Carbon cycling within the upper methanogenic zone of continental rise sediments; An example from the methane-rich sediments overlying the Blake Ridge gas hydrate deposits

Data from piston cores collected from Carolina Rise and Blake Ridge, and from many DSDP/ODP sites indicate that extreme ¹³C-depletion of methane and ΣCO₂ occurs within the uppermost methanogenic zone of continental rise sediments. We infer that ¹³C-depleted methane is generated near the top of the methanogenic zone when carbon of ¹³C-depleted ΣCO₂, produced by microbially-mediated anaerobic methane oxidation, is recycled back to methane through CO₂ reduction. Interstitial water and gas samples were collected in 27 piston cores, 16 of which penetrated through the sulfate reduction zone into methane-bearing sediments of the Carolina Rise and Blake Ridge. Isotopic measurements (δ¹³C_CH4, δ¹³C_CO2, δD_CH4, and δD_H2O) indicate that this methane is microbial in origin, produced by microbially-mediated CO₂ reduction. Methane samples form two distinct isotopic pools. (1) Methane from a seafloor seep site shows a mean δ¹³C_CH4 value of − 69 ± 2%., mirroring values found at ≥ 160 mbsf from a nearby DSDP site. (2) Twenty, areally-separated sites (sample depth, 10 to 25 mbsf) have δ¹³C_CH4 values ranging from −85 to −103%., and δ¹³C_CO2 as negative as −48%.. The very low δ¹³C values from the methane and CO₂ pools highlight the importance of carbon cycling within continental rise sediments at and near the sulfate-methane boundary.     

Association among active seafloor deformation, mound formation, and gas hydrate growth and accumulation within the seafloor of the Santa Monica Basin, offshore California

Seafloor blister-like mounds, methane migration and gas hydrate formation were investigated through detailed seafloor surveys in Santa Monica Basin, offshore of Los Angeles, California. Two distinct deep-water (≥ 800 m water depth) topographic mounds were surveyed using an autonomous underwater vehicle (carrying a multibeam sonar and a chirp sub-bottom profiler) and one of these was explored with the remotely operated vehicle Tiburon. The mounds are > 10 m high and > 100 m wide dome-shaped bathymetric features. These mounds protrude from crests of broad anticlines (~ 20 m high and 1 to 3 km long) formed within latest Quaternary-aged seafloor sediment associated with compression between lateral offsets in regional faults. No allochthonous sediments were observed on the mounds, except slumped material off the steep slopes of the mounds. Continuous streams of methane gas bubbles emanate from the crest of the northeastern mound, and extensive methane-derived authigenic carbonate pavements and chemosynthetic communities mantle the mound surface. The large local vertical displacements needed to produce these mounds suggests a corresponding net mass accumulation has occurred within the immediate subsurface. Formation and accumulation of pure gas hydrate lenses in the subsurface is proposed as a mechanism to blister the seafloor and form these mounds.     

Contribution of thermogenic organic matter to the formation of biogenic gas hydrate: Evidence from geochemical and microbial characteristics of hydrate-containing sediments in the Taixinan Basin,South China Sea

High-saturation (40–100%), microbial gas hydrates have been acquired by expedition GMGS2 from the Taixinan Basin. In this study, geochemical and microbial features of hydrate-containing sediments from the drilling cores (GMGS2-09 and GMGS2-16) were characterized to explore their relationships with gas hydrate formation. Results showed that the average TOC content of GMGS2-09 and GMGS2-16 were 0.45% and 0.63%, respectively. They could meet the threshold for in situ gas hydrate formation, but were not available for the formation of high-saturation gas hydrates. The dominant members of Bacteria at the class taxonomic level were Alphaproteobacteria, Bacilli, Bacteroidia, Epsilonproteobacteria and Gammaproteobacteria, and those in Archaea were Marine_Benthic_Group_B (MBGB), Miscellaneous_Crenarchaeotic_Group (MCG), Group C3, Methanomicrobia and Methanobacteria. Indicators of microbes associated with thermogenic organic matter were measured. These include: (1) most of the dominant microbes had been found dominant in other gas hydrates bearing sediments, mud volcanos as well as oil/coal deposits; (2) hydrogenotrophic methanogens and an oilfield-origin thermophilic, methylotrophic methanogen were found dominant the methanogen community; (3) hydrocarbon-assimilating bacteria and other hyperthermophiles were frequently detected. Therefore, thermogenic signatures were inferred existed in the sediments. This deduction is consistent with the interpretation from the seismic reflection profiles. Owing to the inconsistency between low TOC content and gas hydrates with high saturation, secondary microbial methane generated from the bioconversion of thermogenic organic matters (oil or coal) was speculated to serve as enhanced gas flux for the formation of high-saturation gas hydrates. A preliminary formation model of high-saturation biogenic gas hydrates was proposed, in which diagenesis processes, tectonic movements and microbial activities were all emphasized regarding to their contribution to gas hydrates formation. In short, this research helps explain how microbial act and what kind of organic matter they use in forming biogenic gas hydrates with high saturations.     

Stable carbon isotopic ratios of CH4-CO2-bearing fluid inclusions in fracture-fill mineralization from the Lower Saxony Basin (Germany) - A tool for tracing gas sources and maturity

The stable carbon isotopic ratios (δ¹³C) of methane (CH₄) and carbon dioxide (CO₂) of gas-rich fluid inclusions hosted in fracture-fill mineralization from the southern part of the Lower Saxony Basin, Germany have been measured online using a crushing device interfaced to an isotopic ratio mass spectrometer (IRMS). The data reveal that CH₄ trapped in inclusions seems to be derived from different source rocks with different organic matter types. The δ¹³C values of CH₄ in inclusions in quartz hosted by Carboniferous rocks range between −25 and −19‰, suggesting high-maturity coals as the source of methane. Methane in fluid inclusions in minerals hosted by Mesozoic strata has more negative carbon isotope ratios (−45 to −31‰) and appears to represent primary cracking products from type II kerogens, i.e., marine shales. There is a positive correlation between increasing homogenization temperatures of aqueous fluid inclusions and less negative δ¹³C(CH₄) values of in co-genetic gas inclusions probably indicating different mtaturity of the potential source rocks at the time the fluids were released. The CO₂ isotopic composition of CH₄-CO₂-bearing inclusions shows slight negative or even positive δ¹³C values indicating an inorganic source (e.g., water-rock interaction and dissolution of detrital, marine calcite) for CO₂ in inclusions. We conclude that the δ¹³C isotopic ratios of CH₄-CO₂-bearing fluid inclusions can be used to trace migration pathways, sources of gases, and alteration processes. Furthermore, the δ¹³C values of methane can be used to estimate the maturity of the rocks from which it was sourced. Results presented here are further supported by organic geochemical analysis of surface bitumens which coexist with the gas inclusion-rich fracture-fill mineralization and confirm the isotopic interpretations with respect to fluid source, type and maturity.     

A study of natural and artificially generated light hydrocarbons (C4–C13) in source rocks and petroleum fluids from offshore Mid-Norway and the southernmost Norwegian and Danish sectors

The “free” or “natural” light hydrocarbon composition obtained by thermal extraction-GC of source rock samples is compared with the light fraction generated by pyrolysis products of the kerogens. Even though there are large differences between the composition of the “free” C₄–C₁₃ hydrocarbon fraction and the same fraction generated by pyrolysis, some characteristics have been detected which can be used interchangeably for both data types. Visual inspection of gas chromatograms from thermal extracts and pyrolysates indicates that in particular the relative content of m+p xylene corresponds well between these two analytical methods. The source rock samples used are Upper Jurassic marine shales and Middle and Lower Jurassic coals and coaly shales from offshore Mid-Norway and Denmark. More detailed analysis of the data shows that the most effective parameter which can distinguish between different source rock types in both thermal extracts and pyrolysates is the m+p xylene/nC₈ ratio. This parameter has been used to derive classification diagrams for interpreting the source of light hydrocarbons of both natural petroleum fluids analysed by gas chromatography and the same fraction generated by pyrolysis of asphaltenes from the fluids.The model was first tested on 17 natural petroleum fluids from Mid-Norway since a comprehensive study of light hydrocarbon distributions already has been published. Further, the parameter was applied to correlate with asphaltene pyrolysates of the fluids from Mid-Norway and a total of 22 natural oils and condensates from the southernmost Norwegian and Danish sectors.