RESUMO

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.

Assuntos

RESUMO

This paper analyzes 12 years of tropospheric ozone (O3) concentration measurements using robust techniques. The measurements were taken at an air quality monitoring station called Belisario, which is in Quito, Ecuador; the data collection time period was 1 January 2008 to 31 December 2019, and the measurements were carried out using photometric O3 analyzers. Here, the measurement results were used to build variables that represented hours, days, months, and years, and were then classified and categorized. The index of air quality (IAQ) of the city was used to make the classifications, and robust and nonrobust confidence intervals were used to make the categorizations. Furthermore, robust analysis methods were compared with classical methods, nonparametric methods, and bootstrap-based methods. The results showed that the analysis using robust methods is better than the analysis using nonrobust methods, which are not immune to the influence of extreme observations. Using all of the aforementioned methods, confidence intervals were used to both establish and quantify differences between categories of the groups of variables under study. In addition, the central tendency and variability of the O3 concentration at Belisario station were exhaustively analyzed, concluding that said concentration was stable for years, highly variable for months and hours, and slightly changing between the days of the week. Additionally, according to the criteria established by the IAQ, it was shown that in Quito, the O3 concentration levels during the study period were not harmful to human health.

RESUMO

In this paper, a robust analysis of nitrogen dioxide (NO2) concentration measurements taken at Belisario station (Quito, Ecuador) was performed. The data used for the analysis constitute a set of measurements taken from 1 January 2008 to 31 December 2019. Furthermore, the analysis was carried out in a robust way, defining variables that represent years, months, days and hours, and classifying these variables based on estimates of the central tendency and dispersion of the data. The estimators used here were classic, nonparametric, based on a bootstrap method, and robust. Additionally, confidence intervals based on these estimators were built, and these intervals were used to categorize the variables under study. The results of this research showed that the NO2 concentration at Belisario station is not harmful to humans. Moreover, it was shown that this concentration tends to be stable across the years, changes slightly during the days of the week, and varies greatly when analyzed by months and hours of the day. Here, the precision provided by both nonparametric and robust statistical methods served to comprehensively proof the aforementioned. Finally, it can be concluded that the city of Quito is progressing on the right path in terms of improving air quality, because it has been shown that there is a decreasing tendency in the NO2 concentration across the years. In addition, according to the Quito Air Quality Index, most of the observations are in either the desirable level or acceptable level of air pollution, and the number of observations that are in the desirable level of air pollution increases across the years.