Nd, Pb, and Be isotopes of ferromanaganese crusts of the Atlantic Ocean

The isotopic composition of Nd in present-day deep waters of the central and northeastern Atlantic Ocean is thought to fingerprint mixing of North Atlantic Deep Water with Antarctic Bottom Water. The central Atlantic Romanche and Vema Fracture Zones are considered the most important pathways for deep water exchange between the western and eastern Atlantic basins today. We present new Nd isotope records of the deepwater evolution in the fracture zones obtained from ferromanganese crusts, which are inconsistent with simple water mass mixing alone prior to 3 Ma and require additional inputs from other sources. The new Pb isotope time series from the fracture zones are inexplicable by simple mixing of North Atlantic Deep Water and Antarctic Bottom Water for the entire past 33 Myr. The distinct and relatively invariable Nd and Pb isotope records of deep waters in the fracture zones appear instead to have been controlled to a large extent by contributions from Saharan dust and the Orinoco/Amazon Rivers. Thus the previously observed similarity of Nd and Pb isotope time series from the western and eastern North Atlantic basins is better explainable by direct supply of Labrador Seawater to the eastern basin via a northern pathway rather than by advection of North Atlantic Deep Water via the Romanche and Vema Fracture Zones.

Nd isotope data for planktonic foraminifera from within and around sapropels S1 and S5 from ODP Site 160-967

The development of widespread anoxic conditions in the deep oceans is evidenced by the accumulation and preservation of organic-carbon-rich sediments, but its precise cause remains controversial. The two most popular hypotheses involve (1) circulation-induced increased stratification resulting in reduced oxygenation of deep waters or (2) enhanced productivity in the surface ocean, increasing the raining down of organic matter and overwhelming the oxic remineralization potential of the deep ocean. In the periodic development of deep-water anoxia in the Pliocene-Pleistocene Mediterranean Sea, increased riverine runoff has been implicated both as a source for nutrients that fuel enhanced photic-zone productivity and a source of a less dense freshwater cap leading to reduced circulation, basin-wide stagnation, and deep-water oxygen starvation. Monsoon-driven increases in Nile River discharge and increased regional precipitation due to enhanced westerly activity-two mechanisms that represent fundamentally different climatic driving forces-have both been suggested as causes of the altered freshwater balance. Here we present data that confirm a distinctive neodymium (Nd) isotope signature for the Nile River relative to the Eastern Mediterranean-providing a new tracer of enhanced Nile outflow into the Mediterranean in the past. We further present Nd isotope data for planktonic foraminifera that suggest a clear increase in Nile discharge during the central intense period of two recent anoxic events. Our data also suggest, however, that other regional freshwater sources were more important at the beginning and end of the anoxic events. Taken at face value, the data appear to imply a temporal link between peaks in Nile discharge and enhanced westerly activity.

Isotope ratios and trace element concentrations of basalts from DSDP Leg 15 sites (Appendix 1)

Formation of the Cretaceous Caribbean plateau, including the komatiites of Gorgona, has been linked to the currently active Galápagos hotspot. We use Hf-Nd isotopes and trace element data to characterise both the Caribbean plateau and the Galápagos hotspot, and to investigate the relationship between them. Four geochemical components are identified in the Galápagos mantle plume: two 'enriched' components with epsilon-Hf and epsilon-Nd similar to enriched components observed in other mantle plumes, one moderately enriched component with high Nb/Y, and a fourth component which most likely represents depleted MORB source mantle. The Caribbean plateau basalt data form a linear array in Hf-Nd isotope space, consistent with mixing between two mantle components. Combined Hf-Nd-Pb-Sr-He isotope and trace element data from this study and the literature suggest that the more enriched Caribbean end member corresponds to one or both of the enriched components identified on Galápagos. Likewise, the depleted end member of the array is geochemically indistinguishable from MORB and corresponds to the depleted component of the Galápagos system. Enriched basalts from Gorgona partially overlap with the Caribbean plateau array in epsilon-Hf vs. epsilon-Nd, whereas depleted basalts, picrites and komatiites from Gorgona have a high epsilon-Hf for a given epsilon-Nd, defining a high-epsilon-Hf depleted end member that is not observed elsewhere within the Caribbean plateau sequences. This component is similar, however, in terms of Hf-Nd-Pb-He isotopes and trace elements to the depleted plume component recognised in basalts from Iceland and along the Reykjanes Ridge. We suggest that the Caribbean plateau represents the initial outpourings of the ancestral Galápagos plume. Absence of a moderately enriched, high Nb/Y component in the older Caribbean plateau (but found today on the island of Floreana) is either due to changing source compositions of the plume over its 90 Ma history, or is an artifact of limited sampling. The high-epsilon-Hf depleted component sampled by the Gorgona komatiites and depleted basalts is unique to Gorgona and is not found in the Caribbean plateau. This may be an indication of the scale of heterogeneity of the Caribbean plateau system; alternatively Gorgona may represent a separate oceanic plateau derived from a completely different Pacific plume, such as the Sala y Gomez.

Element abundances and Nd isotopic composition in boninite and tholeiite from DSDP Hole 60-458

Boninites are unusual high MgO-high SiO2 volcanic rocks found in several western Pacific island arcs. Their high Mg/(Mg + total Fe) (0.55-0.83) and compatible element contents (Ni = 70-450 ppm, Cr = 200-1800 ppm) indicate equilibration with mantle peridotite, but their low TiO2 contents (0.1-0.5%) indicate severe depletion of this source. K, Rb, Sr and Ba abundances in boninites are typical of primitive arc basalts, but ratios such as Ti/Zr and La/Yb are variable (Ti/Zr = 23-67, (La/Yb)e.f. = 0.6-4.7). Evidence for both enrichment and depletion of incompatible elements suggests that boninites are derived from refractory peridotite which has been metasomatically enriched in LREE, Zr, Sr, Ba and alkalis. Wide variations in 143Nd/144Nd (0.51262-0.51296) are correlated with La/Sm, Sm/Nd and Ti/Zr, which enables identification of components in the boninite source. Possible LREE depleted components have relative REE and Ti abundances like those in depleted peridotites and high 143Nd/144Nd ratios which reach MORB-like values. Possible LREE enriched components have relative REE abundances similar to those in metasomatized mantle peridotite nodules, and low 143Nd/144Nd ratios which indicate either sedimentary sources or mantle sources with recent to ancient LREE enrichment. Relative abundances of Ba and Sr in boninites decrease with increasing LREE enrichment and suggest a non-sedimentary source for the LREE enriched material. Enrichment in Ba, Sr and alkalis may result from a third component derived from subducted oceanic crust. Two models can account for the successive generation of boninites and arc tholeiites within a single area: 1) boninites can be derived from the peridotite residue of earlier arc tholeiite generation which is metasomatically enriched in LREE before boninite volcanism, or 2) arc tholeiites and boninites can be derived from a variably depleted peridotite source which has been pervasively enriched in LREE. Areas of fertile peridotite would yield tholeiites while refractory areas would yield boninites.

(Appendix A) Geochemical composition of snow and eolian mineral dust from Berkner Island ice sheet, Antarctica

The Sr and Nd isotopic composition of dust extracted from recent snow layers at the top of Berkner Island ice sheet (located within the Filchner-Ronne Ice Shelf at the southern end of the Weddell Sea) enables us, for the first time, to document dust provenance in Antarctica outside the East Antarctic Plateau (EAP) where all previous studies based on isotopic fingerprinting were carried out. Berkner dust displays an overall crust-like isotopic signature, characterized by more radiogenic 87Sr/86Sr and much less radiogenic 143Nd/144Nd compared to dust deposited on the EAP during glacial periods. Differences with EAP interglacial dust are not as marked but still significant, indicating that present-day Berkner dust provenance is distinct, at least to some extent, from that of the dust reaching the EAP. The fourteen snow-pit sub-seasonal samples that were obtained span a two-year period (2002-2003) and their dust Sr and Nd isotopic composition reveals that multiple sources are at play over a yearly time period. Southern South America, Patagonia in particular, likely accounts for part of the observed spring/summer dust deposition maxima, when isotopic composition is shifted towards 'younger' isotopic signatures. In the spring, possible additional inputs from Australian sources would also be supported by the data. Most of the year, however, the measured isotopic signatures would be best explained by a sustained background supply from putative local sources in East Antarctica, which carry old-crust-like isotopic fingerprints. Whether the restricted East Antarctic ice-free areas produce sufficient eolian material has yet to be substantiated however. The fact that large (> 5 µm) particles represent a significant fraction of the samples throughout the entire time-series supports scenarios that involve contributions from proximal sources, either in Patagonia and/or Antarctica (possibly including snow-free areas in the Antarctic Peninsula and other areas as well). This also indicates that additional dust transport, which does not reach the EAP, must occur at low-tropospheric levels to this coastal sector of Antarctica.

Nd, Pb, and Be isotopes of ferromanaganese crusts of the South Pacific

The application of radiogenic isotopes to the study of Cenozoic circulation patterns in the South Pacific Ocean has been hampered by the fact that records from only equatorial Pacific deep water have been available. We present new Pb and Nd isotope time series for two ferromanganese crusts that grew from equatorial Pacific bottom water (D137-01, 'Nova', 7219 m water depth) and southwest Pacific deep water (63KD, 'Tasman', 1700 m water depth). The crusts were dated using 10Be/9Be ratios combined with constant Co-flux dating and yield time series for the past 38 and 23 Myr, respectively. The surface Nd and Pb isotope distributions are consistent with the present-day circulation pattern, and therefore the new records are considered suitable to reconstruct Eocene through Miocene paleoceanography for the South Pacific. The isotope time series of crusts Nova and Tasman suggest that equatorial Pacific deep water and waters from the Southern Ocean supplied the dissolved trace metals to both sites over the past 38 Myr. Changes in the isotopic composition of crust Nova are interpreted to reflect development of the Antarctic Circumpolar Current and changes in Pacific deep water circulation caused by the build up of the East Antarctic Ice Sheet. The Nd isotopic composition of the shallower water site in the southwest Pacific appears to have been more sensitive to circulation changes resulting from closure of the Indonesian seaway.

Chemical analyses of ODP Hole 105-647A basalts (Table 2)

Basalt samples recovered from the lowermost 37 m of Leg 105 Hole 647A in the Labrador Sea are fine- to medium grained, have microphenocrysts of clinopyroxene, and show little evidence of alteration. Chemically, these rocks are low potassium (0.01-0.09 wt% K20), olivine- to quartz-normative tholeiites that are also depleted in other incompatible elements. In terms of many of the incompatible trace elements, the Labrador Sea samples are similar both to iV-type midocean ridge basalts (MORBs) and to the terrestrial Paleocene volcanic rocks in the Davis Strait region of Baffin Island and West Greenland. However, significant differences are found in their strontium and neodymium isotope systematics. Hole 647A samples are more depleted in epsilon-Nd (+9.3) and are anomalously rich in 87Sr/86Sr (0.7040) relative to the Davis Strait basalts (epsilon-Nd +2.54 to + 8.97; mean 87Sr/86Sr, 0.7034). We conclude that the Hole 647A and Davis Strait basalts may have been derived from a similar depleted mantle source composition. In addition, the Davis Strait magmas were generated from mantle of more than one composition. We also suggest that there is no geochemical evidence from the Hole 647A samples to support or to refute the existence of foundered continental crust in the Labrador Sea.

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 and Pb isotopes in ferromanganese crusts

The intensity of North Atlantic Deep Water (NADW) production has been one of the most important parameters controlling the global thermohaline ocean circulation system and climate. Here we present a new approach to reconstruct the overall strength of NADW export from the North Atlantic to the Southern Ocean over the past 14 Myr applying the deep water Nd and Pb isotope composition as recorded by ferromanganese crusts and nodules. We present the first long-term Nd and Pb isotope time series for deep Southern Ocean water masses, which are compared with previously published time series for NADW from the NW Atlantic Ocean. These data suggest a continuous and strong export of NADW, or a precursor of it, into the Southern Ocean between 14 and 3 Ma. An increasing difference in Nd and Pb isotope compositions between the NW Atlantic and the Southern Ocean over the past 3 Myr gives evidence for a progressive overall reduction of NADW export since the onset of Northern Hemisphere glaciation (NHG). The Nd isotope data allow us to assess at least semiquantitatively that the amount of this reduction has been in the range between 14 and 37% depending on location.

CaCO3, foraminifer fragmentation, benthic carbon isotopes, coarse lithic counts and radiogenic isotopes (Sr, Nd, Pb) of the Pliocene and earliest Pleistocene terrigenous component (3.3-2.4 Ma) of IODP Site 306-U1313

We present Plio-Pleistocene records of sediment color, %CaCO3, foraminifer fragmentation, benthic carbon isotopes (d13C) and radiogenic isotopes (Sr, Nd, Pb) of the terrigenous component from IODP Site U1313, a reoccupation of benchmark subtropical North Atlantic Ocean DSDP Site 607. We show that (inter)glacial cycles in sediment color and %CaCO3 pre-date major northern hemisphere glaciation and are unambiguously and consistently correlated to benthic oxygen isotopes back to 3.3 million years ago (Ma) and intermittently so probably back to the Miocene/Pliocene boundary. We show these lithological cycles to be driven by enhanced glacial fluxes of terrigenous material (eolian dust), not carbonate dissolution (the classic interpretation). Our radiogenic isotope data indicate a North American source for this dust (~3.3-2.4 Ma) in keeping with the interpreted source of terrestrial plant wax-derived biomarkers deposited at Site U1313. Yet our data indicate a mid latitude provenance regardless of (inter)glacial state, a finding that is inconsistent with the biomarker-inferred importance of glaciogenic mechanisms of dust production and transport. Moreover, we find that the relation between the biomarker and lithogenic components of dust accumulation is distinctly non-linear. Both records show a jump in glacial rates of accumulation from Marine Isotope Stage, MIS, G6 (2.72 Ma) onwards but the amplitude of this signal is about 3-8 times greater for biomarkers than for dust and particularly extreme during MIS 100 (2.52 Ma). We conclude that North America shifted abruptly to a distinctly more arid glacial regime from MIS G6, but major shifts in glacial North American vegetation biomes and regional wind fields (exacerbated by the growth of a large Laurentide Ice Sheet during MIS 100) likely explain amplification of this signal in the biomarker records. Our findings are consistent with wetter-than-modern reconstructions of North American continental climate under the warm high CO2 conditions of the Early Pliocene but contrast with most model predictions for the response of the hydrological cycle to anthropogenic warming over the coming 50 years (poleward expansion of the subtropical dry zones).

Benthic and planktic foraminiferal stable isotope records combined with Nd isotope ratios of ODP Hole 198-1210B

The Pacific Ocean is the largest water body on Earth, and circulation in the Pacific contributed significantly to climate evolution in the latest Cretaceous, the culmination of a period of long-term cooling. Here, we present new high-resolution late Campanian to Maastrichtian benthic and planktic foraminiferal stable isotope data and a neodymium (Nd) isotope record obtained from sedimentary ferromanganese oxide coatings of Ocean Drilling Program Hole 1210B from the tropical Pacific Ocean (Shatsky Rise). These new records resolve 13 million years in the latest Cretaceous, providing insights into changes in surface and bottom water temperatures and source regions of deep to intermediate waters covering the carbon isotope excursions of the Campanian-Maastrichtian Boundary Event (CMBE) and the Mid-Maastrichtian event (MME). Our new benthic foraminiferal d18O and Nd isotope records together with published Nd isotope data show markedly parallel trends across the studied interval over a broad range of bathyal to abyssal water depths interpreted to reflect changes in the intensity of deep-ocean circulation in the tropical Pacific. In particular, we observe a three-million-year-long period of cooler conditions in the early Maastrichtian (72.5 to 69.5 Ma) when a concomitant change toward less radiogenic seawater Nd isotope signatures probably marks a period of enhanced admixture and northward flow of deep waters with Southern Ocean provenance. We suggest this change to have been triggered by intensified formation and convection of deep waters in the high southern latitudes, a process that weakened during the MME (69.5 to 68.5 Ma). The early Maastrichtian cold interval is closely related to the negative and positive carbon isotope trends of the CMBE and MME. The millions-of-years long duration of these carbon cycle perturbations suggests a tectonic forcing of climatic cooling, possibly related to changes in ocean basin geometry and bathymetry.