Analytical Investigations on a Releasing Agent Application in Aluminium Diecasting (6 pp)

Background, Aims and Scope Releasing agents, applied in the aluminium diecasting process, usually consist of water, oils, waxes, polysiloxanes, as well as of a set of additives like emulsifiers, corrosion inhibitors, and biocides. During spray application and part release, gases and aerosols are emitted into workplace air. The chemical compositions of these emissions are determined by the components of the releasing agents and their reaction products formed during thermal stress of more than 700 °C. In the frame of the joint project, the analytical tasks were to develop an appropriate sampling strategy for this production environment, to draw conclusions about the occurrence of hazardous chemicals from production plant studies and from laboratory-scale thermolysis experiments, and to determine the biodegradability of customary releasing agents. Methods During realistic test production, active air sampling was performed in a production hall using different adsorption materials. Cotton fabric sheets were positioned in the production area as passive samplers. Thermolysis experiments were performed at 600 °C with sealed quartz ampoules. The biodegradability of different releasing agents was determined according to German industry standard DIN 51828 (2000). For analyses, GC/MS (headspace), FTIR, HPLC, IC, and ICP-OES techniques were applied. Results and Discussion The substance spectrum, which was found in workplace air, was dominated by saturated and non-saturated aliphatic hydrocarbons. Besides these, alcohols, alkyl phenols, xylenes and other benzene derivatives, aldehydes, glycols, carboxylic acid esters, and amides were present. The German limiting value of 40 mg/m3 of complex hydrocarbon mixtures in a diecasting workplace atmosphere was clearly under-run. Total hydrocarbon contents ranged between 2.7 and 6.3 mg/m3. Five different PAH were found in the air close to the diecasting machine, with maximum concentrations between 0.05 and 3.06 μg/m3. Concentrations of nonylphenols ranged from 10 to 200 μg/m3, and those of triethanolamine from 20 to 30 μg/m3. From 17 elements analyzed, only B, Fe, P, S, Si, and Ti were emitted in small amounts. It was striking that the PAH patterns resulting from thermolysis experiments were quite the same compared to those determined during the diecasting process. An influence of water and of Fe/Al on the composition of the thermolysis products could mostly be shown. The degrees of biodegradation of three releasing agent extracts after 21 days were 21%, 29%, and 55%, respectively. Conclusion A sampling strategy was developed, which allows an emission assessment for the industrial process of aluminium diecasting. It enabled one to control limiting values, to characterise a wide variety of compounds emitted, and to identify and quantify relevant pollutants. Only a few hazardous substances could be detected during the exemplary use of one releasing agent within the compounds emitted into workplace air. Indications were found, that the prediction of the formation of harmful substances from releasing agent components should be possible via thermolysis experiments. The biodegradability test can serve to assess the expenditure of disposal of the usual leakage run-off of excess agent during production. Recommendation and Outlook Investigations on further differently composed releasing agents, e.g. powders, would be desirable. A substitution of nonylphenol ethoxylates by less harmful components would surely be an improvement of a releasing agent with regard to work safety and health care, because of avoiding the emission of toxic and endocrine active nonylphenols. The surprisingly wide range of biodegradability of the investigated releasing agents points to an optimization potential, that has obviously not yet been considered.     

BTX concentrations near a stage II implemented petrol station

A combined monitoring and dispersion modelling methodology was applied for assessing air quality at three different levels of proximity to the selected service station: (I) next to the fuel pumps, (II) in the surrounding environment, and (III) in the background. Continuous monitoring and passive sampling were used for achieving high temporal and spatial resolution, respectively. A Gaussian dispersion model (CALINE4) was used for assessing the road traffic contribution to the local concentrations under different meteorological conditions. It was established that Stage 2 vapour recovery reduces BTX concentrations not only near the pumps, but also in their surrounding environment. However, there is evidence that the efficiency of the system is wind speed dependent. The modelling simulation of the worst case wind scenario revealed the significance of local traffic emissions. It was shown that the traffic contribution even from a single road in the vicinity of the station can, under certain conditions, be higher than the contribution of the station itself to the local BTX levels. Finally, after comparison with previous studies, the concentrations measured near the service station (which was situated in a rural environment) appear to be lower than those observed in busy street canyons in city centres. It can be concluded, although Stage 2 recovery system effectively reduces working VOC losses in service stations, that it will only have a limited positive impact on local air quality if the service station is located in a heavily polluted area.     

Genotoxic and teratogenic potential of marine sediment extracts investigated with comet assay and zebrafish test

Organic extracts of marine sediments from the North Sea and the Baltic Sea were investigated with two toxicity assays. The comet assay based on the fish cell line Epithelioma papulosum cyprini (EPC) was applied to determine the genotoxic potential; zebrafish embryos (Danio rerio) were used to quantify the teratogenic potential of the samples. EC(50) values were calculated from dose-response curves for both test systems. Highest teratogenic and genotoxic effects normalised to total organic carbon (TOC) content were detected in sediment samples of different origins. Polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) are not likely to be the causes of the observed effects, as demonstrated by a two-step fractionation procedure of selected extracts. The toxic potential was more pronounced in fractions having polarity higher than those possessed by PAHs and PCBs. The suitability of the two in vitro test systems for assessing genotoxic and teratogenic effects of marine sediment extracts could be demonstrated.     

Female choice in a promiscuous wild guinea pig,the yellow-toothed cavy (<Emphasis Type="Italic">Galea musteloides</Emphasis>)

Promiscuity is traditionally considered to increase only male reproductive success but, more recently, female benefits are also assumed to be the driving force for promiscuous mating. The yellow-toothed cavy (Galea musteloides) is characterised by an extremely high degree of multiple paternity (>80%), and females have greater offspring viability after mating multiple males. However, so far it is not clear whether or not it is the female's decision that leads to mating with more than one male. To elucidate the female's role in bringing about promiscuity, female yellow-toothed cavies were given the choice between four different males each, in a mate-choice apparatus that simultaneously prevented monopolisation and harassment of the females by the males. In 10 of the 12 choice tests, mating occurred. Nine of these ten females actively sought copulations with more than one male, and their mating behaviour was displayed in a way that might have favoured the mixing of sperm. At the same time, they significantly preferred heavier and more frequently courting males. These results show that female yellow-toothed cavies are actively involved in mating with more than one male. Thus, the present study is the first to show that in a species in which females produce more viable offspring as a consequence of polyandrous mating, these females are indeed motivated to actively bring about promiscuity. Nevertheless, females are selective in the choice of their mates. Thus, both sperm competition and direct female choice seem to be important for the increased offspring viability due to promiscuous mating.     

Problemfeld Seeufer am Beispiel Bodensee

The shores of many Central European lakes located in the hinterland of large conurbations are heavily endangered by intensive settlement, traffic, sewage input, manipulation of the water level, tourism and recreation. This increasing impact has negatively affected the function of the lake shore in respect to conservation and species protection, to water protection and its importance for recreation. This paper describes the overlap of the multiple uses and the precautions planned since 1981 on the national and international level to guarantee the essential multiple functionality, e.g. as drinking water reservoir for the conurbations in the northern part of Baden-Württemberg, as supraregional centre for water sports and tourism, and as an important environment for endangered plant and animal species. Management measures include regional planning as well as the international water protection and preservation with many contributions from non governmental international organisations Given a high agreement concerning these aims, many indispensable actions could successfully be realised on the political and administrative level. On the basis of 14 topics we follow the development since 1981, most recently also driven by the EU (FFH/Natura 2000), Water framework directive). Backlogs became obvious for four topics: 1. The lack of efficient reviews on completed measures, 2. gaps in basic understanding, 3. The dragging harmonisation of an intergrated shore protection program across the borders, and 4. the lack of concepts for a sustainable development including plans for monitoring.     

Ozone and forests in South-Western Europe

The paper provides basic information about background, objectives and structure of O3SWE (Ozone at the permanent monitoring plots in South-Western Europe), an international co-operative project aimed at evaluating O3 concentrations, cumulative exposure, uptake and effects on forest vegetation in four countries of South-Western Europe (France, Italy, Luxenbourg, Spain and Switzerland). The project covers a total of 83 permanent plots of the EU and UN/ECE intensive forest monitoring programme and span over three years of investigation (2000-2002). The O3SWE project aims to demonstrate how, using data collected routinely in an intensive forest monitoring network, O3 exposure, flux and effects can be assessed and exceedances critically evaluated.     

Preliminary results of modeled ozone uptake for Fagus sylvatica L. trees at selected EU/UN-ECE intensive monitoring plots

The objective of this study was to establish whether EU and UN-ECE/ICP-Forests monitoring data (i) provide the variables necessary to apply the flux-based modeling methods and (ii) meet the quality criteria necessary to apply the flux-based critical level concept. Application of this model has been possible using environmental data collected from the EU and UN-ECE/ICP-Forests monitoring network in Switzerland and Italy for 2000-2002. The test for data completeness and plausibility resulted in 6 out of a possible total of 20 Fagus sylvatica L. plots being identified as suitable from Switzerland, Italy, Spain, and France. The results show that the collected data allow the identification of different spatial and temporal areas and periods as having higher risk to ozone than those identified using the AOT40 approach. However, it was also apparent that the quality and completeness of the available data may severely limit a complete risk assessment across Europe.     

Determination of selected quaternary ammonium compounds by liquid chromatography with mass spectrometry. Part II. Application to sediment and sludge samples in Austria

Soxhlet extraction and high-performance liquid chromatography (HPLC) coupled to tandem mass spectrometry detection (MS/MS) was used for the determination of selected quaternary ammonium compounds (QACs) in solid samples. The method was applied for the determination of alkyl benzyl, dialkyl and trialkyl quaternary ammonium compounds in sediment and sludge samples in Austria. The overall method quantification limits range from 0.6 to 3 microg/kg for sediments and from 2 to 5 microg/kg for sewage sludges. Mean recoveries between 67% and 95% are achieved. In general sediments were especially contaminated by C12 chain benzalkonium chloride (BAC-C12) as well as by the long C-chain dialkyldimethylammonium chloride (DDAC-C18) with a maximum concentration of 3.6 mg/kg and 2.1mg/kg, respectively. Maxima of 27 mg/kg for DDAC-C10, 25 mg/kg for BAC-C12 and 23 mg/kg for BAC-C14 were determined for sludge samples. The sums of the 12 selected target compounds range from 22 mg/kg to 103 mg/kg in the sludge samples.