Assessment of secondary organic carbon in the Southeastern United States: a review

Organic carbon (OC) is one of the major components of ambient PM2.5 (particulate matter [PM] < or = 2.5 microm in aerodynamic diameter) and a significant portion of OC is from secondary organic aerosol (SOA) formation in the southeastern United States. Various approaches (based on measurement and modeling results) are applied to estimate secondary organic carbon (SOC) and its origins in the region. SOC estimates by various methods are consistent as to clear seasonal variation (i.e., relatively higher SOC in summer) and little spatial variability (i.e., a regional characteristic of SOC). However, there are differences as to the origins of SOC. SOA organic tracer and emission-based modeling studies indicate that the biogenic origin of SOC is dominant in the Southeast, showing that biogenic-origin SOC accounts for 90% of SOC in summer and more than 70% even in other seasons. However, results from other studies suggest that the anthropogenic origin of SOC is dominant, significant amounts of anthropogenic-origin SOC, or important roles of anthropogenic pollutants for SOA formation, especially at urban areas, as strong correlations between water-soluble OC (an indicator of SOC) and anthropogenic pollutants, considerable amounts of fossil water-soluble OC, and significant contributions of fossil SOC (37-52% in summer months, 70-73% in winter months) are observed. Therefore, more studies are needed to reconcile the differences in the source attribution of SOC measurements.     

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.     

Natural background visibility and regional haze goals in the Southeastern United States

The goal of the regional haze mitigation program in the United States is to attain "natural conditions" in national parks and wilderness areas by 2064. Results of research investigations on background concentrations of sea salt and biogenic organic matter, of episodic Saharan and Asian dust, and of carbon from natural fires were reviewed to provide a basis for making site-specific estimates of what the concentrations of atmospheric fine particulate matter components might be under natural conditions in the Southeastern United States. Based on this review, rough estimates were made of potential contributions of these aerosol components to natural background visibility. Natural organic particles were the dominant influence on the rate of visibility improvement required to reach natural conditions at an inland, mountainous location, and organic particles and sea salt were the dominant influences on the rate at a coastal location. African dust also had a large episodic effect, but the current regulatory approach is not designed to address episodic background variations. Insufficient data exist to quantify the contributions of wildfires with any detail, although global air pollution modeling provides insight, and their emissions can be locally dominant. Conservative regional refinements to the default natural background estimates do not greatly alter the region-wide rates of reduction of ambient particulate matter concentrations that will be needed to accomplish the first phase of the regional haze program. However, refinements at specific Class I areas may have considerable influence on defining the nature (magnitude and spatial and temporal distribution) of local emission reduction efforts there.     

Biogenic Sulfur Gas Emissions from Soils in Eastern and Southeastern United States

Data are presented for the first systematic measurements of biogenic sulfur gas flux from the major soil orders within the eastern and southeastern United States. Sulfur flux samples were collected and analyzed on-site during the fall of 1977, spring and summer of 1978 and summer of 1979. A total of 27 sampling locales in 17 states were examined. Eight additional sites were visited in 1980.

At some locales, two to four soils were examined, providing an even broader sampling of the soil orders. Three of the locales were revisited two or three times during the course of the study to establish the influence of seasonal climatology upon the measured emission rates and chemical composition of the sulfur flux mixtures.

The sulfur gas enhancement of sulfur-free sweep air passing through dynamic emission flux chambers placed over selected sampling areas was determined by combined cryogenic enrichment sampling and wall-coated, open tubular, capillary column, cryogenic gas chromatography (WCOT/GC) using a sulfur selective, flame photometric detector (FPD).

Sulfur gas mixtures varied with soil order, ambient temperature, insolation, soil moisture, cultivation, and vegetative cover. Statistical analyses indicated strong temperature and soil order relationships for sulfur emissions from soils.

Fluxes ranged from 0.001 g to 1940 g of total sulfur as S/m²/yr. The calculated mean annual sulfur flux, weighted by soil order, was 0.03 g S/m²/yr for the study land area, or 110,872 metric tons (mT). The estimated annual average sulfur flux increased from 65 mT per 6400 km² for the land grids in the northernmost east-west grid tier to an average 1800 mT for the land grids in the southern Florida grid tiers.

This systematic sampling of major soils provides a much broader data base for estimating biogenic sulfur flux than previously reported for isolated intertidal sites, and presents the first sulfur flux estimates for inland soils which make up approximately 93% of the land of the eastern United States.     

A Critical Assessment of Atmospheric Visibility and Aerosol Measurements in the Eastern United States

As part of a study examining the technical basis for a secondary national ambient air quality standard for fine particulate matter to protect visibility, we reviewed available data on atmospheric aerosol and visibility in the eastern U.S. This paper presents the results of that visibility and aerosol characterization.

Analysis of airport visibility data indicates that the annual median visual ranges in the East are in the 16-25 km range. In the absence of a "reference method," limited measurements of visibility using various types of instruments provide data generally in agreement with the airport visibility estimates when a contrast threshold of 0.05 is assumed in calculating visual range from the instrumental measurements.

Both long- and short-term aerosol measurements have yielded consistent results; however, because of the differences in instrumentation and laboratory analytical techniques among various studies, data often are not directly comparable. The measured annual average fine particulate matter mass concentration is about 18 μg/m³ in the rural East; during summer it increases to about 23 μg/m³. If all the sulfur in the fine mass is assumed to exist as ammonium sulfate, it would constitute 46 percent of the annual mean and about 60 percent of the summer mean fine mass concentrations. Carbon and volatiles, including water, are believed to constitute significant fractions of the fine mass; however, there are little data quantifying their contributions to fine mass and visibility impairment. Additional long-term measurements of visibility and fine aerosol and its various components are necessary to completely characterize visibility and aerosol in the East.     

Trends in speciated fine particulate matter and visibility across monitoring networks in the Southeastern United States

Trends in fine particulate matter <2.5 microm in diameter (PM2.5) and visibility in the Southeastern United States were evaluated for sites in the Interagency Monitoring of Protected Visual Environments, Speciated Trends Network, and Southeastern Aerosol Research and Characterization Study networks. These analyses are part of the technical assessment by Visibility Improvement-State and Tribal Association of the Southeast (VISTAS), the regional planning organization for the southeastern states, in support of State Implementation Plans for the regional haze rule. At all of the VISTAS IMPROVE sites, ammonium sulfate and organic carbon (OC) are the largest and second largest contributors, respectively, to light extinction on both the 20% haziest and 20% clearest days. Ammonium nitrate, elemental carbon (EC), soils, and coarse particles make comparatively small contributions to PM2.5 mass and light extinction on most days at the Class I areas. At Southern Appalachian sites, the 20% haziest days occur primarily in the late spring to fall, whereas at coastal sites, the 20% haziest days can occur through out the year. Levels of ammonium sulfate in Class I areas are similar to those in nearby urban areas and are generally higher at the interior sites than the coastal sites. Concentrations of OC, ammonium nitrate, and, sometimes, EC, tend to be higher in the urban areas than in nearby Class I areas, although differences in measurement methods complicate comparisons between networks. Results support regional controls of sulfur dioxide for both regional haze and PM2.5 implementation and suggest that controls of local sources of OC, EC, or nitrogen oxides might also be considered for urban areas that are not attaining the annual National Ambient Air Quality Standard for PM2.5.     

An Upper Limit Analysis of Carbon Monoxide Monitoring in the United States

In performing carbon monoxide (CO) studies, the question is invariably raised as to whether available monitoring data are truly representative of the highest ambient 8-hr average CO levels experienced in major cities. The most practical means for such a determinate is to inventory the critical characteristics of monitor siting. The authors catalogued such data for the worst station in eight of the 12 counties measuring the highest number of CO violations in the nation.     

The use of kriging to estimate monthly ozone exposure parameters for the Southeastern United States

This paper explores the feasibility of (1) using kriging to predict the monthly mean of daily 7-h mean (0900-1559) O3 concentrations, (2) using kriging to estimate the per cent of hourly mean O3 concentrations equal to or greater than 0.07 ppm (137 microg m(-3)) for a specific month, and (3) developing a quantitative relationship between the monthly mean of the daily 7-h (0900-1559) average O3 concentration and the monthly number of hourly concentrations > or = 0.08p ppm (157 microg m(-3)). We found that kriging can be used to estimate the (1) monthly mean of daily 7-h mean O3 concentrations and (2) the percentage of hourly concentrations for a given month > or = 0.07 ppm when sufficient spatial coverage was available. However, the per cent > or = 0.07 ppm parameter exhibited much greater relative variability than the monthly 7-h exposure index. A strong statistical association was found between the monthly number of occurrences > or = 0.08 ppm and monthly 7-h mean concentrations above 0.05 ppm (98 microg m(-3)). Because of the variability that cumulative indices, such as the monthly percentage of hourly concentrations > or = 0.07 ppm , exhibit from site to site, it appears that whether kriging techniques or mathematical regressions are used to estimate the number of elevated O3 hourly concentrations above selected thresholds, large uncertainties associated with the predicted values will exist. These large uncertainties will make it difficult to accurately estimate vegetation effects caused by ambient levels of O3. However, if a generalized quantitative relationship between repeated occurrences of hourly mean concentrations > or = 0.07 ppm or > or = 0.08 and vegetation effects can be developed, it may be possible, using kriged monthly values accompanied with confidence intervals, to identify those areas where vegetation may be at risk. However, before it will be possible to implement such an approach, researchers will have to better quantify the relationship between realistic O3 exposures and vegetation effects.     

Preliminary evaluation of the Community Multiscale Air Quality model for 2002 over the Southeastern United States

The Visibility Improvement State and Tribal Association of the Southeast (VISTAS) is one of five Regional Planning Organizations that is charged with the management of haze, visibility, and other regional air quality issues in the United States. The VISTAS Phase I work effort modeled three episodes (January 2002, July 1999, and July 2001) to identify the optimal model configuration(s) to be used for the 2002 annual modeling in Phase II. Using model configurations recommended in the Phase I analysis, 2002 annual meteorological (Mesoscale Meterological Model [MM5]), emissions (Sparse Matrix Operator Kernal Emissions [SMOKE]), and air quality (Community Multiscale Air Quality [CMAQ]) simulations were performed on a 36-km grid covering the continental United States and a 12-km grid covering the Eastern United States. Model estimates were then compared against observations. This paper presents the results of the preliminary CMAQ model performance evaluation for the initial 2002 annual base case simulation. Model performance is presented for the Eastern United States using speciated fine particle concentration and wet deposition measurements from several monitoring networks. Initial results indicate fairly good performance for sulfate with fractional bias values generally within +/-20%. Nitrate is overestimated in the winter by approximately +50% and underestimated in the summer by more than -100%. Organic carbon exhibits a large summer underestimation bias of approximately -100% with much improved performance seen in the winter with a bias near zero. Performance for elemental carbon is reasonable with fractional bias values within +/- 40%. Other fine particulate (soil) and coarse particular matter exhibit large (80-150%) overestimation in the winter but improved performance in the summer. The preliminary 2002 CMAQ runs identified several areas of enhancements to improve model performance, including revised temporal allocation factors for ammonia emissions to improve nitrate performance and addressing missing processes in the secondary organic aerosol module to improve OC performance.     

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.     

Improving Source Apportionment of Fine Particles in the Eastern United States Utilizing Temperature-Resolved Carbon Fractions

Abstract

The objectives of this study were to examine the use of carbon fractions to identify particulate matter (PM) sources, especially traffic‐related carbonaceous particle sources, and to estimate their contributions to the particle mass concentrations. In recent studies, positive matrix factorization (PMF) was applied to ambient fine PM (PM_2.5) compositional data sets of 24‐hr integrated samples including eight individual carbon fractions collected at three monitoring sites in the eastern United States: Atlanta, GA, Washington, DC, and Brigantine, NJ. Particulate carbon was analyzed using the Interagency Monitoring of Protected Visual Environments/Thermal Optical Reflectance method that divides carbon into four organic carbons (OC): pyrolized OC and three elemental carbon (EC) fractions. In contrast to earlier PMF studies that included only the total OC and EC concentrations, gasoline emissions could be distinguished from diesel emissions based on the differences in the abundances of the carbon fractions between the two sources. The compositional profiles for these two major source types show similarities among the three sites. Temperature‐resolved carbon fractions also enhanced separations of carbon‐rich secondary sulfate aerosols. Potential source contribution function analyses show the potential source areas and pathways of sulfate‐rich secondary aerosols, especially the regional influences of the biogenic, as well as anthropogenic secondary aerosol. This study indicates that temperature‐resolved carbon fractions can be used to enhance the source apportionment of ambient PM_2.5.     

A History of the Production and Use of Carbon Tetrachloride,Tetrachloroethylene, Trichloroethylene and 1,1,1-Trichloroethane in the United States: Part 1--Historical Background; Carbon Tetrachloride and Tetrachloroethylene

Carbon tetrachloride (CTC), tetrachloroethylene (PCE), trichloroethylene (TCE) and 1,1,1-trichloroethane (TCA) were four of the most widely used cleaning and degreasing solvents in the United States. These compounds were also used in a wide variety of other applications. The history of the production and use of these four compounds is linked to the development and growth of the United States' synthetic organic chemical industry, and historical events that affected the development and use of chlorinated solvents in general. Part 1 of this article includes a discussion of the historical background common to each of the four solvents, followed by discussion on the history of CTC and PCE. In the early years of the 20th century, CTC became the first of the four solvents to come into widespread use. CTC was used as a replacement for petroleum distillates in the dry-cleaning industry, but was later replaced by PCE. In the 1990s, CTC was phased out under the Montreal Protocol due to its role in stratospheric ozone depletion.     

Assessment of the Nested Grid Model Estimates for Driving Regional Visibility Models in the Southwestern United States

ABSTRACT

The Nested Grid Model (NGM) is a primitive-equation meteorological model that is routinely exercised over North America for forecasting purposes by the National Meteorological Center. While prognostic meteorological models are being increasingly used to drive air quality models, their use in conducting annual simulations requires significant resources. NGM estimates of wind fields and other meteorological variables provide an attractive alternative since they are typically archived and readily available for an entire year. Preliminary evaluation of NGM winds during the summer of 1992 for application to the region surrounding the Grand Canyon National Park showed serious shortcomings. The NGM winds along the borders between California, Arizona and Mexico tend to be northwesterly with a speed of about 6 m/sec, while the observed flow is predominantly southerly at about 2-5 m/sec. The mesoscale effect of a thermal low pressure area over the highly heated Southern California and western Arizona deserts does not appear to be represented by the NGM because of its coarse resolution and the use of sparse observations in that region. Tracer simulations and statistical evaluation against special high resolution observations of winds in the southwest United States clearly demonstrate the northwest bias in NGM winds and its adverse effect on predictions of an air quality model. The “enhanced” NGM winds, in which selected wind observations are incorporated in the NGM winds using a diagnostic meteorological model provide additional confirmation on the primary cause of the northwest bias. This study has demonstrated that in situations where limited resources prevent the use of prognostic meteorological models, previously archived coarse resolution wind fields in which additional observations are incorporated to correct known biases provide an attractive option.     

Assessment of the nested grid model estimates for driving regional visibility models in the southwestern United States

The Nested Grid Model (NGM) is a primitive-equation meteorological model that is routinely exercised over North America for forecasting purposes by the National Meteorological Center. While prognostic meteorological models are being increasingly used to drive air quality models, their use in conducting annual simulations requires significant resources. NGM estimates of wind fields and other meteorological variables provide an attractive alternative since they are typically archived and readily available for an entire year. Preliminary evaluation of NGM winds during the summer of 1992 for application to the region surrounding the Grand Canyon National Park showed serious shortcomings. The NGM winds along the borders between California, Arizona and Mexico tend to be northwesterly with a speed of about 6 m/sec, while the observed flow is predominantly southerly at about 2-5 m/sec. The mesoscale effect of a thermal low pressure area over the highly heated Southern California and western Arizona deserts does not appear to be represented by the NGM because of its coarse resolution and the use of sparse observations in that region. Tracer simulations and statistical evaluation against special high resolution observations of winds in the southwest United States clearly demonstrate the northwest bias in NGM winds and its adverse effect on predictions of an air quality model. The "enhanced" NGM winds, in which selected wind observations are incorporated in the NGM winds using a diagnostic meteorological model provide additional confirmation on the primary cause of the northwest bias. This study has demonstrated that in situations where limited resources prevent the use of prognostic meteorological models, previously archived coarse resolution wind fields in which additional observations are incorporated to correct known biases provide an attractive option.     

Organic Matter of the Troposphere—II.: Natural Background of biogenic lipid matter in aerosols over the rural western United States

Higher plant waxes are the predominant natural components in the lipid fractions (> C₁₅) of aerosols sampled over rural and oceanic regions. Hydrocarbon, fatty acid, ketone and fatty alcohol fractions of the lipids were characterized in terms of their contents of homologous compound series and specific biogenic molecular markers. Particulate samples from the rural western United States have been analyzed and compared with samples from urban Los Angeles and remote areas over the Atlantic Ocean. The samples from rural sites contained predominantly vascular plant wax and lesser amounts of higher plant sterols and resin residues. Urban samples and, to varying degrees, some rural samples contained primarily higher weight residues of petroleum products. The loadings of hydrocarbons derived from higher plant waxes ranged approximately from 10 to 160 ng m⁻³ of air (for fatty acids, 10–100 ng m⁻³ and for fatty alcohols, 10–200 ng m⁻³). Higher molecular weight lipids (i.e. plant epicuticular wax, terpenes, etc.) from flora comprise a significant component of the organic carbon in rural aerosols. Primary biogenic residues are major components of aerosols in all areas and they are important components in the global cycling of organic carbon.     

Ozone in the urban southeastern United States

Ozone measurements (daily maximum values) from the Aerometric Information Retrieval System database are analyzed for selected sites, during 1980 to 1988, in southeastern USA. Frequency distributions, for most sites during most years, show a typical bell-shaped curve with the higher frequency around the yearly daily maximum ozone mean of about 100 to about 110 microg m(-3) (50-55 ppbv). Abnormal years in ozone concentration may skew the distribution as the mean shifts. A correlation of daily maximum ozone concentrations above 140 microg m(-3) (70 ppbv) between sites shows a division between the sites in the northern protion of the region and those in the southern portion of the region. Variations in ozone levels are well correlated over distances of several hundred kilometers, suggesting that high values are associated with synoptic scale episodes. An ozone exposure analysis also shows higher ozone exposures (250-300 ppm days) in the northerly sites as compared to the southerly sites (150-170 ppm days).     

A principal component analysis of sulfur concentrations in the western United States

Data from a 40 site network of air samplers in the western United States were used in a principal components analysis to obtain spatial patterns of the inter-site correlations of sulfur concentrations. After rotation of the initial eigenvectors, two large regions were identified which accounted for 33.1% of the variance in the data. Three other smaller regions were identified which also had significant variance. The first eigenvector included all sites in the southern part of the network and was attributed to copper smelter emissions in Arizona and New Mexico. The second eigenvector included sites in the northern great plains and was attributed to episodic incursions of sulfur from the east. The third, fourth and fifth eigenvectors were attributed to locally important conditions.     

Rural ozone in the southeastern United States

Ozone measurements are reported for five rural sites in the Tennessee Valley region of the southeastern U.S. for periods ranging from 18 to 83 months during the years 1977 through 1984. Rural ozone (O₃) levels were found to equal or exceed urban values for the same region. The daily maximum 1-h average concentration was found to peak during the summer months, while the 24-h average concentrations were greatest in the spring. The annual cycle of daily maximum concentrations is related to the seasonal photochemical cycle. The annual cycle in 24-h average concentrations is best explained by the combined effects of the annual cycles in solar intensity and noctural O₃ depletion. There was no indication that stratospheric intrusions exhibited a significant influence on the annual O₃ cycles. Evidence was found for elevated O₃ levels during touchdown of plumes from large power plants. No long-term trend in rural O₃ concentrations, either daily maxima or means, was discernible.     

A History of the Production and Use of Carbon Tetrachloride,Tetrachloroethylene, Trichloroethylene and 1,1,1-Trichloroethane in the United States: Part 2--Trichloroethylene and 1,1,1-Trichloroethane

Carbon tetrachloride (CTC), tetrachloroethylene (PCE), trichloroethylene (TCE) and 1,1,1-trichloroethane (TCA) were four of the most widely used cleaning and degreasing solvents in the United States. Part 2 of this article describes the history of TCE and TCA. TCE production in the United States began in the early 1920s. TCE was used as a replacement for petroleum distillates in the dry-cleaning industry, and became the solvent of choice for vapor degreasing in the 1930s. TCE's use as a degreaser decreased in the 1960s due to toxicity concerns and the increasing popularity of TCA. Significant TCA use began in the 1950s with the development of suitable stabilizer formulations. In the 1990s, TCA was phased out under the Montreal Protocol due to its role in stratospheric ozone depletion.