Home Raman spectroscopy of the ilmenite–geikielite solid solution
Article
Licensed
Unlicensed Requires Authentication

Raman spectroscopy of the ilmenite–geikielite solid solution

  • Laura B. Breitenfeld ORCID logo EMAIL logo , M. Darby Dyar , Leif Tokle and Kevin Robertson
Published/Copyright: September 9, 2024
Become an author with De Gruyter Brill

Abstract

Ilmenite (Fe2+TiO3) and geikielite (MgTiO3) are important terrestrial minerals relevant to the geology of the Earth, the Moon, Mars, and meteorite samples. Raman spectroscopy is a powerful technique that allows for mineral cation determination for the ilmenite–geikielite solid solution. We report on a suite of nine samples within the ilmenite–geikielite solid solution and provide context for their quantitative interpretation. We compare a univariate Raman peak position model for predicting ilmenite composition with a multivariate machine learning model. The univariate model is currently recommended, though the multivariate model may become superior if the data set size is increased. This study lays the groundwork for quantifying Fe (ilmenite) and Mg (geikielite) within oxide minerals using a cheap, portable, and efficient technology like Raman spectroscopy.

Acknowledgments and Funding

We are grateful to the NASA SSERVI RIS4E and RISE2 nodes for their support. We thank Steven Jaret and the other reviewer for their insightful feedback that improved the quality of this work. Data Availability: The Raman spectral data are archived in an external data repository at https://zenodo.org/records/10210991 (Breitenfeld et al. 2023).

References Cited

Beattie, I.R., and Gilson, T.R. (1970) The single-crystal Raman spectra of nearly opaque materials. Iron (III) oxide and chromium (III) oxide. Journal of the Chemical Society A: Inorganic, Physical, Theoretical, 980–986.Search in Google Scholar

Breitenfeld, L.B., Dyar, M.D., Tokle, L., and Robertson, K. (2023) Raman spectroscopy of the ilmenite–geikielite solid solution Data set, Zenodo, https://zenodo.org/records/10210991.Search in Google Scholar

Bunch, T.E. and Keil, K. (1971) Chromite and ilmenite in non chondritic meteorites. American Mineralogist, 56, 146–157.Search in Google Scholar

Chopelas, A. (1999) Estimates of mantle relevant Clapeyron slopes in the MgSiO3 system from high-pressure spectroscopic data. American Mineralogist, 84, 233–244, https://doi.Org/10.2138/am-1999-0304.Search in Google Scholar

Cloutis, E.A., Caudill, C., Lalla, E.A., Newman, J., Daly, M., Lymer, E., Freemantle, J., Kruzelecky, R., Applin, D., Chen, H., and others. (2022) LunaR: Overview of a versatile Raman spectrometer for lunar exploration. Frontiers in Astronomy and Space Sciences, 9, 1016359, https://doi.Org/10.3389/fspas.2022.1016359.Search in Google Scholar

Dyar, M.D. and Ytsma, C.R. (2021) Effect of data set size on geochemical quantification accuracy with laser-induced breakdown spectroscopy. Spectrochimica Acta. Part B, Atomic Spectroscopy, 177, 106073, https://doi.Org/10.1016/j.sab.2021.106073.Search in Google Scholar

Geladi, P. and Kowalski, B.R. (1986) Partial least-squares regression: A tutorial. Analytica Chimica Acta, 185, 1–17, https://doi.Org/10.1016/0003-2670(86)80028-9.Search in Google Scholar

Heiken, G.H. and Vaniman, D.T. (1990) Characterization of lunar ilmenite resources. Lunar and Planetary Science Conference, 20th, Houston, Texas, March 13–17, 1989, Proceedings (A90-33456 14–91).Search in Google Scholar

Lemelin, M., Morisset, C.E., Germain, M., Hipkin, V., Goïta, K., and Lucey, P.G. (2013) Ilmenite mapping of the lunar regolith over Mare Australe and Mare Ingenii regions: An optimized multisource approach based on Hapke radiative transfer theory. Journal of Geophysical Research: Planets, 118, 2582–2593, https://doi.Org/10.1002/2013JE004392.Search in Google Scholar

Linton, J.A., Fei, Y., and Navrotsky, A. (1999) The MgTiO3-FeTiO3 join at high pressure and temperature. American Mineralogist, 84, 1595–1603, https://doi.Org/10.2138/am-1999-1013.Search in Google Scholar

McMillan, P.F. and Ross, N.L. (1987) Heat capacity calculations for Al2O3 corundum and MgSiO3 ilmenite. Physics and Chemistry of Minerals, 14, 225–234, https://doi.Org/10.1007/BF00307986.Search in Google Scholar

McSween, H.Y. Jr. (1994) What we have learned about Mars from SNC meteorites. Meteoritics, 29, 757–779, https://doi.Org/10.1111/j.1945-5100.1994.tb01092.x.Search in Google Scholar

Morris, R.V., Klingelhoefer, G., Schröder, C., Rodionov, D.S., Yen, A., Ming, D.W., and others. (2006) Mössbauer mineralogy of rock, soil, and dust at Gusev crater, Mars: Spirit’s journey through weakly altered olivine basalt on the plains and pervasively altered basalt in the Columbia Hills. Journal of Geophysical Research: Planets, 111 (E2), https://doi.Org/10.1029/2005JE002584.Search in Google Scholar

Okada, T., Narita, T., Nagai, T., and Yamanaka, T. (2008) Comparative Raman spectroscopic study on ilmenite-type MgSiO3 (akimotoite), MgGeO3, and MgTiO3 (geikielite) at high temperatures and high pressures. American Mineralogist, 93, 39–47, https://doi.Org/10.2138/am.2008.2490.Search in Google Scholar

Papike, J.J., Hodges, F.N., Bence, A.E., Cameron, M., and Rhodes, J.M. (1976) Mare basalts: Crystal chemistry, mineralogy, and petrology. Reviews of Geophysics, 14, 475–540, https://doi.Org/10.1029/RG014i004p00475.Search in Google Scholar

Papike, J., Taylor, L., and Simon, S. (1991) Lunar minerals. In G.H. Heiken, D.T. Vaniman, and B.M. French, Eds., Lunar Sourcebook: A User’s Guide to the Moon, 121–181. Cambridge University Press.Search in Google Scholar

Pinet, M., Smith, D.C., and Boyer, H. (1986) Raman fingerprinting of opaque and semi-opaque minerals: The natural system geikielite-ilmenite-pyrophanite (GIP). Terra Cognita, 7, 18.Search in Google Scholar

Reusser, E., Gieré, R., and Lumpkin, G.R. (2001) Geikielite exsolution in spinel. American Mineralogist, 86, 1435–1446, https://doi.Org/10.2138/am-2001-11-1212.Search in Google Scholar

Reynard, B. and Guyot, F. (1994) High-temperature properties of geikielite (MgTiO3-ilmenite) from high-temperature high-pressure Raman spectros-copy–Some implications for MgSiO3-ilmenite. Physics and Chemistry of Minerals, 21, 441–450, https://doi.Org/10.1007/BF00202274.Search in Google Scholar

Robertson, K., Milliken, R., Pieters, C., Tokle, L., Cheek, L., and Isaacson, P. (2022) Textural and compositional effects of ilmenite on the spectra of high-titanium lunar basalts. Icarus, 375, 114836, https://doi.Org/10.1016/j.icarus.2021.114836.Search in Google Scholar

Ross, N.L. and McMillan, P. (1984) The Raman spectrum of MgSiO3 ilmenite. American Mineralogist, 69, 719–721.Search in Google Scholar

Rull, F., Martinez-Frias, J., Sansano, A., Medina, J., and Edwards, H.G.M. (2004) Comparative micro-Raman study of the Nakhla and Vaca Muerta meteorites. Journal of Raman Spectroscopy: JRS, 35, 497–503, https://doi.Org/10.1002/jrs.1177.Search in Google Scholar

Sato, H., Robinson, M.S., Lawrence, S.J., Denevi, B.W., Hapke, B., Jolliff, B.L., and Hiesinger, H. (2017) Lunar mare TiO2 abundances estimated from UV/Vis reflectance. Icarus, 296, 216–238, https://doi.Org/10.1016/j.icarus.2017.06.013.Search in Google Scholar

Snetsinger, K.G. and Keil, K. (1969) Ilmenite in ordinary chondrites. American Mineralogist. Journal of Earth and Planetary Materials, 54, 780–786.Search in Google Scholar

Surkov, Y., Shkuratov, Y., Kaydash, V., Korokhin, V., and Videen, G. (2020) Lunar ilmenite content as assessed by improved Chandrayaan-1 M3 data. Icarus, 341, 113661, https://doi.Org/10.1016/j.icarus.2020.113661.Search in Google Scholar

Szymanski, A., Brenker, F.E., Palme, H., and El Goresy, A. (2010) High oxidation state during formation of Martian nakhlites. Meteoritics & Planetary Science, 45, 21–31, https://doi.Org/10.1111/j.1945-5100.2009.01002.x.Search in Google Scholar

Tibshirani, R. (1996) Regression shrinkage and selection via the lasso. Journal of the Royal Statistical Society. Series B, Statistical Methodology, 58, 267–288, https://doi.Org/10.1111/j.2517-6161.1996.tb02080.x.Search in Google Scholar

Tokle, L. and Robertson, K.M. (2019) X-ray diffraction calibration of the Fe2+–Mg2+ solid solution of ilmenite, with application to lunar basalts. European Journal of Mineralogy, 31, 473–483, https://doi.Org/10.1127/ejm/2019/0031-2850.Search in Google Scholar

Tokle, L., Robertson, K.M., and Milliken, R.E. (2018) Development of an Fe-Mg compositional calibration for the ilmenite–geikielite solid-solution using XRD and reflective spectroscopy. 49th Annual Lunar and Planetary Science Conference Proceedings (LPI Contrib. No. 2083), Abstract #2095.Search in Google Scholar

Wang, A., Kuebler, K.E., Jolliff, B.L., and Haskin, L.A. (2004) Raman spectroscopy of Fe-Ti-Cr-oxides, case study: Martian meteorite EETA79001. American Mineralogist, 89, 665–680, https://doi.Org/10.2138/am-2004-5-601.Search in Google Scholar

White, W.B. (1975) Structural interpretation of lunar and terrestrial minerals by Raman spectroscopy. In C.Karr, Jr., Ed., Infrared and Raman Spectroscopy of Lunar and Terrestrial Minerals, 325–358. Academic Press.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, https://doi.Org/10.1007/BFb0062108.Search in Google Scholar

Wold, S., Sjöström, M., and Eriksson, L. (2001) PLS-regression: A basic tool of chemometrics. Chemometrics and Intelligent Laboratory Systems, 58, 109–130, https://doi.Org/10.1016/S0169-7439(01)00155-1.Search in Google Scholar

Wyatt, B.A., Baumgartner, M., Anckar, E., and Grutter, H. (2004) Compositional classification of “kimberlitic” and “non-kimberlitic” ilmenite. Lithos, 77, 819–840, https://doi.Org/10.1016/j.lithos.2004.04.025.Search in Google Scholar

Received: 2023-11-27
Accepted: 2024-03-15
Published Online: 2024-09-09
Published in Print: 2024-09-25

© 2024 by Mineralogical Society of America

Articles in the same Issue

  1. Germanium distribution in Mississippi Valley-Type systems from sulfide deposition to oxidative weathering: A perspective from Fule Pb-Zn(-Ge) deposit, South China
  2. Characterization and potential toxicity of asbestiform erionite from Gawler Downs, New Zealand
  3. First widespread occurrence of rare phosphate chladniite in a meteorite, winonaite Graves Nunataks (GRA) 12510: Implications for phosphide–phosphate redox buffered genesis in meteorites
  4. K isotopic fractionation in K-feldspar: Effects of mineral chemistry
  5. Jarosite formation in Permian-Triassic strata at Xiakou (South China): Implications for jarosite precipitation from H2S upwelling on Mars
  6. The effect of A-site cations on charge-carrier mobility in Fe-rich amphiboles
  7. Calorimetry and structural analysis of uranyl sulfates with rare topologies
  8. Biological control of ultra-skeleton mineralization in coral
  9. Systematic study of high field strength elements during liquid immiscibility between carbonatitic melt and silicate melt
  10. Clustering and interfacial segregation of radiogenic Pb in a mineral host-inclusion system: Tracing two-stage Pb and trace element mobility in monazite inclusions in rutile
  11. First application of scintillator-based photon-counting computed tomography to rock samples: Preliminary results and prospects
  12. GCDkit.Mineral: A customizable, platform-independent R-language environment for recalculation, plotting, and classification of electron probe microanalyses of common rock-forming minerals
  13. Apatite as an archive of pegmatite-forming processes: An example from the Berry-Havey pegmatite (Maine, U.S.A.)
  14. Re-examination of vesbine in vanadate-rich sublimate-related associations of Vesuvius (Italy): Mineralogical features and origin
  15. Temperature and compositional dependences of H2O solubility in majorite
  16. Raman spectroscopy of the ilmenite–geikielite solid solution
Downloaded on 20.9.2025 from https://www.degruyterbrill.com/document/doi/10.2138/am-2023-9262/html?lang=en
Scroll to top button