Sonochemical degradation of neonicotinoid pesticides in natural surface waters. Influence of operational and environmental conditions

Neonicotinoids sonochemical oxidation at high-frequency ultrasound (MHz range) has been carried out in ultrapure and natural surface-water matrices (river, reservoir and wastewater treatment plant effluent). To evaluate the influence of the operating variables, that is initial pollutant concentration, ultrasound frequency, ultrasound power, and pulse-stop time a Box-Behnken experimental design was planned. Optimal results were obtained using a frequency of 578 kHz, a power of 40 W L⁻¹, with a pollutant concentration of 1 μM (for each pesticide), and using a pulse-stop time of 100 ms. The experimental data adjustment using the Langmuir-Hinshelwood heterogeneous kinetic model showed that neonicotinoids oxidation was carried out in the bubble-liquid interface by the attack of hydroxyl radicals. Experiments performed in the presence of radical scavengers, that is, methanol, ethanol and tert-butyl alcohol corroborated this reaction mechanism. The influence of some environmental conditions such as pH, presence of soluble inorganic species (Cl⁻, SO₄²⁻, NO₃⁻, HPO₄²⁻, HCO₃⁻) and soluble organic species (humic acids content) were established. Finally, the aqueous matrix's influence was investigated for three natural surface water cases, and the results were rationalized according to the main water physicochemical characteristics.