Recent developments in high-resolution time-of-flight chemical ionization mass spectrometry (HR-ToF-CIMS) have made it possible to directly detect atmospheric organic compounds in real time with high ...sensitivity and with little or no fragmentation, including low-volatility, highly oxygenated organic vapors that are precursors to secondary organic aerosol formation. Here, using ions identified by high-resolution spectra from an HR-ToF-CIMS with acetate reagent ion chemistry, we develop an algorithm to estimate the vapor pressures of measured organic acids. The algorithm uses identified ion formulas and calculated double bond equivalencies, information unavailable in quadrupole CIMS technology, as constraints for the number of possible oxygen-containing functional groups. The algorithm is tested with acetate chemical ionization mass spectrometry (acetate-CIMS) spectra of O3 and OH oxidation products of α-pinene and naphthalene formed in a flow reactor with integrated OH exposures ranged from 1.2 × 1011 to 9.7 × 1011 molec s cm−3, corresponding to approximately 1.0 to 7.5 days of equivalent atmospheric oxidation. Measured gas-phase organic acids are similar to those previously observed in environmental chamber studies. For both precursors, we find that acetate-CIMS spectra capture both functionalization (oxygen addition) and fragmentation (carbon loss) as a function of OH exposure. The level of fragmentation is observed to increase with increased oxidation. The predicted condensed-phase secondary organic aerosol (SOA) average acid yields and O/C and H/C ratios agree within uncertainties with previous chamber and flow reactor measurements and ambient CIMS results. While acetate reagent ion chemistry is used to selectively measure organic acids, in principle this method can be applied to additional reagent ion chemistries depending on the application.
A size-resolved submicron organic aerosol composition dataset from a high-resolution time-of-flight mass spectrometer (HR-ToF-AMS) collected in Mexico City during the MILAGRO campaign in March 2006 ...is analyzed using 3-dimensional (3-D) factorization models. A method for estimating the precision of the size-resolved composition data for use with the factorization models is presented here for the first time. Two 3-D models are applied to the dataset. One model is a 3-vector decomposition (PARAFAC model), which assumes that each chemical component has a constant size distribution over all time steps. The second model is a vector-matrix decomposition (Tucker 1 model) that allows a chemical component to have a size distribution that varies in time. To our knowledge, this is the first report of an application of 3-D factorization models to data from fast aerosol instrumentation, and the first application of this vector-matrix model to any ambient aerosol dataset. A larger number of degrees of freedom in the vector-matrix model enable fitting real variations in factor size distributions, but also make the model susceptible to fitting noise in the dataset, giving some unphysical results. For this dataset and model, more physically meaningful results were obtained by partially constraining the factor mass spectra using a priori information and a new regularization method. We find four factors with each model: hydrocarbon-like organic aerosol (HOA), biomass-burning organic aerosol (BBOA), oxidized organic aerosol (OOA), and a locally occurring organic aerosol (LOA). These four factors have previously been reported from 2-dimensional factor analysis of the high-resolution mass spectral dataset from this study. The size distributions of these four factors are consistent with previous reports for these particle types. Both 3-D models produce useful results, but the vector-matrix model captures real variability in the size distributions that cannot be captured by the 3-vector model. A tracer m/z-based method provides a useful approximation for the component size distributions in this study. Variation in the size distributions is demonstrated in a case study day with a large secondary aerosol formation event, in which there is evidence for the coating of HOA-containing particles with secondary species, shifting the HOA size distribution to larger particle sizes. These 3-D factorizations could be used to extract size-resolved aerosol composition data for correlation with aerosol hygroscopicity, cloud condensation nuclei (CCN), and other aerosol impacts. Furthermore, other fast and chemically complex 3-D datasets, including those from thermal desorption or chromatographic separation, could be analyzed with these 3-D factorization models. Applications of these models to new datasets requires careful construction of error estimates and appropriate choice of models that match the underlying structure of those data. Factorization studies with these 3-D datasets have the potential to provide further insights into organic aerosol sources and processing.
Quantification of exposure to traffic-related air pollutants near highways is hampered by incomplete knowledge of the scales of temporal variation of pollutant gradients. The goal of this study was ...to characterize short-term temporal variation of vehicular pollutant gradients within 200-400 m of a major highway (>150 000 vehicles/d). Monitoring was done near Interstate 93 in Somerville (Massachusetts) from 06:00 to 11:00 on 16 January 2008 using a mobile monitoring platform equipped with instruments that measured ultrafine and fine particles (6-1000 nm, particle number concentration (PNC)); particle-phase (>30 nm) NO3- , SO42- , and organic compounds; volatile organic compounds (VOCs); and CO2 , NO, NO2 , and O3 . We observed rapid changes in pollutant gradients due to variations in highway traffic flow rate, wind speed, and surface boundary layer height. Before sunrise and peak traffic flow rates, downwind concentrations of particles, CO2 , NO, and NO2 were highest within 100-250 m of the highway. After sunrise pollutant levels declined sharply (e.g., PNC and NO were more than halved) and the gradients became less pronounced as wind speed increased and the surface boundary layer rose allowing mixing with cleaner air aloft. The levels of aromatic VOCs and NO3- , SO42- and organic aerosols were generally low throughout the morning, and their spatial and temporal variations were less pronounced compared to PNC and NO. O3 levels increased throughout the morning due to mixing with O3 -enriched air aloft and were generally lowest near the highway reflecting reaction with NO. There was little if any evolution in the size distribution of 6-225 nm particles with distance from the highway. These results suggest that to improve the accuracy of exposure estimates to near-highway pollutants, short-term (e.g., hourly) temporal variations in pollutant gradients must be measured to reflect changes in traffic patterns and local meteorology.
Organic aerosol (OA) data acquired by the Aerosol Mass Spectrometer (AMS) in 37 field campaigns were deconvolved into hydrocarbon‐like OA (HOA) and several types of oxygenated OA (OOA) components. ...HOA has been linked to primary combustion emissions (mainly from fossil fuel) and other primary sources such as meat cooking. OOA is ubiquitous in various atmospheric environments, on average accounting for 64%, 83% and 95% of the total OA in urban, urban downwind, and rural/remote sites, respectively. A case study analysis of a rural site shows that the OOA concentration is much greater than the advected HOA, indicating that HOA oxidation is not an important source of OOA, and that OOA increases are mainly due to SOA. Most global models lack an explicit representation of SOA which may lead to significant biases in the magnitude, spatial and temporal distributions of OA, and in aerosol hygroscopic properties.
In June 2010, the NOAA WP-3D aircraft conducted two survey flights around the Deepwater Horizon (DWH) oil spill. The Gulf oil spill resulted in an isolated source of secondary organic aerosol (SOA) ...precursors in a relatively clean environment. Measurements of aerosol composition and volatile organic species (VOCs) indicated formation of SOA from intermediate-volatility organic compounds (IVOCs) downwind of the oil spill (Science 2011, 331, doi 10.1126/science.1200320). In an effort to better understand formation of SOA in this environment, we present mass spectral characteristics of SOA in the Gulf and of SOA formed in the laboratory from evaporated light crude oil. Compared to urban primary organic aerosol, high-mass-resolution analysis of the background-subtracted SOA spectra in the Gulf (for short, “Gulf SOA”) showed higher contribution of C x H y O+ relative to C x H y + fragments at the same nominal mass. In each transect downwind of the DWH spill site, a gradient in the degree of oxidation of the Gulf SOA was observed: more oxidized SOA (oxygen/carbon = O/C ∼0.4) was observed in the area impacted by fresher oil; less oxidized SOA (O/C ∼0.3), with contribution from fragments with a hydrocarbon backbone, was found in a broader region of more-aged surface oil. Furthermore, in the plumes originating from the more-aged oil, contribution of oxygenated fragments to SOA decreased with downwind distance. Despite differences between experimental conditions in the laboratory and the ambient environment, mass spectra of SOA formed from gas-phase oxidation of crude oil by OH radicals in a smog chamber and a flow tube reactor strongly resembled the mass spectra of Gulf SOA (r 2 > 0.94). Processes that led to the observed Gulf SOA characteristics are also likely to occur in polluted regions where VOCs and IVOCs are coemitted.
During the 2010 TCEQ Comprehensive Flare Emission Study, a suite of instruments deployed on the Aerodyne Mobile Laboratory performed online measurements of fine particle properties. Steam and ...air-assisted flare emissions from propane and propene vent gases were measured. Black carbon (BC) mass was measured with a soot particle–aerosol mass spectrometer (SP-AMS) and a multi angle absorption photometer (MAAP). The SP-AMS obtained the mass of inorganic and organic species. A scanning mobility particle sizer (SMPS) measured particle number size distributions. Particulate matter (PM) flare emissions changed dramatically with variations in destruction removal efficiencies (DREs). BC was found to be removed at a higher DRE with steam assist (93%) relative to air assist where it remained above background levels through the lowest DRE tested (63%). Unique fullerene BC signatures and black carbon/organic carbon (BC/OC) ratios may be useful as tracers of propene flare emissions.
The Pearl River Delta (PRD) region in South China is one of the most economically developed regions in China, but it is also noted for its severe air pollution due to industrial/metropolitan ...emissions. In order to continuously improve the understanding and quantification of air pollution in this region, an intensive campaign was executed in PRD during October–November 2008. Here, we report and analyze Aerodyne High-Resolution Aerosol Mass Spectrometer measurements at Kaiping, a rural site downwind of the highly-polluted central PRD area, to characterize the general features of submicron particulate pollution in the regional air. The mean measured PMsub>1 mass concentration was 33.1±18.1 μg m−3 during the campaign and composed of organic matter (33.8%), sulfate (33.7%), ammonium (14.0%), nitrate (10.7%), black carbon (6.7%), and chloride (1.1%), which is characterized by high fractions of inorganic ions due to huge emissions of SO2 and NOx in PRD. The average size distributions of the species (except BC) were all dominated by an accumulation mode peaking at ~450 nm in vacuum aerodynamic diameter. Calculations based on high-resolution organic mass spectra indicate that C, H, O, and N on average contributed 56.6, 7.0, 35.1, and 1.3% to the total organic mass, respectively, corresponding to an organic matter mass to organic carbon mass ratio (OM/OC) of 1.77±0.08. Based on the high-resolution organic mass spectral dataset observed, Positive Matrix Factorization (PMF) analysis differentiated the organic aerosol into three components, i.e., biomass burning (BBOA) and two oxygenated (LV-OOA and SV-OOA) organic aerosols, which on average accounted for 24.5, 39.6 and 35.8% of the total organic mass, respectively. The BBOA showed strong features of biomass burning emissions and has been mainly attributed to the open field burning of crop residues after the harvest in PRD rural areas. The LV-OOA and SV-OOA were found to correspond to more aged (and thus less-volatile) and fresher (and semi-volatile) secondary organic aerosol (SOA), respectively. Analysis of meteorological influence supported that regional transport from the central PRD area was the major origin of the PM1 observed at the Kaiping site.
New particle formation and growth events have been observed in several urban areas and are of concern due to their potential negative effects on human health. The main purpose of this study was to ...investigate the chemistry of ultrafine particles during the growth phase of the frequently observed nucleation events in Pittsburgh (∼100 events per year) and therefore infer the mechanisms of new particle growth in the urban troposphere. An Aerodyne aerosol mass spectrometer (AMS) and two SMPS systems were deployed at the U.S. EPA Pittsburgh Supersite during September 2002. Significant nucleation events were observed in 3 out of the 16 days of this deployment, including one of the 10 strongest nucleation events observed in Pittsburgh over a period of 15 months. These events appear to be representative of the climatology of new particle formation and growth in the Pittsburgh region. Distinctive growth of sulfate, ammonium, organics, and nitrate in the ultrafine mode (33−60 nm in a vacuum aerodynamic diameter or ∼18−33 nm in physical diameter) was observed during each of these three events, with sulfate always being the first (and the fastest) species to increase. Ultrafine ammonium usually increased 10−40 min later than sulfate, causing the ultrafine mode particles to be more acidic during the initial stages of the nucleation events. Significant increase of ultrafine organics often happened after 11:00 a.m., when photochemistry is more intense. This observation coupled with a parallel increase of ultrafine m/z 44, a mass fragment generally representative of oxygenated organic compounds, indicates that secondary organic species contribute significantly to the growth of particles at a relatively later time of the event. Among all these four species, nitrate was always a minor component of the ultrafine particles and contributed the least to the new particle growth.
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