(Supplementary Table 1) Proportions of methane (C1) to ethane (C2) and the stable isotope composition of methane (d13CCH4) of gas and oil collected by gas bubble sampler during cruise M 114 in the southern Gulf of Mexico

Hydrocarbon seepage is a widespread process at the continental margins of the Gulf of Mexico. We used a multidisciplinary approach, including multibeam mapping and visual seafloor observations with different underwater vehicles to study the extent and character of complex hydrocarbon seepage in the Bay of Campeche, southern Gulf of Mexico. Our observations showed that seafloor asphalt deposits previously only known from the Chapopote Knoll also occur at numerous other knolls and ridges in water depths from 1230 to 3150 m. In particular the deeper sites (Chapopopte and Mictlan knolls) were characterized by asphalt deposits accompanied by extrusion of liquid oil in form of whips or sheets, and in some places (Tsanyao Yang, Mictlan, and Chapopote knolls) by gas emission and the presence of gas hydrates in addition. Molecular and stable carbon isotopic compositions of gaseous hydrocarbons suggest their primarily thermogenic origin. Relatively fresh asphalt structures were settled by chemosynthetic communities including bacterial mats and vestimentiferan tube worms, whereas older flows appeared largely inert and devoid of corals and anemones at the deep sites. The gas hydrates at Tsanyao Yang and Mictlan Knolls were covered by a 5-to-10 cm-thick reaction zone composed of authigenic carbonates, detritus, and microbial mats, and were densely colonized by 1-2 m-long tube worms, bivalves, snails, and shrimps. This study increased knowledge on the occurrences and dimensions of asphalt fields and associated gas hydrates at the Campeche Knolls. The extent of all discovered seepage structure areas indicates that emission of complex hydrocarbons is a widespread, thus important feature of the southern Gulf of Mexico.

Pore-water concentration of chloride in sediment cores and equilibrium temperatures and gas bubble analysis at ROV stations from the Vodyanitskii mud volcano

Vodyanitskii mud volcano is located at a depth of about 2070 m in the Sorokin Trough, Black sea. It is a 500-m wide and 20-m high cone surrounded by a depression, which is typical of many mud volcanoes in the Black Sea. 75 kHz sidescan sonar show different generations of mud flows that include mud breccia, authigenic carbonates, and gas hydrates that were sampled by gravity coring. The fluids that flow through or erupt with the mud are enriched in chloride (up to 650 mmol L**-1 at 150-cm sediment depth) suggesting a deep source, which is similar to the fluids of the close-by Dvurechenskii mud volcano. Direct observation with the remotely operated vehicle Quest revealed gas bubbles emanating at two distinct sites at the crest of the mud volcano, which confirms earlier observations of bubble-induced hydroacoustic anomalies in echosounder records. The sediments at the main bubble emission site show a thermal anomaly with temperatures at 60 cm sediment depth that were 0.9 °C warmer than the bottom water. Chemical and isotopic analyses of the emanated gas revealed that it consisted primarily of methane (99.8%) and was of microbial origin (dD-CH4 = -170.8 per mil (SMOW), d13C-CH4 = -61.0 per mil (V-PDB), d13C-C2H6 = -44.0 per mil (V-PDB)). The gas flux was estimated using the video observations of the ROV. Assuming that the flux is constant with time, about 0.9 ± 0.5 x 10**6 mol of methane is released every year. This value is of the same order-of-magnitude as reported fluxes of dissolved methane released with pore water at other mud volcanoes. This suggests that bubble emanation is a significant pathway transporting methane from the sediments into the water column.

Carbon isotopic composition of dissolved CO2, CO2 gas and methane in sediments from ODP Leg 172 sites

Carbon isotopic data of interstitial dissolved CO2 (CO2), CO2 gas, and methane show that a variety of microbial diagenetic processes produce the observed isotopic trends. Anaerobic methane oxidation (AMO) is an important process near the sulfate-methane interface (SMI) that strongly influences the isotopic composition of CO2 in the sulfate reduction and upper methanogenic zones, which in turn impacts methane isotopic composition. Dissolved CO2 and methane are maximally depleted in 13C near the SMI, where 13C values are as light as -31.8 and -101 PDB for CO2 and methane, respectively. CO2 reduction links the CO2 and methane pools in the methanogenic zone so that the carbon isotopic composition of both pools evolves in concert, generally showing increasing enrichments of 13C with increasing depth. These isotopic trends mirror those within other methane-rich continental rise sediments worldwide.