Peter C. von der Ohe

Analyzing effects of pesticides on invertebrate communities in streams

The aim of this investigation was to find patterns in aquatic invertebrate community composition that are related to the effects of pesticides. Investigations were carried out in 20 central European streams. To reduce the site-specific variation of community descriptors due to environmental factors other than pesticides, species were classified and grouped according to their vulnerability to pesticides. They were classified as species at risk (SPEAR) and species not at risk (SPEnotAR). Ecological traits used to define these groups were sensitivity to toxicants, generation time, migration ability, and presence of aquatic stages during time of maximum pesticide application. Results showed that measured pesticide concentrations of 1:10 of the acute 48-h median lethal concentration (LC50) of Daphnia magna led to a short- and long-term reduction of abundance and number of SPEAR and a corresponding increase in SPEnotAR. Concentrations of 1:100 of the acute 48-h LC50 of D. magna correlated with a long-term change of community composition. However, number and abundance of SPEAR in disturbed stream sections are increased greatly when undisturbed stream sections are present in upstream reaches. This positive influence compensated for the negative effect of high concentrations of pesticides through recolonization. The results emphasize the importance of considering ecological traits and recolonization processes on the landscape level for ecotoxicological risk assessment.

Organic chemicals jeopardize the health of freshwater ecosystems on the continental scale

Significance Protection of freshwater ecosystems from organic pollutants is important to preserve biodiversity and the goods they provide to society, such as clean drinking water and recreation. Organic chemicals have been shown to adversely impact freshwater ecosystems in local and regional studies. Nevertheless, due to paucity of studies on larger spatial scales, it remains unknown how widespread the risk from organic chemicals is. For the first time, to our knowledge, we provide strong evidence that chemicals threaten the ecological integrity and consequently the biodiversity of almost half of the water bodies on a continental scale, based on the analysis of governmental monitoring data from 4,000 European sites. Due to limitations associated with the monitoring programs, our results are likely to underestimate the actual risks. Organic chemicals can contribute to local and regional losses of freshwater biodiversity and ecosystem services. However, their overall relevance regarding larger spatial scales remains unknown. Here, we present, to our knowledge, the first risk assessment of organic chemicals on the continental scale comprising 4,000 European monitoring sites. Organic chemicals were likely to exert acute lethal and chronic long-term effects on sensitive fish, invertebrate, or algae species in 14% and 42% of the sites, respectively. Of the 223 chemicals monitored, pesticides, tributyltin, polycyclic aromatic hydrocarbons, and brominated flame retardants were the major contributors to the chemical risk. Their presence was related to agricultural and urban areas in the upstream catchment. The risk of potential acute lethal and chronic long-term effects increased with the number of ecotoxicologically relevant chemicals analyzed at each site. As most monitoring programs considered in this study only included a subset of these chemicals, our assessment likely underestimates the actual risk. Increasing chemical risk was associated with deterioration in the quality status of fish and invertebrate communities. Our results clearly indicate that chemical pollution is a large-scale environmental problem and requires far-reaching, holistic mitigation measures to preserve and restore ecosystem health.

Relative sensitivity distribution of aquatic invertebrates to organic and metal compounds

In the field, a multitude of species can be exposed to numerous toxicants; thus, the sensitivity of individual species to particular toxicants must be known to predict effects and to analyze changes in species composition. For most species, no information about their toxicant sensitivity is available. To address this limitation, we have grouped the available information to assign sensitivities to aquatic invertebrate taxa relative to Daphnia magna. With respect to organic compounds, most taxa of the orders Anisoptera, Basommatophora, Coleoptera, Decapoda, Diptera, Ephemeroptera, Eulamellibranchiata, Heteroptera, Hirudinea, Isopoda, Oligochaeta, Prosobranchia, Trichoptera, Tricladida, and Zygoptera are less sensitive than D. magna. Some taxa of the Amphipoda, Plecoptera, and Cladocera (other than D. magna) are significantly more sensitive. For organic compounds, approximately 22% of the investigated taxa were more sensitive than D. magna. Most taxa of the orders Amphipoda, Basommatophora, Diptera, Ephemeroptera, Eulamellibranchiata, Heteroptera, Isopoda, Oligochaeta, and Tricladida are significantly less sensitive than D. magna to metal compounds. The taxa belonging to the Crustacea, with the exception of the order Isopoda, are much more sensitive. For metal compounds, approximately 30% of the investigated taxa were more sensitive than D. magna. Hence, D. magna is among the most sensitive taxa regarding both groups of toxicants. The sensitivities for several taxa are listed, and use of the relative sensitivity distribution to link toxicant effects in mesocosm studies and field investigations is discussed.

A new risk assessment approach for the prioritization of 500 classical and emerging organic microcontaminants as potential river basin specific pollutants under the European Water Framework Directive

Given the huge number of chemicals released into the environment and existing time and budget constraints, there is a need to prioritize chemicals for risk assessment and monitoring in the context of the European Union Water Framework Directive (EU WFD). This study is the first to assess the risk of 500 organic substances based on observations in the four European river basins of the Elbe, Scheldt, Danube and Llobregat. A decision tree is introduced that first classifies chemicals into six categories depending on the information available, which allows water managers to focus on the next steps (e.g. derivation of Environmental Quality Standards (EQS), improvement of analytical methods, etc.). The priority within each category is then evaluated based on two indicators, the Frequency of Exceedance and the Extent of Exceedance of Predicted No-Effect Concentrations (PNECs). These two indictors are based on maximum environmental concentrations (MEC), rather than the commonly used statistically based averages (Predicted Effect Concentration, PEC), and compared to the lowest acute-based (PNEC(acute)) or chronic-based thresholds (PNEC(chronic)). For 56% of the compounds, PNECs were available from existing risk assessments, and the majority of these PNECs were derived from chronic toxicity data or simulated ecosystem studies (mesocosm) with rather low assessment factors. The limitations of this concept for risk assessment purposes are discussed. For the remainder, provisional PNECs (P-PNECs) were established from read-across models for acute toxicity to the standard test organisms Daphnia magna, Pimephales promelas and Selenastrum capricornutum. On the one hand, the prioritization revealed that about three-quarter of the 44 substances with MEC/PNEC ratios above ten were pesticides. On the other hand, based on the monitoring data used in this study, no risk with regard to the water phase could be found for eight of the 41 priority substances, indicating a first success of the implementation of the WFD in the investigated river basins.

Thresholds for the Effects of Pesticides on Invertebrate Communities and Leaf Breakdown in Stream Ecosystems

We compiled data from eight field studies conducted between 1998 and 2010 in Europe, Siberia, and Australia to derive thresholds for the effects of pesticides on macroinvertebrate communities and the ecosystem function leaf breakdown. Dose-response models for the relationship of pesticide toxicity with the abundance of sensitive macroinvertebrate taxa showed significant differences to reference sites at 1/1000 to 1/10,000 of the median acute effect concentration (EC50) for Daphnia magna, depending on the model specification and whether forested upstream sections were present. Hence, the analysis revealed effects well below the threshold of 1/100 of the EC50 for D. magna incorporated in the European Union Uniform Principles (UP) for registration of single pesticides. Moreover, the abundances of sensitive macroinvertebrates in the communities were reduced by 27% to 61% at concentrations related to 1/100 of the EC50 for D. magna. The invertebrate leaf breakdown rate was positively linearly related to the abundance of pesticide-sensitive macroinvertebrate species in the communities, though only for two of the three countries examined. We argue that the low effect thresholds observed were not mainly because of an underestimation of field exposure or confounding factors. From the results gathered we derive that the UP threshold for single pesticides based on D. magna is not protective for field communities subject to multiple stressors, pesticide mixtures, and repeated exposures and that risk mitigation measures, such as forested landscape patches, can alleviate effects of pesticides.

Effects of pesticides monitored with three sampling methods in 24 sites on macroinvertebrates and microorganisms.

Grab water samples, sediment samples, and 2,2,4-trimethylpentane passive samplers (TRIMPS) were used to determine the exposure to 97 pesticides in 24 southeast Australian stream sites over 5 months. Macroinvertebrate communities and selected microorganisms (bacteria, flagellates, ciliates, amoebas, nematodes, and gastrotrichs) were sampled to detect relationships with pesticide toxicity. Sediment samples had the highest estimated toxicities in terms of toxic units (TU) for Daphnia magna (TUDM) and for Selenastrum capricornutum (TUSC). The pesticide-selective SPEARpesticides and the general SIGNAL index for macroinvertebrates exhibited negative linear relationships (r(2) = 0.67 and 0.36, respectively) with pesticide contamination in terms of log maximum TUDM (log mTUDM), suggesting macroinvertebrate community change due to pesticide exposure. Pesticide contamination was the only measured variable explaining variation in ecological quality. Variation in the densities of several microbial groups was best explained by environmental variables other than log TUs. The log mTUDM values derived from sediment concentrations were most important to establish a link with effects on macroinvertebrates, whereas log mTUDM of grab water samples had only minor contribution. Current-use insecticides and fungicides can affect macroinvertebrate communities and monitoring of sediment and continuous water sampling is needed to detect these effects.

Occurrence and toxicity of 331 organic pollutants in large rivers of north Germany over a decade (1994 to 2004).

We analyzed the detection frequencies and concentrations for 331 organic compounds measured between 1994 and 2004 in the four largest rivers of north Germany, the Elbe, Weser, Aller, and Ems Rivers, and we assessed the potential risk for aquatic fauna using experimental and predicted acute toxicity data for the green alga Pseudokirchneriella subcapitata, the crustacean Daphnia magna, and the fish Pimephales promelas. The detection frequency for most compounds decreased significantly from 1994 to 2004. Polycyclic aromatic hydrocarbons (PAHs) were most frequently detected, while pesticides were the most important chemical group concerning toxicity for the standard test organisms. The predicted toxicity for D. magna was significantly higher than for the other organisms and reached levels envisaging acute toxic effects on the invertebrate fauna, still in 2004. Most of the compounds responsible for potential acute effects on aquatic organisms are currently not considered as priority substances in the European Union, while only 2 of 25 priority substances that have been measured occurred at levels that may be relevant in terms of toxicity for the selected test organisms. We conclude that attenuation of pesticides and other organic toxicants should play an increased role in river basin management.

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.

Sediment pollution in the Elbe estuary and its potential toxicity at different trophic levels.

Sediment contamination is one of the most pressing environmental problems in estuaries of industrialized countries and is of special interest to water managers involved in waterway maintenance dredging. In the present study, eight heavy metals (As, Pb, Cd, Cr, Cu, Ni, Hg, and Zn) and 41 organic compounds (pentachlorbenzol (PeCB), hexachlorbenzol (HCB), 7 polychlorinated biphenyls (PCBs), the hexachlorocyclohexanes α-HCH, β-HCH, γ-HCH, 6 dichlorodiphenyltrichloroethane isomers, organochlorine styrene (OCS), octachloronaphthalene (OCN), 15 polycyclic aromatic hydrocarbons (PAHs), and 6 organotin (OT) compounds) were analyzed in surface sediments at 36 sites in the Elbe estuary in 2006. Correlation analysis showed a general decrease in sediment contaminant concentrations from the stations near the port of Hamburg towards the open sea. This decrease was significant (Spearmans rank correlation, p<0.05) with most pollutants. In addition, cluster analysis identified five groups of sites with different sediment contaminant patterns within the Elbe estuary. Worst case toxic risks stemming from sediment-bound organic pollutants were predicted using the Toxic Unit approach, based on estimated pore-water concentrations under equilibrium conditions and acute LC50 values for three standard test organisms of the trophic levels of fish, invertebrates, and algae. The estimated sediment toxicity was significantly higher in the inner part (river-km 630 to 660) compared with the estuarine mouth. Moreover, potential toxicity of organic pollutants estimated for invertebrates and for fish exceeded acute-based effect thresholds at 30 and 24 stations, respectively. Chronic effects for invertebrates are expected at all sites investigated. We conclude that sediment pollution and related potential toxicity in the Elbe estuary may have more influence on the benthos fauna than expected to date.

Identification of a phytotoxic photo-transformation product of diclofenac using effect-directed analysis

The pharmaceutical diclofenac (DCF) is released in considerably high amounts to the aquatic environment. Photo-transformation of DCF was reported as the main degradation pathway in surface waters and was found to produce metabolites with enhanced toxicity to the green algae Scenedesmus vacuolatus. We identified and subsequently confirmed 2-[2-(chlorophenyl)amino]benzaldehyde (CPAB) as a transformation product with enhanced toxicity using effect-directed analysis. The EC(50) of CPAB (4.8 mg/L) was a factor of 10 lower than that for DCF (48.1 mg/L), due to the higher hydrophobicity of CPAB (log K(ow) = 3.62) compared with DCF (log D(ow) = 2.04) at pH 7.0.