Using sulfur as a tracer of outdoor fine particulate matter

Six homes in the metropolitan Boston area were sampled between 6 and 12 consecutive days for indoor and outdoor particle volume and mass concentrations, particle elemental concentrations, and air exchange rates (AERs). Indoor/outdoor (I/O) ratios of nighttime (i.e., particle nonindoor source periods) sulfur, PM2.5 and the specific particle size intervals were used to provide estimates of the effective penetration efficiency. Mixed models and graphical displays were used to assess the ability of the I/O ratios for sulfur to estimate corresponding I/O ratios for PM2.5 and the various particle sizes. Results from this analysis showed that particulate sulfur compounds were primarily of outdoor origin and behaved in a manner that was representative of total PM2.5 in Boston, MA. These findings support the conclusion that sulfur can be used as a suitable tracer of outdoor PM2.5 for the homes sampled in this study. Sulfur was more representative of particles of similar size (0.06-0.5 microm), providing evidence that the size composition of total PM2.5 is an important characteristic affecting the robustness of sulfur-based estimation methods.     

Chemical compositions of fine particulate organic matter emitted from Chinese cooking

Food cooking can be a significant source of atmospheric particulate organic matter. In this study, the chemical composition of particulate organic matter (POM) in PM2.5 emitted from four different Chinese cooking styles were examined by gas chromotography-mass spectrometry (GC-MS). The identified species are consistent in the emissions from different Chinese cooking styles and the quantified compounds account for 5-10% of total POM in PM2.5. The dominant homologue is fatty acids, constituting 73-85% of the quantified compounds. The pattern of n-alkanes and the presence of beta-sitosterol and levoglucosan indicate that vegetables are consumed during Chinese cooking operations. Furthermore, the emissions of different compounds are impacted significantly by the cooking ingredients. The candidates of organic tracers used to describe and distinguish emissions from Chinese cooking in Guangzhou are tetradecanoic acid, hexadecanoic acid, octadecanoic acid, oleic acid, levoglucosan, mannosan, galactosan, nonanal, and lactones. During the sampling period, the relative contribution of Chinese cooking to the mass concentration of atmospheric hexadecanoic acid should be less than 1.3% in Guangzhou.     

Application of land use regression to estimate long-term concentrations of traffic-related nitrogen oxides and fine particulate matter

Land use regression (LUR) is a promising technique for predicting ambient air pollutant concentrations at high spatial resolution. We expand on previous work by modeling oxides of nitrogen and fine particulate matter in Vancouver, Canada, using two measures of traffic. Systematic review of historical data identified optimal sampling periods for NO and N02. Integrated 14-day mean concentrations were measured with passive samplers at 116 sites in the spring and fall of 2003. Study estimates for annual mean NO and NO2 ranged from 5.4-98.7 and 4.8-28.0 ppb, respectively. Regulatory measurements ranged from 4.8-29.7 and 9.0-24.1 ppb and exhibited less spatial variability. Measurements of particle mass concentration (PM2.5) and light absorbance (ABS) were made at a subset of 25 sites during another campaign. Fifty-five variables describing each sampling site were generated in a Geographic Information System (GIS) and linear regression models for NO, NO2, PM2.5, and ABS were built with the most predictive covariates. Adjusted R(2) values ranged from 0.39 to 0.62 and were similar across traffic metrics. Resulting maps show the distribution of NO to be more heterogeneous than that of NO2, supporting the usefulness of this approach for assessing spatial patterns of traffic-related pollution.     

Mass spectral analysis of organic aerosol formed downwind of the deepwater horizon oil spill: field studies and laboratory confirmations

In June 2010, the NOAA WP-3D aircraft conducted two survey flights around the Deepwater Horizon (DWH) oil spill. The Gulf oil spill resulted in an isolated source of secondary organic aerosol (SOA) precursors in a relatively clean environment. Measurements of aerosol composition and volatile organic species (VOCs) indicated formation of SOA from intermediate-volatility organic compounds (IVOCs) downwind of the oil spill (Science2011, 331, doi 10.1126/science.1200320). In an effort to better understand formation of SOA in this environment, we present mass spectral characteristics of SOA in the Gulf and of SOA formed in the laboratory from evaporated light crude oil. Compared to urban primary organic aerosol, high-mass-resolution analysis of the background-subtracted SOA spectra in the Gulf (for short, "Gulf SOA") showed higher contribution of C(x)H(y)O(+) relative to C(x)H(y)(+) fragments at the same nominal mass. In each transect downwind of the DWH spill site, a gradient in the degree of oxidation of the Gulf SOA was observed: more oxidized SOA (oxygen/carbon = O/C ～0.4) was observed in the area impacted by fresher oil; less oxidized SOA (O/C ～0.3), with contribution from fragments with a hydrocarbon backbone, was found in a broader region of more-aged surface oil. Furthermore, in the plumes originating from the more-aged oil, contribution of oxygenated fragments to SOA decreased with downwind distance. Despite differences between experimental conditions in the laboratory and the ambient environment, mass spectra of SOA formed from gas-phase oxidation of crude oil by OH radicals in a smog chamber and a flow tube reactor strongly resembled the mass spectra of Gulf SOA (r(2) > 0.94). Processes that led to the observed Gulf SOA characteristics are also likely to occur in polluted regions where VOCs and IVOCs are coemitted.     

Trimethylsilyl derivatives of organic compounds in source samples and in atmospheric fine particulate matter

Source sample extracts of vegetative detritus, motor vehicle exhaust, tire dust paved road dust, and cigarette smoke have been silylated and analyzed by GC-MS to identify polar organic compounds that may serve as tracers for those specific emission sources of atmospheric fine particulate matter. Candidate molecular tracers were also identified in atmospheric fine particle samples collected in the San Joaquin Valley of California. A series of normal primary alkanols, dominated by even carbon-numbered homologues from C26 to C32, the secondary alcohol 10-nonacosanol, and some phytosterols are prominent polar compounds in the vegetative detritus source sample. No new polar organic compounds are found in the motor vehicle exhaust samples. Several hydrogenated resin acids are present in the tire dust sample, which might serve as useful tracers for those sources in areas that are heavily impacted by motor vehicle traffic. Finally, the alcohol and sterol emission profiles developed for all the source samples examined in this project are scaled according to the ambient fine particle mass concentrations attributed to those sources by a chemical mass balance receptor model that was previously applied to the San Joaquin Valley to compute the predicted atmospheric concentrations of individual alcohols and sterols. The resulting underprediction of alkanol concentrations at the urban sites suggests that alkanols may be more sensitive tracers for natural background from vegetative emissions (i.e., waxes) than the high molecular weight alkanes, which have been the best previously available tracers for that source.     

A probabilistic characterization of the relationship between fine particulate matter and mortality: elicitation of European experts

In support of an assessment of the mortality impacts of the Kuwait Oil Fires we interviewed six European experts in epidemiology and toxicology using formal procedures for elicitation of expert judgment. While the primary focus of the elicitations was to characterize the public health impacts of the fires, the experts provided quantitative estimates of the mortality impacts of hypothetical changes in the levels of ambient fine particulate matter (PM2.5) in both the United States and Europe. Uncertainty was assessed by asking each expert to provide the 5th, 25th, 50th, 75th, and 90th percentiles of their subjective cumulative probability density function for each quantity of interest. The results suggest that many regulatory risk assessments underestimate the impacts of PM2.5 mortality; confirm that only a small fraction of the mortality impact occurs within the first few months after exposure; and indicate that it may be important to better address the differential toxicities of particles from various source classes. By providing quantitative estimates of the uncertainty in current estimates of PM2.5 mortality risks, the study facilitates structured analysis of the value of further research on PM2.5 and its impacts.     

Source apportionment of fine particulate matter by clustering single-particle data: tests of receptor model accuracy

The source apportionment accuracy of a neural network algorithm (ART-2a) is tested on the basis of its application to synthetic single-particle data generated by a source-oriented aerosol processes trajectory model that simulates particle emission, transport, and chemical reactions in the atmosphere. ART-2a successfully groups particles from the majority of sources actually present, when given complete data on ambient particle composition at monitoring sites located near the emission sources. As particles age in the atmosphere, accumulation of gas-to-particle conversion products can act to disguise the source of the primary core of the particles. When ART-2a is applied to synthetic single-particle data that are modified to simulate the biases in aerosol time-of-flight mass spectrometry (ATOFMS) measurements, best results are obtained using the ATOFMS dual ion operating mode that simultaneously yields both positive and negative ion mass spectra. The results of this study suggest that the use of continuous single-particle measurements coupled with neural network algorithms can significantly improve the time resolution of particulate matter source apportionment.     

Sensitivities of ozone and fine particulate matter formation to emissions under the impact of potential future climate change

Impact of climate change alone and in combination with currently planned emission control strategies are investigated to quantify effectiveness in decreasing regional ozone and PM2.5 over the continental U.S. using MM5, SMOKE, and CMAQ with DDM-3D. Sensitivities of ozone and PM2.5 formation to precursor emissions are found to change only slightly in response to climate change. In many cases, mass per ton sensitivities to NO(x) and SO2 controls are predicted to be greater in the future due to both the lower emissions as well as climate, suggesting that current control strategies based on reducing such emissions will continue to be effective in decreasing ground-level ozone and PM2.5 concentrations. SO2 emission controls are predicted to be most beneficial for decreasing summertime PM2.5 levels, whereas controls of NO(x) emissions are effective in winter. Spatial distributions of sensitivities are also found to be only slightly affected assuming no changes in land-use. Contributions of biogenic VOC emissions to PM2.5 formation are simulated to be more important in the future because of higher temperatures, higher biogenic emissions, and lower anthropogenic NO(x) and SO2 emissions.     

Rapid arsenite oxidation by Thermus aquaticus and Thermus thermophilus: field and laboratory investigations

Thermus aquaticus and Thermus thermophilus, common inhabitants of terrestrial hot springs and thermally polluted domestic and industrial waters, have been found to rapidly oxidize arsenite to arsenate. Field investigations at a hot spring in Yellowstone National Park revealed conserved total arsenic transport and rapid arsenite oxidation occurring within the drainage channel. This environment was heavily colonized by Thermus aquaticus. In laboratory experiments, arsenite oxidation by cultures of Thermus aquaticus YT1 (previously isolated from Yellowstone National Park) and Thermus thermophilus HB8 was accelerated by a factor of over 100 relative to a biotic controls. Thermus aquaticus and Thermus thermophilus may therefore play a large and previously unrecognized role in determining arsenic speciation and bioavailability in thermal environments.     

Separation of fine particulate matter emitted from gasoline and diesel vehicles using chemical mass balancing techniques

Samples of fine particulate matter were collected in a roadway tunnel near Houston, TX over a period of 4 days during two separate sampling periods: one sampling period from 1200 to 1400 local time and another sampling period from 1600 to 1800 local time. During the two sampling periods, the tunnel traffic contained roughly equivalent numbers of heavy-duty diesel trucks. However, during the late afternoon sampling period, the tunnel contained twice as many light-duty gasoline-powered vehicles. The effect of this shift in the vehicle fleet affects the overall emission index (grams pollutant emitted per kilogram carbon in fuel) for fine particles and fine particulate elemental carbon. Additionally, this shift in the fraction of diesel vehicles in the tunnel is used to determine if the chemical mass balancing techniques used to track emissions from gasoline-powered and diesel-powered emissions accurately separates these two emission categories. The results show that the chemical mass balancing calculations apportion roughly equal amounts of the particulate matter measured to diesel vehicles between the two periods and attribute almost twice as much particulate matter in the late afternoon sampling period to gasoline vehicles. Both of these results are consistent with the traffic volume of gasoline and diesel vehicles in the tunnel in the two separate periods and validate the ability for chemical mass balancing techniques to separate these two primary sources of fine particles.     

Technical note: Contribution of ammonia emitted from livestock to atmospheric fine particulate matter (PM2.5) in the United States

Ammonia emitted from animal feeding operations is an air pollutant contributing to the formation of fine particulate matter (PM_2.5), considered a major environmental risk to human health. In the United States, farm animals are the greatest contributor to gaseous ammonia emissions. Ammonia reacts with atmospheric nitric and sulfuric acids to form PM_2.5 (nitrate and sulfate), but the proportion of PM_2.5 attributable to ammonia emitted from animal farming operations has not been quantified. Thus, the objective of this analysis was to estimate the contribution of ammonia emitted from farm animals to PM_2.5 in the United States. The following approach was used: (1) the amount of ammonium in sulfate and nitrate PM_2.5 was calculated based on chemically speciated measurements published by the United States Environmental Protection Agency; and (2) the amount of ammonium in sulfate and nitrate PM_2.5 originating from livestock was assumed equal to the fraction of the total ammonia emissions attributable to livestock. Across different regions of the United States and under different weather conditions, PM_2.5 formed from ammonia emitted from livestock operations were estimated to contribute on average from 5 to 11% of the total PM_2.5 concentrations. In certain areas (North Central, for example) and in cool weather, farm animal contribution to atmospheric PM_2.5 concentration may be as much as 20%.     

Characterization of saccharides in size-fractionated ambient particulate matter and aerosol sources: the contribution of primary biological aerosol particles (PBAPs) and soil to ambient particulate matter

Size-fractionated (equivalent to ambient PM2.5 and PM10) local soil, plant, and spore samples were collected in the Sonoran Desert near Phoenix, AZ and measured for saccharide content with the goal of characterizing ambient particulate matter sources including soil and primary biological aerosol particles (PBAPs) from plants and fungi. Different saccharide compositions were observed among soil, plant, and spore samples and between PM2.5 and PM10 fractions. The total measured nonlevoglucosan saccharide content relative to PM mass in ambient aerosols collected in a Phoenix suburb (Higley) was much higher compared to the local soil samples but much lower compared to the PBAP. The enrichment of saccharides from two saccharide-dominated PM source factors resolved by a positive matrix factorization model is also higher than the saccharide content in the size-fractionated local soil samples, but lower than that measured in the size-segregated PBAP samples. This indicates that ambient concentration of particulate saccharides at Higley was dominated by contributions from PBAPs directly injected into the atmosphere from plants and spores rather than from soil and associated biota. Our results also suggest the contribution to the fine size fraction of ambient PM from the primary biologically derived sources may be greater than previously acknowledged.     

Expert judgment assessment of the mortality impact of changes in ambient fine particulate matter in the U.S

In this paper, we present findings from a multiyear expert judgment study that comprehensively characterizes uncertainty in estimates of mortality reductions associated with decreases in fine particulate matter (PM(2.5)) in the U.S. Appropriate characterization of uncertainty is critical because mortality-related benefits represent up to 90% of the monetized benefits reported in the Environmental Protection Agency's (EPA's) analyses of proposed air regulations. Numerous epidemiological and toxicological studies have evaluated the PM(2.5)-mortality association and investigated issues that may contribute to uncertainty in the concentration-response (C-R) function, such as exposure misclassification and potential confounding from other pollutant exposures. EPA's current uncertainty analysis methods rely largely on standard errors in published studies. However, no one study can capture the full suite of issues that arise in quantifying the C-R relationship. Therefore, EPA has applied state-of-the-art expert judgment elicitation techniques to develop probabilistic uncertainty distributions that reflect the broader array of uncertainties in the C-R relationship. These distributions, elicited from 12 of the world's leading experts on this issue, suggest both potentially larger central estimates of mortality reductions for decreases in long-term PM(2.5) exposure in the U.S. and a wider distribution of uncertainty than currently employed in EPA analyses.     

Interactions between Cd,Cu, and Zn influence particulate phytochelatin concentrations in marine phytoplankton: laboratory results and preliminary field data

The effect of metal interactions on phytochelatin production by marine phytoplankton has received little attention but yet is critical to understanding the biochemical production of this potentially important metal-binding ligand in the field. Cd, Cu, and Zn additions were made singly and in combination to three species of laboratory cultures and to a natural algal assemblage from pristine coastal seawater. In the laboratory cultures intracellular phytochelatin varied with metal exposure and demonstrated metal- and concentration-dependent synergisms and antagonisms. Most notably, the addition of all three metals together greatly suppressed phytochelatin production in all cultures. Particulate phytochelatin was also measured at two field sites. In the field, phytochelatin production is related to ambient Cd, Cu, and Zn levels, and the deviations from the dose-response relationship are potentially explained by metal interactions similar to those observed in the laboratory cultures. Though particulate glutathione concentrations were very low in some field samples, it did not appear to limit phytochelatin production. Particulate phytochelatin concentrations in samples from both field sites were very similar to those measured in the laboratory cultures when exposed to all three metals together, and thus phytochelatin levels in the field may be regulated by the interaction of Cd, Cu, and Zn.     

Source contributions to atmospheric gases and particulate matter in the southeastern United States

A new approach for determining the contributions of emission sources to concentrations of particulate matter and gases is developed using the chemical mass balance (CMB) method and the U.S. EPA's National Emission Inventory (NEI). The approach apportions combined gas-phase and condensed-phase concentrations of individual compounds as well as PM(2.5) mass. Because the NEI is used to provide source emission profiles for CMB analysis, the method generates information on the consistency of the NEI with ambient monitoring data. The method also tracks secondary species to primary source emissions, permitting a more complete accounting of the impact of aggregated source types on PM(2.5) mass concentrations. An example application is presented using four years of monitoring data collected at eight sites in the Southeastern Aerosol Research and Characterization (SEARCH) network. Including both primary and secondary species, area sources contributed 2.0-3.7 μg m(-3) (13-26%), point sources contributed 3.0-4.6 μg m(-3) (22-33%), and mobile sources contributed 1.0-6.0 μg m(-3) (9-42%) to mean PM(2.5) mass concentrations. Whereas the NEI generally accounts for the ambient concentrations of gases and particles, certain anomalies are identified, especially related to carbonaceous compounds and dust.     

Development and application of a mobile laboratory for measuring emissions from diesel engines. 2. Sampling for toxics and particulate matter

Limited data are available on the emission rates of speciated volatile and semivolatile organic compounds, as well as the physical and chemical characteristics of fine particulate matter (PM) from mobile, in-use diesel engines operated on the road. A design for the sampling of these fractions and the first data from in-use diesel sources are presented in this paper. Emission rates for carbonyls, 1,3-butadiene, benzene, toluene, xylene, PM, and elemental and organic carbon (EC and OC) are reported for a vehicle driven while following the California Air Resources Board (ARB) four-mode heavy heavy-duty diesel truck (HHDDT) cycle and while transiting through a major transportation corridor. Results show that distance specific emission rates are substantially greater in congested traffic as compared with highway cruise conditions. Specifically, emissions of toxic compounds are 3-15 times greater, and PM is 7 times greater under these conditions. The dependence of these species on driving mode suggests that health and source apportionment studies will need to account for driving patterns in addition to emission factors. Comparison of the PM/NOx ratios obtained for the above tests provides insight into the presence and importance of "off-cycle" emissions during on-road driving. Measurements from a stationary source (operated and tested at constant engine speed) equipped with an engine similar to that in the HHDDT yielded a greater understanding of the relative dependence of emissions on load versus engine transients. These data are indicative of the type of investigations made possible by the development of this novel laboratory.     

Indoor particulate matter of outdoor origin: importance of size-dependent removal mechanisms

Adverse human health effects have been observed to correlate with levels of outdoor particulate matter (PM), even though most human exposure to PM of outdoor origin occurs indoors. In this study, we apply a model and empirical data to explore the indoor PM levels of outdoor origin for two major building types: offices and residences. Typical ventilation rates for each building type are obtained from the literature. Published data are combined with theoretical analyses to develop representative particle penetration coefficients, deposition loss rates, and ventilation-system filter efficiencies for a broad particle size range (i.e., 0.001-10 microm). We apply archetypal outdoor number, surface area, and mass PM size distributions for both urban and rural airsheds. We also use data on mass-weighted size distributions for specific chemical constituents of PM: sulfate and elemental carbon. Predictions of the size-resolved indoor proportion of outdoor particles (IPOP) for various conditions and ambient particle distributions are then computed. The IPOP depends strongly on the ambient particle size distribution, building type and operational parameters, and PM metric. We conclude that an accurate determination of exposure to particles of ambient origin requires explicit consideration of how removal processes in buildings vary with particle size.     

Heterogeneous reactions of glyoxal on particulate matter: identification of acetals and sulfate esters

Reactive uptake of glyoxal onto particulate matter has been studied in laboratory experiments in a 2 m3 Teflon reaction chamber. Inorganic seed particles of different composition were utilized, including (NH4)2SO4, (NH4)2SO4/ H2SO4, NaNO3, and simulated sea salt, while the relative humidity and acid concentration were varied. The organic composition of the growing particles was measured in situ with an aerosol mass spectrometer, providing particle mass spectra as a means of product identification. Aerosol physical characteristics were also measured with a differential mobility analyzer and condensation nucleus counter. Regardless of seed composition, particle growth was rapid and continuous over the course of several hours. Identification of several mass fragments greater than the glyoxal monomer suggested that heterogeneous reactionsto form glyoxal adducts of lowvolatility had occurred. Temporal analysis of the mass fragments was consistent with a proposed acid-catalyzed mechanism whereby glyoxal is first hydrated, followed by self-reaction to form cyclic acetal structures. Increased relative humidity slowed the formation of higher order oligomers, also consistent with the proposed mechanism. The relative contribution of various oligomers to the overall organic composition was strongly dependent on the relative humidity and hence the particulate water concentration. A mild acid catalysis was also observed upon increasing the acidity of the seed particles. Specific mass fragments were found that could only arise from sulfate esters and were not present on the non-sulfur-containing seed particles. This first evidence of the formation of organic sulfates in particles is presented together with a proposed mechanism and molecular structure. These results suggest that the formation of these products of glyoxal uptake can contribute significantly to secondary organic aerosol.     

Regional air quality: local and interstate impacts of NO(x) and SO2 emissions on ozone and fine particulate matter in the eastern United States

While the U.S. air quality management system is largely designed and managed on a state level, many critical air quality problems are now recognized as regional. In particular, concentrations of two secondary pollutants, ozone and particulate matter, are often above regulated levels and can be dependent on emissions from upwind states. Here, impacts of statewide emissions on concentrations of local and downwind states' ozone and fine particulate matter are simulated for three seasonal periods in the eastern United States using a regional Eulerian photochemical model. Impacts of ground level NO(x) (e.g., mobile and area sources), elevated NO(x) (e.g., power plants and large industrial sources), and SO2 emissions are examined. An average of 77% of each state's ozone and PM(2.5) concentrations that are sensitive to the emissions evaluated here are found to be caused by emissions from other states. Delaware, Maryland, New Jersey, Virginia, Kentucky, and West Virginia are shown to have high concentrations of ozone and PM(2.5) caused by interstate emissions. When weighted by population, New York receives increased interstate contributions to these pollutants and contributions to ozone from local emissions are generally higher. When accounting for emission rates, combined states from the western side of the modeling domain and individual states such as Illinois, Tennessee, Indiana, Kentucky, and Georgia are major contributors to interstate ozone. Ohio, Indiana, Tennessee, Kentucky, and Illinois are the major contributors to interstate PM(2.5). When accounting for an equivalent mass of emissions, Tennessee, Kentucky, West Virginia, Virginia, and Alabama contribute large fractions of these pollutants to other states.     

Emerging and re-emerging diseases of agricultural importance: why local perspectives matter

This paper examines local farmers’ perspectives about emerging and re-emerging infectious diseases (EIDs) of humans, crops and livestock and their impact on household food security in the Tanzania-Uganda interface ecosystem to the west of Lake Victoria. While it is increasingly accepted that such an approach could yield vital information not only regarding the extent of the impact of EIDs but also on practical strategies for their control, recent studies have examined only a narrow part of the disease-food security spectrum, often lacking a clear analysis of how local people conceptualise the co-occurrence, interactions and impact on food security of multiple plant, animal and human disease afflictions. Findings of the present study reveal that farmers perceive diseases as products of wider social, economic, environmental and institutional realities. They employ a wide range of names to describe disease problems and often such labels have nothing in common with the binomial nomenclature used in scientific taxonomy. Frequently, local people’s perceptions of severity of the impact of disease on food security are at variance with views held by experts. Consequently, disease control measures and strategies advocated by experts and policy makers are often not adhered to. This paper reveals that local or emic perspectives on diseases not only convey the sense of how local people feel and think about a particular disease but also how such knowledge shapes their response effort. Finally, the paper argues for a strategy to harness and incorporate aspects of local perspectives and practices into formal disease control programmes.