Charles L. Blanchard

The Southeastern Aerosol Research and Characterization Study: Part 1—Overview

Abstract This paper presents an overview of a major, long-term program for tropospheric gas and aerosol research in the southeastern United States. Building on three existing ozone (O3)-focused research sites begun in mid-1992, the Southeastern Aerosol Research and Characterization Study (SEARCH) was initiated in mid-1998 as a 7-year observation and research program with a broader focus including aerosols and an expanded geographical coverage in the Southeast. The monitoring network comprises four urban-rural (or urban-suburban) site pairs at locations along the coast of the Gulf of Mexico and inland, including two moderately sized and two major urban areas (Pensacola, FL; Gulfport, MS; Atlanta, GA; and Birmingham, AL). The sites are equipped with an extensive suite of instruments for measuring particulate matter (PM), gases relevant to secondary O3 and the production of secondary aerosol particles, and surface meteorology. The measurements taken to date have added substantially to the knowledge about the temporal behavior and geographic variability of tropospheric aerosols in the Southeast. Details are presented in four papers to follow.

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 (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.

Effects of Changes in Sulfate, Ammonia, and Nitric Acid on Particulate Nitrate Concentrations in the Southeastern United States

Abstract A thermodynamic equilibrium model, Simulating Composition of Atmospheric Particles at Equilibrium (SCAPE2), was used to investigate the response of fine particulate NO3 − to changes in concentrations of HNO3 , NH3 , and SO4 2− in the southeastern United States. The data consisted of daily, 24-hr time resolution measurements from the Aerosol Research Inhalation Epidemiology Study (ARIES) Jefferson Street (Atlanta) site and five other sites of the Southeastern Aerosol Research and Characterization Project (SEARCH). Reductions of total NH3 (gas-phase NH3 plus particulate NH4 +), total NO3 − (HNO3 plus particulate NO3 −), SO4 2−, or combined total NO3 − (HNO3 plus particulate NO3 −) with SO4 2− were used to estimate the effects of changing emission levels. The conversion of SO2 to SO4 2− and NO2 to HNO3 involves additional nonlinear reactions not incorporated into the model. For all sites, fine particulate NO3 − concentrations decreased in response to reductions of either NH3 or total NO3 −, but the particulate NO3 − decreases were greater for the NH3 reductions than for the total NO3 − reductions. Particulate NO3 − concentrations increased in response to reductions of SO4 2−. For the combined reduction (total NO3 − plus SO4 2−), the resulting particulate NO3 − concentrations were on average no different than the base-case NO3 − levels. Measurements of fine particulate NO3 − and HNO3 support the modeling conclusions and indicate that particulate NO3 − formation is limited by the availability of NH3 at most times at all SEARCH sites.

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 (NOx). 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 NOx reductions on ozone formation, because the relative proportions and levels of ozone precursor species were significantly different on weekends than on weekdays. Weekend NOx 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 NOx-limited.

The Use of Ambient Measurements To Identify which Precursor Species Limit Aerosol Nitrate Formation

ABSTRACT A thermodynamic equilibrium model was used to investigate the response of aerosol NO3 to changes in concentrations of HNO3, NH3, and H2SO4. Over a range of temperatures and relative humidities (RHs), two parameters provided sufficient information for indicating the qualitative response of aerosol NO3. The first was the excess of aerosol NH4 + plus gas-phase NH3 over the sum of HNO3, particulate NO3, and particulate SO4 2- concentrations. The second was the ratio of particulate to total NO3 concentrations. Computation of these quantities from ambient measurements provides a means to rapidly analyze large numbers of samples and identify cases in which inorganic aerosol NO3 formation is limited by the availability of NH3. Example calculations are presented using data from three field studies. The predictions of the indicator variables and the equilibrium model are compared.

The use of ambient data to corroborate analyses of ozone control strategies

Abstract Data from environmental-chamber studies and photochemical box-model simulations were used to evaluate and revise a method for developing a qualitative understanding of the sensitivity of ozone formation at a particular time and place to changes in concentrations of volatile organic compounds (VOC) and oxides of nitrogen (NOx). The revised method requires measurements of ozone, NO, and either NOx or NOy. The sensitivities of the method to biases in measurements were evaluated. The method potentially can be used for qualitative assessment of VOC versus NOx limitation, comparison with the predictions of grid-based photochemical air-quality models, and evaluation of trends over time in the relative effectiveness of VOC versus NOx controls.

Ozone process insights from field experiments – Part III: extent of reaction and ozone formation

Abstract The analysis of ambient data offers a means of developing a qualitative understanding of the sensitivity of ozone formation at specific times and places to changes in VOC and NOx concentrations. The Integrated Empirical Rate (IER) model (Johnson, 1984, Proceedings of the Eighth International Clean Air Conference, Melbourne, Australia, pp. 715–731) and two revisions known as the Smog Production (SP) algorithm (Blanchard et al., 1999, Atmospheric Environment 33, 369–381; Chang et al., 1997, Atmospheric Environment 31, 2787–2794) are reviewed. Applied to ambient data, the algorithm requires measurements of ozone, NO, and either NOx or NOy and computes a quantity known as the extent of reaction. The extent of reaction is shown to be related to photochemical age and serves as an indicator of the sensitivity of instantaneous ozone production to changes in VOC or NOx concentrations. Extent of reaction alone is insufficient as an indicator of the sensitivity of ozone concentration to a complex upwind history of emission changes. Consideration of daily, hourly, and spatial patterns of extent of reaction is needed to interpret applications of the SP algorithm.

The Southeastern Aerosol Research and Characterization (SEARCH) study: Temporal trends in gas and PM concentrations and composition, 1999–2010

The SEARCH study began in mid 1998 with a focus on particulate matter and gases in the southeastern United States. Eight monitoring sites, comprising four urban/nonurban pairs, are located inland and along the coast of the Gulf of Mexico. Downward trends in ambient carbon monoxide (CO), sulfur dioxide (SO2), and oxidized nitrogen species (NOy) concentrations averaged 1.2 ± 0.4 to 9.7 ± 1.8% per year from 1999 to 2010, qualitatively proportional to decreases of 4.7 to 7.9% per year in anthropogenic emissions of CO, SO2, and oxides of nitrogen (NOx) in the SEARCH region. Downward trends in mean annual sulfate (SO4) concentrations ranged from 3.7 ± 1.1 to 6.2 ± 1.1% per year, approximately linear with, but not 1:1 proportional to, the 7.9 ± 1.1% per year reduction in SO2 emissions from 1999 to 2010. The 95th percentile of the March–October peak daily 8-hr ozone (O3) concentrations decreased by 1.1 ± 0.4 to 2.4 ± 0.6 ppbv per year (1.5 ± 0.6 to 3.1 ± 0.8% per year); O3 precursor emissions of NOx and volatile organic compounds (VOC) decreased at rates of 4.7 and 3.3% per year, respectively. Ambient particulate nitrate (NO3) concentrations decreased by 0.6 ± 1.2 to 5.8 ± 0.9% per year, modulated in comparison with mean annual ambient NOy concentration decreases ranging from 6.0 ± 0.9 to 9.0 ± 1.3% per year. Mean annual organic matter (OM) and elemental carbon (EC) concentrations declined by 3.3 ± 0.8 to 6.5 ± 0.3 and 3.2 ± 1.4 to 7.8 ± 0.7% per year. The analysis demonstrates major improvements in air quality in the Southeast from 1999 to 2010. Meteorological variations and incompletely quantified uncertainties for emission changes create difficulty in establishing unambiguous quantitative relationships between emission reductions and ambient air quality. Implications: Emissions and secondary pollutants show complex relationships that depend on year-to-year variations in dispersion and atmospheric chemistry. The observed response of O3 to NOx and VOC emissions in the Southeast implies that continuing reductions of precursor emissions, probably achieved through vehicle fleet turnover and emission control measures, will be needed to attain the National Ambient Air Quality Standard for O3. Reductions in fine particle concentrations have resulted from reductions of primary PM, especially EC and a portion of OM, and from reduction of gas precursors known to form particles, especially SO4 from SO2. Continued reduction of PM2.5 mass concentrations will require attention to organic constituents, which may be complicated by potentially unmanageable biogenic species present in the Southeast.

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 [NOx], carbon moNOxide [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, NOx, 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 NOx 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, NOx, CO, and VOCs declined by 65, 49, 28, and 19%, respectively, from Wednesdays to Sundays (median site responses). Despite the large reductions in ambient NOx 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.

The Southeastern Aerosol Research and Characterization (SEARCH) study: Spatial variations and chemical climatology, 1999–2010

The Southeastern Aerosol Research and Characterization (SEARCH) study, which has been in continuous operation from 1999 to 2012, was implemented to investigate regional and urban air pollution in the southeastern United States. With complementary data from other networks, the SEARCH measurements provide key knowledge about long-term urban/nonurban pollution contrasts and regional climatology affecting inland locations and sites along the Gulf of Mexico coastline. Analytical approaches ranging from comparisons of mean concentrations to the application of air mass trajectories and principal component analysis provide insight into local and area-wide pollution. Gases (carbon monoxide, sulfur dioxide, nitrogen oxides, ozone, and ammonia), fine particle mass concentration, and fine particle species concentrations (including sulfate, elementary carbon, and organic carbon) are affected by a combination of regional conditions and local emission sources. Urban concentrations in excess of regional baselines and intraurban variations of concentrations depend on source proximity, topography, and local meteorological processes. Regional-scale pollution events (95th percentile concentrations) involving more than 6 of the 8 SEARCH sites are rare (< 2% of days), while subregional events affecting 4–6 sites occur on ˜10% of days. Regional and subregional events are characterized by widely coincident elevated concentrations of ozone, sulfate, and particulate organic carbon, driven by persistent synoptic-scale air mass stagnation and higher temperatures that favor formation of secondary species, mainly in the summer months. The meteorological conditions associated with regional stagnation do not favor long-range transport of polluted air masses during episodes. Regional and subregional pollution events frequently terminate with southward and eastward penetration of frontal systems, which may initially reduce air pollutant concentrations more inland than along the Gulf Coast. Implications: Regional distribution of emission sources and synoptic-scale meteorological influences favoring stagnation lead to high regionwide pollution levels. The regional influence is greatest with secondary species, including ozone (O3) particulate sulfate (SO4), and particulate organic matter, some of which is produced by atmospheric oxidation of volatile organic compounds (VOCs) from vegetation and anthropogenic sources. Other species, many of which are from primary emissions, are more influenced by local sources, especially within the Atlanta, GA, and Birmingham, AL, metropolitan areas. Limited measurements of modern and fossil total carbon point to the importance of biological and biogenic emissions in the Southeast.