Catalytic wet-air oxidation (CWAO) of aqueous solutions of bisphenol A (BPA) was investigated in a trickle-bed reactor at temperatures up to 230°C and oxygen partial pressure of 10.0 bar over TiO 2 and Ru/TiO 2 solids. It was observed that in the given range of operating conditions BPA undergoes both noncatalyzed and catalyzed oxidation routes. The employed Ru/TiO 2 catalyst containing 3.0 wt % of metallic phase enabled complete removal of BPA and more than 96% of TOC removal at temperatures of 200°C and above. No catalyst deactivation occurred that could be attributed to the dissolution of active ingredient material. At these conditions, no carbonaceous deposits were accumulated on the catalyst surface. The acute toxicity of end-product solutions to organisms from different taxonomic groups and estrogenicity determined by the genetically modified yeast, compared with those of the feed solutions, was significantly reduced by CWAO treatment over the Ru/TiO 2 catalyst. For comparison, oxidative destruction of BPA was also investigated in this study by means of either photolytic or heterogeneous photocatalytic oxidation. A commercial TiO 2 photocatalyst illuminated by UV light enabled complete removal of BPA; however, lower decrease of toxicity and estrogenicity in the treated solution was observed.

Estrogenic activity has been detected in aquatic ecosystems across the world. However, there is a lack of such data for Slovenian wastewaters and surface waters. The Slovenian monitoring program of effluents discharged into surface waters does not require that emissions of natural and synthetic estrogens into aquatic environments be assessed and controlled. In our study, we assessed the potential estrogenicity of wastewater samples from three wastewater treatment plants using a yeast estrogen screen assay (YES assay). Due to the high inhibition of yeast growth in samples obtained during our first sampling period, it was impossible to detect any estrogenic activity. An additional silica gel clean-up step reduced the toxicity of samples collected during our second sampling period; as a result, we were able to record up to 95% relative estrogenic activity inhibition. Deconjugation of the estrogens did not significantly influence our results. We detected estrogenic activity using a YES assay in almost all influent and effluent samples tested, which suggests that the wastewater treatment plants (WWTPs) examined do not effectively remove (xeno)estrogens from wastewaters. Our results suggest that a YES assay is an appropriate screening method for monitoring estrogenic activity in effluents. However, prediction of the potential impacts of wastewater (xeno)estrogens on aquatic organisms require additional in vitro and in vivo assays.

Abstract:© Versita Sp. z o.o. Commercial product Degussa TiO2 P25, sol-gel produced TiO 2 and TiO 2 modified by carbon nanotubes addition (5% of the TiO 2 mass) are tested as photocatalysts for the degradation of endocrine disrupting compound 17α-ethynylestradiol (1 µM aqueous solution). The molecular and crystal structure, phase composition, crystallite size, specific surface area, pore average diameter, their area and volume distribution, morphology, IR and UV/Vis spectra of the catalysts are characterized. HPLC is used for estrogen analysis. The sorption ability and photocatalytic activity (measured by degradation rate constant and percentage of the pollutant conversion) of the catalysts under UV (17 W, emission maximum at 254 nm) irradiation is determined. Full destruction of the pollutant is reached after 30 min irradiation in presence of Degussa P25. The performance of some of the catalysts is compared with literature data for their activity under 365 nm-illumination.

This study compares efficiency of Fenton's oxidation and ozonation of 17beta-estradiol (E2) and 17alpha-ethinylestradiol (EE2) as two possible processes for removal of estrogens from aqueous solutions. The effectiveness of Fenton's oxidative removal was studied at different ratios of reagents Fe2+:H2O2 (1:0.5; 1:10; 1:20; 1:33), where with some molar ratios up to 100% removal of E2 and EE2 was achieved in the first few minutes of reaction. The best molar ratio for E2 (17beta-estradiol) removal was 1:33, while in the case of EE2 the most efficient one was 1:20 ratio. Ozonation was much faster, because complete removal of estrogens was achieved in 30 seconds (pH approximately eaqual 6), but the time of ozonation was extended up to 60 minutes trying to decompose formed by-products, expressing estrogenic activity, detected by YES (Yeast Estrogen Screening) assay. The obtained results showed that the removal efficiency of estrogens from waters should be assessed by a combination of chemical analyses and bioassay.

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The aim of this research was to assess the efficiency of Fenton's oxidation for degradation of endocrine disruptor bisphenol A (BPA) with emphasis on extent of accompanying adsorption. Adsorption on the waste sludge resulting from the Fenton's oxidation could represent a significant impact on the final removal efficiency of BPA. Fenton's oxidation was accomplished at two concentrations of BPA (0.228 and 22.8 mg L ). In addition to changing concentrations of BPA and sludge, the adsorption process was also influenced by parameters such as temperature, pH and contact time. Adsorption isotherms were determined. Oxidation and adsorption were monitored by gas chromatography combined with mass spectrum. It has been confirmed that BPA is not completely oxidized in Fenton's oxidation, because it is adsorbed to formed waste ferric sludge and thus necessary precautions for sludge deposition must be observed.

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