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.     

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 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.     

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.     

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 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。     

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.     

The Clean Air Act and its Implications for Training Requisite Personnel

The Clean Air Act, Public Law 88-206, was signed into law on December 17, 1963. Among the new provisions was the authorization given to the Secretary of the Department of Health, Education, and Welfare to award grants for the support of State and local air pollution control programs. The Chief, Division of Air Pollution, then requested the Surgeon General’s Air Pollution Training Committee to make recommendations for the most effective way to train the required numbers of people. The Committee called a special three-day meeting at Airlie House with about 30 consultants. Recommendations for training stemming from the meeting included: (1) University-based programs combined with practical experience in control program. (2) Criteria for the selection of trainees. (3) The outline of a model program. These recommendations were submitted to the Chief, Division of Air Pollution and are currently reflected in the activation of one program and a request to the Congress for funds to initiate two more such programs during Fiscal Year 1966.     

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.     

The effect of thymol and its derivatives on reactions generating reactive oxygen species

The effects of thymol (TOH), thymoquinone (TQ) and dithymoquinone (TQ2) on the reactions generating reactive oxygen species (ROS) such as superoxide anion radical (O2*-), hydroxyl radical (HO*) and singlet oxygen (1O2) were tested using the chemiluminescence (CL) and spectrophotometry methods. All tested compounds acted as scavengers of various ROS. The rate constant of 1O2-dimols quenching by thymol was calculated.     

餐厨垃圾及其组分一级水解动力学模型研究

基于一级水解模型推导出含有单位可挥发性有机物理论沼气产量(ym,mg/L)与水解常数(k,d-1)组合项的动力学模型,将其应用于餐厨垃圾及其组分在厌氧消化过程中产沼气的特性规律分析,为研究厌氧消化机制提供理论基础。结果表明,除了脂肪厌氧消化拟合的R2为0.899 0,其余的均大于0.9,其中餐厨垃圾的R2为0.992 5,淀粉的R2为0.972 4。说明该模型能很好地反映厌氧消化的实际效果。厌氧消化水解速率依次为淀粉餐厨垃圾纤维素蛋白质脂肪。淀粉、餐厨垃圾、纤维素的k分别为0.198 3、0.089 7、0.013 9d-1,蛋白质、脂肪的k都小于零。单组分中淀粉lnym+lnk为4.983 6,表现出最好的产沼气特性;其次是蛋白质和纤维素,其值分别为2.157 8、2.046 6;脂肪产沼气特性最差,其值仅为0.902 4,与淀粉相比降低了81.89%;餐厨垃圾lnym+lnk为4.329 6,是淀粉的86.88%,产气特性仅次于淀粉。     

The impact of infield biomass burning on PM levels and its chemical composition

In the South of Italy, it is common for farmers to burn pruning waste from olive trees in spring. In order to evaluate the impact of the biomass burning source on the physical and chemical characteristics of the particulate matter (PM) emitted by these fires, a PM monitoring campaign was carried out in an olive grove. Daily PM10 samples were collected for 1 week, when there were no open fires, and when biomass was being burned, and at two different distances from the fires. Moreover, an optical particle counter and a polycyclic aromatic hydrocarbon (PAH) analyzer were used to measure the high time-resolved dimensional distribution of particles emitted and total PAHs concentrations, respectively. Chemical analysis of PM10 samples identified organic and inorganic components such as PAHs, ions, elements, and carbonaceous fractions (OC, EC). Analysis of the collected data showed the usefulness of organic and inorganic tracer species and of PAH diagnostic ratios for interpreting the impact of biomass fires on PM levels and on its chemical composition. Finally, high time-resolved monitoring of particle numbers and PAH concentrations was performed before, during, and after biomass burning, and these concentrations were seen to be very dependent on factors such as weather conditions, combustion efficiency, and temperature (smoldering versus flaming conditions), and moisture content of the wood burned.     

The effect of spent bleaching earth ageing process on its physicochemical and microbial composition and its potential use as a source of fatty acids and triterpenes

This study was aimed at investigating the physicochemical and microbiological changes that took place during the ageing process of spent bleaching earth in the presence of autochthonous microorganisms. Research material included fresh spent bleaching earth (SBE₀) and the same material after 3 years of storage at the constant temperature of 20 °C, without aeration and moistening (SBE₃). Changes in the chemical composition of analysed waste material were observed during its ageing process point to a spontaneous bioconversion of fat substance towards formation and/or release of free saturated fatty acids C16:0 and C18:0 (14.3 g 100 g^?1 D.M.), triterpenes (8.48 g 100 g^?1 D.M.), cholesterol (3.29 g 100 g^?1 D.M.), small quantities of carbohydrates and esters (0.80 g 100 g^?1 D.M.). This process was accompanied by other changes in physicochemical parameters of the waste material, such as colour, odour and viscosity, decrease in fat content from 28.27 to 24.6 % and that of soluble forms of metals (Mo, Cu, Fe, Zn, Ni, Cr and Mn), ranging from 25 to 75 %, and an increase in pH, from 3.85 to 4.2. At the same time, changes in the microbial consortium were observed.     

美国水质交易政策及其对上海的启示

介绍了美国水质交易政策的概念和实施状况,分析了水质交易必备的要素及取得的经济、环境和社会效益.上海在排污交易方面有多年的积累,可以借鉴美国在水质交易方面的经验,研究点源和非点源间的交易,基于市场的经济刺激政策,解决城市和农田径流产生的排放控制问题.