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Scientific Articles - PTR-MS Bibliography

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Found 5 results
Title [ Year(Desc)]
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Filters: Author is Karl, Thomas  [Reset Search]
2001
[Karl2001a] Karl, T., A. Guenther, A. Jordan, R. Fall, and W. Lindinger, "Eddy covariance measurement of biogenic oxygenated VOC emissions from hay harvesting", Atmospheric Environment, vol. 35, no. 3: Elsevier, pp. 491–495, 2001.
Link: http://www.sciencedirect.com/science/article/pii/S1352231000004052
Abstract
Biogenic oxygenated volatile organic compound (VOC) fluxes have been directly measured by eddy covariance using the combination of a fast response, real-time \{VOC\} sensor and an acoustic anemometer. \{VOC\} detection is based on proton-transfer reaction mass spectrometry which has currently a response time of ca. 0.8 s and the system is suitable for making nearly unattended, long-term and continuous measurements of \{VOC\} fluxes. The eddy covariance system has a detection limit, for most VOCs, of less than 0.1 mg m−2 h−1. The system was field tested above a hayfield near St. Johann, Austria where cut and drying grasses released a variety of VOCs. High fluxes were observed for about 2 days after cutting and were dominated by methanol (1–8.4 mg m−2 h−1), acetaldehyde (0.5–3 mg m−2 h−1), hexenals (0.1–1.5 mg m−2 h−1) and acetone (0.1–1.5 mg m−2 h−1). The eddy covariance measurements generally agreed with flux estimates based on enclosure measurements and surface layer gradients. The sensitivity and selectivity of the system make it suitable for quantifying the fluxes of the dominant biogenic \{VOCs\} from a variety of landscapes and sources.
2004
[Karl2004] Karl, T., M. Potosnak, A. Guenther, D. Clark, J. Walker, J. D. Herrick, and C. Geron, "Exchange processes of volatile organic compounds above a tropical rain forest: Implications for modeling tropospheric chemistry above dense vegetation", Journal of geophysical research, vol. 109, no. D18: American Geophysical Union, pp. D18306, 2004.
Link: http://www.agu.org/pubs/crossref/2004/2004JD004738.shtml
Abstract
Disjunct eddy covariance in conjunction with continuous in-canopy gradient measurements allowed for the first time to quantify the fine-scale source and sink distribution of some of the most abundant biogenic (isoprene, monoterpenes, methanol, acetaldehyde, and acetone) and photooxidized (MVK+MAC, acetone, acetaldehyde, acetic, and formic acid) VOCs in an old growth tropical rain forest. Our measurements revealed substantial isoprene emissions (up to 2.50 mg m−2 h−1) and light-dependent monoterpene emissions (up to 0.33 mg m−2 h−1) at the peak of the dry season (April and May 2003). Oxygenated species such as methanol, acetone, and acetaldehyde were typically emitted during daytime with net fluxes up to 0.50, 0.36, and 0.20 mg m−2 h−1, respectively. When generalized for tropical rain forests, these fluxes would add up to a total emission of 36, 16, 19, 106, and 7.2 Tg/yr for methanol, acetaldehyde, acetone, isoprene, and monoterpenes, respectively. During nighttime we observed strong sinks for oxygenated and nitrogen-containing compounds such as methanol, acetone, acetaldehyde, MVK+MAC, and acetonitrile with deposition velocities close to the aerodynamic limit. This suggests that the canopy resistance (Rc) is very small and not the rate-limiting step for the nighttime deposition of many VOCs. Our measured mean dry deposition velocities of methanol, acetone, acetaldehyde, MVK+MAC, and acetonitrile were a factor 10–20 higher than estimated from traditional deposition models. If our measurements are generalized, this could have important implications for the redistribution of VOCs in atmospheric chemistry models. Our observations indicate that the current understanding of reactive carbon exchange can only be seen as a first-order approximation.
2007
[1488] Karl, T., A. Guenther, R. J. Yokelson, J. Greenberg, M. Potosnak, D. R. Blake, and P. Artaxo, "The tropical forest and fire emissions experiment: Emission, chemistry, and transport of biogenic volatile organic compounds in the lower atmosphere over Amazonia", Journal of Geophysical Research: Atmospheres, vol. 112, pp. n/a–n/a, 2007.
Link: http://dx.doi.org/10.1029/2007JD008539
Abstract
<p>Airborne and ground-based mixing ratio and flux measurements using eddy covariance (EC) and for the first time the mixed layer gradient (MLG) and mixed layer variance (MLV) techniques are used to assess the impact of isoprene and monoterpene emissions on atmospheric chemistry in the Amazon basin. Average noon isoprene (7.8 &plusmn; 2.3 mg/m2/h) and monoterpene fluxes (1.2 &plusmn; 0.5 mg/m2/h) compared well between ground and airborne measurements and are higher than fluxes estimated in this region during other seasons. The biogenic emission model, Model of Emissions of Gases and Aerosols from Nature (MEGAN), estimates fluxes that are within the model and measurement uncertainty and can describe the large observed variations associated with land-use change in the region north-west of Manaus. Isoprene and monoterpenes accounted for &sim;75% of the total OH reactivity in this region and are important volatile organic compounds (VOCs) for modeling atmospheric chemistry in Amazonia. The presence of fair weather clouds (cumulus humilis) had an important impact on the vertical distribution and chemistry of VOCs through the planetary boundary layer (PBL), the cloud layer, and the free troposphere (FT). Entrainment velocities between 10:00 and 11:30 local time (LT) are calculated to be on the order of 8&ndash;10 cm/s. The ratio of methyl-vinyl-ketone (MVK) and methacrolein (MAC) (unique oxidation products of isoprene chemistry) with respect to isoprene showed a pronounced increase in the cloud layer due to entrainment and an increased oxidative capacity in broken cloud decks. A decrease of the ratio in the lower free troposphere suggests cloud venting through activated clouds. OH modeled in the planetary boundary layer using a photochemical box model is much lower than OH calculated from a mixed layer budget approach. An ambient reactive sesquiterpene mixing ratio of 1% of isoprene would be sufficient to explain most of this discrepancy. Increased OH production due to increased photolysis in the cloud layer balances the low OH values modeled for the planetary boundary layer. The intensity of segregation (Is) of isoprene and OH, defined as a relative reduction of the reaction rate constant due to incomplete mixing, is found to be significant: up to 39 &plusmn; 7% in the &sim;800-m-deep cloud layer. The effective reaction rate between isoprene and OH can therefore vary significantly in certain parts of the lower atmosphere.</p>
2012
[1510] Jardine, K. J., R. K. Monson, L. Abrell, S. R. Saleska, A. Arneth, A. Jardine, Fᅢᄃoise. Yoko Ishida, A. Maria Yane Serrano, P. Artaxo, T. Karl, et al., "Within-plant isoprene oxidation confirmed by direct emissions of oxidation products methyl vinyl ketone and methacrolein", Glob Change Biol, vol. 18, pp. 973–984, Mar, 2012.
Link: http://nature.berkeley.edu/ahg/pubs/Jardine et al. 2012 GCB published.pdf
Abstract
<p>Isoprene is emitted from many terrestrial plants at high rates, accounting for an estimated 1/3 of annual global volatile organic compound emissions from all anthropogenic and biogenic sources combined. Through rapid photooxidation reactions in the atmosphere, isoprene is converted to a variety of oxidized hydrocarbons, providing higher order reactants for the production of organic nitrates and tropospheric ozone, reducing the availability of oxidants for the breakdown of radiatively active trace gases such as methane, and potentially producing hygroscopic particles that act as effective cloud condensation nuclei. However, the functional basis for plant production of isoprene remains elusive. It has been hypothesized that in the cell isoprene mitigates oxidative damage during the stress-induced accumulation of reactive oxygen species (ROS), but the products of isoprene-ROS reactions in plants have not been detected. Using pyruvate-2-13C leaf and branch feeding and individual branch and whole mesocosm flux studies, we present evidence that isoprene (i) is oxidized to methyl vinyl ketone and methacrolein (iox) in leaves and that iox/i emission ratios increase with temperature, possibly due to an increase in ROS production under high temperature and light stress. In a primary rainforest in Amazonia, we inferred significant in plant isoprene oxidation (despite the strong masking effect of simultaneous atmospheric oxidation), from its influence on the vertical distribution of iox uptake fluxes, which were shifted to low isoprene emitting regions of the canopy. These observations suggest that carbon investment in isoprene production is larger than that inferred from emissions alone and that models of tropospheric chemistry and biota&ndash;chemistry&ndash;climate interactions should incorporate isoprene oxidation within both the biosphere and the atmosphere with potential implications for better understanding both the oxidizing power of the troposphere and forest response to climate change.</p>
2015
[1760] Seco, R., T. Karl, A. Guenther, K. P. Hosman, S. G. Pallardy, L. Gu, C. Geron, P. Harley, and S. Kim, "Ecosystem-scale volatile organic compound fluxes duringᅡᅠan extreme drought in a broadleaf temperate forestᅡᅠof the Missouri Ozarks (central USA)", Global Change Biology, vol. 21, pp. 3657–3674, Jul, 2015.
Link: http://dx.doi.org/10.1111/gcb.12980
Abstract
<p>Considerable amounts and varieties of biogenic volatile organic compounds (BVOCs) are exchanged between vegetation and the surrounding air. These BVOCs play key ecological and atmospheric roles that must be adequately represented for accurately modeling the coupled biosphere-atmosphere-climate earth system. One key uncertainty in existing models is the response of BVOC fluxes to an important global change process: drought. We describe the diurnal and seasonal variation in isoprene, monoterpene, and methanol fluxes from a temperate forest ecosystem before, during, and after an extreme 2012 drought event in the Ozark region of the central USA. BVOC fluxes were dominated by isoprene, which attained high emission rates of up to 35.4 mg m(-2) h(-1) at midday. Methanol fluxes were characterized by net deposition in the morning, changing to a net emission flux through the rest of the daylight hours. Net flux of CO2 reached its seasonal maximum approximately a month earlier than isoprenoid fluxes, which highlights the differential response of photosynthesis and isoprenoid emissions to progressing drought conditions. Nevertheless, both processes were strongly suppressed under extreme drought, although isoprene fluxes remained relatively high compared to reported fluxes from other ecosystems. Methanol exchange was less affected by drought throughout the season, confirming the complex processes driving biogenic methanol fluxes. The fraction of daytime (7-17 h) assimilated carbon released back to the atmosphere combining the three BVOCs measured was 2% of gross primary productivity (GPP) and 4.9% of net ecosystem exchange (NEE) on average for our whole measurement campaign, while exceeding 5% of GPP and 10% of NEE just before the strongest drought phase. The meganv2.1 model correctly predicted diurnal variations in fluxes driven mainly by light and temperature, although further research is needed to address model BVOC fluxes during drought events.</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).
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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