The existence of methane in the Earth’s mantle does not cause any doubt, however, its possible chemical transformation under the mantle thermobaric conditions is not enough known. Investigation of methane at the upper mantle thermobaric conditions, using diamond anvil cells, demonstrated the possible formation of ethane, propane and n-butane from methane, however, theoretical calculations of methane behaviour at extreme temperature and pressure predicted also heavier hydrocarbons. We experimentally investigated the chemical transformations of methane at the upper mantle thermobaric conditions, corresponding to the depth of 70–80 km (850–1000 K, 2.5 GPa), using “Toroid”-type Large reactive volume device and gas chromatography. The experimental results demonstrated the formation of the complex hydrocarbon mixture up to C₇ with linear, branched and cycled structures and benzene. Unsaturated hydrocarbons were detected on the trace level in the products mixture. The increasing of exposure time leaded to growth of heavier components in the product systems. The data obtained suggest possible existence of complex hydrocarbon mixtures at the upper mantle thermobaric conditions and provide a new insight on the possible pathways of the hydrocarbons synthesis from methane in the upper mantle.

Subducted sediments play a key role in the evolution of the continental crust and upper mantle. As part of the deep carbon cycle, hydrocarbons are accumulated in sediments of subduction zones and could eventually be transported with the slab below the crust, thus affecting processes in the deep Earth’s interior. However, the behavior of hydrocarbons during subduction is poorly understood. We experimentally investigated the chemical interaction of model hydrocarbon mixtures or natural oil with ferrous iron-bearing silicates and oxides (representing possible rock-forming materials) at pressure-temperature conditions of the Earth’s lower crust and upper mantle (up to 2000(±100) K and 10(±0.2) GPa), and characterized the run products using Raman and Mössbauer spectroscopies and X-ray diffraction. Our results demonstrate that complex hydrocarbons are stable on their own at thermobaric conditions corresponding to depths exceeding 50 km. We also found that chemical reactions between hydrocarbons and ferrous iron-bearing rocks during slab subduction lead to the formation of iron hydride and iron carbide. Iron hydride with relatively low melting temperature may form a liquid with negative buoyancy that could transport reduced iron and hydrogen to greater depths.

—The chemical interaction of hydrocarbon systems and iron-bearing minerals was investigated under extreme upper mantle pT conditions. As a result, the formation of iron carbide and iron...

The existence of iron carbide in the upper mantle allows an assumption to be made about its possible involvement in the abyssal abiogenic synthesis of hydrocarbons as a carbon donor. Interacting with hydrogen donors of the mantle, iron carbide can form hydrocarbon fluid. In order to investigate the role of iron carbide in the abiogenic synthesis of hydrocarbons, the chemical reaction between cementite Fe₃C and water was modeled under thermobaric conditions, corresponding to the upper mantle. A series of experiments were conducted using a high-pressure high-temperature Toroid-type large reactive volume unit with further analysis by means of gas chromatography. The results demonstrated the formation of hydrocarbon fluid in a wide range of thermobaric conditions (873–1223 K, 2.5–6.0 GPa) corresponding to the upper mantle. A strong correlation between the composition of the fluid and the pT conditions of the synthesis was illustrated in the investigation. The higher temperature of the synthesis resulted in the formation of a “poor” hydrocarbon mixture, primarily comprising methane, while a higher pressure yielded the opposite effect, converting iron carbide into a complex hydrocarbon system, containing normal and iso-alkanes up to C₇ and benzene. This correlation explains the diversity of hydrocarbon systems produced experimentally, thus expanding the thermobaric range of the possible existence of complex hydrocarbon systems in the upper mantle. The results support the suggestion that the carbide—water reaction can be a source of both the carbon and hydrogen required for the abyssal abiogenic synthesis of hydrocarbons.

The commercial discovery of giant crude oil deposits at depths deeper than 10 km in various petroleum basins worldwide casts doubt on the validity of the theoretical calculations that have determined that the main zone of petroleum formation is at depths of 6–8 km (the ‘oil window’). However, the behavior of complex hydrocarbon systems at thermobaric conditions, which correspond to depths below 6–8 km, is poorly known. We experimentally investigated the thermal stability of a complex hydrocarbon system at the pressure-temperature conditions of Earth’s lower crust by means of Raman and Mössbauer spectroscopies. Our results demonstrated the chemical stability of the complex hydrocarbon system at thermobaric conditions corresponding to depths of 50 km, including the redox stability of the hydrocarbon system in a highly oxidative environment. The results of these experiments allowed us to revise the depth range in which petroleum deposits could occur.

The concentration of carbon dioxide and methane in the atmosphere has significantly increased over the last 60 years. One of the factors in the growth of methane and its homologue emissions is the intense thawing of gas hydrates, mainly from the Arctic shelf, which remains one of the less studied sources of atmospheric hydrocarbon emissions. Oxidation of methane and light-saturated hydrocarbons by ozone in the upper part of the atmosphere leads to the formation of CO₂. The analysis of several datasets presented in this paper allows us to find the correlation between CH₄ and CO₂ concentrations in the atmosphere. This finding suggests that methane and its homologues released from gas hydrates mainly in the Arctic shelf zone become a significant source of carbon dioxide in the atmosphere. Because the amount of hydrocarbons located in gas hydrate deposits on the Arctic shelf is huge, further evolution of this process can become a serious challenge.