Field demonstration for the solvent-based sampling method to perform compound-specific isotope analysis on gas-phase VOC

Abstract

The solvent-based sampling method for collecting gas-phase volatile organic compounds (VOCs) and conducting compound-specific isotope analysis (CSIA) was deployed during a controlled field study. The solvent-based method used methanol as a sink to accumulate petroleum hydrocarbons during the sampling of soil air and effluent gas. For each gaseous sample collected, carbon isotope analysis (δ¹³C) was conducted for a selection of five VOCs (benzene, toluene, o-xylene, cyclopentane and octane) emitted by a synthetic hydrocarbon source emplaced in the subsurface. The δ¹³C values obtained for gaseous VOCs (collected from soil gas and effluent gas) were compared to measurements obtained for the same VOCs present in the source material (none aqueous phase liquid - NAPL) and dissolved in groundwater to evaluate the reliability of the solvent-based sampling method in providing accurate isotope measurements. Since the NAPL source was composed of only 12 VOCs, potential bias related to the analytical procedure (such as co-elution) were avoided, hence emphasizing on field-related bias. This field evaluation demonstrated the capacity of the solvent-based method to produce precise and accurate δ¹³C measurements. The isotopic discrepancies between the gaseous and the NAPL values were < 1 ‰ for 39 out of the 41 comparison points, thus deemed not statistically different based on a common isotopic uncertainty error of ±0.5 ‰. Moreover, the current field study is the first field study to report δ¹³C measurements for up to five gas-phase VOCs obtained from the same sample, which appears to be of interest for VOC fate or forensic studies. The possibility to use several VOC isotopic measurements enabled by the sampling method would contribute to strengthen the connection assessment between gaseous VOCs and the suspected emitting source. Accordingly, the field results presented herein support the application of this sampling methodology to conduct CSIA assessment in the frame of VOC vapor studies.