Occurrence and water-sediment exchange of systemic insecticides and their transformation products in an agriculture-dominated basin

Neonicotinoids (NEOs) and fipronil (FIP) are ubiquitous in aquatic environment, yet the transformation and water-sediment exchange are largely unknown for these systemic insecticides and their transformation products (TPs). Herein, occurrence, field-based partitioning coefficients, and fugacity fractions (ff) of NEOs, FIP, and their TPs were analyzed in the drainage and receiving rivers near a rice paddy field. NEOs and FIPs were frequently detected in the sediments with concentrations of TPs being often higher than the parent compounds. Average ff values of NEOs (0.944-1.00) were larger than those of FIPs (0.399-0.716), indicating NEOs had a greater tendency to diffuse from sediment into water. Similar as well-studied hydrophobic compounds, hydrophobicity was the main factor impacting the water-sediment exchange of moderately hydrophobic FIPs. Alternatively, electrostatic interactions governed the fate of hydrophilic NEOs in water-sediment system. The log Kd values of NEOs were positively correlated with their N/C ratios (p < 0.05), possibly because the negatively charged sediments (zeta potential were from-19.1 & PLUSMN; 0.6 to-5.84 & PLUSMN; 0.57 mV) generated electrostatic attraction with amino functional group. Our study highlighted the ubiquitousness of TPs and distinct water-sediment interaction for moderately hydrophobic and hydrophilic insecticides in an agriculture-dominated watershed.