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Graphene-based materials production and application in textile wastewater

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Graphene-based materials production and

application in textile wastewater treatment: color
removal and phytotoxicity using Lactuca sativa as
bioindicator

Gabriel Filipe Oliveira do Nascimento, Gabriel Rodrigues Bezerra da Costa,

Caroline Maria Bezerra de Araújo, Marcos Gomes Ghislandi & Mauricio Alves
da Motta Sobrinho

To cite this article: Gabriel Filipe Oliveira do Nascimento, Gabriel Rodrigues Bezerra da Costa,
Caroline Maria Bezerra de Araújo, Marcos Gomes Ghislandi & Mauricio Alves da Motta Sobrinho
(2019): Graphene-based materials production and application in textile wastewater treatment: color
removal and phytotoxicity using Lactuca�sativa as bioindicator, Journal of Environmental Science
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JOURNAL OF ENVIRONMENTAL SCIENCE AND HEALTH, PART A
https://doi.org/10.1080/10934529.2019.1665951

Graphene-based materials production and application in textile wastewater

treatment: color removal and phytotoxicity using Lactuca sativa as bioindicator

joa,
Gabriel Filipe Oliveira do Nascimentoa, Gabriel Rodrigues Bezerra da Costab, Caroline Maria Bezerra de Arau
c a
Marcos Gomes Ghislandi , and Mauricio Alves da Motta Sobrinho
a
Chemical Engineering Department, Universidade Federal de Pernambuco (UFPE), Recife, Brazil; bMechanical Engineering Department,
Universidade Federal de Pernambuco (UFPE), Recife, Brazil; cEngineering Campus (UACSA), Universidade Federal Rural de Pernambuco
(UFRPE), Cabo de St. Agostinho, Brazil

ABSTRACT ARTICLE HISTORY

The dyes used in textile industries are usually difficult to degrade in aquatic environments, being Received 3 May 2019
highly toxic to micro fauna and flora. Thus, textile wastewater treatments have been developed, Accepted 16 August 2019
among them, one that stands out is adsorption process. With the rise of nanomaterials applied to
KEYWORDS
adsorption, graphene oxide (GO) shows promise in the removal of dyes. This work aimed to pro-
real textile wastewater;
duce a more economical and environmentally friendly GO by reducing H2SO4 concentration dur- adsorption kinetics;
ing the synthesis. Adsorption tests were performed with methylene blue (MB) and brilliant blue graphene oxide
(BB), adsorbent regeneration tests, as well as a kinetic study using real wastewater, and toxico- regeneration; color removal;
logical assays with lettuce seeds. Results showed that the sample produced with less H2SO4 (GO- phytotoxicity assays
21) performed better for MB (99% removal) and BB (29% removal); and recycling test showed that
despite the decrease in removal efficiency, it remained high in the first cycles. Kinetics showed
that equilibrium was reached in 30 min, removing 67.43% of color and 90.23% of the effluent’s
turbidity. Phytotoxicity assays indicated that the wastewater treated with GO-21 was the least
toxic, compared to other wastewater samples analyzed. Therefore, GO has demonstrated its poten-
tial to be an effective and less toxic option to treat textile effluents.

Introduction
Because of the large volumes and environmental concerning,
wastewaters from textile industries are considered one of the
main environmental polluters. The release of wastewater
contaminated with dyes and other substances can cause
death of the aquatic fauna and flora, due to its toxicity and
low biodegradability, which is linked to their aromatic struc-
tures [1, 2]. Textile wastewater composition changes accord-
ing to the production process, although the dyeing and
finishing stages are the ones generating more effluent. By
the end of these processes, the wastewater normally contains
numerous dyes and other compounds, such as detergents,
gums, antifoams, oxidizing agents, silicones and softeners,
presenting high concentration of organic matter [3, 4]. Even
at lower concentrations, these substances block light pene-
tration, due to the rise in color and turbidity levels, hinder-
ing the oxygenation in waterbodies [4].
Considerable attention is being given to the removal of
dyes from textile wastewater. Therefore, physical, chemical
and/or biological processes are currently being investigated,
including adsorption [2]. Adsorption has been outstanding
in water and wastewaters treatments for being an easy and

CONTACT Caroline Maria Bezerra de Araujo carolinemariaba@gmail.com Chemical Engineering Department, Universidade Federal de Pernambuco (UFPE),
Rua Prof. Arthur de S
a, s/n, Cidade Universit
aria, Recife 50740-521, Brazil.
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/lesa.
ß 2019 Taylor & Francis Group, LLC
2 G. F. O. DO NASCIMENTO ET AL.
economical method [5]. Among the materials used as
adsorbents, carbon nanomaterials have been widely studied
and applied because of their unique characteristics and size-
dependent properties [6, 7]. Recently, graphene and its
nanomaterials have proved to be promising as adsorbents,
since their unique structural properties, high adsorptive and
regenerative capacities have attracted researchers around the
world [8, 9]. The leaders in this research were the research-
ers Novoselov and Geim [10], who successfully isolated and
characterized graphene mono-layer, being awarded with the
Nobel Prize in 2010. Graphene can be defined as a single
layer of graphite, where each carbon atom in the bidimen-
sional lattice has a p-orbital that contributes to make gra-
phene more stable compared to other nanomaterials [11].
Among all the methodologies proposed for graphene-
based materials (MBG) production, the Hummers and
Offeman method (1958) and its variations are widely
applied, because of the viability for larger scale production.
It proposes the chemical oxidation of graphite, using
KMnO4 in drastic medium (H2SO4, HNO3) [12–14]. After
oxidation, followed by sonication, a suspension mostly com-
posed by graphene oxide (GO) is obtained. After passing
through a reduction process, it gives the reduced GO, which
presents similar properties to graphene [1, 15]. Graphene
oxide has a variety of oxygen functional groups coupled to
its surface, such as carboxyl, hydroxyl and epoxy [16]. Its
hydrophilic nature, high theoretical surface area and highly
negative charges density make GO an effective adsorbent in
the removal of several pollutants from water, such as textile
dyes – anionic and cationic [8, 13, 17].
The aim of this work was to produce GO samples with
reduced concentrations of sulfuric acid, without losing the
efficiency to remove dyes from water. Therefore, the study
was done by testing the performance of GO as adsorbent of
both cationic, methylene blue (MB) and anionic, brilliant
blue (BB) dye. Removal efficiencies of apparent color and
turbidity from a raw textile wastewater collected in a textile
mill were also verified by performing kinetic test.
Subsequently, toxicity of the raw effluent samples was inves-
tigated before and after treatment, focusing on obtaining a
more economical material and less aggressive to the envir-
onment for practical real applications.
Materials and methods
GO production, via the modified Hummers and Offeman
method [12], was done following previous studies by Araujo
et al. [1, 5] using for each sample: 1 g of pure graphite, 3 g
KMnO4, about 200 mL of distilled H2O and 10 mL of H2O2
(33% w/w) to finish the oxidation reaction after about 3 h of
contact. Each sample was synthesized using different ratios
of H2SO4 and distilled water so that the total volume in the
reaction medium remained 25 mL – see Table 1. After syn-
thesis, the samples were sealed and stored in amber flasks.
All assays were performed in replicate. The dye solutions
were produced from stock solutions (1,000 mg.L
1) prepared
for each one of the dyes studied – methylene blue and bril-
liant blue. Textile effluent samples (raw and treated) were
Table 1. Variations in H2SO4/H2O (mLH2SO4.mL
1H2O) proportions during GO
production using 1 g of graphite, 3 g KMnO4 in 3 h of contact.
Sample H2SO4 volume (mL) H2O volume (mL)
GO-25 25 0
GO-23 23 2
GO-22 22 3
GO-21 21 4
GO-20 20 5
collected from the industrial wastewater treatment plant
(WWTP) of a textile mill located in the city of Caruaru,
Pernambuco, Brazil – geographic coordinates: –8.275615,
–35.965612. Samples were stored in a freezer at 4 ± 3  C
without any addition of chemicals for the preservation of
the wastewater properties.
Effect of varying H2SO4 concentration in graphite
oxidation on the adsorption process
Studying the effects of varying the acid concentration used
during graphite oxidation in the dye adsorption process,
1 mL of each sample produced was used, together with
50 mL of the respective dye solution with an initial concen-
tration of 50 mg.L
1 (pH ¼ 5.5). The flasks containing the
solutions were placed under constant stirring (250 rpm) for
1 h at room temperature (28 ± 3  C) to ensure the equilib-
rium was reached [1, 5, 8, 18]. After 1 h of contact, separ-
ation of the supernatant was done by centrifugation for
10 min at 4,000 rpm. The initial and final concentrations
were measured and recorded using a UV-Vis
spectrophotometer.
It should be noted that the same test was developed
under the same conditions for methylene blue and brilliant
blue dyes. The aim was to investigate the behavior of the
GBM produced to adsorb both cationic (MB) and a anionic
(BB) dyes dispersed in water, since real textile wastewater
samples usually contains dyes of different natures, along
with many other organic and inorganic components [19,
20]. The removal efficiencies were calculated according to
Eq. (1), in which C0 and Cf are the initial and final concen-
trations of the dye, respectively.
ðC0
Cf Þ
%R ¼ :100 (1)
C0
Graphene oxide measurements
Characteristics of the graphene oxide samples produced
were observed applying different techniques, such as X-ray
diffraction (XRD); ultraviolet-visible (UV-Vis) spectroscopy;
dynamic light scattering (DLS); pH at the point of zero
charge (pHPZC); Fourier transform infrared (FT-IR) spec-
troscopy and micro-Raman spectroscopy.
XRD of graphite powder and GO samples were per-
formed using a X-ray diffractometer (Rigaku, model:
Ultima), with diffraction angle (2h) ranging from 5 to 50 .
XRD analyses were performed in the Center for Strategic
Technologies of the Northeast (CETENE), Brazil. DLS meas-
urements for nanoparticle size analysis was performed using

the GBM samples dispersed in water (Malvern Panalytical,
mastersizer 2000 – Hydro 2000MU), with size range from
0.020 to 2,000.000 lm. UV-vis spectra were obtained by
diluting graphene oxide suspensions in water and scanning
them in a UV-visible spectrophotometer (Genesys 10 uv –
Thermo Scientific, wavelength: 200–800 nm). pHPZC were
measured based on the experiment of 11 points [1, 5]. Thus,
pH solutions of 1, 2, 3, 4, 5, 6, 8, 9, 10, 11, 12 were prepared
using NaOH and HCl solutions, 6 mol.L
1 each. Then,
2.5 mL of the respective GO sample were placed into 100 mL
Erlenmeyer flasks containing 50 mL of aqueous solution
with pH values adjusted. The flasks were transferred to a
MARCONI MA-420 shaker for 24 h under constant stirring
at 50 rpm. The final pH values were determined using a
bench pH meter (PHTEK, PHS-3B). The DLS, pHPZC and
UV-Vis analysis were performed in the laboratories of the
Center for Technologies and Geosciences, located in the
Federal University of Pernambuco, Brazil.
Micro Raman spectroscopy was proceeded in a Senterra
Raman Scope system with a 532 nm wavelength incident
laser (laser power 20 kW), in a range between 800 and
2,700 cm
1 [21]. Fourier transform infrared (FTIR) spectra
were obtained using a PerkinElmer spectrum two spectrom-
eter, ranging from 650 to 4,000 cm
1. Both analyzes were
conducted at the laboratory facilities of the Civil Police
Criminalistics Institute, in the state of Pernambuco (Brazil).
Graphene oxide regenerative capacity using methylene
blue dye
It is known that one of the main costs regarding wastewater
treatment via adsorption are the ones with adsorbent and its
regenerative capacity [19]. Thus, recycle tests were carried
out using 1 mL of the GO sample (0.02 g.mL
1) that pre-
sented the best results in the previous test. The suspension
was added to flasks containing 50 mL of methylene blue
(30 mg.L
1). It was decided to use a lower concentration of
the dye, so that the color of the dye solution would be more
similar to those from textile mill effluents. Only MB dye
was used, since this was the one that presented the best
removal efficiency [8].
The flasks were placed under constant stirring (250 rpm)
for 1 h. Separation was done by centrifugation (10 min,
4,000 rpm). The supernatant was collected for the determin-
ation of concentration. The solid decanted after centrifugation
was placed in Erlenmeyer flasks with 50 mL of ethanol (70
INPM) for the desorption step at 250 rpm for 1 h [22]. After
desorption, the material was washed twice with distilled water
to remove the residual ethanol, with separation being done in
a centrifuge (10 min, 4,000 rpm). After removing the super-
natant, the decanted material was submitted to a new adsorp-
tion test. The cycle was repeated four more times.
Adsorption kinetics in textile wastewater using
graphene oxide
Normally, organic substances and metal ions coexist in real
wastewater. Thus, it is worth starting to investigate the effect
JOURNAL OF ENVIRONMENTAL SCIENCE AND HEALTH, PART A 3
of having all these different substance on graphene-based
materials performance during adsorption in more complex
systems [20, 23].
Preliminary tests regarding the adsorption kinetics of
GO-21 in real textile wastewater was carried out. In this
case, the main parameters evaluated were apparent color
and turbidity. All analyzes were done according to the
Standard Methods for Examination of Water and
Wastewater [24] – method 2130-B to analyze turbidity and
2120-B for apparent color. The choice of the parameters was
made since color is considered an indicative of the visible
contamination in effluents, reducing the oxygenation cap-
acity of water [25]. On the other hand, excessive turbidity
may indicate the development of pathogens in water
bodies [26].
In each Erlenmeyer 50 mL of raw wastewater were placed
together with 2 mL of GO-21 (0.02 g.mL
1). The was put
under constant stirring (250 rpm) at different time intervals
(3, 5, 10, 20, 30 and 60 min) on a shaker at room tempera-
ture (28 ± 3  C). Each sample was centrifuged (10 min,
4,000 rpm) and approximately 20 mL of the supernatants
were collected [5]. Apparent color and turbidity were deter-
mined using a photometer and a bench turbidimeter,
respectively, and the removal efficiencies were calculated
according to Eq. (1).
Preliminary textile wastewater phytotoxicity assays
using Lactuca sativa (lettuce) seeds
The methodology used for the phytotoxicity assays was
based on Mendes et al. [27] and Gerber et al. [28] The bio-
assays were conducted for the raw and treated wastewater
samples. Firstly, adsorption tests were made with GO-21,
using 2 mL of adsorbent and 50 mL of raw textile effluent.
The systems were agitated at 250 rpm for 1 h, then separ-
ation was done by centrifugation (10 min 4,000 rpm), and
the supernatants were collected.
Petri dishes were lined at their base and sides with quali-
tative filter paper (85 g.m
2, Ø12.5 cm), and 10 lettuce seeds
were placed spaced apart on each dish. 4 mL of the raw
wastewater, the wastewater after treatment in the laundry’s
WWTP, and the supernatant of the wastewater after treat-
ment with GO-21 without any dilution (100%); as well as
the positive (0.02 Al2(SO4)3 solution g.L
1), and negative
(distilled H2O) controls were placed part. Each 4 mL of the
above samples was placed in different petri dishes. Tests
were done for each sample in replicate. Each petri dish was
placed in an incubator, where they were stored for 120 h at
22.5 ± 2.5  C, protected from light. After 5 days, the dishes
were taken from the incubator and with the aid of a trans-
parent ruler, the sizes of the roots for each germinated seed
were measured and the number of germinated seeds were
counted. It was assumed the negative control was valid only
when the percentage of germination was above 90% [29].
From the results, the relative growth index (RGI) was
estimated by Eq. (2), and the germination index (GI%) by
Eq. (3). From the equations, the total root length in the
sample is RLS, the total root length in the negative control
4 G. F. O. DO NASCIMENTO ET AL.
is RLC, the number of germinated seeds in the sample is
GSS and the number of germinated seeds in the negative
control is GSC.
RLS
RGI ¼ (2)
RLC
GSS
GI% ¼ RGI: :100 (3)
GSC
Results and discussion
Graphene oxide production varying H2SO4
concentration
Results of the adsorption tests for the samples produced
with different concentrations of H2SO4 are shown in Figure
1. It is observed that as the acid concentration decreases, the
adsorption of BB is favored, while MB adsorption is disad-
vantaged by excessively decreasing the acid concentration.
This occurs because the acid is involved with the formation
of oxygen groups on the materials surface during the oxida-
tion, allowing the penetration KMnO4 in the graphite layers
more effectively [15]. These groups support the interaction
between GO and MB due to the negative density of the
adsorbent and the cationic characteristic of the dye, so that
adsorption occurs both via electrostatic interactions with the
oxygenated groups on the GO surface and by p-p interac-
tions between the aromatic rings [13].
Apparently, a decrease in the amount of acid during GO
production leads to a lower degree of graphite oxidation,
decreasing the number of functional groups on the surface
of the material. This, on the other side, enables a better
interaction of the material with anionic dyes, such as BB
dye, via p-p interactions of the aromatic rings present in
both the adsorbent and adsorbate structures [8].
Yan et al. [13] prepared and analyzed several GO samples
with different degrees of oxidation using the modified
Hummers method, varying the KMnO4 dosage and oxida-
tion time. When analyzing the effects of the oxidation
degree on MB adsorption, it was observed that the adsorp-
tive capacities increased exponentially with the increase of
the degree of oxidation of the sample. The explanation
would be related to the increase in the degree of exfoliation
of graphitic layers, caused by the energetic oxidation; as well
as the production of a larger number of active sites. The
characteristics of GO-MB interaction gradually change from
parallel stacking of MB molecule in the graphemic plane
through the hydrophobic p-p interactions, to the vertical
position by means of electrostatic interaction, as there is an
increase in the oxidation degree.
Araujo et al. [1] were able to decrease the volume of
H2SO4 from 25 mL to 23 mL without considerable reduction
of MB adsorption. This research, on the other hand, demon-
strates that the best experimental point (GO-21) was able
not only to maintain the high MB percentage removal (99%)
but also to increase BB removal by 21% to 29%. Therefore,
the sample prepared with 21 mL H2SO4 will be used in
Figure 1. Variation of H2SO4 volume in the production of graphene oxide vs.
Removal efficiencies of the dyes MB and BB (Adsorption test conditions: 50 mL,
50 mg. L
1 dye, 1 mL of GO, 1 h, 250 rpm, pH ¼ 5.5, T ¼ 28 ± 3  C).
subsequent tests. Important characterizations will also be
presented for this sample.
In overall, a decrease in the amount of acid causes a
reduction in costs with production process, making the
material less aggressive to the environment, without making
it lose the ability to adsorb the dyes. However, it is observed
that sample GO-20 shows a more pronounced decrease in
the percentage removal of MB, while there is a slight
increase in the BB removal efficiency. H2SO4 provides the
energic medium necessary for graphite oxidation to occur
[5]. Thus, it is believed that a greater decrease in the acid
concentration tends to affect even more its effectiveness as
adsorbent by the decrease in the amount of graphite that
becomes GO.
Graphene based materials characterization
The optical absorption spectra of GO-21 and GO-25 suspen-
sions are exhibited in Figure 2a. In general, it is possible to
see in the samples the presence of prominent absorption
peaks in 230 nm, attributed to p-p transition of the C-C
bonds of the aromatic rings; and a shoulder in 296 nm, asso-
ciated with the n-p transition of the C ¼ O bonds on the
surface of GO samples [30, 31]. DLS measurement was per-
formed in aqueous solution to estimate GO lateral sizes. It
was found that the average particle sizes of GO-21 and GO-
25 were respectively 26 lm and 32 lm – see Figure 2b.
DLS measurements could contribute to show that when
comparing both samples (GO-21 and GO-25), the results
were almost the same, indicating that the sample produced
with less H2SO4 presents similar characteristics to the one
produced with more concentrated acid[30, 32].
Crystalline structures of the GO samples and pristine
graphite were characterized by XRD. Graphite powder
exhibited a main basal diffraction (002) peak located at
approximately 2h ¼ 26 , as the diffraction peaks of GO-21
and GO-25 appear at the lower angles of 7.7 and 8.6 ,
respectively. Thus, it can be verified an increase in the inter-
layering spacing in both cases, as the 2h values decreased

Figure 2. Characterization results: (a) UV-Vis measurements; (b) particle size distribution from DLS analysis for samples GO-21 and GO-25; (c) XRD patterns for
graphite, GO-21 and GO-25; (d) pH PZC for GO-21 and GO-25.
from 26 to below 10 (Fig. 2c). The increase in d-spacing is
related to the formation of oxygen functional groups
between the graphitic layers, indicating the successful oxida-
tion of graphite [31, 32]. pH at the Point of Zero Charges
for both samples were determined. As it can be observed in
Figure 2d, it is possible to see the formation of a well-
defined plateau near the final pH 2.5. Therefore, pHPZC val-
ues were 2.64 and 2.37 for samples GO-21 and GO-25,
respectively. For pH values over the pHPZC, adsorption of
cationic dyes is favored. Evaluating the adsorptive removal
of cationic dyes from water using GO, Konicki et al. [33]
found the zeta potential measurements of GO were negative
for a pH range of 1.7 to 12.2.
JOURNAL OF ENVIRONMENTAL SCIENCE AND HEALTH, PART A 5
Raman spectra of graphite, GO-21 and GO-25 in Figure
3a and b exhibited D band at approximately 1,350 cm
1 and
G band at 1,600 cm
1. The D/G peak intensity ratio, known
as ID/IG, usually indicates the lattice disorder of graphitic
and graphene-based materials. Therefore, ID/IG values were
estimated to be 1.20 and 1.60 for samples GO-21 and
GO-25, respectively, indicating as expected, an overall
increase in defects after oxidation. These defects arise from
the disruption of the carbon basal plane structure by the
introduction of functional groups due to oxidation [21, 34].
Comparing the graphite to GO spectra, it can be observed
an increase in the D band intensity for both GO-21 and
GO-25, being this increase more pronounced for the sample
6 G. F. O. DO NASCIMENTO ET AL.
Figure 3. Micro Raman measurements of (a) graphite powder; (b) GO samples; and (c) FT-IR spectra of GO-21 and GO-25.
produced using more sulfuric acid. FT-IR spectra (Fig. 3c)
showed the vibration modes of GO-21 and GO-25. The
bands located in 3,350 cm
1 are assigned to O–H stretching
vibrations from hydroxyl groups on GO surface and water
adsorbed. The bands at 2,100 cm
1 (more pronounced in
GO-25) can be attributed to CC stretching. The absorption
bands at 1,725 cm
1 are the characteristic band of C ¼ O
groups. Bands near 1,600 cm
1 are associated with the skel-
etal vibrations of C ¼ C from unoxidized graphite.
The shoulders at 1,400 cm
1 might be attributed to O-H
or C-H. The bands at 1,170 and 1,050 cm
1 are assigned to
C-O-C and C–O bonds, respectively [14, 21, 35].
Afterall, the sample produced with less concentrated sul-
furic acid (GO-21) was used as adsorbent for the following
experiments.
Regenerative capacity of the graphene-based material
Results for the GBM regeneration tests are shown in Figure
4. In this case, a decrease in removal efficiencies of MB
using GO-21 was observed at each adsorption-desorption
cycle. In the mass estimation, it was found that in 1 mL of
suspension there is approximately 0.02 g GO.
Analyzing the graph, it is observed that at each cycle, a
decrease in removal efficiency gradually occurs. This behav-
ior was already expected, due to the small amount of
adsorbent used in the tests (0.02 g), as well as the losses that
naturally occurs during the desorption and washing stages.
Therefore, the mass, which was already small, tended to
decrease. Furthermore, during the washing and centrifuga-
tion steps, it is important to bear in mind that part of the
dye may still remain adsorbed on graphene oxide surfaces

Figure 4. Results for the regeneration tests in terms of % removal of MB and
Cfinal of the dye (Conditions: 50 mL effluent, 50 mL ethanol, 1 mL of GO-21, 1 h
of contact at 250 rpm, T ¼ 28 ± 3 C).
after each regeneration. All those factors combined can con-
siderably reduce the process efficiency every cycle.
Comparing the cycles, in the 1st one, a drop in the
removal efficiency is very small, and the value remains close
to 95%. However, in the 2nd cycle the removal efficiency
substantially drops to approximately 80%. According to Yan
et al. [13] it can be inferred that GO samples produced with
higher acid concentration present higher regenerative
capacities for MB dye, showing a more significant drop only
from the 4th cycle. This can be explained as oxidation hap-
pens more efficiently with more concentrated acid, produc-
ing an adsorbent with more functional groups. That,
therefore, favors the adsorption of a great number of dye
molecules during the adsorption-desorption cycles.
Nevertheless, after the last cycle, it is verified the percent-
age removal of dye is still nearly 60%. Comparing GO-21 to
active carbon regenerative capacity, for example, Foo and
Hameed [36] applied microwave heating in the regeneration
of methylene blue-loaded activated carbons. After the 4th
adsorption-desorption cycle, oil palm shell activated carbon
presented 54.5% efficiency removal of MB, when initially it
was 98%; as the oil palm fiber activated carbon presented
nearly 60% removal efficiency after the 4th cycle, when ini-
tially was 95% – experimental conditions: 0.20 g adsorbent,
200 mL of MB solutions (300 mg.L
1) at 30  C, 120 rpm
for 24 h.
Kinetics for the removal of color and turbidity from real
textile wastewater
Kinetics results for apparent color and turbidity removal
efficiencies using GO-21 are shown in Figure 5. From the
graph, it is observed that in the first 5 min, removal efficien-
cies quickly increase. After 10 min, the growth become
smoother, obtaining maximum removal efficiencies and
reaching the equilibrium in less than 30 min [5].
Considering the whole process (i.e., including centrifuga-
tion after adsorption), the removal efficiencies exceed 67%
for apparent color and 90% for turbidity, as can also be seen
in Table 2. It is observed that there is no change in pH after
JOURNAL OF ENVIRONMENTAL SCIENCE AND HEALTH, PART A 7
Figure 5. Kinetics of apparent color and turbidity removal in real textile waste-
water (Conditions: 50 mL of effluent, 2 mL of GO-21, 250 rpm, pH ¼ 6,
T ¼ 28 ± 3 C).
treatment with GO, as pH remained equals to 6. These
results are in agreement with those obtained by Aboukaraka
et al. [26], who used GO to remove turbidity in surface
water treatment. In their work, for a sample of water with
initial turbidity of 200 NTU, the percentage removal
exceeded 90% using GO. They also observed that the coagu-
lation potential of GO was directly affected by water alkalin-
ity, as raw surface water containing alkalinity over
100 mg.L
1 indicated higher percentages removal > 97%, for
initial turbidity of 100 NTU.
The effect of ionic strength also has a positive influence
on the adsorption of organics by GO. In this case, ionic salts
can interact with both the organic molecules in solution (or
suspended) and the adsorbent surface, modifying its surface
charge. For the considerable turbidity removal presented,
the effect of ionic salts, which probably is contained in the
textile wastewater, might have decreased the solubility of the
suspended organic matter (salting out effect), favoring the
rapid turbidity removal [26, 37].
From Table 2, the removal efficiencies obtained after the
WWTP were lower (63.4% for color and 77.5% for turbid-
ity) compared to the experimental values obtained with the
proposed treatment. Using adsorption in activated carbon
combined with coagulation/flocculation, Harrelkas et al. [38]
obtained only 50% color removal from textile wastewater.
Thus, it can be inferred that adsorption using graphene
oxide was effective for the removal of color and turbidity of
the effluent, without altering the pH of the effluent by the
end of the treatment.
Phytotoxicity assays with textile wastewater using
Lactuca sativa (lettuce) seeds
With the number of germinated seeds and root length val-
ues, RGI and GI values were calculated. Results are shown
in Figure 6. According to Mendes et al. [27], GI lower than
100% indicates the germination capacity and root length for
the seeds were negatively affected by the contact with the
8 G. F. O. DO NASCIMENTO ET AL.
Table 2. Measurements of the parameters apparent color, turbidity and pH for the textile wastewater samples.
Sample Color (Hazen)
Raw textile wastewater 505.0
Textile wastewater treated in the WWTP 185.0
Textile wastewater treated using GO-21 164.5
Figure 6. Graph of the RGI and GI values for the analyzed samples (Conditions:
4 mL of sample, 120 h of incubation, T ¼ 22.5 ± 2.5  C, 10 seeds L. sativa
in replicate).
solution, as values higher than 100% indicate that both indi-
cators were improved.
Comparing the results obtained for the raw wastewater,
the sample treated in the laundry’s WWTP and the raw
wastewater treated with GO, it is clear the treatment using
GO-21 presented better performance. Although none of the
GI values were even close to 100% (except for the negative
control, H2O), the wastewater sample treated with GO-21
presented GI (20%) and RGI (0.35) values greater than the
others. This may indicate that the treatment applied to the
textile wastewater using GO might have caused the treated
wastewater to be less toxic to the environment, compared to
conventional methods.
Thus, it could be inferred that the results obtained here
were promising, when compared to other treatments.
Studying the toxic effect of multiwalled carbon nanotubes
(another carbonaceous nanomaterial) on lettuce, for
example, Ikhtiari et al. [39] observed that the nanotubes
could decrease the plant growth in a dose dependent man-
ner, in all concentrations range considered.
Nevertheless, Zhao et al. [34] systematically investigated
the toxicity mechanism of graphene oxide, reduced GO and
multi-layer graphene, to algae Chlorella pyrenoidosa. In
overall, GBM exhibited much higher toxicity than other car-
bon materials, including carbon nanotubes and graphite,
and besides all GBMs could adsorb macronutrients from the
algal, GO showed the highest nutrient depletion among all,
due to its functional groups. Their tests were performed
under higher GBM concentrations introduced in the
medium (50 mg.L
1).
Although in the present study there is a different pur-
pose, as only the toxicological effect of a possible reminis-
cent concentration of GO in the treated wastewater was
evaluated, more tests applying this and other toxicological
%Removal color Turbidity (NTU) %Removal turbidity pH
– 262.7 – 6.0
63.4 59.0 77.5 6.0
67.4 25.7 90.2 6.0
bioindicators would be necessary to infer more grounded
conclusions.
Conclusions
Experiments to reduce H2SO4 concentration during gra-
phene oxide production presented satisfactory results, in
which the sample produced with 21 mL of sulfuric acid
(GO-21) showed not only higher removal efficiencies for
BB (29%), but maintained a high removal rate for MB
(99%), being more economical and environmentally
friendly. Kinetics in real textile effluent demonstrated that
GO-21 efficiently removed apparent color and turbidity –
67.43% for color and 90.23% for turbidity – and reached
equilibrium rapidly (30 min), exhibiting better results than
the obtained for the WWTP effluent sample. Comparing
the samples in the phytotoxicity assays, it was observed
that GO-21 obtained the best results (GI% ¼ 20%; RGI ¼
0.35). In the regeneration study, despite the decrease in
percentage removal after each cycle, GO showed high
removal efficiencies in its first cycles. Finally, the results
demonstrate the viability of graphene oxide production
using less H2SO4, being a cheaper, environmentally
friendly product, with good efficacy in color removal
from wastewater.
Acknowledgments
To the Chemical Engineering Department of the Universidade Federal
de Pernambuco and the Laboratory of Mineralogy; the Center for
Strategic Technologies of the Northeast (CETENE); and the Civil
Police Criminalistics Institute, all located in the state of Pernambuco
(Brazil). Also to Ms. Bruna Figueiredo, Ms. Amanda Bel
em Chaves and
Professor Dr. Maria Fernanda Pimentel for all the support.
Disclosure statement
The authors declare they have no conflicts of interest to disclosure.
Funding
This work was supported by the Conselho Nacional de
Desenvolvimento Cient
ıfico e Tecnol
ogico (CNPq) under Grant num-
bers 312128/2018-5 and 311133/2015-0; the Fundaç~ao de Amparo a
Ci^encia e Tecnologia do Estado de Pernambuco (FACEPE) under
Grant number APQ-1086-3.06/15; and the Coordenaç~ao de
Aperfeiçoamento de Pessoal de N
ıvel Superior (CAPES) under Grant
number 206/2018.
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