Evaluation of a reactive plume model with power plant plume data—application to the sensitivity analysis of sulfate and nitrate formation

A reactive plume model that treats secondary aerosol formation is used to investigate the major physical and chemical processes that affect the rate of sulfate and nitrate aerosol formation in power plant plumes. The reactive plume model is evaluated with experimental data collected in three power plant plumes, and model performance is shown to be quite satisfactory. One of these case studies is used to perform singleparameter and multi-parameter analyses of the sensitivity of sulfate and nitrate aerosol concentrations to various meteorological, air quality and chemical kinetic parameters. The results suggest that sulfate aerosol concentrations are most sensitive to relative humidity and temperature at high relative humidity, whereas nitrate aerosol concentrations are most sensitive to temperature, particularly at low relative humidity. The importance of the NO_x/reactive hydrocarbon chemistry to sulfate and nitrate aerosol formation is examined.     

The APCA Exhibition

On June 5 and 6 of 1980, two parallel plume oxidation studies were carried out in the vicinity of the Tennessee Valley Authority's Colbert Steam Plant. One study was performed in a smog chamber into which stack gases were injected and mixed with ambient air. The other study included direct airborne sampling of the power plant plume. Atmospheric oxidation rates for the conversion of SO₂ to SO₄ ^2- and the removal rates of NO _x (which is presumably the rate of NO₃ ^- formation) were estimated for both studies. The SO₂ to SO₄ ^2- rate coefficients were found to be 0.022 ± 0.009 h^-1 for both chamber experiments and the first airborne sampling day. For the second day, a rate constant of 0.041 ± 0.052 h^-1 was estimated from the aircraft data. The large deviation in this value is explained by the fact that the plume from the power plant combined and reacted with the urban plume from the city of Florence, AL. The formation of a very large "O3 bulge" on this day is also attributed to the mixed plumes. The first order rate coefficients for NO _x removal were estimated to be 0.27 ± 0.14 h^-1 for both chamber experiments and the first airborne sampling day. A NO _x removal rate could not be determined for the second airborne sampling day.     

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.     

The evolution of photochemical smog in a power plant plume

The evolution of photochemical smog in a plant plume was investigated with the aid of an instrumented helicopter. Air samples were taken in the plume of the Cumberland Power Plant, located in central Tennessee, during the afternoon of 16 July 1995 as part of the Southern Oxidants Study – Nashville Middle Tennessee Ozone Study. Twelve cross-wind air sampling traverses were made at six distance groups from 35 to 116 km from the source. During the sampling period the winds were from the west–northwest and the plume drifted towards the city of Nashville TN. Ten of the traverses were made upwind of the city, where the power plant plume was isolated, and two traverses downwind of the city when the plumes were possibly mixed. The results revealed that even six hours after the release, excess ozone production was limited to the edges of the plume. Only when the plume was sufficiently dispersed, but still upwind of Nashville, was excess ozone (up to 109 ppbv, 50–60 ppbv above background levels) produced in the center of the plume. The concentrations image of the plume and a Lagrangian particle model suggests that portions of the power plant plume mixed with the urban plume. The mixed urban power plant plume began to regenerate O₃ that peaked at 120 ppbv at a short distance (15–25 km) downwind of Nashville. Ozone productivity (the ratio of excess O₃ to NO_y and NO_z) in the isolated plume was significantly lower compared with that found in the city plume. The production of nitrate, a chain termination product, was significantly higher in the power plant plume compared to the mixed plume, indicating shorter chain length of the photochemical smog chain reaction mechanism.     

Photochemical model performance for PM2.5 sulfate,nitrate, ammonium,and precursor species SO2, HNO3, and NH3 at background monitor locations in the central and eastern United States

Health studies have shown premature death is statistically associated with exposure to particulate matter <2.5 μm in diameter (PM2.5). The United States Environmental Protection Agency requires all States with PM2.5 non-attainment counties or with sources contributing to visibility impairment at Class I areas to submit an emissions control plan. These emission control plans will likely focus on reducing emissions of sulfur oxides and nitrogen oxides, which form two of the largest chemical components of PM2.5 in the eastern United States: ammonium sulfate and ammonium nitrate. Emission control strategies are simulated using three-dimensional Eulerian photochemical transport models.A monitor study was established using one urban (Detroit) and nine rural locations in the central and eastern United States to simultaneously measure PM2.5 sulfate ion (SO₄²⁻), nitrate ion (NO₃⁻), ammonium ion (NH₄⁺), and precursor species sulfur dioxide (SO₂), nitric acid (HNO₃), and ammonia (NH₃). This monitor study provides a unique opportunity to assess how well the modeling system predicts the spatial and temporal variability of important precursor species and co-located PM2.5 ions, which is not well characterized in the central and eastern United States.The modeling system performs well at estimating the PM2.5 species, but does not perform quite as well for the precursor species. Ammonia is under-predicted in the coldest months, nitric acid tends to be over-predicted in the summer months, and sulfur dioxide appears to be systematically over-predicted. Several indicators of PM2.5 ammonium sulfate and ammonium nitrate formation and chemical composition are estimated with the ambient data and photochemical model output. PM2.5 sulfate ion is usually not fully neutralized to ammonium sulfate in ambient measurements and is usually fully neutralized in model estimates. The model and ambient estimates agree that the ammonia study monitors tend to be nitric acid limited for PM2.5 nitrate formation. Regulatory strategies in this part of the country should focus on reductions in NO_X rather than ammonia to control PM2.5 ammonium nitrate.     

Formation of secondary inorganic aerosols by power plant emissions exhausted through cooling towers in Saxony

Background, aim, and scope  The fraction of ambient PM₁₀ that is due to the formation of secondary inorganic particulate sulfate and nitrate from the emissions of two large, brown-coal-fired power stations in Saxony (East Germany) is examined. The power stations are equipped with natural-draft cooling towers. The flue gases are directly piped into the cooling towers, thereby receiving an additionally intensified uplift. The exhausted gas-steam mixture contains the gases CO, CO₂, NO, NO₂, and SO₂, the directly emitted primary particles, and additionally, an excess of ‘free’ sulfate ions in water solution, which, after the desulfurization steps, remain non-neutralized by cations. The precursor gases NO₂ and SO₂ are capable of forming nitric and sulfuric acid by several pathways. The acids can be neutralized by ammonia and generate secondary particulate matter by heterogeneous condensation on preexisting particles. Materials and methods  The simulations are performed by a nested and multi-scale application of the online-coupled model system LM-MUSCAT. The Local Model (LM; recently renamed as COSMO) of the German Weather Service performs the meteorological processes, while the Multi-scale Atmospheric Transport Model (MUSCAT) includes the transport, the gas phase chemistry, as well as the aerosol chemistry (thermodynamic ammonium–sulfate–nitrate–water system). The highest horizontal resolution in the inner region of Saxony is 0.7 km. One summer and one winter episode, each realizing 5 weeks of the year 2002, are simulated twice, with the cooling tower emissions switched on and off, respectively. This procedure serves to identify the direct and indirect influences of the single plumes on the formation and distribution of the secondary inorganic aerosols. Results and conclusions  Surface traces of the individual tower plumes can be located and distinguished, especially in the well-mixed boundary layer in daytime. At night, the plumes are decoupled from the surface. In no case does the resulting contribution of the cooling tower emissions to PM₁₀ significantly exceed 15 μgm⁻³ at the surface. These extreme values are obtained in narrow plumes on intensive summer conditions, whereas different situations with lower turbulence (night, winter) remain below this value. About 90% of the PM₁₀ concentrations in the plumes are secondarily formed sulfate, mainly ammonium sulfate, and about 10% originate from the primarily emitted particles. Under the assumptions made, ammonium nitrate plays a rather marginal role. Recommendations and perspectives  The analyzed results depend on the specific emission data of power plants with flue gas emissions piped through the cooling towers. The emitted fraction of ‘free’ sulfate ions remaining in excess after the desulfurization steps plays an important role at the formation of secondary aerosols and therefore has to be measured carefully.     

Field observations of regional and urban impacts on NO2, ozone,UVB, and nitrate radical production rates in the Phoenix air basin

In the May and June of 1998, field measurements were taken at a site near the Usery Pass Recreation Area, ∼27 miles from the downtown Phoenix area, overlooking Phoenix and Mesa, Arizona. This site was selected to examine the impacts of the Phoenix urban plume on the Usery Pass Recreation Area and surrounding regions. Data were obtained for ultraviolet-B (UVB) radiation, nitrogen dioxide (NO₂), peroxyacetyl nitrate (PAN), ozone (O₃), and carbon monoxide (CO). Nocturnal plumes of NO₂ (in tens of ppb), observed near midnight, were correlated with CO and anti-correlated with O₃. This behavior was consistent with the titration of locally generated NO by boundary layer O₃ to form the nighttime NO₂ plumes that were subsequently transported into the Usery Pass Recreation area. Nitrate radical (NO₃) production rates were calculated to be very high on the edges of these nocturnal plumes. Examination of O₃ and PAN data also indicates that Phoenix is being affected by long-range transport of pollutants from the Los Angeles to San Diego areas. A regional smoke episode was observed in May, accompanied by a decrease in UVB of factor of two and a decrease in O₃ and an increase in methyl chloride. Low level back trajectories and chemical evidence confirm that the smoke event originated in northern Mexico and that the reduced O₃ levels observed at Usery Pass could be partially due to reduced photolysis rates caused by carbonaceous soot aerosols transported in the smoke plume. The results are discussed with regard to potential effects of local pollution transport from the Phoenix air basin as well as an assessment of the contributions from long-range transport of pollutants to the background levels in the Phoenix-Usery Pass area.     

Analysis of the air pollution climate at a central urban background site

Measurements of air pollutants from a background site in central London are analysed. These comprise hourly data for CO, NO, NO₂, O₃, SO₂ and PM₁₀ from 1996 to 2008 and particle number count from 2001 to 2008. The data are analysed in terms of long-term trends, annual, weekly and diurnal cycles, and autocorrelation and cross-correlation functions. CO, NO and NO₂ show a typical traffic-associated pattern with two daily peaks and lesser concentrations at the weekend. Particle number count and PM₁₀ show a similar cycle, but with smaller amplitude. Ozone has an annual cycle with a maximum in May, influenced by the spring maximum in background ozone, but the diurnal and weekly cycles are dominated by losses through reaction with nitric oxide. Particle number count shows a minimum corresponding with maximum air temperatures in August, whereas the CO, NO NO₂ and SO₂ show a minimum in June/July. There is a lower particle count to NO_x ratio at the background site compared to a central London kerbside site (Marylebone Road) and a seasonal pattern in particle count to NO_x and PM₁₀ ratios consistent with loss of nanoparticles by evaporation during atmospheric transport. Sulphur dioxide peaks in the morning in summer, but at midday in winter consistent with emissions from elevated sources mixing down from aloft as the diurnal mixed layer deepens. Implications for epidemiological studies of air quality and health are discussed. Sulphur dioxide, carbon monoxide, nitric oxide and nitrogen dioxide show clear downward trends over the measurement period, PM₁₀ declines initially before levels stabilised, and ozone concentrations increased.     

Modeling of Potential Power Plant Plume Impacts on Dallas-Fort Worth Visibility

ABSTRACT

During wintertime, haze episodes occur in the Dallas-Ft. Worth (DFW) urban area. Such episodes are characterized by substantial light scattering by particles and relatively low absorption, leading to so-called “white haze.” The objective of this work was to assess whether reductions in the emissions of SO₂ from specific coal-fired power plants located over 100 km from DFW could lead to a discernible change in the DFW white haze. To that end, the transport, dispersion, deposition, and chemistry of the plume of a major power plant were simulated using a reactive plume model (ROME). The realism of the plume model simulations was tested by comparing model calculations of plume concentrations with aircraft data of SF₆ tracer concentrations and ozone concentrations. A second-order closure dispersion algorithm was shown to perform better than a first-order closure algorithm and the empirical Pasquill-Gifford-Turner algorithm. For plume impact assessment, three actual scenarios were simulated, two with clear-sky conditions and one with the presence of fog prior to the haze. The largest amount of sulfate formation was obtained for the fog episode. Therefore, a hypothetical scenario was constructed using the meteorological conditions of the fog episode with input data values adjusted to be more conducive to sulfate formation. The results of the simulations suggest that reductions in the power plant emissions lead to less than proportional reductions in sulfate concentrations in DFW for the fog scenario. Calculations of the associated effects on light scattering using Mie theory suggest that reduction in total (plume + ambient) light extinction of less than 13% would be obtained with a 44% reduction in emissions of SO₂ from the modeled power plant.     

Role of ammonia chemistry and coarse mode aerosols in global climatological inorganic aerosol distributions

We use an inorganic aerosol thermodynamic equilibrium model in a three-dimensional chemical transport model to understand the roles of ammonia chemistry and natural aerosols on the global distribution of aerosols. The thermodynamic equilibrium model partitions gas-phase precursors among modeled aerosol species self-consistently with ambient relative humidity and natural and anthropogenic aerosol emissions during the 1990s.Model simulations show that accounting for aerosol inorganic thermodynamic equilibrium, ammonia chemistry and dust and sea-salt aerosols improve agreement with observed SO₄, NO₃, and NH₄ aerosols especially at North American sites. This study shows that the presence of sea salt, dust aerosol and ammonia chemistry significantly increases sulfate over polluted continental regions. In all regions and seasons, representation of ammonia chemistry is required to obtain reasonable agreement between modeled and observed sulfate and nitrate concentrations. Observed and modeled correlations of sulfate and nitrate with ammonium confirm that the sulfate and nitrate are strongly coupled with ammonium. SO₄ concentrations over East China peak in winter, while North American SO₄ peaks in summer. Seasonal variations of NO₃ and SO₄ are the same in East China. In North America, the seasonal variation is much stronger for NO₃ than SO₄ and peaks in winter.Natural sea salt and dust aerosol significantly alter the regional distributions of other aerosols in three main ways. First, they increase sulfate formation by 10–70% in polluted areas. Second, they increase modeled nitrate over oceans and reduce nitrate over Northern hemisphere continents. Third, they reduce ammonium formation over oceans and increase ammonium over Northern Hemisphere continents. Comparisons of SO₄, NO₃ and NH₄ deposition between pre-industrial, present, and year 2100 scenarios show that the present NO₃ and NH₄ deposition are twice pre-industrial deposition and present SO₄ deposition is almost five times pre-industrial deposition.     

Background levels of air and precipitation quality for Europe

This paper is intended to be used by specialists engaged in air and precipitation quality management on regional and continental scales. Major goals are to establish definition, methodology and specific values of background air and precipitation quality for sulfur (S) and nitrogen (N) species to be used in practical applications of air resources management. Major findings are the following:

• 1.(a) 69% of SO₂ and 63 % of NO₂ concentration over Europe originate from continental scale anthropogenic sources,
• 2.(b) 15% of precipitation sulfate and 11% of precipitation nitrate over Europe are contributed by hemispheric background,
• 3.(c) hemispheric background pollution values for Europe were found as 1.25 μg (SO₂-S)m⁻³, 0.80 μg (SO₄²⁻-S)m⁻³, 0.157 mg (SO₄²⁻-S)l⁻¹ and 0.04 mg (NO₃⁻-N)ℓ⁻¹.

     

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.     

Estimating Future NO2 Levels in the Greater Los Angeles Area by Source–Type Contribution

Two indicator pollutants, carbon monoxide (CO) for mobile source influence and sulfur dioxide (SO₂) for stationary source influence, were used to estimate source-type contributions to ambient NO₂ levels in a base year and to predict NO₂ concentrations in a future year. For a specific source-receptor pair, the so-called influence coefficient of each of three source categories (mobile sources, power plants, and other stationary sources) was determined empirically from concurrent measurements of CO and SO₂ concentrations at the receptor site and CO and SO₂ emissions from each source category in the source area. Those coefficients, which are considered time invariant, were used in conjunction with the base year and future year NO _x emission values to estimate source-type contribution to ambient NO₂ levels at seven study sites selected from the Greater Los Angeles area for both the base year period, 1974 through 1976, and the future goal year of 1987 in which the air quality standards for NO₂ are to be attained. The estimated NO₂ air quality at the seven sites is found to meet the national annual standard of 5 pphm and over 99.9% of total hours, the California 1-hr NO₂ standard of 25 pphm in 1987. The estimated power plant contributions to ambient NO₂ levels are found to be considerably smaller than those to total NO _x emissions in the area. Providing that reasonably complete air quality and emissions data are available, the present analysis method may prove to be a useful tool in evaluating source contributions to both short-term peak and long-term average NO₂ concentrations for use in control strategy development.     

Composition and secondary formation of fine particulate matter in the Salt Lake Valley: Winter 2009

Under the National Ambient Air Quality Standards (NAAQS), put in place as a result of the Clean Air Amendments of 1990, three regions in the state of Utah are in violation of the NAAQS for PM₁₀ and PM_2.5 (Salt Lake County, Ogden City, and Utah County). These regions are susceptible to strong inversions that can persist for days to weeks. This meteorology, coupled with the metropolitan nature of these regions, contributes to its violation of the NAAQS for PM during the winter. During January–February 2009, 1-hr averaged concentrations of PM_10-2.5, PM_2.5, NO_x, NO₂, NO, O₃, CO, and NH₃ were measured. Particulate-phase nitrate, nitrite, and sulfate and gas-phase HONO, HNO₃, and SO₂ were also measured on a 1-hr average basis. The results indicate that ammonium nitrate averages 40% of the total PM_2.5 mass in the absence of inversions and up to 69% during strong inversions. Also, the formation of ammonium nitrate is nitric acid limited. Overall, the lower boundary layer in the Salt Lake Valley appears to be oxidant and volatile organic carbon (VOC) limited with respect to ozone formation. The most effective way to reduce ammonium nitrate secondary particle formation during the inversions period is to reduce NO_x emissions. However, a decrease in NO_x will increase ozone concentrations. A better definition of the complete ozone isopleths would better inform this decision.

Implications: Monitoring of air pollution constituents in Salt Lake City, UT, during periods in which PM_2.5 concentrations exceeded the NAAQS, reveals that secondary aerosol formation for this region is NO_x limited. Therefore, NO_x emissions should be targeted in order to reduce secondary particle formation and PM_2.5. Data also indicate that the highest concentrations of sulfur dioxide are associated with winds from the north-northwest, the location of several small refineries.     

Measurements of Rural Sulfur Dioxide and Particle Sulfate: Analysis of CASTNet Data, 1987 through 1996

ABSTRACT

The Clean Air Status and Trends Network (CASTNet) was implemented by the U.S. Environmental Protection Agency (EPA) in 1991 in response to Title IX of the Clean Air Amendments of 1990, which mandated the deployment of a national ambient air monitoring network to track progress of the implementation of emission reduction programs in terms of deposition, air quality, and changes to affected ecosystems. CASTNet evolved from the National Dry Deposition Network (NDDN). CASTNet currently consists of 45 sites in the eastern United States and 28 sites in the West. Each site measures sulfur dioxide (SO₂), nitric acid (HNO₃), particle sulfate (SO₄ ⁼), particle nitrate (NO₃ ^- ), and ozone. Nineteen sites collect precipitation samples. NDDN/CASTNet uses a uniform set of site-selection criteria which provides the data user with consistent measures to compare each site. These criteria also ensure that, to the extent possible, CASTNet sites are located away from local emission sources.

This paper presents an analysis of SO₂ and SO₄ ⁼ concentration data collected from 1987 through 1996 at rural NDDN/CASTNet sites. Annual and seasonal variability is examined. Gradients of SO₂ and SO₄ ⁼ are discussed. The variability of the atmospheric mix of SO₂ and SO₄ ⁼ is explored spatially and seasonally. Data from CASTNet are also compared to SO₂ and SO₄ ⁼ data from concurrent monitoring studies in rural areas.     

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.     

Simultaneous Sulfur Dioxide and Nitrogen Dioxide Removal by Calcium Hydroxide and Calcium Silicate Solids

ABSTRACT

At conditions typical of a bag filter exposed to a coal-fired flue gas that has been adiabatically cooled with water, calcium hydroxide and calcium silicate solids were exposed to a dilute, humidified gas stream of nitrogen dioxide (NO₂) and sulfur dioxide (SO₂) in a packed-bed reactor. A prior study found that NO₂ reacted readily with surface water of alkaline and non-alkaline solids to produce nitrate, nitrite, and nitric oxide (NO). With SO₂ present in the gas stream, NO₂ also reacted with S(IV), a product of SO₂ removal, on the exterior of an alkaline solid. The oxidation of S(IV) to S(VI) by oxygen reduced the availability of S(IV) and lowered removal of NO₂. Subsequent acidification of the sorbent by the removal of NO₂ and SO₂ facilitated the production of NO. However, the conversion of nitrous acid to sulfur-nitrogen compounds reduced NO production and enhanced SO₂ removal. A reactor model based on empirical and semi-empirical rate expressions predicted rates of SO₂ removal, NO₂ removal, and NO production by calcium silicate solids. Rate expressions from the reactor model were inserted into a second program, which predicted the removal of SO₂ and NO_x by a continuous process, such as the collection of alkaline solids in a baghouse. The continuous process model, depending upon inlet conditions, predicted 30-40% removal for NO and 50-90% removal for SO₂. These x 2 results are relevant to dry scrubbing technology for combined SO₂ and NO_x removal that first oxidizes NO to NO₂ by the addition of methanol into the flue duct.     

A simple technique for measuring power station SO2 and NO2 emissions

Emissions of SO₂ and NO₂ from fossil fuel power stations can have serious environmental consequences via conversion to sulphuric and nitric acids and subsequent deposition. Consequently, there is considerable interest in techniques capable of monitoring these emissions, in order to ensure compliance with environmental legislation. Here we present a novel approach to measuring power station SO₂ and NO₂ emissions by traversing underneath the plume by car or on-foot or scanning the power station's plume from a fixed position with a compact and lightweight UV spectrometer. This work was performed at a power station in eastern England during January, February and June 2003, resulting in a SO₂ flux of 5.2 kg s⁻¹, which is in close correspondence with the in-stack measured value of 5.3 kg s⁻¹. This technique is considerably simpler and cheaper than other remote sensing approaches to monitoring these emissions.     

Simulation of Stack Plume Opacity

ABSTRACT

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).     

Modeling wintertime particulate matter formation in central California

A wintertime episode during the 2000 California Regional PM Air Quality Study (CRPAQS) was simulated with the air quality model CMAQ–MADRID. Model performance was evaluated with 24-h average measurements available from CRPAQS. Modeled organic matter (OM) was dominated by emissions, which were probably significantly under-represented, especially in urban areas. In one urban area, modeled daytime nitrate concentrations were low and evening concentrations were high. This diurnal profile was not explained by the partition of nitrate between the gas and particle phases, because gaseous nitric acid concentrations were low compared to PM nitrate. Both measured and simulated nitrate concentrations aloft were lower than at the surface at two tower locations during this episode. Heterogeneous reactions involving NO₃ and N₂O₅ accounted for significant nitrate production in the model, resulting in a nighttime peak. The sensitivity of PM nitrate to precursor emissions varied with time and space. Nitrate formation was on average sensitive to NO_x emissions. However, for some periods at urban locations, reductions in NO_x caused the contrary response of nitrate increases. Nitrate was only weakly sensitive to reductions in anthropogenic VOC emissions. Nitrate formation tended to be insensitive to the availability of ammonia at locations with high nitrate, although the spatial extent of the nitrate plume was reduced when ammonia was reduced. Reductions in PM emissions caused OM to decrease, but had no effect on nitrate despite the role of heterogeneous reactions. A control strategy that focuses on NO_x and PM emissions would be effective on average, but reductions in VOC and NH₃ emissions would also be beneficial for certain times and locations.