Heart-cutting two-dimensional gas chromatography-isotope ratio mass spectrometry analysis of monoaromatic hydrocarbons in complex groundwater and gas-phase samples

Compound-specific isotope analysis (CSIA) is increasingly used to evaluate the origin and fate of petroleum hydrocarbons in the environment. However, as samples often contain a complex mixture of compounds and the method requires a full chromatographic separation, it can be challenging to obtain accurate and precise isotope values. In this study, in order to develop a method to analyze carbon isotopes in benzene, toluene, ethylbenzene, and xylenes (BTEX) in complex environmental samples, a two-dimensional heart-cutting gas chromatograph (GC) was hyphenated to an isotope ratio mass spectrometer (IRMS). The focus was placed on benzene and toluene, which are the main compounds of concern in contaminated sites. A full separation for BTEX was successfully achieved using a 60m polar column in the first dimension and a 30m non-polar column in the second dimension. Accuracy and precision of carbon isotope measurements of standards were not impacted by the new setup compared to classic one-dimensional (1D) GC-C-IRMS. For benzene and toluene, precision remained very good (≤0.2‰) for concentrations comprised between 5 and 20μg/L. A high matrix load did not influence the precision and accuracy of isotope measurements. The method was tested on several samples from two different field sites. For all samples tested, full chromatographic baseline resolution was achieved for benzene and toluene. Spatial variability of isotopes values linked to biodegradation was evidenced for one field site. This new 2D-GC-C-IRMS method will broaden the spectrum of samples suitable for isotope analysis and will be therefore able to give new insights into attenuation processes of BTEX in contaminated sites or source fingerprinting.