Contrast and correlations between coarse and fine particulate matter in the United States.

The characteristics of concentrations of PM10₋2.5, PM2.5, and PM10 at 77 sites in the United States are evaluated. PM10 concentrations show strong spatial variability, with highest levels occurring in the southwestern United States, driven primarily by PM10₋2.5. PM10₋2.5 and PM2.5 concentrations show different spatial patterns. The highest concentrations of PM10₋2.5 were observed at sites in the southwestern US, leading to the highest PM10 concentrations there. The PM2.5 concentrations are the major contributors to the average PM10 concentrations at many sites in the eastern United States. Poor correlations were generally found between PM10₋2.5 and PM2.5, suggesting that PM10₋2.5 and PM2.5 are generally influenced by different sources. PM10₋2.5 is generally more variable than PM2.5 because PM10₋2.5 has a higher deposition velocity and is primarily emitted from mechanical processes (e.g. agricultural harvest and construction) that are more influenced by factors including human operation and wind speed leading to a strong episodic nature. As a result of its high variability, PM10₋2.5 acts as the major driver for PM10 extremes. PM10₋2.5 is significantly correlated with PM10 at all investigated sites, with the average correlation value R(2)=0.79. Correlations of PM2.5 with PM10 (average of 0.37) are overall considerably lower than those between PM10₋2.5 and PM10. Different seasonal, weekly, and diurnal patterns were observed between PM10₋2.5 and PM2.5 at agricultural, on-road traffic, quarrying, airport, and marine sites. At investigated agricultural sites, while the concentrations of PM2.5 are higher in winter when there are few agricultural activities, PM10₋2.5 concentrations are lower in winter months than in summer and autumn months, with highest levels corresponding to harvest and planting. The harvest and planting signatures were not observed in PM2.5 concentrations at any of these sites, suggesting that agricultural activities do not have a strong influence on PM2.5 concentrations.

Positive matrix factorization of PM2.5 - eliminating the effects of gas/particle partitioning of semivolatile organic compounds.

Gas-phase concentrations of semi-volatile organic compounds (SVOCs) were calculated from gas/particle (G/P) partitioning theory using their measured particle-phase concentrations. The particle-phase data were obtained from an existing filter measurement campaign (27 January 2003-2 October 2005) as a part of the Denver Aerosol Sources and Health (DASH) study, including 970 observations of 71 SVOCs (Xie et al., 2013). In each compound class of SVOCs, the lighter species (e.g. docosane in n alkanes, fluoranthene in PAHs) had higher total concentrations (gas + particle phase) and lower particle-phase fractions. The total SVOC concentrations were analyzed using positive matrix factorization (PMF). Then the results were compared with source apportionment results where only particle-phase SVOC concentrations were used (particle only-based study; Xie et al., 2013). For the particle only-based PMF analysis, the factors primarily associated with primary or secondary sources (n alkane, EC/sterane and inorganic ion factors) exhibit similar contribution time series (r = 0.92-0.98) with their corresponding factors (n alkane, sterane and nitrate+sulfate factors) in the current work. Three other factors (light n alkane/PAH, PAH and summer/odd n alkane factors) are linked with pollution sources influenced by atmospheric processes (e.g. G/P partitioning, photochemical reaction), and were less correlated (r = 0.69-0.84) with their corresponding factors (light SVOC, PAH and bulk carbon factors) in the current work, suggesting that the source apportionment results derived from particle-only SVOC data could be affected by atmospheric processes. PMF analysis was also performed on three temperature-stratified subsets of the total SVOC data, representing ambient sampling during cold (daily average temperature < 10 °C), warm (≥ 10 °C and ≤ 20 °C) and hot (> 20 °C) periods. Unlike the particle only-based study, in this work the factor characterized by the low molecular weight (MW) compounds (light SVOC factor) exhibited strong correlations (r = 0.82-0.98) between the full data set and each sub-data set solution, indicating that the impacts of G/P partitioning on receptor-based source apportionment could be eliminated by using total SVOC concentrations.

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.

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.

Trends in fine particle concentration and chemical composition in southern California.

Airborne fine particle mass concentrations in Southern California have declined in recent years. Trends in sulfate and elemental carbon (EC) particle concentrations over the period 1982-1993 are consistent with this overall improvement in air quality and help to confirm some of the reasons for the changes that are seen. Fine particle sulfate concentrations have declined as a strict sulfur oxides (SOx) emission control program adopted in 1978 was implemented over time. Fine particle elemental (black) carbon concentrations have declined over a period when newer diesel engines and improved diesel fuels have been introduced into the vehicle fleet. Organic aerosol concentrations have not declined as rapidly as the EC particle concentrations, despite the fact that catalyst-equipped cars having lower particle emission rates were introduced into the vehicle fleet alongside the diesel engine improvements mentioned above. This situation is consistent with the growth in population and vehicle miles traveled in the air basin over time. Fine particle ammonium nitrate in the Los Angeles area atmosphere contributes more than half of the fine aerosol mass concentration on the highest concentration days of the year, emphasizing both the need for accurate aerosol nitrate measurements and the likely importance of deliberate control of aerosol nitrate as a part of any serious further fine particle control program for the Los Angeles area.

Seasonal and spatial variation of the bacterial mutagenicity of fine organic aerosol in southern california.

The bacterial mutagenicity of a set of 1993 urban particulate air pollution samples is examined using the Salmonella typhimurium TM677 forward mutation assay. Amibent fine particulate samples were collected for 24 hr every sixth day throughout 1993 at four urban sites, including Long Beach, central Los Angeles, Azusa, and Rubidoux, California, and at an upwind background site on San Nicolas Island. Long Beach and central Los Angeles are congested urban areas where air quality is dominated by fresh emissions from air pollution sources; Azuasa and Rubidoux are located farther downwind and receive transported air pollutants plus increased quantities of the products of atmospheric chemical reactions. Fine aerosol samples from Long Beach and Los Angeles show a pronounced seasonal variation in bacterial mutagenicity per cubic meter of- ambient air, with maximum in the winter and a minimum in the summer. The down-wind smog receptor site at Rubidoux shows peak mutagenicity (with postmitochondrial supernatant but no peak without postmitochondrial supernatant) during the September-October periods when direct transport from upwind sources can be expected. At most sites the mutagenicity per microgram of organic carbon from the aerosol is not obviously higher during the summer photochemical smog period than during the colder months. Significant spatial variation in bacterial mutagenicity is observed: mutagenicity per cubic meter of ambient air, on average, is more than an order of magnitude lower at San Nicolas Island than within the urban area. The highest mutagenicity values per microgram of organics supplied to the assay are found at the most congested urban sites at central Los Angeles and Long Beach. The highest annual average values of mutagenicity per cubic meter of air sampled occur at central Los Angeles. These findings stress the importance of proximity to sources of direct emissions of bacterial mutagens and imply that if important mutagen-forming atmospheric reactions occur, they likely occur in the winter and spring seasons as well as the photochemically more active summer and early fall periods.