Lynn M. Hildemann

Source apportionment of airborne particulate matter using organic compounds as tracers

A chemical mass balance receptor model based on organic compounds has been developed that relates sours; contributions to airborne fine particle mass concentrations. Source contributions to the concentrations of specific organic compounds are revealed as well. The model is applied to four air quality monitoring sites in southern California using atmospheric organic compound concentration data and source test data collected specifically for the purpose of testing this model. The contributions of up to nine primary particle source types can be separately identified in ambient samples based on this method, and approximately 85% of the organic fine aerosol is assigned to primary sources on an annual average basis. The model provides information on source contributions to fine mass concentrations, fine organic aerosol concentrations and individual organic compound concentrations. The largest primary source contributors to fine particle mass concentrations in Los Angeles are found to include diesel engine exhaust, paved road dust, gasoline-powered vehicle exhaust, plus emissions from food cooking and wood smoke, with smaller contribution:; from tire dust, plant fragments, natural gas combustion aerosol, and cigarette smoke. Once these primary aerosol source contributions are added to the secondary sulfates, nitrates and organics present, virtually all of the annual average fine particle mass at Los Angeles area monitoring sites can be assigned to its source.

Water-soluble organics in atmospheric particles: A critical review of the literature and application of thermodynamics to identify candidate compounds

Although organic compounds typically constitute a substantial fraction of the fine particulate matter (PM) in the atmosphere, their molecular composition remains poorly characterized. This is largely because atmospheric particles contain a myriad of diverse organic compounds, not all of which extract in a single solvent or elute through a gas chromatograph; therefore, a substantial portion typically remains unanalyzed. Most often the chemical analysis is performed on a fraction that extracts in organic solvents such as benzene, ether or hexane; consequently, information on the molecular composition of the water-soluble fraction is particularly sparse and incomplete.This paper investigates theoretically the characteristics of the water-soluble fraction by splicing together various strands of information from the literature. We identify specific compounds that are likely to contribute to the water-soluble fraction by juxtaposing observations regarding the extraction characteristics and the molecular composition of atmospheric particulate organics with compound-specific solubility and condensibility for a wide variety of organics. The results show that water-soluble organics, which constitute a substantial fraction of the total organic mass, include C2 to C7 multifunctional compounds (e.g., diacids, polyols, amino acids). The importance of diacids is already recognized; our results provide an impetus for new experiments to establish the atmospheric concentrations and sources of polyols, amino acids and other oxygenated multifunctional compounds.

Quantification of urban organic aerosols at a molecular level : identification, abundance and seasonal variation

Organic aerosol samples collected systematically throughout a complete annual cycle at four urban sites in southern California are examined by high-resolution gas chromatography and gas chromatography/mass spectrometry. More than 80 organic compounds are quantified and their seasonal ambient concentration patterns are discussed. Primary organic aerosol constituents are readily identified, revealing an annual pattern, with high winter and low summer concentrations. In contrast, aliphatic dicarboxylic acids of possible secondary origin show a reverse pattern, with high concentrations in late spring/early summer. Concentration patterns similar to the secondary dicarboxylic acids also are found for aromatic polycarboxylic acids, certain lower molecular weight n-alkanoic acids, a nonanal and other compounds. Molecular markers characteristic of woodsmoke are identified, and their concentrations change by season in close agreement with prior estimates of the seasonal use of wood as a fuel. This data set can be used to evaluate the predictions of mathematical models for the atmospheric transport and reaction of organic aerosol constituents defined at a molecular level.

Organics alter hygroscopic behavior of atmospheric particles

The optical and chemical properties of atmospheric particles and their ability to act as cloud condensation nuclei (CCN) depend strongly upon their affinity for water. Laboratory experiments have shown that water soluble substances such as ammonium sulfate, ammonium nitrate, and sodium chloride, which are major inorganic components of atmospheric particles, absorb water in an amount proportional to water vapor pressure. Analogous information about the interactions between water and organics, which are another major component of atmospheric particles, is lacking. Here we analyze concurrent observations of particle chemical composition and water content from a continental nonurban (Grand Canyon) and an urban (Los Angeles) location to determine whether the water content of atmospheric particles is influenced by the presence of organics. By comparing the observed water content with the water content expected to be associated with the inorganic fraction, we find that the aggregate hygroscopic properties of inorganic particles are altered substantially when organics are also present. Furthermore, the alterations can be positive or negative. For the nonurban location, organics enhance water absorption by inorganics. In the relative humidity (RH) range of 80–88% organics account for 25–40% of the total water uptake, on average. For the urban location, on the other hand, the net effect of organics is to diminish water absorption of the inorganics by 25–35% in the RH range of 83–93%.

Sources of Fine Organic Aerosol. 6. Cigarette Smoke in the Urban Atmosphere

Molecular marker compounds that can be used to trace cigarette smoke particles in the outdoor urban atmosphere are identified. While the most abundant resolved organic compounds present are nitrogen-containing heterocyclics (e.g., nicotine), other potential tracers that will be more stable in the outdoor urban atmosphere also are found. Iso- and anteisoalkanes (C_(29)-C_(34)) are enriched in cigarette smoke particles and show a concentration pattern characteristic of tobacco leaf surface waxes that is distinctly different from leaf surface abrasion products shed from plant leaves that grow in the Los Angeles area. Relative to major leaf surface wax n-alkanes, these iso- and anteisoalkanes are enriched by a factor of more than 40 in tobacco and tobacco smoke particles as compared to leaf surface waxes from Los Angeles area plants. It is found that the iso- and anteisoalkanes concentration pattern generated by cigarette smoke is preserved in the urban atmosphere and is measured at levels that are comparable to emissions estimates based on daily cigarette consumption. Using these marker compounds, ambient fine cigarette smoke particles are estimated to be present at a concentration of 0.28-0.36 µg m^(-3) in the Los Angeles outdoor air, accounting for 1.0-1.3% of the fine particle mass concentration.

A Dilution Stack Sampler for Collection of Organic Aerosol Emissions: Design, Characterization and Field Tests

A dilution stack sampler specifically intended to collect fine organic aerosol from combustion sources while minimizing sample contamination has been designed and tested. The sampler simulates the cooling and dilution processes that occur in the plume downwind of a combustion source, so that the organic compounds which condense under ambient conditions will be collected as particulate matter. The special features of this sampler are described in detail, and compared with other stack sampling systems. The results of both laboratory and field tests of the system are discussed. Collection of organic aerosol using this sampler is compared with collection using EPA Method 5.

Submicrometer Aerosol Mass Distributions of Emissions from Boilers, Fireplaces, Automobiles, Diesel Trucks, and Meat-Cooking Operations

The predominant peak in the mass distribution emitted from each source measured in this study occurs at or below about 0.2 μm in particle diameter, whereas the Los Angeles atmospheric aerosol contains peaks at a variety of sizes in the range between 0.1 and 1.0 μm in particle diameter, including peaks at sizes larger than 0.2 μm. This suggests that considerable modification of the primary aerosol size distribution occurs because of subsequent processes in the atmosphere. The data presented here are intended for use in defining the size distribution of the primary combustion source effluent for use with mathematical models of the evolution of the atmospheric aerosol size distribution.

Sources of Urban Contemporary Carbon Aerosol

Emissions from the major sources of fine carbonaceous aerosol in the Los Angeles basin atmosphere have been analyzed to determine the amounts of the ^(12)C and ^(14)C isotopes present. From these measurements, an inventory of the fossil carbon and contemporary carbon particle emissions to the Los Angeles atmosphere has been created. In the winter, more than half of the fine primary carbonaceous aerosol emissions are from sources containing contemporary carbon, including fireplaces, charbroilers, paved road dust, cigarette smoke, and brake lining dust, while in the summer at least one-third of the carbonaceous particle emissions are contemporary. Using a mathematical model for atmospheric transport, predictions are made of the atmospheric fine particulate fossil carbon and contemporary carbon concentrations expected due to primary source emissions. Model predictions are in reasonable agreement with the measured radiocarbon content of the fine ambient aerosol samples. It is concluded that the high fraction of contemporary carbon measured historically in Los Angeles is not due to local emission sources of biogenic material; rather, it is due to a combination of local anthropogenic pollution sources and background marine aerosol advected into the city.

Low demand for nontraditional cookstove technologies

Biomass combustion with traditional cookstoves causes substantial environmental and health harm. Nontraditional cookstove technologies can be efficacious in reducing this adverse impact, but they are adopted and used at puzzlingly low rates. This study analyzes the determinants of low demand for nontraditional cookstoves in rural Bangladesh by using both stated preference (from a nationally representative survey of rural women) and revealed preference (assessed by conducting a cluster-randomized trial of cookstove prices) approaches. We find consistent evidence across both analyses suggesting that the women in rural Bangladesh do not perceive indoor air pollution as a significant health hazard, prioritize other basic developmental needs over nontraditional cookstoves, and overwhelmingly rely on a free traditional cookstove technology and are therefore not willing to pay much for a new nontraditional cookstove. Efforts to improve health and abate environmental harm by promoting nontraditional cookstoves may be more successful by designing and disseminating nontraditional cookstoves with features valued more highly by users, such as reduction of operating costs, even when those features are not directly related to the cookstoves’ health and environmental impacts.

AMMONIA AND NITRIC ACID CONCENTRATIONS IN EQUILIBRIUM WITH ATMOSPHERIC AEROSOLS: EXPERIMENT VS THEORY

The equilibrium between gaseous ammonia, nitric acid, and aerosol nitrate is discussed on the basis of a recent field experiment in southern California. Comparison is drawn between theoretical equilibrium calculations and simultaneous measurements of nitric acid, ammonia, ammonium ion, nitrate ion, sulfate ion, other ionic species, temperature and dewpoint. Particulate and gaseous pollutant concentrations at some inland sampling sites are readily explained if the aerosol is assumed to exist as an external mixture with all particulate nitrate and ammonium available to form pure NH_4NO_3. At other monitoring sites, especially near the coast, aerosol nitrate is found in the presence of NH_3 and HNO_3 concentrations that thermodynamic calculations show are too low to produce pure NH_4NO_3. This can be explained when the amount of aerosol nitrate that can be derived from reaction of nitric acid with sea salt and soil dust is taken into account. A calculation approach that accounts for the presence of mixed sulfate and nitrate salts improves the agreement between predicted and observed pollutant concentrations in the majority of cases studied. Uncertainties in these calculations arise from a number of sources including the thermodynamic quantities, and the effect of these uncertainties on the comparison between theory and experiment is discussed.