Systematic Underestimation of Pesticide Burden for Invertebrates under Field Conditions: Comparing the Influence of Dietary Uptake and Aquatic Exposure Dynamics.

Pesticides used in agriculture can end up in nearby streams and can have a negative impact on nontarget organisms such as aquatic invertebrates. During registration, bioaccumulation potential is often investigated using laboratory tests only. Recent studies showed that the magnitude of bioaccumulation in the field substantially differs from laboratory conditions. To investigate this discrepancy, we conducted a field bioaccumulation study in a stream known to receive pollutant loadings from agriculture. Our work incorporates measurements of stream pesticide concentrations at high temporal resolution (every 20 min), as well as sediment, leaves, and caged gammarid analyses (every 2-24 h) over several weeks. Of 49 investigated pesticides, 14 were detected in gammarids with highly variable concentrations of up to 140 ± 28 ng/gww. Toxicokinetic modeling using laboratory-derived uptake and depuration rate constants for azoxystrobin, cyprodinil, and fluopyram showed that despite the highly resolved water concentrations measured, the pesticide burden on gammarids remains underestimated by a factor of 1.9 ± 0.1 to 31 ± 3.0, with the highest underestimations occurring after rain events. Including dietary uptake from polluted detritus leaves and sediment in the model explained this underestimation only to a minor proportion. However, suspended solids analyzed during rain events had high pesticide concentrations, and uptake from them could partially explain the underestimation after rain events. Additional comparison between the measured and modeled data showed that the pesticide depuration in gammarids is slower in the field. This observation suggests that several unknown mechanisms may play a role, including lowered enzyme expression and mixture effects. Thus, it is important to conduct such retrospective risk assessments based on field investigations and adapt the registration accordingly.

Coupling River Concentration Simulations with a Toxicokinetic Model Effectively Predicts the Internal Concentrations of Wastewater-Derived Micropollutants in Field Gammarids.

Although the exposure assessment of wastewater-derived micropollutants via chemical, bioanalytical, and modeling methods in environmental compartments is becoming more frequent, the whole-body burden (i.e., internal concentrations) in nontarget organisms is rarely assessed. An understanding of the internal concentration fluctuation is especially important when exploring the mechanistic linkage between exposure and effects. In this study, we coupled a simple river model with a first-order toxicokinetic (TK) model to predict the concentrations of wastewater-derived micropollutants in freshwater invertebrates (Gammarus spp.). We applied Monte Carlo simulations and conducted laboratory experiments to account for the uncertain input data and the lack of uptake/depuration rate constants required for the TK model. The internal concentrations in field gammarids were predicted well, and the estimates varied only by a factor of 0.1-1.9. Fast equilibrium may also be assumed such that bioconcentration factors (BCFs) are used together with the daily river dilution patterns to predict internal concentrations. While this assumption is suitable for compounds observed in our experiment to reach the steady state within 48 h in gammarids, the model overpredicted the concentrations of substances that reach this condition after longer periods. Nevertheless, this approach provides conservative estimates and simplifies the coupling of models as BCFs are slightly more accessible than the rate constants. However, if one is interested in a more detailed exposure information (e.g., peak concentration and the whole-body burden recovery after a spill), then the nonsteady-state formulation should be employed.