ABSTRACT
Resumen Se evaluaron diferentes sistemas de medición para titulaciones ácido-base, con el propósito de determinar cuál presenta mejores características metrológicas. Estos sistemas incluyen volumetrías y gravimetrías, las cuales se combinaron con diferentes métodos de detección del punto de equivalencia: (i) potenciometría, (ii) indicador ácido-base y (iii) conductividad electrolítica. Este artículo propone una nueva aproximación para la estimación de la incertidumbre de medición asociada a la detección del punto de equivalencia. Los resultados indicaron que, para la determinación del punto de equivalencia, las incertidumbres más bajas se obtienen mediante el método potenciométrico en comparación con el método conductimétrico cuyo sesgo es hasta 78 veces mayor. Sin embargo, se encontró que el método potenciométrico es fuertemente dependiente de la resolución del instrumento y/o la cantidad de agente titulante que se adiciona en la cercanía al punto de equivalencia. También se encontró que la incertidumbre disminuye cerca del 40% empleando métodos gravimétricos en comparación con los volumétricos. Al realizar la evaluación del sesgo de los sistemas de medición acorde con la guía ISO 33:2015, los resultados mostraron que, de los métodos evaluados, el método gravimétrico con detección potenciométrica presentó las mejores características metrológicas, pues se obtuvieron sesgos e incertidumbres menores.
Abstract Different measurement systems for acid-base titrations were evaluated to determine which one had the best metrological characteristics. These systems included volumetric and gravimetric titrations, which were combined with different detection systems: (i) potentiometry, (ii) acid-base indicator, and (iii) electrolytic conductivity. This article proposes a new approach for estimating the measurement uncertainty associated with the detection of the equivalence point. The results showed that, for the determination of the equivalence point, the lowest uncertainties were obtained by the potentiometric method in comparison with the conductometric method, whose bias was 78 times higher. The potentiometric method, however, was strongly dependent on the instrument resolution and/or the titrant amount that is added close to the equivalence point. It was also found that uncertainty decreases about 40% using gravimetric methods as compared to volumetric methods. When performing bias evaluation of the measurement systems according to the ISO 33:2015 guide, results showed that, among the evaluated methods, the gravimetric method with potentiometric detection presented the best metrological characteristics, with the lowest biases and uncertainties.
Resumo Foram avaliados diferentes sistemas de medida para titulações ácido-base, a fim de determinar quais possuem as melhores características metrológicas. Estes sistemas incluem titulações e gravimétricas, que foram combinadas com diferentes sistemas de detecção do ponto de equivalência: (i) potenciometria, (ii) indicador ácido-base e (iii) condutividade electrolítica. Este artigo propõe uma nova abordagem para estimar a incerteza de medição associada à detecção do ponto de equivalência. Os resultados indicaram que, para a determinação do ponto de equivalência, as incertezas mais baixas são obtidas pelo método potenciométrico enquanto que a incerteza do método condutométrico é até 78 vezes maior que a obtida pela potenciometria. Além disso, a potencimetria é altamente dependente da resolução do instrumento e/ou da quantidade de titulante para ser adicionado na proximidade com o ponto de equivalência. Também verificou-se que a incerteza diminui em torno de 40% utilizando métodos gravimétricos. De acordo à guia de norma ISO 33:2015, os resultados mostraram que os métodos de titulação ácido-base avaliados gravimetricamente com detecção potenciométrica proporcionaram as melhores características de metrologia, porque obtiveram os menores distorções e incertezas.
ABSTRACT
A simple extraction, rapid routine method for the simultaneous determination of sorbic acid, natamycin and tylosin in Dulce de leche, a traditional South American product, by liquid chromatography-tandem mass spectrometry has been developed and fully validated. The limits of detection were set to 24.41mgkg(-1) (sorbic acid), 0.10mgkg(-1) (natamycin) and 2µgkg(-1) (tylosin). Recoveries ranged from 95% to 110%. Proportionally, internal standardization was more efficient than external standard, resulting in a smaller measurement of uncertainty. In total, 35 commercial samples from Brazil, Argentina and Uruguay have been assessed. The proposed method was tested on other dairy desserts, demonstrating to be versatile. Although tylosin was not detected in any sample, a high rate of non-compliance was found, with 67.39% of samples above the maximum allowed for sorbic acid and a maximum concentration of 2105.36±178.60mgkg(-1). In two samples, natamycin was irregularly found.
Subject(s)
Chromatography, Liquid/methods , Dairy Products/analysis , Food Preservatives/analysis , Natamycin/analysis , Sorbic Acid/analysis , Tandem Mass Spectrometry/methods , Tylosin/analysisABSTRACT
A sub-minute capillary zone electrophoresis (CZE) method was optimized and a simple sample preparation procedure based on the extraction of the analytes with water and sodium tetraborate was developed for the simultaneous determination of nitrate and nitrite levels in meat products. The background electrolyte (BGE) was composed of 20mmolL(-1) perchloric acid and 65mmolL(-1) ß-alanine at pH3.83. Thiocyanate was used as the internal standard. The proposed method was validated and the uncertainty estimated according to Eurachem guidelines. The run time was only 30s, allowing analyzing more than 25samples/h, the good analytical performance confirms the suitability of the method for the analysis of meat products. One sample presented residual nitrite levels above the limit established by MERCOSUL legislation (150mgkg(-1)). The use of a fast method in association with a simple sample preparation step means that this procedure represents a possible alternative to fulfill the demand for high throughput in routine laboratory analysis.