vvEPA
EPA/600/R-10/001 | January 2010 | vwwv.epa.gov/athens
United States
Environmental Protection
Agency
Gasoline Composition Regulations
Affecting
LUST Sites
Ecosystems Research Division, Athens, GA 30605
National Exposure Research Laboratory
Office of Research and Development
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EPA/600/R-10/001
January 2010
Gasoline Composition Regulations Affecting
LUST Sites
by
James W. Weaver, Linda R. Exum, Lourdes M. Prieto
Ecosystems Research Division
National Exposure Research Laboratory
Office of Research and Development
United States Environmental Protection Agency
Athens, Georgia 30605
U.S. Environmental Protection Agency
Office of Research and Development
Washington, DC 20460
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Notice
The U.S. Environmental Protection Agency, through its Office of Research and
Development, funded and managed the research described here. It has been subjected to
the Agency's peer and administrative review and approved for publication as an EPA
document. Mention of trade names or commercial products does not constitute
endorsement or recommendation for use. The information provided in this paper is not
intended to determine compliance with state or federal regulations for air quality,
gasoline composition or similar purposes. For those purposes, information should be
obtained from the appropriate local, state and federal regulatory agencies, the Clean Air
Act, the United States Code, the Code of Federal Regulations, the Federal Register and
other sources.
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Abstract
Passage of the Clean Air Act Amendments in 1990 imposed requirements on
gasoline composition in the United States. Impacts to ground water are affected by the
provisions that required oxygenated additives and limited benzene concentration.
Reformulated and oxygenated gasoline were required to contain an oxygenated additive
at 2.0 wt % and 2.7 wt %, respectively. In most cases, the additive initially was methyl
tert-butyl ether (MTBE). The amount of benzene in both reformulated and conventional
gasoline was limited: reformulated gasoline contains less than 1 % benzene by volume,
while benzene levels in conventional gasoline were set by producer baselines. The
allowable benzene levels vary among these producers and, unlike reformulated gasoline,
are not tied to use at specific locations in the U.S. In 2000, states began to pass bans on
MTBE, other ethers, and/or alcohols; consequently, production and use of MTBE in
reformulated gasoline declined. The Energy Policy Act of 2005 removed the oxygenate
requirement from reformulated gasoline and industry responded by removing ethers from
U.S. gasoline, with some limited exceptions.
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Foreword
The National Exposure Research Laboratory's Ecosystems Research Division
(ERD) in Athens, GA conducts research on organic and inorganic chemicals, greenhouse
gas biogeochemical cycles, and land use perturbations that create direct and indirect
chemical and non-chemical stresses, exposures, and potential risks to humans and
ecosystems. ERD scientists develop, test, apply and provide technical support for
exposure and ecosystem response models that assess and manage risks to humans and
ecosystems within a watershed /regional context. The Regulatory Support Branch (RSB)
at ERD conducts problem-driven and applied research, develops technology tools, and
provides technical support to customers in program and regional offices, states,
municipalities, and tribes. Models are distributed and supported by EPA's Center for
Exposure Assessment Modeling (CEAM) and its Internet tools
(www.epa.gov/athens/onsite).
Research on gasoline composition is a fundamental part of assessing exposures to
contamination from leaking underground storage tanks and surface water releases of
petroleum fuels. Statistical analysis of gasoline samples, however, is not a sufficient
basis for understanding variations in gasoline composition across the United States.
Familiarity with the United States' unique regulatory requirements is a necessary
precursor to studying gasoline composition. This report gives an overview of the
regulations affecting major contaminants at leaking underground storage tank sites.
Candida C. West, Ph.D.
Acting Director
Ecosystems Research Division
Athens, Georgia
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Leaking Underground Storage Tank Assessment Report
Series
A series of research reports is planned that will present data and models for leaking
underground storage tank risk assessments. To date, these include:
1. Gasoline Composition
Weaver, James W., Linda R. Exum, Lourdes M. Prieto, 2008, Gasoline Composition
Regulations Affecting LUST Sites, United States Environmental Protection
Agency, Washington, D.C., EPA/600/R-10/001.
Weaver, James W., Sheldon A. Skaggs, David L. Spidle, and Guthrie C. Stone, 2009,
Composition and Behavior of Fuel Ethanol, United States Environmental
Protection Agency, Washington, D.C., EPA/600/R-09/037.
Weaver, James W., Lewis Jordan and Daniel B. Hall, 2005, Predicted Ground Water, Soil
and Soil Gas Impacts from US Gasolines, 2004: First Analysis of the Autumnal
Data, United States Environmental Protection Agency, Washington, D.C.,
EPA/600/R-05/032.
2. Simulation Models
Gorokhovski, Vikenti M. and James W. Weaver, 2007, A Catalog of Ground Water Flow
Solutions for Plume Diving Calculations, United States Environmental Protection
Agency, Washington, D.C.
Weaver, James W., 2004, On-line Tools for Assessing Petroleum Releases, United States
Environmental Protection Agency, Washington, D.C., EPA 600/R-04/101.
3. Model Background and Evaluation
Weaver, James W. and C. S. Sosik, 2007, Assessment of Modeling Reports for Petroleum
Release and Brownfields Sites, United States Environmental Protection Agency,
Washington, D.C., EPA 600/R-07/101.
As reports are added to this series, they can be found on EPA's web site:
http://www.epa.gov/athens/publications.
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Contents
Notice 2
Abstract 3
Foreword 4
Leaking Underground Storage Tank Assessment Report Series 5
Contents 6
Introduction 7
Regulatory History 7
Data Sources 10
Reformulated and Conventional Gasoline 15
Reformulated Gasoline 15
State Cleaner Burning Gasoline Programs 17
Conventional Gasoline 17
Geographic Extent 18
Oxygenated Gasoline 21
MTBEBans 26
Discussion and Conclusions 29
References 31
Acknowledgments 37
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Introduction
The magnitude of environmental contamination from gasoline releases depends,
among other factors, on composition of the gasoline. The amount of certain components
in gasoline varies for a number of reasons, including fuel performance characteristics,
refinery equipment and capabilities, crude oil sources, industry standards and regulation.
Of the many causes of variability, regulatory requirements may be dominant for some
components. Limits on certain component concentrations and properties have been set
by regulation. Benzene, ethers and alcohols are the best examples of components with
limitations, and vapor pressure is the best example of a limited property. In addition to
being regulated for their impact on air pollution, benzene and methyl fert-butyl ether
(MTBE) and other oxygenates are ground water contaminants. This report gives an
overview of the air quality regulations that affect major contaminants at leaking
underground storage tank sites.1
History
The Clean Air Act of 1970 established the framework for setting nation-wide air
quality goals (NAAQs) for pollutants Subsequently, states developed implementation
plans (SIPs) to meet those goals. To date, the U.S. Environmental Protection Agency
(EPA) and states have set goals for six pollutants: sulfur dioxide, particulate matter,
nitrogen oxides, carbon monoxide (CO), ozone, and lead (Ayres and Kornreich, 2004).
EPA was authorized to require registration and testing of specified fuels and fuel
additives (US Federal Register, 1975, 1976). Because of these requirements, we know
MTBE was registered for use in 1979, tert-amyl methyl ether (TAME) in 1981, and ethyl
tert-butyl ether (ETBE) in 1981 (Stikkers, 2002). Under authority granted by the Clean
1 The information provided in this paper is not intended for determining compliance with
state or federal regulations for air quality, gasoline composition or other similar purposes.
For these purposes, information should be obtained from the appropriate local, state and
federal regulatory agencies, the Clean Air Act, the United States Code, the Code of
Federal Regulations, the Federal Register and other sources.
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Air Act, EPA began to phase out leaded gasoline over a period of time that ended on
January 1, 1996. The original focus of the Clean Air Act was to limit emissions through
improved vehicle technology. As time went on this approach became less viable for
solving persistent pollution problems, and Congress believed that lead was being replaced
by toxic organic chemicals (Martels, 2004). Consequently, the Clean Air Act
Amendments (CAAA) of 1990 (42 U.S. Code 4701) expanded regulation of fuels to help
meet NAAQs for ozone and carbon monoxide and reduce toxic air pollutants (e.g.,
benzene).
The CAAA introduced several requirements that have had a major impact on
gasoline composition throughout the United States, beginning with implementation in
1992 and 1995, and continuing to the present. The most important requirements for
LUST sites were the total ban on lead in gasoline, and new requirements for three types
of gasoline: conventional, reformulated, and oxygenated. Both reformulated gasoline
(RFG) and oxygenated gasoline (OG) required oxygen-containing additives, because the
fuel would burn cleaner. Initially, the most common oxygenate was MTBE. The RFG
program limited the amount of benzene and total aromatics in reformulated gasoline.
Since RFG areas were specified at county or partial-county level or, in a few cases, at the
city level, there are different requirements in adjoining counties. This spatial distinction
between RFG and CG might not be absolute, however, because market forces guide
gasoline sales, and there are no restrictions on selling RFG in CG counties.
Parts of the country not using RFG were also affected by the CAAA because the
Act contained an anti-dumping provision to prevent air quality deterioration in areas
using conventional gasoline (CG). This requirement prevented benzene from being
moved out of the RFG and into the CG supply by establishing benzene concentration
limitations from producer/importer baseline conditions that existed in 1990. An
important distinction between CG and RFG is that CG baseline limitations are applied to
producers/importers, while RFG requirements apply to where the fuel is used.
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Consequently, at a given location the benzene concentration in CG is usually variable and
not very predictable2.
In response to dissatisfaction with ground water contamination, a number of state
legislatures banned MTBE and, in some cases, other ethers and alcohols, beginning in
2000. These state bans did not affect federal oxygen requirements for RFG and OG,
however, so MTBE typically was replaced by ethanol. In 2005, Congress passed the
Energy Policy Act (EPAct 2005) which removed the oxygenate mandate from the RFG
program. Gasoline suppliers responded by reducing the use of MTBE and other ethers.
A composition-related aspect of gasoline is octane number. Some gasoline —
called straight run gasoline — is a direct output from distilling crude oil, but its octane
number is too low to prevent engine knock in modern engines. Therefore, the octane
number is boosted in a number of ways. These commonly include the use of alkyl leads,
aromatic hydrocarbons, ethers, alkylate and alcohols (Owen and Coley, 1995). Shifts
among these have occurred, partly due to laws and regulations that address different goals
(see e.g., Stikkers, 2002). Only small amounts of certain additives, 1 g/L or less of alkyl
leads or 0.017 g/L methylcyclopentadienyl manganese tricarbonyl (MMT), are needed to
increase octane levels from 5 to 25 octane numbers, depending on the blendstock (Owen
and Coley, 1995). Blending higher amounts of some organic compounds also increases
resistance to engine knock, but their levels typically must be one percent or higher. In
1979, MTBE was registered as an octane enhancer, so it may have appeared in gasoline
for octane purposes even when there was no regulatory mandate for oxygenated
additives. This has been borne out by gasoline composition studies in which MTBE
appeared in CG when it was not required (Weaver et al., 2005).
Timing of the mandates varied according to federal requirements or state
implementation plans. Nationally, the RFG program had an implementation date of
January 1, 1995, so RFG began appearing on the market in late 1994. Opt-out and opt-in
2 In 2011 the Mobile Sources Air Toxics rule (U. S. Federal Register, 2007) will reduce benzene levels in
all gasoline.
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provisions allowed areas to enter or leave the programs at different times. The
oxygenated gasoline program began in the fall of 1992. Since it specified oxygenated
fuel to be used only during a few months in winter, there was a characteristic pattern of
oxygenate usage in these locations. Where NAAQs for CO were met later,
implementation plans were revised to remove oxygenated gasoline requirements; for
example, see U. S. Federal Register (1999, 2000) for an example from New York State.
Data Sources
In the next two sections, data from three sources were compared to the regulatory
time lines. First was the Northrup-Grumman data set (e.g., Dickson, 2006), which
published results from an industry consortium that has collected data since the 1930s.
This company is the latest successor to the well-known National Institute for Petroleum
and Energy Research (NIPER). Its analyses were performed using ASTM standard
methods for analysis of aromatics, ethers and alcohols. Northrup-Grumman data from
1976-2007 were obtained in an electronic format, then sorted by city and octane number
(ON). Three octane number classes were used: regular (less than 88.5 ON), mid-grade
(88.5 ON to 90 ON), and premium (above 90 ON).
The second source was data from the Reformulated Gasoline Survey Association.
This group conducts surveys of RFG required by the Clean Air Act and reports the results
to EPA, which then evaluates the data for compliance. California is not included in these
surveys.
Lastly, the U.S. Department of Energy's Energy Information Agency (EIA)
collects weekly data from producers on their production of gasoline and a variety of fuel
components.
Leaded Gasoline
Use of lead in gasoline declined throughout the 1980s (Figure 1) and this phasing
out contributed to the rise in use of ether in gasoline (Stikkers, 2002). Averaged data
10
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from NIPER/Northrup-Grumman show that lead usage was highest in premium gasoline
and, on average, lower in mid-grade and regular gasoline. For example, Figure 1 shows
that in 1978, premium gasoline contained at least 1 g/gal, mid-grade at least 0.5 g/gal,
and regular may have contained no lead at all. After reaching levels as high as 4
g/gallon, by 1986 most lead was reduced to concentrations of 1 g/gallon. Complete
removal of lead was mandated by the Clean Air Act Amendments of 1990, and occurred
on January 1, 1996. Lead can still be used, however, in aviation gasoline and racing
fuel.
Premium (>90 Octane)
1976 1978 1980 1982 1984 1986 1988 1990 1992 1994 1996 1998
5 —i
Mid Grade (88.5 < Octane < 90)
1976 1978 1980 1982 1984 1986 1988 1990 1992 1994 1996 1998
Regular (<88.5 Octane)
1976 1978 1980 1982 1984 1986 1988 1990 1992 1994 1996 1998
Year
Figure 1 Data illustrating the phasing out of lead from gasoline in the United States in premium
(top), mid-grade (middle), and regular (bottom). After declining through the 1980s, lead was
completely eliminated by January 1,1996 by the Clean Air Act Amendments of 1990.
11
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Gasoline Production in the United States
Gasoline production data compiled by EIA document the production of
conventional and reformulated gasoline. The data show that production of RFG began in
September 1994, shortly before the RFG program was implemented when RFG replaced
part of total gasoline production in the U.S. (Figure 2 A). The remainder of production
became conventional gasoline (see U.S. CFR, 2007, Title 40, Part 80, Section 2).
Production of both types of gasoline tended to increase over time. In 2004, EIA began
differentiating ether-, alcohol-, and non-oxygenated RFG (Figure 2 B). The data show
declining use of ether in RFG from 2004 until mid-2006, when ethers finally were
replaced by alcohol. The slow decline of ether use corresponds to when MTBE was
being banned by the states. When the oxygenate mandate was removed by the Energy
Policy Act of 2005, ethers were removed from RFG. While ether use was declining,
alcohol use was increasing until almost all RFG produced after the EPAct 2005 took
effect contained alcohol. This legislation also required increased use of ethanol, as
shown by the increased amount of all gasoline containing ethanol. By December 2009,
77% of all U.S. gasoline contained alcohol.
RFG Survey Association data indicate that MTBE in RFG outside California
decreased, on average, from 7.9% to 0.01%; ethanol increased from 2.2% to 9.2%; and
benzene remained nearly the same — 0.61% in 2002 versus 0.69% in 2006. These data
also document removal of ethers from the U.S gasoline supply (
Figure 4). Ether levels in gasoline declined throughout the summer months of
2006, so that the date when the oxygenate requirement was removed did not correspond
to immediate removal of ethers. Some U.S. gasoline is imported, but no RFG with ether
has been imported since June 20063 (Figure 3 A). Production of RFG with ether has
continued sporadically at very low levels from 2004 through 2009 (Figure 3 B)4.
3 Conventional gasoline is also imported, but EIA data show only very small amounts of alcohol-containing
gasoline has been imported, and none since Mar, 2008.
4 EIA export data show only the total of petroleum products exported.
12
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distinction between conventional and reformulated gasoline. Since 1995, the proportion of
conventional gasoline has remained roughly constant. B. Since removal of the oxygenate mandate in
2006, the amount of reformulated gasoline with ether has declined dramatically, although there has
been a commensurate increase in RFG with alcohol. Mandates for increased use of ethanol have
increased the amount of CG with alcohol, while the amount of RFG with alcohol has remained
roughly constant. The total amount of gasoline with alcohol has increased to be approximately 77%
of the total in December 2009.
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have been produced in the U.S.
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Figure 4 RFG Survey Association data, as reported to EPA, show that the removal of ethers from
reformulated gasoline (except in California) occurred over the summer months of 2006.
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Reformulated and Conventional Gasoline
Reformulated Gasoline
EPA defines reformulated gasoline as gasoline that is certified (U.S. CFR, 2007,
Title 40, Part 80, Section 41) to meet requirements and standards specified in U.S CFR,
2007, Title 40, Part 80, Section 42. The requirements varied during four time periods:
1995-1997; 1998-1999; 2000 to May 5, 2006; and May 5, 2006 to the present (April 24,
2006 in California, see U.S. EPA, 2006). Although other requirements of RFG changed
over these times, the required oxygen content and benzene limitation did not change until
the Energy Policy Act passed in 2005 (Table 1). The oxygen requirement was removed
in California effective April 24, 2006, and in the rest of the U.S. effective May 5, 2006.
Beginning in 2011, benzene content in all U.S. gasoline will be reduced to 0.62 vol % to
comply with the Mobile Sources Air Toxics Rule (U.S. Federal Register, 2007).
As shown in Table 1, standards were met on either an averaged or per-gallon
basis. Using average basis, oxygen concentration in a gallon may have been as low as
1.5 wt %, but had to average 2.1 wt %. The total oxygen content could have been limited
to 3.2 wt % when gasoline contained ethanol (U.S. CFR, 2007, Title 40, Part 80, Section
41 i.
Table 1 Oxygen and benzene requirements for reformulated gasoline.
Component
Oxygen (weight percent)
Benzene (volume percent)
Effective Dates
1995 to May 5, 2005
May 5, 2005 to present
1995 to present
RFG Content Requirements
Per-gallon
Basis
>2.0
none
<1.00
Averaged Basis
Standard
>2.1
none
<0.95
Limit
> 1.5
none
< 1.30
The amounts of various ethers and ethanol that were needed to meet the oxygen
requirement are shown in Table 2; for example, a gallon of gasoline containing 11.0 vol
% MTBE met the per gallon oxygen requirement of 2.0 wt %. If the producers chose to
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meet the standard on an averaged basis, there could have been compliant gasoline with
MTBE content as low as 8.25 vol %. Thus, while a gallon of gasoline containing 11.0
vol % MTBE clearly complied with the standard, gasoline containing less than 11.0 vol
% could comply in two ways. First, if the producer chose to meet the standard on an
average basis and the batch met the 2.1 wt % oxygen requirement, then the fuel was
compliant. The second was when more than one oxygenate was present: any single
oxygenate could be present in a relatively low concentration, but the total oxygen
supplied by all compounds had to meet the requirement. Similarly, RFG containing 1.0
vol% benzene complied with the per-gallon basis. One specific gallon of gasoline
containing 1.30 vol % benzene could be compliant if the producer met the standard using
the average basis.
Table 2 Oxygen and required amounts of oxygenates to meet requirements of reformulated and
winter oxygenated gasoline. Values given as weight percent.
Weight percent of oxygen
Required Oxygenate Concentration
RFG
Per-gallon
Basis
2.0 %
Averaged Basis
Standard
2.1%
Minimum
1.5%
Winter Oxygenate
2.7%
oxygen
required
3.1% oxygen
required
Common Oxygenates and Required Content to Meet Oxygen Requirements
Methyl tert-butyl ether
Ethyl fer/-butyl ether
Tert-amyl methyl ether
Diisopropyl ether
Ethanol
11.0%
12.75%
12.75%
12.75%
5.8%
11.6%
13.4%
13.4%
13.4%
6.0%
8.25%
9.6%
9.6%
9.6%
4.3%
14.9%
17.2%
17.2%
17.2%
5.4%
17.1%
19.8%
19.8%
19.8%
6.2%
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State Cleaner Burning Gasoline Programs
Three states, Arizona, California and Nevada, have implemented cleaner burning
gasoline (CBG) programs. A summary of requirements for California's program are
given in Table 3. Arizona requires cleaner burning gasoline in the Phoenix area (U.S.
Federal Register, 2004), and Nevada requires the same for the Las Vegas area (Clark
County, Nevada, 2003). Arizona's cleaner burning gasoline matches the characteristics
of either federal RFG or California CBG. Nevada imposes limits on sulfur and aromatic
composition.
Table 3 MTBE and benzene requirements for California cleaner burning gasoline (CBG), given in
units of volume %. California allows refiners to meet standards for each batch of finished gasoline—
the "flat" limit. Alternatively, a refiner can meet standards on an average over 180 days. In the
latter case, the averaging limit must be met for all batches and no batch can exceed an upper/lower
limit ("cap"). The lower cap limit of 1.8% in Phase 2 and Phase 3 apply to certain counties in the
winter (California, 2003a).
Oxygen content
Benzene
Phase 1
January, 1992
1.8%-2.3%
1.7%
Phase 2
March, 1996
flat
1.8% -2.2%
1.0%
avg
n/a
0.80%
cap
1.8%-3.5%
0%-3.5%
1.20%
Phase 3
January, 2004
flat
1.8% -2. 2%
0.80%
avg
n/a
0.70%
cap
1.8%-3.5%
0%-3.5%
1.10%
Conventional Gasoline
Conventional gasoline is gasoline that has not been certified as RFG (i.e., meeting
the U.S. CFR, 2007, Title 40, Part 80, Section 41 requirements), but it must meet
requirements of anti-dumping provisions of the CAAA (U.S. CFR, 2007, Title 40, Part
80, Section 90 and following sections). These were designed to prevent increased
average per-gallon emissions of volatile organic compounds, nitrogen oxides, carbon
monoxide and toxic air pollutants, in addition to requirements imposed on reformulated
gasoline (CAAA Sec 21 l(k)(8)). Baselines for each refiner and producer were set, using
their production/importation for 1990, or by statutory baseline with a benzene content of
1.53 vol % for winter and 1.64 vol % for summer (U.S. CFR, 2007, Title 40, Part 80,
Section 91(c)(5) and Section 45, (b)(2)). Other features of the statutory baseline are
17
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given in Table 4. Because of different producer baselines, benzene content of gasoline in
conventional gasoline areas can vary. Recent EPA studies have shown benzene content
in conventional gasoline ranged from 0.5 vol % to 3.0 vol % or in very limited instances
to 5% (Weaver et al., 2005)..
Table 4 Selected parameters of the statutory baseline for conventional gasoline (40 CFR 80.91 and
40 CFR 80.45)
Parameter Winter Summer Average
Benzene (vol %)
Aromatics (vol %)
Olefins^ (vol %)
Reid Vapor Pressure
(psi)
API Gravity(**} (°API)
40CFR 80.91(c)(5)(i)
40CFR 80.45(b)(2)
1.64
26.4
11.9
8.7
60.2
40CFR80.91(c)(5)(ii)
40CFR 80.45(b)(2)
1.53
32
9.2
8.7
57.4
40CFR80.91(c)(5)(ii)
1.60
28.6
10.8
8.7
59.1
^Olefms are also known as alkenes
("} API Gravity (°API) is defined by:
141.5
API Gravity =
Specific Gravity
- 131.5
Geographic Extent
A map of locations required to use federal reformulated and conventional gasoline
is shown in Figure 5. The map shows that RFG has been used in the northeast corridor,
large Midwestern cities, Arizona and California. It also shows that geographically, most
of the U.S. uses conventional gasoline. For the majority of counties using RFG, the RFG
oxygenate mandate was in force from January 1, 1995 to May 5, 2006. Counties in the
Los Angeles area were included at the beginning of the program, but had an earlier date
(April 24, 2006) for removing the oxygen mandate. Counties in the Sacramento
metropolitan area were added in 1996, and those in the San Joaquin Valley in 2002.
These latter two groups also share the April 2006 federal oxygen mandate removal date.
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Counties in the St. Louis, Missouri metropolitan area opted into the program on
June 1, 1999. Four counties in Illinois opted into the RFG program in 2007 and, because
of the late date, never were required to use oxygenates. In 1997, the Phoenix
metropolitan area opted into the program, then opted out in 1998 because of Arizona's
cleaner-burning gasoline program (see Figure 5 and U.S Federal Register, 2004). Seven
counties in Maine opted out of the program in 1999.
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^3 State Cleaner Burning Gasoline (CBG)
Federal Oxygenate Requirement Duration
I 1 1.1.95 to 3.10.99
I 1 1.1.95 to 4.24.06
I 1 1.1.95 to 5.5.06
I I 6.1.96 to 4.24.06
I I 8.1.97 to 6.18.98
I 1 6.1.99 to 5.5.06
I I 12.10.02 to 4.24.06
I 1 None
0 200 400 600 800 1000 Kim
Figure 5 Federal reformulated gasoline and state cleaner-burning gasoline programs in the United States (California, 2003a; Clark County, Nevada,
2003; U.S. CFR, 2005, Title 40, Part 80, Section 40 U.S. CFR, 2007, Title 40, Part 80, Section 40, U.S Federal Register, 2004). Durations of oxygenate
mandates are shown on the legend. All areas not highlighted on the map use conventional gasoline. Reformulated gasoline is required above 3500 ft
elevation on Whiteface Mountain in northern New York
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Oxygenated Gasoline
The Clean Air Act Amendments (42 U.S.C. 7545, m, 1) required states to
mandate at least 2.7 wt % oxygen in gasoline sold in areas where carbon monoxide
standards were not attained. This requirement was imposed for at least four months of
the year when ambient CO concentrations were highest. EPA could reduce the duration
if a state demonstrated there were no exceedances of the carbon monoxide standard. If a
carbon monoxide standard was not attained by a required date, gasoline containing 3.1%
by weight was required.
The areas were defined as the larger of Consolidated Metropolitan Statistical
Area or Metropolitan Statistical Area. The program began in late fall 1992 in 39 areas,
with one more added in 1993. Six cities began winter oxygenate programs earlier — in
the 1989/1990 winter season: Denver, Colorado; Reno and Las Vegas, Nevada; Tucson
and Phoenix, Arizona; and Albuquerque, New Mexico (Stikkers, 2001). Table 5 lists the
nine areas still in the program to the present, along with their required oxygen content
and effective months. Table 6 lists areas that no longer implement the program, and their
effective ending dates. The geographic concentration of remaining cities in the southwest
is shown in Figure 6. Table 7 lists cities that have exited the program, but retain the
option of using oxygenated gasoline as a contingency measure.
Six states have state-wide oxygenate mandates (Table 8). Each of the state
requirements differ, but the required ethanol contents do not exceed the federal limit of
10%. Montana imposed a conditional requirement for using ethanol in gasoline, in
conjunction with a conditional ban on MTBE (Montana, 2005) that has so far not been
imposed (Kuhn, 2010).
21
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Table 5 Cities currently implementing the winter oxygenates program (U.S EPA, 2008c).
Control Period Area (Consolidated Metropolitan Statistical Area) Oxygen Content (wt %)
10/1 to 1/31 Reno,NV 3.5
10/1 to 3/31 El Paso, TX 2.7
Las Vegas, NV 3.5
Reno,NV 3.5
Tucson, AZ 1.8
11/1 to 2/29 Albuquerque, NM 2.7
Missoula, MT 2.7
Los Angeles, CA 1.8 to 2.2
11/2 to 3/31 Phoenix, AZ 3.5
22
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Table 6 Cities exiting the winter oxygenates program (U.S. EPA, 2008c).
Area (Consolidated Metropolitan Statistical
Area)
Syracuse, NY
Cleveland, OH
Greensboro, NC
Duluth, MN
Memphis, TN
Raleigh-Durham, NC
Baltimore, MD
Hartford, CT
Philadelphia, PA
Washington, DC
Boston, MA
Seattle, WA
Vancouver, WA
San Diego, Chico, Modesto, Sacramento,
Fresno, San Francisco, and
Stockton, CA
New Haven, CT
Salt Lake City, UT
Northern NJ/
Southwest CT/
New York, NY
Minneapolis/St. Paul, MN
Colorado Springs, CO
Ogden, UT
Ft. Collins, CO
Provo/Orem UT
Portland, OR
Denver/Boulder, CO
Longmont, CO
Effective Exit Date
Sep29, 1993
Mar 7, 1994
Nov7, 1994
Jun 13, 1994
Sep26, 1994
Sep 18, 1995
Dec 15, 1995
Jan 2, 1996
Mar 15,1996
Mar 15, 1996
Apr 1,1996
Octl 1,1996
Oct21, 1996
Jun 1,1998
Dec 4, 1998
Mar 22,1999
Nov22, 1999
Jan 31,2000
May 19,2000
Nov29, 1999
Feb 20, 2000
May 8, 2001
Jan 1,2004
Jan 3, 2006
Feb 23, 2006
Octl 6, 2007
Octl 6, 2007
Table 7 Cities exiting the winter oxygenates program (U.S. EPA, 2008c), with oxygenated gasoline as
a contingency measure in their states' maintenance plans.
Area (Consolidated Metropolitan Statistical Area)
Grants Pass, OR
Klamath Co, OR
Medford, OR
Anchorage, AK
Spokane, WA
Redesignation/SIP Change Published in the
Federal Register
Oct 30, 2000
Nov 19, 2001
Sep 23, 2002
Jul 23, 2004
Aug 29, 2005
23
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Table 8 State ethanol mandates.
State
Florida
Hawaii
Minnesota
Missouri
Oregon
Washington
Ethanol
Requirement
Vol %
9 to 10
10
2.7 (a)
9.2 to 10
20 or max allowed
by EPA
10
10
"2% of gasoline"
Effective Date
Dec 21, 2010
1994
Oct 1, 1997
2003
Aug20, 2013
Jan 1, 2008
Nov 1, 2009
Dec 1, 2008
Citation
Florida, 2009
Hawaii, 2004
Minnesota, 1997
Minnesota, 2003
Minnesota, 2009
Missouri, 2008
Oregon, 2009
Washington, 2009
'^Oxygenated fuel requirement, Minnesota ethanol producer credit caused ethanol usage.
24
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[ .1 State ethanol requirement
Winter oxygenate requirement
© Current Cities
A Past Cities
Figure 6 Oxygenated gasoline programs in the United States. Cities where an oxygenated additive was, or is, required for winter time gasoline are
indicated by triangles and circles, respectively. Six states have imposed year-round oxygenate mandates. Montana has a future requirement that is
conditional on in-state ethanol production.
25
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MTBE Bans
Twenty-six states, two counties, and one city have banned MTBE in gasoline
(Figure 7). Three states have imposed absolute bans, while most allow some MTBE to
remain in gasoline (Table 9). In 17 states, the level was 0.5%, but ranged from 0.05% in
California to 1% in Nebraska. Six states banned MTBE and other oxygenates which
included the other gasoline oxygenate ethers: ethyl tert-buty\ ether (ETBE); fert-amyl
methyl ether (TAME); diisopropyl ether (DIPE); and alcohols, mostly fert-butyl alcohol
(TEA). The bans did not affect requirements to use reformulated or oxygenated-gasoline,
but did cause a shift to another oxygenate. One data set shows that the other oxygenate
most commonly used was ethanol (Weaver et al., 2005). Oregon passed a conditional
ban of various ethers and alcohols, but was only effective if these were banned by each of
the California Air Resources Board, the California Environmental Policy Council and the
US EPA (Oregon, 2009).
26
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New
Hampshire
01/07
Vermont
01/07
Rhode Island
06/07
Connecticut 01/04
New Jersey 01/09
El Dorado
County CA/ /
"4/2000 /Kwashoe
County NV
12/03
Total MTBE ban or not
greater than
| 1 0.05 vol%
I 1 0.3 vol%
I | 0.5 vol%
I | 0.6 vol%
I 11.0 vol%
| 1 Total MTBE ban
| | Trace amounts only
| 1 No ban
Figure 7 State MTBE, ether, and/or alcohol bans, showing effective dates and maximum levels allowed for MTBE. Please refer to Table 9 for full
details on other ethers and alcohols.
27
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Table 9 MTBE and other oxygenate ban dates, maximum allowable limits, and citation.
State/County/City
Arizona
California
Chicago
Colorado
Connecticut
El Dorado
County, California
Illinois
Indiana
Iowa
Kansas
Kentucky
Maine
Michigan
Minnesota
Missouri
Nebraska
New Hampshire
New Jersey
New York
North Carolina
North Dakota
Ohio
Rhode Island
South Dakota
Vermont
Washington
Washoe County,
Nevada
Wisconsin
Ban Dates
Enacted
05/11/04
03/14/03
12/13/00
09/01/00
06/18/03
03/28/00
07/24/01
07/01/02
07/01/00
07/01/01
07/15/02
07/30/05
06/26/00
04/20/00
08/28/02
04/11/00
05/27/04
08/18/05
05/24/00
06/21/05
03/31/05
08/28/02
07/06/05
02/16/00
02/28/01
05/23/05
05/09/01
10/25/00
Revised
09/22/05
08/11/03
Effective
01/01/05
12/31/03
07/01/04
12/31/05
07/01/07
12/13/00
04/30/02
01/01/04
4/28/00
07/24/04
07/23/04
12/31/00
07/01/04
01/01/06
01/01/07
06/01/03
07/01/00
07/01/05
07/01/05
07/13/00
01/01/07*
01/01/09
01/01/04
01/01/08
08/01/05
07/01/05
06/01/07
07/01/00
07/01/01
01/01/07
01/01/04
12/31/03
10/1-1/31
09/22/05
Yr round
08/01/04
de minimis Levels (vol%)
MTBE
0.3
0.60
0.30
0.15
0.05
none
none
0.5
none
0.5
0.5
0.5
0.5
0.5
0.5
^
0.33
none
0.5
1.0
0.5
0.5
0.5
0.5
0.5
0.5
0.5
2.0
0.5
0.5
0.6
0.30
0.30
0.5
ETBE
*
**
**
0.33
none
A
0.5
0.5
TAME
*
**
**
0.33
none
A
0.5
0.5
DIPE
*
**
**
A
0.5
0.5
TEA
*
**
**
0.5
n
Others
*
**
**
0.5
n
Citations
Arizona (2004)
California Air
Resources Board
(2003b)
City of Chicago (2000)
Colorado (2000)
Connecticut (2003)
El Dorado County (2000)
Illinois (2001)
Indiana (2002)
Iowa (2000)
Kansas (2004)
Kentucky (2002)
Maine (2005)
Michigan (2000)
Minnesota (2000)
Missouri (2002)
Nebraska (2000)
New Hampshire (2004)
New Jersey (2005)
New York (2000)
North Carolina (2005)
North Dakota (2005)
Ohio (2002)
Rhode Island ( 2005)
South Dakota (2000)
Vermont (2005)
Washington (2001)
Washoe County District
Board of Health (2005)
Wisconsin (2003)
* Sum of diisopropylether (DIPE), ethyl terf-butylether (ETBE), isobutanol, isopropanol, methanol, n-butanol, n-propanol, sec-butanol, terf-amylmethyl ether
(TAME), terf-butanol, ferf-pentanol (terf-amylalcohol) not to exceed 0.1% by volume, starting 01/01/2006
"Sum of methanol, isopropanol, n-propanol, n-butanol, isobutanol, sec-butanol, terf-butanol terf-pentanol (terf-amylalcohol), ethyl terf-butylether (ETBE),
diisopropylether (DIPE), ferf-amylmethylether (TAME) not to exceed 0.10 weight % oxygen, starting 12/31/2003, sum of same not to exceed 0.06 weight %
oxygen, starting 07/01/2004
»"".. .within 12 months after the Department of Transportation has certified that the State of Montana has produced 40 million gallons of denatured ethanol and
has maintained that level of production on an annualized basis for at least 3 months.. .ensure that all gasoline sold to consumers .. ..may not contain more than
trace amounts of the additive methyl tertiary butyl ether." Montana Code Annotated 2005 82-15-121
• ".. .shall take effect on the later of 01/01/07 or 6 months after federal approval" to opt out of the Federal Reformulated Gasoline Program (see paragraph II,
Section 1 of Act 175-4)
A "No person.. .shall sell.. .any neat gasoline ethers or gasoline containing MTBE, other gasoline ethers or tertiary butyl alcohol (TEA) in quantities greater
than Vi of 1% by volume"
n Other ether oxygenates not greater than 0.5%: methanol, isopropanol, n-propanol, n-butanol, sec-butanol, ferf-butanol, terf-pentanol (tert amylalcohol)
isobutanol
28
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Discussion and Conclusions
The Clean Air Act Amendments of 1990 imposed a set of requirements for gasoline in
the United States. For LUST sites, the three most important are:
1) Final Ban of Leaded Gasoline
Banning leaded gasoline had two major effects on LUST sites. First,
removing lead resulted in new ways to boost the octane rating of gasoline. Most
significant was the introduction of MTBE and other ethers, beginning in 1979;
notably, this predates oxygenate requirements of the Clean Air Act Amendments.
Second was the concurrent removal of lead scavengers. These compounds -
ethylene dibromide and 1,2 dichlorethane - prevent precipitation of lead on
engine parts. They recently were shown to persist in ground water at some sites
(Falta, 2004, Falta et al., 2005), and continue to cause contamination problems.
2) Conventional and Reformulated Gasoline
The Clean Air Act Amendments of 1990 created a framework for the two
major types of gasoline sold in the U.S., reformulated and conventional. With a
few exceptions, use of RFG has been on a county-by-county basis. Although
most of these locations have used RFG for long periods, some changes have
occurred as indicated on Figure 5.
The composition of RFG is specified by provisions of the Clean Air Act.
Relevant for leaking underground storage tanks are provisions that limit benzene
to a nominal level of 1.0% by volume and, until mid-spring of 2006, required an
oxygenated additive at 2.0% by weight. Conventional gasoline is gasoline which
is not reformulated — the remaining gasoline in the U.S. The benzene content in
conventional gasoline is limited by producer/importer baselines set in 1990.
Because the baselines are not tied to point-of-use, they do not provide a guide for
specific locations. Another complicating factor is the use of oxygenates as octane
29
-------
enhancers. These could be used anywhere and evidence of their preferred use in
premium gasoline appears in a companion study.
3) Oxygenated Gasoline Program
The Clean Air Act Amendments of 1990 mandated states to require
oxygenated gasoline in areas that did not attain carbon monoxide standards in the
winter months. Beginning in 1992, these requirements were imposed in selected
cities, but as carbon monoxide standards were met, cities gradually dropped out of
the program.
The CAAA of 1990 indirectly led to a fourth impact on gasoline composition, which
occurred because of the states' reaction to ground water contamination by MTBE:
4) State MTBE and Other Oxygenate Bans
Beginning in 2000, state legislatures enacted bans or restrictions on
oxygenate usage in gasoline. In some cases these included only MTBE, while in
others a whole suite of ethers and alcohols were restricted. Most restrictions
allowed MTBE content of up to 0.5% by volume. There continues to be sporadic
production of small amounts of RFG with ether, which could be used in states
without ether bans.
Despite changes caused by the states' oxygenate limitations and by removal of the
oxygenate mandate for reformulated gasoline, the framework for reformulated and
conventional gasoline is still in place in the United States. State oxygenated gasoline
programs, mostly in the southwestern United States, continue to rely on ethanol to meet
their oxygenate requirements. Ethanol usage has increased steadily so that 77% of U.S.
gasoline now contains ethanol. Benzene concentrations in RFG were limited to 1 vol %,
and will be further reduced to 0.62 vol % in all U.S. gasoline by 2011.
30
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36
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Acknowledgments
The authors appreciate the assistance of Kurt Gustafson, of the US EPA, Office of
Transportation and Air Quality, Tim Hogan of the National Petrochemical and Refiners
Association, Karen Ellenberger and Hal White, USEPA Office of Underground Storage
Tanks; Carol Weisner and Joe Abraham, USEPA San Francisco; Maria Tome and John
Tantlinger, Department of Business, Economic Development, and Tourism, State of
Hawaii; Andy Goodrich and Daniel Inouye, Washoe County Government, Nevada;
Tancred Lidderdale, Elizabeth Scott, and Chuck Shirkey, U.S. Dept. of Energy, Energy
Information Administration; Jeff Kuhn, Montana Department of Environmental Quality,
Brian Oakland and Syed Nayyer, State of South Dakota; Mandy Easter, State Law
Library of Iowa; Ross J Andersen, New York State Department of Agriculture and
Markets; Charlotte Neuner, Missouri Legislative Research; Fred McGarry, New
Hampshire Dept. of Environmental Services; Mark Toso, Minnesota Pollution Control
Agency, Jim Glass and Clark Cooney, Oregon Department of Environmental Quality,
and Fran Rauschenberg USEPA/SEE, Athens, Georgia.
37
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