Armin Zenker

Widespread occurrence of estrogenic UV-filters in aquatic ecosystems in Switzerland

We performed a trace analytical study covering nine hormonally active UV-filters by LC-MS/MS and GC-MS in river water and biota. Water was analysed at 10 sites above and below wastewater treatment plants in the river Glatt using polar organic chemical integrative samplers (POCIS). Four UV-filters occurred in the following order of decreasing concentrations; benzophenone-4 (BP-4) > benzophenone-3 (BP-3) > 3-(4-methyl)benzylidene-camphor (4-MBC) > 2-ethyl-hexyl-4-trimethoxycinnamate (EHMC). BP-4 ranged from 0.27 to 24.0 microg/POCIS, BP-3, 4-MBC and EHMC up to 0.1 microg/POCIS. Wastewater was the most important source. Levels decreased with higher river water flow. No significant in-stream removal occurred. BP-3, 4-MBC and EHMC were between 6 and 68 ng/L in river water. EHMC was accumulated in biota. In all 48 macroinvertebrate and fish samples from six rivers lipid-weighted EHMC occurred up to 337 ng/g, and up to 701 ng/g in 5 cormorants, suggesting food-chain accumulation. UV-filters are found to be ubiquitous in aquatic systems.

Simultaneous trace determination of nine organic UV-absorbing compounds (UV filters) in environmental samples.

A new sensitive method has been successfully developed and validated for the simultaneous determination and quantification of nine estrogenic UV filters (benzophenone-1, benzophenone-2, benzophenone-3, benzophenone-4, 4,4-dihydroxybenzophenone, ethyl-4-aminobenzoate, 2-ethyl-hexyl-4-trimethoxycinnamate, 3-(4-methylbenzylidene)-camphor, 3-benzylidene-camphor) in different environmental matrices. After optimisation of extraction conditions for the best recovery of polar to lipophilic compounds from fish tissue and a subsequent lipid clean-up in HPLC, fish extraction recoveries exceeded 72% for all nine UV filters. Identification and quantification of compounds was performed for lipophilic UV filters with gas chromatography-electroionisation-mass spectrometry and for polar and mid-polar compounds with liquid chromatography coupled to electrospray ionisation mass spectrometry. Instrumental detection limits (IDL) varied between 5 and 260 pg injected and method detection limits (MDL) were in the low ng/g lipids range for all test compounds. The described analytical methods are shown to be useful to screen for estrogenic UV filters in environmental samples such as fish and polar organic chemical integrative samplers.

Bioaccumulation and biomagnification potential of pharmaceuticals with a focus to the aquatic environment

Pharmaceuticals, among the emerging contaminants, are one of the most relevant groups of substances in aquatic ecosystems due to universal use, their chemico-physical properties and known mode of action in aquatic organisms at low concentrations. After administration many drugs and their transformation products are only retained to some extent in wastewater treatment plants therefore entering the aquatic environment in considerable high amounts. The yearly consumption to treat human and animal diseases, also in livestock and aquaculture was estimated to be hundred thousands tons per year leading to high concentrations in surface water of developed countries. Mostly, pharmaceutical residues in effluents of wastewater treatment plants or in the water column of surface waters have been reported, but data about concentrations in the aquatic biota, partitioning of pharmaceuticals to biosolids, soils, and sediments and the bioaccumulation properties are often lacking. Chronic and subtle effects can be expected when aquatic organisms are long term exposed by pseudo-persistent, persistent and accumulative compounds. This review aims to summarize the current state of research about the fate of pharmaceuticals regarding bioconcentration, bioaccumulation and potential biomagnification in aquatic ecosystems. More comprehensive approaches for the evaluation of environmental (ERA) and human health risk assessment (HRA) are included and analytical methods required to detect bioaccumulation of pharmaceuticals are discussed.

A tentative environmental risk assessment of the UV-filters 3-(4-methylbenzylidene-camphor), 2-ethyl-hexyl-4-trimethoxycinnamate, benzophenone-3, benzophenone-4 and 3-benzylidene camphor

UV-filters are increasingly used in cosmetics and in the protection of materials against UV-irradiation. The widespread occurrence of UV-filter residues in aquatic systems has been reported, but still little is known about their environmental effects. Some of these compounds negatively interact with the hormone system of fish, resulting in decreased fecundity and reproduction. Here we report on acute and chronic effects of UV-filters 3-(4-methylbenzylidene-camphor) (4MBC), 2-ethyl-hexyl-4-trimethoxycinnamate (EHMC), benzophenone-3 (BP3) and benzophenone-4 (BP4) on Daphnia magna. The acute toxicity increased with log Pow of the compound. The LC50 values (48h) of 4MBC, EHMC, BP3 and BP4 were 0.56, 0.29, 1.9 and 50mg/L, respectively. A tentative preliminary environmental risk assessment (ERA) based on a limited set of data indicates that individual UV-filters should undergo further ecotoxicological analysis, as an environmental risk cannot be ruled out. Consequently new data on the environmental occurrence and the effects of UV-filters are needed for a more accurate ERA. When regarded as a mixture occurring in surface waters they may pose a risk for sensitive aquatic organisms.

Effects of Diazepam on Gene Expression and Link to Physiological Effects in Different Life Stages in Zebrafish Danio rerio

We applied zebrafish whole genome microarrays to identify molecular effects of diazepam, a neuropharmaceutical encountered in wastewater-contaminated environments, and to elucidate its neurotoxic mode of action. Behavioral studies were performed to analyze for correlations between altered gene expression with effects on the organism level. Male zebrafish and zebrafish eleuthero-embryos were exposed for 14 d or up to 3 d after hatching, respectively, to nominal levels of 273 ng/L and 273 μg/L (determined water concentrations in the adult experiment 235 ng/L and 291 μg/L). Among the 51 and 103 altered transcripts at both concentrations, respectively, the expression of genes involved in the circadian rhythm in adult zebrafish and eleuthero-embryos were of particular significance, as revealed both by microarrays and quantitative PCR. The swimming behavior of eleuthero-embryos was significantly altered at 273 μg/L. The study leads to the conclusion that diazepam-induced alterations of genes involved in circadian rhythm are paralleled by effects in neurobehavior at high, but not at low diazepam concentrations that may occur in polluted environments.

Chemical and natural stressors combined: from cryptic effects to population extinction.

In addition to natural stressors, populations are increasingly exposed to chemical pollutants released into the environment. We experimentally demonstrate the loss of resilience for Daphnia magna populations that are exposed to a combination of natural and chemical stressors even though effects on population size of a single stressor were cryptic, i.e. hard to detect statistically. Data on Daphnia population demography and along with model-based exploration of our predator-prey system revealed that direct trophic interactions changed the population size-structure and thereby increased population vulnerability to the toxicant which acts in a size selective manner. Moreover, population vulnerability to the toxicant increases with predator size and predation intensity whereas indirect trait-mediated interactions via predator kairomones may buffer chemical effects to a certain extent. Our study demonstrates that population size can be a poor endpoint for risk assessments of chemicals and that ignoring disturbance interactions can lead to severe underestimation of extinction risk.

Fate and metabolism of tetrabromobisphenol A in soil slurries without and with the amendment with the alkylphenol degrading bacterium Sphingomonas sp. strain TTNP3.

Transformation of ring-(14)C-labelled tetrabromobisphenol-A (TBBPA) was studied in an oxic soil slurry with and without amendment with Sphingomonas sp. strain TTNP3, a bacterium degrading bisphenol-A. TBBPA degradation was accompanied by mineralization and formation of metabolites and bound-residues. The biotransformation was stimulated in the slurry bio-augmented with strain TTNP3, via a mechanism of metabolic compensation, although this strain did not grow on TBBPA. In the absence and presence of strain TTNP3, six and nine metabolites, respectively, were identified. The initial O-methylation metabolite (TBBPA-monomethyl ether) and hydroxytribromobisphenol-A were detected only when strain TTNP3 was present. Four primary metabolic pathways of TBBPA in the slurries are proposed: oxidative skeletal rearrangements, O-methylation, ipso-substitution, and reductive debromination. Our study provides for the first time the information about the complex metabolism of TBBPA in oxic soil and suggests that type II ipso-substitution could play a significant role in the fate of alkylphenol derivatives in the environment.

Relevance of abiotic criteria used in German lake typology for macroinvertebrate fauna

For lake characterisation, top-down typologies are mostly used throughout Europe, including type criteria such as climate, lake area, catchment geology and conductivity. In Germany, a lake typology was applied comprising ecoregion, calcium concentration, Schindler’s ratio, stratification type and residence time. However, the relevance of these criteria for the macroinvertebrate fauna has not been conclusively demonstrated till now. Benthic invertebrate community data and related environmental parameters of pristine or near-pristine lakes in Germany were analysed by multivariate analysis techniques to elucidate which environmental parameters are reflected by invertebrate composition. Moreover, benthic invertebrate data were transformed to metrics expressing ecological attributes and species richness (summarising functional composition, diversity and sensitivity measures). Multivariate statistics were used to test whether information relevant to ordination was lost and whether variation decreases using metrics which combine data with ecological attributes. Analysis of lake-type criteria revealed that ecoregions and prevailing substrates were characterized by different taxonomic compositions of macroinvertebrates. In addition, a relationship was found between community composition and lake size. Creating a novel bottom-up lake typology based on ecoregions, lake size and prevailing substrate gives better separation of distinct macroinvertebrate communities and a higher level of homogeneity within groups compared to top-down typology or single environmental parameters alone, both on species and metrics data. Despite some data variation due to methodological differences (e.g. different sampling and sorting techniques) and interannual and seasonal variation in the data set, NMDS ordination presented well-separated groups of bottom-up lake types. Lake types were more precisely separated by species data than by metric data in both top-down and bottom-up typology. However, as information loss from species lists to calculated metrics is marginal, type-specific benthic invertebrate assemblages are reflected both on the species level and on the metric level. Species and metric data are both suitable for data ordination, while single environmental parameters affecting macroinvertebrate composition can best be obtained using metrics.

Demographic Toxicokinetic–Toxicodynamic Modeling of Lethal Effects

The aquatic effect assessment of chemicals is largely based on standardized measures of toxicity determined in short-term laboratory tests which are designed to reduce variability. For this purpose, uniform individuals of a species are kept under environmental and chemical exposure conditions which are as constant as possible. In nature, exposure often appears to be pulsed, effects might last longer than a few days, sensitivity might vary among different sized organisms and populations are usually size or age structured and are subject to demographic processes. To overcome this discrepancy, we tested toxicokinetic-toxicodynamic models of different complexities, including body size scaling approaches, for their ability to represent lethal effects observed for Daphnia magna exposed to triphenyltin. The consequences of the different toxicokinetic and toxicodynamic assumptions for population level responses to pulsed exposure are tested by means of an individual based model and are evaluated by confronting model predictions with population data for various pulsed exposure scenarios. We provide an example where increased model complexity reduces the uncertainty in model outputs. Furthermore, our results emphasize the importance of considering population demography in toxicokinetics and toxicodynamics for understanding and predicting potential chemical impacts at higher levels of biological organization.