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Trends of pharmaceutical residues in rivers, suspended particular matter and fish – New insights by new analytical methods for active substances, their metabolites and transformation products

Environmental research is detecting ever more pharmaceutical residues in the aquatic environment as analytical methods become increasingly sensitive. The physicochemical properties of some active substances suggest an accumulation in sediment, suspended matter and biota. Hence, these matrices could be interesting alternative matrices for monitoring of pharmaceutical residues in surface waters. Against this background, modern analytical detection methods for different matrices from water to sediment and suspended matter to biota (fish) were developed and published in 2019 ( FKZ 3715 67 413 ). In the current project sampling concepts were combined with retrospective analyses. In this report, the results of the developed methods from investigations of water, sediment, suspended matter and biota samples from different locations and the German environmental specimen bank are presented in terms of occurrence and distribution. During the project 3 articles have been published: Boulard et al. 2018 ( https://doi.org/10.1016/j.chroma.2017.12.023 ), Boulard et al. 2020 ( https://doi.org/10.1016/j.watres.2019.115366 ), Boulard et al. 2020 ( https://doi.org/10.1016/j.chroma.2020.461612 ). Veröffentlicht in Texte | 94/2022.

Method development for analysis of pharmaceuticals in environmental samples

Since the last decades the increasing currency of pharmaceuticals in the aquatic environment and their risk potential for the aquatic life has become an urgent issue. The number of pharmaceuticals detectable in the low μg/L range in the environment is rising each day. Against this background the aim of this project was the development, optimization, validation and comparison of analytical methods for quantification of selected pharmaceuticals in different environmental matrices (water, sediment, suspended particular matter and biota). High sensitive LC-MS-MS methods for determination of extreme polar, polar ( see also Boulard et al. ) and hormonal pharmaceuticals ( see also Weizel et al. ) in water samples were developed and validated. Using these methods occurrence and distribution of the selected pharmaceuticals in water with different wastewater content were determined. For analysis of pharmaceuticals in particular matter and biota samples extraction and clean-up procedures were tested, but method development is still in process. Furthermore a monitoring campaign was set up and water samples, suspended particular matter and biota (fish) samples from six different sampling sites were taken. During the project 2 articles have been published: Boulard et al. (DOI: 10.1016/j.chroma.2017.12.023) and Weizel at al. (DOI: 10.1021/acs.est.7b06147) . Veröffentlicht in Texte | 42/2019.

Bioaccumulation of ionic compounds - Deriving of alternative screening criteria from experimental studies

Many chemicals for which a ⁠ PBT ⁠ assessment is necessary are ionized in the environment. Therefore, the project aimed to find appropriate screening criteria for ionic organic chemicals (IOCs) to estimate their bioaccumulation potential. Twenty possible parameters were examined. The partitioning coefficient between water and fish calculated with COSMOmic showed the strongest correlation with experimental BMF data. The assumed high bioaccumulation potential was verified but not confirmed for six IOCs by conducting fish feeding studies (⁠ OECD ⁠ 305). Veröffentlicht in Texte | 108/2021.

Retrospective study of triclosan and methyl-triclosan residues in fish and suspended particulate matter: Results from the German Environmental Specimen Bank

Rüdel, Heinz; Böhmer, Walter; Müller, Martin; Fliedner, Annette; Ricking, Mathias; Teubner, Diana; Schröter-Kermani, Christa Chemosphere 91 (2013), 11, 1517-1524 A retrospective monitoring of triclosan (TCS; period 1994-2003 and 2008) and its potential transformation product methyl-triclosan (MTCS; period 1994-2008) was performed using archived fish samples from German rivers (16 sites, including Elbe and Rhine). At four of these sites suspended particulate matter (SPM) was also investigated covering the period 2005-2007. Samples were analyzed by GC/MS, either directly (MTCS) or after derivatization (TCS). TCS burdens of fish muscle tissue ranged from <0.2-3.4 ng g -1 ww (wet weight; corresponding to <2-69 ng g -1 lw, lipid weight) without apparent concentration trends over time. MTCS was detected at considerably higher concentrations in fish ranging from 1.0-33 ng g -1 ww (47-1010 ng g -1 lw) and increased until about 2003-2005. Thereafter, concentrations generally were lower, although at some sites single higher values were observed in recent years. In SPM, decreasing MTCS concentrations in the range 1-4 ng g -1 dry weight were detected while TCS was always below the limit of quantification. Assuming that MTCS concentrations are correlated to TCS consumption, the observed decrease in MTCS levels may be partly a result of the voluntary renunciation of TCS use in detergents for, e.g., laundry or dishwashing declared by a manufacturers’ association in 2001. Because of a lack of ecotoxicity studies for MTCS, a QSAR-derived predicted no effect concentration (PNEC) was compared to averaged ambient water concentrations of fish which were calculated from maximum tissue residues by applying an appropriate bioconcentration factor from literature. Since these calculated water concentrations were below the PNEC it is assumed that MTCS alone poses no immediate risk to aquatic organism. The conversion to a PNEC for SPM organisms and comparison with detected SPM levels of MTCS also revealed no risk. doi:10.1016/j.chemosphere.2012.12.030

Fischgewässer

- Darstellung der als Fischgewässer ausgewiesenen Fließgewässerabschnitte Baden-Württembergs gemäß EU-RL 78/659/EWG- Darstellung der dazugehörigen Messstellen des chem.-phys. Fließgewässermessnetzes Baden-WürttembergGemäß dem natürlichen Temperaturregime der Gewässer wird zwischen den sogenannten Salmoniden- und Cyprinidengewässer unterschieden.Gesetzliche Grundlage:- Anlage 1 der Verordnung des Ministeriums für Umwelt und Verkehr über die Qualität von Fischgewässern (Fischgewässerverordnung, Baden-Württemberg)

Die Anglerprüfung

Den Fischereischein A erhält nur, wer nach einem Vorbereitungslehrgang von mindestens dreißig Stunden Dauer eine Anglerprüfung bestanden hat. In der Prüfung sind ausreichende Kenntnisse auf folgenden Gebieten nachzuweisen: Allgemeine Fischkunde und -hege; spezielle Fischkunde; Pflege der Fischgewässer; Gewässerkunde und einschlägige Fragen der Gewässerökologie sowie über Pflanzen und Tierarten im und am Gewässer; Fanggeräte und deren Gebrauch; Behandlung gefangener Fische; einschlägige Rechtsvorschriften, insbesondere fischereiliche, wasser-, tierschutz-, tierseuchen- und naturschutzrechtliche Vorschriften. Zur Anglerprüfung kann zugelassen werden, wer das vierzehnte Lebensjahr vollendet und am Vorbereitungslehrgang vollständig teilgenommen hat. Vorbereitungslehrgänge mit anschließenden Anglerprüfungen werden durchgeführt vom: VDSF Verband Deutscher Sportfischer – Landesverband Berlin-Brandenburg e. V. Hugo-Cassirer-Straße 46 13587 Berlin Tel.: (030) 7820575 Fax: (030) 7819866 Sprechzeiten: Mo. und Do. 14:00 – 18:00 Uhr E-Mail: info@vdsfberlinbrandenburg.de VDSF – Landesverband Berlin-Brandenburg DAV Deutschen Anglerverband – Landesverband Berlin e.V Hausburgstraße 13 10249 Berlin Tel.: (030) 4271728 Fax: (030) 42808099 Sprechzeiten: Di. und Do. 10:00 – 13:00, 13:30 – 18:00 Uhr E-Mail: info@landesanglerverband-berlin.de DAV – Landesverband Berlin

Fate of 17-ethinylestradiol in the aqueous environment and the associated effects on organisms

Das Projekt "Fate of 17-ethinylestradiol in the aqueous environment and the associated effects on organisms" wird vom Umweltbundesamt gefördert und von RWTH Aachen University, Institut für Umweltforschung, Biologie V, Lehrstuhl für Umweltbiologie und -chemodynamik durchgeführt. Introduction: In aquatic systems, the bioavailability of a compound is dependent on numerous factors such as partitioning between water, different organisms and solids, biotransformation and food web transfer. This project dealt with the fate of an important environmental xeno-estrogen, 17-ethinylestradiol (EE2), in the aquatic environment. Therefore, the kinetics of EE2 in indicator species representing the different trophic levels of an ecosystem were assessed. As primary producers, green algae (Desmodesmus suspicatus) were selected. The water flea Daphnia magna and larvae of the midge Chironomus riparius were introduced as primary consumers of the water phase and the sediment, respectively. Finally, water as well as dietary uptake of EE2 were investigated in a target species and secondary consumer: zebrafish (Danio rerio). Methodology: In a first series of experiments, uptake of 14C-labelled EE2 (14C-EE2) from the water phase and elimination by the different organisms were investigated over time. In a second test series, both primary consumers were fed 14C-EE2 spiked algae in order to study bioaccumulation. Uptake of 14C-EE2 by chironomid larvae after water and sediment spiking was compared, including sediments of different composition. In a third series of experiments, male fish were short term (48 h) exposed to 14C-EE2 through different routes: by water exposure (WE) and by dietary exposure (DE) via both contaminated daphnids and chironomid larvae. Distribution of 14C-EE2 in the fish was studied by measuring the amount of radioactivity (RA) in the different fish tissues. Additionally, the effect of EE2 on the vitellogenin (Vtg) induction in male fish was compared after WE and DE in a long term (14 d) experiment. The RA in liquid samples was quantified by means of liquid scintillation counting (LSC). Solid samples were subjected to combustion in a biological oxidiser, trapping (14)CO2, measured with LSC. Water and organism extracts were analysed by means of HPLC with a radiodetector, except for algae extracts that were subjected to TLC. Metabolites were identified with GC-MS, high resolution LC-MS and enzymatic hydrolysis followed by HPLC with radiodetection. Metabolites, detected in the water phase, were tested for estrogenic activity by means of YES and ER-CALUX assays. Results: Accumulation and effects: Of the four organisms mentioned above, bioconcentration of 14C-EE2 was highest in the algae. Whereas the growth rate of D. subspicatus was significantly affected at high EE2 concentrations compared to unexposed algae, EE2 had no acute effects on D. magna and C. riparius. Daphnids showed a higher bioaccumulation potential after exposure via spiked algae. For chironomids, water exposure was the predominant uptake route. The presence of sediment lowered the bioavailability of 14C-EE2 to the larvae after both water and sediment spiking. Nevertheless, uptake was higher when the nutritional quality of the sediment was better. Etc.

Modellierung der oekologischen Qualitaet von Fluessen in Stadtgebieten: Oekotoxikologische Faktoren, die die Sanierung von Fischbestaenden behindern

Das Projekt "Modellierung der oekologischen Qualitaet von Fluessen in Stadtgebieten: Oekotoxikologische Faktoren, die die Sanierung von Fischbestaenden behindern" wird vom Umweltbundesamt gefördert und von Technische Universität Berlin, Institut für Ökologie, Fachgebiet Landschaftsökologie , Ökotoxikologie durchgeführt. Objective: Problems to be solved: The objectives of the project are to determine the ecotoxicological factors limiting restoration of sustainable fish populations in polluted urban rivers. These factors will be described and modelled for urban river systems in four European countries, Italy, Germany The Netherlands and the UK. By monitoring the conditions in each river and the natural fish population, then using caged fish to sample the environmental and biological factors that limit sustainable fish populations, the project will address the problems relating to the establishment of a standardised and validated array of bio-indicator measurements, for use in water quality surveillance and monitoring schemes, in support of environmental policies for integrated water management. A parallel sociological study of risk perception in stakeholders will provide information on peoples' perceptions and expectations with regard to water. The CEC Council have as their aim the remediation of European surface and ground waters in order that they achieve 'good' ecological status by the year 2010. This project will contribute to the objectives of Key Action 1, Sustainable management and quality of water and in particular, key action 1.2, Ecological quality of freshwater ecosystems and wetlands, and specifically key action 1.2.2, Ecological quality targets. Scientific objectives and approach: At each site, the ecological quality of the study river will be described on a seasonal basis in terms of biotic indices and chemical water quality, and related to the population biology of a resident species of coarse (tolerant) fish. Sub-lethal indicators of pollution will then be measured on fish exposed to the prevailing seasonal water conditions at each site, in floating cages. A range of biochemical indicators (biomarkers) will be used to reveal specific exposure to particular contaminants or classes of contaminants. These will include: - induction of cytochrome P450 and metallothioneins; DNA damage, in terms of strand breaks; estrogenic activity (measured as vitellogenin induction); brain cholinesterase activity. Measurement of swimming performance will be used as an indicator of physiological status, revealing seasonal differences and the response to exposure to the complex changes in water chemistry, following flood spates. These measurements will be related to migration of fish within the river system, using radio-tracking or tag and recapture. The immunological status of fish (e.g. macrophage activity) will be assessed, as urban waters can be subject to elevated contents of pathogenic bacteria from human waste and, furthermore, fish in poor condition as a result of pollution and other physico-chemical stresses may have compromised immune competence. Prime Contrator: University of Birmingham, School of Biological Sciences; Birmingham.

BENEFIT - Maintenance mechanisms of zooplankton and ichthyoplankton populations in frontal systems

Das Projekt "BENEFIT - Maintenance mechanisms of zooplankton and ichthyoplankton populations in frontal systems" wird vom Umweltbundesamt gefördert und von Zentrum für Marine Tropenökologie an der Universität Bremen durchgeführt. Das Benguela-Strom- und Auftriebsgebiet vor Südwestafrika ist eines der vier großen ostozeanischen Auftriebsgebiete in den Weltmeeren. Diese großräumigen hydrographischen Systeme sind durch den Transport von nährstoffreichem Tiefenwasser an die Oberfläche entlang ausgedehnter Küstenabschnitte vor Nord- und Südwestafrika und Nord- und Südwestamerika gekennzeichnet. Die hohen Nährstoffmengen sind die Grundlage für eine enorme Produktion phytoplanktischer Biomasse und damit Nahrung für ausgedehnte Fischschwärme. Die ostozeanischen Auftriebsgebiete sind die produktivsten Fischgewässer der Welt. Das Benguelastromgebiet reicht von der südwestlichen Spitze Südafrikas entlang der namibischen Küste bis ins südliche Angola hinein, ungefähr von 37 bis 14 Grad S. Die nördliche Grenze dieses Gebietes wird von der Angola-Benguela-Front gebildet. Die beiden Ströme, Angola- und Benguelastrom, treffen hier aufeinander, biegen seewärts Richtung Westen ab und bilden eine dauerhafte Konvergenzzone, die bis weit in den Südatlantik hinausreicht. Die Lage dieses Frontsystems variiert mit der Jahreszeit. Für Planktonorganismen bilden solche Frontsysteme im Prinzip unüberwindliche Hindernisse. Da sie per definitionem nicht in der Lage sind, aktiv gegen Strömungen anzuschwimmen, müssten sie theoretisch von den seewärts gehenden Strömungen mitgerissen und auf den offenen Ozean verdriftet werden. Außerdem sollten sie Frontsysteme nicht durchqueren können. In der Realität lässt sich aber aus Verbreitungsmustern vieler Organismen ablesen, dass sie durchaus in der Lage sind, durch Vertikalwanderung und Ausnutzung von Gegenströmen in von ihnen bevorzugten Gebieten zu bleiben und auch hydrographische Fronten zu durchqueren. Das Projekt zielt darauf ab, die Mechanismen zu untersuchen, die planktische Krebse und Fischlarven entwickelt haben, um ihnen den Verbleib in von ihnen bevorzugten Gebieten/Lebensbedingungen zu gewährleisten. Außerdem sollen Nahrungsanalysen und physiologische Untersuchungen Aufschluss über Austauschprozesse zwischen den trophischen Ebenen geben und erklären, wie die Verteilungsmuster der für die Fischerei wichtigen Arten zustande kommen.

Validierung und Einsatz biologischer, chemischer und mathematischer Tests zur Bewertung der Belastung kleiner Fliessgewaesser: Molekulare, biochemische und In-vitro-Biomarker

Das Projekt "Validierung und Einsatz biologischer, chemischer und mathematischer Tests zur Bewertung der Belastung kleiner Fliessgewaesser: Molekulare, biochemische und In-vitro-Biomarker" wird vom Umweltbundesamt gefördert und von Universität Heidelberg, Zoologisches Institut I durchgeführt. Within the scope of a joint project sponsored by the Federal Minister for Education and Science on the use and evaluation of biological, chemical and mathematical tests for the ecotoxicological evaluation of small rivers, biochemical and ultrastructural changes in the livers and gills and brains of Salmo trutta f. fario and Barbatula barbatula in consequence of exposure to the water of small contaminated rivers in Southern Germany are recorded. In addition, permanent and primary cultures of fish cells are exposed to eluates and extracts of water and sediment samples collected from the rivers. In both intact fish and fish cell cultures, the induction of heat shock proteins (hsp 70) is measured as a biomarker of exposure to anthropogenic contaminants. The purpose of the study is (1) to determine contaminant-induced changes at different lower levels within the hierarchy of biological organization, (2) to create a data basis for their interpretation of biological effects at higher levels of organization, and (3) to elucidate the significance of molecular and cellular biomarkers at higher niveaus of biological integration.

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