Secondary ion mass spectrometer analyses for trace elements in glass standards using variably charged silicon ions for normalization
-
Eric N. Carlson
Abstract
Trace element analyses of silicate materials by secondary ion mass spectrometry (SIMS) typically normalize the secondary ion count rate for the isotopes of interest to the count rate for one of the silicon isotopes. While the great majority of SIMS analyses use the signal from Si+, some laboratories have used a multiply charged ion (Si2+ or Si3+). We collected data and constructed calibration curves for lithium, beryllium, and boron using these different normalizing species on synthetic basaltic glass and soda-lime silicate glass standards. The calibrations showed little effect of changing matrix when Si+ was used, but larger effects (up to a factor of ~2) when using Si2+ or Si3+ are a warning that care must be taken to avoid inaccurate analyses. The smallest matrix effects were observed at maximum transmission compared to detecting ions with a few tens of eV of initial kinetic energy (“conventional energy filtering”). Normalizing the light element ion intensities to Al3+ showed a smaller matrix effect than multiply-charged Si ions. When normalized to 16O+ (which includes oxygen from the sample and from the primary beam), the two matrices showed distinct calibration curves, suggesting that changing sputter yields (atoms ejected per primary atom impact) may play a role in the probability of producing multiply charged silicon ions.
Acknowledgments and Funding
The authors thank Lynda Williams for help with the operation of the Cameca IMS 6f SIMS instrument, and Peter Williams for inspiring this study with his work on multiply charged ions. We are grateful to the U. S. National Science Foundation for supporting the operation of the ASU SIMS and NanoSIMS as a multi-user community facility (currently NSF EAR 1819550) since 2007.
References cited
de Hoog, J.C.M. and EIMF (2018) Matrix effects during SIMS measurement of the lithium mass fractions of silicate glasses: correction procedures and updated preferred values of reference materials. Geostandards and Geoanalytical Research, 42, 513–522.Search in Google Scholar
Deng, R.-C. and Williams, P. (1989) Factors affecting precision and accuracy in quantitative analysis by secondary ion mass spectrometry. Analytical Chemistry, 61, 1946–1948, https://doi.org/10.1021/ac00192a035Search in Google Scholar
Dumke, M.F., Tombrello, T.A., Weller, R.A., Housley, R.M., and Cirlin, E.H. (1983) Sputtering of the gallium-indium eutectic alloy in the liquid phase. Surface Science, 124, 407–422, https://doi.org/10.1016/0039-6028(83)90800-2Search in Google Scholar
Dunham, E. T., Wadhwa, M., Desch, S.J., and Hervig, R.L. (2020) Best practices for determination of initial 10Be/9Be in early Solar System materials by SIMS. Geostandards and Geoanalytical Research, DOI: 10.1111/ggr.1232910.1111/ggr.12329Search in Google Scholar
Franzreb, K., Sobers, R.C. Jr., Lorincik, J., and Williams, P. (2004) Formation of doubly positively charged diatomic ions of Mo22+ produced by Ar+ sputtering of an Mo metal surface. The Journal of Chemical Physics, 120, 7983–7986, https://doi.org/10.1063/1.1690234Search in Google Scholar
Guillong, M., Hametner, K., Reusser, E., Wilson, S.A., and Günther, D. (2005) Preliminary characterisation of new glass reference materials (GSA-1G, GSC-1G, GSD-1G and GSE- 1G) by laser ablation-inductively coupled plasma-mass spectrometry using 193 nm, 213 nm and 266 nm wavelengths. Geostandards Newsletter, 29, 315–331, https://doi.org/10.1111/j.1751-908X.2005.tb00903.xSearch in Google Scholar
Harrison, T.M., Heizler, M.T., McKeegan, K.D., and Schmitt, A.K. (2010) In situ 40K–40Ca ‘double-plus’ SIMS dating resolves Klokken feldspar 40K–40Ar paradox. Earth and Planetary Science Letters, 299, 426–433, https://doi.org/10.1016/j.epsl.2010.09.023Search in Google Scholar
Hervig, R.L. (1996) Analyses of geological materials for boron by secondary ion mass spectrometry. In E. S. Grew and L.M. Anovitz, Eds., Boron: Mineralogy, petrology, and geochemistry in the Earth’s crust, 33, 789–804. Reviews in Mineralogy and Geochemistry, Mineralogical Society of America, Chantilly, Virginia.Search in Google Scholar
Hervig, R.L. (2002) Beryllium analyses by secondary ion mass spectrometry. In E.S. Grew, Ed., Beryllium: Mineralogy, petrology, and geochemistry in the Earth’s crust, 50, 319–332. Reviews in Mineralogy and Geochemistry, Mineralogical Society of America, Chantilly, Virginia.Search in Google Scholar
Jochum, K.P., Willbold, M., Raczek, I., Stoll, B., and Herwig, K. (2005) Chemical characterization of the USGS reference glasses GSA-1G, GSC-1G, GSD-1G, GSE-1G, BCR-2G, BHVO-2G and BIR-1G using EPMA, ID-TIMS, ID-ICP-MS, and LA-ICP-MS. Geostandards Newsletter, 29, 285–302, https://doi.org/10.1111/j.1751-908X.2005.tb00901.xSearch in Google Scholar
Jochum, K.P., Weis, U., Stoll, B., Kuzmin, D., Yang, O., Raczek, I., Jacob, D.E., Stracke, A., Birbaum, K., Frick, D.A., and others. (2011) Determination of reference values for NIST SRM 610–617 glasses following ISO guidelines. Geostandards and Geoanalytical Research, 35, 397–429, https://doi.org/10.1111/j.1751-908X.2011.00120.xSearch in Google Scholar
Marschall, H.R. and Monteleone, B.D. (2015) Boron isotope analysis of silicate glass with very low boron concentrations by secondary ion mass spectrometry. Geostandards and Geoanalytical Research, 39, 31–46, https://doi.org/10.1111/j.1751-908X.2014.00289.xSearch in Google Scholar
Ottolini, L. (2002) Accurate SIMS analysis of Ca in olivine based on high-energy doubly charged secondary ions. Journal of Analytical Atomic Spectrometry, 17, 280–283, https://doi.org/10.1039/b108569gSearch in Google Scholar
Ottolini, L., Bottazzi, P., and Vannucci, R. (1993) Quantification of lithium, beryllium, and boron in silicates by secondary ion mass spectrometry using conventional energy filtering. Analytical Chemistry, 65, 1960–1968, https://doi.org/10.1021/ac00063a007Search in Google Scholar
Regier, M.E., Hervig, R.L., Myers, M.L., Roggensack, K., and Wilson, C.J.N. (2016) Analyzing nitrogen in natural and silicate synthetic glasses by secondary ion mass spectrometry. Chemical Geology, 447, 27–39, https://doi.org/10.1016/j.chemgeo.2016.10.019Search in Google Scholar
Riciputi, L.R., Christie, W.H., Cole, D.R., and Rosseel, T.M. (1993) Analysis of rare earth elements in silicates by ion microprobe using doubly charged ions. Analytical Chemistry, 65, 1186–1191, https://doi.org/10.1021/ac00057a014Search in Google Scholar
Schauer, S.N. and Williams, P. (1992) Doubly charged sputtered ions of fourth-row elements. Physical Review B: Condensed Matter, 46, 15452–15464, https://doi.org/10.1103/PhysRevB.46.15452Search in Google Scholar
Shimizu, N. and Hart, S.R. (1982) Applications of the ion microprobe to geochemistry and cosmochemistry. Annual Review of Earth and Planetary Sciences, 10, 483–526, https://doi.org/10.1146/annurev.ea.10.050182.002411Search in Google Scholar
Slodzian, G. (1975) Some problems encountered in secondary ion emission applied to elementary analysis. Surface Science, 48, 161–186, https://doi.org/10.1016/0039-6028(75)90315-5Search in Google Scholar
Zinner, E., Fahey, A.J., and McKeegan, K.D. (1986) Characterization of Electron Multipliers by Charge Distributions. In A. Benninghoven, R.J. Colton, D.S. Simons, and H.W. Werner, Eds., Secondary Ion Mass Spectrometry SIMS V. Springer Series in Chemical Physics, vol. 44, Springer, https://doi.org/10.1007/978-3-642-82724-2_42Search in Google Scholar
© 2023 by Mineralogical Society of America
Articles in the same Issue
- Mineralogy and bulk geochemistry of a fumarole at Hverir, Iceland: Analog for acid-sulfate leaching on Mars
- The crystal structure and chemistry of natural giniite and implications for Mars
- Solid solution of CaSiO3 and MgSiO3 perovskites in the lower mantle: The role of ferrous iron
- Secondary ion mass spectrometer analyses for trace elements in glass standards using variably charged silicon ions for normalization
- Raman shifts of c-BN as an ideal P-T sensor for studying water-rock interactions in a diamond-anvil cell
- Resetting of the U-Pb and Th-Pb systems in altered bastnäsite: Insight from the behavior of Pb at nanoscale
- X-ray diffraction reveals two structural transitions in szomolnokite
- Contamination of heterogeneous lower crust in Hannuoba tholeiite: Evidence from in situ trace elements and strontium isotopes of plagioclase
- Oxygen fugacity buffering in high-pressure solid media assemblies from IW-6.5 to IW+4.5 and application to the V K-edge oxybarometer
- Trace element partitioning between anhydrite, sulfate melt, and silicate melt
- Chemical reaction between ferropericlase (Mg,Fe)O and water under high pressure-temperature conditions of the deep lower mantle
- Composition-dependent thermal equation of state of B2 Fe-Si alloys at high pressure
- Effects of thermal annealing on water content and δ18O in zircon
- Tourmaline and zircon trace the nature and timing of magmatic-hydrothermal episodes in granite-related Sn mineralization: Insights from the Libata Sn ore field
- Cation ordering, twinning, and pseudo-symmetry in silicate garnet: The study of a birefringent garnet with orthorhombic structure
- The occurrence of monoclinic jarosite in natural environments
- Niobium speciation in minerals revealed by L2,3-edges XANES spectroscopy
- The first occurrence of the carbide anion, C4–, in an oxide mineral: Mikecoxite, ideally (CHg4)OCl2, from the McDermitt open-pit mine, Humboldt County, Nevada, U.S.A
- Hydrothermal alteration of Ni-rich sulfides in peridotites of Abu Dahr, Eastern Desert, Egypt: Relationships among minerals in the Fe-Ni-Co-O-S system, fO2 and fS2
- New Mineral Names: Arsenic and Lead
Articles in the same Issue
- Mineralogy and bulk geochemistry of a fumarole at Hverir, Iceland: Analog for acid-sulfate leaching on Mars
- The crystal structure and chemistry of natural giniite and implications for Mars
- Solid solution of CaSiO3 and MgSiO3 perovskites in the lower mantle: The role of ferrous iron
- Secondary ion mass spectrometer analyses for trace elements in glass standards using variably charged silicon ions for normalization
- Raman shifts of c-BN as an ideal P-T sensor for studying water-rock interactions in a diamond-anvil cell
- Resetting of the U-Pb and Th-Pb systems in altered bastnäsite: Insight from the behavior of Pb at nanoscale
- X-ray diffraction reveals two structural transitions in szomolnokite
- Contamination of heterogeneous lower crust in Hannuoba tholeiite: Evidence from in situ trace elements and strontium isotopes of plagioclase
- Oxygen fugacity buffering in high-pressure solid media assemblies from IW-6.5 to IW+4.5 and application to the V K-edge oxybarometer
- Trace element partitioning between anhydrite, sulfate melt, and silicate melt
- Chemical reaction between ferropericlase (Mg,Fe)O and water under high pressure-temperature conditions of the deep lower mantle
- Composition-dependent thermal equation of state of B2 Fe-Si alloys at high pressure
- Effects of thermal annealing on water content and δ18O in zircon
- Tourmaline and zircon trace the nature and timing of magmatic-hydrothermal episodes in granite-related Sn mineralization: Insights from the Libata Sn ore field
- Cation ordering, twinning, and pseudo-symmetry in silicate garnet: The study of a birefringent garnet with orthorhombic structure
- The occurrence of monoclinic jarosite in natural environments
- Niobium speciation in minerals revealed by L2,3-edges XANES spectroscopy
- The first occurrence of the carbide anion, C4–, in an oxide mineral: Mikecoxite, ideally (CHg4)OCl2, from the McDermitt open-pit mine, Humboldt County, Nevada, U.S.A
- Hydrothermal alteration of Ni-rich sulfides in peridotites of Abu Dahr, Eastern Desert, Egypt: Relationships among minerals in the Fe-Ni-Co-O-S system, fO2 and fS2
- New Mineral Names: Arsenic and Lead
