Hydrocarbon gas in the Costa Rica subduction zone:: primary composition and post-genetic alteration

At the active continental margin off Costa Rica substantial amounts of hydrocarbon gases are encountered in sediments. The molecular composition (C-1-C-3) of free hydrocarbon gas as well as the isotopic composition (delta(13)C of methane and ethane and D of methane) was analysed on core samples (ranging between 50 and 380 m depth) collected at sites 1040-1043 which was drilled during ODP Leg 170. In addition, the molecular composition of the C-1-C-3 hydrocarbons and the delta(13)C composition of C-1 and C-2 hydrocarbons was determined on adsorbed gas from selected depth intervals at Site 1041 (50-380 mbsf). The molecular composition, and stable carbon and hydrogen isotope signature of low molecular weight hydrocarbons from core sediments and gas pockets indicate that most of the gas was generated by microbial CO2-reduction. Beside delta(13)C values of about -80parts per thousand for methane (which is typical for microbially-generated methane) extremely light delta(13)C values of -55parts per thousand. were measured for ethane. The carbon isotope composition of methane and ethane, as well as the C-1/(C-2 + C-3) ratio display distinct trends with increasing depth. Gas mixing calculations indicate that the percentage of thermally-generated ethane increases from 10% at about 75 mbsf to almost 80% at 380 mbsf. The fraction of thermogenic methane in this depth interval is calculated to range from 0.03 to 1.8% of the total methane. The small contribution of thermogenic methane would increase the delta(13)C value by <1parts per thousand. Therefore, the increase of delta(13)C of methane (by about 12parts per thousand) with depth cannot be explained by gas mixing alone. Instead, the observed delta(13)C trend is caused by successive isotope depletion of the methane precursor within the sedimentary organic matter due to progressing microbial gas generation. (C) 2002 Elsevier Science Ltd. All rights reserved.