Aqueous picloram degradation by hydroxyl radicals: Unveiling mechanism, kinetics, and ecotoxicity through experimental and theoretical approaches

Pesticides are chemical compounds widely used to combat pests in crops, and they thus play a key role in agricultural production. However, due to their persistence in aquatic environments, even at low concentrations, their use has been considered an environmental problem and caused concern regarding the adverse effects on human health. This paper reports, for the first time, the mechanisms, kinetics, and an evaluation of the toxicity of picloram degradation initiated by center dot OH radicals in the aqueous environment using quantum chemistry and computational toxicology calculations. The rate constants are calculated using a combination of formulations derived from the Transition State Theory in a realistic temperature range (250-310 K). The results indicate that the two favorable pathways (R1 and R5) of center dot OH -based reactions occur by addition to the pyridine ring. The calculated rate constant at 298 K is compared with the overall second-order reaction rate constant, quantified herein experimentally via the competition kinetics method and data available in the literature showing an excellent agreement. The toxicity assessment and a photolysis study provide important information: i) picloram and the majority of degradation products are estimated as harmful; however, ii) these compounds can suffer photolysis in sunlight. The results of the present study can help understand the mechanism of picloram, also providing important clues regarding risk assessment in aquatic environments as well as novel experimental information. (C) 2021 Elsevier Ltd. All rights reserved.

Automated summary

Pesticides play a key role in agricultural production, but their persistence in aquatic environments raises concerns about adverse effects on human health and the environment. This study used quantum chemistry and computational toxicology to analyze the mechanism, kinetics, and toxicity of picloram degradation, revealing potential harm of picloram and its degradation products, as well as their susceptibility to photolysis in sunlight. The results provide important insights for risk assessment and experimental research in aquatic environments.