Source contributions to the mutagenicity of urban particulate air pollution

Using organic compounds as tracers, a chemical mass balance model was employed to investigate the relationship between the mutagenicity of the urban organic aerosol sources and the mutagenicity of the atmospheric samples. The fine particle organic mass concentration present in the 1993 annual average Los Angeles-area composite sample was apportioned among eight emission source types. The largest source contributions to fine particulate organic compound mass concentration were identified as smoke from meat cooking, diesel-powered vehicle exhaust, wood smoke, and paved road dust. However, the largest source contributions to the mutagenicity of the atmospheric sample were natural gas combustion and diesel-powered vehicles. In both the human cell and bacterial assay systems, the combined mutagenicity of the composite of primary source effluents predicted to be present in the atmosphere was statistically indistinguishable from the mutagenicity of the actual atmospheric sample composite. Known primary emissions sources appear to be capable of emitting mutagenic organic matter to the urban atmosphere in amounts sufficient to account for the observed mutagenicity of the ambient samples. The error bounds on this analysis, however, are wide enough to admit to the possible importance of additional mutagenic organics that are formed by atmospheric reaction (e.g., 2-nitrofluoranthene has been identified as an important human cell mutagen in the atmospheric composite studied here, accounting for approximately 1% of the total sample mutagenic potency).     

Source identification of personal exposure to fine particulate matter using organic tracers

Personal exposure to fine particulate matter (PM2.5) is due to both indoor and outdoor sources. Contributions of sources to personal exposure can be quite different from those observed at ambient sampling locations. The primary goal of this study was to investigate the effectiveness of using trace organic speciation data to help identify sources influencing PM2.5 exposure concentrations. Sixty-four 24-h PM2.5 samples were obtained on seven different subjects in and around Boulder, CO. The exposure samples were analyzed for PM2.5 mass, elemental and organic carbon, organic tracer compounds, water-soluble metals, ammonia, and nitrate. This study is the first to measure a broad distribution of organic tracer compounds in PM2.5 personal samples. PM2.5 mass exposure concentrations averaged 8.4 μg m^?3. Organic carbon was the dominant constituent of the PM2.5 mass. Forty-four organic species and 19 water-soluble metals were quantifiable in more than half of the samples. Fifty-four organic species and 16 water-soluble metals had measurement signal-to-noise ratios larger than two after blank subtraction.The dataset was analyzed by Principal Component Analysis (PCA) to determine the factors that account for the greatest variance. Eight significant factors were identified; each factor was matched to its likely source based primarily on the marker species that loaded the factor. The results were consistent with the expectation that multiple marker species for the same source loaded the same factor. Meat cooking was an important source of variability. The factor that represents meat cooking was highly correlated with organic carbon concentrations (r = 0.84). The correlation between ambient PM2.5 and PM2.5 exposure was relatively weak (r = 0.15). Time participants spent performing various activities was generally not well correlated with PCA factor scores, likely because activity duration does not measure emissions intensity. The PCA results demonstrate that organic tracers can aid in identifying factors that influence personal exposures to PM2.5.     

The Denver Aerosol Sources and Health (DASH) Study: Overview and Early Findings

Improved understanding of the sources of air pollution that are most harmful could aid in developing more effective measures for protecting human health. The Denver Aerosol Sources and Health (DASH) study was designed to identify the sources of ambient fine particulate matter (PM(2.5)) that are most responsible for the adverse health effects of short-term exposure to PM (2.5). Daily 24-hour PM(2.5) sampling began in July 2002 at a residential monitoring site in Denver, Colorado, using both Teflon and quartz filter samplers. Sampling is planned to continue through 2008. Chemical speciation is being carried out for mass, inorganic ionic compounds (sulfate, nitrate and ammonium), and carbonaceous components, including elemental carbon, organic carbon, temperature-resolved organic carbon fractions and a large array of organic compounds. In addition, water soluble metals were measured daily for 12 months in 2003. A receptor-based source apportionment approach utilizing positive matrix factorization (PMF) will be used to identify PM (2.5) source contributions for each 24-hour period. Based on a preliminary assessment using synthetic data, the proposed source apportionment should be able to identify many important sources on a daily basis, including secondary ammonium nitrate and ammonium sulfate, diesel vehicle exhaust, road dust, wood combustion and vegetative debris. Meat cooking, gasoline vehicle exhaust and natural gas combustion were more challenging for PMF to accurately identify due to high detection limits for certain organic molecular marker compounds. Measurements of these compounds are being improved and supplemented with additional organic molecular marker compounds. The health study will investigate associations between daily source contributions and an array of health endpoints, including daily mortality and hospitalizations and measures of asthma control in asthmatic children. Findings from the DASH study, in addition to being of interest to policymakers, by identifying harmful PM(2.5) sources may provide insights into mechanisms of PM effect.     

SITING OF A WATER POLLUTION CONTROL FACILITY AT JAMESTOWN,RHODE ISLAND1

ABSTRACT: The town of Jamestown, Rhode Island, located on Conanicut Island in Narragansett Bay, is constructing a secondary treatment plant in order to comply with NPDES regulations. Twelve candidate sites for the plant and marine outfall were initially proposed, and ability to meet State water quality standards at these sites was evaluated using an EPA buoyant plume model. A final outfall site, Taylor Point, was selected by the Town from among the sites considered acceptable. Taylor Point was then subjected to field hydrographic studies including drogue tracking, current recordings, and tracer dye surveys. Results of the measurement program served as input to a two-dimensional effluent dispersion model which predicted excess BOD, coliform, and suspended solids resulting from effluent discharge off Taylor Point. The model predictions demonstrated that State water quality standards can be maintained outside the initial discharge plume.     

Indoor pollutant levels from the use of unvented natural gas fireplaces in Boulder, Colorado

High CO and NO2 concentrations have been documented in homes with unvented combustion appliances, such as natural gas fireplaces. In addition, polycyclic aromatic hydrocarbons (PAH) are emitted from incomplete natural gas combustion. The acute health risks of CO and NO2 exposure have been well established for the general population and for certain high-risk groups, including infants, the elderly, and people with heart disease or asthma. Health effects from PAH exposure are less well known, but may include increased risk of cancer. We monitored CO emissions during the operation of unvented natural gas fireplaces in two residences in Boulder, CO, at various times between 1997 and 2000. During 1999, we expanded our tests to include measurements of NO2 and PAH. Results show significant pollutant accumulation indoors when the fireplaces were used for extended periods of time. In one case, CO concentrations greater than 100 ppm accumulated in under 2 hr of operation; a person at rest exposed for 10 hr to this environment would get a mild case of CO poisoning with an estimated 10% carboxyhemoglobin level. Appreciable NO2 concentrations were also detected, with a 4-hr time average reaching 0.36 ppm. Similar time-average total PAH concentrations reached 35 ng/m3. The results of this study provide preliminary insights to potential indoor air quality problems in homes operating unvented natural gas fireplaces in Boulder.     

Evaluation of retrofit crankcase ventilation controls and diesel oxidation catalysts for reducing air pollution in school buses

This study evaluates the effect of retrofit closed crankcase ventilation filters (CCFs) and diesel oxidation catalysts (DOCs) on the in-cabin air quality in transit-style diesel school buses. In-cabin pollution levels were measured on three buses from the Pueblo, CO District 70 fleet. Monitoring was conducted while buses were driven along their regular routes, with each bus tested three times before and three times after installation of control devices. Ultrafine number concentrations in the school bus cabins were 33–41% lower, on average, after the control devices were installed. Mean mass concentrations of particulate matter less than 2.5 μm in diameter (PM2.5) were 56% lower, organic carbon (OC) 41% lower, elemental carbon (EC) 85% lower, and formaldehyde 32% lower after control devices were installed. While carbon monoxide concentrations were low in all tests, mean concentrations were higher after control devices were installed than in pre-retrofit tests. Reductions in number, OC, and formaldehyde concentrations were statistically significant, but reductions in PM2.5 mass were not. Even with control devices installed, during some runs PM2.5 and OC concentrations in the bus cabins were elevated compared to ambient concentrations observed in the area. OC concentrations inside the bus cabins ranged from 22 to 58 μg m^?3 before and 13 to 33 μg m^?3 after control devices were installed. OC concentrations were correlated with particle-bound organic tracers for lubricating oil emissions (hopanes) and diesel fuel and tailpipe emissions (polycyclic aromatic hydrocarbons (PAH) and aliphatic hydrocarbons). Mean concentrations of hopanes, PAH, and aliphatic hydrocarbons were lower by 37, 50, and 43%, respectively, after the control devices were installed, suggesting that both CCFs and DOCs were effective at reducing in-cabin OC concentrations.     

PM2.5 characterization for time series studies: Organic molecular marker speciation methods and observations from daily measurements in Denver

Particulate matter less than 2.5 microns in diameter (PM_2.5) has been shown to have a wide range of adverse health effects and consequently is regulated in accordance with the US-EPA's National Ambient Air Quality Standards. PM_2.5 originates from multiple primary sources and is also formed through secondary processes in the atmosphere. It is plausible that some sources form PM_2.5 that is more toxic than PM_2.5 from other sources. Identifying the responsible sources could provide insight into the biological mechanisms causing the observed health effects and provide a more efficient approach to regulation. This is the goal of the Denver Aerosol Sources and Health (DASH) study, a multi-year PM_2.5 source apportionment and health study.The first step in apportioning the PM_2.5 to different sources is to determine the chemical make-up of the PM_2.5. This paper presents the methodology used during the DASH study for organic speciation of PM_2.5. Specifically, methods are covered for solvent extraction of non-polar and semi-polar organic molecular markers using gas chromatography–mass spectrometry (GC–MS). Vast reductions in detection limits were obtained through the use of a programmable temperature vaporization (PTV) inlet along with other method improvements. Results are presented for the first 1.5 years of the DASH study revealing seasonal and source-related patterns in the molecular markers and their long-term correlation structure. Preliminary analysis suggests that point sources are not a significant contributor to the organic molecular markers measured at our receptor site. Several motor vehicle emission markers help identify a gasoline/diesel split in the ambient data. Findings show both similarities and differences when compared with other cities where similar measurements and assessments have been made.     

Source Apportionment Using Positive Matrix Factorization on Daily Measurements of Inorganic and Organic Speciated PM(2.5)

Particulate matter less than 2.5 microns in diameter (PM(2.5)) has been linked with a wide range of adverse health effects. Determination of the sources of PM(2.5) most responsible for these health effects could lead to improved understanding of the mechanisms of such effects and more targeted regulation. This has provided the impetus for the Denver Aerosol Sources and Health (DASH) study, a multi-year source apportionment and health effects study relying on detailed inorganic and organic PM(2.5) speciation measurements.In this study, PM(2.5) source apportionment is performed by coupling positive matrix factorization (PMF) with daily speciated PM(2.5) measurements including inorganic ions, elemental carbon (EC) and organic carbon (OC), and organic molecular markers. A qualitative comparison is made between two models, PMF2 and ME2, commonly used for solving the PMF problem. Many previous studies have incorporated chemical mass balance (CMB) for organic molecular marker source apportionment on limited data sets, but the DASH data set is large enough to use multivariate factor analysis techniques such as PMF.Sensitivity of the PMF2 and ME2 models to the selection of speciated PM(2.5) components and model input parameters was investigated in depth. A combination of diagnostics was used to select an optimum, 7-factor model using one complete year of daily data with pointwise measurement uncertainties. The factors included 1) a wintertime/methoxyphenol factor, 2) an EC/sterane factor, 3) a nitrate/polycyclic aromatic hydrocarbon (PAH) factor, 4) a summertime/selective aliphatic factor, 5) an n-alkane factor, 6) a middle oxygenated PAH/alkanoic acid factor and 7) an inorganic ion factor. These seven factors were qualitatively linked with known PM(2.5) emission sources with varying degrees of confidence. Mass apportionment using the 7-factor model revealed the contribution of each factor to the mass of OC, EC, nitrate and sulfate. On an annual basis, the majority of OC and EC mass was associated with the summertime/selective aliphatic factor and the EC/sterane factor, respectively, while nitrate and sulfate mass were both dominated by the inorganic ion factor. This apportionment was found to vary substantially by season. Several of the factors identified in this study agree well with similar assessments conducted in St. Louis, MO and Pittsburgh, PA using PMF and organic molecular markers.     

PM2.5 characterization for time series studies: Pointwise uncertainty estimation and bulk speciation methods applied in Denver

Many studies have identified associations between adverse health effects and short-term exposure to particulate matter less than 2.5 μm in diameter (PM_2.5). These effects, however, are not consistent across geographical regions. This may be due in part to variations in the chemical make-up of PM_2.5 resulting from unique combinations of sources, both primary and secondary, in different regions. The Denver Aerosol Sources and Health (DASH) study is a multi-year time series study designed to characterize the daily chemical composition of PM_2.5 in Denver, identify the major contributing sources, and investigate associations between sources and a broad array of adverse health outcomes.Measurement methodology, field blank correction, pointwise uncertainty estimation and detection limit consideration are discussed in the context of bulk speciation for the DASH study. Results are presented for the first 4.5 years of mass, inorganic ion and bulk carbon speciation. The derived measurement uncertainties were propagated using the root sum of squares method and show good agreement with precision estimates derived from bi-weekly duplicate samples collected on collocated samplers. Gravimetric mass has the most uncertainty of any measurement and reconstructed mass generated from the sum of the individual species shows less uncertainty than measured mass on average. The methods discussed provide a good framework for PM_2.5 speciation measurements and are generalizable to analysis of other environmental measures.