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.     

Weekday/Weekend Ozone Differences: What Can We Learn from Them?

Abstract

A national analysis of weekday/weekend ozone (O₃) differences demonstrates significant variation across the country. Weekend 1-hr or 8-hr maximum O₃ varies from 15% lower than weekday levels to 30% higher. The weekend O₃ increases are primarily found in and around large coastal cities in California and large cities in the Midwest and Northeast Corridor. Both the average and the 95th percentile of the daily 1-hr and 8-hr maxima exhibit the same general pattern. Many sites that have elevated O₃ also have higher O₃ on weekends even though traffic and O₃ precursor levels are substantially reduced on weekends. Detailed studies of this phenomenon indicate that the primary cause of the higher O₃ on weekends is the reduction in oxides of nitrogen (NO_x) emissions on weekends in a volatile organic compound (VOC)-limited chemical regime. In contrast, the lower O₃ on weekends in other locations is probably a result of NO_x reductions in a NO_x-limited regime. The NO_x reduction explanation is supported by a wide range of ambient analyses and several photochemical modeling studies. Changes in the timing and location of emissions and meteorological factors play smaller roles in weekend O₃ behavior. Weekday/weekend temperature differences do not explain the weekend effect but may modify it.     

Evolution of the Magnitude and Spatial Extent of the Weekend Ozone Effect in California’s South Coast Air Basin, 1981–2000

Abstract

Since the mid-1970s, ozone (O₃) levels in portions of California’s South Coast Air Basin (SoCAB) on weekends have been as high as or higher than levels on weekdays, even though emissions of O₃ precursors are lower on weekends. Analysis of the ambient data indicates that the intensity and spatial extent of the weekend O₃ effect are correlated with day-of-week variations in the extent of O₃ inhibition caused by titration with nitric oxide (NO), reaction of hydroxyl radical (OH) with nitrogen dioxide (NO₂), and rates of O₃ accumulation. Lower NO mixing ratios and higher NO₂/oxides of nitrogen (NO_x) ratios on weekend mornings allow O₃ to begin accumulating approximately an hour earlier on weekends. The weekday/weekend differences in the duration of O₃ accumulation remained relatively constant from 1981 to 2000. In contrast, the rate of O₃ accumulation decreased by one-third to one-half over the same period; the largest reductions occurred in the central basin on weekdays. Trends in mixing ratios of O₃ precursors show a transition to lower volatile organic compound (VOC)/NO_x ratios caused by greater reductions in VOC emissions. Reductions in VOC/NO_x ratios were greater on weekdays, resulting in higher VOC/NO_x ratios on weekends relative to weekdays. Trends in VOC/NO_x ratios parallel the downward trend in peak O₃ levels, a shift in the location of peak O₃ from the central to the eastern portion of the basin, and an increase in the magnitude and spatial extent of the weekend O₃ effect.     

Major air pollutants in Bursa,Turkey: their levels,temporal changes,interactions, and sources

Bursa is one of the largest cities of Turkey and it hosts 17 organized industrial zones. Parallel to the increase in population, rapidly growing energy consumption, and increased numbers of transport vehicles have impacts on the air quality of the city. In this study, regularly calibrated automatic samplers were employed to get the levels of air pollution in Bursa. The concentrations of CH₄ and N-CH₄ as well as the major air pollutants including PM₁₀, PM_2.5, NO, NO₂, NO_x, SO₂, CO, and O₃, were determined for 2016 and 2017 calendar years. Their levels were 1641.62?±?718.25, 33.11?±?5.45, 42.10?±?10.09, 26.41?±?9.01, 19.47?±?16.51, 46.73?±?16.56, 66.23?±?32.265, 7.60?±?3.43, 659.397?±?192.73, and 51.92?±?25.63 µg/m³ for 2016, respectively. Except for O₃, seasonal concentrations were higher in winter and autumn for both years. O₃, CO, and SO₂ had never exceeded the limit values specified in the regulations yet PM₁₀, PM_2.5, and NO₂ had violated the limits in some days. The ratios of CO/NO_x, SO₂/NO_x, and PM_2.5/PM₁₀ were examined to characterize the emission sources. Generally, domestic and industrial emissions were dominated in the fall and winter seasons, yet traffic emissions were effective in spring and summer seasons. As a result of the correlation process between O_x and NO_x, it was concluded that the most important source of O_x concentrations in winter was NO_x and O₃ was in summer.     

Assessment of the Ozone-Nitrogen Oxide-Volatile Organic Compound Sensitivity of Mexico City through an Indicator-Based Approach: Measurements and Numerical Simulations Comparison

Abstract

The ozone (O₃) sensitivity to nitrogen oxides (NO_x, or nitric oxide [NO] + nitrogen dioxide [NO₂]) versus volatile organic compounds (VOCs) in the Mexico City metropolitan area (MCMA) is a current issue of scientific controversy. To shed light on this issue, we compared measurements of the indicator species O₃/NO_y (where NO_y represents the sum of NO + NO₂ + nitric acid [HNO₃] + peroxyacetyl nitrate [PAN] + others), NO_y, and the semiempirically derived O₃/NO_{z surrogate} (where NO_{z surrogate} is the derived surrogate NO_z, and NO_z represents NO_x reaction products, or NO_y – NO_x) with results of numerical predictions reproducing the transition regimes between NO_x and VOC sensitivities. Ambient air concentrations of O₃, NO_x, and NO_y were measured from April 14 to 25, 2004 in one downwind receptor site of photo-chemically aged air masses within Mexico City. MCMA-derived transition values for an episode day occurring during the same monitoring period were obtained through a series of photochemical simulations using the Multiscale Climate and Chemistry Model (MCCM). The comparison between the measured indicator species and the simulated spatial distribution of the indicators O₃/NO_y, O₃/NO_{z surrogate}, and NO_y in MCMA suggest that O₃ in this megacity is likely VOC-sensitive. This is in opposition to past studies that, on the basis of the observed morning VOC/NO_x ratios, have concluded that O₃ in Mexico City is NO_x-sensitive. Simulated MCMA-derived sensitive transition values for O₃/NO_y, hydrogen peroxide (H₂O₂)/HNO₃, and NO_y were found to be in agreement with threshold criteria proposed for other regions in North America and Europe, although the transition crossover for O₃/NO_z and O₃/HNO₃ was not consistent with values reported elsewhere. An additional empirical evaluation of weekend/weekday differences in average maximum O₃ concentrations and 6:00- to 9:00-a.m. NO_x and NO levels registered at the same site in April 2004 indirectly confirmed the above results. A preliminary conclusion is that additional reductions in NO_x emissions in MCMA might cause an increase in presently high O₃ levels.     

Processes Influencing Secondary Aerosol Formation in the San Joaquin Valley during Winter

Abstract

Air quality data collected in the California Regional PM₁₀/PM_2.5 Air Quality Study (CRPAQS) are analyzed to qualitatively assess the processes affecting secondary aerosol formation in the San Joaquin Valley (SJV). This region experiences some of the highest fine particulate matter (PM_2.5) mass concentrations in California (≤188 μg/m³ 24-hr average), and secondary aerosol components (as a group) frequently constitute over half of the fine aerosol mass in winter. The analyses are based on 15 days of high-frequency filter and canister measurements and several months of wintertime continuous gas and aerosol measurements. The phase-partitioning of nitrogen oxide (NO_x)-related nitrogen species and carbonaceous species shows that concentrations of gaseous precursor species are far more abundant than measured secondary aerosol nitrate or estimated secondary organic aerosols. Comparisons of ammonia and nitric acid concentrations indicate that ammonium nitrate formation is limited by the availability of nitric acid rather than ammonia. Time-resolved aerosol nitrate data collected at the surface and on a 90-m tower suggest that both the daytime and nighttime nitric acid formation pathways are active, and entrainment of aerosol nitrate formed aloft at night may explain the spatial homogeneity of nitrate in the SJV. NO_x and volatile organic compound (VOC) emissions plus background O₃ levels are expected to determine NO_x oxidation and nitric acid production rates, which currently control the ammonium nitrate levels in the SJV. Secondary organic aerosol formation is significant in winter, especially in the Fresno urban area. Formation of secondary organic aerosol is more likely limited by the rate of VOC oxidation than the availability of VOC precursors in winter.     

Temporal variations of fine and coarse particulate matter sources in Jeddah,Saudi Arabia

This study provides the first comprehensive analysis of the seasonal variations and weekday/weekend differences in fine (aerodynamic diameter <2.5 μm; PM_2.5) and coarse (aerodynamic diameter 2.5–10 μm; PM_2.5–10) particulate matter mass concentrations, elemental constituents, and potential source origins in Jeddah, Saudi Arabia. Air quality samples were collected over 1 yr, from June 2011 to May 2012 at a frequency of three times per week, and analyzed. The average mass concentrations of PM_2.5 (21.9 μg/m³) and PM₁₀ (107.8 μg/m³) during the sampling period exceeded the recommended annual average levels by the World Health Organization (WHO) for PM_2.5 (10 μg/m³) and PM₁₀ (20 μg/m³), respectively. Similar to other Middle Eastern locales, PM_2.5–10 is the prevailing mass component of atmospheric particulate matter at Jeddah, accounting for approximately 80% of the PM₁₀ mass. Considerations of enrichment factors, absolute principal component analysis (APCA), concentration roses, and backward trajectories identified the following source categories for both PM_2.5 and PM_2.5–10: (1) soil/road dust, (2) incineration, and (3) traffic; and for PM_2.5 only, (4) residual oil burning. Soil/road dust accounted for a major portion of both the PM_2.5 (27%) and PM_2.5–10 (77%) mass, and the largest source contributor for PM_2.5 was from residual oil burning (63%). Temporal variations of PM_2.5–10 and PM_2.5 were observed, with the elevated concentration levels observed for mass during the spring (due to increased dust storm frequency) and on weekdays (due to increased traffic). The predominant role of windblown soil and road dust in both the PM_2.5 and PM_2.5–10 masses in this city may have implications regarding the toxicity of these particles versus those in the Western world where most PM health assessments have been made in the past. These results support the need for region-specific epidemiological investigations to be conducted and considered in future PM standard setting.

Implications: Temporal variations of fine and coarse PM mass, elemental constituents, and sources were examined in Jeddah, Saudi Arabia, for the first time. The main source of PM_2.5–10 is natural windblown soil and road dust, whereas the predominant source of PM_2.5 is residual oil burning, generated from the port and oil refinery located west of the air sampler, suggesting that targeted emission controls could significantly improve the air quality in the city. The compositional differences point to a need for health effect studies to be conducted in this region, so as to directly assess the applicability of the existing guidelines to the Middle East air pollution.     

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.     

Response of Fine Particulate Matter to Emission Changes of Oxides of Nitrogen and Anthropogenic Volatile Organic Compounds in the Eastern United States

Abstract

A three-dimensional chemical transport model (Particulate Matter Comprehensive Air Quality Model with Extensions [PMCAMx]) is used to investigate changes in fine particle (PM_2.5) concentrations in response to 50% emissions changes of oxides of nitrogen (NO_x) and anthropogenic volatile organic compounds (VOCs) during July 2001 and January 2002 in the eastern United States. The reduction of NO_x emissions by 50% during the summer results in lower average oxidant levels and lowers PM_2.5 (8% on average), mainly because of reductions of sulfate (9–11%), nitrate (45–58%), and ammonium (7–11%). The organic particulate matter (PM) slightly decreases in rural areas, whereas it increases in cities by a few percent when NO_x is reduced. Reduction of NO_x during winter causes an increase of the oxidant levels and a rather complicated response of the PM components, leading to small net changes. Sulfate increases (8–17%), nitrate decreases (18– 42%), organic PM slightly increases, and ammonium either increases or decreases a little. The reduction of VOC emissions during the summer causes on average a small increase of the oxidant levels and a marginal increase in PM_2.5. This small net change is due to increases in the inorganic components and decreases of the organic ones. Reduction of VOC emissions during winter results in a decrease of the oxidant levels and a 5–10% reduction of PM_2.5 because of reductions in nitrate (4–19%), ammonium (4–10%), organic PM (12–14%), and small reductions in sulfate. Although sulfur dioxide (SO₂) reduction is the single most effective approach for sulfate control, the coupled decrease of SO₂ and NO_x emissions in both seasons is more effective in reducing total PM_2.5 mass than the SO₂ reduction alone.     

Effect of Hydrocarbon and NO x on Photochemical Smog Formation under Simulated Transport Conditions

The body of information presented in this paper is directed to those individuals concerned with the effect of urban pollution on downwind areas. Concern has been expressed over the appropriate hydrocarbon and NO _x control strategy to be used in minimizing the effects of ozone and NO₂ on urban population centers and their downwind environs. O₃ and NO₂ formation were studied in smog chamber irradiations as a function of the initial NO _x concentration at three hydrocarbon concentrations. By carrying out the irradiations for a period of time equivalent to one solar day in a continuously diluting system, smog formation in a chemically reacting pollutant system under transport was simulated. The results of this experimental simulation suggest that hydrocarbon reduction reduces O₃ in urban as well as downwind areas while NO _x reduction increases O₃ in the urban area and has little effect on O₃ in downwind areas. Both hydrocarbon and NO _x reduction will reduce atmospheric NO₂ levels, with the effect of NO _x reduction generally being more pronounced.     

Differences between Weekday and Weekend Air Pollutant Levels in Atlanta; Baltimore; Chicago; Dallas–Fort Worth; Denver; Houston; New York; Phoenix; Washington,DC; and Surrounding Areas

Abstract

We evaluated day-of-week differences in mean concentrations of ozone (O₃) precursors (nitric oxide [NO], nitrogen oxides [NO_x], carbon moNO_xide [CO], and volatile organic compounds [VOCs]) at monitoring sites in 23 states comprising seven geographic focus areas over the period 1998– 2003. Data for VOC measurements were available for six metropolitan areas in five regions. We used Wednesdays to represent weekdays and Sundays to represent weekends; we also analyzed Saturdays. At many sites, NO, NO_x, and CO mean concentrations decreased at all individual hours from 6:00 a.m. to 3:00 p.m. on Sundays compared with corresponding Wednesday means. Statistically significant (p < 0.01) weekend decreases in ambient concentrations were observed for 92% of NO_x sites, 89% of CO sites, and 23% of VOC sites. Nine-hour (6:00 a.m. to 3:00 p.m.) mean concentrations of NO, NO_x, CO, and VOCs declined by 65, 49, 28, and 19%, respectively, from Wednesdays to Sundays (median site responses). Despite the large reductions in ambient NO_x and moderate reductions in ambient CO and VOC concentrations on weekends, ozone and particulate matter (PM) nitrate did not exhibit large changes from week-days to weekends. The median differences between Wednesday and Sunday mean ozone concentrations at all monitoring sites ranged from 3% higher on Sundays for peak 8-hr concentrations determined from all monitoring days to 3.8% lower on Sundays for peak 1-hr concentrations on extreme-ozone days. Eighty-three percent of the sites did not show statistically significant differences between Wednesday and weekend mean concentrations of peak ozone. Statistically significant weekend ozone decreases occurred at 6% of the sites and significant increases occurred at 11% of the sites. Average PM nitrate concentrations were 2.6% lower on Sundays than on Wednesdays. Statistically significant Sunday PM nitrate decreases occurred at one site and significant increases occurred at seven sites.     

Assessment of nitrogen oxides and ground-level ozone behavior in a dense air quality station network: Case study in the Lesser Antilles Arc

ABSTRACT

This paper presents a study on ground-level ozone (O₃), nitrogen oxides (NO_x = NO + NO₂) concentrations, and their variabilities in the ambient air of three sites of a tropical archipelago that is moderately urbanized. Statistical analysis was performed on a quite complete (>80%) set of 5 years of measurements (2008–2012). There are few studies on those pollutants and their seasonal behavior in the Caribbean area, where pollution level and cities configuration are different from megacities. Analyses are focused on pollutant variations at the scale of the day, the week, and the seasons, using hourly data. The observations show that NO_x concentrations are more elevated during the wet season, whereas O₃ concentrations are higher in the dry season. Amplitudes of ozone cycles are strongly influenced by meteorological conditions (temperature, global radiation, and wind speed) and prevailing levels of NO_x. An ozone weekend effect is detected with the highest amplitude in the city, where anthropogenic activity is the lowest during the weekend. Due to the nature and the origin of pollutants, NO_x shows higher variability than O₃ in the time series. Our results evince the need for continuous measurements of volatile organic compounds (VOCs) in order to better quantify their contribution in O₃ formation in an insular context where numerous natural sources have been identified.

Implications: Statistical analyses of observed NO_x and O₃ concentrations for 5 years for a typical low industrialized site of the Caribbean area have been done. Air quality for those components is correct based on the standards of the World Health Orgaization, pollutant source spatial distributions, and level of industrialization. Observations show the same patterns as in megacities but also a strong impact of weather conditions and road traffic. Behaviors of O₃ cannot be fully explained without VOCs monitoring. Localization and type of AQS should be reconsidered to improve the accuracy of concentrations of the pollutant and better understand their behaviors.     

A highly resolved temporal and spatial air pollutant emission inventory for the Pearl River Delta region, China and its uncertainty assessment

A highly resolved temporal and spatial Pearl River Delta (PRD) regional emission inventory for the year 2006 was developed with the use of best available domestic emission factors and activity data. The inventory covers major emission sources in the region and a bottom–up approach was adopted to compile the inventory for those sources where possible. The results show that the estimates for SO₂, NO_x, CO, PM₁₀, PM_2.5 and VOC emissions in the PRD region for the year 2006 are 711.4 kt, 891.9 kt, 3840.6 kt, 418.4 kt, 204.6 kt, and 1180.1 kt, respectively. About 91.4% of SO₂ emissions were from power plant and industrial sources, and 87.2% of NO_x emissions were from power plant and mobile sources. The industrial, mobile and power plant sources are major contributors to PM₁₀ and PM_2.5 emissions, accounting for 97.7% of the total PM₁₀ and 97.2% of PM_2.5 emissions, respectively. Mobile, biogenic and VOC product-related sources are responsible for 90.5% of the total VOC emissions. The emissions are spatially allocated onto grid cells with a resolution of 3 km × 3 km, showing that anthropogenic air pollutant emissions are mainly distributed over PRD central-southern city cluster areas. The preliminary temporal profiles were established for the power plant, industrial and on-road mobile sources. There is relatively low uncertainty in SO₂ emission estimates with a range of −16% to +21% from power plant sources, medium to high uncertainty for the NO_x emissions, and high uncertainties in the VOC, PM_2.5, PM₁₀ and CO emissions.     

Air quality in Yanbu,Saudi Arabia

Yanbu, on the Red Sea, is an affluent Saudi Arabian industrial city of modest size. Substantial effort has been spent to balance environmental quality, especially air pollution, and industrial development. We have analyzed six years of observations of criteria pollutants O₃, SO₂, particles (PM_2.5 and PM₁₀) and the known ozone precursors—volatile organic compounds (VOCs) and nitrogen oxides (NO_x). The results suggest frequent VOC-limited conditions in which ozone concentrations increase with decreasing NO_x and with increasing VOCs when NO_x is plentiful. For the remaining circumstances ozone has a complex non-linear relationship with the VOCs. The interactions between these factors at Yanbu cause measurable impacts on air pollution including the weekend effect in which ozone concentrations stay the same or even increase despite significantly lower emissions of the precursors on the weekends. Air pollution was lower during the Eids (al-Fitr and al-Adha), Ramadan and the Hajj periods. During Ramadan, there were substantial night time emissions as the cycle everyday living is almost reversed between night and day. The exceedances of air pollution standards were evaluated using criteria from the U.S. Environmental Protection Agency (EPA), World Health Organization (WHO), the Saudi Presidency of Meteorology and Environment (PME) and the Royal Commission Environmental Regulations (RCER). The latter are stricter standards set just for Yanbu and Jubail. For the fine particles (PM_2.5), an analysis of the winds showed a major impact from desert dust. This effect had to be taken into account but still left many occasions when standards were exceeded. Fewer exceedances were found for SO₂, and fewer still for ozone. The paper presents a comprehensive view of air quality at this isolated desert urban environment.

Implications: Frequent VOC-limited conditions are found at Yanbu in Saudi Arabia that increase ozone pollution if NO_x is are reduced. In this desert environment, increased nightlife produces the highest levels of VOCs and NO_x at night rather than the day. The effects increase during Ramadan. Fine particles peak twice a day—the morning peak is caused by traffic and increases with decreasing wind, potentially representing health concerns, but the larger afternoon peak is caused by the wind, and it increases with increasing wind speeds. These features suggest that exposure to pollutants must be redefined for such an environment.     

Differences between Weekday and Weekend Air Pollutant Levels in Southern California

Abstract

Ambient air quality data were analyzed to empirically evaluate the effects of reductions of volatile organic compounds (VOCs) and oxides of nitrogen (NO_x) emissions on weekday and weekend levels of ozone (O₃; 1991–1998) and particulate NO₃ ^- (1980–1999) in southern California. Despite significantly lower O₃ precursor levels on weekends, 20 of 28 South Coast Air Basin (SoCAB) sites (28 of all 78 southern California sites) showed statistically significant higher mean O₃ levels on Sundays than on weekdays (p < 0.01); 49 of the remaining 50 sites showed no significant differences between mean weekday and Sunday peak O₃ levels. We also observed no statistically significant differences between mean weekday and weekend concentrations of particulate NO₃ ^- or nitric acid (HNO₃, the precursor of particulate NO₃ ^-). Averaged over sites, the mean Sunday NO_x and nonmethane hydrocarbon concentrations were 25–41% and 16–30% lower, respectively, than on weekdays. Site-to-site differences between weekend and weekday mean peak hourly O₃ levels were related to whether O₃ formation was limited by the availability of NO_x. A thermodynamic equilibrium model predicts that particulate NO₃ ^- levels would decrease in response to a reduction of HNO₃, and that particulate ammonium NO₃ ^- formation was not limited by the availability of ammonia. The similarity of mean weekday and weekend levels of NO₃ ^- therefore did not result from limitations on the formation of particulate NO₃ ^- from its precursor, HNO₃.     

Particulate Matter in California: Part 2—Spatial,Temporal, and Compositional Patterns of PM2.5, PM10–2.5, and PM10

Abstract

Geographic and temporal variations in the concentration and composition of particulate matter (PM) provide important insights into particle sources, atmospheric processes that influence particle formation, and PM management strategies. In the nonurban areas of California, annual-average PM_2.5 and PM₁₀ concentrations range from 3 to 10 [H9262]g/m³ and from 5 to 18 µg/m³, respectively. In the urban areas of California, annual-averages for PM_2.5 range from 7 to 30 [H9262]g/m³, with observed 24-hr peaks reaching levels as high as 160 [H9262]g/m³. Within each air basin, exceedances are a mixture of isolated events as well as periods of elevated PM_2.5 concentrations that are more prolonged and regional in nature. PM_2.5 concentrations are generally highest during the winter months. The exception is the South Coast Air Basin, where fairly high values occur throughout the year. Annual-average PM_2.5 mass, as well as the concentrations of major components, declined from 1988 to 2000. The declines are especially pronounced for the sulfate (SO₄ ^2?) and nitrate (NO₃ ^?) components of PM_2.5 and PM₁₀ and correlate with reductions in ambient levels of oxides of sulfur (SO_x) and oxides of nitrogen (NO_x). Annual averages for PM_10–2.5 and PM₁₀ exhibited similar downwind trends from 1994 to 1999, with a slightly less pronounced decrease in the coarse fraction.     

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.     

Day-of-Week Patterns of Particulate Matter and Its Chemical Components at Selected Sites in California

Abstract

This paper analyzes day-of-week variations in concentrations of particulate matter (PM) in California. Because volatile organic compounds (VOCs) and oxides of nitrogen (NO_x) are not only precursors of ozone (O₃) but also of secondary PM, it is useful to know whether the variations by day of week in these precursors are also evident in PM data. Concentrations of PM ≤10 μm (PM₁₀) and ≤2.5[H9262]m in aerodynamic diameter (PM_2.5) were analyzed. PM concentrations exhibit a general weekly pattern, with the maximum occurring late in the workweek and the minimum occurring on weekends (especially Sunday); however, this pattern does not prevail at all sites and areas. PM nitrate (NO₃ ^-) data from Size Selective Inlet (SSI) samplers in the South Coast Air Basin (SoCAB) tend to be somewhat lower on weekends compared with weekdays. During 1988–1991, the weekend average was lower than the weekday average at 8 of 13 locations, with an average decrease of 1%. During 1997–2000, the weekend average was lower than the weekday average at 10 of 13 locations, with an average decrease of 6%. The weekend averages are generally lower than weekday averages for sulfates, organic carbon, and elemental carbon. Because heavy-duty trucks typically represent a major source of elemental carbon, the weekend decrease in heavy-duty truck traffic may also result in a decrease in ambient elemental carbon concentrations.     

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.     

Analysis of the air pollution climate at a central urban background site

Measurements of air pollutants from a background site in central London are analysed. These comprise hourly data for CO, NO, NO₂, O₃, SO₂ and PM₁₀ from 1996 to 2008 and particle number count from 2001 to 2008. The data are analysed in terms of long-term trends, annual, weekly and diurnal cycles, and autocorrelation and cross-correlation functions. CO, NO and NO₂ show a typical traffic-associated pattern with two daily peaks and lesser concentrations at the weekend. Particle number count and PM₁₀ show a similar cycle, but with smaller amplitude. Ozone has an annual cycle with a maximum in May, influenced by the spring maximum in background ozone, but the diurnal and weekly cycles are dominated by losses through reaction with nitric oxide. Particle number count shows a minimum corresponding with maximum air temperatures in August, whereas the CO, NO NO₂ and SO₂ show a minimum in June/July. There is a lower particle count to NO_x ratio at the background site compared to a central London kerbside site (Marylebone Road) and a seasonal pattern in particle count to NO_x and PM₁₀ ratios consistent with loss of nanoparticles by evaporation during atmospheric transport. Sulphur dioxide peaks in the morning in summer, but at midday in winter consistent with emissions from elevated sources mixing down from aloft as the diurnal mixed layer deepens. Implications for epidemiological studies of air quality and health are discussed. Sulphur dioxide, carbon monoxide, nitric oxide and nitrogen dioxide show clear downward trends over the measurement period, PM₁₀ declines initially before levels stabilised, and ozone concentrations increased.