Chromatographic techniques for PCB and dioxin problems.

PCB 和二恶英问题的色谱技术。

• 批准号: 09044081
• 负责人: TANAKA Nobuo
• 金额: $ 3.78万
• 依托单位: KYOTO INSTITUTE OF TECHNOLOGY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B).
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09044081/
• 关键词: dioxin; PCB; HPLC; photolysis; serum sample treatment; toxic equivalent (TEQ); normal-phase separation; group separation; グループ分離; 環境安定性; 多環芳香族炭化水素; 動電クロマトグラフィー; EKC-MS

(1)PCBs and polychlorodibenzo-p-dioxins (PCDDs) were decomposed in a quartz column packed with octadecylsilylated silica particles (ODS-silica) by external UV irradiation. Continuous photolysis of highly chlorinated PCBs trapped on ODS-silica from aqueous solution was also possible. The photolysis of PCBs having two to eight chlorines allowed the examination of the factors that affect the reaction pathway. Steric congestion and molecular symmetry were found to be the major factors, explaining the seemingly complicated decomposition pathways of various congeners that were not much affected by the light source, a mercury lamp or sunlight. The results indicate that the predominant ortho-dechiorination leads to products having not only higher TEFs but also much longer life under photolysis conditions. PCDDs lose a chlorine atom preferentially from 2378-positions in the presence of H-donor, but preferentially from 1469-positions in the absence increasing TEQs, suggesting potential danger of … More sunlight photolysis of contaminated soil in the absence of H-donor.(2)Electron-acceptor-bonded stationary phase, 3-(p-nitrophenoxy)propylsilyl (NPO), and electron-bonded phases, 3-(N-carbazolyl) propylsisly (CZP), 2-(1-pyrenyl) ethylsilyl (PYE), and 5-coronenylpentylsilyl (COP), were prepared from silica particles, and their selectivities were examined for PCDD isomers, hexachloronaphthalense (HxCNs), and planar and nonplanar PCB congeners. Although no single stationary phase was able to separate all the isomer pairs that are coproduced during the synthesis of the PCDDs and HxCNs, they can be separated by selecting a suitable stationary phase and solvent. The separation of PCDD isomers were found to be most successful with PYE and NPO phases. The two phases yielded the opposite elution orders for each isomer pair that is produced as a mixture. Similar results were obtained for the HxCN isomers that were separated on PYE and CZP phases. The COP phase provided easier separation of non-ortho-substituted and mono-ortho-substituted PCBs from the other PCBs based on the planarity than PYE phase. These stationary phases enabled total separation of all congeners of dioxins as well as group separation between PCDDs, PCBs, and PAHs.(3)The possibility of isolating PCBs and PCDDs into an organic solvent upon deproteinization of a serum sample followed by the class separation of PCDDs from PCBs was shown by using a PYE silica column in addition to a restricted-access reversed-phase column packed with octadecylsilylated silica having diol functionality at the external surfaces. The first step solubilizes PCBs and dioxins from lipoproteins, and the second step provide group separations. The serum sample treatment method will allow shortening the preparation time from 24 h to about 1 h, by avoiding several chromatographic steps leading to cost and time efficient analysis by GC/MS.The results suggest that sunlight photolysis of PCBs and PCDDs already released to the environment is potentially dangerous to living species, and that proper management and disposal of remaining PCBs are very important. The results also suggest that it is important to develop a more selective, sensitive, and rapid analysis method of these pollutants that needs minimum labor for the treatment of biological samples. The utilization of chromatographic techniques, or the use of solid surfaces for separation and decomposition of dioxins and PCBs is expected to lead to faster analysis and safer decomposition of environmental contaminants. Less

(1)在装有十八烷基硅烷化二氧化硅颗粒(ODS-silica)的石英柱中，通过外部紫外线照射分解PCBs和多氯二苯并-对二恶英(PCDDs)。从水溶液中捕获在 ODS-二氧化硅上的高度氯化 PCB 的连续光解也是可能的。具有 2 至 8 个氯的 PCB 的光解可以检查影响反应途径的因素。研究发现，空间拥挤和分子对称性是主要因素，这解释了各种同源物看似复杂的分解途径，而这些途径不受光源、汞灯或阳光的影响太大。结果表明，主要的邻位脱氯作用不仅导致产品具有更高的 TEF，而且在光解条件下具有更长的寿命。在氢供体存在的情况下，PCDD 优先从 2378 位失去一个氯原子，但在不增加 TEQ 的情况下，优先从 1469 位失去一个氯原子，这表明在没有氢供体的情况下，污染土壤存在阳光光解的潜在危险。(2)电子受体键合固定相，3-(对硝基苯氧基)丙基甲硅烷基 (NPO)，和 由二氧化硅颗粒制备了电子键合相 3-(N-咔唑基) 丙基甲硅烷基 (CZP)、2-(1-芘基) 乙基甲硅烷基 (PYE) 和 5-晕烯基戊基甲硅烷基 (COP)，并检查了它们对 PCDD 异构体、六氯萘 (HxCN) 以及平面和非平面 PCB 的选择性 同系物。尽管没有单一的固定相能够分离 PCDD 和 HxCN 合成过程中共同产生的所有异构体对，但可以通过选择合适的固定相和溶剂来分离它们。研究发现，PYE 和 NPO 相可以最成功地分离 PCDD 异构体。对于作为混合物产生的每个异构体对，这两个相产生相反的洗脱顺序。在 PYE 和 CZP 相上分离的 HxCN 异构体也获得了类似的结果。与 PYE 相相比，COP 相更容易根据平面度将非邻位取代和单邻位取代的 PCB 与其他 PCB 分离。这些固定相能够完全分离二恶英的所有同系物，以及 PCDD、PCB 和 PAH 之间的组分离。(3)通过使用 PYE 硅胶柱以及填充有限制性反相色谱柱的限制性反相色谱柱，可以在血清样品脱蛋白后将 PCB 和 PCDD 分离到有机溶剂中，然后将 PCDD 与 PCB 进行类别分离。 十八烷基甲硅烷基化二氧化硅在外表面具有二醇官能团。第一步从脂蛋白中溶解多氯联苯和二恶英，第二步提供组分离。血清样品处理方法可将制备时间从 24 小时缩短至约 1 小时，避免了几个色谱步骤，从而通过 GC/MS 进行成本和时间高效的分析。结果表明，已释放到环境中的 PCB 和 PCDD 的阳光光解对生物物种具有潜在危险，对剩余 PCB 的适当管理和处置非常重要。研究结果还表明，开发一种更具选择性、灵敏性和快速分析这些污染物的方法非常重要，该方法需要最少的劳动力来处理生物样品。利用色谱技术或使用固体表面来分离和分解二恶英和多氯联苯预计将导致更快的分析和更安全的环境污染物分解。较少的

项目成果

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