(Table 1) Nd and Sr isotopic analyses of ODP Leg 127 basalts

Sr and Nd isotopic compositions are reported for basaltic rocks collected during ODP Leg 127 from the Yamato Basin, a rifted backarc basin in the Japan Sea. The basalts are classified into two groups in terms of Nd isotopic composition: the upper sills at Site 797 are characterized by higher 143Nd/144Nd ratios (0.513083-0.513158, epsilon-Nd = 8.68-10.14) and the basalts from Site 794 and the lower sills at Site 797 have lower 143Nd/144Nd ratios (0.512684-0.512862, epsilon-Nd = 0.90-4.37). All of the basalts show higher Sr isotopic compositions than those of the mantle array, which is attributed to seawater alteration. The basalts with lower Nd isotopic values ranging in age from 20.6 to 17.3 Ma have tapped an enriched subcontinental upper mantle (SCUM) with the minor involvement of a depleted asthenospheric mantle (AM). Subsequent change in composition through the physical replacement of SCUM by AM yielded the basalts of the upper sills of higher Nd isotopic compositions. This event within the upper mantle was associated with the breakup of the overlying lithosphere during the rifting of the Japan Sea backarc basin.

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.

Nd, Sr and Pb isotopic composition of eolian dust deposited in the central North Pacific

The silicate fractions of recent pelagic sediments in the central north Pacific Ocean are dominated by eolian dust derived from central Asia. An 11 Myr sedimentary record at ODP Sites 885/886 at 44.7°N, 168.3°W allows the evaluation of how such dust and its sources have changed in response to late Cenozoic climate and tectonics. The extracted eolian fraction contains variable amounts (>70%) of clay minerals with subordinate quartz and plagioclase. Uniform Nd isotopic compositions (epsilon-Nd =38.6 to 310.5) and Sm/Nd ratios (0.170-0.192) for most of the 11 Myr record demonstrate a well-mixed provenance in the basins north of the Tibetan Plateau and the Gobi Desert that was a source of dust long before the oldest preserved Asian loess formed. epsilon-Nd values of up to 36.5 for samples 62.9 Ma indicate <=35 wt% admixture of a young, Kamchatka-like volcanic arc component. The coherence of Pb and Nd in the erosional cycle allows us to constrain the Pb isotopic composition of Asian loess devoid of anthropogenic contamination to 206Pb/204Pb =18.97 +/- 0.06, 207Pb/204Pb =15.67 +/- 0.02, 208Pb/204Pb =39.19 +/- 0.11. 87Sr/86Sr (0.711-0.721) and Rb/Sr ratios (0.39-1.1) vary with dust mineralogy and provide an age indication of ~250 Ma. 40Ar/39Ar ages of six dust samples are uniform around 200 Ma and match the K-Ar ages of modern dust deposited on Hawaii. These data reflect the weighted age average of illite formation. Changes from illite- smectite with significant kaolinite to illite- and chlorite-rich, kaolinite-free assemblages since the late Pliocene document changes in the intensity of chemical weathering in the source region. Such weathering evidently did not disturb the K-Ar systematics, and only induced scatter in the Rb-Sr data. We propose that when smectite forms at the expense of illite, K and Ar are quantitatively lost from what becomes smectite, but are quantitatively retained in adjacent illite layers. 40Ar/39Ar age data, therefore, are insensitive to smectite formation during chemical weathering but date the diagenetic growth of illite, the major K-bearing phase in the dust. Over the past 12 Myr, the dust flux to the north Pacific increased by more than an order of magnitude, documenting a substantial drying of central Asia. This climatic change, however, did not alter the ultimate source of the dust, and neoformational products of chemical weathering always remained subordinate to assemblages reworked by mechanical erosion in dust deposited in eastern Asia and the Pacific Ocean.

Nd isotopes of ODP Sites 146-893 and 167-1017 samples

Changes in the source of intermediate waters to the southern California margin may have caused variations in seafloor oxygen levels on stadial-interstadial time scales. We test this hypothesis using the Nd isotopic composition of benthic foraminifera and fossil fish debris from ODP Sites 893 and 1017 to track the composition of intermediate waters across interstadials 8-14 (~37-52 ka) during Marine Isotope Stage 3. The epsilon-Nd values of waters bathing the seafloor at Site 893 were typically ~-9 and those bathing Site 1017 were ~-7, both of which are significantly less radiogenic than waters that had originated in either the North Pacific or Southern Ocean (by the time such waters reached the southern California margin). Detrital silicate epsilon-Nd values of nearly -12 suggest that this offset toward lower epsilon-Nd values was likely caused by boundary scavenging that partially overprinted the water mass composition with local/regional fluvial Nd inputs. In spite of the evidence for boundary scavenging, the lack of systematic seawater Nd isotope changes on a stadial-interstadial basis suggests that the provenance of the intermediate waters did not change, and that the waters were derived from the Southern Ocean. Instead, changes in local/regional sea surface productivity may have caused the recorded changes in seafloor oxygenation.

Nd concentrations and isotopic composition in the western Mediterranean Sea

The concentration and isotopic composition of Nd in water and particles collected in the western Mediterranean Sea are studied by two complementary approaches. The first examines local vertical profiles and time series; the second considers the global Nd budget of the whole western Mediterranean Sea. These two approaches are used to quantify the Nd inputs and the dissolved/particulate exchange processes in the water column. Two profiles of Nd in seawater in the Ligurian Sea taken in May and October 1992 show an average epsilon-Nd(0) = -9.6 ± 0.5. Seawater from the Strait of Sicily, representative of the eastern waters flowing into the western basin, is more radiogenic [epsilon-Nd(0) = -7.7 ± 0.6]. Profiles of particulate matter collected in sediment traps in coastal (Gulf of Lions) and offshore (Ligurian Sea) environments are also shown. Particles are enriched in Nd and are more radiogenic near the coast than offshore. Measurements of Nd concentration and epsilon-Nd(0) of external sources to the western Mediterranean Sea compared with the literature data demonstrate that particulate flux of atmospheric Saharan origin are more rich ([Nd] = 38 ± 10 µg/g) and less radiogenic [epsilon-Nd(0) = -13.0 ± 1.0] than riverine particulate discharge ([Nd] = 21.5 ± 4.4 µg/g; epsilon-Nd(0) = -10.1 ± 0.5), allowing to trace Nd particulate inputs in the water column. Nd atmospheric flux appears to be the major source into the whole western basin, although lateral advection of riverine material is the prevailing process in the coastal environment. Offshore, the vertical propagation of an important Saharan dust event has been recorded for two months in sediment traps at 80, 200 and 1000 m. The evolution of the resulting negative epsilon-Nd(0) peak along depth and time shows that the particles reach 200 m on a time scale of one week. For the first time, the Nd budget in the western Mediterranean basin is constrained by both concentrations and isotopic compositions measured in particles and seawater. Surface budget requires a remobilization of 30 ± 20% of particulate Nd input. In deep water, dissolved Nd concentrations are balanced by a scavenging of 10 ± 20% of the sinking particulate flux. On the other hand, the deep isotopic compositions suggest an exchange between 30 ± 20% of the sinking particles and the deep waters. The hypothesis of a non-stationary regime for the surface waters in the Ligurian Sea is also considered.

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.

Nd isotope composition of fossil fish teeth of ODP Hole 119-738B

We report an optimized method for extracting neodymium (Nd) from fossil fish teeth with a single-stage column (125 µl stem volume; LN Resin, Eichrom Industries, Darien Illinois) for isotopic analysis by multi-collector inductively coupled mass spectrometry (MC-ICMPS). Three reference materials (basalt: BCR-2, BHVO-2; phosphate: fossil bone composite) and splits of fossil fish teeth samples previously processed with existing two-stage column methods were processed using the single-stage column method. 143Nd/144Nd values of reference materials agree within error with published values, and the values for fish teeth correspond with sample splits processed with two-stage columns. Precision to ± ~0.23 epsilon-Nd was achieved for 30 ng Nd samples of reference materials, and Nd isotope measurements of fossil fish tooth sample replicates as small as 7 ng Nd were reproducible within long term instrumental uncertainty. We demonstrate the utility of the new method with the first high resolution Nd isotope record spanning the ~40.0 Ma middle Eocene Climatic Optimum, which shows an excursion of 0.65 epsilon-Nd during the peak warming at the study site (Ocean Drilling Program Leg 119, Site 738; 30 kyr sample spacing from 40.3 to 39.6 Ma). LN Resin is already used in standard methods for separating Nd, and Nd isotopes are routinely measured by MC-ICPMS with high efficiency inlet systems. Our innovation is a single, small volume LN Resin column for Nd separation. The streamlined approach results in a 10X increase in sample throughput.

Geochemical and Nd isotopic investigations of sediments from the South China Sea

Secular variations in geochemistry and Nd isotopic data have been documented in sediment samples at ODP Site 1148 in the South China Sea. Major and trace elements show significant changes at ca. 29.5 Ma and 26-23 Ma, whereas epsilon-Nd values show a single change at ca. 26-23 Ma. Increases in Al/Ti, Al/K, Rb/Sr, and La/Lu ratios and a decrease in the Th/La ratio of the sediments beginning at 29.5 Ma are consistent with more intense chemical weathering in the source region. The abrupt change in Nd isotopes and geochemistry at ca. 26-23 Ma coincides with a major discontinuity in the sedimentology and physical properties of the sediments, implying a drastic change in sedimentary provenance and environment at the drill site. Comparison of the Nd isotopes of sediments from major rivers flowing into the South China Sea suggests that pre-27 Ma sediments were dominantly derived from a southwestern provenance (Indochina-Sunda Shelf and possibly northwestern Borneo), whereas post-23 Ma sediments were derived from a northern provenance (South China). This change in provenance from southwest to north was largely caused by ridge jumping during seafloor spreading of the South China Sea, associated with a southwestward expansion of the ocean basin crust and a global rise in sea level. Thus, the geochemical and Nd isotopic changes in the sediments at ODP Site 1148 are interpreted as a response to a major plate reorganization in SE Asia at ca. 25 Ma.

(Table A1) Isotopic ratios of Sr, Nd, and Pb for sediments in ODP Leg 138 sites

The provenance of eolian dust supplied to deep-sea sediments has the potential to offer insights into changes in past atmospheric circulation. Specifically, measuring temporal changes in dust provenance can shed light on changes in the mean position of the Intertropical Convergence Zone (ITCZ), a region acting as a barrier separating wind-blown material derived from northern versus southern hemisphere sources. Here we have analyzed Nd, Sr, and Pb isotope ratios in the operationally-defined detrital component extracted from deep-sea sediments in the eastern equatorial Pacific (EEP) along a meridional transect at 110°W from 3°S to 7°N (ODP Leg 138, sites 848-853). Sr isotope results show that barite Sr has a significant influence on 87Sr/86Sr isotope ratios of samples in the upwelling zone of the EEP. However, sites located >3° or more away from the equator (sites 852 and 853) are believed to not be affected by barite Sr and provide useful detrital Sr signals. 208Pb/206Pb and 207Pb/206Pb ratios in all cores fall into the Pb-isotope space of five potential dust sources (Asia, North and Central/South America, Sahara, and Australia), with no distinct isotopic fingerprinting of the dominant source(s). epsilon-Nd values were most valuable for discerning detrital source provenance, and their values at all sites, ranging from ~5.46 to ~3.25, were more unradiogenic for sediments deposited during the last glacial than for those deposited during the Holocene. There are distinct latitudinal trends in the epsilon-Nd values, with more radiogenic values further south and less radiogenic values further north, excluding site 848. This distinction holds true for both Holocene and last glacial periods. For the most southerly site, 848, we invoke, for the first time, a distinct southern hemisphere Australian source as being responsible for the unradiogenic Nd isotope ratios. Both average last glacial and Holocene epsilon-Nd values show similar sharp gradients along the transect between 5.29°N and 2.77°N, suggesting little movement of the glacial ITCZ in the EEP. However, during the deglacial, this gradient is stronger and shifted further north between 5.29°N and 7.21°N, suggesting a more northerly, possibly stronger, deglacial ITCZ.

South Pacific dissolved Nd isotope compositions, rare earth element and nutrient concentrations from SONNE cruise SO213

Despite its enormous extent and importance for global climate, the South Pacific has been poorly investigated in comparison to other regions with respect to chemical oceanography. Here we present the first detailed analysis of dissolved radiogenic Nd isotopes (epsilon-Nd) and rare earth elements (REEs) in intermediate and deep waters of the mid-latitude (~40°S) South Pacific along a meridional transect between South America and New Zealand. The goal of our study is to gain better insight into the distribution and mixing of water masses in the South Pacific and to evaluate the validity of Nd isotopes as a water mass tracer in this remote region of the ocean. The results demonstrate that biogeochemical cycling (scavenging processes in the Eastern Equatorial Pacific) and release of LREEs from the sediment clearly influence the distribution of the dissolved REE concentrations at certain locations. Nevertheless, the Nd isotope signatures clearly trace water masses including AAIW (Antarctic Intermediate Water) (average epsilon-Nd = -8.2 ± 0.3), LCDW (Lower Circumpolar Deep Water) (average epsilon-Nd = -8.3 ± 0.3), NPDW (North Pacific Deep Water) (average epsilon-Nd = -5.9 ± 0.3), and the remnants of NADW (North Atlantic Deep Water) (average epsilon-Nd = -9.7 ± 0.3). Filtered water samples taken from the sediment-water interface under the deep western boundary current off New Zealand suggest that boundary exchange processes are limited at this location and highlight the spatial and temporal variability of this process. These data will serve as a basis for the paleoceanographic application of Nd isotopes in the South Pacific.

H, O, Sr, and Nd isotope ratios and water, Rb, Sr, Sm, and Nd content of ODP Hole 116-717C and 116-718C samples (Table 2)

Mineralogical and H, O, Sr, and Nd isotope compositions have been analyzed on a set of representative samples from the 17-m.y. section in ODP Leg 116 Holes 717C and 718C. Based on the mineralogical composition of the fraction <2 µm together with the lithogenic-biogenic composition of the fraction >63 µm, the whole section can be subdivided into three major periods of sedimentation. Between 17.1 and 6 m.y., and between 0.8 m.y. to present, the sediments are characterized by sandy and silty turbiditic inputs with a high proportion of minerals derived from a gneissic source without alteration. In the fraction <2 µm, illite and chlorite are dominant over smectite and kaolinite. The granulometric fraction >63 µm contains quartz, muscovite, biotite, chlorite, and feldspars. The 6-to 0.8-m.y. period is represented by an alternation of sandy/silty horizons, muds, and calcareous muds rich in smectite, and kaolinite (50% to 85% of the fraction <2 µm) and bioclastic material. The presence of smectite and kaolinite, as well as the 18O/16O and the 87Sr/86Sr ratios of the fraction <2 µm, imply an evolution in a soil environment and exchanges with meteoric ground water. The ranges of isotopic compositions are limited throughout the section: d18O quartz = 11.7 to 13.3 per mil, 87Sr/86Sr = 0.733 to 0.760 and epsilon-Nd (0) = -17.4 to -13.8. These values are within those of the High Himalaya Crystalline series, and they are considered to reflect this source region. The data imply that, since 17 Ma, this formation has supplied the major part of the eroded material.

REE, Ba, and Sr abundances and Sr, Nd, and Ce isotope ratos of ODP Hole 110-504B basalts

Abundances of rare earth elements (REE), Ba, and Sr and isotopic ratios of Sr, Nd, and Ce were determined for six samples of basalts drilled at Hole 504B on Leg 111 of the Ocean Drilling Program. Analyses found that these basalts are the most depleted in Sr, Ba, and light REE among mid-ocean ridge basalts (MORB); Ba depletion is especially notable. On the other hand, Sr, Nd, and Ce isotopic ratios for basalts from Hole 504B are within the range of typical MORB values.

Miocene Mediterranean Nd, Sr, C and O isotope composition

Isotopic compositions of marine sediments and fossils have been investigated from northern basins of the Mediterranean to help constrain local oceanographic and climatic changes adjacent to the uplifting Alps. Stable C and O isotope compositions of benthic and planktonic foraminifera from the Umbria-Marche region (UMC) have an offset characteristic for their habitats and the changes in composition mimic global changes, suggesting that the regional conditions of climate and the carbon cycle were controlled by global changes. The radiogenic isotope composition of these fossil assemblages allows recognition of three distinct periods. In the first period, from 25 to 19 Ma, high epsilon-Nd values and low 87Sr/86Sr of sediments and fossils support intense tectonism and volcanism, related to the opening of the western Mediterranean. In the second period, from 19 to 13 Ma the 87Sr/86Sr ratio of Mediterranean (UMC) deviate from the global ocean, which is compatible with rapid uplift of the hinterland and intense influx of Sr from Mesozoic carbonates of the western Apennines. This local control on the seawater was driven by a humid and warm climate and indicates restricted exchange of water with the global ocean. Generally, the epsilon-Nd values of the fossils are very similar to those of Indian Ocean water, with brief periods of a decrease in the epsilon-Nd values coinciding with volcanic events and maybe sea level variation at 15.2 Ma. In the third period, from 13 to 10 Ma the fossils have 87Sr/86Sr similar to those of Miocene seawater while their epsilon-Nd values change considerably with time. This indicates fluctuating influence of the Atlantic versus the Paratethys and/or locally evolved seawater in the Mediterranean driven by global sea level changes. Other investigated localities near the Alps and from the ODP 900 site are compatible with this oceanographic interpretation. However, in the late early Miocene, enhanced local control, reflecting erosion of old crustal silicate rocks near the Alps, results in higher 87Sr/86Sr.

Sedimentology and Nd isotope ratios of sediment core PS72/410-1

The freshwater budget of the Arctic Ocean is a key component governing the deep water formation in the North Atlantic and the global climate system. We analyzed the isotopic composition of neodymium (epsilon-Nd) in authigenic phases of marine sediments on the Mendeleev Ridge in the western Arctic Ocean spanning an estimated time interval from present to about 75 ka BP. This continuous record was used to reconstruct the epsilon-Nd of the polar deep water (PDW) and changes in freshwater sources to the PDW through time. Three deviations in epsilon-Nd from a long term average of -10.2 were identified at estimated 46-51, 35-39 and 13-21 ka BP. The estimated 46-51 ka BP event can be traced to bursting of ice-dammed lakes accompanying the collapse of the Barents-Kara Ice Sheet, which would have released radiogenic Nd to the eastern Arctic Ocean. The cyclonic surface circulation in the eastern Arctic Ocean must have been stronger than at present for the event to be recorded on the Mendeleev Ridge. For the 35-39 and 13-21 ka BP events, it is likely that the Laurentide Ice Sheet (LIS) supplied the unradiogenic freshwater. The configuration of the anticyclonic circulation in the western Arctic was probably similar to today or expanded eastward. Our simple mass balance calculations suggest that large amounts of freshwater were released but due to significant deep water formation within the Arctic Ocean, the effect on the formation of NADW was probably minor.