Oxidation of gaseous elemental mercury to gaseous divalent mercury during 2003 polar sunrise at Ny-Alesund

The springtime phenomenon, termed as the mercury depletion event (MDE), during which elemental gaseous mercury (Hg0) may be converted to a reactive form that accumulates in polar ecosystems, first noted in the Arctic, has now been observed at both poles and results in an important removal pathway for atmospheric mercury. An intensive international springtime mercury experiment was performed at Ny-Alesund, Spitsbergen, from 19 April to 13 May 2003 to study the atmospheric mercury chemistry in the Arctic environment and, in particular, the MDEs which occurred in the arctic boundary layer after polar sunrise. Automated ambient measurements of Hg0, divalent reactive gaseous mercury (RGM) and fine particulate mercury (<2.5 microm) (Hg(p)) were made at the Zeppelin Mountain Station (ZMS). During the experiment mercury concentrations in the lower atmosphere varied in synchrony with ozone levels throughout the Spring. Hg0 concentrations ranged from background levels (approximately 1.6 ng m(-3)) to undetectable values (<0.1 ng m(-3)) during the first and major MDE, while RGM data showed an opposite trend during the sampling period with concentrations increasing dramatically to a peak of 230 pg m(-3), synchronous with the depletion of Hg0. The results of a meteorological transport analysis indicate the MDEs observed at ZMS were primarily due to air masses being transported in from open water areas in the Arctic Ocean that were already depleted of Hg0 when they arrived and not due to in-situ oxidation mechanisms.     

Reductions in emissions of carbonaceous particulate matter and polycyclic aromatic hydrocarbons from combustion of biomass pellets in comparison with raw fuel burning

Biomass pellets are emerging as a cleaner alternative to traditional biomass fuels. The potential benefits of using biomass pellets include improving energy utilization efficiency and reducing emissions of air pollutants. To assess the environmental, climate, and health significance of replacing traditional fuels with biomass pellets, it is critical to measure the emission factors (EFs) of various pollutants from pellet burning. However, only a few field measurements have been conducted on the emissions of carbon monoxide (CO), particulate matter (PM), and polycyclic aromatic hydrocarbons (PAHs) from the combustion of pellets. In this study, pine wood and corn straw pellets were burned in a pellet burner (2.6 kW), and the EFs of CO, organic carbon, elemental carbon, PM, and PAHs (EF(CO), EF(OC), EF(EC), EF(PM), and EF(PAH)) were determined. The average EF(CO), EF(OC), EF(EC), and EF(PM) were 1520 ± 1170, 8.68 ± 11.4, 11.2 ± 8.7, and 188 ± 87 mg/MJ for corn straw pellets and 266 ± 137, 5.74 ± 7.17, 2.02 ± 1.57, and 71.0 ± 54.0 mg/MJ for pine wood pellets, respectively. Total carbonaceous carbon constituted 8 to 14% of the PM mass emitted. The measured values of EF(PAH) for the two pellets were 1.02 ± 0.64 and 0.506 ± 0.360 mg/MJ, respectively. The secondary side air supply in the pellet burner did not change the EFs of most pollutants significantly (p > 0.05). The only exceptions were EF(OC) and EF(PM) for pine wood pellets because of reduced combustion temperatures with the increased air supply. In comparison with EFs for the raw pine wood and corn straw, EF(CO), EF(OC), EF(EC), and EF(PM) for pellets were significantly lower than those for raw fuels (p < 0.05). However, the differences in EF(PAH) were not significant (p > 0.05). Based on the measured EFs and thermal efficiencies, it was estimated that 95, 98, 98, 88, and 71% reductions in the total emissions of CO, OC, EC, PM, and PAHs could be achieved by replacing the raw biomass fuels combusted in traditional cooking stoves with pellets burned in modern pellet burners.     

Partitioning of metal species during an enriched fuel combustion experiment. speciation in the gaseous and particulate phases

Combustion processes are the most important source of metal in the atmosphere and need to be better understood to improve flue gas treatment and health impact studies. This combustion experiment was designed to study metal partitioning and metal speciation in the gaseous and particulate phases. A light fuel oil was enriched with 15 organometallic compounds of the following elements: Pb, Hg, As, Cu, Zn, Cd, Se, Sn, Mn, V, Tl, Ni, Co, Cr, and Sb. The resulting mixture was burnt in a pilot-scale fuel combustion boiler under controlled conditions. After filtration of the particles, the gaseous species were sampled in the stack through a heated sampling tube simultaneously by standardized washing bottles-based sampling techniques and cryogenically. The cryogenic samples were collected at -80 degrees C for further speciation analysis by LT/GC-ICPMS. Three species of selenium and two of mercury were evidenced as volatile species in the flue gas. Thermodynamic predictions and experiments suggest the following volatile metal species to be present in the flue gas: H2Se, CSSe, CSe2, SeCl2, Hg(0), and HgCl2. Quantification of volatile metal species in comparison between cryogenic techniques and the washing bottles-based sampling method is also discussed. Concerning metal partitioning, the results indicated that under these conditions, at least 60% (by weight) of the elements Pb, Sn, Cu, Co, Tl, Mn, V, Cr, Ni, Zn, Cd, and Sb mixed to the fuel were found in the particulate matter. For As and Se, 37 and 17%, respectively, were detected in the particles, and no particulate mercury was found. Direct metal speciation in particles was performed by XPS allowing the determination of the oxidation state of the following elements: Sb(V), Tl(III), Mn(IV), Cd(II), Zn(II), Cr(III), Ni(II), Co(II), V(V), and Cu(II). Water soluble species of inorganic Cr, As, and Se in particulate matter were determined by HPLC/ICP-MS and identified in the oxidation state Cr(III), As(V), and Se(IV).     

Zinc isotopic composition of particulate matter generated during the combustion of coal and coal + tire-derived fuels

Atmospheric Zn emissions from the burning of coal and tire-derived fuel (TDF) for power generation can be considerable. In an effort to lay the foundation for tracking these contributions, we evaluated the Zn isotopes of coal, a mixture of 95 wt % coal + 5 wt % TDF, and the particulate matter (PM) derived from their combustion in a power-generating plant. The average Zn concentrations and δ(66)Zn were 36 mg/kg and 183 mg/kg and +0.24‰ and +0.13‰ for the coal and coal + TDF, respectively. The δ(66)Zn of the PM sequestered in the cyclone-type mechanical separator was the lightest measured, -0.48‰ for coal and -0.81‰ for coal+TDF. The δ(66)Zn of the PM from the electrostatic precipitator showed a slight enrichment in the heavier Zn isotopes relative to the starting material. PM collected from the stack had the heaviest δ(66)Zn in the system, +0.63‰ and +0.50‰ for the coal and coal + TDF, respectively. Initial fractionation during the generation of a Zn-rich vapor is followed by temperature-dependent fractionation as Zn condenses onto the PM. The isotopic changes of the two fuel types are similar, suggesting that their inherent chemical differences have only a secondary impact on the isotopic fractionation process.     

Emission rates of particulate matter and elemental and organic carbon from in-use diesel engines

Elemental carbon (EC), organic carbon (OC), and particulate matter (PM) emission rates are reported for a number of heavy heavy-duty diesel trucks (HHDDTs) and back-up generators (BUGs) operating under real-world conditions. Emission rates were determined using a unique mobile emissions laboratory (MEL) equipped with a total capture full-scale dilution tunnel connected directly to the diesel engine via a snorkel. This paper shows that PM, EC, and OC emission rates are strongly dependent on the mode of vehicle operation; highway, arterial, congested, and idling conditions were simulated by following the speed trace from the California Air Resources Board HHDDT cycle. Emission rates for BUGs are reported as a function of engine load at constant speed using the ISO 8178B Cycle D2. The EC, OC, and PM emission rates were determined to be highly variable for the HHDDTs. It was determined that the per mile emission rate of OC from a HHDDT in congested traffic is 8.1 times higher than that of an HHDDT in cruise or highway speed conditions and 1.9 times higher for EC. EC/OC ratios for BUGs (which generally operate at steady states) and HHDDTs show marked differences, indicating that the transient nature of engine operation dictates the EC/OC ratio. Overall, this research shows that the EC/OC ratio varies widely for diesel engines in trucks and BUGs and depends strongly on the operating cycle. The findings reported here have significant implications in the application of chemical mass balance modeling, diesel risk assessment, and control strategies such as the Diesel Risk Reduction Program.     

Determination of methoxyphenols in ambient atmospheric particulate matter: tracers for wood combustion

Combustion of wood and other biomass fuels produces source-specific organic compounds arising from pyrolysis of lignin, including substantial amounts of 4-substituted methoxylated phenolic compounds (methoxyphenols). These compounds have been used as atmospheric markers to determine the contribution of wood smoke to ambient atmospheric fine particulate matter (PM). However, reliable quantification of methoxyphenols represents an analytical challenge because these compounds are polar, semi-volatile, and somewhat reactive. We reportherein an improved gas chromatographic-mass spectrometric (GC/MS) method for the sensitive and reliable determination of methoxyphenols in low-volume ambient PM samples. Deuterated standard compounds are added to the environmental samples prior to extraction to determine analyte recoveries in each sample. Analytical figures of merit for the assay, as applied to ambient PM2.5 and PM10 samples are as follows: recovery = 63-100%; precision = 2-6%; analytical limit of detection (S/N 2) = 0.002 microg/mL; limit of quantitation = 0.07-0.45 ng/m3 (assuming a 14 m3 sample). The improved method was applied to ambient PM samples collected between 1999 and 2000 in Seattle, WA. Particle-bound methoxyphenol concentrations in the range <0.1 to 22 ng/m3 were observed and the methoxyphenols were present almost exclusively in the fine (PM2.5) size fraction. We also demonstrated that XRF analysis of samples of atmospheric PM collected on Teflon filters significantly reduced the levels of methoxyphenols measured in the PM samples in subsequent assay of the same filters. Therefore, XRF analysis of filters, commonly undertaken to obtain trace element concentrations for use in source apportionment analyses, would preclude the subsequent analysis of those filters for methoxyphenols and other similarly semivolatile or reactive organic chemicals.     

Time-resolved characterization of diesel particulate emissions. 2. Instruments for elemental and organic carbon measurements

The measurement of elemental carbon (EC) and organic carbon (OC) mass for particles emitted by diesel vehicles is currently accomplished using particle collection on filters, followed by analysis using the thermal/optical reflectance carbon analysis method (TOR) or one of its variations. Such filter methods limit time resolution to a minimum of several minutes, making it impossible to study emissions during transient operating conditions. Testing of five different measurement methods has demonstrated that fast response measurement of diesel exhaust particulate EC and OC concentrations, consistent with TOR filter measurements, is feasible using existing technology. EC mass concentrations are best measured through determination of particulate light absorption with a photoacoustic instrument or determination of light extinction with a smoke meter. The photoacoustic instrument has the better dynamic range and sensitivity, whereas the smoke meter is a simpler instrument. Fast response OC measurements cannot be made with any single instrument tested. However, a combination of real time weighing as implemented in the tapered element oscillating microbalance with the photoacoustic instrument has been shown to be capable of determining OC concentrations with good time response. The addition of a nephelometer to the OC measurement could potentially improve time resolution, freedom from interferences, and sensitivity.     

Characterization of fine particle and gaseous emissions during school bus idling

The particulate matter (PM) and gaseous emissions from six diesel school buses were determined over a simulated waiting period typical of schools in the northeastern U.S. Testing was conducted for both continuous idle and hot restart conditions using a suite of on-line particle and gas analyzers installed in the U.S. Environmental Protection Agency's Diesel Emissions Aerosol Laboratory. The specific pollutants measured encompassed total PM-2.5 mass (PM < or = 2.5 microm in aerodynamic diameter), PM-2.5 number concentration, particle size distribution, particle-surface polycyclic aromatic hydrocarbons (PAHs), and a tracer gas (1,1,1,2,3,3,3-heptafluoropropane) in the diluted sample stream. Carbon monoxide (CO), carbon dioxide, nitrogen oxides (NO(x)), total hydrocarbons (THC), oxygen, formaldehyde, and the tracer gas were also measured in the raw exhaust. Results of the study showed little difference in the measured emissions between a 10 min post-restart idle and a 10 min continuous idle with the exception of THC and formaldehyde. However, an emissions pulse was observed during engine restart. A predictive equation was developed from the experimental data, which allows a comparison between continuous idle and hot restart for NO(x), CO, PM2.5, and PAHs and which considers factors such as the restart emissions pulse and periods when the engine is not running. This equation indicates that restart is the preferred operating scenario as long as there is no extended idling after the engine is restarted.     

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.     

Reduction of particulate matter emissions from diesel backup generators equipped with four different exhaust aftertreatment devices

Diesel particulate matter (PM) reduction efficiencies for backup generators (BUGs) (> 300 kW) equipped with a diesel oxidation catalyst (DOC), DOC+fuel-borne catalyst additive combination (DOC+FBC), passive diesel particulate filter (DPF), and an active DPF were measured. Overall, the DOC and DOC+FBC technologies were found to be effective in reducing mainly organic carbon (OC) emissions (56-77%) while both DPFs showed excellent performance in reducing both elemental carbon (EC) and OC emissions (> 90%). These findings demonstrate the potential for applying DOCs to older engines where PM is dominated by the OC fraction. In most modern engine applications, where the PM consists of mainly EC, the DOC will be largely ineffective. Alternatively, passive and active DPFs are expected to be efficient for most engine technologies. Measurements of particle size distributions provided evidence of the high temperature formation of sulfate nanoparticles across the control technologies despite the use of ultralow sulfur diesel. Changes in the particle size distribution and the organic fraction of PM indicate that the OC component of PM is primarily found in the smaller sized particles.     

Climate sensitivity of gaseous elemental mercury dry deposition to plants: impacts of temperature, light intensity, and plant species

Foliar accumulations of gaseous elemental mercury (GEM) were measured in three plant species between nominal temperatures of 10 and 30 °C and nominal irradiances of 0, 80, and 170 W m(-2) (300 nm-700 nm) in a 19 m(3) controlled environment chamber. The plants exposed were as follows: White Ash (Fraxinus americana; WA); White Spruce (Picea glauca; WS); and Kentucky Bluegrass (Poa partensis; KYBG). Foliar enrichments in the mercury stable isotope ((198)Hg) were used to measure mercury accumulation. Exposures lasted for 1 day after which the leaves were digested in hot acid and the extracted mercury was analyzed with ICPMS. Resistances to accumulative uptake by leaves were observed to be dependent on both light and temperature, reaching minima at optimal growing conditions (20 °C; 170 W m(-2) irradiance between 300-700 nm). Resistances typically increased at lower (10 °C) and higher (30 °C) temperatures and decreased with higher intensities of irradiance. Published models were modified and used to interpret the trends in stomatal and leaf interior resistances to GEM observed in WA. The model captured the experimental trends well and revealed that stomatal and internal resistances were both important across much of the temperature range. At high temperatures, however, stomatal resistance dominated due to increased water vapor pressure deficits. The resistances measured in this study were used to model foliar accumulations of GEM at a northern US deciduous forest using atmospheric mercury and climate measurements made over the 2003 growing season. The results were compared to modeled accumulations for GEM, RGM, and PHg using published deposition velocities. Predictions of foliar GEM accumulation were observed to be a factor of 5-10 lower when the temperature and irradiance dependent resistances determined in this study were used in place of previously published data. GEM uptake by leaves over the growing season was shown to be an important deposition pathway (2.3-3.7 μg m(-2) of one-sided leaf area; OSLA) when compared to total mercury wet deposition (1.2 μg m(-2) OSLA) and estimates of reactive mercury dry deposition (0.1-6 μg m(-2) OSLA). Resistance-Temperature-Irradiance relationships are provided for use in models.     

Detailed characterization and profiles of crankcase and diesel particulate matter exhaust emissions using speciated organics

A monitoring campaign was conducted in August-September 2005 to compare different experimental approaches quantifying school bus self-pollution. As part of this monitoring campaign, a detailed characterization of PM2.5 diesel engine emissions from the tailpipe and crankcase emissions from the road draft tubes was performed. To distinguish between tailpipe and crankcase vent emissions, a deuterated alkane, n-hexatriacontane-d74 (n-C36D74) was added to the engine oil to serve as an intentional quantitative tracer for lubricating oil PM emissions. This paper focuses on the detailed chemical speciation of crankcase and tailpipe PM emissions from two school buses used in this study. We found that organic carbon emission rates were generally higher from the crankcase than from the tailpipe for these two school buses, while elemental carbon contributed significantly only in the tailpipe emissions. The n-C36D74 that was added to the engine oil was emitted at higher rates from the crankcase than the tailpipe. Tracers of engine oil (hopanes and steranes) were present in much higher proportion in crankcase emissions. Particle-associated PAH emission rates were generally very low (< 1 microg/km), but more PAH species were present in crankcase than in tailpipe emissions. The speciation of samples collected in the bus cabins was consistent with most of the bus self-pollution originating from crankcase emissions.     

Polycyclic aromatic hydrocarbon and particulate emissions from two-stage combustion of polystyrene: the effect of the primary furnace temperature

A study is presented on laboratory-scale combustion of polystyrene (PS) to identify staged-combustion conditions that minimize emissions. Batch combustion of shredded PS was conducted in fixed beds placed in a bench-scale electrically heated horizontal muffle furnace. In most cases, combustion of the samples occurred by forming gaseous diffusion flames in atmospheric pressure air. The combustion effluent was mixed with additional air, and it was channeled to a second muffle furnace (afterburner) placed in series. Further reactions took place in the secondary furnace at a residence time of 0.7 s. The gas temperature of the primary furnace was varied in the range of 500-1,000 degrees C, while that of the secondary furnace was kept fixed at 1,000 degrees C. Sampling for CO, CO2, O2, soot, and unburned hydrocarbon emissions (volatile and semivolatile, by GC-MS) was performed at the exits of the two furnaces. Results showed that the temperature of the primary furnace, where PS gasifies, is of paramount importance to the formation and subsequent emissions of organic species and soot. Atthe lowesttemperatures explored, mostly styrene oligomers were identified at the outlet of the primary furnace, but they did not survive the treatment in the secondary furnace. The formation and emission of polycyclic aromatic hydrocarbons (PAH) and soot were suppressed. As the temperature in the first furnace was raised, increasing amounts of a wide range of both unsubstituted and substituted PAH containing up to at least seven condensed aromatic rings were detected. A similar trend was observed for total particulate yields. The secondary furnace treatment reduced the yields of total PAH, but it had an ambiguous effect on individual species. While most low molecular mass PAH were reduced in the secondary furnace, concentrations of some larger PAH increased under certain conditions. Thus, care in the selection of operating conditions of both the primary furnace (gasifier/ burner) and the secondary furnace (afterburner) must be exercised to minimize the emission of hazardous pollutants. The emissions of soot were also reduced in the afterburner but not drastically. This indicates that soot is indeed resistant to oxidation; thus, it would be best to avoid its formation in the first place. An oxidative pyrolysis temperature of PS in the vicinity of 600 degrees C appears to accomplish exactly that. An additional afterburner treatment at a sufficiently high temperature (1,000 degrees C) may be a suitable setting for minimization of most pollutants. To obtain deeper understanding of chemical processes, the experimental results were qualitatively compared with preliminary predictions of a detailed kinetic model that describes formation and destruction pathways of chemical species including most PAH observed in the present work. The modeling was performed forthe secondary furnace assuming plug-flow conditions therein. The experimentally determined chemical composition at the outlet of the primary furnace was part of the input parameters of the model calculation.     

Fate of elemental mercury in the Arctic during atmospheric mercury depletion episodes and the load of atmospheric mercury to the Arctic

Atmospheric mercury depletion episodes (AMDEs) were studied at Station Nord, Northeast Greenland, 81 degrees 36' N, 16 degrees 40' W, during the Arctic Spring. Gaseous elemental mercury (GEM) and ozone were measured starting from 1998 and 1999, respectively, until August 2002. GEM was measured with a TEKRAN 2735A automatic mercury analyzer based on preconcentration of mercury on a gold trap followed by detection using fluorescence spectroscopy. Ozone was measured by UV absorption. A scatter plot of GEM and ozone concentrations confirmed that also at Station Nord GEM and ozone are linearly correlated during AMDEs. The relationship between ozone and GEM is further investigated in this paper using basic reaction kinetics (i.e., Cl, ClO, Br, and BrO have been suggested as reactants for GEM). The analyses in this paper show that GEM in the Arctic troposphere most probably reacts with Br. On the basis of the experimental results of this paper and results from the literature, a simple parametrization for AMDE was included into the Danish Eulerian Hemispheric Model (DEHM). In the model, GEM is converted linearly to reactive gaseous mercury (RGM) over sea ice with temperature below -4 degrees C with a lifetime of 3 or 10 h. The new AMDE parametrization was used together with the general parametrization of mercury chemistry [Petersen, G.; Munthe, J.; Pleijel, K.; Bloxam, R.; Vinod Kumar, A. Atmos. Environ. 1998, 32, 829-843]. The obtained model results were compared with measurements of GEM at Station Nord. There was good agreement between the start and general features periods with AMDEs, although the model could not reproduce the fast concentration changes, and the correlation between modeled and measured values decreased from 2000 to 2001 and further in 2002. The modeled RGM concentrations over the Arctic in 2000 were found to agree well with the temporal and geographical variability of the boundary column of monthly average BrO observed by the GOME satellite. Scenario calculations were performed with and without AMDEs. For the area north of the Polar Circle, the mercury deposition increases from 89 tons/year for calculations without an AMDE to 208 tons/year with the AMDE. The 208 tons/year represent an upper limit for the mercury load to the Artic.     

Household concentrations and exposure of children to particulate matter from biomass fuels in The Gambia

Particulate matter (PM) is an important metric for studying the health effects of household air pollution. There are limited data on PM exposure for children in homes that use biomass fuels, and no previous study has used direct measurement of personal exposure in children younger than 5 years of age. We estimated PM(2.5) exposure for 1266 children in The Gambia by applying the cookhouse PM(2.5)-CO relationship to the child's CO exposure. Using this indirect method, mean PM(2.5) exposure for all subjects was 135 ± 38 μg/m(3); 25% of children had exposures of 151 μg/m(3) or higher. Indirectly estimated exposure was highest among children who lived in homes that used firewood (collected or purchased) as their main fuel (144 μg/m(3)) compared to those who used charcoal (85 μg/m(3)). To validate the indirect method, we also directly measured PM(2.5) exposure on 31 children. Mean exposure for this validation data set was 65 ± 41 μg/m(3) using actual measurement and 125 ± 54 μg/m(3) using the indirect method based on simultaneously-measured CO exposure. The correlation coefficient between direct measurements and indirect estimates was 0.01. Children in The Gambia have relatively high PM(2.5) exposure. There is a need for simple methods that can directly measure PM(2.5) exposure in field studies.     

Lubricating oil and fuel contributions to particulate matter emissions from light-duty gasoline and heavy-duty diesel vehicles

Size-resolved particulate matter emissions from heavy-duty diesel vehicles (HDDVs) and light-duty gasoline vehicles (LDGVs) operated under realistic driving cycles were analyzed for elemental carbon (EC), organic carbon (OC), hopanes, steranes, and polycyclic aromatic hydrocarbons. Measured hopane and sterane size distributions did not match the total carbon size distribution in most cases, suggesting that lubricating oil was not the dominant source of particulate carbon in the vehicle exhaust. A regression analysis using 17alpha(H)-21beta(H)-29-norhopane as a tracer for lubricating oil and benzo[ghi/perylene as a tracer for gasoline showed that gasoline fuel and lubricating oil both make significant contributions to particulate EC and OC emissions from LDGVs. A similar regression analysis performed using 17alpha(H)-21beta(H)-29-norhopane as a tracer for lubricating oil and flouranthene as a tracerfor diesel fuel was able to explain the size distribution of particulate EC and OC emissions from HDDVs. The analysis showed that EC emitted from all HDDVs operated under relatively high load conditions was dominated by diesel fuel contributions with little EC attributed to lubricating oil. Particulate OC emitted from HDDVs was more evenly apportioned between fuel and oil contributions. EC emitted from LDGVs operated underfuel-rich conditions was dominated by gasoline fuel contributions. OC emitted from visibly smoking LDGVs was mostly associated with lubricating oil, but OC emitted from all other categories of LDGVs was dominated by gasoline fuel. The current study clearly illustrates that fuel and lubricating oil make separate and distinct contributions to particulate matter emissions from motor vehicles. These particles should be tracked separately during ambient source apportionment studies since the atmospheric evolution and ultimate health effects of these particles may be different. The source profiles for fuel and lubricating oil contributions to EC and OC emissions derived in this study provide a foundation for future source apportionment calculations.     

The effects of the catalytic converter and fuel sulfur level on motor vehicle particulate matter emissions: gasoline vehicles

Scanning mobility and electrical low-pressure impactor particle size measurements conducted during chassis dynamometer testing reveal that neither the catalytic converter nor the fuel sulfur content has a significant effect on gasoline vehicle tailpipe particulate matter (PM) emissions. For current technology, port fuel injection, gasoline engines, particle number emissions are < or = 2 times higher from vehicles equipped with blank monoliths as compared to active catalysts, insignificant in contrast to the 90+% removal of hydrocarbons. PM mass emission rates derived from the size distributions are equal within the experimental uncertainty of 50-100%. Gravimetric measurements exhibit a 3-10-fold PM mass increase when the active catalyst is omitted, which is attributed to gaseous hydrocarbons adsorbing onto the filter medium. Both particle number and gravimetric measurements show that gasoline vehicle tailpipe PM emissions are independent (within 2 mg/mi) of fuel sulfur content over the 30-990 ppm concentration range. Nuclei mode sulfate aerosol is not observed in either test cell measurements or during wind tunnel testing. For three-way catalyst equipped vehicles, the principal sulfur emission is SO2; however a sulfur balance is not obtained over the drive cycle. Instead, sulfur is stored on the catalyst during moderate driving and then partially removed during high speed/load operation.     

Chemical characterization of ambient particulate matter near the World Trade Center: elemental carbon, organic carbon, and mass reconstruction

Concentrations of elemental carbon (EC), organic carbon matter (OM), particulate matter less than 2.5 microm (PM2.5), reconstructed soil, trace element oxides, and sulfate are reported from four locations near the World Trade Center (WTC) complex for airborne particulate matter (PM) samples collected from September 2001 through January 2002. Across the four sampling sites, daily mean concentrations ranged from 1.5 to 6.8 microg/m3 for EC, from 10.2 to 31.4 microg/m3 for OM, and from 22.6 to 66.2 microg/m3 for PM2.5. Highest concentrations of PM species were generally measured north and west of the WTC complex. Total carbon matter and sulfate constituted the largest fraction of reconstructed PM2.5 concentrations. Concentrations of PM species across all sites decreased from the period when fires were present at the WTC complex (before December 19, 2001) to the period after the fires. Averaged over all sites, concentrations decreased by 25.6 microg/m3 for PM2.5, 2.7 microg/m3 for EC, and 9.2 microg/m3 for OM from the fire period to after fire period.     

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.