Geochemistry of ODP Hole 121-752A

The present study involves the analysis and interpretation of geochemical data from a suite of sediment samples recovered at ODP Hole 752A. The samples encompass the time period that includes the lithospheric extension and uplift of Broken Ridge, and they record deposition below and above the mid-Eocene angular unconformity that denotes this uplift. A Q-mode factor analysis of the geochemical data indicates that the sediments in this section are composed of a mixture of three geochemical end members that collectively account for 94.2% of the total variance in the data. An examination of interelement ratios for each of these end members suggests that they represent the following sedimentary components: (1) a biogenic component, (2) a volcanogenic component, and (3) a hydrothermal component. The flux of the biogenic component decreases almost thirtyfold across the Eocene unconformity. This drastic reduction in the deposition of biogenic materials corresponds to the almost complete disappearance of chert layers, diatoms, and siliceous microfossils and is coincident with the uplift of Broken Ridge. The volcanogenic component is similar in composition to Santonian ash recovered at Hole 755A on Broken Ridge and is the apparent source of the Fe-stained sediment that immediately overlies the angular unconformity. This finding suggests that significant amounts of Santonian ash were subaerially exposed, weathered, and redeposited and is consistent with data that suggest that the vertical uplift of Broken Ridge was both rapid and extensive. The greatest flux of hydrothermal materials is recorded in the sediments immediately below the angular unconformity. This implies that the uplift of Broken Ridge was preceded by a significant amount of rifting, during which faulting and fracturing of the lithosphere led to enhanced hydrothermal circulation. This time sequence of events is consistent with (but not necessarily diagnostic of) the passive model of lithospheric extension and uplift.

Physical properties and abundance of diatoms of the ANDRILL AND1-1B drill core

In the austral summer of 2006/7 the ANDRILL MIS (ANtarctic geological DRILLing- McMurdo Ice Shelf) project recovered a 1285 m sediment core from beneath the Ross Ice Shelf near Hut Point Peninsula, Ross Island, Antarctica in a flexural moat associated with the volcanic loading of Ross Island. Contained within the upper ~600 m of this core are sediments recording 38 glacial to interglacial cycles of Early Pliocene to Pleistocene time, including 13 discrete diatomite units (DU). The longest of these, DU XI, is ~76 m thick, contains two distinct unconformities marked by layers of volcanic brecciated sands, and has been assigned an Early to Mid-Pliocene age (5-3 Ma). A detailed record (avg. sample spacing of 33 cm) of the siliceous microfossil assemblages have been generated for DU XI and used in conjunction with geochemical and sedimentological data to subdivide DU XI into four discrete subunits of continuous sedimentation. Within each unit, changes in diatom assemblages have been correlated with the d18O record, providing a temporal resolution as high as 600 yr, and allowing for the construction of a detailed age model and calculation of associated sediment accumulation rates within DU XI. Results indicate a productivity-dominated sedimentary record with higher sediment accumulation rates containing a greater proportion of hemipelagic mud occurring during relatively cool periods and reduced accumulation during warmer intervals. This implies that even during periods of substantial warmth, Milankovitch-paced changes in Antarctic ice volume can be linked to ecological changes recorded as shifts in diatom assemblages.

Geochemistry of tropical Atlantic sediments of Marine Isotope Stage 4

Antarctic Intermediate Water (AAIW) and Subantarctic Mode Water (SAMW) are the main conduits for the supply of dissolved silicon (silicic acid) from the deep Southern Ocean (SO) to the low-latitude surface ocean and therefore have an important control on low-latitude diatom productivity. Enhanced supply of silicic acid by AAIW (and SAMW) during glacial periods may have enabled tropical diatoms to outcompete carbonate-producing phytoplankton, decreasing the relative export of inorganic to organic carbon to the deep ocean and lowering atmospheric pCO2. This mechanism is known as the "silicic acid leakage hypothesis" (SALH). Here we present records of neodymium and silicon isotopes from the western tropical Atlantic that provide the first direct evidence of increased silicic acid leakage from the Southern Ocean to the tropical Atlantic within AAIW during glacial Marine Isotope Stage 4 (~60-70 ka). This leakage was approximately coeval with enhanced diatom export in the NW Atlantic and across the eastern equatorial Atlantic and provides support for the SALH as a contributor to CO2 drawdown during full glacial development.

Biosiliceous sedimentation at ODP Site 128-798

Upper Pliocene through Holocene sediments recovered at Site 798 in the Japan Sea (Oki Ridge) exhibit rhythmic variation in weight percent biogenic opal at intervals of ~5 m and periods equivalent to the 41-k.y. obliquity cycle. Variance at 17 and 100 k.y. is observed prior to 1.3 Ma. These cycles are also clearly defined by log data and correspond to clusters of decimeter-scale dark-colored sediment units alternating with clusters of light-colored units. Opal content varies between 3% and 22% between 0 and 1.3 Ma and from 3% to 43% between 1.3 and 2.6 Ma. Long-term opal accumulation rates average 1.8 g/cm**2/k.y. in the late Pliocene/early Pleistocene and decrease by about 60% at ~1.3 Ma. Rough calculations suggest that opal accumulation rates increased and terrigenous flux decreased during the Holocene relative to the last glacial period. Our age control is not yet sufficient to allow a similar analysis of the 41-k.y. cyclicity in opal content throughout the Pleistocene. Stable isotope results from planktonic foraminifers confirm previous suggestions of a strong surface-water freshening event during isotope stage 2; however, this episode appears to be unique during the Pleistocene. Benthic foraminifers are depleted in 18O during parts of glacial stages 2 and 6 relative to adjacent interglacials, suggesting unusual warming and/or freshening of deep waters. Collectively, the stable isotope and %opal data are consistent with continuing isolation of the Japan Sea during the Quaternary with important transitions occurring at 1.3, 0.7 to 1.0, and 0.2 to 0.3 Ma. Complex relationships among the stable isotope results, %opal data, and sediment characteristics such as color and organic and inorganic carbon content preclude development of a simple model to explain cyclical sedimentation. Opal maxima occur within both light and dark intervals and the processes that control surface-water productivity are at times decoupled from the factors that regulate deep-water dysaerobia. We suggest that water column overturn is controlled largely by regional atmospheric circulation that must also have an as yet poorly understood effect on surface-water fertility.

Late Miocene carbon isotope and paleoproductivity record

We examine whether or not a relationship exists between the late Miocene carbon isotope shift (~7.6-6.6 Ma) and marine productivity at four sites from the Indian and Pacific Oceans (Ocean Drilling Program Sites 721, 1146, 1172, and 846). We use a multiproxy approach based on benthic foraminiferal accumulation rates, elemental ratios, and dissolution indices, and we compare these data to benthic foraminiferal d13C values measured on the same samples. Although some of these sites have been targeted previously in studies of either the late Miocene/early Pliocene "biogenic bloom" (Sites 721 and 846) or the late Miocene carbon isotope shift (Site 1172), our records are the first to establish paired proxy records of carbon isotopes and paleoproductivity allowing a direct assessment of a potential link. Our results indicate that at all sites, productivity increased sometime during the d13C shift; at three sites (721, 1146, and 846), productivity increased at the beginning of the shift. The correlation coefficients derived from linear regression between micropaleontologically derived productivity and foraminiferal d13C values are relatively high during the time interval containing the late Miocene d13C shift (and statistically significant at three of the sites). Carbon flux and isotope mass balance considerations illustrate that transfer of organic matter between the terrestrial and marine reservoirs together with enhanced oceanic upwelling best approximates observed changes in carbon isotope records and paleoproductivity. We note that long-term trend in the Site 846 paleoproductivity record can be correlated to the long-term trend in the Site 848 eolian flux reconstructions of Hovan (1995, doi:10.2973/odp.proc.sr.138.132.1995) hinting at a link between strengthened wind regime and productivity during the late Miocene.

Data on multidisciplinary research in the Tajura Rift (Gulf of Aden) during Cruise 7 of R/V Akademik Mstislav Keldysh in winter 1983-1984

In the collective monograph results of geological and geophysical studies in the Tadjura Rift carried out by conventional outboard instruments and from deep/sea manned submersibles "Pisces" in winter 1983-1984 are reported. Main features of rift tectonics, geology, petrology, and geochemistry of basalts from the rift are under consideration. An emphasis is made on lithology, stratigraphy, and geochemistry of bottom sediments. Roles of terrigenous, edafogenic, biogenic, and hydrothermal components in formation of bottom sediments from the rift zone are shown.

Sedimentary records of ODP Site 198-1209 on Shatsky Rise

The accumulation of wind blown (eolian) dust in deep-sea sediments reflects the aridity/humidity conditions of the continental region supplying the dust, as well as the "gustiness" of the climate system. Detailed studies of Pleistocene glacial-interglacial dust fluxes suggest changes in accumulation rates corresponding to orbital variations in solar insolation (Milankovitch cycles). While the orbital cycles found in sedimentary archives of the Pleistocene are intricately related to glacial growth and decay, similar global orbital signals recognized in deep-sea sediments of early Paleogene age, the last major greenhouse interval ~65-45 million years ago, could not have been linked to the waxing and waning of large ice sheets. Thus orbital signals recorded in early Paleogene sediments must reflect some other climate response to changes in solar insolation. To explore the potential connection between orbital forcing and the climate processes that control dust accumulation, we generated a high-resolution dust record for ~58 Myr old sediments from Shatsky Rise (ODP Site 1209, paleolatitude ~15°N-20°N). The dust accumulation data provide the first evidence of a correlation between dust flux to the deep sea and orbital cyclicity during the early Paleogene, indicating dust supply responded to insolation forcing during the last major interval of greenhouse climate. Furthermore, the relative amplitude of the dust flux response during the early Paleogene greenhouse was comparable to that during icehouse climates. Thus, subtle variations in solar insolation driven by changes in Earth's orbit about the Sun may have had a similar impact on climate during intervals of overall warmth as they did during glacial-interglacial states.

Sedimentology and Th, Pa, U, and N isotopic composition of core MD84-527

High-resolution records of opal, carbonate, and terrigenous fluxes have been obtained from a high-sedimentation rate core (MD84-527: 43°50'S; 51°19'E; 3269 m) by normalization to 230Th. This method estimates paleofluxes to the seafloor on a point-by-point basis and distinguishes changes in sediment accumulation due to variations in vertical rain rates from those due to changes in syndepositional sediment redistribution by bottom currents. We also measured sediment delta15N to evaluate the changes in nitrate utilization in the overlying surface waters associated with paleoflux variations. Our results show that opal accumulation rates on the seafloor during the Holocene and stage 3, based on 14C dating, were respectively tenfold and fivefold higher than the vertical rain rates, At this particular location, changes in opal accumulation on the seafloor appear to be mainly controlled by sediment redistribution by bottom currents rather than variations in opal fluxes from the overlying water column. Correction for syndepositional sediment redistribution and the improved time resolution that can be achieved by normalization to 230Th disclose important variations in opal rain rates. We found relatively high but variable opal paleoflux during stage 3, with two maxima centered at 36 and 30 kyr B.P., low opal paleoflux during stage 2 and deglaciation and a pronounced maximum during the early Holocene, We interpret this record as reflecting variations in opal production rates associated with climate-induced latitudinal migration of the southern ocean frontal system. Sediments deposited during periods of high opal paleoflux also have high authigenic U concentrations, suggesting more reducing conditions in the sediment, and high Pa-231/Th-230 ratios, suggesting increased scavenging from the water column. Sediment delta15N is circa 1.5 per mil higher during isotopic stage 2 and deglaciation. The low opal rain rates recorded during that period appear to have been associated with increased nitrate depletion. This suggests that opal paleofluxes do not simply reflect latitudinal migration of the frontal system but also changes in the structure of the upper water column. Increased stratification during isotopic stage 2 and deglaciation could have been produced by a meltwater lid, leading to lower nitrate supply rates to surface waters.

Chemical and isotope compositions of main phases of metalliferous sediments from holes of DSDP Leg 92

The carbonate-free metalliferous fraction of thirty-nine sediment samples from four DSDP Leg 92 sites has been analyzed for 12 elements, and a subset of 16 samples analyzed for Pb isotopic composition. The main geochemical features of this component are as follows: i) very high concentrations of Fe and Mn, typically 25-39% and 5-14%, respectively; ii) Al and Ca contents generally less than 2% and 5%, respectively; iii) high Cu (1000-2000 ppm), and Zn and Ni (500-1000 ppm) values; and iv) Co and Pb concentrations of 100-250 ppm. In terms of element partitioning within the metalliferous fraction, amorphous to poorly crystallized oxide-oxyhydroxides removed by the second leach carry virtually all of the Mn, and about 90% of the Ca, Sr and Ni. The well-crystallized goethite-rich material removed by the third leach carries the majority of Fe, Cu, and Pb. These relations hold for sediments as young as ~1-2 Ma, indicating early partitioning of hydrothermal Fe and Mn into separate phases. Calculated mass accumulation rates (MAR) for Fe, Mn, Cu, Pb, Zn and Ni in the bulk sediment show the same overall trends at three of the sites, with greatest MAR values near the basement, and a general decrease in MAR values towards the tops of the holes (for sediments deposited above the lysocline). These relations strongly support the concept of a declining hydrothermal contribution of these elements away from a ridge axis. Nevertheless, MAR values for these metals up to ~200 km from the ridge axis are orders of magnitude higher than on abyssal seafloor plains where there is no hydrothermal influence. Mn/Fe ratios throughout the sediment column at two sites indicate that the composition of the hydrothermal precipitates changed during transport through seawater, becoming significantly depleted in Mn beyond ~200-300 km from the axis, but maintaining roughly the same proportion of Fe. Most of the Pb isotope data for the Leg 92 metalliferous sediments form approximately linear arrays in the conventional isotopic plots, extending from the middle of the field for mid-ocean ridge basalts toward the field for Mn nodules. The array of data lying between these two end-members is most readily interpreted in terms of simple linear mixing of Pb derived from basaltic and seawater end-member sources. The least radiogenic sediments reflect the average Pb isotope composition of discharging hydrothermal solutions and ocean-ridge basalt at the EPR over the ~4-8 Ma B.P. interval. Pb in sediments deposited up to 250 km from the axis can be almost entirely of basaltic-hydrothermal origin. Lateral transport of some basaltic Pb by ocean currents appears to extend to distances of at least 1000 km west of the East Pacific Rise.

Major components and major and trace elements from ODP Site 175-1085

We have analyzed 33 Pliocene bulk sediment samples from Ocean Drilling Program Site 1085 in the Cape Basin, located offshore of western Africa in the Angola-Benguela Current system, for 17 major and trace elements, and interpreted their associations and temporal variations in the context of an allied data set of CaCO3, opal, and Corg. We base our interpretations on elemental ratios, accumulation rates, inter-element correlations, and several multi-element statistical techniques. On the basis of qualitative assessment of downhole changes in the distributions of P and Ba, utilized as proxies of export production, we conclude that highs in bulk and biogenic accumulation that occur at 3.2 Ma, 3.0 Ma, 2.4 Ma, and 2.25 Ma were caused by increases in export production as well as terrigenous flux, and record a greater sequestering of organic matter during these time periods. Studies of refractory elements and other indicator proxies (SiO2, Al2O3, TiO2, Fe2O3, MgO, V, Cr, Sr, and Zr) strongly suggest that the terrigenous component of the bulk sediment is composed of two compositional end-members, one being 'basaltic' in composition and the other similar to an 'average shale'. The basaltic end-member comprises approximately 10-15% of the total bulk sediment and its presence is consistent with the local geology of source material in the drainage basin of the nearby Orange River. The increase in bulk accumulation at 2.4 Ma appears to reflect a greater relative increase in basaltic input than the relative increase in shale-type input. Although studies such as this cannot precisely identify the transport mechanisms of the different terrigenous components, these results are most consistent with variations in sea level (and associated changes in shelf geometry and fluvial input) being responsible for the changing depositional conditions along the Angolan Margin during this time period.

Chemical and isotope compositions of sediments from DSDP Hole 86-576A and Core LL44-GPC-3

A record of changes in Pb and Sr isotopic composition of two cores (DSDP 86-576A and LL44- GPC-3) from the red clay region of the central North Pacific has been determined for the past 60-65 million years. The isotope records of the eolian silicate fraction of the red clays reflect the change in source area as the core sites migrated under different wind systems. The Sr isotope compositions of eolian silicate material are consistent with Asian loess and North American arc volcanism that has been recognized from mineralogical studies. The silicate-bound eolian Pb isotopic compositions similarly reflect Asian loess and arc volcanism. The isotope records of three ferromanganese crusts from similar locations in the central Pacific are similar to the eolian component of red clays, but offset to less radiogenic values. This may be due to two mechanisms: (1) Pb that can be removed from eolian material by seawater is much less radiogenic, or less likely (2) hydrothermal Pb can be transported further away from venting sites through particle exchange with seawater, despite hydrothermal venting acting as a net sink of oceanic Pb. The temporal changes in Pb isotopes in the ferromanganese crusts, bulk red clays and eolian silicates are similar although offset from each other suggesting that eolian deposition is an important source of Pb to seawater and to ferromanganese crusts. This contrasts with the Atlantic and Southern Ocean where more intense deep water flow leads to isotopic gradients in FeMn crusts that do not reflect surface water conditions immediately above the crust. A mechanism is proposed which accounts for Pacific deepwater Pb being isotopically influenced by eolian deposition.

Sedimentation in the vicinity of Leg 92 Drill Sites: Studies of site survey cores

Surveys of the areas surrounding the sites drilled on the Leg 92 19°S transect showed that sedimentation at all except the oldest site is dominated by calcium carbonate deposition. The sediments in the area of the oldest site, west of the Austral Fracture Zone, are being deposited beneath the calcium carbonate compensation depth and are dominated by terrigenous and metal-rich hydrogenous and hydrothermal sediments. The noncarbonate sediments in all of the areas east of the Austral Fracture Zone are dominated by hydrothermal sediment similar in composition to that presently being deposited at the East Pacific Rise. Although no biogenic microfossils were present in smear slides of the sediment, geochemical partitioning suggests that a remnant signal of siliceous biogenic deposition may be preserved, especially in gravity core (GC) 8, which was collected from a high heat flow zone near Site 600. The siliceous sediment may also result from the deposition of amorphous hydrothermal silica from the higher concentrations of pore water SiO2 characteristic of the upwelling waters. Sedimentation on the broad plateaus that characterize each area is quite uniform and suggests that sites on these plateaus will be broadly representative of pelagic sedimentation in the area.

Helium isotope concentrations and ratios in sediments from ODP Hole 130-806B

We have determined the helium abundance and isotopic composition of seafloor carbonate sediments from the flanks of the Ontong Java Plateau, western equatorial Pacific Ocean (ODP Site 806). These results provide a two million year record of the burial flux of extraterrestrial 3He, which we believe is a proxy for the terrestrial accretion rate of interplanetary dust particles. The 3He burial flux prior to ~700 ka was relatively low, ~0.5 pcc/cm**2/kyr, but from 700 ka to the present, the burial flux gradually increased to a value of ~1.0 pcc/cm**2/kyr. 100 kyr periodicity in the 3He burial flux is apparent over the last 700 kyr and correlates with the oxygen isotope record of global climate, with high 3He burial fluxes associated with interglacial periods. This periodicity and phase are consistent with previous 3He measurements in North Atlantic sediments. Although 100 kyr periodicity in 3He burial flux is in agreement with recent predictions of the accretion rate of interplanetary dust based on a model of the orbital evolution of asteroidal debris, the measurements and predictions differ by one half cycle in phase. Nevertheless, our observations suggest the terrestrial accretion rate of interplanetary dust is controlled by orbital eccentricity and/or inclination relative to the solar-system invariable plane. Such control is a necessary but not sufficient condition for the hypothesis of that variations in extraterrestrial dust accretion modulates terrestrial climate with a 100 kyr period. We also identify several brief (<25 kyr) intervals of strongly enhanced 3He burial, possibly related to random and transient fluctuations in the accretion rate of asteroidal or cometary dust particles.