Journal
RAPID COMMUNICATIONS IN MASS SPECTROMETRY
Volume 23, Issue 19, Pages 3183-3193Publisher
JOHN WILEY & SONS LTD
DOI: 10.1002/rcm.4222
Keywords
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Funding
- EPSRC [EP/D013739/1]
- Queen's University of Belfast
- University of Strathclyde, Glasgow
- Engineering and Physical Sciences Research Council [EP/D013739/1] Funding Source: researchfish
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We present an advanced system for on-line position-specific carbon isotope analysis. The main limitation of on-line intramolecular isotope ratio measurements has been that optimal pyrolytic fragments are obtained mostly at temperatures where the analyte has not completely reacted. As a result of undetermined isotopic fractionation, the isotopic signatures of the pyrolysis products are not strictly equal to these of the equivalent moieties in the parent molecule. We designed a pyrolytic unit in which both temperature and reaction time are variable parameters, enabling determination of the enrichment factor of the pyrolysis at optimal temperature by construction of a Rayleigh plot. In the case of methyl tert-butyl ether (MTBE) presented here, a 'pre-pyrolysis' fractionation of MTBE leading to a depletion of 0.9 parts per thousand was discovered and the enrichment factor of the optimal pyrolysis reaction was determined at -1.7 parts per thousand. Absolute delta(13)C values of two functional groups of MTBE - the methoxy group and the 2-methylpropane group - could be determined with 95% confidence intervals of 0.4 parts per thousand and 0.5 parts per thousand, respectively. Copyright (C) 2009 John Wiley & Sons, Ltd.
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