Improvements in Drill-Core Headspace Gas Analysis for Samples from Microbially Active Depths

Abstract

The IsoJar™ container is widely used in headspace gas analysis for gases adsorbed on cuttings or bore cores from oil and gas fields. However, large variations in the carbon isotopic ratios of CH4and CO2are often reported, especially for data obtained from depths of <1000 m. The IsoJar™ method leaves air in the headspace that allows microbial oxidation of CH4to CO2, meaning that isotopic fractionation occurs during storage. This study employed the IsoJar™ method to investigate the causes of differences inδ13C data reported by previous studies in the Horonobe area of Japan. It was found that after 80 d storage,δ13CCO2values decreased by ~2‰, whileδ13CCH4values increased by >30‰, whereas samples analyzed within a week of collection showed no such fluctuations. The conventional amount of microbial suppressant (~0.5 ml of 10% benzalkonium chloride (BKC) solution) is insufficient to suppress microbial activity if groundwater is used as filling water. The significant variations in carbon isotopic compositions previously reported were caused by microbial methane oxidation after sampling and contamination by groundwater from different depths. To avoid these problems, we recommend the following: (1) if long-term sample storage is necessary, >10 ml of 10% BKC solution should be added or >0.3% BKC concentration is required to suppress microbial activity; (2) analyses should be performed within one week of sampling; and (3) for CO2analyses, it is important that samples are not contaminated by groundwater from different depths.