Weekday vs. Weekend Ambient Ozone Concentrations: Discussion and Hypotheses with Focus on Northern California

Abstract

Since the early 1970s, researchers and data analysts have reported differences between weekday and weekend ozone concentrations, with higher ozone concentrations occurring on Sundays in some locations. At that time, the phenomenon was referred to as the “Sunday effect.” In the late 1980s, additional papers focused on weekday/weekend differences in air quality in the South Coast (Los Angeles) Air Basin.

Analyses of ozone concentrations measured at a number of locations in northern California reveal that average ozone concentrations are frequently higher on weekends than on weekdays. Violations of the California 0.09 ppm 1-hour air quality standard for ozone also occur in disproportionately greater frequency on weekends. We hypothesize that this phenomenon is based largely on the differences between weekday and weekend emission patterns. We believe that the observed differences may provide information regarding which pollutant reduction strategy, NO_x or ROG control, may be more effective in reducing ambient ozone concentrations. For the northern California region, the presence of higher weekend ozone concentrations suggests the need for ROG control is greater than for NO_x control. If both NO_x and ROG are to be controlled, it is important to understand the interdependence of the two pollutants in forming ozone. With the current uncertainty and debate regarding official vehicular emission inventories, this phenomenon emphasizes the importance of using observation-based data to examine ambient pollution and emission relationships. This natural experiment of varying emissions provides an interesting test case for sophisticated air pollution model performance and evaluation.

Using a Bay Area emission inventory and an estimate of its change from weekday to weekend, combined with a generic Empirical Kinetic Modeling Approach (EKMA) diagram, we demonstrate the weekend effect. In addition, changes in the Bay Area emission inventory from 1980 to 1990, when combined with the EKMA diagram, also show why the weekend effect is more evident in the 1990s.

It is our hypothesis that the presence of the weekend effect, positive or negative, combined with changes in emission changes, provides a simple clue to whether an area is NO_xor ROG limited with respect to ozone formation.     

Trends in on-road vehicle emissions and ambient air quality in Atlanta,Georgia, USA,from the late 1990s through 2009

On-road vehicle emissions of carbon monoxide (CO), nitrogen oxides (NO_x), and volatile organic compounds (VOCs) during 1995–2009 in the Atlanta Metropolitan Statistical Area were estimated using the Motor Vehicle Emission Simulator (MOVES) model and data from the National Emissions Inventories and the State of Georgia. Statistically significant downward trends (computed using the nonparametric Theil-Sen method) in annual on-road CO, NO_x, and VOC emissions of 6.1%, 3.3%, and 6.0% per year, respectively, are noted during the 1995–2009 period despite an increase in total vehicle distance traveled. The CO and NO_x emission trends are correlated with statistically significant downward trends in ambient air concentrations of CO and NO_x in Atlanta ranging from 8.0% to 11.8% per year and from 5.8% to 8.7% per year, respectively, during similar time periods. Weather-adjusted summertime ozone concentrations in Atlanta exhibited a statistically significant declining trend of 2.3% per year during 2001–2009. Although this trend coexists with the declining trends in on-road NO_x, VOC, and CO emissions, identifying the cause of the downward trend in ozone is complicated by reductions in multiple precursors from different source sectors.

Implications:Large reductions in on-road vehicle emissions of CO and NO_x in Atlanta from the late 1990s to 2009, despite an increase in total vehicle distance traveled, contributed to a significant improvement in air quality through decreases in ambient air concentrations of CO and NO_x during this time period. Emissions reductions in motor vehicles and other source sectors resulted in these improvements and the observed declining trend in ozone concentrations over the past decade. Although these historical trends cannot be extrapolated to the future because pollutant concentration contributions due to on-road vehicle emissions will likely become an increasingly smaller fraction of the atmospheric total, they provide an indication of the benefits of past control measures.     

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.     

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.     

Expected ozone benefits of reducing nitrogen oxide (NOx) emissions from coal-fired electricity generating units in the eastern United States

On hot summer days in the eastern United States, electricity demand rises, mainly because of increased use of air conditioning. Power plants must provide this additional energy, emitting additional pollutants when meteorological conditions are primed for poor air quality. To evaluate the impact of summertime NO_x emissions from coal-fired electricity generating units (EGUs) on surface ozone formation, we performed a series of sensitivity modeling forecast scenarios utilizing EPA 2018 version 6.0 emissions (2011 base year) and CMAQ v5.0.2. Coal-fired EGU NO_x emissions were adjusted to match the lowest NO_x rates observed during the ozone seasons (April 1–October 31) of 2005–2012 (Scenario A), where ozone decreased by 3–4 ppb in affected areas. When compared to the highest emissions rates during the same time period (Scenario B), ozone increased ～4–7 ppb. NO_x emission rates adjusted to match the observed rates from 2011 (Scenario C) increased ozone by ～4–5 ppb. Finally in Scenario D, the impact of additional NO_x reductions was determined by assuming installation of selective catalytic reduction (SCR) controls on all units lacking postcombustion controls; this decreased ozone by an additional 2–4 ppb relative to Scenario A. Following the announcement of a stricter 8-hour ozone standard, this analysis outlines a strategy that would help bring coastal areas in the mid-Atlantic region closer to attainment, and would also provide profound benefits for upwind states where most of the regional EGU NO_x originates, even if additional capital investments are not made (Scenario A).

Implications: With the 8-hr maximum ozone National Ambient Air Quality Standard (NAAQS) decreasing from 75 to 70 ppb, modeling results indicate that use of postcombustion controls on coal-fired power plants in 2018 could help keep regions in attainment. By operating already existing nitrogen oxide (NO_x) removal devices to their full potential, ozone could be significantly curtailed, achieving ozone reductions by up to 5 ppb in areas around the source of emission and immediately downwind. Ozone improvements are also significant (1–2 ppb) for areas affected by cross-state transport, especially Mid-Atlantic coast regions that had struggled to meet the 75 ppb standard.     

Understanding the Effectiveness of Precursor Reductions in Lowering 8-Hr Ozone Concentrations—Part II. The Eastern United States

Abstract

Analyses of ozone (O₃) measurements in conjunction with photochemical modeling were used to assess the feasibility of attaining the federal 8-hr O₃ standard in the eastern United States. Various combinations of volatile organic compound (VOC) and oxides of nitrogen (NO_x) emission reductions were effective in lowering modeled peak 1-hr O₃ concentrations. VOC emissions reductions alone had only a modest impact on modeled peak 8-hr O₃ concentrations. Anthropogenic NO_x emissions reductions of 46–86% of 1996 base case values were needed to reach the level of the 8-hr standard in some areas. As NO_x emissions are reduced, O₃ production efficiency increases, which accounts for the less than proportional response of calculated 8-hr O₃ levels. Such increases in O₃ production efficiency also were noted in previous modeling work for central California. O₃ production in some urban core areas, such as New York City and Chicago, IL, was found to be VOC-limited. In these areas, moderate NO_x emissions reductions may be accompanied by increases in peak 8-hr O₃ levels. The findings help to explain differences in historical trends in 1- and 8-hr O₃ levels and have serious implications for the feasibility of attaining the 8-hr O₃ standard in several areas of the eastern United States.     

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.     

Sensitivity Studies of the Effects of Model Formulation on the Evaluation of Control Strategies for Photochemical Air Pollution Formation in the United Kingdom

In the OZIPP (ozone isopleth plotting package, developed by United States Environmental Protection Agency) a number of model specific assumptions with respect to chemical and physical processes are made. These assumptions are introduced into an alternative model developed at AERE Harwell, United Kingdom, in which a detailed chemistry and mixture of organic emissions is included. The impact on the AERE Harwell model results of the assumptions made in OZIPP of omitting ground removal of ozone (O₃) and peroxyacetylnitrate (PAN) and of employing an incomplete PAN chemistry and adopting a reaction rate coefficient of the key reaction NO + HO₂ → NO₂ + OH which is a factor 10 lower than the accepted value, are discussed. The composition of the organic emissions is an important model parameter, and it is shown how grouping of nonmethane hydrocarbon (NMHC) emissions into a small group of NMHC thought to be representative, often implies that O₃ and other pollutants are overestimated. The O₃ isopleth diagram for London constructed using the AERE Harwell model gives a somewhat different picture from that obtained with OZIPP. OZIPP in general predicts that NO_x control or combined hydrocarbon(HC) and NO_x control is efficient with respect to O₃ reduction whilst the AERE Harwell model predicts that HC control alone usually is more efficient than combined HC and NO_x control. Furthermore NO_x control alone may often increase the O₃ burden downwind in the AERE Harwell model.     

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.     

Real-world fuel use and gaseous emission rates for flex fuel vehicles operated on E85 versus gasoline

Flex fuel vehicles (FFVs) typically operate on gasoline or E85, an 85%/15% volume blend of ethanol and gasoline. Differences in FFV fuel use and tailpipe emission rates are quantified for E85 versus gasoline based on real-world measurements of five FFVs with a portable emissions measurement system (PEMS), supplemented chassis dynamometer data, and estimates from the Motor Vehicle Emission Simulator (MOVES) model. Because of inter-vehicle variability, an individual FFV may have higher nitrogen oxide (NO_x) or carbon monoxide (CO) emission rates on E85 versus gasoline, even though average rates are lower. Based on PEMS data, the comparison of tailpipe emission rates for E85 versus gasoline is sensitive to vehicle-specific power (VSP). For example, although CO emission rates are lower for all VSP modes, they are proportionally lowest at higher VSP. Driving cycles with high power demand are more advantageous with respect to CO emissions, but less advantageous for NO_x. Chassis dynamometer data are available for 121 FFVs at 50,000 useful life miles. Based on the dynamometer data, the average difference in tailpipe emissions for E85 versus gasoline is ?23% for NO_x, ?30% for CO, and no significant difference for hydrocarbons (HC). To account for both the fuel cycle and tailpipe emissions from the vehicle, a life cycle inventory was conducted. Although tailpipe NO_x emissions are lower for E85 versus gasoline for FFVs and thus benefit areas where the vehicles operate, the life cycle NO_x emissions are higher because the NO_x emissions generated during fuel production are higher. The fuel production emissions take place typically in rural areas. Although there are not significant differences in the total HC emissions, there are differences in HC speciation. The net effect of lower tailpipe NO_x emissions and differences in HC speciation on ozone formation should be further evaluated.

Implications: Reported comparisons of flex fuel vehicle (FFV) tailpipe emission rates for E85 versus gasoline have been inconsistent. To date, this is the most comprehensive evaluation of available and new data. The large range of inter-vehicle variability illustrates why prior studies based on small sample sizes led to apparently contradictory findings. E85 leads to significant reductions in tailpipe nitrogen oxide (NO_x) and carbon monoxide (CO) emission rates compared with gasoline, indicating a potential benefit for ozone air quality management in NO_x-limited areas. The comparison of FFV tailpipe emissions between E85 and gasoline is sensitive to power demand and driving cycles.     

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.     

On-Road,In-Use Gaseous Emission Measurements by Remote Sensing of School Buses Equipped with Diesel Oxidation Catalysts and Diesel Particulate Filters

Abstract

A remote sensing device was used to obtain on-road and in-use gaseous emission measurements from three fleets of schools buses at two locations in Washington State. This paper reports each fleet’s carbon monoxide (CO), hydrocarbon (HC), nitric oxide (NO), and nitrogen dioxide (NO₂) mean data. The fleets represent current emission retrofit technologies, such as diesel particulate filters and diesel oxidation catalysts, and a control fleet. This study shows that CO and HC emissions decrease with the use of either retrofit technology when compared with control buses of the same initial emission standards. The CO and HC emission reductions are consistent with published U.S. Environmental Protection Agency verified values. The total oxides of nitrogen (NO_x), NO, and the NO₂/NO_x ratio all increase with each retrofit technology when compared with control buses. As was expected, the diesel particulate filters emitted significantly higher levels of NO₂ than the control fleet because of the intentional conversion of NO to NO₂ by these systems. Most prior research suggests that NO_x emissions are unaffected by the retrofits; however, these previous studies have not included measurements from retrofit devices on-road and after nearly 5 yr of use. Two 2006 model-year buses were also measured. These vehicles did not have retrofit devices but were built to more stringent new engine standards. Reductions in HCs and NO_x were observed for these 2006 vehicles in comparison to other non-retrofit earlier model-year vehicles.     

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

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

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

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

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

Part I: lead peroxide candles and dustfall collectors

A diffusion flame burner was operated to determine the effect of several parameters on the quantity of NO_x and unburned hydrocarbons produced. The statistical analysis indicated the unburned hydrocarbon emissions to be dependent upon the rate of heat release in the system, the amount of excess combustion air, the fuel molecular structure, and the interaction between the fuel structure and the amount of excess air. Analysis of the NO_x emissions, after an adjustment to a common temperature to eliminate the temperature effect, showed them to be dependent upon the fuel molecular structure and the amount of excess air. The NO_x emissions reached a maximum at the conditions which yielded minimum unburned hydrocarbon emissions. Multiple regressions were made which yielded predicting equations for both the unburned hydrocarbon and the NO_x for the apparatus used.     

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.     

Cost-Effective Reduction of NOx Emissions from Electricity Generation

ABSTRACT

This paper analyzes the benefits and costs of policies to reduce NO_x emissions from electricity generation in the United States. Because emissions of NOx contribute to the high concentration of atmospheric ozone in the eastern states associated with health hazards, the U.S. Environmental Protection Agency (EPA) has called on eastern states to formulate state implementation plans (SIPs) for reducing NO_x emissions. Our analysis considers three NO_x reduction scenarios: a summer seasonal cap in the eastern states covered by EPA's NO_x SIP Call, an annual cap in the same SIP Call region, and a national annual cap. All scenarios allow for emissions trading. Although EPA's current policy is to implement a seasonal cap in the SIP Call region, this analysis indicates that an annual cap in the SIP Call region would yield about $400 million more in net benefits (benefits less costs) than would a seasonal policy, based on particulate-related health effects only. An annual cap in the SIP Call region is also the policy that is most likely to achieve benefits in excess of costs. Consideration of omissions from this accounting, including the potential benefits from reductions in ozone concentrations, strengthens the finding that an annual program offers greater net benefits than does a seasonal program.     

Comparison of the MOVES2010a,MOBILE6.2, and EMFAC2007 mobile source emission models with on-road traffic tunnel and remote sensing measurements

The Desert Research Institute conducted an on-road mobile source emission study at a traffic tunnel in Van Nuys, California, in August 2010 to measure fleet-averaged, fuel-based emission factors. The study also included remote sensing device (RSD) measurements by the University of Denver of 13,000 vehicles near the tunnel. The tunnel and RSD fleet-averaged emission factors were compared in blind fashion with the corresponding modeled factors calculated by ENVIRON International Corporation using U.S. Environmental Protection Agency's (EPA's) MOVES2010a (Motor Vehicle Emissions Simulator) and MOBILE6.2 mobile source emission models, and California Air Resources Board's (CARB's) EMFAC2007 (EMission FACtors) emission model. With some exceptions, the fleet-averaged tunnel, RSD, and modeled carbon monoxide (CO) and oxide of nitrogen (NO_x) emission factors were in reasonable agreement (±25%). The nonmethane hydrocarbon (NMHC) emission factors (specifically the running evaporative emissions) predicted by MOVES were insensitive to ambient temperature as compared with the tunnel measurements and the MOBILE- and EMFAC-predicted emission factors, resulting in underestimation of the measured NMHC/NO_x ratios at higher ambient temperatures. Although predicted NMHC/NO_x ratios are in good agreement with the measured ratios during cooler sampling periods, the measured NMHC/NO_x ratios are 3.1, 1.7, and 1.4 times higher than those predicted by the MOVES, MOBILE, and EMFAC models, respectively, during high-temperature periods. Although the MOVES NO_x emission factors were generally higher than the measured factors, most differences were not significant considering the variations in the modeled factors using alternative vehicle operating cycles to represent the driving conditions in the tunnel. The three models predicted large differences in NO_x and particle emissions and in the relative contributions of diesel and gasoline vehicles to total NO_x and particulate carbon (TC) emissions in the tunnel.

Implications: Although advances have been made to mobile source emission models over the past two decades, the evidence that mobile source emissions of carbon monoxide and hydrocarbons in urban areas were underestimated by as much as a factor of 2–3 in past inventories underscores the need for on-going verification of emission inventories. Results suggest that there is an overall increase in motor vehicle NMHC emissions on hot days that is not fully accounted for by the emission models. Hot temperatures and concomitant higher ratios of NMHC emissions relative to NO_x both contribute to more rapid and efficient formation of ozone. Also, the ability of EPA's MOVES model to simulate varying vehicle operating modes places increased importance on the choice of operating modes to evaluate project-level emissions.     

Diurnal and Weekday Variations in the Source Contributions of Ozone Precursors in California’s South Coast Air Basin

Abstract

For at least 30 years, ozone (O₃) levels on weekends in parts of California’s South Coast (Los Angeles) Air Basin (SoCAB) have been as high as or higher than on weekdays, even though ambient levels of O₃ precursors are lower on weekends than on weekdays. A field study was conducted in the Los Angeles area during fall 2000 to test whether proposed relationships between emission sources and ambient nonmethane hydrocarbon (NMHC) and oxides of nitrogen (NO_x) levels can account for observed diurnal and day-of-week variations in the concentration and proportions of precursor pollutants that may affect the efficiency and rate of O₃ formation. The contributions to ambient NMHC by motor vehicle exhaust and evaporative emissions, estimated using chemical mass balance (CMB) receptor modeling, ranged from 65 to 85% with minimal day-of-week variation. Ratios of ambient NO_x associated with black carbon (BC) to NO_x associated with carbon monoxide (CO) were approximately 1.25 ± 0.22 during weekdays and 0.76 ± 0.07 and 0.52 ± 0.07 on Saturday and Sunday, respectively. These results demonstrate that lower NO_x emissions from diesel exhaust can be a major factor causing lower NO_x mixing ratios and higher NMHC/NO_x ratios on weekends. Nonmobile sources showed no significant day-of-week variations in their contributions to NMHC. Greater amounts of gasoline emissions are carried over on Friday and Saturday evenings but are, at most, a minor factor contributing to higher NMHC/NO_x ratios on weekend mornings.     

Climatic forcing of nitrogen oxides through changes in tropospheric ozone and methane; global 3D model studies

A three-dimensional global chemical tracer model and a radiation transfer model have been used to study the role of NO_x emissions for radiative forcing of climate. Through production of tropospheric O₃, NO_x emissions lead to positive radiative forcing and warming. But by affecting the concentration of OH radicals, NO_x also reduces the levels of CH₄, thereby giving negative forcing and cooling. The lifetime of NO_x varies from hours to days, giving large spatial variations in the levels of NO_x. We have selected geographical regions representing different chemical and physical conditions, and chemical and radiative effects of reducing NO_x emissions by 20% in each region are studied. Due to nonlinearities in the O₃ chemistry as well as differences in convective activity, there are large geographical differences in the effect of NO_x on O₃ as well as variations in the annual profile of the changes. The effect of NO_x emissions on methane is also found to depend on the localisation of the emissions. The calculated ozone and methane forcing are of similar magnitude but of opposite sign. The methane effect acts on a global scale with a delay of approximately a decade, while the ozone effect is of regional character and occurs during weeks.