TY - JOUR
T1 - Microanalysis of the iron oxidation state in (Mg,Fe)O and application to the study of microscale processes
AU - Longo, Micaela
AU - McCammon, Catherine A.
AU - Jacobsen, Steven D.
N1 - Funding Information:
Acknowledgments We are grateful to Stephen Mackwell for supplying some of the samples examined in this study, to Hugh O’Neill for valuable advice concerning (Mg,Fe)O synthesis, to Heidi Höfer for her support on the flank method calibration, to Detlef Krauße for his technical support at the electron microprobe, to Nobuyoshi Mi-yajima for TEM investigations and to Florian Heidelbach for SEM analyses. The manuscript was significantly improved by the comments of Andrew Berry and an anonymous reviewer. ML received financial support from the European Commission under the Marie Curie Action for Early Stage Training of Researchers within the 6th Framework Programme (contract number MEST-CT-2005-019700). SDJ is supported in part by the US NSF (EAR-0748707) and by the David and Lucile Packard Foundation.
PY - 2011/12
Y1 - 2011/12
N2 - We report application of the flank method using the electron microprobe to a suite of twelve (Mg,Fe)O samples with composition 2-47 wt% Fe and Fe3+/ΣFe=1 to 11%, where Fe3+/ΣFe was determined independently using Mössbauer spectroscopy on the same grains used for the flank method measurements. A calibration curve of the form Fe2+=A+B× (ΣFe)2+C× (Lβ/Lα) was fit to the data and gave excellent agreement between Fe3+/ΣFe calculated from the flank method and Fe3+/ΣFe determined using Mössbauer spectroscopy. We found the method to be sufficiently sensitive to determine meaningful variations in Fe3+/ΣFe for geophysically relevant compositions of (Mg,Fe)O (<25 wt% Fe), and calibration parameters remained constant within experimental uncertainty over the course of the entire study (20 months). Flank method measurements on an inhomogeneous sample of synthetic (Mg,Fe)O showed evidence of diffusion processes resulting from rupture of the capsule during the high-pressure experiment and the possibility to measure Lβ/Lα variations with a spatial resolution of a few microns. We detected the presence of exsolved magnesioferrite in a suite of (Mg,Fe)O single crystals using transmission electron microscopy and Mössbauer spectroscopy. Flank method measurements on the same suite of single crystals showed enhanced Fe3+/ΣFe values, consistent with the presence of magnesioferrite even though the grains were too small to be resolved by conventional electron microprobe measurements.
AB - We report application of the flank method using the electron microprobe to a suite of twelve (Mg,Fe)O samples with composition 2-47 wt% Fe and Fe3+/ΣFe=1 to 11%, where Fe3+/ΣFe was determined independently using Mössbauer spectroscopy on the same grains used for the flank method measurements. A calibration curve of the form Fe2+=A+B× (ΣFe)2+C× (Lβ/Lα) was fit to the data and gave excellent agreement between Fe3+/ΣFe calculated from the flank method and Fe3+/ΣFe determined using Mössbauer spectroscopy. We found the method to be sufficiently sensitive to determine meaningful variations in Fe3+/ΣFe for geophysically relevant compositions of (Mg,Fe)O (<25 wt% Fe), and calibration parameters remained constant within experimental uncertainty over the course of the entire study (20 months). Flank method measurements on an inhomogeneous sample of synthetic (Mg,Fe)O showed evidence of diffusion processes resulting from rupture of the capsule during the high-pressure experiment and the possibility to measure Lβ/Lα variations with a spatial resolution of a few microns. We detected the presence of exsolved magnesioferrite in a suite of (Mg,Fe)O single crystals using transmission electron microscopy and Mössbauer spectroscopy. Flank method measurements on the same suite of single crystals showed enhanced Fe3+/ΣFe values, consistent with the presence of magnesioferrite even though the grains were too small to be resolved by conventional electron microprobe measurements.
KW - Electron microprobe
KW - Ferropericlase
KW - Flank method
KW - Iron oxidation state
UR - http://www.scopus.com/inward/record.url?scp=80955133945&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=80955133945&partnerID=8YFLogxK
U2 - 10.1007/s00410-011-0649-9
DO - 10.1007/s00410-011-0649-9
M3 - Article
AN - SCOPUS:80955133945
SN - 0010-7999
VL - 162
SP - 1249
EP - 1257
JO - Contributions of Mineralogy and Petrology
JF - Contributions of Mineralogy and Petrology
IS - 6
ER -