Istanbul University, Engineering Faculty, Geology Department, Istanbul, Turkey

We report measurements of resolved 12CH2D2 and 13CH3D at natural abundances in a variety of methane gases produced naturally and in the laboratory. The ability to resolve 12CH2D2 from 13CH3D provides unprecedented insights into the origin and evolution of CH4. The results identify conditions under which either isotopic bond order disequilibrium or equilibrium are expected. Where equilibrium obtains, concordant D12CH2D2 and D13CH3D temperatures can be used reliably for thermometry. We find that concordant temperatures do not always match previous hypotheses based on indirect estimates of temperature of formation nor temperatures derived from CH4/H2 D/H exchange, underscoring the importance of reliable thermometry based on the CH4 molecules themselves. Where D12CH2D2 and D13CH3D values are inconsistent with thermodynamic equilibrium, temperatures of formation derived from these species are spurious. In such situations, while formation temperatures are unavailable, disequilibrium isotopologue ratios nonetheless provide novel information about the formation mechanism of the gas and the presence or absence of multiple sources or sinks. In particular, disequilibrium isotopologue ratios may provide the means for differentiating between methane produced by abiotic synthesis vs. biological processes. Deficits in 12CH2D2 compared with equilibrium values in CH4 gas made by surface-catalyzed abiotic reactions are so large as to point towards a quantum tunneling origin. Tunneling also accounts for the more moderate depletions in 13CH3D that accompany the low 12CH2D2 abundances produced by abiotic reactions. The tunneling signature may prove to be an important tracer of abiotic methane formation, especially where it is preserved by dissolution of gas in cool hydrothermal systems (e.g., Mars). Isotopologue signatures of abiotic methane production can be erased by infiltration of microbial communities, and D12CH2D2 values are a key tracer of microbial recycling.

The Chimaera gas seep, near Antalya (SW Turkey), has been continuously active for thousands of years and it is known to be the source of the first Olympic fire in the Hellenistic period. New and thorough molecular and isotopic analyses including methane (approximately 87% v/v; δ to the power of 13 C1 from -7.9‰ to -12.3‰; δ to the power of 13 D1 from -119‰ to -124‰), light alkanes (C2 + C3 + C4 + C5 = 0.5%; C6+: 0.07%; δ to the power of 13 C2 from -24.2‰ to -26.5‰; δ to the power of 13 C3 from -25.5‰ to -27‰), hydrogen (7.5–11%), carbon dioxide (0.01–0.07%; δ to the power of 13 CCO2: -15‰), helium (approximately 80 ppmv; R/Ra: 0.41) and nitrogen (2–4.9%; δ to the power of 15 N from -2‰ to -2.8‰) converge to indicate that the seep releases a mixture of organic thermogenic gas, related to mature type III kerogen occurring in Palaeozoic and Mesozoic organic-rich sedimentary rocks, and abiogenic gas produced by low-temperature serpentinization in the Tekirova ophiolitic unit. Methane is not related to mantle or magma degassing. The abiogenic fraction accounts for about half of the total gas released, which is estimated to be well beyond 50 ton year to the power of -1. Ophiolites and limestones are in contact along a tectonic dislocation leading to gas mixing and migration to the Earth’s surface. Chimaera represents the biggest emission of abiogenic methane on land discovered so far. Deep and pressurized gas accumulations are necessary to sustain the Chimaera gas flow for thousands of years and are likely to have been charged by an active inorganic source.

The emission of abiotic methane (CH4) into the atmosphere from low temperature serpentinization in ophiolitic rocks is documented to date only in four countries, the Philippines, Oman, New Zealand, and Turkey. Serpentinization produces large amounts of hydrogen (H2) which in theory may react with CO2 or CO to form hydrocarbons (Fischer–Tropsch Type synthesis, FTT). Similar mechanisms have been invoked to explain the CH4 detected on Mars, so that understanding flux and exhalation modality of ophiolitic gas on Earth may contribute to decipher the potential degassing on Mars. This work reports the first direct measurements of gas (CH4, CO2) flux ever done on onshore ophiolites with present-day serpentinization. We investigated the Tekirova ophiolites at Çirali, in Turkey, hosting the Chimaera seep, a system of gas vents issuing from fractures in a 5000 m2 wide ophiolite outcrop. At this site at least 150–190 t of CH4 is annually released into the atmosphere. The molecular and isotopic compositions of C1–C5 alkanes, CO2, and N2 combined with source rock maturity data and thermogenic gas formation modelling suggested a dominant abiotic component (~80– 90%) mixed with thermogenic gas. Abiotic H2-rich gas is likely formed at temperatures below 50 °C, suggested by the low deuterium/hydrogen isotopic ratio of H2 (δDH2: −720‰), consistent with the low geothermal gradient of the area. Abiotic gas synthesis must be very fast and effective in continuously producing an amount of gas equivalent to the long-lasting (N2 millennia) emission of N100 t CH4 yr−1, otherwise pressurised gas accumulation must exist. Over the same ophiolitic formation, 3 km away from Chimaera, we detected an invisible microseepage of abiotic CH4 with fluxes from 0.07 to 1 g m−2 d−1. On Mars similar fluxes could be able to sustain the CH4 plume apparently recognised in the Northern Summer 2003 (104 or 105 t yr−1) over the wide olivine bedrock and outcrops of hydrated silicates in the Syrtis Major and Nili Fossae; just one seep like Chimaera or, more realistically, a weak, spatially sporadic microseepage, would be sufficient to maintain the atmospheric CH4 level on Mars.