Nonparametric estimation of measurement uncertainty arising from sampling.

BACKGROUND: Increasingly, measurement uncertainty has been used by pure and applied analytical chemistry to ensure decision-making in commercial transactions and technical-scientific applications. Until recently, it was considered that measurement uncertainty boiled down to analytical uncertainty; however, over the last two decades, uncertainty arising from sampling has also been considered. However, the second version of the EURACHEM guide, published in 2019, assumes that the frequency distribution is approximately normal or can be normalized through logarithmic transformations, without treating data that deviate from the normality. RESULTS: Here, six examples (four from Eurachem guide) were treated by classical ANOVA and submitted to an innovative nonparametric approach for estimating the uncertainty contribution arising from sampling. Based on bootstrapping method, confidence intervals were used to guarantee metrological compatibility between the uncertainty ratios arising from the results of the traditional parametric tests and the unprecedented proposed nonparametric methodology. SIGNIFICANCE AND NOVELTY: The present study proposed an innovative methodology for covering this gap in the literature based on nonparametric statistics (NONPANOVA) using the median absolute deviation concepts. Supplementary material based on Excel spreadsheets was developed, assisting users in the statistical treatment of their real examples.

Data reconciliation connected to guard bands to set specification limits related to risk assessment for radiopharmaceutical activity.

Radiopharmaceuticals have been used to diagnose several diseases, particularly because the procedure is non-invasive. However, it is important that the correct amount of radiopharmaceutical is used to avoid inaccurate diagnostic results and suboptimal therapeutic outcomes. The amount of the radiopharmaceutical is measured when produced (by the supplier) and a second time (by the receiver), before it's use. When measured at the receiver, the result is corrected for its normal radioactivity decay. Even then, it is possible that both measurements should be considered nominal different or even statistically different when compared through various statistical tools. This research combines two innovative techniques in the field of clinical metrology. The first technique is data reconciliation, which not only enhances measurement accuracy but also reduces measurement uncertainty. The second technique involves using uncertainty information to establish specification limits for compliance assessments. In this way, our proposal aimed to minimize the risk of making incorrect decisions regarding the conformity of the concentration of radiopharmaceutical activity, that is, rejecting an item or batch that is within specification or accepting an item or batch that is outside of specification. A spreadsheet, based on these metrology fundamentals, is available to help the user with the calculations, presenting numerical and graphical results for some common radioisotopes. Reliable specification limits can be calculated and used to determine if the radiopharmaceutical is in accordance with its proposed application.

Drawing Attention to the Measurement Uncertainty Arising from Sampling in Chemical and Physicochemical Analyses: An Overview.

Sometimes, analytical chemicals forget that the measurement process begins with the selection of the sample; thus, it must be understood that the measurement uncertainty is constituted by the association of the uncertainty arising from the sampling and the uncertainty arising from the traditional analytical process, that which is carried out in the laboratory. The analytical process is well-controlled, so its uncertainty is well defined; however, the uncertainty arising from sampling, for not having this controlled environment, is often not evident, so that there is still no culture to consider it for the calculation of measurement uncertainty. This study discusses the importance of the sampling uncertainty concerning the analytical uncertainty and details the current approaches available in the literature, such as the classical analysis of variance, the robust analysis of variance, and the range statistics. Moreover, this work highlights the recent manuscripts that are using these mentioned approaches, correlating them to the matrices, chemical and physical-chemical analytes, and analytical techniques. Finally, some case studies using the uncertainty information in compliance assessment show that the measurement uncertainty arising from sampling in chemical and physicochemical analyses cannot always be neglected.

Shedding Light on Data Reconciliation Techniques Applied to Analytical Chemistry.

Historically, owing to the increase in processing capacity over the years, validation and adjustment of measurements have become imperative. In particular, concerning discussions related to data and results in analytical chemistry, there is always a need to improve their reliability. The data reconciliation technique has the objective of using measurement redundancies to obtain the best estimate of the true value and, consequently to minimize its uncertainty. Unfortunately, this powerful tool is less known and used by analytical chemists compared to other areas. This approach can be satisfactorily performed in decision-making procedures that focus on chemical analysis, chemometrics, biochemistry analysis, forensics, and environmental sciences, such as in a characterization study, regarding conformance or nonconformance with the specification, doubts related to the malfunctioning of meters and about the compatibility of test methods. This work discusses and sheds light on the importance of data reconciliation, including data reconciliation statistics and application of the technique, traditional data reconciliation in analytical chemistry, principal component analysis based on data reconciliation in analytical chemistry, and fuzzy data reconciliation in analytical chemistry.

Modified and Optimized Glass Electrode for pH Measurements in Hydrated Ethanol Fuel.

One of the quality control parameters of ethanol fuel is pH, established by the Brazilian standard ABNT NBR 10891, whose scope is specific for hydrated ethanol fuel, and by the American standard ASTM D 6423, which focuses on anhydrous ethanol fuel. This study presented a modified and optimized structure using a single solvent, both for the glass electrode and the external reference electrode, to minimize the presence of the liquid junction potential for measuring the pH of hydrated ethanol fuel. The Box-Behnken design enabled us to determine the optimal condition expected for the new measurement system, which was compared with the systems proposed by the standard references and the turning range of acid-base indicators using parametric and nonparametric tests. The results revealed that the pH values obtained by the different systems are statistically different, and that only the values obtained by this proposal are suitable for the pH range found by the indicators. The optimized electrode presented an adequate response sensitivity to the Nernst equation, having an operational behavior adequate for the modified and optimized glass electrode for pH measurements in hydrated ethanol fuel.