Sm-Nd isotope and Mn/Ca ratios for cleaned Neogloboquadrina pachyderma from ODP Hole 105-647A (Table 1)

The neodymium (Nd) isotope composition of ancient seawater is a potentially useful tracer of changes in continental inputs and ocean circulation on timescales of a few ka. Here we present the first Nd isotope record for seawater using sedimentary foraminifera cleaned using standard oxidative-reductive techniques. The data, along with Mn/Ca ratios, suggest that cleaned foraminifera provide a reliable record of Nd in seawater and hold out the prospect of using Nd in foraminifera to examine changes in seawater that accompany glacial-interglacial climatic cycles. The principal potential problem to be overcome with the use of forams as records of trace elements in ancient seawater is their diagenetic Fe-Mn coatings. These contain large amounts of Nd and other trace elements but can be cleaned off using highly reducing reagents. Mn(Ca ratios for the majority of the cleaned sedimentary foraminifera analysed here lie within the range (10-100 µmol/mol) that has yielded success in studies of transition elements in forams. Mass-balance modelling suggests that for residual Mn/Ca ratios <100 µmol/mol, Nd added to the foram in the coating will never shift the measured Nd isotope composition significantly away from the seawater value acquired by the foram test in the water column. Additionally, Nd concentrations measured in cleaned sedimentary foraminifera are comparable with those for a modern sample that has never encountered diagenetic fluids. Finally, core-top planktonic foraminifera for two sites have Nd isotope compositions that are identical to local surface seawater. The data we present here for Labrador Sea forams over the past 2.5 m.y. are interpreted in terms of changes in the seawater isotopic composition. The data show a pronounced shift from epsilon-Nd values of ~-12 to ~-19 in the period 2.5-1.5 Ma. This change is interpreted to result from the initiation of Northern Hemisphere glaciation and the increased derivation of Labrador Sea Nd via ice-rafting from Archaean terranes in central Canada. In combination with stable isotope and foraminiferal relative species abundance data, the new Nd data are consistent with the surface hydrography of the Labrador Sea being dominated by a fluctuating balance between cold, polar waters containing unradiogenic Nd and warm, subtropical waters containing more radiogenic Nd. The major change in Labrador Sea Nd that is observed in the past 2.5 Ma can, on its own, account for the change in the Nd isotope composition of North Atlantic Deep Water over the same time period.

Trace element abundance, and Sr and Nd isotope ratios of dust samples in the Pacific Ocean (Table 2)

Eolian dust preserved in deep-sea sediment cores provides a valuable indicator of past atmospheric circulation and continental paleoclimate. In order to identify the provenance of eolian dust, Nd and Sr isotopic compositions and Rb, Sr and rare earth element (REE) concentrations have been determined for the silicate fractions of deep-sea sediments from the north and central Pacific Ocean. Different regions of the Pacific Ocean are characterized by distinct air-borne inputs, producing a large range in epsolin-Nd (-10 to +1), 87Sr/86Sr (0.705-0.721), La/Yb (5-15), EuN/EuN* (0.6-1.0) and Sr/Nd (4-33). The average Nd isotopic composition of Pacific deep-sea sediments (epsilon-Nd = -6), is more radiogenic than the average from the Atlantic (epsilon-Nd = -8). In contrast, the average147Sm/144Nd ratio for Pacific sediments (0.114) is identical to that of Atlantic sediments and to that of global average riverine suspended material. The values of epsilon-Nd and147Sm/144Nd are positively correlated for the Pacific samples but negatively correlated for Atlantic samples, reflecting a fundamental difference between the dominant components in the end members with radiogenic Nd (island-arc components in the Pacific and LREE-enriched intraplate ocean island components in the Atlantic). Samples from the north central Pacific have distinctive unradiogenic epsilon-Nd values of -10, 87Sr/86Sr > 0.715, high La/Yb (> 12), and low EuN/EuN* (0.6) and Sr/Nd (3-6). These data are virtually identical to the values for loess from Asia and endorse the use of these sediments as indicators of Asian paleoclimate and paleowind directions. Island-arc contributions appear to dominate in the northwest Pacific, resulting in higher epsilon Nd (-1 to +1) and lower 87Sr/86Sr (~ 0.705) and La/Yb (~ 5). Sediments from the eastern Pacific tend to have intermediate Sr and Nd isotopic compositions but regionally variable Sr/Nd and REE patterns; they appear to be derived from the west margin of the North and South American continents, rather than from Asia. Our results confirm that dust provenance can be constrained by isotopic and geochemical analyses, which will facilitate reconstructions of past atmospheric circulation and continental paleoclimate.

Chemical and isotope compositions of rocks from altered ocean crust at DSDP/ODP Sites 417/418

Large-scale compositional domains at DSDP/ODP drill sites 417A, 417D and 418A were analyzed for O, Sr and Nd isotope ratios, and REE, U, K, Rb and Sr abundances, to constrain the bulk chemical composition of the oceanic crust that is recycled at subduction zones. The combination of the three sites gives the composition of the upper oceanic crust in this region over a distance of about 8 km. The d18O(SMOW) and 87Sr/86Sr(meas) of compositional domains 10-100 m in size correlate well, with a range of 7.7-19.2 and 0.70364-0.70744, and mean of 9.96 and 0.70475, respectively. The Rb inventory of the upper crust increases by about an order of magnitude, while Sr contents remain constant. U abundances increase moderately under oxidizing alteration conditions and nearly triple in the commonly reducing alteration environments of the upper oceanic crust. REEs are influenced by alteration only to a small extent, and recycled oceanic crust is similar to MORB with respect to 143Nd/144Nd. Even though the average composition of the upper oceanic crust is well defined, the large scale composition varies widely. Highly altered compositional domains may not have a large impact on the average composition of the oceanic crust, but they may preferentially contribute to fluids or partial melts derived from the crust by prograde metamorphic reactions.

Chemistry and boron isotope ratios of Izu arc front volcanic rocks

The process of fluid release from the subducting slab beneath the Izu arc volcanic front (Izu VF) was examined by measuring B concentrations and B isotope ratios in the Neogene fallout tephra (ODP Site 782A). Both were measured by secondary ion mass spectrometry, in a subset of matrix glasses and glassy plagioclase-hosted melt inclusions selected from material previously analyzed for major and trace elements (glasses) and radiogenic isotopes (Sr, Nd, Pb; bulk tephra). These tephra glasses have high B abundances (~10-60 ppm) and heavy delta11B values (+4.5? to +12.0?), extending the previously reported range for Izu VF rocks (delta11B, +7.0? to +7.3?). The glasses show striking negative correlations of delta11B with large ion lithophile element (LILE)/Nb ratios. These correlations cannot be explained by mixing two separate slab fluids, originating from the subducting sediment and the subducting basaltic crust, respectively (model A). Two alternative models (models B and C) are proposed. Model B proposes that the inverse correlations are inherited from altered oceanic crust (AOC), which shows a systematic decrease of B and LILE with increasing depth (from basaltic layer 2A to layer 3), paralleled by an increase in delta11B (from ~ +1? to +10? to +24?). In this model, the contribution of sedimentary B is insignificant (<4% of B in the Izu VF rocks). Model C explains the correlation as a mixture of a low-delta11B (~ +1?) 'composite' slab fluid (a mixture of metasediment- and metabasalt-derived fluids) with a metasomatized mantle wedge containing elevated B (~1-2 ppm) and heavy delta11B (~ +14?). The mantle wedge was likely metasomatized by 11B-rich fluids beneath the outer forearc, and subsequently down dragged to arc front depths by the descending slab. Pb-B isotope systematics indicate that, at arc front depths, ~ 53% of the B in the Izu VF is derived from the wedge. This implies that the heavy delta11B values of Izu VF rocks are largely a result of fluid fractionation, and do not reflect variations in slab source provenance (i.e. subducting sediment vs. basaltic crust). Since the B content of the peridotite at the outer forearc (7-58 ppm B, mean 24 +/- 16 ppm) is much higher than beneath the arc front (~1-2 ppm B), the hydrated mantle wedge must have released a B-rich fluid on its downward path. This 'wedge flux' can explain (1) the across-arc decrease in B and delta11B (e.g. Izu, Kuriles), without requiring a progressive decrease in fluid flux from the subducting slab, and (2) the thermal structure of volcanic arcs, as reflected in the B and delta11B variations of volcanic arc rocks.

Concentrations of Ti, Fe, and Al and radiogenic isotope data for sediments of ODP Leg 177

Identifying terrigenous sources in deep-sea sediments may reveal temporal trends in paleocirculation and the relative role of eolian, upwelled, and hemipelagic Fe sources to surface waters. Bulk elemental and isotopic geochemistry of deep-sea sediments recovered during Ocean Drilling Program Leg 177 in the southeastern Atlantic sector of the Southern Ocean reveal several important aspects of paleocirculation and terrigenous provenance. The sites studied span 43°-53°S and represent different oceanographic settings relative to regional hydrography and sediment type. Bulk sediment geochemistry indicates that terrigenous provenance varied over the past 600 k.y. Site 1089, the northernmost site, exhibits clear glacial-interglacial variability in provenance, while provenance appears to vary regardless of climate state at the more southerly sites (Site 1093 and 1094). Nd and Sr isotopes and Sm/Nd ratios of the terrigenous fraction indicate that study sites have geochemically distinguishable provenance. Nd and Sr isotopes further suggest that Sites 1089 and 1094 both contain detrital components that originated in South America over the past 30 k.y.; however, Site 1089 is also influenced by southern African sources and the strength of the Agulhas Current. The e-Nd data support a more hemipelagic source for the terrigenous material rather than an eolian source based on comparisons with Antarctic ice core data and known sea-ice extent.

Hafnium and neodymium in surface waters of the Atlantic sector of the Southern Ocean

Radiogenic isotopes of hafnium (Hf) and neodymium (Nd) are powerful tracers for water mass transport and trace metal cycling in the present and past oceans. However, due to the scarcity of available data the processes governing their distribution are not well understood. Here we present the first combined dissolved Hf and Nd isotope and concentration data from surface waters of the Atlantic sector of the Southern Ocean. The samples were collected along the Zero Meridian, in the Weddell Sea and in the Drake Passage during RV Polarstern expeditions ANT-XXIV/3 and ANT-XXIII/3 in the frame of the International Polar Year (IPY) and the GEOTRACES program. The general distribution of Hf and Nd concentrations in the region is similar. However, at the northernmost station located 200 km southwest of Cape Town a pronounced increase of the Nd concentration is observed, whereas the Hf concentration is minimal, suggesting much less Hf than Nd is released by the weathering of the South African Archean cratonic rocks. From the southern part of the Subtropical Front (STF) to the Polar Front (PF) Hf and Nd show the lowest concentrations (<0.12 pmol/kg and 10 pmol/kg, respectively), most probably due to the low terrigenous flux in this area and efficient scavenging of Hf and Nd by biogenic opal. In the vicinity of landmasses the dissolved Hf and Nd isotope compositions are clearly labelled by terrigenous inputs. Near South Africa Nd isotope values as low as epsilon-Nd = -18.9 indicate unradiogenic inputs supplied via the Agulhas Current. Further south the isotopic data show significant increases to epsilon-Hf = 6.1 and epsilon-Nd = -4.0 documenting exchange of seawater Nd and Hf with the Antarctic Peninsula. In the open Southern Ocean the Nd isotope compositions are relatively homogeneous (epsilon-Nd ~ -8 to -8.5) towards the STF, within the Antarctic Circumpolar Current, in the Weddell Gyre, and the Drake Pasage. The Hf isotope compositions in the entire study area only show a small range between epsilon-Hf = +6.1 and +2.8 support Hf to be more readily released from young mafic rocks compared to old continental ones. The Nd isotope composition ranges from epsilon-Nd = -18.9 to -4.0 showing Nd isotopes to be a sensitive tracer for the provenance of weathering inputs into surface waters of the Southern Ocean.

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.