Chemical concentrations and fluxes from EPICA ice cores EDML and EDC

Continuous sea salt and mineral dust aerosol records have been studied on the two EPICA (European Project for Ice Coring in Antarctica) deep ice cores. The joint use of these records from opposite sides of the East Antarctic plateau allows for an estimate of changes in dust transport and emission intensity as well as for the identification of regional differences in the sea salt aerosol source. The mineral dust flux records at both sites show a strong coherency over the last 150 kyr related to dust emission changes in the glacial Patagonian dust source with three times higher dust fluxes in the Atlantic compared to the Indian Ocean sector of the Southern Ocean (SO). Using a simple conceptual transport model this indicates that transport can explain only 40% of the atmospheric dust concentration changes in Antarctica, while factor 5-10 changes occurred. Accordingly, the main cause for the strong glacial dust flux changes in Antarctica must lie in environmental changes in Patagonia. Dust emissions, hence environmental conditions in Patagonia, were very similar during the last two glacials and interglacials, respectively, despite 2-4 °C warmer temperatures recorded in Antarctica during the penultimate interglacial than today. 2-3 times higher sea salt fluxes found in both ice cores in the glacial compared to the Holocene are difficult to reconcile with a largely unchanged transport intensity and the distant open ocean source. The substantial glacial enhancements in sea salt aerosol fluxes can be readily explained assuming sea ice formation as the main sea salt aerosol source with a significantly larger expansion of (summer) sea ice in the Weddell Sea than in the Indian Ocean sector. During the penultimate interglacial, our sea salt records point to a 50% reduction of winter sea ice coverage compared to the Holocene both in the Indian and Atlantic Ocean sector of the SO. However, from 20 to 80 ka before present sea salt fluxes show only very subdued millennial changes despite pronounced temperature fluctuations, likely due to the large distance of the sea ice salt source to our drill sites.

Os isotope ratios of Late Eocene sediments from the tropical Pacific

High resolution records (ca. 100 kyr) of Os isotope composition (187Os/188Os) in bulk sediments from two tropical Pacific sites (ODP Sites 1218 and 1219) capture the complete Late Eocene 187Os/188Os excursion and confirm that the Late Eocene 187Os/ 188Os minimum, earlier reported by Ravizza and Peucker-Ehrenbrink (2003, doi:10.1016/S0012-821X(03)00137-7), is a global feature. Using the astronomically tuned age models available for these sites, it is suggested that the Late Eocene 187Os/188Os minimum can be placed at 34.5 +/- 0.1 Ma in the marine records. In addition, two other distinct features of the 187Os/188Os excursion that are correlatable among sections are proposed as chemostratigraphic markers which can serve as age control points with a precision of ca. +/-0.1 Myr. We propose a speculative hypothesis that higher cosmic dust flux in the Late Eocene may have contributed to global cooling and Early Oligocene glaciation (Oi-1) by supplying bio-essential trace elements to the oceans and thereby resulting in higher ocean productivity, enhanced burial of organic carbon and draw down of atmospheric CO2. To determine if the hypothesis that enhanced cosmic dust flux in the Late Eocene was a cause for the 187Os/188Os excursion can be tested by using the paired bulk sediment and leachate Os isotope composition; 187Os/188Os were also measured in sediment leachates. Results of analyses of leachates are inconsistent between the south Atlantic and the Pacific sites, and therefore do not yield a robust test of this hypothesis. Comparison of 187Os/188Os records with high resolution benthic foraminiferal delta18O records across the Eocene-Oligocene transition suggests that 187Os flux to the oceans decreased during cooling and ice growth leading to the Oi-1 glaciation, whereas subsequent decay of ice-sheets and deglacial weathering drove seawater 187Os/188Os to higher values. Although the precise timing and magnitude of these changes in weathering fluxes and their effects on the marine 187Os/188Os records are obscured by recovery from the Late Eocene 187Os/188Os excursion, evidence of the global influence of glaciation on supply of Os to the ocean is robust as it has now been documented in both Pacific and Atlantic records.

Strontium isotope ratios of fish teeth from ODP sites in the central North Pacific

Strontium isotopic compositions of ichthyoliths (microscopic fish remains) in deep-sea clays recovered from the North Pacific Ocean (ODP holes 885A, 886B, and 886C) are used to provide stratigraphic age control within these otherwise undatable sediments. Age control within the deep-sea clays is crucial for determining changes in sedimentation rates, and for calculating fluxes of chemical and mineral components to the sediments. The Sr isotopic ages are in excellent agreement with independent age datums from above (diatom ooze), below (basalt basement) and within (Cretaceous-Tertiary boundary) the clay deposit. The 87Sr/86Sr ratios of fish teeth from the top of the pelagic clay unit (0.7089891), indicate an Late Miocene age (5.8 Ma), as do radiolarian and diatom biostratigraphic ages in the overlying diatom ooze. The 87Sr/86Sr ratio (0.707887) is consistent with a Cretaceous-Tertiary boundary age, as identified by anomalously high iridium, shocked quartz, and sperules in Hole 886C. The 87Sr/86Sr ratios of pretreated fish teeth from the base of the clay unit are similar to Late Cretaceous seawater (0.707779-0.7075191), consistent with radiometric ages from the underlying basalt of 81 Ma. Calculation of sedimentation rates based on Sr isotopic ages from Hole 886C indicate an average sedimentation rate of 17.7 m/Myr in Unit II (diatom ooze), 0.55 m/Myr in Unit IIIa (pelagic clay), and 0.68 m/Myr in Unit IIIb (distal hydrothermal precipitates). The Sr isotopic ages indicate a period of greatly reduced sedimentation (or possible hiatus) between about 35 and 65 Ma (Eocene-Paleocene), with a linear sedimentation rate of only 0.04 m/Myr The calculated sedimentation rates are generally inversely proportional to cobalt accumulation rates and ichthyolith abundances. However, discrepancies between Sr isotope ages and cobalt accumulation ages of l0-15 Myr are evident, particularly in the middle of the clay unit IIIa (Oligocene-Paleocene).

Strontium isotope ratios and concentrations in fossil fish teeth

We analyzed 87Sr/86Sr ratios in foraminifera, pore fluids, and fish teeth for samples ranging in age from Eocene to Pleistocene from four Ocean Drilling Program sites distributed around the globe: Site 1090 in the Cape Basin of the Southern Ocean, Site 757 on the Ninetyeast Ridge in the Indian Ocean, Site 807 on the Ontong-Java Plateau in the western equatorial Pacific, and Site 689 on the Maud Rise in the Southern Ocean. Sr isotopic ratios for dated foraminifera consistently plot on the global seawater Sr isotope curve. For Sites 1090, 757, and 807 Sr isotopic values of the pore fluids are generally less radiogenic than contemporaneous seawater values, as are values for fossil fish teeth. In contrast, pore fluid 87Sr/86Sr values at Site 689 are more radiogenic than contemporaneous seawater, and the corresponding fish teeth also record more radiogenic values. Thus, Sr isotopic values preserved in fossil fish teeth are consistently altered in the direction of the pore fluid values; furthermore, there is a correlation between the magnitude of the offset between the pore fluids and the seawater curve, and the associated offset between the fish teeth and the seawater curve. These data suggest that the hydroxyfluorapatite of the fossil fish teeth continues to recrystallize and exchange Sr with its surroundings during burial and diagenesis. Therefore, Sr chemostratigraphy can be used to determine rough ages for fossil fish teeth in these cores, but cannot be used to fine-tune age models. In contrast to the Sr isotopic system, our Nd concentration data, combined with published isotopic and rare earth element data, suggest that fish teeth acquire Nd during early diagenesis while they are still in direct contact with seawater. The concentrations of Nd acquired at this stage are extremely high relative to the concentrations in surrounding pore fluids. As a result, Nd isotopes are not altered during burial and later diagenesis. Therefore, fossil fish teeth from a variety of marine environments preserve a reliable and robust record of deep seawater Nd isotopic compositions from the time of deposition.

Geochemical data and magnetic measurements of IODP Expedition 308, Hole U1319A from the Gulf of Mexico

A 160 m mostly turbiditic late Pleistocene sediment sequence (IODP Expedition 308, Hole U1319A) from the Brazos-Trinity intraslope basin system off Texas was investigated with paleo- and rock magnetic methods. Numerous layers depleted in iron oxides and enriched by the ferrimagnetic iron-sulfide mineral greigite (Fe3S4) were detected by diagnostic magnetic properties. From the distribution of these layers, their stratigraphic context and the present geochemical zonation, we develop two conceptual reaction models of greigite formation in non-steady depositional environments. The "sulfidization model" predicts single or twin greigite layers by incomplete transformation of iron monosulfides with polysulfides around the sulfate methane transition (SMT). The "oxidation model" explains greigite formation by partial oxidation of iron monosulfides near the iron redox boundary during periods of downward shifting oxidation fronts. The stratigraphic record provides evidence that both these greigite formation processes act here at typical depths of about 12-14 mbsf and 3-4 mbsf. Numerous "fossil" greigite layers most likely preserved by rapid upward shifts of the redox zonation denote past SMT and sea floor positions characterized by stagnant hemipelagic sedimentation conditions. Six diagenetic stages from a pristine magnetite-dominated to a fully greigite-dominated magnetic mineralogy were differentiated by combination of various hysteresis and remanence parameters.

Down-core sedimentary Sr-Nd isotope records from two Cape Basin sediment cores in the South Atlantic: GeoB3603-2 (Meteor cruise M34/1) and MD02-2594 (Marion Dufresne cruise MD128)

We report down-core sedimentary Nd isotope (epsilon Nd) records from two South Atlantic sediment cores, MD02-2594 and GeoB3603-2, located on the western South African continental margin. The core sites are positioned downstream of the present-day flow path of North Atlantic Deep Water (NADW) and close to the Southern Ocean, which makes them suitable for reconstructing past variability in NADW circulation over the last glacial cycle. The Fe-Mn leachates epsilon Nd records show a coherent decreasing trend from glacial radiogenic values towards less radiogenic values during the Holocene. This trend is confirmed by epsilon Nd in fish debris and mixed planktonic foraminifera, albeit with an offset during the Holocene to lower values relative to the leachates, matching the present-day composition of NADW in the Cape Basin. We interpret the epsilon Nd changes as reflecting the glacial shoaling of Southern Ocean waters to shallower depths combined with the admixing of southward flowing Northern Component Water (NCW). A compilation of Atlantic epsilon Nd records reveals increasing radiogenic isotope signatures towards the south and with increasing depth. This signal is most prominent during the Last Glacial Maximum (LGM) and of similar amplitude across the Atlantic basin, suggesting continuous deep water production in the North Atlantic and export to the South Atlantic and the Southern Ocean. The amplitude of the epsilon Nd change from the LGM to Holocene is largest in the southernmost cores, implying a greater sensitivity to the deglacial strengthening of NADW at these sites. This signal impacted most prominently the South Atlantic deep and bottom water layers that were particularly deprived of NCW during the LGM. The epsilon Nd variations correlate with changes in 231Pa/230Th ratios and benthic d13C across the deglacial transition. Together with the contrasting 231Pa/230Th: epsilon Nd pattern of the North and South Atlantic, this indicates a progressive reorganization of the AMOC to full strength during the Holocene.

Cation exchange capacity and water content of ODP sites from Nankai

Pore fluid chlorinity lower than seawater is often observed in accretionary wedges and one of the possible causes of pore water freshening is the smectite to illite reaction. This reaction occurs during diagenesis in the 80-150°C temperature range. Low chlorinity anomalies observed at the toe of accretionary wedges have thus been interpreted as evidence for lateral fluid migration from inner parts of the wedge and the seismogenic zone. However, temperature conditions in Nankai Trough are locally high enough for the smectite to illite transition to occur in situ. Cation exchange capacity is here used as a proxy for smectite content in the sediment and the amount of interlayer water released during the smectite to illite reaction represents in average 12 water molecules per cation charge. Water and chloride budget calculations show that there is enough smectite to explain the chlorinity anomalies by in situ reactions. The shape of the pore fluid chlorinity profiles can be explained if compaction is also taken into account in the model. Lateral flow is not needed. This argument, based solely on chloride concentration, does not imply that lateral flow is absent. However, previous estimations of lateral fluid fluxes, and of the duration of transient flow events along the de.collement, should be reconsidered.

Calcium isotope composition of Oceanic Anoxic Events 1a and 2 sediments

Calcium-isotope ratios (d44/42Ca) were measured in carbonate-rich sedimentary sections deposited during Oceanic Anoxic Events 1a (Early Aptian) and 2 (Cenomanian-Turonian). In sections from Resolution Guyot, Mid-Pacific Mountains; Coppitella, Italy; and the English Chalk at Eastbourne and South Ferriby, UK, a negative excursion in d44/42Ca of ~0.20 per mil and ~0.10 per mil is observed for the two events. These d44/42Ca excursions occur at the same stratigraphic level as the carbon-isotope excursions that define the events, but do not correlate with evidence for carbonate dissolution or lithological changes. Diagenetic and temperature effects on the calcium-isotope ratios can be discounted, leaving changes in global seawater composition as the most probable explanation for d44/42Ca changes in four different carbonate sections. An oceanic box model with coupled strontium- and calcium-isotope systems indicates that a global weathering increase is likely to be the dominant driver of transient excursions in calcium-isotope ratios. The model suggests that contributions from hydrothermal activity and carbonate dissolution are too small and short-lived to affect the oceanic calcium reservoir measurably. A modelled increase in weathering flux, on the order of three times the modern flux, combined with increased hydrothermal activity due to formation of the Ontong-Java Plateau (OAE1a) and Caribbean Plateau (OAE2), can produce trends in both calcium and strontium isotopes that match the signals recorded in the carbonate sections. This study presents the first major-element record of a weathering response to Oceanic Anoxic Events.

Magnetic observation of ODP Site 152-919 in the Irminger Basin, North Atlantic

Component natural remanent magnetizations derived from u-channel and 1-qcm discrete samples from ODP Site 919 (Irminger Basin) indicate the existence of four intervals of negative inclinations in the upper Brunhes Chronozone. According to the age model based on planktic oxygen isotope data, these "excursional" intervals occur in sediments deposited during the following time intervals: 32-34 ka, 39-41 ka, 180-188 ka and 205-225 ka. These time intervals correspond to polarity excursions detected elsewhere, known as Mono Lake, Laschamp, Iceland Basin and Pringle Falls. The isotope-based age model is supported by the normalized remanence (paleointensity) record that can be correlated to other calibrated paleointensity records for the 0-500 ka interval, such as that from ODP Site 983. For the intervals associated with the Mono Lake and Laschamp excursions, virtual geomagnetic poles (VGPs) reach equatorial latitudes and mid-southerly latitudes, respectively. For intervals associated with the Iceland Basin and Pringle Falls excursions, repeated excursions of VGPs to high southerly latitudes indicate rapid directional swings rather than a single short-lived polarity reversal. The directional instability associated with polarity excursions is not often recorded, probably due to smoothing of the sedimentary record by the process of detrital remanence (DRM) acquisition.