Journal of the Korean Society for Marine Environment & Energy (한국해양환경ㆍ에너지학회지)

The Korean Society for Marine Environment and Energy (한국해양환경•에너지학회)
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Identification of Major Crude Oils Imported into Korea using Molecular and Stable Carbon Isotopic Compositions

분자지표 및 탄소안정동위원소 조성비를 이용한 국내 수입 주요 원유의 식별

  • Kim, Eun-Sic (Oil and POPs Research Group, Korea Institute of Ocean Science and Technology) ;
  • An, Jun-Geon (Oil and POPs Research Group, Korea Institute of Ocean Science and Technology) ;
  • Kim, Gi-Beum (Department of Marine Environmental Engineering, Gyeongsang National University) ;
  • Shim, Won-Joon (Oil and POPs Research Group, Korea Institute of Ocean Science and Technology) ;
  • Joo, Chang-Kyu (Oil and POPs Research Group, Korea Institute of Ocean Science and Technology) ;
  • Kim, Moon-Koo (Oil and POPs Research Group, Korea Institute of Ocean Science and Technology)
  • 김은식 (한국해양과학기술원 유류유해물질연구단) ;
  • 안준건 (한국해양과학기술원 유류유해물질연구단) ;
  • 김기범 (국립경상대학교 해양환경공학과) ;
  • 심원준 (한국해양과학기술원 유류유해물질연구단) ;
  • 주창규 (한국해양과학기술원 유류유해물질연구단) ;
  • 김문구 (한국해양과학기술원 유류유해물질연구단)
  • Received : 2012.06.13
  • Accepted : 2012.07.16
  • Published : 2012.08.25
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Abstract

Stable carbon isotope ratio of oil components are known to be unaffected by weathering processes and thus has been widely used to determine the origin of spilled oil. In this study, molecular index and composition of stable carbon isotope in 15 crude oils and petroleum product were analyzed and used as oil fingerprints to determine the discriminating power of each fingerprinting method among target crude oils. Through the fingerprints of alkane distribution only Bintulu and B-C(1%) were distinguishable from other crude oils. The pristane/phytane ratio can classify the crude oils into three groups but differentiation of crude oils within a group was impossible using the ratio. The crude oils of A.L., A.S.L., Foroozan and B-C(1%) were differentiated from the other oils using PAH source recognition indexes of C2D/C2P and C3D/C3P. The usage of 4-mD/1-mD and 2/3-mD/1-mD ratio was able to distinguish A.S.L., Bintulu and Oman from the other crude oils. However the PAH source recognition ratios in the other crude oils were similar and thus they were impractical to be used for source identification among the target crude oils. Stable carbon isotope ratios of alkanes were able to uniquely specify each crude oil in the plot of ${\delta}^{13}C_{C21}$ and ${\delta}^{13}C_{C25}$ except A.L., A.M., Qatar-Marine, B-C(1%). The oil fingerprinting method using stable carbon isotope ratios of individual alkane compounds showed more discriminating power among the target crude oils than the conventional source recognition indexes of PAHs or alkanes.

원유의 탄소안정동위원소비는 증발, 생물분해, 용해 등 풍화작용에 의해 큰 영향을 받지 않는 것으로 알려져 있어, 유출유의 기원을 확인하는 추적자로서 널리 사용되고 있다. 본 연구에서는 국내에 수입되고 있는 유류 중 주요 14종 원유와 제품유 1종의 분자단위 유지문 지표와 탄소안정동위원소비 조성을 분석하고, 이를 유지문으로 활용하여 각 지표의 유류 간 식별력을 비교하였다. Bintulu 원유와 제품유(B-C(1%)) 만이 다른 원유와 구별되는 고유한 alkane 분포패턴을 보였고, 나머지 원유들은 매우 유사한 분포특성을 나타내었다. Alkane 분자지표를 사용하였을 때, 원유를 크게 3개 그룹으로 분류할 수 있었으나 그룹 내 식별은 불가능하였다. PAHs 분자지표인 C2D/C2P와 C3D/C3P 이중지수를 이용해서 A.L., A.S.L., Foroozan, B-C(1%)을 다른 원유들로부터 구별할 수 있었으며, 4-mD/1-mD와 2/3-mD/1-mD 이중지수는 A.S.L., Bintulu, Oman 원유를 뚜렷이 식별할 수 있었다. 하지만 나머지 원유들은 매우 유사한 값을 가지고 있어서 원유 간 식별이 어려웠다. 반면 탄소안정동위원소비를 활용한 식별법은 A.L., A.M., Qatar-Marine, B-C(1%)를 제외한 나머지 모든 원유 사이의 식별을 가능하게 하였다. 개별화합물의 탄소안정동위원소 조성비를 활용한 유지문 분석법은 기존의 PAHs와 alkane의 대표적인 분자지표들과 비교했을 때 상대적으로 높은 원유 간 식별력을 보여 주었다.

Keywords

Acknowledgement

Grant : 유류오염 환경영향평가 및 환경복원 연구

Supported by : 국토해양부

References

  1. Andrusevich, V.E., Engel, M.H., Zumberge, J.E. and Brothers, L.A., 1998, Secular, episodic changes in stable carbon isotope composition of crude oils, Chemical Geology, Vol.152, 59-72. https://doi.org/10.1016/S0009-2541(98)00096-5
  2. Barakat, A.O., Qian, Y., Kim, M. and Kennicutt, M.C., 2001, Chemical characterization of naturally weathered oil residues in arid terrestrial environment in Al-Alamein, Egypt, Environment International, Vol.27, 291-310. https://doi.org/10.1016/S0160-4120(01)00060-5
  3. Boehm, P.D., Douglas, G.S., Burns, W.A., Mankiewicz, P.J., Page, D.S. and Bence, A.E., 1997, Application of petroleum hydrocarbon chemical fingerprinting and allocation techniques after the Exxon Valdez oil spill, Marine Pollution Bulletin, Vol.34, 599-613. https://doi.org/10.1016/S0025-326X(97)00051-9
  4. Cortes, J.E., Rincon, J.M., Jaramillo, J.M., Philp, P.R. and Allen, J., 2010, Biomarkers and compound-specific stable carbon isotope of n-alkanes in crude oils from Eastern Llanos Basin, Colombia, Journal of South American Earth Sciences, Vol.29, 198-213. https://doi.org/10.1016/j.jsames.2009.03.010
  5. Daugla, G.S., Bence, A.E., Prince, R.C., McMillen, S.J. and Butler, E.L., 1996, Environmental stability of selected petroleum hydrocarbon source and weathering ratios, Environmental Science and Technology, Vol.30, 2332-2339. https://doi.org/10.1021/es950751e
  6. Dutta, T.K. and Harayama, S., 2000, Fate of crude oil by combination of potooxidation and biodegradation, Environmental Science and Technology, Vol.34, 1500-1505. https://doi.org/10.1021/es991063o
  7. Enviromental Canada Oil Properties data base, http://www.etccte. ec.gc.ca/databases/oilproperties/default.aspx.
  8. Fingas, M., 2001, The Basics of Oil Spill Cleanup, Lewis Publishers, Boca Raton, 39-59.
  9. Kim, M.,Kennicutt II, M.C. and Qian, Y., 2007, Source characterization using compound composition and stable carbon isotope ratio of PAHs in sediments from lakes, harbor, and shipping waterway, Science of The Total Environment, Vol.389, 367-377.
  10. Li, Y. and Xiong, Y., 2009, Identification and quantification of mixed sources of oil spills based on distributions and isotope profiles of long-chain n-alkanes, Marine Pollution Bulletin, Vol.58, 1868-1873. https://doi.org/10.1016/j.marpolbul.2009.07.020
  11. Li, Y., Xiong, Y. and Yang, W., 2009, Compound-specific stable carbon isotopic composition of petroleum hydrocarbons as a tool for tracing the source of oil spills, Marine Pollution Bulletin, Vol.58, 114-117. https://doi.org/10.1016/j.marpolbul.2008.08.012
  12. Magnier, C., Moretti, I., Lopez, J.O., Gaumet, F., Lopez, J.G. and Letouzey, J., 2004, Geochemical characterization of source rocks, crude oils and gases of Northwest Cuba, Marine and Petroleum Geology, Vol.21, 195-214. https://doi.org/10.1016/j.marpetgeo.2003.11.009
  13. Mansuy, L., Philp, R.P. and Allen, J., 1997, Source identification of oil spills based on the isotope component in weathered oil samples, Environmental Science and Technology, Vol.31, 3417- 3425. https://doi.org/10.1021/es970068n
  14. Mazeas, L. and Budzinski, H., 2001, Polycyclic aromatic hydrocarbon C13/C12 ratio measurement in petroleum and marine sediments. Application to standard reference materials and a sediment suspected of contamination from the Erika oil spill, Journal of Chromatography A, Vol.923, 165-176. https://doi.org/10.1016/S0021-9673(01)00911-6
  15. Mazeas, L. and Budzinski, H., 2002, Molecular and stable carbon isotopic source identification of oil residues and oiled bird feathers sampled along the Atlantic coast of France after the Erika Oil Spill, Environmental Science and Technology, Vol.36, 130-137. https://doi.org/10.1021/es010726a
  16. Mudge, S.M., 2002, Reassessment of the hydrocarbon in Prince William Sound and Gulf of Alaska: identifying the source using partial least-squares, Environmental Science and Technology, Vol.36, 2354-2360. https://doi.org/10.1021/es015572d
  17. Petronet(한국석유공사 석유정보망). http://www.petronet.co.kr/main2.jsp.
  18. Wang, Z. and Fingas, M.F., 2003, Development of oil hydrocarbon fingerprinting and identification techniques, Marine Pollution Bulletin, Vol.47, 423-452. https://doi.org/10.1016/S0025-326X(03)00215-7
  19. Wang, Z., Fingas, M.F. and Page, D.S., 1999, Oil spill identification, Journal of Chromatography A, Vol.843, 369-411. https://doi.org/10.1016/S0021-9673(99)00120-X
  20. Wang, Z., Fingas, M.F. and Sigouin, L., 2000, Characterization and source identification of an unknown spilled oil using fingerprinting techniques by GC-MS and GC-FID, LC-GC North America, Vol.18, 1058-1067.
  21. Wang, Z., Fingas, M. and Sigouin, L., 2001, Characterization and identification of a "mystery" oil spill from Quebec (1999), Journal of Chromatography A, Vol.909, 155-169. https://doi.org/10.1016/S0021-9673(00)01084-0
  22. Yim, U.H., Ha, S.Y., An, J.G., Won, J.H., Han, G.M., Hong, S.H., Kim, M., Jung, J.H. and Shim W.J., 2011, Fingerprint and weathering characteristics of stranded oils after the Hebei Spirit oil spill, Journal of Hazardous Materials, Vol.197, 60-69. https://doi.org/10.1016/j.jhazmat.2011.09.055