Size-resolved aerosol mass and chemical composition were measured during the Pittsburgh Air Quality Study. Daily samples were collected for 12 months from July 2001 to June 2002. Micro-orifice uniform deposit impactors (MOUDIs) were used to collect aerosol samples of fine particulate matter smaller than 10 mm. Measurements of PM 0.056 , PM 0.10 , PM 0.18 , PM 0.32 , PM 0.56 , PM 1.0 , PM 1.8 and PM 2.5 with the MOUDI are available for the full study period. Seasonal variations in the concentrations are observed for all size cuts. Higher concentrations are observed during the summer and lower during the winter.Comparison between the PM 2.5 measurements by the MOUDI and other integrated PM samplers reveals good agreement. Good correlation is observed for PM 10 between the MOUDI and an integrated sampler but the MOUDI underestimates PM 10 by 20%. Bouncing of particles from higher stages of the MOUDI (>PM 2.5 ) is not a major problem because of the low concentrations of coarse particles in the area. The main cause of coarse particle losses appears to be losses to the wall of the MOUDI.Samples were collected on aluminum foils for analysis of carbonaceous material and on Teflon filters for analysis of particle mass and inorganic anions and cations. Daily samples were analyzed during the summer (July 2001) and the winter intensives (January 2002). During the summer around 50% of the organic material is lost from the aluminum foils as compared to a filter-based sampler. These losses are due to volatilization and bounce-off from the MOUDI stages. High nitrate losses from the MOUDI are also observed during the summer (above 70%). Good agreement between the gravimetrically determined mass and the sum of the masses of the individual compounds is obtained, if the lost mass from organics and the aerosol water content are included for the summer. For the winter no significant losses of material are detected and there exists reasonable agreement between the gravimetrical mass and the sum of the concentrations of the individual compounds.Ultrafine particles (below 100 nm) account on average, for o 5% of the PM 2.5 mass, and show different composition for the summer and the winter. During the summer the ultrafine mass is 50% carbonaceous material (organic material and elemental carbon) and 50% inorganic (mainly sulfate and ammonium); during the winter these percentages are 70% and 30%, respectively.

Daily ambient aerosol samples were taken in Pittsburgh, Pennsylvania from the summer 2001 to the winter 2002 as part of the Pittsburgh Air Quality Study (PAQS). The study measured PM 2.5 mass by the Federal Reference Method (FRM) and the PM 2.5 chemical composition by a variety of filter-based and continuous instruments. This paper examines the mass balance between the FRM-measured mass and the sum of the aerosol chemical components. For the 7-month study period, the average FRM-measured mass is 11% greater than the sum of the mass of the aerosol chemical components. This mass balance discrepancy varies seasonally, with the average FRM-measured mass 17% greater than the sum of the chemical components for the summer months, with discrepancies as large as 30% during certain periods. Meanwhile, the FRM-measured mass was at or slightly below the sum of the chemical components for the winter months.The mass balance discrepancy and its seasonal shift cannot be explained by measurement uncertainty; instead the discrepancy is due to combination of retained aerosol water on the conditioned FRM filters and volatilization losses. The relative importance of these different effects varies with aerosol composition and causes the observed seasonal variation in the mass balance. The contribution of the aerosol water to the FRM-measured mass is estimated using continuous measurements of aerosol water at the site; volatilization losses are estimated from other filter-based instruments. Water contributes 16% of the FRM mass in the summer, and 8% of the FRM mass in the winter; it also appears responsible for episodes where the FRM-measured mass is significantly greater than the sum of components. Retention of water is greatest during acidic conditions, which commonly occur during the summer months. Volatilization losses are estimated at 5% of the FRM mass during the summer, and 9% for the winter. Volatilization losses appear to be most significant on days dominated by organic aerosol, or winter days with relatively high nitrate concentration. Accounting for the effects of water and volatilization losses closes the mass balance between the FRM and the sum of the chemical components, providing insight into the FRM measurements. r

A dilution sampler was used to examine the effects of dilution ratio and residence time on the particulate emissions from a pilot-scale pulverized coal combustor. Measurements include the particle size distribution from 0.003 to 2.5 µm, PM 2.5 mass emission rate and PM2.5 composition (OC/EC, major ions, and elemental). Hot filter samples were also collected simultaneously in order to compare the dilution sampler measurement with standard stack sampling methodologies such as EPA Method 5. Measurements were made both before and after the bag-house, the particle control device used on the coal combustor. Measurements were made with three different coal types and a coal-biomass blend.The residence time and dilution ratio do not influence the PM 2.5 mass emission rate, but have a significant effect on the size distribution and total number emissions. Measurements made before the bag-house showed increasing the residence time dramatically decreases the total particle number concentration, and shifts the particle mass to larger sizes. The effects of residence time can be explained quantitatively by the coagulation of the emitted particles. Measurements made after the bag-house were not affected by coagulation due to the lower concentration of particles. Nucleation of sulfuric acid vapor within the dilution was an important source of ultrafine particles. This nucleation is strongly a function of dilution ratio because of the competition between condensation and nucleation. At low dilution ratios condensation dominates and little nucleation is observed; increasing the dilution ratio promotes nucleation because of the corresponding decrease in available surface area per unit volume for condensation. No nucleation was observed after the bag house where conditions greatly favor nucleation over condensation; we suspect that the bag house removed the SO 3 in the flue gas. Exhaust SO 3 levels were not measured during these experiments.Dilution caused the enrichment of selenium, ammonium and sulfate in the PM 2.5 emissions compared to the hot filter samples. The enrichment of selenium was independent of dilution ratio or residence time. The enrichment of ammonium and sulfate increased with increasing dilution ratio. PM 2.5 emission profiles for four different fuels (two eastern bituminous coals, a western sub-bituminous coal, and coal-wood blend) were developed. These profiles compared well with profiles from similar coal sources, while showing unique characteristics due to differences in fuel composition. Executive SummaryIn 1997 the US EPA proposed new standards for particulate matter with an aerodynamic diameter less than 2.5 µm (PM 2.5 ). Development of the regulatory framework necessary to meet these new standards requires improved understanding of the sources for PM 2.5 . Coal-fired utility boilers are one important emission source for particulate matter. Utility boilers are a primary source for both fine particles and gaseous precursors such as SO 2 and NO x that react in the atmosphere to create secondary aeros...