Size and composition distributions of particulate matter emissions: part 2--heavy-duty diesel vehicles

Particulate matter (PM) emissions from heavy-duty diesel vehicles (HDDVs) were collected using a chassis dynamometer/dilution sampling system that employed filter-based samplers, cascade impactors, and scanning mobility particle size (SMPS) measurements. Four diesel vehicles with different engine and emission control technologies were tested using the California Air Resources Board Heavy Heavy-Duty Diesel Truck (HHDDT) 5 mode driving cycle. Vehicles were tested using a simulated inertial weight of either 56,000 or 66,000 lb. Exhaust particles were then analyzed for total carbon, elemental carbon (EC), organic matter (OM), and water-soluble ions. HDDV fine (< or =1.8 microm aerodynamic diameter; PM1.8) and ultrafine (0.056-0.1 microm aerodynamic diameter; PM0.1) PM emission rates ranged from 181-581 mg/km and 25-72 mg/km, respectively, with the highest emission rates in both size fractions associated with the oldest vehicle tested. Older diesel vehicles produced fine and ultrafine exhaust particles with higher EC/OM ratios than newer vehicles. Transient modes produced very high EC/OM ratios whereas idle and creep modes produced very low EC/OM ratios. Calcium was the most abundant water-soluble ion with smaller amounts of magnesium, sodium, ammonium ion, and sulfate also detected. Particle mass distributions emitted during the full 5-mode HDDV tests peaked between 100-180 nm and their shapes were not a function of vehicle age. In contrast, particle mass distributions emitted during the idle and creep driving modes from the newest diesel vehicle had a peak diameter of approximately 70 nm, whereas mass distributions emitted from older vehicles had a peak diameter larger than 100 nm for both the idle and creep modes. Increasing inertial loads reduced the OM emissions, causing the residual EC emissions to shift to smaller sizes. The same HDDV tested at 56,000 and 66,000 lb had higher PM0.1 EC emissions (+22%) and lower PM0.1 OM emissions (-38%) at the higher load condition.     

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.     

Morphology and composition of particles emitted from conventional and alternative fuel vehicles

Size, morphology, and composition of airborne particles strongly affect human health and visibility, precipitation, and the kinetic characteristics of particles. In this study, the morphology and chemical composition of particles emitted from conventional (diesel and gasoline) and alternative (CNG and methanol) fuel vehicles were characterized through scanning electron microscopy (SEM) and energy-dispersive X-ray (EDX). The SEM images revealed that the size of primary particles (without agglomeration) was approximately 10 nm in the exhaust from all the tested vehicles. The particles emitted from gasoline vehicle (GV), CNG vehicle (CNGV), and methanol vehicle (MV) had the same median diameter, 62 nm, which was smaller than those from heavy diesel vehicle (HDV) and light diesel vehicle (LDV). Soot was observed in the HDV, LDV, and GV samples but not in the CNGV and MV. The fractal dimension, which was used to quantify the degree of irregularity of soot, was 1.752 ± 0.014, 1.789 ± 0.076, and 1.769 ± 0.006 in the exhaust from HDV, LDV, and GV samples, respectively. The particles discharged by all tested vehicles contained the elements C, O, Fe, and Na. The main element in the samples of HDV, LDV, and GV was C, while O was the main element in the samples of alternative fuel vehicles. The profiles of minor elements were more complex in the emissions of alternative fuel vehicles than those in the emissions of conventional fuel vehicles. The results improved our understanding of the morphology and elemental composition of particles emitted from vehicles powered by diesel, gasoline, CNG, and methanol.

     

On-road measurement of fine particle and nitrogen oxide emissions from light- and heavy-duty motor vehicles

An updated assessment of fine particle emissions from light- and heavy-duty vehicles is needed due to recent changes to the composition of gasoline and diesel fuel, more stringent emission standards applying to new vehicles sold in the 1990s, and the adoption of a new ambient air quality standard for fine particulate matter (PM_2.5) in the United States. This paper reports the measurement of emissions from vehicles in a northern California roadway tunnel during summer 1997. Separate measurements were made of uphill traffic in two tunnel bores: one bore carried both light-duty vehicles and heavy-duty diesel trucks, and the second bore was reserved for light-duty vehicles. Ninety-eight percent of the light-duty vehicles were gasoline-powered. In the tunnel, heavy-duty diesel trucks emitted 24, 37, and 21 times more fine particle, black carbon, and sulfate mass per unit mass of fuel burned than light-duty vehicles. Heavy-duty diesel trucks also emitted 15–20 times the number of particles per unit mass of fuel burned compared to light-duty vehicles. Fine particle emissions from both vehicle classes were composed mostly of carbon; diesel-derived particulate matter contained more black carbon (51±11% of PM_2.5 mass) than did light-duty fine particle emissions (33±4%). Sulfate comprised only 2% of total fine particle emissions for both vehicle classes. Sulfate emissions measured in this study for heavy-duty diesel trucks are significantly lower than values reported in earlier studies conducted before the introduction of low-sulfur diesel fuel. This study suggests that heavy-duty diesel vehicles in California are responsible for nearly half of oxides of nitrogen emissions and greater than three-quarters of exhaust fine particle emissions from on-road motor vehicles.     

Evolution of vehicle exhaust particles in the atmosphere

Aerosol mass spectrometer (AMS) measurements are used to characterize the evolution of exhaust particulate matter (PM) properties near and downwind of vehicle sources. The AMS provides time-resolved chemically speciated mass loadings and mass-weighted size distributions of nonrefractory PM smaller than 1 microm (NRPM1). Source measurements of aircraft PM show that black carbon particles inhibit nucleation by serving as condensation sinks for the volatile and semi-volatile exhaust gases. Real-world source measurements of ground vehicle PM are obtained by deploying an AMS aboard a mobile laboratory. Characteristic features of the exhaust PM chemical composition and size distribution are discussed. PM mass and number concentrations are used with above-background gas-phase carbon dioxide (CO2) concentrations to calculate on-road emission factors for individual vehicles. Highly variable ratios between particle number and mass concentrations are observed for individual vehicles. NRPM1 mass emission factors measured for on-road diesel vehicles are approximately 50% lower than those from dynamometer studies. Factor analysis of AMS data (FA-AMS) is applied for the first time to map variations in exhaust PM mass downwind of a highway. In this study, above-background vehicle PM concentrations are highest close to the highway and decrease by a factor of 2 by 200 m away from the highway. Comparison with the gas-phase CO2 concentrations indicates that these vehicle PM mass gradients are largely driven by dilution. Secondary aerosol species do not show a similar gradient in absolute mass concentrations; thus, their relative contribution to total ambient PM mass concentrations increases as a function of distance from the highway. FA-AMS of single particle and ensemble data at an urban receptor site shows that condensation of these secondary aerosol species onto vehicle exhaust particles results in spatial and temporal evolution of the size and composition of vehicle exhaust PM on urban and regional scales.     

On-road and laboratory investigation of low-level PM emissions of a modern diesel particulate filter equipped diesel passenger car

Modern diesel particulate filter (DPF) systems are very effective in reducing particle emissions from diesel vehicles. In this work low-level particulate matter (PM) emissions from a DPF equipped EURO-4 diesel vehicle were studied in the emission test laboratory as well as during real-world chasing on a high-speed test track. Size and time resolved data obtained from an engine exhaust particle sizer (EEPS) and a condensation particle counter (CPC) are presented for both loaded and unloaded DPF condition. The corresponding time and size resolved emission factors were calculated for acceleration, deceleration, steady state driving and during DPF regeneration, and are compared with each other. In addition, the DPF efficiency of the tested vehicle was evaluated during the New European Driving Cycle (NEDC) by real time pre-/post-DPF measurements and was found to be 99.5% with respect to PM number concentration and 99.3% for PM mass, respectively. PM concentrations, which were measured at a distance of about 10 m behind the test car, ranged from 1 to 1.5 times background level when the vehicle was driven on the test track under normal acceleration conditions or at constant speeds below 100 kmh^?1. Only during higher speeds and full load accelerations concentrations above 3 times background level could be observed. The corresponding tests in the emission laboratory confirmed these results. During DPF regeneration the total PM number emission of nucleation mode particles was 3–4 orders of magnitude higher compared to those emitted at the same speed without regeneration, while the level of the accumulation mode particles remained about the same. The majority of the particles emitted during DPF regeneration was found to be volatile, and is suggested to originate from accumulated sulfur compounds.     

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.     

Volatile nanoparticle formation and growth within a diluting diesel car exhaust

A major source of particle number emissions is road traffic. However, scientific knowledge concerning secondary particle formation and growth of ultrafine particles within vehicle exhaust plumes is still very limited. Volatile nanoparticle formation and subsequent growth conditions were analyzed here to gain a better understanding of "real-world" dilution conditions. Coupled computational fluid dynamics and aerosol microphysics models together with measured size distributions within the exhaust plume of a diesel car were used. The impact of soot particles on nucleation, acting as a condensational sink, and the possible role of low-volatile organic components in growth were assessed. A prescribed reduction of soot particle emissions by 2 orders of magnitude (to capture the effect of a diesel particle filter) resulted in concentrations of nucleation-mode particles within the exhaust plume that were approximately 1 order of magnitude larger. Simulations for simplified sulfuric acid-water vapor gas-oil containing nucleation-mode particles show that the largest particle growth is located in a recirculation zone in the wake of the car. Growth of particles within the vehicle exhaust plume up to detectable size depends crucially on the relationship between the mass rate of gaseous precursor emissions and rapid dilution. Chassis dynamometer measurements indicate that emissions of possible hydrocarbon precursors are significantly enhanced under high engine load conditions and high engine speed. On the basis of results obtained for a diesel passenger car, the contributions from light diesel vehicles to the observed abundance of measured nucleation-mode particles near busy roads might be attributable to the impact of two different time scales: (1) a short one within the plume, marked by sufficient precursor emissions and rapid dilution; and (2) a second and comparatively long time scale resulting from the mix of different precursor sources and the impact of atmospheric chemistry.     

Identifying the effect of individual emissions sources on particulate air quality within a photochemical aerosol processes trajectory model

A procedure is demonstrated that greatly expands the number of sources whose contribution to ambient particle levels can be followed separately within an aerosol processes trajectory model without significantly increasing the computational burden of the problem. Particles emitted from different sources within the same general class can be differentiated from each other with this technique; for example particles emitted by on-road diesel vehicles can be distinguished from particles emitted by diesel railroad locomotives, and particles emitted from identical sources at different locations can be distinguished from each other as well. The method developed is illustrated by application to the air quality situation in Southern California. The contributions of more than 50 types of air pollution sources to primary particle concentrations at Claremont, CA, are separated from each other by post-processing the output from the aerosol processes trajectory model for an externally mixed aerosol developed previously by Kleeman and Cass (1998, Atmospheric Environment 32, 2803–2816; 1999 Environmental Science and Technology, 33, 177–189).     

Diesel emissions in Vienna

The aerosol in a non-industrial town normally is dominated by emissions from vehicles. Whereas gasoline-powered cars normally only emit a small amount of particulates, the emission by diesel-powered cars is considerable. The aerosol particles produced by diesel engines consist of graphitic carbon (GC) with attached hydrocarbons (HCs) including also polyaromatic HCs. Therefore the diesel particles can be carcinogenic. Besides diesel vehicles, all other combustion processes are also a source for GC; thus source apportionment of diesel emissions to the GC in the town is difficult.A direct apportionment of diesel emissions has been made possible by marking all the diesel fuel used by the vehicles in Vienna by a normally not occurring and easily detectable substance. All emitted diesel particles thus were marked with the tracer and by analyzing the atmospheric samples for the marking substance we found that the mass concentrations of diesel particles in the atmosphere varied between 5 and 23 μg m⁻³. Busy streets and calm residential areas show less difference in mass concentration than expected. The deposition of diesel particles on the ground has been determined by collecting samples from the road surface. The concentration of the marking substance was below the detection limit before the marking period and a year after the period. During the period when marked diesel fuel was used, the concentrations of the diesel particles settling to the ground was 0.012–0.07 g g⁻¹ of collected dust.A positive correlation between the diesel vehicle density and the sampled mass of diesel vehicles exists. In Vienna we have a background diesel particle concentration of 11 μg m⁻³. This value increases by 5.5 μg m⁻³ per 500 diesel vehicles h⁻¹ passing near the sampling location.The mass fraction of diesel particles of the total aerosol mass varied between 12.2 and 33%; the higher values were found in more remote areas, since diesel particles apparently diffuse easily.Estimates of diesel particle concentration by emission inventory or by using lead concentrations as an indicator for vehicle emissions gave similar values to those obtained in this study.Using available cancer risk data and diesel particle concentration found in this study, 1–2.6 additional lung cancers per 100,000 persons yr⁻¹ breathing diesel emissions in the measured concentration the whole lifetime can be expected.     

Factor analysis of submicron particle size distributions near a major United States-Canada trade bridge

A factor analytic model has been applied to resolve and apportion particles based on submicron particle size distributions downwind of a United States-Canada bridge in Buffalo, NY. The sites chosen for this study were located at gradually increasing distances downwind of the bridge complex. Seven independent factors were resolved, including four factors that were common to all of the five sites considered. The common factors were generally characterized by the existence of two or more number and surface area modes. The seven factors resolved were identified as follows: fresh tail-pipe diesel exhaust, local/street diesel traffic, aged/evolved diesel particles, spark-ignition gasoline emissions, background urban emissions, heavy-duty diesel agglomerates, and secondary/transported material. Submicron (<0.5 microm) and ultrafine (<0.1 microm) particle emissions downwind of the bridge were dominated by commercial diesel truck emissions. Thus, this study obtained size distinction between fresh versus aged vehicle exhaust and spark-ignition versus diesel emissions based on the measured high time-resolution particle number concentrations. Because this study mainly used particles <300 nm in diameter, some sources that would usually exhibit number modes >100 nm were not resolved. Also, the resolved profiles suggested that the major number mode for fresh tailpipe diesel exhaust might exist below the detection limit of the spectrometer used. The average particle number contributions from the resolved factors were highest closest to the bridge.     

A study of emissions from a Euro 4 light duty diesel vehicle with the European particulate measurement programme

The California Air Resources Board, CARB, has participated in a program to quantify particulate matter (PM) emissions with a European methodology, which is known as the Particulate Measurement Programme (PMP). The essence of the PMP methodology is that the diesel PM from a Euro 4 vehicle equipped with a Diesel Particulate Filter (DPF) consists primarily of solid particles with a size range greater than 23 nm. The PMP testing and the enhanced testing performed by CARB have enabled an increased understanding of both the progress that has been made in PM reduction, and the future remaining challenges for new and improved DPF-equipped diesel vehicles. A comparison of measured regulated emissions and solid particle number emissions with the results obtained by the PMP participating international laboratories was a success, and CARB’s measurements and standard deviations compared well with the other laboratories. Enhanced measurements of the influence of vehicle conditioning prior to testing on PM mass and solid particle number results were performed, and some significant influences were discovered. For example, the influence of vehicle preconditioning on particle number results was significant for both the European and USA test driving cycles. However, the trends for the cycles were opposite with one cycle showing an increase and the other cycle showing a decrease in particle number emissions. If solid particle size distribution and total particle numbers are to be used as proposed in PMP, then a greater understanding of the quality and errors associated with measurement technologies is advisable.In general, particle counting instruments gave results with similar trends, but cycle-to-cycle testing variation was observed. Continuous measurements of particle number concentrations during test cycles have given detailed insight into PM generation. At the present time there is significant variation in the capabilities of the particle counting instruments in terms of particle size and concentration.Current measurements show the existence of a large number of volatile and semi-volatile particles of yet-to-be-resolved chemical composition in diesel exhaust, especially during DPF regeneration, and these particles are not included in the PMP methodology because they are smaller than 20 nm. It will be very challenging to improve our understanding of this class of diesel particulate matter.     

Particulate organic compounds emitted from motor vehicle exhaust and in the urban atmosphere

The emission rate of particle-phase petroleum biomarkers in vehicular exhaust compared to the concentrations of these biomarkers in ambient air is used to determine the particulate organic compound concentration due to primary particle emissions from motor vehicles in the southern California atmosphere. A material balance on the organic particulate matter emitted from motor vehicle traffic in a Los Angeles highway tunnel first is constructed to show the proportion which is solvent-extractable and which will elute from a GC column, the ratio of resolved to unresolved compound mass, the portion of the resolved material that can be identified as single organic compounds, and the contribution of different classes of organic compounds to the overall identified fraction. It is shown that the outdoor ambient concentrations of the petroleum biomarkers track primary emissions measured in the highway tunnel, confirming that direct emissions of these compounds from vehicles govern the observed ambient petroleum biomarker concentrations. Using organic chemical tracer techniques, the portion of fine organic particulate matter in the Los Angeles atmosphere which is attributable to direct particle emissions from vehicle exhaust is calculated to vary from 7.5 to 18.3% at different sites throughout the air basin during a summertime severe photochemical smog episode. A similar level of variation in the contribution of primary motor vehicle exhaust to fine particulate organic matter concentrations during different times of day is seen. While peak atmospheric concentrations of fine particulate organic carbon are observed during the 1200–1600 PDT afternoon sampling period, only 6.3% of that material is apportioned to the directly emitted particles from vehicle exhaust. During the morning traffic peak between 0600–1000 PDT, 19.1% of the fine particulate organic material is traced to primary emissions from motor vehicles.     

Characterisation of single particles from in-port ship emissions

Emissions from shipping traffic may impact severely upon air quality in port cities. In this study, the size and composition of freshly emitted individual ship exhaust particles has been investigated using an aerosol time-of-flight mass spectrometer (ATOFMS) co-located with a suite of real-time instrumentation at a site in the Port of Cork, Ireland. The collected spectra were clustered using the K-means algorithm and a unique ship exhaust class containing internally mixed elemental and organic carbon, sodium, calcium, iron, vanadium, nickel and sulfate was identified. Over twenty sharp emission events were observed for this particle type during the three week measurement period in August 2008. Coincident increases in mass concentrations of sulfate, elemental carbon and particles below 2.5 μm in diameter (PM_2.5) were also observed during these events. Simultaneous scanning mobility particle sizer (SMPS) measurements indicate that the vast majority of freshly emitted ship exhaust particles lie in the ultrafine mode (<100 nm diameter). A second particle class consisted of internally mixed organic carbon, elemental carbon, ammonium and sulfate, and is tentatively attributed to aged or regionally transported ship exhaust. The results suggest that ATOFMS single particle mass spectra, when used in conjunction with other air quality monitoring instrumentation, may be useful in determining the contribution of local shipping traffic to air quality in port cities.     

Effects of water-emulsified fuel on a diesel engine generator’s thermal efficiency and exhaust

Water-emulsified diesel has proven itself as a technically sufficient improvement fuel to improve diesel engine fuel combustion emissions and engine performance. However, it has seldom been used in light-duty diesel engines. Therefore, this paper focuses on an investigation into the thermal efficiency and pollution emission analysis of a light-duty diesel engine generator fueled with different water content emulsified diesel fuels (WD, including WD-0, WD-5, WD-10, and WD-15). In this study, nitric oxide, carbon monoxide, hydrocarbons, and carbon dioxide were analyzed by a vehicle emission gas analyzer, and the particle size and number concentration were measured by an electrical low-pressure impactor. In addition, engine loading and fuel consumption were also measured to calculate the thermal efficiency. Measurement results suggested that water-emulsified diesel was useful to improve the thermal efficiency and the exhaust emission of a diesel engine. Obviously, the thermal efficiency was increased about 1.2 to 19.9%. In addition, water-emulsified diesel leads to a significant reduction of nitric oxide emission (less by about 18.3 to 45.4%). However, the particle number concentration emission might be increased if the loading of the generator becomes lower than or equal to 1800 W. In addition, exhaust particle size distributions were shifted toward larger particles at high loading. The consequence of this research proposed that the water-emulsified diesel was useful to improve the engine performance and some of exhaust emissions, especially the NO emission reduction.

Implications:The accumulated test results provide a good basis to resolve the corresponding pollutants emitted from a light-duty diesel engine generator. By measuring and analyzing transforms of exhaust pollutant from this engine generator, the effects of water-emulsified diesel fuel and loading on emission characteristics might be more clear. Understanding reduction of pollutant emissions during the use of water-emulsified diesel helps improve the effectiveness of the testing program. The analyzed consequences provide useful information to the government for setting policies to curb pollutant emissions from a light-duty diesel engine generator more effectively.     

Regulated and unregulated emissions from highway heavy-duty diesel engines complying with U.S. Environmental Protection Agency 2007 emissions standards

As part of the Advanced Collaborative Emissions Study (ACES), regulated and unregulated exhaust emissions from four different 2007 model year U.S. Environmental Protection Agency (EPA)-compliant heavy-duty highway diesel engines were measured on an engine dynamometer. The engines were equipped with exhaust high-efficiency catalyzed diesel particle filters (C-DPFs) that are actively regenerated or cleaned using the engine control module. Regulated emissions of carbon monoxide, nonmethane hydrocarbons, and particulate matter (PM) were on average 97, 89, and 86% lower than the 2007 EPA standard, respectively, and oxides of nitrogen (NOx) were on average 9% lower. Unregulated exhaust emissions of nitrogen dioxide (NO2) emissions were on, average 1.3 and 2.8 times higher than the NO, emissions reported in previous work using 1998- and 2004-technology engines, respectively. However, compared with other work performed on 1994- to 2004-technology engines, average emission reductions in the range of 71-99% were observed for a very comprehensive list of unregulated engine exhaust pollutants and air toxic contaminants that included metals and other elements, elemental carbon (EC), inorganic ions, and gas- and particle-phase volatile and semi-volatile organic carbon (OC) compounds. The low PM mass emitted from the 2007 technology ACES engines was composed mainly of sulfate (53%) and OC (30%), with a small fraction of EC (13%) and metals and other elements (4%). The fraction of EC is expected to remain small, regardless of engine operation, because of the presence of the high-efficiency C-DPF in the exhaust. This is different from typical PM composition of pre-2007 engines with EC in the range of 10-90%, depending on engine operation. Most of the particles emitted from the 2007 engines were mainly volatile nuclei mode in the sub-30-nm size range. An increase in volatile nanoparticles was observed during C-DPF active regeneration, during which the observed particle number was similar to that observed in emissions of pre-2007 engines. However, on average, when combining engine operation with and without active regeneration events, particle number emissions with the 2007 engines were 90% lower than the particle number emitted from a 2004-technology engine tested in an earlier program.     

Characterisation of particulate matter and gaseous emissions from a large ship diesel engine

Composition of exhaust from a ship diesel engine using heavy fuel oil (HFO) was investigated onboard a large cargo vessel. The emitted particulate matter (PM) properties related to environmental and health impacts were investigated along with composition of the gas-phase emissions. Mass, size distribution, chemical composition and microphysical structure of the PM were investigated. The emission factor for PM was 5.3 g (kg fuel)^?1. The mass size distribution showed a bimodal shape with two maxima: one in the accumulation mode with mean particle diameter D_P around 0.5 μm and one in the coarse mode at D_P around 7 μm. The PM composition was dominated by organic carbon (OC), ash and sulphate while the elemental carbon (EC) composed only a few percent of the total PM. Increase of the PM in exhaust upon cooling was associated with increase of OC and sulphate. Laser analysis of the adsorbed phase in the cooled exhaust showed presence of a rich mixture of polycyclic aromatic hydrocarbon (PAH) species with molecular mass 178–300 amu while PM collected in the hot exhaust showed only four PAH masses.Microstructure and elemental analysis of ship combustion residuals indicate three distinct morphological structures with different chemical composition: soot aggregates, significantly metal polluted; char particles, clean or containing minerals; mineral and/or ash particles. Additionally, organic carbon particles of unburned fuel or/and lubricating oil origin were observed. Hazardous constituents from the combustion of heavy fuel oil such as transitional and alkali earth metals (V, Ni, Ca, Fe) were observed in the PM samples.Measurements of gaseous composition in the exhaust of this particular ship showed emission factors that are on the low side of the interval of global emission factors published in literature for NO_x, hydrocarbons (HC) and CO.     

SARA Title III,Section 313 —Looking Ahead

This study performed a workplace evaluation of emission control using available air sampling filters and characterized the emitted particles captured in filters. Characterized particles were contained in the exhaust gas released from carbon nanotube (CNT) synthesis using chemical vapor deposition (CVD). Emitted nanoparticles were collected on grids to be analyzed using transmission electron microscopy (TEM). CNT clusters in the exhaust gas were collected on filters for investigation. Three types of filters, including Nalgene surfactant-free cellulose acetate (SFCA), Pall A/E glass fiber, and Whatman QMA quartz filters, were evaluated as emission control measures, and particles deposited in the filters were characterized using scanning transmission electron microscopy (STEM) to further understand the nature of particles emitted from this CNT production. STEM analysis for collected particles on filters found that particles deposited on filter fibers had a similar morphology on all three filters, that is, hydrophobic agglomerates forming circular beaded clusters on hydrophilic filter fibers on the collecting side of the filter. CNT agglomerates were found trapped underneath the filter surface. The particle agglomerates consisted mostly of elemental carbon regardless of the shapes. Most particles were trapped in filters and no particles were found in the exhaust downstream from A/E and quartz filters, while a few nanometer-sized and submicrometer-sized individual particles and filament agglomerates were found downstream from the SFCA filter. The number concentration of particles with diameters from 5 nm to 20 µm was measured while collecting particles on grids at the exhaust piping. Total number concentration was reduced from an average of 88,500 to 700 particle/cm³ for the lowest found for all filters used. Overall, the quartz filter showed the most consistent and highest particle reduction control, and exhaust particles containing nanotubes were successfully collected and trapped inside this filter.

Implications: As concern for the toxicity of engineered nanoparticles grows, there is a need to characterize emission from carbon nanotube synthesis processes and to investigate methods to prevent their environmental release. At this time, the particles emitted from synthesis were not well characterized when collected on filters, and limited information was available about filter performance to such emission. This field study used readily available sampling filters to collect nanoparticles from the exhaust gas of a carbon nanotube furnace. New agglomerates were found on filters from such emitted particles, and the performance of using the filters studied was encouraging in terms of capturing emissions from carbon nanotube synthesis.     

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.     

Dilution-based emissions sampling from stationary sources: Part 2--Gas-fired combustors compared with other fuel-fired systems

With the recent focus on fine particle matter (PM2.5), new, self-consistent data are needed to characterize emissions from combustion sources. Such data are necessary for health assessment and air quality modeling. To address this need, emissions data for gas-fired combustors are presented here, using dilution sampling as the reference. The dilution method allows for collection of emitted particles under conditions simulating cooling and dilution during entry from the stack into the air. The sampling and analysis of the collected particles in the presence of precursor gases, SO2 nitrogen oxide, volatile organic compound, and NH3 is discussed; the results include data from eight gas fired units, including a dual-fuel institutional boiler and a diesel engine powered electricity generator. These data are compared with results in the literature for heavy-duty diesel vehicles and stationary sources using coal or wood as fuels. The results show that the gas-fired combustors have very low PM2.5 mass emission rates in the range of approximately 10(-4) lb/million Btu (MMBTU) compared with the diesel backup generator with particle filter, with approximately 5 x 10(-3) lb/MMBTU. Even higher mass emission rates are found in coal-fired systems, with rates of approximately 0.07 lb/MMBTU for a bag-filter-controlled pilot unit burning eastern bituminous coal. The characterization of PM2.5 chemical composition from the gas-fired units indicates that much of the measured primary particle mass in PM2.5 samples is organic or elemental carbon and, to a much less extent, sulfate. Metal emissions are quite low compared with the diesel engines and the coal- or wood-fueled combustors. The metals found in the gas-fired combustor particles are low in concentration, similar in concentration to ambient particles. The interpretation of the particulate carbon emissions is complicated by the fact that an approximately equal amount of particulate carbon (mainly organic carbon) is found on the particle collector and a backup filter. It is likely that measurement artifacts, mostly adsorption of volatile organic compounds on quartz filters, are positively biasing "true" particulate carbon emission results.