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The structure and crystal chemistry of vernadite in ferromanganese crusts

Journal Article · · Acta Crystallographica. Section B, Structural Science, Crystal Engineering and Materials (Online)
 [1];  [1];  [2];  [3]
  1. Univ. of Wisconsin-Madison, Madison, WI (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
  3. Sun Yat-sen Univ., Guangzhou (People's Republic of China); Provincial Key Laboratory of Marine Resources and Coastal Engineering, Guangzhou (People's Republic of China)
+ Show Author Affiliations

The structure and crystal chemistry of vernadite in ferromanganese crusts from the Magellan Seamount in the north-west Pacific Ocean have been investigated using synchrotron X-ray diffraction (XRD), X-ray pair distribution function (PDF) and high-resolution transmission electron microscopy (TEM). XRD patterns of vernadite mainly show two strong diffraction peaks at 2.42–2.43 Å and 1.41 Å without or with a broad (001) diffraction peak, indicating thin layer nanophases along the c-direction. TEM images show flat and curved sheet-like nanocrystals with (001) layer thickness of ~7.2 Å and ~9.6 Å, and their interstratified structure. PDF patterns of the vernadite are similar to those from synthetic δ-MnO2 and defective birnessite, suggesting a phyllomanganate framework. Combined XRD/PDF patterns suggest that vernadite in the outer part is associated with a higher density interlayer species at triple-edge sharing sites. The proportion of the 10 Å phase increases from the outer (young) part to the inner (old) part of the Mn crusts due to aging and sorption of Mn, Co and Ni from ambient seawater. This study suggests that this combined method of synchrotron radiation XRD/PDF and high-resolution TEM is a powerful tool to determine atomic structures of poorly crystallized nano-minerals. The mixture model of vernadite structure will help to understand the partitioning and distribution of trace elements in the ferromanganese crusts.

Research Organization:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Organization:
Chinese Academy of Sciences (CAS); National Aeronautic and Space Administration (NASA); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Scientific User Facilities Division
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1559941
Journal Information:
Acta Crystallographica. Section B, Structural Science, Crystal Engineering and Materials (Online), Journal Name: Acta Crystallographica. Section B, Structural Science, Crystal Engineering and Materials (Online) Journal Issue: 4 Vol. 75; ISSN ACSBDA; ISSN 2052-5206
Publisher:
International Union of CrystallographyCopyright Statement
Country of Publication:
United States
Language:
English

References (44)

Vernadite is random-stacked birnessite: A discussion of the paper by F. V. Chukhrov et al.: ?Contributions to the mineralogy of authigenic manganese phases from marine manganese deposits? [Mineralium Deposita 14, 249?261 (1979)] journal July 1980
Co–rich Mn crusts from the Magellan Seamount cluster: the long journey through time journal February 2007
Deposition of deep-sea manganese nodules journal February 1974
The uptake of cobalt into ferromanganese nodules, soils, and synthetic manganese (IV) oxides journal January 1976
Sequential leaching of marine ferromanganese precipitates: Genetic implications journal December 1995
Mn-Fe oxyhydroxide crusts from Krylov Seamount (Eastern Atlantic): Mineralogy, geochemistry and genesis journal January 1991
Trace metal partitioning in Fe–Mn nodules from Sicilian soils, Italy journal March 2001
Manganese oxides for lithium batteries journal January 1997
Fast and reversible surface redox reaction of graphene–MnO2 composites as supercapacitor electrodes journal November 2010
In-situ determination of the kinetics and mechanisms of nickel adsorption by nanocrystalline vernadite journal May 2017
Mn, Fe, Zn and As speciation in a fast-growing ferromanganese marine nodule journal July 2004
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
Formation of Zn–Ca phyllomanganate nanoparticles in grass roots journal May 2008
Structural characterization of terrestrial microbial Mn oxides from Pinal Creek, AZ journal February 2009
Diversity of Mn oxides produced by Mn(II)-oxidizing fungi journal May 2011
Structural study of biotic and abiotic poorly-crystalline manganese oxides using atomic pair distribution function analysis journal March 2012
Zn sorption modifies dynamically the layer and interlayer structure of vernadite journal May 2012
Trivalent manganese on vacancies triggers rapid transformation of layered to tunneled manganese oxides (TMOs): Implications for occurrence of TMOs in low-temperature environment journal November 2018
Zn sorption mechanisms onto sheathed Leptothrix discophora and the impact of the nanoparticulate biogenic Mn oxide coating journal May 2009
Ferruginous vernadite in an Indian Ocean ferromanganese nodule journal September 1984
Arsenite Oxidation by a Poorly Crystalline Manganese-Oxide. 2. Results from X-ray Absorption Spectroscopy and X-ray Diffraction journal November 2010
Electrosynthesis, functional, and structural characterization of a water-oxidizing manganese oxide journal January 2012
In situ investigations of a Li-rich Mn–Ni layered oxide for Li-ion batteries journal January 2012
Manganese oxide minerals: Crystal structures and economic and environmental significance journal March 1999
PDFfit2 and PDFgui: computer programs for studying nanostructure in crystals journal July 2007
Short-range and long-range order of phyllomanganate nanoparticles determined using high-energy X-ray scattering journal January 2013
GSAS-II : the genesis of a modern open-source all purpose crystallography software package journal March 2013
PDFgetX3 : a rapid and highly automatable program for processing powder diffraction data into total scattering pair distribution functions journal March 2013
Solid-state transformation of nanocrystalline phyllomanganate into tectomanganate: influence of initial layer and interlayer structure journal September 2014
The Problem with Determining Atomic Structure at the Nanoscale journal April 2007
Transformations of ore minerals in genetically different oceanic ferromanganese rocks journal July 2007
BIOGENIC MANGANESE OXIDES: Properties and Mechanisms of Formation journal May 2004
Crystal structure of Ni-sorbed synthetic vernadite: a powder X-ray diffraction study journal December 2008
Cryptomelane formation from nanocrystalline vernadite precursor: a high energy X-ray scattering and transmission electron microscopy perspective on reaction mechanisms journal September 2015
Structure of synthetic Na-birnessite: Evidence for a triclinic one-layer unit cell journal November 2002
Mineralogy and crystal chemistry of Mn, Fe, Co, Ni, and Cu in a deep-sea Pacific polymetallic nodule journal October 2014
Study on nanophase iron oxyhydroxides in freshwater ferromanganese nodules from Green Bay, Lake Michigan, with implications for the adsorption of As and heavy metals journal September 2016
Environmentally important, poorly crystalline Fe/Mn hydrous oxides: Ferrihydrite and a possibly new vernadite-like mineral from the Clark Fork River Superfund Complex journal April 2005
Structural model for the biogenic Mn oxide produced by Pseudomonas putida journal April 2006
Birnessite polytype systematics and identification by powder X-ray diffraction journal May 2007
Structure of nanocrystalline phyllomanganates produced by freshwater fungi journal November 2010
Structural water in ferrihydrite and constraints this provides on possible structure models journal March 2011
Determination of Mn valence states in mixed-valent manganates by XANES spectroscopy journal May 2012

Figures / Tables (16)

Figure 1(p. 3)figure Figure 1
Figure 2(p. 5)figure Figure 2
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Table 1(p. 10)table Table 1
Figure 7(p. 11)figure Figure 7
Figure 8(p. 13)figure Figure 8
Figure 9(p. 13)figure Figure 9
Figure S1(p. 17)figure Figure S1
Figure S2(p. 18)figure Figure S2
Figure S3(p. 18)figure Figure S3
Figure S4(p. 19)figure Figure S4
Table S1(p. 20)table Table S1
Table S2(p. 21)table Table S2

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Related Subjects

36 MATERIALS SCIENCE
Ferromanganese crusts
Pair distribution function
TEM
Vernadite
XRD