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In-use light-duty gasoline vehicle particulate matter emissions on three driving cycles.

Twenty-four properly functioning and six high carbon monoxide emission light-duty gasoline vehicles were emission tested in Denver, CO, using the Federal Test Procedure (FTP), a hot start Unified Cycle (UC), and the REP05 driving cycles at 35 degrees F. All were 1990-1997 model year vehicles tested on both an oxygenated and a nonoxygenated fuel. PM10 emission rates for the properly functioning vehicles using oxygenated fuel averaged 6.1, 3.6, and 12.7 mg/mi for the FTP, UC, and REP05, respectively. The corresponding values for the high emitters were 52, 28, and 24 mg/mi. Use of oxygenated fuel significantly reduces PM10 on the FTP, with all the reduction occurring during the cold start. MOUDI impactor samples showed that 33 and 69% of the PM mass was smaller than 0.1 microm for the FTP and REP05 cycles, respectively, when collected under standard laboratory conditions. Particle number counts were much higher on the REP05 than the FTP. Counts were obtained using secondary dilution of samples drawn from the standard dilution tunnel. FTP PM10 was mostly carbonaceous material, 36% of which was classified as organic. For the REP05, as much as 20% of the PM10 was sulfate and associated water. Forty-five percent of the REP05 PM carbon emissions was classified as organic. Driving cycle had a significant impact on the distribution of the emitted polynuclear aromatic hydrocarbons.

Automobile Driving↗

Plutonium partitioning to colloidal and particulate matter in an acidic, sandy sediment: implications for remediation alternatives and plutonium migration.

Plutonium partitioning within a bulk, freshwater sediment and to specific size fractions of the sediment was determined. Fission track analysis was used to observe the spatial heterogeneity of fissile isotopes of Pu and U in the sediment. For the bulk sediment, a six-step sequential extraction scheme was used to elucidate Pu partitioning. Although no direct Pu speciation is obtained from our sequential extraction scheme, this study demonstrates that the partitioning information obtained is more useful for evaluating ex-situ remediation treatments than information obtained from complete digestion and analysis of the bulk sediment. The majority of 238Pu and 239 + 240Pu appear to be partitioned in the oxidizable fraction, suggesting that Pu is primarily associated with organic matter in the bulk sediment or may exist as a discrete, oxidizable phase. By varying filter pore size used to separate the sequential extraction leachate solution from the remaining solid phase, a fraction of 238Pu associated with colloidal material was observed, and chemical evidence suggests that this colloidal material is relatively refractory. Pu partitioning to various size fractions of the bulk sediment was also compared to the percent organic carbon present in those size fractions. Interestingly, little correlation was observed between the percentage of organic carbon and concentrations of Pu isotopes in the various size fractions, although differences were observed in the distributions of 238Pu versus 239 + 240Pu in the size fractions. These results suggest that other sediment phases may also be important for Pu partitioning. Our observations are described in the context of feasibility of various remediation options.

Colloids↗

Indoor respirable particulate matter concentrations from an open fire, improved cookstove, and LPG/open fire combination in a rural Guatemalan community.

Improved biomass cookstoves have the potential to reduce pollutant emissions and thereby reduce pollution exposure among populations in developing countries who cook daily with biomass fuels. However, evaluation of such interventions has been very limited. This article presents results from a study carried out in 30 households in rural Guatemala. Twenty-four hour PM3.5 concentrations were compared over 8 months for three fuel/cookstove conditions (n = 10 households for each condition): a traditional open fire cookstove, an improved cookstove called the plancha mejorada, and a liquefied petroleum gas (LPG) stove/open fire combination. Twenty-four hour geometric mean PM3.5 concentrations were 1560 micrograms/m3 (n = 58; 95% C.I. 1310, 1850), 280 micrograms/m3 (n = 59; 95% C.I. 240-320), and 850 micrograms/m3 (n = 60; 95% C.I. 680-1050) for the open fire, plancha, and LPG/open fire combination, respectively. A generalized estimating equation model showed a 45% reduction in PM3.5 concentrations for the LPG/open fire combination as compared to the open fire alone. The difference approached significance (p < 0.0737). The plancha showed an 85% reduction in PM3.5 concentrations as compared to the open fire (p < 0.0001). An analysis of the interaction of time with stove type showed that the temporal trend in pollution did not significantly differ among the three stove types. The reduced PM3.5 concentrations were maintained over time. Season did not affect pollutant concentrations. Of the two interventions, the plancha appears to offer the best prospects for achieving substantial reductions in indoor air pollution levels, although issues of cost and stove maintenance remain to be addressed.

Air Pollution, Indoor↗

Charring characteristics of atmospheric organic particulate matter in thermal analysis.

The charring of organic materials during carbon analysis bythermal methods makes it difficult to differentiate elemental carbon (EC) from organic carbon (OC). Failure to correct for charring results in the overestimation of EC and the underestimation of OC. The charring characteristics andthermal behaviors of aerosol OC are studied by subjecting hexane and water extracts of ambient aerosols to various analysis conditions. The complete evolution of water-soluble organic carbon (WSOC) aerosol materials is found to require a temperature as high as 850 degrees C and the presence of oxygen. EC would be oxidized under these thermal conditions as well. As a result, thermal methods relying only on temperature for the differentiation of EC and OC would give unreliable OC and EC concentrations. Our investigation also reveals that WSOC accounts for a large fraction (13-66%) of charring, while hexane extractable organic compounds produce little charring. The extent of charring from WSOC, defined as the ratio between pyrolytically generated EC to the total WSOC, is found to increase with the WSOC loading in each analysis when the loadings are below a certain value. This ratio remains constant when the loadings are above this value. This may account for the high variability in the extent of charring among aerosol samples from different locations as well as among samples from a single location collected at different times. Charring is reduced if the residence time at each temperature step in a helium atmosphere is sufficiently long to allow for maximum C evolution at each step. Charring is also influenced by the presence of inorganic constituents such as ammonium bisulfate. For the few tested organic materials, it is observed that ammonium bisulfate enhances the charring of starch and cellulose but reduces the charring of levoglucosan.

Aerosols↗

Events affecting levels and seasonal evolution of airborne particulate matter concentrations in the Western Mediterranean.

Time series (1996-2000) of levels of PM (PM10 and TSP) and gaseous pollutants recorded in air quality monitoring networks from Northeastern Spain were interpreted using meteorological data and satellite observations of African dust plumes. The main objective of this study was to identify the processes affecting time variations of PM levels on a day-to-day and seasonal basis. From March to October PM levels at rural, urban, and industrial sites vary as a function of the concatenation of Atlantic air mass advections (Atlantic episodes with low PM levels) and regional circulations (regional events with high PM levels, very often associated with high ozone levels), which favor the aging of air masses in the Western Mediterranean basin. During these regional episodes, PM is transported from urban/industrial to rural sites by meso-scale circulations. From November to February low PM levels are recorded at rural sites, and variations in PM levels at urban/industrial sites are governed by the successive occurrence of Atlantic episodes and local urban/industrial pollution events. The African dust outbreaks take place throughout the year and may induce PM levels to increase simultaneously in large areas of the Iberian peninsula. The difference between PM concentrations measured at urban and rural sites experiences a seasonal trend similar to that of levels of NO(x) and CO, which is characterized by a winter maximum due to the higher frequency of intensive local urban pollution events. However, maximum PM levels are recorded in summer at rural sites owing to the frequent occurrence of regional episodes. Furthermore, in three years of the study period (1997, 1998, and 2000), a second-order PM maximum was also recorded at rural sites in March owing to intensive African dust outbreaks.

Air Movements↗

Sugars--dominant water-soluble organic compounds in soils and characterization as tracers in atmospheric particulate matter.

The presence of saccharides is being reported for aerosols taken in urban, rural, and marine locales. The commonly found primary saccharides are alpha- and beta-glucose, alpha- and beta-fructose, sucrose, and mycose with lesser amounts of other monosaccharides. Saccharide polyols are also found in some airsheds and consist mainly of sorbitol, xylitol, mannitol, erythritol, and glycerol. In temperate climate areas these compounds increase from negligible concentrations in winter aerosols (usually dominated by levoglucosan and related anhydrosaccharides from biomass burning) to a maximum in late spring-summer, followed by a decrease to winter. The composition of the saccharide mixtures suggests soil and associated microbiota as the source. Saccharide analyses of soils confirmed these compositions. Therefore, we propose resuspension of soil (also unpaved road dust) from agricultural activities as a major component of aerosol particles and the saccharides are the source specific tracers. In addition, the saccharides as well as the anhydrosaccharide derivatives from biomass burning are completely water soluble and thus contribute significantly to the total water-soluble mass of aerosols.

Aerosols↗

Carbon monoxide as a tracer for assessing exposures to particulate matter in wood and gas cookstove households of highland Guatemala.

Kitchen-area 22-h gravimetric PM2.5 and passive diffusion stain-tube carbon monoxide (CO) concentrations were measured in homes with open fire and improved wood cookstoves in two studies. In the first study (Guat-2), which also studied homes with gas cookstoves, three samples were collected per stove condition from each of three test houses. In the second study (Guat-3), one sample was collected per house from 15 open fire and 25 improved-stove houses. CO personal samples were also taken for mother and child in both studies. Spearman correlation coefficients (R) between kitchen-area CO and PM2.5 levels in homes using open fires or impoved wood cookstoves were high ranging from 0.92 (Guat-2) to 0.94 (Guat-3), as were those between the personal samples for mother and child ranging from 0.85 (Guat-3) to 0.96 (Guat-2). In general, the correlations were lower for less-polluted conditions. The study found that CO is a good proxy for PM2.5 in homes using open fires or planchas (improved wood cookstove with chimney) but not under gas stove use conditions. It also determined that mother personal CO is a good proxy for child's (under 2 years of age) personal CO and that area CO measurements are not strongly representative of personal CO measurements. These results generally support the use of Draeger CO passive diffusion tubes as a proxy for PM2.5 in such cases where a single type of emission source is the predominant source for CO and PM2.5.

Air Pollution, Indoor↗

Role of free radicals in the toxicity of airborne fine particulate matter.

Exposure to airborne fine particles (PM2.5) is implicated in excess of 50 000 yearly deaths in the USA as well as a number of chronic respiratory illnesses. Despite intense interest in the toxicity of PM2.5, the mechanisms by which it causes illnesses are poorly understood. Since the principal source of airborne fine particles is combustion and combustion sources generate free radicals, we suspected that PM2.5 may contain radicals. Using electron paramagnetic resonance (EPR), we examined samples of PM2.5 and found large quantities of radicals with characteristics similar to semiquinone radicals. Semiquinone radicals are known to undergo redox cycling and ultimately produce biologically damaging hydroxyl radicals. Aqueous extracts of PM2.5 samples induced damage to DNA in human cells and supercoiled phage DNA. PM2.5-mediated DNA damage was abolished by superoxide dismutase, catalase, and deferoxamine, implicating superoxide radical, hydrogen peroxide, and the hydroxyl radical in the reactions inducing DNA damage.

Air Pollutants↗