Paul T. Roberts

Analysis and Apportionment of Organic Carbon and Fine Particulate Matter Sources at Multiple Sites in the Midwestern United States

Abstract Speciated fine particulate matter (PM2.5) data collected as part of the Speciation Trends Network at four sites in the Midwest (Detroit, MI; Cincinnati, OH; Indianapolis, IN; and Northbrook, IL) and as part of the Interagency Monitoring of Protected Visual Environments program at the rural Bondville, IL, site were analyzed to understand sources contributing to organic carbon (OC) and PM2.5 mass. Positive matrix factorization (PMF) was applied to available data collected from January 2002 through March 2005, and seven to nine factors were identified at each site. Common factors at all of the sites included mobile (gasoline)/secondary organic aerosols with high OC, diesel with a high elemental carbon/OC ratio (only at the urban sites), secondary sulfate, secondary nitrate, soil, and biomass burning. Identified industrial factors included copper smelting (North–brook, Indianapolis, and Bondville), steel/manufacturing with iron (Northbrook), industrial zinc (North–brook, Cincinnati, Indianapolis, and Detroit), metal plating with chromium and nickel (Detroit, Indianapolis, and Bondville), mixed industrial with copper and iron (Cincinnati), and limestone with calcium and iron (Bondville). PMF results, on average, accounted for 96% of the measured PM2.5 mass at each site; residuals were consistently within tolerance (±3), and goodness–of–fit (Q) was acceptable. Potential source contribution function analysis helped identify regional and local impacts of the identified source types. Secondary sulfate and soil factors showed regional characteristics at each site, whereas industrial sources typically appeared to be locally influenced. These regional factors contributed approximately one third of the total PM2.5 mass, on average, whereas local mobile and industrial sources contributed to the remaining mass. Mobile sources were a major contributor (55–76% at the urban sites) to OC mass, generally with at least twice as much mass from nondiesel sources as from diesel. Regional OC associated with secondary sulfate and soil was generally low.

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

Abstract Air quality data collected in the California Regional PM10/PM2.5 Air Quality Study (CRPAQS) are analyzed to qualitatively assess the processes affecting secondary aerosol formation in the San Joaquin Valley (SJV). This region experiences some of the highest fine particulate matter (PM2.5) mass concentrations in California (≤188 μg/m3 24-hr average), and secondary aerosol components (as a group) frequently constitute over half of the fine aerosol mass in winter. The analyses are based on 15 days of high-frequency filter and canister measurements and several months of wintertime continuous gas and aerosol measurements. The phase-partitioning of nitrogen oxide (NOx)-related nitrogen species and carbonaceous species shows that concentrations of gaseous precursor species are far more abundant than measured secondary aerosol nitrate or estimated secondary organic aerosols. Comparisons of ammonia and nitric acid concentrations indicate that ammonium nitrate formation is limited by the availability of nitric acid rather than ammonia. Time-resolved aerosol nitrate data collected at the surface and on a 90-m tower suggest that both the daytime and nighttime nitric acid formation pathways are active, and entrainment of aerosol nitrate formed aloft at night may explain the spatial homogeneity of nitrate in the SJV. NOx and volatile organic compound (VOC) emissions plus background O3 levels are expected to determine NOx oxidation and nitric acid production rates, which currently control the ammonium nitrate levels in the SJV. Secondary organic aerosol formation is significant in winter, especially in the Fresno urban area. Formation of secondary organic aerosol is more likely limited by the rate of VOC oxidation than the availability of VOC precursors in winter.

Source Apportionment of Fine Particulate Matter in Phoenix, AZ, Using Positive Matrix Factorization

Abstract Speciated particulate matter (PM)2.5 data collected as part of the Interagency Monitoring of Protected Visual Environments (IMPROVE) program in Phoenix, AZ, from April 2001 through October 2003 were analyzed using the multivariate receptor model, positive matrix factorization (PMF). Over 250 samples and 24 species were used, including the organic carbon and elemental carbon analytical temperature fractions from the thermal optical reflectance method. A two-step approach was used. First, the species excluding the carbon fractions were used, and initially eight factors were identified; non-soil potassium was calculated and included to better refine the burning factor. Next, the mass associated with the burning factor was removed, and the data set rerun with the carbon fractions. Results were very similar (i.e., within a few percent), but this step enabled a separation of the mobile factor into gasoline and diesel vehicle emissions. The identified factors were burning (on average 2% of the mass), secondary transport (7%), regional power generation (13%), dust (25%), nitrate (9%), industrial As/Pb/Se (2%), Cu/Ni/V (7%), diesel (9%), and general mobile (26%). The overall contribution from mobile sources also increased, as some mass (OC and nitrate) from the nitrate and regional power generation factors were apportioned with the mobile factors. This approach allowed better apportionment of carbon as well as total mass. Additionally, the use of multiple supporting analyses, including air mass trajectories, activity trends, and emission inventory information, helped increase confidence in factor identification.

Wintertime Vertical Variations in Particulate Matter (PM) and Precursor Concentrations in the San Joaquin Valley during the California Regional Coarse PM/Fine PM Air Quality Study

Abstract Air quality monitoring was conducted at a rural site with a tower in the middle of California’s San Joaquin Valley (SJV) and at elevated sites in the foothills and mountains surrounding the SJV for the California Regional PM10/M2.5 Air Quality Study. Measurements at the surface and on a tower at 90 m were collected in Angiola, CA, from ecember 2000 through February 2001 and included hourly black carbon (BC), particle counts from optical particle counters, nitric oxide, ozone, temperature, relative humidity, wind speed, and direction. Boundary site measurements were made primarily using 24-hr integrated particulate matter (PM) samples. These measurements were used to understand the vertical variations of PM and PM precursors, the effect of stratification in the winter on concentrations and chemistry aloft and at the surface, and the impact of aloft-versus-surface transport on PM concentrations. Vertical variations of concentrations differed among individual species. The stratification may be important to atmospheric chemistry processes, particularly nighttime nitrate formation aloft, because NO2 appeared to be oxidized by ozone in the stratified aloft layer. Additionally, increases in accumulation-mode particle concentrations in the aloft layer during a fine PM (PM2.5) episode corresponded with increases in aloft nitrate, demonstrating the likelihood of an aloft nighttime nitrate formation mechanism. Evidence of local transport at the surface and regional transport aloft was found; transport processes also varied among the species. The distribution of BC appeared to be regional, and BC was often uniformly mixed vertically. Overall, the combination of time-resolved tower and surface measurements provided important insight into PM stratification, formation, and transport.

Transport and dispersion during wintertime particulate matter episodes in the San Joaquin Valley, California.

Abstract Data analysis and modeling were performed to characterize the spatial and temporal variability of wintertime transport and dispersion processes and the impact of these processes on particulate matter (PM) concentrations in the California San Joaquin Valley (SJV). Radar wind profiler (RWP) and radio acoustic sounding system (RASS) data collected from 18 sites throughout Central California were used to estimate hourly mixing heights for a 3-month period and to create case studies of high-resolution diagnostic wind fields, which were used for trajectory and dispersion analyses. Data analyses show that PM episodes were characterized by an upper-level ridge of high pressure that generally produced light winds through the entire depth of the atmospheric boundary layer and low mixing heights compared with nonepisode days. Peak daytime mixing heights during episodes were ~400 m above ground level (agl) compared with ~800 m agl during nonepisodes. These episode/nonepisode differences were observed throughout the SJV. Dispersion modeling indicates that the range of influence of primary PM emitted in major population centers within the SJV ranged from ~15 to 50 km. Trajectory analyses revealed that little intrabasin pollutant transport occurred among major population centers in the SJV; however, interbasin transport from the northern SJV and Sacramento regions into the San Francisco Bay Area (SFBA) was often observed. In addition, this analysis demonstrates the usefulness of integrating RWP/RASS measurements into data analyses and modeling to improve the understanding of meteorological processes that impact pollution, such as aloft transport and boundary layer evolution.

Variations in the OM/OC ratio of urban organic aerosol next to a major roadway

Understanding the organic matter/organic carbon (OM/OC) ratio in ambient particulate matter (PM) is critical to achieve mass closure in routine PM measurements, to assess the sources of and the degree of chemical processing organic aerosol particles have undergone, and to relate ambient pollutant concentrations to health effects. Of particular interest is how the OM/OC ratio varies in the urban environment, where strong spatial and temporal gradients in source emissions are common. We provide results of near-roadway high-time-resolution PM1 OM concentration and OM/OC ratio observations during January 2008 at Fyfe Elementary School in Las Vegas, NV, 18 m from the U.S. 95 freeway soundwall, measured with an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-AMS). The average OM/OC ratio was 1.54 (± 0.20 standard deviation), typical of environments with a low amount of secondary aerosol formation. The 2-min average OM/OC ratios varied between 1.17 and 2.67, and daily average OM/OC ratios varied between 1.44 and 1.73. The ratios were highest during periods of low OM concentrations and generally low during periods of high OM concentrations. OM/OC ratios were low (1.52 ± 0.14, on average) during the morning rush hour (average OM = 2.4 µg/m3), when vehicular emissions dominate this near-road measurement site. The ratios were slightly lower (1.46 ± 0.10) in the evening (average OM = 6.3 µg/m3), when a combination of vehicular and fresh residential biomass burning emissions was typically present during times with temperature inversions. The hourly averaged OM/OC ratio peaked at 1.66 at midday. OM concentrations were similar, regardless of whether the monitoring site was downwind or upwind of the adjacent freeway throughout the day, though they were higher during stagnant conditions (wind speed < 0.5 m/sec). The OM/OC ratio generally varied more with time of day than with wind direction and speed. Implications: Day-to-day variability in the fine particle OM/OC ratio is quite large, suggesting that using a fixed OM/OC value in PM mass closure calculations, even one that changes seasonally, may be insufficient to achieve accurate mass closure on individual days. Health studies that rely on OC measurements may under- or overestimate exposure to OM, and converting OC to OM with a fixed OM/OC ratio represents a significant source of uncertainty; thus, air quality managers may not have sufficient information about the importance of OM contributions to PM2.5 to make optimal regulatory decisions. Supplemental Materials: Supplemental materials are available for this paper. Go to the publishers online edition of the Journal of the Air & Waste Management Association.

Combining continuous near–road monitoring and inverse modeling to isolate the effect of highway expansion on a school in Las Vegas

The impact of a highway expansion on a school adjacent to the highway is investigated with a novel method called the Sustained Wind Incidence Method (SWIM). SWIM falls under the broad group of environmental forensics methods where measured concentration data are used to identify possible contributors such as a point, line or a sectional source. SWIM helps to identify potential sources by highlighting spatial domains associated with the markers unique to potential contributors. In this study, SWIM is used to identify sources of traffic related emissions. The marker used to measure the impact of the traffic due to expansion is black carbon (BC), a key traffic related emission mostly associated with large vehicles (>12 m in length), collected both before and after the expanded lanes were open for use. Using this method, multiple source domains may be simultaneously identified. For this study, the data collection site was situated at the school about 20 meters from the sound wall (7 meters high) separating the school and the highway. SWIM results show that the road expansions may have impacted the traffic patterns of the nearby non–highway feeder road and on–ramp (adjacent to the sound wall) traffic to the highway. This sector showed a surprisingly larger change than the highway in the observed increase in their relative contribution to the receptor site. Some domains (apportioned sector) show a dramatic increase ranging roughly from 10% to 50% in relative contributions. Using the output from SWIM and knowledge of local contributors, a local source landscape is painted.

Changes in air quality at near-roadway schools after a major freeway expansion in Las Vegas, Nevada

Near-roadway ambient black carbon (BC) and carbon monoxide (CO) concentrations were measured at two schools adjacent to a freeway and at an urban background school 2 km from the freeway to determine the change in concentrations attributable to vehicle emissions after the three-lane expansion of U.S. Highway 95 (US 95) in Las Vegas, Nevada. Between summer 2007 and summer 2008, average weekday small-vehicle volume increased by 40% ± 2% (standard error). Average weekday large-vehicle volume decreased by 17% ± 5%, due to a downturn in the economy and an associated decline in goods movement. Average vehicle speed increased from 58 to 69 mph, a 16% ± 1% increase. The authors compared BC and CO concentrations in summer 2007 with those in summer 2008 to understand what effect the expansion of the freeway may have had on ambient concentrations: BC and CO were measured 17 m north of the freeway sound wall, CO was measured 20 m south of the sound wall, and BC was measured at an urban background site 2 km south of the freeway. Between summer 2007 and summer 2008, median BC decreased at the near-road site by 40% ± 2% and also decreased at the urban background site by 24% ± 4%, suggesting that much of the change was due to decreases in emissions throughout Las Vegas, rather than only on US 95. CO concentrations decreased by 14% ± 2% and 10% ± 3% at the two near-road sites. The decrease in BC concentrations after the expansion is likely due to the decrease in medium- and heavy-duty-vehicle traffic resulting from the economic recession. The decrease in CO concentrations may be a result of improved traffic flow, despite the increase in light-duty-vehicle traffic. Implications Monitoring of BC and CO at near-road locations in Las Vegas demonstrated the impacts of changes in traffic volume and vehicle speed on near-road concentrations. However, urban-scale declines in concentrations were larger than near-road changes due to the impacts of the economic recession that occurred contemporaneously with the freeway expansion.

Particle count and black carbon measurements at schools in Las Vegas, NV and in the greater Salt Lake City, UT area

ABSTRACT As part of two separate studies aimed to characterize ambient pollutant concentrations at schools in urban areas, we compare black carbon and particle count measurements at Adcock Elementary in Las Vegas, NV (April–June 2013), and Hunter High School in the West Valley City area of greater Salt Lake City, UT (February 2012). Both schools are in urban environments, but Adcock Elementary is next to the U.S. 95 freeway. Black carbon (BC) concentrations were 13% higher at Adcock compared to Hunter, while particle count concentrations were 60% higher. When wind speeds were low—less than 2 m/sec—both BC and particle count concentrations were significantly higher at Adcock, while concentrations at Hunter did not have as strong a variation with wind speed. When wind speeds were less than 2 m/sec, emissions from the adjacent freeway greatly affected concentrations at Adcock, regardless of wind direction. At both sites, BC and particle count concentrations peaked in the morning during commute hours. At Adcock, particle count also peaked during midday or early afternoon, when BC was low and conditions were conducive to new particle formation. While this midday peak occurred at Adcock on roughly 45% of the measured days, it occurred on only about 25% of the days at Hunter, since conditions for particle formation (higher solar radiation, lower wind speeds, lower relative humidity) were more conducive at Adcock. Thus, children attending these schools are likely to be exposed to pollution peaks during school drop-off in the morning, when BC and particle count concentrations peak, and often again during lunchtime recess when particle count peaks again. Implications: Particle count concentrations at two schools were shown to typically be independent of BC or other pollutants. At a school in close proximity to a major freeway, particle count concentrations were high during the midday and when wind speeds were low, regardless of wind direction, showing a large area of effect from roadway emissions even when the school was not downwind of the roadway. At the second school, which sits in an urban neighborhood away from freeways, high particle counts occurred even though solar radiation was low during wintertime conditions, meaning that exposure to high particle counts can occur throughout the year.