Abstract
Microanalysis of Fe3+/ΣFe in geological samples using synchrotron-based X-ray absorption spectroscopy has become routine since the introduction of standards and model compounds. Existing calibrations commonly use least-squares linear combinations of pre-edge data from standard reference spectra with known coordination number and valence state acquired on powdered samples to avoid preferred orientation. However, application of these methods to single mineral grains is appropriate only for isometric minerals and limits their application to analysis of in situ grains in thin sections. In this work, a calibration suite developed by acquiring X-ray absorption near-edge spectroscopy (XANES) data from amphibole single crystals with the beam polarized along the major optical directions (X, Y, and Z) is employed. Seven different methods for predicting %Fe3+ were employed based on (1) area-normalized pre-edge peak centroid, (2) the energy of the main absorption edge at the location where the normalized edge intensity has the highest R2 correlation with Fe3+/ΣFe, (3) the ratio of spectral intensities at two energies determined by highest R2 correlation with Fe3+/ΣFe, (4) use of the slope (first derivative) at every channel to select the best predictor channel, (5 and 6) partial least-squares models with variable and constant numbers of components, and (7) least absolute shrinkage and selection operator models. The latter three sophisticated multivariate analysis techniques for predicting Fe3+/ΣFe show significant improvements in accuracy over the former four types of univariate models. Fe3+/ΣFe can be measured in randomly oriented amphibole single crystals with an accuracy of ±5.5–6.2% absolute. Multivariate approaches demonstrate that for amphiboles main edge and EXAFS regions contain important features for predicting valence state. This suggests that in this mineral group, local structural changes accommodating site occupancy by Fe3+ vs. Fe2+ have a pronounced (and diagnostic) effect on the XAS spectra that can be reliably used to precisely constrain Fe3+/ΣFe.
Acknowledgments
We are grateful to Katy Evans and an anonymous reviewer for their thoughtful comments on this manuscript, which greatly improved it. We thank Paul Moore for the use of samples PBM-1B, PBM-2, PBM-4, and PBM-6, and George Rossman for permission to show his visible-region amphibole spectra. We are grateful for support of this research from NSF grants EAR-0809459 and EAR-1219761 and the RIS4E Virtual Institute. Portions of this work were performed at Beamline X26A, National Synchrotron Light Source (NSLS), Brookhaven National Laboratory. X26A is supported by the Department of Energy (DOE)–Geosciences (DE-FG02-92ER14244 to The University of Chicago, CARS). Use of the NSLS was supported by DOE under Contract No. DE-AC02-98CH10886. Finally, graduate student support for this project came from NASA grant NNA14AB04A. This is RIS4E Virtual Institute publication #SSERVI-2016-059.
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