Modeled response of ozone to electricity generation emissions in the northeastern United States using three sensitivity techniques

Electrical generation units (EGUs) are important sources of nitrogen oxides (NO_x) that contribute to ozone air pollution. A dynamic management system can anticipate high ozone and dispatch EGU generation on a daily basis to attempt to avoid violations, temporarily scaling back or shutting down EGUs that most influence the high ozone while compensating for that generation elsewhere. Here we investigate the contributions of NO_x from individual EGUs to high daily ozone, with the goal of informing the design of a dynamic management system. In particular, we illustrate the use of three sensitivity techniques in air quality models—brute force, decoupled direct method (DDM), and higher-order DDM—to quantify the sensitivity of high ozone to NO_x emissions from 80 individual EGUs. We model two episodes with high ozone in the region around Pittsburgh, PA, on August 4 and 13, 2005, showing that the contribution of 80 EGUs to 8-hr daily maximum ozone ranges from 1 to >5 ppb at particular locations. At these locations and on the two high ozone days, shutting down power plants roughly 1.5 days before the 8-hr ozone violation causes greater ozone reductions than 1 full day before; however, the benefits of shutting down roughly 2 days before the high ozone are modest compared with 1.5 days. Using DDM, we find that six EGUs are responsible for >65% of the total EGU ozone contribution at locations of interest; in some locations, a single EGU is responsible for most of the contribution. Considering ozone sensitivities for all 80 EGUs, DDM performs well compared with a brute-force simulation with a small normalized mean bias (–0.20), while this bias is reduced when using the higher-order DDM (–0.10).

Implications: Dynamic management of electrical generation has the potential to meet daily ozone air quality standards at low cost. We show that dynamic management can be effective at reducing ozone, as EGU contributions are important and as the number of EGUs that contribute to high ozone in a given location is small (<6). For two high ozone days and seven geographic regions, EGUs would best be shut down or their production scaled back roughly 1.5 days before the forecasted exceedance. Including online sensitivity techniques in an air quality forecasting model can provide timely and useful information on which EGUs would be most beneficial to shut down or scale back temporarily.     

The sensitivity of modeled ozone to the temporal distribution of point, area, and mobile source emissions in the eastern United States

Ozone remains one of the most recalcitrant air pollution problems in the US. Hourly emissions fields used in air quality models (AQMs) generally show less temporal variability than corresponding measurements from continuous emissions monitors (CEM) and field campaigns would imply. If emissions control scenarios to reduce emissions at peak ozone forming hours are to be assessed with AQMs, the effect of emissions' daily variability on modeled ozone must be understood. We analyzed the effects of altering all anthropogenic emissions' temporal distributions by source group on 2002 summer-long simulations of ozone using the Community Multiscale Air Quality Model (CMAQ) v4.5 and the Carbon Bond IV (CBIV) chemical mechanism with 12 km resolution. We find that when mobile source emissions were made constant over the course of a day, 8-h maximum ozone predictions changed by ±7 parts per billion by volume (ppbv) in many urban areas on days when ozone concentrations greater than 80 ppbv were simulated in the base case. Increasing the temporal variation of point sources resulted in ozone changes of +6 and −6 ppbv, but only for small areas near sources. Changing the daily cycle of mobile source emissions produces substantial changes in simulated ozone, especially in urban areas at night; results suggest that shifting the emissions of NO_x from day to night, for example in electric powered vehicles recharged at night, could have beneficial impacts on air quality.     

Investigation of the influence of transport from oil and natural gas regions on elevated ozone levels in the northern Colorado front range

The Northern Colorado Front Range (NCFR) has been in exceedance of the ozone National Ambient Air Quality Standard (NAAQS) since 2004, which has led to much debate over the sources of ozone precursors to the region, as this area is home to both the Denver, CO, metropolitan area and the Denver–Julesburg Basin, which has experienced rapid growth of oil and natural gas (O&NG) operations and associated emissions. Several recent studies have reported elevated levels of atmospheric volatile organic compounds (VOCs) as a result of O&NG emissions and the potential for significant ozone production from these emissions, despite implementation of stricter O&NG VOC emissions regulations in 2008. Approximately 88% of 1-hr elevated ozone events (>75 ppbv) occur during June–August, indicating that elevated ozone levels are driven by regional photochemistry. Analyses of surface ozone and wind observations from two sites, namely, South Boulder and the Boulder Atmospheric Observatory, both near Boulder, CO, show a preponderance of elevated ozone events associated with east-to-west airflow from regions with O&NG operations in the N-ESE, and a relatively minor contribution of transport from the Denver Metropolitan area to the SE-S. Transport from upwind areas associated with abundant O&NG operations accounts for on the order of 65% (mean for both sites) of 1-hr averaged elevated ozone levels, while the Denver urban corridor accounts for 9%. These correlations contribute to mounting evidence that air transport from areas with O&NG operation has a significant impact on ozone and air quality in the NCFR.

Implications: This article builds on several previous pieces of research that implied significant contributions from oil and natural gas emissions on ozone production in the Northern Colorado Front Range. By correlating increased ozone events with transport analyses we show that there is a high abundance of transport events with elevated ozone originating from the Denver–Julesburg oil and natural gas basin. These findings will help air quality regulators to better assess contributing sources to ozone production and in directing policies to curb ozone pollution in this region.     

Future land use and land cover influences on regional biogenic emissions and air quality in the United States

A regional modeling system was applied with inputs from global climate and chemistry models to quantify the effects of global change on future biogenic emissions and their impacts on ozone and biogenic secondary organic aerosols (BSOA) in the US. Biogenic emissions in the future are influenced by projected changes in global and regional climates and by variations in future land use and land cover (LULC). The modeling system was applied for five summer months for the present-day case (1990–1999, Case 1) and three future cases covering 2045–2054. Individual future cases were: present-day LULC (Case 2); projected-future LULC (Case 3); and future LULC with designated regions of tree planting for carbon sequestration (Case 4). Results showed changing future meteorology with present-day LULC (Case 2) increased average isoprene and monoterpene emission rates by 26% and 20% due to higher temperature and solar insolation. However when LULC was changed together with climate (Case 3), predicted isoprene and monoterpene emissions decreased by 52% and 31%, respectively, due primarily to projected cropland expansion. The reduction was less, at 31% and 14% respectively, when future LULC changes were accompanied by regions of tree planting (Case 4). Despite the large decrease in biogenic emission, future average daily maximum 8-h (DM8H) ozone was found to increase between +8 ppbv and +10 ppbv due to high future anthropogenic emissions and global chemistry conditions. Among the future cases, changing LULC resulted in spatially varying future ozone differences of ?5 ppbv to +5 ppbv when compared with present-day case. Future BSOA changed directly with the estimated monoterpene emissions. BSOA increased by 8% with current LULC (Case 2) but decreased by 45%–28% due to future LULC changes. Overall, the results demonstrated that on a regional basis, changes in LULC can offset temperature driven increases in biogenic emissions, and, thus, LULC projection is an important factor to consider in the study of future regional air quality.     

Evaluation of light-duty vehicle mobile source regulations on ozone concentration trends in 2018 and 2030 in the western and eastern United States

To improve U.S. air quality, there are many regulations on-the-way (OTW) and on-the-books (OTB), including mobile source California Low Emission Vehicle third generation (LEV III) and federal Tier 3 standards. This study explores the effects of those regulations by using the U.S. Environmental Protection Agency's (EPA) Community Multiscale Air Quality (CMAQ) model for 8-hr ozone concentrations in the western and eastern United States in the years 2018 and 2030 during a month with typical high ozone concentrations, July. Alterations in pollutant emissions can be due to technological improvements, regulatory amendments, and changes in growth. In order to project emission rates for future years, the impacts of all of these factors were estimated. This study emphasizes the potential light-duty vehicle emission changes by year to predict ozone levels. The results of this study show that most areas have decreases in 8-hr ozone concentrations in the year 2030, although there are some areas with increased concentrations. Additionally, there are areas with 8-hr ozone concentrations greater than the current U.S. National Ambient Air Quality Standard level, which is 75 ppb.

Implications:

To improve U.S. air quality, many regulations are on the way and on the books, including mobile source California LEV III and federal Tier 3 standards. This study explores the effects of those regulations for 8-hr ozone concentrations in the western and eastern United States in the years 2018 and 2030. The results of this study show that most areas have decreases in 8-hr ozone concentrations in 2030, although there are some areas with increased concentrations. Additionally, there are areas with 8-hr ozone concentrations greater than the current U.S. National Ambient Air Quality Standard level.     

Modelling study of the impact of isoprene and terpene biogenic emissions on European ozone levels

The impact of biogenic volatile organic compound (BVOC) emissions on European ozone distributions has not yet been evaluated in a comprehensive way. Using the CHIMERE chemistry-transport model the variability of surface ozone levels from April to September for 4 years (1997, 2000, 2001, 2003) resulting from biogenic emissions is investigated. It is shown that BVOC emissions increased on average summer daily ozone maxima over Europe by 2.5 ppbv (5%). The impact is most significant in Portugal (up to 15 ppbv) and in the Mediterranean region (about 5 ppbv), being smaller in the northern part of Europe (1.3 ppbv north of 47.5°N). The average impact is rather similar for the three summers (1997, 2000, 2001), but is much larger during the extraordinarily hot summer of 2003. Here, the biogenic contribution to surface ozone doubles compared to other years at some locations. Interaction with anthropogenic NO_x emissions is found to be a key process for ozone production of biogenic precursors. Comparing the impact of the state-of-the-art BVOC emission inventory compiled within the NatAir project and an earlier, widely used BVOC inventory derived from Simpson et al. [1999. Inventorying emissions from nature in Europe. Journal of Geophysical Research 104(D7), 8113–8152] on surface ozone shows that ozone produced from biogenic precursors is less in central and northern Europe but in certain southern areas much higher e.g. Iberian Peninsula and the Mediterranean Sea. The uncertainty in the regionally averaged impact of BVOC on ozone build-up in Europe is estimated to be ±50%.     

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.     

The photochemical pollution episode of 5–16 July 1983 in North-West England

Ground level ozone, NO_x and specific C₂-C₆ hydrocarbon measurements from a rural site in N-W England during a photochemical pollution episode are presented. Maximum hourly ozone concentrations exceeded 80 ppb for ten consecutive days with a maximum of 156 ppb. Mid-morning ozone concentrations were found to be indicative of the amount of ozone from continental sources. The air mass trajectories, total NMHC and alkane : alkene ratios all indicate that in the early to middle stages of the episode the air had been exposed to recent precursor emissions relative to more aged air before and after this period. The measurements are compared with the predictions of recent theoretical models of ozone formation over England.     

Effects of land use data on dry deposition in a regional photochemical model for eastern Texas

Land use data are among the inputs used to determine dry deposition velocities for photochemical grid models such as the Comprehensive Air Quality Model with extensions (CAMx) that is currently used for attainment demonstrations and air quality planning by the state of Texas. The sensitivity of dry deposition and O3 mixing ratios to land use classification was investigated by comparing predictions based on default U.S. Geological Survey (USGS) land use data to predictions based on recently compiled land use data that were collected to improve biogenic emissions estimates. Dry deposition of O3 decreased throughout much of eastern Texas, especially in urban areas, with the new land use data. Predicted 1-hr averaged O3 mixing ratios with the new land use data were as much as 11 ppbv greater and 6 ppbv less than predictions based on USGS land use data during the late afternoon. In addition, the area with peak O3 mixing ratios in excess of 100 ppbv increased significantly in urban areas when deposition velocities were calculated based on the new land use data. Finally, more detailed data on land use within urban areas resulted in peak changes in O3 mixing ratios of approximately 2 ppbv. These results indicate the importance of establishing accurate, internally consistent land use data for photochemical modeling in urban areas in Texas. They also indicate the need for field validation of deposition rates in areas experiencing changing land use patterns, such as during urban reforestation programs or residential and commercial development.     

Impact of biogenic emission uncertainties on the simulated response of ozone and fine particulate matter to anthropogenic emission reductions

The role of emissions of volatile organic compounds and nitric oxide from biogenic sources is becoming increasingly important in regulatory air quality modeling as levels of anthropogenic emissions continue to decrease and stricter health-based air quality standards are being adopted. However, considerable uncertainties still exist in the current estimation methodologies for biogenic emissions. The impact of these uncertainties on ozone and fine particulate matter (PM2.5) levels for the eastern United States was studied, focusing on biogenic emissions estimates from two commonly used biogenic emission models, the Model of Emissions of Gases and Aerosols from Nature (MEGAN) and the Biogenic Emissions Inventory System (BEIS). Photochemical grid modeling simulations were performed for two scenarios: one reflecting present day conditions and the other reflecting a hypothetical future year with reductions in emissions of anthropogenic oxides of nitrogen (NOx). For ozone, the use of MEGAN emissions resulted in a higher ozone response to hypothetical anthropogenic NOx emission reductions compared with BEIS. Applying the current U.S. Environmental Protection Agency guidance on regulatory air quality modeling in conjunction with typical maximum ozone concentrations, the differences in estimated future year ozone design values (DVF) stemming from differences in biogenic emissions estimates were on the order of 4 parts per billion (ppb), corresponding to approximately 5% of the daily maximum 8-hr ozone National Ambient Air Quality Standard (NAAQS) of 75 ppb. For PM2.5, the differences were 0.1-0.25 microg/m3 in the summer total organic mass component of DVFs, corresponding to approximately 1-2% of the value of the annual PM2.5 NAAQS of 15 microg/m3. Spatial variations in the ozone and PM2.5 differences also reveal that the impacts of different biogenic emission estimates on ozone and PM2.5 levels are dependent on ambient levels of anthropogenic emissions.     

Effects of Nighttime Chemistry upon the Transport of Ozone and Ozone Precursors

It has been recognized for several years that ozone in rural areas can exceed the National Ambient Air Quality Standard (NAAQS) for photochemical oxidant whirh was 0.08 ppm for one hour, not to be exceeded more than once per year. During the summer of 1973, the NAAQS was exceeded from 15 to 37% of the time at four rural monitoring sites in Maryland, Pennsylvania, Ohio, and West Virginia.¹ This is a greater violation rate than is found in many urban areas. Dimitriades and Altshuller² have enumerated four possible sources for this rural ozone: (a) transport from urban areas, (b) local photochemical generation from urban ozone precursors, (c) local photochemical generation from precursors of rural origin which may be man-made or natural, and (d) injection of stratospheric ozone into the rural area. This paper considers the chemistry pertinent to the first two of these possible sources of rural ozone, namely the long distance (overnight) transport of ozone and ozone precursors.     

The geographic distribution and economic value of climate change-related ozone health impacts in the United States in 2030

In this United States-focused analysis we use outputs from two general circulation models (GCMs) driven by different greenhouse gas forcing scenarios as inputs to regional climate and chemical transport models to investigate potential changes in near-term U.S. air quality due to climate change. We conduct multiyear simulations to account for interannual variability and characterize the near-term influence of a changing climate on tropospheric ozone-related health impacts near the year 2030, which is a policy-relevant time frame that is subject to fewer uncertainties than other approaches employed in the literature. We adopt a 2030 emissions inventory that accounts for fully implementing anthropogenic emissions controls required by federal, state, and/or local policies, which is projected to strongly influence future ozone levels. We quantify a comprehensive suite of ozone-related mortality and morbidity impacts including emergency department visits, hospital admissions, acute respiratory symptoms, and lost school days, and estimate the economic value of these impacts. Both GCMs project average daily maximum temperature to increase by 1–4°C and 1–5 ppb increases in daily 8-hr maximum ozone at 2030, though each climate scenario produces ozone levels that vary greatly over space and time. We estimate tens to thousands of additional ozone-related premature deaths and illnesses per year for these two scenarios and calculate an economic burden of these health outcomes of hundreds of millions to tens of billions of U.S. dollars (2010$).

Implications:?Near-term changes to the climate have the potential to greatly affect ground-level ozone. Using a 2030 emission inventory with regional climate fields downscaled from two general circulation models, we project mean temperature increases of 1 to 4°C and climate-driven mean daily 8-hr maximum ozone increases of 1–5 ppb, though each climate scenario produces ozone levels that vary significantly over space and time. These increased ozone levels are estimated to result in tens to thousands of ozone-related premature deaths and illnesses per year and an economic burden of hundreds of millions to tens of billions of U.S. dollars (2010$).     

A comparison of measured and simulated ozone concentrations in the rural areas of the eastern United States during summer 1995

The recent regulatory actions toward a longer-term (i.e., 8-hr) average ozone standard have brought forth the potential for many rural areas in the eastern United States to be in noncompliance. However, since a majority of these rural areas have generally few sources of anthropogenic emissions, the measured ozone levels primarily reflect the effects of the transport of ozone and its precursor pollutants and natural emissions. While photochemical grid models have been applied to urban areas to develop ozone mitigation measures, these efforts have been limited to high ozone episode events only and do not adequately cover rural regions. In this study, we applied a photochemical modeling system, RAMS/UAM-V, to the eastern United States from June 1-August 31, 1995. The purpose of the study is to examine the predictive ability of the modeling system at rural monitoring stations that are part of the Clean Air Status Trends Network (CASTNet) and the Gaseous Pollutant Monitoring Program (GPMP). The results show that the measured daily 1-hr ozone maxima and the seasonal average of the daily 1-hr ozone maxima are in better agreement with the predictions of the modeling system than those for the daily 8-hr ozone maxima. Also, the response of the modeling system in reproducing the measured range of ozone levels over the diurnal cycle is poor, suggesting the need for improvement in the treatment of the physical and chemical processes of the modeling system during the nighttime and morning hours if it is to be used to address the 8-hr ozone standard.     

A Comparison of Measured and Simulated Ozone Concentrations in the Rural Areas of the Eastern United States during Summer 1995

ABSTRACT

The recent regulatory actions toward a longer-term (i.e., 8-hr) average ozone standard have brought forth the potential for many rural areas in the eastern United States to be in noncompliance. However, since a majority of these rural areas have generally few sources of anthropogenic emissions, the measured ozone levels primarily reflect the effects of the transport of ozone and its precursor pollutants and natural emissions. While photochemical grid models have been applied to urban areas to develop ozone mitigation measures, these efforts have been limited to high ozone episode events only and do not adequately cover rural regions. In this study, we applied a photochemical modeling system, RAMS/UAM-V, to the eastern United States from June 1-August 31, 1995. The purpose of the study is to examine the predictive ability of the modeling system at rural monitoring stations that are part of the Clean Air Status Trends Network (CASTNet) and the Gaseous Pollutant Monitoring Program (GPMP).

The results show that the measured daily 1-hr ozone maxima and the seasonal average of the daily 1-hr ozone maxima are in better agreement with the predictions of the modeling system than those for the daily 8-hr ozone maxima. Also, the response of the modeling system in reproducing the measured range of ozone levels over the diurnal cycle is poor, suggesting the need for improvement in the treatment of the physical and chemical processes of the modeling system during the nighttime and morning hours if it is to be used to address the 8-hr ozone standard.     

The benefits of lower ozone due to air pollution emission reductions (2002–2011) in the Eastern United States during extreme heat

ABSTRACT

Using the Community Multiscale Air Quality (CMAQ) model and the Benefits Mapping and Analysis Program – Community Edition (BenMAP-CE) tool, we estimate the benefits of anthropogenic emission reductions between 2002 and 2011 in the Eastern United States (US) with respect to surface ozone concentrations and ozone-related health and economic impacts, during a month of extreme heat, July 2011. Based on CMAQ simulations using emissions appropriate for 2002 and 2011, we estimate that emission reductions since 2002 likely prevented 10– 15 ozone exceedance days (using the 2011 maximum 8-hr average ozone standard of 75 ppbv) throughout the Ohio River Valley and 5– 10 ozone exceedance days throughout the Washington, DC – Baltimore, MD metropolitan area during this extremely hot month. CMAQ results were fed into the BenMAP-CE tool to determine the health and health-related economic benefits of anthropogenic emission reductions between 2002 and 2011. We estimate that the concomitant health benefits from the ozone reductions were significant for this anomalous month: 160–800 mortalities (95% confidence interval (CI): 70–1,010) were avoided in July 2011 in the Eastern U.S, saving an estimated $1.3–$6.6 billion (CI: $174 million–$15.5 billion). Additionally, we estimate that emission reductions resulted in 950 (CI: 90–2,350) less hospital admissions from respiratory symptoms, 370 (CI: 180–580) less hospital admissions for pneumonia, 570 (CI: 0–1650) less Emergency Room (ER) visits from asthma symptoms, 922,020 (CI: 469,960–1,370,050) less minor restricted activity days (MRADs), and 430,240 (CI: ?280,350–963,190) less symptoms of asthma exacerbation during July 2011.

Implications: We estimate the benefits of air pollution emission reductions on surface ozone concentrations and ozone-related impacts on human health and the economy between 2002 and 2011 during an extremely hot month, July 2011, in the eastern United States (US) using the CMAQ and BenMAP-CE models. Results suggest that, during July 2011, emission reductions prevented 10-15 ozone exceedance days in the Ohio River Valley and 5-10 ozone exceedance days in the Mid Atlantic; saved 160-800 lives in the Eastern US, saving $1.3 - $6.5 billion; and resulted in 950 less hospital admissions for respiratory symptoms, 370 less hospital admissions for pneumonia, 570 less Emergency Room visits for asthma symptoms, 922,020 less minor restricted activity days, and 430,240 less symptoms of asthma exacerbation.     

Day-of-Week behavior of atmospheric ozone in three U.S. cities

The weekly cycles of atmospheric ozone (O3) are of interest because they provide information about the response of O3 to changes in anthropogenic emissions from weekdays to weekends. The weekly behavior of O3 in Chicago, IL; Philadelphia, PA; and Atlanta, GA, is contrasted. In Chicago and Philadelphia, maximum 1-hr average O3 increases on weekends. In Atlanta, O3 builds up from Mondays to Fridays and declines during weekends. In all three areas, volatile organic compound (VOC)/nitrogen oxides (NOx) ratios are higher during weekends, resulting from greater than proportionate decreases in NOx relative to VOC emissions. The VOC/NOx ratios correlate with maximum 1-hr O3 concentrations in Chicago, a response consistent with a VOC-sensitive airshed. A weak correlation between O3 concentrations and VOC/NOx ratios in Philadelphia suggests the impact of transported O3, which is formed in upwind VOC-sensitive locations that may be hundreds of kilometers away. Ozone concentrations in Atlanta do not correlate with VOC/NOx ratios but with concentrations of NOx and total reactive nitrogen (NOy) carried over from the previous day. When data from 1986-1990 and 1995-1999 are compared, only small differences in the weekly behavior of O3 are observed in Chicago and Philadelphia. The day-of-week differences in O3 are amplified in the more recent period in Atlanta, a possible result of urban growth.     

Spatial distribution of tropospheric ozone in western Washington, USA

We quantified the distribution of tropospheric ozone in topographically complex western Washington state, USA (total area approximately 6000 km(2)), using passive ozone samplers along nine river drainages to measure ozone exposure from near sea level to high-elevation mountain sites. Weekly average ozone concentrations were higher with increasing distance from the urban core and at higher elevations, increasing a mean of 1.3 ppbv per 100 m elevation gain for all mountain transects. Weekly average ozone concentrations were generally highest in Cascade Mountains drainages east and southeast of Seattle (maximum=55-67 pbv) and in the Columbia River Gorge east of Portland (maximum=59 ppbv), and lowest in the western Olympic Peninsula (maximum=34 ppbv). Higher ozone concentrations in the Cascade Mountains and Columbia River locations downwind of large cities indicate that significant quantities of ozone and ozone precursors are being transported eastward toward rural wildland areas by prevailing westerly winds. In addition, temporal (week to week) variation in ozone distribution is synchronous within and between all drainages sampled, which indicates that there is regional coherence in air pollution detectable with weekly averages. These data provide insight on large-scale spatial variation of ozone distribution in western Washington, and will help regulatory agencies optimize future monitoring networks and identify locations where human health and natural resources could be at risk.     

A long-term study of background ozone concentrations in the central Mediterranean—diurnal and seasonal variations on the island of Gozo

A four and a half year study of ozone concentrations in the Central Mediterranean was carried out between January 1997 and August 2001 on a background monitoring station located on the island of Gozo midway between Southern Europe and North Africa.Seasonal and diurnal variations of background ozone are documented. They show the existence of seasonal cycles with a primary maximum in spring followed by a secondary, more variable maximum in summer which indicates that photochemically produced ozone is being transported over the Mediterranean to the rural island of Gozo. Although peak ozone concentrations seldom exceeded 100 ppbv during summer, the background ozone-mixing ratios (as monthly averages) are some of the highest values which can be found at low latitude sites throughout the world. An increasing trend in the annual background ozone concentration from 48.2 ppbv in 1997 to 52.2 ppbv in 2000 is observed. During wintertime the average ozone mixing-ratio (as monthly averages) of 44 ppbv in December is approximately twice as high as on the European continent. This may imply that on Malta, due to higher average ozone concentrations between autumn and spring (the main growing season), crop damage of high economic value may occur.     

Comparison of the 1-hr and 8-hr National Ambient Air Quality Standards for ozone using Models-3

In 1997, the U.S. Environmental Protection Agency revised the National Ambient Air Quality Standard governing ozone (O3), adding an 8-hr standard of 0.08 ppm and phasing out the 1-hr requirement of 0.12 ppm. The 8-hr standard is intended to provide greater protection for human health. This research examines spatial and temporal patterns of exceedances of the standards using monitoring data and modeled estimates. The Penn State/National Center for Atmospheric Research Mesoscale Model and Models-3 framework were used to estimate hourly O3 concentrations for 4-km resolution in the Maryland/Virginia/Delaware/Washington, DC, and northern Georgia domains. Results reveal that the spatial and temporal nature of compliance is considerably different under the 8-hr standard. In the modeling simulations, the 8-hr standard was exceeded 2-5.2 times more often and in a 1.8-16.2 times larger area than the 1-hr standard. The 8-hr standard was exceeded in areas that generally comply with the 1-hr standard and are not well covered by the monitoring network. These results imply that a larger population resides in areas with unhealthy O3 levels than noncompliance with the original 1-hr standard suggests. For the MD/VA/DE/DC domains, 80 and 98% of the total population live in areas with 8-hr National Ambient Air Quality Standards (NAAQS) exceedances for the 1990 and 1995 episodes, respectively.     

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.