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Scientific Articles - PTR-MS Bibliography

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Found 8 results
Title [ Year(Asc)]
Filters: Author is Goldstein, Allen H.  [Clear All Filters]
2015
[1637] Wood, E. C., B. W Knighton, E. C. Fortner, S. C. Herndon, T. B. Onasch, J. P. Franklin, D. R. Worsnop, T. R. Dallmann, D. R. Gentner, A. H. Goldstein, et al., "Ethylene glycol emissions from on-road vehicles.", Environ Sci Technol, vol. 49, pp. 3322–3329, Mar, 2015.
Link: http://dx.doi.org/10.1021/acs.est.5b00557
Abstract
<p>Ethylene glycol (HOCH2CH2OH), used as engine coolant for most on-road vehicles, is an intermediate volatility organic compound (IVOC) with a high Henry&#39;s law coefficient. We present measurements of ethylene glycol (EG) vapor in the Caldecott Tunnel near San Francisco, using a proton transfer reaction mass spectrometer (PTR-MS). Ethylene glycol was detected at mass-to-charge ratio 45, usually interpreted as solely coming from acetaldehyde. EG concentrations in bore 1 of the Caldecott Tunnel, which has a 4% uphill grade, were characterized by infrequent (approximately once per day) events with concentrations exceeding 10 times the average concentration, likely from vehicles with malfunctioning engine coolant systems. Limited measurements in tunnels near Houston and Boston are not conclusive regarding the presence of EG in sampled air. Previous PTR-MS measurements in urban areas may have overestimated acetaldehyde concentrations at times due to this interference by ethylene glycol. Estimates of EG emission rates from the Caldecott Tunnel data are unrealistically high, suggesting that the Caldecott data are not representative of emissions on a national or global scale. EG emissions are potentially important because they can lead to the formation of secondary organic aerosol following oxidation in the atmospheric aqueous phase.</p>
2011
[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>
2009
[1505] Bouvier-Brown, N. C., R. Holzinger, K. Palitzsch, and A. H. Goldstein, "Large emissions of sesquiterpenes and methyl chavicol quantified from branch enclosure measurements", Atmospheric Environment, vol. 43, pp. 389–401, Jan, 2009.
Link: http://dx.doi.org/10.1016/j.atmosenv.2008.08.039
Abstract
<p>Multiple field studies have suggested chemistry within a forest canopy is poorly understood due to inadequate detection and quantification of reactive biogenic emissions, such as terpenes. To measure emission rates of terpenes at Blodgett Forest, a coniferous forest in the Sierra Nevada mountains of California, we placed enclosures over branches of the dominant species at the site &ndash; Ponderosa pine, manzanita, and ceanothus &ndash; in the summer of 2005. Zero air, with ambient CO2 concentrations, flowed through the chamber system and volatile organic compound (VOC) emission measurements were made by proton transfer reaction mass spectrometry (PTR-MS), solid phase microextraction (SPME) on fibers followed by direct injection into a gas chromatograph with an ion trap mass spectrometer (GC-ITMS), and by in situ GC with a flame ionization detector (GC-FID). We show that previously undetected sesquiterpenes and methyl chavicol significantly contribute to the total reactive biogenic emission profile from this field site.</p>
2007
[Bouvier-Brown2007] Bouvier-Brown, N. C., R. Holzinger, K. Palitzsch, and A. H. Goldstein, "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. nbouvier@nature.berkeley.edu, pp. 113–120, Aug, 2007.
Link: http://dx.doi.org/10.1016/j.chroma.2007.05.094
Abstract
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.
[Shaw2007] Shaw, S. L., F. M. Mitloehner, W. Jackson, E. J. Depeters, J. G. Fadel, P. H. Robinson, R. Holzinger, and A. H. Goldstein, "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. slshaw@alum.mit.edu, pp. 1310–1316, Feb, 2007.
Link: http://pubs.acs.org/doi/abs/10.1021/es061475e
Abstract
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.
2006
[Ng2006] Ng, N. L., J. H. Kroll, M. D. Keywood, R. Bahreini, V. Varutbangkul, R. C. Flagan, J. H. Seinfeld, A. Lee, and A. H. Goldstein, "Contribution of first- versus second-generation products to secondary organic aerosols formed in the oxidation of biogenic hydrocarbons.", Environ Sci Technol, vol. 40, no. 7: Department of Environmental Science, California Institute of Technology, Pasadena, California 91125, USA., pp. 2283–2297, Apr, 2006.
Link: http://pubs.acs.org/doi/abs/10.1021/es052269u
Abstract
Biogenic hydrocarbons emitted by vegetation are important contributors to secondary organic aerosol (SOA), but the aerosol formation mechanisms are incompletely understood. In this study, the formation of aerosols and gas-phase products from the ozonolysis and photooxidation of a series of biogenic hydrocarbons (isoprene, 8 monoterpenes, 4 sesquiterpenes, and 3 oxygenated terpenes) are examined. By comparing aerosol growth (measured by Differential Mobility Analyzers, DMAs) and gas-phase concentrations (monitored by a Proton Transfer Reaction Mass Spectrometer, PTR-MS), we study the general mechanisms of SOA formation. Aerosol growth data are presented in terms of a "growth curve", a plot of aerosol mass formed versus the amount of hydrocarbon reacted. From the shapes of the growth curves, it is found that all the hydrocarbons studied can be classified into two groups based entirely on the number of double bonds of the hydrocarbon, regardless of the reaction systems (ozonolysis or photooxidation) and the types of hydrocarbons studied: compounds with only one double bond and compounds with more than one double bond. For compounds with only one double bond, the first oxidation step is rate-limiting, and aerosols are formed mainly from low volatility first-generation oxidation products; whereas for compounds with more than one double bond, the second oxidation step may also be rate-limiting and second-generation products contribute substantially to SOA growth. This behavior is characterized by a vertical section in the growth curve, in which continued aerosol growth is observed even after all the parent hydrocarbon is consumed.
[1500] Lee, A., A. H. Goldstein, M. D. Keywood, S. Gao, V. Varutbangkul, R. Bahreini, N. L. Ng, R. C. Flagan, and J. H. Seinfeld, "Gas-phase products and secondary aerosol yields from the ozonolysis of ten different terpenes", Journal of Geophysical Research, vol. 111, 2006.
Link: http://nature.berkeley.edu/ahg/pubs/gas.pdf
Abstract
<p>The ozonolyses of six monoterpenes (α-pinene, β-pinene, 3-carene, terpinolene, α-terpinene, and myrcene), two sesquiterpenes (α-humulene and β-caryophyllene), and two oxygenated terpenes (methyl chavicol and linalool) were conducted individually in Teflon chambers to examine the gas-phase oxidation product and secondary organic aerosol (SOA) yields from these reactions. Particle size distribution and number concentration were monitored and allowed for the calculation of the SOA yield from each experiment, which ranged from 1 to 54%. A proton transfer reaction mass spectrometer (PTR-MS) was used to monitor the evolution of gas-phase products, identified by their mass to charge ratio (m/z). Several gas-phase oxidation products, formaldehyde, acetaldehyde, formic acid, acetone, acetic acid, and nopinone, were identified and calibrated. Aerosol yields, and the yields of these identified and calibrated oxidation products, as well as many higher m/z oxidation products observed with the PTR-MS, varied significantly between the different parent terpene compounds. The sum of measured oxidation products in the gas and particle phase ranged from 33 to 77% of the carbon in the reacted terpenes, suggesting there are still unmeasured products from these reactions. The observations of the higher molecular weight oxidation product ions provide evidence of previously unreported compounds and their temporal evolution in the smog chamber from multistep oxidation processes. Many of the observed ions, including m/z 111 and 113, have also been observed in ambient air above a Ponderosa pine forest canopy, and our results confirm they are consistent with products from terpene + O3 reactions. Many of these products are stable on the timescale of our experiments and can therefore be monitored in field campaigns as evidence for ozone oxidative chemistry.</p>
[1502] Lee, A., A. H. Goldstein, J. H. Kroll, N. L. Ng, V. Varutbangkul, R. C. Flagan, and J. H. Seinfeld, "Gas-phase products and secondary aerosol yields from the photooxidation of 16 different terpenes", Journal of Geophysical Research, vol. 111, 2006.
Link: http://dx.doi.org/10.1029/2006JD007050
Abstract
<p>The photooxidation of isoprene, eight monoterpenes, three oxygenated monoterpenes, and four sesquiterpenes were conducted individually at the Caltech Indoor Chamber Facility under atmospherically relevant HC:NOx ratios to monitor the time evolution and yields of SOA and gas-phase oxidation products using PTR-MS. Several oxidation products were calibrated in the PTR-MS, including formaldehyde, acetaldehyde, formic acid, acetone, acetic acid, nopinone, methacrolein + methyl vinyl ketone; other oxidation products were inferred from known fragmentation patterns, such as pinonaldehyde; and other products were identified according to their mass to charge (m/z) ratio. Numerous unidentified products were formed, and the evolution of first- and second-generation products was clearly observed. SOA yields from the different terpenes ranged from 1 to 68%, and the total gas- plus particle-phase products accounted for &sim;50&ndash;100% of the reacted carbon. The carbon mass balance was poorest for the sesquiterpenes, suggesting that the observed products were underestimated or that additional products were formed but not detected by PTR-MS. Several second-generation products from isoprene photooxidation, including m/z 113, and ions corresponding to glycolaldehyde, hydroxyacetone, methylglyoxal, and hydroxycarbonyls, were detected. The detailed time series and relative yields of identified and unidentified products aid in elucidating reaction pathways and structures for the unidentified products. Many of the unidentified products from these experiments were also observed within and above the canopy of a Ponderosa pine plantation, confirming that many products of terpene oxidation can be detected in ambient air using PTR-MS, and are indicative of concurrent SOA formation.</p>

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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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