Direct determination of five polycyclic aromatic hydrocarbons including fluorene, anthracene, phenanthrene, pyrene and fluoranthene was accomplished by excitation–emission matrix fluorescence coupled with chemometric methods based on an alternating trilinear decomposition (ATLD) algorithm. A uniform design and orthogonal design are proposed for the creation of the calibration set. Results showed that no significant difference in the recoveries for each of the PAHs was observed. Thus, both of the designs can be used for the calibration set. In addition, some statistical parameters and figures of merit, such as average recovery, root-mean-square error of prediction, sensitivity, and selectivity were investigated to evalute the performance of the proposed method. The results showed that fluoranthene was the most selective, whereas fluorene was more sensitive than any other compound. This method was also employed for the determination of samples of drinking water spiked with all these PAHs. It can be observed that the results were not as satisfying as those in synthetic samples due to the negative effects of humic acid or fulvic acid in drinking water.
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