Air-quality implications of widespread adoption of cool roofs on ozone and particulate matter in southern California.

The installation of roofing materials with increased solar reflectance (i.e., "cool roofs") can mitigate the urban heat island effect and reduce energy use. In addition, meteorological changes, along with the possibility of enhanced UV reflection from these surfaces, can have complex impacts on ozone and PM2.5 concentrations. We aim to evaluate the air-quality impacts of widespread cool-roof installations prescribed by California's Title 24 building energy efficiency standards within the heavily populated and polluted South Coast Air Basin (SoCAB). Development of a comprehensive rooftop area database and evaluation of spectral reflectance measurements of roofing materials allows us to project potential future changes in solar and UV reflectance for simulations using the Weather Research Forecast and Community Multiscale Air Quality (CMAQ) models. 2012 meteorological simulations indicate a decrease in daily maximum temperatures, daily maximum boundary layer heights, and ventilation coefficients throughout the SoCAB upon widespread installation of cool roofs. CMAQ simulations show significant increases in PM2.5 concentrations and policy-relevant design values. Changes in 8-h ozone concentrations depend on the potential change in UV reflectance, ranging from a decrease in population-weighted concentrations when UV reflectance remains unchanged to an increase when changes in UV reflectance are at an upper bound. However, 8-h policy-relevant ozone design values increase in all cases. Although the other benefits of cool roofs could outweigh small air-quality penalties, UV reflectance standards for cool roofing materials could mitigate these negative consequences. Results of this study motivate the careful consideration of future rooftop and pavement solar reflectance modification policies.

Primary particulate matter from ocean-going engines in the Southern California Air Basin.

The impact of primary fine particulate matter (PM2.5) from ship emissions within the Southern California Air Basin is quantified by comparing in-stack vanadium (V) and nickel (Ni) measurements from in-use ocean-going vessels (OGVs) with ambient measurements made at 10 monitoring stations throughout Southern California. V and Ni are demonstrated as robust markers for the combustion of heavy fuel oil in OGVs, and ambient measurements of fine particulate V and Ni within Southern California are shown to decrease inversely with increased distance from the ports of Los Angeles and Long Beach (ports). High levels of V and Ni were observed from in-stack emission measurements conducted on the propulsion engines of two different in-use OGVs. The in-stack V and Ni emission rates (g/h) normalized by the V and Ni contents in the fuel tested correlates with the stack total PM emission rates (g/h). The normalized emission rates are used to estimate the primary PM2.5 contributions from OGVs at 10 monitoring locations within Southern California. Primary PM2.5 contributions from OGVs were found to range from 8.8% of the total PM2.5 at the monitoring location closest to the port (West Long Beach) to 1.4% of the total PM2.5 at the monitoring location 80 km inland (Rubidoux). The calculated OGV contributions to ambient PM2.5 measurements at the 10 monitoring sites agree well with estimates developed using an emission inventory based regional model. Results of this analysis will be useful in determining the impacts of primary particulate emissions from OGVs upon worldwide communities downwind of port operations.

Secondary particulate matter in the United States: insights from the Particulate Matter Supersites Program and related studies.

Secondary aerosols comprise a major fraction of fine particulate matter (PM2.5) in all parts of the country, during all seasons, and times of day. The most abundant secondary species include sulfate, nitrate, ammonium, and secondary organic aerosols (SOAs). The relative abundance of each species varies in space and time as a function of meteorology, source emissions strength and type, thermodynamics, and atmospheric processing. Transport of secondary aerosols from upwind locations can contribute significantly at downwind receptor sites, especially regionally in the eastern United States, and across a given urbanized area, such as in Los Angeles. Processes governing the formation of the inorganic secondary species (sulfate, nitrate, and ammonium) are fairly well understood, although the occurrence of nucleation bursts initiated with the formation of ultrafine sulfuric acid particles observed regionally on clean days in the eastern United States was unexpected. Because of the complex nature of organic material in air, much is still to be learned about the sources, formation, and even spatial and temporal distributions of SOAs. For example, a considerable fraction of ambient organic PM is oxidized organic species, many of which still need to be identified, quantified, and their sources and formation mechanisms determined. Furthermore, significant uncertainty (approaching 50% or more) is associated with estimating the SOA fraction of organic material in air with current methods. This review summarizes the findings of the Supersites Program and related studies addressing secondary particulate matter (PM), including spatial and temporal variations of secondary PM and its precursor species, data and methods for determining the primary and secondary fractions of PM mass, and findings on the anthropogenic and natural fractions of secondary PM.

Exceeding of Henry's law by hydrogen peroxide associated with urban aerosols.

Simultaneous measurements of gas- and aerosol-phase hydrogen peroxide (H2O2) have been made at two sites in Los Angeles, one near the Pacific coast at the University of California at Los Angeles (UCLA), and the other in downtown Los Angeles with close proximity to a heavily traveled freeway (freeway site). At both the freeway and UCLA sites, gas-phase H2O2 levels were similar, averaging 1.17 +/- 1.0 and 1.05 +/- 0.6 ppb, respectively. The particle-associated H2O2 in both fine (PM2.5) and coarse (>PM2.5) modes was higher at the freeway site, as compared to UCLA, by a factor of 2. However, when aerosol-phase H2O2 is normalized to particle mass loadings, the fine-mode H2O2 levels are very similar at the two sites: 0.42 +/- 0.3 and 0.58 +/- 0.3 ng H2O2/microg particle mass at the freeway and UCLA sites, respectively. The normalized coarse-mode H2O2 levels were significantly higher at the freeway site than at UCLA, 1.05 +/- 0.3 and 0.51 +/- 0.3 ng/microg, respectively. Estimating aerosol liquid water content on the basis of relative humidity and aerosol mass, a calculated equivalent H2O2 in aerosol liquid water averages 70 mM, more than 2 orders of magnitude higher than concentrations predicted by gas-particle partitioning (Henry's law), which averages 0.1 mM. This indicates that the sampled particles are capable of generating H2O2 in aqueous solution. These corresponding aqueous-phase H2O2 concentrations in aerosol liquid water exceed levels that have been observed to produce cellular damage to lung epithelial cells in laboratory experiments by at least 3 orders of magnitude. Although most measurements of H2O2 in particles were made using an extraction solution adjusted to pH 3.5, a set of measurements indicates that H2O2 from fine-mode particles extracted in the physiologically relevant pH range 5-7.5 also generate H2O2 with only slightly lowered efficiency; coarse-mode H2O2 production dropped by 75% at the upper end of this range. Finally, a small set of measurements was performed to investigate the degree to which the recently developed Versatile Aerosol Concentrator Enrichment System (VACES) affects H2O2 levels in concentrated ambient aerosols. The VACES appeared to a have minimal impact on particulate H2O2.

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.

Development of a wet-chemical method for the speciation of iron in atmospheric aerosols.

The ability to quantify the chemical and physical forms of transition metals in atmospheric particulate matter (PM) is essential in determining potential human health and ecological effects. A method for the speciation of iron in atmospheric PM has been adapted which involves extraction in a well-defined solution followed by oxidation state specific detection. The method was applied to a suite of environmental aerosols. Ambient atmospheric aerosols in an urban area of St. Louis (the St. Louis-Midwest Supersite) were collected on Teflon substrates and were leached in one of four different solutions: (1) >18.0 Momega water; (2) 140 microM NaCl solution; (3) pH = 7.4 NaHCO3 solution; and (4) pH = 4.3 acetate buffering system. Fe(ll) was determined directly using the Ferrozine method as adapted to liquid waveguide spectrophotometry using a 1 m path-length cell. Fe(lll) was determined similarly after reduction to Fe(ll). It was found that, at low ionic strength, pH exerted a major influence on Fe(ll) solubility with the greatest Fe(ll) concentration consistently found in the pH = 4.3 acetate buffer. Soluble Fe(lll) (as defined by a 0.2 microm filter) varied little with extractant, which implies that most of the Fe(lll) detected was colloidal. To characterize well-defined materials for future reference, NIST standard reference materials were also analyzed for soluble Fe(ll) and Fe(lll). For all SRMs tested, a maximum of 2.4% of the total iron (Urban Dust 1649a) was soluble in pH = 4.3 acetate buffer. For calibration curves covering the ranges of 0.5-20 microg/L Fe(ll), excellent linearity was observed in all leaching solutions with R2 values of > 0.999. Co-located filters were used to test the effect of storage time on iron oxidation state in the ambient particles as a function of time. On two samples, an average Fe(ll) decay rate of 0.89 and 0.57 ng Fe(ll) g(-1) PM day(-1) was determined from the slope of the regression, however this decrease was determined not to be significant over 3 months (95% confidence). As an application of this method to mobile source emissions, size-resolved PM10 samples were collected at the inlet and outlet of the Caldecott Motor Vehicle Tunnel in northern California. These samples indicate that the coarse fraction (PM10-PM2.5) contains almost 50% of the total soluble Fe(ll) in the aerosol.

Effects of sampling artifacts and operating parameters on the performance of a semicontinuous particulate elemental carbon/organic carbon monitor.

The carbonaceous component of atmospheric particulate matter (PM) is considered very important with respect to the observed adverse health effects of PM. Particulate organic and elemental carbon have traditionally been measured off-line after daily, time-integrated particle collection on filters. However, the subdaily or hourly variability of elemental carbon (EC) and organic carbon (OC) can help to assess the variability of sources, ambient levels, and human exposure. In this study, the performance of the Sunset Laboratory Inc. semicontinuous EC/OC monitorwas assessed in a Los Angeles location representing typical urban pollution. An intermonitor comparison showed high precision (R2 of 0.98 and 0.97 for thermal OC and EC, respectively). By changing the inlet configurations of one of the monitors (adding a denuder, a Teflon filter, or both), the influences of positive and negative sampling artifacts were investigated. The positive artifact was found to be relatively large (7.59 microg/m3 on average), more than 50% of measured OC, but it was practically eliminated with a denuder. The negative artifact was much smaller (less than 20% of the positive artifact) and may be neglected in most cases. A comparison of different temperature profiles, including a fast 4-min analysis using optical EC correction, showed good agreement among methods. Finally, a novel configuration using a size selective inlet impactor removing particles greater than 250 nm in diameter allowed for semicontinuous size-fractionated EC/OC measurements. Evolution of OC at different temperatures of the thermal analysis showed higher volatility OC in larger particles.

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.

A miniaturized active sampler for the assessment of personal exposure to nitrogen dioxide.

A personalized, miniaturized air sampling system was evaluated to estimate the daily exposure of pediatric asthmatics to nitrogen dioxide (NO2). The lightweight device (170 g) uses a sampling pump connected to a solid sorbent tube containing triethanolamine (TEA)-impregnated molecular sieve. The pump is powered by a 9 V battery and samples air over a 24 h period at a collection rate of 0.100 L/min. After exposure, the solid sorbent is removed from the tubes for spectrophotometric analysis (Griess Assay). The lower detection limit of the overall method for NO2 is 11 microg/m3. The linearity, precision and accuracy of the sampler was evaluated. Different NO2 concentrations generated in the laboratory (range: 50 to 340 microg/m3) were simultaneously measured by the TEA tube samplers and colocated continuous chemiluminescent NO(x) analyzers (reference method). The coefficient of determination for the laboratory test derived from ordinary linear regression (OLR) was r2 = 0.99 (y(OLR) = 0.94 x -4.58) and the precision 3.6%. Further, ambient NO2 concentrations in the field (range: 10-120 microg/m3) were verified with continuous chemiluminescent monitors next to the active samplers. Re-weighted least squares analysis (RLS) based on the least median squares procedure (LMS) resulted in a correlation of r2 = 0.68 for a field comparison in Riverside, CA (y(RLS) = 1.01 x -0.94) and r2 = 0.92 in Los Angeles, CA (y(RLS) = 1.31 x -7.12). The precision of the TEA tube devices was 7.4% (at 20-60 microg/m3 NO2) under outdoor conditions. Data show that the performance of this small active sampling system was satisfactory for measuring environmental concentrations of NO2 under laboratory and field conditions. It is useful for personal monitoring of NO2 in environmental epidemiology studies where daily measurements are desired.

Size-fractionated measurements of ambient ultrafine particle chemical composition in Los Angeles using the NanoMOUDI.

Ambient ultrafine particles have gained attention with recent evidence showing them to be more toxic than larger ambient particles. Few studies have investigated the distribution of chemical constituents within the ultrafine range. The current study explores the size-fractionated ultrafine (10-180 nm) chemical composition at urban source sites (USC and Long Beach) and inland receptor sites (Riverside and Upland) in the Los Angeles basin over three different seasons. Size-fractionated ultrafine particles were collected by a NanoMOUDI over a period of 2 weeks at each site. Measurements of ultrafine mass concentrations varied from 0.86 to 3.5 microg/m3 with the highest concentrations observed in the fall. The chemical composition of ultrafine particles ranged from 32 to 69% for organic carbon (OC), 1-34% for elemental carbon (EC), 0-24% for sulfate, and 0-4% for nitrate. A distinct OC mode was observed between 18 and 56 nm in the summer, possibly indicating photochemical secondary organic aerosol formation. The EC levels are higher in winter at the source sites due to lower inversion heights and are higher in summer at the receptor sites due to increased long-range transport from upwind source areas. Nitrate and sulfate were measurable only in the larger particle size ranges of ultrafine PM. Collocated continuous measurements of particle size distributions and gaseous pollutants helped to differentiate ultrafine particle sources at each site.

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.

Associations between particle number and gaseous co-pollutant concentrations in the Los Angeles Basin.

Continuous measurements of particle number (PN), particle mass (PM10), and gaseous pollutants [carbon monoxide (CO), nitric oxide (NO), oxides of nitrogen (NOx), and ozone (O3)] were performed at five urban sites in the Los Angeles Basin to support the University of Southern California Children's Health Study in 2002. The degree of correlation between hourly PN and concentrations of CO, NO, and nitrogen dioxide (NO2) at each site over the entire year was generally low to moderate (r values in the range of 0.1-0.5), with a few notable exceptions. In general, associations between PN and O3 were either negative or insignificant. Similar analyses of seasonal data resulted in levels of correlation with large variation, ranging from 0.0 to 0.94 depending on site and season. Summertime data showed a generally higher correlation between the 24-hr average PN concentrations and CO, NO, and NO2 than corresponding hourly concentrations. Hourly correlations between PN and both CO and NO were strengthened during morning rush-hour periods, indicating a common vehicular source. Comparing hourly particle number concentrations between sites also showed low to moderate spatial correlations, with most correlation coefficients below 0.4. Given the low to moderate associations found in this study, gaseous co-pollutants should not be used as surrogates to assess human exposure to airborne particle number concentrations.

Diurnal variations of individual organic compound constituents of ultrafine and accumulation mode particulate matter in the Los Angeles Basin.

Individual organic compounds can be used as tracers for primary sources of ambient particulate matter (PM) in chemical mass balance receptor models. Previous work has examined PM2.5 only and usually over long sampling periods encompassing entire days or longer. In this study, a high-flow-rate, low-pressure-drop ultrafine particle separator was deployed to collect sufficient mass for organic speciation of ultrafine and accumulation mode aerosol on a diurnal basis. Particles between 0.18 and 2.5 microm in diameter were collected on a quartz-fiber impaction substrate, and ultrafine particles below 0.18 microm were collected downstream on a high-volume filter. Four daily time period samples (morning, midday, evening, and overnight) were sampled over five weekdays to form a weekly average composite for each diurnal period. Sampling was conducted at two sites over two seasons; summer (August) and winter (January) samples were collected at both an urban site near downtown Los Angeles (University of Southern California) and a downwind, inland site in Riverside, CA. Hopanes, used as organic markers for vehicular emissions, were found to exist primarily in the ultrafine mode. Levoglucosan, an indicator of wood combustion, was quantified in both size ranges, but more was present in the accumulation mode particles. An indicator of photochemical secondary organic aerosol formation, 1,2-benzenedicarboxylic acid, was found primarily in the accumulation mode and varied with site, season, and time of day as one would expect for a photochemical product. The atmospheric variations of particulate cholesterol and other organic acids were also considered. By examining the diurnal variation, size-fractionation, and intercorrelations of individual organic compounds, the sources and atmospheric fate of these tracers can be better understood and their utility as molecular markers can be assessed.

Chemical characterzation of fine particle emissions from the fireplace combustion of woods grown in the Southern United States.

The fireplace combustion of wood is a significant and largely unregulated source of fine particle pollution in the United States. Source apportionment techniques that use particulate organic compounds as tracers have been successful in determining the contribution of wood smoke to ambient fine particle levels in specific areas in California. To apply these techniques to the rest of the United States, the differences in emissions profiles between different wood smoke sources and fuel types should be resolved. To this end, a series of fireplace source tests was conducted on six fuel wood species found in the Southern United States to determine fine particulate emission factors for total mass, ionic and elemental species, elemental and organic carbon, and over 250 individual organic compounds. The wood species tested, chosen for their high abundance and availability in the Southern U.S. region, were yellow poplar, white ash, sweetgum, mockernut hickory, loblolly pine, and slash pine. The differences in the emissions of compounds such as substituted phenols and resin acids help to distinguish between the smoke from hardwood and softwood combustion. Levoglucosan, a cellulose pyrolysis product which may serve as a tracer for wood smoke in general, was quantified in the emissions from all the wood species burned. The furofuran lignan, yangambin, which was emitted in significant quantities from yellow poplar combustion and not detected in any of the other North American wood smokes, is a potential species-specific molecular tracer which may be useful in qualitatively identifying particulate emissions from a specific geographical area where yellow poplar is being burned.

Health effects of subchronic exposure to low levels of wood smoke in rats.

Wood smoke is a significant source of air pollution in many parts of the United States, and epidemiological data suggest a causal relationship between elevated wood smoke levels and health effects. The present study was designed to provide information on the potential respiratory health responses to subchronic wood smoke exposures in a Native American community in New Mexico. Therefore, this study used the same type of wood under similar burning conditions and wood smoke particle concentrations to mimic the conditions observed in this community. Brown Norway rats were exposed 3 h/day, 5 days/week for 4 or 12 weeks to air as control, or to 1 or 10 mg/m3 concentrations of wood smoke particles from pinus edulis. The wood smoke consisted of fine particles (< 1 microm) that formed larger chains and aggregates having a size distribution of 63-74% in the < 1-microm fraction and 26-37% in the > 1-microm fraction. The particle-bound material was primarily composed of carbon, and the majority of identified organic compounds consisted of sugar and lignin derivatives. Pulmonary function, specifically carbon monoxide-diffusing capacity and pulmonary resistance, was somewhat affected in the high-exposure group. Mild chronic inflammation and squamous metaplasia were observed in the larynx of the exposed groups. The severity of alveolar macrophage hyperplasia and pigmentation increased with smoke concentration and length of exposure, and the alveolar septae were slightly thickened. The content of mucous cells lining the airways changed from Periodic Acid Schiff- to Alcian Blue-positive material in the low-exposure group after 90 days. Together, these observations suggest that exposure to wood smoke caused minor but significant changes in Brown Norway rats. Further studies are needed to establish whether exposure to wood smoke exacerbates asthmalike symptoms that resemble those described for children living in homes using wood stoves for heating and cooking.