Reactivity of hydroxyl radicals with neonicotinoid insecticides: mechanism and changes in toxicity

The reactivity of hydroxyl radicals (HO center dot) towards three neonicotonoid insecticides, namely imidacloprid, thiacloprid and acetamiprid was investigated. These radicals were generated by photolysis of H2O2 solutions. Flash photolysis experiments were used to determine the rate constants of 5.5 x 10(10) M(-1)s(-1), 6 x 10(10) M(-1)s(-1), and 7.5 x 10(10) M(-1)s(-1), for the reactions of HO. with acetamiprid, imidacloprid, and thiacloprid, respectively. Continuous irradiation experiments in the absence and presence of H2O2 allowed the identification and toxicity evaluation of the primary photo- and oxidation products of the insecticides. In all cases, the less toxic 6-chloronicotinic acid was found to be the major product at higher degrees of oxidation. The results reported here indicate that the half life of the insecticides due to their reaction with HO center dot radicals in natural aquatic reservoirs may vary between 5 h and 19 days, and therefore the hydroxyl radical-mediated oxidation may be a significant abiotic elimination route. However, elimination of the insecticide under such conditions might not improve the quality of the contaminated water, as the primary products of degradation still show considerable toxicity to Vibrio fischeri assays.