ALBERT

Description: Organosulfates are components of secondary organic aerosols (SOA) that form from oxidation of volatile organic compounds (VOCs) in the presence of sulfate. In this study, the composition and abundance of organosulfates were determined in fine particulate matter (PM2.5) collected from Centreville, AL, during the Southern Oxidant and Aerosol Study (SOAS) in summer 2013. Six organosulfates were quantified using hydrophilic interaction liquid chromatography (HILIC) with triple quadrupole mass spectrometry (TQD) against authentic standards. Among these, the three most abundant species were glycolic acid sulfate (0.5–52.5 ng m−3), lactic acid sulfate (0.5–36.7 ng m−3), and hydroxyacetone sulfate (0.5–14.3 ng m−3). These three species were strongly inter-correlated, suggesting similar precursors and/or formation pathways. Further correlations with sulfate, isoprene, and isoprene oxidation products indicate important roles for these precursors in organosulfate formation in Centreville. Positive filter sampling artifacts associated with these organosulfates due to gas adsorption or reaction of gas phase precursors of organosulfates with sulfuric acid were assessed for a subset of samples and were less than 7.8 % of their PM2.5 concentrations. Together, the quantified organosulfates accounted for  

Description: New analytical techniques are needed to improve our understanding of the intertwined physical and chemical processes that affect the composition of aerosol particles in the Earth's atmosphere, such as gas–particle partitioning and homogenous or heterogeneous chemistry, and their ultimate relation to air quality and climate. We describe a new laboratory setup that couples an electrodynamic balance (EDB) to a mass spectrometer (MS). The EDB stores a single laboratory-generated particle in an electric field under atmospheric conditions for an arbitrarily long length of time. The particle is then transferred via gas flow to an ionization region that vaporizes and ionizes the analyte molecules before MS measurement. We demonstrate the feasibility of the technique by tracking evaporation of polyethylene glycol molecules and finding agreement with a kinetic model. Fitting data to the kinetic model also allows determination of vapor pressures to within a factor of 2. This EDB–MS system can be used to study fundamental chemical and physical processes involving particles that are difficult to isolate and study with other techniques. The results of such measurements can be used to improve our understanding of atmospheric particles.

Description: Molecules with hydroperoxide functional groups are of extreme importance to both the atmospheric and biological chemistry fields. In this work, an analytical method is presented for the identification of organic hydroperoxides and peroxy acids (ROOH) by direct infusion of liquid samples into a positive-ion atmospheric pressure chemical ionization–tandem mass spectrometer ((+)-APCI-MS/MS). Under collisional dissociation conditions, a characteristic neutral loss of 51 Da (arising from loss of H2O2+NH3) from ammonium adducts of the molecular ions ([M + NH4]+) is observed for ROOH standards (i.e. cumene hydroperoxide, isoprene-4-hydroxy-3-hydroperoxide (ISOPOOH), tert-butyl hydroperoxide, 2-butanone peroxide and peracetic acid), as well as the ROOH formed from the reactions of H2O2 with aldehydes (i.e. acetaldehyde, hexanal, glyoxal and methylglyoxal). This new ROOH detection method was applied to methanol extracts of secondary organic aerosol (SOA) material generated from ozonolysis of α-pinene, indicating a number of ROOH molecules in the SOA material. While the full-scan mass spectrum of SOA demonstrates the presence of monomers (m∕z = 80–250), dimers (m∕z = 250–450) and trimers (m∕z = 450–600), the neutral loss scan shows that the ROOH products all have masses less than 300 Da, indicating that ROOH molecules may not contribute significantly to the SOA oligomeric content. We anticipate this method could also be applied to biological systems with considerable value.

Description: An instrumented NASA P-3B aircraft was used for airborne sampling of trace gases in a plume that had emanated from a small forest understory fire in Georgia, USA. The plume was sampled at its origin to derive emission factors and followed  ∼ 13.6 km downwind to observe chemical changes during the first hour of atmospheric aging. The P-3B payload included a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS), which measured non-methane organic gases (NMOGs) at unprecedented spatiotemporal resolution (10 m spatial/0.1 s temporal). Quantitative emission data are reported for CO2, CO, NO, NO2, HONO, NH3, and 16 NMOGs (formaldehyde, methanol, acetonitrile, propene, acetaldehyde, formic acid, acetone plus its isomer propanal, acetic acid plus its isomer glycolaldehyde, furan, isoprene plus isomeric pentadienes and cyclopentene, methyl vinyl ketone plus its isomers crotonaldehyde and methacrolein, methylglyoxal, hydroxy acetone plus its isomers methyl acetate and propionic acid, benzene, 2,3-butanedione, and 2-furfural) with molar emission ratios relative to CO larger than 1 ppbV ppmV−1. Formaldehyde, acetaldehyde, 2-furfural, and methanol dominated NMOG emissions. No NMOGs with more than 10 carbon atoms were observed at mixing ratios larger than 50 pptV ppmV−1 CO. Downwind plume chemistry was investigated using the observations and a 0-D photochemical box model simulation. The model was run on a nearly explicit chemical mechanism (MCM v3.3) and initialized with measured emission data. Ozone formation during the first hour of atmospheric aging was well captured by the model, with carbonyls (formaldehyde, acetaldehyde, 2,3-butanedione, methylglyoxal, 2-furfural) in addition to CO and CH4 being the main drivers of peroxy radical chemistry. The model also accurately reproduced the sequestration of NOx into peroxyacetyl nitrate (PAN) and the OH-initiated degradation of furan and 2-furfural at an average OH concentration of 7.45 ± 1.07 × 106 cm−3 in the plume. Formaldehyde, acetone/propanal, acetic acid/glycolaldehyde, and maleic acid/maleic anhydride (tentatively identified) were found to be the main NMOGs to increase during 1 h of atmospheric plume processing, with the model being unable to capture the observed increase. A mass balance analysis suggests that about 50 % of the aerosol mass formed in the downwind plume is organic in nature.

Description: Different approaches to estimate organic sampling artifacts have been adopted by US long-term air quality monitoring networks. This study documents field blank (bQF) and backup filter (quartz-fiber behind quartz-fiber filter; QBQ) carbon levels for the: 1) Interagency Monitoring of Protected Visual Environments (IMPROVE); 2) Speciation Trends Network (STN; part of the Chemical Speciation Network [CSN]; and 3) Southeastern Aerosol Research and Characterization (SEARCH) networks. Filter pack sample handling procedures and blank correction methods are examined. Due to a relatively short (1–15 min) passive exposure period, STN/CSN and SEARCH network bQF organic carbon (OC; 0.8–1 μg/cm2) may underestimate positive and negative OC artifacts, respectively, resulting from passive adsorption or volatilization of volatile or semi-volatile organic compounds on quartz-fiber filters while they are in the sampler. This is evidenced by a lack of temporal or spatial variability and low bQF levels. With ~7 d of ambient passive exposure, average IMPROVE bQF and QBQ OC are comparable (2.4±0.5 and 3.1±0.8 μg/cm2) and more than twice those found in the STN/CSN and SEARCH networks. Lower STN/CSN flow rates and larger filter deposit areas result in 9–20% of the areal density (μg/cm2) compared to IMPROVE areal deposits. STN/CSN bQF values are 11–34% lower than linear regression intercepts derived from collocated IMPROVE-STN/CSN data pairs. Using a preceding organic denuder in the SEARCH network reduces the organic vapor adsorption on QBQ, though the longer QBQ period in the sampler may result from passive organic vapor adsorption as well as evaporated OC from the front filter deposits.

Description: Field blanks (bQF) and backup filters (quartz-fiber behind quartz-fiber filter; QBQ) have been adopted by US long-term air quality monitoring networks to estimate PM2.5 organic carbon (OC) sampling artifacts. This study documents bQF and QBQ carbon levels for the: 1) Interagency Monitoring of Protected Visual Environments (IMPROVE); 2) Speciation Trends Network (STN; part of the Chemical Speciation Network [CSN]); and 3) Southeastern Aerosol Research and Characterization (SEARCH) networks and examines the similarities/differences associated with network-specific sampling protocols. A higher IMPROVE sample volume and smaller filter deposit area results in PM2.5 areal density (μg/cm2 on filter) 3–11 times those of STN/CSN and SEARCH samples for the same ambient PM2.5 concentrations, thus reducing the relative contribution of sampling artifacts from passive OC adsorption. A relatively short (1–15 min) passive exposure period of STN/CSN and SEARCH bQF OC (0.8–1 μg/cm2) underestimates positive and negative OC artifacts resulting from passive adsorption or evaporation of semi-volatile organic compounds on quartz-fiber filters. This is supported by low STN/CSN and SEARCH bQF levels and lack of temporal or spatial variability among the sites within the networks. With a much longer period, ~7 days of ambient passive exposure, average IMPROVE bQF and QBQ OC are comparable (2.4±0.5 and 3.1±0.8 μg/cm2, respectively) and more than twice levels found in the STN/CSN and SEARCH networks. Sampling artifacts in STN/CSN were estimated from collocated IMPROVE samples based on linear regression. At six of the eight collocated sites in this study, STN/CSN bQFs underestimated OC artifacts by 11–34%. Using a preceding organic denuder in the SEARCH network minimized passive adsorption on QBQ, but OC on QBQ may not be attributed entirely to the negative sampling artifact (e.g., evaporated or volatilized OC from the front filter deposits after sample collection).

Description: Archived Federal Reference Method (FRM) Teflon filters used by state regulatory agencies for measuring PM2.5 mass were acquired from 15 sites throughout the southeastern US and analyzed for water-soluble organic carbon (WSOC), water-soluble ions and carbohydrates to investigate biomass burning contributions to fine aerosol mass. Based on over 900 filters that spanned all of 2007, levoglucosan and K+ were studied in conjunction with MODIS Aqua fire count data to compare their performances as biomass burning tracers. Levoglucosan concentrations exhibited a distinct seasonal variation with large enhancement in winter and spring and a minimum in summer, and were well correlated with fire counts, except in winter when residential wood burning contributions were significant. In contrast, K+ concentrations had no apparent seasonal trend and poor correlation with fire counts. Levoglucosan and K+ only correlated well in winter (r2=0.59) when biomass burning emissions were highest, whereas in other seasons they were not correlated due to the presence of other K+ sources. Levoglucosan also exhibited larger spatial variability than K+. Both species were higher in urban than rural sites (mean 44% higher for levoglucosan and 86% for K+). Positive Matrix Factorization (PMF) was applied to analyze PM2.5 sources and four factors were resolved: biomass burning, refractory material, secondary light absorbing WSOC and secondary sulfate/WSOC. The biomass burning source contributed 13% to PM2.5 mass annually, 27% in winter, and less than 2% in summer, consistent with other souce apportionment studies based on levoglucosan, but lower in summer compared to studies based on K+.

Description: Secondary organic aerosol (SOA) in the southeastern US is investigated by analyzing the spatial-temporal distribution of water-soluble organic carbon (WSOC) and other PM2.5 components from 900 archived 24-h Teflon filters collected at 15 urban or rural EPA Federal Reference Method (FRM) network sites throughout 2007. Online measurements of WSOC at an urban/rural-paired site in Georgia in the summer of 2008 are contrasted to the filter data. Based on FRM filters, excluding biomass-burning events (levoglucosan 〈 50 ng m−3), WSOC and sulfate were highly correlated with PM2.5 mass (r2~0.7). Both components comprised a large mass fraction of PM2.5 (13% and 31%, respectively, or ~25% and 50% for WSOM and ammonium sulfate). Sulfate and WSOC both tracked ambient temperature throughout the year, suggesting the temperature effects were mainly linked to faster photochemistry and/or synoptic meteorology and less due to enhanced biogenic hydrocarbon emissions. FRM WSOC, and to a lesser extent sulfate, were spatially homogeneous throughout the region, yet WSOC was moderately enhanced (27%) in locations of greater predicted isoprene emissions in summer. A Positive Matrix Factorization (PMF) analysis identified two major source types for the summer WSOC; 22% of the WSOC were associated with ammonium sulfate, and 56% of the WSOC were associated with brown carbon and oxalate. A small urban excess of FRM WSOC (10%) was observed in the summer of 2007, however, comparisons of online WSOC measurements at one urban/rural pair (Atlanta/Yorkville) in August 2008 showed substantially greater difference in WSOC (31%) relative to the FRM data, suggesting a low bias for urban filters. The measured Atlanta urban excess, combined with the estimated boundary layer heights, gave an estimated Atlanta daily WSOC production rate in August of 0.55 mgC m−2 h−1 between mid-morning and mid-afternoon. This study characterizes the regional nature of fine particles in the southeastern US, confirming the importance of SOA and the roles of both biogenic and anthropogenic emissions.

Description: Light absorption of fine particle (PM2.5) aqueous extracts between wavelengths of 200 and 800 nm were investigated from two data sets: 24-h Federal Reference Method (FRM) filter extracts from 15 Southeastern US monitoring sites over the year of 2007 (900 filters), and online measurements from a Particle-Into-Liquid Sampler deployed from July to mid-August 2009 in Atlanta, Georgia. Three main sources of soluble chromophores were identified: biomass burning, mobile source emissions, and compounds linked to secondary organic aerosol (SOA) formation. Absorption spectra of aerosol solutions from filter extracts were similar for different sources. Angstrom exponents were ~7±1 for biomass burning and non-biomass burning-impacted 24-h filter samples (delineated by a levoglucosan concentration of 50 ng m−3) at both rural and urban sites. The absorption coefficient from measurements averaged between wavelength 360 and 370 nm (Abs365, in units m−1) was used as a measure of overall brown carbon light absorption. Biomass-burning-impacted samples were highest during winter months and Abs365 was correlated with levoglucosan at all sites. During periods of little biomass burning in summer, light absorbing compounds were still ubiquitous and correlated with fine particle Water-Soluble Organic Carbon (WSOC), but comprised a much smaller fraction of the WSOC, where Abs365/WSOC (i.e., mass absorption efficiency) was typically ~3 times higher in biomass burning-impacted samples. Factor analysis attributed 50% of the yearly average Abs365 to biomass burning sources. Brown carbon from primary urban emissions (mobile sources) was also observed and accounted for ~10% of the regional yearly average Abs365. Summertime diurnal profiles of Abs365 and WSOC showed that morning to midday increases in WSOC from photochemical production were associated with a decrease in Abs365/WSOC. After noon, this ratio substantially increased, indicating that either some fraction of the non-light absorbing fresh SOA was rapidly (within hours) converted to chromophores heterogeneously, or that SOA from gas-particle partitioning later in the day was more light-absorbing. Factor analysis on the 24-h integrated filter data associated ~20 to 30% of Abs365 over 2007 with a secondary source that was highest in summer and also the main source for oxalate, suggesting that aqueous phase reactions may account for the light-absorbing fraction of WSOC observed throughout the Southeastern US in summer.

Description: Data from the Interagency Monitoring of Protected Visual Environments (IMPROVE) network are used to estimate organic mass to organic carbon (OM/OC) ratios across the United States by extending previously published multiple regression techniques. Our new methodology addresses common pitfalls of multiple regression including measurement uncertainty, colinearity of covariates, dataset selection, and model selection. As expected, summertime OM/OC ratios are larger than wintertime values across the US with all regional median OM/OC values tightly confined between 1.80 and 1.95. Further, we find that OM/OC ratios during the winter are distinctly larger in the eastern US than in the West (regional medians are 1.58, 1.64, and 1.85 in the great lakes, southeast, and northeast regions, versus 1.29 and 1.32 in the western and central states). We find less spatial variability in long-term averaged OM/OC ratios across the US (90% of our multiyear regressions estimate OM/OC ratios between 1.37 and 1.94) than previous studies (90% fell between 1.30 and 2.10). We attribute this difference largely to the inclusion of EC as a covariate in previous regression studies. Due to the colinearity of EC and OC, we find that up to one-quarter of the OM/OC estimates in a previous study are biased low. Assumptions about OC measurement artifacts add uncertainty to our estimates of OM/OC. In addition to estimating OM/OC ratios, our technique reveals trends that may be contrasted with conventional assumptions regarding nitrate, sulfate, and soil across the IMPROVE network. For example, our regressions show pronounced seasonal and spatial variability in both nitrate volatilization and sulfate neutralization and hydration.