Roger Sassen

Products and distinguishing criteria of bacterial and thermochemical sulfate reduction

Bacterial and thermochemical sulfate reduction apparently occur in two mutually exclusive thermal regimes, i.e., low-temperature diagenetic environments with0 < T < 60–80°C and high-temperature diagenetic environments with80–100 < T < 150–200°C, respectively. The major reaction products and by-products are identical in both thermal regimes and include altered and oxidized hydrocarbons (originally mainly crude oil, gas condensate, and/or methane), hydrogen sulfide, base and transition metal sulfides, elemental sulfur, and carbonates (mainly calcite and dolomite). The mere presence of the above reaction products and by-products does not discriminate between the low- and high-temperature diagenetic environments. However, petrographic, isotopic and compositional data of these products and by-products may permit identification of a bacterial versus a thermochemical origin. Regarding the inorganic phases, the carbon isotope ratios of the carbonates, sulfur isotope ratios of elemental sulfur and sulfides, and fluid inclusion data appear to yield the best discriminating geochemical criteria. Among the organic phases, reservoir bitumen and gas condensates display a number of useful isotopic and compositional (chromatographic) criteria. The most reliable approach for discriminating bacterial versus thermochemical sulfate reduction is to combine as many of these criteria as possible. These criteria can be used in exploration or deposits of hydrocarbons, sour gas, elemental sulfur, and certain metal sulfides.

Gas hydrate that breaches the sea floor on the continental slope of the Gulf of Mexico

We report observations that concern formation and dissociation of gas hydrate near the sea floor at depths of ∼540 m in the northern Gulf of Mexico. In August 1992, three lobes of gas hydrate were partly exposed beneath a thin layer of sediment. By May 1993, the most prominent lobe had evidently broken free and floated away, leaving a patch of disturbed sediment and exposed hydrate. The underside of the gas hydrate was about 0.2 °C warmer than ambient sea water and had trapped a large volume of oil and free gas. An in situ monitoring device, deployed on a nearby bed of mussels, recorded sustained releases of gas during a 44 day monitoring period. Gas venting coincided with a temporary rise in water temperature of 1 °C, which is consistent with thermally induced dissociation of hydrate composed mainly of methane and water. We conclude that the effects of accumulating buoyant force and fluctuating water temperature cause shallow gas hydrate alternately to check and release gas venting.

Bacteria and Archaea Physically Associated with Gulf of Mexico Gas Hydrates

ABSTRACT Although there is significant interest in the potential interactions of microbes with gas hydrate, no direct physical association between them has been demonstrated. We examined several intact samples of naturally occurring gas hydrate from the Gulf of Mexico for evidence of microbes. All samples were collected from anaerobic hemipelagic mud within the gas hydrate stability zone, at water depths in the ca. 540- to 2,000-m range. The δ13C of hydrate-bound methane varied from −45.1‰ Peedee belemnite (PDB) to −74.7‰ PDB, reflecting different gas origins. Stable isotope composition data indicated microbial consumption of methane or propane in some of the samples. Evidence of the presence of microbes was initially determined by 4,6-diamidino 2-phenylindole dihydrochloride (DAPI) total direct counts of hydrate-associated sediments (mean = 1.5 × 109 cells g−1) and gas hydrate (mean = 1.0 × 106 cells ml−1). Small-subunit rRNA phylogenetic characterization was performed to assess the composition of the microbial community in one gas hydrate sample (AT425) that had no detectable associated sediment and showed evidence of microbial methane consumption. Bacteria were moderately diverse within AT425 and were dominated by gene sequences related to several groups of Proteobacteria, as well asActinobacteria and low-G + C Firmicutes. In contrast, there was low diversity of Archaea, nearly all of which were related to methanogenic Archaea, with the majority specifically related to Methanosaeta spp. The results of this study suggest that there is a direct association between microbes and gas hydrate, a finding that may have significance for hydrocarbon flux into the Gulf of Mexico and for life in extreme environments.

Natural oil slicks in the Gulf of Mexico visible from space

Natural oil seepage in the Gulf of Mexico causes persistent surface slicks that are visible from space in predictable locations. A photograph of the sun glint pattern offshore from Louisiana taken from the space shuttle Atlantis on May 5, 1989, shows at least 124 slicks in an area of about 15,000 km2; a thematic mapper (TM) image collected by the Landsat orbiter on July 31, 1991, shows at least 66 slicks in a cloud-free area of 8200 km2 that overlaps the area of the photograph. Samples and descriptions made from a surface ship, from aircraft, and from a submarine confirmed the presence of crude oil in floating slicks. The imagery data show surface slicks near eight locations where chemosynthetic communities dependent upon seeping hydrocarbons are known to occur on the seafloor. Additionally, a large surface slick above the location of an active mud volcano was evident in the TM image. In one location the combined set of observations confirmed the presence of a flourishing chemosynthetic community, active seafloor oil and gas seepage, crude oil on the sea surface, and slick features that were visible in both images. We derived an analytical expression for the formation of floating slicks based on a parameterization of seafloor flow rate, downstream movement on the surface, half-life of floating oil, and threshold thickness for detection. Applying this equation to the lengths of observed slicks suggested that the slicks in the Atlantis photograph and in the TM image represent seepage rates of 2.2–30 m3 1000 km−2 d−1 and 1.4–18 m3 1000 km−2 d−1, respectively. Generalizing to an annual rate suggests that total natural seepage in this region is of the order of at least 20,000 m3 yr−1 (120,000 barrels yr−1).

Global gas flux from mud volcanoes: A significant source of fossil methane in the atmosphere and the ocean

[1] There are yet unidentified sources of fossil methane (CH 4 ) in the atmosphere. Mud volcanoes (MVs) are a potentially significant but poorly quantified geologic source of fossil hydrocarbon gases and CO 2 to the atmosphere and the ocean not included in the current models of sources and sinks. Our statistical analysis of 36 previous measurements and estimates of gas flux from individual MVs suggests that the global gas flux may be as high as ∼33 Tg yr -1 (∼15.9 Tg yr during quiescent periods plus ∼17.1 Tg yr -1 during eruptions). Onshore and shallow offshore MVs are estimated to contribute ∼6 Tg yr -1 of greenhouse gases directly to the atmosphere. MVs may contribute 9% of fossil CH 4 missing in the modern atmospheric CH 4 budget, and ∼12% in the preindustrial budget. Large volumes (∼27 Tg yr -1 ) of gas may escape from deep-water MVs, suggesting that global gas flux from the seafloor may be underestimated.

Chemosynthetic bacterial mats at cold hydrocarbon seeps, Gulf of Mexico continental slope

Abstract White and pigmented filamentous bacterial mats dominated by several undescribed species of Beggiatoa were sampled during research submersible dives to cold hydrocarbon seep sites on the upper continental slope off Louisiana (130–550 m). Mats occur at the interface between reducing sediments and the oxygenated water column. They are localized at sea floor features related to seepage of biogenic methane and crude oil, but there is little evidence that the organisms utilize the hydrocarbons directly. Granules of elemental sulfur (S0) are visible within cells of Beggiatoa, and mat material is characterized by high contents of S0 (up to 193,940 ppm). The Beggiatoa biomass is isotopically light ( δ 13 C = −27.9‰ PDB ). Our geochemical data suggest that the Beggiatoa species are part of a complex bacterial assemblage in cold seep sediments. They oxidize H2S derived from the bacterial sulfate reduction that accompanies bacterial hydrocarbon oxidation when O2 is depleted in sediments, and fix isotopically light carbon from CO2 that is the result of bacterial hydrocarbon oxidation. Beggiatoa mats appear to retard loss of hydrocarbons to the water column by physically retaining fluids in sediments, a function that could enhance production by other bacteria of the H2S and CO2 needed by Beggiatoa.

Economic geology of offshore gas hydrate accumulations and provinces

The economic potential of well-studied offshore gas hydrate accumulations and provinces is assessed qualitatively based on consideration of geological, technological, and economic factors. Three types of gas hydrate accumulations are suggested. Structural accumulations occur where thermogenic, bacterial, or mixed gases are rapidly transported from the subsurface petroleum system to the gas hydrate stability zone along faults, mud volcanoes, and other structures (e.g. northwestern Gulf of Mexico, Hydrate Ridge, and Haakon Mosby mud volcano). These accumulations are generally characterized by high gas hydrate concentration in sediment, high resource density, high recovery factors, as well as low development and production costs. It is likely that structural accumulations provide marginal or economic gas hydrate reserves if they represent significant volumes of hydrate-bound gas. Stratigraphic accumulations occur in relatively permeable sediments and form largely from bacterial methane generated in situ or slowly migrated from depth in the section (e.g. Blake Ridge, Gulf of Mexico minibasins). These accumulations are generally characterized by low gas hydrate concentration in sediments and low recovery factor, as well as high development and production costs. Stratigraphic accumulations mainly provide a subeconomic gas hydrate resource. However, in cases such as the Nankai Trough province, high gas hydrate concentration occurs in permeable sand layers and may represent a viable exploration and exploitation target. Less geological data are available on the combination gas hydrate accumulations controlled both by structures and stratigraphy. On the global scale, gas hydrate reserves are likely to represent only a small fraction of the gas hydrate resource because the largest volume of gas hydrate is in subeconomic stratigraphic accumulations. However, some concentrated gas hydrate accumulations may be exploited profitably, and those should be subjected to detailed quantitative economic analysis.

Evidence of structure H hydrate, Gulf of Mexico continental slope

Abstract A research submarine was used to sample an amber-colored gas hydrate exposed on the sea-floor at 540 m water depth in the Gulf of Mexico continental slope, offshore Louisiana. The hydrate composition is novel for a natural occurrence because i -C 5 comprises 41.1% of the total C 1 –C 5 hydrocarbon distribution. The relative abundance of i -C 5 is consistent with an hexagonal (H) lattice structure that is capable of enclosing larger hydrocarbon molecules than either structure I or II hydrates. Structure H hydrate, which has not been identified previously in nature, coexists with structure II hydrate on the Gulf slope.

Bacterial methane oxidation in sea-floor gas hydrate: Significance to life in extreme environments

Samples of thermogenic hydrocarbon gases, from vents and gas hydrate mounds within a sea-floor chemosynthetic community on the Gulf of Mexico continental slope at about 540 m depth, were collected by research submersible. The study area is characterized by low water temperature (mean = 7 C), high pressure (about 5,400 kPa), and abundant structure II gas hydrate. Bacterial oxidation of hydrate-bound methane (CH{sub 4}) is indicated by three isotopic properties of gas hydrate samples. Relative to the vent gas from which the gas hydrate formed, (1) methane-bound methane is enriched in {sup 13}C by as much as 3.8% PDB (Peedee belemnite), (2) hydrate-bound methane is enriched in deuterium (D) by as much as 37% SMOW (standard mean ocean water), and (3) hydrate-bound carbon dioxide (CO{sub 2}) is depleted in {sup 13}C by as much as 22.4% PDB. Hydrate-associated authigenic carbonate rock is also depleted in {sup 13}C. Bacterial oxidation of methane is a driving force in chemosynthetic communities, and in the concomitant precipitation of authigenic carbonate rock that modifies sea-floor geology. Bacterial oxidation of hydrate-bound methane expands the potential boundaries of life in extreme environments.

Organic geochemistry of sediments from chemosynthetic communities, Gulf of Mexico slope

We used a research submersible to obtain 33 sediment samples from chemosynthetic communities at 541–650 m water depths in the Green Canyon (GC) area of the Gulf of Mexico slope. Sediment samples from beneath an isolated mat of H2S-oxidizing bacteria at GC 234 contain oil (mean = 5650 ppm) and C1–C5 hydrocarbons (mean = 12,979 ppm) that are altered by bacterial oxidation. Control cores away from the mat contain lower concentrations of oil (mean = 2966 ppm) and C1–C5 hydrocarbons (mean = 83.6 ppm). Bacterial oxidation of hydrocarbons depletes O2 in sediments and triggers bacterial sulfate reduction to produce the H2S required by the mats. Sediment samples from GC 185 (Bush Hill) contain high concentrations of oil (mean = 24,775 ppm) and C1–C5 hydrocarbons (mean = 11,037 ppm) that are altered by bacterial oxidation. Tube worm communities requiring H2S occur at GC 185 where the sea floor has been greatly modified since the Pleistocene by accumulation of oil, thermogenic gas hydrates, and authigenic carbonate rock. Venting to the water column is suppressed by this sea-floor modification, enhancing bacterial activity in sediments. Sediments from an area with vesicomyid clams (GC 272) contain lower concentrations of oil altered by bacterial oxidation (mean = 1716 ppm) but C1–C5 concentrations are high (mean = 28,766 ppm). In contrast to other sampling areas, a sediment associated with the methanotrophic Seep Mytilid I (GC 233) is characterized by low concentration of oil (82 ppm) but biogenic methane (C1) is present (8829 ppm).