新型全氟化合物——全氟烷基磷酸对环境影响的研究综述

全氟烷基磷酸是一种新型全氟化表面活性剂,被广泛应用于匀染剂、湿润剂和农药中的消泡添加剂等。在美国,基于对其潜在毒性的考虑,美国环境保护总署已禁止全氟烷基磷酸在粮食作物农药中使用。从全氟烷基磷酸的注册使用情况、结构与环境行为、环境介质中的浓度水平和生物暴露毒性等方面分别展开论述,旨在为中国开展该类物质的环境研究提供可借鉴依据。     

Bioanalytical characterisation of multiple endocrine- and dioxin-like activities in sediments from reference and impacted small rivers

A comprehensive evaluation of organic contamination was performed in sediments sampled in two reference and three impacted small streams where endocrine disruptive (ED) effects in fish have been evidenced. The approach combined quantitative chemical analyses of more than 50 ED chemicals (EDCs) and a battery of in vitro bioassays allowing the quantification of receptor-mediated activities, namely estrogen (ER), androgen (AR), dioxin (AhR) and pregnane X (PXR) receptors. At the most impacted sites, chemical analyses showed the presence of natural estrogens, organochlorine pesticides, parabens, polycyclic aromatic hydrocarbons (16 PAHs), bisphenol A and alkylphenols, while synthetic steroids, myco-estrogens and phyto-estrogens were not detected. Determination of toxic-equivalent amounts showed that 28-96% of estrogenic activities in bioassays (0.2-6.3 ng/g 17β-estradiol equivalents) were explained by 17β-estradiol and estrone. PAHs were major contributors (20-60%) to the total dioxin-like activities. Interestingly, high PXR and (anti)AR activities were detected; however, the targeted analysed compounds could not explain the measured biological activities. This study highlighted the presence of multiple organic EDCs in French river sediments subjected to mixed diffuse pollution, and argues for the need to further identify AR and PXR active compounds in the aquatic environment.     

Chlortetracycline and tylosin runoff from soils treated with antimicrobial containing manure

This study assessed the runoff potential of tylosin and chlortetracycline (CTC) from soils treated with manure from swine fed rations containing the highest labeled rate of each chemical. Slurry manures from the swine contained either CTC at 108 μ g/g or tylosin at 0.3 μ g/g. These manures were surface applied to clay loam, silty clay loam, and silt loam soils at a rate of 0.22 Mg/ha. In one trial, tylosin was applied directly to the soil surface to examine runoff potential of water and chemical when manure was not present. Water was applied using a sprinkler infiltrometer 24-hr after manure application with runoff collected incrementally every 5 min for about 45 min. A biofilm crust formed on all manure-treated surfaces and infiltration was impeded with > 70% of the applied water collected as runoff. The total amount of CTC collected ranged from 0.9 to 3.5% of the amount applied whereas tylosin ranged from 8.4 to 12%. These data indicate that if surface-applied manure contains antimicrobials, runoff could lead to offsite contamination.     

Use of fugacity model to analyze temperature-dependent removal of micro-contaminants in sewage treatment plants

Effluents from sewage treatment plants (STPs) are known to contain residual micro-contaminants including endocrine disrupting chemicals (EDCs) despite the utilization of various removal processes. Temperature alters the efficacy of removal processes; however, experimental measurements of EDC removal at various temperatures are limited. Extrapolation of EDC behavior over a wide temperature range is possible using available physicochemical property data followed by the correction of temperature dependency. A level II fugacity-based STP model was employed by inputting parameters obtained from the literature and estimated by the US EPA’s Estimations Programs Interface (EPI) including EPI’s BIOWIN for temperature-dependent biodegradation half-lives. EDC removals in a three-stage activated sludge system were modeled under various temperatures and hydraulic retention times (HRTs) for representative compounds of various properties. Sensitivity analysis indicates that temperature plays a significant role in the model outcomes. Increasing temperature considerably enhances the removal of β-estradiol, ethinyestradiol, bisphenol, phenol, and tetrachloroethylene, but not testosterone with the highest biodegradation rate. The shortcomings of BIOWIN were mitigated by the correction of highly temperature-dependent biodegradation rates using the Arrhenius equation. The model predicts well the effects of operating temperature and HRTs on the removal via volatilization, adsorption, and biodegradation. The model also reveals that an impractically long HRT is needed to achieve a high EDC removal. The STP model along with temperature corrections is able to provide some useful insight into the different patterns of STP performance, and useful operational considerations relevant to EDC removal at winter low temperatures.     

危险化学品运输事故初探

危险化学品运输是一种动态危险源,在运输过程中火灾、爆炸、泄漏、中毒事故时有发生,对人类生命、物质财产和生态环境的安全构成极大威胁.对危险化学品在运输过程中事故发生的类型、事故的成因、事故的危害进行了探讨,阐述了事故的预防措施以及事故后如何做好减灾工作.     

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.     

Impacts on industry of Europe's emerging chemicals policy REACh

For Europe, a new regime in chemicals regulation is about to start. After the proposal of the European Commission concerning the Registration, Evaluation and Authorization of Chemicals (REACh) passed its readings in the European Parliament and some differences with the European Council of Ministers were resolved, the regulation will come into force in June 2007. This paper is focused on the question how serious the cost burdens for industry induced by REACh will be, and whether the New European Member States (NMS) which joined the European Union in May 2004 will be able to cope with the regulation. This evaluation has been done by assessing the legislative, administrative and economic framework in New Member States and by analysing real business cases in companies. The empirical showcase business impact studies are at the same time of interest for companies of EU-15 states, other European countries who may implement the regulation, and even for exporters of raw materials and chemicals outside Europe, who will also have to comply with REACh if they market in the European Community. The results give no indications that REACh adoption will bring significant drawbacks to companies in the NMS. The emerging regulation will bring challenges for individual companies, especially for small and medium-sized ones, but for the European chemical industry as a whole, there is no question that it will be able to cope with REACh burdens without losing its global competitiveness.     

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.