The Effect of NMOC and Ozone Aloft on Modeled Urban Ozone Production and Control Strategies

Carbon bond (CB-III) fractions for non-methane organic carbon compounds (NMOC) measured in the background alrmass adverted into several urban areas in the eastern and southern United States are reported. These, together with ozone measured aloft, were used In an Empirical Kinetic Modeling Approach (EKMA) to model urban ozone production and urban ozone control strategies.

Over a range of zero to double the mean of the measured NMOC concentrations aloft (0 to 70 ppbC) and zero to the highest ozone levels recorded aloft (0 to 65 ppb), it was found that urban ozone production and control strategies were relatively insensitive to NMOC from aloft. However, urban ozone production was sensitive to ozone from aloft, while ozone control strategies were insensitive to ozone from aloft.     

Assessing multi-year changes in modeled and observed urban NOX concentrations from a dynamic model evaluation perspective

An investigation of the concentrations of nitrogen oxides (NO_X) from an air quality model and observations at monitoring sites was performed to assess the changes in NO_X levels attributable to changes in mobile emissions. This evaluation effort focused on weekday morning rush hours since urban NO_X concentrations are strongly influenced by the significant loading of emissions associated with heavy commuter traffic. On-road vehicle NO_X emissions generated by the MOBILE6 model revealed a steady decline with an overall decrease of 25% for 2002–2006. In this study, a dynamic model evaluation was undertaken that entails an assessment of the predicted concentration response of the Community Multiscale Air Quality (CMAQ) model due to changes in NO_X emissions as well as to meteorological variability spanning 3-month summer periods over five consecutive years (2002–2006) against observed concentration changes at NO_X monitoring sites located primarily in urban areas of the eastern United States. Both modeled and observed hourly NO_X concentrations exhibited maximum values that coincided with the morning peak NO_X emissions. The notable results, based on 3-h average (6–9 AM local time) NO_X concentrations, derived between the 50th and 95th percentiles of cumulative concentration distributions, revealed that modeled changes at these elevated NO_X levels generally tracked the year-to-year variations in the observed concentration changes. When summer 2002 values were used as a reference, both modeled and observed results also showed definitive decreases in weekday morning urban NO_X concentrations over this multi-year period, which can be primarily attributed to the reductions in mobile source emissions. Whereas observed NO_X concentrations have declined by about 25% over this period consistent with the decline in the modeled mobile emission sector, modeled NO_X concentration changes were close to the decreases exhibited in all (mobile + other sectors) surface NO_X emissions whose overall decline was about 15% over this multi-year period.     

A diagnostic comparison of measured and model-predicted speciated VOC concentrations

This study compares speciated model-predicted concentrations (i.e., mixing ratios) of volatile organic compounds (VOCs) with measurements from the Photochemical Assessment Monitoring Stations (PAMS) network at sites within the northeastern US during June–August of 2006. Measurements of total non-methane organic compounds (NMOC), ozone (O₃), oxides of nitrogen (NO_x) and reactive nitrogen species (NO_y) are used for supporting analysis. The measured VOC species were grouped into the surrogate classes used by the Carbon Bond IV (CB4) chemical mechanism. It was found that the model typically over-predicted all the CB4 VOC species, except isoprene, which might be linked to overestimated emissions. Even with over-predictions in the CB4 VOC species, model performance for daily maximum O₃ was typically within ±15%. Analysis at an urban site in NY, where both NMOC and NO_x data were available, suggested that the reasonable ozone performance may be possibly due to compensating overestimated NO_x concentrations, thus modulating the NMOC/NO_x ratio to be in similar ranges as that of observations.     

NMOC,ozone, and organic aerosol in the southeastern United States, 1999–2007: 1. Spatial and temporal variations of NMOC concentrations and composition in Atlanta,Georgia

Volatile organic compounds (VOCs) are emitted from anthropogenic and natural (biogenic) sources into the atmosphere. Characterizing their ambient mixing ratios or concentrations is a challenge because VOCs comprise hundreds of species, and accurate measurements are difficult. Long-term hourly and daily-resolution data have been collected in the metropolitan area of Atlanta, Georgia, a major city dominated by motor vehicle emissions. A series of observations of daily, speciated C₂–C₁₀ non-methane organic compounds (NMOC) and oxygenated hydrocarbons (OVOC) in mid-town Atlanta (Jefferson Street, JST) are compared with data from three urban-suburban sites and a nearby non-urban site. Annual-average mixing ratios of NMOC and OVOC at JST declined from 1999 through 2007. Downward trends in NMOC, CO, and NO_y corroborate expected emission changes as reflected in emission inventories for Atlanta’s Fulton County. Comparison of the JST NMOC composition with data from roadside and tunnel sampling reveals similarities to motor vehicle dominated samples. The JST annual average VOC-OH reactivities from 1999 to 2007 were relatively constant compared with the decline in annual-average NMOC mixing ratios. Mean reactivity at JST, in terms of concentration*k_OH, was approximately 40% alkenes, 22% aromatics, 16% isoprene and 6% other biogenics, 13% C₇–C₁₀ alkanes and 3% C₂-C₆ alkanes, indicating that biogenic NMOCs are important but not dominant contributors to the urban reactive NMOC mix. In contrast, isoprene constituted ～50% of the VOC-OH reactivities at two non-urban sites. Ratios of 24-hour average CO/benzene, CO/isopentane, and CO/acetylene concentrations indicate that such species are relatively conserved, consistent with their low reactivity. Ratios of more-reactive to less-reactive species show diurnal variability largely consistent with expected emission patterns, transport and mixing of air, and chemical processing.     

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

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

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

Modeling wintertime particulate matter formation in central California

A wintertime episode during the 2000 California Regional PM Air Quality Study (CRPAQS) was simulated with the air quality model CMAQ–MADRID. Model performance was evaluated with 24-h average measurements available from CRPAQS. Modeled organic matter (OM) was dominated by emissions, which were probably significantly under-represented, especially in urban areas. In one urban area, modeled daytime nitrate concentrations were low and evening concentrations were high. This diurnal profile was not explained by the partition of nitrate between the gas and particle phases, because gaseous nitric acid concentrations were low compared to PM nitrate. Both measured and simulated nitrate concentrations aloft were lower than at the surface at two tower locations during this episode. Heterogeneous reactions involving NO₃ and N₂O₅ accounted for significant nitrate production in the model, resulting in a nighttime peak. The sensitivity of PM nitrate to precursor emissions varied with time and space. Nitrate formation was on average sensitive to NO_x emissions. However, for some periods at urban locations, reductions in NO_x caused the contrary response of nitrate increases. Nitrate was only weakly sensitive to reductions in anthropogenic VOC emissions. Nitrate formation tended to be insensitive to the availability of ammonia at locations with high nitrate, although the spatial extent of the nitrate plume was reduced when ammonia was reduced. Reductions in PM emissions caused OM to decrease, but had no effect on nitrate despite the role of heterogeneous reactions. A control strategy that focuses on NO_x and PM emissions would be effective on average, but reductions in VOC and NH₃ emissions would also be beneficial for certain times and locations.     

Ozone Control Strategies Based on the Ratio of Volatile Organic Compounds to Nitrogen Oxides

The 1990 Clean Air Act Amendments require states with O₃ nonattainment areas to adopt regulations to enforce reasonable available control technologies (RACT) for NO_X stationary sources by November 1992. However, if the states can demonstrate that such measures will have an adverse effect on air quality, NO_X requirements may be waived. To assist the states in making this decision, the U.S. EPA is attempting to develop guidelines for the states to use in deciding whether NO_X reductions will have a positive or negative impact on O3 air quality. Although NO_X is a precursor of O₃, at low VOC/NO_X ratios, the reduction of NO_X can result in increased peak O₃. EPA is examining existing information on VOC/NO_X ratios to develop “rules of thumb” to guide the states in their decision-making process. An examination of 6 a.m. to 9 a.m. VOC/NO_X ratios at a number of sites in the eastern U.S. indicates that the ratio is highly variable from day-to-day and there is no apparent relationship between ratios measured at different sites within the same area. In addition, statistical analysis failed to identify significant relationships between the 6 a.m. to 9 a.m. VOC/NO_X ratio and the maximum 1-hr. O₃ within a given area. Since we know from smog chamber and modeling studies that such a relationship exists, this further invalidates the assumption that a ratio measured at a single site is representative of the ratio for the entire region. Based on this Information, we conclude that having the 6 a.m. to 9 a.m. ambient VOC/NO_X ratio for a given area is insufficient information, by itself, to decide whether a VOC-alone, a NO_x-alone, or a combined VOC-NO_X reduction strategy is a viable or optimum O₃-reduction strategy.     

NMOC,ozone, and organic aerosol in the southeastern United States, 1999–2007: 2. Ozone trends and sensitivity to NMOC emissions in Atlanta,Georgia

Non-methane organic carbon (NMOC) measurements made in Atlanta, Georgia from 1999–2007 are used with nitrogen oxide (NO_x or NO_y) and ozone (O₃) data to investigate relationships between O₃ precursors and peak 8-hour O₃ concentrations in the city. Data from a WNW-to-ENE transect of sites illustrate that the mean urban peak 8-hour O₃ excess constitutes about 20% of the peak 8-hour O₃ measured at the area-wide maximum O₃ site when air-mass movement is from the northwest quadrant; local influence is potentially greater on days with more stagnation or recirculation. The peak 8-hour O₃ concentrations in Atlanta increase as (1) surface temperature (T), ambient NMOC and NO_y concentrations, and previous-day peak O₃ concentrations increase, and as (2) relative humidity, surface wind speeds, and ratios of NMOC-to-NO_y decrease. An observation-based statistical model is introduced to relate area-wide peak 8-hour O₃ concentrations to ambient NMOC and NO_y concentrations, while accounting for the non-linear dependences of peak 8-hour O₃ concentrations on meteorological factors. On the majority of days when the area-wide peak 8-hour O₃ exceeds 75 ppbv, meteorologically-adjusted peak 8-hour O₃ concentrations increase as ambient NMOC concentrations increase (NMOC sensitive) and ambient NO_y concentrations decrease. This result contrasts with regional conditions in which O₃ formation appears to be NO_x-sensitive in character. The results offer observationally-based information of relevance to O₃ management strategies in the Atlanta area, potentially contributing to “weight-of-evidence” assessments.     

Trend analysis of urban NO2 concentrations and the importance of direct NO2 emissions versus ozone/NOx equilibrium

The annual air quality standard of NO₂ is often exceeded in urban areas near heavy traffic locations. Despite significant decrease of NO_x emissions in 1986–2005 in the industrial and harbour area near Rotterdam, NO₂ concentrations at the urban background remain at the same level since the end of the nineties. Trend analysis of monitoring data revealed that the ozone/NO_x equilibrium is a more important factor than increasing direct NO₂ emissions by traffic. The latter has recently been identified as an additional NO₂ source due to the introduction of oxy-catalytic converters in diesel vehicles and the growing number of diesel vehicles. However, in Rotterdam over the period 1986–2005 direct NO₂ emissions by road traffic only increased 3–4%. Due to the importance of the ozone/NO_x equilibrium, it is concluded that local NO_x emissions in Rotterdam need substantial reduction to achieve lower NO₂ urban background levels. This is a relatively costly abatement strategy and, therefore, a “hotspot” approach aiming at reducing NO_x emissions by local traffic measures is more effective to meet European air quality standards.     

Development of Instrumentation for Continuous On-line Monitoring of Non-Methane Organic Carbon in Air Emissions

ABSTRACT

Non-methane organic carbon (NMOC) is a measure of total organic carbon in an air emission, excluding that from methane. Thus, it measures the total amount of carbon, irrespective of the structure and functional groups in the molecule. The U.S. Environmental Protection Agency (EPA) Method 25 is used for quantification of NMOC in emission sources and in ambient air. This method involves laboratory analysis of collected air samples and cannot be used for real-time measurements. It is prone to interferences from CO₂, CH₄, and CO, as well as moisture. In this paper, a novel method for continuous, on-line monitoring of NMOC in air emissions and ambient air is presented. Detection limits are at ppb levels, and interference of permanent gases have been eliminated.     

Shock Wave Cleaning of Air Filters

The trends in and relationships between ambient air concentrations of sulfur dioxide and sulfate aerosols at 48 urban sites and 27 nonurban sites throughout the U.S. between 1963 and 1972 have been analyzed. The substantial decreases in ambient SO₂ concentrations measured at urban sites in the eastern and midwestern U.S. are consistent with the corresponding reductions in local SO₂ emissions, but these decreases have been accompanied by only modest decreases in ambient sulfate concentrations. Large differences in the amounts of SO₂ emitted within individual air quality control regions are associated with much smaller differences in the corresponding ambient sulfate concentrations. Substantial changes in the patterns of SO₂ emissions between air quality regions result in essentially no differences between ambient sulfate concentrations in those air quality regions. Comparisons of several air quality regions in the eastern and western U.S. with similar SO₂ emission levels and patterns of emissions clearly demonstrates the higher ambient sulfate concentration levels in eastern air quality control regions. Relationships between SO₂, sulfates, and vanadium concentrations at eastern nonurban U.S. sites cannot be explained by local emission sources. These various observed results can be best explained by long distance sulfur oxide transport with chemical conversion of SO₂ to sulfates occurring over ranges of hundreds of kilometers. This conclusion has been suggested earlier and the present analysis strongly supports previous discussions. An impact of long range transport of sulfates is to emphasize the need for Consistent strategies for reduction of sulfur oxides throughout large geographical regions. Additions of large capacities involving elevated sources in mid-continental or western regions could result in significant increases in sulfate concentrations well downwind of such sources. Some of the types of research activities required to quantitate crucial experimental parameters are discussed.     

The sensitivity of modeled ozone to the temporal distribution of point, area, and mobile source emissions in the eastern United States

Ozone remains one of the most recalcitrant air pollution problems in the US. Hourly emissions fields used in air quality models (AQMs) generally show less temporal variability than corresponding measurements from continuous emissions monitors (CEM) and field campaigns would imply. If emissions control scenarios to reduce emissions at peak ozone forming hours are to be assessed with AQMs, the effect of emissions' daily variability on modeled ozone must be understood. We analyzed the effects of altering all anthropogenic emissions' temporal distributions by source group on 2002 summer-long simulations of ozone using the Community Multiscale Air Quality Model (CMAQ) v4.5 and the Carbon Bond IV (CBIV) chemical mechanism with 12 km resolution. We find that when mobile source emissions were made constant over the course of a day, 8-h maximum ozone predictions changed by ±7 parts per billion by volume (ppbv) in many urban areas on days when ozone concentrations greater than 80 ppbv were simulated in the base case. Increasing the temporal variation of point sources resulted in ozone changes of +6 and −6 ppbv, but only for small areas near sources. Changing the daily cycle of mobile source emissions produces substantial changes in simulated ozone, especially in urban areas at night; results suggest that shifting the emissions of NO_x from day to night, for example in electric powered vehicles recharged at night, could have beneficial impacts on air quality.     

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.     

An empirical model for predicting urban roadside nitrogen dioxide concentrations in the UK

An annual mean concentration of 40 μg m⁻³ has been proposed as a limit value within the European Union Air Quality Directives and as a provisional objective within the UK National Air Quality Strategy for 2010 and 2005, respectively. Emissions reduction measures resulting from current national and international policies are likely to deliver significant reductions in emissions of oxides of nitrogen from road traffic in the near future. It is likely that there will still be exceedances of this target value in 2005 and in 2009 if national measures are considered in isolation, particularly at the roadside. It is envisaged that this `policy gap’ will be addressed by implementing local air quality management to reduce concentrations in locations that are at risk of exceeding the objective. Maps of estimated annual mean NO₂ concentrations in both urban background and roadside locations are a valuable resource for the development of UK air quality policy and for the identification of locations at which local air quality management measures may be required. Maps of annual mean NO₂ concentrations at both background and roadside locations for 1998 have been calculated using modelling methods, which make use of four mathematically straightforward, empirically derived linear relationships. Maps of projected concentrations in 2005 and 2009 have also been calculated using an illustrative emissions scenario. For this emissions scenario, annual mean urban background NO₂ concentrations in 2005 are likely to be below 40 μg m⁻³, in all areas except for inner London, where current national and international policies are expected to lead to concentrations in the range 40–41 μg m⁻³. Reductions in NO_x emissions between 2005 and 2009 are expected to reduce background concentrations to the extent that our modelling results indicate that 40 μg m⁻³ is unlikely to be exceeded in background locations by 2009. Roadside NO₂ concentrations in urban areas in 2005 and 2009 are expected to be significantly higher than in background locations. 21% of urban major road links are expected to have roadside NO₂ greater than or equal to 40 μg m⁻³ in 2005 for our illustrative emissions scenario. The continuing downward trend in traffic emissions is likely to further reduce the number of links exceeding this value by 2009, with about 6% of urban major road links predicted to have concentrations higher than 40 μg m⁻³. The majority of these links are in the London area. The remaining links are generally confined to the most heavily trafficked roads in other big cities.     

Comparison of Air Pollutant Emissions from Vaporizing and Air Atomizing Waste Oil Heaters

Information presented in this paper is directed to individuals concerned with emissions from combustion of waste crankcase oil for space heating. Studies were performed to characterize gaseous and particulate emissions and vaporizing pot solid residues resulting from the combustion of waste crankcase oil. Two types of waste oil burners were tested. One was a vaporizing oil burner rated at 35.2 kW (120,000 Btu/h heat input), and the other was an air atomizing oil burner rated at 73.3 kW (250,000 Btu/h heat input). Except for NO_X and SO_X, gaseous emissions were similar to those from conventional distillate oil combustion. NO_X and SO_X emissions were higher due to higher fuel nitrogen and sulfur concentrations. Waste oil from automotive use showed higher inorganic levels than crankcase oil used for truck engine lubrication. Both burner types discharged high levels of metallic species, but the air atomizing unit had much higher stack emission levels than did the vaporizing pot system. Also, particulate loading levels were an order of magnitude higher for the air atomizing burner than for the vaporizing pot burner when firing the waste oils. However, the vaporizing pot burner generated a waste residue containing the majority of its elemental emissions. Elements which exceeded threshold limit values for one or both heaters were cadmium, chromium, cobalt, copper, iron, lead, nickel, phosphorus, and zinc. However, the nickel and much of chromium appeared to be a sampling artifact caused by the stainless steel sampling system.     

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.     

Comparison of the SCAQS Tunnel Study with Other On Road Vehicle Emission Data

The Van Nuys Tunnel experiment conducted in 1987 by Ingalls et al. (see A&WMA Paper 89-137.3), to verify automotive emission inventories as part of the Southern California Air Quality Study (SCAQS), gave higher CO and HC emission-rate values than expected on the basis of automotive-emission models—by factors of approximately 3 and 4, respectively. The CO/NO_X and HC/NO_X emission-rate ratios moreover were higher than expected—by similar factors (NO_X emission rates were about as expected). The purpose of the present paper is to review the literature on dynamometer and on-road (in tunnels and along roadways) testing of in-use vehicles, and on urban-air CO/HC/NO_X concentration ratios, to see whether the Van Nuys Tunnel results are reasonable in terms of previous experience. The conclusions are that (1) on-road CO and HC emissions higher than expected have been reported before, (2) on-road CO and HC emissions consistent with the Van Nuys Tunnel results have been reported before, and (3) on-road CO/NO_X and HC/NO_X emission-rate ratios higher than expected have been reported before. The Van Nuys Tunnel NO_X results actually are lower than in other on-road experiments, and the CO/NO_X and HC/NO_X ratios consequently are higher. The higher-than-predicted CO/NO_X and HC/NO_X ratios at Van Nuys and other on-road sites suggest richer operation on-road than predicted or than observed in the inuse- vehicle dynamometer tests which serve as the model inputs. Support for these suggestions and conclusions is found in comparison of urban-air and emission-inventory HC/NO_X ratios.     

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.     

Air Quality Modeling of Interpollutant Trading for Ozone Precursors in an Urban Area

Abstract

Emission trading is a market‐based approach designed to improve the efficiency and economic viability of emission control programs; emission trading has typically been confined to trades among single pollutants. Interpollutant trading (IPT), as described in this work, allows for trades among emissions of different compounds that affect the same air quality end point, in this work, ambient ozone (O₃) concentrations. Because emissions of different compounds impact air quality end points differently, weighting factors or trading ratios (tons of emissions of nitrogen oxides (NO_x) equivalent to a ton of emissions of volatile organic compounds [VOCs]) must be developed to allow for IPT. In this work, IPT indices based on reductions in O₃ concentrations and based on reductions in population exposures to O₃ were developed and evaluated using a three‐dimensional gridded photochemical model for Austin, TX, a city currently on the cusp of nonattainment with the National Ambient Air Quality Standards for O₃ concentrations averaged over 8 hr. Emissions of VOC and NO_x from area and mobile sources in Austin are larger than emissions from point sources. The analysis indicated that mobile and area sources exhibited similar impacts. Trading ratios based on maximum O₃ concentration or population exposure were similar. In contrast, the trading ratios did exhibit significant (more than a factor of two) day‐to‐day variability. Analysis of the air quality modeling indicated that the daily variability in trading ratios could be attributed to daily variations in both emissions and meteorology.     

Comparative evaluation of nitrogen oxides and ozone passive diffusion tubes for exposure studies

Passive diffusion tubes are recognised as a cost-effective sampling method for characterising the spatial variability, as well as the seasonal and annual trends, of NO₂ concentrations in urban areas. In addition, NO_X and O₃ passive diffusion tubes have been developed and deployed in urban and rural areas. Despite their many advantages (e.g. low operational and analysis cost, small size and no need for power supply), they have certain limitations mainly related to their accuracy and precision. In particular, the absorbent solution used, the length of the exposure period, the exact location and use of protective devices, and other environmental conditions (e.g. wind, ambient temperature and relative humidity) may have a significant impact on the performance of passive diffusion tubes. The aim of this study is to evaluate the performance of co-located NO₂, NO_X and O₃ diffusion tubes in an urban environment.A one-year passive sampling campaign was carried out in Birmingham (UK) for this purpose. NO₂, NO_X and O₃ diffusion tubes (including triplicate sets of each) were co-located at one urban background and two roadside permanent air quality monitoring stations equipped with standard gas analysers. In addition, meteorological data, such as wind speed and direction, ambient temperature and relative humidity, were obtained during the same period of time. A thorough QA/QC procedure, including storage and laboratory blanks was followed throughout the campaign. The analysis of results showed a very good agreement of NO₂ passive samplers with co-located chemiluminescence analysers, but substantial underestimations of total NO_X levels by the diffusion tubes. The O₃ diffusion sampler appeared to marginally overestimate the automatic UV analyser results, especially during warm weather periods.