Lithology, stratigraphy, organic carbon content, extract and liquid chromatography yields, and Rock-Eval pyrolysis at DSDP Holes 75-530A and 75-532

Seventeen sediment samples of Albian-Cenomanian to early Pliocene age from DSDP Hole 530A in the Angola Basin and six sediment samples of early Pliocene to late Pleistocene age from the Walvis Ridge were investigated by organic geochemical methods, including organic carbon determination, Rock-Eval pyrolysis, gas chromatography and combined gas chromatography/mass spectrometry of extractable hydrocarbons, and kerogen microscopy. The organic matter in all samples is strongly influenced by a terrigenous component from the nearby continent. The amount of marine organic matter present usually increases with the total organic carbon content, which reaches an extreme value of more than 10% in a Cenomanian black shale from Hole 530A. At Site 530 the extent of preservation of organic matter in the deep sea sediments is related to mass transport down the continental slope, whereas the high organic carbon contents in the sediments from Site 532 reflect both high bioproductivity in the Benguela upwelling regime and considerable supply of terrigenous organic matter. The maturation level of the organic matter is low in all samples.

Background heat flow values in the region of the Sea of Okhotsk

Particular features of tectonic structure and anomalous distribution of geothermal, geomagnetic, and gravity fields in the region of the Sea of Okhotsk are considered. On the basis of heat flow data, ages of large-scale structures in the Sea of Okhotsk are estimated at 65 Ma for the Central Okhotsk Rise and 36 Ma for the South Okhotsk Basin. Age of the South Okhotsk Basin is confirmed by data on kinematics and corresponds to 50 km thickness of the lithosphere. This is in accordance with thickness value obtained by magnetotelluric soundings. Comparative analysis of model geothermal background and measured heat flow values on the Akademii Nauk Rise is performed. Analysis points to abnormally high (~20%) measured heat flow agrees with high negative gradient of gravity anomalies. Estimates of deep heat flow and basement age of riftogenic basins in the Sea of Okhotsk were carried out in the following areas: Deryugin Basin (18 Ma, Early Miocene), TINRO Basin (12 Ma, Middle Miocene), and West Kamchatka Basin (23 Ma, Late Oligocene). Temperatures at boundaries of the main lithological complexes of the sedimentary cover are calculated and zones of oil and gas generation are defined. On the basis of geothermal, magnetic, structural, and other geological-geophysical data a kinematic model of the region of the Sea of Okhotsk for period of 36 Ma was calculated and constructed.

Gas hydrate structures and C1-C5 hydrocarbons at individual sites in the Gulf of Mexico

Gas hydrate samples from various locations in the Gulf of Mexico (GOM) differ considerably in their microstructure. Distinct microstructure characteristics coincide with discrete crystallographic structures, gas compositions and calculated thermodynamic stabilities. The crystallographic structures were established by X-ray diffraction, using both conventional X-ray sources and high-energy synchrotron radiation. The microstructures were examined by cryo-stage Field-Emission Scanning Electron Microscopy (FE-SEM). Good sample preservation was warranted by the low ice fractions shown from quantitative phase analyses. Gas hydrate structure II samples from the Green Canyon in the northern GOM had methane concentrations of 70-80% and up to 30% of C2-C5 of measured hydrocarbons. Hydrocarbons in the crystallographic structure I hydrate from the Chapopote asphalt volcano in the southern GOM was comprised of more than 98% methane. Fairly different microstructures were identified for those different hydrates: Pores measuring 200-400 nm in diameter were present in structure I gas hydrate samples; no such pores but dense crystal surfaces instead were discovered in structure II gas hydrate. The stability of the hydrate samples is discussed regarding gas composition, crystallographic structure and microstructure. Electron microscopic observations showed evidence of gas hydrate and liquid oil co-occurrence on a micrometer scale. That demonstrates that oil has direct contact to gas hydrates when it diffuses through a hydrate matrix.

Heat-flow studies in the Peru Trench subduction zone

New heat-flow values were obtained in the central Peru Trench area during site surveys and drilling of Ocean Drilling Program (ODP) Leg 112 by measuring temperatures with ordinary surface heat-flow probes and in the drill holes and by estimating from bottom-simulating reflectors resulting from gas hydrates. The values determined by these methods are consistent with each other within the limits of error. When combined with existing data, heat-flow distribution from the trench to the coast was delineated. Heat flow is lower than 40 mW/m**2 at the bottom of the trench and 40 to 50 mW/m**2 on the landward slope. The low heat flow at the trench bottom can be explained partly by a high sedimentation rate. Heat flow is variable about where the Mendana Fracture Zone meets the trench. This low heat flow might result from hydrothermal circulation in the fracture zone, which some scientists believe is a new propagating rift. On the landward slope, no significant difference in heat flow is recognized between the northern side and the southern side of the fracture zone, in spite of differences in the age of the subducting plate and the tectonic history. Heat flow on the landward slope may be slightly higher than that in most other subduction zones.

Pore water geochemistry of Håkon Mosby mud volcano sediments measured at station PS74/169-1_PUC-15 (Z1-S1, new flow surface)

Pore water and turnover rates were determined for surface sediment cores obtained in 2009 and 2010. The pore water was extracted with Rhizons (Rhizon CSS: length 5 cm, pore diameter 0.15 µm; Rhizosphere Research Products, Wageningen, Netherlands) in 1 cm-resolution and immediately fixed in 5% zinc acetate (ZnAc) solution for sulfate, and sulfide analyses. The samples were diluted, filtered and the concentrations measured with non-suppressed anion exchange chromatography (Waters IC-Pak anion exchange column, waters 430 conductivity detector). The total sulfide concentrations (H2S + HS- + S**2-) were determined using the diamine complexation method (doi:10.4319/lo.1969.14.3.0454). Samples for dissolved inorganic carbon (DIC) and alkalinity measurements were preserved by adding 2 µl saturated mercury chloride (HgCl2) solution and stored headspace-free in gas-tight glass vials. DIC and alkalinity were measured using the flow injection method (detector VWR scientific model 1054) (doi:10.4319/lo.1992.37.5.1113). Dissolved sulfide was eliminated prior to the DIC measurement by adding 0.5 M molybdate solution (doi:10.4319/lo.1995.40.5.1011). Nutrient subsamples (10 - 15 ml) were stored at - 20 °C prior to concentration measurements with a Skalar Continuous-Flow Analyzer (doi:10.1002/9783527613984).

Pore water geochemistry of Håkon Mosby mud volcano sediments measured at station MSM16/2_847-1 (Z2-S2, aged flow surface)

Pore water and turnover rates were determined for surface sediment cores obtained in 2009 and 2010. The pore water was extracted with Rhizons (Rhizon CSS: length 5 cm, pore diameter 0.15 µm; Rhizosphere Research Products, Wageningen, Netherlands) in 1 cm-resolution and immediately fixed in 5% zinc acetate (ZnAc) solution for sulfate, and sulfide analyses. The samples were diluted, filtered and the concentrations measured with non-suppressed anion exchange chromatography (Waters IC-Pak anion exchange column, waters 430 conductivity detector). The total sulfide concentrations (H2S + HS- + S**2-) were determined using the diamine complexation method (doi:10.4319/lo.1969.14.3.0454). Samples for dissolved inorganic carbon (DIC) and alkalinity measurements were preserved by adding 2 µl saturated mercury chloride (HgCl2) solution and stored headspace-free in gas-tight glass vials. DIC and alkalinity were measured using the flow injection method (detector VWR scientific model 1054) (doi:10.4319/lo.1992.37.5.1113). Dissolved sulfide was eliminated prior to the DIC measurement by adding 0.5 M molybdate solution (doi:10.4319/lo.1995.40.5.1011). Nutrient subsamples (10 - 15 ml) were stored at - 20 °C prior to concentration measurements with a Skalar Continuous-Flow Analyzer (doi:10.1002/9783527613984).

Pore water geochemistry of Håkon Mosby mud volcano sediments measured at station MSM16/2_838-1 (Z1-S3, new flow surface)

Pore water and turnover rates were determined for surface sediment cores obtained in 2009 and 2010. The pore water was extracted with Rhizons (Rhizon CSS: length 5 cm, pore diameter 0.15 µm; Rhizosphere Research Products, Wageningen, Netherlands) in 1 cm-resolution and immediately fixed in 5% zinc acetate (ZnAc) solution for sulfate, and sulfide analyses. The samples were diluted, filtered and the concentrations measured with non-suppressed anion exchange chromatography (Waters IC-Pak anion exchange column, waters 430 conductivity detector). The total sulfide concentrations (H2S + HS- + S**2-) were determined using the diamine complexation method (doi:10.4319/lo.1969.14.3.0454). Samples for dissolved inorganic carbon (DIC) and alkalinity measurements were preserved by adding 2 µl saturated mercury chloride (HgCl2) solution and stored headspace-free in gas-tight glass vials. DIC and alkalinity were measured using the flow injection method (detector VWR scientific model 1054) (doi:10.4319/lo.1992.37.5.1113). Dissolved sulfide was eliminated prior to the DIC measurement by adding 0.5 M molybdate solution (doi:10.4319/lo.1995.40.5.1011). Nutrient subsamples (10 - 15 ml) were stored at - 20 °C prior to concentration measurements with a Skalar Continuous-Flow Analyzer (doi:10.1002/9783527613984).

Pore water geochemistry of Håkon Mosby mud volcano sediments measured at station MSM16/2_855-1 (Z2-S3, aged flow surface)

Pore water and turnover rates were determined for surface sediment cores obtained in 2009 and 2010. The pore water was extracted with Rhizons (Rhizon CSS: length 5 cm, pore diameter 0.15 µm; Rhizosphere Research Products, Wageningen, Netherlands) in 1 cm-resolution and immediately fixed in 5% zinc acetate (ZnAc) solution for sulfate, and sulfide analyses. The samples were diluted, filtered and the concentrations measured with non-suppressed anion exchange chromatography (Waters IC-Pak anion exchange column, waters 430 conductivity detector). The total sulfide concentrations (H2S + HS- + S**2-) were determined using the diamine complexation method (doi:10.4319/lo.1969.14.3.0454). Samples for dissolved inorganic carbon (DIC) and alkalinity measurements were preserved by adding 2 µl saturated mercury chloride (HgCl2) solution and stored headspace-free in gas-tight glass vials. DIC and alkalinity were measured using the flow injection method (detector VWR scientific model 1054) (doi:10.4319/lo.1992.37.5.1113). Dissolved sulfide was eliminated prior to the DIC measurement by adding 0.5 M molybdate solution (doi:10.4319/lo.1995.40.5.1011). Nutrient subsamples (10 - 15 ml) were stored at - 20 °C prior to concentration measurements with a Skalar Continuous-Flow Analyzer (doi:10.1002/9783527613984).

(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 geochemistry of Håkon Mosby mud volcano sediments measured at station PS74/168-1 (Z1-S2, new flow surface)

Pore water and turnover rates were determined for surface sediment cores obtained in 2009 and 2010. The pore water was extracted with Rhizons (Rhizon CSS: length 5 cm, pore diameter 0.15 µm; Rhizosphere Research Products, Wageningen, Netherlands) in 1 cm-resolution and immediately fixed in 5% zinc acetate (ZnAc) solution for sulfate, and sulfide analyses. The samples were diluted, filtered and the concentrations measured with non-suppressed anion exchange chromatography (Waters IC-Pak anion exchange column, waters 430 conductivity detector). The total sulfide concentrations (H2S + HS- + S**2-) were determined using the diamine complexation method (doi:10.4319/lo.1969.14.3.0454). Samples for dissolved inorganic carbon (DIC) and alkalinity measurements were preserved by adding 2 µl saturated mercury chloride (HgCl2) solution and stored headspace-free in gas-tight glass vials. DIC and alkalinity were measured using the flow injection method (detector VWR scientific model 1054) (doi:10.4319/lo.1992.37.5.1113). Dissolved sulfide was eliminated prior to the DIC measurement by adding 0.5 M molybdate solution (doi:10.4319/lo.1995.40.5.1011). Nutrient subsamples (10 - 15 ml) were stored at - 20 °C prior to concentration measurements with a Skalar Continuous-Flow Analyzer (doi:10.1002/9783527613984).

Pore water geochemistry of Håkon Mosby mud volcano sediments measured at station PS74/172-1_PUC-136 (Z3-S2, old flow surface)

Pore water and turnover rates were determined for surface sediment cores obtained in 2009 and 2010. The pore water was extracted with Rhizons (Rhizon CSS: length 5 cm, pore diameter 0.15 µm; Rhizosphere Research Products, Wageningen, Netherlands) in 1 cm-resolution and immediately fixed in 5% zinc acetate (ZnAc) solution for sulfate, and sulfide analyses. The samples were diluted, filtered and the concentrations measured with non-suppressed anion exchange chromatography (Waters IC-Pak anion exchange column, waters 430 conductivity detector). The total sulfide concentrations (H2S + HS- + S**2-) were determined using the diamine complexation method (doi:10.4319/lo.1969.14.3.0454). Samples for dissolved inorganic carbon (DIC) and alkalinity measurements were preserved by adding 2 µl saturated mercury chloride (HgCl2) solution and stored headspace-free in gas-tight glass vials. DIC and alkalinity were measured using the flow injection method (detector VWR scientific model 1054) (doi:10.4319/lo.1992.37.5.1113). Dissolved sulfide was eliminated prior to the DIC measurement by adding 0.5 M molybdate solution (doi:10.4319/lo.1995.40.5.1011). Nutrient subsamples (10 - 15 ml) were stored at - 20 °C prior to concentration measurements with a Skalar Continuous-Flow Analyzer (doi:10.1002/9783527613984).