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.     

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.     

Formaldehyde,Melhanol and Hydrocarbon Emissions from Methanol-fueled Cars

Exhaust and evaporative emissions tests were conducted on several methanol- and gasoline-fueled vehicles. Separate samples for chromatographlc analysis of formaldehyde, methanol, and Individual hydrocarbons were collected in each of the three phases of the driving cycle and in each of the two portions of the evaporative emissions test. One vehicle, equipped with an experimental variable-fuel engine, was tested using methanol/gasoline fuel mixtures of 100, 85, 50,15, and 0 percent methanol. Combustion-generated hydrocarbons were lowest using methanol fuel, and increased several-fold as the gasoline fraction was increased. Gasoline components In the exhaust Increased from zero as the gasoline fraction of the fuel was Increased. On the other hand, formaldehyde emissions were several times higher using methanol fuel than they were using gasoline. A dedicated methanol car and the variable-fuel car gave similar emissions patterns when they both were tested using methanol fuel. The organic-carbon composition of the exhaust was 85-90 percent methanol, 5-7 percent formaldehyde, and 3-9 percent hydrocarbons. Several cars that were tested using gasoline emitted similar distributions of hydrocarbons, even through the vehicles represented a broad range of current and developmental engine families and emissions control systems. These vehicles continue the trend of the past twenty years toward less photochemically reactive exhaust, with higher percentages of methane and total alkanes, and correspondingly lower percentages of oleflns and aromatlcs.     

The Role of the Computer in Air Pollution Control

The search for ways of reducing vehicular emissions has led to numerous investigations of the relationships between fuel composition and the pollutants discharged from automobiles. The most obvious fuel effects result from evaporation of gasoline components from the fuel tanks and carburetors of vehicles which lack effective mechanical devices (such as those required on all 1971 model cars) to control evaporative losses. Thus, several laboratories and cooperative study groups (Coordinating Research Council and American Petroleum Institute) have investigated the ways in which fuel properties (especially the amounts and types of C₄-C₅ hydrocarbons) influence both the amount and the potential atmospheric reactivity of evaporative emissions.^1–6 But fuel evaporation accounts for only a small portion of the total hydrocarbons emitted by automobiles, and gasoline modifications (such as volatility reductions) that reduce evaporative losses can lead to higher levels of hydrocarbons in automobile exhaust.^4–6     

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.     

Cold-start emissions of modern passenger cars at different low ambient temperatures and their evolution over vehicle legislation categories

The emissions of modern gasoline and diesel passenger cars are reduced by catalysts except in cold-starting. Since catalysts require a certain temperature (typically above 300 °C) to work to full efficiency, emissions are significantly higher during the warm-up phase of the car. The duration of this period and the emissions produced depend on the ambient temperature as well as on the initial temperature of the car's propulsion systems.The additional emissions during a warm-up phase, known as “cold-start extra emissions” (CSEEs) for emission inventory modelling, are mostly assessed by emission measurements at an ambient temperature of 23 °C. However, in many European countries average ambient temperatures are below 23 °C. This necessitates emission measurements at lower temperatures in order to model and assess cold-start emissions for real-world temperature conditions.This paper investigates the influence of regulated pollutants and CO₂ emissions of recent gasoline and diesel car models (Euro-4 legislation) at different ambient temperatures, 23, ?7 and ?20 °C. We present a survey and model of the evolution of cold-start emissions as a function of different car generations (pre-Euro-1 to Euro-4 legislations). In addition the contribution of CSEEs to total fleet running emissions is shown to highlight their increasing importance.For gasoline cars, it turns out that in average real-world driving the majority of the CO (carbon monoxide) and HC (hydrocarbon) total emissions are due to cold-start extra emissions. Moreover, the cold-start emissions increase considerably at lower ambient temperatures. In contrast, cold-start emissions of diesel cars are significantly lower than those of gasoline cars. Furthermore, the transition from Euro-3 to Euro-4 gasoline vehicles shows a trend for a smaller decline for cold-start extra emissions than for legislative limits. Particle and NO_x emission of cold-starts are less significant.     

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.     

Composition of Automobile Evaporative and Tailpipe Hydrocarbon Emissions

Mathematical modeling of ambient air photochemistry requires comprehensive mobile source hydrocarbon emission speciation. Passenger car tailpipe and evaporative hydrocarbon emissions have been examined using procedures described in the Federal Register for emissions certification. Hydrocarbon emission rates and compositions were determined for four passenger cars: a 1963 Chevrolet, a 1977 Ford Mustang II, a 1978 Mercury Monarch, and a 1979 Ford LTD-II. These vehicles are representative of a wide range of exhaust and evaporative emissions control configurations. Both emission rates and compositions were dependent on the emissions control devices used with the vehicles, and the fuel composition and vapor pressure. In agreement with the literature, tailpipe catalyst control systems removed unsaturated olefinic, aromatic, and acetylenic hydrocarbons to a greater extent than saturated paraffinic hydrocarbons. The impact of evaporative control devices on composition was not well defined, however the limited data suggested a sensitivity to fuel aromatic content. The emission rate of benzene, emphasized because of its potential carcinogenicity, was sensitive to both fuel benzene and total aromatic content.     

Penetration of evaporative emissions into a home from an M85-fueled vehicle parked in an attached garage

The use of both oxygenated fuels in carbon monoxide (CO) nonattainment areas and reformulated gasoline in ozone nonattainment areas has been mandated by the 1990 Clean Air Act Amendments. Methanol has been proposed as an alternative fuel for CO nonattainment areas. Its use will potentially increase indoor methanol inhalation exposure resulting from the evaporation of methanol vapor from methanol-fueled vehicles parked in residential garages. Indoor air concentrations of methanol, benzene, and toluene were measured in a residential home with an attached garage. The effects of vehicle emission control devices (charcoal canister hose connection); home heating, ventilation, and air conditioning (HVAC) fans; ambient air, garage, and fuel tank temperatures; and wind speed were examined. The disconnection of the charcoal canister hose, which simulates a spent evaporative emission control device, resulted in elevated benzene, toluene, and methanol concentrations in the garage and attached home. Higher fuel tank temperatures resulted in higher benzene and toluene concentrations in the garage, but not methanol. The concentrations for all compounds in the garage and concentrations of benzene and toluene in the adjacent room were lower when the HVAC fan was on than when it was off, while the concentrations of all three compounds in the rest of the house were higher, although these differences were not statistically significant. Thus, the portion of the population that parks cars in garages attached to homes will experience increased methanol exposures if methanol is used as an automotive fuel.     

Influence of Oxygenated Fuels on the Emissions from Three Pre-1985 Light-Duty Passenger Vehicles

Tailpipe and evaporative emissions from three pre-1985 passenger motor vehicles operating on an oxygenated blend fuel and on a nonoxygenated base fuel were characterized. Emission data were collected for vehicles operating over the Federal Test Procedure at 40,75, and 90°F to simulate ambient driving conditions. The two fuels tested were a commercial summer grade regular gasoline (the nonoxygenated base fuel) and an oxygenated fuel containing 9.5 percent methyl tert-butyl ether (MTBE), more olefins, and fewer aromatics than the base fuel. The emissions measured were total hydrocarbons (THCs), speciated hydrocarbons, speciated aldehydes, carbon monoxide (CO), oxides of nitrogen (NO_x), benzene, and 1,3-butadiene.

This study showed no pattern of tailpipe regulated emission reduction when oxygenated fuel was used. Tailpipe emissions from the 1984 Buick Century without a catalyst and the 1977 Mustang with catalyst decreased with the MTBE fuel. However, emissions from the 1984 Buick Century and the 1980 Chevrolet Citation, both fitted with catalysts increased. The vehicles emitted more 1,3- butadiene and, in general, more NO_x when operated with the base fuel.

THC, CO, benzene, and 1,3-butadiene emissions from both fuels and all vehicles, in general, decreased with increasing test temperature, whereas NO_x emissions, in general, increased with increasing test temperature. Formaldehyde, acetaldehyde, and total aldehydes also showed a decrease in emissions as test temperature increased. More formaldehyde was emitted when the MTBE fuel was used.

Evaporative, diurnal, and hot soak emissions from the base fuel were greater than those from the MTBE fuel. The evaporated emissions from both fuels increased with increasing test temperatures. Diurnal data indicate that canister conditioning (bringing the evaporative charcoal canister to equilibrium) is required before testing.     

Penetration of Evaporative Emissions into a Home from an M85-Fueled Vehicle Parked in an Attached Garage

ABSTRACT

The use of both oxygenated fuels in carbon monoxide (CO) nonattainment areas and reformulated gasoline in ozone nonattainment areas has been mandated by the 1990 Clean Air Act Amendments. Methanol has been proposed as an alternative fuel for CO nonattainment areas. Its use will potentially increase indoor methanol inhalation exposure resulting from the evaporation of metha-nol vapor from methanol-fueled vehicles parked in residential garages. Indoor air concentrations of metha-nol, benzene, and toluene were measured in a residential home with an attached garage. The effects of vehicle emission control devices (charcoal canister hose connection); home heating, ventilation, and air conditioning (HVAC) fans; ambient air, garage, and fuel tank temperatures; and wind speed were examined.

The disconnection of the charcoal canister hose, which simulates a spent evaporative emission control device, resulted in elevated benzene, toluene, and metha-nol concentrations in the garage and attached home. Higher fuel tank temperatures resulted in higher benzene and toluene concentrations in the garage, but not methanol. The concentrations for all compounds in the garage and concentrations of benzene and toluene in the adjacent room were lower when the HVAC fan was on than when it was off, while the concentrations of all three compounds in the rest of the house were higher, although these differences were not statistically significant. Thus, the portion of the population that parks cars in garages attached to homes will experience increased methanol exposures if methanol is used as an automotive fuel.     

Regulated and unregulated emissions from an internal combustion engine operating on ethanol-containing fuels

In the present work, the effect of ethanol addition to gasoline on regulated and unregulated emissions is studied. A 4-cylinder OPEL 1.6 L internal combustion engine equipped with a hydraulic brake dynamometer was used in all the experiments. For exhaust emissions treatment a typical three-way catalyst was used. Among the various compounds detected in exhaust emissions, the following ones were monitored at engine and catalyst outlet: methane, hexane, ethylene, acetaldehyde, acetone, benzene, 1,3-butadiene, toluene, acetic acid and ethanol. Addition of ethanol in the fuel up to 10% w/w had as a result an increase in the Reid vapour pressure of the fuel, which indicates indirectly increased evaporative emissions, while carbon monoxide tailpipe emissions were decreased. For ethanol-containing fuels, acetaldehyde emissions were appreciably increased (up to 100%), especially for fuel containing 3% w/w ethanol. In contrast, aromatics emissions were decreased by ethanol addition to gasoline. Methane and ethanol were the most resistant compounds to oxidation while ethylene was the most degradable compound over the catalyst. Ethylene, methane and acetaldehyde were the main compounds present at engine exhaust while methane, acetaldehyde and ethanol were the main compounds in tailpipe emissions for ethanol fuels after the catalyst operation.     

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.     

Emissions profile from new and in-use handheld, 2-stroke engines

The objective of this study was to characterize exhaust emissions from a series of handheld, 2-stroke small engines. A total of 23 new and used engines from model years 1981–2003 were studied; these engines spanned three phases of emission control (pre-control, phase-1, phase-2). Measured emissions included carbon monoxide (CO), carbon dioxide (CO₂), nitrogen oxides (NO_x), hydrocarbons (HC), fine particulate matter (PM_2.5), and sulfur dioxide (SO₂). Emissions reductions in CO (78%) and HC (52%) were significant between pre-control and phase-2 engines. These reductions can be attributed to improvements in engine design, reduced scavenging losses, and implementation of catalytic exhaust control. Total hydrocarbon emissions were strongly correlated with fuel consumption rates, indicating varying degrees of scavenging losses during the intake/exhaust stroke. The use of a reformulated gasoline containing 10% ethanol resulted in a 15% decrease in HC and a 29% decrease in CO emissions, on average. Increasing oil content of 2-stroke engine fuels results in a substantial increase of PM_2.5 emissions as well as smaller increases in HC and CO emissions. Results from this study enhance existing emission inventories and appear to validate predicted improvements to ambient air quality through implementation of new phase-2 handheld emission standards.     

Examining the temperature dependence of ethanol (E85) versus gasoline emissions on air pollution with a largely-explicit chemical mechanism

The increased use of ethanol in transportation fuels warrants an investigation of its consequences. An important component of such an investigation is the temperature dependence of ethanol and gasoline exhaust chemistry. We use the Master Chemical Mechanism (MCM, version 3.1, LEEDS University) with the SMVGEAR II chemical ordinary differential solver to provide the speed necessary to simulate complex chemistry to examine such effects. The MCM has over 13,500 organic reactions and 4600 species. SMVGEAR II is a sparse-matrix Gear solver that reduces the computation time significantly while maintaining any specified accuracy. Although we use a box model for this study, we determine and demonstrate in a separate study that the speed of the MCM with SMVGEAR II allows the MCM to be modeled in 3-dimensions. We also verified the accuracy of the model in comparison with smog chamber data. We then use the model with species-resolved tailpipe emissions data for E85 (15% gasoline, 85% ethanol fuel blend) and gasoline vehicles to compare the impact of each on nitrogen oxides, organic gases, and ozone as a function of ambient temperature and background concentrations, using Los Angeles in 2020 as a base case. We use two different emissions sets – one is a compilation of exhaust and evaporative data taken near 24 °C and the other from exhaust data taken at ?7 °C – to determine how atmospheric chemistry and emissions are affected by temperature. We include diurnal effects by examining two day scenarios. We find that, accounting for chemistry and dilution alone, the average ozone concentrations through the range of temperatures tested are higher with E85 than with gasoline by ～7 part per billion volume (ppbv) at higher temperatures (summer conditions) to ～39 ppbv at low temperatures and low sunlight (winter conditions) for an area with a high nitrogen oxide (NOx) to non-methane organic gas (NMOG) ratio. The results suggest that E85's effect on health through ozone formation becomes increasingly more significant relative to gasoline at colder temperatures due to the change in exhaust emission composition at lower temperatures. Acetaldehyde and formaldehyde concentrations are also much higher with E85 at cold temperatures, which is a concern because both are considered to be carcinogens. These could have implications for wintertime use of E85. Peroxy acetyl nitrate (PAN), another air pollutant of concern, increases with E85 by 0.3–8 ppbv. The sensitivity of the results to box size, initial background concentrations, background emissions, and water vapor were also examined.     

Exhaust Emissions From In-Use Alternative Fuel Vehicles

Abstract

This study examines exhaust emissions from 11 vehicles tested on compressed natural gas, liquefied petroleum gas, methanol, ethanol, and reformulated gasoline fuels (22 vehicle/ fuel combinations). The paper highlights ozone precursor and toxic emissions. Emission rates from some of the presumably well-maintained, low-mileage test vehicles were higher than expected, but fuel effects were consistent with findings of similar studies. Aggregate toxic and non-methane organic emission rates from the variable/flexible fuel vehicles were higher with alcohol fuels than with reformulated gasoline. Lower specific reactivities for emissions with the alcohol fuels offset this negative trait. Specific reactivities of the organic emissions with the alternative fuels were consistently lower than those with the gasoline blends. Compressed natural gas and liquefied petroleum gas fuels had the lowest values. Although specific reactivities were expected to vary from fuel-to-fuel, they also varied considerably from vehicle-to-vehicle.     

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.     

The impact of motor vehicle control technologies on future photochemical ozone formation in the United Kingdom

Legislation to control motor vehicle exhaust emissions has been introduced in the United Kingdom in stages since the early 1970s. Recently, a further step has been taken towards reducing future exhaust emissions of carbon monoxide, unburnt hydrocarbons and oxides of nitrogen in the 'Luxembourg agreement' (Lubinska, 1985). In this paper, the possible impact of these proposed controls on photochemical air pollution formation in the United Kingdom is investigated, including an evaluation of the relative merits of the two principal emission control options for petrol-driven cars: 'Lean Burn' engines and 'Catalyst' exhaust gas treatment.     

机动车尾气VOCs排放特征及减排措施研究

分析了机动车尾气挥发性有机物(VOCs)的排放特征,发现尾气VOCs排放具有明显的日变化和季节变化特征。不同区域不同车型机动车尾气VOCs成分谱略有差异,轻型汽油车尾气VOCs中芳香烃和烷烃含量较高,柴油车烷烃含量较高。尾气排放受机动车保有量、行驶里程、维护保养水平、行驶速度和燃油标准、排放标准等因素影响。从优先控制汽油车、加快机动车更新、采取本地化减排措施、加强多元管理措施、提高科研水平等方面提出了针对性的减排措施。