Simulation of stack plume opacity

The visual impact of primary particles emitted from stacks is regulated according to stack opacity criteria. In-stack monitoring of the flue gas opacity allows plant operators to ensure that the plant meets U.S. Environmental Protection Agency opacity regulations. However, the emission of condensable gases such as SO3 (that hydrolyzes to H2SO4), HCl, and NH3, which may lead to particle formation after their release from the stack, makes the prediction of stack plume opacity more difficult. We present here a computer simulation model that calculates the opacity due to both primary particles emitted from the stack and secondary particles formed in the atmosphere after the release of condensable gases from the stack. A comprehensive treatment of the plume rise due to buoyancy and momentum is used to calculate the location at which the condensed water plume has evaporated (i.e., where opacity regulations apply). Conversion of H2SO4 to particulate sulfate occurs through nucleation and condensation on primary particles. A thermodynamic aerosol equilibrium model is used to calculate the amount of ammonium, chloride, and water present in the particulate phase with the condensed sulfate. The model calculates the stack plume opacity due to both primary and secondary particles. Examples of model simulations are presented for three scenarios that differ by the emission control equipment installed at the power plant: (1) electrostatic precipitators (ESP), (2) ESP and flue gas desulfurization, and (3) ESP and selective catalytic reduction. The calculated opacity is most sensitive to the primary particulate emissions. For the conditions considered here, SO3 emissions showed only a small effect, except if one assumes that most H2SO4 condenses on primary particles. Condensation of NH4Cl occurs only at high NH3 emission rates (about 25 ppm stack concentration).     

Opacity Reduction Using Dry Hydrated Lime Injection

Abstract

This investigation studied the effects of injecting dry hydrated lime into flue gas to reduce sulfur trioxide, (SO₃) concentrations and consequently stack opacity at the University of Missouri-Columbia power plant. The opacity was due to sulf uric acid mist forming at the stack from high SO₃ concentrations. As a result of light scattering by the mist, a visible plume leaves the stack. Therefore, reducing high concentrations of SO₃ reduces the sulfuric acid mist and consequently the opacity. To reduce SO₃ concentrations, dry hydrated lime is periodically injected into the flue gas upstream of a baghouse and downstream of an induced draft fan. The hydrated lime is transported downstream by the flue gas and deposited on the filter bags in the baghouse forming a filter cake. The reaction between the SO₃ and the hydrated lime takes place on the filter bags. The hydrated lime injection system has resulted in at least 95% reduction in the SO₃ concentration and has reduced the opacity to acceptable limits. Low capital equipment requirements, low operating cost, and increased bag life make the system very attractive to industries with similar problems.     

Opacity of monodisperse sulfuric acid aerosols

The plume opacity and droplet diameters of a monodisperse sulfuric acid aerosol were calculated as a function of the initial H₂SO₄ concentration, initial H₂O concentration and final gas temperature after cooling from an original stack gas temperature of 300°C. Calculation assumptions include heterogeneous heteromolecular condensation of H₂SO₄ and H₂O onto monodisperse nuclei of 0.05 μm dia., three aerosol particle nuclei concentrations of 10⁶, 10⁷ and 10⁸ cm⁻³ (at 300°C and 760 mm Hg); and a stack or plume diameter of 6 m. The calculated results show that for the conditions considered and with the stack temperatures in excess of 125°C, initial H₂SO₄ stack gas concentrations of 10ppm or less will result in calculated opacities of less than 20 % for a plume diameter of 6 m. The results show that the calculated opacity is significantly affected by the initial H₂SO₄ and initial H₂O concentrations and the final gas temperature. The increases in the calculated opacities upon cooling of the stack gases are similar in general to the increases in the measured opacities between instack and outstack reported by Nader and Conner (1978) for an oil-fired boiler.     

Emissions of Sulfur Trioxide from Coal-Fired Power Plants

Abstract

Emissions of sulfur trioxide (SO₃) are a key component of plume opacity and acid deposition. Consequently, these emissions need to be low enough to not cause opacity violations and acid deposition. Generally, a small fraction of sulfur (S) in coal is converted to SO₃ in coal-fired combustion devices such as electric utility boilers. The emissions of SO₃ from such a boiler depend on coal S content, combustion conditions, flue gas characteristics, and air pollution devices being used. It is well known that the catalyst used in the selective catalytic reduction (SCR) technology for nitrogen oxides control oxidizes a small fraction of sulfur dioxide in the flue gas to SO₃. The extent of this oxidation depends on the catalyst formulation and SCR operating conditions. Gas-phase SO₃ and sulfuric acid, on being quenched in plant equipment (e.g., air preheater and wet scrubber), result in fine acidic mist, which can cause increased plume opacity and undesirable emissions. Recently, such effects have been observed at plants firing high-S coal and equipped with SCR systems and wet scrubbers. This paper investigates the factors that affect acidic mist production in coal-fired electric utility boilers and discusses approaches for mitigating emission of this mist.     

The Evolution of Particles in the Plume from a Large Coal-Fired Boiler with Flue Gas Desulfurization

ABSTRACT

Airborne measurements were made of gaseous and particulate species in the plume of a large coal-fired power plant after flue gas desulfurization (FGD) controls were installed. These measurements were compared with measurements made before the controls were installed. The light scattering and number and volume distributions of plume excess particles were determined by nephelometry and optical particle counting techniques. The plume impact based on optical techniques was much lower than that observed in earlier measurements. Indeed, plume excess volumes as a function of particle size were of the same magnitude as the variability of the background volume distribution. In situ excess plume scattering actually decreased with distance from the source, in contrast to pre-FGD conditions. The upper limit for the dry rate of SO₂-to-SO₄ ^2- conversion was estimated from plume excess volume measurements to be about 4% lir¹. This is slightly greater than the upper limit, 3.5% lir¹, estimated by earlier researchers, but the same as that estimated using the present technique with the earlier data. The cross-plume profile of volume suggests SO₂-to-SO₄ ^2- conversion is highest at the plume edges. The greatest benefit of SO₂ reduction on plume excess volume and visibility appears to occur far downwind of the source.     

Cloud nucleus formation in a power plant plume

A rate of production of ca 10¹⁶ particles s⁻¹ of H₂SO₄ aerosol that acts as cloud condensation nuclei at 1% supersaturation has been estimated to take place in the emission plume from the Four Comers power plant near Farmington, N.M. This generating plant produces about 2175MW at full capacity and emits about 3.7kgs⁻¹ of SO₂, 2.2 kgs⁻¹ of NO_x, and 0.9 kgs⁻¹ of particulates. The site area is desert; annual precipitation averages around 15cm, daytime relative humidity is typically 10–20% and annual sunshine is 75% of possible.An instrumented aircraft was utilized during five investigative periods over a 2-year span to measure plume parameters and to collect plume aerosol samples.The estimated production rate of 10¹⁶ particles s⁻¹ in the plume is equivalent to a gas phase oxidation of SO₂ and homogeneous nucleation-condensation of about 5 μg m⁻³h⁻¹ of H₂SO₄ and is consistent with this mechanism being the primary route for removal of SO₂.     

Removal of SO2 from Simulated Flue Gases Using Non-Thermal Plasma-Based Microgap Discharge

Abstract

The removal of sulfur dioxide (SO₂) from simulated flue gases streams (N₂/O₂/H₂O/SO₂) was experimentally investigated using microgap discharge. In the experiment, the thinner dielectric layers of aluminum oxide (Al₂O₃) were used to form the microgap discharge. With this physical method, a high concentration of hydroxyl (OH·) radicals were produced using the ionization of O₂ and H₂O to further the conversion of SO₂ into sulfuric acid (H₂SO₄) at 120° C in the absence of any catalysts and absorbents, which were captured with the electrostatic precipitator (ESP). As a result, the increase of discharge power and concentrations of O₂ and H₂O increased the production of OH· radicals resulting in enhanced removal of SO₂ from gas streams. With the test and analysis, a number of H₂SO₄ droplets were produced in experiment. Therefore, a new method for removal of SO₂ in semidry method without ammonia (NH₃) additive was found.     

A study of production and growth of sulfate particles in plumes from a coal-fired power plant

A number of airborne plume sampling experiments designed to examine the importance of sulfate particle-generating chemical reactions within coal-burning power station plumes are described. The flights were conducted downwind of the Keystone Generating Station in western Pennsylvania, with The Penn State University research aircraft, an Aerocommander 680E. On-board aerosol sampling instrumentation included a condensation nucleus counter, an optical particle counter and an electrical aerosol analyzer. A casella cascade impactor containing electron microscope copper grids coated with carbon film was used to collect particles at varying distances from the stacks. These samples were analyzed for sulfate content and particle size distribution. Measurements of SO₂ were made with a rapid-response pulsed fluorescent analyzer. Atmospheric pressure, temperature, dewpoint, winds and aircraft position were also monitored. For each flight, a vertical spiral aircraft sounding was made upwind of the power station to determine atmospheric stability and background aerosol particle and SO₂ concentrations. Downwind, the flight pattern consisted of a series of cross wind and longitudinal plume penetrations out to distances at which SO₂ reached background levels. During the case in which cooling tower plume and stack plume merger occurred, sampling continued out to regions where the liquid plume had dissipated. It was found that when relative humidity was low, stability near-neutral and solar radiation intense, the production of new Aitken particles was the primary mechanism of SO₂ oxidation. In the case of merger between the stack plume and the cooling tower plume, the formation of sulfate on pre-existing particles predominated over the formation of new particles. During cases with intermediate meteorological conditions both processes were of equal importance.     

Investigation of aerosol and gas emissions from a coal-fired power plant under various operating conditions

The concentrations of fine particles and selected gas pollutants in the flue gas entering the stack were measured under several common operation modes in an operating coal power plant producing electricity. Particle size distributions in a diameter range from 10 nm to 20 μm were measured by a scanning mobility particle sizer (SMPS), and the flue gas temperature and concentrations of CO₂ and SO₂ were monitored by a continuous emission monitoring system (CEMS). During the test campaign, five plant operating modes were studied: soot blowing, bypass of flue-gas desulfurization (FGD), reheat burner operating at 0% (turned off), 27%, and 42% (normal condition) of its full capacity. For wet and dry aerosols, the measured mode sizes were both around 40 nm, but remarkable differences were observed in the number concentrations (#/cm³, count per square centimeter). A prototype photoionizer enhanced electrostatic precipitator (ESP) showed improved removal efficiency of wet particles at voltages above +11.0 kV. Soot blowing and FGD bypass both increased the total particle number concentration in the flue gas. The temperature was slightly increased by the FGD bypass mode and varied significantly as the rating of reheat burner changed. The variations of CO₂ and SO₂ emissions showed correlations with the trend of total particle number concentration possibly due to the transitions between gas and particle phases. The results are useful in developing coal-fired power plant operation strategies to control fine particle emissions and developing amine-based CO₂ capture technologies without operating and environmental concerns associated with volatile amine emissions.

Implications: The measurement of the fine particle size distributions in the exhaust gas under several common operating conditions of a coal-fired power plant revealed different response relations between aerosol number concentration and the operating condition. A photo-ionizer enhanced ESP was demonstrated to capture fine particles with higher efficiency compared to conventional ESPs, and the removal efficiency increased with the applied voltage. The characteristic information of aerosols and main gaseous pollutants in the exhaust gas is extremely important for developing and deploying CO₂ scrubbers, whose amine emissions and operating effectiveness depends greatly on the upstream concentrations of fine particles, SO₂, from the power plant.     

Relationship of Particulate Control,SO2 Removal,and Waste Management

Results with the EPRI 2.5 MW(e) Integrated Environmental Control Pilot Plant (IECPP) indicate the interrelationship of particulate penetration, SO₂ scrubber operation, waste production, and waste properties. Tests compared a fabric filter/wet scrubber and ESP/wet scrubber, the latter operated to simulate 1979 New Source Performance Standards (NSPS), 1971 NSPS, and pre-NSPS ESP units. Tests were conducted with low-sulfur coal producing a flue gas concentration of400ppm; flue gas spiking could be used to increase SO₂ to 2000 ppm. Scrubber waste was dewatered in a thickener and vacuum belt filter (to 55 percent solids content), and mixed with fly ash. The pilot SO₂ scrubber—when preceded by an ESP and forced to operate in zero-discharge—captured less SO₂ than when preceded by a fabric filter. Also, scrubber operation with the ESP produced a greater quantity of waste with difficult handling characteristics, as compared to operation with the fabric filter. These difficulties occurred with particulate penetration above 0.10 lb/MBtu, which could reduce reagent utilization to 80percent. These results are attributable to inhibited limestone dissolution due to accumulation of an aluminum/fluoride compound. For both lowsulfur and simulated high-sulfur test conditions, allowing wastewater discharge to purge aluminum/fluoride content restored performance to design levels. Particulate control efficiency also affected solid waste physical properties. The fabric filter/wet scrubber produced the lowest solid waste permeability (10^?8 cm/s). ESP operation at 1979 NSPS and pre-1971 NSPS ESPs increased solid waste permeability to 10^?7 and 10^?6 cm/s, respectively. These results are meaningful for SO₂ scrubbers both for new plants and for retrofit to units with pre-NSPS ESPs, and could become significant with the increasing trend to restricted water discharge.     

Improving Baghouse Performance at the Monticello Generating Station

At the Monticello station, operated by the Texas Utilities Generating Company, lignite coal obtained locally in Titus and Hopkins Counties fuels each of the three units. Units 1 and 2 are identical 575-MW Combustion Engineering (CE) boilers, each of which discharges its effluent to a 36- compartment shake/deflate cleaned baghouse paralleled with four electrostatic precipitators (ESP). Unit 3 is a larger boiler and is followed by an ESP and a scrubber. The Unit 1 and 2 baghouses were designed to clean 80 percent of the flue gas. Since startup, these baghouses have regularly experienced flange-to-flange pressure drops in excess of 10 in. H₂O, with large opacity spikes caused by ash bleeding through the bags after compartment cleanings. Because of higher-than-expected pressure drop, the baghouses receive only about 45-50 percent of the flue gas. Analysis has shown the Monticello lignite ash significantly differs from most other coal ashes. Testing has shown that the Monticello ash is not filtered effectively by many "standard" bag materials. However, this testing indicates that there are fabrics that show promise of eliminating the ash bleedthrough with little pressure drop penalty. Testing has also shown that injection of low concentrations (10-15 ppm) of ammonia (NH₃) into the flue gas significantly decreases ash bleedthrough, so that with NH₃ injection "standard" bag materials may perform adequately. Currently, fullcompartment testing of four fabrics, with and without NH₃ injection, is under way at the Unit 1 baghouse. The research conducted at the Monticello station is reviewed in this paper and the encouraging results from the full-compartment tests are presented.     

Flue gas discharge from cooling towers. Wind tunnel investigation of building downwash effects on ground-level concentrations

German power plants are required to meet new emission standards which limit the maximum sulfur dioxide (SOs) concentration in flue gas discharges to 400 mg m⁻³. To achieve this level of reduction in SO₂ concentration, wet scrubbing is necessary for large plants using lignite or hard coal.Wet scrubbing results in a significant reduction in the flue gas temperature leading to low effective stack heights. Instead of using stack gas reheating to achieve the plume rise necessary to satisfy local environmental standards, it was proposed to discharge the scrubbed flue gas from the existing natural-draft cooling towers (NDCT). This method should be effective in reducing local ground-level concentrations since NDCT-plumes are typically very buoyant (densimetric Froude number below 1 ) and normally reach considerable heights of rise. Only under strong wind conditions does the situation reverse itself. For such strong winds, the NDCT-plume is subject to tower and building downwash with the possibility of unacceptably high ground-level concentrations.For a 2700 MW_e lignite-fired power plant near Cologne, a wind tunnel study was carried out to investigate the effects of tower and building downwash effects on the ground-level concentrations of SO₂ produced by discharging the scrubbed flue gas from the natural-draft cooling towers. Also, a comparison was made between the ground-level concentrations produced by the cooling tower discharge method and those produced by a traditional stack. It was found that for low and intermediate wind speeds, the groundlevel concentrations are lower for the case of the cooling tower discharge. Only for strong winds, which occur only very rarely at most German sites, did the conventional stack discharge appear to be superior.     

Estimation of Organic Compound Emissions from Waste Lagoons

Abstract

With the recent focus on fine particle matter (PM_2.5),new, self-consistent data are needed to characterize emissions from combustion sources. Such data are necessary for health assessment and air quality modeling. To address this need, emissions data for gas-fired combustors are presented here, using dilution sampling as the reference.The dilution method allows for collection of emitted particles under conditions simulating cooling and dilution during entry from the stack into the air. The sampling and analysis of the collected particles in the presence of precursor gases, SO₂, nitrogen oxide, volatile organic compound, and NH₃ is discussed; the results include data from eight gas fired units, including a dual-fuel institutional boiler and a diesel engine powered electricity generator. These data are compared with results in the literature for heavy-duty diesel vehicles and stationary sources using coal or wood as fuels. The results show that the gas-fired combustors have very low PM_2.5 mass emission rates in the range of ～10_-4 lb/million Btu (MMBTU) compared with the diesel backup generator with particle filter, with ～5 × 10_-3 lb/MMBTU. Even higher mass emission rates are found in coal-fired systems, with rates of ～0.07 lb/MMBTU for a bag-filter-controlled pilot unit burning eastern bituminous coal. The characterization of PM_2.5 chemical composition from the gas-fired units indicates that much of the measured primary particle mass in PM_2.5 samples is organic or elemental carbon and, to a much less extent, sulfate. Metal emissions are quite low compared with the diesel engines and the coal- or woodfueled combustors. The metals found in the gas-fired combustor particles are low in concentration, similar in concentration to ambient particles. The interpretation of the particulate carbon emissions is complicated by the fact that an approximately equal amount of particulate carbon (mainly organic carbon) is found on the particle collector and a backup filter. It is likely that measurement artifacts, mostly adsorption of volatile organic compounds on quartz filters, are positively biasing “true” particulate carbon emission results.     

The Contribution of Sulfate and Nitrate to Atmospheric Fine Particles During Winter Inversion Fogs in Cache Valley,Utah

Abstract

Air pollutants were collected in Logan, Cache County, UT, in February 1993 during two periods of atmospheric inversion accompanied by fog. The following atmospheric species were determined: (1) gaseous SO₂, NO₂ (semi-quantitatively),HNO3, NH3, and HF; (2) fine particulate SO₄ ⁼, NO₃ ^-, NH₄ ⁺, F–, H⁺, C, Si, S, K, Ca, Ti, Mn, Fe, Ni, Cu, Zn, Pb, Se, Br, and Sr, and; (3) fine particulate mass, which was calculated. The major components of fine particulate matter were carbonaceous material, ammonium nitrate, and ammonium sulfate, while the soil component was small. Calculated, fine particulate mass averaged 80 μg/m³ and reached concentrations as high as 120 μg/m³. SO₂/So_x and NO₂/NO_y mole ratios generally varied between 0.2 and 0.1 during inversions. These ratios also showed moderate but consistent diurnal patterns. The emission inventory for Cache County indicates sources of SO₂ and NO_x but not significant amounts of primary sulfate and nitrate. The observations reported here indicate there is significant conversion of SO₂ and NO_x in the presence of excess oxidants to sulfuric and nitric acid that are neutralized by excess ammonia.     

Influence of sulfur dioxide-related interactions on PM2.5 formation in iron ore sintering

The formation of PM_2.5 (aerosol particulate matter less than 2.5 µm in aerodynamic diameter) in association with SO₂ emission during sintering process has been studied by dividing the whole sintering process into six typical sampling stages. A low-pressure cascade impactor was used to collect PM_2.5 by automatically segregating particulates into six sizes. It was found that strong correlation existed between the emission properties of PM_2.5 and SO₂. Wet mixture layer (overwetted layer and raw mixture layer) had the function to simultaneously capture SO₂ and PM_2.5 during the early sintering stages, and released them back into flue gas mainly in the flue gas temperature-rising period. CaSO₄ crystals constituted the main SO₂-related PM_2.5 during the disappearing process of overwetted layer, which was able to form perfect individual crystals or to form particles with complex chemical compositions. Besides the existence of individual CaSO₄ crystals, mixed crystals of K₂SO₄-CaSO₄ in PM_2.5 were also found during the first half of the temperature-rising period of flue gas. The interaction between fine-grained Ca-based fluxes, potassium vapors, and SO₂ was the potential source of SO₂-related PM_2.5.

Implications: The emission property of PM_2.5 and SO₂ throughout the sintering process exhibited well similarity. This phenomenon tightened the relationship between the formation of PM_2.5 and the emission of SO₂. Through revealing the properties of SO₂-related PM_2.5 during sintering process, the potential interaction between fine-grained Ca-based fluxes, potassium vapors, and SO₂ was found to be the source of SO₂-related PM_2.5. This information can serve as the guidance to develop efficient techniques to control the formation and emission of PM_2.5 in practical sintering plants.     

An Analysis of Extinction Coefficients of Particles and Water Moisture in the Stack after Flue Gas Desulfurization at a Coal-Fired Power Plant

ABSTRACT

Two important factors that affect in-stack opacity—light extinction by emitted particles and that by water moisture after a flue gas desulfurization (FGD) unit—are investigated. The mass light extinction coefficients for particles and water moisture, k _p and k _w, respectively, were determined using the Lambert-Beer law of opacity with a nonlinear least-squares regression method. The estimated k _p and k _w values vary from 0.199 to 0.316 m²/g and 0.000345 to 0.000426 m²/g, respectively, and the overall mean estimated values are 0.229 and 0.000397 m²/g, respectively. Although k _w is 3 orders of magnitude smaller than k _p, experimental results show that the effect on light extinction by water moisture was comparable to that by particles because of the existence of a considerable mass of water moisture after a FGD unit. The mass light extinction coefficient was also estimated using Mie theory with measured particle size distributions and a complex refractive index of 1.5-ni for fly ash particles. The k _p obtained using Mie theory ranges from 0.282 to 0.286 m²/g and is slightly greater than the averaged estimated k _p of 0.229 m²/g from measured opacity. The discrepancy may be partly due to a difference in the microstructure of the fly ash from the assumption of solid spheres because the fly ash may have been formed as spheres attached with smaller particles or as hollow spheres that contained solid spheres. Previously reported values of measured k _p obtained without considering the effects of water moisture are greater than that obtained in this study, which is reasonable because it reflects the effect of extinction by water moisture in the flue gas. Additionally, the moisture absorbed by particulate matter, corresponding to the effect of water moisture on the particulates, was clarified and found to be negligible.

IMPLICATIONS In-stack opacity is used as a surrogate for particle concentration and can be measured using light transmission meters as part of a continuous emission monitoring system. Because emission standards have become increasingly strict, FGD with wet scrubbing is generally used for coal-fired power plants. However, after a FGD unit with wet scrubbing is set up, the concentration of water moisture increases, affecting the measured opacity. This study evaluates the contributions of particles and water moisture to opacity. The results should provide useful information and can be utilized for modifying measurements for monitoring particulate emissions using opacity.     

Second Generation Chemical Mass Balance Source Apportionment of Sulfur Oxides and Sulfate at the Grand Canyon during the Project MOHAVE Summer Intensive

ABSTRACT

Receptor-based chemical mass balance (CMB) analysis techniques are designed to apportion species that are conserved during pollutant transport using conserved source profiles. The techniques will fail if non-conservative species (or profiles) are not properly accounted for in the CMB model. The straightforward application of the CMB model developed for Project MOHAVE using regional profiles resulted in a significant under-prediction of total sulfate oxides (SO_x, SO₂ plus fine particulate sulfate) for many samples at Meadview, AZ. In addition, for these samples the concentration of the inert tracer emitted from the MOHAVE Power Project (MPP), ocPDCH, was also under-predicted. A second-generation model has been developed which assumes that separation of particles and SO₂ can occur in the MPP plume during nighttime stable plume conditions. This second-generation CMB model accounts for all SO_x present at the various receptor sites. In addition, the concentrations of ocPDCH and the presence of other inert tracers of emission from regional sources are accurately predicted. The major source of SO_x at Meadview was the MPP, but the major source of sulfate at this site was the Las Vegas urban area. At Hopi Point in the Grand Canyon, the Baja California region (Imperial Valley and northwestern Mexico) was the major source of both SO_x and sulfate.     

Rates of Conversion of Sulfur Dioxide to Sulfate in a Scrubbed Power Plant Plume

ABSTRACT

The rate of conversion of SO₂ to SO₄ ^2- was re-estimated from measurements made in the plume of the Cumberland power plant, located on the Cumberland River in north-central Tennessee, after installation of flue gas desulfurization (FGD) scrubbers for SO₂ removal in 1994. The ratio of SO₂ to NO_y emissions into the plume has been reduced to ~0.1, compared with a prescrubber value of ~2. To determine whether the SO₂ emissions reduction has correspondingly reduced plume-generated particulate SO₄ ^2- production, we have compared the rates of conversion before and after scrubber installation. The prescrubber estimates were developed from measurements made during the Tennessee Plume Study conducted in the late 1970s. The post-scrubber estimates are based upon two series of research flights in the summers of 1998 and 1999. During two of these flights, the Cumberland plume did not mix with adjacent power plant plumes, enabling rate constants for conversion to be estimated from samples taken in the plume at three downwind distances. Dry deposition losses and the fact the fact that SO₂ is no longer in large excess compared with SO₄ ^2- have been taken into account, and an upper limit for the conversion rate constant was re-estimated based on plume excess aerosol volume. The estimated upper limit values are 0.069 hr^-1 and 0.034 hr^-1 for the 1998 and 1999 data, respectively. The 1999 rate is comparable with earlier values for nonscrubbed plumes, and although the 1998 upper limit value is higher than expected, these estimates do not provide strong evidence for deviation from a linear relationship between SO₂ emissions and SO₄ ^2- formation.     

Specific determination of aerosol sulfuric acid in the presence of ammonium sulfate. A laboratory study

A method has been developed to specifically determine H₂SO₄ aerosol in the presence of other particulate sulfates, including (NH₄)₂SO₄. Prior to collection, the sample stream is heated to reduce relative humidity to ~40% such that (NH₄)₂SO₄ as well as other particulate sulfates are collected as solid particulates and do not react with the collection filter impregnating reagent. The glass fiber collection filter is impregnated with 2-perimidinylammonium bromide and collected H₂SO₄ is immobilized as the sulfate salt. The collected particulate sulfates are converted to BaSO₄ by treatment with a barium acetate solution in methanol-acetone. Excess impregnating reagent is removed by frontal elution chromatography with methanol and then the organic sulfate is converted into an intensely colored compound, 2-amino, 4,6,9-trinitroperimidine, by reaction with HNO₃. This compound behaves as an indicator and after adding excess base the intensity of the developed color is measured at 550 nm. The sensitivity of the method is 0.1 μg H₂SO₄ and the working range is 0.2–50 μg H₂SO₄.