Monte Carlo bottom-up evaluation of global instrumental quantification uncertainty: Flexible and user-friendly...

Many instrumental methods of analysis require the daily collection of calibrator signals to calibrate their response. The quality of quantifications based on these calibrations depends on calibrators quality, instrumental signal performance and regression model fitness. Linear Ordinary Least Squares (LOLS), Linear Weighted Least Squares (LWLS) or Linear Bivariate Least Squares (LBLS) regression models can be used to calibrate and evaluate the uncertainty from instrumental quantifications, but require the fulfilment of some assumptions, namely, constant signal variance (LOLS), high calibrators quality (LOLS and LWLS) and linear variation of instrumental signal with calibrator values. The LBLS is flexible regarding calibrator values uncertainty and correlation but requires the determination of calibrator values and signals covariances. This work developed a computational tool for the bottom-up evaluation of global instrumental quantifications uncertainty which simulates calibrator values correlations from entered calibrators preparation procedure and simulates calibrators and samples signals precision from prior precision data, allowing accurate uncertainty evaluation from a few replicate signals of the daily calibration. The used signal precision models were built from previously observed repeatability variation throughout the calibration interval adjusted to daily precision condition from a residual standard deviation adjustment factor. This approach was implemented in a user-friendly MS-Excel file and was successfully applied to the analysis of As, Cd, Ni and Pb in marine sediment extracts by Absorption Spectroscopy. Evaluations were tested by the metrological compatibility of estimated and reference values of control standards for confidence levels of 95% and 99%. The success rates of the compatibility tests were statistically equivalent to the confidence level (p-value>0.01).