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Title: Iron transformation pathways and redox micro-environments in seafloor sulfide-mineral deposits: Spatially resolved Fe XAS and δ57/54Fe observations

Abstract

Hydrothermal sulfide chimneys located along the global system of oceanic spreading centers are habitats for microbial life during active venting. Hydrothermally extinct, or inactive, sulfide deposits also host microbial communities at globally distributed sites. The main goal of this study is to describe Fe transformation pathways, through precipitation and oxidation-reduction (redox) reactions, and examine transformation products for signatures of biological activity using Fe mineralogy and stable isotope approaches. The study includes active and inactive sulfides from the East Pacific Rise 9°50'N vent field. First, the mineralogy of Fe(III)-bearing precipitates is investigated using microprobe X-ray absorption spectroscopy (μXAS) and X-ray diffraction (μXRD). Second, laser-ablation (LA) and micro-drilling (MD) are used to obtain spatially-resolved Fe stable isotope analysis by multicollector-inductively coupled plasma-mass spectrometry (MC-ICP-MS). Eight Fe-bearing minerals representing three mineralogical classes are present in the samples: oxyhydroxides, secondary phyllosilicates, and sulfides. For Fe oxyhydroxides within chimney walls and layers of Si-rich material, enrichments in both heavy and light Fe isotopes relative to pyrite are observed, yielding a range of δ57Fe values up to 6‰. Overall, several pathways for Fe transformation are observed. Pathway 1 is characterized by precipitation of primary sulfide minerals from Fe(II)aq-rich fluids in zones of mixing between vent fluidsmore » and seawater. Pathway 2 is also consistent with zones of mixing but involves precipitation of sulfide minerals from Fe(II)aq generated by Fe(III) reduction. Pathway 3 is direct oxidation of Fe(II) aq from hydrothermal fluids to form Fe(III) precipitates. Finally, Pathway 4 involves oxidative alteration of pre-existing sulfide minerals to form Fe(III). The Fe mineralogy and isotope data do not support or refute a unique biological role in sulfide alteration. The findings reveal a dynamic range of Fe transformation pathways consistent with a continuum of micro-environments having variable redox conditions. Lastly, these micro-environments likely support redox cycling of Fe and S and are consistent with culture-dependent and -independent assessments of microbial physiology and genetic diversity of hydrothermal sulfide deposits.« less

Authors:
 [1];  [2];  [3];  [4];  [5]
  1. Univ. of Minnesota-Twin Cities, St. Paul, MN (United States)
  2. Institut Francais de Recherche pour l'Exploitation de la Mer, Plouzane (France)
  3. Univ. of Minnesota-Twin Cities, Minneapolis, MN (United States)
  4. Univ. of Bremen, Bremen (Germany)
  5. Univ. of Southern California, Los Angeles, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1257607
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Frontiers in Microbiology
Additional Journal Information:
Journal Volume: 7; Journal ID: ISSN 1664-302X
Publisher:
Frontiers Research Foundation
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 58 GEOSCIENCES; hydrothermal; East Pacific Rise; X-ray absorption spectroscopy; stable isotopes; micro-environment; mineral alteration; iron; biosignature

Citation Formats

Toner, Brandy M., Rouxel, Olivier J., Santelli, Cara M., Bach, Wolfgang, and Edwards, Katrina J. Iron transformation pathways and redox micro-environments in seafloor sulfide-mineral deposits: Spatially resolved Fe XAS and δ57/54Fe observations. United States: N. p., 2016. Web. doi:10.3389/fmicb.2016.00648.
Toner, Brandy M., Rouxel, Olivier J., Santelli, Cara M., Bach, Wolfgang, & Edwards, Katrina J. Iron transformation pathways and redox micro-environments in seafloor sulfide-mineral deposits: Spatially resolved Fe XAS and δ57/54Fe observations. United States. https://doi.org/10.3389/fmicb.2016.00648
Toner, Brandy M., Rouxel, Olivier J., Santelli, Cara M., Bach, Wolfgang, and Edwards, Katrina J. Tue . "Iron transformation pathways and redox micro-environments in seafloor sulfide-mineral deposits: Spatially resolved Fe XAS and δ57/54Fe observations". United States. https://doi.org/10.3389/fmicb.2016.00648. https://www.osti.gov/servlets/purl/1257607.
@article{osti_1257607,
title = {Iron transformation pathways and redox micro-environments in seafloor sulfide-mineral deposits: Spatially resolved Fe XAS and δ57/54Fe observations},
author = {Toner, Brandy M. and Rouxel, Olivier J. and Santelli, Cara M. and Bach, Wolfgang and Edwards, Katrina J.},
abstractNote = {Hydrothermal sulfide chimneys located along the global system of oceanic spreading centers are habitats for microbial life during active venting. Hydrothermally extinct, or inactive, sulfide deposits also host microbial communities at globally distributed sites. The main goal of this study is to describe Fe transformation pathways, through precipitation and oxidation-reduction (redox) reactions, and examine transformation products for signatures of biological activity using Fe mineralogy and stable isotope approaches. The study includes active and inactive sulfides from the East Pacific Rise 9°50'N vent field. First, the mineralogy of Fe(III)-bearing precipitates is investigated using microprobe X-ray absorption spectroscopy (μXAS) and X-ray diffraction (μXRD). Second, laser-ablation (LA) and micro-drilling (MD) are used to obtain spatially-resolved Fe stable isotope analysis by multicollector-inductively coupled plasma-mass spectrometry (MC-ICP-MS). Eight Fe-bearing minerals representing three mineralogical classes are present in the samples: oxyhydroxides, secondary phyllosilicates, and sulfides. For Fe oxyhydroxides within chimney walls and layers of Si-rich material, enrichments in both heavy and light Fe isotopes relative to pyrite are observed, yielding a range of δ57Fe values up to 6‰. Overall, several pathways for Fe transformation are observed. Pathway 1 is characterized by precipitation of primary sulfide minerals from Fe(II)aq-rich fluids in zones of mixing between vent fluids and seawater. Pathway 2 is also consistent with zones of mixing but involves precipitation of sulfide minerals from Fe(II)aq generated by Fe(III) reduction. Pathway 3 is direct oxidation of Fe(II) aq from hydrothermal fluids to form Fe(III) precipitates. Finally, Pathway 4 involves oxidative alteration of pre-existing sulfide minerals to form Fe(III). The Fe mineralogy and isotope data do not support or refute a unique biological role in sulfide alteration. The findings reveal a dynamic range of Fe transformation pathways consistent with a continuum of micro-environments having variable redox conditions. Lastly, these micro-environments likely support redox cycling of Fe and S and are consistent with culture-dependent and -independent assessments of microbial physiology and genetic diversity of hydrothermal sulfide deposits.},
doi = {10.3389/fmicb.2016.00648},
journal = {Frontiers in Microbiology},
number = ,
volume = 7,
place = {United States},
year = {Tue May 10 00:00:00 EDT 2016},
month = {Tue May 10 00:00:00 EDT 2016}
}

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Iron isotope composition of some Archean and Proterozoic iron formations
journal, March 2012

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Sulfur, sulfides, oxides and organic matter aggregated in submarine hydrothermal plumes at 9°50′N East Pacific Rise
journal, July 2012


Experimental determination of iron isotope fractionations among Feaq2+–FeSaq–Mackinawite at low temperatures: Implications for the rock record
journal, July 2012


Fractionation of Fe isotopes during Fe(II) oxidation by a marine photoferrotroph is controlled by the formation of organic Fe-complexes and colloidal Fe fractions
journal, September 2015

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Iron mineral structure, reactivity, and isotopic composition in a South Pacific Gyre ferromanganese nodule over 4 Ma
journal, December 2015

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O phototroph, o chemotroph, where art thou?
journal, June 2001


Microbe–metal interactions in marine hydrothermal environments
journal, April 2003


Atom Exchange between Aqueous Fe(II) and Goethite: An Fe Isotope Tracer Study
journal, February 2009

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  • Environmental Science & Technology, Vol. 43, Issue 4
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Presence and activity of anaerobic ammonium-oxidizing bacteria at deep-sea hydrothermal vents
journal, July 2008

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Colonization of subsurface microbial observatories deployed in young ocean crust
journal, November 2010


Abundance and diversity of microbial life in ocean crust
journal, May 2008

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Microbial iron uptake as a mechanism for dispersing iron from deep-sea hydrothermal vents
journal, February 2014

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Hydrothermal vents as a kinetically stable source of iron-sulphide-bearing nanoparticles to the ocean
journal, May 2011

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  • Nature Geoscience, Vol. 4, Issue 6
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Slow-spreading submarine ridges in the South Atlantic as a significant oceanic iron source
journal, August 2013

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  • Nature Geoscience, Vol. 6, Issue 9
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A seafloor microbial biome hosted within incipient ferromanganese crusts
journal, November 2009

  • Templeton, A. S.; Knowles, E. J.; Eldridge, D. L.
  • Nature Geoscience, Vol. 2, Issue 12
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High resolution x‐ray absorption spectroscopy with absolute energy calibration for the determination of absorption edge energies
journal, March 1996

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Distal transport of dissolved hydrothermal iron in the deep South Pacific Ocean
journal, October 2014

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Mineralogy Drives Bacterial Biogeography of Hydrothermally Inactive Seafloor Sulfide Deposits
journal, February 2013


Iron speciation in soils and soil aggregates by synchrotron-based X-ray microspectroscopy (XANES, ?-XANES)
journal, October 2007


Distribution, phylogenetic diversity and physiological characteristics of epsilon-Proteobacteria in a deep-sea hydrothermal field
journal, October 2005


Temporal and spatial archaeal colonization of hydrothermal vent deposits
journal, April 2008


Evidence for the presence of thermophilic Fe(III)-reducing microorganisms in deep-sea hydrothermal vents at 13°N (East Pacific Rise)
journal, July 2001


Iron Isotope Constraints on the Archean and Paleoproterozoic Ocean Redox State
journal, February 2005


GEOCHEMISTRY: Biogeochemical Cycling of Iron Isotopes
journal, August 2005


Evidence for Microbial Carbon and Sulfur Cycling in Deeply Buried Ridge Flank Basalt
journal, March 2013


Neutrophilic Fe-Oxidizing Bacteria Are Abundant at the Loihi Seamount Hydrothermal Vents and Play a Major Role in Fe Oxide Deposition
journal, June 2002


Incidence and Diversity of Microorganisms within the Walls of an Active Deep-Sea Sulfide Chimney
journal, June 2003


Mid-Ocean Ridge Hydrothermal Fluxes and the Chemical Composition of the Ocean
journal, May 1996


Balancing the Global Carbon Budget
journal, May 2007


The Iron Isotope Fingerprints of Redox and Biogeochemical Cycling in Modern and Ancient Earth
journal, May 2008


X-ray absorption spectroscopic study of Fe reference compounds for the analysis of natural sediments
journal, April 2004

  • O’Day, Peggy A.; Rivera, Nelson; Root, Robert
  • American Mineralogist, Vol. 89, Issue 4
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Quantitative Speciation of Heavy Metals in Soils and Sediments by Synchrotron X-ray Techniques
journal, January 2002

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Geomicrobiology of the Ocean Crust: A Role for Chemoautotrophic Fe-Bacteria
journal, April 2003

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Sulfur Metabolisms in Epsilon- and Gamma-Proteobacteria in Deep-Sea Hydrothermal Fields
journal, January 2011


Mineralogy of Iron Microbial Mats from Loihi Seamount
journal, January 2012


The Irony of Iron – Biogenic Iron Oxides as an Iron Source to the Ocean
journal, January 2016


Generation of Seafloor Hydrothermal Vent Fluids and Associated Mineral Deposits
journal, March 2007


Works referencing / citing this record:

Inactive Sulfide Ecosystems in the Deep Sea: A Review
journal, July 2019


Low Energy Subsurface Environments as Extraterrestrial Analogs
journal, July 2018

  • Jones, Rose M.; Goordial, Jacqueline M.; Orcutt, Beth N.
  • Frontiers in Microbiology, Vol. 9
  • DOI: 10.3389/fmicb.2018.01605

Oxidative Weathering and Microbial Diversity of an Inactive Seafloor Hydrothermal Sulfide Chimney
journal, July 2017


Low Energy Subsurface Environments as Extraterrestrial Analogs
journal, July 2018

  • Jones, Rose M.; Goordial, Jacqueline M.; Orcutt, Beth N.
  • Frontiers in Microbiology, Vol. 9
  • DOI: 10.3389/fmicb.2018.01605