Identification and quantification of known polycyclic aromatic hydrocarbons and pesticides in complex mixtures using fluorescence excitation-emission matrices and parallel factor analysis.
Polycyclic aromatic hydrocarbons (PAHs) and pesticides are among the most widespread organic contaminants in aquatic environments. Because of their aromatic structure, PAHs and pesticides have intrinsic fluorescence properties in the ultraviolet/blue spectral range. In this study, excitation-emission matrix (EEM) fluorescence spectroscopy and parallel factor (PARAFAC) analysis were used to characterise and discriminate fluorescence signatures of nine PAHs and three pesticides at the μg L(-1) level in the presence of humic substances (0.1-10 mgCL(-1)). These contaminants displayed a diversity of fluorescence signatures regarding spectral position (λEx: 220-335 nm, λEm: 310-414 nm), Stokes shift (39-169 nm) and number of peaks (1-8), with detection limits ranging from 0.02 to 1.29μgL(-1). The EEM/PARAFAC method applied to mixtures of PAHs with humic substances validated a seven-component model that included one humic-like fluorophore and six PAH-like fluorophores. The EEM/PARAFAC method applied to mixtures of pesticides with humic substances validated a six-component model that included one humic-like fluorophore and three pesticide-like fluorophores. The EEM/PARAFAC method adequately quantified most of the contaminants for humic substance concentrations not exceeding 2.5 mg CL(-1). The application of this method to natural (marine) samples was demonstrated through (1) the match between the Ex and Em spectra of PARAFAC components and the Ex and Em spectra of standard PAHs, and (2) the good linear correlations between the fluorescence intensities of PARAFAC components and the PAH concentrations determined by GC-MS.
Aix-Marseille Université, Université du Sud Toulon-Var, CNRS/INSU, IRD, Mediterranean Institute of Oceanography (MIO), UM 110, 13288 Marseille Cedex 09, France. Electronic address: nicolas.ferretto@univ-amu.fr.
Nicolas
N
Ferretto
Aix-Marseille Université, Université du Sud Toulon-Var, CNRS/INSU, IRD, Mediterranean Institute of Oceanography (MIO), UM 110, 13288 Marseille Cedex 09, France.
Marc
M
Tedetti
Aix-Marseille Université, Université du Sud Toulon-Var, CNRS/INSU, IRD, Mediterranean Institute of Oceanography (MIO), UM 110, 13288 Marseille Cedex 09, France.
Catherine
C
Guigue
Laboratoire des PROcessus de Transferts et d'Echanges dans l'Environnement (PROTEE), Université de Toulon, BP 20132, 83957 La Garde Cedex, France.
Stéphane
S
Mounier
Laboratoire des PROcessus de Transferts et d'Echanges dans l'Environnement (PROTEE), Université de Toulon, BP 20132, 83957 La Garde Cedex, France.
Roland
R
Redon
Aix-Marseille Université, Université du Sud Toulon-Var, CNRS/INSU, IRD, Mediterranean Institute of Oceanography (MIO), UM 110, 13288 Marseille Cedex 09, France.
Madeleine
M
Goutx
D005163:Factor Analysis, Statistical; D005453:Fluorescence; D005456:Fluorescent Dyes; D006812:Humic Substances / Q000032:analysis; D010575:Pesticides / Q000032:analysis* / Q000737:chemistry*; D011084:Polycyclic Aromatic Hydrocarbons / Q000032:analysis* / Q000737:chemistry*; D012623:Seawater / Q000737:chemistry; D013050:Spectrometry, Fluorescence / Q000379:methods*; D014874:Water Pollutants, Chemical / Q000032:analysis* / Q000737:chemistry*
D005456:Fluorescent Dyes; D006812:Humic Substances; D010575:Pesticides; D011084:Polycyclic Aromatic Hydrocarbons; D014874:Water Pollutants, Chemical
Contaminants; EEM; Fluorescence; PAHs; PARAFAC; Pesticides