Third-order calibration applied to process surfactant-modulated excitation-emission matrix four-way fluorescence data for the direct determination of four polycyclic aromatic hydrocarbons in oilfield produced water.

Fluorescence spectroscopy is a powerful tool to determine polycyclic aromatic hydrocarbons (PAHs) owing to the strong endogenous fluorescence of these compounds. However, the presence of unknown interferences and overlapped spectra hinders the accurate determination of PAHs in oilfield produced water. Moreover, surfactants frequently coexist in oilfield produced water and will seriously affect the fluorescence signals of PAHs. Herein, a new methodology applying third-order calibration to process four-way (4D) fluorescence data was proposed to solve these problems and achieve accurate determination of pyrene, fluorene, phenanthrene, and fluoranthene as an example in oilfield produced water. The methodology is based on excitation-emission matrix fluorescence modulated by different concentrations of sodium dodecyl benzene sulfonate (SDBS) in the analyzed samples. The 4D fluorescence data were processed by third-order calibration methods including four-way parallel factor analysis (4-PARAFAC) and alternating weighted residue constraint quadrilinear decomposition (AWRCQLD), and the results were compared with those of second-order calibration methods. It was proved that third-order calibration was capable of accurately identifying and quantifying PAHs together with SDBS in oilfield produced water, which has better quantitative results and figures of merit compared to second-order calibration. This study provided a new approach to generating 4D fluorescence data and opened up an avenue for the accurate determination of PAHs in complex oilfield produced water with surfactants.