On the interference of Kr during carbon isotope analysis of methane using continuous-flow combustion-isotope ratio mass spectrometry

J. Schmitt, B. Seth, M. Bock, C. Van Der Veen, L. Möller, C. J. Sapart, M. Prokopiou, Todd Anthony Sowers, T. Röckmann, H. Fischer

Research output: Contribution to journalArticle

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Abstract

Stable carbon isotope analysis of methane (δ13C of CH 4) on atmospheric samples is one key method to constrain the current and past atmospheric CH4 budget. A frequently applied measurement technique is gas chromatography (GC) isotope ratio mass spectrometry (IRMS) coupled to a combustion-preconcentration unit. This report shows that the atmospheric trace gas krypton (Kr) can severely interfere during the mass spectrometric measurement, leading to significant biases in δ 13C of CH4, if krypton is not sufficiently separated during the analysis. According to our experiments, the krypton interference is likely composed of two individual effects, with the lateral tailing of the doubly charged 86Kr peak affecting the neighbouring m/z 44 and partially the m/z 45 Faraday cups. Additionally, a broad signal affecting m/z 45 and especially m/z 46 is assumed to result from scattered ions of singly charged krypton. The introduced bias in the measured isotope ratios is dependent on the chromatographic separation, the krypton-to-CH4 mixing ratio in the sample, the focusing of the mass spectrometer as well as the detector configuration and can amount to up to several per mil in δ13C. Apart from technical solutions to avoid this interference, we present correction routines to a posteriori remove the bias.

Original languageEnglish (US)
Pages (from-to)1425-1445
Number of pages21
JournalAtmospheric Measurement Techniques
Volume6
Issue number5
DOIs
StatePublished - Aug 28 2013

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krypton
carbon isotope
mass spectrometry
combustion
methane
isotope
atmospheric gas
trace gas
mixing ratio
tailings
gas chromatography
stable isotope
spectrometer
analysis
ion
experiment

All Science Journal Classification (ASJC) codes

  • Atmospheric Science

Cite this

Schmitt, J. ; Seth, B. ; Bock, M. ; Van Der Veen, C. ; Möller, L. ; Sapart, C. J. ; Prokopiou, M. ; Sowers, Todd Anthony ; Röckmann, T. ; Fischer, H. / On the interference of Kr during carbon isotope analysis of methane using continuous-flow combustion-isotope ratio mass spectrometry. In: Atmospheric Measurement Techniques. 2013 ; Vol. 6, No. 5. pp. 1425-1445.
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Schmitt, J, Seth, B, Bock, M, Van Der Veen, C, Möller, L, Sapart, CJ, Prokopiou, M, Sowers, TA, Röckmann, T & Fischer, H 2013, 'On the interference of Kr during carbon isotope analysis of methane using continuous-flow combustion-isotope ratio mass spectrometry', Atmospheric Measurement Techniques, vol. 6, no. 5, pp. 1425-1445. https://doi.org/10.5194/amt-6-1425-2013

On the interference of Kr during carbon isotope analysis of methane using continuous-flow combustion-isotope ratio mass spectrometry. / Schmitt, J.; Seth, B.; Bock, M.; Van Der Veen, C.; Möller, L.; Sapart, C. J.; Prokopiou, M.; Sowers, Todd Anthony; Röckmann, T.; Fischer, H.

In: Atmospheric Measurement Techniques, Vol. 6, No. 5, 28.08.2013, p. 1425-1445.

Research output: Contribution to journalArticle

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T1 - On the interference of Kr during carbon isotope analysis of methane using continuous-flow combustion-isotope ratio mass spectrometry

AU - Schmitt, J.

AU - Seth, B.

AU - Bock, M.

AU - Van Der Veen, C.

AU - Möller, L.

AU - Sapart, C. J.

AU - Prokopiou, M.

AU - Sowers, Todd Anthony

AU - Röckmann, T.

AU - Fischer, H.

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Y1 - 2013/8/28

N2 - Stable carbon isotope analysis of methane (δ13C of CH 4) on atmospheric samples is one key method to constrain the current and past atmospheric CH4 budget. A frequently applied measurement technique is gas chromatography (GC) isotope ratio mass spectrometry (IRMS) coupled to a combustion-preconcentration unit. This report shows that the atmospheric trace gas krypton (Kr) can severely interfere during the mass spectrometric measurement, leading to significant biases in δ 13C of CH4, if krypton is not sufficiently separated during the analysis. According to our experiments, the krypton interference is likely composed of two individual effects, with the lateral tailing of the doubly charged 86Kr peak affecting the neighbouring m/z 44 and partially the m/z 45 Faraday cups. Additionally, a broad signal affecting m/z 45 and especially m/z 46 is assumed to result from scattered ions of singly charged krypton. The introduced bias in the measured isotope ratios is dependent on the chromatographic separation, the krypton-to-CH4 mixing ratio in the sample, the focusing of the mass spectrometer as well as the detector configuration and can amount to up to several per mil in δ13C. Apart from technical solutions to avoid this interference, we present correction routines to a posteriori remove the bias.

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