Past studies have leveraged distinct observed weekly patterns in emissions of two ozone precursors, volatile organic compounds (VOCs) and nitrogen oxides (NOX = NO + NO2), to better understand ozone chemistry. These studies evaluated day-of-week (DOW) patterns in ozone concentrations to characterize whether ozone formation in certain locations occurs in VOC-limited or NOX-limited chemical regimes. In this work, we analyze 18 years (2002–2019) of Community Multi-scale Air Quality (CMAQ) model data from EPA’s Air QUAlity TimE Series Project (EQUATES) in combination with measured data to evaluate the CMAQ model’s ability to capture changes in ozone formation chemistry in nonattainment areas across the U.S. Statistically significant ozone DOW patterns are quantified using the Welsch t-test. Multi-year trends in DOW patterns were determined using Theil-Sen regression with the Mann–Kendall test for significance. The trends analysis is demonstrated using data from the Phoenix, Arizona and Amador County, California nonattainment areas. In Phoenix, observed and modeled ozone weekend-weekday differences started out positive (VOC-limited) and became negative over the analysis period indicating a trend towards NOX-limited conditions. In Amador County, observed and modeled ozone weekend-weekday differences were negative indicating NOx-limited conditions but diminished over time potentially indicating a reduced role of local weekly varying NOx sources on ozone production in this area. Overall, the model captures DOW ozone trends well across 51 U.S. nonattainment areas.

Past work has shown that traffic patterns in the USA and resulting NOx emissions vary by day of week, with NOx emissions typically being higher on weekdays than weekends. This pattern of emissions leads to different levels of ozone on weekends versus weekdays and can be leveraged to understand how local ozone formation changes in response to NOx emission perturbations in different urban areas. Specifically, areas with lower NOx but higher ozone on the weekends (the weekend effect) can be characterized as NOx-saturated and areas with both lower NOx and ozone on weekends (the weekday effect) can be characterized as NOx-limited. In this analysis, we assess maximum daily 8 h average (MDA8) ozone weekend–weekday differences across 51 USA nonattainment areas using 18 years of observed and modeled data from 2002–2019, using the following two metrics: mean MDA8 ozone and percentage of days with MDA8 ozone > 70 ppb (parts per billion). In addition, we quantify the modeled and observed trends in these weekend–weekday differences across this period of substantial NOx emission reductions in the USA. The model assessment is carried out using U.S. Environmental Protection Agency (EPA)'s Air QUAlity TimE Series Project (EQUATES) Community Multiscale Air Quality (CMAQ) model dataset. We identify three types of MDA8 ozone trends occurring across the USA, namely transitioning chemical regime, disappearing weekday effect, and no trend. The transitioning chemical regime trend occurs in a subset of large urban areas that were NOx-saturated (i.e., volatile organic compound (VOC)-limited) at the beginning of the analysis period but transitioned to mixed chemical regimes or NOx-limited conditions by the end of the analysis period. Nine areas have strong transitioning chemical regime trends using both modeled and observed data and with both metrics indicating strong agreement that they are shifting to more NOx-limited conditions: Milwaukee, Houston, Phoenix, Denver, the Northern Wasatch Front, the Southern Wasatch Front, Las Vegas, Los Angeles – San Bernardino County, Los Angeles – South Coast, and San Diego. The disappearing weekday effect was identified for multiple rural and agricultural areas of California which were NOx-limited for the entire analysis period but appear to become less influenced by local day-of-week emission patterns in more recent years. Finally, we discuss a variety of reasons why there are no trends in certain areas including complex impacts of heterogeneous source mixes and stochastic impacts of meteorology. Overall, this assessment finds that the EQUATES modeling simulations indicate more NOx-saturated conditions than the observations but do a good job of capturing year-to-year changes in weekend–weekday MDA8 ozone patterns.

Extra figures showing area-specific observed and modeled ozone distributions, modeled NOX distributions, modeled formaldehyde distributions and trends in ∆ , ̅̅̅̅̅̅̅̅̅̅ Figure S-1.Door County, WI nonattianment area 2002-2019 May-Sep: observed (top left) and modeled (top center) MDA8 ozone distribution by day of week; modeled NOX (bottom left) and modeled formaldehyde (bottom center) distribution by day of week; observed and modeled trends in ∆ , ̅̅̅̅̅̅̅̅̅̅ (top right); modeled trends in WE-WD NOX and formaldehyde differences (bottom right).The distributions by day of the week are for the entire 18 years with each box representing the 25 th to 75 th percentile for that day of the week across all 18 years, the whiskers representing the 1.5 times the interquartile range, and the bold line inside the box representing the median.WE-WD differences (top and bottom right) are based on 5-year rolling periods.0.221 (0.198,0.25) p-val < 0.

Abstract. Past work has shown that traffic patterns in the US and resulting NOX emissions vary by day of week, with NOX emissions typically higher on weekdays than weekends. This pattern of emissions leads to different levels of ozone on weekends versus weekdays and can be leveraged to understand how local ozone formation changes in response to NOX emissions perturbations in different urban areas. Specifically, areas with lower NOX but higher ozone on the weekends (the weekend effect) can be characterized as NOX -saturated and areas with both lower NOX and ozone on weekends (the weekday effect) can be characterized as NOX-limited. In this analysis we assess ozone weekend-weekday differences across US nonattainment areas using 18 years of observed and modeled data from 2002–2019 using two metrics: mean ozone and percentage of days > 70 ppb. In addition, we quantify the modeled and observed trends in these weekend-weekday differences across this period of substantial NOX emissions reductions in the US. The model assessment is carried out using EPA’s Air QUAlity TimE Series Project (EQUATES) CMAQ dataset. We identify 3 types of ozone trends occuring across the US: disappearing weekend effect, disappearing weekday effect, and no trend. The disappearing weekend effect occurs in a subset of large urban areas that were NOX -saturated (i.e., VOC-limited) at the beginning of the analysis period but transitioned to mixed chemical regimes or NOX-limited conditions by the end of the analysis period. Nine areas have disappearing weekend effect trends in both datasets and with both metrics indicating strong agreement that they are shifting to more NOX-limited conditions: Milwaukee, Houston, Phoenix, Denver, Northern Wasatch Front, Southern Wasatch Front, Las Vegas, Los Angeles – San Bernardino County, Los Angeles – South Coast, and San Diego. The disappearing weekday effect was identified for multiple rural and agricultural areas of California which were NOX -limited for the entire analysis period but appear to become less influenced by local day of week emission patterns in more recent years. Finally, we discuss a variety of reasons why there are no statistically significant trends in certain areas including complex impacts of heterogeneous source mixes and stochastic impacts of meteorology. Overall, this assessment finds that the EQUATES modeling simulations indicate more NOX-saturated conditions than the observations but do a good job of capturing year-to-year changes in weekend-weekday ozone patterns.

Daily maximum 8-hour average (MDA8) ozone (O3) concentrations are well-known to be influenced by local meteorological conditions, which vary across both daily and seasonal temporal scales. Previous studies have adjusted long-term trends in O3 concentrations for meteorological effects using various statistical and mathematical methods in order to get a better estimate of the long-term changes in O3 concentrations due to changes in precursor emissions such as nitrogen oxides (NOX) and volatile organic compounds (VOCs). In this work, the authors present improvements to the current method used by the United States Environmental Protection Agency (US EPA) to adjust O3 trends for meteorological influences by making refinements to the input data sources and by allowing the underlying statistical model to vary locally using a variable selection procedure. The current method is also expanded by using a quantile regression model to adjust trends in the 90th and 98th percentiles of the distribution of MDA8 O3 concentrations, allowing for a better understanding of the effects of local meteorology on peak O3 levels in addition to seasonal average concentrations. The revised method is used to adjust trends in the May to September mean, 90th percentile, and 98th percentile MDA8 O3 concentrations at over 700 monitoring sites in the U.S. for years 2000 to 2016. The utilization of variable selection and quantile regression allow for a more in-depth understanding of how weather conditions affect O3 levels in the U.S. This represents a fundamental advancement in our ability to understand how interannual variability in weather conditions in the U.S. may impact attainment of the O3 National Ambient Air Quality Standards (NAAQS).

Anthropogenic nitrogen oxide (NOx) and volatile organic compound (VOC) emissions in the United States have declined substantially over the last decade, altering the NOx-VOC chemistry and ozone (O3) production characteristics of many areas. In this work, we use multiple air quality analysis tools to assess how these large reductions in NOx and VOC have affected O3 production regimes across the United States between 2007 and 2016. We first compare observed and modeled evolution of NOx-limited and NOx-saturated O3 formation regimes using a day-of-week (DOW) analysis. This comparison builds confidence in the model's ability to qualitatively capture O3 changes due to chemistry and meteorology both within years and across periods of large emission decreases. DOW analysis, however, cannot definitively differentiate between emissions and meteorology impacts. We therefore supplement this analysis with sensitivity calculations from the Comprehensive Air Quality Model with Extensions higher-order decoupled direct method (CAMx HDDM) to characterize modeled shifts in O3 formation chemistry between 2007 and 2016 in different regions of the United States. We also conduct a more detailed investigation of the O3 chemical behavior observed in Chicago and Detroit, two complex urban areas in the Midwest. Both the ambient and modeling data show that more locations across the United States have shifted toward NOx-limited regimes between 2007 and 2016. The model-based HDDM sensitivity analysis shows only a few locations remaining NOx-saturated on high-O3 days in 2016, including portions of New York City, Chicago, Minneapolis, San Francisco, and Los Angeles. This work offers insights into the current state of O3 production chemistry in large population centers across the United States, as well as how O3 chemistry in these areas may evolve in the future.

Epidemiologic studies relating ambient ozone concentrations to adverse health outcomes have typically relied on spatial averages of concentrations from nearby monitoring stations, referred to as “composite monitors.” This practice reflects the assumption that ambient ozone concentrations within an urban area are spatially homogenous. We tested the validity of this assumption by comparing ozone data measured at individual monitoring sites within selected US urban areas to their respective composite monitor time series. We first characterized the temporal correlation between the composite monitor and individual monitors in each area. Next, we analyzed the heteroskedasticity of each relationship. Finally, we compared the distribution of concentrations measured at individual monitors to the composite monitor distribution. Individual monitors showed high correlation with the composite monitor over much of the range of ambient ozone concentrations, though correlations were lower at higher concentrations. The variance between individual monitors and the composite monitor increased as a function of concentration in nearly all the urban areas. Finally, we observed statistical bias in the composite monitor concentrations at the high end of the distribution. The degree to which these results introduce uncertainty into studies that utilize composite monitors depends on the contributions of peak ozone concentrations to reported health effect associations.

Assessment of spatial and temporal variation in the impacts of ozone on human health, vegetation, and climate requires appropriate metrics. A key component of the Tropospheric Ozone Assessment Report (TOAR) is the consistent calculation of these metrics at thousands of monitoring sites globally. Investigating temporal trends in these metrics required that the same statistical methods be applied across these ozone monitoring sites. The nonparametric Mann-Kendall test (for significant trends) and the Theil-Sen estimator (for estimating the magnitude of trend) were selected to provide robust methods across all sites. This paper provides the scientific underpinnings necessary to better understand the implications of and rationale for selecting a specific TOAR metric for assessing spatial and temporal variation in ozone for a particular impact. The rationale and underlying research evidence that influence the derivation of specific metrics are given. The form of 25 metrics (4 for model-measurement comparison, 5 for characterization of ozone in the free troposphere, 11 for human health impacts, and 5 for vegetation impacts) are described. Finally, this study categorizes health and vegetation exposure metrics based on the extent to which they are determined only by the highest hourly ozone levels, or by a wider range of values. The magnitude of the metrics is influenced by both the distribution of hourly average ozone concentrations at a site location, and the extent to which a particular metric is determined by relatively low, moderate, and high hourly ozone levels. Hence, for the same ozone time series, changes in the distribution of ozone concentrations can result in different changes in the magnitude and direction of trends for different metrics. Thus, dissimilar conclusions about the effect of changes in the drivers of ozone variability (e.g., precursor emissions) on health and vegetation exposure can result from the selection of different metrics.

The impacts of surface ozone (O3) on human health and vegetation have prompted O3 precursor emission reductions in the European Union (EU) and United States (US). In contrast, until recently, emissions have increased in East Asia and most strongly in China. As emissions change, the distribution of hourly O3 concentrations also changes, as do the values of exposure metrics. The distribution changes can result in the exposure metric trend patterns changing in a similar direction as trends in emissions (e.g., metrics increase as emissions increase) or, in some cases, in opposite directions. This study, using data from 481 sites (276 in the EU, 196 in the US, and 9 in China), investigates the response of 14 human health and vegetation O3 exposure metrics to changes in hourly O3 concentration distributions over time. At a majority of EU and US sites, there was a reduction in the frequency of both relatively high and low hourly average O3 concentrations. In contrast, for some sites in mainland China and Hong Kong, the middle of the distribution shifted upwards but the low end did not change and for other sites, the entire distribution shifted upwards. The responses of the 14 metrics to these changes at the EU, US, and Chinese sites were varied, and dependent on (1) the extent to which the metric was determined by relatively high, moderate, and low concentrations and (2) the relative magnitude of the shifts occurring within the O3 concentration distribution. For example, the majority of the EU and US sites experienced decreasing trends in the magnitude of those metrics associated with higher concentrations. For the sites in China, all of the metrics either increased or had no trends. In contrast, there were a greater number of sites that had no trend for those metrics determined by a combination of moderate and high O3 concentrations. A result of our analyses is that trends in mean or median concentrations did not appear to be well associated with some exposure metrics applicable for assessing human health or vegetation effects. The identification of shifting patterns in the O3 distribution and the resulting changes in O3 exposure metrics across regions with large emission increases and decreases is an important step in examining the linkage between emissions and exposure metric trends. The results provide insight into the utility of using specific exposure metrics for assessing emission control strategies.

Background:Ambient monitoring data show spatial gradients in ozone (O3) across urban areas. Nitrogen oxide (NOx) emissions reductions will likely alter these gradients. Epidemiological studies often use exposure surrogates that may not fully account for the impacts of spatially and temporally changing concentrations on population exposure.Objectives:We examined the impact of large NOx decreases on spatial and temporal O3 patterns and the implications on exposure.Methods:We used a photochemical model to estimate O3 response to large NOx reductions. We derived time series of 2006–2008 O3 concentrations consistent with 50% and 75% NOx emissions reduction scenarios in three urban areas (Atlanta, Philadelphia, and Chicago) at each monitor location and spatially interpolated O3 to census-tract centroids.Results:We predicted that low O3 concentrations would increase and high O3 concentrations would decrease in response to NOx reductions within an urban area. O3 increases occurred across larger areas for the seasonal mean metric than for the regulatory metric (annual 4th highest daily 8-hr maximum) and were located only in urban core areas. O3 always decreased outside the urban core (e.g., at locations of maximum local ozone concentration) for both metrics and decreased within the urban core in some instances. NOx reductions led to more uniform spatial gradients and diurnal and seasonal patterns and caused seasonal peaks in midrange O3 concentrations to shift from midsummer to earlier in the year.Conclusions:These changes have implications for how O3 exposure may change in response to NOx reductions and are informative for the design of future epidemiology studies and risk assessments.Citation:Simon H, Wells B, Baker KR, Hubbell B. 2016. Assessing temporal and spatial patterns of observed and predicted ozone in multiple urban areas. Environ Health Perspect 124:1443–1452; http://dx.doi.org/10.1289/EHP190

Several participants in Phase 2 of the Air Quality Model Evaluation International Initiative (AQMEII-2) who are applying coupled models to the North American domain are comparing model results for two years, 2006 and 2010, with the goal of performing dynamic model evaluation. From a modeling perspective, the differences of interest are the large reductions in domain total emissions of NOx (21%) and SO2 (37%) from 2006 to 2010 and significant differences in meteorological conditions between these two years. The emission reductions occurred mostly in the eastern U.S, with some reduction in emissions from western wildfires in 2010. Differences in meteorological conditions both confound the impact of emission reductions on ambient air quality and provide an opportunity to examine how models respond to changing meteorology. This study is aimed at documenting changes in emissions, modeled large-scale background concentrations used as boundary conditions for the regional models, and observed meteorology and air quality to provide a context for the dynamic model evaluation studies performed within AQMEII-2. In addition to warmer summer temperatures, conditions in the eastern U.S. summer of 2010 were characterized by less precipitation than in 2006, while western portions of the U.S. and Canada were much cooler in 2010 due to a strengthening of the thermal trough over the Southwest and associated onshore flow. Summer ozone levels in many portions of the Northeast and Midwest were largely unchanged in 2010 despite reductions in precursor emissions. Normalization of the ozone trend, to account for differences in meteorological conditions, including warmer summer temperatures in 2010, shows that the emission reductions would have resulted in lower ozone levels at these locations if not for the countervailing influence of meteorological conditions. Winter mean surface temperatures were generally above average in 2006 whereas below average temperatures were noted in the Southeast and northern plains in 2010, consistent with a greater frequency of cold arctic air outbreaks. In general, changes in observed air quality as measured at U.S. monitoring sites appear to be consistent with differences in emissions and meteorological conditions between 2006 and 2010. Two potential inconsistencies were noted which warrant further investigation: 1) an increase in particulate nitrate during the winter in the Midwest despite lower emissions of NOx and 2) lower than expected SO2 reductions in the Southeast during the winter.

In this work, we evaluate ambient ozone trends at urban, suburban, and rural monitoring sites across the United States over a period of decreasing NOx and VOC emissions (1998-2013). We find that decreasing ozone trends generally occur in the summer, in less urbanized areas, and at the upper end of the ozone distribution. Conversely, increasing ozone trends generally occur in the winter, in more urbanized areas, and at the lower end of the ozone distribution. The 95(th) percentile ozone concentrations decreased at urban, suburban, and rural monitors by 1-2 ppb/yr in the summer and 0.5-1 ppb/yr in the winter. In the summer, there are both increasing and decreasing trends in fifth percentile ozone concentrations of less than 0.5 ppb/yr at urban and suburban monitors, while fifth percentile ozone concentrations at rural monitors decreased by up to 1 ppb/yr. In the winter, fifth percentile ozone concentrations generally increased by 0.1-1 ppb/yr. These results demonstrate the large scale success of U.S. control strategies targeted at decreasing peak ozone concentrations. In addition, they indicate that as anthropogenic NOx emissions have decreased, the ozone distribution has been compressed, leading to less spatial and temporal variability.

In setting primary ambient air quality standards, the EPA's responsibility under the law is to establish standards that protect public health. As part of the current review of the ozone National Ambient Air Quality Standard (NAAQS), the US EPA evaluated the health exposure and risks associated with ambient ozone pollution using a statistical approach to adjust recent air quality to simulate just meeting the current standard level, without specifying emission control strategies. One drawback of this purely statistical concentration rollback approach is that it does not take into account spatial and temporal heterogeneity of ozone response to emissions changes. The application of the higher-order decoupled direct method (HDDM) in the community multiscale air quality (CMAQ) model is discussed here to provide an example of a methodology that could incorporate this variability into the risk assessment analyses. Because this approach includes a full representation of the chemical production and physical transport of ozone in the atmosphere, it does not require assumed background concentrations, which have been applied to constrain estimates from past statistical techniques. The CMAQ-HDDM adjustment approach is extended to measured ozone concentrations by determining typical sensitivities at each monitor location and hour of the day based on a linear relationship between first-order sensitivities and hourly ozone values. This approach is demonstrated by modeling ozone responses for monitor locations in Detroit and Charlotte to domain-wide reductions in anthropogenic NOx and VOCs emissions. As seen in previous studies, ozone response calculated using HDDM compared well to brute-force emissions changes up to approximately a 50% reduction in emissions. A new stepwise approach is developed here to apply this method to emissions reductions beyond 50% allowing for the simulation of more stringent reductions in ozone concentrations. Compared to previous rollback methods, this application of modeled sensitivities to ambient ozone concentrations provides a more realistic spatial response of ozone concentrations at monitors inside and outside the urban core and at hours of both high and low ozone concentrations.