A new model equation for determining the measurement result in standard addition experiments was derived and successfully applied to the quantitative determination of rhodium in automotive catalysts. Existing equations for standard addition experiments with gravimetric preparation were changed in order to integrate the novel idea of including the uncertainty associated with the standard into the model equation. Using this novel equation combined with the ordinary least squares algorithm for the regression line also yielded a new formula for the associated measurement uncertainty. This uncertainty accounts for the first time for the uncertainty associated with the standard. The derivation for the model equation and the resulting associated measurement uncertainty is shown for gravimetric standard addition experiments both with and without an internal standard.

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The determination of thermal diffusivity is at the heart of modern materials characterisation. The evaluation of the associated uncertainty is difficult because the determination is performed in an indirect way, in the sense that the thermal diffusivity cannot be measured directly. The well-known GUM uncertainty framework does not provide a reliable evaluation of measurement uncertainty for such inverse problems, because in that framework the underlying measurement model is supposed to be a direct relationship between the measurand (the quantity intended to be measured) and the input quantities on which the measurand depends. This paper is concerned with the development of a Bayesian approach to evaluate the measurement uncertainty associated with thermal diffusivity. A Bayesian model is first developed for a single thermogram and is then extended to the case of several thermograms obtained under repeatability and reproducibility conditions. This multi-thermogram based model is able to take into consideration a large set of influencing quantities that occur during the measurements and yields a more reliable uncertainty evaluation than the one obtained from a single thermogram. Different aspects of the Bayesian model are discussed, including the sensitivity to the choice of the prior distribution, the Metropolis-Hastings algorithm used for the inference and the convergence of the Markov chains.

In this paper we provide guidance on a Bayesian uncertainty evaluation for a large class of GUM measurement models covering linear and non-linear models. Bayesian analysis takes advantage of useful prior knowledge on the measurand, which is often available from a metrologist’s genuine expertise and opinion, or from previous experiments and which is neither taken into account by the GUM nor by its Supplement 1. For the considered class of measurement models, we establish the equivalence with the related statistical models and derive analytical expressions of the posterior distribution for an appropriate family of prior distributions, which allows one to gain insight into the result of the Bayesian uncertainty evaluation. We extend this work to the formulation of arbitrary prior distributions for the measurand and provide some guidance to set hyperparameter values within a class of priors based on elicitation techniques, so that the resulting priors reflect the prior knowledge. Posterior distributions are calculated by Markov Chain Monte Carlo methods. We apply the Bayesian uncertainty evaluation to the mass calibration example of Supplement 1 and compare our results with those obtained by the GUM and its Supplement 1. In order to study the impact of the choice of method for this example, we carry out a sensitivity analysis of the results with respect to the choice of prior. We show a virtually strong effect of the prior distribution which results in reduced uncertainty estimates for a small number of observations. When using noninformative priors, we obtain results comparable to those achieved by GUM-S1. Python code is made available that enables a Bayesian uncertainty evaluation also in other applications covered by the considered class of GUM measurement models.

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