Mirco Bundschuh

Fate and effects of poly‐ and perfluoroalkyl substances in the aquatic environment: A review

Polyfluoroalkyl and perfluoroalkyl substances (PFASs) are distributed ubiquitously in the aquatic environment, which raises concern for the flora and fauna in hydrosystems. The present critical review focuses on the fate and adverse effects of PFASs in the aquatic environment. The PFASs are continuously emitted into the environment from point and nonpoint sources such as sewage treatment plants and atmospheric deposition, respectively. Although concentrations of single substances may be too low to cause adverse effects, their mixtures can be of significant environmental concern. The production of C8 -based PFASs (i.e., perfluorooctane sulfonate [PFOS] and perfluorooctanoate [PFOA]) is largely phased out; however, the emissions of other PFASs, in particular short-chain PFASs and PFAS precursors, are increasing. The PFAS precursors can finally degrade to persistent degradation products, which are, in particular, perfluoroalkane sulfonates (PFSAs) and perfluoroalkyl carboxylates (PFCAs). In the environment, PFSAs and PFCAs are subject to partitioning processes, whereby short-chain PFSAs and PFCAs are mainly distributed in the water phase, whereas long-chain PFSAs and PFCAs tend to bind to particles and have a substantial bioaccumulation potential. However, there are fundamental knowledge gaps about the interactive toxicity of PFAS precursors and their persistent degradation products but also interactions with other natural and anthropogenic stressors. Moreover, because of the continuous emission of PFASs, further information about their ecotoxicological potential among multiple generations, species interactions, and mixture toxicity seems fundamental to reliably assess the risks for PFASs to affect ecosystem structure and function in the aquatic environment.

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.

Ecotoxicological impact of the fungicide tebuconazole on an aquatic decomposer‐detritivore system

Leaf litter breakdown is a fundamental process in aquatic ecosystems that is realized by microbial decomposers and invertebrate detritivores. Although this process may be adversely affected by fungicides, among other factors, no test design exists to assess combined effects on such decomposer-detritivore systems. Hence, the present study assessed effects of the model fungicide tebuconazole (65 µg/L) on the conditioning of leaf material (by characterizing the associated microbial community) as well as the combined effects (i.e., direct toxicity and food quality-related effects (=indirect)) on the energy processing of the leaf-shredding amphipod Gammarus fossarum using a five-week semistatic test design. Gammarids exposed to tebuconazole produced significantly less feces (≈ 20%), which in turn significantly increased their assimilation (≈ 30%). Moreover, a significantly reduced lipid content (≈ 20%) indicated lower physiological fitness. The conditioning process was altered as well, which was indicated by a significantly reduced fungal biomass (≈ 40%) and sporulation (≈ 30%) associated with the leaf material. These results suggest that tebuconazole affects both components of the investigated decomposer-detritivore system. However, adverse effects on the level of detritivores cannot be explicitly attributed to direct or indirect pathways. Nevertheless, as the endpoints assessed are directly related to leaf litter breakdown and associated energy transfer processes, the protectiveness of environmental risk assessment for this ecosystem function may be more realistically assessed in future studies by using this or comparable test designs.

Evaluation of pesticide monitoring strategies in agricultural streams based on the toxic-unit concept — Experiences from long-term measurements

The European Water Framework Directive requires surface water bodies to have a good chemical and ecological status. Although relatively few pesticides are included in the list of priority pollutants, they pose, due to their intrinsic biological activity, a significant risk for the integrity of aquatic ecosystems. In this context, the pesticide (up to 128 pesticides including some transformation products) exposure pattern in four agricultural streams and two rivers was determined from 2002 to 2011 under the umbrella of the Swedish national monitoring program employing time-proportional and grab sampling strategies, respectively. After transforming the measured pesticide concentrations into toxic units, the European Uniform Principles for algae (chronic), invertebrates and fish (both acute), which are partly employed as benchmark for pesticide regulation, were only occasionally (<2%) exceeded. Moreover, this evaluation showed no long-term trends over the years. However, recent publications suggested that those thresholds are not protective for ecosystem structure and function, indicating a risk of up to 20% and 35% of the samples from the agricultural streams and the rivers, respectively. Moreover, the monitoring data show a continuous but rather low toxic potential of pesticides for all three trophic levels throughout the year, which suggests pesticides as an evolutionary force in agriculturally impacted aquatic ecosystems. However, the flow-triggered sampling, which was implemented as an additional sampling strategy in one of the agricultural streams starting in 2006, displayed an up to 7-fold underestimation of the maximum concentration in terms of toxic units for daphnids and fish during run-off events. The present study thus underpins that the optimal sampling design for pesticide monitoring strongly depends on its overall purpose. If the long-term exposure pattern is of concern a time-proportional composite sampling strategy is recommended, while for an assessment of peak exposures a flow-event-triggered high-resolution sampling strategy is superior.

Antibiotics as a chemical stressor affecting an aquatic decomposer-detritivore system.

Recent evidence indicates that a variety of antibiotic residues may affect the integrity of streams located downstream from wastewater treatment plants. Aquatic communities comprising bacterial and fungal decomposers and invertebrate detritivores (shredders) play an important role in the decomposition of allochthonous leaf litter, which acts as a primary energy source for small running waters. The aim of the present study was to assess whether an antibiotic mixture consisting of sulfamethoxazole, trimethoprim, erythromycin-H2O, roxithromycin, and clarithromycin has an effect on such a decomposer-detritivore system. Leaf discs were exposed to these antibiotics (total concentration of 2 or 200 microg/L) for approximately 20 d before offering these discs and corresponding control discs to an amphipod shredder, Gammarus fossarum, in a food choice experiment. Gammarus preferred the leaf discs conditioned in the presence of the antibiotic mixture at 200 microg/L over the control discs (pair-wise t test; p = 0.006). A similar tendency, while not significant, was observed for leaves conditioned with antibiotics at a concentration of 2 microg/L. The number of bacteria associated with leaves did not differ between treatments at either antibiotic concentration (t test; p = 0.57). In contrast, fungal biomass (measured as ergosterol) was significantly higher in the 200 microg/L treatment (t test; p = 0.038), suggesting that the preference of Gammarus may be related to a shift in fungal communities. Overall these results indicate that mixtures of antibiotics may disrupt important ecosystem processes such as organic matter flow in stream ecosystems, although effects are likely to be weak at antibiotic concentrations typical of streams receiving wastewater treatment plant effluents.

Review on the effects of toxicants on freshwater ecosystem functions

We reviewed 122 peer-reviewed studies on the effects of organic toxicants and heavy metals on three fundamental ecosystem functions in freshwater ecosystems, i.e. leaf litter breakdown, primary production and community respiration. From each study meeting the inclusion criteria, the concentration resulting in a reduction of at least 20% in an ecosystem function was standardized based on median effect concentrations of standard test organisms (i.e. algae and daphnids). For pesticides, more than one third of observations indicated reductions in ecosystem functions at concentrations that are assumed being protective in regulation. Moreover, the reduction in leaf litter breakdown was more pronounced in the presence of invertebrate decomposers compared to studies where only microorganisms were involved in this function. High variability within and between studies hampered the derivation of a concentration-effect relationship. Hence, if ecosystem functions are to be included as protection goal in chemical risk assessment standardized methods are required.

The functional and physiological status of Gammarus fossarum (Crustacea; Amphipoda) exposed to secondary treated wastewater

Climate change scenarios predict lower flow rates during summer that may lead to higher proportions of wastewater in small and medium sized streams. Moreover, micropollutants (e.g. pharmaceuticals and other contaminants) continuously enter aquatic environments via treated wastewater. However, there is a paucity of knowledge, whether extended exposure to secondary treated wastewater disrupts important ecosystem functions, e.g. leaf breakdown. Therefore, the amphipod shredder Gammarus fossarum was exposed to natural stream water (n=34) and secondary treated wastewater (n=32) for four weeks in a semi-static test system under laboratory conditions. G. fossarum exposed to wastewater showed significant reductions in feeding rate (25%), absolute consumption (35%), food assimilation (50%), dry weight (18%) and lipid content (22%). Thus, high proportions of wastewater in the stream flow may affect both the breakdown rates of leaf material and thus the availability of energy for the aquatic food web as well as the energy budget of G. fossarum.

Heavy Metal Uptake and Toxicity in the Presence of Titanium Dioxide Nanoparticles: A Factorial Approach Using Daphnia magna.

Unintentionally released titanium dioxide nanoparticles (nTiO2) may co-occur in aquatic environments together with other stressors, such as, metal ions. The effects of P25-nTiO2 on the toxicity and uptake of the elements silver (Ag), arsenic (As) and copper (Cu) were assessed by applying a factorial test design. The test design consisted of two developmental stages of Daphnia magna, two levels of nTiO2 (0 versus 2 mg/L) as well as seven nominal test concentrations of the respective element. The presence of nTiO2 increased Ag toxicity for juveniles as indicated by a 40% lower 72-h EC50, while the toxicities of As and Cu were reduced by up to 80%. This reduction was even more pronounced for Cu in the presence of dissolved organic carbon (i.e., seaweed extract) and nTiO2. This outcome coincides with the body burden of the elements, which was elevated 2-fold for Ag and decreased 14-fold for Cu in the presence of nTiO2. Although the underlying mechanisms could not be uncovered, the data suggest that the carrier function of nTiO2 plays a central role. However, to understand the processes and mechanisms occurring in the field due to the presence of nTiO2 further systematic investigations considering environmental variables and nanoparticle characteristics are required.

Nanoparticle toxicity in Daphnia magna reproduction studies: The importance of test design

The increasing use of titanium dioxide nanoparticles (nTiO(2)) inevitably results in their release into the environment, raising concerns about potential adverse effects in wildlife. By following standard test protocols, several studies investigated the ecotoxicity of nTiO(2) among others to Daphnia magna. These studies indicated a large variability - several orders of magnitude - in the response variables. However, other factors, like nanoparticle characteristics and test design, potentially triggering these differences, were largely ignored. Therefore, the present study assessed the chronic ecotoxicity of two nTiO(2) products with varying crystalline structure (A-100; P25) to D. magna. A semi-static and a flow-through exposure scenario were compared, ensuring that both contained environmentally relevant concentrations of dissolved organic carbon. Utilizing the semi-static test design, a concentration as low as 0.06 mg/L A-100 (∼330 nm) significantly reduced the reproduction of daphnia indicating environmental risk. In contrast, no implication in the number of released offspring was observed during the flow-through experiment with A-100 (∼140 nm). Likewise, P25 (∼130 nm) did not adversely affect reproduction irrespective of the test design utilized. Given the present studys results, the particle size, the product composition, i.e. the crystalline structure, and the accumulation of nTiO(2) at the bottom of the test vessel - the latter is relevant for a semi-static test design - may be suggested as factors potentially triggering differences in nTiO(2) toxicity to D. magna. Hence, these factors should be considered to improve environmental risk assessment of nanoparticles.

Effects of pesticide toxicity, salinity and other environmental variables on selected ecosystem functions in streams and the relevance for ecosystem services

Effects of anthropogenic and environmental stressors on freshwater communities can propagate to ecosystem functions and may in turn impede ecosystem services. We investigated potential shifts in ecosystem functions that provide energy for freshwater ecosystems due to pesticides and salinity in 24 sites in streams of southeast Australia. First, effects on allochthonous organic matter (AOM) breakdown using three different substrates (leaves, cotton strips, wood sticks) in coarse and fine bags were investigated. Second, we examined effects on stream metabolism that delivers information on the ecosystem functions of gross primary production and ecosystem respiration. We found up to a fourfold reduction in AOM breakdown due to exposure to pesticides and salinity, where both stressors contributed approximately equally to the reduction. The effect was additive as, no interaction or correlation between the two stressors was found. Leaf breakdown responded strongly and exclusively to exposure to pesticides and salinity, whereas cotton strip breakdown was less sensitive and responded also to other stressors such as nutrients. No functional redundancy for the effects of pesticides and salinity on leaf breakdown was observed. For wood stick breakdown, no relationship to environmental gradients was found, however, the sample size was lower. We did not detect effects of pesticides or salinity on gross primary production or ecosystem respiration. A reduction in AOM breakdown by pesticides and salinity may impair the ecosystem services of food provision and possibly water purification. Hence, future studies should examine the spatial extent of these effects.