Comparison of the Annular Denuder System and the Transition Flow Reactor for Measurements of Selected Dry Deposition Species

An intensive field study was conducted in Research Triangle Park, North Carolina in the fall of 1986. Ambient concentrations of the following constituents were obtained: nitric acid, nitrous acid, nitrogen dioxide, sulfur dioxide, ammonia, hydrogen ion, and particulate nitrate, sulfate, and ammonium. Results collected using the annular denuder system (ADS) and the transition flow reactor (TFR) are presented and compared.

Both types of samplers had operational detection limits on daily (22-hour) samples that were generally below 1 μg m_-3 suggesting that both samplers can provide sensitive measurements for most of the constituents of interest. Both the ADS and TFR show reasonable (>25 percent) within-sampler precision for most of the measured species concentrations, except TFR fine particulate nitrate measurements where results were frequently negative (The TFR fine particulate nitrate measurement is calculated using subtraction of positive numbers).

Comparison of ADS and TFR daily results showed good agreement for total particulate sulfate, the sum of total (coarse plus fine) particulate and gaseous nitrate, and ammonia. As a result of different inlet particle collection efficiencies, the ADS fine particulate sulfate exceeded the TFR (5 percent). In the absence of a filter to collect volatilized particulate ammonium in the ADS, the sum of total particulate and gaseous ammonium in the TFR exceeded that in the ADS. Of potentially more importance, ADS measurements of SO₂ and H⁺ exceeded those of the TFR, while TFR measurements of HNO₃ exceeded those of the ADS. Results of this study suggest that the TFR may provide biased measurements of SO₂, H⁺, HNO₃, and Fine NO₃ ^- that cannot be corrected without modifications to the fundamental design of the sampling system.     

Validation of Models for Predicting Formaldehyde Concentrations in Residences due to Pressed-Wood Products

This paper describes a laboratory project to assess the accuracy of emission and indoor air quality models to be used in predicting formaldehyde (HCHO) concentrations in residences due to pressed-wood products made with urea-formaldehyde bonding resins. The products tested were partlcleboard underlayment, hardwood- plywood paneling and medium-density fiberboard (mdf). The products were initially characterized in chambers by measuring their formaldehyde surface emission rates over a range of formaldehyde concentrations, air exchange rates and two combinations of temperature and relative humidity (23° C and 5 0% RH; 26°C and 60% RH). They were then installed in a two-room prototype house in three different combinations (underlayment flooring only; underlayment flooring and paneling; and underlayment flooring, paneling, and mdf). The equilibrium formaldehyde concentrations were monitored as a function of air exchange rate. Particleboard underlayment and mdf, but not paneling, behaved as the emission model predicted over a large concentration range, under both sets of temperature and relative humidity. Good agreement was also obtained between measured formaldehyde concentrations and those predicted by a mass-balance indoor air quality model.     

Rotary Kiln Incineration II. Laboratory-Scale Desorption and Kiln-Simulator Studies—Solids

With landfill costs increasing and regulations on landfilling becoming more stringent, alternatives to conventional hazardous waste treatment strategies are becoming more desirable. Incineration Is presently a permanent, proven solution for the disposal of most organic contaminants, but also a costly one, especially in the case of solids which require some auxiliary fuel. The goal of this research is to develop an understanding of the phenomena associated with the evolution of contaminants from solids In the primary combustor of an Incineration system. A four-fold approach is being used. First, a bench-scale particle characterization reactor was developed to study the transport phenomena on a particle basis, where the controlling processes are mainly intraparticle. Second, a bed-characterization reactor was built to examine the controlling transport phenomena within a bed of particles, where the processes are primarily interparticle. The results of these studies can be applied to any primary combustor. A pilot-scale rotary kiln was developed to study the evolution of contaminants from solids within a realistic temperature and rotation environment. Finally, in situ measurements are being obtained from a full-scale rotary-kiln.

This paper describes results obtained in a study using a commercial sorbent contaminated with toluene. The data are from the particle-characterization reactor and the rotary-kiln simulator. The results show that the method of contamination and charge size do not have a large effect on desorption, while temperature and contaminant concentration are important parameters In the evolution of contaminants in a rotary kiln.     

A Management Systems Review of the Superfund RI/FS: Opportunities for Streamlining

The Management Systems Review is an important component of EPA’s quality assurance program. MSRs enable managers to assess the effectiveness of environmental data operations and the quality assurance/ quality control activities designed to ensure that the results are of the expected quality. These reviews inform managers about aspects of the environmental data operation that are working well and those which may warrant some improvement. A recent review of the Superfund remedial investigation/feasibility study (RI/FS) has shown that the MSR is an excellent tool for providing a systematic definition of complex environmental data operations and for enabling a thorough analysis of these operations. The MSR utilized information gathered from interviews of Regional staff and management and from case studies of recently completed RI/FSs. The findings indicated that environmental data play an important role in most RI/FS decisions and that thorough and structured scoping is critical to the effectiveness of the RI/ FS. Analysis of the RI/FS process using a comprehensive flow model identified several opportunities for changes that may increase efficiency in data collection and the reliability of RI/FS decisions. These changes provide for more effective scoping activities, a streamlined feasibility study, and increased use of treatability studies during the RI. A pilot demonstration of these process changes is being planned for a Regional RI/FS.     

An Evaluation of the Effects of Ozone Injury on Radial Growth of Ponderosa Pine (Pinus ponderosa) in the Southern Sierra Nevada

Growth of ponderosa pines with visible symptoms of ozone injury was compared with that of asymptomatic trees in the southern Sierra Nevada, California. Time series analysis indicated that there was no significant reduction in annual radial increment of symptomatic trees during recent years compared to past growth and growth of asymptomatic trees. First order autocorrelation and climatic variables accounted for a large proportion of the variance in growth index, and winter precipitation was positively correlated with growth for all size and age classes. Although ozone concentrations are high enough to cause chlorosis and premature needle senescence in ponderosa pine, there has been no significant change in growth associated with ozone injury.     

Determination of Room Temperature OH Rate Constants for Acetylene,Ethylene Dichloride,Ethylene Dibromide,p-Dichlorobenzene and Carbon Disulfide

A relative rate procedure was used to measure hydroxyl rate constants at room temperature in the presence of oxygen. The photolysis of methyl nitrite in the presence of nitric oxide was used to generate OH radicals. The rate of loss of the test compounds was measured relative to that of ethane (k_OH = 2.74 × 10^-13 cm³ molec^-1 s^-1). The rates obtained at 297 ± 2 K are: acetylene = (7.8 ± 1.6) × 10^-13 cm³ molec^-1 s^-1,1,2-dichloroethane (2.8 ± Q.6) × 10^-13 cm³ molec^-1 s^-1, 1,2-dibromoethane (2.4 ± 0.5) × 10^-13 cm³ molec^-1 s^-1, p-dichlorobenzene (4.3 ± 0.9) × 10^-13 cm³ molec^-1 s^-1 and carbon disulfide (29 ± 6) × 10^-13 cm³ molec^-1 s^-1. Under a proposed EPA rule, this OH rate determination procedure could be used to determine if a given volatile organic will be subject to control for reduction of photochemical ozone.     

Transportation-Related Volatile Hydrocarbon Source Profiles Measured in Atlanta

Abstract

Samples representative of transportation-related hydrocarbon emissions were collected as part of the 1990 Atlanta Ozone Precursor Monitoring Study. Motor vehicle emissions were sampled in canisters beside a roadway in a tunnel-like underpass during periods of heavy traffic. Airport and aircraft emissions were approximated by canister samples obtained at a major airport facility. Three octane grades of gasoline were purchased from six major vendors in Atlanta. Canister samples were prepared using these fuels to approximate the whole gasoline and gasoline vapor composition of the fuels in use during the study. All samples were analyzed by gas chromatography/flame ionization detection (GC/FID) for their hydrocarbon content. Detailed speciated hydrocarbon profiles were developed from this source sampling and analysis program for use in the Chemical Mass Balance (CMB) model. Profiles presented and discussed here represent the hydrocarbon composition of emissions from a roadway, composite headspace gasoline at two temperatures, composite whole gasoline, whole gasoline at three octane grades, and an airport. The roadway profile is compared with similar profiles in the literature, and recommendations are made regarding its use in the CMB model. The roadway and fuel profiles are discussed in the context of the MOBILE5 model outputs. The headspace gasoline vapor profile presented here is compared with a headspace gasoline vapor profile calculated from the whole gasoline profile by means of Raoult’s law. Agreement between the measured and calculated headspace profiles is excellent. The airport profile demonstrates the importance of high molecular weight volatile hydrocarbons in airport and aircraft emissions.     

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.