Dioxins and dioxin-like PCBs in different fish from the river Elbe and its tributaries, Germany.

In a long-term program polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) as well as dioxin-like polychlorinated biphenyls (DL-PCBs) were analyzed in the muscle tissue of eels (Anguilla anguilla), bream (Abramis brama), European chub (Leuciscus cephalus) and ide (Leuciscus idus) from the river Elbe and its tributaries Mulde and Saale. The variation of the PCDD/F and DL-PCB concentrations in all fish samples is very large, whereby the DL-PCBs predominate in comparison to the PCDD/Fs. In the eels, the concentrations (pg WHO-TEQ/g ww) for the PCDD/Fs lie in the range of 0.48-22 and for the DL-PCBs between 8.5 and 59. In the whitefish, the concentration range is 0.48-12 for the PCDD/Fs and 1.2-14 for the DL-PCBs. Statistical analysis using relative congener patterns for PCDD/Fs allow spatial correlations to be examined for sub-populations of eels and whitefish. The results are compared to the maximum levels laid down in the European Commission Regulation (EC) No. 466/2001 and the action levels of the European Commission Recommendation 2006/88/EC. Eels caught directly after the major flood in August 2002 as well as eels near Hamburg (years 1996 and 1998) show high concentration peaks. Compared to the eels whitefish is less contaminated with PCDD/Fs and DL-PCBs.

Contamination of the alluvial plain, feeding-stuffs and foodstuffs with polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans (PCDD/Fs), dioxin-like polychlorinated biphenyls (DL-PCBs) and mercury from the River Elbe in the light of the flood event in August 2002.

Meadow soils, feeding-stuffs and foodstuffs from the alluvial plain of the river Elbe were analyzed in respect of PCDD/Fs, DL-PCBs and mercury with a view to assessing the consequences of the extreme flood of August 2002. The PCDD/F concentrations in the soils range from 3 to 2100 ng WHO-TEQ/kg dm, and for the DL-PCBs the range was 0.32 to 28 ng WHO-TEQ/kg dm. On the basis of established threshold values >40% of the areas are only fit for restricted usage. Mercury concentrations range from 0.11 to 17 mg/kg dm, whereby the action value of 2 mg/kg dm is exceeded in about 50% of the soil samples. A cumulative memory effect from past floods rather than a recent contamination from August 2002 is documented. Soils taken from behind broken dykes showed significantly lower concentrations. Grass, hay and grass silage originating from pasture land in Lower Saxony were taken before and immediately after the flooding. PCDD/Fs range from 0.29 to 16 ng WHO-TEQ/kg, the maximum permitted value of 0.75 ng WHO-TEQ/kg was exceeded in about 50% of the samples. Muscle-tissue from cattle, sheep, lamb and a roe deer as well as untreated milk from individual cows returned values ranging from 0.76 to 5.9 pg WHO-PCDD/F-TEQ/g fat, and 10% of the samples returned values higher than the permitted maximum of 3 pg WHO-PCDD/F-TEQ/g fat. The action value of 2 pg WHO-PCDD/F-TEQ/g fat was exceeded in 33% of the samples. No direct connection between these results and the effects of the flood could be established. A major input path for PCDD/Fs is the tributary Mulde, which discharges contaminated sediments from its catchment area into the Elbe.

The Elbe flood in August 2002--occurrence of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans (PCDD/F) and dioxin-like PCB in suspended particulate matter (SPM), sediment and fish.

As a result of extreme precipitation in August 2002 major flooding occurred in the catchment area of the rivers Elbe, Vltava (Moldau) and Mulde. Pollutants from industrial sites and from municipal sewage treatment works (STW) entered the Elbe and led to a serious pollution problem in the river. PCDD/F concentrations (in pg WHO-TEQ/g dw) in SPM ranged from 7-150, in sediments from 3-140; the "safe sediment value" of 20 was exceeded in 46% of the samples. 24 eels showed a wide concentration variation for these contaminants. The WHO-PCDD/F+PCB-TEQ values lay in the range from 11-56 pg/g ww, whereby the WHO-PCB-TEQ values were several times higher than the WHO-PCDD/F-TEQ values. The maximum permitted value of 4 pg WHO-PCDD/F/g ww (EU Directive No. 2375/2001) was reached or exceeded in 54% of the individuals. A statistical analysis using data from SPM and sediment samples showed that in the Czech river section the flooding activated a contamination source in the vicinity of the Spolana works. The influence of the tributary Mulde could be clearly demonstrated. Only a major clean-up of the contaminated sites in Bitterfeld can lead to a mid to long term improvement in respect of PCDD/F and dioxin-like PCB input into the Elbe.

Pharmaceuticals in the river Elbe and its tributaries.

Medicinal drugs were found to be ubiquitous in the river Elbe, its tributary the river Saale and in other tributaries at their points of entry into the Elbe. The distribution of concentration peaks along the investigated river stretches provides an indication that they are mainly due to the emission of treated waste water from municipal sewage treatment works. This leads to the conclusion that medicinal substances can be regarded as faecal indicators for water pollution caused by human activity. The main substances found in the Elbe in 1998 were diclofenac, ibuprofen and carbamazepine as well as various antibiotics and lipid regulators in the concentration range of <20-140 ng/l. The more thorough investigations carried out in 1999 and 2000 show that in addition to the drugs (phenazone, isopropyl-phenazone and paracetamol) metabolite concentrations contributed significantly to the total concentration of pharmaceuticals in the Elbe. The metamizole metabolites N-acetyl-4-aminoantipyrine (AAA) and N-formyl-4-aminoantipyrine (FAA) were found in concentrations from <20 to 939 ng/l. A multivariate statistical analysis revealed a high correlation in respect of the distribution of persistent substances. The metoprolol distribution throughout the Saale demonstrated that the tributaries cause either an increase (Weisse Elster, Unstrut, Ilm) or a reduction (Wipper, Bode) in the concentration, depending on the respective load of waste water. Wide scale sampling in Saxony during 2002 showed the ubiquitous occurrence of carbamazepine in surface waters. The ecotoxicological effects of this contamination cannot be assessed at present. This is due to the fact that no legal framework in respect of these medicinal drugs for human consumption has been established and therefore little research and no risk assessment has been carried out. Therefore it is urgently necessary to include at least the quantitatively most significant substances in the new assessment concept of the EC White Paper.

The occurrence of xenoestrogens in the Elbe river and the North Sea.

The xenoestrogens Bisphenol A (BPA), p-alkylphenols and p-alkylphenol ethoxylates were determined in water samples of the North Sea, the Elbe river, and its tributaries Schwarze Elster, Mulde, Saale and the Weisse Elster. The sampling sites of the Elbe river reached from Schmilka at the German-Czech border to Cuxhaven at the estuary. Samples of the North Sea were taken in the German Bight. Additionally, freshly deposed sediments of the River Elbe and its tributaries were analyzed. Partitioning coefficients of these compounds for the distribution between suspended particulate matter (SPM) and the aqueous phase were calculated for samples of the River Elbe at sampling site Geesthacht. The analytical procedure consisted of liquid-liquid extractions of the acidified water samples using dichloromethane. Sediments and SPM samples were extracted by Accelerated Solvent Extraction with n-hexane/acetone. Following a clean-up by HPLC, the analytes were derivatized with heptafluorobutyric acid anhydride and quantified using GC-MSD. The concentration ranges of the compounds analyzed in water samples of the Elbe river were as follows (in ng l(-1)): BPA 9-776, alkylphenols 10-221 and alkylphenol ethoxylates 18-302. In sediment samples the concentrations were (in microg kg(-1) dry mass): BPA 66-343, alkylphenols 17-1378 and alkylphenol ethoxylates 30-1797. In samples of the North Sea the concentrations were generally about 1 order of magnitude lower. As shown by the concentration profiles following the River Elbe into the North Sea, the Elbe river must be considered as a major pollution source for the North Sea concerning the compounds analyzed. The SPM/water-partitioning coefficients calculated (mean values) amounted to: BPA 4.50, alkylphenols 5.52-5.58 and alkylphenol ethoxylates 5.60-6.38. A comparison of the results with data from other surface waters showed that concentrations of these xenoestrogens in the River Elbe and its tributaries were relatively low. The evaluation of the data based on the lowest observable effect concentration (LOEC) for alkylphenols (endpoint: vitellogenin synthesis in male trout) indicated that the concentrations were well below the effectivity threshold.

On-line determination of mercury in river water at the German monitoring station Schnackenburg/Elbe.

A monitor is described which provides the on-line determination of mercury in river water at concentrations from 20 to 1000 ng/L. The measurement includes an on-line digestion with Br-/BrO3- and UV-radiation. Each determination is controlled by an on-line addition of 50 and 100 ng/L mercury carried out by pre-dilution of a 500 and 1000 ng/L stock solution using sequential injection analysis (SIA). One cycle of analysis takes 20 min and results in nine signals. A five days stand-alone operation has been performed successfully. Details are also published at web page: "http/www.rzbd.fh-hamburg.de/-prmercol".

Temporal variability of organic micropollutants in suspended particulate matter of the River Elbe at Hamburg and the River Mulde at Dessau, Germany.

The compound classes of n-alkanes, polycyclic aromatic hydrocarbons (PAHs), and a number of chlorinated hydrocarbons (CHs) in the River Elbe and its tributary Mulde were investigated on the basis of monthly mixed samples of suspended particulate matter (SPM). Covering the period from September 1994 to August 1995, samples from the River Elbe were taken at Hamburg, those from the River Mulde at Dessau. The samples were extracted by supercritical fluid extraction (SFE). Analysis of all substance groups were performed by highperformance liquid chromatography (HPLC), followed by gas chromatography with mass spectrometric detection (GC/MSD). As a statistical approach for the interpretation of data, hierarchical cluster analysis of the individual compound classes were performed to determine differences or similarities between the sampling sites Hamburg and Dessau to find spatial and seasonal concentration patterns. These analysis showed that, with a high significance, the concentration patterns of n-alkanes, PAHs, and CHs were sampling site-specific in both the Elbe and Mulde throughout the entire sampling period. In all cases, clustering of mostly consecutive months indicated continuous, slow changes of input, which moreover showed a constancy with respect to annual cycles. Correlation analysis of pollutant loads with different hydrographic parameters showed a number of linear dependencies of the contaminants with temperature, SPM content, and water discharge. Annual fluxes of particle-bound pollutants were calculated for each sampling site, taking into account the average monthly SPM levels and the water discharge. The particle-bound pollutant loads for the River Elbe at Hamburg were estimated to 13.4 t/a n-alkanes, 4.1 t/a PAHs, and 175. 8 kg/a CHs. The pollutant loads for the River Mulde at Dessau amounted 0.55 t/a n-alkanes, 0.14 t/a PAHs, and 15.5 kg/a CHs during the monitoring period. The input of n-alkanes originated from different sources. The n-alkane pattern of samples of the River Elbe showed a predominance of odd-numbered compounds in the range of C-20 and C-30 originating from terrestrial plants and, depending on the season, high concentrations of C-15 and C-17 due to aquatic organisms. Only a small proportion of n-alkane input originated from petroleum sources. Samples from the River Mulde showed high amounts of the n-alkanes C-12 to C-15, indicating the input of light oil throughout the entire sampling period, constituting approximately 25% of the total n-alkane concentration. PAHs, which are considered combustion products, were widely distributed in all samples. Although the major inputs of PAHs were probably combustion sources and urban runoff, unusually high concentrations were found for some PAHs, which can be explained by point sources. A comparison of the standardized PAH patterns in samples from both stations clearly showed that higher fused ring systems, which mainly originate from combustion processes (four- to six-ring systems), had considerably higher relative concentrations in SPM from the Elbe than from the Mulde, where higher relative concentrations of the two- and three-ring systems were measured. This confirms findings that petroleum input was higher in the Mulde than in the Elbe. Concentrations of chlorinated hydrocarbons in SPM samples from the river Mulde had comparatively high levels. The largest differences were found for p,p'-DDT and its metabolites p,p'-DDD and p,p'-DDE. On average, concentrations of p,p'-DDT, p,p'-DDD, and p,p'-DDE in the Mulde were about 10, 15, and 25 times higher, respectively, than in the Elbe. Concentrations of HCB, which in the samples from Hamburg had the highest concentrations of all CHs, were found to be higher by about a factor of 3 in the Mulde River. The PCB levels in samples from the Mulde and Elbe were about equal, although there were differences in the pattern of PCB congeners.

Dioxin (PCDD/F) in the river Elbe--investigations of their origin by multivariate statistical methods.

With several multivariate statistical methods a classification of dioxin data has been tried. As a main result one significant source of dioxin in the river Elbe, in the harbour of Hamburg as well as in soils of the flooding areas of the river Elbe could be identified: the dioxin contaminated region Bitterfeld. Our statistical results indicate that the dioxin contamination in the Bitterfeld region was caused partly by metallurgy processes and not only by chemical production.

Toxic environmental chemicals in human semen: analytical method and case studies.

In 1982, 89 men from all over the FRG participated in an investigation of sperm density and the presence of selected persistent environmental chemicals in their semen. Semen concentrations for the following chemicals were measured: lead, cadmium, hexachlorobenzene (HCBC), a-hexachlorocyclohexane (a-BHC), DDT and metabolites, dieldrin and polychlorobiphenyls (PBC). Heavy metal analyses were performed by Zeeman-AAS with direct sample measurement. A method for the quantitative determination of chlorinated hydrocarbons in semen by liquid-liquid extraction, clean-up and quantitation by gas chromatography with an electron capture detector. Recovery rates ranged from 72 to 120%. Compound identification in samples was confirmed by negative chemical ionization mass spectrometry. Heavy metals and organochlorine compounds in semen were present in the same concentration range as in blood or other biofluids. Occupational exposure as well as extraordinary environmental exposure appeared to influence semen concentrations. Students in chemistry showed elevated levels of organochlorine compounds. Men who lived in the vicinity of an atmospheric source of heavy metals showed strikingly the vicinity of an atmospheric source of heavy metals showed strikingly elevated levels of semen lead and cadmium. We were unable to find a statistically significant correlation between sperm density and any of the variables examined in this study including: orgonochlorine compounds summed or individually; lead and/or cadmium; and tobacco consumption. Significant correlations were found between the simultaneous occurrence of lead and cadmium and between the simultaneous occurrence of HCB, DDT and DDE.