APCI as an innovative ionization mode compared with EI and CI for the analysis of a large range of organophosphate esters using GC‐MS/MS

Abstract

Organophosphate esters (OPEs) are chemical compounds incorporated into materials as flame-proof and/or plasticizing agents. In this work, 13 non-halogenated and 5 halogenated OPEs were studied. Their mass spectra were interpreted and compared in terms of fragmentation patterns and dominant ions via various ionization techniques [electron ionization (EI) and chemical ionization (CI) under vacuum and corona discharge atmospheric pressure chemical ionization (APCI)] on gas chromatography coupled to mass spectrometry (GC-MS). The novelty of this paper relies on the investigation of APCI technique for the analysis of OPEs via favored protonation mechanism, where the mass spectra were mostly dominated by the quasi-molecular ion [M + H] . The EI mass spectra were dominated by ions such as [H PO ] , [M-R] , [M-Cl] , and [M-Br] , and for some non-halogenated aryl OPEs, [M] was also observed. The CI mass spectra in positive mode were dominated by [M + H] and sometimes by [M-R] , while in negative mode, [M-R] and more particularly [X] and [X ] were mainly observed for the halogenated OPEs. Both EI and APCI techniques showed promising results for further development of instrumental method operating in selective reaction monitoring mode. Instrumental detection limits by using APCI mode were 2.5 to 25 times lower than using EI mode for the non-brominated OPEs, while they were determined at 50-100 times lower by the APCI mode than by the EI mode, for the two brominated OPEs. The method was applied to fish samples, and monitored transitions by using APCI mode showed higher specificity but lower stability compared with EI mode. The sensitivity in terms of signal-to-noise ratio varying from one compound to another. Copyright © 2016 John Wiley & Sons, Ltd.

An Overview of Chemical Additives on (Micro)Plastic Fibers: Occurrence, Release, and Health Risks

“…Some soft ionization techniques such as electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) interfaces can effectively solve this limitation (Wang et al 2020 ). For example, Halloum et al ( 2017 ) found that the detection limits of GC-APCI-MS/MS were 2.5–25 and 50–100 times lower than those of GC-EI-MS/MS, respectively, for the quantification of non-brominated OPEs and brominated OPEs.…”

Development of an Atmospheric Pressure Chemical Ionization Interface for GC-MS

“…The ion source housing is normally open to ambient air or not sealed, and this causes high background signals and irreproducible conditions inside the ion source [ 12 , 13 ]. Therefore, the majority of these APCI sources show relative standard derivations of approximately 10 to 60% [ 14 , 15 , 16 , 17 ]. Hence, performance criteria for analytical methods are not always met, and the aim of this work was to develop a more reproducible APCI ion source for GC-MS instrumentation.…”

Characterizing chain‐end structures formed during initiation reactions of radical polymerization for MMA‐St‐BA terpolymer using pyrolysis‐gas chromatography/atmospheric pressure chemical ionization high‐resolution time‐of‐flight mass spectrometry

“…12 Because of the soft ionization nature of APCI, spectral data rich in molecular or molecule-related ion information are typically generated. [13][14][15][16][17][18][19] Successful applications of GC/APCI-TOFMS range from screening organic contaminants in water 20 to analyzing various components in pesticides 21 metabolites, [22][23][24] avocados, 25 pharmaceuticals, 26 and blood. 27 In this study, Py-GC/APCI-TOFMS was used for end-group analysis of an MMA-St-butyl acrylate (BA) terpolymer radically polymerized using AMBN as an initiator.…”