Determination of the oxidation state for iron oxide minerals by energy-filtering TEM.

The oxidation state of iron oxide nanoparticles was determined using the two principally different technical realisations of energy filtering TEM, in one case using the JEOL 3010 equipped with a LaB6 cathode and a post-column GIF and in the second, the newly designed LIBRA 200FE equipped with an corrected in-column 90 degrees energy filter and a field emission gun (Schottky emitter). The samples studied were oxide-coated iron nanoparticles, and iron oxide inclusions in feldspars in granites. Five possible candidates exist for the iron-oxide phases: FeO, alpha-Fe2O3 (hematite), gamma-Fe2O3 (maghemite), Fe3O4 (magnetite) or alpha-FeO(OH) (goethite). Fingerprinting the O K-edge ELNES allows to distinguish between oxide phases with the same stochiometry and enables to make a first selection of possible candidates. The additional determination of the chemical composition allows unique identification of the phase present. For the oxide coated iron nanoparticles the most probable iron oxide phase of the shell is maghemite, which was additionally confirmed by HRTEM studies. The second studied system were iron oxide needles in alkali feldspar, where we obtained hematite as the most probable phase. There we additionally demonstrated the drastic changes of the ELNES of the O K-edge for the alkali feldspar and iron oxide needle by spatially resolved EELS.