Spatial Variation in Acidic Sulfate and Ammonia Concentrations within Metropolitan Philadelphia

Abstract

Acidic sulfate concentrations were measured in metropolitan Philadelphia during the summers of 1992 and 1993, as part of a continuing effort to characterize particle concentrations in urban environments. Sampling was performed simultaneously at eight sites located within and around metropolitan Philadelphia. Sites were selected based on their population density and on their distance and direction from the city center. Air pollution sampling was conducted every other day during the summer of 1992 and every day during the summer of 1993. All samples were collected for 24-h periods beginning at 9 a.m. (EDT). All acidic sulfate and ammonia samples were collected using modified Harvard-EPA Annular Denuder Systems (HEADS).

In this paper, we examine the spatial variation in acidic sulfate and ammonia concentrations within the metropolitan Philadelphia area. We also identify factors that may influence their variation and develop models to predict their concentrations. Outdoor sulfate (SO₄ ^2?) concentrations were uniform within metropolitan Philadelphia; however, aerosol strong acidity (H⁺) concentrations varied spatially. This variation generally was independent of wind direction, but was related to local factors, such as the NH₃ concentration, population density, and distance from the center of the city. Physico-chemical models, which were developed using data collected during the summer of 1992, were excellent predictors of 24-h and mean summertime H⁺ concentrations measured during the summer of 1993. Models accounted for 78% of the variation in 24-h H⁺ levels. Results suggest that a single stationary ambient (SAM) monitor would be sufficient to estimate SO₄ ^2? exposures for populations living in Philadelphia. For H⁺, however, multiple monitoring sites or models should be used to determine the outdoor H+ exposures of populations living in urban environments, although a single SAM site may provide an excellent index of H⁺ variation over time.     

Limestone Dissolution in Flue Gas Scrubbing: Effect of Sulfite

Batch limestone dissolution experiments were carried out in a pH stat apparatus at 55°C with CO2 sparging and dissolved sulfite. Particle size distribution, utilization, sulfite in solution, limestone type, and the approach to calcite equilibrium were all found to contribute to the limestone reactivity. In the absence of sulfite, limestone dissolution was controlled solely by mass transfer. For a given stone under mass transfer control, film thickness was found to be independent of pH. The dissolution rate in the presence of sulfite was controlled by a combined surface kinetics/mass transfer regime. SEM micrographs supported this conclusion. A surface rate correlation was developed which accounted for observed inhibition by an inverse dependence on calcium sulfite concentration at the limestone surface. While the form of the rate expression was applicable to all stones, the surface rate constant was stone dependent. A computer code which accounted for mass transfer with surface kinetics was tested against experimental observations of four limestone types. Changes in pH and the concentrations of calcium, carbonate, sulfite, sulfate, and adipic acid were accurately modeled.     

Solvent Extraction Processes: A Survey of Systems in the SITE Program

Solvent extraction of contaminated soils, sludges and sediments has been successfully completed at a number of Superfund sites. Each commercialized process uses a unique operating system to extract organic contaminants from solids. These operating systems may be classified by the properties of the solvents each utilizes: (1) standard solvents, (2) near-critical fluids/liquified gases, and (3) critical solution temperature solvents. Pretreatment and post-treatment requirements vary depending upon the operating systems of the solvent extraction system. Future demonstrations of these technologies by the U.S. EPA’s Superfund Innovative Technology Evaluation Program will provide additional information regarding the efficacy of these processes.     

Ozone Control Strategies Based on the Ratio of Volatile Organic Compounds to Nitrogen Oxides

The 1990 Clean Air Act Amendments require states with O₃ nonattainment areas to adopt regulations to enforce reasonable available control technologies (RACT) for NO_X stationary sources by November 1992. However, if the states can demonstrate that such measures will have an adverse effect on air quality, NO_X requirements may be waived. To assist the states in making this decision, the U.S. EPA is attempting to develop guidelines for the states to use in deciding whether NO_X reductions will have a positive or negative impact on O3 air quality. Although NO_X is a precursor of O₃, at low VOC/NO_X ratios, the reduction of NO_X can result in increased peak O₃. EPA is examining existing information on VOC/NO_X ratios to develop “rules of thumb” to guide the states in their decision-making process. An examination of 6 a.m. to 9 a.m. VOC/NO_X ratios at a number of sites in the eastern U.S. indicates that the ratio is highly variable from day-to-day and there is no apparent relationship between ratios measured at different sites within the same area. In addition, statistical analysis failed to identify significant relationships between the 6 a.m. to 9 a.m. VOC/NO_X ratio and the maximum 1-hr. O₃ within a given area. Since we know from smog chamber and modeling studies that such a relationship exists, this further invalidates the assumption that a ratio measured at a single site is representative of the ratio for the entire region. Based on this Information, we conclude that having the 6 a.m. to 9 a.m. ambient VOC/NO_X ratio for a given area is insufficient information, by itself, to decide whether a VOC-alone, a NO_x-alone, or a combined VOC-NO_X reduction strategy is a viable or optimum O₃-reduction strategy.     

The Potential of Pulse-Jet Baghouses for Utility Boilers. Part 2: Performance of Pulse-Jet Fabric Filter Pilot Plants

Pulse-jet fabric filters (PJFFs) are widely used in U.S. industrial boiler applications and in utility and industrial boilers abroad. Their small size and reduced cost relative to more conventional reverse-gas baghouses makes the use of PJFFs appear to be an attractive particulate control option for utility boilers. This paper (Part 2 of a three-part series) summarizes the results of pilot PJFF studies sponsored by the Electric Power Research Institute at different utility sites in the United States. The purpose of these tests is to evaluate PJFF performance for U.S. fossil-fuel-fired applications. These data are also used to corroborate the results of a recent worldwide survey of PJFF user experience, as described in Part 1 of this series. Part 3 will provide a cost comparison of PJFFs to other particulate control options such as electrostatic precipitators and reverse-gas baghouses.     

Controlled Enrichment System for Experimental Fumigation of Plants in the Field with Sulfur Dioxide

A prototype Free-Air Controlled Enrichment (FACE) system was developed at Brookhaven National "Laboratory (BNL) for the experimental control of gas concentrations in an open field, without any form of enclosure. This FACE system consists of a toroidal plenum chamber, 15 m in diameter, with a series of 32 vertical vent pipes from which the release of a test gas can be controlled. Data on gas concentration at the center of the array and wind velocity are fed to a microprocessor where a proportional, integrative, differential (PID) algorithm is used to regulate a mass-flow controller. Data on wind direction are used to control the opening and closing of the vertical vent pipes to maintain an upwind release. In 72 hours of continuous operation during which wind velocity varied between 0.3 to 8 m sec^-1, the FACE prototype maintained 1 -min averaged concentrations within twenty percent of the 40 ppb set point 94 percent of the time.     

Flow Injection Analysis of MWC Fly Ash Leaching Characteristics

Abstract

A completely mixed batch reactor leaching method utilizing flow injection analysis (the CMBR-FIA method) was developed to study the lead leaching characteristics of municipal waste combustor fly ash. Flow injection analysis (FIA) coupled with atomic absorption spectrophotometry enabled the determination of lead concentrations at one minute intervals. The pH and oxidation-reduction potential of the solution were continuously monitored to characterize the leaching conditions. Automatic titration was used to alter the solution pH to defined endpoints. The CMBR-FIA method offers the ability to immediately observe alterations to the leaching solution, and grants the freedom to study a number of parameters concurrently. The CMBR-FIA method is a rapid and reliable means to investigate leaching characteristics. This paper describes the method and demonstrates its use to monitor the leaching of lead from municipal solid waste combustor fly ash as a function of pH. Soluble lead concentrations are shown to increase quickly with decreasing pH.

A maximum of 50% of the total lead concentration was available in solution at pH 2. This value gradually decreased with time to over 35% of the total.     

Controlled Exposures of Volunteers to Respirable Carbon and Sulf uric Acid Aerosols

Respirable carbon or fly ash particles are suspected to increase the respiratory toxicity of coexisting acidic air pollutants, by concentrating acid on their surfaces and so delivering it efficiently to the lower respiratory tract. To investigate this issue, we exposed 15 healthy and 15 asthmatic volunteers in a controlled- environment chamber (21°C, 50 percent relative humidity) to four test atmospheres: (i) clean air; (ii) 0.5-μm H2SO4 aerosol at =100 μg/m³, generated from water solution; (iii) 0,5-μm carbon aerosol at =250 μg/m³, generated from highly pure carbon black with specific surface area comparable to ambient pollution particles; and (iv) carbon as in (iii) plus =100 μg/m³ of ultrafine H2SO4 aerosol generated from fuming sulfuric acid. Electron microscopy showed that nearly all acid in (iv) became attached to carbon particle surfaces, and that most particles remained in the sub-μm size range. Exposures were performed double-blind, 1 week apart. They lasted 1 hr each, with alternate 10-min periods of heavy exercise (ventilation =50 L/min) and rest. Subjects gargled citrus juice before exposure to suppress airway ammonia. Lung function and symptoms were measured pre-exposure, after initial exercise, and at endexposure. Bronchial reactivity to methacholine was measured after exposure. Statistical analyses tested for effects of H₂SO₄ or carbon, separate or interactive, on health measures. Group data showed no more than small equivocal effects of any exposure on any health measure. One individual's responses were consistent with a clinically significant excess airway constriction from H₂SO₄ plus carbon, and 2-3 others showed slight excess responses to the combined pollutants, but all these observations might have reflected chance variations. We conclude that coexisting carbon aerosol did not increase respiratory irritancy of H₂SO₄, in most healthy and asthmatic subjects exposed for 1 hr under simulated "worst-case" ambient conditions.     

Rotary Kiln Incineration of Dichloromethane and Xylene: A Comparison of Incinerability Characteristics Under Various Operating Conditions

Comparisons are made, for the first time, between the combustion characteristics of dichloromethane and xylene in an industrial rotary kiln incinerator. The comparisons are made under different operating conditions, including variable kiln rotation rate and operation both with and without turbulence air. Continuous gas composition and temperature measurements and batch gas composition measurements were obtained from two vertical locations hear the exit region of the rotary kiln. The measurements show that there is significant vertical stratification at the exit of the kiln. Addition of turbulence air enhanced combustion conditions throughout the kiln during xylene processing. During dichloromethane processing, however, the addition of turbulence air had minimal effect and only promoted greater bulk mixing; chlorinated compounds transported from the lower kiln during operation with turbulence air were not efficiently processed in the upper kiln. Evolution of test liquids from the bed was not constant but rather was characterized by intermittent peaks. The field-scale data of this work suggest that the evolution rate of the test liquid was increased as kiln rotation rate increased. Many of the differences between xylene and dichloromethane processing during these experiments are explained by a simple stoichiometric analysis.     

Economic Benefits of Improvements in Visibility: Acid Rain Provisions of the 1990 Clean Air Act Amendments

The Acid Rain Provisions (Title IV) of the Clean Air Act Amendments of 1990 call for about a 10 million ton reduction in annual SO₂ emissions in the United States. Although the provisions apply nationwide, most of the reduction will occur in the eastern half of the country, where use of high-sulfur coal for electricity generation is most common. One potentially large benefit of Title IV is the expected improvement in visibility conditions in the eastern United States due to the reductions in secondary sul-fate aerosols. This paper combines available economic estimates of willingness to pay for improvements in visibility with current estimates of the difference between expected visibility conditions in the eastern United States with and without Title I V, to estimate the expected visibility benefits of Title IV. The results suggest an annual value of $2.3 billion (in 1994 dollars) in the year 2010, as a result of visibility improvements due to Title IV in residential areas of the eastern United States. The results also suggest a possible additional annual value for eastern U.S. residents of as much as $1-2 billion for visibility improvements at national parks in the Southeast.