Characterization of PM2.5-bound polycyclic aromatic hydrocarbons in Atlanta

Twenty-four hour PM_2.5 samples from a rural site, an urban site, and a suburban site (next to a major highway) in the metropolitan Atlanta area in December 2003 and June 2004 were analyzed for 19 polycyclic aromatic hydrocarbons (PAH). Extraction of the air samples was conducted using an accelerated solvent extraction method followed by isotope dilution gas chromatography/mass spectrometry determination. Distinct seasonal variations were observed in total PAH concentration (i.e. significantly higher concentrations in December than in June). Mean concentrations for total particulate PAHs in December were 3.16, 4.13, and 3.40 ng m^?3 for the urban, suburban and rural sites, respectively, compared with 0.60, 0.74, and 0.24 ng m^?3 in June. Overall, the suburban site, which is impacted by a nearby major highway, had higher PAH concentration than did the urban site. Total PAH concentrations were found to be well correlated with PM_2.5, organic carbon (OC), and elemental carbon (EC) in both months (r² = 0.36–0.78, p < 0.05), although the slopes from the two months were different. PAHs represented on average 0.006% of total PM_2.5 mass and 0.017% of OC in June, compared with 0.033% of total PM_2.5 and 0.14% of OC in December. Total PAH concentrations were also correlated with potassium ion (r² = 0.39, p = 0.014) in December, but not in June, suggesting that in winter biomass burning can potentially be an important source for particulate PAH. Retene was found at a higher median air concentration at the rural site than at the urban and suburban sites—unlike the rest of the PAHs, which were found at lower levels at the rural site. Retene also had a larger seasonal difference and had the weakest correlation with the rest of the PAHs measured, suggesting that retene, in particular, might be associated with biomass burning.     

Temporal and Spatial Distributions of Ozone in Atlanta: Regulatory and Epidemiologic Implications

ABSTRACT

Relationships between ambient levels of selected air pollutants and pediatric asthma exacerbation in Atlanta were studied retrospectively. As a part of this study, temporal and spatial distributions of ambient ozone concentrations in the 20-county Atlanta metropolitan area during the summers of 1993, 1994, and 1995 were assessed. A universal kriging procedure was used for spatial interpolation of aerometric monitoring station data. In this paper, the temporal and spatial distributions of ozone are described, and regulatory and epidemiologic implications are discussed. For the study period, the Atlanta ozone nonattainment area based on the 1-h, exceedance-based standard of 0.12 ppm is estimated to expand—from 56% of the Atlanta MSA by area and 71% by population to 88% by area and 96% by population—under the new 8-h, concentration-based standard of 0.08 ppm. Regarding asthma exacerbation, a 4% increase in pediatric asthma rate per 20-ppb increase in ambient ozone concentration was observed (p-value = 0.001), with ambient ozone level representing a general indicator of air quality due to its correlations with other pollutants. The use of spatial ozone estimates in the epidemiologic analysis demonstrates the need for control of demographic covariates in spatiotem poral assessments of associations of ambient air pollutant concentrations with health outcome.     

Polychlorinated dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF) isomer patterns from municipal waste combustion: formation mechanism fingerprints

Polychlorinated dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF) byproducts can be formed in combustion systems by a variety of mechanisms. While total PCDD/F emissions and, to a lesser extent, homologue distributions from incinerators have been found to vary widely depending on combustion conditions, PCDD/F isomer distributions do not. Formation mechanisms can be grouped into two general categories: condensation of precursors, such as chlorinated phenols, and formation from particulate carbon, termed de novo synthesis. In addition to these mechanisms, chlorination and dechlorination reactions may affect isomer patterns. In this work, isomer patterns from field and laboratory municipal waste combustion samples are compared with computed thermodynamic distributions and those from the following experimental investigations: both gas-phase and metal-catalyzed condensation of chlorinated phenols, chlorination of dibenzo-p-dioxin and dibenzofuran, and dechlorination of octachlorodibenzo-p-dioxin and octachlorodibenzofuran. PCDD/F isomer patterns produced by different formation mechanisms in controlled experiments are distinct and robust, largely unaffected by combustion conditions. PCDD isomer patterns from municipal waste combustion are most similar to those produced by CuCl(2)-catalyzed phenol condensation from 10 chlorinated phenols. PCDF isomer patterns are most similar to those produced by chlorination and dechlorination.     

Development of outcome-based, multipollutant mobile source indicators

Multipollutant indicators of mobile source impacts are developed from readily available CO, NOx, and elemental carbon (EC) data for use in air quality and epidemiologic analysis. Two types of outcome-based Integrated Mobile Source Indicators (IMSI) are assessed. The first is derived from analysis of emissions of EC, CO, and NOx such that pollutant concentrations are mixed and weighted based on emission ratios for both gasoline and diesel vehicles. The emission-based indicators (IMSI(EB)) capture the impact of mobile sources on air quality estimated from receptor models and their uncertainty is comparable to measurement and source apportionment uncertainties. The IMSI(EB) have larger correlation between two different receptor sites impacted by traffic than single pollutants, suggesting they are better indicators of the local impact ofmobile sources. A sensitivity analysis of fractions of pollutants in a two-pollutant mixture and the inclusion in an epidemiologic model is conducted to develop a second set of indicators based on health outcomes. The health-based indicators (IMSI(HB)) are weighted combinations of CO, NOx, and EC pairs that have the lowest P value in their association with cardiovascular disease emergency department visits, possibly due to their better spatial representativeness. These outcome-based, multipollutant indicators can provide support for the setting of multipollutant air quality standards and other air quality management activities.     

PAH Growth from the pyrolysis of CPD, indene and naphthalene mixture

In this study, the addition of cyclopentadienyl (CPDyl) moieties to aromatic rings has been investigated experimenNaphthalene was selected as the representative aromatic compound and its pyrolytic reactivity was studied first to obtain background information for the pyrolysis of cyclopentadiene-indene-naphthalene mixture. The experiments were conducted in a 5 s laminar flow reactor over the temperature range of 700-850 degrees C with 50 degrees C increments. PAH growth from naphthalene pyrolysis is mainly attributed to aryl-aryl addition of naphthyl radicals and naphthalene fragmentation, with lower product formation rates comparing with hydrocarbons with CPDyl moieties. The results indicate that naphthalene is less reactive than the CPDyl containing hydrocarbon radical-molecule addition of CPDyl radicals to naphthalene results in phenanthrene, which can also be formed substantially from other growth pathways. This addition occurs mainly at low temperatures and is less favored due to the competition from more reactive indenyl and CPDyl radicals. CPDyl radical addition to naphthalene exhibits limited aromatic growth due to the aromaticity restrictions of naphthalene. The studies of hydrocarbons with and without CPDyl moieties suggest that the reaction pathways of CPDyl bearing hydrocarbons are different from those without these moieties and cannot be adequately accounted for by the existing acetylene addition and aryl-aryl addition mechanisms.     

IMPACTS OF CLIMATE CHANGE ON AQUATIC ECOSYSTEM FUNCTIONING AND HEALTH1

ABSTRACT: We review published analyses of the effects of climate change on goods and services provided by freshwater ecosystems in the United States. Climate-induced changes must be assessed in the context of massive anthropogenic changes in water quantity and quality resulting from altered patterns of land use, water withdrawal, and species invasions; these may dwarf or exacerbate climate-induced changes. Water to meet instream needs is competing with other uses of water, and that competition is likely to be increased by climate change. We review recent predictions of the impacts of climate change on aquatic ecosystems in eight regions of North America. Impacts include warmer temperatures that alter lake mixing regimes and availability of fish habitat; changed magnitude and seasonality of runoff regimes that alter nutrient loading and limit habitat availability at low flow; and loss of prairie pothole wetlands that reduces waterfowl populations. Many of the predicted changes in aquatic ecosystems are a consequence of climatic effects on terrestrial ecosystems; shifts in riparian vegetation and hydrology are particularly critical. We review models that could be used to explore potential effects of climate change on freshwater ecosystems; these include models of instream flow, bioenergetics models, nutrient spiraling models, and models relating riverine food webs to hydrologic regime. We discuss potential ecological risks, benefits, and costs of climate change and identify information needs and model improvements that are required to improve our ability to predict and identify climate change impacts and to evaluate management options.     

Characterization of fuel gas products from the treatment of solid waste streams with a plasma arc torch

This work addresses the plasma treatment of two solid waste streams and production of fuel gases from the process. In this study, carpet waste and simulated solid wastes generated by a United States Air Force Basic Expeditionary Airfield Resources Base deployment were used. Waste was treated in a furnace fitted with a 100kW plasma arc torch. The off gas was analyzed to determine its composition. The product gas was composed primarily of carbon monoxide and hydrogen, with small amounts of methane, benzene and toluene also detected. These experiments demonstrate the feasibility of producing fuel gases by plasma treatment of the solid waste streams. While the thermal energy value of the fuel gas produced in these experiments was less than the energy input, a higher waste-to-fuel gas conversion efficiency is expected in full-scale application.