Photochemical model performance for PM2.5 sulfate,nitrate, ammonium,and precursor species SO2, HNO3, and NH3 at background monitor locations in the central and eastern United States

Health studies have shown premature death is statistically associated with exposure to particulate matter <2.5 μm in diameter (PM2.5). The United States Environmental Protection Agency requires all States with PM2.5 non-attainment counties or with sources contributing to visibility impairment at Class I areas to submit an emissions control plan. These emission control plans will likely focus on reducing emissions of sulfur oxides and nitrogen oxides, which form two of the largest chemical components of PM2.5 in the eastern United States: ammonium sulfate and ammonium nitrate. Emission control strategies are simulated using three-dimensional Eulerian photochemical transport models.A monitor study was established using one urban (Detroit) and nine rural locations in the central and eastern United States to simultaneously measure PM2.5 sulfate ion (SO₄²⁻), nitrate ion (NO₃⁻), ammonium ion (NH₄⁺), and precursor species sulfur dioxide (SO₂), nitric acid (HNO₃), and ammonia (NH₃). This monitor study provides a unique opportunity to assess how well the modeling system predicts the spatial and temporal variability of important precursor species and co-located PM2.5 ions, which is not well characterized in the central and eastern United States.The modeling system performs well at estimating the PM2.5 species, but does not perform quite as well for the precursor species. Ammonia is under-predicted in the coldest months, nitric acid tends to be over-predicted in the summer months, and sulfur dioxide appears to be systematically over-predicted. Several indicators of PM2.5 ammonium sulfate and ammonium nitrate formation and chemical composition are estimated with the ambient data and photochemical model output. PM2.5 sulfate ion is usually not fully neutralized to ammonium sulfate in ambient measurements and is usually fully neutralized in model estimates. The model and ambient estimates agree that the ammonia study monitors tend to be nitric acid limited for PM2.5 nitrate formation. Regulatory strategies in this part of the country should focus on reductions in NO_X rather than ammonia to control PM2.5 ammonium nitrate.     

Improving source apportionment of fine particles in the eastern United States utilizing temperature-resolved carbon fractions

The objectives of this study were to examine the use of carbon fractions to identify particulate matter (PM) sources, especially traffic-related carbonaceous particle sources, and to estimate their contributions to the particle mass concentrations. In recent studies, positive matrix factorization (PMF) was applied to ambient fine PM (PM2.5) compositional data sets of 24-hr integrated samples including eight individual carbon fractions collected at three monitoring sites in the eastern United States: Atlanta, GA, Washington, DC, and Brigantine, NJ. Particulate carbon was analyzed using the Interagency Monitoring of Protected Visual Environments/Thermal Optical Reflectance method that divides carbon into four organic carbons (OC): pyrolized OC and three elemental carbon (EC) fractions. In contrast to earlier PMF studies that included only the total OC and EC concentrations, gasoline emissions could be distinguished from diesel emissions based on the differences in the abundances of the carbon fractions between the two sources. The compositional profiles for these two major source types show similarities among the three sites. Temperature-resolved carbon fractions also enhanced separations of carbon-rich secondary sulfate aerosols. Potential source contribution function analyses show the potential source areas and pathways of sulfate-rich secondary aerosols, especially the regional influences of the biogenic, as well as anthropogenic secondary aerosol. This study indicates that temperature-resolved carbon fractions can be used to enhance the source apportionment of ambient PM2.5.     

Compilation and assessment of recent positive matrix factorization and UNMIX receptor model studies on fine particulate matter source apportionment for the eastern United States

In 1997, the U.S. Environmental Protection Agency (EPA) revised its particulate matter standards to include an annual standard for fine particulate matter (PM2.5; 15 microg/m3) and a 24-hr standard (65 microg/m3). The 24-hr standard was lowered to 35 microg/m3 in 2006 in an effort to further reduce overall ambient PM2.5 concentrations. Identifying and quantifying sources of particulate matter affecting a particular location through source apportionment methods is now an important component of the information available to decision makers when evaluating the new standards. This literature compilation summarizes a subset of the source apportionment research and general findings on fine particulate matter in the eastern half of the United States using Positive Matrix Factorization. The results between studies are generally comparable when comparable datasets are used; however, methodologies vary considerably. Commonly identified source categories include: secondary sulfate/coal burning (sometimes over 50% of total mass), secondary organic carbon/mobile sources, crustal sources, biomass burning, nitrate, various industrial processes, and sea salt. The source apportionment tools and methodologies have passed the proof-of-concept stage and are now being used to understand the ambient composition of particulate matter for sites across the United States and the spatial relationship of sources to the receptor. Recommendations are made for further and standardized method development for source apportionment studies, and specific research areas of interest for the eastern United States are proposed.     

Improving Source Apportionment of Fine Particles in the Eastern United States Utilizing Temperature-Resolved Carbon Fractions

Abstract

The objectives of this study were to examine the use of carbon fractions to identify particulate matter (PM) sources, especially traffic‐related carbonaceous particle sources, and to estimate their contributions to the particle mass concentrations. In recent studies, positive matrix factorization (PMF) was applied to ambient fine PM (PM_2.5) compositional data sets of 24‐hr integrated samples including eight individual carbon fractions collected at three monitoring sites in the eastern United States: Atlanta, GA, Washington, DC, and Brigantine, NJ. Particulate carbon was analyzed using the Interagency Monitoring of Protected Visual Environments/Thermal Optical Reflectance method that divides carbon into four organic carbons (OC): pyrolized OC and three elemental carbon (EC) fractions. In contrast to earlier PMF studies that included only the total OC and EC concentrations, gasoline emissions could be distinguished from diesel emissions based on the differences in the abundances of the carbon fractions between the two sources. The compositional profiles for these two major source types show similarities among the three sites. Temperature‐resolved carbon fractions also enhanced separations of carbon‐rich secondary sulfate aerosols. Potential source contribution function analyses show the potential source areas and pathways of sulfate‐rich secondary aerosols, especially the regional influences of the biogenic, as well as anthropogenic secondary aerosol. This study indicates that temperature‐resolved carbon fractions can be used to enhance the source apportionment of ambient PM_2.5.     

Processes influencing secondary aerosol formation in the San Joaquin Valley during winter

Air quality data collected in the California Regional PM10/ PM(2.5) Air Quality Study (CRPAQS) are analyzed to qualitatively assess the processes affecting secondary aerosol formation in the San Joaquin Valley (SJV). This region experiences some of the highest fine particulate matter (PM(2.5)) mass concentrations in California (< or = 188 microg/m3 24-hr average), and secondary aerosol components (as a group) frequently constitute over half of the fine aerosol mass in winter. The analyses are based on 15 days of high-frequency filter and canister measurements and several months of wintertime continuous gas and aerosol measurements. The phase-partitioning of nitrogen oxide (NO(x))-related nitrogen species and carbonaceous species shows that concentrations of gaseous precursor species are far more abundant than measured secondary aerosol nitrate or estimated secondary organic aerosols. Comparisons of ammonia and nitric acid concentrations indicate that ammonium nitrate formation is limited by the availability of nitric acid rather than ammonia. Time-resolved aerosol nitrate data collected at the surface and on a 90-m tower suggest that both the daytime and nighttime nitric acid formation pathways are active, and entrainment of aerosol nitrate formed aloft at night may explain the spatial homogeneity of nitrate in the SJV. NO(x) and volatile organic compound (VOC) emissions plus background O3 levels are expected to determine NO(x) oxidation and nitric acid production rates, which currently control the ammonium nitrate levels in the SJV. Secondary organic aerosol formation is significant in winter, especially in the Fresno urban area. Formation of secondary organic aerosol is more likely limited by the rate of VOC oxidation than the availability of VOC precursors in winter.     

Measurement, analysis, and modeling of fine particulate matter in eastern North Carolina

An analysis of fine particulate data in eastern North Carolina was conducted to investigate the impact of the hog industry and its emissions of ammonia into the atmosphere. The fine particulate data are simulated using ISORROPIA, an equilibrium thermodynamic model that simulates the gas and aerosol equilibrium of inorganic atmospheric species. The observational data analyses show that the major constituents of fine particulate matter (PM2.5) are organic carbon, elemental carbon, sulfate, nitrate, and ammonium. The observed PM2.5 concentration is positively correlated with temperature but anticorrelated with wind speed. The correlation between PM2.5 and wind direction at some locations suggests an impact of ammonia emissions from hog facilities on PM2.5 formation. The modeled results are in good agreement with observations, with slightly better agreement at urban sites than at rural sites. The predicted total inorganic particulate matter (PM) concentrations are within 5% of the observed values under conditions with median initial total PM species concentrations, median relative humidity (RH), and median temperature. Ambient conditions with high PM precursor concentrations, low temperature, and high RH appear to favor the formation of secondary PM.     

Estimating fine particulate matter component concentrations and size distributions using satellite-retrieved fractional aerosol optical depth: part 2--a case study

We use the fractional aerosol optical depth (AOD) values derived from Multiangle Imaging Spectroradiometer (MISR) aerosol component measurements, along with aerosol transport model constraints, to estimate ground-level concentrations of fine particulate matter (PM2.5) mass and its major constituents in the continental United States. Regression models using fractional AODs predict PM2.5 mass and sulfate (SO4) concentrations in both the eastern and western United States, and nitrate (NO3) concentrations in the western United States reasonably well, compared with the available ground-level U.S. Environment Protection Agency (EPA) measurements. These models show substantially improved predictive power when compared with similar models using total-column AOD as a single predictor, especially in the western United States. The relative contributions of the MISR aerosol components in these regression models are used to estimate size distributions of EPA PM2.5 species. This method captures the overall shapes of the size distributions of PM2.5 mass and SO4 particles in the east and west, and NO3 particles in the west. However, the estimated PM2.5 and SO4 mode diameters are smaller than those previously reported by monitoring studies conducted at ground level. This is likely due to the satellite sampling bias caused by the inability to retrieve aerosols through cloud cover, and the impact of particle hygroscopicity on measured particle size distributions at ground level.     

Size fractionated speciation of nitrate and sulfate aerosols in a sub-tropical industrial environment

Size fractionated chemical speciation of acidic aerosols were performed for ammonium sulfate, other sulfates, ammonium nitrate and other nitrates in a sub-tropical industrial area, Bina, India during December 2003 to November 2004. Analysis of variance (ANOVA) revealed highly significant temporal variations (p > .001) in the concentrations of nitrate and sulfate aerosols in all the three size fractions (fine, mid-size and coarse). Winter demonstrated utmost concentrations of ammonium sulfate, which ranged from 3.2 to 26.4 microg m(-3) in fine particles and 0.20-0.34 microg m(-3) in coarse particles. Ammonium sulfate was chiefly in fine mode (43.77% of total particulate sulfate) as compared to coarse particles (28.60% of total particulate sulfate). The major fraction Ammonium sulfate existed in different forms in atmospheric aerosols, for example NH4Fe(SO4)2, (NH4)2SO4, (NH4)3H(SO4)2 in fine particles, and (NH4)4(NO3)SO4+ in coarse particles. Other sulfate concentrations were also higher during winter ranging from 1.89 to 14.3 microg m(-3) in fine particles and 0.12-0.65microg m(-3) in coarse particles. Ammonium nitrate constituted the major fraction of total particulate nitrate all through the year and was principally in fine particles (the highest concentration in January i.e. 14.2 microg m(-3)). Other nitrates were mainly distributed in the fine particles (highest concentration in January i.e. 11.2 microg m(-3)) All the sulfate and nitrate species were mainly distributed in fine mode and have significant impact on human health.     

Mass-size distributions of particulate sulfate, nitrate, and ammonium in a particulate matter nonattainment region in southern Taiwan

Concentrations and distributions of three major water-soluble ion species (sulfate, nitrate, and ammonium) contained in ambient particles were measured at three sampling sites in the Kao-ping ambient air quality basin, Taiwan. Ambient particulate matter (PM) samples were collected in a Micro-orifice Uniform Deposit Impactor from February to July 2003 and were analyzed for water-soluble ion species with an ion chromatograph. The PM1/ PM2.5 and PM1/PM10 concentration ratios at the emission source site were 0.73 and 0.53 and were higher than those (0.68 and 0.48) at the background site because there are more combustion sources (i.e., industrial boilers and traffic) around the emission source site. Mass-size distributions of PM NO3- were found in both the fine and coarse modes. SO4(2-)and NH4+ were found in the fine particle mode (PM2.5), with significant fractions of submicron particles (PM1). The source site had higher PM1/PM10(79, 42, and 90%) and PM1/PM2.5 concentration ratios (90, 58, and 93%) for the three major inorganic secondary aerosol components (SO4(2-), NO3-, and NH4+) than the receptor site (65, 27, and 65% for PM1/PM10, 69, 51, and 70% for PM1/PM2.5. Results obtained in this study indicate that the PM1 (submicron aerosol particles) fraction plays an important role in the ambient atmosphere at both emission source and receptor sites. Further studies regarding the origin and formation of ambient secondary aerosols are planned.     

Seasonal variations in the chemical composition of particulate matter: a case study in the Po Valley. Part I: macro-components and mass closure

The seasonal variability in the mass concentration and chemical composition of atmospheric particulate matter (PM₁₀ and PM_2.5) was studied during a 2-year field study carried out between 2010 and 2012. The site of the study was the area of Ferrara (Po Valley, Northern Italy), which is characterized by frequent episodes of very stable atmospheric conditions in winter. Chemical analyses carried out during the study allowed the determination of the main components of atmospheric PM (macro-elements, ions, elemental carbon, organic matter) and a satisfactory mass closure was obtained. Accordingly, chemical components could be grouped into the main macro-sources of PM: soil, sea spray, inorganic compounds from secondary reactions, vehicular emission, organics from domestic heating, organics from secondary formation, and other sources. The more significant seasonal variations were observed for secondary inorganic species in the fine fraction of PM; these species were very sensitive to air mass age and thus to the frequency of stable atmospheric conditions. During the winter ammonium nitrate, the single species with the highest concentration, reached concentrations as high as 30 μg/m³. The intensity of natural sources was fairly constant during the year; increases in natural aerosols were linked to medium and long-range transport episodes. The ratio of winter to summer concentrations was roughly 2 for combustion product, close to 3 for secondary inorganic species, and between 2 and 3 for organics. The winter increase of organics was due to poorer atmospheric dispersion and to the addition of the emission from domestic heating. A similar winter to summer ratio (around 3) was observed for the fine fraction of PM.     

Developing intake fraction estimates with limited data: Comparison of methods in Mexico City

In order to estimate the health benefits of reducing mobile source emissions, analysts typically use detailed atmospheric models to estimate the change in population exposure that results from a given change in emissions. However, this may not be feasible in settings where data are limited or policy decisions are needed in the short term. Intake fraction (iF), defined as the fraction of emissions of a pollutant or its precursor that is inhaled by the population, is a metric that can be used to compare exposure assessment methods in a health benefits analysis context. To clarify the utility of rapid-assessment methods, we calculate particulate matter iFs for the Mexico City Metropolitan Area using five methods, some more resource intensive than others. First, we create two simple box models to describe dispersion of primary fine particulate matter (PM_2.5) in the Mexico City basin. Second, we extrapolate iFs for primary PM_2.5, ammonium sulfate, and ammonium nitrate from US values using a regression model. Third, we calculate iFs by assuming a linear relationship between emissions and population-weighted concentrations of primary PM_2.5, ammonium nitrate, and ammonium sulfate (a particle composition method). Finally, we estimate PM iFs from detailed atmospheric dispersion and chemistry models run for only a short period of time. Intake fractions vary by up to a factor of five, from 23 to 120 per million for primary PM_2.5. Estimates of 60, 7, and 0.7 per million for primary PM, secondary ammonium sulfate, and secondary ammonium nitrate, respectively, represent credible central estimates, with an approximate factor of two uncertainty surrounding each estimate. Our results emphasize that multiple rapid-assessment methods can provide meaningful estimates of iFs in resource-limited environments, and that formal uncertainty analysis, with special attention to model biases and uncertainty, would be important for health benefits analyses.     

Apportionment of ambient primary and secondary pollutants during a 2001 summer study in Pittsburgh using U.S. Environmental Protection Agency UNMIX

Apportionment of primary and secondary pollutants during the summer 2001 Pittsburgh Air Quality Study (PAQS) is reported. Several sites were included in PAQS, with the main site (the supersite) adjacent to the Carnegie Mellon University campus in Schenley Park. One of the additional sampling sites was located at the National Energy Technology Laboratory, located approximately 18 km southeast of downtown Pittsburgh. Fine particulate matter (PM2.5) mass, gas-phase volatile organic material (VOM), particulate semivolatile and nonvolatile organic material (NVOM), and ammonium sulfate were apportioned at the two sites into their primary and secondary contributions using the U.S. Environmental Protection Agency UNMIX 2.3 multivariate receptor modeling and analysis software. A portion of each of these species was identified as originating from gasoline and diesel primary mobile sources. Some of the organic material was formed from local secondary transformation processes, whereas the great majority of the secondary sulfate was associated with regional transformation contributions. The results indicated that the diurnal patterns of secondary gas-phase VOM and particulate semivolatile and NVOM were not correlated with secondary ammonium sulfate contributions but were associated with separate formation pathways. These findings are consistent with the bulk of the secondary ammonium sulfate in the Pittsburgh area being the result of contributions from distant transport and, thus, decoupled from local activity involving organic pollutants in the metropolitan area.     

Secondary organic aerosol formation from the oxidation of aromatic hydrocarbons in the presence of dry submicron ammonium sulfate aerosol

A laboratory study was conducted to examine formation of secondary organic aerosols. A smog chamber system was developed for studying gas–aerosol interactions in a dynamic flow reactor. These experiments were conducted to investigate the fate of gas and aerosol phase compounds generated from hydrocarbon–nitrogen oxide (HC/NO_x) mixtures irradiated in the presence of fine (<2.5 μm) particulate matter. The goal was to determine to what extent photochemical oxidation products of aromatic hydrocarbons contribute to secondary organic aerosol formation through uptake on pre-existing inorganic aerosols in the absence of liquid water films. Irradiations were conducted with toluene, p-xylene, and 1,3,5-trimethylbenzene in the presence of NO_x and ammonium sulfate aerosol, with propylene added to enhance the production of radicals in the system. The secondary organic aerosol yields were determined by dividing the mass concentration of organic fraction of the aerosol collected on quartz filters by the mass concentration of the aromatic hydrocarbon removed by reaction. The mass concentration of the organic fraction was obtained by multiplying the measured organic carbon concentration by 2.0, a correction factor that takes into account the presence of hydrogen, nitrogen, and oxygen atoms in the organic species. The mass concentrations of ammonium, nitrate, and sulfate concentrations as well as the total mass of the aerosols were measured. A reasonable mass balance was found for each of the aerosols. The largest secondary organic aerosol yield of 1.59±0.40% was found for toluene at an organic aerosol concentration of 8.2 μm⁻³, followed by 1.09±0.27% for p-xylene at 6.4 μg m⁻³, and 0.41±0.10% for 1,3,5-trimethylbenzene at 2.0 μg m⁻³. In general, these results agree with those reported by Odum et al. and appear to be consistent with the gas–aerosol partitioning theory developed by Pankow. The presence of organic in the aerosol did not affect significantly the hygroscopic properties of the aerosol.     

Response of Fine Particulate Matter to Emission Changes of Oxides of Nitrogen and Anthropogenic Volatile Organic Compounds in the Eastern United States

Abstract

A three-dimensional chemical transport model (Particulate Matter Comprehensive Air Quality Model with Extensions [PMCAMx]) is used to investigate changes in fine particle (PM_2.5) concentrations in response to 50% emissions changes of oxides of nitrogen (NO_x) and anthropogenic volatile organic compounds (VOCs) during July 2001 and January 2002 in the eastern United States. The reduction of NO_x emissions by 50% during the summer results in lower average oxidant levels and lowers PM_2.5 (8% on average), mainly because of reductions of sulfate (9–11%), nitrate (45–58%), and ammonium (7–11%). The organic particulate matter (PM) slightly decreases in rural areas, whereas it increases in cities by a few percent when NO_x is reduced. Reduction of NO_x during winter causes an increase of the oxidant levels and a rather complicated response of the PM components, leading to small net changes. Sulfate increases (8–17%), nitrate decreases (18– 42%), organic PM slightly increases, and ammonium either increases or decreases a little. The reduction of VOC emissions during the summer causes on average a small increase of the oxidant levels and a marginal increase in PM_2.5. This small net change is due to increases in the inorganic components and decreases of the organic ones. Reduction of VOC emissions during winter results in a decrease of the oxidant levels and a 5–10% reduction of PM_2.5 because of reductions in nitrate (4–19%), ammonium (4–10%), organic PM (12–14%), and small reductions in sulfate. Although sulfur dioxide (SO₂) reduction is the single most effective approach for sulfate control, the coupled decrease of SO₂ and NO_x emissions in both seasons is more effective in reducing total PM_2.5 mass than the SO₂ reduction alone.     

Revised algorithm for estimating light extinction from IMPROVE particle speciation data

The Interagency Monitoring of Protected Visual Environments (IMPROVE) particle monitoring network consists of approximately 160 sites at which fine particulate matter (PM2.5) mass and major species concentrations and course particulate matter (PM10) mass concentrations are determined by analysis of 24-hr duration sampling conducted on a 1-day-in-3 schedule A simple algorithm to estimate light extinction from the measured species concentrations was incorporated in the 1999 Regional Haze Rule as the basis for the haze metric used to track haze trends. A revised algorithm was developed that is more consistent with the recent atmospheric aerosol literature and reduces bias for high and low light extinction extremes. The revised algorithm differs from the original algorithm in having a term for estimating sea salt light scattering from Cl(-) ion data, using 1.8 instead of 1.4 for the mean ratio of organic mass to measured organic carbon, using site-specific Rayleigh scattering based on site elevation and mean temperature, employing a split component extinction efficiency associated with large and small size mode sulfate, nitrate and organic mass species, and adding a term for nitrogen dioxide (NO2) absorption for sites with NO2 concentration information. Light scattering estimates using the original and the revised algorithms are compared with nephelometer measurements at 21 IMPROVE monitoring sites. The revised algorithm reduces the underprediction of high haze periods and the overprediction of low haze periods compared with the performance of the original algorithm. This is most apparent at the hazier monitoring sites in the eastern United States. For each site, the PM10 composition for days selected as the best 20% and the worst 20% haze condition days are nearly identical regardless of whether the basis of selection was light scattering from the original or revised algorithms, or from nephelometer-measured light scattering.     

Retained nitrate, hydrated sulfates, and carbonaceous mass in federal reference method fine particulate matter for six eastern U.S. cities

Material balance of fine particulate matter (PM2.5) measured with the Federal Reference Method (FRM) is developed for one rural and five urban locations in the eastern half of the United States using routine Speciation Trends Network (STN) and FRM chemical measurements and thermodynamic models. The Aerosol Inorganics Model is used to estimate retained particle bound water, and an ammonium nitrate evaporation model is used to estimate nitrate concentrations retained on the Teflon-membrane filter of the FRM. To address large uncertainties in carbonaceous mass calculated from STN carbon measurements, retained carbonaceous mass is derived by material balance between PM2.5 FRM mass and estimates of its non-carbon constituents. The resulting sulfate, adjusted nitrate, derived water, inferred carbonaceous material balance approach (SANDWICH) is compared with reconstructed fine mass (RCFM) using the Interagency Monitoring of Protected Visual Environments monitoring program equation. For this study, the SANDWICH method resulted in approximately 21-27% higher sulfate mass and approximately 24-85% lower nitrate mass. The combined mass associated with sulfates and nitrates, however, are well within +/- 10% of the proportion derived using the more traditional RCFM method. The discrepancies between SANDWICH and measurement-derived carbonaceous mass vary from -21% to +56% on an annual basis and are attributed in part to urban-rural source influences and uncertainties in estimating FRM-retained carbonaceous mass.     

Long-term assessment of particulate matter using CHIMERE model

Particulate matter (PM) and aerosols have became a critical pollutant and object of several research applications, due to their increasing levels, especially in urban areas, causing air pollution problems and thus effects on human health. The main purpose of this study is to perform a first long-term air quality assessment for Portugal, regarding aerosols and PM pollution. The CHIMERE chemistry-transport model, forced by the MM5 meteorological fields, was applied over Portugal for 2001 year, with 10 km horizontal resolution, using an emission inventory obtained from a spatial top-down disaggregation of the 2001 national inventory database. The evaluation model exercise shows a model trend to overestimate particulate pollution episodes (peaks) at urban sites, especially in winter season. This could be due to an underprediction of the winter model vertical mixing and also to an overestimation of PM emissions. Simulated inorganic components (ammonium and sulfate) and secondary organic aerosols (SOA) were compared to measurements taken at Aveiro (northwest coast of Portugal). An underestimation of the three components was verified. However, the model is able to predict their seasonal variation. Nevertheless, as a first approach, and despite the complex topography and coastal location of Portugal affected by sea salt natural aerosols emissions, the results obtained show that the model reproduces the PM levels, temporal evolution, and spatial patterns. The concentration maps reveal that the areas with high PM values are covered by the air quality monitoring network.     

The Denver Aerosol Sources and Health (DASH) Study: Overview and Early Findings

Improved understanding of the sources of air pollution that are most harmful could aid in developing more effective measures for protecting human health. The Denver Aerosol Sources and Health (DASH) study was designed to identify the sources of ambient fine particulate matter (PM(2.5)) that are most responsible for the adverse health effects of short-term exposure to PM (2.5). Daily 24-hour PM(2.5) sampling began in July 2002 at a residential monitoring site in Denver, Colorado, using both Teflon and quartz filter samplers. Sampling is planned to continue through 2008. Chemical speciation is being carried out for mass, inorganic ionic compounds (sulfate, nitrate and ammonium), and carbonaceous components, including elemental carbon, organic carbon, temperature-resolved organic carbon fractions and a large array of organic compounds. In addition, water soluble metals were measured daily for 12 months in 2003. A receptor-based source apportionment approach utilizing positive matrix factorization (PMF) will be used to identify PM (2.5) source contributions for each 24-hour period. Based on a preliminary assessment using synthetic data, the proposed source apportionment should be able to identify many important sources on a daily basis, including secondary ammonium nitrate and ammonium sulfate, diesel vehicle exhaust, road dust, wood combustion and vegetative debris. Meat cooking, gasoline vehicle exhaust and natural gas combustion were more challenging for PMF to accurately identify due to high detection limits for certain organic molecular marker compounds. Measurements of these compounds are being improved and supplemented with additional organic molecular marker compounds. The health study will investigate associations between daily source contributions and an array of health endpoints, including daily mortality and hospitalizations and measures of asthma control in asthmatic children. Findings from the DASH study, in addition to being of interest to policymakers, by identifying harmful PM(2.5) sources may provide insights into mechanisms of PM effect.     

Evaluation of multisectional and two-section particulate matter photochemical grid models in the Western United States

Version 4.10s of the comprehensive air-quality model with extensions (CAMx) photochemical grid model has been developed, which includes two options for representing particulate matter (PM) size distribution: (1) a two-section representation that consists of fine (PM2.5) and coarse (PM2.5-10) modes that has no interactions between the sections and assumes all of the secondary PM is fine; and (2) a multisectional representation that divides the PM size distribution into N sections (e.g., N = 10) and simulates the mass transfer between sections because of coagulation, accumulation, evaporation, and other processes. The model was applied to Southern California using the two-section and multisection representation of PM size distribution, and we found that allowing secondary PM to grow into the coarse mode had a substantial effect on PM concentration estimates. CAMx was then applied to the Western United States for the 1996 annual period with a 36-km grid resolution using both the two-section and multisection PM representation. The Community Multiscale Air Quality (CMAQ) and Regional Modeling for Aerosol and Deposition (REMSAD) models were also applied to the 1996 annual period. Similar model performance was exhibited by the four models across the Interagency Monitoring of Protected Visual Environments (IMPROVE) and Clean Air Status and Trends Network monitoring networks. All four of the models exhibited fairly low annual bias for secondary PM sulfate and nitrate but with a winter overestimation and summer underestimation bias. The CAMx multisectional model estimated that coarse mode secondary sulfate and nitrate typically contribute <10% of the total sulfate and nitrate when averaged across the more rural IMPROVE monitoring network.     

Examining impacts of visibility and PM strategies before implementation

One of the major challenges facing the world today is defining paths to sustainable futures. Part of the challenge is developing a national energy strategy that promotes an adequate energy supply for the United States, while enhancing environmental quality and maintaining U.S. competitiveness in the world economy. To assist in this challenge, we have developed a screening technique to analyze the effectiveness of different proposed emissions reduction strategies. The technique, referred to as the visibility assessment screening technique (VAST), is designed to examine possible impacts on visibility of emission changes of sulfur oxides, nitrogen oxides, volatile organic compounds (i.e., SO2, NOx, and VOC) and fine and coarse particulate matter (PM). The influence of relative humidity, natural aerosols, and the chemical interconnections among sulfur and nitrogen components of aerosols in determining the effectiveness of Clean Air Act Amendment and other projected energy-related emissions changes on eastern and western visibility are explored. The effectiveness of these strategies on particulate matter impacts and potentially on ozone is also noted.