Gaseous Sulfur Pollutants from Urban and Natural Sources

Major aspects of the circulation through the atmospheric environment of sulfur pollutants have been estimated, including source magnitudes, residual atmospheric concentrations, and scavenging processes. The compounds considered include SO₂ and H₂S, as well as sulfates. One-third of the sulfur reaching the atmosphere comes from pollutant sources, mainly as SO₂. Within the atmosphere there is a net transfer of sulfur from land to ocean areas. Pollutant sources annually amount to 73 × 10⁶ tons as sulfur while natural sources amount to 142 × 10⁶ tons, mainly as H₂S and sulfate sea spray. More than two thirds of the natural and pollutant sulfur emissions occur in the northern hemisphere. When only pollutant emissions are considered, 93 per cent occur in the northern hemisphere.     

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.     

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.     

Nonmethane Organic Compound to Nitrogen Oxide Ratios and Organic Composition in Cities and Rural Areas

The observed ranges in nonmethane organic compound (NMOC) concentrations, NMOC composition and nitrogen oxides (NO_X) concentrations have been evaluated for urban and nonurban areas at ground level and aloft of the contiguous United States. The ranges in NMOC to NO_X ratios also are considered. The NMOC composition consistently shifts towards less reactive compounds, especially the alkanes, in air parcels over nonurban areas compared to the NMOC composition near ground level within urban areas. The values for the NMOC to NO_X ratios, 1.2 to 4.2, in air aloft over nonurban areas are lower than in air at ground level urban sites, ≥8, and much lower than in air at ground level nonurban sites, ≥20.

The layers of air aloft over a number of nonurban areas of the United States tend to accumulate NO_X emissions from the tall stacks of large fossil fuel power plants located at nonurban sites. During the night into the morning hours, the air aloft is isolated from any fresh NMOC emissions predominately coming from near surface sources. Conversely, during this extended period of restricted vertical mixing, air near the surface accumulates NMOC emissions while this air is isolated from the major NO_X sources emitting aloft. These differences in the distribution of NMOC and NO_X sources appear to account for the much larger NMOC to NO_X ratios reported near ground level compared to aloft over nonurban areas.

Two types of experimental results are consistent with these conclusions: (1) observed increases in surface rural NO_X concentrations during the morning hours during which the mixing depth increases to reach the altitude at which NO_X from the stacks of fossil fuel power plants is being transported downwind; (2) high correlations of total nitrate at rural locations with Se, which is a tracer for coal-fired power plant NO_X emissions.

The implications of these conclusions from the standpoint of air quality strategies are suggested by use of appropriate scenarios applied to both urban and regional scale photochemical air quality models. The predictions from urban model scenarios with NMOC to NO_X ratios up to 20 are that NO_X control will result in the need for the control of more NMOC emissions than necessary in the absence of NO_X control, in order to meet the O₃ standard. On a regional scale, control of NO_X emissions from fossil fuel power plants has little overall effect regionally but does result on a more local scale in both small decreases and increases in O₃ concentrations compared to the baseline scenario without NO_X control. The regional modeling results obtained to date suggest that NO_X control may be effective in reducing O₃ concentrations only for a very limited set of conditions in rural areas.     

Atmospheric Sulfates from Biological Sources

Bacteriogenic production of H₂S occurs in fine-grained anoxic muds, is promoted by organic and nutrient pollution of water, peaks in the warm months of the year, and is the source of most of the estimated 100 to 200 million tons of biogenic sulfur annually contributed to the global atmosphere. We tested the hypothesis that biogenic sulfur contributes to the atmospheric load of sulfate in urban and nonurban sites by statistical analyses of the 24 hour sulfate levels measured in 4 coastal and 3 Inland nonurban sites where pollutant sulfur dioxide emissions are absent or negligible, and in 8 coastal and 10 inland urban sites, all located in New England or Middle Atlantic states.

Comparisons of annual and seasonal mean sulfate levels show that in nonurban groups summertime sulfate levels significantly exceed wintertime levels, and in summer, sulfate levels in urban sites are nearly the same as in nonurban sites. Comparisons of group sulfate means in 4 New York cities near extended bodies of polluted water with those in 10 inland upstate New York cities show significantly higher levels in the cities near polluted water in spring, summer, and fall and for the year as a whole, but not in winter, when the levels were similar. When the nonurban and urban sites are grouped for proximity to coasts (where bacterial sulfate reduction is active in sediments) paired groups of coastal and inland urban and nonurban sites show no significant differences in sulfate levels in summer and fall.

Studies of the summertime sulfate means in New York state show no evidence of an elevated anthropogenic background which could explain the high summertime sulfate level observed in one nonurban site in that state, while analyses of the day to day fluctuations in urban and nonurban sites support the conclusion that nonurban sites have large local (biogenic) sulfate sources in summer and fall, and that local sulfate sources also exist in spring and may exist in winter.

We conclude that biogenic sulfate sources contribute most of the sulfate observed in the cities studied during summer and fall, and in some cities also contribute in other seasons. These biogenic contributions vary with local conditions and are estimated to contribute up to 6 µg/m³ (50%) or more to the annual geometric mean sulfate levels observed in some cities located near extensive bodies of polluted water.     

Midwest/western/eastern U.S. precipitation and aerosol sulfate: Differences attributable to natural source inputs?

Factor analysis comparisons between the MAP3S network and Minnesota precipitation chemistry data show marked differences. An assessment of ambient aerosol and precipitation chemistry data obtained at several Colorado and Minnesota sites suggests that natural source inputs may contribute to the sulfate observed in ambient aerosol and at least partly, explain the marked differences of Minnesota and Colorado precipitation chemistry data from that of MAP3S (eastern U.S.). However, a recently proposed mechanism, SO₂ to SO₄ conversion on the surface of dust particles, may be more important than natural sources in explaining western and midwestern precipitation chemistry data. It is concluded that these predominantly non-acidic SO₄ sources may explain the poor association between the H⁺ and SO₄ in many western and some midwestern precipitation chemistry data sets.     

Understanding of regional air pollution over China using CMAQ,part I performance evaluation and seasonal variation

The U.S. EPA Models-3 Community Multiscale Air Quality (CMAQ) modeling system with the process analysis tool is applied to China to study the seasonal variations and formation mechanisms of major air pollutants. Simulations show distinct seasonal variations, with higher surface concentrations of sulfur dioxide (SO₂), nitrogen dioxide (NO₂), and particulate matter with aerodynamic diameter less than or equal to 10 μm (PM₁₀), column mass of carbon monoxide (CO) and NO₂, and aerosol optical depth (AOD) in winter and fall than other seasons, and higher 1-h O₃ and troposphere ozone residual (TOR) in spring and summer than other seasons. Higher concentrations of most species occur over the eastern China, where the air pollutant emissions are the highest in China. Compared with surface observations, the simulated SO₂, NO₂, and PM₁₀ concentrations are underpredicted throughout the year with NMBs of up to ?51.8%, ?32.0%, and ?54.2%, respectively. Such large discrepancies can be attributed to the uncertainties in emissions, simulated meteorology, and deviation of observations based on air pollution index. Max. 1-h O₃ concentrations in Jan. and Jul. at 36-km are overpredicted with NMBs of 12.0% and 19.3% and agree well in Apr. and Oct. Simulated column variables can capture the high concentrations over the eastern China and low values in the central and western China. Underpredictions occur over the northeastern China for column CO in Apr., TOR in Jul., and AODs in both Apr. and Jul.; and overpredictions occur over the eastern China for column CO in Oct., NO₂ in Jan. and Oct., and AODs in Jan. and Oct. The simulations at 12-km show a finer structure in simulated concentrations than that at 36-km over higher polluted areas, but do not always give better performance than 36-km. Surface concentrations are more sensitive to grid resolution than column variables except for column NO₂, with higher sensitivity over mountain and coastal areas than other regions.     

Regional trends in wet deposition of sulfate in the United States and SO2 emissions from 1980 through 1995

Regional trends of seasonal and annual wet deposition and precipitation-weighted concentrations (PWCs) of sulfate in the United States over the period 1980–1995 were developed from monitoring data and scaled to a mean of unity. To reduce some effects of year to year climatological variability, the unitless regional deposition and PWC trends were averaged (hereafter termed CONCDEP). The SO₂ emissions data over the same period from the United States, Canada, and northern Mexico, aggregated by state and province, were weighted appropriately for each deposition region in turn to produce scaled trends of the emissions affecting each region. The emission-weighting factors, which were held constant year to year, were estimated by exercise of a regional transport model. The sulfate CONCDEP regional trends are generally similar to those of regionally weighted SO₂ emissions, although the latter trends are less steep and the former trends have more year to year variability. In eastern regions, sulfate CONCDEPs and SO₂ emissions patterns both generally show an initial decrease, an essentially trendless middle period, and a final decrease as reductions mandated by the Acid Rain Provisions of the 1990 Clean Air Act Amendments began. Linear regressions of regional sulfate CONCDEPs on corresponding regionally weighted SO₂ emissions produced statistically significant relationships in all regions. The analysis indicated that although regional sulfate CONCDEPs decreased relatively faster than did SO₂ emissions during the period in all regions except the Great Plains, in general the slopes were not significantly different from unity.     

NCAQ Report to Congress: Review and Response

Airborne measurements of gaseous and particulate sulfur and nitrogen pollutants were made in southwestern Kentucky on the afternoon of October 21, 1979. Back-trajectory analysis indicates that the sampled air parcel moved over northern Florida, Alabama, and western Tennessee during the two days prior to sampling. Before moving over Florida, the air parcel was over the Atlantic Ocean for at least five days. Analytical long-range transport (LRT) model predictions based on anthropogenic emissions account for only about 75% of the airborne measured concentrations of 14.7 μg m^?3 for SO₂ and 4.8 μg m^?3 for SO₄ ^2?. The remaining 25 % is thought to be due to biogenic sulfur emissions from the extensive wetland areas along the Gulf Coast.

Forward-trajectory analysis indicates that the air parcel moved to the Adirondack Mountains of New York State 24 hours after sampling. Model predictions indicate that SO₂ and SO₄ ^2? mean layer concentrations at the Adirondacks were 24 and 16 μg^?3, respectively. Almost half of this sulfur was estimated to come from emissions in the heavily industrialized region along the Ohio River Valley.

Further comparisons used a measurement data base obtained in southeastern Canada and the state of Arkansas during August 1976. An air parcel was tracked for seven days as it entered the north central United States, stagnated over the lower midwest, and then moved to eastern Canada. Model predictions were in substantial agreement with regional SO₄ ^2? concentrations measured at a number of ground-level sites. Average SO₄ ^2? concentrations measured in central Arkansas on August 10, 1976 were 20 μ m^?3 vs. a modeled value of 19 μ m^?3. Average SO₄ ^2? concentrations measured in Nova Scotia four days later were 22 μg^?3 vs. a modeled estimate of 24 μg^?3.     

Assessment of ambient air quality in the port of Naples

Two experimental monitoring campaigns were carried out in 2012 to investigate the air quality in the port of Naples, the most important in southern Italy for traffic of passengers and one of the most important for goods. Therefore, it represents an important air pollution source located close to the city of Naples. The concentrations of sulfur dioxide (SO₂), nitrogen dioxide (NO₂), and BTEX (benzene, toluene, ethylbenzene, and xylenes) in the air were measured at 15 points inside the Naples port area through the use of passive samplers. In addition, a mobile laboratory was positioned in a fixed point inside the port area to measure continuous concentration of pollutants together with particulate matter, ambient parameters, and wind direction and intensity. The pollution levels monitored were compared with those observed in the urban area of Naples and in other Mediterranean ports. Even though the observation time was limited, measured concentrations were also compared with limit values established by European legislation. All the measured pollutants were below the limits with the exception of nitrogen dioxide: its average concentration during the exposition time exceeded the yearly limit value. A spatial analysis of data, according to the measured wind direction and intensity, provided information about the effects that ship emissions have on ambient air quality in the port area. The main evidence indicates that ship emissions influence sulfur dioxide concentration more than any other pollutants analyzed.

Implications: Two monitoring campaigns were carried out to measure BTEX, SO₂, NO₂, and PM₁₀ (particulate matter with an aerodynamic diameter <10 μm) air concentrations in the port of Naples. NO₂ hourly average and PM₁₀ daily average comply with European legislative standards. Spatial variation of pollutants long the axis corresponding to the prevailing wind direction seems to indicate a certain influence of ship emissions for SO₂. For NO₂ and PM₁₀, a correlation between concentrations in the harbor and those measured by the air quality monitoring stations sited in the urban area of Naples was observed, indicating a possible contribution of the near road traffic to the air pollution in the port of Naples.     

Assessment of contribution of SO2 and NO2 from different sources in Jamshedpur region, India

Contribution of pollution from different types of sources in Jamshedpur, the steel city of India, has been estimated in winter 1993 using two approaches in order to delineate and prioritize air quality management strategies for the development of region in an environmental friendly manner. The first approach mainly aims at preparation of a comprehensive emission inventory and estimation of spatial distribution of pollution loads in terms of SO₂ and NO₂ from different types of industrial, domestic and vehicular sources in the region. The results indicate that industrial sources account for 77% and 68% of the total emissions of SO₂ and NO₂, respectively, in the region, whereas vehicular emissions contributed to about 28% of the total NO₂ emissions. In the second approach, contribution of these sources to ambient air quality levels to which the people are exposed to, was assessed through air pollution dispersion modelling. Ambient concentration levels of SO₂ and NO₂ have been predicted in winter season using the ISCST3 model. The analysis indicates that emissions from industrial sources are responsible for more than 50% of the total SO₂ and NO₂ concentration levels. Vehicular activities contributed to about 40% of NO₂ pollution and domestic fuel combustion contributed to about 38% of SO₂ pollution. Predicted 24-h concentrations were compared with measured concentrations at 11 ambient air monitoring stations and good agreement was noted between the two values. In-depth zone-wise analysis of the above indicates that for effective air quality management, industrial source emissions should be given highest priority, followed by vehicular and domestic sources in Jamshedpur region.     

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.     

Regional-scale impacts of Phase I of the Clean Air Act Amendments in the USA: the relation between emissions and concentrations,both wet and dry

A comparison of data records in the 1990s, both before (1991–1994) and after (1995–1997) implementation of Phase I of the Clean Air Act Amendments (CAAA) of 1990 for the eastern US, shows a significant reduction in SO₂ emissions for most states, except for Texas, North Carolina, Illinois, Florida, and Alabama. However, of the major NO_x emitting states, only two eastern states (New York and Pennsylvania) show significant declines in NO_x. A pattern of large declines in SO₂ emissions (>20%) after CAAA implementation, and large declines in precipitation SO₄²⁻ and H⁺, as well as air concentrations of SO₂ and SO₄²⁻ (components of dry deposition), exists for most regions of the eastern US. In most cases, the emission/concentration relations are close to 1 : 1 when the source region based on 15-h back trajectories is used for the New England region, and source regions based on 9-h back trajectories are used for the six other eastern US regions that were studied. The southern Appalachian Mountain region, an acid-sensitive area receiving high levels of acidic deposition, has not seen an appreciable improvement in precipitation acidity. This area has also shown the least improvement in wet and dry sulfur concentrations, of the areas examined. Precipitation base cations (Ca²⁺ and Mg²⁺) show a pattern of either increasing or level concentrations when comparing 1990–1994 to 1995–1998 data, for six of the seven regions examined. Ammonium concentrations have generally changed <10%, except for the Illinois and southern Appalachian Mtn. regions, which increased >15%.     

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.     

Interannual variability of transboundary sulphur flux

A study was conducted by the Atmospheric Environment Service (AES) to compute the transboundary sulphur flux between eastern Canada and the eastern United States on a monthly and annual basis for the years 1980–1983.The S fluxes were calculated using the AES Lagrangian model. SO₂ and SO₄ concentrations were computed at 16 line segment mid-points along the Canada-U.S. border from western Ontario through Quebec to the Maritimes. Sulphur fluxes were determined at 6-h intervals and summed temporally and spatially to obtain the total transboundary S flux. By using only the Canadian and only the U.S. emissions, the total S flux contributions from each country could be determined.Canadian and U.S. emissions declined from 1980 to 1983 by 20% and 11%, respectively, then increased slightly in 1983. The total annual S flux from the U.S. to Canada ranged from 1.86 Mt S (1980) to 1.61 Mt S (1983) while the flux from Canada to the U.S. ranged from 0.75 Mt S (1980) to 0.52 Mt S (1982). Fluxes between both countries were highest (lowest) in the winter (summer) because of the stronger (lighter) winds and higher (lower) SO₂ concentrations. However, SO₄ mass flux peaked in summer and early fall because of higher chemical conversion rates.Annual transboundary fluxes were observed to change by up to 20% in response to emissions changes and meteorological variability and these two influences should be considered together when assessing flux changes.     

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.     

Source apportionment of emissions from light-duty gasoline vehicles and other sources in the United States for ozone and particulate matter

Federal Tier 3 motor vehicle emission and fuel sulfur standards have been promulgated in the United States to help attain air quality standards for ozone and PM_2.5 (particulate matter with an aerodynamic diameter <2.5 μm). The authors modeled a standard similar to Tier 3 (a hypothetical nationwide implementation of the California Low Emission Vehicle [LEV] III standards) and prior Tier 2 standards for on-road gasoline-fueled light-duty vehicles (gLDVs) to assess incremental air quality benefits in the United States (U.S.) and the relative contributions of gLDVs and other major source categories to ozone and PM_2.5 in 2030. Strengthening Tier 2 to a Tier 3-like (LEV III) standard reduces the summertime monthly mean of daily maximum 8-hr average (MDA8) ozone in the eastern U.S. by up to 1.5 ppb (or 2%) and the maximum MDA8 ozone by up to 3.4 ppb (or 3%). Reducing gasoline sulfur content from 30 to 10 ppm is responsible for up to 0.3 ppb of the improvement in the monthly mean ozone and up to 0.8 ppb of the improvement in maximum ozone. Across four major urban areas—Atlanta, Detroit, Philadelphia, and St. Louis—gLDV contributions range from 5% to 9% and 3% to 6% of the summertime mean MDA8 ozone under Tier 2 and Tier 3, respectively, and from 7% to 11% and 3% to 7% of the maximum MDA8 ozone under Tier 2 and Tier 3, respectively. Monthly mean 24-hr PM_2.5 decreases by up to 0.5 μg/m³ (or 3%) in the eastern U.S. from Tier 2 to Tier 3, with about 0.1 μg/m³ of the reduction due to the lower gasoline sulfur content. At the four urban areas under the Tier 3 program, gLDV emissions contribute 3.4–5.0% and 1.7–2.4% of the winter and summer mean 24-hr PM_2.5, respectively, and 3.8–4.6% and 1.5–2.0% of the mean 24-hr PM_2.5 on days with elevated PM_2.5 in winter and summer, respectively.

Implications: Following U.S. Tier 3 emissions and fuel sulfur standards for gasoline-fueled passenger cars and light trucks, these vehicles are expected to contribute less than 6% of the summertime mean daily maximum 8-hr ozone and less than 7% and 4% of the winter and summer mean 24-hr PM_2.5 in the eastern U.S. in 2030. On days with elevated ozone or PM_2.5 at four major urban areas, these vehicles contribute less than 7% of ozone and less than 5% of PM_2.5, with sources outside North America and U.S. area source emissions constituting some of the main contributors to ozone and PM_2.5, respectively.     

Emissions Variability Processor (EMVAP): Design,evaluation, and application

Emissions of pollutants such as SO₂ and NOx from external combustion sources can vary widely depending on fuel sulfur content, load, and transient conditions such as startup, shutdown, and maintenance/malfunction. While monitoring will automatically reflect variability from both emissions and meteorological influences, dispersion modeling has been typically conducted with a single constant peak emission rate. To respond to the need to account for emissions variability in addressing probabilistic 1-hr ambient air quality standards for SO₂ and NO₂, we have developed a statistical technique, the Emissions Variability Processor (EMVAP), which can account for emissions variability in dispersion modeling through Monte Carlo sampling from a specified frequency distribution of emission rates. Based upon initial AERMOD modeling of from 1 to 5 years of actual meteorological conditions, EMVAP is used as a postprocessor to AERMOD to simulate hundreds or even thousands of years of concentration predictions. This procedure uses emissions varied hourly with a Monte Carlo sampling process that is based upon the user-specified emissions distribution, from which a probabilistic estimate can be obtained of the controlling concentration. EMVAP can also accommodate an advanced Tier 2 NO₂ modeling technique that uses a varying ambient ratio method approach to determine the fraction of total oxides of nitrogen that are in the form of nitrogen dioxide. For the case of the 1-hr National Ambient Air Quality Standards (NAAQS, established for SO₂ and NO₂), a “critical value” can be defined as the highest hourly emission rate that would be simulated to satisfy the standard using air dispersion models assuming constant emissions throughout the simulation. The critical value can be used as the starting point for a procedure like EMVAP that evaluates the impact of emissions variability and uses this information to determine an appropriate value to use for a longer term (e.g., 30-day) average emission rate that would still provide protection for the NAAQS under consideration. This paper reports on the design of EMVAP and its evaluation on several field databases that demonstrate that EMVAP produces a suitably modest overestimation of design concentrations. We also provide an example of an EMVAP application that involves a case in which a new emission limitation needs to be considered for a hypothetical emission unit that has infrequent higher-than-normal SO₂ emissions.

ImplicationsEmissions of pollutants from combustion sources can vary widely depending on fuel sulfur content, load, and transient conditions such as startup and shutdown. While monitoring will automatically reflect this variability on measured concentrations, dispersion modeling is typically conducted with a single peak emission rate assumed to occur continuously. To realistically account for emissions variability in addressing probabilistic 1-hr ambient air quality standards for SO₂ and NO₂, the authors have developed a statistical technique, the Emissions Variability Processor (EMVAP), which can account for emissions variability in dispersion modeling through Monte Carlo sampling from a specified frequency distribution of emission rates.     

Response of Fine Particulate Matter to Emission Changes of Oxides of Nitrogen and Anthropogenic Volatile Organic Compounds in the Eastern United States

Abstract

A three-dimensional chemical transport model (Particulate Matter Comprehensive Air Quality Model with Extensions [PMCAMx]) is used to investigate changes in fine particle (PM_2.5) concentrations in response to 50% emissions changes of oxides of nitrogen (NO_x) and anthropogenic volatile organic compounds (VOCs) during July 2001 and January 2002 in the eastern United States. The reduction of NO_x emissions by 50% during the summer results in lower average oxidant levels and lowers PM_2.5 (8% on average), mainly because of reductions of sulfate (9–11%), nitrate (45–58%), and ammonium (7–11%). The organic particulate matter (PM) slightly decreases in rural areas, whereas it increases in cities by a few percent when NO_x is reduced. Reduction of NO_x during winter causes an increase of the oxidant levels and a rather complicated response of the PM components, leading to small net changes. Sulfate increases (8–17%), nitrate decreases (18– 42%), organic PM slightly increases, and ammonium either increases or decreases a little. The reduction of VOC emissions during the summer causes on average a small increase of the oxidant levels and a marginal increase in PM_2.5. This small net change is due to increases in the inorganic components and decreases of the organic ones. Reduction of VOC emissions during winter results in a decrease of the oxidant levels and a 5–10% reduction of PM_2.5 because of reductions in nitrate (4–19%), ammonium (4–10%), organic PM (12–14%), and small reductions in sulfate. Although sulfur dioxide (SO₂) reduction is the single most effective approach for sulfate control, the coupled decrease of SO₂ and NO_x emissions in both seasons is more effective in reducing total PM_2.5 mass than the SO₂ reduction alone.     

Assessment of air quality benefits from national air pollution control policies in China. Part II: Evaluation of air quality predictions and air quality benefits assessment

Following the meteorological evaluation in Part I, this Part II paper presents the statistical evaluation of air quality predictions by the U.S. Environmental Protection Agency (U.S. EPA)’s Community Multi-Scale Air Quality (Models-3/CMAQ) model for the four simulated months in the base year 2005. The surface predictions were evaluated using the Air Pollution Index (API) data published by the China Ministry of Environmental Protection (MEP) for 31 capital cities and daily fine particulate matter (PM_2.5, particles with aerodiameter less than or equal to 2.5 μm) observations of an individual site in Tsinghua University (THU). To overcome the shortage in surface observations, satellite data are used to assess the column predictions including tropospheric nitrogen dioxide (NO₂) column abundance and aerosol optical depth (AOD). The result shows that CMAQ gives reasonably good predictions for the air quality.The air quality improvement that would result from the targeted sulfur dioxide (SO₂) and nitrogen oxides (NO_x) emission controls in China were assessed for the objective year 2010. The results show that the emission controls can lead to significant air quality benefits. SO₂ concentrations in highly polluted areas of East China in 2010 are estimated to be decreased by 30–60% compared to the levels in the 2010 Business-As-Usual (BAU) case. The annual PM_2.5 can also decline by 3–15 μg m^?3 (4–25%) due to the lower SO₂ and sulfate concentrations. If similar controls are implemented for NO_x emissions, NO_x concentrations are estimated to decrease by 30–60% as compared with the 2010 BAU scenario. The annual mean PM_2.5 concentrations will also decline by 2–14 μg m^?3 (3–12%). In addition, the number of ozone (O₃) non-attainment areas in the northern China is projected to be much lower, with the maximum 1-h average O₃ concentrations in the summer reduced by 8–30 ppb.