Furnace Sorbent Injection

Abstract

This paper summarizes information on the spatial and temporal variability of selected air toxics pollutants collected on a national basis primarily for a period encompassing 1990–2003. Spatial information on pollutant concentrations is characterized in terms of within-city and between-city variability. Temporal information is summarized as diurnal and seasonal variability and in multiyear trends. The information on variability is presented in the framework of a larger need for systematic documentation of information on air toxics pollutants to assess progress in air pollution control programs.     

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.     

A method of assessing air toxics concentrations in urban areas using mobile platform measurements

The objective of this paper is to demonstrate an approach to characterize the spatial variability in ambient air concentrations using mobile platform measurements. This approach may be useful for air toxics assessments in Environmental Justice applications, epidemiological studies, and environmental health risk assessments. In this study, we developed and applied a method to characterize air toxics concentrations in urban areas using results of the recently conducted field study in Wilmington, DE. Mobile measurements were collected over a 4- x 4-km area of downtown Wilmington for three components: formaldehyde (representative of volatile organic compounds and also photochemically reactive pollutants), aerosol size distribution (representing fine particulate matter), and water-soluble hexavalent chromium (representative of toxic metals). These measurements were,used to construct spatial and temporal distributions of air toxics in the area that show a very strong temporal variability, both diurnally and seasonally. An analysis of spatial variability indicates that all pollutants varied significantly by location, which suggests potential impact of local sources. From the comparison with measurements at the central monitoring site, we conclude that formaldehyde and fine particulates show a positive correlation with temperature, which could also be the reason that photochemically generated formaldehyde and fine particulates over the study area correlate well with the fine particulate matter measured at the central site.     

Temporal variability of selected air toxics in the United States

Ambient measurements of hazardous air pollutants (HAPs, air toxics) collected in the United States from 1990 to 2005 were analyzed for diurnal, seasonal, and/or annual variability and trends. Visual and statistical analyses were used to identify and quantify temporal variations in air toxics at national and regional levels. Sufficient data were available to analyze diurnal variability for 14 air toxics, seasonal variability for 24 air toxics, and annual trends for 26 air toxics. Four diurnal variation patterns were identified and labeled invariant, nighttime peak, morning peak, and daytime peak. Three distinct seasonal patterns were identified and labeled invariant, cool, and warm. Multiple air toxics showed consistent decreasing trends over three trend periods, 1990–2005, 1995–2005, and 2000–2005. Trends appeared to be relatively consistent within chemically similar pollutant groups. Hydrocarbons such as benzene, 1,3-butadiene, styrene, xylene, and toluene decreased by approximately 5% or more per year at more than half of all monitoring sites. Concentrations of carbonyl compounds such as formaldehyde, acetaldehyde, and propionaldehyde were equally likely to have increased or decreased at monitoring sites. Chlorinated volatile organic compounds (VOCs) such as tetrachloroethylene, dichloromethane, and methyl chloroform decreased at more than half of all monitoring sites, but decreases among these species were much more variable than among the hydrocarbons. Lead particles decreased in concentration at most monitoring sites, but trends in other metals were not consistent over time.     

Analysis of air toxics emission inventory: inhalation toxicity-based ranking

Air toxics emission inventories play an important role in air quality regulatory activities. Recently, Minnesota Pollution Control Agency (MPCA) staff compiled a comprehensive air toxics emission inventory for 1996. While acquiring data on the mass of emissions is a necessary first step, equally important is developing information on the potential toxicity of the emitted pollutants. To account for the toxicity of the pollutants in the emission inventory, inhalation health benchmarks for acute effects, chronic effects, and cancer were used to weight the mass of emissions. The 1996 Minnesota emissions inventory results were ranked by mass of emissions and by an index comprised of emissions divided by health benchmarks. The results show that six of eight pollutants ranked highest by toxicity were also the pollutants of concern indicated in environmental monitoring data and modeling data. Monitoring data and modeling results did not show high impacts of the other two pollutants that were identified by the toxicity-based emission ranking method. The biggest limitation in this method is the lack of health benchmark values for many pollutants. Despite uncertainties and limited information, this analysis provides useful information for further targeting pollutants and source categories for control.     

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.     

Sampling frequency guidance for ambient air toxics monitoring

The U.S. Environmental Protection Agency (EPA) is in the process of designing a national network to monitor hazardous air pollutants (HAPs), also known as air toxics. The purposes of the expanded monitoring are to (1) characterize ambient concentrations in representative areas; (2) provide data to support and evaluate dispersion and receptor models; and (3) establish trends and evaluate the effectiveness of HAP emission reduction strategies. Existing air toxics data, in the form of an archive compiled by EPA's Office of Air Quality Planning and Standards (OAQPS), are used in this paper to examine the relationship between estimated annual average (AA) HAP concentrations and their associated variability. The goal is to assess the accuracy, or bias and precision, with which the AA can be estimated as a function of ambient concentration levels and sampling frequency. The results suggest that, for several air toxics, a sampling schedule of 1 in 3 days (1:3) or 1:6 days maybe appropriate for meeting some of the general objectives of the national network, with the more intense sampling rate being recommended for areas expected to exhibit relatively high ambient levels.     

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.     

Sampling Frequency Guidance for Ambient Air Toxics Monitoring

Abstract

The U.S. Environmental Protection Agency (EPA) is in the process of designing a national network to monitor hazardous air pollutants (HAPs), also known as air toxics. The purposes of the expanded monitoring are to (1) characterize ambient concentrations in representative areas; (2) provide data to support and evaluate dispersion and receptor models; and (3) establish trends and evaluate the effectiveness of HAP emission reduction strategies. Existing air toxics data, in the form of an archive compiled by EPA’s Office of Air Quality Planning and Standards (OAQPS), are used in this paper to examine the relationship between estimated annual average (AA) HAP concentrations and their associated variability. The goal is to assess the accuracy, or bias and precision, with which the AA can be estimated as a function of ambient concentration levels and sampling frequency. The results suggest that, for several air toxics, a sampling schedule of 1 in 3 days (1:3) or 1:6 days may be appropriate for meeting some of the general objectives of the national network, with the more intense sampling rate being recommended for areas expected to exhibit relatively high ambient levels.     

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.     

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.     

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.     

Air toxics in Canada measured by the National Air Pollution Surveillance (NAPS) program and their relation to ambient air quality guidelines

This study reports ambient concentrations of 63 air toxics that were measured in Canada by the National Air Pollution Surveillance (NAPS) program over the period 2009–2013. Measured concentrations are compared with ambient air quality guidelines from Canadian jurisdictions, and compounds that exceeded guidelines are identified and discussed. Although this study does not assess risk or cumulative effects, air toxics that approached guidelines are also identified so that their potential contribution to ambient air toxics pollution can be considered. Eleven air toxics exceeded at least one guideline, and an additional 16 approached guidelines during the study period. Four compounds were measured using methods whose detection limits exceeded a guideline value, three of which could not be compared with guidelines, since they were not detected in any samples. The assessment of several metal(loid) concentrations is tentative, since they were measured only in fine particulate matter (PM) but compared with guidelines based on coarse or total PM. Improvements to sampling and analysis techniques for the latter compounds as well as for those whose methods are subject to known uncertainties would improve confidence in reported concentrations and their relation to applicable guidelines. Analysis of sampling strategies for all compounds found to exceed or approach guidelines would contribute to ensuring that their spatiotemporal coverage is adequate. Examination of the air toxics not measured by NAPS but having guidelines in Canadian jurisdictions or being included in other programs such as the U.S. National-Scale Air Toxics Assessment (NATA) would contribute to ensuring that the full suite of pollutants relevant to ambient air quality in Canada is subject to adequate study. The results of this study can be applied to evaluating the effectiveness of toxic substances management in Canada.

Implications: Recent measurements of 63 air toxics in Canada by the National Air Pollution Surveillance (NAPS) program showed that 11 compounds exceeded daily or annual ambient air quality guidelines and that an additional 16 compounds approached such guidelines within an order of magnitude. The results of this study can be applied to evaluating the effectiveness of toxic substances management in Canada and to identifying compounds that merit further investigation.     

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.     

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.     

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.     

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.     

Applicability of the Mass Concentration Standards for Particulate Matter in Alaskan Areas

The so-called “Six Month Study” of the air toxics problem in the United States was initiated in November 1983 by the U.S. Environmental Protection Agency. The study focused on the magnitude, nature, and distribution of the problem—three major issues that were felt to be most useful to policy makers as they attempted to define the scope and direction of a national program for controlling toxic air pollutants. The following paper is based on a draft staff report on the study released for review in September 1984. The report has not been formally released by the U.S. EPA; a final report is due by late spring of 1985.     

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%.     

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.