Pesticide dynamics in three small agricultural creeks in Hesse, Germany

BACKGROUND: Due to their high biodiversity, small water bodies play an important role for freshwater ecosystems. Nonetheless, systematic pesticide monitoring in small creeks with a catchment <30 km(2) is rarely conducted. METHODS: In this study, event-driven water samples were taken from May until November 2017 and March until July 2018 after 20 rain events at three sampling sites with catchment areas of <27 km(2) in the Wetterau, a region with intensive agriculture in Southern Hesse, Germany. Additionally, enriched extracts of the native water samples from the campaign in 2018 were used for the Microtox assay to determine baseline toxicity to invertebrates over time and sum of toxic units (STU) were calculated to compare the potential toxicity of the samples. RESULTS: Overall, 37 pesticides and 17 transformation products were found, whereby the herbicide metamitron (79 µg/L) showed the highest concentration. Regularly, pesticide concentrations peaked at the time of the highest water level within each sampling event. Within each sampling event maximum pesticide concentration was mostly reached in water samples taken during the first two hours. The sum of the time-weighted mean concentration values of all pesticides was between 2.0 µg/L and 7.2 µg/L, whereby the measured concentrations exceeded their regulatory acceptable concentration (RAC) at 55% of all sampling events for at least one pesticide. The mean EC(50) values varied between 28.6 ± 13.1 to 41.3 ± 12.1 REF (relative enrichment factor). The results indicated that several samples caused baseline toxicity, whereby the highest activity was measured at the time of highest water levels and pesticides concentrations, and then steadily decreased in parallel with the water level. Median STUs of invertebrates ranged from −2.10 to −3.91, of algae/aquatic plants from −0.79 to −1.84 and of fish from −2.47 to −4.24. For one of the three sampling sites, a significant linear correlation between baseline toxicity and STU(invertebrate)was found (r(2) = 0.48). CONCLUSION: The results of the present study suggest that (1) current pesticide monitoring programs underestimate risks posed by the exposure to pesticides for aquatic organisms and (2) pre-authorization regulatory risk assessment schemes are insufficient to protect aquatic environments.