No abstract

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.

Abstract. Nitrous acid (HONO) can strongly affect atmospheric photochemistry in polluted regions through the production of hydroxyl radicals (OHs). In January 2017, a severe pollution episode occurred in the Pearl River Delta (PRD) of China, with maximum hourly PM2.5, ozone, and HONO levels reaching 400 µg m−3, 150 ppb, and 8 ppb, respectively, at a suburban site. The present study investigated the sources and processes generating such high HONO concentrations and the role of HONO chemistry in this severe winter episode. Four recently reported HONO sources were added to the Community Multiscale Air Quality (CMAQ) model, including RH-dependent (relative humidity) and light-enhancing effects on heterogeneous reactions, photolysis of particulate nitrate in the atmosphere, and photolysis of HNO3 and nitrate on surfaces. The revised model reproduced the observed HONO and significantly improved its performance for O3 and PM2.5. The model simulations showed that the heterogeneous generation on surfaces (with RH and light effects) was the largest contributor (72 %) to the predicted HONO concentrations, with the RH-enhancing effects more significant at nighttime and the light-enhancing effects more important in the daytime. The photolysis of total nitrate in the atmosphere and deposited on surfaces was the dominant HONO source during noon and afternoon, contributing above 50 % of the simulated HONO. The HONO photolysis was the dominant contributor to HOx production in this episode. With all HONO sources, the daytime average O3 at the Heshan site was increased by 24 ppb (or 70 %), compared to the simulation results without any HONO sources. Moreover, the simulated mean concentrations of TNO3 (HNO3+ fine particle NO3-) at the Heshan site, which was the key species for this haze formation, increased by about 17 µg m−3 (67 %) due to the HONO chemistry, and the peak enhancement reached 55 µg m−3. This study highlights the key role of HONO chemistry in the formation of winter haze in a subtropical environment.

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