Startseite In-situ mapping of ferric iron variations in lunar glasses using X-ray absorption spectroscopy
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In-situ mapping of ferric iron variations in lunar glasses using X-ray absorption spectroscopy

  • Molly C. McCanta EMAIL logo , M. Darby Dyar , Antonio Lanzirotti , Matthew Newville und Laura B. Breitenfeld
Veröffentlicht/Copyright: 26. Februar 2019
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American Mineralogist
Aus der Zeitschrift American Mineralogist Band 104 Heft 3

Abstract

This paper presents a new X-ray absorption spectroscopy (XAS) method for making two-dimensional maps of Fe3+ in-situ in polished glass samples, which opens the door to study redox changes associated with magmatic processes such as crystallization, assimilation, ascent, and eruption. Multivariate analysis (MVA) allows selection of specific channels in a spectrum to inform predictions of spectral characteristics. Here, the sparse model of the least absolute shrinkage and selection operator (Lasso) is used to select key channels in XAS channels that can be used to predict accurate in-situ Fe3+ analyses of silicate glasses. By tuning the model to use only six channels, analytical time is decreased enough to allow mapping of Fe3+ variations in samples by making gridded point analyses at the scale of the XAS beam (1–2 μm). Maps of Fe3+ concentration can then be constructed using freely available, open source software (http://cars.uchicago.edu/xraylarch/). This result shows the enormous potential of using MVA to select indicative spectral regions for predicting variables of interest across a wide variety of spectroscopic applications. Redox gradients in lunar picritic glass beads first observed with point analyses are confirmed through this XAS mapping and suggest degassing processes during ascent and eruption are responsible for the range of Fe3+ values measured in these samples.

Keywords: Glass; redox; X-ray absorption spectroscopy; lunar glass

  1. Funding This research was supported by NASA grant NNX16AR18G to M.C.M., NSF grants EAR-1219761 to M.D.D. and EAR-1219850 to M.C.M., and RIS4E, SEEED, and VORTICES nodes of NASA SSERVI.

Acknowledgments

We thank J. Boesenberg and A. Patchen for their assistance with electron microprobe analyses. The authors also thank the NASA Curation and Analysis Planning Team for Extraterrestrial Materials (CAPTEM) and M. Rutherford for access to the lunar glass beads used in this study.

References cited

Barnes, J.J., Tartèse, R., Anand, M., McCubbin, F.M., Franchi, I.A., Starkey, N.A., and Russell, S.S. (2014) The origin of water in the primitive Moon as revealed by the lunar highlands samples. Earth and Planetary Science Letters, 390, 244–252.10.1016/j.epsl.2014.01.015Suche in Google Scholar

Breitenfeld, L.B., Dyar, M.D., Carey, C.J., Tague, T.J. Jr., Wang, P., Mullen, T., and Parente, M. (2018) Predicting olivine composition using Raman spectroscopy through band shift and multivariate analyses. American Mineralogist, 11, 1827–1837.10.2138/am-2018-6291Suche in Google Scholar

Canil, D., O’Neill, H.St.C., Pearson, D.G., Rudnick, R.L., McDonough, W.F., and Carswell, D.A. (1994) Ferric iron in peridotites and mantle oxidation states. Earth and Planetary Science Letters, 123, 205–220.10.1016/0012-821X(94)90268-2Suche in Google Scholar

Carey, C., Dyar, M.D., Boucher, T., and Giguere, S. (2017) Web-based software for preprocessing, matching, fitting, prediction, and visualization of spectroscopic data: The data exploration, visualization, and analysis of spectra (DEVAS) website. 48th Lunar and Planetary Science Conference, abstract 1097.Suche in Google Scholar

Christie, D.M., Carmichael, I.S.E., and Langmuir, C.H. (1986) Oxidation states of mid-ocean ridge basalt glasses. Earth and Planetary Science Letters, 79, 397–411.10.1016/0012-821X(86)90195-0Suche in Google Scholar

Cottrell, E., Kelley, K.A., Lanzirotti, A., and Fisher, R.A. (2009) High-precision determination of iron oxidation state in silicate glasses using XANES. Chemical Geology, 268, 167–179.10.1016/j.chemgeo.2009.08.008Suche in Google Scholar

Cuikerman, M., and Uhlmann, D.R. (1974) Effects of iron oxidation state on viscosity, lunar composition 15555. Journal of Geophysical Research, 797, 1594–1598.10.1029/JB079i011p01594Suche in Google Scholar

Dyar, M.D., and Birnie, D.P. III (1984) Quench media effects on iron partitioning and ordering in a lunar glass. Journal of Non-Crystalline Solids, 67, 397–412.10.1016/0022-3093(84)90165-0Suche in Google Scholar

Dyar, M.D., Breves, E.A., Emerson, E., Bell, S.M., Nelms, M., Ozanne, M.V., Peel, S.E., Carmosino, M.L., Tucker, J.M., Gunter, M.E., and others. (2012a) Accurate determination of ferric iron in garnets in bulk Mössbauer spectroscopy and synchrotron micro-XANES. American Mineralogist, 97, 1726–1740.10.2138/am.2012.4107Suche in Google Scholar

Dyar, M.D., Breves, E.A., Gunter, M.E., Lanzirotti, A., Tucker, J.M., Carey, C.J., Peel, S.E., Brown, E.B., Oberti, R., Lerotic, M., and Delaney, J.S. (2016b) Synchrotron micro-XAS analysis of Fe3+ in amphiboles. American Mineralogist, 101, 1171–1189.10.2138/am-2016-5556Suche in Google Scholar

Dyar, M.D., Carmosino, M.L., Breves, E.A., Ozanne, M.V., Clegg, S.M., and Wiens, R.C. (2012b) Comparison of partial least squares and lasso regression techniques as applied to laser-induced breakdown spectroscopy of geological samples. Spectrochimica Acta Part B, 70, 51–67.10.1016/j.sab.2012.04.011Suche in Google Scholar

Dyar, M.D., McCanta, M.C., Breves, E.A., Carey, C.J., and Lanzirotti, A. (2016a) Accurate predictions of iron redox state in silicate glasses: A multivariate approach using X-ray absorption spectroscopy. American Mineralogist, 101, 744–748.10.2138/am-2016-5555Suche in Google Scholar

Etschmann, B.E., Donner, E., Brugger, J., Howard, D.L., de Jonge, M.D. Paterson, D., Naidu, R., Scheckel, K.G., Ryan, C.G., and Lombi, E. (2014) Speciation mapping of environmental samples using XANES imaging. Environmental Chemistry 11, 341–350.10.1071/EN13189Suche in Google Scholar

Filzmoser, P., Gschwandtner, M., and Todorov, V. (2012) Review of sparse methods in regression and classification with application to chemometrics. Journal of Chemometrics, 26, 42–51.10.1002/cem.1418Suche in Google Scholar

Füri, E., Deloule, E., Gurenko, A., and Marty, B. (2014) New evidence for chondritic lunar water from combined D/H and noble gas analyses of single Apollo 17 volcanic glasses. Icarus, 229, 109–120.10.1016/j.icarus.2013.10.029Suche in Google Scholar

Hafner, S.S., Virgo, D., and Warburton, D. (1971) Oxidation state of iron in plagioclase from lunar basalts. Earth and Planetary Science Letters, 12, 159–166.10.1016/0012-821X(71)90072-0Suche in Google Scholar

Hastie, T., Tibshirani, R., and Friedman, J. (2009) The Elements of Statistical Learning, 2nd ed., 745 pp. Springer.10.1007/978-0-387-84858-7Suche in Google Scholar

Hauri, E.H., Saal, A.E., Rutherford, M.C., and Van Orman, J.A. (2015) Water in the Moon’s interior: Truth and consequences. Earth and Planetary Science Letters, 409, 252–264.10.1016/j.epsl.2014.10.053Suche in Google Scholar

Hauri, E.H., Weinreich, T., Saal, A.E., Rutherford, M.C., and Van Orman, J.A. (2011) High pre-eruptive water contents preserved in lunar melt inclusions. Science, 333, 213–215.10.1126/science.1204626Suche in Google Scholar PubMed

Hirschmann, M.M. (2006) Water, melting and the deep Earth H2O cycle. Annual Review of Earth and Planetary Sciences, 34, 629–653.10.1146/annurev.earth.34.031405.125211Suche in Google Scholar

Huffman, G.P., Schwerer, F.C., Fisher, R.M., and Nagata, T. (1974) Iron distributions and metallic-ferrous ratios for Apollo lunar samples: Mössbauer and magnetic analyses. Proceedings of the 5th Lunar Conference, 3, 2779–2794.Suche in Google Scholar

Hui, H., Peslier, A.H., Zhang, Y., and Neal, C.R. (2013) Water in lunar anorthosites and evidence for a wet early Moon. Nature Geoscience, 6, 177–180.10.1038/ngeo1735Suche in Google Scholar

Ito, E., Harris, D.M., and Anderson, A.T. (1983) Alteration of oceanic crust and geologic cycling of chlorine and water. Geochimica et Cosmochimica Acta, 47, 1613–1624.10.1016/0016-7037(83)90188-6Suche in Google Scholar

Kraft, S., Stumpel, J., Becker, P., and Kuetgens, U. (1996) High resolution X-ray absorption spectroscopy with absolute energy: Calibration for the determination of absorption edge energies. Review of Scientific Instruments, 67, 681–687.10.1063/1.1146657Suche in Google Scholar

Lanzirotti, A., Dyar, M.D., Sutton, S., Newville, M., Head, E., Carey, C.J., McCanta, M.C., Lee, L., King, P.L., and Jones, J. (2018) Accurate predictions of microscale oxygen barometry in basaltic glasses using V K-edge X-ray absorption spectroscopy: A multivariate approach. American Mineralogist, 103, 1282–1297.10.2138/am-2018-6319Suche in Google Scholar

Mayhew, L.E., Webb, S.M., and Templeton, A.S. (2011) Microscale imaging and identification of Fe speciation and distribution during fluid–mineral reactions under highly reducing conditions. Environmental Science and Technology, 45, 4468–4474.10.1021/es104292nSuche in Google Scholar PubMed

McCanta, M.C., Dyar, M.D., Rutherford, M.J., Lanzirotti, A., Sutton, S.R., and Thomson, B.J. (2017) In-situ measurement of ferric iron in lunar glass beads using Fe-XAS. Icarus, 285, 95–102.10.1130/abs/2016AM-284822Suche in Google Scholar

McCanta, M.C., Dyar, M.D., Steven, C., Gunter, M., and Lanzirotti, A. (2018) In-situ measurements of Fe3+ in pyroxene using X-ray absorption spectroscopy: Using an oriented crystal calibration to refine geothermobarometric calculations. Proceedings of the 49th Lunar and Planetary Science conference, 1074 (abstract).Suche in Google Scholar

McCubbin, F.M., Steele, A., Hauri, E.H., Nekvasil, H., Yamashita, S., and Hemley, R.J. (2010) Nominally hydrous magmatism on the Moon. Proceedings of the National Academy of Sciences, 107, 11,223–11,228.10.1073/pnas.1006677107Suche in Google Scholar PubMed PubMed Central

Muñoz, M., De Andrade, V., Vidal, O., Lewin, E., Pascarelli, S., and Susini, J. (2006) Redox and speciation micromapping using dispersive X-ray absorption spectroscopy: Application to iron in chlorite mineral of a metamorphic rock thin section. Geochemistry, Geophysics, Geosystems, 7, 10.1029/2006GC001381Suche in Google Scholar

Niebuhr, H.H., Zeira, S., and Hafner, S.S. (1973) Ferric iron in plagioclase crystals from anorthosite 15415. Proceedings of the Lunar Science Conference, 4, 971–982.Suche in Google Scholar

Nielsen, C.H. and Sigurdsson, H. (1981) Quantitative methods of electron microprobe analysis of sodium in natural and synthetic glasses. American Mineralogist, 66, 547–552.Suche in Google Scholar

Pedregosa, F., Varoquaux, G., Gramfort, A., Michel, V., Thirion, B., Grisel, O., Blondel, M., Prettenhofer, P., Weiss, R., Dubourg, V., and others. (2011) Scikit-learn: Machine learning in Python. Journal of Machine Learning Research, 2825–2830.Suche in Google Scholar

Ravel, B., and Newville, M. (2005) ATHENA, ARTEMIS, HEPHAESTUS: data analysis for X-ray absorption spectroscopy using IFEFFIT. Journal of Synchrotron Radiation, 12, 537–541.10.1107/S0909049505012719Suche in Google Scholar PubMed

Rutherford, M.J., Head, J.W., Saal, A.E., Hauri, E., and Wilson, L. (2017) Model for the origin, ascent, and eruption of lunar picritic magmas. American Mineralogist, 102, 2045–2053.10.2138/am-2017-5994Suche in Google Scholar

Saal, A.E., Hauri, E.H., Lo Cascio, M., Van Orman, J.A., Rutherford, M.J., and Cooper, R.F. (2008) Volatile content of lunar volcanic glasses and the presence of water in the Moon’s interior. Nature, 454, 192–195.10.1038/nature07047Suche in Google Scholar PubMed

Sato, M. (1976) Oxygen fugacity and other thermochemical parameters of Apollo 17 high-Ti basalts and their implications on the reduction mechanism. Proceedings of the Lunar Science Conference VII, 1323–1344.Suche in Google Scholar

Schümann, K., and Hafner, S.S. (1972) On the amount of ferric iron in plagioclases from lunar igneous rocks. Proceedings of the Lunar Science Conference, 3, 615–621.Suche in Google Scholar

Tibshirani, R. (1996) Regression shrinkage and selection via the Lasso. Journal of the Royal Statistical Society, Series B, 58, 267–288.10.1111/j.2517-6161.1996.tb02080.xSuche in Google Scholar

Virgo, D., and Mysen, B.O. (1985) The structural state of iron in oxidized vs. reduced glasses at 1 atm: A 57Fe Mössbauer study. Physics and Chemistry of Minerals, 12, 65–76.10.1007/BF01046829Suche in Google Scholar

Wilke, M., Farges, F., Petit, P.-E., Brown, G.E. Jr., and Martin, F. (2001) Oxidation state and coordination of Fe in minerals: An Fe K-XANES spectroscopic study. American Mineralogist, 86, 714–730.10.2138/am-2001-5-612Suche in Google Scholar

Received: 2018-10-29
Accepted: 2018-12-06
Published Online: 2019-02-26
Published in Print: 2019-03-26

© 2019 Walter de Gruyter GmbH, Berlin/Boston

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https://doi.org/10.2138/am-2019-6863
Schlagwörter für diesen Artikel
Glass; redox; X-ray absorption spectroscopy; lunar glass

Artikel in diesem Heft

  1. Letter
  2. Chessboard structures: Atom-scale imaging of homologs from the kobellite series
  3. Special collection: Microporous materials: Crystal-chemistry, properties, and utilizations
  4. Highlighting the capability of zeolites for agro-chemicals contaminants removal from aqueous matrix: Evidence of 2-ethyl-6-methylaniline adsorption on ZSM-12
  5. Special collection: Physics and chemistry of earth's deep mantle and core
  6. Origin and consequences of non-stoichiometry in iron carbide Fe7C3
  7. Special collection: Isotopes, minerals, and petrology: Honoring John Valley
  8. Application of mineral equilibria to estimate fugacities of H2O, H2, and O2 in mantle xenoliths from the southwestern U.S.A.
  9. Review
  10. Composition, paragenesis, and alteration of the chevkinite group of minerals
  11. Articles
  12. Spinel-anorthosites on the Moon: Impact melt origins suggested by enthalpy constraints
  13. Fast diffusion path for water in silica glass
  14. Micro- and nano-scale textural and compositional zonation in plagioclase at the Black Mountain porphyry Cu deposit: Implications for magmatic processes
  15. A XANES and EPMA study of Fe3+ in chlorite: Importance of oxychlorite and implications for cation site distribution and thermobarometry
  16. Sound velocities across calcite phase transitions by Brillouin scattering spectroscopy
  17. Trace element distributions in (Cu)-Pb-Sb sulfosalts from the Gutaishan Au-Sb deposit, South China: Implications for formation of high fineness native gold
  18. A-type carbonate in strontium phosphate apatites
  19. Discovery of a zinc-rich mineral on the surface of lunar orange pyroclastic beads
  20. In-situ mapping of ferric iron variations in lunar glasses using X-ray absorption spectroscopy
  21. Book Review
  22. Book Review
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