Michael J. Kleeman

Influence of vapor wall loss in laboratory chambers on yields of secondary organic aerosol

Significance Atmospheric secondary organic aerosol (SOA) has important impacts on climate and air quality, yet models continue to have difficulty in accurately simulating SOA concentrations. Nearly all SOA models are tied to observations of SOA formation in laboratory chamber experiments. Here, a comprehensive analysis of new experimental results demonstrates that the formation of SOA in laboratory chambers may be substantially suppressed due to losses of SOA-forming vapors to chamber walls, which leads to underestimates of SOA in air-quality and climate models, especially in urban areas where anthropogenic SOA precursors dominate. This analysis provides a time-dependent framework for the interpretation of laboratory chamber experiments that will allow for development of parameterized models of SOA formation that are appropriate for use in atmospheric models. Secondary organic aerosol (SOA) constitutes a major fraction of submicrometer atmospheric particulate matter. Quantitative simulation of SOA within air-quality and climate models—and its resulting impacts—depends on the translation of SOA formation observed in laboratory chambers into robust parameterizations. Worldwide data have been accumulating indicating that model predictions of SOA are substantially lower than ambient observations. Although possible explanations for this mismatch have been advanced, none has addressed the laboratory chamber data themselves. Losses of particles to the walls of chambers are routinely accounted for, but there has been little evaluation of the effects on SOA formation of losses of semivolatile vapors to chamber walls. Here, we experimentally demonstrate that such vapor losses can lead to substantially underestimated SOA formation, by factors as much as 4. Accounting for such losses has the clear potential to bring model predictions and observations of organic aerosol levels into much closer agreement.

Comparison of Real-Time Instruments Used To Monitor Airborne Particulate Matter

ABSTRACT Measurements collected using five real-time continuous airborne particle monitors were compared to measurements made using reference filter-based samplers at Bakers-field, CA, between December 2, 1998, and January 31, 1999. The purpose of this analysis was to evaluate the suitability of each instrument for use in a real-time continuous monitoring network designed to measure the mass of airborne particles with an aerodynamic diam less than 2.5 μm (PM2.5) under wintertime conditions in the southern San Joaquin Valley. Measurements of airborne particulate mass made with a beta attenuation monitor (BAM), an integrating nephelometer, and a continuous aerosol mass monitor (CAMM) were found to correlate well with reference measurements made with a filter-based sampler. A Dusttrak aerosol sampler overestimated airborne particle concentrations by a factor of ~3 throughout the study. Measurements of airborne particulate matter made with a tapered element oscillating microbalance (TEOM) were found to be lower than the reference filter-based measurements by an amount approximately equal to the concentration of NH4NO3 observed to be present in the airborne particles. The performance of the Dusttrak sampler and the integrating nephelometer was affected by the size distribution of airborne particulate matter. The performance of the BAM, the integrating nephelometer, the CAMM, the Dusttrak sampler, and the TEOM was not strongly affected by temperature, relative humidity, wind speed, or wind direction within the range of conditions encountered in the current study. Based on instrument performance, the BAM, the integrating nephelometer, and the CAMM appear to be suitable candidates for deployment in a real-time continuous PM2.5 monitoring network in central California for the range of winter conditions and aerosol composition encountered during the study.

The chemical composition of atmospheric ultrafine particles

Atmospheric ultrafine particles (with diameter less than 0.1 μm) may be responsible for some of the adverse health effects observed due to air–pollutant exposure. To date, little is known about the chemical composition of ultrafine particles in the atmosphere of cities. Ultrafine particle samples collected by inertial separation on the lower stages of cascade impactors can be analysed to determine a material balance on the chemical composition of such samples. Measurements of ultrafine particle mass concentration made in seven Southern California cities show that ultrafine particle concentrations in the size range 0.056–0.1 μm aerodynamic diameter average 0.55–1.16 μg m−3. The chemical composition of these ultrafine particle samples averages 50% organic compounds, 14% trace metal oxides, 8.7% elemental carbon, 8.2% sulphate, 6.8% nitrate, 3.7% ammonium ion (excluding one outlier), 0.6% sodium and 0.5% chloride. The most abundant catalytic metals measured in the ultrafine particles are Fe, Ti, Cr, Zn, with Ce also present. A source emissions inventory constructed for the South Coast Air Basin that surrounds Los Angeles shows a primary ultrafine particle emissions rate of 13 tonnes per day. Those ultrafine particle primary emissions arise principally from mobile and stationary fuel combustion sources and are estimated to consist of 65% organic compounds, 7% elemental carbon, 7% sulphate, 4% trace elements, with very small quantities of sodium, chloride and nitrate. This information should assist the community of inhalation toxicologists in the design of realistic exposure studies involving ultrafine particles.

Source contributions to the size and composition distribution of urban particulate air pollution

A mechanistic air quality model is developed that represents the atmospheric aerosol as a source-oriented external mixture of particles. A source-oriented external mixture is created when particles are released to the atmosphere from sources having distinctly different particle size and composition distributions. These particles evolve separately in the atmosphere while interacting with a common gas phase distribution of pollutants. The model represents advection, turbulent diffusion, gas-phase photochemistry, diffusion of reactants and products to and from the particles, aerosol thermodynamics, heterogeneous chemical reactions within fogs, and dry deposition. Calculations track individual particles from specific sources and then quantify the contribution which each source makes to the size and composition distribution of ambient suspended particulate matter at downwind receptor sites. Model results that simulate the August 28, 1987, episode of the Southern California Air Quality Study (SCAQS) experiments show that hygroscopic background particles advected into the Los Angeles area are transformed significantly by secondary chemical reactions in the urban atmosphere in a way that shapes the largest peak in the ambient fine particle (PM2.5) size distribution. Source contributions from more than 50 separate types of primary particle emissions sources also are revealed through a new technique for displaying model outputs. The air quality model is used to calculate the effects that alternative specific emissions control measures would have on air quality. Calculations show that a control plan which combines nearly all available emissions reduction techniques for gas- and particle-phase pollutants could have cut atmospheric fine particle (PM2.5) concentrations approximately in half at Claremont, CA, on August 28, 1987, in the absence of any other changes. Source tests are conducted to measure the size and chemical composition distribution of particles released from diesel vehicles, catalyst-equipped gasoline-powered vehicles, non-catalyst-equipped gasoline vehicles, meat cooking, wood burning, and cigarette smoke. These improved emissions data are combined with the air quality model, which then is used to determine the source origin of particulate matter in the Southern California atmosphere during field experiments conducted for purposes of model evaluation in September, 1996.

Associations of Mortality with Long-Term Exposures to Fine and Ultrafine Particles, Species and Sources: Results from the California Teachers Study Cohort

Background Although several cohort studies report associations between chronic exposure to fine particles (PM2.5) and mortality, few have studied the effects of chronic exposure to ultrafine (UF) particles. In addition, few studies have estimated the effects of the constituents of either PM2.5 or UF particles. Methods We used a statewide cohort of > 100,000 women from the California Teachers Study who were followed from 2001 through 2007. Exposure data at the residential level were provided by a chemical transport model that computed pollutant concentrations from > 900 sources in California. Besides particle mass, monthly concentrations of 11 species and 8 sources or primary particles were generated at 4-km grids. We used a Cox proportional hazards model to estimate the association between the pollutants and all-cause, cardiovascular, ischemic heart disease (IHD), and respiratory mortality. Results We observed statistically significant (p < 0.05) associations of IHD with PM2.5 mass, nitrate, elemental carbon (EC), copper (Cu), and secondary organics and the sources gas- and diesel-fueled vehicles, meat cooking, and high-sulfur fuel combustion. The hazard ratio estimate of 1.19 (95% CI: 1.08, 1.31) for IHD in association with a 10-μg/m3 increase in PM2.5 is consistent with findings from the American Cancer Society cohort. We also observed significant positive associations between IHD and several UF components including EC, Cu, metals, and mobile sources. Conclusions Using an emissions-based model with a 4-km spatial scale, we observed significant positive associations between IHD mortality and both fine and ultrafine particle species and sources. Our results suggest that the exposure model effectively measured local exposures and facilitated the examination of the relative toxicity of particle species. Citation Ostro B, Hu J, Goldberg D, Reynolds P, Hertz A, Bernstein L, Kleeman MJ. 2015. Associations of mortality with long-term exposures to fine and ultrafine particles, species and sources: results from the California Teachers Study cohort. Environ Health Perspect 123:549–556; http://dx.doi.org/10.1289/ehp.1408565

Modeling the airborne particle complex as a source‐oriented external mixture

A Lagrangian air quality model is developed which represents the airborne particle complex as a source-oriented external mixture. In a source-oriented external mixture, particles of the same size can evolve to display different chemical compositions that depend on the chemical and hygroscopic properties of the primary seed particles initially emitted from different sources. In contrast, previous models initialize the airborne particles as an internal mixture in which all particles of the same size are assumed to have the same chemical composition. Test cases show that representation of the aerosol as an internal mixture can distort the predicted particle composition and concentration in the HNO_3/NH_3/HCl/H_2SO_4/aerosol Cl^−/SO_4=/NO_3^−/NH_4^+/Na^+ system when Na^+ and SO_4^(=) exist in separate particles, as may occur when sea spray coexists with long-distance transport of anthropogenic sulfates. Tests also indicate that the external mixture model can predict the evolution of a nearly monodisperse aerosol into a bimodally distributed aerosol as relative humidity increases, qualitatively matching observations. The source-oriented external mixture model is applied to predict the size and composition distribution of airborne particles observed at Claremont, California, on August 28, 1987. Calculations produce an aerosol mass distribution that is distinctly bimodal in the size range from 0.1 μm to 1.0 μm particle diameter, matching field observations. External mixture calculations also predict specific differences in composition between particles of the same diameter. The external mixture model is expected to have applications including exploration of the cause of the particle-to-particle differences seen by time-of-flight mass spectrometers that measure single particle size and composition in the atmosphere.

What we breathe impacts our health: improving understanding of the link between air pollution and health

Air pollution contributes to the premature deaths of millions of people each year around the world, and air quality problems are growing in many developing nations. While past policy efforts have succeeded in reducing particulate matter and trace gases in North America and Europe, adverse health effects are found at even these lower levels of air pollution. Future policy actions will benefit from improved understanding of the interactions and health effects of different chemical species and source categories. Achieving this new understanding requires air pollution scientists and engineers to work increasingly closely with health scientists. In particular, research is needed to better understand the chemical and physical properties of complex air pollutant mixtures, and to use new observations provided by satellites, advanced in situ measurement techniques, and distributed micro monitoring networks, coupled with models, to better characterize air pollution exposure for epidemiological and toxicological research, and to better quantify the effects of specific source sectors and mitigation strategies.

Secondary organic aerosol 3. Urban/regional scale model of size- and composition-resolved aerosols

The California Institute of Technology (CIT) three-dimensional urban/regional atmospheric model is used to perform comprehensive gas- and aerosol-phase simulations of the 8 September 1993 smog episode in the South Coast Air Basin of California (SoCAB) using the atmospheric chemical mechanism of part 1 [Griffin et al., 2002] and the thermodynamic module of part 2 [Pun et al., 2002]. This paper focuses primarily on simulations of secondary organic aerosol (SOA) and determination of the species and processes that lead to this SOA. Meteorological data and a gas and particulate emissions inventory for this episode were supplied directly by the South Coast Air Quality Management District. A summer 1993 atmospheric sampling campaign provides data against which the performance of the model is evaluated. Predictions indicate that SOA formation in the SoCAB is dominated by partitioning of hydrophobic secondary products of the oxidation of anthropogenic organics. The biogenic contribution to total SOA increases in the more rural eastern portions of the region, as does the fraction of hydrophilic SOA, the latter reflecting the increasing degree of oxidation of SOA species with atmospheric residence time.

Dominant Mechanisms that Shape the Airborne Particle Size and Composition Distribution in Central California

The size and composition of ambient airborne particulate matter is reported for winter conditions at five locations in (or near) the San Joaquin Valley in central California. Two distinct types of airborne particles were identified based on diurnal patterns and size distribution similarity: hygroscopic sulfate/ammonium/nitrate particles and less hygroscopic particles composed of mostly organic carbon with smaller amounts of elemental carbon. Daytime PM10 concentrations for sulfate/ammonium/nitrate particles were measured to be 10.1 μ g m−3, 28.3 μ g m−3, and 52.8 μ g m−3 at Sacramento, Modesto and Bakersfield, California, respectively. Nighttime concentrations were 10–30% lower, suggesting that these particles are dominated by secondary production. Simulation of the data with a box model suggests that these particles were formed by the condensation of ammonia and nitric acid onto background or primary sulfate particles. These hygroscopic particles had a mass distribution peak in the accumulation mode (0.56–1.0 μ m) at all times. Daytime PM10 carbon particle concentrations were measured to be 9.5 μ g m−3, 15.1 μ g m−3, and 16.2 μ g m−3 at Sacramento, Modesto, and Bakersfield, respectively. Corresponding nighttime concentrations were 200–300% higher, suggesting that these particles are dominated by primary emissions. The peak in the carbon particle mass distribution varied between 0.2–1.0 μ m. Carbon particles emitted directly from combustion sources typically have a mass distribution peak diameter between 0.1–0.32 μ m. Box model calculations suggest that the formation of secondary organic aerosol is negligible under cool winter conditions, and that the observed shift in the carbon particle mass distribution results from coagulation in the heavily polluted concentrations experienced during the current study. The analysis suggests that carbon particles and sulfate/ammonium/nitrate particles exist separately in the atmosphere of the San Joaquin Valley until coagulation mixes them in the accumulation mode.

Size and Composition Distributions of Particulate Matter Emissions: Part 1—Light-Duty Gasoline Vehicles

Abstract Size-resolved particulate matter (PM) emitted from light-duty gasoline vehicles (LDGVs) was characterized using filter-based samplers, cascade impactors, and scanning mobility particle size measurements in the summer 2002. Thirty LDGVs, with different engine and emissions control technologies (model years 1965–2003; odometer readings 1264–207,104 mi), were tested on a chassis dynamometer using the federal test procedure (FTP), the unified cycle (UC), and the correction cycle (CC). LDGV PM emissions were strongly correlated with vehicle age and emissions control technology. The oldest models had average ultrafine PM0.1 (0.056- to 0.1-μm aerodynamic diameter) and fine PM1.8 (≤1.8-μm aerodynamic diame ter) emission rates of 9.6 mg/km and 213 mg/km, respectively. The newest vehicles had PM0.1 and PM1.8 emis sions of 51 μg/km and 371 μg/km, respectively. Light duty trucks and sport utility vehicles had PM0.1 and PM1.8 emissions nearly double the corresponding emission rates from passenger cars. Higher PM emissions were associated with cold starts and hard accelerations. The FTP driving cycle produced the lowest emissions, followed by the UC and the CC. PM mass distributions peaked between 0.1-and 0.18-μm particle diameter for all vehicles except those emitting visible smoke, which peaked between 0.18 and 0.32 μm. The majority of the PM was composed of carbonaceous material, with only trace amounts of water-soluble ions. Elemental carbon (EC) and organic matter (OM) had similar size distributions, but the EC/OM ratio in LDGV exhaust particles was a strong function of the adopted emissions control technology and of vehicle maintenance. Exhaust from LDGV classes with lower PM emissions generally had higher EC/OM ratios. LDGVs adopting newer technologies were characterized by the highest EC/OM ratios, whereas OM dominated PM emissions from older vehicles. Driving cycles with cold starts and hard accelerations produced higher EC/OM ratios in ultrafine particles.