Polycyclic aromatic hydrocarbons in pine and spruce shoots-temporal trends and spatial distribution

In the framework of the German environmental specimen bank one-year old spruce shoots (Picea abies) and pine shoots (Pinus sylvestris) serve as bioindicators for the atmospheric pollution. Sampling is performed in two urbanized areas in western and eastern Germany (Warndt and Duebener Heide, respectively), and in seven different rural locations. Prior to archiving conifer shoots are continuously analyzed for a set of 17 individual polycyclic aromatic hydrocarbons (PAHs). The results from the two urbanized areas show that the atmospheric contamination with PAH has declined by about 75% between 1985 and 2004 at Warndt and by about 85% between 1991 and 2004 at Duebener Heide. However, summation operatorPAH concentrations stayed virtually constant at both locations since the end of the 1990s at levels of about 100 ng g(-1) wet weight (ww). In spruce shoots from rural areas current concentrations of PAHs are significantly lower and vary between 8 and 61 ng g(-1) ww. In all shoot samples the four low molecular aromatics phenanthrene, fluoranthene, pyrene, and chrysene dominate the pattern by contributing 60 to 90% to summation operatorPAH. The group of high molecular weight aromatics is dominated by benzo[b,j,k]fluoranthene, especially in spruce shoots originating from greater altitudes remarkable amounts of six and seven ringed PAHs could be detected. Despite the strong decrease of PAH concentrations in urban areas patterns of aromatics remained nearly unchanged in the observation period 1985 to 2004.     

Dispersion in Urban Environments; Comparison of Field Measurements with Wind Tunnel Results

A wind tunnel study was performed to determine the dispersion characteristics of vehicle exhaust gases within the urban canopy layer. The results were compared with those from a field monitoring station located in a street canyon with heavy traffic load. The agreement found was fair. In the second part of the paper it is shown how wind tunnel data can be utilized to supplement and thereby enhance the value of field data for model validation purposes. Uncertainty ranges were quantified which are inherent to mean concentration values measured in urban streets.     

Exposure reduction of seed treatments through dehusking behaviour of the wood mouse <Emphasis Type="Bold">(</Emphasis><Emphasis Type="Italic">Apodemus sylvaticus</Emphasis><Emphasis Type="Bold">)</Emphasis>

Background, aim and scope  

Seed treatments are widely used on cereals and other annual crops throughout Europe. Most of the formulated pesticide is found on the outside of the seed, the husk. Risk assessments of seed treatments are especially needed for granivorous mice living in the agricultural landscape e.g. for registration using the guidance for risk assessment for birds and mammals (EFSA 2009). The dehusking of seeds before consumption is a known behaviour of these mammals, but so far, no quantitative data on the reduction of exposure of seed treatments by dehusking were published. Therefore, we aimed at providing a first quantitative estimate of this behaviour-related exposure reduction for the wood mouse (Apodemus sylvaticus) with different seed types.     

Levoglucosan and other cellulose and lignin markers in emissions from burning of Miocene lignites

Levoglucosan (L), mannosan (M), galactosan (G) and other cellulose and lignin markers from burn tests of Miocene lignites of Poland were determined by gas chromatography–mass spectrometry (GC–MS) to assess their distributions and concentrations in the smoke. Their distributions were compared to those in the pyrolysis products of the lignites. Levoglucosan and other anhydrosaccharides are products from the thermal degradation of cellulose and hemicellulose and are commonly used as tracers for wood smoke in the atmosphere. Here we report emission factors of levoglucosan in smoke particulate matter from burning of lignite varying from 713 to 2154 mg kg^?1, which are similar to those from burning of extant plant biomass. Solvent extracts of the lignites revealed trace concentrations of native levoglucosan (0.52–3.7 mg kg^?1), while pyrolysis yielded much higher levels (1.6–3.5 × 10⁴ mg kg^?1), indicating that essentially all levoglucosan in particulate matter of lignite smoke is derived from cellulose degradation. The results demonstrate that burning of lignites is an additional input of levoglucosan to the atmosphere in regions where brown coal is utilized as a domestic fuel. Interestingly, galactosan, another tracer from biomass burning, is not emitted in lignite smoke and mannosan is emitted at relatively low concentrations, ranging from 7.8 to 70.5 mg kg^?1. Thus, we propose L/M and L/(M + G) ratios as discriminators between products from combustion of lignites and extant biomass. In addition, other compounds, such as shonanin, belonging to lignans, and some saccharides, e.g., α- and β-glucose and cellobiose, are reported for the first time in extracts of bulk lignites and of smoke particulate matter from burning these lignites.     

Stereochemistry of LinB-catalyzed biotransformation of δ-HBCD to 1R,2R,5S,6R,9R,10S-pentabromocyclododecanol

The haloalkane dehalogenase LinB from Sphingobium indicum B90A converts β-hexachlorocyclohexane (β-HCH), the most persistent HCH stereoisomer, to mono- and dihydroxylated metabolites. Recently, we reported that LinB also transforms α-, β- and γ-hexabromocyclododecanes (HBCDs), which are structurally related to HCHs. Here, we show that LinB catalyzes the hydroxylation of δ-HBCD to two pentabromocyclododecanols (PBCDOHs) and two tetrabromocyclododecadiols (TBCDDOHs). The stereochemistry of this enzymatic transformation was deduced from XRD crystal structure data of the substrate δ-HBCD and α₂-PBCDOH, one of the biotransformation products. Five stereocenters of δ-HBCD are unchanged but the one at C6 is converted to an alcohol with inversion from S- to R-configuration in a nucleophilic, S_N2-like substitution reaction. Only α₂-PBCDOH with the 1R,2R,5S,6R,9R,10S-configuration is obtained but not its enantiomer. With only two of the 64 PBCDOHs formed, these transformations indeed are regio- and stereoselective. A conformational analysis revealed that the triple-turn motive, which is predominant in δ-HBCD and in several other HBCD stereoisomers, is also found in the product. This shows that LinB preferentially converted reactive bromine atoms but not those in the conserved triple-turn motive. The widespread contamination with HCHs triggered the bacterial evolution of dehalogenases which acquired the ability to convert these pollutants and their metabolites. We here demonstrate that LinB of S. indicum also transforms HBCDs regio- and stereoselectively following a similar mechanism.     

Substance-related environmental monitoring strategies regarding soil, groundwater and surface water — an overview

Substance-related monitoring is an essential tool within environmental risk assessment processes. The soundness of policy decisions including risk management measures is often directly related to the reliability of the environmental monitoring programs. In addition, monitoring programs are required for identifying new and less-investigated pollutants of concern in different environmental media. Scientifically sound and feasible monitoring concepts strongly depend on the aim of the study. The proper definition of questions to be answered is thus of pivotal importance. Decisions on sample handling, storage and the analysis of the samples are important steps for the elaboration of problem-oriented monitoring strategies. The same applies to the selection of the sampling sites as being representative for scenarios to be investigated. These steps may become critical to handle for larger international monitoring programs and thus trigger the quality of their results. This study based on the work of an IUPAC (International Union of Pure and Applied Chemistry) task group addresses different kinds and approaches of substance-related monitoring of different compartments of soil, groundwater and surface water, and discusses their advantages and limitations. Further important aspects are the monitoring across policies and the monitoring data management using information systems.     

Air Emission Inventories in North America: A Critical Assessment

Abstract

Although emission inventories are the foundation of air quality management and have supported substantial improvements in North American air quality, they have a number of shortcomings that can potentially lead to ineffective air quality management strategies. Major reductions in the largest emissions sources have made accurate inventories of previously minor sources much more important to the understanding and improvement of local air quality. Changes in manufacturing processes, industry types, vehicle technologies, and metropolitan infrastructure are occurring at an increasingly rapid pace, emphasizing the importance of inventories that reflect current conditions. New technologies for measuring source emissions and ambient pollutant concentrations, both at the point of emissions and from remote platforms, are providing novel approaches to collecting data for inventory developers. Advances in information technologies are allowing data to be shared more quickly, more easily, and processed and compared in novel ways that can speed the development of emission inventories. Approaches to improving quantitative measures of inventory uncertainty allow air quality management decisions to take into account the uncertainties associated with emissions estimates, providing more accurate projections of how well alternative strategies may work. This paper discusses applications of these technologies and techniques to improve the accuracy, timeliness, and completeness of emission inventories across North America and outlines a series of eight recommendations aimed at inventory developers and air quality management decision-makers to improve emission inventories and enable them to support effective air quality management decisions for the foreseeable future.     

Comparative evaluation of life cycle assessment models for solid waste management

This publication compares a selection of six different models developed in Europe and America by research organisations, industry associations and governmental institutions. The comparison of the models reveals the variations in the results and the differences in the conclusions of an LCA study done with these models. The models are compared by modelling a specific case - the waste management system of Dresden, Germany - with each model and an in-detail comparison of the life cycle inventory results. Moreover, a life cycle impact assessment shows if the LCA results of each model allows for comparable and consecutive conclusions, which do not contradict the conclusions derived from the other models' results. Furthermore, the influence of different level of detail in the life cycle inventory of the life cycle assessment is demonstrated. The model comparison revealed that the variations in the LCA results calculated by the models for the case show high variations and are not negligible. In some cases the high variations in results lead to contradictory conclusions concerning the environmental performance of the waste management processes. The static, linear modelling approach chosen by all models analysed is inappropriate for reflecting actual conditions. Moreover, it was found that although the models' approach to LCA is comparable on a general level, the level of detail implemented in the software tools is very different.     

Crystal structure analysis of enantiomerically pure (+) and (-) beta-hexabromocyclododecanes

The molecular structures of individual HBCD stereoisomers are not elucidated yet. Recently, we isolated 8 of the 16 possible stereoisomers from a technical HBCD mixture and tentatively assigned their relative configurations. Herein we report on the isolation of enantiomerically pure (+) and (-) beta-HBCDs, both obtained from preparative chiral-phase liquid chromatography, and we present their absolute configurations determined from X-ray diffraction analysis. The absolute configuration of (+) beta-HBCD was found to be (1S,2S,5S,6R,9S,10R), while the one of (-) beta-HBCD was assigned to (1R,2R,5R,6S,9R,10S). The given structural information allows, for the first time, the unambiguous identification of these two important HBCD stereoisomers, which are typically found in technical products at proportions of about 3-5% for each enantiomer.     

Solid-state conformations and absolute configurations of (+) and (-) alpha-, beta-, and gamma-hexabromocyclododecanes (HBCDs)

Hexabromocyclododecanes (HBCDs) are high production volume chemicals used as flame retardants for plastics and textiles. They are currently produced in quantities exceeding 20,000 t/y. Despite this fact, the correct stereochemistry of most HBCDs is still not known. Six stereocenters are formed during bromination of cyclododecatrienes, resulting in mixtures of different stereoisomers. Considering all elements of symmetry, 16 different stereoisomers including six pairs of enantiomers as well as 4 meso forms are possible theoretically. Recently, we isolated 8 of the 16 possible stereoisomers from a technical HBCD mixture and assigned their relative configurations. Herein, we report on the isolation of 6 enantiomerically pure alpha-, beta-, and gamma-HBCDs, obtained from preparative chiral-phase liquid chromatography, and we present their absolute configurations, which were determined from X-ray diffraction analysis. The absolute configuration of (-) alpha-HBCD was found to be (1R,2R,5S,6R,9R,10S), while the one of (+) beta-HBCD is assigned to (1S,2S,5S,6R,9S,10R), whereas the one of (-) gamma-HBCD corresponds to (1S,2S,5S,6R,9R,10S). The given structural information allows the unambiguous identification of the six most important HBCD stereoisomers, which typically account for more than 95% of technical HBCDs. In addition, we compared the solid-state conformations of racemic and enantiomerically pure alpha-, beta-, and gamma-HBCDs. In all cases, vicinal dibromides adopted a synclinal (sc) conformation with torsion angles of 69+/-6 degrees. A unique structural motive was common to all examined HBCD solid-state conformations. This conserved structure was described as an extended triple turn consisting of an arrangement of three pairs of synclinal and two antiperiplanar torsion angles.