A reassessment of the quasi-simultaneous arrival effect in secondary ion mass spectrometry

Quasi-simultaneous arrival (QSA) effects in secondary ion mass spectrometry can create mass-independent inaccuracies in isotope measurements when using electron multiplier detectors (EMs). The simple Poisson statistical model of QSA does not explain most experimental data. We present pulse-height distributions (PHDs) and time-series measurements to better study QSA. Our data show that PHDs and the distribution of multiple arrivals on the EM are not consistent with the Poisson model. Multiple arrivals are over-dispersed compared to Poisson and are closer to a negative binomial distribution. Through an emission–transmission–detection model we show that the QSA correction depends on the non-Poisson emission of multiple secondary ions, the secondary ion energy distribution, and other factors, making an analytical correction impractical. A standards-based correction for QSA is the best approach, and we show the proper way to calculate standards-normalized δ values to minimize the effect of QSA.