Simultaneous Determination of Pesticides in Fruits by Using Second-Order Fluorescence Data Resolved by Unfolded Partial Least-Squares Coupled to Residual Bilinearization

Abstract

In the present work, a chemometric-assisted spectrofluorimetric method has been developed for the simultaneous determination of natural fluorescent pesticides, carbaryl, carbendazim, and thiabendazole, in orange and banana. Only a simple extraction with methanol was required as sample pretreatment. Emission-excitation fluorescence matrices were obtained and resolved by using a second-order multivariate calibration method based on unfolded partial least-squares combined with residual bilinearization (U-PLS/RBL) for achieving “second-order advantage.” In this way, pesticides were determined in fruits even in the presence of inner filter effects, background interactions, strong spectral overlapping, and unexpected components. U-PLS can cope with effects that cause trilinearity loss such as, inner filter effects, including background in the calibration set; meanwhile, RBL allows to resolve the presence of unexpected components. The extraction technique was validated against a commonly applied technique based on the use of ethyl acetate and sodium sulfate. Besides, results obtained for real samples were statistically compared with those obtained by using HPLC. LODs of 0.038, 0.054, and 0.018 mg·kg−1 and 0.044, 0.072, and 0.020 mg·kg−1 were obtained for carbaryl, carbendazim, and thiabendazole in banana and orange samples, respectively; values were in accordance with the MRLs (Maximum Residue Limits) established by different official control organizations such as National Food Safety and Quality Service (SENASA), Codex Alimentarius (based on Food and Agriculture Organization (FAO) of the United Nations and World Health Organization (WHO), and Environmental Protection Agency (EPA).