Petroleum Systems and Mixed Oil in the Barents Sea and Northern Timan-Pechora Basin, Russia*

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Petroleum Systems and Mixed Oil in the Barents Sea and Northern Timan-Pechora Basin, Russia* Meng He 1, Kenneth E. Peters 2, J. Michael Moldowan 3, and Alla Rovenskaya 4 Search and Discovery Article #10357 (2011) Posted September 26, 2011 *Adapted from oral presentation at 3P-Polar Petroleum Potential Conference & Exhibition, Halifax, Nova Scotia, Canada, August 30-September 2, 2011, hosted and organized by AAPG and Allworld Exhibitions. 1 Geological & Environmental Sciences, Stanford University, Stanford, CA (KPeters2@slb.com) 2 Schlumberger, Mill Valley, CA 3 Biomarker Technology, Sebastopol, CA 4 Foundation for East-West Cooperation, Moscow, Russian Federation Abstract Biomarkers and diamondoids were used to identify petroleum systems and infer source rocks for 34 oil samples from the Barents Sea and northern Timan-Pechora Basin. Chemometric analysis indicates five oil families from Triassic, Devonian (carbonate), Devonian (marl), Lower-Middle Jurassic, and Upper Jurassic source rocks. Based on the method of Dahl et al. (1999), 14 samples are mixtures of mature oil and highly mature condensate from deep, previously undetected source rock. Compound-specific isotope analyses of biomarkers and diamondoids show that highly mature Devonian source rock contributes to most of the mixed oil samples. The Triassic oil family occurs in Triassic and Permian reservoirs in the northern Timan-Pechora Basin and the southern Barents Sea. The oils have high extended tricyclic terpane ratios (ETR), consistent with Triassic source rock. The Devonian carbonate oil family occurs in Permian and Devonian reservoirs in the northern Timan-Pechora Basin and Pechora Sea. The oils show high C 29 /C 30 hopane, pristane/phytane (Pr/Ph) <1, elevated C 34 -homohopanes and C 29 steranes, and low dinosteroids. The oils from Devonian marl source rock occur in Devonian reservoirs in the northern Timan-Pechora Basin. They are similar to the carbonate family, but have Pr/Ph >1 and lack elevated C 34 homohopanes. The two Jurassic oil families have high bicadinanes and triaromatic dinosteroids, consistent with Jurassic source rock having terrigenous input. The Lower-Middle Jurassic oils occur in Lower-Middle Jurassic reservoirs in the Shtokmanovskoye Field and on Spitsbergen Island. These oils have Pr/Ph >3, high C 19 /(C 19 +C 23 ), low C 22 /C 21, and high C 24 /C 23 tricyclic terpane ratios, and elevated C 29 steranes indicating paralic marine shale source rock with higher plant-input, similar to oil generated from the Tyumen Formation Copyright AAPG. Serial rights given by author. For all other rights contact author directly.

in West Siberia (Peters et al., 2007). The Upper Jurassic oil family occurs in Triassic and Permian reservoirs on Kolguyev Island and the Pechora Sea. The oils show geochemical properties like those previously ascribed to the Bazhenov Formation in West Siberia (Peters et al., 2007). References Dahl, J.E., J.M. Moldowan, K.E. Peters, G.E. Claypool, M.A. Rooney, G.E. Michael, M.R. Mello, and M.L. Kohnen, 1999, Diamondoid hydrocarbons as indicators of natural oil cracking: Nature, v. 399, p. 54-57. Peters, K.E., L.S. Ramos, J.E. Zumberge, Z.C. Valin, C.R. Scotese, and D.L. Gautier, 2007, Circum-Arctic petroleum systems identified using decision-tree chemometrics: AAPG Bulletin, v. 91, p. 877-913.

3P Arctic Conference & Exhibition Halifax, Nova Scotia; 30 August-2 September, 2011 Arctic Petroleum Systems; 8:55 am Thursday Petroleum Systems and Mixed Oil in the Barents Sea and Northern Timan-Pechora Basin, Russia Meng He 1, Ken Peters 1,2, Michael Moldowan 1,3, and Alla Rovenskaya 4 1 Stanford University, Stanford, CA 94305; hmenglxq@stanford.edu 2 Schlumberger, Mill Valley, CA 94941; kpeters2@slb.com 3 Biomarker Technology, Sebastopol, CA 95472; moldowan@stanford.edu 4 Foundation for East-West Cooperation, Moscow, Russia; tnemchenko@mail.ru

Notes by Presenter: Map of the Timan-Pechora Basin shows identified oil families.

Notes by Presenter: Four proposed source rocks (Dore, 1995): Jurassic Triassic (Middle Tr. in Northern Barents Sea; Lower Tr. in Southern Barents Sea) 3) Lower Permian (insufficient TOC 0.75-1.0%; Ulmishek, 1982) 4) Domanik (Upper Devonian)

PCA of 22 Source-Related Biomarker and Isotope Ratios Identifies Six Oil Families 34 Oil Samples Family I II III IV V VI

Mesozoic Oil Families I, V, and VI Occur in the Barents Sea 34 Oil Samples I Triassic V Upper Jurassic Family I II III IV V VI VI Lower-Middle Jurassic

Mesozoic Families I (Triassic), V (U. Jurassic), and VI (L.-M. Jurassic) Occur in the Barents Sea 0 o 30 o 60 o 90 o 75 o Family I) Triassic V) Upper Jurassic VI) Lower-Middle Jurassic Modified from Ulmishek (1982) and Lindquist (1999)

Notes by Presenter: TA-Dino = Triaromatic dinosteranes/(ta-dino+3-methylstigmastane 20R) TA-DMD3/C 28 S = Triaromatic 23,24-dimethylcholesteroids (TA-DMC)/C 28 stigmastane = C 28 triaromatic demethyldinosterane/c 28 stigmastane

Notes by Presenter: Holba et al. (2001) studied a suite of worldwide crude oil samples with Triassic or Jurassic source rocks based on geochemical and geological evidence. All Triassic oil samples (39) had ETR 2.0, except for three Late Triassic samples from the Adriatic Basin that probably originated from a hypersaline source-rock setting. Early Jurassic oil samples (17) had ETR 2.0, except for two samples with slightly higher values. Middle or Late Jurassic oil samples (73) had ETR 2.0 with most <1.2 (63). The sharp drop in ETR at the end of the Triassic corresponds to a major mass extinction, which may have had an impact on the principal biological sources of tricyclic terpanes (e.g., Tasmanites?).

Families V-VI Contain Bicadinanes Indicating Jurassic or Younger Source Rock Jurassic and younger From resinous angiosperms Triassic and older Barbanti and Moldowan, unpubl.

Families V-VI are from Jurassic or Younger Source Rocks with Terrigenous Input 0.018 Bicadinane Ratio 0.016 0.014 0.012 0.010 0.008 0.006 0.004 0.002 Triassic and older 144 Jurassic and younger 0.000 1 2 3 4 5 6 I II III IV V VI Family

Notes by Presenter: Note: The TA-Dino on the y-axis in the figure is not exactly the same as our TA-Dino = Triaromatic dinosteranes/(ta-dino+3-methylstigmastane 20R)

Notes by Presenter: TA-DMD3/C 28 S = Triaromatic 23,24-dimethylcholesteroids (TA-DMC)/C 28 stigmastane = C 28 triaromatic demethyldinosterane/c 28 stigmastane

Notes by Presenter: Triaromatic dinosteroids (dinoflagellates) are abundant in Mesozoic and undetected or in low abundance in most Paleozoic marine rock extracts

PCA of 22 Source-Related Biomarker and Isotope Ratios Identifies Six Oil Families 34 Oil Samples Family I II III IV V VI IV Mixed III Devonian carbonate II Devonian marl

Notes by Presenter: TA-Dino = Triaromatic dinosteranes/(ta-dino+3-methylstigmastane 20R) TA-DMD3/C 28 S = Triaromatic 23,24-dimethylcholesteroids (TA-DMC)/C 28 stigmastane = C 28 triaromatic demethyldinosterane/c 28 stigmastane

PCA Identifies Several Oil Samples that May Represent Mixtures 34 Oil Samples Family I II III IV V VI IV 144 81(3) Mixtures? III II 81(2)

Families I (Triassic) and IV (Mixed) are Isotopically Distinct from V (Jurassic) -27-28 U. Jurassic Family I -29 IV -30 V δ 13 C, -31-32 Triassic- Devonian Triassic -33-34 -35-36 16 18 20 22 24 26 28 30 32 34 n-alkane

Oil 144 is a Mixture of Families I and V -27-28 -29 144 U. Jurassic Family I IV -30 V δ 13 C, -31-32 Triassic- Devonian Triassic -33-34 Bicadinanes in oil 144 indicate Jurassic input -35-36 16 18 20 22 24 26 28 30 32 34 n-alkane

δ 13 C, Families I (Triassic) and IV (Mixed) are Distinct from II and III (Devonian) -27-28 -29-30 -31-32 -33 Triassic Triassic-Devonian Family I II III IV -34-35 -36 Devonian marl Devonian carbonate 16 18 20 22 24 26 28 30 32 34 n-alkane

δ 13 C, Oils 81(2) and 81(3) are Mixtures of Triassic (I) and Devonian (II, III) Input -27-28 -29-30 -31-32 -33 81(3) 81(2) Family I II III IV -34-35 -36 16 18 20 22 24 26 28 30 32 34 n-alkane

Diamondoids Concentrations Increase During Cracking of Petroleum Low Maturity No Cracking Biomarkers High Maturity No Cracking 3-Methyldiamantane 4-Methyldiamantane Slightly Cracked Intensely Cracked Diamondoids Dahl et al. (1999)

Diamondoid Plot Identifies Mixtures of Mature and Highly Cracked Oil Biomarkers Mixed Normal Maturity and Highly Cracked Input Diamondoids Dahl et al. (1999)

Many Samples are Mixtures Containing Mature Oil and Highly Cracked Products Biomarker (ppm) C 29 ααα20r Sterane 200 160 120 80 40 0 No cracking Light cracking 52(1) 0 10 20 30 40 50 60 70 274 44 Diamondoids (ppm) 3- and 4-Methyldiamantanes Family I II III IV V VI Highly cracked mixed oils 102(1)

Notes by Presenter: 1=1-methyladamantane, 2=1,4-dimethyladamantane(cis), 3=1,4-dimethyladamantane(trans), 4=1,3-dimethyladamantane, 5= 1,3,4- trimethyladamantane(cis), 6= 1,3,4-trimethyladamantane(trans), 7=1,3,6-trimethyladamantane, 8=1,3,5-trimethyladamantane, 9= 3- dimethyldiamantane

Oils 44 and 274 are Mixtures of Triassic with Highly Cracked Devonian Input -18 Family I δ 13 C, per mil -20-22 -24-26 Triassic 44 274 Devonian marl II III IV -28 Devonian carbonate -30 1 2 3 4 5 6 7 8 9 Methylated Adamantanes and Diamantane

3P Arctic Conference & Exhibition Halifax, Nova Scotia; 30 August-2 September, 2011 Arctic Petroleum Systems; 8:55 am Thursday Conclusions: Six Major Oil Families and Five Source Rocks in the Study Area Mesozoic Paleozoic Mixed Age Lithology Fam Occurrence Comment Triassic Shale(N) Marl (S) U Jurassic Shale V L-M Jurassic Shale I VI Devonian Marl II Widespread in Barents Sea, Timan-Pechora (Spitsbergen, Kolguyev I., Kolva Megaswell) Pechora Shelf, Kolguyev Island Barents Sea (Shtokman field, Spitsbergen) Timan-Pechora (Adzva- Varandey Zone) Devonian Carbonate III Timan-Pechora, Pechora Shelf Triassic- Devonian -- IV Pechora Shelf Thickens northward on Pechora Shelf; cracked Triassic from one source Bazhenov equivalent; no mixing on Pechora Shelf Tyumen equivalent Domanik; deep cosource in Timan-Pechora Domanik; deep cosource in Timan-Pechora Mixed Triassic and deep, high-maturity Domanik

Acknowledgements Fred Fago, Paul Lipton, Shaun Moldowan, Peter Denisevich, Ye Wang, David Zinniker, Jeremy Dahl, Robert Dunbar, Dave Mucciarone Stanford Molecular Organic Geochemistry Industrial Affiliates (MOGIA) Stanford Basin and Petroleum System Modeling (BPSM) Industrial Affiliates

3P Arctic Conference & Exhibition Halifax, Nova Scotia; 30 August-2 September, 2011 Arctic Petroleum Systems; 8:55 am Thursday References Barbanti, S.M., J.M. Moldowan, D.S. Watt, and E. Kolaczkowska, 2011. New triaromatic steroids distinguish Paleozoic from Mesozoic oil. Organic Geochemistry 42: 409-424. Dahl, J.E.. J.M. Moldowan, K.E. Peters, G.E. Claypool, M.A. Rooney, G.E. Michael, M.R. Mello, and M.L. Kohnen, 1999. Diamondoid hydrocarbons as indicators of natural oil cracking. Nature 399, 55-57. Holba, A. G., L. Ellis, I. L. Dzou, A. Hallam, W. D. Masterson, J. Françu, and A. L. Fincannon, 2001. Extended tricyclic terpanes as age discriminators between Triassic, Early Jurassic and Middle-Late Jurassic oils: 20th International Meeting on Organic Geochemistry, p. 464. Dore, A.G., 1995. Barents Sea geology, petroleum resources and commercial potential. Arctic 48, 207-221. Lindquist, S.J., 1999. The Timan-Pechora Basin province of northwest Arctic Russia: Domanik-Paleozoic total petroleum system. USGS Open-File Report 99-50-G, 24 p. Moldowan, J.M., S.R. Jacobsen, B.J. Huizinga, D.S. Watt, K.E. Peters, and F. Fago, 1996. Chemostratigraphic reconstruction of biofacies: Molecular evidence linking cystforming dinoflagellates with pre-triassic ancestors. Geology 24, 159-162. Peters, K.E., C.C. Walters, and J.M. Moldowan, 2005. The Biomarker Guide. Cambridge University Press, Cambridge, U.K., 1155 p. Ulmishek, G., 1985. Petroleum geology and resource assessment of the Timan-Pechora Basin, USSR, and the adjacent Barents-northern Kara shelf. Argonne National Laboratory Energy and Environmental System Division Report ANL/EES-TM-199, p. 197.