Online Third-Order Liquid Chromatographic Data with Native and Photoinduced Fluorescence Detection for the...

Third-order liquid chromatographic data were generated online for the simultaneous quantitation of six organic environmental pollutants. The employed strategy consists in reducing the linear flow rate at the column outlet. A postcolumn UV reactor and a fluorimetric detector allowed to properly record both photoinduced and native excitation-emission fluorescence matrices (EEPIFMs and EEFMs, respectively). The obtained third-order liquid chromatography data were chemometrically processed with the multivariate curve resolution-alternating least-squares model. The sensitivity of the overall analytical method was enhanced by a very simple solid-phase extraction with C18 membranes, to be able to successfully apply it to natural water samples tested as real matrices. Favorable detection limits for the investigated pollutants, ranging from 0.02 to 0.27 ng mL^-1, were attained, with relative prediction errors between 2 and 7%. Since the studied samples contain uncalibrated interferents, the applied strategy achieves the second-order advantage. Implications regarding the potential achievement of the third-order advantage are discussed.