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Position‐specific carbon isotope analysis of trichloroacetic acid by gas chromatography/isotope ratio mass spectrometry
Author(s) -
Breider Florian,
Hunkeler Daniel
Publication year - 2011
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.5276
Subject(s) - chemistry , decarboxylation , kinetic isotope effect , isotope ratio mass spectrometry , isotope , isotopes of carbon , isotope analysis , trichloroacetic acid , mass spectrometry , isotope fractionation , gas chromatography , chromatography , fractionation , organic chemistry , deuterium , total organic carbon , catalysis , ecology , physics , quantum mechanics , biology
Trichloroacetic acid (TCAA) is an important environmental contaminant present in soils, water and plants. A method for determining the carbon isotope signature of the trichloromethyl position in TCAA using gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS) was developed and tested with TCAA from different origins. Position‐specific isotope analysis (PSIA) can provide direct information on the kinetic isotope effect for isotope substitution at a specific position in the molecule and/or help to distinguish different sources of a compound. The method is based on the degradation of TCAA into chloroform (CF) and CO 2 by thermal decarboxylation. Since thermal decarboxylation is associated with strong carbon isotope fractionation (ε = −34.6 ± 0.2‰) the reaction conditions were optimized to ensure full conversion. The combined isotope ratio of CF and CO 2 at the end of the reaction corresponded well to the isotope ratio of TCAA, confirming the reliability of the method. A method quantification limit (MQL) for TCAA of 18.6 µg/L was determined. Samples of TCAA produced by enzymatic and non‐enzymatic chlorination of natural organic matter (NOM) and some industrially produced TCAA were used as exemplary sources. Significant different PSIA isotope ratios were observed between industrial TCAA and TCAA samples produced by chlorination of NOM. This highlights the potential of the method to study the origin and the fate of TCAA in the environment. Copyright © 2011 John Wiley & Sons, Ltd.