Heterogeneous oxidation of the insecticide cypermethrin as thin film and airborne particles by hydroxyl radicals and ozone

Abstract

Evaluation of pesticides' fate in the atmosphere is important in terms of environmental effects on non-target areas and risk assessments analysis. This evaluation is usually done in the laboratory using analytical grade materials and is then extrapolated to more realistic conditions. To assess the effect of the pesticide purity level (i.e. analytical vs. technical) and state (i.e. sorbed film vs. airborne particles), we have investigated the oxidation rates and products of technical grade cypermethrin as thin film and in its airborne form, and compared it with our former results for analytical grade material. Technical grade thin film kinetics for both ozone and OH radicals revealed reaction rates similar to the analytical material, implying that for these processes, the analytical grade can be used as a good proxy. Oxidation products, however, were slightly different with two additional condensed phase products: formanilide, N-phenyl and 2-biphenyl carboxylic acid, which were seen with the technical grade material only. OH experiments revealed spectral changes that suggest the immediate formation of surface products containing OH functionalities. For the ozonolysis studies of airborne material, a novel set-up was used, which included a long-path FTIR cell in conjugation with a Scanning Mobility Particle Sizer (SMPS) system. This set-up allowed monitoring of real-time reaction kinetics and product formation (gas and condensed phases) together with aerosol size distribution measurements. Similar condensed phase products were observed for airborne and thin film technical grade cypermethrin after ozonolysis. Additionally, CO, CO(2) and possibly acetaldehyde were identified as gaseous oxidation products in the aerosols experiments only. A kinetic model fitted to our experimental system enabled the identification of both primary and secondary products as well as extraction of a formation rate constant. Kinetic calculations (based on gaseous products formation rate) have revealed values similar to that of the thin film experiments. Interestingly, heterogeneous oxidation of cypermethrin was also found to generate ultra fine secondary organic aerosols. Again, no significant difference was observed between analytical and technical grade materials. However, particle size distribution was much broader when films were exposed to OH and ozone than to ozone alone.