Dynamic intermediate ocean circulation in the North Atlantic during Heinrich Stadial 1: a radiocarbon and neodymium isotope perspective

The last deglaciation was characterised by a series of millennial scale climate events that have been linked to deep ocean variability. While often implied in interpretations, few direct constraints exist on circulation changes at mid-depths. Here we provide new constraints on the variability of deglacial mid-depth circulation using combined radiocarbon and neodymium isotopes in 24 North Atlantic deep-sea corals. Their aragonite skeletons have been dated by uranium-series, providing absolute ages and the resolution to record centennial scale changes, while transects spanning the lifetime of a single coral allow sub-centennial tracer reconstruction. Our results reveal that rapid fluctuations of water mass sourcing and radiocarbon affected the mid-depth water column (1.7-2.5 km) on timescales of less than 100 years during the latter half of Heinrich Stadial 1. The neodymium isotopic variability (−14.5 to −11.0) ranges from the composition of the modern northern-sourced waters towards more radiogenic compositions that suggest the presence of a greater southern-sourced component at some times. However, in detail, simple two-component mixing between well-ventilated northern-sourced and radiocarbon-depleted southern-sourced water masses cannot explain all our data. Instead, corals from ~15.0 ka and ~15.8 ka may record variability between southern-sourced intermediate waters and radiocarbon-depleted northern-sourced waters, unless there was a major shift in the neodymium isotopic composition of the northern endmember. In order to explain the rapid shift towards the most depleted radiocarbon values at ~15.4 ka, we suggest a different mixing scenario involving either radiocarbon-depleted deep water from the Greenland-Iceland-Norwegian Seas or a southern-sourced deep water mass. Since these mid-depth changes preceded the Bolling-Allerod warming, and were apparently unaccompanied by changes in the deep Atlantic, they may indicate an important role for the intermediate ocean in the early deglacial climate evolution

Rare Earth Element Distribution in the NE Atlantic: Evidence for Benthic Sources, Longevity of the Seawater Signal, and Biogeochemical Cycling

Seawater rare earth element (REE) concentrations are increasingly applied to reconstruct water mass histories by exploiting relative changes in the distinctive normalised patterns. However, the mechanisms by which water masses gain their patterns are yet to be fully explained. To examine this, we collected water samples along the Extended Ellett Line (EEL), an oceanographic transect between Iceland and Scotland, and measured dissolved REE by offline automated chromatography (SeaFAST) and ICP-MS. The proximity to two continental boundaries, the incipient spring bloom coincident with the timing of the cruise, and the importance of deep water circulation in this climatically sensitive gateway region make it an ideal location to investigate sources of REE to seawater and the effects of vertical cycling and lateral advection on their distribution. The deep waters have REE concentrations closest to typical North Atlantic seawater and are dominated by lateral advection. Comparison to published seawater REE concentrations of the same water masses in other locations provides a first measure of the temporal and spatial stability of the seawater REE signal. We demonstrate the REE pattern is replicated for Iceland-Scotland Overflow Water (ISOW) in the Iceland Basin from adjacent stations sampled 16 years previously. A recently published Labrador Sea Water (LSW) dissolved REE signal is reproduced in the Rockall Trough but shows greater light and mid REE alteration in the Iceland Basin, possibly due to the dominant effect of ISOW and/or continental inputs. An obvious concentration gradient from seafloor sediments to the overlying water column in the Rockall Trough, but not the Iceland Basin, highlights release of light and mid REE from resuspended sediments and pore waters, possibly a seasonal effect associated with the timing of the spring bloom in each basin. The EEL dissolved oxygen minimum at the permanent pycnocline corresponds to positive heavy REE enrichment, indicating maximum rates of organic matter remineralisation and associated REE release. We tentatively suggest a bacterial role to account for the observed heavy REE deviations. This study highlights the need for fully constrained REE sources and sinks, including the temporary nature of some sources, to achieve a balanced budget of seawater REE

Weathering fluxes and sediment provenance on the SW Scottish shelf during the last deglaciation

The reconstruction of past ice sheet dynamics can shed a light on long-term ice stream activity, and in turn provide constraints on the response of modern ice sheets to climate change. The Hebrides Ice Stream (HIS) flowed across part of the western Scottish shelf to the shelf-break during the last glacial cycle and drained a large portion of the northern sector of the British Irish-Ice Sheet. To investigate the deglacial dynamics of the HIS following the Last Glacial Maximum, lead (Pb) isotope records were extracted from the FeMn oxyhydroxide and detrital fractions of recovered laminated glacimarine mud sequences to monitor the changing activity of HIS during its retreat. These provide timing and some source information of glacially weathered inputs to the marine environment. The FeMn oxyhydroxide fraction in the samples is dominated by allochthonous particles (pre-formed) and shows a marked decrease from radiogenic (≤ 20.05 206Pb/204Pb) at ~ 21 cal ka BP to less radiogenic Pb isotope compositions (~ 19.48) towards the Windermere Interstadial (15.4–13 ka). This decrease represents a reduction in the flux of subglacially-derived radiogenic Pb to the continental shelf is interpreted as being associated with the break-up of the ice-stream in western Scotland around that time. The Pb, Sr and Nd isotopic signatures of the detrital fraction indicate a preponderance of Moine-sourced fine sediments (originated from the NW Highlands) in the core locations from ~ 21 to 15 cal ka BP (Dimlington Stadial - Windermere Interstadial), most likely dictated by the orientation of ice flow, tidal and oceanic current directions and sediment delivery. In contrast, ice rafted debris in a ~ 21 cal ka BP old basal diamicton contains volcanic-derived material, suggesting different provenance for different grain sizes. The FeMn oxyhydroxide 208Pb/204Pb ratio shows an unusual inversion relative to the other Pb isotope ratios, and is attributed to the introduction of secondary weathering phases from a source with contrasting 208Pb/204Pb but similar 206Pb/204Pb and 207Pb/204Pb. In the detrital fraction, the inversions are constrained to periodic spikes, which may indicate an increased contribution from a high Th/U source, potentially the neighbouring Archaean amphibolitic Lewisian basement in the Outer Hebrides. This study demonstrates how geochemical investigation on continental shelves can be used to constrain the timing, activity and flow sources of palaeo-ice streams

Neodymium isotopes and concentrations in aragonitic scleractinian cold-water coral skeletons - Modern calibration and evaluation of palaeo-applications

TvdF and TS acknowledge financial support for a bursary by the Grantham Institute of Climate Change and the Environment and a Marie Curie Reintegration grant (IRG 230828), as well as funding from the Leverhulme Trust (RPG-398) and the NERC (NE/N001141/1). Additional financial support was provided to LFR by the USGS-WHOI Co-operative agreement, NSF-ANT grants 0636787 and 80295700, The European Research Council, the Leverhulme Trust and a Marie Curie Reintegration grant. LB was supported by a NOAA/UCAR Climate and Global Change Postdoctoral Fellowship and KJM acknowledges funding from a Marie Curie International Outgoing fellowship (IOF 236962).Cold-water corals (CWCs) are unique archives of mid-depth ocean chemistry and have been used successfully to reconstruct the neodymium (Nd) isotopic composition of seawater from a number of species. High and variable Nd concentrations in fossil corals however pose the question as to how Nd is incorporated into their skeletons. We here present new results on modern specimens of Desmophyllum dianthus, Balanophyllia malouinensis, and Flabellum curvatum, collected from the Drake Passage, and Madrepora oculata, collected from the North Atlantic. All modern individuals were either collected alive or uranium-series dated to be < 500 years old for comparison with local surface sediments and seawater profiles. Modern coral Nd isotopic compositions generally agree with ambient seawater values, which in turn are consistent with previously published seawater analyses, supporting small vertical and lateral Nd isotope gradients in modern Drake Passage waters. Two Balanophyllia malouinensis specimens collected live however deviate by up to 0.6 epsilon units from ambient seawater. We therefore recommend that this species should be treated with caution for the reconstruction of past seawater Nd isotopic compositions. Seventy fossil Drake Passage CWCs were furthermore analysed for their Nd concentrations, revealing a large range from 7.3 to 964.5 ng/g. Samples of the species D. dianthus and Caryophyllia spp. show minor covariation of Nd with 232Th content, utilised to monitor contaminant phases in cleaned coral aragonite. Strong covariations between Nd and Th concentrations are however observed in the species B. malouinensis and G. antarctica. In order to better constrain the source and nature of Nd in the cleaned aragonitic skeletons, a subset of sixteen corals was investigated for its rare earth element (REE) content, as well as major and trace element geochemistry. Our new data provide supporting evidence that the applied cleaning protocol efficiently removes contaminant lithogenic and ferromanganese oxyhydroxide phases. Mass balance calculations and seawater-like REE patterns rule out lithogenic and ferromanganese oxyhydroxide phases as a major contributor to elevated Nd concentrations in coral aragonite. Based on mass balance considerations, geochemical evidence, and previously published independent work by solid-state nuclear magnetic resonance (NMR) spectroscopy, we suggest authigenic phosphate phases as a significant carrier of skeletal Nd. Such a carrier phase could explain sporadic appearance of high Nd concentrations in corals and would be coupled with seawater-derived Nd isotopic compositions, lending further confidence to the application of Nd isotopes as a water mass proxy in CWCs.Publisher PDFPeer reviewe

Neodymium isotope analyses after combined extraction of actinide and lanthanide elements from seawater and deep-sea coral aragonite

Author Posting. © American Geophysical Union, 2016. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geochemistry, Geophysics, Geosystems 17 (2016): 232–240, doi:10.1002/2015GC006130.Isotopes of the actinide elements protactinium (Pa), thorium (Th), and uranium (U), and the lanthanide element neodymium (Nd) are often used as complementary tracers of modern and past oceanic processes. The extraction of such elements from low abundance matrices, such as seawater and carbonate, is however labor-intensive and requires significant amounts of sample material. We here present a combined method for the extraction of Pa, Th, and Nd from 5 to 10 L seawater samples, and of U, Th, and Nd from <1 g carbonate samples. Neodymium is collected in the respective wash fractions of Pa-Th and U-Th anion exchange chromatographies. Regardless of the original sample matrix, Nd is extracted during a two-stage ion chromatography, followed by thermal ionization mass spectrometry (TIMS) analysis as NdO+. Using this combined procedure, we obtained results for Nd isotopic compositions on two GEOTRACES consensus samples from Bermuda Atlantic Time Series (BATS), which are within error identical to results for separately sampled and processed dedicated Nd samples (εNd = −9.20 ± 0.21 and −13.11 ± 0.21 for 15 and 2000 m water depths, respectively; intercalibration results from 14 laboratories: εNd = −9.19 ± 0.57 and −13.14 ± 0.57). Furthermore, Nd isotope results for an in-house coral reference material are identical within analytical uncertainty for dedicated Nd chemistry and after collection of Nd from U-Th anion exchange chromatography. Our procedure does not require major adaptations to independently used ion exchange chromatographies for U-Pa-Th and Nd, and can hence be readily implemented for a wide range of applications.Funding that supported this work was received from the National Science Foundation (NSF 0752402), the Leverhulme Trust (RPG-398), the Natural Environmental Research Council (NE/J021636/1 and NE/N003861/1), the European Research Council (278705), and the Grantham Institute for Climate Change.2016-07-0