Peter A. Gabele

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 Californias 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.

Variations in Speciated Emissions from Spark-Ignition and Compression-Ignition Motor Vehicles in California's South Coast Air Basin

Abstract 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.

Methods of Characterizing the Distribution of Exhaust Emissions from Light-Duty, Gasoline-Powered Motor Vehicles in the U.S. Fleet

Abstract Mobile sources significantly contribute to ambient concentrations of airborne particulate matter (PM). Source apportionment studies for PM10 (PM ≤ 10 µm in aerodynamic diameter) and PM2.5 (PM ≤ 2.5 µm 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.

EMISSION PATTERNS OF DIESEL-POWERED PASSENGER CARS, PART II

An experimental program was conducted to characterize the gaseous and particulate emissions from a 1975 Peugeot 504D light duty diesel-powered vehicle. The vehicle was tested over the 1975 Federal Test Procedure, Highway Fuel Economy Test, and Sulfate Emissions Test driving cycles using four different fuels covering a fair range of composition, density, and sulfur content. In addition to fuel economy and regulated gaseous emission measurements of hydrocarbons, carbon monoxide, and oxides of nitrogen, emission measurements were also obtained for non-regulated pollutants including sulfur dioxide, surfates, aldehydes, benzo(a)pyrene, carbonyl sulfide, hydrogen cyanide, nonreactive hydrocarbons, and particulate matter. The results are discussed in terms of emission trends due to either fuel type or driving cycle influence. /GMRL/

Factors Influencing the Composition and Quantity of Passenger Car Refueling Emissions — Part I

This paper describes the results of a study to examine the effects of various experimental variables on the quantity and composition of emissions associated with motor vehicle refueling. Problems related to accurate laboratory simulation of vehicle refueling are discussed. Preliminary results include emission rates for total hydrocarbons, benzene and 82 other hydrocarbon compounds for a single test vehicle under a variety of temperature and test conditions.

A CHARACTERIZATION OF EMISSIONS FROM AN EARLY MODEL FLEXIBLE-FUEL VEHICLE

An emission study was conducted on a 1987 Ford Crown Victoria flexible-fuel vehicle, an early prototype which had been driven about 25,000 miles. The vehicle was run on both gasoline and a blend of 85 percent methanol and 15 percent gasoline. Emission rates of regulated pollutants (hydrocarbons, carbon monoxide, nitrogen oxides, formaldehyde, and methanol) and nonregulated pollutants (speciated organic materials) were determined for both exhaust and evaporative emissions. Tests were run varying the driving cycle, ambient temperature and catalytic converter. In general, hydrocarbon composition of exhaust emissions was significantly affected by catalyst replacement and cold starts, slightly affected by driving schedule, and unaffected by ambient temperature and test fuel. Hydrocarbon composition of evaporative emissions was only sensitive to the type of evaporative test being performed: diurnal tests typically had larger fractions of lower molecular weight paraffins than hot soak tests. 11 refs., 4 figs., 7 tabs.

AMBIENT TEMPERATURE AND DRIVING CYCLE EFFECTS ON CNG MOTOR VEHICLE EMISSION

This paper describes an emissions study of two vans powered by compressed natural gas (CNG). One van was relatively new, while the other had been driven more than 120,000 mi. The purpose of the study was to obtain emissions information which could be used to predict the impact of CNG use on ambient air quality and air toxic concentrations, and to develop a better understanding of the effect of ambient temperature variations on CNG emissions. Using four different driving cycles, emission tests were carried out at 20{degree}F, 75{degree}F, and 105{degree}F. Test results agree with previous findings that document low emissions of nonmethane hydrocarbons from CNG vehicles. Results also confirm the expectation that CNG emissions are not significantly affected by ambient temperature variations, although an increase in formaldehyde emission was noted for the 20{degree}F cold-start tests.

A Computer-Controlled, Real-Time Automobile Emissions Monitoring System

A minicomputer controlled automotive emissions sampling and analysis system was developed to determine vehicular modal emissions over various test cycles. This data acquisition system can sample real-time emissions at a rate of 10 samples/s. A buffer utilization program enables incoming digital data from an entire test sequence to be logged rapidly and stored on disc, thus permitting the user to reassess the data at later dates for processing in accordance with modal schemes.

A Characterization of Exhaust Emissions from Lean Burn, Rotary, and Stratified Charge Engines

This paper reports the results of an exhaust emissions characterization from the noncatalyst control systems employed on the Mazda RX-4 rotary, the Honda CVCC, and the Chrysler electronic lean burn. Throughout the paper, exhaust emissions from these vehicles are compared to those from a Chrysler equipped with an oxidation catalyst and an air pump. The emissions characterized are carbon monoxide, hydrocarbons, nitrogen oxides, sulfur dioxide, sulfates, hydrogen sulfide, carbonyl sulfide, hydrogen cyanide, aldehydes, particulate matter, and detailed hydrocarbons. A brief description of the sampling and analysis procedures used is included within the discussion. /SASI/

Study on infrared gas-filter correlation spectrometer for measuring low-concentration methanol gases

A gas-filter correlation spectrometer that employed a wide spectral band of infrared radiation and gas-filter cell has been built and successfully tested to measure methanol concentrations up to 113 ppm. The instrument demonstrates a detection limit of approximately 1.0 um. The interference of nonmethanol gases is negligible when automobile exhausts are used for the test. The most prominent, though not serious, problem appears to be the signal drift, which is believed to be improved by thermally insulating the instrument. The analyzer demonstrated its capability for real-time analysis of emissions from methanol-fueled vehicles due to its simplicity and fast response as compared with wet chemical methods.