Reference scenarios for exposure to plant protection products and invertebrate communities in stream mesocosms.

Higher tier aquatic risk assessment for plant protection products (PPPs) is often based on pond-like mesocosm studies in which transient and dynamic PPP exposure scenarios as observed in lotic systems are hardly achievable. Thus, the present study presents dynamic PPP exposure scenarios at different time scales under flow-through conditions as typical for streams in agricultural landscapes. The stream mesocosm setup allows testing the influence of spatial gradients of exposure over the length of themesocosms. The use of the fluorescent tracer uranine revealed the hydraulic processes generally underlying peak- and hour-scale exposure scenarios and demonstrated an optimized application technique to achieve stable day-scale exposures. Furthermore, to account for potential reactions of invertebrates to PPP exposures in streams (e.g. avoidance behavior and drift), the present study thus aimed at a comprehensive evaluation on how PPP exposure and the establishment of invertebrates can be advanced within streammesocosm testing. For both, peak- and hour-scale exposure as well as the experiments considering the establishment of invertebrates, the presented compilation of experiments was able to highlight the influence of aquatic macrophyteswithin streammesocosms. Since the field relevance of the higher tier aquatic risk assessment for PPPs relies qualitatively on the presence of potentially sensitive or vulnerable species, those species were especially considered. Thus, the establishment of aquatic invertebrates in nondosed streams was evaluated with respect to (i) the presence of different aquatic macrophytes and (ii) the duration of the pre-experimental period. The present study highlights the beneficial influence of complex-structured macrophytes and prolonged pre-experimental periods on the abundance of invertebrate taxa. Furthermore, population dynamics were evaluated statistically by simulating PPP-related declines of 30, 50 and 70%. Thereby,

Experiments in water-macrophyte systems to uncover the dynamics of pesticide mitigation processes in vegetated surface waters/streams.

Knowledge on the dynamics and the durability of the processes governing the mitigation of pesticide loads by aquatic vegetation in vegetated streams, which are characterized by dynamic discharge regimes and short chemical residence times, is scarce. In a static long-term experiment (48 h), the dissipation of five pesticides from the aqueous phase followed a biphasic pattern in the presence of aquatic macrophytes. A dynamic concentration decrease driven by sorption to the macrophytes ranged from 8.3 to 60.4% for isoproturon and bifenox, respectively, within the first 2 h of exposure. While the aqueous concentrations of imidacloprid, isoproturon, and tebufenozide remained constant thereafter, the continuous but decelerated concentration decrease of difenoconazole and bifenox in the water-macrophyte systems used here was assumed to be attributed to macrophyte-induced degradation processes. In addition, a semi-static short-term experiment was conducted, where macrophytes were transferred to uncontaminated medium after 2 h of exposure to simulate a transient pesticide peak. In the first part of the experiment, adsorption to macrophytes resulted in partitioning coefficients (logK D_Adsorp) ranging from 0.2 for imidacloprid to 2.2 for bifenox. One hour after the macrophytes were transferred to the uncontaminated medium, desorption of the compounds from the macrophytes resulted in a new phase equilibrium and K D_Desorp values of 1.46 for difenoconazole and 1.95 for bifenox were determined. A correlation analysis revealed the best match between the compound affinity to adsorb to macrophytes (expressed as K D_Adsorp) and their soil organic carbon-water partitioning coefficient (K OC) compared to their octanol-water partitioning coefficient (K OW) or a mathematically derived partitioning coefficient.

Role of submerged vegetation in the retention processes of three plant protection products in flow-through stream mesocosms.

Quantitative information on the processes leading to the retention of plant protection products (PPPs) in surface waters is not available, particularly for flow-through systems. The influence of aquatic vegetation on the hydraulic- and sorption-mediated mitigation processes of three PPPs (triflumuron, pencycuron, and penflufen; logKOW 3.3-4.9) in 45-m slow-flowing stream mesocosms was investigated. Peak reductions were 35-38% in an unvegetated stream mesocosm, 60-62% in a sparsely vegetated stream mesocosm (13% coverage with Elodea nuttallii), and in a similar range of 57-69% in a densely vegetated stream mesocosm (100% coverage). Between 89% and 93% of the measured total peak reductions in the sparsely vegetated stream can be explained by an increase of vegetation-induced dispersion (estimated with the one-dimensional solute transport model OTIS), while 7-11% of the peak reduction can be attributed to sorption processes. However, dispersion contributed only 59-71% of the peak reductions in the densely vegetated stream mesocosm, where 29% to 41% of the total peak reductions can be attributed to sorption processes. In the densely vegetated stream, 8-27% of the applied PPPs, depending on the logKOW values of the compounds, were temporarily retained by macrophytes. Increasing PPP recoveries in the aqueous phase were accompanied by a decrease of PPP concentrations in macrophytes indicating kinetic desorption over time. This is the first study to provide quantitative data on how the interaction of dispersion and sorption, driven by aquatic macrophytes, influences the mitigation of PPP concentrations in flowing vegetated stream systems.

Effects of peak exposure scenarios on Gammarus fossarum using field relevant pesticide mixtures.

The present study investigated sublethal effects of a field relevant pesticide mixture (one herbicide, three fungicides, five insecticides) on Gammarus fossarum by considering different peak exposure scenarios, which may be generated by the inherent properties of vegetated ditches. Additional experiments aimed at the identification of germane exposure pathways (food and water). Therefore, G. fossarum were exposed in independent experiments to three scenarios, which differed besides in the peak concentration of the pesticide mixture also in the mixture's composition and exposure duration (n=20 per treatment). The exposure duration of 12 or 120 min was followed by a seven-day post-exposure observation period. At a constant concentration-time product, a lower exposure duration in concert with a proportionally higher peak concentration caused a substantially elevated ecotoxicity compared to a treatment with a longer exposure duration at a lower peak concentration. Given the importance of the insecticide lambda-cyhalothrin for the mixture's ecotoxicity it may be concluded that the fast mode of action of pyrethroids mainly explains this observation. Moreover, field relevant concentrations of the pesticide mixture applied at an exposure duration of 120 min resulted in reduced gammarids' feeding rate, which may be indicative for shifts in the ecosystem function of leaf litter breakdown and hence the provision of energy for local and downstream communities. Finally, the present study indicated that both pathways of exposure, namely via food or water, reduce gammarids' feeding rate synergistically. This suggests that both exposure pathways should be considered for compounds exhibiting a high Kow (e.g. pyrethroids) during the risk assessment of single substances and mixtures.

The Landau Stream Mesocosm Facility: pesticide mitigation in vegetated flow-through streams.

Vegetated treatment systems have the ability to reduce the risk of adverse effects of nonpoint source pesticide pollution in agricultural surface waters, however, flow-through systems have rarely been evaluated. Peak concentrations of a mixture of two insecticides and two fungicides (Indoxacarb, Tebuconazole, Thiacloprid and Trifloxystrobin) were reduced by more than 90% in 45 m experimental stream mesocosms. Plant density and solubility had the highest explanatory power for the response variable reduction of peak concentration (R² = 0.70, p < 0.001). Optimized vegetated streams can be highly effective in reduction of runoff related pesticide peak concentrations.

Mitigation of biocide and fungicide concentrations in flow-through vegetated stream mesocosms.

Organic chemicals entering surface waters may interact with aquatic macrophytes, which in turn may reduce potential negative effects on aquatic organisms. The overall objective of the present study was to determine the significance of aquatic macrophytes to the retention of organic chemicals in slow-flowing streams and thus their contribution to the mitigation of the risks that these compounds may pose to aquatic ecosystems. Hence, we conducted a study on the mitigation of the biocides triclosan and triclocarban and the fungicides imazalil, propiconazole and thiabendazole, which were experimentally spiked to five flow-through stream mesocosms (45 m length, 0.4 m width, 0.26 m water depth, discharge 1 L/s), four of which were planted with the submerged macrophyte (Planch.). Chemical analyses were performed using liquid chromatography-tandem mass spectrometry following solid-phase extraction for water samples and accelerated solvent extraction for macrophyte and sediment samples. The peak reductions of biocide and fungicide concentrations from the inlet to the outlet sampling sites were ≥48% in all stream mesocosms, and the peak reductions in the vegetated stream mesocosms were 20 to 25% greater than in the unvegetated mesocosm. On average, 7 ± 3 to 10 ± 3% and 28 ± 8 to 34 ± 14% of the initially applied amount of fungicides and biocides, respectively, were retained by macrophytes. There was a significant correlation between retention by macrophytes and the lipophility of the compounds.

Ecotoxicological evaluation of three tertiary wastewater treatment techniques via meta-analysis and feeding bioassays using Gammarus fossarum.

Advanced treatment techniques, like ozone, activated carbon and TiO(2) in combination with UV, are proposed to improve removal efficiency of micropollutants during wastewater treatment. In a meta-analysis of peer-reviewed literature, we found significantly reduced overall ecotoxicity of municipal wastewaters treated with either ozone (n=667) or activated carbon (=113), while TiO(2) and UV was not yet assessed. As comparative investigations regarding the detoxification potential of these advanced treatment techniques in municipal wastewater are scarce, we assessed them in four separate Gammarus-feeding trials with 20 replicates per treatment. These bioassays indicate that ozone concentrations of approximately 0.8mg ozone/mg DOC may produce toxic transformation products. However, referred effects are removed if higher ozone concentrations are used (1.3mg ozone/mg DOC). Moreover, the application of 1g TiO(2)/l and ambient UV consistently reduced ecotoxicity. Although activated carbon may remove besides micropollutants also nutrients, which seemed to mask its detoxification potential, this treatment technique reduced the ecotoxicity of the wastewater following its amendment with nutrients. Hence, all three advanced treatment techniques are suitable to reduce the ecotoxicity of municipal wastewater mediated by micropollutants and may hence help to meet the requirements of the European Water Framework Directive.

Fungal composition on leaves explains pollutant-mediated indirect effects on amphipod feeding.

The energy stored in coarse particulate organic matter, e.g. leaf litter, is released to aquatic ecosystems by breakdown processes involving microorganisms and leaf shredding invertebrates. The palatability of leaves and thus the feeding of shredders on leaf material are highly influenced by microorganisms. However, implications in the colonization of leaves by microorganisms (=conditioning) caused by chemical stressors are rarely studied. Our laboratory experiments, therefore, investigated for the first time effects of a fungicide on the conditioning process of leaf material by means of food-choice experiments using Gammarus fossarum (Crustacea: Amphipoda). Additionally, microbial analyses were conducted to facilitate the mechanistic understanding of the observed behavior. Gammarids significantly preferred control leaf discs over those conditioned in presence of the fungicide tebuconazole at concentrations of 50 and 500 µg/L. Besides the decrease of fungal biomass with increasing fungicide concentration, also the leaf associated fungal community composition showed that species preferred by gammarids, such as Alatospora acumunata, Clavariopsis aquatica, or Flagellospora curvula, were more frequent in the control. Tetracladium marchalianum, however, which is rejected by gammarids, was abundant in all treatments suggesting an increasing importance of this species for the lower leaf palatability--as other more palatable fungal species were almost absent--in the fungicide treatments. Hence, the food-choice behavior of G. fossarum seems to be a suitable indicator for alterations in leaf associated microbial communities, especially fungal species composition, caused by chemical stressors. Finally, this or similar test systems may be a reasonable supplement to the environmental risk assessment of chemicals in order to achieve its protection goals, as on the one hand, indirect effects may occur far below concentrations known to affect gammarids directly, and on the other hand, the observed shifts in leaf associated microbial communities may have perpetuating implications in leaf shredding invertebrates.