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Incorporation of Technetium into Spinel Ferrites

Journal Article · · Environmental Science and Technology
 [1];  [2];  [3];  [4];  [1]
  1. Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
  2. Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States; European Commission, Joint Research Centre, Institute for Transuranium Elements, 76125 Karlsruhe, Germany
  3. Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
  4. Geosciences Group, Pacific Northwest National Laboratory, Richland, Washington 99354, United States

Technetium (99Tc) is a problematic fission product for the long-term disposal of nuclear waste due to its long half-life, high fission yield, and to the environmental mobility of pertechnetate, the stable species in aerobic environments. One approach to preventing 99Tc contamination is using sufficiently durable waste forms. We report the incorporation of technetium into a family of synthetic spinel ferrites that have environmentally durable natural analogs. A combination of X-ray diffraction, X-ray absorption fine structure spectroscopy, and chemical analysis reveals that Tc(IV) replaces Fe(III) in octahedral sites and illustrates how the resulting charge mismatch is balanced. When a large excess of divalent metal ions is present, the charge is predominantly balanced by substitution of Fe(III) by M(II). When a large excess of divalent metal ions is absent, the charge is largely balanced by creation of vacancies among the Fe(III) sites (maghemitization). In most samples, Tc is present in Tc-rich regions rather than being homogeneously distributed.

Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
DOE Contract Number:
AC05-76RL01830
OSTI ID:
1406815
Report Number(s):
PNNL-SA-127418
Journal Information:
Environmental Science and Technology, Journal Name: Environmental Science and Technology Journal Issue: 23 Vol. 50; ISSN 0013-936X
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English

References (65)

Thermodynamic Model for the Solubility of TcO 2 · xH 2 O(am) in the Aqueous Tc(IV) – Na + – Cl - – H + – OH - – H 2 O System journal February 2004
Strong magnetic x-ray dichroism in 2 p absorption spectra of 3 d transition-metal ions journal June 1991
An investigation of the local environments of tin in tin-doped α-Fe 2 O 3 journal May 2000
Simultaneous Evaporation of CS and TC During Vitrification-A Thermochemical Approach journal January 1989
The biogeochemistry of technetium: A review of the behavior of an artificial element in the natural environment journal October 2010
Impeding 99Tc(IV) mobility in novel waste forms journal June 2016
Heterogeneous reduction of Tc(VII) by Fe(II) at the solid–water interface journal March 2008
The Formation of Manganese and Cobalt Ferrites by the Air Oxidation of Aqueous Suspensions and Their Properties journal January 1978
Removal of technetium-99 from contaminated groundwater with sorbents and reductive materials journal April 1996
[環境におけるテクネチウム] journal January 2006
Magnesioferrite from the Cretaceous-Tertiary boundary, Caravaca, Spain journal December 1986
Soft X-ray microscopy and spectroscopy at the molecular environmental science beamline at the Advanced Light Source journal February 2006
Reduction of pertechnetate [Tc(VII)] by aqueous Fe(II) and the nature of solid phase redox products journal May 2007
Redox behavior of Tc(VII)/Tc(IV) under various reducing conditions in 0.1 M NaCl solutions journal May 2013
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides journal September 1976
Hematite and Goethite from Duricrusts Developed by Lateritic Chemical Weathering of Precambrian Banded Iron Formations, Minas Gerais, Brazil journal January 1996
Energetics of Spinels in the FeTiO System at the Nanoscale journal September 2014
Location of tin and charge balance in materials of composition Fe3-xSnxO4 (x < 0.3) journal January 1998
Tc-99 and Cs-137 Volatility from the DWPF Production Melter During Vitrification of the First Macrobatch of HLW Sludge at the Savannah River Site journal January 1999
Altérabilité des minéraux titanés (ilménite et rutile) et mobilité du titane dans les profils d'altération du secteur d'Ovala (Gabon) journal August 1995
The 2p absorption spectra of 3d transition metal compounds in tetrahedral and octahedral symmetry journal April 1992
Crystal chemistry of some technetium-containing oxides journal December 1964
Computational Investigation of Technetium(IV) Incorporation into Inverse Spinels: Magnetite (Fe 3 O 4 ) and Trevorite (NiFe 2 O 4 ) journal April 2016
Weathering geochronology by (U-Th)/He dating of goethite journal February 2005
Treatment of radioactive wastes: An X-ray absorption spectroscopy study of the reaction of technetium with green rust journal December 2003
Immobilisation of high level nuclear reactor wastes in SYNROC journal March 1979
Determination of ferrous and total iron in silicate rocks by automated colorimetry journal March 1975
Preparation of manganese ferrite fine particles from aqueous solution journal October 1991
ATHENA and ARTEMIS Interactive Graphical Data Analysisusing IFEFFIT journal January 2005
Interactions of Tc(IV) with Humic Substances journal April 2011
Climatic implications of surface domains in arrays of δD and δ18O from hydroxyl minerals: goethite as an example journal June 2000
Synthesis, Structure Elucidation, and Redox Properties of 99 Tc Complexes of Lacunary Wells−Dawson Polyoxometalates: Insights into Molecular 99 Tc−Metal Oxide Interactions journal March 2011
Compositional and structural control on anion sorption capability of layered double hydroxides (LDHs) journal September 2006
Synthesis and properties of titanomagnetite (Fe3−xTixO4) nanoparticles: A tunable solid-state Fe(II/III) redox system journal December 2012
Products of Pertechnetate Radiolysis in Highly Alkaline Solution:  Structure of TcO2·xH2O journal February 2002
Technetium Incorporation into Hematite (α-Fe 2 O 3 ) journal August 2010
Direct determination of cation site occupancies in natural ferrite spinels by L2,3 X-ray absorption spectroscopy and X-ray magnetic circular dichroism journal May 2006
Technetium Volatilization During HLLW Vitrification journal January 1984
Nitrate-ion-selective exchange ability of layered double hydroxide consisting of MgII and FeIII journal May 2012
Thermodynamic description of Tc( iv ) solubility and hydrolysis in dilute to concentrated NaCl, MgCl 2 and CaCl 2 solutions journal January 2016
Incorporation and Retention of 99-Tc(IV) in Magnetite under High pH Conditions journal October 2014
Crystal chemistry of the magnetite-ulvospinel series journal January 2009
Immobilization of 99-Technetium (VII) by Fe(II)-Goethite and Limited Reoxidation journal June 2011
A Variation of the F-Test for Determining Statistical Relevance of Particular Parameters in EXAFS Fits
  • Downward, L.; Booth, C. H.; Lukens, W. W.
  • X-RAY ABSORPTION FINE STRUCTURE - XAFS13: 13th International Conference, AIP Conference Proceedings https://doi.org/10.1063/1.2644450
conference January 2007
The solubility of technetium in the near-field environment of a radioactive waste repository journal July 1990
Synthesis and characterization of ultrafine nickel( II )-bearing ferrites (Ni x Fe 3 –x O 4 , x= 0.14–1.0) journal January 1995
Iron oxide waste form for stabilizing 99Tc journal October 2012
Synthesis and characterisation of tin-doped iron oxides journal January 1999
Studies on the Immobilization of Technetium under Near Field Geochemical Conditions journal January 1996
Dissolution of Technetium(IV) Oxide by Natural and Synthetic Organic Ligands under both Reducing and Oxidizing Conditions journal June 2011
IFEFFIT  : interactive XAFS analysis and FEFF fitting journal March 2001
Formation of uniform spherical magnetite particles by crystallization from ferrous hydroxide gels journal March 1980
Cation site occupancy in spinel ferrites studied by X-ray magnetic circular dichroism: developing a method for mineralogists [Cation site occupancy in spinel ferrites studied by X-ray magnetic circular dichroism: developing a method for mineralogists] journal November 2002
Mechanisms of Nucleation and Growth of Nanoparticles in Solution journal July 2014
Reduction of Pertechnetate by Ferrous Iron in Solution: Influence of Sorbed and Precipitated Fe(II) journal January 1996
Complexation of Technetium with Humic Acid journal January 1993
Fe site occupancy in magnetite-ulvospinel solid solutions: A new approach using X-ray magnetic circular dichroism journal March 2010
Ab initio curved-wave x-ray-absorption fine structure journal September 1991
The Formation of Mg-bearing Ferrite by the Air Oxidation of Aqueous Suspensions journal March 1979
Solubility study of Tc(IV) in a granitic water journal September 2007
Characterization of natural titanomagnetites (Fe3−xTixO4) for studying heterogeneous electron transfer to Tc(VII) in the Hanford subsurface journal March 2014
The micro-determination of ferrous iron in silicate minerals by a volumetric and a colorimetric method journal January 1960
Structural and Magnetic Properties of Sn-, Ti-, and Mg-Substituted α-Fe2O3: A Study by Neutron Diffraction and Mössbauer Spectroscopy journal May 2000
The structure of ammonium pertechnetate at 295, 208 and 141 K journal February 1980
Reduction of Tc(VII) by Fe(II) Sorbed on Al (hydr)oxides journal August 2008

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