Daily variation in chemical characteristics of urban ultrafine aerosols and inference of their sources.

A summer air quality monitoring campaign focusing on daily variation of ultrafine (<180 nm in diameter) particle chemical characteristics was conducted in a typical urban site in Los Angeles during June-July 2006. Ultrafine particles (UFP) were collected weekly for two 3 h periods each day, one to capture the morning commute (06:00-09:00 PDT) (Pacific Daylight Time) and one to investigate photochemically altered particles (13:00-16:00 PDT). Samples were analyzed for ionic compounds, metals, trace elements, elemental carbon, and organic carbon. In addition, measurements of individual organic species and their variation with time of day at the urban site were conducted. The relative abundances of alkanes, PAH, and hopanes in the morning denote a strong influence of commute traffic emissions on ultrafine particle concentrations. By contrast, afternoon concentrations of oxygenated organic acids and sulfate rose, while other species were diluted by increased mixing height or lost due to increasing temperature. These are clear indicators that secondary photochemical reactions are a major formation mechanism of ultrafine aerosols in the afternoon. The concentrations of organic species originating from vehicular emissions measured in this study compare favorably to those from freeway-adjacent measurements by using CO2 concentrations to adjust for dilution, demonstrating the effectiveness of this tool for relating sites affected by vehicular emissions.

Particle concentration and Characteristics near a major freeway with heavy-duty diesel traffic.

This study presents the number, surface and volume concentrations, and size distribution of particles next to the 1-710 freeway during February through April 2006. 1-710 has the highest ratio (up to 25%) of heavy-duty diesel vehicles in the Los Angeles highway network. Particle concentration measurements were accompanied by measurements of black carbon, elemental and organic carbon, and gaseous species (CO, CO2). Using the incremental increase of CO2 over the background to calculate the dilution ratio, this study makes it possible to compare particle concentrations measured next to the freeway to concentrations measured in roadway tunnels and in vehicle exhaust. In addition to the effect of the dilution ratio on the measured particle concentrations, multivariate linear regressions showed that light and heavy organic carbon concentrations are positively correlated with the particle volume in the nucleation and accumulation modes, respectively. Solar radiation was also positively correlated with the particle surface concentration and the particle volume in the accumulation (40-638 nm) mode, presumably as a result of secondary particle formation. The methods developed in this study may be used to decouple the effect of sampling position, meteorology, and fleet operation on particle concentrations in the proximity of freeways, roadway tunnels, and in street canyons.

Size-resolved emissions of organic tracers from light- and heavy-duty vehicles measured in a California roadway tunnel.

Individual organic compounds found in particulate emissions from vehicles have proven useful in source apportionment of ambient particulate matter. Species of interest include the hopanes, originating in lube oil, and selected PAHs generated via combustion. Most efforts to date have focused on emissions and apportionment PM10 or PM2.5 However, examining how these compounds are segregated by particle size in both emissions and ambient samples will help efforts to apportion size-resolved PM, especially ultrafine particles which have been shown to be more potent toxicologically. To this end, high volume size-resolved (coarse, accumulation, and ultrafine) PM samples were collected inside the Caldecott tunnel in Orinda, California to determine the relative emission factors for these compounds in different size ranges. Sampling occurred in two bores, one off-limits to heavy-duty diesel vehicles, which allows determination of the different emissions profiles for diesel and gasoline vehicles. Although tunnel measurements do not measure emissions over a full engine duty cycle, they do provide an average emissions profile over thousands of vehicles that can be considered characteristic of "freeway" emissions. Results include size-fractionated emission rates for hopanes, PAHs, elemental carbon, and other potential organic markers apportioned to diesel and gasoline vehicles. The results are compared to previously conducted PM2.5 emissions testing using dynamometer facilities and othertunnel environments.

Measurements of particle number and mass concentrations and size distributions in a tunnel environment.

Particulate matter emissions were measured in two bores of the Caldecott Tunnel in Northern California during August and September 2004. One bore (Bore 1) is open to both heavy- and light-duty vehicles while heavy-duty vehicles are prohibited from entering the second bore (Bore 2). Particulate matter number and mass size distributions, chemical composition, and gaseous copollutants were recorded for four consecutive days near the entrance and exit of each bore. Size-resolved emission factors were determined for particle number, particle mass, elemental carbon, organic carbon (OC), sulfate, nitrate, and selected elements. The size distributions in both the bores showed a single large mode at roughly 15-20 nm in mobility diameter, with occasional smaller modes around 100 nm. The PM10 mass emission factor for heavy-duty vehicles was 14.5 times higher than that of light-duty vehicles. The particles derived from diesel are more abundant in elemental carbon, 70.9% of PM10 emissions, as compared to the light-duty vehicles. Conversely, a greater percentage of OC was found in light-duty emissions than heavy-duty emissions. In comparison to previous studies at the Caldecott Tunnel, less particle mass but more particle numbers are emitted by vehicles than was the case 7 years ago.

Respiratory responses to exposures with fine particulates and nitrogen dioxide in the elderly with and without COPD.

Elderly people, with and without chronic obstructive pulmonary disease (COPD), may be susceptible to particulate matter (PM) air pollution. However, the respiratory impacts of inhaled PM combined with copollutant(s) in controlled exposure studies are unclear and warrant investigation since exposures to PMgas mixtures constitute realistic scenarios. Thus, we exposed 6 healthy subjects and 18 volunteers with COPD (mean age 71 yr) on separate days to (a) filtered air (FA); (b) 0.4 ppm NO2; (c) concentrated ambient particles (CAP), predominantly in the fine (PM2.5) size range, at concentrations near 200 microg/m3; and (d) CAP and NO2 together. Each 2-h exposure included exercise for 15 min every half hour. Most respiratory responses, including symptoms, spirometry, and total and differential counts of induced sputum cells, showed no statistically significant responses attributable to separate or combined effects of CAP and NO2. However, maximal mid-expiratory flow and arterial O2 saturation (measured by pulse oximetry) showed small but statistically significant decrements associated with CAP, greater in healthy than COPD subjects. CAP exposure was also associated with decreased percentages of columnar epithelial cells in sputum. The results suggest that the respiratory effect of the PMNO2 mixture may be primarily PM driven since coexposure to NO2 did not significantly enhance the responses. In conclusion, older adults exposed to urban fine particles may experience acute small-airways dysfunction with impaired gas exchange. Healthy subjects appear more susceptible, suggesting that the respiratory effect may be related to efficient penetration and deposition of inhaled toxic particles in distal small airways. More clinical investigation of the elderly population is warranted.

The relationship between real-time and time-integrated coarse (2.5-10 micrm), intermodal (1-2.5 microm), and fine (<2.5 microm) particulate matter in the Los Angeles basin.

A periodic review of the National Ambient Air Quality Standards for Particulate Matter by the U.S. Environmental Protection Agency (EPA) will assess the standards with respect to levels, particle size, and averaging times. Some members of the scientific community in the United States and Europe have suggested the use of PM1 instead of PM2.5 as the fine particle measurement standard. This proposed standard is intended to reduce the influence of coarse particle sources on PM2.5, because some evidence suggests that PM1-2.5 is dominated by coarse particulate matter (PM) sources. In this study, coarse (PM2.5-10), intermodal (PM1-2.5), and fine (PM2.5) mass concentrations at four different sites are measured with continuous and time-integrated sampling devices. The main objective is to compare variations in these three size ranges while considering the effects of location, sources, weather, wind speed, and wind direction. Results show strong correlations between PM1 and intermodal PM in receptor sites. The contribution of PM1-2.5 to PM2.5 is highest in the summer months, most likely due to enhanced long-range transport. Coarse PM is poorly correlated with intermodal PM. Continuous data suggest that PM1 is growing into PM1-2.5 via complex processes involving stagnation of the aerosol during high relative humidity conditions, followed by advection during daytime hours.

Altered heart-rate variability in asthmatic and healthy volunteers exposed to concentrated ambient coarse particles.

Twelve mildly asthmatic and four healthy adults were exposed to filtered air (FA) and concentrated ambient coarse particles (CCP) supplied to a whole-body exposure chamber via a coarse particle concentrator with 15 parallel virtual impactors. Exposures were conducted in a Los Angeles suburb with high levels of motor-vehicle pollution and lasted 2 h with intermittent exercise. Mean CCP concentration was 157 microg/m(3) (range: 56-218 microg/m(3)) measured by continuous monitoring with a tapered-element oscillating microbalance (TEOM). On average, 80% of mass was coarse (2.5-10 microm aerodynamic diameter) and the rest <2.5 microm. Relative to FA, CCP exposure did not significantly alter respiratory symptoms, spirometry, arterial oxygen saturation, or airway inflammation according to exhaled nitric oxide and total and differential cell counts of induced sputum. After CCP exposure, Holter electrocardiograms showed small (p <.05) increases in heart rate and decreases in heart-rate variability, which were larger in healthy than in asthmatic subjects. Cardiac ectopy did not increase. In conclusion, acute exposure to elevated concentrations of ambient coarse particles elicited no obvious pulmonary effects but appeared to alter the autonomic nervous system of the heart in adult volunteers.