Bakterielle Biotestverfahren zur Bestimmung der Toxizität von Abfällen

For a risk assessment of wastes, fast and sensitive screening methods are required to detect possible toxic effects. In this study, different leachability methods (DIN 38414, part 4; EPA 1310; EPA 1320) were used to prepare aqueous leachates from different wastes; these leachates were rested in different bacterial toxicity test systems for possible toxic effects. As bacterial toxicity tests, the luminescent bacteria test and the growth inhibition test with activated sludge bacteria were used. The test systems showed a good agreement of the results from the different leaching methods, thereby indicating the reliability of the test systems used. The luminescent bacteria inhibition test showed a higher sensitivity than the growth inhibition test which is in good accordance with literature data. We conclude that both test systems are well suited to assess the toxic potential of aqueous waste leachates.     

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.     

Ansätze zur regionalen Quantifizierung von Methan aus Pflanzen

Background

Methane as a gas influencing our climate is of high importance according to the Kyoto-Protocol. The more precisely we can determine anthropogenic and biogenic sources, the more effective measures we can take to reduce the gas. Direct emission of methane from plants apparently contributes significantly to the total emission but has not been accounted for in emission balances until now.

Methods

A model was created to calculate methane emission for a short time period in regional resolution for Lower Austria and to relate the results to known literature.

Results and Discussion

First model results suggest that the amount of methane released from plants in relation to emissions from other known sources are of importance.

Perspectives

The uncertainties associated with both measurements and quantification require reduction by further research.     

Untersuchung von Abfällen mit biologischen Testverfahren zur Bewertung der Wassergefährdung

Wastes from three different types of waste treatment facilities (slag from a municipal waste incineration plant, slag granules from a pilot plant combining carbonization and incineration, mechanical and biological treated wastes) were examined to determine their hazard potential to different waters sites. The process temperature is seen to be the main difference between the three treatment processes. The wastes were extracted with water according to the German standard DIN 38414 S 4 and additionally at a constant pH value of 4. The leachates were investigated in a battery of aquatic bioassays and characterised physically and chemically. Every leachate revealed in a toxic effect at least in one test. The toxicity of the leachates prepared at a pH of 4 was significantly higher than the toxicity of the leachates prepared by extraction with water without pH adjustment. The leachates of the slag granules showed the lowest toxicity. On the basis of these experimental results, a scheme to derive Water Hazard Classes of wastes, which is presented in part II of this publication, was developed.     

Untersuchung von Abfällen mit biologischen Testverfahren zur Bewertung der Wassergefährdung

Wastes from three different types of waste treatment facilities were examined with bioassays to determine their hazard potential to waters (→Part I). All examined wastes showed toxic effects and have to be classified as hazardous to waters according to section 19g of the German Federal Water Management Act. The toxicity is probably caused by heavy metals in the leachates, especially copper. An evaluation pattern to classify wastes in the German system of Water Hazard Classes is presented. According to this proposal, a classification of the examined wastes into Water Hazard Class 1 seems to be appropriate. This classification does not describe the hazards resulting from the regular disposal on a landfill or from the utilisation of the treated wastes.     

Mikrobiologisch-ökotoxikologische Bodenuntersuchungen von zwei zur Unkrautbekämpfung mit hohen Dosierungen eingesetzten Fettsäure-Herbiziden

Goal and Scope

Products based on fatty acids (including acetic acid) are known in plant protection since more than 100 years to control several harmful organisms. In the following decades, however, they lost their importance due to the rapid development of ‘modern’ chemical pesticides. In the meantime some trials were run to control weeds with relatively high doses. The knowledge on its ecotoxic effects on soil microorganisms as a part of the soil fertility, however, is still incomplete.

Methods

Under laboratory conditions two agricultural soils were treated with different dosages of two products based on acetic acid and pelargonic acid (=nonanoic acid) as well as with a biocidal reference compound (e.g. dinitrophenol herbicide). The applied dosages were related to the concentrations in soil reached after simulated penetration of practical field amounts into upper soil layers. In some cases green manuring was simulated by adding lucerne meal to the soil. During the incubation for several weeks biomass-related microbial activities (dehydrogenase activity, substrate-induced shortterm respiration) as well as the mineralization of carbon and nitrogen (including nitrification) were measured.

Results and Conclusion

As compared to ‘normal’ pesticides (e.g. the reference compound) the effects of both test substances on soil microorganisms showed different behaviour. Nearly none of the effects typical for strongly biocidal compounds, namely a dose-related inhibition of microbial biomass combined with a stimulated mineralization (especially of nitrogen), occurred with the fatty acid products. Depending on the marked input of organic carbon by the higher dosages of fatty acid products and their rapid decomposition, especially of acetic acid, an increase of biomass-related parameters and of carbon mineralization combined with a reduction of the available nitrate content (e.g biological nitrogen immobilization) occurred for several weeks. By combining the results of the soil with that of lucerne meal-amended soil ‘real effects’ can be distinguished from those depending on the decomposition of the introduced carbon. In comparison with the strongly biocidal reference compound the two fatty acid products not only caused little microbiological-ecotoxicological impacts on the soil, but often stimulated important microbiological parameters for some time.

Recommendation and Perspective

As result of the trials we recommend an extended microbiological-ecotoxicological test spectrum especially for those plant protection products (pesticides) which should be applied at high dosages or if they contain higher amounts of well decomposable organic substances. This is necessary to distinguish dose-related enhanced biocidal activities induced by biocidal effects (including the subsequent mineralization of the killed microorganisms) from ‘real’ stimulations directly produced by the substrate.     

Auswahl repräsentativer Standorte zur Modellierung der Ausbreitung von gentechnisch veränderten Pflanzen in Nord-Deutschland

Goal and Scope

The use of genetically modified plants (GMP) in agriculture is increasing rapidly. While GMP in North and South America are already established an extensive cultivation in Germany is yet to come. Risk assessment on possible effects of released GMP are mainly based on empirical studies with a small spatial extent (laboratories, small-scale field trials). The joint research project ‘Generic detection and extrapolation of genetically modified rape (GenEERA)’ aimed at estimating the dispersal and persistence of genetically modified oilseed rape (Brassica napus) by the use of individual based models. The objective of the article at hand is to give a detailed account of the spatial variability of climate in Northern Germany (German Federal States of Brandenburg, Lower Saxony and Bremen Mecklenburg Western Pomerania, Schleswig-Holstein and Hamburg). Based on this, a method was developed that includes both, the determination of representative oilseed rapefields for modelling the dispersal of GM oilseed rape at field scale, and the subsequent generalisation of the results to landscapes.

Data and Methods

The statistically founded selection of modelling sites was performed by a compilation of available indicators within a GIS environment which are supposed to be important for the dispersal and the persistence of oilseed rape. Meteorological data on precipitation (P), air temperature (T), and sunshine duration (S) collected at up to 1,200 monitoring sites from 1961–1990 were as well as data on wind conditions (W) aggregated multivariate-statistically by Ward cluster analysis. An ecoregionalisation was used for characterising Northern Germany ecologically. Phenological data on the start of the oil seed rape bloom differentiated in the monitoring periods 1961–1990 and 1991–1999, respectively, were regionalised by performing variogram analysis and kriging interpolation. These maps were used to select appropriate Landsat images to identify rape fields by remote sensing algorithms as well as to define the respective flowering periods for individual based modelling.

Results

The separately generated P-T-S-W-Cluster were aggregated to four homogenic climatic regions. In combination with agricultural clusters defining typical landuse patterns (crop rotation, cultivation management) eight model regions were derived which describe the climatic and agronomic variations in Northern Germany. For each of these regions a representative monitoring site was selected serving for individual based modelling. At last, the modelling results were extrapolated back to the model regions applying corresponding GIS queries.

Discussion

The generated climatic regions reflect the transition of marine climate at the North Sea to continental climate in Northeast Germany. The shift in flowering of oil seed rape coincides with other studies on phenological changes of agricultural crops and wild plants.

Conclusions

Due to the huge calculation efforts and the lack of adequate land registers it was not possible to simulate the potential dispersal of GM oil seed rape at farm scale. Thus, generalisations were used to describe the variations of relevant ecological drivers affecting the dispersal of GMP. It could be shown that the aggregation of those factors to homogenic climatic regions was a successful approximation.

Recommendations and Perspectives

Due to the limited empirical data base it is necessary to validate and substantiate the modelling results by a GMP monitoring. The EU Directive 2001/18/EC on the deliberate release of genetically modified organisms into the environment stipulates assessment of direct and indirect effects of GMP on humans and the environment by case-specific monitoring and general surveillance. It should be realised as soon as possible, since the release and the cultivation of GMP in Germany have been started, already. The monitoring should be complemented by the implementation of a web-based geoinformation system (WebGIS) which enables access to relevant geodata and monitoring data and assists in analysing possible GMP impacts.     

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.     

Analyse „stetigkeitsbasierter“ Methoden zur Bestimmung von Stofffrachten in Fließgewässern

Aim and background

Increasing ecological awareness puts the load as a tool for water quality assessment in the foreground. Therefore it is very desirable to find optimal procedures for any given situation on basis of existing data. Criteria will be derived to fill that desire.

Method

The load for a water ingredient is an integrated entity of time-continuous loads (product of concentration and flow) for a given time, i.?e. a year (yearly load). Normally you can only observe a sample (in a statistical meaning) of these data. Therefore, load calculations vary with the concrete sample given. Each such calculation represents an estimation of the load, afflicted with some uncertainty. This uncertainty can be quantified, at least approximatively, by adding variance (scatter around “expected” mean) and the square of bias (divergence of “expected” mean from true mean). This quantity is called “mean squared error”. The methodological results will be illustrated by examples.

Focus

The main focus lies on the methodologies, which, besides data of concentrations observed discretely in time, additionally use quasi-continuously recorded data of other variates, namely the flow. For that situation, statistical models are developed and the load derived and estimated according to existing data. Hereby it is seen that all model based estimation formulae can be described as standard sampling formulae plus some additional terms which stem from comparison of some measurements (i.?e. mean) for quasi-continuous and discrete samples. This way a “continuity-correction” is performed on the standard formulae for the sampling case. This method is called “continuity-based” load determination.

Results

A surprising result is that no complicated mathematical-statistical models are necessary to determine the load. A simple linear concentration- or load-flow-model is sufficient. Additional variates lead, most of the time, to a larger mean squared error in load estimation, even when it is well known that they cannot detoriate the model fit. Only models which describe the concentration extraordinarily precise, near perfection, result in a smaller error.

Implications

It is enough to use one of the given formulae with some “continuity correction” to calculate a load. That can be done without using any software.     

Existierende dioxininventare weltweit und neue methodik zur erstellung von vergleichbaren und vollständigen emissionsinventaren

Presently, there are less than 20 inventories to estimate releases of dioxins and furans. According to a recent survey, 12,900 g TEQ of these unwanted byproducts are emitted into the atmosphere by 16 countries. Highest emissions are from the densely populated industrialized countries of the Northern hemisphere — Japan and the United States of America. Whereas the metal producing and recycling industry is the sector with the highest dioxin emissions in Europe, waste incineration is considered to be the major source in many other countries. Measures to reduce dioxin emissions have resulted in strong downward trends, as shown e.g. in Germany and Japan; however, potentials for further reduction have been identified. So far, countries have utilized own methods to calculate their dioxin emissions and the majority has addressed releases to air only. The future Stockholm Convention on POPs will require to continuously reduce dioxin emissions. In order to assist countries in inventory making, UNEP has produced the Toolkit, a methodology to establish comparable dioxin inventories that address releases to air, water and land, with products and in residues.     

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.     

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.     

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.     

Identifizierung toxischer Verbindungen in Sedimenten: Ansätze zur Integration von Wirkung und Bioverfügbarkeit

Sediments play an important role for aquatic ecosystem functions. However, they also act as sink, storage and source of lipophilic toxicants and metals. Effect-directed analysis (EDA) is a powerful tool to identify compounds causing adverse effects. In order to avoid misinterpretations and biased prioritization bioavailability needs to be considered together with effects. Bioavailability is a complex process finally resulting in the transfer of a so far particle bound molecule to the target location within the organism where it causes an effect. In order to operationalize this concept for EDA it can be divided into several partial processes. These include desorption from sediments and thus bioaccessibility, equilibrium partitioning of desorbable compounds between sediment, water and organisms driven by activity, and toxicological bioavailability as a result of toxicokinetics including resorption, transport, metabolization and excretion. Bioaccessibility is based on desorption kinetics and can be simulated with mild extraction methods e.?g. using TENAX. Equilibrium partitioning can be simulated with partition-based dosing techniques. First results with these approaches indicate that consideration of bioavailability increases the significance of polar sediment-associated toxicants relative to classical non-polar contaminants such as polycyclic aromatic hydrocarbons.     

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.