Xenoestrogens in the River Elbe and its tributaries

4-Alkylphenols, 4-alkylphenol ethoxylates, 4-alkylphenoxy carboxylates, bisphenol A, bisphenol F, 4-hydroxyacetophenon, 4-hydroxybenzoic acid and steroid hormones were analyzed in water samples of the River Elbe and its tributaries Schwarze Elster, Mulde, Saale, Havel and Schwinge. Additionally, freshly deposited sediments (FDS, composite samples) of the River Elbe and its tributaries were analyzed. The concentrations in water samples ranged from (in ng/l): bisphenol A 4 to 92, branched nonylphenol 13 to 87, branched nonylphenol ethoxylates <0.5 to 120, 4-tert. nonylphenoxy carboxylates <10 to 940 and 4-hydroxybenzoic acid 4 to 12. Steroid hormones were only detected in the Czech tributaries Jizera and Vltava in concentrations near the limit of quantification. In FDS samples the concentrations amounted to (in g/kg d.w.): bisphenol A 10-380, branched nonylphenol 27-430, branched nonylphenol ethoxylates 24-3700, nonylphenoxy carboxylates <50 and 4-hydroxybenzoic acid 23-4400. Increased bisphenol A concentrations were found in water and FDS samples taken from the Czech-German border at Schmilka and the mouth of the Schwinge (only water sample). According to studies conducted in the Elbe Estuary and the German Bight, the River Elbe must be considered as a major source of pollution for the North Sea in respect of the compounds analyzed. A comparison of bisphenol A concentrations, 4-alkylphenols and the corresponding ethoxylates analyzed in the River Elbe and its tributaries with those found in other German surface waters indicated a low level of contamination. The evaluation of the data based on LOEC-values indicated that the concentrations were well below the effectivity threshold for some 4-alkylphenols. According to recent ecotoxicological investigations, for example, with prosobranch snails, bisphenol A concentrations found in water samples of the River Elbe and its tributaries may well be detrimental to aquatic organisms. On the basis of the monitoring data and its implications for estrogenic potency the inclusion of bisphenol A in the list of priority substances (European Union Directive 2000/60/EC, Annex X) should be considered.     

Vertical profile of PCDD/Fs, dioxin-like PCBs, other PCBs, PAHs, chlorobenzenes, DDX, HCHs, organotin compounds and chlorinated ethers in dated sediment/soil cores from flood-plains of the river Elbe, Germany

Concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) and other organic micropollutants were determined in dated sediment/soil cores collected from the flood-plain of the river Elbe near Pevestorf (PT), approximately 125 km upstream of Hamburg, and Heuckenlock (HL) in southeast of Hamburg. Concentrations of PCDD/Fs peaked sharply at PT in the 1950s and at HL at the end of the 1940s. Cluster analyses provide evidence that the region of Bitterfeld-Wolfen (about 350-400 km upstream of Hamburg) could be the source of the PCDD/F contamination existing in the cores PT and HL since the 1940s. Obviously it is caused by sediments of the river Elbe of a similar composition. Whereas the PCDD/Fs, HCHs (hexacyclohexane isomers), DDX (DDT, DDD, DDE), and tetrachlorinated ethers in PT and HL presumably originated predominantly from the Bitterfeld-Wolfen region, organotin compounds in HL and dichlorinated haloethers in HL during the 1940s and 1950s can probably largely be attributed to emissions from the Hamburg region. Although they are separated by a large distance, in both sediment cores PT and HL concentrations and composition patterns of most organic micropollutants analyzed widely match. Inductively it can be concluded that similar contaminations will be found in many of the river bank soils between the Bitterfeld-Wolfen region and Hamburg. Excavation of top soils may uncover highly contaminated materials. Since the dated sediment cores show the variation in contaminants in the Elbe sediments over a defined time period, it is possible to make an approximate assessment of the actual degree of contamination to be expected in areas where in previous decades contaminated dredged sediments from the Elbe and from the Port of Hamburg have been deposited on land and used for building plots or for agricultural purposes.     

Impact of a flood disaster on sediment toxicity in a major river system--the Elbe flood 2002 as a case study

The ecotoxicological implications of a flooding disaster were investigated with the exceptional Elbe flood in August 2002 as an example. Sediment samples were taken shortly after the flood at 37 sites. For toxicity assessment the midge Chironomus riparius (Insecta) and the mudsnail Potamopyrgus antipodarum (Gastropoda) were exposed to the sediment samples for 28 days. For a subset of 19 sampling sites, the contamination level and the biological response of both species were also recorded before the flood in 2000. The direct comparison of biological responses at identical sites revealed significant differences for samples taken before and immediately after the flood. After flood sediments of the river Elbe caused both higher emergence rates in the midge and higher numbers of embryos in the mudsnail. Contrary to expectations the toxicity of the sediments decreased after the flood, probably because of a dilution of toxic substances along the river Elbe and a reduction in bioavailability of pollutants as a result of increasing TOC values after the flood.     

Das neue Chemikalienprogramm von UNEP Chemicals

Zusammenfassung  UNEP International Register of Potentially Toxic Chemicals (IRPTC) wurde von der ersten VN-Umweltkonferenz 1972 geschaffen. Sein Einfu? und Zusammenwirken in den 80ziger Jahren mit anderen internationalen Programmen der WHO, FAO, OECD und EG in der Chemikalienkontrolle wird beschrieben. Nach dem Erdgipfel von Rio 1992 werden im VN-Rahmen drei neue Gremien gebildet, die das Fachprogramm des Kapitels 19 der Agenda 21 (umweltfreundliches Chemikalienmanagement) umsetzen sollen: die United nations Commission of Sustainable Development, das Intergovernmental Forum on Chemical Safety und das Interorganization Programme for the Sound Management of Chemicals. Der Erdgipfel brachte auch für IRPTC eine Neuorientierung. Seit 1996 hat UNEP Chemicals, wie sich IRPTC nunmehr nennt, drei Aufgaben in sein Arbeitsprogramm aufgenommen, die beschrieben werden: das internationale übereinkommen zum Prior Informed Consent, das internationale übereinkommen zur Kontrolle der Persistent Organic Pollutants, und schlie?lich sein traditionelles Arbeitsgebiet des Informations-austausches über Stoffe wird weitergeführt.

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Die Aussagen dieses Beitrages sind die Meinung des Autors. Sie müssen nicht mit der Auffassung des Umweitbundesamtes oder von UNEP Chemicals übereinstimmen.     

CAREAIR: A Computer Aided Modeling Toolbox to Generate and Analyze Emission Data in High Temporal and Spatial Resolution

ABSTRACT

For the evaluation of air quality improvement strategies, emission data in high temporal and spatial resolution is necessary, including all emission sources and all relevant pollutant species. Computer aided models are usually used to generate this emission data because it is not possible to obtain measurements from all sources, and, furthermore, a large amount of data has to be handled. For the development of emission modeling systems, a software tool called CAREAIR has been created. The intention of this paper is to introduce CAREAIR to the international community dealing with emission inventories and air quality improvement strategies.

CAREAIR is not just a single emission model but a flexible modeling toolbox. The database contains data and formulas for data manipulation, which is performed by using a set of flexible operators with different specifications. The emission calculation is carried out by combining several data manipulation operators. The CAREAIR modeling toolbox allows model implementation for the calculation of emissions from different pollutants in a high spatial and temporal resolution. The application of CAREAIR within various investigation projects in Germany, Europe, and Nigeria shows that CAREAIR is an appropriate instrument for the development of flexible emission models by meeting the various demands of these projects. The function and the data structures of this modeling toolbox are described and, towards the end of the paper, an example of an emission calculation with CAREAIR is given.     

Das neue Chemikalienprogramm von UNEP Chemicals

The UNEP International Register of Potentially Toxic Chemicals (IRPTC) was created by the UN Conference on the Human Environment of 1972. Its influence and co-operation in the 80ies with other international programmes of the WHO, FAO, OECD, and EC for the control of chemicals is presented here. The follow-up of the UN Conference on the Environment and Development (1992) created three new bodies that are to implement chapter 19 of Agenda 21 (Environmentally Sound Management of Chemicals): The UN Commission of Sustainable Development, the International Forum on Chemical Safety, and the Interorganisation Programme for the Sound Management of Chemicals. This UN Conference also brought about a new orientation ofIIRPTC. In 1996, IRPTC was renamed as UNEP Chemicals and has been functioning in three major fields since then: The international convention on Prior Informed Consent, the international convention on the control of Persistent Organic Pollutants and, finally, a continuation of is traditional field of information exchange on chemicals.     

Fate of the veterinary antibiotic 14C-difloxacin in soil including simultaneous amendment of pig manure with the focus on non-extractable residues

The fate of ¹⁴C-labeled difloxacin (¹⁴C-DIF) was studied in time course experiments after application on soil (Ap horizon of silt loam) and amendment of authentic DIF containing pig manure (146 mL kg^?1; 4.17 MBq kg^?1; 0.85 mg kg^?1) or water (124 mL kg^?1; 0.42 MBq kg^?1; 0.09 mg kg^?1) for 56 and 120 days of incubation, respectively.

Mineralization of ¹⁴C-DIF was below 0.2% in both experiments after 56 days or 120 days. In the course of the experiments, portions of extractable radioactivity (Accelerated Solvent Extraction (ASE); acetonitrile-water) decreased to 19–21% depending only little on manure amendment. Non-extractable residues of ¹⁴C-DIF increased to 70–74% after 56 days and 120 days, respectively, and therefore were the main route of ¹⁴C-DIF in soil. According to radioanalytical HPLC and LC-MS/MS, only the parent compound was found in all extracts over the whole time of the experiment. According to fractionation of the non-extractable residues (NER) into particle size fractions, ¹⁴C portions were associated to the water used for fractionation, the silt and clay fractions, whereas no radioactivity was detected in the sand fraction. The majority of ¹⁴C was found within the clay fractions.

Fractionation of humic components showed that radioactivity derived from ¹⁴C-DIF was associated with humic acids, fulvic acids, humins and minerals and very little with soluble, non-humic HCl fraction. The highest portions of radioactivity were found in the fulvic acid fraction. Results obtained by size exclusion chromatography (SEC) of the purified fulvic acids were similar for every sample analyzed. One large portion of ¹⁴C co-eluted with fulvic acids of a molecular weight below 910 g mol^?1. Both fractionation methods demonstrated that the parent compound DIF or initial metabolites were rapidly integrated into humic materials and, thus, were major components of NER.     

Persistence revisited

We are happy and proud to announce that our book ‘Atmospheric Degradation of Organic Substances — Data for Persistence and Long-range Transport’ (see pp. 143–144) has recently been published by Wiley-VCH [1]. It contains a critical compilation of photo degradation rate constants and quantum efficiencies relevant for calculating the atmospheric persistence of volatile and a few semi-volatile organic compounds. In addition to the data of nearly 1100 substances, the importance of persistence in air and long-range transport potential is presented in two chapters from the point of view of chemicals legislation and of atmospheric photochemistry.