Analysis of emission databases for regional models

General procedures for adapting emission inventories to regional models and for studying the impact of differences in inventories on model predictions are outlined. To illustrate the methods, analysis of two inventories which are still being validated is presented. The inventories together satisfy current requirements for the NCAR regional acid deposition model (RADM). These include anthropogenic emissions of SO₂, sulfate aerosol, NO, NO₂, NH₃ and volatile organic compounds (VOC) in 10 reactivity classes, from United States and Canadian point and area sources on 80-km grid resolutions, for weekend and weekday seasonally representative days on a diurnal basis during the 1980–1982 period. Application of checking procedures, designed by our group to screen for subtle anomalies not identified at previous stages of quality assurance employed by the inventory developers, resulted in adjustments primarily to VOC emissions. Comparisons of the modified inventories, which provide an indication of uncertainties in emissions due to variations in inventory development procedures, revealed differences in the eastern United States total daily emissions to be at most on the order of 5 % for SO_x, and NO_x, 20% for VOC and 85% for NH₃. Studies of the impact of inventory differences on predictions of RADM were conducted for the 22–24 April 1981 period, which was monitored as part of the Oxidation and Scavenging Characteristics of April Rains program. Event total wet sulfate deposition differed by 10% or less while midday O₃ concentrations differed by 1% or less for individual grids over the modeling domain.     

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.     

Spatial and temporal variations of aerosol sulfate and trace elements in a sourcedominated urban environment

Time-resolved measurements of SO₂, sulfate, particulate carbon and trace metal (Pb, As, K, Mn, Fe and V) concentrations were performed simultaneously at four locations in Ljubljana, Yugoslavia, during February and April of 1985. During the winter three different SO₄²⁻ formation regimes are identified: A—morning period coinciding with maximum emissions and high humidity resulting in maximum SO₄²⁻ concentrations, with the sulfate formation during this period attributed to fast heterogeneous, aqueous oxidation of local SO₂ involving combustion products; B—late evening period with low humidity and high emissions when most SO₄²⁻ is primary; C—the remainder of the day when SO₄²⁻ appears to be of a regional origin and formed by a combination of heterogeneous and homogeneous processes. During the non-heating season, the SO₄²⁻ appears to be of regional origin.     

Shock Wave Cleaning of Air Filters

The trends in and relationships between ambient air concentrations of sulfur dioxide and sulfate aerosols at 48 urban sites and 27 nonurban sites throughout the U.S. between 1963 and 1972 have been analyzed. The substantial decreases in ambient SO₂ concentrations measured at urban sites in the eastern and midwestern U.S. are consistent with the corresponding reductions in local SO₂ emissions, but these decreases have been accompanied by only modest decreases in ambient sulfate concentrations. Large differences in the amounts of SO₂ emitted within individual air quality control regions are associated with much smaller differences in the corresponding ambient sulfate concentrations. Substantial changes in the patterns of SO₂ emissions between air quality regions result in essentially no differences between ambient sulfate concentrations in those air quality regions. Comparisons of several air quality regions in the eastern and western U.S. with similar SO₂ emission levels and patterns of emissions clearly demonstrates the higher ambient sulfate concentration levels in eastern air quality control regions. Relationships between SO₂, sulfates, and vanadium concentrations at eastern nonurban U.S. sites cannot be explained by local emission sources. These various observed results can be best explained by long distance sulfur oxide transport with chemical conversion of SO₂ to sulfates occurring over ranges of hundreds of kilometers. This conclusion has been suggested earlier and the present analysis strongly supports previous discussions. An impact of long range transport of sulfates is to emphasize the need for Consistent strategies for reduction of sulfur oxides throughout large geographical regions. Additions of large capacities involving elevated sources in mid-continental or western regions could result in significant increases in sulfate concentrations well downwind of such sources. Some of the types of research activities required to quantitate crucial experimental parameters are discussed.     

Seasonal,Episodic and Targeted Control of Sulfate Deposition

The large differences in seasonal rates of wet sulfate deposition observed at many receptors in eastern North America imply that reducing SO₂ emissions only in the summer half of the year (April-September) would bring about greater annual wet sulfate deposition reductions than reducing emissions by the same amount year-round. Targeting the emission reductions to those source areas which contribute the bulk of summer depositions in ecologically sensitive areas would increase further the gain factor, defined as the ratio of annual fractional deposition decrement to annual fractional emission decrement. In the northeastern U.S., between 10 and 15 rain episodes deposit about 60 percent of the annual wet sulfate; reducing emissions in the dry periods preceding these heavy deposition episodes could further increase the gain factor. However, it is difficult to predict these episodes, and they do not occur simultaneously over large regions of the country.     

The sensitivity of a 3-dimensional Eulerian model to uncertainties in emissions and dry deposition velocities

A 3-dimensional STEM-I Eulerian, regional scale transport/chemistry model for SO₂ and sulfate is used to investigate the relationships between model predictions and the resolution and uncertainty in the emissions and dry deposition velocities. Model results for conditions of 4 July 1974 where the emissions are time modulated, where the emissions are increased and decreased, and where the dry deposition velocities are increased and decreased are presented and discussed.     

Natural sulfur dioxide emissions from sulfuric soils

Soils have long been recognised as sulfur dioxide (SO₂) sinks, but we show that they can also be sources of atmospheric SO₂. Using static chambers and micrometeorological techniques, we have measured emissions of SO₂ from coastal lowland soils containing sulfides (mostly pyrite), commonly referred to as acid sulfate soils in Australia. SO₂ evolution seems coupled to evaporation of soil water containing sulfite. The global emissions of S from acid sulfate soils is estimated at about 3 Tg/year, which is of the same order as emissions from terrestrial biogenic sources and biomass burning and is about 3% of known anthropogenic emissions of S.     

The change in O3, SO2 and NO2 concentrations in Lithuania

Due to the dynamic nature of the atmosphere, substantial amounts of gaseous and particulate pollutants are transported to the areas distant from their sources. In order to determine the regional concentration levels of atmospheric pollutants in Lithuania, concentrations of gaseous O₃, SO₂, NO₂ and other pollutants have been measured at the Preila background station (55°20′ N and 21°00′ E, 5 m a.s.l.) since 1981. The long-term concentration data set enabled us to get temporal trends, both on a seasonal and longer time scale, to identify source areas of pollutants and to relate them to the emission data. Based on the data obtained, the different tendencies in the pollutant concentration changes were revealed. Positive trends for ozone (of 2.9% per year during 1983–2000) and a distinct negative trend for both sulphur dioxide (of 3.8% per year during 1981–2000) and nitrogen dioxide (of 3.8% per year during 1983–2000) were found. The air mass back-trajectory analysis was used to assess the source region of air pollutants transported to Lithuania. The pollutant concentration levels were compared with their emission changes in Europe and Lithuania. The general trends in SO₂ as well as in NO₂ concentrations observed are consistent with changes in SO₂ and NO₂ emissions in Europe and Lithuania.     

Significant geographic gradients in particulate sulfate over Japan determined from multiple-site measurements and a chemical transport model: Impacts of transboundary pollution from the Asian continent

We found a significant geographic gradient (longitudinal and latitudinal) in the sulfate (SO₄^2?) concentrations measured at multiple sites over the East Asian Pacific Rim region. Furthermore, the observed gradient was well reproduced by a regional chemical transport model. The observed and modeled SO₄^2? concentrations were higher at the sites closer to the Asian continent. The concentrations of SO₄^2? from China as calculated by the model also showed the fundamental features of the longitudinal/latitudinal gradient. The proportional contribution of Chinese SO₄^2? to the total in Japan throughout the year was above 50–70% in the control case, using data for Chinese sulfur dioxide (SO₂) emission from the Regional Emission Inventory in Asia (40–60% in the low Chinese emissions case, using Chinese SO₂ emissions data from the State Environmental Protection Administration of China), with a winter maximum of approximately 65–80%, although the actual concentrations of SO₄^2? from China were highest in summer. The multiple-site measurements and the model analysis strongly suggest that the SO₄^2? concentrations in Japan were influenced by the outflow from the Asian continent, and this influence was greatest in the areas closer to the Asian continent. In contrast, we found no longitudinal/latitudinal gradient in SO₂ concentrations; instead SO₂ concentrations were significantly correlated with local SO₂ emissions. Our results show that large amounts of particulate sulfate are transported over long distances from the East Asian Pacific Rim region, and consequently the SO₄^2? concentrations in Japan are controlled by the transboundary outflow from the Asian continent.     

Wet and dry deposition monitoring in Southeastern Michigan

Wet and dry deposition as collected by a bucket were measured at two sites in southeastern Michigan for two years. The precipitation had an average pH of 4.27 and a SO²⁻₄ to NO⁻₃ ratio of 2.0. Particulate dry deposition velocities of 0.6 cm s⁻¹ for SO²⁻₄ and NO⁻₃ and > 2 cm s⁻¹ for Cl⁻, Ca²⁺, Mg²⁺,Na⁺ and K⁺ were calculated. The ambient particle composition, dry bucket collection and wet deposition were compared at two sites, one urban and the other rural. Higher ambient particle concentrations and dry deposition rates were measured at the urban site than the rural site, indicating the influence of local emissions. However, local emissions had no effect on the wet deposition concentrations. The influence of more distant source regions was examined by separating the precipitation events by wind direction. The events from the south and east had the highest SO²⁻₄ to NO⁻₃ ratios, which corresponded to the areas with the highest sulfur emissions. NO⁻₃ showed no directional dependence.Wet deposition was examined for the effect of storm type and seasonal trends. Contrary to a recent study on Long Island, we found higher concentrations of H⁺, SO²⁻₄ and NH⁺₄ in winter rain compared to snow. The wet deposition concentrations of H⁺, SO²⁻₄, and NH⁺₄ were highest in the summer, while only Na⁺ and Cl⁻ concentrations were highest in the winter, presumably due to winter road salting. The total deposition of acidic ions was highest in the summer and lowest in the winter, due both to lower concentrations and lower precipitation volumes in the winter. The dry deposition as collected by a bucket accounted for 1 % of total H⁺ deposition, 21 % of SO²⁻₄ deposition, 27% of NO⁻₃ deposition, 50% of Cl⁻ deposition and 61 % of Ca²⁺ deposition.     

Spatial variability of sulfur dioxide and sulfate over complex terrain in East Tennessee,USA

In 2004 and 2005, the East Tennessee Ozone Study (ETOS) enhanced its regional measurement program with annular denuder systems to quantify sulfur dioxide (SO₂) and PM_2.5 sulfate (SO₄^2?) at five sampling sites that were representative of the complex terrain and physiographic features of East Tennessee. Intersite spatial variability was more defined for SO₂ than for SO₄^2?, which showed a fairly uniform structure in both daytime and nighttime measurements. Pollution roses indicated that two sites may have been influenced by the proximity of SO₂ emission sources. The data suggest that SO₂ is affected by nearby sources in the study area while the sources of SO₄^2? are regionally distributed.     

A Study of Primary Sulfate Emissions From a Coal-Fired Boiler with FGD

A study was carried out to investigate the emissions of SO₂ and primary sulfate materials (H₂SO₄ and inorganic particulate matter) from a boiler burning fossil fuel and using a wet-limestone scrubber for SO₂ removal. Experiments were designed to assess the scrubbing efficiency for SO₂ and sulfate, as well as the potential for scrubber liquor reentrainment. The boiler studied was an 820 MW cyclone-fired unit equipped with a wet, limestone scrubber, consisting of eight two-stage venturi-absorber modules designed to treat a flue gas flow rate of 2,760,000 acfm. The boiler fuel was a low-grade sub-bituminous coal with ash and sulfur contents of 25 and 5%, respectively. Multiple-sampling methods were employed concurrently on the inlet and outlet of a candidate absorber module to measure SO₂, total water-soluble sulfate, and free H₂SO₄. Samples were collected during three field experiments from September 1977 through April 1978. The average SO₂ scrubbing efficiency was 76% and was observed to decrease over the 5 day operation/maintenance cycle of the module. The total water-soluble sulfate input to the scrubber amounted to approximately 1% of the total sulfur oxides and was composed of a 5:1 ratio of H₂SO₄ to particulate sulfate. The total sulfate scrubbing efficiency, averaging about 29%, was invariant with respect to SO₂ removal. The sulfate emissions measured in the scrubber exit gas consisted of about 85 % H₂SO₄ as a fine aerosol. Mass emissions of acid and particulate sulfate were calculated as 1730 Ib/hr and 305 Ib/hr, respectively.     

Assessing the impact of the acid deposition control program

A goal of the acidic deposition control program in the United States has been to link emissions control policies, such as those mandated under Title IV of the US Clean Air Act Amendments (CAAA) of 1990, to improvements in air and water quality. Recently, several researchers have reported trends in the time series of pollutant data in an effort to evaluate the effectiveness of the CAAA in reducing the acidic deposition problem. It is well known that pollutant concentrations are highly influenced by meteorological and climatic variations. Also, spatial and temporal inhomogeneities in time series of pollutant concentrations, induced by differences in the data collection, reduction, and reporting practices, can significantly affect the trend estimates. We present a method to discern breaks or discontinuities in the time series of pollutants stemming from emission reductions in the presence of meteorological and climatological variability. Using data from a few sites, this paper illustrates that linear trend estimates of concentrations of SO₂, aerosol SO₄²⁻, and precipitation-weighted SO₄²⁻ and NO₃⁻ can be biased because of such complex features embedded in pollutant time series.     

Modelling the atmospheric transport and deposition of sulphur and nitrogen over the United Kingdom and assessment of the influence of SO2 emissions from international shipping

A statistical Lagrangian atmospheric transport model was used to generate annual maps of deposition of sulphur and oxidised and reduced nitrogen for the UK at a 5×5 km² resolution. The model was run using emissions for the year 2002. The model was compared with measurements of gas concentrations (SO₂, NO_x, HNO₃ and NH₃) and of wet deposition and aerosol concentrations of SO₄²⁻, NO₃⁻ and NH₄⁺ from national monitoring networks. Good correlation was obtained, demonstrating that the model is capable of accurately estimating the mass balance and spatial distribution of sulphur and nitrogen compounds in the atmosphere. A future emissions scenario for the year 2020 was used to test the influence of shipping emissions on sulphur deposition in the UK. The results show that, if shipping emissions are assumed to increase at a rate of 2.5% per year, their relative contribution to sulphur deposition is expected to increase from 9% to 28% between 2002 and 2020. The model was compared to both a European scale and a global scale chemical transport model and found to give broad agreement with the magnitude and location of sulphur deposition associated with shipping emissions. Enforcement of the MARPOL convention to reduce the sulphur content in marine fuel to 1% was estimated to result in a 6% reduction in total sulphur deposition to the UK for the year 2020. The percentage area of sensitive habitats with exceedance of critical loads for acidity in the UK was predicted to decrease by 1% with the implementation of the MARPOL convention.     

Reduction of atmospheric emissions due to switching from fuel oil to natural gas at a power plant in a critical area in Central Mexico

ABSTRACT

A case study was conducted to evaluate the SO₂ emission reduction in a power plant in Central Mexico, as a result of the shifting of fuel oil to natural gas. Emissions of criteria pollutants, greenhouse gases, organic and inorganic toxics were estimated based on a 2010 report of hourly fuel oil consumption at the “Francisco Pérez Ríos” power plant in Tula, Mexico. For SO₂, the dispersion of these emissions was assessed with the CALPUFF dispersion model. Emissions reductions of > 99% for SO₂, PM and Pb, as well as reductions >50% for organic and inorganic toxics were observed when simulating the use of natural gas. Maximum annual (993 µg/m³) and monthly average SO₂ concentrations were simulated during the cold-dry period (152–1063 µg/m³), and warm-dry period (239–432 µg/m³). Dispersion model results and those from Mexico City’s air quality forecasting system showed that SO₂ emissions from the power plant affect the north of Mexico City in the cold-dry period. The evaluation of model estimates with 24 hr SO₂ measured concentrations at Tepeji del Rio suggests that the combination of observations and dispersion models are useful in assessing the reduction of SO₂ emissions due to shifting in fuels. Being SO₂ a major precursor of acid rain, high transported sulfate concentrations are of concern and low pH values have been reported in the south of Mexico City, indicating that secondary SO₂ products emitted in the power plant can be transported to Mexico City under specific atmospheric conditions.

Implications: Although the surroundings of a power plant located north of Mexico City receives most of the direct SO₂ impact from fuel oil emissions, the plume is dispersed and advected to the Mexico City metropolitan area, where its secondary products may cause acid rain. The use of cleaner fuels may assure significant SO₂ reductions in the plant emissions and consequent acid rain presence in nearby populated cities and should be compulsory in critical areas to comply with annual emission limits and health standards.     

Wet and dry deposition of sulfur and nitrogen compounds in Ontario

Measurements have been made of sulfur and nitrogen compounds in precipitation since 1980 and in air since 1981 in Ontario. This paper presents results of the atmospheric deposition measurement program to the end of 1985. As is to be expected from the distribution of emission sources, annual concentrations of SO₄²⁻ andNO₃⁻ in precipitation, and of SO₂,SO₄²⁻ andNO₃⁻ in air are higher in southern Ontario than in northern Ontario. The corresponding distribution pattern for deposition is similar to that of concentration. A wet SO₄²⁻ deposition rate of 20 kg ha¹⁻ y¹⁻, a value considered critical for the acidification of sensitive water bodies, is exceeded in all of central and southern Ontario. On a province-wide basis, sulfur wet deposition is about four times higher than sulfur dry deposition. For nitrogen, wet and dry deposition are more comparable, though the former is still higher. The S- and N-species display different seasonal trends in concentration and deposition reflecting a dependence on meteorological factors, and on the associated chemical transformation rates. On the other hand, year to year variations are small.     

Non-linear response of wet deposition to emissions reduction: A model study

An Eulerian atmospheric model with complex chemistry (Acidic Deposition and Oxidant Model) and a Lagrangian model with linear chemistry (Ontario Ministry of the Environment Trajectory Model) were used to simulate the wet SO₄²⁻ deposition pattern over eastern North America for 16 days during April 1981.The two model results agree reasonably well with each other when the 16 day average values are compared. They also show reasonable agreement with observed data. Having established the ability of the models to predict deposition patterns for 1981 emissions, reduction scenarios with 50% SO_x and 50% SO_x and NO_x of the 1981 emissions were studied through the Eulerian model. Near the heavy emissions area, the reduction in SO₄²⁻ wet deposition is only about 30–40%. In this respect the linear Lagrangian model departs significantly from the Eulerian model. This non-linearity in response is attributed to the role of oxidants in controlling the conversion of SO₂ to SO₄²⁻.     

Needed: A National R&D Effort To Develop Individual Air Pollution Monitor Instrumentation

The results from the regional air quality analysis for the Four Corners Study are discussed in this paper. This study was one of five regional studies conducted for the National Commission on Air Quality. Potential regional air quality impacts were evaluated through the year 1995 for alternative energy scenarios under current and alternative regulatory policies. The alternative regulatory policies include emission fees, technology standards, emission ceilings, and prevention of significant deterioration class elimination. The alternatives were compared in terms of their impacts on regional visibility and on the ambient concentrations of SO₂, SO₄, and primary fine particulates. The fate of the pollutants was estimated. The alternative regulatory policies were quite different with respect to their control of SO_X emissions and their impacts on regional visibility. Sources located outside of the study region were estimated to have a major impact on regional air quality within the study region.     

Sulfur Dioxide Emissions and Market Effects under the Clean Air Act Acid Rain Program

ABSTRACT

The Clean Air Act Amendments of 1990 (CAAA90) established a national program to control sulfur dioxide (SO₂) emissions from electricity generation. CAAA90's market-based approach includes trading and banking of Soumissions allowances. We analyzed data describing electric utility SO₂ emissions in 1995, the first year of the program's Phase I, and market effects over the 1990-1995 period. Fuel switching and flue-gas desulfurization were the dominant means used in 1995 by targeted generators to reduce emissions to 51% of 1990 levels. Flue-gas desulfur-ization costs, emissions allowance prices, low-sulfur coal prices, and average sulfur contents of coals shipped to electric utilities declined over the 1990-1995 period. Projections indicate that 13-15 million allowances will have been banked during the program's Phase I, which ends in 1999, a quantity expected to last through the first decade of the program's stricter Phase II controls. In 1995, both allowance prices and SO₂ emissions were below pre-CAAA90 expectations. The reduction of SO₂ emissions beyond pre-CAAA90 expectations, combined with lower-than-expected allowance prices and declining compliance costs, can be viewed as a success for market-based environmental controls.     

Supply Curves for Using Powder River Basin Coal to Reduce Sulfur Emissions

Abstract

Supply curves were prepared for coal-fired power plants in the contiguous United States switching to Wyoming's Powder River Basin (PRB) low-sulfur coal. Up to 625 plants, representing ～44% of the nameplate capacity of all coal-fired plants, could switch. If all switched, more than $8.8 billion additional capital would be required and the cost of electricity would increase by up to $5.9 billion per year, depending on levels of plant derating. Coal switching would result in sulfur dioxide (SO₂) emissions reduction of 4.5 million t/yr. Increase in cost of electricity would be in the range of 0.31-0.73 cents per kilowatt-hour. Average cost of S emissions reduction could be as high as $1298 per t of SO₂. Up to 367 plants, or 59% of selected plants with 32% of 44% nameplate capacity, could have marginal cost in excess of $1000 per t of SO₂. Up to 73 plants would appear to benefit from both a lowering of the annual cost and a lowering of SO₂ emissions by switching to the PRB coal.