Science of the Total Environment 609 (2017) 329340

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Science of the Total Environment

journal homepage: www.elsevier.com/locate/scitotenv

Photocatalytic ozonation using doped TiO2 catalysts for the removal of

parabens in water
Joo F. Gomes a,, Ins Leal a, Katarzyna Bednarczyk b, Marta Gmurek c,, Marek Stelmachowski b,
Magdalena Diak d, M. Emlia Quinta-Ferreira e, Raquel Costa a, Rosa M. Quinta-Ferreira a, Rui C. Martins a
a
CIEPQPF Chemical Engineering Processes and Forest Products Research Center, Department of Chemical Engineering, Faculty of Sciences and Technology, University of Coimbra, Rua Slvio Lima,
3030-790 Coimbra, Portugal
b
Faculty of Process and Environmental Engineering, Department of Safety Engineering Lodz University of Technology, Wolczanska 213, 90-924 Lodz, Poland
c
Faculty of Process and Environmental Engineering, Department of Bioprocess Engineering, Lodz University of Technology, Wolczanska 213, 90-924 Lodz, Poland
d
Faculty of Chemistry, Department of Environmental Technology, University of Gdansk, ul. Wita Stwosza 63, 80-308 Gdask, Poland
e
CNC Center for Neuroscience and Cell Biology and Department of Physics, Faculty of Sciences and Technology, University of Coimbra, Rua Larga, Coimbra P-3004-516, Portugal

H I G H L I G H T S G R A P H I C A L A B S T R A C T

Parabens degradation by photocatalytic

ozonation with UVA and doped TiO2
Photocatalytic ozonation improves the
endocrine disruptor compounds degra-
dation.
Photolytic and photocatalytic ozonation
promotes toxicity reduction of
parabens.
Hydroxylation seems to be the most
relevant reaction pathway.
Ag-TiO2 shows the best performance on
photocatalytic ozonation.

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

Article history: Conventional wastewater treatments are inefcient for the removal of parabens. The aim of this study was nd-
Received 23 May 2017 ing a suitable solution using ozone and UVA irradiation combined with TiO2 catalysts doped with different noble
Received in revised form 14 July 2017 metals (Ag, Pt, Pd, Au). Photocatalytic ozonation required lower amounts of ozone for higher efciency on the re-
Accepted 20 July 2017
moval of parabens, chemical oxygen demand (COD) and total organic carbon (TOC). The best catalyst for the ini-
Available online 25 July 2017
tial contaminants degradation was 0.5% Ag-TiO2 leading to total parabens removal using 46 mgO3/L. Due to the
Editor: D. Barcelo relative low mineralization achieved, the toxicity of the treated solutions was still compared with the initial one
over several species (Vibrio scheri, Lepidium sativum and Corbicula uminea). All the treatments applied led to a
Keywords: clear decrease on the toxicity compared with initial mixture of parabens. From an economical point of view, it
Photocatalytic ozonation was concluded that the presence of UVA irradiation increased the energy consumption compared with catalytic
Parabens degradation ozonation with these catalysts but it can decrease the time of reaction. From the by-products analysis, it was con-
Doped TiO2 cluded that hydroxylation appears to be the most signicant reaction pathway and the main responsible for
Toxicity parabens degradation.
Cost evaluation
2017 Elsevier B.V. All rights reserved.
By-products analysis

Corresponding authors.
E-mail addresses: [email protected] (J.F. Gomes), [email protected] (M. Gmurek).

http://dx.doi.org/10.1016/j.scitotenv.2017.07.180
0048-9697/ 2017 Elsevier B.V. All rights reserved.
330 J.F. Gomes et al. / Science of the Total Environment 609 (2017) 329340

1. Introduction 400 nm) (Chong et al., 2010; Pelaez et al., 2012). Doping TiO2 with
nanoparticles of noble metals (such as Pt, Pd, Au, Ag) decreases the
The demand for potable water will be one of the main challenges of band gap energy allowing TiO2 absorption in UVA and visible region
this century, since the water resources are being continuously polluted (Zheng et al., 2011; Wang et al., 2012).
by different types of emerging contaminants. The application of conven- Titanium dioxide with enough photon energy enhances the
tional wastewater treatment technologies for its degradation reveals a photogeneration hole-electron pair (Eq. (1)). The adsorption of ozone
lack of efciency (Bledzka et al., 2014; Bolz et al., 2001; Gibs et al., molecules on photocatalyst surface can occur by different ways, such
2007; Kasprzyk-Hordern et al., 2008; Yu et al., 2011). A particular case as, physical adsorption, formation of hydrogen bonds with surface of
of emerging contaminants it should be referred to widely used com- hydroxyl groups, molecular adsorption into weak Lewis sites and disso-
pounds such as parabens. These compounds are used as antimicrobial ciative adsorption with strong Lewis sites (Bulanin et al., 1995). This
and preservatives in drinks, pharmaceutical and personal care products way, the photogenerated electrons can react with ozone molecules
(Calafat et al., 2010; Canosa et al., 2007; Meeker et al., 2013), and appear adsorbed on the catalyst surface, that works as electron acceptor pro-
as a group of emerging compounds reaching the water resources since ducing ozonide radicals (Eq. (2)) (Mehrjouei et al., 2015; Rivas et al.,
they are hardly degraded. Some parabens (methyl, ethyl and propyl) 2006; Rodrguez et al., 2013). Besides, ozone works as electrons scaven-
were found in rivers and in wastewater treatment plants (Yu et al., ger decreasing the recombination rate of hole-electron pairs. This re-
2011). The presence of these contaminants on water and the scarcity combination phenomenon also decreases in the presence of metallic
of water resources, make as priority the implementation of municipal nanoparticles on the semiconductor catalyst surface that scavenge the
wastewater (MWW) reclamation and reuse strategies (Bixio et al., photogenerated electrons (Anpo and Takeuchi, 2003; Bahruji et al.,
2006). On this way, several new technologies, such advanced oxidation 2010). It is expected that the mechanism of photocatalytic ozonation
processes, are required to improve the degradation of parabens. is similar to photocatalysis, therefore the photogenerated holes can
Ozone is a powerful oxidant and under water treatment conditions react with water molecules adsorbed on the catalyst surface to produce
can act in a direct pathway or produce hydroxyl radicals, which can ox- hydroxyl radicals (Eq. (3)), this reaction preferably occurs at acidic con-
idize a large spectrum of organic compounds (Gomes et al., 2017a; ditions (Mehrjouei et al., 2015).
Martins and Quinta-Ferreira, 2009a; Martins and Quinta-Ferreira,

2009b). However, predominantly single ozonation cannot mineralize TiO2 h h e 1
the organic compounds. Moreover, refractory by-products are produced
that can be more or less toxic compared to the initial organic pollutants O3ads e O3 2
(Martins and Quinta-Ferreira, 2009a). The UVA irradiation with

photocatalysts possibly improves the degradation of organic com- H2 Oads h OH 3
pounds. In this system, the photogenerated holes and electrons are
the main responsible for this improvement of degradation. For this pro- The ozonide radicals generated during ozone adsorption can react
cess, molecules such as oxygen and water are required to generate su- directly with organic contaminants or, at acidic conditions, the hydroxyl
peroxide (O
2 ) and hydroxyl radicals ( OH), capable of mineralizing radicals formation can be favored, as shown by Eq. (4) (Hernndez-
the contaminants into water and carbon dioxide (Chong et al., 2010). Alonso et al., 2002).
In fact, photocatalysis in the absence of oxygen or even single photolysis
normally are not efcient on the degradation of some organic com- O3 H HO 3
OH O2 4
pounds (Gomes et al., 2017b; Lin et al., 2011; Oarska et al., 2016;
Oros-Ruiz et al., 2013; Velegraki et al., 2015). Therefore, for improving Hydroxyl radicals can also be formed from the subsequent rapid
the efciency of the process, the addition of a compound that will act equilibrium of ozonide, as can be seen in the Eq. (5) (Merenyi et al.,
as electron scavenger is necessary. Thus, the application of a more reac- 2010).
tive molecule than oxygen, such as ozone, would be interesting. Follow-
ing that, for the elimination of hardly degraded organic contaminants, O3 O O2 O H2 O OH OH 5
the combination of photocatalysis and ozone, will probably push the re-
action towards mineralization. In fact, ozone is a stronger oxidant than In photocatalytic ozonation, it is predictable that other reactive oxy-
oxygen which will speed up the degradation rate leading to a more ef- gen species can appear, such as superoxide radicals (O 2 ), because as it
fective process (Agustina et al., 2005). Moreover, Hernndez-Alonso can be seen in Eq. (4), oxygen molecules, are resultant products of hy-
et al. (2002) conrmed by Electron Spin Resonance (ESR) signals analy- droxyl radical formation from hydrogenation of ozonide, and can be re-
sis that oxygen adsorbed on TiO2 surface has lower electroafnity com- duced by the remaining photogenerated electrons. These superoxide
pared to ozone. Thus, ozone will allow to trap a higher amount of radicals can oxidize organic compounds or react with other intermedi-
photogenerated electrons reducing the electron-hole recombination ates to produce hydroxyl radicals (Mehrjouei et al., 2015).
phenomenon. This will enhance the contaminants degradation The photocatalytic ozonation has been recently studied on the deg-
efciency. radation of emerging contaminants. The photocatalytic ozonation (O3/
In this context, the combination of ozonation, heterogeneous cataly- UV/TiO2) led to complete mineralization of amoxicilin and diclofenac
sis and UVA irradiation allows an increase in photogenerated electron- after 30 and 120 min respectively (Moreira et al., 2015). Rodrguez
holes pairs at the photocatalyst surface, that can reduce electron accep- et al. (2013) showed that at acid conditions (pH 4) the total polypheno-
tor or oxidize water and contaminants. This will improve the production lic content and total organic carbon (TOC) removal of atenolol, hydro-
of reactive oxygen species, such as hydroxyl radicals (OH), superoxide chlorothiazide, ooxacin and trimethoprim mixture, were improved
radicals (O
2 ) and ozonide radicals (O3 ) (Mehrjouei et al., 2015). Bear- under TiO2/O3/UVA irradiation. This was related to the formation of hy-
ing this in mind, photocatalytic ozonation appears as a promising tech- droxyl radicals through ozonide resulting at these conditions
nology that will improve contaminants mineralization for water (Rodrguez et al., 2013). For these compounds with O3/TiO2/solar radia-
reclamation. Nevertheless, it is necessary to select a photocatalyst tion 70% of TOC and 90% of toxicity removal were achieved in 2 h
with a band gap lower or equal to the photon energy resulting from (Mrquez et al., 2014).
UVA irradiation. Titanium dioxide (TiO2) is the most frequently used Bearing in mind the novelty and interest of this technology for water
photocatalyst, because this semiconductor presents good optical and reclamation, the aim of this work was to evaluate the degradation of a
electronic properties, low cost and non-toxic characteristics. This mixture ve water contaminants namely methylparaben (MP),
photocatalyst normally presents a band gap higher than 3 eV ( b ethylparaben (EP), propylparaben (PP), butylparaben (BuP) and
 J.F. Gomes et al. / Science of the Total Environment 609 (2017) 329340 331

benzylparaben (BeP) under photocatalytic ozonation. For this purpose (Fig. 1). The photon ux was obtained using ferrioxalate actinometer ac-
the noble metals Ag, Au, Pd, Pt, at loadings of 0.5 wt%, doped onto TiO2 cording to the method proposed by Kuhn et al. (2004) and was calculat-
were tested. The next goal was to check if metals are able to improve ed at 5.75 107 Einstein (Ls) 1. In photocatalytic ozonation
TiO2 photocatalytic activity since they are capable to reduce the energy experiments, 5 min before ozone fed and the light irradiation started,
band gap and avoid electron-hole recombination. Moreover, photocata- the reaction solution containing parabens (10 mg L1 each) as well as
lytic ozonation (O3/catalyst/UVA irradiation) was compared with pho- catalysts (70 mg L1) was placed inside the reactor to test the catalyst
tolytic ozonation (O3/UVA irradiation). adsorption capacity (Gomes et al., 2017b). The stirring speed was previ-
Furthermore, the toxicity assessment was performed. To cover a ously established at 700 rpm to ensure chemical regime, which means
wide range of trophic levels, three different species such as Vibrio that external and internal diffusion limitations can be neglected
scheri (bacteria), Corbicula uminea (clam) and Lepidium sativum (Martins and Quinta-Ferreira, 2009a). Moreover, the catalyst particles
(plant) were used. had an average diameter of 500 nm (determined through SEM). During
To the best of our knowledge, this is the rst time noble-metal doped the reaction, samples were withdrawn at 1, 2, 5, 10, 15, 30, 45, 60, 90
TiO2 catalysts are applied in photocatalytic ozonation for parabens deg- and 120 min and immediately centrifuged at 3500 rpm (Nahita 2655
radation Moreover, the analysis of the degradation of a mixture rather Centrifuge) to remove the catalyst and posterior analysis of degradation
than individual compounds is a novel feature of the work. The use of by HPLC. The volume taken never exceeded 10% of total volume. The
mixtures increases the difculty of degradation compared to individual inlet ([O3]in) and outlet ([O3]out) ozone concentration were measured
parabens. Moreover it can give more realistic data regarding the behav- using two ozone analysers (BMT 963 and 964 vent, BMT), allowing
ior of treatment processes when applied for the degradation of real the determination of transferred ozone dose (TOD) according to Eq. (6)
wastewaters containing these dangerous compounds. In fact, usually
in pharmaceutical and personal care products, these substances are
Zt  
used as a mixture to increase the preservative spectrum. It should be re- Q Gas
TOD  O3 in O3 out  dt 6
inforced the novelty related with toxicity analysis. Since the treatment V Liquid
0
processes proposed are not able to totally mineralize organic matter it
is essential to understand the potential effect of the resulting treated ef-
uents over the ecosystems. This implies the analysis of the impact of Where QGas represents the gas ow rate (0.2 L min1), VLiquid is the vol-
raw and treated waters over a wide range of species with different sen- ume of the efuent used in the reactor. The TOD were expressed in mg
sitivities towards contaminants. O3 L1.
Ozone was produced by ozone generator (802N, BMT) from pure ox-
2. Materials and methods ygen stream (99.9%). The remaining ozone that leaves the reactor was
trapped by a solution of Potassium iodide (Panreac).
2.1. Chemicals and catalysts preparation
2.3. Analytical methods
Titanium (IV) isopropoxide (97%) was used as titanium source for
the preparation of catalysts and was purchased from Aldrich Chem. The microstructural analysis of the catalyst surface and particles av-
Butylparaben (BuP) was purchased from Fluka and methylparaben erage diameter were performed using a TESCAN VEGA 3 SBH - Easy
(MP), ethylparaben (EP), propylparaben (PP) and benzylparaben Probe Scanning Electron Microscopy (SEM) with a tungsten heated
(BeP), were obtained from Sigma-Aldrich. The solution used in these cathode. The dispersion of metals on catalyst surface was analyzed by
tests was prepared from a mixture of these ve parabens (10 mg L1 Energy Dispersive X-Ray Analysis (EDS) using a Bruker QUANTAX sys-
each) in ultrapure water. This concentration is commonly used in stud- tem that includes the Bruker Nano XFlash detector, which works ac-
ies involving these contaminants (Lin et al., 2011; Gmurek et al., 2015; cording to the principle of the silicon drift detector (SDD). EDS
Lin et al., 2009; Martins et al., 2016). The standards of 4- analysis was carried out using an accelerating potential of 20 kV and
Hydroxybenzoic acid (4-HBA), 3,4-Dihydroxybenzoic acid (3,4- real time for the spectrum accumulation of 60 s at a dwell time of
diHBA), 2,4-Dihydroxybenzoic acid, Hydroquinone, 1,4-Benzoquinone 16 ms. Energy-Channel calibration was used with a copper standard
and 3,4,5-Trihydroxybenzoic acid were acquired from Sigma-Aldrich. (Ka 8.0463 keV). EDS was performed to several random selected points
Titanium (IV) isopropoxide was used to prepare all catalysts. It is of the samples. The crystalline structure of the catalysts powders was
known to be a source for the anatase-type TiO2. An adequate amount evaluated by X-ray diffraction (XRD) analysis, through a diffractometer
of the KAuCl4 (0.5 wt%), methanol and distilled water were mixed (Bruker D8 Advance). The diffractometer works with Cu K radiation
with titanium (IV) isopropoxide for preparing Au-modied TiO2. This (2.2 kW ceramic tube). Using a 1D LynxEye detector (Silicon Drift De-
mixture was stirred at room temperature during 2 h, followed by a tector) covering an angle of ~3 and with ~25% energy resolution. SDT
24 h thermal treatment at 45 C and calcination at 400 C for 2 h. Q600 (TA Instruments) was used for thermogravimetric analysis
The other catalysts (Pt-TiO2, Pd-TiO2 and Ag-TiO2) were obtained (TGA), for evaluating the thermal resistance of catalysts at higher tem-
through photo-deposition by UV-reduction of Pt4+, Pd2+, Ag+ ions in peratures (maximum 1200 C). The BET (BrunauerEmmetTeller
the titanium dioxide suspension. An aqueous solution of isopropanol (SBET)) specic surface area of the catalysts were analyzed using nitro-
containing H2PtCl6 (0.5 wt%) or PdCl2 (0.5 wt%) was degassed with ni- gen (196 C) with an accelerated surface area and porosimetry ana-
trogen and irradiated by UVVis light (1000 W Xe lamp) for 6 h. An lyzer (ASAP 2000, Micrometrics). According to De Lange et al. (2014),
aqueous solution of ethanol containing AgNO3 (0.5 wt%) was degassed adsorptive characterization using N2 can be employed if the solids pres-
with nitrogen and irradiated by UVVis light (1000 W Xe lamp) for ent a specic surface area higher than 5 m2 g1.
100 min. The modied TiO2 catalysts were separated by centrifugation XPS (X-ray photoelectron spectroscopy) analyses were carried out
and dried at 65120 C for 12 h. with a Kratos AXIS Ultra spectrometer using monochromatic Al K X-
Rays source of an excitation energy equal to 1486.6 eV. The spectra
2.2. Experimental apparatus were obtained using an analysis area of 300 m 700 m. The power
of anode was set at 150 W and the hemispherical electron energy ana-
The experiments were carried out in a 2 L glass photoreactor lyzer was operated at a pass energy 20 eV for all high resolution mea-
equipped with 3 lamps (Philips TL 6 W BLB, tube diameter of 16 mm) surements. All measurements were performed with the use of a
which transmit UVA irradiation (main emission 365 nm), at controlled charge neutralizer due to semiconducting character of the samples.
temperature (25 1 C) by a thermostatic bath during 120 min The background subtraction of XPS spectra was performed with Shirley
332 J.F. Gomes et al. / Science of the Total Environment 609 (2017) 329340

Fig. 1. Scheme of experimental photoreactor.

algorithm and the adventitious carbon main peak (C 1s, 284.8 eV) was C. uminea (clams) individuals were collected from a canal in Mira,
used for a nal calibration of each spectrum. Portugal (N402506.90/W84413.18). Individuals with shell length
High-performance liquid chromatography HPLC (UFLC, Shimadzu, in the range 2030 mm were selected and transported in eld water
equipped with a diode array detector), was used for the determination to the laboratory, where they were gradually acclimated for one week
of each paraben concentration along the reaction time. The injection before experiments. Two replicates were used for each efuent concen-
volume of samples was 20 L and the mobile phase (0.5 mL min 1) tration (50, 75 and 100% V/V) with a blank control (dechlorinated
consisted in a mixture of 50:50 methanol: acidic water (0.1% orthophos- water). The efuents were dosed after 24 h acclimation to the test
phoric acid). A C18 (SiliaChrom) column at 40 C was used and the pots in a ratio of 1 L of test medium to 20 clams. The vessels were
parabens detection occurred at 255 nm. The identication of by- kept at constant temperature (20 2 C), under a 16 hLight:8 hDark pho-
products followed the same procedure. Reaction samples were directly toperiod cycle and continuous aeration. The mortality of clams was
injected and the compounds identication was performed by compar- assessed every 24 h along the test period based on siphoning activity ev-
ing peaks retention times with those obtained when each compound idence or resistance to valve opening when forced with a blunt dissec-
standard solutions were injected. Calibration curves were obtained for tion needle (Gomes et al., 2014).
each substance and Table S1 shows the respective coefcient of deter- To evaluate the phytotoxicity of the samples, the number of L.
mination (R2), limit of detection (LOD) and limit of quantication sativum (plant) germinated seeds and the radicle growth were deter-
(LOQ). The LOD was calculated using the coefcient of 3.3 with quotient mined to calculate the germination index (GI) (Trautmann and
between standard deviation and slope of calibration curve. LOQ was de- Krasny, 1997). In this test, 10 seeds of L. sativum were evenly spread
termined using the coefcient of 10 with the same quotient. over a lter paper on a petri dish. The volume of sample used was
The total organic carbon (TOC) for initial and treated solutions was 5 mL. The tests were performed using the treated efuents (120 min
determined using a TOC analyzer (TOC-V CPN model, Shimadzu, of photocalytic ozonation) (100% V/V). The petri dishes lled with the
Japan) coupled to an autosampler (model V-ASI, Shimadzu, Japan). samples were placed in an oven for 48 h at constant temperature of
Chemical oxygen demand (COD) was measured according to the stan- 27 C in the dark. After this, the number of seeds germinated and radicle
dard method 5220D (Greenberg et al., 1985). Potassium hydrogen growth of each one is recorded. GI is the product of relative seed germi-
phthalate, obtained from Panreac, was used to prepare a calibration nation (RSG) and relative radicle growth (RRG). The phytotoxicity was
curve with COD values within the range 0100 mg O2 L1. After 2 h of classied using the germination index according to Trautmann and
digestion at 150 C (ECO25 Velp Scientica), the absorbance was mea- Krasny (1997) criteria. The pH of all the samples was corrected to 7
sured at 445 nm in a WTW photolab S6 photometer. using a NaOH solution prior to the toxicity tests.
pH was determined using a Crison micropH 2002 apparatus. The pH
of the ultrapure water with 10 mg L1 of parabens at the beginning of 3. Results and discussion
photocatalytic ozonation was 5.7 and at the nal pH value after
120 min of reaction falls to 3.2 whichever the operating conditions 3.1. Catalyst characterization
tested.
The SEM analysis (Fig. 2) shows that sol-gel preparation method use
2.4. Toxicity assessment for Au-TiO2, did not change signicantly the shape and morphology of
original TiO2 particles (Fig. 2a). Besides, the well-dened shape of Au-
The inhibition of luminescence was measured to evaluate the toxic- TiO2 particles (Fig. 2b), with higher agglomeration of particles can be
ity of samples against V. scheri bacteria using a LUMIStox 300 appara- observed. The size of particles is higher comparatively to other catalysts
tus from Dr. Lange GmbH (HACH). The untreated and treated samples, (Fig. 2c, d, e). On the other hand, the shape and morphology of TiO2 par-
for the different reaction conditions, were inoculated with the bacteria ticles suffer some alterations after photo-deposition of noble metals
solution at 15 C in a LUMISTherm (HACH). Luminescence was mea- (Ag, Pt and Pd). For these catalysts the size of the particles is lower at
sured directly in the LUMIStox 300 after 15 min of incubation and com- the nanoscale and the materials show a certain roughness on their sur-
pared with a blank, where bacteria were placed in a NaCl solution (2%). faces (Fig. 2c, d, e). It can be concluded that the sol-gel methodology for
 J.F. Gomes et al. / Science of the Total Environment 609 (2017) 329340 333

Fig. 2. SEM images (25,000) of different materials (a - TiO2; b - Au-TiO2; c - Ag-TiO2; d - Pt-TiO2; e - Pd-TiO2).

preparation of catalysts is more efcient than photo-deposition in what Morphological and surface characterization of the samples (Pt, Pd,
regards metal dispersion. On the other hand, EDS analysis revealed a Ag and Au nanoparticles photodeposited on TiO2) were studied and
good dispersion of metals on TiO2 surfaces except for Pt-TiO2 which published elsewhere (Gomes et al., 2017a; Gomes et al., 2017b; Diak
conrmed a low metal dispersion (Gomes et al., 2017a). et al., 2015; Grabowska et al., 2016).
The surface composition of the samples was determined from the in- The XRD analysis of the catalysts showed that anatase phase is pre-
tensities of the characteristic photoelectron lines taken in high resolution, dominant which means that band gap of pure titanium dioxide is prob-
and atomic sensitivity factors provided by the manufacturer of the XPS ably close to 3.2 eV. Therefore, the UVA irradiation used in this work is
system. The relative concentrations of elements in Pt-TiO2 as well as in enough to cause the production of photogenerated electron-hole pairs.
Pd-TiO2 and Ag-TiO2, are provided in Table 1. Based previous research However, it is likely that application of noble metals for TiO2 doping re-
where Au-TiO2 catalysts exhibits the lowest photochemical activity the sults in the reduction of band gap. For the other catalysts, doped with
XPS analysis was not performed. Pt shows the lowest incorporation per- noble metals, no signicant variations occurred on XRD patterns com-
centage, while for Ag the percentage found was near the theoretical one. pared to the one observed for pure TiO2. It is probably due to the low
334 J.F. Gomes et al. / Science of the Total Environment 609 (2017) 329340

Table 1
Relative elemental concentrations obtained from the XPS composition analysis.

Catalysts O (%) Ti (%) C (%) Ag content (at.%) Pt content (at.%) Pd content (at.%)

0.5 Pt-TiO2 48.70 0.55 20.73 0.01 30.46 0.54 0.13 0.01
0.5 Pd-TiO2 55.88 0.05 23.66 0.62 20.24 0.66 0.23 0.01
0.5 Ag-TiO2 58.63 0.66 23.84 0.25 17.06 0.88 0.47 0.04

load of metals used for their preparation (0.5% wt.) (Gomes et al., TiO2 (149 m2 g1) Pt-TiO2 (238 m2 g1) (Gomes et al., 2017a). The
2017b). higher specic surface area of Pt-TiO2 can be related to the low metal
For evaluating the thermal stability of the catalysts powders, the dispersion conrmed previously by EDS analysis.
thermogravimetric analysis was performed for a wide range of temper-
ature from 25 C to a maximum of 1200 C, with a heat rate of 10 C 3.2. Photocatalytic ozonation
min1. The maximum weight loss, to Au-TiO2, Pd-TiO2 and pure TiO2,
occurred between room temperature and 300 C, which represents Total parabens degradation for all tested conditions in the photocat-
the evaporation of water from the surface of the catalysts. For Pt and alytic ozonation experiments was achieved (Fig. 3). The presence of cat-
Au-TiO2, the thermogravimetric analysis reveals high weight loss be- alysts improves the parabens degradation, as can be seen in Fig. 3. Using
tween 400 and 1100 C which can be attributed to the decomposition the catalysts, the transferred ozone doses required for total depletion
of organic solvents. But weight losses lower than 10% in this range of are lower compared to the single photoozonation. In fact, for single
temperatures conrms the thermo stability of the catalysts (Gomes photoozonation total parabens degradation was achieved using about
et al., 2017b). 118 mg L1 of TOD, while for the worst catalyst in terms of efciency
The BET analysis of catalysts powders reveals that specic surface of parabens degradation (0.5% Au-TiO2) only about 84 mg L1 of TOD
areas of catalysts increase accordingly (values between brackets): Ag- was necessary. This reduction on the amount of ozone makes the
TiO2 (34 m2 g 1) b Pd-TiO2 (73 m2 g1) b Au-TiO2 (135 m2 g 1) b usage of catalyst coupled with UVA irradiation an interesting option

Fig. 3. Normalized concentration of individual parabens (a methylparaben (MP); b ethylparaben (EP); c propylparaben (PP); d buthylparaben (BuP) and e benzylparaben (BeP))
during photolytic and photocatalytic ozonation of the mixture as a function of TOD.
 J.F. Gomes et al. / Science of the Total Environment 609 (2017) 329340 335

on parabens degradation. Furthermore, in a previous work, the single 125 kJ mol1 which means that not too much energy is necessary for re-
ozonation without UVA irradiation required around 170 mg L 1 of leasing an electron compared with platinum (205 kJ mol1) and gold
TOD for achieving total parabens degradation (Gomes et al., 2017a). (223 kJ mol1).
Therefore, the presence of UVA irradiation allows a reduction around
30% in the amount of ozone. This reduction was further enhanced in 3.3. COD removal and mineralization of parabens mixture
the presence of catalysts (Fig. 3).
From all tested compounds, the benzylparaben has highest molecu- The initial parabens mixture has a COD value of 95 mg L1. Even if
lar weight and comprises two aromatic rings. So, these two characteris- total degradation of the parent parabens is achieved for all treatments
tics can explain the lower amount of ozone necessary for achieving its applied, the COD is never totally removed, which means that the degra-
complete degradation. Martins and Quinta-Ferreira (2009b) studied dation of parabens produces some refractory by-products. The presence
the ozonation for phenolic content removal and veried that ozone is of catalyst improves photolytic ozonation on COD removal (Fig. 4). The
very reactive with the nucleophilic sites of phenolic ring. 0.5% Ag-TiO2 photolytic ozonation using a TOD of 118 mg L1 can remove 27% of the
was the most efcient catalyst on parabens degradation leading to initial COD. In fact, after an ozone dose of 88 mg L1 the further increase
total degradation of BeP using 30 mg L 1 of TOD. On other hand the on oxidant had no signicant effect over COD removal. Gomes et al.
worst catalyst, 0.5% Au-TiO2, needed about the double amount of TOD (2017a) using a TOD of 118 mg L1 with single ozonation achieved a
(60 mg L 1) for achieving the same result. The BET analysis reveals COD removal of around 22%, therefore the presence of UVA irradiation
that specic surface area of Au-TiO2 (135 m2 g1) is higher than the do not change signicantly the amount of organic matter removed
one of Ag-TiO2 (34 m2 g1). It seems that the type of active sites rather when compared with O3 by itself. Ozone is the main responsible for
than the surface area available for reactions determines the process ef- parabens degradation with this kind radiation without photocatalysts
ciency. As described above, for the remaining parabens the 0.5% Au- On the other hand, the lowest value of COD, corresponding to 50% of
TiO2 was the most inefcient catalyst. As can be seen in Fig. 3, pure the initial COD, was achieved for the Pt-TiO2 using a TOD of 60 mg
TiO2 was more efcient than Au-TiO2. This result can be probably ex- L1. However, Ag-TiO2 reduced the COD to 44% of the initial value
plained by the electronegativity of gold. According to Pauling scale, using a TOD of 46 mg L1 (Fig. 4). In a previous study, for catalytic ozon-
the electronegativity of the noble metals used in these catalysts de- ation with Ag-TiO2 the COD removal was very low (around 6% with a
creases following this order (values between brackets): Au (2.54) N Pt TOD of 95 mg L1 (Gomes et al., 2017a)). So with this result it may be
(2.28) N Pd (2.20) N Ag (1.93). Gold is the noble metal with the highest concluded that the improvement on organic matter degradation was
capacity to retain photogenerated electrons (Eq. (1)), therefore lower due to the UV-A irradiation. Maybe the presence of photogenerated
amount of ozone can be reduced. Besides this, higher electron afnity electrons and holes promotes organic matter degradation through an
of gold (223 kJ mol1) when compared with the other metals difcult increase of reactive oxygen species. Until a TOD of 20 mg L1 for Ag-
the release of electrons, so few ozonides radicals (O
3 ) can be produced TiO2 the behavior of COD removal was similar to photolytic ozonation,
(Eq. (2)), and consequently lower amount of hydroxyl radicals (OH) achieving for this TOD 6% of COD removal. After this COD removal suf-
may be generated (Eq. (4)) (Oros-Ruiz et al., 2013). Therefore with fers a signicant abatement, around 20% for an increase of 10 mg L1
pure TiO2 probably the photogenerated electrons (Eq. (1)) were not of TOD. This can be explain by the fact that until a TOD of 20 mg L1
retained and were available to reduce O3. The difference between pure total degradation of BeP and about 90% of remaining parabens are re-
TiO2 and the remaining catalysts maybe the result of the noble metals moved. Ozone by itself is very reactive with these contaminants due
present on the catalyst surface (Zheng et al., 2011; Wang et al., 2012). their nucleophilic sites. Thus, until a TOD of 20 mg L1 the COD removal
On one hand, more electrons are generated since the energy gap is is most likely due parabens abatement. Therefore, the main differences
lower, but the presence of metals reduces electron-hole recombination. on COD removal veried afterwards between photolytic ozonation and
Besides the metals with low electron afnity makes the photogenerated photocalytic ozonation using Ag-TiO2 will be due to intermediates de-
electrons available to react with ozone hence producing higher amount composition which are probably less reactive with ozone.
of ozonide and hydroxyl radicals. Using a TOD of 25 mg L1, the catalytic system involving Pd-TiO2
The catalytic ozonation with these catalysts was investigated previ- only removed 2% of initial COD. Thus, using a low ozone dose in the
ously (Gomes et al., 2017a). The best results for parabens degradation presence of UVA irradiation applying Pd-TiO2 as catalyst inhibits the
(MP, EP, PP, BuP and BeP) were achieved for platinum and palladium degradation of organic matter. Possibly for this ozone dose occur the
supported on TiO2 surface. Total parabens degradation was complete production of refractory intermediate compounds that are still
for a TOD of about 70 and 80 mg L1 with these two catalysts, respec- accounted as COD, since the parent parabens degradation for this TOD
tively (Gomes et al., 2017a). In the present study, the best results on is above 75%. After this TOD value, the photocalatyic ozonation with
parabens degradation were obtained using Ag-TiO2 and Pt-TiO2. For Pd-TiO2 leads to higher COD removal rates and, using a TOD of 80 mg
Pd-TiO2 the total parabens (MP, EP and PP) degradation was achieved
using about 64 mg L1 of TOD, which is a small difference for the TOD
required by ozonation using this catalyst (80 mg L1) without UVA. In
the case of pure TiO2, the total degradation of parabens was achieved
using a TOD of 70 mg L1, which is a similar result to the one obtained
with ozone and catalyst (Gomes et al., 2017a). The same behavior oc-
curred with 0.5% Au-TiO2. Therefore, the presence of light had no signif-
icant improvement on the catalytic activity of these catalysts. This may
be related to the high electronegativity of Au and the low photoactivity
of pure TiO2 for UVA. Thus the amount of hydroxyl radicals produced by
these two catalysts will not be largely improved by the presence of light.
Contrarily Ag-TiO2 was the most photoreactive catalyst because total
parabens degradation was achieved using a TOD of 40 mg L1 which
is much lower (94 mg L1) compared to catalytic ozonation without
UVA irradiation (Gomes et al., 2017a) for the same catalyst. This good
result for 0.5% Ag-TiO2 can be explained by the higher amount of
photogenerated electrons available for reducing ozone. In fact, silver
has the lowest value for electronegativity and the electron afnity of Fig. 4. COD removal as function of TOD during photolytic and photocatalytic ozonation.
336 J.F. Gomes et al. / Science of the Total Environment 609 (2017) 329340

L1, a COD abatement of 41% is achieved (Fig. 4). Gomes et al. (2017a) Table 3
for the catalytic ozonation of the same mixture using Pd-TiO2 attained V. scheri luminescence inhibition after 15 min of exposure, and GI for L. sativum (%) after
120 min treatment and for initial mixture of parabens.
35% of COD removal. So, with this catalyst the presence of light had no
signicant improvement on COD degradation. However, with catalytic Luminescence inhibition after 15 min Germination
ozonation the TOC removal was 18% (Gomes et al., 2017a), and in the (%) index
(95% CI in brackets) (%) (SD)
present study this value increased to 38% for the same value of TOD
(80 mg L1). So, for this catalyst the presence of light maybe improves Initial mixture 95.6 0.0 42 11
parabens
mineralization rather than partial oxidation.
Photolytic ozonation 59.9 1.8 93 11
TOC analysis to the treated solution after 120 min was performed to 0.5% Pd-TiO2 44.2 1.4 108 7
measure the mineralization degree. Table 2 summarizes the TOC and 0.5% Pt-TiO2 61.4 1.2 107 11
COD removal and the oxidation yield (CODPartox). The oxidation yield 0.5% Au-TiO2 55.4 1.0 107 5
was calculated to compare the selectivity of different treatments, fol- 0.5% Ag-TiO2 43.4 1.4 112 1
Pure TiO2 36.3 0.0 90 0
lowing Eqs. (7) and (8) (Hellenbrand et al., 1997).

CODPartox
CODPartox 7
COD0 COD C. uminea (no data shown) was submitted for acute toxicity tests
  during 72 h. The mortality of clams was measured at each 24 h and
COD0 COD the nal results represent to the cumulative mortality after 72 h. In
CODPartox  TOC 8
TOC0 TOC these tests the mortality of the clams at different concentrations of
treated efuents (100, 75, 50% V/V) was examined. For the samples ob-
The CODPartox was calculated to understand if COD is removed by tained after 120 min of photolytic ozonation and photocatalytic ozona-
partial oxidation or mineralization. This parameter can be within the tion with different catalysts no mortality was veried for all
range of 0 (total mineralization) and 1 (100% of partial oxidation). As concentrations tested after 72 h of exposure. However, for the initial
can be seen in Table 2 the best results for CODPartox were obtained for mixture of parabens 100% mortality was achieved after 72 h. Therefore,
0.5% Pd-TiO2 which means that about 92% of COD removed was trans- the treatments applied to the initial mixture of parabens clearly reduced
formed into carbon dioxide and water. The TOC removal increase ac- the toxicity towards C. uminea despite the fact that the total COD re-
cording the following order: 0.5% Au-TiO2 b photolytic moval was not achieved. This indicates that the refractory by-products
ozonation b Pure TiO2 b 0.5% Ag-TiO2 b 0.5% Pt-TiO2 b 0.5% Pd-TiO2. produced are less toxic than parabens.
This is different from the order obtained for COD removal, where the Table 3 presents the results obtained in the tests with V. scheri and
0.5% Pt-TiO2 has the highest value of COD removed (about 50%) and L. sativum. For V. scheri the initial mixture of parabens leads to 95% lu-
0.5% Ag-TiO2 the second highest value (44%). The values of CODPartox minescence inhibition after 15 min of exposure. Miralles-Cuevas et al.
for these catalytic systems reveal that 84% and 75% of COD removed (2017) suggested that if the luminescence inhibition was higher than
was transformed in CO2 and H2O, when Ag-TiO2 and Pt-TiO2 were ap- 30%, the samples can be considered toxic. So, the initial mixture of
plied respectively. Meanwhile these values of CODPartox were obtained parabens is very toxic for this bacteria. The photocatalytic ozonation
using a lower TOD comparing with Pd-TiO2 (Table 1). The photolytic provided signicant reduction of initial toxicity. For the treated samples,
ozonation has the highest CODPartox which means that ozone and the higher luminescence inhibition was achieved for 0.5% Pt-TiO2 treat-
UVA removed organic matter by partial oxidation way. Ag-TiO2 was se- ed efuent, about 61%, which corresponds to a reduction of about 30%
lected as the best catalyst since it required lower TOD to achieve total re- compared with the initial mixture of parabens. For 0.5% Pd-TiO2, 0.5%
moval of parabens mixture. However, if the oxidation yield (function of Ag-TiO2 and pure TiO2 the luminescence inhibition was not so far
COD and TOC removals) is considered, Pd-TiO2 led to the best results. from 30%, so these three catalysts exhibits a potential effect on acute
Globally in terms of efciency on organic matter degradation the Ag, toxicity over V. scheri abatement. Gomes et al. (2017a), for the same
Pt and Pd-TiO2 appear as promising catalysts for UVA aided ozonation. parabens mixture achieved about 39% and 26% of luminescence inhibi-
Since TOC is not totally removed in any of the processes tested, it tion when bacteria was exposed to the samples coming from single
means that organic by-compounds are still present in solution after ozonation and catalytic ozonation applying pure TiO2, respectively.
treatments. Therefore, it is necessary to understand if the resulting solu- Thus, it can be concluded that, generally, the treatment involving UVA
tions are less or more toxic over different species compared to the initial irradiation, ozone and catalysts leads to higher toxicity removals.
mixture of parabens. Table 3 also shows the results for GI of L. sativum in contact with the
samples obtained after 120 min of treatment with photolytic and photo-
3.4. Toxicity assessment catalytic ozonation compared with the initial mixture of parabens. Ac-
cording to Trautmann and Krasny (1997) criteria, the initial mixture
The initial mixture of parabens was highly toxic to the different spe- of parabens, with GI around 40%, must be considered very phytotoxic.
cies tested (Table 3). The treatments applied reduced the toxicity of the As can be seen in Table 3, all treatments applied increased the GI for
initial mixture. For this toxicity assessment the pH of different efuents values around and above 90% which means that all treated samples
was adjusted to a near neutral value, because the species used are sen- are considered non-phytotoxic. For noble metal doped catalysts the GI
sitive to a non-neutral pH value. values are above of 100%, which means that the transformation by-
products can somehow improve the growth of L. sativum. The worst re-
Table 2 sult was obtained for pure TiO2 with GI around 90%, which according to
TOD, COD removal, TOC removal and Oxidation yield for different treatments applied after Trautmann and Krasny (1997) criteria can be considered as non-
120 min of reaction. phytotoxic. Gomes et al. (2017a), using ozonation with these catalysts
Condition TOD (mg L1) CODremoval (%) TOCremoval (%) CODPartox achieved the GIs of about 80%. Moreover, single ozonation led to a mod-
erately phytotoxic behavior (GI 65%).
O3/UV 118 27 26 0.68
O3/UV/0.5% Au-TiO2 84 38 25 0.40
O3/UV/TiO2 73 39 28 0.30 3.5. Implications
O3/UV/0.5% Pd-TiO2 80 41 38 0.08
O3/UV/0.5% Ag-TiO2 46 44 37 0.16 The cost evaluation is an important step when deciding the industri-
O3/UV/0.5% Pt-TiO2 60 50 37 0.25
al implementation of a treatment technology. Hollender et al. (2009)
 J.F. Gomes et al. / Science of the Total Environment 609 (2017) 329340 337

describes that the energy consumption at a treatment plant for ozone of the samples obtained during the photocatalytic ozonation for the dif-
production along with oxygen production is 12 kWh kg1 O3. Table 4 ferent catalysts tested. These compounds were quantied and repre-
shows the energy consumption for reaching total parabens degradation sented as function of TOD along photocatalytic ozonation experiments
at different applied conditions (Ozone + catalyst and Ozone + UVA (Fig. 5b). Hydroquinone, 4-HBA, 3,4-diHBA and 2,4-diHBA are the
irradiation + catalyst). The data for ozone treatment without UVA irra- most common identied by-products resulting from ozonation, hydrox-
diation was determined using the data from previous study (Gomes yl radical degradation or photocatalytic oxidation of parabens (Lin et al.,
et al., 2017a). 2011; Gmurek et al., 2015; Lin et al., 2009; Tay et al., 2010). Some com-
In the experiments using UVA irradiation, light consumption was pounds such as mono-, di- and tri-hydroxyderivatives from parabens
about 6.7513 kWh m 3. This range of energy consumption is ex- may also be found because the hydroxyl radicals and molecular ozone
plained by the fact that for photolytic experiments 1.5 h of UVA irradia- can react with the phenolic ring to produce hydroxylated parabens
tion were necessary to achieve total parabens degradation (highest (Hollender et al., 2009). From the C mass balance bearing in mind the
value) while for photocatalytic ozonation only 45 min of UVA irradia- detected by-products, it can be concluded that these compounds repre-
tion were needed. As can be seen in the Table 4 the presence of UVA ir- sent b 0.5% of the samples TOC. This means that other by-products are
radiation makes the treatment more expensive compared with being produced. In fact, from Criegee mechanism several aliphatic com-
ozonation and catalyst. The presence of light improves the parabens pounds (such as carboxylic acids) may be obtained through the ring
degradation but the energy consumption is higher compared with the opening. Moreover, other hydroxyderivatives of parabens are surely
worst result of single ozonation (2.04 kWh m3). The energy consump- produced. As can be seen in Fig. 5a, the 4-HBA (B) production can
tion is higher with the presence of UVA irradiation, but the use of occur through hydroxyl radical attack of O\\R bond (R can be methyl,
radiation allows a reduction of retention time required for treat- ethyl, propyl, butyl or benzyl group). The removal of this group pro-
ment implying consequently smaller reactors which will probably duces a radical that can react with water to form B or this radical
lower the investment on the layout of wastewater treatment can react again with hydroxyl radical that can break the C\\C bond
plant. If one considers that the retention time required for a contin- releasing CO2 resulting on hydroquinone (D) (Velegraki et al.,
uous system to achieve total parabens degradation is the same that 2015; Lin et al., 2009). The dihydroxylated benzoic acid, such as
the reaction time obtained for the batch system (Table 4), it can be 3,4-diHBA (C) and 2,4-diHBA production can occur via direct molec-
concluded that, for the same wastewater owrate, the reactor ular ozone attack of the benzenic ring due to the electrophilic charac-
would be 60% smaller when 0.5% Ag-TiO 2 was used as catalyst It ter of this molecule (Fig. 5a), or can be produced by hydroxyl radical
should be though considered that the reactor conguration used reaction with benzenic ring. 3,4,5-Trihydroxybenzoic acid (data not
for the real scale application will have strong implications over shown) was also identied, but only when two catalysts were ap-
the process efciency. In fact, if a slurry system is designed, a sedi- plied (0.5% Ag-TiO2 and 0.5% Pt-TiO2) and using high values of TOD.
mentation/ltration unit must be considered for catalyst removal Possibly, at those conditions higher amount of molecular ozone
and recovery. On the other hand, the immobilization of the doses are available to react with benzenic rings. Also, as can be
photocatalysts in a support would avoid the need of a separation seen in the Fig. 5a, due to the presence of UV-light and water the hy-
step. However, the process would lose some of the efciency since droquinone can oxide to produce 1,4 benzoquinone (E). All by-
light penetration and eventual mass transport limitations would products (identied and other not identied) can react with ozone
probably be not be negligible. and hydroxyl radicals to produce low molecular weight compounds
that can be mineralized into CO2 and H2O.
3.6. By-products analysis Fig. 5b describes the identied by-products concentration during the
photocatalytic ozonation experiments. From all identify by-products,
The photocatalytic ozonation of parabens degradation showed to be the highest concentration was achieved for 4-HBA. As can be seen, the
efcient in degrading compounds, but total mineralization was never production of this by-product starts to occur on early stages of photocat-
achieved. Therefore it is important identifying the resulting by- alytic ozonation. In fact, this compound is referred as an important by-
products of the reaction. The hydroxylation appears to be the most sig- product of parabens oxidation (Gmurek et al., 2015; Lin et al., 2009; Tay
nicant reaction pathway during photocatalytic ozonation, as can be et al., 2010). The 4-HBA concentration prole shows a maximum for a
seen in Fig. 5a. Fig. 5a reveals the possible pathways on parabens TOD of 10 mg L1 when 0.5% Ag-TiO2 and 0.5% Pt-TiO2 catalysts were ap-
(A) degradation in the presence of molecular ozone, hydroxyl radicals plied. A similar behavior was veried for hydroquinone, possibly due to
and UV light (Lin et al., 2011; Gmurek et al., 2015; Lin et al., 2009; Tay the high concentration of hydroxyl radicals. For these catalysts higher
et al., 2010). By-products identication was made by HPLC. The stan- TOD values than 10 mg L1 promoted a decrease on 4-HBA concentra-
dards of 4-Hydroxybenzoic acid (4-HBA), 3,4-Dihydroxybenzoic acid tion. It is probably that 4-HBA decomposition may lead to low molecular
(3,4-diHBA), 2,4-Dihydroxybenzoic acid Hydroquinone and 1,4-Benzo- weight by-products which were not detected (Gmurek et al., 2015; Lin
quinone were used. Their peaks were identied on the chromatograms et al., 2009). As well as 4-HBA decay may lead to an increase of 3,4-
diHBA and 2,4-diHBA production, possible due to its hydroxylation with
molecular ozone or hydroxyl radicals (Gmurek et al., 2015; Tay et al.,
2010). The concentration of 3,4-diHBA is slightly higher compared to
Table 4 2,4-diHBA, but the concentration proles are alike along TOD values.
Energy consumption and time required for total parabens degradation using Ozone and The hydroquinone concentration prole for 0.5%Au-TiO2 and pure TiO2
UVA irradiation for different catalysts.
can be an explanation for the lower efciency of these catalysts regarding
Conditions Energy consumption single or Energy consumption single or parabens, TOC and COD removal. The low hydroquinone production ob-
catalytic ozonation (kWh m3) catalytic ozonation + UVA served for these two catalysts may be due to the low concentration of hy-
(time needed to total parabens irradiation (kWh m3) (time
droxyl radicals generated in this system. On other hand, as it can be
removal) needed to total parabens
removal) observed, hydroquinone concentration for 0.5% Ag-TiO2 and 0.5% Pt-
TiO2 decays while 1.4-benzoquinone concentration increases which can
O3 2.04 (120 min) 15 (90 min)
O3/0.5% Au-TiO2 1.01 (120 min) 14.2 (90 min) be due to higher amount of holes (h+) on TiO2 surface in these two cat-
O3/TiO2 0.84 (120 min) 9.4 (60 min) alysts that can promote the oxidation of adsorbed hydroquinone.
O3/0.5% Pd-TiO2 0.96 (120 min) 9.5 (60 min) The identied by-products remain after photocatalytic ozonation
O3/0.5% Ag-TiO2 1.13 (120 min) 7.2 (45 min) treatment in some of conditions tested, which explains the low TOC
O3/0.5% Pt-TiO2 0.84 (120 min) 9.4 (60 min)
and COD removal values obtained for some of the studied processes.
338 J.F. Gomes et al. / Science of the Total Environment 609 (2017) 329340

Fig. 5. a) Possible pathways for parabens degradation using photocatalytic ozonation and b) by-products (4-HBA; 3,4 diHBA; 2,4-diHBA; Hydroquinone and 1,4 benzoquinone) formation
for different catalysts tested.
 J.F. Gomes et al. / Science of the Total Environment 609 (2017) 329340 339

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