The photoinduced degradation of three anilinopyrimidine fungicides (cyprodinil, pyrimethanil and mepanipyrim) by Fe(III)–polycarboxylate complexes in aqueous solution was investigated. A photochemical redox reaction of Fe(III) complexes of oxalate and citrate occurs during irradiation (simulating sunlight) and is an important source of Fe(II) and a series of oxidants such as H2O2 and O radicals. The mechanism involves the formation of polycarboxylate radicals and/or carbon-centred radicals derived from decarboxylation, whereas the contribution of Fe(OH)2+ to O radical formation is negligible. The attack of O radicals on the fungicide molecules produces numerous photodegradation products, which were identified by means of LC-ES-MS and turned out to be mono- or dihydroxylated derivatives of the active ingredients, except for 2-amino-4,6-dimethylpyrimidine, which is only formed by pyrimethanil. The half-lives of the active ingredients, when submitted to irradiation in the presence of iron(III)– polycarboxylate complexes, were estimated to vary between 28 and 79min (photodegradation rates in the same conditions: mepanipyrim > cyprodinil > pyrimethanil), and photodegradation is slower in citrate than in oxalate solutions. Photoproducts and their kinetics of formation are very similar for the three fungicides. The OH substitution involves the aromatic and the heterocyclic ring and the nitrogen bridge between the two rings, except for mepanipyrim when the hydroxylation also involves the propynylic side chain
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