SIMS stable isotope measurement: counting statistics and analytical precision

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 analyses 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.