<p>We measured isocyanic acid (HNCO) in laboratory biomass fires at levels up to 600 parts per billion by volume (ppbv), demonstrating that it has a significant source from pyrolysis/combustion of biomass. We also measured HNCO at mixing ratios up to 200 pptv (parts-per-trillion by volume) in ambient air in urban Los Angeles, CA, and in Boulder, CO, during the recent 2010 Fourmile Canyon fire. Further, our measurements of aqueous solubility show that HNCO is highly soluble, as it dissociates at physiological pH. Exposure levels &gt; 1 ppbv provide a direct source of isocyanic acid and cyanate ion (NCO(-)) to humans at levels that have recognized health effects: atherosclerosis, cataracts, and rheumatoid arthritis, through the mechanism of protein carbamylation. In addition to the wildland fire and urban sources, we observed HNCO in tobacco smoke, HNCO has been reported from the low-temperature combustion of coal, and as a by-product of urea-selective catalytic reduction (SCR) systems that are being phased-in to control on-road diesel NO(x) emissions in the United States and the European Union. Given the current levels of exposure in populations that burn biomass or use tobacco, the expected growth in biomass burning emissions with warmer, drier regional climates, and planned increase in diesel SCR controls, it is imperative that we understand the extent and effects of this HNCO exposure.</p>

We have developed a negative-ion proton-transfer chemical-ionization mass spectrometry (NI-PT-CIMS) technique for on-line analysis of gaseous organic and inorganic acids. In this detection scheme, acetate ions (CH3C(O)O−) react very selectively with atmospheric trace acids, by proton transfer, to produce unique product ion species. We tested this ion chemistry for 11 species of which only four showed measurable fragmentation. We investigated both the time response of the inlet and humidity dependence for both formic acid and pyruvic acid measurements. A formic acid calibration was performed and found a sensitivity of 21 ± 4.3 counts per second per pptv. Formic acid measurements made during two separate informal ambient air intercomparisons: (1) with a quantum cascade IR laser absorption system (QCL) and (2) a proton-transfer reaction mass spectrometer (PTR-MS) show good agreement validating this measurement technique. The measurements of the NI-PT-CIMS and PTR-MS agree to within 5% with a high degree of correlation (r2 > 0.93). We have found the NI-PT-CIMS detection limit for formic acid is approximately 80–90 pptv for a 1 s integration period, and is currently limited by the formate background in the instrument. The fast time response and high sensitivity of the NI-PT-CIMS method make it a promising technique for the measurement of organic acids in ambient conditions.

We have used a newly developed proton-transfer ion-trap mass spectrometry (PIT-MS) instrument for online trace gas analysis of volatile organic compounds (VOCs) during the 2004 New England Air Quality Study-Intercontinental Transport and Chemical Transformation study. The PIT-MS instrument uses proton-transfer reactions with H3O+ ions to ionize VOCs, similarto a PTR-MS (proton-transfer reaction mass spectrometry) instrument but uses an ion trap mass spectrometer to analyze the product ions. The advantages of an ion trap are the improved identification of VOCs and a near 100% duty cycle. During the experiment, the PIT-MS instrument had a detection limit between 0.05 and 0.3 pbbv (S/N = 3 (signal-to-noise ratio)) for 2-min integration time for most tested VOCs. PIT-MS was used for ambient air measurements onboard a research ship and agreed well with a gas chromatography mass spectrometer). The comparison included oxygenated VOCs, aromatic compounds, and others such as isoprene, monoterpenes, acetonitrile, and dimethyl sulfide. Automated collision-induced dissociation measurements were used to determine the contributions of acetone and propanal to the measured signal at 59 amu; both species are detected at this mass and are thus indistinguishable in conventional PTR-MS.

Plant roots release about 5% to 20% of all photosynthetically-fixed carbon, and as a result create a carbon-rich environment for numerous rhizosphere organisms, including plant pathogens and symbiotic microbes. Although some characterization of root exudates has been achieved, especially of secondary metabolites and proteins, much less is known about volatile organic compounds (VOCs) released by roots. In this communication, we describe a novel approach to exploring these rhizosphere VOCs and their induction by biotic stresses. The VOC formation of Arabidopsis roots was analyzed using proton-transfer-reaction mass spectrometry (PTR-MS), a new technology that allows rapid and real time analysis of most biogenic VOCs without preconcentration or chromatography. Our studies revealed that the major VOCs released and identified by both PTR-MS and gas chromatography-mass spectrometry were either simple metabolites, ethanol, acetaldehyde, acetic acid, ethyl acetate, 2-butanone, 2,3,-butanedione, and acetone, or the monoterpene, 1,8-cineole. Some VOCs were found to be produced constitutively regardless of the treatment; other VOCs were induced specifically as a result of different compatible and noncompatible interactions between microbes and insects and Arabidopsis roots. Compatible interactions of Pseudomonas syringae DC3000 and Diuraphis noxia with Arabidopsis roots resulted in the rapid release of 1,8-cineole, a monoterpene that has not been previously reported in Arabidopsis. Mechanical injuries to Arabidopsis roots did not produce 1,8-cineole nor any C6 wound-VOCs; compatible interactions between Arabidopsis roots and Diuraphis noxia did not produce any wound compounds. This suggests that Arabidopsis roots respond to wounding differently from above-ground plant organs. Trials with incompatible interactions did not reveal a set of compounds that was significantly different compared to the noninfected roots. The PTR-MS method may open the way for functional root VOC analysis that will complement genomic investigations in Arabidopsis.

Proton-transfer-reaction mass spectrometry (PTR-MS) has emerged as a useful tool to study volatile organic compounds (VOCs) in the atmosphere. In PTR-MS, proton-transfer reactions with H30+ ions are used to ionize and measure VOCs in air with a high sensitivity and fast time response. Only the masses of the ionized VOCs and their fragments, if any, are determined, and these product ions are not unique indicators of VOC identities. Here, a combination of gas chromatography and PTR-MS (GC-PTR-MS) is used to validate the measurements by PTR-MS of a number of common atmospheric VOCs. We have analyzed 75 VOCs contained in standard mixtures by GC-PTR-MS, which allowed detected masses to be unambiguously related to a specific compound. The calibration factors for PTR-MS and GC-PTR-MS were compared and showed that the loss of VOCs in the sample acquisition and GC system is small. GC-PTR-MS analyses of 56 air samples from an urban site were used to address the specificity of PTR-MS in complex air masses. It is demonstrated that the ions associated with methanol, acetonitrile, acetaldehyde, acetone, benzene, toluene, and higher aromatic VOCs are free from significant interference. A quantitative intercomparison between PTR-MS and GC-PTR-MS measurements of the aforementioned VOCs was performed and shows that they are accurately measured by PTR-MS.

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;m−2&#xa0;h−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 (1–8.4&#xa0;mg&#xa0;m−2&#xa0;h−1), acetaldehyde (0.5–3&#xa0;mg&#xa0;m−2&#xa0;h−1), hexenals (0.1–1.5&#xa0;mg&#xa0;m−2&#xa0;h−1) and acetone (0.1–1.5&#xa0;mg&#xa0;m−2&#xa0;h−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.

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.

Numerous publications have described measurements of breath isoprene in humans, and there has been a hope that breath isoprene analyses could be a noninvasive diagnostic tool to assess blood cholesterol levels or cholesterol synthesis rate. However, significant analytic problems in breath isoprene analysis and variability in isoprene levels with age, exercise, diet, etc., have limited the usefulness of these measurements. Here, we have applied proton transfer reaction-mass spectrometry to this problem, allowing on-line detection of breath isoprene. We show that breath isoprene concentration increases within a few seconds after exercise is started as a result of a rapid increase in heart rate and then reaches a lower steady state when breath rate stabilizes. Additional experiments demonstrated that increases in heart rate associated with standing after reclining or sleeping are associated with increased breath isoprene concentrations. An isoprene gas-exchange model was developed and shows excellent fit to breath isoprene levels measured during exercise. In a preliminary experiment, we demonstrated that atorvastatin therapy leads to a decrease in serum cholesterol and low-density-lipoprotein levels and a parallel decrease in breath isoprene levels. This work suggests that there is constant endogenous production of isoprene during the day and night and reaffirms the possibility that breath isoprene can be a noninvasive marker of cholesterologenesis if care is taken to measure breath isoprene under standard conditions at constant heart rate.

An extensive dataset of VOC measurements was collected at the Sonnblick Observatory, Austria (3106 m) in Fall/Winter 1999/2000, showing high mixing ratios of anthropogenic and biogenic VOCs at this high altitude site due to upward mixing of air masses (Geophys. Res. Lett. 2F (2001) 507). Here we give an interpretation of proton-transfer-reaction (PTR-MS) mass scans obtained in November 1999 based on fragmentation data, GC-PTR-MS analysis and the variability-lifetime relationship, described by the power law, σ(ln(x))=Aτ−b. The variability-lifetime plot of anthropogenic VOCs gave a proportionality factor A of 1.40 and a,b exponent (sink term) of 0.44 and allowed an estimate of average HO-densities on the order of (1.5±0.4)×105 molecules cm−3. Additionally we were able to indirectly determine a diurnal HO-profile with peak values of (1.3±0.5)×106 molecules cm−3 around midday. HO-reaction rate coefficients for higher aldehydes (heptanal to nonanal) were estimated due to photochemical losses during a stagnant air episode (27 November) and from the variability-lifetime relationship. Combining long term PTR-MS analysis of VOCs and the variability-lifetime method provides a valuable tool for assessing the dominant cause of the variability in VOC concentrations. This information is essential in understanding the sources and photochemical processing of VOCs detected in ambient air at field measurement sites.

The wounding and drying of plant material during crop harvest could be a significant source of volatile organic compounds (VOCs) that enter the atmosphere. Here, we show that these primarily oxygenated VOCs can be measured using proton-transfer chemical-ionization mass spectrometry (PT-CIMS), a method that allows online and simultaneous monitoring of oxygenated VOC levels. For clover, alfalfa, and corn, leaf wounding and in particular drying were shown to lead to strongly enhanced emissions of a series of C6 aldehydes, alcohols, and esters derived from (Z)-3-hexenal. Additionally, for the forage crops clover and alfalfa, enhanced emissions of methanol, acetaldehyde, acetone, and butanone were observed. The identities of the measured carbonyl compounds were confirmed using high-pressure liquid chromatography. For clover, initial cutting led to a VOC release of about 175 μg of C (g dry wt)-1, while during drying the cut clover released >1000 μg of C (g dry wt)-1; qualitatively, similar amounts of VOCs were released from alfalfa, the major hay crop in the United States. The atmospheric implications of these findings may include effects on the local air quality in agricultural areas, contributions to long-range transport of pollutants, and effects on the formation of HOx (=OH + HO2) radicals in the upper troposphere.

Volatile organic compounds (VOCs) released from vegetation, including wound-induced VOCs, can have important effects on atmospheric chemistry. The analytical methods for measuring wound-induced VOCs, especially the hexenal family of VOCs (hexenals, hexenols, and hexenyl esters), are complicated by their chemical instability and the transient nature of their formation after leaf and stem wounding. Here we demonstrate that formation and emission of hexenal family compounds can be monitored on-line using proton-transfer-reaction mass spectrometry (PTR-MS), avoiding the need for preconcentration or chromatography. These measurements allow direct analysis of the rapid emission of the parent compound, (Z)-3-hexenal, within 1–2 s of wounding of aspen leaves and then its disappearance and the appearance of its metabolites including (E)-2-hexenal, hexenols, and hexenyl acetates. Similar results were seen in wounded beech leaves and clover. The emission of hexenal family compounds was proportional to the extent of wounding, was not dependent on light, occurred in attached or detached leaves, and was greatly enhanced as detached leaves dried out. Emission of (Z)-3-hexenal from detached drying aspen leaves averaged 500 μg C g−1 (dry leaf weight). Leaf wound compounds were not emitted in a nitrogen atmosphere but were released within seconds of reintroduction of oxygen; this indicates that there are not large pools of hexenyl compounds in leaves. The PTR-MS method also allows the simultaneous detection of less abundant hexanal family VOCs including hexanal, hexanol, and hexyl acetate and VOCs formed in the light (isoprene) or during anoxia (acetaldehyde). PTR-MS may be a useful tool for the analysis of VOC emissions resulting from grazing, herbivory, and other physical damage to vegetation, from harvesting of crops, and from senescing leaves.

Numerical assessments of global air quality and potential changes in atmospheric chemical constituents require estimates of the surface fluxes of a variety of trace gas species. We have developed a global model to estimate emissions of volatile organic compounds from natural sources (NVOC). Methane is not considered here and has been reviewed in detail elsewhere. The model has a highly resolved spatial grid (0.5°×0.5° latitude/longitude) and generates hourly average emission estimates. Chemical species are grouped into four categories: isoprene, monoterpenes, other reactive VOC (ORVOC), and other VOC (OVOC). NVOC emissions from oceans are estimated as a function of geophysical variables from a general circulation model and ocean color satellite data. Emissions from plant foliage are estimated from ecosystem specific biomass and emission factors and algorithms describing light and temperature dependence of NVOC emissions. Foliar density estimates are based on climatic variables and satellite data. Temporal variations in the model are driven by monthly estimates of biomass and temperature and hourly light estimates. The annual global VOC flux is estimated to be 1150 Tg C, composed of 44% isoprene, 11% monoterpenes, 22.5% other reactive VOC, and 22.5% other VOC. Large uncertainties exist for each of these estimates and particularly for compounds other than isoprene and monoterpenes. Tropical woodlands (rain forest, seasonal, drought-deciduous, and savanna) contribute about half of all global natural VOC emissions. Croplands, shrublands and other woodlands contribute 10–20% apiece. Isoprene emissions calculated for temperate regions are as much as a factor of 5 higher than previous estimates.