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.     

Airborne Particulate Emissions from a Chromic Acid Anodizing Process Tank

Particulate mass concentration, particle size distribution, and particle chemical composition measurements have been conducted on the gases exhausting from a chromic acid anodizing process tank. Particle mass concentrations in the 200 to 20,000 μg/m³ range were measured using open-faced filters (47 mm diameter) adjacent to the process tank liquid and with closed filters (90 mm diameter) in the exhaust duct. Particle size distributions, measured using University of Washington Mark 3 and Mark 20 Cascade Impactors, showed the particle aerodynamic mass median diameter was about 3 microns. Chemical analysis of the particle samples obtained by the Modified EPA Method 5 sampling train, the Mark 20 UW Cascade Impactors, and by the 47 mm and 90 mm diameter filters showed Cr⁺⁶ concentrations in the 20 to 1,500 μg/m³ range with over 99 percent of the chromium in particles larger than 1.0 microns diameter. An integrating nephelometer was used to measure the light scattering coefficient of the exhaust gases upstream of the wet scrubber. The light scattering coefficient increased by a factor of about 2–3 over the background level during the 40 minute time period while a part was being anodized. The bscat values ranged from 3 × 10^?5 to 3 × 10^?4 meters^?1 for the aerosol particles less than about 6 microns aerodynamic diameter.     

Measurement of Volatile Organics at Part per Billion Concentrations Using a Cold Trap Inlet and High Speed Gas Chromatography

Direct inlet gas chromatography (GC) is becoming one of the most frequently used techniques for measurement of volatile organics in air. Although GC is an effective tool, its usefulness as a field method can be limited by retention times of several minutes or more, and by the limits of detection. In order to address these issues, a high speed GC system featuring a capillary cold trap inlet and variable speed electrometeramplifier was developed and tested.

The gas cooled inlet was used to collect and focus organic vapors from injection volumes of up to 1 ml. Resistance heating of the metal cold trap produced a narrow injection band that allowed simple separations to be completed in 5 to 20 seconds. Use of a variable speed electrometer-amplifier allowed the response time and noise suppression characteristics to be adjusted to the needs of the specific analysis.

Simple mixtures of organics including aromatics, alkanes and chlorinated hydrocarbons were separated in 20 seconds or less. The limits of detection for 13 test compounds ranged from less than 1 part per billion by volume (ppbv) to about 50 ppbv. Data presented here indicate that high speed GC using a cold trap inlet may be a feasible approach for near real-time measurement of volatile organics in ambient air.     

Modeling Emissions from Elevated Cylindrical Bins

Abstract

This paper demonstrates how wind tunnel modeling data that accurately describe plume characteristics near an unconventional emission source can be used to improve the near-field downwind plume profiles predicted by conventional air pollution dispersion models. The study considers a vertical, cylindrical-shaped, elevated bin similar to large product storage bins that can be found at many industrial plant sites. Two dispersion models are considered: the U.S. Environmental Protection Agency's ISC2(ST) model and the Ontario Ministry of the Environment and Energy's GAS model. The wind tunnel study showed that plume behavior was contrary to what was predicted using conventional dispersion models such as ISC2(ST) and GAS and default values of input parameters. The wind tunnel data were used to develop a protocol for correcting the dispersion models inputs, resulting in a substantial improvement in the accuracy of the dispersion estimates.     

Estimating Maximum Concentrations for Open Path Monitoring Along a Fixed Beam Path

ABSTRACT

Researchers have applied open path optical sensing techniques to a variety of workplace and environmental monitoring problems. Usually these data are reported in terms of a path-average (or path-integrated) concentration. When assessing potential human exposures along a beam path, this path-average value is not always informative, since concentrations along the path can vary substantially from the beam average. The focus of this research is to arrive at a method for estimating the upper-bound in contaminant concentrations over a fixed open beam path. The approach taken here uses a statistical model to estimate an upper-bound concentration based on a combination of the path-average and a measure of the spatial variability computed from point samples along the beam path. Results of computer simulations and experimental testing in a controlled ventilation chamber indicate that the model produced conservative estimates for the maximum concentration along the beam path. This approach may have many applications for open path monitoring in workplaces or wherever maximum concentrations are a concern.     

Aerosol Research and Inhalation Epidemiological Study (ARIES): Air Quality and Daily Mortality Statistical Modeling— Interim Results

ABSTRACT

The Aerosol Research and Inhalation Epidemiological Study (ARIES) is an EPRI-sponsored project to collect air quality and meteorological data at a single site in northwestern Atlanta, GA. Seventy high-resolution air quality indicators (AQIs) are used to examine statistical relationships between air quality and health outcome end points. Contemporaneous mortality data are collected for Fulton and DeKalb counties in Georgia. Currently, 12 months of air quality and weather data are available for analysis, from August 1998 through July 1999.

The interim mortality analysis used Poisson regression in generalized additive models (GAMs). The estimated log-linear association of mortality with various AQIs was adjusted for smoothed functions of time and meteorological data. The analysis considered daily deaths due to all nonaccidental causes, deaths to persons 65 years or older, and deaths in each of the two constituent counties. The fine particle effect associated with the four mortality subgroups, using only today (lag 0), yesterday (lag 1), 2-day average (average of today and yesterday), and first difference (today minus yesterday) measurements of the air quality relative to today's number of deaths was positive for lag 0, lag 1, and 2-day average and positive only for decedents at least 65 years of age using first difference. The t values ranged from 0.81 to 1.15 for lag 0, 1.04 to 1.53 for lag 1, 1.10 to 1.66 for 2-day average, and -0.32 to 0.33 for first difference with 346 or 347 days of data. No statistically significant estimate of the linear coefficient was found for the other 14 air quality variables in our interim analysis for the four mortality subgroups. We discuss diagnostics to support these models.

These interim analyses did not include an evaluation of sensitivity to a larger set of lag structures, nonlinear model specifications, multipollutant analyses, alternative weather model and smoothing model specifications, air pollution imputation schemes, or cause-specific mortality indicators, nor did they include a full reporting of model selection or goodness-of-fit indicators. No conclusion can be drawn at this time about whether the findings from subsequent studies have sufficiently greater power to detect effects comparable to those found in other U.S. cities including at least 2 or 3 years of data.     

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.