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Scientific Articles - PTR-MS Bibliography

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[Ammann2004] Ammann, C., C. Spirig, A. Neftel, M. Steinbacher, M. Komenda, and A. Schaub, "Application of PTR-MS for measurements of biogenic VOC in a deciduous forest", International Journal of Mass Spectrometry, vol. 239, no. 2: Elsevier, pp. 87–101, 2004.
The vegetation–atmosphere-exchange is an important process controlling the atmospheric concentration of various volatile organic compounds (VOCs) that play a major role in atmospheric chemistry. However, the quantification of VOC exchange on the ecosystem scale is still an analytical challenge. In the present study we tested and applied a proton-transfer-reaction mass spectrometry system (PTR-MS) for the measurement of biogenic VOCs in a mixed deciduous forest. VOC concentrations were calculated from the raw instrument signals based on physical principles. This method allows a consistent quantification also of compounds for which regular calibration with a gas standard is not available. It requires a regular and careful investigation of the mass-dependent ion detection characteristics of the PTR-MS, which otherwise could become a considerable error source. The PTR-MS method was tested in the laboratory for a range of oxygenated and non-oxygenated VOCs using a permeation source. The agreement was within 16% or better, which is well within the expected uncertainty. During the field measurement campaign in a deciduous forest stand, an on-line intercomparison with a state-of-the-art gas-chromatography system showed a generally good agreement. However, the relatively low ambient VOC concentrations revealed some systematic difference for acetone and isoprene, that may indicate an error in the determination of the PTR-MS offset or an interference of an unidentified isobaric compound on the detected ion mass. With the presentation of selected field results, we demonstrate the ability of the PTR-MS system to measure continuous vertical concentration profiles of biogenic VOCs throughout a forest canopy at a time resolution of 20 min. The resulting datasets provide valuable information for the study of the interactions between emission, photochemical transformation and transport processes within and above the forest canopy.
[Spirig2005] Spirig, C., A. Neftel, C. Ammann, J. Dommen, W. Grabmer, A. Thielmann, A. Schaub, J. Beauchamp, A. Wisthaler, A. Hansel, et al., "Eddy covariance flux measurements of biogenic VOCs during ECHO 2003 using proton transfer reaction mass spectrometry", Atmospheric Chemistry and Physics, vol. 5, no. 2, pp. 465–481, 2005.
Within the framework of the AFO 2000 project ECHO, two PTR-MS instruments were operated in combination with sonic anemometers to determine biogenic VOC fluxes from a mixed deciduous forest site in North-Western Germany. The measurement site was characterised by a forest of inhomogeneous composition, complex canopy structure, limited extension in certain wind directions and frequent calm wind conditions during night time. The eddy covariance (EC) technique was applied since it represents the most direct flux measurement approach on the canopy scale and is, therefore, least susceptible to these non-ideal conditions. A specific flux calculation method was used to account for the sequential multi-component PTR-MS measurements and allowing an individual delay time adjustment as well as a rigorous quality control based on cospectral analysis. The validated flux results are consistent with light and temperature dependent emissions of isoprene and monoterpenes from this forest, with average daytime emissions of 0.94 and 0.3µg m-2s-1, respectively. Emissions of methanol reached on average 0.087µg m-2s-1 during daytime, but fluxes were too small to be detected during night time. Upward fluxes of the isoprene oxidation products methyl vinyl ketone (MVK) and methacrolein (MACR) were also found, being two orders of magnitude lower than those of isoprene. Calculations with an analytical footprint model indicate that the observed isoprene fluxes correlate with the fraction of oaks within the footprints of the flux measurement.

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Selected PTR-MS related Reviews

F. Biasioli, C. Yeretzian, F. Gasperi, T. D. Märk: PTR-MS monitoring of VOCs and BVOCs in food science and technology, Trends in Analytical Chemistry 30 (7) (2011).

J. de Gouw, C. Warneke, T. Karl, G. Eerdekens, C. van der Veen, R. Fall: Measurement of Volatile Organic Compounds in the Earth's Atmosphere using Proton-Transfer-Reaction Mass Spectrometry. Mass Spectrometry Reviews, 26 (2007), 223-257.

W. Lindinger, A. Hansel, A. Jordan: Proton-transfer-reaction mass spectrometry (PTR–MS): on-line monitoring of volatile organic compounds at pptv levels, Chem. Soc. Rev. 27 (1998), 347-375.


Lists with PTR-MS relevant publications of the University of Innsbruck can be found here: Atmospheric and indoor air chemistry, IMR, Environmental Physics and Nano-Bio-Physics


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