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.     

Evaluations of the chemical mass balance method for determining contributions of gasoline and diesel exhaust to ambient carbonaceous aerosols

The US. Department of Energy Gasoline/Diesel PM Split Study was conducted to assess the sources of uncertainties in using an organic compound-based chemical mass balance receptor model to quantify the relative contributions of emissions from gasoline (or spark ignition [SI]) and diesel (or compression ignition [CI]) engines to ambient concentrations of fine particulate matter (PM2.5) in California's South Coast Air Basin (SOCAB). In this study, several groups worked cooperatively on source and ambient sample collection and quality assurance aspects of the study but worked independently to perform chemical analysis and source apportionment. Ambient sampling included daily 24-hr PM2.5 samples at two air quality-monitoring stations, several regional urban locations, and along freeway routes and surface streets with varying proportions of automobile and truck traffic. Diesel exhaust was the dominant source of total carbon (TC) and elemental carbon (EC) at the Azusa and downtown Los Angeles, CA, monitoring sites, but samples from the central part of the air basin showed nearly equal apportionments of CI and SI. CI apportionments to TC were mainly dependent on EC, which was sensitive to the analytical method used. Weekday contributions of CI exhaust were higher for Interagency Monitoring of Protected Visual Environments (IMPROVE; 41+/-3.7%) than Speciation Trends Network (32+/-2.4%). EC had little effect on SI apportionment. SI apportionments were most sensitive to higher molecular weight polycyclic aromatic hydrocarbons (indeno[123-cd]pyrene, benzo(ghi)perylene, and coronene) and several steranes and hopanes, which were associated mainly with high emitters. Apportionments were also sensitive to choice of source profiles. CI contributions varied from 30% to 60% of TC when using individual source profiles rather than the composites used in the final apportionments. The apportionment of SI vehicles varied from 1% to 12% of TC depending on the specific profile that was used. Up to 70% of organic carbon (OC) in the ambient samples collected at the two fixed monitoring sites could not be apportioned to directly emitted PM emissions.     

Chemical characterization of fine particles from on-road vehicles in the Wutong tunnel in Shenzhen, China

Vehicle populations in China have been increasing sharply since 1990s. Vehicle emissions including various gaseous pollutants and particulate matter cause deterioration of air quality. However, measurements of particulate mater from on-road vehicles in China are scarcely reported, and thus the chemical compositions of particles emitted from vehicles in China are unknown. In this research, tunnel experiments were performed to measure PM2.5 in the Wutong tunnel, Shenzhen, China. Detailed PM2.5 chemical compositions, with organic compounds determined by GC/MS, in the tunnel were presented. Elemental carbon and organic matter composed 63% and 34% of the total PM2.5 mass in the Wutong tunnel, respectively. Alkanes, PAHs, hopanes, fatty acids, and dicarboxylic acids were the major identified organic compounds, and their source profiles in the PM2.5 in the Wutong tunnel were characterized. The comparisons of our measurements with those in the literature were also made to demonstrate the characteristics of the vehicle source profiles in the Wutong tunnel. The experimental results in this paper can improve understanding of particulate matter emitted from vehicles in China.     

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.     

Characterisation and determination of profiles of polycyclic aromatic hydrocarbons in a traffic tunnel in Gothenburg, Sweden

The concentrations of semi-volatile polycyclic aromatic hydrocarbons (PAHs), hydrocarbons (HCs), particulate matter (PM 1, 2.5 and 10 μm) and total suspended particles (TSPs) were measured in a traffic tunnel in Gothenburg, Sweden. Emission factors (EFs) were also calculated. These variables are assumed to provide good estimates of average vehicle emissions, since all types of vehicle, using all types of fuel, pass through this tunnel. It was shown that the majority of particle-associated PAHs were found on particles with an aerodynamic diameter of <1 μm. The concentrations of PAHs were one order higher in magnitude in air samples from the tunnel than in air samples at two urban locations. However, the PAH profiles of air samples from the tunnel and the urban sites were similar. This was demonstrated using principal component analysis (PCA). Finally, and notably, there was no significant change in the total emissions when the proportion of heavy-duty vehicles (HDVs) increased from 8% to 24%. Previously, diesel vehicles had been found to release larger quantities of PAHs and related substances. Advances in fuel quality, and HDV motor and exhaust system design during the last decade may have contributed to this promising result. However, it was shown, using partial least squares regression to latent structures (PLS), that some of the parameters measured displayed correlations with the proportions of HDVs and light-duty vehicles (LDVs). Concentrations of total HCs, TSPs, dibenzothiopene, phenantrene, anthracene and monomethyl-derivatives of phenantrene and anthracene were all correlated to the proportion of HDVs. The concentrations of naphthalene, some mono- and dimethylnaphthalenes and most large PAHs (with 5–7 fused rings) were correlated to the proportion of LDVs.     

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.     

Time-series analysis of above-road particulate matter at the Caldecott Tunnel exit

On November 18, 1997, above-road particulate matter (PM) lidar (light detection and ranging) signals and heavy-duty (HD) and light-duty (LD) vehicle counts were simultaneously collected for 894 10-sec sampling periods at the Caldecott Tunnel in Orinda, CA, for the purpose of measuring the relative contributions of LD and HD vehicles to the PM lidar signal under real-world driving conditions. The relationship between the PM lidar signal and traffic activity (i.e., LD and HD traffic volumes) was examined using a time-series analysis technique, multilagged regression. The time-series model results indicate that the PM lidar signal in the current sampling period (PMt) depended on the level recorded in the previous three sampling periods (i.e., PMt-1, PMt-2, and PMt-3), the number of LD vehicles in the seventh past sampling period (LDt-7), and the number of HD vehicles measured 80 sec previous to the current sampling period (HDt-8). On a 10-sec period basis, the model results indicate that HD vehicles contributed, on average, 3 times more to above-road PM lidar signals than did LD vehicles. The observed lag in the relationship between vehicle types and the lidar signal 20 m above the road suggests that resuspended road dust, rather than tailpipe exhaust emissions, was the main source of the detected PM. Detection of road dust at such heights above the road suggests the need for investigating the processes governing the vertical transport and recycling of PM over the road as a function of vehicle dynamics under a range of meteorological conditions.     

Measurements of ultrafine particles and other vehicular pollutants inside a mobile exposure system on Los Angeles freeways

A mobile exposure and air pollution measurement system was developed and used for on-freeway ultrafine particle health effects studies. A nine-passenger van was modified with a high-efficiency particulate air (HEPA) filtration system that can deliver filtered or unfiltered air to an exposure chamber inside the van. State-of-the-art instruments were used to measure concentration and size distribution of fine and ultrafine particles and the concentration of carbon monoxide (CO), black carbon (BC), particle-bound polycyclic aromatic hydrocarbons (PAHs), fine particulate matter (PM2.5) mass, and oxides of nitrogen (NOx) inside the exposure chamber. This paper presents the construction and technical details of the van and air pollutant concentrations collected in 32 2-hr runs on two major Los Angeles freeways, Interstate 405 (1-405; mostly gasoline traffic) and Interstate 710 (1-710; large proportion of heavy-duty diesel traffic). More than 97% of particles were removed when the flow through the filter box was switched from bypass mode to filter mode while the vehicle was driving on both freeways. The filtration system thus provides a great particulate matter exposure contrast while keeping gas-phase pollutant concentrations the same. Under bypass mode, average total particle number concentration observed inside the exposure chamber was around 8.4 x 10(4) and 1.3 x 10(5) particles cm(-3) on the I-405 and the I-710 freeways, respectively. Bimodal size distributions were consistent and similar for both freeways with the first mode around 16-20 nm and the second mode around 50-55 nm. BC and particle-bound PAH concentrations were more than two times greater on the I-710 than on the I-405 freeway. Very weak correlations were observed between total particle number concentrations and other vehicular pollutants on the freeways.     

Multiple-year black carbon measurements and source apportionment using delta-C in Rochester, New York

Black carbon (BC), an important component ofthe atmospheric aerosol, has climatic, environmental, and human health significance. In this study, BC was continuously measured using a two-wavelength aethalometer (370 nm and 880 nm) in Rochester; New York, from January 2007 to December 2010. The monitoring site is adjacent to two major urban highways (I-490 and I-590), where 14% to 21% of the total traffic was heavy-duty diesel vehicles. The annual average BC concentrations were 0.76 microg/m3, 0.67 microg/m3, 0.60 microg/m3, and 0.52 microg/m3 in 2007, 2008, 2009, and 2010, respectively. Positive matrix factorization (PMF) modeling was performed using PM2.5 elements, sulfate, nitrate, ammonia, elemental carbon (EC), and organic carbon (OC) data from the US. Environmental Protection Agency (EPA) speciation network and Delta-C (UVBC370nm-BC880nm) data. Delta-C has been previously shown to be a tracer of wood combustion factor It was used as an input variable in source apportionment models for the first time in this study and was found to play an important role in separating traffic (especially diesel) emissions from wood combustion emissions. The result showed the annual average PM2.5 concentrations apportioned to diesel emissions in 2007, 2008, 2009, and 2010 were 1.34 microg/m3, 1.25 microg/m3, 1.13 microg/m3, and 0.97 microg/m3, respectively. The BC conditional probability function (CPF) plots show a large contribution from the highway diesel traffic to elevated BC concentrations. The measurements and modeling results suggest an impact of the US Environmental Protection Agency (EPA) 2007 Heavy-Duty Highway Rule on the decrease ofBC and PM2.5 concentrations during the study period.     

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.     

Idle Emissions from Heavy-Duty Diesel and Natural Gas Vehicles at High Altitude

ABSTRACT

Idle emissions of total hydrocarbon (THC), CO, NO_x, 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 NO_x, and 0.030 g/min PM. Diesel buses averaged 0.137 g/min THC, 1.326 g/min CO, 2.015 g/min NO_x, 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 NO_x emissions were significantly higher (30-100%) than model predictions. For the pre-1999 (pre-consent decree) truck engines examined in this study, idle NO_x emissions increased with Health and Environment; June 30, 1999 (available from the authors).     

Air pollutant concentrations near three Texas roadways, part II: Chemical characterization and transformation of pollutants

Spatial gradients of vehicular emitted air pollutants were measured in the vicinity of three roadways in the Austin, Texas area: (1) State Highway 71 (SH-71), a heavily traveled arterial highway dominated by passenger vehicles; (2) Interstate 35 (I-35), a limited access highway north of Austin in Georgetown; and (3) Farm to Market Road 973 (FM-973), a heavily traveled surface roadway with significant truck traffic. A mobile monitoring platform was used to characterize the gradients of CO and NO_x concentrations with increased distance from each roadway, while concentrations of carbonyls in the gas-phase and fine particulate matter mass and composition were measured at stationary sites upwind and at one (I-35 and FM-973) or two (SH-71) downwind sites. Regardless of roadway type or wind direction, concentrations of carbon monoxide (CO), nitric oxide (NO), and oxides of nitrogen (NO_x) returned to background levels within a few hundred meters of the roadway. Under perpendicular wind conditions, CO, NO and NO_x concentrations decreased exponentially with increasing distance perpendicular to the roadways. The decay rate for NO was more than a factor of two greater than for CO, and it comprised a larger fraction of NO_x closer to the roadways than further downwind suggesting the potential significance of near roadway chemical processing as well as atmospheric dilution. Concentrations of most carbonyl species decreased with distance downwind of SH-71. However, concentrations of acetaldehyde and acrolein increased farther downwind of SH-71, suggesting chemical generation from the oxidation of primary vehicular emissions. The behavior of particle-bound organic species was complex and further investigation of the size-segregated chemical composition of particulate matter (PM) at increasing downwind distances from roadways is warranted. Fine particulate matter (PM_2.5) mass concentrations, polycyclic aromatic hydrocarbons (PAHs), hopanes, and elemental carbon (EC) concentrations generally exhibited concentrations that decreased with distance downwind of SH-71. Concentrations of organic carbon (OC) increased from upwind concentrations immediately downwind of SH-71 and continued to increase further downwind from the roadway. This behavior may have primarily resulted from condensation of semi-volatile organic species emitted from vehicle sources with transport downwind of the roadway.     

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.     

Emissions from charbroiling and grilling of chicken and beef

Emission rates for fine particle (<2.5 microm) mass (PM2.5), carbon (organic/elemental), inorganic ions (SO4(2-), NO3-, NH4+), elements (primarily metals), and speciated organic compounds are reported for charbroiling hamburger, steak, and chicken. The PM2.5 rates for charbroiling meats ranged from 4.4 to 11.6 g/kg of uncooked meat in this study. No mass-emission rates are available from grilling, but the speciated organic data are available for these samples. Emission rates varied by type of appliance, meat, meat-fat content, and cooking conditions. High-fat hamburger cooked on an underfired charbroiler emitted the highest amount of PM2.5. The emissions were almost exclusively composed of organic carbon, with small amounts of elements and inorganic ions. Water-soluble K+ and Cl-, which are used as indicators of wood smoke in source apportionment studies, were also present in meat-cooking emissions. The speciated organic compounds that were measured include polycyclic aromatic hydrocarbons (PAHs), cholesterol, and the long-chain gamma-lactones. Charbroiling emissions yielded an average of approximately 3-5 times more PAHs, approximately 20 times more cholesterol, and approximately 10 times more lactones than grilling. These data were utilized in the ambient source apportionment analysis for the 1997 Northern Front Range Air Quality Study source apportionment.     

Regulated and unregulated emissions from modern 2010 emissions-compliant heavy-duty on-highway diesel engines

The U.S. Environmental Protection Agency (EPA) established strict regulations for highway diesel engine exhaust emissions of particulate matter (PM) and nitrogen oxides (NO_x) to aid in meeting the National Ambient Air Quality Standards. The emission standards were phased in with stringent standards for 2007 model year (MY) heavy-duty engines (HDEs), and even more stringent NO_X standards for 2010 and later model years. The Health Effects Institute, in cooperation with the Coordinating Research Council, funded by government and the private sector, designed and conducted a research program, the Advanced Collaborative Emission Study (ACES), with multiple objectives, including detailed characterization of the emissions from both 2007- and 2010-compliant engines. The results from emission testing of 2007-compliant engines have already been reported in a previous publication. This paper reports the emissions testing results for three heavy-duty 2010-compliant engines intended for on-highway use. These engines were equipped with an exhaust diesel oxidation catalyst (DOC), high-efficiency catalyzed diesel particle filter (DPF), urea-based selective catalytic reduction catalyst (SCR), and ammonia slip catalyst (AMOX), and were fueled with ultra-low-sulfur diesel fuel (~6.5 ppm sulfur). Average regulated and unregulated emissions of more than 780 chemical species were characterized in engine exhaust under transient engine operation using the Federal Test Procedure cycle and a 16-hr duty cycle representing a wide dynamic range of real-world engine operation. The 2010 engines’ regulated emissions of PM, NO_X, nonmethane hydrocarbons, and carbon monoxide were all well below the EPA 2010 emission standards. Moreover, the unregulated emissions of polycyclic aromatic hydrocarbons (PAHs), nitroPAHs, hopanes and steranes, alcohols and organic acids, alkanes, carbonyls, dioxins and furans, inorganic ions, metals and elements, elemental carbon, and particle number were substantially (90 to >99%) lower than pre-2007-technology engine emissions, and also substantially (46 to >99%) lower than the 2007-technology engine emissions characterized in the previous study.

Implications:?Heavy-duty on-highway diesel engines equipped with DOC/DPF/SCR/AMOX and fueled with ultra-low-sulfur diesel fuel produced lower emissions than the stringent 2010 emission standards established by the U.S. Environmental Protection Agency. They also resulted in significant reductions in a wide range of unregulated toxic emission compounds relative to older technology engines. The increased use of newer technology (2010+) diesel engines in the on-highway sector and the adaptation of such technology by other sectors such as nonroad, displacing older, higher emissions engines, will have a positive impact on ambient levels of PM, NOx, and volatile organic compounds, in addition to many other toxic compounds.     

Concentrations of aliphatic and polycyclic aromatic hydrocarbons in ambient PM2.5 and PM10 particulates in Doha,Qatar

Organic carbon (OC), elemental carbon (EC), and 90 organic compounds (36 polycyclic aromatic hydrocarbons [PAHs], 25 n-alkane homologues, 17 hopanes, and 12 steranes) were concurrently quantified in atmospheric particulate matter of PM_2.5 and PM₁₀. The 24-hr PM samples were collected using Harvard Impactors at a suburban site in Doha, Qatar, from May to December 2015. The mass concentrations (mean ± standard deviation) of PM_2.5 and PM₁₀ were 40 ± 15 and 145 ± 70 µg m^?3, respectively, exceeding the World Health Organization (WHO) air quality guidelines. Coarse particles comprised 70% of PM₁₀. Total carbonaceous contents accounted for 14% of PM_2.5 and 10% of PM₁₀ particulate mass. The major fraction (90%) of EC was associated with the PM_2.5. In contrast, 70% of OC content was found in the PM_2.5–10 fraction. The secondary OC accounted for 60–68% of the total OC in both PM fractions, indicating photochemical conversions of organics are much active in the area due to higher air temperatures and solar radiations. Among the studied compounds, n-alkanes were the most abundant group, followed by PAHs, hopanes, and steranes. n-Alkanes from C₂₅ to C₃₅ prevailed with a predominance of odd carbon numbered congeners (C₂₇–C₃₁). High-molecular-weight PAHs (5–6 rings) also prevailed, within their class, with benzo[b + j]fluoranthene (Bb + jF) being the dominant member. PAHs were mainly (80%) associated with the PM_2.5 fraction. Local vehicular and fugitive emissions were predominant during low-speed southeasterly winds from urban areas, while remote petrogenic/biogenic emissions were particularly significant under prevailing northwesterly wind conditions.

Implications: An unprecedented study in Qatar established concentration profiles of EC, OC, and 90 organic compounds in PM_2.5 and PM₁₀. Multiple tracer organic compounds for each source can be used for convincing source apportionment. Particle concentrations exceeded WHO air quality guidelines for 82–96% of the time, revealing a severe problem of atmospheric PM in Doha. Dominance of EC and PAHs in fine particles signifies contributions from combustion sources. Dependence of pollutants concentrations on wind speed and direction suggests their significant temporal and spatial variability, indicating opportunities for improving the air quality by identifying sources of airborne contaminants.     

Large PAHs detected in fine particulate matter emitted from light-duty gasoline vehicles

Emission factors of large PAHs with 6–8 aromatic rings with molecular weights (MW) of 300–374 were measured from 16 light-duty gasoline-powered vehicles (LDGV) and one heavy-duty diesel-powered vehicle (HDDV) operated under realistic driving conditions. LDGVs emitted PAH isomers of MW 302, 326, 350, and 374, while the HDDV did not emit these compounds. This suggests that large PAHs may be useful tracers for the source apportionment of gasoline-powered motor vehicle exhaust in the atmosphere. Emission rates of MW 302, 326, and 350 isomers from LDGVs equipped with three-way catalysts (TWCs) ranged from 2 to 10 (μg L⁻¹ fuel burned), while emissions from LDGVs classified as low emission vehicles (LEVs) were almost a factor of 10 lower. MW 374 PAH isomers were not quantified due to the lack of a quantification-grade standard. The reduced emissions associated with the LEVs are likely attributable to improved vapor recovery during the “cold-start” phase of the Federal Test Procedure (FTP) driving cycle before the catalyst reaches operating temperature. Approximately 2 (μg g⁻¹ PM) of MW 326 and 350 PAH isomer groups were found in the National Institute of Standards and Technology standard reference material (SRM)#1649 (Urban Dust). The pattern of the MW 302, 326, and 350 isomers detected in SRM#1649 qualitatively matched the ratio of these compounds detected in the exhaust of TWC LDGVs suggesting that each gram of Urban Dust SRM contained 5–10 mg of PM originally emitted from gasoline-powered motor vehicles.Large PAHs made up 24% of the total LEV PAH emissions and 39% of the TWC PAH emissions released from gasoline-powered motor vehicles. Recent studies have shown certain large PAH isomers have greater toxicity than benzo[a]pyrene. Even though the specific toxicity measurements on PAHs with MW >302 have yet to be performed, the detection of significant amounts of MW 326 and 350 PAHs in motor vehicle exhaust in the current study suggests that these compounds may pose a significant public health risk.     

Time-Series Analysis of Above-Road Particulate Matter at the Caldecott Tunnel Exit

ABSTRACT

On November 18, 1997, above-road particulate matter (PM) lidar (light detection and ranging) signals and heavy-duty (HD) and light-duty (LD) vehicle counts were simultaneously collected for 894 10-sec sampling periods at the Caldecott Tunnel in Orinda, CA, for the purpose of measuring the relative contributions of LD and HD vehicles to the PM lidar signal under real-world driving conditions. The relationship between the PM lidar signal and traffic activity (i.e., LD and HD traffic volumes) was examined using a time-series analysis technique, multilagged regression. The time-series model results indicate that the PM lidar signal in the current sampling period (PM_t) depended on the level recorded in the previous three sampling periods (i.e., PM_t-1, PM_t-2, and PM_t-3), the number of LD vehicles in the seventh past sampling period (LD_t-7), and the number of HD vehicles measured 80 sec previous to the current sampling period (HD_t-8). On a 10-sec period basis, the model results indicate that HD vehicles contributed, on average, 3 times more to above-road PM li-dar signals than did LD vehicles. The observed lag in the relationship between vehicle types and the lidar signal 20 m above the road suggests that resuspended road dust, rather than tailpipe exhaust emissions, was the main source of the detected PM. Detection of road dust at such heights above the road suggests the need for investigating the processes governing the vertical transport and recycling of PM over the road as a function of vehicle dynamics under a range of meteorological conditions.     

Sensitivity of source apportionment of urban particulate matter to uncertainty in motor vehicle emissions profiles

A sensitivity analysis was conducted to characterize sources of uncertainty in results of a molecular marker source apportionment model of ambient particulate matter using mobile source emissions profiles obtained as part of the Gasoline/Diesel PM Split Study. A chemical mass balance (CMB) model was used to determine source contributions to samples of fine particulate matter (PM2.5) collected over 3 weeks at two sites in the Los Angeles area in July 2001. The ambient samples were composited for organic compound analysis by the day of the week to investigate weekly trends in source contributions. The sensitivity analysis specifically examined the impact of the uncertainty in mobile source emissions profiles on the CMB model results. The key parameter impacting model sensitivity was the source profile for gasoline smoker vehicles. High-emitting gasoline smoker vehicles with visible plumes were seen to be a significant source of PM in the area, but use of different measured profiles for smoker vehicles in the model gave very different results for apportionment of gasoline, diesel, and smoker vehicle tailpipe emissions. In addition, the contributions of gasoline and diesel emissions to total ambient PM varied as a function of the site and the day of the week.     

Emissions of organic compounds and trace metals in fine particulate matter from motor vehicles: a tunnel study in Houston, Texas

Fine particulate matter (PM) samples collected in a highway tunnel in Houston, TX, were analyzed to quantify the concentrations of 14 n-alkanes, 12 polycyclic aromatic hydrocarbons, and nine petroleum biomarkers, as well as 21 metals, with the ultimate aim of identifying appropriate tracers for diesel engines. First, an exploratory multivariate dimensionality reduction technique called principal component analysis (PCA) was employed to identify all potential candidates for tracers. Next, emission indices were calculated to interpret PCA results physically. Emission indices of n-heneicosane, n-docosane, n-tricosane, n-tetracosane, n-pentacosane, fluoranthene, and pyrene were correlated highly and increased strongly with percentage carbon present in the tunnel emanating from diesel vehicles. This suggests that these organic compounds are useful molecular markers to separate emissions from diesel and gasoline engines. Additionally, the results are the first quantification of the metal composition of PM with aerodynamic diameters smaller than 2.5 microm (PM2.5) emissions from mobile sources in Houston. PCA of trace metal concentrations followed by emission index calculations revealed that barium in fine airborne particles can be linked quantitatively to diesel engine emissions, demonstrating its role as an elemental tracer for heavy-duty trucks.