Rb, Sr, Sm and Nd concentrations and isotopic composition of basalts from DSDP Leg 74 (Table 1)

Basement intersected in DSDP holes 525A, 528 and 527 on the Walvis Ridge consists of submarine basalt flows and pillows with minor intercalated sediments. These holes are situated on the crest and mid and lower northwest flank of a NNW-SSE-trending ridge block which would have closely paralleled the paleo mid-ocean ridge (Rabinowitz and LaBrecque, 1979 doi:10.1029/JB084iB11p05973, Moore et al. (1983 doi:10.1130/0016-7606(1983)94<907:TWRTDS>2.0.CO;2). The basalts were erupted approximately 70 m.y. ago, an age equivalent to that of immediately adjacent oceanic crust in the Angola Basin and coraistent with formation at the paleo mid-ocean ridge (Moore et al., 1983). The basalt types vary from aphyric quartz tholeiites on the ridge crest to highly plagioclase phyric olivine tholeiites on the ridge flank. These show systematic differences in incompatible trace element and isotopic composition. Many element and isotope ratio pairs form systematic trends with the ridge crest basalts at one end and the highly phyric ridge flank basalts at the other. The low 143Nd/144Nd (0.51238), 206Pb/204Pb (17.54), 207Pb/204Pb (15.47), 208Pb/204Pb (38.14) and high 87Sr/86Sr (0.70512) ratios of the ridge crest basalts suggest derivation from an old Nd/Sm-, Rb/Sr- and Pb/U-enriched mantle source. This isotopic signature is similar to that of alkaline basalts on Tristan da Cunha but offset to significantly lower Nd and Pb isotopic ratios. The isotopic ratio trends may be extrapolated beyond the ridge flank basalts with higher 143Nd/144Nd (0.51270), 206Pb/204Pb (18.32), 207Pb/204Pb (15.52), 208Pb/204Pb (38.77) and lower 87Sr/86Sr (0.70417) ratios in the direction of increasingly Nd/Sm-, Rb/Sr- and Pb/U-depleted source compositions. These isotopic correlations are equally consistent with mixing of depleted and enriched end member melts or partial melting of an inhomogeneous, variably enriched mantle source. However, observed Zr-Ba-Nb-Y interelement relationships are inconsistent with any simple two-component model of magma mixing, as might result from the rise of a lower mantle plume through the upper mantle. Incompatible element and Pb isotopic systematics also preclude extensive involvement of depleted (N-type) MORB material or its mantle sources. In our preferred petrogenetic model the Walvis Ridge basalts were derived by partial melting of mantle similar to an enriched (E-type) MORB source which had become heterogeneous on a small scale due to the introduction of small-volume melts and metasomatic fluids.

Concentrations of natural and anthropogenic organohalogens in water and air samples in the Canadian Arctic during IPY (2007-2008)

Shipboard measurements of organohalogen compounds in air and surface seawater were conducted in the Canadian Arctic in 2007-2008. Study areas included the Labrador Sea, Hudson Bay, and the southern Beaufort Sea. High volume air samples were collected at deck level (6 m), while low volume samples were taken at 1 and 15 m above the water or ice surface. Water samples were taken within 7 m. Water concentration ranges (pg/L) were as follows: alpha-hexachlorocyclohexane (alpha-HCH) 465-1013, gamma-HCH 150-254, hexachlorobenzene (HCB) 4.0-6.4, 2,4-dibromoanisole (DBA) 8.5-38, and 2,4,6-tribromoanisole (TBA) 4.7-163. Air concentration ranges (pg/m**3) were as follows: alpha-HCH 7.5-48, gamma-HCH 2.1-7.7, HCB 48-71, DBA 4.8-25, and TBA 6.4-39. Fugacity gradients predicted net deposition of HCB in all areas, while exchange directions varied for the other chemicals by season and locations. Net evasion of alpha-HCH from Hudson Bay and the Beaufort Sea during open water conditions was shown by air concentrations that averaged 14% higher at 1 m than 15 m. No significant difference between the two heights was found over ice cover. The alpha-HCH in air over the Beaufort Sea was racemic in winter (mean enantiomer fraction, EF = 0.504 ± 0.008) and nonracemic in late spring-early summer (mean EF = 0.476 ± 0.010). This decrease in EF was accompanied by a rise in air concentrations due to volatilization of nonracemic alpha-HCH from surface water (EF = 0.457 ± 0.019). Fluxes of chemicals during the southern Beaufort Sea open water season (i.e., Leg 9) were estimated using the Whitman two-film model, where volatilization fluxes are positive and deposition fluxes are negative. The means ± SD (and ranges) of net fluxes (ng/m**2/d) were as follows: alpha-HCH 6.8 ± 3.2 (2.7-13), gamma-HCH 0.76 ± 0.40 (0.26-1.4), HCB -9.6 ± 2.7 (-6.1 to -15), DBA 1.2 ± 0.69 (0.04-2.0), and TBA 0.46 ± 1.1 ng/m**2/d (-1.6 to 2.0).

Nd and Sr isotopic composition of Cretaceous MORB

Chemical and isotopic (Nd and Sr) compositions have been determined for 12 Cretaceous basaltic samples (108 Ma old) from Holes 417D and 418A of Legs 51,52 and 53. We have found that: (1) The chemical compositions are typical of MORB. They do not vary systematically with the stratigraphic positions of the analyzed samples; thus, the chemical evolution is independent of the eruption sequence that occurred at this Cretaceous ridge. (2) REE patterns for all rocks are characterized by a strong LREE depletion with (La/Sm)N = 0.38-0.50; no significant Eu anomalies are found; HREE are nearly flat or slightly depleted towards Yb-Lu and have 12-18 * chondritic abundances. Combining the results of previous studies, it suggests that no significant temporal and spatial variation in magma chemistry (especially for LIL elements) has occurred in the 'normal' ridge segments over the last 150 Ma. (3) lsotopically, 143Nd/144Nd ratios vary from 0.513026 to 0.513154, corresponding to epsilon-Nd(0) = +7.5 to +10, and they fall in the typical range of MORB. However, these rocks have unexpectedly high 87Sr/86Sr ratios (0.70355-0.70470) which are attributed to the result of seawater-rock interaction. (4) The Nd model ages (Tin), ranging from 1.53 to 2.47 (average 2.06) AE, suggest that the upper mantle source(s) underwent a large scale chemical differentiation leading to LREE and other LIL element depletion about 2 AE ago, assuming a simple two-stage model. More realistically, the variation in Tm(Nd) or epsilon-Nd could be derived from mixing of heterogeneous mantle sources that were a consequence of continuous mantle differentiation and continental formation. (5) Because of the low mg values (0.52-0.63), the analyzed basaltic rocks do not represent primary liquids of mantle melting. The variation in La/Sm ratios and TiO2 are not compatible with a model in which all rocks are genetically related by a simple fractional crystallization. Rather, it is proposed that the basaltic rocks might have been derived from some heterogeneous upper mantle source with or without later magmatic mixing, and followed by some shallow-level fraetionations.

Barium concentration in sediments of the central Equatorial Pacific

High resolution pore-water dissolved Ba concentration-depth profiles were determined at seven sites across an Equatorial Pacific productivity gradient from 12°S to 9°N, at 140°W. These data are important for understanding the physical, chemical, and biological controls on Ba recycling in the ocean, and for evaluating the paleo-oceanographic significance of Ba content in central Equatorial Pacific sediments. Pore-water Ba concentrations at all sites are higher than in the overlying bottom water, leading to a diffusive flux of Ba into the ocean. A pronounced subsurface concentration maximum exceeding barite solubility characterizes the dissolved Ba pore-water profiles, suggesting that the Ba regenerated in the upper few millimeters of sediment is not controlled by barite solubility. A few centimeters down-core Ba concentrations reach a relatively constant value of approximately barite saturation. The benthic Ba flux shows a clear zonal trend, with a maximum between 2°S and 2°N, most probably due to higher productivity at the equatorial divergence zone, and with lowest values at the southern and northern extremes of the transect. The dissolved Ba flux between 2°S and 2°N is ~30 nmol/cm**2 yr and drops to 6 nmol/cm**2 yr at 12°S. Even the lowest fluxes are significantly higher than those previously reported for the open ocean. In the Equatorial Pacific the calculated Ba recycling efficiency is about 70%. Thus, ~30% of the particulate Ba flux to the deep ocean is preserved in the sediments, compared with less than 1% for organic carbon and ~5% for biogenic silica. Mass balance calculation of the oceanic Ba cycle, using a two-box model, implies benthic Ba fluxes similar to those reported here for a steady-state ocean.

Noble gases sampled from three cruises in the eastern tropical Atlantic in September 2005 and June/July 2006

Upwelling velocities w in the equatorial band are too small to be directly observed. Here, we apply a recently proposed indirect method, using the observed helium isotope (3He or 4He) disequilibria in the mixed layer. The helium data were sampled from three cruises in the eastern tropical Atlantic in September 2005 and June/July 2006. A one-dimensional two-box model was applied, where the helium air-sea gas exchange is balanced by upwelling from 3He-rich water below the mixed layer and by vertical mixing. The mixing coefficients Kv were estimated from microstructure measurements, and on two of the cruises, Kv exceeded 1 x 10**-4 m**2/s, making the vertical mixing term of the same order of magnitude as the gas exchange and the upwelling term. In total, helium disequilibrium was observed on 54 stations. Of the calculated upwelling velocities, 48% were smaller than 1.0 x 10**-5 m/s, 19% were between 1.0 and 2.0 x 10**-5 m/s, 22% were between 2.0 and 4.0 x 10**-5 m/s, and on 11% of upwelling velocities exceeded this limit. The highest upwelling velocities were found in late June 2006. Meridional upwelling distribution indicated an equatorial asymmetry with higher vertical velocities between the equator and 1° to 2° south compared to north of the equator, particularly at 10°W. Associated heat flux into the mixed layer could be as high as 138 W/m**2, but this depends strongly on the chosen depths where the upwelled water comes from. By combining upwelling velocities with sea surface temperature and productivity distributions, a mean monthly equatorial upwelling rate of 19 Sv was estimated for June 2006 and a biweekly mean of 24 Sv was estimated for September 2005.

C and H geochemistry of altered oceanic crus of ODP/IODP Hole 1256D

Carbon and hydrogen concentrations and isotopic compositions were measured in 19 samples from altered oceanic crust cored in ODP/IODP Hole 1256D through lavas, dikes down to the gabbroic rocks. Bulk water content varies from 0.32 to 2.14 wt% with dD values from -64per mil to -25per mil. All samples are enriched in water relative to fresh basalts. The dD values are interpreted in terms of mixing between magmatic water and another source that can be either secondary hydrous minerals and/or H contained in organic compounds such as hydrocarbons. Total CO2, extracted by step-heating technique, ranges between 564 and 2823 ppm with d13C values from -14.9per mil to -26.6per mil. As for water, these altered samples are enriched in carbon relative to fresh basalts. The carbon isotope compositions are interpreted in terms of a mixing between two components: (1) a carbonate with d13C = -4.5per mil and (2) an organic compound with d13C = -26.6per mil. A mixing model calculation indicates that, for most samples (17 of 19), more than 75% of the total C occurs as organic compounds while carbonates represent less than 25%. This result is also supported by independent estimates of carbonate content from CO2 yield after H3PO4 attack. A comparison between the carbon concentration in our samples, seawater DIC (Dissolved Inorganic Carbon) and DOC (Dissolved Organic Carbon), and hydrothermal fluids suggests that CO2 degassed from magmatic reservoirs is the main source of organic C addition to the crust during the alteration process. A reduction step of dissolved CO2 is thus required, and can be either biologically mediated or not. Abiotic processes are necessary for the deeper part of the crust (>1000 mbsf) because alteration temperatures are greater than any hyperthermophilic living organism (i.e. T > 110 °C). Even if not required, we cannot rule out the contribution of microbial activity in the low-temperature alteration zones. We propose a two-step model for carbon cycling during crustal alteration: (1) when "fresh" oceanic crust forms at or close to ridge axis, alteration starts with hot hydrothermal fluids enriched in magmatic CO2, leading to the formation of organic compounds during Fischer-Tropsch-type reactions; (2) when the crust moves away from the ridge axis, these interactions with hot hydrothermal fluids decrease and are replaced by seawater interactions with carbonate precipitation in fractures. Taking into account this organic carbon, we estimate C isotope composition of mean altered oceanic crust at ? -4.7per mil, similar to the d13C of the C degassed from the mantle at ridge axis, and discuss the global carbon budget. The total flux of C stored in the altered oceanic crust, as carbonate and organic compound, is 2.9 ± 0.4 * 10**12 molC/yr.

Volcanic rocks from the submarine Vityaz Ridge: their age, chemical and isotopic compositions

Results of geological studies at the submarine Vityaz Ridge carried out during cruises 37 and 41 of R/V Akademik Lavrent'ev in 2005 and 2006 are reported. The studied area is located at an near-island trench of the slope in the central part of the Kuril Island arc. Morphologically it consists of two parts: an inner volcanic arc represented by the Great Kuril Range and an outer arc corresponding to the submarine Vityaz Ridge. Diverse rocks composing the basement and the sedimentary cover of the ridge were recovered by dredging. Based on K-Ar dating and geochemistry, volcanics were divided into Paleocene, Eocene, late Oligocene, and Pliocene-Pleistocene complexes. Each of the complexes reflects a tectonomagmatic stage in the ridge evolution. Geochemical and isotope data on the volcanics indicate contribution of ancient crustal material in the magma source and, correspondingly, formation of this structure on the continental basement. Two-stage model ages (TDM2) vary in a wide range from zero values in mafic rocks to 0.77 Ga in felsic varieties, pointing to presence of Precambrian protolith in the source of the felsic rocks of the Vityaz Ridge. The Pliocene-Pleistocene volcanics are classed with tholeiitic, calc-alkaline, and subalkaline series, which differ in alkali contents and REE fractionation. Values of (La/Sm)_n and (La/Yb)_n ratios vary from 0.74 and 0.84 in the tholeiitic varieties to 1.19 and 1.44 in the calc-alkaline and 2.32 and 3.73 in the subalkaline rocks. All three varieties occur within the same volcanic edifices and formed during differentiation of magmatic melts that were channeled along fault zones from the mantle source slightly enriched in crustal component.

Major and trace elements and Nd and Sr isotope geochemistry of basalts at DSDP Leg 74 Holes

Basement intersected in Holes 525A, 528, and 527 on the Walvis Ridge consists of submarine basalt flows and pillows with minor intercalated sediments. These holes are situated on the crest and mid- and lower NW flank of a NNW-SSE-trending ridge block which would have closely paralleled the paleo mid-ocean ridge. The basalts were erupted approximately 70 Ma, a date consistent with formation at the paleo mid-ocean ridge. The basalt types vary from aphyric quartz tholeiites on the Ridge crest to highly Plagioclase phyric olivine tholeiites on the flank. These show systematic differences in incompatible trace element and isotopic composition, and many element and isotope ratio pairs form systematic trends with the Ridge crest basalts at one end and the highly phyric Ridge flank basalts at the other. The low 143Nd/144Nd (0.51238) and high 87Sr/86Sr (0.70512) ratios of the Ridge crest basalts suggest derivation from an old Nd/Sm and Rb/Sr enriched mantle source. This isotopic signature is similar to that of alkaline basalts on Tristan da Cunha but offset by somewhat lower 143Nd/144Nd values. The isotopic ratio trends may be extrapolated beyond the Ridge flank basalts (which have 143Nd/144Nd of 0.51270 and 87Sr/86Sr of 0.70417) in the direction of typical MORB compositions. These isotopic correlations are equally consistent with mixing of depleted and enriched end-member melts or partial melting of an inhomogeneous, variably enriched mantle source. However, observed Zr-Ba-Nb-Y interelement relationships are inconsistent with any simple two-component model of magma mixing or partial melting. They also preclude extensive involvement of depleted (N-type) MORB material or its mantle sources in the petrogenesis of Walvis Ridge basalts.

Carbonate sedimentation beneath the Carlifornia Current system

A north-south transect of 17 cores was constructed along the eastern boundary of the California Current system from 33° to 42°N to investigate the changes in biogenic sedimentation over the past 30 kyr. Percentages and mass accumulation rates of CaCO3, Corg, and biogenic opal were assembled at 500 to 1000 years/sample to provide relatively high resolution. Time-space maps reveal a complex pattern of changes that do not follow a simple glacial-interglacial two-mode model. Biogenic sedimentation shows responses that are sometimes time-transgressive and sometimes coeval, and most of the responses show more consistency within a limited geographic area than any temporal consistency. Reconstructed conditions during late oxygen isotope stage 3 were more like early Holocene conditions than any other time during the last 30 kyr. Coastal upwelling and productivity during oxygen isotope stage 3 were relatively strong along the central California margin but were weak along the northern California margin. Precipitation increased during the last glacial interval in the central California region, and the waters of the southern California margin had relatively low productivity. Productivity on the southern Oregon margin was relatively low at the beginning of the last glacial interval, but by about 20 ka, productivity in this area significantly increased. This change suggests that the center of the divergence of the West Wind Drift shifted south at this time. The end of the last glacial interval was characterized by increased productivity in the southern California margin and increased upwelling along the central California margin but upwelling remained weak along the northern California margin. A sudden (<300 years) decrease in CaCO3, Corg, and biogenic opal occurred at 13 ka. The changes suggest a major reorientation of the atmospheric circulation in the North Pacific and western North America and the establishment of a strong seasonality in the central California region. A carbonate preservation event occurred at 10 ka that appears to reflect the uptake of CO2 by the terrestrial biosphere as the northern latitudes were reforested following retreat of the glaciers. The Holocene has been a period of relatively high productivity in the southern California margin, relatively strong coastal upwelling along the central California margin, relatively weak upwelling along the northern California margin, and the northward migration of the divergence zone of the West Wind Drift.

Plio-Pleistocene diatom biostratigraphy from ODP Leg 177, Atlantic sector of the Southern Ocean

Seven sites were drilled during Ocean Drilling Program Leg 177 in the Atlantic sector of the Southern Ocean (SO) on a transect over the Antarctic Circumpolar Current from the Subantarctic to the Antarctic Zone. At four sites sediments were recovered with a Pliocene/Pleistocene sediment package of up to 580 m allowing the refinement of previous diatom zonation concepts. Samples were analyzed on stratigraphic distribution and abundance of diatom species. A refined diatom biozonation tied to the geomagnetic polarity record is proposed. For the middle and late Pleistocene two zonations applicable to the northern and southern area of the SO were constructed, considering different latitudinal distributions of biostratigraphic diatom marker species. The southern zonation for the Pleistocene relies on the occurrence of species of the genus Rouxia, R. leventerae and R. constricta n. sp. as well as on a revised last occurrence datum (LOD) of Actinocyclus ingens (0.38 Ma, late marine isotope stage (MIS) 11). The use of these new stratigraphic marker species refines the temporal resolution for biostratigraphic age assignment to up to 0.1 Myr. In particular the LOD of R. leventerae as an indicator for the MIS 6/5 boundary (Termination II) will improve future dating of carbonate-free Antarctic sediments. These new data were obtained from sediments of Sites 1093 and 1094 (Antarctic Zone). The northern zonation for the middle and late Pleistocene time interval is based on the Pleistocene abundance pattern of Hemidiscus karstenii which was already proposed by previous investigations (e.g. Gersonde and Barcena, 1998). One new species (R. constricta) and two new combinations (Fragilariopsis clementia, Fragilariopsis reinholdii) are proposed in this study.

Two-dimensional (2-D) peat microtopographical model

Matlab script file of a two-dimensional (2-D) peat microtopographical model together with other supplementary files that are required to run the model.

Radiolarian-based paleotemperatures of ODP Site 177-1089 in the Atlantic Sector of the Southern Ocean

Two cores, Site 1089 (ODP Leg 177) and PS2821-1, recovered from the same location (40°56'S; 9°54'E) at the Subtropical Front (STF) in the Atlantic Sector of the Southern Ocean, provide a high-resolution climatic record, with an average temporal resolution of less than 600 yr. A multi-proxy approach was used to produce an age model for Core PS2821-1, and to correlate the two cores. Both cores document the last climatic cycle, from Marine Isotopic Stage 6 (MIS 6, ca. 160 kyr BP, ka) to present. Summer sea-surface temperatures (SSSTs) have been estimated, with a standard error of ca. +/-1.16°C, for the down core record by using Q-mode factor analysis (Imbrie and Kipp method). The paleotemperatures show a 7°C warming at Termination II (last interglacial, transition from MIS 6 to MIS 5). This transition from glacial to interglacial paleotemperatures (with maximum temperatures ca. 3°C warmer than present at the core location) occurs earlier than the corresponding shift in delta18O values for benthic foraminifera from the same core; this suggests a lead of Southern Ocean paleotemperature changes compared to the global ice-volume changes, as indicated by the benthic isotopic record. The climatic evolution of the record continues with a progressive temperature deterioration towards MIS 2. High-frequency, millennial-scale climatic instability has been documented for MIS 3 and part of MIS 4, with sudden temperature variations of almost the same magnitude as those observed at the transitions between glacial and interglacial times. These changes occur during the same time interval as the Dansgaard-Oeschger cycles recognized in the delta18Oice record of the GRIP and GISP ice cores from Greenland, and seem to be connected to rapid changes in the STF position in relation to the core location. Sudden cooling episodes ('Younger Dryas (YD)-type' and 'Antarctic Cold Reversal (ACR)-type' of events) have been recognized for both Termination I (ACR-I and YD-I events) and II (ACR-II and YD-II events), and imply that our core is located in an optimal position in order to record events triggered by phenomena occurring in both hemispheres. Spectral analysis of our SSST record displays strong analogies, particularly for high, sub-orbital frequencies, to equivalent records from Vostok (Antarctica) and from the Subtropical North Atlantic ocean. This implies that the climatic variability of widely separated areas (the Antarctic continent, the Subtropical North Atlantic, and the Subantarctic South Atlantic) can be strongly coupled and co-varying at millennial time scales (a few to 10-ka periods), and eventually induced by the same triggering mechanisms. Climatic variability has also been documented for supposedly warm and stable interglacial intervals (MIS 1 and 5), with several cold events which can be correlated to other Southern Ocean and North Atlantic sediment records.

Abundance and opal input of radiolarian species of two sediment cores from the Atlantic sector of the Southern Ocean

Radiolarian-based paleoceanographic reconstructions generally use the abundance of selected radiolarian species. However, the recent focus on the opal flux and the development of isotope measurements in biogenic opal and the organic matter embedded in it demands a better knowledge of the origin of the opal. We present here an estimation of the opal content of the skeleton of 63 radiolarian species from two sites in the Southern Ocean. The skeletons are modelled as associations of simple geometrical shapes, and the volume thus obtained is combined with opal density to obtain the amount of opal. These data are, thus, used to determine the most important opal carriers in the radiolarian assemblage in both cores.

Age model of firn core DML03C98_09

The influence of atmospheric circulation patterns on sea salt aerosol deposition in the study area of the new EPICA (European Project for Ice Coring in Antarctica) deep drilling in Dronning Maud Land (DML), Antarctica, has been investigated. Comparison of ice core records with reanalysis data showed that recent sea salt concentrations are strongly influenced by the occurrence of a blocking high pressure ridge over the eastern and enhanced storm activity over the western Atlantic sector of the Southern Ocean (SO) leading to marine intrusions, thus enhanced sea salt export, into DML. These variations occur with periods of 4-5 and 12-14 yr, the prior being associated with the Antarctic Circumpolar Wave (ACW). The prevalence of these periodicities in a 2000 year ice core record from DML shows for the first time that the ACW is a prevalent feature of SO atmosphere dynamics over the last two millennia.

Diatom-bound N isotope records over the last two glacial cycles in sediment core PS75/072-4

In a sediment core from the Pacific sector of the Antarctic Zone (AZ) of the Southern Ocean, we report diatom-bound N isotope (d15Ndb) records for total recoverable diatoms and two distinct diatom assemblages (pennate and centric rich). These data indicate tight coupling between the degree of nitrate consumption and Antarctic climate across the last two glacial cycles, with d15Ndb (and thus the degree of nitrate consumption) increasing at each major Antarctic cooling event. Coupled with evidence from opal- and barium-based proxies for reduced export production during ice ages, the d15Ndb increases point to ice age reductions in the supply of deep ocean-sourced nitrate to the AZ surface. The two diatom assemblages and species abundance data indicate that the d15Ndb changes are not the result of changing species composition. The pennate and centric assemblage d15Ndb records indicate similar changes but with a significant decline in their difference during peak ice ages. A tentative seasonality-based interpretation of the centric-to-pennate d15Ndb difference suggests that late summer surface waters became nitrate free during the peak glacials.