Origin of methane and heavier hydrocarbons entrapped within Miocene methane-seep carbonates from central Japan.

Abstract We examined the carbon isotopic and molecular compositions of residual gases within Miocene methane-derived carbonates collected in Japan. Methane, ethane, and propane were extracted by acid digestion of powdered carbonates. The isotopic and molecular compositions of the extracted hydrocarbons are inconsistent with conventional thermogenic and microbial gases. Despite a range of δ13C values from −67‰ to −38‰ (relative to Vienna Pee Dee Belemnite (VPDB)), the liberated hydrocarbons yielded consistently low methane to ethane + propane ratios (2–30). The extracted ethane and propane yielded anomalous δ13C values as low as −84‰, lower than those of the coexisting methane. The ethane and propane were most likely produced through thermal cracking of organic compounds preserved within the seep carbonates during burial. The observed unusual isotopic trends may be explained by the mixing of two thermogenic gas components with different carbon isotopic and molecular compositions. Nevertheless, a positive correlation between δ13C values of methane and relatively immature carbonates at one study site (Nakanomata) indicates that while methane was oxidized to bicarbonate from which carbonates precipitated, it was preserved within the host carbonate cements. Such a scenario indicates that the residual methane at least partly originates from the Miocene seep fluid. Smaller amounts of methane were also released during heating and crushing of chipped samples. The results suggest that methane was entrapped mainly within intracrystal inclusions, which is supported by the observation of abundant nanometer-scale voids in an individual crystal. Highlights • Hydrocarbon gases were extracted from Miocene methane-seep carbonates in Japan. • Most hydrocarbons are thermogenic gases produced from organic matter in carbonates. • The original seep methane could partly be preserved in immature carbonate crystals. [ABSTRACT FROM AUTHOR]