Chemical Characterization of Polychlorinated Biphenyls, -Dibenzo-p-Dioxins, and -Dibenzofurans in Technical Kanechlor PCB Formulations in Japan

  • Takumi Takasuga
  • Kurunthachalam Senthil Kumar
  • Yukio Noma
  • Shinichi Sakai
Article

Abstract

Technical polychlorinated biphenyl (PCB) formulations—Kanechlor KC-200, KC-300, KC-400, KC-500, KC-600 and KC-1000—produced in Japan were analyzed for the chemical characterization of PCBs, -dibenzo-p-dioxins (PCDDs), and -dibenzofurans (PCDFs) using high-resolution gas chromatography–high-resolution mass spectrometry (HRGC-HRMS) by isotope dilution technique. The homologue/congener profiles of Kanechlor formulations resembled those of Clophen, Aroclor, and Delor, respectively, from Germany, the United States, and Czechoslovakia. Twenty-seven major PCB congeners contributed 50% (in KC-200) to 69–71% (in KC-600, 1000, and 500) to total PCBs. Average total PCB concentrations were 510,000, 800,000, 830,000, 840,000, 870,000, and 880,000 μg/g in KC-1000 (51%), KC-200 (80%), KC-500 (83%), KC-400 (84%), KC-300 (87%), and KC-600 (88%), respectively. Kanechlors also contained PCDDs and PCDFs (4.3 to 0.35 μg/g) as impurities which were approximately 1/10,000 to the PCB concentrations. Congener characterization and concentrations of PCBs and PCDFs were considerably varied in between Kanechlor formulations. The potential for the emissions of PCDDs and PCDFs from Kanechlor was estimated to be 1.94 kg and 464.4 kg, respectively. The average WHO-toxic equivalent (TEQ) was 16 (KC-500) >12 (KC-400) >10 (KC-1000) >4.1 (KC-600) >3.5 (KC-300) >1.9 (KC-200) on μgTEQ/g. Non- and mono-ortho PCBs were the major contributors to the total TEQ in Kanechlor formulations, whereas the PCDD/DF contribution was <2.0%. The environmental input of TEQs from Kanechlors can be estimated to be between 112 and 941 kg.

References

  1. Abad E, Adrados MA, Caixach J, Fabrellas B, Rivera J (2000) Dioxin mass balance in a municipal waste incinerator. Chemosphere 40:1143–1147CrossRefPubMedGoogle Scholar
  2. Addink R, Espourteille F, Altwicker ER (1998a) Role of inorganic chlorine in the formation of polychlorinated dibenzo-p-dioxins/dibenzofurans from residual carbon on incinerator fly ash. Environ Sci Technol 32:3356–3359CrossRefGoogle Scholar
  3. Addink R, Govers HAJ, Olie K (1998b) Isomer distributions of polychlorinated dibenzo-p-dioxins/dibenzofurans formed during de Novo synthesis on incinerator fly ash. Environ Sci Technol 32:1888–1893CrossRefGoogle Scholar
  4. Ahlborg UG, Hanberg A, Kenne K (1992) Risk assessment of polychlorinated biphenyls (PCBs), Nord 1992:26. ISBN 92 9120 075 1. Nordic Council of Ministers. Copenhagen, Denmark, p. 99Google Scholar
  5. Ballschmiter K, Zell M (1980) Analysis of polychlorinated biphenyls (PCB) by glass capillary gas chromatography. Fresen J Anal Chem 302:20–31CrossRefGoogle Scholar
  6. Breivik K, Sweetman A, Pacyna JM, Jones KC (2002) Towards a global historical emission inventory for selected PCB congeners—a mass balance approach 2. Emissions. The Sci Tot Environ 290:181–198CrossRefGoogle Scholar
  7. Deutsches Institut fur Normung e. V. (1987) PCB method no. DIN 51527-1 Revised for European Standard DIN EN 12766-2Google Scholar
  8. Dietrich D, Hickey WJ, Lamar R (1995) Degradation of 4,4’-dichlorobiphenyl, 3,3’,4,4’-tetrachlorobiphenyl, and 2,2’,4,4’,5,5’-hexachlorobiphenyl by the white rot fungus Phanerochaete chrysosporium. Appl Environ Microbiol 61:3904–3909PubMedGoogle Scholar
  9. Falandysz J, Yamashita N, Tanabe S, Tatsukawa R (1992) Composition of PCB isomers and congeners in technical Chlorofen formulation produced in Poland. Intern J Environ Anal Chem 47:129–136Google Scholar
  10. Frame G (1997) A collaborative study of 209 PCB congeners and 6 Aroclors on 20 different HRGC columns. 2. Semi-quantitative Aroclor congener distributions. Fresen J Anal Chem 357:714–722CrossRefGoogle Scholar
  11. Harnly ME, Petreas MX, Flattery F, Goldman LR (2000) Polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran contamination in soil and home-produced chicken eggs near pentachlorophenol sources. Environ Sci Technol 34:1143–1149CrossRefGoogle Scholar
  12. Ivanov V, Sandell E (1992) Characterization of polychlorinated biphenyl isomers in Sovol and Trichlorodiphenyl formulations by high resolution gas chromatography with electron capture detection and high-resolution gas chromatography-mass spectrometry techniques. Environ Sci Technol 26:2012–2017CrossRefGoogle Scholar
  13. Kannan N, Tanabe S, Wakimoto T, Tatsukawa R (1987) Coplanar polychlorinated biphenyls in Aroclor and Kanechlor mixtures. J Assoc Official Anal Chemists 70:451–454Google Scholar
  14. Kannan K, Falandysz J, Yamashita N, Tanabe S, Tatsukawa R (1992) Temporal trends of organochlorine concentrations in cod-liver oil from the southern Baltic proper, 1971–1989. Mar Pollut Bull 24: 358–363CrossRefGoogle Scholar
  15. Kannan N, Schulz-Bull DE, Petrick G, Duinker JC (1992) High resolution PCB analysis in Kanechlor, Phenoclor and Sovol mixtures using multidimensional gas chromatography. Int J Environ Anal Chem 47:201–215Google Scholar
  16. Kannan K, Maruya KA, Tanabe S (1997) Distribution and characterization of polychlorinated biphenyl congeners in soil and sediments from a Superfund site contaminated with Aroclor 1268. Environ Sci Technol 31:1483–1488CrossRefGoogle Scholar
  17. Kannan K, Yamashita N, Imagawa T, Villeneuve DL, Hashimoto S, Miyazaki A, Giesy JP (2000) Vertical profile of polychlorinated dibenzo-p-dioxins, -dibenzofurans, -napthalenes, -biphenyls, polycyclic aromatic hydrocarbons and alkylphenols in a sediment core from Tokyo Bay, Japan. Environ Sci Technol 34:3560–3567CrossRefGoogle Scholar
  18. Kim KS, Hirai Y, Kato M, Urano K, Masunaga S (2004) Detailed PCB congener patterns in incinerator flue gas and commercial PCB formulations (Kanechlor). Chemosphere 55:539–553CrossRefPubMedGoogle Scholar
  19. Loganathan BG, Kannan K (1991) Time perspectives of organochlorine contamination in the global environment. Mar Pollut Bull 22:582–584CrossRefGoogle Scholar
  20. Loganathan BG, Kannan K (1994) Global organochlorine contamination trends: an overview. Ambio 23:187–191Google Scholar
  21. Masunaga S, Takasuga T, Nakanishi J (2001) Dioxin and dioxin-like PCBs impurities in some Japanese agrochemical formulations. Chemosphere 44:873–885CrossRefPubMedGoogle Scholar
  22. Mullin MD, Pochini CM, McCrindle S, Romkes M, Safe SH, Safe LM (1984) High-resolution PCB analysis: synthesis and chromatographic properties of all 209 PCB congeners. Environ Sci Technol 18:468–476CrossRefGoogle Scholar
  23. Schulz DE, Petrick G, Duinker JC (1989) Complete characterization of polychlorinated biphenyl congeners in commercial Aroclor and Clophen mixtures by multidimensional gas chromatography-electron capture detection. Environ Sci Technol 23:852–859Google Scholar
  24. Takasuga T (2001) Investigation of analytical and environmental chemistry for trace organohalogen compounds in waste management. PhD thesis. The University of Tokyo, Japan (in Japanese)Google Scholar
  25. Takasuga T, Inoue T, Ohi E (1992) Evaluation of high-resolution gas chromatography/high-resolution mass spectrometry method for the determination of dioxin and related compounds. J Environ Chem 2:599–613 (in Japanese)Google Scholar
  26. Takasuga T, Inoue T, Ohi E (1995) All congener specific analytical method for polychlorinated biphenyls (PCBs) with various chromatographic clean-up and HRGC-HRMS. J Environ Chem 5:647–675 (in Japanese)Google Scholar
  27. Takasuga T, Inoue T, Ishida Y, Ireland P (1996) Determination of the composition of the commercial PCBs: Kanechlor, Clophen, Aroclor, Chlorofen, and Sovol, by HRGC-HRMS. Organohalogen Compd 27:391–396Google Scholar
  28. Takasuga T, Matsumura T, Shiozaki K, Sakai S (2002) Determination of PCBs in transformer oil and chemically degraded oil by isotope dilution method with HRGC/MS: 3-lab intercalibration study and evaluation of new calibration PCB mixture. Organohalogen Compd 59:415–418Google Scholar
  29. Takasuga T, Noma Y, Sakai S (2003) Polychlorinated biphenyls and PCDD/DFs in Kanechlor technical PCB formulation from Japan by isotope dilution method using HRGC-HRMS. Organohalogen Compd 62:491–494Google Scholar
  30. Takasuga T, Senthil Kumar K, Matsumura T, Shiozaki K, Sakai S (2005) Isotope dilution analysis of polychlorinated biphenyls (PCBs) in transformer oil and global commercial PCB formulations by high resolution gas chromatography-high resolution mass spectrometry. Chemosphere (in press)Google Scholar
  31. Tanabe S (1988) PCB problems in the future: foresight from current knowledge. Environ Pollut 50:5–28CrossRefPubMedGoogle Scholar
  32. Tanabe S, Tatsukawa R, Phillips DJH (1987) Mussels as bioindicators of PCB pollution: a case study on uptake and release of PCB isomers and congeners in green-lipped mussels (Perna viridis) in Hong Kong coastal waters. Environ Pollut 47:41–62CrossRefPubMedGoogle Scholar
  33. Taniyasu S, Kannan K, Holoubek I, Ansorgova A, Horii Y, Hanari N, Yamashita N, Aldous KM (2003) Isomer-specific analysis of chlorinated biphenyls, naphthalenes and dibenzofurans in Delor: polychlorinated biphenyl preparations from the former Czechoslovakia. Environ Pollut 126:169–178CrossRefPubMedGoogle Scholar
  34. Tatsukawa R (1976) In: Higuchi K. (ed) PCB poisoning and pollution. Kodansha Ltd., Academic Press, Tokyo, pp 147–179Google Scholar
  35. Triska J, Kuncova G, Mackova M, Novakova H, Paasivirta J, Lahtiperia M, Vrchotova N (2004) Isolation and identification of intermediates from biodegradation of low chlorinated biphenyls (Delor-103). Chemosphere 54:725–733CrossRefPubMedGoogle Scholar
  36. Van den Berg M, Birnbaum L, Bosveld ATC, Brunstrom B, Cook P, Feeley M, Giesy JP, Hanberg A, Hasegawa R, Kennedy SW, Kubiak TJ, Larsen JC, Rolaf van Leeuwen FX, Liem AKD, Nolt C, Peterson RE, Poellinger L, Safe S, Schrenk D, Tillitt D, Tysklind M, Younes M, Waern F, Zacharewski T (1998) Toxic equivalency factors (TEFs) for PCBs, PCDDs, PCDFs for humans and wildlife. Environ Health Perspect 106:775–792Google Scholar
  37. Wakimoto T, Kannan N, Ono M, Tatsukawa R, Masuda Y (1988) Isomer-specific determination of polychlorinated dibenzofurans in Japanese and American polychlorinated biphenyls. Chemosphere 17:743–750CrossRefGoogle Scholar
  38. Yao Y, Takasuga T, Masunaga S, Nakanishi J (2002) Detailed study on the levels of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and polychlorinated biphenyls in Yusho rice oil. Chemosphere 46:1461–1469CrossRefPubMedGoogle Scholar

Copyright information

© Springer Science+Business Media, Inc. 2005

Authors and Affiliations

  • Takumi Takasuga
    • 1
  • Kurunthachalam Senthil Kumar
    • 1
  • Yukio Noma
    • 2
  • Shinichi Sakai
    • 2
  1. 1.Shimadzu Techno ResearchNakagyo-kuJapan
  2. 2.Research Center for Material Cycles and Waste ManagementNational Institute for Environmental StudiesTsukubaJapan

Personalised recommendations