Tag: methane

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ESTIMATION OF THE METHANE-GENERATING CAPACITY OF FOSSIL ORGANIC MATTER

Home > Archive > No. 1 (201) 2026 > 51–62

Geology & Geochemistry of Combustible Minerals No. 1 (201) 2026, 51–62

ISSN 0869-0774 (Print), ISSN 2786-8621 (Online)

https://doi.org/10.15407/ggcm2026.201.051

Yurii KHOKHAa, Oleksandr LYUBCHAKb, Myroslava YAKOVENKOc

Institute of Geology and Geochemistry of Combustible Minerals of the National Academy of Sciences of Ukraine, Lviv, Ukraine

a e-mail: khoha_yury@ukr.net, https://orcid.org/0000-0002-8997-9766
b e-mail: oleksandr.lyubchak@gmail.com, https://orcid.org/0000-0002-0700-6929
c e-mail: myroslavakoshil@ukr.net, https://orcid.org/0000-0001-8967-0489

Abstract

The methane-generative capacity of fossil organic matter (FOM) controls both the resource potential of sedimentary successions (natural gas) and the environmental implications of CH4 generation and migration. While equilibrium thermodynamic models provide an upper bound for methane yield, methane generation in geological settings is predominantly kinetic-controlled, and comprehensive equilibrium/kinetic reconstructions often require detailed structural inputs that are unavailable in routine practice.

Aim. To develop a minimal-parameter, chemically consistent framework for quantifying methane generation from FOM in the “solid organic matrix–fluid” system using measurable quantities and a kinetics-centered descriptor applicable under limited structural information.

Approach and methods. Methane formation is treated as a radical-controlled demethanation process, formalized by the rate expression d[CH4]/dt = k[CH3][H]. Here [CH3] denotes the amount of structural methyl fragments (–CH3) bound within the macromolecular matrix (kerogen/coal/peat), whereas [H] represents the pool of chemically bound donor hydrogen, excluding –OH and –COOH hydrogen in the baseline formulation. Conditions under which protonic (heterolytic) stages may become significant (high polarity, pore water, strong acidity/alkalinity, Lewis-acid catalysis, oxidants, transition metals, mineral surfaces, irradiation) are outlined, and it is shown that explicitly accounting for such pathways would substantially complicate the kinetic equation set. An analytical solution is discussed together with a practical reduction to an exponential law, [CH4] = [CH4]0 + [CH3]0 (1 − e−t/τ), where the characteristic time τ is defined from the initial slope of the methane accumulation curve CH4(t) and can be estimated graphically via the tangent at t = 0. The paper specifies an experimental–analytical workflow to determine [CH4]0 by gas chromatography and to quantify the –CH3 reservoir using direct structural methods: FTIR spectroscopy (integration of –CH3/–CH2 bands with spectral approximation and peak separation of overlapping features) and quantitative solid-state 13C MAS NMR (integration of methyl carbon at 0–22 ppm, with explicit separation of methoxyl O–CH3 at 55–60 ppm when peat/soils are considered). Product-oriented techniques (pyrolysis GC/GC-MS and Rock-Eval) are discussed as complementary controls of CH4 release during thermal decomposition.

Key results and interpretation. The proposed framework reduces methane-generative capacity to two experimentally anchored descriptors: the structural reservoir of methyl fragments and the kinetic parameter τ, interpreted as an integral measure of reactive-site accessibility and the overall rate of radical transformations in a given matrix. Using τ enables laboratory characterization within shortened observation windows, by passing the impracticality of directly determining k on geological time scales, and provides a consistent basis for comparing samples of different origin and maturity. The applicability domain is delineated, emphasizing external factors capable of shifting mechanisms and kinetics (O2, water, mineral/metal catalysis, oxidants, irradiation), and the necessity to discriminate aliphatic –CH3 from methoxyl O–CH3 in oxygen-rich matrices is highlighted.

Conclusion and significance. The study delivers an analytically transparent and experimentally verifiable route to quantify methane-generative capacity of FOM as the coupled outcome of a measurable –CH3 structural reserve and the characteristic time τ. The approach is suitable for comparative assessments across kerogen, coal, peat and soil organic matrices and provides a methodological foundation for further predictive modelling.

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Keywords

organic matter, kerogen, methane, methane generation, kinetics, FTIR, 13C MAS NMR, programmed pyrolysis

Referenses

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Galimov, E. M. (1988). Sources and mechanisms of formation of gaseous hydrocarbons in sedimentary rocks. Chemical Geology, 71(1–3), 77–95. https://doi.org/10.1016/0009-2541(88)90107-6

Henry, A. A., & Lewan, M. D. (1999). Comparison of kinetic-model predictions of deep gas generation (No. 99-326). U.S. Department of the Interior, U.S. Geological Survey. https://doi.org/10.3133/ofr99326

Ibarra, J. V., Muñoz, E., & Moliner, R. (1996). FTIR study of the evolution of coal structure during the coalification process. Organic Geochemistry, 24(6–7), 725–735. https://doi.org/10.1016/0146-6380(96)00063-0

Johnson, R. L., & Schmidt-Rohr, K. (2014). Quantitative solid-state 13C NMR with signal enhancement by multiple cross polarization. Journal of Magnetic Resonance, 239, 44–49. https://doi.org/10.1016/j.jmr.2013.11.009

Kenney, J. F., Kutcherov, V. A., Bendeliani, N. A., & Alekseev, V. A. (2002). The evolution of multicomponent systems at high pressures: VI. The thermodynamic stability of the hydrogen–carbon system: The genesis of hydrocarbons and the origin of petroleum. Proceedings of the National Academy of Sciences, 99(17), 10976–10981. https://doi.org/10.1073/pnas.172376899

Khokha, Yu., Liubchak, O., & Yakovenko, M. (2019). Termodynamika transformatsii kerohenu II typu. Heolohiia i heokhimiia horiuchykh kopalyn, 3(180), 25–40. https://doi.org/10.15407/ggcm2019.03.025 [in Ukrainian]

Khokha, Yu. V., Pavliuk, M. I., Yakovenko, M. B., & Liubchak, O. V. (2020). Termodynamichna rekonstruktsiia rezhymiv evoliutsii orhanichnoi rechovyny Dniprovsko-Donetskoi zapadyny. Zbirnyk naukovykh prats Instytutu heolohichnykh nauk NAN Ukrainy, 13, 3–13. https://doi.org/10.30836/igs.2522-9753.2020.215156 [in Ukrainian]

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Khramov, V., & Liubchak, O. (2009). Mekhanizm heneratsii metanu v porovomu prostori vuhillia. Heolohiia i heokhimiia horiuchykh kopalyn, 3–4(148–149), 44–54. [in Ukrainian]

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Received: January 25, 2026
Accepted: February 20, 2026
Published: April 21, 2026

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BOWELS OF THE EARTH – NATURAL PHYSICAL-CHEMICAL REACTOR: IS THE SEARCH FOR NATURAL METHANE A FUNDAMENTAL SCIENCE OR A TECHNICAL PROBLEM?

Home > Archive > No. 4 (181) 2019 > 104-115

Geology & Geochemistry of Combustible Minerals No. 4 (181) 2019, 104-115.

https://doi.org/10.15407/ggcm2019.04.104

Yosyp Svoren

Institute of Geology and Geochemistry of Combustible Minerals of National Academy of Sciences of Ukraine, Lviv, Ukraine,
e-mail: igggk@mail.lviv.ua

Abstract

It is shown that the hypothesis of organic origin of hydrocarbons doesn’t respond to the presence of a dominant concentration of methane in sediments, deposits, “shale’ series and so on, hence prospecting and exploration for hydrocarbon deposits in them are conducted in most cases intuitively, but not on the fundamental scientific basis.

Experimental studies based on the heating of slightly modified organic matter (peat) show that up to 200 °C in the process of its decomposition the following gases were delivered (vol. %): CO2 = 49.5; H2O = 49.3; CH4, C2H6, C3H8, N2, H2, SO2, H2S within 1.2 % in total.

It is confirmed that there is no coal methane, there is no shale gas-methane, but there is methane of one genesis with slightly different isotope composition of carbon, but synthesized according to the same mechanism in the high-thermobaric processes that after migration into the earth’s crust accumulated in the form of deposits in cavities of coal seams, terrigenous units, sandstones and so on.

Prospecting for pool-deposits of hydrocarbons should be carried out in conformity with developed “new technology of determination of prospects for oil and gas presence in the local area”, “physical-chemical model of synthesis of hydrocarbons and the way of geochemical searching for their occurrences”, “new theory of hydrocarbon synthesis and genesis in the earth’s lithosphere: abiogenic-biogenic dualism”.

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Keywords

fluid inclusions, minerals, methane, origin of hydrocarbons, exploration, pool-deposits, new technologies.

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DISTRIBUTION AND ORIGIN OF HYDROCARBON GASES IN COAL-BEARING DEPOSITS OF THE LVIV-VOLYN COAL BASIN

Home > Archive > No. 3-4 (172-173) 2017 > 87-105

Geology & Geochemistry of Combustible Minerals No. 1-2 (174-175) 2018, 87-105.

Mykhailo MATROFAILO, Iryna BUCHYNSKA, Andriy POBEREZHSKYY

Institute of Geology and Geochemistry of Combustible Minerals of National Academy of Sciences of Ukraine, Lviv, e-mail:igggk@mail.lviv.ua

Abstract

After sufficient study, generalizations of all the data available as to stratigraphy, tectonics, lithological composition of coal-bearing series of the basin from the point of view of its potential for gas presence was possible. The composition, nature of coal gases, forms of occurrence and the mode of their burial have been considered. Problems of generation of hydrocarbon gases in the process of coalification of organic substance and their abiogenic origin connected with subsurface processes of the Earth have been studied. The influence of reservoir properties of coal and coal-enclosing rocks, the composition and physical-mechanical features of the immediate roof and the foot of coal seams have been analysed, the dependence of the gas distribution in coal seams and coal-enclosing rocks upon disjunctive tectonic dislocations has been ascertained. The influence of intraformational and epigene washouts upon degassing of coal seams has been investigated. On the basis of construction of schemes of the gas presence in coal seams of some mine fields and on the whole basin the conclusions have been made about the methane distribution in coal-bearing series.
Materials on the assessment of methane resources of the gas-coal fields have been accumulated and systematized as well as the prospects of the modern natural gas presence in coal seams of the deep levels of the basin have been outlined. Optimum conditions of the formation of hydrocarbon gases accumulations have been cited. The conclusions have been made as to the modern extractive potential of gases of coal-bearing series of the Lviv-Volyn Basin as possible source of the improvement of the up-to-date state of the fuel-power complex of the Ukraine.

Full Text

Keywords

methane, gas presence, generation, migration, deposits, coal seam, gas-coal fields, resources, Lviv-Volyn coal basin.

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