Passive sampling of herbicides above sediments at sites with losses of submerged macrophytes in a mesotrophic lake.

Declines of submerged macrophytes (SUM) were monitored in littoral zones of the deep, mesotrophic lake Suhrer See (Northern Germany) since 2017. Drastic losses coincided with intense agriculture in sandy sub-catchments and precipitation. All lines of evidence pointed to a causal connection with subsurface discharge indicating that herbicide application might have caused the effects. Passive sampling was applied in 2022 to elucidate, whether herbicides were really present at sites of losses and if so, in ecotoxicological relevant concentrations. Samplers were exposed on top of lake sediments in 2 m depth and under worst case conditions, i.e., at sites, known for losses of the whole functional group of SUM and at the beginning of the vegetation period. At this time, SUM diaspores were most vulnerable to repression of development and the subsurface discharge was high in the same instance. The potential ecotoxicological relevance of detected herbicide concentrations was assessed with a toxic units (TU) approach, with reference to acute effect concentrations (EC50 of green algae, 72 h, growth). The TU ranged from 0.001 to 0.03. Most concentrations exceeded the threshold of relevance set by an assessment factor of 1000, i.e., TU > 0.001. Locally applied herbicides acted by suppressing developmental stages, and the sum of TU exceeded 0.02 at all sites, mainly due to diflufenican. Not applied locally, terbuthylazine and its relevant metabolites, including terbutryn, acted by inhibiting photosynthesis, and the sum of TU reached 0.005. On this base, diflufenican was assessed to be likely a main stressor, all other detected herbicides to be potentially relevant. Uncertainties and knowledge gaps were specified. The result of the chemical risk assessment was counterchecked for consistence with biological monitoring data within a whole lake perspective. Concepts of empirical and advanced causal attribution methodology were applied to get a grip to the ecological causal field and to protection.