Modeling of Sulfur Dioxide Emissions and Acidic Precipitation at Mesoscale Distances

A steady state mesoscale model developed to predict primary SO₂ concentrations from a single point source is presented. The model was validated with data from the Midwest Interstate Sulfur Transport and Transformation (MISTT) project, with root mean square errors of 9.69 μg m^?3 and 0.42 μg m^?3 for SO₂ and SO₄ respectively. Wet deposition (washout and rainout), eddy dispersivity, dry deposition of SO₂ and mean wind speed were found to be the most important factors controlling sulfur dioxide and sulfate concentrations. Estimation of precipitation acidity was then carried out using scavenging theory. The greatest potential acidification occurred approximately 200 km from the source along plume centerllne, which indicates a rather local effect as opposed to a long distance effect. The cross-plume influence was up to 60 km in width at a distance of 400 km from the source.     

Alternative Strategies for Control of Sulfur Dioxide Emissions

Achievement of air quality goals now more than ever requires careful consideration of alternative control strategies in view of national concerns with energy and the economy. Three strategies which might be used by coal-fired steam electric plants to achieve ambient air quality standards for sulfur dioxide have been compared, and the analysis shows that the desired objective can be achieved using the intermittent control strategy with substantially less impact on the environment, less consumption of energy, and at a much lower economic cost than using either stack gas scrubbing or low-sulfur coal.     

Modeling Evidence of Incloud Transformation Of Sulfur Dioxide to Sulfate

Methylene chloride (CH₂Cl₂) is presently under study by the U.S. EPA and other agencies to determine if the compound presents an unreasonable risk to human health and to determine if regulatory action is needed to reduce the risk. This paper describes one portion of the study which required the development and validation of a method of sampling and analysis for source emission measurements.

Prior to source sampling, laboratory experiments were conducted to determine the best sample container in which to collect an integrated sample. It was found that CH₂Cl₂ remained stable in Tedlar bags for at least four weeks. The analytical method selected was gas chromatography with flame ionization detection (GC/FID). During the field portion of the study, both manufacturer and user emission sources of CH₂Cl₂ were tested. Multiple sets of simultaneous quadruplicate bag samples were collected to determine the precision of both sampling and analysis in the field. All samples were analyzed at the test site after collection and then returned to Research Triangle Park. Samples were subsequently reanalyzed in the laboratories of Radian and the U.S. EPA using three GC/FID instruments and two types of GC columns. The range of concentrations from the sources was 100 ppm to 27,000 ppm CH₂Cl₂. A statistical analysis of samples collected simultaneously showed no difference in the samples, proving good precision In both sampling and analysis. Some of the sample bags returned from the test sites developed leaks indicating that immediate on-site analysis is best. A comparison of results obtained in the field and the two laboratories showed that interand intra-laboratory precision was within 10 percent.     

A Maximum Entropy Approach to Estimating Emissions

ABSTRACT

A maximum information entropy method of calculating probabilistic estimates of volatile organic compound (VOC) emissions by the wood furniture and fixture coating industry is presented. The maximum entropy approach is used to produce minimally biased probability distributions for number of firms, coating use, and coating emission factors from existing summary statistics. These distributions are combined to estimate VOC emissions. The maximum entropy emissions estimate provides information to support probabilistic modeling of regional air quality, probabilistic assessment of emission reduction strategies, and risk assessments. Accurate estimation of emission distributions produces more informed regulatory decisionmaking, risk comparisons, and regulatory and scientific priority setting.     

A Rapid Titrimetric Method for Sulfate in Lead Dioxide Exposed to Atmospheric Sulfur Pollution

A titrimetric method is described for the analysis of sulfate in lead dioxide candles which have been exposed to atmospheric sulfur pollution. The time taken to analyse one sample is 3 hr. Sixty milliliters of 8% ammonium carbonate solution is used to convert the lead sulfate present on the candle to ammonium sulfate. The solution is filtered lc remove lead dioxide, and an aliquot of the filtrate is heated to remove ammonium carbonate. The solution of ammonium sulfate remaining is titrated directly for sulfate with 0.02 M barium perchlorate, using Thoron as indicator. The accuracy of the method is ±10 and ±6 % of theoretical, for 10 mg, and 40 mg or greater amounts of sulfate, respectively. For 2 mg of sulfate, results are about 20% high. Good agreement has been obtained between results for duplicate field candles, analyzed by the standard sodium carbonate gravimetric method, and the method presented, over a five-month period.     

A Short-Term Air Quality Model for Sulfur Dioxide in Louisville,Kentucky

The conventional gausslan plume equation for ground level concentrations was used to estimate hourly average sulfur dioxide concentrations at selected points in Louisville, KY, on specific days during 1973. Area emission sources were not included in the model since they are not substantial. The trajectory of the emissions from each continuous point source was calculated by a procedure that allowed for spatial variability in wind direction. All other meteorological parameters were held constant during each hour. The twenty-four individual hourly estimates at each location for a given day were arithmetically averaged yielding a daily mean. The model predictions were compared to actual measurements conducted by Jefferson County Air Pollution Control District personnel using the West-Gaeke sampling procedure. The sample correlation coefficient for all predictions was low, but after only about 30% of the predictions were eliminated on statistical grounds, the sample correlation coefficient was increased to 0.72. The statistical analysis appeared to discard a reasonable number of predictions on the basis of observed variability in the measured air quality.     

A Strategy for the Evaluation of Sensory and Pulmonary Irritation Due to Chemical Emissions from Indoor Sources

Abstract

Sensory and pulmonary irritation are physiological responses to chemical exposure which result in characteristic, measurable changes in respiratory activity in mice. A standard method has been applied to the estimation of sensory irritation associated with a specific chemical exposure. This method has been correlated with human responses to these chemicals. Symptoms associated with chemical irritants are consistent with complaints due to problems with indoor air quality, which may include eye and upper respiratory tract irritation, headaches, and nausea. A stepwise strategy for assessing the contribution of indoor products to sensory and pulmonary irritation is discussed in the current paper. The strategy includes product emissions testing using dynamic environmental chambers, the selection of suspected irritants for respiratory irritation testing, respiratory irritation testing of individual compounds and representative mixtures using synthesized atmospheres, and the evaluation of test data to determine those compounds which may contribute to sensory and pulmonary irritation in humans. The current strategy is being applied to evaluate carpet system materials and their constituent chemicals.     

Modeling the Reduction of Vapor Phase Emissions from Surface Soils Due to Soil Matrix Effects: Porosity/Tortuosity Concepts

ABSTRACT

A major route for transport of volatile organic compounds within porous media is vapor phase diffusion. The diffusion rate through a porous medium is less than that through free-air due to the decreased cross-sectional area available for gas movement and the increased path length due to pore tortuosity. Numerous empirical expressions have been published that relate the diffusion coefficient in porous media to the diffusion coefficient in free-air (unobstructed gas phase). Published measurements of relative diffusivity and air-filled porosity were combined into a database. Empirical expressions available in the literature, including the popular Millington-Quirk equation, were evaluated along with a fourth-degree polynomial expression developed by the authors to determine the best type of equation to predict relative diffusivity as a function of air-filled porosity over the domain of values for porosity ranging from 0.071 to 1 for different types of materials. Mean square deviations were used as the statistical test to compare equations. The polynomial expression developed in this project produced a significantly different effective diffusion coefficient (1.3 x 10^-6 m²/sec) compared to values of 9.2 x 10^-6 m²/sec and 3.1 x 10^-6 m²/ sec predicted by forms of the Millington-Quirk equation for a specific case.     

Continuous Monitoring for Sulfur Dioxide at A Utility Boiler Equipped with a Limestone Scrubber

The results of a 30-day sulfur dioxide monitoring program conducted at a utility boiler equipped with a limestone scrubber are presented. Program objectives were twofold: to demonstrate the reliable use of continuous monitoring equipment for determining scrubber performance and to support the proposed New Source Performance Standards (NSPS) published in the September 19, 1978, Federal Register. In general, continuous monitoring equipment is reliable as a source surveillance method. Results of the data collected indicate that the test site monitored was capable of performing under the guidelines of the proposed NSPS, and were incorporated in the final NSPS promulgated on June 11, 1979.     

Electro-Deposited Lead Dioxide Plates: A New Technique for Sulfation Rate Studies

Sulfation rates have long been used to estimate roughly atmospheric SO2 content on a monthly basis. Either lead dioxide coated candles or petri dishes (Huey plates) have so far been used.^1-6 Although in many advanced countries there are now commercially available duly coated petri dishes which are relatively rugged and can stand moderately rough handling during routine operations, small working groups, particularly in developing countries have to be content with “homemade” plates. In tropical climate we find the Huey plates prone to peeling and damage under adverse climatic conditions or routine operations. Besides, the Pb02 slurry deposition technique demands uniformity and submicron size of deposited PbC>2 which is hard to obtain particularly in “homemade” plates.     

On a Strategy for Reducing Short-range Daytime Ground Level Concentrations Due to Emissions from Very Tall Stacks

Abstract

Airborne fine particle sulfur data from the summer intensive of Project MOHAVE (Measurement of Haze and Visual Effects) was analyzed by the Receptor Model Applied to Patterns in Space (RMAPS) model, a novel multivariate receptor-oriented model that applies to secondary and primary species. The sulfur data from 17 sites were found to be well predicted by three spatial patterns interpreted as sources along the valley of the Colorado River; transport from sources located to the southwest; and transport from sources located to the southeast. The model was tested by using parameters derived from the 17-site data set to apportion sulfur for six sites that were not part of the original data set. The sulfur apportionment for these six sites was in agreement with the original apportionment and the physical interpretation of the spatial patterns given above. The effects of systematic and random error on the sulfur apportionment were estimated. The amount of sulfur associated with the Colorado River valley sources was rather insensitive to both types of error. For the two sites in the Grand Canyon National Park, the fraction of total particulate sulfur from the Colorado River valley source is estimated to be in the range of 27-65% at Meadview and 11-28% at Hopi Point.     

A Simplified Technique Used to Evaluate Atmospheric Dispersion of Emissions from Large Power Plants

A simplified method which is used by the Tennessee Valley Authority to estimate ambient concentrations of atmospheric emissions from its large power plants is presented. The technique requires the use of three nomogrdms for the rapid graphic solution of three dispersion models—coning, inversion breakup, and trapping. A discussion of the meteorological conditions that are associated with these dispersion models, supporting appendices, and a worked example are also presented.     

The Effectiveness of a Tall Stack for Reduction of Ambient Sulfur Dioxide Concentrations:A Field Investigation

Of many available methods for limiting ground level pollutant concentrations, tall stacks are many times the simplest, most effective, and least costly. Although this is theoretically explicit, field validation of the soundness of this approach is often hampered by lack of comparable "before" and "after" data. In this study at the Alma Power Plant, appropriate air quality and meteorological measurements were made for several years before and after conversion from short to tall stacks. Comparison of these data show that the tall stack has reduced ambient levels of SO₂ by from 50 to 95 % in the vicinity of the plant. This study also found that use of a Turner-Briggs dispersion model in a valley situation gave fairly accurate and reliable estimates of air quality. The model was useful in designing the tall stack, assessing its impact and locating air quality monitors.     

Feasibility of Applying a Stable Isotopic Tracer for Direct Determination of Dry Particulate Deposition to Soybean Plants

ABSTRACT

A stable rare-earth isotopic tracer was used to measure the deposition of KNO₃ particles on soybean leaves by direct measurement of the tracer on the plant surfaces by thermal-ionization mass spectrometry. Submicrometer particles, made from a solution containing 3 |mg mL^-1 neodymium isotope (¹⁴⁸Nd, 87.9%) and 1,000 mg mL^-1 KNO₃, were dispersed with a two-fluid nozzle and released upwind of a soybean field. Total suspended- and size-fractionated-aerosol particles were collected on an open-face filter and in a micro-orifice impactor, respectively, at a distance of 40 m from the release point. Soybean leaves exposed to the plume were collected at distances ranging from 25 to 100 m. As little as 5.5 pg of the tracer (i.e., excess ¹⁴⁸Nd) was detected in soybean leaves at signal-to-noise ratios ranging from 7,500 to 240,000, in the presence of 200 to 2,700 pg of naturally occurring Nd. The dry-particle deposition velocity, determined from the ratio of the aerial concentration and directly deposited aerosol (geometric mass mean diameter, 0.20 mm) flux, and its corresponding analytical uncertainty were 0.30 cm sec^-1 and 2.5%, respectively.     

Receptor Modeling for Elemental Source Contributions to Fine Aerosols in New York State

ABSTRACT

Fine atmospheric particulate material was collected at five sites in upstate New York and analyzed for its trace element composition by instrumental neutron activation analysis. Of the 3700 daily samples collected over a 2-yr period, 1459 were analyzed for 39 elements, providing a large and detailed data set. Factor analysis (FA) was used to identify potential pollution sources or source regions and to construct inorganic source profiles for each. Following FA, the method of absolute factor scores-multiple linear regression was used to estimate the absolute elemental contribution of each of the identified sources. Factor analysis identified nine sources impacting the sampling region. Seven of these were found to be present in varying degrees among of the sampling sites. The other two sources had more localized impacts and were observed at only one of the sites each. Regional sources (such as the midwestern United States and eastern Canada) and crustal/ soil material accounted for the greatest amount of the trace elements measured in the collected material.     

A Technique for Estimating the Age of Regular/Mid-grade Gasolines Released to the Subsurface Since the Early 1970's

Investigators, regulators, and litigants having interest in gasoline hydrocarbon releases are almost always concerned with knowing when a release occurred. Gasoline releases to the subsurface have, historically, been the most difficult to age date because of their volatile nature and highly aromatic composition. Age dating of gasolines in the past has depended on the degree of weathering of the lower boiling hydrocarbons in gasoline, the use and disuse of lead, lead isotopes, the use of other additives such as methyl-tertiary-butyl ether, and major refining and formulation changes. However, these approaches are limited and many times difficult to demonstrate and apply. This paper describes a new age dating technique using gas chromatographic data. It is based on the progressive enhancement of the aromatics and the reduction of the normal alkanes (paraffins) in the manufacture of regular and mid-grade gasolines since the 1970s. The changing composition of gasoline was necessary to maintain octane ratings during the removal of lead from the gasoline and while meeting increasingly stringent air quality regulations over the past 30 years. This paper proposes the use of an index that reflects these changes in gasoline composition over time and can be correlated to when the gasoline was manufactured. The resulting curve can be used to estimate the age of release (manufacture) of gasolines. This forensic application can be successfully applied to liquid gasoline samples where the evaporation of the gasoline is less than 50%. Case histories and examples are presented to demonstrate application of the technique.