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Title: Iron mineral structure, reactivity, and isotopic composition in a South Pacific Gyre ferromanganese nodule over 4 Ma

Journal Article · · Geochimica et Cosmochimica Acta
 [1];  [2];  [3];  [1];  [2];  [4];  [5];  [4];  [4]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source
  2. Univ. of Southern California, Los Angeles, CA (United States). Dept. of Biological Sciences
  3. French Research Institute for the Exploitation of the Sea (IFREMER), Plouzane (France); Univ. Inst. European De La Mer, Plouzane (France); Yale Univ., New Haven, CT (United States). Dept. of Geology and Geophysics
  4. Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Soil, Water, and Climate
  5. French Research Institute for the Exploitation of the Sea (IFREMER), Plouzane (France)
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Deep-sea ferromanganese nodules accumulate trace elements from seawater and underlying sediment porewaters during the growth of concentric mineral layers over millions of years. These trace elements have the potential to record past ocean geochemical conditions. The goal of this study was to determine whether Fe mineral alteration occurs and how the speciation of trace elements responds to alteration over ~3.7Ma of marine ferromanganese nodule (MFN) formation, a timeline constrained by estimates from 9 Be/ 10 Be concentrations in the nodule material. We determined Fe-bearing phases and Fe isotope composition in a South Pacific Gyre (SPG) nodule. Specifically, the distribution patterns and speciation of trace element uptake by these Fe phases were investigated. The time interval covered by the growth of our sample of the nodule was derived from 9 Be/ 10 Be accelerator mass spectrometry (AMS). The composition and distribution of major and trace elements were mapped at various spatial scales, using micro-X-ray fluorescence (μXRF), electron microprobe analysis (EMPA), and inductively coupled plasma mass spectrometry (ICP-MS). Fe phases were characterized by micro-extended X-ray absorption fine structure (μEXAFS) spectroscopy and micro-X-ray diffraction (μXRD). Speciation of Ti and V, associated with Fe, was measured using micro-X-ray absorption near edge structure (μXANES) spectroscopy. Iron isotope composition (δ 56/54 Fe) in subsamples of 1-3mm increments along the radius of the nodule was determined with multiple-collector ICP-MS (MC-ICP-MS). The SPG nodule formed through primarily hydrogeneous inputs at a rate of 4.0±0.4mm/Ma. The nodule exhibited a high diversity of Fe mineral phases: feroxyhite (δ-FeOOH), goethite (α-FeOOH), lepidocrocite (γ-FeOOH), and poorly ordered ferrihydrite-like phases. These findings provide evidence that Fe oxyhydroxides within the nodule undergo alteration to more stable phases over millions of years. Trace Ti and V were spatially correlated with Fe and found to be adsorbed to Fe-bearing minerals. Ti/Fe and V/Fe ratios, and Ti and V speciation, did not vary along the nodule radius. The δ 56/54 Fe values, when averaged over sample increments representing 0.25-0.75Ma, were homogeneous within uncertainty along the nodule radius, at -0.12±0.07‰ (2sd, n=10). Our results indicate that the Fe isotope composition of the nodule remained constant during nodule growth and that mineral alteration did not affect the primary Fe isotope composition of the nodule. Furthermore, the average δ 56/54 Fe value of -0.12‰ we find is consistent with Fe sourced from continental eolian particles (dust). Despite mineral alteration, the trace element partitioning of Ti and V, and Fe isotope composition, do not appear to change within the sensitivity of our measurements. These findings suggest that Fe oxyhydroxides within hydrogenetic ferromanganese nodules are out of geochemical contact with seawater once they are covered by subsequent concentric mineral layers. Even though Fe-bearing minerals are altered, trace element ratios, speciation and Fe isotope composition are preserved within the nodule.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1378694
Alternate ID(s):
OSTI ID: 1244118
Journal Information:
Geochimica et Cosmochimica Acta, Vol. 171, Issue C; ISSN 0016-7037
Publisher:
The Geochemical Society; The Meteoritical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 30 works
Citation information provided by
Web of Science

References (82)

Analytical Methods for Non-Traditional Isotopes journal January 2004
Ferromanganese oxide deposits from the Central Pacific Ocean, II. Nodules and associated sediments journal February 1985
Multielemental analysis of Mn–Fe nodules by ICP-MS: optimisation of analytical method journal December 2001
Petrogenesis of ferromanganese nodules from east of the Chagos Archipelago, Central Indian Basin, Indian Ocean journal May 1999
Iron isotope constraints on Fe cycling and mass balance in oxygenated Earth oceans journal January 2003
The mineralogy and morphology of iron and manganese oxides in an imperfectly-drained Scottish soil journal September 1991
Metal Oxide Surfaces and Their Interactions with Aqueous Solutions and Microbial Organisms journal January 1999
Demonstration of significant abiotic iron isotope fractionation in nature journal January 2001
Natural Occurrence of Feroxyhite (δ′-FeOOH) journal January 1980
Determination of the 10Be half-life by multicollector ICP-MS and liquid scintillation counting
  • Chmeleff, Jérôme; von Blanckenburg, Friedhelm; Kossert, Karsten
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 268, Issue 2 https://doi.org/10.1016/j.nimb.2009.09.012
journal January 2010
Evidence for hydrothermal venting in Fe isotope compositions of the deep Pacific Ocean through time journal May 2006
Feroxyhyte, a new modification of FeOOH journal August 1977
Quantification of dissolved iron sources to the North Atlantic Ocean journal July 2014
The Effect of Nickel on the Conversion of Amorphous Iron(III) Hydroxide into more Crystalline Iron Oxides in Alkaline Media journal January 1992
Manganese nodules and other ferromanganese oxide deposits from the Atlantic Ocean journal September 1975
Mass spectrometry and natural variations of iron isotopes journal January 2006
Geochemical composition and inferred accretion rates of sediments and managanese nodules from a submarine hill in the Madeira Abyssal Plain, eastern North Atlantic journal December 1992
Subseafloor sedimentary life in the South Pacific Gyre journal June 2009
Iron isotopes in natural carbonate minerals determined by MC-ICP-MS with a 58Fe–54Fe double spike journal January 2006
Structure of Feroxyhite as Determined by Simulation of X-Ray Diffraction Curves journal June 1993
Goethite aging explains Ni depletion in upper units of ultramafic lateritic ores from New Caledonia journal July 2015
Ferromanganese nodules from MANOP Sites H, S, and R—Control of mineralogical and chemical composition by multiple accretionary processes journal May 1984
Meteoric 10Be concentrations from saprolite and till in northern Sweden: Implications for glacial erosion and age journal October 2012
Nickel partitioning in biogenic and abiogenic ferrihydrite: The influence of silica and implications for ancient environments journal September 2014
Rare earth element zonation in Pacific ferromanganese nodules journal July 1981
Controls on Fe(II)-Activated Trace Element Release from Goethite and Hematite journal January 2012
Trace element cycling through iron oxide minerals during redox-driven dynamic recrystallization journal November 2011
News Reports journal September 2002
Chronostratigraphy of ODP 181, Site 1121 sediment core (Southwest Pacific Ocean), using 10Be/9Be dating of entrapped ferromanganese nodules journal April 2004
The influence of the carbonate dissolution rate on the growth and composition of Co-rich ferromanganese crusts from Central Pacific seamount areas journal April 1984
Geochemical and mineralogical control of different genetic types of deep-sea nodules from the Pacific Ocean journal May 1981
Trace metals in metalliferous sediments, MANOP Site M: interfacial pore water profiles journal October 1986
Global occurrence of tellurium-rich ferromanganese crusts and a model for the enrichment of tellurium journal March 2003
Deep-ocean mineral deposits as a source of critical metals for high- and green-technology applications: Comparison with land-based resources journal June 2013
Using (234U/238U) to assess diffusion rates of isotope tracers in ferromanganese crusts journal July 1999
Persistence of deeply sourced iron in the Pacific Ocean journal January 2015
The global ocean flux of particulate organic carbon: Areal distribution and magnitude journal March 1996
The flux of iron and iron isotopes from San Pedro Basin sediments journal September 2012
Experimental constraints on Fe isotope fractionation during magnetite and Fe carbonate formation coupled to dissimilatory hydrous ferric oxide reduction journal February 2005
Metal diagenesis in oxic marine sediments journal December 1982
A new value for the half-life of 10Be by Heavy-Ion Elastic Recoil Detection and liquid scintillation counting
  • Korschinek, G.; Bergmaier, A.; Faestermann, T.
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 268, Issue 2 https://doi.org/10.1016/j.nimb.2009.09.020
journal January 2010
Sequential leaching of marine ferromanganese precipitates: Genetic implications journal December 1995
Uptake of elements from seawater by ferromanganese crusts: solid-phase associations and seawater speciation journal July 2003
Effects of phosphatization on the geochemical and mineralogical composition of marine ferromanganese crusts journal October 1997
Mid-Cretaceous tectonic evolution of the Tongareva triple junction in the southwestern Pacific Basin journal January 2002
Influence of Fe2+-catalysed iron oxide recrystallization on metal cycling journal November 2012
The global variation in the iron isotope composition of marine hydrogenetic ferromanganese deposits: implications for seawater chemistry? journal July 2004
Comparison study on transformation of iron oxyhydroxides: Based on theoretical and experimental data journal August 2011
Mineralogy and crystal chemistry of Mn, Fe, Co, Ni, and Cu in a deep-sea Pacific polymetallic nodule journal October 2014
Beamline 10.3.2 at ALS: a hard X-ray microprobe for environmental and materials sciences journal April 2004
Mn, Fe, Zn and As speciation in a fast-growing ferromanganese marine nodule journal July 2004
Classification of Fe-bearing species from K -edge XANES data using two-parameter correlation plots journal August 2008
Iron deficiency limits phytoplankton growth in the north-east Pacific subarctic journal January 1988
Characteristics of manganese nodules from the Central Indian Basin: Relationship with the sedimentary environment journal October 1991
The synthesis of birnessite, cryptomelane, and some other oxides and hydroxides of manganese journal December 1971
The geochemistry of redox sensitive trace metals in sediments journal June 1999
Size-Driven Structural and Thermodynamic Complexity in Iron Oxides journal March 2008
IFEFFIT  : interactive XAFS analysis and FEFF fitting journal March 2001
Physiochemical controls on the crystal-chemistry of Ni in birnessite: Genetic implications for ferromanganese precipitates journal June 2009
Iron isotopes in the seawater of the equatorial Pacific Ocean: New constraints for the oceanic iron cycle journal June 2011
The Iron Biogeochemical Cycle Past and Present journal January 2012
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT journal June 2005
Iron Isotope Constraints on the Archean and Paleoproterozoic Ocean Redox State journal February 2005
Integrated Fe- and S-isotope study of seafloor hydrothermal vents at East Pacific Rise 9–10°N journal July 2008
Trace metal remobilization in the interstitial waters of red clay and hemipelagic marine sediments journal August 1983
On the isotope composition of reactive iron in marine sediments: Redox shuttle versus early diagenesis journal December 2014
Growth rate variations of manganese nodules and crusts induced by paleoceanographic events journal October 1989
The continental shelf benthic iron flux and its isotope composition journal July 2010
Kinetic and equilibrium Fe isotope fractionation between aqueous Fe(III) and hematite journal September 2002
A new method for the determination of CeIII/CeIV ratios in geological materials; application for weathering, sedimentary and diagenetic processes journal November 2000
Chemical and structural control of the partitioning of Co, Ce, and Pb in marine ferromanganese oxides journal February 2007
X-Ray absorption spectroscopy (EXAFS/XANES) evidence for the preferential formation of isolated VO4 species on highly photoactive V2O5/SiO2 catalysts journal January 1987
Biogenic iron oxyhydroxide formation at mid-ocean ridge hydrothermal vents: Juan de Fuca Ridge journal January 2009
A comparative analysis of compositional variations in and between marine ferromanganese nodules and crusts in the South Pacific and their environmental controls journal November 2004
Characterization of the manganese oxide produced by pseudomonas putida strain MnB1 journal July 2003
Biogenic Origin of Polymetallic Nodules from the Clarion-Clipperton Zone in the Eastern Pacific Ocean: Electron Microscopic and EDX Evidence journal August 2008
Long-term stability of global erosion rates and weathering during late-Cenozoic cooling journal May 2010
Meteoric cosmogenic Beryllium-10 adsorbed to river sediment and soil: Applications for Earth-surface dynamics journal January 2010
K -edge absorption spectra of selected vanadium compounds journal November 1984
Stable Iron Isotope Fractionation Between Aqueous Fe(II) and Hydrous Ferric Oxide journal March 2011
The relationship between manganese minerals and metallic elements in deep-sea manganese nodules journal October 1991
Secular Variation of Iron Isotopes in North Atlantic Deep Water journal March 2000

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