Rural and Urban Ozone Relationships In New York State

High ozone concentrations, often in excess of the national ambient air quality standard for photochemical oxidants, have been measured simultaneously in urban and rural areas of New York State. Average daily rural ozone concentrations were found to correlate well with daily maximum urban ozone concentrations suggesting a common source. Estimations of the quantity of ozone advectively transported into New York State are more than an order of magnitude greater than estimations of the potential photochemical generation of ozone from hydrocarbon emissions within New York State. It is suggested thai the high rural ozone levels are not primarily due to the transport of ozone and ozone precursors from olher urban areas, but are rather due to natural phenomena such as photochemical generation from naturally occurring precursors or transport of ozone from the stratosphere to the troposphere. The effectiveness of a hydrocarbon control strategy for New York State to meet the ambient air quality standard for photochemical oxidants when background levels themselves may be above the standard is questioned.     

The long range transport of ozone within Europe and its control

It is widely accepted that the ozone concentrations experienced during photochemical episodes over large areas of Europe may exceed levels at which adverse environmental effects could be expected. These peak ozone concentrations can be reduced by controlling atmospheric emissions of the hydrocarbon and nitrogen oxide precursors. For ozone control to be successful over the spatial scale of Europe, long term international cooperation is required in the formulation of emission abatement strategies. A significant barrier to rapid progress has been the complexity of the processes that describe ozone formation. Highly sophisticated computer models of chemistry and transport have, up to now, been the only means to study the impact of abatement strategies. An alternative approach has been adopted here involving the development of a simplified long range transport model for ozone based on the analysis of over 60 experimental runs of a photochemical trajectory model applied to a wide range of hydrocarbon-nitrogen oxide emission combinations. Using the ozone-precursor relationship obtained, it has been possible to examine various policy options in the European context. Although taken together, three illustrative emission control scenarios reduce NO(x) and hydrocarbon emissions substantially through controls on motor vehicle exhaust, large combustion plant and solvent usage, a significant potential for photochemical ozone formation and long range transport may still remain after their implementation. The extents of precursor emission abatement that will be required, if the potential for ozone formation is to be reduced below published air quality criteria guidelines or critical levels, have been determined for each European country. The implied reductions in NO(x) and hydrocarbons relative to current levels amount to between 50 and 90%.     

Air pollution and health studies in China--policy implications

During the rapid economic development in China, ambient air pollutants in major cities, including PM10 (particulate matter with aerodynamic diameter < or =10 microm) and SO2 have been reduced due to various measures taken to reduce or control sources of emissions, whereas NO2 is stable or slightly increased. However, air pollution levels in China are still at the higher end of the world level. Less information is available regarding changes in national levels of other pollutants such as PM2.5 and ozone. The Chinese Ministry of Environmental Protection (MOEP) set an index for "controlling/reducing total SO2 emissions" to evaluate the efficacy of air pollution control strategy in the country. Total SO2 emissions declined for the first time in 2007. Chinese epidemiologic studies evidenced adverse health effects of ambient air pollution similar to those reported from developed countries, though risk estimates on mortality/morbidity per unit increase of air pollutant are somewhat smaller than those reported in developed countries. Disease burden on health attributable to air pollution is relatively greater in China because of higher pollution levels. Improving ambient air quality has substantial and measurable public health benefits in China. It is recommended that the current Chinese air quality standards be updated/revised and the target for "controlling/reducing total SO2 emissions" be maintained and another target for "reducing total NO2 emissions" be added in view of rapid increase in motor vehicles. Continuous and persistent efforts should be taken to improve ambient air quality.     

Ozone Transport

Elevated concentrations of ozone, often above the national ambient air quality standard for photochemical oxidants, have been measured in both urban and rural areas of Connecticut. One such episode took place on June 10, 1974. Ozone levels, after stabilizing at values slightly above the standard (i.e., 80 to 110 ppb; Connecticut generated ozone concentrations), rose sharply late in the afternoon reaching concentrations as high as 310 ppb (almost 4 times the standard) in Hartford. The trajectory of the air mass, which arrived in Hartford at the time of maximum O₃ occurence, had its origin in the metropolitan New York area during the early morning rush hour on the episode day. This illustrates that the advective transport of O₃ and O₃ precursors into Connecticut from New York are probably responsible for a significant portion (approximately two-thirds) of the elevated O₃ concentrations measured throughout Connecticut on days when winds are from the south-southwest direction. The fact that peak O₃ levels occur late in the afternoon, several hours after maximum sunlight intensity, reinforces the conclusion that excessive O₃ concentrations developed as O₃ and ozone precursors were generated in the vicinity of New York City and then drifted inland into Connecticut on the afternoon sea breeze.

It appears to be unrealistic to develop a hydrocarbon control strategy for Connecticut in order to meet the photochemical oxidant ambient air quality standard when O₃ and/or ozone precursors ad-vectively transported into the State cause oxidant levels to exceed the standard. The complete cessation of all anthropogenic hydrocarbon emissions in Connecticut would not necessarily assure that the standard would be attained here. The implication is that a regional (i.e., the eastern part of the United States) hydrocarbon control strategy is needed to reduce adequately ozone formation and transport so as to allow Connecticut to meet the current oxidant standard.     

European abatement of surface ozone in a global perspective

EU's programme Clean Air for Europe (CAFE) is presently revising the policy on air quality which will lead to the adoption of a thematic strategy on air pollution under the Sixth Environmental Action Programme by mid-2005. For the abatement of surface ozone it is becoming evident that processes outside European control will be crucial for meeting long-term aims and air quality guidelines in Europe in the future. Measurements and modelling results indicate that there is a strong link between climate change and surface ozone. A warmer and dryer European climate is very likely to lead to increased ozone concentrations. Furthermore, increased anthropogenic emissions in developing economies in Asia are likely to raise the hemispheric background level of ozone. A significant increase in the background concentration of ozone has been observed at several sites in Northern Europe although the underlying causes are not settled. The photochemical formation of tropospheric ozone from increased concentrations of methane and CO may also lead to a higher ozone level on a global scale. Gradually, these effects may outweigh the effect of the reduced European ozone precursor emissions. This calls for a global or hemispheric perspective in the revision of the European air quality policy for ozone.     

Non-Methane Hydrocarbon Air Quality Measurements

It is important in the implementation of the air quality standard for ozone/oxidants and non-methane hydrocarbons to develop quantitative relationships between these pollutants in air quality regions. Analyses for ambient air non-methane hydrocarbon give a direct measure of the progress in control of hydrocarbon emissions and in the reduction of oxidant/ozone concentration levels. Total hydrocarbon concentrations are much more available than non-hydrocarbon levels. An empirical relationship between total hydrocarbons and non-methane hydrocarbons has been obtained from measurements at both west and east coast sites in the U. S. The comparability of measurements from flame ionization analyzers and gas chromatography has been demonstrated. Either analytical technique can be applied to samples collected at monitoring sites to provide the 6-9 A.M. non-methane hydrocarbon aerometric results specified in the air quality standards.     

Demonstrating attainment of the air quality standards: integration of observations and model predictions into the probabilistic framework

This paper introduces an integrated observational-modeling approach to transform the deterministic nature of attainment demonstrations of the National Ambient Air Quality Standard (NAAQS) into the probabilistic framework. While the methods presented here can be used to address any air quality standard that is based on extreme values, this paper focuses on the application to the 1-hr and 8-hr NAAQS for ozone. Extreme value statistics and resampling techniques are applied to estimate the probability of exceeding the NAAQS for both 1-hr and 8-hr ozone concentrations. Within the integrated observation-modeling analysis approach, we show that the model-to-model differences in the predicted responses to emission reductions are smaller than the model-to-model differences in predicted absolute ozone concentrations. We illustrate that the emission reductions stemming from a real-world emission control strategy would substantially reduce the probability of exceeding the NAAQS over a large portion of the eastern United States, especially for the 8-hr average ozone concentrations.     

Demonstrating Attainment of the Air Quality Standards: Integration of Observations and Model Predictions into the Probabilistic Framework

ABSTRACT

This paper introduces an integrated observational-modeling approach to transform the deterministic nature of attainment demonstrations of the National Ambient Air Quality Standard (NAAQS) into the probabilistic framework. While the methods presented here can be used to address any air quality standard that is based on extreme values, this paper focuses on the application to the 1-hr and 8-hr NAAQS for ozone. Extreme value statistics and resampling techniques are applied to estimate the probability of exceeding the NAAQS for both 1-hr and 8-hr ozone concentrations. Within the integrated observation-modeling analysis approach, we show that the model-to-model differences in the predicted responses to emission reductions are smaller than the model-to-model differences in predicted absolute ozone concentrations. We illustrate that the emission reductions stemming from a real-world emission control strategy would substantially reduce the probability of exceeding the NAAQS over a large portion of the eastern United States, especially for the 8-hr average ozone concentrations.     

Evaluation of the optimum volatile organic compounds control strategy considering the formation of ozone and secondary organic aerosol in Seoul, Korea

The characteristics of volatile organic compounds (VOCs) and their annual trends in Seoul, Korea were investigated, with their optimal control strategy suggested. The annual concentration of VOCs (96.2–121.1 ppbC) has shown a decreasing trend from 2004 to 2008, suggesting the control strategy via the “Special Measures for Metropolitan Air Quality Improvement,” which was implemented in 2005, has been successful. The contributions of individual VOC to the production of ambient ozone and secondary organic aerosol (SOA) are discussed to assess the adequacy of current control strategies. The contribution of aromatics (C6–C10) to the production of ozone accounted for 38.7–46.3 % of the total ozone production, followed by low carbon alkanes (C2–C6) (27.0–35.9 %). The total SOA formation potential of VOCs was found to range from 2.5 to 3.5 μg m^?3, mainly as a result of aromatics (C6–C10) (over 85 %). Considering the contributions from ozone and SOA production, it was concluded that solvent use was the most important emission source, followed by vehicle exhaust emissions. Thus, the current emission control strategy focused on these two emission sources is appropriate to reduce the VOCs related pollution level of the Seoul Metropolitan Region. Still, an additional control strategy, such as controlling the emissions from meat cooking, which is an emission source of high carbon alkanes (C7–C10), needs to be considered to further reduce the VOCs related pollution level in Seoul.     

Daily surface UV exposure and its relationship to surface pollutant measurements

For the past 30 years, the stratospheric ozone layer has decreased in the Northern Hemisphere. The main effect of this ozone decrease was an expected increase in the UV radiation at the Earth's surface, but there has been no clear evidence of an increasing urban trend in surface UV. This study shows that specific air pollutants can reduce the increased surface levels of UV radiation and offers an explanation for why the expected surface UV increases have not been observed, especially in urban regions. A U.S. Environmental Protection Agency (EPA) UV monitoring site at the University of California at Riverside combined with air pollution data from a site operated by the California Air Resources Board in Rubidoux, CA, provided the basis of this study. The 1997 South Coast Ozone Study (SCOS-97) provided three key ingredients: black carbon, PM10 concentrations, and collocated radiometric measurements. The Total Ozone Mapping Spectrometer (TOMS) satellite data were used to provide the stratospheric ozone levels that were included in the statistical model. All of these input parameters would be used to test this study's hypothesis: the expected increase of surface UV radiation, caused by decreases in stratospheric ozone, can be masked by increases in anthropogenic emissions. The values for the pollutants were 7:00 a.m.-5:00 p.m. averages of the instrument's values taken during summer 1997. A statistical linear regression model was employed using the stratospheric ozone, black carbon, PM10, and surface ozone concentrations, and the sin (theta) and cos (theta). The angle theta is defined by theta = 2pi (Julian date/365). This model obtained a coefficient of determination of 0.94 with an uncertainty level (p value) of less than 0.3% for all of the variables in the model except ground-level ozone. The final model, regressed against a data set from a remote, western North Carolina site, resulted in a coefficient of determination of 0.92. The model shows that black carbon can reduce the Diffey-weighted UV levels that reach the surface by as much as 35%, depending on the season.     

Predicting ozone levels

This paper presents a statistical model that is capable of predicting ozone levels from precursor concentrations and meteorological conditions during daylight hours in the Shuaiba Industrial Area (SIA) of Kuwait. The model has been developed from ambient air quality data that was recorded for one year starting from December 1994 using an air pollution mobile monitoring station. The functional relationship between ozone level and the various independent variables has been determined by using a stepwise multiple regression modelling procedure. The model contains two terms that describe the dependence of ozone on nitrogen oxides (NOx) and nonmethane hydrocarbon precursor concentrations, and other terms that relate to wind direction, wind speed, sulphur dioxide (SO₂) and solar energy. In the model, the levels of the precursors are inversely related to ozone concentration, whereas SO₂ concentration, wind speed and solar radiation are positively correlated. Typically, 63 % of the variation in ozone levels can be explained by the levels of NOx. The model is shown to be statistically significant and model predictions and experimental observations are shown to be consistent. A detailed analysis of the ozone-temperature relationship is also presented; at temperatures less than 27 °C there is a positive correlation between temperature and ozone concentration whereas at temperatures greater than 27 °C a negative correlation is seen. This is the first time a non-monotonic relationship between ozone levels and temperature has been reported and discussed.     

Integrated assessment modeling of atmospheric pollutants in the Southern Appalachian Mountains. Part I: hourly and seasonal ozone

Recently, a comprehensive air quality modeling system was developed as part of the Southern Appalachians Mountains Initiative (SAMI) with the ability to simulate meteorology, emissions, ozone, size- and composition-resolved particulate matter, and pollutant deposition fluxes. As part of SAMI, the RAMS/EMS-95/URM-1ATM modeling system was used to evaluate potential emission control strategies to reduce atmospheric pollutant levels at Class I areas located in the Southern Appalachians Mountains. This article discusses the details of the ozone model performance and the methodology that was used to scale discrete episodic pollutant levels to seasonal and annual averages. The daily mean normalized bias and error for 1-hr and 8-hr ozone were within U.S. Environment Protection Agency guidance criteria for urban-scale modeling. The model typically showed a systematic overestimation for low ozone levels and an underestimation for high levels. Because SAMI was primarily interested in simulating the growing season ozone levels in Class I areas, daily and seasonal cumulative ozone exposure, as characterized by the W126 index, were also evaluated. The daily ozone W126 performance was not as good as the hourly ozone performance; however, the seasonal ozone W126 scaled up from daily values was within 17% of the observations at two typical Class I areas of the SAMI region. The overall ozone performance of the model was deemed acceptable for the purposes of SAMI's assessment.     

Projected changes in particulate matter concentrations in the South Coast Air Basin due to basin-wide reductions in nitrogen oxides,volatile organic compounds,and ammonia emissions

An ozone abatement strategy for the South Coast Air Basin (SoCAB) has been proposed by the South Coast Air Quality Management District (SCAQMD) and the California Air Resources Board (ARB). The proposed emissions reduction strategy is focused on the reduction of nitrogen oxide (NO_x) emissions by the year 2030. Two high PM_2.5 concentration episodes with high ammonium nitrate compositions occurring during September and November 2008 were simulated with the Community Multi-scale Air Quality model (CMAQ). All simulations were made with same meteorological files provided by the SCAQMD to allow them to be more directly compared with their previous modeling studies. Although there was an overall under-prediction bias, the CMAQ simulations were within an overall normalized mean error of 50%; a range that is considered acceptable performance for PM modeling. A range of simulations of these episodes were made to evaluate sensitivity to NO_x and ammonia emissions inputs for the future year 2030. It was found that the current ozone control strategy will reduce daily average PM_2.5 concentrations. However, the targeted NO_x reductions for ozone were not found to be optimal for reducing PM_2.5 concentrations. Ammonia emission reductions reduced PM_2.5 and this might be considered as part of a PM_2.5 control strategy.

Implications: The SCAQMD and the ARB have proposed an ozone abatement strategy for the SoCAB that focuses on NO_x emission reductions. Their strategy will affect both ozone and PM_2.5. Two episodes that occurred during September and November 2008 with high PM_2.5 concentrations and high ammonium nitrate composition were selected for simulation with different levels of nitrogen oxide and ammonia emissions for the future year 2030. It was found that the ozone control strategy will reduce maximum daily average PM_2.5 concentrations but its effect on PM_2.5 concentrations is not optimal.     

Integrated Assessment Modeling of Atmospheric Pollutants in the Southern Appalachian Mountains. Part I: Hourly and Seasonal Ozone

Abstract

Recently, a comprehensive air quality modeling system was developed as part of the Southern Appalachians Mountains Initiative (SAMI) with the ability to simulate meteorology, emissions, ozone, size- and composition-resolved particulate matter, and pollutant deposition fluxes. As part of SAMI, the RAMS/EMS-95/URM-1ATM modeling system was used to evaluate potential emission control strategies to reduce atmospheric pollutant levels at Class I areas located in the Southern Appalachians Mountains. This article discusses the details of the ozone model performance and the methodology that was used to scale discrete episodic pollutant levels to seasonal and annual averages. The daily mean normalized bias and error for 1-hr and 8-hr ozone were within U.S. Environment Protection Agency guidance criteria for urban-scale modeling. The model typically showed a systematic overestimation for low ozone levels and an underestimation for high levels. Because SAMI was primarily interested in simulating the growing season ozone levels in Class I areas, daily and seasonal cumulative ozone exposure, as characterized by the W126 index, were also evaluated. The daily ozone W126 performance was not as good as the hourly ozone performance; however, the seasonal ozone W126 scaled up from daily values was within 17% of the observations at two typical Class I areas of the SAMI region. The overall ozone performance of the model was deemed acceptable for the purposes of SAMI’s assessment.     

Statistical Analysis of Trends in Urban Ozone Air Quality

The purpose of this paper is to demonstrate the use of some statistical methods for examining trends in ambient ozone air quality downwind of major urban areas. To this end, daily maximum 1 -hr ozone concentrations measured over New Jersey, metropolitan New York City and Connecticut for the period 1980 to 1989 were assembled and analyzed. This paper discusses the application of the bootstrap method, extreme value statistics and a nonparametric test for evaluating trends in urban ozone air quality. The results indicate that although there is an improvement in ozone air quality downwind of New York City, there has been little change in ozone levels upwind of New York City during this ten-year period.     

Ozone and Radionuclide Correlations In Air of Marine Trajectory At Quillayute,Washington

A large number of radioactive and non-radioactive airborne constituents are being measured continually at our coastal air reference station located in northwestern Washington State. Important correlations have been observed between many of these materials. There are also apparent relationships between changing concentrations and meteorological parameters. Interesting fluctuations in the ozone levels with incoming clean air masses may help explain some of the high ozone levels observed by workers elsewhere. Positive correlations between certain known high altitude source region particulate radionuclides and ozone on a daily basis point to the upper level origin of the higher ozone concentrations observed at this site. This view is reinforced by the more usual negative correlations observed between general particulate levels at Quillayute and ozone concentrations when measured on a continuous monitoring basis.     

Ground-Level Ozone in Eastern Canada: Seasonal Variations,Trends, and Occurrences of High Concentrations

Over the past few years, concern has increased in Canada over the health and environmental impacts of elevated concentrations of ground-level ozone. During the summer the most populated regions of Canada frequently record ozone concentrations that exceed the one-hour average maximum acceptable air quality objective of 32 parts per billion (ppb). In 1988 the Canadian Council of Ministers of the Environment agreed to develop a federal/provincial management plan to control nitrogen oxide and volatile organic compound emissions to reduce ozone concentrations in all affected regions of the country. In addition to the proposed interim control measures, the plan recommended that studies be undertaken to acquire the information necessary to develop sound control strategies. This report represents one of those studies and provides a summary of ground-level ozone measurements for eastern Canada for the 1980 to 1991 period with an emphasis on seasonal variations, trends, and occurrences of high concentrations.

Southwestern Ontario experiences the highest maximum hourly ozone concentrations and the greatest frequency of hours greater than the 82 ppb acceptable objective. Urban sites have the highest frequencies of ozone concentration measurements in the < 10 ppb range, while rural and remote sites show peaks in frequency distribution in the 20 to 30 ppb range. Trend analysis of summertime (May to September) average daily maximum ozone concentration showed no consistent pattern for eastern Canadian sites during 1980 to 1991. Sites in Montreal showed statistically insignificant downward trends while sites in Toronto showed small but statistically significant upward trends. These ozone-increasing trends are associated with reductions in nitric oxide concentrations. At all sites there was large year-to-year variability in peak ozone levels and in the frequency of hours with ozone concentrations above the maximum acceptable objective.     

Study of atmospheric ozone formation by means of a neural network-based model

The occurrence of high ozone levels in the atmosphere of urban areas has become a serious pollution problem in a number of large cities in the world. Although mathematical models have been proposed for predicting ozone concentrations as a function of a number of gas components, sometimes there are uncertainties due to lack of the combined effects of meteorological factors and the complex chemical reaction system involved. The application of neural network models, based on measured values of air pollutants and meteorological factors at different locations within the S?o Paulo Metropolitan Area, combine chemical and meteorological information. This has shown to be a promising tool for predicting ozone concentration. Simulations carried out with the model indicate the sensitivity of ozone in relation to different air pollution and weather conditions. Predictions using this model have shown good agreement with measured values of ozone concentrations.     

Conjunctive use of models to design cost-effective ozone control strategies

The management of tropospheric ozone (O3) is particularly difficult. The formulation of emission control strategies requires considerable information including: (1) emission inventories, (2) available control technologies, (3) meteorological data for critical design episodes, and (4) computer models that simulate atmospheric transport and chemistry. The simultaneous consideration of this information during control strategy design can be exceedingly difficult for a decision-maker. Traditional management approaches do not explicitly address cost minimization. This study presents a new approach for designing air quality management strategies; a simple air quality model is used conjunctively with a complex air quality model to obtain low-cost management strategies. A simple air quality model is used to identify potentially good solutions, and two heuristic methods are used to identify cost-effective control strategies using only a small number of simple air quality model simulations. Subsequently, the resulting strategies are verified and refined using a complex air quality model. The use of this approach may greatly reduce the number of complex air quality model runs that are required. An important component of this heuristic design framework is the use of the simple air quality model as a screening and exploratory tool. To achieve similar results with the simple and complex air     

The potential near-source ozone impacts of upstream oil and gas industry emissions

Increased drilling in urban areas overlying shale formations and its potential impact on human health through decreased air quality make it important to estimate the contribution of oil and gas activities to photochemical smog. Flares and compressor engines used in natural gas operations, for example, are large sources not only of NOx but also offormaldehyde, a hazardous air pollutant and powerful ozone precursor We used a neighborhood scale (200 m horizontal resolution) three-dimensional (3D) air dispersion model with an appropriate chemical mechanism to simulate ozone formation in the vicinity ofa hypothetical natural gas processing facility, based on accepted estimates of both regular and nonroutine emissions. The model predicts that, under average midday conditions in June, regular emissions mostly associated with compressor engines may increase ambient ozone in the Barnett Shale by more than 3 ppb beginning at about 2 km downwind of the facility, assuming there are no other major sources of ozone precursors. Flare volumes of 100,000 cubic meters per hour ofnatural gas over a period of 2 hr can also add over 3 ppb to peak 1-hr ozone somewhatfurther (>8 km) downwind, once dilution overcomes ozone titration and inhibition by large flare emissions of NOx. The additional peak ozone from the hypothetical flare can briefly exceed 10 ppb about 16 km downwind. The enhancements of ambient ozone predicted by the model are significant, given that ozone control strategy widths are of the order of a few parts per billion. Degrading the horizontal resolution of the model to 1 km spuriously enhances the simulated ozone increases by reducing the effectiveness of ozone inhibition and titration due to artificial plume dilution.