Geochemistry and pyrolysis at DSDP Hole 77-535

There are substantial differences in the character of organic matter contained in the Pleistocene and Cretaceous sedimentary sequences of DSDP Site 535. The argillaceous Pleistocene section contains type III, gas-prone organic matter whereas the calcareous Cretaceous section is dominated by type II, oil-prone organic matter. A more detailed investigation of the Cretaceous section reveals that the finely laminated limestones of Valanginian to Barremian age are of good to excellent source quality. The indigenous organic matter contained within this organically rich section is thermally immature, not having undergone sufficient thermal diagenesis for the generation and expulsion of hydrocarbons. Within this stratigraphic section, however, staining by mature hydrocarbons was detected. These stains are associated with a fractured interval. These fractures may in turn represent potential migration pathways.

Subgrain boundaries and related microstructural features in EDML (Antarctica) deep ice core

Subgrain boundaries revealed as shallow sublimation grooves on ice sample surfaces are a direct and easily observable feature of intracrystalline deformation and recrystallization. Statistical data obtained from the EPICA Dronning Maud Land (EDML) deep ice core drilled in East Antarctica cannot detect a depth region of increased subgrain-boundary formation. Grain-boundary morphologies show a strong influence of internal strain energy on the microstructure at all depths. The data do not support the classical view of a change of dominating recrystallization regimes with depth. Three major types of subgrain boundaries, reflecting high mechanical anisotropy, are specified in combination with crystal-orientation analysis.

Magnetic state of ocean basalts (Table 1)

The natural remanent magnetization (NRM) of ocean basalts, giving rise to the pattern of marine magnetic anomalies, is known to be of comparatively low intensity for about 20 Ma old oceanic crust. The aim of this study is to detect possible peculiarities in the rock magnetic properties of ocean basalts of this age, and to establish a link between magnetomineralogy, rock magnetic parameters, and the low NRM intensity. Ocean basalts covering ages from 0.7 to 135 Ma were selected for rock magnetic experiments and their room temperature hysteresis parameters, Curie temperature and temperature dependence of saturation magnetization MS(T) was determined and complemented by reflected light microscopy. The majority of samples is magnetically dominated by titanomagnetite and titanomaghemite with increasing oxidation state with age. For these, a strong dependence of hysteresis parameters on the age of the samples is found. The samples have a minimum in saturation magnetization and a maximum in magnetic stability in the age interval ranging from approximately 10 to 40 Ma, coinciding with the age interval of low NRM intensity. The observed change in saturation magnetization is in the same order as that for the NRM intensity. A further peculiarity of the titanomaghemites from this age interval is the shape of their MS(T) curves, which display a maximum above room temperature (Neel P-type) and, sometimes, a self-reversal of magnetization below room temperature (Neel N-type). These special rock magnetic properties can be explained by titanomagnetite low-temperature oxidation and highly oxidized titanomaghemites in the age interval 10-40 Ma. A corresponding measurement of the NRM at elevated temperature allows to identify a maximum in NRM intensity above room temperature for the samples in that age interval. This provides evidence that the NRM is equally carried by titanomaghemites and that the low NRM intensities for about 20 Ma old ocean basalts are caused consequently by the low saturation magnetization of these titanomaghemites.

Chemical composition of zoobenthos and bottom sediments from the gas-hydrate seep area near the Paramushir Island, Kuril Island arc

Bioaccumulation of metals by zoobenthos was investigated during cruise 11A of R/V Akademik Mstislav Keldysh in the vicinity of a gas-hydrate seep off Paramushir Island in the Sea of Okhotsk. Atomic absorption studies of concentrations of Al, Fe, Mn, Ni, Cu and Zn in zoobenthos (polychaetes, bivalves, ophiurans and echinoderms) collected from depths of 700-800 m indicated that their concentrations in individuals near the seep were not significantly different from those in individuals from other communities. Obtained results indicate that sea urchins and holothurians (non-sorting bottom-feeders) can separate mineral fraction of ingested bottom material.

(Table 1) Zoobenthos from the gas-hydrate seep area near the Paramushir Island and its chemical composition

Distributions of Mn, Fe, Cu, Cd, Cr, Co and Ni in sea water are investigated (42 samples, dissolved and particulate forms) in the vicinity of the underwater gas vent field on the northwestern slope of the Paramushir Island. While regular background distributions of the elements occur in the shore zone, there is a column of elevated concentrations of particulate matter, particulate Mn, and dissolved Mn, Fe, Cu, Cd, Cr, Co and Ni that coincides with location of the gas plume. This column can be traced as high as 780 m above the bottom. High metal concentrations in water of the plume are attributable to physico-chemical concentration at the phase interface; the source of elevated mineral concentrations is obviously flux of dissolved minerals from interstitial waters, which extends to considerable distances in vertical direction.

Gas analysis of sediment cores from the Batumi seep area

Detailed knowledge of the extent of post-genetic modifications affecting shallow submarine hydrocarbons fueled from the deep subsurface is fundamental for evaluating source and reservoir properties. We investigated gases from a submarine high-flux seepage site in the anoxic Eastern Black Sea in order to elucidate molecular and isotopic alterations of low-molecular-weight hydrocarbons (LMWHC) associated with upward migration through the sediment and precipitation of shallow gas hydrates. For this, near-surface sediment pressure cores and free gas venting from the seafloor were collected using autoclave technology at the Batumi seep area at 845 m water depth within the gas hydrate stability zone. Vent gas, gas from pressure core degassing, and from hydrate dissociation were strongly dominated by methane (>99.85 mol.% of Sum[C1-C4, CO2]). Molecular ratios of LMWHC (C1/[C2 + C3] > 1000) and stable isotopic compositions of methane (d13C = -53.5 per mill V-PDB; D/H around -175 per mill SMOW) indicated predominant microbial methane formation. C1/C2+ ratios and stable isotopic compositions of LMWHC distinguished three gas types prevailing in the seepage area. Vent gas discharged into bottom waters was depleted in methane by >0.03 mol.% (Sum[C1-C4, CO2]) relative to the other gas types and the virtual lack of 14C-CH4 indicated a negligible input of methane from degradation of fresh organic matter. Of all gas types analyzed, vent gas was least affected by molecular fractionation, thus, its origin from the deep subsurface rather than from decomposing hydrates in near-surface sediments is likely. As a result of the anaerobic oxidation of methane, LMWHC in pressure cores in top sediments included smaller methane fractions [0.03 mol.% Sum(C1-C4, CO2)] than gas released from pressure cores of more deeply buried sediments, where the fraction of methane was maximal due to its preferential incorporation in hydrate lattices. No indications for stable carbon isotopic fractionations of methane during hydrate crystallization from vent gas were found. Enrichments of 14C-CH4 (1.4 pMC) in short cores relative to lower abundances (max. 0.6 pMC) in gas from long cores and gas hydrates substantiates recent methanogenesis utilizing modern organic matter deposited in top sediments of this high-flux hydrocarbon seep area.

(Table 1) Hydrocarbon gas composition of sediment and gas hydrate collected in video-guided grabs from Chapopote

In the Campeche Knolls, in the southern Gulf of Mexico, lava-like flows of solidified asphalt cover more than 1 square kilometer of the rim of a dissected salt dome at a depth of 3000 meters below sea level. Chemosynthetic tubeworms and bivalves colonize the sea floor near the asphalt, which chilled and contracted after discharge. The site also includes oil seeps, gas hydrate deposits, locally anoxic sediments, and slabs of authigenic carbonate. Asphalt volcanism creates a habitat for chemosynthetic life that may be widespread at great depth in the Gulf of Mexico.

Gas hydrate investigation at the Amsterdam mud volcano

We investigated gas hydrate in situ inventories as well as the composition and principal transport mechanisms of fluids expelled at the Amsterdam mud volcano (AMV; 2,025 m water depth) in the Eastern Mediterranean Sea. Pressure coring (the only technique preventing hydrates from decomposition during recovery) was used for the quantification of light hydrocarbons in near-surface deposits. The cores (up to 2.5 m in length) were retrieved with an autoclave piston corer, and served for analyses of gas quantities and compositions, and pore-water chemistry. For comparison, gravity cores from sites at the summit and beyond the AMV were analyzed. A prevalence of thermogenic light hydrocarbons was inferred from average C1/C2+ ratios <35 and d13C-CH4 values of -50.6 per mil. Gas venting from the seafloor indicated methane oversaturation, and volumetric gas-sediment ratios of up to 17.0 in pressure cores taken from the center demonstrated hydrate presence at the time of sampling. Relative enrichments in ethane, propane, and iso-butane in gas released from pressure cores, and from an intact hydrate piece compared to venting gas suggest incipient crystallization of hydrate structure II (sII). Nonetheless, the co-existence of sI hydrate can not be excluded from our dataset. Hydrates fill up to 16.7% of pore volume within the sediment interval between the base of the sulfate zone and the maximum sampling depth at the summit. The concave-down shapes of pore-water concentration profiles recorded in the center indicate the influence of upward-directed advection of low-salinity fluids/fluidized mud. Furthermore, the SO42- and Ba2+ pore-water profiles in the central part of the AMV demonstrate that sulfate reduction driven by the anaerobic oxidation of methane is complete at depths between 30 cm and 70 cm below seafloor. Our results indicate that methane oversaturation, high hydrostatic pressure, and elevated pore-water activity caused by low salinity promote fixing of considerable proportions of light hydrocarbons in shallow hydrates even at the summit of the AMV, and possibly also of other MVs in the region. Depending on their crystallographic structure, however, hydrates will already decompose and release hydrocarbon masses if sediment temperatures exceed ca. 19.3°C and 21.0°C, respectively. Based on observations from other mud volcanoes, the common occurrence of such temperatures induced by heat flux from below into the immediate subsurface appears likely for the AMV.