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Abstract: Bankside groundwater is widely used as drinking water resource and, therefore, contamination has to be avoided. In the European Union groundwater protection is explicit subject to Water Framework Directive. While groundwater pollution may originate from different sources, this study investigated on impacts via flood events. Groundwater was sampled with increasing distance to the river Rhine near Karlsruhe, Germany. Samples were HPLC–MS–MS analyzed for the river contaminant carbamazepine to indicate river water infiltration, giving permanent presence in 250m distance to the river (14–47μgL−1). Following a flood event, concentrations of about 16–20μgL−1 could also be detected in a distance of 750m to the river. Furthermore, estrogenic activity as determined with the Yeast Estrogen Screen assay was determined to increase up to a 17β-ethinylestradiol equivalent concentration (E-EQ)=2.9ngL−1 near the river, while activity was initially measured following the flood with up to E-EQ=2.6ngL−1 in 750m distance. Detections were delayed with increasing distance to the river indicating river water expansion into the aquifer. Flood suspended matter and floodplain soil were fractionated and analyzed for estrogenic activity in parallel giving up to 1.4ngg−1 and up to 0.7ngg−1, respectively. Target analysis focusing on known estrogenic active substances only explained <1% of measured activities. Nevertheless, river water infiltration was shown deep into bankside groundwater, thus, impacting groundwater quality. Therefore, flood events have to be in the focus when aiming for groundwater and drinking water protection as well as for implementation of Water Framework Directive. [Copyright &y& Elsevier]

Sediment extracts from three polluted sites of the river Elbe basin were fractionated using a novel online fractionation procedure. Resulting fractions were screened for mutagenic, aryl hydrocarbon receptor (AhR)-mediated, transthyretin (TTR)-binding, and estrogenic activities and their potency to inhibit gap junctional intercellular communication (GJIC) to compare toxicity patterns and identify priority fractions. Additionally, more than 200 compounds and compound classes were identified using GC-MS/MS, LC-MS/MS, and HPLC-DAD methods. For all investigated end points, major activities were found in polar fractions, which are defined here as fractions containing dominantly compounds with at least one polar functional group. Nonpolar PAH fractions contributed to mutagenic and AhR-mediated activities while inhibition of GJIC and estrogenic and TTR-binding activities were exclusively observed in the polar fractions. Known mutagens in polar fractions included nitro- and dinitro-PAHs, azaarenes, and keto-PAHs, while parent and monomethylated PAHs such as benzo[a]pyrene and benzofluoranthenes were identified in nonpolar fractions. Additionally, for one sample, high AhR-mediated activities were determined in one fraction characterized by PCDD/Fs, PCBs, and PCNs. Estrone, 17β-estradiol, 9H-benz[de]anthracen-7-one, and 4-nonylphenol were identified as possible estrogenic and TTR-binding compounds. Thus, not only nonpolar compounds such as PAHs, PCBs, and PCDD/Fs but also the less characterized and investigated more polar substances should be considered as potent mutagenic, estrogenic, AhR-inducing, TTR-binding, and GJIC-inhibiting components for future studies.

The environmental risk assessment of toxicants is often derived from chemical monitoring, based on single species tests performed in the laboratory. However, to provide ecologically relevant information, community approaches are required. The aim of this study was to causally link prometryn exposure to community-level effects in complex field situations and to identify response times of adaptation to pollution and recovery from pollution. For this reason sensitivity shifts in communities were detected and related to structural changes within the periphyton community. Furthermore, it was intended to illustrate the possibility of a combined approach of community translocation and sensitivity assessment for active monitoring of polluted sites. Periphyton was grown at a reference (R) and at a polluted (P) site of the river Elbe basin for 26 days, was subsequently transferred from the polluted site to the reference site and vice versa. Sensitivity of communities to prometryn was determined according to the pollution-induced community tolerance (PICT)-concept in short-term tests by measuring photosynthesis inhibition and was related to structural changes in algal class and diatom species composition. Exposure to prometryn was determined using polar organic integrative samplers (POCIS), giving time-weighted average concentrations. Environmental concentrations of prometryn were significantly higher at the polluted site compared to the reference site. Communities grown at the polluted site showed a higher tolerance to prometryn in comparison to the reference site. 17 Days after the translocation to the reference site, EC(50) decreased 2-fold compared to the non-translocated P-community of the same age. By contrast, EC(50) of the community grown at the reference site was 5 times higher after 17 days exposure at the polluted site. Furthermore, P-R communities were less sensitive to prometryn (higher EC(50)) than R-P communities, 24 days after translocation. These changes in sensitivity to prometryn were consistent with changes in species composition and clearly indicate that the exposure history of communities is defining the time-response of recovery and adaptation. In conclusion, the PICT-concept is shown to be a suitable tool for analysis of recovery and adaptation processes of communities under natural conditions. Therefore, it improves the link between cause and effect in field situations. In situ translocation studies provide an ecological relevant assessment of pesticide effects under field conditions and could be used as a diagnostic tool in active monitoring for decision-making frameworks as used in the implementation of the European Water Framework Directive (WFD)., (Copyright © 2010 Elsevier B.V. All rights reserved.)

Benthic algae are the dominant primary producers in many rivers and may be at risk of being affected by sediment-associated toxicants. Toxicity as well as bioaccessibility should be considered for the identification of major toxicants affecting benthic algae. Thus, effect-directed analysis (EDA) combining biotesting, fractionation, and chemical analysis was combined with both exhaustive and bioaccessibility-directed extraction to identify the major toxicants in sediments at three industrial sites in the Elbe River basin (Bitterfeld, Most, and Prelouc). Exhaustive accelerated solvent extraction was used together with bioaccessibility-directed extraction with TENAX in aqueous suspension. Growth inhibition of the green alga Scenedesmus vacuolatus identified polycyclic aromatic compounds as important algal toxicants at all three sites, while in Bitterfeld and Prelouc additional toxicants, such as N-phenyl-2-naphthylamine and 7H-benzo[de]anthracen-7-one, played an important role. Confirmation of the identified compounds was based on the index of confirmation quality (ICQ) comparing the effect of an artificial mixture to that of the original sample. The results suggest a successful confirmation of identified toxicants for most fractions with ICQ values between 0.5 and 2. The bioaccessibility of toxicants decreased in the order Prelouc > Bitterfeld > Most as determined by the investigation of TENAX samples. Similar total concentrations of toxicants in Prelouc and Most sediment result in bioaccessible concentrations in Prelouc that exceed those in Most by a factor of 10 to 20. The extraction with TENAX with a subsequent EDA proved to be a powerful tool for prioritizing contaminants and contaminated sites with respect to the hazard of sediment-associated toxicants to green algae.