Comparison of second-order multivariate methods for screening and determination of PAHs by total fluorescence spectroscopy

• PARAFAC, MCR–ALS and U-PLS/RBL analyzed EEM samples of 10 PAHs and interferences.
• PARAFAC and MCR are best for fast qualitative and quantitative sample screening.
• Partial trilinear models and selectivity constraints crucial for complex EEM samples
• U-PLS/RBL is best for quantification but RBL step is critical and time intensive.

This work explores the feasibility of screening and determination of ten polycyclic aromatic hydrocarbons (PAHs) through excitation–emission fluorescence matrices (EEMs) and in the presence of interferences by using different second-order data analysis algorithms: parallel factor analysis (PARAFAC), multivariate curve resolution–alternating least squares (MCR–ALS), and unfolded partial least squares coupled to residual bilinearization (U-PLS/RBL).The scope of the proposed techniques is discussed for qualitative and quantitative analysis of the selected PAHs in the presence of interferences and sample matrix effects. The target compounds were 9 of the 16 United States Environmental Protection Agency (US-EPA) priority PAHs: fluoranthene, benzo[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenzo[a,h]anthracene, benzo[ghi]perylene, indeno[1,2,3-cd]pyrene, and one internal standard: 2-2′ binaphthyl.The suitability of these methods was compared under different chemical situations, where they were demonstrated to be powerful tools to resolve complex mixtures of analytes of similar structure in the presence of unexpected compounds. Qualitative and quantitative analysis of samples required the joint effort of the different algorithms to exploit the advantages of fast screening (PARAFAC and MCR–ALS) and accurate analyte determination (U-PLS/RBL) provided by the different methods.