Chemistry of Atmospheric Oxidants

All of the important oxidants in polluted air are formed there by chemical reactions which occur among the primary pollutants. The most abundant of these oxidants is ozone which is formed in a cycle involving nitric oxide, nitrogen dioxide, atmospheric oxygen, and hydrocarbons. This ozone is best understood, not as a reaction product, but as an intermediate in steady-state concentration between formation and disappearance reactions. Hydrocarbons permit accumulation of ozone by reacting to scavenge the nitric oxide which would otherwise remove the ozone. The amount of ozone which can be formed in ambient polluted air is limited to about 1 ppm because these scavenging reactions become less effective when the nitric oxide concentration becomes very small. The peroxyacyl nitrates are a group of oxidants which result from reactions between oxides of nitrogen and organic pollutants. Olefinic and aromatic hydrocarbons make the largest contribution to PAN formation; saturates contribute little if any. The role of nitrogen dioxide and other oxidizing agents is also discussed.     

Systematic development of an artificial neural network model for real-time prediction of ground-level ozone in Edmonton, Alberta, Canada

Ground-level ozone is a secondary pollutant that has recently gained notoriety for its detrimental effects on human and vegetation health. In this paper, a systematic approach is applied to develop artificial neural network (ANN) models for ground-level ozone (O3) prediction in Edmonton, Alberta, Canada, using ambient monitoring data for input. The intent of these models is to provide regulatory agencies with a tool for addressing data gaps in ambient monitoring information and predicting O3 events. The models are used to determine the meteorological conditions and precursors that most affect O3 concentrations. O3 time-series effects and the efficacy of the systematic approach are also assessed. The developed models showed good predictive success, with coefficient of multiple determination values ranging from 0.75 to 0.94 for forecasts up to 2 hr in advance. The inputs most important for O3 prediction were temperature and concentrations of nitric oxide, total hydrocarbons, sulfur dioxide, and nitrogen dioxide.     

An assessment of the impact of California's Phase 2 Reformulated Gasoline on ozone air quality

California's Phase 2 Reformulated Gasoline (CaRFG), introduced early in 1996, represents an important step toward attainment of ozone standards. Studies of vehicle emissions and ambient air quality data have reported substantial reductions of ozone precursors due to CaRFG. This study uses daily measurements of regional ozone and meteorology to estimate the effect of CaRFG on ozone concentrations in three areas of California. In each area, a regression model was used to partially account for the daily effects of meteorology on area-wide ozone maxima for May-October. The statistical models are based on combinations of air temperature aloft (approximately 5000 ft), surface air temperatures, and surface wind speeds. Estimated ozone benefits were attributed to CaRFG after accounting for meteorology, which improved the precision of the estimates by approximately 37-57% based on a resampling analysis. The ozone benefits were calculated as the difference in ozone times the proportion of the reductions of hydrocarbons and nitrogen oxides attributed to CaRFG by the best available emission inventories. Ozone benefits attributed to CaRFG (with approximately 90% confidence) are 8-13% in the Los Angeles area, -2-6% in the San Francisco Bay area overall with greater benefits in two major subregions, and 3-15% in the Sacramento area.     

Non-Methane Hydrocarbon Air Quality Measurements

It is important in the implementation of the air quality standard for ozone/oxidants and non-methane hydrocarbons to develop quantitative relationships between these pollutants in air quality regions. Analyses for ambient air non-methane hydrocarbon give a direct measure of the progress in control of hydrocarbon emissions and in the reduction of oxidant/ozone concentration levels. Total hydrocarbon concentrations are much more available than non-hydrocarbon levels. An empirical relationship between total hydrocarbons and non-methane hydrocarbons has been obtained from measurements at both west and east coast sites in the U. S. The comparability of measurements from flame ionization analyzers and gas chromatography has been demonstrated. Either analytical technique can be applied to samples collected at monitoring sites to provide the 6-9 A.M. non-methane hydrocarbon aerometric results specified in the air quality standards.     

Factors influencing the reactivity of polycyclic aromatic hydrocarbons adsorbed on filters and ambient POM with ozone

Five polycyclic aromatic hydrocarbons (PAH), pyrene (PY), fluoranthene (FL), benz(a)anthracene (BaA), benzo(a)pyrene (BaP), and benzo(e)pyrene (BeP) adsorbed on glass fiber (GF) and Teflon impregnated glass fiber (TIGF) filters and on ambient particulate organic matter (POM) were exposed to ozone (50–300 ppb) passively in a 360-liter Teflon chamber and actively in a flow system. The influence of ozone concentration, exposure time and relative humidity (RH) on the degree of degradation of these PAH was established. The most reactive PAH both on filters and in ambient POM were PY, BaA and BaP. Up to 50–80% of these PAH degraded in 3-hr exposures to 200 ppb of ozone at ∼1% RH; in a flow system, most of the degradation occurred within the first 10 minutes of exposure. With the exception of BaP, the degradation of the PAH tested on GF and TIGF filters were much lower at 50% RH than at 1% RH, whether they were exposed to ozone in an active or passive mode. Interestingly, RH did not significantly affect the reactivity of PAH present in ambient POM passively exposed to ozone. Our results show that PAH are susceptible to ozone degradation under many typical atmospheric conditions.     

Seedling insensitivity to ozone for three conifer species native to Great Smoky Mountains National Park

Field symptoms typical of ozone injury have been observed on several conifer species in Great Smoky Mountains National Park, and tropospheric ozone levels in the Park can be high, suggesting that ozone may be causing growth impairment of these plants. The objective of this research was to test the ozone sensitivity of selected conifer species under controlled exposure conditions. Seedlings of three species of conifers, Table Mountain pine (Pinus pungens), Virginia pine (Pinus virginiana), and eastern hemlock (Tsuga canadensis), were exposed to various levels of ozone in open-top chambers for one to three seasons in Great Smoky Mountains National Park in Tennessee, USA. A combination of episodic profiles (1988) and modified ambient exposure regimes (1989-92) were used. Episodic profiles simulated an average 7-day period from a monitoring station in the Park. Treatments used in 1988 were: charcoal-filtered (CF), 1.0x ambient, 2.0x ambient, and ambient air-no chamber (AA). In 1989 a 1.5x ambient treatment was added, and in 1990, additional chambers were made available, allowing a 0.5x ambient treatment to be added. Height, diameter, and foliar injury were measured most years. Exposures were 3 years for Table Mountain pine (1988-90), 3 years for hemlock (1989-91), and 1 and 2 years for three different sets of Virginia pine (1990, 1990-91, and 1992). There were no significant (p<0.05) effects of ozone on any biomass fraction for any of the species, except for older needles in Table Mountain and Virginia pine, which decreased with ozone exposure. There were also no changes in biomass allocation patterns among species due to ozone exposure, except for Virginia pine in 1990, which showed an increase in the root:shoot ratio. There was foliar injury (chlorotic mottling) in the higher two treatments (1.0x and 2.0x for Table Mountain and 2.0x for Virginia pine), but high plant-to-plant variability obscured formal statistical significance in many cases. We conclude, at least for growth in the short-term, that seedlings of these three conifer species are insensitive to ambient and elevated levels of ozone, and that current levels of ozone in the Park are probably having minimal impacts on these particular species.     

Responses of spring wheat (Triticum aestivum L.) to ozone produced by either electric discharge and dry air or by UV-lamps and ambient air

The aim of the present study was to examine if ozone produced similar effects on spring wheat growth with and without small amounts of nitrogen oxides. Two methods were used to produce ozone: the first method consisted of dry pressurized air fed to an electric discharge generator generating the byproducts, N2O5 and N2O, the second method consisted of ambient air fed to UV-lamps. Two spring wheat cultivars (Triticum aestivum L. cvs Minaret and Eridano) were exposed in small open-top chambers to charcoal-filtered air, non-filtered ambient air, and non-filtered ambient air with the addition of ozone for 8 h (0900 to 1700 h) daily, for five weeks. Plants were harvested every week. The growth of Minaret was shown to be more sensitive to O3 than that of Eridano. Leaf senescence increased with increasing ozone level in both cultivars. The total above-ground biomass dry weight decreased with increasing ozone concentration in Minaret, but not in Eridano. The Minaret plants reacted with more damaged leaf dry weight and inhibition of growth when O3 was produced by UV-lamps than when O3 was produced by air fed to an electric discharge generator. This could be explained by more nitrogen content per plant but not by increased nitrogen concentration in plant tissue in plants exposed to increased O3 and small amounts of incidental nitrogen oxides.     

Ambient Air Measurements of Petroleum Refinery Emissions

An ambient air monitoring program to characterize airborne emissions from the Exxon petroleum refinery at Benicia, California was conducted during September 8–22, 1975. Ground level sampling facilities and an instrumented aircraft provided an integrated, three-dimensional monitoring network. Measurements made during the study included ozone, oxides of nitrogen, methane, carbon monoxide, individual C₂-C₆ hydrocarbons, halocarbons, condensation nuclei, visual distance and various meteorological parameters. The study focused on three major areas: (1) the characterization of gaseous components within the refinery effluent, especially non-methane hydrocarbons and ozone, (2) natural sunlight bag irradiation experiments to determine the ozone forming potential of refinery emissions, and (3) an investigation of changes in plume chemistry as refinery emissions were transported downwind.     

Temporal and Spatial Distributions of Ozone in Atlanta: Regulatory and Epidemiologic Implications

ABSTRACT

Relationships between ambient levels of selected air pollutants and pediatric asthma exacerbation in Atlanta were studied retrospectively. As a part of this study, temporal and spatial distributions of ambient ozone concentrations in the 20-county Atlanta metropolitan area during the summers of 1993, 1994, and 1995 were assessed. A universal kriging procedure was used for spatial interpolation of aerometric monitoring station data. In this paper, the temporal and spatial distributions of ozone are described, and regulatory and epidemiologic implications are discussed. For the study period, the Atlanta ozone nonattainment area based on the 1-h, exceedance-based standard of 0.12 ppm is estimated to expand—from 56% of the Atlanta MSA by area and 71% by population to 88% by area and 96% by population—under the new 8-h, concentration-based standard of 0.08 ppm. Regarding asthma exacerbation, a 4% increase in pediatric asthma rate per 20-ppb increase in ambient ozone concentration was observed (p-value = 0.001), with ambient ozone level representing a general indicator of air quality due to its correlations with other pollutants. The use of spatial ozone estimates in the epidemiologic analysis demonstrates the need for control of demographic covariates in spatiotem poral assessments of associations of ambient air pollutant concentrations with health outcome.     

Systematic Development of an Artificial Neural Network Model for Real-Time Prediction of Ground-Level Ozone in Edmonton,Alberta, Canada

Abstract

Ground-level ozone is a secondary pollutant that has recently gained notoriety for its detrimental effects on human and vegetation health. In this paper, a systematic approach is applied to develop artificial neural network (ANN) models for ground-level ozone (O₃) prediction in Edmonton, Alberta, Canada, using ambient monitoring data for input. The intent of these models is to provide regulatory agencies with a tool for addressing data gaps in ambient monitoring information and predicting O₃ events. The models are used to determine the meteorological conditions and precursors that most affect O₃ concentrations. O₃ time-series effects and the efficacy of the systematic approach are also assessed. The developed models showed good predictive success, with coefficient of multiple determination values ranging from 0.75 to 0.94 for forecasts up to 2 hr in advance. The inputs most important for O₃ prediction were temperature and concentrations of nitric oxide, total hydrocarbons, sulfur dioxide, and nitrogen dioxide.     

The potential near-source ozone impacts of upstream oil and gas industry emissions

Increased drilling in urban areas overlying shale formations and its potential impact on human health through decreased air quality make it important to estimate the contribution of oil and gas activities to photochemical smog. Flares and compressor engines used in natural gas operations, for example, are large sources not only of NOx but also offormaldehyde, a hazardous air pollutant and powerful ozone precursor We used a neighborhood scale (200 m horizontal resolution) three-dimensional (3D) air dispersion model with an appropriate chemical mechanism to simulate ozone formation in the vicinity ofa hypothetical natural gas processing facility, based on accepted estimates of both regular and nonroutine emissions. The model predicts that, under average midday conditions in June, regular emissions mostly associated with compressor engines may increase ambient ozone in the Barnett Shale by more than 3 ppb beginning at about 2 km downwind of the facility, assuming there are no other major sources of ozone precursors. Flare volumes of 100,000 cubic meters per hour ofnatural gas over a period of 2 hr can also add over 3 ppb to peak 1-hr ozone somewhatfurther (>8 km) downwind, once dilution overcomes ozone titration and inhibition by large flare emissions of NOx. The additional peak ozone from the hypothetical flare can briefly exceed 10 ppb about 16 km downwind. The enhancements of ambient ozone predicted by the model are significant, given that ozone control strategy widths are of the order of a few parts per billion. Degrading the horizontal resolution of the model to 1 km spuriously enhances the simulated ozone increases by reducing the effectiveness of ozone inhibition and titration due to artificial plume dilution.     

Characterization of hydrocarbons, halocarbons and carbonyls in the atmosphere of Hong Kong

Ambient air quality measurements of 156 species including 39 alkanes, 32 alkenes, 2 alkynes, 24 aromatic hydrocarbons, 43 halocarbons and 16 carbonyls, were carried out for 120 air samples collected at two sampling stations (CW and TW) in 2001 throughout Hong Kong. Spatial variations of volatile organic compounds (VOCs) in the atmosphere were investigated. Levels of most alkanes and alkenes at TW site were higher than that at the CW site, while the BTEX concentrations at the two sites were close. The BTEX ratios at CW and TW were 1.6:10.1:1.0:1.6 and 2.1:10.8:1.0:2.0, respectively. For major halogenated hydrocarbons, the mean concentrations of chloromethane, CFCs 12 and 22 did not show spatial variations at the two sites. However, site-specific differences were observed for trichloroethene and tetrachloroethene. Furthermore, there were no significant differences for carbonyls such as formaldehyde, acetaldehyde and acetone between the two sites. The levels of selected hydrocarbons in winter were 1-5 times that in summer. There were no common seasonal trends for carbonyls in Hong Kong. The ambient level of formaldehyde, the most abundant carbonyl, was higher in summer. However, levels of acetaldehyde, acetone and benzaldehyde in winter were 1.6-3.8 times that in summer. The levels of CFCs 11 and 12, and chloromethane in summer were higher than that in winter. Strong correlation of most hydrocarbons with propene and n-butane suggested that the primary contributors of hydrocarbons were vehicular emissions in Hong Kong. In addition, gasoline evaporation, use of solvents, leakage of liquefied petroleum gas (LPG), natural gas leakage and other industrial emissions, and even biogenic emissions affected the ambient levels of hydrocarbons. The sources of halocarbons were mainly materials used in industrial processes and as solvents. Correlation analysis suggested that photochemical reactions made significant contributions to the ambient levels of carbonyls in summer whereas in winter motor vehicle emissions would be the major sources of the carbonyls. The photochemical reactivity of selected VOCs was estimated in this study. The largest contributors to ozone formation were formaldehyde, toluene, propene, m,p-xylene, acetaldehyde, 1-butene/i-butene, isoprene and n-butane, suggesting that motor vehicles, gasoline evaporation, use of solvents, leakage of LPG, photochemical processes and biogenic emission are sources in the production of ozone. On the other hand, VOCs from vehicles and gasoline evaporation were predominant with respect to reactions with OH radical.     

The relation between ozone,NOx and hydrocarbons in urban and polluted rural environments

Research over the past ten years has created a more detailed and coherent view of the relation between O₃ and its major anthropogenic precursors, volatile organic compounds (VOC) and oxides of nitrogen (NO_x). This article presents a review of insights derived from photochemical models and field measurements. The ozone–precursor relationship can be understood in terms of a fundamental split into a NO_x-senstive and VOC-sensitive (or NO_x-saturated) chemical regimes. These regimes are associated with the chemistry of odd hydrogen radicals and appear in different forms in studies of urbanized regions, power plant plumes and the remote troposphere. Factors that affect the split into NO_x-sensitive and VOC-sensitive chemistry include: VOC/NO_x ratios, VOC reactivity, biogenic hydrocarbons, photochemical aging, and rates of meteorological dispersion. Analyses of ozone–NO_x–VOC sensitivity from 3D photochemical models show a consistent pattern, but predictions for the impact of reduced NO_x and VOC in indivdual locations are often very uncertain. This uncertainty can be identified by comparing predictions from different model scenarios that reflect uncertainties in meteorology, anthropogenic and biogenic emissions. Several observation-based approaches have been proposed that seek to evaluate ozone–NO_x–VOC sensitivity directly from ambient measurements (including ambient VOC, reactive nitrogen, and peroxides). Observation-based approaches have also been used to evaluate emission rates, ozone production efficiency, and removal rates of chemically active species. Use of these methods in combination with models can significantly reduce the uncertainty associated with model predictions.     

Validation of in-situ measurements of volatile organic compounds through flask sampling and gas chromatography/mass spectrometry analysis

Continuous monitoring of ambient non-methane hydrocarbons (NMHCs) by automated gas chromatographs equipped with flame ionization detection (termed in-situ GC/FID) with hourly data resolution was instated in ozone non-attainment areas throughout Taiwan. Performance of these on-site in-situ GCs was validated by manual flask sampling, as well as by in-lab gas chromatography/mass spectrometry (GC/MS) analysis. More than 50 VOCs from C₂ to C₁₁ were analyzed by both methods. Ninety flask samples were collected in series near an in-situ GC monitoring station in order to closely compare with the in-situ measurements. Both time-series and scatter plots from the two methods are displayed and discussed. It was found that over-simplified, un-humidified single-point calibration leading to surface loss was responsible for the bias in the in-situ method, resulting in greater error in accuracy as VOC volatility decreased. Although this over-estimate of the concentrations was found across all target VOCs, both methods were able to consistently capture the variability of ambient VOCs, with R² values greater than 0.9 for most of the major VOCs.     

Ozone measurements in South Carolina using passive samplers

Passive samplers with two different collection substrates were used to obtain an average ozone concentration for 1 month during the summer of 2002 for each South Carolina county. One sampler contained a filter coated with indigo carmine, whose color fades when exposed to ozone. The fading was measured by reflectance spectroscopy. The other sampler contained filters that were coated with nitrite, which is oxidized to nitrate when exposed to ozone. The nitrate was measured by ion chromatography. Calibration curves were developed for the two methods by comparing color fading from indigo carmine and nitrate ion concentration from the nitrite filter with ambient ozone concentration measured by a co-located reference continuous UV ozone analyzer. These curves were used to calculate integrated ozone concentrations for samplers distributed across South Carolina. Using the indigo carmine method, the average ozone concentrations ranged from 21 to 64 ppb (average = 46 +/- 7.9 ppb, n = 58) across the 46 counties in the state during one summer month of 2002. Concentrations for the same time period from the nitrite-coated filters ranged from 23 to 62 ppb (average = 41 +/- 8.1 ppb, n = 58). Also for the same time period, the 23 continuous UV photometric ozone monitors operated by the South Carolina Department of Health and Environmental Control at sites within 10 miles of some of the passive monitors showed ozone concentrations ranging from 28 to 50 ppb (average = 39 +/- 6.3 ppb, n = 22).     

Source characterization of ozone precursors by complementary approaches of vehicular indicator and principal component analysis

Measurements of speciated non-methane hydrocarbons (NMHCs) were conducted in an ozone non-attainment metropolis with pronounced industrial emissions in addition to traffic ones. Highly variable and complex natures of industrial sources make their composition profiles difficult to determine. In the circumstances of no reliable source profiles, two simple complementary approaches were attempted to characterize sources of NMHCs. First, a robust vehicular indicator, 3-methylpentane (3MC5A), which is an intrinsic component of gasoline, was used to estimate contributions of traffic versus non-traffic sources for major NMHCs with high ozone-forming potentials (OFPs), such as ethene, toluene, xylene, isoprene, etc. Second, the method of principal component analysis (PCA) was employed to further discern non-traffic emissions into various source groups. A total of 454 ambient samples were sampled in the urban-industrial complex metropolis (Kaohsiung, Taiwan) to build up a large dataset to be tested by the two complementary approaches. It was found that four types of emissions, i.e., traffic, household fuel leakage, industrial, and biogenic, were responsible for the observed ambient NMHCs. The industrial contribution was significant for ethene and toluene (with 48–67% and 33–62%, respectively), whereas xylene was found to be mainly vehicular. In addition, isoprene revealed its biogenic nature. OFPs arising from vehicular, industrial and biogenic contributions could be further assessed for the purpose of emission control of NMHCs in the ozone non-attainment area.     

Meta-analysis of the Chinese studies of the association between ambient ozone and mortality

To investigate short-term effects of ambient ozone exposure on mortality in Chinese cities, we conducted a meta-analysis of 10 effect estimates of 5 short-term studies, which reported associations between ambient ozone and mortality in Chinese mainland cities. And we estimated pooled effects by non-accidental mortality, cardiovascular mortality, and respiratory mortality. Combined estimates and their 95%CI were tested by RevMan 5, and Funnel plots were used for the bias analysis. For a 10 μg m⁻³ increase of maximum 8-h average concentration of ozone, the percent change for non-accidental mortality, cardiovascular mortality, and respiratory mortality were 0.42 (95%CI, 0.32–0.52%), 0.44% (95%CI, 0.17–0.70%) and 0.50% (95%CI, 0.22–0.77%), respectively. Compared with pooled estimates from other meta-analyses on ambient ozone-associated mortality, our pooled estimate for non-accidental mortality was slightly higher than previous ones and pooled estimate for cardiovascular mortality was consistent with others. However, we observed significantly positive association between ambient ozone and respiratory mortality, which were generally nonsignificant in earlier studies. By combining estimates from published evidence, a small but substantial association between ambient ozone level and mortality was observed in Mainland China.     

Differential response of buddleia (Buddleia davidii Franch.) to ozone

Five cultivars of buddleia, Buddleia davidii Franch., were exposed to sub-ambient, ambient, and twice-ambient levels of ozone in open-top chambers for 8 weeks (June-August) during 1995: Plants were evaluated for foliar injury, growth index, and inflorescence characteristics during and following exposure. Destructive harvests were conducted at the end of the exposure period to determine dry weights of both above- and below-ground plant components. All cultivars had symptoms of visible injury in the twice-ambient treatment at both three and eight weeks after exposures began. No visible symptoms were observed at ambient ozone concentrations. At three weeks of exposure, 'Pink Delight' had the highest percentage of the leaves injured (PLI), 46.2%, followed by 'Opera' with a PLI of 23.3%. The other three cultivars had similar PLIs of less than 15%. After eight weeks of exposure, visible injury was equally severe on all cultivars with a mean PLI of 50.2% and mean Horsfall-Barratt rating of 5.4, indicating 12 to 25% of the leaf area was injured. No ozone x cultivar interaction was found for any growth variable measured. Across cultivars, growth index was reduced by 6%, total dry weight by 35%, and the number of developing floral buds and inflorescences by 29% for plants in twice-ambient ozone concentrations compared to ambient ozone concentrations. Percent biomass allocated to inflorescences was significantly greater for plants exposed to sub-ambient levels compared to those exposed to ozone at either ambient or twice-ambient concentrations. Results indicate that ozone levels similar to those in large urban areas in the southeastern United States have the potential to reduce growth and flowering of this important landscape plant.     

Oxidant denuder sampling for analysis of polycyclic aromatic hydrocarbons and their oxygenated derivates in ambient aerosol: evaluation of sampling artefact

The concentrations of some polycyclic aromatic hydrocarbons (PAH) and oxygenated PAH (O-PAH) can be changed by oxidation reactions during sampling. This can lead to an over- or underestimation of the corresponding adverse health effects. The aim of this study was the evaluation of these sampling artefacts. The potential of using an oxidant denuder was shown by parallel low-volume sampling with and without MnO₂ ozone denuder. Twenty-three PAH and 11 O-PAH in ambient air were analysed, both in the vapour and particulate phase. The denuder was proven to be highly efficient for stripping ozone from air while causing no significant particle losses. In general, the concentrations of 5- to 7-ring PAH, which are predominantly associated with particles, were underestimated in non-denuded samples. The highest losses due to reaction with ozone and other atmospheric oxidants were observed for benzo[a]pyrene and perylene. Concurrently, the concentrations of most of the mainly particle-associated 4- to 5-ring O-PAH were higher in the non-denuded samples. The denuder did not only remove ozone, moreover other gaseous species such as more volatile PAH and O-PAH were partially oxidized on the catalytic surface, too. Degradation of PAH and concurrent degradation/formation reactions of O-PAH occurred. The corresponding reactivities of selected PAH and O-PAH are discussed.     

Growth and nutrition of Quercus rubra L. seedlings and mature trees after three seasons of ozone exposure

Seedling growth and nutritional status have been shown to be sensitive to ozone, but the influence of multi-season ozone exposure on mature tree growth and nutrition has not been examined. To determine if seedlings and mature trees were similarly affected by ozone exposure, growth and nutrient concentrations in northern red oak (Quercus rubra L.) 4-year-old seedlings and 32-year-old mature trees were examined after treatment with subambient, ambient and twice ambient concentrations of ozone for three growing seasons. SUM00 values summed over the three growing seasons were 147, 255 and 507 ppm-h, respectively, for the subambient, ambient and twice ambient exposures. For mature trees, no influence of ozone treatment on lower stem diameter growth, stem growth within the mid-canopy and foliar biomass was observed. Seedling height was increased by ozone, but biomass and diameter were unaffected. A reduction in the specific leaf weight of leaves in response to ozone coincident with the loss of recurrent flushing was observed in seedlings. Ozone exposure reduced foliar nitrogen concentrations and increased woody tissue nutrient concentrations in seedlings and mature trees at the end of the third growing season. These results suggest an influence of ozone on retranslocation processes in seedlings and mature trees.