Regio- and stereoselective isomerization of hexabromocyclododecanes (HBCDs): kinetics and mechanism of beta-HBCD racemization

Hexabromocyclododecanes (HBCDs) are high production volume chemicals currently produced in quantities exceeding 20000ty(-1). They are used as flame retardants for plastics and textiles. HBCDs are thermally labile compounds, rapidly decomposing at temperatures above 250 degrees C to form bromine radicals, which scavenge other radicals formed during pyrolysis. But certain HBCD stereoisomers must reach the environment without decomposition, because their levels in soils, sediments, and biota are increasing worldwide. The fate of individual HBCD stereoisomers during production, product use, disposal, and transformation in the environment remains unclear. Herein we report on the thermally induced, highly selective isomerization of (+) and (-)beta-HBCD. Regio- and stereoselective migration of only two of the six bromine atoms resulted in the racemization of both beta-HBCDs. First order rate constants (k(rac)) increased from 0.005, 0.011, 0.021, to 0.055min(-1) at 130, 140, 150, and 160 degrees C, corresponding to half life times tau(1/2) of 143, 63, 29, and 14min, respectively. From the deduced kinetic model, we conclude that any thermal treatment of enantiomerically enriched beta-HBCDs in the range of 100-160 degrees C will result in a loss of most optical activity within few hours. The simultaneous inversion of two asymmetric centers occurred with perfect stereocontrol. Selectively, vicinal dibromides with the RR- and the SS-configurations migrated at these temperatures. An intramolecular reaction mechanism with a four-center transition state is postulated, based on the obtained stereoisomer pattern and the observed reaction kinetics. Crystal structure analysis revealed that all vicinal dibromides in beta-HBCDs prefer synclinal (gauche) conformations. However, an antiperiplanar (staggered) conformation is assumed to facilitate the concerted 1.2-shifts of both bromine atoms, resulting in an inversion of both neighboring carbon atoms. First experiments with other HBCD stereoisomers suggest that the presented isomerization mechanism is of relevance for those stereoisomers as well.     

Recycling-oriented characterization of polyolefin packaging waste

Packaging waste is one of the main sources of secondary polyolefins. It is essential to characterize polyolefins derived from this waste stream in such way, that not only mechanical sorting methods can effectively separate, but also that on-line sensor systems can quantitatively assess their distribution. The characterization methodology is hierarchical, relating all properties of waste particles in any phase of the processing ultimately to the input End-Of-Life products. The present paper documents a pre-concentrate obtained by hand picking of mixed Romanian household waste. Investigations have been addressed to identify the composition of this polyolefin waste stream, to study the polyolefin density distribution, to distinguish the polymer manufacturing methods (i.e. injection molding and blow molding) by flake physical properties and finally to perform all the required characterization and identification by hyperspectral imaging. On the basis of these analyses, polyolefins from packaging wastes can be recycled by density separation and their rheological properties and wall thickness indicate the molding procedures. Hyperspectral imaging based procedures have been also applied to set up quality control actions for recycled products.     

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.     

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.     

Design of an institutional decision-making process: the case of urban water management

Urban water infrastructure expenditures cause a major financial burden to municipalities. In the opinion of many policy-makers, public funds may alleviate this burden and facilitate environmental policies. However, practice has shown that despite ambitious policies, funding often follows traditional cost-dominated thinking. In Austria, national policy-makers were interested in new guidelines for funding that increase the transparency of the planning, ensure the adequate treatment of ecological problems, and foster stakeholder involvement, but keep the process as simple as possible, and require minimal changes of the current guidelines. An interdisciplinary project team conducted such a study. Its outcome was tested in two pilot projects. Based on these experiences, policy-makers finally implemented the recommended guidelines for the funding of communal urban water infrastructure projects. A general observation about the policy-making process was a conservative attitude of policy-makers. They prefer simple constraints (precautionary principle) and flexible negotiations (delegation) to complex assessment and decision-aid methodologies.     

Internal ecosystem feedbacks enhance nitrogen-fixing cyanobacteria blooms and complicate management in the Baltic Sea

Eutrophication of the Baltic Sea has potentially increased the frequency and magnitude of cyanobacteria blooms. Eutrophication leads to increased sedimentation of organic material, increasing the extent of anoxic bottoms and subsequently increasing the internal phosphorus loading. In addition, the hypoxic water volume displays a negative relationship with the total dissolved inorganic nitrogen pool, suggesting greater overall nitrogen removal with increased hypoxia. Enhanced internal loading of phosphorus and the removal of dissolved inorganic nitrogen leads to lower nitrogen to phosphorus ratios, which are one of the main factors promoting nitrogenfixing cyanobacteria blooms. Because cyanobacteria blooms in the open waters of the Baltic Sea seem to be strongly regulated by internal processes, the effects of external nutrient reductions are scale-dependent. During longer time scales, reductions in external phosphorus load may reduce cyanobacteria blooms; however, on shorter time scales the internal phosphorus loading can counteract external phosphorus reductions. The coupled processes inducing internal loading, nitrogen removal, and the prevalence of nitrogen-fixing cyanobacteria can qualitatively be described as a potentially self-sustaining "vicious circle." To effectively reduce cyanobacteria blooms and overall signs of eutrophication, reductions in both nitrogen and phosphorus external loads appear essential.     

Operating problems in anaerobic digestion plants resulting from nitrogen in MSW

Organic waste and municipal solid waste usually contain considerable amounts of different nitrogen compounds, which may inhibit anaerobic degradation processes and cause problems in the downstream and peripheral devices. This refers particularly to the different process stages of anaerobic digestion, to wastewater treatment, and to exhaust air treatment. Neither the knowledge about nitrogen problems nor the technologies for elimination of nitrogen compounds from the wastewater or the exhaust air of anaerobic digestion can be regarded as state-of-the-art. Most of the technologies in question have already been applied in other areas, but are barely tested for application in anaerobic digestion plants. The few performance data and experiences at hand were mainly derived from pilot and demonstration facilities. In this paper, the problem of nitrogen will be discussed in detail according to the separate problem fields based on the authors' experience, as well as on the basis of a review of the relevant literature. Furthermore, possible solutions will be proposed and the need for further research and development will be formulated.