Organic aerosol (OA) emissions from motor vehicles, meat-cooking and trash burning are analyzed here using a high-resolution aerosol mass spectrometer (AMS). High resolution data show that aerosols emitted by combustion engines and plastic burning are dominated by hydrocarbon-like organic compounds. Meat cooking and especially paper burning emissions contain significant fractions of oxygenated organic compounds; however, their unit-resolution mass spectral signatures are very similar to those from ambient hydrocarbon-like OA, and very different from the mass spectra of ambient secondary or oxygenated OA (OOA). Thus, primary OA from these sources is unlikely to be a significant direct source of ambient OOA. There are significant differences in high-resolution tracer m/zs that may be useful for differentiating some of these sources. Unlike in most ambient spectra, all of these sources have low total m/z 44 and this signal is not dominated by the CO2+ ion. All sources have high m/z 57, which is low during high OOA ambient periods. Spectra from paper burning are similar to some types of biomass burning OA, with elevated m/z 60. Meat cooking aerosols also have slightly elevated m/z 60, whereas motor vehicle emissions have very low signal at this m/z.
The chemical composition of secondary organic aerosol formed in an environmental chamber from ozonolysis of 1-tetradecene in humid and dry air was determined using a thermal desorption particle beam mass spectrometer (TDPBMS). The major products are α-hydroxytridecyl hydroperoxide and bis(α-hydroxytridecyl) peroxide in humid air and symmetric C26 and asymmetric C14 secondary ozonides in dry air. The hydroperoxide is formed by reaction of stabilized Criegee biradicals with water vapor, and the peroxide (a peroxyhemiacetal) is formed by subsequent reaction of the hydroperoxide with tridecanal. The secondary ozonides are formed by reactions of stabilized Criegee biradicals with tridecanal and formaldehyde. Tridecanoic acid was also observed in both experiments. These compounds have very low vapor pressures and are stable on the 3-h time scale of the environmental chamber experiments. When collected aerosol was analyzed by gas chromatography, the hydroperoxides, peroxides, and secondary ozonides thermally decomposed to more volatile compounds, including tridecanal, tridecanoic acid, and a few unidentified products.
Abstract. Secondary organic aerosol (SOA) was generated by irradiating 1,3-butadiene (13BD) in the presence of H2O2 or NOx. Experiments were conducted in a smog chamber operated in either flow or batch mode. A filter/denuder sampling system was used for simultaneously collecting gas- and particle-phase products. The chemical composition of the gas phase and SOA was analyzed using derivative-based methods (BSTFA, BSTFA + PFBHA, or DNPH) followed by gas chromatography–mass spectrometry (GC-MS) or high-performance liquid chromatography (HPLC) analysis of the derivative compounds. The analysis showed the occurrence of more than 60 oxygenated organic compounds in the gas and particle phases, of which 31 organic monomers were tentatively identified. The major identified products include glyceric acid, d-threitol, erythritol, d-threonic acid, meso-threonic acid, erythrose, malic acid, tartaric acid, and carbonyls including glycolaldehyde, glyoxal, acrolein, malonaldehyde, glyceraldehyde, and peroxyacryloyl nitrate (APAN). Some of these were detected in ambient PM2.5 samples and could potentially serve as organic markers of 1,3-butadiene (13BD). Furthermore, a series of oligoesters were detected and found to be produced from esterification reactions among compounds bearing alcoholic groups and compounds bearing acidic groups. Time profiles are provided for selected compounds. SOA was analyzed for organic mass to organic carbon (OM / OC) ratio, effective enthalpy of vaporization (ΔHvapeff), and aerosol yield. The average OM / OC ratio and SOA density were 2.7 ± 0.09 and 1.2 ± 0.05, respectively. The average ΔHvapeff was 26.1 ± 1.5 kJ mol−1, a value lower than that of isoprene SOA. The average laboratory SOA yield measured in this study at aerosol mass concentrations between 22.5 and 140.2 μg m−3 was 0.025 ± 0.011, a value consistent with the literature (0.021–0.178). While the focus of this study has been examination of the particle-phase measurements, the gas-phase photooxidation products have also been examined. The contribution of SOA products from 13BD oxidation to ambient PM2.5 was investigated by analyzing a series of ambient PM2.5 samples collected in several locations around the United States. In addition to the occurrence of several organic compounds in field and laboratory samples, glyceric acid, d-threitol, erythritol, erythrose, and threonic acid were found to originate only from the oxidation of 13BD based on our previous experiments involving chamber oxidation of a series of hydrocarbons. Initial attempts have been made to quantify the concentrations of these compounds. The average concentrations of these compounds in ambient PM2.5 samples from the California Research at the Nexus of Air Quality and Climate Change (CalNex) study ranged from 0 to approximately 14.1 ng m−3. The occurrence of several other compounds in both laboratory and field samples suggests that SOA originating from 13BD oxidation could contribute to the ambient aerosol mainly in areas with high 13BD emission rates.
Abstract. The influence of losses of organic vapors to chamber walls during secondary organic aerosol (SOA) formation experiments has recently been established. Here, the influence of such losses on simulated ambient SOA concentrations and properties is assessed in the University of California at Davis / California Institute of Technology (UCD/CIT) regional air quality model using the statistical oxidation model (SOM) for SOA. The SOM was fit to laboratory chamber data both with and without accounting for vapor wall losses following the approach of Zhang et al. (2014). Two vapor wall-loss scenarios are considered when fitting of SOM to chamber data to determine best-fit SOM parameters, one with “low” and one with “high” vapor wall-loss rates to approximately account for the current range of uncertainty in this process. Simulations were run using these different parameterizations (scenarios) for both the southern California/South Coast Air Basin (SoCAB) and the eastern United States (US). Accounting for vapor wall losses leads to substantial increases in the simulated SOA concentrations from volatile organic compounds (VOCs) in both domains, by factors of ∼ 2–5 for the low and ∼ 5–10 for the high scenarios. The magnitude of the increase scales approximately inversely with the absolute SOA concentration of the no loss scenario. In SoCAB, the predicted SOA fraction of total organic aerosol (OA) increases from ∼ 0.2 (no) to ∼ 0.5 (low) and to ∼ 0.7 (high), with the high vapor wall-loss simulations providing best general agreement with observations. In the eastern US, the SOA fraction is large in all cases but increases further when vapor wall losses are accounted for. The total OA ∕ ΔCO ratio captures the influence of dilution on SOA concentrations. The simulated OA ∕ ΔCO in SoCAB (specifically, at Riverside, CA) is found to increase substantially during the day only for the high vapor wall-loss scenario, which is consistent with observations and indicative of photochemical production of SOA. Simulated O : C atomic ratios for both SOA and for total OA increase when vapor wall losses are accounted for, while simulated H : C atomic ratios decrease. The agreement between simulations and observations of both the absolute values and the diurnal profile of the O : C and H : C atomic ratios for total OA was greatly improved when vapor wall-losses were accounted for. These results overall demonstrate that vapor wall losses in chambers have the potential to exert a large influence on simulated ambient SOA concentrations, and further suggest that accounting for such effects in models can explain a number of different observations and model–measurement discrepancies.
Abstract. Although laboratory studies show that biogenic volatile organic compounds (VOCs) yield substantial secondary organic aerosol (SOA), production of biogenic SOA as indicated by upward fluxes has not been conclusively observed over forests. Further, while aerosols are known to deposit to surfaces, few techniques exist to provide chemically-resolved particle deposition fluxes. To better constrain aerosol sources and sinks, we have developed a new technique to directly measure fluxes of chemically-resolved submicron aerosols using the high-resolution time-of-flight aerosol mass spectrometer (HR-AMS) in a new, fast eddy covariance mode. This approach takes advantage of the instrument's ability to quantitatively identify both organic and inorganic components, including ammonium, sulphate and nitrate, at a temporal resolution of several Hz. The new approach has been successfully deployed over a temperate ponderosa pine plantation in California during the BEARPEX-2007 campaign, providing both total and chemically resolved non-refractory (NR) PM1 fluxes. Average deposition velocities for total NR-PM1 aerosol at noon were 2.05 ± 0.04 mm s−1. Using a high resolution measurement of the NH2+ and NH3+ fragments, we demonstrate the first eddy covariance flux measurements of particulate ammonium, which show a noon-time deposition velocity of 1.9 ± 0.7 mm s−1 and are dominated by deposition of ammonium sulphate.
Abstract. In this study we compile and present results from the factor analysis of 43 Aerosol Mass Spectrometer (AMS) datasets (27 of the datasets are reanalyzed in this work). The components from all sites, when taken together, provide a holistic overview of Northern Hemisphere organic aerosol (OA) and its evolution in the atmosphere. At most sites, the OA can be separated into oxygenated OA (OOA), hydrocarbon-like OA (HOA), and sometimes other components such as biomass burning OA (BBOA). We focus on the OOA components in this work. In many analyses, the OOA can be further deconvolved into low-volatility OOA (LV-OOA) and semi-volatile OOA (SV-OOA). Differences in the mass spectra of these components are characterized in terms of the two main ions m/z 44 (CO2+) and m/z 43 (mostly C2H3O+), which are used to develop a new mass spectral diagnostic for following the aging of OA components in the atmosphere. The LV-OOA component spectra have higher f44 (ratio of m/z 44 to total signal in the component mass spectrum) and lower f43 (ratio of m/z 43 to total signal in the component mass spectrum) than SV-OOA. A wide range of f44 and O:C ratios are observed for both LV-OOA (0.17±0.04, 0.73±0.14) and SV-OOA (0.07±0.04, 0.35±0.14) components, reflecting the fact that there is a continuum of OOA properties in ambient aerosol. The OOA components (OOA, LV-OOA, and SV-OOA) from all sites cluster within a well-defined triangular region in the f44 vs. f43 space, which can be used as a standardized means for comparing and characterizing any OOA components (laboratory or ambient) observed with the AMS. Examination of the OOA components in this triangular space indicates that OOA component spectra become increasingly similar to each other and to fulvic acid and HULIS sample spectra as f44 (a surrogate for O:C and an indicator of photochemical aging) increases. This indicates that ambient OA converges towards highly aged LV-OOA with atmospheric oxidation. The common features of the transformation between SV-OOA and LV-OOA at multiple sites potentially enable a simplified description of the oxidation of OA in the atmosphere. Comparison of laboratory SOA data with ambient OOA indicates that laboratory SOA are more similar to SV-OOA and rarely become as oxidized as ambient LV-OOA, likely due to the higher loadings employed in the experiments and/or limited oxidant exposure in most chamber experiments.
Abstract. We present a rapid method for apportioning the sources of atmospheric organic aerosol composition measured by gas chromatography–mass spectrometry methods. Here, we specifically apply this new analysis method to data acquired on a thermal desorption aerosol gas chromatograph (TAG) system. Gas chromatograms are divided by retention time into evenly spaced bins, within which the mass spectra are summed. A previous chromatogram binning method was introduced for the purpose of chromatogram structure deconvolution (e.g., major compound classes) (Zhang et al., 2014). Here we extend the method development for the specific purpose of determining aerosol samples' sources. Chromatogram bins are arranged into an input data matrix for positive matrix factorization (PMF), where the sample number is the row dimension and the mass-spectra-resolved eluting time intervals (bins) are the column dimension. Then two-dimensional PMF can effectively do three-dimensional factorization on the three-dimensional TAG mass spectra data. The retention time shift of the chromatogram is corrected by applying the median values of the different peaks' shifts. Bin width affects chemical resolution but does not affect PMF retrieval of the sources' time variations for low-factor solutions. A bin width smaller than the maximum retention shift among all samples requires retention time shift correction. A six-factor PMF comparison among aerosol mass spectrometry (AMS), TAG binning, and conventional TAG compound integration methods shows that the TAG binning method performs similarly to the integration method. However, the new binning method incorporates the entirety of the data set and requires significantly less pre-processing of the data than conventional single compound identification and integration. In addition, while a fraction of the most oxygenated aerosol does not elute through an underivatized TAG analysis, the TAG binning method does have the ability to achieve molecular level resolution on other bulk aerosol components commonly observed by the AMS.
