[Knighton2007a] "Laboratory evaluation of an aldehyde scrubber system specifically for the detection of acrolein.",
J Air Waste Manag Assoc
, vol. 57, no. 11: MT 59717, USA. email@example.com, pp. 1370–1378, Nov, 2007.
We demonstrate the use of an aldehyde scrubber system to resolve isobaric aldehyde/alkene interferences in a proton transfer reaction mass spectrometer (PTR-MS) by selectively removing the aldehydes from the gas mixture without loss of quantitative information for the alkene components. The aldehyde scrubber system uses a bisulfite solution, which scrubs carbonyl compounds from the gas stream by forming water-soluble carbonyl bisulfite addition products, and has been evaluated using a synthetic mixture of acrolein and isoprene. Trapping efficiencies of acrolein exceeded 97%, whereas the transmission efficiency of isoprene was better than 92%. Quantification of the PTR-MS response to acrolein was validated through an intercomparison study that included two derivatization methods, dinitrophenylhydrazine (DNPH) and O-(4-cyano-2-ethoxybenzyl)hydroxylamine (CNET), and a spectroscopic method using a quantum cascade laser infrared absorption spectroscopy (QCL) instrument. Finally, using cigarette smoke as a complex matrix, the acrolein content was assessed using the scrubber and compared with direct QCL-based detection.
[Wehinger2007] "Lung cancer detection by proton transfer reaction mass-spectrometric analysis of human breath gas",
International Journal of Mass Spectrometry
, vol. 265, no. 1, pp. 49 - 59, 2007.
Background: Determination of the diagnostic usefulness of proton transfer reaction mass spectrometry (PTR-MS) for detecting primary lung cancer through analysis of volatile organic compounds (VOCs) in exhaled human breath was demonstrated in this investigation. Unlike, for example, gas-chromatographic analyses, PTR-MS can be used without time-consuming preconcentration of the gas samples.
[Bartolome2007] "Mass scans from a proton transfer mass spectrometry analysis of air over Mediterranean shrubland browsed by horses.",
J Environ Biol
, vol. 28, no. 4: Unitat Ecofisiologia CSIC-CREAF CREAF, Edifici C, Universitat AutÃ³noma de Barcelona, Bellaterra-08193 Barcelona, Spain. firstname.lastname@example.org, pp. 697–700, Oct, 2007.
Plants usually emit large amount and varieties of volatiles after being damaged by herbivores. However, analytical methods for measuring herbivore-induced volatiles do not normally monitor the whole range of volatiles and the response to large herbivores such as large mammals is much less studied than the response to other herbivores such as insects. In this paper we present the results of using a highly sensitive proton transfer reaction-mass spectrometry (PTR-MS) technique that allows simultaneous monitoring of leaf volatiles in the pptv range. The resulting mass scans in air over Mediterranean shrubland browsed by horses show 70 to 100% higher concentrations of the masses corresponding to mass fragments 57, 43 and 41 (mostly hexenals, acetone and acetic acid) than scans over control non-browsed shrubland. These compounds are biogeochemically active and they are significant components of the volatile organic carbon found in the atmosphere. They influence the performance of living organisms and, the chemical and physical processes of Earth's atmosphere.
[deGouw2007] "Measurements of volatile organic compounds in the earth's atmosphere using proton-transfer-reaction mass spectrometry.",
Mass Spectrom Rev
, vol. 26, no. 2: Chemical Sciences Division, Earth System Research Laboratory, National Oceanic and Atmospheric Administration, Boulder, Colorado 80305, USA. Jost.email@example.com, pp. 223–257, 2007.
<p>Proton-transfer-reaction mass spectrometry (PTR-MS) allows real-time measurements of volatile organic compounds (VOCs) in air with a high sensitivity and a fast time response. The use of PTR-MS in atmospheric research has expanded rapidly in recent years, and much has been learned about the instrument response and specificity of the technique in the analysis of air from different regions of the atmosphere. This paper aims to review the progress that has been made. The theory of operation is described and allows the response of the instrument to be described for different operating conditions. More accurate determinations of the instrument response involve calibrations using standard mixtures, and some results are shown. Much has been learned about the specificity of PTR-MS from inter-comparison studies as well the coupling of PTR-MS with a gas chromatographic interface. The literature on this issue is reviewed and summarized for many VOCs of atmospheric interest. Some highlights of airborne measurements by PTR-MS are presented, including the results obtained in fresh and aged forest-fire and urban plumes. Finally, the recent work that is focused on improving the technique is discussed.</p>
[Penuelas2007] "Methyl salicylate fumigation increases monoterpene emission rates",
, vol. 51, no. 2: Springer, pp. 372–376, 2007.
We aimed to assess the potential effects of fumigation by methyl salicylate (MeSA) on plant monoterpene production and emissions. We evaluated monoterpene production and emissions both by chromatographic and proton transfer reaction mass spectrometry at the whole plant-and leaf-scales, in MeSa-fumigated (ca. 60 mm3 m−3 in air) and control (without MeSa fumigation) holm oak (Quercus ilex L.) plants exposed to temperatures ranging from 25 to 50 °C. The MeSa-fumigated plants showed ca. 3–4-fold greater leaf monoterpene concentrations and emission rates than the control plants between the temperatures of 25 to 45 °C.
[Norman2007] "O2+ as reagent ion in the PTR-MS instrument: Detection of gas-phase ammonia",
International Journal of Mass Spectrometry
, vol. 265, no. 2: Elsevier, pp. 382–387, 2007.
Oxygen was used as a source gas in a conventional Innsbruck PTR-MS instrument to produce O2+ ions as chemical ionization (CI) reagents instead of H3O+ ions. The use of O2+ ions as CI reagents allows for fast, highly sensitive and specific measurements of gas-phase ammonia (NH3) via the electron transfer reaction O2+ + NH3 → NH3+ + O2. The instrument was tested to be linear in the 2–2000 ppbv range. Instrument sensitivity was observed to be humidity-independent and amounted to ∼40 cps/ppbv. The instrumental background was determined by sampling NH3-free air from a heated platinum/palladium catalyst. A humidity-dependent increase of the instrumental background from 70 pptv at dry conditions to 470 pptv at humid conditions was observed. The corresponding 2σ-detection limits at 1 s signal integration time were 90 pptv for dry conditions and 230 pptv for humid conditions, respectively. The observed background may be intrinsically formed in the instrument's ion source but it may also be the result of incomplete NH3 oxidation in the catalyst used for zeroing. The reported background levels and detection limits are thus to be considered as upper limits. The 1/e response time of the instrument was in the range of 3–5 s. The PTR-MS instrument was successfully deployed in the field to monitor changes in gas-phase NH3 concentrations in the few seconds to tens of seconds time range. Laboratory intercomparison measurements between the PTR-MS instrument and a commercial NH3 analyzer (AiRRmonia) were in good agreement. The use of O2+ ions as CI reagents will significantly improve the analytical capabilities of the Innsbruck PTR-MS instrument.
[Steeghs2007] "An off-line breath sampling and analysis method suitable for large screening studies.",
, vol. 28, no. 5: Molecular and Laser Physics, Institute for Molecules and Materials, Radboud University, Nijmegen, The Netherlands., pp. 503–514, May, 2007.
We present a new, off-line breath collection and analysis method, suitable for large screening studies. The breath collection system is based on the guidelines of the American Thoracic Society for the sampling of exhaled NO. Breath containing volatile gases is collected in custom-made black-layered Tedlar bags and analyzed by proton-transfer reaction mass spectrometry (PTR-MS). The collection method and data analysis is validated for its accuracy, precision, selectivity, limits of detection, sensitivity and reproducibility. Consecutive fillings of five bags by the same person gave reproducible results to within 12% relative standard deviation (RSD) for methanol, acetaldehyde, acetone and water content from breath, whereas isoprene was constant to within 30% RSD. In an exploratory small-scale case-control study, we monitor the exhaled breath of 11 lung cancer patients on the day before surgery. The control group consisted of 57 age-matched subjects, the so-called 'healthy smokers'. This study is used as an example of the use of the system presented here.
[Bunge2007] "An On-line PTR-MS System for the Sensitive Real-time Detection of Volatile Metabolites from Microbial Cultures",
International Conference on Proton Transfer Reaction Mass Spectrometry and Its Applications
, vol. 3, 2007.
AN ON-LINE PTR-MS SYSTEM FOR THE SENSITIVE REAL-TIME DETECTION OF VOLATILE METABOLITES FROM MICROBIAL CULTURES
[Weschler2007] "Ozone-initiated chemistry in an occupied simulated aircraft cabin",
Environmental Science & Technology
, vol. 41, no. 17: ACS Publications, pp. 6177–6184, 2007.
We have used multiple analytical methods to characterize the gas-phase products formed when ozone was added to cabin air during simulated 4-hour flights that were conducted in a reconstructed section of a B-767 aircraft containing human occupants. Two separate groups of 16 females were each exposed to four conditions: low air exchange (4.4 h-1), <2 ppb ozone; low air exchange, 61−64 ppb ozone; high air exchange (8.8 h-1), <2 ppb ozone; and high air exchange, 73−77 ppb ozone. The addition of ozone to the cabin air increased the levels of identified byproducts from 70 to 130 ppb at the lower air exchange rate and from 30 to 70 ppb at the higher air exchange rate. Most of the increase was attributable to acetone, nonanal, decanal, 4-oxopentanal (4-OPA), 6-methyl-5-hepten-2-one (6-MHO), formic acid, and acetic acid, with 0.25−0.30 mol of quantified product volatilized per mol of ozone consumed. Several of these compounds reached levels above their reported odor thresholds. Most byproducts were derived from surface reactions with occupants and their clothing, consistent with the inference that occupants were responsible for the removal of >55% of the ozone in the cabin. The observations made in this study have implications for other indoor settings. Whenever human beings and ozone are simultaneously present, one anticipates production of acetone, nonanal, decanal, 6-MHO, geranyl acetone, and 4-OPA.
[Tani2007] "A proton transfer reaction mass spectrometry based system for determining plant uptake of volatile organic compounds",
, vol. 41, no. 8: Elsevier, pp. 1736–1746, 2007.
In order to evaluate the contribution that higher plants make to the removal of volatile organic compounds from the atmosphere, a measurement system consisting of a proton transfer reaction mass spectrometer (PTR-MS), CO2 analyzer, diffusion devise and leaf enclosure was established. The uptake of VOCs by Golden Pothos (Epipremnum aureum) was investigated. The overall relative error associated with measurements made using this system was <2.2% when a Golden Pothos leaf was exposed to 75–750 ppbv of methyl isobutyl ketone (MIBK). Even at the lowest MIBK concentration, more than 2.2% of the inflowing VOC was lost to the leaf, representing a detectable and positive MIBK uptake rate by the plant. The results of the investigation were compared with a measurement system based on gas chromatography analysis and it was shown that the use of a PTR-MS based system can significantly increase the certainties in determining the rate of VOC uptake by plants.
[Maleknia2007] "PTR-MS analysis of reference and plant-emitted volatile organic compounds",
International Journal of Mass Spectrometry
, vol. 262, no. 3: Elsevier, pp. 203–210, 2007.
Proton transfer reaction-mass spectrometry (PTR-MS) was applied to the analysis of a series of volatile organic compounds (VOCs) that emit from various plants. These include a group of alcohols (methanol, ethanol and butanol), carbonyl-containing compounds (acetic acid, acetone and benzaldehyde), isoprene, acetonitrile, tetrahydrofuran (THF), pyrazine, toluene and xylene and a series of terpenes (p-cymene, camphene, 2-carene, limonene, β-myrcene, α-pinene, β-pinene, γ-tepinene and terpinolene) and oxygen-containing terpenes (1,8-cineole and linalool). These mass spectral data were compared to an electron ionization (EI) database identifying that not all PTR-MS fragments were common to EI. PTR-MS studies of these reference compounds were utilized to identify VOCs emitted from Eucalyptus grandis leaf at a temperature range of 30–100 °C. In addition to protonated molecules (M + H)+, abundant proton-bound dimers or trimers were detected for alcohols, acetone, acetonitrile and THF. Abundant fragment ions attributed to the loss of water from these proton-bound clusters were also observed. The stability of butyl (C4H9+m/z 57) and acetyl (CH3CO+m/z 43) fragment ions directed the proton-transfer reactions of butanol and acetic acid. Abundant (M + H)+ ions were detected for pyrazine, THF, toluene and xylene, as well as for all terpenes except those containing oxygen. For linalool and 1,8-cineole, the loss of water generated an abundant fragment ion at m/z 137. PTR-MS fragmentation patterns for terpenes were proposed for m/z 81 (C6H9+), 93 (C7H9+), 95 (C7H11+), 107 (C8H11+), 109 (C8H13+), 119 (C9H11+), 121 (C9H13+) and 137 (loss of water for oxygen-containing terpenes; C10H17+). The relative abundances of (M + H)+ and fragments for all terpenes (except linalool) were dependent on the drift tube voltage and the optimum voltage for detection of molecular ions was different for various terpenes.
[Wisthaler2007] "PTR-MS assessment of photocatalytic and sorption-based purification of recirculated cabin air during simulated 7-h flights with high passenger density.",
Environ Sci Technol
, vol. 41, no. 1: Institut fuer Ionenphysik, Leopold-Franzens- Universitaet Innsbruck, A-6020 Innsbruck, Austria. firstname.lastname@example.org, pp. 229–234, Jan, 2007.
Four different air purification conditions were established in a simulated 3-row 21-seat section of an aircraft cabin: no air purifier; a photocatalytic oxidation unit with an adsorptive prefilter; a second photocatalytic unit with an adsorptive prefilter; and a two-stage sorption-based air filter (gas-phase absorption and adsorption). The air purifiers placed in the cabin air recirculation system were commercial prototypes developed for use in aircraft cabin systems. The four conditions were established in balanced order on 4 successive days of each of 4 successive weeks during simulated 7-h flights with 17 occupants. Proton-transfer reaction mass spectrometry was used to assess organic gas-phase pollutants and the performance of each air purifier. The concentration of most organic pollutants present in aircraft cabin air was efficiently reduced by all three units. The photocatalytic units were found to incompletely oxidize ethanol released by the wet wipes commonly supplied with airline mealsto produce unacceptably high levels of acetaldehyde and formaldehyde.
[Spitaler2007] "PTR-MS in enology: Advances in analytics and data analysis",
International Journal of Mass Spectrometry
, vol. 266, no. 1: Elsevier, pp. 1–7, 2007.
The present communication deals with the improvement of proton transfer reaction mass spectrometry (PTR-MS) wine headspace analyses. In contrast to previous PTR-MS investigations of wine, where wine headspace was ionized by protonated ethanol clusters, the headspace was diluted by a factor of 1:40 with N2 and ionized by H3O+ ions. This method is better suited for routine applications than the previously reported method since it is simpler, faster, and the mass spectra obtained are less complex. A test wine was mixed with ethanol and with water to yield ethanol contents ranging from 10 to 15% (v/v) and these mixtures were analyzed to assess whether any quantitative differences in the composition of volatiles were detectable. The data showed no impact of the ethanol content on the wine headspace composition. The new method was applied to eight different wine samples produced from two different grape varieties: Pinot Noir and Cabernet Sauvignon. Each variety was grown in two different locations in South Tyrol (Northern Italy) and harvested at two different dates. Quantitative (but not qualitative) differences in PTR-MS spectra between the two wine varieties were observed. Using principal component analysis of selected m/z signals differentiation between Pinot Noir and Cabernet Sauvignon samples was achievable.
[Aprea2007] "PTR-MS study of esters in water and water/ethanol solutions: Fragmentation patterns and partition coefficients",
International journal of mass spectrometry
, vol. 262, no. 1: Elsevier, pp. 114–121, 2007.
Esters strongly influence the perceived aroma of alcoholic beverages and their rapid monitoring can play an important role in the quality control of these products. Proton transfer reaction mass spectrometry (PTR-MS) allows the rapid and non invasive monitoring of foodstuff but there is still a lack of information about the proton transfer induced fragmentation and on the effect of high ethanol concentration. PTR-MS fragmentation patterns of 21 esters are reported, most of them for the first time. For linear methyl and ethyl esters the fragmentation dependence on E/N was also evaluated. Acetate esters, with exception of methyl acetate, show as main peaks the characteristic fragment ions at m/z 61 and m/z 43, whereas propanoate esters, but methyl propanoate, exhibit as main peaks the typical signals at m/z 75 and m/z 57. For all the other esters, here reported, the spectra are dominated by the protonated molecular ion. For methyl and ethyl esters we also report, in many cases for the first time, the water-solution/air partition coefficients (Henry's law constant) and the ethanol-solution/air partition coefficients at different ethanol concentrations. The information provided in this work may be useful as a basis for further studies for the identification and quantification of esters in the headspace of alcoholic beverages extending the application field of PTR-MS.
[Knighton2007] "Quantification of aircraft engine hydrocarbon emissions using proton transfer reaction mass spectrometry",
Journal of Propulsion and Power
, vol. 23, no. 5, pp. 949–958, 2007.
[Bouvier-Brown2007] "Quantifying sesquiterpene and oxygenated terpene emissions from live vegetation using solid-phase microextraction fibers.",
J Chromatogr A
, vol. 1161, no. 1-2: University of California, Berkeley, CA, USA. email@example.com, pp. 113–120, Aug, 2007.
Biogenic terpenes play important roles in ecosystem functioning and atmospheric chemistry. Some of these compounds are semi-volatile and highly reactive, such as sesquiterpenes and oxygenated terpenes, and are thus difficult to quantify using traditional air sampling and analysis methods. We developed an alternative approach to quantify emissions from live branches using a flow through enclosure and sample collection on solid-phase microextraction (SPME) fibers. This method allows for collection and analysis of analytes with minimal sample transfer through tubing to reduce the potential for losses. We characterized performance characteristics for 65 microm polydimethylsiloxane-divinylbenzene (PDMS/DVB) fibers using gas chromatography followed by mass spectrometry and optimized experimental conditions and procedures for field collections followed by laboratory analysis. Using 10-45 min sampling times and linear calibration curves created from mixtures of terpenes, emissions of methyl chavicol, an oxygenated terpene, and an array of sesquiterpenes were quantified from a Ponderosa pine branch. The detection limit was 4.36 pmol/mol (ppt) for methyl chavicol and 16.6 ppt for beta-caryophyllene. Concentrations determined with SPME fibers agreed with measurements made using proton transfer reaction mass spectrometry (PTR-MS) within the estimated error of the method for well calibrated compounds. This technique can be applied for quantification of biogenic oxygenated terpene and sesquiterpene emissions from live branches in the field.
[Granitto2007] "Rapid and non-destructive identification of strawberry cultivars by direct PTR-MS headspace analysis and data mining techniques",
Sensors and actuators B: Chemical
, vol. 121, no. 2: Elsevier, pp. 379–385, 2007.
Proton transfer reaction-mass spectrometry (PTR-MS) is a spectrometric technique that allows direct injection and analysis of mixtures of volatile compounds. Its coupling with data mining techniques provides a reliable and fast method for the automatic characterization of agroindustrial products. We test the validity of this approach to identify samples of strawberry cultivars by measurements of single intact fruits. The samples used were collected over 3 years and harvested in different locations. Three data mining techniques (random forests, penalized discriminant analysis and discriminant partial least squares) have been applied to the full PTR-MS spectra without any preliminary projection or feature selection. We tested the classification models in three different ways (leave-one-out and leave-group-out internal cross validation, and leaving a full year aside), thereby demonstrating that strawberry cultivars can be identified by rapid non-destructive measurements of single fruits. Performances of the different classification methods are compared.
[Aprea2007b] "Rapid white truffle headspace analysis by proton transfer reaction mass spectrometry and comparison with solid-phase microextraction coupled with gas chromatography/mass spectrometry.",
Rapid Commun Mass Spectrom
, vol. 21, no. 16: IASMA Research Center, Agri-Food Quality Department, Via E. Mach 1, 38010 S. Michele all'Adige (TN), Italy. firstname.lastname@example.org, pp. 2564–2572, 2007.
The gastronomic relevance and high price of white truffle are related mainly to its unique aroma. Here we evaluate, for the first time, the possibility of characterizing in a rapid and non-destructive way the aroma of white truffles based on proton transfer reaction mass spectrometry (PTR-MS). We indicate that anonymous PTR-MS fingerprinting allows sample classification and we also compare qualitatively and quantitatively PTR-MS data with measurements made by solid-phase microextraction gas chromatography (SPME-GC) of the same samples under the same conditions. PTR-MS fragmentation data of truffle-relevant compounds are also published here for the first time. Most of the sulfur-containing compounds detected by GC and relevant for white truffle aroma have a high positive correlation with single PTR-MS peaks. Our work indicates that, after preliminary comparison with GC data, PTR-MS is a new tool for the rapid, quantitative and non-invasive characterization of white truffle by direct headspace injection without any pre-concentration.
[Mateus2007] "Release kinetics of volatile organic compounds from roasted and ground coffee: online measurements by PTR-MS and mathematical modeling.",
J Agric Food Chem
, vol. 55, no. 25: NestlÃ© Product Technology Center, CH-1350 Orbe, Switzerland. email@example.com, pp. 10117–10128, Dec, 2007.
The present work shows the possibilities and limitations in modeling release kinetics of volatile organic compounds (VOCs) from roasted and ground coffee by applying physical and empirical models such as the diffusion and Weibull models. The release kinetics of VOCs were measured online by proton transfer reaction-mass spectrometry (PTR-MS). Compounds were identified by GC-MS, and the contribution of the individual compounds to different mass fragments was elucidated by GC/PTR-MS. Coffee samples roasted to different roasting degrees and ground to different particle sizes were studied under dry and wet stripping conditions. To investigate the accuracy of modeling the VOC release kinetics recorded using PTR-MS, online kinetics were compared with kinetics reconstituted from purge and trap samplings. Results showed that uncertainties in ion intensities due to the presence of isobaric species may prevent the development of a robust mathematical model. Of the 20 identified compounds, 5 were affected to a lower extent as their contribution to specific m/z intensity varied by <15% over the stripping time. The kinetics of these compounds were fitted using physical and statistical models, respectively, the diffusion and Weibull models, which helped to identify the underlying release mechanisms. For dry stripping, the diffusion model allowed a good representation of the release kinetics, whereas for wet stripping conditions, release patterns were very complex and almost specific for each compound analyzed. In the case of prewetted coffee, varying particle size (approximately 400-1200 microm) had no significant effect on the VOC release rate, whereas for dry coffee, the release was faster for smaller particles. The absence of particle size effect in wet coffee was attributed to the increase of opened porosity and compound diffusivity by solubilization and matrix relaxation. To conclude, the accurate modeling of VOC release kinetics from coffee allowed small variations in compound release to be discriminated. Furthermore, it evidenced the different aroma compositions that may be obtained depending on the time when VOCs are recovered.
[Steeghs2007a] "The suitability of Tedlar bags for breath sampling in medical diagnostic research",
, vol. 28, no. 1, pp. 73, 2007.
Tedlar bags are tested for their suitability for breath sampling for medical diagnostic purposes. Proton-transfer reaction-mass spectrometry was used to monitor the changes in composition of various mixtures contained in custom-made black-layered Tedlar bags. Characteristic ions at m / z 88 and 95 amu reflect considerable pollution from the bag material. The pollutant found on m / z 88 amu is most probably N , N -dimethylacetamide, a latent solvent used in the production of Tedlar film. Gas composition losses during filling were found to range from 5 to 47%, depending on the compound. Once stored, the half-lives of methanol, acetaldehyde, acetone, isoprene, benzene, toluene and styrene were estimated between 5 and 13 days. Losses from breath samples (52 h after filling) were found to be less than 10%. No observable decrease was found for ethylene over 3 days, using laser-based photoacoustic detection. For the use of Tedlar bags, a standardized protocol is advised, where the time point of analysis is fixed for all samples and should be kept as close as possible to the time of sampling.
 "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.
<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 ± 2.3 mg/m2/h) and monoterpene fluxes (1.2 ± 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 ∼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 8–10 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 ± 7% in the ∼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>
[Karl2007] "The Tropical Forest and Fire Emissions Experiment: method evaluation of volatile organic compound emissions measured by PTR-MS, FTIR, and GC from tropical biomass burning",
Atmospheric Chemistry and Physics
, vol. 7, no. 22: Copernicus GmbH, pp. 5883–5897, 2007.
Volatile Organic Compound (VOC) emissions from fires in tropical forest fuels were quantified using Proton-Transfer-Reaction Mass Spectrometry (PTRMS), Fourier Transform Infrared Spectroscopy (FTIR) and gas chromatography (GC) coupled to PTRMS (GC-PTR-MS). We investigated VOC emissions from 19 controlled laboratory fires at the USFS (United States Forest Service) Fire Sciences Laboratory and 16 fires during an intensive airborne field campaign during the peak of the burning season in Brazil in 2004. The VOC emissions were dominated by oxygenated VOCs (OVOC) (OVOC/NMHC 4:1, NMHC: non-methane hydrocarbons) The specificity of the PTR-MS instrument, which measures the mass to charge ratio of VOCs ionized by H3O+ ions, was validated by gas chromatography and by intercomparing in-situ measurements with those obtained from an open path FTIR instrument. Emission ratios for methyl vinyl ketone, methacrolein, crotonaldehyde, acrylonitrile and pyrrole were measured in the field for the first time. Our measurements show a higher contribution of OVOCs than previously assumed for modeling purposes. Comparison of fresh (<15 min) and aged (>1 h–1 d) smoke suggests altered emission ratios due to gas phase chemistry for acetone but not for acetaldehyde and methanol. Emission ratios for numerous, important, reactive VOCs with respect to acetonitrile (a biomass burning tracer) are presented.
[Shaw2007] "Volatile organic compound emissions from dairy cows and their waste as measured by proton-transfer-reaction mass spectrometry.",
Environ Sci Technol
, vol. 41, no. 4: Department of Environmental Science, Policy, and Management, University of California, Berkeley, Hilgard Hall, Berkeley, California 94720, USA. firstname.lastname@example.org, pp. 1310–1316, Feb, 2007.
California dairies house approximately 1.8 million lactating and 1.5 million dry cows and heifers. State air regulatory agencies view these dairies as a major air pollutant source, but emissions data are sparse, particularly for volatile organic compounds (VOCs). The objective of this work was to determine VOC emissions from lactating and dry dairy cows and their waste using an environmental chamber. Carbon dioxide and methane were measured to provide context for the VOCs. VOCs were measured by proton-transfer-reaction mass spectrometry (PTR-MS). The compounds with highest fluxes when cows plus waste were present were methanol, acetone + propanal, dimethylsulfide, and m/z 109 (likely 4-methyl-phenol). The compounds with highest fluxes from fresh waste (urine and feces) were methanol, m/z 109, and m/z 60 (likely trimethylamine). Ethanol fluxes are reported qualitatively, and several VOCs that were likely emitted (formaldehyde, methylamine, dimethylamine) were not detectable by PTR-MS. The sum of reactive VOC fluxes measured when cows were present was a factor of 6-10 less than estimates historically used for regulatory purposes. In addition, ozone formation potentials of the dominant VOCs were -10% those of typical combustion or biogenic VOCs. Thus dairy cattle have a comparatively small impact on ozone formation per VOC mass emitted.
[Filella2007] "Volatile organic compounds emissions in Norway spruce (Picea abies) in response to temperature changes",
, vol. 130, no. 1: Wiley Online Library, pp. 58–66, 2007.
Volatile organic compound (VOC) emissions from Norway spruce (Picea abies) saplings were monitored in response to a temperature ramp. Online measurements were made with a proton transfer reaction – mass spectrometer under controlled conditions, together with plant physiological variables. Masses corresponding to acetic acid and acetone were the most emitted VOCs. The emission rates of m137 (monoterpenes), m59 (acetone), m33 (methanol), m83 (hexanal, hexenals), m85 (hexanol) and m153 (methyl salicylate, MeSa) increased exponentially with temperature. The emission of m61 (acetic acid) and m45 (acetaldehyde), however, increased with temperature only until saturation around 30°C, closely following the pattern of transpiration rates. These results indicate that algorithms that use only incident irradiance and leaf temperature as drivers to predict VOC emission rates may be inadequate for VOCs with lower H, and consequently higher sensitivity to stomatal conductance.
[Galbally2007] "Volatile organic compounds in marine air at Cape Grim, Australia",
, vol. 4, no. 3: CSIRO, pp. 178–182, 2007.
Measurements were made of volatile organic compounds (VOCs) at Cape Grim using proton transfer reaction mass spectrometry (PTR-MS) during the Precursors to Particles (P2P) Campaign from 10 February to 1 March 2006. Approximately 14 days of clean air data were obtained along with 4 days of data from when polluted air, first from a smoke plume from a fire on Robbins Island adjacent to the station and then air from Victoria, was present. This paper deals with the results obtained in clean air, the focus of the P2P campaign. The protonated masses and probable VOCs measured in the clean marine air were: methanol, 33; acetonitrile, 42; acetaldehyde, 45; acetone, 59; isoprene, 69; methylvinyl ketone/methacrolein (MVK/MACR), 71; methylethyl ketone, 73; and benzene, 79. The measurements at Cape Grim were in some cases near the detection limit and an analytical challenge. The range of concentrations detected in clean maritime air, the relationship to the limited range of previous measurements in marine air in the Northern Hemisphere tropics, and the physical, chemical and biological processes controlling these compounds in the marine air are discussed. The methanol concentrations observed at Cape Grim are consistent with global modelling, incorporating sources that are mainly of vegetation origin. Isoprene has recently been implicated as a precursor to cloud condensation nuclei over the Southern Ocean. In this snapshot of observations at Cape Grim, Tasmania, isoprene and the isoprene oxidation products MVK and MACR appeared to be absent in air from the Southern Ocean. However, isoprene has a very short atmospheric lifetime and the spatial distribution of its emissions may be very heterogeneous. The concentrations of the other VOCs in marine air at Cape Grim, acetonitrile, acetaldehyde, acetone, methylethyl ketone and benzene, were typically a factor of four lower than that observed over the remote tropical ocean in the Northern Hemisphere. The lower concentrations of carbonyls and their precursor hydrocarbons may indicate a limitation on ozone production potential in the Southern Hemisphere compared with the Northern Hemisphere troposphere.