A green chemometrics-assisted fluorimetric detection method for the direct and simultaneous determination of six polycyclic aromatic hydrocarbons in oil-field wastewaters

Oil-field wastewaters contain high level of polycyclic aromatic hydrocarbons (PAHs), which have to be analyzed to assess the environmental effects before discharge. In this work, a green fluorimetric detection method that combines excitation-emission matrix (EEM) fluorescence with parallel factor analysis (PARAFAC) algorithm was firstly developed to achieve the direct and simultaneous determination of six U.S. EPA PAHs in two different kinds of complex oil-field wastewaters. Due to the distinctive “second-order advantage”, neither time-consuming sample pretreatments nor toxic organic reagents were involved in the determination. By using the environment-friendly “mathematical separation” of PARAFAC, satisfactory quantitative results and reasonable spectral profiles for six PAHs were successfully extracted from the total EEM signals of oil-field wastewaters without need of chromatographic separation. The limits of detection of six PAHs were in the range of 0.09–0.72   ng   mL −1 , and the average spiked recoveries were between (89.4   ±   4.8)% and (109.1   ±   5.8)%, with average relative predictive errors <2.93%. In order to further confirm the accuracy of the proposed method, the same batch oil-field wastewater samples were analyzed by the recognized GC–MS method. t -test demonstrated that no significant differences exist between the quantitative results of the two methods. Given the advantages of green, fast, low-cost and high-sensitivity, the proposed method is expected to be broadened as an appealing alternative method for multi-residue analysis of overlapped PAHs in complex wastewater samples.