DOI: 10.1016/j.epsl.2020.116619
论文题名: Evidence for methane isotopic bond re-ordering in gas reservoirs sourcing cold seeps from the Sea of Marmara
作者: Giunta T. ; Labidi J. ; Kohl I.E. ; Ruffine L. ; Donval J.P. ; Géli L. ; Çağatay M.N. ; Lu H. ; Young E.D.
刊名: Earth and Planetary Science Letters
ISSN: 0012821X
出版年: 2021
卷: 553 语种: 英语
中文关键词: bond-ordering
; clumped isotopologues
; cold seeps
; methane
英文关键词: Gas emissions
; Isotopes
; Methane
; Mixing
; Offshore gas fields
; Paraffins
; Petroleum reservoirs
; Anaerobic oxidation of methanes
; Apparent temperature
; Carbon and hydrogens
; Equilibrium temperatures
; Formation mechanism
; Sedimentary reservoirs
; Subsurface temperature
; Thermodynamic equilibria
; Temperature
; chemical bonding
; equilibrium
; gas seepage
; geothermometry
; isotopic composition
; methane
; temperature
; Sea of Marmara
; Turkey
英文摘要: The measurement of methane clumped isotopologues (Δ13CH3D and Δ12CH2D2) allows exploring isotope bond ordering within methane molecules, and may reveal equilibrium temperatures. Whether such temperature reflects the formation or re-equilibration temperature of the methane is not well understood, but would have critical implications for the use of methane clumped isotopologues as geo-thermometers. Here we investigate gas bubbles from vigorous emissions at cold seeps (n = 14) in the Sea of Marmara, Turkey. These cold seeps are sourced from deeper sedimentary reservoirs. Conventional geochemical tracers such as carbon and hydrogen bulk isotopic ratios (13C/12C and D/H) or n-alkane molecular ratios, suggest these gases reflect various degrees of mixing between thermogenic and microbial sources. Some samples would generally be considered purely microbial in origin (C1/C2+>1500; δ13C<−60‰). We report measurements of Δ13CH3D and Δ12CH2D2 showing that a fraction of those gases are in internal thermodynamic equilibrium, with the abundances of the two mass-18 isotopologues indicating concordant temperatures of ∼90 °C and ∼130 °C. These concordant temperatures are recorded by gases of putative microbial and thermogenic origin; the temperatures of equilibration are irrespective of the formation mechanism of the gases. We conclude that the two high-temperatures recorded by Δ13CH3D and Δ12CH2D2 are best explained by non-enzymatic re-equilibration at two local subsurface temperatures. First principles suggest that unequal rates of exchange are possible. Disequilibrium signatures where the two isotopologues yield discordant apparent temperatures are exhibited by other samples. In those cases the data define a trend of variable Δ13CH3D at nearly constant Δ12CH2D2. These signatures are enigmatic, and we investigate and reject multiple possible explanations including mixing, diffusion or Anaerobic Oxidation of Methane. Different rates of re-equilibration between the two rare isotopologues are implied, although lacks experimental foundation at present. In general, all of these data point towards re-equilibration of the mass-18 methane isotopologues as an important process. © 2020 Elsevier B.V. Citation statistics:
资源类型: 期刊论文
标识符: http://119.78.100.158/handle/2HF3EXSE/165480
Appears in Collections: 气候变化与战略
There are no files associated with this item.
作者单位: IFREMER, Unité des Géosciences Marines, Plouzané, 29280, France; Université de Bretagne Occidentale, Laboratoire Géosciences Océan, Plouzané, 29280, France; Université de Paris, Institut de Physique du Globe de Paris, CNRS, Paris, F-75005, France; University of California Los Angeles, Department of Earth, Planetary and Space Sciences, Los Angeles, CA 90095, United States; Istanbul Teknik University, Faculty of Mines, Department of Geological Engineering, Istanbul, TR-34469, Turkey; Peking University, Department of Energy & Sciences, College of Engineering, Beijing, 100871, China
Recommended Citation:
Giunta T.,Labidi J.,Kohl I.E.,et al. Evidence for methane isotopic bond re-ordering in gas reservoirs sourcing cold seeps from the Sea of Marmara[J]. Earth and Planetary Science Letters,2021-01-01,553