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

Atmospheric Dust Inputs, Iron Cycling, and Biogeochemical Connections in the South Pacific Ocean from Thorium Isotopes

One of the primary sources of micronutrients to the sea surface in remote ocean regions is the deposition of atmospheric dust. Geographic patterns in biogeochemical processes such as primary production and nitrogen fixation that require micronutrients like iron (Fe) are modulated in part by the spatial distribution of dust supply. Global models of dust deposition rates are poorly calibrated in the open ocean, owing to the difficulty of determining dust fluxes in sparsely sampled regions. We present new estimates of dust and Fe input rates from measurements of dissolved and particulate thorium isotopes ²³⁰Th and ²³²Th on the FS Sonne SO245 section (GEOTRACES process study GPpr09) in the South Pacific. We first discuss high‐resolution upper water column profiles of Th isotopes and the implications for the systematics of dust flux reconstructions from seawater Th measurements. We find dust fluxes in the center of the highly oligotrophic South Pacific Gyre that are the lowest of any mean annual dust input rates measured in the global oceans, but that are 1–2 orders of magnitude higher than those estimated by global dust models. We also determine dust‐borne Fe fluxes and reassess the importance of individual Fe sources to the surface South Pacific Gyre, finding that dust dissolution, not vertical or lateral diffusion, is the primary Fe source. Finally, we combine our estimates of Fe flux in dust with previously published cellular and enzymatic quotas to determine theoretical upper limits on annual average nitrogen fixation rates for a given Fe deposition rate

Atmospheric Dust Inputs, Iron Cycling, and Biogeochemical Connections in the South Pacific Ocean from Thorium Isotopes

One of the primary sources of micronutrients to the sea surface in remote ocean regions is the deposition of atmospheric dust. Geographic patterns in biogeochemical processes such as primary production and nitrogen fixation that require micronutrients like iron (Fe) are modulated in part by the spatial distribution of dust supply. Global models of dust deposition rates are poorly calibrated in the open ocean, owing to the difficulty of determining dust fluxes in sparsely sampled regions. We present new estimates of dust and Fe input rates from measurements of dissolved and particulate thorium isotopes ²³⁰Th and ²³²Th on the FS Sonne SO245 section (GEOTRACES process study GPpr09) in the South Pacific. We first discuss high‐resolution upper water column profiles of Th isotopes and the implications for the systematics of dust flux reconstructions from seawater Th measurements. We find dust fluxes in the center of the highly oligotrophic South Pacific Gyre that are the lowest of any mean annual dust input rates measured in the global oceans, but that are 1–2 orders of magnitude higher than those estimated by global dust models. We also determine dust‐borne Fe fluxes and reassess the importance of individual Fe sources to the surface South Pacific Gyre, finding that dust dissolution, not vertical or lateral diffusion, is the primary Fe source. Finally, we combine our estimates of Fe flux in dust with previously published cellular and enzymatic quotas to determine theoretical upper limits on annual average nitrogen fixation rates for a given Fe deposition rate

Deep-Sea Oxygen Depletion and Ocean Carbon Sequestration During the Last Ice Age

Enhanced ocean carbon storage during the Pleistocene ice ages lowered atmospheric CO2 concentrations by 80 to 100 ppm relative to interglacial levels. Leading hypotheses to explain this phenomenon invoke a greater efficiency of the ocean's biological pump, in which case carbon storage in the deep sea would have been accompanied by a corresponding reduction in dissolved oxygen. We exploit the sensitivity of organic matter preservation in marine sediments to bottom water oxygen concentration to constrain the level of dissolved oxygen in the deep central equatorial Pacific Ocean during the last glacial period (18,000–28,000 years BP) to have been within the range of 20–50 μmol/kg, much less than the modern value of ~168 μmol/kg. We further demonstrate that reduced oxygen levels characterized the water column below a depth of ~1,000 m. Converting the ice age oxygen level to an equivalent concentration of respiratory CO2, and extrapolating globally, we estimate that deep‐sea CO2 storage during the last ice age exceeded modern values by as much as 850 Pg C, sufficient to balance the loss of carbon from the atmosphere (~200 Pg C) and from the terrestrial biosphere (~300–600 Pg C). In addition, recognizing the enhanced preservation of organic matter in ice age sediments of the deep Pacific Ocean helps reconcile previously unexplained inconsistencies among different geochemical and micropaleontological proxy records used to assess past changes in biological productivity of the ocean.Several grants from the U.S. National Science Foundation supported the production of the data reported here during the course of previous studies. However, the synthesis of results presented here was carried out without directed grant support except that S. L. J. acknowledges financial support by the Swiss National Science Foundation (grants PP00P2‐144811 and PP00P2‐172915)

\u3csup\u3e230\u3c/sup\u3eTh and \u3csup\u3e231\u3c/sup\u3ePa on GEOTRACES GA03, the U.S. GEOTRACES North Atlantic transect, and implications for modern and paleoceanographic chemical fluxes

The long-lived uranium decay products 230Th and 231Pa are widely used as quantitative tracers of adsorption to sinking particles (scavenging) in the ocean by exploiting the principles of radioactive disequilibria. Because of their preservation in the Pleistocene sediment record and through largely untested assumptions about their chemical behavior in the water column, the two radionuclides have also been used as proxies for a variety of chemical fluxes in the past ocean. This includes the vertical flux of particulate matter to the seafloor, the lateral flux of insoluble elements to continental margins (boundary scavenging), and the southward flux of water out of the deep North Atlantic. In a section of unprecedented vertical and zonal resolution, the distributions of 230Th and 231Pa across the North Atlantic shed light on the marine cycling of these radionuclides and further inform their use as tracers of chemical flux. Enhanced scavenging intensities are observed in benthic layers of resuspended sediments on the eastern and western margins and in a hydrothermal plume emanating from the Mid-Atlantic Ridge. Boundary scavenging is clearly expressed in the water column along a transect between Mauritania and Cape Verde which is used to quantify a bias in sediment fluxes calculated using 230Th-normalization and to demonstrate enhanced 231Pa removal from the deep North Atlantic by this mechanism. The influence of deep ocean ventilation that leads to the southward export of 231Pa is apparent. The 231Pa/230Th ratio, however, predominantly reflects spatial variability in scavenging intensity, complicating its applicability as a proxy for the Atlantic meridional overturning circulation

230Th and 231Pa on GEOTRACES GA03, the U.S. GEOTRACES North Atlantic transect, and implications for modern and paleoceanographic chemical fluxes

The long-lived uranium decay products 230Th and 231Pa are widely used as quantitative tracers of adsorption to sinking particles (scavenging) in the ocean by exploiting the principles of radioactive disequilibria. Because of their preservation in the Pleistocene sediment record and through largely untested assumptions about their chemical behavior in the water column, the two radionuclides have also been used as proxies for a variety of chemical fluxes in the past ocean. This includes the vertical flux of particulate matter to the seafloor, the lateral flux of insoluble elements to continental margins (boundary scavenging), and the southward flux of water out of the deep North Atlantic. In a section of unprecedented vertical and zonal resolution, the distributions of 230Th and 231Pa across the North Atlantic shed light on the marine cycling of these radionuclides and further inform their use as tracers of chemical flux. Enhanced scavenging intensities are observed in benthic layers of resuspended sediments on the eastern and western margins and in a hydrothermal plume emanating from the Mid-Atlantic Ridge. Boundary scavenging is clearly expressed in the water column along a transect between Mauritania and Cape Verde which is used to quantify a bias in sediment fluxes calculated using 230Th-normalization and to demonstrate enhanced 231Pa removal from the deep North Atlantic by this mechanism. The influence of deep ocean ventilation that leads to the southward export of 231Pa is apparent. The 231Pa/230Th ratio, however, predominantly reflects spatial variability in scavenging intensity, complicating its applicability as a proxy for the Atlantic meridional overturning circulation

Intensity of Th and Pa scavenging partitioned by particle chemistry in the North Atlantic Ocean

Author Posting. © The Author(s), 2015. This is the author's version of the work. It is posted here by permission of Elsevier for personal use, not for redistribution. The definitive version was published in Marine Chemistry 170 (2015): 49-60, doi:10.1016/j.marchem.2015.01.006.The natural radionuclides 231Pa and 230Th are incorporated into the marine sediment record by scavenging, or adsorption to various particle types, via chemical reactions that are not fully understood. Because these isotopes have potential value in tracing several oceanographic processes, we investigate the nature of scavenging using trans-Atlantic measurements of dissolved (<0.45 μm) and particulate (0.8-51 μm) 231Pa and 230Th, together with major particle composition. We find widespread impact of intense scavenging by authigenic Fe/Mn (hydr)oxides, in the form of hydrothermal particles emanating from the Mid-Atlantic ridge and particles resuspended from reducing conditions near the seafloor off the coast of West Africa. Biogenic opal was not found to be a significant scavenging phase for either element in this sample set, essentially because of its low abundance and small dynamic range at the studied sites. Distribution coefficients in shallow (< 200 m) depths are anomalously low which suggests either the unexpected result of a low scavenging intensity for organic matter or that, in water masses containing abundant organic-rich particles, a greater percentage of radionuclides exist in the colloidal or complexed phase. In addition to particle concentration, the oceanic distribution of particle types likely plays a significant role in the ultimate distribution of sedimentary 230Th and 231Pa.Cruise management for GA03 was funded by the U. S. National Science Foundation to W. Jenkins (OCE-0926423), E. Boyle (OCE-0926204), and G. Cutter (OCE-0926092). Radionuclide studies were supported by NSF (OCE-0927064 to LDEO, OCE-0926860 to WHOI, OCE- 0927757 to URI, and OCE-0927754 to UMN). Additional support came from the European Research Council (278705) to LFR and the Ford Foundation Predoctoral Fellowship to SMV. Particle studies were supported by NSF OCE-0963026 to PJL

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

Replacement times of a spectrum of elements in the North Atlantic based on thorium supply

The measurable supply of 232Th to the ocean can be used to derive the supply of other elements, which is more difficult to quantify directly. The measured inventory of an element divided by the derived supply yields a replacement time estimate, which in special circumstances is related to a residence time. As a proof of concept, Th‐based supply rates imply a range in the replacement times of the rare earth elements (REEs) in the North Atlantic that is consistent with the chemical reactivity of REEs related to their ionic charge density. Similar estimates of replacement times for the bioactive trace elements (Fe, Mn, Zn, Cd, Cu and Co), ranging from \u3c5 years to \u3e50,000 years, demonstrate the broad range of elemental reactivity in the ocean. Here, we discuss how variations in source composition, fractional solubility ratios or non‐continental sources such as hydrothermal vents lead to uncertainties in Th‐based replacement time estimates. We show that the constraints on oceanic replacement time provided by the Th‐based calculations are broadly applicable in predicting how elements are distributed in the ocean and for some elements, such as Fe, may inform us on how the carbon cycle may be impacted by trace element supply and removal