Size and composition distributions of particulate matter emissions: part 1--light-duty gasoline vehicles

Size-resolved particulate matter (PM) emitted from light-duty gasoline vehicles (LDGVs) was characterized using filter-based samplers, cascade impactors, and scanning mobility particle size measurements in the summer 2002. Thirty LDGVs, with different engine and emissions control technologies (model years 1965-2003; odometer readings 1264-207,104 mi), were tested on a chassis dynamometer using the federal test procedure (FTP), the unified cycle (UC), and the correction cycle (CC). LDGV PM emissions were strongly correlated with vehicle age and emissions control technology. The oldest models had average ultrafine PM0.1 (0.056- to 0.1-microm aerodynamic diameter) and fine PM1.8 (< or =1.8-microm aerodynamic diameter) emission rates of 9.6 mg/km and 213 mg/km, respectively. The newest vehicles had PM0.1 and PM1.8 emissions of 51 microg/km and 371 microg/km, respectively. Light duty trucks and sport utility vehicles had PM0.1 and PM1.8 emissions nearly double the corresponding emission rates from passenger cars. Higher PM emissions were associated with cold starts and hard accelerations. The FTP driving cycle produced the lowest emissions, followed by the UC and the CC. PM mass distributions peaked between 0.1- and 0.18-microm particle diameter for all vehicles except those emitting visible smoke, which peaked between 0.18 and 0.32 microm. The majority of the PM was composed of carbonaceous material, with only trace amounts of water-soluble ions. Elemental carbon (EC) and organic matter (OM) had similar size distributions, but the EC/OM ratio in LDGV exhaust particles was a strong function of the adopted emissions control technology and of vehicle maintenance. Exhaust from LDGV classes with lower PM emissions generally had higher EC/OM ratios. LDGVs adopting newer technologies were characterized by the highest EC/OM ratios, whereas OM dominated PM emissions from older vehicles. Driving cycles with cold starts and hard accelerations produced higher EC/OM ratios in ultrafine particles.     

Size and Composition Distributions of Particulate Matter Emissions: Part 1—Light-Duty Gasoline Vehicles

Abstract

Size-resolved particulate matter (PM) emitted from light-duty gasoline vehicles (LDGVs) was characterized using filter-based samplers, cascade impactors, and scanning mobility particle size measurements in the summer 2002. Thirty LDGVs, with different engine and emissions control technologies (model years 1965–2003; odometer readings 1264–207,104 mi), were tested on a chassis dynamometer using the federal test procedure (FTP), the unified cycle (UC), and the correction cycle (CC). LDGV PM emissions were strongly correlated with vehicle age and emissions control technology. The oldest models had average ultrafine PM_0.1 (0.056- to 0.1-μm aerodynamic diameter) and fine PM_1.8 (≤1.8-μm aerodynamic diame ter) emission rates of 9.6 mg/km and 213 mg/km, respectively. The newest vehicles had PM_0.1 and PM_1.8 emis sions of 51 μg/km and 371 μg/km, respectively. Light duty trucks and sport utility vehicles had PM_0.1 and PM_1.8 emissions nearly double the corresponding emission rates from passenger cars. Higher PM emissions were associated with cold starts and hard accelerations. The FTP driving cycle produced the lowest emissions, followed by the UC and the CC. PM mass distributions peaked between 0.1-and 0.18-μm particle diameter for all vehicles except those emitting visible smoke, which peaked between 0.18 and 0.32 μm. The majority of the PM was composed of carbonaceous material, with only trace amounts of water-soluble ions. Elemental carbon (EC) and organic matter (OM) had similar size distributions, but the EC/OM ratio in LDGV exhaust particles was a strong function of the adopted emissions control technology and of vehicle maintenance. Exhaust from LDGV classes with lower PM emissions generally had higher EC/OM ratios. LDGVs adopting newer technologies were characterized by the highest EC/OM ratios, whereas OM dominated PM emissions from older vehicles. Driving cycles with cold starts and hard accelerations produced higher EC/OM ratios in ultrafine particles.     

Characterization of exhaust particles from military vehicles fueled with diesel,gasoline, and JP-8

Diluted exhaust from selected military aircraft ground-support equipment (AGE) was analyzed for particulate mass, elemental carbon (EC) and organic carbon (OC), SO4(2-), and size distributions. The experiments occurred at idle and load conditions and utilized a chassis dynamometer. The selected AGE vehicles operated on gasoline, diesel, and JP-8. These military vehicles exhibited concentrations, size distributions, and emission factors in the same range as those reported for nonmilitary vehicles. The diesel and JP-8 emission rates for PM ranged from 0.092 to 1.1 g/kg fuel. The EC contributed less and the OC contributed more to the particulate mass than reported in recent studies of vehicle emissions. Overall, the particle size distribution varied significantly with engine condition, with the number of accumulation mode particles and the count median diameter (CMD) increasing as engine load increased. The SO4(2-) analyses showed that the distribution of SO4(2-) mass mirrored the distribution of particle mass.     

Effects of improved spatial and temporal modeling of on-road vehicle emissions

Numerous emission and air quality modeling studies have suggested the need to accurately characterize the spatial and temporal variations in on-road vehicle emissions. The purpose of this study was to quantify the impact that using detailed traffic activity data has on emission estimates used to model air quality impacts. The on-road vehicle emissions are estimated by multiplying the vehicle miles traveled (VMT) by the fleet-average emission factors determined by road link and hour of day. Changes in the fraction of VMT from heavy-duty diesel vehicles (HDDVs) can have a significant impact on estimated fleet-average emissions because the emission factors for HDDV nitrogen oxides (NOx) and particulate matter (PM) are much higher than those for light-duty gas vehicles (LDGVs). Through detailed road link-level on-road vehicle emission modeling, this work investigated two scenarios for better characterizing mobile source emissions: (1) improved spatial and temporal variation of vehicle type fractions, and (2) use of Motor Vehicle Emission Simulator (MOVES2010) instead of MOBILE6 exhaust emission factors. Emissions were estimated for the Detroit and Atlanta metropolitan areas for summer and winter episodes. The VMT mix scenario demonstrated the importance of better characterizing HDDV activity by time of day, day of week, and road type. More HDDV activity occurs on restricted access road types on weekdays and at nonpeak times, compared to light-duty vehicles, resulting in 5-15% higher NOx and PM emission rates during the weekdays and 15-40% lower rates on weekend days. Use of MOVES2010 exhaust emission factors resulted in increases of more than 50% in NOx and PM for both HDDVs and LDGVs, relative to MOBILE6. Because LDGV PM emissions have been shown to increase with lower temperatures, the most dramatic increase from MOBILE6 to MOVES2010 emission rates occurred for PM2.5 from LDGVs that increased 500% during colder wintertime conditions found in Detroit, the northernmost city modeled.     

Idle emissions from heavy-duty diesel and natural gas vehicles at high altitude

Idle emissions of total hydrocarbon (THC), CO, NOx, and particulate matter (PM) were measured from 24 heavy-duty diesel-fueled (12 trucks and 12 buses) and 4 heavy-duty compressed natural gas (CNG)-fueled vehicles. The volatile organic fraction (VOF) of PM and aldehyde emissions were also measured for many of the diesel vehicles. Experiments were conducted at 1609 m above sea level using a full exhaust flow dilution tunnel method identical to that used for heavy-duty engine Federal Test Procedure (FTP) testing. Diesel trucks averaged 0.170 g/min THC, 1.183 g/min CO, 1.416 g/min NOx, and 0.030 g/min PM. Diesel buses averaged 0.137 g/min THC, 1.326 g/min CO, 2.015 g/min NOx, and 0.048 g/min PM. Results are compared to idle emission factors from the MOBILE5 and PART5 inventory models. The models significantly (45-75%) overestimate emissions of THC and CO in comparison with results measured from the fleet of vehicles examined in this study. Measured NOx emissions were significantly higher (30-100%) than model predictions. For the pre-1999 (pre-consent decree) truck engines examined in this study, idle NOx emissions increased with model year with a linear fit (r2 = 0.6). PART5 nationwide fleet average emissions are within 1 order of magnitude of emissions for the group of vehicles tested in this study. Aldehyde emissions for bus idling averaged 6 mg/min. The VOF averaged 19% of total PM for buses and 49% for trucks. CNG vehicle idle emissions averaged 1.435 g/min for THC, 1.119 g/min for CO, 0.267 g/min for NOx, and 0.003 g/min for PM. The g/min PM emissions are only a small fraction of g/min PM emissions during vehicle driving. However, idle emissions of NOx, CO, and THC are significant in comparison with driving emissions.     

Idle emissions from heavy-duty diesel vehicles: review and recent data

Heavy-duty diesel vehicle idling consumes fuel and reduces atmospheric quality, but its restriction cannot simply be proscribed, because cab heat or air-conditioning provides essential driver comfort. A comprehensive tailpipe emissions database to describe idling impacts is not yet available. This paper presents a substantial data set that incorporates results from the West Virginia University transient engine test cell, the E-55/59 Study and the Gasoline/Diesel PM Split Study. It covered 75 heavy-duty diesel engines and trucks, which were divided into two groups: vehicles with mechanical fuel injection (MFI) and vehicles with electronic fuel injection (EFI). Idle emissions of CO, hydrocarbon (HC), oxides of nitrogen (NOx), particulate matter (PM), and carbon dioxide (CO2) have been reported. Idle CO2 emissions allowed the projection of fuel consumption during idling. Test-to-test variations were observed for repeat idle tests on the same vehicle because of measurement variation, accessory loads, and ambient conditions. Vehicles fitted with EFI, on average, emitted approximately 20 g/hr of CO, 6 g/hr of HC, 86 g/hr of NOx, 1 g/hr of PM, and 4636 g/hr of CO2 during idle. MFI equipped vehicles emitted approximately 35 g/hr of CO, 23 g/hr of HC, 48 g/hr of NOx, 4 g/hr of PM, and 4484 g/hr of CO2, on average, during idle. Vehicles with EFI emitted less idle CO, HC, and PM, which could be attributed to the efficient combustion and superior fuel atomization in EFI systems. Idle NOx, however, increased with EFI, which corresponds with the advancing of timing to improve idle combustion. Fuel injection management did not have any effect on CO2 and, hence, fuel consumption. Use of air conditioning without increasing engine speed increased idle CO2, NOx, PM, HC, and fuel consumption by 25% on average. When the engine speed was elevated from 600 to 1100 revolutions per minute, CO2 and NOx emissions and fuel consumption increased by >150%, whereas PM and HC emissions increased by approximately 100% and 70%, respectively. Six Detroit Diesel Corp. (DDC) Series 60 engines in engine test cell were found to emit less CO, NOx, and PM emissions and consumed fuel at only 75% of the level found in the chassis dynamometer data. This is because fan and compressor loads were absent in the engine test cell.     

Emission rates and comparative chemical composition from selected in-use diesel and gasoline-fueled vehicles

Emission samples for toxicity testing and detailed chemical characterization were collected from a variety of gasoline- and diesel-fueled in-use vehicles operated on the Unified Driving Cycle on a chassis dynamometer. Gasoline vehicles included normal particle mass (particulate matter [PM]) emitters (tested at 72 and 30 degrees F), "black" and "white" smokers, and a new-technology vehicle (tested at 72 degrees F). Diesel vehicles included current-technology vehicles (tested at 72 and 30 degrees F) and a high PM emitter. Total PM emission rates ranged from below 3 mg/mi up to more than 700 mg/mi for the white smoker gasoline vehicle. Emission rates of organic and elemental carbon (OC/EC), elements (metals and associated analytes), ions, and a variety of particulate and semi-volatile organic compounds (polycyclic aromatic hydrocarbons [PAH], nitro-PAH, oxy-PAH, hopanes, and steranes) are reported for these vehicles. Speciated organic analysis also was conducted on the fuels and lube oils obtained from these vehicles after the emissions testing. The compositions of emissions were highly dependent on the fuel type (gasoline vs. diesel), the state of vehicle maintenance (low, average, or high emitters; white or black smokers), and ambient conditions (i.e., temperature) of the vehicles. Fuel and oil analyses from these vehicles showed that oil served as a repository for combustion byproducts (e.g., PAH), and oil-burning gasoline vehicles emitted PAH in higher concentrations than did other vehicles. These PAH emissions matched the PAH compositions observed in oil.     

Theoretical versus observed gas-particle partitioning of carbonyl emissions from motor vehicles

A state-of-the-science thermodynamic model describing gas-particle absorption processes was used to predict the gas-particle partitioning of mixtures of approximately 60 carbonyl compounds emitted from low-emission gasoline-powered vehicles, three-way catalyst gasoline-powered vehicles, heavy-duty diesel vehicles under the idle-creep condition (HDDV idle), and heavy-duty diesel vehicles under the five-mode test (HDDV 5-mode). Exhaust was diluted by a factor of 120-580 with a residence time of approximately 43 sec. The predicted equilibrium absorption partitioning coefficients differed from the measured partitioning coefficients by several orders of magnitude. Time scales to reach equilibrium in the dilution sampling system were close to the actual residence time during the HDDV 5-mode test and much longer than the actual residence time during the other vehicle tests. It appears that insufficient residence time in the sampling system cannot uniformly explain the failure of the absorption mechanism to explain the measured partitioning. Other gas-particle partitioning mechanisms (e.g., heterogeneous reactions, capillary adsorption) beyond the simple absorption theory are needed to explain the discrepancy between calculated carbonyl partitioning coefficients and observed partitioning. Both of these alternative partitioning mechanisms imply great challenges for the measurement and modeling of semi-volatile primary organic aerosol (POA) species from motor vehicles. Furthermore, as emitted particle concentrations from newer vehicles approach atmospheric background levels, dilution sampling systems must fundamentally change their approach so that they use realistic particle concentrations in the dilution air to approximately represent real-world conditions. Samples collected with particle-free dilution air yielding total particulate matter concentrations below typical ambient concentrations will not provide a realistic picture of partitioning for semi-volatile compounds.     

Theoretical versus Observed Gas-Particle Partitioning of Carbonyl Emissions from Motor Vehicles

Abstract

A state-of-the-science thermodynamic model describing gas-particle absorption processes was used to predict the gas-particle partitioning of mixtures of approximately 60 carbonyl compounds emitted from low-emission gasoline-powered vehicles, three-way catalyst gasoline-powered vehicles, heavy-duty diesel vehicles under the idle-creep condition (HDDV idle), and heavy-duty diesel vehicles under the five-mode test (HDDV 5-mode). Exhaust was diluted by a factor of 120–580 with a residence time of approximately 43 sec. The predicted equilibrium absorption partitioning coefficients differed from the measured partitioning coefficients by several orders of magnitude. Time scales to reach equilibrium in the dilution sampling system were close to the actual residence time during the HDDV 5-mode test and much longer than the actual residence time during the other vehicle tests. It appears that insufficient residence time in the sampling system cannot uniformly explain the failure of the absorption mechanism to explain the measured partitioning. Other gas-particle partitioning mechanisms (e.g., heterogeneous reactions, capillary adsorption) beyond the simple absorption theory are needed to explain the discrepancy between calculated carbonyl partitioning coefficients and observed partitioning. Both of these alternative partitioning mechanisms imply great challenges for the measurement and modeling of semi-volatile primary organic aerosol (POA) species from motor vehicles. Furthermore, as emitted particle concentrations from newer vehicles approach atmospheric background levels, dilution sampling systems must fundamentally change their approach so that they use realistic particle concentrations in the dilution air to approximately represent real-world conditions. Samples collected with particle-free dilution air yielding total particulate matter concentrations below typical ambient concentrations will not provide a realistic picture of partitioning for semi-volatile compounds.     

Emission factors for high-emitting vehicles based on on-road measurements of individual vehicle exhaust with a mobile measurement platform

Fuel-based emission factors for 143 light-duty gasoline vehicles (LDGVs) and 93 heavy-duty diesel trucks (HDDTs) were measured in Wilmington, CA using a zero-emission mobile measurement platform (MMP). The frequency distributions of emission factors of carbon monoxide (CO), nitrogen oxides (NO(x)), and particle mass with aerodynamic diameter below 2.5 microm (PM2.5) varied widely, whereas the average of the individual vehicle emission factors were comparable to those reported in previous tunnel and remote sensing studies as well as the predictions by Emission Factors (EMFAC) 2007 mobile source emission model for Los Angeles County. Variation in emissions due to different driving modes (idle, low- and high-speed acceleration, low- and high-speed cruise) was found to be relatively small in comparison to intervehicle variability and did not appear to interfere with the identification of high emitters, defined as the vehicles whose emissions were more than 5 times the fleet-average values. Using this definition, approximately 5% of the LDGVs and HDDTs measured were high emitters. Among the 143 LDGVs, the average emission factors of NO(x), black carbon (BC), PM2.5, and ultrafine particle (UFP) would be reduced by 34%, 39%, 44%, and 31%, respectively, by removing the highest 5% of emitting vehicles, whereas CO emission factor would be reduced by 50%. The emission distributions of the 93 HDDTs measured were even more skewed: approximately half of the NO(x) and CO fleet-average emission factors and more than 60% of PM2.5, UFP, and BC fleet-average emission factors would be reduced by eliminating the highest-emitting 5% HDDTs. Furthermore, high emissions of BC, PM2.5, and NO(x) tended to cluster among the same vehicles.     

Development of molecular marker source profiles for emissions from on-road gasoline and diesel vehicle fleets

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

Idle Emissions from Heavy-Duty Diesel Vehicles: Review and Recent Data

Abstract

Heavy-duty diesel vehicle idling consumes fuel and reduces atmospheric quality, but its restriction cannot simply be proscribed, because cab heat or air-conditioning provides essential driver comfort. A comprehensive tailpipe emissions database to describe idling impacts is not yet available. This paper presents a substantial data set that incorporates results from the West Virginia University transient engine test cell, the E-55/59 Study and the Gasoline/Diesel PM Split Study. It covered 75 heavy-duty diesel engines and trucks, which were divided into two groups: vehicles with mechanical fuel injection (MFI) and vehicles with electronic fuel injection (EFI). Idle emissions of CO, hydrocarbon (HC), oxides of nitrogen (NO_x), particulate matter (PM), and carbon dioxide (CO₂) have been reported. Idle CO₂ emissions allowed the projection of fuel consumption during idling. Test-to-test variations were observed for repeat idle tests on the same vehicle because of measurement variation, accessory loads, and ambient conditions. Vehicles fitted with EFI, on average, emitted [~20 g/hr of CO, 6 g/hr of HC, 86 g/hr of NO_x, 1 g/hr of PM, and 4636 g/hr of CO₂ during idle. MFI equipped vehicles emitted ~35 g/hr of CO, 23 g/hr of HC, 48 g/hr of NO_x, 4 g/hr of PM, and 4484 g/hr of CO₂, on average, during idle. Vehicles with EFI emitted less idleCO, HC, and PM, which could be attributed to the efficient combustion and superior fuel atomization in EFI systems. Idle NO_x, however, increased with EFI, which corresponds with the advancing of timing to improve idle combustion. Fuel injection management did not have any effect on CO₂ and, hence, fuel consumption. Use of air conditioning without increasing engine speed increased idle CO₂, NO_x, PM, HC, and fuel consumption by 25% on average. When the engine speed was elevated from 600 to 1100 revolutions per minute, CO₂ and NO_x emissions and fuel consumption increased by >150%, whereas PM and HC emissions increased by ~100% and 70%, respectively. Six Detroit Diesel Corp. (DDC) Series 60 engines in engine test cell were found to emit less CO, NO_x, and PM emissions and consumed fuel at only 75%of the level found in the chassis dynamometer data. This is because fan and compressor loads were absent in the engine test cell.     

Methods of characterizing the distribution of exhaust emissions from light-duty, gasoline-powered motor vehicles in the U.S. fleet

Mobile sources significantly contribute to ambient concentrations of airborne particulate matter (PM). Source apportionment studies for PM10 (PM < or = 10 microm in aerodynamic diameter) and PM2.5 (PM < or = 2.5 microm in aerodynamic diameter) indicate that mobile sources can be responsible for over half of the ambient PM measured in an urban area. Recent source apportionment studies attempted to differentiate between contributions from gasoline and diesel motor vehicle combustion. Several source apportionment studies conducted in the United States suggested that gasoline combustion from mobile sources contributed more to ambient PM than diesel combustion. However, existing emission inventories for the United States indicated that diesels contribute more than gasoline vehicles to ambient PM concentrations. A comprehensive testing program was initiated in the Kansas City metropolitan area to measure PM emissions in the light-duty, gasoline-powered, on-road mobile source fleet to provide data for PM inventory and emissions modeling. The vehicle recruitment design produced a sample that could represent the regional fleet, and by extension, the national fleet. All vehicles were recruited from a stratified sample on the basis of vehicle class (car, truck) and model-year group. The pool of available vehicles was drawn primarily from a sample of vehicle owners designed to represent the selected demographic and geographic characteristics of the Kansas City population. Emissions testing utilized a portable, light-duty chassis dynamometer with vehicles tested using the LA-92 driving cycle, on-board emissions measurement systems, and remote sensing devices. Particulate mass emissions were the focus of the study, with continuous and integrated samples collected. In addition, sample analyses included criteria gases (carbon monoxide, carbon dioxide, nitric oxide/nitrogen dioxide, hydrocarbons), air toxics (speciated volatile organic compounds), and PM constituents (elemental/organic carbon, metals, semi-volatile organic compounds). Results indicated that PM emissions from the in-use fleet varied by up to 3 orders of magnitude, with emissions generally increasing for older model-year vehicles. The study also identified a strong influence of ambient temperature on vehicle PM mass emissions, with rates increasing with decreasing temperatures.     

Determination of single particle mass spectral signatures from heavy-duty diesel vehicle emissions for PM2.5 source apportionment

The size and chemical composition of individual diesel exhaust particles were measured in order to determine unique mass spectral signatures that can be used to identify particle sources in future ambient studies. The exhaust emissions from seven in-use heavy-duty diesel vehicles (HDDVs) operating on a chassis dynamometer were passed through a dilution tunnel and residence chamber and analyzed in real time by aerosol time-of-flight mass spectrometry (ATOFMS). Seven distinct particle types describe the majority of particles emitted by HDDVs and were emitted by all seven vehicles. The dominant chemical types originated from unburned lubricant oil, and the contributions of the various types varied with particle size and driving conditions. A comparison of light-duty vehicle (LDV) exhaust particles with the HDDV signatures provide insight into the challenges associated with developing an accurate source apportionment technique and possible ways of how they may be overcome.     

An investigation on the physical,chemical and ecotoxicological characteristics of particulate matter emitted from light-duty vehicles

Particulate matter (PM) emitted from three light-duty vehicles was studied in terms of its physicochemical and ecotoxicological character using Microtox^® bioassay tests. A diesel vehicle equipped with an oxidation catalyst emitted PM which consisted of carbon species at over 97%. PM from a diesel vehicle with a particle filter (DPF) consisted of almost equal amounts of carbon species and ions, while a gasoline vehicle emitted PM consisting of ～90% carbon and ～10% ions. Both the DPF and the gasoline vehicles produced a distinct nucleation mode at 120 km/h. The PM emitted from the DPF and the gasoline vehicles was less ecotoxic than that of conventional diesel, but not in direct proportion to the emission levels of the different vehicles. These results indicate that PM emission reductions are not equally translated into ecotoxicity reductions, implying some deficiencies on the actual environmental impact of emission control technologies and regulations.     

Review of light-duty diesel and heavy-duty diesel gasoline inspection programs

Emissions from diesel vehicles and gas-powered heavy-duty vehicles are becoming a new focus of many inspection and maintenance (I/M) programs. Diesel particulate matter (PM) is increasingly becoming more recognized as an important health concern, while at the same time, the public awareness of diesel PM emissions because of their visibility have combined to increase the focus on diesel emissions in the United States. This has resulted in an increased interest by some states in including heavy-duty vehicle testing in their I/M program. This paper provides an overview of existing I/M programs focused on testing light-duty diesel vehicles, heavy-duty diesel vehicles, and heavy-duty gasoline vehicles (HDGVs). Information on 39 I/M programs in 27 different states in the United States plus 9 international inspection programs is included. Information on the status of diesel emissions technology and current test procedures is also presented. The goal is to provide useful information for air quality managers as they work to decide whether such I/M programs would be worth pursuing in their respective areas and in evaluating the emissions measurement technology to be used in the program. Testing of HDGVs is generally limited to idle testing, because dynamometer testing of these vehicles is not practical, and most were not certified on a chassis basis. Testing of diesel vehicles has mostly been limited to SAE J1667 "snap-idle" opacity testing. Cost-effective technology for measuring diesel emissions currently does not exist, and, therefore, opacity-type measurements, although not effective at reducing the pollutants of most significant health concern, will continue to be used.     

Source contributions to primary organic aerosol: Comparison of the results of a source-resolved model and the chemical mass balance approach

A source-resolved model has been developed to predict the contribution of different sources to primary organic aerosol concentrations. The model was applied to the eastern US during a 17 day pollution episode beginning on 12 July 2001. Primary organic matter (OM) and elemental carbon (EC) concentrations are tracked for eight different sources: gasoline vehicles, non-road diesel vehicles, on-road diesel vehicles, biomass burning, wood burning, natural gas combustion, road dust, and all other sources. Individual emission inventories are developed for each source and a three-dimensional chemical transport model (PMCAMx) is used to predict the primary OM and EC concentrations from each source. The source-resolved model is simple to implement and is faster than existing source-oriented models. The results of the source-resolved model are compared to the results of chemical mass balance models (CMB) for Pittsburgh and multiple urban/rural sites from the Southeastern Aerosol Research and Characterization (SEARCH) network. Significant discrepancies exist between the source-resolved model and the CMB model predictions for some of the sources. There is strong evidence that the organic PM emissions from natural gas combustion are overestimated. It also appears that the OM and EC emissions from wood burning and off-road diesel are too high in the Northeastern US. Other similarities and discrepancies between the source-resolved model and the CMB model for primary OM and EC are discussed along with problems in the current emission inventory for certain sources.     

Variations in speciated emissions from spark-ignition and compression-ignition motor vehicles in California's south coast air basin

The U.S. Department of Energy Gasoline/Diesel PM Split Study examined the sources of uncertainties in using an organic compound-based chemical mass balance receptor model to quantify the contributions of spark-ignition (SI) and compression-ignition (CI) engine exhaust to ambient fine particulate matter (PM2.5). This paper presents the chemical composition profiles of SI and CI engine exhaust from the vehicle-testing portion of the study. Chemical analysis of source samples consisted of gravimetric mass, elements, ions, organic carbon (OC), and elemental carbon (EC) by the Interagency Monitoring of Protected Visual Environments (IMPROVE) and Speciation Trends Network (STN) thermal/optical methods, polycyclic aromatic hydrocarbons (PAHs), hopanes, steranes, alkanes, and polar organic compounds. More than half of the mass of carbonaceous particles emitted by heavy-duty diesel trucks was EC (IMPROVE) and emissions from SI vehicles contained predominantly OC. Although total carbon (TC) by the IMPROVE and STN protocols agreed well for all of the samples, the STN/IMPROVE ratios for EC from SI exhaust decreased with decreasing sample loading. SI vehicles, whether low or high emitters, emitted greater amounts of high-molecular-weight particulate PAHs (benzo[ghi]perylene, indeno[1,2,3-cd]pyrene, and coronene) than did CI vehicles. Diesel emissions contained higher abundances of two- to four-ring semivolatile PAHs. Diacids were emitted by CI vehicles but are also prevalent in secondary organic aerosols, so they cannot be considered unique tracers. Hopanes and steranes were present in lubricating oil with similar composition for both gasoline and diesel vehicles and were negligible in gasoline or diesel fuels. CI vehicles emitted greater total amounts of hopanes and steranes on a mass per mile basis, but abundances were comparable to SI exhaust normalized to TC emissions within measurement uncertainty. The combustion-produced high-molecular-weight PAHs were found in used gasoline motor oil but not in fresh oil and are negligible in used diesel engine oil. The contributions of lubrication oils to abundances of these PAHs in the exhaust were large in some cases and were variable with the age and consumption rate of the oil. These factors contributed to the observed variations in their abundances to total carbon or PM2.5 among the SI composition profiles.     

Chemical speciation of PM emissions from heavy-duty diesel vehicles equipped with diesel particulate filter (DPF) and selective catalytic reduction (SCR) retrofits

Four heavy-duty diesel vehicles (HDDVs) in six retrofitted configurations (CRT^®, V-SCRT^®, Z-SCRT^®, Horizon, DPX and CCRT^®) and a baseline vehicle operating without after--treatment were tested under cruise (50 mph), transient UDDS and idle driving modes. As a continuation of the work by Biswas et al. [Biswas, S., Hu, S., Verma, V., Herner, J., Robertson, W.J., Ayala, A., Sioutas, C., 2008. Physical properties of particulate matter (PM) from late model heavy-duty diesel vehicles operating with advanced emission control technologies. Atmospheric Environment 42, 5622–5634.] on particle physical parameters, this paper focuses on PM chemical characteristics (Total carbon [TC], Elemental carbon [EC], Organic Carbon [OC], ions and water-soluble organic carbon [WSOC]) for cruise and UDDS cycles only. Size-resolved PM collected by MOUDI–Nano-MOUDI was analyzed for TC, EC and OC and ions (such as sulfate, nitrate, ammonium, potassium, sodium and phosphate), while Teflon coated glass fiber filters from a high volume sampler were extracted to determine WSOC. The introduction of retrofits reduced PM mass emissions over 90% in cruise and 95% in UDDS. Similarly, significant reductions in the emission of major chemical constituents (TC, OC and EC) were achieved. Sulfate dominated PM composition in vehicle configurations (V-SCRT^®-UDDS, Z-SCRT^®-Cruise, CRT^® and DPX) with considerable nucleation mode and TC was predominant for configurations with less (Z-SCRT^®-UDDS) or insignificant (CCRT^®, Horizon) nucleation. The transient operation increases EC emissions, consistent with its higher accumulation PM mode content. In general, solubility of organic carbon is higher (average ～5 times) for retrofitted vehicles than the baseline vehicle. The retrofitted vehicles with catalyzed filters (DPX, CCRT^®) had decreased OC solubility (WSOC/OC: 8–25%) unlike those with uncatalyzed filters (SCRT^®s, Horizon; WSOC/OC ～ 60–100%). Ammonium was present predominantly in the nucleation mode, indicating that ternary nucleation may be the responsible mechanism for formation of these particles.     

Metals emitted from heavy-duty diesel vehicles equipped with advanced PM and NOX emission controls

Emission factors for elemental metals were determined from several heavy-duty diesel vehicles (HDDV) of 1998–2007 vintage, operating with advanced PM and/or NO_X emissions control retrofits on a heavy-duty chassis dynamometer, under steady state cruise, transient, and idle conditions. The emission control retrofits included diesel particulate filters (DPF): catalyzed and uncatalyzed, passive and active prototype vanadium- or zeolite-based selective catalytic reduction (SCR) systems, and a catalyzed DPF fitted on a hybrid diesel electric drive vehicle. The prototype SCR systems in combination with DPF retrofits are of particular interest because they represent the expected emissions controls for compliance with PM and NO_X regulations in 2010. PM samples from a full-exhaust dilution tunnel were collected on bulk filters, and on a Personal Cascade Impactor Sampler (PCIS) for total and water-soluble elemental analysis. All the DPFs significantly reduced emissions of total trace elements (>85% and >95% for cruise and for the Urban Dynamometer Driving Schedule (UDDS), respectively). However, we observed differences in the post-retrofit metals emissions due to driving cycle effects (i.e., exhaust temperature) and type of retrofit. In general, the metals emissions over cruise conditions (which leads to higher exhaust temperatures) were substantially different from the emissions over a transient cycle or while idling. For instance, during cruise, we observed higher levels of platinum (1.1 ± 0.6–4.2 ± 3.6 ng km^?1) for most of the retrofit-equipped vehicle tests compared to the baseline configuration (0.3 ± 0.1 ng km^?1). The vanadium-based DPF + SCR vehicle during cruise operation exhibited emissions of vanadium (562 ± 265 ng km^?1) and titanium (5841 ± 3050 ng km^?1), suggesting the possible release of actual SCR wash-coat (V₂O₅/TiO₂) from the catalyst under the higher temperatures characteristic of cruise operation. The vanadium emissions exhibited a bi-modal mass size distribution, with modes at <0.25 μm and 1.0–2.5 μm size ranges for the vanadium-based SCR system. For the DPF + SCR systems, a greater fraction of the metal emissions from the zeolite-based system is water-soluble compared to emissions from the vanadium-based system.