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.     

Ozone uptake to the polar snowpack at Summit,Greenland

The uptake of atmospheric ozone to the polar, year-round snowpack on glacial ice was studied at Summit, Greenland during three experiments in 2003, 2004, and 2005. Ozone was measured at up to three depths in the snowpack, on the surface, and above the surface at three heights on a tower along with supporting meteorological parameters. Ozone in interstitial air decreased with depth, albeit ozone gradients showed a high variation depending on environmental conditions of solar radiation and wind speed. Under low irradiance levels, up to 90% of ozone was preserved up to 1 m depth in the snowpack. Ozone depletion rates increased significantly with the seasonal and diurnal cycle of solar irradiance, resulting in only 10% of ozone remaining in the snowpack following solar noon during summertime. Faster snowpack air exchange from wind pumping resulted in smaller above-surface-to-within snowpack ozone gradients. These data indicate that the uptake of ozone to polar snowpack is strongly dependent on solar irradiance and wind pumping. Ozone deposition fluxes to the polar snowpack are consequently expected to follow incoming solar radiation levels and to exhibit diurnal and seasonal cycles. The Summit observations are in stark contrast to recent findings in the seasonal, midlatitude snowpack [Bocquet, F., Helmig, D., Oltmans, S.J., 2007. Ozone in the mid-latitude snowpack at Niwot Ridge, Colorado. Arctic, Antarctic and Alpine Research, in press], where mostly light-independent ozone behavior was observed. These contrasting results imply different ozone chemistry and snowpack–atmosphere gas exchange in the snow-covered polar, glacial conditions compared to the temperate, mid-latitude environment.     

Fluorophotometric Determination of Trace Amounts of Atmospheric Ozone

This work was initiated in an effort to obtain a better method for the manual determination of trace amounts of atmospheric ozone. The method described depends upon the fact that ozone oxidizes nonfluorescent 9, 10-dihydroacridine to fluorescent acridine. When the ethyl alcohol solution of acridine is acidified by 6N acetic acid, the fluorescence maximum occurs approximately at 482 mμ and its intensity is sufficiently strong to be useful in this analysis. Linear relationships between acridine concentrations and fluorescence intensities were obtained from 0.1 to 3.5 μg per ml. by measurement with a commercial fluorophotometer. The results indicated that the low concentrations of experimentally prepared ozone measured by this method were in good agreement with those obtained by the phenolphthalin method. This method appeared to be about twice as sensitive as the phenolphthalin method, but it is subject to some interference from nitrogen dioxide.     

Atmospheric lead concentration distribution in Northern Taiwan

Atmospheric lead concentrations were measured randomly, approximately once per week, at five traffic sites in northern Taiwan from September 1994 to May 1995. Three types of theoretical distributions, lognormal, Weibull and gamma were selected to fit the frequency distribution of the measured lead concentration. Four goodness-of-fit criteria were used to judge which theoretical distribution is the most appropriate to represent the frequency distributions of atmospheric lead.The results show that atmospheric lead concentrations in total suspended particulates fit the lognormal distribution reasonably well in northern Taiwan. The intervals of fitted theoretical cumulative frequency distributions (CFDs) can successfully contain the measured data when the population mean is estimated with a 95% confidence interval. In addition, atmospheric lead concentration exceeding a critical concentration is also predicted from the fitted theoretical CFDs.     

Atmospheric transport and deposition of trace elements onto the Greenland Ice Sheet

Airborne particles of diameter > 0.4 μm reaching Dye 3, Greenland during April–May 1983 were highly variable in size and concentration from day to day. Five-day backward air mass trajectories suggest the importance of long-range transport from more northerly latitudes on days with high concentrations; particle sizes were larger on these days. Lower concentrations and smaller particle sizes were associated with transport from the south. It is inferred that Dye 3 may receive material emitted from Eurasian sources and transported over the Pole, similar to inferences for more northern Arctic sites.Elemental analysis of individual particles showed an abundance of crustal material, with many particles also containing sulfur. Bulk chemical analyses of airborne particles and fresh snow, collected during three snowstorms where ice nucleation dominated, provided data which were used to estimate mass-basis scavenging ratios. Average scavenging ratios were in the range ~1000–2000 for the crustal elements Al, Fe, K, Mg, Mn, and Na. Similar values were observed for Cd, Cu and NO₃⁻. The corresponding ratios for Pb and SO₄²⁻ averaged less than 200. These ratios were used with precipitation rate data to estimate wet deposition velocities in the order of ~2 cm s⁻¹ for the first nine species, and ~0.2 cm s⁻¹ for Pb and SO₄²⁻. Comparing fresh and older surface snow concentrations gave an average dry deposition velocity of roughly 0.2 cm s⁻¹ for the crustal elements, with the small fraction of large particles (~5–10 μm) dominating deposition; much smaller values were associated with the remaining species. When used with other data in the literature, the results of this study suggest that total deposition velocities of Pb and SO₄²⁻ may be as small as 0.05 cm s⁻¹ in relatively dry regions of the Arctic.     

Atmospheric mercury distribution in Northern Europe and in the Mediterranean region

Mercury species in air have been measured at five sites in Northwest Europe and at five coastal sites in the Mediterranean region during measurements at four seasons. Observed concentrations of total gaseous mercury (TGM), total particulate mercury (TPM) and reactive gaseous mercury (RGM) were generally slightly higher in the Mediterranean region than in Northwest Europe. Incoming clean Atlantic air seems to be enriched in TGM in comparison to air in Scandinavia. Trajectory analysis of events where high concentrations of TPM simultaneously were observed at sites in North Europe indicate source areas in Central Europe and provide evidence of transport of mercury on particles on a regional scale.     

Analysis of Ozone and Nitric Oxide by a Chemiluminescent Method in Laboratory and Atmospheric Studies of Photochemical Smog

A prototype instrument monitoring ozone or nitric oxide has been used for photochemical smog studies in the laboratory and the atmosphere. The principle of the detector is based on the chemiluminescent reaction     

Beryllium-7 Measurements in the Houston and Phoenix Urban Areas: An Estimation of Upper Atmospheric Ozone Contributions

Abstract

Natural radionuclides have been proposed as a means of assessing the transport of ozone (O₃) and aerosols in the troposphere. Beryllium-7 (⁷Be) is produced in the upper troposphere and lower stratosphere by the interaction of cosmogenic particles with atmospheric nitrogen and oxygen. ⁷Be has a 53.29-day half-life (478 keV γ) and is known to attach to fine particles in the atmosphere once it is formed. It has been suggested that O₃ from aloft can be transported into rural and urban regions during stratospheric–tropospheric folding events leading to increased background levels of O₃ at the surface. ⁷Be can be used as a tracer of upper atmospheric air parcels and the O₃ associated with them. Aerosol samples with a 2.5-µm cutoff were collected during 12-hr cycles (day/night) for a 30-day period at Deer Park, TX, near Houston, in August– September of 2000, and at Waddell, AZ, near Phoenix, in June–July of 2001. A comparison of ⁷Be levels with 12-hr O₃ averages and maxima shows little correlation. Comparison of nighttime and daytime O₃ levels indicate that during the day, when mixing is anticipated to be higher, the correlation of ⁷Be with O₃ in Houston is approximately twice that observed at night. This is consistent with mixing and with the anticipated loss of O₃ by reaction with nitric oxide (NO) and dry deposition. At best, 30% of the O₃ variance can be explained by the correlation with ⁷Be for Houston, less than that for Phoenix where no significant correlation was seen. This result is consistent with the intercept values obtained for ⁷Be correlations with either O₃ 24-hr averages or O₃ 12-hr maxima and is also in the range of the low O₃ levels (25 ppb) observed at Deer Park during a tropical storm event where the O₃ is attributable primarily to background air masses. That is, maximum background O₃ level contributions from stratospheric sources aloft are estimated to be in the range of 15–30 ppb in the Houston, TX, and Phoenix, AZ, area, and levels above these are because of local tropospheric photochemical production.     

Atmospheric deposition of PCDD/Fs measured via automated and traditional samplers in Northern Taiwan

Most polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in the atmosphere are bound to particles which are suspended in the atmosphere, and eventually settle on soil, vegetation, water bodies or other receptors in the environment. Monitoring atmospheric deposition fluxes (dry/wet) is important in tracing the environmental fate and behavior of PCDD/Fs. PCDD/F depositions were collected via an automated PCDD/F ambient sampler and traditional cylindrical vessels, respectively, from April 2007 to February 2008. The automated PCDD/F ambient sampler used in this study can prevent both re-suspension and photo degradation of the PCDD/Fs collected and effectively separates the PCDD/F samples into dry and wet contributions. The results indicated that the ambient PCDD/F concentrations collected using the PS-1 sampler ranged from 0.02 pg I-TEQ/m³ to 0.16 pg I-TEQ/m³ in Northern Taiwan. The results also indicated that the PCDD/F deposition flux collected using the automated PCDD/F sampler (17.5 pg I-TEQ/m² d to 25.8 pg I-TEQ/m² d) was significantly higher than that sampled with the cylindrical vessels (2.0 pg I-TEQ/m² d to 9.9 pg I-TEQ/m² d). The difference was attributed to the fact that part of the PCDD/F depositions collected using the traditional cylindrical vessels had undergone photo degradation and evaporation. In addition, the wet deposition flux of PCDD/Fs (39.4 pg I-TEQ/m² rainy day to 228 pg I-TEQ/m² rainy day) observed in this study was significantly higher than the dry deposition flux (12.3 pg I-TEQ/m² sunny day to 16.7 pg I-TEQ/m² sunny day). These results demonstrated that wet deposition is the major PCDD/F removal mechanism in the atmosphere.     

Integrated Assessment Modeling of Atmospheric Pollutants in the Southern Appalachian Mountains. Part I: Hourly and Seasonal Ozone

Abstract

Recently, a comprehensive air quality modeling system was developed as part of the Southern Appalachians Mountains Initiative (SAMI) with the ability to simulate meteorology, emissions, ozone, size- and composition-resolved particulate matter, and pollutant deposition fluxes. As part of SAMI, the RAMS/EMS-95/URM-1ATM modeling system was used to evaluate potential emission control strategies to reduce atmospheric pollutant levels at Class I areas located in the Southern Appalachians Mountains. This article discusses the details of the ozone model performance and the methodology that was used to scale discrete episodic pollutant levels to seasonal and annual averages. The daily mean normalized bias and error for 1-hr and 8-hr ozone were within U.S. Environment Protection Agency guidance criteria for urban-scale modeling. The model typically showed a systematic overestimation for low ozone levels and an underestimation for high levels. Because SAMI was primarily interested in simulating the growing season ozone levels in Class I areas, daily and seasonal cumulative ozone exposure, as characterized by the W126 index, were also evaluated. The daily ozone W126 performance was not as good as the hourly ozone performance; however, the seasonal ozone W126 scaled up from daily values was within 17% of the observations at two typical Class I areas of the SAMI region. The overall ozone performance of the model was deemed acceptable for the purposes of SAMI’s assessment.     

Atmospheric polycyclic aromatic hydrocarbons and isomer ratios as tracers of biomass burning emissions in Northern India

Emission from large-scale post-harvest agricultural-waste burning (paddy-residue burning during October–November and wheat-residue burning in April–May) is a conspicuous feature in northern India. The poor and open burning of agricultural residue result in massive emission of carbonaceous aerosols and organic pollutants to the atmosphere. In this context, concentrations of atmospheric polycyclic aromatic hydrocarbons (PAHs) and their isomer ratios have been studied for a 2-year period from a source region (Patiala: 30.2°N; 76.3°E) of two distinct biomass burning emissions. The concentrations of 4—6 ring PAHs are considerably higher compared to 2–3 ring PAHs in the ambient particulate matter (PM_2.5). The crossplots of PAH isomer ratios, fluoranthene?/?(fluoranthene?+?pyrene) and indeno[1,2,3-cd]pyrene/(indeno[1,2,3-cd]pyrene?+?benzo[g,h,i]perylene) for two biomass burning emissions, exhibit distinctly different source characteristics compared to those for fossil-fuel combustion sources in south and south-east Asia. The PAH isomer ratios studied from different geographical locations in northern India also exhibit similar characteristics on the crossplot, suggesting their usefulness as diagnostic tracers of biomass burning emissions.     

Weekday vs. Weekend Ambient Ozone Concentrations: Discussion and Hypotheses with Focus on Northern California

Abstract

Since the early 1970s, researchers and data analysts have reported differences between weekday and weekend ozone concentrations, with higher ozone concentrations occurring on Sundays in some locations. At that time, the phenomenon was referred to as the “Sunday effect.” In the late 1980s, additional papers focused on weekday/weekend differences in air quality in the South Coast (Los Angeles) Air Basin.

Analyses of ozone concentrations measured at a number of locations in northern California reveal that average ozone concentrations are frequently higher on weekends than on weekdays. Violations of the California 0.09 ppm 1-hour air quality standard for ozone also occur in disproportionately greater frequency on weekends. We hypothesize that this phenomenon is based largely on the differences between weekday and weekend emission patterns. We believe that the observed differences may provide information regarding which pollutant reduction strategy, NO_x or ROG control, may be more effective in reducing ambient ozone concentrations. For the northern California region, the presence of higher weekend ozone concentrations suggests the need for ROG control is greater than for NO_x control. If both NO_x and ROG are to be controlled, it is important to understand the interdependence of the two pollutants in forming ozone. With the current uncertainty and debate regarding official vehicular emission inventories, this phenomenon emphasizes the importance of using observation-based data to examine ambient pollution and emission relationships. This natural experiment of varying emissions provides an interesting test case for sophisticated air pollution model performance and evaluation.

Using a Bay Area emission inventory and an estimate of its change from weekday to weekend, combined with a generic Empirical Kinetic Modeling Approach (EKMA) diagram, we demonstrate the weekend effect. In addition, changes in the Bay Area emission inventory from 1980 to 1990, when combined with the EKMA diagram, also show why the weekend effect is more evident in the 1990s.

It is our hypothesis that the presence of the weekend effect, positive or negative, combined with changes in emission changes, provides a simple clue to whether an area is NO_xor ROG limited with respect to ozone formation.     

A Comparison Study of Various Types of Ozone and Oxidant Detectors Which Are Used for Atmospheric Air Sampling

Four continuous automatic analyzers for measurement of atmospheric levels of ozone were used in a calibration and field study. These were (1) a colorimetric instrument based upon detection of iodine released from neutral potassium iodide reagent, {2) a coulometric instrument utilizing the polarization current as a measurement of iodine released by ozone in a cell contacted by potassium iodide reagent, (8) a galvanic cell measuring bromine release by ozone, and (4) an ultraviolet photometer. Some ozone determinations by the manual rubber cracking procedure were included. After calibration with ozone the average relative response to atmospheric ozone levels for each instrument was determined using the colorimetric oxidant analyzer as an arbitrary standard. These responses ranged from 77 percent for the galvanic cell 90 percent for the photometer. The instrument of choice for any given application would seem to be governed by requirements for precision specificity, portability, reliability, and ease of operation.     

Eight-Hour Ozone Trends at Sites in Lake Michigan Ozone Nonattainment Areas

ABSTRACT

Temperature-adjusted trends in 1-hr and 8-hr ozone averages were calculated for ten sites near Lake Michigan for 1980-1995. Results show that ozone trends declined similarly according to both metrics for sites on the west side of the lake. This suggests that the factors underlying the trends were similar. These factors include, among others, ozone control programs designed to address the 1-hr standard. Thus, these control programs may have been similarly effective in moving these sites toward compliance with the 8-hr standard.     

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.     

Ozone decay rates in residences

In urban and suburban settings, indoor ozone exposures can represent a significant fraction of an individual's total exposure. The decay rate, one of the factors determining indoor ozone concentrations, is inadequately understood in residences. Decay rates were calculated by introducing outdoor air containing 80-160 parts per billion ozone into 43 residences and monitoring the reduction in indoor concentration as a function of time. The mean decay rate measured in the living rooms of 43 Southern California homes was 2.80 +/- 1.30 hr-1, with an average ozone deposition velocity of 0.049 +/- 0.017 cm/sec. The experimental protocol was evaluated for precision by repeating measurements in one residence on five different days, collecting 44 same-day replicate measurements, and by simultaneous measurements at two locations in six homes. Measured decay rates were significantly correlated with house type and the number of bedrooms. The observed decay rates were higher in multiple-family homes and homes with fewer than three bedrooms. Homes with higher surface-area-to-volume ratios had higher decay rates. The ratio of indoor-to-outdoor ozone concentrations in homes not using air conditioning and open windows was 68 +/- 18%, while the ratio of indoor-to-outdoor ozone was less than 10% for the homes with air conditioning in use.     

Ozone Decay Rates in Residences

ABSTRACT

In urban and suburban settings, indoor ozone exposures can represent a significant fraction of an individual's total exposure. The decay rate, one of the factors determining indoor ozone concentrations, is inadequately understood in residences. Decay rates were calculated by introducing outdoor air containing 80-160 parts per billion ozone into 43 residences and monitoring the reduction in indoor concentration as a function of time. The mean decay rate measured in the living rooms of 43 Southern California homes was 2.80 + 1.30 hr^-1, with an average ozone deposition velocity of 0.049 + 0.017 cm/sec. The experimental protocol was evaluated for precision by repeating measurements in one residence on five different days, collecting 44 same-day replicate measurements, and by simultaneous measurements at two locations in six homes. Measured decay rates were significantly correlated with house type and the number of bedrooms. The observed decay rates were higher in multiple-family homes and homes with fewer than three bedrooms. Homes with higher surface-area-to-volume ratios had higher decay rates. The ratio of indoor-to-outdoor ozone concentrations in homes not using air conditioning and open windows was 68 + 18%, while the ratio of indoor-to-outdoor ozone was less than 10% for the homes with air conditioning in use.     

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.