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Minerals
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Genesis of Hydrocarbons in the Upper Mantle
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Genesis of Hydrocarbons in the Upper Mantle

A special issue of Minerals (ISSN 2075-163X). This special issue belongs to the section "Mineral Geochemistry and Geochronology".

Deadline for manuscript submissions: closed (29 February 2020) | Viewed by 11066

Special Issue Editor

Dr. Alexander G. Sokol

E-Mail Website
Guest Editor
V.S. Sobolev Institute of Geology and Mineralogy of the Siberian Branch, Russian Academy of Sciences, 630090 Novosibirsk, Russia
Interests: mantle petrology; fluid regime; abiotic hydrocarbons; diamond genesis; kimberlite

Special Issue Information

Dear Colleagues,

Hydrocarbons were key agents in the origin of life on the Earth and have influenced the history of civilization. The amount of abiotic hydrocarbons formed on a global scale is presumably minor compared to those produced by microbial processes or by thermogenic degradation of organic matter in sedimentary rocks. Has the Earth’s mantle been capable of generating essential volumes of hydrocarbons since its origin, and where may the constituent volatiles have come from? The answers can be found in integrated studies of samples of mantle rock, mineral, and fluids, as well as laboratory experiments and thermodynamic calculations. This work is just beginning, and only a few steps have been made on the long way to reconstruct the physicochemical conditions for the generation of hydrocarbons in the upper mantle and to understand the role of hydrocarbons in deep cycles of volatiles, mantle fluid regime, magma generation, and the formation of minerals. This Special Issue aims at bringing all relevant studies together. We welcome experimental and theoretical studies that provide insights into the formation of hydrocarbons at extreme pressures and temperatures and furnish petrological, geochemical, and mineralogical evidence for the participation of deep, abiotic hydrocarbons in the global crust and mantle processes.

Dr. Alexander G. Sokol
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Minerals is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2400 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • Hydrocarbons
  • Volatiles
  • Mantle
  • Subduction
  • Redox conditions

Published Papers (4 papers)

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Research

8 pages, 1602 KiB  
Article
Stability of a Petroleum-Like Hydrocarbon Mixture at Thermobaric Conditions That Correspond to Depths of 50 km
by Aleksandr Serovaiskii, Leonid Dubrovinky and Vladimir Kutcherov
Minerals 2020, 10(4), 355; https://doi.org/10.3390/min10040355 - 16 Apr 2020
Cited by 4 | Viewed by 2508
Abstract
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 [...] Read more.
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. Full article
(This article belongs to the Special Issue Genesis of Hydrocarbons in the Upper Mantle)
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18 pages, 2847 KiB  
Article
Formation of Hydrocarbons in the Presence of Native Iron under Upper Mantle Conditions: Experimental Constraints
by Alexander Sokol, Anatoly Tomilenko, Ivan Sokol, Pavel Zaikin and Taras Bul’bak
Minerals 2020, 10(2), 88; https://doi.org/10.3390/min10020088 - 21 Jan 2020
Cited by 2 | Viewed by 2255
Abstract
The formation of hydrocarbons (HCs) upon interaction of metal and metal–carbon phases (solid Fe, Fe3C, Fe7C3, Ni, and liquid Fe–Ni alloys) with or without additional sources of carbon (graphite, diamond, carbonate, and H2O–CO2 fluids) [...] Read more.
The formation of hydrocarbons (HCs) upon interaction of metal and metal–carbon phases (solid Fe, Fe3C, Fe7C3, Ni, and liquid Fe–Ni alloys) with or without additional sources of carbon (graphite, diamond, carbonate, and H2O–CO2 fluids) was investigated in quenching experiments at 6.3 GPa and 1000–1400 °C, wherein hydrogen fugacity (fH2) was controlled by the Fe–FeO + H2O or Mo–MoO2 + H2O equilibria. The aim of the study was to investigate abiotic generation of hydrocarbons and to characterize the diversity of HC species that form in the presence of Fe/Ni metal phases at P–T–fH2 conditions typical of the upper mantle. The carbon donors were not fully depleted at experimental conditions. The ratio of H2 ingress and consumption rates depended on hydrogen permeability of the capsule material: runs with low-permeable Au capsules and/or high hydrogenation rates (H2O–CO2 fluid) yielded fluids equilibrated with the final assemblage of solid phases at fH2sample ≤ fH2buffer. The synthesized quenched fluids contained diverse HC species, predominantly light alkanes. The relative percentages of light alkane species were greater in higher temperature runs. At 1200 °C, light alkanes (C1 ≈ C2 > C3 > C4) formed either by direct hydrogenation of Fe3C or Fe7C3, or by hydrogenation of graphite/diamond in the presence of Fe3C, Fe7C3, and a liquid Fe–Ni alloy. The CH4/C2H6 ratio in the fluids decreased from 5 to 0.5 with decreasing iron activity and the C fraction increased in the series: Fe–Fe3C → Fe3C–Fe7C3 → Fe7C3–graphite → graphite. Fe3C–magnesite and Fe3C–H2O–CO2 systems at 1200 °C yielded magnesiowüstite and wüstite, respectively, and both produced C-enriched carbide Fe7C3 and mainly light alkanes (C1 ≈ C2 > C3 > C4). Thus, reactions of metal phases that simulate the composition of native iron with various carbon donors (graphite, diamond, carbonate, or H2O–CO2 fluid) at the upper mantle P–T conditions and enhanced fH2 can provide abiotic generation of complex hydrocarbon systems that predominantly contain light alkanes. The conditions favorable for HC formation exist in mantle zones, where slab-derived H2O-, CO2- and carbonate-bearing fluids interact with metal-saturated mantle. Full article
(This article belongs to the Special Issue Genesis of Hydrocarbons in the Upper Mantle)
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17 pages, 2110 KiB  
Article
C- and N-Bearing Species in Reduced Fluids in the Simplified C–O–H–N System and in Natural Pelite at Upper Mantle P–T Conditions
by Ivan Sokol, Alexander Sokol, Taras Bul’bak, Andrey Nefyodov, Pavel Zaikin and Anatoly Tomilenko
Minerals 2019, 9(11), 712; https://doi.org/10.3390/min9110712 - 18 Nov 2019
Cited by 1 | Viewed by 2625
Abstract
C- and N-bearing species in reduced fluids weree studied experimentally in C–O–H–N and muscovite–C–O–H–N systems and in natural carbonate-bearing samples at mantle P–T parameters. The experiments reproduced three types of reactions leading to formation of hydrocarbons (HCs) at 3.8–7.8 GPa and 800–1400 °C [...] Read more.
C- and N-bearing species in reduced fluids weree studied experimentally in C–O–H–N and muscovite–C–O–H–N systems and in natural carbonate-bearing samples at mantle P–T parameters. The experiments reproduced three types of reactions leading to formation of hydrocarbons (HCs) at 3.8–7.8 GPa and 800–1400 °C and at hydrogen fugacity (fH2) buffered by the Fe–FeO (IW) + H2O or Mo–MoO2 (MMO) + H2O equilibria: (i) Thermal destruction of organic matter during its subduction into the mantle (with an example of docosane), (ii) hydrogenation of graphite upon interaction with H2-enriched fluids, and (iii) hydrogenation of carbonates and products of their reduction in metamorphic clayey rocks. The obtained quenched fluids analyzed after the runs by gas chromatography-mass spectrometry (GC–MS) and electronic ionization mass-spectrometry (HR–MS) contain CH4 and C2H6 as main carbon species. The concentrations of C2-C4 alkanes in the fluids increase as the pressure and temperature increase from 3.8 to 7.8 GPa and from 800 to 1400 °C, respectively. The fluid equilibrated with the muscovite–garnet–omphacite–kyanite–rutile ± coesite assemblage consists of 50–80 rel.% H2O and 15–40 rel.% alkanes (C1 > C2 > C3 > C4). Main N-bearing species are ammonia (NH3) in the C–O–H–N and muscovite–C–O–H–N systems or methanimine (CH3N) in the fluid derived from the samples of natural pelitic rocks. Nitrogen comes either from air or melamine (C3H6N6) in model systems or from NH4+ in the runs with natural samples. The formula CH3N in the quenched fluid of the C–O–H–N system is confirmed by HR–MS. The impossibility of CH3N incorporation into K-bearing silicates because of a big CH3NH+ cation may limit the solubility of N in silicates at low fO2 and hence may substantially influence the mantle cycle of nitrogen. Thus, subduction of slabs containing carbonates, organic matter, and N-bearing minerals into strongly reduced mantle may induce the formation of fluids enriched in H2O, light alkanes, NH3, and CH3N. The presence of these species must be critical for the deep cycles of carbon, nitrogen, and hydrogen. Full article
(This article belongs to the Special Issue Genesis of Hydrocarbons in the Upper Mantle)
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11 pages, 2201 KiB  
Article
Fate of Hydrocarbons in Iron-Bearing Mineral Environments during Subduction
by Aleksandr Serovaiskii, Elena Mukhina, Leonid Dubrovinsky, Aleksey Chernoutsan, Daniil Kudryavtsev, Catherine McCammon, Georgios Aprilis, Ilya Kupenko, Aleksandr Chumakov, Michael Hanfland and Vladimir Kutcherov
Minerals 2019, 9(11), 651; https://doi.org/10.3390/min9110651 - 23 Oct 2019
Cited by 6 | Viewed by 3291
Abstract
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 [...] Read more.
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. Full article
(This article belongs to the Special Issue Genesis of Hydrocarbons in the Upper Mantle)
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