Geochemistry of ODP Leg 127 igneous rocks

Legs 127 and 128 of the Ocean Drilling Program cored basement samples from two sites in the Yamato Basin (Sites 794 and 797) and one site in the Japan Basin (Site 795) of the Japan Sea. These samples represent sills and lava flows erupted or shallowly intruded in a marine environment during backarc extension and spreading in the middle Miocene. In this paper, we describe the geochemical characteristics of these igneous units using 52 new instrumental neutron activation analyses (INAA), 8 new X-ray fluorescence (XRF) analyses, and previous shipboard XRF analyses. The sills intruded into soft sediment at Sites 794 and 797 were subject to extensive hydrothermal activity, estimated at <230° C under subgreenschist facies conditions, which heavily to totally altered the fine-grained unit margins and moderately to heavily altered the coarse-grained unit interiors. Diagenesis further altered the composition of these igneous bodies and lava flows at Sites 794, 795, and 797, most intensely at unit margins. Our study of two well-sampled units shows that Mg, Ca, Sr, and the large-ion lithophile elements (LILE) mobilized during alteration, and that the concentrations of Y, Yb, and Lu decreased and Ce increased in the most severely altered samples. Nevertheless, our study shows that the rare-earth elements (REE) were relatively immobile in the majority of the samples, even where secondary mixed-layer clays comprised the great majority of the rock. Fresher Yamato Basin samples are compositionally heterogenous tholeiitic basalts and dolerites. At Site 794 in the north-central portion of the basin, Units 1 to 5 (upper basement) comprise mildly light rare-earth element (LREE) enriched basalts and dolerites (chondrite-normalized La/Sm of 1.4-1.8), while the stratigraphically lower Units 6 to 9 are less enriched dolerites with (La/Sm)N of 0.7-1.3. All Site 794 samples lack Nb and Ta depletions and LILE enrichments, lacking a strong subduction-related incompatible element geochemical signature. At Site 797 in the western margin of the basin, two stratigraphically-definable unit groups also occur. The upper nine units are incompatible-element depleted tholeiitic sills and flows with strong depletions of Nb and Ta relative to normal mid-ocean ridge basalt (N-MORB). The lower twelve sills represent LREE-enriched tholeiites (normalized La/Sm ranges from 1.1 to 1.8), with distinctly higher LILE and high field-strength element (HFSE) contents. At Site 795 at the northern margin of the Japan Sea, three eruptive units consist of basaltic andesite to calc-alkaline basalt (normalized La/Sm of 1.1 to 1.5) containing moderate depletions of the HFSE relative to N-MORB. The LILE-depleted nature of these samples precludes their origin in a continental arc, indicating that they more likely erupted within a rifting oceanic arc system. The heterogenous nature of the Japan Sea rocks indicate that they were derived at each site from multiple parental magmas generated from a compositionally heterogenous mantle source. Their chemistry is intermediate in character between arc basalts, MORB, and intraplate basalts, and implies little involvement of continental crust at any point in their genesis. Their flat chondrite-normalized, medium-to-heavy rare earth patterns indicate that the primary magmas which produced them last equilibrated with and segregated from spinel lherzolite at shallow depths (<30 kbar). In strong contrast to their isotopic compositional arrays, subduction-related geochemical signatures are usually poorly defined. No basin-wide temporal or geographic systematics of rock chemistry may be confidently detailed; instead, the data show both intimate (site-specific) and widespread backarc mantle heterogeneity over a narrow (2 Ma or so) range in time, with mantle heterogeneity most closely resembling a "plum-pudding" model.

Diatom stratigraphy of ODP Leg 150 holes

Diatoms are present in middle to lower upper Miocene sections of all holes examined during Leg 150, but are generally absent or in low abundance in Pleistocene to middle upper Miocene sediments. An exception is the alternating diatom-rich, diatom-poor intervals in upper Quaternary sediments. Five new diatom zones, covering an interval from near the lower/middle Miocene boundary to the lower upper Miocene, are proposed. Some of the taxon used to define these zones are also used in zonal schemes for the East Coast of the United States, and allow for correlations to be drawn between this region and Leg 150 sites. Lower Miocene and older levels are not included in this study. Although older Tertiary diatoms are present at some of the sites, dissolution has largely compromised their usefulness as zonal markers.

Hydrocarbon gases in ODP Leg 104 samples

Geochemical studies at three ODP Leg 104 sites on the Wring Plateau help define the distribution of hydrocarbon gases in sediment of this prominent feature of the Norwegian continental margin. Low levels of hydrocarbon gas were encountered in sediment of the outer part of the plateau, but sediment of the inner part of the plateau is very gassy. The molecular composition of inner plateau gases (>99.9% methane) and the carbon isotopic composition of the methane (avg. = -76 per mil relative to the PDB standard) clearly show that the gas is biogenic. Heavier hydrocarbon gases accompany this methane, and their presence is probably a result of both chemical and microbial low-temperature diagenesis. Although these heavier hydrocarbons were not detected in sediment of the outer part of the plateau during shipboard analyses, subsequent shore-based analyses showed that these compounds are present at very low concentrations. Methane in the gassy sediment of the inner part of the plateau may be present as gas hydrates, judging from sedimentological and inorganic geochemical considerations, but no discernible gas hydrates were recovered during drilling.

Carbonat-free sediment components of ODP Leg 115 holes

From the equatorial Indian Ocean, carbonate-free portions of sediment samples of Paleocene to Miocene calcareous oozes and chalks from Sites 707, 709, and 711 were studied using X-ray diffraction measurements and the scanning electron microscope. Downhole variations in biogenic opal, quartz, barite, and clinoptilolite were investigated. The abundance patterns of these major mineral phases show several similarities and may be used for additional lithologic correlations. Variations in biogenic opal contents reflect biogenic silica productivity. Beside the general pattern, a succession in biogenic silica decrease through time is generally recorded since the Oligocene. This succession started earliest at northernmost Site 711 and latest at southernmost Site 707, including Site 709 within these two. Opal-A variations as well as the barite distribution may be influenced by the paleoposition of the sites in relation to the high-productivity zone, which today lies south of the equator. Authigenic clinoptilolite apparently formed in two different modes. In deeper sediment intervals, clinoptilolite was the last mineral phase formed associated with enhanced silica diagenesis. In late Oligocene to middle Miocene sediments, clinoptilolite was the only authigenic silica phase encountered where otherwise strong opal dissolution was observed. The sponge spicules showed special dissolution features probably related to microbiological activity. Silica concretions mainly composed of opal-CT and authigenic quartz occur in carbonate-rich environments and are formed during later diagenesis when burial depth causes the sediments to reach higher temperatures. Opal-CT concretions in carbonate-free siliceous oozes were found at Site 711 and are probably formed during an early stage of silica diagenesis.

Sedimentology of ODP Leg 126 deep-water volcaniclastics

Three sites were drilled in the Izu-Bonin forearc basin during Ocean Drilling Program (ODP) Leg 126. High-quality formation microscanner (FMS) data from two of the sites provide images of part of a thick, volcaniclastic, middle to upper Oligocene, basin-plain turbidite succession. The FMS images were used to construct bed-by-bed sedimentary sections for the depth intervals 2232-2441 m below rig floor (mbrf) in Hole 792E, and 4023-4330 mbrf in Hole 793B. Beds vary in thickness from those that are near or below the resolution of the FMS tool (2.5 cm) to those that are 10-15 m thick. The bed thicknesses are distributed according to a power law with an exponent of about 1.0. There are no obvious upward thickening or thinning sequences in the bed-by-bed sections. Spaced packets of thick and very thick beds may be a response to (1) low stands of global sea level, particularly at 30 Ma, (2) periods of increased tectonic uplift, or (3) periods of more intense volcanism. Graded sandstones, most pebbly sandstones, and graded to graded-stratified conglomerates were deposited by turbidity currents. The very thick, mainly structureless beds of sandstone, pebbly sandstone, and pebble conglomerate are interpreted as sandy debris-flow deposits. Many of the sediment gravity flows may have been triggered by earthquakes. Long recurrence intervals of 0.3-1 m.y. for the very thickest beds are consistent with triggering by large-magnitude earthquakes (M = 9) with epicenters approximately 10-50 km away from large, unstable accumulations of volcaniclastic sand and ash on the flanks of arc volcanoes. Paleocurrents were obtained from the grain fabric of six thicker sandstone beds, and ripple migration directions in about 40 thinner beds; orientations were constrained by the FMS images. The data from ripples are very scattered and cannot be used to specify source positions. They do, however, indicate that the paleoenvironment was a basin plain where weaker currents were free to follow a broad range of flow paths. The data from sandstone fabric are more reliable and indicate that turbidity currents flowed toward 150? during the time period from 28.9 to 27.3 Ma. This direction is essentially along the axis of the forearc basin, from north to south, with a small component of flow away from the western margin of the basin.

Geochemistry of primary and secondary mineral phases in ODP Leg 209 sediments

Primary and secondary mineral phases from Holes 1268A (11 samples), 1272A (9 samples), and 1274A (12 samples) were analyzed by electron microprobe in Bonn and Cologne (Germany). Bulk rock powders of these samples were also analyzed geochemically, including major and trace elements (Paulick et al., 2006, doi:10.1016/j.chemgeo.2006.04.011). Ocean Drilling Program (ODP) Leg 209 Holes 1268A, 1272A, and 1274A differ remarkably in alteration intensity and mineralogy, and details regarding their lithologic characteristics are presented in Bach et al. (2004, doi:10.1029/2004GC000744) and Shipboard Scientific Party (2004, doi:10.2973/odp.proc.ir.209.101.2004). Because of the least altered character of peridotite in Hole 1274A, abundant clinopyroxene, orthopyroxene, olivine, and spinel were analyzed at this site. In Hole 1272A, primary silicates are rare and analyses were restricted to some samples that contain traces of olivine and orthopyroxene. Because of the intensity of alteration, Hole 1268A is devoid of primary phases except spinel. Commonly, alteration is pseudomorphic and serpentinization of olivine and orthopyroxene can be distinguished. Accordingly, compositional variations of the alteration minerals with regard to the precursor minerals are one of the issues investigated in this data report.

Consolidation properties and hydraulic conductivities of sediments from ODP Leg 207 sites

The stress history, permeability, and compressibility of sediments from Demerara Rise recovered during Ocean Drilling Program Leg 207 were determined using one-dimensional incremental load consolidation and low-gradient flow pump permeability tests. Relationships among void ratio, effective stress, and hydraulic conductivity are presented for sampled lithologic units and used to reconstruct effective stress, permeability, and in situ void ratio profiles for a transect of three sites across Demerara Rise. Results confirm that a significant erosional event occurred on the northeastern flank of the rise during the late Miocene, resulting in the removal of ~220 m of upper Oligocene-Miocene deposits. Although Neogene and Paleogene sediments tend to be overconsolidated, Cretaceous sediments are normally consolidated to underconsolidated, suggesting the presence of overpressure. A pronounced drop in permeability occurs at the transition from the Cretaceous black shales into the overlying Maastrichtian-upper Paleocene chalks and clays. The development of a hydraulic seal at this boundary may be responsible for overpressure in the Cretaceous deposits, leading to the lower overconsolidation ratios of these sediments. Coupled with large regional variations in sediment thickness (overburden stresses), the higher permeability overpressured Cretaceous sediments represent a regional lateral fluid conduit on Demerara Rise, possibly venting methane-rich fluids where it outcrops on the margin's northeastern flank.

Geochemical investigations of volcanic ash layers from ODP Leg 119

Geochemical investigations were carried out on 19 discrete ash layers and on 42 dispersed ash accumulations in Oligocene to Pleistocene sediments from Sites 736, 737, 745, and 746 of ODP Leg 119 (Kerguelen Plateau in the southern Indian Ocean). The chemical data obtained from more than 500 single-grain glass analyses allow the characterization of two dominant petrographic rock series. The first consists of transitional- to alkali-basalts, the second mainly of trachytes with subordinated alkali-rhyolites and rhyolites. Chemical correlation with possible source areas indicates that the tephra layers from the northern Kerguelen Plateau Sites 736 and 737 were probably erupted from the nearby Kerguelen Islands. The investigated ash layers clearly reflect the Oligocene to recent changes in the composition of the volcanic material recorded from the Kerguelen Islands. The dispersed ashes from Sites 745 and 746 in the Australian-Antarctic Basin display almost the same range in chemical compositions as those from the north. Heard Island and other sources may have contributed to their formation, in addition to the Kerguelen Islands. Dispersed ash of calc-alkaline composition is most probably derived from the South Sandwich island arc, indicating sea-ice rafting as an important mechanism of transport.

Chemical and Sr isotopic compositions and timing of carbonate mineral precipitation, ODP Leg 115

The strontium isotope ratios of authigenic carbonates from Indian Ocean sea-floor basalts have been used to determine the timing of carbonate mineral precipitation and fluid flow. The samples include calcites from 57.2 Ma crust from Ocean Drilling Project (ODP) Site 715, and calcites, aragonites, and siderites from 63.7 Ma crust from ODP Site 707. At Site 715, calcite precipitation may have begun at any time after the basalts cooled, and it continued until approximately 31 Ma, or 26 m.y. after basalt eruption. At Site 707, aragonite and siderite did not begin to precipitate until about 36 Ma, almost 30 m.y. after basalt eruption, and continued to precipitate until at least 30 and 28 Ma, respectively. Calcite precipitation began at approximately 32 Ma and continued until 22 Ma. These ages suggest that vein mineral deposition and low-temperature fluid circulation in the ocean crust may continue for much longer periods of time than previously observed.

Oligocene-Miocene calcareous nannofossils in ODP Leg 149 holes

During Ocean Drilling Program (ODP) Leg 149, five sites were drilled on the Iberia Abyssal Plain in the northeastern Atlantic Ocean. Both Mesozoic and Cenozoic sediments were recovered. Oligocene to Miocene sediments were cored at deepwater Sites 897, 898, 899, and 900. Except for a few intervals, occurrences of generally abundant and well-preserved calcareous nannofossils suggest that the deposition of the turbidite-type sediments occurred above the calcite compensation depth (CCD). One major unconformity in the middle late Miocene is present. Detailed quantitative analyses of calcareous nannofossils are used to determine the changes occurring among the nannoflora in relation to sea-level variation. A succession of 89 biohorizons from the early Oligocene to the late Miocene are defined by combining the biostratigraphic results of the four sites studied in the Iberia Abyssal Plain. One new genus and eight new species are described: Camuralithus, Camuralithus pelliculatus, Ericsonia detecta, Helicosphaera limasera, Sphenolithus akropodus, Sphenolithus aubryae, Sphenolithus cometa, Reticulofenestra circus, and Syracosphaera lamina. Two new variations and seven new combinations are also introduced.