Preparation and X-ray structural characterization of further stereoisomers of 1,2,5,6,9,10-hexabromocyclododecane

Technical 1,2,5,6,9,10-hexabromocyclododecane (HBCD) consists largely of three diastereomers (α-, β-, and γ-HBCD) produced by the trans addition of bromine to cis,trans,trans-cyclododeca-1,5,9-triene (CDT). However, another seven diastereomers are theoretically possible and may be produced by trans addition of bromine across the double bonds of the other three isomers of 1,5,9-CDT. There are indications that small amounts of the minor HBCD isomers may be present in commercial HBCD mixtures or in products containing this brominated flame retardant (BFR). Such minor components may indeed derive from traces of other 1,5,9-CDTs in the cis, trans, trans starting material, however their formation may also be possible through isomerizations during the processing of this BFR or by bioisomerization subsequent to its release into the environment. Two of the seven additional diastereomers (δ- and ε-HBCD) were synthesized previously from trans,trans,trans-CDT. We now report the preparation of the remaining five diastereomers, ζ-, η-, and θ-HBCD from cis,cis,trans-CDT and ι- and κ-HBCD from cis,cis,cis-CDT, and their characterization by ¹H NMR spectroscopy and X-ray crystallography. The availability of these further diastereomers of HBCD should aid in determining if the minor isomers are present in commercial samples of this BFR, in products containing HBCDs, or in environmental samples. We have also carried out an X-ray crystal structure determination on ε-HBCD, so that crystal structures are now available for all 10 HBCD diastereomers.     

Nuclear magnetic resonance spectral characterization and semi-empirical calculations of conformations of alpha- and gamma-1,2,5,6,9,10-hexabromocyclododecane

The full 1H and 13C NMR spectral characterization of alpha- and gamma-1,2,5,6,9,10-hexabromocyclododecane (HBCD) is reported in this paper. The use of various NMR experiments, an analysis of the magnitude of the NMR chemical shifts and coupling constants, and computer modeling has enabled the visualization of the three-dimensional structures for both the alpha- and gamma-diastereomers. This information may provide insight into the different behavior of the alpha- and gamma-HBCD diastereomers in the environment.     

Synthesis of the two minor isomers, delta- and epsilon-1,2,5,6,9,10-hexabromocyclododecane, present in commercial hexabromocyclododecane

Hexabromocyclododecane (HBCD) is prepared commercially by bromination of cis,trans,trans-cyclododecatriene (ctt-CDT) and widely used as a flame retardant, particularly in polystyrene foams. Commercial HBCD consists largely of three diastereomers, alpha-, beta-, and gamma-HBCD, the structures of which have been known for many years. Recently, the presence in the mixture of small amounts of two minor diastereomers, delta- and epsilon-HBCD, has been reported. Bearing in mind the manner in which commercial HBCD is generated, it was anticipated that these components are probably formed by bromination of trans,trans,trans-cyclododecatriene (ttt-CDT), a common contaminant in commercial ctt-CDT. Indeed, when a sample of ttt-CDT was brominated it gave two products, the NMR spectra and LC/MS and GC/MS behaviour of which confirmed that they are identical to the minor components, delta- and epsilon-HBCD, present in commercial HBCD.     

Biodegradability of antineoplastic compounds in screening tests: influence of glucosidation and of stereochemistry

Some pharmaceuticals such as antineoplastics are carcinogenic, mutagenic, teratogenic and fetotoxic. Antineoplastics and their metabolites are excreted by patients into waste water. In laboratory testing the frequently used isomeric anti-tumour agents cyclophosphamide (CP) and ifosfamide (IF) were shown to be not biodegradable. They are not eliminated in municipal sewage treatment plants and therefore detected in their effluents. Structural related compounds are beta-D-glucosylisophosphoramidmustard (beta-D-Glc-IPM; INN = glufosfamide) and beta-L-glucosylisophosphoramidmustard (beta-L-Glc-IPM). beta-L-Glc-IPM has no antineoplastic effects whereas beta-D-Glc-IPM is active against tumours. In contrast to IF and CP and almost all other investigated antineoplastics beta-D-Glc-IPM is inherently biodegradable. Improved biodegradability of beta-D-Glc-IPM compared to IF shows that reducing the impact of pharmaceuticals on the aquatic environment is feasible by changing the chemical structure of a given compound exerting a similar mode of action and therapeutic activity. Stereochemistry may be crucial for pharmaceutical activity of the compounds as well as for its biodegradability in the environment.     

Analysis of air pollution data by the combined use of interactive graphic presentation and a clustering technique

Interactive graphic techniques and the “one-way splitting algorithm” have been used in analysing a number of data sets connected to air pollution problems. The combination of these methods seems to offer an easy and convenient way to extract information from data in analytical chemistry.     

环境材料及其评价方法

本文综述了环境材料的实质、特点及其与传统材料在主要内涵、研究重点、评价指标体系和材料选择原则的差异 ,并介绍了环境材料的评价体系与方法和设计原则     

On the laboratory representation of rain impingement on buildings

A study of rain penetration of buildings comprises three separate divisible parts:

• 1.(i) A study of the meteorological conditions in the locality
• 2.(ii) A study of the wind velocity and rain content of the air at the point of impingement considered
• 3.(iii) A study of the mechanisms of penetration of the building surface at joints in the cladding coupled with a study of the impingement and run-off of rain on real surfaces away from joints.

Whereas the first and third parts of the problem have received considerable study, the second part has been largely neglected. This note describes possible forms of investigation whereby the second part of this problem could be satisfactorily studied.     

藻类在环境保护中的作用及其资源化利用研究进展

作为地球上最庞大的生物群体,藻类在环境保护中具有重要意义.主要述评了藻类在固定二氧化碳、去除有毒有害物质,去除难降解有机物、吸附重金属等方面的作用,并从制油,提取色素、藻胆蛋白、生理活性物质等方面评价了藻类的资源化用途,最后对其资源化利用的未来研究方向进行了展望.     

The long range transport of ozone within Europe and its control

It is widely accepted that the ozone concentrations experienced during photochemical episodes over large areas of Europe may exceed levels at which adverse environmental effects could be expected. These peak ozone concentrations can be reduced by controlling atmospheric emissions of the hydrocarbon and nitrogen oxide precursors. For ozone control to be successful over the spatial scale of Europe, long term international cooperation is required in the formulation of emission abatement strategies. A significant barrier to rapid progress has been the complexity of the processes that describe ozone formation. Highly sophisticated computer models of chemistry and transport have, up to now, been the only means to study the impact of abatement strategies. An alternative approach has been adopted here involving the development of a simplified long range transport model for ozone based on the analysis of over 60 experimental runs of a photochemical trajectory model applied to a wide range of hydrocarbon-nitrogen oxide emission combinations. Using the ozone-precursor relationship obtained, it has been possible to examine various policy options in the European context. Although taken together, three illustrative emission control scenarios reduce NO(x) and hydrocarbon emissions substantially through controls on motor vehicle exhaust, large combustion plant and solvent usage, a significant potential for photochemical ozone formation and long range transport may still remain after their implementation. The extents of precursor emission abatement that will be required, if the potential for ozone formation is to be reduced below published air quality criteria guidelines or critical levels, have been determined for each European country. The implied reductions in NO(x) and hydrocarbons relative to current levels amount to between 50 and 90%.     

The study of urban metabolism and its applications to urban planning and design

Following formative work in the 1970s, disappearance in the 1980s, and reemergence in the 1990s, a chronological review shows that the past decade has witnessed increasing interest in the study of urban metabolism. The review finds that there are two related, non-conflicting, schools of urban metabolism: one following Odum describes metabolism in terms of energy equivalents; while the second more broadly expresses a city's flows of water, materials and nutrients in terms of mass fluxes. Four example applications of urban metabolism studies are discussed: urban sustainability indicators; inputs to urban greenhouse gas emissions calculation; mathematical models of urban metabolism for policy analysis; and as a basis for sustainable urban design. Future directions include fuller integration of social, health and economic indicators into the urban metabolism framework, while tackling the great sustainability challenge of reconstructing cities.     

The use of wastewater in livestock production and its socioeconomic and welfare implications

Although epidemiological studies have found a significant amount of toxins in surface water, a complex link between animals’ access to wastewater and associated animal and human welfare losses needs to be explored. The scarcity of safe water has put stress on the utilization of wastewater for crops and livestock production. The access of animals to wastewater is related to the emergence of dangerous animal’s diseases, hampering productivity, increasing economic losses, and risking human health along the food chain. This review explores use of wastewater for agriculture, epidemiological evidence of microbial contamination in wastewater, and animal and human welfare disruption due to the use of wastewater for crop and livestock production. More specifically, the review delves into animals exposure to wastewater for bathing, drinking, or grazing on a pasture irrigated with contaminated water and related animal and human welfare losses. We included some scientific articles and reviews published from 1970 to 2017 to support our rational discussions. The selected articles dealt exclusively with animals direct access to wastewater via bathing and indirect access via grazing on pasture irrigated with contaminated wastewater and their implication for animal and human welfare losses. The study also identified that some policy options such as wastewater treatments, constructing wastewater stabilization ponds, controlling animal access to wastewater, and dissemination of necessary information to ultimate consumers related to the source of agricultural produce and wastewater use in animal and crop production are required to protect the human and animal health and welfare.     

中文智能pH在线监控仪及其算法开发

介绍了中文智能ｐＨ在线监控仪的性能、工作原理，功能及软件硬件设置，分析讨论了几咱不同的控制算法。     

The wet deposition of sulphate and its relationship to sulphur dioxide emissions

The factors that need to be considered when comparing rainfall data with emission data are summarized, and it is indicated that trend analysis cannot be done properly without the use of a transport model. An optimization procedure is then used to fit the Fisher statistical model to European sulphate in rain data. This indicates moderately efficient to efficient wet removal of sulphate on average across Europe which is consistent with limited aqueous oxidation close to major source areas and a more linear behaviour at greater distances. At such distances, particularly in remote high rainfall areas, the results demonstrate the importance of ‘background’ sulphate. The results are all consistent with the latest U.K. rainfall data.     

The excretion of pesticides in saliva and its value in assessing exposure

The possibility that pesticides are secreted in the saliva and that this secretion can be used to assess exposure to pesticides is discussed. Both Kepone and carbaryl were tested through a series of in vitro studies and in vivo experiments including both acute and subchronic studies. In the in vivo studies, both Kepone and carbaryl were detected in the saliva in the first twenty-four hours, but seldom thereafter. Analysis of urinary samples indicated a rapid clearance of the substances from the animals. In vitro uptake and efflux studies suggested that movement of both substances was by passive diffusion and reached a plateau after 60 minutes of incubation. Efflux rates were unaffected by experimental conditions, but were ten times faster for carbaryl.     

杭州市城区冬季大雾频发的原因及防治对策

杭州市１９９８年冬季大雾频发,这是气象因素与环境共同作用的结果,加强环境管理,减少大气层中颗粒物的排放,降低大气中颗粒物的浓度,是控制冬季大雾频发的有效途径。     

污染物与蒙脱石层间域的界面反应及其环境意义

系统地评述了无机、有机阳离子、农药分子、细菌等环境污染物在蒙脱石层间域中的吸附、脱附、氧化还原、催化降解等界面反应机理 ,并指出它们的环境化学行为对环境的影响和意义     

The dissipation rates of trichlorfon and its degradation product dichlorvos in cabbage and soil

The residual levels and dissipation rate of trichlorfon, and its degradation product, dichlorvos, in cabbage crops and the soil in which these were grown, were determined by gas chromatography at two geographically distant experimental sites, one in Kunming and one in Beijing, China. Trichlorfon was applied at two dosages (900 g ai ha⁻¹ and 1350 g ai ha⁻¹). Maximum final residues of trichlorfon in soil and cabbage were 1.23 mg kg⁻¹ and 1.81 mg kg⁻¹ respectively at Kunming, and 0.35 mg kg⁻¹ and 0.70 mg kg⁻¹ respectively at Beijing. However, the final residues of dichlorvos in both cabbage and soil was only 0.04 mg kg⁻¹ at Kunming, and only 0.03 mg kg⁻¹, or “not detectable”, at Beijing. The mean half-life of trichlorfon in cabbage was 1.80 d with a dissipation rate of 90% over 5 d, while that in soil was 3.05 d with a dissipation rate of 90% over 14 d at one experimental site. The dissipation rates of trichlorfon and its degradation product dichlorvos at the two experimental sites were different, suggesting that degradation of these pesticides was affected by local soil characteristics and climate. When applied at both the recommended dosage and at 1.5 times this, no detectable residues of either trichlorfon or dichlorvos were found in soil or cabbage at harvest. Although trichlorfon can easily degrade into dichlorvos, which is highly toxic to humans and other animals, the observed low residual levels of dichlorvos suggest that trichlorfon is safe when applied at the recommended dosage.     

Joint representation of physical locations and volatile organic compounds in indoor air from a healthy and a sick building

Many modern, energy-efficient buildings have been labeled “sick”, in view of the fact that their occupants display an unusually large number of sensory symptoms (e.g. eye irritation, dry skin and perception of persistent odors). Air samples were taken from locations (17) in two Stockholm preschools, one considered healthy, the other, sick. The samples (170) were analyzed by gas chromatography/mass spectrometry (GC/MS) and 33 volatile organic compounds were identified and quantified by GC peak heights. The relationship between chemicals and locations in the two preschools was represented spatially by correspondence analysis and other statistical techniques. The analyses clearly distinguish among the buildings and among locations within each building, including whether the sample was collected outdoors or indoors. Within the sick preschool, concentrations of light aromatic hydrocarbons increased with distance from the air supply, but there was no similar gradient in the healthy preschool. The chief results obtained by the comparatively new method of correspondence analysis are supported further by a discriminant analysis and a principal components analysis.     

渗滤液中污染物的粒度分布及其应用

渗滤液是一种难于处理的废水.论述了渗滤液中污染物的粒度分布.指出了不同粒度污染物中胶体态组分富含难降解有机物和重金属,其性质稳定,含量较高,对渗滤液的处理工艺选择和去除效果影响重大.最后对渗滤液的资源化进行了初步探讨.