Kinetics and Products of Air Plasma Induced Oxidation in Water of Imidacloprid and Thiamethoxam Treated Individually and in Mixture

Imidacloprid (I) and thiamethoxam (T) are widely used neonicotinoid insecticides with high persistence in the environment and thus included in the watch list of substances for European Union-wide monitoring reported in the Decision 2015/495/EU. In this work aqueous solutions of I, T and I+T were subjected to advanced oxidation by air plasma produced by negative DC corona discharges above the liquid surface. The oxidative degradation of each pollutant was investigated by monitoring the rate and the products of its decay when treated alone and in the presence of variable amounts of the other compound. The results show that both I and T are readily degraded and that mineralization can be achieved in this process, as proven by the measurement of the residual organic carbon and by the quantitative conversion of chlorine and sulfur into inorganic chloride and sulfate, respectively. The major organic intermediates formed during the complex stepwise oxidation of I and T were identified and monitored by HPLC-MS/MS analysis. The results of kinetic studies show that both for I and T the reaction rate depends inversely on the insecticide initial concentration, that I and T have similar reactivities and that they do not interfere reciprocally in any specific way when treated in mixture at a total concentration of ca 1x10(-4) M. Based on literature data and on previous results with the same reactor, it is reasonable to propose that the oxidation of I and T is initiated by the reaction with OH radicals.