Incorporation of Technetium into Spinel Ferrites

Environ Sci Technol. 2016 Dec 6;50(23):13160-13168. doi: 10.1021/acs.est.6b04209. Epub 2016 Nov 22.

Abstract

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.

Publication types

  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Ferric Compounds / chemistry*
  • Technetium / chemistry*
  • X-Ray Absorption Spectroscopy
  • X-Ray Diffraction

Substances

  • Ferric Compounds
  • Technetium