Catalysis Today 209 (2013) 7983

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Catalysis Today
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Photodegradation of petrol station wastewater after coagulation/occulation with tannin-based coagulant

A.M. Ferrari-Lima , R.G. Marques, N.R.C. Fernandes-Machado, M.L. Gimenes
Universidade Estadual de Maring, Av. Colombo, 5790 Maring, Brazil

a r t i c l e

i n f o

a b s t r a c t
This work investigates the combined treatment of petrol station wastewater by coupling coagulation/occulation and heterogeneous photocatalysis processes. Coagulation/occulation was performed using a tannin-based coagulant, Tanoc. Commercial TiO2 , ZnO and Nb2 O5 were applied as photocatalysts, after calcination at 500 C/5 h. In order to evaluate synergic effects, the semiconductor oxides were mixed (50 wt%) and their activities were investigated under UV and VIS radiations. High reductions of absorbance, chemical oxygen demand and elimination of toxicity to Artemia salina was achieved with TiO2 ZnO under UV radiation. Chemical oxygen demand was reduced from 1363 mg L1 (untreated) to 362 mg L1 after coagulation/occulation and nally to 104 mg L1 after photocatalytic treatment. 2012 Elsevier B.V. All rights reserved.

Article history: Received 29 June 2012 Received in revised form 6 September 2012 Accepted 22 October 2012 Available online 11 December 2012 Keywords: Photocatalysis TiO2 catalyst ZnO catalyst Petrol station wastewater

1. Introduction Generated by spills during fuel supply, forecourt washing, car washing systems and convenience stores, petrol station wastewater (PSW) has a huge amount of hydrocarbons that are not removed by oilwater separators, which is the unique treatment system required for petrol stations. These hydrocarbons are formed by the soluble fraction of petrol and diesel in water, derived mainly from spills during fuel supply. Moreover, the presence of ethanol can contribute by increasing the solubility of these hydrocarbons in water [1], raising the toxicity of PSW. Many efforts have been applied in order to eliminate several types of hydrocarbons present in wastewater such as phenolic and other aromatic compounds [24]. Owing to the high toxicity of these compounds the oxidation of the hydrocarbons to CO2 and H2 O by means of advanced oxidation processes (AOPs) are of particular interest when compared to conventional processes of wastewater treatment. Among the AOPs, heterogeneous photocatalysis has been the subject of several studies on the degradation of toxic efuents [58] and has shown good results in the removal of several contaminants from wastewater. When a semiconductor is subjected to radiation whose energy is equal to or greater than its band gap energy, the excitation promotes a valence band electron to the conduction band, creating a gap in the valence band with enough positive potential to generate OH radicals from adsorbed water molecules. These radicals are

highly oxidising and react with organic compounds mineralising them. Among the huge variety of catalysts that have been investigated, TiO2 is undoubtedly the most used due to its well known structure and high activity [911]. However, TiO2 activity is still not high enough to be suitable for commercial application [12], especially due to the charge recombination and the need of ultraviolet radiation for the activation of the catalyst. In this sense, many efforts have been dedicated in order to enhance its activity by mixing semiconductor oxides to achieve better charge separation and avoid recombination centres [1214]. With this background, the aim of this work was to investigate the activity of mixed semiconductor oxides (TiO2 , ZnO and Nb2 O5 ) in the photodegradation of petrol station wastewater under ultraviolet and visible light radiations after pre-treatment by coagulation/occulation process using a tannin-based coagulant. The reduction of chemical oxygen demand and toxicity were discussed as well as the kinetics of the photodegradation and the overall efciency of the combined treatment. 2. Experimental 2.1. Wastewater collection and characterisation PSW samples were collected after oilwater separation in a petrol station located in an urban area of Maringa-Parana-Brazil and characterised following the Standard Methods for Examination of Water and Wastewater [15]. The petrol station offers fuel supply (ethanol, gasoline, and diesel), oil change services, vehicle washing and convenience store.

Corresponding author. Tel.: +55 44 3011 4777; fax: +55 44 3261 4792. E-mail address: ana eq@hotmail.com (A.M. Ferrari-Lima). 0920-5861/$ see front matter 2012 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.cattod.2012.10.022

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A.M. Ferrari-Lima et al. / Catalysis Today 209 (2013) 7983

2.2. Coagulation/occulation process Coagulation/occulation was performed in jar test Milan JT101. Wastewater was stirred (100 rpm) for 1 min, after adding Tanoc at 500 mg L1 concentration and followed by 30 min of slow agitation (50 rpm). After 2 h ocs settling down, the supernatant aqueous phase was separated for characterisation. 2.3. Catalysts preparation and characterisation The photocatalysts TiO2 (Kronos), ZnO (Dynamics) and Nb2 O5 (Companhia Brasileira de Minerac o e Metalurgia) were used plain and in simple mixture (50 wt%) after calcination at 500 C/5 h. Prior to calcination, the catalysts were submitted to agglomeration process (particle size 0.1500.300 mm). Textural analysis was carried out by nitrogen adsorption isotherm at 77 K using QuantaChrome Nova 1200 equipment. Xray diffraction (XRD) was performed in a Bruker D8 Advance X-ray diffractometer with Cu 40 K radiation, 30 mA and Ni lter. The observed peaks were compared with the data published by JCPDS (10). Scanning electron microscopy (SEM) analysis was carried out on Shimadzu SS-550 Superscan Microscope. Photoacoustic spectroscopy (PAS) was performed in equipment consisting of a monochromatic light provided by a xenon lamp of 1000 W (Oriel Corporation 68820), a monochromator (Oriel Instruments 77,250), a high sensitivity capacitive microphone (Bruel and Kjaer) and a lock-in amplier (EG & G 5110). The light beam was modulated with a mechanical modulator (Stanford Research Systems SR540). The photoacoustic spectrum was obtained on modulation frequency of 21 Hz at wavelength from 200 to 800 nm. Emission spectra of the lamps were acquired in a VS140 Linear Array UV-VIS & VIS Spectrometer (HORIBA). 2.4. Photocatalytic reactions The reaction system was formed by a 500 mL glass beaker equipped with magnetic agitation, temperature control and radiation isolation. The photographic illustration of the reactor is showed in Fig. 1. Radiation was provided by a 250 W low pressure mercury lamp (EMPALUX) whose bulb has been removed to obtain UV radiation or maintained to obtain VIS radiation. The distance between the lamp and the surface of the suspension was 15 cm. The UV light intensity was measured by an Instrutherm UV light meter MRU-201 and the VIS light intensity was measured by an Instrutherm luximeter LD300. Photocatalytic assays were performed with 1 g L1 of catalyst concentration, in accordance with previous work [16]. Catalyst activity was evaluated by chemical oxygen demand (COD), biotoxicity to Artemia salina and absorbance reductions after 300 min of irradiation. Absorbance was measured at 254, 280, 310 and 500 nm (HACH DR5000 spectrophotometer), corresponding to aliphatic groups, aromatic groups, conjugated aromatic rings and light-absorbing molecules, respectively [16,17]. 2.5. Biotoxicity tests Toxicity tests were performed following the methodology described in Santana and Fernandes-Machado [14]. Artemia saline (brine shrimp) was used as bioindicator of the toxicity. Cysts of Artemia saline were incubated in a 35 g L1 marine salt solution for 24 h at 28 C with continuous illumination and aeration. After 24 h the most active organisms were transferred to a new marine salt solution at the same concentration of the previous one and maintained for more 24 h at the same conditions. For toxicity testing, the following solutions were prepared: for the control, a solution of potassium dichromate (1 g L1 ) was prepared and diluted in saline solution at the concentrations of 0, 10, 20, 40 and 60 mL L1 . 2 mL
Table 1 Surface area and band gap of the catalysts. Catalyst Surface area BET (m2 g1 ) As prepared After annealing at 500 C/5 h 8.8 6.5 47.8 8.5 39.6 33.0 Band gap (eV) 3.20 3.12 3.17 3.17 3.15 3.21 Absorption threshold (nm) 388 397 391 391 394 386

Fig. 1. Photograph of the photocatalytic reactor.

aliquots of these solutions were added to the wells. For the wastewater, aliquots of 2 mL (before and after treatment) were added to the wells at the following dilutions in saline solution: 0, 1/2, 1/4, 1/8, 1/16 and 1/32 and 1, corresponding to percent concentrations of 100, 50, 25, 12.5, 6.25, 3.12 and 0% of wastewater, respectively. About 10 nauplii were added to each well and maintained in these solutions for 24 h under illumination (triplicate). The mortality of the nauplii for each dilution was evaluated and the lethal concentration for 50% of the nauplii (LC50) after 24 h of exposition was determined by probit analysis. 3. Results 3.1. Catalysts characterisation Textural analysis (Table 1) showed that surface area and pore size distributions of mixed catalysts were approximately the average of those for plain oxides. A slight reduction on the surface area with the thermal treatment means an increase in the crystal size by the sintering of small particles. XRD analysis (Fig. 2) identied anatase phase for TiO2 , hexagonal structure for Nb2 O5 and wurzita phase for ZnO after calcination at 500 C/5 h. New phases were not identied by mixing the oxides. PAS analysis showed that all the catalysts have similar bandgap energies, around 3.2 eV (Fig. 3), it means that the catalysts need

TiO2 ZnO Nb2 O5 TiO2 ZnO Nb2 O5 ZnO TiO2 Nb2 O5

10.6 6.8 69.6 8.7 49.0 47.5

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Fig. 2. XRD of the catalysts (x = TiO2 anatase, o = ZnO, * = Nb2 O5 ).

around the same amount of energy to promote the electron. This energy is located in the ultraviolet region of the electromagnetic spectra, as it is well known for TiO2 , ZnO and Nb2 O5 oxides (Table 1). SEM analysis showed that all the catalysts have similar morphology, consisting of well distributed spherical grains. Some grain agglomerates were found and can be associated with the sintering caused by the heat treatment. The particle size inside the reactor was in the interval of 0.1500.300 mm. By measuring the emission spectra of the lamps (Fig. 4) it is possible to note that when the bulb is removed both UV and VIS radiations are emitted with main peaks located at the ultraviolet region and also strong peaks located at 440, 550 and 580 nm (visible region). When the bulb is maintained the majority of the peaks are found at the visible region with two peaks corresponding to the ultraviolet region, 365 and 410 nm. In this way, the emission provided by the lamp with and without the bulb was called VIS and UV radiations, respectively. Comparing the peaks of the lamps with the absorption threshold of the catalysts (Table 1) it can be proposed that the 365 nm peak is the responsible for the activation of the catalysts whereas at this wavelength the minimum energy required by the semiconductors to promote the electron is provided. 3.2. Wastewater characterisation and coagulation In general, as depicted in Table 2, the efuent has neutral pH, high turbidity and COD. Reductions in all the parameters after coagulation/occulation certify the capability of Tanoc to remove

Fig. 4. UV/VIS and VIS lamps emission spectra.

organic and colloidal matter from the efuent. Beltrn-Heredia and Snchez-Martn [18] determined the adsorption capacity (q) as being an efciency parameter for the coagulation process. It was dened as q = (C0 C1 )V/W, where C0 and C1 are, respectively, the initial and nal COD concentrations (mg L1 ), V is the volume of solution (L) and W is Tanoc mass (g). In the present work, the equation gave a q value of 2002 mg of COD per g of Tanoc for PSW coagulation/occulaltion while other authors achieved q values of 490 mg and 359 mg for dye and surfactant removal, respectively, applying the same coagulant [19,20]. Pre-treatment can represent a fundamental step in heterogeneous photocatalysis systems, given that high turbidity and organic matter concentration can affect the scattering of light into the solution. Some authors report that for successful photocatalysis, COD values must be lower than 800 mg L1 [16,17,21]. Tanoc can be considered a good alternative to inorganic coagulants since the coagulant did not drastically reduce the pH of the efuent and showed satisfactory COD, TOC and turbidity removal capability. Additionally, the advantages associated with the use of organic coagulants such as no pH adjustment requirements, no addition of metal ions to the system, and biodegradable sludge generation [22] can represent a promising use of organic coagulants in wastewater treatment. 3.3. Photocatalytic degradation After coagulation/occulation process, the supernatant was separated from sludge and submitted to photodegradation under UV and VIS radiations with an irradiation time of 300 min. Radiation intensity on the suspension surface was 3570 W cm2 at 390 nm for the UV light and for the VIS light it was 700 W cm2 at 390 nm and 15,780 lx. Despite the similarity of the catalysts characteristics, mixing TiO2 and ZnO enhanced both TiO2 and ZnO activities under UV radiation (Fig. 5). Although the reduction of COD was 68% for both TiO2
Table 2 PSW characterisation before and after coagulation/occulation with Tanoc. Parameter pH COD (mg L1 ) TOC (mg L1 ) Turbidity (NTU) Total solids (mg L1 ) Grease (mg L1 ) In natura 6.9 1363 187 326 1287 56 After coagulation 6.8 362 90 34 632 45 Reduction (%) 73 52 90 51 18

Fig. 3. UV/VIS photoacoustic spectra of the catalysts.

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A.M. Ferrari-Lima et al. / Catalysis Today 209 (2013) 7983 Table 3 Rate constants of apparent rst order (k1 ), half-life time (t1/2 ) and R2 for COD reduction of PSW. Selected system TiO2 /UV TiO2 ZnO/UV TiO2 /VIS k1 (103 min1 ) 2.38 5.73 2.34 t1/2 (min) 291 121 296 R2 0.9974 0.9986 0.9823

Fig. 5. Residual absorbance of pre-claried PSW after 300 min of UV irradiation.

and TiO2 ZnO catalysts, the reduction of absorbance was higher for TiO2 ZnO, reaching 76, 78, 81 and 88% for the wavelengths of 254, 280, 310 and 500 nm, respectively. These values show that the hydrocarbons are being degraded and the organic matter is being removed from the wastewater by means of photocatalysis. Other authors have also reported synergic effect between semiconductor oxides at the same proportion of 50% [14]. This synergic behaviour can be attributed to the electron transfer from the conduction band of ZnO to the conduction band of TiO2 under illumination and the hole transfer from the valence band of TiO2 to the valence band of ZnO, leading to an decrease in the recombination rate and increase in the lifetime of the electron-hole pair, improving the occurrence of redox processes [23,24]. A slight reduction in COD and absorbance was observed when reaction was carried out without the catalyst, indicating that UVabsorbing compounds are probably present in the PSW and can compete with catalyst for absorption of radiation [25]. When the pre-claried wastewater was submitted to VIS radiation the reductions of COD and absorbance were lower than that obtained when UV radiation was applied (Fig. 6). This fact is clearly related to the band gaps of the catalysts which according to Table 1 are located in the UV region. Nevertheless, 53% of COD reduction was reached with TiO2 and VIS radiation. Absorbance reductions greater than 40% were achieved for all the wavelengths monitored

for both TiO2 and TiO2 ZnO catalysts. Some authors associate the lower activity of Nb2 O5 to the low stability of its hydrocolloid, keeping the catalyst usually precipitated in water [26,27], thus the lower activity of the Nb2 O5 containing catalysts even with its higher surface area. In general, absorbance reduction occurs at the following order: 500 nm > 310 nm > 280 nm > 254 nm. This fact occurs because as the aromatic hydrocarbons are degraded, aromatic rings are broken down into smaller compounds (single rings or aliphatic groups), increasing the absorbance in the wavelengths related to these compounds. Herrmann [28] points out that the aromatics rings are easily dearomatised and if there are aliphatic groups attached to the rings, this bond is quickly broken. Furthermore, the oxidation process preferentially occurs at the highest electronic density positions [16]. 3.4. Kinetics of COD reduction Kinetics studies were performed with the following systems: TiO2 /UV, TiO2 ZnO/UV and TiO2 /VIS. For the selected systems, the data t the LangmuirHinshelwood kinetics model for reactions of apparent rst order for COD oxidation (Table 3). The total irradiation time considered for kinetic studies was 300 min. The same behaviour has been reported for the photodegradation of several compounds [2,2932]. The more active catalyst was TiO2 ZnO/UV which showed the shortest half-life time for COD reduction (121 min). The rate constants showed the same magnitude found by An et al. [33] for COD removal from reactive dye-containing wastewater applying TiO2 . The cited authors reported a rate constant of 0.0046 min1 for the mentioned process while in the present work the rate constants were 0.0024, 0.0057 and 0.0023 min1 for the systems TiO2 /UV, TiO2 ZnO/UV and TiO2 /VIS, respectively. 3.5. Toxicity reduction and combined treatment It is known that photocatalysis can generate side-compounds that are toxic to aquatic environment. Therefore, biotoxicity assays were carried out with A. salina (brine shrimp) in order to evaluate the nal toxicity of the treated water after the combined treatment. The brine shrimp A. salina has been successfully employed to detect the toxicity of several media including vinasse, cyanobacteria, aldehydes and biocides [14,3437]. Toxicity was evaluated in terms of LC50 percentage, which corresponds to the lethal concentration in percentage of wastewater that causes death of 50% of Artemia nauplii after 24 h of exposition. The toxicity was measured only after the end of the reaction (after 300 min of irradiation), so there is no toxicity data to predict the behaviour of the formation of more or less toxic oxidation intermediates throughout the photodegradation. In the case of TiO2 and TiO2 ZnO catalysts applied under UV radiation, the LC50 was greater than 100% after 300 min of irradiation (Table 4), values with different letters are statistically different while values with the same letter are statistically identical. This fact indicates that when the nauplii were submitted to the efuent treated with these catalysts the percentage of deaths was lower

Fig. 6. Residual absorbance of pre-claried PSW after 300 min of VIS radiation.

A.M. Ferrari-Lima et al. / Catalysis Today 209 (2013) 7983 Table 4 PSW LC50%a under various conditions after 300 in of irradiation. PSW Untreated After coagulation Catalyst After photocatalysis TiO2 ZnO Nb2 O5 TiO2 ZnO TiO2 Nb2 O5 Without catalyst LC50(%)b 1.31 2.91b UV 102.08c 11.04d 21.38e 115.1f 60.37g 2.97b VIS 22.69e 9.30h 9.20h 14.22i 13.23i 2.97b
a

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a Lethal concentration of PSW that causes death of 50% Artemia nauplii after 24 h of exposition. b Different letters imply values statistically different (P < 0.05 by Tukey test). n = 3 samples analysed.

than 50% for the efuent undiluted. It can be considered that the toxicity of the efuent was eliminated. For Nb2 O5 catalyst no synergic effect has been observed with TiO2 . However the nal result showed to be the average between both catalysts concerning toxicity reduction (Table 4). No signicant pH variation occurred during the photocatalytic processes and signicant reductions of turbidity and COD were achieved. The COD of the efuent in natura reduced from 1363 to 362 mg L1 after coagulation/occulation and to 152 and 104 mg L1 after photocatalysis with the systems TiO2 /VIS and TiO2 ZnO/UV, respectively. The nal turbidity of the treated water was 3.78 and 9.58 NTU after combination of coagulation/occulation and photocatalysis with the systems TiO2 /VIS and TiO2 ZnO/UV, respectively. After combined treatment, no colour and no odour remained in the treated water. 4. Conclusions The combined treatment of petrol station efuent by coagulation/occulation followed by heterogeneous photocatalysis allows the reduction of pollutants and removal of toxic compounds, especially with TiO2 and ZnOTiO2 photocatalysts. Additionally, a good efciency was achieved under visible radiation, which would facilitate the practical use of the process. Synergic effect occurred between TiO2 and ZnO, leading to a higher activity to TiO2 ZnO catalyst when compared with the respective activities of TiO2 and ZnO singly. The elimination of toxicity to A. salina was achieved after combined treatment. Considering the overall efciency of the investigated process, the combined treatment exhibited promising potential for full scale application. Compared to the exiting PSW treatment systems some drawbacks like available space for installation and catalyst separation would have to be considered. Acknowledgments This work was sponsored by the Brazilian agencies CNPq and CAPES.