Model Based Determination of Detection Limits for Proton Transfer Reaction Mass Spectrometer

Anton Amann, Konrad Schwarz, Gejza Wimmer and Viktor Witkovský 6
  • 1 Breath Research Institute, Austrian Academy of Sciences, Dornbirn, Austria
  • 2 University Clinic for Anesthesia, Innsbruck Medical University, Innsbruck, Austria
  • 3 Matej Bel University, Banská Bystrica, Slovakia
  • 4 Mathematical Institute, Slovak Academy of Sciences, Bratislava, Slovakia
  • 5 Masaryk University, Brno, Czech Republic
  • 6 Institute of Measurement Science, Slovak Academy of Sciences, Bratislava, Slovakia

Model Based Determination of Detection Limits for Proton Transfer Reaction Mass Spectrometer

Proton Transfer Reaction Mass Spectrometry (PTR-MS) is a chemical ionization mass spectrometric technique which allows to measure trace gases as, for example, in exhaled human breath. The quantification of compounds at low concentrations is desirable for medical diagnostics. Typically, an increase of measuring accuracy can be achieved if the duration of the measuring process is extended. For real time measurements the time windows for measurement are relatively short, in order to get a good time resolution (e.g. with breath-to-breath resolution during exercise on a stationary bicycle). Determination of statistical detection limits is typically based on calibration measurements, but this approach is limited, especially for very low concentrations. To overcome this problem, a calculation of limit of quantification (LOQ) and limit of detection (LOD), respectively, based on a theoretical model of the measurement process is outlined.

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  • Arendacká, B., Schwarz, K., Štolc, S., Wimmer, G., Witkovský, V. (2008). Variability issues in determining the concentration of isoprene in human breath by PTR-MS. Journal of Breath Research 2(3), 037007 (8pp).

  • Arinbruster, D., Tillman, M., Hubbs, L. (1994). Limit of detection (LOD) / limit of quantitation (LOQ): Comparison of the empirical and the statistical methods exemplified with GC-MS assays of abused drugs. Clinical Chemistry 40(7), 1233-1238.

  • Cox, C. (2005). Limits of quantitation for laboratory assays. Appl. Statist. 54(1), 63-76.

  • Currie, L. (1997). Detection: International update, and some emerging dilemmas involving calibration, the blank, and multiple detection decisions. Chemometrics and Intelligent Laboratory Systems 37, 151-181.

  • de Gouw, J., Warneke, C. (2007). Measurements of volatile organic compounds in the earth's atmosphere using proton-transfer-reaction mass spectrometry. Mass Spectrom Rev 26(2), 223-57.

  • de Gouw, J. A., Goldan, P. D., Warneke, C., Kuster, W. C., Roberts, J. M., Marchewka, M., Bertman, S. B., Pszenny, A. P., Keene, W. C. (2003). Validation of proton transfer reaction-mass spectrometry (PTR-MS) measurements of gas-phase organic compounds in the atmosphere during the new england air quality study (NEAQS). J. Geophys. Res. 108(D21), 4682.

  • de Gouw, J., Warneke, C., Karl, T., Eerdekens, G., van der Veen, C., Fall, R. (2003). Sensitivity and specificity of atmospheric trace gas detection by proton-transfer-reaction mass spectrometry. Int J Mass Spec 223-224, 365 - 382.

  • Eurachem (2002). Accreditation for chemical laboratories. Environ Sci Technol. 36(7), 1554-60.

  • Hansel, A., Jordan, A., Holzinger, R., Prazeller, P., Vogel, W., Lindinger, W. (1995). Proton transfer reaction mass spectrometry: on-line trace gas analysis at the ppb level. Int. J. Mass Spectrom. Ion Processes 149/150, 609 - 619.

  • Hayward, S., Hewitt, C., Sartin, J., Owen, S. (2002). Performance characteristics and applications of a proton transfer reaction-mass spectrometer for measuring volatile organic compounds in ambient air. Environ Sci Technol. 36(7), 1554-60.

  • Janiga, I., Mocák, J., Garaj, I. (2008). Comparison of minimum detectable concentration with the IUPAC detection limit. Measurement Science Review 8(5), 108-110.

  • Lavagnini, I., Magno, F. (2007). A statistical overview on univariate calibration, inverse regression, and detection limits: Application to gas chromatography/mass spectrometry technique. Mass Spectrom Rev 26(1), 1-18.

  • Lindinger, W., Hansel, A., Jordan, A. (1998). On-line monitoring of volatile organic compounds at pptv levels by means of proton-transfer-reaction mass spectrometry (PTR-MS) medical applications, food control and environmental research. Int. J. Mass Spectrom. Ion Processes 173, 191 - 241.

  • Mocák, J., Bond, A. M., Mitchell, S., Scollary, G. (1997). A statistical overview of standard (IUPAC and ACS) and new procedures for determining the limits of detection and quantification: Application to voltammetric and stripping techniques (technical report). Pure and Applied Chemistry 69(2), 297-328.

  • PUBL-TS-056-96 (1996). Analytical detection limit guidance & Laboratory guide for determining method detection limits. Wisconsin Department of Natural Resources - Laboratory Certification Program.

  • Schwarz, K., Filipiak, W., Amann, A. (2009). Determining concentration patterns of volatile compounds in exhaled breath by PTR-MS. Journal of Breath Research 3(2), 027002 (15pp).

  • Smith, D., O P. (2005). Selected ion flow tube mass spectrometry (SIFT-MS) for on-line trace gas analysis. Mass Spectrom Rev 24(5), 661-700.

  • Warneke, C., van der Veen, C., Luxembourg, S., de Gouw, J. A., Kok, A. (2001). Measurements of benzene and toluene in ambient air using proton-transfer-reaction mass spectrometry: calibration, humidity dependence, and field intercomparison. International Journal of Mass Spectrometry 207(3), 167-182.

  • Zhao, J., Zhang, R. Y. (2004). Proton transfer reaction rate constants between hydronium ion (H3O(+)) and volatile organic compounds. Atmospheric Environment 38(14), 2177-2185.


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