Crystal structure of δ-isobutoxypentabromo-cyclododecanes, kinetics and selectivity of their isomerization during thermal treatment of flame-proofed polystyrenes

Hexabromocyclododecanes (HBCDs) are persistent organic pollutants now ubiquitous in the environment. Technical HBCD mixtures and with it flame-proofed polystyrenes (FP-PS) also contain isobutoxypentabromocyclododecanes (iBPBCDs) as minor constituents, which are possibly released together with HBCDs. So far, eight diastereomeric pairs of enantiomers named as α-, β-, γ-, δ-, ?-, ξ-, η-, and θ-iBPBCDs with proportions of 10%, 5%, 2%, 21%, 11%, 11%, 12% and 28% were found in technical HBCD. Herein the crystal structure of racemic δ-iBPBCD, the second most prominent diastereomer, is presented and assigned to (1S)-1-isobutoxy-(2R,5R,6S,9S,10S)-2,5,6,9,10-pentabromocyclododecane and its enantiomer. During thermal treatment of FP-PS, e.g. the production of extruded polystyrenes (XPS), proportions of δ-iBPBCDs decrease and those of other stereoisomers increase. Evidence was found that δ-iBPBCDs isomerize stereo- and regioselectively to β-iBPBCDs. Based on structural and kinetic data, a transformation mechanism was proposed. Apparent first-order rate constants (k_iso) of 0.0019, 0.0050, and 0.012 min⁻¹ are found for the δ- to β-iBPBCD isomerization at 120, 130, and 140 °C, respectively, corresponding to half-lives of 360, 140, and 56 min. These transformations also occur during the production of XPS, which predominantly contain β-iBPBCDs, whereas δ-iBPBCDs dominate in materials experiencing lower thermal stress, e.g. expanded polystyrenes (EPS). The relative configurations of δ- and θ-iBPBCDs are TtCtCt, like the one of γ-HBCDs. γ-HBCDs are the kinetically and α-HBCDs with a TcCtCc configuration the thermodynamically favored products. In analogy, β-iBPBCDs are assumed to have a TcCtCc configuration like α-HBCDs because they are formed from δ-iBPBCDs under thermodynamic control. In conclusion, HBCD- and iBPBCD-patterns in flame-proofed polystyrenes vary substantially, reflecting the thermal stress these materials have experienced. When released to the environment, these patterns might further change, as observed for HBCDs.     

Economic water management decisions: trade-offs between conflicting objectives in the sub-middle region of the São Francisco watershed

Hydro-economic models can measure the economic effects of different reservoir operating rules, environmental restrictions, maintenance of ecosystems, technical constraints, institutional constraints, land use change, and climate change. To determine the optimal economic water allocation, for its main uses in the sub-middle of the São Francisco River Basin, a hydro-economic optimization model was developed and applied. Demand curves were used rather than fixed requirements for water resources. The results show that operation rules of reservoirs and institutional constraints, such as priorities for human consumption, have high impacts on costs and benefits of the principal economic uses in the study area. Especially, costs of environmental demands, like minimum ecological river flow, have high impacts on the water resource management. Scarcity costs of irrigation users associated with maintaining ecosystems and environmental constraints are particularly significant. The results from this study provide a better understanding of the water trade-offs for future policymaking and efficient water management. Policymaking for the water resources should consider the food-water-energy-environment nexus at a regional scale to minimize environmental and economic cost under water scarcity and land use change.     

The Impact of Map and Data Resolution on the Determination of the Agricultural Utilisation of Organic Soils in Germany

Due to its nature, agricultural land use depends on local site characteristics such as production potential, costs and external effects. To assess the relevance of the modifying areal unit problem (MAUP), we investigated as to how a change in the data resolution regarding both soil and land use data influences the results obtained for different land use indicators. For the assessment we use the example of the greenhouse gas (GHG) emissions from agriculturally used organic soils (mainly fens and bogs). Although less than 5 % of the German agricultural area in use is located on organic soils, the drainage of these areas to enable their agricultural utilization causes roughly 37 % of the GHG emissions of the German agricultural sector. The abandonment of the cultivation and rewetting of organic soils would be an effective policy to reduce national GHG emissions. To assess the abatement costs, it is essential to know which commodities, and at what quantities, are actually produced on this land. Furthermore, in order to limit windfall profits, information on the differences of the profitability among farms are needed. However, high-resolution data regarding land use and soil characteristics are often not available, and their generation is costly or the access is strictly limited because of legal constraints. Therefore, in this paper, we analyse how indicators for land use on organic soils respond to changes in the spatial aggregation of the data. In Germany, organic soils are predominantly used for forage cropping. Marked differences between the various regions of Germany are apparent with respect to the dynamics and the intensity of land use. Data resolution mainly impairs the derived extent of agriculturally used peatland and the observed intensity gradient, while its impact on the average value for the investigated set of land-use indicators is generally minor.     

Aryl hydrocarbon receptor-mediated activity of atmospheric particulate matter from an urban and a rural site in Switzerland

Atmospheric particulate matter (PM) is an air-suspended mixture of solid and liquid particles that vary in size, shape, and chemical composition. Long-term exposure to elevated concentrations of fine atmospheric particles is considered to pose a health threat to humans and animals. In this context, it has been hypothesized that toxic chemicals such as polycyclic aromatic hydrocarbons (PAHs) play an important role. Some PAHs are known to be carcinogenic and it has been shown that carcinogenic effects of PAHs are mediated by the aryl hydrocarbon receptor (AhR). In this study, PM1 was collected at a rural and an urban traffic site during an intense winter smog period, in which concentration of PM1 often exceeded 50 μg m^?3. We applied an in vitro reporter gene assay (DR-CALUX) to detect and quantify PM1-associated chemicals that induce AhR-mediated gene expression. This activity was expressed as CALUX equivalents of 2,3,7,8-tetrachlorodibenzodioxin (PM-TCDD-CEQs). In addition, concentrations of PAHs in the PM1 extracts were determined using gas chromatography/high-resolution mass spectrometry. Concentrations of PM-TCDD-CEQs ranged from 10 to 85 pg m^?3 and from 19 to 87 pg m^?3 at the urban and rural site, respectively. By the use of known relative potency factors, the measured concentration of a PAH was converted into a PAH-TCDD-CEQ concentration. ΣPAH-TCDD-CEQ and PM-TCDD-CEQ were highly correlated at both sites (r² = 0.90 and 0.69). The calculated ΣPAH-TCDD-CEQs explain between 2% and 20% of the measured PM-TCDD-CEQs. Benzo[k]fluoranthene was the most important PAH causing approximately 60% of the total ΣPAH-TCDD-CEQ activity. In contrast to NO, CO, PM10, and PM1, the concentration of PM-TCDD-CEQs showed no significant difference between the two sites. No indications were found that road traffic emissions caused elevated concentrations of PM-TCDD-CEQs at the urban traffic site.     

The influence of maize residues on the mobility and binding of benazolin: investigating physically extracted soil fractions

The amount of non-extractable residues and the distribution of benazolin and its metabolites were evaluated three months after herbicide application (14C-labelled) in physically extracted soil fractions of topsoil layers of undisturbed soil columns with and without incorporated maize straw (14C-labelled). In addition, a variety of wet-chemical and spectroscopic methods were used to characterise the structure of organic carbon within the different soil fractions. The addition of crop residues increased the amount of dissolved organic carbon, enhanced the aromaticity of the organic carbon structure and enforced the aggregation of organomineral complexes. After incorporation of crop residues, an increase in the formation of metabolic compounds of benazolin and of non-extractable residues was detected. These results indicate that the addition of crop residues leads to a decrease in mobility and bioaccessibility of benazolin and its metabolites.     

Bendiocarbamate induced structural alterations in rabbit thymus after experimental peroral administration

In this study histological structure of rabbit thymus after bendiocarbamate (2,3-isopropyledene-dioxyphenyl methylcarbamate) administration was studied. Bendiocarbamate was perorally administered for 90 days. At Day 3, 10, 20, 30, 60, 90 morphometric analysis was realized. Quantitative evaluation showed that in the control group thymus cortex forms 57.94 +/- 7.10% and medulla 35.94+/- 7.38%. In almost all experimental groups significantly higher relative volume of cortex and lower relative volume of medulla was detected. Detail morphometric analysis found that the number of thymocytes per constant area and the diameter of tymocytes was decresed after bendiocarbamate administration. The number and diameter of reticular cells was not affected. Results of this study suggest negative effect of bendiocarbamate on the formation of thymus structures.     

Zoning a Protected Area: Proposal Based on a Multi-thematic Approach and Final Decision

The Madrid Regional Government (Central Spain) proposes a zone of the Guadarrama Mountains to be declared as a National Park. This paper reports on the zoning method developed to this end. The procedure followed considers compatibility of land uses with landscape characteristics and proposes protecting a part of the zone through declaration of National Park status and declaring another part as a Regional Park. The approach is based upon a multivariate environmental analysis aimed at zoning for optimal location of potential activities. The zoning permits the design of protected areas following the criteria underlying the declaration of these two categories in accordance with the Spanish environmental legislation in force. A practical tool for policy decision-making is provided. However, the final decision taken by policymakers in the design and zoning of protected areas differed from the model output used by the scientists. This is discussed in the paper to illustrate the interactions between political decision-making and scientific modelling.     

Concentration of heavy metals in various children's herbal tea types and their correlations

This investigation was undertaken to determine the concentrations of cadmium, lead, mercury, zinc, copper and magnesium in six tea types used as children's tea. Six types of tea of different herbal composition used for children's consumption (T1, T2, T3, T4, T5 and T6) were analyzed in three subsequent collections. The analysis of cadmium showed that the concentration was very similar in all types of children's tea, ranging from 0.233 to 0.369 mg/kg. Lead concentrations were in the range of 0.340–1.564 mg/kg without any significant differences. The analysis of mercury detected very low concentration of this metal in all samples (0.002–0.004 mg/kg). In zinc, the values ranged from 36.633 to 71.711 mg/kg, with significant differences (p < 0.001) according to tea type. Copper concentration was 10.089–30.178 mg/kg with the highest value in T4. The concentration of magnesium was significantly higher in tea T1 and T2 (102.311 and 129.422 mg/kg) in comparison with other tea types where the level was 19.811–37.411 mg/kg. The maximum tolerable limit determined by Codex Alimentarius was not exceeded in any sample. In general, correlation analysis detected high positive correlation between cadmium and lead (r = 0.89), cadmium and mercury (r = 0.92) and between lead and mercury (r = 0.77).     

Spindle dynamics identification using particle swarm optimization

Optimal parameters to eliminate machining chatter may be identified using analytical stability models which require the dynamics of the tool-holder-spindle-machine assembly. Receptance coupling substructure analysis (RCSA) provides a useful analytical tool to couple measured spindle-machine dynamics with tool-holder models to predict the tool point frequency response function for the assembly. Previous research has demonstrated a procedure to determine all required spindle receptances from a single measurement, where each mode within the measurement bandwidth was modeled as a fixed-free Euler–Bernoulli beam and fit using a manual, iterative procedure. Here, a particle swarm optimization technique is described for fitting the spindle-machine measurement using a fixed-free Euler–Bernoulli beam model for each mode. The performance of the optimization process and RCSA in predicting the tool tip frequency response is evaluated and the results are presented.