Advanced oxidation of the pharmaceutical drug diclofenac with UV/H2O2 and ozone.

Diclofenac, a widely used anti-inflammatory drug, has been found in many Sewage Treatment Plant effluents, rivers and lake waters, and has been reported to exhibit adverse effects on fish. Advanced oxidation processes, ozonation and H2O2/UV were investigated for its degradation in water. The kinetic of the degradation reaction and the nature of the intermediate products were still poorly defined. Under the conditions adopted in the present study, both ozonation and H2O2/UV systems proved to be effective in inducing diclofenac degradation, ensuring a complete conversion of the chlorine into chloride ions and degrees of mineralization of 32% for ozonation and 39% for H2O2/UV after a 90 min treatment. The reactions were found to follow similar, but not identical, reaction pathways leading to hydroxylated intermediates (e.g. 2-[(2,6-dichlorophenyl)amino]-5-hydroxyphenylacetic acid) and C-N cleavage products (notably 2,5-dihydroxyphenylacetic acid) through competitive routes. Subsequent oxidative ring cleavage leads to carboxylic acid fragments via classic degradation pathways. In the pH range 5.0-6.0 kinetic constants (1.76 x 10(4)-1.84 x 10(4) M(-1) s(-1)) were estimated for diclofenac ozonation.

Kinetic and chemical assessment of the UV/H2O2 treatment of antiepileptic drug carbamazepine.

The UV/H2O2-induced degradation of carbamazepine, a worldwide used antiepileptic drug, recently found as contaminant in many municipal sewage treatment plant (STP) effluents and other aquatic environments, is investigated. The oxidation treatment caused an effective removal of the drug. At complete abatement of the substrate after 4 min treatment, a 35% value of removed total organic carbon (TOC) was obtained. A kinetic constant of (2.05+/-0.14) x 10(9) lmol(-1)s(-1) was determined for OH radical attack to carbamazepine in the UV/H2O2 process. Preparative TLC of the reaction mixture led to the isolation of acridine-9-carboxaldehyde as a reaction intermediate. HPLC and GC/MS analysis indicated formation of small amounts of acridine, salicylic acid, catechol and anthranilic acid among the reaction products. Under the same reaction conditions, synthetically prepared 10,11-epoxycarbamazepine was easily degraded to acridine as main product, suggesting that this epoxide is a likely intermediate in the oxidative conversion of carbamazepine to acridine. Under sunlight irradiation, carbamazepine in water underwent slow degradation to afford likewise acridine as main product. In view of the mutagenic properties of acridine, these results would raise important issues concerning the possible environmental impact of carbamazepine release through domestic wastewaters and support the importance of prolonged oxidation treatments to ensure complete degradation of aromatic intermediates.

Paracetamol oxidation from aqueous solutions by means of ozonation and H2O2/UV system.

Paracetamol oxidation from aqueous solutions is studied by means of ozonation and H(2)O(2) photolysis. Both oxidative systems are able to destroy the aromatic ring of the substrate with a partial conversion of the initial carbon content into carbon dioxide. For the adopted experimental conditions mineralization degrees up to 30% and 40% are observed with ozonation and H(2)O(2) photolysis, respectively. Main reaction intermediates and products are identified for both systems by HPLC and GC-MS analyses and a kinetic characterization is achieved.

Advanced oxidation chemistry of paracetamol. UV/H(2)O(2)-induced hydroxylation/degradation pathways and (15)N-aided inventory of nitrogenous breakdown products.

The advanced oxidation chemistry of the antipyretic drug paracetamol (1) with the UV/H(2)O(2) system was investigated by an integrated methodology based on (15)N-labeling and GC-MS, HPLC, and 2D (1)H, (13)C, and (15)N NMR analysis. Main degradation pathways derived from three hydroxylation steps, leading to 1,4-hydroquinone/1,4-benzoquinone, 4-acetylaminocatechol and, to a much lesser extent, 4-acetylaminoresorcine. Oxidation of the primary aromatic intermediates, viz. 4-acetylaminocatechol, 1,4-hydroquinone, 1,4-benzoquinone, and 1,2,4-benzenetriol, resulted in a series of nitrogenous and non-nitrogenous degradation products. The former included N-acetylglyoxylamide, acetylaminomalonic acid, acetylaminohydroxymalonic acid, acetylaminomaleic acid, diastereoisomeric 2-acetylamino-3-hydroxybutanedioic acids, 2-acetylaminobutenedioic acid, 3-acetylamino-4-hydroxy-2-pentenedioic acid, and 2,4-dihydroxy-3-acetylamino-2-pentenedioic acid, as well as two muconic and hydroxymuconic acid derivatives. (15)N NMR spectra revealed the accumulation since the early stages of substantial amounts of acetamide and oxalic acid monoamide. These results provide the first insight into the advanced oxidation chemistry of a 4-aminophenol derivative by the UV/H(2)O(2) system, and highlight the investigative potential of integrated GC-MS/NMR methodologies based on (15)N-labeling to track degradation pathways of nitrogenous species.