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Scientific Articles - PTR-MS Bibliography

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[Mueller2006] Müller, K., S. Haferkorn, W. Grabmer, A. Wisthaler, A. Hansel, J. Kreuzwieser, C. Cojocariu, H. Rennenberg, and H. Herrmann, "Biogenic carbonyl compounds within and above a coniferous forest in Germany", Atmospheric Environment, vol. 40: Elsevier, pp. 81–91, 2006.
Diurnal mixing ratios of aldehydes and ketones were investigated during two joint experiments in summer months to identify biogenic contributions from coniferous forests to tropospheric chemistry. In a Norway spruce forest, the diurnal variation of carbonyl compounds was measured at 12 m (in the treetop) and at 24 m (above the canopy). The main findings of the experiment are that acetone (up to 9.1 ppbv), formaldehyde (up to 6.5 ppbv), acetaldehyde (up to 5.5 ppbv) and methyl ethyl ketone (MEK, up to 1.8 ppbv) were found in highest concentrations. For all major compounds with the exception of MEK, primary emissions are supposed. From α-pinene oxidation, pinonaldehyde was found with its peak concentrations (up to 0.15 ppbv) during the early morning hours. The diurnal variation of concentrations for most other compounds shows maximum concentrations near midday in 2,4-dinitrophenylhydrazine (DNPH) measurements but not for proton-transfer reaction mass spectrometry (PTR-MS) measurements of acetaldehyde and acetone. A clear correlation of carbonyl compound concentration to the radiation intensity and the temperature (R2=0.66) was found. However, formaldehyde did not show distinct diurnal variations. A very high correlation was observed for both heights between mixing ratios of acetaldehyde and acetone (R2=0.84), acetone and MEK (R2=0.90) as well as acetaldehyde and MEK (R2=0.88) but not for formaldehyde and the others. For the most time, the observed carbonyl compound concentrations above the canopy are higher than within the forest stand. This indicates an additional secondary formation in the atmosphere above the forest. The differences of acetone and acetaldehyde mixing ratios detected by DNPH technique and the PTR-MS could not be fully clarified by a laboratory intercomparison.
[Forkel2006] Forkel, R., O. Klemm, M. Graus, B. Rappenglück, W. R. Stockwell, W. Grabmer, A. Held, A. Hansel, and R. Steinbrecher, "Trace gas exchange and gas phase chemistry in a Norway spruce forest: A study with a coupled 1-dimensional canopy atmospheric chemistry emission model", Atmospheric Environment, vol. 40: Elsevier, pp. 28–42, 2006.
Numerical modelling is an efficient tool to investigate the role of chemical degradation of biogenic volatile organic compounds (BVOC) and the effect of dynamical processes on BVOC and product mixing ratios within and above forest canopies. The present study shows an application of the coupled canopy-chemistry model CACHE to a Norway spruce forest at the Waldstein (Fichtelgebirge, Germany). Simulated courses of temperature, trace gas mixing ratios, and fluxes are compared with measurements taken during the BEWA2000 field campaigns. The model permits the interpretation of the observed diurnal course of ozone and VOC by investigating the role of turbulent exchange, chemical formation and degradation, emission, and deposition during the course of the day. The simulation results show that BVOC fluxes into the atmosphere are 10–15% lower than the emission fluxes on branch basis due to chemical BVOC degradation within the canopy. BVOC degradation by the NO3 radical was found to occur in the lower part of the canopy also during daytime. Furthermore, the simulations strongly indicate that further research is still necessary concerning the emission and deposition of aldehydes and ketones.

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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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