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.

Survey of Appearance and temporal concentrations of polar organic pollutants in Saxon waters.

Integrative passive samplers such as the Chemcatcher are often proposed as alternatives for conventional grab sampling of surface waters. So far, their routine application for regulatory monitoring is hampered (among others) by the fact that TWA concentrations may depend significantly on the design and specifics of the samplers employed. The presented study addresses this issue, focusing on the uptake of polar organic pollutants in three different Chemcatcher configurations and polydimethylsiloxane (PDMS) sheets in the field. Covering waste water treatment plant effluents, creeks, and rivers, samplers were deployed for periods of 14-21 days in eight trials over the course of one year. 33 organic pesticides, 14 transformation products and 31 pharmaceuticals could be detected at least once in TWA concentrations ranging from 0.03 ng/L to 16.5 µg/L. We show that through employing generic, i.e. sampler specific, rather than compound specific sampling rates, the variation among results from three integrative passive sampler designs yields linear correlations with an offset of less than 0.1 and correlation coefficients r2 > 0.8. In this way, TWA concentrations enable the identification of low-concentration xenobiotics of concern, which may support regulatory monitoring correspondingly.

Calibration of the Chemcatcher® passive sampler and derivation of generic sampling rates for a broad application in monitoring of surface waters.

We determined sampling rates for 34 pesticides, five pesticide transformation products, and 34 pharmaceutical compounds with the Chemcatcher (CC) passive sampler in a laboratory-based continuous-flow system at 40 cm/s and ambient temperature. Three different sampling phases were used: styrene divinylbenzene disks (SDB-XC), styrene divinylbenzene reversed phase sulfonate disks (SDB-RPS), and hydrophilic lipophilic balance disks (HLB), in all cases covered with a diffusion-limiting polyethersulfone membrane. The measured sampling rates range from 0.007 L/d to 0.193 L/d for CC with SDB-XC (CC-XC), from 0.055 L/d to 0.796 L/d for CC with SDB-RPS (CC-RPS), and from 0.018 L/d to 0.073 L/d for CC equipped with HLB (CC-HLB). Comparison with sampling rates from literature enabled to derive generic sampling rates that can be used for compounds with unknown uptake kinetics such as transformations products and new compounds of interest. Field trial results demonstrate that the presently derived generic sampling rates are suitable for estimating time-weighted average concentrations within reasonable uncertainty limits. In this way, Chemcatcher passive sampling can be applied approximately to a broad range of solutes without the need for deriving compound-specific sampling rates, which enable compliance checks against environmental quality standards and further risk assessment.