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Compound-specific stable isotope analysis of organic contaminants in natural environments: a critical review of the state of the art, prospects, and future challenges

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Abstract

Compound-specific stable isotope analysis (CSIA) using gas chromatography-isotope ratio mass spectrometry (GC/IRMS) has developed into a mature analytical method in many application areas over the last decade. This is in particular true for carbon isotope analysis, whereas measurements of the other elements amenable to CSIA (hydrogen, nitrogen, oxygen) are much less routine. In environmental sciences, successful applications to date include (i) the allocation of contaminant sources on a local, regional, and global scale, (ii) the identification and quantification of (bio)transformation reactions on scales ranging from batch experiments to contaminated field sites, and (iii) the characterization of elementary reaction mechanisms that govern product formation. These three application areas are discussed in detail. The investigated spectrum of compounds comprises mainly n-alkanes, monoaromatics such as benzene and toluene, methyl tert-butyl ether (MTBE), polycyclic aromatic hydrocarbons (PAHs), and chlorinated hydrocarbons such as tetrachloromethane, trichloroethylene, and polychlorinated biphenyls (PCBs). Future research directions are primarily set by the state of the art in analytical instrumentation and method development. Approaches to utilize HPLC separation in CSIA, the enhancement of sensitivity of CSIA to allow field investigations in the µg L−1 range, and the development of methods for CSIA of other elements are reviewed. Furthermore, an alternative scheme to evaluate isotope data is outlined that would enable estimates of position-specific kinetic isotope effects and, thus, allow one to extract mechanistic chemical and biochemical information.

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Abbreviations

BTEX:

benzene, toluene, ethylbenzene, xylenes

MTBE:

methyl tert-butyl ether

PAHs:

polycyclic aromatic hydrocarbons

VOCs:

volatile compounds

PCBs:

polychlorinated biphenyls

CSIA:

compound-specific (stable) isotope (ratio) analysis

GC-IRMS, GC/IRMS or GCIRMS:

gas chromatography-isotope ratio mass spectrometry

GC-C-IRMS, GC/C/IRMS or GCC-IRMS:

gas chromatography-combustion-isotope ratio mass spectrometry

irmGC/MS:

isotope ratio monitoring gas chromatograph-mass spectrometry

GC/P/IRMS:

gas chromatography-pyrolysis-isotope ratio mass spectrometry (used for D/H)

KIE:

kinetic isotope effect

PSIA:

position-specific isotope analysis (for intramolecular isotope distribution)

SNIF-NMR:

site-specific natural isotopic fractionation by nuclear magnetic resonance spectroscopy

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Acknowledgements

We thank W.A. Brand for helpful remarks on isotope referencing strategies.

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Author notes

  1. Rainer U. Meckenstock

    Present address: Institute for Hydrology, GSF-Research Center for Environment and Health, Ingolstädter Landstr. 1, 85764, Neuherberg, Germany

Authors and Affiliations

  1. Environmental Mineralogy, Center for Applied Geoscience, Eberhard-Karls-University Tübingen, Wilhelmstr. 56, 72074, Tübingen, Germany

    Torsten C. Schmidt, Rainer U. Meckenstock & Stefan B. Haderlein

  2. Swiss Federal Institute for Environmental Science and Technology (EAWAG), Ueberlandstr. 133, 8600, Dübendorf, Switzerland

    Luc Zwank, Martin Elsner & Michael Berg

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  1. Torsten C. Schmidt
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Schmidt, T.C., Zwank, L., Elsner, M. et al. Compound-specific stable isotope analysis of organic contaminants in natural environments: a critical review of the state of the art, prospects, and future challenges. Anal Bioanal Chem 378, 283–300 (2004). https://doi.org/10.1007/s00216-003-2350-y

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