Incubation experiments to constrain the production of methane and carbon dioxide in organic-rich shales of the Permian Irati Formation, Parana Basin

The Permian Irati Formation in Brazil hosts organic-rich shales and heavy hydrocarbons suitable for biogenic production of methane (CH4) and carbon dioxide (CO2). In this study, shale samples from the irati Formation were used in laboratory incubation experiments performed under different temperatures (22 degrees C, 50 degrees C, 70 degrees C and 80 degrees C) to evaluate the generation of CH4 and CO2 under thermal conditions compatible with biodegradation in shallow gas systems (< 80 degrees C). Despite our laboratory experiments do not represent natural subsurface temperature conditions, it is observed that the concentrations of CH4 and CO2 increase when shale samples are incubated under temperature higher than 22 degrees C. Samples incubated at 80 degrees C presented a maximum CH4 yield of 2.45 ml/t.d (milliliter per ton of shale per day) compared to 0,49 ml/t.d at 22 degrees C, 1.75 ml/t.d at 50 degrees C and 2.09 ml/t.d at 70 degrees C. The same trend of increasing production rates with higher temperatures was observed for CO2, with maximum potential production observed under a laboratory temperature of 80 degrees C, reaching 23.47 ml/t.d. Stable carbon isotopes (delta C-13) on CH4 and CO2 suggest a mixture of thermogenic and secondary microbial gas. However, the measured CH4 and CO2 can be generated through methanogenic degradation of heavy hydrocarbons present in the studied shales, difficulting the use of carbon isotope composition to discriminate between biogenic and thermogenic gases. The studied shale samples showed significant differences in CH4 and CO2 production rates, which are possibly related to the major elements composition of the mineral matrix. Higher CH4 and CO2 production rates occurred in samples with higher amount of sulfur. Besides sulfur, we highlight that others soluble elements in the mineral matrix, such as Ca and Mg, can play an important role for the generation of biogenic CH4 and CO2. The present work intends to alert for the impo