Differences between weekday and weekend air pollutant levels in southern California

Ambient air quality data were analyzed to empirically evaluate the effects of reductions of volatile organic compounds (VOCs) and oxides of nitrogen (NOx) 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 NOx 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 NOx. 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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

Deposition and adsorption of the air pollutant HNO3 vapor to soil surfaces

Deposition of nitric acid (HNO₃) vapor to soils has been evaluated in three experimental settings: (1) continuously stirred tank reactors with the pollutant added to clean air, (2) open-top chambers at high ambient levels of pollution with and without filtration reducing particulate nitrate levels, (3) two field sites with high or low pollution loads in the coastal sage plant community of southern California. The results from experiment (1) indicated that the amount of extractable NO₃⁻ from isolated sand, silt and clay fractions increased with atmospheric concentration and duration of exposure. After 32 days, the highest absorption of HNO₃ was determined for clay, followed by silt and sand. While the sand and silt fractions showed a tendency to saturate, the clay samples did not after 32 days of exposure under highly polluted conditions. Absorption of HNO₃ occurred mainly in the top 1 mm layer of the soil samples and the presence of water increased HNO₃ absorption by about 2-fold. Experiment (2) indicated that the presence of coarse particulate NO₃⁻ could effectively block absorption sites of soils for HNO₃ vapor. Experiment (3) showed that soil samples collected from open sites had about 2.5 more extractable NO₃⁻ as compared to samples collected from beneath shrub canopies. The difference in NO₃⁻ occurred only in the upper 1–2 cm as no significant differences in NO₃⁻ concentrations were found in the 2–5 cm soil layers. Extractable NO₃⁻ from surface soils collected from a low-pollution site ranged between 1 and 8 μg NO₃–N g⁻¹, compared to a maximum of 42 μg NO₃–N g⁻¹ for soils collected from a highly polluted site. Highly significant relationship between HNO₃ vapor doses and its accumulation in the upper layers of soils indicates that carefully prepared soil samples (especially clay fraction) may be useful as passive samplers for evaluation of ambient concentrations of HNO₃ vapor.     

Annual and weekly patterns of ozone and particulate matter in Jeddah,Saudi Arabia

Air pollution has been an increasing concern within the Kingdom of Saudi Arabia and other Middle Eastern countries. In this work the authors present an analysis of daily ozone (O₃), nitrogen oxide (NO_x), and particulate matter (<10 μm aerodynamic diameter; PM₁₀) concentrations for two years (2010 and 2011) at sites in and around the coastal city of Jeddah, as well as a remote background site for comparison. Monthly and weekly variations, along with their implications and consequences, were also examined. O₃ within Jeddah was remarkably low, and exhibited the so-called weekend effect—elevated O₃ levels on the weekends, despite reduced emissions of O₃ precursors on those days. Weekend O₃ increases averaged between 12% and 14% in the city, suggesting that NO_x/volatile organic compound (VOC) ratios within cities such as Jeddah may be exceptionally high. Sites upwind or far removed from Jeddah did not display this weekend effect. Based on these results, emission control strategies in and around Jeddah must carefully address NO_x/VOC ratios so as to reduce O₃ at downwind locations without increasing it within urban locations themselves. PM₁₀ concentrations within Jeddah were elevated compared with North American cites of similar climatology, though comparable to other large cities within the Middle East.

Implications:Daily concentrations of O₃, PM₁₀, and NO_x in and around the city of Jeddah, Saudi Arabia, are analyzed and compared with those of other reference cities. Extremely low O₃ levels, along with a significant urban weekend effect (higher weekend O₃, despite reduced NO_x concentrations), is apparent, along with high levels of PM₁₀ within the city. Urban O₃ in Jeddah was found to be lower than that of other comparable cities, but the strong weekend effect suggests that care must be taken to reduce downwind O₃ levels without increasing them within the city itself. Further research into the emissions and chemistry contributing to the reduced O₃ levels within the city is warranted.     

Intercomparison of Clean Air Status and Trends Network Nitrate and Nitric Acid Measurements with Data from Other Monitoring Programs

Abstract

The U.S. Environmental Protection Agency Clean Air Status and Trends Network (CASTNET) utilizes an open-face filter pack system to measure concentrations of atmospheric sulfur and nitrogen species. Concentration data for nitrogen species measured with filter pack systems sometimes deviate from data collected by other measurement systems used to measure the same species. The nature of these differences suggests that more than one sampling mechanism or atmospheric process is involved. The study presented here examines these differences by intercomparing CASTNET data with data from other studies, examining the results from earlier intercomparison studies, and conducting a field test to investigate the effect of particle size on filter pack measurement systems. Measurements of nitrogen species from the Maryland Aerosol Research and Characterization (MARCH) monitoring site were compared with nitrogen concentrations at three nearby CASTNET sites. Results indicate that CASTNET measured higher particulate nitrate (NO₃ ^-) and lower gaseous nitric acid (HNO₃) concentrations. Comparisons of NO₃ ^- from 34 collocated CASTNET and Inter-agency Monitoring of Protected Visual Environments (IMPROVE) sites show that CASTNET NO₃ ^- measurements were typically higher than the corresponding IM PROVE values. Also, results from the Lake Michigan Air Director’s Consortium Midwest Ammonia Monitoring Project demonstrated NO₃ ^- dissociation on Teflon filters. To investigate the effect of particle size, filter pack measurement systems were operated at three CASTNET sites with and without cyclones during six 7-day measurement periods from March to August 2006. Results indicate the size-selection cyclones had a significant effect on both NO₃ ^- and HNO₃ concentrations, but little effect on sulfate (SO₄ ^2-) and ammonium (NH₄ ⁺) levels. NO₃ ^- concentrations sampled with the open-face filters were significantly higher than concentrations measured with a 2.5-μm cut point, as were HNO₃ concentrations. Although limited in spatial and temporal coverage, the field study showed that the use of an open-face filter pack may allow for the collection of coarse NO₃ ^- particles and for the reaction of HNO₃ with metals/salts on the Teflon filter.     

Day-of-week patterns of particulate matter and its chemical components at selected sites in California

This paper analyzes day-of-week variations in concentrations of particulate matter (PM) in California. Because volatile organic compounds (VOCs) and oxides of nitrogen (NOx) 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 < or = 10 microm (PM10) and < or = 2.5 microm in aerodynamic diameter (PM2.5) 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.     

Multispecies remote sensing measurements of vehicle emissions on Sherman Way in Van Nuys,California

As part of the 2010 Van Nuys tunnel study, researchers from the University of Denver measured on-road fuel-specific light-duty vehicle emissions from nearly 13,000 vehicles on Sherman Way (0.4 miles west of the tunnel) in Van Nuys, California, with its multispecies Fuel Efficiency Automobile Test (FEAT) remote sensor a week ahead of the tunnel measurements. The remote sensing mean gram per kilogram carbon monoxide (CO), hydrocarbon (HC), and oxide of nitrogen (NO_x) measurements are 8.9% lower, 41% higher, and 24% higher than the tunnel measurements, respectively. The remote sensing CO/NO_x and HC/NO_x mass ratios are 28% lower and 20% higher than the comparable tunnel ratios. Comparisons with the historical tunnel measurements show large reductions in CO, HC, and NO_x over the past 23 yr, but little change in the HC/NO_x mass ratio since 1995. The fleet CO and HC emissions are increasingly dominated by a few gross emitters, with more than a third of the total emissions being contributed by less than 1% of the fleet. An example of this is a 1995 vehicle measured three times with an average HC emission of 419 g/kg fuel (two-stroke snowmobiles average 475 g/kg fuel), responsible for 4% of the total HC emissions. The 2008 economic downturn dramatically reduced the number of new vehicles entering the fleet, leading to an age increase (>1 model year) of the Sherman Way fleet that has increased the fleet's ammonia (NH₃) emissions. The mean NH₃ levels appear little changed from previous measurements collected in the Van Nuys tunnel in 1993. Comparisons between weekday and weekend data show few fleet differences, although the fraction of light-duty diesel vehicles decreased from the weekday (1.7%) to Saturday (1.2%) and Sunday (0.6%).

Implications: On-road remote sensing emission measurements of light-duty vehicles on Sherman Way in Van Nuys, California, show large historical emission reductions for CO and HC emissions despite an older fleet arising from the 2008 economic downturn. Fleet CO and HC emissions are increasingly dominated by a few gross emitters, with a single 1995 vehicle measured being responsible for 4% of the entire fleet's HC emissions. Finding and repairing and/or scrapping as little as 2% of the fleet would reduce on-road tailpipe emissions by as much as 50%. Ammonia emissions have locally increased with the increasing fleet age.     

Seasonal variation of atmospheric ammonia and particulate ammonium concentrations in the urban atmosphere of yokohama over a 5-year period

Measurements of ammonia and particulate ammonium were made in the daytime (1200–1500) at a urban site in Yokohama during the 5-year period, 1982–1986. Diurnal NH₃ concentrations showed a distinct seasonal trend with a maximum in summer. The diurnal monthly average concentrations were above 10 ppb during the late spring and summer months, while the concentrations during the winter months were between 1 and 5 ppb. The seasonal variation was found to be very similar to that of the average air temperature and showed a periodic pattern over 1 year. A good correlation was observed between diurnal NH₃ concentrations and average air temperatures during the 5-year period. The annual mean concentrations were in the range of 6.6–7.6 ppb with only a minor deviation. The diurnal monthly average concentrations of particulate NH₄⁺ were between 1 and 4 μg m⁻³ and no significant seasonal variations were seen. As a short-term study, simultaneous measurements of NH₃, HNO₃ and particulate NO₃⁻ were made. The diurnal mean concentrations of NH₃ and HNO₃ were 7.6 and 0.8 ppb, respectively. The concentration of particulate NO₃⁻ ranged from 0.3 to 6μg⁻³. Both HNO₃ and particulate NO₃⁻ concentrations were relatively low and constant. Thus, NH₃ and HNO₃ levels did not agree with the concentrations predicted from the NH₄NO₃ equilibrium constant.     

Multi-year hourly PM2.5 carbon measurements in New York: Diurnal,day of week and seasonal patterns

Multi-year hourly measurements of PM_2.5 elemental carbon (EC) and organic carbon (OC) from a site in the South Bronx, New York were used to examine diurnal, day of week and seasonal patterns. The hourly carbon measurements also provided temporally resolved information on sporadic EC spikes observed predominantly in winter. Furthermore, hourly EC and OC data were used to provide information on secondary organic aerosol formation. Average monthly EC concentrations ranged from 0.5 to 1.4 μg m^?3 with peak hourly values of several μg m^?3 typically observed from November to March. Mean EC concentrations were lower on weekends (approximately 27% lower on Saturday and 38% lower on Sunday) than on weekdays (Monday to Friday). The weekday/weekend difference was more pronounced during summer months and less noticeable during winter. Throughout the year EC exhibited a similar diurnal pattern to NO_x showing a pronounced peak during the morning commute period (7–10 AM EST). These patterns suggest that EC was impacted by local mobile emissions and in addition by emissions from space heating sources during winter months. Although EC was highly correlated with black carbon (BC) there was a pronounced seasonal BC/EC gradient with summer BC concentrations approximately a factor of 2 higher than EC. Average monthly OC concentrations ranged from 1.0 to 4.1 μg m^?3 with maximum hourly concentrations of 7–11 μg m^?3 predominantly in summer or winter months. OC concentrations generally correlated with PM_2.5 total mass and aerosol sulfate and with NO_x during winter months. OC showed no particular day of week pattern. The OC diurnal pattern was typically different than EC except in winter when OC tracked EC and NO_x indicating local primary emissions contributed significantly to OC during winter at the urban location. On average secondary organic aerosol was estimated to account for 40–50% of OC during winter and up to 63–73% during summer months.     

In situ measurements of HNO3, NOy,NO, and O3 in the lower stratosphere and upper troposphere

In situ measurements of nitric acid (HNO₃), reactive nitrogen (NO_y), nitric oxide (NO), and ozone (O₃) made in the upper troposphere (UT) and lower stratosphere (LS) between 29° and 33°N latitudes during September 1999 are used to examine NO_y partitioning and correlations between the measured species in these regions. The fast-response (1 s) HNO₃ measurements are acquired with a new autonomous CIMS instrument. In the LS, HNO₃ accounts for the majority of NO_y, and the sum of HNO₃ and NO_x accounts for approximately 90% of NO_y. In the UT, the sum of HNO₃ and NO_x varies between 40% and 100% of NO_y. Both HNO₃ and NO_y are strongly positively correlated with O₃, with larger correlation slopes in the UT than in the LS. In the UT at low values of the quantity (NO_y–NO_x–HNO₃), it is uncorrelated with O₃, while at higher values, a positive correlation with O₃ is found. Of these two air mass types, those with higher (NO_y–NO_x–HNO₃) mixing ratios are likely associated with the presence of peroxyacetyl nitrate (PAN) that is produced by NO_x-hydrocarbon chemistry.     

Seasonal variations of acidic air pollutants in Seoul,South Korea

The annular denuder system (ADS) was used to characterize seasonal variations of acidic air pollutants in Seoul, South Korea. Fifty- four 24 h samples were collected over four seasons from October 1996 to September 1997. The annual mean concentrations of HNO₃, HNO₂, SO₂ and NH₃ in the gas phase were 1.09, 4.51, 17.3 and 4.34 μg m^-3, respectively. The annual mean concentrations of PM_2.5(d_p≤2.5 μm in aerodynamic diameter, 50% cutoff), SO^2-₄, NO^-₃ and NH⁺₄ in the particulate phase were 56.9, 8.70, 5.97 and 4.19 μg m^-3, respectively. All chemical species monitored from this study showed statistical seasonal variations. Nitric acid (HNO₃) and ammonia (NH₃) exhibited substantially higher concentrations during the summer, while nitrous acid (HNO₂) and sulfur dioxide(SO₂) were higher during the winter. Concentrations of PM_2.5, SO^2-₄, NO^-₃ and NH⁺₄ in the particulate phase were higher during the winter months. SO^2-₄, NO^-₃ and NH⁺₄ accounted for 26–38% of PM_2.5. High correlations were found among PM_2.5, SO^2-₄, NO^-₃ and NH⁺₄. The mean H⁺ concentration measured only in the fall was 5.19 nmole m^-3.