Laboratory studies in support of the detection of sesquiterpenes by proton-transfer-reaction-mass-spectrometry

Demarcke, M.; Amelynck, Crist; Schoon, Niels; Dhooghe, Frederik; Langenhove, Herman Van; Dewulf, Jo

doi:10.1016/j.ijms.2008.10.023

Cited by 46 publications

(56 citation statements)

References 19 publications

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“…This fragmentation results in a decrease of the detection efficiency with respect to other VOCs, which are not or hardly subjected to fragmentation following protonation (Dhoogle et al, 2008). The PTR-MS technique has already been applied for the detection of sesquiterpenes on several occasions and expected product ions and their relative abundances have been reported for some sesquiterpenes at standard PTR-MS conditions (Ezra et al, 2004;Lee et al, 2006;Demarcke et al, 2009;Kim et al, 2009Kim et al, , 2010. The relative abundance of parent SQT ion signal quantified as 32 ± 2 % and comes in line with the previous values reported.…”

Section: Ptr-ms Measurementssupporting

confidence: 86%

Ozone stress as a driving force of sesquiterpene emissions: a suggested parameterisation

et al. 2012

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Abstract. Sesquiterpenes (C 15 H 24 ) are semi-volatile organic compounds emitted by vegetation and are of interest in atmospheric research because they influence the oxidative capacity of the atmosphere and contribute to the formation of secondary organic aerosols. However, little is known about their emission pattern and no established parameterisation is available for global emission models. The aim of this study is to investigate a Central European spruce forest and its emission response to meteorological and environmental parameters, looking for a parameterisation that incorporates heat and oxidative stress as the main driving forces of the induced emissions. Therefore, a healthy ca. 80 yr old Norway spruce (Picea abies) tree was selected and a dynamical vegetation enclosure technique was applied from April to November 2011. The emissions clearly responded to temperature changes with small variations in the β-factor along the year (β spring = 0.09 ± 0.01, β summer = 0.12± 0.02, β autumn = 0.11 ± 0.02). However, daily calculated values revealed a vast amount of variability in temperature dependencies ((0.02 ± 0.002) < β < (0.27 ± 0.04)) with no distinct seasonality.By separating the complete dataset in 10 different ozone regimes, we found that in moderately or less polluted atmospheric conditions the main driving force of sesquiterpene emissions is the temperature, but when ambient ozone mixing ratios exceed a critical threshold of (36.6 ± 3.9) ppb v , the emissions become primarily correlated with ozone. Considering the complete dataset, cross correlation analysis resulted in highest correlation with ambient ozone mixing ratios (CC O 3 = 0.63 ± 0.01; CC T = 0.47 ± 0.02 at t = 0 h for temperature) with a time shift 2-4 h prior to the emissions. An only temperature dependent algorithm was found to substantially underestimate the induced emissions (20 % of the measured; R 2 = 0.31). However, the addition of an ozone dependent term improved substantially the fitting between measured and modelled emissions (81 % of the modelled emissions could be explained by the measurements; R 2 = 0.63), providing confidence about the reliability of the suggested parameterisation for the spruce forest site investigated.

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Section: Ptr-ms Measurementssupporting

confidence: 86%

Ozone stress as a driving force of sesquiterpene emissions: a suggested parameterisation

et al. 2012

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“…Frequent calibrations for the PTR-MS were performed with a gas standard containing about 1 ppm of formaldehyde, methanol, acetaldehyde, ethanol, acetone, isoprene and α-pinene (L4763, Ionimed Analytic GmbH, Austria), while SQTs were calibrated using a permeation oven technique and a β-caryophyllene standard (W225207, Sigma-Aldrich Inc.). Analytical fragmentation patterns were either derived experimentally or calculated according to the literature (Dhooghe et al, 2008;Kim et al, 2009;Demarcke et al, 2009). The tuning of the mass spectrometer and the transmission curve were frequently checked to achieve the best-optimized conditions.…”

Section: Ptr-ms Measurementsmentioning

confidence: 99%

From emissions to ambient mixing ratios: online seasonal field measurements of volatile organic compounds over a Norway spruce-dominated forest in central Germany

et al. 2014

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Abstract. Biogenic volatile organic compounds (BVOCs) are substantial contributors to atmospheric chemistry and physics and demonstrate the close relationship between biosphere and atmosphere. Their emission rates are highly sensitive to meteorological and environmental changes with concomitant impacts on atmospheric chemistry. We have investigated seasonal isoprenoid and oxygenated VOC (oxVOC) fluxes from a Norway spruce (Picea abies) tree in central Germany and explored the emission responses under various atmospheric conditions. Emission rates were quantified by using dynamic branch enclosure and proton-transfer-reaction mass spectrometry (PTR-MS) techniques. Additionally, ambient mixing ratios were derived through application of a new box model treatment on the dynamic chamber measurements. These are compared in terms of abundance and origin with the corresponding emissions. Isoprenoids dominate the BVOC emissions from Norway spruce, with monoterpenes and sesquiterpenes accounting for 50.8 ± 7.2 % and 19.8 ± 8.1 % respectively of the total emissions. Normalizing the VOC emission rates, we have observed a trend of reduction of carbon-containing emissions from April to November, with an enhancement of oxVOC. Highest emission rates were observed in June for all measured species, with the exception of sesquiterpenes, which were emitted most strongly in April. Finally, we evaluate the temperature-dependent algorithm that seems to describe the temperature-dependent emissions of methanol, acetaldehyde and monoterpenes but only with the use of the monthly derived values for emission potential, E s , and temperature dependency, β factor.

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“…Typically, MT (Tani et al, 2003) and SQT (Dhooghe et al, 2008;Kim et al, 2009;Demarcke et al, 2009) decompose by splitting off the same 56 amu (C 4 H 8 ) neutral fragment. This leaves the fragment ions m/z 81 + for MT and m/z 149 + for SQT as the dominant fragments regardless of the structure of the isomers.…”

Section: Fragmentation Patternsmentioning

confidence: 99%

“…This leads for example to a relatively small parent ion abundance for MBO (20-30%) and a negligible parent ion abundance (e.g., less than 5%) for substituted MT alcohols, such as linalool (Demarcke et al, 2009) or borneol. Substituted MT alcohols are therefore detected at the same masses as MT, m/z 81 + and 137 + .…”

Section: Fragmentation Patternsmentioning

confidence: 99%

Emissions and ambient distributions of Biogenic Volatile Organic Compounds (BVOC) in a ponderosa pine ecosystem: interpretation of PTR-MS mass spectra

et al. 2010

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Abstract. Two proton-transfer-reaction mass spectrometry systems were deployed at the Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H 2 O, Organics and Nitrogen-Southern Rocky Mountain 2008 field campaign (BEACHON-SRM08; July to September, 2008) at the Manitou Forest Observatory in a ponderosa pine woodland near Woodland Park, Colorado USA. The two PTR-MS systems simultaneously measured BVOC emissions and ambient distributions of their oxidation products. Here, we present mass spectral analysis in a wide range of masses (m/z 40 + to 210 + ) to assess our understanding of BVOC emissions and their photochemical processing inside of the forest canopy. The biogenic terpenoids, 2-methyl-3-butene-2-ol (MBO, 50.2%) and several monoterpenes (MT, 33.5%) were identified as the dominant BVOC emissions from a transmission corrected mass spectrum (PTR-MS), averaged over the daytime (11 a.m. to 3 p.m., local time) of three days. To assess contributions of oxidation products of local BVOC, we calculate an oxidation product spectrum with the OH-and ozone-initiated oxidation product distribution mass spectra of two major BVOC emissions at the ecosystem (MBO and β-pinene) that were observed from laboratory oxidation experiments. The majority (∼ 76%) of the total signal in the transmission corrected PTR-MS spectra could be explained by identified compounds. The remainder are attributed to oxidation products of BVOC emitted from nearby ecosystems and transported to the site, and oxidation products of unidentified BVOC emitted from the ponderosa pine ecosystem.

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Laboratory studies in support of the detection of sesquiterpenes by proton-transfer-reaction-mass-spectrometry

Cited by 46 publications

References 19 publications

Ozone stress as a driving force of sesquiterpene emissions: a suggested parameterisation

Ozone stress as a driving force of sesquiterpene emissions: a suggested parameterisation

From emissions to ambient mixing ratios: online seasonal field measurements of volatile organic compounds over a Norway spruce-dominated forest in central Germany

Emissions and ambient distributions of Biogenic Volatile Organic Compounds (BVOC) in a ponderosa pine ecosystem: interpretation of PTR-MS mass spectra

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