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Scientific Articles - PTR-MS Bibliography

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[1795] Schroeder, J. R., J. H. Crawford, A. Fried, J. Walega, A. Weinheimer, A. Wisthaler, M. Müller, T. Mikoviny, G. Chen, M. Shook, et al., "Formaldehyde column density measurements as a suitable pathway to estimate near-surface ozone tendencies from space", Journal of Geophysical Research: Atmospheres, vol. 121, 2016.
Link: http://onlinelibrary.wiley.com/doi/10.1002/2016JD025419/full
Abstract
<p>In support of future satellite missions that aim to address the current shortcomings in measuring air quality from space, NASA&#39;s Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality (DISCOVER-AQ) field campaign was designed to enable exploration of relationships between column measurements of trace species relevant to air quality at high spatial and temporal resolution. In the DISCOVER-AQ data set, a modest correlation (r2&thinsp;=&thinsp;0.45) between ozone (O3) and formaldehyde (CH2O) column densities was observed. Further analysis revealed regional variability in the O3-CH2O relationship, with Maryland having a strong relationship when data were viewed temporally and Houston having a strong relationship when data were viewed spatially. These differences in regional behavior are attributed to differences in volatile organic compound (VOC) emissions. In Maryland, biogenic VOCs were responsible for &nbsp;28% of CH2O formation within the boundary layer column, causing CH2O to, in general, increase monotonically throughout the day. In Houston, persistent anthropogenic emissions dominated the local hydrocarbon environment, and no discernable diurnal trend in CH2O was observed. Box model simulations suggested that ambient CH2O mixing ratios have a weak diurnal trend (&plusmn;20% throughout the day) due to photochemical effects, and that larger diurnal trends are associated with changes in hydrocarbon precursors. Finally, mathematical relationships were developed from first principles and were able to replicate the different behaviors seen in Maryland and Houston. While studies would be necessary to validate these results and determine the regional applicability of the O3-CH2O relationship, the results presented here provide compelling insight into the ability of future satellite missions to aid in monitoring near-surface air quality.</p>
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[1791] Müller, M., B. E. Anderson, A. J. Beyersdorf, J. H. Crawford, G. S. Diskin, P. Eichler, A. Fried, F. N. Keutsch, T. Mikoviny, K. L. Thornhill, et al., "In situ measurements and modeling of reactive trace gases in a small biomass burning plume", Atmospheric Chemistry and Physics, vol. 16, pp. 3813–3824, 2016.
Link: http://www.atmos-chem-phys.net/16/3813/2016/
Abstract
<p>An instrumented NASA P-3B aircraft was used for airborne sampling of trace gases in a plume that had emanated from a small forest understory fire in Georgia, USA. The plume was sampled at its origin to derive emission factors and followed &thinsp;&sim;&thinsp;13.6 km downwind to observe chemical changes during the first hour of atmospheric aging. The P-3B payload included a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS), which measured non-methane organic gases (NMOGs) at unprecedented spatiotemporal resolution (10 m spatial/0.1 s temporal). Quantitative emission data are reported for CO2, CO, NO, NO2, HONO, NH3, and 16 NMOGs (formaldehyde, methanol, acetonitrile, propene, acetaldehyde, formic acid, acetone plus its isomer propanal, acetic acid plus its isomer glycolaldehyde, furan, isoprene plus isomeric pentadienes and cyclopentene, methyl vinyl ketone plus its isomers crotonaldehyde and methacrolein, methylglyoxal, hydroxy acetone plus its isomers methyl acetate and propionic acid, benzene, 2,3-butanedione, and 2-furfural) with molar emission ratios relative to CO larger than 1 ppbV ppmV&minus;1. Formaldehyde, acetaldehyde, 2-furfural, and methanol dominated NMOG emissions. No NMOGs with more than 10 carbon atoms were observed at mixing ratios larger than 50 pptV ppmV&minus;1 CO. Downwind plume chemistry was investigated using the observations and a 0-D photochemical box model simulation. The model was run on a nearly explicit chemical mechanism (MCM v3.3) and initialized with measured emission data. Ozone formation during the first hour of atmospheric aging was well captured by the model, with carbonyls (formaldehyde, acetaldehyde, 2,3-butanedione, methylglyoxal, 2-furfural) in addition to CO and CH4 being the main drivers of peroxy radical chemistry. The model also accurately reproduced the sequestration of NOx into peroxyacetyl nitrate (PAN) and the OH-initiated degradation of furan and 2-furfural at an average OH concentration of 7.45 &plusmn; 1.07 &times; 106 cm&minus;3 in the plume. Formaldehyde, acetone/propanal, acetic acid/glycolaldehyde, and maleic acid/maleic anhydride (tentatively identified) were found to be the main NMOGs to increase during 1 h of atmospheric plume processing, with the model being unable to capture the observed increase. A mass balance analysis suggests that about 50 % of the aerosol mass formed in the downwind plume is organic in nature.</p>

Featured Articles

Download Contributions to the International Conference on Proton Transfer Reaction Mass Spectrometry and Its Applications:

 

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).
Link

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.
Link

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.
Link

 

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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