Quantification of organic and inorganic hydrogen in mudstones: a novel approach using the difference between organic-rich and organic-free mudstones during pyrolysis process

Whether mudstone is rich in or free of organic matter has a great influence on the occurrence of water. Comparing different types of water in organic-rich and organic-free mudstones is helpful for further understanding the role of water in hydrocarbon generation. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) combined with mass spectrometry (MS) afford the opportunity to identify the mass change, reactions and products of the sample in a real-time monitored heating process. This study compared the pyrolysis characteristics of an organic-rich mudstone (CN1) and an organic-free mudstone (CW1) by using the TGA/DTA-MS method to estimate the content of different types of H2O and CO2 in organic-rich mudstones. The results show that the mass changes in CN1 and CW1 can be divided into the three thermogravimetric (TG) stages of 0°C–200°C, 200°C–650°C, and 650°C–900°C, while the peak temperatures of H2O and CO2 obtained through MS are different for CN1 and CW1. The differences in mineral components and organic matter between CN1 and CW1 suggest that the MS peaks of H2O and CO2 in CW1 are mainly influenced by clay and carbonate minerals, and that those of CN1 are also influenced by organic matter. In addition, quantification equations for CO2 and H2O contents from both the organic and inorganic origin of the organic-rich mudstone can be established by using the MS peak area of CO2 and H2O, mass loss in TGA and the mineral composition of the organic-free mudstone. This work provides useful insights for further understanding the hydrocarbon generation mechanism, as well as quantifying different types of water in organic-rich mudstones.