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Scientific Articles - PTR-MS Bibliography

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Found 767 results
Title [ Year(Asc)]
2012
[Karl2012] Karl, T., A. Hansel, L. Cappellin, L. Kaser, I. Herdlinger-Blatt, and W. Jud, "Selective measurements of isoprene and 2-methyl-3-buten-2-ol based on NO+ ionization mass spectrometry", Atmospheric Chemistry and Physics, vol. 12, no. 24: Copernicus GmbH, pp. 11877–11884, 2012.
Link: http://www.atmos-chem-phys.net/12/11877/2012/acp-12-11877-2012.html
Abstract
Biogenic VOC emissions are often dominated by 2-methyl-1,3-butadiene (isoprene) and 2-methyl-3-buten-2-ol (232 MBO). Here we explore the possibility to selectively distinguish these species using NO+ as a primary ion in a conventional PTR-MS equipped with an SRI unit. High purity of NO+ (>90%) as a primary ion was utilized in laboratory and field experiments using a conventional PTR-TOF-MS. Isoprene is ionized via charge transfer leading to the major product ion C5H8+ (>99%) (e.g. Spanel and Smith, 1998). 232 MBO undergoes a hydroxide ion transfer reaction resulting in the major product ion channel C5H9+ (>95%) (e.g. Amelynck et al., 2005). We show that both compounds are ionized with little fragmentation (>5%) under standard operating conditions. Typical sensitivities of 11.1 ± 0.1 (isoprene) and 12.9 ± 0.1 (232 MBO) ncps ppbv−1 were achieved, which correspond to limit of detections of 18 and 15 pptv respectively for a 10 s integration time. Sensitivities decreased at higher collisional energies. Calibration experiments showed little humidity dependence. We tested the setup at a field site in Colorado dominated by ponderosa pine, a 232 MBO emitting plant species. Our measurements confirm 232 MBO as the dominant biogenic VOC at this site, exhibiting typical average daytime concentrations between 0.2–1.4 ppbv. The method is able to detect the presence of trace levels of isoprene at this field site (90–250 ppt) without any interference from 232 MBO, which would not be feasible using H3O+ ionization chemistry, and which currently also remains a challenge for other analytical techniques (e.g. gas chromatographic methods).
[Nolscher2012] Nölscher, AC., J. Williams, V. Sinha, T. Custer, W. Song, AM. Johnson, R. Axinte, H. Bozem, H. Fischer, N. Pouvesle, et al., "Summertime total OH reactivity measurements from boreal forest during HUMPPA-COPEC 2010", Atmospheric Chemistry and Physics, vol. 12, no. 17: Copernicus GmbH, pp. 8257–8270, 2012.
Link: http://www.atmos-chem-phys.net/12/8257/2012/acp-12-8257-2012.html
Abstract
Ambient total OH reactivity was measured at the Finnish boreal forest station SMEAR II in Hyytiälä (Latitude 61°51' N; Longitude 24°17' E) in July and August 2010 using the Comparative Reactivity Method (CRM). The CRM – total OH reactivity method – is a direct, in-situ determination of the total loss rate of hydroxyl radicals (OH) caused by all reactive species in air. During the intensive field campaign HUMPPA-COPEC 2010 (Hyytiälä United Measurements of Photochemistry and Particles in Air – Comprehensive Organic Precursor Emission and Concentration study) the total OH reactivity was monitored both inside (18 m) and directly above the forest canopy (24 m) for the first time. The comparison between these two total OH reactivity measurements, absolute values and the temporal variation have been analyzed here. Stable boundary layer conditions during night and turbulent mixing in the daytime induced low and high short-term variability, respectively. The impact on total OH reactivity from biogenic emissions and associated photochemical products was measured under "normal" and "stressed" (i.e. prolonged high temperature) conditions. The advection of biomass burning emissions to the site caused a marked change in the total OH reactivity vertical profile. By comparing the OH reactivity contribution from individually measured compounds and the directly measured total OH reactivity, the size of any unaccounted for or "missing" sink can be deduced for various atmospheric influences. For "normal" boreal conditions a missing OH reactivity of 58%, whereas for "stressed" boreal conditions a missing OH reactivity of 89% was determined. Various sources of not quantified OH reactive species are proposed as possible explanation for the high missing OH reactivity.
[Kirsch2012] Kirsch, F., J. Beauchamp, and A. Buettner, "Time-dependent aroma changes in breast milk after oral intake of a pharmacological preparation containing 1,8-cineole.", Clin Nutr, vol. 31, no. 5: Department of Chemistry and Pharmacy, Food Chemistry, Emil Fischer Center, University Erlangen-Nuremberg, 91052 Erlangen, Germany., pp. 682–692, Oct, 2012.
Link: http://dx.doi.org/10.1016/j.clnu.2012.02.002
Abstract
This study investigates time-dependent aroma changes in human milk after intake of an odorant-containing pharmaceutical preparation by correlating sensory evaluation with quantitative results.Human milk donors ingested 100 mg of encapsulated 1,8-cineole. 21 milk samples from 12 participants underwent sensory analysis, of which 14 samples were quantified by stable isotope dilution assay (SIDA) analysis. Furthermore, several consecutive breast milk and exhaled breath gas samples from one volunteer after intake of 1,8-cineole were analysed by proton-transfer-reaction mass spectrometry (PTR-MS) and sensory evaluation on three separate days.The emergence of the characteristic eucalyptus-like odour of 1,8-cineole in exhaled breath after capsule ingestion coincided with its transfer into milk; its presence in breath was therefore used to indicate the time at which milk should be expressed for gathering samples. Odorant transfer could not be confirmed by sensory analysis in 7 of the 21 milk samples, most likely due to disadvantageous timing of milk expression. The other 14 samples exhibited a distinct eucalyptus-like odour. Quantitative results matched these observations with <20 ?g/kg 1,8-cineole in the odourless samples and 70 to an estimated 2090 ?g/kg 1,8-cineole in the other samples.Transfer of 1,8-cineole into human milk after oral intake is time dependent and exhibits large inter and intra-individual differences.
[Benjamin2012] Benjamin, O.., P.. Silcock, J.. Beauchamp, A.. Buettner, and D.. W. Everett, "Tongue pressure and oral conditions affect volatile release from liquid systems in a model mouth.", J Agric Food Chem, vol. 60, no. 39: Riddet Institute, Massey University , Palmerston North 4442, New Zealand. ofir.benjamin@otago.ac.nz, pp. 9918–9927, Oct, 2012.
Link: http://dx.doi.org/10.1021/jf3028232
Abstract
The release of volatile organic compounds (VOCs) into the mouth cavity is an integral part of the way flavor is perceived. An in vitro model mouth with an artificial tongue was developed to measure the dynamic release of VOCs from liquid model systems [e.g., aqueous solution, oil, and oil-in-water (O/W) emulsions] under oral conditions. The release of seven selected VOCs was affected by the different polarity and vapor pressure of the compounds and their affinity to the liquid system media. Different tongue pressure patterns were applied to the liquid systems, and the release of VOCs was monitored in real time using proton transfer reaction-mass spectrometry. The release was significantly more intense for longer tongue pressure duration and was influenced by the tongue altering the sample surface area and the distribution of the VOCs. The role of saliva (artificial versus human) and the sample temperature had a significant effect on VOC release. Saliva containing mucin and a higher sample temperature enhanced the release.
[Dolgorouky2012] Dolgorouky, C., V. Gros, R. Sarda-Esteve, V. Sinha, J. Williams, N. Marchand, S. Sauvage, L. Poulain, J. Sciare, and B. Bonsang, "Total OH reactivity measurements in Paris during the 2010 MEGAPOLI winter campaign", Atmospheric Chemistry and Physics, vol. 12, no. 20: Copernicus GmbH, pp. 9593–9612, 2012.
Link: http://www.atmos-chem-phys.net/12/9593/2012/
Abstract
Hydroxyl radicals play a central role in the troposphere as they control the lifetime of many trace gases. Measurement of OH reactivity (OH loss rate) is important to better constrain the OH budget and also to evaluate the completeness of measured VOC budget. Total atmospheric OH reactivity was measured for the first time in an European Megacity: Paris and its surrounding areas with 12 million inhabitants, during the MEGAPOLI winter campaign 2010. The method deployed was the Comparative Reactivity Method (CRM). The measured dataset contains both measured and calculated OH reactivity from CO, NOx and VOCs measured via PTR-MS, GC-FID and GC-MS instruments. The reactivities observed in Paris covered a range from 10 s−1 to 130 s−1, indicating a large loading of chemical reactants. The present study showed that, when clean marine air masses influenced Paris, the purely local OH reactivity (20 s−1) is well explained by the measured species. Nevertheless, when there is a continental import of air masses, high levels of OH reactivity were obtained (120–130 s−1) and the missing OH reactivity measured in this case jumped to 75%. Using covariations of the missing OH reactivity to secondary inorganic species in fine aerosols, we suggest that the missing OH reactants were most likely highly oxidized compounds issued from photochemically processed air masses of anthropogenic origin.
[Danner2012] Danner, H., D. Samudrala, S. M. Cristescu, and N. M. { van Dam}, "Tracing hidden herbivores: time-resolved non-invasive analysis of belowground volatiles by proton-transfer-reaction mass spectrometry (PTR-MS).", J Chem Ecol, vol. 38, no. 6: Department of Ecogenomics, Institute for Water and Wetland Research (IWWR), Radboud University, PO Box 9010, 6500 GL, Nijmegen, The Netherlands. h.danner@science.ru.nl, pp. 785–794, Jun, 2012.
Link: http://dx.doi.org/10.1007/s10886-012-0129-3
Abstract
Root herbivores are notoriously difficult to study, as they feed hidden in the soil. However, root herbivores may be traced by analyzing specific volatile organic compounds (VOCs) that are produced by damaged roots. These VOCs not only support parasitoids in the localization of their host, but also may help scientists study belowground plant-herbivore interactions. Herbivore-induced VOCs are usually analyzed by gas-chromatography mass spectrometry (GC-MS), but with this off-line method, the gases of interest need to be preconcentrated, and destructive sampling is required to assess the level of damage to the roots. In contrast to this, proton-transfer-reaction mass spectrometry (PTR-MS) is a very sensitive on-line, non-invasive method. PTR-MS already has been successfully applied to analyze VOCs produced by aboveground (infested) plant parts. In this review, we provide a brief overview of PTR-MS and illustrate how this technology can be applied to detect specific root-herbivore induced VOCs from Brassica plants. We also specify the advantages and disadvantages of PTR-MS analyses and new technological developments to overcome their limitations.
[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.
[Vesin2012] Vesin, A., G. Bouchoux, E. Quivet, B. Temime-Roussel, and H. Wortham, "Use of the HS-PTR-MS for online measurements of pyrethroids during indoor insecticide treatments.", Anal Bioanal Chem, vol. 403, no. 7: Aix-Marseille Univ, LCE-IRA, 13331 Marseille, France., pp. 1907–1921, Jun, 2012.
Link: http://dx.doi.org/10.1007/s00216-012-6003-x
Abstract
A high-sensitivity proton transfer reaction mass spectrometer (HS-PTR-MS) has been used to study the temporal evolution of pesticide concentrations in indoor environments. Because of the high time variability of the indoor air concentrations during household pesticide applications, the use of this online high time resolution instrument is found relevant. Four pyrethroid pesticides of the latest generation that are commonly found in electric vaporizer refills, namely, transfluthrin, empenthrin, tetramethrin, and prallethrin, were considered. A controlled pesticide generation system was settled and coupled to a HS-PTR-MS analyzer, and a calibration procedure based on the fragmentation patterns of the protonated molecules was performed. To illustrate the functionality of the method, measurements of the concentration-time profiles of transfluthrin contained in an electric vaporizer were carried out in a full-scale environmental room under air exchange rate-controlled conditions. This study demonstrates that the HS-PTR-MS technique can provide online and high time-resolved measurements of semi-volatile organic compounds such as pyrethroid insecticides.
[Ni2012] Ni, J-Q., W. P. Robarge, C. Xiao, and A. J. Heber, "Volatile organic compounds at swine facilities: a critical review.", Chemosphere, vol. 89, no. 7: Department of Agricultural and Biological Engineering, Purdue University, West Lafayette, IN 47907, USA. jiqin@purdue.edu, pp. 769–788, Oct, 2012.
Link: http://dx.doi.org/10.1016/j.chemosphere.2012.04.061
Abstract
Volatile organic compounds (VOCs) are regulated aerial pollutants that have environmental and health concerns. Swine operations produce and emit a complex mixture of VOCs with a wide range of molecular weights and a variety of physicochemical properties. Significant progress has been made in this area since the first experiment on VOCs at a swine facility in the early 1960s. A total of 47 research institutions in 15 North American, European, and Asian countries contributed to an increasing number of scientific publications. Nearly half of the research papers were published by U.S. institutions. Investigated major VOC sources included air inside swine barns, in headspaces of manure storages and composts, in open atmosphere above swine wastewater, and surrounding swine farms. They also included liquid swine manure and wastewater, and dusts inside and outside swine barns. Most of the sample analyses have been focusing on identification of VOC compounds and their relationship with odors. More than 500 VOCs have been identified. About 60% and 10% of the studies contributed to the quantification of VOC concentrations and emissions, respectively. The largest numbers of VOC compounds with reported concentrations in a single experimental study were 82 in air, 36 in manure, and 34 in dust samples. The relatively abundant VOC compounds that were quantified in at least two independent studies included acetic acid, butanoic acid (butyric acid), dimethyl disulfide, dimethyl sulfide, iso-valeric, p-cresol, propionic acid, skatole, trimethyl amine, and valeric acid in air. They included acetic acid, p-cresol, iso-butyric acid, butyric acid, indole, phenol, propionic acid, iso-valeric acid, and skatole in manure. In dust samples, they were acetic acid, propionic acid, butyric acid, valeric acid, p-cresol, hexanal, and decanal. Swine facility VOCs were preferentially bound to smaller-size dusts. Identification and quantification of VOCs were restricted by using instruments based on gas Chromatography (GC) and liquid chromatography (LC) with different detectors most of which require time-consuming procedures to obtain results. Various methodologies and technologies in sampling, sample preparation, and sample analysis have been used. Only four publications reported using GC based analyzers and PTR-MS (proton-transfer-reaction mass spectrometry) that allowed continuous VOC measurement. Because of this, the majority of experimental studies were only performed on limited numbers of air, manure, or dust samples. Many aerial VOCs had concentrations that were too low to be identified by the GC peaks. Although VOCs emitted from swine facilities have environmental concerns, only a few studies investigated VOC emission rates, which ranged from 3.0 to 176.5mgd(-1)kg(-1) pig at swine finishing barns and from 2.3 to 45.2gd(-1)m(-2) at manure storages. Similar to the other pollutants, spatial and temporal variations of aerial VOC concentrations and emissions existed and were significantly affected by manure management systems, barn structural designs, and ventilation rates. Scientific research in this area has been mainly driven by odor nuisance, instead of environment or health concerns. Compared with other aerial pollutants in animal agriculture, the current scientific knowledge about VOCs at swine facilities is still very limited and far from sufficient to develop reliable emission factors.
[Weise2012] Weise, T., M. Kai, A. Gummesson, A. Troeger, S. { von Reuß}, S. Piepenborn, F. Kosterka, M. Sklorz, R. Zimmermann, W. Francke, et al., "Volatile organic compounds produced by the phytopathogenic bacterium Xanthomonas campestris pv. vesicatoria 85-10.", Beilstein J Org Chem, vol. 8: University of Rostock, Institute of Biological Sciences, Albert-Einstein-Str. 3, 18059 Rostock, Germany., pp. 579–596, 2012.
Link: http://dx.doi.org/10.3762/bjoc.8.65
Abstract
Xanthomonas campestris is a phytopathogenic bacterium and causes many diseases of agricultural relevance. Volatiles were shown to be important in inter- and intraorganismic attraction and defense reactions. Recently it became apparent that also bacteria emit a plethora of volatiles, which influence other organisms such as invertebrates, plants and fungi. As a first step to study volatile-based bacterial-plant interactions, the emission profile of Xanthomonas c. pv. vesicatoria 85-10 was determined by using GC/MS and PTR-MS techniques. More than 50 compounds were emitted by this species, the majority comprising ketones and methylketones. The structure of the dominant compound, 10-methylundecan-2-one, was assigned on the basis of its analytical data, obtained by GC/MS and verified by comparison of these data with those of a synthetic reference sample. Application of commercially available decan-2-one, undecan-2-one, dodecan-2-one, and the newly synthesized 10-methylundecan-2-one in bi-partite Petri dish bioassays revealed growth promotions in low quantities (0.01 to 10 ?mol), whereas decan-2-one at 100 ?mol caused growth inhibitions of the fungus Rhizoctonia solani. Volatile emission profiles of the bacteria were different for growth on media (nutrient broth) with or without glucose.
[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
[Warneke2011] Warneke, C., P. Veres, JS. Holloway, J. Stutz, C. Tsai, S. Alvarez, B. Rappenglueck, FC. Fehsenfeld, M. Graus, JB. Gilman, et al., "Airborne formaldehyde measurements using PTR-MS: calibration, humidity dependence, inter-comparison and initial results", Atmospheric Measurement Techniques Discussions, vol. 4, no. 4: Copernicus GmbH, pp. 4631–4665, 2011.
Link: http://www.atmos-meas-tech-discuss.net/4/4631/2011/amtd-4-4631-2011.html
Abstract
We present quantitative, fast time response measurements of formaldehyde (HCHO) onboard an aircraft using a Proton-Transfer-Reaction Mass-Spectrometry (PTR-MS) instrument. The HCHO measurement by PTR-MS is strongly humidity dependent and therefore airborne measurements are difficult and have not been reported. The PTR-MS instrument was run in the normal operating mode, where about 15 volatile organic compounds (VOCs) are measured together with HCHO onboard the NOAA WP-3 aircraft during the CalNex 2010 campaign in California. We compare the humidity dependence determined in the laboratory with in-flight calibrations of HCHO and calculate the HCHO mixing ratio during all flights using the results from both. The detection limit for HCHO was between 100 pptv in the dry free troposphere and 300 pptv in the humid marine boundary layer for a one second acquisition time every 17 s. The PTR-MS measurements are compared with HCHO measurements using a DOAS instrument and a Hantzsch monitor at a ground site in Pasadena. The PTR-MS agreed with both instruments within the stated uncertainties. We also compare HCHO enhancement ratios in the Los Angeles basin and in the free troposphere with literature values and find good agreement. The usefulness of the PTR-MS HCHO measurements in atmospheric observations is demonstrated by following an isolated anthropogenic plume. The photochemical production of HCHO can be observed simultaneously with production of acetaldehyde and the photochemical degradation of aromatic compounds using the PTR-MS.
[Kameyama2011] Kameyama, S., H. Tanimoto, S. Inomata, K. Suzuki, D. D. Komatsu, A. Hirota, U. Konno, and U. Tsunogai, "Application of PTR-MS to an incubation experiment of the marine diatom Thalassiosira pseudonana", Geochemical Journal, vol. 45, no. 5: Geochemical Society of Japan, pp. 355–363, 2011.
Link: http://eprints.lib.hokudai.ac.jp/dspace/handle/2115/50151
Abstract
Emission of trace gases from the marine diatom Thalassiosira pseudonana (CCMP 1335) was continuously monitored with a proton transfer reaction-mass spectrometry (PTR-MS) in an axenic batch culture system under a 13:11-h light:dark cycle. Substantial increases in the signals at m/z 49, 63, and 69, attributable to methanethiol, dimethyl sulfide (DMS), and isoprene, respectively, were observed in response to increases in cell density. Signals at m/z 69 showed diurnal variations throughout the experiment whereas those at m/z 49 were more pronounced at the beginning of the incubation. Interestingly, the signals at m/z 49 and 69 changed immediately following the light-dark and dark-light transitions, suggesting that light plays a crucial role in the production of methanethiol and isoprene. However, in the latter half of the experiment, methanethiol showed negligible diurnal variations regardless of light conditions, suggesting the production of methanethiol from enzymatic cleavage of DMS. The trend ill signals at m/z 63 was similar to that of the abundance of senescent cells plus cell debris rather than vegetative cells. The results suggest that aging or death of phytoplankton cells could also substantially control DMS production in natural waters along with the other microbial processes related to bacteria and zooplankton.
[Singer2011] Singer, W., J. Herbig, R. Gutmann, K. Winkler, I. Kohl, and A. Hansel, "Applications of PTR-MS in medicine and biotechnology", American Laboratory, vol. 43, no. 7: AMER LABORATORY-LABCOMPARE 30 CONTROLS DRIVE, SHELTON, CT 06484 USA, pp. 34–37, 2011.
Link: http://www.americanlaboratory.com/913-Technical-Articles/19001-Applications-of-PTR-MS-in-Medicine-and-Biotechnology/
Abstract
Proton transfer reaction-mass spectrometry (PTR-MS) is a well-established analytical tool for the measurement of volatile organic compounds (VOCs), and offers real-time detection and quantification of VOCs at trace concentrations. This paper focuses on the measurement of VOCs in biological systems. Both microorganisms and cells, e.g., in the human body, constantly produce a large variety of volatile organic metabolites. Analyzing VOCs in exhaled human breath reveals information about the status of the body. In a similar manner, monitoring the off-gas of fermentations in the biopharmaceutical industry allows microbial activity to be gauged. Undesired compounds (those that are harmful to the human body or impurities in biotechnical processes) can also be tracked in real time using the technique.
[Kohl2011a] Kohl, I.., J.. Dunkl, and A.. Hansel, "The average composition of exhaled breath of healthy women by PTR-TOF-MS", 5th International PTR-MS Conference on Proton Transfer Reaction Mass Spectrometry and Its Applications, pp. 34, 2011.
Link: http://www.ionicon.com/sites/default/files/uploads/doc/contributions_ptr_ms_Conference_5.pdf
Abstract
We analysed the exhaled breath of a cohort of 50 healthy women using Proton-Transfer-Reaction Time-of-Flight Mass Spectrometry (PTR-TOF-MS). To ensure that end-tidal exhaled air was collected, we used a Breath Collecting Unit, which sampled breath gas only when the CO2 signal was high. Samples were stored in inert Silco cans and analysed subsequently by PTR-TOF-MS. Components are characterized by their sum formula and were extracted from the raw data by matching them with a list of candidate compounds. A description of the average composition of the investigated cohort is given. These data can be helpful to identify compounds in breath measurements with quadrupole PTRMS systems, where a separation of isobaric compounds is not possible.
[1507] Fares, S., D. R. Gentner, J-H. Park, E. Ormeno, J. Karlik, and A. H. Goldstein, "Biogenic emissions from Citrus species in California", Atmospheric Environment, vol. 45, pp. 4557–4568, Sep, 2011.
Link: http://dx.doi.org/10.1016/j.atmosenv.2011.05.066
Abstract
<p>Biogenic Volatile Organic Compounds (BVOC) emitted from plants are the dominant source of reduced carbon chemicals to the atmosphere and are important precursors to the photochemical production of ozone and secondary organic aerosols. Considering the extensive land used for agriculture, cultivated Citrus plantations may play an important role in the chemistry of the atmosphere especially in regions such as the Central Valley of California. Moreover, the BVOC emissions from Citrus species have not been characterized in detail and more species-specific inputs for regional models of BVOC emissions are needed. In this study, we measured the physiological parameters and emissions of the most relevant BVOC (oxygenated compounds, monoterpenes, and sesquiterpenes) for four predominant Citrus species planted in California ( Citrus sinensis var. &#39;Parent Navel&#39;, Citrus limon var. &#39;Meyer&#39;, Citrus reticulata var. &#39;W. Murcott&#39; and &#39;Clementine&#39;). We used two analytical techniques to measure a full range of BVOC emitted: Proton Transfer Reaction Mass Spectrometry (PTR-MS) and gas chromatography with mass spectrometry. Methanol, followed by acetone and acetaldehyde, were the dominant BVOC emitted from lemon and mandarin trees (basal emission rates up to 300 ng(C) g(DW) -1 h -1), while oxygenated monoterpenes, monoterpenes, and sesquiterpenes were the main BVOC emitted from orange trees (basal emission rates up to = 2500 ng(C) g(DW) -1 h -1). Light and temperature-dependent algorithms were better predictors of methanol, acetaldehyde, acetone, isoprene and monoterpenes for all the Citrus species. Whereas, temperature-dependent algorithms were better predictors of oxygenated monoterpenes, and sesquiterpenes. We observed that flowering increased emissions from orange trees by an order of magnitude with the bulk of BVOC emissions being comprised of monoterpenes, sesquiterpenes, and oxygenated monoterpenes. Chemical speciation of BVOC emissions show that the various classes of terpene emissions among all Citrus species are dominated by ocimenes, β-caryophyllene, and linalool, respectively. In addition to utilizing our reported emission factors in BVOC emission models, we recommend that future BVOC emission models consider additional emissions from flowering and harvest, which occur seasonally and may have a significant impact on regional atmospheric chemistry.</p>
[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>
[Herbig2011] Herbig, J.., M.. Seger, I.. Kohl, K.. Winkler, H.. Jamnig, A.. Zabernigg, C.. Baumgartner, and A.. Hansel, "Breath Analysis with PTR-MS: More breath markers for lung cancer", 5th International PTR-MS Conference on Proton Transfer Reaction Mass Spectrometry and Its Applications, pp. 31-33, 2011.
Link: http://www.ionicon.com/sites/default/files/uploads/doc/contributions_ptr_ms_Conference_5.pdf
Abstract
In a clinical screening study we have measured several hundred subjects using real-time breath analysis with PTR-MS. We present and discuss potential breath markers for lung cancer with a critical view on the data analysis. The presented problems and solutions are also applicable to other analytical methods used in breath analysis.
[Mair2011] Mair, V.., J.. Dunkl, A.. Hansel, and I.. Kohl, "Breath gas analysis by PTR-TOF-MS in a clinical setting", 5th International PTR-MS Conference on Proton Transfer Reaction Mass Spectrometry and Its Applications, pp. 231, 2011.
Link: http://www.ionicon.com/sites/default/files/uploads/doc/contributions_ptr_ms_Conference_5.pdf
Abstract
Typical clinical (breath analysis) studies take several months to years. Employing a Proton-Transfer-Reaction Time-of-Flight Mass Spectrometer (PTR-TOF-MS) as an analytical tool for breath analysis, a constant performance of the instrument is essential. Here we report on the longterm performance of a PTR-TOF-MS for the analysis of exhaled breath gas in the frame of a clinical study. Performance data are shown for a period of 7 months. We characterized the sampling procedure, sample storage, and measured sensitivity and detection limit for a set of VOCs with relevance in breath analysis. Over the period of 7 months, we were able to achieve a high mass accuracy and precision in the range of ppm.
[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>
[Simpraga2011] Šimpraga, M., H. Verbeeck, M. Demarcke, É. Joó, O. Pokorska, C. Amelynck, N. Schoon, J. Dewulf, H. Van Langenhove, B. Heinesch, et al., "Clear link between drought stress, photosynthesis and biogenic volatile organic compounds in Fagus sylvatica L.", Atmospheric Environment, vol. 45, no. 30: Elsevier, pp. 5254–5259, 2011.
Link: http://www.sciencedirect.com/science/article/pii/S1352231011006996
Abstract
Direct plant stress sensing is the key for a quantitative understanding of drought stress effects on biogenic volatile organic compound (BVOC) emissions. A given level of drought stress might have a fundamentally different effect on the BVOC emissions of different plants. For the first time, we continuously quantified the level of drought stress in a young potted beech (Fagus sylvatica L.) with a linear variable displacement transducer (LVDT) installed at stem level in combination with simultaneous measurements of BVOC emissions and photosynthesis rates at leaf level. This continuous set of measurements allowed us to examine how beech alters its pattern of photosynthesis and carbon allocation to BVOC emissions (mainly monoterpenes, MTs) and radial stem growth during the development of drought stress. We observed an increasing-decreasing trend in the MT emissions as well as in the fraction of assimilated carbon re-emitted back into the atmosphere (ranging between 0.14 and 0.01%). We were able to link these dynamics to pronounced changes in radial stem growth, which served as a direct plant stress indicator. Interestingly, we detected a sudden burst in emission of a non-identified, non-MT BVOC species when drought stress was acute (i.e. pronounced negative stem growth). This burst might have been caused by a certain stress-related green leaf volatile, which disappeared immediately upon re-watering and thus the alleviation of drought stress. These results highlight that direct plant stress sensing creates opportunities to understand the overall complexity of stress-related BVOC emissions.
[Simpraga2011a] Šimpraga, M., H. Verbeeck, M. Demarcke, É. Joó, C. Amelynck, N. Schoon, J. Dewulf, H. Van Langenhove, B. Heinesch, M. Aubinet, et al., "Comparing monoterpenoid emissions and net photosynthesis of beech ( Fagus sylvatica L.) in controlled and natural conditions", Atmospheric Environment, vol. 45, no. 17: Elsevier, pp. 2922–2928, 2011.
Link: http://www.sciencedirect.com/science/article/pii/S1352231011000884
Abstract
<p>Although biogenic volatile organic compounds (BVOCs) only represent a very limited fraction of the plant&rsquo;s carbon (C) budget, they play an important role in atmospheric chemistry for example as a precursor of tropospheric ozone. We performed a study comparing BVOC emissions of European beech (Fagus sylvatica L.) in controlled and natural environmental conditions. A young and adult beech tree was exposed to short-term temperature variations in growth room conditions and in an experimental forest, respectively. This study attempts to clarify how short-term temperature variations between days influenced the ratio between monoterpenoid (MT) emissions and net photosynthesis (Pn). Within a temperature range of 17&ndash;27 &deg;C and 13&ndash;23 &deg;C, the MT/Pn carbon ratio increased 10&ndash;30 fold for the growth room and forest, respectively. An exponential increasing trend between MT/Pn C ratio and air temperature was observed in both conditions. Beech trees re-emitted a low fraction of the assimilated C back into the atmosphere as MT: 0.01&ndash;0.12% and 0.01&ndash;0.30% with a temperature rise from 17 to 27 &deg;C and 13&ndash;23 &deg;C in growth room and forest conditions, respectively. However, the data showed that the MT/Pn C ratio of young and adult beech trees responded significantly to changes in temperature.</p>
[Joo2011] Joó, É., J. Dewulf, C. Amelynck, N. Schoon, O. Pokorska, M. Šimpraga, K. Steppe, M. Aubinet, and H. Van Langenhove, "Constitutive versus heat and biotic stress induced BVOC emissions in Pseudotsuga menziesii", Atmospheric Environment, vol. 45, no. 22: Elsevier, pp. 3655–3662, 2011.
Link: http://www.sciencedirect.com/science/article/pii/S1352231011004377
Abstract
Induced volatiles have been a focus of recent research, as not much is known of their emission behavior or atmospheric contribution. BVOC emissions were measured from Pseudotsuga menziesii saplings under natural environmental conditions, using a dynamic branch enclosure system and GC–MS for their analysis. We determined temperature and light dependency of the individual compounds, studied seasonality of the emissions and discuss the effect of heat stress in comparison with two specific biotic stresses that occurred naturally on the trees. A standardized emission rate of 6.8 μg g(dw)−1 h−1 for monoterpenes under stressed conditions was almost a magnitude higher than that obtained for healthy trees (0.8 ± 0.2 μg g(dw)−1 h−1), with higher beta factors characterizing the stressed trees. The response of the emissions to light intensity was different for the individual compounds, suggesting a distinct minimum light intensity to reach saturation. Heat stress changed the relative contribution of specific volatiles, with larger extent of increase of sesquiterpenes, methyl salicylate and linalool emissions compared to monoterpenes. Biotic stress kept low the emissions of sesquiterpenes, (E)-4,8-dimethyl-1,3,7-nonatriene and methylbutenol isomers, and increased the level of methyl salicylate and monoterpenes. The ratio of β-pinene/α-pinene was also found to be significantly enhanced from 1.3 to 2.4 and 3.2 for non-stressed, heat stressed and combined biotic and heat stressed, respectively.

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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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