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271.
Heeb NV Schweizer WB Mattrel P Haag R Gerecke AC Schmid P Zennegg M Vonmont H 《Chemosphere》2008,73(8):1201-1210
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. 相似文献
272.
D'Affonseca FM Blum P Finkel M Melzer R Grathwohl P 《Journal of contaminant hydrology》2008,102(1-2):120-139
A coal tar contaminated site was characterized using traditional and innovative investigation methods. A careful interpretation of hydrogeological and hydrogeochemical data allowed for the conceptualization of the heterogeneous coal tar distribution in the subsurface. Past and future contaminant release from the source zone was calculated using a modeling framework consisting of a three-dimensional steady-state groundwater flow model (MODFLOW) and two hydrogeochemical models (MIN3P). Computational time of long-term simulations was reduced by simplifying the coal tar composition using 3 composite and 2 individual constituents and sequential application of a 2D centerline model (for calibration and predictions) and a 3D model (only for predictions). Predictions were carried out for a period of 1000 years. The results reveal that contaminant mass flux is governed by the geometry of zones containing residual coal tar, amount of coal tar, its composition and the physicochemical properties of the constituents. The long-term predictions made using the 2D model show that even after 1000 years, source depletion will be small with respect to phenanthrene, 89% of initial mass will be still available, and for the moderately and sparingly soluble composite constituents, 60% and 98%, respectively. 相似文献
273.
道路条件安全性分析 总被引:4,自引:2,他引:2
对道路上发生的相关交通事故情况与道路条件安全性的关系进行了分析,对比分析了大量国内外事故绝对数、事故率等统计数据.结果表明,简单的交通事故的绝对数反映的道路条件安全性不够准确;交通事故的事故率能够很好地反映道路路面、道路线形、道路横断面、道路交叉口以及道路照明等道路条件的安全性;其中路面摩阻系数是道路条件安全性的一个重要表征指标;道路平纵曲线的重合对道路条件安全性的影响较大.揭示了道路交通事故多发与各种不利道路条件之间存在的内在关系,证明了道路条件的安全性可以用道路上发生的相关交通事故情况来分析与评价的可行性. 相似文献
274.
Modelling municipal solid waste generation: a review 总被引:1,自引:0,他引:1
The objective of this paper is to review previously published models of municipal solid waste generation and to propose an implementation guideline which will provide a compromise between information gain and cost-efficient model development. The 45 modelling approaches identified in a systematic literature review aim at explaining or estimating the present or future waste generation using economic, socio-demographic or management-orientated data. A classification was developed in order to categorise these highly heterogeneous models according to the following criteria--the regional scale, the modelled waste streams, the hypothesised independent variables and the modelling method. A procedural practice guideline was derived from a discussion of the underlying models in order to propose beneficial design options concerning regional sampling (i.e., number and size of observed areas), waste stream definition and investigation, selection of independent variables and model validation procedures. The practical application of the findings was demonstrated with two case studies performed on different regional scales, i.e., on a household and on a city level. The findings of this review are finally summarised in the form of a relevance tree for methodology selection. 相似文献
275.
Modelling of stable isotope fractionation by methane oxidation and diffusion in landfill cover soils 总被引:2,自引:0,他引:2
Mahieu K De Visscher A Vanrolleghem PA Van Cleemput O 《Waste management (New York, N.Y.)》2008,28(9):1535-1542
A technique to measure biological methane oxidation in landfill cover soils that is gaining increased interest is the measurement of stable isotope fractionation in the methane. Usually to quantify methane oxidation, only fractionation by oxidation is taken into account. Recently it was shown that neglecting the isotope fractionation by diffusion results in underestimation of the methane oxidation. In this study a simulation model was developed that describes gas transport and methane oxidation in landfill cover soils. The model distinguishes between (12)CH(4), (13)CH(4), and (12)CH(3)D explicitly, and includes isotope fractionation by diffusion and oxidation. To evaluate the model, the simulations were compared with column experiments from previous studies. The predicted concentration profiles and isotopic profiles match the measured ones very well, with a root mean square deviation (RMSD) of 1.7vol% in the concentration and a RMSD of 0.8 per thousand in the delta(13)C value, with delta(13)C the relative (13)C abundance as compared to an international standard. Overall, the comparison shows that a model-based isotope approach for the determination of methane oxidation efficiencies is feasible and superior to existing isotope methods. 相似文献
276.
277.
K. Pritsch D. Ernst F. Fleischmann S. Gayler T. E. E. Grams A. Göttlein W. Heller N. Koch H. Lang R. Matyssek J. C. Munch M. Olbrich H. Scherb S. Stich J. B. Winkler M. Schloter 《Water, Air, & Soil Pollution: Focus》2008,8(2):139-154
A lysimeter study was performed to monitor effects of elevated ozone on juvenile trees of Fagus sylvatica L. as well as on the plant–soil system. During a fumigation period over almost three growing seasons, parameters related
to plant growth, phenological development and physiology as well as soil functions were studied. The data analyses identified
elevated ozone to delay leaf phenology at early and to accelerate it at late developmental stages, to reduce growth, some
leaf nutrients (Ca, K) as well as some soluble phenolics (hydroxycinnamic acid derivatives, total flavonol glycosides). No
or very weak ozone effects were found in mobile carbon pools of leaves (starch, sucrose), and other phenolic compounds (flavans).
Altered gene expression related to stress and carbon cycling corresponded well with findings from leaf phenology and chemical
composition analyses indicating earlier senescence and oxidative stress in leaves under elevated ozone. Conversely in the
soil system, no effects of ozone were detected on soil enzyme activities, rates of litter degradation and lysimeter water
balances. Despite the fact that the three reported years 2003–2005 were climatically very contrasting including a hot and
dry as well as an extremely wet summer, and also mild as well as cold winters, the influence of ozone on a number of plant
parameters is remarkably consistent, further underlining the phytotoxic potential of elevated tropospheric ozone levels. 相似文献
278.
Peter J. Auster 《Conservation biology》1998,12(6):1198-1203
279.
In 1995, common tern (Sterna hirundo) eggs from the big German rivers, the Rhine, Weser and Elbe were collected to study the contamination with organochlorines and mercury. We found distinct differences between the rivers: common tern eggs from the Rhine had higher concentrations of PCBs and HCHs, while eggs from the Elbe had higher residues of DDT, HCB and mercury. Also toxic PCB congeners had higher residue levels in the Rhine. Considering all organochlorines, samples from the Rhine also had the highest concentrations, while those from the Elbe were the lowest. With 5.7 μg×g?1 fresh weight, the ΖCBs had a level endangering breeding success. Fish eating birds should be used as indicators of the contamination of the rivers with environmental chemicals and should be included in monitoring programmes. 相似文献
280.