James J. Schauer

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.

Levoglucosan, a tracer for cellulose in biomass burning and atmospheric particles

Abstract The major organic components of smoke particles from biomass burning are monosaccharide derivatives from the breakdown of cellulose, accompanied by generally lesser amounts of straight-chain, aliphatic and oxygenated compounds and terpenoids from vegetation waxes, resins/gums, and other biopolymers. Levoglucosan and the related degradation products from cellulose can be utilized as specific and general indicator compounds for the presence of emissions from biomass burning in samples of atmospheric fine particulate matter. This enables the potential tracking of such emissions on a global basis. There are other compounds (e.g. amyrones, friedelin, dehydroabietic acid, and thermal derivatives from terpenoids and from lignin—syringaldehyde, vanillin, syringic acid, vanillic acid), which are additional key indicators in smoke from burning of biomass specific to the type of biomass fuel. The monosaccharide derivatives (e.g. levoglucosan) are proposed as specific indicators for cellulose in biomass burning emissions. Levoglucosan is emitted at such high concentrations that it can be detected at considerable distances from the original combustion source.

Atmospheric brown clouds: Hemispherical and regional variations in long-range transport, absorption, and radiative forcing

polluted oceanic regions, the EC mass exceeds 0.5 m gm 3 , the OC mass exceeds 2 m gm 3 and sulfate mass exceeds 10 m gm 3 from the surface to 3 km. The brown clouds also have strong seasonal dependence. In the tropics the seasonal dependence is driven by pollution accumulating during the dry seasons, December to February in Northern Hemisphere tropics and June to August in Southern Hemisphere tropics. In the extratropics the pollution peaks during the summer. The brown cloud problem is not restricted to the tropical regions. Over the eastern half of US and western Europe the AODs exceeds 0.2 and absorption AODs exceed 0.02. Brown clouds also extend well into the western Pacific Ocean, the Indian Ocean reaching as far south as 60S and the eastern Atlantic Ocean. The largest total SO2 emission occurs over China and US, while SO2 emission per unit surface area is maximum over Germany and England. The largest total EC and OC emissions occur over China, but the largest OC emission per unit surface area occur over India. As a result, the maximum negative annual mean TOA direct forcing is over India and Germany. The surface annual-diurnal mean dimming over the regional hot spots is of the order of 10 W m 2 and 20 W m 2 over megacity hotpots.

Characterization of organic aerosols emitted from the combustion of biomass indigenous to South Asia

[1] Throughout South Asia biomass is commonly used as a fuel source for cooking and heating homes. The smoke from domestic use of these fuels is expected to be a major source of atmospheric particulate matter in the region and needs to be characterized for input in regional source apportionment models and global climate models. Biomass fuel samples including coconut leaves, rice straw, jackfruit branches, dried cowdung patties, and biomass briquettes manufactured from compressed biomass material were obtained from Bangladesh. The fuel samples were burned in a wood stove to collect and characterize the particulate matter emissions. The bulk chemical composition including total organic and elemental carbon, sulfate, nitrate, ammonium and chloride ions, and bulk elements such as potassium and sodium did not show conclusive differences among the biomass samples tested. Unique features, however, exist in the detailed organic characterization of the combustion smoke from the different sources. The organic compound fingerprints of the particulate matter are shown to be distinct from one another and distinct from North American wood fuels. Fecal stanols including 5b-stigmastanol, coprostanol, and cholestanol are found to be good molecular markers for the combustion of cowdung. Additionally, the patterns of methoxyphenols and plant sterols provide a unique signature for each biomass sample and are conducive as source apportionment tracers. INDEX TERMS: 0305 Atmospheric Composition and Structure: Aerosols and particles (0345, 4801); 0345 Atmospheric Composition and Structure: Pollution—urban and regional (0305); 0399 Atmospheric Composition and Structure: General or miscellaneous; 1699 Global Change: General or miscellaneous; KEYWORDS: biomass aerosol, molecular marker, organic

Evaluation of elemental carbon as a marker for diesel particulate matter

Elemental carbon (EC) in atmospheric particulate matter originates from a broad range of sources in many urban locations. As health and air quality studies are using elemental carbon measurements to better understand the impact of diesel engines and other combustion sources, there is a great need to clearly understand the relative source contributions to EC concentrations in the atmosphere. However, the different analytical techniques currently used to measure EC do not show good agreement for many particulate matter samples. To this end, studies that use EC as a tracer and integrate different analytical techniques for EC can significantly bias estimates of source contributions to atmospheric particulate matter. In addition, source attribution studies that do not properly address all sources of EC in the atmosphere can also lead to inaccuracies and biases. To better understand the use of EC as a tracer, a review of the distribution of EC in the primary particulate matter emissions from air pollution sources using different analytical methods is discussed. A review of previous apportionment studies of particulate matter is presented to elucidate the fraction of EC that results from emissions from diesel engines in urban locations. These results demonstrate that EC is not a unique tracer for diesel exhaust and efforts to utilize EC as an indicator of diesel exhaust must properly address other sources of EC as well as utilize a consistent measurement technique for EC when comparing source and ambient EC measurements to avoid significant biases.

The adjuvant effect of ambient particulate matter is closely reflected by the particulate oxidant potential

Background It has been demonstrated that ambient particulate matter (PM) can act as an adjuvant for allergic sensitization. Redox-active organic chemicals on the particle surface play an important role in PM adverse health effects and may determine the adjuvant effect of different particle types according to their potential to perturb redox equilibrium in the immune system. Objectives We determined whether the adjuvant effect of ambient fine particles versus ultrafine particles (UFPs) is correlated to their prooxidant potential. Methods We have established an intranasal sensitization model that uses ambient PM as a potential adjuvant for sensitization to ovalbumin (OVA), which enhances the capacity for secondary OVA challenge to induce allergic airway inflammation. Results UFPs with a greater polycyclic aromatic hydrocarbon (PAH) content and higher oxidant potential enhanced OVA sensitization more readily than did fine particles. This manifests as enhanced allergic inflammation upon secondary OVA challenge, leading to eosinophilic inflammation and mucoid hyperplasia starting at the nasal turbinates all the way down to the small pulmonary airways. The thiol antioxidant N-acetyl cysteine was able to suppress some of these sensitization events. Conclusions The adjuvant effects of ambient UFP is determined by their oxidant potential, which likely plays a role in changing the redox equilibrium in the mucosal immune system.

Indoor air pollution and blood pressure in adult women living in rural China.

Background: Almost half of the world’s population uses coal and biomass fuels for domestic energy. Limited evidence suggests that exposure to air pollutants from indoor biomass combustion may be associated with elevated blood pressure (BP). Objective: Our aim was to assess the relationship between air pollution exposure from indoor biomass combustion and BP in women in rural China. Methods: We measured 24-hr personal integrated gravimetric exposure to fine particles < 2.5 µm in aerodynamic diameter (PM2.5) and systolic BP (SBP) and diastolic BP (DBP) in the winter and summer among 280 women ≥ 25 years of age living in rural households using biomass fuels in Yunnan, China. We investigated the association between PM2.5 exposure and SBP and DBP using mixed-effects models with random intercepts to account for correlation among repeated measures. Results: Personal average 24-hr exposure to PM2.5 ranged from 22 to 634 µg/m3 in winter and from 9 to 492 µg/m3 in summer. A 1-log-µg/m3 increase in PM2.5 exposure was associated with 2.2 mm Hg higher SBP [95% confidence interval (CI), 0.8 to 3.7; p = 0.003] and 0.5 mm Hg higher DBP (95% CI, –0.4 to 1.3; p = 0.31) among all women; estimated effects varied by age group. Among women > 50 years of age, a 1-log-µg/m3 increase in PM2.5 exposure was associated with 4.1 mm Hg higher SBP (95% CI, 1.5 to 6.6; p = 0.002) and 1.8 mm Hg higher DBP (95% CI, 0.4 to 3.2; p = 0.01). PM2.5 exposure was positively associated with SBP among younger women, but the association was not statistically significant. Conclusion: PM2.5 exposure from biomass combustion may be a risk factor for elevated BP and hence for cardiovascular events. Our findings should be corroborated in longitudinal studies.

Emissions of Particulate Trace Elements, Metals and Organic Species from Gasoline, Diesel, and Biodiesel Passenger Vehicles and Their Relation to Oxidative Potential

Three light-duty passenger vehicles were tested in five configurations in a chassis dynamometer study to determine the chemical and oxidative potential of the particulate exhaust emissions. The first vehicle was a diesel Honda with a three-stage oxidation system. Its main catalyst was replaced with a diesel particulate filter (DPF) and tested as a second configuration. The second vehicle was a gasoline-fuelled Toyota Corolla with a three-way catalytic converter. The last vehicle was an older Volkswagen Golf, tested using petro-diesel in its original configuration, and biodiesel with an oxidation catalyst as an alternative configuration. Particulate matter (PM) was collected on filters and subsequently analyzed using various chemical and toxicological assays. The production of reactive oxygen species (ROS), quantified by the dithiothreitol (DTT) and macrophage-ROS assays, was used to measure the PM-induced oxidative potential. The results showed that the Golf vehicle in both configurations had the highest emissions of organic species (PAHs, hopanes, steranes, and organic acids). The DPF-equipped diesel Accord car emitted PM with the lowest amounts of organic species and the lowest oxidative potential. Correlation analyses showed that soluble Fe is strongly associated with particulate ROS activity (R = 0.99), while PAHs and hopanes were highly associated with DTT consumption rates (R = 0.94 and 0.91, respectively). In particular, tracers of lube oil emissions, namely Zn, P, Ca, and hopanes, were strongly correlated with distance-based DTT consumption rates (R = 0.96, 0.92, 0.83, and 0.91, respectively), suggesting that incomplete combustion of lube oil might be important driving factors of the overall PM-induced oxidative stress.

Development of Molecular Marker Source Profiles for Emissions from On-Road Gasoline and Diesel Vehicle Fleets

As part of the Gasoline/Diesel PM Split Study, relatively large fleets of gasoline vehicles and diesel vehicles were tested on a chassis dynamometer to develop chemical source profiles for source attribution of atmospheric particulate matter in Californias South Coast Air Basin. Gasoline vehicles were tested in cold-start and warm-start conditions, and diesel vehicles were tested through several driving cycles. Tailpipe emissions of particulate matter were analyzed for organic tracer compounds, including hopanes, steranes, and polycyclic aromatic hydrocarbons. Large intervehicle variation was seen in emission rate and composition, and results were averaged to examine the impacts of vehicle ages, weight classes, and driving cycles on the variation. Average profiles, weighted by mass emission rate, had much lower uncertainty than that associated with intervehicle variation. Mass emission rates and elemental carbon/organic carbon (EC/OC) ratios for gasoline vehicle age classes were influenced most by use of cold-start or warm-start driving cycle (factor of 2-7). Individual smoker vehicles had a large range of mass and EC/OC (factors of 40 and 625, respectively). Gasoline vehicle age averages, data on vehicle ages and miles traveled in the area, and several assumptions about smoker contributions were used to create emissions profiles representative of on-road vehicle fleets in the Los Angeles area in 2001. In the representative gasoline fleet profiles, variation was further reduced, with cold-start or warm-start and the representation of smoker vehicles making a difference of approximately a factor of two in mass emission rate and EC/OC. Diesel vehicle profiles were created on the basis of vehicle age, weight class, and driving cycle. Mass emission rate and EC/OC for diesel averages were influenced by vehicle age (factor of 2-5), weight class (factor of 2-7), and driving cycle (factor of 10-20). Absolute and relative emissions of molecular marker compounds showed levels of variation similar to those of mass and EC/OC.

Sampling methods used for the collection of particle-phase organic and elemental carbon during ACE-Asia

Abstract The semi-volatile nature of carbonaceous aerosols complicates their collection, and for this reason special air sampling configurations must be utilized. ACE-Asia provided a unique opportunity to compare different sampling techniques for collecting carbonaceous aerosols. In this paper detailed comparisons between filter-based carbonaceous aerosol sampling methods are made. The majority of organic carbon (OC) present on a backup quartz fiber filter (QFF) in an undenuded-filter sampler resulted from the adsorption of native gaseous OC rather than OC evaporated from collected particles. The level of OC on a backup QFF placed behind a QFF was lower than the level present on a backup QFF placed behind a Teflon membrane filter (TMF) indicating that gas/filter equilibrium may not be achieved in some QFF front and backup filter pairs. Gas adsorption artifacts can result in a 20–100% overestimation of the ambient particle-phase OC concentration. The gas collection efficiency of XAD-coated and carbon-impregnated filter-lined denuders were not always 100%, but, nonetheless, such denuders minimize gas adsorption artifacts. The median fraction of particle-phase OC that is estimated to evaporate from particles collected by denuder-filter samplers ranged from 0 to 0.2; this value depends on the sampler configuration, chemical composition of the OC, and sampling conditions. After properly correcting for sampling artifacts, the measured OC concentration may differ by 10% between undenuded- and denuder-filter samplers. Uncorrected, such differences can be as large as a factor two, illustrating the importance of sampling configurations in which gas adsorption or evaporation artifacts are reduced or can be corrected.