Interstitial water chemistry at DSDP Leg 67 Holes

Interstitial water chemistry has proved to be a sensitive indicator for early diagenetic reactions, particularly those related to organic matter oxidation. Downhole chemical variations in the pore waters from Deep Sea Drilling Project Holes 496 and 497 on the Middle America Trench slope off Guatemala are anomalous because both salinity and chlorinity show strong decreases to half the values of seawater, and d18O values become positive (maximum of about +2.5% at the bottom of the holes). These observations are explained in terms of dilution of pore waters after retrieval as a result of decomposition of the gas hydrates before removal of pore waters by shipboard squeezing techniques. In all holes, except Hole 495 (drilled in pelagic sediments), decomposition of organic matter leads to rapid sulfate depletion and subsequent methane generation. Associated with methane generation are large increases in alkalinity and dissolved ammonia. The latter component causes ion exchange reactions with clay minerals, which results in maxima in magnesium and perhaps potassium. At greater depths, as yet unidentified reactions cause the removal of magnesium. Especially in the deeper Trench Sites 499 and 500, rapid variations in calcium, magnesium, and alkalinity occur in turbidite sequences.

Geochemistry of carbon at DSDP Legs 56-57 Holes

Forty-three core sections from Sites 434, 435, 438, 439, and 440 on the landward side and six core sections from Site 436 on the seaward side of the Japan Trench were obtained through the JOIDES Organic Geochemistry Advisory Panel for study of the origin and state of genesis of the organic matter associated with these continental slope, accretionary wedge, and outer trench slope sediments of the Japan Trench. The lipid fraction of these sediments is derived primarily from terrigenous organic matter and thus is allochthonous to the area. The associated kerogen fraction is of mixed allochthonous and autochthonous origin. The total organic carbon content seaward of the trench is less than that on the landward side. The composition of this organic matter is similar but not identical to that found in the landward side sediments. The organic matter within these sediments is in a diagenetic state in which geopolymerization of biogenic organic matter is nearly complete, but microbial alteration is still occurring.

Rare and trace element analyses from DSDP Holes 31-291 and 31-294 from the Philippine Sea

Metal-rich sediments were found in the West Philippine Basin at DSDP sites 291 (located about 500 km SW of the Philippine Ridge or Central Basin Fault) and 294/295 (located about 580 km NE of the Philippine Ridge). In both cases the metalliferous deposits constitute a layer, probably Eocene in age, resting directly above the basaltic basement at the bottom of the sediment column. The chemistry of the major (including Fe and Mn) and trace elements (including trace metals, rare earth elements, U and Th) suggest a strong similarity of these deposits to metalliferous deposits produced by hydrothermal activity at oceanic spreading centers. Well-crystallized hematite is a major component of the metal-rich deposits at site 294/295. We infer that the Philippine Sea deposits were formed at some spreading center by hydrothermal processes of metallogenesis, similar to processes occurring at oceanic spreading centers. A locus for their formation might have been the Philippine Ridge (Central Basin Fault), probably an extinct spreading center. We conclude that metallogenesis of the type occurring at oceanic spreading centers can take place also in marginal basins. This has implications for the origin of metal deposits found in some ophiolite complexes, such as those in Luzon (Philippines), which may represent fragments of former marginal basins rather than of oceanic lithosphere.

Magnetic measurements on ODP holes 178-1095A, 178-1095B and 178-1101A

We have determined the azimuth of bottom-current flow in drift deposit sediments recovered at ODP Sites 1095 and 1101, Antarctic Peninsula, using paleomagnetic reorientation of anisotropy of magnetic susceptibility (AMS) ellipsoids. A total of 38 cores from the two ODP sites have been measured, providing spatial and directional information on the physical record of the ACC (Antarctic Circumpolar Current) in the Plio-Pleistocene. Declination and inclination of the paleomagnetic vector of each core segment were used to reorient the AMS principal axes to the geographic coordinates. The cores were reoriented using the measured direction of the characteristic remanent magnetization (ChRM) with respect to a common reference line for the core, from which we are able to determine the orientation of the paleocurrent flow for Sites 1095 (Drift 7) and 1101 (Drift 4) relative to the geographic coordinates. Both sites have paleocurrent directions trending ~NW-SE, which in the former locality are parallel to a sediment wave field. Our study shows that a combination of magnetic fabric analysis and paleomagnetism allows deep-sea sedimentary fabric to be used as a long-term proxy of bottom-current flow history.

Cretaceous calcareous nannofossils of ODP Leg 103 holes

Ocean Drilling Program Leg 103 recovered Lower Cretaceous sediments from the Galicia margin off the coast of Iberia. The high diversity and abundance of assemblages makes this excellent material for the study of Early Cretaceous calcareous nannofossils. With the exception of a hiatus between the upper Hauterivian and lower Barremian, nannofossil distributions form a continuous composite section from the lower Valanginian to lower Cenomanian sediments recovered at the four sites. The sedimentation history of this rifted continental margin is complex, and careful examination of the nannofossil content and lithology is necessary in order to obtain optimum biostratigraphic resolution. The Lower Cretaceous sequence consists of a lower Valanginian calpionellid marlstone overlain by terrigenous sandstone turbidites deposited in the Valanginian and Hauterivian during initial rifting of this part of the margin. Interbedded calcareous marl and claystone microturbidites overlie the sandstone turbidites. Rifting processes culminated in the late Aptian-early Albian, resulting in the deposition of a calcareous, clastic turbidite sequence. The subsequent deposition of dark carbonaceous claystones (black shales) represents the beginning of seafloor spreading, as the margin continued to subside to depths near or below the CCD. The diversity, abundance, and preservation of nannofossils within these varied lithologies differ, and an attempt to distinguish between near shore and open-marine assemblages is made. Genera used for this purpose include Nannoconus, Micrantholithus, Pickelhaube, and Lithraphidites. In this study, six new species and one new subspecies are described and documented. Ranges of other species are extended, and an attempt is made to clarify existing, yet poorly understood, taxonomic concepts. A technique in which a single specimen is viewed with both light and scanning electron microscopes was used extensively to aid in this task. In addition, further subdivisions of the Sissingh (1977) zonation are suggested in order to increase biostratigraphic resolution.

Occurrence of hiatuses PH and NH 1 through NH 7 in DSDP holes

Miocene paleoceanographic evolution exhibits major changes resulting from the opening and closing of passages, the subsequent changes in oceanic circulation, and development of major Antarctic glaciation. The consequences and timing of these events can be observed in variations in the distribution of deep-sea hiatuses, sedimentation patterns, and biogeographic distribution of planktic organisms. The opening of the Drake Passage in the latest Oligocene to early Miocene (25-20 Ma) resulted in the establishment of the deep circumpolar current, which led to thermal isolation of Antarctica and increased global cooling. This development was associated with a major turnover in planktic organisms, resulting in the evolution of Neogene assemblages and the eventual extinction of Paleogene assemblages. The erosive patterns of two widespread hiatuses (PH, 23.0-22.5 Ma; and NH 1, 20-18 Ma) indicate that a deep circumequatorial circulation existed at this time, characterized by a broad band of carbonate-ooze deposition. Siliceous sedimentation was restricted to the North Atlantic and a narrow band around Antarctica. A major reorganization in deep-sea sedimentation and hiatus distribution patterns occurred near the early/middle Miocene boundary, apparently resulting from changes in oceanic circulation. Beginning at this time, deep-sea erosion occurred throughout the Caribbean (hiatus NH 2, 16-15 Ma), suggesting disruption of the deep circumequatorial circulation and northward deflection of deep currents, and/or intensification of the Gulf Stream. Sediment distribution patterns changed dramatically with the sudden appearance of siliceous-ooze deposition in the marginal and east equatorial North Pacific by 16.0 to 15.5 Ma, coincident with the decline of siliceous sedimentation in the North Atlantic. This silica switch may have been caused by the introduction of Norwegian Overflow Water into the North Atlantic acting as a barrier to outcropping of silica-rich Antarctic Bottom Water. The main aspects of the present oceanic circulation system and sediment distribution pattern were established by 13.5 to 12.5 Ma (hiatus NH 3), coincident with the establishment of a major East Antarctic ice cap. Antarctic glaciation resulted in a broadening belt of siliceous-ooze deposition around Antarctica, increased siliceous sedimentation in the marginal and east equatorial North Pacific and Indian Oceans, and further northward restriction of siliceous sediments in the North Atlantic. Periodic cool climatic events were accompanied by lower eustatic sea levels and widespread deep-sea erosion at 12 to 11 Ma (NH 4), 10 to 9 Ma (NH 5), 7.5 to 6.2 Ma (NH 6), and 5.2 to 4.7 Ma (NH 7).

Physical properties and bulk minerals from IODP Holes 308-U1322B, U1322D and U1324B

How the micro-scale fabric of clay-rich mudstone evolves during consolidation in early burial is critical to how they are interpreted in the deeper portions of sedimentary basins. Core samples from the Integrated Ocean Drilling Program Expedition 308, Ursa Basin, Gulf of Mexico, covering seafloor to 600 meters below sea floor (mbsf) are ideal for studying the micro-scale fabric of mudstones. Mudstones of consistent composition and grain size decrease in porosity from 80% at the seafloor to 37% at 600 mbsf. Argon-ion milling produces flat surfaces to image this pore evolution over a vertical effective stress range of 0.25 (71 mbsf) to 4.05 MPa (597 mbsf). With increasing burial, pores become elongated, mean pore size decreases, and there is preferential loss of the largest pores. There is a small increase in clay mineral preferred orientation as recorded by high resolution X-ray goniometry with burial.

Bitumen and n-alkanes in organic matter from sedimentary rocks sampled in DSDP Holes 47-397A and 47-398

A study of samples from DSDP Leg 47 shows that transformation of organic matter in deep sea sediments is completly analogous to evolution of organic matter in sedimentary sequences on continents and depends on the same factors. Crucial among these factors are: genesis of organic matter, nature of its diagenetic changes, and current stage of catagenesis.

Concentrations of tektites and chemical elements in sediments from ODP Holes 121-758B and 124-769A

Recently published studies of Ocean Drilling Project (ODP) cores from near southeast Asia revealed microtektite contents much higher than those in previously studied cores, suggesting that Ir contents might be enhanced in the tektite-bearing horizons. We determined a positive Ir anomaly in ODP core 758B from the Ninetyeast Ridge, eastern Indian Ocean; the peak Ir concentration of 190 pg/ g was ~2X the continuum level. The net Ir fluence is 1.8+/-0.5 ng/cm**2 over the depth interval from 10.87 to 11.32 m; a small additional peak also associated with microtektites contributes another 0.5 ng Ir/cm**2. Concentrations of Ir in core 769A show more scatter, but a small Ir enhancement is associated with the peak microtektite abundance; our best estimate of the poorly constrained fluence is 1.3+/-0.7 ng/cm**2. Data on deep-sea cores show that the microtektite fluence falls exponentially away from southeast Asia, the fluence dropping a factor of 2 in ~400 km. In southeast Asia the trend merges with a roughly estimated mass fluence of ~1.1 g/cm**2 inferred from evidence of a melt sheet in northeast Thailand. Integration of the inferred distribution yields a total mass of Australasian tektites of 3.2x10**16 g, much higher than previous estimates. Assuming a similar fallout distribution for the impactor and a chondritic composition allows us to calculate its mass to be 1.5x10**15 g, about 3 orders of magnitude smaller than the minimum mass of the impactor responsible for the extinctions at the end of the Cretaceous.

Concentration of the rare-earth elements in metalliferous sediments from DSDP Leg 92 holes

DSDP Leg 92 drilled at four sites along an east-west transect at 19°S on the western flank of the East Pacific Rise (EPR), in an area where sediments are essentially a mixture of hydrothermal and biogenic components, with only a minimal contribution of clastic material. Rare-earth element (REE) data on the metalliferous (non-carbonate) fraction of samples ranging in age from ~2 to ~27 Ma indicate the existence of two distinct groups of patterns corresponding to two broad age groups, one <=8 Ma, the other >=10 Ma. Within each group, REE patterns have characteristics which are near-uniform, despite large variations in total REE abundances. Sediments of the younger group are enriched in light REE (LREE) relative to deep bottom waters influenced by the hydrothermal plume extending west from the EPR at 19°S. Sediments of the older groups show further relative LREE enrichment and/or heavy REE (HREE) depletion. Surficial sediments deposited beneath the lysocline have high Sum REE concentrations resulting from slow accumulation rates, and patterns resembling older sediments due to early diagenetic effects. A correlation between the mass accumulation rates (MAR) of Sum REE and Fe + Mn suggests that ferromanganese particulate matter supplied by the hydrothermal plume scavenges REE; during this process the LREE are preferentially removed from plume seawater. The MAR of Fe + Mn shows a general decrease with age above basement, whereas Sum REE concentrations in the metalliferous component increase with age above basement. This supports the Ruhlin and Owen model wherein limited scavenging of REE, due to rapid burial of sediment near the palaeo-axis, leads to low concentrations (but high MAR-values) for the REE. Following deposition and burial of the hydrothermal component, further relative flattening of the REE pattern takes place, probably the result of diagenetic reactions over several million years. Phase partitioning data indicate that the proportion of REE residing in more poorly crystalline phases tends to increase with age (from ~45% to 90% of Sum REE). This suggests that as initial ferromanganese precipitates undergo diagenetic recrystallization, REE are transferred to the poorly crystalline phases, and/or are scavenged from pore waters by these phases. Because of the various modifications to REE patterns apparently produced both in the water column and post-depositional settings, the REE patterns of metalliferous sediments will not reflect fine-scale REE variations in associated oceanic water masses.

Uranium concentrations and isotope ratios Bahamas seawater and ODP holes pore-water

The geometry, timing, and rate of fluid-flow through carbonate margins and platforms is not well constrained. In this study, we use U concentrations and isotope ratios measured on small volumes of pore-water from Bahamas slope sediment, coupled with existing chlorinity data, to place constraints on the fluid-flow in this region and, by implication, other carbonate platforms. These data also allow an assessment of the behaviour of U isotopes in an unusually well constrained water-rock system. We report pore-water U concentrations which are controlled by dissolution of high-U organic material at shallow depths in the sediment and by reduction of U to its insoluble 4+ state at greater depths. The dominant process influencing pore-water (234U/238U) is alpha recoil. In Holocene sediments, the increase of pore-water (234U/238U) due to recoil provides an estimate of the horizontal flow rate of 11 cm/year, but with considerable uncertainty. At depths in the sediment where conditions are reducing, features in the U concentration and (234U/238U) profiles are offset from one another which constrains the effective diffusivity for U in these sediments to be c. 1-2 * 10**-8 cm**2/s. At depths between the Holocene and these reducing sediments, pore-water (234U/238U) values are unusually low due to a recent increase in the dissolution rate of grain surfaces. This suggests a strengthening of fluid flow, probably due to the flooding of the banks at the last deglaciation and the re-initiation of thermally-driven venting of fluid on the bank top and accompanying recharge on the slopes. Interpretation of existing chlorinity data, in the light of this change in flow rate, constrain the recent horizontal flow rate to be 10.6 ( 3.4) cm/year. Estimates of flow rate from (234U/238U) and Cl[-] are therefore in agreement and suggest flow rates close to those predicted by thermally-driven models of fluid flow. This agreement supports the idea that flow within the Bahamas Banks is mostly thermally driven and suggests that flow rates on the order of 10 cm/year are typical for carbonate platforms where such flow occurs.

Geochemistry of the gabbroic lithosphere in IODP Holes 304-U1309D and 305-U1309D

IODP Hole U1309D (Atlantis Massif, Mid-Atlantic Ridge 30°N) is the second deepest hole drilled into slow spread gabbroic lithosphere. It comprises 5.4% of olivine-rich troctolites (~ > 70% olivine), possibly the most primitive gabbroic rocks ever drilled at mid-ocean ridges. We present the result of an in situ trace element study carried out on a series of olivine-rich troctolites, and neighbouring troctolites and gabbros, from olivine-rich intervals in Hole U1309D. Olivine-rich troctolites display poikilitic textures; coarse-grained subhedral to medium-grained rounded olivine crystals are included into large undeformed clinopyroxene and plagioclase poikiloblasts. In contrast, gabbros and troctolites have irregularly seriate textures, with highly variable grain sizes, and locally poikilitic clinopyroxene oikocrysts in troctolites. Clinopyroxene is high Mg# augite (Mg# 87 in olivine-rich troctolites to 82 in gabbros), and plagioclase has anorthite contents ranging from 77 in olivine-rich troctolites to 68 in gabbros. Olivine has high forsterite contents (82-88 in olivine-rich troctolites, to 78-83 in gabbros) and is in Mg-Fe equilibrium with clinopyroxene. Clinopyroxene cores and plagioclase are depleted in trace elements (e.g., Ybcpx ~ 5-11 * Chondrite), they are in equilibrium with the same MORB-type melt in all studied rock-types. These compositions are not consistent with the progressively more trace element enriched (evolved) compositions expected from olivine rich primitive products to gabbros in a MORB cumulate sequence. They indicate that clinopyroxene and plagioclase crystallized concurrently, after melts having the same trace element composition, consistent with crystallization in an open system with a buffered magma composition. The slight trace element enrichments and lower Cr contents observed in clinopyroxene rims and interstitial grains results from crystallization of late-stage differentiated melts, probably indicating the closure of the magmatic system. In contrast to clinopyroxene and plagioclase, olivine is not in equilibrium with MORB, but with a highly fractionated depleted melt, similar to that in equilibrium with refractory oceanic peridotites, thus possibly indicating a mantle origin. In addition, textural relationships suggest that olivine was in part assimilated by the basaltic melts after which clinopyroxene and plagioclase crystallized (impregnation). These observations suggest a complex crystallization history in an open system involving impregnation by MORB-type melt(s) of an olivine-rich rock or mush. The documented magmatic processes suggest that olivine-rich troctolites were formed in a zone with large magmatic transfer and accumulation, similar to the mantle-crust transition zone documented in ophiolites and at fast spreading ridges.

(Table 2) Sedimentation and accumulation rates of DSDP Holes 38-337 and 38-338

The modern depositional environment of the deep Norwegian-Greenland Sea is highly asymmetric in an E-W direction because of the hydrography of the surface water masses and because of the more or less permanent pack ice cover of the East Greenland Current regime along the Greenland continental margin. By means of sedimentation rates we have tried to investigate whether this hydrographic asymmetry influenced the sediment input to the Norwegian-Greenland Sea over the past 60 m.y. Sediment input can be quantified if thicknesses of sediment sections accumulated over known time intervals can be measured and if some of their physical properties have been determined. Sedimentation rates have been estimated for Tertiary and Quaternary times, and their temporal as well as their spatial changes are discussed. Basin structure and morphology exerted an important influence on sediment distribution. During the Early Tertiary major sediment source regions in the southern Barents Sea and to the north and west of Iceland could be identified; these source regions supplied the bulk of the sediment fill of the Norwegian-Greenland Sea. Since inception of a "glacial" type sedimentation major elements of the sea surface circulation seem to have controlled the sediment input into this polar and subpolar deep-sea basin.