title: Identifying and quantifying contaminants contributing to endogenous analytes in gas chromatography/mass spectrometry.
abstract: Contaminants from various sources including medical devices, laboratory materials and the environment, and analytical apparatus may contribute to their endogenous congeners at different stages of the analytical process. Here, an approach is reported for the identification and quantification of contaminating analytes in biological fluids by stable-isotope dilution gas chromatography/mass spectrometry (GC/MS) and gas chromatography/tandem mass spectrometry (GC/MS/MS) methods. This approach is based on the analysis of different sample volumes and determination of the peak area ratio (PAR) of the endogenous analyte to the stable-isotope labeled analogue serving as the internal standard. The PAR is obtained by selected-ion monitoring or selected-reaction monitoring of appropriate ions. Generation of PAR values that correlate inversely with the sample volume subjected to analysis reveals the existence of contamination. The extent of contamination is obtained by plotting the PAR of endogenous analyte to internal standard versus the reciprocal of the sample volume analyzed. Examples are given for uncontaminated and contaminated endogenous analytes in biological samples, including nitrite and nitrate analyzed by GC/MS, and the fatty acid metabolites oleic acid oxide, oleic acid ethanol amide, and arachidonic acid ethanol amide analyzed by GC/MS/MS. Dependence of the PAR of endogenous analyte to its internal standard upon derivatization time reveals a unique kind of contamination that was identified in the GC/MS analysis of nitrate in plasma as pentafluorobenzyl ester. This kind of contamination occurs at the latest stage of GC/MS analysis and cannot be controlled by reference to the internal standard.
authors.affiliation: Institute of Clinical Pharmacology, Hannover Medical School, Hannover, Germany. tsikas.dimitros@mh-hannover.de
authors.forename: Dimitrios
authors.initials: D
authors.lastname: Tsikas
mesh_terms: D016477:Artifacts; D005227:Fatty Acids / Q000097:blood / Q000378:metabolism; D005464:Fluorobenzenes / Q000737:chemistry; D008401:Gas Chromatography-Mass Spectrometry / Q000379:methods* / Q000592:standards; D006801:Humans; D009566:Nitrates / Q000097:blood; D009573:Nitrites / Q000097:blood; D012015:Reference Standards
chemical_list: D005227:Fatty Acids; D005464:Fluorobenzenes; D009566:Nitrates; D009573:Nitrites