Apportionment of primary and secondary organic aerosols in Southern California during the 2005 Study of Organic Aerosols in Riverside (SOAR-1)

Ambient sampling was conducted in Riverside, California during the 2005 Study of Organic Aerosols in Riverside to characterize the composition and sources of organic aerosol using a variety of state-of-the-art instrumentation and source apportionment techniques. The secondary organic aerosol (SOA) mass is estimated by elemental carbon and carbon monoxide tracer methods, water soluble organic carbon content, chemical mass balance of organic molecular markers, and positive matrix factorization of high-resolution aerosol mass spectrometer data. Estimates obtained from each of these methods indicate that the organic fraction in ambient aerosol is overwhelmingly secondary in nature during a period of several weeks with moderate ozone concentrations and that SOA is the single largest component of PM1 aerosol in Riverside. Average SOA/OA contributions of 70−90% were observed during midday periods, whereas minimum SOA contributions of ~45% were observed during peak morning traffic periods. These results are contrary to previous estimates of SOA throughout the Los Angeles Basin which reported that, other than during severe photochemical smog episodes, SOA was lower than primary OA. Possible reasons for these differences are discussed

Understanding atmospheric organic aerosols via factor analysis of aerosol mass spectrometry: a review

Organic species are an important but poorly characterized constituent of airborne particulate matter. A quantitative understanding of the organic fraction of particles (organic aerosol, OA) is necessary to reduce some of the largest uncertainties that confound the assessment of the radiative forcing of climate and air quality management policies. In recent years, aerosol mass spectrometry has been increasingly relied upon for highly time-resolved characterization of OA chemistry and for elucidation of aerosol sources and lifecycle processes. Aerodyne aerosol mass spectrometers (AMS) are particularly widely used, because of their ability to quantitatively characterize the size-resolved composition of submicron particles (PM1). AMS report the bulk composition and temporal variations of OA in the form of ensemble mass spectra (MS) acquired over short time intervals. Because each MS represents the linear superposition of the spectra of individual components weighed by their concentrations, multivariate factor analysis of the MS matrix has proved effective at retrieving OA factors that offer a quantitative and simplified description of the thousands of individual organic species. The sum of the factors accounts for nearly 100% of the OA mass and each individual factor typically corresponds to a large group of OA constituents with similar chemical composition and temporal behavior that are characteristic of different sources and/or atmospheric processes. The application of this technique in aerosol mass spectrometry has grown rapidly in the last six years. Here we review multivariate factor analysis techniques applied to AMS and other aerosol mass spectrometers, and summarize key findings from field observations. Results that provide valuable information about aerosol sources and, in particular, secondary OA evolution on regional and global scales are highlighted. Advanced methods, for example a-priori constraints on factor mass spectra and the application of factor analysis to combined aerosol and gas phase data are discussed. Integrated analysis of worldwide OA factors is used to present a holistic regional and global description of OA. Finally, different ways in which OA factors can constrain global and regional models are discussed

A Technique for Rapid Gas Chromatography Analysis Applied to Ambient Organic Aerosol Measurements from the Thermal Desorption Aerosol Gas Chromatograph (TAG)

<div><p>While automated techniques exist for the integration of individual gas chromatograph peaks, manual inspection of integration quality and peak choice is still required due to drifting retention times and changing peak shapes near detection limits. The feasibility of a simplified method to obtain multiple bulk species classes from complex gas chromatography data is investigated here with data from the thermal desorption aerosol gas chromatograph (TAG). Chromatograms were divided into many “chromatography bins” containing total eluting mass spectra (both from resolved species and unresolved complex mixture [UCM]), instead of only integrating resolved peaks as is performed in the traditional chromatography analysis method. Positive matrix factorization (PMF) was applied to the mass spectra of the chromatography bins to determine major factors contributing to the observed chemical composition. PMF factors are not highly sensitive to the specific PMF error estimation method applied. Increasing the number of chromatography bins that each chromatogram was divided into improved PMF results until reaching 400 bins. Increasing the number of bins above 400 does not significantly improve the PMF results. This is likely due to 400 bin separation providing bin widths (4.6 s) that match the narrowest peak widths (4.8 s) of compounds found in the TAG chromatograms. The bin-based method took only a small fraction of the time to complete compared to peak-integrated method, significantly saving operator time and effort. Finally, high-factor solutions (e.g., 20 factors) of bin-based PMF can separate many individual compounds, homologues compound series, and UCM from chromatography data.</p><p>Copyright 2014 American Association for Aerosol Research</p></div

Wintertime Aerosol Chemistry in Sub-Arctic Urban Air

<div><p>Measurements of submicron particulate matter (PM) were performed at an urban background station, in Helsinki, Finland during wintertime to investigate the chemical characteristics and sources of PM₁. The PM₁ was dominated by sulfate and organics. The source apportionment indicated that organic aerosol (OA) was a mixture from local sources (biomass burning (BBOA), traffic, coffee roaster (CROA)), secondary compounds formed in local wintertime conditions (nitrogen containing OA (NOA), semivolatile oxygenated OA (SV-OOA), and regional and long-range transported compounds (low volatile oxygenated OA, LV-OOA). BBOA was dominated by the fragments C₂H₄O₂⁺ and C₃H₄O₂⁺ (m/z 60.021 and 73.029) from levoglucosan, or other similar sugar components, comprising on average 32% of the BBOA mass concentration. The ratio between fragments C₂H₄O₂⁺/C₃H₄O₂⁺ was significantly lower for CROA (=1.1) when compared to BBOA (=2.1), indicating that they consisted of different sugar compounds. In addition, a component containing substantial amount of nitrogen compounds (NOA) was observed in a sub-arctic region for the first time. The NOA contribution to OA ranged from 1% to 29% and elevated concentrations were observed when ambient relative humidity was high and the visibility low. Low solar radiation and temperature in wintertime were observed to influence the oxidation of compounds. A change in aerosol composition, with an increase of LV-OOA and decrease in BBOA, SV-OOA and NOA was noticed during the transition from wintertime to springtime. Size distribution measurements with high-time resolution enabled chemical characterization of externally mixed aerosol from different sources. Aged regional long-range transported aerosols were dominant at around 0.5 μm (vacuum aerodynamic diameter), whereas traffic and CROA emissions dominated at around 120 nm.</p> <p>Copyright 2014 American Association for Aerosol Research</p> </div