a fixed mass of the sorbents (100.0 mg
(Bagassa guianensis Aubl). “Tabajara” is a wood three largely for CM and 200.0 mg for SD) in 10.0 mL of dyes solution. After the
employed in the Amazonic region (d ¼ 0.75e0.85 gcm3). sorption process, the suspensions were centrifuged and the dye
The mesocarp was manually separated from the epicarp and concentration in the supernatant was determined by Spectropho-
endocarp, air dried, grounded and sieved so that the particle size tometry in the Uvevis. All tests were made at a temperature of
ranged from 0.088 to 0.177 mm. The sawdust was also milled and 298 K, and under defined pH conditions. The contact time varied
sieved in the same metric. Both were washed in deionized water from 5 min to 1440 min.
until reaching constant conductivity, and oven dried at 50  C. In order to verify the pH effect on the sorption process, exper-
iments were performed using dye solutions ([RR] ¼ 64 mg L1
2.2. Reagents and solutions (0.0648 mmolL), [RBV] ¼ 80 mg L1 (0.1088 mmolL1) at pH from
1.0 to 6.0, prepared with HCl or NaOH, in 0.10 mol L1 KCl. The
All reagents used were of analytical grade (Merck and Aldrich). different concentrations were chose taken into account the
The dyes (Dye Star) were kindly provided by Sa ~o Carlos Towel In- different solubilities of the investigated dyes.
~o Carlos/SP/Brazil. The purity of the dyes is unknown,
dustries SA, Sa The dye solution was in contact with the sorbent under constant
but the literature suggests around 50% m/m (Cestari et al., 2009). stirring for 1440 min, and then the suspension was centrifuged and
All solutions were prepared using deionized water and all the the supernatant was separated to determine the amount of residual
buffers were prepared according to the literature (Vieira et al., 2009) dye concentration.
and employed in the pH studies. The stock solutions of the dyes were The isotherms were obtained similarly, but varying the con-
prepared in pre-determined pH at concentration of 150.0 mg L1. centration of the dyes from 20 to 200 mg L1 at pH 2.0 and the
Further dilutions enabled the kinetics and equilibrium studies. sorption equilibrium time.
The experimental data were fitted to kinetic models of pseudo
2.3. Materials characterization first order (Eq. (1)) and second order (Eq. (2)), as well as the
isothermal models of Langmuir (Eqs. (3a) and (3b)) and Freundlich
The physicochemical analyzes (moisture, carbohydrate, protein, (Eqs. (4a) and (4b)), as expressed by the following equations
lipid, ash and fiber) of the adsorbents (CM and SD) were performed (Holanda et al., 2015):
according to official standards of the Adolfo Lutz Instituto Adolfo
k1
Lutz (2008). logðGe  Gt Þ ¼ log Ge  t (1)
Microanalyses; i.e, the determination of carbon, hydrogen and 2; 303
nitrogen contained in the studied solids, were performed in a
Perkin Elmer equipment, Model 2400. t 1 1
¼ þ :t (2)
Surface area, volume and pore diameter of the materials were Gt k2 :G2e Ge
calculated from the nitrogen adsorption isotherm at 77 K obtained
using the Micromeritics ASAP 2010 instrument. Gmax :Kads :Ce
The thermogravimetric curves were obtained using a thermog- Ge ¼ (3a)
1 þ Kads :Ce
ravimetric apparatus from TG Instruments, model Hi-Res TGA 2950.
The temperature range explored was 25  C (298 K) at 967  C (1240 K)
M.S. Monteiro et al. / Journal of Environmental Management 204 (2017) 23e30 25

Table 2
Ce 1 Ce CNH percentages for the coconut mesocarp (CM) and sawdust (SD).
¼ þ (3b)
Ge Gmax :Kads Gmax CM (%) SD (%)

Value Average Value Average


Ge ¼ Kf $Ce1=n (4a) Carbon 43.62 43.73 ± 0.16 47.14 47.28 ± 20
43.85 47.42
Nitrogen 0.65 0.56 ± 0.12 0.31 0.32 ± 0.21
1
logGe ¼ logKf þ logGe (4b) 0.48 0.34
n Hydrogen 5.70 5.77 ± 0.11 6.47 6.32 ± 0.20
In these equations Ge, Gt and Gmax (mg g1), respectively, 5.85 6.18

correspond to the adsorbed amount at equilibrium at time t and


maximum; k1 (min1) and k2 (g mg1 min1) are the speed con-
stants of first and second order, respectively; Kads is the Langmuir The X-ray diffractograms of the wood sawdust and the coconut
adsorption constant (L g1); Kf and n are the adsorption parameters mesocarp showed that the peak intensities and peak broadening
of the Freundlich model; Ce is the concentration of the adsorbate at differ from one to another. They exhibited maximum peaks in 2q
equilibrium (mg L1). values equal to 16.4 , 22.4 and 34.7 (SD), and 15.5 and 22.4
The adsorbed quantities (G, mg g1) were obtained by the (CM). These maxima correspond to crystallographic planes (110),
following expression: (200), (023) or (004) and (1_10), respectively (Tserki et al., 2005).
The graphs showed that the sawdust has a structure with superior
½ðCi  Ce Þ:V crystallinity than coconut mesocarp.
G¼ (5)
m With respect to the thermal behavior and stability, TG and DTG
data for both adsorbents (Table 3) showed that these materials
where: Ci represents the initial concentration of the adsorbate (mg behave slightly differently. The first event, near to 373 K, it was
L1); V is the volume of the adsorbate solution (L); and m is the attributed the weight loss of physically adsorbed water on the
mass of adsorbent (mg). surface. Such contents were slightly lower than those observed in
the moisture analysis, representing only the more weakly adsorbed
2.5. Quantum chemical calculations water. The intermediate zone, here represented between 423 and
720 K, it was little more intense for the CM than for SD. In addition,
All quantum chemical calculations were performed by using SD showed less peaks in this temperature zone, probably due to
Spartan'16 (Wavefunction Inc., Irvine, California, USA, 2016), Semi- higher cellulose content (XRD).
Empirical (PM6) method. The last event, temperature range of 723e1273 K, can be
attributed to the final degradation of the lignocellulosic matrices.
3. Results and discussion These events are consistent with the literature (Vieira et al., 2009;
Penha et al., 2016).
3.1. Characterization of adsorbents Both adsorbents showed structures with misshapen surface, of
varying sizes and irregularly distributed external fibers. Small
Because both adsorbents are lignocellulosic matrices, their granular particles predominated in the CM, while the majority
infrared spectra were very similar (Table 1). Differences can be forms in the SD were fibrillar. Also, from the pictures it can be seen
better perceived from elemental analysis according to Table 2. that the SD has a channel structure with pore diameters greater
These arrays differ quantitatively, as to the physicochemical than CM.
composition, which, however, essentially consist of compounds According to BET's results, the SD had higher surface area, pore
containing carbon, hydrogen, oxygen and little nitrogen. For the volume and diameter than the CM. However, both materials can be
coconut mesocarp, Nogueira (2009) found C, N and H contents of classified as mesoporous and with small specific area (Masoud
43.2%, 5.24% and 0.92%, respectively, which are in agreement with et al., 2004).
the results observed in this study, as well as by other lignocellulosic The pH at the point of zero charge (pHzpc) was estimated for SD
(Penha et al., 2016; Vieira et al., 2009). and CM from protonation equilibrium measurements, and the
observed values were 6.1 and 4.0, respectively. This means that
Table 1 below these pH's the surface of such adsorbents will present pos-
Vibrational frequencies and spectral assignments for the main transitions observed
itive net charge, due to protonation equilibria.
in the infrared spectra of SD and CM solids.

Functional group Wavenumber (cm1)


3.2. Adsorption test
SD CM Reference

n(OH) 3415 3419 3200e36009 3.2.1. Effect of pH on dyes adsorption


n(CH, CH2) 2889 2858 2850, 28299 Fig. 1 illustrates the efficiency of the adsorption processes of the
n(C]O) 1730 1735 1735e17509 two lignocellulosic matrices against the RBV and RR anionic dyes as
d(OH) 1640 1625 1600e16509
n(C]C) 1602 1608 161314
a function of the pH. As can be seen, the very acidic environment
n(CeC)ring 1508 1520 15009 increases the efficiency of the process.
d(CeH)ass 1465 1456 1440e14609 For these pH values (1 and 2), and according to the pHzpc values,
1425 1436 the adsorbents' surface shows positive, i.e., with protonated groups,
1419 1415
favoring the interaction with the sulfonic groups of the dyes. By
d(CH)out 1377 1386 13759
n(CO) 1260 1292 1235e12709 increasing the pH, although the dye remains anionic, there is a
n(CeOeC) 1126 1109 11689 decrease in the adsorbent's protonated sites, thus following a
n(CeO)cellulose 1041 1070 10449 consequent adsorption decrease. The pH 2 was set as optimum
d(CeH)ring 898 783 8989 adsorption pH for the following experiments.
d(OH)out 615 667 600e6699
Hence, the obtained results suggests the acidification of a textile
26 M.S. Monteiro et al. / Journal of Environmental Management 204 (2017) 23e30

Table 3
Weight loss data of the SD and CM adsorbents.

Material 1st Step 2nd Step 3nd Step

T range (K) W loss (%) T range (K) W loss (%) T range (K) W loss (%)

SD 323e373 3.8 423e720 64.7 723e1273 12.2


CM 323e393 6.3 423e720 45.2 723e1273 20.2

100
Table 4
CM:RBV Kinetic parameters of the pseudo-first and second order models.
80
CM:RR Model System Parameters
SD:RBV
k1.2 Gexp/Gteo (mg g1) R2
SE:RR
% Removal

60
Pseudo-1st order CM:RBV 0.002 4.03/1.08 0.9695
CM:RR 0.003 2.68/0.15 0.9940
SD:RBV 0.005 1.51/0.22 0.9259
40 SD:RR 0.003 1.22/3.09 0.9845
2nd order CM:RBV 0.258 4.03/4.02 0.9996
CM:RR 0.032 2.68/2.68 1.0000
20
SD:RBV 0.242 1.51/1.51 1.0000
SD:RR 0.052 1.22/1.22 0.9997

0
1 2 3 4 5 6

pH

Fig. 1. Percentages removal of RBV and RR dyes by wood sawdust (SD) and coconut
mesocarp (CM), as a function of pH. Conditions: aqueous solution, [RR] ¼ 64 mg L1;
[RBV] ¼ 80 mg L1; mSD ¼ 0.200 mg; mCM ¼ 0.100 mg; contact time ¼ 24 h.

industry effluent can be a successfully strategy to enhance the ef-


ficiency of the investigates substrates (CM and SR).

3.2.2. Kinetic studies


Fig. 2 shows the contact time results for the adsorption of the
RBV and RR on CM and SD. As can be seen, it takes approximately
8 h (480 min) to reach the equilibria. No change was observed for
24 h of the contact time, so this time was used to obtain the
isotherms.
These experimental data were fitted to the linear mathematical
equations of the pseudo-first and pseudo-second order models
(Montanher et al., 2005; Cantanhede et al., 2006) and the kinetic Fig. 3. Adsorption isotherms of (-) RBV and () RR dyes onto coconut mesocarp (CM).
pH 2.0 (HCl/KCl; m ¼ 1.0 mol L1), T ¼ 300 K, contact time ¼ 24 h, constant stirring.

Fig. 2. Kinetics adsorption of RR and RBV onto SD and CM adsorbents. pH 2,


V ¼ 10.0 mL; 300 K; CM: mCM ¼ 0.100 g; [RR] ¼ 100.0 mg L1; [RBV] ¼ 150.0 mg L1; Fig. 4. Adsorption Isotherms of () RBV and (B) RR dyes onto wood sawdust (SD). pH
SD: mSD ¼ 0.200 g; [RR] ¼ 64.0 mg L1; [RBV] ¼ 64.0 mg L1. 2.0 (HCl/KCl; m ¼ 1.0 mol L1), T ¼ 300 K, contact time ¼ 24 h, constant stirring.
M.S. Monteiro et al. / Journal of Environmental Management 204 (2017) 23e30 27

parameters are listed in Table 4. Despite the similarity in the composition of the adsorbents, the
As observed, the second-order model presented the highest uptake-curves clearly show distinct profiles. The isotherms for the
coefficient of determination (R2) and a better correlation between CM can be classified as L2, while the SD-curves most resemble the
the experimental (Gexp) and estimated (Gteo) adsorbed amounts S2 type (Giles et al., 1960). As the shape of the curves expresses the
(Gexp/Gteo) (Holanda et al., 2015). Hence, a closer to 1 (Gexp/Gteo) forces acting on the system, then the CM presented higher affinity
relation is a good indication that a pseudo-second order model for the dyes than the SD. A possible explanation for this fact can be
provides a better description of the adsorption process. thought from pHzpc values, assuming that the major contribution to
the adsorption is from the interaction between protonated surface
3.2.3. Adsorption isotherms and sulfonic dye grouping. CM presented lower value of pHzpc than
The isotherm adsorptions graphics are shown in Figs. 3 and 4. SD (4.0 and 6.1, respectively). This means that there are groups

Fig. 5. Modeling for adsorption isotherms of RBV and RR onto coconut mesocarp (CM) according to Langmuir and Freundlich models: (a) non-linear modeling; (b) Langmuir and (c)
Freundlich linearized curves.
28 M.S. Monteiro et al. / Journal of Environmental Management 204 (2017) 23e30

more acid on its surface, requiring higher concentrations of Hþ to penetrate more easily through the pores of the material, facilitating
protonate them, then on SD, with positive impact on its efficiency the adsorption process.
(GCM [ GSD). The settings for the Langmuir and Freundlich models are illus-
Another aspect is that the removal of RBV dye was always trated in Figs. 5 and 6, and the main parameters determined by
greater than the removal of RR. As both are anionic dyes, this should these linear fits are shown in Table 5. The results suggest that only
be related to their structures (size). As the RBV is smaller than the the CM systems follow more closely the Langmuir model, while SD-
RR, it may take up less area on the adsorbent surface, and can also adsorptions approached more of the Freundlich model.

Fig. 6. Modeling for adsorption isotherms of RBV and RR onto wood sawdust (SD) according to Langmuir and Freundlich models: (a) non-linear modeling; (b) Langmuir and (c)
Freundlich linearized curves.
M.S. Monteiro et al. / Journal of Environmental Management 204 (2017) 23e30 29

Table 5 Acknowledgements
Values of calculated equilibrium parameters and correlation data according to the
Langmuir and Freundlich models.
The authors are indebted to FAPEMA for financial support and to
Systems Langmuir Freundlich ~o Carlos for its donation of the dye samples.
Indústria de Toalhas Sa
GM (mg g1) KL R2 n K R2

CM:RBV 7.28 0.037 0.9996 4.29 1.92 0.9706 References


CM:RR 3.97 0.022 0.9887 2.72 0.49 0.9197
SD:RBV 2.01 0.005 0.8482 0.64 0.001 0.9885 Armagan, B., Toprak, F., 2013. Optimum isotherm parameters for reactive azo dye
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Freundlich, and Redlich-Peterson isotherms it was verified modified mesoporous silica in the presence of anionic surfactant e the tem-
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Giles, C.H., Macewan, T.H., Nakhwa, S.N., Smith, D., 1960. Studies in adsorption. Part
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adsorption capacity GM (mg g1) for RBV and RR are 7.28 and 3.97 Hameed, K.S., Muthirulan, P., Sundaram, M.M., 2017. Adsorption of chromotrope dye
towards CM and 0.64 and 0.71 towrads SD. onto activated carbons obtained from the seeds of various plants: equilibrium
and kinetics studies. Arab. J. Chem. 10, S2225eS2233.
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pacity of RBV in comparison with RR, can be explained based on the Schultz, M.S., Bezerra, C.W.B., 2015. Remoç~ ao do corante te ^xtil turquesa de
volume, area and polar surface area (PSA) calculated for both dyes. remazol empregando aguape  (Eichhornia crassipes) como adsorvente. Orbit.
Electron. J. Chem. 7, 141e154.
To RBV, area (A2) ¼ 543.46, PSA (A2) ¼ 237.78 and Volume Instituto Adolfo Lutz, 2008. Normas Analíticas do Instituto Adolfo Lutz: me todos
(A3) ¼ 528.23. To RR, the same sequence of parameters has the físico-químicos para ana lise de alimentos, fourth ed. IAL, Sa ~o Paulo.
values: 759.10, 294.21 and 718.65. As can be verified, the bulky dye Kabir, M.P., Islam, M.M., Massum, S.M., Hossain, M.M., 2014. Adsorption of remazol
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4. Conclusion Masoud, M.S., Ali, A.E., Shaker, A.A., Ghani, M.A., 2004. Solvatochromic behavior of
the electronic absorption spectra of some azo derivatives of amino pyridines.
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