Gas hydrates stored in the continental margins of the world’s oceans represent the largest global reservoirs of methane. Determining the source and history of methane from gas hydrate deposits informs the viability of sites as energy resources, and potential hazards from hydrate dissociation or intense methane degassing from ocean warming. Stable isotope ratios of methane (13C/12C, D/H) and the molecular ratio of methane over ethane plus propane (C1/C2+3) have traditionally been applied to infer methane sources, but often yield ambiguous results when two or more sources are mixed, or when compositions were altered by physical (e.g., diffusion) or microbial (e.g., methanotrophy) processes. We measured the abundance of clumped methane isotopologue (13CH3D) alongside 13C/12C and D/H of methane, and C1/C2+3 for 46 submarine gas hydrate specimens and associated vent gases from 11 regions of the world’s oceans. These samples are associated with different seafloor seepage features (oil seeps, pockmarks, mud volcanoes, and other cold seeps). The average apparent equilibration temperatures of methane from the Δ13CH3D (the excess abundance of 13CH3D relative to the stochastic distribution) geothermometer increase from cold seeps (15 to 65 ℃) and pockmarks (36 to 54 ℃), to oil-associated gas hydrates (48 to 120 ℃). These apparent temperatures are consistent with, or a few tens of degrees higher than, the temperature expected for putative microbial methane sources. Apparent methane generation depths were derived for cold seep, pockmark, and oil seep methane from isotopologue-based temperatures and the local geothermal gradients. Estimated methane generation depths ranged from 0.2 to 5.3 kmbsf, and are largely consistent with source rock information, and other chemical geothermometers based on clay mineralogy and fluid chemistry (e.g., Cl, B, and Li). Methane associated with mud volcanoes yielded a wide range of apparent temperatures (15 to 313℃). Gas hydrates from mud volcanoes the Kumano Basin and Mediterranean Sea yielded δ13C-CH4 values from -36.9 to -51.0‰, typical for thermogenic sources. Δ13CH3D values (3.8 to 6.0‰) from these sites, however, are consistent with prevailing microbial sources. These mud volcanoes are located at active convergent plate margins, where hydrogen may be supplied from basement rocks, and fuel methanogenesis to the point of substrate depletion. In contrast, gas hydrate from mud volcanoes located on km-thick sediments in tectonically less active or passive settings (Black Sea, North Atlantic) yielded microbial-like δ13C-CH4 and C1/C2+3 values, and low Δ13CH3D values (1.6 to 3.3‰), which may be due to kinetic isotope effects. This study is the first to document the link between methane isotopologue-based temperature estimates and key submarine gas hydrate seepage features, and validate previous models about their geologic driving forces.

Gas hydrate dynamics and the fluid flow systems from two active pockmarks along Vestnesa Ridge (offshore west Svalbard) were investigated through the pore fluid geochemistry obtained during the 2016 MARUM-MeBo 70 drilling cruise. Based on the pore water chloride concentration profiles from Lunde and Lomvi pockmarks, we estimated up to 47% pore space occupied by gas hydrate in the sediments shallower than 11.5 mbsf. These gas hydrates were formed during periods of gaseous methane seepage, but are now in a state of dynamic equilibrium sustained by a relatively low methane supply at present. We detect a saline formation pore fluid around nine meters below seafloor from one of the seepage sites in Lunde pockmark. This formation pore fluid has elevated dissolved chloride concentrations and B/Cl ratios, higher δO and δD isotopic signatures of water and lower δB signatures, which collectively hint to a high temperature modification of this fluid at great depths. By integrating our findings with the previous work from Vestnesa Ridge, we show that the variable fluid phases (gaseous vs. aqueous fluid) and migration pathways are controlled by the sediment properties, such as buried carbonate crusts, and the state of fluid reservoirs.

Natural methane gas release from the seafloor is a widespread phenomenon that occurs at cold seeps along most continental margins. Since their discovery in the early 1980s, seeps have been the focus of intensive research, partly aimed to refine the global carbon budget. However, deep-sea research is challenging and expensive and, to date, few works have successfully monitored the variability of methane gas release over long time periods (> 1 yr). Long-term monitoring is necessary to study the mechanisms that control seabed gas release. The M³ project, funded by the German Ministry of Education and Research, aims to study the temporal and spatial variability of gas emissions at the Southern Hydrate Ridge (SHR) by acoustically monitoring and quantifying gas effluxes over several years. Located 850 m deep on the Cascadia accretionary prism offshore Oregon, the SHR is one of the most studied seep sites and persistent but variable gas release has been observed for more than 20 years. Since 2015, the Ocean Observatories Initiative’s (OOI) Cabled Array observatory, provides power supply and two-way communication to the SHR, making it an ideal site for continuous long-term monitoring work. In this work, we present how we will take advantage of the OOI infrastructure and deploy several instruments on the seabed for at least 1.5 year. A multi-beam “overview” sonar mounted on a rotor will identify every gas bubble stream located within 200 m from the sonar location. A scanning “quantification” sonar will be used to estimate the amount of gas that is released from discrete gas streams. A camera system and a CTD probe will help process and analyze the hydro-acoustic data. All instruments will be powered and controlled from land through the OOI infrastructure. We present the instrument design, the operation protocol, as well as the data processing steps and expected results.