Significance of Atmospheric Ozone as a Phytotoxicant

Since the recognition of ozone as a major phytotoxicant in crop plants in 1957, ozone type symptoms have been observed in a wide range of vegetation. These observations include leafy vegetables, field, forage, and textile crops, also shrubs, broad-leafed ornamental, fruit and forest trees, and various conifers. Fumigation experiments at various institutions have confirmed the etiological relation of ozone in many of these observations. Such visible injuries fail to provide a reliable index to the damaging impact of ozone on the numerous plants affected. Hidden injury or damage by ozone at sub-necrotic levels has been reported and experimentally established in a number of crop plants. Evidence is available which indicats that citrus varieties are so affected, and that much of the citrus decline in Southern California may be ozone induced. Photochemically induced ozone may prove to be the most persistent, if not the most difficult, of atmospheric phytotoxicants to control. Ozone type injury has been reported from eighteen different states, and from Canada to Japan.     

The Effects Of Ozone On Tobacco And Pinto Bean as Conditioned by Several Ecological Factors

The sensitivity of tobacco and/or pinto bean to ozone, as an air pollutant, is increased by growing plants in a shortened photoperiod under reduced light intensity and in a light potting mix. Sensitivity also is influenced by carbon dioxide concentration, time of day, and age of plant at time of exposure. Plants are more severely injured by a given dose under continuous exposure than when the exposure is split into two time periods. Tobacco shows cumulative development of injury when exposed to low concentrations intermittently over several days.     

Effect of Nitrogen Nutrition on the Response of Tobacco to Ozone in the Atmosphere

Experiments were conducted to determine the effect of nitrogen nutrition on the response of tobacco to ozone in the atmosphere. With Nicotiana rustica L., a noncommercial tobacco, plants receiving an “optimum” nitrogen supply were found to be more susceptible to ozone injury than those receiving deficient or luxury supplies. Furthermore, it was found on analyses of the third oldest tobacco leaf that, while these “optimum” plants showed little or no increase in respiration as a result of ozone in concentrations too low to produce visible injury, plants grown with deficient or excess nitrogen showed a significant increase in respiration under these same conditions. The increase in respiration was accompanied by a comparable and equally significant decrease in carbohydrate con-lent in the latter plants which was not apparent in plants at the “optimum” nitrogen supply, as well as an increase in total nitrogen, protein-nitrogen, and amino-acid nitrogen. In conclusion, it is suggested that the carbohydrate reserve built up in plants grown with deficient nitrogen nutrition serves as protection against the ozidative potential of ozone. Likewise, a decrease in carbohydrate content below that of “optimum” plants provides protection in plants grown with an overabundance of nitrogen fertilization, though possibly by a more complex mechanism.     

Response of Bean and Tobacco to Ozone: Effect of Light Intensity,Temperature and Relative Humidity

Pinto bean (Phaseolus vulgaris, L.) and Bel W₃ tobacco (Nicotiana tabacum, L.) were grown and exposed to 40 pphm ozone for 1 hr under a range of light intensities, temperatures, and relative humidities. Foliar injury to the more sensitive plant leaves was determined on the third day after exposure. Each atmospheric factor was independently assessed. Two significant three-way interactions were found: exposure light intensity by growth light intensity by species, and growth temperature by exposure temperature by species. Three significant two-way interactions were found for humidity: growth humidity by exposure humidity, growth humidity by species, and exposure humidity by species. The sensitivity of each species to ozone changed with changes in each environmental condition.     

Ozone exposure

Increased tropospheric ozone concentrations cause damage to both human health and the environment. To assess the exposure of forest areas and selected tree species to ozone, it is necessary to calculate the ozone exposure distribution. The present article describes the application of an ozone interpolation model to the calculation of the ozone exposure distribution in combination with forest inventory data. The exposure of forest regions to ozone was assessed by means of an AOT40 map (accumulated ozone exposure over a threshold of 40 ppb). The calculation was performed by hourly running of the model during the summer term and accumulation of the patterns that exceeded 40 ppb. The exposure of the primary Austrian tree species to ozone can be assessed due to the spatial relation of ozone exposure and tree species patterns. This spatial relation also allows the verification of assumptions concerning ozone-related tree damage.     

Ozone Transport

Elevated concentrations of ozone, often above the national ambient air quality standard for photochemical oxidants, have been measured in both urban and rural areas of Connecticut. One such episode took place on June 10, 1974. Ozone levels, after stabilizing at values slightly above the standard (i.e., 80 to 110 ppb; Connecticut generated ozone concentrations), rose sharply late in the afternoon reaching concentrations as high as 310 ppb (almost 4 times the standard) in Hartford. The trajectory of the air mass, which arrived in Hartford at the time of maximum O₃ occurence, had its origin in the metropolitan New York area during the early morning rush hour on the episode day. This illustrates that the advective transport of O₃ and O₃ precursors into Connecticut from New York are probably responsible for a significant portion (approximately two-thirds) of the elevated O₃ concentrations measured throughout Connecticut on days when winds are from the south-southwest direction. The fact that peak O₃ levels occur late in the afternoon, several hours after maximum sunlight intensity, reinforces the conclusion that excessive O₃ concentrations developed as O₃ and ozone precursors were generated in the vicinity of New York City and then drifted inland into Connecticut on the afternoon sea breeze.

It appears to be unrealistic to develop a hydrocarbon control strategy for Connecticut in order to meet the photochemical oxidant ambient air quality standard when O₃ and/or ozone precursors ad-vectively transported into the State cause oxidant levels to exceed the standard. The complete cessation of all anthropogenic hydrocarbon emissions in Connecticut would not necessarily assure that the standard would be attained here. The implication is that a regional (i.e., the eastern part of the United States) hydrocarbon control strategy is needed to reduce adequately ozone formation and transport so as to allow Connecticut to meet the current oxidant standard.     

Indoor Ozone Exposures

Indoor and outdoor ozone concentrations were measured from late May through October at three office buildings with very different ventilation rates. The indoor values closely tracked the outdoor values, and, depending on the ventilation rate, were 20 to 80 percent of those outdoors. The Indoor/outdoor data are adequately described with a mass balance model. The model can also be coupled with reported air exchange rates to estimate indoor/outdoor ratios for other structures. The results from this and previous studies indicate that Indoor concentrations are frequently a significant fraction of outdoor values. These observations, and the fact that most people spend greater than 90 percent of their time indoors, indicate that indoor ozone exposure (concentration × time) is greater than outdoor exposure for many people. Relatively Inexpensive strategies exist to reduce indoor ozone levels, and these could be implemented to reduce the public’s total ozone exposure.     

Ozone and grosswetterlagen

Meteorological conditions have a decisive impact on surface ozone concentrations. In this study, an empirical model is used to explain the interdependence of ozone and grosswetterlagen. Different meteorological parameters such as air temperature, global solar radiation, relative humidity, wind direction and wind speed are used. Additional nitric oxide (NO) was taken as a representative for the emission situation and ozone maximum of the preceding day in order to evaluate the development of the photochemical situation. The dataset includes data collected over a period of three years (1992–1994) from three stations outside of Munich and one in the center of Munich. All values become variables by calculating means, sums or maxima of the basic dataset consisting of half-hour means. Seasonal periodicity of data is detected with Fourier analysis and eliminated by a division method after computing a seasonal index. The dataset is divided into three different grosswetterlagen groups, depending on main wind direction. One mostly cyclonic (westerly winds), onemixed (alternating winds) and one onlyanticyclonic (easterly winds). The last is completed with one summertime group including values from April to August. Factor analysis is performed for each group to obtain independent linear variable combinations. Overall, relative humidity is the dominant parameter, a typical value indicating meteorological conditions during a grosswetterlage. Linear multiple regression analysis is performed using the factors obtained to reveal how the ozone concentrations are explained in terms of meteorological parameters and NO. The results improve from cyclonic to anticyclonic grosswetterlagen in conformance with the increasing significance of photochemistry, indicated by the high solar radiation and high temperature, and the low relative humidity and low wind speed. The explained variance r² reaches its maximum with more than 50 % of the time in Munich center. This empirical model is applicable to the forecasting of local ozone maximum concentrations with a total standard error deviation of 8.5 to 12.8 % and, if ozone concentrations exceed 80 ppb, with a standard error deviation of 5.4 to 9.5 %.     

Ozone pre-treatment as improver of PAH removal during anaerobic digestion of urban sludge

Polycyclic aromatic hydrocarbons are ubiquitous persistent pollutants. They may accumulate in sludge during wastewater treatment because of their low biodegradability and their hydrophobic characteristics. Combination of ozonation and anaerobic digestion may be efficient to remove PAHs naturally present in sludge. The objective of this study was to investigate the impact of ozone pre-treatment, with and without surfactant addition, on the anaerobic degradation of 12 PAHs (from low to high molecular weight). Under anaerobic digestion without ozonation pre-treatment, the highest removals were obtained for the lightest PAHs (3-aromatic rings). Ozonation pre-treatment of sludge allowed to increase biodegradability or bioavailability of each PAH, and the PAH removals were well correlated to the PAH solubility. Finally, addition of tyloxapol before sludge ozone pre-treatment had antagonist effects on PAH removal during anaerobic digestion: negative impact on anaerobic ecosystem activity and improvement of PAH bioaccessibility (particularly the PAHs with the highest octanol water partition coefficients).     

Effects of Nighttime Chemistry upon the Transport of Ozone and Ozone Precursors

It has been recognized for several years that ozone in rural areas can exceed the National Ambient Air Quality Standard (NAAQS) for photochemical oxidant whirh was 0.08 ppm for one hour, not to be exceeded more than once per year. During the summer of 1973, the NAAQS was exceeded from 15 to 37% of the time at four rural monitoring sites in Maryland, Pennsylvania, Ohio, and West Virginia.¹ This is a greater violation rate than is found in many urban areas. Dimitriades and Altshuller² have enumerated four possible sources for this rural ozone: (a) transport from urban areas, (b) local photochemical generation from urban ozone precursors, (c) local photochemical generation from precursors of rural origin which may be man-made or natural, and (d) injection of stratospheric ozone into the rural area. This paper considers the chemistry pertinent to the first two of these possible sources of rural ozone, namely the long distance (overnight) transport of ozone and ozone precursors.     

Measurement of Ozone Concentration

A method based on hourly NWS cloud amount reports is presented for developing a simple model to account for cloud cover in the determination of the nitrogen dioxide photolysis rate constant, k ₁ The model is parameterized and verified with direct UV radiometer and k ₁ measurements (vs. time of day) collected by Sickles, et al. ¹ at Research Triangle Park. Application of our model to variable cloud condition situations indicates that significant improvement in k ₁ prediction is obtained by including the influence of cloud cover. Comparison of our model with the radiative transfer calculations of Peterson⁷ indicates that the particular parameterization of k ₁ given here is most representative of average albedo and relatively heavy aerosol loading conditions. Comparison of ozone predictions using hourly averaged k ₁ and instantaneous k ₁ under conditions of varying cloud cover suggest that the errors resulting from averaging k ₁ are largest when variations in solar zenith angle are significant over the hour.     

Ozone Air Quality Models

Abstract

The field of ozone air quality modeling, or as it is commonly referred to, photochemical air quality modeling, has undergone rapid change in recent years. Improvements in model components, as well as in methods of interpreting model performance, have contributed to this change. Attendant with this rapid change has been a growing need for those developing and using air quality models and policy makers to have a common understanding of the use and role of models in the decision making process. This Critical Review highlights recent advances and continuing problem areas in photochemical air quality modeling. Emphasis is placed on the components and input data for such models, model performance evaluation, and the implications for their use in regulatory decisions.     

Indoor/Outdoor Ozone Concentrations at a Contemporary Art Gallery

Ozone concentrations were measured both inside and outside the Sainsbury Centre for Visual Arts, near a small city in rural eastern England, during a three-week period in summer. The inside concentration was typically 70 ± 10% of the outside concentration during the period of expected maximum outside levels. During the period of observation the maximum outside ozone levels ranged up to 60 ppb, although there have been periods at this location where outside ozone levels have been well in excess of 120 ppb. The relatively high indoor/outdoor ozone ratio is a function of the Centre’s design, its internal geometry, and its ventilation system. Conventional art galleries and museums experience much lower indoor ozone exposure. The measured indoor ozone levels imply deleterious effects on the gallery exhibits and an enhanced ozone exposure may have to be considered in the design of modern galleries and museums.     

Nicotine as a Marker for Environmental Tobacco Smoke: Implications of Sorption on Indoor Surface Materials

ABSTRACT

Recently developed models and data describing the interactions of gas-phase semi-volatile organic compounds with indoor surfaces are employed to examine the effects of sorption on nicotine's suitability as an environmental tobacco smoke (ETS) marker. Using parameters from our studies of nicotine sorption on carpet, painted wallboard, and stainless steel and previously published data on ETS particle deposition, the dynamic behavior of nicotine was modeled in two different indoor environments: a house and a stainless steel chamber. The results show that apparently contradictory observations of nicotine's behavior in indoor air can be understood by considering the effects of sorption under different experimental conditions. In indoor environments in which smoking has occurred regularly for an extended period, the sorbed mass of nicotine is very large relative to the mass emitted by a single cigarette. The importance of nicotine adsorption relative to ventilation as a gas-phase removal mechanism is reduced. Where smoking occurs less regularly or the indoor surfaces are cleaned prior to smoking (as in a laboratory chamber), nicotine deposition is more significant. Nicotine concentrations closely track the levels of other ETS constituents in environments with habitual smoking if the data are averaged over a period significantly longer than the period between cigarette combustion episodes. However, nicotine is not a suitable tracer for predicting ETS exposures at fine time scales or in settings where smoking occurs infrequently and irregularly.     

The Need for a More Robust Ozone Air Quality Standard

The present National Ambient Air Quality Standard for ozone has many statistical problems, including use of extreme values which have inherent large fluctuations, a compliance test that can gradually lower the target of the design value below the standard level, and inconsistencies between the number-of-exceedances criterion and the design value. The above problems can be avoided or minimized by using a more robust statistic, such as the 95th percentile, and applying a statistical compliance test, without sacrificing the stringency of the standard. Analysis of EPA’s ozone data shows that the annual 95th percentiles and their three-year means have less variability than the annual second highest values and the fourth highest values in three years, respectively. A t test for the mean of the annual 95th percentiles is proposed for compliance testing not only to preserve the averaging concept of the present standard, but also to take account of ozone concentration fluctuations in order to increase the stability of the compliance status of a site or a Metropolitan Statistical Area. A procedure is provided to adjust the level of the 95th-percentile standard so that the stringency of the present standard is preserved.     

Ozone Predictions in Atlanta,Georgia: Analysis of the 1999 Ozone Season

ABSTRACT

Ozone prediction has become an important activity in many U.S. ozone nonattainment areas. In this study, we describe the ozone prediction program in the Atlanta metropolitan area and analyze the performance of this program during the 1999 ozone-forecasting season. From May to September, a team of 10 air quality regulators, meteorologists, and atmospheric scientists made a daily prediction of the next-day maximum 8-hr average ozone concentration. The daily forecast was made aided by two linear regression models, a 3-dimensional air quality model, and the no-skill ozone persistence model. The team's performance is compared with the numerical models using several numerical indicators. Our analysis indicated that (1) the team correctly predicted next-day peak ozone concentrations 84% of the time, (2) the two linear regression models had a better performance than a 3-dimensional air quality model, (3) persistence was a strong predictor of ozone concentrations with a performance of 78%, and (4) about half of the team's wrong predictions could be prevented with improved meteorological predictions.     

Ozone Injury to Pinus Strobus

In a study of the ozone-induced needle blight of eastern white pine in central New York, acute injuries naturally induced on field trees during a year of relatively low ozone concentrations (1 966) were compared with injuries induced during a year of higher concentrations (1967). Injuries were more frequent and severe and were associated with higher mean ozone concentrations in 1967 than in 1966. Characteristic symptoms were induced on foliage of pine branches exposed to controlled doses of ozone as low as 7 ± 1 pphm for four hours or 3 ± 1 pphm for 48 hours. Such doses were equalled or exceeded two and four times, respectively, in the field during the 1 967 season. Ozone sensitivity of pine needle tissue was increased by fumigation in atmospheres containing water mist. High concentrations of ozone (40-60 pphm) caused general injury of foliage of both ozone-susceptible and resistant trees; the symptoms were unlike those found in the field or caused by fumigation with low concentrations of ozone.     

An Ozone Event in Indianapolis

There are doubts concerning the sources of the pollutant ozone in an urban location. Current control regulations,¹ for example, are based on local sources. Many studies suggest that plumes of pollutants released by upwind areas are the cause. For example, New York City has been associated with high O₃ in New England,² Chicago with O₃ in Milwaukee,³ and St. Louis with O₃ in rural Illinois.⁴ Others^5,6 have suggested the problem must be treated on a synoptic scale. In an effort to understand the problem at Indianapolis better, a series of experiments involving aircraft flights were conducted in the Indianapolis area and their results are herein reported. Specifically, a cross country flight of over 100 mi both to the northeast and southwest of Indianapolis, a vertical spiral to 28,000 ft, low level data associated with takeoff and landing of the aircraft, and ground data at four sites, are available for the afternoon of June 9,1976.