Structure characterization and thermal stabilities of the isomers of the brominated flame retardant 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane

1,2-Dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH) is used primarily as an additive flame retardant. 1H NMR spectroscopy and an X-ray structure determination have revealed that a technical mixture consists largely of two (of the four possible) diastereomers, rac-(1R,2R)-1,2-dibromo-(4S)-4-((1S)-1,2-dibromoethyl)cyclohexane (alpha-TBECH) and rac-(1R,2R)-1,2-dibromo-(4S)-4-((1R)-1,2-dibromoethyl)cyclohexane (beta-TBECH), in a mole ratio of approximately 1:1. The two other possible isomers, gamma- and delta-TBECH, were not detected in a technical mixture. The TBECH isomers are thermally sensitive and can easily interconvert at temperatures of 125 degrees C. A thermal equilibrium mixture of alpha-, beta-, gamma- and delta-TBECH consists of approximately 33%, 33%, 17% and 17% of these isomers, respectively. Separation of all four TBECH diastereomers, with minimal thermal interconversion of the isomers, was achieved by careful selection of GC-capillary column length and injector temperature. Although technical TBECH does not contain the gamma- and delta-isomers, they may still be relevant environmental contaminants since manufacturing processes utilize thermal processes which may induce their formation.     

Optimal Carbon Capture and Storage Policies

The IPCC recommends the use of carbon capture and sequestration (CCS) technologies in order to achieve the Kyoto environmental goals. This paper sheds light on this issue by assessing the optimal strategy regarding the long-term use of CCS technologies. The aim is to analyze the optimal CCS policy when the sequestration rate is endogenous, being therefore one specific tool of the environmental policy. We develop a simple growth model to identify the main driving forces that should determine the optimal CCS policy. We show that, under some conditions on the cost of extractions, CCS may be a long-term solution to curb carbon emissions. We also show that over time the social planner will choose to decrease the rate of capture and sequestration. We then derive the decentralized equilibrium outcome by considering the programs of the fossil resource-holder and of the representative consumer. Finally, we determine the optimal environmental policy, i.e. the carbon tax scheme, as well as the dynamics of the fossil fuel price needed to implement it.     

Effect of selected organic and inorganic snow and cloud components on the photochemical generation of nitrite by nitrate irradiation

The effect of selected organic and inorganic compounds, present in snow and cloudwater was studied. Photolysis of solutions of nitrate to nitrite was carried out in the laboratory using a UVB light source. The photolysis and other reactions were then modelled. It is shown that formate, formaldehyde, methanesulphonate, and chloride to a lesser extent, can increase the initial formation rate of nitrite. The effect, particularly significant for formate and formaldehyde, is unlikely to be caused by scavenging of hydroxyl radicals. The experimental data obtained in this work suggest that possible causes are the reduction of nitrogen dioxide and nitrate by radical species formed on photooxidation of the organic compounds. Hydroxyl scavenging by organic and inorganic compounds would not affect the initial formation rate of nitrite, but would protect it from oxidation, therefore, increasing the concentration values reached at long irradiation times. The described processes can be relevant to cloudwater and the quasi-liquid layer on the surface of ice and snow, considering that in the polar regions irradiated snow layers are important sources of nitrous acid to the atmosphere. Formate and (at a lesser extent) formaldehyde are the compounds that play the major role in the described processes of nitrite/nitrous acid photoformation by initial rate enhancement and hydroxyl scavenging.     

Biological and ecophysiological reactions of white wall rocket (Diplotaxis erucoides L.) grown on sewage sludge compost

We studied the effects of sewage sludge compost on white wall rocket (Diplotaxis erucoides L.) compared with mineral fertilization and control (without any fertilizer) in a greenhouse experiment. The plants grown on the compost-amended soil showed a different growth dynamic: a significant delay in flowering and a bigger root system. Both the compost and the fertilization treatments increased biomass and seed yield. Heavy metal (Cu, Cd, Zn, Ni) distribution within the plant was in the following order: roots > leaves > stems, except for zinc which was homogeneously distributed. The balance of mineral nutrition was not affected by treatments. Zinc was the trace element which was most taken up. Unlike many species of Brassicaceae, white wall rocket is not a hyperaccumulator. Although sewage sludge compost improved plant growth, delay in flowering shows that it is necessary to take precautions when spreading sewage sludge in natural areas.     

Screening of high production volume chemicals for estrogen receptor binding activity (II) by the MultiCASE expert system

A structurally and functionally diverse and cross-validated quantitative structure-activity knowledge database generated by the MultiCASE expert system was used to screen 2526 high production volume chemicals (HPVCs) for their estrogen receptor binding activity. 73 HPVCs were found to contain structural features or biophores that have been documented as having the ability to bind to the estrogen receptor. Potential chemicals were ranked according to their quantitatively predicted ER binding potential and the details of the biophores found in them are discussed.     

PM2.5 source apportionment in a French urban coastal site under steelworks emission influences using constrained non-negative matrix factorization receptor model

The constrained weighted-non-negative matrix factorization(CW-NMF) hybrid receptor model was applied to study the influence of steelmaking activities on PM_(2.5)(particulate matter with equivalent aerodynamic diameter less than 2.5 μm) composition in Dunkerque,Northern France. Semi-diurnal PM_(2.5)samples were collected using a high volume sampler in winter 2010 and spring 2011 and were analyzed for trace metals, water-soluble ions, and total carbon using inductively coupled plasma – atomic emission spectrometry(ICP-AES),ICP- mass spectrometry(ICP-MS), ionic chromatography and micro elemental carbon analyzer. The elemental composition shows that NO_3~-, SO_4~(2-), NH_4~+and total carbon are the main PM_(2.5)constituents. Trace metals data were interpreted using concentration roses and both influences of integrated steelworks and electric steel plant were evidenced. The distinction between the two sources is made possible by the use Zn/Fe and Zn/Mn diagnostic ratios. Moreover Rb/Cr, Pb/Cr and Cu/Cd combination ratio are proposed to distinguish the ISW-sintering stack from the ISW-fugitive emissions. The a priori knowledge on the influencing source was introduced in the CW-NMF to guide the calculation. Eleven source profiles with various contributions were identified: 8 are characteristics of coastal urban background site profiles and 3 are related to the steelmaking activities. Between them,secondary nitrates, secondary sulfates and combustion profiles give the highest contributions and account for 93% of the PM_(2.5)concentration. The steelwork facilities contribute in about 2%of the total PM_(2.5)concentration and appear to be the main source of Cr, Cu, Fe, Mn, Zn.