Molecular and isotopic compositions of gases adsorbed to near surface sediments at Starunia palaeontological site and vicinity (Carpathian region, Ukraine)

The near-surface geochemical survey of gases desorbed from sediment samples was carried out in the area of an abandoned ozokerite mine in Starunia, where remnants of mammoth and three woolly rhinoceroses and one almost completely preserved rhinoceros carcass were discovered in 1907 and 1929. Numerous hydrocarbon seeps (gas and oil "eyes") occur on the surface of the study area. Analyses of molecular and stable carbon isotope compositions of adsorbed gases were carried out in two variants. The first included sampling of cuttings from 30 auger boreholes at depths of 4.8, 5.6 and 6.4 m. In total, 88 samples were collected. In the second variant core samples were collected from 17 selected boreholes. In total, 78 samples were taken from various depths to 12 m. The results of molecular composition analyses of desorbed gases indicated high saturation of near-surface sediments with the oil. The highest concentrations of alkanes were detected in Miocene strata. Hydrocarbon migration from deep accumulations to the surface was relatively fast and proceeded along the faults, fractures and cracks. In the near-surface zone hydrocarbons were subjected to oxidation and dehydrogenation, which resulted in generation of unsaturated hydrocarbons and hydrogen. These processes were most intensive in the Pleistocene sediments and in the mine dumps. Increased concentrations of hydrogen may also originate from water radiolysis in the presence of hydrocarbons. Concentrations of carbon dioxide in the adsorbed gases show the higher values in comparison with the analysed gaseous compounds. However, a slight increase in CO2 concentration was detected in the mine dump, which may indicate conditions more favourable for hydrocarbon oxidation. Carbon dioxide from the analysed adsorbed gases is of thermogenic origin. Occasionally, insignificant influence of secondary hydrocarbon oxidation and/or Quaternary organic matter can be observed. Concentrations of alkanes, alkenes and carbon dioxide in the gas derived from desorption of rock samples are lower and the concentration of hydrogen is higher than those measured in free gases. This indicates that additional effects from recent (e.g. microbial) processes are absent.