Regio- and stereoselective isomerization of hexabromocyclododecanes (HBCDs): kinetics and mechanism of gamma- to alpha-HBCD isomerization

Hexabromocyclododecanes (HBCDs) are high production volume chemicals (>20000 ty(-1)) used as flame retardants for plastics and textiles. Lately, we reported on the stereoselective isomerization of beta-HBCDs. Herein we present insights into the mechanism and kinetics of (+)gamma- to (+)alpha- and of (-)gamma- to (-)alpha-HBCD isomerization. Only two of the six bromine atoms migrated, indicating that rearrangements of gamma- to alpha-HBCDs are regio- and stereoselective as well. The apparent first-order isomerization rate constants increased from 0.0013 to 0.0031 to 0.0070 min(-1) at 120, 130, and 140 degrees C, respectively, corresponding to half-lives of 540, 230, and 99 min. Thus, a thermal treatment of materials containing gamma-HBCDs at temperatures >100 degrees C may induce the formation of alpha-HBCDs and, hence, may alter the diastereomeric ratio of a HBCD mixture. The inversion of vicinal dibromides in like-configurations (RR/SS) prevailed, whereas unlike-configurations (RS/SR) were not affected. An intramolecular, stereoselective migration of neighboring bromine atoms via a four-center transition state would explain the observed stereoisomer pattern and first-order kinetics. Despite the fact that vicinal dibromides in HBCDs prefer synclinal (gauche) conformations, antiperiplanar (staggered) conformations are assumed to facilitate concerted 1.2-shifts of both bromine atoms. A conformation analysis revealed that under kinetic control, only those bromine atoms in the more flexible part of the molecules are migrating, whereas those in the conserved triple-turn motive were not affected. Thus, this structural motive, common to all alpha-, beta-, and gamma-HBCDs, is more rigid and less reactive than the flexible part, containing the reacting dibromides in like-configurations.     

CO2/H2O gas exchange parameters of one- and two-year-old needles of spruce and fir

Gas exchange was characterized in one- and two year-old spruce (Picea abies L. Karst.) and fir seedlings (Abies alba Mill.) which had been exposed to low levels of ozone, sulfur dioxide and simulated rain or a combination of all three variables in open top chambers from 1983 through 1988. The gas exchange measurements were carried out in March 1988 at the end of the five year experiment. The twigs examined did not exhibit any visible sign of injury, specifically no differences were apparent between trees under the treatments of simulated acidic rain at pH 5.0 and pH 4.0. The study of carbon dioxide response curves showed different effects of the pollutants on the tree species. One-Year-old spruce needles treated with O(3) and simulated acidic precipitation pH 4.0 showed noticeable reduction of net photosynthetic rate. Exposure to the combination O(3) and SO(2) at pH 4.0 resulted in a significant depression of photosynthesis in two-year-old needles Transpiration rate was not decreased to a similar extent. No changes either in photosynthesis or transpiration were found in spruce under fumigation with SO(2) alone. These results indicate that ozone is the principal cause of changes in photosynthetic performance of spruce. It alters mesophyll response rather than reducing stomatal conductance. The specific changes that occur in the mesophyll could be diagnosed as inactivation of a carbon fixing enzyme as well as damage of the electron transport system. Fir seem to be more tolerant to ozone. No changes in photosynthesis and transpiration following exposure to O(3) alone were found. However, SO(2) fumigation, alone or in combination with O(3), resulted in a marked decrease of photosynthetic performance. Particularly, carboxylation efficiency and also maximum carboxylation velocity were depressed indicating a reduction in carbon fixing enzyme activity. No differences between single and combined fumigation treatments regarding these variables were determined. However, parameters measured to determine changes in electron transport rate showed a higher depression in the presence of both pollutants. Transpiration also was reduced by SO(2).     

Laboratory and field evaluation of real-time and near real-time PM2.5 smoke monitors

ABSTRACT

Increases in large wildfire frequency and intensity and a longer fire season in the western United States are resulting in a significant increase in air pollution, including concentrations of PM_2.5 (particulate matter <2.5 µm in aerodynamic diameter) that pose significant health risks to nearby communities. During wildfires, government agencies monitor PM_2.5 mass concentrations providing information and actions needed to protect affected communities; this requires continuously measuring instruments. This study assessed the performance of seven candidate instruments: (1) Met One Environmental beta attenuation monitor (EBAM), (2) Met One ES model 642 (ES642), (3) Grimm Environmental Dust Monitor 164 (EDM), (4) Thermo ADR 1500 (ADR), (5) TSI DRX model 8543 (DRX), (6) Dylos 1700 (Dylos), and (7) Purple Air II (PA-II) in comparison with a BAM 1020 (BAM) reference instrument. With the exception of the EBAM, all candidates use light scattering to determine PM_2.5 mass concentrations. Our comparison study included environmental chamber and field components, with two of each candidate instrument operating next to the reference instrument. The chamber component involved 6 days of comparisons for biomass combustion emissions. The field component involved operating all instruments in an air monitoring station for 39.5 days with hourly average relative humidity (RH) ranging from 19% to 98%. Goals were to assess instrument precision and accuracy and effects of RH, elemental carbon (EC), and organic carbon (OC) concentrations. All replicate candidate instruments showed high hourly correlations (R² ≥ 0.80) and higher daily average correlations (R² ≥ 0.90), where all instruments correlated well (R² ≥ 0.80) with the reference. The DRX and Purple Air overestimated PM_2.5 mass concentrations by a factor of ~two. Differences between candidates and reference were more pronounced at higher PM_2.5 concentrations. All optical instruments were affected by high RH and by the EC/OC ratio. Equations to convert candidate instruments data to FEM BAM type data are provided to enhance the usability of data from candidate instruments.

Implications: This study tested the performance of seven candidate PM_2.5 mass concentration measuring instruments in two settings - environmental chamber and field. The instruments were tested to determine their suitability for use during biomass combustion events and the effects of RH, PM mass concentrations, and concentrations of EC and OC on their performance. The accuracy and precision of each monitor and effect of RH, PM concentration, EC and OC concentrations are varied. The data show that most of these candidate instruments are suitable for measuring PM_2.5 concentration during biomass combustions with a proper correction factor for each instrument type.     

Biosynthese und Struktur des Fettsäuresynthetase-Komplexes der Hefe

Genetic as well as biochemical data suggest that the yeast fatty-acid synthetase complex has an (AB)₆ protein structure where A and B represent multifunctional polypeptide chains with molecular weights of 185000 and 180000 daltons, respectively. Subunit A contains at least 3 and subunit B4 of the 8 known biochemical functions of the multienzyme complex. It is concluded that this complex structure has evolved from the corresponding prokaryotic system of monofunctional enzymes due to a selective advantage regarding the biosynthesis and assembly of the complex components.     

2,5,6,9,10-Pentabromocyclododecanols (PBCDOHs): a new class of HBCD transformation products

Pentabromocyclododecanols (PBCDOHs) are potential environmental transformation products of hexabromocyclododecanes (HBCDs). They are also potential stage one metabolites of biological HBCD transformations. Herein, we present analytical evidence that PBCDOHs are also constituents of technical HBCDs and flame-proofed polystyrenes (FP-PSs). PBCDOHs are possibly formed during the synthesis of technical HBCD, presumably during the bromination of cyclododecatrienes in aqueous isobutanol together with isobutoxypentabromocyclododecanes (iBPBCDs), which have been identified in these materials recently. Of the 64 stereoisomers possible, eight pairs of enantiomers, named α-, β-, γ-, δ-, ε-, ζ-, η-, and θ-PBCDOHs were separated with a combination of normal-, reversed- and chiral-phase LC. Crystal structure analysis revealed the stereochemistry of the α-PBCDOH pair of enantiomers, which was assigned to (1S,2S,5R,6S,9S,10R)-2,5,6,9,10-pentabromocyclododecanol and its enantiomer. Mass spectrometric data are in accordance with the expected isotope patterns. On a C₁₈-RP-column, the polar PBCDOHs eluted before the HBCD and iBPBCD classes of compounds. PBCDOHs were also found in FP-PS materials. The stereoisomer patterns varied considerably in these materials like those of HBCDs and iBPBCDs. Expanded polystyrenes were rich in late-eluting stereoisomers, similar to technical HBCD mixtures. Extruded polystyrenes contained more of the polar, faster-eluting isomers. The presented chromatographic and analytical methods allow a stereoisomer-specific search for PBCDOHs in biota samples, which might have experienced metabolic HBCD transformation reactions. Besides this potential source, it has to be recognized that PBCDOHs are by-products in technical HBCDs and in flame-proofed polystyrenes. Therefore, it is likely that PBCDOHs and iBPBCDs are released to the environment together with HBCD-containing plastic materials.     

Decisions to reduce greenhouse gases from agriculture and product transport: LCA case study of organic and conventional wheat

A streamlined hybrid life cycle assessment is conducted to compare the global warming potential (GWP) and primary energy use of conventional and organic wheat production and delivery in the US. Impact differences from agricultural inputs, grain farming, and transport processes are estimated. The GWP of a 1 kg loaf of organic wheat bread is about 30 g CO₂-eq less than the conventional loaf. When organic wheat is shipped 420 km farther to market, organic and conventional wheat systems have similar impacts. These results can change dramatically depending on soil carbon accumulation and nitrous oxide emissions from the two systems. Key parameters and their variability are discussed to provide producers, wholesale and retail consumers, and policymakers metrics to align their decisions with low-carbon objectives.     

Batterienrecycling: Möglichkeiten zur Erhöhung der Rücklaufquote

Separate collection and exploitation of used batteries facilates the recycling and eventual waste management of such heavy metals as mercury and cadmium. It is thereby possible to regain raw materials like zinc, manganese and iron for the raw material cycle. Although the collection and recycling of used batteries in Switzerland is financed by a prepaid disposal fee, their returning rate of almost 60% is too low for several reasons. A questionnaire survey carried out on 2000 households revealed the following frequenthy: People collecting paper, glass, aluminium, compost and tinplate, are more separate used batteries from ordinary garbage. The number of collecting points is supposed to be sufficient, but not all of them are sufficiently marked. The prepaid disposal fee (VEG) should become obligatory so that it would be possible to compensate the collecting points. It is not obvious from the results of the survey if the introduction of a deposit of batteries would raise the retourning rate. As far as advertising is concerned, only the “battery bag” sent to every household by the BESO seemed to influence the collecting behaviour in a positive way, poster advertising had only little effect. Appeals in newspapers, radio and television did not show any changement of the collecting behaviour. However, information and knowledge about batteries and their recycling do have a positive influence in the collecting behaviour of the consumers in this specific case.     

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.