Environmental photochemical fate of pesticides ametryn and imidacloprid in surface water (Paranapanema River, São Paulo, Brazil)

Abstract

In addition to direct photolysis studies, in this work the second-order reaction rate constants of pesticides imidacloprid (IMD) and ametryn (AMT) with hydroxyl radicals (HO●), singlet oxygen (1O2), and triplet excited states of chromophoric dissolved organic matter (3CDOM*) were determined by kinetic competition under sunlight. IMD and AMT exhibited low photolysis quantum yields: (1.23 ± 0.07) × 10–2 and (7.99 ± 1.61) × 10–3 mol Einstein−1, respectively. In contrast, reactions with HO● radicals and 3CDOM* dominate their degradation, with 1O2 exhibiting rates three to five orders of magnitude lower. The values of kIMD,HO● and kAMT,HO● were (3.51 ± 0.06) × 109 and (4.97 ± 0.37) × 109 L mol−1 s−1, respectively, while different rate constants were obtained using anthraquinone-2-sulfonate (AQ2S) or 4-carboxybenzophenone (CBBP) as CDOM proxies. For IMD this difference was significant, with kIMD,3AQ2S* = (1.02 ± 0.08) × 109 L mol−1 s−1 and kIMD,3CBBP* = (3.17 ± 0.14) × 108 L mol−1 s−1; on the contrary, the values found for AMT are close, kAMT,3AQ2S* = (8.13 ± 0.35) × 108 L mol−1 s−1 and kAMT,3CBBP* = (7.75 ± 0.80) × 108 L mol−1 s−1. Based on these results, mathematical simulations performed with the APEX model for typical levels of water constituents (NO3−, NO2−, CO32−, TOC, pH) indicate that the half-lives of these pesticides should vary between 24.1 and 18.8 days in the waters of the Paranapanema River (São Paulo, Brazil), which can therefore be impacted by intensive agricultural activity in the region.