Source apportionment: findings from the U.S. Supersites Program

Receptor models are used to identify and quantify source contributions to particulate matter and volatile organic compounds based on measurements of many chemical components at receptor sites. These components are selected based on their consistent appearance in some source types and their absence in others. UNMIX, positive matrix factorization (PMF), and effective variance are different solutions to the chemical mass balance (CMB) receptor model equations and are implemented on available software. In their more general form, the CMB equations allow spatial, temporal, transport, and particle size profiles to be combined with chemical source profiles for improved source resolution. Although UNMIX and PMF do not use source profiles explicitly as input data, they still require measured profiles to justify their derived source factors. The U.S. Supersites Program provided advanced datasets to apply these CMB solutions in different urban areas. Still lacking are better characterization of source emissions, new methods to estimate profile changes between source and receptor, and systematic sensitivity tests of deviations from receptor model assumptions.     

Secondary particulate matter in the United States: insights from the Particulate Matter Supersites Program and related studies

Secondary aerosols comprise a major fraction of fine particulate matter (PM2.5) in all parts of the country, during all seasons, and times of day. The most abundant secondary species include sulfate, nitrate, ammonium, and secondary organic aerosols (SOAs). The relative abundance of each species varies in space and time as a function of meteorology, source emissions strength and type, thermodynamics, and atmospheric processing. Transport of secondary aerosols from upwind locations can contribute significantly at downwind receptor sites, especially regionally in the eastern United States, and across a given urbanized area, such as in Los Angeles. Processes governing the formation of the inorganic secondary species (sulfate, nitrate, and ammonium) are fairly well understood, although the occurrence of nucleation bursts initiated with the formation of ultrafine sulfuric acid particles observed regionally on clean days in the eastern United States was unexpected. Because of the complex nature of organic material in air, much is still to be learned about the sources, formation, and even spatial and temporal distributions of SOAs. For example, a considerable fraction of ambient organic PM is oxidized organic species, many of which still need to be identified, quantified, and their sources and formation mechanisms determined. Furthermore, significant uncertainty (approaching 50% or more) is associated with estimating the SOA fraction of organic material in air with current methods. This review summarizes the findings of the Supersites Program and related studies addressing secondary particulate matter (PM), including spatial and temporal variations of secondary PM and its precursor species, data and methods for determining the primary and secondary fractions of PM mass, and findings on the anthropogenic and natural fractions of secondary PM.     

Overview of the U.S. Environmental Protection Agency's Hazardous Air Pollutant Early Reduction Program.

Under provision of the Clean Air Act Amendments of 1990 Title III, the EPA has proposed a regulation (Early Reduction Program) to allow a six-year compliance extension from Maximum Achievable Control Technology (MACT) standards for sources that voluntarily reduce emissions of Hazardous Air Pollutants (HAPs) by 90 percent or more (95 percent or more for particulates) from a base year of 1987 or later. The emission reduction must be made before the applicable MACT standard is proposed for the source category or be subject to an enforceable commitment to achieve the reduction by January 1, 1994 for sources subject to MACT standards prior to 1994. The primary purpose of this program is to encourage reduction of HAPs emissions sooner than otherwise required. Industry would be allowed additional time in evaluating emission reduction options and developing more cost-effective compliance strategies, although, under strict guidelines to ensure actual, significant and verifiable emission reductions occur.     

Visibility reductions from soil dust in the Western U.S.

Soil dust can at times contribute significantly to atmospheric turbidity in the western U.S.A. An examination of meteorological surface observations from three sites in the west shows an increase in the number of cases of blowing dust (BD) over the past 30 years, while the mean wind speed associated with BD has decreased in growing, urban areas. Dust is reported more often in developing areas (such as Denver and Tucson) than in less disturbed areas (Winslow, AZ). Dust turbidity models, whose development was stimulated by the 1930s great plains dust bowl catastrophe are applicable to western soils as well and help explain visibility reductions caused by dust. Vehicle generated dust from unpaved roads can limit visibilities to values of one-third or less than the molecular scattering limit. The upper limits to the amounts of dust and visibility reduction to be expected in the west for differing meteorological conditions are calculated. It is estimated that dust devils may occasionally contribute 247 μg m ⁻³ of dust to the lower atmosphere in the west and a possible correlation between dust devils and human activity is noted.     

Air Pollution in Six Major U. S. Cities as Measured by the Continuous Air Monitoring Program

Data obtained by the Continuous Air Monitoring Program (CAMP) in six cities during two years are summarized. Six gaseous pollutants were monitored in Cincinnati, Chicago, New Orleans, Philadelphia, San Francisco, and Washington, D. C. during 1962 and 1963. The data serve as a basis for describing several contrasts and similarities in the nature of air pollution experienced in six cities, which represent a broad geographical and climatological range of urbayi environments. Specific topics covered are: typical pollutant levels, patterns of daily and seasonal variations, and unusual phenomena such as atmospheric stagnation periods and photochemical smog formation.     

Apportionment of Ambient Primary and Secondary Pollutants during a 2001 Summer Study in Pittsburgh Using U.S. Environmental Protection Agency UNMIX

Abstract

Apportionment of primary and secondary pollutants during the summer 2001 Pittsburgh Air Quality Study (PAQS) is reported. Several sites were included in PAQS, with the main site (the supersite) adjacent to the Carnegie Mellon University campus in Schenley Park. One of the additional sampling sites was located at the National Energy Technology Laboratory, located ～18 km southeast of downtown Pittsburgh. Fine particulate matter (PM_2.5) mass, gas-phase volatile organic material (VOM), particulate semivolatile and nonvolatile organic material (NVOM), and ammonium sulfate were apportioned at the two sites into their primary and secondary contributions using the U.S. Environmental Protection Agency UNMIX 2.3 multivariate receptor modeling and analysis software. A portion of each of these species was identified as originating from gasoline and diesel primary mobile sources. Some of the organic material was formed from local secondary transformation processes, whereas the great majority of the secondary sulfate was associated with regional transformation contributions. The results indicated that the diurnal patterns of secondary gas-phase VOM and particulate semivolatile and NVOM were not correlated with secondary ammonium sulfate contributions but were associated with separate formation pathways. These findings are consistent with the bulk of the secondary ammonium sulfate in the Pittsburgh area being the result of contributions from distant transport and, thus, decoupled from local activity involving organic pollutants in the metropolitan area.     

Source Apportionment of Fine Particulate Matter in the Southeastern United States

Abstract

Particulate matter (PM) less than 2.5 μm in size (PM_2.5)source apportionment by chemical mass balance receptor modeling was performed to enhance regional characterization of source impacts in the southeastern United States. Secondary particles, such as NH₄HSO₄, (NH₄)₂SO₄,NH₄NO₃, and secondary organic carbon (OC) (SOC), formed by atmospheric photochemical reactions, contribute the majority (<50%) of ambient PM_2.5 with strong seasonality. Source apportionment results indicate that motor vehicle and biomass burning are the two main primary sources in the southeast, showing relatively more motor vehicle source impacts rather than biomass burning source impacts in populated urban areas and vice versa in less urbanized areas. Spatial distributions of primary source impacts show that each primary source has distinctively different spatial source impacts. Results also find impacts from shipping activities along the coast. Spatiotemporal correlations indicate that secondary particles are more regionally distributed, as are biomass burning and dust, whereas impacts of other primary sources are more local.     

Characterization of DNAPL from the U.S. DOE Savannah River Site

The composition of chlorinated hydrocarbon DNAPLs (dense non-aqueous phase liquids) from field sites can be substantially different than the material originally purchased for use as a solvent. Waste management practices at the U.S. Department of Energy's (DOE) Savannah River Site (SRS) included co-disposal of a wide range of organic and inorganic wastes. In 1991, a clear, orange-colored DNAPL was found in two wells near the SRS M-area settling basin. Waste effluent from the fuel and target fabrication facilities that were discharged to this settling basin included acids, caustics, metals and chlorinated solvents. The characterization of the SRS DNAPL suggests that numerous constituents partitioned into the DNAPL during its use as a solvent, co-disposal and ultimate migration through the subsurface. Trace constituents in the DNAPL include metals, from processing operations or co-disposal practices and subsurface minerals, high molecular weight hydrocarbons and alkyl esters, and acids. This complex mixture results in DNAPL-water interfacial properties that are substantially different than would be expected from a simple mixture of PCE and TCE. Under conditions when there is a high DNAPL to water volume ratio, a semi-rigid film accumulates on water droplets suspended in the DNAPL. It is concluded that the array of precipitated metal species comprising this film contributes to the interfacial tension that is over an order of magnitude lower than expected for a "clean" PCE/TCE mixture.     

Apportionment of ambient primary and secondary pollutants during a 2001 summer study in Pittsburgh using U.S. Environmental Protection Agency UNMIX

Apportionment of primary and secondary pollutants during the summer 2001 Pittsburgh Air Quality Study (PAQS) is reported. Several sites were included in PAQS, with the main site (the supersite) adjacent to the Carnegie Mellon University campus in Schenley Park. One of the additional sampling sites was located at the National Energy Technology Laboratory, located approximately 18 km southeast of downtown Pittsburgh. Fine particulate matter (PM2.5) mass, gas-phase volatile organic material (VOM), particulate semivolatile and nonvolatile organic material (NVOM), and ammonium sulfate were apportioned at the two sites into their primary and secondary contributions using the U.S. Environmental Protection Agency UNMIX 2.3 multivariate receptor modeling and analysis software. A portion of each of these species was identified as originating from gasoline and diesel primary mobile sources. Some of the organic material was formed from local secondary transformation processes, whereas the great majority of the secondary sulfate was associated with regional transformation contributions. The results indicated that the diurnal patterns of secondary gas-phase VOM and particulate semivolatile and NVOM were not correlated with secondary ammonium sulfate contributions but were associated with separate formation pathways. These findings are consistent with the bulk of the secondary ammonium sulfate in the Pittsburgh area being the result of contributions from distant transport and, thus, decoupled from local activity involving organic pollutants in the metropolitan area.     

Source Apportionment of Phoenix PM2.5 Aerosol with the Unmix Receptor Model

Abstract

The multivariate receptor model Unmix has been used to analyze a 3-yr PM_2.5 ambient aerosol data set collected in Phoenix, AZ, beginning in 1995. The analysis generated source profiles and overall average percentage source contribution estimates (SCEs) for five source categories: gasoline engines (33 ± 4%), diesel engines (16 ± 2%), secondary SO₄ ^2? (19 ± 2%), crustal/soil (22 ± 2%), and vegetative burning (10 ± 2%). The Unmix analysis was supplemented with scanning electron microscopy (SEM) of a limited number of filter samples for information on possible additional low-strength sources. Except for the diesel engine source category, the Unmix SCEs were generally consistent with an earlier multivariate receptor analysis of essentially the same data using the Positive Matrix Factorization (PMF) model. This article provides the first demonstration for an urban area of the capability of the Unmix receptor model.     

Particulate emissions from U.S. Department of Defense artillery backblast testing

There is a dearth of information on dust emissions from sources that are unique to the U.S. Department of Defense testing and training activities. However, accurate emissions factors are needed for these sources so that military installations can prepare accurate particulate matter (PM) emission inventories. One such source, coarse and fine PM (PM10 and PM2.5) emissions from artillery backblast testing on improved gun positions, was characterized at the Yuma Proving Ground near Yuma, AZ, in October 2005. Fugitive emissions are created by the shockwave from artillery pieces, which ejects dust from the surface on which the artillery is resting. Other contributions of PM can be attributed to the combustion of the propellants. For a 155-mm howitzer firing a range of propellant charges or zones, amounts of emitted PM10 ranged from -19 g of PM10 per firing event for a zone 1 charge to 92 g of PM10 per firing event for a zone 5. The corresponding rates for PM2.5 were approximately 9 g of PM2.5 and 49 g of PM2.5 per firing. The average measured emission rates for PM1o and PM2.5 appear to scale with the zone charge value. The measurements show that the estimated annual contributions of PM10 (52.2 t) and PM2.5 (28.5 t) from artillery backblast are insignificant in the context of the 2002 U.S. Environment Protection Agency (EPA) PM emission inventory. Using national-level activity data for artillery fire, the most conservative estimate is that backblast would contribute the equivalent of 5 x 10(-4) % and 1.6 x 10(-3)% of the annual total PM10 and PM2.5 fugitive dust contributions, respectively, based on 2002 EPA inventory data.     

Continuous and semicontinuous monitoring techniques for particulate matter mass and chemical components: a synthesis of findings from EPA's Particulate Matter Supersites Program and related studies

The U.S. Environmental Protection Agency (EPA) established the Particulate Matter (PM) Supersites Program to provide key stakeholders (government and private sector) with significantly improved information needed to develop effective and efficient strategies for reducing PM on urban and regional scales. All Supersites projects developed and evaluated methods and instruments, and significant advances have been made and applied within these programs to yield new insights to our understanding of PM accumulation in air as well as improved source-receptor relationships. The tested methods include a variety of continuous and semicontinuous instruments typically with a time resolution of an hour or less. These methods often overcome many of the limitations associated with measuring atmospheric PM mass concentrations by daily filter-based methods (e.g., potential positive or negative sampling artifacts). Semicontinuous coarse and ultrafine mass measurement methods also were developed and evaluated. Other semicontinuous monitors tested measured the major components of PM such as nitrate, sulfate, ammonium, organic and elemental carbon, trace elements, and water content of the aerosol as well as methods for other physical properties of PM, such as number concentration, size distribution, and particle density. Particle mass spectrometers, although unlikely to be used in national routine monitoring networks in the foreseeable future because of their complex technical requirements and cost, are mentioned here because of the wealth of new information they provide on the size-resolved chemical composition of atmospheric particles on a near continuous basis. Particle mass spectrometers likely represent the greatest advancement in PM measurement technology during the last decade. The improvements in time resolution achieved by the reported semicontinuous methods have proven to be especially useful in characterizing ambient PM, and are becoming essential in allowing scientists to investigate sources of particulate pollution and to probe into the dynamics and mechanisms of aerosol formation in the atmosphere.     

Carbon Monoxide in an Urban Environment: Application of a Receptor Model for Source Apportionment

During the winter of 1985-86 the authors took 6-h integrated air samples and measured the concentrations of carbon monoxide and other gases at a residential site in Olympia, Washington. The 6-h average concentrations were between about 0.2 and 3.2 ppmv. For each 6-h period the observed concentration of CO was apportioned among its sources which were residential wood burning and automobiles. Small and generally insignificant amounts of CO were also observed from unidentified sources. A chemical mass balance (CMB) was formulated and applied to apportion the observed CO among its sources. Methylchloride (CH₃CI), in excess of background levels, was used as a unique tracer of wood burning and excess hydrogen (H₂) served as a tracer of CO from automobiles. The source emission factors to carry out the calculations were estimated from other experiments. The results showed that in Olympia, wood burning can often contribute as much CO as automobiles during winter. The maximum 6-h average contribution of CO from wood burning was about 2 ppmv and from automobiles it was 2.2 ppmv, and the average ambient concentration was about 1 ppmv. When pollution from wood burning was present, it contributed 0.5 ppmv on average while automobiles also contributed 0.5 ppmv. Unidentified sources contributed 0.1 ppmv and the background level was 0.15 ppmv. During the winter many times wood burning did not affect CO concentrations, while CO from automobiles was always present. On average, during the winter, automobiles contributed some 50 percent of the CO mass to the lower urban atmosphere and wood burning contributed about 30 percent. Diurnal cycles became evident in the calculated concentrations of CO from wood burning and automobiles even though the measured concentrations did not show strong diurnal variations. Wood burning contributed most during evening and nighttime and very little during the day, while automobiles contributed most during the morning and evening hours and very little at night. These patterns lend support to the accuracy of the model and source emission factors since they are as expected from the diurnal variations of the sources and atmospheric mixing.     

Systematic error and uncertain carbon dioxide emissions from U.S. power plants

Carbon dioxide (CO₂) emissions from U.S. power plants are independently reported by the U.S. Energy Information Administration (EIA) and the Clean Air Markets Division (CAMD) within the U.S. Environmental Protection Agency (EPA). Differences between the CAMD and EIA emission tallies show that the amount of CO₂ produced by an individual power plant is less certain than might be imagined or desired. These differences are attributed to systematic error and random measurement error. Random error cannot be retroactively corrected, whereas systematic error can be corrected where relevant data are available. Accordingly, this study identified and, where possible, corrected systematic error affecting the CAMD and EIA CO₂ emission tallies for 1065 power plants that emitted more than 25,000 tons of CO₂ during 2013. The EIA tallies were corrected by accounting for emission factor error, acid-gas sorbent consumption, and combustion of biogenic fuel. The CAMD tallies were likewise corrected by accounting for unreported unit emissions. It was not possible to objectively correct systematic error affecting about 11% of the power plants, and subjective corrections were not attempted. At these plants, the CAMD and EIA emission tallies sometimes differed by more than 20% due to missing unit error, plant identification error, temporal measurement error, or inferred reporting error. Comparisons of the CAMD and EIA emission tallies before and after correction for systematic error show the effectiveness of these corrections. The comparisons also show the persistence of random measurement error.

Implications: Understanding the uncertainty of CO2 emission tallies for USA power plants might inform emission inventories, atmospheric flow models or inversions, and emission reduction policies. Knowing the cause and size of measurement errors that contribute to this uncertainty might also help to identify ways to improve the measurement methods and reporting protocols that these CO2 emission tallies are based on.     

The Steubenville Comprehensive Air Monitoring Program (SCAMP): Concentrations and Solubilities of PM2.5 Trace Elements and Their Implications for Source Apportionment and Health Research

Abstract

The elemental compositions of the water-soluble and acid-digestible fractions of 24-hr integrated fine particulate matter (PM_2.5) samples collected in Steubenville, OH, from 2000 to 2002 were determined using dynamic reaction cell inductively coupled plasma-mass spectrometry. The water-soluble elemental compositions of PM_2.5 samples collected at four satellite monitoring sites in the surrounding region were also determined. Fe was the most abundant but least water soluble of the elements determined at the Steubenville site, having a mean ambient concentration of 272 µg/m³ and a median fractional solubility of 6%. Fe solubility and its correlations with SO₄ ^2? and temperature varied significantly by season, consistent with the hypothesis that secondary sulfates may help to mobilize soluble Fe under suitable summertime photochemical conditions. Significantly higher ambient concentrations were observed at Steubenville than at each of the four satellite sites for 10 of the 18 elements (Al, As, Ca, Cd, Fe, Mg, Mn, Na, Pb, and Zn) determined in the water-soluble PM_2.5 fraction. Concentrations of Fe, Mn, and Zn at Steubenville were substantially higher than concentrations reported recently for larger U.S. cities. Receptor modeling identified seven sources affecting the Steubenville site. An (NH₄)₂SO₄-dominated source, likely representing secondary PM_2.5 from coal-fired plants to the west and southwest of Steubenville, accounted for 42% of the PM_2.5 mass, and two sources likely dominated by emissions from motor vehicles and from iron and steel facilities in the immediate Steubenville vicinity accounted for 20% and 10%, respectively. Other sources included an NH₄NO₃ source (15%), a crustal source (6%), a mixed nonferrous metals and industrial source (3%), and a primary coal combustion source (3%). Results suggest the importance of very different regional and local source mechanisms in contributing to PM_2.5 mass at Steubenville and reinforce the need for further research to elucidate whether metals such as Fe, Mn, and Zn play a role in the PM_2.5 health effects observed previously there.     

Source identifications of airborne fine particles using positive matrix factorization and U.S. Environmental Protection Agency positive matrix factorization

The widely used source apportionment model, positive matrix factorization (PMF2), has been applied to various air pollution data. Recently, U.S. Environmental Protection Agency (EPA) developed EPA positive matrix factorization (PMF), a version of PMF that will be freely distributed by EPA. The objectives of this study were to conduct source apportionment studies for particulate matter less than 2.5 microm in aerodynamic diameter (PM(2.5)) speciation data using PMF2 and EPA PMF (version 1.1) and to compare identified sources between the two models. In the present study, ambient PM(2.5) compositional datasets of 24-hr integrated samples collected at EPA Speciation Trends Network monitoring sites in Chicago, IL, and Portland, OR, were analyzed. Both PMF2 and EPA PMF extracted eight sources for the Chicago data and 10 sources for the Portland data. The model-resolved source profiles were similar between two models for both datasets. However, in several sources, the average contributions did not agree well and the time series contributions were not highly correlated. The differences between PMF2 and EPA PMF solutions were caused by the different least-square algorithm and the different nonnegativity constraints. Most of the average source contributions resolved by both models were within 5-95% uncertainty provided by EPA PMF, indicating that the sources resolved by both models were reproducible.     

Feasibility of Soil Dust Source Apportionment by the Pyrolysis-Gas Chromatography/Mass Spectrometry Method

Abstract

This study tested the feasibility of using pyrolysis (Py)-gas chromatography (GC)/mass spectrometry (MS) to obtain organic chemical species data suitable for source apportionment modeling of soil-derived coarse particulate matter (PM₁₀) dust on ambient filters. A laboratory resuspension apparatus was used with known soils to generate simulated receptor filter samples loaded with ～0.4 mg of PM₁₀ dust, which is within the range of mass loading on ambient filters. Py-GC/MS at 740 °C generated five times more resolvable compounds than were obtained with thermal desorption GC/MS at 315 °C. The identified compounds were consistent with literature from Py experiments using larger samples of bulk soils. A subset of 91 organic species out of the 178 identified Py products was used as input to CMB8 software in a demonstration of source apportionment using laboratory-generated mixtures simulating ambient filter samples. The 178 quantified organic species obtained by Py of soil samples is an improvement compared with the 38 organic species obtained by thermal desorption of soils and the four functionally defined organic fractions reported by thermal/optical reflectance. Significant differences in the concentration of specific species were seen between samples from different sites, both geographically distant and close, using analysis of variance and cluster analysis. This feasibility study showed that Py-GC/MS can generate useful source profile data for receptor modeling and justifies continued method development.