Characterization of Fine Particulate Matter Produced by Combustion of Residual Fuel Oil

ABSTRACT

Combustion experiments were carried out on four different residual fuel oils in a 732-kW boiler. PM emission samples were separated aerodynamically by a cyclone into fractions that were nominally less than and greater than 2.5 |j.m in diameter. However, examination of several of the samples by computer-controlled scanning electron microscopy (CCSEM) revealed that part of the PM_2.5 fraction consists of carbonaceous cenospheres and vesicular particles that range up to 10 |j.m in diameter. X-ray absorption fine structure (XAFS) spectroscopy data were obtained at the S, V, Ni, Fe, Cu, Zn, and As K-edges and at the Pb L-edge. Deconvolution of the X-ray absorption near edge structure (XANES) region of the S spectra established that the dominant molecular forms of S present were sulfate (26-84% of total S) and thiophene (13-39% of total S). Sulfate was greater in the PM_2.5 samples than in the PM₂₅₊ samples. Inorganic sulfides and elemental sulfur were present in lower percentages. The Ni XANES spectra from all of the samples agreed fairly well with that of NiSO₄, while most of the V spectra closely resembled that of vanadyl sulfate (VO?SO₄?xH₂O). The other metals investigated (i.e., Fe, Cu, Zn, and Pb) also were present predominantly as sulfates. Arsenic was present as an arsen-ate (As⁺⁵). X-ray diffraction patterns of the PM_2.5 fraction exhibit sharp lines due to sulfate compounds (Zn, V, Ni, Ca, etc.) superimposed on broad peaks due to amorphous carbons. All of the samples contain a significant organic component, with the loss on ignition (LOI) ranging from 64 to 87% for the PM_2.5 fraction and from 88 to 97% for the PM_2.5+ fraction. Based on ¹³C nuclear magnetic resonance (NMR) analysis, the carbon is predominantly condensed in graphitic structures. Aliphatic structure was detected in only one of seven samples examined.     

Estimates of Particle Hygroscopicity during the Southeastern Aerosol and Visibility Study

ABSTRACT

Aerosol water content was determined from relative humidity controlled optical particle counter (ASASP-X) size distribution measurements made during the Southeastern Aerosol and Visibility Study (SEAVS) in the Great Smoky Mountains National Park during summer 1995. Since the scattering response function of the ASASP-X is sensitive to particle refractive index, a technique for calibrating the ASASP-X for any real refractive index was developed. A new iterative process was employed to calculate water mass concentration and wet refractive index as functions of relative humidity. Experimental water mass concentrations were compared to theoretically predicted values assuming only ammonium sulfate compounds were hygroscopic. These comparisons agreed within experimental uncertainty. Estimates of particle hygroscopicity using a rural aerosol model of refractive index as a function of relative humidity demonstrated no significant differences from those made with daily varying refractive index estimates. Although aerosol size parameters were affected by the assumed chemical composition, forming ratios of these parameters nearly canceled these effects.     

Analysis of a Summertime PM2.5 and Haze Episode in the Mid-Atlantic Region

Abstract

Observations of the mass and chemical composition of particles less than 2.5 μm in aerodynamic diameter (PM_2.5), light extinction, and meteorology in the urban Baltimore-Washington corridor during July 1999 and July 2000 are presented and analyzed to study summertime haze formation in the mid-Atlantic region. The mass fraction of ammoniated sulfate (SO₄ ^2-) and carbonaceous material in PM_2.5 were each ～50% for cleaner air (PM_2.5 < 10 μg/m³) but changed to ～60% and ～20%, respectively, for more polluted air (PM_2.5 > 30 μg/m³). This signifies the role of SO₄ ^2- in haze formation. Comparisons of data from this study with the Interagency Monitoring of Protected Visual Environments network suggest that SO₄ ^2? is more regional than carbonaceous material and originates in part from upwind source regions. The light extinction coefficient is well correlated to PM_2.5 mass plus water associated with inorganic salt, leading to a mass extinction efficiency of 7.6 ± 1.7 m²/g for hydrated aerosol. The most serious haze episode occurring between July 15 and 19, 1999, was characterized by westerly transport and recirculation slowing removal of pollutants. At the peak of this episode, 1-hr PM_2.5 concentration reached ～45 μg/m³, visual range dropped to ～5 km, and aerosol water likely contributed to ～40% of the light extinction coefficient.     

Critique of “Precipitation in Light Extinction Reconstruction” by P.A. Ryan

Abstract

The goal of the Regional Haze Rule (RHR) is to return visibility in class I areas (CIAs) to natural levels, excluding weather-related events, by 2064. Whereas visibility, the seeing of scenic vistas, is a near instantaneous and sight-path-dependent phenomenon, reasonable progress toward the RHR goal is assessed by tracking the incremental changes in 5-yr average visibility. Visibility is assessed using a haze metric estimated from 24-hr average aerosol measurements that are made at one location representative of the CIA. It is assumed that, over the 5-yr average, the aerosol loadings and relative humidity along all of the site paths are the same and can be estimated from the 24-hr measurements. It is further assumed that any time a site path may be obscured by weather (e.g., clouds and precipitation), there are other site paths within the CIA that are not. Therefore, when calculating the haze metric, sampling days are not filtered for weather conditions. This assumption was tested by examining precipitation data from multiple monitors for four CIAs. It is shown that, in general, precipitation did not concurrently occur at all monitors for a CIA, and precipitation typically occurred 3-8 hr or less in a day. In a recent paper in this journal, Ryan asserts that the haze metric should include contributions from precipitation and conducted a quantitative assessment incorrectly based on the assumption that the Optec NGN-2 nephelometer measurements include the effects of precipitation. However, these instruments are programmed to shut down during rain events, and any data logged are in error. He further assumes that precipitation occurs as often on the haziest days as the clearest days and that precipitation light scattering (bprecip) is independent of geographic location and applied an average bprecip derived for Great Smoky Mountains to diverse locations including the Grand Canyon. Both of these assumptions are shown to be in error.     

Integrated Assessment Modeling of Atmospheric Pollutants in the Southern Appalachian Mountains. Part I: Hourly and Seasonal Ozone

Abstract

Recently, a comprehensive air quality modeling system was developed as part of the Southern Appalachians Mountains Initiative (SAMI) with the ability to simulate meteorology, emissions, ozone, size- and composition-resolved particulate matter, and pollutant deposition fluxes. As part of SAMI, the RAMS/EMS-95/URM-1ATM modeling system was used to evaluate potential emission control strategies to reduce atmospheric pollutant levels at Class I areas located in the Southern Appalachians Mountains. This article discusses the details of the ozone model performance and the methodology that was used to scale discrete episodic pollutant levels to seasonal and annual averages. The daily mean normalized bias and error for 1-hr and 8-hr ozone were within U.S. Environment Protection Agency guidance criteria for urban-scale modeling. The model typically showed a systematic overestimation for low ozone levels and an underestimation for high levels. Because SAMI was primarily interested in simulating the growing season ozone levels in Class I areas, daily and seasonal cumulative ozone exposure, as characterized by the W126 index, were also evaluated. The daily ozone W126 performance was not as good as the hourly ozone performance; however, the seasonal ozone W126 scaled up from daily values was within 17% of the observations at two typical Class I areas of the SAMI region. The overall ozone performance of the model was deemed acceptable for the purposes of SAMI’s assessment.     

Apportionment of Ambient Primary and Secondary Pollutants during a 2001 Summer Study in Pittsburgh Using U.S. Environmental Protection Agency UNMIX

Abstract

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 ～18 km southeast of downtown Pittsburgh. Fine particulate matter (PM_2.5) 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.     

Aerosol species concentrations and source apportionment of ammonia at Rocky Mountain National Park

Changes in ecosystem function at Rocky Mountain National Park (RMNP) are occurring because of emissions of nitrogen and sulfate species along the Front Range of the Colorado Rocky Mountains, as well as sources farther east and west. The nitrogen compounds include both oxidized and reduced nitrogen. A year-long monitoring program of various oxidized and reduced nitrogen species was initiated to better understand their origins as well as the complex chemistry occurring during transport from source to receptor. Specifically, the goals of the study were to characterize the atmospheric concentrations of nitrogen species in gaseous, particulate, and aqueous phases (precipitation and clouds) along the east and west sides of the Continental Divide; identify the relative contributions to atmospheric nitrogen species in RMNP from within and outside of the state of Colorado; identify the relative contributions to atmospheric nitrogen species in RMNP from emission sources along the Colorado Front Range versus other areas within Colorado; and identify the relative contributions to atmospheric nitrogen species from mobile sources, agricultural activities, and large and small point sources within the state of Colorado. Measured ammonia concentrations are combined with modeled releases of conservative tracers from ammonia source regions around the United States to apportion ammonia to its respective sources, using receptor modeling tools.

Implications: Increased deposition of nitrogen in RMNP has been demonstrated to contribute to a number of important ecosystem changes. The rate of deposition of nitrogen compounds in RMNP has crossed a crucial threshold called the “critical load.” This means that changes are occurring to park ecosystems and that these changes may soon reach a point where they are difficult or impossible to reverse. Several key issues need attention to develop an effective strategy for protecting park resources from adverse impacts of elevated nitrogen deposition. These include determining the importance of previously unquantified nitrogen inputs within the park and identification of important nitrogen sources and transport pathways.     

Estimating the Cumulative Ecological Effect of Local Scale Landscape Changes in South Florida

Ecosystem restoration in south Florida is a state and national priority centered on the Everglades wetlands. However, urban development pressures affect the restoration potential and remaining habitat functions of the natural undeveloped areas. Land use (LU) planning often focuses at the local level, but a better understanding of the cumulative effects of small projects at the landscape level is needed to support ecosystem restoration and preservation. The South Florida Ecosystem Portfolio Model (SFL EPM) is a regional LU planning tool developed to help stakeholders visualize LU scenario evaluation and improve communication about regional effects of LU decisions. One component of the SFL EPM is ecological value (EV), which is evaluated through modeled ecological criteria related to ecosystem services using metrics for (1) biodiversity potential, (2) threatened and endangered species, (3) rare and unique habitats, (4) landscape pattern and fragmentation, (5) water quality buffer potential, and (6) ecological restoration potential. In this article, we demonstrate the calculation of EV using two case studies: (1) assessing altered EV in the Biscayne Gateway area by comparing 2004 LU to potential LU in 2025 and 2050, and (2) the cumulative impact of adding limestone mines south of Miami. Our analyses spatially convey changing regional EV resulting from conversion of local natural and agricultural areas to urban, industrial, or extractive use. Different simulated local LU scenarios may result in different alterations in calculated regional EV. These case studies demonstrate methods that may facilitate evaluation of potential future LU patterns and incorporate EV into decision making.