Distribution and origin of gaseous hydrocarbons and carbon dioxide in the Quaternary sediments at Starunia palaeontological site and vicinity (Carpathian region, Ukraine)

Maciej J. Kotarba, Henryk Sechman, Marek Dzieniewicz


Near-surface gases were investigated in Starunia, where remains of mammoth and woolly rhinoceroses were discovered at the beginning of the 20th century. Samples were collected at 30 measurement sites, from 0.8, 1.6, 2.4, 3.2 and 4.0 m depths and analysed for their molecular and isotopic compositions. Most of the methane and all higher gaseous hydrocarbons accumulated within the near-surface zone are of thermogenic origin. The distribution of thermogenic methane and higher gaseous hydrocarbons in Quaternary sediments is variable and, generally, increases with depth. Microbial methane or a mixture of microbial and thermogenic methane also occurs at the near-surface zone. The presence of hydrogen and alkenes in the near-surface gases also suggests a contribution from recent, microbial processes. Helium of crustal origin migrated through the Rinne Fault and other tectonic zones located in the study area, and was subsequently dispersed during migration through the lithologically diversified Pleistocene and Holocene sediments. The high variability of the carbon dioxide concentration and stable carbon isotope composition at various depths in the near-surface zone is caused by its polygenetic origin (thermogenic, microbial, and oxidation of hydrocarbons and Quaternary organic matter), and also by its dissolution in water and oil during migration through lithologically diversified Pleistocene and Holocene sediments. Zones of thermogenic methane occurrence within Pleistocene sediments, dominated by muds saturated with bitumen and brines, provide the most favourable environment for preservation of large extinct mammals. It is likely that during the Pleistocene winters, when thick ice and snow covered the tundra lake and swamp, zones of outflow of brines, oils, helium, and thermogenic gaseous hydrocarbons had a higher temperature, which could have resulted in melting and cracking of the ice cover and drowning of large mammals. The most favourable conditions for preservation of large, extinct mammals probably still exists in the vicinity of sampling probe sites Nos 21, 22, 23 and 36. Zones of dominance of microbial methane concentrations are less favourable sites for preservation of extinct mammals, because this methane was generated within recent swamps and also within recent descending meteoric waters which infiltrated into Pleistocene and Holocene sediments. Older Pleistocene microbial gases have already escaped to the atmosphere.

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