Improved quality control in gas chromatography interfaced to stable isotope ratio mass spectrometry by application of...

Compound-specific isotope analysis using gas chromatography interfaced to isotope ratio mass spectrometry (GC-IRMS) is a versatile technique for applications ranging from source appointment and the elucidation of biochemical pathways. When delta(13)C values are going to be determined, the sample is combusted to CO(2) and the resulting gas is analyzed relative to a standard with known stable carbon isotope ratio. With the combustion step any information on the identity of a peak is lost. Co-eluting compounds can no more be identified which can lead to significant alterations of the delta(13)C value of the analyte. For improvement of the QA/QC protocols in GC-IRMS, we used first, second, and third order derivative chromatography. The suitability of the technique was studied using mixtures of 2,3,3',4,4',5,5'-heptachloro-1'-methyl-1,2'-bipyrrole (Q1) and 2,2',4,5,5'-pentachlorobiphenyl (PCB 101). By application of different GC oven programs four scenarios ranging from baseline separation to full co-elution were obtained. Derivative chromatography enabled identification of the interference of Q1 with PCB 101 even when both peaks fully co-eluted. Although the delta(13)C values could not be determined from interfered scenarios, the use of derivative spectroscopy will help to prevent acceptance of incorrect data due to co-elutions. Derivative chromatography was finally used to study the peak purity of 2,2',3,4,4'-pentabromodiphenyl ether (BDE 85) in technical pentabromo diphenyl ether (DE-71). Already the first order derivative demonstrated that this key-BDE congener was interfered by a compound identified as 2,2',4,4',6,6'-hexabromodiphenyl ether (BDE 155).