Solutions with 1.07 mmol dm(-3) aniline or with 1.38 mmol dm(-3) 4-chlorophenol at pH ca. 3 have been treated with ozone and ozonation catalyzed with Fe2+ and/or UVA. The initial mineralization rate increases as more oxidizing hydroxyl radical is produced in the medium by the catalyzed ozonations. Direct ozone treatment leads to stable oxidation products, which are quickly destroyed under UVA illumination. In the presence of Fe2+ as catalyst, the degradation process is inhibited by the formation of Fe3+ complexes with short organic diacids, being photodecomposed by UVA light. Each initial pollutant is destroyed at similar rate in all processes, p-Benzoquinone and nitrobenzene are identified as intermediates of aniline oxidation. The former product is only detected when high amounts of hydroxyl radical are produced by the action of Fe2+. Ammonium ion released during p-benzoquinone formation is also generated in larger extension under the same conditions. Nitrate ion reaches maximum production under UVA irradiation, indicating that generation of nitrobenzene from selective attack of O-3 on the amino group of aniline is photocatalyzed. Reaction of 4-chlorophenol with ozone leads to 4-chloro-1,3-dihydroxybenzene and 4-chloro-1,2-dihydroxybenzene. The last product is produced in larger extension when high amounts of hydroxyl radical can selectively attack the initial pollutant. Chloride ion is completely lost during the further degradation of both dihydroxylated derivatives. Oxidation of all aromatic intermediates detected during aniline and 4-chlorophenol degradation gives maleic acid, which is further mineralized via oxalic acid. A general reaction pathway for the degradation of each pollutant is proposed. (C) 2001 Elsevier Science B.V. All rights reserved.