The development and application of a simplified ozone modeling system (SOMS)

This paper describes the development and evaluation of a computationally efficient semi-empirical photochemical model that can be used as a screening tool to obtain quick estimates of the effect of a large number of VOC and NO_x emission control strategies on ozone concentrations. Selected control strategies can subsequently be examined with a more complex model. The model is one component of an ozone management system, the regional ozone decision model (RODM), designed to examine the costs and environmental consequences of alternate ozone abatement strategies.The model was developed by systematic simplification of a detailed photochemical model. At each step of the simplification, the simplified model was tested against observations and against results from the detailed model. The first major simplification was the introduction of a highly parameterized chemistry mechanism, originally developed by Azzi et al. (1992 Proc. 11th Int. Clean Air Conf., 4th Regional IUAPPA Conf.). This modification resulted in a factor of 5 improvement in the computational efficiency of the model. The model with the simplified chemistry was then tested by applying it to a photochemical oxidant episode in the San Joaquin Valley of California. Further improvements in computational speed and efficiency were obtained by uncoupling the chemistry from the transport of VOC and NO_x.     

Rapid measurement of indoor mass-transfer coefficients

Indoor air pollutant concentrations can be influenced by how rapidly species are transported to and from surfaces. Consequently, a greater understanding of indoor transport phenomena to surfaces improves estimates of human exposure to indoor air pollutants. Here, we introduce two methods of rapidly and directly measuring species fluxes at indoor surfaces, allowing us to evaluate the transport-limited deposition velocity, v_t (a mass-transfer coefficient). The deposition velocity sensor (DeVS) method employs a small microbalance coated with a pure hydrocarbon, preferably octadecane. We quantify flux (or evaporation rate) of the hydrocarbon into a room by observing the rate of mass loss on the microbalance. The transport-limited deposition velocity, v_t,octadecane, is then obtained by combining the flux with the vapor pressure of the hydrocarbon. Simultaneously, v_t,ozone is quantified using the deposition velocity of ozone (DeVO) method, which acts as a standard to calibrate and evaluate DeVS. Specifically, DeVO evaluates ozone transport to surfaces by quantifying the conversion by ozone of nitrite to nitrate on a glass fiber filter. Simultaneous laboratory chamber experiments demonstrates that v_t for octadecane and ozone are strongly correlated, with the values for ozone 1.5 times greater than that for octadecane. In an office experiments, the DeVS method responds within minutes to step changes in conditions such as occupancy, activities and ventilation. At present, the results are in order-of-magnitude agreement with predicted indoor mass-transfer coefficients.     

High ozone levels in the northeast of Portugal: Analysis and characterization

Each summer period extremely high ozone levels are registered at the rural background station of Lamas d'Olo, located in the Northeast of Portugal. In average, 30% of the total alert threshold registered in Portugal is detected at this site. The main purpose of this study is to characterize the atmospheric conditions that lead to the ozone-rich episodes at this site. Synoptic patterns anomalies and back trajectories cluster analysis were performed, for the period between 2004 and 2007, considering 76 days when ozone maximum hourly concentrations were above 200 μg m^?3. The obtained atmospheric anomaly fields suggested that a positive temperature anomaly is visible above the Iberian Peninsula. A strong wind flow pattern from NE is observable in the North of Portugal and Galicia, in Spain. These two features may lead to an enhancement of the photochemical production and to the transport of pollutants from Spain to Portugal. In addition, the 3D mean back trajectories associated to the ozone episode days were analysed. A clustering method has been applied to the obtained back trajectories. Four main clusters of ozone-rich episodes were identified, with different frequencies of occurrence: north-westerly flows (11%); north-easterly flows (45%), southern flow (4%) and westerly flows (40%). Both analyses highlight the NE flow as a dominant pattern over the North of Portugal during summer. The analysis of the ozone concentrations for each selected cluster indicates that this northeast circulation pattern, together with the southern flow, are responsible for the highest ozone peak episodes. This also suggests that long-range transport of atmospheric pollutants is the main contributor to the ozone levels registered at Lamas d'Olo. This is also highlighted by the correlation of the ozone time-series with the meteorological parameters analysed in the frequency domain.     

Estimating long-term population exposure to ozone in urban areas of Europe

Tropospheric ozone concentrations regarded as harmful for human health are frequently encountered in Central Europe in summertime. Although ozone formation generally results from precursors transported over long distances, in urban areas local effects, such as reactions due to nearby emission sources, play a major role in determining ozone concentrations. Europe-wide mapping and modeling of population exposure to high ozone concentrations is subject to many uncertainties, because small-scale phenomena in urban areas can significantly change ozone levels from those of the surroundings. Currently the integrated assessment modeling of European ozone control strategies is done utilizing the results of large-scale models intended for estimating the rural background ozone levels. This paper presents an initial study on how much local nitrogen oxide (NOx) concentrations can explain variations between large-scale ozone model results and urban ozone measurements, on one hand, and between urban and nearby rural measurements, on the other. The impact of urban NOx concentrations on ozone levels was derived from chemical equations describing the ozone balance. The study investigated the applicability of the method for improving the accuracy of modeled population exposure, which is needed for efficient control strategy development. The method was tested with NOx and ozone measurements from both urban and rural areas in Switzerland and with the ozone predictions of the large-scale photochemical model currently used in designing Europe-wide control strategies for ground-level ozone. The results suggest that urban NOx levels are a significant explanatory factor in differences between urban and nearby rural ozone concentrations and that the phenomenon could be satisfactorily represented with this kind of method. Further research efforts should comprise testing of the method in more locations and analyzing the performance of more widely applicable ways of deriving the initial parameters.     

Ozone Measurements in South Carolina Using Passive Samplers

Abstract

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).     

On ground truth in cross-border ozone transport

Cross-border transport of ozone is one of the most contentious issues of air pollution management in the U.S. Yet, both the modeling and observational studies are lacking. Models are normally validated by comparing predicted and observed ozone concentrations. However, proper validation of cross-border transport model requires a comparison of predictions against observation-based benchmarks of cross-border ozone transport. Such benchmarks are unavailable, as published observation-based studies always deal only with a combination of local production and cross-border transport, not a cross-border transport itself. We show how to extract necessary benchmarks from observations of rural monitoring sites near state borders. On example of the western border of New York, we find that in about two-thirds of the most polluted days all the ozone came in a steady cross-border inflow after previously passing over one or more large urban areas to the west. In all the enumerated days with direct cross-border inflow, daily maximum 8-hr concentrations of ozone just upwind of the border were over 60 ppb, with an average value of 68 ppb, just short of the 70 ppb ozone regulatory threshold, information also useful to state air pollution authorities.

Implications: The purpose of the cross-border ozone pollution models is to predict cross-border transport of ozone, so the ability of the model to accurately represent observed ozone concentrations is necessary but not sufficient for model validation. The accuracy of predicted ozone concentrations is not necessarily the same as the accuracy of the predictions of ozone transport. Proper model validation requires comparisons against observation-based benchmarks of cross-border transport. Such observations, so far absent, can be obtained from rural monitoring sites near state borders, as illustrated by the example of western New York.     

Future-year ozone prediction for the United States using updated models and inputs

The relationship between emission reductions and changes in ozone can be studied using photochemical grid models. These models are updated with new information as it becomes available. The primary objective of this study was to update the previous Collet et al. studies by using the most up-to-date (at the time the study was done) modeling emission tools, inventories, and meteorology available to conduct ozone source attribution and sensitivity studies. Results show future-year, 2030, design values for 8-hr ozone concentrations were lower than base-year values, 2011. The ozone source attribution results for selected cities showed that boundary conditions were the dominant contributors to ozone concentrations at the western U.S. locations, and were important for many of the eastern U.S. locations. Point sources were generally more important in the eastern United States than in the western United States. The contributions of on-road mobile emissions were less than 5 ppb at a majority of the cities selected for analysis. The higher-order decoupled direct method (HDDM) results showed that in most of the locations selected for analysis, NOx emission reductions were more effective than VOC emission reductions in reducing ozone levels. The source attribution results from this study provide useful information on the important source categories and provide some initial guidance on future emission reduction strategies.

Implications: The relationship between emission reductions and changes in ozone can be studied using photochemical grid models, which are updated with new available information. This study was to update the previous Collet et al. studies by using the most current, at the time the study was done, models and inventory to conduct ozone source attribution and sensitivity studies. The source attribution results from this study provide useful information on the important source categories and provide some initial guidance on future emission reduction strategies.     

Ozone pollution and ozone biomonitoring in European cities. Part I: Ozone concentrations and cumulative exposure indices at urban and suburban sites

In the frame of a European research project on air quality in urban agglomerations, data on ozone concentrations from 23 automated urban and suburban monitoring stations in 11 cities from seven countries were analysed and evaluated. Daily and summer mean and maximum concentrations were computed based on hourly mean values, and cumulative ozone exposure indices (Accumulated exposure Over a Threshold of 40 ppb (AOT40), AOT20) were calculated. The diurnal profiles showed a characteristic pattern in most city centres, with minimum values in the early morning hours, a strong rise during the morning, peak concentrations in the afternoon, and a decline during the night. The widest amplitudes between minimum and maximum values were found in central and southern European cities such as Düsseldorf, Verona, Klagenfurt, Lyon or Barcelona. In the northern European cities of Edinburgh and Copenhagen, by contrast, maximum values were lower and diurnal variation was much smaller. Based on ozone concentrations as well as on cumulative exposure indices, a clear north–south gradient in ozone pollution, with increasing levels from northern and northwestern sites to central and southern European sites, was observed. Only the Spanish cities did not fit this pattern; there, ozone levels were again lower than in central European cities, probably due to the direct influence of strong car traffic emissions. In general, ozone concentrations and cumulative exposure were significantly higher at suburban sites than at urban and traffic-exposed sites. When applying the newly established European Union (EU) Directive on ozone pollution in ambient air, it was demonstrated that the target value for the protection of human health was regularly surpassed at urban as well as suburban sites, particularly in cities in Austria, France, northern Italy and southern Germany. European target values and long-term objectives for the protection of vegetation expressed as AOT40 were also exceeded at many monitoring sites.     

Detecting and Tracking Changes in Ozone Air Quality

This paper presents a statistical method for filtering out or moderating the influence of meteorological fluctuations on ozone concentrations. Use of this technique in examining trends in ambient ozone air quality is demonstrated with ozone data from a monitoring location in New Jersey. The results indicate that this method can detect changes in ozone air quality due to changes in emissions in the presence of meteorological fluctuations. This method can be useful in examining the effectiveness of regulatory initiatives in improving ozone air quality.     

Suitability of Nicotiana tabacum 'Bel W3' for biomonitoring ozone in São Paulo, Brazil

Nicotiana tabacum 'Bel W3' is a widely used sensitive bioindicator for ambient ozone, but it is rarely used in tropical countries. Our goal was to determine the suitability of this plant for biomonitoring ozone in the city of S?o Paulo by evaluating the relationships between leaf necroses and ozone under field conditions and measurements of chlorophyll a fluorescence and antioxidants in plants exposed to different concentrations of ozone in closed chambers. While a weak linear relationship between leaf injury and ozone concentrations (R(2)=0.10) was determined in the field, a strong linear relationship was observed in the chamber experiments. Maximum leaf injury was observed in plants submitted to 40 ppb, which coincided with a significant decrease in fluorescence and total ascorbic acid. The relationship between leaf damage observed in the field and ozone was improved when the concentrations were limited to 40 ppb (R(2)=0.28).     

A Regujatory Framework for Setting Air Emission Limits for Noncriteria Pollutants

The information presented in this paper is concerned with the effects of ambient ozone on crop yield reduction and the resultant economic losses. Yield data for nine crops within the South Coast Air Basin (SCAB) of California were obtained for the 12-year period, 1964 through 1975. Ozone concentrations, temperature, precipitation, and relative humidity data were related to the yields by using regression models. Estimated yield reductions due to ozone for 1975, varied from zero to 57% depending on crop and location. Economic welfare losses calculated from the yield reductions were $57.3 and $45.7 million for producer’s and consumer’s surplus, respectively. The total loss from ozone to agriculture related economic sectors determined by input-output analysis was $276 million in the SCAB and $36.6 million in the remainder of the state.     

Impact of downward-mixing ozone on surface ozone accumulation in southern Taiwan

The ozone that initially presents in the previous day's afternoon mixing layer can remain in the nighttime atmosphere and then be carried over to the next morning. Finally, this ozone can be brought to the ground by downward mixing as mixing depth increases during the daytime, thereby increasing surface ozone concentrations. Variation of ozone concentration during each of these periods is investigated in this work. First, ozone concentrations existing in the daily early morning atmosphere at the altitude range of the daily maximum mixing depth (residual ozone concentrations) were measured using tethered ozonesondes on 52 experimental days during 2004-2005 in southern Taiwan. Daily downward-mixing ozone concentrations were calculated by a box model coupling the measured daily residual ozone concentrations and daily mixing depth variations. The ozone concentrations upwind in the previous day's afternoon mixing layer were estimated by the combination of back air trajectory analysis and known previous day's surface ozone distributions. Additionally, the relationship between daily downward-mixing ozone concentration and daily photochemically produced ozone concentration was examined. The latter was calculated by removing the former from daily surface maximum ozone concentration. The measured daily residual ozone concentrations distributed at 12-74 parts per billion (ppb) with an average of 42 +/- 17 ppb are well correlated with the previous upwind ozone concentration (R2 = 0.54-0.65). Approximately 60% of the previous upwind ozone was estimated to be carried over to the next morning and became the observed residual ozone. The daily downward-mixing ozone contributes 48 +/- 18% of the daily surface maximum ozone concentration, indicating that the downward-mixing ozone is as important as daily photochemically produced ozone to daily surface maximum ozone accumulation. The daily downward-mixing ozone is poorly correlated with the daily photochemically produced ozone and contributes significantly to the daily variation of surface maximum ozone concentrations (R2 = 0.19). However, the contribution of downward-mixing ozone to daily ozone variation is not included in most existing statistical models developed for predicting daily ozone variation. Finally, daily surface maximum ozone concentration is positively correlated with daily afternoon mixing depth, attributable to the downward-mixing ozone.     

Meteorologically adjusted trends of daily maximum ozone concentrations in Taipei,Taiwan

The meteorological conditions exert large impacts on ozone concentrations, and may mask the long-term trends in ozone concentrations resulting from precursor emissions. Estimation of long-term trends of ozone concentrations due to the changes in precursor emissions is important for corresponding control strategy. Multiple linear regression (method I), multilayer perceptron (MLP) neural network (method II) and Komogorov-Zurbenko (KZ) filter method plus MLP methodology (method III), are used to estimate the meteorologically adjusted long-term trends of daily maximum ozone concentrations by removing the masking effects of meteorological conditions in this study. The daily maximum ozone concentrations and relative meteorological variables were extracted from six air-monitoring stations in Taipei area from 1994 to 2001. The data collected during 1994–2000 period were used as modeling set and utilized to estimate the meteorologically adjusted trends, and the data of 2001 were used as the validation data. The meteorologically adjusted trends of ozone for these three methods were calculated and compared. The results show that both MLP and KZ filter +MLP models are more suitable than multiple linear regression for estimating the long-term trends of ozone in Taipei, Taiwan. The long-term linear trends of meteorologically adjusted ozone concentrations due to the precursor emissions show an increase trend at all stations, and the percent changes per year range from 1.0% to 2.25% during the modeling period in Taipei area.     

Ozone Regimes in or near Forests of the Western United States: Part 2. Factors Influencing Regional Patterns

Abstract

Ozone levels in or near forests of the western United States resulted from transport of ozone from urban areas, photochemical formation of ozone in nonurban areas from either natural or manmade precursors, and downward mixing of ozone from the tropospheric reservoir. Similarities in ozone exposure regimes were clearly associated with ozone characteristics, such as the shape of the diurnal curve in hourly ozone concentrations and the magnitudes of ozone levels. No single site characteristic dominated across the region. Eight classes of ozone regimes were identified: largeurban, medium-urban, small-urban, urban downwind-urban, urban-transport, rural, rural-remote, and remote. Sites in the western United States can be classified according to these classes. Of the sites included in the analysis, Olympic National Park, Colorado National Monument, Redwood National Park, Grand Canyon, and Crook County in Oregon showed the lowest impact from urban-generated ozone. The greatest impact of manmade ozone was found in forests of southern and central California, and to some extent in Rocky Mountain National Park and along the western slopes of the Cascades in Washington.

The eight groups of sites showing similar ozone exposure regimes as identified by Böhm et al.¹ corresponded closely with the eight classes of ozone regimes, indicating that regional similarities in ozone exposure regimes can be linked to ozone formation and transport processes despite a lack of geographic cohesion. Sixty-four percent of variance in ozone exposure regimes can be expressed in a twodimensional space called diurnal-curve space. Group membership is more cohesive in diurnal-curve than geographic space. Applications of diurnal-curve space include (1) a sensitive regional analysis of the nature and magnitudes of ozone exposure regimes in or near western forests; (2) a pro-active means for identifying sites with changing ozone exposure regimes; and (3) guidelines from which biologists can develop realistic experimental fumigation protocols. It is suggested that univariate statistics, such as 7-hour mean, 24-hour mean, SUM06, and SUM08, cannot identify up to 39% of the variance in ozone exposure regimes among sites in or near forests of the western United States.     

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.     

Ozone Levels in the Vicinity of 33 Cities

Hourly concentrations of ozone were measured by the chemiluminescence method during the summer of 1971 in the vicinity of 33 cities. A listing was made of the percent of time the National Air Quality Standard for photochemical oxidants was violated. At 4 selected cities the daytime and nighttime average concentrations were related to wind directions showing the direction to source areas. Another set of tables and graphs was used to show the source directions for high concentrations (equal to or above 120 µg/m³) and disregarding the times of more usual or background concentrations. Numerous occasions of high ozone concentrations occurred when wind directions were apparently from areas with low concentrations of the known precursors. Because of this, other sources of ozone were considered such as thunderstorms and the transport of ozone for long distances. Examples of ozone concentrations during thunderstorms or related to long distance transport are cited.     

Synoptic-scale transport of ozone into Southern Ontario

This study focuses on synoptic-scale transport of ozone as it affects Southern Ontario. This process has been analyzed for the summer in 2001, as an example period of a frequent event that usually occurs during summer in this region. The work was carried out using the mesoscale modeling system generation 5 (MM5)/sparse matrix operator kernel emission modeling system (SMOKE)/community multiscale air quality (CMAQ) regional air quality modeling system, together with observational data from monitoring stations located throughout the modeling domain. Other different analyses have been carried out to supply more information apart from that obtained by the modeling system. A back-trajectory cluster methodology was used to evaluate the magnitude of the effects studied and an analysis of wind direction and cloud cover revealed a significant correlation with ozone concentration (R²=0.5–0.6). Synoptic sea-surface level pressure (SLP) patterns were also analyzed to examine other meteorological aspects. The contribution of natural background ozone to the total amount within the region was compared with that from synoptic-scale transport. The influence of emission of pollutants from selected areas on ozone concentrations in Southern Ontario was also analyzed. As relevant results of these analyses, the model predicts that background ozone is the largest contribution to the ground-level ozone concentration during days in which low values were recorded. However, when smog episodes occurred, the model predicts that around 60% of the ozone formed by anthropogenic emissions of pollutants is due to releases from nearby US states.     

The effect of variability in industrial emissions on ozone formation in Houston, Texas

Ambient observations have indicated that high concentrations of ozone observed in the Houston/Galveston area are associated with plumes of highly reactive hydrocarbons, mixed with NO_x, from industrial facilities. Ambient observations and industrial process data, such as mass flow rates for industrial flares, indicate that the VOCs associated with these industrial emissions can have significant temporal variability. To characterize the effect of this variability in emissions on ozone formation in Houston, data were collected on the temporal variability of industrial emissions or emission surrogates (e.g., mass flow rates to flares). The observed emissions variability was then used to construct regionwide emission inventories with variable industrial emissions, and the impacts of the variability on ozone formation were examined for two types of meteorological conditions, both of which lead to high ozone concentrations in Houston. The air quality simulations indicate that variability in industrial emissions has the potential to cause increases and decreases of 10–52 ppb (13–316%), or more, in ozone concentration. The largest of these differences are restricted to regions of 10–20 km², but the variability also has the potential to increase regionwide maxima in ozone concentrations by up to 12 ppb.     

Estimated tropospheric ozone levels on the southeast Spanish Mediterranean coast

The objective of this study is to estimate the spatial variability of tropospheric ozone in an area using a simple model. The area in this case was applied in the western Mediterranean basin. The study period was from May to September in 2003 and 2004.A multiple linear regression between ozone concentrations, altitude and distance to the precursor sources in a fluvial basin can be used to estimate ozone values at other sites during the warmer seasons. The correlation coefficients obtained with 2-week ozone values measured at five points with a passive sampling technique were high enough to apply the model (0.77<r<0.99).To verify the model, ozone concentrations were measured with passive samplers and continuous analyzers at some selected sites, and the values were compared with the estimated concentration. The results of the validations were satisfactory, in 80% of the measurements the estimated levels differ from measured less than 20%, which is included in the bound error for the type of sampler used in this study.     

The Chemical and Meteorological Conditions Associated with High and Low Ozone Concentrations in Southeastern Michigan and Nearby Areas of Ontario

This analysis represents the first characterization of the photochemistry and transport of ozone in the Detroit metropolitan area and provides a basis for comparing data for Detroit to that for other cities. The characterization is based on a comprehensive set of meteorological and chemical measurements obtained at a site in the urban core of Detroit during the summer of 1981, together with measurements of O₃, nitrogen oxides (NO _X ), and nonmethane organic compounds (NMOC) from rural, suburban, and urban areas in southeastern Michigan and adjacent areas of Ontario.

For the quartile (23 days) with highest ozone maxima (97-180 ppb), the maxima occurred 10-70 km north-northeast of the city on days that were warm and hazy with light southsouthwest winds. On such days there was a marked accumulation of ozone precursors (NMOC and NO_X) in the early morning, as well as a rapid chemical removal of NO _X (NO _X half-life of ～5 h) from morning to midday. The timing of the daily ozone increase across the study region suggests that local photochemical generation in a moving plume was responsible for more than half of the ozone measured downwind. However, there was also evidence that ozone transported into Detroit as part of the regional background was a significant part of the O₃ maxima on high ozone days. The average contributions of photochemistry and transport for the 23 days with the highest ozone maxima were estimated to be 57 ppb and 47 ppb, respectively.