DDT und Metaboliten in Sedimenten Berliner Gewässer

Sediment samples from rivers and lakes of Berlin (Germany) were analysed for their contamination with organic compounds by means of qualitative and quantitative GC/MS analysis. The principal compounds detected were PAH, organotin derivates, several classes of chlorinated, brominated and mixed halogenated compounds and some of their related metabolites. The DDT metabolites DDD, DDE, DDCN, DDMU and DDMS were the most abundant compounds of halogenated pesticides in a wide range of samples. The main metabolite determined was p,p′-DDD, with concentrations up to 1230 μg/kg dw. The parent DDT compound was detected in only a few samples. The acute cytotoxicity of selected DDT-metabolites was determined with the permanent cell line RTG-2 from the gonads of the rainbow trout (Oncorhynchus mykiss). The results indicate a high cytotoxic potential of these metabolites. The oestrogenic potential was determined by the Dot-Blot/RNase-Protection-Assay an the order from o,p′-DDT>p,p′-DDMS>p,p′-DDMU≥p,p′-DDCN. Risk assessments based on chemical analysis of DDT, DDD and DDE alone is not able to estimate the real toxic potential of DDT and its metabolites. The development of a method for bioassay directed assessment seems to be an effective strategy to solve this problem. Especially scarce or not available data of combinatory effects, differences between different trophic levels and their availability to biota and low knowledge about the metabolism in situ as well as the enantioselective characteristics of most chiral DDT metabolites warrant future analyses.     

Simultaneous monitoring of profiles of polycyclic aromatic hydrocarbons in contaminated air with semipermeable membrane devices and spruce needles

Gaseous emissions of combusted electronic scrap, PVC, carpet and wood were monitored for polycyclic aromatic hydrocarbons (PAHs) by simultaneous use of semipermeable membrane devices (SPMDs) and shoots of spruce needles (Picea abies). It was found that phenanthrene, acenaphthylene and fluorene were the dominating PAHs in all samples. SPMDs and needles mainly sequestered PAH associated with the vapor phase. Particle-bound PAHs were only detected in small amounts, at which the needles tended to uptake more of these compounds in comparison to the SPMDs. Nevertheless, the logarithm of the concentrations of PAHs analyzed in both passive samplers after the same sampling period exhibited a significant linear correlation with correlation coefficients larger than 0.8073. SPMDs and spruce needles can complement each other in passive air sampling for compounds with a preference to the gas phase rather than aerosols.     

Atmospheric PCDD/F and PCB levels implicated by pine (Cedrus deodara) needles at Dalian, China

Dalian is a seaside city situated in the northeastern monsoon area of China. For the first time, levels of PCDD/F and PCB congeners in pine (Cedrus deodara) needles of Dalian urban areas were investigated. Two sampling campaigns with 17 sampling points were performed in 2002. The summation of tetra- to octachlorinated PCDD/Fs and summation of 209 PCB congeners in Dalian pine needles averaged 127+/-40 ng/kg (dry) and 4389+/-1575 ng/kg (dry), respectively. Average toxic equivalence (TEQ) for PCDD/Fs and PCBs are 2.1 and 0.4 ng/kg (dry), respectively. The pine needles can differentiate spatial variation of the pollutants. The PCDD/F and PCB levels in Dalian pine needles are low or comparable with other international regions that were not impacted by evident point sources. The data can serve as a base for long-term spatial and temporal studies of PCDD/Fs and PCBs in China.     

Endocrine disrupters in the aquatic environment

Possible mechanisms to explain endocrine effects on reproduction and sex differentiation are presented for selected pharmaceuticals, agrochemicals, industrial chemicals and plant sterols which are known to be present in the aquatic environment. Disruptions of the hormonal coordination can be induced by xenobiotics on various levels of the hierachically organised endocrine system of vertebrates. Phthalate plasticisers, for example, may disrupt the pituitary control of gonadal functions; prenatal/larval exposure to synthetic estrogen impairs sex differentiation and neuroendocrine sexual determination of the central nervous system; phenylurea herbicides block the androgen receptor; the biotransformation of weakly estrogenic plant sterol components of paper mill wastewater (e.g. βsitosterol) may lead to androgenic compounds. The effect of hypolipidemic drugs on lipid homeostasis (peroxysom proliferation) is transmitted via a receptor protein that seems to be closely related to the endocrine system both functionally as well as phylogenetically; possible interferences with the neuroendocrine control of sex differentiation are also discussed. In invertebrates, tributyltin is known to effect the biosynthesis of steroidal sexual hormones. PCBs are suspected to be competitive inhibitors of the steroid catabolism. In order to identify potential risks caused by chemicals to the reproductive capacities of aquatic animals and to the quality of drinking water, methods should be established to detect endocrine disrupters at the various levels of the endocrine system.     

Sorption behavior of U(VI) on phyllite: experiments and modeling

The sorption of U(VI) onto low-grade metamorphic rock phyllite was modeled with the diffuse double layer model (DDLM) using the primary mineralogical constituents of phyllite, i.e. quartz, chlorite, muscovite, and albite, as input components, and as additional component, the poorly ordered Fe oxide hydroxide mineral, ferrihydrite. Ferrihydrite forms during the batch sorption experiment as a weathering product of chlorite. In this process, Fe(II), leached from the chlorite, oxidizes to Fe(III), hydrolyses and precipitates as ferrihydrite. The formation of ferrihydrite during the batch sorption experiment was identified by M?ssbauer spectroscopy, showing a 2.8% increase of Fe(III) in the phyllite powder. The ferrihydrite was present as Fe nanoparticles or agglomerates with diameters ranging from 6 to 25 nm, with indications for even smaller particles. These Fe colloids were detected in centrifugation experiments of a ground phyllite suspension using various centrifugal forces. The basis for the successful interpretation of the experimental sorption data of uranyl(VI) on phyllite were: (1) the determination of surface complex formation constants of uranyl with quartz, chlorite, muscovite, albite, and ferrihydrite in individual batch sorption experiments, (2) the determination of surface acidity constants of quartz, chlorite, muscovite, and albite obtained from separate acid-base titration, (3) the determination of surface site densities of quartz, chlorite, muscovite, and albite evaluated independently of each other with adsorption isotherms, and (4) the quantification of the secondary phase ferrihydrite, which formed during the batch sorption experiments with phyllite. The surface complex formation constants and the protolysis constants were optimized by using the experimentally obtained data sets and the computer code FITEQL. Surface site densities were evaluated from adsorption isotherms at pH 6.5. The uranyl(VI) sorption onto phyllite was accurately modeled with these newly determined constants and parameters of the main mineralogical constituents of phyllite and the secondary mineralization phase ferrihydrite. The modeling indicated that uranyl sorption to ferrihydrite clearly dominates uranyl sorption, showing the great importance of secondary iron phases for sorption studies.     

Genetic homogeneity and circum-Antarctic distribution of two benthic shrimp species of the Southern Ocean, Chorismus antarcticus and Nematocarcinus lanceopes

During the last years, molecular studies revealed significant population differentiation and cryptic species within various benthic and pelagic marine Antarctic taxa. This is unexpected due to the lack of obvious barriers to gene flow and strong current systems. Using mitochondrial (COI, 16S rDNA) and nuclear (28S rDNA: D2) gene fragments, we tested whether two circum-Antarctic benthic shrimps with planktotrophic larvae, Chorismus antarcticus and Nematocarcinus lanceopes, show patterns of regional differentiation. For both species, the 16S and the 28S fragment were invariant. However, for COI we found 24 different haplotypes for Chorismus antarcticus and 54 for Nematocarcinus lanceopes. No significant differentiation was observed among populations or regions. Furthermore, we found signatures of a population expansion in the late Pleistocene hinting at an impact of large-scale glaciations in particular on the shallow-water shrimp Chorismus antarcticus, supporting a (re)colonization and demographic expansion of this shrimp species in response to climate oscillation.     

Pesticide residues in products of plant origin in the European Union

The results of a co-ordinated monitoring programme for pesticide residues in the European Union and Norway carried out in 1996 and 1997 are presented. The aim of this programme is to work towards a system, which makes it possible to estimate actual dietary pesticide intake for the population of the European Union. Based on a statistically dérived sampling plan and within the limited number of pesticides/commodities analysed, the most critical pesticides (benomyl group and dithiocarbamates) and commodities (mandarine and lettuce) were identified. In case of detected non-compliances, repeated sampling and, if necessary, enforcement actions are to be taken by national authorities. The programme will be continued in the next years.