Intermediate-volatility organic compounds: a large source of secondary organic aerosol.

Secondary organic aerosol (SOA) is a major component of atmospheric fine particle mass. Intermediate-volatility organic compounds (IVOCs) have been proposed to be an important source of SOA. We present a comprehensive analysis of atmospheric IVOC concentrations and their SOA production using measurements made in Pasadena, California during the California at the Nexus of Air Quality and Climate Change (CalNex) study. The campaign-average concentration of primary IVOCs was 6.3 ± 1.9 µg m(-3) (average ± standard deviation), which is comparable to the concentration of organic aerosol but only 7.4 ± 1.2% of the concentration of speciated volatile organic compounds. Only 8.6 ± 2.2% of the mass of the primary IVOCs was speciated. Almost no weekend/weekday variation in the ambient concentration of both speciated and total primary IVOCs was observed, suggesting that petroleum-related sources other than on-road diesel vehicles contribute substantially to the IVOC emissions. Primary IVOCs are estimated to produce about 30% of newly formed SOA in the afternoon during CalNex, about 5 times that from single-ring aromatics. The importance of IVOCs in SOA formation is expected to be similar in many urban environments.

Vertically resolved measurements of nighttime radical reservoirs in Los Angeles and their contribution to the urban radical budget.

Photolabile nighttime radical reservoirs, such as nitrous acid (HONO) and nitryl chloride (ClNO(2)), contribute to the oxidizing potential of the atmosphere, particularly in early morning. We present the first vertically resolved measurements of ClNO(2), together with vertically resolved measurements of HONO. These measurements were acquired during the California Nexus (CalNex) campaign in the Los Angeles basin in spring 2010. Average profiles of ClNO(2) exhibited no significant dependence on height within the boundary layer and residual layer, although individual vertical profiles did show variability. By contrast, nitrous acid was strongly enhanced near the ground surface with much smaller concentrations aloft. These observations are consistent with a ClNO(2) source from aerosol uptake of N(2)O(5) throughout the boundary layer and a HONO source from dry deposition of NO(2) to the ground surface and subsequent chemical conversion. At ground level, daytime radical formation calculated from nighttime-accumulated HONO and ClNO(2) was approximately equal. Incorporating the different vertical distributions by integrating through the boundary and residual layers demonstrated that nighttime-accumulated ClNO(2) produced nine times as many radicals as nighttime-accumulated HONO. A comprehensive radical budget at ground level demonstrated that nighttime radical reservoirs accounted for 8% of total radicals formed and that they were the dominant radical source between sunrise and 09:00 Pacific daylight time (PDT). These data show that vertical gradients of radical precursors should be taken into account in radical budgets, particularly with respect to HONO.

Organosulfates as tracers for secondary organic aerosol (SOA) formation from 2-methyl-3-buten-2-ol (MBO) in the atmosphere.

2-Methyl-3-buten-2-ol (MBO) is an important biogenic volatile organic compound (BVOC) emitted by pine trees and a potential precursor of atmospheric secondary organic aerosol (SOA) in forested regions. In the present study, hydroxyl radical (OH)-initiated oxidation of MBO was examined in smog chambers under varied initial nitric oxide (NO) and aerosol acidity levels. Results indicate measurable SOA from MBO under low-NO conditions. Moreover, increasing aerosol acidity was found to enhance MBO SOA. Chemical characterization of laboratory-generated MBO SOA reveals that an organosulfate species (C(5)H(12)O(6)S, MW 200) formed and was substantially enhanced with elevated aerosol acidity. Ambient fine aerosol (PM(2.5)) samples collected from the BEARPEX campaign during 2007 and 2009, as well as from the BEACHON-RoMBAS campaign during 2011, were also analyzed. The MBO-derived organosulfate characterized from laboratory-generated aerosol was observed in PM(2.5) collected from these campaigns, demonstrating that it is a molecular tracer for MBO-initiated SOA in the atmosphere. Furthermore, mass concentrations of the MBO-derived organosulfate are well correlated with MBO mixing ratio, temperature, and acidity in the field campaigns. Importantly, this compound accounted for an average of 0.25% and as high as 1% of the total organic aerosol mass during BEARPEX 2009. An epoxide intermediate generated under low-NO conditions is tentatively proposed to produce MBO SOA.

Isocyanic acid in the atmosphere and its possible link to smoke-related health effects.

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 > 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.

Source identification of reactive hydrocarbons and oxygenated VOCs in the summertime in Beijing.

It is important to identify the sources of reactive volatile organic compounds (VOCs) in Beijing for effective ground-level ozone abatement. In this paper, semihourly measurements of hydrocarbons and oxygenated VOCs (OVOCs) were taken at an urban site in Beijing in August2005. C2-C5 alkenes, isoprene, and C1-C3 aldehydes were determined as "key reactive species" by their OH loss rates. Principal component analysis (PCA) was used to define the major sources of reactive species and to classify the dominant air mass types at the sampling site. Vehicle exhaust was the largest contributor to reactive alkenes. More aged air masses with enriched OVOCs traveled mainly from the east or southeast of Beijing. The OVOC sources were estimated by a least-squares fit approach and included primary emissions, secondary sources, and background. Approximately half of the C1-C3 aldehydes were attributed to secondary sources, while regional background accounted for 21-23% of the mixing ratios of aldehydes. Primary anthropogenic emissions were comparable to biogenic contributions (10-16%).

Online volatile organic compound measurements using a newly developed proton-transfer ion-trap mass spectrometry instrument during New England Air Quality Study--Intercontinental Transport and Chemical Transformation 2004: performance, intercomparison, and compound identification.

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.

Inter-comparison of laser photoacoustic spectroscopy and gas chromatography techniques for measurements of ethene in the atmosphere.

Laser photoacoustic spectroscopy (LPAS) is highly suitable for the detection of ethene in air due to the overlap between its strongest absorption lines and the wavelengths accessible by high-powered CO2 lasers. Here, we test the ability of LPAS to measure ethene in ambient air by comparing the measurements in urban air with those from a gas chromatography flame-ionization detection (GC-FID) instrument. Over the course of several days, we obtained quantitative agreement between the two measurements. Over this period, the LPAS instrument had a positive offset of 330 +/- 140 pptv (parts-per-trillion by volume) relative to the GC-FID instrument, possibly caused by interference from other species. The detection limit of the LPAS instrument is currently estimated around 1 ppbv and is limited by this offset and the statistical noise in the data. We conclude that LPAS has the potential to provide fast-response measurements of ethene in the atmosphere, with significant advantages over existing techniques when measuring from moving platforms and in the vicinity of emission sources.

Temporal changes in U.S. benzene emissions inferred from atmospheric measurements.

The 1990 Clean Air Act Amendments required the United States Environmental Protection Agency (U.S. EPA) to enact stricter regulations aimed at reducing benzene emissions. In an effort to determine whether these new regulations have been successful in reducing atmospheric benzene concentrations, we have evaluated benzene-to-acetylene ratios from data sets spanning nearlythree decades, collected during several field studies and from the U.S. EPA's Photochemical Assessment Monitoring Station (PAMS) network. The field-study data indicate a decrease in benzene relative to acetylene of approximately 40% from 1994 to 2002. This corresponds to a decrease in benzene alone of approximately 56% over the same period. In contrast, the PAMS data exhibit high interannual variability with no discernible trend. This discrepancy is attributed to measurement problems in the PAMS data sets.

Validation of atmospheric VOC measurements by proton-transfer-reaction mass spectrometry using a gas-chromatographic preseparation method.

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.