Amy P. Sullivan

Refinements to the particle-into-liquid sampler (PILS) for ground and airborne measurements of water soluble aerosol composition

An improved particle-into-liquid sampler (PILS) has proven successful in both ground-based and aircraft experiments for rapid measurements of soluble aerosol chemical composition. Major modifications made to the prototype PILS (Aerosol Sci. Technol. 35 (2001) 718) improve particle collection at higher sample flow (15–17 l min � 1 ) while maintaining minimal sample dilution. Laboratory experiments using a fluorescent calibration aerosol aided in designing the present system and characterized the PILS collection efficiency as a function of particle size. Collection efficiency for particle diameters Dp between 0.03 and 10mm is greater than 97%. In addition, the instrument now samples at low pressures (0.3 atmosphere) necessary for airborne measurements up to approximately 8 km in altitude. An ion chromatograph (IC) is coupled to the PILS for direct on-line analysis of the collected sample (hence the name ‘PILS-IC’). Proper selection of columns and eluants allows for 3.5–4 min separation of 9 major inorganic species (Na + , NH4 ,K + ,C a 2+ ,M g 2+ ,C l � ,N O 3 ,N O 2 ,S O 4� ), while acetate, formate, and oxalate, are also possible in 15 min. Any analytical technique capable of continuous online analysis of a liquid sample can be coupled to the PILS for quantitative semi-continuous measurements of aerosol composition. Changes made to the prototype are explained and data from a recent experiment are compared with standard integrated filter measurements. r 2003 Elsevier Science Ltd. All rights reserved.

Emissions of trace gases and aerosols during the open combustion of biomass in the laboratory

[1] We characterized the gas- and speciated aerosol-phase emissions from the open combustion of 33 different plant species during a series of 255 controlled laboratory burns during the Fire Laboratory at Missoula Experiments (FLAME). The plant species we tested were chosen to improve the existing database for U.S. domestic fuels: laboratory-based emission factors have not previously been reported for many commonly burned species that are frequently consumed by fires near populated regions and protected scenic areas. The plants we tested included the chaparral species chamise, manzanita, and ceanothus, and species common to the southeastern United States (common reed, hickory, kudzu, needlegrass rush, rhododendron, cord grass, sawgrass, titi, and wax myrtle). Fire-integrated emission factors for gas-phase CO2, CO, CH4 ,C 2–4 hydrocarbons, NH3 ,S O2, NO, NO2, HNO3, and particle-phase organic carbon (OC), elemental carbon (EC), SO4� ,N O3 ,C l � ,N a + ,K + , and NH4 generally varied with both fuel type and with the fire-integrated modified combustion efficiency (MCE), a measure of the relative importance of flaming- and smoldering-phase combustion to the total emissions during the burn. Chaparral fuels tended to emit less particulate OC per unit mass of dry fuel than did other fuel types, whereas southeastern species had some of the largest observed emission factors for total fine particulate matter. Our measurements spanned a larger range of MCE than prior studies, and thus help to improve estimates of the variation of emissions with combustion conditions for individual fuels.

Airborne measurements of carbonaceous aerosol soluble in water over northeastern United States: Method development and an investigation into water-soluble organic carbon sources

[1] A particle-into-liquid sampler (PILS) was coupled to a total organic carbon (TOC) analyzer for 3 s integrated measurements of water-soluble organic carbon (WSOC) in PM1 ambient particles. The components of the instrument are described in detail. The PILS-TOC was deployed on the NOAA WP-3D aircraft during the NEAQS/ITCT 2004 program to investigate WSOC sources over the northeastern United States and Canada. Two main sources were identified: biomass burning emissions from fires in Alaska and northwestern Canada and emissions emanating from urban centers. Biomass burning WSOC was correlated with carbon monoxide (CO) and acetonitrile (r 2 > 0.88). These plumes were intercepted in layers at altitudes between 3 and 4 km and contained the highest fine particle volume and WSOC concentrations of the mission. Apart from the biomass burning influence, the lowest WSOC concentrations were recorded in rural air masses that included regions of significant biogenic emissions. Highest concentrations were at low altitudes in distinct plumes from urban centers. WSOC and CO were highly correlated (r 2 > 0.78) in these urban plumes. The ratio of the enhancement in WSOC relative to CO enhancement was found to be low (� 3 mg C/m 3 /ppmv) in plumes that had been in transit for a short time, and increased with plume age, but appeared to level off at � 32 ± 4 mg C/m 3 /ppmv after � 1 day of transport from the sources. The results suggest that the production of WSOC in fine particles depends on compounds coemitted with CO and that this process is rapid with a time constant of � 1 day.

Sources of particulate matter in the northeastern United States in summer: 1. Direct emissions and secondary formation of organic matter in urban plumes

[1] Ship and aircraft measurements of aerosol organic matter (OM) and water-soluble organic carbon (WSOC) were made in fresh and aged pollution plumes from major urban areas in the northeastern United States in the framework of the 2004 International Consortium for Atmospheric Research on Transport and Transformation (ICARTT) study. A large part of the variability in the data was quantitatively described by a simple parameterization from a previous study that uses measured mixing ratios of CO and either the transport age or the photochemical age of the sampled air masses. The results suggest that OM was mostly due to secondary formation from anthropogenic volatile organic compound (VOC) precursors in urban plumes. Approximately 37% of the secondary formation can be accounted for by the removal of aromatic precursors using newly published particulate mass yields for low-NOx conditions, which are significantly higher than previous results. Of the secondary formation, 63% remains unexplained and is possibly due to semivolatile precursors that are not measurable by standard gas chromatographic methods. The observed secondary OM in urban plumes may account for 35% of the total source of OM in the United States and 8.5% of the global OM source. OM is an important factor in climate and air quality issues, but its sources and formation mechanisms remain poorly quantified.

Sources of Bacteria in Outdoor Air across Cities in the Midwestern United States

ABSTRACT Bacteria are abundant in the atmosphere, where they often represent a major portion of the organic aerosols. Potential pathogens of plants and livestock are commonly dispersed through the atmosphere, and airborne bacteria can have important effects on human health as pathogens or triggers of allergic asthma and seasonal allergies. Despite their importance, the diversity and biogeography of airborne microorganisms remain poorly understood. We used high-throughput pyrosequencing to analyze bacterial communities present in the aerosol fraction containing fine particulate matter of ≤2.5 μm from 96 near-surface atmospheric samples collected from cities throughout the midwestern United States and found that the communities are surprisingly diverse and strongly affected by the season. We also directly compared the airborne communities to those found in hundreds of samples representing potential source environments. We show that, in addition to the more predictable sources (soils and leaf surfaces), fecal material, most likely dog feces, often represents an unexpected source of bacteria in the atmosphere at more urbanized locations during the winter. Airborne bacteria are clearly an important, but understudied, component of air quality that needs to be better integrated into efforts to measure and model pollutants in the atmosphere.

Chemical Smoke Marker Emissions During Flaming and Smoldering Phases of Laboratory Open Burning of Wildland Fuels

Smoke emitted by prescribed and wild fires can make a substantial contribution to ambient aerosol (McMeeking et al. 2006; Park et al. 2007; Spracklen et al. 2007). Approaches to investigate these contributions have used a variety of different chemical smoke markers, including levoglucosan, produced by thermal degradation of cellulose, and water-soluble potassium (Andreae 1983; Engling et al. 2006; Hays et al. 2002; Simoneit 2002;Ward et al. 2006). Filter sampling is commonly employed to measure smoke markers in ambient and source samples; however, these time-integrated measurements limit knowledge about variability of smoke marker emissions, especially between flaming and smoldering fire phases.

Volatile organic compound measurements at Trinidad Head, California, during ITCT 2K2: Analysis of sources, atmospheric composition, and aerosol residence times

[1] We report hourly in-situ observations of C(1)-C(8) speciated volatile organic compounds (VOCs) obtained at Trinidad Head CA in April and May 2002 as part of the NOAA Intercontinental Transport and Chemical Transformation study. Factor analysis of the VOC data set was used to define the dominant processes driving atmospheric chemical composition at the site, and to characterize the sources for measured species. Strong decreases in background concentration were observed for several of the VOCs during the experiment due to seasonal changes in OH concentration. CO was the most important contributor to the total measured OH reactivity at the site at all times. Oxygenated VOCs were the primary component of both the total VOC burden and of the VOC OH reactivity, and their relative importance was enhanced under conditions when local source contributions were minimal. VOC variability exhibited a strong dependence on residence time (s(lnX) = 1.55(tau)(-0.44), r(2) = 0.98; where s(lnX) is the standard deviation of the natural logarithm of the mixing ratio), and this relationship was used, in conjunction with measurements of (222)Rn, to estimate the average OH concentration during the study period (6.1 x 10(5) molec/cm(3)). We also employed the variability-lifetime relationship defined by the VOC data set to estimate submicron aerosol residence times as a function of chemical composition. Two independent measures of aerosol chemical composition yielded consistent residence time estimates. Lifetimes calculated in this manner were between 3 - 7 days for aerosol nitrate, organics, sulfate, and ammonium. The lifetime estimate for methane sulfonic acid ( similar to 12 days) was slightly outside of this range. The lifetime of the total aerosol number density was estimated at 9.8 days.

Deposition of reactive nitrogen during the Rocky Mountain Airborne Nitrogen and Sulfur (RoMANS) study.

Increases in reactive nitrogen deposition are a growing concern in the U.S. Rocky Mountain west. The Rocky Mountain Airborne Nitrogen and Sulfur (RoMANS) study was designed to improve understanding of the species and pathways that contribute to nitrogen deposition in Rocky Mountain National Park (RMNP). During two 5-week field campaigns in spring and summer of 2006, the largest contributor to reactive nitrogen deposition in RMNP was found to be wet deposition of ammonium (34% spring and summer), followed by wet deposition of nitrate (24% spring, 28% summer). The third and fourth most important reactive nitrogen deposition pathways were found to be wet deposition of organic nitrogen (17%, 12%) and dry deposition of ammonia (14%, 16%), neither of which is routinely measured by air quality/deposition networks operating in the region. Total reactive nitrogen deposition during the spring campaign was determined to be 0.45 kg ha(-1) and more than doubled to 0.95 kg ha(-1) during the summer campaign.

No evidence for acid‐catalyzed secondary organic aerosol formation in power plant plumes over metropolitan Atlanta, Georgia

Aircraft-based measurements of the water-soluble fraction of fine PM organic carbon (WSOC) and inorganic salt composition in the Atlanta, GA region were conducted in the summer of 2004. Five notable plumes of SO{sub 2}, apparently from coal-fired power plants, were intercepted, and had NH{sub 4}{sup +}/SO4{sup 2-} molar ratios ranging from approximately 0.8 to 1.4 compared to molar ratios near 2 outside of the plumes. Sulfate aerosol concentrations increased from a regional background of 5 - 8 {mu} g m{sup -3} to as high as 19.5 {mu} g m{sup -3} within these plumes. No increase in WSOC concentrations was observed in plumes compared to out-of-plumes within a WSOC measurement uncertainty of 8%. These measurements suggest that secondary organic aerosol formation via heterogeneous acid-catalyzed reactions within power plant plumes are not likely a significant contributor to the ambient aerosol mass loading in Atlanta and the surrounding region. Because this region is rich in both biogenic and anthropogenic volatile organic carbon (VOC), the results may be widely applicable.

Aerosol emissions from prescribed fires in the United States: A synthesis of laboratory and aircraft measurements

Aerosol emissions from prescribed fires can affect air quality on regional scales. Accurate representation of these emissions in models requires information regarding the amount and composition of the emitted species. We measured a suite of submicron particulate matter species in young plumes emitted from prescribed fires (chaparral and montane ecosystems in California; coastal plain ecosystem in South Carolina) and from open burning of over 15 individual plant species in the laboratory. We report emission ratios and emission factors for refractory black carbon (rBC) and submicron nonrefractory aerosol and compare field and laboratory measurements to assess the representativeness of our laboratory-measured emissions. Laboratory measurements of organic aerosol (OA) emission factors for some fires were an order of magnitude higher than those derived from any of our aircraft observations; these are likely due to higher-fuel moisture contents, lower modified combustion efficiencies, and less dilution compared to field studies. Nonrefractory inorganic aerosol emissions depended more strongly on fuel type and fuel composition than on combustion conditions. Laboratory and field measurements for rBC were in good agreement when differences in modified combustion efficiency were considered; however, rBC emission factors measured both from aircraft and in the laboratory during the present study using the Single Particle Soot Photometer were generally higher than values previously reported in the literature, which have been based largely on filter measurements. Although natural variability may account for some of these differences, an increase in the BC emission factors incorporated within emission inventories may be required, pending additional field measurements for a wider variety of fires.