(Table 1) Clay mineralogy at DSDP Sites 86-576 and 86-578

Late Cretaceous and Cenozoic sediments deposited on the eastern and western sides of the Shatsky Rise show similar clay assemblages of chlorite, illite, mixed layers, smectite, kaolinite, and palygorskite, and a similar vertical differentiation into three units. The deep-sea pelagic red clay is dominated by terrigenous components, which suggests that diagenesis is minor in this part of the western North Pacific and that eolian supply is very important. The role of the Shatsky Rise as a submarine barrier is of minor importance. The volcanic contribution to the clay component appears very small, as in some other parts of the Pacific Ocean. Stratigraphic correlations between Sites 576 and 578, which can be made from mineralogical data, partly offset the rareness of biostratigraphic markers.

Depth and ages of calcareous nannofossil events from ODP Leg 184 sites, South China Sea

Sites 1146 and 1148 of Ocean Drilling Program Leg 184, in the South China Sea (SCS), comprise long sediment sections with a time span from the early Oligocene to the Pleistocene. Calcareous nannofossils from these two sites were biostratigraphically studied. We recognized 53 early Oligocene to Pleistocene events that are commonly found in open sea areas and can therefore be correlated within a large geographic range. This study also revealed that a few conventionally used nannofossil events are not suitable for the SCS, and further evaluation is needed. The lower Oligocene to Pleistocene sequences recovered at Sites 1146 and 1148 were subdivided into the 4 Paleogene zones and 21 Neogene to Quaternary zones of Martini, in correlation with the Paleogene to Quaternary zones of Okada and Bukry. This provided a lower Oligocene through Pleistocene nannofossil biostratigraphic framework. A significant unconformity was recognized in the Oligocene-Miocene transition, in which the upper part of Oligocene Zone NP25 and lower part of Miocene Zone NN1 were missing. The time span of the unconformity was estimated to be ~1 m.y. Very high sedimentation rates were seen in the Oligocene, relative low values were seen in the Miocene, and the highest values were seen in the Pleistocene, which was believed to be the result of tectonic and sedimentation history of the SCS.

(Table A1) Isotopic ratios of Sr, Nd, and Pb for sediments in ODP Leg 138 sites

The provenance of eolian dust supplied to deep-sea sediments has the potential to offer insights into changes in past atmospheric circulation. Specifically, measuring temporal changes in dust provenance can shed light on changes in the mean position of the Intertropical Convergence Zone (ITCZ), a region acting as a barrier separating wind-blown material derived from northern versus southern hemisphere sources. Here we have analyzed Nd, Sr, and Pb isotope ratios in the operationally-defined detrital component extracted from deep-sea sediments in the eastern equatorial Pacific (EEP) along a meridional transect at 110°W from 3°S to 7°N (ODP Leg 138, sites 848-853). Sr isotope results show that barite Sr has a significant influence on 87Sr/86Sr isotope ratios of samples in the upwelling zone of the EEP. However, sites located >3° or more away from the equator (sites 852 and 853) are believed to not be affected by barite Sr and provide useful detrital Sr signals. 208Pb/206Pb and 207Pb/206Pb ratios in all cores fall into the Pb-isotope space of five potential dust sources (Asia, North and Central/South America, Sahara, and Australia), with no distinct isotopic fingerprinting of the dominant source(s). epsilon-Nd values were most valuable for discerning detrital source provenance, and their values at all sites, ranging from ~5.46 to ~3.25, were more unradiogenic for sediments deposited during the last glacial than for those deposited during the Holocene. There are distinct latitudinal trends in the epsilon-Nd values, with more radiogenic values further south and less radiogenic values further north, excluding site 848. This distinction holds true for both Holocene and last glacial periods. For the most southerly site, 848, we invoke, for the first time, a distinct southern hemisphere Australian source as being responsible for the unradiogenic Nd isotope ratios. Both average last glacial and Holocene epsilon-Nd values show similar sharp gradients along the transect between 5.29°N and 2.77°N, suggesting little movement of the glacial ITCZ in the EEP. However, during the deglacial, this gradient is stronger and shifted further north between 5.29°N and 7.21°N, suggesting a more northerly, possibly stronger, deglacial ITCZ.

Amino acid concentrations in interstitial waters from ODP Sites 113-689 and 113-690

Biogenic calcareous and siliceous sediments were drilled at ODP Sites 689 and 690 on the Maud Rise, Antarctic Ocean. We analyzed dissolved combined amino acids (DCAA) and dissolved free amino acids (DFAA) in interstitial waters in order to characterize the amino acids in dissolved organic matter. The DFAA was predominant over the DCAA in interstitial waters at Sites 689 and 690, which contradicted the previous results from interstitial water and seawater studies. The DCAA in the interstitial waters probably originated from calcareous biogenic debris with less amounts of siliceous debris. Although glutamic acid constituted 41% of the total concentration of DCAA, it accounted for only 1% of the total concentration of DFAA due to the adsorption and/or reaction with biogenic carbonate. Ornithine, a nonprotein amino acid, is a decomposed product of arginine and made up 17 mol% of the total DFAA and. The total hydrolyzable amino acids (=DCAA + DFAA) accounted for 5 to 28% of the dissolved organic carbon (DOC) concentration, which implied that high molecular weight organic matter was a major contributor for the DOM (dissolved organic matter) in interstitial waters. Fairly positive correlation between the dissolved manganese and the total DCAA values suggested that the redox condition plays a significant role in controlling the total DCAA content. A small decrease in the sulfate concentration in the interstitial waters from both sites suggested fairly low microbial activity by sulfate-reducing bacteria.

(Table 1) Percentage of non-opaque heavy minerals, heavy residue, magnetite, and opaque heavy minerals, DSDP Sites 58-445 and 58-446

Heavy-mineral analyses were made for 39 samples, 27 from DSDP Site 445 and 12 from Site 446. About one-fourth of the samples were so loose that they were easily disaggregated in water. The amount of heavy residue and the magnetite content of the heavy fraction were very high, 0.2 to 44 per cent and (on the average) more than 20 per cent, respectively. Among the non-opaque heavy minerals, common hornblende (0 to 80%) and augite (0 to 98%) are most abundant. Pale-green and bluish-green amphiboles (around 10%) and the epidote group (a few to 48%) are next in abundance. Euhedral apatite and biotite and irregularly shaped chromite are not abundant, but are present throughout the sequence. Hacksaw structure is developed in pale-green amphibole and augite. At Site 445, a fair amount of chlorite and a few glauconite(?) grains are present from Core 445-81 downward. The content of common hornblende and opaque minerals also changes from Core 445-81 downward. A geological boundary may exist between Cores 445-77 and 445-81. Source rocks of the sediments at both sites were basaltic volcanic rocks (possibly alkali suite), schists, and ultramafic rocks. The degree of lithification and amount of heavy residue, and the content of magnetite, non-opaque heavy minerals (excluding mafic minerals), and mafic minerals in the cores were compared with Eocene, Oligocene, and Miocene sandstones of southwest Japan. In many respects, the sediments at Sites 445 and 446 are quite different from those of southwest Japan. From the early Eocene to the early Miocene, the area of these sites belonged to a different geologic province than southwest Japan.

Paleogene and early Neogene planktonic foraminifera of ODP sites 119-738 and 119-744

A virtually complete composite history of Cenozoic pelagic sedimentation was recovered from ODP Sites 738 (62°43' S) and 744 (61°35' S), drilled during Leg 119 on the Kerguelen Plateau. An excellent magnetobiochronologic record was obtained from upper Eocene through Holocene sediments at Site 744, and an expanded lower Paleocene through lower Oligocene sequence was cored at Hole 738. Analysis of the stratigraphic distribution of over 125 planktonic foraminifer taxa from these sites reveals changes in species composition that were strongly influenced by the climatic evolution of Antarctic water masses. Early Paleocene planktonic foraminifer assemblages are nearly identical in species composition to coeval assemblages from low and middle latitude sites, showing the same patterns of post-extinction recovery and taxonomic radiation. Biogeographic isolation, revealed by the absence of tropical keeled species, became apparent by late early Paleocene time. Diversity increased near the Paleocene/Eocene boundary when keeled morozovellids immigrated to the Kerguelen Plateau. Greatest diversity (23 species) was achieved by early Eocene time, corresponding to a Cenozoic warming maximum that has been recognized in lower Eocene deep sea and terrestrial sediments worldwide. A gradual decline in diversity from the late early through middle Eocene, primarily due to the disappearance of acarininids, parallels the record of cooling paleotemperatures in Southern Ocean surface waters. Chiloguembelina-dominated assemblages appeared in the late middle Eocene and persisted through the early Oligocene as Antarctic surface waters became thermally isolated. Late Eocene and early Oligocene assemblages exhibit considerably lower diversity than the older Eocene faunas, and were dominated by chiloguembelinids, subbotinids, and catapsydracids during a time of pronounced climatic cooling and development of continental glaciation on East Antarctica. The small foraminifer Globigerinit? juvenilis replaced chiloguembelinids as the dominant taxon during the late Oligocene. Diversity increased slightly toward the end of the late Oligocene with new appearances of several tenuitellid, globoturborotalitid, and globigerinid species. The trend toward diminishing planktonic foraminifer diversity was renewed during the late early Miocene as siliceous productivity increased in the Antarctic surface waters, culminating with the reduction to nearly monospecific assemblages of Neogloboqu?drin? p?chyderm? that occur in Pliocene-Holocene biosiliceous sediments. An Antarctic Paleogene zonal scheme previously devised for ODP Sites 689 and 690 in the Weddell Sea is used to biostratigraphically subdivide the Kerguelen Plateau sequence. The definition of one Antarctic Paleogene biozone is modified in the present study to facilitate correlation within the southern high latitudes. The ages of 13 late Eoceneearly Miocene datum events are calibrated based on a magnetobiochronologic age model developed for Site 744.

Mineral composition and experimental results from XRD analyses of sediments from ODP Leg 190 sites

X-ray diffraction analyses of the clay-sized fraction of sediments from the Nankai Trough and Shikoku Basin (Sites 1173, 1174, and 1177 of the Ocean Drilling Program) reveal spatial and temporal trends in clay minerals and diagenesis. More detrital smectite was transported into the Shikoku Basin during the early-middle Miocene than what we observe today, and smectite input decreased progressively through the late Miocene and Pliocene. Volcanic ash has been altered to dioctahedral smectite in the upper Shikoku Basin facies at Site 1173; the ash alteration front shifts upsection to the outer trench-wedge facies at Site 1174. At greater depths (lower Shikoku Basin facies), smectite alters to illite/smectite mixed-layer clay, but reaction progress is incomplete. Using ambient geothermal conditions, a kinetic model overpredicts the amount of illite in illite/smectite clays by 15%-20% at Site 1174. Numerical simulations come closer to observations if the concentration of potassium in pore water is reduced or the time of burial is shortened. Model results match X-ray diffraction results fairly well at Site 1173. The geothermal gradient at Site 1177 is substantially lower than at Sites 1173 and 1174; consequently, volcanic ash alters to smectite in lower Shikoku Basin deposits but smectite-illite diagenesis has not started. The absolute abundance of smectite in mudstones from Site 1177 is sufficient (30-60 wt%) to influence the strata's shear strength and hydrogeology as they subduct along the Ashizuri Transect.

Mineral composition, major element oxides and trace element concentration of sediments from ODP Leg 180 sites

Middle Miocene to Holocene fine-grained argillaceous sediments (clays, claystones/muds, and mudstones), which volumetrically dominated the sediment recovery in the Woodlark Basin during Leg 180, were chemically analyzed for major elements, trace elements, and some rare earth elements by X-ray fluorescence. Selected samples also underwent X-ray diffraction (XRD) analysis for mineral determination. The results shed light on sediment provenance when combined with shipboard sediment descriptions, smear slide study, and XRD. The oldest sediments recovered (Site 1108) of middle-late Miocene age include volcanogenic muds with distinctive high MgO and K2O, indicative of a relatively basic calc-alkaline source related to an inferred Miocene forearc succession. The forearc basement, composed of diabase and basalt, was locally exposed (Site 1109) and eroded in the late Miocene (<5.4-9.93 Ma), giving rise to fluvial conglomerates (Sites 1109, 1115, and 1118). Chemically distinctive fine-grained claystones and siltstones (with relatively high Ti, low K) are compatible with derivation from tropically weathered basic igneous rocks, correlated with the Paleogene Papuan ophiolite. Overlying latest Miocene-Pleistocene fine-grained sediments throughout the Woodlark Basin were partly derived from calc-alkaline volcanic sources. However, relatively high abundances of Al2O3 and related element oxides (K2O and Na2O) and trace elements (e.g., Rb and Y) reflect an additional terrigenous input throughout the basin, correlated with pelitic metamorphic rocks exposed on Papua New Guinea and adjacent areas. In addition, sporadic high abundances of Cr and Ni, some other trace metals, and related minerals (talc, crysotile, and chlorite) reflect input from an ophiolitic terrain dominated by ultramafic rocks, correlated with the Paleogene Papuan ophiolite. The source areas possibly included serpentinized ultramafic ophiolitic rocks exposed in the Papua New Guinea interior highlands. Chemical evidence further indicates that fine-grained terrigenous sediment reached the Woodlark Basin throughout its entire late Miocene-Holocene history. Distinctive high-K volcanogenic muds rich in tephra and volcanic ash layers that appear at <2.3 Ma (Sites 1109 and 1115) are indicative of high-K calc-alkaline volcanic centers, possibly located in the Dawson Strait, Moresby Strait, or Dobu Seamount area. Chemical diagenesis of fine-grained sediments within the Woodlark Basin is reflected in clay neomorphism and localized formation of minerals including dolomite, ankerite, and zeolite but has had little effect on the bulk chemical composition of most samples.

Paleomagnetic characterization and age of several ODP Leg 198 sites, Shatsky Rise

Shatsky Rise, a medium-sized large igneous province in the west Central Pacific Ocean, has three main topographic highs that preserve a thick sedimentary record from Cretaceous through Cenozoic. During Ocean Drilling Program (ODP) Leg 198 to Shatsky Rise, a total of ~768 m of late Miocene-Holocene sediments was recovered from six sites. Sites 1207 and 1208 were drilled on the Northern and Central Highs, respectively, and yielded expanded late Miocene-Holocene sequences. Sites 1209, 1210, 1211, and 1212 were drilled on the Southern High and yielded shorter sequences of similar age. Clearly interpretable magnetic stratigraphies were obtained from all sites using the shipboard pass-through magnetometer. These results were augmented using discrete sample cubes (7 cm**3) collected shipboard and measured postcruise. Miocene age sediments are separated by a hiatus from Oligocene, Eocene, and Cretaceous age sediments beneath. An astrochronological age model was developed for the six sites based on cycles observed in reflectance data, measured shipboard. This age model is in good agreement with published astrochronological polarity chron ages in the 1 to 6 Ma interval.

Temperature and d18O measurements from different ODP Sites at the shelf and upper slope of the Peru Margin

The first experimentally determined temperature dependent oxygen-18 fractionation factor between dolomite and water at low temperatures [Vasconcelos et al. 1995 doi:10.1130/G20992.1] allows now the precise calculation of temperatures during early diagenetic dolomite precipitation. We use d18O values of early diagenetic dolomite beds sampled during ODP Legs 112 and 201 on the Peru continental margin (Sites 1227, 1228 and 1229) [Meister et al. 2007, doi:10.1111/j.1365-3091.2007.00870.x] to calculate paleo-porewater temperatures at the time of dolomite precipitation. We assumed unaltered seawater d18O values in the porewater, which is supported by d18O values of the modern porewater presented in this study. The dolomite layers in the Pleistocene part of the sedimentary columns showed oxygen isotope temperatures up to 5 °C lower than today. Since Sites 1228 and 1229 are located at 150 and 250 m below sealevel, respectively, their paleo-porewater temperatures would be influenced by considerably colder surface water during glacial sealevel lowstands. Thus, Pleistocene dolomite layers in the Peru Continental margin probably formed during glacial times. This finding is consistent with a model for dolomite precipitation in the Peru Margin recently discussed by Meister et al. [Meister et al. 2007, doi:10.1111/j.1365-3091.2007.00870.x], where dolomite forms episodically at the sulphate methane interface. It was shown that the sulphate methane interface migrates upwards and downwards within the sedimentary column, but dolomite layers may only form when the sulphate-methane interface stays at a fixed depth for a sufficient amount of time. We hypothesize that the sulphate-methane interface persists within TOC-rich interglacial sediments, while this zone is buried by TOC-poor sedimentation during glacial times. Thus, the presented oxygen isotope data provide additional information on the timing of early diagenetic dolomite formation and a possible link between episodicity in dolomite formation and sealevel variations. A similar link between early diagenesis and oceanography may also explain spacing of dolomite layers in a Milankovitch type pattern observed in the geological record, such as in the Miocene Monterey Formation.

Eolian grain-size record of early Paleogene sediments from DSDP Hole 22-215 and ODP Leg 208 sites

To date, the only Southern Hemisphere eolian grain-size record constructed for the early Paleogene comes from Deep Sea Drilling Project Site 215. Ten early Paleogene sediment samples from Site 215 were collected and processed to show that the existing eolian grain-size record at this site can be reproduced. Five samples each from Ocean Drilling Program Sites 1263 and 1267 were similarly examined to test the possibility of generating new Southern Hemisphere eolian grain-size records for the early Paleogene. Our results indicate that an eolian grain-size signal can be constructed at Walvis Ridge, although the record will be complicated by hemipelagic terrigenous inputs. Further, we assert that a record generated at a site located on the deep flanks of Walvis Ridge is particularly susceptible to hemipelagic influence.

Physical properties of ODP Sites 123-765 and 123-766

During Ocean Drilling Program Leg 123, two sites were drilled in the deep Indian Ocean. Physical properties were measured in soft Quaternary and Lower Cretaceous sediments to relatively fresh, glass-bearing pillow lavas and massive basalts. Porosities ranged from 89% near the seafloor to 1.6% for the dense basalts. This self-consistent set of measurements permitted some descriptive models of physical properties to be more rigorously tested than before. Predictive relationships between porosity and compressional-wave velocity have generally been based upon the Wyllie time average equation. However, this equation does not adequately describe the actual relationship between these two parameters, and many have attempted to improve it. In most cases, models were derived by testing them against a set of data representing a relatively narrow range of porosity values. Similarly, the use of the Wyllie equation has often been justified by a pseudolinear fit to the data over a narrow range of porosity values. The limitations of the Wyllie relationship have been re-emphasized here. A semi-empirical acoustic impedance equation is developed that provides a more accurate porosity-velocity transform, using realistic material parameters, than has hitherto been possible. A closer correlation can be achieved with this semi-empirical relationship than with more theoretically based equations. In addition, a satisfactory empirical equation can be used to describe the relationship between thermal conductivity and porosity. If enough is known about core sample lithologies to provide estimates of the matrix and pore water parameters, then these predictive equations enable one to describe completely the behavior of a saturated rock core in terms of compressional-wave velocity, thermal conductivity, porosity, and bulk density.

Paleomagnetic reconstructions of sediments at ODP Sites 135-840 and 135-841

The geometry of the Tonga Arc implies that it has rotated approximately 17° clockwise away from the Lau Ridge as the Lau Basin formed in between. Questions have arisen about the timing of the opening, whether the arc behaved rigidly, and whether the opening occurred instead from motion of the Lau Ridge, the remanent arc. We undertook to address these questions by taking paleomagnetic samples from sediment cores drilled on the Tonga Arc at Sites 840 and 841, orienting the samples in azimuth, and comparing the paleodeclinations to expected directions. Advanced hydraulic piston corer (APC) cores from Holes 840C and 841A were oriented during drilling with a tool based on a magnetic compass and attached to the core barrel. Samples from Hole 841B were drilled with a rotary core barrel (RCB) and therefore are azimuthally unoriented. They were oriented by identifying faults and dipping beds in the core and aligning them with the same features in the Formation MicroScanner (FMS) wireline logs, which were themselves oriented with a three-axis magnetometer in the FMS tool. The best results came from the APC cores, which yielded a mean pole at -69.0°S, 112.2°E for an age of 4 Ma. This pole implies a declination anomaly of 20.8° ± 12.6° (95% confidence limit), which appears to have occurred by tectonic rotation of the Tonga Arc. This value is almost exactly that expected from the geometry of the arc and implies that it did indeed rotate clockwise as a rigid body. The large uncertainty in azimuth results from core orientation errors, which have an average standard deviation of 18.6°. The youngest cores used to calculate the APC pole contain sediments deposited during Subchron 2A (2.48-3.40 Ma), and their declinations are indistinguishable from the others. This observation suggests that most of the rotation occurred after their deposition; this conclusion must be treated with caution, however, because of the large azimuthal orientation errors. Poles from late and early Miocene sediments of Hole 841B are more difficult to interpret. Samples from this hole are mostly normal in polarity, fail a reversal test, and yield poles that suggest that the normal-polarity directions may be a recent overprint. Late Miocene reversed-polarity samples may be unaffected by this overprint; if so, they imply a declination anomaly of 51.1° ± 11.5°. This observation may indicate that, for older sediments, Tonga forearc rotations are larger than expected.