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Compound‐specific hydrogen isotope analysis of fluorine‐, chlorine‐, bromine‐ and iodine‐bearing organics using gas chromatography–chromium‐based high‐temperature conversion (Cr/HTC) isotope ratio mass spectrometry
Author(s) -
Renpenning Julian,
Schimmelmann Arndt,
Gehre Matthias
Publication year - 2017
Publication title -
rapid communications in mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.528
H-Index - 136
eISSN - 1097-0231
pISSN - 0951-4198
DOI - 10.1002/rcm.7872
Subject(s) - chemistry , mass spectrometry , isotope ratio mass spectrometry , chromium , hydrogen , gas chromatography , isotope fractionation , bromine , fractionation , analytical chemistry (journal) , isotope analysis , halogen , chlorine , chromatography , organic chemistry , ecology , alkyl , biology
Rationale The conventional high‐temperature conversion (HTC) approach towards hydrogen compound‐specific isotope analysis (CSIA) of halogen‐bearing (F, Cl, Br, I) organics suffers from incomplete H 2 yields and associated hydrogen isotope fractionation due to generation of HF, HCl, HBr, and HI byproducts. Moreover, the traditional off‐line combustion of highly halogenated compounds results in incomplete recovery of water as an intermediary compound for hydrogen isotope ratio mass spectrometry (IRMS), and hence also leads to isotope fractionation. This study presents an optimized chromium‐based high‐temperature conversion (Cr/HTC) approach for hydrogen CSIA of various fluorinated, chlorinated, brominated and iodinated organic compounds. The Cr/HTC approach is fast, economical, and not affected by low H 2 yields and associated isotope fractionation. Methods The performance of the modified gas chromatography/chromium‐based high‐temperature conversion (GC‐Cr/HTC) system was monitored and optimized using an ion trap mass spectrometer. Quantitative conversion of organic hydrogen into H 2 analyte gas was achieved for all halogen‐bearing compounds. The corresponding accuracy of CSIA was validated using (i) manual dual‐inlet (DI)‐IRMS after off‐line conversion into H 2 , and (ii) elemental analyzer (EA)‐Cr/HTC‐IRMS (on‐line conversion). Results The overall hydrogen isotope analysis of F‐, Cl‐, Br‐ and I‐bearing organics via GC‐Cr/HTC‐IRMS achieved a precision σ ≤ 3 mUr and an accuracy within ±5 mUr along the VSMOW‐SLAP scale compared with the measured isotope compositions resulting from both validation methods, off‐line and on‐line. The same analytical performance as for single‐compound GC‐Cr/HTC‐IRMS was achieved compound‐specifically for mixtures of halogenated organics following GC separation to baseline resolution. Conclusions GC‐Cr/HTC technology can be implemented in existing analytical equipment using commercially available materials to provide a versatile tool for hydrogen CSIA of halogenated and non‐halogenated organics. Copyright © 2017 John Wiley & Sons, Ltd.