Ökotoxikologische Charakterisierung von Nonylphenol Isomeren

Background, Aim and Scope

Acute toxicity and estrogenic potency of six nonylphenol isomers, with nearly the same chemical structure and the same physico-chemical properties, were investigated in this study. Thes datasets give some insight into how far structure activity relationships can be used for these modes of action.

Methods

The toxicity of the isomers was investigated by the daphnia immobilisation test as well as the duckweed growth inhibition test. The estrogenic potency of the p-NP isomers was analyzed by MVLN-Reportergen-Assay.

Results

No differences between the isomers were found for baseline toxicity, neither in the daphnia immobilisation test nor in the duckweed growth inhibition test. Estrogenic potency of the isomers in the MVLN reportergen assay was markedly different for the tested isomers. The highest estrogenic potency was found for p353-NP, whereas p262-NP and p22-NP exhibited no estrogenic, but partial antagonistic potency in this assay.

Discussion

The results from this study clearly indicate how far simplification and structure activity relationships can be used in risk analysis. For bioconcentration and baseline toxicity structure activity relationships are possible and will allow simplification of the risk analysis. For special modes of action simple structure activity relationships are per se impossible. This was shown especially for the estrogen receptor interactions, where only small structural differences can lead to different modes of action.

Conclusions

It seems possible to reduce the effort for risk analysis, using combinations of measured data and predictive models. At the moment it seems unlikely that predictive models alone will and can be used for risk analysis.     

GIS-basierte Modellierung von Gewässerimmissionen

Goal and Scope

Environmental assessment of aquatic micro pollutants should consider the spatial and temporal variability of emission, transport and transformation. Simulation models coupled with Geographic Information Systems (GIS) provide digital maps of concentration patterns caused by the overlay of multipoint and diffuse emissions and natural attenuation processes in river basins. The paper gives an overview on GIS-based models for river basins and demonstrates the applicability by using some illustrating examples with GREAT-ER.

Main Features

Georeferenced models have several advantages: visualization of concentration patterns, investigation of spatial and temporal concentration profiles, analysis of exceedance of environmental quality standards, embedding in integrated river basin management systems.

Results and Discussion

GIS-based models allow a more realistic assessment. Monitoring programmes should be designed to deliver appropriate measured data for the evaluation and improvement of models.

Recommendation and Perspectives

The combination of digital maps, simulation models and environmental monitoring would provide better approaches for the risk assessment and water quality management of aquatic micro pollutants.     

Abschätzung des umweltchemischen und ökotoxikologischen Verhaltens von Stoffen durch computergestützte Analyse von Struktur und Verhalten sowie von Struktur und Wirkung

Risk assessment of chemicals requires comprehensive data material, which often is not available. To provide substitutes for the lacking experimental ecotoxicological and physico-chemical data, a software-system (SAR-System) has been developed comprising more than 90 estimation models for relevant endpoints. The approach is based on quantitative structure-activity relationships (QSAR). Two major aspects characterize the SAR-System:

1. The implemented models were tested for their validity and application range.
2. The QSARs are accessible by a menu-driven programme package.

The following endpoints are included: Thysico-Chemical Data: 1-Octanol/water-partition-coefficient log P_ow, vapour pressure, water solubility, pK_a-value, boiling point Biological Data: Toxicity towards fish, daphnia, tetrahymenae, algae, bacteria and mammals, mutagenicity. Distribution: soil sorption, bioconcentration, Henry-Constant, Mackay (Level I). Degradation: photodegradation, biodegradability.     

Nutzen und Grenzen von Modellökosystemen zur Erfassung der Wirkung von Schadstoffen auf benthische Lebensgemeinschaften

The aim of this short article is to deliver insight into the prospects and constraints of model ecosystems in the assessment of effects of contaminants on benthic communities, especially the meiofauna. Numerous substances accumulate in sediments and thus a complex contamination exists which is able to impair benthic organisms. Besides direct effects, indirect effects are of importance and should be considered. Changes in competition and predator-prey-relationships lead to a variety of effects in the benthic food web that cannot be explained by direct toxicity of contaminants. In this article two microcosm studies, one with the heavy metal cadmium and one with the veterinary pharmaceutical Ivermectin, are presented which both showed direct as well as indirect effects. A significant change in abundance and composition of the meiofauna community has been observed. The prediction of field-effects of a certain substance as well as the interpretation of field data are the aims of model ecosystems. Both studies proofed that the investigation of meiofauna in microcosms is a promising tool to achieve these aims. Furthermore, microcosms with meiofauna might be able to assist the effect-directed analysis (EDA) in a risk assessment by identifying the effect-causing contaminants of complex environmental samples.     

Bioassay zur Bestimmung von TCDD-Toxizitätsäquivalenten (TEQ) von Umweltproben und Reststoffen

Polychlorinated aromatic hydrocarbons (HAH) like 2,3,7,8-tetrachloro-p-dioxin (TCDD) elicit a multitude of toxic and biological effects. A common trait of these substances is their affinity for a cytosolic receptor protein and the subsequent induction of the synthesis of several gene products, including cytochrome P450 1A1 (CYP 1A1). In this publication we present a bioassay to determine the induction of CYP 1A1 as a sum parameter for the total toxic potential of critical halogenated compounds in complex environmental matrices. In order to eliminate compounds like polycyclic aromatic hydrocarbons (PAH) and naturally occurring substances which might interfere with the bioassay we developed a simple cleanup procedure. TEQ values derived from bioassay are in good agreement with those obtained from chemical analysis. This bioassay in combination with the simplified “single column” clean up represents a cost and time effective alternative to chemical analysis for the screening of large numbers of environmental matrices.     

Untersuchungen zur Eignung von Neutralsalzen als Referenzmittel bei der mikrobiologisch-ökotoxikologischen Bewertung von Pflanzenschutzmitteln im Boden

Goal and Scope

The information value of microbiologicalecotoxicological investigations of pesticides in soil increases if reference compounds with known biocidal effects are included. But those reference compounds used until now often are of remarkable environmental and human toxicity and therefore are difficult to handle. Inorganic neutral salts sometimes were discussed as alternatives, but their suitability needs to be tested before.

Methods

For laboratory experiments some microbial activities in soil were selected whose effects had been proved in several microbiological-ecotoxicological investigations. They include the mineralization of carbon and nitrogen (+ nitrification) as well as the biomass-related parameters dehydrogenase activity and substrate-induced short-term respiration. Several agricultural soils were used to confirm the results.     

Messung und Quantifizierung von Mineralölkohlenwasserstoffen

Investigations concerning the measurement and evaluation of mineral oil hydrocarbons using Fourier-transform-infrared (FT/IR-)-spectroscopy,¹H-Nuclear magnetic resonance (¹H-NMR)-spectroscopy and Capillary gas chromatography — Flame ionisation detection (GC-FID) are presented. By means of various mineral oils and three certified reference materials (CRM) all tested methods were within a ±7%-range to the mineral oil nominal value and the 95% confidence intervals of the CRM’s, respectively. The GC-FID evaluation could be done without calibration using an relative response ratio of mineral oil to an internal standard (n-tetracontane). A¹H-NMR-method was developed for the quantitative determination of mineral oil hydrocarbons, successfully applied down to 0.2 mg/ml. Due to the determination limit achieved, the¹H-NMR-spectroscopy gain in importance as a reference method for the analysis of mineral oils.     

Photometrische Bestimmung der Zytotoxizität von Chemikalien

Two test methods are presented to assess the cytotoxicity of chemicals. On one hand the protozoonTetrahymena pyriformis and on the other the bacteriumPseudomonas aeruginosa is cultured in defined media containing the test chemicals. Test parameter is the quantity of living cells surviving exposure. The conversion of the tetrazolium salt MTT into formazan is equivalent to cell viability. A mixture of detergent and isopropanol is used to dissolve the blue formazan which is not soluble in water, prior to photometric measurement. For cetyltrimethylammonium bromide, benzyldimethyldodecylammonium chloride, dodecylbenzenesulfonic acid sodium salt, potassium dichromate, 4-toluenesulfonic acid sodium salt, and 4-nitrophenol the EC50-values (mol/l) in theTetrahymena pyriformis- (Pseudomonas aeruginosa) test system were: 10^?5,81 (10^?5,08); 10^?4,68) (10^?3,80; 10^?4,50 (10^?4,14); 10^?3,97 (10^?5,11); 10^?2,71 (10^?2,50) and 10^?4,00 (10^?3,64). — With the assays described here it is possible to measure a large number of samples by quick and simple means.     

Die ökologische Bewertung von Seeufern in Deutschland

Goal and Scope

Details about the ecological function of lake shores as ecotones between land and lakes are not well-known. These ecotones are also heavily exploited and, in part, considerably changed. Whereas anthropogenic nutrient loading is decreasing, structural changes are increasing. Unfortunately, there is a deficit in methods of evaluation and decision processes.

Main Focus

Even the EU-water framework directive was no remedy for this deficit, as lake shores were included only implicitly. In this article several evaluation methods and their conceptual groundwork are presented. However, these methods were not developed for lake shore research. Therefore, criteria are proposed which could fulfill the specific demands of lake shore assessments. The management of lakes shores should consider structural and biological parameters, and be agreeable to local residents.

Results and Conclusions

In addition to conventional biodiversity methods, the ecology of lake shores could also be represented by a functional food net, for example in benthic invertebrates. But even quantification of biodiversity alone creates many problems. A simple biodiversity index cannot meet all the demands placed on a method of evaluation in complex situations, especially when coupled with additional information on structure, practicability, costs, etc. For these reasons, assessments for future management cannot be based on such an index.

Outlook

A possible approach to include this complexity in assessments is to apply mathematical models and theoretical order concepts.     

Management von schadstoffbelasteten Feinsedimenten in Bundeswasserstraßen

The Federal Institute of Hydrology has developed operating strategies in order to deal with dredged material within the scope of the Waterways and Shipping Administration. Sediments will be assessed based on certain quality parameters. The potential environmental impact at the source and relocation areas has to be evaluated in respect to ecological and economical issues. A coordinated sediment management plan for the Rhine River was commissioned. The most important contaminated sedimentation areas were identified, and special sedimentation areas were classified based on ecological impact or even risk. Proposals for economical and ecological strategies are discussed. Further developments for operational instructions dealing with sediments and dredged material in federal waterways are still being processed. The objectives of the river basin commissions as well as those of the stakeholders have to be met in an appropriate manner. In the framework of the analysis and impact of climate change on both sediment quantity and quality for optimizing sediment management, one or more dimensional hydraulic models will be applied. This will help gain a better insight into the understanding of contaminant transport in freshwater bodies.     

Schnelle Elementanalytik zur Abschätzung von Dioxinbelastungen: Ein neues Werkzeug zur Untersuchung von Brandschäden?

A car and a railway coach with an InterCityExpress interior were combusted in a tunnel. The deposition of pollutants could be detected by passive sampling devices over the distance of several hundred meters. Cotton passive collectors were analyzed for the elements Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Sb, Sn, V and Zn. A comparison with analytical results of PCDD/F and PAH (US EPA) showed a close similarity between the concentration profiles of some elements and the organic pollutants. As one outcome, Cd, Cu, Pb, Sb, Sn and Zn could be used as indicators for the estimation of surface contamination with PCDD/F or PAH in the event of such fires, thereby providing the advantages of faster results and lower costs.     

Schnelle vor-ort-analytik zur untersuchung von rüstungsaltlasten

Field screening methods for the analysis of explosives (for which commercial test kits are generally available) are reviewed. These techniques include immunoassays, photometric methods, bio and chemical sensors as well as thin layer chromatography. Basic aspects of these techniques are discussed, their validation is presented and their application to water and soil samples from hazardous ammunition waste is described. An evaluation of field studies with commercial test kits demonstrates that these techniques can be applied successfully for both the exploration of suspected contaminated sites and their sanitation. These methods are used on-site. In general, they allow short analysis times and a high sample throughput, thus leading to a significant reduction of the number of samples to be analysed in the laboratory and the costs.     

Entwicklung von ökotoxikologischen Instrumenten und ihre rechtliche Implementierung zur marinen ökologischen Risikobewertung von Chemikalien, Pestiziden und Baggergut

Background, aim, and scope The marine environment is often the final sink for pollutants, especially for persistent organic pollutants (POPs) and for persistent, bioaccumulative and toxic (PBT) substances. The body burden of marine top predators in the Baltic Sea, in the North Sea and also in the Arctic seas is alarming. Thus, the question was investigated if the European environmental law considers a prospective marine ecological risk assessment of chemicals, pesticides and dredged material before they are launched on the market or disposed to the sea. Results The analysis of European environmental law showed that the European environmental protection goals demand a good quality status of coastal waters until 2015 (Waterframework Directive) and a good quality status of European seas until 2020 (Marine Strategy Directive), but a specific marine ecological risk assessment of chemicals and pesticides is not sufficiently required in current European legislation. Discussion It was shown that the ecological risk assessment for freshwater ecosystems is, due to the pecularities of pollutant impacts in the marine environment, not adequate to predict marine effects and to protect the marine environment sufficiently. A statistical analysis of international databases on the relative toxicity of narcotics revealed that marine organisms can be significantly more sensitive than freshwater organisms towards substances with an unspecific mode of action (narcotics). Approximately 60?% of the industrial chemicals are classified as narcotics by their mode of action. Thus, this substance class is of environmental importance. Due to the hydrophobic properties and the low solubility of narcotics in seawater, the ecotoxicological assessment of marine sediments was of interest. An estuarine and marine bioassay test set was established and further developed to assess the ecotoxicological potential of brackish and seawater sediments. It was important that the test procedures were adapted to brackish and marine conditions and were harmonised between each other as well as on the international level. Conclusions Beside two bioassays for the ecotoxicological assessment of elutriates of marine and brackish sediments (bacteria bioluminescence test and marine algae test), the implementation and further development of the whole sediment bioassay with the marine amphipod Corophium volutator was important for enhancing the risk assessment. In order to gain a more standardised, all-season available test organism, the marine amphipod was for the first time reproduced under laboratory conditions the whole year round (also in winter), which is the essential basis for the urgently needed chronic whole sediment bioassay. The results of this investigation were implemented in the international (ISO), European (EN) and national (DIN) standardisations. Therefore, a standardised test set is ready for the implementation in the marine ecological risk assessment of chemicals, pesticides and dredged material in international, European and national legislation. Recommendations and perspectives Recommendations to improve the implementation of a marine risk assessment in European regulations are given with the goal to reach the internationally required objective of a sustainable development of the seas.     

Neue Aspekte in der Behandlung von Siedlungsabflüssen

The surface runoff from urban areas is one of the most important sources of pollutants emitted into surface waters. Suspended solids which act as a transport vehicle for many anthropogenic pollutants (e.?g. heavy metals, PAH) are a key factor in this regard. The development of efficient measures of storm water runoff treatment thus requires a further differentiation of suspended solids in a fine (clay and silt) and coarse (sand and gravel) fraction. Both fractions show distinctly different characteristics in pollutant loading, transport and retention on urban surfaces and sewer systems. The primary aim of storm water runoff treatment is the reduction of the fine particles which are always highly loaded with anthropogenic pollutants. In contrast the coarse particles are almost unpolluted especially if they have a low organic share. The widespread sedimentation tanks with surface loadings between 10 and 2?m/h are very inefficient. A significant, save and lasting reduction of the emitted load of fine particles requires a considerable reduction of the surface loads. That can be achieved with the installation of lamellar settler or the utilization of the very large volumes of flood management tanks frequently present in urban areas. Filtration plants are highly efficient but there application in urban areas is limited due to their high space demands.     

Bewertung der potenziellen Grundwasserbelastung von deponierten Hochofengasschlämmen

Goal and Scope

Blast-furnace sludge is a waste originating from pig-iron production and contains contaminants such as lead, zinc, fluoride and cyanide assumably contaminating the groundwater by leaching.

Methods

We investigated the chemical composition of 27 samples of landfilled blast-furnace sludge in pore waters which were obtained by the centrifugation of fresh material and elution with water according to DIN 38414 part 4 (S 4).

Results

The pore waters as well as the eluates were neutral to alkaline (pH 7.3 to 10.7) and were dominated by alkali and alkaline-earth metals as well as sulphate and nitrate. The concentrations of all elements and compounds investigated were mostly clearly larger in the pore waters than in the eluates. The average concentrations of environmentally relevant constituents such as lead (0,18 mg?1), zinc (1,5 mg l?1), fluoride (10,6 mg l?1), and total cyanide (1.8 mg l?1) in the pore waters were distinctly larger than the inspection value of the German Federal soil Protection Ordinance for the pathway soil-groundwater. Lead, zinc, and total cyanide concentrations in the pore waters were largely underestimated by the eluates, as these concentrations were 70 to 90% lower in the eluates compared to the pore waters.

Conclusion

In the case of landfilled blast-furnace sludge, eluates according to DIN 38414 part 4 (S 4) provide low concentrations which are unrealistic to forecast concentrations in the seepage water.     

Teil II: Verfahren zur Monetarisierung von Ökosystemleistungen

As it is practically impossible in an industrial society to reduce impacts into ecosystems to a level that would preclude any damages, the need for damage valuation arises. One of the available valuation tools is the economic approach. Subsequent publications present this approach using the example of soils. In this second part, two methods are presented for monetarising ecosystem services, the contingent valuation method, the valuation on the basis of restoration and replacement costs. Common arguments against the monetarisation of ecosystems, like the omission of intrinsic values or the incomplete information of individuals, are then discussed. In conclusion, limits and possibilities of monetarising ecosystem services are described.     

Toxizitätsänderungen in Photoreaktionen von Azaarenen

The azaarenes and the structurally analogous PAH accompany each other and occur ubiquitously in nature. Photochemical conversions like direct photolysis or the photoreaction with nitrate are important natural degradation reactions of azaarenes. Furthermore, photoreactions with chlorine and bromine radicals can be expected in nature. The reactions generate a large number of oxidized, nitrated and halogenated products with unknown toxicity. In this paper, a first screening of changes is reported in acute toxicity during the course of the photochemical reactions. As test system luminescent bacteria are used. For quinoline, isoquinoline and phthalazine the investigations show different changes of the toxicity of the reaction mixtures in dependence on the respective reaction type. The toxicity of the reaction mixtures of quinazoline and quinoxaline increases in all reactions investigated. Furthermore the reactions of bromine radicals with azaarenes also show an increase of the toxicity in all cases. Compared with the azaarenes in all reactions products with significantly higher toxicity are formed.     

Bestimmung von Redoxzonen in einem mineralölbelasteten Grundwasserleiter

Goal and Scope

The goal of this study is the investigation and the grafic presentation of the characteristic redox zonation in a mineral oil contaminated aquifer which will be formed in the plume downstream of the contamination source. Methanogenic conditions, sulfate-reduction, Fe(III)-reduction, Mn(IV)-reduction, nitrate-reduction, aerobic conditions. By that indications type and degree of microbial degradation which is the most important part in Natural Attenuation (NA) processes can be obtained easily.

Methods

Changes of the groundwater parameters Eh, O₂, NO ₃ ^? , SO₄ ^2?, Fe²⁺, Mn²⁺, HCO₃ ^?, Ca²⁺ will be measured upstream, downstream and also in the centre of the plume. The results will be presented in a sequence of special diagrams.

Results and Conclusion

When microbial degradation of hydrocarbons takes place, a microbial community will always use that electron acceptor from which it will gain a maximum of energy by the corresponding redox-reactions. This means as long as oxygen is available this will be used. After its depletion nitrate serves as electron acceptor leading via nitrite to the formation of nitrogen or ammonia. Manganese (IV) and Iron (III) species which are rather insoluble are mainly available from the soil-phase, can act as electron acceptor as next, leading to soluble Manganese (II) and Iron (II) compounds in groundwater. Finally before methanogenic conditions occur sulphate will become a suitable electron acceptor leading to the formation of hydrogen sulphide. All these processes of mineralization of the hydrocarbons will lead to the production of CO₂ and as consequence to an increase of HCO₃ ^? in groundwater changing the calcareous/carbonic acid-equilibrium. By that more soluble Ca(HCO₃)₂ is formed from insoluble CaCO₃, so the concentration from Ca²⁺ will also inerease. Thus, by the action of microorganisms, a typical redox-zonation and changes of other parameters will occur.

Recommendations and Perspective

To follow the changes in time and space of some characteristic groundwater parameters is a simple way to estimate the potential of microbial degradation in a contaminated aquifer considering Natural Attenuation (NA)-processes.