对化学品登记要求的数据解释——急性毒性和急性刺激

本文对化学品登记时所要求的部分健康效应数据一急性毒性和急性刺激做了解释.涉及到的测试参数包括:急性经口毒性、急性经皮毒性、急性吸入毒性、急性皮肤刺激/腐蚀和急性眼睛刺激/腐蚀.     

Bioconcentration of n-dodecane and its highly branched isomer 2,2,4,6,6-pentamethylheptane in fathead minnows

Petroleum products are complex mixtures of hydrocarbons. They are important as constituents of fuels and lubricants, and as key raw materials for the chemicals industry. Since there is a potential for accidental releases to the aquatic environment, bioaccumulation of higher hydrocarbons is of concern. Here, the bioconcentration behaviour of two representative hydrocarbons, the dodecane isomers n-dodecane and 2,2,4,6,6-pentamethylheptane (PMH), was investigated in fathead minnows at concentrations in water below their maximum aqueous solubility. The concentration of n-dodecane in fish did not exceed our method limit of detection of 60 μg/kg. In contrast, PMH could be quantified in fish. No significant increase in the ratio of PMH concentrations in fish to water could be detected indicating that an exposure time of 4–10 days is sufficient to approach steady-state. For n-dodecane the upper limit of the bioconcentration factor (BCF) is estimated by dividing the method limit of detection by the exposure concentration and a value of 240 l/kg is derived. For PMH the bioconcentration factor, estimated as the average fish/water concentration ratio during the steady-state part of the experiment, ranges between 880 and 3500 l/kg. The BCFs of both compounds are small compared to their hydrophobicity. Given that both linear and branched hydrocarbons are known to be biotransformed by fish, it appears that efficient metabolism of the test compounds in fathead minnows prevents bioaccumulation.     

Endocrine disruption of water and sediment extracts in a non-radioactive dot blot/RNAse protection-assay using isolated hepatocytes of rainbow trout

Goal, Scope and Background In order to evaluate the estrogenic activity of sediments and XAD water extracts of selected sites of the catchment area of the River Neckar, a river system in Southern Germany, an integrative assessment approach was used to assess the ecological hazard potential of endocrine-disrupting compounds in sediment and water. Methods The approach is based on estrogen receptor-mediated vitellogenin synthesis induced in isolated hepatocytes of rainbow trout and quantified in a non-radioactive dot blot/RNAse protection-assay in parallel to comprehensive chemical analyses of estrogenic substances. Results and Discussion Numerous investigated extracts revealed an estrogen activity comparable to that of the positive control (1 nM 17?-estradiol corresponding to 270 ng/L in the test medium). Based on a concentration factor of 30 in the extracts and a recovery of XAD resins of approximately 80 %, 17?-estradiol equivalent concentrations between 20 and 26.7 ng/L could be calculated downstream of a sewage treatment plant (< 0.1 ng/L for a reference site). A comparison of the bioassay-derived Bio-TEQs (toxicity equivalents) and the Chem-TEQs revealed a high correlation with a Pearson coefficient of 0.85, indicating that the same ranking of the samples could be obtained with respect to the endocrine disrupting potential with both chemical and bioanalytical analysis. However, the TEQ concentrations computed from chemical analyses were significantly lower than the bioassay-derived TEQ concentrations. In fact, in none of the samples, more than 14 % of the vitellogenin-inducing potency could be attributed to the substances (steroids, alkylphenols, bisphenol A, diethylstilbestrol) analyzed. A comparison of the endocrine disrupting potential of sediments extracted by the solvents acetone and methanol revealed lower biological effects for acetone-extracted samples. Possible reasons may be a masking of endocrine effects in acetone extracts by cytotoxicity, a low extraction efficiency of the solvent acetone, or anti-estrogen potencies of some extracted sediment compounds. Using a mass balance approach, the contribution of the compounds analyzed chemically (Chem-TEQs) to the total endocrine activity (Bio-TEQs) was calculated. Based on the very low detection limits, particularly of the steroids with their high TEF factors, results revealed that a calculation of the Chem-TEQs is associated with considerable scale inaccuracy: Whereas only 7-15 % of the biological effectiveness (Bio-TEQs) could be explained by endocrine substances identified above the detection limits, the assumption of concentrations slightly below the given detection limits would result in a significant over estimation (137-197 %) of the Bio-TEQs. Even the interassay variation of the dot blot assay with different fish donors for primary hepatocyte (factor 2 - 2.5) is relatively low, when compared to the large range of the Chem-TEQ concentrations (factor 20) obtained when applying different modes of calculation. Conclusions and Outlook Overall, only a minor portion of the endocrine activity detected by bioassays could be linked to compounds identified by chemical analysis. In vitro assays for assessment of endocrine activities are useful as sensitive integrating methods that provide quantitative estimates of the total activity of particular receptor-mediated responses. Although discrepancies may also result from different bioanalytical approaches, it is overall likely that bioanalytical and not chemical analytical approaches give the correct estimate of endocrine disrupting potencies in environmental samples. As a conclusion, assessment of endocrine disruption based on chemical analysis alone does not appear sufficient and further research into the spectrum of substances with potential endocrine activity as well as into additive or even synergistic effects in complex environmental samples is urgently needed.     

苯酚及其氯代物对大型[氵蚤]的毒性效应和微观机理探讨

采用静态生物急性试验的方法，研究了5种酚类化合物对大型[氵蚤]的急性毒性效应，并利用正辛醇／水分配系数（Kow）对实验测得的毒性数值进行了统计分析，得到了有效的毒性估测模型。研究结果表明，大型[氵蚤]的幼溪接触不同化合物的不同浓度，活动会受到抑制，甚至死亡，苯酚、4-氯酚、2，4-二氯酚、2，3，4-三氯酚和五氯酚的48hEC50分别为9．15、4．64、4．40、1．92、0．37mg／L；根据化学物质对[氵蚤]类的毒性评价标准，这5种化合物都属高毒物质，其中五氯酚具有极高毒性。另外，五氯酚对大型[氵蚤]的致毒关键步骤不仅包括传输分配过程还有生化反应。     

Model reactor for photocatalytic degradation of persistent chemicals in ponds and waste water

A laboratory scale flow-through model reactor for the degradation of persistent chemicals using titanium dioxide (TiO₂) as photocatalyst immobilized on glass beads is presented. In the test system with a volume of 18 L contaminated water is pumped to the upper part of the floating reactor and flows over the coated beads which are exposed to UV-radiation. The degradation of two dyes of different persistance was investigated. Primary degradation of methylene blue did not fit a first order kinetic due to coincident adsorption onto the photocatalyst and direct photolysis, resulting in a half-life of 6 h. A filtrate of a green algae suspension accelerated the colour removal. In contrast, reactive red 2 was degraded only by photocatalysis; neither adsorption nor direct photolysis led to a colour removal. The course of primary degradation followed a first order kinetic with a half-life of 18 h and a rate constant of 0.04 h⁻¹. Analysis of the degradation products indicated mineralization by detection of NO₂⁻ and NO₃⁻, accompanied by a decrease of pH and an increase of conductivity. A successful adaptation of the model reactor (scale 1:10) to dimensions required for surface waters and waste water treatment plants would be a costefficient and environmentally sustainable application of photocatalysis for the treatment of industrially polluted water and could be of relevance for third world contries, particularly those favoured by high solar radiation.     

有机物的结构──活性定量关系及其在环境化学和环境毒理学中的应用

有机物的结构──活性定量关系及其在环境化学和环境毒理学中的应用王飞越（北京大学城市与环境学系，北京１００８７１）陈雁飞（武汉大学环境科学系）最近几十年来，有机物结构──活性定量关系研究（ＱＳＡＲ，ＱｕａｎｔｉｔａｔｉｖｅＳｔｒｕｃｔｕｒｅ－Ａｃｔｉｖ...     

改性无烟煤去除水中内分泌干扰物的性能探究

以KOH为改性剂对无烟煤改性,研究了改性前后无烟煤对3种内分泌干扰物EDCs(17α-乙炔基雌二醇EE2、双酚A BPA、磺胺甲噁唑SMZ)的吸附性能。结果表明,KOH改性对无烟煤的孔结构和表面性质产生影响,提高了无烟煤对3种EDCs的吸附量,其中对EE2的吸附量提高了近2倍。3种EDCs在改性前后2种无烟煤上的吸附过程均可用伪二级动力学描述,吸附等温线更符合Langmuir吸附等温方程,表现为化学吸附。改性前后2种无烟煤对EE2均表现出最高吸附能力,平衡吸附量(qe)分别为0.214 7μg/mg与0.622 9μg/mg;其次是BPA;最差是SMZ,qe仅为0.095 9μg/mg与0.124 2μg/mg。进一步研究表明,目标物的吸附情况与其憎水性质和分子结构有关,无烟煤吸附目标物的能力与其正辛醇/水分配系数正相关。     

生物法-人工湿地工艺处理采油废水及其有机物的降解特性

采用水解酸化-好氧-人工湿地和水解酸化-人工湿地2种工艺流程处理油田某联合处理站经隔油、混凝处理的采油废水,并运用气相色谱-质谱(GC-MS)技术研究采油废水处理过程中有机物的迁移降解规律.结果表明,水解酸化(水力停留时间HRT=20 h)好-氧(HRT=10 h人)-工湿地(HRT=2 d)与水解酸化(HRT=20 h人)-工湿地(HRT=4 d),2种工艺的出水水质都能达到COD≤80 mg/L、NH+4-N≤15 mg/L.GC-MS分析结果表明,水解酸化能显著改善采油废水的可生化性,好氧及人工湿地对含苯环类有机污染物处理效果显著.     

浅析化学事故应急响应专线的发展

纵观国外同类化学事故应急咨询机构30多年的发展经验,结合化学事故应急响应专线的现状,提出了扩大化学事故应急响应专线的服务范围、加强化学事故技术支持体系的建设及加强与国内外同类机构的交流与合作等发展建议。     

煤层气产出水处理与资源化技术研究进展

煤层气田的大规模开发会带来一系列的环境问题,其中,煤层气产出水的污染控制及资源化问题最为突出。综述了国内外煤层气产出水的主要处理工艺和技术,结合我国的主要煤层气田的具体情况,提出了相应的建议。