title: A STEM/EELS method for mapping iron valence ratios in oxide minerals.
abstract: The valence state of iron in minerals has useful applications in the geosciences for estimating redox conditions during mineral formation or re-equilibration. STEM/EELS techniques offer the advantage over other methods of being able to measure Fe valence with very high spatial resolution across mineral grains and grain boundaries. We have modified an EELS method for point analyses of iron valence ratios (Fe(3+)/SigmaFe) making it possible to generate line scans and maps of Fe valence. We demonstrate this method with measurements at an interface between iron-bearing oxides in a finely intergrown sample of magnetite and ilmenite. The STEM/EELS method is based on a calibrated relationship between Fe(3+)/SigmaFe and the relative intensities of the Fe L(3) and L(2) white lines in core energy-loss spectra for oxide and silicate minerals. Our method overcomes problems of energy drift in spectrum images by aligning energy-loss edges at a fixed energy position prior to background removal. An automated routine for batch processing of core loss spectra, including additional background removal and calculation of Fe L(3)/L(2) intensity ratios, allows for rapid Fe(3+)/SigmaFe determinations of multiple point analyses or spectrum images and the preparation of Fe valence maps, with an analytical error of +/-0.05 to +/-0.09 in the Fe(3+)/SigmaFe measurements.
authors.affiliation: Department of Geology, University of New Brunswick, Fredericton, NB, Canada E3B 5A3.
authors.forename: Lisa
authors.initials: L
authors.lastname: Cavé
authors.forename: Tom
authors.initials: T
authors.lastname: Al
authors.forename: Diana
authors.initials: D
authors.lastname: Loomer
authors.forename: Steven
authors.initials: S
authors.lastname: Cogswell
authors.forename: Louise
authors.initials: L
authors.lastname: Weaver