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The treatment of a pharmaceutical wastewater resulting from the production of an antibacterial drug (nalidixic acid) was investigated employing a membrane bioreactor (MBR) integrated with either ozonation or UV/H(2)O(2) process. This was achieved by placing chemical oxidation in the recirculation stream of the MBR. A conventional configuration with chemical oxidation as polishing for the MBR effluent was also tested as a reference. The synergistic effect of MBR when integrated with chemical oxidation was assessed by monitoring (i) the main wastewater characteristics, (ii) the concentration of nalidixic acid, (iii) the 48 organics identified in the raw wastewater and (iv) the 55 degradation products identified during wastewater treatment. Results showed that MBR integration with ozonation or UV/H(2)O(2) did not cause relevant drawbacks to both biological and filtration processes, with COD removal rates in the range 85-95%. Nalidixic acid passed undegraded through the MBR and was completely removed in the chemical oxidation step. Although the polishing configuration appeared to give better performances than the integrated system in removing 15 out of 48 secondary organics while similar removals were obtained for 19 other compounds. The benefit of the integrated system was however evident for the removal of the degradation products. Indeed, the integrated system allowed higher removals for 34 out of 55 degradation products while for only 4 compounds the polishing configuration gave better performance. Overall, results showed the effectiveness of the integrated treatment with both ozone and UV/H(2)O(2).

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The effectiveness of ozone treatment for improving the biodegradability of recalcitrant pollutants has been proved by investigating the ozonation reaction of FAST-VIOLET-B (FVB) a bioresistant chemical intermediate of azo-dyes. Laboratory scale experiments have been carried out, at room temperature, by bubbling, for 90 min, ozonated air (9ppmO3/min) into 0.35 1 of an alkaline (pH=11) aqueous solution (50 ppm) of FVB. The experimental results indicate that during the ozonation, even though complete FVB degradation occurs in 10 min, ozone consumption goes on for a further 20 min after which time most degradation reactions are completed. The main ozonation by-products, identified by HPLC, IC, and GC-MS are formaldehyde, acetaldehyde, glyoxal, acetone, acetic-, formic-, oxalic- and carbonic-acid, plus six FVB derivatives scarcely biodegradable. At the end of the ozonation, i.e. after 30 min., the initial values of TOC (35 mgC/l) and COD (103 mgO2/l) are respectively 27 and 25 and correspond to a relative removal of about 23% and 76%. As for FVB solution biodegradability expressed as (BOD5)/(COD) ratio, during the first 10 min its value regularly increases from zero up to a maximum of 0.75 that corresponds to an ozone consumption of 2.4 mg per each mg of organic carbon initially present in the solution.

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