Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

Synthesis and characterization of redox-active ferric nontronite

Journal Article · · Chemical Geology
 [1];  [2];  [3];  [3];  [4];  [5];  [6];  [7];  [1];  [1]
  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Geochemistry Dept.
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  3. Univ. of New Mexico, Albuquerque, NM (United States). Advanced Materials Lab.
  4. Univ. of New Mexico, Albuquerque, NM (United States). Dept. of Civil Engineering
  5. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Nuclear Waste Disposal Research and Analysis
  6. Univ. of Connecticut, Storrs, CT (United States). Materials Science and Engineering
  7. Argonne National Lab. (ANL), Argonne, IL (United States). X-ray Science Division
+ Show Author Affiliations
Heterogeneous redox reactions on clay mineral surfaces control mobility and bioavailability of redox-sensitive nutrients and contaminants. Iron (Fe) residing in clay mineral structures can either catalyze or directly participate in redox reactions; but, chemical controls over its reactivity are not fully understood. In our previous work we demonstrated that converting a minor portion of Fe(III) to Fe(II) (partial reduction) in the octahedral sheet of natural Fe-rich clay mineral nontronite (NAu-1) activates its surface, making it redox-active. In this study we produced and characterized synthetic ferric nontronite (SIP), highlighting structural and chemical similarities and differences between this synthetic nontronite and its natural counterpart NAu-1, and probed whether mineral surface is redox-active by reacting it with arsenic As(III) under oxic and anoxic conditions. Here, we demonstrate that synthetic nontronite SIP undergoes the same activation as natural nontronite NAu-1 following the partial reduction treatment. Similar to NAu-1, SIP oxidized As(III) to As(V) under both oxic (catalytic pathway) and anoxic (direct oxidation) conditions. The similar reactivity trends observed for synthetic nontronite and its natural counterpart make SIP an appropriate analog for laboratory studies. The development of chemically pure analogs for ubiquitous soil minerals will allow for systematic research of the fundamental properties of these minerals.
Research Organization:
Argonne National Lab. (ANL), Argonne, IL (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Chemical Sciences, Geosciences, and Biosciences Division; USDOE Office of Science (SC), Biological and Environmental Research (BER); USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)
Contributing Organization:
https://www.osti.gov/elink/enhancement.do?action=load&ostiid=1402054
Grant/Contract Number:
AC02-06CH11357; AC04-94AL85000; AC05-76RL01830; AC52-06NA25396; NA0003525
OSTI ID:
1390580
Alternate ID(s):
OSTI ID: 1402054
OSTI ID: 1406702
OSTI ID: 1547089
Report Number(s):
PNNL-SA--124893; PII: S0009254117304084
Journal Information:
Chemical Geology, Journal Name: Chemical Geology Vol. 470; ISSN 0009-2541
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English

References (46)

Polarized EXAFS, distance-valence least-squares modeling (DVLS), and quantitative texture analysis approaches to the structural refinement of Garfield nontronite journal May 1998
Voigt-based methods for arbitrary-shape static hyperfine parameter distributions in Mössbauer spectroscopy journal May 1991
Interaction between aqueous chromium solutions and layer silicates journal October 2000
Synthesis of clay minerals journal September 2010
Control of Fe(III) site occupancy on the rate and extent of microbial reduction of Fe(III) in nontronite journal December 2005
Heterogeneous reduction of Tc(VII) by Fe(II) at the solid–water interface journal March 2008
Pertechnetate (TcO4−) reduction by reactive ferrous iron forms in naturally anoxic, redox transition zone sediments from the Hanford Site, USA journal September 2012
Role of structural Fe in nontronite NAu-1 and dissolved Fe(II) in redox transformations of arsenic and antimony journal October 2012
Fe/Mg smectite formation under acidic conditions on early Mars journal January 2016
Elevated Concentrations of U and Co-occurring Metals in Abandoned Mine Wastes in a Northeastern Arizona Native American Community journal July 2015
Production of Abundant Hydroxyl Radicals from Oxygenation of Subsurface Sediments journal December 2015
Reactivity of Fe(II) Species Associated with Clay Minerals journal February 2003
Reduction of Nitroaromatic Compounds by Fe(II) Species Associated with Iron-Rich Smectites journal January 2006
Spectroscopic Evidence for Interfacial Fe(II)−Fe(III) Electron Transfer in a Clay Mineral journal January 2011
Redox Properties of Structural Fe in Clay Minerals. 1. Electrochemical Quantification of Electron-Donating and -Accepting Capacities of Smectites journal August 2012
Redox Properties of Structural Fe in Clay Minerals. 2. Electrochemical and Spectroscopic Characterization of Electron Transfer Irreversibility in Ferruginous Smectite, SWa-1 journal August 2012
Spectroscopic Evidence for Fe(II)–Fe(III) Electron Transfer at Clay Mineral Edge and Basal Sites journal March 2013
Redox Properties of Structural Fe in Clay Minerals: 3. Relationships between Smectite Redox and Structural Properties journal November 2013
X-ray Absorption Fine-Structure Spectroscopy Study of Photocatalyzed, Heterogeneous As(III) Oxidation on Kaolin and Anatase journal May 1998
New Method for the Direct Determination of Dissolved Fe(III) Concentration in Acid Mine Waters journal January 1999
Insights into the Mechanism of Fe(II) Adsorption and Oxidation at Fe–Clay Mineral Surfaces from First-Principles Calculations journal October 2013
Origin of the two quadrupole doublets in NAu-1 nontronite journal March 2010
Near-edge x-ray-absorption fine structure of Pb: A comparison of theory and experiment journal June 1993
Multiple-scattering calculations of x-ray-absorption spectra journal July 1995
Reduction and analysis of SANS and USANS data using IGOR Pro journal November 2006
Synchrotron X-ray study of the electron density in α-Fe 2 O 3 journal August 1994
IFEFFIT  : interactive XAFS analysis and FEFF fitting journal March 2001
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT journal June 2005
Synthesis and crystallogenesis at low temperature of Fe(III)-smectites by evolution of coprecipitated gels: experiments in partially reducing conditions journal December 1986
Isotropic/nematic and sol/gel transitions in aqueous suspensions of size selected nontronite NAu1 journal December 2013
Site Occupancies by Iron in Nontronites journal April 2002
Synthesis of Iron Layer Silicate Minerals under Natural Conditions journal January 1978
The Mössbauer Spectra of Nontronites: Consideration of an Alternative Assignment journal January 1978
Infrared and Mössbauer Studies of Reduced Nontronites journal January 1979
Preparation and Handling of Dithionite-Reduced Smectite Suspensions journal January 1984
Effects of Reduction and Reoxidation of Structural Iron on the Surface Charge and Dissolution of Dioctahedral Smectites journal January 1984
Synthesis of 1:1 and 2:1 Iron Phyllosilicates and Characterization of their Iron State by Mössbauer Spectroscopy journal January 1991
Synthetic Allophane and Layer-Silicate Formation in SiO2-Al2O3-FeO-Fe2O3-MgO-H2O Systems at 23°C and 89°C in a Calcareous Environment journal January 1991
hk-Ordering in Aluminous Nontronite and Saponite Synthesized Near 90°C: Effects of Synthesis Conditions on Nontronite Composition and Ordering journal January 1994
Synthesis of Smectite Clay Minerals: A Critical Review journal January 1999
Geology and Characterization of Two Hydrothermal Nontronites from Weathered Metamorphic Rocks at the Uley Graphite Mine, South Australia journal January 2000
Quantitative X-Ray Diffraction Analysis of Clay-Bearing Rocks from Random Preparations journal January 2001
Partitioning of Fe(II) in reduced nontronite (NAu-2) to reactive sites: reactivity in terms of Tc(VII) reduction journal April 2008
Hydrothermal Synthesis, Between 75 and 150ºC, of High-Charge, Ferric Nontronites journal June 2008
Comparisons of structural iron reduction in smectites by bacteria and dithionite: II. A variable-temperature Mössbauer spectroscopic study of Garfield nontronite journal July 2009
Oxidation-reduction mechanism of iron in dioctahedral smectites: I. Crystal chemistry of oxidized reference nontronites journal January 2000

Cited By (2)

“Switching on” iron in clay minerals journal January 2019
Interfacial reactions of Cu( ii ) adsorption and hydrolysis driven by nano-scale confinement journal January 2020

Similar Records

Synthesis and characterization of redox-active ferric nontronite
Journal Article · Sun Oct 01 00:00:00 EDT 2017 · Chemical Geology · OSTI ID:1406702
Role of structural Fe in nontronite NAu-1 and dissolved Fe(II) in redox transformations of arsenic and antimony
Journal Article · Thu Nov 01 00:00:00 EDT 2012 · Geochim. Cosmochim. Acta · OSTI ID:1050740

Related Subjects

58 GEOSCIENCES
Arsenic oxidation
Iron speciation
Phyllosilicate
Smectite
Synthetic nontronite
aresenic oxidation
iron speciation
phyllosilicate
smectite