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

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

Modeling the Effects of VOC/NOx Emissions on Ozone Synthesis in the Cascadia Airshed of the Pacific Northwest

ABSTRACT

A modeling system consisting of MM5, Calmet, and Calgrid was used to investigate the sensitivity of anthropogenic volatile organic compound (VOC) and oxides of nitrogen (NO_x) reductions on ozone formation within the Cascadia airshed of the Pacific Northwest. An ozone episode that occurred on July 11-14, 1996, was evaluated. During this event, high ozone levels were recorded at monitors downwind of Seattle, WA, and Portland, OR, with one monitor exceeding the 1 hr/120 ppb National Ambient Air Quality Standard (at 148 ppb), and six monitors above the proposed 8 hr/80 ppb standard (at 82-130 ppb). For this particular case, significant emissions reductions, between 25 and 75%, would be required to decrease peak ozone concentrations to desired levels. Reductions in VOC emissions alone, or a combination of reduced VOC and NO_x emissions, were generally found to be most effective; reducing NO_x emissions alone resulted in increased ozone in the Seattle area. When only VOC emissions were curtailed, ozone reductions occurred in the immediate vicinity of densely populated areas, while NO_x reductions resulted in more widespread ozone reductions.     

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.     

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%.     

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.     

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.     

Sensitivity of biogenic secondary organic aerosols to future climate change at regional scales: An online coupled simulation

Biogenic emissions and secondary organic aerosols (SOA) are strongly dependent on climatic conditions. To understand the SOA levels and their sensitivity to future climate change in the United States (U.S.), we present a modeling work with the consideration of SOA formation from the oxidation of biogenic emissions with atmospheric oxidants (e.g., OH, O₃, and NO₃). The model simulation for the present-day climate is evaluated against satellite and ground-based aerosol measurements. Although the model underestimates aerosol concentrations over the northwestern U.S. due to the lack of fire emissions in the model simulations, overall, the SOA results agree well with previous studies. Comparing with the available measurements of organic carbon (OC) concentrations, we found that the amount of SOA in OC is significant, with the ratio ranging from 0.1 to 0.5/0.6. The enhanced modeling system driven by global climate model output was also applied for two three-year one-month simulations (July, 2001–2003 and 2051–2053) to examine the sensitivity of SOA to future climate change. Under the future two emissions scenarios (A1B and A2), future temperature changes are predicted to increase everywhere in the U.S., but with different degrees of increase in different regions. As a result of climate change in the future, biogenic emissions are predicted to increase everywhere, with the largest increase (～20%) found in the southeastern and northwestern U.S. under the A1B scenario. Changes in SOA are not identical with those in biogenic emissions. Under the A1B scenario, the biggest increase in SOA is found over Texas, with isoprene emissions being the major contributor to SOA formation. The range of change varies from 5% over the southeast region to 26% over Texas. The changes in either biogenic emissions or SOA under the two climate scenarios are different due to the differences in climatic conditions. Our results also suggest that future SOA concentrations are also influenced by several other factors such as the partitioning coefficients, the atmospheric oxidative capability, primary organic carbon aerosols and anthropogenic emissions.     

Greenhouse effect of NOX

Through various processes the nitrogen oxides (NO_X) interact with trace gases in the troposphere and stratosphere which do absorb in the spectral range relevant to the greenhouse effect (infrared wavelengths). The net effect is an enhancement of the greenhouse effect. The catalytic role of NO_X in the production of tropospheric ozone provides the most prominent contribution. The global waming potential is estimated as GWP (NO_X = 30 – 33 and 7 – 10 for the respective time horizons of 20 and 100 years, and is thereby comparable to that of methane. NO_X emissions in rural areas of anthropogenically influenced regions, or those in the vicinity of the txopopause caused by air traffic, cause the greenhouse effectivity to be substantially more intense. We estimate an additional 5–23 % for Germany’s contribution to the anthropogenic greenhouse effect as a result of the indirect greenhouse effects stemming from NO_X. Furthermore, a small and still inaccurately defined amount of the deposited NO_X which has primarily been converted into nitrates is again released from the soil into the atmosphere in the form of the long-lived greenhouse gas nitrous oxide (N₂O). Thus, anthropogenically induced NO_X emissions contribute to enhanced greenhouse effect and to stratospheric ozone depletion in the time scale of more than a century.     

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.     

Modeling and direct sensitivity analysis of biogenic emissions impacts on regional ozone formation in the Mexico-U.S. border area

A spatially and temporally resolved biogenic hydrocarbon and nitrogen oxides (NOx) emissions inventory has been developed for a region along the Mexico-U.S. border area. Average daily biogenic non-methane organic gases (NMOG) emissions for the 1700 x 1000 km2 domain were estimated at 23,800 metric tons/day (62% from Mexico and 38% from the United States), and biogenic NOx was estimated at 1230 metric tons/day (54% from Mexico and 46% from the United States) for the July 18-20, 1993, ozone episode. The biogenic NMOG represented 74% of the total NMOG emissions, and biogenic NOx was 14% of the total NOx. The CIT photochemical airshed model was used to assess how biogenic emissions impact air quality. Predicted ground-level ozone increased by 5-10 ppb in most rural areas, 10-20 ppb near urban centers, and 20-30 ppb immediately downwind of the urban centers compared to simulations in which only anthropogenic emissions were used. A sensitivity analysis of predicted ozone concentration to emissions was performed using the decoupled direct method for three dimensional air quality models (DDM-3D). The highest positive sensitivity of ground-level ozone concentration to biogenic volatile organic compound (VOC) emissions (i.e., increasing biogenic VOC emissions results in increasing ozone concentrations) was predicted to be in locations with high NOx levels, (i.e., the urban areas). One urban center--Houston--was predicted to have a slight negative sensitivity to biogenic NO emissions (i.e., increasing biogenic NO emissions results in decreasing local ozone concentrations). The highest sensitivities of ozone concentrations to on-road mobile source VOC emissions, all positive, were mainly in the urban areas. The highest sensitivities of ozone concentrations to on-road mobile source NOx emissions were predicted in both urban (either positive or negative sensitivities) and rural (positive sensitivities) locations.     

Modelling study of the impact of isoprene and terpene biogenic emissions on European ozone levels

The impact of biogenic volatile organic compound (BVOC) emissions on European ozone distributions has not yet been evaluated in a comprehensive way. Using the CHIMERE chemistry-transport model the variability of surface ozone levels from April to September for 4 years (1997, 2000, 2001, 2003) resulting from biogenic emissions is investigated. It is shown that BVOC emissions increased on average summer daily ozone maxima over Europe by 2.5 ppbv (5%). The impact is most significant in Portugal (up to 15 ppbv) and in the Mediterranean region (about 5 ppbv), being smaller in the northern part of Europe (1.3 ppbv north of 47.5°N). The average impact is rather similar for the three summers (1997, 2000, 2001), but is much larger during the extraordinarily hot summer of 2003. Here, the biogenic contribution to surface ozone doubles compared to other years at some locations. Interaction with anthropogenic NO_x emissions is found to be a key process for ozone production of biogenic precursors. Comparing the impact of the state-of-the-art BVOC emission inventory compiled within the NatAir project and an earlier, widely used BVOC inventory derived from Simpson et al. [1999. Inventorying emissions from nature in Europe. Journal of Geophysical Research 104(D7), 8113–8152] on surface ozone shows that ozone produced from biogenic precursors is less in central and northern Europe but in certain southern areas much higher e.g. Iberian Peninsula and the Mediterranean Sea. The uncertainty in the regionally averaged impact of BVOC on ozone build-up in Europe is estimated to be ±50%.     

Secondary organic aerosol importance in the future atmosphere

In order to investigate the secondary organic aerosol (SOA) response to changes in biogenic volatile organic compounds (VOC) emissions in the future atmosphere and how important will SOA be relative to the major anthropogenic aerosol component (sulfate), the global three-dimensional chemistry/transport model TM3 has been used. Emission estimates of biogenic VOC (BVOC) and anthropogenic gases and particles from the literature for the year 2100 have been adopted.According to our present-day model simulations, isoprene oxidation produces 4.6 Tg SOA yr⁻¹, that is less than half of the 12.2 Tg SOA yr⁻¹ formed by the oxidation of other BVOC. In the future, nitrate radicals and ozone become more important than nowadays, but remain minor oxidants for both isoprene and aromatics. SOA produced by isoprene is estimated to almost triple, whereas the production from other BVOC more than triples. The calculated future SOA burden change, from 0.8 Tg at present to 2.0 Tg in the future, is driven by changes in emissions, oxidant levels and pre-existing particles. The non-linearity in SOA formation and the involved chemical and physical feedbacks prohibit the quantitative attribution of the computed changes to the above-mentioned individual factors. In 2100, SOA burden is calculated to exceed that of sulfate, indicating that SOA might become more important than nowadays. These results critically depend on the biogenic emissions and thus are subject to the high uncertainty associated with these emissions estimated due to the insufficient knowledge on plant response to carbon dioxide changes. Nevertheless, they clearly indicate that the change in oxidants and primary aerosol caused by human activities can contribute as much as the change in BVOC emissions to the increase of the biogenic SOA production in the future atmosphere.     

Future land use and land cover influences on regional biogenic emissions and air quality in the United States

A regional modeling system was applied with inputs from global climate and chemistry models to quantify the effects of global change on future biogenic emissions and their impacts on ozone and biogenic secondary organic aerosols (BSOA) in the US. Biogenic emissions in the future are influenced by projected changes in global and regional climates and by variations in future land use and land cover (LULC). The modeling system was applied for five summer months for the present-day case (1990–1999, Case 1) and three future cases covering 2045–2054. Individual future cases were: present-day LULC (Case 2); projected-future LULC (Case 3); and future LULC with designated regions of tree planting for carbon sequestration (Case 4). Results showed changing future meteorology with present-day LULC (Case 2) increased average isoprene and monoterpene emission rates by 26% and 20% due to higher temperature and solar insolation. However when LULC was changed together with climate (Case 3), predicted isoprene and monoterpene emissions decreased by 52% and 31%, respectively, due primarily to projected cropland expansion. The reduction was less, at 31% and 14% respectively, when future LULC changes were accompanied by regions of tree planting (Case 4). Despite the large decrease in biogenic emission, future average daily maximum 8-h (DM8H) ozone was found to increase between +8 ppbv and +10 ppbv due to high future anthropogenic emissions and global chemistry conditions. Among the future cases, changing LULC resulted in spatially varying future ozone differences of ?5 ppbv to +5 ppbv when compared with present-day case. Future BSOA changed directly with the estimated monoterpene emissions. BSOA increased by 8% with current LULC (Case 2) but decreased by 45%–28% due to future LULC changes. Overall, the results demonstrated that on a regional basis, changes in LULC can offset temperature driven increases in biogenic emissions, and, thus, LULC projection is an important factor to consider in the study of future regional air quality.     

Natural emissions for regional modeling of background ozone and particulate matter and impacts on emissions control strategies

Natural emissions adopted in current regional air quality modeling are updated to better describe natural background ozone and PM concentrations for North America. The revised natural emissions include organosulfur from the ocean, NO from lightning, sea salt, biogenic secondary organic aerosol (SOA) precursors, and pre-industrial levels of background methane. The model algorithm for SOA formation was also revised. Natural background ozone concentrations increase by up to 4 ppb in annual average over the southeastern US and Gulf of Mexico due to added NO from lightning while the revised biogenic emissions produced less ozone in the central and western US. Natural PM_2.5 concentrations generally increased with the revised natural emissions. Future year (2018) simulations were conducted for several anthropogenic emission reduction scenarios to assess the impact of the revised natural emissions on anthropogenic emission control strategies. Overall, the revised natural emissions did not significantly alter the ozone responses to the emissions reductions in 2018. With revised natural emissions, ozone concentrations were slightly less sensitive to reducing NOx in the southeastern US than with the current natural emissions due to higher NO from lightning. The revised natural emissions have little impact on modeled PM_2.5 responses to anthropogenic emission reductions. However, there are substantial uncertainties in current representations of natural sources in air quality models and we recommend that further study is needed to refine these representations.     

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.     

Effects of uncertainty in the reaction of the hydroxyl radical with nitrogen dioxide on model-simulated ozone control strategies

We evaluated the effect of a 20% reduction in the rate constant of the reaction of the hydroxyl radical with nitrogen dioxide to produce nitric acid (OH+NO₂→HNO₃) on model predictions of ozone mixing ratios ([O₃]) and the effectiveness of reductions in emissions of volatile organic compounds (VOC) and nitrogen oxides (NO_x) for reducing [O₃]. By comparing a model simulation with the new rate constant to a base case scenario, we found that the [O₃] increase was between 2 and 6% for typical rural conditions and between 6 and 16% for typical urban conditions. The increases in [O₃] were less than proportional to the reduction in the OH+NO₂ rate constant because of negative feedbacks in the photochemical mechanism. Next, we used two different approaches to evaluate how the new OH+NO₂ rate constant changed the effectiveness of reductions in emissions of VOC and NO_x: first, we evaluated the effect on [O₃] sensitivity to small changes in emissions of VOC (d[O₃]/dE_VOC) and NO_x (d[O₃]/dE_NOx); and secondly, we used the empirical kinetic modeling approach to evaluate the effect on the level of emissions reduction necessary to reduce [O₃] to a specified level. Both methods showed that reducing the OH+NO₂ rate constant caused control strategies for VOC to become less effective relative to NO_x control strategies. We found, however, that d[O₃]/dE_VOC and d[O₃]/dE_NOx did not quantitatively predict the magnitude of the change in the control strategy because the [O₃] response was nonlinear with respect to the size of the emissions reduction. We conclude that model sensitivity analyses calculated using small emissions changes do not accurately characterize the effect of uncertainty in model inputs (in this case, the OH+NO₂ rate constant) on O₃ attainment strategies. Instead, the effects of changes in model inputs should be studied using large changes in precursor emissions to approximate realistic attainment scenarios.     

An assessment of the impact of climate change on air quality at two UK sites

Possible effects of climate change on air quality are studied for two urban sites in the UK, London and Glasgow. Hourly meteorological data were obtained from climate simulations for two periods representing the current climate and a plausible late 21st century climate. Of the meteorological quantities relevant to air quality, significant changes were found in temperature, specific humidity, wind speed, wind direction, cloud cover, solar radiation, surface sensible heat flux and precipitation. Using these data, dispersion estimates were made for a variety of single sources and some significant changes in environmental impact were found in the future climate. In addition, estimates for future background concentrations of NO_x, NO₂, ozone and PM₁₀ upwind of London and Glasgow were made using the meteorological data in a statistical model. These showed falls in NO_x and increases in ozone for London, while a fall in NO₂ was the largest percentage change for Glasgow. Other changes were small. With these background estimates, annual-average concentrations of NO_x, NO₂, ozone and PM₁₀ were estimated within the two urban areas. For London, results averaged over a number of sites showed a fall in NO_x and a rise in ozone, but only small changes in NO₂ and PM₁₀. For Glasgow, the changes in all four chemical species were small. Large-scale background ozone values from a global chemical transport model are also presented. These show a decrease in background ozone due to climate change. To assess the net impact of both large scale and local processes will require models which treat all relevant scales.     

Summer ozone episodes in the Greater Madrid area. Analyzing the ozone response to abatement strategies by modelling

The development of ozone control strategies requires analysing the sensitivity of the dispersion model used to changes in emissions of nitrogen oxides (NO_X) and volatile organic compounds. The ozone response to variations in road traffic and total anthropogenic emissions is evaluated for two different summer ozone episodes in the Greater Madrid Area (GMA). This study uses the TVM model and a transport/chemistry module in which different chemical mechanisms (EMEP, RACM) are implemented. The results show that the areas of maximum impact and ozone responses are notably influenced by the different transport and dispersion patterns established in the area. However, the contribution of anthropogenic sources other than road traffic is patent in both episodes. Strategies based only on decreasing road traffic emissions were not sufficient for an effective control of the air quality in the GMA. Moreover, certain discrepancies observed in the predicted trends, as a response to these control strategies posed, reflect the importance of variations in the precursors balance. The ozone production regime associated to these ozone episodes and the sensitivity of the ozone response to changes in this balance has been investigated. A chemical indicator has been used to deepen in that evaluation.     

Impact of biogenic emission uncertainties on the simulated response of ozone and fine particulate matter to anthropogenic emission reductions

The role of emissions of volatile organic compounds and nitric oxide from biogenic sources is becoming increasingly important in regulatory air quality modeling as levels of anthropogenic emissions continue to decrease and stricter health-based air quality standards are being adopted. However, considerable uncertainties still exist in the current estimation methodologies for biogenic emissions. The impact of these uncertainties on ozone and fine particulate matter (PM2.5) levels for the eastern United States was studied, focusing on biogenic emissions estimates from two commonly used biogenic emission models, the Model of Emissions of Gases and Aerosols from Nature (MEGAN) and the Biogenic Emissions Inventory System (BEIS). Photochemical grid modeling simulations were performed for two scenarios: one reflecting present day conditions and the other reflecting a hypothetical future year with reductions in emissions of anthropogenic oxides of nitrogen (NOx). For ozone, the use of MEGAN emissions resulted in a higher ozone response to hypothetical anthropogenic NOx emission reductions compared with BEIS. Applying the current U.S. Environmental Protection Agency guidance on regulatory air quality modeling in conjunction with typical maximum ozone concentrations, the differences in estimated future year ozone design values (DVF) stemming from differences in biogenic emissions estimates were on the order of 4 parts per billion (ppb), corresponding to approximately 5% of the daily maximum 8-hr ozone National Ambient Air Quality Standard (NAAQS) of 75 ppb. For PM2.5, the differences were 0.1-0.25 microg/m3 in the summer total organic mass component of DVFs, corresponding to approximately 1-2% of the value of the annual PM2.5 NAAQS of 15 microg/m3. Spatial variations in the ozone and PM2.5 differences also reveal that the impacts of different biogenic emission estimates on ozone and PM2.5 levels are dependent on ambient levels of anthropogenic emissions.     

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.