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.

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 (O 3) on human health and vegetation have prompted O 3 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 O 3 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 O 3 exposure metrics to changes in hourly O 3 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 O 3 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 O 3 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 O 3 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

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.