A GC-SSIM-CRDS System: Coupling a Gas Chromatograph with a Cavity Ring-Down Spectrometer for Onboard Twofold Analysis of Molecular and Isotopic Compositions of Natural Gases during Ocean-Going Research Expeditions

Type Article
Date 2021-11
Language English
Author(s) Brandily Christophe1, Le Cuff Nolwenn2, Donval Jean-Pierre2, Guyader VivienORCID2, de Prunele Alexis2, Cathalot CecileORCID2, Croguennec Claire2, Caprais Jean-Claude1, Ruffine LivioORCID2
Affiliation(s) 1 : Ifremer, REM/EEP-Laboratoire Environnements Profonds, Centre de Brest, ZI Pointe Du Diable, CS100, F-29280 Plouzané, France
2 : fremer, REM/GM-Laboratoire Cycles Géochimiques et Ressources, Centre de Brest, ZI Pointe Du Diable, CS100, F-29280 Plouzané, France
Source Analytica Chimica Acta (00032670) (Elsevier BV), 2021-11 , Vol. 1184 , P. 339040 (14p.)
DOI 10.1016/j.aca.2021.339040
Keyword(s) Coupled analytical technique, cavity ring-down spectroscopy, carbon dioxide, gas chromatography, methane, molecular composition, natural gases, onboard analysis, stable carbon isotope ratio
Abstract

Carbon dioxide (CO2) and methane (CH4) are two climate-sensitive components of gases migrating within sediments and emitted into the water column on continental margins. They are involved in several key biogeochemical processes entering into the global carbon cycle. In order to perform onboard measurements of both the molecular and stable carbon isotope ratios (δ13C) of CH4 and CO2 of natural gases during oceanic cruises, we have developed a novel approach coupling gas chromatography (GC) with cavity ring-down spectroscopy (CRDS). The coupled devices are connected to a small sample isotope module (SSIM) to form a system called GC-SSIM-CRDS. Small volumes of natural gas samples (<1 mL) are injected into the GC using a headspace autosampler or a gas-tight syringe to separate the chemical components using a Shincarbon ST packed column and for molecular quantification by thermal conductivity detection (TCD). Subsequently, CO2 from the sample is trapped in a 7 mL loop at 32 °C before being transferred to the CRDS analyzer for sequential determination of the stable carbon isotope ratios of CH4 and CO2 in 24 min. The loop is an open column (without stationary phase). This approach does not require the use of adsorbents or cooling for the trapping step. Optimization of the separation step prior to analysis was focused on the influence of two key separation factors 1) the flow of the carrier gas and 2) the temperature of the oven. Our analytical system and the measurement protocol were validated on samples collected from gas seeps in the Sea of Marmara (Turkey). Our results show that the GC-SSIM-CRDS system provides a reliable determination of the molecular identification of CH4 and CO2 in complex natural gases, followed by the stable carbon isotope ratios of methane and carbon dioxide.

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Brandily Christophe, Le Cuff Nolwenn, Donval Jean-Pierre, Guyader Vivien, de Prunele Alexis, Cathalot Cecile, Croguennec Claire, Caprais Jean-Claude, Ruffine Livio (2021). A GC-SSIM-CRDS System: Coupling a Gas Chromatograph with a Cavity Ring-Down Spectrometer for Onboard Twofold Analysis of Molecular and Isotopic Compositions of Natural Gases during Ocean-Going Research Expeditions. Analytica Chimica Acta, 1184, 339040 (14p.). Publisher's official version : https://doi.org/10.1016/j.aca.2021.339040 , Open Access version : https://archimer.ifremer.fr/doc/00721/83298/