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.

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.

Freshwater lake to salt-water sea causing widespread hydrate dissociation in the Black Sea.

Gas hydrates, a solid established by water and gas molecules, are widespread along the continental margins of the world. Their dynamics have mainly been regarded through the lens of temperature-pressure conditions. A fluctuation in one of these parameters may cause destabilization of gas hydrate-bearing sediments below the seafloor with implications in ocean acidification and eventually in global warming. Here we show throughout an example of the Black Sea, the world's most isolated sea, evidence that extensive gas hydrate dissociation may occur in the future due to recent salinity changes of the sea water. Recent and forthcoming salt diffusion within the sediment will destabilize gas hydrates by reducing the extension and thickness of their thermodynamic stability zone in a region covering at least 2800 square kilometers which focus seepages at the observed sites. We suspect this process to occur in other world regions (e.g., Caspian Sea, Sea of Marmara).

New insights into the transport processes controlling the sulfate-methane-transition-zone near methane vents.

Over the past years, several studies have raised concerns about the possible interactions between methane hydrate decomposition and external change. To carry out such an investigation, it is essential to characterize the baseline dynamics of gas hydrate systems related to natural geological and sedimentary processes. This is usually treated through the analysis of sulfate-reduction coupled to anaerobic oxidation of methane (AOM). Here, we model sulfate reduction coupled with AOM as a two-dimensional (2D) problem including, advective and diffusive transport. This is applied to a case study from a deep-water site off Nigeria's coast where lateral methane advection through turbidite layers was suspected. We show by analyzing the acquired data in combination with computational modeling that a two-dimensional approach is able to accurately describe the recent past dynamics of such a complex natural system. Our results show that the sulfate-methane-transition-zone (SMTZ) is not a vertical barrier for dissolved sulfate and methane. We also show that such a modeling is able to assess short timescale variations in the order of decades to centuries.