Pliocene-Plistocene deposition of carbonate and organic carbon in ODP Hole 159-959C

During Ocean Drilling Program (ODP) Leg 159, four sites (Sites 959-962) were drilled along a depth transect on the Côte d'Ivoire/Ghana Transform Margin. In this study, the Pliocene-Pleistocene history of carbonate and organic carbon accumulation at Hole 959C is reconstructed for the eastern equatorial Atlantic off the Ivory Coast/Ghana based on bulk carbonate, sand fraction, organic carbon, and other organic geochemical records (d13Corg, marine organic matter percentages derived from organic petrology, hydrogen index, C/N). Pliocene-Pleistocene sedimentation off the Ivory Coast/Ghana was strongly affected by low mean sedimentation rates, which are attributed to persistently enhanced bottom-water velocities related to the steep topography of the transform margin. Sand fraction and bulk carbonate records reveal typical glacial/interglacial cycles, preserved, however, with low time resolution. Intermediate carbonate accumulation rates observed throughout the Pliocene-Pleistocene suggest intense winnowing and sediment redistribution superimposed by terrigenous dilution. 'Atlantic-type' sand and carbonate cycles, consistent with records from pelagic areas of the eastern equatorial Atlantic, are encountered at Hole 959C prior to about 0.9 Ma. Total organic carbon (TOC) records are frequently inversely correlated to carbonate contents, indicating mainly productivity-driven carbonate dissolution related to changes in paleoproductivity. During Stages 22-24, 20, 16, 12, 8, and 4, sand and carbonate records reveal a 'Pacific-type' pattern, showing elevated contents during glacials commonly in conjunction with enhanced TOC records. Formation of 'Pacific-type' patterns off the Ivory Coast/Ghana is attributed to drastically increased bottom-water intensities along the transform margin in accordance with results reported from the Walvis Ridge area. Short-term glacial/interglacial changes in paleoproductivity off the Ivory Coast/Ghana are to some extend recognizable during glacials prior to 1.7 Ma and interglacial Stages 21, 19, 13, 9, and 1. Enhanced coastal upwelling during interglacials is attributed to local paleoclimatic and oceanographic conditions off the Ivory Coast/Ghana. Quantitative estimates of marine organic carbon based on organic petrologic and d13Corg records reveal an offset in concentration ranging from 15% to 60%. Highest variabilities of both records are recorded since ~0.9 Ma. Discrepancies between the isotopic and microscopic records are attributed to an admixture of C4 plant debris approaching the eastern equatorial Atlantic via atmospheric dust. Terrestrial organic material likely originated from the grass-savannah-covered Sahel zone in central Africa. Estimated C4 plant concentrations and accumulation rates range from 10% to 37% and from almost zero to 0.006 g/cm**2/k.y., respectively. The strongest eolian supply to the northern Gulf of Guinea is indicated between 1.9 and 1.68 Ma and during glacial isotopic Stages 22-24, 20, 14, and 12. The presence of grass-type plant debris is further supported by organic petrologic studies, which reveal well-preserved cell tissues of vascular plants or tube-shaped, elongated terrestrial macerals showing different levels of oxidation.

Geochemistry of sediment cores of the Southern Ocean

We examine the possibility that glacial increase in the areal extent of reducing sediments might have changed the oceanic Cd inventory, thereby decoupling Cd from PO4. We suggest that the precipitation of Cd-sulfide in suboxic sediments is the single largest sink in the oceanic Cd budget and that the accumulation of authigenic Cd and U is tightly coupled to the organic carbon flux into the seafloor. Sediments from the Subantarctic Ocean and the Cape Basin (South Atlantic), where oxic conditions currently prevail, show high accumulation rates of authigenic Cd and U during glacial intervals associated with increased accumulation of organic carbon. These elemental enrichments attest to more reducing conditions in glacial sediments in response to an increased flux of organic carbon. A third core, overlain by Circumpolar Deep Water (CPDW) as are the other two cores but located south of the Antarctic Polar Front, shows an approximately inverse pattern to the Subantarctic record. The contrasting patterns to the north and south of the Antarctic Polar Front suggest that higher accumulation rates of Cd and U in Subantarctic sediments were driven primarily by increased productivity. This proposal is consistent with the hypothesis of glacial stage northward migration of the Antarctic Polar Front and its associated belt of high siliceous productivity. However, the increase in authigenic Cd and U glacial accumulation rates is higher than expected simply from a northward shift of the polar fronts, suggesting greater partitioning of organic carbon into the sediments during glacial intervals. Lower oxygen content of CPDW and higher organic carbon to biogenic silica rain rate ratio during glacial stages are possible causes. Higher glacial productivity in the Cape Basin record very likely reflects enhanced coastal up-welling in response to increased wind speeds. We suggest that higher productivity might have doubled the areal extent of suboxic sediments during the last glacial maximum. However, our calculations suggest low sensitivity of seawater Cd concentrations to glacial doubling of the extent of reducing sediments. The model suggests that during the last 250 kyr seawater Cd concentrations fluctuated only slightly, between high levels (about 0.66 nmol/kg) on glacial initiations and reaching lowest values (about 0.57 nmol/kg) during glacial maxima. The estimated 5% lower Cd content at the last glacial maximum relative to modern levels (0.60 nmol/kg) cannot explain the discordance between Cd and delta13C, such as observed in the Southern Ocean. This low sensitivity is consistent with foraminiferal data, suggesting minimal change in the glacial Cd mean oceanic content.

Geochemistry, physical properties, diatom abundance and datums of ODP Site 186-1150 and Hole 186-1151A

Detection of climate response to orbital forcing during Cenozoic long-term global cooling is a key to understanding the behavior of Earth's icehouse climate. Sedimentary rhythm, which is a rhythmic or cyclic variation in the sequence of sediments and sedimentary rocks, is useful for quantitative reconstruction of Earth's evolution during geological time. In this study, we attempt to (1) identify sources of natural gamma ray (NGR) emissions of core recovered during Ocean Drilling Program (ODP) Leg 186 by analyses of physical properties, major element concentrations, diatom abundances, and total organic carbon contents, (2) integrate whole-core NGR intensity of recovered core with wireline logging NGR measurements in order to construct a continuous sedimentary sequence, and (3) discuss changes in the NGR signal in the time domain. This attempt gives us preliminary information to discuss climate stability in relation to orbital forcing thorough geologic time. NGR values are obtained mainly by indirectly measuring the amount of terrigenous minerals including potassium and related elements in the sediments. NGR intensity is also affected by high porosity, which in these sediments was related to the amount of diatom valves. NGR signals might be a proxy of the intensity of the East Asian monsoon off Sanriku. A continuous sedimentary record was constructed by integration of the whole-core NGR intensity measured in sediments obtained from the drilled holes with that measured directly in the borehole by wireline logging, then using a stratigraphic age model to convert to a time series covering 1.3-9.7 Ma with a short break at ~5 Ma. High sedimentation rate (H) stages were identified in the sequence, related to intervals of low-amplitude precession and eccentricity variations. The transition of the dominant periodicities through the four H stages may correlate to major shifts in the climate system, including the onset of major Northern Hemisphere glaciation, the initial stage of the East Asian monsoon intensification, and the onset of the East Asian monsoon with uplift of the Himalayas and the Tibetan Plateau.

Age-depth correlations for Ontong Java Plateau sites

We used well logs, in some cases combined with shipboard physical properties measurements to make more complete profiles and to correlate between sites on the Ontong Java Plateau. By comparing sediment bulk density, velocity, and resistivity logs from adjacent holes at the same site, we showed that even subtle features of the well logs are reproducible and are caused by variations in sedimentation. With only minor amounts of biostratigraphic information, we could readily correlate these sedimentary features across the entire top of the Ontong Java Plateau, demonstrating that for most of the Neogene the top of the plateau is a single sedimentary province. We found it more difficult, but still possible, to correlate in detail sites from the top of the plateau to those drilled on the flanks. The pattern of sedimentation rate variation down the flank of the plateau cannot be interpreted as simply controlled by dissolution. Site 805, in particular, oscillates between accumulating sediment at roughly the same rate as cores on top of the Ontong Java Plateau, and accumulating sediment as slowly as Site 803, 200 m deeper in the water column. These oscillations do not match earlier reconstructions of central Pacific carbonate compensation depth variations.

Geochemistry, fluxes and nitrogen isotopic composition data of traps LP1 and EBC2-1 and cores GeoB4242-4 and Geo4301-1

We compare total and biogenic particle fluxes and stable nitrogen isotope ratios (d15N) at three mooring sites along a productivity gradient in the Canary Islands region with surface sediment accumulation rates and sedimentary d15N. Higher particle fluxes and sediment accumulation rates, and lower d15N were observed in the upwelling influenced eastern boundary region (EBC) compared to the oligotrophic sites north of Gran Canaria [European Station for Time-Series in the Ocean, Canary Islands (ESTOC]] and north of La Palma (LP). The impact of organic matter degradation and lateral particle advection on sediment accumulation was quantified with respect to the multi-year flux record at the ESTOC. Remineralisation of organic matter in the water column and at the sediment surface resulted in an organic carbon preservation of about 0.8% and total nitrogen preservation of about 0.4% of the estimated export production. Higher total and carbonate fluxes and accumulation rates in the lower traps and surface sediment compared to the upper traps indicated that at least 50% of the particulate matter at the ESTOC was derived from allochthonous sources. Low d15N values in the lower traps of the ESTOC and LP point to a source region influenced by coastal upwelling. We conclude from this study that the reconstruction of export production or nutrient regimes from sedimentary records in regions with strong productivity gradients might be biased due to the mixture of particles originating from autochthonous and allochthonous sources. This could result in an imprint of high productivity signatures on sedimentation processes in oligotrophic regions.

XRF scanning, pollen and spores of ODP Site 108-659

Pliocene vegetation dynamics and climate variability in West Africa have been investigated through pollen and XRF-scanning records obtained from sediment cores of ODP Site 659 (18°N, 21°W). The comparison between total pollen accumulation rates and Ti/Ca ratios, which is strongly correlated with the dust input at the site, showed elevated aeolian transport of pollen during dusty periods. Comparison of the pollen records of ODP Site 659 and the nearby Site 658 resulted in a robust reconstruction of West African vegetation change since the Late Pliocene. Between 3.6 and 3.0 Ma the savannah in West Africa differed in composition from its modern counterpart and was richer in Asteraceae, in particular of the Tribus Cichorieae. Between 3.24 and 3.20 Ma a stable wet period is inferred from the Fe/K ratios, which could stand for a narrower and better specified mid-Pliocene (mid-Piacenzian) warm time slice. The northward extension of woodland and savannah, albeit fluctuating, was generally greater in the Pliocene. NE trade wind vigour increased intermittently around 2.7 and 2.6 Ma, and more or less permanently since 2.5 Ma, as inferred from increased pollen concentrations of trade wind indicators (Ephedra, Artemisia, Pinus). Our findings link the NE trade wind development with the intensification of the Northern Hemisphere glaciations (iNHG). Prior to the iNHG, little or no systematic relation could be found between sea surface temperatures of the North Atlantic with aridity and dust in West Africa.

Cretaceous stable isotopic record and sea surface temperture estimation for ODP Site 207-1259

The Turonian (93.5 to 89.3 million years ago) was one of the warmest periods of the Phanerozoic eon, with tropical sea surface temperatures over 35°C. High-amplitude sea-level changes and positive d18O excursions in marine limestones suggest that glaciation events may have punctuated this episode of extreme warmth. New d18O data from the tropical Atlantic show synchronous shifts ~91.2 million years ago for both the surface and deep ocean that are consistent with an approximately 200,000-year period of glaciation, with ice sheets of about half the size of the modern Antarctic ice cap. Even the prevailing supergreenhouse climate was not a barrier to the formation of large ice sheets, calling into question the common assumption that the poles were always ice-free during past periods of intense global warming.

Sand fraction, carbonate and organic carbon contents of ODP Hole 175-1085A

Site 1085 is located on the continental rise of southwest Africa at a water depth of 1713 m off the mouth of the Orange River in the Cape Basin. The site is part of the suite of locations drilled during Leg 175 on the Africa margin to reconstruct the onset and evolution of the elevated biological productivity associated with the Benguela Current upwelling system (Wefer, Berger, Richter, et al., 1998, doi:10.2973/odp.proc.ir.175.1998). Three sediment samples were collected per section from Cores 170-1085A-28H through 45X (251-419 mbsf) to provide a survey of the sediment record of paleoproductivity from the middle late Miocene to the early Pliocene (~8.7-4.7 Ma), which is a period that includes the postulated northward migration and intensification of the Benguela Current and the establishment of modern circulation off southwest Africa (Siesser, 1980; Diester-Haass et al., 1992; Berger et al., 1998). Core 170-1085A-30H (270-279 mbsf) had essentially no recovery; this coring gap was filled with samples from Cores 170-1085B-29H and 30H (261-280 mbsf). The results of measurements of multiple paleoproductivity proxies are summarized in this report. Included in these proxies are the radiolarian, foraminiferal, and echinoderm components of the sand-sized sediment fraction. Opal skeletons of radiolarians (no diatoms were found) relate to paleoproductivity and water mass chemistry (Summerhayes et al., 1995, doi:10.1016/0079-6611(95)00008-5; Lange and Berger, 1993, doi:10.2973/odp.proc.sr.130.011.1993; Nelson et al., 1995, doi:10.1029/95GB01070). The accumulation rates of benthic foraminifers are useful proxies for paleoproductivity (Herguera and Berger, 1991, doi:10.1130/0091-7613(1991)019<1173:PFBFAG>2.3.CO;2; Nees, 1997, doi:10.1016/S0031-0182(97)00012-6; Schmiedl and Mackensen, 1997, doi:10.1016/S0031-0182(96)00137-X) because these fauna subsist on organic matter exported from the photic zone. Echinoderms also depend mainly on food supply from the photic zone (Gooday and Turley, 1990), and their accumulation rates are an additional paleoproductivity proxy. Concentrations of calcium carbonate (CaCO3) and organic carbon in sediment samples are fundamental measures of paleoproductivity (e.g., Meyers, 1997, doi:10.1016/S0146-6380(97)00049-1). In addition, organic matter atomic carbon/nitrogen (C/N) ratios and delta13C values can be used to infer the origin of the organic matter contained within the sediments and to explore some of the factors affecting its preservation and accumulation (Meyers, 1994, doi:10.1016/0009-2541(94)90059-0).

Hydrocarbons in surface layer bottom sediments from the North Dvina Riverand the southern part of the Dvina Bay, White Sea

Analysis of molecular composition of alkanes in bottom sediments of the southern part of Dvina Bay (White Sea) in October 2001 revealed the following main peculiarities of hydrocarbon behavior in the estuary: dominating of high molecular C23-C45 compounds and irregular distribution of hydrocarbons in bottom sediments as a result of high sedimentation rate and active hydrodynamics in the studied area.

Sediments and tephra layers from the southern Tyrrhenian abyssal plain near Marsili Seamount

From the south-eastern Tyrrhenian deep-sea floor, four sediment cores of "Meteor" cruise 22 (1971) are described. These cores were taken in the basin between the Aeolian Islands and the Marsili Seamount, an elevation of more tha 3000 m above the sea floor. The sedimentation of the deep-sea basin is distinguished by a sequence of turbidites with a high sedimentation rate. The composition of the clastic material and the position of the cores in the mouth area of the morphologically very pronounced Stromboli Canyon suggest an interpretation of the turbidite sequence as fan of this canyon onto the deep-sea floor. A white rhyolitic pumice-tephra at the base of the 4 m thick sequence of turbidites in core M22-102 has been correlated with the Pelato eruption of the island of Liparo in the 6th century A.D. At the foot of the Marsili Seamount - apparently in morphologically elevated positions - the influence of the turbidite sedimentation increases, the rate of sedimentation is lower and stratigraphic omissions are probable. Here, rather compacted globigerina marls have been found in only 15 -25 cm depth. In addition, volcanic material in the form of lapilli layers, palagonitized ashes and detrital volcanic sands of the Marsili Seamount have been encountered in this area. An up to 3 cm thick layer of completely palagonitized basaltic ash intercalates with the marls at the base of two cores. Layers of very fresh olivine basaltic lapilli in core 103 and palagonitized lapilli of latitic composition in core 104 testify to an explosive submarine volcanism of the Marsili Seamount. According to the stratigraphy of core 103, the latest manifestations of this basaltic volcanism belong to the late Pleistocene (Emiliana huxleyi-zone of Nannoplankton stratigraphy) The basaltic lapilli are glassy to perhyaline with phenocrysts or microphenocrysts predominantely of olivine. The petrological character of the basaltic volcanites with high MgO, Ni, Cr and high MgO/FeO- and Ni/Co-ratios exhibits primitive basaltic features. These basalts clearly differ from basalts of the ocean floors, mid-ocean ridges and marginal basins. Prominent features are a missing iron-enrichment trend and low TiO2. Al2O3 tends to be high, as well as K2O and related trace elements (Ba, Sr). In spite of silica undrsaturation and high color index, the Marsili basalt exhibit some analogies with the calcalkaline basalts of the Aeolian arc, as well as the undersaturated basalts of some other circumoceanic areas.

Chemistry and accumulation rates of Jurassic to early Cretaceous sediments from the central equatorial Pacific

Sedimentation in the central Pacific during the Jurassic and Early Cretaceous was dominated by abundant biogenic silica. A synthesis of the stratigraphy, lithology, petrology, and geochemistry of the radiolarites in Sites 801 and 800 documents the sedimentation processes and trends in the equatorial central Pacific from the Middle Jurassic through the Early Cretaceous. Paleolatitude and paleodepth reconstructions enable comparisons with previous DSDP sites and identification of the general patterns of sedimentation over a wide region of the Pacific. Clayey radiolarites dominated sedimentation on Pacific oceanic crust within tropical paleolatitudes from at least the latest Bathonian through Tithonian. Radiolarian productivity rose to a peak within 5° of the paleoequator, where accumulation rates of biogenic silica exceeded 1000 g/cm**2/m.y. Wavy-bedded radiolarian cherts developed in the upper Tithonian at Site 801 coinciding with the proximity of this site to the paleoequator. Ribbon-bedding of some radiolarian cherts exposed on Pacific margins may have formed from silicification of radiolarite deposited near the equatorial high-productivity zone where radiolarian/clay ratios were high. Silicification processes in sediments extensively mixed by bioturbation or enriched in clay or carbonate generally resulted in discontinuous bands or nodules of porcellanite or chert, e.g., a "knobby" radiolarite. Ribbon-bedded cherts require primary alternations of radiolarian-rich and clay-rich layers as an initial structural template, coupled with abundant biogenic silica in both layers. During diagenesis, migration of silica from clay-rich layers leaves radiolarian "ghosts" or voids, and the precipitation in adjacent radiolarite layers results in silicification of the inter-radiolarian matrix and infilling of radiolarian tests. Alternations of claystone and clay-rich radiolarian grainstone were deposited during the Callovian at Site 801 and during the Berriasian-Valanginian at Site 800, but did not silicify to form bedded chert. Carbonate was not preserved on the Pacific oceanic floor or spreading ridges during the Jurassic, perhaps due to an elevated level of dissolved carbon dioxide. During the Berriasian through Hauterivian, the carbonate compensation depth (CCD) descended to approximately 3500 m, permitting the accumulation of siliceous limestones at near-ridge sites. Carbonate accumulation rates exceeded 1500 g/cm**2/m.y. at sites above the CCD, yet there is no evidence of an equatorial carbonate bulge during the Early Cretaceous. In the Barremian and Aptian, the CCD rose, coincident with the onset of mid-plate volcanic activity. Abundance of Fe and Mn and the associated formation of authigenic Fe-smectite clays was a function of proximity to the spreading ridges, with secondary enrichments occurring during episodes of spreading-center reorganizations. Callovian radiolarite at Site 801 is anomalously depleted in Mn, which resulted either from inhibited precipitation of Mn-oxides by lower pH of interstitial waters induced by high dissolved oceanic CO2 levels or from diagenetic mobilization of Mn. Influx of terrigenous (eolian) clay apparently changed with paleolatitude and geological age. Cyclic variations in productivity of radiolarians and of nannofossils and in the influx of terrigenous clay are attributed to Milankovitch climatic cycles of precession (20,000 yr) and eccentricity (100,000 yr). Diagenetic redistribution of biogenic silica and carbonate enhanced the expression of this cyclic sedimentation. Jurassic and Lower Cretaceous sediments were deposited under oxygenated bottom-water conditions at all depths, accompanied by bioturbation and pervasive oxidation of organic carbon and metals. Despite the more "equable" climate conditions of the Mesozoic, the super-ocean of the Pacific experienced adequate deep-water circulation to prevent stagnation. Efficient nutrient recycling may have been a factor in the abundance of radiolarians in this ocean basin.

Geochemistry of DSDP Hole 91-596

Geochemical analyses of sediments from the top 24.5 m of Deep Sea Drilling Project hole 596 (23°51.20'S, 169°39.27'W) show great variability in the composition of pelagic clays accumulated in the South Pacific since the late Cretaceous. Elemental associations indicate that most of this variability can be attributed to variations in abundances of six sediment end-member components: detrital (eolian), andesitic (volcanic), hydrothermal, hydrogenous, phosphate (fish debris), and biogenic silica. We develop a sedimentation model which is used to infer processes that might have influenced the accumulation rates of these components over the last 85 million years. The accumulation of eolian detritus in the South Pacific shows some similarities to that observed in the North Pacific and has been largely controlled by global climate trends in the Cenozoic. Much of the variation in the accumulation of other sediment components likely reflects the paleoceanographic evolution of the South Pacific. The most notable change in the sedimentary environment occurred at about the Paleogene/Neogene boundary. At that time, significant changes in the color, mineralogy, and chemistry of the sediment probably reflect major shifts in climate mode as well as oceanic circulation in the central South Pacific region.

Paleomagnetic, stable oxygen isotope ratios, and U/Th activities of ODP Site 172-1062

Geomagnetic excursions are recognized as intrinsic features of the Earth's magnetic field. High-resolution records of field behaviour, captured in marine sedimentary cores, present an opportunity to determine the temporal and geometric character of the field during geomagnetic excursions and provide constraints on the mechanisms producing field variability. We present here the highest resolution record yet published of the Blake geomagnetic excursion (~125 ka) measured in three cores from Ocean Drilling Program (ODP) Site 1062 on the Blake-Bahama Outer Ridge. The Blake excursion has a controversial structure and timing but these cores have a sufficiently high sedimentation rate (~10cm/ka) to allow detailed reconstruction of the field behaviour at this site during the excursion. Palaeomagnetic measurements of the cores reveal rapid transitions (<500 yr) between the contemporary stable normal polarity and a completely reversed state of long duration which spans a stratigraphic interval of 0.7 m. We determine the duration of the reversed state during the Blake excursion using oxygen isotope stratigraphy, combined with 230Th excess measurements to assess variations in the sedimentation rates through the sections of interest. This provides an age and duration for the Blake excursion with greater accuracy and with constrained uncertainty. We date the directional excursion as falling between 129 and 122 ka with a duration for the deviation of 6.5±1.3 kyr. The long duration of this interval and the fully reversed field suggest the existence of a pseudo-stable, reversed dipole field component during the excursion and challenge the idea that excursions are always of short duration.

Paleointensity record of Site 320-U1336

We present a high-resolution magnetostratigraphy and relative paleointensity (RPI) record derived from the upper 85 meters of IODP Site U1336, an equatorial Pacific early to middle Miocene succession recovered during Expedition 320/321. The magnetostratigraphy is well resolved with reversals typically located to within a few centimeters resulting in a well-constrained age model. The lowest normal polarity interval, from 85 to 74.87 meters, is interpreted as the upper part of Chron C6n (18.614-19.599 Ma). Another 33 magnetozones occur from 74.87 to 0.85 m, which are interpret to represent the continuous sequence of chrons from Chron C5Er (18.431-18.614 Ma) up to the top of Chron C5An.1n (12.014 Ma). We identify three new possible subchrons within Chron C5Cn.1n, Chron 5Bn.1r, and C5ABn. Sedimentation rates vary from about 7 to 15 m/Myr with a mean of about 10 m/Myr. We observe rapid, apparent changes in the sedimentation rate at geomagnetic reversals between ~16 and 19 Ma that indicate a calibration error in geomagnetic polarity timescale (ATNTS2004). The remanence is carried mainly by non-interacting particles of fine-grained magnetite, which have FORC distributions characteristic of biogenic magnetite. Given the relative homogeneity of the remanence carriers throughout the 85-m-thick succession and the quality with which the remanence is recorded, we have constructed a relative paleointensity (RPI) record that provides new insights into middle Miocene geomagnetic field behavior. The RPI record indicates a gradual decline in field strength between 18.5 Ma and 14.5 Ma, and indicates no discernible link between RPI and either chron duration or polarity state.