Organic carbon concentrations and Cd/Ca ratios of sediment core RC13-229

A comparison of cadmium/calcium (Cd/Ca) records of benthic foraminifera from a deep Cape Basin and a deep eastern equatorial Pacific core suggests that over the past 400,000 years, the nutrient concentration of Circumpolar Deep Water (CPDW) has always been lower than that of the deep Pacific. The data further suggest that at the 100,000- and 23,000-year orbital periods, the contribution of North Atlantic Deep Water to CPDW is at a maximum during periods of ice growth and at a minimum during periods of ice decay. These results are not in agreement with results based on carbon isotope records of benthic foraminifera, which suggest intervals of CPDW nutrient enrichment relative to the deep Pacific and an approximately in-phase relationship between CPDW nutrient concentration and ice volume. Resolution of the apparent conflict between delta13C and Cd/Ca data may provide important constraints on past deep-ocean circulation and nutrient variability.

Mineralogy and major element oxide composition of sediments from ODP Hole 172-1063D

Dansgaard-Oeschger (D-O) cycles in sediment at Site 1063 are characterized by distinct fluctuations in physical properties. Stadials are marked by low bulk density and interstadials by high bulk density. Compressional (P-)wave velocity is in phase with bulk density over some but not all depth intervals. Four of the D-O cycles straddling the oxygen isotope Stage 4/5 boundary have been studied in detail to understand the origin of the physical properties changes. Sediment on the Bermuda Rise is comprised of three main components: calcite, aluminosilicate minerals, and biogenic silica. Calcite concentrations vary from 1% to 43% of bulk sediment and are highest during interstadials. Aluminosilicate concentrations vary from 52% to 92% of bulk sediment and are highest during stadials. The major element ratios Al2O3/TiO2 and K2O/Al2O3 show increases across bulk density cycles, suggesting a change in the composition of aluminosilicates. This interpretation is supported by mineralogical analyses, which show a subtle change in clay composition. Biogenic silica concentrations vary from 0% to 23% of bulk sediment and are also highest during stadials. However, the abundance of silica varies significantly from one D-O cycle to another. Silt and fine sand abundance also increase during the first of the four stadials. This coarsening of sediment coincides with the increase in biogenic silica. The low grain density and high porosity associated with biogenic silica result in intervals of low bulk-sediment density. The abundance of biogenic silica closely matches P-wave velocity, suggesting that silica imparts a greater rigidity to the sediment.

Magnetic susceptibility and electric conductivity of marine surficial sediments by benthic electromagnetic profiling

Distribution, accumulation and diagenesis of surficial sediments in coastal and continental shelf systems follow complex chains of localized processes and form deposits of great spatial variability. Given the environmental and economic relevance of ocean margins, there is growing need for innovative geophysical exploration methods to characterize seafloor sediments by more than acoustic properties. A newly conceptualized benthic profiling and data processing approach based on controlled source electromagnetic (CSEM) imaging permits to coevally quantify the magnetic susceptibility and the electric conductivity of shallow marine deposits. The two physical properties differ fundamentally insofar as magnetic susceptibility mostly assesses solid particle characteristics such as terrigenous or iron mineral content, redox state and contamination level, while electric conductivity primarily relates to the fluid-filled pore space and detects salinity, porosity and grain-size variations. We develop and validate a layered half-space inversion algorithm for submarine multifrequency CSEM with concentric sensor configuration. Guided by results of modeling, we modified a commercial land CSEM sensor for submarine application, which was mounted into a nonconductive and nonmagnetic bottom-towed sled. This benthic EM profiler Neridis II achieves 25 soundings/second at 3-4 knots over continuous profiles of up to hundred kilometers. Magnetic susceptibility is determined from the 75 Hz in-phase response (90% signal originates from the top 50 cm), while electric conductivity is derived from the 5 kHz out-of-phase (quadrature) component (90% signal from the top 92 cm). Exemplary survey data from the north-west Iberian margin underline the excellent sensitivity, functionality and robustness of the system in littoral (~0-50 m) and neritic (~50-300 m) environments. Susceptibility vs. porosity cross-plots successfully identify known lithofacies units and their transitions. All presently available data indicate an eminent potential of CSEM profiling for assessing the complex distribution of shallow marine surficial sediments and for revealing climatic, hydrodynamic, diagenetic and anthropogenic factors governing their formation.

(Table 1) Gas tie points used to correlate NorthGRIP and Vostol records

North Atlantic sediment records (MD95-2042), Greenland (Greenland Ice Core Project (GRIP)) and Antarctica (Byrd and Vostok) ice core climate records have been synchronized over marine isotopic stage 3 (MIS 3) (64 to 24 kyr B.P.) (Shackleton et al., 2000). The resulting common timescale suggested that MD95-2042 d18Obenthic fluctuations were synchronous with temperature changes in Antarctica (dDice or d18Oice records). In order to assess the persistency of this result we have used here the recent Greenland NorthGRIP ice core covering the last glacial inception. We transfer the Antarctic Vostok GT4 timescale to NorthGRIP d18Oice and MD95-2042 d18Oplanktonic records and precisely quantify all the relative timing uncertainties. During the rapid warming of Dansgaard-Oeschger 24, MD95-2042 d18Obenthic decrease is in phase with d18Oplanktonic decrease and therefore with NorthGRIP temperature increase, but it takes place 1700 ± 1100 years after the Antarctic warming. Thus the present study reveals that the results obtained previously for MIS 3 cannot be generalized and demonstrates the need to improve common chronologies for marine and polar archives.

Osmium isotope composition of ODP Hole 121-758A

This study presents osmium (Os) isotope and elemental data for cleaned planktic foraminifera, authigenic Fe-Mn oxyhydroxides and pelagic carbonate host sediments from ODP site 758 in the southernmost reaches of the Bay of Bengal. The Os in the bulk sediments appears to be dominantly hydrogeneous (sourced by carbonate and Fe-Mn oxyhydroxide), but variations in this particular core are controlled by the presence of volcanic ash. Fe-Mn oxyhydroxide leachates (of the bulk sediments) from Holocene samples also yield an Os isotope composition close to that of seawater, but the record diverges from that of foraminifera at a depth corresponding to the oxic/post-oxic boundary, suggesting diagenetic mobilization of Os at depths below this. Holocene planktic foraminifera, cleaned using oxidative-reductive techniques, also give Os isotope compositions indistinguishable from modern seawater, but the record obtained for the past 150 kyr shows strong covaraitions of 187Os/188Os with both the local and global oxygen isotope record, with less radiogenic Os isotope compositions during glacial intervals. These results indicate that foraminifera provide a robust record of seawater Os isotope compositions, and comparison of the data obtained here with records from the other major oceans demonstrate global changes in 187Os/188Os over this time interval, while the covariation with oxygen isotopes suggest a process controlling the Os isotope composition that is in phase with global climate cycles. Global excursions to relatively unradiogenic 187Os/188Os during glacial intervals are consistent with decreased input of radiogenic continental material, reflecting cooler temperatures and reduced continental runoff. Modelling indicates that the shift to unradiogenic values during glacial intervals could be caused by an ~30% decrease in the global river flux, with an ~5% change in river composition. If the residence time of Os in the oceans is ~5 ka then the post-glacial recovery to present-day seawater values is consistent with a corresponding increase in the river flux of around 30%. However, if the residence time of Os is closer to 40 ka, as is suggested by the global river flux, then this demands either significant changes in both the riverine Os flux and composition of around 40% and 30%, respectively, that closely follow the oxygen isotope record, or else a short-lived post-glacial pulse of weathering some 75% greater than the steady-state flux. In either case, these results clearly indicate that climatic changes affect both the flux and composition of weathered material delivered to the oceans on glacial-interglacial timescales.

Lead isotopes inthe Eastern Equatorial Pacific

The influence of atmospheric dust on climate and biogeochemical cycles in the oceans is well understood but poorly quantified. Glacial atmospheric dust loads were generally greater than those during the Holocene, as shown, for example, by the covariation of dust fluxes in the Equatorial Pacific and Antarctic ice cores. Nevertheless, it remains unclear whether these increases in dust flux were associated with changes in sources of dust, which would in turn suggest variations in wind patterns, climate or paleo-environment. Such questions can be answered using radiogenic isotope tracers of dust provenance. Here, we present a 160-kyr high-precision lead isotope time-series of dust input to the Eastern Equatorial Pacific (EEP) from core ODP Leg 138, Site 849 (0°11.59' N, 110°31.18' W). The Pb isotope record, combined with Nd isotope data, rules out contributions from Northern Hemisphere dust sources, north of the Intertropical Convergence Zone, such as Asia or North Africa/Sahara; similarly, eolian sources in Australia, Central America, the Northern Andes and Patagonia appear insignificant based upon the radiogenic isotope data. Fluctuations in Pb isotope ratios throughout the last 160 kyr show, instead, that South America remained the prevailing source of dusts to the EEP. There are two distinct South American Pb isotope end-members, constrained to be located in the south Central Volcanic Zone (CVZ, 22° S - 27.5° S) and the South Volcanic Zone (SVZ, 33° S - 43° S), with the former most likely originating in the Atacama Desert. Dust availability in the SVZ appears to be related to the weathering of volcanic deposits and the development of ash-derived Andosols, and influenced by local factors that might include vegetation cover. Variations in the dust fluxes from the two sources are in phase with both the dust flux and temperature records from Antarctican ice cores. We show that the forcing of dust provenance over time in the EEP overall is influenced by high-southerly-latitude climate conditions, leading to changes in the latitudinal position and strength of the South Westerlies as well as the coastal winds that blow northward along the Chilean margin. The net result is a modulation of dust emission from the Atacama Desert and the SVZ via a northward migration of the South Westerlies during cold periods and southward retreat during glacial terminations.

Late Quaternary carbonate and isotope stratigraphy of DSDP Site 90-594 east of South Island, New Zealand

The late Quaternary sequence off eastern South Island, New Zealand, consists of ~100 m of alternating bluish gray pelagic oozes and greenish gray hemipelagic oozes that extend uninterruptedly back to the Brunhes/Matuyama boundary (0.73 m.y.). A very high resolution (~2400 yr.) record of sediment texture, calcium carbonate content, and planktonic and benthic foraminiferal oxygen and carbon isotope composition demonstrates an in-phase cyclical fluctuation between the sedimentary parameters that closely correspond to the pelagic-hemipelagic sedimentation cycles and the isotope composition. Pelagic oozes, formed during interglacial periods of high eustatic sea level, are characterized by calcareous microfossils, relative enrichment in sand and clay sizes, high carbonate contents, reduced delta18O values, and increased delta13C values. Hemipelagic oozes, associated with glacial episodes and lowered eustatic sea level, include common terrigenous material and siliceous microfossils, are enriched in silt sizes, have low carbonate contents, high delta18O values, and low delta13C values. The history of alpine glaciations and associated erosion of the South Island of New Zealand, as expressed by the appearance of hemipelagic oozes, can be correlated directly with the major fluctuations of Northern Hemisphere ice sheets as expressed by the influence of eustatic sea-level changes on the oxygen isotope composition of both planktonic and benthic foraminifers. This high-accumulation-rate record contains conspicuous intervals of highfrequency, high-amplitude isotope variability including the presence of multiple glacial/interglacial intervals within single isotope stages, and offers one of the best sections cored to date for detailed study of the evolution and history of climate change over the last 0.75 m.y.

Temperatures, salinity, and stable oxygen isotope values of bottom water and of the mollusc shell Arctica islandica from Nantucket Shoals

The carbonate shell of the bivalve Arctica islandica has been recognized, for more than a decade, as a potentially important marine geochemical biorecorder owing to this species' great longevity (200+ years) and wide geographic distribution throughout the northern North Atlantic Ocean, a region vital to global climate and ocean circulation. However, until now this potential has not been realized owing to the difficulty of precisely sampling the shell of this slow growing species. Using newly available automated microsampling techniques combined with micromass stable isotope mass spectrometry, a stable oxygen isotope record (1956-1957 and 1961-1970) has been obtained from a live-captured, 38-year-old A. islandica specimen collected near the former position of the Nantucket Shoals Lightship (41°N. 69°W). The shell's delta18O signal is compared with an expected signal derived from ambient bottom temperature and salinity data recorded at the lightship for the same period. The results show that A islandica's delta18O record (1) is in phase with its growth banding, confirming the annual periodicity of this species' growth bands, (2) is in oxygen isotopic equilibrium with the ambient seawater, (3) shows a consistent shell growth shutdown temperature of ~6°C. which translates into an ~8-month (May-December) shell growth period at this location, and (4) records the ambient bottom temperature with a precision of ~ +/-1.2°C. These results add important information on the life history of this commercially important shellfish species and demonstrate that A. islandica shells can be used to reconstruct inter- and intra-annual records of the continental shelf bottom temperature.

Neodymium isotope composition of planktonic foraminifera from ODP Hole 121-758A

This study presents neodymium isotope and elemental data for cleaned planktonic foraminifera from ODP site 758 in the southernmost reaches of the Bay of Bengal in the north-east Indian Ocean. Cleaning experiments using oxidative-reductive techniques suggest that diagenetic Fe-Mn oxyhydroxide coatings can be effectively removed, and that the measured Nd isotope composition reflects the composition of seawater from which the foraminiferal calcium carbonate was precipitated. Modern core-top Pulleniatina obliquiloculata and Globorotalia menardii give epsilon-Nd values of 310.12 +/- 0.16 and 310.28 +/- 0.16, respectively, indistinguishable from recent direct measurements of surface seawater in this area. A high-resolution Nd isotope record obtained from G. menardii for the past 150 kyr shows systematic variations (Delta epsilon-Nd = 3) on glacial-interglacial timescales. The timing of those variations shows a remarkable correspondence with the global oxygen isotope record, which suggests a process controlling the Nd isotope composition that responds in phase with global climate cycles. Palaeoclimate reconstruction indicates that during the last glacial maximum changes in monsoon circulation resulted in a reduction in rainfall over the Indian subcontinent, and a decrease in the flux of river water delivered to the Bay of Bengal. Thus, changes in the riverine input of Nd, a change in either flux or composition, most likely caused the isotope variations, although changes in dust source or local ocean circulation may have also played a role. These results clearly establish a link between climate change and variations in radiogenic isotopes in the oceans, and illustrate the potential of Nd isotopes in foraminifera for highresolution palaeoceanographic reconstruction.

30 years of synoptic observations from Neumayer Station with links to datasets

High temporal resolution (three hours) records of temperature, wind speed and sea level pressure recorded at Antarctic research station Neumayer (70°S, 8°W) during 1982-2011 are analysed to identify oscillations from daily to intraseasonal timescales. The diurnal cycle dominates the three-hourly time series of temperature during the Antarctic summer and is almost absent during winter. In contrast, the three-hourly time series of wind speed and sea level pressure show a weak diurnal cycle. The dominant pattern of the intraseasonal variability of these quantities, which captures the out-of-phase variation of temperature and wind speed with sea level pressure, shows enhanced variability at timescales of ~ 40 days and ~ 80 days, respectively. Correlation and composite analysis reveal that these oscillations may be related to tropical intraseasonal oscillations via large-scale eastward propagating atmospheric circulation wave-trains. The second pattern of intraseasonal variability, which captures in-phase variations of temperature, wind and sea level pressure, shows enhanced variability at timescales of ~ 35, ~ 60 and ~ 120 days. These oscillations are attributed to the Southern Annular Mode/Antarctic Oscillation (SAM/AAO) which shows enhanced variability at these timescales. We argue that intraseasonal oscillations of tropical climate and SAM/AAO are related to distinct patterns of climate variables measured at Neumayer.

Geochemistry on ferromanganese crusts and nodules from Green Bay, Lake Michigan

The differential solubility of ferromanganese oxides can lead to stratigraphic separation of iron and manganese. Results of chemical analysis of a sequence of ferromanganese nodules overlying iron-rich crusts in northern Green Bay show that selec¬tive ion transport is important in concentrating manganese and associated trace elements near the oxygenated water-sediment interface. Manganese carbonate, which cements ferromanganese nodules, occurs in dark-gray silty sands that are located adjacent to the organic-rich muds of southern Green Bay. These muds contain an average of approximately 3.5 ppm (6x10-5M) interstitial Mn with 2.8 meq/l carbonate alkalinity. Thermodynamic calculation shows that interstitial water approaches equilibrium with MnCO3 in the upper 10 cm of sediment. This carbonate has a composition (Mn73Ca22Fe5)CO3 and has been identified as rhodochrosite.

Carbonate composition of Pliocene-Pleistocene sediments of the Maledives

Ocean Drilling Program (ODP) Leg 115 post-cruise research was focused on two Maldives sites, more precisely on the top 108 m of Hole 716B (water depth, 540 m), equivalent to the past 3.5 m.y., and the top 19.5 m of Hole 714A (water depth, 2195 m), equivalent to the past 0.55 m.y. These sediments consist of mostly unaltered and undisturbed, turbidite-free, periplatform ooze. Results of our research are compared with existing data on Hole 633A (water depth, 1681 m), drilled in the Bahamas during ODP Leg 101, using age/depth models built on the basis of oxygen isotope, nannofossil, and magnetic stratigraphies. Climate-induced, long-term (roughly 0.5 m.y.) aragonite cycles, superposed on short-term (roughly 0.04 and 0.1 m.y.) aragonite cycles, have been established at least during the past 2.0 m.y., in the Maldives and the Bahamas. Our most interesting result is the clear correlation among the aragonite long-term cycles in the Maldives and the Bahamas and the carbonate-preservation, long-term cycles from the open Pacific, Indian, and North Atlantic oceans. The mid-Brunhes dissolution interval, corresponding to the youngest preservation minima of the carbonate-preservation, longterm cycles, is clearly defined by fine aragonite minimum values in the deep periplatform sites, and by maximum fragmentation of pteropod tests in the shallow sites. Aragonite and planktonic d18O records, usually in phase during the late Pleistocene, display, further back in time, discreet intervals where the two records do not match with one another. Major mismatches between both records occur synchronously in the Maldives and Bahamas periplatform sites and seem to correspond to extreme events of either carbonate-preservation or dissolution in the deep pelagic carbonate sites of the equatorial Pacific Ocean. Based on our findings, short- and long-term aragonite cycles can no longer be explained only by variations of aragonite input from the nearby shallow carbonate banks, in response to their alternate flooding and exposure through cyclic sea-level fluctuations. The aragonite long-term cycles in the periplatform environments are interpreted as carbonatepreservation cycles at intermediate-water depths. Their occurrence shows, therefore, that the carbonate chemistry of the entire water column has been influenced by long-term (0.5 m.y.) cyclic variations during the past 2.0 m.y. These major changes of the water-column carbonate chemistry are linked to the climate-induced carbon cycling among the different atmospheric, oceanic, and sedimentary carbon reservoirs.

Variability of the Brazil Current during the late Holocene analysed on two marine sediment cores

Our understanding of the centennial-scale variability of the Brazil Current (BC) during the late Holocene is elusive because of the lack of appropriate records. Here we used the Mg/Ca and oxygen isotopic composition of planktonic foraminifera from two marine sediment cores collected at 27° S and 33° S off southeastern South America to assess the late Holocene variability in the upper water column of the BC. Our results show in phase fluctuations of up to 3 °C in sea surface temperatures (SST), and 0.8 per mil in oxygen isotopic composition of surface sea water, a proxy for relative sea surface salinity (SSS). Time-series analyses of our records indicate a cyclicity with a period of ca. 730 yr. We suggest that the observed cyclicity reflects variability in the strength of the BC associated to changes in the Atlantic meridional overturning circulation (AMOC). Positive (negative) SST and SSS anomalies are related to a strong (weak) BC and a weak (strong) AMOC. Moreover, periods of peak strength in the BC occur synchronously to a weak North Brazil Current, negative SST anomalies in the high latitudes of the North Atlantic, and positive (negative) precipitation anomalies over southeastern South America (equatorial Africa), further corroborating our hypothesis. This study shows a tight coupling between the variability of the BC and the high latitudes of the North Atlantic mediated by the AMOC even under late Holocene boundary conditions.

Geochemistry of dark-light rhythm sediments of the Japan Sea

Ocean Drilling Program Legs 127 and 128 in the Japan Sea have revealed the existence of numerous dark-light rhythms of remarkable consistency in sediments of late Miocene, latest Pliocene, and especially Pleistocene age. Light-colored units within these rhythms are massive or bioturbated, consist of diatomaceous clays, silty clays, or nannofossil-rich clays, and are generally poor in organic matter. Dark-colored units are homogeneous, laminated, or thinly bedded and include substantial amounts of biogenic material such as well-preserved diatoms, planktonic foraminifers, calcareous nannofossils, and organic matter (maximum 7.4 wt%). The dark-light rhythms show a similar geometrical pattern on three different scales: First-order rhythms consist of a cluster dominated by dark-colored units followed by a cluster dominated by light-colored units (3-5 m). Spectral analysis of a gray-value time series suggests that the frequencies of the first-order rhythms in sediments of latest Pliocene and Pleistocene age correlate to the obliquity and the eccentricity cycles. The second-order dark-light rhythms include a light and a dark-colored unit (10-160 cm). They were formed in time spans of several hundred to several ten thousand years, with variance centering around 10,500 yr. This frequency may correspond to half the precessional cycle. Third-order rhythms appear as laminated or thinly bedded dark-light couplets (2-15 mm) within the dark-colored units of the second-order rhythms and may represent annual frequencies. In interpreting the rhythms, we have to take into account that (1) the occurrence of the first- and second-order rhythms is not necessarily restricted to glacial or interglacial periods as is shown by preliminary stable-isotope analysis and comparison with the published d18O record; (2) they appear to be Milankovitch-controlled; and (3) a significant number of the rhythms are sharply bounded. The origin of the dark-light rhythms is probably related to variations in monsoonal activity in the Japan Sea, which show annual frequencies, but also operates in phase with the orbital cycles.

Iberian Margin 420 kyr geochemical and color variations record

Here we report 420 kyr long records of sediment geochemical and color variations from the southwestern Iberian Margin. We synchronized the Iberian Margin sediment record to Antarctic ice cores and speleothem records on millennial time scales and investigated the phase responses relative to orbital forcing of multiple proxy records available from these cores. Iberian Margin sediments contain strong precession power. Sediment "redness" (a* and 570-560 nm) and the ratio of long-chain alcohols to n-alkanes (C26OH/(C26OH + C29)) are highly coherent and in-phase with precession. Redder layers and more oxidizing conditions (low alcohol ratio) occur near precession minima (summer insolation maxima). We suggest these proxies respond rapidly to low-latitude insolation forcing by wind-driven processes (e.g., dust transport, upwelling, precipitation). Most Iberian Margin sediment parameters lag obliquity maxima by 7-8 ka, indicating a consistent linear response to insolation forcing at obliquity frequencies driven mainly by high-latitude processes. Although the lengths of the time series are short (420 ka) for detecting 100 kyr eccentricity cycles, the phase relationships support those obtained by Shackleton []. Antarctic temperature and the Iberian Margin alcohol ratios (C26OH/(C26OH + C29)) lead eccentricity maxima by 6 kyr, with lower ratios (increased oxygenation) occurring at eccentricity maxima. CO2, CH4, and Iberian SST are nearly in phase with eccentricity, and minimum ice volume (as inferred from Pacific d18Oseawater) lags eccentricity maxima by 10 kyr. The phase relationships derived in this study continue to support a potential role of the Earth's carbon cycle in contributing to the 100 kyr cycle.