## Scientific Articles - PTR-MS Bibliography

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## Publications

Found 63 results
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1997
[Lindinger1997] "Endogenous production of methanol after the consumption of fruit", Alcoholism: Clinical and Experimental Research, vol. 21, no. 5: Wiley Online Library, pp. 939–943, 1997.
Abstract
After the consumption of fruit, the concentration of methanol in the human body increases by as much as an order of magnitude. This is due to the degradation of natural pectin (which is esterified with methyl alcohol) in the human colon. In vivo tests performed by means of proton-transfer-reaction mass spectrometry show that consumed pectin in either a pure form (10 to 15 g) or a natural form (in 1 kg of apples) induces a significant increase of methanol in the breath (and by inference in the blood) of humans. The amount generated from pectin (0.4 to 1.4 g) is approximately equivalent to the total daily endogenous production (measured to be 0.3 to 0.6 g/day) or that obtained from 0.3 liters of 80-proof brandy (calculated to be 0.5 g). This dietary pectin may contribute to the development of nonalcoholic cirrhosis of the liver.
[Hansel1997] "Energy dependencies of the proton transfer reactions H3O++ CH2O CH2OH++ H2O", International journal of mass spectrometry and ion processes, vol. 167: Elsevier, pp. 697–703, 1997.
Abstract
The proton transfer reaction system View the MathML source has been investigated in both directions as a function of the mean relative kinetic energy, KEcm, between the reactants from 0.05 eV to 1 eV in a selected ion flow drift tube (SIFDT) experiment. The rate constant kf for the forward channel follows closely the calculated collisional limiting value, kc, showing a slightly negative energy dependence. The rate constant, kr, for the reverse channel, which is endoergic by 5.2 kcal mol−1, increases from kr = 2.3 × 10−12 cm3 s−1 at KEcm = 0.05 eV to kr = 2 × 10−10 cm3 s−1 at KEcm = 1 eV. This endoergic reaction is paralleled by an associative channel forming CH2OH+·H2O, which undergoes ligand switching with water molecules to produce H3O+·H2O, yielding a bond energy BE(CH2OH+−H2O) = 27.7 kcal mol−1 in agreement with previous data. The present results are important requisites to monitor the formaldehyde concentrations in air using proton transfer reactionmass spectrometry (PTR-MS).
1999
[Gouw1999] "Emissions of volatile organic compounds from cut grass and clover are enhanced during the drying process", Geophysical Research Letters, vol. 26, no. 7: American Geophysical Union, pp. 811–814, 1999.
2000
[Holzinger2000] "Emissions of volatile organic compounds from Quercus ilex L. measured by proton transfer reaction mass spectrometry under different environmental conditions", Journal of Geophysical Research, vol. 105, no. D16, pp. 20573–20579, 2000.
2001
[Karl2001a] "Eddy covariance measurement of biogenic oxygenated VOC emissions from hay harvesting", Atmospheric Environment, vol. 35, no. 3: Elsevier, pp. 491–495, 2001.
Abstract
Biogenic oxygenated volatile organic compound (VOC) fluxes have been directly measured by eddy covariance using the combination of a fast response, real-time \{VOC\} sensor and an acoustic anemometer. \{VOC\} detection is based on proton-transfer reaction mass spectrometry which has currently a response time of ca. 0.8&#xa0;s and the system is suitable for making nearly unattended, long-term and continuous measurements of \{VOC\} fluxes. The eddy covariance system has a detection limit, for most VOCs, of less than 0.1&#xa0;mg&#xa0;mâˆ’2&#xa0;hâˆ’1. The system was field tested above a hayfield near St. Johann, Austria where cut and drying grasses released a variety of VOCs. High fluxes were observed for about 2 days after cutting and were dominated by methanol (1â€“8.4&#xa0;mg&#xa0;mâˆ’2&#xa0;hâˆ’1), acetaldehyde (0.5â€“3&#xa0;mg&#xa0;mâˆ’2&#xa0;hâˆ’1), hexenals (0.1â€“1.5&#xa0;mg&#xa0;mâˆ’2&#xa0;hâˆ’1) and acetone (0.1â€“1.5&#xa0;mg&#xa0;mâˆ’2&#xa0;hâˆ’1). The eddy covariance measurements generally agreed with flux estimates based on enclosure measurements and surface layer gradients. The sensitivity and selectivity of the system make it suitable for quantifying the fluxes of the dominant biogenic \{VOCs\} from a variety of landscapes and sources.
[Lindinger2001] Lindinger, W., R. Fall, and T. Karl, "Environmental, food and medical applications of proton-transfer-reaction mass spectrometry (PTR-MS)", , vol. 4: Elsevier: Amsterdam, The Netherlands, pp. 1-48, 2001.
Abstract
The development of proton-transfer-reaction mass spectrometry (PTR-MS) as a tool for the analysis of volatile organic compounds (VOCs) is described. PTR-MS is based on the rapid, non-dissociative transfer of protons from H3Oþ to most common VOCs, but not to the principal gases in the air sample. Recent developments in the design of PTR-MS instruments allow detection of some VOCs in the parts per trillion by volume range. This sensitivity and the capability of PTR-MS instruments to be operated for extended periods in both laboratory and ﬁeld settings has allowed exploration of many aspects of VOC analysis in environmental, food and medical applications.
2003
[Lirk2003] "Elective haemodialysis increases exhaled isoprene.", Nephrol Dial Transplant, vol. 18, no. 5: Department of Anesthesiology and Critical Care Medicine, Leopold Franzens University of Innsbruck, Anichstrasse 35, A-6020 Innsbruck, Austria., pp. 937–941, May, 2003.
Abstract
Uraemic odour is a characteristic feature of patients with end-stage renal disease (ESRD). However, few investigations have been carried out into the composition of exhaled air in ESRD patients undergoing haemodialysis (HD). Increases of exhaled isoprene levels by a factor of up to 2.7 following HD have been reported.We attempted to confirm these findings in 50 patients undergoing HD using haemophan (n=23) or polysulphone (n=27) dialysis membranes. Parallel evaluation of ambient air, calorie intake, medication and haemodynamic variables was performed. Samples were analysed using proton transfer reaction-mass spectrometry (PTR-MS).Significant changes in breath isoprene concentration were observed when comparing patients before [39.14+/-14.96 parts per billion (ppbv)] and after (63.54+/-27.59 ppbv) dialysis (P<0.001). The quotient of values before and after dialysis was 1.84 (SD 1.41). No significant differences in isoprene kinetics were found between the use of haemophan and polysulphone membranes. No significant correlations were observed between isoprene quotients and variations in blood pressure during HD, calorie intake, ingestion of lipid-lowering drugs or serum lipid levels.Isoprene concentration was higher in the exhaled air of patients after HD as compared with values before HD. Large interindividual variability existed in isoprene kinetics. Oxidative stress appears to be an unlikely cause for this rise. An alternative hypothesis is an influence of respiratory variables on isoprene exhalation based upon Henry's law constant. We therefore propose to perform online monitoring of isoprene exhalation by PTR-MS during the HD session to investigate the possible influence of respiratory variables.
[DeGouw2003] "Emission sources and ocean uptake of acetonitrile (CH3CN) in the atmosphere", Journal of geophysical research, vol. 108, no. D11: American Geophysical Union, pp. 4329, 2003.
Abstract
Airborne measurements of acetonitrile (CH3CN) were made off the U.S. west coast, over California, and during two transfer flights over the U.S. in April and May of 2002. Acetonitrile was strongly enhanced in the plumes from two forest fires, confirming the usefulness of the measurement as an indicator for biomass burning emissions. The emission ratios relative to CO of acetonitrile in the two plumes were slightly higher than previously reported values for fires burning in other fuel types. No significant acetonitrile release was observed in the Los Angeles basin or from other point sources (ships and a power plant). Acetonitrile concentrations were significantly reduced in the marine boundary layer indicating the presence of an ocean uptake sink. Increased loss of acetonitrile was observed close to the coast, suggesting that acetonitrile was efficiently lost by dissolving in the upwelling ocean water, or by biological processes in the surface water.
2004
[Jaksch2004] "The effect of ozone treatment on the microbial contamination of pork meat measured by detecting the emissions using PTR-MS and by enumeration of microorganisms", International Journal of Mass Spectrometry, vol. 239, no. 2: Elsevier, pp. 209–214, 2004.
Abstract
In this paper, we report the results of treating commercial samples of pork meat with ozone in order to determine whether such treatment reduces microbial growth and hence extends the shelf lifetime of such products. The technique of Proton-Transfer-Reaction Mass Spectrometry (PTR-MS) was used to study volatile emissions with the signal detected at mass 63 (assumed to be a measure for dimethylsulphide) being used as a diagnostic of bacterial activity. Such a signal was found to strongly increase with time for an untreated meat sample whereas ozone-treated meat samples showed much reduced emissions—suggesting that the microbial activity had been greatly suppressed by ozone treatment. An independent analysis, however, revealed that microbial counts were very high, independent of the treatment.
[Tani2004] "Effect of water vapour pressure on monoterpene measurements using proton transfer reaction-mass spectrometry (PTR-MS)", International Journal of Mass Spectrometry, vol. 239, no. 2: Elsevier, pp. 161–169, 2004.
Abstract
The effects of water vapour pressure (WVP) on the fragmentation of seven monoterpene and related C10 volatile organic compounds (VOCs) in the drift tube of a proton transfer reaction-mass spectrometer (PTR-MS) were investigated. In addition, the combined effects of varying WVP and the ratios of electric field strength to number density of the buffer gas (E/N) were investigated in detail for three of these compounds, the monoterpenes α-pinene and sabinene plus the related C10 VOC p-cymene. Under normal operating conditions (E/N = 124 Td), WVP affected the fragment patterns of all compounds with the exception of β-pinene and the three oxygenated C10 VOCs. WVP had a significant effect on the fragment patterns of α-pinene and sabinene at the lower E/N ratios (around 80 Td) but had little effect on fragmentation towards the higher E/N ratios used here (∼142 Td). On the other hand, p-cymene fragmentation was most affected by WVP under normal operating conditions. PTR-MS sensitivity towards the three compounds was also considered under three conditions where reaction was assumed with (1) H3O+ only; (2) H3O+ and H3O+H2O; and (3) H3O+, H3O+H2O and H3O+(H2O)2. Our results indicate that α-pinene and sabinene react not only with H3O+ and H3O+H2O via direct proton transfer but also with H3O+(H2O)2 via ligand switching. p-Cymene seems to react only with H3O+ via direct proton transfer and with H3O+H2O via ligand switching. It is speculated that the WVP effect on fragmentation results from the differing abundances of hydrated reagent ions which causes different frequencies of individual reactions to occur, thus, determining how ‘soft’ the overall reaction is. These results also indicate that under normal conditions, a correction should be made for WVP if the concentration of p-cymene in air samples is to be determined from the single ion signal of either protonated molecular ions or the most dominant fragment ions.
[Northway2004] "Evaluation of the role of heterogeneous oxidation of alkenes in the detection of atmospheric acetaldehyde", Atmospheric Environment, vol. 38, no. 35: Elsevier, pp. 6017–6028, 2004.
Abstract
Unexpectedly high values for acetaldehyde have been observed in airborne measurements using a proton-transfer-reaction mass spectrometry instrument. The acetaldehyde values increase with increasing ambient ozone levels with a ratio up to 5 pptv acetaldehyde per ppbv of ozone in the free troposphere. The elevated values of acetaldehyde cannot easily be explained from known tropospheric chemistry. Here, we investigate the possibility that the elevated acetaldehyde signals are due to a sampling artifact. Laboratory experiments show that the elevated signals are not due to changes of the ion chemistry in the instrument, or from the instrument materials reacting with ozone. The heterogeneous oxidation of a number of unsaturated organic compounds is investigated as a possible source for a chemical artifact produced in the instrument inlet. The products of the heterogeneous reactions are consistent with gas phase chemistry, and the ozonolysis of some alkenes does produce acetaldehyde when they have the appropriate hydrocarbon structure. The amount of reactive material in the free troposphere expected to accumulate in the aircraft inlet is unknown, and the exact origin of reactive compounds that contribute to the artifact production remains unresolved.
[Karl2004] "Exchange processes of volatile organic compounds above a tropical rain forest: Implications for modeling tropospheric chemistry above dense vegetation", Journal of geophysical research, vol. 109, no. D18: American Geophysical Union, pp. D18306, 2004.
Abstract
Disjunct eddy covariance in conjunction with continuous in-canopy gradient measurements allowed for the first time to quantify the fine-scale source and sink distribution of some of the most abundant biogenic (isoprene, monoterpenes, methanol, acetaldehyde, and acetone) and photooxidized (MVK+MAC, acetone, acetaldehyde, acetic, and formic acid) VOCs in an old growth tropical rain forest. Our measurements revealed substantial isoprene emissions (up to 2.50 mg m−2 h−1) and light-dependent monoterpene emissions (up to 0.33 mg m−2 h−1) at the peak of the dry season (April and May 2003). Oxygenated species such as methanol, acetone, and acetaldehyde were typically emitted during daytime with net fluxes up to 0.50, 0.36, and 0.20 mg m−2 h−1, respectively. When generalized for tropical rain forests, these fluxes would add up to a total emission of 36, 16, 19, 106, and 7.2 Tg/yr for methanol, acetaldehyde, acetone, isoprene, and monoterpenes, respectively. During nighttime we observed strong sinks for oxygenated and nitrogen-containing compounds such as methanol, acetone, acetaldehyde, MVK+MAC, and acetonitrile with deposition velocities close to the aerodynamic limit. This suggests that the canopy resistance (Rc) is very small and not the rate-limiting step for the nighttime deposition of many VOCs. Our measured mean dry deposition velocities of methanol, acetone, acetaldehyde, MVK+MAC, and acetonitrile were a factor 10–20 higher than estimated from traditional deposition models. If our measurements are generalized, this could have important implications for the redistribution of VOCs in atmospheric chemistry models. Our observations indicate that the current understanding of reactive carbon exchange can only be seen as a first-order approximation.
2005
[Spirig2005] "Eddy covariance flux measurements of biogenic VOCs during ECHO 2003 using proton transfer reaction mass spectrometry", Atmospheric Chemistry and Physics, vol. 5, no. 2, pp. 465–481, 2005.
Abstract
Within the framework of the AFO 2000 project ECHO, two PTR-MS instruments were operated in combination with sonic anemometers to determine biogenic VOC fluxes from a mixed deciduous forest site in North-Western Germany. The measurement site was characterised by a forest of inhomogeneous composition, complex canopy structure, limited extension in certain wind directions and frequent calm wind conditions during night time. The eddy covariance (EC) technique was applied since it represents the most direct flux measurement approach on the canopy scale and is, therefore, least susceptible to these non-ideal conditions. A specific flux calculation method was used to account for the sequential multi-component PTR-MS measurements and allowing an individual delay time adjustment as well as a rigorous quality control based on cospectral analysis. The validated flux results are consistent with light and temperature dependent emissions of isoprene and monoterpenes from this forest, with average daytime emissions of 0.94 and 0.3µg m-2s-1, respectively. Emissions of methanol reached on average 0.087µg m-2s-1 during daytime, but fluxes were too small to be detected during night time. Upward fluxes of the isoprene oxidation products methyl vinyl ketone (MVK) and methacrolein (MACR) were also found, being two orders of magnitude lower than those of isoprene. Calculations with an analytical footprint model indicate that the observed isoprene fluxes correlate with the fraction of oaks within the footprints of the flux measurement.
2006
[Klemm2006] "Experiments on forest/atmosphere exchange: Climatology and fluxes during two summer campaigns in NE Bavaria", Atmospheric Environment, vol. 40: Elsevier, pp. 3–20, 2006.
Abstract
During two summer field campaigns in 2001 and 2002, biosphere/atmosphere exchange fluxes of energy, gases, and particles were quantified in a Norway spruce forest in NE Bavaria at 775 m a.s.l. The overall goal of the BEWA campaigns was to study the influence of the emissions of reactive biogenic volatile organic compounds (BVOCs) on chemical and physical processes in the atmosphere, and an overview over the meteorological conditions, experimental frame, and the achieved results is provided. A rigorous quality assurance/quality control plan was implemented. From analysis of meteorological conditions and experimental success, golden day periods were selected for coordinated data analysis. These periods cover typical summertime conditions with various wind directions, NOx mixing ratios between 2 and 10 ppb, and O3 mixing ratios ranging between 13 and 98 ppb. Diurnal patterns of trace gas concentrations resulted from the dynamics of the boundary layer, from regional atmospheric processes (for example production of O3 in the atmosphere), and deposition. Turbulence also exhibited a diurnal pattern indicating thermal production during daytime and calm conditions during nighttime. However, in many cases, turbulence was often well developed during the nights. Horizontal advection of air masses into the trunk space occurred due to the patchiness of the forest. Nevertheless, for most conditions, the application of a one-dimensional model to describe the vertical exchange processes was appropriate. Therefore, the use of one single meteorological tower to study biosphere/atmosphere exchange is valid. Measured turbulent vertical exchange fluxes were estimated to be representative within an error of less than 25%. The results for VOC concentrations and fluxes were rather heterogeneous. Both model and measurements demonstrated that the Norway spruce trees acted as a weak source of formaldehyde.
2007
[Song2007] "Effect of hydrophobic primary organic aerosols on secondary organic aerosol formation from ozonolysis of $\alpha$-pinene", Geophysical Research Letters, vol. 34, no. 20, 2007.
Abstract
Semi-empirical secondary organic aerosol (SOA) models typically assume a well-mixed organic aerosol phase even in the presence of hydrophobic primary organic aerosols (POA). This assumption significantly enhances the modeled SOA yields as additional organic mass is made available to absorb greater amounts of oxidized secondary organic gases than otherwise. We investigate the applicability of this critical assumption by measuring SOA yields from ozonolysis of α-pinene (a major biogenic SOA precursor) in a smog chamber in the absence and in the presence of dioctyl phthalate (DOP) and lubricating oil seed aerosol. These particles serve as surrogates for urban hydrophobic POA. The results show that these POA did not enhance the SOA yields. If these results are found to apply to other biogenic SOA precursors, then the semi-empirical models used in many global models would predict significantly less biogenic SOA mass and display reduced sensitivity to anthropogenic POA emissions than previously thought.
[1503] "Emission, oxidation, and secondary organic aerosol formation of volatile organic compounds as observed at Chebogue Point, Nova Scotia", Journal of Geophysical Research, vol. 112, 2007.
Abstract
<p>We report the detection of a class of related oxygenated compounds by proton-transfer-reaction mass-spectrometry (PTR-MS) that have rarely or never been observed as a group using in situ instrumentation. Measurements were made as part of the International Consortium for Atmospheric Research on Transport and Transformation (ICARTT) 2004 in Chebogue Point, Nova Scotia. The detected class of compounds discussed here includes acetic acid, formaldehyde, acetaldehyde, tentatively identified formic acid and hydroxyacetone, and unidentified compounds detected at mass to charge ratios 85, 87, 99, 101, 113, 115, and 129. Typical concentrations were 800, 2500, 450, 700, 85, 25, 50, 50, 60, 35, 20, and 25 ppt, respectively. The uniqueness of this class of compounds is illustrated by showing they were poorly related to trace gases found in the US outflow, local pollution, primary biogenic emissions and other oxygenated compounds such as acetone, methanol, and MEK measured by other in situ instrumentation. On the other hand these oxidized volatile organic compounds were related to chemical species in aerosols and their abundance was high during nucleation events. Thus they likely are gas phase species that are formed in parallel to biogenic secondary organic aerosol production. We clearly show these compounds do not originate from local sources. We also show these compounds match the oxidation products of isoprene observed in smog chamber studies, and we therefore suggest they must be mainly produced by oxidation of biogenic precursor compounds.</p>
[GomezAlvarez2007] "Experimental confirmation of the dicarbonyl route in the photo-oxidation of toluene and benzene.", Environ Sci Technol, vol. 41, no. 24: FundaciÃ³n Centro de Estudios Ambientales del MediterrÃ¡neo (CEAM), C/Charles Darwin 14, 46980 Paterna, Valencia, Spain. elena@ceam.es, pp. 8362–8369, Dec, 2007.
Abstract
The methodology of solid phase microextraction (SPME) with O-(2,3,4,5,6)-pentafluorobenzylhydroxylamine hydrochloride (PFBHA) on-fiber derivatization for the determination of carbonyls has been applied to the photo-oxidation of benzene and toluene carried out in the EUPHORE chambers. This work focuses on the results obtained for a number of highly reactive carbonyls, crucial in the determination of branching ratios and confirmation of the carbonylic route. The observed yields and kinetic behavior were compared to simulations with the Master Chemical Mechanism model, version 3.1 (MCMv3.1). The following yields were measured in the toluene system: glyoxal, (37 +/- 2)%; methylglyoxal, (37 +/- 2)%; 4-oxo-2-pentenal, > (13.8 +/- 1.5)%; and total butenedial, (13 +/- 7)% (cis-butenedial, (6 +/- 3)%; trans-butenedial, (7 +/- 4)%]. For benzene, the experimental glyoxal yields were (42 +/- 3) and (36 +/- 2)% for the two successive experiments (September 24 and 25, 2003), (17 +/- 9)% for total butenedial [(8 +/- 4)% cis-butenedial and (9 +/- 5)% trans-butenedial (September 24, 2003)] and (15 +/- 6)% total butenedial (September 25, 2003) [(7 +/- 3) and (7 +/- 3)% for the cis and trans isomers, respectively]. PTR-MS estimations for butenedial also allowed the two isomers of butenedial to be distinguished, but the measurements showed signs of interference from other products. The results presented confirm the fast ring cleavage and provide further experimental confirmation of the dicarbonylic route.
2008
[Keck2008] Keck, L., C. Hoeschen, and U. Oeh, "Effects of carbon dioxide in breath gas on proton transfer reaction-mass spectrometry (PTR-MS) measurements", International Journal of Mass Spectrometry, vol. 270, no. 3: Elsevier, pp. 156–165, 2008.
Abstract
PTR-MS is becoming a common method for the analysis of volatile organic compounds (VOCs) in human breath. Breath gas contains substantial and, particularly for bag samples, highly variable concentrations of water vapour (up to ∼6.3%) and carbon dioxide (up to ∼6.5%). The goal of this study was to investigate the effects of carbon dioxide on PTR-MS measurements; such effects can be expected in view of the already well known effects of water vapour. Carbon dioxide caused an increase of the pressure in the PTR-MS drift tube (∼1% increase for 5% CO2), and this effect was used to assess the CO2 concentration of breath gas samples along the way with the analysis of VOCs. Carbon dioxide enhanced the concentration ratio of protonated water clusters (H3O+H2O) to protonated water (H3O+) in the drift tube. Using the observed increase, being ∼60% for 5% CO2, it is estimated that the mobility of water cluster ions in pure CO2 is almost 65% lower than in air. Carbon dioxide had a significant effect on the mass spectra of the main breath gas components methanol, ethanol, 1-propanol, 2-propanol, acetone, and isoprene. Carbon dioxide caused a small increase (<10% for 5% CO2) of the normalised main signals for the non-fragmenting molecules methanol and acetone. The increase can be much higher for the fragmenting VOCs (ethanol, propanol, and isoprene) and was, for 5% CO2, up to ∼60% for ethanol. This effect of CO2 on fragment patterns is mainly a consequence of the increased abundance of protonated water clusters, which undergo softer reactions with VOCs than the hydronium ions. Breath gas samples stored in Teflon bags lost ∼80% of CO2 during 3 days, the decrease of VOC signals, however, is mainly attributed to decreasing VOC concentrations and to the loss of humidity from the bags.
[Kim2008] "Emissions and Photochemistry of BVOCs in a Ponderosa Pine woodland", AGU Fall Meeting Abstracts, vol. 1, pp. 0057, 2008.
Abstract
We deployed two proton-transfer-reaction mass spectrometry instruments (PTR-MS, IONICON ANALYTIK) for ambient and branch enclosure measurements at the Manitou Experimental Forest, located in the Southern Rocky Mountain area as a part of the Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics and Nitrogen (BEACHON) field campaign in 2008. Vegetation at the field site is dominated by Ponderosa Pine. BVOC emissions from Ponderosa Pine along with temperature, photosynthetic photon flux density (ppfd), relative humidity, and CO2 uptake were measured from two branch-enclosures (shade and sun). Diurnal variations and the emission response to environmental conditions are described and compared to existing models. In addition, we analyzed the speciation of BVOCs from enclosures by GC-MS. We will present quantitative and qualitative characteristics of BVOC emissions from Ponderosa Pine and analytical characteristics of PTR-MS such as fragmentation patterns of semi-volatile compounds (sesquiterpene, bornyl acetate etc) that we identified as major emissions from the enclosures. BVOC emissions observed in the enclosures will be quantitatively compared to BVOC distributions in ambient air. We explore the presence of possibly unidentified BVOCs in the forest canopy by examining PTR-MS mass spectra of enclosure and ambient air samples based on mass scans between 40 - 210 amu.
2009
[Sinha2009] "The effect of relative humidity on the detection of pyrrole by PTR-MS for OH reactivity measurements", International Journal of Mass Spectrometry, vol. 282, no. 3: Elsevier, pp. 108–111, 2009.
Abstract
The hydroxyl radical (OH) is the most important atmospheric oxidant. Recently Sinha et al. [V. Sinha, J. Williams, J.N. Crowley, J. Lelieveld, Atmos. Chem. Phys. 8 (2008) 2213] developed a new method to measure the total OH reactivity of ambient air (OH sink) employing a proton transfer reaction mass spectrometer (PTR-MS) as a detector. The new method uses pyrrole (C4H4NH) as a reagent and for an OH reactivity measurement this species must be measured under both dry (∼0% RH) and humid air (>30% RH). Here, we investigate the sensitivity dependence of the PTR-MS for pyrrole, as a function of relative humidity in the sampled air. Various normalizations with respect to the H3O+ ion and its different hydrated cluster ions H3O+(H2O)n=1,2,3 are compared. It is shown that both the primary ion signal (H3O+ ion m/z = 19) and the first water cluster ion H3O+(H2O) (m/z = 37) should be used for pyrrole quantification. However, in spite of using this normalization, the PTR-MS sensitivity for pyrrole changes by as much as 16% between dry (∼0% RH) and humid air (above 30% RH), with higher sensitivity when the sampled air is humid. Thus, for accurate quantification of pyrrole using a PTR-MS, calibration factors appropriate to dry and humid air should be employed. We recommend that humidity dependence of the PTR-MS be taken into account when reactivity measurements are performed using the pyrrole based comparative reactivity method (CRM).
[Leclercq2009] "Effects of cross-linking, capsule wall thickness, and compound hydrophobicity on aroma release from complex coacervate microcapsules.", J Agric Food Chem, vol. 57, no. 4: Department of Food Science and Nutrition, University of Minnesota, 1334 Eckles Avenue, St. Paul, Minnesota 55108, USA. lecle003@umn.edu, pp. 1426–1432, Feb, 2009.
Abstract
Microcapsules were produced by complex coacervation with a gelatin-gum acacia wall and medium-chain-triglyceride core. Dry capsules were partially rehydrated and then loaded with model aroma compounds covering a range of volatility, hydrophobicity, and molecular structure. An experimental design was prepared to evaluate the effects of cross-linking, wall/core ratio, and volatile load level on aroma release from capsules in a hot, aqueous environment. The real-time release on rehydration was measured by monitoring the headspace of a vessel containing the capsules to proton transfer reaction mass spectrometry (PTR-MS). Data collected showed no effects of cross-linking or wall/core ratio on volatile release in hot water for any of the volatiles studied. When comparing real-time release of the prepared coacervates to a spray-dried equivalent, there was no difference in the release from hot water but the release was slower when coacervates were added to ambient-temperature water. We found volatile release to be primarily determined by compound partition coefficients (oil/water and water/air) and temperature.
[Gasperi2009] "Effects of supercritical CO< sub> 2 and N< sub> 2 O pasteurisation on the quality of fresh apple juice", Food chemistry, vol. 115, no. 1: Elsevier, pp. 129–136, 2009.
Abstract
Supercritical pasteurisation is receiving increasing attention as an alternative technology for foodstuff pasteurisation, but often the possible effects on the perceptible quality are not sufficiently considered. To address this latter issue, besides standard microbial analysis, we here investigate the impact of CO2/N2O supercritical pasteurisation (100 bar, 36 °C and 10 min treatment time) on the quality traits of fresh apple juice, linked to consumer perception. Discriminative sensory analysis (triangle test) and basic chemical characterization (total solids, sugars, organic acids, polyphenols) could not clearly demonstrate any induced modification of the treated juice, while head space analysis of volatile compounds (both by GC–MS and PTR–MS) indicated a general depletion of the volatile compounds that must be considered in the development of a stabilization method based on supercritical gases.
[Karl2009] "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.
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%).
[OHara2009a] "Endogenous volatile organic compounds in breath and blood of healthy volunteers: examining breath analysis as a surrogate for blood measurements", Journal of Breath Research, vol. 3, no. 2, pp. 027005, 2009.
Abstract
To investigate the premise that levels of endogenous volatile organic compounds (VOC) in breath reflect those in blood, the concentration of acetone and isoprene were measured in radial arterial blood, peripheral venous blood and breath samples from ten healthy volunteers. Coefficients of repeatability as a percentage of mean are less than 30% in breath but greater than 70% in blood. The volunteer-mean ratios of arterial to venous blood concentration are 1.4 (0.9-2.1) for acetone and 0.55 (0.3-1.0) for isoprene. Concentration in breath showed a significant inter-subject correlation with concentration in arterial blood (CAB) for acetone but not for isoprene. Arterial blood/breath ratios are 580 (280-1060) for acetone and 0.47 (0.22-0.77) for isoprene. The sample-mean blood/breath ratio was used to calculate an estimate of CAB and the standard deviation of this estimate was lower than that of arterial blood measured directly. For most subjects, estimated CAB was within uncertainty limits of the actual CAB. Owing to the poor repeatability of VOC concentrations from consecutive blood samples, and the capacitive effects of the lung, this study suggests that breath VOC measurements may provide a more consistent measure than blood measurements for investigating underlying physiological function or pathology within individuals.
[Kameyama2009] "Equilibrator inlet-proton transfer reaction-mass spectrometry (EI-PTR-MS) for sensitive, high-resolution measurement of dimethyl sulfide dissolved in seawater.", Anal Chem, vol. 81, no. 21: National Institute for Environmental Studies, Tsukuba, 305-8506, Japan., pp. 9021–9026, Nov, 2009.
Abstract
We developed an equilibrator inlet-proton transfer reaction-mass spectrometry (EI-PTR-MS) method for fast detection of dimethyl sulfide (DMS) dissolved in seawater. Dissolved DMS extracted by bubbling pure nitrogen through the sample was continuously directed to the PTR-MS instrument. The equilibration of DMS between seawater and the carrier gas, and the response time of the system, were evaluated in the laboratory. DMS reached equilibrium with an overall response time of 1 min. The detection limit (50 pmol L(-1) at 5 s integration) was sufficient for detection of DMS concentrations in the open ocean. The EI-PTR-MS instrument was deployed during a research cruise in the western North Pacific Ocean. Comparison of the EI-PTR-MS results with results obtained by means of membrane tube equilibrator-gas chromatography/mass spectrometry agreed reasonably well on average (R(2) = 0.99). EI-PTR-MS captured temporal variations of dissolved DMS concentrations, including elevated peaks associated with patches of high biogenic activity. These results demonstrate that the EI-PTR-MS technique was effective for highly time-resolved measurements of DMS in the open ocean. Further measurements will improve our understanding of the biogeochemical mechanisms of the production, consumption, and distribution of DMS on the ocean surface and, hence, the air-sea flux of DMS, which is a climatically important species.

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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).

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.