Second generation chemical mass balance source apportionment of sulfur oxides and sulfate at the Grand Canyon during the Project MOHAVE summer intensive

Receptor-based chemical mass balance (CMB) analysis techniques are designed to apportion species that are conserved during pollutant transport using conserved source profiles. The techniques will fail if non-conservative species (or profiles) are not properly accounted for in the CMB model. The straightforward application of the CMB model developed for Project MOHAVE using regional profiles resulted in a significant under-prediction of total sulfate oxides (SOx, SO2 plus fine particulate sulfate) for many samples at Meadview, AZ. In addition, for these samples the concentration of the inert tracer emitted from the MOHAVE Power Project (MPP), ocPDCH, was also under-predicted. A second-generation model has been developed which assumes that separation of particles and SO2 can occur in the MPP plume during nighttime stable plume conditions. This second-generation CMB model accounts for all SOx present at the various receptor sites. In addition, the concentrations of ocPDCH and the presence of other inert tracers of emission from regional sources are accurately predicted. The major source of SOx at Meadview was the MPP, but the major source of sulfate at this site was the Las Vegas urban area. At Hopi Point in the Grand Canyon, the Baja California region (Imperial Valley and northwestern Mexico) was the major source of both SOx and sulfate.     

Development,Evaluation, and Application of a Primary Aerosol Model

ABSTRACT

The Segmented-Plume Primary Aerosol Model (SPPAM) has been developed over the past several years. The earlier model development goals were simply to generalize the widely used Industrial Source Complex Short-Term (ISCST) model to simulate plume transport and dispersion under light wind conditions and to handle a large number of roadway or line sources. The goals have been expanded to include development of improved algorithm for effective plume transport velocity, more accurate and efficient line and area source dispersion algorithms, and recently, a more realistic and computationally efficient algorithm for plume depletion due to particle dry deposition. A performance evaluation of the SPPAM has been carried out using the 1983 PNL dual tracer experimental data. The results show the model predictions to be in good agreement with observations in both plume advection-dispersion and particulate matter (PM) depletion by dry deposition. For PM_2.5 impact analysis, the SPPAM has been applied to the Rubidoux area of California. Emission sources included in the modeling analysis are: paved road dust, diesel vehicular exhaust, gasoline vehicular exhaust, and tire wear particles from a large number of roadways in Rubidoux and surrounding areas. For the selected modeling periods, the predicted primary PM_2.5 to primary PM10 concentration ratios for the Rubidoux sampling station are in the range of 0.39–0.46. The organic fractions of the primary PM_2.5 impacts are estimated to be at least 34–41%. Detailed modeling results indicate that the relatively high organic fractions are primarily due to the proximity of heavily traveled roadways north of the sampling station. The predictions are influenced by a number of factors; principal among them are the receptor locations relative to major roadways, the volume and composition of traffic on these roadways, and the prevailing meteorological conditions.     

Control of Fly Ash from Conventional Coal-Fired Utility Boilers

This paper presents a detailed review and critical evaluation of current technologies as applied to fine particulate emissions from coal-fired utility boilers. Quantitative assessments of the capabilities of both conventional and novel air pollution control devices to meet three different performance standards—the present New Source Performance Standard (NSPS) of 0.03 Ib particulate/MBtu heat input, and standards of 0.05 and 0.1 Ib particulate/MBtu are included. Each of the three conventional devices (electrostatic precipitator, fabric filter baghouse, and wet scrubber) is compared and rated with respect to eight different performance categories. This information can be used to determine the relative effectiveness and attractiveness of these three control devices. Novel devices are compared and rated in the same manner, the conclusions from which may provide the research administrator with a guide for the selection of those novel devices which offer the best potential for commercialization.

The major conclusions of the investigation are: (1) The use of conventional scrubbers for fine particulate control on coal-fired utility boilers may no longer be feasible at the new NSPS of 0.03 Ib/MBtu. (2) At the old NSPS (0.1 Ib/MBtu) conventional electrostatic precipitators and baghouses were often competitive. For the new stricter standard, however, the baghouse generally is the more attractive alternative. (3) Novel devices appear to offer almost no hope for this particular application (at a commercial level) between now and 1985 and only little hope before 1990.     

Assessment of the Nested Grid Model Estimates for Driving Regional Visibility Models in the Southwestern United States

ABSTRACT

The Nested Grid Model (NGM) is a primitive-equation meteorological model that is routinely exercised over North America for forecasting purposes by the National Meteorological Center. While prognostic meteorological models are being increasingly used to drive air quality models, their use in conducting annual simulations requires significant resources. NGM estimates of wind fields and other meteorological variables provide an attractive alternative since they are typically archived and readily available for an entire year. Preliminary evaluation of NGM winds during the summer of 1992 for application to the region surrounding the Grand Canyon National Park showed serious shortcomings. The NGM winds along the borders between California, Arizona and Mexico tend to be northwesterly with a speed of about 6 m/sec, while the observed flow is predominantly southerly at about 2-5 m/sec. The mesoscale effect of a thermal low pressure area over the highly heated Southern California and western Arizona deserts does not appear to be represented by the NGM because of its coarse resolution and the use of sparse observations in that region. Tracer simulations and statistical evaluation against special high resolution observations of winds in the southwest United States clearly demonstrate the northwest bias in NGM winds and its adverse effect on predictions of an air quality model. The “enhanced” NGM winds, in which selected wind observations are incorporated in the NGM winds using a diagnostic meteorological model provide additional confirmation on the primary cause of the northwest bias. This study has demonstrated that in situations where limited resources prevent the use of prognostic meteorological models, previously archived coarse resolution wind fields in which additional observations are incorporated to correct known biases provide an attractive option.     

Relating Summer Ambient Particulate Sulfur,Sulfur Dioxide,and Light Scattering to Gaseous Tracer Emissions from the MOHAVE Power Project

ABSTRACT

Project MOHAVE was initiated in 1992 to examine the role of emissions from the 1580 MW coal-fired MOHAVE Power Project (MPP) on haze at the Grand Canyon National Park (GCNP), located about 130 km north-northeast of the power plant. Statistical relationships were analyzed between summertime ambient concentrations of a gaseous perfluorocarbon tracer released from MPP and ambient SO₂, particulate sulfur, and light scattering to evaluate whether MPP's emissions could be transported to the GCNP and then impact haze levels there. Spatial analyses indicated that particulate sulfur levels were strongly correlated across the monitoring network, regardless of whether the monitoring stations were upwind or downwind of MPP. This indicates that particulate sulfur levels in this region were influenced by distant regional emission sources. A significant particulate sulfur contribution from a point source such as MPP would result in a non-uniform pattern downwind. There was no suggestion of this in the data.

Furthermore, correlations between the MPP tracer and ambient particulate sulfur and light scattering at locations in the park were virtually zero for averaging times ranging from 24 hr to 1 hr. Hour-by-hour MPP tracer levels and light scattering were individually examined, and still no positive correlations were detected. Finally, agreement between tracer and particulate sulfur did not improve as a function of meteorological regime, implying that, even during cloudy monsoon days when more rapid conversion of SO₂ to par-ticulate sulfur would be expected, there was no evidence for downwind particulate sulfur impacts. Despite the fact that MPP was a large source of SO₂ and tracer, neither time series nor correlation analyses were able to detect any meaningful relationship between MPP's SO₂ and tracer emission “signals” to particulate sulfur or light scattering.     

Evaluation of Wind Fields Used in Grand Canyon Visibility Transport Commission Analyses

ABSTRACT

The Grand Canyon Visibility Transport Commission (GCVTC) was established by the U.S. Congress to assess the potential impacts of projected growth on atmospheric visibility at Grand Canyon National Park and to make recommendations to the U.S. Environmental Protection Agency on what measures could be taken to avoid such adverse impacts. A critical input to the assessment tool used by the commission was three-dimensional model-derived wind fields used to transport the emissions. This paper describes the evaluation of the wind fields used at various stages in the assessment. Wind fields evaluated included those obtained from the Colorado State University Regional Atmospheric Modeling System (RAMS), the National Meteorological Center's Nested Grid Model (NGM), and the National Oceanic and Atmospheric Administration's Atmospheric Transport and Dispersion (ATAD) trajectory model. The model-derived wind fields were evaluated at multiple vertical levels at several locations in the southwestern United States by determining differences between model predicted winds and winds that were measured using radiosonde and radar wind profiler data. Model-derived winds were also evaluated by determining the percent of time that they were within acceptable differences from measured winds.

All models had difficulties, generally meeting the acceptable criteria for less than 50% of the predictions. The RAMS model had a persistent bias toward southwesterly winds at the expense of other directions, especially failing to represent channeling by north-south mountain ranges in the lower levels. The NGM model exhibited a substantial bias in the summer months by extending northwesterly winds in the eastern Pacific Ocean well inland, in contrast to the observed southwesterlies at inland locations. The simpler ATAD trajectory model performed somewhat better than the other models, probably because of its use of more upper air sites. The results of the evaluation indicated that these wind fields could not be used to reliably predict source-receptor impacts on a particular day; thus, seasonally averaged impacts were used in the GCVTC assessment.     

Fine Particulate Chemical Composition and Light Extinction at Meadview,AZ

Abstract

The concentration of fine particulate nitrate, sulfate, and carbonaceous material was measured for 12-hr day-night samples using diffusion denuder samplers during the Project Measurement of Haze and Visibility Effects (MOHAVE) July to August 1992 Summer Intensive study at Meadview, AZ, just west of Grand Canyon National Park. Organic material was measured by several techniques. Only the diffusion denuder method measured the semivolatile organic material. Fine particulate sulfate and nitrate (using denuder technology) determined by various groups agreed. Based on the various collocated measurements obtained during the Project MOHAVE study, the precision of the major fine particulate species was ±0.6 μg/m³ organic material, ±0.3 μg/m³ ammonium sulfate, and ±0.07 μg/m³ ammonium nitrate. Data were also available on fine particulate crustal material, fine and coarse particulate mass from the Interagency Monitoring of Protected Visual Environments sampling system, and relative humidity (RH), light absorption, particle scattering, and light extinction measurements from Project MOHAVE. An extinction budget was obtained using mass scattering coefficients estimated from particle size distribution data. Literature data were used to estimate the change in the mass scattering coefficients for the measured species as a function of RH and for the absorption of light by elemental carbon. Fine particulate organic material was the principal particulate contributor to light extinction during the study period, with fine particulate sulfate as the second most important contributor. During periods of highest light extinction, contributions from fine particulate organic material, sulfate, and light-absorbing carbon dominated the extinction of light by particles. Particle light extinction was dominated by sulfate and organic material during periods of lowest light extinction. Combination of the extinction data and chemical mass balance analysis of sulfur oxides sources in the region indicate that the major anthropogenic contributors to light extinction were from the Los Angeles, CA, and Las Vegas, NV, urban areas. Mohave Power Project associated secondary sulfate was a negligible contributor to light extinction.     

Evaluation of the Effects of Emission Reductions on Secondary Particulate Matter in the South Coast Air Basin of California

An Aerosol Trajectory Model (ATM) is applied to the South Coast Air Basin of California for a two-day episode in August 1982 to evaluate proposed control strategies that aim to reduce atmospheric aerosols. Model predictions Indicate that secondary organic aerosols decrease linearly with reactive hydrocarbon emissions. In addition, the model shows that If sulf ate is produced only in the gas phase by oxidation of SO₂, then reduction In SO₂ emissions yields a nearly proportional decrease In sulfate levels. Reduction in ammonia emissions, combined with reduction of NO_x emissions, gives the best results In terms of nitrate control. The order in which the emission controls are implemented Is predicted to have a major impact on the reduction of secondary atmospheric aerosols.     

Fine particulate chemical composition and light extinction at Meadview, AZ

The concentration of fine particulate nitrate, sulfate, and carbonaceous material was measured for 12-hr day-night samples using diffusion denuder samplers during the Project Measurement of Haze and Visibility Effects (MOHAVE) July to August 1992 Summer Intensive study at Meadview, AZ, just west of Grand Canyon National Park. Organic material was measured by several techniques. Only the diffusion denuder method measured the semivolatile organic material. Fine particulate sulfate and nitrate (using denuder technology) determined by various groups agreed. Based on the various collocated measurements obtained during the Project MOHAVE study, the precision of the major fine particulate species was +/- 0.6 microg/m3 organic material, +/- 0.3 microg/m3 ammonium sulfate, and +/- 0.07 microg/m3 ammonium nitrate. Data were also available on fine particulate crustal material, fine and coarse particulate mass from the Interagency Monitoring of Protected Visual Environments sampling system, and relative humidity (RH), light absorption, particle scattering, and light extinction measurements from Project MOHAVE. An extinction budget was obtained using mass scattering coefficients estimated from particle size distribution data. Literature data were used to estimate the change in the mass scattering coefficients for the measured species as a function of RH and for the absorption of light by elemental carbon. Fine particulate organic material was the principal particulate contributor to light extinction during the study period, with fine particulate sulfate as the second most important contributor. During periods of highest light extinction, contributions from fine particulate organic material, sulfate, and light-absorbing carbon dominated the extinction of light by particles. Particle light extinction was dominated by sulfate and organic material during periods of lowest light extinction. Combination of the extinction data and chemical mass balance analysis of sulfur oxides sources in the region indicate that the major anthropogenic contributors to light extinction were from the Los Angeles, CA, and Las Vegas, NV, urban areas. Mohave Power Project associated secondary sulfate was a negligible contributor to light extinction.