Dissolved cadmium in the Southern Ocean: Distribution, speciation, and relation to phosphate

We report isotope dilution analyses of dissolved cadmium (Cd) and electrochemical Cd speciation measurements in the Atlantic sector of the Southern Ocean. Bioavailable inorganic Cd is > 100 times higher in near-surface waters south of the Polar Front compared to the Subantarctic Zone because of upwelling and reduced complexation by organic Cd ligands. To trace local changes in the relation between Cd and P, we examine the deviations from a linear deep-water Cd vs. P relation (Cd*), and find that changes in Cd* coincide with the position of frontal systems and covary with primary productivity and total dissolved Mn and Fe concentrations. These covariations agree with potential local changes in phytoplankton Cd uptake rates, resulting from differences in the availability of Cd, Zn, Mn, and Fe. A band of negative Cd* values is associated with formation of Subantarctic Mode Water (SAMW) and Antarctic Intermediate Water (AAIW). In contrast to SAMW, which may export low Cd : P ratios from the Southern Ocean, the Cd : P ratios in AAIW increase by mixing with underlying Upper Circumpolar Deep Water before being exported from the Southern Ocean. Deep waters show constant Cd : P ratios, and both elements behave conservatively with end-member mixing between deep waters of the Weddell Gyre, the Antarctic Circumpolar Current, and inflowing North Atlantic Deep Water. Overall, our results support the hypothesis that the kink in the global Cd vs. P relation is largely caused by high Cd : P uptake ratios in the trace-nutrient–limited Southern Ocean

Calcium Isotopes in Human Urine as a Diagnostic Tool for Bone Loss: Additional Evidence for Time Delays in Bone Response to Experimental Bed Rest

The calcium (Ca) isotopic composition in urine during bed rest has been demonstrated to be systematically light, indicating a negative bone mineral balance (i.e., bone loss). Here we present new Ca isotope data on urine during the “nutritional countermeasures” (NUC) bed rest study. We analyzed the Ca isotopic composition of 24 h pooled urine samples from seven healthy male subjects during baseline data collection (BDC), head-down-tilt bed rest and recovery. Additionally, we analyzed urine from two follow-up examinations after the regeneration phase. We observed a change in Ca isotopic composition during the bed rest phase, indicative of bone loss with a time delay of 10 to 21 days. We also observe that the Ca isotopic composition of urine is strongly dependent on the individual Ca metabolism and varies between subjects. We relate this individuality in Ca metabolism to differences in the amounts of Ca being recycled in the kidneys. Previous studies have shown that the more Ca is reabsorbed in the kidneys the more enriched the urine becomes in heavy isotopes of calcium. The Ca isotopic composition of urine is thus modified by more than one process and cannot be used in a straightforward manner to monitor net bone mineral balance. To overcome this problem, we propose a new baseline approach for using Ca isotopes, which effectively cancels out the effects of individual renal Ca reabsorption. This allows us to detect bone loss in patients without ambiguity by combining measurements of the Ca isotopic composition of urine and daily Ca excretion rate and comparing these to data collected on healthy individuals with a normal steady-state bone balance

Bioactive Trace Metals and Their Isotopes as Paleoproductivity Proxies: An Assessment Using GEOTRACES-Era Data

86 pages, 33 figures, 2 tables, 1 appendix.-- Data Availability Statement: The majority of the dissolved data were sourced from the GEOTRACES Intermediate Data Products in 2014 (Mawji et al., 2015) and 2017 (Schlitzer et al., 2018), and citations to the primary data sources are given in the caption for each figure. Data sources for Figure 1 are given below. Figure 1: Iron: Conway & John, 2014a (Atlantic); Conway & John, 2015a (Pacific); Abadie et al., 2017 (Southern). Zinc: Conway & John, 2014b (Atlantic); Conway & John, 2015a (Pacific); R. M. Wang et al., 2019 (Southern). Copper: Little et al., 2018 (Atlantic); Takano et al., 2017 (Pacific); Boye et al., 2012 (Southern). Cadmium: Conway and John, 2015b (Atlantic); Conway & John, 2015a (Pacific); Abouchami et al., 2014 (Southern). Molybdenum: Nakagawa et al., 2012 (all basins). Barium: Bates et al., 2017 (Atlantic); Geyman et al., 2019 (Pacific); Hsieh & Henderson, 2017 (Southern). Nickel: Archer et al., 2020 (Atlantic); Takano et al., 2017 (Pacific); R. M. Wang et al., 2019 (Southern). Chromium: Goring-Harford et al., 2018 (Atlantic); Moos & Boyle, 2019 (Pacific); Rickli et al., 2019 (Southern). Silver: Fischer et al., 2018 (Pacific); Boye et al., 2012 (Southern)Phytoplankton productivity and export sequester climatically significant quantities of atmospheric carbon dioxide as particulate organic carbon through a suite of processes termed the biological pump. Constraining how the biological pump operated in the past is important for understanding past atmospheric carbon dioxide concentrations and Earth's climate history. However, reconstructing the history of the biological pump requires proxies. Due to their intimate association with biological processes, several bioactive trace metals and their isotopes are potential proxies for past phytoplankton productivity, including iron, zinc, copper, cadmium, molybdenum, barium, nickel, chromium, and silver. Here, we review the oceanic distributions, driving processes, and depositional archives for these nine metals and their isotopes based on GEOTRACES-era datasets. We offer an assessment of the overall maturity of each isotope system to serve as a proxy for diagnosing aspects of past ocean productivity and identify priorities for future research. This assessment reveals that cadmium, barium, nickel, and chromium isotopes offer the most promise as tracers of paleoproductivity, whereas iron, zinc, copper, and molybdenum do not. Too little is known about silver to make a confident determination. Intriguingly, the trace metals that are least sensitive to productivity may be used to track other aspects of ocean chemistry, such as nutrient sources, particle scavenging, organic complexation, and ocean redox state. These complementary sensitivities suggest new opportunities for combining perspectives from multiple proxies that will ultimately enable painting a more complete picture of marine paleoproductivity, biogeochemical cycles, and Earth's climate historyThis contribution grew (and grew) out of a joint workshop between GEOTRACES and Past Global Changes (PAGES) held in Aix-en-Provence in December 2018. The workshop was funded by the U.S. National Science Foundation (NSF) through the GEOTRACES program, the international PAGES project, which received support from the Swiss Academy of Sciences and NSF, and the French program Les Envelopes Fluides et l'Environnement. [...] T. J. Horner acknowledges support from NSF; S. H. Little from the UK Natural Environment Research Council (NE/P018181/1); T. M. Conway from the University of South Florida; and, J. R. Farmer from the Max Planck Society, the Tuttle Fund of the Department of Geosciences of Princeton University, the Grand Challenges Program of the Princeton Environmental Institute, and the Andlinger Center for Energy and the Environment of Princeton University. [...] With the institutional support of the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000928-S

The GEOTRACES Intermediate Data Product 2014

The GEOTRACES Intermediate Data Product 2014 (IDP2014) is the first publicly available data product of the international GEOTRACES programme, and contains data measured and quality controlled before the end of 2013. It consists of two parts: (1) a compilation of digital data for more than 200 trace elements and isotopes (TEIs) as well as classical hydrographic parameters, and (2) the eGEOTRACES Electronic Atlas providing a strongly inter-linked on-line atlas including more than 300 section plots and 90 animated 3D scenes. The IDP2014 covers the Atlantic, Arctic, and Indian oceans, exhibiting highest data density in the Atlantic. The TEI data in the IDP2014 are quality controlled by careful assessment of intercalibration results and multi-laboratory data comparisons at cross-over stations. The digital data are provided in several formats, including ASCII spreadsheet, Excel spreadsheet, netCDF, and Ocean Data View collection. In addition to the actual data values the IDP2014 also contains data quality flags and 1-? data error values where available. Quality flags and error values are useful for data filtering. Metadata about data originators, analytical methods and original publications related to the data are linked to the data in an easily accessible way. The eGEOTRACES Electronic Atlas is the visual representation of the IDP2014 data providing section plots and a new kind of animated 3D scenes. The basin-wide 3D scenes allow for viewing of data from many cruises at the same time, thereby providing quick overviews of large-scale tracer distributions. In addition, the 3D scenes provide geographical and bathymetric context that is crucial for the interpretation and assessment of observed tracer plumes, as well as for making inferences about controlling processes

High-precision cadmium isotope measurements determined by double spike thermal ionisation mass spectrometry

International audienc

Mass-dependent cadmium isotopic variations in nature with emphasis on the marine environment

International audienc

Effect of cadmium sulphide precipitation on the partitioning of Cd isotopes: Implications for the oceanic Cd cycle

International audienceThe biogeochemical cycling of cadmium (Cd) and its isotopes in the surface ocean is dominated by biological uptake into phytoplankton, while regeneration of the sinking particulate Cd governs the shapes of Cd profiles in the deeper ocean. Additionally, the water mass circulation plays an important role in the redistribution of Cd and its isotopes. Superimposed on this general cycle, it has recently been argued that cadmium sulphide (CdS) precipitation can occur in oceanic Oxygen Deficient Zones (ODZ). This has been proposed to account for the decrease in Cd/PO4 ratios and the positive Cd isotope excursion in seawater compared to sinking particles. To assess whether CdS precipitation results in a fractionation of Cd isotopes, we performed cadmium-sulphide precipitation experiments under controlled low-oxygen conditions in low (pure water) and high ionic strength (synthetic seawater) water, with variable reaction times and cadmium/sulphide ratios. Enrichment in light Cd isotopes is systematically observed in the precipitated CdS phase, in agreement with recent ab initio simulations of isotope effects associated with Cd speciation in aqueous solution. Our experimental results follow a closed-system Rayleigh fractionation model with the fractionation factor (αCdsol-CdS) for 112Cd/110Cd decreasing with increasing salinity - from 1.00026 for pure water to 1.00014 for a salinity twice that of modern seawater, indicating a salinity control on the magnitude of Cd isotope fractionation. We propose that this fractionation, varying with salinity, is controlled by isotope equilibrium between the various Cd aqueous species present in solution, with preferential involvement of free Cd2+ ion in CdS formation. The magnitude of Cd isotope fractionation in seawater (αCdsol-CdS = 1.00016) determined in our study is in accord with the Cd isotope shift observed in modern oceanic ODZ and attributed to removal by CdS. Our experiments show that CdS precipitation could have significant local impact on the cycling of Cd, and further demonstrates the utility of Cd isotopes as tracers of the sequestration of cadmium into sulphides in restricted euxinic basins, such as the Black Sea

Lead isotopes inthe Eastern Equatorial Pacific

The influence of atmospheric dust on climate and biogeochemical cycles in the oceans is well understood but poorly quantified. Glacial atmospheric dust loads were generally greater than those during the Holocene, as shown, for example, by the covariation of dust fluxes in the Equatorial Pacific and Antarctic ice cores. Nevertheless, it remains unclear whether these increases in dust flux were associated with changes in sources of dust, which would in turn suggest variations in wind patterns, climate or paleo-environment. Such questions can be answered using radiogenic isotope tracers of dust provenance. Here, we present a 160-kyr high-precision lead isotope time-series of dust input to the Eastern Equatorial Pacific (EEP) from core ODP Leg 138, Site 849 (0°11.59' N, 110°31.18' W). The Pb isotope record, combined with Nd isotope data, rules out contributions from Northern Hemisphere dust sources, north of the Intertropical Convergence Zone, such as Asia or North Africa/Sahara; similarly, eolian sources in Australia, Central America, the Northern Andes and Patagonia appear insignificant based upon the radiogenic isotope data. Fluctuations in Pb isotope ratios throughout the last 160 kyr show, instead, that South America remained the prevailing source of dusts to the EEP. There are two distinct South American Pb isotope end-members, constrained to be located in the south Central Volcanic Zone (CVZ, 22° S - 27.5° S) and the South Volcanic Zone (SVZ, 33° S - 43° S), with the former most likely originating in the Atacama Desert. Dust availability in the SVZ appears to be related to the weathering of volcanic deposits and the development of ash-derived Andosols, and influenced by local factors that might include vegetation cover. Variations in the dust fluxes from the two sources are in phase with both the dust flux and temperature records from Antarctican ice cores. We show that the forcing of dust provenance over time in the EEP overall is influenced by high-southerly-latitude climate conditions, leading to changes in the latitudinal position and strength of the South Westerlies as well as the coastal winds that blow northward along the Chilean margin. The net result is a modulation of dust emission from the Atacama Desert and the SVZ via a northward migration of the South Westerlies during cold periods and southward retreat during glacial terminations