title: Chemometric-based determination of polycyclic aromatic hydrocarbons in aqueous samples using ultrasound-assisted emulsification microextraction combined to gas chromatography-mass spectrometry.
abstract: In the present research, ultrasonic-assisted emulsification-microextraction (USAEME) coupled with gas chromatography-mass spectrometry (GC-MS) has been proposed for analysis of thirteen environmental protection agency (EPA) polycyclic aromatic hydrocarbons (PAHs) in aqueous samples. Tetrachloroethylene was selected as extraction solvent. The main parameters of USAEME affecting the efficiency of the method were modeled and optimized using a central composite design (CCD). Under the optimum conditions (9μL for extraction solvent, 1.15% (w/v) NaCl (salt concentration) and 10min for ultrasonication time), preconcentration factor (PF) of the PAHs was in the range of 500-950. In order to have a comprehensive analysis, multivariate curve resolution-alternating least squares (MCR-ALS) as a second-order calibration algorithm was used for resolution, identification and quantification of the target PAHs in the presence of uncalibrated interferences. The regression coefficients and relative errors (REs, %) of calibration curves of the PAHs were in the satisfactory range of 0.9971-0.9999 and 1.17-6.59%, respectively. Furthermore, analytical figures of merit (AFOM) for univariate and second-order calibrations were obtained and compared. As an instance, the limit of detections (LODs) of target PAHs were in the range of 1.87-18.9 and 0.89-6.49ngmL(-1) for univariate and second-order calibration, respectively. Finally, the proposed strategy was used for determination of target PAHs in real water samples (tap and hookah waters). The relative recoveries (RR) and the relative standard deviations (RSDs) were 68.4-109.80% and 2.15-6.93%, respectively. It was concluded that combination of multivariate chemometric methods with USAEME-GC-MS can be considered as a new insight for the analysis of target analytes in complex sample matrices.
authors: Department of Chemistry, Faculty of Science, University of Tehran, Tehran, Iran.
authors: Mohammad
authors: M
authors: Ahmadvand
authors: Department of Chemistry, Faculty of Science, University of Tehran, Tehran, Iran. Electronic address: sereshti@ut.ac.ir.
authors: Hassan
authors: H
authors: Sereshti
authors: Department of Chemistry, Sharif University of Technology, P.O. Box 11155-3516, Tehran, Iran. Electronic address: h.parastar@sharif.edu.
authors: Hadi
authors: H
authors: Parastar
mesh_terms: D002138:Calibration; D008401:Gas Chromatography-Mass Spectrometry / Q000379:methods; D057230:Limit of Detection; D059627:Liquid Phase Microextraction; D011084:Polycyclic Aromatic Hydrocarbons / Q000032:analysis*; D000069453:Ultrasonic Waves; D014481:United States; D014867:Water / Q000737:chemistry*; D014874:Water Pollutants, Chemical / Q000032:analysis*
chemical_list: D011084:Polycyclic Aromatic Hydrocarbons; D014874:Water Pollutants, Chemical; D014867:Water
keywords: Central composite design; Gas chromatography–mass spectrometry; Multivariate curve resolution-alternating least squares; Polycyclic aromatic hydrocarbons; Ultrasound-assisted emulsification microextraction