The photocatalytic degradation of bisphenol A (BPA), a representative endocrine disruptor, was carried out in TiO2 aqueous suspension. The main purposes were to confirm the total mineralization of BPA and to evaluate the estrogenic activity in the treated water during the photocatalytic reaction. An initial BPA concentration of 175 microM in water was totally degraded to carbon dioxide by TiO2-photocatalyzed reactions under UV irradiation of 10 mW cm-2 for 20 h. Four HPLC peaks indicating intermediate products appeared in chromatograms monitored at 275 nm, but the heights relative to that of the initial BPA were very low, at most 0.04 in the time period 5-10 h after the start of UV irradiation. All of the peaks finally disappeared after 20 h. For the treated water, the transcriptional estrogenic activity in response to human estrogen receptor in a yeast hybrid assay decreased drastically to less than 1% of the initial BPA's activity within 4 h. On the basis of these results, we conclude that TiO2 photocatalysis could be a useful technology for the purification of water containing BPA without generating any serious secondary pollution.
The degradation of 17 beta-estradiol (E2) in water by TiO2 photocatalysis was investigated; concurrently the estrogenic activity of the treated water was evaluated during the photocatalytic reactions by an estrogen screening assay. As a result, 10(-6) M of E2 was totally mineralized to CO2 in 1.0 g L-1 TiO2 suspension under UV irradiation for 3 h. 10 epsilon-17 beta-Dihydroxy-1,4-estradien-3-one and testosterone-like species were elucidated as intermediate products by GC/MS analysis. The mechanisms of E2 degradation by TiO2 photocatalysis were discussed not only experimentally but also theoretically by calculating the frontier electron densities of the E2 molecule. On the basis of the results obtained, it was concluded that the phenol moiety of the E2 molecule, one of the essential functional groups to interact with the estrogen receptor, should be the starting point of the photocatalytic oxidation of E2. This means that the estrogenic activity should be almost lost concurrently with the initiation of the photocatalytic degradation. Actually, the estrogenic activities of the intermediate products were negligible. TiO2 photocatalysis could be applied to water treatment to effectively remove natural and synthetic estrogens without producing biologically active intermediary products.
The electrochemical incineration of organic pollutants on a boron-doped diamond (BDD) thin film electrode was examined by bulk electrolysis, and the mechanism of oxidation was investigated. A comparative study with other electrodes such as Pt and glassy carbon (GC) electrodes revealed the superiority of the BDD over these electrodes. The extent of degradation of phenol and formate due to direct oxidation and hydroxyl radicalmediated oxidation were quantified by amperometric measurements. The extent of direct oxidation was found to decrease with increasing potentials due to the competing hydroxyl radical-mediated reactions. The extent of direct oxidation for formate was found to be higher than that for phenol, indicating the probability of higher adsorption of formate on the oxygen-terminated diamond surface. Finally, bulk electrolysis of phenol at the BDD resulted in the complete destruction of phenol to CO 2 with a removal efficiency of 96%, indicating the promising use of BDD for electrochemical waste treatment applications.
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