R. Holzinger

Proton transfer reaction mass spectrometry: on-line trace gas analysis at the ppb level

Abstract A system for trace gas analysis using proton transfer reaction mass spectrometry (PTR-MS) has been developed which allows for on-line measurements of components with concentrations as low as 1 ppb. The method is based on reactions of H 3 O + ions, which perform non-dissociative proton transfer to most of the common organic trace constituents but do not react with any of the components present in clean air. Examples of analysis of breath taken from smokers and non-smokers as well as from patients suffering from cirrhosis of the liver, and of air in buildings as well as of ambient air taken at a road crossing demonstrate the wide range of applicability of this method. An enhanced level of acetonitrile in the breath is a most suitable indicator that a person is a smoker. Enhanced levels of propanol strongly indicate that a person has a severe liver deficiency.

Comprehensive laboratory measurements of biomass‐burning emissions: 1. Emissions from Indonesian, African, and other fuels

Trace gas and particle emissions were measured from 47 laboratory fires burning 16 regionally to globally significant fuel types. Instrumentation included the following: open-path Fourier transform infrared spectroscopy; proton transfer reaction mass spectrometry; filter sampling with subsequent analysis of particles with diameter <2.5 μm for organic and elemental carbon and other elements; and canister sampling with subsequent analysis by gas chromatography (GC)/flame ionization detector, GC/electron capture detector, and GC/mass spectrometry. The emissions of 26 compounds are reported by fuel type. The results include the first detailed measurements of the emissions from Indonesian fuels. Carbon dioxide, CO, CH 4 , NH 3 , HCN, methanol, and acetic acid were the seven most abundant emissions (in order) from burning Indonesian peat. Acetol (hydroxyacetone) was a major, previously unobserved emission from burning rice straw (21-34 g/kg). The emission factors for our simulated African fires are consistent with field data for African fires for compounds measured in both the laboratory and the field. However, the higher concentrations and more extensive instrumentation in this work allowed quantification of at least 10 species not previously quantified for African field fires (in order of abundance): acetaldehyde, phenol, acetol, glycolaldehyde, methylvinylether, furan, acetone, acetonitrile, propenenitrile, and propanenitrile. Most of these new compounds are oxygenated organic compounds, which further reinforces the importance of these reactive compounds as initial emissions from global biomass burning. A few high-combustion-efficiency fires emitted very high levels of elemental (black) carbon, suggesting that biomass burning may produce more elemental carbon than previously estimated.

Biomass burning as a source of formaldehyde, acetaldehyde, methanol, acetone, acetonitrile, and hydrogen cyanide

Using a novel experimental technique, based on proton transfer reaction mass spectrometry, from measurements of emissions from laboratory scale biomass burning experiments, we have estimated the source strengths of several potential HOx producing gases: formaldehyde, acetaldehyde, methanol and acetone. The derived global average emissions are 5–13; 3.8–10; 1.5-4; 2.3-6.1 Tg y−1, respectively. The resulting global average HOx production from photochemical decay of these gases is 3 × 109 molecules cm−2 s−1. Although relatively small in a global context, these emissions are significant for the photochemistry in fresh fire plumes. From our measurements are also estimated global source strengths from biomass burning for CH3CN and HCN of 0.4-1.0; 0.2-0.6 Tg y−1 respectively. The biomass burning emissions of CH3CN may well dominate the global source of this compound, which thus might well be a unique tracer for biomass burning. Some discrepancies between experimental studies must, however, be resolved.

An Atmospheric Chemistry Interpretation of Mass Scans Obtained from a Proton Transfer Mass Spectrometer Flown over the Tropical Rainforest of Surinam

Data on a variety of organic gases are presented, obtained with a protontransfer mass spectrometer (PTR-MS) operated during the March 1998 LBA/CLAIREairborne measurement campaign, between 60 and 12500 m over the rainforest inSurinam (2° N–5° N, 54° W–57° W). The instrumentcan detect molecules with a proton affinity greater than water, includingalkenes, dialkenes, carbonyls, alcohols, and nitriles. Many such molecules areemitted from the rainforest (e.g., isoprene) or formed from the oxidation ofprimary emissions (e.g., methylvinylketone (MVK) and methacrolein (MACR)).From a comparison with modelled data; the variation with altitude; previouslyreported biogenic emissions and the time and location of the measurement,possible and probable identities for the significant masses encountered in therange 33–140 amu have been deduced.The main observed protonated masses, postulated identities and observedaverage boundary layer mixing ratios over the rainforest were: 33 methanol(1.1 nmol/mol); 42 acetonitrile (190 pmol/mol); 43 multiple possibilities (5.9nmol/mol), 45 acetaldehyde (1.7 nmol/mol), 47 formic acid (not quantified);59 acetone (2.9 nmol/mol), 61 acetic acid (not quantified), 63 dimethylsulphide (DMS) (289 pmol/mol), 69 isoprene (1.7 nmol/mol), 71 MVK + MACR (1.3nmol/mol), 73 methyl ethyl ketone (1.8 nmol/mol), 75 hydroxyacetone (606pmol/mol), 83 C5 isoprene hydroxy carbonylsC5H8O2, methyl furan, and cis 3-hexen-1-ol(732 pmol/mol), 87 C5 carbonyls and methacrylic acid, 95 possibly2-vinyl furan (656 pmol/mol), 97 unknown (305 pmol/mol), 99 cis hexenal (512pmol/mol) and 101 isoprene C5 hydroperoxides (575 pmol/mol). Somespecies agreed well with those derived from an isoprene only photochemicalmodel (e.g., mass 71 MVK + MACR) while others did not and were observed athigher than previously reported mixing ratios (e.g., mass 59 acetone, mass 63DMS). Monoterpenes were not detected above the detection limit of 300pmol/mol. Several species postulated are potentially important sources ofHOx in the free troposphere, e.g., methanol, acetone, methyl ethylketone, methyl vinyl ketone and methacrolein.

Emissions of volatile organic compounds from Quercus ilex L. measured by Proton Transfer Reaction Mass Spectrometry under different environmental conditions.

Volatile organic compound (VOC) emissions of the Mediterranean holm oak (Quercus ilex L.) were investigated using a fast Proton Transfer Reaction Mass Spectrometry (PTR-MS) instrument for analysis. This technique is able to measure compounds with a proton affinity higher than water with a high time resolution of 1 s per compound. Hence nearly all VOCs can be detected on-line. We could clearly identify the emission of methanol, acetaldehyde, ethanol, acetone, acetic acid, isoprene, monoterpenes, toluene, and C10-benzenes. Some other species could be tentatively denominated. Among these are the masses 67 (cyclo pentadiene), mass 71 (tentatively attributed to methyl vinyl ketone (MVK) and metacrolein (MACR)), 73 (attributed to methyl ethyl ketone (MEK)), 85 (C6H12 or hexanol), and 95 (vinylfuran or phenol). The emissions of all these compounds (identified as well as nonidentified) together represent 99% of all masses detected and account for a carbon loss of 0.7–2.9% of the net photosynthesis. Of special interest was a change in the emission behavior under changing environmental conditions such as flooding or fast light/dark changes. Flooding of the root system caused an increase of several VOCs between 60 and 2000%, dominated by the emission of ethanol and acetaldehyde, which can be explained by the well described production of ethanol under anoxic conditions of the root system and the recently described subsequent transport and partial oxidation to acetaldehyde within the green leaves. However, ethanol emissions were dominant. Additionally, bursts of acetaldehyde with lower ethanol emission were also found under fast light/dark changes. These bursts are not understood.

High spatial and temporal resolution measurements of primary organics and their oxidation products over the tropical forests of Surinam.

Tropical forests with emissions greater than 10(15) g C of reactive hydrocarbons per year strongly affect atmospheric chemistry. Here we report aircraft-borne measurements of organics during March 1998 in Surinam, a largely unpolluted region which is optimally located to study chemical processes induced by tropical forest emissions. Isoprene and its degradation products methylvinyl ketone (MVK) and methacrolein (MACR) and possibly isoprene hydroperoxides (ISOHP), were measured in the nmol mol(-1) volume mixing ratio (VMR) range, consistent with estimated emissions and model calculations. In addition, high VMRs of some non-isoprene-derived organics were measured, such as acetone (approximate to 2-4 nmol mol(1) up to 12 km altitude), an important source of HO and HO(2) in the upper troposphere. Moreover, several masses were measured at significant mixing ratios which could not be identified by reference to previous field measurements or gas-phase isoprene chemistry. High VMRs, almost 0.4 nmol mol(-1), were also recorded for a compound which is most likely dimethyl sulphide (DMS). If so, boundary layer loss of HO by reactions with hydrocarbons and their oxidation products strongly prolongs the lifetime of DMS, allowing its transport deep into the Amazon forest south of the intertropical convergence zone (ITCZ). We postulate greater sulphate production and deposition north than south of the (ITCZ) with possible consequences for cloud and ecosystem properties

Active atmosphere-ecosystem exchange of the vast majority of detected volatile organic compounds.

Two-Way Street Most studies of volatile organic compounds (VOCs) found in the atmosphere, which play important roles in atmospheric chemistry, have concentrated on dominant species such as isoprene. There are thousands of other classes of VOCs, and how they are exchanged between the biosphere and the atmosphere is unclear. Park et al. (p. 643) measured the fluxes of more than 500 types of VOCs using a highly sensitive type of mass spectrometry and an absolute value eddy covariance method. The majority of these species were actively exchanged between the atmosphere and the biosphere, with more than a quarter showing net deposition. These results should help to improve air quality and global climate models, and strengthen our understanding of atmospheric VOC chemistry. Many volatile organic compounds emitted by vegetation are actively exchanged between plants and the atmosphere. Numerous volatile organic compounds (VOCs) exist in Earth’s atmosphere, most of which originate from biogenic emissions. Despite VOCs’ critical role in tropospheric chemistry, studies for evaluating their atmosphere-ecosystem exchange (emission and deposition) have been limited to a few dominant compounds owing to a lack of appropriate measurement techniques. Using a high–mass resolution proton transfer reaction–time of flight–mass spectrometer and an absolute value eddy-covariance method, we directly measured 186 organic ions with net deposition, and 494 that have bidirectional flux. This observation of active atmosphere-ecosystem exchange of the vast majority of detected VOCs poses a challenge to current emission, air quality, and global climate models, which do not account for this extremely large range of compounds. This observation also provides new insight for understanding the atmospheric VOC budget.

Isoprene and Its Oxidation Products Methyl Vinyl Ketone, Methacrolein, and Isoprene Related Peroxides Measured Online over the Tropical Rain Forest of Surinam in March 1998

Airborne measurements of volatile organic compounds (VOC) were performed overthe tropical rainforest in Surinam (0–12 km altitude,2°–7° N, 54°–58° W) using the proton transferreaction mass spectrometry (PTR-MS) technique, which allows online monitoringof compounds like isoprene, its oxidation products methyl vinyl ketone,methacrolein, tentatively identified hydroxy-isoprene-hydroperoxides, andseveral other organic compounds. Isoprene volume mixing ratios (VMR) variedfrom below the detection limit at the highest altitudes to about 7 nmol/molin the planetary boundary layer shortly before sunset. Correlations betweenisoprene and its product compounds were made for different times of day andaltitudes, with the isoprene-hydroperoxides showing the highest correlation.Model calculated mixing ratios of the isoprene oxidation products using adetailed hydrocarbon oxidation mechanism, as well as the intercomparisonmeasurement with air samples collected during the flights in canisters andlater analysed with a GC-FID, showed good agreement with the PTR-MSmeasurements, in particular at the higher mixing ratios.Low OH concentrations in the range of 1–3 × 105molecules cm-3 averaged over 24 hours were calculated due to lossof OH and HO2 in the isoprene oxidation chain, thereby stronglyenhancing the lifetime of gases in the forest boundary layer.

Acetonitrile and benzene in the breath of smokers and non-smokers investigated by proton transfer reaction mass spectrometry (PTR-MS)

Abstract Benzene and acetonitrile are both present in greater concentrations in the breath of smokers than in non-smokers. The concentrations of these neutrals can be readily detected in the gas phase by their proton transfer reactions with H3O+. The concentration of benzene in the breath of smokers rapidly decreases with the time since the last cigarette was smoked, declining to values similar to those of non-smokers within an hour. In contrast, the concentration of acetonitrile in the breath of smokers takes nearly a week to decrease to that of non-somokers, once smoking stops. Thus the analysis of acetonitrile in the breath is a most suitable indicator of whether a given subject is or is not a smoker.

Secondary organic aerosols formed from oxidation of biogenic volatile organic compounds in the Sierra Nevada Mountains of California

Received 7 February 2006; revised 14 April 2006; accepted 17 May 2006; published 25 August 2006. [1] Biogenic volatile organic compound (BVOC) emissions, such as isoprene and terpenes, can be oxidized to form less volatile carbonyls, acids, and multifunctional oxygenated products that may condense to form secondary organic aerosols (SOA). This research was designed to assess the contribution of oxidized BVOC emissions to SOA in coniferous forests by collecting high-volume particulate samples for 6 days and 5 nights in the summer of 2003. The samples were analyzed for acids, carbonyls, polyols and alkanes to quantify oxidized BVOCs. Terpene and isoprene oxidation products were among the most abundant chemical species detected with the exception of hexadecanoic acid, octadecanoic acid and two butyl esters of unknown origin. The terpene oxidation products of pinonic acid, pinic acid, nopinone and pinonaldehyde showed clear diurnal cycles with concentrations two- to eight-fold higher at night. These cycles resulted from the diurnal cycles in gaseous terpene concentrations and lower temperatures that enhanced condensation of semivolatile chemicals onto aerosols. The terpene-derived compounds averaged 157 ± 118 ng/m 3 of particulate organic matter while the isoprene oxidation compounds, namely the 2-methyltetrols and 2-methylglyceric acid, accounted for 53 ± 19 ng/m 3 . Together, the terpene and isoprene oxidation products represented 36.9% of the identified organic mass of 490 ± 95 ng/m 3 .P M10 organic matter loadings in the region were approximately 2.1 ± 1.2 mg/m 3 , so about 23% of the organic matter was identified and at least 8.6% was oxidized BVOCs. The BVOC oxidation products we measured were significant, but not dominant, contributors to the regional SOA only 75 km downwind of the Sacramento urban area.