Size distribution of trace organic species emitted from light-duty gasoline vehicles

Size distributions for particulate hopanes+steranes and nonvolatile polycyclic aromatic hydrocarbons (PAHs) emitted from five classes of light-duty gasoline-powered vehicles were measured using the federal test procedure (FTP), unified cycle (UC), and correction cycle (CC) driving cycles. 17alpha(H)-21beta(H)-29-norhopane, 17alpha(H)-21beta(H)-hopane, alpha beta beta-20R-stigmastane, and alpha beta beta-20S-stigmastane were highly correlated and behaved consistently across sampling methods. Coronene and benzo[ghi]perylene were the most ubiquitous heavy PAHs detected in the vehicle exhaust. The emission rates of hopanes, steranes, and PAHs contained in particles with aerodynamic diameters of less than 1.8 ,m varied by 2 orders of magnitude between the lowest- and highest-emitting vehicle classes. Hopane+sterane size distributions emitted from vehicles without an operating catalyst (including "cold-start" emissions from catalyst-equipped vehicles) were bimodal with one mode between 0.10 and 0.18 microm and the second mode >0.32 microm particle diameter. Hopane+sterane emissions released from vehicles with a catalyst at operating temperature had a single mode between 0.1 and 0.18 microm diameter. Hopane+sterane emissions from visibly smoking vehicles had a single mode between 0.18 and 0.32 microm diameter. Heavy PAH size distributions for all vehicle classes consistently had a single mode between 0.10 and 0.18 microm particle diameter (0.1-0.32 microm diameter for smoking vehicles). The geometric standard deviations for PAH size distributions were generally smaller than the corresponding hopane+sterane distributions. These trends suggest that hopanes+steranes and heavy PAHs act as tracers for separate processes of particulate organic carbon formation. PAH and hopane+sterane emissions shifted to smaller sizes during the more aggressive UC and CC driving cycles relative to the FTP. The fraction of PAH and hopane+sterane emissions in the ultrafine (Dp < 0.1 microm) range more than doubled during "warm-start" UC and CC cycles vs the FTP cycle. The enhancement of ultrafine PAHs during "cold-start" UC driving cycles was less pronounced.     

On-road measurement of particle emission in the exhaust plume of a diesel passenger car

Particle size distributions were measured under real world dilution conditions in the exhaust plume of a diesel passenger car closely followed by a mobile laboratory on a high speed test track. Under carefully controlled conditions the exhaust plume was continuously sampled and analyzed inside the mobile laboratory. Exhaust particle size distribution data were recorded together with exhaust gas concentrations, i.e., CO, CO2, and NO(x), and compared to data obtained from the same vehicle tested on a chassis dynamometer. Good agreement was found for the soot mode particles which occurred at a geometric mean diameter of approximately 50 nm and a total particle emission rate of 10(14) particles km(-1). Using 350 ppm high sulfur fuel and the standard oxidation catalyst a bimodal size distribution with a nucleation mode at 10 nm was observed at car velocities of 100 km h(-1) and 120 km h(-1), respectively. Nucleation mode particles were only present if high sulfur fuel was used with the oxidation catalyst installed. This is in agreement with prior work that these particles are of semivolatile nature and originate from the nucleation of sulfates formed inside the catalyst. Temporal effects of the occurrence of nucleation mode particles during steady-state cruising and the dynamical behavior during acceleration and deceleration were investigated.     

Nucleation mode particles with a nonvolatile core in the exhaust of a heavy duty diesel vehicle

The characteristics of the nucleation mode particles of a Euro IV heavy-duty diesel vehicle exhaust were studied. The NOx and PM emissions of the vehicle were controlled through the use of cooled EGR and high-pressure fuel injection techniques; no exhaust gas after-treatment was used. Particle measurements were performed in vehicle laboratory and on road. Nucleation mode dominated the particle number size distribution in all the tested driving conditions. According to the on-road measurements, the nucleation mode was already formed after 0.7 s residence time in the atmosphere and no significant changes were observed for longer residence times. The nucleation mode was insensitive to the fuel sulfur content, dilution air temperature, and relative humidity. An increase in the dilution ratio decreased the size of the nucleation mode particles. This behavior was observed to be linked to the total hydrocarbon concentration in the diluted sample. In volatility measurements, the nucleation mode particles were observed to have a nonvolatile core with volatile species condensed on it. The results indicate that the nucleation mode particles have a nonvolatile core formed before the dilution process. The core particles have grown because of the condensation of semivolatile material, mainly hydrocarbons, during the dilution.     

Influence of real-world engine load conditions on nanoparticle emissions from a DPF and SCR equipped heavy-duty diesel engine

The experiments aimed at investigating the effect of real-world engine load conditions on nanoparticle emissions from a Diesel Particulate Filter and Selective Catalytic Reduction after-treatment system (DPF-SCR) equipped heavy-duty diesel engine. The results showed the emission of nucleation mode particles in the size range of 6-15 nm at conditions with high exhaust temperatures. A direct result of higher exhaust temperatures (over 380 °C) contributing to higher concentration of nucleation mode nanoparticles is presented in this study. The action of an SCR catalyst with urea injection was found to increase the particle number count by over an order of magnitude in comparison to DPF out particle concentrations. Engine operations resulting in exhaust temperatures below 380 °C did not contribute to significant nucleation mode nanoparticle concentrations. The study further suggests the fact that SCR-equipped engines operating within the Not-To-Exceed (NTE) zone over a critical exhaust temperature and under favorable ambient dilution conditions could contribute to high nanoparticle concentrations to the environment. Also, some of the high temperature modes resulted in DPF out accumulation mode (between 50 and 200 nm) particle concentrations an order of magnitude greater than typical background PM concentrations. This leads to the conclusion that sustained NTE operation could trigger high temperature passive regeneration which in turn would result in lower filtration efficiencies of the DPF that further contributes to the increased solid fraction of the PM number count.     

Effect of advanced aftertreatment for PM and NOx reduction on heavy-duty diesel engine ultrafine particle emissions

Four heavy-duty and medium-duty diesel vehicles were tested in six different aftertreament configurations using a chassis dynamometer to characterize the occurrence of nucleation (the conversion of exhaust gases to particles upon dilution). The aftertreatment included four different diesel particulate filters and two selective catalytic reduction (SCR) devices. All DPFs reduced the emissions of solid particles by several orders of magnitude, but in certain cases the occurrence of a volatile nucleation mode could increase total particle number emissions. The occurrence of a nucleation mode could be predicted based on the level of catalyst in the aftertreatment, the prevailing temperature in the aftertreatment, and the age of the aftertreatment. The particles measured during nucleation had a high fraction of sulfate, up to 62% of reconstructed mass. Additionally the catalyst reduced the toxicity measured in chemical and cellular assays suggesting a pathway for an inverse correlation between particle number and toxicity. The results have implications for exposure to and toxicity of diesel PM.     

Apportionment of motor vehicle emissions from fast changes in number concentration and chemical composition of ultrafine particles near a roadway intersection

High frequency spikes in ultrafine number concentration near a roadway intersection arise from motor vehicles that accelerate after a red light turns green. The present work describes a method to determine the contribution of motor vehicles to the total ambient ultrafine particle mass by correlating these number concentration spikes with fast changes in ultrafine particle chemical composition measured with the nano aerosol mass spectrometer, NAMS. Measurements were performed at an urban air quality monitoring site in Wilmington, Delaware during the summer and winter of 2009. Motor vehicles were found to contribute 48% of the ultrafine particle mass in the winter measurement period, but only 16% of the ultrafine particle mass in the summer period. Chemical composition profiles and contributions to the ultrafine particle mass of spark vs diesel vehicles were estimated by correlating still camera images, chemical composition and spike contribution at each time interval.. The spark and diesel contributions were roughly equal, but the uncertainty in the split was large. The distribution of emissions from individual vehicles was determined by correlating camera images with the spike contribution to particle number concentration at each time interval. A small percentage of motor vehicles were found to emit a disproportionally large concentration of ultrafine particles, and these high emitters included both spark ignition and diesel vehicles.     

Are emissions of black carbon from gasoline vehicles underestimated? Insights from near and on-road measurements

Measurements of black carbon (BC) with a high-sensitivity laser-induced incandescence (HS-LII) instrument and a single particle soot photometer (SP2) were conducted upwind, downwind, and while driving on a highway dominated by gasoline vehicles. The results are used with concurrent CO(2) measurements to derive fuel-based BC emission factors for real-world average fleet and heavy-duty diesel vehicles separately. The derived emission factors from both instruments are compared, and a low SP2 bias (relative to the HS-LII) is found to be caused by a BC mass mode diameter less than 75 nm, that is most prominent with the gasoline fleet but is not present in the heavy-duty diesel vehicle exhaust on the highway. Results from both the LII and the SP2 demonstrate that the BC emission factors from gasoline vehicles are at least a factor of 2 higher than previous North American measurements, and a factor of 9 higher than currently used emission inventories in Canada, derived with the MOBILE 6.2C model. Conversely, the measured BC emission factor for heavy-duty diesel vehicles is in reasonable agreement with previous measurements. The results suggest that greater attention must be paid to black carbon from gasoline engines to obtain a full understanding of the impact of black carbon on air quality and climate and to devise appropriate mitigation strategies.     

Receptor model comparisons and wind direction analyses of volatile organic compounds and submicrometer particles in an arid, binational, urban air shed

The relationship between continuous measurements of volatile organic compounds sources and particle number was evaluated at a Photochemical Assessment Monitoring Station Network (PAMS) site located near the U.S.-Mexico Border in central El Paso, TX. Sources of volatile organic compounds (VOCs) were investigated using the multivariate receptor model UNMIX and the effective variance least squares receptor model known as Chemical Mass Balance (CMB, Version 8.0). As expected from PAMS measurements, overall findings from data screening as well as both receptor models confirmed that mobile sources were the major source of VOCs. Comparison of hourly source contribution estimates (SCEs) from the two receptor models revealed significant differences in motor vehicle exhaust and evaporative gasoline contributions. However, the motor vehicle exhaust contributions were highly correlated with each other. Motor vehicle exhaust was also correlated with the ultrafine and accumulation mode particle count, which suggests that motor vehicle exhaust is a source of these particles at the measurement site. Wind sector analyses were performed using the SCE and pollutant data to assess source location of VOCs, particle count, and criteria pollutants. Results from this study have application to source apportionment studies and mobile source emission control strategies that are ongoing in this air shed.     

Effects of a catalytic volatile particle remover (VPR) on the particulate matter emissions from a direct injection spark ignition engine

Emissions of fine particles have been shown to have a large impact on the atmospheric environment and human health. Researchers have shown that gasoline engines, especially direct injection spark ignition (DISI) engines, tend to emit large amounts of small size particles compared to diesel engines fitted with diesel particulate filters (DPFs). As a result, the particle number emissions of DISI engines will be restricted by the forthcoming EU6 legislation. The particulate emission level of DISI engines means that they could face some challenges in meeting the EU6 requirement. This paper is an experimental study on the size-resolved particle number emissions from a spray guided DISI engine and the performance of a catalytic volatile particle remover (VPR), as the EU legislation seeks to exclude volatile particles. The performance of the catalytic VPR was evaluated by varying its temperature and the exhaust residence time. The effect of the catalytic VPR acting as an oxidation catalyst on particle emissions was also tested. The results show that the catalytic VPR led to a marked reduction in the number of particles, especially the smaller size (nucleation mode) particles. The catalytic VPR is essentially an oxidation catalyst, and when post three-way catalyst (TWC) exhaust was introduced to the catalytic VPR, the performance of the catalytic VPR was not affected much by the use of additional air, i.e., no significant oxidation of the PM was observed.     

On-road emission rates of PAH and n-alkane compounds from heavy-duty diesel vehicles

This paper presents the quantification of the emission rates of PAH and n-alkane compounds from on-road emissions testing of nine heavy-duty diesel (HDD) vehicles tested using CE-CERT's Mobile Emissions Laboratory (MEL) over the California Air Resources Board (ARB) Four Phase Cycle. Per mile and per CO2 emission rates of PAHs and n-alkanes were highest for operation simulating congested traffic (Creep) and lowest for cruising conditions (Cruise). Significant differences were seen in emission rates over the different phases of the cycle. Creep phase fleet average emission rates (mg mi(-1)) of PAHs and n-alkanes were approximately an order of magnitude higher than Cruise phase. This finding indicates that models must account for mode of operation when performing emissions inventory estimates. Failure to account for mode of operation can potentially lead to significant over- and underpredictions of emissions inventories (up to 20 times), especially in small geographic regions with significant amounts of HDD congestion. Howeverthe PAH and n-alkane source profiles remained relatively constant for the different modes of operation. Variability of source profiles within the vehicle fleet exceeded the variability due to different operating modes. Analysis of the relative risk associated with the compounds indicated the importance of naphthalene as a significant contributor to the risk associated with diesel exhaust. This high relative risk is driven by the magnitude of the emission rate of naphthalene in comparison to other compounds.     

机动车尾气监测技术及监测平台的实现研究

随着城市化进程不断加快,机动车保有量激增,尾气污染问题日益严重,在国内大、中城市多呈现以机动车污染为特点的大气复合型污染城市病,机动车尾气排放已成为影响空气质量的主要来源.本文对汽车尾气遥感监测平台进行了研究,并从尾气监测、车辆筛选等方面分析了该平台的应用情况.该监测平台能够获得较客观的尾气监测结果,有助于强化机动车尾...     

Hydrogen cyanide exhaust emissions from in-use motor vehicles

Motor vehicle exhaust emissions are known to contain hydrogen cyanide (HCN), but emission rate data are scarce and, in the case of idling vehicles, date back over 20 years. For the first time, vehicular HCN exhaust emissions from a modern, in-use fleet at idle have been measured. The 14 tested light duty motor vehicles were operating at idle as these conditions are associated with the highest risk exposure scenarios (i.e., enclosed spaces). Vehicular HCN was detected in 89% of the sampled exhaust streams and did not correlate with instantaneous air-fuel-ratio or with any single, coemitted pollutant. However, a moderate correlation between HCN emissions and the product of carbon monoxide and nitric oxide emissions was observed under cold-start conditions. Fleet average, cold-start, undiluted HCN emissions were 105 +/- 97 ppbV (maximum: 278 ppbV), whereas corresponding emissions from vehicles operating under stabilized conditions were 79 +/- 71 ppbV (maximum: 245 ppbV); mean idle fleet HCN emission rates were 39 +/- 35 and 21 +/- 18 microg-min(-1) for cold-start and stabilized vehicles, respectively. The significance of these results is discussed in terms of HCN emissions inventories in the South Coast Air Basin of California and of health risks due to exposure to vehicular HCN.     

Single particle characterization of ultrafine and accumulation mode particles from heavy duty diesel vehicles using aerosol time-of-flight mass spectrometry

The aerodynamic size and chemical composition of individual ultrafine and accumulation mode particle emissions (Da = 50-300 nm) were characterized to determine mass spectral signatures for heavy duty diesel vehicle (HDDV) emissions that can be used for atmospheric source apportionment. As part of this study, six in-use HDDVs were operated on a chassis dynamometer using the heavy heavy-duty diesel truck (HHDDT) five-cycle driving schedule under different simulated weight loads. The exhaust emissions were passed through a dilution/residence system to simulate atmospheric dilution conditions, after which an ultrafine aerosol time-of-flight mass spectrometer (UF-ATOFMS) was used to sample and characterize the HDDV exhaust particles in real-time. This represents the first study where refractory species including elemental carbon and metals are characterized directly in HDDV emissions using on-line mass spectrometry. The top three particle classes observed with the UF-ATOFMS comprise 91% of the total particles sampled and show signatures indicative of a combination of elemental carbon (EC) and engine lubricating oil. In addition to the vehicle make/year, the effects of driving cycle and simulated weight load on exhaust particle size and composition were investigated.     

Polycyclic aromatic hydrocarbon emissions from the combustion of alternative fuels in a gas turbine engine

We report on the particulate-bound polycyclic aromatic hydrocarbons (PAH) in the exhaust of a test-bed gas turbine engine when powered by Jet A-1 aviation fuel and a number of alternative fuels: Sasol fully synthetic jet fuel (FSJF), Shell gas-to-liquid (GTL) kerosene, and Jet A-1/GTL 50:50 blended kerosene. The concentration of PAH compounds in the exhaust emissions vary greatly between fuels. Combustion of FSJF produces the greatest total concentration of PAH compounds while combustion of GTL produces the least. However, when PAHs in the exhaust sample are measured in terms of the regulatory marker compound benzo[a]pyrene, then all of the alternative fuels emit a lower concentration of PAH in comparison to Jet A-1. Emissions from the combustion of Jet A-1/GTL blended kerosene were found to have a disproportionately low concentration of PAHs and appear to inherit a greater proportion of the GTL emission characteristics than would be expected from volume fraction alone. The data imply the presence of a nonlinear relation between fuel blend composition and the emission of PAH compounds. For each of the fuels, the speciation of PAH compounds present in the exhaust emissions were found to be remarkably similar (R(2) = 0.94-0.62), and the results do provide evidence to support the premise that PAH speciation is to some extent indicative of the emission source. In contrast, no correlation was found between the PAH species present in the fuel with those subsequently emitted in the exhaust. The results strongly suggests that local air quality measured in terms of the particulate-bound PAH burden could be significantly improved by the use of GTL kerosene either blended with or in place of Jet A-1 kerosene.     

Measurements of particle number and mass concentrations and size distributions in a tunnel environment

Particulate matter emissions were measured in two bores of the Caldecott Tunnel in Northern California during August and September 2004. One bore (Bore 1) is open to both heavy- and light-duty vehicles while heavy-duty vehicles are prohibited from entering the second bore (Bore 2). Particulate matter number and mass size distributions, chemical composition, and gaseous copollutants were recorded for four consecutive days near the entrance and exit of each bore. Size-resolved emission factors were determined for particle number, particle mass, elemental carbon, organic carbon (OC), sulfate, nitrate, and selected elements. The size distributions in both the bores showed a single large mode at roughly 15-20 nm in mobility diameter, with occasional smaller modes around 100 nm. The PM10 mass emission factor for heavy-duty vehicles was 14.5 times higher than that of light-duty vehicles. The particles derived from diesel are more abundant in elemental carbon, 70.9% of PM10 emissions, as compared to the light-duty vehicles. Conversely, a greater percentage of OC was found in light-duty emissions than heavy-duty emissions. In comparison to previous studies at the Caldecott Tunnel, less particle mass but more particle numbers are emitted by vehicles than was the case 7 years ago.     

Global emission of black carbon from motor vehicles from 1960 to 2006

Black carbon (BC) is a key short-lived climate change forcer. Motor vehicles are important sources of BC in the environment. BC emission factors (EF(BC)), defined as BC emitted per mass of fuel consumed, are critical in the development of BC emission inventories for motor vehicles. However, measured EF(BC) for motor vehicles vary in orders of magnitude, which is one of the major sources of uncertainty in the estimation of emissions. In this study, the main factors affecting EF(BC) for motor vehicles were investigated based on 385 measured EF(BC) collected from the literature. It was found that EF(BC) for motor vehicles of a given year in a particular country can be predicted using gross domestic product per capita (GDP(c)), temperature, and the year a country's GDP(c) reached 3000 USD (Y(3000)). GDP(c) represents technical progress in terms of emission control, while Y(3000) suggest the technical transfer from developed to developing countries. For global BC emission calculations, 87 and 64% of the variation can be eliminated for diesel and gasoline vehicles by using this model. In addition to a reduction in uncertainty, the model can be used to develop a global on-road vehicle BC emission inventory with spatial and temporal resolution.     

Characterization of residential wood combustion particles using the two-wavelength aethalometer

In the United States, residential wood combustion (RWC) is responsible for 7.0% of the national primary PM(2.5) emissions. Exposure to RWC smoke represents a potential human health hazard. Organic components of wood smoke particles absorb light at 370 nm more effectively than 880 nm in two-wavelength aethalometer measurements. This enhanced absorption (Delta-C = BC(370 nm) - BC(880 nm)) can serve as an indicator of RWC particles. In this study, aethalometer Delta-C data along with measurements of molecular markers and potassium in PM(2.5) were used to identify the presence of airborne RWC particles in Rochester, NY. The aethalometer data were corrected for the loading effect. Delta-C was found to strongly correlate with wood smoke markers (levoglucosan and potassium) during the heating season. No statistically significant correlation was found between Delta-C and vehicle exhaust markers. The Delta-C values were substantially higher during winter compared to summer. The winter diurnal pattern showed an evening peak around 21:00 that was particularly enhanced on weekends. A relationship between Delta-C and PM(2.5) was found that permits the estimation of the contribution of RWC particles to the PM mass. RWC contributed 17.3% to the PM(2.5) concentration during the winter. Exponential decay was a good estimator for predicting Delta-C concentrations at different winter precipitation rates and different wind speeds. Delta-C was also sensitive to remote forest fire smoke.     

Uncertainty in particle number modal analysis during transient operation of compressed natural gas, diesel, and trap-equipped diesel transit buses

The relationships between transient vehicle operation and ultrafine particle emissions are not well-known, especially for low-emission alternative bus technologies such as compressed natural gas (CNG) and diesel buses equipped with particulate filters/traps (TRAP). In this study, real-time particle number concentrations measured on a nominal 5 s average basis using an electrical low pressure impactor (ELPI) for these two bus technologies are compared to that of a baseline catalyst-equipped diesel bus operated on ultralow sulfur fuel (BASE) using dynamometer testing. Particle emissions were consistently 2 orders of magnitude lower for the CNG and TRAP compared to BASE on all driving cycles. Time-resolved total particle numbers were examined in terms of sampling factors identified as affecting the ability of ELPI to quantify the particulate matter number emissions for low-emitting vehicles such as CNG and TRAP as a function of vehicle driving mode. Key factors were instrument sensitivity and dilution ratio, alignment of particle and vehicle operating data, sampling train background particles, and cycle-to-cycle variability due to vehicle, engine, after-treatment, or driver behavior. In-cycle variability on the central business district (CBD) cycle was highest for the TRAP configuration, but this could not be attributed to the ELPI sensitivity issues observed for TRAP-IDLE measurements. Elevated TRAP emissions coincided with low exhaust temperature, suggesting on-road real-world particulate filter performance can be evaluated by monitoring exhaust temperature. Nonunique particle emission maps indicate that measures other than vehicle speed and acceleration are necessary to model disaggregated real-time particle emissions. Further testing on a wide variety of test cycles is needed to evaluate the relative importance of the time history of vehicle operation and the hysteresis of the sampling train/dilution tunnel on ultrafine particle emissions. Future studies should monitor particle emissions with high-resolution real-time instruments and account for the operating regime of the vehicle using time-series analysis to develop predictive number emissions models.     

Determination of single particle mass spectral signatures from light-duty vehicle emissions

In this study, 28 light-duty gasoline vehicles (LDV) were operated on a chassis dynamometer at the California Air Resources Board Haagen-Smit Facility in El Monte, CA. The mass spectra of individual particles emitted from these vehicles were measured using aerosol time-of-flight mass spectrometry (ATOFMS). A primary goal of this study involves determining representative size-resolved single particle mass spectral signatures that can be used in future ambient particulate matter source apportionment studies. Different cycles were used to simulate urban driving conditions including the federal testing procedure (FTP), unified cycle (UC), and the correction cycle (CC). The vehicles were selected to span a range of catalytic converter (three-way, oxidation, and no catalysts) and engine technologies (vehicles models from 1953 to 2003). Exhaust particles were sampled directly from a dilution and residence chamber system using particle sizing instruments and an ATOFMS equipped with an aerodynamic lens (UF-ATOFMS) analyzing particles between 50 and 300 nm. On the basis of chemical composition, 10 unique chemical types describe the majority of the particles with distinct size and temporal characteristics. In the ultrafine size range (between 50 and 100 nm), three elemental carbon (EC) particle types dominated, all showing distinct EC signatures combined with Ca, phosphate, sulfate, and a lower abundance of organic carbon (OC). The relative fraction of EC particle types decreased as particle size increased with OC particles becoming more prevalent above 100 nm. Depending on the vehicle and cycle, several distinct OC particle types produced distinct ion patterns, including substituted aromatic compounds and polycyclic aromatic hydrocarbons (PAH), coupled with other chemical species including ammonium, EC, nitrate, sulfate, phosphate, V, and Ca. The most likely source of the Ca and phosphate in the particles is attributed to the lubricating oil. Significant variability was observed in the chemical composition of particles emitted within the different car categories as well as for the same car operating under different driving conditions. Two-minute temporal resolution measurements provide information on the chemical classes as they evolved during the FTP cycle. The first two minutes of the cold start produced more than 5 times the number of particles than any other portion of the cycle, with one class of ultrafine particles (EC coupled with Ca, OC, and phosphate) preferentially produced. By number, the three EC with Ca classes (which also contained OC, phosphate, and sulfate) were the most abundant classes produced by the nonsmoking vehicles. The smoker category produced the highest number of particles, with the dominant classes being OC comprised of substituted monoaromatic compounds and PAHs, coupled with Ca and phosphate, thus suggesting used lubricating oil was associated with many of these particles. These studies show, by number, EC particles dominate gasoline emissions in the ultrafine size range particularlyforthe lowest emitting newer vehicles, suggesting the EC signature alone cannot be used as a unique tracer for diesels. This represents the first report of high time- and size-resolved chemical composition data showing the mixing state of nonrefractory elements in particles such as EC for vehicle emissions during dynamometer source testing.     

Phase and size distribution of polycyclic aromatic hydrocarbons in diesel and gasoline vehicle emissions

Emission measurements were obtained for a variety of military vehicles at Hill Air Force Base (Ogden, UT) in November 2000 as part of a Strategic Environmental Research and Development Program. Aircraft ground support equipment vehicles using gasoline, diesel, and JP8 fuels were tested using chassis dynamometers under predetermined load. The exhaust from the tested vehicle was passed to a dilution tunnel where it was diluted 30-40 times and collected using Micro-Orifice Uniform Deposit Impactor (MOUDI) fitted with aluminum substrates, an XAD-coated annular denuder, and a filter followed by a solid adsorbent. All MOUDI substrates were analyzed for mass and for organic and elemental (EC) carbon by the thermal/optical reflectance method and for polycyclic aromatic hydrocarbons (PAHs) by GC/MS. Black carbon was measured with a photoacoustic instrument. The denuder and filter/solid adsorbent samples were analyzed for semivolatile PAH. Overall, there is more mass and higher EC contribution when the vehicle is run under higher load in comparison with the low load. However, older vehicles generally show more mass and EC emissions than newer vehicles, and there is a shift toward smaller particle sizes for the low load, which is most pronounced for newer vehicles. The particle-associated semivolatile PAHs and nonvolatile four-through six-ring PAHs are present predominantly on the submicron particles collected on MOUDI stages 0.1-0.18, 0.18-0.32, and 0.32-0.56 microm. For the low-load runs, the distribution of PAHs seems to be shifted toward smaller size particles. The gas-particle phase distribution of semivolatile PAHs depends also on the engine loading. For idle, not only are the more volatile two- and three-ring PAHs, from naphthalene to dimethylphenanthrenes, retained on the denuder portion, but also less volatile four-ring PAHs, such as fluoranthene and pyrene, are retained by the denuder at the 80-90% range, which implies that they are present predominantly in the gas phase. In contrast, for engines under high loads, a much larger portion of three- and four-ring PAHs are partitioned to the particle phase.