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

Journal Article · · Frontiers in Microbiology
 [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)
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.
Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1257607
Journal Information:
Frontiers in Microbiology, Journal Name: Frontiers in Microbiology Vol. 7; ISSN 1664-302X
Publisher:
Frontiers Research FoundationCopyright Statement
Country of Publication:
United States
Language:
English

References (105)

The Structure of Ferrihydrite, a Nanocrystalline Material. journal October 2007
Mass spectrometry and natural variations of iron isotopes journal January 2006
Ancient geochemical cycling in the Earth as inferred from Fe isotope studies of banded iron formations from the Transvaal Craton journal February 2003
Biogeochemical insights into microbe–mineral–fluid interactions in hydrothermal chimneys using enrichment culture journal March 2015
Formation of ferric oxides from aqueous solutions: A polyhedral approach by X-ray absorption spectroscdpy: I. Hydrolysis and formation of ferric gels journal March 1989
The influence of hydrothermal fluid composition and advection rates on black smoker chimney mineralogy: Insights from modeling transport and reaction journal May 1995
Hydrothermal oxide and nontronite deposits on seamounts in the eastern Pacific journal June 1988
Tracing Cu and Fe from source to porphyry: in situ determination of Cu and Fe isotope ratios in sulfides from the Grasberg Cu–Au deposit journal July 2004
Heavy iron isotope composition of granites determined by high resolution MC-ICP-MS journal October 2005
Integrated Fe- and S-isotope study of seafloor hydrothermal vents at East Pacific Rise 9–10°N journal July 2008
Sulfur isotope measurement of sulfate and sulfide by high-resolution MC-ICP-MS journal August 2008
Sulfur cycling at the Mid-Atlantic Ridge: A multiple sulfur isotope approach journal January 2010
MC-ICP-MS measurement of δ34S and ∆33S in small amounts of dissolved sulfate journal May 2013
Iron isotope fractionation between aqueous ferrous iron and goethite journal June 2010
The stabilisation and transportation of dissolved iron from high temperature hydrothermal vent systems journal August 2013
Iron isotope fractionation by Fe(II)-oxidizing photoautotrophic bacteria 1 1Associate editor: D. E. Canfield journal March 2004
Theoretical investigation of iron isotope fractionation between Fe(H2O)63+ and Fe(H2O)62+: Implications for iron stable isotope geochemistry journal February 2005
Zinc sorption to biogenic hexagonal-birnessite particles within a hydrated bacterial biofilm journal January 2006
In situ iron isotope ratio determination using UV-femtosecond laser ablation with application to hydrothermal ore formation processes journal July 2006
Low-oxygen and chemical kinetic constraints on the geochemical niche of neutrophilic iron(II) oxidizing microorganisms journal July 2008
Iron isotope fractionation in subterranean estuaries journal July 2008
Biogenic iron oxyhydroxide formation at mid-ocean ridge hydrothermal vents: Juan de Fuca Ridge journal January 2009
Grain-scale iron isotopic distribution of pyrite from Precambrian shallow marine carbonate revealed by a femtosecond laser ablation multicollector ICP-MS technique: Possible proxy for the redox state of ancient seawater journal May 2010
Catabolic and anabolic energy for chemolithoautotrophs in deep-sea hydrothermal systems hosted in different rock types journal October 2011
Iron isotope composition of some Archean and Proterozoic iron formations journal March 2012
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
Iron mineral structure, reactivity, and isotopic composition in a South Pacific Gyre ferromanganese nodule over 4 Ma journal December 2015
Dissolved and particulate Fe in a hydrothermal plume at 9°45′N, East Pacific Rise: journal February 2000
Evidence for the presence of thermophilic Fe(III)-reducing microorganisms in deep-sea hydrothermal vents at 13°N (East Pacific Rise) journal July 2001
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
Presence and activity of anaerobic ammonium-oxidizing bacteria at deep-sea hydrothermal vents journal July 2008
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
Microbial iron uptake as a mechanism for dispersing iron from deep-sea hydrothermal vents journal February 2014
Hydrothermal vents as a kinetically stable source of iron-sulphide-bearing nanoparticles to the ocean journal May 2011
Slow-spreading submarine ridges in the South Atlantic as a significant oceanic iron source journal August 2013
A seafloor microbial biome hosted within incipient ferromanganese crusts journal November 2009
High resolution x‐ray absorption spectroscopy with absolute energy calibration for the determination of absorption edge energies journal March 1996
Distal transport of dissolved hydrothermal iron in the deep South Pacific Ocean journal October 2014
Mineralogy Drives Bacterial Biogeography of Hydrothermally Inactive Seafloor Sulfide Deposits journal February 2013
Scanning X-ray microdiffraction with submicrometer white beam for strain/stress and orientation mapping in thin films journal February 2003
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
An experimental and theoretical approach to determining linkages between geochemical variability and microbial biodiversity in seafloor hydrothermal chimneys: Determining linkages between geochemical variability and microbial biodiversity journal August 2010
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
Quantitative Speciation of Heavy Metals in Soils and Sediments by Synchrotron X-ray Techniques journal January 2002
Geomicrobiology of the Ocean Crust: A Role for Chemoautotrophic Fe-Bacteria journal April 2003
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
Spherulitic pyrite in seafloor hydrothermal deposits: Products of rapid crystallization from mixing fluids book January 2005
Ridge crest hydrothermal activity and the balances of the major and minor elements in the ocean: The Galapagos data journal December 1979
Hydrothermal plumes along the East Pacific Rise, 8°40′ to 11°50′N: Particle distribution and composition journal November 1994
Rare earth element geochemistry of hydrothermal deposits from the active TAG Mound, 26°N Mid-Atlantic Ridge journal September 1995
Application of Fe isotopes to tracing the geochemical and biological cycling of Fe journal April 2003
Iron isotopes in hot springs along the Juan de Fuca Ridge journal December 2001
Seafloor bioalteration of sulfide minerals: results from in situ incubation studies journal August 2003
Kinetic and equilibrium Fe isotope fractionation between aqueous Fe(II) and Fe(III) journal November 2003
Secondary mineralization pathways induced by dissimilatory iron reduction of ferrihydrite under advective flow journal August 2003
Microbiology of ancient and modern hydrothermal systems journal February 2001
Microbe–metal interactions in marine hydrothermal environments journal April 2003
Iron isotope fractionation during oceanic crust alteration journal December 2003
The effect of plume processes on the Fe isotope composition of hydrothermally derived Fe in the deep ocean as inferred from the Rainbow vent site, Mid-Atlantic Ridge, 36°14′N journal August 2004
The distribution and stabilisation of dissolved Fe in deep-sea hydrothermal plumes journal June 2008
Subsurface processes at the lucky strike hydrothermal field, Mid-Atlantic ridge: evidence from sulfur, selenium, and iron isotopes journal May 2004
The effect of early diagenesis on the Fe isotope compositions of porewaters and authigenic minerals in continental margin sediments journal April 2006
Comparison of iron isotope variations in modern and Ordovician siliceous Fe oxyhydroxide deposits journal February 2014
Continuous sampling of hydrothermal fluids from Loihi Seamount after the 1996 event journal August 2000
Heat flow through a basaltic outcrop on a sedimented young ridge flank: HEAT FLOW THROUGH A BASALTIC OUTCROP journal December 2004
Variability in the microbial communities and hydrothermal fluid chemistry at the newly discovered Mariner hydrothermal field, southern Lau Basin: BIOGEOCHEMISTRY IN LAU BASIN VENT FIELD journal June 2008
Geodiversity of hydrothermal processes along the Mid-Atlantic Ridge and ultramafic-hosted mineralization: A new type of oceanic Cu-Zn-Co-Au volcanogenic massive sulfide deposit book January 2010
Tracking the dispersal of hydrothermal plumes from the Juan de Fuca Ridge using suspended matter compositions journal March 1992
Constraints on hydrothermal heat flux through the oceanic lithosphere from global heat flow journal February 1994
Physical and Chemical Processes of Seafloor Mineralization at Mid-Ocean Ridges
  • Hannington, Mark D.; Jonasson, Ian R.; Herzig, Peter M.
  • Seafloor Hydrothermal Systems: Physical, Chemical, Biological, and Geological Interactions https://doi.org/10.1029/GM091p0115
book January 2013
Ultra-diffuse hydrothermal venting supports Fe-oxidizing bacteria and massive umber deposition at 5000 m off Hawaii journal May 2011
Basin-scale transport of hydrothermal dissolved metals across the South Pacific Ocean journal July 2015
Preservation of iron(II) by carbon-rich matrices in a hydrothermal plume journal February 2009
In situ determination of sulfur isotopes in sulfur-rich materials by laser ablation multiple-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) journal January 2006
Microbial and hydrothermal aspects of ferric oxyhydroxides and ferrosic hydroxides: the example of Franklin Seamount, Western Woodlark Basin, Papua New Guinea journal January 2001
Submicron x-ray diffraction and its applications to problems in materials and environmental science journal March 2002
Scanning X-ray microdiffraction with submicrometer white beam for strain/stress and orientation mapping in thin films journal February 2003
Beamline 10.3.2 at ALS: a hard X-ray microprobe for environmental and materials sciences journal April 2004
Classification of Fe-bearing species from K -edge XANES data using two-parameter correlation plots journal August 2008
The Structure of Ferrihydrite, a Nanocrystalline Material journal June 2007
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
Life and Death of Deep-Sea Vents: Bacterial Diversity and Ecosystem Succession on Inactive Hydrothermal Sulfides journal January 2012
Iron isotope fractionation during microbial reduction of iron: The importance of adsorption journal January 2004
Neotethyan Late Cretaceous volcanic arc hydrothermal vent fauna journal January 2007
SIXPack a Graphical User Interface for XAS Analysis Using IFEFFIT journal January 2005

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