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Scientific Articles - PTR-MS Bibliography

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Found 8 results
Title [ Year(Asc)]
Filters: Author is Holzinger, R.  [Clear All Filters]
2014
[1703] Timkovsky, J.., P.. Gankema, R.. Pierik, and R.. Holzinger, "A plant chamber system with downstream reaction chamber to study the effects of pollution on biogenic emissions.", Environ Sci Process Impacts, vol. 16, pp. 2301–2312, 2014.
Link: http://dx.doi.org/10.1039/c4em00214h
Abstract
<p>A system of two plant chambers and a downstream reaction chamber has been set up to investigate the emission of biogenic volatile organic compounds (BVOCs) and possible effects of pollutants such as ozone. The system can be used to compare BVOC emissions from two sets of differently treated plants, or to study the photochemistry of real plant emissions under polluted conditions without exposing the plants to pollutants. The main analytical tool is a proton-transfer-reaction time-of-flight mass spectrometer (PTR-TOF-MS) which allows online monitoring of biogenic emissions and chemical degradation products. The identification of BVOCs and their oxidation products is aided by cryogenic trapping and subsequent in situ gas chromatographic analysis.</p>
2013
[Park2013] Park, J-H.., A.. H. Goldstein, J.. Timkovsky, S.. Fares, R.. Weber, J.. Karlik, and R.. Holzinger, "Active atmosphere-ecosystem exchange of the vast majority of detected volatile organic compounds.", Science, vol. 341, no. 6146: Department of Environmental Science, Policy, and Management, University of California at Berkeley, Berkeley, CA 94720, USA., pp. 643–647, Aug, 2013.
Link: http://nature.berkeley.edu/ahg/pubs/Park%20et%20al%20Science%202013.pdf
Abstract
<p>Numerous volatile organic compounds (VOCs) exist in Earth&#39;s atmosphere, most of which originate from biogenic emissions. Despite VOCs&#39; critical role in tropospheric chemistry, studies for evaluating their atmosphere-ecosystem exchange (emission and deposition) have been limited to a few dominant compounds owing to a lack of appropriate measurement techniques. Using a high-mass resolution proton transfer reaction-time of flight-mass spectrometer and an absolute value eddy-covariance method, we directly measured 186 organic ions with net deposition, and 494 that have bidirectional flux. This observation of active atmosphere-ecosystem exchange of the vast majority of detected VOCs poses a challenge to current emission, air quality, and global climate models, which do not account for this extremely large range of compounds. This observation also provides new insight for understanding the atmospheric VOC budget.</p>
[1513] Holzinger, R.., A.. H. Goldstein, P.. L. Hayes, J.. L. Jimenez, and J.. Timkovsky, "Chemical evolution of organic aerosol in Los Angeles during the CalNex 2010 study", Atmospheric Chemistry and Physics, vol. 13, pp. 10125–10141, Oct, 2013.
Link: http://dx.doi.org/10.5194/acp-13-10125-2013
Abstract
<p>During the CalNex study (15 May to 16 June 2010) a large suite of instruments was operated at the Los Angeles area ground supersite to characterize the sources and atmospheric processing of atmospheric pollution. The thermal-desorption proton-transfer-reaction mass-spectrometer (TD-PTR-MS) was deployed to an urban area for the first time and detected 691 organic ions in aerosol samples, the mean total concentration of which was estimated as 3.3 μg m&minus;3. Based on comparison to total organic aerosol (OA) measurements, we estimate that approximately 50% of the OA mass at this site was directly measured by the TD-PTR-MS. Based on correlations with aerosol mass spectrometer (AMS) OA components, the ions were grouped to represent hydrocarbon-like OA (HOA), local OA (LOA), semi-volatile oxygenated OA (SV-OOA), and low volatility oxygenated OA (LV-OOA). Mass spectra and thermograms of the ion groups are mostly consistent with the assumed sources and/or photochemical origin of the OA components. The mass spectra of ions representing the primary components HOA and LOA included the highest m/z, consistent with their higher resistance to thermal decomposition, and they were volatilized at lower temperatures (&nbsp; 150 &deg;C). Photochemical ageing weakens C-C bond strengths (also resulting in chemical fragmentation), and produces species of lower volatility (through the addition of functional groups). Accordingly the mass spectra of ions representing the oxidized OA components (SV-OOA, and LV-OOA) lack the highest masses and they are volatilized at higher temperatures (250&ndash;300 &deg;C). Chemical parameters like mean carbon number (nC), mean carbon oxidation state (OSC), and the atomic ratios O / C and H / C of the ion groups are consistent with the expected sources and photochemical processing of the aerosol components. Our data suggest that chemical fragmentation gains importance over functionalization as photochemical age of OA increases. Surprisingly, the photochemical age of OA decreases during the daytime hours, demonstrating the importance of rapid production of new (photochemically young) SV-OOA during daytime. The PTR detects higher organic N concentrations than the AMS, the reasons for which are not well understood and cannot be explained by known artifacts related to PTR or the AMS. The median atomic N / C ratio (6.4%) of the ion group representing LV-OOA is a factor 2 higher than N / C of any other ion group. This suggests a multiphase chemical source involving ammonium ions is contributing to LV-OOA.</p>
2012
[1512] Park, J.-H.., A.. H. Goldstein, J.. Timkovsky, S.. Fares, R.. Weber, J.. Karlik, and R.. Holzinger, "Eddy covariance emission and deposition flux measurements using proton transfer reaction-time of flight-mass spectrometry (PTR-TOF-{MS}): comparison with PTR-{MS} measured vertical gradients and fluxes", Atmospheric Chemistry and Physics Discussions, vol. 12, pp. 20435–20482, Aug, 2012.
Link: http://dx.doi.org/10.5194/acpd-12-20435-2012
Abstract
<p>During summer 2010, a proton transfer reaction-time of flight-mass spectrometer (PTR-TOF-MS) and a standard proton transfer reaction mass spectrometer (PTR-MS) were deployed simultaneously for one month in an orange orchard in the Central Valley of California to collect continuous data suitable for eddy covariance (EC) flux calculations. The high time resolution (5 Hz) and high mass resolution (up to 5000 m Δ m&minus;1) data from the PTR-TOF-MS provided the basis for calculating the concentration and flux for a wide range of volatile organic compounds (VOC). Throughout the campaign, 664 mass peaks were detected in mass-to-charge ratios between 10 and 1278. Here we present PTR-TOF-MS EC fluxes of the 27 ion species for which the vertical gradient was simultaneously measured by PTR-MS. These EC flux data were validated through spectral analysis (i.e. co-spectrum, normalized co-spectrum, and ogive). Based on inter-comparison of the two PTR instruments, no significant instrumental biases were found in either mixing ratios or fluxes, and the data showed agreement within 5% on average for methanol and acetone. For the measured biogenic volatile organic compounds (BVOC), the EC fluxes from PTR-TOF-MS were in agreement with the qualitatively inferred flux directions from vertical gradient measurements by PTR-MS. For the 27 selected ion species reported here, the PTR-TOF-MS measured total (24 h) mean net flux of 299 μg C m&minus;2 h&minus;1. The dominant BVOC emissions from this site were monoterpenes (m/z 81.070 + m/z 137.131 + m/z 95.086, 34%, 102 μg C m&minus;2 h&minus;1) and methanol (m/z 33.032, 18%, 72 μg C m&minus;2 h&minus;1). The next largest fluxes were detected at the following masses (attribution in parenthesis): m/z 59.048 (mostly acetone, 12.2%, 36.5 μg C m&minus;2 h&minus;1), m/z 61.027 (mostly acetic acid, 11.9%, 35.7 μg C m&minus;2 h&minus;1), m/z 93.069 (para-cymene + toluene, 4.1%, 12.2 μg C m&minus;2 h&minus;1), m/z 45.033 (acetaldehyde, 3.8%, 11.5 μg C m&minus;2 h&minus;1), m/z 71.048 (methylvinylketone + methacrolein, 2.4%, 7.1 μg C m&minus;2 h&minus;1), and m/z 69.071 (isoprene + 2-methyl-3-butene-2-ol, 1.8%, 5.3 μg C m&minus;2 h&minus;1). Low levels of emission and/or deposition (&lt;1.6% for each, 5.8% in total flux) were observed for the additional reported masses. Overall, our results show that EC flux measurements using PTR-TOF-MS is a powerful new tool for characterizing the biosphere-atmosphere exchange including both emission and deposition for a large range of BVOC and their oxidation products.</p>
2009
[1504] Schurgers, G.., A.. Arneth, R.. Holzinger, and A.. H. Goldstein, "Process-based modelling of biogenic monoterpene emissions combining production and release from storage", Atmospheric Chemistry and Physics, vol. 9, pp. 3409–3423, May, 2009.
Link: http://dx.doi.org/10.5194/acp-9-3409-2009
Abstract
<p>Monoterpenes, primarily emitted by terrestrial vegetation, can influence atmospheric ozone chemistry, and can form precursors for secondary organic aerosol. The short-term emissions of monoterpenes have been well studied and understood, but their long-term variability, which is particularly important for atmospheric chemistry, has not. This understanding is crucial for the understanding of future changes. In this study, two algorithms of terrestrial biogenic monoterpene emissions, the first one based on the short-term volatilization of monoterpenes, as commonly used for temperature-dependent emissions, and the second one based on long-term production of monoterpenes (linked to photosynthesis) combined with emissions from storage, were compared and evaluated with measurements from a Ponderosa pine plantation (Blodgett Forest, California). The measurements were used to parameterize the long-term storage of monoterpenes, which takes place in specific storage organs and which determines the temporal distribution of the emissions over the year. The difference in assumptions between the first (emission-based) method and the second (production-based) method, which causes a difference in upscaling from instantaneous to daily emissions, requires roughly a doubling of emission capacities to bridge the gap to production capacities. The sensitivities to changes in temperature and light were tested for the new methods, the temperature sensitivity was slightly higher than that of the short-term temperature dependent algorithm.</p>
2007
[1503] Holzinger, R.., D.. B. Millet, B.. Williams, A.. Lee, N.. Kreisberg, S.. V. Hering, J.. Jimenez, J.. D. Allan, D.. R. Worsnop, and A.. H. Goldstein, "Emission, oxidation, and secondary organic aerosol formation of volatile organic compounds as observed at Chebogue Point, Nova Scotia", Journal of Geophysical Research, vol. 112, 2007.
Link: http://dx.doi.org/10.1029/2006JD007599
Abstract
<p>We report the detection of a class of related oxygenated compounds by proton-transfer-reaction mass-spectrometry (PTR-MS) that have rarely or never been observed as a group using in situ instrumentation. Measurements were made as part of the International Consortium for Atmospheric Research on Transport and Transformation (ICARTT) 2004 in Chebogue Point, Nova Scotia. The detected class of compounds discussed here includes acetic acid, formaldehyde, acetaldehyde, tentatively identified formic acid and hydroxyacetone, and unidentified compounds detected at mass to charge ratios 85, 87, 99, 101, 113, 115, and 129. Typical concentrations were 800, 2500, 450, 700, 85, 25, 50, 50, 60, 35, 20, and 25 ppt, respectively. The uniqueness of this class of compounds is illustrated by showing they were poorly related to trace gases found in the US outflow, local pollution, primary biogenic emissions and other oxygenated compounds such as acetone, methanol, and MEK measured by other in situ instrumentation. On the other hand these oxidized volatile organic compounds were related to chemical species in aerosols and their abundance was high during nucleation events. Thus they likely are gas phase species that are formed in parallel to biogenic secondary organic aerosol production. We clearly show these compounds do not originate from local sources. We also show these compounds match the oxidation products of isoprene observed in smog chamber studies, and we therefore suggest they must be mainly produced by oxidation of biogenic precursor compounds.</p>
2006
[1501] Holzinger, R.., A.. Lee, M.. McKay, and A.. H. Goldstein, "Seasonal variability of monoterpene emission factors for a ponderosa pine plantation in California", Atmospheric Chemistry and Physics, vol. 6, pp. 1267–1274, Apr, 2006.
Link: http://nature.berkeley.edu/ahg/pubs/seasonal.pdf
Abstract
<p>Monoterpene fluxes have been measured over an 11 month period from June 2003 to April 2004. During all seasons ambient air temperature was the environmental factor most closely related to the measured emission rates. The monoterpene flux was modeled using a basal emission rate multiplied by an exponential function of a temperature, following the typical practice for modelling temperature dependent biogenic emissions. A basal emission of 1.0 μmol h&minus;1 m&minus;2 (at 30&deg;C, based on leaf area) and a temperature dependence (β) of 0.12&deg;C&minus;1 reproduced measured summer emissions well but underestimated spring and winter measured emissions by 60&ndash;130%. The total annual monoterpene emission may be underestimated by &nbsp;50% when using a model optimized to reproduce monoterpene emissions in summer. The long term dataset also reveals an indirect connection between non-stomatal ozone and monoterpene flux beyond the dependence on temperature that has been shown for both fluxes.</p>
2005
[1498] Holzinger, R.., A.. Lee, K.. T. Paw, and U.. A. H. Goldstein, "Observations of oxidation products above a forest imply biogenic emissions of very reactive compounds", Atmospheric Chemistry and Physics, vol. 5, pp. 67–75, Jan, 2005.
Link: http://dx.doi.org/10.5194/acp-5-67-2005
Abstract
<p>Vertical gradients of mixing ratios of volatile organic compounds have been measured in a Ponderosa pine forest in Central California (38.90&deg; N, 120.63&deg; W, 1315m). These measurements reveal large quantities of previously unreported oxidation products of short lived biogenic precursors. The emission of biogenic precursors must be in the range of 13-66&micro;mol m-2h-1 to produce the observed oxidation products. That is 6-30 times the emissions of total monoterpenes observed above the forest canopy on a molar basis. These reactive precursors constitute a large fraction of biogenic emissions at this site, and are not included in current emission inventories. When oxidized by ozone they should efficiently produce secondary aerosol and hydroxyl radicals.</p>

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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).
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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.
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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.
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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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