Characterization of emissions from a variable gasoline/methanol fueled car.

In response to the occurrence of the increasingly severe ambient ozone exceedances, regional environmental managers are examining the possibility of a cleaner fuel for automobiles. At this time the leading candidate appears to be methanol. In anticipation of a shift to methanol, flexible-fueled automobiles capable of operating on gasoline and/or methanol are being developed. This study examines both the exhaust and evaporative emissions from a prototype General Motors Variable Fuel Corsica. Results are reported for tests conducted at temperatures of 40 degrees, 75 degrees, and 90 degrees F, and for fuels M0 M25, M50, M85, and M100. In addition to regulated emissions and fuel economy, emission rates for methanol, aldehydes, and a large number of hydrocarbon compounds were measured. The data indicate that increasing the fuel's methanol content does not affect the exhaust organic emission rate (calculated in accordance with the regulation) from flexible-fueled cars, but formaldehyde and methanol comprise increasingly greater portions of the organic material while hydrocarbons comprise less. Increasing fuel methanol content has no significant effect on exhaust regulated emission rates (organic material, carbon monoxide, and nitrogen oxides) nor on the composition of total hydrocarbons, except for methane, which increases substantially. The effect of ambient temperature on both exhaust and evaporative emissions is similar to its effect on gasoline cars: organic and carbon monoxide exhaust emissions increase substantially at the lower temperatures, and evaporative emissions increase steadily with increases in temperature.     

The Influence of Gasoline Formulation on Specific Pollutant Emissions

ABSTRACT

Many recent works have dealt with the influence of fuel composition on regulated and specific pollutant emissions from spark ignition engines. While many qualitative correlations have been already proposed, only a few quantitative ones are known (benzene remains an exception).

This paper describes qualitative and quantitative correlations between fuel composition and specific pollutant emissions (individual hydrocarbons, aldehydes, ketones, alcohols, and organic acids) of a spark ignition engine. The aim of this work was to find the precursors of the main specific pollutants. Then, for each of them, a multilinear equation has been calculated, illustrating the correlation between its concentration in exhaust gases and its content in the fuel. The results of these calculations point out which initial compound favors the formation of a determined pollutant. As lean conditions are probably going to be used in future commercial engines, the fuel effect has been studied for a broad range of equivalence ratios (from 0.8 to 1.2).     

Characterization of Emissions from a Variable Gasoline/Methanol Fueled Car

In response to the occurrence of the increasingly severe ambient ozone exceedances, regional environmental managers are examining the possibility of a cleaner fuel for automobiles. At this time the leading candidate appears to be methanol. In anticipation of a shift to methanol, flexible-fueled automobiles capable of operating on gasoline and/or methanol are being developed. This study examines both the exhaust and evaporative emissions from a prototype General Motors Variable Fuel Corsica. Results are reported for tests conducted at temperatures of 40°, 75°, and 90° F, and for fuels MO M25, M50, M85, and M100. In addition to regulated emissions and fuel economy, emission rates for methanol, aldehydes, and a large number of hydrocarbon compounds were measured. The data indicate that increasing the fuel's methanol content does not affect the exhaust organic emission rate (calculated in accordance with the regulation) from flexible-fueled cars, but formaldehyde and methanol comprise increasingly greater portions of the organic material while hydrocarbons comprise less. Increasing fuel methanol content has no significant effect on exhaust regulated emission rates (organic material, carbon monoxide, and nitrogen oxides) nor on the composition of total hydrocarbons, except for methane, which increases substantially. The effect of ambient temperature on both exhaust and evaporative emissions is similar to its effect on gasoline cars: organic and carbon monoxide exhaust emissions increase substantially at the lower temperatures, and evaporative emissions increase steadily with increases in temperature.     

Experimental investigation of regulated and unregulated emissions from a diesel engine fueled with Euro V diesel fuel and fumigation methanol

Experiments were conducted on a four-cylinder direct-injection diesel engine with part of the engine load taken up by fumigation methanol injected into the air intake of each cylinder to investigate the regulated and unregulated gaseous emissions and particulate emission of the engine under five engine loads at an engine speed of 1920 rev min^?1. The fumigation methanol was injected to top up 10%, 20% and 30% of the engine load under different engine operating conditions.The experimental results show that at low engine loads, the brake thermal efficiency (BTE) decreases with increase in fumigation methanol; but at high engine loads, the BTE is not significantly affected by fumigation methanol. The fumigation methanol results in significant increase in hydrocarbon (HC), carbon monoxide (CO) and nitrogen dioxide (NO₂) emissions, but decrease in nitrogen oxides (NO_x). For the unregulated gaseous emissions, unburned methanol, formaldehyde and BTX (benzene, toluene and xylene) emissions increase but ethyne, ethene and 1,3-butadiene emissions decrease. Particulate mass and number concentrations also decrease with increase in fumigation methanol. A diesel oxidation catalyst (DOC) is found to reduce significantly most of the pollutants, including the air toxics, when the exhaust gas temperature is sufficiently high.     

Hydrocarbon emissions speciation in diesel and biodiesel exhausts

Diesel engine emissions are composed of a long list of organic compounds, ranging from C₂ to C₁₂₊, and coming from the hydrocarbons partially oxidized in combustion or produced by pyrolisis. Many of these are considered as ozone precursors in the atmosphere, since they can interact with nitrogen oxides to produce ozone under atmospheric conditions in the presence of sunlight. In addition to problematic ozone production, Brookes, P., and Duncan, M. [1971. Carcinogenic hydrocarbons and human cells in culture. Nature.] and Heywood, J. [1988. Internal Combustion Engine Fundamentals.Mc Graw-Hill, ISBN 0-07-1000499-8.] determined that the polycyclic aromatic hydrocarbons present in exhaust gases are dangerous to human health, being highly carcinogenic.The aim of this study was to identify by means of gas chromatography the amount of each hydrocarbon species present in the exhaust gases of diesel engines operating with different biodiesel blends. The levels of reactive and non-reactive hydrocarbons present in diesel engine exhaust gases powered by different biodiesel fuel blends were also analyzed.Detailed speciation revealed a drastic change in the nature and quantity of semi-volatile compounds when biodiesel fuels are employed, the most affected being the aromatic compounds. Both aromatic and oxygenated aromatic compounds were found in biodiesel exhaust. Finally, the conservation of species for off-side analysis and the possible influence of engine operating conditions on the chemical characterization of the semi-volatile compound phase are discussed.The use of oxygenated fuel blends shows a reduction in the Engine-Out emissions of total hydrocarbons. But the potential of the hydrocarbon emissions is more dependent on the compositions of these hydrocarbons in the Engine-Out, to the quantity; a large percent of hydrocarbons existing in the exhaust, when biodiesel blends are used, are partially burned hydrocarbons, and are interesting as they have the maximum reactivity, but with the use of pure biodiesel and diesel, the most hydrocarbons are from unburned fuel and they have a less reactivity. The best composition in the fuel, for the control of the hydrocarbon emissions reactivity, needs to be a fuel with high-saturated fatty acid content.     

Effect of Methanol on Exhaust Composition of a Fuel Containing Toluene,n-Heptane,and Isooctane

This study describes the variations in the chemical composition of the exhaust from a single cylinder engine when up to 25% methanol is added to a fuel blend of toluene, isooctane, and n-heptane. Under fuel-rich conditions, and with increasing methanol concentration, it is observed that unburned fuel and benzene emissions increase, exhaust acetylene remains constant, and propylene, isobutylene, methane, ethylbenzene, and styrene concentrations decrease. As oxygen becomes more available, the effects of methanol are reduced, and at an equivalence ratio of 1.25—excess oxygen now is present—methanol no longer affects the concentration of exhaust hydrocarbons. These observations are explained by the reactions of formaldehyde—an incomplete combustion product of methanol— with alkyl radicals derived from the fuel. The photochemical reactivity of the exhaust is unchanged when up to 15% of methanol is present in the fuel at an equivalence ratio of 0.85, but increases at higher methanol contents because of the increase in unburned toluene in the exhaust.     

Characterization of Emissions from Vehicles Using Methanol and Methanol-Gasoline Blended Fuels

Exhaust and evaporative emissions were examined from vehicles fueled with methanol or a gasoline-methanol blend. Regulated automobile pollutants, as well as detailed hydrocarbons, methanol, and aldehydes were measured, and exhaust emission trends were obtained for vehicle operation over five different driving cycles. Results indicated that use of the blended fuel does not generally have any significant effect on base-line exhaust emission rates of regulated pollutants; however, emission rates of aldehydes increased during the Federal Test Procedure. Aldehyde emissions from the methanol-fueled car were roughly an order of magnitude higher than those resulting from blended fuel usage. The hydrocarbon composition of evaporative emissions with the blended fuel was similar to that with the base-line fuel except when canister breakthrough occurred. Evaporative emissions during breakthrough were comprised chiefly of N-butane.     

Seasonal impact of blending oxygenated organics with gasoline on motor vehicle tailpipe and evaporative emissions.

Emissions from a 1988 GM Corsica with adaptive learning closed loop control were measured with 4 fuels at 40, 75, and 90 degrees F. Evaporative and exhaust emissions were examined from each fuel at each test temperature. Test fuels were unleaded summer grade gasoline; a blend of this gasoline containing 8.1 percent ethanol; a refiner's blend stock; and the blend stock containing 16.2 percent methyl tertiary butyl ether. The ethanol and MTBE blends contained 3.0 percent oxygen by weight. Regulated emissions (total hydrocarbons, carbon monoxide, and oxides of nitrogen), detailed aldehydes, detailed hydrocarbons, ethanol, MTBE, benzene, and 1,3-butadiene were determined. The highest levels of regulated emissions were produced at the lower temperature. Blended fuels produced almost twice the evaporative hydrocarbon emissions at high temperatures as did the base fuels. Benzene emissions varied with fuels and operating temperatures, while 1,3-butadiene emissions decreased slightly with increasing temperatures. Formaldehyde emissions were not sensitive to fuel or temperature changes. Ethanol fuel blend total aldehyde emissions increased by 40 percent due to increased acetaldehyde emissions. Fuel blends had approximately a 3 percent economy decrease. The MTBE fuel blend appeared to offer the most reduction in total hydrocarbon, carbon monoxide, and oxides of nitrogen for the fuels and temperatures tested.     

Hazardous air pollutants from mobile sources in the Metropolitan Area of Mexico City

Environmental agencies are currently in the process of implementing a new air management program, which includes the improvement of fuel quality. In this work, exhaust emissions data and estimated relative risk for various fuels testing in-use vehicles, equipped with three different exhaust emission control technologies, are presented. Aromatics, sulfur, and olefins contents; type of oxygenated compound; and Reid vapor pressure were varied. The aim also includes calculating the ozone (O3) forming potential and a relative cancer risk of emissions from current and formulated gasoline blends in Mexico. The proposed gasoline decreases carbon monoxide, total hydrocarbons (THC), and nitrogen oxides emissions by 18 and 14%, respectively, when compared with gasoline sold in the rest of the country and within ozone nonattainment metropolitan areas in Mexico, respectively.     

Seasonal Impact of Blending Oxygenated Organics with Gasoline on Motor Vehicle Tailpipe and Evaporative Emissions

Emissions from a 1988 GM Corsica with adaptive learning closed loop control were measured with 4 fuels at 40, 75, and 90° F. Evaporative and exhaust emissions were examined from each fuel at each test temperature. Test fuels were unleaded summer grade gasoline; a blend of this gasoline containing 8.1 percent ethanol; a refiner’s blend stock; and the blend stock containing 16.2 percent methyl tertiary butyl ether. The ethanol and MTBE blends contained 3.0 percent oxygen by weight. Regulated emissions (total hydrocarbons, carbon monoxide, and oxides of nitrogen), detailed aldehydes, detailed hydrocarbons, ethanol, MTBE, benzene, and 1, 3-butadiene were determined.

The highest levels of regulated emissions were produced at the lower temperature. Blended fuels produced almost twice the evaporative hydrocarbon emissions at high temperatures as did the base fuels. Benzene emissions varied with fuels and operating temperatures, while 1, 3-butadiene emissions decreased slightly with increasing temperatures. Formaldehyde emissions were not sensitive to fuel or temperature changes. Ethanol fuel blend total aldehyde emissions Increased by 40 percent due to increased acetaldehyde emissions.

Fuel blends had approximately a 3 percent economy decrease. The MTBE fuel blend appeared to offer the most reduction in total hydrocarbon, carbon monoxide, and oxides of nitrogen for the fuels and temperatures tested.     

The impacts of combustion emissions on air quality and climate – From coal to biofuels and beyond

Combustion processes have inherent characteristics that lead to the release in the environment of both gaseous and particulate pollutants that have primary and secondary impacts on air quality, human health, and climate. The emissions from the combustion of fossil fuels and biofuels and their atmospheric impacts are reviewed here with attention given to the emissions of the currently regulated pollutant gasses, primary aerosols, and secondary aerosol precursors as well as the emissions of non-regulated pollutants. Fuels ranging from coal, petroleum, liquefied petroleum gas (LPG), natural gas, as well as the biofuels; ethanol, methanol, methyl tertiary-butyl ether (MTBE), ethyl tertiary-butyl ether (ETBE), and biodiesel, are discussed in terms of the known air quality and climate impacts of the currently regulated pollutants. The potential importance of the non-regulated emissions of both gasses and aerosols in air quality issues and climate is also discussed with principal focus on aldehydes and other oxygenated organics, polycyclic aromatic hydrocarbons (PAHs), and nitrated organics. The connection between air quality and climate change is also addressed with attention given to ozone and aerosols as potentially important greenhouse species.     

Speciated Hydrocarbon Emissions from the Combustion of Single Component Fuels. I. Effect of Fuel Structure

Speciated hydrocarbon emissions data have been collected for six single-component fuels run in a laboratory pulse flame combustor (PFC). The six fuels include n-heptane, isooctane (2, 2, 4-trimethylpentane), cyclohexane, 1-hexene, toluene, and methyl-t-butyl ether (MTBE: an oxygenated fuel extender). Combustion of non-aromatic fuels in the PFC (at a fuel/air equivalence ratio of Φ = 1.02) produced low levels of unburned fuel and high yields of methane and olefins (> 75 percent combined) irrespective of the molecular structure of the fuel. In contrast, hydrocarbon emissions from toluene combustion in the PFC were comprised predominantly of unburned fuel (72 percent). With the PFC, low levels of 1, 3-butadiene (0.3-1.8 percent) were observed from all the fuels except MTBE, for which no measurable level (<0.2 percent) was detected; low levels of benzene were observed from isooctane, heptane, and 1-hexene, but significant levels (9 percent) from cyclohexane and toluene. No measurable amount of benzene (< 0.2 percent) was observed in the MTBE exhaust.

For isooctane and toluene the speciated hydrocarbon emissions from a spark-ignited (SI) single-cylinder engine were also determined. HC emissions from the SI engine contained the same species as observed from the PFC, although the relative composition was different. For the non-aromatic fuel isooctane, unburned fuel represented a larger fraction (50 percent) of the HC emissions when run in the engine. HC emissions from toluene combustion in the engine were similar to those from the PFC.     

Hazardous Air Pollutants from Mobile Sources in the Metropolitan Area of Mexico City

Abstract

Environmental agencies are currently in the process of implementing a new air management program, which includes the improvement of fuel quality. In this work, exhaust emissions data and estimated relative risk for various fuels testing in-use vehicles, equipped with three different exhaust emission control technologies, are presented. Aromatics, sulfur, and olefins contents; type of oxygenated compound; and Reid vapor pressure were varied. The aim also includes calculating the ozone (O₃)of forming potential and a relative cancer risk of emissions from current and formulated gasoline blends in Mexico. The proposed gasoline decreases carbon monoxide, total hydrocarbons (THC), and nitrogen oxides emissions by 18 and 14%, respectively, when compared with gasoline sold in the rest of the country and within ozone nonattainment metropolitan areas in Mexico, respectively.     

Mixing ratios of volatile organic compounds (VOCs) in the atmosphere of Karachi,Pakistan

Mixing ratios of carbon monoxide (CO), methane (CH₄), non-methane hydrocarbons, halocarbons and alkyl nitrates (a total of 72 species) were determined for 78 whole air samples collected during the winter of 1998–1999 in Karachi, Pakistan. This is the first time that volatile organic compound (VOC) levels in Karachi have been extensively characterized. The overall air quality of the urban environment was determined using air samples collected at six locations throughout Karachi. Methane (6.3 ppmv) and ethane (93 ppbv) levels in Karachi were found to be much higher than in other cities that have been studied. The very high CH₄ levels highlight the importance of natural gas leakage in Karachi. The leakage of liquefied petroleum gas contributes to elevated propane and butane levels in Karachi, although the propane and butane burdens were lower than in other cities (e.g., Mexico City, Santiago). High levels of benzene (0.3–19 ppbv) also appear to be of concern in the Karachi urban area. Vehicular emissions were characterized using air samples collected along the busiest thoroughfare of the city (M.A. Jinnah Road). Emissions from vehicular exhaust were found to be the main source of many of the hydrocarbons reported here. Significant levels of isoprene (1.2 ppbv) were detected at the roadside, and vehicular exhaust is estimated to account for about 20% of the isoprene observed in Karachi. 1,2-Dichloroethane, a lead scavenger added to leaded fuel, was also emitted by cars. The photochemical production of ozone (O₃) was calculated for CO and the various VOCs using the Maximum Incremental Reactivity (MIR) scale. Based on the MIR scale, the leading contributors to O₃ production in Karachi are ethene, CO, propene, m-xylene and toluene.     

Speciated hydrocarbon and carbon monoxide emissions from an internal combustion engine operating on methyl tertiary butyl ether-containing fuels

In the present work, engine and tailpipe (after a three-way catalytic converter) emissions from an internal combustion engine operating on two oxygenated blend fuels [containing 2 and 11% weight/weight (w/w) methyl tertiary butyl ether (MTBE)] and on a nonoxygenated base fuel were characterized. The engine (OPEL 1.6 L) was operated under various conditions, in the range of 0-20 HP. Total unburned hydrocarbons, carbon monoxide, methane, hexane, ethylene, acetaldehyde, acetone, 2-propanol, benzene, toluene, 1,3-butadiene, acetic acid, and MTBE were measured at each engine operating condition. As concerns the total HC emissions, the use of MTBE was beneficial from 1.90 to 3.81 HP, which were by far the most polluting conditions. Moreover, CO emissions in tailpipe exhaust were decreased in the whole operation range with increasing MTBE in the fuel. The greatest advantage of MTBE addition to gasoline was the decrease in ethylene, acetaldehyde, benzene, toluene, and acetic acid emissions in engine exhaust, especially when MTBE content in the fuel was increased to 11% w/w. In tailpipe exhaust, the catalyst operation diminished the observed differences. Ethylene, methane, and acetaldehyde were the main compounds present in exhaust gases. Ethylene was easily oxidized over the catalyst, while acetaldehyde and methane were quite resistant to oxidation.     

Effects of Air-Fuel Ratio on Composition of Hydrocarbon Exhaust from Toluene,Toluene-n Heptane Mixture and Isooctane

This study describes the variations in the chemical composition of the exhaust at various air-fuel ratios when toluene, toluene-n-heptane mixture, and isooctane are used as fuels in a Labeco single cylinder engine. The exhaust products from toluene are divided into three groups: those which decrease as the equivalence ratio is increased: toluene, benzene, methane, and dimethylacetylene; those which increase with increasing equivalence ratio: benzaldehyde, and products which exhibit a maximum at an equivalence ratio of 1, then decrease: acetylene, ethyl acetylene, ethyl benzene, and styrene. Combustion of the mixture of 25 volume percent n-heptane in toluene reveals interesting information, compared to emissions from pure toluene: concentrations of ethyl benzene, styrene, and dimethylacetylene surprisingly are increased by factors of 1.9, 1.9, and 2.1 respectively, probably because reactive radicals derived from heptane interact with toluene to form unsaturated molecules. Ethyl acetylene, benzene, and benzaldehyde remained unchanged but the fractional mole concentration of unreacted toluene decreased. These results show that fuels rich in aromatics may produce less unsaturates than when diluted with aliphatic fuels. For isooctane fuel, methane, and isooctane in the exhaust decrease as the equivalence ratio is increased, while isobutylene, propylene, ethylene, and propadiene concentrations exhibit maxima at an equivalence ratio of 1.     

Toxic Emissions from Mobile Sources: A Total Fuel-Cycle Analysis for Conventional and Alternative Fuel Vehicles

ABSTRACT

Mobile sources are among the largest contributors of four hazardous air pollutants—benzene, 1,3-butadiene, acetal-dehyde, and formaldehyde—in urban areas. At the same time, federal and state governments are promoting the use of alternative fuel vehicles as a means to curb local air pollution. As yet, the impact of this movement toward alternative fuels with respect to toxic emissions has not been well studied. The purpose of this paper is to compare toxic emissions from vehicles operating on a variety of fuels, including reformulated gasoline (RFG), natural gas, ethanol, methanol, liquid petroleum gas (LPG), and electricity. This study uses a version of Argonne National Laboratory's Greenhouse Gas, Regulated Emissions, and Energy Use in Transportation (GREET) model, appropriately modified to estimate toxic emissions. The GREET model conducts a total fuel-cycle analysis that calculates emissions from both downstream (e.g., operation of the vehicle) and upstream (e.g., fuel production and distribution) stages of the fuel cycle. We find that almost all of the fuels studied reduce 1,3-buta-diene emissions compared with conventional gasoline (CG). However, the use of ethanol in E85 (fuel made with 85% ethanol) or RFG leads to increased acetaldehyde emissions, and the use of methanol, ethanol, and compressed natural gas (CNG) may result in increased formaldehyde emissions. When the modeling results for the four air toxics are considered together with their cancer risk factors, all the fuels and vehicle technologies show air toxic emission reduction benefits.     

Speciated Hydrocarbon Emissions from the Combustion of Single Component Fuels. II. Catalyst Effects

Six single-component fuels (isooctane, n-heptane, 1-hexene, cyclohexane, methyl-t-butyl ether (MTBE), and toluene) and a multicomponent tracer fuel were burned in a pulse flame combustor (PFC) and reacted over a three-way automotive catalyst. The composition of the raw, uncatalyzed PFC exhaust was characterized in Part I of this study. In Part II, we focus on the conversions of the individual exhaust HC species over the catalyst. In accord with previous studies, the order of reactivity observed for the various classes of HC species was: methane (least reactive) < saturated HC < aromatics < unsaturated HC (most reactive). These differences in catalytic reactivity led to increases in the relative concentrations of methane and some saturated hydrocarbons in the post catalyst exhaust, and corresponding decreases in the relative concentrations of aromatic and unsaturated hydrocarbons. Oxygenated organic compounds showed wide variability in catalytic reactivity depending on the specific compounds involved. Catalytic conversion of the air toxic, 1,3-butadiene, was essentially complete to within detection limits. Benzene and toluene appeared to have similar intrinsic catalytic reactivities. However, net conversion of benzene in most instances was significantly less than that of toluene owing to demethylation of toluene (to form benzene) occurring in parallel with benzene oxidation. Rich combustion of both isooctane and tracer fuel led to the production of methane by the catalyst, primarily from reactions of acetylene and small olefins.     

Speciated Hydrocarbon and Carbon Monoxide Emissions from an Internal Combustion Engine Operating on Methyl Tertiary Butyl Ether-Containing Fuels

ABSTRACT

In the present work, engine and tailpipe (after a three-way catalytic converter) emissions from an internal combustion engine operating on two oxygenated blend fuels [containing 2 and 11% weight/weight (w/w) methyl tertiary butyl ether (MTBE)] and on a nonoxygenated base fuel were characterized. The engine (OPEL 1.6 L) was operated under various conditions, in the range of 0-20 HP. Total unburned hydrocarbons, carbon monoxide, methane, hexane, ethylene, acetaldehyde, acetone, 2-propanol, benzene, toluene, 1,3-butadiene, acetic acid, and MTBE were measured at each engine operating condition. As concerns the total HC emissions, the use of MTBE was beneficial from 1.90 to 3.81 HP, which were by far the most polluting conditions. Moreover, CO emissions in tailpipe exhaust were decreased in the whole operation range with increasing MTBE in the fuel.

The greatest advantage of MTBE addition to gasoline was the decrease in ethylene, acetaldehyde, benzene, toluene, and acetic acid emissions in engine exhaust, especially when MTBE content in the fuel was increased to 11% w/w. In tailpipe exhaust, the catalyst operation diminished the observed differences. Ethylene, methane,and acetaldehyde were the main compounds present in exhaust gases. Ethylene was easily oxidized over the catalyst,while acetaldehyde and methane were quite resistant to oxidation.     

Summer and winter nonmethane hydrocarbon emissions from on-road motor vehicles in the Midwestern United States

On-road vehicle emission rates of nonmethane hydrocarbons (NMHCs) were measured in two tunnels in Milwaukee, WI, in summer 2000 and winter 2001. Seasonal ambient temperatures in the Midwestern United States vary more widely than in locations where most studies of NMHC emissions from vehicle fleets have been conducted. Ethanol is the added fuel oxygenate in the area, and, thus, emissions measured here are of interest as other regions phase out methyl tertiary butyl ether and increase the use of ethanol. Total emissions of NMHCs in three types of tunnel tests averaged 4560 +/- 800 mg L(-1) fuel burned (average +/- standard error). To investigate the impact of cold start on vehicle emissions, samples were collected as vehicles exited a parking structure in subzero temperatures. NMHC emissions in the subzero cold-start test were 8830 +/- 190 mg L(-1) fuel-nearly double the tunnel emissions. Comparison of ambient data for the Milwaukee area with tunnel emissions showed the impact of seasonal differences in fuels and emissions on the urban atmosphere. Composition of fuel samples collected from area gas stations in both seasons was correlated with vehicle emissions; the predominant difference was increased winter emissions of lighter hydrocarbons present in winter gasoline. A chemical mass balance model was used to determine the contributions of whole gasoline and gasoline headspace vapors to vehicle emissions in the tunnel and cold-start tests, which were found to vary with season. Results of the mass balance model also indicate that partially combusted components of gasoline are a major contributor to emissions of aromatic compounds and air toxic compounds, including benzene, toluene, xylenes, napthalene, and 1,3-butadiene, whereas air toxics hexane and 2,2,4-trimethylpentane are largely attributed to gasoline and headspace vapors.