有机化学品不同温度下(过冷)液体蒸气压预测模型的建立与评价

(过冷)液体蒸气压(PL)是评价化学品在环境中分配、迁移和归趋行为的重要参数。PL具有较强的温度依附性。发展一种能够精确预测不同环境温度下化学品PL的方法,有助于填补化学品生态风险评估的大量数据缺失。本研究收集整理了661种有机化合物在不同温度下(200~830 K)共计10 478个log PL值。在此基础上,采用偏最小二乘(PLS)回归和支持向量机(SVM)方法,构建了PL的线性和非线性预测模型。结果表明:2种模型均具有良好的拟合度、稳健性及预测能力,SVM模型的预测性能略高于PLS模型(PLS:R2adj.tra=0.912,RMSEtra=0.477,Q2ext=0.910;SVM:R2adj.tra=0.997,RMSEtra=0.092,Q2ext=0.967)。机理分析表明,温度是影响PL的主要因素,温度越高,蒸气压越大;其次,X1sol也影响PL大小,X1sol用来描述分子间的色散作用,分子间色散力越小,蒸气压越大;此外,化合物的氢键个数、极性和分子构型等因素也影响PL大小。采用Wiliams plot方法表征了PLS模型应用域。所建立的模型可用来预测烷烃、烯烃、醇、酮、羧酸、苯、酚、联苯、卤代芳香烃、含N化合物及含S化合物在不同温度下的PL数据。     

爆炸超压场景下危化品社会风险对允许规划人口密度的影响分析*

为研究危化品重大危险源基于社会风险基准的规划管控影响,采用我国标准规定的定量风险评价方法,TNT当量炸药简化方法,针对最大TNT当量炸药、事故发生总累计频率、人口密度分布控制参数等不同工况条件,对比分析国土开发强度的允许人口密度受社会风险约束影响的变化规律。研究结果表明:人口密度指数分布控制参数Nk与Nb的允许取值随最大TNT当量炸药和事故发生总累计频率降低而提高;确定工况下,允许总人口规模受最大TNT当量炸药影响很小;在最大TNT当量炸药大于100 t或事故发生总累计频率小于1×10-8次/a时可按最大事故场景进行规划控制分析。     

壬基酚的环境生物地球化学研究进展及对新污染物管理的建议

近年来,我国大气环境、水环境和土壤环境质量得到一定的改善,“碧水蓝天”已经成为常态.但随着持久性有机污染物、内分泌干扰物、抗生素和微塑料等新污染物在环境中不断被检出,新污染物正逐步受到广泛的关注,壬基酚作为一种典型的内分泌干扰物也备受研究人员的关注.系统地概括了我国水体中壬基酚的环境行为和暴露水平,并基于风险商法和联合概率曲线法对壬基酚可能造成的生态风险进行了评估.结果表明,壬基酚对水生生物的毒性效应主要包括急性毒性、生长发育毒性、雌激素效应和繁殖毒性;壬基酚在我国主要流域水体中普遍存在,其浓度平均值在60～1 000 ng·L^-1,浓度最高值可达4 628 ng·L^-1;基于风险商法和联合概率曲线法的风险评估结果表明,壬基酚对我国主要流域里的水生生物均存在一定的风险.最后,总结了目前比较常用的壬基酚处理处置和风险管控技术,比较了国际上内分泌干扰物的监管方法,针对我国在新污染物环境管理中存在的问题,提出了针对性政策建议,研究结果可以为我国新污染物管理和管控提供参考.     

Gasoline-derived methyl tert-butyl ether as a potential obesogen linked to metabolic syndrome

正The power and efficiency of gasoline engines is often improved through the use of fuel with high octane ratings.The octane rating of fuel could be further increased with oxygenate additives such as alcohols and ethers, with methyl tert-butyl ether (MTBE) being one of the most common gasoline additives. The Agency for Toxic Substances and Disease     

城市污水处理厂内分泌干扰物浓度分布和去除规律

采集南方某城市3个污水处理厂进出水及各工艺单元的水样,通过固相萃取-衍生化过程对水样进行预处理,并用气相色谱-质谱联用仪定量检测水样中的17α-雌二醇(17α-E2)、雌酮(E1)、雌二醇(E2)、雌炔醇(EE2)、雌三醇(E3)、辛基酚(OP)、正壬基酚(NP)和双酚A(BPA)等8种内分泌干扰物(EDCs).连续4个季度的分析结果显示,3个污水厂进出水及各工艺单元中均有EDCs检出,EE2和BPA是含量最高的两种EDCs,出水中最高浓度分别达到498.9ng.L-1和2652.5ng.L-1,其他6种EDCs浓度均不超过100ng.L-1;生物处理工艺对EE2、E3、NP、OP和BPA有较高的去除率,平均去除率约为57%～85%,但对于E1、E2和17α-E2的去除率较低且不稳定;一级处理工艺对EDCs仅有低于18%的去除率;紫外辐照消毒工艺对EDCs的去除没有明显效果;EDCs浓度季节差异显著,由于雨水的稀释作用,旱季浓度约为雨季的2.5～7.8倍.本文对于了解我国南方地区污水处理工艺中EDCs类物质的分布和转化特点有一定的参考意义.     

A monoclonal antibody against Lates calcarifer vitellogenin and a competitive ELISA to evaluate vitellogenin induction after exposure to xenoestrogen

A monoclonal antibody specific to sea bass(Lates calcarifer) vitellogenin(VTG) was developed,for use as a tool for monitoring endocrine disrupting chemicals(EDCs). VTG was induced in sea bass by intramuscular injection of 17β-estradiol(E_2: 2 mg/kg) every three days. Blood was collected three days after the last injection. Plasma VTG was then purified by chromatography in hydroxyapatite and a sephacryl-S300 column. Characterizations of purified VTG were done by phospholipoglycoprotein staining on a native-PAGE with confirmation by mass spectrometry(LC-MS/MS). Antibody was raised in mice by injection of purified VTG. After monoclonal antibody production, the hybridoma clone No. 41(MAb-sea bass VTG 41)was selected and developed for quantification of VTG by competitive enzyme-linked immunosorbent assay(ELISA). The ELISA method was sensitive with a detection limit of VTG 40 ng/mL. MAb-sea bass VTG 41 was specific to VTG from E_2-treated sea bass and others EDCs(Nonylphenol, Benzo[a]pyrene and CdCl_2). Moreover, cross-reactivity was also found in E_2-treated coral grouper(Epinephelus corallicola). The ELISA method obtained from this work can be further applied for the assessment of EDCs in Thailand and Southeast Asia's aquatic environment.     

Perfluorinated Surfactants in Surface and Drinking Waters (9 pp)

Background, Aim and Scope In this paper recent results are provided of an investigation on the discovery of 12 perfluorinated surfactants (PS) in different surface and drinking waters (Skutlarek et al. 2006 a, Skutlarek et al. 2006 b). In the last years, many studies have reported ubiquitous distribution of this group of perfluorinated chemicals, especially perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) in the environment, particularly in wildlife animal and human samples (Giesy and Kannan 2001, Houde et al. 2006, Prevedouros et al. 2006). Perfluorinated surfactants (e.g. PFOS and PFOA) have shown different potentials for reproductory interference and carcinogenity in animal experiments as well as partly long half-lives in humans (Guruge et al. 2006, FSA UK 2006a, FSA UK 2006b, 3M 2005, OECD 2002, Yao and Zhong 2005). They possess compound-dependent extreme recalcitrance against microbiological and chemical degradation and, in addition, they show variable potentials for bioaccumulation in animals and humans (Houde et al. 2006). Materials and Methods: Surface and drinking water samples were collected from different sampling sites: - Surface waters: samples taken from the rivers Rhine, Ruhr, Moehne and some of their tributaries. Further samples were taken from the Rhine-Herne-Canal and the Wesel-Datteln-Canal. - Drinking waters: samples taken in public buildings of the Rhine-Ruhr area. After sample clean-up and concentration by solid-phase extraction, the perfluorinated surfactants were determined using HPLC-MS/MS. Results: All measured concentrations (sum of seven mainly detected components) in the Rhine river and its main tributaries (mouths) were determined below 100 ng/L. The Ruhr river (tributary of the Rhine) showed the highest concentration (94 ng/L), but with a completely different pattern of components (PFOA as major component), as compared with the other tributaries and the Rhine river. Further investigations along the Ruhr river showed remarkably high concentrations of PS in the upper reaches of the Ruhr river and the Moehne river (tributary of the Ruhr) (Ruhr: up to 446 ng/L, Moehne: up to 4385 ng/L). The maximum concentration of all drinking water samples taken in the Rhine-Ruhr area was determined at 598 ng/L with the major component PFOA (519 ng/L). Discussion: The surface water contaminations most likely stem from contaminated inorganic and organic waste materials (so-called 'Abfallgemisch'). This waste material was legally applied to several agricultural areas on the upper reaches of the Moehne. Perfluorinated surfactants could be detected in some suchlike soil samples. They contaminated the river and the reservoir belonging to it, likely by superficial run-off over several months or probably years. Downstream, dilution effects are held responsible for decreasing concentrations of PS in surface waters of the Moehne and the Ruhr river. In analogy to the surface water samples, PS (major component PFOA) can be determined in many drinking water samples of the Rhine-Ruhr area where the water supplies are mainly based on bank filtration and artificial recharge. Conclusions: The concentrations found in drinking waters decreased with the concentrations of the corresponding raw water samples along the flow direction of the Ruhr river (from east to west) and were not significantly different from surface water concentrations. This indicates that perfluorinated surfactants are at present not successfully removed by water treatment steps. Recommendations and Perspectives: Because of their different problematic properties (persistence, mobility, toxicity, bioaccumulation), the concentrations of specific perfluorinated surfactants and their precursors in drinking waters and food have to be minimised. Therefore, it is of utmost importance to take the initiative to establish suitable legal regulations (limitations/ban) concerning the production and use of these surfactants and their precursors. Furthermore, it is indispensable to protect water resources from these compounds. A discussion on appropriate limit values in drinking water and foodstuffs is urgently needed. Concerning the assumed soil contamination, the corresponding regulation (Bioabfall-Verordnung 1998 – Regulation on Organic Waste 1998) should be extended to allow the control of relevant organic pollutants.     

The Precautionary Principle and Chemicals Regulation: Past Achievements and Future Possibilities (8 pages)

Background, Aim and Scope

The paper investigates the development of the institutional basis of the present modes of chemicals regulation and management, with special attention to interrelations with the precautionary principle. Main Features: The paper elucidates on how the precautionary principle has been shaped in relation to chemicals regulation and management since Carson's Silent Spring (years before the principle was confirmed as a policy-principle in German and European legislation. Furthermore, it is examined how the precautionary principle interacted with the development of the present chemicals regulatory regime, in a complex interplay within the OECD and Member Countries. The present modes of precaution in the new EU chemical legislation – REACH – are investigated with respect to the precautionary principle, and tested against two contemporary problems; brominated flame retardants and endocrine disrupting substances. Results: The analysis demonstrates the changing character of the integration of the precautionary principle. The main tendencies are from implicit to more explicit precaution and from a closed expert-orientation towards a more deliberative approach to scientific knowledge and uncertainty. The results demonstrate that the precautionary principle is manifest in both the design of the testing strategy and in policy provisions. In particular, the substitution of hazardous substances with less hazardous is important. Discussion: Despite explicit attention to the precautionary principle, is the present reformulation of the European Chemicals policy in danger of falling into loop-holes that equal problems related to the present regulation of existing chemicals? 'Precaution' has been reduced virtually to an abstract concept that is more or less devoid of practical meaning in the regulatory process. Conclusions: It is concluded that the role of the precautionary principle in chemicals regulation will require continued scrutiny in the future shaping of the REACH strategy. Perspectives: Continued development of robust and precaution-based chemicals regulation will have to involve both new data-generation strategies and new forms of political decision-making, with special attention given to transparency and deliberative policymaking.     

我国危险化学品道路运输的现状与对策研究

随着我国工业和经济的发展,危险化学品的需求量越来越大,危险化学品的道路运输也越来越频繁,由危险化学品道路运输而引发的事故也越来越多。为此,必须基于我国危险化学品道路运输的现状,借鉴发达国家在危险化学品道路运输方面较成熟的经验,提出符合我国国情的危险化学品道路运输安全管理的对策,以达到减少危险化学品道路运输事故发生的目的,最大限度地降低由危险化学品道路运输事故引起的生命财产的损失。     

TA-FTIR/MS用于硝酸铵及其混合物的热化学行为研究

为评价物料混合对危险化学品热化学行为的影响,采用热分析-红外/质谱联用技术(TA-FTIR/MS)研究硝酸铵、柠檬酸和蔗糖的混合物的热化学行为。通过对硝酸铵及其混合物的分解温度和分解过程中逸出气体的分析,发现硝酸铵、柠檬酸和蔗糖的混合物热分解温度分别降低至135℃和153℃,而硝酸铵与甲基纤维素的混合物分解温度与硝酸铵基本相同为201℃,且各混合体系的气相分解产物均有氮氧化物(NOX),H2O和CO2。结果表明,混合物受热后其中的硝酸铵首先分解为硝酸和氨气;酸性物质和还原性物质由于对硝酸的分解反应有催化作用,使得混合物的热稳定性下降。