Chemometric‐Assisted Determination of Benzo[a]pyrene (BaP) and Benzo[a]anthracene (BaA) in Water Samples Using Fluorescence and Commercial Membranes: A White Analytical Chemistry Approach

ABSTRACT This study evaluates different solid membranes to develop an analytical method for the immobilization of two priority PAHs, benzo[a]pyrene (BaP) and benzo[a]anthracene (BaA), followed by the measurement of excitation–emission fluorescence matrices (directly measured over the membrane) coupled to second‐order multivariate calibration. Commercially available membranes, such as nylon and C18, proved to be suitable supports for these purposes, especially for aqueous samples. The multivariate curve resolution‐alternating least squares (MCR‐ALS) algorithm showed adequate flexibility to fit the data and achieve the second‐order advantage, even in the presence of unmodeled interferences. Even though both membranes showed different selectivity, the developed method allows quantification of PAH at ng L −1 levels with a prediction error below 10%. The proposed methodology was successfully applied to spiked real water samples, demonstrating its suitability for detecting PAHs at trace levels. Finally, the proposed method was evaluated and compared with reported analytical approaches based on white analytical chemistry principles, showing remarkable analytical performance for monitoring PAHs in natural water samples.