On-line generation of third-order liquid chromatography–excitation-emission fluorescence matrix data. Quantitation of heavy-polycyclic aromatic hydrocarbons

For the first time, third-order liquid chromatography with excitation-emission fluorescence matrix detection (LC-EEFM) data were generated on-line and chemometrically processed for the simultaneous quantitation of the heavy-polycyclic aromatic hydrocarbons fluoranthene, pyrene, benz[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, and dibenz[a,h]anthracene. The applied experimental strategy is very simple, and is based on the reduction of the linear flow rate by fitting a larger diameter connecting-tube between the column outlet and the fluorimetric detector. In this way, EEFMs were successfully recorded on-line, without involving a large total analysis time. Because in the studied system quadrilinearity was fulfilled, four-way parallel factor (PARAFAC) analysis was applied for data processing. The second-order advantage, which is an intrinsic property of data of at least second-order, allowed the quantification of the analytes in interfering media. Moreover, resolution of the system with a high degree of collinearity was achieved thanks to the third-order advantage. In addition to a selectivity improvement, third-order/four-way calibration increased the sensitivity, with limits of detection in the range of 0.4 − 2.9 ng mL−1. After a solid-phase extraction procedure with C18 membranes, considerably lower concentrations (between 0.033–2.70 ng mL−1) were determined in real waters, with most recoveries in the range 90–106%.