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Mineralogical transformations in polymetallic nodules and the change of Ni, Cu and Co crystal-chemistry upon burial in sediments

Journal Article · · Geochimica et Cosmochimica Acta
 [1];  [2];  [3];  [1];  [1]
  1. Federal Inst. for Geoscience and Natural Resources (BGR), Hannover (Germany)
  2. BRGM, Orleans (France)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Polymetallic nodules from the Clarion and Clipperton Zone of the equatorial Pacific Ocean were studied using X-ray diffraction, X-ray absorption, Fourier-transformed infrared spectroscopy and transmission electron microscopy. Here, this study includes nodules found at the sediment surface as well as subsurface (14–16 cm sediment depth) and deeply buried (530–985 cm sediment depth) nodules. The surface and subsurface nodules are currently under oxic conditions whereas the deeply buried nodules are under suboxic conditions. Surface nodules consist mainly of turbostratic phyllomanganates (7 Å and 10 Å vernadite and Fe-vernadite); todorokite is a minor phase, if present at all. In contrast, subsurface and especially deeply buried nodules predominantly consist of todorokite, which increases in abundance with depth in the sediment. Thus, upon burial of nodules within the shallow sediment, phyllomanganates transform to todorokite, probably through the combined action of time and change in the ambient chemical conditions. Nodules from deeper sediment depth (>500 cm) consist primarily of todorokite and additionally show signs of dissolution. The transformation of phyllomanganates to todorokite and their further dissolution upon nodule burial under suboxic conditions induces modifications in the crystal-chemistry of Ni, Co, and Cu. In surface nodules, Ni and Co are incorporated in the octahedral sheets of phyllomanganates, whereas Cu mainly is located at the edges of those phyllomanganate sheets. In buried nodules Cu and to a lesser extent Ni are incorporated in todorokite by forming outer-sphere complexes within the tunnels. However, Ni is predominantly incorporated within the octahedra of the newly formed todorokite structure. Co is also enriched in the octahedra of todorokite as a result of dissolution of hydrogenetic vernadite and re-incorporation in the more stable Mn-phase formed during the diagenetic transformation. Co enrichment under suboxic conditions after burial within the sediments is noteworthy since Co in surface nodules is characteristic for oxic conditions.
Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
National Institutes of Health (NIH); USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER)
Grant/Contract Number:
AC02-76SF00515
OSTI ID:
1646794
Journal Information:
Geochimica et Cosmochimica Acta, Journal Name: Geochimica et Cosmochimica Acta Vol. 282; ISSN 0016-7037
Publisher:
Elsevier; The Geochemical Society; The Meteoritical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

References (49)

Buried nodules and associated sediments from the central Indian basin journal June 1991
Plankton: Its chemical composition and its significance as a source of pelagic sediments journal December 1974
Sequential leaching of marine ferromanganese precipitates: Genetic implications journal December 1995
The growth of buried manganese nodules journal July 1979
A new synthetic route to todorokite-type manganese oxides journal November 1999
Lattice vibrations of manganese oxides journal February 2004
Phase associations and potential selective extraction methods for selected high-tech metals from ferromanganese nodules and crusts with siderophores journal April 2014
Sorption of Ni by birnessite: Equilibrium controls on Ni in seawater journal March 2007
Focused Ion Beam (FIB) combined with SEM and TEM: Advanced analytical tools for studies of chemical composition, microstructure and crystal structure in geomaterials on a nanometre scale journal April 2009
Copper sorption by the edge surfaces of synthetic birnessite nanoparticles journal March 2015
The geochemical behavior of metals during early diagenetic alteration of buried manganese nodules journal December 2018
Cobalt-doped todorokites prepared by refluxing at atmospheric pressure as cathode materials for Li batteries journal December 2010
Natural speciation of Ni, Zn, Ba, and As in ferromanganese coatings on quartz using X-ray fluorescence, absorption, and diffraction journal January 2007
Formation of todorokite from vernadite in Ni-rich hemipelagic sediments journal December 2007
Physiochemical controls on the crystal-chemistry of Ni in birnessite: Genetic implications for ferromanganese precipitates journal June 2009
Surface complexation of Cu on birnessite (δ-MnO2): Controls on Cu in the deep ocean journal December 2010
Nucleation and growth of todorokite from birnessite: Implications for trace-metal cycling in marine sediments journal November 2014
Release of Ni from birnessite during transformation of birnessite to todorokite: Implications for Ni cycling in marine sediments journal September 2016
Transformation of Co-containing birnessite to todorokite: Effect of Co on the transformation and implications for Co mobility journal February 2019
Nanoporous manganese oxides as environmental protective materials—Effect of Ca and Mg on metals sorption journal August 2010
Synthesis of metal-doped todorokite-type MnO2 and its cathode characteristics for rechargeable lithium batteries journal August 2005
Do manganese nodules grow or dissolve after burial? Results from the Central Indian Ocean Basin journal July 2007
The influence of suboxic diagenesis on the formation of manganese nodules in the Clarion Clipperton nodule belt of the Pacific Ocean journal November 2014
Deep-ocean mineral deposits as a source of critical metals for high- and green-technology applications: Comparison with land-based resources journal June 2013
IR spectra of manganese oxides with either layered or tunnel structures journal July 2007
54 Mn Radiotracers Demonstrate Continuous Dissolution and Reprecipitation of Vernadite (δ-MnO 2 ) during Interaction with Aqueous Mn(II) journal July 2016
Reductive Transformation of Birnessite by Aqueous Mn(II) journal August 2011
Manganese-Cycling Microbial Communities Inside Deep-Sea Manganese Nodules journal June 2015
MINERALOGY AND INTERNAL STRUCTURE OF Fe-Mn NODULES FROM THE CLARION-CLIPPERTON FRACTURE ZONE journal March 1987
Deposition of hydrogenetic and hydrothermal manganese minerals in the Ogasawara (Bonin) Arc Area, Northwest Pacific journal April 1997
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT journal June 2005
Solid-state transformation of nanocrystalline phyllomanganate into tectomanganate: influence of initial layer and interlayer structure journal September 2014
Focused Ion Beam (FIB): A novel technology for advanced application of micro- and nanoanalysis in geosciences and applied mineralogy [Focused Ion Beam (FIB): A novel technology for advanced application of micro- and nanoanalysis in geosciences and applied mineralogy] journal December 2004
Nucleation and growth of feitknechtite from nanocrystalline vernadite precursor [Nucleation and growth of feitknechtite from nanocrystalline vernadite precursor] journal October 2017
Widespread seawater circulation in 18–22 Ma oceanic crust: Impact on heat flow and sediment geochemistry journal June 2017
Natural and synthetic manganese minerals journal February 2013
Geochemical oxidation fronts in NE Atlantic distal turbidites and their effects in the sedimentary record journal January 1987
Growth history of manganese nodules and crusts of the Peru Basin journal January 1997
Inorganic speciation of dissolved elements in seawater: the influence of pH on concentration ratios journal January 2002
Cryptomelane formation from nanocrystalline vernadite precursor: a high energy X-ray scattering and transmission electron microscopy perspective on reaction mechanisms journal September 2015
Ion Exchange, Thermal Transformations, and Oxidizing Properties of Birnessite journal January 1986
Marine Ferromanganese Encrustations: Archives of Changing Oceans journal June 2017
Structural mechanism of Co (super 2+) oxidation by the phyllomanganate buserite journal December 1997
Structure of synthetic monoclinic Na-rich birnessite and hexagonal birnessite; I, Results from X-ray diffraction and selected-area electron diffraction journal October 1997
Synchrotron X-ray diffraction study of the structure and dehydration behavior of todorokite journal January 2003
Mineralogy and crystal chemistry of Mn, Fe, Co, Ni, and Cu in a deep-sea Pacific polymetallic nodule journal October 2014
Mineralogical characterization of individual growth structures of Mn-nodules with different Ni+Cu content from the central Pacific Ocean journal November 2015
Birnessite polytype systematics and identification by powder X-ray diffraction journal May 2007
Crystal-chemistry of Ni in marine ferromanganese crusts and nodules journal July 2007

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