Nitrogen oxides,regional transport,and ozone air quality: Results of a regional-scale model for the midwestern United States

An overview of the role of NO _x in the formation of rural O₃, regional transport and its potential impact on urban air quality is presented. An analysis of a specific O₃ excursion in southeast Michigan (8-2-90) is performed based on a combined urban and regional-scale model. The regional component of the model represents transport and photochemistry from sources as far away as Texas. Results suggest that rural O₃ and regional transport sensitive to NO _x emissions and relatively insensitive to changes in volatile organic carbon (VOC) emissions. This differs from the situation in urban areas, where O₃ is sensitive to both NO _x and VOC. Regional transport and upwind NO _x emissions have a significant impact on peak O₃ in Detroit. Implications for urban and regional-scale abatement strategies are discussed.     

Regulatory options under the U.S. Clean Air Act: The federal view

This paper documents the evolution of Environmental Protection Agency (EPA) policy concerning the relative roles that volatile organic compounds (VOCs) and oxides of nitrogen (NO_x) emissions play in ozone nonattainment planning for State implementation plans (SIPs). It further discusses possible new control requirements, including NO_x measures, that may be required as a result of pending Clean Air Act Amendments. In the early 1970's EPA guidance emphasized the use of VOC control measures to attain the ozone (formerly oxidant) ambient air quality standard. Little if any, control requirements applied to NO_x emissions. EPA continued to focus guidance requirements upon the control of VOCs during the planning efforts associated with the 1977 Clean Air Act amendments... 1979 SIPs, 1982 plans for long-term problem areas (extension areas), and other revisions to SIPs. Preliminary air quality modeling work to support these later planning efforts revealed that, in certain cases, there were potential benefits of NO_x control in addition to VOC. With this new insight, EPA's post-1987 policy proposal required states to look at the potential benefits of NO_x controls in areas with a nonmethane organic compound to NO_x ratio of 10∶1 or greater. In Clean Air Act Amendments currently being debated in the House and Senate, there is an uncertainty with regard to the role of NO_x controls. Possibilities under consideration range from the application of reasonably available control technology for 100 ton sources of NO_x to a clean fuel motor vehicle program within 42 months of enactment.     

A Modeling Study of the Impact of a Power Plant on Ground-Level Ozone in Relation to its Location: Southwestern Spain as a Case Study

The impact of atmospheric industrial emissions on secondary pollutant formation depends on many factors; one of the most important being the environmental setting in which the industry is located. The environmental setting affects an industry’s impact on ozone levels through both the air mass dispersion (a function of topography and wind patterns) and the emissions of organic volatile compounds (VOC) and nitrogen oxides (NO _x ) in the area. This model-based study shows how the sensitivity of surface ozone changes with the choice of source location. For the analysis, seven points distributed along the Tinto–Guadalquivir Basin (in the Southwestern Iberian Peninsula) were selected. This area is characterized by the close proximity of natural environments and crop fields to cities, roads, and industrial areas with high NO _x emissions. Natural VOC emissions represent more than 60% of the total non-methane volatile organic compounds emitted in the study area. The results reveal that the largest increases in ozone levels are produced when the industry is located both far away from NO _x emission sources and near to biogenic VOC emissions. Furthermore, the highest increases over the hourly and 8-hourly maximums, as well as the highest accumulated daily values, are found in areas characterized by high VOC/NO _x emission ratios and NO _x sensitivity. The study of the recurrent meteorological patterns along with the distribution of chemical indicators of the O₃–NO _x –VOC sensitivity allows the determination of the industry’s geographical impact on ozone levels. This information enables air quality managers to decide the future location of an industry minimizing its impact on smog levels.     

Efficacy of nitrogen oxides and hydrocarbons emissions controls in ozone attainment strategies as predicted by the Urban Airshed Model

The primary object of this paper is to provide a preliminary assessment of the effectiveness of NO _x vs Volatile Organic Compounds (VOC) emissions control options in improving O₃ air quality over the New York metropolitan area. To this end, we have applied the Urban Airshed Model (UAM) with the Carbon Bond IV (CB-IV) chemical mechanism utilizing the results of the Regional Oxidant Model (ROM) for the specification of initial/boundary concentrations and wind fields to the UAM. After examining the sensitivity of the predicted O₃ concentrations to initial/boundary conditions and biogenic emissions, we have evaluated the impact of various hypothetical emissions reduction options on O₃ air quality. Nested ROM/UAM simulations with an across-the-board reduction of 75% in the NO _x and VOC emissions from sources located within the New York metropolitan area indicate that the option of VOC-only control is superior to the NO _x -only control in reducing not only peak O₃ levels over the entire modeling domain but also population exposure to unhealthy O₃ levels. The model predicts that the combined 75% NO _x and VOC control option also reduces the peak O₃ concentration, but the improvement in O₃ air quality is less than that predicted for the 75% VOC-only control strategy. Additional modeling analyses with different mix and levels of emissions control and meteorological conditions are needed to confirm these preliminary findings.     

Measurement needs for developing and assessing ozone-control strategies

The monitoring programs needed to design control strategies differ from those required to assess the impact of the strategies on air quality. The former are short-term and intensive. They are designed to obtain the data required to apply an urban-scale grid model, like the Urban Airshed Model, or a combination of an urban-scale and regional-scale model, like the Regional Oxidant Model, to an area without having to assume important input data. Such measurements include three-dimensional pollutant and meteorological measurements throughout the modeling domain. Detailed and accurate emissions inventories are also required. Model validation should compare not only the O₃ predictions with actual data, but also include comparisons for NO _x , individual volatile organic compounds (VOC), and if possible, additional species such as PAN, H₂O₂, formaldehyde, and HNO₃. To assess the impact of control strategies, long-term monitoring networks that measure O₃, NO _x and speciated VOC are needed. O₃ trends should be examined using robust, meteorologically-adjusted O₃ statistics. Such statistics need to be related to a robust National Ambient Air Quality Standard.     

The role of nitrogen oxides in oxidant production as predicted by the Regional Acid Deposition Model (RADM)

Regional oxidant distributions produced under various atmospheric conditions and emission scenarios are investigated using the Regional Acid Deposition Model (RADM). RADM is a complex, evolving three-dimensional Eulerian model that describes the chemistry, transport and deposition of tropospheric trace species including SO₂, sulfate, NO _x and volatile organic compounds as well as O₃, other major oxidants and acids. The model calculates the short-term temporal evolution of atmospheric trace gas concentrations and their deposition on the regional scale. This study is focused on oxidant production in the eastern United States and southeastern Canada. The influence of atmospheric conditions is explored by comparing three characteristic winter, summer and spring/fall cases. Base-case 1985 emissions of SO _x , NO _x , volatile organic compounds (VOCs), NH₃ and CO are specified using the comprehensive pollutant emissions inventory developed as part of the National Acid Precipitation Assessment Program (NAPAP). The perturbed case, which represents projected anthropogenic emission changes for 2010, indicates changes in daily total 80 km grid average NO _x emissions ranging from increases of 75% to decreases of 45% and VOC emission changes ranging from increases of 65% to decreases of 20%. The largest NO _x emission changes occur in the northeast, and the largest VOC changes occur in the Gulf Coast area. Ground level grid average midday O₃ concentrations for the 1985 emission cases are highest (on the order of 70 to 100 ppb) in the New York City and Houston metropolitan areas for the summer and spring cases; the summer case also indicates relatively high grid average O₃ concentrations of greater than 80 ppb in the southeast. Winter case values are much lower than summer O₃ values throughout the region, with highs of 40 to 50 ppb occurring in the southeast and the Great Lakes area. Changes in NO _x and other emissions under the complex 2010 emissions scenario for the summer case result in maximum O₃ concentration reductions of 10% in the Houston area and increases in O₃ of a few percent in some rural areas of the southeast. This study underscores the need for more comprehensive assessment of the complex relationships among regional emission changes, oxidant production and atmospheric conditions.     

An Integrated Assessment Model for Fine Particulate Matter in Europe

Exposure to fine particles in the ambient air is recognized as a significant threat to human health. Two pathways contribute to the particle burden in the atmosphere: Fine particles originate from primary emissions, and secondary organic and inorganic particles are formed from the gas phase from the emissions of 'conventional' pollutants such as SO₂, NO_x, VOC and NH₃. Both types of particulate matter can be transported over long distances in the atmosphere. An integrated assessment model for particulate matter developed at IIASA addresses the relative importance of the different types of particulates, distinguishing primary and secondary particles and two size fractions. The model projects these emissions into the future and seeks cost-effective strategies for reducing health risks to population. The model integrates the control of primary emissions of fine particles with strategies to reduce the precursor emissions for the secondary aerosols. Preliminary results addressing the PM_2.5 fraction of both primary and secondary particulate matter indicate that in Europe the exposure to particulates will be significantly reduced as a side effect of the emission controls for conventional air pollutants (SO₂, NO_x, NH₃).     

Tropospheric Ozone in Alpine Forest Sites: Air Quality Monitoring and Statistical Data Analysis

Plants represent one of the major sinks for tropospheric ozone that, at high concentrations, can affect plants' physiological activity with consequent serious damage. A research project has been promoted by the Lombardy Foundation for the Environment to investigate the effects of air pollution on forest ecosystems. The areas of study are located on the southern slopes of the Italian Alps in two valleys, only 10 km apart, selected because of their different plant injury: Val Gerola and Val Masino. Air quality (O₃, NO_x, SO_x, VOC) and meteorological parameters were monitored during four summer seasons (1994-97) using automatic sampling devices providing hourly mean values for each variable. Data analysis showed very different ambient ozone concentrations at the two sites, with average concentration values observed in the more damaged valley (Val Gerola) twice those measured at the other site. Multivariate data analyses have been used to interpret the observed differences in long-term O₃ exposure between the two sites and to identify possible underlying processes.     

Trends and uncertainties in volatile organic compound emissions from anthropogenic sources

This paper discusses trends and uncertainties in the anthropogenic emission inventory for VOC. EPA's trend analysis indicates that emissions increased almost across the board until about 1970. After 1970, emissions continued to increase for industrial solvents, but declined for transportation, nonindustrial solvents, and combustion and waste disposal. With the current emphasis on using grid models to define NO_x and VOC control strategies, the uncertainty of emission inventories is becoming increasingly important. However, the volume of data in an emissions inventory makes the detailed assessment of uncertainty difficult if not impossible.     

Projections of SO2, NOx,NH3 and VOC Emissions in East Asia Up to 2030

Starting from an inventory of SO₂, NO_x, VOC and NH₃ emissions for the years 1990 and 1995 in East Asia (Japan, South and North Korea, China, Mongolia and Taiwan), the temporal development of the emissions of the four air pollutants is projected to the year 2030 based on scenarios of economic development. The projections are prepared at a regional level (prefectures or provinces of individual countries) and distinguish more than 100 source categories for each region. The emission estimates are presented with a spatial resolution of 1×1 degree longitude/latitude. First results suggest that, due to the emission control legislation taken in the region, SO₂ emissions would only grow by about 46 percent until 2030. Emissions of NO_x and VOC may increase by 95 and 65 percent, respectively, mainly driven by the expected increase in road traffic volume. Ammonia, mainly emitted from agriculture, is projected to double by 2030.     

Analysis of major photochemical pollutants with meteorological factors for high ozone days in Istanbul, Turkey

Hourly ozone, NO _x and VOC concentrations, measured during 2001–2003 summer periods, are analyzed in order to examine the interaction patterns between the major photochemical pollutants in ?stanbul. 34 high ozone days throughout the summer periods of the three years are determined and examined in the study together with the meteorological parameters like temperature, wind and vertical structure of the atmosphere. The results show that high levels of ozone are observed mostly under anticyclonic conditions with relatively low wind speeds. High ozone days generally experienced maximum concentrations at afternoon hours and minimum concentrations are reached at rush hours due to NO _x – titration by traffic emissions. High negative correlations with NO _x up to -0.84 are observed at the Saraçhane station while higher correlations for VOC species, up to ?0.75, are calculated for Kadiköy station. Some individual episodes experiencing high ozone concentrations up to 310 μg m^?3 in the early morning hours are also studied. It is found that decreasing inversion heights in the early hours of the day led to suppression of pollutants close to surface and thus, an increase in ozone concentrations was observed. Low wind speeds played a major role in the increase of pollution levels in the region. HYSPLIT model is applied to some particular episodes and the results show that the northeasterly transport to the region was dominant, especially in the early-morning maximums.     

Towards a Science-Based Integrated Ozone-Fine Particle Control Strategy

Epidemiology studies relating health effects to ambient levels of ozone and fine particles have led to the modification of standards in the United States for these pollutants (substitution of an 8-h standard for ozone at 80 ppbv, and addition of 24-h and annual standards for fine particles). The interrelationships of these pollutants in the atmosphere suggest the need for an integrated, science-based strategy for their control. Secondary ozone formation has been controlled through emission controls on VOC and NO_x precursors. Fine particles are secondary products largely resulting from the oxidation of precursors (SO₂, NO_x, and VOCs). The key intermediates in both types of secondary process are free radical species and the photochemically labile compounds that produce them in the atmosphere. However, due to the complex and nonlinear nature of the processes, reductions in precursors may lead to unexpected changes in ozone and fine particle formation rates. For example, reduction in NO_x emissions may reduce ozone and nitric acid levels, but lead also to increased rates of sulfate formation in clouds and increased ammonia availability for neutralization of acidic sulfate aerosols. Reductions of SO₂ may reduce aerosol sulfate levels in the summer, but have no effect in other seasons. Reductions in VOCs may reduce ozone levels in urban core areas, but not elsewhere. An integrated, regionally and seasonally specific, emission reduction strategy is needed to cost-effectively reduce both ozone and fine particle levels.     

A Module to Calculate Primary Particulate Matter Emissions and Abatement Measures in Europe

Primary particulate matter is emitted directly into the atmosphere from various anthropogenic and natural sources such as power plants (combustion of fossil fuels) or forest fires. Secondary particles are formed by transformation of SO₂, NO_x, NH₃, and VOC in the atmosphere. They both contribute to ambient particulate matter concentrations, which may have adverse effects on human health. Health hazards are caused by small particulate size, high number of especially fine (< 2.5 µm) and ultra-fine (< 0.1 µm) particles and/or their chemical composition. As part of an integrated assessment model developed at IIASA, a module on primary particulate matter (PM) emissions has been added to the existing SO₂, NO_x, NH₃ and VOC sections. The module considers so far primary emissions of total suspended particles (TSP), PM₁₀ and PM_2.5 from aggregated stationary and mobile sources. A primary PM emission database has been established. Country specific emission factors for stationary sources have been calculated within the module using the ash content of solid fuels.     

Nitrogen Deposition and Strategies for the Control of Acidification and Eutrophication across Great Britain

It is now recognised that a multi-pollutant, multi-effect approach needsto be adopted to address the range of problems caused by atmosphericpollution. In this paper we use a relatively simple trajectory model (HARM)to explore the coupled behaviour of sulphur dioxide (SO₂),oxides of nitrogen (NO_x) and ammonia (NH₃) andthe possible effects of future reductions in emissions of these pollutantson depositions of S and N across Great Britain. The performance of HARM withrespect to concentrations and depositions of NO_y andNH_x is assessed by comparison with data from nationalmonitoring networks. A range of emissions scenarios are modelled and theeffects of these reductions on critical loads exceedance are explored usingthe critical loads function (CLF), which allows both the acidification andeutrophication effects of S and N deposition to be explored simultaneously.Spatial variations in the reductions of deposition of S and/or N required tomeet critical loads are described. Reductions in emissions of the precursorsof strong acids (SO₂ and NO_x) yield benefits interms of ammonium deposition as a result of their coupled chemistry. Thedevelopment of strategies to control nitrogen deposition will need to take this non-linearity in to account.     

土壤氮氧化物排放及其对中国地区对流层光化学特性影响的数值模拟研究

利用Williams的模型估计中国地区土壤氮氧化物(NOX,包括NO和NO2)的排放,并运用中尺度气象模式MM5以及光化学模式Calgrid模拟不同季节和不同人为源情况下土壤NOX排放对中国地区光化学的影响。模拟结果表明,中国地区土壤NOX排放总量为225.8 Gg N,是人为源的7%,这一比例在夏季将达到23.4%;排放量有明显季节变化和空间变化。土壤源不仅使NOX、O3、HNO3和过氧乙酰硝酸酯(PeroxyacetylNitrate,PAN)的全国平均浓度增加,还显著改变了污染物的空间分布。4种污染物全国平均浓度的最大增量分别为2.37、26.08、9.79和0.43μg m-3,增量在夏季明显高于其他季节,在各地区的增减随排放源、气象条件和光化学特性的不同而不同。随着人为NOX排放的增加,土壤源在光化学中的作用会更加显著。土壤NOX排放在对流层光化学过程中的作用不容忽视。     

Natural emissions of oxidant precursors

This paper provides an overview of the sources, the estimation methodology, and the relative amounts of natural hydrocarbon and NO_x emissions. The most recent estimate of natural nonmethane hydrocarbon (NMHC) emissions for the United States is 28 Tg yr^?1. This compares with 20 Tg yr^?1 for anthropogenic NMHC sources. The southeastern and southcentral portions of the United States account for approximately 43% of the annual U.S. natural NMHC estimate. These emissions exhibit strong diurnal and seasonal dependencies related to temperature, solar radiation, and active biomass. Forests are the primary vegetative source of hydrocarbons. The major sources of natural NO_X emissions in North America are biomass burning, lightning, and microbial activity in soil. We present a comparison of hourly gridded NO_X emissions from lightning, soil, and man-made sources for the northeastern United States. We also provide results from preliminary investigations of the sensitivity of O₃ predictions from the U.S. Environmental Protection Agency's Regional Oxidant Model to natural NMHC and nitric oxide emissions.     

Emission Inventories,Emission Control Options and Control Strategies: An Overview of Recent Developments

Accurate emission inventories are crucial for informed decisions about emission control strategies. Emission inventory activities are now well established throughout the world and a large body of resources is available to assist in estimating emissions at the global, regional and local scale. Work is ongoing to refine methodologies and to address additional sources and pollutants such as fine particulate matter. During the last decade innovative concepts for emission control legislation were developed. Market based instruments can achieve envisaged emission reductions at lower costs than conventional approaches. Air quality management is now understood as a multi-pollutant, multi-effect task, which offers a significant cost saving potential if synergistic effects are fully utilized. Integrated assessment models proved useful in managing the vast volume of relevant information needed for the design of cost-effective emission control strategies. Europe and North America have embarked on ambitious control strategies that will lead to significant reductions in the emissions of some of the conventional pollutants (e.g., SO₂, NO_x, VOC). There are also first indications of a structural break that could reverse the long-term growth trend of SO₂ emissions also in the fast developing nations of Asia.     

Cost-Effective Abatement of Acidifying Emissions with Flue Gas Cleaning vs. Fuel Switching in Finland

Acidifying emissions from energy production and industry have decreased considerably during the last two decades in Finland. Especially the emissions of sulphur dioxide have dropped sharply with 85% in 1980–1998, although the energy use has increased 30% during the same period. The reduction has occurred through two mechanisms: by replacing the combustion of heavy fuel oil with cleaner energy carriers, and by direct emission reduction controls, e.g. flue gas desulphurization. In this study the Finnish cost curves for SO₂ and NO_x were first calculated to produce a consistent comprehensive view on further emission reduction costs and potentials. The data on technical and cost-related parameters were based on actual national experiences from power plants and industry. Most of the cost-efficient sulphur emission controls were already in use. For NO_x, a large share of further reduction potential still remained. Second, a case on the emission reductions and costs for fuel switching in a 205 MW_th peat power plant of Tampere Power Utility in Finland was studied. Fuel switching to natural gas was found less cost-efficient in SO₂ and NO_x emission reduction when compared to flue gas cleaning techniques. The findings provided new information on fuel switching as an alternative potential reduction measure, which is not considered in international assessments.     

Calculating nitrogen deposition in Europe

Nitrogen deposition calculations for Europe were performed by separate models describing the long-range transport of ammonia and oxidized N. A linearized version of a non-linear atmospheric chemistry model was used for calculating oxidized N. Model computations were found to be consistent with the observed spatial pattern of wet nitrate deposition in Europe. Interannual meteorological variability was estimated to cause a typical year-to-year variation in annual oxidized N deposition of about 6 to 10%. Nitrogen deposition was computed for several NO _x emissions reduction scenarios. These scenarios were derived from an OECD study and applied to the 27 largest countries in Europe. Most reduction scenarios affected the deposition pattern of oxidized N, but the most extreme NO _x emission reduction scenario did not change very much the overall pattern of total (oxidized N plus ammonia N) N deposition. Depending on the desired level of environmental protection, it may be necessary to reduce ammonia emissions in addition to NO _x emissions in order to reduce N deposition in Europe.     

A novel method to evaluate the phytotoxic potential of low ozone concentrations using poplar cuttings

Six-week-old rooted cuttings of Populus nigra L. ‘LOENEN’ and Populus maximowiczii Henri X Populus nigra L. ‘ROCHESTER’, differing in their phenomenological sensitivity to O₃, were submitted to low concentrations of O₃, NO_x, and SO₂. Exposure was performed in open top-chambers from 25.5. until 6.7.1988. Comparing the response of the two poplars by 77 biochemical criteria the macroscopic O₃- sensitivity of ‘LOENEN’ was clearly reflected in changes of the pool sizes of the different nonstructural carbohydrates, polyols, and phenolics of the leaf-lamina, petiole, shoot-axis, and roots. In contrast, both varieties revealed the same response to NO_x/SO₂-mixtures. It can be concluded that ‘LOENEN’ together with ‘ROCHESTER’-poplars as controls, are an appropriate system to specifically indicate O₃ in a mixture of air pollutants.