Prüfung der Auswirkungen von Pflanzenschutzmitteln auf Laufkäfer

The testing procedure for the effects of pesticides on carabid beetles is described and examples are given for important factors, e.g. temperature, type of soil, testing method and physiology of the test animal, which can influence the results of such tests. Risk assessment for pesticides, therefore, has to be carried out by experts. Additionally, a monitoring of effects should be carried out after the registration process in certain cases.     

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.     

Biozide in Gebäudefassaden – ökotoxikologische Effekte, Auswaschung und Belastungsabschätzung für Gewässer

Background, aim and scope Sources of organic micropollutants occuring in surface waters are often unknown. Regarding environmental risk assessments for surface waters, construction materials have as till now, not been given much consideration, although biocides used as preservatives are known to reach urban storm water runoff. The study focused on biocides for facades coatings and aimed (1) to determine ecotoxicological effect values, (2) to quantify the leaching behaviour and (3) to assess the environmental risk for surface waters using a dynamic transport model. Materials and methods Eight biocides used in resin based facade coatings were investigated. Some biocides are substances known as pesticides for agricultural purposes like diuron, carbendazim and terbutryn. Ecotoxicological effect values for aquatic organisms were determined for every biocide. Leaching of four biocides from a render under UV-irradiation has been investigated in the laboratory including the influence of varying temperatures. Using 80 irrigation intervals over 28 days, facade runoff was sampled and followed by biocide chemical analysis. The total losses were calculated based on the concentration patterns. These data were used for modelling the transport of cybutryn from facades to surface waters. Biocide specific effect values and leaching characteristics have been taken into consideration. Results Acute and chronic effect values as well as predicted no effect concentrations for the investigated biocides indicate their high potential to affect aquatic organisms. The leaching of four biocides (diuron, terbutryn, cybutryn, carbendazim) from the facade render under the experimental conditions delivers high concentrations in the beginning followed by an exponential decrease. Rising temperature increased the concentration of biocides in the runoff. The total losses were between 7?% and 29?% depending on the substances. More than half of the losses occur in the runoff within the first 15 min of runoff from a 60 min irrigation cycle. The modelling result for cybutryn underlines its high environmental risk for small surface waters. Discussion The leaching of the biocides, their potential ecotoxic effects and persistence show clearly that the environmental risk for surface waters and soils seems to be high for certain biocides; whereas for others the risk seems to be significantly lower. With respect water quality criteria, polluted facades runoff has to be diluted before runoff can enter the discharge. Diuron and carbendazim are however also used as pesticides and preservatives for other materials and cybutryn is also used as an antifouling agent. All pathways have to be evaluated in order to identify relevant sources and to act more efficiently with respect to water and soil protection. Conclusions Concentrations with high environmental risk are expected at new facades, especially at facades with thermal insulation. With the given low predicted no effect concentrations in a range of a few ng/L and large amounts of biocides applied in paints and renders, the environmental risk for common biocides used in facade coatings has to be investigated in laboratory and field scale. It seems plausible that source control measures as the most efficient and sustainable precautionary principle need to be evaluated. Recommendations and perspectives Biocides and additives applied in construction materials have to be taken into consideration as relevant sources when evaluating the quality of storm water runoff, discharge into urban areas and the impact to soil and surface waters. A sustainable construction material management and storm water management are required. It is expected that ongoing laboratory and field studies with exterior paints, renders and flat sheets for waterproofing containing biocides and additives will give further insight into their environmental impact.     

Bestimmung von Phthalsäureestern in Lebensmitteln, Frauenmilch, Hausstaub und Textilien

25 food samples, 5 mother’s milk specimens, 4 dust samples, and 16 textiles were analysed for phthalic acid esters. Phthalic acid esters were detected in all samples, with di (2-ethylhexyl) phthalate (DEHP) and di-n-butyl phthalate (DBP) being the most abundant phthalates. Raw milk samples revealed average concentrations of total phthalate of 0.1 mg/kg. Retail milk did not contain higher loads than raw milk, even storing samples until their “best-before” date did not result in elevated levels. Skimmed milk was less contaminated than whole milk. The higher concentrations of DEHP and total phthalates in cream samples are due to their higher fat content. With concentrations up to 1.54 mg/kg, ground hazelnuts, almonds, and nutmeg in plastic packagings showed relatively high levels. In infant food, only traces of DEHP and DBP could be found while other phthalic acid esters were not detectable. The mother’s milk samples also exhibited only low amounts of approx. 0.1 mg/kg, thus indicating that there is no accumulation of phthalate esters in the human body. Extraordinarily high concentrations were found in dust samples; with the levels ranging from 300 to 5370 mg/kg and DEHP being the major compound. This leads to the conclusion that the air path must play a considerable role in the transfer of phthalic acid esters. As dust contains considerable amounts of textile fibres, textiles were also included in the investigation. The phthalic ester levels in the textile samples ranged from 3.42 to 34.44 mg/kg. Therefore, the high phthalate contaminations of dust cannot be explained by textile fibres.     

Troposphärisches Ozon: Entstehung, Konzentrationsvariabilität und Wirkung unter dem Gesichtspunkt der Ozonminderung

This paper is an attempt to summarise and critically assess our knowledge on the formation, variation in concentrations and impact of ozone under the aspect of abatement strategies. The present ozone budget is determined to about 50% through human activities where methane and carbon monoxide contribute more than 80% to ozone formation. This “residual” or “background” ozone determines the annual mean ozone concentration. Due to the long time period (months and years) required for CH₄ and CO oxidation, both compounds do not contribute to the excessive ozone concentrations often found in the summer. Moreover, the increase in tropospheric ozone is becoming a global problem. Because emissions of CH₄ and CO are increasing globally, the “background” ozone will also increase in the future. Non-methanehydrocarbons (NMHC) may produce O₃ within a few days because of their high reactivity concerning oxidants. For photochemical O₃ formation, the source-sink budget has to be taken into account for making an estimation of the net ozone formation. Ozone accumulation only occurs when the removal potential (especially heterogeneous processes within clouds, but also a reduction in the net photochemical formation) of the air mass is small. This “excess” ozone has been reduced successfully within the last decade, most likely as a result of automobile catalyst use. An impact of O₃ on humans has been found only for concentrations >100 ppb. Thus, O₃ should not be a problem for people. Although vegetation is much more sensitive (esp. conifers), it is not possible to present reliable thresholds at present. There is evidence that the dose (accumulation exposure) is an important criterion. Therefore, a mean annual concentration which may possibly be increasing further should be the target of air pollution controls. Former measures and ideas of ozone controlling have no usefulness in this sense.     

Abschätzung des Beitrages kommunaler Kläranlagen an Schadstoffkonzentrationen in Oberflächengewässern

A number of products, such as washing agents or pharmaceuticals, enter the hydrosphere mainly with municipal wastewater. In this case the predicted environmental concentrations (PEC) of substances are largely determined by their elimination in municipal wastewater treatment plants and by the dilution ratio of wastewater in the rivers. In this article some rough estimates of the wastewater ratio in German rivers are presented and as a starting point for a more complex model for calculating the PEC more exactly, data on the fluctuation of river flow rates are shown.     

Raumbezug und Repräsentativität in der Ökologischen Flächenstichprobe

The quality of regionalizations can only be evaluated with regard to its specific purposes. In environmental monitoring, regionalizations, besides being an analysis tool, has a great importance on the selection of monitoring sites. The article describes the relationship between regionalization, selection procedure and representativeness using the example of Ecological Area Sampling (EAS) and presents the regionalization which was tested in an EAS pilot study.     

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.     

PEPC-Aktivität

The criteria currently used to determine the extent of novel forest decline areleaf loss andyellowing of leaves. However, these criteria have only a limited value for indicating damage of woody trees, especially the early stages. Therefore, physiological-biochemical parameters will be useful to measure the extent of forest decline. Results from several natural spruce stands indicate that in needles with early signs of damage and needles with severe damage PEPC activity is significantly higher than in needles of healthy plants. Therefore, PEPC activity can reveal beginning damage and may be used as abiochemical indicator for damage assessments of spruce. The influence of air pollutants on PEPC activity in spruce needles was measured in fumigation chambers and open-top chambers; PEPC activity was shown to be affected by long-term exposition only.     

Probabilistische Schätzung der inhalativen Exposition vs. Punktschätzung, dargestellt am Beispiel der Freisetzung von Xylol aus Farben

Estimations of consumer exposure by inhalation have been calculated taking point estimates and were compared to estimates from a probabilistic approach using Monte Carlo analysis. The calculation is based on a model in which the liberation of the highly volatile substance, xylene is only limited by the velocity of administration. The loss of the substance is limited by the air exchange rate. It is also assumed that the substance is used in a single room. Other compartments were not considered. The distribution of xylene in solvent based paints was evaluated by probability analysis of the BgVV product data base. In the products there were xylene concentrations in a range between ～1 and 44% with a median concentration of 11,2%. For “normal-case” assumptions the exposure estimate differed between single-point and probabilistic calculations: The peak concentration in a room was 0,99 g/m³ taking the single-point and 0,49 g/m³ taking the distribution. The average concentration during duration of use was 0,16 g/m³ and 0,083 g/m³, respectively. Interestingly, comparison with calculations taking the EPA-SCIES programme revealed similar concentrations showing that models are comparable.     

Abschätzung der Einträge von polyzyklischen aromatischen Kohlenwasserstoffen in deutsche Gewässer

Background, aim, and scope Polycyclic aromatic hydrocarbons (PAH) result from incomplete combustion of almost every organic materials, e.?g. due to forest fires, residential heating, combustion engines, grilling, or smoking. PAH are predominantly distributed over the air-path. Their usage in products (e.?g. moth-balls) has been limited strictly or completely forbidden in the past. In the context of the EU Water Framework Directive (WFD), the single substances anthracene, fluoranthene and naphthalene, as well as PAHs as group of substances, are listed as “priority” substances. Background of this work is a first compilation of sources of PAH emissions, and in this context, the collection of all relevant data and information to calculate the total emissions into surface waters in Germany. Materials and methods Within the scope of diverse research projects, funded by the German Environmental Agency, the available data material concerning PAH input in surface waters has been analyzed by the Fraunhofer Institute for Systems and Innovation Research. On the basis of the collected data, a first evaluation of relevance of the different sources has been conducted using the model MONERIS. Results As a result of the atmospheric deposition, PAHs enter, to a large extent, surface waters directly or indirectly through surface runoff (e.?g. urban areas, wastewater treatment plants, erosion). Discussion Although there is still additional research need for some of the covered PAH sources, a noticeable distribution pattern of relevance emerges. Conclusions The scenarios, based on the currently known sources, show that the implementation or the neglect of emission reduction measures in the field of diffuse air-borne PAHs are crucial for the further development of the deposition of PAHs in surface waters. More far-reaching studies are necessary, e.?g. concerning emissions from inland navigation/motor boats, the inhomogeneous source “products”, or the path “erosion”. Recommendations and perspectives According to the EU-WFD, all depositions, emissions and losses of “priority hazardous” classified substances, such as the group of PAHs, have to be stopped or gradually finished in the long term. Until the year 2015, environmental quality standards (EQS) have to be met for all “priority substances”. Presently, the EQS often are not completely fulfilled for many substances of the PAH group, including benzo(a)pyrene. Reduction measures are necessary within diverse areas, especially concerning diffuse atmospheric emissions (e.?g. “residential heating”).     

Huminstoffe in Sedimentporenwässern ausgewählter Bundeswasserstraßen

Humic substances are an important component of organic carbon in natural waters. Their character and properties are determined by the sources and the processes of their origin. Humic substances are not exclusively refractory compounds, but they are involved in several transformation processes in the water. It is not possible to directly analyze humic substances, therefore several methods were applied for their characterization. The presented LC-OCD-technique is a size-exclusion-chromatography with online UV- and carbon detection. Carbon fractions, e.?g. humic substances were differentiated by their molecular size. The portion of humic substances in sediment porewaters of the rivers Elbe, Rhine, Danube, Oder, Müritz-Elde-Waterway was determined. With only a few exceptions it ranges from 50 to 67?% of the dissolved organic carbon. The high molecular weight fraction accounts for 10 to 34?%, and the fraction of the low molecular weight substances was from 7 to 37?%. The ratio between the spectral absorption coefficient (254?nm) and the organic carbon is called SUVA (L/mg × m) and is an inidicator of the proportion of unsaturated bonds in the humic substances. Both high molecular herbal components (e.?g. cellulose, lignin) and biological degradiation products (e.?g. amino acids, sugar) are involved in sediment porewater transformation and degradiation processes. This demonstrates the distribution of the dissolved organic carbon between the fractions.     

Stabilitätsverhalten von ausgewählten anorganischen Spurenstoffen in Niederschlagsproben

The stability of H⁺, NH ₄ ⁺ , and PO ₄ ^3? ions in rainwater samples was in vestigated under different conditions cf storage and transport. Microbiological and physicochemical processes account for changes. Suppression of microbiological activities in deposition networks using conventional analyses may be achieved by adding AgCl-powder and by cooling to +4 °C.