Aircraft measurements during the 2006 Gulf of Mexico Atmospheric Composition and Climate Study (GoMACCS) are used to examine the influence of shallow cumulus clouds on vertical profiles of aerosol chemical composition, size distributions, and secondary aerosol precursor gases. The data show signatures of convective transport of particles, gases and moisture from near the surface to higher altitudes, and of aqueous-phase production of aerosol mass (sulfate and organics) in cloud droplets and aerosol water. In cloudy conditions, the average aerosol volume concentration at an altitude of 2850 m, above typical cloud top levels, was found to be 34% of that at 450 m; for clear conditions, the same ratio was 13%. Both organic and sulfate mass fractions were on average constant with altitude (around 50%); however, the ratio of oxalate to organic mass increased with altitude (from 1% at 450 m to almost 9% at 3450 m), indicative of the influence of in-cloud production on the vertical abundance and characteristics of secondary organic aerosol (SOA) mass. A new metric termed “residual cloud fraction� is introduced as a way of quantifying the “cloud processing history� of an air parcel. Results of a parcel model simulating aqueous phase production of sulfate and organics reproduce observed trends and point at a potentially important role of SOA production, especially oligomers, in deliquesced aerosols. The observations emphasize the importance of shallow cumulus clouds in altering the vertical distribution of aerosol properties that influence both their direct and indirect effect on climate.

<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>

A negative-ion proton transfer chemical ionization mass spectrometric technique (NI-PT-CIMS), using acetate as the reagent ion, was applied to the measurement of volatile inorganic acids of atmospheric interest: hydrochloric (HCl), nitrous (HONO), nitric (HNO3), and isocyanic (HNCO) acids. Gas phase calibrations through the sampling inlet showed the method to be intrinsically sensitive (6–16 cts/pptv), but prone to inlet effects for HNO3 and HCl. The ion chemistry was found to be insensitive to water vapor concentrations, in agreement with previous studies of carboxylic acids. The inlet equilibration times for HNCO and HONO were 2 to 4 s, allowing for measurement in biomass burning studies. Several potential interferences in HONO measurements were examined: decomposition of HNO3·NO3- clusters within the CIMS, and NO2-water production on inlet surfaces, and were quite minor (≤1%, 3.3%, respectively). The detection limits of the method were limited by the instrument backgrounds in the ion source and flow tube, and were estimated to range between 16 and 50 pptv (parts per trillion by volume) for a 1 min average. The comparison of HONO measured by CIMS and by in situ FTIR showed good correlation and agreement to within 17%. The method provided rapid and accurate measurements of HNCO and HONO in controlled biomass burning studies, in which both acids were seen to be important products.

Emissions from 34 laboratory biomass fires were investigated at the combustion facility of the U.S. Department of Agriculture Fire Sciences Laboratory in Missoula, Montana. Gas-phase organic and inorganic acids were quantified using negative-ion proton-transfer chemical-ionization mass spectrometry (NI-PT-CIMS), open-path Fourier transform infrared spectroscopy (OP-FTIR), and proton-transfer-reaction mass spectrometry (PTR-MS). NI-PT-CIMS is a novel technique that measures the mass-to-charge ratio (m/z) of ions generated from reactions of acetate (CH3C(O)O−) ions with inorganic and organic acids. The emission ratios for various important reactive acids with respect to CO were determined. Emission ratios for isocyanic acid (HNCO), 1,2 and 1,3-benzenediols (catechol, resorcinol), nitrous acid (HONO), acrylic acid, methacrylic acid, propionic acid, formic acid, pyruvic acid, and glycolic acid were measured from biomass burning. Our measurements show that there is a significant amount of HONO in fresh smoke. The NI-PT-CIMS measurements were validated by comparison with OP-FTIR measurements of HONO and formic acid (HCOOH) and with PTR-MS measurements of HCOOH.

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.

<p>Proton-transfer-reaction mass spectrometry (PTR-MS) allows real-time measurements of volatile organic compounds (VOCs) in air with a high sensitivity and a fast time response. The use of PTR-MS in atmospheric research has expanded rapidly in recent years, and much has been learned about the instrument response and specificity of the technique in the analysis of air from different regions of the atmosphere. This paper aims to review the progress that has been made. The theory of operation is described and allows the response of the instrument to be described for different operating conditions. More accurate determinations of the instrument response involve calibrations using standard mixtures, and some results are shown. Much has been learned about the specificity of PTR-MS from inter-comparison studies as well the coupling of PTR-MS with a gas chromatographic interface. The literature on this issue is reviewed and summarized for many VOCs of atmospheric interest. Some highlights of airborne measurements by PTR-MS are presented, including the results obtained in fresh and aged forest-fire and urban plumes. Finally, the recent work that is focused on improving the technique is discussed.</p>

We use a global three-dimensional model simulation of atmospheric methanol to examine the consistency between observed atmospheric concentrations and current understanding of sources and sinks. Global sources in the model include 128 Tg yr−1 from plant growth, 38 Tg yr−1 from atmospheric reactions of CH3O2 with itself and other organic peroxy radicals, 23 Tg yr−1 from plant decay, 13 Tg yr−1 from biomass burning and biofuels, and 4 Tg yr−1 from vehicles and industry. The plant growth source is a factor of 3 higher for young than from mature leaves. The atmospheric lifetime of methanol in the model is 7 days; gas-phase oxidation by OH accounts for 63% of the global sink, dry deposition to land 26%, wet deposition 6%, uptake by the ocean 5%, and aqueous-phase oxidation in clouds less than 1%. The resulting simulation of atmospheric concentrations is generally unbiased in the Northern Hemisphere and reproduces the observed correlations of methanol with acetone, HCN, and CO in Asian outflow. Accounting for decreasing emission from leaves as they age is necessary to reproduce the observed seasonal variation of methanol concentrations at northern midlatitudes. The main model discrepancy is over the South Pacific, where simulated concentrations are a factor of 2 too low. Atmospheric production from the CH3O2 self-reaction is the dominant model source in this region. A factor of 2 increase in this source (to 50–100 Tg yr−1) would largely correct the discrepancy and appears consistent with independent constraints on CH3O2 concentrations. Our resulting best estimate of the global source of methanol is 240 Tg yr−1. More observations of methanol concentrations and fluxes are needed over tropical continents. Better knowledge is needed of CH3O2 concentrations in the remote troposphere and of the underlying organic chemistry.

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.

Proton-transfer-reaction mass spectrometry (PTR-MS) has emerged as a useful tool to study the atmospheric chemistry of volatile organic compounds (VOCs). The technique combines a fast response time with a low detection limit, and allows atmospheric measurements of many important VOCs and their oxidation products. Here, we inter-compare the results obtained with two differently configured PTR-MS instruments operated onboard a Falcon aircraft during the Mediterranean Intensive Oxidants Study (MINOS) campaign in the Mediterranean region. One PTR-MS was operated at a drift tube pressure of 2.3 mbar and an electric field divided by gas number density value (E/N) of 120 Td for the detection of VOCs and aromatic hydrocarbons. The other PTR-MS was operated at an increased pressure of 2.8 mbar and a reduced E/N of 97 Td for the detection of peroxyacetyl nitrate (PAN). As a consequence, more H3O+(H2O)n cluster ions were present in the drift tube, which undergo proton-transfer reactions with VOCs similar to H3O+ ions. The results for methanol (CH3OH), acetonitrile (CH3CN) and acetone (CH3COCH3) obtained with the instruments compared very well. The agreement between the two results was relatively independent of the ambient mixing ratio of water, which influences the H3O+(H2O)n cluster ion distribution, and of ozone, which has been implicated in the artificial formation of aldehydes and ketones.

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.