Effects of SO2 and NOx emission reductions on PM2.5 mass concentrations in the southeastern United States

Measurements from sites of the Southeastern Aerosol Research and Characterization (SEARCH) program, made from 1998 to 2001, are used with a thermodynamic equilibrium model, Simulating Composition of Atmospheric Particles at Equilbrium (SCAPE2), to extend an earlier investigation of the responses of fine particulate nitrate (NO3-) and fine particulate matter (PM2.5) mass concentrations to changes in concentrations of nitric acid (HNO3) and sulfate (SO42-). The responses were determined for a projected range of variations of SO42- and HNO3 concentrations resulting from adopted and proposed regulatory initiatives. The predicted PM2.5 mass concentration decreases averaged 1.8-3.9 microg/m3 for SO42- decreases of 46-63% from current concentrations. Combining the S042- decrease with a 40% HNO3 decrease from current concentrations (approximating expected mobile-source oxides of nitrogen [NOx] reductions by 2020) yielded additional incremental reductions of mean predicted PM2.5 mass concentration of 0.2 microg/m3 for three nonurban sites and 0.8-1 microg/m3 for one nonurban and two urban sites. Increasing the HNO3 reduction to 55% (an estimate of adding Clear Skies Phase II NOx reductions) yielded additional incremental reductions of mean predicted PM2.5 mass concentration of 0-0.4 microg/m3. Because of the well-documented losses of particulate NO3- from Federal Reference Method (FRM) filters, only a fraction of these incremental changes would be observed.     

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.     

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.     

Loss of PM2.5 nitrate from filter samples in central California

Evaporative loss of particulate matter (with aerodynamic diameter < 2.5 microm, [PM2.5]) ammonium nitrate from quartz-fiber filters during aerosol sampling was evaluated from December 3, 1999, through February 3, 2001, at two urban (Fresno and Bakersfield) and three nonurban (Bethel Island, Sierra Nevada Foothills, and Angiola) sites in central California. Compared with total particulate nitrate, evaporative nitrate losses ranged from < 10% during cold months to > 80% during warm months. In agreement with theory, evaporative loss from quartz-fiber filters in nitric acid denuded samplers is controlled by the ambient nitric acid-to-particulate nitrate ratio, which is determined mainly by ambient temperature. Accurate estimation of nitrate volatilization requires a detailed thermodynamic model and comprehensive chemical measurements. For the 14-month average of PM2.5 acquired on Teflon-membrane filters, measured PM2.5 mass was 8-16% lower than actual PM2.5 mass owing to nitrate volatilization. For 24-hr samples, measured PM2.5 was as much as 32-44% lower than actual PM2.5 at three California Central Valley locations.     

Indoor/outdoor relationships for ambient PM2.5 and associated pollutants: epidemiological implications in Lindon, Utah

Outdoor and indoor fine particulate species were measured at the Lindon Elementary School in Lindon, Utah, to determine which components of ambient fine particles have strong indoor and outdoor concentration correlations. PM2.5 mass concentrations were measured using tapered element oscillating microbalance (TEOM) monitors and by gravimetric analysis of Teflon filter samples. Gas-phase HNO3, sulfur dioxide, particulate nitrate, strong acid, and particulate sulfate were measured using annular denuder samplers. Soot was measured using quartz filters in filter packs. Total particulate number was measured with a condensation nucleus counter (CNC). Total particulate number and fine particulate sulfate and soot were correlated for ambient and indoor measurements. Indoor PM2.5 mass showed a low correlation with outdoor PM2.5 mass because of the influence of coarse material from student activities on indoor PM2.5. Fine particle acidity and the potentiation of biological oxidative mechanisms by iron were not correlated indoors and outdoors.     

Spatial and temporal characterization of PM2.5 mass concentrations in California, 1980-2007

Systematic measurement of fine particulate matter (aerodynamic diameter less than 2.5 microm [PM2.5]) mass concentrations began nationally with implementation of the Federal Reference Method (FRM) network in 1998 and 1999. In California, additional monitoring of fine particulate matter (PM) occurred via a dichotomous sampler network and several special studies carried out between 1982 and 2002. The authors evaluate the comparability of FRM and non-FRM measurements of PM2.5 mass concentrations and establish conversion factors to standardize fine mass measurements from different methods to FRM-equivalent concentrations. The authors also identify measurements of PM2.5 mass concentrations that do not agree with FRM or other independent PM2.5 mass measurements. The authors show that PM2.5 mass can be reconstructed to a high degree of accuracy (r2 > 0.9; mean absolute error approximately 2 microg m(-3)) from PM with an aerodynamic diameter < or =10 microm (PM10) mass and species concentrations when site-specific and season-specific conversion factors are used and a statewide record of fine PM mass concentrations by combining the FRM PM2.5 measurements, non-FRM PM2.5 measurements, and reconstructions of PM2.5 mass concentrations. Trends and spatial variations are evaluated using the integrated data. The rates of change of annual fine PM mass were negative (downward trends) at all 22 urban and 6 nonurban (Interagency Monitoring of Protected Visual Environments [IMPROVE]) monitoring locations having at least 15 yr of data during the period 1980-2007. The trends at the IMPROVE sites ranged from -0.05 to -0.25 microg m(-3) yr(-1) (median -0.11 microg m(-3) yr(-1)), whereas urban-site trends ranged from -0.13 to -1.29 microg m(-3) yr(-1) (median -0.59 microg m(-3) yr(-1)). The urban concentrations declined by a factor of 2 over the period of record, and these decreases were qualitatively consistent with changes in emissions of primary PM2.5 and gas-phase precursors of secondary PM. Mean PM2.5 mass concentrations ranged from 3.3 to 7.4 microg m(-3) at IMPROVE sites and from 9.3 to 37.1 microg m(-3) at urban sites.     

Particulate matter in California: part 2--Spatial, temporal, and compositional patterns of PM2.5, PM10-2.5, and PM10

Geographic and temporal variations in the concentration and composition of particulate matter (PM) provide important insights into particle sources, atmospheric processes that influence particle formation, and PM management strategies. In the nonurban areas of California, annual-average PM2.5 and PM10 concentrations range from 3 to 10 microg/m3 and from 5 to 18 microg/m3, respectively. In the urban areas of California, annual-averages for PM2.5 range from 7 to 30 microg/m3, with observed 24-hr peaks reaching levels as high as 160 microg/m3. Within each air basin, exceedances are a mixture of isolated events as well as periods of elevated PM2.5 concentrations that are more prolonged and regional in nature. PM2.5 concentrations are generally highest during the winter months. The exception is the South Coast Air Basin, where fairly high values occur throughout the year. Annual-average PM2.5 mass, as well as the concentrations of major components, declined from 1988 to 2000. The declines are especially pronounced for the sulfate (SO4(2-)) and nitrate (NO3-) components of PM2.5 and PM10) and correlate with reductions in ambient levels of oxides of sulfur (SOx) and oxides of nitrogen (NOx). Annual averages for PM10-2.5 and PM10 exhibited similar downwind trends from 1994 to 1999, with a slightly less pronounced decrease in the coarse fraction.     

Aerosol ion characteristics during the Big Bend Regional Aerosol and Visibility Observational study

The ionic compositions of particulate matter with aerodynamic diameter < or = 2.5 microm (PM2.5) and size-resolved aerosol particles were measured in Big Bend National Park, Texas, during the 1999 Big Bend Regional Aerosol and Visibility Observational study. The ionic composition of PM2.5 aerosol was dominated by sulfate (SO4(2-)) and ammonium (NH4+). Daily average SO4(2-) and NH4+ concentrations were strongly correlated (R2 = 0.94). The molar ratio of NH4+ to SO4(2-) averaged 1.54, consistent with concurrent measurements of aerosol acidity. The aerosol was observed to be comprised of a submicron fine mode consisting primarily of ammoniated SO4(2-) and a coarse particle mode containing nitrate (NO3-). The NO3- appears to be primarily associated with sea salt particles where chloride has been replaced by NO3-, although formation of calcium nitrate (Ca(NO3)2) is important, too, on several days. Size-resolved aerosol composition results reveal that a size cut in particulate matter with aerodynamic diameter < or = 1 microm would have provided a much better separation of fine and coarse aerosol modes than the standard PM2.5 size cut utilized for the study. Although considerable nitric acid exists in the gas phase at Big Bend, the aerosol is sufficiently acidic and temperatures sufficiently high that even significant future reductions in PM2.5 SO4(2-) are unlikely to be offset by formation of particulate ammonium nitrate in summer or fall.     

Characterization of particulate matter for three sites in Kuwait

Many studies have shown strong associations between particulate matter (PM) levels and a variety of health outcomes, leading to changes in air quality standards in many regions, especially the United States and Europe. Kuwait, a desert country located on the Persian Gulf, has a large petroleum industry with associated industrial and urban land uses. It was marked by environmental destruction from the 1990 Iraqi invasion and subsequent oil fires. A detailed particle characterization study was conducted over 12 months in 2004-2005 at three sites simultaneously with an additional 6 months at one of the sites. Two sites were in urban areas (central and southern) and one in a remote desert location (northern). This paper reports the concentrations of particles less than 10 microm in diameter (PM10) and fine PM (PM2.5), as well as fine particle nitrate, sulfate, elemental carbon (EC), organic carbon (OC), and elements measured at the three sites. Mean annual concentrations for PM10 ranged from 66 to 93 microg/m3 across the three sites, exceeding the World Health Organization (WHO) air quality guidelines for PM10 of 20 microg/m3. The arithmetic mean PM2.5 concentrations varied from 38 and 37 microg/m3 at the central and southern sites, respectively, to 31 microg/m3 at the northern site. All sites had mean PM2.5 concentrations more than double the U.S. National Ambient Air Quality Standard (NAAQS) for PM2.5. Coarse particles comprised 50-60% of PM10. The high levels of PM10 and large fraction of coarse particles comprising PM10 are partially explained by the resuspension of dust and soil from the desert crust. However, EC, OC, and most of the elements were significantly higher at the urbanized sites, compared with the more remote northern site, indicating significant pollutant contributions from local mobile and stationary sources. The particulate levels in this study are high enough to generate substantial health impacts and present opportunities for improving public health by reducing airborne PM.     

Marginal PM25: Nonlinear Aerosol Mass Response to Sulfate Reductions in the Eastern United States

ABSTRACT

Reductions in airborne sulfate concentration may cause inorganic fine particulate matter (PM₂₅) to respond nonlinearly, as nitric acid gas may transfer to the aerosol phase. Where this occurs, reductions in sulfur dioxide (SO₂) emissions will be much less effective than expected at reducing PM_2.5. As a measure of the efficacy of reductions in sulfate concentration on PM , we define marginal PM_2.5 as the local change in PM_2.5 resulting from a small change in sulfate concentration. Using seasonal-average conditions and assuming thermodynamic equilibrium, we find that the conditions for PM_2.5 to respond nonlinearly to sulfate reductions are common in the eastern United States in winter, occurring at half of the sites considered, and uncommon in summer, due primarily to the influence of temperature. Accounting for diurnal and intraseasonal variability, we find that seasonal-average conditions provide a reasonable indicator of the time-averaged PM_2.5 response. These results indicate that reductions in sulfate concentration may be up to 50% less effective at reducing the annual-average PM_2.5 than if the role of nitric acid is neglected. Further, large reductions in sulfate will also cause an increase in aerosol nitrate in many regions that are the most acidic.     

The transformation of outdoor ammonium nitrate aerosols in the indoor environment

Recent studies associate particulate air pollution with adverse health effects; however, the exposure to indoor particles of outdoor origin is not well characterized, particularly for individual chemical species. We conducted a field study in an unoccupied, single-story residence in Clovis, California to provide data and analyses to address issues important for assessing exposure. We used real-time particle monitors both outdoors and indoors to quantify nitrate, sulfate, and carbon particulate matter of particle size 2.5 μm or less in diameter (PM-2.5). The results show that measured indoor ammonium nitrate concentrations were significantly lower than would be expected based solely on penetration and deposition losses. The additional reduction can be attributed to the transformation indoors of ammonium nitrate into ammonia and nitric acid gases, which are subsequently lost by deposition and sorption to indoor surfaces. A mass balance model that accounts for the kinetics of ammonium nitrate evaporation was able to reproduce measured indoor ammonium nitrate and nitric acid concentrations, resulting in a fitted value of the deposition velocity for nitric acid of 0.56 cm s⁻¹. The results indicate that indoor exposure to outdoor ammonium nitrate in Central Valley of California are small, and suggest that exposure assessments based on total particle mass measured outdoors may obscure the actual causal relationships for indoor exposure to particles of outdoor origin.     

Modeling inorganic aerosols and their response to changes in precursor concentration in Mexico City

Based on data from the 1997 Investigación sobre Materia Particulada y Deterioro Atmosférico-Aerosol and Visibility Evaluation Research (IMADA-EVER) campaign and the inorganic aerosol model ISORROPIA, the response of inorganic aerosols to changes in precursor concentrations was calculated. The aerosol behavior is dominated by the abundance of ammonia and thus, changes in ammonia concentration are expected to have a small effect on particle concentrations. Changes in sulfate and nitrate are expected to lead to proportional reductions in inorganic fine particulate matter (PM2.5). Comparing the predictions of ISORROPIA with the observations, the lowest bias and error are achieved when the aerosols are assumed to be in the efflorescence branch. Including crustal species reduces the bias and error for nitrate but does not improve overall model performance. The estimated response of inorganic PM2.5 to changes in precursor concentrations is affected by the inclusion of crustal species in some cases, although average responses are comparable with and without crustal species. Observed concentrations of particle chloride suggest that gas phase concentrations of hydrogen chloride may not be negligible, and future measurement campaigns should include observations to test this hypothesis. Our ability to model aerosol behavior in Mexico City and, thus, design control strategies, is constrained primarily by a lack of observations of gas phase precursors. Future campaigns should focus in particular on better understanding the temporal and spatial distribution of ammonia concentrations. In addition, gas phase observations of nitric acid are needed, and a measure of particle water content will allow stable versus metastable aerosol behavior to be distinguished.     

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.     

Processes Influencing Secondary Aerosol Formation in the San Joaquin Valley during Winter

Abstract

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 (≤188 μg/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.     

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.     

Wintertime vertical variations in particulate matter (PM) and precursor concentrations in the San Joaquin Valley during the California Regional Coarse PM/Fine PM Air Quality Study

Air quality monitoring was conducted at a rural site with a tower in the middle of California's San Joaquin Valley (SJV) and at elevated sites in the foothills and mountains surrounding the SJV for the California Regional PM10/ PM2.5 Air Quality Study. Measurements at the surface and n a tower at 90 m were collected in Angiola, CA, from December 2000 through February 2001 and included hourly black carbon (BC), particle counts from optical particle counters, nitric oxide, ozone, temperature, relative humidity, wind speed, and direction. Boundary site measurements were made primarily using 24-hr integrated particulate matter (PM) samples. These measurements were used to understand the vertical variations of PM and PM precursors, the effect of stratification in the winter on concentrations and chemistry aloft and at the surface, and the impact of aloft-versus-surface transport on PM concentrations. Vertical variations of concentrations differed among individual species. The stratification may be important to atmospheric chemistry processes, particularly nighttime nitrate formation aloft, because NO2 appeared to be oxidized by ozone in the stratified aloft layer. Additionally, increases in accumulation-mode particle concentrations in the aloft layer during a fine PM (PM2.5) episode corresponded with increases in aloft nitrate, demonstrating the likelihood of an aloft nighttime nitrate formation mechanism. Evidence of local transport at the surface and regional transport aloft was found; transport processes also varied among the species. The distribution of BC appeared to be regional, and BC was often uniformly mixed vertically. Overall, the combination of time-resolved tower and surface measurements provided important insight into PM stratification, formation, and transport.     

A retrospective comparison of model-based forecasted PM2.5 concentrations with measurements

This study presents an assessment of the performance of the Community Multiscale Air Quality (CMAQ) photochemical model in forecasting daily PM2.5 (particulate matter < or = 2.5 microm in aerodynamic diameter) mass concentrations over most of the eastern United States for a 2-yr period from June 14, 2006 to June 13, 2008. Model predictions were compared with filter-based and continuous measurements of PM2.5 mass and species on a seasonal and regional basis. Results indicate an underprediction of PM2.5 mass in spring and summer, resulting from under-predictions in sulfate and total carbon concentrations. During winter, the model overpredicted mass concentrations, mostly at the urban sites in the northeastern United States because of overpredictions in unspeciated PM2.5 (suggesting possible overestimation of primary emissions) and sulfate. A comparison of observed and predicted diurnal profiles of PM2.5 mass at five sites in the domain showed significant discrepancies. Sulfate diurnal profiles agreed in shape across three sites in the southern portion of the domain but differed at two sites in the northern portion of the domain. Predicted organic carbon (OC) profiles were similar in shape to mass, suggesting that discrepancies in mass profiles probably resulted from the underprediction in OC. The diurnal profiles at a highly urbanized site in New York City suggested that the overpredictions at that site might be resulting from overpredictions during the morning and evening hours, displayed as sharp peaks in predicted profiles. An examination of the predicted planetary boundary layer (PBL) heights also showed possible issues in the modeling of PBL.     

The Southeastern Aerosol Research and Characterization Study: Part II. Filter-based measurements of fine and coarse particulate matter mass and composition

The Southeastern Aerosol Research and Characterization Study (SEARCH) was implemented in 1998-1999 to provide data and analyses for the investigation of the sources, chemical speciation, and long-term trends of fine particulate matter (PM2.5) and coarse particulate matter (PM10-2.5) in the Southeastern United States. This work is an initial analysis of 5 years (1999-2003) of filter-based PM2.5 and PM10-2.5 data from SEARCH. We find that annual PM2.5 design values were consistently above the National Ambient Air Quality Standards (NAAQS) 15 microg/m3 annual standard only at monitoring sites in the two largest urban areas (Atlanta, GA, and North Birmingham, AL). Other sites in the network had annual design values below the standard, and no site had daily design values above the NAAQS 65 microg/m3 daily standard. Using a particle composition monitor designed specifically for SEARCH, we found that volatilization losses of nitrate, ammonium, and organic carbon must be accounted for to accurately characterize atmospheric particulate matter. In particular, the federal reference method for PM2.5 underestimates mass by 3-7% as a result of these volatilization losses. Organic matter (OM) and sulfate account for approximately 60% of PM2.5 mass at SEARCH sites, whereas major metal oxides (MMO) and unidentified components ("other") account for > or = 80% of PM10-2.5 mass. Limited data suggest that much of the unidentified mass in PM10-2.5 may be OM. For paired comparisons of urban-rural sites, differences in PM2.5 mass are explained, in large part, by higher OM and black carbon at the urban site. For PM10, higher urban concentrations are explained by higher MMO and "other." Annual means for PM2.5 and PM10-2.5 mass and major components demonstrate substantial declines at all of the SEARCH sites over the 1999-2003 period (10-20% in the case of PM2.5, dominated by 14-20% declines in sulfate and 11-26% declines in OM, and 14-25% in the case of PM10-2.5, dominated by 17-30% declines in MMO and 14-31% declines in "other"). Although declining national emissions of sulfur dioxide and anthropogenic carbon may account for a portion of the observed declines, additional investigation will be necessary to establish a quantitative assessment, especially regarding trends in local and regional emissions, primary carbon emissions, and meteorology.     

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.     

Wintertime Vertical Variations in Particulate Matter (PM) and Precursor Concentrations in the San Joaquin Valley during the California Regional Coarse PM/Fine PM Air Quality Study

Abstract

Air quality monitoring was conducted at a rural site with a tower in the middle of California’s San Joaquin Valley (SJV) and at elevated sites in the foothills and mountains surrounding the SJV for the California Regional PM₁₀/M_2.5 Air Quality Study. Measurements at the surface and on a tower at 90 m were collected in Angiola, CA, from ecember 2000 through February 2001 and included hourly black carbon (BC), particle counts from optical particle counters, nitric oxide, ozone, temperature, relative humidity, wind speed, and direction. Boundary site measurements were made primarily using 24-hr integrated particulate matter (PM) samples. These measurements were used to understand the vertical variations of PM and PM precursors, the effect of stratification in the winter on concentrations and chemistry aloft and at the surface, and the impact of aloft-versus-surface transport on PM concentrations. Vertical variations of concentrations differed among individual species. The stratification may be important to atmospheric chemistry processes, particularly nighttime nitrate formation aloft, because NO₂ appeared to be oxidized by ozone in the stratified aloft layer. Additionally, increases in accumulation-mode particle concentrations in the aloft layer during a fine PM (PM_2.5) episode corresponded with increases in aloft nitrate, demonstrating the likelihood of an aloft nighttime nitrate formation mechanism. Evidence of local transport at the surface and regional transport aloft was found; transport processes also varied among the species. The distribution of BC appeared to be regional, and BC was often uniformly mixed vertically. Overall, the combination of time-resolved tower and surface measurements provided important insight into PM stratification, formation, and transport.