231Pa/230Th evidence for a weakened but persistent Atlantic meridional overturning circulation during Heinrich Stadial 1

The strength of Atlantic meridional overturning circulation is believed to affect the climate over glacial-interglacial and millennial timescales. The marine sedimentary ²³¹Pa/²³⁰Th ratio is a promising paleocirculation proxy, but local particle effects may bias individual reconstructions. Here we present new Atlantic sedimentary ²³¹Pa/²³⁰Th data from the Holocene, the last glacial maximum and Heinrich Stadial 1, a period of abrupt cooling ca. 17,500 years ago. We combine our results with published data from these intervals to create a spatially distributed sedimentary ²³¹Pa/²³⁰Th database. The data reveal a net ²³¹Pa deficit during each period, consistent with persistent ²³¹Pa export. In highly resolved cores, Heinrich ²³¹Pa/²³⁰Th ratios exceed glacial ratios at nearly all depths, indicating a significant reduction, although not cessation, of overturning during Heinrich Stadial 1. These results support the inference that weakened overturning was a driver of Heinrich cooling, while suggesting that abrupt climate oscillations do not necessarily require a complete shutdown of overturning

Improvements to 232-thorium, 230-thorium, and 231-protactinium analysis in seawater arising from GEOTRACES intercalibration

The GEOTRACES program requires the analysis of large numbers of seawater samples for ^(232)Th, ^(230)Th, and ^(231)Pa. During the GEOTRACES international intercalibration exercise, we encountered unexpected difficulties with recovery and contamination of these isotopes, ^(232)Th in particular. Experiments were carried out to identify the source of these issues, leading to a more streamlined and efficient procedure. The two particular problems that we identified and corrected were (1) frits in columns supplied by Bio-Rad Laboratories caused loss of Th during column chemistry and (2) new batches of AG1-X8 resin supplied by Bio-Rad Laboratories released more than 100 pg of ^(232)Th during elution of sample. To improve yields and blanks, we implemented a series of changes including switching to Eichrom anion exchange resin (100-200 μm mesh) and Environmental Express columns. All Th and Pa samples were analyzed on a Neptune multi-collector inductively-coupled-plasma mass spectrometer (MC-ICP-MS) using peak hopping of ^(230)Th and ^(229)Th on the central SEM, with either ^(232)Th, ^(236)U (or both) used to monitor for beam intensity. We used in-house laboratory standards to check for machine reproducibility, and the GEOTRACES intercalibration standard to check for accuracy. Over a 1-y period, the 2 s.d. reproducibility on the GEOTRACES SW STD 2010-1 was 2.5% for ^(230)Th, 1.8% for ^(232)Th, and 4% for ^(231)Pa. The lessons learned during this intercalibration process will be of value to those analyzing U-Th-Pa and rare earth elements as part of the GEOTRACES program as well as those using U-series elements in other applications that require high yields and low blanks, such as geochronology

Changes in biological productivity along the northwest African margin over the past 20,000 years

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 Paleoceanography 31 (2016): 185–202, doi:10.1002/2015PA002862.The intertropical convergence zone and the African monsoon system are highly sensitive to climate forcing at orbital and millennial timescales. Both systems influence the strength and direction of the trade winds along northwest Africa and thus directly impact coastal upwelling. Sediment cores from the northwest African margin record upwelling-related changes in biological productivity connected to changes in regional and hemispheric climate. We present records of 230Th-normalized biogenic opal and Corg fluxes using a meridional transect of four cores from 19°N–31°N along the northwest African margin to examine changes in paleoproductivity since the last glacial maximum. We find large changes in biogenic fluxes synchronous with changes in eolian fluxes calculated using end-member modeling, suggesting that paleoproductivity and dust fluxes were strongly coupled, likely linked by changes in wind strength. Opal and Corg fluxes increase at all sites during Heinrich Stadial 1 and the Younger Dryas, consistent with an overall intensification of the trade winds, and changes in the meridional flux gradient indicate a southward wind shift at these times. Biogenic fluxes were lowest, and the meridional flux gradients were weakest during the African Humid Period when the monsoon was invigorated due to precessional changes, with greater rainfall and weaker trade winds over northwest Africa. These results expand the spatial coverage of previous paleoproxy studies showing similar changes, and they provide support for modeling studies showing changes in wind strength and direction consistent with increased upwelling during abrupt coolings and decreased upwelling during the African Humid Period.NSF Grant Numbers: OCE-1103262, OCE-1030784, OCE-0402348; Center for Climate and Life2016-07-2

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

Comparing glacial and Holocene opal fluxes in the Pacific sector of the Southern Ocean

Author Posting. © American Geophysical Union, 2009. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Paleoceanography 24 (2009): PA2214, doi:10.1029/2008PA001693.The silicic acid leakage hypothesis (SALH) predicts that during glacial periods excess silicic acid was transported from the Southern Ocean to lower latitudes, which favored diatom production over coccolithophorid production and caused a drawdown of atmospheric CO2. Downcore records of 230Th-normalized opal (biogenic silica) fluxes from 31 cores in the Pacific sector of the Southern Ocean were used to compare diatom productivity during the last glacial period to that of the Holocene and to examine the evidence for increased glacial Si export to the tropics. Average glacial opal fluxes south of the modern Antarctic Polar Front (APF) were less than during the Holocene, while average glacial opal fluxes north of the APF were greater than during the Holocene. However, the magnitude of the increase north of the APF was not enough to offset decreased fluxes to the south, resulting in a decrease in opal burial in the Pacific sector of the Southern Ocean during the last glacial period, equivalent to approximately 15 Gt opal ka−1. This is consistent with the work of Chase et al. (2003a), and satisfies the primary requirement of the SALH, assuming that the upwelled supply of Si was approximately equivalent during the Holocene and the glacial period. However, previous results from the equatorial oceans are inconsistent with the other predictions of the SALH, namely that either the Corg:CaCO3 ratio or the rate of opal burial should have increased during glacial periods. We compare the magnitudes of changes in the Southern Ocean and the tropics and suggest that Si escaping the glacial Southern Ocean must have had an alternate destination, possibly the continental margins. There is currently insufficient data to test this hypothesis, but the existence of this sink and its potential impact on glacial pCO2 remain interesting topics for future study.Funding for this research was provided in part by the U.S. NSF (grant OPP02-30268). We thank the core repository at LDEO and the Antarctic Research Facility at FSU for providing samples

Application of an inverse method to interpret 231Pa/230Th observations from marine sediments

Records of 231Pa/230Th from Atlantic sediments have been interpreted to reflect changes in ocean circulation during the geologic past. Such interpretations should be tested with due regard to the limited spatial coverage of 231Pa/230Th data and the uncertainties in our current understanding of the behavior of both nuclides in the ocean. Here an inverse method is used to evaluate the information contained in 231Pa/230Th compilations for the Holocene, Last Glacial Maximum (LGM), and Heinrich Event 1 (H1). An estimate of the abyssal circulation in the modern Atlantic Ocean is obtained by combining hydrographic observations and dynamical constraints. Then sediment 231Pa/230Th data for each time interval are combined with an advection-scavenging model in order to determine their (in)consistency with the modern circulation estimate. We find that the majority of sediment 231Pa/>230Th data for the Holocene, LGM, or H1 can be brought into consistency with the modern circulation if plausible assumptions are made about the large-scale distribution of 231Pa and about model uncertainties. Moreover, the adjustments in the data needed to reach compatibility with a hypothetical state of no flow (no advection) are positively biased for each time interval, suggesting that the 231Pa/230Th data (including that for H1) are more consistent with a persistence of some circulation than with no circulation. Our study does not imply that earlier claims of a circulation change during the LGM or H1 are inaccurate, but that these claims cannot be given a rigorous basis given the current uncertainties involved in the analysis of the 231Pa/230Th data. An edited version of this paper was published by AGU. Copyright 2011 American Geophysical UnionScience, Faculty ofEarth and Ocean Sciences, Department ofReviewedFacult

(Table 2) Age determination of Southern Ocean sediments

The silicic acid leakage hypothesis (SALH) predicts that during glacial periods excess silicic acid was transported from the Southern Ocean to lower latitudes, which favored diatom production over coccolithophorid production and caused a drawdown of atmospheric CO2. Downcore records of 230Th-normalized opal (biogenic silica) fluxes from 31 cores in the Pacific sector of the Southern Ocean were used to compare diatom productivity during the last glacial period to that of the Holocene and to examine the evidence for increased glacial Si export to the tropics. Average glacial opal fluxes south of the modern Antarctic Polar Front (APF) were less than during the Holocene, while average glacial opal fluxes north of the APF were greater than during the Holocene. However, the magnitude of the increase north of the APF was not enough to offset decreased fluxes to the south, resulting in a decrease in opal burial in the Pacific sector of the Southern Ocean during the last glacial period, equivalent to approximately 15 Gt opal/ka1. This is consistent with the work of Chase et al. (2003, doi:10.1016/S0967-0645(02)00595-7), and satisfies the primary requirement of the SALH, assuming that the upwelled supply of Si was approximately equivalent during the Holocene and the glacial period. However, previous results from the equatorial oceans are inconsistent with the other predictions of the SALH, namely that either the Corg:CaCO3 ratio or the rate of opal burial should have increased during glacial periods. We compare the magnitudes of changes in the Southern Ocean and the tropics and suggest that Si escaping the glacial Southern Ocean must have had an alternate destination, possibly the continental margins. There is currently insufficient data to test this hypothesis, but the existence of this sink and its potential impact on glacial pCO2 remain interesting topics for future study