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Differential Behavior of Metal Sulfides in Hydrothermal Plumes and Diffuse Flows

  • Emily R. Estes*
    Emily R. Estes
    University of Delaware, School of Marine Science and Policy, 700 Pilottown Road, Lewes, Delaware 19958, United States
    *Email: [email protected]
  • Debora Berti
    Debora Berti
    Virginia Tech National Center of Earth and Environmental Nanotechnology Infrastructure (NanoEarth), Institute for Critical Technology and Applied Science, Virginia Tech, Blacksburg, Virginia 24061, United States
    More by Debora Berti
  • Alyssa J. Findlay
    Alyssa J. Findlay
    Center for Geomicrobiology, Department of Bioscience, Aarhus University, Aarhus C 8000, Denmark
  • Michael F. Hochella Jr.
    Michael F. Hochella, Jr.
    Virginia Tech National Center of Earth and Environmental Nanotechnology Infrastructure (NanoEarth), Institute for Critical Technology and Applied Science, Virginia Tech, Blacksburg, Virginia 24061, United States
  • Timothy J. Shaw
    Timothy J. Shaw
    Department of Chemistry and Biochemistry, University of South Carolinia, Columbia, South Carolina 29208 United States
  • Mustafa Yücel
    Mustafa Yücel
    Institute of Marine Sciences, Middle East Technical University, 33731 Mersin, Turkey
  • Eric H. De Carlo
    Eric H. De Carlo
    Department of Oceanography, School of Ocean and Earth Science and Technology, University of Hawaii at Manoa, 2500 Campus Road, Honolulu, Hawaii 96822, United States
  • , and 
  • George W. Luther III
    George W. Luther, III
    University of Delaware, School of Marine Science and Policy, 700 Pilottown Road, Lewes, Delaware 19958, United States
Cite this: ACS Earth Space Chem. 2022, 6, 6, 1429–1442
Publication Date (Web):May 16, 2022
https://doi.org/10.1021/acsearthspacechem.1c00377
Copyright © 2022 American Chemical Society

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    Abstract

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    Extensive sampling of high-temperature hydrothermal fluids and diffuse flows within <2 m of the vent orifices at the 9°50′N East Pacific Rise (EPR) hydrothermal vent field reveals formation of nanoparticulate phases and rapid precipitation/aggregation of metal sulfide minerals upon mixing of vent fluid with ambient seawater. Here, we characterize metal sulfide phases via scanning and transmission electron microscopy (SEM, TEM) in addition to quantifying the concentrations of major and trace metals in filtered and unfiltered fluid samples. Analyses demonstrate that, despite coprecipitation in phases such as chalcopyrite, iron speciation and transport is decoupled from that of copper and zinc. We observe the formation of ∼10–500 nm diameter (nano)particulate Zn and Cu sulfide phases that are near-quantitatively removed by filtration. Iron sulfides, conversely, are typically present in SEM images as larger particles up to tens of microns in diameter. Few small nanoparticles (20–100 nm diameter) are captured on the filter, but determination of nitric-acid-soluble iron in 0.2 μm filtered samples indicates the presence of pyrite nanoparticles. Physical mixing and temperature play a larger role in determining the extent of nanoparticulate pyrite formation than fluid chemistry. In diffuse flow environments, Fe and Cu more commonly co-occur as aggregates of very small crystallites, with the Zn sulfide phases occurring separately. Sample pH and the ZPC (zero point of charge) of metal sulfides exhibit chemical control on nanoparticle and large particle formation versus aggregation. The concentrations of the additional trace metals analyzed vary between vent sites, despite the short distances between the sites and likely similar magmatic sources. Measured trace metal concentrations highlight the importance of diffuse flow systems in hydrothermal metal emissions. These near-vent behavioral differences have implications for the long-distance transport of metals away from vent fields in buoyant and nonbuoyant plumes.

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsearthspacechem.1c00377.

    • A map of vent sites (Figure S1), the linear correlation between Fe concentrations measured by ferrozine and ICP-MS (Figure S2), ICP-MS data from filtered samples correlated with fraction seawater (Figure S3), and additional SEM and TEM images (Figure S4) (PDF)

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    Cited By

    This article is cited by 3 publications.

    1. Xue-Bin Zhang, Hao Tian, Song-Hai Wu, Yong Liu, Xu Han. Speciation Differences in the Surface Oxidizing Species on FeS2 and NiS2: Reactivity in Hydrogen Atom Transfer and Oxygen Atom Transfer. ACS Earth and Space Chemistry 2023, 7 (5) , 998-1008. https://doi.org/10.1021/acsearthspacechem.2c00365
    2. Nadine Kabengi, (Guest Editor)Udo Becker, (Guest Editor)Gordon E. Brown, Jr. (Guest Editor). Virtual Special Issue of ACS Earth and Space Chemistry in Honor of Prof. Michael F. Hochella, Jr.. ACS Earth and Space Chemistry 2022, 6 (9) , 2115-2117. https://doi.org/10.1021/acsearthspacechem.2c00250
    3. George W. Luther. Review on the physical chemistry of iodine transformations in the oceans. Frontiers in Marine Science 2023, 10 https://doi.org/10.3389/fmars.2023.1085618