Effects of instrument precision and spatial variability on the assessment of the temporal variation of ambient air pollution in Atlanta, Georgia

Data from the U.S. Environmental Protection Agency Air Quality System, the Southeastern Aerosol Research and Characterization database, and the Assessment of Spatial Aerosol Composition in Atlanta database for 1999 through 2002 have been used to characterize error associated with instrument precision and spatial variability on the assessment of the temporal variation of ambient air pollution in Atlanta, GA. These data are being used in time series epidemiologic studies in which associations of acute respiratory and cardiovascular health outcomes and daily ambient air pollutant levels are assessed. Modified semivariograms are used to quantify the effects of instrument precision and spatial variability on the assessment of daily metrics of ambient gaseous pollutants (SO2, CO, NOx, and O3) and fine particulate matter ([PM2.5] PM2.5 mass, sulfate, nitrate, ammonium, elemental carbon [EC], and organic carbon [OC]). Variation because of instrument imprecision represented 7-40% of the temporal variation in the daily pollutant measures and was largest for the PM2.5 EC and OC. Spatial variability was greatest for primary pollutants (SO2, CO, NOx, and EC). Population-weighted variation in daily ambient air pollutant levels because of both instrument imprecision and spatial variability ranged from 20% of the temporal variation for O3 to 70% of the temporal variation for SO2 and EC. Wind     

Effects of stream channelization on exports of nitrogen and phosphorus from north Carolina coastal plain watersheds

Nitrogen and phosphorus exports from channelizedstream watersheds were elevated over those from nearby natural swamp-stream watersheds. Nitrate exports were significantly greater from channelized-stream watersheds, and higher exports were attributed to faster groundwater drawdown, continual streamflow, and transformation of former floodplain to croplands following channelization. Exports of total organic nitrogen and total nitrogen were also significantly greater from channelized-stream watersheds. Differences in the exports of ammonium, filterable reactive phosphorus, and filterable unreactive phosphorus between the two watershed types were not detectable. Particulate phosphorus exports were significantly higher from channelized-stream watersheds, presumably because of greater erosion potential of nearby croplands and steep channel banks in the altered watersheds. The presence of nonpoint sources of pollution increased watershed exports of nutrients regardless of stream morphology. Examination of nutrient budgets for a portion of swamp floodplain at the base of one natural-stream watershed revealed that changes in local groundwater hydrology and stream morphology associated with channelization appeared to have greater effect on nutrient exports than simply the loss of bordering forested floodplain.     

Comparison of SOC estimates and uncertainties from aerosol chemical composition and gas phase data in Atlanta

In the Southeastern US, organic carbon (OC) comprises about 30% of the PM_2.5 mass. A large fraction of OC is estimated to be of secondary origin. Long-term estimates of SOC and uncertainties are necessary in the evaluation of air quality policy effectiveness and epidemiologic studies. Four methods to estimate secondary organic carbon (SOC) and respective uncertainties are compared utilizing PM_2.5 chemical composition and gas phase data available in Atlanta from 1999 to 2007. The elemental carbon (EC) tracer and the regression methods, which rely on the use of tracer species of primary and secondary OC formation, provided intermediate estimates of SOC as 30% of OC. The other two methods, chemical mass balance (CMB) and positive matrix factorization (PMF) solve mass balance equations to estimate primary and secondary fractions based on source profiles and statistically-derived common factors, respectively. CMB had the highest estimate of SOC (46% of OC) while PMF led to the lowest (26% of OC). The comparison of SOC uncertainties, estimated based on propagation of errors, led to the regression method having the lowest uncertainty among the four methods. We compared the estimates with the water soluble fraction of the OC, which has been suggested as a surrogate of SOC when biomass burning is negligible, and found a similar trend with SOC estimates from the regression method. The regression method also showed the strongest correlation with daily SOC estimates from CMB using molecular markers. The regression method shows advantages over the other methods in the calculation of a long-term series of SOC estimates.     

Assessment of non-occupational exposure to polycyclic aromatic hydrocarbons through personal air sampling and urinary biomonitoring

Non-occupational inhalation and ingestion exposure to polycyclic aromatic hydrocarbons (PAHs) has been studied in 8 non-smoking volunteers through personal air sampling and urinary biomonitoring. The study period was divided into 4 segments (2 days/segment), including weekdays with regular commute and weekends with limited traffic related exposures; each segment had a high or low PAH diet. Personal air samples were collected continuously from the subjects while at home, at work, and while commuting to and from work. All urine excretions were collected as individual samples during the study. In personal air samples, 28 PAHs were measured, and in urine samples 9 mono-hydroxylated metabolites (OH-PAHs) from 4 parent PAHs (naphthalene, fluorene, phenanthrene and pyrene) were measured. Naphthalene was found at higher concentrations in air samples collected at the subjects' residences, whereas PAHs with four or more aromatic rings were found at higher levels in samples taken while commuting. Urinary OH-PAH biomarker levels increased following reported high inhalation and/or dietary exposure. On days with a low PAH diet, the total amount of inhaled naphthalene during each 24-hour period was well correlated with the amount of excreted naphthols, as was, to a lesser extent, fluorene with its urinary metabolites. During days with a high dietary intake, only naphthalene was significantly correlated with its excreted metabolite. These findings suggest that this group of non-occupational subjects were exposed to naphthalene primarily through indoor air inhalation, and exposed to other PAHs such as pyrene mainly through ingestion.     

Emissions from carpet combustion in a pilot-scale rotary kiln: comparison with coal and particle-board combustion

The use of post-consumer carpet as a potential fuel substitute in cement kilns and other high-temperature processes is being considered to address the problem of huge volumes of carpet waste and the opportunity of waste-to-energy recovery. Carpet represents a high volume waste stream, provides high energy value, and contains other recoverable materials for the production of cement. This research studied the emission characteristics of burning 0.46-kg charges of chopped nylon carpet squares, pulverized coal, and particle-board pellets in a pilot-scale natural gas-fired rotary kiln. Carpet was tested with different amounts of water added. Emissions of oxygen, carbon dioxide, nitric oxide (NO), sulfur dioxide (SO2), carbon monoxide (CO), and total hydrocarbons and temperatures were continuously monitored. It was found that carpet burned faster and more completely than coal and particle board, with a rapid volatile release that resulted in large and variable transient emission peaks. NO emissions from carpet combustion ranged from 0.06 to 0.15 g/MJ and were inversely related to CO emissions. Carpet combustion yielded higher NO emissions than coal and particle-board combustion, consistent with its higher nitrogen content. SO2 emissions were highest for coal combustion, consistent with its higher sulfur content than carpet or particle board. Adding water to carpet slowed its burn time and reduced variability in the emission transients, reducing the CO peak but increasing NO emissions. Results of this study indicate that carpet waste can be used as an effective alternative fuel, with the caveats that it might be necessary to wet carpet or chop it finely to avoid excessive transient puff emissions due to its high volatility compared with other solid fuels, and that controlled mixing of combustion air might be used to control NO emissions from nylon carpet.     

Mutualism among parasitic nematodes: A population model

An apparently mutualistic association between Metastrongylus apri and M. pudendotectus, described on the basis of field and experimental infections of swine, is analyzed using a compartment model. Exploration of the model suggests that M. apri may be facultative mutualist and M. pudendotectus, and obligate mutualist.     

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.     

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.