Selecting ozone exposure statistics for determining crop yield loss from air pollutants

Numerous ozone exposure statistics were calculated using hourly ozone data from crop yield loss experiments previously conducted for alfalfa, fresh market and processing tomatoes, cotton, and dry beans in an ambient ozone gradient near Los Angeles, California. Exposure statistics examined included peak (maximum daily hourly) and mean concentrations above specific threshold levels, and concentrations during specific time periods of the day. Peak and mean statistics weighted for ozone concentration and time period statistics weighted for hour of the day were also determined. Polynomial regression analysis was used to relate each of 163 ozone statistics to crop yield. Performance of the various statistics was rated by comparing residual mean square (RMS) values. The analyses demonstrated that no single statistic was best for all crop species. Ozone statistics with a threshold level performed well for most crops, but optimum threshold level was dependent upon crop species and varied with the particular statistics calculated. The data indicated that daily hours of exposure above a critical high-concentration threshold related well to crop yield for alfalfa, market tomatoes, and dry beans. The best statistic for cotton yield was an average of all daily peak ozone concentrations. Several different types of ozone statistics performed similarly for processing tomatoes. These analyses suggest that several ozone summary statistics should be examined in assessing the relationship of ambient ozone exposure to crop yield. Where no clear statistical preference is indicated among several statistics, those most biologically relevant should be selected.     

Trends in exceedances of the ozone air quality standard in the continental United States, 1980–1998

In 1997, the United States National Ambient Air Quality Standard (NAAQS) for ozone was revised from a 1-h average of 0.12 parts per million (ppm) to an 8-h average of 0.08 ppm. Analysis of ozone data for the ensemble of the contiguous United States and for the period 1980–1998 shows that the average number of summer days per year in exceedance of the new standard is in the range 8–24 in the Northeast and in Texas, and 12–73 in southern California. The probability of exceedance increases with temperature and exceeds 20% in the Northeast for daily maximum temperatures above 305 K. We present the results of several different approaches to analyzing the long-term trends in the old and new standards over the continental United States from 1980 to 1998. Daily temperature data are used to resolve meteorological variability and isolate the effects of changes in anthropogenic emissions. Significant negative trends are found in the Northeast urban corridor, in the Los Angeles Basin and on the western bank of Lake Michigan. Temperature segregation enhances the detection of negative trends. Positive trends occur at isolated sites, mostly in the Southeast; a strong positive trend is found in Nashville (Tennessee). There is some evidence that, except in the Southwest, air quality improvements from the 1980s to the 1990s have leveled off in the past decade.     

Site Redundancy in Urban Ozone Monitoring

This article describes two statistical methods that enable air pollution control agencies to assess the effectiveness of the spatial distribution of current stationary ozone monitoring networks by providing measures of site redundancy. These methods analyze site redundancy by determining the degree to which ozone measurements at one site can be successfully predicted from data collected at other monitoring sites. The first method, the similarity (SIM) measure, calculates redundancy based on the percentage of common operational days during which two monitoring stations report similar daily maximum ozone concentrations. The second method, a modeling technique, relates site redundancy in ozone measurement to an R-squared statistic from an autoregressive model. The model uses meteorological components recorded at a central location and ozone concentrations reported by the network’s other monitoring stations. Both techniques can assist in effective allocation of limited monitoring resources and offer a statistical approach to ambient air monitoring network design. The techniques are applied to data collected at six ozone monitoring stations in Harris County, Texas, during an eight-year period in the 1980s. The methods identified two sites in the six-site network that exhibit a high degree of redundancy.     

A climatology of regional background ozone at different elevations in Switzerland (1992–1998)

The ozone records of several monitoring stations in Switzerland from 1992 to 1998 are investigated with respect to the variability observed during regional background conditions, i.e. conditions with little detectable local or regional-scale influences as evident by NO_x and CO concentrations. The sites cover different altitudes between 490 and 3600 m asl. They are characteristic of near-surface conditions, the top of the planetary boundary layer or residual layer, the complex atmosphere in an alpine valley, and the free troposphere. The results reveal a distinctly different ozone variability (diurnal cycles, seasonal cycles, trends) during regional background conditions compared to all days. The estimated annual average ozone concentration under these conditions is between 33 and 50 ppb, dependent on altitude, with a spring maximum and an autumn/winter minimum. Differences in background ozone are found depending on the synoptic weather type. For all sites a positive ozone trend is calculated for background conditions that is larger than for all data. For the latter, the trends appear to be stronger positive for the last 7 years than for the last 11 years.     

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.     

Enhanced ozone over western North America from biomass burning in Eurasia during April 2008 as seen in surface and profile observations

During April 2008, as part of the International Polar Year (IPY), a number of ground-based and aircraft campaigns were carried out in the North American Arctic region (e.g., ARCTAS, ARCPAC). The widespread presence during this period of biomass burning effluent, both gaseous and particulate, has been reported. Unusually high ozone readings for this time of year were recorded at surface ozone monitoring sites from northern Alaska to northern California. At Barrow, Alaska, the northernmost point in the United States, the highest April ozone readings recorded at the surface (hourly average values >55 ppbv) in 37 years of observation were measured on April 19, 2008. At Denali National Park in central Alaska, an hourly average of 79 ppbv was recorded during an 8-h period in which the average was over 75 ppbv, exceeding the ozone ambient air quality standard threshold value in the U.S. Elevated ozone (>60 ppbv) persisted almost continuously from April 19–23 at the monitoring site during this event. At a coastal site in northern California (Trinidad Head), hourly ozone readings were >50 ppbv almost continuously for a 35-h period from April 18–20. At several sites in northern California, located to the east of Trinidad Head, numerous occurrences of ozone readings exceeding 60 ppbv were recorded during April 2008. Ozone profiles from an extensive series of balloon soundings showed lower tropospheric features at ～1–6 km with enhanced ozone during the times of elevated ozone amounts at surface sites in western Canada and the U.S. Based on extensive trajectory calculations, biomass burning in regions of southern Russia was identified as the likely source of the observed ozone enhancements. Ancillary measurements of atmospheric constituents and optical properties (aerosol optical thickness) supported the presence of a burning plume at several locations. At two coastal sites (Trinidad Head and Vancouver Island), profiles of a large suite of gases were measured from airborne flask samples taken during probable encounters with burning plumes. These profiles aided in characterizing the vertical thickness of the plumes, as well as confirming that the plumes reaching the west coast of North America were associated with biomass burning events.     

Statistical Analysis of Trends in Urban Ozone Air Quality

The purpose of this paper is to demonstrate the use of some statistical methods for examining trends in ambient ozone air quality downwind of major urban areas. To this end, daily maximum 1 -hr ozone concentrations measured over New Jersey, metropolitan New York City and Connecticut for the period 1980 to 1989 were assembled and analyzed. This paper discusses the application of the bootstrap method, extreme value statistics and a nonparametric test for evaluating trends in urban ozone air quality. The results indicate that although there is an improvement in ozone air quality downwind of New York City, there has been little change in ozone levels upwind of New York City during this ten-year period.     

A review of statistical methods for the meteorological adjustment of tropospheric ozone

A variety of statistical methods for meteorological adjustment of ozone have been proposed in the literature over the last decade for purposes of forecasting, estimating ozone time trends, or investigating underlying mechanisms from an empirical perspective. The methods can be broadly classified into regression, extreme value, and space–time methods. We present a critical review of these methods, beginning with a summary of what meteorological and ozone monitoring data have been considered and how they have been used for statistical analysis. We give particular attention to the question of trend estimation, and compare selected methods in an application to ozone time series from the Chicago area. We conclude that a number of approaches make useful contributions to the field, but that no one method is most appropriate for all purposes and all meteorological scenarios. Methodological issues such as the need for regional-scale analysis, the nonlinear dependence of ozone on meteorology, and extreme value analysis for trends are addressed. A comprehensive and reliable methodology for space–time extreme value analysis is attractive but lacking.     

Daily surface UV exposure and its relationship to surface pollutant measurements

For the past 30 years, the stratospheric ozone layer has decreased in the Northern Hemisphere. The main effect of this ozone decrease was an expected increase in the UV radiation at the Earth's surface, but there has been no clear evidence of an increasing urban trend in surface UV. This study shows that specific air pollutants can reduce the increased surface levels of UV radiation and offers an explanation for why the expected surface UV increases have not been observed, especially in urban regions. A U.S. Environmental Protection Agency (EPA) UV monitoring site at the University of California at Riverside combined with air pollution data from a site operated by the California Air Resources Board in Rubidoux, CA, provided the basis of this study. The 1997 South Coast Ozone Study (SCOS-97) provided three key ingredients: black carbon, PM10 concentrations, and collocated radiometric measurements. The Total Ozone Mapping Spectrometer (TOMS) satellite data were used to provide the stratospheric ozone levels that were included in the statistical model. All of these input parameters would be used to test this study's hypothesis: the expected increase of surface UV radiation, caused by decreases in stratospheric ozone, can be masked by increases in anthropogenic emissions. The values for the pollutants were 7:00 a.m.-5:00 p.m. averages of the instrument's values taken during summer 1997. A statistical linear regression model was employed using the stratospheric ozone, black carbon, PM10, and surface ozone concentrations, and the sin (theta) and cos (theta). The angle theta is defined by theta = 2pi (Julian date/365). This model obtained a coefficient of determination of 0.94 with an uncertainty level (p value) of less than 0.3% for all of the variables in the model except ground-level ozone. The final model, regressed against a data set from a remote, western North Carolina site, resulted in a coefficient of determination of 0.92. The model shows that black carbon can reduce the Diffey-weighted UV levels that reach the surface by as much as 35%, depending on the season.     

The distribution of particle-phase organic compounds in the atmosphere and their use for source apportionment during the Southern California Children''s Health Study

Atmospheric particulate matter (PM) samples from 12 sites in southern California, collected as part of the Southern California Children's Health Study (SCCHS), were analyzed using gas chromatography/mass spectrometry (GC/MS) techniques. Ninety-four organic compounds were quantified in these samples, including n-alkanes, fatty acids, polycyclic aromatic hydrocarbons (PAH), hopanes, steranes, aromatic diacids, aliphatic diacids, resin acids, methoxyphenols, and levoglucosan. Annual average concentrations of all detected compounds, as well as average concentrations for three seasonal periods, were determined at all 12 sites for the calendar year of 1995. These measurements provide important information about the seasonal and spatial distribution of particle-phase organic compounds in southern California. Also, co-located samples from one site were analyzed to assess precision of measurement. Excellent agreement was observed between annual average concentrations for the broad range of organic compounds measured in this study. Measured concentrations from the 12 sampling sites were used in a previously developed molecular-marker source apportionment model to quantify the primary source contributions to the PM10 organic carbon and mass concentrations at these 12 sites. Source contributions to atmospheric PM from six important air pollution sources were quantified: gasoline-powered motor vehicle exhaust, diesel vehicle exhaust, wood smoke, vegetative detritus, tire wear, and natural gas combustion. Important trends in the seasonal and spatial patterns of the impact of these six sources were observed. In addition, contributions from meat smoke were detected in selected samples.     

Source apportionment of airborne particulate matter using organic compounds as tracers

A chemical mass balance receptor model based on organic compounds has been developed that relates source contributions to airborne fine particle mass concentrations. Source contributions to the concentrations of specific organic compounds are revealed as well. The model is applied to four air quality monitoring sites in southern California using atmospheric organic compound concentration data and source test data collected specifically for the purpose of testing this model. The contributions of up to nine primary particle source types can be separately identified in ambient samples based on this method, and approximately 85% of the organic fine aerosol is assigned to primary sources on an annual average basis. The model provides information on source contributions to fine mass concentrations, fine organic aerosol concentrations and individual organic compound concentrations. The largest primary source contributors to fine particle mass concentrations in Los Angeles are found to include diesel engine exhaust, paved road dust, gasoline-powered vehicle exhaust, plus emissions from food cooking and wood smoke, with smaller contribution from tire dust, plant fragments, natural gas combustion aerosol, and cigarette smoke. Once these primary aerosol source contributions are added to the secondary sulfates, nitrates and organics present, virtually all of the annual average fine particle mass at Los Angeles area monitoring sites can be assigned to its source.     

Prediction of the vertical profile of ozone based on ground-level ozone observations and cloud cover

A number of statistical techniques have been used to develop models to predict high-elevation ozone (O3) concentrations for each discrete hour of day as a function of elevation based on ground-level O3 observations. The analyses evaluated the effect of exclusion/inclusion of cloud cover as a variable. It was found that a simple model, using the current maximum ground-level O3 concentration and no effect of cloud cover provided a reasonable prediction of the vertical profile of O3, based on data analyzed from O3 sites located in North Carolina and Tennessee. The simple model provided an approach that estimates the concentration of O3 as a function of elevation (up to 1800 m) based on the statistical results with a +/- 13.5 ppb prediction error, an R2 of 0.56, and an index of agreement, d1, of 0.66. The inclusion of cloud cover resulted in a slight improvement in the model over the simple regression model. The developed models, which consist of two matrices of 24 equations (one for each hour of day for clear to partly cloudy conditions and one for cloudy conditions), can be used to estimate the vertical O3 profile based on the inputs of the current day's 1-hr maximum ground-level O3 concentration and the level of cloud cover.     

Temporal variability of selected air toxics in the United States

Ambient measurements of hazardous air pollutants (HAPs, air toxics) collected in the United States from 1990 to 2005 were analyzed for diurnal, seasonal, and/or annual variability and trends. Visual and statistical analyses were used to identify and quantify temporal variations in air toxics at national and regional levels. Sufficient data were available to analyze diurnal variability for 14 air toxics, seasonal variability for 24 air toxics, and annual trends for 26 air toxics. Four diurnal variation patterns were identified and labeled invariant, nighttime peak, morning peak, and daytime peak. Three distinct seasonal patterns were identified and labeled invariant, cool, and warm. Multiple air toxics showed consistent decreasing trends over three trend periods, 1990–2005, 1995–2005, and 2000–2005. Trends appeared to be relatively consistent within chemically similar pollutant groups. Hydrocarbons such as benzene, 1,3-butadiene, styrene, xylene, and toluene decreased by approximately 5% or more per year at more than half of all monitoring sites. Concentrations of carbonyl compounds such as formaldehyde, acetaldehyde, and propionaldehyde were equally likely to have increased or decreased at monitoring sites. Chlorinated volatile organic compounds (VOCs) such as tetrachloroethylene, dichloromethane, and methyl chloroform decreased at more than half of all monitoring sites, but decreases among these species were much more variable than among the hydrocarbons. Lead particles decreased in concentration at most monitoring sites, but trends in other metals were not consistent over time.     

Factors influencing the ground level distribution of ozone in Europe

Ozone is a widely distributed pollutant in the atmospheric boundary layer over north west Europe. Three main sources have been identified: the stratosphere, the free troposphere and boundary layer photochemical production. The pattern of ground level ozone concentrations resulting from these three sources cannot be accurately specified. Ozone shows significant variations in space and time but because of the high cost of continuous monitoring equipment, spatial variations on a national and international basis have not been studied in detail. Variations in ozone concentrations at individual monitoring sites have been given a great deal of attention and experience gained from United Kingdom monitoring sites is described in some detail. The averaging time statistical model of Larsen is employed to relate the exposure levels measured over different averaging periods. Diurnal variations have a major influence on exposure levels at sites nominally exposed to the same regional ozone distribution. The physical and chemical mechanisms which give rise to diurnal variations are detailed so that sites can be screened for different diurnal behaviour characteristics.     

Operational ozone forecasts for the region of Copenhagen by the Danish Meteorological Institute

The Danish Meteorological Institute (DMI) has developed an operational forecasting system for ozone concentrations in the Atmospheric Boundary Layer; this system is called the Danish Atmospheric Chemistry FOrecasting System (DACFOS). At specific sites where real-time ozone concentration measurements are available, a statistical after-treatment of DACFOS’ results adjusts the next 48 h ozone forecasts. This post-processing of DACFOS’ forecasts is based on an adaptive linear regression model using an optimal state estimator algorithm. The regression analysis uses different linear combinations of meteorological parameters (such as temperature, wind speed, surface heat flux and atmospheric boundary layer height) supplied by the Numerical Weather Prediction model DMI-HIRLAM. Several regressions have been tested for six monitoring stations in Denmark and in England, and four of the linear combinations have been selected to be employed in an automatic forecasting system. A statistical study comparing observations and forecasts shows that this system yields higher correlation coefficients as well as smaller biases and RMSE values than DACFOS; the present post-processing thus improves DACFOS’ forecasts. This system has been operational since June 1998 at the DMI's monitoring station in the north of Copenhagen, for which a new ozone forecast is presented every 6 h on the DMI's internet public homepage.     

The Distribution of Particle-Phase Organic Compounds in the Atmosphere and Their Use for Source Apportionment during the Southern California Children’s Health Study

Abstract

Atmospheric particulate matter (PM) samples from 12 sites in southern California, collected as part of the Southern California Children’s Health Study (SCCHS), were analyzed using gas chromatography/mass spectrometry (GC/MS) techniques. Ninety-four organic compounds were quantified in these samples, including n-alkanes, fatty acids, polycyclic aromatic hydrocarbons (PAH), ho-panes, steranes, aromatic diacids, aliphatic diacids, resin acids, methoxyphenols, and levoglucosan. Annual average concentrations of all detected compounds, as well as average concentrations for three seasonal periods, were determined at all 12 sites for the calendar year of 1995. These measurements provide important information about the seasonal and spatial distribution of particle-phase organic compounds in southern California. Also, co-located samples from one site were analyzed to assess precision of measurement. Excellent agreement was observed between annual average concentrations for the broad range of organic compounds measured in this study. Measured concentrations from the 12 sampling sites were used in a previously developed molecular-marker source apportionment model to quantify the primary source contributions to the PM₁₀ organic carbon and mass concentrations at these 12 sites. Source contributions to atmospheric PM from six important air pollution sources were quantified: gasoline-powered motor vehicle exhaust, diesel vehicle exhaust, wood smoke, vegetative detritus, tire wear, and natural gas combustion. Important trends in the seasonal and spatial patterns of the impact of these six sources were observed. In addition, contributions from meat smoke were detected in selected samples.     

The Characterization of Ozone and Sulfur Dioxide Air Quality Data for Assessing Possible Vegetation Effects

Since the 1960s, much effort has been devoted to collecting and formatting air quality data. This paper discusses 1) the availability of air quality data for assessing potential biological impacts associated with ozone and sulfur dioxide ambient exposures, 2) examples of how air quality data can be characterized for assessing vegetation effects, and 3) the limitations associated with some exposure parameters used for developing relevant vegetation doseresponse yield reduction models. Data are presented showing that some ozone monitoring sites not continuously affected by local urban sources experience consecutive hourly ozone exposures ≥0.10 ppm in the late evening and early morning hours. These sites experience their maximum ozone concentrations either in the spring or summer months. Sites influenced by local rural sources experience their maximum ozone concentrations during the summer months. It is suggested that further research be performed to identify whether the sensitivity of a target organism at the time of exposure, as well as the pollutant concentration and chemical form that enters into the target organism, is as important in defining effects as air pollutant exposure alone.     

The Characterization of Ozone Data for Sites Located in Forested Areas of the Eastern United States

Six years (1978-1983) of ozone monitoring data from sites located within six forested areas were examined. Areas that experienced the lowest to the highest ozone exposures were located in (1) northern New England/New York and upper Great Lakes, (2) New York/Pennsylvania/Maryland, (3) southeastern/southern, and (4) New Jersey pinelands. In general, higher ozone concentrations were observed in 1978, 1980 and 1983 as compared to the other three years examined. Ozone concentrations varied considerably within the areas. Recommendations for additional ozone monitoring sites are made. A concentrated effort should be made to examine ozone monitoring data from subsequent years (1984, 1985, and 1986) to explore whether the 6-year period 1978 through 1983 is representative of the annual variability of ozone concentrations over eastern forested areas. To better understand the relationship between ozone exposure and possible forest effects, we recommend that the temporal distributions of elevated ozone concentrations over a growing season be examined. The occurrence of elevated ozone levels during specific growth periods during a season may be an important aspect that biologists may wish to explore.     

Modeling the long-term frequency distribution of regional ozone concentrations

Efficient methods are developed for modeling emissions – air quality relationships that govern ozone and NO₂ concentrations over very long periods of time. A baseline model evaluation study is conducted to assess the accuracy and speed with which the relationship between pollutant emissions and the frequency distribution of O₃ concentrations throughout the year can be computed along with annual average NO₂ values using a deterministic photochemical airshed model driven by automated objective analysis of measured meteorological parameters. Methods developed are illustrated by application to the air quality situation that exists in Southern California. Model performance statistics for O₃ are similar to the results obtained in previous short-term episodic model evaluation studies that were based on hand-crafted meteorological inputs that are supplemented by expensive field measurement campaigns. Model predictions at one of the highest NO₂ concentration sites in the US indicate that measured violation of the US annual average NO₂ air quality standard at that site occurs because other species such as HNO₃ and PAN are measured as if they were NO₂ by the chemiluminescent NO_x monitors in current use.     

Estimating contribution of wildland fires to ambient ozone levels in National Parks in the Sierra Nevada, California

Data from four continuous ozone and weather monitoring sites operated by the National Park Service in Sierra Nevada, California, are used to develop an ozone forecasting model and to estimate the contribution of wildland fires on ambient ozone levels. The analyses of weather and ozone data pointed to the transport of ozone precursors from the Central Valley as an important source of pollution in these National Parks. Comparisons of forecasted and observed values demonstrated that accurate forecasts of next-day hourly ozone levels may be achieved by using a time series model with historic averages, expected local weather and modeled PM values as explanatory variables. Results on fire smoke influence indicated occurrence of significant increases in average ozone levels with increasing fire activity. The overall effect on diurnal ozone values, however, was small when compared with the amount of variability attributed to sources other than fire.