Chromatographic techniques for PCB and dioxin problems.

（1）在填充十八烷基硅烷化二氧化硅颗粒（ODS-silica）的石英柱中，采用紫外光照射降解多氯联苯（PCBs）和多氯二苯并二恶英（PCDDs）。吸附在臭氧消耗物质二氧化硅上的高氯化多氯联苯也可能从水溶液中连续光解。具有二至八个氯的多氯联苯的光解允许检查影响反应途径的因素。空间拥挤和分子对称性被认为是主要因素，解释了各种同系物看似复杂的分解途径，这些途径不受光源（汞灯或阳光）的影响。结果表明，主要的邻位脱氯导致产物不仅具有更高的TEF，而且在光解条件下具有更长的寿命。多氯二苯并对二恶英在有H-供体的情况下优先从2378-位失去一个氯原子，但在没有增加TEQ的情况下优先从1469-位失去一个氯原子，这表明潜在的危险是 关于我们 在没有H-供体的情况下，污染土壤的阳光光解。（2）以SiO2颗粒为载体，制备了电子受体键合固定相3-（p-nitrophenoxy）propylsilyl（NPO）和电子键合固定相3-（N-carbazolyl）propylsilyl（CZP）、2-（1-pyrenyl）ethyl silyl（PYE）和5-coronenylpentylsilyl（COP），考察了它们对PCDD异构体、六氯萘（HxCNs）、平面和非平面PCB同系物的选择性。虽然没有一种固定相能够分离在多氯二苯并对二恶英和六氯化萘合成过程中同时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。分离的PCDD异构体被认为是最成功的PYE和NPO相。两相对于作为混合物产生的每种异构体对产生相反的洗脱顺序。对于在PYE和CZP相上分离的HxCN异构体获得了类似的结果。与PYE相相比，COP相提供了基于平面性的非邻位取代和单邻位取代的PCB与其他PCB的更容易分离。这些固定相能够完全分离二恶英的所有同系物以及PCDDs，PCBs和PAH之间的基团分离。（3）通过使用PYE硅胶柱以及填充有十八烷基硅烷化硅胶的限制进入反相柱，证明了在血清样品脱蛋白后将多氯联苯和多氯二苯并对二恶英分离到有机溶剂中的可能性，所述十八烷基硅烷化硅胶在外表面具有二醇官能度。第一步溶解脂蛋白中的多氯联苯和二恶英，第二步提供基团分离。血清样品的处理方法将允许缩短准备时间从24小时到约1小时，通过避免几个色谱步骤，导致成本和时间效率的分析GC/MS。结果表明，阳光光解的多氯联苯和多氯二苯并对二恶英已经释放到环境中是潜在的危险生物物种，并妥善管理和处置剩余的多氯联苯是非常重要的。研究结果还表明，重要的是要开发一种更有选择性，灵敏度和快速的分析方法，这些污染物，需要最少的劳动力用于处理生物样品。利用色谱技术，或利用固体表面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分解环境污染物。少

(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