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  1. Reversible scavenging, the oceanographic process by which dissolved metals exchange onto and off sinking particles and are thereby transported to deeper depths, has been well established for the metal thorium for decades. Reversible scavenging both deepens the elemental distribution of adsorptive elements and shortens their oceanic residence times in the ocean compared to nonadsorptive metals, and scavenging ultimately removes elements from the ocean via sedimentation. Thus, it is important to understand which metals undergo reversible scavenging and under what conditions. Recently, reversible scavenging has been invoked in global biogeochemical models of a range of metals including lead, iron, copper, and zinc to fit modeled data to observations of oceanic dissolved metal distributions. Nonetheless, the effects of reversible scavenging remain difficult to visualize in ocean sections of dissolved metals and to distinguish from other processes such as biological regeneration. Here, we show that particle-rich “veils” descending from high-productivity zones in the equatorial and North Pacific provide idealized illustrations of reversible scavenging of dissolved lead (Pb). A meridional section of dissolved Pb isotope ratios across the central Pacific shows that where particle concentrations are sufficiently high, such as within particle veils, vertical transport of anthropogenic surface–dissolved Pb isotope ratios toward the deep ocean is manifested as columnar isotope anomalies. Modeling of this effect shows that reversible scavenging within particle-rich waters allows anthropogenic Pb isotope ratios from the surface to penetrate ancient deep waters on timescales sufficiently rapid to overcome horizontal mixing of deep water Pb isotope ratios along abyssal isopycnals. 
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    Free, publicly-accessible full text available June 6, 2024
  2. Changes in chromium (Cr) isotope ratios due to fractionation between trivalent [Cr(III)] and hexavalent [Cr(VI)] are being utilized by geologists to infer oxygen conditions in past environments. However, there is little information available on Cr in the modern ocean to ground-truth these inferences. Transformations between the two chromium species are important processes in oceanic Cr cycling. Here we present profiles of hexavalent and trivalent Cr concentrations and stable isotope ratios from the eastern tropical North Pacific (ETNP) oxygen-deficient zone (ODZ) which support theoretical and experimental studies that predict that lighter Cr is preferentially reduced in low-oxygen environments and that residual dissolved Cr becomes heavier due to removal of particle-reactive Cr(III) on sinking particles. The Cr(III) maximum dominantly occurs in the upper portion of the ODZ, implying that microbial activity (dependent on the sinking flux of organic matter) may be the dominant mechanism for this transformation, rather than a simple inorganic chemical conversion between the species depending on the redox potential.

     
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  3. null (Ed.)
  4. Abstract

    Ocean time‐series sites are influenced by both temporal variability, as in situ conditions change, as well as spatial variability, as water masses move across the fixed observation point. To remove the effect of spatial variability, this study made sub‐daily Lagrangian observations of trace elements and isotopes (Al, Sc, Mn, Fe, Co, Ni, Cu, Zn, Cd, Pb,232Th, and230Th) in surface water over a 12‐day period (July–August 2015) in the North Pacific near the Hawaii Ocean Time‐series Station ALOHA. Additionally, a vertical profile in the upper 250 m was analyzed. This dataset is intercalibrated with GEOTRACES standards and provides a consistent baseline for trace element studies in the oligotrophic North Pacific. No diel changes in trace elements could be resolved, although day‐to‐day variations were resolved for some elements (Fe, Cu, and Zn), which may be related to organic matter cycling or ligand availability. Pb concentrations remained relatively constant during 1997–2015, presenting a change from previous decreases. Nutrient to trace element stoichiometric ratios were compared to those observed in phytoplankton as an indication of the extent of biological trace element utilization in this ecosystem, providing a basis for future ecological trace element studies.

     
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