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Chromatographic techniques for PCB and dioxin problems.

Research Project

Project/Area Number 09044081
Research Category

Grant-in-Aid for Scientific Research (B).

Allocation TypeSingle-year Grants
Section一般
Research Field 環境保全
Research InstitutionKYOTO INSTITUTE OF TECHNOLOGY

Principal Investigator

TANAKA Nobuo  Dep. Polymer Science, Kyoto Inst. Tech., Professor, 繊維学部, 教授 (60127165)

Co-Investigator(Kenkyū-buntansha) OIDA Tatsuo  Dep. Chem. Mat. Tech., Kyoto Inst. Tech., Assoc. Prof., 工芸学部, 助教授 (90152032)
OTSUKA Koji  Dep. Material Science, Himeji Inst. Tech., Assoc. Prof., 理学部, 助教授 (70183762)
TERABE Shigeru  Dep. Material Science, Himeji Inst. Tech., Professor, 理学部, 教授 (50115888)
IKEGAMI Tohru  Dep. Polymer Science, Kyoto Inst. Tech., Instructor, 繊維学部, 助手 (20301252)
HOSOYA Ken  Dep. Polymer Science, Kyoto Inst. Tech., Assoc. Prof., 繊維学部, 助教授 (00209248)
PATTERSON Do  公衆保健局, 防疫センター(米国), 室長
Project Period (FY) 1997 – 1999
Project Status Completed (Fiscal Year 1999)
Budget Amount *help
¥5,900,000 (Direct Cost: ¥5,900,000)
Fiscal Year 1999: ¥1,900,000 (Direct Cost: ¥1,900,000)
Fiscal Year 1998: ¥1,800,000 (Direct Cost: ¥1,800,000)
Fiscal Year 1997: ¥2,200,000 (Direct Cost: ¥2,200,000)
Keywordsdioxin / 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
Research Abstract

(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

Report

(4 results)
  • 1999 Annual Research Report   Final Research Report Summary
  • 1998 Annual Research Report
  • 1997 Annual Research Report
  • Research Products

    (42 results)

All Other

All Publications (42 results)

  • [Publications] K. Kimata, et al.: "Selectivity of electron-donor- and electron-acceptor-bonded silica packing materials for hydrophobic environmental contaminants in polar and nonpolar eluent"Journal of Cromatography. 786. 237-248 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] K. Otsuka, et al.: "Stereoselective separation and detection of phenoxy acid herbicide enantiomers by cyclodextrin-modified CZE-electrospray ionization MS"Journal of Cromatography. 817. 75-81 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] H. Go, et al.: "Effects of mobile phase composition and temperature on the selectivity of poly-(N-isopropylacrylamide)-bonded silica gel in reversed-phase LC"Analytical Chemistry. 70. 4086-4093 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. Oida, et al.: "Photolysis of polychlorinated biphenyls on octadensylsilylated silica particles"Chemosphere. 39. 1795-1807 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. Ikegami, et al.: "Isolation of polychlorodibenzo-p-dioxins and polychlorobiphenyls upon deproteinization of a serum sample by HPLC with restricted-access packing materials"Journal of High Resolution Cromatography. 22. 287-293 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] N. Ishizuka, et al.: "Performance of silica rod column in a capillary under pressure-driven and electro-driven conditions"Analytical Chemistry. 72(In Press). (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] N. Tanaka, et al.: "Separation of Fullerenes"Royal Chemical Society(分担). 107-128 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] K. Kimata, et al.: "Selectivity of electron-donor-and electron-acceptor-bonded silica packing materials for hydrophobic environmental contaminants in polar and non-polar eluents."J. Chromatogr.. 786. 237-248 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] K. Kimata, et al.: "Direct chromatographic separation of racemates on the basis of isotopic chirality."Anal. Chem.. 69. 2610-2612 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] N. Tanaka, et al.: "Starburst dendrimer-supported pseudo-stationary phases for electrokinetic chromatography."J. High Resol. Chromatogr.. 20. 529-538 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] N. Tanaka: "Polyallylamine-supported pseudo-stationary phases for electrokinetic chromatography. Effect of alkyl chain length of the pseudo-stationary phase and methanol content of aqueous buffer on the separation of hydrophobic compounds."J. Chromatogr. A.. 139-150 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] K. Otsuka, et al.: "Stereoselective separation and detection of phenoxy acid herbicide enantiomers by cyclodextrin-modified capillary zone electrophoresis-electrospray ionization mass spectrometry."J. Chromatogr. A. 817. 75-81 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] K. Otsuka, et al.: "Effects of compositions of β-cyclodextrins on enantiomer separations by cyclodextrin modified capillary zone electrophoresis"J. Pharm. Biomed. Anal.. 17. 1177-1190 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] N. Tanaka, et al.: "Control of migration time window and selectivity in electrokinetic chromatography with mixed polymeric pseudo-stationary phases."J. Chromatogr. A. 802. 23-33 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] H. Go, et al.: "Effects of mobile phase composition and temperature on the selectivity of poly (N-iso-propylacrylamide) -bonded silica gel in reversed-phase liquid chromatography."Anal. Chem. 70. 4086-4093 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] N. Tanaka, et al.: "Effects of electrokinetic-chromatography conditions on the structure and properties of polyallylamine-supported pseudo-stationary phase : A study by dynamic light scattering."J. Chromatogr. A. 836. 295-303 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] N. Tanaka: "An approach to high-performance packing materials for HPLC."Chromatography. 20. 1-10 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] B. Buszewski, et al.: "Determination of Hazardous Compounds isolated from Environmental Samples Utilizing Various Stationary Phases and Columns for Chromatographic Techniques."Chem. Anal.. 44. 327 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. Oida, et al.: "Photolysis of polychlorinated biphenyls on octadecylsilylated silica particles."Chemosphere. 39/11. 1795-1807 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. lkegami, et al.: "lsolation of polychlorodibenzo-p-dioxins and polychlorobiphenyls upon deproteinization of a serum sample by HPLC with restricted-access reversed-phase packing materials"J. High Resol. Chromatogr.. 22. 287-293 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Nobuo Tanaka, et al.: "Monolithic Silica Columns for HPLC, micro-HPLC, and CEC."J. High Resol. Chromatogr.. 23. 111-116 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] N. lshizuka, et al.: "Performance of a silica rod column in a capillary under pressure-driven and electro-driven conditions."Anal. Chem. 72. 1275-1280 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T.Oida et al.: "Photolysis of polychlorinated biphenyls on octadecylsilylated silica particles"Chemosphere. 39. 1795-1807 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] T.Ikegami et al.: "Isolation of Polychlorodibenzo-p-dioxins and polychlorobiphenyls upon deproteinization of a serum sample by HPLC with restricted-access packing materials"Journal of High Resolution Chromatography. 22. 287-293 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] 田中 信男: "HPLC充填剤の高性能化への基礎的アプローチ"Chromatography. 20. 1-10 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] N.Tanaka et al.: "Effects of electrokinetic-chromatography conditions on the structure and properties of polyallylamine-supported pseudo-stationary phase: A study by dynamic light scattering"Journal of Chromatography. 836. 295-303 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] N.Ishizuka et al.: "Performance of a silica rod column in a capillary under pressure-driven and electro-driven conditions"Analytical Chemistry. 72(in press). (2000)

    • Related Report
      1999 Annual Research Report
  • [Publications] N.Tanaka et al.: "Monolithic Silica Columns for HPLC,micro-HPLC,and CEC"Journal of High Resolution Chromatography. 23. 111-116 (2000)

    • Related Report
      1999 Annual Research Report
  • [Publications] N.Tanaka et al.: "Separation of Fullerenes"Royal Chemical Society(分担). 107-128 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] N.Tanaka, et al.: "Control of migration time window and selectivity in electrokinetic chromatography with mixed polymeric pseudostationary phases" Journal of Chromatography. 802. 23-33 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] H.Minakuchi, et al.: "Effect of domain size on the performance of octadecylsilylated continuous porous silica colunns in reversed-phase liquid chromatography." Journal of Chromatography. 797. 121-131 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] K.Otsuka, et al.: "Stereoselective separation and detection of phenoxy acid herbicide enantiomers by cyclodextrin-modified CZE-electrospray ionization MS" Journal of Chromatography. 817. 75-81 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] K.Otsuka, et al.: "Effects of compositions of β-cyclodextrins on enantiomer separations by cyclodextrin modified capillary zone electrphoresis." Journal of Pharmaceutical Biomedical Analysis. 17. 1177-1190 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] N.Tanaka, et al.: "Effects of electrokinetic-chromatography conditions on the structure and properties of polyallylamine-supported pseudo-stationary phase:A study by DLS." Journal of Chromatography. (印刷中). (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] T.Lkegami, et al.: "Isolation of polychlorodibenzo-p-dioxins and polychlorobiphenyls upon depro-teinization of a serum sample by HPLC with restricted-access RPLC materials." Journal of High Resolution Chromatography. (印刷中). (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] N.Tanaka, et al.(分担): "Separation of Fullerenes" Royal Chemical Society, 印刷中 (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] K.Kimata, et al.: "Selectivity of electron-donor- and electron-acceptor-bonded silica packing materials for hydrophobic environmental contaminants in polar and nonpolar eluent" Journal of Chromatography. 786. 237-248 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] H.Minakuchi, et al.: "Effect of skeleton size on the performance of octadecylsilylated continuous porous silica columns." Journal of Chromatography. 762. 135-146 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] K.Kimata, et al.: "Direct chromatographic separation of racemates on the basis of isotopic chirality." Analytical Chemistry. 69. 2610-2612 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] H.Minakuchi, et al.: "Effect of domain size on the performance of octadecylsilylated continuous porous silica columns in reversed-phase liquid chromatography." J.Chromatogr.(印刷中). (1998)

    • Related Report
      1997 Annual Research Report
  • [Publications] N.Tanaka, et al.: "Polyallylamine-supported pseudo-stationary phases for electrokinetic chromatography.Effect of alkyl chain length and methanol content." J.Chromatogr.781. 139-150 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] N.Tanaka, et al.: "Control of migration time window and selectivity in electrokinetic chromatography with mixed polymeric pseudostationary phases" J.Chromatogr.(印刷中). (1998)

    • Related Report
      1997 Annual Research Report

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Published: 1997-04-01   Modified: 2016-04-21  

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