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Predicting olivine composition using Raman spectroscopy through band shift and multivariate analyses

  • Laura B. Breitenfeld EMAIL logo , M. Darby Dyar , C.J. Carey , Thomas J. Tague Jr. , Peng Wang , Terry Mullen and Mario Parente
Published/Copyright: October 30, 2018
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American Mineralogist
From the journal American Mineralogist Volume 103 Issue 11

Abstract

Olivine group minerals are ubiquitous in extrusive igneous rocks and play an important role in constraining equilibria for samples in the upper mantle and above. All Raman spectra of the olivine group minerals in the solid solution between forsterite (Fo, Mg2SiO4) and fayalite (Fa, Fe2SiO4) have a high-intensity doublet between 800 and 880 cm–1. Previous studies used small sample suites with limited compositional ranges and varying spectrometers to relate energy shifts of these two bands to Mg/Fe contents. In this work, Raman spectra of 93 olivine samples were acquired on either Bruker’s 532 nm (laser wavelength) Senterra or BRAVO (785/852.3 nm) spectrometer. This paper compares the two-peak band shift univariate method with two multivariate methods: partial least squares (PLS) and the least absolute shrinkage operator (Lasso). Data sets from several instruments are also examined to assess the most accurate method for predicting olivine composition from a Raman spectrum.

Our 181-spectra PLS model is recommended for use when determining olivine composition from a Raman spectrum. For Raman spectra of mixed phases where only the olivine doublet can be identified, composition can best be determined using the position of the peak ca. 838–857 cm–1 through use of the regression equation %Fo = –0.179625x2 + 310.077x –133 717 (where x = DB2 centroid in units of cm–1).

In situ methods for predicting mineral composition on planetary surfaces are critically important to extraterrestrial exploration going forward; of these, Raman spectroscopy is likely the best, as shown by the impending deployment of several Raman instruments to Mars (ExoMars and Mars 2020). More broadly, application of machine learning methods to spectral data processing have implications to multiple fields that use spectroscopic data.

Keywords: Raman spectroscopy; olivine; forsterite; fayalite; PLS; Lasso

Acknowledgments

We thank the Massachusetts Space Grant Consortium for student funding in support of this project.

References cited

Abdu, Y.A., Varela, M.E., and Hawthorne, F.C. (2011) Raman, FTIR, and Mössbauer spectroscopy of olivines from the D’Orbigny meteorite. Annual Meteoritical Society Meeting, 74, 5112 (abstract).Search in Google Scholar

Allen, F.S., Zhao, J., and Butterfield, D.S. (2000) Apparatus for Measuring and Applying Instrumentation Correction to Produce a Standard Raman Spectrum. U.S. Patent 6,141,095.Search in Google Scholar

Banfield, J.M., Dyar, M.D., and McGuire, A.V. (1992) The defect microstructure of oxidized mantle olivine from Dish Hill, California. American Mineralogist, 77, 959–975.Search in Google Scholar

Breitenfeld, L.B. (2017) Predicting olivine composition using Raman spectroscopy through band shift and multivariate analyses, 55–56 p. B.A. thesis, Mount Holyoke College, South Hadley.Search in Google Scholar

Butler, N.A., and Denham, M.C. (2000) The peculiar shrinkage properties of partial least squares regression. Journal of the Royal Statistical Society, 62, 585–593.10.1111/1467-9868.00252Search in Google Scholar

Byrne, S.A., Dyar, M.D., Bessette, E.E., Breitenfeld, L.B., Crowley, M.C., Hoff, C.M., Marchand, G.J., Ketley, M.N., Roberts, A.L., Sklute, E.C., and Parente, M. (2015) Pure mineral separates for mixing experiments to simulate planetary surfaces. Lunar and Planetary Science Conference, 46, 1499 (abstract).Search in Google Scholar

Carey, C., Dyar, M.D., Boucher, T., and Mahadevan, S. (2015) Machine learning tools for mineral recognition and classification from Raman spectroscopy. Journal of Raman Spectroscopy, 46, 894–903.10.1002/jrs.4757Search 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. Lunar and Planetary Science Conference, 48, 1097 (abstract).Search in Google Scholar

Chopelas, A. (1991) Single crystal Raman spectra of forsterite, fayalite, and monticellite. American Mineralogist, 76, 1101–1109.Search in Google Scholar

Dyar, M.D. (2003) Ferric iron in SNC meteorites as determined by Mössbauer spectroscopy: Implications for Martian landers and Martian oxygen fugacity. Meteoritics & Planetary Science, 38, 1733–1752.10.1111/j.1945-5100.2003.tb00012.xSearch in Google Scholar

Dyar, M.D., McGuire, A.V., and Ziegler, R.D. (1989) Redox equilibria and crystal chemistry of coexisting minerals from spinel lherzolite mantle xenoliths. American Mineralogist, 74, 969–980.Search in Google Scholar

Dyar, M.D., McGuire, A.V., and Harrell, M.D. (1992) Crystal chemistry of iron in two styles of metasomatism in the upper mantle. Geochimica et Cosmochimica Acta, 56, 2579–2586.10.1016/0016-7037(92)90212-2Search in Google Scholar

Dyar, M.D., Delaney, J.S., Sutton, S.R., and Schaefer, M.W. (1998) Fe3+ distribution in oxidized olivine: A synchrotron micro-XANES study. American Mineralogist, 83, 1361–1365.10.2138/am-1998-11-1227Search in Google Scholar

Dyar, M.D., Sklute, E.C., Menzies, O.N., Bland, P.A., Lindsley, D., Glotch, T., Lane, M.D., Wopenka, B., Klima, R., Bishop, J.L., and others. (2009) Spectroscopic characteristics of synthetic olivines, with an emphasis on fayalite: An integrated multi-wavelength approach. American Mineralogist, 94, 883–898.10.2138/am.2009.3115Search in Google Scholar

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

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

Dyar, M.D., Fassett, C.I., Giguere, S., Lepore, K., Byrne, S., Boucher, T., Carey, C., and Mahadevan, S. (2016a) Comparison of univariate and multivariate models for prediction of major and minor elements from laser-induced breakdown spectra with and without making. Spectrochimica Acta B, 123, 93–104.10.1016/j.sab.2016.07.010Search in Google Scholar

Dyar, M.D., Breves, E.A., Gunter, M.E., Lanzirotti, A., Tucker, J.M., Carey, C., Peel, S.E., Brown, E.B., Oberti, R., Lerotic, M., and Delaney, J.S. (2016b) Use of multivariate analysis for synchrotron micro-XANES analysis of iron valence state in amphiboles. American Mineralogist, 101, 1171–1189.10.2138/am-2016-5556Search in Google Scholar

Dyar, M.D., Breitenfeld, L.B., Carey, CJ, Bartholomew, P., Tague, T.J., Wang, P., Mertzman, S., Byrne, S.A., Crowley, M.C., Leight, C., and others. (2016c) Interlaboratory and cross-instrument comparison of Raman spectra of 96 minerals. Lunar and Planetary Science 47, Abstract 2240.Search in Google Scholar

Floran, R.J., Prinz, M., Hlava, P.F., Keil, K., Nehru, C.E., and Hinthorne, J.R. (1978) The Chassigny meteorite: A cumulate dunite with hydrous amphibole-bearing melt inclusions. Geochimica et Cosmochimica Acta, 42, 1213–1229.10.1016/0016-7037(78)90115-1Search in Google Scholar

Foster, N.J., Wozniakiewicz, P.J., Burchell, M.J., Kearsley, A.T., Creighton, A.J., and Cole, M.J. (2007) Identification by Raman spectroscopy of processing effects in forsterite-fayalite samples during hypervelocity impacts on foils and capture in aerogel. Annual Meteoritical Society Meeting, 70, 5186 (abstract).Search in Google Scholar

Gaisler, S.V., and Kolesov, B.A. (2007) Raman spectra of olivine solid solution (FexMg1-x)2 SiO4 and spin-vibration interaction. Journal of Structural Chemistry, 48, 61–65.10.1007/s10947-007-0009-9Search in Google Scholar

Giguere, S., Boucher, T., Carey, C.J., Mahadevan, S., and Dyar, M.D. (2017) A fully-customized baseline removal framework for spectroscopic applications. Applied Spectroscopy, 71, 1457–1470.10.1177/0003702817695624Search in Google Scholar

Guyot, F., Boyer, H., Madon, M., Velde, B., and Poirier, J.P. (1986) Comparison of the Raman microprobe spectra of (Mg, Fe)2SiO4 and Mg2GeO4 with olivine and spinel structures. Physics and Chemistry of Minerals, 13, 91–95.10.1007/BF00311898Search in Google Scholar

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

Iishi, K. (1978) Lattice dynamics of forsterite. American Mineralogist, 63, 1198–1208.Search in Google Scholar

Isaacson, P.J., Klima, R.L., Sunshine, J.M., Pieters, C.M., Hiroi, T., and Dyar, M.D. (2014) Visible to near-infrared reflectance spectroscopy of pure synthetic olivine across the olivine solid solution. American Mineralogist, 99, 467–478.10.2138/am.2014.4580Search in Google Scholar

Ishibashi, H., Arakawa, M., Ohi, S., Yamamoto, J., Miyake, A., and Kagi, H. (2008) Relationship between Raman spectral pattern and crystallographic orientation of a rock-forming mineral: a case study of Fo89Fa11 olivine. Journal of Raman Spectroscopy, 39, 1653–1659.10.1002/jrs.2094Search in Google Scholar

Ishibashi, H., Arakawa, M., Yamamoto, J., and Kagi, H. (2011) Precise determination of Mg/Fe ratios applicable to terrestrial olivine samples using Raman spectroscopy. Journal of Raman Spectroscopy, 43, 331–337.10.1002/jrs.3024Search in Google Scholar

Kolesov, B.A., and Geiger, C.A. (2004) A Raman spectroscopic study of Fe–Mg olivines. Physics and Chemistry of Minerals, 31, 142–154.10.1007/s00269-003-0370-ySearch in Google Scholar

Kolesov, B.A., and Tanskaya, J.V. (1996) Raman spectra and cation distribution in the lattice of olivines. Materials Research Bulletin, 31, 1035–1044.10.1016/S0025-5408(96)00085-2Search in Google Scholar

Kuebler, K.E., Jolliff, B.L., Wang, A., and Haskin, L.A. (2006) Extracting olivine (Fo-Fa) compositions from Raman spectral peak positions. Geochimica et Cosmochimica Acta, 70, 6201–6222.10.1016/j.gca.2006.07.035Search in Google Scholar

Lane, M.D., Glotch, T.D., Dyar, M. D., Pieters, C.M., Klima, R., Hiroi, T., Bishop, J.L., and Sunshine, J. (2011) Midinfrared spectroscopy of synthetic olivines: Thermal emission, specular and diffuse reflectance, and attenuated total reflectance studies of forsterite to fayalite. Journal of Geophysical Research, 116, E08010, DOI: 10.1029/2010JE003588.10.1029/2010JE003588Search in Google Scholar

McCanta, M.C., Treiman, A.H., Dyar, M.D., Alexander, C.M.O’D., Rumble, D., and Essene, E.J. (2008) The LaPaz Icefield 04840 meteorite: Mineralogy, metamorphism, and origin of an amphibole-and biotite-bearing R chondrite. Geochimica et Cosmochimica Acta, 72, 5757–5780.10.1016/j.gca.2008.07.034Search in Google Scholar

McGuire, A.V., Dyar, M.D., and Nielson, J.E. (1991) Metasomatic oxidation of upper mantle periodotite. Contributions to Mineralogy and Petrology, 109, 252–264.10.1007/BF00306483Search in Google Scholar

McGuire, A.V., Francis, C.A., and Dyar, M.D. (1992) Mineral standards for electron microprobe analysis of oxygen. American Mineralogist, 77, 1087–1087.Search in Google Scholar

McKeown, D.A., Bell, M.I., and Caracas, R. (2010) Theoretical determination of the Raman spectra of single-crystal forsterite (Mg2SiO4 American Mineralogist, 95, 980–986.10.2138/am.2010.3423Search in Google Scholar

McKillup, S., and Dyar, M.D. (2010) Geostatistics explained: An introductory guide for earth scientists, 396 p. Cambridge University Press, Cambridge, U.K.10.1017/CBO9780511807558Search in Google Scholar

McSween, H.Y., and Jarosewich, E. (1983) Petrogenesis of the Elephant Moraine A79001 meteorite: Multiple magma pulses on the shergottite parent body. Geochimica et Cosmochimica Acta, 47, 1501–1513.10.1016/0016-7037(83)90309-5Search in Google Scholar

Mikouchi, T., and Kurihara, T. (2008) Mineralogy and petrology of paired lherzolitic shergottites Yamato 000027, Yamato 000047, and Yamato 000097: Another fragment from a Martian “lherzolite” block. Polar Science, 2, 175–194.10.1016/j.polar.2008.06.003Search in Google Scholar

Mohanan, K., Sharma, S.K., and Bishop, F.C. (1993) A Raman spectral study of forsteritemonticellite solid solutions. American Mineralogist, 78, 42–48.Search in Google Scholar

Moral, A.G., Rull, F., Maurice, S., Hutchinson, I., Canora, C.P., Seoane, L., Canchal, R., Gallego, P., Ramos, G., Prieto, J.A.R., and others. (2018) Raman laser spectrometer for 2020 ExoMars Mission. Engineering and qualification model capabilities and future activities. Lunar and Planetary Science Conference, 49, 2449 (abstract).Search in Google Scholar

Morse, S.A. (1996) Kiglapait mineralogy. 3. Olivine compositions and Rayleigh fractionation models. Journal of Petrology, 37, 1037–1061.10.1093/petrology/37.5.1037Search in Google Scholar

Morse, S.A. (2001) Augite-olivine equilibria in the Kiglapait intrusion, Labrador, Canada. Canadian Mineralogist, 39, 267–274.10.2113/gscanmin.39.2.267Search in Google Scholar

Mouri, T., and Enami, M. (2008) Raman spectroscopic study of olivine-group minerals. Journal of Mineralogical and Petrological Sciences, 103, 100–104.10.2465/jmps.071015Search in Google Scholar

Mullen, T., Dyar, M.D., Parente, M., and Breitenfeld, L.B. (2018) Improving matching accuracy in Raman spectroscopy by quantifying the wavenumber shift between instruments. Lunar and Planetary Science, 49, Abstract 1185.Search in Google Scholar

Parques-Ledent, M.T., and Tarte, P. (1973) Vibrational studies of olivine-type compound—I. The i.r. and Raman spectra of the isotopic species of Mg2SiO4 Spectrochimica Acta A, 29, 1007–1016.Search in Google Scholar

Piriou, B. (1983) The high-frequency vibrational spectra of vitreous and crystalline orthosilicates. American Mineralogist, 68, 426–443.Search in Google Scholar

Price, G.D., Parker, S.C., and Leslie, M. (1987) The lattice dynamics of forsterite. Mineralogical Magazine, 51, 157–170.10.1180/minmag.1987.051.359.18Search in Google Scholar

Schaefer, M.W. (1983) Crystal chemistry of ferric-rich fayalites, 38–56 p. Ph.D. thesis, MIT, Cambridge.Search in Google Scholar

Servoin, J., Piriou, B., and Alain, P. (1972) Diffusion Raman de la forsterite sythetique pure, Mg2SiO4 Comptes Rendus de l’Académie des Sciences Paris, 274, 135–137.Search in Google Scholar

Sklute, E.C. (2006) Mössbauer spectroscopy of synthetic olivine across the Fe-Mg solid solution, 1–38 p. B.A. thesis, Mount Holyoke College, South Hadley.Search in Google Scholar

Stone, M., and Brooks, R.J. (1990) Continuum regression: cross-validated sequentially constructed predictions embracing ordinary least-squares, partial least-squares, and principal components regression. Journal of the Royal Statistical Society B, 52, 237–269.10.1111/j.2517-6161.1990.tb01786.xSearch in Google Scholar

Tibshirani, R. (1995) Regression shrinkage and selection via the Lasso. Journal of the Royal Statistical Society, 58, 267–288.10.1111/j.2517-6161.1996.tb02080.xSearch in Google Scholar

Tucker, J.M., Dyar, M.D., Schaefer, M.W., Clegg, S.M., and Wiens, R.C. (2010) Optimization of laser-induced breakdown spectroscopy for rapid geochemical analysis. Chemical Geology, 277, 137–148.10.1016/j.chemgeo.2010.07.016Search in Google Scholar

Wang, A., Kuebler, K., Jolliff, B., and Haskin, L.A. (2004) Mineralogy of a Martian meteorite as determined by Raman spectroscopy. Journal of Raman Spectroscopy, 35, 504–514.10.1002/jrs.1175Search in Google Scholar

Weber, I., Bottger, U., Pavlov, S.G., Jessberger, E.K., and Hubers, H.W. (2014) Mineralogical and Raman spectroscopy studies of natural olivines exposed to different planetary environments. Planetary and Space Science, 104, 163–172.10.1016/j.pss.2014.08.016Search in Google Scholar

Wiens, R.C., Newell, R., Clegg, S., Sharma, S.K., Misra, A., Bernardi, P., Maurice, S., McCabe, K., Cais, P., and the SuperCam Science Team (2017) The SuperCam remote Raman spectrometer for Mars 2020. Lunar and Planetary Science, 48, 2600 (abstract).Search in Google Scholar

Wold, S., Martens, H., and Wold, H. (1983) The multivariate calibration problem in chemistry solved by the PLS method. Lecture Notes in Mathematics, 973, 286–293.10.1007/BFb0062108Search in Google Scholar

Yasuzuka, T., Ishibashi, H., Arakawa, M., Yamamoto, J., and Kagi, H. (2009) Simultaneous determination of Mg# and residual pressure in olivine using micro-Raman spectroscopy. Journal of Mineralogical and Petrological Sciences, 104, 395–400.10.2465/jmps.090615Search in Google Scholar

Zhang, Z.M., Chen, S., and Liang, Y.Z. (2010) Baseline correction using adaptive iteratively reweighted penalized least squares. Royal Society of Chemistry, 135, 1138–1146.10.1039/b922045cSearch in Google Scholar PubMed

Received: 2017-08-31
Accepted: 2018-06-23
Published Online: 2018-10-30
Published in Print: 2018-11-27

© 2018 Walter de Gruyter GmbH, Berlin/Boston

Articles in the same Issue

  1. Highlights and Breakthroughs
  2. Probing planetary core structure and dynamics using density and sound velocity
  3. Mapping the distribution of melt during anatexis at the source area of crustal granites by synchrotron μ-XRF
  4. Geochemical constraints on residual metal and sulfide in the sources of lunar mare basalts
  5. High-temperature behavior of natural ferrierite: In-situ synchrotron X-ray powder diffraction study
  6. The crystal chemistry of the sakhaite–harkerite solid solution
  7. Quantitative analysis of H-species in anisotropic minerals by unpolarized infrared spectroscopy: An experimental evaluation
  8. Liquid properties in the Fe-FeS system under moderate pressure: Tool box to model small planetary cores
  9. Solution mechanisms of COHN fluids in melts to upper mantle temperature, pressure, and redox conditions
  10. Dating phosphates of the strongly shocked Suizhou chondrite
  11. Quantitative measurement of olivine composition in three dimensions using helical-scan X-ray micro-tomography
  12. Chemical fingerprints and residence times of olivine in the 1959 Kilauea Iki eruption, Hawaii: Insights into picrite formation
  13. Predicting olivine composition using Raman spectroscopy through band shift and multivariate analyses
  14. Dehydrogenation and dehydroxylation as drivers of the thermal decomposition of Fe-chlorites
  15. High-pressure granulite facies metamorphism (~1.8 GPa) revealed in silica-undersaturated garnet-spinel-corundum gneiss, Central Maine Terrane, Connecticut, U.S.A.
  16. Letter
  17. Raman elastic geobarometry for anisotropic mineral inclusions
  18. Synthesis and crystal structure of Mg-bearing Fe9O11: New insight in the complexity of Fe-Mg oxides at conditions of the deep upper mantle
https://doi.org/10.2138/am-2018-6291
Keywords for this article
Raman spectroscopy; olivine; forsterite; fayalite; PLS; Lasso

Articles in the same Issue

  1. Highlights and Breakthroughs
  2. Probing planetary core structure and dynamics using density and sound velocity
  3. Mapping the distribution of melt during anatexis at the source area of crustal granites by synchrotron μ-XRF
  4. Geochemical constraints on residual metal and sulfide in the sources of lunar mare basalts
  5. High-temperature behavior of natural ferrierite: In-situ synchrotron X-ray powder diffraction study
  6. The crystal chemistry of the sakhaite–harkerite solid solution
  7. Quantitative analysis of H-species in anisotropic minerals by unpolarized infrared spectroscopy: An experimental evaluation
  8. Liquid properties in the Fe-FeS system under moderate pressure: Tool box to model small planetary cores
  9. Solution mechanisms of COHN fluids in melts to upper mantle temperature, pressure, and redox conditions
  10. Dating phosphates of the strongly shocked Suizhou chondrite
  11. Quantitative measurement of olivine composition in three dimensions using helical-scan X-ray micro-tomography
  12. Chemical fingerprints and residence times of olivine in the 1959 Kilauea Iki eruption, Hawaii: Insights into picrite formation
  13. Predicting olivine composition using Raman spectroscopy through band shift and multivariate analyses
  14. Dehydrogenation and dehydroxylation as drivers of the thermal decomposition of Fe-chlorites
  15. High-pressure granulite facies metamorphism (~1.8 GPa) revealed in silica-undersaturated garnet-spinel-corundum gneiss, Central Maine Terrane, Connecticut, U.S.A.
  16. Letter
  17. Raman elastic geobarometry for anisotropic mineral inclusions
  18. Synthesis and crystal structure of Mg-bearing Fe9O11: New insight in the complexity of Fe-Mg oxides at conditions of the deep upper mantle
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