Neonicotinoid Hydrolysis and Photolysis: Rates and Residual Toxicity

University of Minnesota M.S. thesis. May 2018. Major: Civil Engineering. Advisor: William Arnold. 1 computer file (PDF); vi, 73 pages.Neonicotinoid insecticides are currently the most widely used class of insecticides worldwide, accounting for 25% of total insecticide use. They are registered in 120 countries for use on more than 140 crops. Concern has grown, however, over their widespread detection in global surface waters, soil, finished drinking water, and wastewater, and for their potential role in colony collapse disorder in honey bees. This work set out to examine hydrolysis and photolysis reaction rates of neonicotinoids, as well as to identify reaction products and determine the toxicity of the reaction products on mosquitoes. Hydrolysis rates were tested between pH 4 and pH 10. Reaction rates were pseudo-first order and highly pH dependent. Calculated half-lives ranged from >1000 days to 10 days. Divalent metal ions (Cu2+, Ni2+, Zn2+) and minerals (kaolinite, goethite, TiO2) were found to have little to no effect on neonicotinoid hydrolysis. Experiments from pH 4 to pH 10 revealed a non-elementary rate law for neonicotinoid degradation, with the hydroxide concentration being raised to a power of 0.55 ± 0.09. Nitenpyram, imidacloprid, thiamethoxam, and clothianidin were found to undergo direct photolysis, with quantum yields of 0.025 ± 0.001, 0.0119 ± 0.0001, 0.0167 ± 0.0002, and 0.0133 ± 0.0001, respectively. Acetamiprid degraded very slowly via direct photolysis, but was found to undergo indirect photolysis due to reaction with OH∙ with a bimolecular rate constant of 1.7 ± 0.2×109 M-1 s-1. Reaction products were identified for all reactions, with the urea derivative as the most commonly detected product. Toxicity experiments on mosquitoes indicate no residual toxicity from hydrolysis or photolysis products, which may be expected given the removal of the pharmacophore during reactions. While abiotic reaction products were found to be non-toxic, results from experimental work indicates long environmental half-lives for the tested neonicotinoids, which may help to explain their observed persistence in environmental matrices