Chemosphere 236 (2019) 124309

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Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Real textile effluents treatment using coagulation/flocculation

followed by electrochemical oxidation process and ecotoxicological
assessment
Na
dia Hortense Torres a, b, *, Bruno Santos Souza c, Luiz Fernando Romanholo Ferreira a, b,


ucia Nicolau dos Santos a, b, Eliane Bezerra Cavalcanti a, b
Alvaro Silva Lima a, b, Gla
a
Graduate Program on Process Engineering, Tiradentes University, Av. Murilo Dantas, 300, Farola^ndia, 49032-490, Aracaju, Sergipe, Brazil
b ^ndia, 49032-490, Aracaju, Sergipe, Brazil
Institute of Technology and Research, Av. Murilo Dantas, 300, Farola
c ~o Cristo
Department of Environmental Engineering, Federal University of Sergipe, Av. Marechal Rondon, S/n, Jd. Rosa Elze, Sa ~o, SE, Brazil

va

h i g h l i g h t s

Coagulation/flocculation can remove color from real textile effluent with >70% of efficiency.

L. sativa and R. subcapitata can be used for ecotoxicological essays in effluent treated.

C/F and EOP has proved an efficient process to remove TOC from real textile effluents (~82%).

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

Article history: As it is well known, the textile industry generates a large amount of wastewater with varied composition
Received 22 March 2019 that need to be treated. In particular, the Sergipe state, in Brazil, is a region that requires attention due
Received in revised form the presence of several local textile industries. In this study, the efficiency of electrochemical oxidation
3 July 2019
(EO) process applied in the samples of Brazilian textile industry effluents previously treated by physical-
Accepted 5 July 2019
Available online 11 July 2019
chemical process coagulation-flocculation (CF) was evaluated by the reduction in TOC parameter and by
the ecotoxicity using Lactuca sativa and Raphidocelis subcapitata bioassays. The optimized experiments
Handling Editor: E. Brillas achieved for the CF ([Al2(SO4)3]0 ¼ 1.5 mg L1, pH ¼ 6.0, alkalinity ¼ 0.675 mg L1, [flocculating
agent] ¼ 61 mg L1, rapid mixing ¼ 100 rpm for 1 min, slow stage ¼ 20e60 rpm for 20 min) a reduction
Keywords: of 20% on TOC. The best results obtained for EO was using the DSA electrode (I ¼ 300 mA) reaching a TOC
Environmental contamination removal efficiency of 82% after an electrolysis time of 180 min. The ecotoxicity experiments indicated
Water body that the proposed treatment (CF þ EO, I ¼ 300 mA) was effective to decrease the dissolved pollutants
Industry presented in the treated samples. In comparison with raw samples, the treatment achieved a reduction of
Toxicity
52% for IC5072h value using R. subcapitata as bioindicator, and a 98% reduction of LC50 (Lactuca sativa).
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction Europe, around 600 million m3 of freshwater is used annually by

For any industries, in order to attend the environmental regu-
lations, the wastewater treatment requires attention. In particular,
the textile industry produces a complex and variable effluent
depending on the processed fabric and the type of involved process,
as washing, bleaching, dyeing, printing, starching and coating. In
* Corresponding author. Post-Graduated Program on Process Engineering, Tira-
dentes University, Av. Murilo Dantas, 300, Farol^
andia, 49032-490, Aracaju, Sergipe,
Brazil.
E-mail address: nadiahortense@gmail.com (N.H. Torres).
this sector in order to prepare textile products, and are estimated
that 108 million tons of wastewater is produced (Vajnhandl and
Valh, 2014). Textile wastewaters untreated can be considered one
of the major pollutants for the aquatic environment due to specific
characteristics, such as high organic and inorganic carbon con-
centration, strong color, high pH and temperature, toxicity and low
biodegradability (Anvari et al., 2014; Garcia-Segura et al., 2018). In
fact, textile wastewater is rich in several contaminants, as organic
compounds, such as dyes and colorants, surfactants and other
substances used (Punzi et al., 2015), as well as inorganic salts
content (Duenser, 1992; GilPavas et al., 2018). In environmental

https://doi.org/10.1016/j.chemosphere.2019.07.040
0045-6535/© 2019 Elsevier Ltd. All rights reserved.
2 N.H. Torres et al. / Chemosphere 236 (2019) 124309
terms, this wastewater can present highest values of suspended
solids, COD, BOD, as well as high pH, conductivity and color.
Many factories are designed to operate with wastewater recy-
cling and reusing system to improve the process (Majewska-
Nowak, 1989; Bhuiyan et al., 2016). However, in general these
methods are insufficient for obtaining the required final water
quality established by regulators agencies. A major environmental
issue associated at textile production is the wastewater treatment.
Due the presence of several recalcitrant compounds, the conven-
tional biological treatment is ineffective and the application of
specific treatments is required (Vlyssides et al., 1999; Asghar et al.,
2015). In particular, the coagulation-flocculation treatment is a
relatively simple physical-chemical technique that uses coagulants
agents as aluminum sulphate and ferric chloride achieving in
general positive response for the wastewater treatment. Other
specific treatment is the electrochemical advanced oxidation pro-
cess, characterized by the generation of oxidant species in water,
where the most important is the OH radical (Moreira et al., 2017;
Silva et al., 2017). These OH radical are able to oxidize saturated and
unsaturated organic compounds such as azo dyes (Fo €ldva
ry and
Wojna
rovits, 2007).
Electrochemical oxidation process has been successfully used to
treat a wide range of pollutants from different kinds of wastewater:
(i) domestic wastewater (Daghrir et al., 2014); (ii) agro-industrial
effluents (Tatoulis et al., 2016); (iii) petrochemical effluent
(Santos et al., 2006, 2013; Abdelwahab et al., 2009); (iv) textile
industry (Radha et al., 2009; Aquino et al., 2014; Torres et al., 2018);
(v) synthetic hospital wastewater (Ouarda et al., 2018); (vi) paper
mill industry wastewater (Chanworrawoot and Hunsom, 2012);
(vii) tannery wastewater (Costa et al., 2008; Szpyrkowicz et al.,
1995); (viii) sanitary landfill leachate (Torres et al., 2018).
The efficient treatment to eliminate effectively pollutants and
toxicity to organisms is one of the greatest challenges in waste-
water controlling. While pollutants present in water matrices are,
in general, relatively easy to characterize physical-chemically,
assessing their impact on the environment is usually difficult, and
therefore, ecotoxicological methods have been used to complete
the characterization. Phytotoxicity tests as those that use seeds as
test organisms are vantage, because they are simple, rapid, inex-
pensive and only require a relatively small amount of sample. In
relation of algae, they make a part as important elements in aquatic
ecosystems due oxygen producer function, for their self-purifying
activity and as staple food for primary consumer organisms.
Therefore, the main objective of this study is to treat textile
wastewater by a combined treatment: physical-chemical procedure
followed by an electrochemical oxidation process. In addition, this
paper explores the ecotoxicological assessment on treated and
untreated samples using algae Raphidocelis subcapitata and lettuce
seed Lactuca sativa as test organisms.
2. Materials and methods
2.1. Textile wastewater samples
For this work, the wastewater samples were supplied from a
dyeing solutions tank of exhaust at a textile factory located at
northeast Brazil (10 420 49.900 S 37120 43.200 W, Riachuelo city - Ser-
gipe state). Samples were collected (20 L) at the reservoir entrance
in April 2017 and stored in polypropylene bottle and kept at ± 4  C
until moments before the experiments were carried-out. The prior
experimental optimization of Coagulation-Flocculation was per-
formed using synthetic textile matrix solution. Bright green dye
indanthren C-FFB (Dystar) was spiked in the deionized water in
order to obtain a final synthetic solution of 100 mg L1.
2.2. Chemicals reagents
The reagents used in physical chemical treatment in precursor
solution preparation, as well as in the electrochemical process,
were aluminum sulphate (Al2(SO4)3, P.A, VETEC®), n-hexane (C6H14,
Sigma-Aldrich®, 99%), sodium hydroxide (NaOH, 1.0 M, Synth®),
sulfuric acid (H2SO4, 0,5 M, Synth®), flocculating agent Engeclean
CA 34. All reagents (P.A. grade) used on ecotoxicological assessment
were purchased from VETEC®.
2.3. Experimental setup
Firstly, the samples were treated using a jar test equipment in
order to optimize the experimental parameters. Both physical-
chemical treatment and electrochemical process were adapted
following (Torres et al., 2018). Thus, the experimental steps follow:
(i) Optimization of CF parameters with synthetic effluent; (ii)
optimization of electrochemical treatments using real textile
wastewater samples treated by CF process; (iii) Toxicity bioassays
using Raphidocelis subcapitata and Lactuca sativa applied in samples
from treatment optimized with CF þ EO.
2.4. Raw textile waste physicochemical characterization
The textile effluent was characterized (Table 1) according to the
methodologies described by the 20th Standard Methods for
Examination of Water and Wastewater (2012), as follows: total
oils and grease content (TOG) (gravimetric method of extraction by
n-hexane, 5220 B/F); biochemical oxygen demand (BOD) (method
5210 B); chemical oxygen demand (COD) (method 5220 B); hard-
ness (method 2340 C); total solids (method 2540 B). Others pa-
rameters were determined using different equipment: the
electrical conductivity (method 2510 B) was measured by a conduct
meter (Hanna Instruments, HI 2300 model); pH was analyzed by a
pH meter (PG1800, GEHAKA); the turbidity was measured by a
turbid meter (MS Tecnopon, TB100P model); a TOC-LCSN Shimadzu
equipment was used to determine the total organic carbon (TOC).
According to Garcia-Segura et al. (2018), typically the textile dye
effluents present a chemical oxygen demand ranging of 250e1400
mgO2 L1.
2.5. Coagulation-flocculation procedure
The CF pretreatment was carried out using a synthetic textile
effluent with adaptation from D2035 ASTM Standard Method
(1995). This step was performed in order to optimize the experi-
mental parameters (pH, dosages of coagulant and flocculating) and
the equipment used was a conventional jar test at room tempera-
ture (22 ± 2  C) model Floc Control II (PoliControl). The response
parameter used was the effluent mineralization, expressed by the
TOC. Initially, the procedure was carried out setting the solution pH
Table 1
Physicochemical parameters of raw textile effluent.
Parameter Result
pH 7.8
Conductivity (mS cm1) 4640
Turbidity (NTU) 220
TOC (mg L1) 734
BOD (mg L1) 289
COD (mg O2 L1) 1130
Alkalinity (mgCaCO3 L1) 857
Total Hardness (mg L1) 19.4
Oils and greases (mg L1) 19
Total solids (mg L1) 3570
 N.H. Torres et al. / Chemosphere 236 (2019) 124309
and varying doses of Al2(SO4)3 added in jars (from 1,0e50 mg L1).
The rapid mixing stage took place for 1 min at 100 rpm, followed by
a slow stage for 20 min varying at 20e60 rpm. The concentration of
the Engeclean CA 34 flocculating ranged from 8 to 230 mg L 1.
Then the sludge was left to settle for 60 min. After the settling
period, the supernatant was withdrawn and used for TOC analysis.
Then, the optimization process was carried out setting the dose of
Al2(SO4)3 and ranging the pH value from 3 to 8.
2.6. Electrochemical oxidation
All experimental procedures were conducted in batch mode
using a compartment electrochemical cell made of Pyrex® glass and
using 100 mL of sample at room temperature (±23  C). The elec-
trode used was an expanded Dimensionally Stable Anode Ti/
Ti0.7Ru0.3O2 (DSA®, DeNora, Brazil) and a 316 stainless steel perfo-
rated cathode plate with an exposed area of 8 cm2 (Iniesta et al.,
2001; Martinez-Huitle and Ferro, 2006). The current intensity in
the potentiostat/galvanostat BIOLOGIC, VMP3, was set to 100, 200
and 300 mA and the distance between the cathode and anode was
2 cm (Jaruwat et al., 2010). Samples were electrolyzed for 180 min
under constant magnetic stirring and 1 mL aliquots were collected
at determined time points to monitor TOC.
2.7. Ecotoxicological assays using Raphidocelis subcapitata
The test organisms of Raphidocelis subcapitata algae used in the
toxicity bioassays were provided by the Group of Studies on Aquatic
Ecosystems (GEEA) of Environmental Engineering Department,
Federal University of Sergipe (Brazil), and were maintained ac-
cording to the recommendations of (Blaise et al., 2000). The bio-
assays were adapted from a pre-existing methodology, which
evaluates the solution concentration that effectively inhibited 50%
of algal growth after 72 h of incubation (IC5072h) in comparison to
the negative control. The test was performed in triplicate and the
method used a series of dilutions ranging from 3.125 to 75% (Blaise
et al., 2000; Calomeni and Rodgers Jr, 2015; Torres et al., 2018).
2.8. Ecotoxicological assays using Lactuca sativa
In order to assess the toxicological response, lettuce seeds
(Lactuca sativa) were used as toxicity level bioindicators due to
their fast response to concentrated and diluted solutions. The bio-
tests applied in this paper were developed according to the
methodology described by (Sobrero and Ronco, 2004). Three rep-
licates were tested on a set of dilutions (1.56, 3.125, 6.25, 12.5, 25, 50
and 75%, containing 20 lettuce seeds each) using treated and un-
treated samples. Negative control applying 0.2 M NaCl solution and
a positive control with distilled water were used. Using Petri plates
(100  15 mm), the lettuce seeds were put on a layer of the
filtration-type paper containing solutions (samples or distilled
water) and properly covered. Then they were germinated inside an
incubator at constant temperature of 22 ± 2  C. The germination
Table 2
Percentages of turbidity, ratio of [TOC]/[TOC]0 and color removal for samples with different pH values, and coagulant and flocculating concentrations at 1000 and 153 mg L1,
respectively.
[coagulant] ¼ 1000 mg L1; [flocculant] ¼ 153 mg L1 pH
3.0
4.0
5.0
6.0
7.0
8.0
3
was registered after 120 h of exposure and %RG and LC50 calcu-
lated. The values determined the germination rate (RG) used Eq. (1),
where SGA is the number of seeds germinated in the sample and
SGC is the number of seeds germinated in the control.
N  SGA
%RG ¼ *100 (1)
N SGC
The LD50 values were estimated according to the methodology
described by (Hamilton et al., 1977), using the software Trimmed
Spearman-Karber Method version 1.5.
3. Results and discussions
3.1. Coagulation-flocculation procedure
Initially, experiments were performed to determine the opti-
mum pH value for the CF treatment. The total organic carbon, color
(lmax ¼ 416 nm) and turbidity were obtained as response parame-
ters. Thus, the pH values analyzed were 3.0; 4.0; 5.0; 6.0; 7.0 and
8.0, using concentrations of coagulant and flocculating settled at
1000 and 153 mg L1, respectively (Table 2). For CF experiments, the
effect of turbidity removal depends on the samples pH variation
(Simate et al., 2012).
The solution pH is an important parameter in the CF procedure
because affects the ionic characteristics. A turbidity and color
reduction behavior is clearly observed by raising the pH values
from 3.0 to 6.0, and it was basically unchanged from 6.0 to 8.0. For
both parameters, the highest reduction efficiency was reached
around 90%. This situation illustrates a favorable region for the
pollutant destabilization process through adsorption-
neutralization of charges, as described by (Furlan et al., 2010),
however, a part of the organic matter in solution cannot react with
coagulant to form insoluble precipitation, even in alkaline media.
These results may be due to the amount of ions remaining in the
solution, since the neutral and basic media may have provided a
greater adsorption between the coagulant and the particles.
Another possibility is associated to the effect of repulsion between
particles in acidic solution (Kuo and Lin, 2009). The polymeric
cationic flocculating used, and the particles presented in acidic
solution, both with positive ions would hinder the agglomeration,
influencing the TOC removal. Thus, the best TOC removal efficiency
was obtained at pH 8.0, with 17%, which was the pH value adopted
in the following experiments as the optimum pH.
3.2. CF optimization: optimum coagulant dosage
The coagulant Al2(SO4)3 concentration used is one of the factors
contributing to the contaminants removal from an effluent (Furlan
et al., 2010). Thus, the effect of varying the coagulant dosage from
10 to 50 mg L1 on the turbidity, TOC and color (lmax ¼ 416 nm)
removal of the samples at pH 8.0 and using a flocculating settled at
40 mg L1 was evaluated (Table 3).
It was observed that with the coagulant dose increase from 10 to
% turbidity reduction [TOC]/[TOC]0 % color removal
72.1 1.00 68.8
83.5 0.97 79.6
82.9 0.99 80.3
91.3 0.90 88.8
90.5 0.92 88.1
90.8 0.83 89.0
4 N.H. Torres et al. / Chemosphere 236 (2019) 124309

Table 3
Percentages of turbidity and color removal, and [TOC]/[TOC]0 ratio for samples at pH ¼ 8.0 and flocculating concentration at 40 mg L1.

pH ¼ 8.0 [flocculant] ¼ 40 mg L1 Coagulant concentration (mg L1) % turbidity reduction [TOC]/[TOC]0 % color removal

10 60.9 1.09 84.9

20 86.0 0.78 66.3
30 86.0 0.80 86.2
40 35.9 1.31 60.9
50 54.8 0.99 96.9

20 mg L1, an improvement occurred in the parameters analyzed,
and from the concentration of 30 mg L1, a reverse effect was
verified. This response profile was also observed in other studies in
the literature (Zou et al., 2011). The most probable explanation is
that the treatment efficiency is limited, and the concentration of
20 mg L1, for these samples, reached a maximum efficiency, and
the additional coagulant input caused a negative effect on the
process. Thus, the optimum coagulant dosage was determined as
20 mg L1.
3.3. CF optimization: optimum flocculating dosage
In order to optimize CF treatment, the optimum conditions
found in the previous steps (pH ¼ 8.0 and coagulant concentra-
tion ¼ 20 mg L1) were used, and the effect of varying flocculating
concentration from 76.7 to 230 mg L1 on the turbidity, TOC and
color (lmax ¼ 416 nm) removal of the samples was evaluated
(Table 4). The best results were obtained using flocculating con-
centration of 76.7 mg L1, achieving a TOC removal efficiency of
62.9%.
The increase in the concentration of the flocculating provided in
the samples an augment in the TOC parameter, which can be
explained by the low solubility of this polymeric compound in the
solution, and this way, it was not used to promote the flocculation
process, remaining in solution. Negative effects with the use of the
flocculating large doses in the CF treatment was reported in the
literature (Golob et al., 2005). As observed, the concentrations of
the flocculating of 153.3 and 230 mg L1, did not promote good
efficiency when compared to the 76.7 mg L1, thus, this was the
value chosen for optimized concentration.
3.4. Electrochemical oxidation time effect
Due to their high conductivity (4640 mS cm1), the EO experi-
ments could be performed without the further addition of salts,
which acts as supporting electrolyte (Garcia-Segura et al., 2018),
thus no salts were added on samples. Based on CF experimental
optimization, the electrochemical oxidation reactions were con-
ducted settling initial pH at 6.0. Then, the experiments were carried
out ranging the current intensity (100, 200 and 300 mA) and
monitoring the TOC over the reaction time of textile wastewater
(Fig. 1). As observed, a faster TOC decay can be observed up to
45 min for all current intensities used, suggesting the electro-
chemical treatment conditions are conducive to the oxidation of
the organic pollutant in more simple forms. For the different cur-
rent intensities studied, the removal efficiency obtained after
45 min were: 75; 71 and 75%, for 100, 200 and 300 mA, respectively,
and after 180 min were: 80; 80 and 82%, for 100, 200 and 300 mA,
respectively. In order to work at low power consumption on the
oxidation treatment, the best result seems to be on condition using
12.5 mA cm2 for 45 min, in the other hand, the top mineralization
was reached using 37.5 mA cm2 for 180 min. At the beginning,
under higher current density (37.5 mA cm2) the TOC decreased
exhibiting an exponential decay with respect to time, suggesting
that the TOC oxidation is under mass-transport control. EO exper-
iments carried out by (Chatzisymeon et al., 2006) (stainless steel
cathode and titanium anode covered by a thin film of tantalum,
platinum and iridium, 4% salinity, pH at 9.5, COD0 of 440 mgO2 L1),
achieved a final COD reduction for the real effluent at 29, 34 and
39% using current intensity of 5, 10 and 20 A, respectively, and in
this work electrochemical oxidation achieved an interesting value
of 82% at 0.3 A, which means low power consumption.
In this work, all kinetics shows similar kinetic profiles (Fig. 1),
and the TOC degradation data could be fitted using a pseudo-first-
order kinetic model. The results shows an reaction period charac-
terized by an initial fast degradation rate for I ¼ 100 mA (k ¼ 0.0021
min1; ro ¼ 0.0046 mg min1 L1; R2 ¼ 0,99), I ¼ 200 mA
(k ¼ 0.0025 min1; ro ¼ 0.0049 mg min1 L1; R2 ¼ 0.98) and
I ¼ 300 mA (k ¼ 0.0026 min1; ro ¼ 0.0051 mg min1 L1;
R2 ¼ 0.98). The pseudo-first-order kinetic constant k increases with
increasing current intensity. Other than the early stages of the re-
action, the conditions employed in this study does not seem to be
critical to TOC removal since a major quantitative abatement could
be achieved within 45 min of reaction.
For major applications, energy consumption is an important
factor in valuing the treatment capability. In this work, the specific
energy consumption Esc (kWh$kg1 TOC), was calculated using Eq.
(2).
Ecell :I:Dt
Esc ¼ (2)
1000:V:DTOC
where Ecell is the average cell voltage (V), I is the applied current
(A), Dt is the duration of the electrolysis (h), V represents the vol-
ume of feed wastewater (m3), and DTOC results from the removed
TOC during the time Dt (kg m3).
Based on Eq. (2), the specific energy consumption obtained in
the treatment were 52.4; 102.2 and 149.5 kWh kg1 TOC for the
applied currents of 100; 200 and 300 mA, respectively. As expected,
the increasing of current intensity improved the TOC removal and
that could achieve higher TOC oxidation kinetics. The reason for
this behavior is that treatment conditions can effectively overcome
the mass transport limitation of organics for the case of OH radical
mediated oxidation. In different operational conditions to treat real

Table 4
Percentages of turbidity and color removal, and [TOC]/[TOC]0 ratio for samples at pH ¼ 8.0 and coagulant concentration at 20 mg L1.

pH ¼ 8.0; [coagulant] ¼ 20 mg L1 Flocculating concentration (mg L1) % turbidity reduction [TOC]/[TOC]0 % color removal

76.7 95.3 0.37 92.2

153.3 88.1 1.27 60.9
230.0 88.5 1.01 85.7
 N.H. Torres et al. / Chemosphere 236 (2019) 124309 5

Fig. 1. TOC removal rate as a function of treatment time. Conditions: DSA electrode and I ¼ 100 mA ( ); DSA electrode and I ¼ 200 mA ( ); and DSA electrode and I ¼ 300 mA
( ); All samples at T ¼ 23 ± 1  C and pHi ¼ 6.0.

textile wastewater (60 mA cm2; pH ¼ 2.0; [NaCl] ¼ 3 g L1, elec-

trolysis times of 3 h, and using a bipolar boron-doped diamond
electrode) (Zou et al., 2017) reported a specific energy consumption
of 11.1 kWh kg1 COD.
The use of a DSA electrode also promoted COD abatement,
because the use of both non-active (Ling et al., 2016) and active
(Basha et al., 2012) anodes allows achieving the complete decol-
orization indifferently. Additionally, the dimensionally stable anode
containing ruthenium (DSA® e RuO2eTiO2) might be another
important electrode material for the pollutants removal due to its
chemical stability, low cost and long lifetime (Aquino et al., 2014).
At 100, 200 and 300 mA were achieved 78, 80 and 82% of total
organic carbon removal, as mentioned by (Raju et al., 2009), at high
current densities, bubble density increases resulting in improved
upward momentum of bubble flux and it favors the suspended
solids removal by flotation. As shown by (Raju et al., 2009), current Fig. 2. Percent IC5072h for R. subcapitata exposed to the untreated and treated
intensity at 2717 mA cm2 achieved higher COD abatement, which (CF þ EO/DSA, I ¼ 300 mA) samples.
was 80% if compared with current intensities at 1089 and 3,792,
that was 60 and 50%, respectively. In this work the best COD
removal achieved was 82% at 3 mA cm2. The ecotoxicity decrease was proportional to the chemical
According to the possible reaction mechanisms at the anode, the parameter TOC decrease (Fig. 1), confirming the remediation power
direct anodic oxidation rate will increase with increasing current effectiveness of the treatment applied. Regarding the inhibition
density if the pollutants can transport efficiently to the anode values, it is clear that the combined treatment proposed in this
surface (Wang et al., 2009). study achieved a positive response on toxicity elimination com-
pounds present in the textile wastewater sample used. In absence
of precise analysis from this textile wastewater samples, this study
3.5. Ecotoxicological tests can only hypothesize that the toxicity of the untreated sample
could be due, in parts, to azo dyes used in this industry and present
3.5.1. Raphidocelis subcapitata bioassay in the wastewater collected. In fact, azo dyes and/or their byprod-
According to Croce et al. (2017), algae are one of the main ucts were reported by several authors related at negative impacts
aquatic ecosystems components as oxygen producers, for their self- (Øllgaard et al., 1998; Mohan et al., 2002; Ferraz et al., 2011).
purifying activity in rivers and lakes and as staple food for primary
consumer organisms. Green algae R. subcapitata are ubiquitous in 3.5.2. Lactuca sativa bioassay
freshwater ecosystems and often used as a phytoplankton model. In The toxicological results observed at dilution effects of treated
this study was used the 72 h growth inhibition assay with (CF þ OE/DSA, I ¼ 300 mA) and untreated samples on the germi-
R. subcapitata to investigate the chronic toxicity of the treated and nation are shown in Fig. 3 and in Table 5. The L. sativa germination
untreated samples for both limit test and concentration-response was totally inhibited, with respect to the control, when the seeds
studies. Fig. 2 shows the IC5072h values obtained for treated were exposed to untreated textile wastewater samples. Their in-
(CF þ EO/DSA, I ¼ 300 mA) and untreated samples tested. The re- hibition slightly decreased with the dilution effects. While the
sults were considered potentially toxic based on growth rate treated textile wastewater samples (CF þ OE/DSA, I ¼ 300 mA)
response. Apparently, the bioassay with the alga test was most presented a lower inhibition on germination with a remaining
sensitive in assessing eventual toxicity caused by this kind of toxicity level, indicating that the combined treatment removed a
wastewater. major part of soluble toxic compounds.
6 N.H. Torres et al. / Chemosphere 236 (2019) 124309
Fig. 3. Germination rate of lettuce seeds on untreated and treated (CF þ OE/DSA, I ¼ 300 mA) samples.
In this study, the terminology presented by Vilar et al. (2018) for
evaluating the development degree of lettuce seeds (L. sativa) in
toxicity tests was considered. Results of GR lower 40% indicate a
sensitivity to seed inhibition, values between 40 and 80% suggest a
slight inhibition, values between 80 and 120% are not considered
significant and values over to 120% are considered as increasing
stimuli. The inhibition results of treated and untreated samples are
shown in Table SM-5. All values obtained for treated textile
wastewater were classified within of not significant to inhibition.
The combined treatment used in this study minimized the toxic
compounds present in the textile wastewater samples, as can be
observed by the ecotoxicological response.
The dissolved salts concentration can cause very negative hydric
potentials, which influence the water absorption by the seeds. In
this textile wastewater samples, the high value of conductivity
(4640 mg L1) may negatively affected the sequence of events
related to the lettuce seeds germination process.
In this context, it was verified that L. sativa is a fundamental test
organism to indicate the toxic level of the textile effluent, and the
lettuce seeds ecotoxicological response variability can be linked
with the chemical composition of the samples.
4. Conclusions
This study showed that the combination of coagulation-
flocculation and electrochemical oxidation was able to remove
TOC and turbidity and reduce the toxicity of textile wastewater
samples. The initial TOC of 734 mg L1 was reduced to
132.12 mg L1 (efficiency of 82%) after CF and electrochemical
oxidation using DSA as electrode. When the R. subcapitata and
L. sativa were used as test organism, a consistent indicator of the
detoxifying capacity of the samples treated by a combined process
(CF þ EO) can be verified.
Acknowledgements
The authors would like to thank CAPES (Coordination for the
Improvement of Higher Education Personnel), CNPq (National
Counsel of Technological and Scientific Development), and Fapitec
for their financial support.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.chemosphere.2019.07.040.
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