Abstract
Aromatic fractions of 140 oils and condensates that originated from different types of source rocks (marine shale, terrestrial shale and marine carbonate) were analyzed using gas chromatographymass spectrometry (GC-MS) to investigate the relative distributions of methylated dibenzothiophenes with respect to thermal maturity. The positions of methyl groups of trimethyldibenzothiophene isomers (TMDBTs) including those used in the definition of maturity indicator TMDBT index in previous studies were firmly identified by co-elution of internal standards in GC-MS analysis and by comparing with reported retention indices. A new maturity ratio related to dimethyldibenzothiophenes (DMDBTs) is proposed on the basis of the differences in thermodynamic stability among different DMDBT isomers. Another maturity index (TMDBT-I2) based on TMDBTs is also suggested on the basis of our empirical observations and presumed thermodynamic stability of TMDBT isomers. These two newly proposed (2,6 + 3,6)-/l,4-DMDBT ratio and TMDBT-I2 correlate well with MDR (4-/l-methyldibenzothiophene) and 2,4-/1,4-DMDBT ratios, suggesting their common chemical reaction mechanisms and similar behavior with increasing maturity. Therefore, they can be effectively applied for maturity assessments. Furthermore, the TMDBTs related maturity parameters are more reliable for over-mature oils and condensates due to the relatively higher concentrations of thermodynamically unstable TMDBT isomers, i.e. 1,4,6-, 1,4,8- and 3,4,6-TMDBT in this study than those of 1-methyldibenzothiophene (1-MDBT) or 1,4-DMDBT. In contrast with 4,6-/1,4-DMDBT, the newly proposed (2,6 + 3,6)-/1,4-DMDBT ratios for oils that originated from different types of source rocks have approximately same relationship with the oil maturity (Rc %). This suggests that the lithology and organic facies may have relatively less influence on (2,6 + 3,6)-/1,4-DMDBT ratio compared to 4,6-/1,4-DMDBT. The maturity parameters based on methylated dibenzothiophenes are particularly useful in the maturity assessments of post- and over-mature oils and condensates and can complement maturity indicators based on steranes and terpanes.
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Alexander R, Kagi R I, Rowland S J, et al. The effects of thermal maturity on distributions of dimethylnaphthalenes and trimethylnaphthalenes in some ancient sediments and petroleums. Geochimica et Cosmochimica Acta. 1985. 49(2): 385–395
Asif M, Alexander R, Fazelat T, et al. Geosynthesis of dibenzothiophene and alkyldibenzothiophenes in crude oils and sediments by carbon catalysis. Organic Geochemistry. 2009. 40: 895–901
Asif M. Geochemical applications of polycyclic aromatic hydrocarbons in crude oils and sediments from Pakistan. Ph.D. thesis, University of Engineering and Technology, Lahore, Pakistan. 2010
Bao J P, Wang T. -G and Chen F J. Relative abundance of alkyl dibenzothiophenes in the source rocks and their geochemical significances. Journal of China University of Petroleum. 1996. 20: 19–23 (in Chinese)
Bao J P and Zhu C S. The effects of biodegradation on the compositions of aromatic hydrocarbons and maturity indicators in biodegraded oils from Liaohe Basin. Science in China Series D: Earth Sciences. 2009. 52: 59–68
Bastow T P, Alexander R, Fisher S J, et al. Geosynthesis of organic compounds. Part V — methylation of alkylnaphthalenes. Organic Geochemistry. 2000. 31(6): 523–534
Budzinski H, Garrigues P, Corrnan J, et al. Determination of maturity indicators in alkylated aromatic series by gas chromatographymass spectrometry (GC-MS). In: Manning D.A.C. (Ed.), Organic Geochemistry: Advances and Applications in Energy and the Natural Environment. Manchester University Press. 1991. 619–623
Budzinski H, Garrigues P, Radke M, et al. Use of molecular modeling as a tool to evaluate thermodynamic stability of alkylated polycyclic aromatic hydrocarbons. Energy & Fuels. 1993. 7(4): 505–511
Chakhmakhchev A and Suzuki N. Saturate biomarkers and aromatic sulfur compounds in oils and condensates from different source rock lithologies of Kazakhstan, Japan and Russia. Organic Geochemistry. 1995. 23: 289–299
Chakhmakhchev A, Suzuki M and Takayama K. Distribution of alkylated dibenzothiophenes in petroleum as a tool for maturity assessments. Organic Geochemistry. 1997. 26: 483–490
Connan J, Brououllec J, Dessort D, et al. The microbial input in carbonate-anhydrite facies of Sabkha palaeoenvironment from Guatemala: A molecular approach. In: Leythhaeuser D., Rullkötter J. (Eds.), Advances in Organic Geochemistry. Organic Geochemistry. 1986. 10:29–50
Cui J, Wang T, Li M, et al. Oil filling history of the Bashituo Oilfield in the Markit Slope, SW Tarim Basin, China. Petroleum Science. 2013. 10(1): 58–64
Ding W X, Wang W and Ma Y. Characteristics of Liushagang Formation petroleum system in Fushan Depression of Beibuwan Basin. Offshore Petroleum. 2003. 23(2): 1–6 (in Chinese)
Douglas A G and Mair B J. Sulfur: role in genesis of petroleum. Science. 1965. 147: 99–501
Dzou L P, Noble R A and Senftle J T. Maturation effects on absolute biomarker concentration in a suite of coals and associated vitrinite concentrates. Organic Geochemistry. 1995. 10: 29–50
Farrington J W, Davis A C, Tarafa M E, et al. Bitumen molecular maturity parameters in the Ikpikpuk well, Alaskan North Slope. Organic Geochemistry. 1988. 13(1–3): 303–310
Gransch J A and Posthuma J. On the origin of sulphur in crudes. Advances in Organic Geochemistry. 1974. 727–739
Hanson W E. Origin of petroleum. In: Gruse W.A., Stevens D.R. (Eds.), Chemical Technology of Petroleum. New York: McGraw-Hill. 1960. Chap. 5, p. 247
Ho T Y, Rogers M A, Drushel H V, et al. Evolution of sulfur compounds in crude oils. AAPG Bulletin. 1974. 58(11): 2338–2348
Huang H and Pearson M J. Source rock palaeoenvironments and controls on the distribution of dibenzothiophenes in lacustrine crude oils, Bohai Bay Basin, eastern China. Organic Geochemistry. 1999. 30: 1455–1470
Hughes W B. Use of thiophenic organosulfur compounds in characterizing crude oils derived from carbonate versus siliclastic sources. In: Palacas J.B. (Ed.), Petroleum Geochemistry and Source Rocks Potential of Carbonate Rocks. AAPG Studies in Geology No. 18, Oklahoma, AAPG Press. 1984. 181–196
Hughes W B, Holba A G and Dzou L I P. The ratios of dibenzothiophene to phenanthrene and pristane to phytane as indicators of depositional environment and lithology of petroleum source rocks. Geochemica et Cosmochimica Acta. 1995. 59: 3581–3598
Kruge M A. Determination of thermal maturity and organic matter type by principal components and analysis of the distributions of polycyclic aromatic compounds. International Journal of Coal Geology. 2000. 43: 27–51
Lee M L, Vassilaros D L, White C M, et al. Retention indices for programmed-temperature capillary-column gas chromatography of polycyclic aromatic hydrocarbons. Journal of Chromatography A. 1979. 51(6): 768–774
Li M J, Wang T G, Liu J, et al. Oil charging orientation and accumulation characteristics of oil reservoirs in the Fushan Sag, Beibuwan Basin. Petroleum Geology and Experiment. 2007a. 29(2): 172–176 (in Chinese)
Li M, Simoneit B R T, Zhong N, et al. The distribution and origin of dimethyldibenzothiophenes in sediment extracts from the Liaohe Basin, East China. Organic Geochemistry. 2013b. 65: 63–73
Li M, Wang T, Liu J, et al. Characteristics of oil and gas accumulation in Yong’an-Meitai Area of the Fushan Depression, Beibuwan Basin, South China Sea. Petroleum Science. 2007b. 4(4): 23–33
Li M, Wang T, Liu J, et al. Total alkyl dibenzothiophenes content tracing the filling pathway of condensate reservoir in the Fushan Depression, South China Sea. Science in China Series D: Earth Sciences. 2008a. 51(Supp.II): 138–145
Li M, Wang T, Liu J, et al. Occurrence and origin of carbon dioxide in the Fushan Depression, Beibuwan Basin, South China Sea. Marine and Petroleum Geology. 2008b. 25(6): 500–513
Li M, Wang T, Liu J, et al. The occurrence of oleananes in the Beibuwan Basin and its application to the study of maturity and oil-source rock correlation. Acta Geologica Sinica (English Edition). 2008c. 82(3): 585–595.
Li M, Wang T, Liu J, et al. Alkyl naphthalenes and phenanthrenes: molecular markers for tracing filling pathways of light oil and condensate reservoirs. Acta Geologica Sinica (English Edition). 2010. 84(5): 1294–1305
Li M, Wang T, Simoneit B R T, et al. Qualitative and quantitative analysis of dibenzothiophene, its methylated homologues, and benzonaphthothiophenes in crude oils, coal, and sediment extracts. Journal of Chromatography A. 2012. 1233: 126–136
Li M, Wang T, Zhong N, et al. Ternary diagram of fluorenes, dibenzothiophenes and dibenzofurans: Indicating depositional environment of crude oil source rocks. Energy Exploration & Exploitation. 2013c. 31: 569–588
Li M, Zhong N, Shi S, et al. The origin of trimethyldibenzothiophenes and their application as maturity indicators in sediments from the Liaohe Basin, East China. Fuel. 2013a. 103: 299–307
Li S, Pang X, Shi Q, et al. Origin of the unusually high dibenzothiophene concentrations in Lower Ordovician oils from the Tazhong Uplift, Tarim Basin, China. Petroleum Science. 2011. 8(4): 382–391
Luo J, Cheng K M, Fu L X, et al. Alkylated dibenzothiophene Index-a new method to assess thermal maturity of source rocks. Acta Petrolei Sinica. 2001. 22(3): 27–31 (in Chinese)
Moldowan J M, Dahl J, Huizinga B J, et al. The molecular fossil record of oleanane and its relation to angiosperms. Science. 1994. 265: 768–771
Mössner S G, de Alda M J L, Sandera L C, et al. Gaschromatographic retention behavior of polycyclicaromatic sulfur heterocyclic compounds, (dibenzothiophene, naphtho[b]thiophenes, benzo[b] naphthothiophenes and alkyl-substituted derivatives) on stationary phases of different selectivity. Journal of Chromatography A. 1999. 841(2): 207–228
Murray A P, Sosrowidjojo I B, Alexander R, et al. Oleananes in oils and sediments: Evidence of marine influence during early diagenesis. Geochemica et Cosmochimica Acta. 1997. 61(6): 1261–1276
Orr W L. Kerogen/asphaltene/sulfur relationships in sulfur-rich Monterey oils. Organic Geochemistry. 1986. 10: 499–516
Payzant J D, Mojelsky T W and Strausz O P. Improved methods for the selective isolation of the sulfide and thiophenic classes of compounds from petroleum. Energy & Fuels. 1989. 3(4): 449–454
Peters K E, Walters C C and Moldowan J M. The Biomarker Guide (2nd ed). New York: Cambridge University Press. 2005
Radke M. Application of aromatic compounds as maturity indicators in source rocks and crude oils. Marine and Petroleum Geology. 1988. 5: 224–236
Radke M and Welte D H. The methylphenanthrene index (MPI): a maturity parameter based on aromatic hydrocarbons. In: Bjoroy M. (Eds.), Advances in Organic Geochemistry. 1981. Chichester: Wiley. 504–512
Radke M and Willsch H. Extractable alkyldibenzothiophenes in Posidonia Shale (Toarcian) source rocks: Relationship of yields to petroleum formation and expulsion. Geochimica et Cosmochimica Acta. 1994. 58(23): 5223–5244
Radke M, Horsfield B, Littke R, et al. Maturation and petroleum generation. In: Welte D.H., Horsfield B., Baker D.R. (Eds.), Petroleum and Basin. Verlag: Springer. 1997. 171–229
Radke M, Vriend S P and Ramanampisoa L R. Alkydibenzofurans in terrestrial rocks: Influence of organic facies and maturation. Geochimica et Cosmochimica Acta. 2000. 64(2): 275–286
Radke M, Welte D H and Willsch H. Maturity parameters based on aromatic hydrocarbons: Influence of the organic matter type. Organic Geochemistry. 1986. 10(1–3): 51–63
Radke M, Welte D H and Willsch H. Distribution of alkylated aromatic hydrocarbons and dibenzothiophenes in rocks of the Upper Rhine Graben. Chemical Geology. 1991. 93: 325–341
Radke M, Willsch H, Leythaeuser, et al. Aromatic components of coal: relation of distribution pattern to rank. Geochimica et Cosmochimica Acta. 1982. 46(10): 1831–1848
Richard L. Calculation of the standard molal thermodynamic properties as a function of temperature and pressure of some geochemically important organic sulfur compounds. Geochimica et Cosmochimica Acta. 2001. 65: 3827–3877
Rowland S J, Alexander R, Kagi R I, et al. Microbial degradation of aromatic components of crude oils: A comparison of laboratory and field observations. Organic Geochemistry. 1986. 9(4): 153–161
Santamaría-Orozco D, Horsfield B, Primio R D I, et al. Influence of maturity on distributions of benzo- and dibenzothiophenes in Tithonian source rocks and crude oils, Sonda de Campeche, Mexico. Organic Geochemistry. 1998. 28: 423–439
Schade T and Andersson J T. Speciation of alkylated dibenzothiophenes through correlation of structure and gas chromatographic retention indexes. Journal of Chromatography A. 2006. 1117: 206–213
Schou L and Myhr M B. Sulfur aromatic compounds as maturity parameters. Organic Geochemistry. 1988. 13(1–3): 61–66
Shen P, Wang W, Zhang X, et al. Differentiating depositional environments and maturity of crude oils using GC-AED benzothiophenic spectra. Science in China Series D: Earth Sciences. 1998. 41(4): 401–407
Strachan M G, Alexander R and Kagi R I. Trimethylnaphthalenes in crude oils and sediments: Effects of source and maturity. Geochimica et Cosmochimica Acta. 1988. 52(5): 1255–1264
van Aarssen B G K, Bastow T P, Alexander R, et al. Distributions of methylated naphthalenes in crude oils: indicators of maturity, biodegradation and mixing. Organic Geochemistry. 1999. 30(10): 1213–1227
Vassilaros D L, Kong R C, Later D W, et al. Linear retention index system for polycyclic aromatic compounds: Critical evaluation and additional indices. Journal of Chromatography A. 1982. 252: 1–20
Wan L, Liu J, Mao F, et al. The petroleum geochemistry of the Termit Basin, Eastern Niger. Marine and Petroleum Geology. 2014. 51: 167–183
Wang T.-G, He F, Li M, et al. Alkyl-dibenzothiophenes: molecular tracers for filling pathway in oil reservoirs. Chinese Science Bulletin. 2004. 49: 2399–2404
Wang T.-G, He F, Wang C, et al. Oil filling history of the Ordovician oil reservoir in the major part of the Tahe Oilfield, Tarim Basin, NW China. Organic Geochemistry. 2008. 38: 1637–1646
Xia Y and Zhang G. Investigation of mechanisms of formation of biphenyls and benzonaphthothiophenes by simulation experiment. Science in China Series D: Earth Science. 2002. 45(5): 392–398
Zhang S and Huang H. Geochemistry of Palaeozoic marine petroleum from the Tarim Basin, NW China: Part 1. Oil family classification. Organic Geochemistry. 2005. 36: 1204–1214
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Li, M., Wang, T.G., Shi, S. et al. Oil maturity assessment using maturity indicators based on methylated dibenzothiophenes. Pet. Sci. 11, 234–246 (2014). https://doi.org/10.1007/s12182-014-0336-3
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DOI: https://doi.org/10.1007/s12182-014-0336-3