An analysis of candidates for addition to the Clean Air Act list of hazardous air pollutants

There are 188 air toxics listed as hazardous air pollutants (HAPs) in the Clean Air Act (CAA), based on their potential to adversely impact public health. This paper presents several analyses performed to screen potential candidates for addition to the HAPs list. We analyzed 1086 HAPs and potential HAPs, including chemicals regulated by the state of California or with emissions reported to the Toxics Release Inventory (TRI). HAPs and potential HAPs were ranked by their emissions to air, and by toxicity-weighted (tox-wtd) emissions for cancer and noncancer, using emissions information from the TRI and toxicity information from state and federal agencies. Separate consideration was given for persistent, bioaccumulative toxins (PBTs), reproductive or developmental toxins, and chemicals under evaluation for regulation as toxic air contaminants in California. Forty-four pollutants were identified as candidate HAPs based on three ranking analyses and whether they were a PBT or a reproductive or developmental toxin. Of these, nine qualified in two or three different rankings (ammonia [NH3], copper [Cu], Cu compounds, nitric acid [HNO3], N-methyl-2-pyrrolidone, sulfuric acid [H2SO4], vanadium [V] compounds, zinc [Zn], and Zn compounds). This analysis suggests further evaluation of several pollutants for possible addition to the CAA list of HAPs.     

National estimates of outdoor air toxics concentrations

The Clean Air Act identifies 189 hazardous air pollutants (HAPs), or "air toxics," associated with a wide range of adverse human health effects. The U.S. Environmental Protection Agency has conducted a modeling study with the Assessment System for Population Exposure Nationwide (ASPEN) to gain a greater understanding of the spatial distribution of concentrations of these HAPs resulting from contributions of multiple emission sources. The study estimates year 1990 long-term outdoor concentrations of 148 air toxics for each census tract in the continental United States, utilizing a Gaussian air dispersion modeling approach. Ratios of median national modeled concentrations to estimated emissions indicate that emission totals without consideration of emission source type can be a misleading indicator of air quality. The results also indicate priorities for improvements in modeling methodology and emissions identification. Model performance evaluation suggests a tendency for underprediction of observed concentrations, which is likely due, at least in part, to a number of limitations of the Gaussian modeling formulation. Emissions estimates for HAPs have a high degree of uncertainty and contribute to discrepancies between modeled and monitored concentration estimates. The model's ranking of concentrations among monitoring sites is reasonably good for most of the gaseous HAPs evaluated, with ranking accuracy ranging from 66 to 100%.     

Development of a speciated, hourly, and gridded air pollutants emission modeling system--a case study on the precursors of photochemical smog in the Seoul metropolitan area, Korea

A speciated, hourly, and gridded air pollutants emission modeling system (SHEMS) was developed and applied in predicting hourly nitrogen dioxide (NO2) and ozone (O3) levels in the Seoul Metropolitan Area (SMA). The primary goal of the SHEMS was to produce a systemized emission inventory for air pollutants including ozone precursors for modeling air quality in urban areas. The SHEMS is principally composed of three parts: (1) a pre-processor to process emission factors, activity levels, and spatial and temporal information using a geographical information system; (2) an emission model for each source type; and (3) a post-processor to produce report and input data for air quality models through database modeling. The source categories in SHEMS are point, area, mobile, natural, and other sources such as fugitive emissions. The emission database produced by SHEMS contains 22 inventoried compounds: sulfur dioxide, NO2, carbon monoxide, and 19 speciated volatile organic compounds. To validate SHEMS, the emission data were tested with the Urban Airshed Model to predict NO2 and O3 concentrations in the SMA during selected episode days in 1994. The results turned out to be reliable in describing temporal variation and spatial distribution of those pollutants.     

Emission factors of air toxics from semiconductor manufacturing in Korea

The development of local, accurate emission factors is very important for the estimation of reliable national emissions and air quality management. For that, this study is performed for pollutants released to the atmosphere with source-specific emission tests from the semiconductor manufacturing industry. The semiconductor manufacturing industry is one of the major sources of air toxics or hazardous air pollutants (HAPs); thus, understanding the emission characteristics of the emission source is a very important factor in the development of a control strategy. However, in Korea, there is a general lack of information available on air emissions from the semiconductor industry. The major emission sources of air toxics examined from the semiconductor manufacturing industry were wet chemical stations, coating applications, gaseous operations, photolithography, and miscellaneous devices in the wafer fabrication and semiconductor packaging processes. In this study, analyses of emission characteristics, and the estimations of emission data and factors for air toxics, such as acids, bases, heavy metals, and volatile organic compounds from the semiconductor manufacturing process have been performed. The concentration of hydrogen chloride from the packaging process was the highest among all of the processes. In addition, the emission factor of total volatile organic compounds (TVOCs) for the packaging process was higher than that of the wafer fabrication process. Emission factors estimated in this study were compared with those of Taiwan for evaluation, and they were found to be of similar level in the case of TVOCs and fluorine compounds.     

Emission Factors of Air Toxics from Semiconductor Manufacturing in Korea

Abstract

The development of local, accurate emission factors is very important for the estimation of reliable national emissions and air quality management. For that, this study is performed for pollutants released to the atmosphere with source-specific emission tests from the semiconductor manufacturing industry. The semiconductor manufacturing industry is one of the major sources of air toxics or hazardous air pollutants (HAPs); thus, understanding the emission characteristics of the emission source is a very important factor in the development of a control strategy. However, in Korea, there is a general lack of information available on air emissions from the semiconductor industry. The major emission sources of air toxics examined from the semiconductor manufacturing industry were wet chemical stations, coating applications, gaseous operations, photolithography, and miscellaneous devices in the wafer fabrication and semiconductor packaging processes. In this study, analyses of emission characteristics, and the estimations of emission data and factors for air toxics, such as acids, bases, heavy metals, and volatile organic compounds from the semiconductor manufacturing process have been performed. The concentration of hydrogen chloride from the packaging process was the highest among all of the processes. In addition, the emission factor of total volatile organic compounds (TVOCs) for the packaging process was higher than that of the wafer fabrication process. Emission factors estimated in this study were compared with those of Taiwan for evaluation, and they were found to be of similar level in the case of TVOCs and fluorine compounds.     

Air pollutant emissions associated with forest,grassland, and agricultural burning in Texas

Outdoor fires, such as wildfires and prescribed burns, can emit substantial amounts of particulate matter and other pollutants into the atmosphere. In Texas, an inventory of forest, grassland and agricultural burning activities revealed that fires consumed vegetation on 1.6 and 1.7 million acres of land, in 1996 and 1997, respectively. Emissions from the fires were estimated based on survey and field data on acres burned and land cover and literature data on fuel consumption and emission factors. Fire data were allocated spatially by county and temporally by month. While fire events can cause high transient air pollutant concentrations, for most criteria pollutants, the fire emissions were a relatively small fraction of the annual emission inventory for the State. For fine particulate matter, however, the annual emission estimates were 40,000 tons/yr, which is likely to represent a significant fraction of the State's emission inventory, especially in the counties where the emissions are concentrated.     

Resolving local-scale emissions for modeling air quality near roadways

A large body of literature published in recent years suggests increased health risk due to exposure of people to air pollution in close proximity to roadways. As a result, there is a need to more accurately represent the spatial concentration gradients near roadways to develop mitigation strategies. In this paper, we present a practical, readily adaptable methodology, using a "bottom-up" approach to develop a detailed highway vehicle emission inventory that includes emissions for individual road links. This methodology also takes advantage of geographic information system (GIS) software to improve the spatial accuracy of the activity information obtained from a Travel Demand Model. In addition, we present an air quality modeling application of this methodology in New Haven, CT. This application uses a hybrid modeling approach, in which a regional grid-based model is used to characterize average local ambient concentrations, and a Gaussian dispersion model is used to provide texture within the modeling domain because of spatial gradients associated with highway vehicle emissions and other local sources. Modeling results show substantial heterogeneity of pollutant concentrations within the modeling domain and strong spatial gradients associated with roadways, particularly for pollutants dominated by direct emissions.     

Development of a Speciated,Hourly, and Gridded Air Pollutants Emission Modeling System—A Case Study on the Precursors of Photochemical Smog in the Seoul Metropolitan Area,Korea

ABSTRACT

A speciated, hourly, and gridded air pollutants emission modeling system (SHEMS) was developed and applied in predicting hourly nitrogen dioxide (NO₂) and ozone (O₃) levels in the Seoul Metropolitan Area (SMA). The primary goal of the SHEMS was to produce a systemized emission inventory for air pollutants including ozone precursors for modeling air quality in urban areas.

The SHEMS is principally composed of three parts: (1) a pre-processor to process emission factors, activity levels, and spatial and temporal information using a geographical information system; (2) an emission model for each source type; and (3) a post-processor to produce report and input data for air quality models through database modeling. The source categories in SHEMS are point, area, mobile, natural, and other sources such as fugitive emissions. The emission database produced by SHEMS contains 22 inventoried compounds: sulfur dioxide, NO₂, carbon monoxide, and 19 speciated volatile organic compounds. To validate SHEMS, the emission data were tested with the Urban Airshed Model to predict NO₂ and O₃ concentrations in the SMA during selected episode days in 1994. The results turned out to be reliable in describing temporal variation and spatial distribution of those pollutants.     

Traffic and Meteorological Impacts on Near-Road Air Quality: Summary of Methods and Trends from the Raleigh Near-Road Study

Abstract

A growing number of epidemiological studies conducted worldwide suggest an increase in the occurrence of adverse health effects in populations living, working, or going to school near major roadways. A study was designed to assess traffic emissions impacts on air quality and particle toxicity near a heavily traveled highway. In an attempt to describe the complex mixture of pollutants and atmospheric transport mechanisms affecting pollutant dispersion in this near-highway environment, several real-time and time-integrated sampling devices measured air quality concentrations at multiple distances and heights from the road. Pollutants analyzed included U.S. Environmental Protection Agency (EPA)-regulated gases, particulate matter (coarse, fine, and ultrafine), and air toxics. Pollutant measurements were synchronized with real-time traffic and meteorological monitoring devices to provide continuous and integrated assessments of the variation of near-road air pollutant concentrations and particle toxicity with changing traffic and environmental conditions, as well as distance from the road. Measurement results demonstrated the temporal and spatial impact of traffic emissions on near-road air quality. The distribution of mobile source emitted gas and particulate pollutants under all wind and traffic conditions indicated a higher proportion of elevated concentrations near the road, suggesting elevated exposures for populations spending significant amounts of time in this microenvironment. Diurnal variations in pollutant concentrations also demonstrated the impact of traffic activity and meteorology on near-road air quality. Time-resolved measurements of multiple pollutants demonstrated that traffic emissions produced a complex mixture of criteria and air toxic pollutants in this microenvironment. These results provide a foundation for future assessments of these data to identify the relationship of traffic activity and meteorology on air quality concentrations and population exposures.     

Traffic and meteorological impacts on near-road air quality: summary of methods and trends from the Raleigh Near-Road Study

A growing number of epidemiological studies conducted worldwide suggest an increase in the occurrence of adverse health effects in populations living, working, or going to school near major roadways. A study was designed to assess traffic emissions impacts on air quality and particle toxicity near a heavily traveled highway. In an attempt to describe the complex mixture of pollutants and atmospheric transport mechanisms affecting pollutant dispersion in this near-highway environment, several real-time and time-integrated sampling devices measured air quality concentrations at multiple distances and heights from the road. Pollutants analyzed included U.S. Environmental Protection Agency (EPA)-regulated gases, particulate matter (coarse, fine, and ultrafine), and air toxics. Pollutant measurements were synchronized with real-time traffic and meteorological monitoring devices to provide continuous and integrated assessments of the variation of near-road air pollutant concentrations and particle toxicity with changing traffic and environmental conditions, as well as distance from the road. Measurement results demonstrated the temporal and spatial impact of traffic emissions on near-road air quality. The distribution of mobile source emitted gas and particulate pollutants under all wind and traffic conditions indicated a higher proportion of elevated concentrations near the road, suggesting elevated exposures for populations spending significant amounts of time in this microenvironment. Diurnal variations in pollutant concentrations also demonstrated the impact of traffic activity and meteorology on near-road air quality. Time-resolved measurements of multiple pollutants demonstrated that traffic emissions produced a complex mixture of criteria and air toxic pollutants in this microenvironment. These results provide a foundation for future assessments of these data to identify the relationship of traffic activity and meteorology on air quality concentrations and population exposures.     

High time-resolved measurements of organic air toxics in different source regimes

High time-resolved (HTR) measurements can provide significant insight into sources and exposures of air pollution. In this study, an automated instrument was developed and deployed to measure hourly concentrations of 18 gas-phase organic air toxics and 6 volatile organic compounds (VOCs) at three sites in and around Pittsburgh, Pennsylvania. The sites represent different source regimes: a site with substantial mobile-source emissions; a residential site adjacent to a heavily industrialized zone; and an urban background site. Despite the close proximity of the sites (less than 13 km apart), the temporal characteristic of outdoor concentrations varied widely. Most of the compounds measured were characterized by short periods of elevated concentrations or plume events, but the duration, magnitude and composition of these events varied from site to site. The HTR data underscored the strong role of emissions from local sources on exposure to most air toxics. Plume events contributed more than 50% of the study average concentrations for all pollutants except chloroform, 1,2-dichloroethane, and carbon tetrachloride. Wind directional dependence of air toxic concentrations revealed that emissions from large industrial facilities affected concentrations at all of the sites. Diurnal patterns and weekend/weekday variations indicated the effects of the mixing layer, point source emissions patterns, and mobile source air toxics (MSATs) on concentrations. Concentrations of many air toxics were temporally correlated, especially MSATs, indicating that they are likely co-emitted. It was also shown that correlations of the HTR data were greater than lower time resolution data (24-h measurements). This difference was most pronounced for the chlorinated pollutants. The stronger correlations in HTR measurements underscore their value for source apportionment studies.     

Sources of variability in ambient air toxics monitoring data

Under the Clean Air Act Amendments, the United States Environmental Protection Agency is required to regulate emissions of 188 hazardous air pollutants. The EPA, Office of Air Quality Planning and Standards is currently conducting a National-scale Air Toxics Assessment with a goal to identify air toxics which are of greatest concern, in terms of contribution to population inhalation risk. The results will be used to set priorities for the collection of additional air toxics emissions and monitoring data. Expanded ambient air toxics monitoring will take the form of a national air toxics monitoring network. With all monitoring data, however, comes uncertainty in the form of environmental variability (spatial and temporal) and monitoring error (sample collection and laboratory analysis). With this in mind, existing data from the Urban Air Toxics Monitoring Program (UATMP) were analyzed to obtain a general understanding of these sources of variability and then provide recommendations for managing the data uncertainties of a national network. The results indicate that environmental variability, in particular temporal, comprises most of the overall variability observed in the UATMP data. However, at lower ambient levels (on the order of 0.1–0.5 ppbv or lower) environmental variability tends to dissipate and monitoring error takes over, most notably analytical error. Overall, the results suggest that common techniques in ambient air toxics monitoring for carbonyls and volatile organic compounds may satisfy many of the primary objectives of a national air toxics monitoring network.     

Improved spatial allocation methodology for on-road mobile emissions

Emissions from automobiles and trucks operating on public roads represent a major portion of the air pollutants included in emission inventories. When emission data are prepared for air quality modeling studies, such as those supporting development of a State Implementation Plan, an emission processor matches the spatial and temporal resolution of the emissions to the requirements of the modeling study. However, the spatial location of vehicular emissions is not known and must be estimated. This paper presents a methodology for determining the spatial distribution of the roads belonging to a road class using geospatial data functions, such as those commonly provided by a geographic information system. Vehicle-miles traveled (VMT) are then allocated to medium-resolution (12 x 12-km) and fine-resolution (4 x 4-km) modeling grids using both this methodology and the existing top-down methodology, which uses population density. The results show a significant difference in the spatial distribution of VMT between these two methodologies. Based upon these results, we recommend using the road class-specific methodology in lieu of the population methodology for spatially allocating vehicular emissions for medium- and finer-resolution modeling grids.     

Improved Spatial Allocation Methodology for On-Road Mobile Emissions

ABSTRACT

Emissions from automobiles and trucks operating on public roads represent a major portion of the air pollutants included in emission inventories. When emission data are prepared for air quality modeling studies, such as those supporting development of a State Implementation Plan, an emission processor matches the spatial and temporal resolution of the emissions to the requirements of the modeling study. However, the spatial location of vehicular emissions is not known and must be estimated. This paper presents a methodology for determining the spatial distribution of the roads belonging to a road class using geospatial data functions, such as those commonly provided by a geographic information system. Vehicle-miles traveled (VMT) are then allocated to medium-resolution (12 x 12-km) and fine-resolution (4 x 4-km) modeling grids using both this methodology and the existing top-down methodology, which uses population density. The results show a significant difference in the spatial distribution of VMT between these two methodologies. Based upon these results, we recommend using the road class-specific methodology in lieu of the population methodology for spatially allocating vehicular emissions for medium- and finer-resolution modeling grids.     

Impact of underestimating the effects of cold temperature on motor vehicle start emissions of air toxics in the United States

Analyses of U.S. Environmental Protection Agency (EPA) certification data, California Air Resources Board surveillance testing data, and EPA research testing data indicated that EPA's MOBILE6.2 emission factor model substantially underestimates emissions of gaseous air toxics occurring during vehicle starts at cold temperatures for light-duty vehicles and trucks meeting EPA Tier 1 and later standards. An unofficial version of the MOBILE6.2 model was created to account for these underestimates. When this unofficial version of the model was used to project emissions into the future, emissions increased by almost 100% by calendar year 2030, and estimated modeled ambient air toxics concentrations increased by 6-84%, depending on the pollutant. To address these elevated emissions, EPA recently finalized standards requiring reductions of emissions when engines start at cold temperatures.     

Emission of specific pollutants from a compression ignition engine. Influence of fuel hydrotreatment and fuel/air equivalence ratio

A compression ignition engine is used for the study of the fuel (one reference and one hydrotreated) and the fuel/air equivalence ratio influence on the exhaust emissions of specific pollutants. Under the experimental conditions used, seven hydrocarbons, nine aldehydes and three organic acids are detected in the exhaust gas. No alcohols are detected under these conditions, indicating that these compounds are emitted only if they (or probably other oxygenated compounds) are introduced in the fuel. Fuel hydrotreatment decreases most of the exhaust pollutants, the four toxics and also the quantity of the ozone that could be formed from the exhaust gas. It also changes the composition of exhaust gas: it increases the proportion of methane, benzene, formaldehyde, acetaldehyde, acroleine, and propionic acid, while it decreases the proportion of all other pollutants detected. Fuel/air equivalence ratio also decreases most of the exhaust emissions, the emission of the total toxics and the quantity of the ozone that could be formed. It also changes the proportion of each pollutant in exhaust gas: the percentages of methane, benzene, acetone and acetic acid increase, while those of the other pollutants detected decrease. The majority of the specific pollutants detected corresponds to organic acids, followed by hydrocarbons and aldehydes.     

Impact of three interactive Texas state regulatory programs to decrease ambient air toxic levels

The Federal Clean Air Act (FCAA) framework envisions a federal-state partnership whereby the development of regulations may be at the federal level or state level with federal oversight. The U.S. Environmental Protection Agency (EPA) establishes National Ambient Air Quality Standards to describe “safe” ambient levels of criteria pollutants. For air toxics, the EPA establishes control technology standards for the 187 listed hazardous air pollutants (HAPs) but does not establish ambient standards for HAPs or other air toxics. Thus, states must ensure that ambient concentrations are not at harmful levels. The Texas Clean Air Act authorizes the Texas Commission on Environmental Quality (TCEQ), the Texas state environmental agency, to control air pollution and protect public health and welfare. The TCEQ employs three interactive programs to ensure that concentrations of air toxics do not exceed levels of potential health concern (LOCs): air permitting, ambient air monitoring, and the Air Pollutant Watch List (APWL). Comprehensive air permit reviews involve the application of best available control technology for new and modified equipment and ensure that permits protect public health and welfare. Protectiveness may be demonstrated by a number of means, including a demonstration that the predicted ground-level concentrations for the permitted emissions, evaluated on a case-by-case and chemical-by-chemical basis, do not cause or contribute to a LOC. The TCEQ's ambient air monitoring program is extensive and provides data to help assess the potential for adverse effects from all operational equipment in an area. If air toxics are persistently monitored at a LOC, an APWL area is established. The purpose of the APWL is to reduce ambient air toxic concentrations below LOCs by focusing TCEQ resources and heightening awareness. This paper will discuss examples of decreases in air toxic levels in Houston and Corpus Christi, Texas, resulting from the interactive nature of these programs.

Implications: Texas recognized through the collection of ambient monitoring data that additional measures beyond federal regulations must be taken to ensure that public health is protected. Texas integrates comprehensive air permitting, extensive ambient air monitoring, and the Air Pollutant Watch List (APWL) to protect the public from hazardous air toxics. Texas issues air permits that are protective of public health and also assesses ambient air to verify that concentrations remain below levels of concern in heavily industrialized areas. Texas developed the APWL to improve air quality in those areas where monitoring indicates a potential concern. This paper illustrates how Texas engaged its three interactive programs to successfully address elevated air toxic levels in Houston and Corpus Christi.     

Innovative methods for emission inventory development and evaluation: workshop summary

Emission inventories are an essential tool for evaluating, managing, and regulating air pollution. Refinements and innovations in instruments that measure air pollutants, models that calculate emissions, and techniques for data management and uncertainty assessment are needed to enhance emission inventories. This workshop provided recommendations for improving emission factors, improving emission models, and reducing inventory uncertainty. Communication that increases cooperation between developers and users of inventories is essential. Emission inventories that incorporate these improvements will meet the challenges of the future.     

Air quality modeling of hazardous pollutants: current status and future directions

The current requirements and status of air quality modeling of hazardous pollutants are reviewed. Many applications require the ability to predict the local impacts from industrial sources or large roadways as needed for community health characterization and evaluating environmental justice concerns. Such local-scale modeling assessments can be performed by using Gaussian dispersion models. However, these models have a limited ability to handle chemical transformations. A new generation of Eulerian grid-based models is now capable of comprehensively treating transport and chemical transformations of air toxics. However, they typically have coarse spatial resolution, and their computational requirements increase dramatically with finer spatial resolution. The authors present and discuss possible advanced approaches that can combine the grid-based models with local-scale information.     

Biofiltration: an innovative air pollution control technology for VOC emissions

Biofiltration is a relatively recent air pollution control (APC) technology in which off-gases containing biodegradable volatile organic compounds (VOC) or inorganic air toxics are vented through a biologically active material. This technology has been successfully applied in Germany and The Netherlands in many full-scale applications to control odors, VOC and air toxic emissions from a wide range of industrial and public sector sources. Control efficiencies of more than 90 percent have been achieved for many common air pollutants. Due to lower operating costs, biofiltration can provide significant economic advantages over other APC technologies if applied to off-gases that contain readily biodegradable pollutants in low concentrations. Environmental benefits include low energy requirements and the avoidance of cross media transfer of pollutants. This paper reviews the history and current status of biofiltration, outlines its underlying scientific and engineering principles, and discusses the applicability of biofilters for a wide range of specific emission sources.