印刷电路板(PCB)厂挥发性有机物(VOCs)排放指示物筛选

采用VOCs快速测定仪和SUMMA罐采样、GC/MS分析方法,采样分析了上海某工业区3个印刷电路板厂生产车间和废气排放口的VOCs含量水平、组成特征和源成分谱.结果表明,在9月和12月2次采样期间,A、B、H厂生产车间总挥发性有机物(TVOCs)(9月/12月)最高浓度分别为(2.94/2.01)×10-9、(3.18/1.11)×10-6、(0.70/0.18)×10-9;废气排放口TVOCs最高浓度则分别为(0.86/0.90)×10-9、(31.2/12.0)×10-6、(1.24/0.30)×10-9.GC/MS分析结果表明,主要检出了烷烃、烯烃、苯系物、酮类、氯代烷烃、氯代苯类、酯类等7大类共67种VOCs化合物;A、B、H厂生产车间/废气排放口最高检出物和检出浓度分别为:2-丁酮6.73 mg.m-3/2-甲基己烷5.93 mg.m-3、乙酸乙酯8.90 mg.m-3/丙烷9.64 mg.m-3、丙烷2.04 mg.m-3/丙烷1.69 mg.m-3.苯、甲苯、二甲苯检出率均为100%,三厂各点位最高检出浓度/平均浓度分别为0.077 mg.m-3/0.035 mg.m-3、0.56 mg.m-3/0.31 mg.m-3、0.21 mg.m-3/0.12 mg.m-3(间+对-二甲苯)和0.081 mg.m-3/0.050 mg.m-3(邻-二甲苯).源成分谱和PCA分析结果表明,A、B厂的VOCs特征轮廓图谱较相似,特征化合物为苯、甲苯、二甲苯以及丙酮和2-丁酮;H厂主要特征污染物除三苯外,还有氯苯和氯代烷烃类化合物.结合原辅材料及生产工艺分析,溶剂、涂料使用和工艺过程的逸散是生产车间面源VOCs排放的主要来源,废气排放口是VOCs重点排放点源.     

三-(2,3-二溴丙基)异氰脲酸酯和17β-雌二醇复合暴露对雄性斑马鱼的毒性效应

三-(2,3-二溴丙基)异氰脲酸酯(TBC)是近年来在环境中新检测到的一种杂环溴化阻燃剂,但其毒性效应尚不明确.我们以雄性斑马鱼为受试动物,开展了TBC和17β-雌二醇(E2)的复合暴露实验,以研究TBC潜在的致毒机制.结果显示TBC可显著抑制E2所引起的斑马鱼肥满度指数上升,并能改善E2暴露所造成的斑马鱼精子细胞比例降低和性腺发育迟缓;E2暴露可造成斑马鱼肝组织脂肪样病变,肝中MDA含量上升,但SOD活力没有显著改变;TBC复合暴露后,MDA含量呈现下降趋势,但鱼肝仍有明显的脂肪样病变,对肝脏中的SOD活力也没有显著影响;更重要的是,TBC可显著抑制E2单一暴露所诱导的雄鱼肝脏中卵黄蛋白原基因的表达,这些数据表明TBC具有明显的内分泌干扰效应.因此,需要进一步关注TBC这类杂环溴化阻燃剂对水环境的潜在危害.     

机场货站易爆危险品存储区外部安全防护距离研究*

为合理设定机场货站易爆危险品存储区外部安全防护距离,基于爆炸威力计算模型,利用有限元分析软件AUTODYN模拟包装约束下爆炸品爆炸冲击波特性,通过引入包装约束系数,描述包装材料对爆炸威力影响,计算航空运输易爆危险品存储区外部安全防护距离。结果表明:1 mm厚度聚碳酸酯、钢和铝材质外包装的包装约束系数分别为0.904 7,0.860 1,0.870 6,相较于聚碳酸酯和铝材质,钢材质外包装对易爆危险品爆炸威力削弱程度较大。研究结果可为机场货站外部安全防护距离规划设置提供参考。     

Annual production and molecular weight as an influential factor for environmental distribution of chemicals — a case study in Japan

The changes promoted by treatment of a highly polluted soil with sulphuric acid or calcium hydroxide for changing its pH value are studied by controlling physical properties (particle size, TGA and DTA curves), evolution of metal species (exchangeable, as carbonates, related to Fe‐Mn oxides, linked to organic matter and residual) and metal uptake by plant cultures. Metal contents were determined, after wet digestion with HF—HNO₃—HC1O₄ when necessary, by AAS (Ca, Mg, Cu, Pb, Mn, Fe, Zn) or emission (Na, K). The treatment of soil with successive amounts of sulphuric leads to changes in particle size, hydration properties and exothermic peak for organic matter combustion. Very small changes were, however, detected in the alkaline treatment of soil. Soil treatments do not have practical influence on speciation of some metals (Na, K, Mg, Pb, Mn, Fe), but the intensity of the acid treatment leads to both an increase in the Cu extraction and a decrease in the Ca solubilization, probably through gypsum formation. In the case of zinc a maximum solubility in the middle of the range of acid treatment was observed. The comparison among extractants shows solubilities high for two pollutants (Pb, Cu), associated mainly to Fe—Mn oxides and organic matter, and low for two macrocomponents (Fe, K). The rest of metals, basically present in soil as carbonates or oxides, have intermediate extractions. Pot cultures weights depended mainly on both the treatment of soil (poor development in the more acid sample and drainage difficulties in the rest of acid treatments) and the situation (very low weights in laboratory runs as compared with outside), but the irrigation with water or a diluted sulphuric acid solution (at pH = 4.0) did not produce significant weight changes. Tendencies to increase plant pollution were observed for smaller soil pH, acid irrigation and probably for outside cultures, due to uptake by leaves.     

Rapid resolution liquid chromatography-tandem mass spectrometry method for the determination of endocrine disrupting chemicals (EDCs), pharmaceuticals and personal care products (PPCPs) in wastewater irrigated soils

A multiresidue analytical method was developed for the determination of 9 endocrine disrupting chemicals (EDCs) and 19 pharmaceuticals and personal care products (PPCPs) including acidic and neutral pharmaceuticals in water and soil samples using rapid resolution liquid chromatography-tandem mass spectrometry (RRLC-MS/MS). Solid phase extraction (SPE), and ultrasonic extraction combined with silica gel purification were applied as pretreatment methods for water and soil samples, respectively. The extracts of the EDCs and PPCPs in water and soil samples were then analyzed by RRLC-MS/MS in electrospray ionization (ESI) mode in three independent runs. The chromatographic mobile phases consisted of Milli-Q water and acetonitrile for EDCs and neutral pharmaceuticals, and Milli-Q water containing 0.01 % acetic acid (v/v) and acetonitrile: methanol (1:1, v/v) for acidic pharmaceuticals at a flow rate of 0.3 mL/min. Most of the target compounds exhibited signal suppression due to matrix effects. Measures taken to reduce matrix effects included use of isotope-labeled internal standards, and application of matrix-match calibration curves in the RRLC-MS/MS analyses. The limits of quantitation ranged between 0.15 and 14.08 ng/L for water samples and between 0.06 and 10.64 ng/g for solid samples. The recoveries for the target analytes ranged from 62 to 208 % in water samples and 43 to 177 % in solid samples, with majority of the target compounds having recoveries ranging between 70–120 %. Precision, expressed as the relative standard deviation (RSD), was obtained less than 7.6 and 20.5 % for repeatability and reproducibility, respectively. The established method was successfully applied to the water and soil samples from four irrigated plots in Guangzhou. Six compounds namely bisphenol-A, 4-nonylphenol, triclosan, triclocarban, salicylic acid and clofibric acid were detected in the soils.     

Accumulation, distribution and transformation of DDT and PCBs by Phragmites australis and Oryza sativa L.: I. Whole plant study

Glasshouse experiments were conducted to determine the accumulation, distribution and transformation of o,p′-DDT, p,p′-DDT and PCBs by common reed (Phragmites australis) and rice (Oryza sativa L.) under hydroponic conditions. The culture solution was spiked with the organic pollutants and samples were collected daily. Analysis of the plants at harvest showed that both species had removed DDT and PCBs from the solution. DDT appeared to have accumulated within P. australis by both passive adsorption and active absorption. Both o,p′-DDT and p,p′-DDT were transformed within P. australis. DDD was the major metabolite and the transformation was mediated by reductive dehalogenation. Plant long-distance transportation systems may be involved in the translocation of PCBs within P. australis and the affinity of the PCBs for lipids is one of the major factors affecting their uptake and translocation within the plants. Similar but less pronounced results were found in O. sativa and suggest that these wetland plants may be used for the plant-mediated remediation of persistent organic pollutants.     

Registering and analysing data on detection of chemicals in the environment

As part of the research project “information system for environmental chemicals” a factual databank on a testset of 68 chemicals was developed. The set-up of the databank is described and the analysis of the results is shown for benzo(k)fluoranthene using a graphical boxplot illustration.     

Life Cycle Assessment as Part of Sustainability Assessment for Chemicals (5 pp)

Background LCA is the only internationally standardized environmental assessment tool (ISO 14040-43) for product systems, including services and processes. The analysis is done ‘from cradle-to-grave’, i.e. over the whole life cycle. LCA is essentially a comparative method: different systems fulfilling the same function (serving the same purpose) are compared on the basis of a ‘functional unit’ - a quantitative measure of this function or purpose. It is often believed that LCA can be used for judging the (relative) sustainability of product systems. This is only partly true, however, since LCA is restricted to the environmental part of the triad ‘environment/ecology - economy - social aspects (including intergenerational fairness)’ which constitutes sustainability. Standardized assessment tools for the second and the third part are still lacking, but Life Cycle Costing (LCC) seems to be a promising candidate for the economic part. Social Life Cycle Assessment still has to be developed on the basis of known social indicators.Method and Limitations LCA is most frequently used for the comparative assessment or optimization analysis of final products. Materials and chemicals are difficult to analyse from cradle-to-grave, since they are used in many, often innumerable product systems, which all would have to be studied in detail to give a complete LCA of a particular material or substance! This complete analysis of a material or chemical is evidently only possible in such cases where one main application exists. But even if one main application does exist, e.g. in the case of surfactants (chemicals) and detergents (final products), the latter may exist in a great abundance of compositions. Therefore, chemicals and materials are better analysed ‘from cradle-to-factory gate’, leaving the analysis of the final product(s), the use phase and the ‘end-of-life’ phases to specific, full LCAs.Conclusion A comparative assessment of production processes is possible, if the chemicals (the same is true for materials) produced by different methods have exactly the same properties. In this case, the downstream phases may be considered as a ‘black box’ and left out of the assessment. Such truncated LCAs can be used for environmental comparisons, but less so for the (environmental) optimization analysis of a specific chemical: the phases considered as ‘black box’ and left out may actually be the dominant ones. A sustainability assessment should be performed at the product level and contain the results of LCC and social assessments. Equal and consistent system boundaries will have to be used for these life cycle tools which only together can fulfil the aim of assessing the sustainability of product systems.     

Ecotoxicological Characterisation and Classification of Existing Chemicals

GOAL, SCOPE AND BACKGROUND: In 1998, the International Council of Chemical Associations (ICCA) launched a global initiative to investigate more than 1,000 HPV chemicals (High Production Volume, > or = 1,000 t/a) within the refocused OECD HPV Chemicals Programme. Up to the OECD SIDS Initial Assessment Meeting in April 2004 (SIAM 18) 147 ICCA dossiers (ca. 230 CAS-No) have been assessed based on a harmonised data set. The environmental profile and an ecotoxicological characterisation of these chemicals are presented here. Data for acute aquatic toxicity were correlated among each other, as well as data for fish (LC50, LD50) and rodents (LD50). The data for acute aquatic toxicity are compared with other existing chemicals. METHODS: Data of the ICCA HPV chemicals from the OECD SIAM 11-18 are presented for: log Kow (as an indicator for bioaccumulation potential), biodegradation, acute aquatic toxicity and availability of long-term toxicity data. Correlation analysis was performed with log transformed data and a linear regression model was fitted to the data, if a significant correlation was found. Acute toxicity for fish and acute oral toxicity for rodents were correlated on a molar basis. Acute aquatic toxicity of the chemicals is compared with data from BUA reports 1-234 and a random EINECS sample (Knacker et al. 1995). RESULTS AND DISCUSSION: According to the dossier information, 71 of the 147 ICCA chemicals are not 'readily biodegradable', 21 have a log Kow > or = 3, and 44 are 'toxic' (LC/EC50 < or = 10 mg/L) or 'very toxic' (LC/EC50 < or = 1 mg/L) to aquatic organisms. For 77, only the base set (acute fish, Daphnia and algae) is available, for the rest at least one long-term test (fish or Daphnia) is available and three tests for a mere 14 others. Based on the data presented, the SIAM gives recommendations for Environment and Human Health. 22 chemicals have been identified as a 'candidate for further work' for Environment and 16 for Human Health. The highest correlation coefficient was obtained correlating fish and Daphnia (r2 = 0.79). LC50 (fish) is significantly correlated with LD50 (rodent), but data are widely scattered. The correlation is not improved after transforming LC50 (fish) to LD50 (fish), using BCF QSAR. Based on acute aquatic toxicity, 25.1% of the chemicals from the BUA reports 1-234 are classified as 'very toxic' (LC/EC50 < or = 1 mg/L). This proportion is 2.5-fold higher than the ICCA HPV chemicals and 1.4-fold higher than the random EINECS sample. CONCLUSIONS: Correlation coefficients for aquatic toxicity data are rather uniform (0.57-0.79) compared with literature data, but also the best correlation was observed between fish and Daphnia. Because the scatter around the regression lines is still considerable, simple predictions of ecotoxicity between species are not possible. Correlation of LC50 (fish) and LD50 (rodent) indicates that toxicity is different. Surprisingly, the correlation of fish and rodent toxicity is not improved by transforming LC50 values to internal LD50s. The selection of ICCA chemicals by market significance (production volume) leads to a classification of toxicity, which is more comparable to a random sample of EINECS chemicals than to German BUA chemicals. The latter were chosen for concern (for Environment or Human Health). RECOMMENDATIONS AND OUTLOOK: Of 147 dossiers assessed between SIAM 11-18, ca. 75% were sponsored by the three following countries: Germany (42), USA (37) and Japan (33). The current output is about 50 dossiers per year (70-100 CAS-No), but a trend for an increase of output is noticeable. Industry, national authorities, and OECD work on a further development to speed up the output. The number of chemicals with 'low priority for further work' and the work recommended for the 'candidates' (mainly exposure assessment) indicate that the data presented were adequate for an initial hazard assessment according to OECD requirements. From the ICCA HPV list (n = 880, state of 1999) 44% of the chemicals have data available to cover all SIDS endpoints for Environment and only 33% for Human Health (Allanou et al. 1999). This indicates the importance of the Initiative to provide information on existing chemicals. The authors agree with the expectation "...that the scientific information provided by this global initiative will be considered as an internationally accepted and harmonised basis for further steps of chemicals management." (ICCA 2002 b).     

危险化学品运输中的安全问题

危险化学品运输是一种动态危险源 ,发生事故涉及面广 ,危害严重 ,对人民生命财产、社会公共安全构成威胁。危险化学品安全运输越来越受到人们的关注。笔者分析了危险化学品运输中引发事故的诸因素和安全运输中应特别注意的几个问题 ,强调从业单位、从业人员的资质、法律意识和业务素质 ,并探讨了发生事故的应急处置措施 :尽快报警 ,组织抢救 ,杜绝一切火源 ,消毒 ,现场监测。