The structure of the fire fighting foam surfactant Forafac®1157 and its biological and photolytic transformation products

For several decades, perfluorooctane sulfonate (PFOS) has widely been used as a fluorinated surfactant in aqueous film forming foams used as hydrocarbon fuel fire extinguishers. Due to concerns regarding its environmental persistence and toxicological effects, PFOS has recently been replaced by novel fluorinated surfactants such as Forafac®1157, developed by the DuPont company. The major component of Forafac®1157 is a 6:2 fluorotelomer sulfonamide alkylbetaine (6:2 FTAB), and a link between the trade name and the exact chemical structure is presented here to the scientific community for the first time. In the present work, the structure of the 6:2 FTAB was elucidated by ¹H, ¹³C and ¹⁹F nuclear magnetic resonance spectroscopy and high-resolution mass spectrometry. Moreover, its major metabolites from blue mussel (Mytilus edulis) and turbot (Scophthalmus maximus) and its photolytic transformation products were identified. Contrary to what has earlier been observed for PFOS, the 6:2 FTAB was extensively metabolized by blue mussel and turbot exposed to Forafac®1157. The major metabolite was a deacetylated betaine species, from which mono- and di-demethylated metabolites also were formed. Another abundant metabolite was the 6:2 fluorotelomer sulfonamide. In another experiment, Forafac®1157 was subjected to UV-light induced photolysis. The experimental conditions aimed to simulate Arctic conditions and the deacetylated species was again the primary transformation product of 6:2 FTAB. A 6:2 fluorotelomer sulfonamide was also formed along with a non-identified transformation product. The environmental presence of most of the metabolites and transformation products was qualitatively demonstrated by analysis of soil samples taken in close proximity to an airport fire training facility.     

Concentrations of organochlorine pesticides and 2,4,6-trichloroanisole in cork bark

Organochlorine pesticides are persistent lipophilic organic pollutants and tend to accumulate in growing plants. During growth, cork is in contact with the open air for long periods (9-12 years). Owing to the previous widespread use of organochlorine pesticides and their high persistence in the environment, there is a risk that residues of such pesticides may be present in cork.In this study, the concentrations of 14 organochlorine pesticides—all of which are indicators of environmental pollution—were analyzed in cork bark samples from three regions in Spain and one in Portugal. In addition, the concentrations of 2,4,6-trichlorophenol (TCP) and 2,4,6-trichloroanisole (TCA) were also analyzed.Our results show only very low concentrations of lindane, γ-HCH (<2.6 ng g⁻¹) and its byproducts α-HCH (<3.5 ng g⁻¹) and β-HCH (<0.6 ng g⁻¹).Among the DDT and its metabolites, only two were found: p,p′-DDT was found in a cork sample from Extremadura (0.1 ng g⁻¹) and p,p′-DDE was present at a maximum concentration of 2.9 ng g⁻¹ in a cork sample from Castile-La Mancha. However, all concentrations were well below the legal limit established by Regulation (EC) No. 396/2005 (10 ng g⁻¹ in foodstuffs). We can conclude, therefore, that the cork samples we studied complied with food safety standards.     

还原－衍生化高分辨气相色谱法测定复杂样品中痕量硝基多环芳烃（NO2－PAH）的研究

研究了还原－七氟丁酸酐性生化高分辨气相色谱－ＥＣＤ测定痕量硝基多环芳烃的方法。该法具有选择性好，灵敏度高的特点，适合于复杂样品痕量硝基多环芳的测定。建议采用以氨基多环芳烃ＨＦＢＡ衍生物为参比的ＨＦＢＡＰＡＨ保留指数体系，利用保留指数进行双柱定性成功地在碳黑样品提取中检出包括１－ＮＯ２茈在内的９种ＮＯ２－ＰＡＨ并提出了定量结果。     

钢铁企业排放的烟气及厂区土壤中二噁英类污染研究

对国内某钢铁企业厂区内土壤和烧结厂排放烟气中二噁英类物质进行了采样研究,得出土壤中二噁英类物质浓度范围是1.05~6.91pgⅠ-TEQ/g,平均值为3.22pgⅠ-TEQ/g;烟气中的浓度范围是0.23~0.48 ngⅠ-TEQ/Nm3,平均值为0.32 ngⅠ-TEQ/Nm3,给出了土壤和烟气中二噁英类物质形态分布特点,并根据形态分布存在的相似性推断出土壤中二噁英类物质主要来源于烧结厂烟气的排放。     

Retention time profiling of all 136 tetra- through octa- chlorinated dibenzo-p-dioxins and dibenzofurans on a variety of Si-Arylene gas chromatographic stationary phases

The applicability of three different Silphenylene Silicone co-polymer (Si-Arylene) GC stationary phases (J&W Scientific DB-5ms, Varian VF-5ms, and VF-Xms) has been evaluated for the separation of all 136 tetra- through the octa- chlorinated dibenzo-p-dioxins (PCDD) and chlorinated dibenzofurans (PCDF) from closely eluting isomers using gas chromatography/high resolution mass spectrometry (GC/HRMS). Their relative performance data are compared to the “conventional” 5% diphenyl 95% dimethylpolysiloxane GC column (Supelco Equity-5) and to each other based on absolute retention times, visualized mass chromatograms, and the separation of 2,3,7,8-substituted isomers. VF-Xms GC column was able to demonstrate a better performance towards separation of 2,3,7,8-substituted PCDD/PCDF compared to other Si-Arylene GC columns tested, where only 2,3,4,7,8-PnCDF can not be resolved from 1,2,3,6,9-PnCDF and 2,3,4,6,7,8-/1,2,3,6,8,9-HxCDF and 1,2,3,7,8,9-/1,2,3,4,8,9-HxCDF can be at least partially resolved. These data suggest that the development of a single GC column for the separation of all 17 2,3,7,8-substituted dioxins and furans is feasible, which therefore could be used as a standard tool for the PCDD/PCDF methods globally including USEPA methods 1613b, 8290A, 8280B, European Standard Method EN 1948, Canadian methods DFPCB-E3418, EPS 1/RM/19, Japanese methods JIS K0311 and JIS K0312. Having one specific GC column to separate all 2,3,7,8-substituted PCDD/PCDF will significantly improve the data quality, comparability by the various methods and assessment techniques while simultaneously leading to a more cost and time efficient operation.     

二恶英类化合物检测方法的研究现状及展望

介绍了二恶英类化合物的检测方法,并对各种检测方法的原理和应用进行了对比分析;其中高分辨率色谱/质谱法、荧光素酶报告基因法及酶免役分析法在实践中取得了很好的检测效果;CALUX 法与其他生物检测方法相比更适合于大批量样品中二恶英含量的快速定量筛选,对于二恶英污染调查有广阔的应用前景;综述了我国二恶英类化合物检测方法的研究现状,并对我国开展二恶英分析监测提出了建议和展望.     

焚烧源二噁英连续采样技术与运行评价

将研发的二噁英连续采样装置与G4型常规烟道气等速采样器同步采样,通过示范运行,考察该连续采样装置的长期采样性能。试验表明,2种采样设备同步采集的样品具有一致性,其二噁英指纹、二噁英浓度和毒性当量相符合。1周的示范运行连续采样试验表明,该连续采样装置中的二噁英捕集材料未发生穿透。1个月的连续采样实测表明,连续采样测定中烟道气排放二噁英毒性当量浓度(以I-TEQ计)为35.0 pg/m3(标况下),采样回收率为71.2%。     

京杭运河杭州市区段表层沉积物中二噁(口英)的分布

采用同位素稀释一高分辨气质联用技术对京杭运河杭州市区段表层沉积物中二噁(口英)的分布进行研究.京杭运河杭州市区段表层沉积物中∑P4-8 CDD/Fs的含量为108.7～513.124pg/g,毒性当量范围为1.788～4.777pg TEQ/g.研究发现,运河表层沉积物5处样品中二噁(口英)分布相似,17种2,3,7,8取代二噁(口英)基本上都有检出.OCDD占据主导地位,并且1,2,3,4,6,7,8-HpCDD与OCDD的比值相近,表明沉积物中的二噁(口英)分布具有明显的交通燃烧源排放特征.     

电子垃圾焚烧排放的二噁英对周围大气环境的影响

为了研究电子垃圾焚烧产生的二噁英对周围环境的影响,同时在E1和E2采样点分别采集9个大气样品.E1周围分布大量的电子垃圾焚烧点,E2则位于E1南9 km处,周围无其他明显的二噁英排放源.所采样品用同位素稀释法进行分析测定,结果表明,E1和E2大气样品中二噁英的平均质量浓度分别为127.37、22.37 pg/m3,平均毒性当量浓度分别为8.777、1.305 pg I-TEQ/m3.八氯代二苯并呋喃(OCDF)、八氯代二苯并二噁英(OCDD)、七氯代二苯并呋喃(1,2,3,4,6,7,8-HpCDF)和七氯代二苯并二噁英(1,2,3,4,6,7,8-HpCDD)对2,3,7,8位氯代的二噁英的总浓度贡献较大,而五氯代二苯并呋喃(2,3,4,7,8-PeCDF)则对总毒性当量浓度贡献最大,其贡献率超过40%.在E1和E2两个采样点,二噁英在气相中的比例均随着氯原子取代数的增加而降低.两采样点相似的二噁英分布模式和气固分配,说明E2大气中二噁英主要来自于E1电子垃圾焚烧产生的二噁英.     

二恶英类物质的生物检测方法

我国的食品卫生、环境安全和公共健康正受到二恶英污染的威胁。国内虽已建成或在建少数HRGC-HRMS二恶英检测实验室,但其检测能力十分有限。笔者介绍二恶英类化合物生物检测方法,对各分析方法的原理和应用进行了对比分析;重点探讨CALUX法,与HRGC-HRMS及其他生物法相比,认为CALUX法更适于对大批量样品二恶英含量的快速定量筛选,对于二恶英污染调查有广阔的应用前景;同时对我国开展二恶英类分析检测提出了建议和展望,为完善二恶英类物质检测分析体系提供了依据。