Receptor Model Evaluation of the Southeast Michigan Ozone Study Ambient NMOC Measurements

Abstract

Large-scale studies like the Southeast Michigan Ozone Study (SEMOS) have focused attention on quantifying and spedating inventories for volatile organic compounds (VOCs). One approach for evaluating the accuracy of a VOC emission inventory is the development of a chemical mass balance (CMB) receptor model for ambient non-methane organic compound (NMOC) measurements. CMB evaluations of ambient hydrocarbon data provide a sample-specific allocation of emissions to individual source categories. This study summarizes the results of an application of the CMB model to the NMOC data from the SEMOS study. Comparison of CMB results with emission inventory values for the Detroit area show that vehicle emissions are well represented by the inventory, as are architectural coatings and coke ovens. Estimated emissions from petroleum refineries and graphic arts industries are much lower in the inventory than determined from the receptor allocation. Under-reporting of fugitive VOC emissions from petroleum refineries is an ongoing problem. Emissions from graphic arts industries are underestimated in the inventory partly because of the broad characterization of the emission factor (i.e., mass emitted/capita), which may be less useful when specific locations and days are under consideration. This study also demonstrates the effectiveness of the CMB approach when used prospectively to track the implementation of emission control strategies. While vehicle emission concentrations were unchanged from 1988 to 1993, measurement-based CMB results suggest a decrease in evaporative emissions during this time period resulting from Reid vapor pressure (RVP) reductions (from 11.0 psi in 1988 to 8.6 psi in 1993) and fleet turnover. Changes in emissions from coke plants and petroleum refineries were also seen in the CMB allocations for these sources.     

A Comparative Analysis of Emissions Deterioration for In-Use Alternative Fuel Vehicles

Abstract

Although there have been several studies examining emissions from in–use alternative fuel vehicles (AFVs), little is known about the deterioration of these emissions over vehicle lifetimes and how this deterioration compares with deterioration from conventional vehicles (CVs). This paper analyzes emissions data from 70 AFVs and 70 CVs operating in the federal government fleet to determine whether AFV emissions deterioration differs significantly from CV emissions deterioration. An analysis is conducted on three alternative fuel types (natural gas, methanol, and ethanol) and on four pollutants (carbon monoxide, total hydrocarbons, non-methane hydrocarbons, and nitrogen oxides). The results indicate that for most cases studied, deterioration differences are not statistically significant; however, several exceptions (most notably with natural gas vehicles) suggest that air quality planners and regulators must further analyze AFV emissions deterioration to properly include these technologies in broader air quality management schemes.     

Method Comparisons for Particulate Nitrate,Elemental Carbon,and PM2.5 Mass in Seven U.S. Cities

ABSTRACT

Methods that measure PM₂₅ mass, total particulate NO₃ ^-, and elemental carbon (EC) were evaluated in seven U.S. cities from 1997 to 1999. Sampling was performed in Bakersfield, CA; Boston, MA; Chicago, IL; Dallas, TX; Philadelphia, PA; Phoenix, AZ; and Riverside, CA. Evaluating and validating methods that measure the components of fine mass are important to the effort of establishing a speciation-monitoring network. The Harvard Impactor (HI), which measures fine particle mass, showed excellent agreement (r² = 0.99) with the PM₂₅ Federal Reference Method (FRM) for 81 24-hr samples in Riverside and Bakersfield. The HI also showed good precision (4.8%) for 243 24-hr collocated samples over eight studies.

The Aethalometer was employed in six of the sampling locations to measure black carbon (BC). These values were compared to EC as measured from a quartz filter using thermal analysis. For the six cities combined, the two methods were highly correlated (r² = 0.94; 187 24-hr samples); however, the BC values were approximately 24% less than the EC measurements consistently across all six cites. This compares well to results observed for EC/BC measurements observed in other semi-urban areas. Par-ticulate NO₃ ^- was measured using the Harvard-EPA Annular Denuder System (HEADS). This was compared to the NO₃ ^- measured from the HI Teflon (DuPont) filter to assess NO₃ ^- artifacts. Significant NO₃ ^- losses (approximately 50% of total NO₃ ^-) were found in Riverside, Philadelphia, and Boston, while minimal artifacts were observed in the other sites. Two types of HEADS configurations were employed in five cities. One system used a Na₂CO₃-coated glass fiber filter, and the other type used a nylon filter to collect volatilized NO₃ ^- from the Teflon filter. The HEADS with the Na₂CO₃-coated filter consistently underestimated the total particulate NO₃ ^- by approximately 20% compared to the nylon HEADS.     

Biological Removal of Gaseous Ammonia in Biofilters: Space Travel and Earth-Based Applications

ABSTRACT

Gaseous NH₃ removal was studied in laboratory-scale biofilters (14-L reactor volume) containing perlite inoculated with a nitrifying enrichment culture. These biofilters received 6 L/min of airflow with inlet NH₃ concentrations of 20 or 50 ppm, and removed more than 99.99% of the NH₃ for the period of operation (101, 102 days). Comparison between an active reactor and an autoclaved control indicated that NH₃ removal resulted from nitrification directly, as well as from enhanced absorption resulting from acidity produced by nitrification. Spatial distribution studies (20 ppm only) after 8 days of operation showed that nearly 95% of the NH₃ could be accounted for in the lower 25% of the biofilter matrix, proximate to the port of entry. Periodic analysis of the biofilter material (20 and 50 ppm) showed accumulation of the nitrification product NO₃ ^- early in the operation, but later both NO₂ ^- and NO₃ ^- accumulated. Additionally, the N-mass balance accountability dropped from near 100% early in the experiments to ~95 and 75% for the 20- and 50-ppm biofilters, respectively. A partial contributing factor to this drop in mass balance accountability was the production of NO and N₂O, which were detected in the biofilter exhaust.     

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.     

Comparison of Aerobic and Anaerobic Biotreatment of Municipal Solid Waste

Abstract

To increase the operating lifetime of landfills and to lower leachate treatment costs, an increasing number of municipal solid waste (MSW) landfills are being managed as either aerobic or anaerobic bioreactors. Landfill gas composition, respiration rates, and subsidence were measured for 400 days in 200-L tanks filled with fresh waste materials to compare the relative effectiveness of the two treatments. Tanks were prepared to provide the following conditions: (1) air injection and leachate recirculation (aerobic), (2) leachate recirculation (anaerobic), and (3) no treatment (anaerobic). Respiration tests on the aerobic wet tank showed a steady decrease in oxygen consumption rates from 1.3 mol/day at 20 days to 0.1 mol/day at 400 days. Aerobic wet tanks produced, on average, 6 mol of carbon dioxide (CO₂)/kg of MSW as compared with anaerobic wet tanks, which produced 2.2 mol methane/kg of MSW and 2.0 mol CO₂/kg methane. Over the test period, the aerobic tanks settled on average 35%, anaerobic tanks settled 21.7%, and the no-treatment tank settled 7.5%, equivalent to overall mass loss in the corresponding reactors. Aerobic tanks reduced stabilization time and produced negligible odor compared with anaerobic tanks, possibly because of the 2 orders of magnitude lower leachate ammonia levels in the aerobic tank. Both treatment regimes provide the opportunity for disposal and remediation of liquid waste.     

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.     

Evaluation of Vegetation Near Coal-burning Power Plants in Southwestern Pennsylvania. II. Ozone Injury on Foliage of Hybrid Poplar

The objective of this study was to determine if the incidence or severity of foliar injury induced by regional, ambient ozone was influenced by local emissions from a complex of coal-burning power plants in southwestern Pennsylvania. Plantings of an ozonesensitive hybrid poplar clone {Populus maximowizii x trichocarpa, clone NE 388) were established in 1972 at various distances and directions from the power plants. Foliar injury caused by ambient ozone was evaluated annually from 1973 to 1990 in early to mid- August. Data are presented for the 12-year period, 1979 to 1990 inclusive, for which the most complete data sets were available. Injury from ambient ozone varied spatially and temporally, but with little relationship to power plant location. There was an apparent negative relationship between emission trends and ozone-induced symptoms, but only for one power plant. The correlation between annual mean levels of ozone-induced stipple and frequency of days (per year) with a 1-hr ozone maximum exceeding 0.04 ppm was weak, but significant. Ozone-induced bifacial necrosis was not observed on the foliage of the hybrid poplar during the drought year of 1988 in spite of record high levels of ozone; however, ozoneinduced stipple was observed.     

IAPCS: A Computer Model that Evaluates Pollution Control Systems for Utility Boilers

The IAPCS model, developed by U.S. EPA’s Air and Energy Engineering Research Laboratory and made available to the public through the National Technical Information Service, can be used by utility companies, architectural and engineering companies, and regulatory agencies at all levels of government to evaluate commercially available technologies for control of SO₂, NO_x, and particulate matter emissions from coal-fired utility boilers with respect to performance and cost. The model is considered to be a useful tool to compare alternative control strategies to be used by utilities to comply with the requirements of the CAA, and to evaluate the sensitivity of control costs with respect to many of the significant variables affecting costs.

To illustrate the use of the model for site-specific studies, the authors used the model to estimate control costs for SO₂ and NO_x control at Detroit Edison’s Monroe plant and two hypothetical plants under consideration and at three plants operated by New York State Electric and Gas Corporation. The economic and technical assumptions used to drive the model were those proposed by the utilities if cited, and if not cited, the model default values were used. The economic format and methodologies for costs cited in the Electric Power Research Institute’s Technical Assessment Guide are used in the IAPCS model. Depending on the specific conditions and assumptions for the cases evaluated, SO₂ control costs ranged from $417 to $3,159 per ton of SO₂ removed, and NO_x control costs ranged from $461 to $3,537 per ton of NO_x removed or reduced.