Identification of chlorinated fatty acids in fish by gas chromatography/mass spectrometry with negative ion chemical ionization of pentafluorobenzyl esters.
This paper reports the development of a technique for identifying and confirming chlorinated fatty acids previously detected in fish by gas chromatography (GC) with halogen-specific detection (XSD). Fatty acid methyl esters (FAMEs) including chlorinated FAMEs within fractions of reversed-phase high-performance liquid chromatography of transesterified fish extracts were derivatized to pentafluorobenzyl esters, which were subjected to GC/mass spectrometry (MS) with negative ion chemical ionization (NICI). Pentafluorobenzyl esters displayed reasonably good GC characteristics, a very high ionization efficiency and a low degree of fragmentation. Chloride ion chromatograms extracted at m/z 35 and 37 from full scans were utilized for locating traces of chlorinated unknowns in the GC elution profile so that their mass spectra could be readily displayed. Significant ions displayed in the mass spectrum scanned in a narrow range of retention time where a chlorinated unknown was located were evaluated using ion chromatograms extracted at the m/z of these ions. The chromatographic peaks of those ions derived from the analyte were expected to center at that specific retention time, whereas those originating from matrix compounds were not. The isotopic patterns of chlorinated ions were also examined against their theoretical relative abundances. Using this approach, three metabolism-related dichloro fatty acids previously identified by GC/XSD in filet extracts of white sucker sampled downstream from a bleached kraft pulp mill were confirmed: dichlorooctadecanoic, dichlorohexadecanoic and dichlorotetradecanoic acids. In addition, an isomer of dichlorotetradecanoic acid was found in a reference fish sample. As sample preparation is critical in this application, improved conditions for hydrolysis and pentafluorobenzyl esterification are also discussed.
Zhuang
Wenshan
W
Department of Chemical Engineering and Applied Chemistry, University of Toronto, 200 College Street, Toronto, Ontario M5S 3E5, Canada. bzhuang@taro.ca
McKague
A Bruce
AB
Reeve
Douglas W
DW
Carey
John H
JH
D000818:Animals; D002713:Chlorine / Q000737:chemistry*; D004952:Esters / Q000737:chemistry*; D005227:Fatty Acids / Q000032:analysis* / Q000737:chemistry*; D005399:Fishes; D005618:Fresh Water; D008401:Gas Chromatography-Mass Spectrometry / Q000379:methods*; D007220:Industrial Waste; D008297:Male; D009227:Myristic Acids / Q000032:analysis / Q000737:chemistry
C400744:5,6-dichloromyristic acid; D004952:Esters; D005227:Fatty Acids; D007220:Industrial Waste; D009227:Myristic Acids; D002713:Chlorine