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Found 83 results
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2012
[1511] Fares, S.., J.-H.. Park, D.. R. Gentner, R.. Weber, E.. Ormeᅢᄆo, J.. Karlik, and A.. H. Goldstein, "Seasonal cycles of biogenic volatile organic compound fluxes and concentrations in a California citrus orchard", Atmospheric Chemistry and Physics, vol. 12, pp. 9865–9880, Oct, 2012.
Link: http://dx.doi.org/10.5194/acp-12-9865-2012
Abstract
<p>Orange trees are widely cultivated in Mediterranean climatic regions where they are an important agricultural crop. Citrus have been characterized as emitters of volatile organic compounds (VOC) in chamber studies under controlled environmental conditions, but an extensive characterization at field scale has never been performed using modern measurement methods, and is particularly needed considering the complex interactions between the orchards and the polluted atmosphere in which Citrus is often cultivated. For one year, in a Valencia orange orchard in Exeter, California, we measured fluxes using PTRMS (Proton Transfer Reaction Mass Spectrometer) and eddy covariance for the most abundant VOC typically emitted from citrus vegetation: methanol, acetone, and isoprenoids. Concentration gradients of additional oxygenated and aromatic compounds from the ground level to above the canopy were also measured. In order to characterize concentrations of speciated biogenic VOC (BVOC) in leaves, we analyzed leaf content by GC-MS (Gas Chromatography &ndash; Mass Spectrometery) regularly throughout the year. We also characterized in more detail concentrations of speciated BVOC in the air above the orchard by in-situ GC-MS during a few weeks in spring flowering and summer periods. Here we report concentrations and fluxes of the main VOC species emitted by the orchard, discuss how fluxes measured in the field relate to previous studies made with plant enclosures, and describe how VOC content in leaves and emissions change during the year in response to phenological and environmental parameters. The orchard was a source of monoterpenes and oxygenated VOC. The highest emissions were observed during the springtime flowering period, with mid-day fluxes above 2 nmol m&minus;2 s&minus;1 for methanol and up to 1 nmol m&minus;2 s&minus;1 for acetone and monoterpenes. During hot summer days emissions were not as high as we expected considering the known dependence of biogenic emissions on temperature. We provide evidence that thickening of leaf cuticle wax content limited gaseous emissions during the summer.</p>
[Simpraga2012] Simpraga, M., "Understanding the link between photosynthesis, growth and emissions of biogenic volatile organic compounds (BVOCs) in beech, oak and ash", : Ghent University, 2012.
Link: https://biblio.ugent.be/publication/2915124
Abstract
Gas exchange between vegetation and the atmosphere is very dynamic. In addition to gases such as carbon dioxide (CO2), water vapor, oxygen, nitrogen oxides (NOx), sulphur dioxide, ammonia and ozone (O3), also biogenic volatile organic compounds (BVOCs) are exchanged between the vegetation and the atmosphere. This PhD focussed on the exchange of CO2 and BVOCs, since net photosynthesis (Pn) and BVOC emission are two plant processes important in plant functioning. Vegetation, and forests in particular, acts as a major source of BVOCs. The importance of the study lays in understanding the link between Pn, BVOC emissions and tree growth. BVOC emissions indirectly affect climate change as BVOCs are in combination with atmospheric NOx the main precursors of photochemical O3 in the troposphere, where it acts as potential greenhouse gas, damaging vegetation and affecting human respiratory organs. BVOCs are therefore dominant reactive compounds in the troposphere and important in atmospheric chemistry and climatology. Understanding tree chemistry and ecophysiology is crucial to predict future changes in the Earth’s carbon balance as well as to update BVOC inventories and improve predictions in tropospheric air chemistry. Accordingly, the main goals of the PhD were to identify and quantify the effects of temperature, drought, seasonality and vertical canopy gradients on Pn and BVOC emissions. The general methodology consisted of developing and constructing enclosure systems for gas exchange measurements indoors and outdoors, where coupling of an infra-red gas analysis (IRGA), proton transfer reaction-mass spectrometry (PTR-MS) and thermal desorption gas chromatography/mass spectrometry (TD-GC/MS) represented a major challenge. With respect to tree species, the focus was on European beech (Fagus sylvatica L.), while additionally common ash (Fraxinus excelsior L.) and northern red oak (Quercus rubra L.) were examined in Chapter 4. The trees were examined in growth room conditions, at the campus and in the Aelmoeseneie experimental forest. The main variables measured were Pn and BVOC emissions, in particular of monoterpenoids (MTs). In addition, microclimatic variables (air temperature, photosynthetic photon flux density, soil water potential, and vapor pressure deficit) and leaf characteristics (specific leaf area, leaf temperature, leaf pigments, and leaf water potentials) were measured. In the growth room experiments, stem diameter variations and chlorophyll indices were measured to explain the behavior of MT emissions by young beech trees. In the forest, the experimental tower showed to be an important facility for adequate local characterization of adult beech Pn and BVOC chemistry. Leaf level studies showed to be crucial for unraveling the mechanisms behind the emission of BVOCs. The results indicated a large variability in BVOC emission patterns of different tree species. Temperature, drought, seasonality, vertical canopy gradients differently influenced Pn and BVOC emissions (and in particular MTs), as well as their ratio. Indoors and outdoors day-time Pn, MT emissions and MT/Pn carbon ratio varied in a systematic manner following light and temperature changes. The results indicated that not only light affected Pn, MT emissions and MT/Pn ratio, but also showed a pronounced temperature effect on MT emissions (and hence on the MT/Pn carbon ratio), with an increasing exponential trend with rising air temperatures. Furthermore, during drought stress MT emissions showed an increasing-decreasing trend depending on the drought severity. Linear variable displacement transducers (LVDTs) showed to be useful for stress quantification in BVOC studies. Another notable finding was that, under severe drought stress, two PTR-MS signals diverged from each other, indicating the possible presence of BVOC species other than MT such as green leaf volatiles (GLVs). Seasonal measurements on anatomically different trees indicated a strong temperature rather than light dependency when looking at total BVOC emission trends. Beside substantial quantities of MTs released from leaves into the atmosphere, driven by light and temperature, beside non-MTs, MTs also showed to play a role in plant-insect interactions. Detected stress compounds proved infestiation-based emissions. Consequently, plant-insect relationships require additional research, identifying individual MT species using the GC/MS speciation approach and looking at their relationships with ecophysiological parameters. In conclusion, the performed indoor and outdoor studies demonstrated that Pn and BVOC emissions are strongly interrelated. Proposed hypotheses were tested and confirmed. However, many unanswered questions remain, e.g. how the distribution of individual BVOC compounds correlated with temperature and drought stress as well as along the vertical canopy gradient.
[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>
2011
[Ghirardo2011] Ghirardo, A., J. Gutknecht, I. Zimmer, N. Brueggemann, and J-P. Schnitzler, "Biogenic volatile organic compound and respiratory CO2 emissions after 13C-labeling: online tracing of C translocation dynamics in poplar plants.", PLoS One, vol. 6, no. 2: Karlsruhe Institute of Technology, Institute for Meteorology and Climate Research, Garmisch-Partenkirchen, Germany., pp. e17393, 2011.
Link: http://dx.doi.org/10.1371/journal.pone.0017393
Abstract
Globally plants are the primary sink of atmospheric CO(2), but are also the major contributor of a large spectrum of atmospheric reactive hydrocarbons such as terpenes (e.g. isoprene) and other biogenic volatile organic compounds (BVOC). The prediction of plant carbon (C) uptake and atmospheric oxidation capacity are crucial to define the trajectory and consequences of global environmental changes. To achieve this, the biosynthesis of BVOC and the dynamics of C allocation and translocation in both plants and ecosystems are important.We combined tunable diode laser absorption spectrometry (TDLAS) and proton transfer reaction mass spectrometry (PTR-MS) for studying isoprene biosynthesis and following C fluxes within grey poplar (Populus x canescens) saplings. This was achieved by feeding either (13)CO(2) to leaves or (13)C-glucose to shoots via xylem uptake. The translocation of (13)CO(2) from the source to other plant parts could be traced by (13)C-labeled isoprene and respiratory (13)CO(2) emission.In intact plants, assimilated (13)CO(2) was rapidly translocated via the phloem to the roots within 1 hour, with an average phloem transport velocity of 20.3 ± 2.5 cm h(-1). (13)C label was stored in the roots and partially reallocated to the plants' apical part one day after labeling, particularly in the absence of photosynthesis. The daily C loss as BVOC ranged between 1.6% in mature leaves and 7.0% in young leaves. Non-isoprene BVOC accounted under light conditions for half of the BVOC C loss in young leaves and one-third in mature leaves. The C loss as isoprene originated mainly (76-78%) from recently fixed CO(2), to a minor extent from xylem-transported sugars (7-11%) and from photosynthetic intermediates with slower turnover rates (8-11%).We quantified the plants' C loss as respiratory CO(2) and BVOC emissions, allowing in tandem with metabolic analysis to deepen our understanding of ecosystem C flux.
[1587] Hörtnagl, L., I. Bamberger, M. Graus, T. M. Ruuskanen, R. Schnitzhofer, M. Müller, A. Hansel, and G. Wohlfahrt, "Biotic, abiotic and management controls on methanol exchange above a temperate mountain grassland.", J Geophys Res Biogeosci, vol. 116, Sep, 2011.
Link: http://dx.doi.org/10.1029/2011jg001641
Abstract
<p>Methanol (CH3OH) fluxes were quantified above a managed temperate mountain grassland in the Stubai Valley (Tyrol, Austria) during the growing seasons 2008 and 2009. Half-hourly methanol fluxes were calculated by means of the virtual disjunct eddy covariance (vDEC) method using 3-dimensional wind data from a sonic anemometer and methanol volume mixing ratios measured with a proton-transfer-reaction mass spectrometer (PTR-MS). During (undisturbed) mature and growing phases methanol fluxes exhibited a clear diurnal cycle with close-to-zero fluxes during nighttime and emissions, up to 10 nmol m(-2) s(-1), which followed the diurnal course of radiation and air temperature. Management events were found to represent the largest perturbations of methanol exchange at the studied grassland ecosystem: Peak emissions of 144.5 nmol m(-2) s(-1) were found during/after cutting of the meadow reflecting the wounding of the plant material and subsequent depletion of the leaf internal aqueous methanol pools. After the application of organic fertilizer, elevated methanol emissions of up to 26.7 nmol m(-2) s(-1) were observed, likely reflecting enhanced microbial activity associated with the applied manure. Simple and multiple linear regression analyses revealed air temperature and radiation as the dominant abiotic controls, jointly explaining 47 % and 70 % of the variability in half-hourly and daily methanol fluxes. In contrast to published leaf-level laboratory studies, the surface conductance and the daily change in the amount of green plant area, used as ecosystem-scale proxies for stomatal conductance and growth, respectively, were found to exert only minor biotic controls on methanol exchange.</p>
[FeilbergTavsNyord2011] Nyord}, A. {Feilberg, M. N. Ã. ¸rrega Hansen, and S. Lindholst, "Chemical evaluation of odor reduction by soil injection of animal manure.", J Environ Qual, vol. 40, no. 5: Dep. of Biosystem Engineering, Faculty of Science and Technology, Aarhus Univ., Denmark. anders.feilberg@agrsci.dk, pp. 1674–1682, 2011.
Link: http://dx.doi.org/10.2134/jeq2010.0499
Abstract
Field application of animal manure is a major cause of odor nuisance in the local environment. Therefore, there is a need for methods for measuring the effect of technologies for reducing odor after manure application. In this work, chemical methods were used to identify key odorants from field application of pig manure based on experiments with surface application by trailing hoses and soil injection. Results from three consecutive years of field trials with full-scale equipment are reported. Methods applied were: membrane inlet mass spectrometry (MIMS), proton-transfer-reaction mass spectrometry (PTR-MS), gold-film hydrogen sulfide (H?S) detection, all performed on site, and thermal desorption gas chromatography with mass spectrometry (TD-GC/MS) based on laboratory analyses of field samples. Samples were collected from a static flux chamber often used for obtaining samples for dynamic olfactometry. While all methods were capable of detecting relevant odorants, PTR-MS gave the most comprehensive results. Based on odor threshold values, 4-methylphenol, H?S, and methanethiol are suggested as key odorants. Significant odorant reductions by soil injection were consistently observed in all trials. The flux chamber technique was demonstrated to be associated with critical errors due to compound instabilities in the chamber. This was most apparent for H?S, on a time scale of a few minutes, and on a longer time scale for methanethiol.
[1506] Wolfe, G.. M., J.. A. Thornton, N.. C. Bouvier-Brown, A.. H. Goldstein, J.-H.. Park, M.. McKay, D.. M. Matross, J.. Mao, W.. H. Brune, B.. W. LaFranchi, et al., "The Chemistry of Atmosphere-Forest Exchange (CAFE) Model ¬タモ Part 2: Application to BEARPEX-2007 observations", Atmospheric Chemistry and Physics, vol. 11, pp. 1269–1294, Feb, 2011.
Link: http://nature.berkeley.edu/ahg/pubs/Wolf et al acp-11-1269-2011.pdf
Abstract
<p>In a companion paper, we introduced the Chemistry of Atmosphere-Forest Exchange (CAFE) model, a vertically-resolved 1-D chemical transport model designed to probe the details of near-surface reactive gas exchange. Here, we apply CAFE to noontime observations from the 2007 Biosphere Effects on Aerosols and Photochemistry Experiment (BEARPEX-2007). In this work we evaluate the CAFE modeling approach, demonstrate the significance of in-canopy chemistry for forest-atmosphere exchange and identify key shortcomings in the current understanding of intra-canopy processes. CAFE generally reproduces BEARPEX-2007 observations but requires an enhanced radical recycling mechanism to overcome a factor of 6 underestimate of hydroxyl (OH) concentrations observed during a warm (&nbsp;29 &deg;C) period. Modeled fluxes of acyl peroxy nitrates (APN) are quite sensitive to gradients in chemical production and loss, demonstrating that chemistry may perturb forest-atmosphere exchange even when the chemical timescale is long relative to the canopy mixing timescale. The model underestimates peroxy acetyl nitrate (PAN) fluxes by 50% and the exchange velocity by nearly a factor of three under warmer conditions, suggesting that near-surface APN sinks are underestimated relative to the sources. Nitric acid typically dominates gross dry N deposition at this site, though other reactive nitrogen (NOy) species can comprise up to 28% of the N deposition budget under cooler conditions. Upward NO2 fluxes cause the net above-canopy NOy flux to be &nbsp;30% lower than the gross depositional flux. CAFE under-predicts ozone fluxes and exchange velocities by &nbsp;20%. Large uncertainty in the parameterization of cuticular and ground deposition precludes conclusive attribution of non-stomatal fluxes to chemistry or surface uptake. Model-measurement comparisons of vertical concentration gradients for several emitted species suggests that the lower canopy airspace may be only weakly coupled with the upper canopy. Future efforts to model forest-atmosphere exchange will require a more mechanistic understanding of non-stomatal deposition and a more thorough characterization of in-canopy mixing processes.</p>
[Bamberger2011] Bamberger, I., L. Hörtnagl, TM. Ruuskanen, R. Schnitzhofer, M. Müller, M. Graus, T. Karl, G. Wohlfahrt, and A. Hansel, "Deposition fluxes of terpenes over grassland", Journal of Geophysical Research: Atmospheres (1984–2012), vol. 116, no. D14: Wiley Online Library, 2011.
Link: http://onlinelibrary.wiley.com/doi/10.1029/2010JD015457/full
Abstract
Eddy covariance flux measurements were carried out for two subsequent vegetation periods above a temperate mountain grassland in an alpine valley using a proton-transfer-reaction-mass spectrometer (PTR-MS) and a PTR time-of-flight-mass spectrometer (PTR-TOF). In 2008 and during the first half of the vegetation period 2009 the volume mixing ratios (VMRs) for the sum of monoterpenes (MTs) were typically well below 1 ppbv and neither MT emission nor deposition was observed. After a hailstorm in July 2009 an order of magnitude higher amount of terpenes was transported to the site from nearby coniferous forests causing elevated VMRs. As a consequence, deposition fluxes of terpenes to the grassland, which continued over a time period of several weeks without significant reemission, were observed. For days without precipitation the deposition occurred at velocities close to the aerodynamic limit. In addition to monoterpene uptake, deposition fluxes of the sum of sesquiterpenes (SQTs) and the sum of oxygenated terpenes (OTs) were detected. Considering an entire growing season for the grassland (i.e., 1 April to 1 November 2009), the cumulative carbon deposition of monoterpenes reached 276 mg C m−2. This is comparable to the net carbon emission of methanol (329 mg C m−2), which is the dominant nonmethane volatile organic compound (VOC) emitted from this site, during the same time period. It is suggested that deposition of monoterpenes to terrestrial ecosystems could play a more significant role in the reactive carbon budget than previously assumed.
[1492] Misztal, P.. K., E.. Nemitz, B.. Langford, C.. F. Di Marco, G.. J. Phillips, C.. N. Hewitt, A.. R. MacKenzie, S.. M. Owen, D.. Fowler, M.. R. Heal, et al., "Direct ecosystem fluxes of volatile organic compounds from oil palms in South-East Asia", Atmospheric Chemistry and Physics, vol. 11, pp. 8995–9017, 2011.
Link: http://www.atmos-chem-phys.net/11/8995/2011/
Abstract
<p>This paper reports the first direct eddy covariance fluxes of reactive biogenic volatile organic compounds (BVOCs) from oil palms to the atmosphere using proton-transfer-reaction mass spectrometry (PTR-MS), measured at a plantation in Malaysian Borneo. At midday, net isoprene flux constituted the largest fraction (84 %) of all emitted BVOCs measured, at up to 30 mg m&minus;2 h&minus;1 over 12 days. By contrast, the sum of its oxidation products methyl vinyl ketone (MVK) and methacrolein (MACR) exhibited clear deposition of 1 mg m&minus;2 h&minus;1, with a small average canopy resistance of 230 s m&minus;1. Approximately 15 % of the resolved BVOC flux from oil palm trees could be attributed to floral emissions, which are thought to be the largest reported biogenic source of estragole and possibly also toluene. Although on average the midday volume mixing ratio of estragole exceeded that of toluene by almost a factor of two, the corresponding fluxes of these two compounds were nearly the same, amounting to 0.81 and 0.76 mg m&minus;2 h&minus;1, respectively. By fitting the canopy temperature and PAR response of the MEGAN emissions algorithm for isoprene and other emitted BVOCs a basal emission rate of isoprene of 7.8 mg m&minus;2 h&minus;1 was derived. We parameterise fluxes of depositing compounds using a resistance approach using direct canopy measurements of deposition. Consistent with Karl et al. (2010), we also propose that it is important to include deposition in flux models, especially for secondary oxidation products, in order to improve flux predictions.</p>
[Ruuskanen2011] Ruuskanen, TM., M. Müller, R. Schnitzhofer, T. Karl, M. Graus, I. Bamberger, L. Hoertnagl, F. Brilli, G. Wohlfahrt, and A. Hansel, "Eddy covariance VOC emission and deposition fluxes above grassland using PTR-TOF", Atmos. Chem. Phys, vol. 11, pp. 611–625, 2011.
Link: http://www.atmos-chem-phys.net/11/611/2011/acp-11-611-2011.html
Abstract
Eddy covariance (EC) is the preferable technique for flux measurements since it is the only direct flux determination method. It requires a continuum of high time resolution measurements (e.g. 5–20 Hz). For volatile organic compounds (VOC) soft ionization via proton transfer reaction has proven to be a quantitative method for real time mass spectrometry; here we use a proton transfer reaction time of flight mass spectrometer (PTR-TOF) for 10 Hz EC measurements of full mass spectra up to m/z 315. The mass resolution of the PTR-TOF enabled the identification of chemical formulas and separation of oxygenated and hydrocarbon species exhibiting the same nominal mass. We determined 481 ion mass peaks from ambient air concentration above a managed, temperate mountain grassland in Neustift, Stubai Valley, Austria. During harvesting we found significant fluxes of 18 compounds distributed over 43 ions, including protonated parent compounds, as well as their isotopes and fragments and VOC-H+ – water clusters. The dominant BVOC fluxes were methanol, acetaldehyde, ethanol, hexenal and other C6 leaf wound compounds, acetone, acetic acid, monoterpenes and sequiterpenes.
[Stavrakou2011] Stavrakou, T., A. Guenther, A. Razavi, L. Clarisse, C. Clerbaux, P-F. Coheur, D. Hurtmans, F. Karagulian, M. De Mazière, C. Vigouroux, et al., "First space-based derivation of the global atmospheric methanol emission fluxes", Atmospheric chemistry and physics, vol. 11, no. 10: Copernicus GmbH, pp. 4873–4898, 2011.
Link: http://www.atmos-chem-phys.net/11/4873/2011/acp-11-4873-2011.html
Abstract
This study provides improved methanol emission estimates on the global scale, in particular for the largest methanol source, the terrestrial biosphere, and for biomass burning. To this purpose, one complete year of spaceborne measurements of tropospheric methanol columns retrieved for the first time by the thermal infrared sensor IASI aboard the MetOp satellite are compared with distributions calculated by the IMAGESv2 global chemistry-transport model. Two model simulations are performed using a priori biogenic methanol emissions either from the new MEGANv2.1 emission model, which is fully described in this work and is based on net ecosystem flux measurements, or from a previous parameterization based on net primary production by Jacob et al. (2005). A significantly better model performance in terms of both amplitude and seasonality is achieved through the use of MEGANv2.1 in most world regions, with respect to IASI data, and to surface- and air-based methanol measurements, even though important discrepancies over several regions are still present. As a second step of this study, we combine the MEGANv2.1 and the IASI column abundances over continents in an inverse modelling scheme based on the adjoint of the IMAGESv2 model to generate an improved global methanol emission source. The global optimized source totals 187 Tg yr−1 with a contribution of 100 Tg yr−1 from plants, only slightly lower than the a priori MEGANv2.1 value of 105 Tg yr−1. Large decreases with respect to the MEGANv2.1 biogenic source are inferred over Amazonia (up to 55 %) and Indonesia (up to 58 %), whereas more moderate reductions are recorded in the Eastern US (20–25 %) and Central Africa (25–35 %). On the other hand, the biogenic source is found to strongly increase in the arid and semi-arid regions of Central Asia (up to a factor of 5) and Western US (factor of 2), probably due to a source of methanol specific to these ecosystems which is unaccounted for in the MEGANv2.1 inventory. The most significant error reductions achieved by the optimization concern the derived biogenic emissions over the Amazon and over the Former Soviet Union. The robustness of the derived fluxes to changes in convective updraft fluxes, in methanol removal processes, and in the choice of the biogenic a priori inventory is assessed through sensitivity inversions. Detailed comparisons of the model with a number of aircraft and surface observations of methanol, as well as new methanol measurements in Europe and in the Reunion Island show that the satellite-derived methanol emissions improve significantly the agreement with the independent data, giving thus credence to the IASI dataset.
[1509] Goldstein, A. H., J. F. Karlik, S. Fares, E. Ormeno Lafuente, D. Gentner, J-H. Park, R. Weber, and M. McKay, "Flux Measurements of Biogenic Precursors to Ozone and Particulate Matter in the Central Valley", Report for the California Air Resources Board and the California Environmental Protection Agency, Aug, 2011.
Link: http://nature.berkeley.edu/ahg/pubs/ARB FR 2011 CITRUS Final Report Contract 06-329.pdf
[1491] Hewitt, C.. N., K.. Ashworth, A.. Boynard, A.. Guenther, B.. Langford, A.. R. MacKenzie, P.. K. Misztal, E.. Nemitz, S.. M. Owen, M.. Possell, et al., "Ground-level ozone influenced by circadian control of isoprene emissions", Nature Geoscience, vol. 4, pp. 671–674, 2011.
Abstract
<p>The volatile organic compound isoprene is produced by many plant species, and provides protection against biotic and abiotic stresses1. Globally, isoprene emissions from plants are estimated to far exceed anthropogenic emissions of volatile organic compounds2. Once in the atmosphere, isoprene reacts rapidly with hydroxyl radicals3 to form peroxy radicals, which can react with nitrogen oxides to form ground-level ozone4. Here, we use canopy-scale measurements of isoprene fluxes from two tropical ecosystems in Malaysia&mdash;a rainforest and an oil palm plantation&mdash;and three models of atmospheric chemistry to explore the effects of isoprene fluxes on ground-level ozone. We show that isoprene emissions in these ecosystems are under circadian control on the canopy scale, particularly in the oil palm plantation. As a result, these ecosystems emit less isoprene than present emissions models predict. Using local-, regional- and global-scale models of atmospheric chemistry and transport, we show that accounting for circadian control of isoprene emissions brings model predictions of ground-level ozone into better agreement with measurements, especially in isoprene-sensitive regions of the world.</p>
[Laffineur2011a] Laffineur, Q., M. Aubinet, N. Schoon, C. Amelynck, J-F. Müller, J. Dewulf, H. Van Langenhove, K. Steppe, M. Šimpraga, and B. Heinesch, "Isoprene and monoterpene emissions from a mixed temperate forest", Atmospheric Environment, vol. 45, no. 18: Elsevier, pp. 3157–3168, 2011.
Link: http://www.sciencedirect.com/science/article/pii/S1352231011001981
Abstract
<p>We measured the isoprene and monoterpene fluxes continuously above a mixed forest site at Vielsalm in the eastern part of Belgium, using the disjunct eddy covariance technique with proton transfer reaction-mass spectrometry. Simultaneously, we also measured the carbon dioxide fluxes in order to deduce the gross primary production. The measurements were conducted from July to September 2009. During the day, the seasonal evolution of the isoprene/monoterpene emissions was studied using a monthly temperature and light dependence function deduced from our results to standardize the fluxes. A seasonal decrease in the standard emission factors was observed, probably linked to acclimation or senescence. The standard emission factor for isoprene fluxes (30 &deg;C, 1000 μmol m&minus;2 s&minus;1) fell from 0.91 &plusmn; 0.01 to 0.56 &plusmn; 0.02 μg m&minus;2 s&minus;1 and for monoterpene fluxes from 0.74 &plusmn; 0.03 to 0.27 &plusmn; 0.03 μg m&minus;2 s&minus;1. During the night, a slight positive flux of monoterpenes was observed that seemed to be driven by air temperature. The standard emission factor (30&deg;C) for nighttime monoterpene fluxes was equal to 0.093 &plusmn; 0.019 μg m&minus;2 s&minus;1. Finally, we studied the seasonal evolution of the relationship between the gross primary production and the isoprene/monoterpenes fluxes. A linear relationship was observed, highlighting the strong link between carbon assimilation and isoprene/monoterpene emissions.</p>
2010
[1585] Bamberger, I.., L.. Hortnagl, R.. Schnitzhofer, M.. Graus, T.. M. Ruuskanen, M.. Muller, J.. Dunkl, G.. Wohlfahrt, and A.. Hansel, "BVOC fluxes above mountain grassland.", Biogeosciences, vol. 7, May, 2010.
Link: http://www.biogeosciences.net/7/1413/2010/bg-7-1413-2010.html
Abstract
<p>Grasslands comprise natural tropical savannah over managed temperate fields to tundra and cover one quarter of the Earth&#39;s land surface. Plant growth, maintenance and decay result in volatile organic compound (VOCs) emissions to the atmosphere. Furthermore, biogenic VOCs (BVOCs) are emitted as a consequence of various environmental stresses including cutting and drying during harvesting. Fluxes of BVOCs were measured with a proton-transfer-reaction-mass-spectrometer (PTR-MS) over temperate mountain grassland in Stubai Valley (Tyrol, Austria) over one growing season (2008). VOC fluxes were calculated from the disjunct PTR-MS data using the virtual disjunct eddy covariance method and the gap filling method. Methanol fluxes obtained with the two independent flux calculation methods were highly correlated (y = 0.95&times;-0.12, R (2) = 0.92). Methanol showed strong daytime emissions throughout the growing season - with maximal values of 9.7 nmol m(-2) s(-1), methanol fluxes from the growing grassland were considerably higher at the beginning of the growing season in June compared to those measured during October (2.5 nmol m(-2) s(-1)). Methanol was the only component that exhibited consistent fluxes during the entire growing periods of the grass. The cutting and drying of the grass increased the emissions of methanol to up to 78.4 nmol m(-2) s(-1). In addition, emissions of acetaldehyde (up to 11.0 nmol m(-2) s(-1)), and hexenal (leaf aldehyde, up to 8.6 nmol m(-2) s(-1)) were detected during/after harvesting.</p>
[Bamberger2010] Bamberger, I., L. Hörtnagl, R. Schnitzhofer, M. Graus, TM. Ruuskanen, M. Müller, J. Dunkl, G. Wohlfahrt, and A. Hansel, "BVOC fluxes above mountain grassland", Biogeosciences, vol. 7, no. 5: Copernicus GmbH, pp. 1413–1424, 2010.
Link: http://www.biogeosciences.net/7/1413/2010/bg-7-1413-2010.pdf
[1584] Hörtnagl, L., R. Clement, M. Graus, A. Hammerle, A. Hansel, and G. Wohlfahrt, "Dealing with disjunct concentration measurements in eddy covariance applications: a comparison of available approaches.", Atmos Environ (1994), vol. 44, May, 2010.
Link: http://www.sciencedirect.com/science/article/pii/S1352231010001810
Abstract
<p>Using proton transfer reaction mass spectrometry equipped with a quadrupol mass analyser to quantify the biosphere-atmosphere exchange of volatile organic compounds (VOC), concentrations of different VOC are measured sequentially. Depending on how many VOC species are targeted and their respective integration times, each VOC is measured at repeat rates on the order of a few seconds. This represents an order of magnitude longer sample interval compared to the standard eddy covariance (EC) method (5-20 Hz sampling rates). Here we simulate the effect of disjunct sampling on EC flux estimates by decreasing the time resolution of CO2 and H2O concentrations measured at 20 Hz above a temperate mountain grassland in the Austrian Alps. Fluxes for one month are calculated with the standard EC method and compared to fluxes calculated based on the disjunct data (1, 3 and 5 s sampling rates) using the following approaches: i) imputation of missing concentrations based on the nearest neighbouring samples (iDECnn), ii) imputation by linear interpolation (iDECli), and iii) virtual disjunct EC (vDEC), i.e. flux calculation based solely on the disjunct concentrations. It is shown that the two imputation methods result in additional low-pass filtering, longer lag times (as determined with the maximum cross-correlation method) and a flux loss of 3-30 % as compared to the standard EC method. A novel procedure, based on a transfer function approach, which specifically corrects for the effect of data treatment, was developed, resulting in improved correspondence (to within 2 %). The vDEC method yields fluxes which approximate the true (20 Hz) fluxes to within 3-7 % and it is this approach we recommend because it involves no additional empirical corrections. The only drawback of the vDEC method is the noisy nature of the cross-correlations, which poses problems with lag determination - practical approaches to overcome this limitation are discussed.</p>
[Karl2010] Karl, T., P. Harley, L. Emmons, B. Thornton, A. Guenther, C. Basu, A. Turnipseed, and K. Jardine, "Efficient atmospheric cleansing of oxidized organic trace gases by vegetation", Science, vol. 330, no. 6005: American Association for the Advancement of Science, pp. 816–819, 2010.
Link: http://www.sciencemag.org/content/330/6005/816.short
Abstract
The biosphere is the major source and sink of nonmethane volatile organic compounds (VOCs) in the atmosphere. Gas-phase chemical reactions initiate the removal of these compounds from the atmosphere, which ultimately proceeds via deposition at the surface or direct oxidation to carbon monoxide or carbon dioxide. We performed ecosystem-scale flux measurements that show that the removal of oxygenated VOC via dry deposition is substantially larger than is currently assumed for deciduous ecosystems. Laboratory experiments indicate efficient enzymatic conversion and potential up-regulation of various stress-related genes, leading to enhanced uptake rates as a response to ozone and methyl vinyl ketone exposure or mechanical wounding. A revised scheme for the uptake of oxygenated VOCs, incorporated into a global chemistry-transport model, predicts appreciable regional changes in annual dry deposition fluxes.
[Mueller2010] Müller, M., M. Graus, TM. Ruuskanen, R. Schnitzhofer, I. Bamberger, L. Kaser, T. Titzmann, L. Hoertnagl, G. Wohlfahrt, T. Karl, et al., "First eddy covariance flux measurements by PTR-TOF", Atmospheric Measurement Techniques, vol. 3, pp. 387–395, 2010.
Link: http://adsabs.harvard.edu/abs/2010AMT.....3..387M
Abstract
We have developed a High-Temperature Proton-Transfer-Reaction Mass Spectrometer (HT-PTR-MS) in which both the ion source and the ion drift tube can be continuously operated at temperatures up to 250 °C. The instrument was characterized in a high E/N-mode (130 Td) and in a low E/N-mode (87 Td) at an operating temperature of 200 °C. Instrumental sensitivities and 2σ-detection limits were on the order of 50–110 cps/ppb and 100 ppt (1 s signal integration time), respectively. The HT-PTR-MS is primarily intended for measuring "sticky" or semi-volatile trace gases. Alternatively, it may be coupled to a particle collection/thermal desorption apparatus to measure particle-bound organics in near real-time. In view of these applications, we have measured instrumental response times for a series of reference compounds. 1/e2-response times for dimethyl sulfoxide, ammonia and monoethanolamine were in the sub-second to second regime. 1/e2-response times for levoglucosan, oxalic acid and cis-pinonic acid ranged from 8 to 370 s.
[1493] Langford, B.., P.. K. Misztal, E.. Nemitz, B.. Davison, C.. Helfter, T.. A. M. Pugh, A.. R. MacKenzie, S.. F. Lim, and C.. N. Hewitt, "Fluxes and concentrations of volatile organic compounds from a South-East Asian tropical rainforest", Atmospheric Chemistry and Physics, vol. 10, pp. 8391–8412, 2010.
Link: http://www.atmos-chem-phys.net/10/8391/2010/
Abstract
<p>As part of the OP3 field study of rainforest atmospheric chemistry, above-canopy fluxes of isoprene, monoterpenes and oxygenated volatile organic compounds were made by virtual disjunct eddy covariance from a South-East Asian tropical rainforest in Malaysia. Approximately 500 hours of flux data were collected over 48 days in April&ndash;May and June&ndash;July 2008. Isoprene was the dominant non-methane hydrocarbon emitted from the forest, accounting for 80% (as carbon) of the measured emission of reactive carbon fluxes. Total monoterpene emissions accounted for 18% of the measured reactive carbon flux. There was no evidence for nocturnal monoterpene emissions and during the day their flux rate was dependent on both light and temperature. The oxygenated compounds, including methanol, acetone and acetaldehyde, contributed less than 2% of the total measured reactive carbon flux. The sum of the VOC fluxes measured represents a 0.4% loss of daytime assimilated carbon by the canopy, but atmospheric chemistry box modelling suggests that most (90%) of this reactive carbon is returned back to the canopy by wet and dry deposition following chemical transformation. The emission rates of isoprene and monoterpenes, normalised to 30 &deg;C and 1000 μmol m&minus;2 s&minus;1 PAR, were 1.6 mg m&minus;2 h&minus;1 and 0.46mg m&minus;2 h&minus;1 respectively, which was 4 and 1.8 times lower respectively than the default value for tropical forests in the widely-used MEGAN model of biogenic VOC emissions. This highlights the need for more direct canopy-scale flux measurements of VOCs from the world&#39;s tropical forests.</p>
[Taipale2010] Taipale, R., T. M. Ruuskanen, and J. Rinne, "Lag time determination in DEC measurements with PTR-MS", Atmospheric Measurement Techniques Discussions, vol. 3, no. 1: Copernicus GmbH, pp. 405–429, 2010.
Link: http://www.atmos-meas-tech-discuss.net/3/405/2010/
Abstract
The disjunct eddy covariance (DEC) method has emerged as a popular technique for micrometeorological flux measurements of volatile organic compounds (VOCs). It has usually been combined with proton transfer reaction mass spectrometry (PTR-MS), an online technique for VOC concentration measurements. However, the determination of the lag time between wind and concentration measurements has remained an important challenge. To address this conundrum, we studied the effect of different lag time methods on DEC fluxes. The analysis was based on both actual DEC measurements with PTR-MS and simulated DEC data derived from high frequency H2O measurements with an infrared gas analyzer. Conventional eddy covariance fluxes of H2O served as a reference in the DEC simulation. The individual flux measurements with PTR-MS were rather sensitive to the lag time methods, but typically this effect averaged out when the median fluxes were considered. The DEC simulation revealed that the maximum covariance method was prone to overestimation of the absolute values of fluxes. The constant lag time methods, one resting on a value calculated from the sampling flow and the sampling line dimensions and the other on a typical daytime value, had a tendency to underestimate. The visual assessment method and our new averaging approach based on running averaged covariance functions did not yield statistically significant errors and thus fared better than the habitual choice, the maximum covariance method. Given this feature and the potential for automatic flux calculation, we recommend using the averaging approach in DEC measurements with PTR-MS.
[Ghirardo2010a] Ghirardo, A., K. Koch, R. Taipale, I. Zimmer, J-P. Schnitzler, and J. Rinne, "Monoterpene emissions from boreal tree species: Determination of de novo and pool emissions", EGU General Assembly Conference Abstracts, vol. 12, pp. 2448, 2010.
Link: http://adsabs.harvard.edu/abs/2010EGUGA..12.2448G
Abstract
Boreal forests emit a large amount of monoterpenes into the atmosphere. Traditionally these emissions are assumed to originate as evaporation from large storage pools. Thus their diurnal cycle would depend mostly on temperature. However, there is indication that a significant part of the monoterpene emission would originate directly from de novo synthesis. By applying 13CO2 fumigation and analyzing the isotope fractions with proton transfer reaction mass spectrometry (PTR-MS) and classical GC-MS we studied the origin of monoterpene emissions from some major Eurasian boreal and alpine tree species. We determined the fractions originating from de novo biosynthesis and from large internal monoterpene storages for three coniferous tree species with specialized monoterpene storage structures and one dicotyledon species without such structures. The emission from dicotyledon species Betula pendula originated solely from the de novo synthesis. The origin of the emissions from coniferous species was mixed with varying fraction originating from de novo synthesis (Pinus sylvestris 58 %, Picea abies 33.5 %, Larix decidua 9.8 %) and the rest from large internal monoterpene storage pools. We have also measured the ecosystem scale monoterpene emission fluxes from a boreal Pinus sylvestris forest by disjunct eddy covariance technique. Application of the observed fraction of emission originating from de novo synthesis and large storage pools in a hybrid emission algorithm resulted in a better description of ecosystem scale monoterpene emissions, as compared to the measured fluxes.
[Ruuskanen2010] Ruuskanen, TM., M. Müller, R. Schnitzhofer, T. Karl, M. Graus, I. Bamberger, L. Hoertnagl, F. Brilli, G. Wohlfahrt, and A. Hansel, "VOC Emission and Deposition Eddy Covariance Fluxes above Grassland using PTR-TOF", AGU Fall Meeting Abstracts, vol. 1, pp. 0219, 2010.
Link: http://adsabs.harvard.edu/abs/2010AGUFM.A53C0219R
Abstract
Eddy covariance (EC) is the preferable technique for flux measurements since it is the only direct flux determination method. It requires a continuum of high time resolution measurements (e.g. 5-20 Hz). For volatile organic compounds (VOC) soft ionization via proton transfer reaction has proven to be a quantitative method for real time mass spectrometry; here we use a proton transfer reaction time of flight mass spectrometer (PTR-TOF) for 10 Hz EC measurements of full mass spectra up to m/z 315. The mass resolution of the PTR-TOF enabled the identification of chemical formulas and separation of oxygenated and hydrocarbon species exhibiting the same nominal mass. We determined 481 ion mass peaks from ambient air concentration above a managed, temperate mountain grassland in Neustift, Stubai Valley, Austria. During harvesting we found significant fluxes of 18 compounds distributed over 43 ions, including protonated parent compounds, as well as their isotopes and fragments and VOC-H+ - water clusters. The dominant BVOC fluxes were methanol, acetaldehyde, ethanol, hexenal and other C6 leaf wound compounds, acetone, acetic acid, monoterpenes and sequiterpenes. The smallest reliable fluxes we determined were less than 0.1 nmol m-2 s-1, as in the case of sesquiterpene emissions from freshly cut grass. Terpenoids, including mono- and sesquiterpenes, were also deposited to the grassland before and after the harvesting. During cutting, total VOC emission fluxes up to 200 nmolC m-2 s-1 were measured. Methanol emissions accounted for half of the emissions of oxygenated VOCs and a third of the carbon of all measured VOC emissions during harvesting.
2009
[Davison2009] Davison, B., R. Taipale, B. Langford, P. Misztal, S. Fares, G. Matteucci, F. Loreto, JN. Cape, J. Rinne, and CN. Hewitt, "Concentrations and fluxes of biogenic volatile organic compounds above a Mediterranean macchia ecosystem in western Italy", Biogeosciences, vol. 6: EGU, pp. 1655–1670, 2009.
Link: http://nora.nerc.ac.uk/8091/
Abstract
Emission rates and concentrations of biogenic volatile organic compounds (BVOCs) were measured at a Mediterranean coastal site at Castelporziano, approximately 25 km south-west of Rome, between 7 May and 3 June 2007, as part of the ACCENT-VOCBAS field campaign on biosphere–atmosphere interactions. Concentrations and emission rates were measured using the disjunct eddy covariance (DEC) method utilizing three different proton transfer reaction mass spectrometers (PTR-MS) so allowing a comparison between the instruments. The high resolution data from the PTR-MS instruments considerably enhances the original BEMA measurements of the mid 1990s. Depending on the measurement period, the volume mixing ratios were in the range 1.6–3.5 ppbv for methanol, 0.44–1.3 ppbv for acetaldehyde, 0.96–2.1 ppbv for acetone, 0.10–0.14 ppbv for isoprene, and 0.13–0.30 ppbv for monoterpenes. A diurnal cycle in mixing ratios was apparent with daytime maxima for methanol, acetaldehyde, acetone, and isoprene. The fluxes ranged from 370–440 μg m−2 h−1 for methanol, 180–360 μg m−2 h−1 for acetaldehyde, 180–450 μg m−2 h−1 for acetone, 71–290 μg m−2 h−1 for isoprene, and 240–860 μg m−2 h−1 for monoterpenes. From the measured flux data (7 May–3 June) an average basal emission rate for the Macchia vegetation was calculated of 430 μg m−2 h−1 for isoprene and 1100 μg m−2 h−1 for monoterpenes.
[Karl2009] Karl, T., E. Apel, A. Hodzic, DD. Riemer, DR. Blake, and C. Wiedinmyer, "Emissions of volatile organic compounds inferred from airborne flux measurements over a megacity", Atmospheric Chemistry and Physics, vol. 9, no. 1: Copernicus GmbH, pp. 271–285, 2009.
Link: http://www.atmos-chem-phys.net/9/271/2009/acp-9-271-2009.html
Abstract
Toluene and benzene are used for assessing the ability to measure disjunct eddy covariance (DEC) fluxes of Volatile Organic Compounds (VOC) using Proton Transfer Reaction Mass Spectrometry (PTR-MS) on aircraft. Statistically significant correlation between vertical wind speed and mixing ratios suggests that airborne VOC eddy covariance (EC) flux measurements using PTR-MS are feasible. City-median midday toluene and benzene fluxes are calculated to be on the order of 14.1±4.0 mg/m2/h and 4.7±2.3 mg/m2/h, respectively. For comparison the adjusted CAM2004 emission inventory estimates toluene fluxes of 10 mg/m2/h along the footprint of the flight-track. Wavelet analysis of instantaneous toluene and benzene measurements during city overpasses is tested as a tool to assess surface emission heterogeneity. High toluene to benzene flux ratios above an industrial district (e.g. 10–15 g/g) including the International airport (e.g. 3–5 g/g) and a mean flux (concentration) ratio of 3.2±0.5 g/g (3.9±0.3 g/g) across Mexico City indicate that evaporative fuel and industrial emissions play an important role for the prevalence of aromatic compounds. Based on a tracer model, which was constrained by BTEX (BTEX– Benzene/Toluene/Ethylbenzene/m, p, o-Xylenes) compound concentration ratios, the fuel marker methyl-tertiary-butyl-ether (MTBE) and the biomass burning marker acetonitrile (CH3CN), we show that a combination of industrial, evaporative fuel, and exhaust emissions account for >87% of all BTEX sources. Our observations suggest that biomass burning emissions play a minor role for the abundance of BTEX compounds in the MCMA (2–13%).

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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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