Hazardous halogenated substances formed during combustion processes

The results of the emissions from combustion processes and/or from fire accidents show the risk to man and his environment and thus the need for strict legislation and critical analysis of unwanted compounds. These substances or their thermolysis products are often due to incomplete combustion or may result from the interaction of various substances.

In the following we report the formation of octachlorostyrene (OCS) and of high‐toxic substances such as polybrominated dioxins (PBrDD's), dibenzofurans (PBrDF's) by the combustion.

In order to determine a possible source of the non‐manufactured compound OCS, we conducted several model experiments in a combustion chamber at various temperatures from 400 °C to 800 °C. The thermolysis of chlorinated solvents like chloroform or of chlorinated aromatice like pentachlorobenzene produced—among other chlorinated substances—OCS as one of the major products.

Analogous combustion experiments with polyester plastics containing decabromodiphenylether as flame retardant and antimony trioxide as Synergist led to PBrDD's and PBrDF's. Here antimony trioxide seems to play an important role because in absence of this oxide, PBrDD's and PBrDF's were not found in our experimental conditions.     

Current state of heavy metal contents in Vienna soils

This study presents the current state of heavy metal contents in both urban and forest soils within the city area of Vienna, Austria. Based on a systematic survey of urban soils and on targeted sampling in forest areas, local and regional anomaly thresholds are derived using statistical methods and considering regional distribution patterns. For urban soils, local anomaly thresholds of elements Cu (60?mg/kg), Hg (0.5?mg/kg), Pb (100?mg/kg) and Zn (200?mg/kg) exceed national guideline values for uncontaminated urban soils and according to Austrian legislation fall into the category “anthropogenic contamination present but no damage to plants, animals or humans detectable”. In forest soils within the city, thresholds are very similar to reference values for similar geological settings outside the city, apart from higher concentrations of elements Cr and Ni (threshold values of 107 and 64?mg/kg, respectively). Grouping urban soils according to land use reveals that Cd contents are 25?% higher, Pb contents 36?% higher, in traffic and industrial areas than in parks and like Cu, Hg and Zn, these elements can be shown to be at least partly caused by anthropogenic contamination. A dependency between heavy metal concentrations in soils and underlying geological units is shown within the flysch zone at the western city margin where the contents of elements Co, Cr, Cu, Ni and V are controlled by geology and reveal distinct differences between geological units. In built-up areas, no clear dependency between heavy metal contents in soils and geology is evident as urban soils represent accumulations by anthropogenic activity rather than in situ weathering products of underlying sediments.     

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.     

Beurteilung des Ozonrisikos für die Waldregionen Bayerns am Beispiel des Jahres 2002 und des Extremtrockenjahres 2003 auf der Basis der externen Ozonexposition und der internen Ozonaufnahme

Background, aim, and scope Increasing background concentrations of ground-level tropospheric ozone and more frequent and prolonged summer drought incidences due to climate change are supposed to increase the stress on Bavarian forests. For such scenarios growth reduction and yield losses are predicted. Sustainable forest management in Bavaria aims to significantly increase the proportion of beech (Fagus sylvatica L.) because of its broad ecological amplitude. In our regional study different approaches for calculating ozone impact were used to estimate the risks for Bavarian forests in the average climatic, rather moist year 2002 and the extremely dry year 2003.Materials and methods Measurements were conducted for eleven forest ecosystem sites and two forest research sites representing typical Bavarian forest stands under different climatic conditions and situated in different altitudes. For risk assessment currently used approaches were applied either based on the calculation of the cumulative ozone exposure (external dose; MPOC maximal permitted ozone concentration; critical level AOT40_phen? accumulated ozone exposure over a threshold of 40 nl [O₃] l^–1, for the effective phenolgy of beech) or based on the calculation of the phytomedically relevant ozone flux into the stomata (internal dose, critical level AF_st>1,6, accumulated stomatal flux above a flux threshold of 1.6 nmol O₃?m^–2 PLA; PLA = projected leaf area). For calculations continuously recorded ozone concentrations and meteorological and phenological data from nearby rural open field background measuring stations from the national air pollution control and from forested sites were used. Additionally ozone induced leaf symptoms were assessed.Results The exposure-based indices AOT40_phen and MPOC as well as the flux-based index AF_st>1.6suggest that Bavarian forests are at risk from O₃ during a rather moist average year concerning climate conditions (2002) as well as in an extreme dry year (2003). Thus, growth reductions of 5?% are predicted when thresholds are exceeded. Threshold exceedance occurred in both years at all plots, mostly already at the beginning of the growing season and often even many times over. Ozone induced leaf symptoms could be detected only on a few plots in a very slight occurrence.Discussion The results for the applied critical level indices differed depending on climatic conditions during the growing seasons: Regarding exposure-based indices, the highest degree of threshold exceedance occurred in the dry year of 2003 at all plots; the flux-based approach indicated the highest stomatal ozone uptake and thus an increased risk at moist sites or during humid years, whereas the risk was decreasing at dry sites with prolonged water limitation. Hence, soil and accordingly plant water availability was the decisive factor for the flux-modelled internal ozone uptake via stomata. Drought and increased ozone impact can generate synergistic, but also antagonistic effects for forest trees. At water limited rather dry forest sites restricted transpiration and thus production, but concurrently lower ozone uptake and reduced risk for damage can be expected.Conclusions, recommendations, and perspectives For realistic site-specific risk assessment in forest stands the determination of the internal ozone dose via modeling flux based internal stomatal ozone uptake is more appropriate than the calculation of the external ozone dose. The predicted 5?% growth reductions are in discrepancy with the frequently observed increment increase during the last decades in forest stands. Comprehensive and significant statistical verification for ozone induced forest growth reduction as well as the systematic validation of thresholds for ozone in the field is still lacking. However, a multiplicity of different specific new and retrospective growth analysis data should allow closing the gap. Moreover, the determination of canopy transpiration with sap flow measurements is a novel approach to provide cause-effect related, site specific results for the effective internal ozone dose as well as for canopy water supply and consecutively for regional risk estimation. A further future objective is the refinement of O₃ flux modelling by further consideration of soil/water budget characteristics and the above mentioned improved estimations of crown and canopy transpiration. Further, the introduction of threshold ranges for forest trees in view of their specific regional climatic conditions and their validation in real forest stands is necessary for developing meaningful ozone risk predictions for forests.     

Database-driven models of the world's Large Marine Ecosystems

We present a new methodology for database-driven ecosystem model generation and apply the methodology to the world's 66 currently defined Large Marine Ecosystems. The method relies on a large number of spatial and temporal databases, including FishBase, SeaLifeBase, as well as several other databases developed notably as part of the Sea Around Us project. The models are formulated using the freely available Ecopath with Ecosim (EwE) modeling approach and software. We tune the models by fitting to available time series data, but recognize that the models represent only a first-generation of database-driven ecosystem models. We use the models to obtain a first estimate of fish biomass in the world's LMEs. The biggest hurdles at present to further model development and validation are insufficient time series trend information, and data on spatial fishing effort.     

Importance of jumbo squid Dosidicus gigas (Orbigny, 1835) in the pelagic ecosystem of the central Gulf of California

The Humboldt squid is an important predator in the pelagic ecosystem of the central Gulf of California and the commercial catch of this species has increased over the past decade, probable due to a decrease of several top predators (sharks, large pelagic fish and the marine mammals) and the optimal feeding conditions in this area. Its high abundance and important position in the pelagic food web was quantified through two trophic models of the pelagic ecosystem of the central Gulf of California. Models represented conditions in 1980 and 2002, to document the decadal changes in ecosystem structure and function. The models were composed of 18 functional groups, including marine mammals, birds, fish, mollusks, crustaceans, and primary producers. Model results show direct negative effects on principal prey groups such as myctophids and pelagic red crab and positive effects on sharks, marine mammals and specifically sperm whales. It thus appears that the jumbo squid has an important role in the ecosystem and plays a central part in the overall energy flow as main food item for most top predators, and due to its predation of organisms on lower tropic levels.     

Ecological scenarios analyzed and evaluated by a shallow lake model

We applied the complex ecosystem model EMMO, which was adopted to the shallow lake Müggelsee (Germany), in order to evaluate a large set of ecological scenarios. By means of EMMO, 33 scenarios and 17 indicators were defined to characterize their effects on the lake ecosystem. The indicators were based on model outputs of EMMO and can be separated into biological indicators, such as chlorophyll-a and cyanobacteria, and hydro-chemical indicators, such as phosphorus. The question to be solved was, what is the ranking of the scenarios based on their characterization by these 17 indicators? And how can we handle high quantities of complex data within evaluation procedures? The scenario evaluation was performed by partial order theory which, however, did not provide a clear result. By subsequently applying the hierarchical cluster analysis (complete linkage) it was possible to reduce the data matrix to indicator and scenario representatives. Even though this step implies losses of information, it simplifies the application of partial order theory and the post processing by METEOR. METEOR is derived from partial order theory and allows the stepwise aggregation of indicators, which subsequently leads to a distinct and clear decision. In the final evaluation result the best scenario was the one which defines a minimum nutrient input and no phosphorus release from the sediment while the worst scenario is characterized by a maximum nutrient input and extensive phosphorus release from the sediment. The reasonable and comprehensive results show that the combination of partial order, cluster analysis and METEOR can handle big amounts of data in a very clear and transparent way, and therefore is ideal in the context of complex ecosystem models, like that we applied.     

Chemisch-analytische Untersuchung von Arsenkampfstoffen und ihren Metaboliten

Arsenic containing chemical warfare agents (cwa) are persistent in the environment and continue to contaminte soil and ground water. In this paper the chemical rections of the cwa diphenylarsine chloride (CLARK I), phenylarsine dichloride (PFIFFIKUS), ethylarsine dichloride (DICK) and of chlorovinyl arsenic compounds (LEWISITE) are shown. The posibilities of the detection and determination of this cwa and their metabolites are presented.