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The formation of giant tubular concretions triggered by anaerobic oxidation of methane as revealed by archaeal molecular fossils (Lower Eocene, Varna, Bulgaria)
De Boever, E.; Birgel, D; Thiel, V.; Muchez, P.; Peckmann, J.; Dimitrov, L.; Swennen, R. (2009). The formation of giant tubular concretions triggered by anaerobic oxidation of methane as revealed by archaeal molecular fossils (Lower Eocene, Varna, Bulgaria). Palaeogeogr. Palaeoclimatol. Palaeoecol. 280(1-2): 23-36. dx.doi.org/10.1016/j.palaeo.2009.05.010
In: Palaeogeography, Palaeoclimatology, Palaeoecology. Elsevier: Amsterdam; Tokyo; Oxford; New York. ISSN 0031-0182; e-ISSN 1872-616X, more
Peer reviewed article  

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Keyword
    Marine/Coastal
Author keywords
    Carbonates; Methane seepage; Lipid biomarkers; Geochemistry; Eocene; Varna

Authors  Top 
  • De Boever, E., more
  • Birgel, D
  • Thiel, V.
  • Muchez, P., more
  • Peckmann, J.
  • Dimitrov, L.
  • Swennen, R., more

Abstract
    Impressive, several meters high tubular concretions in shallow marine calcareous sands and sandstones represent part of the well-exposed, subsurface plumbing network of an Early Eocene methane seep system in the Balkanides foreland (Pobiti Kamani area, Varna, NE Bulgaria). An integrated approach, including petrography, inorganic geochemistry and lipid biomarker analyses was used to reconstruct the evolution of pore fluids and cementation conditions during tube formation and particularly, the role of methane-related carbonate diagenesis. Host sediment lithification from marine pore waters was perturbed soon after deposition by oxidation of predominantly microbial methane causing pervasive cementation by a 13C-poor, homogeneous calcite cement (d13C values as low as - 44.5‰ V-PDB). The importance of microbially mediated anaerobic oxidation of methane (AOM) is confirmed by extremely 13C-depleted archaeal biomarkers (d13C values as low as - 123‰ V-PDB). A suite of macrocyclic dialkyl glycerol diethers (MDGD-0 to -2) and sn-3-hydroxyarchaeol comprises a characteristic trait of the Eocene tubular concretions and might represent molecular fossils of so far unknown methane-oxidizing archaea (ANME). Subsurface calcite cementation surrounding the ascending methane plume, resulted from the changing pore water chemistry in response to AOM and could have, on a local scale, been encouraged by the concurrent alteration of detrital feldspar. Fluctuating d13C (up to - 8‰ V-PDB) and d18O (- 0.5 to - 9‰ V-PDB) signatures within a single tubular sandstone concretion are at least partly the consequence of isotopic resetting during late meteoric water circulation.

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