The relative effectiveness of NOx and VOC strategies in reducing Northeast U.S. ozone concentrations

This investigation was conducted to compare the relative benefits of controlling emissions of VOC vs. NO_x for reducing tropospheric O₃ (smog) concentrations in the Northeast United States. Because of the nonlinear nature of O₃ photochemistry, controls on NO_x emissions could actually result in increases in O₃ depending on the relative amount of VOC present and meteorological conditions. The Regional Oxidant Model (ROM) was used as the tool for estimating the impacts of different VOC and NO₃ strategies. Scenarios simulated include a future baseline and separate strategies with controls on just NO, just VOC, and a combination of VOC and NO_x controls. The results indicate that in general, NO_x controls are more beneficial across the region than VOC controls. However, for several large urban areas, NO_x controls were predicted to result in higher O₃ than VOC controls. Also, the relative benefits of VOC and NO_x controls varied from day-to-day suggesting a dependency on meteorological conditions. Given the variable nature of the effects of NO_x controls, additional modeling using more spatially resolved models is warranted to identify specific strategies for attainment of the ozone NAAQS in individual areas.     

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 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.     

Quantifying Local Creation and Regional Transport Using a Hierarchical Space–Time Model of Ozone as a Function of Observed NO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>, a Latent Space–Time VOC Process,Emissions, and Meteorology

We explore the ability of a process-based space–time model to decompose 8-hour ozone on a given day and site into parts attributable to local emissions and regional transport, to provide space–time predictions, and to assess the efficacy of past and future emission controls. We model ozone as created plus transported plus an error with seasonally varying spatial covariance parameters. Created ozone is a function of the observed NO _x concentration, the latent VOC concentration, and solar radiation surrogates. Transported ozone is a weighted average of the ozone observed at all sites on the previous day, where the weights are a function of wind speed and direction. The latent VOC process mean includes emissions, temperature, and a workday indicator, and the error has seasonally varying spatial covariance parameters. Using likelihood methods, we fit the model and obtain one set of predictions appropriate for prediction backward in time, and another appropriate for predicting under hypothetical emission scenarios. The first set of predictions has a lower root-mean-squared error (RMSE) when compared to point observations than do the 36 km gridcell averages from the Community Mesoscale Air Quality Model (CMAQ) used by the EPA; the second set has the same RMSE as CMAQ, but under-predicts high ozone values.     

Integrated assessment of emission control scenarios,including the impact of tropospheric ozone

The RAINS (Regional Air Pollution INformation and Simulation) model was developed at IIASA as an integrated assessment tool to assist policy advisors in evaluating options for reducing acid rain. In recent years, the European implementation of this model has been used to support the negotiations on an updated, effect-based Sulphur Protocol under the Convention on Long-range Transboundary Air Pollution. The development of future strategies for reducing the environmental damage caused by air pollutants requires a multi-pollutant, multi-effect approach. In this context, the RAINS model is being further developed to include ozone. This paper outlines the development of an integrated assessment model for tropospheric ozone, which combines information on the emissions of ozone precursors (NO_x and VOCs), the available control technologies and abatement costs, the formation and transport of ozone and its environmental effects in Europe.     

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.     

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.     

Ozone Formation Potentials of Volatile Organic Compounds and Ozone Sensitivity to Their Emission in the Megacity of São Paulo, Brazil

In the present study, a three-dimensional Eulerian photochemical model was employed to estimate the impact that organic compounds have on tropospheric ozone formation in the Metropolitan Area of São Paulo (MASP). In the year 2000, base case simulations were conducted in two periods: August 22–24 and March 13–15. Based on the pollutant concentrations calculated by the model, the correlation coefficient relative to observations for ozone ranged from 0.91 to 0.93 in both periods. In the simulations employed to evaluate the ozone potential of individual VOCs, as well as the sensitivity of ozone to the VOC/NO _x emission ratio, the variation in anthropogenic emissions was estimated at 15% (according to tests performed previously variations of 15% were stable). Although there were significant differences between the two periods, ozone concentrations were found to be much more sensitive to VOCs than to NO _x in both periods and throughout the study domain. In addition, considering their individual rates of emission from vehicles, the species/classes that were most important for ozone formation were as follows: aromatics with a kOH?>?2?×?10⁴ ppm^?1 min^?1; olefins with a kOH?<?7?×?10⁴ ppm^?1 min^?1; olefins with a kOH?>?7?×?10⁴ ppm^?1 min^?1; ethene; and formaldehyde, which are the principal species related to the production, transport, storage and combustion of fossil fuels.     

Improvements in Urban Air Quality: Case Studies from New York State, USA

Air quality levels vary over regions due to meteorological factors, proximity to sources, and local conditions (i.e., topography). The Northeast USA is subjected to pollution inputs from both local sources and those from the upwind Midwest USA that are transported by prevailing meteorological patterns. With the passage of the Clean Air Act in 1970 and the establishment of the National Ambient Air Quality Standards (NAAQS), national levels of air pollutants have declined significantly. Our study compared air quality time trends between five of the largest cities within New York State (Albany, Buffalo, New York City, Rochester, and Syracuse) and statewide means to national trends. Data were obtained from the NYS Department of Environmental Conservation (DEC) Bureau of Air Quality Surveillance for six criteria pollutants: carbon monoxide (CO), sulfur dioxide (SO₂), nitrogen dioxide (NO₂), ozone (O₃), particulate matter (PM_2.5), and lead (Pb). Regional Kendall tests found significant downward trends for each pollutant statewide from 1980 to 2007, while trends by city varied by decade and pollutant. The evaluation of historical trends of pollution in industrialized nations is useful in showing recent air quality improvements and also in the understanding what can be the result in air pollutant controls in those developing nations currently experiencing high levels of pollution.     

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.     

Best management practices for storm water at industrial facilities

Contaminated storm water runoff has been identified as a significant source of degradation to our nation's waterways. Industrial and construction activities are primary sources of this contamination. After identifying this problem, Congress passed the Clean Water Act Amendments of 1987 which required EPA to publish regulations to control storm water discharges from certain activities. As a result, industrial facilities subject to the program are required to obtain permits and implement controls referred to as Best Management Practices (BMPs) to reduce the pollutants in the storm water runoff from their sites. BMPs can be implemented to reduce contaminants from entering storm water (source controls) or to treat storm water after it has contacted industrial areas (treatment controls). In general, source controls are more effective in reducing pollutant levels in storm water runoff, and are therefore, preferred by EPA and other regulatory agencies. This paper provides an overview of the EPA Storm Water Program which also applies to most state programs and discusses methods to identify and implement BMPs.     

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.     

Testing trends in environmental compliance

Many environmentalregulations are based on threshold levels. Such a level is generally set such that exposure to a toxin above the level is considered a hazard to health. In many instances, the level may be exceeded a certain number of times before regulatory action is taken. Such is the case with the National Ambient Air Quality Standards (NAAQS) set by the Environmental Protection Agency (EPA) in accordance with the 1990 amendment of the Clean Air Act of 1970. This set of standards sets threshold levels for several pollutants including carbon monoxide, nitrogen dioxide, ground-level ozone, and lead. Many areas of the United States, which the EPA designates as nonattainment areas, persistently exceed the air pollution levels set by the NAAQS. Progress in these areas is of ten slow but can be studied through data collected on the elapsed time between violations. The purpose of this article is to present a relatively easy but flexible statistical method for assessing whether an area is making progress with compliance to the NAAQS. The method presented in this article is based on a randomization test of a general model for the mean time between violations of the standard. The modeling-type approach of this method makes it flexible enough to study many types of trends. The use of the randomization test makes the method simple to apply and requires fewer assumptions than many other proposed methods. We discuss some general theoretical conditions for which the method is well suited and study the performance of this method empirically, Finally, we apply the method to a well-known set of interviolation times corresponding to data collected on ground-level ozone in Houston, Texas.     

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.     

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.     

Changes in the Chemistry of Precipitation in the United States, 1981–1998

Regulatory measures in the United States, such as Title IV of the Clean Air Act Amendments of 1990, have primarily restricted sulfur dioxide emissions as a way to control acidic deposition. These restrictions, coupled with increasing concentrations of NH₄ ⁺ in wet deposition in some regions of the U.S. and continued high emissions of nitrogen oxides have generated a significant shift in the chemistry of precipitation as measured at National Atmospheric Deposition Program/National Trends Network sites. Trends in precipitation chemistry at NADP/NTN sites were evaluated for statistical significance for the period 1981–1998 using a Seasonal Mann-Kendall Test, a robust non-parametric test for detection of monotonic trends. SO₄ ^2? declines were detected at 100 of the 147 sites examined while no sites exhibited increasing SO₄ ^2? trends. On average, SO₄ ^2? declined 35% over the period 1981–1998 with downward SO₄ ^2? trends being most pronounced in the north-eastern United States. In contrast, no consistent trends in NO₃ ^? concentrations were observed in precipitation in any major region of the United States. Although the majority of sites did not exhibit significant trends in NH₄ ⁺ concentration, 30 sites exhibited upward trends. For Ca²⁺ concentration in precipitation, 64 sites exhibited a significant decreasing trend and no sites exhibited an upward trend.     

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.     

The Importance of Nitrogen Oxides for the Exceedance of Critical Thresholds in the Nordic Countries

Impacts of air pollutants and especially acidification in ecosystems have been of serious concern in the Nordic countries since the 1970s. The current approach to assess several pollutants (sulfur and nitrogen oxides, ammonia, volatile organic compounds) and their effects (acidification, eutrophication and ground-level ozone) simultaneously is extremely complex. This study explored the relative role of nitrogen oxides in environmental impacts in the Nordic countries. The share of NO_x in the exceedances of critical loads, the long-term ecosystem protection targets, was found to be roughly 25% in acidification and 50% in eutrophication. The contribution of NO_x emissions to ground-level ozone formation was considered important, as NO_x is the limiting precursor in ozone formation in the Nordic countries. The comparison of observed and modeled accumulated ozone concentrations (AOT40) for the early 1990s shows noticeable differences in the Nordic area, partly due to the sensitivity of the AOT40 indicator to the 40 ppb threshold value.     

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.     

Investigating the Real Air Pollution Exchange at Urban Sites Based on Time Variation of Columnar Content of the Components

As a new approach, urban air pollution was characterised by the variation of columnar content of the pollutants. Columnar content (CC) was estimated as the product of the pollutant??s mixing ratio and the mixing height. Mixing ratio data of the Metropolitan Air Quality Monitoring Network of Budapest were used, whilst mixing height was calculated by the meteorological AERMET model code. Time variation of CC refers to the real pollution exchange in the atmosphere that allows direct investigation of the emissions as well as post-emission modifications of the pollutants (such as chemical degradation or production). The diurnal urban CO cycle was found to be determined by two or three main influx peaks according to the traffic pattern of the site. The diurnal variation of NO _x level was found to be driven by traffic emission as well. Variant ratios of NO _x to CO influxes obtained for the different locations of the city range from 0.12 to 0.23, probably according to the vehicle composition of the traffic. The daily balance of photochemical production, chemical degradation and deposition of ozone yielded negative or positive depending on the location. Negative balances imply that the polluted urban atmosphere is a net ozone neutraliser source. Entrainment from the free troposphere yielded the major contributor to the diurnal ozone level at each site. The diurnal urban PM₁₀ cycle was found to be determined by traffic emission during the morning and evening rush hours whilst secondary aerosol formation around noon. In the evening, high PM₁₀ level rise was observed due to direct traffic emission as well as rapid conversion of the fine aerosol fraction to the coarse fraction.