Sediment, isotopic and geochemical record during Marine Isotope Stages 29 to 34 of IODP Site 339-U1387

Centennial-to-millennial scale records from IODP Site U1387, drilled during IODP Expedition 339 into the Faro Drift at 558 m water depth, now allow evaluating the climatic history of the upper core of the Mediterranean Outflow (MOW) and of the surface waters in the northern Gulf of Cadiz during the early Pleistocene. This study focuses on the period from Marine Isotope Stage (MIS) 29 to 34, i.e. the interval surrounding extreme interglacial MIS 31. Conditions in the upper MOW reflect obliquity, precession and millennial-scale variations. The benthic d18O signal follows obliquity with the exception of an additional, smaller d18O peak that marks the MIS 32/31 transition. Insolation maxima (precession minima) led to poor ventilation and a sluggish upper MOW core, whereas insolation minima were associated with enhanced ventilation and often also increased bottom current velocity. Millennial-scale periods of colder sea-surface temperatures (SST) were associated with short-term maxima in flow velocity and better ventilation, reminiscent of conditions known from MIS 3. A prominent contourite layer, coinciding with insolation cycle 100, was formed during MIS 31 and represents one of the few contourites developing within an interglacial period. MIS 31 surface water conditions were characterized by an extended period (1065-1091 ka) of warm SST, but SST were not much warmer than during MIS 33. Interglacial to glacial transitions experienced 2 to 3 stadial/interstadial cycles, just like their mid-to-late Pleistocene counterparts. Glacial MIS 30 and 32 recorded periods of extremely cold (< 12°C) SST that in their climatic impact were comparable to the Heinrich events of the mid and late Pleistocene. Glacial MIS 34, on the other hand, was a relative warm glacial period off southern Portugal. Overall, surface water and MOW conditions at Site U1387 show strong congruence with Mediterranean climate, whereas millennial-scale variations are closely linked to North Atlantic circulation changes.

Physical properties and AMS characteristics of ODP Site 185-1149 sediments

During Ocean Drilling Program Leg 185, we studied progressive changes of microfabrics of unconsolidated pelagic and hemipelagic sediments in Holes 1149A and 1149B in the northwest Pacific at 5818 m water depth. We paid particular attention to the early consolidation and diagenetic processes without tectonic deformation before the Pacific plate subduction at the Izu-Bonin Trench. Shape, size, and arrangement of pores were analyzed by scanning electron microscope (SEM) and were compared to anisotropy of magnetic susceptibility (AMS) data. The microfabric in Unit I is nondirectional fabric and is characterized by large peds of ~10-100 µm diameter, which are made up of clay platelets (mainly illite) and siliceous biogenic fragments. They are ovoid in shape and are mechanically packed by benthic animals. Porosity decreases from 0 to 60 meters below seafloor (mbsf) in Unit I (from 60% to 50%) in association with macropore size decreases. The microfabric of coarser grain particles other than clay in Unit II is characterized by horizontal preferred orientation because of depositional processes in Subunit IIA and burial compaction in Subunit IIB. On the other hand, small peds, which are probably made of fragments of fecal pellets and are composed of smectite and illite (3-30 µm diameter), are characterized by random orientation of clay platelets. The clay platelets in the small peds in Subunit IIA are in low-angle edge-to-face (EF) or face-to-face (FF) contact. These peds are electrostatically connected by long-chained clay platelets, which are interconnected by high-angle EF contact. Breaking of these long chains by overburden pressure diminishes the macropores, and the clay platelets in the peds become FF in contact, resulting in decreases in the volume of the micropores between clay platelets. Thus, porosity in Subunits IIA and IIB decreases remarkably downward. The AMS indicates random fabric and horizontal preferred orientation fabric in Units I and II, respectively. This result corresponds to that of SEM microfabric observations.In Subunit IIB, pressure solutions around radiolarian tests and clinoptilolite veins with normal displacement sense are seen distinctively below ~170 mbsf, probably in correspondence to the transition zone from opal-A to opal-CT.

Geochemistry and petrography of organic matter at DSDP Site 93-603

A series of 22 sediment samples of Cretaceous and Cenozoic age from DSDP Holes 603, 603B, and 603C at the continental rise off the northeastern American coast near Cape Hatteras was investigated by organic geochemical methods including organic carbon determination, Rock-Eval pyrolysis, gas chromatography and combined gas chromatography/mass spectrometry of extractable hydrocarbons, and kerogen microscopy. An abundance of terrigenous organic matter, including larger coal particles (almost exclusively consisting of huminite/vitrinite macerals), is the dominant characteristic of the organofacies types at Site 603. Marine organic matter, mostly structurally degraded and in the form of fecal pellets, was preserved in the Valanginian laminated marls and in Cenomanian black claystone turbidites. Long-chain nalkanes reflect the terrigenous imprint in the nonaromatic hydrocarbon fractions, whereas a second maximum at lower carbon numbers in most cases is caused by the presence of more mature recycled organic matter. Abundant isoprenoid and steroid hydrocarbons were found in sediments containing mainly marine organic matter, whereas hopanoids reflect the ubiquitous microbial activity. The organic matter in the Site 603 sediments, in so far as it is not recycled, is thermally immature.

Composition of hydrothermal massive sulfide deposits from ODP Site 158-957 and Leg 169 sites

Sulfide mineral major and trace element analyses were performed on more than 50 polished slabs representing mineralization from three seafloor hydrothermal massive sulfide deposits. Samples from the Bent Hill and ODP Mound massive sulfide deposits, both on the Juan de Fuca Ridge, can be contrasted with samples from the Trans-Atlantic Geotraverse (TAG) hydrothermal mound on the Mid-Atlantic Ridge. The massive sulfide at Bent Hill is predominantly pyrite and pyrrhotite, with increasing amounts of copper-bearing sulfide minerals at the base of the massive sulfide body and through the stockwork to an interval 200 m below seafloor that hosts high copper mineralization (Deep Copper Zone). ODP Mound contains much more abundant sphalerite and copper-bearing sulfides as compared to either Bent Hill or TAG, which are predominantly pyrite with much less abundant chalcopyrite. Copper-bearing sulfides from the Deep Copper Zone beneath Bent Hill and the lowest sampled interval of ODP Mound are petrographically and chemically similar, but distinct from copper-bearing minerals higher in either sequence.

Iodine and boron concentrations in pore fluids, ultramafic clasts and interstitial serpentinite mud of ODP Hole 125-779A and Site 195-1200

Iodine and boron were analyzed in pore fluids, serpentinized ultramafic clasts, and the serpentinized mud matrix of the South Chamorro Seamount mud volcano (Ocean Drilling Program Leg 195 Site 1200) to determine the distribution of these elements in deep forearc settings. Similar analyses of clasts and muds from the Conical Seamount mud volcano (Leg 125 Site 779) were also carried out. Interstitial pore fluids are enriched in boron and iodine without appreciable change in chloride concentration relative to seawater. Both the ultramafic clasts and the associated serpentinized mud present the highest documented iodine concentrations for all types of nonsedimentary rocks (6.3-101.7 µmol/kg). Such high iodine concentrations, if commonplace in marine forearc settings, may constitute a significant, previously unknown reservoir of iodine. This serpentinized forearc mantle reservoir may potentially contribute to the total crustal iodine budget and provide a mechanism for its recycling at convergent plate margins. Both clasts and mud show concurrent enrichments in boron and iodine, and the similarity in pore fluid profiles also suggests that these two incompatible, fluid-mobile elements behave similarly at convergent plate margins.

Dinoflagellate abundance and events of ODP Site 189-1172 sediments

Palynomorphs were studied in samples from Ocean Drilling Program (ODP) Leg 189, Holes 1172A and 1172D (East Tasman Plateau; 2620 m water depth). Besides organic walled dinoflagellate cysts (dinocysts), broad categories of other palynomorphs were quantified in terms of relative abundance. In this contribution, we provide an overview of the dinocyst distribution from the Maastrichtian to lowermost Oligocene and Quaternary intervals and illustrate main trends in palynomorph distribution. The uppermost Cretaceous-lowermost Oligocene succession of Site 1172 has a confident biomagnetostratigraphy, enabling us to tie early Paleogene Southern Hemisphere dinocyst events to the geomagnetic polarity timescale for the first time. Dinocyst species from the Maastrichtian to earliest Oligocene at Site 1172 are largely endemic ("Transantarctic Flora") or bipolar; cosmopolitan taxa are present in the background as well. The Maastrichtian-early late Eocene dinocyst assemblages are indicative of shallow-marine to restricted marine, pro-deltaic conditions, closely tied to a massive siliciclastic sequence. By middle late Eocene times (~35.5 Ma), the siliciclastic sequence gave way to a thin glauconitic unit, considered to reflect the deepening of the Tasmanian Gateway. This transition coincides with the most prominent change in dinocyst associations of the Paleogene. The turnover is inferred to reflect a change from marginal marine to more offshore conditions, with increased winnowing and oxidation. Overlying pelagic carbonate ooze of middle early Oligocene and younger age is virtually barren of organic microfossils, although Quaternary assemblages have been recovered. This aspect is taken to reflect average low sedimentation rates and well-oxygenated water masses during most of the Oligocene and Neogene. The few palynologically productive samples from the Oligocene-Quaternary interval have a stronger cosmopolitan to subtropical signature, with warm-water species being common to abundant.

Log-ratio of silica to aluminium counts (ln(Si/Al)) from ODP site 108-658

Growing evidence suggests that the low atmospheric CO2 concentration of the ice ages resulted from enhanced storage of CO2 in the ocean interior, largely as a result of changes in the Southern Ocean1. Early in the most recent deglaciation, a reduction in North Atlantic overturning circulation seems to have driven CO2 release from the Southern Ocean**2, 3, 4, 5, but the mechanism connecting the North Atlantic and the Southern Ocean remains unclear. Biogenic opal export in the low-latitude ocean relies on silicate from the underlying thermocline, the concentration of which is affected by the circulation of the ocean interior. Here we report a record of biogenic opal export from a coastal upwelling system off the coast of northwest Africa that shows pronounced opal maxima during each glacial termination over the past 550,000 years. These opal peaks are consistent with a strong deglacial reduction in the formation of silicate-poor glacial North Atlantic intermediate water**2 (GNAIW). The loss of GNAIW allowed mixing with underlying silicate-rich deep water to increase the silicate supply to the surface ocean. An increase in westerly-wind-driven upwelling in the Southern Ocean in response to the North Atlantic change has been proposed to drive the deglacial rise in atmospheric CO2 (refs 3, 4). However, such a circulation change would have accelerated the formation of Antarctic intermediate water and sub-Antarctic mode water, which today have as little silicate as North Atlantic Deep Water and would have thus maintained low silicate concentrations in the Atlantic thermocline. The deglacial opal maxima reported here suggest an alternative mechanism for the deglacial CO2 release**5, 6. Just as the reduction in GNAIW led to upward silicate transport, it should also have allowed the downward mixing of warm, low-density surface water to reach into the deep ocean. The resulting decrease in the density of the deep Atlantic relative to the Southern Ocean surface promoted Antarctic overturning, which released CO2 to the atmosphere.

Middle Eocene bulk sediment, benthic and planktic foraminiferal stable isotope values, and relative weight percent CaCO3 content from ODP Site 207-1260

Major ice sheets were permanently established on Antarctica approximately 34 million years ago, close to the Eocene/ Oligocene boundary, at the same time as a permanent deepening of the calcite compensation depth in the world's oceans. Until recently, it was thought that Northern Hemisphere glaciation began much later, between 11 and 5million years ago. This view has been challenged, however, by records of ice rafting at high northern latitudes during the Eocene epoch and by estimates of global ice volume that exceed the storage capacity of Antarctica at the same time as a temporary deepening of the calcite compensation depth 41.6 million years ago. Here we test the hypothesis that large ice sheets were present in both hemispheres 41.6 million years ago using marine sediment records of oxygen and carbon isotope values and of calcium carbonate content from the equatorial Atlantic Ocean. These records allow, at most, an ice budget that can easily be accommodated on Antarctica, indicating that large ice sheets were not present in the Northern Hemisphere. The records also reveal a brief interval shortly before the temporary deepening of the calcite compensation depth during which the calcite compensation depth shoaled, ocean temperatures increased and carbon isotope values decreased in the equatorial Atlantic. The nature of these changes around 41.6 million years ago implies common links, in terms of carbon cycling, with events at the Eocene/Oligocene boundary and with the 'hyperthermals' of the Early Eocene climate optimum. Our findings help to resolve the apparent discrepancy between the geological records of Northern Hemisphere glaciation and model results that indicate that the threshold for continental glaciation was crossed earlier in the Southern Hemisphere than in the Northern Hemisphere.

Mineralogy, grain size composition, bulk carbonate isotopic ratios and ages of ODP Site 182-1128 sediments

This report presents mineralogic and geochemical data from Ocean Drilling Program Leg 182 Site 1128 in the Great Australian Bight. Clay mineralogy is dominated by mixed-layer illite-smectite, followed by minor amounts of kaolinite and illite, with intervals of pure smectite. Carbonate mineralogy is exclusively low-Mg calcite, except for one interval of dolomite in lower Oligocene sediments. Carbonate increases significantly in upper Eocene sediments, decreases through the lower Oligocene, then increases again in the Neogene. Quartz is present as a minor component that covaries inversely with carbonate. High-resolution sampling associated with Chron 13 normal (early Oligocene) reveals high-frequency (~23 k.y.) fluctuations in clay mineralogy and carbonate abundance and a positive oxygen and carbon isotope excursion (in bulk carbonates) related to Antarctic glaciation.

Geochemistry of Pliocene-Pleistocene volcanic sands of ODP Site 136-842

Several distinct, thin (2-7 cm), volcanic sand layers ("ashes") were recovered in the upper portions of Holes 842A and 842B. These holes were drilled 320 km west of the island of Hawaii on the outer side of the arch that surrounds the southern end of the Hawaiian chain. These layers are Pliocene to Pleistocene in age, graded, and contain fresh glass and mineral fragments (mainly olivine, plagioclase, and clinopyroxene) and tests of Pleistocene to Eocene radiolarians. The glass fragments are weakly vesicular and blocky to platy in shape. The glass and olivine fragments from individual layers have large ranges in composition (i.e, larger than expected for a single eruption). These features are inconsistent with an explosive eruption origin for the sands. The only other viable mechanism for transporting these sands hundreds of kilometers from their probable source, the Hawaiian Islands, is turbidity currents. These currents were probably related to several of the giant debris slides that were identified from Gloria sidescan images around the islands. These currents would have run over the ~500-m-high Hawaiian Arch on their way to Site 842. This indicates that the turbidity currents were at least 325 m thick. Paleomagnetic and biostratigraphic data allow the ages of the sands to be constrained and, thus, related to particular Hawaiian debris flows. These correlations were checked by comparing the compositions of the glasses from the sands with those of glasses and rocks from islands with debris flows directed toward Site 842. Good correlations were found for the 110-ka slide from Mauna Loa and the ~1.4-Ma slide from Lanai. The correlation with Kauai is poor, probably because the data base for that volcano is small. The low to moderate sulfur content of the sand glasses indicates that they were derived from moderately to strongly degassed lavas (shallow marine or subaerially erupted), which correlates well with the location of the landslide scars on the flanks of the Hawaiian volcanoes. The glass sands may have been formed by brecciation during the landslide events or spallation and granulation as lava erupted into shallow water.

Biostratigraphy, magnetostratigraphy, granulometry, isotopes and clay mineral composition of ODP Site 188-1165

During Ocean Drilling Program Leg 188 to Prydz Bay, East Antarctica, several of the shipboard scientists formed the High-Resolution Integrated Stratigraphy Committee (HiRISC). The committee was established in order to furnish an integrated data set from the Pliocene portion of Site 1165 as a contribution to the ongoing debate about Pliocene climate and climate evolution in Antarctica. The proxies determined in our various laboratories were the following: magnetostratigraphy and magnetic properties, grain-size distributions (granulometry), near-ultraviolet, visible, and near-infrared spectrophotometry, calcium carbonate content, characteristics of foraminifer, diatom, and radiolarian content, clay mineral composition, and stable isotopes. In addition to the HiRISC samples, other data sets contained in this report are subsets of much larger data sets. We included these subsets in order to provide the reader with a convenient integrated data set of Pliocene-Pleistocene strata from the East Antarctic continental margin. The data are presented in the form of 14 graphs (in addition to the site map). Text and figure captions guide the reader to the original data sets. Some preliminary interpretations are given at the end of the manuscript.

Planktonic foraminifera stratigraphy of ODP Holes 198-1209C and 198-1211C

During Leg 198, the Cretaceous/Paleocene (K/P) boundary was recovered in a remarkable set of cores in nine separate holes at Sites 1209, 1210, 1211, and 1212 on the Southern High of Shatsky Rise. The boundary succession includes an uppermost Maastrichtian white to very pale orange, slightly indurated nannofossil ooze overlain by lowermost Paleocene grayish orange foraminiferal ooze. The boundary between the uppermost Maastrichtian and the lowermost Paleocene is clearly bioturbated. The contact surface is irregular, and pale orange burrows extend 10 cm into the white Maastrichtian ooze. Preliminary investigations conducted on board revealed that the deepest sections of these burrows yielded highly abundant, minute planktonic foraminiferal assemblages dominated by Guembelitria with rare Hedbergella holmdelensis and Hedbergella monmouthensis, possibly attributable to the lowermost Paleocene Zone P0. The substantial thickness of the uppermost Maastrichtian Micula prinsii (CC26) nannofossil Zone and the lowermost Danian Parvularugoglobigerina eugubina (Palpha) foraminiferal Zone suggested that the K/P boundary was rather expanded compared to the majority of deep-sea sites (see Bralower, Premoli Silva, Malone, et al., 2002, doi:10.2973/odp.proc.ir.198.2002). This data report concerns the planktonic foraminiferal biostratigraphy across the K/P boundary in Hole 1209C, the shallowest site (2387 m water depth), and in Hole 1211C, the deepest site (2907 m water depth), where the foraminiferal record across the boundary appeared to be best preserved.

Stable oxygen and carbon isotope ratios of foraminifera from Oligocene to Miocene sediments of DSDP Hole 39-354 from Ceara Rise, West Altlantic (Table 1)

The oxygen- and carbon-isotope compositions of planktic and benthic foraminifera and calcareous nannofossils from Middle Oligocene-Early Miocene Equatorial Atlantic sediments (DSDP Site 354) indicate two important paleoceanographic changes, in the Late Oligocene (foraminiferal Zone P.21) and in the Early Miocene (foraminiferal Zone N.5). The first change, reflected by a delta18O increase of 1.45? in Globigerina venezuelana, affected only intermediate pelagic and not surface, deep or bottom waters. The second change affected surface and intermediate waters, whereas deep and bottom waters showed only minor fluctuations. In the case of the former the isotope effect of the moderate ice accumulation on the Antarctic continent is amplified in the Equatorial Atlantic by changes in the circulation pattern. The latter paleoceanographic change, reflected by a significant increase in 18O in both planktic and benthic forms (about 1.0? and 0.5?, respectively), may have been caused by ice volume increase and temperature decrease. Both oxygen- and carbon-isotope compositions indicate a marked depth-habitat stratification for planktic foraminifera and calcareous nannofossils. Three different dwelling groups are recognized: shallow Globigerinoides, Globoquadrina dehiscens, Globorotalia mayeri and nannofossils; intermediate Globigerina venezuelana; and deep Catapsydrax dissimilis. The comparison of foraminifera and calcareous nannofossils suggests that the isotopic compositions of nannofossils are generally controlled by the same parameters which control the isotopic composition of shallow-dwelling foraminifera, but the former are more enriched in 18O.

Geochemistry of minerals at DSDP Holes 68-501 and 69-504B

The interaction of seawater with basalts in DSDP Hole 501 and the upper part of Hole 504B (Costa Rica Rift) produced oxidative alteration and a zonation of clay minerals along cracks. From rock edges to interiors in many cracks the following succession occurs, based on microscopic observations and microprobe analysis: iron hydroxides (red), "protoceladonite" (green), iddingsite (orange), and saponite (yellow). Clay minerals replace olivines and fill vesicles and cracks. Other secondary minerals are phillipsite, aragonite, and unidentified carbonates. Some glass is transformed to Mg-rich palagonite. Bulk rock chemistry is related to the composition of the secondary minerals. The zonation can be interpreted as a succession of postburial nonoxidative and oxidative diagenesis similar to that described in the Leg 34 basalts.