Optimization of Calibration Strategies for the Quantification of Volatile Compounds in Virgin Olive Oil

The quantification of volatile compounds in virgin olive oil poses several analytical challenges due to the existence of different concentrations, chemical families, and the possible matrix effect. Accurate quantification, using adequate methodological calibration and statistical procedures, is essential for obtaining reliable results. The aim of this work was to develop and validate an analytical-statistical approach for the quantification of volatile compounds in virgin olive oil. Therefore, several analytical parameters were determined for four calibrations. The ordinary least square (OLS) linear adjustment was selected over the weighted least square due to the homoscedasticity of the variable errors. Additionally, standard addition (AC) and AC with an internal standard (IS) exhibited greater variability, whereas external matrix-matched calibration (EC) was identified as the most reliable approach for quantifying volatile compounds in virgin olive oil. The employment of an IS did not improve the performance of the method in any case. Thus, based on the statistical results, the OLS linear adjustment with EC was selected as the best statistical-analytical approach for quantifying volatiles in olive oil matrices. The volatiles of nine virgin olive oil samples were quantified, applying different methodological calibrations, and no differences were detected, underscoring EC as a superior alternative.