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Correction of H_3^+ Contributions in Hydrogen Isotope Ratio Monitoring Mass Spectrometry

Sessions, Alex L. and Burgoyne, Thomas W. and Hayes, John M. (2001) Correction of H_3^+ Contributions in Hydrogen Isotope Ratio Monitoring Mass Spectrometry. Analytical Chemistry, 73 (2). pp. 192-199. ISSN 0003-2700. https://resolver.caltech.edu/CaltechAUTHORS:20130604-075847754

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Abstract

Two fundamentally different approaches, termed “pointwise” and “peakwise,” are currently used to correct hydrogen isotope ratio monitoring data for the presence of H_3^+ ion contributions. Consideration of the underlying assumptions shows that the peakwise approach is valid only for peaks with the same functional shape and only when background signals do not vary. The pointwise correction is much more versatile and can be used even when peak shapes and sizes, as well as background signals, vary significantly. It is not exact and is limited in accuracy by (1) the signal-broadening effects of electronic time constants, (2) the analog-to-digital conversion frequency, and (3) the highest frequency of the sample signal. To minimize errors for typical gas chromatographic signals, time constants of <500 ms and analog-to-digital sampling intervals of ≤250 ms are needed. Errors are further minimized by matching sample and standard peaks in both amplitude and D/H ratio. Using the pointwise algorithm, we demonstrate that a series of 14 homologous n-alkanes varying in concentration over a 5-fold range can be analyzed with a mean precision of 2.3‰ and no systematic errors.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ac000489e DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ac000489ePublisherArticle
ORCID:
AuthorORCID
Sessions, Alex L.0000-0001-6120-2763
Additional Information:© 2001 American Chemical Society. Received for review April 28, 2000. Accepted October 19, 2000. Publication Date (Web): December 8, 2000. We thank Arndt Schimmelmann at Indiana University for preparing and analyzing the C_(16)-C_(30) n-alkane standard used here. Bob Dias provided thoughtful review of the manuscript. We gratefully acknowledge many helpful discussions with Hans-Jürgen Schlüter, Andreas Hilkert, and Willi Brand at Finnigan-MAT during the course of this work. This project was supported by National Science Foundation Grant OCE-9711284 to J.M.H. and a National Science Foundation postdoctoral fellowship to T.W.B.
Funders:
Funding AgencyGrant Number
NSFOCE-9711284
NSF Postdoctoral FellowshipUNSPECIFIED
Issue or Number:2
Record Number:CaltechAUTHORS:20130604-075847754
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20130604-075847754
Official Citation:Correction of H3+ Contributions in Hydrogen Isotope Ratio Monitoring Mass Spectrometry Alex L. Sessions, Thomas W. Burgoyne, and John M. Hayes Analytical Chemistry 2001 73 (2), 192-199
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:38770
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:25 Jun 2013 16:04
Last Modified:03 Oct 2019 05:00

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