Organic geochemistry of DSDP Site 467

Results of the analyses of twenty-three samples from the Middle Miocene to Lower Pliocene strata from DSDP Site 467, offshore California, are presented. The analyses were performed with the aim of determining the origin of the organic matter, the stratigraphic section's hydrocarbon generation potential and extent of organic diagenesis. Organic carbon contents are an order of magnitude greater than those typically found in deep sea sediments, suggesting an anoxic depositional environment and elevated levels of primary productivity. Hydrocarbon generation potentials are above average for most samples. The results of elemental analyses indicate that the kerogens are primarily composed of type II organic matter and are thermally immature. Analysis of the bitumen fractions confirms that the samples are immature. In cores from 541 to 614 meters, the gas chromatograms of the C15+ non-aromatic hydrocarbon fractions are dominated by a single peak which was identified as 17*(H), 18*(H), 21beta(H)-28, 30-bisnorhopane. This interval is the same area in which the highest degrees of anoxia are observed as reflected by the lowest pristane/phytane ratios. This correlation may have some implications with regard to the origin of the bisnorhopane and its possible use as an indicator of anoxic depositional conditions within thermally immature sediments.

Sedimentary facies, clay mineralogy and geochemistry of the Paleogene sediments of ODP Site 105-647

Claystones immediately overlying the early Eocene age ocean-floor basalt, cored at Ocean Drilling Program (ODP) Site 647, underwent hydrothermal and thermal alterations originating from the basalt, which resulted in changes in both the mineralogical and chemical composition of the sediments. Chlorites and higher magnesium and iron concentrations were found in the lowermost sediment sequence. Upcore, changes in the bulk chemical composition of the sediments become smaller, when compensated for variations in the carbonate content originating from biogenic and authigenic components. Chlorite disappears upcore, but still only part of the swelling clay minerals have survived the thermal influence. Thirty meters above the basalt, the clay mineralogy and chemical composition become uniform throughout the Paleogene section. Iron-rich smectites (i.e., nontronitic types), totally dominate the clay mineral assemblage. Biogenic components, responsible for the dominant part of the calcite and cristobalite contents, vary in amount in the upper part, and so do the authigenic carbonate and sulfide contents. Detrital components, such as kaolinite, illite, quartz, and feldspars, make up a very small proportion of the sediment record. The nontronitic smectites are believed to be authigenic, formed by a supply of iron from the continuous formation of ocean-floor basalt in the ridge area that reacted with the detrital and biogenic silicates and alumina silicates.

Stress tests of ODP Site 131-808 sediments

Sediments undergoing accretion in trench-forearc systems are subjected to conditions of large lateral thrusting. This stress regime controls the mechanism of faulting as well as the yield and strength properties of the sediment. Understanding them is therefore crucial for the construction of quantitative models of sediment dynamics in convergent margin settings. For this purpose triaxial and oedometer tests were performed on six whole-round core samples recovered from Site 808 from depths between 173 and 705 mbsf. Samples from five depth intervals were subjected to a triaxial test program that was primarily designed to define yield and strength behavior. Test specimens were cut parallel and normal to the core axis. Additional five oedometer tests with similarly prepared specimens were performed on samples from four depth intervals to evaluate the directional state and degree of sediment compaction. Test results show that the degree of sediment compaction is higher than expected from overburden. This overcompaction increases with depth. A well-developed mechanical anisotropy is evident in all samples tested, regardless of their depth and lithology. Values of yield limit, stiffness, and shear strength are up to 40% higher in the horizontal direction compared to the vertical direction. In addition the test data demonstrate that the axis of the volumetric yield loci have rotated into extensional stress field. This verifies that the mechanical state of sediment in the accretionary wedge is controlled by in-situ stress conditions of extensional nature. The coefficients of lateral stress inferred suggest that the extensional stress regime becomes increasingly effective with depth.

Petrographic description and mineral composition of ODP Site 161-975 sediments

Ocean Drilling Program Site 975 is located near the base of the Menorca Rise in the South Balearic Basin of the western Mediterranean Sea. Coring at this site penetrated the Pliocene/Miocene boundary and recovered a sequence of sediments that represent the final stages of salt deposition and the transition from evaporitic to open marine conditions at the end of the Miocene (Messinian). Detailed petrographic observations and bulk mineralogical analyses by X-ray diffraction form the basis for preliminary interpretations of depositional environments for this section. Gypsum is thought to have been deposited in an evaporating basin below wave base. Cycles consisting of a clay layer overlain by gypsiferous chalk, laminated gypsum, and finally pinch-and-swell gypsum suggest upsection increases in salinity. The gypsum section is overlain by two exotic sand layers thought to mark events of fresher water (marine or meteoric) inflow to the basin. Gypsum deposition terminated and was replaced by inorganic precipitation of micritic calcite with periodic, variable dilution by fine-grained terrigenous sediment. The micritic sediments have fine, slightly wavy, laminations indicating either an algal/microbial mat origin, or varve-like fluctuations in deposition, perhaps in a deep basin. The Pliocene/Miocene boundary falls within an interval of banded micritic silty clays that reflect the final environmental fluctuations during the transition to the open marine conditions of the Pliocene.

n-Alkane, fatty acid and hopanoic acid concentrations of ODP Site 190-1178 samples

Ocean Drilling Program (ODP) Leg 190 was programmed to investigate deformational, diagenetic, and hydrologic processes and their interactions in the Nankai Trough accretionary prism. Site 1178 is the northernmost site in the Muroto Transect. Slope sediments and the underlying landward-dipping reflector zone were successfully cored. Temperature measurements and Cl concentrations in pore water indirectly indicate the presence of gas hydrate between 120 and 400 meters below seafloor (mbsf) at Site 1178, with the highest concentrations between 150 and 200 mbsf (Shipboard Scientific Party, 2001, doi:10.2973/odp.proc.ir.190.109.2001). Sedimentary structures show a broad range of deformation structures rich in fractures, suggesting active fluid circulation in the Nankai Trough prism. One of the objectives of Leg 190 was to clarify the interplay of various fundamental processes taking place in the Nankai Trough accretionary prism. Bacteria or prokaryotes in deep subsurface sediment play an important role for material transformation and circulation in an accretionary prism. Significant amounts of bacteria are detected in many of the samples examined (Shipboard Scientific Party, 2001, doi:10.2973/odp.proc.ir.190.109.2001). The type of organic matter in sediments is an important factor related to bacterial activity. To assist investigations on material circulation in deep subsurface sediments, the samples from Site 1178 were analyzed for geolipids (extractable organic matter). The basic data set is preliminarily compiled in the present report to show the types of organic matter and their concentrations in sediments from Site 1178.

Alkenone composition, UK'37 index, and carbon, sulphur, nitrogen and element oxides of ODP Site 186-1151

Ocean Drilling Program (ODP) Site 1151 (Sacks, Suyehiro, Acton, et al., 2000, doi:10.2973/odp.proc.ir.186.2000) is located in an area where the surface water mass is influenced by both the Kuroshio and Oyashio Currents. The site also receives a relatively high flux of detrital materials from riverine input from Honsyu Island and eolian input from Central and East Asia. We analyzed alkenones and alkenoates in the sediments to reconstruct alkenone unsaturation index (Uk'37)-based sea-surface temperature (SST), total organic carbon, and total nitrogen to estimate the terrigenous contribution by the C/N ratio during the last glacial-interglacial cycle. The major elements were also analyzed to examine the variation in terrigenous composition.

Lithologic description and vertical permeability measurements of ODP Site 180-1109

Vertical permeability testing was conducted on four samples collected from Site 1109, a borehole advanced during Ocean Drilling Program Leg 180. Closed conditions were applied during each test, and the samples were measured using a constant flow approach and permeant solutions that matched the geochemistry of nearby interstitial waters. Vertical permeabilities measured at 34.5 kPa effective stress generally decreased with depth and ranged from 10**-14 m**2 at 212.53 meters below seafloor (mbsf) to 10**-18 m**2 at 698.10 mbsf. The three deepest samples differed in permeability by less than one order of magnitude. Reconsolidation testing on the shallowest sample yielded a minimum permeability of 1.56 x 10**-16 m**2 at 276 kPa effective stress. Subsequent rebound testing yielded a hysteresis-type curve, with the final permeability measuring lower than the initial permeability by nearly 1.5 orders of magnitude. Dilution experiments indicated that use of a permeant solution matching the geochemistry of the interstitial waters may be necessary for accuracy in measurements and mitigation of clay swellage and collapse during testing, but further research is mandated.

Stable carbon and oxygen isotope ratios of carbonates of ODP Site 103-639

A Tithonian sequence of shallow-water limestones, intercalated with siliciclastics and overlain by dolomite, was recovered during drilling at ODP Site 639 on the edge of a tilted fault block. The carbonates were strongly affected by fracturing, dolomitization, dedolomitization, and compaction. The chronology and nature of the fractures, fracture infilling, and diagenesis of the host rock are established and correlated for both the limestone and the dolomite. A first phase of dolomitization affected limestone that was already, at least partially, indurated. In the limestone unit, fractures were filled by calcite and dolomite; most of the dolomite was recrystallized into calcite, except for the upper part. In the dolomitic unit, the first-formed dolomite was progressively recrystallized into saddle dolomite, as fractures were simultaneously activated. The dolomitic textures become less magnesian (the molar ratio mMg/mCa goes from 1.04-0.98 to 0.80), and the d18O (PDB) ranges from -10 per mil to -8 per mil. The varying pores and fissures are either cemented by a calcic saddle dolomite (mMg/mCa ranging from 0.95 to 0.80) or filled with diverse internal sediments of detrital calcic dolomite, consisting of detrital dolomite silt (d18O from -9 per mil to -7 per mil) and laminated yellow filling (with different d18O values that range from -4 per mil to +3 per mil). These internal sediments clearly contain elements of the host rock and fragments of saddle crystals. They are covered by marls with calpionellids of early Valanginian age, which permits dating of most of the diagenetic phases as pre-Valanginian. The dolomitization appears to be related to fracturing resulting from extensional tectonics; it is also partially related to an erosional episode. Two models of dolomitization can be proposed from the petrographic characteristics and isotopic data. Early replacement of aragonite bioclasts by sparite, dissolution linked to dolomitization, and negative d18O values of dolomite suggest a freshwater influence and 'mixing zone' model. On the other hand, the significant presence of saddle dolomite and repeated negative d18O values suggest a temperature effect; because we can dismiss deep burial, hydrothermal formation of dolomite would be the most probable model. For both of these hypotheses, the vadose filling of cavities and fractures by silt suggests emersion, and the different, and even positive, d18O values of the last-formed yellow internal sediment could suggest dolomitization of the top of the sequence under saline to hypersaline conditions. Fracturing resulting in the reopening of porosity and the draining of dolomitizing fluids was linked to extensional tectonics prior to the tilting of the block. These features indicate an earlier beginning to the rifting of the Iberian margin than previously known. Dolomitization, emersion, and erosion correspond to eustatic sea-level lowering at the Berriasian/Valanginian boundary. Diagenesis, rather than sedimentation, seems to mark this global event and to provide a record of the regional tectonic history.

Organic carbon analyses of ODP Site 160-971 in the Mediterranean Sea

Mud volcanism on the Mediterranean Ridge is caused by extrusion of overpressured sediments, with consequent formation of spectacular dome-shaped features composed of mud breccias at the seafloor. The organic material in the mud breccia of the Napoli mud volcano is a mixture of different facies, stratigraphic origin and thermal maturities. One portion is synsedimentary organic material with only minor diagenetic alterations and represents sedimenting material that was embedded into the mud volcano during its extrusion. The mud breccia also contains thermally mature organic material of mainly terrestrial provenance with algae of fresh- and brackish-water origin. Vitrinite reflectance data of this maturity generation range from 0.65 to 0.90% R(oil) and thus characterize thermally mature source rocks, a rank which is corroborated by fluorescence and molecular characteristics. The predominance of vitrinite in the maceral assemblages and the occurrence of biomarkers of terrigenous origin suggest that the major part of the mud matrix derives from a lacustrine or riverine sedimentary unit in the subsurface, possibly from the Messinian stage. A third generation of organic material includes inertinites and vitrinites of high reflectance, which represent recycled organic matter present in any marine sediment. By use of the Lopatin method for modelling the thermal maturation of hydrocarbon source rocks from the vitrinite reflectance data, we calculated that the depth of mobilization ranges from 4900 m to 7500 m, depending upon the temperature gradient used.

Grain sizes and mineral composition of the basement of ODP Site 206-1256

Hole 1256C was cored 88.5 m into basement, and Hole 1256D, the deep reentry hole, was cored 502 m into basement during Ocean Drilling Program Leg 206. Hole 1256D is located ~30 m south of Hole 1256C (Wilson, Teagle, Acton, et al., 2003, doi:10.2973/odp.proc.ir.206.2003). A thick massive flow drilled in both holes, Units 1256C-18 and 1256D-1, consists of a single cooling unit of cryptocrystalline to fine-grained basalt, interpreted as a ponded lava, 32 m and at least 74.2 m thick, respectively. This ponded flow gives us a unique opportunity to examine textural variations from the glassy, folded crust of the lava pond recovered from the top of Unit 1256C-18 through the coarse-grained, thick massive lava body to the unusually recrystallized and deformed base cored in Unit 1256C-18. Some detailed descriptions of the textures and grain size variations through the lava pond (Units 1256C-18 and 1256D-1), with special reference to the recrystallization of the base of Unit 1256C-18, are presented here.