Analysis of Endocrine Disrupting Steroids: Investigation of Their Release into the Environment and Their Behavior During Bank Filtration

A reliable and sensitive analytical method for the determination of estrone (E1), 17β-estradiol (E2), and the synthetic hormone 17α-ethinylestradiol (EE2) has been established. Samples are concentrated using automated solid-phase extraction and analysis is performed by liquid chromatography with detection by tandem mass spectrometry. Recoveries of all analytes were between 93% and 107%, and limits of quantification (LOQs) between 0.1 and 0.4 ng/L for purified sewage, and surface, ground, and drinking water, and between 1 and 2 ng/L in case of raw sewage. For the investigation of estrogen release into the environment and its behavior during sewage and surface water treatment, and during ground water recharge, samples from municipal waste water treatment plants (WWTPs), a surface water treatment plant, a bank filtration site, and a ground water enrichment (GWE) pond were analyzed. El was found in the raw waste water with an average concentration of 157 ng/L, whereas E2 and EE2 were found with mean concentrations of only 18 and 9 ng/L, respectively. Sewage treatment by municipal WWTPs affected a removal of EE2 (76%), El (92%), and E2 (94%). In the investigated surface water of Berlin, only E1 could be detected at concentrations around or below 1 ng/L. E2 and EE2 were not present in the Berlin surface water above the LOQ of 0.2 ng/L, respectively. Surface water treatment also leads to a significant removal of E1 (> 80%). In the ground water samples from the GWE site near Lake Tegel, only a few samples contained detectable concentrations of E1. These samples were collected from a shallow monitoring well located very close to the bank of the pond. Even a short distance between the bank and observation wells led to concentrations of El below the LOQ showing the potential of ground water recharge systems for the retention of estrogenic steroids depending on the environmental setting.     

Endoparasites in common eiders Somateria mollissima from birds killed by an oil spill in the northern Wadden Sea

Mass mortalities of common eiders Somateria mollissima have been ascribed to high parasite loads. However, the actual role of parasites in mortalities is disputed as in the case of a mass mortality of eiders in the Wadden Sea in the winter of 1999/2000. A critical evaluation of the role of parasites in eider mass mortalities is hampered by (1) a lack of data on actual parasite loads of the birds involved, (2) missing regional data for comparison, and (3) a lack of unbiased samples: investigations are often based on dead beached individuals, which are presumably the more heavily infected birds of a population and thus more likely to die and be washed ashore. Although published data on parasite loads in birds of the winter 1999/2000 mortality are available, no data on background parasitism in eiders from the Wadden Sea exist, making an evaluation of the potential role of parasites in this mortality event difficult. By investigating endoparasites of 102 eiders affected by an oil spill in the northern Wadden Sea in winter 1998/1999, we provide a data set of background parasitism in wintering eiders from the Wadden Sea. We found 13 different parasite taxa with high prevalence values (% infected birds) in the acanthocephalan Profilicollis botulus, the nematode Amidostomum acutum, cestodes and trematodes. In some taxa we observed pronounced differences in prevalence values between juvenile eiders and adults, as well as between adult sexes. The parasite composition shows that bivalves, crabs (Carcinus maenas) and other crustaceans are important sources of infections by being intermediate hosts. This is partly mirrored in the food content of eider stomachs where bivalves and crabs were predominantly found. Intensities of the acanthocephalan P. botulus, suspected of causing eider mortalities, were especially high in juveniles (1112 ± 416 ind per infected host), but lower in adult males (40 ± 7) and adult females (81 ± 18). However, no extraordinary mortality event was observed in the winter of 1998/1999, indicating no or a very weak effect of the parasites on host condition. A comparison with the parasite loads of eiders from the mass mortality in the winter of 1999/2000 shows that parasite numbers were by no means exceptional for birds from the area. Hence, parasites alone are unlikely to have caused this mortality. Regional background parasite loads are important to differentiate between primary and secondary roles of parasites in anomalous mortality events.     

Numerical studies of dispersion due to tidal flow through Moskstraumen, northern Norway

The effect of horizontal grid resolution on the horizontal relative dispersion of particle pairs has been investigated on a short time scale, i.e. one tidal M ₂ cycle. Of particular interest is the tidal effect on dispersion and transports in coastal waters where small-scale flow features are important. A three-dimensional ocean model has been applied to simulate the tidal flow through the Moskstraumen Maelstrom outside Lofoten in northern Norway, well known for its strong current and whirlpools (Gjevik et al., Nature 388(6645):837–838, 1997; Moe et al., Cont Shelf Res 22(3):485–504, 2002). Simulations with spatial resolution down to 50 m have been carried out. Lagrangian tracers were passively advected with the flow, and Lyapunov exponents and power law exponents have been calculated to analyse the separation statistics. It is found that the relative dispersion of particles on a short time scale (12–24 h) is very sensitive to the grid size and that the spatial variability is also very large, ranging from 0 to 100 km² over a distance of 100 m. This means that models for prediction of transport and dispersion of oil spills, fish eggs, sea lice etc. using a single diffusion coefficient will be of limited value, unless the models actually resolves the small-scale eddies of the tidal current.     

Transformation of Aerosol Chemical Properties due to Transport Over a City

The change of the chemical composition of the near-ground level atmospheric aerosol was studied during two summer episodes by a Lagrangian type of experimental approach. Bulk and single-particle chemical analyses of ions and elements in the particulate phase were deployed. N(-III) and N(V) components were also measured in the gas-phase. The measurements were completed by particle size distributions.Secondary inorganic aerosols (SIA) and fine particles of ≈0.2–0.4 μm size were still elevated 50 km downwind of the city. The direct comparison of transport over the city in contrast to transport over the surrounding areas showed that SIA was formed from emission from the city within less than 3 h. Relative increases, i.e., enrichment during transport were observed for primary and secondary aerosol components. The degree of mixing on the individual particle level increased significantly during transport in the area. In particular, newly emitted carbonaceous particles became internally mixed within hours with pre-existing sulphate particles. Mostly due to secondary aerosol formation the average particle size (mass median diameter) of major constituents of the aerosol was significantly decreased while being transported over 13 h. Given recent insights which link fine particles number and mass concentrations with health risks, the results suggest that rural populations in areas which frequently are located within an urban plume might run an elevated health risk relative to populations in areas not affected by urban plumes.     

Fluid and gas migration in the North German Basin: fluid inclusion and stable isotope constraints

Fluid inclusions have been studied in minerals infilling fissures (quartz, calcite, fluorite, anhydrite) hosted by Carboniferous and Permian strata from wells in the central and eastern part of the North German Basin in order to decipher the fluid and gas migration related to basin tectonics. The microthermometric data and the results of laser Raman spectroscopy reveal compelling evidence for multiple events of fluid migration. The fluid systems evolved from a H₂O–NaCl±KCl type during early stage of basin subsidence to a H₂O–NaCl–CaCl₂ type during further burial. Locally, fluid inclusions are enriched in K, Cs, Li, B, Rb and other cations indicating intensive fluid–rock interaction of the saline brines with Lower Permian volcanic rocks or sediments. Fluid migration through Carboniferous sediments was often accompanied by the migration of gases. Aqueous fluid inclusions in quartz from fissures in Carboniferous sedimentary rocks are commonly associated with co-genetically trapped CH₄–CO₂ inclusions. P–T conditions estimated, via isochore construction, yield pressure conditions between 620 and 1,650 bar and temperatures between 170 and 300°C during fluid entrapment. The migration of CH₄-rich gases within the Carboniferous rocks can be related to the main stage of basin subsidence and stages of basin uplift. A different situation is recorded in fluid inclusions in fissure minerals hosted by Permian sandstones and carbonates: aqueous fluid inclusions in calcite, quartz, fluorite and anhydrite are always H₂O–NaCl–CaCl₂-rich and show homogenization temperatures between 120 and 180°C. Co-genetically trapped gas inclusions are generally less frequent. When present, they show variable N₂–CH₄ compositions but contain no CO₂. P–T reconstructions indicate low-pressure conditions during fluid entrapment, always below 500 bar. The entrapment of N₂–CH₄ inclusions seems to be related to phases of tectonic uplift during the Upper Cretaceous. A potential source for nitrogen in the inclusions and reservoirs is C_org-rich Carboniferous shales with high nitrogen content. Intensive interaction of brines with Carboniferous or even older shales is proposed from fluid inclusion data (enrichment in Li, Ba, Pb, Zn, Mg) and sulfur isotopic compositions of abundant anhydrite from fissures. The mainly light δ³⁴S values of the fissure anhydrites suggest that sulfate is either derived through oxidation and re-deposition of biogenic sulfur or through mixing of SO₄²⁻-rich formation waters with variable amounts of dissolved biogenic sulfide. An igneous source for nitrogen seems to be unlikely since these rocks have low total nitrogen content and, furthermore, even extremely altered volcanic rocks from the study area do not show a decrease in total nitrogen content.     

Investigation of the fate of nitrogen in Palaeozoic shales of the Central European Basin

Nitrogen geochemistry of Upper Carboniferous shales from the Central European Basin (CEB) was investigated by elemental analysis, stable isotope mass spectrometry and non-isothermal pyrolysis. Total N-contents of Namurian shales from four deep wells (4400–7000 m) in NE Germany ranged between 520 and 2680 ppm. Up to 90% of this nitrogen occurs as ammonium in minerals with δ¹⁵N values between + 1‰ and + 3.5‰. Low nitrogen contents (down to 460 ppm) and high δ¹⁵N values (up to + 5.6‰) in one well in the basin centre suggest a large-scale release of nitrogen associated with isotopic fractionation. Pyrolytic liberation of N₂ from pelagic Namurian A shales of NW and NE Germany occurred at significantly lower temperatures than from paralic Namurian B shales and terrestrial Westphalian samples. On-line isotope analysis of N₂ liberated between 400 and 1200 °C indicates the presence of precursor pools with different thermal stability and nitrogen isotopic composition.