Soil and unsaturated zone as a long-term source for pesticide metabolites in groundwater

Abstract

Pesticide metabolites are frequently detected in groundwater, often exceeding the concentrations of their parent pesticides. Ceasing the application of certain pesticides has often not led to the expected decrease in metabolite concentrations in groundwater, which is potentially caused by residues in soil. Whereas pesticide residues in soils are well-documented, there are only few studies about metabolite residues. We investigated if the soil/unsaturated zone can act as a long-term source for metabolites in groundwater by combining soil analysis, groundwater analysis and numerical modelling. The field study focused on the herbicide chloridazon (CLZ) and its frequently detected metabolites desphenyl-chloridazon (DPC) and methyl-desphenyl-chloridazon (MDPC) while in the model additional pesticides and metabolites were considered. In soil samples from an agricultural area, where the last CLZ application was 5 to 10 years ago, we observed 10 times (DPC: 0.22 – 7.4 µg kg−1) and 6 times (MDPC: 0.12 – 3.1 µg kg−1) higher metabolite concentrations compared to CLZ (< 0.050 – 1.0 µg kg−1). Calculations suggested that the majority of the metabolites (DPC: 63 - 96%, MDPC: 74 – 97%) were sorbed despite their lower sorption tendency. The metabolite retention was in particular related to the organic carbon content. The calculated pore water concentrations were highest in the deepest part of the soil profile (75 – 100 cm) with median concentrations of 3.6 and 1.7 µg L−1 for DPC and MDPC, respectively. The groundwater concentrations of DPC and MDPC were 3 to 3.5 times higher in monitoring wells downgradient from the agricultural zone than upgradient of it. This increase highlights the potential of soil and unsaturated zone as a long-term metabolite source after the application stop of pesticides, consistent with the calculated elevated pore water concentrations. Numerical flow and transport model simulations suggested that this input from soil and unsaturated zone can cause elevated metabolite concentrations (> 0.1 µg L−1) in groundwater over more than one decade. The study highlights that soil and unsaturated zone can act as a long-term source of pesticide metabolites even if they have much higher mobility than the parent compound.