The use of ambient data to corroborate analyses of ozone control strategies

Data from environmental-chamber studies and photochemical box-model simulations were used to evaluate and revise a method for developing a qualitative understanding of the sensitivity of ozone formation at a particular time and place to changes in concentrations of volatile organic compounds (VOC) and oxides of nitrogen (NO_x). The revised method requires measurements of ozone, NO, and either NO_x or NO_y. The sensitivities of the method to biases in measurements were evaluated. The method potentially can be used for qualitative assessment of VOC versus NO_x limitation, comparison with the predictions of grid-based photochemical air-quality models, and evaluation of trends over time in the relative effectiveness of VOC versus NO_x controls.     

Photochemical Smog Modeling for Assessment of Potential Impacts of Different Management Strategies on Air Quality of the Bangkok Metropolitan Region,Thailand

Abstract

A photochemical smog model system, the Variable-Grid Urban Airshed Model/Systems Applications International Mesoscale Model (UAM-V/SAIMM), was used to investigate photochemical pollution in the Bangkok Metropolitan Region (BMR). The model system was first applied to simulate a historical photochemical smog episode of two days (January 13-14, 1997) using the 1997 anthropogenic emission database available at the Pollution Control Department and an estimated biogenic emission. The output 1-hr ozone (O₃) for BMR, however, did not meet the U.S. Environmental Protection Agency suggested performance criteria. The simulated minimum and maximum O₃ values in the domain were much higher than the observations. Multiple model runs with different precursor emission reduction scenarios showed that the best model performance with the simulated 1-hr O₃ meeting all the criteria was obtained when the volatile organic compound (VOC) and oxides of nitrogen (NO_x) emission from mobile source reduced by 50% and carbon monoxide by 20% from the original database. Various combinations of anthropogenic and biogenic emissions in Bangkok and surrounding provinces were simulated to assess the contribution of different sources to O₃ pollution in the city. O₃ formation in Bangkok was found to be more VOC-sensitive than NO_x-sensitive. To attain the Thailand ambient air quality standard for 1-hr O₃ of 100 ppb, VOC emission in BMR should be reduced by 50-60%. Management strategies considered in the scenario study consist of Stage I, Stage II vapor control, replacement of two-stroke by four-stroke motorcycles, 100% compressed natural gas bus, 100% natural gas-fired power plants, and replacement of methyltertiarybutylether by ethanol as an additive for gasoline.     

Influence of nocturnal vertical stability on daytime chemistry: A one-dimensional model study

Nocturnal chemistry can play an important role in determining the initial morning conditions for daytime chemistry in urban areas. However, the impact on daytime O₃ levels is difficult to assess as the suppression of vertical trace gas transport leads to highly altitude dependent nocturnal chemistry, in particular with respect to the removal and conversion of nitrogen oxides (NO_x) and volatile organic compounds (VOC). One-dimensional (1-D) chemical transport model calculations for different nighttime vertical stabilities and different ozone formation regimes (i.e. NO_x- vs. VOC-sensitive) were performed assuming a 1000 m high daytime boundary layer and a growing nocturnal boundary layer reaching 200 m height at the end of the night. Exclusion of NO₃ chemistry from the model leads to daytime O₃ concentration changes from ?4% to +16% for different O₃ sensitivities. In all cases strong nocturnal vertical concentration profiles of NO_x, O₃, NO₃ and N₂O₅ and a dependence of these profiles on vertical stability were found at night. The nocturnal NO_x loss averaged over the lowest 1000 m changes by 9–24% for different vertical stabilities and ozone sensitivities. The impact of nocturnal vertical stability leads to 7–12% difference in O₃ concentration in the morning and ～0–2.5% in the afternoon.     

Summertime photochemical ozone formation in Santiago,Chile

The city of Santiago, Chile experiences frequent high pollution episodes and as a consequence very high ozone concentrations, which are associated with health problems including increasing daily mortality and hospital admissions for respiratory illnesses. The development of ozone abatement strategies requires the determination of the potential of each pollutant to produce ozone, taking into account known mechanisms and chemical kinetics in addition to ambient atmospheric conditions. In this study, the photochemical formation of ozone during a summer campaign carried out from March 8–20, 2005 has been investigated using an urban photochemical box model based on the Master Chemical Mechanism (MCMv3.1). The MCM box model has been constrained with 10 min averages of simultaneous measurements of HONO, HCHO, CO, NO, j(O¹D), j(NO₂), 31 volatile organic compounds (VOCs) and meteorological parameters. The O₃–NO_x–VOC sensitivities have been determined by simulating ozone formation at different VOC and NO_x concentrations. Ozone sensitivity analyses showed that photochemical ozone formation is VOC-limited under average summertime conditions in Santiago. The results of the model simulations have been compared with a set of potential empirical indicator relationships including H₂O₂/HNO₃, HCHO/NO_y and O₃/NO_z. The ozone forming potential of each measured VOC has been determined using the MCM box model. The impacts of the above study on possible summertime ozone control strategies in Santiago are discussed.     

Variability of indicator values for ozone production sensitivity: a model study in Switzerland and San Joaquin Valley (California)

The threshold values of indicator species and ratios delineating the transition between NO_x and VOC sensitivity of ozone formation are assumed to be universal by various investigators. However, our previous studies suggested that threshold values might vary according to the locations and conditions. In this study, threshold values derived from various model simulations at two different locations (the area of Switzerland by UAM Model and San Joaquin Valley of Central California by SAQM Model) are examined using a new approach for defining NO_x and VOC sensitive regimes. Possible definitions for the distinction of NO_x and VOC sensitive ozone production regimes are given. The dependence of the threshold values for indicators and indicator ratios such as NO_y, O₃/NO_z, HCHO/NO_y, and H₂O₂/HNO₃ on the definition of NO_x and VOC sensitivity is discussed. Then the variations of threshold values under low emission conditions and in two different days are examined in both areas to check whether the models respond consistently to changes in environmental conditions. In both cases, threshold values are shifted similarly when emissions are reduced. Changes in the wind fields and aging of the photochemical oxidants seem to cause the day-to-day variation of the threshold values. O₃/NO_z and HCHO/NO_y indicators are predicted to be unsatisfactory to separate the NO_x and VOC sensitive regimes. Although NO_y and H₂O₂/HNO₃ provide a good separation of the two regimes, threshold values are affected by changes in the environmental conditions studied in this work.     

Intercomparison of chemical mechanisms for air quality policy formulation and assessment under North American conditions

The intercomparison of seven chemical mechanisms for their suitability for air quality policy formulation and assessment is described. Box modeling techniques were employed using 44 sets of background environmental conditions covering North America to constrain the chemical development of the longer lived species. The selected mechanisms were modified to enable an unbiased assessment of the adequacy of the parameterizations of photochemical ozone production from volatile organic compound (VOC) oxidation in the presence of NO_x. Photochemical ozone production rates responded differently to 30% NO_x and VOC reductions with the different mechanisms, despite the striking similarities between the base-case ozone production rates. The 30% reductions in NO_x and VOCs also produced changes in OH. The responses in OH to 30% reductions in NO_x and VOCs appeared to be more sensitive to mechanism choice, compared with the responses in the photochemical ozone production rates. Although 30% NO_x reductions generally led to decreases in OH, 30% reductions in VOCs led to increases in OH, irrespective of mechanism choice and background environmental conditions. The different mechanisms therefore gave different OH responses to NO_x and VOC reductions and so would give different responses in terms of changes in the fate and behavior of air toxics, acidification and eutrophication, and fine particle formation compared with others, in response to ozone control strategies. Policymakers need to understand that there are likely to be inherent differences in the responses to ozone control strategies between different mechanisms, depending on background environmental conditions and the extents of NO_x and VOC reductions under consideration.

Implications: The purpose of this paper is to compare predicted ozone responses to NO_x and VOC reductions with seven chemical mechanisms under North American conditions. The good agreement found between the tested mechanisms should provide some support for their application in the air quality models used for policymaking.     

Photochemical reactivities of common solvents: comparison between urban and regional domains

Solvents are one of the most abundant sources of anthropogenic VOCs in the atmosphere, and can comprise a large number of organic compounds having different impacts on the rate and amount of ozone formation. A three-dimensional photochemical air quality model has been used to study the relative impacts of eight solvents, acetone, ethane, ethanol, isobutane, m-xylene, tertiary butyl acetate (TBA), para-chlorobenzotrifluoride (PCBTF) and benzotrifluoride (BTF) in three very different domains: Los Angeles, an urban area with high ozone and NO_x levels; the Swiss Plateau, a more regional domain with much lower ozone and NO_x levels: and Mexico City, a very high VOC urban area with high ozone levels. The results show that there can be a wide range of VOC reactivities under variable environmental conditions. Variability also exists between metrics, which are used to quantify reactivity. In most cases, halogenated aromatics were the least reactive and isobutane and m-xylene the most. The results here, finding that normalized reactivities are less variable than the absolute reactivity, support the applicability of relative VOC reactivity scales for use in air quality management.     

Spatial mapping of VOC and NOx-limitation of ozone formation in central California

Ambient aerometric data were used to predict whether ozone formation at specific times and locations in central California was limited by the availability of volatile organic compounds (VOC) or oxides of nitrogen (NO_x). The predictions were compared with differences between mean weekday and weekend peak ozone values. The comparison with weekend and weekday ozone levels provided a means for empirically investigating the effects of VOC and NO_x reductions on ozone formation, because the relative proportions and levels of ozone precursor species were significantly different on weekends than on weekdays. Weekend NO_x levels averaged 27 percent lower than weekday levels at the time of the peak ozone hour. Daytime weekend levels of VOC species were also consistently lower than weekday values throughout the region, though the differences between weekends and weekdays were not always statistically significant (p<0.05). Site-to-site differences between weekend and weekday mean peak hourly ozone were related to whether ozone formation was VOC- or NO_x-limited.     

The impacts of reactive terpene emissions from plants on air quality in Las Vegas,Nevada

A three-part study was conducted to quantify the impact of landscaped vegetation on air quality in a rapidly expanding urban area in the arid southeastern United States. The study combines in situ, plant-level measurements, a spatial emissions inventory, and a photochemical box model. Maximum plant-level basal emission rates were moderate: 18.1 μgC gdw^?1 h^?1 (Washingtonia spp., palms) for isoprene and 9.56 μgC gdw^?1 h^?1 (Fraxinus velutina, Arizona ash) for monoterpenes. Sesquiterpene emission rates were low for plant species selected in this study, with no measurement exceeding 0.1 μgC gdw^?1 h^?1. The high ambient temperatures combined with moderate plant-level emission factors resulted in landscape emission factors that were low (250–640 μgC m^?2 h^?1) compared to more mesic environments (e.g., the southeastern United States). The Regional Atmospheric Chemistry Mechanism (RACM) was modified to include a new reaction pathway for ocimene. Using measured concentrations of anthropogenic hydrocarbons and other reactive air pollutants (NO_x, ozone), the box model employing the RACM mechanism revealed that these modest emissions could have a significant impact on air quality. For a suburban location that was downwind of the urban core (high NO_x; low anthropogenic hydrocarbons), biogenic terpenes increased time-dependent ozone production rates by a factor of 50. Our study demonstrates that low-biomass density landscapes emit sufficient biogenic terpenes to have a significant impact on regional air quality.     

Uncertainties in predicted ozone concentrations due to input uncertainties for the UAM-V photochemical grid model applied to the July 1995 OTAG domain

The photochemical grid model, UAM-V, has been used by regulatory agencies to make decisions concerning emissions controls, based on studies of the July 1995 ozone episode in the eastern US. The current research concerns the effect of the uncertainties in UAM-V input variables (emissions, initial and boundary conditions, meteorological variables, and chemical reactions) on the uncertainties in UAM-V ozone predictions. Uncertainties of 128 input variables have been estimated and most range from about 20% to a factor of two. 100 Monte Carlo runs, each with new resampled values of each of the 128 input variables, have been made for given sets of median emissions assumptions. Emphasis is on the maximum hourly-averaged ozone concentration during the 12–14 July 1995 period. The distribution function of the 100 Monte Carlo predicted domain-wide maximum ozone concentrations is consistently close to log-normal with a 95% uncertainty range extending over plus and minus a factor of about 1.6 from the median. Uncertainties in ozone predictions are found to be most strongly correlated with uncertainties in the NO₂ photolysis rate. Also important are wind speed and direction, relative humidity, cloud cover, and biogenic VOC emissions. Differences in median predicted maximum ozone concentrations for three alternate emissions control assumptions were investigated, with the result that (1) the suggested year-2007 emissions changes would likely be effective in reducing concentrations from those for the year-1995 actual emissions, that (2) an additional 50% NO_x emissions reductions would likely be effective in further reducing concentrations, and that (3) an additional 50% VOC emission reductions may not be effective in further reducing concentrations.     

Precursor reductions and ground-level ozone in the Continental United States

Numerous papers analyze ground-level ozone (O₃) trends since the 1980s, but few have linked O₃ trends with observed changes in nitrogen oxide (NO_x) and volatile organic compound (VOC) emissions and ambient concentrations. This analysis of emissions and ambient measurements examines this linkage across the United States on multiple spatial scales from continental to urban. O₃ concentrations follow the general decreases in both NO_x and VOC emissions and ambient concentrations of precursors (nitrogen dioxide, NO₂; nonmethane organic compounds, NMOCs). Annual fourth-highest daily peak 8-hr average ozone and annual average or 98th percentile daily maximum hourly NO₂ concentrations show a statistically significant (p < 0.05) linear fit whose slope is less than 1:1 and intercept is in the 30 to >50 ppbv range. This empirical relationship is consistent with current understanding of O₃ photochemistry. The linear O₃–NO₂ relationships found from our multispatial scale analysis can be used to extrapolate the rate of change of O₃ with projected NO_x emission reductions, which suggests that future declines in annual fourth-highest daily average 8-hr maximum O₃ concentrations are unlikely to reach 65 ppbv or lower everywhere in the next decade. Measurements do not indicate increased annual reduction rates in (high) O₃ concentrations beyond the multidecadal precursor proportionality, since aggressive measures for NO_x and VOC reduction are in place and have not produced an accelerated O₃ reduction rate beyond that prior to the mid-2000s. Empirically estimated changes in O₃ with emissions suggest that O₃ is less sensitive to precursor reductions than is found by the CAMx (v. 6.1) photochemical model. Options for increasing the rate of O₃ change are limited by photochemical factors, including the increase in NO_x sensitivity with time (NMOC/NO_x ratio increase), increase in O₃ production efficiency at lower NO_x concentrations (higher O₃/NO_y ratio), and the presence of natural NO_x and NMOC precursors and background O₃.

Implications:?This analysis demonstrates empirical relations between O₃ and precursors based on long term trends in U.S. locations. The results indicate that ground-level O₃ concentrations have responded predictably to reductions in VOC and NO_x since the 1980s. The analysis reveals linear relations between the highest O₃ and NO₂ concentrations. Extrapolation of the historic trends to the future with expected continued precursor reductions suggest that achieving the 2014 proposed reduction in the U.S. National Ambient Air Quality Standard to a level between 65 and 70 ppbv is unlikely within the next decade. Comparison of measurements with national results from a regulatory photochemical model, CAMx, v. 6.1, suggests that model predictions are more sensitive to emissions changes than the observations would support.     

Isoprene and its degradation products as strong ozone precursors in Insubria,Northern Italy

Frequent smog episodes occur during spring, summer, and autumn in Insubria, Northern Italy. On a test site in this area the atmospheric concentration of the photo-oxidants ozone and peroxyacetyl nitrate has been monitored over a year (2000) together with ozone precursors listed in the European Union Air Quality Directive 2002/3/EC, such as nitrous oxides (NO_X) and volatile organic compounds (VOC) including hydrocarbons and carbonyls. The results of this study revealed a strong impact of biogenic isoprene on the air quality.In winter isoprene was detected at the ppt level and correlated with anthropogenic VOC. However, during the growing season isoprene exhibited a distinct diurnal variation with maximum concentrations late in the afternoon reaching up 70 ppbC attributed to strong emissions from the abundant vegetation of broad-leaf deciduous trees in this area. A new HPLC-MS method was developed for the determination of isoprene's primary atmospheric oxidation products methacrolein as its 2,4-dinitrophenylhydrazone and methyl vinyl ketone as an unusual double derivative with 2,4-dinitrophenylhydrazine. Methacrolein and methyl vinyl ketone followed the same diurnal and annual trends as isoprene. The average monthly concentration of isoprene and these products ranged from around 10 ppbC in June, July and September to 20 ppbC in August, which constitutes 15–30% of C₃–C₉ VOCs. The contribution from isoprene photo-oxidation to the ambient air formaldehyde concentrations was also found to be high during this period ranging from 30% to 60% in May, June, July and August.From the atmospheric VOC and NO_X concentrations the local photochemical ozone formation was estimated by the incremental reactivity approach. The calculations showed that in summer isoprene's contribution to the local ozone formation was as high as 50–75%.     

Measurement and analysis of atmospheric concentrations of isoprene and its reaction products in central Texas

A field experiment was conducted in August 1998 to investigate the concentrations of isoprene and isoprene reaction products in the surface and mixed layers of the atmosphere in Central Texas. Measured near ground-level concentrations of isoprene ranged from 0.3 (lower limit of detection – LLD) to 10.2 ppbv in rural regions and from 0.3 to 6.0 ppbv in the Austin urban area. Rural ambient formaldehyde levels ranged from 0.4 ppbv (LLD) to 20.0 ppbv for 160 rural samples collected, while the observed range was smaller at Austin (0.4–3.4 ppbv) for a smaller set of samples (37 urban samples collected). Methacrolein levels did not vary as widely, with rural measurements from 0.1 ppbv (LLD) to 3.7 ppbv and urban concentrations varying between 0.2 and 5.7 ppbv. Isoprene flux measurements, calculated using a simple box model and measured mixed-layer isoprene concentrations, were in reasonable agreement with emission estimates based on local ground cover data. Ozone formation attributable to biogenic hydrocarbon oxidation was also calculated. The calculations indicated that if the ozone formation occurred at low VOC/NO_x ratios, up to 20 ppbv of ozone formed could be attributable to biogenic photooxidation. In contrast, if the biogenic hydrocarbon reaction products were formed under low NO_x conditions, ozone production attributable to biogenics oxidation would be as low as 1 ppbv. This variability in ozone formation potentials implies that biogenic emissions in rural areas will not lead to peak ozone levels in the absence of transport of NO_x from urban centers or large rural NO_x sources.     

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.     

Estimation of the Natural Background of Ozone Present at Surface Rural Locations

The natural background in the ozone concentration at rural locations in the United States and western Europe has been estimated by use of several approaches. The approaches utilized include the following: (1) historical trends in ozone concentration measurements, (2) recent ozone measurements at remote sites, (3) use of tracers of air originating in the stratosphere or upper troposphere and (4) results from applications of tropospheric photochemical models. While each of these approaches has its own limitations it appears that the natural background of ozone during the warmer months of the year is in the range of 10 to 20 ppb. Most of the ozone originating in the lower stratosphere or upper troposphere is lost by chemical or physical removal processes as well as undergoing dilution by air in the lower troposphere before reaching ground level rural locations. Lower tropospheric photochemical processes, those below 5 km, are likely to account for most of the ozone measured at rural locations during the warmer months of the year.

A key aspect to improved quantitation of the contributions from lower tropospheric photochemical processes to ozone concentrations continues to be more extensive atmospheric measurements of the distribution of reactive species of nitrogen. The emission densities of anthropogenic sources of NO_x are known to be highly variable over populated areas of continents as well as between continental areas and the oceans. The emission densities of biogenic sources of NO_x are small, likely to be highly variable, but poorly quantitated. These wide variations indicate the need for use of three dimensional tropospheric photochemical models over large continental regions.

Available results do indicate higher efficiencies for ozone formation at lower NO_x concentrations, especially below 1 ppb.     

Projected ozone trends and changes in the ozone-precursor relationship in the South Coast Air Basin in response to varying reductions of precursor emissions

This study examined the effects of varying future reductions in emissions of oxides of nitrogen (NO_x) and volatile organic compounds (VOC) on the location and magnitude of peak ozone levels within California’s South Coast Air Basin (SoCAB or Basin). As ozone formation is currently VOC-limited in the Basin, model simulations with 2030 baseline emissions (?61% for NO_x and ?32% for VOC from 2008) predict 10–20% higher peak ozone levels (i.e., NO_x disbenefit) in the western and central SoCAB compared with the 2008 base simulation. With additional NO_x reductions of 50% beyond the 2030 baseline emissions (?81% from 2008), the predicted ozone levels are reduced by about 15% in the eastern SoCAB but remain comparable to 2008 levels in the western and central Basin. The Basin maximum ozone site shifts westward to more populated areas of the Basin and will result potentially in greater population-weighted exposure to ozone with even a relatively small shortfall in the required NO_x reductions unless accompanied by additional VOC reductions beyond 2030 baseline levels. Once committed to a NO_x-focused control strategy, NO_x reductions exceeding 90% from 2008 levels will be necessary to attain the ozone National Ambient Air Quality Standards (NAAQS). The findings from this study and other recent work that the current VOC emission estimates are underestimated by about 50% suggest that greater future VOC reductions will be necessary to reach the projected 2030 baseline emissions. Increasing the base year VOC emissions by a factor of 1.5 result in higher 2008 baseline ozone predictions, lower relative response factors, and about 20% lower projected design values. If correct, these findings have important implications for the total and optimum mix of VOC and NO_x emission reductions that will be required to attain the ozone NAAQS in the SoCAB.

Implications: Results of this study indicate that ozone levels in the western and central SoCAB would remain the same or increase with even a relatively small shortfall in the projected NO_x reductions under planned NO_x-focused controls. This possibility, therefore, warrants a rigorous analysis of the costs and effects of varying reductions of VOC and NO_x on the formation and combined health impacts of ozone and secondary particles. Given the nonlinearity of ozone formation, such analyses should include the implications of gradually increasing global background ozone concentrations and the Basin’s topography and meteorology on the practical limits of alternative emission control strategies.     

Volatile organic compounds from Italian vegetation and their interaction with ozone

Volatile Organic Compounds (VOCs) emitted from vegetation (particularly isoprenoids) represent an important source of atmospheric hydrocarbons almost double the anthropogenic source. When biogenic VOC mix with NO_x in the presence of UV radiation, ozone (O₃) is formed. In Italy, optimal conditions for O₃ formation in terms of VOC/NO_x ratios and abundance of UV radiation occur for long periods of the year. Moreover, Italian vegetation includes several species that are strong and evergreen isoprenoid emitters, and high temperatures for part of the year further stimulate these temperature-dependent emissions. We review emission of isoprenoids from Italian vegetation, current knowledge on the impact of rising O₃ levels on isoprenoid emission, and evidence showing that isoprenoids can increase both the O₃ flux to the plant and protection against oxidative stress because of their antioxidant functions. This trait not only influences plant tolerance to O₃ but also may substantially alter the flux of O₃ between atmosphere and biosphere.     

Long term changes in nitrogen oxides and volatile organic compounds in Toronto and the challenges facing local ozone control

Ground level ozone represents a significant air quality concern in Toronto, Canada, where the national 65 ppb 8-h standard is repeatedly exceeded during the summer. Here we present an analysis of nitrogen dioxide (NO₂), ozone (O₃), and volatile organic compound (VOC) data from federal and provincial governmental monitoring sites from 2000 to 2007. We show that summertime VOC reactivity and ambient concentrations of NO₂ have decreased over this period of time by up to 40% across Toronto and the surrounding region. This has not resulted in significant summertime ozone reductions, and in some urban areas, it appears to be increasing. We discuss the competing effects of decreased ozone titration leading to an increase in O₃, and decreased local ozone production, both caused by significant decreases in NO_x concentrations. In addition, by using local meteorological data, we show that annual variability in summer ozone correlates strongly with maximum daily temperatures, and we explore the effect of atmospheric transport from the southwest which has a significant influence on early morning levels before local production begins. A mathematical model of instantaneous ozone production is presented which suggests that, given the observed decreases in NO_x and VOC reactivity, we would not expect a significant change in local ozone production under photochemically relevant conditions. These results are discussed in the context of Toronto's recent commitment to cutting local smog-causing pollutants by 20% by 2012.     

C2–C10 nonmethane hydrocarbons measured in Dallas,USA—Seasonal trends and diurnal characteristics

Nonmethane hydrocarbons (NMHCs) are important precursors of ozone and other photo oxidants. We presented continuous hourly average concentrations of 45 C₂–C₁₀ NMHCs measured in urban area of Dallas, USA from 1996 to 2004. Most of the selected compounds are good variables with less noise. The top 10 species with high ozone-generating potential were identified according to their concentrations and reactivities. The ambient concentrations of abundant anthropogenic emission hydrocarbons measured in Dallas were about 2–4 times of the background values measured in the remote areas with adjacent latitude. The time series for anthropogenic emission hydrocarbons showed an obvious seasonal cycle with relatively high concentration in winter and low concentration in summer. The sinusoidal function with a linearly decreasing factor could well fit the time series of NMHCs. The phase of seasonal cycle for the aromatic hydrocarbons of toluene, m/p xylene and o-xylene that might come from both vehicle emission and solvent utilities evaporation was about 1 month earlier than that for alkanes and alkenes that mainly came from vehicle emission. Ambient NMHCs in Dallas decreased with a stable rate during 1996–2004. For most of compounds with high ozone-generating potential, the rate of ambient concentration decrease was higher or much higher than the rate of volatile organic compounds (VOCs) source emission reduction estimated by EPA's National Emission Inventory. On weekdays, the morning hydrocarbon concentration peak was coincident with morning traffic rush time in Dallas. Another concentration peak was delayed to afternoon traffic rush time. The characteristics of VOCs sources, photochemical removal processes and atmospheric dilution could be interpreted by the diurnal variations of benzene/ethylbenzene (B/E), toluene/ethylbenzene (T/E) and xylene/ethylbenzene (X/E). The ratio of VOC/NO_x measured in Dallas was substantially smaller than that calculated for USA cities. Ozone formation in Dallas was VOC sensitive.