Shelley Tanenbaum

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.

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 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.

Weekday/Weekend differences in ambient air pollutant concentrations in atlanta and the southeastern United States.

Abstract The authors quantified changes between mean weekday and weekend ambient concentrations of ozone (O3) precursors (volatile organic compounds [VOC], carbon monoxide [CO], nitric oxide, and oxides of nitrogen [NOx]) in Atlanta and surrounding areas to observe how weekend precursor emission levels influenced ambient O3 levels.The authors analyzed CO, nitric oxide (NO), and NOx measurements from 1998 to 2002 and speciated VOC from 1996 to 2003. They observed a strong weekend effect in the Atlanta region, with median daytime (6:00 a.m. to 3:00 p.m. Eastern Standard Time) decreases of 62%, 57%, and 31%, respectively, in the ambient levels of NO, NOx,and CO from Wednesdays to Sundays, during the ozone season (March to October). They also observed significant decreases in ambient VOC levels between Wednesdays and Sundays, with decreases of 28% for the sum of aromatic compounds and 19% for the sum of Photochemical Assessment Monitoring Stations target compounds. Despite large reductions in O3 precursor levels on weekends, day-of-week differences in O3 mixing ratios in and near Atlanta were much smaller. Averaging overall O3-season days, the 1-hr and 8-hr mean peak daily O3 maxima on Sundays were 4.5% and 2.3% lower, respectively, than their mean levels on Wednesdays (median of 14 site differences), with no sites showing statistically significant Wednesday-to-Sunday differences. When restricted to high-O3 days (highest 3 peak O3 days per day of week per site per year), the 1-hr and 8-hr Sunday O3 mixing ratios were 11% and 10% lower, respectively, than their mean peak levels on Wednesdays (median of 14 site differences), with 6 of 14 sites showing statistically significant Wednesday-to-Sunday differences. The analyses of week-day/weekend differences in O3 precursor concentrations show that different emission reductions than normally take place each weekend will be required to achieve major reductions in ambient ozone levels in the Atlanta area.

Source Contributions to Atmospheric Gases and Particulate Matter in the Southeastern United States

A new approach for determining the contributions of emission sources to concentrations of particulate matter and gases is developed using the chemical mass balance (CMB) method and the U.S. EPAs National Emission Inventory (NEI). The approach apportions combined gas-phase and condensed-phase concentrations of individual compounds as well as PM(2.5) mass. Because the NEI is used to provide source emission profiles for CMB analysis, the method generates information on the consistency of the NEI with ambient monitoring data. The method also tracks secondary species to primary source emissions, permitting a more complete accounting of the impact of aggregated source types on PM(2.5) mass concentrations. An example application is presented using four years of monitoring data collected at eight sites in the Southeastern Aerosol Research and Characterization (SEARCH) network. Including both primary and secondary species, area sources contributed 2.0-3.7 μg m(-3) (13-26%), point sources contributed 3.0-4.6 μg m(-3) (22-33%), and mobile sources contributed 1.0-6.0 μg m(-3) (9-42%) to mean PM(2.5) mass concentrations. Whereas the NEI generally accounts for the ambient concentrations of gases and particles, certain anomalies are identified, especially related to carbonaceous compounds and dust.

Effects of sulfur dioxide and oxides of nitrogen emission reductions on fine particulate matter mass concentrations : Regional comparisons

Abstract Two thermodynamic equilibrium models were applied to estimate changes in mean airborne fine particle (PM2.5)mass concentrations that could result from changes in ambient concentrations of sulfate, nitric acid, or ammonia in the southeastern United States, the midwestern United States, and central California. Pronounced regional differences were found. Southeastern sites exhibited the lowest current mean concentrations of nitrate, and the smallest predicted responses of PM2.5 nitrate and mass concentrations to reductions of nitric acid, which is the principal reaction product of the oxidation of nitrogen dioxide (NO2) and the primary gas-phase precursor of fine particulate nitrate. Weak responses of PM2.5 nitrate and mass concentrations to changes in nitric acid levels occurred even if sulfate concentrations were half of current levels. The midwestern sites showed higher levels of fine particulate nitrate, characterized by cold-season maxima, and were projected to show decreases in overall PM levels following decreases of either sulfate or nitric acid. For some midwestern sites, predicted PM2.5 nitrate concentrations increased as modeled sulfate levels declined, but sulfate reductions always reduced the predicted fine PM mass concentrations; PM2.5 nitrate concentrations became more sensitive to reductions of nitric acid as modeled sulfate concentrations were decreased. The California sites currently have the highest mean concentrations of fine PM nitrate and the lowest mean concentrations of fine PM sulfate. Both the estimated PM2.5 nitrate and fine mass concentrations decreased in response to modeled reductions of nitric acid at all California sites. The results indicate important regional differences in expected PM2.5 mass concentration responses to changes in sulfate and nitrate precursors. Analyses of ambient data, such as described here, can be a key part of weight of evidence (WOE) demonstrations for PM2.5 attainment plans. Acquisition of the data may require special sampling efforts, especially for PM2.5 precursor concentration data.

Source attribution of air pollutant concentrations and trends in the southeastern aerosol research and characterization (SEARCH) network.

A new approach for determining the contributions of emission sources to trends in concentrations of particulate matter and gases is developed using the chemical mass balance (CMB) method and the U.S. EPAs National Emission Inventory (NEI). The method extends our earlier analysis by using temporally varying emission profiles and includes accounting of primary and secondary particulate organic carbon with an empirical regression calculation. The model offers a potentially important tool for verifying that annual emission reductions by major source category have yielded changes in ambient pollutant concentrations. Using long-term measurements from well-instrumented monitoring sites, observed trends in ambient pollutant concentrations at urban and rural locations can be attributed to emission changes. Trends apportionment is conducted on 2000-2011 ambient monitoring data from the SEARCH network with NEI emissions data adjusted to improve interinventory consistency. The application accounts for major source category influences in southeastern U.S. regional trends; local anomalies are noted. In the SEARCH region, open burning is important as a source of CO and carbonaceous particles. Improved agreement between predicted and measured particulate carbon is obtained by increasing mobile diesel exhaust and area-source particulate carbon emissions by 1 and 20%, respectively, compared with NEI values. The method is general and is applicable to data from any monitoring site that is instrumented for criteria air pollutants, associated gases, and particle composition.

Spatial and Temporal Characterization of PM2.5 Mass Concentrations in California, 1980–2007

ABSTRACT Systematic measurement of fine particulate matter (aerodynamic diameter less than 2.5 μm [PM2.5]) mass concentrations began nationally with implementation of the Federal Reference Method (FRM) network in 1998 and 1999. In California, additional monitoring of fine particulate matter (PM) occurred via a dichotomous sampler network and several special studies carried out between 1982 and 2002. The authors evaluate the comparability of FRM and non-FRM measurements of PM2.5 mass concentrations and establish conversion factors to standardize fine mass measurements from different methods to FRM-equivalent concentrations. The authors also identify measurements of PM2.5 mass concentrations that do not agree with FRM or other independent PM2.5 mass measurements. The authors show that PM2.5 mass can be reconstructed to a high degree of accuracy (r 2 > 0.9; mean absolute error ∼2 μg m−3) from PM with an aerodynamic diameter ≤10 μm (PM10) mass and species concentrations when site-specific and season-specific conversion factors are used and a statewide record of fine PM mass concentrations by combining the FRM PM2.5 measurements, non-FRM PM2.5 measurements, and reconstructions of PM2.5 mass concentrations. Trends and spatial variations are evaluated using the integrated data. The rates of change of annual fine PM mass were negative (downward trends) at all 22 urban and 6 nonurban (Interagency Monitoring of Protected Visual Environments [IMPROVE]) monitoring locations having at least 15 yr of data during the period 1980–2007. The trends at the IMPROVE sites ranged from -0.05 to -0.25 μg m−3 yr−1 (median -0.11 μg m−3 yr−1), whereas urban-site trends ranged from -0.13 to -1.29 μg m−3 yr−1 (median -0.59 μg m−3 yr−1). The urban concentrations declined by a factor of 2 over the period of record, and these decreases were qualitatively consistent with changes in emissions of primary PM2.5 and gas-phase precursors of secondary PM. Mean PM2.5 mass concentrations ranged from 3.3 to 7.4 μg m−3 at IMPROVE sites and from 9.3 to 37.1 μg m−3 at urban sites. IMPLICATIONS Mean measured and reconstructed fine particulate matter mass concentrations declined by about a factor of 2 in California over the period 1980 to 2007 and varied by about a factor of 4 among air basins. The integrated data record is of interest for epidemiological studies and for assessments of emission control programs.