title: Searching for non-target chlorinated pesticides in food by liquid chromatography/time-of-flight mass spectrometry.
abstract: In this study the unique and most salient features of liquid chromatography/time-of-flight-mass spectrometry (LC/TOFMS) were applied for the identification of non-target chlorinated pesticides in complex food extracts 'a priori', i.e., without the use of standards. The combination of high sensitivity full-scan spectra incorporating accurate mass measurements (routinely better than 2 ppm accuracy) of the protonated molecules with the evidence from resolved isotopic clusters provides the ability to obtain a reduced number of possible elemental compositions (typically 1-2). Databases were then used to find the identity of the suspected species using the elemental composition as a searching criterion. The accurate mass and the generated elemental composition of characteristic fragment ions of the suspected species provide further evidence for the proposed species. With this approach we have identified the following chlorinated pesticides in different market-purchased fruit and vegetable extracts: Chlorotoluron (tomato), iprodione (apple), and procymidone (grapes). Finally, the confirmation and quantitation of these suspected species were successfully accomplished with standards. Other unknown compounds could be partially identified based on the data obtained within this study. As an example, a chlorinated species ('m/z 311') is discussed; the elemental composition and possible structures were proposed and the analytical potential, advantages and disadvantages of the proposed approach critically discussed.
authors.affiliation: Pesticide Residue Research Group, Department of Hydrogeology and Analytical Chemistry, University of Almería, 04120 La Cañada de San Urbano, Almería, Spain. jfgreyes@ujaen.es
authors.forename: Juan F
authors.initials: JF
authors.lastname: García-Reyes
authors.forename: Imma
authors.initials: I
authors.lastname: Ferrer
authors.forename: E Michael
authors.initials: EM
authors.lastname: Thurman
authors.forename: Antonio
authors.initials: A
authors.lastname: Molina-Díaz
authors.forename: Amadeo R
authors.initials: AR
authors.lastname: Fernández-Alba
mesh_terms: D000465:Algorithms; D002853:Chromatography, Liquid / Q000379:methods*; D005504:Food Analysis / Q000379:methods*; D005506:Food Contamination / Q000032:analysis*; D005638:Fruit / Q000737:chemistry; D006843:Hydrocarbons, Chlorinated / Q000032:analysis*; D008832:Microchemistry / Q000379:methods; D008970:Molecular Weight; D010575:Pesticides / Q000032:analysis*; D019032:Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization / Q000379:methods*; D014675:Vegetables / Q000737:chemistry
chemical_list: D006843:Hydrocarbons, Chlorinated; D010575:Pesticides