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.     

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.     

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.     

Ground level ozone concentrations and its association with NOx and meteorological parameters in Kathmandu valley, Nepal

This paper summarizes the results of a yearlong continuous measurements of gaseous pollutants, NO, NO₂, NO_x and O₃ in the ambient air at Kathmandu valley. Measured concentration of the pollutants in study area is a function of time. NO, NO₂ and O₃ peak occurred in succession in presence of sunlight. At the time of maximum O₃ concentration most of the NO_x are utilized. The diurnal cycle of ground level ozone concentrations, revealed mid-day peak with lower nocturnal concentrations and inverse relationship exists between O₃ and NO_x, which are evidences of photochemical O₃ formation. The observed ground level ozone during monsoon is slight lower than the pre-monsoon value. Further, lack of rainfall and higher temperature, solar radiation in the pre-monsoon have given rise to the gradual build up of ozone and it is lowest during winter. Ground level ozone concentrations measured during bandha (general strike) and weekend are 19% and 13% higher than those measured during weekdays. The most effective ozone abatement strategy for Kathmandu Valley may be control of NO_x emissions.     

Measurement of surface ozone and its precursors in an urban area in South Brazil

Weekly and seasonal variations of surface ozone and their precursors – nitrogen oxides, carbon monoxide-associated with meteorological parameters (wind direction, temperature, solar radiation) – are reported. Measurements were performed continuously during 2006 at two sampling stations located in the metropolitan area of Porto Alegre, Brazil. Results have shown that O₃ concentrations remained almost constant between weekdays. Levels of NO_x precursors decreased especially on Sundays, due to lighter traffic. The seasonal variation has shown a maximum O₃ concentration during summer and spring while NO_x and NO₂ have maxima at the colder months. The daily cycle of highest ozone concentrations reveals a lower nightly level and an inverse relation between O₃ and NO_x, evidencing the photochemical formation of O₃. There are seasonal variation and source heterogeneity.     

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.     

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.     

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.     

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.     

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.     

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.     

Differences in airborne particle and gaseous concentrations in urban air between weekdays and weekends

Airborne particle number concentrations and size distributions as well as CO and NO_x concentrations monitored at a site within the central business district of Brisbane, Australia were correlated with the traffic flow rate on a nearby freeway with the aim of investigating differences between weekday and weekend pollutant characteristics. Observations over a 5-year monitoring period showed that the mean number particle concentration on weekdays was (8.8±0.1)×10³ cm⁻³ and on weekends (5.9±0.2)×10³ cm⁻³—a difference of 47%. The corresponding mean particle number median diameters during weekdays and weekends were 44.2±0.3 and 50.2±0.2 nm, respectively. The differences in mean particle number concentration and size between weekdays and weekends were found to be statistically significant at confidence levels of over 99%. During a 1-year period of observation, the mean traffic flow rate on the freeway was 14.2×10⁴ and 9.6×10⁴ vehicles per weekday and weekend day, respectively—a difference of 48%. The mean diurnal variations of the particle number and the gaseous concentrations closely followed the traffic flow rate on both weekdays and weekends (correlation coefficient of 0.86 for particles). The overall conclusion, as to the effect of traffic on concentration levels of pollutant concentration in the vicinity of a major road (about 100 m) carrying traffic of the order of 10⁵ vehicles per day, is that about a 50% increase in traffic flow rate results in similar increases of CO and NO_x concentrations and a higher increase of about 70% in particle number concentration.     

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

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

Photochemical production of ozone and control strategy for Southern Taiwan

An observation-based method (OBM) is developed to evaluate the ozone (O₃) production efficiency (O₃ molecules produced per NO_x molecule consumed) and O₃ production rate (P(O₃)) during a field campaign in southern Taiwan. The method can also provide an estimate of the concentration of OH. A key step in the method is to use observed concentrations of two aromatic hydrocarbons, namely ethylbenzene and m,p-xylene, to estimate the degree of photochemical processing and amounts of photochemically consumed NO_x and NMHCs by OH. In addition, total oxidant (O₃+NO₂) instead of O₃ itself turns out to be very useful for representing ozone production in the OBM approach. The average O₃ production efficiency during the field campaign in Fall (2003) is found to be about 10.2±3.9. The relationship of P(O₃) with NO_x is examined and compared with a one-dimensional (1D) photochemical model. Values of P(O₃) derived from the OBM are slightly lower than those calculated in the 1D model. However, OH concentrations estimated by the OBM are about a factor of 2 lower than the 1D model. Fresh emissions, which affect the degree of photochemical processing appear to be a major cause of the underestimate. We have developed a three-dimensional (3D) OBM O₃ production diagram that resembles the EKMA ozone isopleth diagram to study the relationship of the total oxidant versus O₃ precursors. The 3D OBM O₃ production diagram suggests that reducing emissions of NMHCs are more effective in controlling O₃ than reducing NO_x. However, significant uncertainties remain in the OBM, and considerable more work is required to minimize these uncertainties before a definitive control strategy can be reached. The observation-based approach provides a good alternative to measuring peroxy radicals for evaluating the production of O₃ and formulating O₃ control strategy in urban and suburban environments.     

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.     

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.     

Simple model for estimating dry deposition velocity of ozone and its destruction in a polluted nocturnal boundary layer

Determining the destructions of both ozone and odd oxygen, O_x, in the nocturnal boundary layer (NBL) is important to evaluate the regional ozone budget and overnight ozone accumulation. This work develops a simple method to determine the dry deposition velocity of ozone and its destruction at a polluted nocturnal boundary layer. The destruction of O_x can also be determined simultaneously. The method is based on O₃ and NO₂ profiles and their surface measurements. Linkages between the dry deposition velocities of O₃ and NO₂ and between the dry deposition loss of O_x and its chemical loss are constructed and used. Field measurements are made at an agricultural site to demonstrate the application of the model. The model estimated nocturnal O₃ dry deposition velocities from 0.13 to 0.19 cm s^?1, very close to those previously obtained for similar land types. Additionally, dry deposition and chemical reactions account for 60 and 40% of the overall nocturnal ozone loss, respectively; ozone dry deposition accounts for 50% of the overall nocturnal loss of O_x, dry deposition of NO₂ accounts for another 20%, and chemical reactions account for the remaining 30%. The proposed method enables the use of measurements made in typical ozone field studies to evaluate various nocturnal destructions of O₃ and O_x in a polluted environment.     

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.     

Analysis of the relationship between ambient levels of O3, NO2 and NO as a function of NOx in the UK

Monitoring data from the UK Automatic Urban and Rural Network are used to investigate the relationships between ambient levels of ozone (O₃), nitric oxide (NO) and nitrogen dioxide (NO₂) as a function of NO_x, for levels ranging from those typical of UK rural sites to those observed at polluted urban kerbside sites. Particular emphasis is placed on establishing how the level of ‘oxidant’, OX (taken to be the sum of O₃ and NO₂) varies with the level of NO_x, and therefore to gain some insight into the atmospheric sources of OX, particularly at polluted urban locations. The analyses indicate that the level of OX at a given location is made up of NO_x-independent and NO_x-dependent contributions. The former is effectively a regional contribution which equates to the regional background O₃ level, whereas the latter is effectively a local contribution which correlates with the level of primary pollution. The local oxidant source has probable contributions from (i) direct NO₂ emissions, (ii) the thermal reaction of NO with O₂ at high NO_x, and (iii) common-source emission of species which promote NO to NO₂ conversion. The final category may include nitrous acid (HONO), which appears to be emitted directly in vehicle exhaust, and is potentially photolysed to generate HO_x radicals on a short timescale throughout the year at southern UK latitudes. The analyses also show that the local oxidant source has significant site-to-site variations, and possible reasons for these variations are discussed. Relationships between OX and NO_x, based on annual mean data, and fitted functions describing the relative contributions to OX made by NO₂ and O₃, are used to define expressions which describe the likely variation of annual mean NO₂ as a function of NO_x at 14 urban and suburban sites, and which can take account of possible changes in the regional background of O₃.     

Measurements and analyses of nitrogen oxides and ozone in the yard and on the roof of a street-canyon in Suzhou

The concentrations of air pollutants such as nitrogen oxides and ozone characterised by very fast chemical reactions can significantly vary within urban street-canyon due to the short distances between sources and receptor. With the primary objective to analyse this issue, NO, NO₂, NO_x, O₃, BTX, and wind flow field were continuously measured for 1 week at two heights (a street-level yard and a 25-m-high rooftop) in an urban canyon in Suzhou (China). The yard ozone concentrations were found to be up to six times lower than on the roof. Different frequency distributions (FD), dynamical and chemical processes of the pollutant variations from yard to roof are discussed to explain the findings. The predominant factors for the dissimilar pollutant vertical diffusion at the two measurement locations were associated to dissimilar fluid-dynamic and heterogeneous removal effects that likely induced dissimilar ozone chemical processes relative to NO_x and BTX precursors.