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It has been reported that isotope fractionation can occur on gaschromatography (GC), yet little is known about concurrent dual-elements isotopefractionations on GC. Revelation of concurrent two-dimensional carbon andchlorine/bromine isotope fractionations of halogenated organic compounds (HOCs)on GC may be of important significance for compound-specific isotope analysis(CSIA). This study presents an in-depth investigation of the two-dimensional Cand Cl/Br isotope fractionations of HOCs on GC using GC-double focusmagnetic-sector high resolution mass spectrometry (GC-DFS-HRMS). Thetwo-dimensional C and Cl/Br isotope fractionations of four organochlorines andfour bromobenzenes on GC were simultaneously measured by GC-DFS-HRMS. Theisotope fractionations were evaluated with isotope ratios, relative variationsof isotope ratios and isotope fractionation extents. All the HOCs exhibitedsignificant inverse C and Cl/Br isotope fractionations. The isotopefractionations were significant in both ends of chromatographic peaks, whilethe isotope ratios in center retention-time segments were the closest tocomprehensive isotope ratios in the whole peaks. Significant correlationsbetween C isotope fractionation and Cl/Br isotope fractionation were observed,indicating that the isotope fractionations might have strong relationshipsand/or be dominated by similar factors. Relevant mechanisms for thetwo-dimensional C and Cl/Br isotope fractionations were tentatively proposed onbasis of a modified two-film model and the theories related to zero pointenergy. The results of this study gains new insights into concurrenttwo-dimensional isotope fractionation behaviors of HOCs during physicalprocesses, and are conducive to CSIA studies involving C, Cl and Br forobtaining high-quality data, particularly to dual-elements CSIA of C and Cl/Br.

analytica chimica acta

Simultaneous observation of concurrent two-dimensional carbon and  chlorine/bromine isotope fractionations of halogenated organic compounds on  gas chromatography