Geo-Marine Letters

, Volume 38, Issue 2, pp 121–129 | Cite as

Can hydrocarbons entrapped in seep carbonates serve as gas geochemistry recorder?

  • Martin Blumenberg
  • Thomas Pape
  • Richard Seifert
  • Gerhard Bohrmann
  • Stefan Schlömer


The geochemistry of seep gases is useful for an understanding of the local petroleum system. Here it was tested whether individual light hydrocarbons in seep gases are representatively entrapped in authigenic carbonates that formed near active seep sites. If applicable, it would be possible to extract geochemical information not only on the origin but also on the thermal maturity of the hydrocarbon source rocks from the gases entrapped in carbonates in the past. Respective data could be used for a better understanding of paleoenvironments and might directly serve as calibration point for, amongst others, petroleum system modeling. For this approach, (sub)-recent seep carbonates from the Black Sea (Paleodnjepr region and Batumi seep area), two sites of the Campeche Knoll region in the Gulf of Mexico, and the Venere mud volcano (Mediterranean Sea) were selected. These seep carbonates derive from sites for which geochemical data on the currently seeping gases exist. During treatment with phosphoric acid, methane and higher hydrocarbons were released from all carbonates, but in low concentrations. Compositional studies demonstrate that the ratio of methane to the sum of higher hydrocarbons (C1/(C2+C3)) is (partly strongly) positively biased in the entrapped gas fraction. δ13C values of C1 were determined for all samples and, for the samples from the Gulf of Mexico and the Mediterranean Sea, also of C2 and C3. The present dataset from six seep sites indicates that information on the seeped methane can be—although with a scatter of several permil—recorded in seep carbonate matrices, but other valuable information like the composition and δ13C of ethane and propane appears to be modified or lost during, for example, enclosure or at an early stage of diagenesis.



BGR (PANORAMA project) is thanked for financial support, and the crews and captains of research cruises POS317/2, M72/3, M114 are thanked for excellent cooperation during field work. We also thank two anonymous reviewers and the editors Burg W. Flemming and Monique T. Delafontaine for their helpful comments. Jürgen Poggenburg, Daniela Graskamp, Dietmar Laszinski and Petra Adam are acknowledged for analytical support, and Eckhard Faber, Heiko Sahling, and Georg Scheeder for helpful discussions.

Compliance with ethical standards

Conflict of interest

The authors declare that there is no conflict of interest with third parties.


  1. Abrams MA (2005) Significance of hydrocarbon seepage relative to petroleum generation and entrapment. Mar Petrol Geol 22:457–477. CrossRefGoogle Scholar
  2. Abrams MA (2017) Evaluation of near-surface gases in marine sediments to assess subsurface petroleum gas generation and entrapment. Geosciences 7.
  3. Abrams MA, Dahdah NF (2010) Surface sediment gases as indicators of subsurface hydrocarbons – examining the record in laboratory and field studies. Mar Petrol Geol 27:273–284. CrossRefGoogle Scholar
  4. Aloisi G, Bouloubassi I, Heijs SK, Pancost RD, Pierre C, Sinninghe Damsté JS, Gottschal JC, Forney LJ, Rouchy JM (2002) CH4-consuming microorganisms and the formation of carbonate crusts at cold seeps. Earth Planet Sci Lett 203:195–203CrossRefGoogle Scholar
  5. Bahr A, Pape T, Bohrmann G, Mazzini A, Haeckel M, Reitz A, Ivanov M (2009) Authigenic carbonate precipitates from the NE Black Sea: a mineralogical, geochemical, and lipid biomarker study. Int J Earth Sci 98:677–695CrossRefGoogle Scholar
  6. Bayon G, Loncke L, Dupré S, Caprais JC, Ducassou E, Duperron S, Etoubleau J, Foucher JP, Fouquet Y, Gontharet S, Henderson GM, Huguen C, Klaucke I, Mascle J, Migeon S, Olu-Le Roy K, Ondréas H, Pierre C, Sibuet M, Stadnitskaia A, Woodside J (2009) Multi-disciplinary investigation of fluid seepage on an unstable margin: the case of the Central Nile deep sea fan. Mar Geol 261:92–104. CrossRefGoogle Scholar
  7. Beal EJ, House CH, Orphan VJ (2009) Manganese- and iron-dependent marine methane oxidation. Science 325:184–187CrossRefGoogle Scholar
  8. Bernard B, Brooks JM, Sackett WM (1977) A geochemical model for characterization of hydrocarbon gas sources in marine sediments. Proc Annu Offshore Technol Conf 3:435–438Google Scholar
  9. Birgel D, Himmler T, Freiwald A, Peckmann J (2008) A new constraint on the antiquity of anaerobic oxidation of methane: late Pennsylvanian seep limestones from southern Namibia. Geology 36:543–546. CrossRefGoogle Scholar
  10. Blumenberg M, Seifert R, Reitner J, Pape T, Michaelis W (2004) Membrane lipid patterns typify distinct anaerobic methanotrophic consortia. PNAS 101:11111–11116CrossRefGoogle Scholar
  11. Blumenberg M, Lutz R, Schlömer S, Krüger M, Scheeder G, Berglar K, Heyde I, Weniger P (2016) Hydrocarbons from near-surface sediments of the Barents Sea north of Svalbard – indication of subsurface hydrocarbon generation? Mar Petrol Geol 76:432–443. CrossRefGoogle Scholar
  12. Bohrmann G and The shipboard party (2015) Report and preliminary results of R/V METEOR cruise M112, dynamic of mud volcanoes and seeps in the calabrian accretionary prism, Ionian Sea, Catania (Italy) – Catania (Italy), November 6 – December 15, 2014. Berichte, MARUM – Zentrum für Marine Umweltwissenschaften, Fachbereich Geowissenschaften, Universität Bremen, No. 306. urn:nbn:de:gbv:46-00104282-14Google Scholar
  13. Bohrmann G, Greinert J, Suess E, Torres M (1998) Authigenic carbonates from the Cascadia subduction zone and their relation to gas hydrate stability. Geology 26:647–650CrossRefGoogle Scholar
  14. Brekke T, Lønne Ø, Ohm SE (1997) Light hydrocarbon gases in shallow sediments in the northern North Sea. Mar Geol 137:81–108CrossRefGoogle Scholar
  15. Campbell KA, Farmer JD, Des Marais D (2002) Ancient hydrocarbon seeps from the Mesozoic convergent margin of California: carbonate geochemistry, fluids and palaeoenvironments. Geofluids 2:63–94CrossRefGoogle Scholar
  16. Ceramicola S, Praeg D, Cova A, Accettella D, Zecchin M (2014) Seafloor distribution and last glacial to postglacial activity of mud volcanoes on the Calabrian accretionary prism, Ionian Sea. Geo-Mar Lett 34:111–129CrossRefGoogle Scholar
  17. Devol AH, Anderson JJ, Kuivila K, Murray JW (1984) A model for coupled sulfate reduction and methane oxidation in the sediments of Saanich inlet. Geochim Cosmochim Acta 48:993–1004CrossRefGoogle Scholar
  18. Ettwig KF, Shima S, van de Pas-Schoonen KT, Kahnt J, Medema MH, Den Camp HJM O, MSM J, Strous M (2008) Denitrifying bacteria anaerobically oxidize methane in the absence of archaea. Environ Microbiol 10:3164–3173CrossRefGoogle Scholar
  19. Faber E, Stahl W (1983) Analytical procedure and results of an isotope geochemical survey in an area of the British North Sea. Geol Soc Lond, Spec Publ 12:51–63CrossRefGoogle Scholar
  20. Faber E, Stahl WJ, Whiticar MJ, Lietz J, Brooks JM (1990) Thermal hydrocarbons in Gulf Coast sediments. In: 9th Annu res Conf Gulf Coast oils and gases: their characteristics, origin, distribution, and exploration and production significance, pp 297–308Google Scholar
  21. Faber E, Berner U, Hollerbach A, Gerling P (1997) Isotope geochemistry in surface exploration for hydrocarbons. Geol Jahrb D103:103–127Google Scholar
  22. Faber E, Schmidt M, Feyzullayev A (2015) Geochemical hydrocarbon exploration - insights from stable isotope models. Oil Gas Sci Technol 2:93–98Google Scholar
  23. Formolo MJ, Lyons TW, Zhang CL, Kelley C, Sassen R, Horita J, Cole DR (2004) Quantifying carbons sources in the formation of authigenic carbonates at gas hydrate sites in the Gulf of Mexico. Chem Geol 205:253–264CrossRefGoogle Scholar
  24. Hantschel T, Kauerauf AI (2009) Fundamentals of basin and petroleum systems modeling. Springer, BerlinGoogle Scholar
  25. Hayes J (1983) Practice and principles in biosynthetic processes. In: Meinschein WG (ed) Organic geochemistry of contemporaneous and ancient sediments. Great lakes section. SPEM, Bloomington, pp 5–31Google Scholar
  26. Head IM, Jones DM, Larter SR (2003) Biological activity in the deep subsurface and the origin of heavy oil. Nature 426:344–352CrossRefGoogle Scholar
  27. Himmler T, Birgel D, Bayon G, Pape T, Ge L, Bohrmann G, Peckmann J (2015) Formation of seep carbonates along the Makran convergent margin, northern Arabian Sea and a molecular and isotopic approach to constrain the carbon isotopic composition of parent methane. Chem Geol 415:102–117CrossRefGoogle Scholar
  28. Ijiri A, Tsunogai U, Gamo T, Nakagawa F, Sakamoto T, Saito S (2009) Enrichment of adsorbed methane in authigenic carbonate concretions of the Japan Trench. Geo-Mar Lett 29:301–308CrossRefGoogle Scholar
  29. Ivanov MV, Pimenov NV, Rusanov II, Lein AY (2002) Microbial processes of the methane cycle at the north-western shelf of the Black Sea. Estuar. Coast Shelf Sci 54:589–599CrossRefGoogle Scholar
  30. James AT (1983) Correlation of natural gas by use of carbon isotopic distribution between hydrocarbon components. AAPG Bulletin 67:1176–1191Google Scholar
  31. Kniemeyer O, Musat F, Sievert SM, Knittel K, Wilkes H, Blumenberg M, Michaelis W, Classen A, Bolm C, Joye SB, Widdel F (2007) Anaerobic oxidation of short-chain hydrocarbons by marine sulphate-reducing bacteria. Nature 449:898–901CrossRefGoogle Scholar
  32. Liebetrau V, Eisenhauer A, Linke P (2010) Cold seep carbonates and associated cold-water corals at the Hikurangi margin, New Zealand: new insights into fluid pathways, growth structures and geochronology. Mar Geol 272:307–318. CrossRefGoogle Scholar
  33. Luff R, Wallmann K, Aloisi G (2004) Numerical modeling of carbonate crust formation at cold vent sites: significance for fluid and methane budgets and chemosynthetic biological communities. Earth Planet Sci Lett 221:337–353CrossRefGoogle Scholar
  34. MacDonald IR, Bohrmann G, Escobar E, Abegg F, Blanchon P, Blinova V, Brückmann W, Drews M, Eisenhauer A, Han X, Heeschen K, Meier F, Mortera C, Naehr T, Orcutt B, Bernard B, Brooks J, de Faragó M (2004) Asphalt volcanism and chemosynthetic life in the Campeche knolls, Gulf of Mexico. Science 304:999–1002CrossRefGoogle Scholar
  35. Michaelis W, Seifert R, Nauhaus K, Treude T, Thiel V, Blumenberg M, Knittel K, Gieseke A, Peterknecht K, Pape T, Boetius A, Amann R, Jørgensen BB, Widdel F, Peckmann J, Pimenov NV, Gulin MB (2002) Microbial reefs in the Black Sea fueled by anaerobic oxidation of methane. Science 297:1013–1015CrossRefGoogle Scholar
  36. Morales C, Rogov M, Wierzbowski H, Ershova V, Suan G, Adatte T, Föllmi KB, Tegelaar E, Reichart G-J, de Lange GJ, Middelburg JJ, van de Schootbrugge B (2017) Glendonites track methane seepage in Mesozoic polar seas. Geology 45:503–506. CrossRefGoogle Scholar
  37. Murray JW, Grundmanis V, Smethie WM Jr (1978) Interstitial water chemistry in the sediments of Saanich inlet. Geochim Cosmochim Acta 42:1011–1026CrossRefGoogle Scholar
  38. Naehr TH, Birgel D, Bohrmann G, MacDonald IR, Kasten S (2009) Biogeochemical controls on authigenic carbonate formation at the Chapopote “asphalt volcano”, bay of Campeche. Chem Geol 266:399–411CrossRefGoogle Scholar
  39. Niemann H, Elvert M (2008) Diagnostic lipid biomarker and stable carbon isotope signatures of microbial communities mediating the anaerobic oxidation of methane with sulphate. Org Geochem 39:1668–1677CrossRefGoogle Scholar
  40. Panieri G, Polonia A, Lucchi RG, Zironi S, Capotondi L, Negri A, Torelli L (2013) Mud volcanoes along the inner deformation front of the Calabrian arc accretionary wedge (Ionian Sea). Mar Geol 336:84–98CrossRefGoogle Scholar
  41. Pape T, Blumenberg M, Seifert R, Egorov VN, Gulin SB, Michaelis W (2005) Lipid geochemistry of methane-seep-related Black Sea carbonates. Palaeogeogr Palaeoclimatol Palaeoecol 227:31–47CrossRefGoogle Scholar
  42. Pape T, Bahr A, Rethemeyer J, Kessler JD, Sahling H, Hinrichs K-U, Klapp SA, Reeburgh WS, Bohrmann G (2010) Molecular and isotopic partitioning of low-molecular-weight hydrocarbons during migration and gas hydrate precipitation in deposits of a high-flux seepage site. Chem Geol 269:350–363CrossRefGoogle Scholar
  43. Peckmann J, Thiel V (2004) Carbon cycling at ancient methane-seeps. Chem Geol 205:443–467CrossRefGoogle Scholar
  44. Peckmann J, Birgel D, Kiel S (2009) Molecular fossils reveal fluid composition and flow intensity at a cretaceous seep. Geology 37:847–850CrossRefGoogle Scholar
  45. Praeg D, Ceramicola S, Barbieri R, Unnithan V, Wardell N (2009) Tectonically-driven mud volcanism since the late Pliocene on the Calabrian accretionary prism, central Mediterranean Sea. Mar Pet Geol 26:1849–1865CrossRefGoogle Scholar
  46. Reitner J, Peckmann J, Reimer A, Schumann G, Blumenberg M, Thiel H (2003) Anatomy of methane-derived carbonate concretions and associated microbial communities in Black Sea sediments. Geophys Res Abstr 5:03647Google Scholar
  47. Ritger S, Carson B, Suess E (1987) Methane-derived authigenic carbonates formed by subduction-induced pore-water expulsion along the Oregon/Washington margin. Geol Soc Am Bull 98:147–156CrossRefGoogle Scholar
  48. Rubin-Blum M, Antony CP, Borowski C, Sayavedra L, Pape T, Sahling H, Bohrmann G, Kleiner M, Redmond MC, Valentine DL, Dubilier N (2017) Short-chain alkanes fuel mussel and sponge Cycloclasticus symbionts from deep-sea gas and oil seeps. Nat Microbiol 2:17093. CrossRefGoogle Scholar
  49. Sahling H, Borowski C, Escobar-Briones E, Gaytán-Caballero A, Hsu C-W, Loher M, MacDonald I, Marcon Y, Pape T, Römer M, Rubin-Blum M, Schubotz F, Smrzka D, Wegener G, Bohrmann G (2016) Massive asphalt deposits, oil seepage, and gas venting support abundant chemosynthetic communities at the Campeche knolls, southern Gulf of Mexico. Biogeosciences 13:4491–4512. CrossRefGoogle Scholar
  50. Sassen R, Joye S, Sweet ST, DeFreitas DA, Milkov AV, MacDonald IR (1999) Thermogenic gas hydrates and hydrocarbon gases in complex chemosynthetic communities, Gulf of Mexico continental slope. Org Geochem 30:485–497. CrossRefGoogle Scholar
  51. Schmale O, Beaubien SE, Rehder G, Greinert J, Lombardi S (2010) Gas seepage in the Dnepr paleo-delta area (NW-Black Sea) and its regional impact on the water column methane cycle. J Mar Syst 80:90–100. CrossRefGoogle Scholar
  52. Schoell M (1983) Genetic classification of natural gases. AAPG Bulletin 67:2225–2238Google Scholar
  53. Schubotz F, Lipp JS, Elvert M, Kasten S, Mollar XP, Zabel M, Bohrmann G, Hinrichs K-U (2011) Petroleum degradation and associated microbial signatures at the Chapopote asphalt volcano, southern Gulf of Mexico. Geochim Cosmochim Acta 75:4377–4398. CrossRefGoogle Scholar
  54. Suess E (2014) Marine cold seeps and their manifestations: geological control, biogeochemical criteria and environmental conditions. Int J Earth Sci 103:1889–1916. CrossRefGoogle Scholar
  55. Ueno Y, Yamada K, Yoshida N, Maruyama S, Isozaki Y (2006) Evidence from fluid inclusions for microbial methanogenesis in the early Archaean era. Nature 440:516–519CrossRefGoogle Scholar
  56. Wacker U, Fiebig J, Tödter J, Schöne BR, Bahr A, Friedrich O, Tütken T, Gischler E, Joachimski MM (2014) Empirical calibration of the clumped isotope paleothermometer using calcites of various origins. Geochim Cosmochim Acta 141:127–144. CrossRefGoogle Scholar
  57. Whiticar MJ (1999) Carbon and hydrogen isotope systematics of bacterial formation and oxidation of methane. Chem Geol 161:291–314CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany 2017

Authors and Affiliations

  1. 1.Federal Institute for Geosciences and Natural Resources (BGR)HannoverGermany
  2. 2.MARUM – Center for Marine Environmental Sciences and Department of GeosciencesUniversity of BremenBremenGermany
  3. 3.Department of Earth Sciences, Institute for GeologyUniversity of HamburgHamburgGermany

Personalised recommendations