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.     

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.     

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.     

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.     

Untersuchungen zum ökotoxikologischen Schädigungspotenzial und Erosionsrisiko von kontaminierten Sedimenten in staugeregelten Flüssen

Particle-bound pollutants accumulate in river-bottom sediments, a process which results in a significant decrease in the ecotoxicological availability of toxicants for the majority of aquatic organisms. Under normal hydrologic conditions, the release of contaminants from bottom sediments is usually of minor importance. In contrast, flood events may remobilize highly contaminated sediments via in-stream erosion. The objective of this study was to develop a combined ecotoxicological and hydraulic approach to elucidate the ecotoxicological implications associated with the risk of erosion of contaminated sediments. This integrated strategy was applied to the lock-regulated Neckar river in Southern Germany. Both the bottom-sediment cores and suspended matter from two intensive flood events were investigated. Sediment samples below an erosional unconformity showed a sharp increase in the ecotoxicological load. Moreover, it was found that major flood events (HQ₅ and higher) could possibly erode even very old, well-consolidated and highlycontaminated sediments. The suspended matter of the high discharge events investigated (return periods of 15 to 20 years) exerted significantly higher cytotoxicity and mutagenicity than a moderate flood with a 1-year return period. These findings support the conclusion that the observed ecotoxicological effects during major floods may at least in part be due to the in-stream erosion of highly contaminated bottom sediments.     

Screening zur Mobilisierbarkeit von Kupfer aus Böden und Schlämmen

In the presented paper, the pHstat-procedure is compared with four simple extraction procedures. These procedures make use of the following extraction solutions: distilled water (based on DIN 38414 part 4, DIN-S4), 1 mol/L ammonium nitrate, 1 mol/L ammonium acetate at pH 7.0 and 1 mol/L sodium acetate at pH 5.0, respectively. The extraction procedures were applied to 10 different soil samples and 2 sludges. The DIN-S4-procedure shows the lowest amounts of mobilized copper. The highest parts are extracted by sodium acetate solution. For the procedures investigated, the mobilized amounts extracted by ammonium acetate solution are most comparable with those of the pHstat-procedure. The simple sodium acetate procedure is useful for screening to select significant samples from a large number of soils. Thus, the high effort caused by the pHstat-procedure can be reduced to a minimum through the application of this screening procedure. The application of this screening, however, is difficult for samples containing large parts of organic compounds, e.g. sewage sludge. These samples show a different extracting behaviour.     

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.     

Gasförmige Stickstoffemissionen im Lebensweg von Getreide zur Energiebereitstellung

The reduction of energy-based environmental pollution is a declared goal of governmental action in all industrialised countries. In this context, the aim of this paper is to investigate the emissions of volatile nitrogen species with regard to their resulting environmental impacts by the example of the heat provision from whole cereal crops as a substitute for light oil products. First, the applied methodology of a Life Cycle Assessment is discussed. The emissions of volatile nitrogen species and their resulting environmental impacts are subsequently quantified putting a special focus on the emissions of gases from biogenic sources in the agroecosystem. The comparison of heat provision based on whole cereal crops versus light oil over the entire life cycle shows that heat from biomass results in a lower environmental impact regarding the anthropogenic greenhouse effect, but a higher one with respect to eutrophication, acidification and the depletion of the stratospheric ozone layer. These results may change if the energy crops are produced extensively during agricultural processes, if other mitigation measures are undertaken or if the emissions from the combustion in the biomass-fired boiler are reduced.     

Entwicklung und Einsatz eines standardisierten Labortests für Dungkäfer (Aphodius constans) zur Prüfung der Ökotoxizität von Veterinärpharmaka

Goal, Scope, and Background

According to European legislation, an environmental risk assessment of veterinary pharmaceuticals for dung beetles is required if the substance is a parasiticide for the treatment of pasture animals. However, the demonstration of the environmental safety of those substances for dung beetles is strongly hampered by the fact that no standardized test system is available so far. Therefore, starting with recommendations from the SETAC advisory group DOTTS (Dung Organism Toxicity Test Standardization), a test system using the widespread temperate dung beetle species Aphodius constans was developed.

Methods

Using experiences gained at the University of Montpellier (e.g. in field studies) and in other terrestrial tests, details of culturing and testing of A. constans were investigated in a project sponsored by the German Environment Protection Agency (UBA). Basically, the survival of young larvae of A. constans exposed to the test substance spiked into formulated (i.e. dried, grounded and re-wetted) or fresh dung is measured over a period of three weeks. Using the model substance dimethoate (an insecticide required as positive control in tests with the predatory mite Hypoaspis aculeifer) the suitability of the new test was checked. Afterwards, the new test method was used to determine the toxicity of four common veterinary pharmaceuticals (ivermectin, dicyclanil, moxidectin, praziquantel) in formulated and fresh dung. Finally, the effects of ivermectin on the dung beetles were determined in a test using fresh dung from treated cattle.

Results and Conclusions

For Dmethoate LC₅₀-values were found in a range of 1–3 mg a.s./kg dung (dew.), depending on the dung type. Praziquantel did not show eirecis in the tested concentration range (i.e. up to 1000 mg a.s./kg Dung (DW). The LC₅₀-values of the other three pharmaceuticals were very low (<6 mg a.s./kg dung (DW)). With the exception of Dicyclanil no differences between formulated and fresh dung were identified. In the case of ivermectin the LC₅₀-value were even lower: about 0.5 mg a.s./kg dung (DW). No differences between the results of test in which the substance was spiked into dung and those tests which were performed with dung from treated cattle were found. These results prove the sensitivity as well as the robustness of this test method.

Recommendations and Perspectives

Based on the experiences reported here, it is recommended to standardize this test in an international ring test so that it can be incorporated in the risk assessment process for veterinary pharmaceuticals as described in the currently developed international registration guidelines.     

Bestimmung von leicht freisetzbarem Cyanid in Böden und Wässern mit der Mikrodestillation

Easy-liberatable cyanide has to be analysed if soils and waters are contaminated by cyanide. The aim of this study was to determine easy-liberatable cyanide in these environmental samples using a micro-distillation apparatus by means of a modified digestion vessel. Pure aqueous solutions of different cyanide species, five contaminated and uncontaminated soil samples and two water samples were analysed by micro-distillation according to the German standards. Recovery was determined by analysis of spiked samples. When using the modified digestion vessels, the pH of 4 which is demanded by the standard method can be adjusted. The recovery of potassium cyanide and weakly-complexed zinc-cyanide ranged from 93–101% for standards, and from 87–98% for spiked samples. In contrast, the recovery of strong iron-cyanide complexes was below 4% both for pure solutions and spiked samples. The precision of the method expressed as a relative standard deviation was 25% in cases of very low easy-liberatable cyanide contents (< 1 mg CN kg^?1) and below 12% in case of high easy-liberatable cyanide contents (> 1 mg CN kg^?1) for contaminated soils. The determination of easily-liberatable cyanide in soils and waters using micro-distillation combined with the modified digestion sample is an alternative to other distillation methods.     

Batterienrecycling: Möglichkeiten zur Erhöhung der Rücklaufquote

Separate collection and exploitation of used batteries facilates the recycling and eventual waste management of such heavy metals as mercury and cadmium. It is thereby possible to regain raw materials like zinc, manganese and iron for the raw material cycle. Although the collection and recycling of used batteries in Switzerland is financed by a prepaid disposal fee, their returning rate of almost 60% is too low for several reasons. A questionnaire survey carried out on 2000 households revealed the following frequenthy: People collecting paper, glass, aluminium, compost and tinplate, are more separate used batteries from ordinary garbage. The number of collecting points is supposed to be sufficient, but not all of them are sufficiently marked. The prepaid disposal fee (VEG) should become obligatory so that it would be possible to compensate the collecting points. It is not obvious from the results of the survey if the introduction of a deposit of batteries would raise the retourning rate. As far as advertising is concerned, only the “battery bag” sent to every household by the BESO seemed to influence the collecting behaviour in a positive way, poster advertising had only little effect. Appeals in newspapers, radio and television did not show any changement of the collecting behaviour. However, information and knowledge about batteries and their recycling do have a positive influence in the collecting behaviour of the consumers in this specific case.     

Bewertungsmaßstäbe zur Beurteilung von Schadstoffbelastungen in Böden anhand der Bioverfügbarkeit

Until now, assessment of contaminated sites is based on variable protection goals, whereby total contents and in part mobile contents are considered. Due to interactions of pollutants in soil and bound residues, total contents do not reflect the actual risk. In contrast an investigation based on availability/bioavailability of contaminants would enable a harmonization of the protection-goal-based evaluation and a closer-to-reality risk assessment for the individual location.     

Erprobung und Erfolgskontrolle eines Phytoremediationsverfahrens zur Sanierung Sprengstoff-kontaminierter Böden

The final article of a series of three evaluates the in situ-remediation of TNT(trinitrotoluene)-contaminated soil from ‘Werk Tanne’. The multidisciplinary approach allows a differentiated assessment. Grading with large-scale machinery leads to a depletion of TNT for almost 90% within the first 6 months, while ADNT(amino-dinitrotoluene)-content decreases more or less steadily over 1,5 years. Grading reduces the heterogenous distribution of the contamination only slightly. Results from field-monitoring and biotest-battery indicate residual toxicities of ecotoxicological relevance and a reduced capacity for biological regeneration, in comparison with the uncontamined site. Mycorrhized plants safe-guard the site and improve the soilecological conditions. Their role in reducing lower level residual toxicity requires further investigation. There is need for future research (1) on the dynamics and mechanisms of the initial decrease of TNT followed by stagnation, (2) on the fate of the primary metabolites, (3) on long-term effects of the phytoremediation, and (4) on the establishment of the complex monitoring for routine work.     

Erprobung und Erfolgskontrolle eines Phytoremediations-verfahrens zur Sanierung Sprengstoff-kontaminierter Böden

Results of a field experiment (please refer to Warrelmann et al. 2000a) document TNT-degradation and regeneration after the establishment of a phytoremediation. Various approaches are included in a complex monitoring system, which are conducted in the field (nitroaromatics in soil, seepage water, and plants; soil fauna; soil fungi; decomposition) as well as in the lab (a battery of 6 biotests). The data document a high heterogeneity of the TNT-contamination, a rapid initial decrease and a mediocre displacement of nitroaromatics in plants and seepage water. The initial rapid transformation of TNT to aminodinitrotoluenes ceases significantly after 3 months. Results of the biotest battery allow a sophisticated assessment of soil toxicity; the results from the soil ecological field investigations make the long-term effects of TNT-contamination likely. In a third part of the series of articles, a synopsis and judgement of the project will be delivered.     

Ökologische Optimierungspotenziale der energetischen Nutzung von Palmöl

Aim and Background The use of palm oil for bioenergy has become increasingly important for Europe in the last years because of its favourable proportion of yield to area under cultivation. Thus, palm oil presents a low-priced alternative to other energy sources, e.?g. rapeseed oil. Currently, however, palm oil gets a bad press due to new studies about the negative environmental consequences of cultivation practices. Due to the high demand for palm oil, land is becoming scarce. This results in the clearing of primary forests and consequently in the loss of biodiversity and in an increase of greenhouse gas emissions. To reduce the latter, not only the process of oil palm cultivation has to be optimised but also the practice of establishing new plantations by clearing natural forests has to be questioned. The aim of this article is to disclose potentials for greenhouse gas reductions in existing as well as in newly-planned oil palm plantations. Results and Discussion For existing oil palm plantations, two main fields for possible optimisation can be identified: one is improving the plantation management, the other is increasing the efficiency of the utilisation of waste products such as fibres and husks or oil mill effluents. For newly-planned oil palm plantations alternative land use scenarios have to be considered. The results show a big potential for optimisation. Thus, the greenhouse gas balance improves slightly if plantations are run more efficiently. If the waste products are used to generate energy, there are significantly positive effects on the greenhouse gas balance, especially through the reduction of methane emissions. By running a plantation in a professional best-practice way, 4.8 t of greenhouse gases can be saved annually per hectare cultivation area, expressed as CO₂ equivalents. If newly-planned oil palm plantations are established on fallow land, greenhouse gas emissions can be further reduced by an additional 4.8 t of CO₂ equivalents per hectare and year. From an economic perspective, this may be more costly than clearing primary forest but it is advantageous for both the greenhouse gas balance and the biodiversity of the concerned areas. All in all, exploiting the whole potential for optimisation could result in the saving of 10.2 t CO₂ equivalents per hectare and year more than it is the case in the existing mode of cultivation. Conclusions and Perspectives Due to the high demand of palm oil by the world market, cultivation areas for oil palms are becoming increasingly scarce. Thus, it is vital to exploit the full potential of oil palm cultivation in an environmentally and economically sustainable way. The management of plantations has to be optimised and a generally valid waste management system must be implemented in existing and future plantations. New plantations should preferably be established on fallow land, not by the clearing of primary forests. It is essential for a sustainable palm oil production to tap the full potential for optimisation. This, however, is currently not happening due to the high start-up investments. It is thus recommended to introduce an internationally valid certification system which may provide an incentive for more sustainable and effective production methods.