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.     

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.     

Verteilung und Abnahme von bodennahem Ozon in städtischen und ländlichen Regionen

The compilation of ozone data for the federal states of Hesse and Northrhine-Westphalia (NRW) in Germany indicated that the concentration of ozone level slightly decreased during the years 1990–1998. The average concentration of ozone over forest areas is significantly higher than over cities. Only the maximum figures in the years approached one another. However, values passing the legal thresholds (180 μg ozone/m³) were two to three-fold higher over forests than over cities. The ozone concentration in air is inversely proportional to the traffic density. It is suggested that the lower NOx concentration over the forest than over cities is involved in the maintenance of the higher ozone-concentration over forest areas. In the cities, the ozone is reduced by NO to almost zero at night, whereas it is reduced by only about 50% over forests with lower NO concentrations. This reduction is only partially compensated in connection with the photolysis of NO₂ and the subsequent oxidation of O₂ to O₃ during the day. The ozone situation is principally the same in the federal states of Hesse and Northrhine-Westphalia.     

Einstufung und Kennzeichnung: das Instrumentarium von GHS und REACH für das Risikomanagement

For the safe use of chemicals it is necessary to identify risks in different fields of application. Not until then harmful effects to man and the environment can possibly be reduced by adequate measures. Here the identification of intrinsic properties of chemicals is an important fundamental for evaluation. Broad examination of exposition follows. REACH and GHS deliver new instruments which, due to their requirements on information quality and transparency as well as on harmonization, contribute to the improvement of risk management measures (RMM). With the coming into force of the CLP-regulation and the implementation of the GHS within the EU on 20.?1.?2009, as suggested in the white book on European Chemicals policy in 2001, the new system of European chemical law has been completed at a regulatory level. This article shows the development so far from the first directive on the regulation on the labeling of chemicals, to the establishment of application and test procedures, and then to the instruments of risk communication and risk management introduced by REACH and the CLP-regulation.     

Die Rolle der Globalisierung und Klimaveränderung auf die Entwicklung von Stechmücken und von ihnen übertragenen Krankheiten in Zentral-Europa

Mosquitoes and mosquito-borne diseases know no borders, and their spread is a consequence of globalization related to high mobility of humans and international trade as well as on climate change. Higher temperatures and precipitation favour the development of mosquitoes as well as the pathogens and parasites which are transmitted by mosquitoes. An increase of about 2?°C would shorten the time for the development of larvae and pupae of Anopheles messeae (vector of malaria) by almost three days resulting in an increase of gonotrophic cycles and number of generations. The higher numbers of breeding sites for Anopheles species such as An. plumbeus in cess pools due to the change of agricultural practises increase the contact with potential vectors of malaria as well. However, at least in Germany, malaria will not play an important role anymore. The invasion of new species such as Stegomyia albopicta (formerly Aedes albopictus) is enhanced by human migration and international trade. St. albopicta was first discovered in Germany in 2007. Nowadays, this species, originally from Southeast Asia, occurs in 13 European states. Thus, the risk for outbreaks of arboviroses is increased.     

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.     

Anreicherung atmosphärischer Depositionen von Metallen und Stickstoff in Moosen Mecklenburg-Vorpommerns von 1990 bis 2005

Background, aim and scope Since 1990 the UN ECE Heavy Metals in Mosses Surveys provide data inventories of the atmospheric heavy metal bioaccumulation across Europe. In the survey 2005 the nitrogen accumulation was measured for the first time in most of the participating countries. In Germany, the surveys were conducted in close cooperation of the relevant authorities of both the Federal Republic and the sixteen states. Therefore, statistical evaluations of the moss survey data with regard to the whole German territory and single federal states are of interest. This article concentrates on Mecklenburg-Western Pomerania, dealing with the mapping of the spatiotemporal trends of metal accumulation from 1990 to 2005, the spatial patterns of nitrogen accumulation in 2005, and the spatial variability of bioaccumulation due to characteristics of the sampling sites and their surroundings. Materials and methods The bioaccumulation of up to 40 trace elements in mosses was determined according to a Europe-wide harmonised methodology. The according experimental protocol regulates the selection of sampling sites and moss species, the chemical analysis and quality control and the classification of the measured values for mapping spatial patterns. In Mecklenburg-Western Pomerania all sampling sites were described with regard to topographical and ecological characteristics and several criteria to be fulfilled according to the guideline. Together with the measurements this metadata was combined with other information regarding land use in the surroundings of the sampling sites in the WebGIS MossMet. The spatial structure of the metal bioaccumulation was analysed and modelled by variogram analyses and then mapped by applying different kriging techniques. Furthermore, multi metal indices (MMI) were derived for both the sampling sites and raster maps with help of percentile statistics: The MMI_1990–2005 was calculated for As, Cd, Cr, Cu, Fe, Ni, Pb, Ti, V and Zn. The statistical association of the metal bioaccumulation, site specific characteristics as well as information on land use and emissions was analysed by bivariate nonparametric correlation analysis, contingency tables and Chi-square Automatic Interaction Detection (CHAID). Results The results of the quality controlled chemical analyses show a significant decrease of the metal bioaccumulation in Germany from 1990 to 2000 for all elements. However, in Mecklenburg-Western Pomerania the concentrations of Cr and Zn are even significantly higher than those found in 1990. From 2000 to 2005?a further non-significant increase can be stated for As, Cu, Ni and Ti. The concentrations of Cd and Pb decreased significantly throughout all four surveys. The MMI illustrates the temporal trend of the metal bioaccumulation as a whole: After a significant decrease from 1990 to 2000 it increased significantly till 2005. The N concentration in mosses in Mecklenburg-Western Pomerania reaches from 1.3 to 2.3?% in dry mass and is negatively correlated with the forest ratio in the surroundings of the moss sampling sites and to the same degree positively correlated with the area ratio of agricultural land uses. Except for Cd, Pb and Sb all metal concentrations in the mosses are negatively correlated with the forest ratio around the sampling sites. With the exception of Cr all metal concentrations are further negatively correlated with the precipitation sums of the accumulation periods. Only the Cu and Zn concentrations show no or rather a negative correlation with the tree height whereas all other elements exhibit positive correlations. Furthermore, all elements except Cr are significantly associated to the sampled moss species, the growth pattern and the frequency of occurrence of the mosses at the respective sampling sites. Exemplified for Cu multivariate correlations were furthermore detected by CHAID. It could be shown that the frequency of the mosses, the sampled moss species, the distance to motorways and the distance to the Baltic Sea are the statistically most significant boundary conditions of the Cu concentrations in the mosses sampled in Mecklenburg-Western Pomerania in 2005. No correlations were found between the modelled total depositions and the concentrations of Cd, Hg and Pb in the mosses at p < 0.1. For Pb in 1995?r is 0.52 at p = 0.012, for the other surveys no correlations at p < 0.05 could be found. Discussion The increase of the Cr bioaccumulation from 2000 till 2005 is particularly pronounced in Mecklenburg-Western Pomerania. This trend is confirmed with regional differences in the national average as well as in other participating countries like in Switzerland. Deposition measurements did not register this trend. In contrast to the UNECE area, the federal territory and several federal states no correlations were found between the modelled total depositions and the metal concentrations in the mosses. Conclusions The fact that no correlations were found between the modelled total depositions and the element concentrations in the mosses may be caused by the low spatial resolution (50?×?50?km) of the EMEP data. The moss surveys contribute to the heavy metal and the multi-component-model of CLRTAP because they prove on different spatial scales how air pollution control influences the accumulation of emitted substances in environmental subjects of protection like vegetation. In contrast to deposition measurement networks the moss monitoring identified a trend reversal in Mecklenburg-Western Pomerania: The continuous decrease of the metal bioaccumulation in mosses from 1990 till 2000 has changed to an increase of several metals between 2000 and 2005. This increase is significant for Cr and Zn. Recommendations and perspectives The spatial resolution of the EMEP deposition data should be enhanced based on the Europe-wide regression relationship between the element concentrations in the deposition and in the mosses. For regional studies the existing but so far not useable deposition measurement data of the federal states should be made available. It should further be investigated what caused the increase of the Cr concentrations above the level of 1990 – perhaps emissions or biogenic effects as a consequence of simultaneously increased nitrogen loads? The Heavy Metals in Mosses Surveys are a positive example for environmental monitoring activities reaching across three spatial and administrative levels: regional (e.?g. federal state or natural landscape), nation wide (e.?g. Germany) and continental (e.?g. Europe). In Germany the harmonised and quality controlled moss data are made available via a WebGIS portal. Therefore the moss data may easily be accessed for environmental monitoring purposes and the control of environmental political actions. Hence, the continuous task of environmental monitoring can be met and carried on in the future. It should further be considered to expand the moss monitoring on the survey of persistent organic pollutants and apply it in human-biomonitoring. This would facilitate the acquisition of indoor and outdoor pollution with the same receptor.     

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.     

Bestimmung von Nitrodiphenylaminen und verwandten Verbindungen im Sickerwasser einer Rüstungsaltlast

Goal, Scope and Background

Nitrodiphenylamines can be found at abandoned military sites where the explosive 2,2′,4,4′,6,6′-hexanitrodiphenylamine (hexyl) or diphenylamine as a stabilizer of smokeless powder was handled. Aim of the present study is the development of HPLC methods for the analysis of contaminants which can be expected in particular under aerobic conditions at premises which are contaminated by nitrodiphenyl-amines and related compounds.

Methods

A list of 13 compounds which can be expected at these explosives factories was deduced from literature studies. HPLC methods were developed for the analytes. Water samples from the unsaturated zone of a former hexyl-producing factory were collected by suction cups and the material was analysed according to these procedures to demonstrate the practicability of the new methods and to verify the existence of the postulated compounds in the environment of the former nitration plant.

Results and Conclusion

The new HPLC methods are suitable for the exploration of sites contaminated by nitrodiphenylamines. Beside some hexyl its intermediates 1-chloro-2,4-dinitrobenzene, 2,4-dinitrodiphenylamine und 2,2′,4,4′-tetranitrodiphenylamine were identified in the leachate water.

Recommendation and Perspective

It is advisable to include at least these 4 compounds in the examination of former hexyl-producing plants. Several unknown peaks were observed in the HPLC-chromatogram. It is recommendable to perform further investigations of the unidentified compounds to compile a final list of analytes for military sites polluted by nitrodiphenylamines.     

Konzentration und Verteilung von Platingruppenelementen (PGE) in Böden

In Germany automobile exhaust control by platinum-group element (PGE) loaded catalysts is now well established. By mechanical or chemical attrition, these catalysts could act as a potential source for a significant increase of PGE abundances in the environment. During a recent research program concentrations and distributions of PGE in different soils were measured along the highway A66 Frankfurt-Wiesbaden. 71 nearsurface soil samples were analysed by graphite furnace atomic absorption spectrometry (GFAAS). The results revealed average abundances of 10 ppb platinum and 3 ppb ruthenium. Palladium as well as rhodium were below the analytical detection limit of 2 ppb. With increasing distance from the highway edge PGE values gradually decreased. Only the upmost soil layer, down to 20 cm depth, contains measurable PGE concentrations. Results: There are irregular PGE concentrations of anthropogenic origin in different soils along the highway A66 Frankfurt-Wiesbaden possibly arising from automobile exhaust catalysts. Further monitoring could help to avoid potential environmental hazards. *** DIRECT SUPPORT *** A00HP020 00002     

Einsatz der Hasse-Diagrammtechnik zur vergleichenden Datenanalyse von Biomarkerantworten und ökotoxikologischen Tests

Ecotoxicological investigations focus on biological systems and their response to chemically induced stress. Experimental techniques are much more developed than deterministic dynamic modelling. In this methodological contribution a technique is presented, based on lattice theory. This technique, also calledHasse diagram technique, allows data analysis with respect to comparative evaluation. Hasse diagrams are used

? to suggest a possible measure of microbial diversity,

? to analyze dependencies between phospholipid fatty acids and simple geochemical parameters on an ordinal scale and

? to visualise complex results of interactions of humic substances with xenobiotics.

     

Versuchsanlage zur energetischen Beurteilung von Substraten und Kofermentaten für Biogasanlagen

Goal, Scope and Background

Worldwide energy requirements are constantly increasing. Rising prices and the necessity to secure the future energy supply have led the decision-makers in politics and economy to focus on the more intensive use of their own resources. Before the background of possible climatic effects caused by the use of fossil energies, the use of renewable resources as primary energies, with its narrow C-circulation, have gained in importance, particularly in terms of economic aspects. The production of biogas is of specific interest here. It is a sensible ecological investment and a solid source of income for our agriculture.

Material and Methods

The operator uses a complex biological system in a plant with high investment costs. An economic operation is only possible if the process parameters are optimized and the properties of the substrates and the co-ferments are known. For the important determination of the blogas potential, we present an efficient and robust system, which is easy to handle and low cost, that has been developed by the LHL and LLH at the Eichhof. This procedure enables one to make statements on the implementation dynamics and is also suited to judge the fermentation process depending on the size of particles, as the co-ferments are used in a practice-oriented consistency.

Results

With the described fermentation apparatus you can not only assess the potential development of biogas and methane, but also the process of fermentation. The sum-graphs determined allow one to make conclusions on the implementation dynamics and, thus, on the optimization of the process. The advanced equipment makes it possible to determine the process of fermentation and the gas yield under different retention times and digester loads. The determination of the potential of the biogas and also the evaluation of the continuous fermentation are related to a specific correction factor won from the standard.

Discussion

A prerequisite for economic process management is the knowledge of the attainable gas yield and the fermentation process of substrates and co-ferments. A precise calibration is the quality basis for the results achieved with this method, as is the case with other fermentation tests as well. For the tests, a highly homogeneous substrate, which guarantees a continuous biological activity in the digesters, ought to be used. The possibility of determining optimum retention times and digester loads with this equipment makes costly tests with a full scale reactor unnecessary.

Conclusions

All tests run demonstrated that the fermentation apparatus originally developed to determine the biogas yield is absolutely suited to also assess the impact of different digester loads and retention times.

Recommendations

The problem of the suitability and the potential of different materials, the optimum reactor performance and the combination of different processes of energy generation from renewable but also conventional resources will increaseingly become the focus of laboratory tests. The following subjects have to be taken into account:

- Testing different materials on their suitability

- Evaluation security of common and new co-ferments

- Guidelines for mixtures to optimize reactor performance

- Mixtures of different substrates and co-ferments available to a particular operator (also with the help of simulation models)

- Processing changing quantity proportions of plants won from a rotation of crops altered for energy generation

- Other parameters like pre-fermentation, particle size and fer mentation supplements.

Perspective

These tests with a high practical relevance are supposed to contribute to a reliable method of producing biogas, in order to optimize the yield of gas production, but also to find a calibration of less costly procedures like those involving Near Infrared Spectroscopy (NIRS).     

Bakterielle Mineralisierung von Dibenzofuran,Dibenzo-p-dioxin und 1,2,4,5-Tetrachlorbenzol in Böden

Quantitative degradation of dibenzofuran (DBF), dibenzo-p-dioxin (DBD), and 1,2,4,5-tetrachlorbenzene (TeCB) by the bacterial strains sphingomonas sp. HH 69, sphingomonas sp. RW1 and pseudomonas sp. PS 14 was investigated by radio-tracer techniques in liquid cultures and especially in samples of different soils. Pure strains converted DBF, DBD and TeCB up to 80% to CO₂ within few days. This degradation occurred not only in aerated liquid cultures but also in heterogeneous soils, with low levels of other pollutatns at favourable pH-values. Rate and degree of the mineralization of DBF, DBD and TeCB were independent of the DBF-, DBD-, or TeCB-concentration in the soils within a broad range. There was obviously a close correlation between the starting concentration of active cells (starting bacterial count) and the rate of degradation of the test substances in soil; by raising the starting bacterial count in the soil samples, mineralization of DBF, DBD, and TeCB, respectively, was clearly accelerated. However, under nearly the same coniditions in more acid soils (pH-values < 4) no significant degradation of DBF, DBD, and TeCB to CO₂ took place. As expected, this difficulty can be overcome by mixing CaCO₂ into the acid soils (liming). Easily utilizable substances like peptone, triolein, and glucose added as special carbon and energy sources to low contaminated soils, had only a small—if any—effect on the mineralization of DBF, DBD, and TeCB. In soils contaminated by a mixture of pollutants, the bacterial strains could develop their degradation capacity only to a limited extent and showed different degradation effects depending on the basic type of contamination. The efficiency of the degradation specialists was thus dependent on the “Chemical Environment” (type and concentration of contaminants present).     

PCB-/DDT-Kontaminationsbestimmung und Bewertung von Proben aus einem früheren Transformatorenhaus

The PCB and DDT contamination is described in the immediate vicinity of a transformer house (Odenwald, Germany). Samples were taken inside and outside the house and analyzed. For a toxicological assessment the measured values (according toBallschmiter PCB 77 and PCB 126) are converted into toxic equivalents.     

Metallakkumulation in Moosen: Standörtliche und regionale Randbedingungen des Biomonitoring von Luftverunreinigungen

Goal and Scope

Several studies show that the concentration of metals in mosses depends not only on metal deposition but also on factors such as moss species, canopy drip, precipitation, altitude, distance to the sea and the analytical technique used. However, contrasting results have been reported and the interpretation of the spatial variability of the metal accumulation in mosses remains difficult. In the presented study existing monitoring data from the European Heavy Metals in Mosses Surveys together with surface data on precipitation, elevation and land use are statistically analysed to assess factors other than emissions that have an influence on the metal accumulation in the mosses.

Main Features

Inference statistics and Spearman correlation analysis were applied to examine the association of the metal accumulation and the distance of the monitoring sites to the sea as well as the altitude. Whether or not significant differences of the metal loads in the mosses exist at national borders was examined with help of the U-test after Mann and Whitney. In order to identify and rank the factors that are assumed to have an influence on the metal uptake of the mosses Classification and Regression Trees (CART) were applied.

Results

No clear tendency could be derived from the results of the inference statistical calculations and the correlation analyses with regard to the distance of the monitoring site to the sea and the altitude. According to the results of the CART-analyses mainly the moss species, potential emission sources around the monitoring sites, canopy drip and precipitation have an effect on the metal bioaccumulation. Assuming that each participating country followed strictly the manual for sampling and sample preparation the results of the inference statistical calculations furthermore suggest that in most cases different techniques for digestion and analysis bias the measurements significantly.

Discussion

For the first time a national monitoring data base consisting of measurement data and metadata as well as surface information on precipitation, land use and elevation was applied to examine influence factors on the metal bioaccumulation in mosses. The respective results mirror existing knowledge from other national studies to a large extend, although further analyses are necessary to affirm the findings. These analyses should include data from other national monitoring programmes and should additionally be carried out with other decision tree algorithms than CART.

Conclusions

The local variability in the metal concentration in mosses can be uncovered in terms of predictors or underlying hidden causes by using CART. Ideally, such an approach should be applied across the whole of Europe. This will only be feasible if all participating countries provide additional information about site characteristics as currently is done in for example the German moss surveys.

Recommendations

The UNECE Metals in Mosses Survey experimental protocol should be improved in order to reduce the observed influences, to enhance standardisation, and to strengthen the quality control. This implies the integration of sampling site describing metadata into the assessment. Furthermore, basis research is needed to test the hypothesis concerning moss species-specific accumulation of depositions.

Perspectives

Provided that the presented results hold true in further analyses correction factors should be applied on the moss data in order to get the depicted spatial patterns and temporal trends of metal bioaccumulation unbiased. Such factors should be calculated for natural landscape units or ecoregions that are homogeneous with regard to climate, vegetation and altitude.     

Identifikation geeigneter Nachweismöglichkeiten von hormonaktiven und reproduktionstoxischen Wirkungen in aquatischen Ökosystemen

Background and objectives There is an urgent need to detect, assess, and reduce effects of hormonally active compounds and endocrine disrupters in aquatic systems, as reflected in national research programs like the Swiss NRP 50 “Endocrine Disruptors” and its consensus platforms. As a medium-term measure, the EU strategy on endocrine disruptors (SEC(2007)1635) uses the Endocrine Disruptor Testing and Assessment (EDTA) Task Force of the Organisation for Economic Co-operation and Development (OECD) along with other research activities. In particular the test methods of the OECD that are currently in validation or already validated may contribute to a better understanding of the extent of endocrine disruption, in particular if they are applied on environmental samples and in the context of risk-assessment strategies, for instance in waste water treatment. This article aims to give an overview and an evaluation on available and validated biological test systems for the detection of endocrine disruptive and reproductive effects in aquatic systems. Based on this a recommendation for a modular ecotoxicological test platform is given. The study focuses on test methods for sex hormone active substances. Material and methods On the basis of an extensive literature search and ongoing international validation efforts by the OECD for methods to detect endocrine disruptive effects, 15 biological test methods (5 in vivo and 10 in vitro) were selected. Comprising, for example, of eight OECD methods and three out of five in-vitro methods mentioned in the Global Water Research Coalition (GWRC) report “Tools to detect estrogenic activity in environmental waters” (Leusch 2008). Experienced users and developers were then asked to rate the test according to given relevant criteria. The resulting criteria profiles were compiled, compared, and evaluated. Results The methods were selected on the basis of validation status, distribution, their suitability for standardisation, and their proven sensitivity for environmental samples. We assumed that specific YES/YAS-procedures and the ER/AR Calux systems achieve the mentioned criteria. In the case that strong cytotoxicity of environmental samples affects the applicability of cellular reporter gene assays, alternatively a molecular receptor binding assay (e.?g. ELRA) could be used. Additional molecular receptor binding assays are currently in validation by the OECD. Modulating effects on steroidgenesis and probably even on aromatase activity can be detected by the OECD validated H295R Steroidgenesis Assay. Its applicability for environmental samples is currently tested. As in-vivo methods different fish assays (e.?g. Fish Screening Assay and the Zebrafish Embryo Test) were evaluated. For the detection of effects on the thyroid-associated hormone system the Amphibian Metamorphosis Assay (XEMA, for Xenopus Metamorphosis Assay) will soon be available as an OECD-Guideline. Because of trends in the international community to avoid tests with vertebrates in the future, only an optional recommendation was given for such tests. Reproduction toxicity, on the other hand, can be sensitively tested by the tests using the gastropod Potamopyrgus antipodarum, which, as invertebrate tests, do not require a permit to perform animal testing procedures. This test is also sensitive for many substances which are able to induce an endocrine disruption in vertebrates. Its validation is currently performed by the OECD. The applicability of the herein proposed test methods of the modular test platform for environmental-sample assessments were previously confirmed by several published scientific studies. Discussion We propose several test methods to be included in an application-oriented modular test platform. These tests should be suitable to efficiently indicate different mechanisms of endocrine disruption and reproduction toxicity, and may be employed in different situations according to their respective advantages. The modular test platform is able to detect impacts on the reproduction relevant effects in invertebrates, amphibians, and fishes. Furthermore the different mode of actions of estrogenic and androgenic receptor binding, steroid genesis and perhaps even the modulation of aromatase are detectable. A research report on the relevance of endocrine substances and pharmaceuticals in aquatic environments (Moltmann et al. 2007) showed that endocrine end-points of in-vivo tests (31 of 71 tested substances) tend to be more sensitive than general ecotoxicological end-points, such as mortality and growth. Consequently, endocrine and general-toxic effects should be detected in an integrative manner by ecotoxicological test platforms. Conclusions By combining literature research with a targeted query for information about the chosen test procedures it was possible to obtain a detailed overview about the current state-of-the-art of science and technology in the detection of hormone-active effects and reproduction toxicity. Ecotoxicological and regulative aspects were considered equally, and the applicability of the test procedures was evaluated. Because of the diversity of endocrine disrupting mechanisms, a modular combination of in-vivo and in-vitro methods in a joint test platform is needed to recognise and differentiate the transitions from hormone-active effects to endocrine disruption. Recommendations and perspectives Our study leads to a proposal of a modular ecotoxicological test platform, which offers an integrative detection of hormone-active and reproduction-relevant effects in the aquatic environment. The modular system presented here allows the switching between test modules according to the continuously developing state-of-the-art of science and technology as well as the incorporation of novel developments. Further standardisation of such methods for regulative applications is recommended.     

Qualität und Verwertungsmöglichkeiten von Holzaschen aus naturbelassenen Hölzern

Background, aim and scope The increasing use of wood for generating heat and electricity requires that more and more fuels be obtained directly or indirectly from the forest. Sound, sustainable recycling management calls for the return of any generated wood ash back to the forest to make use of the nutrients it contains. Similarly, recycling this ash in other locations such as agricultural land or private gardens can serve equally well as fertilizer. At the same time, it is critical that no accumulated pollutants be introduced into the nutrient loop. Wood ash that is heavily laden with such pollutants must not be considered for recycling. As part of this research project, commissioned by the Ministry for the Environment and Conservation, Agriculture and Consumer Protection of the State of North Rhine-Westphalia in Germany (MUNLV), ash samples of 209 wood-fired appliances generating between 10 and 4000?kW of heat performance were taken from throughout the federal state of North Rhine-Westphalia. Untreated wood, either forested or scrap, was used as the sole fuel for these appliances. Materials and methods All course ash and fly ash samples were analyzed to determine their composition of main nutrients, heavy metals, and the elements Fe, Cl, Si, Al and Na. The purpose of this analysis was to evaluate the suitability of this wood ash for reintroduction to forest soils or as fertilizer in other types of soil. Results The majority of the wood ash samples in this study contained sufficiently high amounts of nutrients to match the requirement for stand-alone fertilizers (PK-fertilizer, potash fertilizer). However, the heavy metal content was highly variable, with a mean content high enough to prohibit them from being classified per se as PK- or potash fertilizer for agricultural land. Due to the high quantities of cadmium, application of this ash to garden soils would likewise be ill-advised. Discussion On forest soils German law permits application of a mixture of potash fertilizer containing, at most, 30?% wood ash (course ash). Because of the high amounts of cadmium and copper, wood ash from our samples can only comprise a maximum of 28?% when added to typically used potash fertilizers. Higher percentage of wood ash would exceed the cut-off value established by the German Fertilizer Ordinance (Düngemittelverordnung – DüMV). Conclusions The application of wood ash on agricultural land and in private gardens is, rightfully so, highly regulated by law. However, the rules governing application of wood ash in the forest are much more lax. Determination of heavy metal content in wood ash cannot be used to determine compliance with DüMV standards because of the high content and fluctuating nature of heavy metals found. Recommendations and perspectives Presently an alternative approach for classifying the ecologic risk of wood ash recycling is being developed.