Hydrogen, carbon, and oxygen isotope ratios of interstitial fluides of ODP Leg 104 holes

Carbon, hydrogen, and oxygen isotope ratios determined on 32 squeezed interstitial fluid samples show remarkable variations with depth. For the most part these variations are related to diagenetic and alteration reactions taking place in the sediments, and in the underlying basalts. delta13C SumCO2 depth distributions at Sites 642 and 643 are the result of mixing of original SumCO2 of the paleo bottom water with SumCO2 released by remineralization of organic matter. At Site 644, where sulfate exhaustion occurs, the processes of methanogenesis by CO2 reduction and anaerobic methanotrophy strongly influence the delta13C SumCO2 distribution. Hydrogen and oxygen isotopes roughly covary, and become enriched in 16O and1H with depth. This effect is most pronounced at Sites 642 and 643, possibly due to the influence of the directly underlying basalts. Isotope depletions at Site 644 are much lower, corresponding to the greater sediment depth to basement. The alternative, that the O, H isotope shifts are due primarily to autochthonous diagenetic and exchange reactions, is not supported by the data available.

Miocene to Holocene diatom biostratigraphy of ODP Leg 105 sites

Diatoms occur sporadically in lower Miocene to Holocene sediments recovered at ODP Site 645 and in upper Pliocene to Holocene sediments at ODP Site 646. The diatom assemblage at Site 645 contains rare stratigraphic indicators. Fragmentation of frustules and the occurrence of species characteristic of high-latitude shelf, upper-slope environments suggest current transportation from the shelf. The diatom abundance and preservation at Site 646 probably reflect climatic changes and are also affected by dissolution, but it is not possible to detect the dominant factor. Therefore, the stratigraphic ranges of the primary and secondary biostratigraphic indicators are often unreliable.

Geochemistry of DSDP Leg 65 basalts

Leg 65 of the Deep Sea Drilling Project successfully recovered basalts from four sites in the mouth of the Gulf of California, thus completing a transect begun during Leg 64 from the continental margin of Baja California to the east side of the East Pacific Rise (EPR). Sixty-three whole-rock samples from Sites 482, 483, and 485 have been analyzed by X-ray fluorescence techniques, and a further eleven samples by instrumental neutron-activation techniques, in order to assess magma variability within and between sites. Although the major element compositions and absolute hygromagmatophile (HYG) element abundances are quite variable, all of the basalts are subalkaline tholeiites exhibiting strong more-HYG element (e.g., Rb, La, Nb, Ta) depletion (LaN/YbN ~ 0.4; Nb/Zr ~ 0.02; Ba/Zr ~ 0.23; Th/Hf ~ 0.05). These ratios, together with La/Ta ratios of 20 and Th/Ta ratios of 1.25, demonstrate that the Leg 65 basalts resemble the depleted "N-type" ocean ridge basalts recovered from the Mid-Atlantic Ridge (MAR) at 22 °N and other sections of the EPR. Zr/Ti, Zr/Y, and La/Yb ratios increase with increasing fractionation. It is clear that the basalts recovered from Sites 482, 483, and 485 were all derived from a compositionally similar source and that the compositional differences observed between lithological units can be explained by varying degrees of open system fractional crystallization (magma mixing) in subridge magma chambers. The basaltic rocks recovered from Site 474 near the margin of Baja California, and Sites 477, 478, and 481 in the Guaymas Basin, all drilled during Leg 64, have consistently higher Th/Hf, La/Sm, Zr/Ti, and Zr/Y ratios and higher absolute Sr contents than the Leg 65 basalts. While some of these variations may be explained by different conditions of partial melting, it is considered more likely that the mantle source underlying the Guaymas Basin is chemically distinct from that feeding the EPR at the mouth of the Gulf. These source variations probably reflect the complex tectonic setting of the Gulf of California, the magmas formed at the inception of spreading and in the central part of the Gulf containing a minor but significant component of sub-continental (calc-alkaline) material.

Geochemical composition and atomic formulas of saponites, celadonites and carbonates from ODP Leg 168 sites

With this study, we investigate the mineralogical variations associated with the low-temperature (<100°C) alteration of normal tholeiitic pillow basalts varying in age from 0.8 to 3.5 Ma. Their alteration intensity varies systematically and is related to several factors, including (1) the aging of the igneous crust, (2) the increase of temperatures from the younger to the older sites, measured at the sediment/basement interface, (3) the local and regional variations in lithology and primary porosity, and (4) the degree of pillow fracturing. Fractures represent the most important pathways that allow significant penetration of fluids into the rock and are virtually the only factor controlling the alteration of the glassy rim and the early stages of pillow alteration. Three different alteration stages have been recognized: alteration of glassy margin, oxidizing alteration through fluid circulation in fracture systems, and reducing alteration through diffusion. All the observed mineralogical and chemical variations occurring during the early stages of alteration are interpreted as the result of the rock interaction with "normal," alkaline, and oxidizing seawater, along preferential pathways represented by the concentric and radial crack systems. The chemical composition of the fluid progressively evolves while moving into the basalt, leading to a reducing alteration stage, which is initially responsible for the precipitation of Fe-rich saponite and minor sulfides and subsequently for the widespread formation of carbonates. At the same time, the system evolved from being "water dominated" to being "rock dominated." No alteration effects in pillow basalts were observed that must have occurred at temperatures higher than those measured during Leg 168 at the basement/sediment interface (e.g., between 15° and 64°C).

Volcaniclastic sediments of ODP Leg 136 sites

Sediment cores recovered from three holes drilled during Ocean Drilling Program Leg 136 include volcaniclastics probably derived from the Hawaiian islands. The volcaniclastics shallower than 10 meters below seafloor are fresh and are composed of basaltic glass (sideromelane), basaltic fragments (mainly tachylite), plagioclase, olivine, pyroxene, and opaque minerals. Most of these glasses are probably products of hydrovolcanism. Visibly, some of these volcaniclastics are recognized as bedded ash layers having thicknesses that range from 5 to 10 cm. However, many volcaniclastics are disrupted by bioturbation to some degree, and are sometimes totally mixed with ambient brown clays. No visible correlative ash layer among these holes was found. It seems that many ash layers thinner than the bedded layers were disrupted by bioturbation because of the low sedimentation rate of volcaniclastics. The volcaniclastics were probably transported one of two ways: through air fall and pelagic settling or through turbidity-current transport. Other archipelagic apron volcaniclastic sediments of volcanic seamounts suggest that turbidite transport is the favored explanation of origin.

Ice-rafted debris of Late Cenozoic sediments from ODP Leg 104 holes

The abundance and composition of the upper Cenozoic terrigenous coarse-sand fraction (250 µm-2 mm) at ODP Sites 642, 643, and 644 were investigated to date the onset of significant ice-rafting in the Norwegian Sea, establish the regional chronology of ice-rafting, and determine the relative importance of global vs. regional controls on ice-rafting in this area. The first input of ice-rafted debris (IRD) occurs at approximately 2.9 Ma, with significant ice-rafting beginning at about 2.5 Ma. IRD abundances increase significantly in sediments younger than 0.9 Ma at all three holes, indicating climatic deterioration in the late Pleistocene. Differences in the timing of this IRD increase between holes result from regional patterns of IRD supply and surface circulation. Variations in IRD sources and dispersal patterns may also explain the slightly higher background level of IRD abundance at Hole 642B, a seaward site. Major peaks in the generalized IRD records from the Norwegian Sea are tentatively correlated to glacial stages or glacial-to-interglacial transitions in the globally defined oxygen isotope record. This correlation indicates the effect of global conditions on the regional climate of the Norwegian Sea, although the detailed IRD records at these sites are also affected by local/regional processes (e.g., circulation patterns and source area differences).

Radiolarians from ODP Leg 116 holes

Cores recovered from three sites of Leg 116 were studied for radiolarians. Generally, radiolarians were absent from most samples prepared for examination. Moderate to well-preserved radiolarian assemblages are found only in the uppermost one or two cores that were the focus of this study. All of the radiolarian assemblages in the upper cores belong to the Buccinosphaera invaginata Zone of latest Quaternary age. However, there is one stratum where a few Miocene radiolarians are reworked into the modern assemblages. Local seamounts are suggested sources for the reworked radiolarians.

Ice-rafted debris in sites of ODP Leg 114

All holes drilled during Leg 114 contained ice-rafted debris. Analysis of samples from Hole 699A, Site 701, and Hole 704A yielded a nearly complete history of ice-rafting episodes. The first influx of ice-rafted debris at Site 699, on the northeastern slope of the Northeast Georgia Rise, occurred at a depth of 69.94 m below seafloor (mbsf) in sediments of early Miocene age (23.54 Ma). This material is of the same type as later ice-rafted debris, but represents only a small percentage of the coarse fraction. Significant ice-rafting episodes occurred during Chron 5. Minor amounts of ice-rafted debris first reached Site 701, on the western flank of the Mid-Atlantic Ridge (8.78 Ma at 200.92 mbsf), and more arrived in the late Miocene (5.88 Ma). The first significant quantity of sand and gravel appeared at a depth of 107.76 mbsf (4.42 Ma). Site 704, on the southern part of the Meteor Rise, received very little or no ice-rafted debris prior to 2.46 Ma. At this time, however, the greatest influx of ice-rafted debris occurred at this site. This time of maximum ice rafting correlates reasonably well with influxes of ice-rafted debris at Sites 701 (2.24 Ma) and 699 (2.38 Ma), in consideration of sample spacing at these two sites. These peaks of ice rafting may be Sirius till equivalents, if the proposed Pliocene age of Sirius tills can be confirmed. After about 1.67 Ma, the apparent mass-accumulation rate of the sediments at Site 704 declined, but with major fluctuations. This decline may be the result of a decrease in the rate of delivery of detritus from Antarctica due to reduced erosive power of the glaciers or a northward shift in the Polar Front Zone, a change in the path taken by the icebergs, or any combination of these factors.

Geochemistry and minerals at DSDP LEg 58 Holes

Leg 58 successfully recovered basalt at Sites 442, 443, and 444, in the Shikoku Basin, and at Site 446 in the Daito Basin. Only at Site 442 did penetration reach unequivocal oceanic layer 2; at the other sites, only off-axis sills and flows were sampled. Petrographic observations indicate that back-arc basalts from the Shikoku Basin, with the exception of the kaersutite-bearing upper sill at Site 444, are mineralogically similar to basalts being erupted at normal mid-ocean ridges. However, the Shikoku Basin basalts are commonly very vesicular, indicating a high volatile content in the magmas. Site 446 in the Daito Basin penetrated a succession of 23 sills which include both kaersutite-bearing and kaersutite-free basalt varieties. A total of 187 samples from the four sites has been analyzed for major and trace elements using X-ray-fluorescence techniques. Chemically, the basalts from Sites 442 and 443 and the lower sill of Site 444 are subalkaline tholeiites and resemble N-type ocean-ridge basalts found along the East Pacific Rise and at 22° N on the Mid-Atlantic Ridge (MAR), although they are not quite as depleted in certain hygromagmatophile (HYG) elements. They do not show any chemical affinities with island-arc tholeiites. The basalts from Site 446 and from the upper sill at Site 444 show alkaline and tholeiitic tendencies, and are enriched in the more-HYG elements; they chemically resemble enriched or E-type basalts and their differentiates found along sections of the MAR (e.g., 45°N) and on ocean islands (e.g., Iceland and the Azores). Most of the intra-site variation may be attributed to crystal settling within individual massive flows and sills, to high-level fractional crystallization in sub-ridge magma chambers, or, where there is evidence of a long period of magmatic quiescence between units, to batch partial melting. However, the basalts from Sites 442 and 443 and from the lower sill at Site 444 cannot easily be related to those from Site 446 and the upper sill at Site 444, and it is possible that the different basalt types were derived from chemically distinct mantle sources. From comparison of the Leg 58 data with those already available for other intra-oceanic back-arc basins, it appears that the mantle sources giving rise to back-arc-basin basalts are chemically as diverse as those for mid-ocean ridges. In addition, the high vesicularity of the Shikoku Basin basalts supports previous observations that the mantle source of back-arc-basin basalts may be contaminated by a hydrous component from the adjacent subduction zone.

Diatom abundances in ODP Leg 114 holes

The practically continuous, paleomagnetically dated late Gauss-Brunhes sediment profiles of ODP Sites 699 and 701, south of the present Polar Front Zone (PFZ), and Site 704, north of the present PFZ, are used for a high-resolution study of abundance fluctuations of eight stratigraphic marker species in space and time. Ecological restrictions and preferences of the diatom species Hemidiscus karstenii, Actinocyclus ingens f. planus, Thalassiosira elliptipora, Thalassiosira kolbei, Thalassiosira vulnifica, Simonseniella barboi, Cosmiodiscus insignis, and Nitzschia weaveri are deduced. The ages of their first abundant appearance datums (FAAD), last-appearance datums (LAD), and last abundant appearance datums (LAAD) at the three sites are determined. The interpolated datum ages agree relatively well with those determined by other authors, if one interprets most of their LADs as LAADs. FAADs and LAADs produce more accurate datums than LADs. For the late Matuyama (younger than approximately 2.0 Ma), when PFZ fluctuations effected all three site sites, the datum ages determined agree within the methodically caused limits of accuracy for each datum. For the early Matuyama (older than approximately 2.0 Ma) the results can be interpreted as either that the ages of the FAAD of T. kolbei and LAAD of T. vulnifica datums determined at Sites 699 and 701 are more reliable or that these datums are diachronous between these two sites and Site 704. Such a diachroneity could be caused by different paleoceanographic conditions (stable subantarctic conditions over Site 704 and stable antarctic conditions over Sites 699 and 701). A few taxonomic changes were necessary. One new genus is defined (Simonseniella gen. nov.) and five new combinations are proposed: Simonseniella barboi (Brun) comb, nov., Simonseniella praebarboi (Schrader) comb, nov., Simonseniella curvirostris (Jousé) comb, nov., Thalassiosira elliptipora (Donahue) comb, nov., and Thalassiosira vulnifica (Gombos) comb. nov.

Geochemistry of carbonate cements of ODP Leg 112 samples

The evolution of pore fluids migrating through the forearc basins, continental massif, and accretionary prism of the Peru margin is recorded in the sequence of carbonate cements filling intergranular and fracture porosities. Petrographic, mineralogic, and isotopic analyses were obtained from cemented clastic sediments and tectonic breccias recovered during Leg 112 drilling. Microbial decomposition of the organic-rich upwelling facies occurs during early marine diagenesis, initially by sulfate-reduction mechanisms in the shallow subsurface, succeeded by carbonate reduction at depth. Microcrystalline, authigenic cements formed in the sulfate-reduction zone are 13C-depleted (to -20.1 per mil PDB), and those formed in the carbonate-reduction zone are 13C-enriched (to +19.0 per mil PDB). Calcium-rich dolomites and near-stoichiometric dolomites having uniformly heavy d18O values (+2.7 to +6.6 per mil PDB) are typical organic decomposition products. Quaternary marine dolomites from continental-shelf environments exhibit the strongest sulfate-reduction signatures, suggesting that Pleistocene sea-level fluctuations created a more oxygenated water column, caused periodic winnowing of the sediment floor, and expanded the subsurface penetration of marine sulfate. We have tentatively identified four exotic cement types precipitated from advected fluids and derived from the following diagenetic environments: (1) meteoric recharge, (2) basalt alteration, (3) seafloor venting and (4) hypersaline concentration. Coarsely crystalline, low-magnesium (Lo-Mg) calcite cements having pendant and blocky-spar morphologies, extremely negative d18O values (to -7.5 per mil PDB), and intermediate d13C values (-0.4 per mil to +4.6 per mil PDB) are found in shallow-marine Eocene strata. These cements are evidently products of meteoric diagenesis following subaerial emergence during late Eocene orogenic movements, although the strata have since subsided to greater than 4,000 m below sea level. Lo-Mg calcite cements filling scaly fabrics in the late Miocene accretionary prism sediments are apparently derived from fluids having lowered magnesium/calcium (Mg/Ca) and 18O/16O ratios; such fluids may have reacted with the subducting oceanic crust and ascended through the forearc along shallow-dipping thrust faults. Micritic, high-magnesium (Hi-Mg) calcite cements having extremely depleted d13C values (to -37.3%c PDB), and a benthic fauna of giant clams (Calyptogena sp.) supported by a symbiotic, chemoautotrophic metabolism, provide evidence for venting of methane-charged waters at the seafloor. Enriched d18O values (to +6.6%c PDB) in micritic dolomites from the continental shelf may be derived from hypersaline fluids that were concentrated in restricted lagoons behind an outer-shelf basement ridge, reactivated during late Miocene orogenesis.