The ozone productivity of n-propyl bromide: Part 2--An exception to the Maximum Incremental Reactivity Scale

In an earlier paper the ozone-forming potential of n-propyl bromide (NPB) was studied with a new methodology designed to address issues associated with a marginal smog-forming compound. However, the U.S. Environmental Protection Agency (EPA) subsequently revised its policy and now recommends using the Maximum Incremental Reactivity (MIR) scale to rank the ozone-forming potential of all volatile organic compounds (VOCs), including those of marginal ozone productivity. Nevertheless, EPA contemplated exceptions to the box-model-derived MIR scale by allowing use of photochemical grid-model simulations for case specific reactivity assessments. The California Air Resources Board (CARB) also uses the MIR scale and CARB has a Reactivity Scientific Advisory Committee that can consider exceptions to the MIR scale. In this study, grid-model simulations that were recommended by EPA are used to evaluate the incremental ozone impacts of NPB using an update to the chemical mechanism developed in an earlier paper. New methods of analysis of the grid-model output are further developed here to quantify the relative reactivities between NPB and ethane over a wide range of conditions. The new grid-model-based analyses show that NPB is significantly different and generally less in ozone-forming potential (i.e., reactivity) than predicted by the box-model-based MIR scale relative to ethane, EPA's "bright-line" test for non-VOC status. Although NPB has low reactivity compared to typical VOCs on any scale, the new grid-model analyses developed here show that NPB is far less reactive (and even has negative reactivity) compared to the reactivity predicted by the MIR scale.     

The Ozone Productivity of n-Propyl Bromide: Part 2—An Exception to the Maximum Incremental Reactivity Scale

Abstract

In an earlier paper the ozone-forming potential of n-propyl bromide (NPB) was studied with a new methodology designed to address issues associated with a marginal smog-forming compound. However, the U.S. Environmental Protection Agency (EPA) subsequently revised its policy and now recommends using the Maximum Incremental Reactivity (MIR) scale to rank the ozone-forming potential of all volatile organic compounds (VOCs), including those of marginal ozone productivity. Nevertheless, EPA contemplated exceptions to the box-model-derived MIR scale by allowing use of photochemical grid-model simulations for case specific reactivity assessments. The California Air Resources Board (CARB) also uses the MIR scale and CARB has a Reactivity Scientific Advisory Committee that can consider exceptions to the MIR scale. In this study, grid-model simulations that were recommended by EPA are used to evaluate the incremental ozone impacts of NPB using an update to the chemical mechanism developed in an earlier paper. New methods of analysis of the grid-model output are further developed here to quantify the relative reactivities between NPB and ethane over a wide range of conditions. The new grid-model-based analyses show that NPB is significantly different and generally less in ozone-forming potential (i.e., reactivity) than predicted by the box-model-based MIR scale relative to ethane, EPA’s “bright-line” test for non-VOC status. Although NPB has low reactivity compared to typical VOCs on any scale, the new grid-model analyses developed here show that NPB is far less reactive (and even has negative reactivity) compared to the reactivity predicted by the MIR scale.     

Development of the SAPRC-07 chemical mechanism

An updated version of the SAPRC-99 gas-phase atmospheric chemical mechanism, designated SAPRC-07, is described. The rate constants and reactions have been updated based on current data and evaluations, the aromatics mechanisms have been reformulated and are less parameterized, chlorine chemistry has been added, the method used to represent peroxy reactions has been reformulated to be more appropriate for modeling gas-phase secondary organic aerosol precursors, and representations for many types of VOCs have been added or improved. This mechanism was evaluated against the result of ～2400 environmental chamber experiments carried out in 11 different environmental chambers, including experiments to test mechanisms for over 110 types of VOCs. The performance in simulating the chamber data was generally satisfactory for most types of VOCs but some biases were seen in simulations of some types of experiments. The mechanism was used to derive updated MIR and other ozone reactivity scales for almost 1100 types of VOCs, though in most cases the changes in MIR values relative to SAPRC-99 were not large. This mechanism update results in somewhat lower predictions of ozone in one-day ambient model scenarios under low VOC/NO_x conditions. The files needed to implement the mechanism and additional documentation is available at the SAPRC mechanism web site at http://www.cert.ucr.edu/～carter/SAPRC.     

Mixing ratios of volatile organic compounds (VOCs) in the atmosphere of Karachi,Pakistan

Mixing ratios of carbon monoxide (CO), methane (CH₄), non-methane hydrocarbons, halocarbons and alkyl nitrates (a total of 72 species) were determined for 78 whole air samples collected during the winter of 1998–1999 in Karachi, Pakistan. This is the first time that volatile organic compound (VOC) levels in Karachi have been extensively characterized. The overall air quality of the urban environment was determined using air samples collected at six locations throughout Karachi. Methane (6.3 ppmv) and ethane (93 ppbv) levels in Karachi were found to be much higher than in other cities that have been studied. The very high CH₄ levels highlight the importance of natural gas leakage in Karachi. The leakage of liquefied petroleum gas contributes to elevated propane and butane levels in Karachi, although the propane and butane burdens were lower than in other cities (e.g., Mexico City, Santiago). High levels of benzene (0.3–19 ppbv) also appear to be of concern in the Karachi urban area. Vehicular emissions were characterized using air samples collected along the busiest thoroughfare of the city (M.A. Jinnah Road). Emissions from vehicular exhaust were found to be the main source of many of the hydrocarbons reported here. Significant levels of isoprene (1.2 ppbv) were detected at the roadside, and vehicular exhaust is estimated to account for about 20% of the isoprene observed in Karachi. 1,2-Dichloroethane, a lead scavenger added to leaded fuel, was also emitted by cars. The photochemical production of ozone (O₃) was calculated for CO and the various VOCs using the Maximum Incremental Reactivity (MIR) scale. Based on the MIR scale, the leading contributors to O₃ production in Karachi are ethene, CO, propene, m-xylene and toluene.     

Airshed Model Evaluation of Reactivity Adjustment Factors Calculated with the Maximum Incremental Reactivity Scale for Transitional-Low Emission Vehicles

Abstract

The California Air Resources Board recently adopted regulations for light- and medium-duty vehicles that require reductions in the ozone-forming potential or “reactivity,” rather than the mass, of nonmethane organic gas (NMOG) emissions. The regulations allow sale of all alternatively fueled vehicles (AFVs) that meet NMOG exhaust emission standards equivalent in reactivity to those set for vehicles fueled with conventional gasoline. Reactivity adjustment factors (RAFs), the ratio of the reactivity (per gram) of the AFV exhaust to that of the conventionally fueled vehicle (CFV), are used to correct the stringent exhaust emission standards. Complete chemical speciation of the exhaust and conversion of each NMOG species to an appropriate mass of ozone using the maximum incremental reactivity (MIR) scale of Carter determines the RAF. The MIR approach defines reactivity where NMOG control is the most effective strategy in reducing ozone concentrations, and assumes it is not important to define reactivity at other conditions, i.e., where NO_x is the limiting precursor.

This study used the Carnegie/California Institute of Technology airshed model to evaluate whether the RAF-adjusted AFV emissions result in ozone impacts equivalent to those of CFV emissions. A matrix of two ozone episodes in the South Coast Air Basin (SoCAB) of California, two base emission inventories, and exhaust emissions from three alternative fuels that meet the first level of the low emission vehicle standards bounds the expected range of conditions. Although very good agreement was found previously for individual NMOG species,² this study noted deviations of up to ±15 percent from the equal ozone impacts for any vehicle/fuel combination required by the California regulations. These deviations appear to be attributable to differences in spatial and temporal patterns of emissions between vehicle fleets, rather than a problem with the MIR approach. The first formally adopted RAF, a value of 0.41 for 85 percent methanol/15 percent gasoline-fueled vehicles, includes a 10 percent increase based on the airshed modeling. The correction to the RAF is different for other fuels and may be different for air basins other than the SoCAB.     

Application of OMI observations to a space-based indicator of NOx and VOC controls on surface ozone formation

We investigated variations in the relative sensitivity of surface ozone formation in summer to precursor species concentrations of volatile organic compounds (VOCs) and nitrogen oxides (NO_x) as inferred from the ratio of the tropospheric columns of formaldehyde to nitrogen dioxide (the “Ratio”) from the Aura Ozone Monitoring Instrument (OMI). Our modeling study suggests that ozone formation decreases with reductions in VOCs at Ratios <1 and NO_x at Ratios >2; both NO_x and VOC reductions may decrease ozone formation for Ratios between 1 and 2. Using this criteria, the OMI data indicate that ozone formation became: 1. more sensitive to NO_x over most of the United States from 2005 to 2007 because of the substantial decrease in NO_x emissions, primarily from stationary sources, and the concomitant decrease in the tropospheric column of NO₂, and 2. more sensitive to NO_x with increasing temperature, in part because emissions of highly reactive, biogenic isoprene increase with temperature, thus increasing the total VOC reactivity. In cities with relatively low isoprene emissions (e.g., Chicago), the data clearly indicate that ozone formation became more sensitive to NO_x from 2005 to 2007. In cities with relatively high isoprene emissions (e.g., Atlanta), we found that the increase in the Ratio due to decreasing NO_x emissions was not obvious as this signal was convolved with variations in the Ratio associated with the temperature dependence of isoprene emissions and, consequently, the formaldehyde concentration.     

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.     

Estimate of initial isoprene contribution to ozone formation potential in Beijing, China

Volatile organic compounds (VOCs) are important precursors of tropospheric ozone formation. Isoprene contributions to ozone formation by using ambient mixing ratios are generally underestimated because of rapid chemical losses. In this study, ambient mixing ratios of major VOC species were continuously measured at Peking university (PKU) and YUFA, urban and sub-urban sites in Beijing, the city that will host 2008 Olympic Games. The observed mixing ratios of methyl vinyl ketone (MVK), methacrolein (MACR) and isoprene were used to derive the mixing ratios of initial isoprene, which means the ambient isoprene level before it undergoes any photochemical reaction with OH radicals. The average mixing ratios of initial isoprene were 3.3±1.6 and 2.9±1.5 ppbv at PKU and YUFA sites, respectively. The percentages of initial isoprene in total initial VOCs were 10.8% at PKU site and 11.4% at YUFA site, in reasonable agreement with the isoprene contribution in total VOC emissions as derived from source inventories. Maximum increment reactivity (MIR) was used to evaluate the ozone formation potential (OFP) for major VOC species. The OFP for initial isoprene accounted for 23% of the total OFPs for all measured species, compared to 11% using ambient mixing ratios of isoprene at PKU site. Similarly, at YUFA site, the ambient measured isoprene and initial isoprene contributed 10% and 22%, respectively, to the OFPs for total measured VOCs. It seems that isoprene has similar contribution to ozone formation at both sites in Beijing city.     

Dynamic evaluation of a regional air quality model: Assessing the emissions-induced weekly ozone cycle

Air quality models are used to predict changes in pollutant concentrations resulting from envisioned emission control policies. Recognizing the need to assess the credibility of air quality models in a policy-relevant context, we perform a dynamic evaluation of the Community Multiscale Air Quality (CMAQ) modeling system for the “weekend ozone effect” to determine if observed changes in ozone due to weekday-to-weekend (WDWE) reductions in precursor emissions can be accurately simulated. The weekend ozone effect offers a unique opportunity for dynamic evaluation, as it is a widely documented phenomenon that has persisted since the 1970s. In many urban areas of the Unites States, higher ozone has been observed on weekends than weekdays, despite dramatically reduced emissions of ozone precursors (nitrogen oxides [NO_x] and volatile organic compounds [VOCs]) on weekends. More recent measurements, however, suggest shifts in the spatial extent or reductions in WDWE ozone differences. Using 18 years (1988–2005) of observed and modeled ozone and temperature data across the northeastern United States, we re-examine the long-term trends in the weekend effect and confounding factors that may be complicating the interpretation of this trend and explore whether CMAQ can replicate the temporal features of the observed weekend effect. The amplitudes of the weekly ozone cycle have decreased during the 18-year period in our study domain, but the year-to-year variability in weekend minus weekday (WEWD) ozone amplitudes is quite large. Inter-annual variability in meteorology appears to influence WEWD differences in ozone, as well as WEWD differences in VOC and NO_x emissions. Because of the large inter-annual variability, modeling strategies using a single episode lasting a few days or a few episodes in a given year may not capture the WEWD signal that exists over longer time periods. The CMAQ model showed skill in predicting the absolute values of ozone concentrations during the daytime. However, early morning NO_x concentrations were underestimated and ozone levels were overestimated. Also, the modeled response of ozone to WEWD differences in emissions was somewhat less than that observed. This study reveals that model performance may be improved by (1) properly estimating mobile source NO_x emissions and their temporal distributions, especially for diesel vehicles; (2) reducing the grid cell size in the lowest layer of CMAQ; and, (3) using time-dependent and more realistic boundary conditions for the CMAQ simulations.     

VOC concentration profiles in an ozone non-attainment area: A case study in an urban and industrial complex metroplex in southern Taiwan

VOCs are important precursors of the atmospheric ozone formation species. This study investigated the airborne concentrations of 52 VOCs at two air quality monitoring stations, Daliao and Tzouying, during wintertime in southern Taiwan. Airborne VOCs samples were taken in stainless steel canisters four times per day and analyzed via gas chromatography/mass spectrometry. Maximum increment reactivity (MIR) was used to evaluate the ozone formation potential in this ozone non-attainment region. Toluene, propane, isopentane, propene, n-butane, n-pentane and isoprene contributed 78–79% of the 52 VOCs in Daliao. Toluene, 1-butene, isopentane, propene, propane, n-undecane, and n-butane contributed 71–77% of the 52 VOCs in Tzouying. The VOCs concentrations were higher in Daliao due to the high toluene emissions from a paint plant and a solvent plant in the nearby industrial district. The 24-h VOC concentrations averaged 25 ppb higher in Tzouying than in Daliao. The ozone formation potential of airborne VOCs was 1687–2730 and 1717–2261 μg-O₃/g-VOCs in Daliao and Tzouying, respectively. Ozone concentrations in Tzouying were 44 ppb higher than in Daliao during the 1200–1600 sampling period.     

Rural Ozone Across the Eastern United States: Analysis of CASTNet Data, 1988–1995

ABSTRACT

A predominantly rural ozone monitoring network was operated under the auspices of the Clean Air Status and Trends Network (CASTNet) from 1988 until 1995. Ozone data from sites in the eastern United States are presented and several indices are used to describe the spatial and temporal distribution of ozone concentration and exposure. These indices are SUM06, W126, the 8-hour rolling average (MAX_8hr>80), and the current National Ambient Air Quality Standards (NAAQS) for ozone. Ozone indices were selected to illustrate the spatial and temporal distribution of ozone, and the sensitivity of this distribution to different representations of concentration or exposure.

CASTNet is unique in that a uniform set of site selection criteria and uniform procedures, including traceability to a single primary standard, provide a high degree of comparability across sites. Sites were selected to avoid undue influence from point sources, area sources, or local activities. The sites reflect a wide range of land use and terrain types including agricultural and forested, in flat, rolling, and complex terrain from the eastern seaboard across the Appalachian Mountains to the Midwest.

Results indicate that ozone concentrations varied greatly in time and space across the eastern United States. Sites in the upper northeast, upper midwest, and southern periphery subregions experienced relatively low ozone during the years of record compared to sites in the northeast, midwest, and south central subregions. Ozone exposures at an individual rural site are dependent on many factors, including terrain, meteorology, and distance from sources of precursors. Relative to the current (as of 1996) NAAQS, only a handful of CASTNet sites near major urban areas report exceedances. In contrast, the majority of CASTNet sites might exceed the proposed new primary standard for ozone.

Sites at high elevation (>900m) in the east exhibit relatively high exposure statistics (e.g., SUM06 and W126), but no exceedance of the current ozone standard from 1988 through 1995. Terrain effects explain some of the variability within subregions and are an important consideration in the design of monitoring networks for ozone and possibly other pollutants.     

Nonpoint sources of volatile organic compounds in urban areas-relative importance of land surfaces and air

Volatile organic compounds (VOCs) commonly detected in urban waters across the United States include gasoline-related compounds (e.g. toluene, xylene) and chlorinated compounds (e.g. chloroform, tetrachloroethane [PCE], trichloroethene [TCE]). Statistical analysis of observational data and results of modeling the partitioning of VOCs between air and water suggest that urban land surfaces are the primary nonpoint source of most VOCs. Urban air is a secondary nonpoint source, but could be an important source of the gasoline oxygenate methyl-tert butyl ether (MTBE). Surface waters in urban areas would most effectively be protected by controlling land-surface sources.     

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.     

An experimental investigation of incremental reactivities of volatile organic compounds

California has adopted a set of VOC reactivity factors for regulatory purposes that is based on a model of the ozone formation process. These incremental reactivity factors (derived by Carter) describe the amount of ozone each exhaust VOC will form under a certain set of conditions in an urban atmosphere. The main objective of this study is to measure reactivity factors using smog chamber experiments, and to compare the measurements to the Carter factors. A new facility was constructed explicitly for this study. The facility has four identical smog chambers and a temperature-controlled enclosure for the chambers. The chambers are irradiated using a set of filtered xenon arc lamps to approximate “sunlight”. The reactivities of 14 individual VOCs representative of those found in automobile exhaust and several mixtures of VOCs have been measured. The measured and Carter-reactivity factors were highly correlated, suggesting that the chemical model used by Carter accounts for the reactivities of a wide range of compounds with dramatically different uncertainties in their mechanisms. The measured results, in general, are consistent with the Carter-reactivity factors for comparing the relative reactivities of VOCs in the atmosphere. However, additional kinetic and mechanistic studies of many VOC species including aromatic isomers are needed to improve reactivity scales.     

An observation-based model for analyzing ozone precursor relationships in the urban atmosphere

An Observation-Based Model (OBM) is described, which uses in-situ atmospheric observations to determine the sensitivity of ozone concentrations in an urban atmosphere to changes in the emissions of ozone precursors (i.e., volatile organic compounds and nitrogen oxides). The model is formulated following the concept of Relative Incremental Reactivity (RIR) developed by Carter and Atkinson. In the OBM, however, observed concentrations rather than emission inventories are used to drive the photochemical simulations and thereby ensure that the calculations are carried out for the proper mix of nitrogen oxides and volatile organic compounds. From these calculations, a series of sensitivity factors, or RIRs, are inferred that can be used to (1) determine whether reducing emissions of nitrogen oxide or emissions of hydrocarbons would be most effective in abating ozone in a given urban area, and (2) identify the most critical subset of hydrocarbons present in an urban atmosphere causing ozone exceedances. Because the OBM is relatively easy and inexpensive to operate and makes use of data that are increasingly available, it can be used to analyze a wide array of ozone episodes and, thus, could prove to be a relatively cost-effective tool for the analysis of ozone precursor relationships in an urban atmosphere. On the other hand, because the OBM is diagnostic rather than prognostic, it cannot be used in a predictive mode to estimate exactly how much emission reduction is needed to reduce ozone concentrations. For this reason, the OBM should be viewed as a complement to, rather than a substitute for, more sophisticated gridded, emission-based models. To illustrate the characteristics of the OBM and to demonstrate its applicability, we first compare the results of the OBM to those obtained from a series of simulations of the Atlanta metropolitan area using the Urban Airshed Model (UAM), a three-dimensional Eulerian grid model. The OBM is then used to analyze a dataset obtained from the 1990 Atlanta Ozone Study, an EPA field sampling program conducted during the summer of 1990. Because of limitations and potential flaws in the 1990 Atlanta dataset, the results of this OBM analysis are largely illustrative rather than definitive. Nevertheless, a few important issues are elucidated by the analysis. These include (1) the importance of accounting for biogenic hydrocarbons produced from urban vegetation; (2) the potential flaw in using early-morning VOC-to-NOx ratios to infer whether ozone production is limited by VOC or NOx; (3) the critical need for high-sensitivity nitrogen oxide measurements to quantify the sub-ppbv concentrations of NO during the afternoon hours; and (4) the need to consider a number of individual ozone episodes in studying an urban atmosphere because of the possibility that the degree of VOC- and NOx-limitation may vary from one episode to another.     

A simple model for estimating emissions of volatile organic compounds from grass and cut grass in urban airsheds and its application to two Australian cities

Grass, and particularly cut grass, recently has been shown to emit significant amounts of volatile organic compounds (VOCs) into the atmosphere. Some components of these emissions are highly reactive and may contribute to photochemical smog in urban areas. A simple model for estimating the VOC emissions from grass and for grass cutting that allows these processes to be included in urban/regional emissions inventories is presented here. Using previous work and recent literature values, estimates are made of these biogenic volatile organic compound (BVOC) emissions for two typical urban airsheds, those including the cities of Sydney and Melbourne in Australia. Grass and cut grass could contribute approximately 2% for Sydney and 3% for Melbourne of the total VOCs emitted into these urban atmospheres annually. These contributions could rise to 4 and 5%, respectively, during the weekends of the summer growing season and, thus, could contribute to weekday/weekend ozone differences. It is recommended that the emissions of BVOCs from grass and cut grass be included in urban and global emissions inventories so that more accurate predictions of smog chemistry can be determined.     

Estimating the ozone formation potential of volatile aromatic compounds in vehicle tunnels.

Two vehicle tunnels located in the Taipei area were selected to study the ozone formation potential of volatile aromatic compounds (VACs). Air samples in the two tunnels were collected using canisters. Analysis of VACs was conducted with a gas chromatograph equipped with a mass spectrometer. The total VOCs concentrations in Zefun tunnel ranged from 483.5 to 1032.2 (micrograms/m3) which increased with the increase in traffic volume. In the Lishin tunnel, the total VACs concentration ranged from 356.6 to 1961.3 (micrograms/m3) which was not well correlated with the traffic volume. The most predominant VACs in these vehicle tunnels were toluene and xylenes. Although the traffic volume and types of vehicles were not exactly the same, the characteristic ratios of the VACs concentrations were found to be similar. These results indicated that the existence of a specific characteristic ratio of VAC concentration was affected by the mobile sources. The maximum ozone formation potential resulted from the vehicles in the Lishin motorcycle tunnel which had higher values than the Zefun tunnel and much higher than the SPECIATE databases in the US via weighting the maximum incremental reactivity (MIR) scale.     

Modeling an air pollution episode in northwestern United States: Identifying the effect of nitrogen oxide and volatile organic compound emission changes on air pollutants formation using direct sensitivity analysis

Air quality impacts of volatile organic compound (VOC) and nitrogen oxide (NO_x) emissions from major sources over the northwestern United States are simulated. The comprehensive nested modeling system comprises three models: Community Multiscale Air Quality (CMAQ), Weather Research and Forecasting (WRF), and Sparse Matrix Operator Kernel Emissions (SMOKE). In addition, the decoupled direct method in three dimensions (DDM-3D) is used to determine the sensitivities of pollutant concentrations to changes in precursor emissions during a severe smog episode in July of 2006. The average simulated 8-hr daily maximum O₃ concentration is 48.9 ppb, with 1-hr O₃ maxima up to 106 ppb (40 km southeast of Seattle). The average simulated PM_2.5 (particulate matter with an aerodynamic diameter <2.5 μm) concentration at the measurement sites is 9.06 μg m^?3, which is in good agreement with the observed concentration (8.06 μg m^?3). In urban areas (i.e., Seattle, Vancouver, etc.), the model predicts that, on average, a reduction of NO_x emissions is simulated to lead to an increase in average 8-hr daily maximum O₃ concentrations, and will be most prominent in Seattle (where the greatest sensitivity is??0.2 ppb per % change of mobile sources). On the other hand, decreasing NO_x emissions is simulated to decrease the 8-hr maximum O₃ concentrations in remote and forested areas. Decreased NO_x emissions are simulated to slightly increase PM_2.5 in major urban areas. In urban areas, a decrease in VOC emissions will result in a decrease of 8-hr maximum O₃ concentrations. The impact of decreased VOC emissions from biogenic, mobile, nonroad, and area sources on average 8-hr daily maximum O₃ concentrations is up to 0.05 ppb decrease per % of emission change, each. Decreased emissions of VOCs decrease average PM_2.5 concentrations in the entire modeling domain. In major cities, PM_2.5 concentrations are more sensitive to emissions of VOCs from biogenic sources than other sources of VOCs. These results can be used to interpret the effectiveness of VOC or NO_x controls over pollutant concentrations, especially for localities that may exceed National Ambient Air Quality Standards (NAAQS).

Implications: The effect of NO_x and VOC controls on ozone and PM_2.5 concentrations in the northwestern United States is examined using the decoupled direct method in three dimensions (DDM-3D) in a state-of-the-art three-dimensional chemical transport model (CMAQ). NO_x controls are predicted to increase PM_2.5 and ozone in major urban areas and decrease ozone in more remote and forested areas. VOC reductions are helpful in reducing ozone and PM_2.5 concentrations in urban areas. Biogenic VOC sources have the largest impact on O₃ and PM_2.5 concentrations.     

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.