Multivariate calibration of polycyclic aromatic hydrocarbon mixtures from excitation–emission fluorescence spectra Original Research Article

The excitation–emission fluorescence spectra (EEM) of mixtures of 10 polycyclic aromatic hydrocarbons (PAHs) have been analyzed using different multivariate calibration procedures (partial least squares regression, PLSR; and parallel factor analysis, PARAFAC). The compounds studied were anthracene, benz[a]anthracene, benzo[a]pyrene, chrysene, phenanthrene, fluoranthene, fluorene, naphthalene, perylene and pyrene. Several algorithms (PARAFAC, PLS1, PLS2, Tri-PLS1 and Tri-PLS2) were tested for the quantification of these compounds from the EEM spectra of a set of standards, at ng ml−1 levels. The best results were obtained by the application of a three-way multivariate calibration method (Tri-PLS2). This method was selected for the determination of samples of tap and mineral waters spiked with all these PAHs. Excitation and emission wavelength ranges were between 240 and 300 nm and 310 and 478 nm, respectively. In the working conditions, an EEM spectrum covering this range could be recorded in about 2 min.