Organic geochemistry of Late Cretaceous to Paleogene sediments from MITI Sanriku-oki borehole

Perylene is present in high concentration in Paleogene sediments from the Sanriku-oki borehole of the Ministry of International Trade and Industry (MITI), northeastern Japan. The borehole penetrates a thick sequence of Late Cretaceous to Neogene sediments deposited under a range of conditions, including fluvial-deltaic and shallow marine. Organic petrological and geochemical data show the sediments to be rich in organic matter (OM) derived from higher plants. Biomarker analysis of aliphatic and aromatic hydrocarbons confirms a significant input from higher plants, with extracts dominated by numerous gymnosperm- and angiosperm-derived biomarkers such as diterpanes, oleanenes, des-A-triterpanes and their aromatized counterparts. The highest concentration of perylene occurs in Middle Eocene sediments deposited in a relatively reducing environment. Stable carbon isotope compositions show 13C enrichment in perylene compared to gymnosperm and angiosperm biomarkers, consistent with a fungal origin. This elevated abundance of sedimentary perylene could relate to a Paleogene continental climate where fungi probably flourished.

Dinoflagellate cysts of ODP Leg 101 holes

The Albian-Cenomanian sediments in Holes 627B and 635B contain diverse dinoflagellate-cyst assemblages, which show affinities with coeval assemblages from offshore Morocco and northwest Europe. A total of 34 samples were analyzed from the shallow-water platform sediments and neritic marly chalk of Hole 627B and from the argillaceous chalk and limestone of Hole 635B. Dinoflagellate cysts indicate that the top of the shallow-water platform drilled at Hole 627B must be attributed to the late Albian. Dinocysts also date the drowning of the carbonate platform of the Blake Plateau. This drowning started in the latest Albian (Vraconian) and continued into the Cenomanian. The site area changed from an inner to intermediate or outer(?) neritic environment. The area around Hole 635B from the late Albian appears to have been situated in a deeper environment than the area around Hole 627B during the same period. The new dinoflagellate-cyst species Compositosphaeridiuml bahamaensis n. sp., Maghrebinia breviornata n. sp., and Subtilisphaeral habibi n. sp. are described, and Pervosphaeridium truncatum is emended. Additional taxonomic remarks about other species are included.

Neogene benthic foraminiferal community and organic carbon at DSDP Holes 95-612 and 95-613

Quantitative study of benthic foraminifers from the upper Miocene to lower Pliocene section at Site 612 (1404 m present water depth) and the Pliocene section at Site 613 (2323 m present water depth) shows no evidence of widespread downslope transport of shallow-water biofacies or reworking of older material in the greater than 150 µm size fraction. In contrast, upper Miocene sediments from Site 604 (2364 m present water depth) show extensive reworking and downslope transport. At Site 612, benthic foraminifers show a succession from an upper Miocene Bolivina alata-Nonionella sp. biofacies, to an uppermost Miocene Bulimina alazanensis biofacies, to a lower Pliocene Cassidulina reflexa biofacies, to an upper Pliocene Melonis barleeanum-Islandiella laevigata biofacies. Evidence suggests that the Pliocene biofacies are in situ, although they could have been transported downslope from the upper-middle bathyal zone. At Site 613, Uvigerina peregrina dominated the "middle" Pliocene, while Globocassidulina subglobosa was dominant in the early and late Pliocene. High abundances of U. peregrina at Site 613 are associated with high values of sedimentary organic carbon.

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.

Neogene planktonic foraminifera of ODP Leg 101 holes

Leg 101 of the Ocean Drilling Program recovered a large volume of Neogene sediments from sites in the Straits of Florida, Little Bahama Bank, and Exuma Sound. In varying amounts, shallow-water, platform-derived carbonate debris is nearly ubiquitous. Reworked planktonic foraminifers are common, especially in the Pliocene-Pleistocene. At Site 626 in the Straits of Florida, a sequence of Holocene to upper Oligocene sediments was recovered. The greatest Neogene hiatus at this site spans the latest Miocene through Pliocene. Below this, several minor hiatuses are present in a generally conformable sequence. From the Little Bahama Bank transect (Sites 627, 628, and 630), a nearly complete composite Neogene section was sampled. At Site 627, a major unconformity separates lowermost Miocene sediments from middle to upper Eocene sediments. A second major unconformity occurs at Site 628. Here, middle Miocene sediments lie above uppermost Oligocene deposits. Sites 632, 633, and 631 in Exuma Sound all bottomed in a thick, lower Pliocene section. The mid-Pliocene is very thin at Sites 633 and 631, while it is better represented at Site 632. Major unconformities at Sites 627 and 628 appear to correlate with periods of elevated sea level, which suggests that carbonate platform shedding may be greatest during this part of the sea-level cycles. One of the salient features of the Bahamas is the lack of any systematic temporal distribution of hiatuses. Only a brief hiatus in the late Pliocene may be regional. It appears that local platform-shedding events were of equal or greater importance in developing the stratigraphy of the Bahamas than regional or eustatic events.

Geochemistry, lithology and maceral analysis at DSDP Hole 71-511

The quantity, type, and maturity of the organic matter in Recent through Upper Jurassic sediments from the Falkland Plateau, DSDP Site 511, have been determined. Sediments were investigated for their hydrocarbon potential by organic carbon and Rock-Eval pyrolysis. Kerogen concentrates were prepared and analyzed in reflected and transmitted light to determine vitrinite reflectance and maceral content. Total extractable organic compounds were analyzed for their elemental composition, and the fraction of the nonaromatic hydrocarbons was determined by capillary column gas chromatography and combined gas chromatography/mass spectrometry. Three main classes of organic matter can be determined at DSDP Site 511 by a qualitative and quantitative evaluation of microscopic and geochemical results. The Upper Jurassic to lower Albian black shales contain high amounts of organic matter of dominantly marine origin. The content of terrigenous organic matter increases at the base of the black shales, whereas the shallowest black shales near the Aptian/Albian boundary are transitional in composition, with increasing amounts of inert, partly oxidized organic matter which is the dominant component in all Albian through Tertiary sediments investigated. The organic matter in the black shales has a low level of maturity and has not yet reached the onset of thermal hydrocarbon generation. This is demonstrated by the low amounts of total extractable organic compounds, low percentages of hydrocarbons, and the pattern and composition of nonaromatic hydrocarbons. The observed reflectance of huminite and vitrinite particles (between 0.4% and 0.5% Ro at bottom-hole depth of 632 m) is consistent with this interpretation. Several geochemical parameters indicate, however, a rapid increase in the maturation of organic matter with depth of burial. This appears to result from the relatively high heat flow observed at Site 511. If we relate the level of maturation of the black shales at the bottom of Hole 511 to their present shallow depth of burial, they appear rather mature. On the basis of comparisons with other sedimentary basins of a known geothermal history, a somewhat higher paleotemperature gradient and/or additional overburden are required to give the observed maturity at shallow depth. A comparison with contemporaneous sediments of DSDP Site 361, Cape Basin, which was the basin adjacent and to the north of the Falkland Plateau during the early stages of the South Atlantic Ocean, demonstrates differences in sedimentological features and in the nature of sedimentary organic matter. We interpret these differences to be the result of the different geological settings for Sites 361 and 511.

Concentrations of rare earth elements in pore waters of IODP Holes 323-U1345A and 323-U1345B

We studied the diagenetic behavior of rare earth elements (REEs) in a highly productive passive margin setting of the Bering Sea Slope. Site U1345 was drilled during the Integrated Ocean Drilling Program Expedition 323 at a water depth of 1008 m currently in the center of an oxygen minimum zone. Pore water concentrations of fourteen REEs were determined down to ~ 140 meters below the seafloor (mbsf). The REE concentrations were higher in the pore water than the deep seawater, indicating that there was significant liberation from the sediments during diagenesis. There was a major peak at ~ 10 mbsf that was more pronounced for the heavy REE (HREE); this peak occurred below the sulfate-methane transition zone (6.3 mbsf) and coincided with high concentrations of dissolved iron and manganese. At ~ 2 mbsf, there was a minor peak in REE and Mn contents. Below ~ 40 mbsf, the REE concentration profiles remained constant. The Ce anomaly was insignificant and relatively constant (PAAS-normalized Ce/Ce = 1.1 ± 0.2) throughout the depth profile, showing that the Ce depleted in seawater was restored in the pore water. HREE-enrichment was observed over the entire 140 m except for the upper ~ 1 m, where a middle REE (MREE)-bulge was apparent. REE release in shallow depths (2-4 mbsf) is attributed to the release of light REEs (LREEs) and MREEs during the organoclastic reduction of Mn oxides in anoxic sediments. The high HREE concentrations observed at ~ 10 mbsf can be attributed to the reduction of Fe and Mn minerals tied to anaerobic oxidation of methane or, less significantly, to ferromagnesian silicate mineral weathering. The upward diffusion flux across the sediment-water interface was between 3 (for Tm) and 290 (for Ce) pmol/m**2/y.

Nd isotopes of sediments, foraminifera and fish debris of the western North Atlantic

Understanding changes in ocean circulation during the last deglaciation is crucial to unraveling the dynamics of glacial-interglacial and millennial climate shifts. We used neodymium isotope measurements on postdepositional iron-manganese oxide coatings precipitated on planktonic foraminifera to reconstruct changes in the bottom water source of the deep western North Atlantic at the Bermuda Rise. Comparison of our deep water source record with overturning strength proxies shows that both the deep water mass source and the overturning rate shifted rapidly and synchronously during the last deglacial transition. In contrast, any freshwater perturbation caused by Heinrich event 1 could have only affected shallow overturning. These findings show how changes in upper-ocean overturning associated with millennial-scale events differ from those associated with whole-ocean deglacial climate events.

Minerals and geochemistry abundance and occurance, as well as K-Ar determinations for DSDP Site 92-597 basalts

Preliminary studies of hydrothermally altered massive basalts formed at the fast-spreading Mendoza Rise and recovered from DSDP Holes 597B and 597C indicate the presence of three secondary mineral assemblages which formed in the following order: (1) trioctahedral chlorite and talc, (2) goethite and smectite, and (3) calcite and celadonite. The sequential precipitation of these mineral assemblages denotes high water:rock ratios and time-varying conditions of temperature (early >200°C to late <30°C) and state of oxidation (early nonoxidative to late oxidative). A decrease in the relative proportion of oxidative mineral assemblages with depth to 70 m in Site 597 basement indicates a zone of oxidative alteration that became shallower with time as the deeper, more constricted fracture systems were filled by secondary mineralization. In this report we present the first results of the K-Ar dating of celadonite formation age; celadonite formation reflects end-stage hydrothermal alteration in Site 597 basement. Three celadonite dates obtained from Site 597 samples include 13.1 ± 0.3 m.y. from 17 m basement depth (Hole 597B), 19.9 ± 0.4 m.y. from 18 m basement depth (Hole 597C), and 19.3 ± 1.6 m.y. from 60 m basement depth (Hole 597C). The age of host rock crystallization (28.6 m.y.) and the K-Ar dates of celadonite formation establish that hydrothermal alteration in the upper 70 m of Site 597 basement continued for at least 10 m.y. and possibly as long as 16 m.y. after basalt crystallization at the ridge crest. Assuming a half-spreading rate of 55 km/m.y., we calculate that hydrothermal circulation was active in shallow basement at a distance of at least 550 km off ridge crest and possibly as far as 1000 km off ridge crest.

Major- and trace-element chemistry of DSDP Leg 70 Holes basalts and their alteration products

Major and trace element compositions of basalts from the lower part of Hole 504B indicate their cogenetic nature. The cored sequence of interlayered pillow lavas and massive lava flows was produced by eruption of lavas, slightly variable in composition. Plagioclase and olivine crystallization in a shallow magma chamber, followed by small-scale fractionation at higher levels, is responsible for these variations. Except in highly fractured zones within the basement, there are systematic variations in the style and degree of rock alteration with depth. Trace element characteristics of altered rocks and secondary minerals indicate that progressive changes in sea water composition occurred as it reacted with basaltic crust.

Molecular and isotopic properties of gases from ODP Holes of ODP Leg 204

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.

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.