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Diagnostic Morphology and Solid-State Chemical Speciation of Hydrothermally Derived Particulate Fe in a Long-Range Dispersing Plume

  • Colleen L. Hoffman
    Colleen L. Hoffman
    Department of Earth Sciences, University of Minnesota-Twin Cities, Minneapolis, Minnesota 55455, United States
  • Collin S. Schladweiler
    Collin S. Schladweiler
    Department of Soil, Water, and Climate, University of Minnesota-Twin Cities, Saint Paul, Minnesota 55108, United States
  • Nicholas C. A. Seaton
    Nicholas C. A. Seaton
    University of Minnesota, College of Science and Engineering Characterization Facility, Minneapolis, Minnesota 55455, United States
  • Sarah L. Nicholas
    Sarah L. Nicholas
    Department of Soil, Water, and Climate, University of Minnesota-Twin Cities, Saint Paul, Minnesota 55108, United States
  • Jessica N. Fitzsimmons
    Jessica N. Fitzsimmons
    Department of Oceanography, Texas A&M University, College Station, Texas 77843, United States
  • Robert M. Sherrell
    Robert M. Sherrell
    Department of Marine and Coastal Sciences and Department of Earth and Planetary Sciences, Rutgers University, New Brunswick, New Jersey 08901, United States
  • Christopher R. German
    Christopher R. German
    Department of Geology and Geophysics, Woods Hole Oceanographic Institution, Woods Hole, Massachusetts 02543, United States
  • Phoebe J. Lam
    Phoebe J. Lam
    Department of Ocean Sciences, University of California-Santa Cruz, Santa Cruz, California 95064, United States
  • , and 
  • Brandy M. Toner*
    Brandy M. Toner
    Department of Earth Sciences, University of Minnesota-Twin Cities, Minneapolis, Minnesota 55455, United States
    Department of Soil, Water, and Climate, University of Minnesota-Twin Cities, Saint Paul, Minnesota 55108, United States
    *Email: [email protected]
Cite this: ACS Earth Space Chem. 2020, 4, 10, 1831–1842
Publication Date (Web):September 21, 2020
https://doi.org/10.1021/acsearthspacechem.0c00067
Copyright © 2020 American Chemical Society

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    Abstract

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    Deep-sea hydrothermal vents are a source of Fe to the ocean with potential impact on surface ocean primary productivity. Long-range horizontal transport of hydrothermally derived Fe in suspended particles (pFe) has been demonstrated recently. However, the biogeochemical mechanisms allowing for this sustained transport of Fe, in a size class that should otherwise sink to the sediments, are unknown. In this study, we measured particle morphology and pFe speciation in the far-field Southern East Pacific Rise (SEPR) neutrally buoyant hydrothermal plume to understand the properties of pFe transported over 1000s of km. Particles were collected by in situ filtration over an 8000 km transect that included the 4300 km SEPR neutrally buoyant plume. Particle morphology was investigated using scanning electron microscopy (SEM) with elemental analysis. Solid-state pFe speciation was measured by microfocused X-ray absorption near edge structure (μXANES) spectroscopy, microfocused extended X-ray absorption fine structure (μEXAFS) spectroscopy, and bulk EXAFS spectroscopy. We identified two diagnostic hydrothermal signatures for plume pFe emanating from the SEPR. First, the morphological signature is best described as large rounded aggregates (∼3 μm in diameter) composed of mostly Fe nanoparticles (≤100 nm in diameter). Second, the chemical speciation signature is best described as an Fe(III) oxyhydroxide nanomineral having short-range structural order. This pFe speciation signature has properties consistent with precipitation in the presence of organic or inorganic ligands or within a microbial biofilm. To our knowledge, this study is the first of its kind in terms of the overall length and coherency of the far-field hydrothermal plume sampled, as well as the use of EXAFS to describe Fe speciation in the particulate size class. Our findings can be used to design controlled experiments to investigate processes and their rates, such as precipitation, aggregation/disaggregation, and settling. The outcomes of carefully designed experiments should lead to more realistic representations of transport and bioavailability of hydrothermally derived Fe in ocean biogeochemical models.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsearthspacechem.0c00067.

    • Samples names, characteristics, and analyses; filtration artifacts and settling of composite particles; SEM images; electron dispersion X-ray spectroscopy; microprobe iron 1s X-ray absorption near edge structure (μ-XANES) spectroscopy; iron XANES reference materials and corresponding linear combination fit (LCF) bins; iron 1s extended X-ray absorption fine structure (EXAFS) spectroscopy; and supplemental references (PDF)

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    Cited By

    This article is cited by 7 publications.

    1. Emily R. Estes, Debora Berti, Alyssa J. Findlay, Michael F. Hochella, Jr., Timothy J. Shaw, Mustafa Yücel, Eric H. De Carlo, George W. Luther, III. Differential Behavior of Metal Sulfides in Hydrothermal Plumes and Diffuse Flows. ACS Earth and Space Chemistry 2022, 6 (6) , 1429-1442. https://doi.org/10.1021/acsearthspacechem.1c00377
    2. Hilary G. Close, (Guest Editor)Phoebe J. Lam, (Guest Editor)Brian N. Popp (Guest Editor). Marine Particle Chemistry: Influence on Biogeochemical Cycles and Particle Export. ACS Earth and Space Chemistry 2021, 5 (5) , 1210-1211. https://doi.org/10.1021/acsearthspacechem.1c00091
    3. Christopher R. German, Susan Q. Lang, Jessica N. Fitzsimmons. Hydrothermal processes. 2024https://doi.org/10.1016/B978-0-323-99762-1.00048-6
    4. Phoebe J. Lam, Yang Xiang. The geochemistry of marine particles. 2024https://doi.org/10.1016/B978-0-323-99762-1.00053-X
    5. Isabel R Baker, Sarick L Matzen, Christopher J Schuler, Brandy M Toner, Peter R Girguis, . Aerobic iron-oxidizing bacteria secrete metabolites that markedly impede abiotic iron oxidation. PNAS Nexus 2023, 2 (12) https://doi.org/10.1093/pnasnexus/pgad421
    6. Gabriel Dulaquais, Pierre Fourrier, Cécile Guieu, Léo Mahieu, Ricardo Riso, Pascal Salaun, Chloé Tilliette, Hannah Whitby. The role of humic-type ligands in the bioavailability and stabilization of dissolved iron in the Western Tropical South Pacific Ocean. Frontiers in Marine Science 2023, 10 https://doi.org/10.3389/fmars.2023.1219594
    7. Brandy D. Stewart, Jeffry V. Sorensen, Kathleen Wendt, Jason B. Sylvan, Christopher R. German, Karthik Anantharaman, Gregory J. Dick, John A. Breier, Brandy M. Toner. A multi-modal approach to measuring particulate iron speciation in buoyant hydrothermal plumes. Chemical Geology 2021, 560 , 120018. https://doi.org/10.1016/j.chemgeo.2020.120018

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