ALBERT

Description: The seawater radiogenic neodymium (143Nd/144Nd) isotope signature is an invaluable tool for the reconstruction of past deep water provenance. Sedimentary foraminifera or fish teeth are among the most reliable archives known for Nd isotope based reconstructions of past seawater. As the distribution and preservation of these archives are limited, the extraction of hydrogenetic ferromanganese oxyhydroxides from bulk sediments provide an easily applicable alternative. This method, however, implies the risk of generating artefacts due to the possible release of non-seawater derived Nd during the extraction procedure. Here we revisit and further investigate the reliability of the extraction of seawater derived Nd isotope signatures via leaching of bulk deep sea sediments with two commonly used buffered acetic acid and acid-reductive mix solutions. Repeated application of such stepwise leaching procedures to different non-decarbonated sediments from distinct settings across the deep Atlantic Ocean shows pronounced elemental and Nd isotope trends during the leaching process in the laboratory. Our results show that seawater Nd isotope compositions are extracted together with carbonates and manganese oxides only at the beginning of the leaching series. During chemical extraction, the carbonates effectively work as a buffer preventing acid-induced mobilisation of Fe oxides and volcanogenic material. Once this buffer is consumed, potentially present volcanogenic phases are considerably attacked, leading to shifts in the extracted Nd isotope signal of up to + 12 epsilon units. Such volcanogenic phases are a significant source of contaminant Nd reflected by markedly elevated Al/Nd signatures. We consequently propose a revised weak leaching protocol for carbonate bearing deep sea sediments, which is simple to use, provides excellent agreement with data obtained from uncleaned foraminifera, and can be easily screened for contamination.

Description: Heinrich events are intervals of rapid iceberg-sourced freshwater release to the high latitude North Atlantic Ocean that punctuate late Pleistocene glacials. Delivery of fresh water to the main North Atlantic sites of deep water formation during Heinrich events may result in major disruption to the Atlantic Meridional Overturning Circulation (AMOC), however, the simple concept of an AMOC shutdown in response to each freshwater input has recently been shown to be overly simplistic. Here we present a new multi-proxy dataset spanning the last 41,000 years that resolves four Heinrich events at a classic mid-depth North Atlantic drill site, employing four independent geochemical tracers of water mass properties: boron/calcium, carbon and oxygen isotopes in foraminiferal calcite and neodymium isotopes in multiple substrates. We also report rare earth element distributions to investigate the fidelity by which neodymium isotopes record changes in water mass distribution in the northeast North Atlantic. Our data reveal distinct geochemical signatures for each Heinrich event, suggesting that the sites of fresh water delivery and/or rates of input played at least as important a role as the stage of the glacial cycle in which the fresh water was released. At no time during the last 41 kyr was the mid-depth northeast North Atlantic dominantly ventilated by southern-sourced water. Instead, we document persistent ventilation by Glacial North Atlantic Intermediate Water (GNAIW), albeit with variable properties signifying changes in supply from multiple contributing northern sources.

Description: A high-resolution authigenic Nd isotope record has been extracted from the Fe–Mn oxyhydroxide fraction of drift sediments along the Blake Ridge in the North Atlantic. These sediments facilitate reconstruction of the timing and extent of major hydrographic changes in the western North Atlantic since the Last Glacial Maximum (LGM). This is one of the few locations where sediments were deposited in the major flow path of the Western Boundary Undercurrent (WBUC), which transports North Atlantic Deep Water (NADW) southward at the present day. The hydrodynamic setting, however, also causes problems. Authigenic Nd isotope compositions similar to the typical present-day NADW εNd value of − 13.5 ± 0.5 were only extracted from sediments located within the main water body of the WBUC coinciding with the highest along slope current velocity below 3200 m water depth. Above this depth the authigenic Nd-isotopic composition is more radiogenic than measured in a nearby seawater profile and appears to be influenced by downslope and lateral sediment redistribution. Our data suggest that these radiogenic signals were formed at shallow depths in Florida current waters, compromising the recorded ambient deep water Nd isotope signal in the Blake Ridge Fe–Mn oxyhydroxide coatings from intermediate depths during the Holocene and the deglaciation. The unradiogenic Nd-isotopic composition typical of present-day NADW is not detectable along the Blake Ridge for any water depth during the LGM. Unlike the deglacial and Holocene sections, the intermediate core from 1790 m water depth did not experience significant sediment focusing during the LGM, in accord with the higher current velocities at this depth, suggesting that at this site an ambient LGM bottom water Nd isotope signal was recorded. Assuming this to be correct, our results indicate that the εNd of the shallower glacial equivalent of NADW, the Glacial North Atlantic Intermediate Water (GNAIW) may have been as radiogenic as − 9.7 ± 0.4. Since the authigenic Nd isotope compositions of the Holocene and the deglacial sections of the intermediate depth sediment core were biased towards a shallow water signal, this first determination of a GNAIW εNd for the LGM will have to be corroborated by results from other locations and archives. The LGM and deglacial sediments below 3400 m water depth bear no evidence of an ambient deep water εNd as unradiogenic as − 13.5. Although the deep core sites also experienced enhanced degrees of sediment focusing before the Younger Dryas, the εNd values of between − 11 and − 10 are more readily explained in terms of increased presence of Southern Source Waters. If this is the case, the change to Nd-isotopic compositions that reflect a modern circulation pattern, including the presence of Lower NADW, only occurred after the Younger Dryas.

Description: During the Last Glacial Maximum much of North America was covered by the Laurentide ice sheet. Its melting during termination 1 led to systematic changes in proglacial lake formation, continental runoff, and possibly North Atlantic Meridional Overturning Circulation. The accompanying change in chemical weathering rates in the interior of North America throughout the deglaciation resulted in a pronounced change in seawater Pb isotope composition in the western North Atlantic Ocean. Here we present the first high-resolution records of seawater Pb isotope variations of North Atlantic Deep Water extracted from authigenic Fe–Mn oxyhydroxides in three sediment cores (51GGC, 1790 m depth; 31GGC, 3410 m depth; 12JPC, 4250 m depth) from the Blake Ridge off Florida. These data reveal a striking excursion from relatively unradiogenic 206Pb/204Pb as low as 18.93 towards highly radiogenic Pb isotope compositions that was initiated during the Bølling–Allerød interstadial and was most pronounced in both intermediate and deep waters during and after the Younger Dryas (206Pb/204Pb as high as 19.38 at 8.8 ka in 4250 m). This pattern is interpreted to be a direct function of increased inflow of continent-derived radiogenic Pb into the western North Atlantic, supplied through chemical weathering of North American rocks that had been eroded and freshly exposed during the preceding glacial cycle. These sediment-derived data are complemented by new laser ablation Pb isotope data from a ferromanganese crust from the Blake Plateau at 850 m water depth, which show only small glacial–interglacial Pb isotope variations of the Florida Current (206Pb/204Pb between 19.07 and 19.16). The lack of change in the Blake Plateau record at the same time as the radiogenic excursion in the deeper sediments supports a northern origin of the pulse of radiogenic Pb. After the Younger Dryas, the deep western North Atlantic has experienced a persistent highly radiogenic Pb supply that was most pronounced during the first half of the Holocene and still lasts until today.

Description: The warm and saline North Atlantic inflow to the Arctic Ocean is a major component of high northern latitude circulation and the main mechanism of deep water renewal in the Arctic Ocean. Knowledge of its past variability is critical for understanding the high latitude feedback mechanisms of the climate system. Here we present the first combined seawater Hf and Nd isotope compositions of past Arctic Intermediate Water extracted from the authigenic Fe–Mn oxyhydroxide fraction of two sediment cores recovered near the North Pole, to reconstruct changes in contributions from glacial brines of the Eurasian shelf and past inflow of Atlantic waters. The Hf and Nd isotopic compositions obtained from leachates of the authigenic fraction show closely coupled and environmentally controlled variations over the past 14 million years. An observed offset of these data from seawater εHf and εNd compositions from other ocean basins (seawater array) is interpreted as the result of continuously prevailing glacial weathering conditions on the high latitude Eurasian continent. In the late Quaternary, large amplitude Hf and Nd isotopic variations of Arctic Intermediate Water (AIW) was characterized by more radiogenic isotope signatures generally prevailing under glacial conditions and less radiogenic values during interglacial periods. On the basis of the close coupling between Nd and Hf isotopes, we suggest that the evolution of Hf isotope compositions of central Arctic AIW has primarily been controlled by changes in ocean circulation and provenance of weathering inputs, rather than changes in weathering regime.

Description: Highlights • Records of seawater εNdεNd are highly unradiogenic across the OMT at Ceara Rise. • Strong influence of Amazon particulate Nd on seawater εNdεNd at Ceara Rise. • Point-sourced riverine Nd influences seawater far from continental shelf. • Regional sedimentary Nd flux can be confused with water mass mixing signals. Abstract Dissolved and particulate neodymium (Nd) are mainly supplied to the oceans via rivers, dust, and release from marine sediments along continental margins. This process, together with the short oceanic residence time of Nd, gives rise to pronounced spatial gradients in oceanic 143Nd/144Nd ratios (εNdεNd). However, we do not yet have a good understanding of the extent to which the influence of riverine point-source Nd supply can be distinguished from changes in mixing between different water masses in the marine geological record. This gap in knowledge is important to fill because there is growing awareness that major global climate transitions may be associated not only with changes in large-scale ocean water mass mixing, but also with important changes in continental hydroclimate and weathering. Here we present εNdεNd data for fossilised fish teeth, planktonic foraminifera, and the Fe–Mn oxyhydroxide and detrital fractions of sediments recovered from Ocean Drilling Project (ODP) Site 926 on Ceara Rise, situated approximately 800 km from the mouth of the River Amazon. Our records span the Mi-1 glaciation event during the Oligocene–Miocene transition (OMT; ∼23 Ma). We compare our εNdεNd records with data for ambient deep Atlantic northern and southern component waters to assess the influence of particulate input from the Amazon River on Nd in ancient deep waters at this site. εNdεNd values for all of our fish teeth, foraminifera, and Fe–Mn oxyhydroxide samples are extremely unradiogenic (εNd≈−15εNd≈−15); much lower than the εNdεNd for deep waters of modern or Oligocene–Miocene age from the North Atlantic (εNd≈−10εNd≈−10) and South Atlantic (εNd≈−8εNd≈−8). This finding suggests that partial dissolution of detrital particulate material from the Amazon (εNd≈−18εNd≈−18) strongly influences the εNdεNd values of deep waters at Ceara Rise across the OMT. We conclude that terrestrially derived inputs of Nd can affect εNdεNd values of deep water many hundreds of kilometres from source. Our results both underscore the need for care in reconstructing changes in large-scale oceanic water-mass mixing using sites proximal to major rivers, and highlight the potential of these marine archives for tracing changes in continental hydroclimate and weathering.

Description: We have retrieved radiogenic hafnium (Hf) isotope compositions (ɛHf) from authigenic Fe–Mn oxyhydroxides of deep northwest Atlantic sediments deposited over the past 26 ka to investigate the oceanic evidence of changes in dissolved weathering inputs from NE America during the last deglaciation. The extraction of seawater-derived Hf isotopic compositions from Fe–Mn oxyhydroxides is not a standard procedure. Comparisons between the Al/Hf ratios and Hf isotopic compositions of the chemically extracted authigenic phase on the one hand, and those of the corresponding detrital fractions on the other, provide evidence that the composition of past seawater has been reliably obtained for most sampled depths with our leaching procedures. This is endorsed most strongly by data for a sediment core from 4250 m water depth at the deeper Blake Ridge, for which consistent replicates were produced throughout. The Hf isotopic composition of the most recent sample in this core also closely matches that of nearby present day central North Atlantic seawater. Comparison with previously published seawater Nd and Pb isotope compositions obtained on the same cores shows that both Hf and Pb were released incongruently during incipient chemical weathering, but responded differently to the deglacial retreat of the Laurentide Ice Sheet. Hafnium was released more congruently during peak glacial conditions of the Last Glacial Maximum (LGM) and changed to typical incongruent interglacial ɛHf signatures either during or shortly after the LGM. This indicates that some zircon-derived Hf was released to seawater during the LGM. Conversely, there is no clear evidence for an increase in the influence of weathering of Lu-rich mineral phases during deglaciation, possibly since relatively unradiogenic Hf contributions from feldspar weathering were superimposed. While the authigenic Pb isotope signal in the same marine sediment samples traced peak chemical weathering rates on continental North America during the transition to the Holocene a similar incongruent excursion is notably absent in the Hf isotope record. The early change towards more radiogenic ɛHf in relation to the LGM may provide direct evidence for the transition from a cold-based to a warm-based Laurentide Ice Sheet on the Atlantic sector of North America.

Description: We present Plio-Pleistocene records of sediment color, %CaCO3, foraminifer fragmentation, benthic carbon isotopes (δ13C) 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).

Description: Multiple palaeo-proxy and modelling studies suggest that Mediterranean Outflow Water (MOW) is an important driver of Atlantic Meridional Overturning Circulation (AMOC), particularly during periods of weak overturning. Here, we employ the HadCM3 ocean–atmosphere General Circulation Model (GCM) to investigate the effect of using different parameterisations of Mediterranean–Atlantic water exchange on global ocean circulation and climate. In HadCM3, simulating flow through the Gibraltar Straits with an ‘open seaway’ rather than a ‘diffusive pipe’ causes a shoaling and strengthening of the MOW plume. This reorganises shallow Atlantic circulation, producing regional surface air temperature anomalies of up to + 11 °C and −7.5 °C. We conclude that when investigating the influence of MOW on modelled ocean circulation and climate, an accurate parameterisation of Mediterranean–Atlantic exchange is important and should match observed fresh water and salinity flux constraints. This probably cannot be achieved through a simple ‘diffusive pipe’ with depth invariant mixing coefficient.

Description: Radiocarbon and uranium-thorium dating results are presented from a genus of calcitic Antarctic cold-water octocorals (family Coralliidae), which were collected from the Marie Byrd Seamounts in the Amundsen Sea (Pacific sector of the Southern Ocean) andwhich to date have not been investigated geochemically. The geochronological results are set in contextwith solution and laser ablation-basedelement/Ca ratios (Li, B,Mg,Mn, Sr,Ba, U,Th). Octocoral radiocarbon ages on living corals are in excellent agreement with modern ambient deep-water Δ14C, while multiple samples of individual fossil coral specimens yielded reproducible radiocarbon ages. Provided that local radiocarbon reservoir ages can be derived for a given time, fossil Amundsen Sea octocorals should be reliably dateable by means of radiocarbon. In contrast to the encouraging radiocarbon findings, the uranium-series data are more difficult to interpret. The uranium concentration of these calcitic octocorals is an order of magnitude lower than in the aragonitic hexacorals that are conventionally used for geochronological investigations. While modern and Late Holocene octocorals yield initial δ234U in good agreement with modern seawater, our results reveal preferential inward diffusion of dissolved alpha-recoiled 234U and its impact on fossil coral δ234U. Besides alpha-recoil related 234U diffusion, high-resolution sampling of two fossil octocorals further demonstrates that diagenetic uraniummobility has offset apparent coral U-series ages. Combined with the preferential alpha-recoil 234U diffusion, this process has prevented fossil octocorals from preserving a closed system U-series calendar age for longer than a few thousand years. Moreover, several corals investigated contain significant initial thorium, which cannot be adequately corrected for because of an apparently variable initial 232Th/230Th. Our results demonstrate that calcitic cold-water corals are unsuitable for reliable U-series dating. Mg/Ca ratios within single octocoral specimens are internally strikingly homogeneous, and appear promising in terms of their response to ambient temperature. Magnesium/lithium ratios are significantly higher than usually observed in other deep marine calcifiers and for many of our studied corals are remarkably close to seawater compositions. Although this family of octocorals is unsuitable for glacial deep-water Δ14C reconstructions, our findings highlight some important differences between hexacoral (aragonitic) and octocoral (calcitic) biomineralisation. Calcitic octocorals could still be useful for trace element and some isotopic studies, such as reconstruction of ambient deep water neodymium isotope composition or pH, via boron isotopic measurements.