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SIMS stable isotope measurement: counting statistics and analytical precision

Published online by Cambridge University Press:  25 June 2018

I. C. W. Fitzsimons ,
B. Harte  and
R. M. Clark
I. C. W. Fitzsimons*
Affiliation:
Department of Geology and Geophysics, The University of Edinburgh, The Grant Institute, West Mains Road, Edinburgh EH9 3JW, UK
B. Harte
Affiliation:
Department of Geology and Geophysics, The University of Edinburgh, The Grant Institute, West Mains Road, Edinburgh EH9 3JW, UK
R. M. Clark
Affiliation:
Department of Mathematics and Statistics, Monash University, Clayton, Victoria 3168, Australia
*
*E-mail: ianf@lithos.curtin.edu.au
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Abstract

Analytical precision is vital in the interpretation of stable isotope data collected by secondary ion mass spectrometry (SIMS) given the small analysis volumes and the small magnitude of natural isotopic variations. The observed precision of a set of measurements is represented by the standard deviation(precision of an individual measurement) or the standard error of the mean (precision of the mean value). The SIMS data show both systematic variations with time and random Poisson variability, but the former largely cancel out when data for two different isotopes are expressed as a ratio. The precision of a SIMS isotope ratio routinely matches that predicted by Poisson counting statistics and can approach that of conventional bulk analysis techniques for counting times of several hours. All sample analyse must be calibrated for instrumental mass fractionation using SIMS analyses of a standard material. There is often a gradual drift in the mass fractionation with time, but this can be modelled by least-squares regression of the standard isotope ratios. Drift in the sample analyses is eliminated by using the relevant point on this regression line to calibrate each sample. The final precision of a corrected isotope ratio must take into account the scatter in both the sample and the standard data.

Keywords

analytical precisioncalibrationmass fractionationPoisson counting statisticssecondary ion mass spectrometrystable isotopes
Type
Research Article
Information
Mineralogical Magazine , Volume 64 , Issue 1 , February 2000 , pp. 59 - 83
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2000

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Footnotes

†

Present address: School of Applied Geology, Curtin University of Technology, GPO Box U1987, Perth, WA 6845, Australia

References

Clifford, A.A. (1973) Multivariate Error Analysis. Applied Science Publishers, Barking, UK.Google Scholar
Deloule, E., Chaussidon, M. and Allé, P. (1992) Instrumental limitations for isotope measurements with a Caméca ims-3f ion microprobe: example of H, B, S and Sr. Chem. Geol., 101, 187–92.Google Scholar
Eiler, J.M., Valley, J.W., Graham, C.M. and Baumgartner, L.P. (1995 a) Ion microprobe evidence for the mechanisms of stable isotope retrogression in high-grade metamorphic rocks. Contrib. Mineral. Petrol., 118, 365–78.CrossRefGoogle Scholar
Eiler, J.M., Valley, J.W., Graham, C.M. and Baumgartner, L.P. (1995b) The oxygen isotope anomaly of a slowly cooled metamorphic rock. Amer. Mineral., 80, 757–64.CrossRefGoogle Scholar
Eiler, J.M., Graham, C.M. and Valley, J.W. (1997) SIMS analysis of oxygen isotopes: matrix effects in complex minerals and glasses. Chem. Geol., 138, 221–44.CrossRefGoogle Scholar
Fitzsimons, I.C.W., Harte, B., Chinn, I.L., Taylor, W.R. and Gurney, J.J. (1999) Extreme chemical variation in complex diamonds from George Creek, Colorado: a SIMS study of carbon isotope composition and nitrogen abundance. Mineral. Mag., 63, 857–78.CrossRefGoogle Scholar
Graham, C.M., Valley, J.W. and Winter, B.L. (1996) Ion microprobe analysis of 18O/16O in authigenic and detrital quartz in the St. Peter Sandstone, Michigan Basin and Wisconsin Arch, USA: contrasting diagenetic histories. Geochim. Cosmochim. Acta, 60, 5101–16.CrossRefGoogle Scholar
Harte, B. and Otter, M. (1992) Carbon isotope measurements on diamonds. Chem. Geol., 101, 177–83.Google Scholar
Harte, B., Fitzsimons, I.C.W., Harris, J.W. and Otter, M.L. (1999) Carbon isotope ratios and nitrogen abundances in relation to cathodoluminescence characteristics for some diamonds from the Kaapvaal Province, S. Africa. Mineral. Mag., 63, 829–856.CrossRefGoogle Scholar
Hervig, R.L., Williams, P., Thomas, R.M., Schauer, S.N. and Steele, I.M. (1992) Microanalysis of oxygen isotopes in insulators by secondary ion mass spectrometry. Int.. J. Mass Spectr. Ion Proc., 120, 45–63.CrossRefGoogle Scholar
Hervig, R.L., Williams, L.B., Kirkland, I.K. and Longstaffe, F.J. (1995) Oxygen isotope microanalyses of diagenetic quartz: possible low temperature occlusion of pores. Geochim. Cosmochim. Acta, 59, 2537–43.CrossRefGoogle Scholar
Hinton, R.W. (1995) Ion microprobe analysis in geology. Pp. 235–89 in: Microprobe Techniques in the Earth Sciences (Potts, P.J., Bowles, J.F.W., Reed, S.J.B. and Cave, M.R., editors). Mineralogical Society Series, Chapman & Hall, London.CrossRefGoogle Scholar
Kinny, P.D., Trautman, R.L., Griffin, B.J., Fitzsimons, I.C.W. and Harte, B. (in press) Carbon isotopic composition of microdiamonds. In: Proc. 7th Int. Kimberlite Conf. Google Scholar
Kyser, T.K. (1995) Micro-analytical techniques in stable-isotope geochemistry. Canad. Mineral., 33, 261–78.Google Scholar
Long, J.V.P. (1995) Microanalysis from 1950 to the 1990s. Pp. 1–48 in: Microprobe Techniques in the Earth Sciences (Potts, P.J., Bowles, J.F.W., Reed, S.J.B. and Cave, M.R., editors). Mineralogical Society Series, Chapman & Hall, London.Google Scholar
MacRae, N.D. (1995) Secondary-ion mass spectrometry and geology. Canad. Mineral., 33, 219–36.Google Scholar
Moore, D.S. and McCabe, G.P. (1993) Introduction to the Practice of Statistics, 2nd edition. W.H. Freeman and Co., New York.Google Scholar
Potts, P.J. (1987) A Handbook of Silicate Rock Analysis. Blackie, Glasgow.CrossRefGoogle Scholar
Reed, S.J.B. (1989) Ion microprobe analysis – a review of geological applications. Mineral. Mag., 53, 3–24.CrossRefGoogle Scholar
Riciputi, L.R. and Paterson, B.A. (1994) High-spatial resolution measurement of O isotope ratios in silicates and carbonates by ion microprobe. Amer. Mineral., 79, 1227–30.Google Scholar
Shimizu, N. and Hart, S.R. (1982) Isotope fractionation in secondary ion mass spectrometry. J. Appl. Phys., 53, 1303–11.CrossRefGoogle Scholar
Slodzian, G. (1980) Microanalyzers using secondary ion emission. Adv. Electronics Electron Phys. Suppl., 13B, 1–44.Google Scholar
Slodzian, G., Lorin, J.C. and Havette, A. (1980) Isotopic effect on the ionization probabilities in secondary ion emission. J. Physique Lett., 41, L555–8.CrossRefGoogle Scholar
Smith, M.P. and Yardley, B.W.D. (1996) The boron isotopic composition of tourmaline as a guide to fluid processes in the SW England orefield: an ion microprobe study. Geochim. Cosmochim. Acta, 60, 1415–27.CrossRefGoogle Scholar
Storms, H.A. and Peterson, C.L. (1994) Contributions of deadtime and mass bias uncertainties to isotopic composition measurement error. Pp. 39–44 in: Secondary Ion Mass Spectrometry: SIMS IX (Benninghoven, A. et al., editors). John Wiley & Sons, Chichester, UK.Google Scholar
Valley, J.W. and Graham, C.M. (1991) Ion microprobe analysis of oxygen isotope ratios on granulite facies magnetites: diffusive exchange as a guide to cooling history. Contrib. Mineral. Petrol., 109, 38–52.CrossRefGoogle Scholar
Valley, J.W., Graham, C.M., Harte, B., Eiler, J.M. and Kinny, P.D. (1998) Ion microprobe analysis of oxygen, carbon and hydrogen isotope ratios. SEG Reviews in Economic Geology, 7, 73–98.Google Scholar
Wackerly, D.D., Mendenhall, W. and Scheaffer, R.L. (1996) Mathematical Statistics with Applications, 5th edition. Wadsworth Publishing Co., Belmont, CA, USA.Google Scholar
Zinner, E. (1989) Isotopic measurements with the ion microprobe. US Geol. Surv. Bull., 1890, 145–62.Google Scholar
Zinner, E., Fahey, A.J. and McKeegan, K.D. (1986) Characterization of electron multipliers by charge distributions. Pp. 170–2 in: Secondary Ion Mass Spectrometry: SIMS V (Benninghoven, A. et al., editors). Springer-Verlag, Berlin.CrossRefGoogle Scholar