Ozone and Other Air Quality-Related Variables Affecting Visibility in the Southeast United States

Abstract

An analysis of ozone (O₃) concentrations and several other air quality-related variables was performed to elucidate their relationship with visibility at five urban and semi-urban locations in the southeast United States during the summer seasons of 1980-1996. The role and impact of O₃ on aerosols was investigated to ascertain a relationship with visibility. Regional trend analysis over the 1980s reveals an increase in maximum O₃ concentration coupled with a decrease in visibility. However, a similar analysis for the 1990s shows a leveling-off of both O₃ and visibility; in both cases, the results were not statistically significant at the 5% level. A case study of site-specific trends at Nashville, TN, followed similar trends. To better understand the relationships between O₃ concentration and visibility, the analysis was varied from yearly through daily to hourly averaged values. This increased temporal resolution showed a statistically significant inverse relationship between visibility and O₃. Site-specific hourly r² values ranged from 0.02 to 0.43. Additionally, by performing back-trajectory analysis, it was found that the visibility degraded by air mass migration over polluted areas.     

Characterizing changes in surface ozone levels in metropolitan and rural areas in the United States for 1980–2008 and 1994–2008

In this analysis, we characterize urban and rural ozone (O₃) trends across the US for the periods 1980–2008 (29 years) and 1994–2008 (15 years) using three exposure metrics, which summarize daily O₃ concentrations to reflect different ways O₃ may affect human health and vegetation. We observe that a statistically significant trend at a specific monitoring site, using one exposure metric, does not necessarily result in a similar trend using the other two metrics. The two most common trends among the monitoring sites are either a continuation of negative trending over the 29-year period or a shift from negative to no trend status, indicating a leveling off of the trending. Very few sites exhibit statistically significant increases in the exposure indices. In characterizing the statistically significant changes in the distribution of hourly average O₃, we observe subtle statistically significant changes in the lower part of the distribution (i.e., below 50 ppb) that are not necessarily captured by the trending patterns associated with the three exposure metrics. Using multisite data from 12 metropolitan cities, we find that as the frequency of higher hourly average concentrations is reduced, the lower hourly average concentrations also move upward toward the mid-level values. The change in the number of the hourly average concentrations in the lower range is consistent with decreased NO scavenging. We recommend assessing possible subtle shifts in O₃ concentrations by characterizing changes in the distribution of hourly average concentrations by month. Identifying statistically significant monthly changes in the mid- and low-level hourly average concentrations may provide important information for assessing changes in physical processes associated with global climate change, long-range transport, and the efficacy of models used for emission and risk reductions. Our results indicate that it is important to investigate the change in the trending pattern with time (e.g., moving 15-year trending) in order to assess how year-to-year variability may influence the trend calculation.     

Ambient ozone and crop loss: establishing a cause-effect relationship

This paper provides the results of a retrospective mathematical analysis of the US NCLAN (National Crop Loss Assessment Network) open-top chamber data. Some 77% of the 73 crop harvests examined, showed no statistically significant yield differences between NF (non-filtered open-top chamber) and AA (chamberless, ambient air) treatments (no easily discernable chamber effects on yield). However, among these cases only seven acceptable examples showed statistically significant yield reductions in NF compared to the CF (charcoal filtered open-top chamber) treatment. An examination of the combined or cumulative hourly ambient O3 frequency distribution for cases with yield loss in NF compared to a similar match of cases without yield loss showed that the mean, median and the various percentiles were all higher (>/= 3 X) in the former in contrast to the latter scenario. The combined frequency distribution of hourly O3 concentrations for the cases with yield loss in NF were clearly separated from the corresponding distribution with no yield loss, at O3 concentrations > 49 ppb. Univariate linear regressions between various O3 exposure parameters and per cent yield losses in NF showed that the cumulative frequency of occurrence of O3 concentrations between 50 and 87 ppb was the best predictor (adjusted R2 = 0.712 and p = 0.011). This analysis also showed that the frequency distribution of hourly concentrations up to 87 ppb O3 represented a critical point, since the addition of the frequency distributions of > 87 ppb O3 did not improve the R2 values. In fact as the frequency of hourly O3 concentrations included in the regression approached 50-100 ppb, the R2 value decreased substantially and the p value increased inversely. Further, univariate linear regressions between the frequencies of occurrence of various O3 concentrations between 50 and 90 ppb and: (a) cases with no yield difference in NF and (b) cases with yield increase in NF compared to the CF treatment (positive effect) provided no meaningful statistical relationship (adjusted R2 = 0.000) in either category. These results support the basis that additional evaluation of the frequency of occurrence of hourly O3] concentrations between 50 and 87 ppb for cases with the yield reductions could provide a meaningful ambient O3 standard, objective or guideline for vegetation.     

Ground-Level Ozone in Eastern Canada: Seasonal Variations,Trends, and Occurrences of High Concentrations

Over the past few years, concern has increased in Canada over the health and environmental impacts of elevated concentrations of ground-level ozone. During the summer the most populated regions of Canada frequently record ozone concentrations that exceed the one-hour average maximum acceptable air quality objective of 32 parts per billion (ppb). In 1988 the Canadian Council of Ministers of the Environment agreed to develop a federal/provincial management plan to control nitrogen oxide and volatile organic compound emissions to reduce ozone concentrations in all affected regions of the country. In addition to the proposed interim control measures, the plan recommended that studies be undertaken to acquire the information necessary to develop sound control strategies. This report represents one of those studies and provides a summary of ground-level ozone measurements for eastern Canada for the 1980 to 1991 period with an emphasis on seasonal variations, trends, and occurrences of high concentrations.

Southwestern Ontario experiences the highest maximum hourly ozone concentrations and the greatest frequency of hours greater than the 82 ppb acceptable objective. Urban sites have the highest frequencies of ozone concentration measurements in the < 10 ppb range, while rural and remote sites show peaks in frequency distribution in the 20 to 30 ppb range. Trend analysis of summertime (May to September) average daily maximum ozone concentration showed no consistent pattern for eastern Canadian sites during 1980 to 1991. Sites in Montreal showed statistically insignificant downward trends while sites in Toronto showed small but statistically significant upward trends. These ozone-increasing trends are associated with reductions in nitric oxide concentrations. At all sites there was large year-to-year variability in peak ozone levels and in the frequency of hours with ozone concentrations above the maximum acceptable objective.     

Differences between weekday and weekend air pollutant levels in southern California

Ambient air quality data were analyzed to empirically evaluate the effects of reductions of volatile organic compounds (VOCs) and oxides of nitrogen (NOx) emissions on weekday and weekend levels of ozone (O3; 1991-1998) and particulate NO3- (1980-1999) in southern California. Despite significantly lower O3 precursor levels on weekends, 20 of 28 South Coast Air Basin (SoCAB) sites (28 of all 78 southern California sites) showed statistically significant higher mean O3 levels on Sundays than on weekdays (p < 0.01); 49 of the remaining 50 sites showed no significant differences between mean weekday and Sunday peak O3 levels. We also observed no statistically significant differences between mean weekday and weekend concentrations of particulate NO3- or nitric acid (HNO3, the precursor of particulate NO3-). Averaged over sites, the mean Sunday NOx and nonmethane hydrocarbon concentrations were 25-41% and 16-30% lower, respectively, than on weekdays. Site-to-site differences between weekend and weekday mean peak hourly O3 levels were related to whether O3 formation was limited by the availability of NOx. A thermodynamic equilibrium model predicts that particulate NO3- levels would decrease in response to a reduction of HNO3, and that particulate ammonium NO3- formation was not limited by the availability of ammonia. The similarity of mean weekday and weekend levels of NO3- therefore did not result from limitations on the formation of particulate NO3- from its precursor, HNO3.     

The use of kriging to estimate monthly ozone exposure parameters for the Southeastern United States

This paper explores the feasibility of (1) using kriging to predict the monthly mean of daily 7-h mean (0900-1559) O3 concentrations, (2) using kriging to estimate the per cent of hourly mean O3 concentrations equal to or greater than 0.07 ppm (137 microg m(-3)) for a specific month, and (3) developing a quantitative relationship between the monthly mean of the daily 7-h (0900-1559) average O3 concentration and the monthly number of hourly concentrations > or = 0.08p ppm (157 microg m(-3)). We found that kriging can be used to estimate the (1) monthly mean of daily 7-h mean O3 concentrations and (2) the percentage of hourly concentrations for a given month > or = 0.07 ppm when sufficient spatial coverage was available. However, the per cent > or = 0.07 ppm parameter exhibited much greater relative variability than the monthly 7-h exposure index. A strong statistical association was found between the monthly number of occurrences > or = 0.08 ppm and monthly 7-h mean concentrations above 0.05 ppm (98 microg m(-3)). Because of the variability that cumulative indices, such as the monthly percentage of hourly concentrations > or = 0.07 ppm , exhibit from site to site, it appears that whether kriging techniques or mathematical regressions are used to estimate the number of elevated O3 hourly concentrations above selected thresholds, large uncertainties associated with the predicted values will exist. These large uncertainties will make it difficult to accurately estimate vegetation effects caused by ambient levels of O3. However, if a generalized quantitative relationship between repeated occurrences of hourly mean concentrations > or = 0.07 ppm or > or = 0.08 and vegetation effects can be developed, it may be possible, using kriged monthly values accompanied with confidence intervals, to identify those areas where vegetation may be at risk. However, before it will be possible to implement such an approach, researchers will have to better quantify the relationship between realistic O3 exposures and vegetation effects.     

Ambient ozone (O3) and adverse crop response: a unified view of cause and effect

This paper presents a cohesive view of the dynamics of ambient O(3) exposure and adverse crop response relationships, coupling the properties of photochemical O(3) production, flux of O(3) from the atmosphere into crop canopies and the crop response per se. The results from two independent approaches ((a) statistical and (b) micrometeorological) were analyzed for understanding cause-effect relationships of the foliar injury responses of tobacco cv Bel-W3 to the exposure dynamics of ambient O(3) concentrations. Similarly, other results from two independent approaches were analyzed in: (1) establishing a micrometeorological relationship between hourly ambient O(3) concentrations and their vertical flux from the air into a natural grassland canopy; and (2) establishing a statistical relationship between hourly ambient O(3) concentrations in long-term, chronic exposures and crop yield reductions. Independent of the approach used, atmospheric conditions appeared to be most conducive and the crop response appeared to be best explained statistically by the cumulative frequency of hourly ambient O(3) concentrations between 50 ppb and 90 ppb (100 and 180 microg m(-3)). In general, this concentration range represents intermediate or moderately enhanced hourly O(3) values in a polluted environment. Further, the diurnal occurrence of this concentration range (often approximately between 0900 and 1600 h in a polluted, agricultural environment) coincided with the optimal CO(2) flux from the atmosphere into the crop canopy, thus high uptake. The frequency of occurrence of hourly O(3) concentrations > 90 ppb (180 microg m(-3)) appeared to be of little importance and such concentrations in general appeared to occur during atmospheric conditions which did not facilitate optimal vertical flux into the crop canopy, thus low uptake. Alternatively, when > 90 ppb (180 microg m(-3)) O(3) concentrations occurred during the 0900-1600 h window, their frequency of occurrence was low in comparison to the 50-90 ppb (100-180 microg m(-3)) range. Based on the overall results, we conclude that if the cumulative frequency of hourly ambient O(3) concentrations between 50-62 ppb (100-124 microg m(-3)) occurred during 53% of the growing season and the corresponding cumulative frequency of hourly O(3) concentrations between 50-74 ppb (100-148 microg m(-3)) occurred during 71% of the growing season, then yield reductions in sensitive crops could be expected, if other factors supporting growth, such as adequate soil moisture are not limiting.     

Extending the Kolmogorov-Zurbenko filter: application to ozone, particulate matter, and meteorological trends

Tropospheric ozone (O3) and particulate matter (PM) are pollutants of great concern to air quality managers. Federal standards for these pollutants have been promulgated in recent years because of the known adverse effects of the pollutants on human health, the environment, and visibility. Local meteorological conditions exert a strong influence over day-to-day variations in pollutant concentrations; therefore, the meteorological signal must be removed in order for air quality planners and managers to examine underlying emissions-related trends and make better air quality management decisions for the future. Although the Kolmogorov-Zurbenko (KZ) filter has been widely used for this type of trend separation in O3 studies in the eastern United States, this article aims to extend the method in three key ways. First, whereas the KZ filter is known as a useful tool for O3 analysis, this study also evaluates its effectiveness when applied to PM. Second, the method was applied to Tucson, AZ, a city in the semi-arid southwestern United States (Southwest), to evaluate the appropriateness of the method in a region with weaker synoptic weather controls on air quality than the eastern United States. Third, additional forms of output were developed and tailored to be more applicable to decision-makers' needs through a partnership between academic researchers and air quality planners and managers. Results of the study indicate that the KZ filter is a useful method for examining emissions-related PM trends, resulting in small, but potentially significant, differences after adjustment. For the Tucson situation with weaker synoptic controls, the KZ method identified mixing height as a more important variable than has been found in other cities.     

The development of sulfur dioxide and ozone exposure profiles that mimic ambient conditions in the rural southeastern united states

A design for constructing experimental mixed-pollutant exposure profiles that reflect regional O₃ and SO₂ ambient air quality is described. The profiles were developed using hour-by-hour O₃ and SO₂ concentration data from monitoring sites in the southeastern United States where slash pine is indigenous. Only sites designated rural or remote, with co-monitored O₃ and SO₂, and at least 75% of the hourly values reported for the period April– October, were used. Each site was characterized by concentration, frequency of occurrence and duration of concentration values, length of time between episodes, and frequency of cooccurrence. A base profile, a 30-day hour-by-hour concentration regime, was constructed using averaged air quality characteristics from the selected sites. Using the base profile, additional regimes were constructed by increasing the concentration of all hourly values above a designated minimum, or by increasing the frequency of occurrence of selected hourly concentrations.     

Visibility trends in Korea during the past two decades

Temporal trends and spatial distributions of visibility measured by the human eye over 60 stations in Korea between 1980 and 2000 are analyzed and discussed. Generally, visibility is lowest on winter mornings and highest on summer afternoons throughout Korea. Visibility in Seoul is now in an increasing trend while it has decreased nationwide, especially in clean coastal areas. Spatial distribution of visibility in the 1990s was related negatively to that of relative humidity (RH). However, visibility generally decreased despite an overall decrease in RH throughout the country. Air pollutants should have played a role in this dissonant variation, particularly in relatively clean areas and on summer afternoons. It was interpreted that the visibility increase in major metropolitan areas, including the greater Seoul area, in the 1990s was caused mainly by the reduction in pollutant emissions by rigorous government policy. But the effect of the emission reduction was manifested with decreasing RH.     

Assessment of a regulatory model's performance relative to large spatial heterogeneity in observed ozone in Houston, Texas

In Houston, some of the highest measured 8-hr ozone (O3) peaks are characterized by sudden increases in observed concentrations of at least 40 ppb in 1 hr or 60 ppb in 2 hr. Measurements show that these large hourly changes appear at only a few monitors and span a narrow geographic area, suggesting a spatially heterogeneous field of O3 concentrations. This study assessed whether a regulatory air quality model (AQM) can simulate this observed behavior. The AQM did not reproduce the magnitude or location of some of the highest observed hourly O3 changes, and it also failed to capture the limited spatial extent. On days with measured large hourly changes in O3 concentrations, the AQM predicted high O3 over large regions of Houston, resulting in overpredictions at several monitors. This analysis shows that the model can make high O3, but on these days the predicted spatial field suggests that the model had a different cause. Some observed large hourly changes in O3 concentrations have been linked to random releases of industrial volatile organic compounds (VOCs). In the AQM emission inventory, there are several emission events when an industrial point source increases VOC emissions in excess of 10,000 mol/hr. One instance increased predicted downwind O3 concentrations up to 25 ppb. These results show that the modeling system is responsive to a large VOC release, but the timing and location of the release, and meteorological conditions, are critical requirements. Attainment of the O3 standard requires the use of observational data and AQM predictions. If the large observed hourly changes are indicative of a separate cause of high O3, then the model may not include that cause, which might result in regulators enacting control strategies that could be ineffective.     

Interpretation of trends of PM2.5 and reconstructed visibility from the IMPROVE network

Under the IMPROVE visibility monitoring network, federal land managers have monitored visibility and fine particle concentrations at 29 Class I area sites (mostly national parks and wilderness areas) and Washington, DC since 1988. This paper evaluates trends in reconstructed visibility and fine particles for the 10th (best visibility days), 50th (average visibility days), and 90th (worst visibility days) percentiles over the nine-year period from 1988-96. Data from these sites provides an indication of regional trends in air quality and visibility resulting from implementation of various emission reduction strategies.     

Interpretation of Trends of PM25 and Reconstructed Visibility from the IMPROVE Network

ABSTRACT

Under the IMPROVE visibility monitoring network, federal land managers have monitored visibility and fine particle concentrations at 29 Class I area sites (mostly national parks and wilderness areas) and Washington, DC since 1988. This paper evaluates trends in reconstructed visibility and fine particles for the 10th (best visibility days), 50th (average visibility days), and 90th (worst visibility days) percentiles over the nine-year period from 1988-96. Data from these sites provides an indication of regional trends in air quality and visibility resulting from implementation of various emission reduction strategies.     

Fine particulate matter and visibility in the Lake Tahoe Basin: chemical characterization, trends, and source apportionment

Speciated PM2.5 (particulate matter with an aerodynamic diameter相似文献   

Application of spectral coherence analysis to describe the relationships between ambient ozone exposure and crop growth

Growth season-based time series spectral coherence analysis was performed between weekly changes in hourly ambient O(3) concentrations and weekly changes in alfalfa height growth. Weekly median hourly O(3) concentration and the corresponding weekly cumulative integral (sum of all hourly concentrations within the week) were used as indicators of weekly O(3) spectral density and coherence with the change in weekly alfalfa height growth. In general, the weekly cumulative integral performed much better than the weekly median O(3) concentration. A conceptual analysis of the results is presented, along with a recommendation that crop growth stage-based cumulative integrals merit further evaluation towards a better understanding of cause-effect relationships.     

Haze trends over the United States, 1980–1995

The patterns and trends of haze over the United States for the period of 1980–1995 are presented. Haze measurements are based on human visual range observations at 298 synoptic meteorological stations operated by the United States Weather Service. There was a significant (∼10%) decline in haziness over the 15-yr period. The reductions were evident throughout the eastern United States as well as over the hazy air basins of California. During the same period, in the eastern United States sulfur emissions also declined by about 10%. However, a causality for the reductions has not been established. This report is an update of an earlier survey of haze patterns and trends from 1950 to 1980.     

Trends of nitrogen in air and precipitation: model results and observations at EMEP sites in Europe, 1980--2003

We analyze trends of some nitrogen compounds using long-term measurements and results from the EMEP (co-operative programme for monitoring and evaluation of the long-range transmissions of air pollutants in Europe) chemical transport model at EMEP sites. We find statistically significant declines at the majority of sites for NH(x) (sum of ammonia and ammonium) in air and for nitrate and ammonium in precipitation, but only at a few sites for xNO3 (sum of nitrate and nitric acid) in air. Model calculations and measurements give similar results. We demonstrate that the lack of trends for xNO3 in air at least partly can be attributed to a shift in the equilibrium between nitric acid and ammonium nitrate towards particulate phase, caused by reductions in the sulfur dioxide emissions.     

Characterization and identification of trends in average ambient ozone and fine particulate matter levels through trajectory cluster analysis in eastern Canada

In many locations in Eastern Canada, ambient levels of fine particulate matter (PM,25) and surface ozone (O3) depend on airflow direction and synoptic scale meteorological conditions. In this study, a cluster analysis was performed on 10 yr (1994-2003) of back-trajectory data for 11 locations in Eastern Canada, resulting in the identification of 10 unique back-trajectory clusters (or airflows) for each location. The airflows were then used to characterize and identify spatial and temporal trends in the daily maximum 8-hr average O3 (dmax 8-hr O3) and the daily average PM2.5 levels. Results showed that airflows from the southwest passing over Michigan and Southern Ontario were associated, on average, with the highest O3 levels at most locations in Eastern Canada. For PM2.5, the highest levels occurred with airflows from the Eastern Ohio River Valley. At major urban locations in Ontario and Quebec, the warm season mean (May to September) dmax 8-hr O3 and the annual mean PM2.5 were, on average, 12 parts per billion and 7.6 microg/m3 higher, respectively, than airflows from the north. Elevated levels of O3 and PM2.5 also occurred under light airflows, and, on average, the levels under light airflows were higher than their nonlight counterparts. At several locations in Canada, including Toronto, Montreal, Quebec City, and Kejimkujik, the annual warm season mean dmax 8-hr O3 experienced a statistically significant (95% confidence) increasing trend over the 10-yr period. When airflow direction was considered, a number of locations experienced statistically significant upward trends in O3 for airflow from the north and northwest. Several locations also showed significant upward trends associated with airflow from the southwest passing over Michigan and Southwestern Ontario. Although there are no statistically significant downward trends, airflows from the southwest have shown a reduction in O3 levels in Southwestern Ontario in more recent years.     

Ozone air quality over North America: part I--a review of reported trends

Ozone and precursor trends can be used to measure the effectiveness of regulatory programs that have been implemented. In this paper, we review trends in the concentrations of O3 NOx, and HCs over North America that have been reported in the literature. Although most existing trend studies are confounded by meteorological variability, both the raw data trends and the trends adjusted for meteorology collectively indicate a general decreasing trend in O3 concentrations in most areas of the United States during 1985-1996. In Canada, mean daily maximum 1-hr O3 concentrations at urban sites show mixed trends with a majority of sites showing an increase from 1980 to 1993. Mean daily maximum 1-hr O3 at most regionally representative Canadian sites appears to decrease from 1985 to 1993 or shows no significant change. There are far fewer data and analyses of NOx and HC trends. Available studies covering various ranges of years indicate decreases in ambient NO and HC concentrations in Los Angeles, CA, decreases in HC concentrations in northeastern U.S. cities, and decreases in NOx concentrations in Canadian cities. Two key needs are long-term HC and NOx measurements, particularly at rural sites, and a systematic comparison of trend detection techniques on a reference data set.     

Plume analysis from field evaluations of a portable air quality monitoring system

ABSTRACT

Near-road measurements in Rochester, NY with a Portable Air Quality Monitoring System indicate a significant plume control of PM_2.5 black carbon (BC) concentrations. This study evaluates the performance of two portable air quality enclosures deployed at collocated research sites to determine their accuracy and usefulness in field deployments, and specifically in pollution plume analysis. One system deployed collocated sensors for measurement of particulate matter mass concentration (Thermo pDR 1500 against Tapered Element Oscillating Microbalance (TEOM) measurement) and the second system deployed sensors for measurement of black carbon (Magee AE33 aethalometer and Brechtel Tricolor Absorption Photometer) in ambient and near-road locations in Rochester, New York, respectively. While the optical PM_2.5 sensors tended to be biased in their determination of concentration by ~15%, they followed changes and trends in concentration very well. The black carbon sensors in the portable systems agreed very well with each other and with the collocated sensor. As a case study to determine the contribution from statistically significant short-lived excursions of pollutant concentration, Morlet wavelet analysis was performed on data from the portable system sensors. Black carbon was found to be strongly influenced by plume behavior with significant plume excursions representing just over 12% of all data points and contributing on average 1 µg/m³ of black carbon above ambient concentrations.

Implications: This paper first evaluates two air pollutant monitoring enclosures with wide applicability including near-road detection of pollutants. Then, we present a novel method to designate isolate statistically significant excursions in air pollution concentration which can be used to determine the impact of pollutant plumes as observed in PM and black carbon behavior near road.