HR: 0800h
AN: V51A-0331    [Abstracts]
TI: Improved EPMA Trace Element Accuracy Using a Matrix Iterated Quantitative Blank Correction
AU: * Donovan, J J
EM: donovan@uoregon.edu
AF: University of Oregon, Department of Chemistry 1253 University of Oregon, Eugene, OR 97403-1253, United States
AU: Wark, D A
EM: wark@research.ge.com
AF: General Electric Global Research, One Research Circle Building K1, Room 1D-37A, Niskayuna, NY 12180, United States
AU: Jercinovic, M J
EM: mjj@geo.umass.edu
AF: University of Massachusetts, Department of Geosciences, Amherst, MA 01003-9297, United States
AB: At trace element levels below several hundred PPM, accuracy is more often the limiting factor for EPMA quantification rather than precision. Modern EPMA instruments equipped with low noise detectors, counting electronics and large area analyzing crystals can now routinely achieve sensitivities for most elements in the 10 to 100 PPM levels (or even lower). But due to various sample and instrumental artifacts in the x-ray continuum, absolute accuracy is often the limiting factor for ultra trace element quantification. These artifacts have various mechanisms, but are usually attributed to sample artifacts (e.g., sample matrix absorption edges)1, detector artifacts (e.g., Ar or Xe absorption edges) 2 and analyzing crystal artifacts (extended peak tails preventing accurate determination of the true background and ¡§negative peaks¡¨ or ¡§holes¡¨ in the x-ray continuum). The latter being first described3 by Self, et al. and recently documented for the Ti kƒÑ in quartz geo-thermometer. 4 Ti (ka) Ti (ka) Ti (ka) Ti (ka) Ti (ka) Si () O () Total Average: -.00146 -.00031 -.00180 .00013 .00240 46.7430 53.2563 99.9983 Std Dev: .00069 .00075 .00036 .00190 .00117 .00000 .00168 .00419 The general magnitude of these artifacts can be seen in the above analyses of Ti ka in a synthetic quartz standard. The values for each spectrometer/crystal vary systematically from ¡V18 PPM to + 24 PPM. The exact mechanism for these continuum ¡§holes¡¨ is not known but may be related to secondary lattice diffraction occurring at certain Bragg angles depending on crystal mounting orientation for non-isometric analyzing crystals5. These x-ray continuum artifacts can produce systematic errors at levels up to 100 PPM or more depending on the particular analytical situation. In order to correct for these inaccuracies, a ¡§blank¡¨ correction has been developed that applies a quantitative correction to the measured x-ray intensities during the matrix iteration, by calculating the intensity contribution from the systematic quantitative offset from a known (usually zero level) blank standard. Preliminary results from this new matrix iterated trace element blank correction demonstrate that systematic errors can be reduced to single digit PPM levels for many situations. 1B.W. Robinson, N.G. Ware and D.G.W. Smith, 1998. "Modern Electron-Microprobe Trace-Element Analysis in Mineralogy". In Cabri, L.J. and Vaughan, D.J., Eds. "Modern Approaches to Ore and Environmental Mineralogy", Short Course 27. Mineralogical Association of Canada, Ottawa 153-180 2Remond, G., Myklebust, R. Fialin, M. Nockolds, C. Phillips, M. Roques-Carmes, C. ¡§Decomposition of Wavelength Dispersive X-ray Spectra¡¨, Journal of Research of the National Institute of Standards and Technology (J. Res. Natl. Inst. Stand. Technol., v. 107, 509-529 (2002) 3Self, P.G., Norrish, K., Milnes, A.R., Graham, J. & Robinson, B.W. (1990): Holes in the Background in XRS. X-ray Spectrom. 19 (2), 59-61 4Wark, DA, and Watson, EB, 2006, TitaniQ: A Titanium-in-Quartz geothermometer: Contributions to Mineralogy and Petrology, 152:743-754, doi: 10.1007/s00410-006-0132-308
DE: 1065 Major and trace element geochemistry
DE: 1094 Instruments and techniques
SC: Volcanology, Geochemistry, Petrology [V]
MN: 2007 Fall Meeting