Gas hydrate systems at Hydrate Ridge offshore Oregon inferred from molecular and isotopic properties of hydrate-bound and void gases

We report and discuss molecular and isotopic properties of hydrate-bound gases from 55 samples and void gases from 494 samples collected during Ocean Drilling Program (ODP) Leg 204 at Hydrate Ridge offshore Oregon. Gas hydrates appear to crystallize in sediments from two end-member gas sources (deep allochthonous and in situ) as mixtures of different proportions. In an area of high gas flux at the Southern Summit of the ridge (Sites 1248-1250), shallow (0-40 m below the seafloor [mbsf]) gas hydrates are composed of mainly allochthonous mixed microbial and thermogenic methane and a small portion of thermogenic C₂₊ gases, which migrated vertically and laterally from as deep as 2- to 2.5-km depths. In contrast, deep (50-105 mbsf) gas hydrates at the Southern Summit (Sites 1248 and 1250) and on the flanks of the ridge (Sites 1244-1247) crystallize mainly from microbial methane and ethane generated dominantly in situ. A small contribution of allochthonous gas may also be present at sites where geologic and tectonic settings favor focused vertical gas migration from greater depth (e.g., Sites 1244 and 1245). Non-hydrocarbon gases such as CO₂ and H₂S are not abundant in sampled hydrates. The new gas geochemical data are inconsistent with earlier models suggesting that seafloor gas hydrates at Hydrate Ridge formed from gas derived from decomposition of deeper and older gas hydrates. Gas hydrate formation at the Southern Summit is explained by a model in which gas migrated from deep sediments, and perhaps was trapped by a gas hydrate seal at the base of the gas hydrate stability zone (GHSZ). Free gas migrated into the GHSZ when the overpressure in gas column exceeded sealing capacity of overlaying sediments, and precipitated as gas hydrate mainly within shallow sediments. The mushroom-like 3D shape of gas hydrate accumulation at the summit is possibly defined by the gas diffusion aureole surrounding the main migration conduit, the decrease of gas solubility in shallow sediment, and refocusing of gas by carbonate and gas hydrate seals near the seafloor to the crest of the local anticline structure.     

Quantification of adamantane in organic media via infrared attenuated total reflection spectroscopy

In the present study, the quantitative determination of the diamondoid compound adamantane in organic solvents via infrared attenuated total reflection (IR-ATR) spectroscopy at unmodified waveguide surfaces was established. Limits of detection (LOD) and quantification (LOQ) of adamantane in dichloromethane, hexane and carbon tetrachloride were determined. Quantitative IR-ATR measurements additionally facilitated the determination of adamantane solubility limit in dichloromethane, hexane and carbon tetrachloride. The developed analytical strategy further enabled the successful detection and quantification of adamantane in crude oil matrices. Consequently, IR-ATR spectroscopy provides a promising strategy for on ship and in situ diamondoid analysis in harsh real world environments.     

Use of atmospheric radiation measurement program data from Barrow, Alaska, for evaluation and development of snow-albedo parameterizations

Summary Snow albedo is determined from the ratio of out-going to incoming solar radiation using three years of broadband shortwave radiometer data obtained from the Barrow, Alaska, Atmospheric Radiation Measurement (ARM) site. These data are used for the evaluation of various types of snow-albedo parameterizations applied in numerical weather prediction or climate models. These snow-albedo parameterizations are based on environmental conditions (e.g., air or snow temperature), snow related characteristics (e.g., snow depth, snow age), or combinations of both. The ARM data proved to be well suited for snow-albedo evaluation purposes for a low-precipitation tundra environment. The evaluation confirms that snow-age dependent parameterizations of snow albedo work well during snowmelt, while parameterizations considering meteorological conditions often perform better during snow accumulation. Current difficulties in parameterizing snow albedo occur for long episodes of snow-event free conditions and episodes with a high frequency of snow events or strong snowfall. In a further step, the first two years of the ARM albedo dataset is used to develop a snow-albedo parameterization, and the third year’s data serves for its evaluation. This parameterization considers snow depth, wind speed, and air temperature which are found to be significant parameters for snow-albedo modeling under various conditions. Comparison of all evaluated snow-albedo parameterizations with this new parameterization shows improved snow-albedo prediction. Correspondence: Nicole M?lders, Geophysical Institute and College of Natural Science and Mathematics, University of Alaska Fairbanks, 903 Koyukuk Drive, P.O. Box 757320, Fairbanks, AK 99775-7320, USA     

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).     

Biodegradation of crude oil and mineral deposition in a shallow Gulf Coast salt dome

Crude oil biodegradation and related mineral deposition are taking place at the present time in the shallow caprock and overlaying Heterostegina limestone of the Damon Mound Salt Dome, Brazoria County, Texas. Scanning electron microscopy shows calcite, pyrite, and some elemental sulfur in intimate association with microbes, biodegraded crude oil, and gypsum. Similar processes, involving aerobic and anaerobic microbial activity, are suggested to explain the massive deposition of secondary minerals which occurred at Damon Mound in the geologic past.     

Effects of radiation exposure on indicators of thermal maturity

Study of fossil wood samples with varying contents of uranium suggests that radiation exposure over geologic time results in alteration of vitrinite. The alteration is shown by increased reflectance of vitrinite, increased values of Thermal Alteration Index, decreased atomic H/C ratios, and by loss of fluorescence. Each of these parameters is used to estimate the thermal maturity of kerogen. Unless recognized during interpretation of analytical results, radiation damage of vitrinite results in over-estimation of thermal maturity.     

Geomechanical property estimation of unconventional reservoirs using seismic data and rock physics

An extension of a previously developed rock physics model is made that quantifies the relationship between the ductile fraction of a brittle/ductile binary mixture and the isotropic seismic reflection response. By making a weak scattering (Born) approximation and plane wave (eikonal) approximation, with a subsequent ordering according to the angles of incidence, singular value decomposition analyses are performed to understand the stack weightings, number of stacks, and the type of stacks that will optimally estimate two fundamental rock physics parameters – the ductile fraction and the compaction and/or diagenesis. It is concluded that the full PP stack, i.e., sum of all PP offset traces, and the “full” PS stack, i.e., linear weighted sum of PS offset traces, are the two optimal stacks needed to estimate the two rock physics parameters. They dominate over both the second‐order amplitude variation offset “gradient” stack, which is a quadratically weighted sum of PP offset traces that is effectively the far offset traces minus the near offset traces, and the higher order fourth order PP stack (even at large angles of incidence). Using this result and model‐based Bayesian inversion, the seismic detectability of the ductile fraction (shown by others to be the important rock property for the geomechanical response of unconventional reservoir fracking) is demonstrated on a model characteristic of the Marcellus shale play.     

Sea floor responses to hydrocarbon seeps,Louisiana continental slope

Observations and samples from research submersible dives confirm that brines, crude oil, fluid mud, and gases are common seep products. Through this mechanism a unique interplay of geochemical, geologic, and biological processes resulting in unusual sea floor features ranging from carbonate-rich nodular sediments to mounds with tens of meters relief. Stable carbon isotopes occluded in the carbonates provide a permanent imprint that links these authigenic carbonates to by-products of microbial breakdown of crude oil and gas. Recent DSV ALVIN dives confirm that hydrocarbon seeps and their accompanying chemosynthetic communities and authigenic carbonate mounds occur over the entire depth range of the slope.     

Fixed-ammonium in clays associated with crude oils

The association of ammonium (NH₄⁺) silicates with organic-rich sedimentary environments has stimulated interest in the chemical cycle of N, and its possible application as an indicator of in situ organic maturation reactions or crude oil migration. Fixed-NH₄ in clay minerals was determined from three hydrocarbon occurrences of similar depositional environment but different ages, depth and thermal maturity, to determine whether anomalously high NH₄-substitution occurs near mature hydrocarbons. Results show higher fixed-NH₄ concentrations in marginally mature mudstones than in immature sediments. The highest fixed-NH₄ concentrations were found in clays from sandstone reservoirs containing migrated crude oil.Fixed-NH₄ in clays from Holocene oil seep sediments in the Gulf of Mexico continental slope, offshore Louisiana, averages 0.08 wt % and increases with depth in shallow cores (420 cm), reflecting an early diagenetic trend that is apparently not influenced by migrating crude oil. Programmed pyrolysis shows that the sediments are thermally immature (av.T_max = 419°C). High Hydrogen Index values (av.= 359mg/g) are the result of biodegraded crude oil, and a high Oxygen Index (av.= 182mg/g) reflects the presence of authigenic carbonate.Fixed-NH₄ averages 0.16 wt % in Wilcox Group (Eocene) mudstones enclosing two sandstone reservoirs at Fordoche Field, onshore Louisiana. In comparison to these mudstones, anomalously high NH₄-fixation appears to occur in reservoir clay minerals. Pyrolysis shows that the sediments are marginally mature for crude oil generation (av.T_max = 432°C). Average Hydrogen Index (187 mg/g) and Oxygen Index values (75 mg/g) are consistent with oil-prone Type II and Type III kerogen. Increased pyrolysis Production Index values and solvent extraction shows the presence of migrated crude oil. This suggests that a reaction which releases NH₃ during crude oil generation or migration is recorded byNH₄⁺ substitution in clays.Fixed-NH₄ and total organic carbon (TOC) at Fordoche Field show no statistically significant correlation, suggesting that NH₄⁺ substitution in clay minerals is not simply related to the amount of organic matter in the section, but is also influenced by the presence of crude oil. Once NH₄⁺ has been fixed in clays, it is a more stable hydrocarbon proximity indicator than pore fluid tracers, because it is less influenced by later chemical or geological changes.     

The Clouds of the Middle Troposphere: Composition, Radiative Impact, and Global Distribution

The clouds of the middle troposphere span the temperature range where both ice and liquid water in a supercooled state can exist. However, because one phase tends to dominate, of the two midlevel cloud types, altostratus are deep ice-dominated, while altocumulus are shallow water-dominated, mixed-phase clouds with ice crystal virga typically trailing below. Multiple remote sensor examples of these cloud types are given to illustrate their main features, and the radiative consequences of the different cloud microphysical compositions are discussed. Spaceborne radar and lidar measurements using the CloudSat and CALIPSO satellites are analyzed to determine the global distributions of cloud frequencies and heights of these clouds. It is found that together these little-studied clouds cover ~25% of the Earth’s surface, which is about one-third of the total cloud cover, and thus represent a significant contribution to the planet’s energy balance.