Diagnosis of aged prescribed burning plumes impacting an urban area

An unanticipated wind shift led to the advection of plumes from two prescribed burning sites that impacted Atlanta, GA, producing a heavy smoke event late in the afternoon on February 28, 2007. Observed PM2.5 concentrations increased to over 140 microg/m3 and O3 concentrations up to 30 ppb in a couple of hours, despite the late hour in February when photochemistry is less vigorous. A detailed investigation of PM2.5 chemical composition and source apportionment analysis showed that the increase in PM2.5 mass was driven mainly by organic carbon (OC). However, both results from source apportionment and an observed nonlinear relationship between OC and PM2.5 potassium (K) indicate that the increased OC was not due solely to primary emissions. Most of the OC was water-soluble organic carbon (WSOC) and was dominated by hydrophobic compounds. The data are consistent with large enhancements in isoprenoid (isoprene and monoterpenes) and other volatile organic compounds emitted from prescribed burning that led to both significant O3 and secondary organic aerosol (SOA) production. Formation of oligomers from oxidation products of isoprenoid compounds or condensation of volatile organic compounds (VOCs) with multiple functional groups emitted during prescribed burning appears to be a major component of the secondary organic contributor of the SOA. The results from this study imply that enhanced emissions due to the fire itself and elevated temperature in the burning region should be considered in air quality models (e.g., receptor and emission-based models) to assess impacts of prescribed burning emissions on ambient air quality.     

Response of atmospheric particulate matter to changes in precursor emissions: a comparison of three air quality models

Three mathematical models of air quality (CMAQ, CMAQ-MADRID, and REMSAD) are applied to simulate the response of atmospheric fine particulate matter (PM2.5) concentrations to reductions in the emissions of gaseous precursors for a 10 day period of the July 1999 Southern Oxidants Study (SOS) in Nashville. The models are shown to predict similar directions of the changes in PM2.5 mass and component (sulfate, nitrate, ammonium, and organic compounds) concentrations in response to changes in emissions of sulfur dioxide (SO2), nitrogen oxides (NO(x)), and volatile organic compounds (VOC), except for the effect of SO2 reduction on nitrate and the effect of VOC reduction on PM2.5 mass. Furthermore, in many cases where the directional changes are consistent, the magnitude of the changes are significantly different among models. Examples are the effects of SO2 and NO(x) reductions on nitrate and PM2.5 mass and the effects of VOC reduction on organic compounds, sulfate and nitrate. The spatial resolution significantly influences the results in some cases. Operational model performance for a PM2.5 component appears to provide some useful indication on the reliability of the relative response factors (RRFs) for a change in emissions of a direct precursor, as well as for a change in emissions of a compound that affects this component in an indirect manner, such as via oxidant formation. However, these results need to be confirmed for other conditions and caution is still needed when applying air quality models for the design of emission control strategies. It is advisable to use more than one air quality model (or more than one configuration of a single air quality model) to span the full range of plausible scientific representations of atmospheric processes when investigating future air quality scenarios.     

Speciation of gas-phase and fine particle emissions from burning of foliar fuels

Fine particle matter with aerodynamic diameter <2.5 microm (PM2.5) and gas-phase emissions from open burning of six fine (foliar) fuels common to fire-prone U.S. ecosystems are investigated. PM2.5 distribution is unimodal within the 10-450 nm range, indicative of an accumulation mode. Smoldering relative to flaming combustion shows smaller particle number density per unit time and median size. Over 100 individual organic compounds in the primarily carbonaceous (>70% by mass) PM2.5 are chemically speciated by gas chromatography/mass spectrometry. Expressed as a percent of PM2.5 mass, emission ranges by organic compound class are as follows: n-alkane (0.1-2%), polycyclic aromatic hydrocarbon (PAH) (0.02-0.2%), n-alkanoic acid (1-3%), n-alkanedioic acid (0.06-0.3%), n-alkenoic acid (0.3-3%), resin acid (0.5-6%), triterpenoid (0.2-0.5%), methoxyphenol (0.5-3%), and phytosterol (0.2-0.6%). A molecular tracer of biomass combustion, the sugar levoglucosan is abundant and constitutes a remarkably narrow PM2.5 mass range (2.8-3.6%). Organic chemical signatures in PM2.5 from open combustion of fine fuels differ with those of residential wood combustion and other related sources, making them functional for source-receptor modeling of PM. Inorganic matter [PM2.5 - (organic compounds + elemental carbon)] on average is estimated to make up 8% of the PM2.5. Wavelength dispersive X-ray fluorescence spectroscopy and ion chromatography identify 3% of PM2.5 as elements and water-soluble ions, respectively. Compared with residential wood burning, the PM2.5 of fine fuel combustion is nitrate enriched but shows lower potassium levels. Gas-phase C2-C13 hydrocarbon and C2-C9 carbonyl emissions are speciated by respective EPA Methods T0-15 and T0-11A. They comprise mainly low molecular weight C2-C3 compounds and hazardous air pollutants (48 wt % of total quantified volatile organic carbon).     

Fine particle emissions from on-road vehicles in the Zhujiang Tunnel, China

Little is known about the characteristics of particulate matter emissions from vehicles in China, although such information is critical in source apportionment modeling, emission inventories, and health effect studies. In this paper, we report a comprehensive characterization of PM2.5 emissions in the Zhujiang Tunnel in the Pearl River Delta region of China. The chemical speciation included elemental carbon, organic carbon, inorganic ions, trace elements, and organic compounds. The emission factors of individual species and their relative distributions were obtained for a mixed fleet of heavy-duty vehicles (19.8%) and light-duty vehicles (80.2%). In addition, separate emission factors of PM2.5 mass, elemental carbon, and organic matter for heavy-duty vehicles and light-duty vehicles also were derived. As compared to the results of other tunnel studies previously conducted, we found that the abundances and distributions of the trace elements in PM2.5 emissions were more varied. In contrast, the characteristics of the trace organic compounds in the PM2.5 emissions in our study were consistent with characteristics found in other tunnel studies and dynamometer tests. Our results suggested that vehicular PM2.5 emissions of organic compounds are less influenced by the geographic area and fleet composition and thereby are more suitable for use in aerosol source apportionment modeling implemented across extensive regions.     

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 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.     

Contribution of biogenic emissions to the formation of ozone and particulate matter in the eastern United States

As anthropogenic emissions of ozone (O3) precursors, fine particulate matter (PM2.5), and PM2.5 precursors continue to decrease in the United States, the fraction of O3 and PM2.5 attributable to natural sources may become significant in some locations, reducing the efficacy that can be expected from future controls of anthropogenic sources. Modeling studies were conducted to estimate the contribution of biogenic emissions to the formation of O3 and PM2.5 in Nashville/TN and the northeastern United States. Two approaches were used to bound the estimates. In an anthropogenic simulation, biogenic emissions and their influence at the domain boundaries were eliminated. Contributions of biogenic compounds to the simulated concentrations of O3 and PM2.5 were determined by the deviation of the concentrations in the anthropogenic case from those in the base case. A biogenic simulation was used to assess the amounts of O3 and PM2.5 produced in an environment free from anthropogenic influences in emissions and boundary conditions. In both locations, the contribution of biogenic emissions to O3 was small (<23%) on a domain-wide basis, despite significant biogenic volatile organic compounds (VOC) emissions (65-89% of total VOC emissions). However, the production of O3 was much more sensitive to biogenic emissions in urban areas (22-34%). Therefore, the effects of biogenic emissions on O3 manifested mostly via their interaction with anthropogenic emissions of NOx. In the anthropogenic simulations, the average contribution of biogenic and natural sources to PM2.5 was estimated at 9% in Nashville/TN and 12% in the northeast domain. Because of the long atmospheric lifetimes of PM2.5, the contribution of biogenic/natural PM2.5 from the boundary conditions was higher than the contribution of biogenic aerosols produced within the domain. The elimination of biogenic emissions also affected the chemistry of other secondary PM2.5 components. Very little PM2.5 was formed in the biogenic simulations.     

Emissions from laboratory combustion of wildland fuels: emission factors and source profiles

Combustion of wildland fuels represents a major source of particulate matter (PM) and light-absorbing elemental carbon (EC) on a national and global scale, but the emission factors and source profiles have not been well characterized with respect to different fuels and combustion phases. These uncertainties limit the accuracy of current emission inventories, smoke forecasts, and source apportionments. This study investigates the evolution of gaseous and particulate emission and combustion efficiency by burning wildland fuels in a laboratory combustion facility. Emission factors for carbon dioxide (CO2), carbon monoxide (CO), total hydrocarbon (THC), nitrogen oxides (NO(x)), PM, light extinction and absorption cross sections, and spectral scattering cross sections specific to flaming and smoldering phases are reported. Emission factors are generally reproducible within +/- 20% during the flaming phase, which, despite its short duration, dominates the carbon emission (mostly in the form of CO2) and the production of light absorption and EC. Higher and more variable emission factors for CO, THC, and PM are found during the smoldering phase, especially for fuels containing substantial moisture. Organic carbon (OC) and EC mass account for a majority (i.e., > 60%) of PM mass; other important elements include potassium, chlorine, and sulfur. Thermal analysis separates the EC into subfractions based on analysis temperature demonstrating that high-temperature EC (EC2; at 700 degrees C) varies from 1% to 70% of PM among biomass burns, compared to 75% in kerosene soot. Despite this, the conversion factor between EC and light absorption emissions is rather consistent across fuels and burns, ranging from 7.8 to 9.6 m2/g EC. Findings from this study should be considered in the development of PM and EC emission inventories for visibility and radiative forcing assessments.     

Characteristics of particulate carbon emissions from real-world Chinese coal combustion

Particulate matter emissions from a series of different Chinese coal combustion systems were collected and analyzed for elemental and organic carbon (EC, OC), and molecular markers. Emissions from both industrial boilers and residential stoves were investigated. The coal used in this study included anthracite, bituminite, and brown coal, as well as commonly used coal briquettes produced in China for residential coal combustion. Results show significant differences in the contribution of carbonaceous species to particulate mass emissions. Industrial boilers had much higher burn out of carbon yielding particulate matter emissions with much lower levels of OC, EC, and speciated organic compounds, while residential stoves had significantly higher emissions of carbonaceous particulate matter with emission rates of approximately 100 times higher than that of industrial boilers. Quantified organic compounds emitted from industrial boilers were dominated by oxygenated compounds, of which 46-68% were organic acids, whereas the dominate species quantified in the emissions from residential stoves were PAHs (38%) and n-alkanes (20%). An important observation was the fact that emission factors of PAHs and the distribution of hopanoids were different among the emissions from industrial and residential coal combustion even using the same coal for combustion. Although particulate matter emissions from industrial and residential combustion were different in many regards, picene was detected in all samples with detectable OC mass concentrations, which supports the use of this organic tracer for OC from all types of coal combustion. 17alpha(H),21beta(H)-29-norhopane was the predominant hopanoid in coal combustion emissions, which is different from mobile source emissions and may be used to distinguish emissions from these different fossil fuel sources.     

Particulate-phase and gaseous elemental mercury emissions during biomass combustion: controlling factors and correlation with particulate matter emissions

Mercury emissions from wildfires are significant natural sources of atmospheric mercury, but little is known about what controls speciation of emissions important to mercury deposition processes. The goal of this study was to quantify gaseous elemental mercury (GEM) and particulate-phase mercury (PHg) emissions from biomass combustion to identify key factors controlling the speciation. Emissions were characterized in an exhaust stack 17 m above fires using a gaseous mercury analyzer and quartz-fiber filters. Fuels included fresh and air-dried leaves, needles, and branches with different fuel moistures (9-95% of dry weight) and combustion properties (e.g., from < 10 to 90% of fire durations characterized by flaming phases). Fuel moisture was the overall driving factor defining emissions, with GEM being the dominant fraction (> or = 95%) in low moisture fuels and substantial PHg contributions--up to 50% of total mercury emissions--in fresh fuels. High PHg emissions were observed during smoldering combustion whereas flaming-dominated fires showed insignificant PHg emissions. PHg mass emissions were correlated with particulate matter (PM; r2 = 0.67), organic carbon (OC; r2 = 0.63) and sulfur (S; r2 = 0.46) mass emissions, but not with elemental carbon (EC) nor with the total mercury emissions. These data suggest that the formation of PHg involves similar processes as the formation of particulate OC, for example condensation of volatile species onto preexisting smoke particles during cooling and dilution. Based on the observed relationship between PM and OC mass concentrations and published emission inventories, we estimate global PHg emissions by wildfires of 4-5 Mg yr(-1).     

Real-time gaseous, PM and ultrafine particle emissions from a modern marine engine operating on biodiesel

Emissions from harbor-craft significantly affect air quality in populated regions near ports and inland waterways. This research measured regulated and unregulated emissions from an in-use EPA Tier 2 marine propulsion engine on a ferry operating in a bay following standard methods. A special effort was made to monitor continuously both the total Particulate Mass (PM) mass emissions and the real-time Particle Size Distribution (PSD). The engine was operated following the loads in ISO 8178-4 E3 cycle for comparison with the certification standards and across biodiesel blends. Real-time measurements were also made during a typical cruise in the bay. Results showed the in-use nitrogen oxide (NOx) and PM(2.5) emission factors were within the not to exceed standard for Tier 2 marine engines. Comparing across fuels we observed the following: a) no statistically significant change in NO(x) emissions with biodiesel blends (B20, B50); b) ～ 16% and ～ 25% reduction of PM(2.5) mass emissions with B20 and B50 respectively; c) a larger organic carbon (OC) to elemental carbon (EC) ratio and organic mass (OM) to OC ratio with B50 compared to B20 and B0; d) a significant number of ultrafine nuclei and a smaller mass mean diameter with increasing blend-levels of biodiesel. The real-time monitoring of gaseous and particulate emissions during a typical cruise in the San Francisco Bay (in-use cycle) revealed important effects of ocean/bay currents on emissions: NO(x) and CO(2) increased 3-fold; PM(2.5) mass increased 6-fold; and ultrafine particles disappeared due to the effect of bay currents. This finding has implications on the use of certification values instead of actual in-use emission values when developing inventories. Emission factors for some volatile organic compounds (VOCs), carbonyls, and poly aromatic hydrocarbons (PAHs) are reported as supplemental data.     

Origins of primary and secondary organic aerosol in Atlanta: results of time-resolved measurements during the Atlanta Supersite Experiment

Time-resolved ambient particulate organic (OC) and elemental carbon (EC) data measured in Atlanta, GA, during the Atlanta Supersite Experiment (August3-September 1, 1999) were investigated to determine the temporal trends of atmospheric carbonaceous aerosol and to examine the relative contributions of primary and secondary OC to measured particulate OC. Mean 1-h average concentrations (ranges in parentheses) of PM2.5 OC, EC, and total carbon were 8.3 (3.6-15.8), 2.3 (0.3-9.6), and 10.6 (4.6-24.6) microg of C m(-3), respectively, based on Rutgers University/Oregon Graduate Institute in situ thermal-optical carbon analyzer measurements. Carbonaceous matter (organic material 40%; EC 8%) comprised approximately 48% of PM2.5 mass in Atlanta. Primary and secondary OC concentrations were estimated using an EC tracer method. Secondary OC contributed approximately 46% of measured particulate OC, and 1-h average contributions ranged up to 88%. Vehicle emissions appear to be the dominant contributors to measured EC and primary OC concentrations based on temporal patterns of EC, primary OC, and CO. This research suggests that secondary OC concentrations in Atlanta were influenced by (1) "fresh" secondary organic aerosol formed by photochemical reactions locally in the early afternoons as seen in the Los Angeles air basin and (2) "aged" secondary organic aerosol transported from upwind regions or formed on previous days. Nocturnal peaks in secondary OC and ozone concentrations were observed on several days. The most probable explanation for this is the favorable partitioning of semivolatile organic compounds to the particulate phase driven by temperature decreases and relative humidity increases at night and vertical transport of regional pollutants from above to ground level.     

Using aerosol light absorption measurements for the quantitative determination of wood burning and traffic emission contributions to particulate matter

A source apportionment study was performed for particulate matter in the small village of Roveredo, Switzerland, where more than 70% of the households use wood burning for heating purposes. A two-lane trans-Alpine highway passes through the village and contributes to the total aerosol burden in the area. The village is located in a steep Alpine valley characterized by strong and persistent temperature inversions during winter, especially from December to February. During two winter and one early spring campaigns, a seven-wavelength aethalometer, high volume (HIVOL) samplers, an Aerodyne quadrupole aerosol mass spectrometer (AMS), an optical particle counter (OPC), and a Sunset Laboratory OCEC analyzer were deployed to study the contribution of wood burning and traffic aerosols to particulate matter. A linear regression model of the carbonaceous particulate mass in the submicrometer size range CM(PM1) as a function of aerosol light absorption properties measured by the aethalometer is introduced to estimate the particulate mass from wood burning and traffic (PM(wb), PM(traffic)). This model was calibrated with analyses from the 14C method using HIVOL filter measurements. These results indicate that light absorption exponents of 1.1 for traffic and 1.8-1.9 for wood burning calculated from the light absorption at 470 and 950 nanometers should be used to obtain agreement of the two methods regarding the relative wood burning and traffic emission contributions to CM(PM1) and also to black carbon. The resulting PM(wb) and PM(traffic) values explain 86% of the variance of the CM(PM1) and contribute, on average, 88 and 12% to CM(PM1), respectively. The black carbon is estimated to be 51% due to wood burning and 49% due to traffic emissions. The average organic carbon/total carbon (OC/TC) values were estimated to be 0.52 for traffic and 0.88 for wood burning particulate emissions.     

On-road particulate matter (PM2.5 and PM10) emissions in the Sepulveda Tunnel, Los Angeles, California

Total and speciated particulate matter (PM2.5 and PM10) emission factors from in-use vehicles were measured for a mixed light- (97.4% LD) and heavy-duty fleet (2.6% HD) in the Sepulveda Tunnel, Los Angeles, CA. Seventeen 1-h test runs were performed between July 23, 1996, and July 27, 1996. Emission factors were calculated from mass concentration measurements taken at the tunnel entrance and exit, the volume of airflow through the tunnel, and the number of vehicles passing through the 582 m long tunnel. For the mixed LD and HD fleet, PM2.5 emission factors in the Sepulveda Tunnel ranged from 0.016 (+/-0.007) to 0.115 (+/-0.019) g/vehicle-km traveled with an average of 0.052 (+/-0.027) g/vehicle.km. PM10 emission factors ranged from 0.030 (+/-0.009) to 0.131 (+/-0.024) g/vehicle. km with an average of 0.069 (+/-0.030) g/vehicle.km. The PM2.5 emission factor was approximately 74% of the PM10 factor. Speciated emission rates and chemical profiles for use in receptor modeling were also developed. PM2.5 was dominated by organic carbon (OC) (31.0 +/- 19.5%) and elemental carbon (EC) (48.5 +/- 20.5%) that together account for 79% (+/-24%) of the total emissions. Crustal elements (Fe, Mg, Al, Si, Ca, and Mn) contribute approximately 7.8%, and the ions Cl-, NO3-, NH3+, SO4(2-), and K+ together constitute another 9.8%. In the PM10 size fraction the particulate emissions were also dominated by OC (31 +/- 12%) and EC (35 +/- 13%). The third most prominent species was Fe (18.5 +/- 9.0%), which is greater than would be expected from purely geological sources. Other geological components (Mg, Al, Si, K, Ca, and Mn) accounted for an additional 12.6%. PM10 emission factors showed some dependence on vehicle speed, whereas PM2.5 did not. For test runs in which the average vehicle speed was 42.6 km/h a 1.7 times increase in PM10 emission factor was observed compared to those runs with an average vehicle speed of 72.6 km/h. Speciated emissions were similar. However, there is significantly greater mass attributable to geological material in the PM10, indicative of an increased contribution from resuspended road dust. The PM2.5 shows relatively good correlation with NOx emissions, which indicates that even at the low percent of HD vehicles, which emit significantly more NOx than LD vehicles, they may also have a significant impact on the PM2.5 levels.     

Molecular characteristics of urban organic aerosols from Nanjing: a case study of A mega-city in China

Over 90 organic species have been determined in fine aerosols (PM2.5) collected during the summer and winter in Nanjing, a typical mega-city in China, using gas chromatography-mass spectrometry. The organic compounds detected were apportioned to four emission sources (i.e., plant emission, fossil fuel combustion, biomass burning, and soil resuspension) and secondary oxidation products. The most abundant classes of compounds are fatty acids, followed by sugars, dicarboxylic acids excluding oxalic and malonic acids, and n-alkanes, while alcohols, polyols/polyacids and lignin/sterols are less abundant. Total amounts of the seven classes of compounds were on average 938 ng m(-3) in the summer and 1301 ng m(-3) in the winter, respectively, contributing 0.26-1.96% of particle mass (PM2.5). In the summer, n-alkanes were heavily enhanced by vegetation emissions with a maximum carbon number (Cmax) at C29, whereas they were dominated by emissions from fossil fuels combustion with a Cmax at C22/ C23 in the winter. Concentrations of unsaturated fatty acids were lower in the summer than in the winter, being consistent with enhanced photooxidation of unsaturated fatty acids in the summer. Concentrations of dicarboxylic acids for the summer aerosols were much higher in the daytime than in the nighttime, indicating increased photochemical production in the daytime. In the summer, plant emissions were the most significant source of organic aerosols, contributing more than 33% of total compound mass (TCM), followed by fossil fuel combustion or secondary oxidation. In contrast, fossil fuel combustion was the dominant source of winter organic aerosols, contributing more than 51% of TCM, followed by plant emissions and secondary oxidation products. The quantitative results on sugars and lignin pyrolysis products further suggested that biomass burning and soil resuspension are also significant sources of urban organic aerosols.     

Emission factors, size distributions, and emission inventories of carbonaceous particulate matter from residential wood combustion in rural China

Published emission factors (EFs) often vary significantly, leading to high uncertainties in emission estimations. There are few reliable EFs from field measurements of residential wood combustion in China. In this study, 17 wood fuels and one bamboo were combusted in a typical residential stove in rural China to measure realistic EFs of particulate matter (PM), organic carbon (OC), and elemental carbon (EC), as well as to investigate the influence of fuel properties and combustion conditions on the EFs. Measured EFs of PM, OC, and EC (EF(PM), EF(OC), and EF(EC), respectively) were in the range of 0.38-6.4, 0.024-3.0, and 0.039-3.9 g/kg (dry basis), with means and standard derivation of 2.2 ± 1.2, 0.62 ± 0.64, and 0.83 ± 0.69 g/kg, respectively. Shrubby biomass combustion produced higher EFs than tree woods, and both species had lower EFs than those of indoor crop residue burning (p < 0.05). Significant correlations between EF(PM), EF(OC), and EF(EC) were expected. By using a nine-stage cascade impactor, it was shown that size distributions of PM emitted from tree biomass combustions were unimodal with peaks at a diameter less than 0.4 μm (PM(0.4)), much finer than the PM from indoor crop residue burning. Approximately 79.4% of the total PM from tree wood combustion was PM with a diameter less than 2.1 μm (PM(2.1)). PM size distributions for shrubby biomasses were slightly different from those for tree fuels. On the basis of the measured EFs, total emissions of PM, OC, and EC from residential wood combustion in rural China in 2007 were estimated at about 303, 75.7, and 92.0 Gg.     

Emissions of metals associated with motor vehicle roadways

Emissions of metals and other particle-phase species from on-road motor vehicles were measured in two tunnels in Milwaukee, WI during the summer of 2000 and winter of 2001. Emission factors were calculated from measurements of fine (PM2.5) and coarse (PM10) particulate matter at tunnel entrances and exits, and effects of fleet composition and season were investigated. Cascade impactors (MOUDI) were used to obtain size-resolved metal emission rates. Metals were quantified with inductively-coupled plasma mass spectrometry (ICP-MS) and X-ray fluorescence (XRF). PM10 emission rates ranged from 38.7 to 201 mg km(-1) and were composed mainly of organic carbon (OC, 30%), inorganic ions (sulfate, chloride, nitrate, ammonium, 20%), metals (19%), and elemental carbon (EC, 9.3%). PM10 metal emissions were dominated by crustal elements Si, Fe, Ca, Na, Mg, Al, and K, and elements associated with tailpipe emissions and brake and tire wear, including Cu, Zn, Sb, Ba, Pb, and S. Metals emitted in PM2.5 were lower (11.6% of mass). Resuspension of roadway dust was dependent on weather and road surface conditions, and increased emissions were related to higher traffic volumes and fractions of heavy trucks. Emission of noble metals from catalytic converters appeared to be impacted by the presence of older vehicles. Elements related to brake wear were impacted by enriched road dust resuspension, but correlations between these elements in PM2.5 indicate that direct brake wear emissions are also important. A submicrometer particle mode was observed in the emissions of Pb, Ca, Fe, and Cu.     

Development and evaluation of a personal particulate organic and mass sampler

Accurate measurement of personal exposure to particulate matter and its constituents requires samplers that are accurate, compact, lightweight, inexpensive, and convenient to use. The personal particulate organic and mass sampler (PPOMS) has been developed to meet these criteria. The PPOMS uses activated carbon-impregnated foam as a combined 2.5-microm size-selective inlet and denuder for assessment of fine particle mass and organic carbon. Proof of the PPOMS concept has been established by comparing mass and organic carbon in particles collected with collocated samplers in Seattle, at a central outdoor site, and in residences. Daily particulate mass concentrations averaged 10.0 +/- 5.2, 12.0 +/- 5.3, and 11.2 +/- 5.1 microg m(-3) for the Federal Reference Method, the Harvard Personal Exposure Monitor, and the PPOMS, respectively, for 10 24-h sampling periods. During a series of PM2.5 indoor organic carbon (OC) measurements from single quartz filters, the apparent indoor OC averaged 7.7 +/- 0.8 microg of C m(-3), which was close to the indoor PM2.5 mass from collocated Teflon filters (7.3 +/- 2.3 microg of C m(-3)), indicating the presence of a large positive OC artifact. In collocated measurements, the PPOMS eliminated this artifact just as well as the integrated gas and particle sampler that incorporated a macroreticular polystyrene-divinylbenzene (XAD-4) resin-coated denuder, yielding OC concentrations of 2.5 +/- 0.4 and 2.4 +/- 1.0 microg of C m(-3), respectively. Thermal analysis for OC indicated that the indoor positive artifact was due to adsorption of gas-phase semivolatile organic compounds (SVOC). This study shows that the PPOMS design provides a 2.5-microm size-selective inlet that also prevents the adsorption of gas-phase SVOC onto quartz filters, thus eliminating the filter positive artifact The PPOMS meets a significant current challenge for indoor and personal sampling of particulate organic carbon. The PPOMS design can also simplify accurate ambient sampling for PM2.5.     

Emissions of air pollutants from household stoves: honeycomb coal versus coal cake

Domestic coal combustion can emit various air pollutants. In the present study, we measured emissions of particulate matter (PM) and gaseous pollutants from burning a specially formulated honeycomb coal (H-coal) and a coal cake (C-coal). Flue gas samples for PM2.5, PM coarse (PM2.5-10), and TSP were collected isokinetically using a cascade impactor; PM mass concentrations were determined gravimetrically. Concentrations of SO2, NOx, and ionic Cr(VI) in PM were analyzed using spectrometric methods. Fluoride concentrations were measured using a specific ion electrode method. PM elemental components were analyzed using an X-ray fluorescence technique. Total (gas and particle phase) benzo[a]pyrene (BaP) concentration was determined using an HPLC/fluorescence method. Elemental and organic carbon contents of PM were analyzed using a thermal/optical reflectance technique. The compositional and structural differences between the H-coal and C-coal resulted in different emission characteristics. In generating 1 MJ of delivered energy, the H-coal resulted in a significant reduction in emissions of SO2 (by 68%), NOx (by 47%), and TSP (by 56%) as compared to the C-coal, whereas the emissions of PM2.5 and total BaP from the H-coal combustion were 2-3-fold higher, indicating that improvements are needed to further reduce emissions of these pollutants in developing future honeycomb coals. Although the H-coal and the C-coal had similar emission factors for gas-phase fluoride, the H-coal had a particle-phase fluoride emission factor that was only half that of the C-coal. The H-coal had lower energy-based emissions of all the measured toxic elements in TSP but higher emissions of Cd and Ni in PM2.5.     

VOC and particulate emissions from commercial cigarettes: analysis of 2,5-DMF as an ETS tracer

Emissions of particulate matter (PM) and a broad suite of target volatile organic compounds (VOCs) in total, main-stream (MS) and side-stream (SS) smoke emissions are measured for six types of commercial cigarettes. The suitability of 2,5-dimethyl furan (DMF) as a tracer for environmental tobacco smoke (ETS) is investigated using laboratory results and a field study of 47 residences. Over 30 VOCs were characterized in cigarette smoke, including several that have not been reported previously. "regular tar", "low tar", menthol, and nonmenthol cigarettes showed only minor differences in PM and VOC emissions. When total emissions are considered, PM emissions averaged 18 +/- 2 mg cigarette(-1) and VOC emissions averaged 3644 +/- 160 mg cigarette(-1). DMF appears to satisfy all requirements for a tracer, namely, uniqueness, detectability, similar emission factors across tobacco products (211 +/- 16 microg cigarette(-1)), consistent proportions to other ETS compounds, and behavior similar to other ETS components in relevant environments. On the basis of field study results, DMF more reliably indicated smoking status than occupant-completed questionnaires, and cigarette smoking was responsible for significant fractions of benzene (50%), styrene (49%), and other VOCs in the smoker's homes.