Determination of selected pharmaceuticals and caffeine in sewage and seawater from Tromsø/Norway with emphasis on ibuprofen and its metabolites

Selected pharmaceuticals, among them analgesics, ss-blockers and anti-depressants as well as caffeine, the anti-bacterial triclosan and the insect repellent N,N-diethyl-3-toluamide (DEET) were determined in different sewage samples (sewage treatment plants, hospital effluents) from Troms?/Norway and in seawater from Troms?-Sound, into which the sewage is discharged. While caffeine, triclosan, ibuprofen and its major metabolites hydroxy- and carboxy-ibuprofen were present in all sewage samples, additional pharmaceuticals were observed in sewage containing hospital effluents. Concentrations were in the range of 20-293 microg/l (caffeine), 0.2-2.4 microg/l (triclosan) and 0.1-20 microg/l (sum ibuprofen + metabolites). In seawater, only caffeine (7-87 ng/l), DEET (0.4-13 ng/l) and ibuprofen + metabolites (sum concentration < LOQ-7.7 ng/l) were detected. Ibuprofen and its metabolites hydroxy- and carboxy-ibuprofen were quantified individually by use of the respective reference compounds. Relative amounts of the three compounds were determined in different types of water showing characteristic patterns, with hydroxy-ibuprofen being the major component in sewage whereas carboxy-ibuprofen was dominant in seawater samples. The patterns which were compared to those observed in similar samples from Germany indicated different transformation behaviour under limnic and marine conditions.     

Development of an immuno-immobilized androgen receptor assay (IRA) and its application for the characterization of the receptor binding affinity of different pesticides

Pesticides are synthetic chemicals used not only for improving food and feed production but also for the protection of materials and of human health and well-being. Some of these substances are suspected for adverse effects attributable to an interaction with the endocrine system of vertebrates by mimicking or inhibiting endogenous hormones. One of the biological targets important in this relation is the androgen receptor (AR). To be able to screen environmental samples for the presence of compounds which might interfere with androgen action, we aimed to develop a receptor assay based on recombinant human AR (rhAR). We herein describe an rhAR assay in which the receptor is immobilized in microtiter plates via a specific antibody. The assay can be used for high throughput screening of chemicals spread into the environment. 29 of the most recommended pesticides of the Federal Country Hessen, Germany, were tested for their ability to displace [3H]-DHT bound to the rhAR. This evaluation included the major part of the most common herbicides, insecticides and fungicides and covered three potential groups of endocrine disrupting chemicals. For 28 of the substances evaluated, the relative binding affinity to the rhAR was below 0.1% when compared to dihydrotestosterone (DHT) (100%), only fentinacetate exhibited an affinity of 1.42%. An exchange assay indicated that the binding inhibition was reversible. In consequence, fentinacetate seems to be a hormonally active substance which may be present in vegetables or fish, but also on clothing. We conclude that further investigations on this compound and its metabolites are necessary.     

Carbon and hydrogen isotope effects during sorption of organic contaminants on carbonaceous materials

Stable carbon and hydrogen isotopes can be an efficient means to validate biodegradation of organic contaminants in groundwater since it results in an isotopic fractionation. A prerequisite in applying this method in the field is the proof that other processes decreasing the contaminant concentration are conservative with respect to isotope effects. In this paper we show for carbon isotopes of halogenated hydrocarbon compounds [trichloroethene (TCE), cis-dichloroethene (c-DCE), vinylchloride (VC)] and carbon and hydrogen isotopes of BTEX compounds (benzene, toluene, p-xylene) that no significant fractionation occurs during equilibrium sorption onto activated carbon, lignite coke and lignite. In general, effects were in the range of the reproducibility limit of the analytical instrument (0.5 per thousand for delta13C, and 8 per thousand for delta2H). This observation was made for fractions sorbed of less than 5% to more than 95%. Also for rate-limited sorption of TCE onto activated carbon, no significant fractionation in carbon isotopes could be observed. These findings support the assumption that for these classes of compounds, sorption processes in aquifer systems are conservative with respect to isotope effects.     

Genotoxic and teratogenic potential of marine sediment extracts investigated with comet assay and zebrafish test

Organic extracts of marine sediments from the North Sea and the Baltic Sea were investigated with two toxicity assays. The comet assay based on the fish cell line Epithelioma papulosum cyprini (EPC) was applied to determine the genotoxic potential; zebrafish embryos (Danio rerio) were used to quantify the teratogenic potential of the samples. EC(50) values were calculated from dose-response curves for both test systems. Highest teratogenic and genotoxic effects normalised to total organic carbon (TOC) content were detected in sediment samples of different origins. Polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) are not likely to be the causes of the observed effects, as demonstrated by a two-step fractionation procedure of selected extracts. The toxic potential was more pronounced in fractions having polarity higher than those possessed by PAHs and PCBs. The suitability of the two in vitro test systems for assessing genotoxic and teratogenic effects of marine sediment extracts could be demonstrated.     

Winter foraging at carcasses by three sympatric corvids,with emphasis on recruitment by the raven,Corvus corax

Summary Large animal carcasses provide a highly clumped rich source of food for ravens that should be worth defending, yet in the forests of Maine and Vermont ravens commonly feed in groups. Ravens discover baits flying singly or in pairs, but after a bait is discovered they usually arrive in groups. In contrast, the maximum number of blue jays and crows eventually attending a bait is close to those discovering it. Unlike in crows and jays, two patterns of bait use are seen in ravens: baits are used by mated resident pairs or by large crowds (sometimes exceeding 40 individuals). This pattern is unrelated to bait size from at least 9 kg to 400 kg. Eightytwo of 91 individually marked ravens from 4 feeding crowds were juveniles and/or non-breeders. Observations of the marked ravens for parts of two winters indicate that the non-breeders are vagrant and/or they range over at least 1800 km² in their foraging. Most of the over 135 baits (totalling nearly 8 t of meat) distributed over 50 km were discovered by ravens within a week, and most were consumed by crowds of ravens. The vagrants coming in crowds have (unlike the territorial adults) specific vocalizations in the bait vicinity that are a powerful recruitment stimulus in playback experiments. Vagrants sometimes feed alone, but in the presence of territorial adults they feed only in groups. Resident adults chase or attack vagrants, but mildly tolerate them (and even join them) when they come in large groups. I conclude from my observations that the feeding crowds of ravens consist primarily of juvenile non-breeding vagrants who (unlike some resident adults) roost communally and who vigorously recruit each other in part to neutralize the aggressiveness of resident adults defending prized food bonanzas. The ravens' recruitment results in a sharing that reduces the temporal patchiness of extremely rare food bonanzas, and it permits the non-territorial vagrants to specialize on carcasses in the winter.