The herbicide 4-chlorophenoxyacetic acid (4-CPA) has been degraded in aqueous medium by advanced electrochemical oxidation processes such as electro-Fenton and photoelectro-Fenton with UV light, using an undivided cell containing a Pt anode. In these environmentally clean methods, the main oxidant is the hydroxyl radical produced from Fenton's reaction between Fe2+ added to the medium and H2O2 electrogenerated from an 02-diffusion cathode. Solutions of a 4-CPA concentration <400 ppm within the pH range of 2.0-6.0 at 35 degrees C can be completely mineralized at low current by photoelectro-Fenton, while electro-Fenton leads to ca. 80% of mineralization. 4-CPA is much more slowly degraded by anodic oxidation in the absence and presence of electrogenerated H2O2. 4-Chlorophenol, 4-chlorocatechol, and hydroquinone are identified as aromatic intermediates by CG-MS and quantified by reverse-phase chromatography. Further oxidation of these chloroderivatives yields stable chloride ions. Generated carboxylic acids such as glycolic, glyoxylic, formic, malic, maleic, fumaric, and oxalic are followed by ion exclusion chromatography. The highest mineralization rate found for photoelectro-Fenton is accounted for by the fast photodecomposition of complexes of Fe3+ with such short-chain acids, mainly oxalic acid, under the action of UV light.

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