The effect of reformulated gasoline on ambient carbon monoxide concentrations in southeastern Wisconsin

Reformulated gasoline (RFG) contains oxygen additives such as methyl tertiary butyl ether or ethanol. The additives enable vehicles to burn fuel with a higher air/fuel ratio, thereby lowering the emission of carbon monoxide (CO) and volatile organic compounds (VOCs). Because VOCs react with sunlight to form ozone (O3), the Clean Air Act requires severe O3 nonattainment areas such as southeastern Wisconsin to use RFG. On July 17, 2001, the U.S. Environmental Protection Agency (EPA) granted Milwaukee, WI, and Chicago, IL, a waiver from the VOC reduction requirement of Phase II RFG. The VOC reduction requirement was lowered from 27.4% of the 1990 baseline fuel to 25.4%. The assumption was that ethanol-blended RFG would lower summertime CO concentrations sufficiently to offset the increased VOC emissions. The waiver is estimated to increase VOC emissions by approximately 0.8%, or 0.4 t of VOC on a hot summer weekday. This study evaluates whether RFG has been effective in lowering southeastern Wisconsin ambient CO concentrations. Three years of ambient CO data before RFG was introduced were compared with the first three years of ambient CO data after RFG was introduced. This paper also evaluates how the meteorology, vehicle inspection/maintenance program, vehicle miles traveled, and stationary source emissions influence CO concentrations. The winter decrease in ambient CO concentrations was found to be statistically significant, while the summer data showed no statistically significant change, indicating that RFG is most effective lowering ambient CO concentrations in cold weather.     

Evaluation of combustion by-products of MTBE as a component of reformulated gasoline

Methyl tertiary-butyl ether (MTBE) is a gasoline oxygenate that is widely used throughout the US and Europe as an octane-booster and as a means of reducing automotive carbon monoxide (CO) emissions. The combustion by-products of pure MTBE have been evaluated in previous laboratory studies, but little attention has been paid to the combustion by-products of MTBE as a component of gasoline. MTBE is often used in reformulated gasoline (RFG), which has chemical and physical characteristics distinct from conventional gasoline. The formation of MTBE by-products in RFG is not well-understood, especially under "worst-case" vehicle emission scenarios such as fuel-rich operations, cold-starts or malfunctioning emission control systems, conditions which have not been studied extensively. Engine-out automotive dynamometer studies have compared RFG with MTBE to non-oxygenated RFG. Their findings suggest that adding MTBE to reformulated gasoline does not impact the high temperature flame chemistry in cylinder combustion processes. Comparison of tailpipe and exhaust emission studies indicate that reactions in the catalytic converter are quite effective in destroying most hydrocarbon MTBE by-product species. Since important reaction by-products are formed in the post-flame region, understanding changes in this region will contribute to the understanding of fuel-related changes in emissions.     

The Effect of Reformulated Gasoline on Ambient Carbon Monoxide Concentrations in Southeastern Wisconsin

Abstract

Reformulated gasoline (RFG) contains oxygen additives such as methyl tertiary butyl ether or ethanol. The additives enable vehicles to burn fuel with a higher air/fuel ratio, thereby lowering the emission of carbon monoxide (CO) and volatile organic compounds (VOCs). Because VOCs react with sunlight to form ozone (O₃), the Clean Air Act requires severe O₃ nonattainment areas such as southeastern Wisconsin to use RFG. On July 17, 2001, the U.S. Environmental Protection Agency (EPA) granted Milwaukee, WI, and Chicago, IL, a waiver from the VOC reduction requirement of Phase II RFG. The VOC reduction requirement was lowered from 27.4% of the 1990 baseline fuel to 25.4%. The assumption was that ethanol-blended RFG would lower summertime CO concentrations sufficiently to offset the increased VOC emissions. The waiver is estimated to increase VOC emissions by ～0.8%, or 0.4 t of VOC on a hot summer weekday. This study evaluates whether RFG has been effective in lowering southeastern Wisconsin ambient CO concentrations. Three years of ambient CO data before RFG was introduced were compared with the first three years of ambient CO data after RFG was introduced. This paper also evaluates how the meteorology, vehicle inspection/maintenance program, vehicle miles traveled, and stationary source emissions influence CO concentrations. The winter decrease in ambient CO concentrations was found to be statistically significant, while the summer data showed no statistically significant change, indicating that RFG is most effective lowering ambient CO concentrations in cold weather.     

Combustion of gasolines in premixed laminar flames European certified and California phase 2 reformulated gasoline

Two gasoline qualities, European unleaded certified gasoline (EUCG) and California phase 2 reformulated gasoline (P2 RFG), were analysed. EUCG contained about twice the amount of alkyl benzenes compared to P2 RFG and a large amount of cyclohexane. As a balance, P2 RFG contained higher amounts of isooctane and MTBE. The gasolines were burned in a premixed laminar flame burner at 1 atm and at about stoichiometric fuel/air ratio. The species profiles were measured using on-line GC/MS. About 40 compounds were be detected in the gasoline flames. The EUCG resulted in formation of more reactive and toxic compounds. The combustion profiles of the fuel components showed a similar slope, which suggests that the fuel components burn quite independently of each other. Ethene and propene were the dominating species produced from the two gasolines. Commonly, substantial amounts of higher alkenes were found. Combustion of P2 RFG produced higher amounts of isobutene, propene, propyne, propadiene and methanol compared to combustion of EUCG. The high amount of isobutene is reasonably a result of high concentration of isooctane and MTBE in the fuel. The high amount of methanol formed is probably due to the MTBE present in the gasoline. EUCG produced significantly higher amounts of 1,3-butadiene, which quite likely is formed from the cyclohexane in the fuel. The benzene profiles from both gasolines shows an almost constant level up to 800 microm from the burner surface; this is probably due to formation of benzene from alkyl benzenes.     

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.     

Toxic emissions from mobile sources: a total fuel-cycle analysis for conventional and alternative fuel vehicles

Mobile sources are among the largest contributors of four hazardous air pollutants--benzene, 1,3-butadiene, acetaldehyde, 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-butadiene 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.     

Accurate Chemical Analysis of MTBE in Environmental Media

The new millennium ushers in changes for refiners of automobile gasoline in the United States, as well as for the state and federal regulators who establish guidelines for gasoline formulation and environmental regulation governing the fate of gasoline-related chemicals in the nation's air, soil and groundwater. One current issue in the gasoline formulation debate centers on the comparison of the proven benefits of the addition of chemical oxygenates—especially methyltert -butyl ether (MTBE)—to gasoline (to improve tailpipe emission quality) against the presumed environmental problems caused by the presence of oxygenates in ground- and surface waters due to fugitive releases of gasoline. Credible debate on this subject presumes that current and past environmental monitoring data for MTBE in environmental samples is accurate and precise. Experience suggests that this assumption is not correct, in part because certain analytical methodologies—particularly older methods supported by the U.S. Environmental Protection Agency—can fall short of reasonable data quality goals for measurement of MTBE. This Technical Note summarizes the standard EPA methods available to site investigators who need to measure MTBE in environmental media, the limitations and advantages of these measurement techniques, and recommendations for improving these standard EPA methods to yield the highest quality MTBE environmental residue data.     

Germany

ABSTRACT

The 1988 Alternative Motor Fuels Act and the 1990 Clean Air Act Amendments require examination of the potential to favorably influence air quality by changing the composition of motor vehicle fuels. Motor vehicle tailpipe and evaporative emissions were characterized using laboratory simulations of roadway driving conditions and a variety of vehicle-fuel technologies (reformulated gasoline (RFG), methanol (M85), ethanol (E85), and natural gas (CNG)). Speciated organic compound (with Carter MIR ozone potential), CO, and NO_x emission rates and fuel economy were characterized. The Carter MIR ozone potential of combined Federal Test Procedure (FTP) tailpipe and evaporative emissions was reduced more than 90% with CNG relative to RFG, M85, and E85 fuels. FTP toxic compound emissions (benzene, formaldehyde, acetalde-hyde, and 1,3-butadiene) were greater with M85 and E85 fuels than with RFG fuel, and less with CNG fuel than RFG fuel. The most abundant toxic compound was benzene with RFG fuel, formaldehyde with M85 fuel, and acetaldehyde with E85 fuel. FTP MPG fuel economies were reduced with M85 and E85 fuels relative to RFG fuel, consistent with their lower BTU/gal. Energy efficiencies (BTU/mi) were improved with all the alternative fuels relative to RFG. Carter MIR ozone potential was generally reduced with the alternative fuels relative to RFG fuel under REP05 (high speeds and acceleration rates) driving conditions (most significantly with CNG). Toxic aldehyde emissions were reduced under REP05 conditions relative to FTP conditions with all the tested fuels, and toxic benzene emissions were elevated under high acceleration conditions.     

U. S. EPA Views as “Unwarranted” Federal Regulatory Involvement in Odor Control

ABSTRACT

Although there have been several studies examining emissions of criteria pollutants from in-use alternative fuel vehicles (AFVs), little is known about emissions of hazardous air pollutants (HAPs) from these vehicles. This paper explores HAP tailpipe emissions from a variety of AFVs operating in the federal government fleet and compares these emissions to emissions from identical vehicles operating on reformulated gasoline. Emissions estimates are presented for a variety of fuel/model combinations and on four HAPs (acetaldehyde, 1,3-butadi-ene, benzene, and formaldehyde). The results indicate that all AFVs tested offer reduced emissions of HAPs, with the following exceptions: ethanol fueled vehicles emit more acetaldehyde than RFG vehicles, and ethanol- and methanol-fueled vehicles emit more formaldehyde than RFG vehicles. The results from this paper can lead to more accurate emissions factors for HAPs, thus improving HAP inventory and associated risk estimates for both AFVs and conventional vehicles.     

Microbially mediated cadmium sorption/desorption processes in soil amended with sewage sludge

A multi-compartment system was used to study the importance of microorganisms for Cd desorption from soil amended with sewage sludge and simultaneous resorption of the mobilized metal by soil constituents. Using this system made it possible to study the participation of microorganisms (Arthrobacter, Trichoderma), montmorillonite, humic acids, and iron oxides in resorption of the released Cd. A filter-sterilized water extract of root-free soil of pH 6.7 (RF) or RF supplemented with glucose (RFG) were used to mobilize Cd from soil at 14 degrees C in 48 h. Cadmium found in those extracts after 48-h incubation was recognized as bioavailable. Changes in pH values and enrichment of soil extracts with organic acids and siderophores resulted from microbial growth. RFG with lower pH and a higher content of ligands mobilized, on average, 40% of Cd introduced with sewage sludge amended soil, whereas RF mobilized only 20% of it. Sequential extractions of Cd at time 0 and Cd remaining in soil showed that RFG had mobilized Cd mostly from the fraction bound with Fe and Mn oxides. Microbial biomass accounted for only up to 3.4% (w/w) of the soil constituents used in the experiments but resorbed 25% of mobilized Cd. The chemical composition of mobilizing soil extracts and the solid-to-mobilizing-extracts volume ratio had a significant effect on the amount of bioavailable Cd. The results of the study suggest that microbial metabolites were involved in Cd mobilization, while the biomass of microorganisms was involved in Cd resorption as a biosorbent.     

A physical-chemical screening model for anticipating widespread contamination of community water supply wells by gasoline constituents

Continuing modifications of fuels like gasoline should include evaluations of the proposed constituents for their potential to damage environmental resources such as subsurface water supplies. Consequently, we developed a screening model to estimate well water concentrations and transport times for gasoline components migrating from underground fuel tank (UFT) releases to typical at-risk community water supply wells. Representative fuel release volumes and hydrogeologic characteristics were used to parameterize the transport calculation. Subsurface degradation processes were neglected in the model in order to make risk-conservative assessments. The model was tailored to individual compounds based on their abundances in gasoline, gasoline-water partition coefficients (Kgw), and organic matter-water partition coefficients (Kom). Transport calculations were conducted for 20 polar and 4 nonpolar compounds found in gasoline, including methyl tert-butyl ether (MTBE) and other ether oxygenates, ethanol, methanol, and some aromatic hydrocarbons. With no calibration, the screening model successfully captured the reported magnitude of MTBE contamination of at-risk community supply wells. Such screening indicates that other oxygenates would cause similar widespread problems unless they were biodegradable. Stochastic analysis of field parameter variability concluded that community supply well contamination estimates had order-of-magnitude reliability. This indicated that such pre-manufacturing analyses may reasonably anticipate widespread environmental problems and/or inspire focused investigations into chemical properties (e.g., biodegradability) before industrial adoption of new fuel formulations.     

Integrated catchment modeling for nutrient reduction: scenarios showing impacts, potential, and cost of measures

A hydrological-based model (HBV-NP) was applied to a catchment (1900 km2) in the southern part of Sweden. Careful characterization of the present load situation and the potential for improved treatment or reduced soil leaching were analyzed. Several scenarios were modeled to find strategies to reach the Swedish environmental goals of reducing anthropogenic nitrogen load by 30% and phosphorus load by 20%. It was stated that the goals could be reached by different approaches that would affect different polluters and social sectors. However, no single measure was enough by itself. Instead, a combination of measures was necessary to achieve the goals. The nitrogen goal was the most difficult to attain. In order to be cost-effective, these measures should be applied to areas contributing the most to the net loading of the sea. This strategy could reduce the costs by 70%-80% when compared with implementing the measures in the entire catchment. Integrated catchment models may thus be helpful tools for reducing costs in environmental control programs.     

Concentrations and trends of benzene in ambient air over New York State during 1990–2003

Since 1990s, a systematic program to measure air toxics has been active in New York State with monitors located both in urban and rural areas. In this study we examined the spatial and temporal characteristics of benzene, a known human carcinogen that is emitted by many source categories. The analysis indicates that ambient concentration levels of benzene have decreased by as much as 60% over this period not only in the ozone non-attainment area of New York City that had the reformulated gas (RFG) requirements, but also over the rest of the state as well. Although the rate of decrease appears to have flattened out in recent years, the annual average concentration levels are found to be above the health risk threshold even at the remote location, Whiteface Mountain, suggesting the need for further reductions in benzene emissions.     

Exhibition

The objective of this critical review is to evaluate and summarize the literature on economic tools used to improve environmental decision making. Environmental decisions are complicated by pervasive uncertainty, and the lack of consensus on goals and on tradeoffs, such as air versus water pollution and versus loss of coal mining jobs. Five decision frameworks are used by regulatory agencies to simplify decision making. Congress’ choice of a decision framework designates the amount of data and analysis that will be required and the range and depth of social values that must be considered. Economic incentives have worked well for phasing out lead in gasoline, for increasing recycling and for reducing the volume of municipal solid waste. Congress has mandated incentives for acid rain and CFCs, and several countries have implemented carbon taxes to abate greenhouse gas emissions. Economic tools have become more central to the analysis and implementation of environmental policies; their role should continue to increase. We conclude that economic tools are extremely valuable, although their application is difficult.     

甲基叔丁基醚(MTBE)对环境的污染及其对我国汽油生产的影响

本文简要介绍了汽油添加剂MTBE对环境的污染及减少MTBE污染机理研究的进展 ,同时介绍了对我国汽油生产的影响     

Improving the environmental and performance characteristics of vehicles by introducing the surfactant additive into gasoline

The operation of modern vehicles requires the introduction of package of fuel additives to ensure the required level of operating characteristics, some of which cannot be achieved by current oil refining methods. The use of additives allows flexibility of impact on the properties of the fuel at minimal cost, increasing the efficiency and environmental safety of vehicles. Among the wide assortment of additives available on the world market, many are surfactants. It has been shown that the introduction of some surfactants into gasoline concurrently reduces losses from gasoline evaporation, improves the mixture formation during injection of gasoline into the engine and improves detergent and anticorrosive properties. The surfactant gasoline additive that provides significant improvement in the quality of gasoline used and environmental and operating characteristics of vehicles has been developed and thoroughly investigated. The results of studies confirming the efficiency of the gasoline additive application are herein presented.     

The Use of Stable Isotopes to Differentiate Specific Source Markers for MTBE

The recent controversy over the use of MTBE within gasoline to boost oxygen content and decrease carbon monoxide emissions to the atmosphere has led to a proposed phase-out of this compound by 2002. This paper is a preliminary investigation into the use of gas chromatography isotope-ratio mass spectrometry (GCIRMS) to determine both carbon and hydrogen isotopic compositions of MTBE as a means of differentiating sources of MTBE. Three pure MTBE samples were purchased from chemical distributors. Little variation of the i 13 C values were observed although the samples had isotopically distinct i -D values. Four different methods of obtaining carbon isotope ratios of neat MTBE, MTBE in gasoline, and MTBE in water are described, and the precision and accuracy of each is discussed. The carbon isotopic compositions of MTBE within 10 gasoline samples from three different areas of the United States show a wide range of carbon isotope compositions. This novel method of MTBE analysis could be valuable in forensic investigations.     

The Use of Stable Isotopes to Differentiate Specific Source Markers for MTBE

The recent controversy over the use of MTBE within gasoline to boost oxygen content and decrease carbon monoxide emissions to the atmosphere has led to a proposed phase-out of this compound by 2002. This paper is a preliminary investigation into the use of gas chromatography isotope-ratio mass spectrometry (GCIRMS) to determine both carbon and hydrogen isotopic compositions of MTBE as a means of differentiating sources of MTBE. Three pure MTBE samples were purchased from chemical distributors. Little variation of the δ¹³C values were observed although the samples had isotopically distinct δ-D values. Four different methods of obtaining carbon isotope ratios of neat MTBE, MTBE in gasoline, and MTBE in water are described, and the precision and accuracy of each is discussed. The carbon isotopic compositions of MTBE within 10 gasoline samples from three different areas of the United States show a wide range of carbon isotope compositions. This novel method of MTBE analysis could be valuable in forensic investigations.     

Identification of a potential source of chloroform in urban air: Preliminary Communication

A new potential source of elevated chloroform (CHCl₃) concentrations in urban air is reported. The exhaust gases from gasoline internal combustion engines operated on conventional “leaded” fuel and not equipped with catalytic converters contain parts-per-billion concentrations of chloroform which can, in congested urban areas, contribute significantly to the ambient concentration of chloroform. Exhaust gases from engines burning conventional “leaded” gasoline contain much higher levels of chloroform than do exhaust gases from engines equipped with catalytic converters and operating on “nonleaded” gasoline.     

Soviet and post-Soviet environmental management: lessons from a case study on lead pollution

Through a case study on lead pollution in the former Soviet Union, the linkage of policy, environmental science, and environmental management is explored, and compared with the US experience. Soviet bans on leaded gasoline and lead-based paint appear to have been effective. Regional governments, in cooperation with the petroleum industry, are taking the initiative in phasing out leaded gasoline, to some extent in defiance of federal policy. Problems with management of lead-acid batteries have been worsened by the collapse of the political system. Lack of reliable environmental data impedes reliable environmental assessment. The types of environmental measurements reflect an emphasis on multipollutant environmental contamination, rather than on human exposure to single pollutants.