Increase of apoplastic ascorbate induced by ozone is insufficient to remove the negative effects in tobacco, soybean and poplar.

Apoplastic ascorbate (ASCapo) is an important contributor to the detoxification of ozone (O3). The objective of the study is to explore whether ASCapo is stimulated by elevated O3 concentrations. The detoxification of O3 by ASCapo was quantified in tobacco (Nicotiana L), soybean (Glycine max (L.) Merr.) and poplar (Populus L), which were exposed to charcoal-filtered air (CF) and elevated O3 treatments (E-O3). ASCapo in the three species were significantly increased by E-O3 compared with the values in the filtered treatment. For all three species, E-O3 significantly increased the malondialdehyde (MDA) content and decreased light-saturated rate of photosynthesis (Asat), suggesting that high O3 has induced injury/damage to plants. E-O3 significantly increased redox state in the apoplast (redox stateapo) for all species, whereas no effect on the apoplastic dehydroascorbate (DHAapo) was observed. In leaf tissues, E-O3 significantly enhanced reduced-ascorbate (ASC) and total ascorbate (ASC+DHA) in soybean and poplar, but significantly reduced these in tobacco, indicating different antioxidative capacity to the high O3 levels among the three species. Total antioxidant capacity in the apoplast (TACapo) was significantly increased by E-O3 in tobacco and poplar, but leaf tissue TAC was significantly enhanced only in tobacco. Leaf tissue superoxide anion (O2•-) in poplar and hydrogen peroxide (H2O2) in tobacco and soybean were significantly increased by E-O3. The diurnal variation of ASCapo, with maximum values occurring in the late morning and lower values experienced in the afternoon, appeared to play an important role in the harmful effects of O3 on tobacco, soybean and poplar.

Tropospheric ozone assessment report: Global ozone metrics for climate change, human health, and crop/ecosystem research.

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.

Establishing policy relevant background (PRB) ozone concentrations in the United States.

Policy Relevant Background (PRB) ozone concentrations are defined by the United States (U.S.) Environmental Protection Agency (EPA) as those concentrations that would occur in the U.S. in the absence of anthropogenic emissions in continental North America (i.e., the U.S, Canada, and Mexico). Estimates of PRB ozone have had an important role historically in the EPA's human health and welfare risk analyses used in establishing National Ambient Air Quality Standards (NAAQS). The margin of safety for the protection of public health in the ozone rulemaking process has been established from human health risks calculated based on PRB ozone estimates. Sensitivity analyses conducted by the EPA have illustrated that changing estimates of PRB ozone concentrations have a progressively greater impact on estimates of mortality risk as more stringent standards are considered. As defined by the EPA, PRB ozone is a model construct, but it is informed by measurements at relatively remote monitoring sites (RRMS). This review examines the current understanding of PRB ozone, based on both model predictions and measurements at RRMS, and provides recommendations for improving the definition and determination of PRB ozone.

An alternative form and level of the human health ozone standard.

Controlled human laboratory studies have shown that there is a disproportionately greater pulmonary function response from higher hourly average ozone (O3) concentrations than from lower hourly average values and thus, a nonlinear relationship exists between O3 dose and pulmonary function (FEV1) response. The nonlinear dose-response relationship affects the efficacy of the current 8-h O3 standard to describe adequately the observed spirometric response to typical diurnal O3 exposure patterns. We have reanalyzed data from five controlled human response to O3 health laboratory experiments as reported by Hazucha et al. (1992), Adams (2003, 2006a, 2006b), and Schelegle et al. (2009). These investigators exposed subjects to multi-hour variable/stepwise O3 concentration profiles that mimicked typical diurnal patterns of ambient O3 concentrations. Our findings indicate a common response pattern across most of the studies that provides valuable information for the development of a lung function (FEV1)-based alternate form for the O3 standard. Based on our reanalysis of the realistic exposure profiles used in these experiments, we suggest that an alternative form of the human health standard, similar to the proposed secondary (i.e., vegetation) standard form, be considered. The suggested form is an adjusted 5-h cumulative concentration weighted O3 exposure index, which addresses both the delay associated with the onset of response (FEV1 decrement) and the nonlinearity of response (i.e., the greater effect of higher concentrations over the mid- and low-range values) on an hourly basis.

The use of critical levels for determining plant response to ozone in Europe and in North America.

Critical levels to determine plant response to ozone (O3) have been used in Europe since the 1980s, utilizing the concentration-based AOT40 to relate plant response to ambient O3 exposure. More recently, there has been progress in Europe toward utilizing flux-based critical levels, because plant response is more closely related to O3 uptake than to the amount of O3 in ambient air. Flux-based critical levels are plant species specific; data for parameterization of flux-based critical levels models are lacking for most plant species. Although flux-based critical levels are now being used for a limited number of agricultural crops and tree species where data are available, the use of flux-based critical levels is limited by the lack of adequate consideration and incorporation of plant internal detoxification mechanisms in flux modeling. Critical levels have not been used in North America; however, recent interest in the U.S. and Canada for using critical loads for nitrogen and sulfur has generated interest in using critical levels for O3. A major obstacle for utilization of critical levels in North America is that ambient air quality standards for O3 in the U.S. and Canada are concentration based. It appears that cumulative exposure-based metrics, particularly when implemented with a quantification of peak concentrations and environmental variables, such as a drought index, are currently the most useful to relate O3 to vegetation response. Because data are unavailable to quantify detoxification potential of vegetation, effective flux models are not available to determine plant response to O3.

Spatial variability of PM2.5 in urban areas in the United States.

Data from the U.S. Environmental Protection Agency's Aerometric Information Retrieval System (now known as the Air Quality System) database for 1999 and 2000 have been used to characterize the spatial variability of concentrations of particulate matter with aerodynamic diameter < or = 2.5 microg (PM2.5) in 27 urban areas across the United States. Different measures were used to quantify the degree of uniformity of PM2.5 concentrations in the urban areas characterized. It was observed that PM2.5 concentrations varied to differing degrees in the urban areas examined. Analyses of several urban areas in the Southeast indicated high correlations between site pairs and spatial uniformity in concentration fields. Considerable spatial variation was found in other regions, especially in the West. Even within urban areas in which all site pairs were highly correlated, a variable degree of heterogeneity in PM2.5 concentrations was found. Thus, even though concentrations at pairs of sites were highly correlated, their concentrations were not necessarily the same. These findings indicate that the potential for exposure misclassification errors in time-series epidemiologic studies exists.

Background Ozone in the Planetary Boundary Layer Over the United States.

Reliable estimates of background O3 in the planetary boundary layer are needed as part of the current review by the U.S. EPA of O3 health and welfare criteria and of the National Ambient Air Quality Standards for O3. Such estimates are especially necessary for comparing O3 concentrations at which vegetation effects occur to O3 concentrations reported to represent background levels. Some vegetation researchers have used the seasonal average of the daily 7-h (0900- 1559 h) average as the exposure parameter in exposure-response models. The 7-h (0900-1559 h) seasonal mean reference point for O3 was assumed to be 0.025 ppm. Ozone aerometric data are presented from the monitoring sites in the United States which experience some of the lowest maximum hourly average concentrations, as identified in the U.S. EPA AIRS database. Criteria are enumerated and discussed for determining whether O3 concentrations at a given site can be considered to be "background" O3. The paper also suggests statistical techniques for estimating background O3 concentrations. Linear regression techniques yield valuable information about O3 concentration data from the literature. Coupled with other criteria, such analyses can be used to select sites that represent "background" sites for O3. Selection of such sites thus allows estimations of background O3 in different areas of the country, at different elevations, and for different averaging times. Using several techniques, the current O3 background at inland sites in the United States and Canada for the daylight 7-h (0900-1559 h) seasonal (April-October) average concentrations usually occurred within the range of 35 ± 10 ppb. For coastal sites, the corresponding O3 concentrations were somewhat lower, occurring within the range of 25 ± 10 ppb for locations in the northern hemisphere, but with most O3 concentrations at the coastal sites in the range of 30 ± 5 ppb. The 50th percentile concentrations range from 16 ppb to 45 ppb at inland sites and range from 10 ppb to 33 ppb at coastal sites. The maximum hourly concentrations range from 50 ppb to 98 ppb at inland sites and range from 44 ppb to 80 ppb at coastal sites. We believe that the maximum hourly concentration of 98 ppb experienced in 1988 was influenced by the massive fires in Yellowstone National Park. These ranges suggest that the background O3 is somewhat dependent on a number of conditions such as the nature of upwind flow, lack of pollution sources, and terrain conditions including deposition with respect to forest or agricultural areas.