New evidence for a mixed inorganic and organic origin of the Olympic Chimaera fire (Turkey): a large onshore seepage of abiogenic gas

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

New evidence for a mixed inorganic and organic origin of the Olympic Chimaera fire (Turkey): a large onshore seepage of abiogenic gas

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; delta C-13(1) from -7.9 parts per thousand to -12.3 parts per thousand; delta D-13(1) from -119 parts per thousand to -124 parts per thousand), light alkanes (C-2 + C-3 + C-4 + C-5 = 0.5%; C6+: 0.07%; delta C-13(2) from -24.2 parts per thousand to -26.5 parts per thousand; delta C-13(3) from -25.5 parts per thousand to -27 parts per thousand), hydrogen (7.5-11%), carbon dioxide (0.01-0.07%; delta C-13(CO2): -15 parts per thousand), helium (approximately 80 ppmv; R/Ra: 0.41) and nitrogen (2-4.9%; delta N-15 from -2 parts per thousand to -2.8 parts per thousand) 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(-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

New evidence for a mixed inorganic and organic origin of the Olympic Chimaera fire (Turkey): a large onshore seepage of abiogenic gas

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.Published263-2733.8. Geofisica per l'ambienteJCR Journalreserve

Origin of the hydrocarbon gases carbon dioxide and hydrogen sulfide in Dodan Field (SE-Turkey)

Gas occurrences consisting of carbon dioxide (CO2), hydrogen sulfide (H2S), and hydrocarbon (HC) gases and oil within the Dodan Field in southeastern Turkey are located in Cretaceous carbonate reservoir rocks in the Garzan and Mardin Formations. The aim of this study was to determine gas composition and to define the origin of gases in Dodan Field. For this purpose, gas samples were analyzed for their molecular and isotopic composition. The isotopic composition of CO2, with values of -1.5 parts per thousand and -2.8 parts per thousand, suggested abiogenic origin from limestone. delta S-34 values of H2S ranged from +11.9 to +13.4 parts per thousand. H2S is most likely formed from thermochemical sulfate reduction (TSR) and bacterial sulfate reduction (BSR) within the Bakuk Formation. The Bakuk Formation is composed of a dolomite dominated carbonate succession also containing anhydrite. TSR may occur within an evaporitic environment at temperatures of approximately 120-145 degrees C. Basin modeling revealed that these temperatures were reached within the Bakuk Formation at 10 Ma. Furthermore, sulfate reducing bacteria were found in oil-water phase samples from Dodan Field. As a result, the H2S in Dodan Field can be considered to have formed by BSR and TSR

Adsorption equilibria between dye and surfactant in single and binary systems onto geological materials

Adsorption characteristics of cationic dyes and surfactants onto clay and sandstone from a single component system were studied using toluidine blue (TB) and cetyl trimethylammonium bromide (CTAB). Equilibrium data of TB and CTAB in the single solute systems fit well to the Langmuir and the Freundlich adsorption isotherms. Competitive adsorption was observed between dye and surfactant cations. The effect of sodium chloride on dye and surfactant adsorption was studied in TB-NaCl and CTAB-NaCl binary systems. Equilibrium adsorption for binary systems was analyzed by using the extended Langmuir and the extended Freundlich models. Adsorption results for the TB-CTAB system onto both adsorbents were also well described by the Sheindorf-Rebuhn-Sheintuch (SRS) model for multi-component systems. Free energy changes for adsorption systems were calculated using thermodynamic equilibrium constants evaluated from selectivity coefficients of the binary systems. The site distribution functions estimated using Freundlich model parameters gave valuable information about the ratio of the adsorption sites on adsorbent surface having different affinity for competing cations. (C) 2009 Elsevier B.V. All rights reserved

The relative abundances of resolved lCH2D2 and mCH3D and mechanisms controlling isotopic bond ordering in abiotic and biotic methane gases

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 Δ12CH2D2 and Δ13CH3D 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 Δ12CH2D2 and Δ13CH3D 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 versus 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 Δ12CH2D2 values are a key tracer of microbial recycling

The relative abundances of resolved lCH2D2 and mCH3D and mechanisms controlling isotopic bond ordering in abiotic and biotic methane gases

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 Δ12CH2D2 and Δ13CH3D 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 Δ12CH2D2 and Δ13CH3D 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 versus 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 Δ12CH2D2 values are a key tracer of microbial recycling