title: Determination of organophosphate flame retardants and plasticizers in lipid-rich matrices using dispersive solid-phase extraction as a sample cleanup step and ultra-high performance liquid chromatography with atmospheric pressure chemical ionization mass spectrometry.
abstract: A fast, robust and highly sensitive analysis method for determination of trace levels of organophosphate ester (OPE) flame retardants and plasticizers in lipid-rich samples was presently developed, and based on ultra-high performance liquid chromatography-tandem mass spectrometry coupled to a positive atmospheric pressure chemical ionization source (UHPLC-MS/MS-APCI(+)). The target OPEs in the sample were extracted from the biota samples, such as egg and liver, by ultrasonic extraction, and cleaned up further by dispersive solid phase extraction (d-ESP). As a result, background contamination was largely reduced. Different dispersive ESP sorbents were tested and primary secondary amine (PSA) bonded silica sorbents showed the best recoveries for these target OPEs. The recoveries obtained were in the range 54-113% (RSD<17%), with method limits of quantification (MLOQs) ranging between 0.06 and 0.29ng/g in egg, and 0.05 and 0.50ng/g w.w. in liver sample. The matrix effects (MEs) associated with using APCI(+) and ESI(+) sources were investigated. APCI(+) showed much less ion suppression than ESI(+) for the determination of these OPEs. For egg and liver samples, the APCI(+) ME values ranged from 40% to 94%, while ESI(+) ME values ranged from 0% to 36%. Although APCI(+) was used for the determination of OPEs, the ionization mechanism might mainly be a thermospray ionization process. This UHPLC-MS/MS-APCI(+) method showed good response linearity for calibration (R2>0.99). The proposed method was applied to real environmental bird egg and fish samples, where several OPE were quantifiable and different OPE patterns was observed between samples.
authors.affiliation: Wildlife and Landscape Science Directorate, Science and Technology Branch, Environment Canada, National Wildlife Research Centre, Carleton University, 1125, Colonel By Dr. (Raven Road), Ottawa, ON K1A 0H3, Canada. Electronic address: shaogang.chu@ec.gc.ca.
authors.forename: Shaogang
authors.initials: S
authors.lastname: Chu
authors.affiliation: Wildlife and Landscape Science Directorate, Science and Technology Branch, Environment Canada, National Wildlife Research Centre, Carleton University, 1125, Colonel By Dr. (Raven Road), Ottawa, ON K1A 0H3, Canada. Electronic address: robert.letcher@ec.gc.ca.
authors.forename: Robert J
authors.initials: RJ
authors.lastname: Letcher
keywords: Dispersive solid phase extraction; Egg, fish and liver samples; Flame retardants; Organophosphate esters; Ultra-high performance liquid chromatography-tandem mass spectrometry