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INFLUENCE OF THE PORE STRUCTURE OF FOSSIL ORGANIC MATTER ON METHANOGENESIS IN FREE-CHAIN RADICAL REACTIONS

Home > Archive > No. 2 (202) 2026 > 62–75


Geology & Geochemistry of Combustible Minerals No. 2 (202) 2026, 62–75

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

https://doi.org/

Myroslava YAKOVENKOa, Yurii KHOKHAb, Oleksandr LYUBCHAKc

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

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


Abstract

The paper considers the role of pore structure in the formation of local thermobaric conditions that may support methane generation in fossil organic matter through chain free-radical reactions. The gas–organic matter system is treated as a heterogeneous dispersed medium in which nano-, micro- and mesopores cannot be described only by bulk pressure and temperature. A dimensionless pore-pressure coefficient π = Pp/P is used, where Pp is the pore pressure and P is the geostatic pressure. The value π = 1 corresponds to equality between pore and geostatic pressures, whereas π < 1 indicates a pore-pressure deficit; therefore, 1 − π can be interpreted as a relative measure of rarefaction. Model data are analysed for pore diameters of 0.5, 1, 2, 5, 10, 20, 50, 100 and 1000 nm within the depth range 0–10 km. Additional trends are discussed for peat and brown coal, medium-rank coal and anthracite under heat flows of 40 and 100 mW/m2. The results show that pore size is the main factor controlling the deviation of pore pressure from geostatic pressure. In pores of 0.5–2 nm, π remains far below unity even at a depth of 10 km, whereas pores of 100–1000 nm approach a quasi-equilibrium state. A higher heat flow slightly lowers π in small pores and can promote the formation of free radicals, but this effect is secondary to the geometric restriction imposed by pore size and shape. The evolution from peat and brown coal to anthracite is therefore interpreted not only as a change in sorption capacity and transport properties, but also as a change in the abundance of local pore domains favourable to the mechanical destruction of organic matter, radical stabilization, and methane generation. The proposed interpretation links pore-scale pressure heterogeneity with the kinetics of homolytic reactions and provides a basis for further quantitative modelling of methane formation in a three-phase coal matrix.

Keywords

coal, peat, anthracite, porosity, methane, pore pressure, rarefaction, free radicals, geostatic pressure, heat flow

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Received: April 21, 2026
Accepted: May 08, 2026
Published: May, 2026