Improving source apportionment of fine particles in the eastern United States utilizing temperature-resolved carbon fractions

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 (PM2.5) 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 PM2.5.     

Gas-phase mercury reduction to measure total mercury in the flue gas of a coal-fired boiler

Gaseous elemental and total (elemental + oxidized) mercury (Hg) in the flue gas from a coal-fired boiler was measured by a modified ultraviolet (UV) spectrometer. Challenges to Hg measurement were the spectral interferences from other flue gas components and that UV measures only elemental Hg. To eliminate interference from flue gas components, a cartridge filled with gold-coated sand removed elemental Hg from a flue gas sample. The Hg-free flue gas was the reference gas, eliminating the spectral interferences. To measure total Hg by UV, oxidized Hg underwent a gas-phase, thermal-reduction in a quartz cell heated to 750 degrees C. Simultaneously, hydrogen was added to flash react with the oxygen present forming water vapor and preventing Hg re-oxidation as it exits the cell. Hg concentration results are in parts per billion by volume Hg at the flue gas oxygen concentration. The modified Hg analyzer and the Ontario Hydro method concurrently measured Hg at a field test site. Measurements were made at a 700-MW steam turbine plant with scrubber units and selective catalytic reduction. The flue gas sampled downstream of the selective catalytic reduction contained 2100 ppm SO2 and 75 ppm NOx. Total Hg measured by the Hg analyzer was within 20% of the Ontario Hydro results.     

Source identification of atlanta aerosol by positive matrix factorization

Data characterizing daily integrated particulate matter (PM) samples collected at the Jefferson Street monitoring site in Atlanta, GA, were analyzed through the application of a bilinear positive matrix factorization (PMF) model. A total of 662 samples and 26 variables were used for fine particle (particles < or = 2.5 microm in aerodynamic diameter) samples (PM2.5), and 685 samples and 15 variables were used for coarse particle (particles between 2.5 and 10 microm in aerodynamic diameter) samples (PM10-2.5). Measured PM mass concentrations and compositional data were used as independent variables. To obtain the quantitative contributions for each source, the factors were normalized using PMF-apportioned mass concentrations. For fine particle data, eight sources were identified: SO4(2-) -rich secondary aerosol (56%), motor vehicle (22%), wood smoke (11%), NO(3-) -rich secondary aerosol (7%), mixed source of cement kiln and organic carbon (OC) (2%), airborne soil (1%), metal recycling facility (0.5%), and mixed source of bus station and metal processing (0.3%). The SO4(2-) -rich and NO(3-) -rich secondary aerosols were associated with NH(4+). The SO4(2-) -rich secondary aerosols also included OC. For the coarse particle data, five sources contributed to the observed mass: airborne soil (60%), NO(3-)-rich secondary aerosol (16%), SO4(2-) -rich secondary aerosol (12%), cement kiln (11%), and metal recycling facility (1%). Conditional probability functions were computed using surface wind data and identified mass contributions from each source. The results of this analysis agreed well with the locations of known local point sources.     

Source characterization of ambient fine particles at multiple sites in the Seattle area

To identify major PM_2.5 (particulate matter ≤2.5 μm in aerodynamic diameter) sources with a particular emphasis on the ship engine emissions from a major port, integrated 24 h PM_2.5 speciation data collected between 2000 and 2005 at five United State Environmental Protection Agency's Speciation Trends Network monitoring sites in Seattle, WA were analyzed. Seven to ten PM_2.5 sources were identified through the application of positive matrix factorization (PMF). Secondary particles (12–26% for secondary nitrate; 17–20% for secondary sulfate) and gasoline vehicle emissions (13–31%) made the largest contributions to the PM_2.5 mass concentrations at all of the monitoring sites except for the residential Lake Forest site, where wood smoke contributed the most PM_2.5 mass (31%). Other identified sources include diesel vehicle emissions, airborne soil, residual oil combustion, sea salt, aged sea salt, metal processing, and cement kiln. Residual oil combustion sources identified at multiple monitoring sites point clearly to the Port of Seattle suggesting ship emissions as the source of oil combustion particles. In addition, the relationship between sulfate concentrations and the oil combustion emissions indicated contributions of ship emissions to the local sulfate concentrations. The analysis of spatial variability of PM_2.5 sources shows that the spatial distributions of several PM_2.5 sources were heterogeneous within a given air shed.     

EXPERIMENTAL EVALUATION OF MULTIPLE CRITERIA DECISION MODELS FOR APPLICATION TO WATER RESOURCES PLANNING1

ABSTRACT: A research project was undertaken for the U.S. Army Corps of Engineers to determine the relative utility and effectiveness of four well-known multicriteria decision making (MCDM) models for applications in realistic water resources planning settings. A series of experiments was devised to examine the impact of rating and ranking procedures on the decision making behavior of users (e.g., planners, managers, analysts, etc.) when faced with situations involving multiple evaluation criteria and numerous alternative planning projects. The four MCDM models tested were MATS-PC, EXPERT CHOICE, ARIADNE, and ELECTRE. Two groups of analysts and decision makers were tested. One group consisted of experienced U.S. Army Corps planners, while the other was comprised of graduate students. Based on a series of nonparametric statistical tests, the results identified EXPERT CHOICE as the preferred MCDM model by both groups based largely on ease of use and understandability. ARIADNE fostered the largest degree of agreement within and among the two groups of individuals tested. The tests also lend support to the claim that rankings are not affected significantly by the choice of decision maker (i.e., who uses any of these MCDM models) or which of these four models is used.     

Immobilizing a light,nonaqueous phase liquid

A new technique has been developed to immobilize organic chemicals at a Superfund site. In the course of predesign studies in preparing the Remedial Design for the Pioneer Sand Superfund site in Pensacola, Florida, a light, nonaqueous phase liquid (LNAPL) was discovered floating on the groundwater within the on-site landfill. The liquid, with a viscosity similar to SAE 20 motor oil, was made up of heavy organic chemicals and volatile organic chemicals (VOCs), but no pesticides or polychlorinated biphenyls (PCBs). The volatiles present included toluene, ethylbenzene, and xylenes. Regulatory agencies expressed concern over the possibility of LNAPL migration and asked that a method of LNAPL immobilization be devised.     

Soil and water characteristics of a young surface mine wetland

Coal companies are reluctant to include wetland development in reclamation plans partly due to a lack of information on the resulting characteristics of such sites. It is easier for coal companies to recreate terrestrial habitats than to attempt experimental methods and possibly face significant regulatory disapproval. Therefore, we studied a young (10 years) wetland on a reclaimed surface coal mine in southern Illinois so as to ascertain soil and water characteristics such that the site might serve as a model for wetland development on surface mines. Water pH was not measured because of equipment problems, but evidence (plant life, fish, herpetofauna) suggests suitable pH levels. Other water parameters (conductivity, salinity, alkalinity, chloride, copper, total hardness, iron, manganese, nitrate, nitrite, phosphate, and sulfate) were measured, and only copper was seen in potentially high concentrations (but with no obvious toxic effects). Soil variables measured included pH, nitrate, nitrite, ammonia, potassium, calcium, magnesium, manganese, aluminum, iron, sulfate, chloride, and percent organic matter. Soils were slightly alkaline and most parameters fell within levels reported for other studies on both natural and manmade wetlands. Aluminum was high, but this might be indicative more of large amounts complexed with soils and therefore unavailable, than amounts actually accessible to plants. Organic matter was moderate, somewhat surprising given the age of the system.     

Spectroscopic characterization of the structural and functional properties of natural organic matter fractions

Natural organic matter (NOM) is known to be complex in nature with varying structural and functional characteristics. In this study, an aquatic NOM was fractionated into the polyphenolic-rich (NOM-PP) and the carbohydrate-rich (NOM-CH) fractions in an attempt to better characterize their chemical and structural properties along with a reference soil humic acid (SHA). Various spectroscopic techniques were employed for the study, including ultraviolet-visible (UV/Vis). 13C-nuclear magnetic resonance, Fourier-transform infrared, fluorescence, and electron paramagnetic resonance spectroscopies. Results indicate that the relative abundance of aromatic C=C and methoxyl (-OCH3) functional groups are in the order of SHA > NOM-PP > NOM-CH. However, the aquatic NOM-PP and NOM-CH fractions are characterized by high contents of carboxylic and alcoholic functional groups relative to the SHA. In particular, the NOM-PP fraction appears to contain more phenolic and ketonic functional groups than the NOM-CH and SHA fractions, and it gives a strong fluorescence and high paramagnetic spin count. On the other hand, the NOM-CH fraction possesses a relatively low amount of carbon but a high amount of oxygen or oxygen-containing structural features, such as carbohydrate-OH and carboxylic groups, and shows the least fluorescence intensity and paramagnetic spin counts. Results of these spectroscopic studies confirm the heterogeneous nature of NOM, and point out the importance of isolation and improved characterization of various NOM subcomponents in order to better understand the behavior and roles of NOM in the natural environment.     

Source apportionment of fine particles in Washington, DC, utilizing temperature-resolved carbon fractions

Integrated ambient particulate matter < or =2.5 microm in aerodynamic diameter (PM2.5) samples were collected at a centrally located urban monitoring site in Washington, DC, on Wednesdays and Saturdays using Interagency Monitoring of Protected Visual Environments samplers. Particulate carbon was analyzed using the thermal optical reflectance method that divides carbon into four organic carbon fractions, pyrolyzed organic carbon, and three elemental carbon fractions. A total of 35 variables measured in 718 samples collected between August 1988 and December 1997 were analyzed. The data were analyzed using Positive Matrix Factorization and 10 sources were identified: sulfate (SO4(2-))-rich secondary aerosol I (43%), gasoline vehicle (21%), SO4(2-)-rich secondary aerosol II (11%), nitrate-rich secondary aerosol (9%), SO4(2-)-rich secondary aerosol III (6%), incinerator (4%), aged sea salt (2%), airborne soil (2%), diesel emissions (2%), and oil combustion (2%). In contrast to a previous study that included only total organic carbon and elemental carbon fractions, motor vehicles were separated into fractions identified as gasoline vehicle and diesel emissions containing carbon fractions whose abundances were different between the two sources. This study indicates that the temperature-resolved carbon fraction data can be utilized to enhance source apportionment, especially with respect to the separation of diesel emissions from gasoline vehicle sources. Conditional probability functions using surface wind data and deduced source contributions aid in the identifications of local sources.     

Tracking the anthropogenic drivers of ecological impacts

Despite the pivotal role human factors (anthropogenic drivers) are presumed to play in global environmental change, substantial uncertainties and contradictory conclusions about them continue. We attempt to further discipline the human factors issue by estimating the effects of two anthropogenic drivers, population and affluence, on a wide variety of global environmental impacts, including greenhouse gas emissions, emissions of ozone depleting substances, and the ecological footprint. Population proportionately increases all types of impacts examined. Affluence typically increases impacts, but the specific effect depends on the type of impact. These findings refocus attention on population and material affluence as principal threats to sustainability and challenge predictions of an ameliorating effect of rising affluence on impacts.