Environ Sci Pollut Res

DOI 10.1007/s11356-013-1934-0

RESEARCH ARTICLE

Insights into real cotton-textile dyeing wastewater treatment

using solar advanced oxidation processes
Petrick A. Soares & Tânia F. C. V. Silva &
Diego R. Manenti & Selene M. A. G. U. Souza &
Rui A. R. Boaventura & Vítor J. P. Vilar

Received: 15 April 2013 / Accepted: 11 June 2013

# Springer-Verlag Berlin Heidelberg 2013

Abstract Different advanced oxidation processes (AOPs) of mineralization t 30W ¼ 3:2 min; T ¼ 30:7  C; pH ¼ 2:80;
were applied to the treatment of a real cotton-textile dyeing UVG;n ¼ 13 W m−2 Þ:
wastewater as a pre-oxidation step to enhance the biodegrad-
ability of the recalcitrant compounds, which can be further Keywords Cotton-textile dyeing wastewater . Solar
oxidized using a biological process. Tests were conducted on advanced oxidation processes . Biodegradability . Lab-scale
a lab-scale prototype using artificial solar radiation and at pilot prototype with Suntest simulator . Pilot plant with CPCs
scale with compound parabolic collectors using natural solar
radiation. The cotton-textile dyeing wastewater presents a lilac Nomenclature
color, with a maximum absorbance peak at 641 nm, alkaline pH Δtn Time period (s)
(pH=8.2), moderate organic content (DOC=152 mg C L−1, ACPC Compound parabolic collector area (m2)
COD=684 mg O2 L−1) and low-moderate biodegradability AOP Advanced oxidation process
(40 % after 28 days in Zahn–Wellens test). All the tested Ar Illuminated collector surface area (m2)
processes contributed to an effective decolorization and miner- BOD5 Biochemical oxygen demand (mg O2 L−1)
alization, but the most efficient process was the solar-photo- CA Dissolved organic carbon in the sample after
Fenton with an optimum catalyst concentration of 60 mg Fe2+ 3 h the beginning of the Zahn–Wellens test (in
L−1, leading to 98.5 % decolorization and 85.5 % mineraliza- milligram carbon per liter)
tion after less than 0.1 and 5.8 kJUV L−1, respectively. In order CBA Dissolved organic carbon in the blank after 3 h
to achieve a final wastewater with a COD below 250 mg O2 L−1 the beginning of the Zahn–Wellens test (in
(discharge limit into water bodies imposed by the Portuguese milligram carbon per liter)
Legislation-Portaria no. 423/97 of 25 June 1997), considering CB Dissolved organic carbon in the blank, mea-
the combination of a solar-photo-Fenton reaction with a biolog- sured at the sampling time t, of the Zahn–
ical process, the phototreatment energy required is 0.5 kJUV L−1, Wellens test (in milligram carbon per liter)
consuming 7.5 mM hydrogen peroxide, resulting in 58.4 % COD Chemical oxygen demand (in milligram oxy-
gen per liter)
Responsible editor: Bingcai Pan COS Carbon oxidation state (dimensionless)
P. A. Soares : T. F. C. V. Silva : D. R. Manenti : CPC Compound parabolic collector
R. A. R. Boaventura : V. J. P. Vilar (*) Ct Dissolved organic carbon in the sample, mea-
LSRE—Laboratory of Separation and Reaction
sured at the sampling time t, of the Zahn–
Engineering—Associate Laboratory LSRE/LCM, Faculdade de
Engenharia, Universidade do Porto, Rua Dr. Roberto Frias, Wellens test (in milligram carbon per liter)
4200-465 Porto, Portugal DOC Dissolved organic carbon (in milligram carbon
e-mail: vilar@fe.up.pt per liter)
DOC0 Initial dissolved organic carbon (in milligram
S. M. A. G. U. Souza
Departamento de Engenharia Química, Universidade Federal de carbon per liter)
Santa Catarina, 88040-900 Florianópolis, SC, Brazil Dt Percentage of biodegradation (in percent)
 Environ Sci Pollut Res

I Average irradiation intensity (in watt per Although biological processes present competitive costs
square meter) they are usually ineffective in degradation of complex organic
k Pseudo-first order kinetic constant (in liter per dye molecules. Other processes, such as, coagulation/
kilojoule) flocculation, activated carbon adsorption and membrane sep-
kH Hydrogen peroxide consumption rate (in mil- aration can only transfer the contaminants from one phase to
limole per kilojoule) another leaving the problem essentially unsolved (Torrades
LMCA Low-molecular-weight carboxylate anions (in et al. 2004). Therefore, much attention has been paid to the
milligram carbon per liter) development of wastewater treatment techniques that lead to
QUV Accumulated ultraviolet energy (in kilojoule the complete destruction of the dye molecules into CO2, H2O
per liter) and mineral acids or transforming them into biodegradable
pH Average pH (Sorensen scale) compounds that can be easily eliminated by biological oxida-
r0 Initial dissolved organic carbon reaction rate tion. In this context, AOPs are recognized by its effectiveness
(mg kJ−1) in the treatment of recalcitrant wastewaters through the for-
SFM Six-flux absorption scattering model mation of highly reactive and non-selective hydroxyl radicals
SUNTEST Solar radiation simulator (Blanco et al. 2012; Oller et al. 2011). Several studies propose
T Average temperature (in degrees Celsius) the use of AOPs for the treatment of textile effluents:
t30 W Typical solar UV power on a perfectly sunny H2O2/UV (Schrank et al. 2007); TiO2/UV (Byberg et al.
day around noon (in minute) 2013; Pekakis et al. 2006); TiO2/H2O2/UV (Garcia et al.
tdark Dark time (in second) 2007); H2O2/Fe2+ (Fenton reaction) (Blanco et al. 2012;
ti Illuminated time (in second) Karthikeyan et al. 2011; Nidheesh et al. 2013); H2O2/Fe2+/UV
tn Time corresponding to n-water sample (in (photo-Fenton reaction) (Módenes et al. 2012).
second) However, the costs involved with the energy requirements
TSS Total suspended solids (in milligram per liter) and chemicals, especially when the goal is the complete
UV G n Average solar ultraviolet radiation intensity (in mineralization, are high and eventually make these technol-
watt per square meter) ogies non-competitive (Oller et al. 2011). An alternative is
Vi Illuminated reactor volume (in liter) the use of solar radiation, as UV–Vis photon source (Malato
VSS Volatile suspended solids (in milligram per et al. 2007) and apply the chemical oxidation as a pre-
liter) treatment to enhance the biodegradability through the deg-
Vt Total reactor volume (in liter) radation of the most persistent organic compounds (Aytar
WWTP Wastewater treatment plant et al. 2013; Dhir et al. 2012).
The photo-Fenton reaction was found to be the best solar
driven AOP in the treatment of different recalcitrant waste-
waters (de Morais and Zamora 2005; Renou et al. 2008),
Introduction including real textile wastewaters, which is related to the
higher light sensitivity up to 580 nm, corresponding to
The Portuguese textile industry is an important economic 35 % of solar radiation spectrum.
pillar representing 21 % of all exports from this country Therefore, this work compares the efficiency of different
(Serra et al. 2012). The textile industry is one of the largest AOPs in the treatment of a real cotton-textile dyeing waste-
consumers of water in the world, and consequently, one of water at pilot scale under natural sunlight and evaluates the
the largest producers of wastewaters (until 300 L kg−1 ma- influence of the main photo-Fenton reaction variables, such
terial) (El-Dein et al. 2006). Textile wastewaters resulting as iron concentration, pH, temperature, and light intensity, in
mainly from dyeing and finishing processes, present differ- a lab-scale prototype under controlled conditions using arti-
ent dyes with a complex organic structure, surfactants, de- ficial solar radiation.
tergents and inorganic salts, which constitutes a risk for the
environment and ecosystems when unloaded improperly in
the environment (Prigione et al. 2008). Experimental methodology
During the last 10 years, publications regarding textile
wastewaters treatment rose continuously, achieving more than Real cotton-textile dyeing wastewater
250 papers in 2009 (Fig. 1). Scientific community research
interests has been focused in biological, membrane and ad- Wastewater sample was collected after the cotton-textile
vanced oxidation processes (AOPs) technologies for the treat- dyeing process, from an industrial plant located in northern
ment of textile wastewaters. Portugal. Table 1 presents the main physico-chemical
Environ Sci Pollut Res

Fig. 1 Numbers of research 280 100

articles appearing on textile AOPs
wastewater treatment 90
technologies per year: search 240 Biological Processes
results in the period 1998–2011 Membrane Processes 80
with the SCOPUS (keyword
“Textile Wastewater 200 Others 70

Number of Publications
Treatment”). For interpretation

Percentage (%)
of the references to color in this 60
160
figure legend, the reader is
referred to the web version of 50
this article 120
40

80 30

20
40
10

0 0

Year

characteristics of the sample used in the phototreatment Chemicals

experiments.
AOPs were performed employing titanium dioxide (Degussa,
P25, 80 % anatase and 20 % rutile), hydrogen peroxide (50 %
(w/v), 1.10 g cm −3 , Quimitécnica, S.A.), iron sulfate
heptahydrated (Panreac) and sulfuric acid (96 %, 1.84 g cm−3,
Table 1 Cotton-textile dyeing wastewater characterization Pronalab) for pH adjustment. Ultrapure and deionized water was
Parameters Units Values produced by a Millipore system (Direct-Q model) and a reverse
osmosis system (Panice®), respectively.
pH Sorensen scale 8.20
Temperature °C 32.5 Analytical determinations
Conductivity mS cm−1 4.3
COD mg O2 L−1 684 Evaluation of H2O2 concentration during experiments was
Total dissolved carbon mg C L−1 460 performed by the vanadate method (Nogueira et al. 2005), based
Inorganic carbon mg C L−1 308 on the reaction of H2O2 with ammonium metavanadate in acidic
DOC mg C L−1 152 medium, which results in the formation of a red-orange color
Biodegradability—Zahn–Wellens test % 40 peroxovanadium cation, with maximum absorbance at 450 nm.
Absorbance at 641 nm – 0.198 Colorimetric determination of dissolved iron concentration was
Chloride mg Cl− L−1 105 achieved with 1,10-phenanthroline according to ISO 6332
Sulfate mg SO42− L−1 35 (1988).
Total dissolved nitrogen mg N L−1 117 Sulfate, chloride, nitrate, phosphates, nitrite, ammonium,
Nitrate mg N-NO3− L−1 <0.2 sodium, potassium, calcium, and magnesium were measured
Nitrite mg N-NO2− L−1 5.3 by ion chromatography (Dionex ICS-2100 and Dionex DX-
Ammonia mg N-NH4+ L−1 79 120 for anions and cations, respectively), using a Dionex
Phosphate mg P-PO43− L−1 6.7 Ionpac (columns: AS9-HC/CS12A 4 mm×250 mm; suppres-
Sodium mg Na+ L−1 495 sor: ASRS®300/CSRS®300 4 mm, respectively for anions
Potassium mg K+ L−1 42 and cations). The program for anions/cations determination
Magnesium mg Mg2+ L−1 11 comprises a 12 min run with 30 mM NaOH/20 mM
Calcium mg Ca2+ L−1 20
methanesulfonic acid at a flow rate of 1.5/1.0 mL min−1. Total
Total suspended solids mg TSS L−1 193
suspended solids (TSS) and Volatile suspended solids (VSS)
Volatile suspended solids mg VSS L−1 171
were determined according to Standard Methods (Clesceri
et al. 2005).

Dissolved organic carbon (DOC) was measured by NDIR
spectrometry in a TC-TOC-TN analyzer equipped with ASI-V
auto sampler (Shimadzu, model TOC-VCSN) and calibrated
with standard solutions of potassium hydrogen phthalate (total
carbon) and a mixture of sodium hydrogen carbonate/sodium
carbonate (inorganic carbon). Total dissolved nitrogen was
measured in the same TC-TOC-TN analyzer coupled with a
TNM-1 unit (Shimadzu, model TOC-VCSN) by thermal de-
composition and NO detection by chemiluminescence meth-
od, calibrated with standard solutions of potassium nitrate.
COD concentration was measured by Merck Spectroquant
kits (ref: 1.14541.0001). UV–Vis spectrum between 200 and
700 nm, absorbance at 450 nm (vanadate method), 510 nm
(phenanthroline method) and 641 nm (maximum absorbance
of the wastewater in the visible region) were obtained using a
UNICAM Helios spectrophotometer. Due to the textile waste-
water’s absorption at the selected wavelengths, a blank/control
sample (diluted as for the colorimetric analyses) was always
prepared, and the absorbance measured at the same wave-
length for correction. pH, temperature and conductivity were
measured using a pH meter HANNA HI 4522. Before analy-
sis, all samples were centrifuged in a HIMAC CT 6E centri-
fuge at 4,000 rpm for 5 min, except for the determination of
TSS, VSS and COD.
Biodegradability assays
Before biodegradability tests and other analyses involving
chemical oxidation, excess H2O2 present in samples was re-
moved by adding a small volume of 0.1 g L−1 catalase solution
(2,500 U mg−1 bovine liver) after adjusting the sample pH to
approximately 7. Biochemical oxygen demand (BOD5) deter-
mination was carried out according to Standard Methods using
an OXITOP# system (Clesceri et al. 2005). A 28-day biode-
gradability test (Zahn–Wellens test) was performed according
to the EC protocol, Directive 88/ 303/EEC (OECD 1992). A
volume of 240 mL of the pre-treated samples, obtained at
different reaction times, without hydrogen peroxide, was added
to an open glass vessel, magnetically stirred and kept in the
dark inside a thermostatic refrigerator at 25 °C. Activated
sludge from the municipal WWTP of Freixo (Porto, Portugal),
previously centrifuged, and mineral nutrients (KH2PO4,
K2HPO4, Na2HPO4, NH4Cl, CaCl2, MgSO4 and FeCl3) were
added to the samples. The control and blank experiments were
prepared using glucose and distilled water, respectively. The
percentage of biodegradation (Dt) was determined by the fol-
lowing equation (EPA 1996):
 
C t −C B
Dt ¼ 1−  100 ð1Þ
C A −C BA
where CA and CBA are the DOC (mg L−1) in the sample and in
the blank, measured 3 h after the beginning of the experiment,
Environ Sci Pollut Res
Ct and CB are the DOC (mg L−1) in the sample and in the blank,
measured at the sampling time t.
Using chemical oxidation demand (COD) values of the
pre-treated samples, the carbon oxidation state (COS) pa-
rameter was calculated by Eq. (2), which is used to evaluate
the oxidation degree and effectiveness of the oxidative pro-
cess (Amat et al. 2007).
COD
COS ¼ 4−1:5 ð2Þ
DOC0
where DOC0 is the initial dissolved organic carbon of the
solution (in milligram carbon per liter), and COD is the
chemical oxygen demand at time t (in milligram oxygen
per liter). COS takes values between +4 for CO2, the most
oxidized state of carbon, and −4 for CH4, its most reduced
state. COS takes into consideration the organic matter in
solution and the CO2 eliminated (Arques et al. 2007).
Solar CPC pilot plant
The solar driven AOPs experiments were carried out in a
CPC pilot plant installed at the roof of the Chemical Engi-
neering Department of the Faculty of Engineering, Univer-
sity of Porto, Portugal. The solar collector consists of a CPC
unit (0.91 m2) of four borosilicate (Duran) tubes (Schott-
Duran type 3.3, Germany, cut-off at 280 nm, internal diam-
eter 50 mm, length 1,500 mm and width 1.8 mm) connected
in series by polypropylene junctions, with their CPC mirrors
in anodized aluminum, supported by a aluminum structure,
oriented to south and tilted 41° (local latitude). The pilot
plant has also two recirculation tanks (10 and 20 L), two
recirculation pumps (20 L min−1), two flow meters, five
polypropylene valves and an electric board for process con-
trol. The pilot plant can be operated in two ways: using the
total CPCs area (0.91 m2) or using 0.455 m2 of CPCs area
individually, giving the possibility of performing two differ-
ent experiments at the same time and under the same solar
radiation conditions. The intensity of solar UV radiation is
measured by a global UV radiometer (ACADUS 85-PLS)
mounted on the pilot plant with the same inclination, which
provides data in terms of incident WUV m−2. A schematic
representation of the pilot plant has been published else-
where (Pereira et al. 2011).
The amount of accumulated UV energy (QUV,n in kilo-
joule per liter) received on any surface in the same position
with regard to the sun, per unit of volume of water inside the
reactor, in the time interval Δt is calculated using the fol-
lowing equation:
Ar
QUV;n ¼ QUV;n−1 þ Δt n UVG;n ; Δt n ¼ t n −t n−1 ð3Þ
1; 000  V t
where tn is the time corresponding to n-water sample (s), Vt
the total reactor volume (in liter), Ar the illuminated collector
Environ Sci Pollut Res
surface area (in square meter) and UVG;n the average solar
ultraviolet radiation (in watt per square meter) measured
during the period Δtn (in second).
Lab-scale photoreactor prototype
The optimization of the photo-Fenton reaction variables was
carried out in a lab-scale photoreactor with a sunlight simu-
lator. Figure 2 presents a scheme of the photocatalytic system
which comprises: (1) a solar radiation simulator (ATLAS,
model SUNTEST XLS+) with 1,100 cm2 of exposition area,
a 1,700 W air-cooled xenon arc lamp, a daylight filter and
quartz filter with IR coating; (2) a compound parabolic
collector (CPC) with 0.023 m2 of illuminated area with
anodized aluminum reflectors and a borosilicate tube
(Schott-Duran type 3.3, Germany, cut-off at 280 nm, internal
diameter 46.4 mm, length 160 mm and thickness 1.8 mm);
(3) one glass vessel (capacity of 1.5 L) with a cooling jacket
coupled to a refrigerated thermostatic bath (Lab. Compan-
ion, model RW-0525G) to ensure a constant temperature
during the experiment; (4) a magnetic stirrer (Velp
Scientifica, model ARE) to ensure complete homogenization
of the solution inside the glass vessel; (5) one peristaltic
pump (Ismatec, model Ecoline VC-380 II, with a flow rate
of 0.63 L min−1) to recirculate the water between the CPC
and the glass vessel; (6) pH and temperature meter (VWR
symphony—SB90M5). All the systems are connected using
Teflon tube. The intensity of the UV radiation was measured
by a broadband UV radiometer (Kipp & Zonen B.V., model
CUV5), which was placed inside the sunlight simulator at the
same level than the photoreactor center. The radiometer was
plugged into a handheld display unit (Kipp & Zonen B.V.,
Fig. 2 Schematic
representation of the
experimental set-up constituted
by the lab-scale reactor and
sunlight simulator
model Meteon) to record the incident irradiance (in watt per
square meter).
Experimental procedure
Solar pilot plant
A volume of 15 L of wastewater was added to the recirculation
tank of the CPC units (illuminated volume (Vi)=5.1 L;
Vi/Vt =0.34; illuminated time (ti)=0.25 min; dark time
(tdark)=0.50 min; ACPC =0.455 m2) and homogenized by turbu-
lent recirculation, during 15 min, in darkness (a first control
sample was taken for further characterization). For heteroge-
neous photocatalytic tests (TiO2/UV and TiO2/H2O2/UV), after
taking the first sample, titanium dioxide was added up to a
concentration of 200 mg L−1 and the mixture recirculated for
more than 15 min. It should also be underlined that catalyst
concentration (200 mg TiO2 L−1) is the optimum concentration
for the photoreactors used in this work, with an internal diameter
of 46.4 mm (Malato Rodrı́guez et al. (2004); Vilar et al. 2009),
which has recently been supported by accurate modeling of
radiation field in a CPC solar photoreactor by a six-flux absorp-
tion scattering model (SFM), showing that TiO2 in the concen-
tration of 200 mg L−1 is able to absorb 100 % of the solar UV
photons (Colina-Márquez et al. 2010). For TiO2/UV tests, a
second sample was collected just before uncovering the CPC
units, in order to evaluate the pollutants adsorption onto the
catalyst surface. In the case of TiO2/H2O2/UV experiments, a
second sample was as well collected and hydrogen peroxide
(500 mg L−1) was added to the mixture TiO2/effluent, just before
uncovering the CPCs. The two heterogeneous photocatalytic
tests were performed after adjusting the pH to 4.5 with sulfuric

acid, in order to eliminate carbonates and bicarbonates and
compare the results with the photo-Fenton tests. In all cases,
samples were taken at successive time intervals to evaluate the
progress of the photocatalytic oxidation.
For the photo-Fenton tests, pH was adjusted to 2.7–2.9 with
sulfuric acid and another sample was taken 15 min later to
confirm this value. Afterwards, iron salt (60 mg Fe2+ L−1) was
added, the mixture was well homogenized for 15 min and a
third sample was taken for iron concentration control. Finally,
the first dose of hydrogen peroxide (500 mg L−1) was added,
the CPCs were uncovered and samples were taken at different
time intervals to evaluate the degradation process. Regarding
the photolysis and H2O2/UVexperiments, reactions occurred at
pH 4.5, without addition of any reagent in the case of photol-
ysis. Whenever hydrogen peroxide was used, its concentration
was maintained between 100 and 500 mg L−1, during the entire
runs, through the addition of small amounts of hydrogen per-
oxide to compensate the consumption.
Lab-scale photoreactor
In order to evaluate the photo-Fenton reaction parameters, the
recirculation glass vessel of the lab-scale prototype was filled
with 1 L of wastewater (Vi =270 mL; Vi/Vt =0.27; ti =0.43 min;
tdark =1.16 min; ACPC =0.023 m2), which was pumped to the
CPC unit and homogenized by recirculation in the closed
system during 15 min in the darkness. pH was adjusted to the
desired value (2.4, 2.8, 3.2, 3.6, and 4.5) using sulfuric acid and
another sample was taken 15 min later to confirm this value.
The temperature set-point of the refrigerated thermostatic bath
was controlled to keep the intended wastewater temperature
(10, 20, 30, 40, or 50 °C). The SUNTEST was turned on and
the radiation intensity was defined as 250, 500, and 750 W m−2,
which is equivalent to 22, 44, and 68 WUV m−2, measure in the
wavelength range from 280 to 400 nm. Ferrous sulfate was
added to obtain the concentrations of 20, 40, 60, 80, and
100 mg L−1. After 15 min, another sample was taken for iron
concentration control. Finally, the first dose of hydrogen per-
oxide was added and samples were taken at pre-defined times
to evaluate the degradation process. The concentration of hy-
drogen peroxide was maintained in excess, between 100 and
500 mg L−1 during the entire reaction, by adding amounts to
compensate the consumed ones, as determined by analyses
throughout the experiments. The operational conditions of the
experiments are presented in Table 2.
Results and discussion
Cotton-textile dyeing wastewater characterization
Table 1 shows a brief characterization of the cotton-textile
dyeing wastewater used in this study, which was collected in a
Environ Sci Pollut Res
textile company located at the north of Portugal, before being
subjected to any form of treatment. The selected effluent is
exclusively originating from the dyeing process of cotton
fibers. The wastewater presents a lilac color, resulting from
the mixture of different reactive dyes, originating a maximum
absorbance peak at 641 nm. The wastewater presents a rela-
tively high pH value (8.20) and temperature (32.5 °C), and a
moderate organic load (COD=684 mg O2 L−1 and
DOC=152 mg C L−1). High values were found for total
dissolved nitrogen and ammonia, 117 mg N L−1 and
79 mg N-NH4+ L−1, respectively. The concentration of chlo-
ride and sulfate ions is relatively small when compared with
other textile wastewaters (Somensi et al. 2010; Vilar et al.
2011). According to the Zahn–Wellens test, the wastewater
presents a moderate biodegradability, mainly attributed to
some organic compounds leached from the cotton fibers dur-
ing the chemical washing (scouring process), which removes
natural wax and non-fibrous impurities (e.g., the remains of
seed fragments) from the fibers and any added soiling or dirt.
Solar driven AOPs
Preliminary treatment studies at pilot scale were performed in
order to compare the efficiency of different advanced oxida-
tion processes (UV; TiO2/UV; H2O2/UV; TiO2/H2O2/UV; and
Fe2+/H2O2/UV) under natural solar conditions. Figure 3
shows the mineralization profiles for all the solar driven AOPs
tested and Table 2 presents the operational conditions and
pseudo-first-order kinetic constants.
Preliminary acidification of the textile wastewater to ap-
proximately 4.5 was performed for all tests, with exception
of photo-Fenton (pH=2.8), in order to eliminate the carbon-
ates and bicarbonates, which act as HO• scavengers, leading
to formation of less reactive species (Kormann et al. 1991).
The acidification procedure to pH 4.5 or 2.8 (photo-Fenton
reaction) resulted in a DOC abatement of approximately 13
and 23 %, attributed to the formation of small amount of
foam (which can retain a certain amount of organic matter)
and precipitation of some organic compounds as observed by
the sludge formation.
Figure 3 shows clearly that the solar-photo-Fenton pro-
cess is the most efficient of all solar AOPs studied, achieving
85.5 % mineralization after 5.8 kJUV L−1 and consuming
68.4 mM of H2O2. The initial reaction rate of the photo-
Fenton reaction, considering a pseudo-first order reaction
kinetics, is more than 47 times higher than that of the
TiO2/H2O2/UV system. Similar results have been also re-
ported by Vilar et al. (2011) for the treatment of a real textile
wastewater.
Table 2 shows the percentage of decolorization for each
treatment proposed. All AOPs resulted in a decolorization greater
than 70 %, being the photo-Fenton process the most efficient and
faster one. Following the trend of the mineralization process, the
Table 2 Operational conditions and pseudo-first order kinetic constants

Experiments I a (W m−2) Feb (mg L−1) T c (°C) pHd Mineralization Decolorization Kinetic parameters

Red.e QUV H2O2 Red.f QUV H2O2 DOC degradation H2O2 consumption QUV j
−1
(%) (kJ L ) (mM) (%) (kJ L−1) (mM) (kJ L−1)
kg (L kJ−1) r0h (mg kJ−1) R2 kHi (mmol kJ−1) R2
Environ Sci Pollut Res

Natural sunlight UV 19.0 – 17.7 4.51 16.9 27.8 – 70.9 17.7 – 0.0010±0.0001 0.20±0.02 0.995 – – >7.2
H2O2/UV 25.0 – 25.2 4.47 38.9 56.2 10.6 73.1 56.2 7.3 0.0050±0.0004 0.60±0.07 0.999 0.200±0.004 0.999 >19.7
TiO2/UV 17.0 – 25.8 4.46 31.9 15.3 – 85.5 15.3 – 0.014±0.002 1.9±0.3 0.993 – – >3.2
TiO2/H2O2/UV 22.1 – 22.3 4.45 69.0 51.4 59.9 76.4 36.7 40.8 0.020±0.002 2.4±0.3 0.995 1.20±0.08 0.994 >1.2
Fe2+/H2O2/UV 26.0 47.1 40.7 2.80 85.5 5.8 68.4 98.5 <0.1 1.9 1.0±0.6 76±50 0.997 9±2 0.984 >0.2
Artificial sunlight Fe=20 mg L−1 22.0 16.9 30.2 2.8 74.5 8.3 26.5 82.4 1.6 10.7 0.081±0.009 6±1 0.999 2.6±0.3 0.997 >0.8
Fe=40 mg L−1 22.0 35.0 30.2 2.8 81.8 8.3 37.5 89.7 1.6 10.8 0.11±0.02 7±2 0.997 3.9±0.2 0.999 >1.6
Fe=60 mg L−1 22.0 51.6 30.3 2.8 84.6 5.9 38.8 97.9 <0.1 1.8 0.26±0.04 15±4 0.992 5±1 0.983 >0.4
Fe=80 mg L−1 22.0 75.2 30.2 2.8 86.2 7.2 56.2 97.8 <0.1 3.2 0.25±0.05 17±4 0.991 7±2 0.994 >0.2
Fe=100 mg L−1 22.0 100.5 30.2 2.8 88.9 7.2 60.7 97.4 <0.1 3.2 0.30±0.03 19±4 0.996 7±3 0.979 >0.2
pH=2.4 22.0 54.7 30.6 2.4 78.4 9.5 47.4 83.9 1.8 7.7 0.13±0.01 11±2 0.994 5.1±0.5 0.994 >0.8
pH=2.8 22.0 51.6 30.3 2.8 84.6 5.9 38.8 97.9 <0.1 1.8 0.26±0.04 15±4 0.992 5±1 0.983 >0.4
pH=3.2 22.0 48.8 30.4 3.2 82.7 7.2 47.3 89.4 <0.1 2.2 0.26±0.04 20±4 0.997 6.6±0.9 0.990 >0.8
pH=3.6 22.0 27.4 30.3 3.6 81.3 7.2 48.7 90.2 3.5 22.2 0.24±0.01 17±3 0.999 6.6±0.8 0.996 >0.2
pH=4.5 22.0 14.3 30.2 4.4 35.5 9.5 22.8 90.1 4.7 13.1 – – – 2.1±0.1 0.999 >0.1
T=10 °C 22.0 60.2 10.2 2.8 60.0 9.5 15.5 91.3 1.2 2.7 0.029±0.008 2.5±0.7 0.960 1.5±0.1 0.994 >0.8
T=20 °C 22.0 57.9 20.4 2.8 62.8 9.5 32.2 94.2 1.2 3.9 0.043±0.007 3.4±0.8 0.988 3.8±0.1 0.999 >0.4
T=30 °C 22.0 51.6 30.3 2.8 84.6 5.9 38.8 97.9 <0.1 1.8 0.26±0.04 15±4 0.992 5±1 0.983 >0.4
T=40 °C 22.0 54.1 40.2 2.8 86.1 9.5 63.2 97.5 3.5 21.7 0.28±0.02 19±3 0.999 7±2 0.988 >0.2
T=50 °C 22.0 56.3 50.0 2.8 87.4 9.5 84.8 97.1 1.2 28.2 0.49±0.04 34±6 0.996 9±2 0.980 >0.2
I=22 W m−2 22.0 55.0 30.3 2.8 79.1 9.5 38.7 97.1 <0.1 2.1 0.32±0.06 22±5 0.990 7.9±0.9 0.996 >1.2
I=44 W m−2 44.0 51.6 30.3 2.8 84.6 5.9 38.8 97.9 <0.1 1.8 0.26±0.04 15±4 0.992 5±1 0.983 >0.4
I=68 W m−2 68.0 38.7 30.3 2.8 88.0 9.2 44.0 97.8 <0.1 1.9 0.4±0.2 22±11 0.999 6±2 0.988 >0.6

a
Average irradiation intensity
b
Average dissolved iron concentration
c
Average solution temperature
d
Average pH
e
Percentage of mineralization
f
Percentage of decolorization
g
Pseudo-first-order kinetic constant
h
Initial DOC reaction rate
i
H2O2 consumption rate
j
Energy range considered in calculating the coefficients
 Environ Sci Pollut Res

RAD-ON
be optimized for each particular application, aiming at cost
1.0 reduction and reaction rate maximization.
Figure 4 presents the textile wastewater mineralization
profiles for five different initial iron concentrations (20, 40,
0.8 60, 80, and 100 mg Fe2+ L−1), at a constant temperature of
approximately 30 °C, similar to the real cotton-textile waste-
DOC/DOC0

water conditions, and pH 2.8. A similar DOC abatement

0.6 (15 %) was observed after pH adjustment to pH 2.8 due to
the formation of foam and sludge (possible precipitation of
some compounds at low pH).
0.4 Afterwards, it can be observed a small induction period (up to
UV 0.4 kJUV L−1), characterized by low mineralization and low
TiO2/UV hydrogen peroxide consumption (which is more visible in the
0.2 H2O2/UV experiment with the lowest iron dose), although decolorization
TiO2/H2O2/UV is very rapid suggesting a fast breaking down of the dyes
2+
Fe /H2O2/UV molecules. Fenton tests were performed (only data for 60 mg
0.0 Fe2+ L−1 is showed in Fig. 4) and it was observed the same
0 10 20 30 40 50
-1 mineralization in the same period according to the amount of
QUV (kJUV L )
iron added, and afterwards the reaction almost stopped, achiev-
Fig. 3 Mineralization of the cotton-textile dyeing wastewater: compar- ing a constant DOC concentration. This suggests that after the
ison between the different AOPs evaluated first iron oxidation in the presence of hydrogen peroxide, the

photo-Fenton reaction resulted in 98.5 % decolorization after 1.0

RAD-ON
80
only 0.1 kJ L−1 (t30 W =2.1 min) of accumulated energy, con-
0.8 70
suming 1.9 mM H2O2.
60

H2O2 consumed (mM)

Photo-Fenton reaction: process variables and their influence 0.5
50
DOC/DOC0

As the photo-Fenton reaction showed the highest efficiency in 0.4

40
the treatment of the cotton-textile wastewater, considering all
0.3
the AOPs applied, the influence of the main reaction variables, 30
such as, iron concentration, pH, temperature and radiation 0.2 20
intensity, were evaluated under controlled conditions in a
lab-scale photoreactor with a sunlight simulator. Table 2 pre- 0.1 10
sents the photo-Fenton reaction conditions used in all sets of
0
experiments. 0.0
Dissolved Iron (mg L )
-1

100
Iron concentration 80
60

Malato Rodrı́guez et al. (2004) reported that the optimum iron 40

concentration for the solar-photo-Fenton reactions, using 20

0
CPCs with borosilicate tubes with an internal diameter of 0.0 0.1 0.2 1 2 3 4 5 6 7 8 9 10
46.4 mm, is between 0.2 and 0.5 mM (amount of iron neces- -1
QUV (kJUV L )
sary to absorb all the UV–Vis photons). However, if there are
Fig. 4 Evolution of the DOC concentration, H2O2 consumed and total
other light-absorbing species present in solution, especially in
iron dissolved during the photo-Fenton reaction for different dissolved
colored wastewaters, such as textile effluent (dyes presents an total iron concentrations, as well as the Fenton reaction. Photo-Fenton´s
aromatic structure that absorbs UV and visible light), de- operation conditions: pH=2.8; T=30 °C; I=44 W m−2; solid symbols
creases the number of photons that can be absorbed by the DOC; open symbols H2O2 consumed; cross symbols dissolved iron.
( , , )—[Fe2+]=20 mg L−1; ( , , )—[Fe2+]=40 mg L−1;
iron complexes, being necessary higher iron concentrations
( , , )—[Fe2+]=60 mg L−1; ( , , )—[Fe2+]=80 mg L−1;
(above 1 mM) to achieve the desired reaction rates (Malato ( , , )—[Fe2+]=100 mg L−1. Fenton’s operation conditions:
et al. 2009). Therefore, the optimum iron concentration must pH=2.8; T=30 °C; [Fe2+]=60 mg L−1; ( , , )
Environ Sci Pollut Res
limiting step of the reaction is the availability of radiation for the
regeneration of ferrous ions (reduction of Fe3+ to Fe2+) (Silva
et al. 2007), as absorption of photons by other light-absorbing
species (inner filter effects), such as, dyes and its initial degra-
dation molecules with aromatic structure, decreases the number
of photons absorbed by the iron complexes. Normally, the direct
photolysis of dyes has a low quantum yield, and consequently
originates a loss of the photons absorbed (Feng et al. 1999). The
higher the iron concentration, the smaller is the induction period,
being almost eliminated for the highest iron concentration tested,
which means that a high catalyst concentration is needed to
compete efficiently for the photons with the other absorbing
species present in the dark solution.
After this induction time, the mineralization profile follows
a pseudo-first-order kinetic model. Although the kinetic con-
stants increase with iron concentration, the increment is very
small for concentrations higher than 60 mg L−1, being neces-
sary higher amounts of H2O2 (Table 2). After approximately
4 kJUV L−1, a very small mineralization rate is observed,
principally for iron concentrations above 60 mg L−1, indicating
the formation of iron complexes with some low-molecular
weight carboxylic acids, which are very stable and are not
photodecarboxylated (for example, ferrioxalate and ferricitrate
complexes are easily photodecarboxylated), being necessary
high energy doses for their complete mineralization.
pH
Different authors reported that the optimum pH value for the
photo-Fenton reaction is 2.8 mainly due to the fact that the
predominant iron species in solution is FeOH2+, which is the
most photoactive ferric ion-water complex, but also because
it avoids ferric hydroxide precipitation (Pignatello et al.
2006). However, the need for acidification in the photo-
Fenton process is often outlined as one of its major draw-
backs, due to the additional cost associated to acidification
and subsequent neutralization.
Figure 5 presents the mineralization of the textile waste-
water at five different initial pH values (2.4, 2.8, 3.2, 3.6, and
4.5) using the same initial iron concentration (60 mg L−1).
For an initial pH value of 4.5, after the first oxidation of
ferrous ions to ferric ions caused by hydrogen peroxide, it is
observed a rapid decay of dissolved iron concentration for
values lower than 5 mg L−1. The formation of hydroxyl
radicals during the first oxidation leads to a small initial
oxidation and after that DOC remained approximately con-
stant. For the reaction at an initial pH value of 2.4, after the
first oxidation of ferrous ions with H2O2, the higher induc-
tion period in DOC abatement until 3 kJUV L−1, is related to
higher percentage of FeSO4+ species in solution, which is
much less photoactive than FeOH2+ (Table 3), and also leads
to the formation of less oxidant species SO4•− when
compared with HO• radicals, respectively, according to
Eqs. (2) to (4) (Machulek Júnior et al. 2011):
FeSOþ
4 þ hv→Fe
2þ
þ SO•−
4 ð4Þ
FeOH2þ þ hv→Fe2þ þ HO• ð5Þ
After the induction time, the kinetic rate increases substan-
tially which can be associated to the photolysis of some
ferricarboxylate complexes, formed during the induction pe-
riod, accelerating the reduction of ferric ions.
For the reaction at an initial pH value of 3.6, after the first
oxidation of ferrous ions with H2O2, the dissolved iron
concentration decreased to about 35 mg L−1 until 3.0 kJUV
L−1, and then started to precipitate leading to dissolved iron
concentrations below 5 mg L−1, which can be associated to
the decarboxylation of ferricarboxylate complexes, and con-
sequently precipitation of iron as Fe(OH)3. The DOC abate-
ment for the experiment at pH 3.2 is similar to that obtained
at pH 3.6, although dissolved iron concentration remained
near 50 mg L−1 during the entire run. This indicates that the
photodecarboxylation of ferricarboxylates complexes repre-
sents the main mechanism after an accumulated UV energy
of 3 kJUV L−1. Figure 5 shows a faster kinetic rate for the
experiment at an initial pH 2.8 than 3.2, although the amount
of dissolved iron during the experiments was very similar.
Considering the amount of sulfate and chloride ions present
in solution at each pH value, a higher amount of FeOH2+
species is obtained for pH 3.2, however the reaction rate is
slower than at pH 2.8. Different iron complexes species are
present in solution, which can have different photoactivity at
different pH values. For example, Balmer and Sulzberger
(1999) showed that iron(III) in the presence of oxalic acid
can form different species, such as, Fe(C2O4)+, Fe(C2O4)2−,
and Fe(C2O4)33−, which speciation depends greatly on the
solution pH, iron, and oxalic acid concentration. Fe(C2O4)2−
and Fe(C2O4)33− are much more efficiently photolyzed than
Fe(C2O4)+ and Fe(OH)2+, leading to higher reaction rates.
For example, Balmer and Sulzberger (1999) showed that
atrazine degradation was much faster at pH 4.2 than 3.2 since
the concentrations of the most efficiently photolyzed species,
Fe(C2O4)2− and Fe(C2O4)33− are the highest ones around
pH 4.0, considering the iron and oxalate concentrations used.
Influence of temperature
Typically, textile wastewaters present temperatures higher
than 30 °C (Ali et al. 2009), which is not in agreement with
the discharge limits into receiving waters. The oxygen solu-
bility decreases with the increase of temperature, promoting
 Environ Sci Pollut Res

Fig. 5 Evolution of the DOC

concentration, H2O2 consumed, 1.0 RAD-ON RAD-ON
60
0.9

H2O2 consumed (mM)

pH, and dissolved iron concen-
tration during the photo-Fenton 0.8 50
reaction for different pHs. Oper- 0.7

DOC/DOC0
ation conditions: [Fe2+]=60 mg- 40
0.6
L−1; I=44 W 0.5 30
m−2; T=30 °C. Solid symbols 0.4
DOC; open symbols H2O2 con- 20
0.3
sumed; cross symbols dissolved
iron; half-painted symbols pHs. 0.2
10
( , , , )—pH=2.4; 0.1
( , , , )—pH=2.8; 0.0 0
( , , , )—pH=3.2; 70 RAD-ON RAD-ON
( , , , )—pH=3.6; 9.0

Dissolved Iron (mg L )

-1
( , , , )—pH=4.5 60
7.5
50
40 6.0

pH
30
4.5
20
3.0
10
0 1.5
0.0 0.2 1 2 3 4 5 6 7 8 9 0.0 0.2 1 2 3 4 5 6 7 8 9
-1 -1
QUV (kJUV L ) QUV (kJUV L )

algal growth, fish mortality and a decrease in water biodiver- ferric ion, particularly Eqs. 6–8, which use radiation of wave-
sity. However, high temperatures (until 50 °C) favor the solar- lengths higher than 500 nm.
photo-Fenton reaction, which is an advantage when applied to
Fe3þ þ H2 O2 ↔Fe2þ þ HO•2 þ Hþ ð6Þ
the treatment of textile wastewaters (Malato et al. 2009).
Figure 6 shows the mineralization of the textile wastewater
at different temperatures (10 °C, 20 °C, 30 °C, 40 °C and Fe3þ þ HO•2 ↔Fe2þ þ O2 þ Hþ ð7Þ
50 °C), using a iron concentration of 60 mg L−1 and a pH
value of 2.8. For temperatures between 10 °C and 20 °C the Fe3þ þ O•−
2 ↔Fe þ O2 ð8Þ
2þ
kinetics rates were extremely low achieving a mineralization
efficiency of about 60 % after 9 kJUV L−1, however the
consumption of H2O2 doubled when increasing the tempera- The increase from 30 to 50 °C did not affect mineraliza-
ture from 10 °C to 20 °C (Table 2). For temperatures between tion, approximately 85 % after 5 kJUV L−1, although the
40 and 50 °C, the Fenton reaction was more efficient and H2O2 consumption increased by a factor of 1.6 due to two
faster due to the thermal reactions involved in the reduction of mains factors: (1) thermal ferric ion reduction reactions without

Table 3 Concentrations of chloride, sulfate and iron species percentage for different pH values (2.0; 2.4; 2.8; 3.2; 3.6 and 4.5) (Machulek Júnior
et al. 2011)

pH [SO42−] [Cl−] Iron species percentage (%)

(g L−1) (g L−1)
Fe3+ FeOH2+ Fe(OH)2+ FeCl+ FeSO4+ Fe(SO4)2−

2.4 1.830 0.096 9.1 13.4 1.7 0.2 62.8 12.8

2.8 1.443 0.095 11.2 16.5 2.1 0.2 60.4 9.6
3.2 1.325 0.095 8.5 31.7 10.0 0.2 43.2 6.4
3.6 1.286 0.096 4.2 39.6 31.5 0.1 21.4 3.2
4.5 1.215 0.095 0.2 13.5 85.2 <0.1 0.9 0.1
Environ Sci Pollut Res

Fig. 6 Evolution of the DOC

concentration, H2O2 consumed, 1.0 RAD-ON RAD-ON
90
80

H2O2 consumed (mM)

temperature and dissolved iron 0.8
concentration during the reaction 70
of photo-Fenton for different 0.5 60

DOC/DOC0
temperatures. Operation condi-
tions: pH=2.8; [Fe2+]=60 mg- 0.4 50
L−1; I=44 W m−2; solid symbols 0.3 40
DOC; open symbols H2O2 30
consumed; cross symbols 0.2
20
temperature; half-painted 0.1
symbols dissolved iron. 10
( , , , )—T=10 °C; 0.0 0
( , , , )—T=20 °C; RAD-ON RAD-ON 70
60
( , , , )—T=30 °C;

Dissolved Iron (mg L )

60

-1
( , , , )—T=40 °C;
( , , , )—T=50 °C 50
50
40
T (ºC) 40
30 30
20
20
10
10
0
0.0 0.2 1 2 3 4 5 6 7 8 9 0.0 0.2 1 2 3 4 5 6 7 8 9
-1 -1
QUV (kJUV L ) QUV (kJUV L )

hydroxyl radicals production in contrast with the photo reduc-
tion pathway, where H2O2 is not necessary and leads to the
production of more hydroxyl radicals and (2) hydrogen perox-
ide decomposition at high temperatures (the rate of decompo-
sition of hydrogen peroxide doubles every time the tempera-
ture rises by 10 °C). The results obtained at pilot scale showed
high H2O2 consumption rates, which are similar to those
obtained at lab-scale photoreactor, considering the average
temperature observed in the experiment under real solar con-
ditions (see Table 2).
According to Zapata et al. (2010), iron precipitation occurs
due to the decrease of iron solubility for temperature higher
than 42 °C, considering maximum iron concentrations of
55 mg L−1. In our study, precipitation of iron was not observed,
however, for the experiments at 40 and 50 °C, the iron concen-
tration decreased slightly to values of 54.1 and 56.3 mg L−1
respectively. Iron solubility depends also on the solution ionic
strength, as well as on the type of ions present in solution,
which can form more soluble iron complexes. In the study
reported by Zapata et al. (2010), synthetic solutions were used,
with a low ionic strength, and in our study, real wastewater was
used, with different ions and a high ionic strength, which can
greatly influence iron solubility.
Influence of radiation intensity
Normally, in the north of Portugal, UV radiation power can
achieve maximum values of around 50 W m−2 between 12:00
and 16:00 hours and an average daily intensity of 20 W m−2 in
spring and summer seasons. Considering the irradiation inten-
sity variation during the day, location and season and, high
radiation intensities are associated to higher temperatures,
assays were performed at different radiation intensities: 22,
44 and 68 WUV m−2, within the limits of the SUNTEST
equipment (Fig. 7). Kinetic profiles show a slight improve-
ment in the mineralization with the increase of radiation
intensity in terms of accumulated energy, with similar hydro-
gen peroxide consumption (Table 2). This means that the
reaction rate remains approximately constant within the range
of radiation intensities studied, which proves that the photo-
Fenton reaction can be used efficiently during all the year.
Considering the reaction velocity as a function of time, higher
radiation intensities allows the same mineralization rates in
less time, since more photons per unit of time are available for
the production of hydroxyl radicals.
Biodegradability assays
A Zahn–Wellens test was carried out to evaluate the wastewater
biodegradability at different stages of the solar-photo-Fenton
treatment, in order to determine the optimum phototreatment
time for coupling with a biological process. To collect pre-
treated samples for this test, the previous solar-photo-Fenton
experiment at pilot scale under natural solar conditions was
repeated (pH=2.8; [Fe2+]=60 mg L−1), adding small amounts
of hydrogen peroxide, and after total H2O2 consumption, a
 Environ Sci Pollut Res

1.0 RAD-ON 1.0 RAD-ON

photoreactors, showing that the Fenton process is efficient in
0.8 the decolorization.

DOC/DOC0
0.8 0.5 Figure 8a shows also a fast increase of the DOC correspond-
0.4 ing to low-molecular-weight carboxylate anions (LMCA/DOC
0.5 0.3 ratio) after the beginning of the photo-Fenton reaction, achieving
maximum values of 20.5 % (considering the LMCA analyzed)
DOC/DOC0

0.2
0.4 0.1
at 7.5 mM H2O2 consumed (sample 4) (6.6, 2.8 and 1.5 mg C
0.0
L−1 for propionate, malonate, and oxalate, respectively), follow-
0.3 0 2 20 40 60 80 100 120 ed by a fast decrease, since those acids correspond to the last
t (h)
oxidation products.
0.2 According to the Zahn–Wellens test (Fig. 8b) the cotton-
textile dyeing wastewater presents a moderate biodegrad-
0.1
ability of 40 % related to the aspects reported above. The
0.0
a
Dissolved Iron (mg L )

H2O2 consumed (mM)

-1

75 60
4
50 S0 RAD-ON COD
60 700
DOC
45 40 S2 20
LMCA/DOC ratio 3
30 600
COS
30 S1 S3
20 500 S4 2
15 10 S5

COS (dimensionles)
15

LMCA/DOC (%)
0 0 400
COD, DOC (mg L )
-1 1
0.0 0.2 2 4 6 8 10 12 14 16 300 S6
-1
QUV (kJUV L ) 150
0
10

Fig. 7 Evolution of the DOC concentration, H2O2 consumed and 120 -1

dissolved iron concentration during the photo-Fenton reaction for dif- 90
ferent radiation intensities. Operation conditions: [Fe2+]=60 mg L−1; 5
-2

pH=2.8; T=30 °C. Solid symbols DOC; open symbols H2O2 consumed; 60

cross symbols dissolved iron. ( , , )—I=22 W m−2; 30

-3

( , , )—I=44 W m−2; ( , , )—I=68 W m−2

0 0 -4
0 4 8 12 16
sample was taken for bioassays and another amount of H2O2 H2O2 consumed (mM)
was added. This process was very important not only to prevent
any reaction under dark conditions after sample collection but b
100 100
also to prevent the inhibition of microorganisms in bioassays
due to the presence of residual H2O2. Besides the biodegrad- 90 90

ability test, some other analyses, such as COD, BOD5, total 80 80

dissolved nitrogen, and low-molecular-weight carboxylate an- 70 70
ions were also performed for a more thorough analysis of each
60 60
step of the photo treatment.
Dt (%)
Dt (%)

The COD and DOC concentration decreased 63 and 67 %, 50 50

respectively, showing a strong oxidation of the organics, 40 40
which is well correlated with the COS parameter as it in-
30 30
creased from −2.8, indicating the presence of some reduced
20 20
organic compounds, to +1.5 after 19.6 mM of H2O2 consump-
tion, meaning strong mineralization and generation of highly 10 10
oxidized intermediates (Fig. 8a). Analyzing the different pro- 0 0
cess phases, more oxidized organic intermediates were formed 0 4 8 12 16 20 24 28
at the beginning of the process, with substantial mineraliza- Time (days)
tion, principally during the Fenton oxidation, which is corrob- Fig. 8 a Solar-photo-Fenton treatment of the cotton-textile dyeing
orated by fast COD and DOC decrease until H2O2 consump- wastewater: COD, DOC, COS and LMCA/DOC ratio. b Zahn–Wellens
tion of 2.3 mM. To achieve almost complete decolorization test for selected samples during the solar-photo-Fenton treatment:
(98 %), it was necessary less than 2.3 mM of H2O2, following —S0, DOC=151.2 mg L−1; —S1, DOC=148.0 mg L−1; —S2,
DOC=97.4 mg L−1; —S3, DOC=93.1 mg L−1; —S4, DOC=62.9-
the same trend of the mineralization process and in agreement mg L−1; —S5, DOC=56.9 mg L−1; —S6, DOC=50.1 mg L−1;
with the kinetic tests conducted, both at lab and pilot scale —reference (DOC=107.6 mg L1)
Environ Sci Pollut Res
biodegradability remained approximately constant for the
sample that suffered the acidification process until pH 2.8,
however, decreased for 32 % for the sample after the addition
of iron, which can be attributed to the sedimentation of some
biodegradable compounds during the precipitation of iron
phosphate, which is in agreement with the decrease of phos-
phates concentration from 6.7 mg L−1 to values lower than
the detection limit of the analytical method, and dissolved
iron concentration reduction from 60.0 to 48.7 mg L−1. How-
ever, as expected, the biodegradability of the textile waste-
water was enhanced during the photo-Fenton treatment,
achieving values of 38, 40, 48, and 58 %, corresponding to
2.5, 7.5, 12.7, and 17.0 mM of H2O2 consumed (samples 3,
4, 5, and 6), respectively. Taking into consideration three
main factors: (a) higher LMCA/DOC ratio; (b) Zahn–
Wellens results and (c) UV energy and H2O2 savings; sample
4 can be considered the best point to stop the pre-oxidation
process to achieve a COD<250 mg O2 L−1 (discharge limit
into water bodies imposed by the Portuguese Legislation-
Portaria no. 423/97 of 25 June 1997) after the 28 days of the
Zahn–Wellens test. Considering the combination of a photo-
Fenton reaction with a biological oxidation process in order
to reach a final COD below 250 mg O2 L−1, the energy dose
required for the photo-Fenton reaction is 0.5 kJUV L−1


t 30W ¼ 3:2 min; T ¼ 30:7  C; pH ¼ 2:80; UVG;n ¼ 13W m−2
consuming 7.5 mM of hydrogen peroxide (added in excess),
as calculated from the kinetic studies performed at pilot plant
under natural solar radiation, and leading to 58.4 % miner-
alization (DOCfinal =62.9 mg C L−1). Throughout the treat-
ment, the dissolved nitrogen concentration remained approx-
imately constant (113–117 mg N L−1). Nitrite concentration
decreased from 5.3 to 1.9 N-NO2− L−1 principally after the
acidification process, although no nitrates were detected. On
the other hand, ammonia increased from 79 to 91 mg N-
NH4+ L−1 mainly due to the oxidation of the organic nitro-
gen. Sulfates increased from 34 to 1,600 mg L−1 as the result
of the addition of sulfuric acid for the acidification and iron
sulfate. Chloride concentration remained at around 108 mg
Cl− L−1.
Conclusions
Cotton-textile dyeing wastewater present a moderate organic
load and low to moderate biodegradability mainly due to the
presence of a mixture of recalcitrant dyes used in the dyeing
process, which must be removed before discharge into the
water bodies. The solar-photo-Fenton treatment was the
most efficient of all solar AOPs studied, enhancing the
biodegradability of the effluent and making possible its
combination with a biological oxidation process, being possi-
ble to achieve a wastewater with a COD below 250 mg O2 L−1.
The minimum iron concentration needed to compete efficiently
for the photons with the other absorbing species in solution,
leading to the highest reaction efficiency, is 60 mg L−1. Al-
though the better results with photo-Fenton reaction were
obtained at pH 2.8, the efficiency remained approximately
constant until pH of 3.6, decreasing the costs associated with
acid and base consumption. The photo-Fenton efficiency in-
creased greatly with the temperature, principally from 10 to
30 °C, mainly due to the thermal reactions involved in the
reduction of ferric ion, which use radiation of wavelengths
higher than 500 nm. This condition is favorable, because the
textile wastewater normally presents temperatures higher than
30 °C. The reaction rate remained approximately constant
within the range of radiation intensities studied, which
proves that the photo-Fenton reaction can be used effi-
ciently during all the year or in regions with lower solar
radiation intensities. Finally, considering the combina-
tion of a photo-Fenton reaction with a biological oxida-
tion system for the treatment of the textile wastewater in order to
reach a COD below 250 mg O2 L−1, the energy dose required for
the photo-Fenton reaction is 0.5 kJUV L−1 t 30W ¼ 3:2 min; T ¼
30:7  C; pH ¼ 2:80; UVG;n ¼ 13W m−2 Þ consuming 7.5 mM
of hydrogen peroxide and leading to 58.4 % mineralization
(DOCfinal =62.9 mg C L−1).
Acknowledgments This work was partially supported by project PEst-C/
EQB/LA0020/2011, financed by FEDER through COMPETE—Programa
Operacional Factores de Competitividade and by FCT—Fundação para a
Ciência e a Tecnologia. Petrick A. Soares and Diego R. Manenti acknowledge
their Ph.D. fellowships (BEX 5512-10-7 and 9794-11-5) supported by
CAPES. Tânia Silva also wants to acknowledge her Ph.D. scholarship,
reference SFRH/BD/73510/2010, supported by FCT. Vítor Vilar acknowl-
edges Ciência 2008 Program.
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