Environ Sci Pollut Res
DOI 10.1007/s11356-016-6157-8
AOPS: RECENT ADVANCES TO OVERCOME BARRIERS IN THE TREATMENT OF WATER, WASTEWATER AND AIR
Optimized treatment conditions for textile wastewater reuse
using photocatalytic processes under UV and visible light sources
Maria Clara V. M. Starling 1 & Luiz Augusto S. Castro 1 &
Rafaela B. P. Marcelino 1 & Mônica M. D. Leão 1 & Camila C. Amorim 1
Received: 27 November 2015 / Accepted: 20 January 2016
# Springer-Verlag Berlin Heidelberg 2016
Abstract In this study, photo-Fenton systems using visible
light sources with iron and ferrioxalate were tested for the
DOC degradation and decolorization of textile wastewater.
Textile wastewaters originated after the dyeing stage of
dark-colored tissue in the textile industry, and the optimi-
zation of treatment processes was studied to produce water
suitable for reuse. Dissolved organic carbon, absorbance,
turbidity, anionic concentrations, carboxylic acids, and
preliminary cost analysis were performed for the proposed
treatments. Conventional photo-Fenton process achieved
near 99 % DOC degradation rates and complete absor-
bance removal, and no carboxylic acids were found as
products of degradation. Ferrioxalate photo-Fenton system
achieved 82 % of DOC degradation and showed complete
absorbance removal, and oxalic acid has been detected
through HPLC analysis in the treated sample. In contrast,
photo-peroxidation with UV light was proved effective only
for absorbance removal, with DOC degradation efficiency
near 50 %. Treated wastewater was compared with reclaimed
water and had a similar quality, indicating that these processes
can be effectively applied for textile wastewater reuse. The
results of the preliminary cost analysis indicated costs of
0.91 to 1.07 US$ m−3 for the conventional and ferrioxalate
photo-Fenton systems, respectively.
Responsible editor: Bingcai Pan
* Camila C. Amorim
camila@desa.ufmg.br
1
Department of Sanitary and Environmental Engineering,
Universidade Federal de Minas Gerais, Av. Antônio Carlos, 6627,
Belo Horizonte, Minas Gerais 31270-901, Brazil
Keywords Textile wastewater . Water reuse . Advanced
oxidation processes . Photo-Fenton . Visible light irradiation
Introduction
The textile industry is generally regarded as pollution in-
tensive, not only because of the quantity of water expended
by the processes but also the variety of aesthetic and envi-
ronmental problems it could cause (Alaton et al. 2002).
Wastewater is one of the major environmental aspects as-
sociated with the textile industry that can be generated
during stages of bleaching, dyeing, rinsing, washing, and
finishing (dos Santos et al. 2007; Lu et al. 2010; Manenti
et al. 2014). Therefore, the wastewater generated differs
significantly in respect of chemical, color, and organic con-
tent (Verma et al. 2012).
Among the different types of wastewater generated in the
textile industry, dyeing wastewater is of major concern
(Módenes et al. 2012; Vajnhandl and Majcen Le Marechal
2005). The capacity of dye adsorption onto fibers varies sig-
nificantly according to the type of fiber, machinery, and dye
properties; and the percentage of dyes lost in wastewater
ranges from 10 to 50 % (Carneiro et al. 2007; Forgacs et al.
2004; Khandegar and Saroha 2013). Dyeing wastewater con-
sists of a complex mix of dyes, salts, and other chemicals such
as surfactants, and it is estimated that approximately 80 % of
the salts and 90 % of the color are released from the process
(Lu et al. 2010).
It is known that most dyes used in the textile industry are
water-soluble and non-biodegradable because of their recalci-
trant compounds, which are often toxic to the environment
and could be carcinogenic (dos Santos et al. 2007; Verma
et al. 2012; Vilar et al. 2011). Consequently, the conventional
biological treatment of most textile wastewaters is usually

ineffective (Rodrigues et al. 2013). Therefore, the treatment of
this wastewater should be combined with, or even replaced by,
other types of treatment, if the intention is water reuse or even
discharge (Ahmad and Hameed 2010).
The advanced oxidation processes (AOPs) are alterna-
tives for the treatment of textile wastewater and aim at the
production of hydroxyl radicals (HO•), which are extreme-
ly strong non-selective oxidant species (Eh = 2.8 V) that
are able to mineralize recalcitrant compounds, such as
dyes, in ideal conditions, to CO2, water, and inorganic ions
(Blanco et al. 2012). Moreover, AOPs are considered ver-
satile, since HO• can be formed in different systems, such
as H2O2/UV, O3/H2O2, Fe/H2O2, Fe/H2O2/UV, and others,
including process under visible light (Gernjak et al. 2003).
Using AOPs to treat dyeing textile wastewater could be a
good choice because of the reduced flow that improve seg-
regation and reuse, compared with other wastewater lines
in the textile industry. A number of European industries have
already explored the use of AOPs to improve the water reuse
system. The application of AOPs would be an alternative to
treatment system, where the non-concentrated stream of water
is separated and treated for reuse (Arslan-Alaton et al. 2009;
Vajnhandl and Valh 2014).
Various AOPs have been tested for the treatment of tex-
tile wastewater, such as ozonation (O3) (Constapel et al.
2009), photo-peroxidation (H 2 O 2 /UV-C) (Rosa et al.
2015), photocatalysis (TiO2/UV-A) (Alaton et al. 2002),
and Fenton systems (Rodrigues et al. 2013; Blanco et al.
2014). Good results for the removal of color and organic
matter were obtained by these systems. However, most of
the studies have had to use synthetic textile wastewater
because of the heterogeneity of the real wastewater
(Rodrigues et al. 2013; Doumic et al. 2015; Grčić et al.
2011; Hernández-Rodríguez et al. 2014).
In the Fenton systems, the HO· radical is produced
when hydrogen peroxide (H2O2) is exposed to iron salts,
as shown by Eqs. 1 and 2 (Tarr 2003). When exposed to
UV or UV-Vis light, the Fenton system is known as photo-
Fenton. Additionally, there is a secondary route for radical
formation in the photo-Fenton systems which is faster than
that which occurs in the Fenton systems and increases the
number of oxidative species formed, as illustrated by
Eqs. 3 to 6 (Tarr 2003). Consequently, irradiated Fenton
systems are usually more effective than non-irradiated
systems.
Fe2þ þ H2 O2 → Fe3þ þ HO• þ OH− ð1Þ
Fe3þ þ H2 O2 → Fe2þ þ Hþ þ HO•2 ð2Þ
FeðIIIÞOH3þ þ hv → Fe2þ þ HO• ð3Þ
Fe3þ þ H2 O2 → FeðOOHÞ2þ ð4Þ
Environ Sci Pollut Res
FeðOOHÞ2þ ↔ HO•2 þ Fe2þ ð5Þ
Fe3þ ðL− Þ þ hv↔ Fe2þ þ L− ð6Þ
Photo-Fenton systems are considered the most effective
treatment for the decolorization of wastewater and, addition-
ally, are particularly energy efficient (Gogate and Pandit
2004). Employing solar radiation could be a low-cost alterna-
tive and represents an advantage of the photo-Fenton systems.
As the ferric iron-water complexes can use a fraction of the
solar radiation spectrum (Dias et al. 2014), the solar photo-
Fenton process is particularly efficient for the discoloration
and DOC degradation of wastewaters (Manenti et al. 2015;
Vilar et al. 2011).
In addition, various iron species (Fe2+, Fe3+, Fe(OH)2+,
Fe-radical, etc.) may act as catalysts in photo-Fenton sys-
tems, increasing the versatility of the process. The forma-
tion of each of these iron species varies according to sys-
tem pH and molar ratio (Souza 2014). When Fe2+ is used
as a catalyst, pre-adjusting the pH to ≈ 3 is required, as,
once high, the pH will affect the course of the reactions
and could cause catalyst precipitation (Wang et al. 2008).
One of the alternatives is using ferrioxalate ([Fe(C2O4)3]3−)
(Dias et al. 2014). According to iron speciation diagrams
(Souza et al. 2014), in the absence of oxalate, Fe(OH)2+,
the most photo-reactive ferric ion complex, is present in
solution in high concentrations from pH 3 to 5. Whereas
in the presence of ferrioxalate complexes, Fe(OH)2+ is
present at higher concentrations of pH 7. However, higher
concentrations of oxalate are necessary to guarantee effi-
cient DOC removal rates at near-neutral pH (Soares et al.
2015). In addition, ferrioxalate complex has higher light
spectrum absorbance and reduces the absorption of light
by the other chemical compounds. In this way, the efficien-
cy of the UV-Vis photo-Fenton and solar photo-Fenton
treatments is increased (Manenti et al. 2015).
For both the photo-Fenton and the photochemical systems,
the concentrations of the reagents (H2O2; Fe2+) should be
carefully planned, as the optimal conditions could vary
depending on the properties of the wastewater. In addition,
extremely high concentrations of H2O2 could lead to the con-
sumption of the hydroxyl radical (known as the scavenger
effect), which lowers the degradation rate (Tarr 2003).
Therefore, to achieve the best results, the optimum conditions
should be established.
The cost effectiveness of the technology is one of the
main concerns of decision-makers in the selection of pro-
posed treatment systems (Kalbar et al. 2013). Therefore,
the initial investment expenses, the cost of the reagents,
and the operational costs have to be considered when a
specific treatment is proposed.
The present study is aimed at the optimization of the treat-
ment conditions for the different photo-Fenton systems, under
Environ Sci Pollut Res
visible light radiation, employed to treat textile wastewater,
with the aim of producing suitable reuse water.
Materials and methods
Textile wastewater
The wastewater used for this study was collected from a
textile mill that, on average, produces 260 tons of finished
fabric per month and uses approximately 26,000 m3 of
water. In this mill, fresh water is used for the stages of
dyeing, rinsing, and finishing. After dyeing and rinsing
the dark-colored tissue, the high chemical and color con-
tent precludes reusing the water in the production process.
Thus, rinsing wastewater, mixed with the dyeing waste-
water, flows directly to an industrial wastewater treatment
plant (WWTP), where the activated-sludge biologic treat-
ment method is applied (Fig. 1). However, the presence of
color in the discharged wastewater is currently a major
problem regarding the WWTP. Reclaimed water is the
wastewater which is treated after the dyeing stage of
light-colored tissue and is returned to the process to dye
dark-colored tissue.
This present work focuses on the production of reuse water
and, therefore, explores the treatment of the textile wastewater
before it flows to the WWTP, with a flow rate equivalent to
10 m3 h−1. Two aliquots of 20 L each were collected during
10 h of production (2 L of samples per hour) over two con-
secutive production days.
Fig. 1 Scheme of water and wastewater flow in the textile plant where wastewater was collected
Analytical procedures
The textile wastewater and the reclaimed water were charac-
terized for chemical oxygen demand (COD, mg O2 L−1) by
the colorimetric method (APHA et al. 2005), for pH (potenti-
ometric method), for the total dissolved carbon (TDC; mg
L−1), and the dissolved organic carbon (DOC; mg L−1) and
the inorganic carbon (IC; mg L−1) by a total organic carbon
analyzer (Shimadzu, TOC-V CPN), after filtration with nitro-
cellulose membrane 0.45 μm (Sartorius). Filtration was per-
formed to all of the samples (non-treated and treated) using
this same membrane in order to eliminate possible interfer-
ences in the DOC and absorbance analysis. The turbidity
(NTU) (HACH 2100AN) and maximum absorbance
− λ = 425 nm (PerkinElmer Lambda XLS, 200–900 nm) were
also evaluated. The ionic concentrations of chloride (Cl−),
nitrate (NO3−), nitrite (NO2−), phosphate (PO43−), and sulfate
(SO 4 − ) were determined by ion chromatography (850
Professional IC Metrohm) (APHA et al. 2005). After the pro-
posed treatments, the textile wastewater was again character-
ized using the same parameters.
Generation of carboxylic acids—such as oxalic acid,
malic acid, formic acid, acetic acid, propionic acid, citric
acid, and butyric acid—was analyzed and quantified by
ion-exclusion high-performance liquid chromatography
(HPLC) (Perkin Elmer Series 200, fitted with a Bio-Rad
Aminex HPX-87H, 300 mm × 7.8 mm, column at 35 °C)
and setting the pulsed amperometric detector (PAD) at
λ = 210 nm. Samples (20 μL) were injected into the
HPLC, with a mobile phase of 4 mM at 0.6 mL min−1,
as described by Moreira et al. (2013).

Experimental procedures and lab-scale photo-reactor
Photo-Fenton and photochemical experiments were conduct-
ed in a laboratory-scale photo-reactor (Fig. 2). The interior
glass container of the reactor has a total volume of 0.9 L
(10-cm diameter and 15-cm height), and the temperature dur-
ing the experiment was kept constant at 25 °C by the attached
cooling system. Photochemical experiments were conducted
by using UV light, for which a mercury vapor lamp (12 W),
with a quartz-covered light bulb, was used. For the photo-
Fenton experiments applying visible light, a similar lamp
(Hg; 12 W) covered by a borosilicate glass was used. Iron
was added as FeSO4·7H2O for all the photo-Fenton experi-
ments. For the systems using Fe2+, the pH was pre-adjusted to
3 by adding sulfuric acid (0.1 M) (Robinson et al. 2001). In
addition to iron sulfate, oxalic acid at a concentration of 80 mg
L−1 was added for the ferrioxalate photo-Fenton systems
(pH = 5) with different iron concentrations (4; 12 and 20 mg
L−1 of Fe2+ for 80 mg L−1 of H2C2O4). Ferrioxalate complexes
were formed in situ under agitation for 15 min, in the dark,
before the beginning of reaction.
Optimizing treatment conditions: factorial design
In order to determine the optimal reaction conditions, a
factorial design was performed using MiniTab 17. In this
two-factor experimental design, Fe2+ and H2O2 were tested
in three different concentrations (4, 12, 20 mg L−1 and 100,
300, and 500 mg L−1, respectively) which were classified
in three different levels (−1; 0; 1). The choice of the initial
concentrations for each reagent was based on the organic
matter content of the wastewater and the information
Fig. 2 Representative scheme of the photo-reactor used in the tests.
Adapted from Amorim et al. (2013)
Environ Sci Pollut Res
gleaned from the literature review. Table 1 shows all of
the conditions tested for both conventional and ferrioxalate
photo-Fenton systems. The response variable was set to
DOC removal (%). Suitability of the factorial design was
performed at a 95 % confidence interval.
All of the reactions were conducted for 120 min. The
experiments were evaluated by DOC removal analysis and
absorbance removal at 425 nm, the highest absorbance peak
in the visible spectrum for this textile wastewater sample.
Reactions were stopped by the addition of a catalase enzyme
solution (Synth) (460 mg L−1 in phosphate buffer 0.04 M) in a
ratio (catalase solution/sample) of 0.05:1 after adjusting the
pH to 7 in order to remove the residual hydrogen peroxide.
The DOC values of this reagent were appropriately eliminated
from the samples DOC final values (Poole 2004).
For the photochemical reaction, the H2O2 concentration
applied to the system achieved the best results in the photo-
Fenton experiments. In addition, six control systems were
used, namely, photolysis (UV light only), coagulation (iron
chloride Fe3+, 20 mg L−1), UV-Vis/H2O2 (500 mg L−1),
Fenton (20 mg L −1 of Fe2+; 500 mg L −1of H2O 2) and
UV-Vis only.
Preliminary operational cost analysis
A preliminary cost analysis was performed considering only
operational costs related to reagents consumption and energy,
necessary to treat, proportionally, 1 m3 of textile wastewater,
and the optimized treatments in laboratory scale. The reagent
prices listed on Table 2 was based on ICIS Chemical Pricing
(ICIS 2015), and the energy cost was based on Mahamuni and
Adewuyi 2010 (0.08 US$ kWh−1). The reaction time consid-
ered for each one of the processes was that required to obtain a
quality similar to that of the reclaimed water (40 min for both
photo-Fenton systems and 2 h for the H2O2/UV), which is
currently reused in this industry (ICIS 2015, Mahamuni and
Adewuyi 2010).
Chemical reagent concentrations applied for pH adjust-
ment to 3 or 5 were calculated considering wastewater initial
Table 1 Experimental conditions tested according to factorial design:
reagents used and different levels (−1 lowest concentrations, 0 central
points, and +1 highest concentrations) and conditions tested
Condition Chemical (mg L−1) Level
H2O2 Fe2+ H2O2/Fe2+
1 100 4 −1:−1
2 100 20 −1:+1
3 300 12 0:0
4 500 4 1:−1
5 500 20 +1:+1
Environ Sci Pollut Res

Table 2 Reagent prices

according to the Chemicals Price (kg)
international chemical US$
supplier and energy costs H2SO4 0.085
NaOH 0.76
H2O2 1.10
FeSO4·7H2O 0.21
H2C2O4 3.00
Resources US$
Energy (kWh)a 0.08
a
(Mahamuni and Adewuyi 2010)

pH (8.2) according to pH equation (pH = log[H+]). Energy

costs were calculated for 40 min of reaction for both photo-
Fenton systems and for 2 h of reaction for the UV/H2O2 sys-
tems, accordingly to DOC removal efficiency required for
treated wastewater reuse, and considered a 12-W lamp in a
photo-reactor of 0.9 L (13.3 kW in 1 m3).

Results and discussion

Optimizing treatment conditions

Following a factorial design, the photo-Fenton experiments

were carried out for treating the textile wastewater. Results
indicate that the optimum conditions differed for each of the
tested systems, as indicated by the response surface graphs
(software Statistica 10) (Fig. 3), H 2 O 2 /UV-Vis/Fe 2+
(Fig. 3a), and H2O2/UV-Vis/Fe3+ (Fig. 3b).
For the conventional photo-Fenton system (pH 3), all the
tested conditions obtained a DOC removal efficiency rate
higher than 94 % (Fig. 3a). The optimal condition was 20 mg
L−1 of Fe2+ and 500 mg L−1 of H2O2 (+1; +1), which removed
100 % DOC. However, the condition using the lowest
concentrations of both reagents (−1; −1) also showed a high
efficiency rate for DOC removal (94 %). Therefore, the type
of treatment chosen has to be evaluated to reduce the con-
sumption of reagents and, consequently, reduce costs.
Residual hydrogen peroxide was lower than 0.5 mg L−1 for
Fig. 3 Surface response graphs for dissolved organic carbon (DOC)
all the conditions tested, and it is likely that its consumption reduction by conventional photo-Fenton system (a) on pH 3 and
was related to hydroxyl radicals formation rather than second- ferrioxalate photo-Fenton ferrioxalate system (b) on pH 5
ary routes of degradation of H2O2 which do not lead to radical
production (Tarr 2003), once DOC percentage removals were
>90 % for all of the conditions tested. 0.9 mg L−1. When the highest concentration of both reagents
Although photo-Fenton conventional system showed very was applied (+1;+1), a reduction rate of DOC of 76 % was
stable DOC removal results, regardless of reagents concentra- obtained, and the residual hydrogen peroxide was 15 mg L−1,
tions, the DOC removal results obtained for photo-Fenton indicating process inefficiency. This result could be attribut-
ferrioxalate system showed significant differences (Fig. 3b). able to an excess of reagents being present in the system.
In this system, a greater efficiency rate (82 %) of DOC reduc- Therefore, the scavenger effect had probably taken place in
tion was obtained when using 20 mg L−1 of Fe3+ and 100 mg this condition (Eqs. 8 and 9) (Tarr 2003) as previously de-
L−1 of H2O2 (+1; −1), while the residual hydrogen peroxide was scribed in other Fenton and Fenton-like systems (Amorim

et al. 2013). These results demonstrate the economic and tech-
nical advantages of testing different conditions for treatment
optimization.
HO• þ H2 O2 →HO•2 þ H2 O ð8Þ
HO•2 þ HO• →H2 O þ O2 ð9Þ
The main difference between the processes is that a higher
concentration of iron is necessary in the ferrioxalate system.
On the other hand, the pH for this process is near neutral.
Efficiency analysis of the proposed treatments
Figure 4 shows the DOC reduction, absorbance removal
(λ = 425 nm), and the hydrogen peroxide consumption for
the optimal conditions of the photo-Fenton systems (4 mg
L−1 of Fe2+ and 500 mg L−1 of H2O2, 20 mg L−1 of Fe3+,
and 100 mg L−1 of H2O2) and the controls tests.
Kinetics results (Fig. 4) show that absorbance removal
takes place faster than does DOC degradation, since the
Fig. 4 DOC, absorbance
removal, and hydrogen peroxide
consumption (percentage) for op-
timal photo-Fenton conditions,
photo-peroxidation, and controls
Environ Sci Pollut Res
chromophore groups were initially broken down into smaller
organic molecules, which are easier to degrade, as was also
reported by other authors (dos Santos et al. 2007; Rodrigues
et al. 2013).
In the UV/H2O2 system, 88 % of the H2O2 initial concen-
tration was consumed after 10 min of reaction, remaining
12 mg L−1 of H2O2. The degradation of chromophore groups
was verified, thus removing color from textile wastewater, but
not necessarily leading to high rates of mineralization proba-
bly due to the formation of intermediates. In this case, the
photolysis may have influenced the degradation of formed
intermediates which are easier to degrade than the original
compounds and may have been broken by UV light, even in
low concentrations or absence of H2O2. The experiment
which used only UV agrees with these results and presents
40 % of DOC degradation.
For photo-Fenton systems (Fig. 4), reactions show two
different stages which are in agreement with H2O2 consump-
tion pattern. The first stage is defined as the 15 initial minutes
of high DOC (74 % with Fe2+ and 62 % with Fe3+) and color
Environ Sci Pollut Res

(95 % for both) removal rates and during which H2O2 was
almost totally consumed (94 %). In the second stage, discol-
oration and DOC removal continue in a slower rate probably
due to the reduction of Fe(OH)3+ species into hydroxyl
radicals in the presence of light (Eq. 3) and is increased by
photolytic reactions and reactions mediated by weaker active
radicals, formed from inorganic 7ions (i.e., Cl−; PO43−, SO42−,
and CO32−), which are generated from the oxidation of organ-
ic compounds originally present in textile wastewater in the
first stage of reaction (Kalsoom et al. 2012). Additionally,
since these ions are also present in the non-treated textile
wastewaters, the formation of these reactive radicals is prob-
ably also taking place in the H2O2/UV system which also
contributes to further removal of DOC after H2O2 total con-
sumption in this system.
On the other hand, according to some authors, in the ab-
sence of hydroxyl radicals, iron compounds could function as
absorbers, leading to coagulation (Soon and Hameed 2011;
Wang et al. 2008). This could explain the 40 % of DOC deg-
radation and absorbance removal when Fe3+ was used alone.
In the Fenton system, DOC degradation occurs to a certain
extent only and the removal of DOC is only approximately
50 %. Furthermore, if the wastewater submitted to coagulation
or Fenton were to be reused in the dyeing process, the organic
matter still present in the wastewater could damage the quality
of the final product. Consequently, water reuse was limited to
the wastewater treated with the photo-Fenton systems.
Since, both photo-Fenton systems achieve high efficiency
of DOC and color removal in different conditions (H2O2 and
iron concentrations), a cost analysis would be particularly im-
portant. Moreover, presented results suggest that this waste-
water could be treated with the solar photo-Fenton systems,
since the UV-Vis artificial light spectrum was proved
successful. Numerous authors have indicated solar photo-
Fenton system as efficient for treating textile wastewater
(Vedrenne et al. 2012; Vilar et al. 2011). The solar photo-
Fenton treatment is particularly appealing as the energy costs
for treatment could be reduced (Carra et al. 2013; Monteagudo
et al. 2012). The installation costs of the solar photo-Fenton
system certainly have to be taken into account to evaluate its
economic applicability (Rodrigues et al. 2013).
The characterizations of textile wastewater, reclaimed wa-
ter, and the treated wastewater are presented in Table 3. A
comparison of the characterization of photo-Fenton treated
wastewaters and the reclaimed water parameter values
indicates similarities between the samples. Therefore, the
wastewater treated by the photo-Fenton systems could be con-
sidered as suitable for reuse in the production process.
Furthermore, it was found that the quality of the wastewater
treated with both photo-Fenton systems and photo-
peroxidation in this research was within the limits prescribed
by the European textile sector for reuse water in the finishing
and dyeing processes (Vajnhandl and Valh 2014).
It is clear that DOC degradation is reflected by the COD,
TDC, and the DOC values after treatment. It is important to
note that the phosphate concentrations increased after apply-
ing both photo-Fenton systems. High PO43− concentrations
are probably generated from oxidation of auxiliaries applied
to the textile process in different stages of production such as
bleaching, mercerizing, and dyeing (dos Santos et al. 2007),
including surfactants compounds, such as phosphorous de-
tergents which are commonly used to release non-bonded
dyes from recently dyed fabric and other chelating agents
that contain phosphorous in their organic structures
(Alaton 2002; Duomic 2015). Phosphate ions are formed
after their oxidation and may remain in solution, complex

Table 3 Physicochemical
characterization of textile Parameter Textile Reclaimed Conventional Ferrioxalate H2O2/
wastewater before and after wastewater water photo-Fenton photo- UV
proposed treatments in optimum Fenton
conditions
pH 8.2 7 7a 7a 7a
−1
COD (mg O2 L ) 242 27 30 36 40
Turbidity 25.6 5 2.3 1.3 4.1
TDC (mg L−1) 60.5 34 7.1 22.6 30.6
DOC (mg L−1) 41.2 10 6 10.4 13.3
IC (mg L−1) 19.3 23.17 1.1 12.1 17.3
Cl− (mg L−1) 66.5 165.1 28.4 32.4 29
NO2− (mg L−1) 28.2 21.3 ND 37.5 ND
NO3− (mg L−1) 44.2 44.4 42.3 70.4 37.7
PO43− (mg L−1) 58 77.1 278.5 385 ND
SO4− (mg L−1) 26.7 35.2 118.8 37.5 39.7

ND not detected (conventional 4 mg L−1 of Fe2+ and 100 mg L−1 of H2O2, ferrioxalate 20 mg L−1 of Fe3+ and
100 mg L−1 of H2O2, photo-peroxidation 100 mg L−1 of H2O2)
a
Adjusted

with Fe2+ or generate phosphate radicals, usually in the
presence of UV light (Kalsoom et al. 2012). The phosphate
concentration was found lower after the conventional
photo-Fenton system than it was after the ferrioxalate
photo-Fenton system. This could be explained by the for-
mation of Fe-PO43− complexes (Vilar et al. 2012) in the
conventional system, which precipitate with iron. In the
beginning of reaction, PO 4 3− concentration was low
(58 mg L −1 ) and H 2 O 2 was still present, thus photo-
Fenton reactions were probably more likely to occur than
the formation of these complexes and catalytic activity was
not reduced. These complexes were not formed in the photo-
Fenton ferrioxalate system, in which the Fe-oxalate com-
plexes were present and stable. Therefore, PO43− remained
in solution in the aqueous media. For the H2O2/UV system,
the absence of PO43− ions in the treated sample is probably
due to the transformation of these ions into PO4•2− which
occurs only in the presence of UV irradiation. Then, PO4•2−
reacts with water with the formation of HPO42− and HO• lead-
ing to further oxidation (Rosso et al. 1998).
Furthermore, the post-treatment sulfate concentrations
were higher in the conventional photo-Fenton system.
This is due to the addition of a significant volume of sul-
furic acid for pre-adjusting the pH to 3, while a smaller
volume of sulfuric acid was added in the ferrioxalate sys-
tem (pH = 5).
Fig. 5 HPLC of textile wastewater and treated wastewater samples for
the identification of generated carboxylic acids. a Oxalic acid control at
0.1 mol L−1. b Non-treated textile wastewater. c Wastewater treated by
Environ Sci Pollut Res
Carboxylic acids analysis
An analysis of the generated carboxylic acids (Fig. 5) indicat-
ed that oxalic acid was the only remaining product of the
degradation of the textile wastewater after 120 min of reaction.
The first chromatogram shows the pure solution of oxalic acid
(Fig. 5a–Control). It is important to note that because oxalic
acid is a component of the additives applied in the textile
processes of bleaching and dyeing, this acid was detected in
the non-treated textile wastewater sample (Fig. 5b–Textile
Wastewater). All the samples show a small peak before the
oxalic acid peak, which represents the sulfate present in the
mobile phase.
Moreira et al. (2013) have detected the presence of four
distinct carboxylic acids when various AOPs were tested for
the degradation of an azo dye. The authors detected the initial
formation of the carboxylic acids, followed by their degrada-
tion. In the present work, final samples of each proposed sys-
tem were analyzed after 120 min of treatment; therefore, other
acids could have been formed and degraded during the reac-
tion. For the conventional photo-Fenton system, no remaining
oxalic acid was detected after 120 min of reaction (Fig. 5c–
H2O2/UV-Vis/Fe2+), validating the total DOC degradation ob-
tained by this treatment. For the ferrioxalate photo-Fenton
system (Fig. 5d–H2O2/UV-Vis/Fe 3+), which achieved a
DOC reduction rate of 82 %, oxalic acid was detected as
photo-Fenton conventional (visible light). d Wastewater treated by photo-
Fenton ferrioxalate (visible light). e Wastewater treated by H2O2/UV
Environ Sci Pollut Res
expected. Note that for the H2O2/UV system (Fig. 5e–H2O2/
UV) during which 60 % of DOC was reduced, oxalic acid was
detected at a higher intensity, even higher than in the untreated
wastewater (Fig. 5b). The increase in the oxalic acid peak
could be explained by the fact that this acid is one of the
ultimate products of degradation, as was also observed by
other authors (Moreira et al. 2013; Salazar et al. 2011).
Preliminary cost analysis
Table 4 shows the costs calculated for each of the proposed
treatments. Energy costs correspond to 70 % of the total treat-
ment costs for the photo-Fenton systems and 95 % for the
H2O2/UV. Among the three alternatives, H2O2/UV is the most
expensive treatment (2.24 US$ m−3), due to the time of artifi-
cial light operation (2 h) in order to achieve 63 % DOC
removal, while photo-Fenton systems lead to > 90 % DOC
degradation in 40 min. For the photo-Fenton systems, costs
were calculated to be higher for the ferrioxalate system (1.07
US$ m−3) due to the price of the oxalic acid, which increased
the total cost of this treatment. Consequently, considering op-
erational costs only, it would be less costly to use Fe2+ (0.91
US$ m−3), even if all of the costs related to the pH adjustment
are considered. Once reactor material corrosion must be
prevented when working on pH 3, resources used to build this
reactor will probably be more costly. However, on the long-
term basis, costs related to conventional photo-Fenton appli-
cation will probably pay off faster than if ferrioxalate solar
photo-Fenton was to be applied.
The calculated treatment prices were either lower than the
prices indicated by other authors (Chong et al. 2012;
Mahamuni and Adewuyi 2010) or were consistent with the
operating costs observed in the European water reuse projects
(Vajnhandl and Valh 2014). The lower treatment costs we
obtained were only possible because of our resolve to use
lower concentrations of chemicals in order to improve the
cost-effectiveness of the treatments.
It is important to elucidate that these costs have been
raised based only on laboratory bench-scale experiments
Table 4 Operational treatment costs for each of the proposed photo-
Fenton systems in laboratory scale, calculated at international reagent and
energy prices
Proposed treatment Removal efficiency (%)
Absorbance removal DOC US$/m3
H2O2/UV-Vis/Fe2+ (100 mg L−1 100 98
H2O2/4 mg L−1 Fe2+)
H2O2/UV-Vis/Fe3+ (100 mg L−1 100 82
H2O2/20 mg L−1 Fe3+/80 mg
L−1 H2C2O4)
H2O2/UV (100 mg L−1 H2O2) 100 60
and that other costs may be considered such as system
installation, lamp and reactors maintenance, operation,
and safe storage of chemicals. In addition, the results
achieved for the photo-Fenton systems using visible light
also indicate that the conversion of the organic content of
textile wastewater to biodegradable carboxylic acids, CO2,
and inorganic ions could be possible when applying the
solar photo-Fenton system. Since the solar photo-Fenton
system utilizes sunlight, the treatment costs in respect of en-
ergy are reduced, which renders an economically feasible
treatment method to the industry. The potential for the appli-
cation of this treatment is increased in tropical countries, like
Brazil, where solar radiation is available throughout the whole
year (Marcelino et al. 2015). However, in order to certify that
solar photo-Fenton system will be effective, a solar reactor
must be properly designed according incident solar radiation
pattern, wastewater flow hydraulic conditions, and operational
conditions of the processes (batch or continuous) (Malato
et al. 2009).
Assuming that 80 % (8 m3 h−1) of the treated wastewater
could be reused after, applying the proposed optimized treat-
ment technologies of photo-Fenton would also reduce the cost
in respect of the water supply. If the local water supply price
was taken into account as 2.55 US$ m−3, it is estimated that up
to 20.4 US$ h−1 could be saved by the textile mill due to
treated wastewater reuse.
Conclusions
The results presented here show that the photo-Fenton systems
using visible light spectrum were able to achieve considerable
DOC degradation rates and complete absorbance removal of
real textile wastewater. The conventional photo-Fenton system
(pH 3) was shown to be more effective (99 % DOC degrada-
tion) than ferrioxalate system (pH 5) (82 % DOC degradation),
whereas H2O2/UV achieved 63 % DOC degradation. In all of
these systems, absorbance has been removed faster than DOC
due to degradation of chromophores. In addition, oxalic acid
has been shown to be one of the ultimate products of degrada-
tion before total conversion to water, CO2, and inorganic ions.
Physicochemical quality of photo-Fenton systems and UV/
H2O2 treated wastewaters was compared to reclaimed water,
indicating similarities among these waters and their potential to
Price be reused in the industry. Preliminary operational cost analysis
of the proposed treatments indicates costs amounting to less
than 1 US$ m−3 of wastewater for both photo-Fenton conven-
tional systems. Also, energy has been proved to be the factor
0.91
with biggest influence on total cost. Moreover, the high effi-
1.07 ciency of the bench-scale UV-Vis irradiated photo-Fenton sys-
tem for the treatment of textile wastewater suggests that the
solar photo-Fenton system could be a viable alternative for the
2.24
treatment of textile wastewater and production of water reuse.

Acknowledgements The authors would like to thank FAPEMIG,
CAPES, CNPQ, and BNDES for their financial support and the textile
industry for their trustworthy collaboration.
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