ARTICLE IN PRESS

Atmospheric Environment 42 (2008) 4498–4516

www.elsevier.com/locate/atmosenv

Emissions from light duty gasoline vehicles operating on

low blend ethanol gasoline and E85
Lisa A. Graham, Sheri L. Belisle, Cara-Lynn Baas1
Emissions Research and Measurement Division, Environmental Science and Technology Centre, Environment Canada,
335 River Road, Ottawa, Ontario, Canada K1A 0H3
Received 19 September 2007; received in revised form 24 January 2008; accepted 29 January 2008

Abstract

The results of two recent vehicle emission studies are described in this paper, along with a statistical analysis of the
changes in tailpipe emissions due to the use of ethanol that includes the results from these two studies in combination with
results from other literature reports. The first study evaluates the effect of two low blend ethanol gasolines (E10, E20) on
tailpipe and evaporative emissions from three multi-port fuel injection vehicles and one gasoline direct injection vehicle at
two different test temperatures. The second study evaluates the differences in tailpipe emissions and fuel consumptions of
paired flexible fuel and conventional gasoline vehicles operating on California RFG Phase 2 and/or E85 fuels at 20 1C. The
vehicles were tested over the four-phase FTP or UDDS and US06 driving cycles. Tailpipe emissions were characterized for
criteria pollutants (CO, NOX, NMHC, NMOG), greenhouse gases (CO2, CH4, N2O), and a suite of unregulated emissions
including important air toxics (benzene, 1,3-butadiene, formaldehyde, acetaldehyde, acrolein), and ozone reactivity. In the
low blend ethanol study, evaporative emissions were quantified and characterized for NMHC. While contradicting, results
can be seen among the various literature reports and with these two new studies, the statistical analyses of the aggregated
data offers much clearer pictures of the changes in tailpipe emissions that may be expected using either low blend ethanol
gasoline (E10) or E85. The results of the statistical analysis suggest that the use of E10 results in statistically significant
decreases in CO emissions (16%); statistically significant increases in emissions of NMHC (9%), NMOG (14%),
acetaldehyde (108%), 1,3-butadiene (16%), and benzene (15%); and no statistically significant changes in NOX, CO2, CH4,
N2O or formaldehyde emissions. The statistical analysis suggests that the use of E85 results in statistically significant
decreases in emissions of NOX (45%), NMHC (48%), 1,3-butadiene (77%), and benzene (76%); statistically
significant increases in emissions of formaldehyde (73%) and acetaldehyde (2540%), and no statistically significant change
in CO, CO2, and NMOG emissions.
Crown Copyright r 2008 Published by Elsevier Ltd. All rights reserved.

Keywords: Ethanol–gasoline blends; Mobile source air toxics; Greenhouse gas emissions; Evaporative emissions

1. Introduction

Corresponding author. Tel.: +1 613 990 1270;

Today, the motivations for blending ethanol with
gasoline are different in Canada and the USA.
fax: +1 613 952 1006.
E-mail address: Lisa.Graham@ec.gc.ca (L.A. Graham).
However, these motivations have evolved over the
1
Present address: Industry Canada, 50 Victoria St., Gatineau, last 15 years from a common starting point:
Quebec, Canada, K1A 0C9. reducing the negative impacts on local and regional

1352-2310/$ - see front matter Crown Copyright r 2008 Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.atmosenv.2008.01.061
 ARTICLE IN PRESS
L.A. Graham et al. / Atmospheric Environment 42 (2008) 4498–4516
air quality that arise from gasoline-powered vehicle
emissions, specifically ground level ozone, toxic air
pollutants, and carbon monoxide. In 1992, the US
Clean Air Act implemented a wintertime oxyge-
nated fuels program for cities with elevated ambient
concentrations of CO during the cold months. This
program required 2.7% by weight of oxygen in
gasoline and the oxygenate of choice for this
program was ethanol (US EPA, 2007a). In Canada,
similar fuels were available, but were not mandated
as in the USA. In 1995, the US Federal Reformu-
lated Gasoline (RFG) regulations were introduced.
RFG is required by the US Clean Air Act in cities
with the worst smog pollution and other cities with
smog problems may choose to use RFG. RFG is
currently used in 17 states and the District of
Columbia and about 30% of gasoline sold in
the USA is reformulated (US EPA, 2007b). The
RFG regulations established emissions performance
requirements for gasoline and required an oxygen
content of at least 2% by weight. This regulation
also served to enhance energy security by extending
the gasoline supply with the use of domestically
produced and renewable energy sources. California
has RFG regulations that are more stringent than
the federal requirements and are intended to achieve
similar goals. The oxygenate of choice in federal
RFG was MTBE (methyl-t-butyl ether) (US EPA,
2007b) which accounted up to 87% of the oxygenate
use. Ethanol was also used in RFG. Given the
environmental concerns that have emerged concern-
ing the detection of MTBE in groundwater and
drinking water in the United States (McCarthy and
Tiemann, 2001), many states have banned the use of
MTBE in RFG (US EPA, 2007c). In February
2006, the federal RFG regulations were amended
to remove the requirement for oxygenate content
(US EPA, 2007d). With the US Energy Policy Act
of 2005, energy security (reducing the dependence
on foreign suppliers) has become the primary
motivator for the use of ethanol in gasoline, as it
can be produced domestically (US EPA, 2007f).
Canada has regulations controlling the level of
sulphur and benzene in gasoline (Environment
Canada, 2007a). In December 2006, the government
announced that it intends to mandate a 5% by
volume renewable fuel content based on the gaso-
line pool, starting in 2010 (Environment Canada,
2007b). The primary environmental motivation for
the use of renewable fuels in gasoline in Canada is
to achieve a reduction in lifecycle greenhouse gas
emissions. Economic motivators for Canadian
4499
farmers and rural communities are equally as
important as the Canadian bio-economy grows.
Low blend ethanol gasoline results in changes in
some vehicle tailpipe emissions. While individual
studies often showed contradictory results, gener-
ally, emissions of CO are reduced, effects on NOX,
NMHC and some air toxic emissions are generally
minimal, while emissions of formaldehyde and
acetaldehyde are increased compared to traditional
gasoline.
Higher ethanol blends, up to 85% ethanol in
gasoline, have been available on a limited basis in
both Canada and the USA for many years. Since
these fuels cannot be used in conventional vehicles
for several reasons, specially equipped flexible-fuel
vehicles are required (US EPA, 2007e). Interest in
these higher blends has increased very recently with
the new US Energy Policy Act of 2005, and the
Renewable Fuel Standard which took effect in
September 2007. This program is designed to
significantly increase the volume of renewable fuel
that is blended into gasoline with the primary
motivation of energy security. Renewable fuels also
offer lifecycle greenhouse gas emission reduction
opportunities.
As seen with low blend ethanol studies, individual
E85 studies show conflicting results, but generally,
E85 results in emission reductions for NOX, 1,3-
butadiene, benzene, and NMHC, emission increases
for formaldehyde and acetaldehyde and little
change (sometimes positive, sometimes negative) in
CO and NMOG emissions.
This paper begins by presenting selected results of
two recent studies conducted at Environment
Canada’s Emissions Research and Measurement
Division. The first study (Baas and Graham,
2006a, b, c) was conducted over 2 years (2004–05)
and involved four light duty gasoline vehicles of
different technologies operating on low blend
ethanol gasolines at two test temperatures (20 and
10 1C). The tailpipe emissions were characterized
for criteria pollutants (CO, NOX, NMHC, NMOG),
greenhouse gases (CO2, CH4, N2O), and particulate
matter (PM2.5). Detailed speciation was completed
for non-methane hydrocarbons, carbonyl com-
pounds, vapor phase organic acids, sulphur dioxide,
ammonia, polycyclic aromatic hydrocarbons, and
particulate matter (organic and elemental carbon,
particle phase organic and inorganic ions). Eva-
porative emissions at 20 1C were also quantified and
characterized for NMHC. Only the criteria, green-
house gas, and selected air toxic emissions are
 ARTICLE IN PRESS
4500 L.A. Graham et al. / Atmospheric Environment 42 (2008) 4498–4516
presented in this paper. The second study (Belisle
and Graham, 2006), conducted in November and
December of 2005, involved paired flexible fuel and
conventional vehicles with the objective to evaluate
changes in emissions due to flexible fuel vehicle
(FFV) operation on gasoline and E85 as compared
to similar conventional vehicles operating on gaso-
line. Emissions characterization included criteria
pollutants (CO, NOX, NMHC, NMOG) and green-
house gases (CO2, CH4, N2O). Detailed speciation
was completed for NMHC and carbonyl com-
pounds. Since the results of individual studies often
contradict one another, we also present statistical
analyses of the results of these two studies,
combined with literature results, in order to present
a clearer picture of potential emissions changes due
to use of either low ethanol gasolines or E85.
2. Methodology
Many of the test procedures used in these two
studies are common and are summarized below.
Differences between the two test programs, where
they exist, are noted.
2.1. Tailpipe emissions
Emissions measurements were conducted using
the chassis dynamometer testing facility at the
Emissions Research and Measurement Division of
Environment Canada. The procedures used are
detailed in the US EPA Federal Code of Regula-
tions, Schedule 40 Part 86. For the low blend
ethanol study, a four-phase implementation of the
FTP was used rather than the usual three-phase
FTP in order to facilitate particulate matter sample
collection. The FTP is representative of a non-
demanding style of urban driving and allows for
comparison of cold- and hot-start emissions. Emis-
sions were also characterized on the US06 cycle to
capture emissions during aggressive and high speed
driving. For the E85 study, emissions were char-
acterized for each phase of the standard three-phase
FTP cycle, with a 10-min soak between Phases 2
and 3. Samples for determining emissions of CO,
CO2, NOX, and total hydrocarbons (THC) were
collected on a per phase basis. For each dilute
exhaust sample collected, a corresponding dilution
air sample was collected. Dilute exhaust samples
for determining methane, nitrous oxide, ethanol,
and for speciation of NMHC were collected on
a per phase basis. A single dilution air sample
was collected over each test (FTP or US06). For
the carbonyl compound analysis, dilute exhaust
samples were collected on a per phase basis and
one dilution air sample was collected over each
sampling day.
2.2. Evaporative emissions
For the low blend ethanol study, evaporative
emissions were measured over the 1 h diurnal heat
build and hot soak cycles. The diurnal heat build
cycle simulated non-running emissions released as
fuel in the vehicle expands as a result of increases in
ambient temperature. The hot soak cycle simulates
non-running emissions released after the vehicle has
been running for a period of time. Although the
vehicle has been turned off, residual heat from the
engine continues to heat the fuel system compo-
nents, causing evaporative emissions. Samples for
determining evaporative emissions were automati-
cally taken from the SHED at the end of each cycle.
These samples were immediately directed to the
automated analyzer. Separate samples for determin-
ing evaporative emissions of NMHC and ethanol
were drawn from the SHED and collected in
TedlarTM bags.
2.3. Analytical methods
All analytical methods used in these studies are
accredited to ISO 17025 standards.
Concentrations of CO, CO2, NOX, and THC
were determined with standard test cell analyzers
(non-dispersive infrared, chemiluminescence, and
flame ionization). Concentrations of ethanol were
determined using an Innova Model 1312 Photo-
acoustic Multi-Gas Analyzer following procedures
similar to Loo and Parker (2000).
Samples for determining carbonyl compounds
were collected on Sep-Pak silica cartridges coated
with 2,4-dinitrophenylhydrazine (DNPH). The sam-
ples were extracted and analyzed by reverse phase
high performance liquid chromatography using an
Agilent 1100 Series Liquid Chromatograph with an
ultraviolet–visible (UV–vis) diode array detector. A
total of 18 carbonyl compounds (C1–C8) were
determined using this method.
Approximately, 160 NMHC were determined
using a Hewlett-Packard 6890 gas chromatograph
(GC) with a flame ionization detector (FID). An
Entech M7000 cryogenic concentrator was used for
sample concentration and introduction.
 ARTICLE IN PRESS
L.A. Graham et al. / Atmospheric Environment 42 (2008) 4498–4516 4501

Methane was determined and confirmation of
the C2 and C3 hydrocarbons was accomplished by
simple gas loop injection onto a capillary column. A
Hewlett-Packard 6890 gas chromatograph equipped
with a gas sampling valve and a FID was used for
the analysis.
Nitrous oxide was determined using a Hewlett-
Packard 5890A Series II GC with an electron
capture detector.
The detection limits for each method and sample
type are summarized in the Supplementary material
along with details of the analytical methods.
have matching octane number, fuel sulphur content,
and vapor pressure within each seasonal grade. For
each seasonal grade, the test fuels included a base
fuel containing no ethanol, a 20% ethanol tailor
blend, a 10% ethanol tailor blend, and a 10%
ethanol splash blend. The splash blend fuels were
made by simply ‘‘splash’’ blending a volume of
ethanol with the base fuel, resulting in lower
sulphur, higher octane, and higher vapor pressure
than the base fuel. Selected fuel properties are
presented in Table 1. Complete fuel specifications
are given in the Supplementary material.

2.4. Low blend study 2.4.3. Test procedure

2.4.1. Test vehicles
Three multi-port fuel injected (MPFI) vehicles
representing different technologies (emission stan-
dards) and one gasoline direct injection (GDI)
vehicle were tested. These vehicles were a 1998
Ford Escort ZX2 (US EPA Tier 1 emission
standard, approximately 80,000 km), a 2001 Nissan
Sentra CA (California SULEV zero evaporative
emission standard, approximately 12,000 km), a
2003 Dodge Caravan (US EPA LEV emission
standard, flexible fuel, approximately 25,000 km),
and a 2000 Mitsubishi Dion Exceed (Japanese LEV
emission standard, not currently sold in North
America, approximately 25,000 km). The Escort
and the Sentra were tested at 20 and 10 1C. The
Caravan and the Dion were tested at 20 1C only.
Tests were performed using four summer grade fuels
(for tests at 20 1C) and four winter grade fuels
(for tests at 10 1C).
2.4.2. Test fuels
The test fuels were blended for this project by
Halterman Fuels of Texas and were designed to
As the vehicles used for testing were in-use and
potentially exposed to gasoline with sulphur content
higher than the test fuels, it was necessary to
perform a conditioning sequence on each vehicle
to remove residual sulphur from the catalytic
converter. The procedure involved running the
vehicle at a rich air/fuel ratio and at a high catalyst
temperature to facilitate the formation of hydrogen
sulphide from the residual sulphur on the catalyst
and is described in more detail in Durbin et al.
(2003).
The charcoal canister of the vehicle collects
evaporative hydrocarbon emissions during the
SHED tests, which are then purged into the engine
while driving. These canisters are never fully purged
but maintain a fixed amount of trapped vapor called
the canister ‘‘heel’’. This presented a problem
because of the possibility of carryover of fuel
vapors. To mitigate this problem, two new OEM
canisters were purchased for each vehicle at the
beginning of the program and seasoned using the
summer grade E0 fuel. The 20 1C testing began
using the first canister, and the fuels were tested in
ascending ethanol content starting with the base

Table 1
Low blend ethanol gasoline study fuel properties

Summer grade fuels Winter grade fuels

S-E0 S-E10 S-E10-Spl S-E20 W-E0 W-E10 W-E10-Spl W-E20

1
Specific gravity (kg L ) 0.705 0.725 0.717 0.734 0.693 0.726 0.705 0.714
Net heating value (BTU lbm1) 18,927 18,127 18,182 17,319 18,975 18,096 18,200 17,494
Fuel fraction oxygen 0 0.036 0.036 0.073 0 0.036 0.037 0.073
Sulphur content (ppm) 34 34 31 35 33 33 26 27
Benzene (vol%) 0.1 0.5 0.7 0.8 0.5 0.5 0.4 0.3
Total aromatics (vol%) 7.9 11.0 8.1 14.1 8.3 12.6 7.3 6.3
Motor octane number 86.0 85.0 89.0 85.7 85.0 84.3 89.5 90.0
RVP (psi) 8.8 8.6 9.4 8.7 13.4 13.1 13.8 13.2
 ARTICLE IN PRESS
4502 L.A. Graham et al. / Atmospheric Environment 42 (2008) 4498–4516
fuel. Before the repeat 20 1C tests were performed,
the first canister was replaced with the second
seasoned canister. The repeat base fuel tests were
therefore performed with identical canister condi-
tions as the initial base fuel tests.
To prepare for the 10 1C testing, the first
canister was purged continuously for approximately
4 weeks alternately with pressurized clean air and
under vacuum to remove as much of the canister
heel as possible. The 10 1C testing began using the
second canister and the fuels were tested in
ascending ethanol content starting with the base
fuel. Before the repeat 10 1C tests were performed,
the first canister was re-installed. Although it had
been exposed to ethanol fuels from the 20 1C testing,
it was hoped that the purging process removed most
of the ethanol contamination making the initial and
repeat base fuel tests as similar as possible with
regards to canister conditions. The vehicle prepara-
tion and test sequence that was followed is provided
in the Supplementary material.
2.5. E85 study
The objective of this project was to determine
whether FFVs, when run on regular gasoline,
produced increased emissions as compared to
operation on E85 and as compared to conventional
vehicles of the same make and model operating on
gasoline.
2.5.1. Test vehicles
Two 2002 Chrysler Caravans meeting California
LEV 1 LDT emission standards, each with approxi-
mately 50,000 km; and two 2004 Chrysler Sebrings
meeting California ULEV 1 emission standards,
each with approximately 50,000 km were selected
for the study. These vehicles were obtained from
federal fleet operators in the Ottawa, Canada
region. Upon receipt of the test vehicles, it was
determined that the conventional Sebring did not
meet the same emission standards as its flexible fuel
counterpart and therefore would not render valid
comparisons. A suitable replacement vehicle could
not be found, so the project was continued using
only three vehicles.
2.5.2. Test fuels
The three vehicles were tested on the current
certification gasoline (California RFG Phase 2
certification fuel). The two FFVs were also tested
on a commercial E85 blend obtained from a local
Table 2
E85 study fuel properties
E85 California RFG
Phase 2
Specific gravity (kg L1) 0.784 0.743
Net heating value (BTU lb1) 13,867 18,132
Fuel fraction oxygen 0.294 0.018 (MTBE)
Sulphur content (ppm) 17 37
Benzene (vol%) n/a 0.8
Total aromatics (vol%) 6.6 26.2
Research octane number 104 96.8
RVP (psi) 7.3 5.7
distributor. The fuel parameters are summarized
in Table 2.
2.5.3. Test procedure
The vehicles were fuel exchanged to the certifica-
tion fuel and the evaporative emissions control
systems were purged with butane as prescribed in
the FTP procedure. The vehicles were driven over
two repeats of the LA4 cycle, fuel exchanged again
and driven over two more repeats of the LA4 cycle.
The conventional vehicle was ready for emissions
testing at this point.
Being designed to be capable of running on
ethanol–gasoline blends of up to 85% ethanol, the
FFV fuel system incorporates a fuel composition
sensor that measures ethanol content in the fuel.
This information is used to adjust the engine
parameters to best suit the fuel blend. The status
of this sensor can be surveyed through the OBD II
system. It was observed in other testing at the
laboratory that the fuel sensors took longer than
expected to report the correct ethanol reading,
although according to one vehicle manufacturer
representative, the sensor should nearly instantly
sense the fuel composition. At the beginning of the
study, additional mileage accumulation was per-
formed on the two FFVs until the fuel sensor read
the correct fuel composition (zero ethanol). After a
final fuel exchange and overnight soak, three repeats
of the FTP were conducted with emissions char-
acterization over consecutive days. The two FFVs
were then fuel exchanged to E85 and immediately
tested for emissions while the fuel sensor was
reading incorrectly. After fuel exchanges and mile-
age accumulation on E85, with periodic checks to
ensure the fuel sensor was reading the fuel
composition correctly, the FFVs were again tested
 ARTICLE IN PRESS
L.A. Graham et al. / Atmospheric Environment 42 (2008) 4498–4516
for three repeats of the FTP with emissions
characterization on consecutive days.
3. Results
3.1. Low blend ethanol study
The complete set of measured emission rates is
provided in the Supplementary material.
ANOVA and regression analyses were used to
identify and evaluate changes in emissions due to fuel
ethanol content. For the regression analysis, the
emission rate was plotted as a function of fuel ethanol
content and the slope of the regression line and its 95%
confidence limits were determined. If the confidence
limits did not include zero, then the slope was
considered statistically significantly different from zero.
The Caravan ‘‘flex fuel’’ operation during this
testing program was found to be unreliable as
continuous monitoring of the on-board fuel ethanol
sensor showed a fuel composition of zero ethanol
for all test fuels. Therefore, it is possible that the
engine did not realize any specially designed engine
parameters for ethanol fuel operation.
3.1.1. Criteria emissions
The usual trends of generally increased emissions
on cold start and cold temperature operation and
during aggressive driving were observed with these
vehicles and will not be further discussed.
The FTP composite and US06 emission rates for
each vehicle and fuel are shown in Fig. 1. The slopes
obtained from the regression analyses are presented
in the Supplementary material. A negative slope
was observed for CO, a positive slope for NOX,
and a slope of approximately zero was observed
for NMHC and NMOG; however, most of the
observed trends were not statistically significantly
different from zero.
Referring to the per phase emission rates pre-
sented in the Supplementary material, ethanol
blends tended to decrease the CO emissions and
increase the NOX emissions primarily during engine
cold start and aggressive driving conditions for the
MPFI and GDI vehicles. There was minimal effect
during hot engine start and stabilized driving. The
reason for the elevated NOX emissions from the
Sentra with E20 fuel at 10 1C for both the FTP
and US06 is not known.
Compared to the E10 tailor blend fuel, the splash
blended E10 fuel resulted in 35–50% higher CO
emissions during cold engine start at cold tempera-
4503
ture for the MPFI vehicles. At 20 1C, there was no
statistical difference in CO, NOX, NMHC or
NMOG emissions between the two fuels for any
of the vehicles.
As shown in Fig. 1, fuel ethanol content did not
affect the specific reactivity or ozone forming
potential of the exhaust from the MPFI vehicles.
For the GDI vehicle, increasing fuel ethanol content
resulted in decreasing specific reactivity and ozone
forming potential of the exhaust.
3.1.2. Air toxic emissions
The FTP composite and US06 emission rates for
each vehicle and fuel are shown in Fig. 2. The slopes
obtained from the regression analyses are presented
in the Supplementary material. Formaldehyde and
acetaldehyde emissions tended to increase, and 1,3-
butadiene and benzene emissions tended to decrease
with increasing ethanol content. The changes for
formaldehyde, 1,3-butadiene, and benzene were not
statistically significant while the changes in acet-
aldehyde were nearly always statistically significant.
The benzene response to change in ethanol content
should be considered with caution as the total
aromatics and benzene content of the fuels were
different but did not change as a direct function of
ethanol content as shown in Table 1.
Referring to the Supplementary material, the
presence of ethanol in the fuel increased the
formaldehyde and acetaldehyde emissions primarily
during cold engine start and under aggressive
driving conditions, not usually for the hot start or
stabilized driving. There were no statistically sig-
nificant differences in these air toxic emissions
between the E10 and E10-splash fuels.
For all vehicles, ethanol emissions were highest
for cold engine start. Once the catalyst was up to
normal operating temperature, ethanol emissions
were essentially not measurable. Operation at cold
temperature resulted in higher ethanol emission
rates as compared to standard temperature and
mainly affected cold engine start emissions. Rela-
tively low ethanol emissions were present during
some of the tests with E0 fuel, likely due to hang up
of ethanol in the vehicle fuel system. These findings
indicate that the canister conditioning and vehicle
preparation procedures minimized but did not
completely eliminate fuel carry-over.
3.1.3. GHG emissions
The FTP composite and US06 emission rates for
each vehicle and fuel are shown in Fig. 3. The slopes
 ARTICLE IN PRESS
4504 L.A. Graham et al. / Atmospheric Environment 42 (2008) 4498–4516

4.5 12
E0
4.0
E10 10
3.5

US06 CO (g/km)
E10-Spl
FTP CO (g/km)

3.0 8
E20
2.5
6
2.0
1.5 4
1.0
2
0.5
0.0 0
Escort Escort Sentra Sentra Caravan Dion Escort Escort Sentra Sentra Caravan Dion
(20C) (-10C) (20C) (-10C) (20C) (20C) (20C) (-10C) (20C) (-10C) (20C) (20C)

0.9 3.0
0.8
2.5
0.7

US06 NOX (g/km)

FTP NOX (g/km)

0.6 2.0
0.5
1.5
0.4
0.3 1.0
0.2
0.5
0.1
0.0 0.0
Escort Escort Sentra Sentra Caravan Dion Escort Escort Sentra Sentra Caravan Dion
(20C) (-10C) (20C) (-10C) (20C) (20C) (20C) (-10C) (20C) (-10C) (20C) (20C)

0.35 0.10
0.09
0.30
0.08
US06 NMOG (g/km)
FTP NMOG (g/km)

0.25 0.07
0.20 0.06
0.05
0.15 0.04
0.10 0.03
0.02
0.05
0.01
0.00 0.00
Escort Escort Sentra Sentra Caravan Dion Escort Escort Sentra Sentra Caravan Dion
(20C) (-10C) (20C) (-10C) (20C) (20C) (20C) (-10C) (20C) (-10C) (20C) (20C)

6.0 6.0
E0 E10
US06 Specific Reactivity
FTP Specific Reactivity

5.0 E10-Spl E20 5.0

(g O3/g NMOG)

(g O3/g NMOG)

4.0 4.0

3.0 3.0

2.0 2.0

1.0 1.0

0.0 0.0
Escort Escort Sentra Sentra Caravan Dion Escort Escort Sentra Sentra Caravan Dion
(20C) (-10C) (20C) (-10C) (20C) (20C) (20C) (-10C) (20C) (-10C) (20C) (20C)

1.2 0.35

1.0 0.30
US06 OFP (g O3/km)
FTP OFP (g O3/km)

0.25
0.8
0.20
0.6
0.15
0.4
0.10
0.2 0.05
0.0 0.00
Escort Escort Sentra Sentra Caravan Dion Escort Escort Sentra Sentra Caravan Dion
(20C) (-10C) (20C) (-10C) (20C) (20C) (20C) (-10C) (20C) (-10C) (20C) (20C)

Fig. 1. Comparison of FTP composite and US06 criteria emissions, specific reactivity and ozone forming potential from the low blend
study.
 ARTICLE IN PRESS
L.A. Graham et al. / Atmospheric Environment 42 (2008) 4498–4516 4505

1.4 0.7

US06 Formaldehyde (mg/km)

FPT Formaldehyde (mg/km)

E0 E10
1.2 0.6
E10-Spl E20
1.0 0.5
0.8 0.4
0.6 0.3
0.4 0.2
0.2 0.1
0.0 0.0
Escort Escort Sentra Sentra Caravan Dion Escort Escort Sentra Sentra Caravan Dion
(20C) (-10C) (20C) (-10C) (20C) (20C) (20C) (-10C) (20C) (-10C) (20C) (20C)

6.0 0.6

US06 Acetaldehyde (mg/km)

FPT Acetaldehyde (mg/km)

5.0 0.5

4.0 0.4

3.0 0.3

2.0 0.2

1.0 0.1

0.0 0.0

Escort Escort Sentra Sentra Caravan Dion Escort Escort Sentra Sentra Caravan Dion
(20C) (-10C) (20C) (-10C) (20C) (20C) (20C) (-10C) (20C) (-10C) (20C) (20C)

0.12 0.040
0.035
US06 Acrolein (mg/km)
FPT Acrolein (mg/km)

0.10
0.030
0.08
0.025
0.06 0.020
0.015
0.04
0.010
0.02
0.005
0.00 0.000
Escort Escort Sentra Sentra Caravan Dion Escort Escort Sentra Sentra Caravan Dion
(20C) (-10C) (20C) (-10C) (20C) (20C) (20C) (-10C) (20C) (-10C) (20C) (20C)

0.7 0.20
US06 1.3-Butadiene (mg/km)
FPT 1.3-Butadiene (mg/km)

0.6
0.5 0.15

0.4
0.10
0.3
0.2 0.05
0.1
0.0 0.00
Escort Escort Sentra Sentra Caravan Dion Escort Escort Sentra Sentra Caravan Dion
(20C) (-10C) (20C) (-10C) (20C) (20C) (20C) (-10C) (20C) (-10C) (20C) (20C)

6.0 7.0
US06 Benzene (mg/km)
FPT Benzene (mg/km)

5.0 6.0
5.0
4.0
4.0
3.0
3.0
2.0
2.0
1.0
1.0
0.0 0.0
Escort Escort Sentra Sentra Caravan Dion Escort Escort Sentra Sentra Caravan Dion
(20C) (-10C) (20C) (-10C) (20C) (20C) (20C) (-10C) (20C) (-10C) (20C) (20C)

Fig. 2. Comparison of FTP composite and US06 toxic emissions from the low blend study.
 ARTICLE IN PRESS
4506 L.A. Graham et al. / Atmospheric Environment 42 (2008) 4498–4516

obtained from the regression analyses are summar- no change at 20 1C but a statistically significant
ized in the Supplementary material. decrease at 10 1C.
For all vehicles and test temperatures, distance-
based CO2 emission rates were essentially un- 3.1.4. Evaporative emissions
changed as ethanol content increased. The lower The evaporative emissions results are shown in
volumetric energy density of the ethanol blend fuels Fig. 4. The differences in evaporative emissions
canceled out the lower carbon content. standards were quite evident with these vehicles.
In general, increasing ethanol content did not The Sentra had the lowest diurnal and hot soak
result in any statistically significant changes to the NMOG emissions (o0.04 g per test). The Caravan
CH4 emission rates. The exception was the Escort and the Escort had similar diurnal and hot soak
where CH4 emission rates decreased with increasing NMOG emissions (o0.7 and o0.25 g per test,
ethanol content at 20 1C only. N2O emissions in respectively). The Dion had the highest diurnal and
general tended to increase with ethanol content, hot soak NMOG emissions with diurnal emissions
though some changes were not statistically signifi- approaching 8 g per test and hot soak emissions
cant. The exception was the Sentra where there was around 1.5 g per test. The response of NMOG

300 300
E0 E10
FTP Composite CO2 (g/km)

250 E10-Spl E20 250

US06 CO2 (g/km)
200 200

150 150

100 100

50 50

0 0
Escort Escort Sentra Sentra Caravan Dion Escort Escort Sentra Sentra Caravan Dion
(20C) (-10C) (20C) (-10C) (20C) (20C) (20C) (-10C) (20C) (-10C) (20C) (20C)

25 18
FTP Composite N2O (mg/km)

16
20 14
US06 N2O (mg/km)

12
15
10
8
10
6
5 4
2
0 0
Escort Escort Sentra Sentra Caravan Dion Escort Escort Sentra Sentra Caravan Dion
(20C) (-10C) (20C) (-10C) (20C) (20C) (20C) (-10C) (20C) (-10C) (20C) (20C)

30 30
FTP Composite CH4 (mg/km)

25 25
US06 CH4 (mg/km)

20 20

15 15

10 10

5 5

0 0
Escort Escort Sentra Sentra Caravan Dion Escort Escort Sentra Sentra Caravan Dion
(20C) (-10C) (20C) (-10C) (20C) (20C) (20C) (-10C) (20C) (-10C) (20C) (20C)

Fig. 3. Comparison of FTP composite and US06 emissions for greenhouse gas emissions from the low blend study.
 ARTICLE IN PRESS
L.A. Graham et al. / Atmospheric Environment 42 (2008) 4498–4516 4507

0.6 100
E0 E10
0.5 10
E10-Spl E20

Evap NMOG (g/test)

0.4
Evap Ethanol (mg/test)

1
0.3
0.1
0.2
0.01
0.1

0 0.001
Diurnal Soak Diurnal Soak Diurnal Soak Diurnal Soak Diurnal Soak Diurnal Soak Diurnal Soak Diurnal Soak

Escort Sentra Caravan Dion Escort Sentra Caravan Dion

4.0 100
3.5
Evap Specific Reactivity

10

Evap OFP (g O3/test)

3.0
(g O3/g NMOG)

2.5 1
2.0
1.5 0.1

1.0
0.01
0.5
0.0 0.001
Diurnal Soak Diurnal Soak Diurnal Soak Diurnal Soak Diurnal Soak Diurnal Soak Diurnal Soak Diurnal Soak

Escort Sentra Caravan Dion Escort Sentra Caravan Dion

Fig. 4. Comparison of evaporative emissions from the low blend study.

emissions to ethanol content was different for each lower emissions than the conventional vehicle
vehicle as shown in Fig. 4. The results of the during Phase 1 of the FTP.
regression analysis are summarized in the Supple- When compared to the conventional Caravan
mentary material and show that each vehicle on certification 2 fuel, the FFV Caravan on E85
responds differently, and that in general, the showed statistically significant decreases in CO,
responses were not statistically significant. The NOX, and NMHC emissions by 72%, 48%, and
differences observed between the E10 and E10- 55%, respectively. There was no statistically sig-
splash fuels were also not statistically significant. nificant difference in NMOG emissions.
For the FFV Caravan, operation on E85 resulted
in statistically significant decreases in CO, NOX and
3.2. E85 study
NMHC emissions but no change in NMOG
emissions, as compared to operation on certification
The complete set of measured emission rates
fuel. The decreases in CO and NMHC emissions
is provided in the Supplementary material. FTP
occurred in Phases 1 and 3 while the decrease in
composite emission rates are compared in Figs. 5–7.
NOX emissions occurred only in Phase 1.
For the FFV Sebring, operation on E85 also
3.2.1. Criteria emissions resulted in statistically significant decreases in CO,
The first step of the study was to determine if the NOX, and NMHC emissions, as compared to
paired vehicles differed in emissions when operated operation on certification fuel. The decrease in CO
on certification fuel. Since the conventional Sebring occurred across all three phases. The decreases in
was certified to a different emission standard than NOX and NMHC emissions occurred in Phases 1
the FFV Sebring, it was excluded from the study. As and 3. While there was no statistically significant
seen in Figs. 5 and 6, the two Caravans showed no change in FTP composite NMOG emissions, Phase
statistically significant differences in emissions, 1 showed a statistically significant increase and
except for NOX for which the FFV showed 23% Phase 3 showed a statistically significant decrease.
 ARTICLE IN PRESS
4508 L.A. Graham et al. / Atmospheric Environment 42 (2008) 4498–4516

0.9 0.20
Cal. RFG 2
0.8 0.18
E85
0.7 0.16

FTP NOX (g/km)

0.14
FTP CO (g/km)

0.6
0.12
0.5
0.10
0.4
0.08
0.3
0.06
0.2 0.04
0.1 0.02
0.0 0.00
Conv Caravan FFV Caravan FFV Sebring Conv Caravan FFV Caravan FFV Sebring

0.07 0.07

0.06 0.06

FTP NMOG (g/km)

FTP NMHC (g/km)

0.05 0.05

0.04 0.04

0.03 0.03

0.02 0.02

0.01 0.01

0.00 0.00
Conv Caravan FFV Caravan FFV Sebring Conv Caravan FFV Caravan FFV Sebring

4.5 0.18
4.0 0.16
FTP SR (g O3/g NMOG)

3.5 0.14
FTP OFP (g O3/km)

3.0 0.12
2.5 0.10
2.0 0.08
1.5 0.06
1.0 0.04
0.5 0.02
0.0 0.00
Conv Caravan FFV Caravan FFV Sebring Conv Caravan FFV Caravan FFV Sebring

Fig. 5. Criteria emissions for conventional and flexible fuel vehicles operating on Cal. RFG 2 fuel and E85.

3.2.2. Air toxic emissions now, a statistically significant increase in formalde-

Fig. 6 shows FTP composite emission rates for hyde emissions was observed. Comparing the FFV
selected air toxics. As summarized in the Supple- Sebring operation on E85 to its operation on the
mentary material, there were no statistically signi- certification fuel, similar trends to the FFV Caravan
ficant differences in air toxic emissions between the were observed. The 1,3-butadiene emissions from
conventional Caravan and FFV Caravan operating all vehicles on the certification fuel were below
on certification fuel. Operation of the FFV on E85 detection limits so changes could not be reliably
resulted in no statistically significant change in evaluated.
formaldehyde emissions, a statistically significant
increase in acetaldehyde emissions, and statistically 3.2.3. GHG emissions
significant decreases in benzene and BTEX emis- Fig. 7 shows FTP composite emission rates for
sions, as compared to the conventional Caravan. the greenhouse gases. As summarized in the
Comparing the FFV Caravan operation on E85 to Supplementary material, there were no statistically
its operation on the certification fuel, similar trends significant differences in GHG emissions between
to the conventional Caravan were observed, except the conventional Caravan and the FFV Caravan
 ARTICLE IN PRESS
L.A. Graham et al. / Atmospheric Environment 42 (2008) 4498–4516 4509

0.12 1.0
Cal. RFG 2
0.9
E85
FTP Formaldehyde (mg/km)

FTP Acetaldehyde (mg/km)

0.10
0.8
0.7
0.08
0.6
0.06 0.5
0.4
0.04
0.3
0.2
0.02
0.1
0.00 0.0
Conv Caravan FFV Caravan FFV Sebring Conv Caravan FFV Caravan FFV Sebring

0.012 1.8
1.6

FTP Total Carbonyl (mg/km)

0.010
1.4
FTP Acrolein (mg/km)

0.008 1.2
1.0
0.006
0.8
0.004 0.6
0.4
0.002
0.2
0.000 0.0
Conv Caravan FFV Caravan FFV Sebring Conv Caravan FFV Caravan FFV Sebring

0.35 2.0
1.8
0.30
FTP 1.3-butadiene (mg/km)

1.6
FTP Benzene (mg/km)

0.25 1.4

0.20 1.2
1.0
0.15 0.8
0.10 0.6
0.4
0.05
0.2
0.00 0.0
Conv Caravan FFV Caravan FFV Sebring Conv Caravan FFV Caravan FFV Sebring

12 30

10 25
FTP BTEX (mg/km)

FTP Ethanol (mg/km)

8 20

6 15

4 10

2 5

0 0
Conv Caravan FFV Caravan FFV Sebring Conv Caravan FFV Caravan FFV Sebring

Fig. 6. Air toxic emissions for conventional and flexible fuel vehicles operating on Cal. RFG 2 fuel and E85.

operating on certification fuel. The FFV Caravan emissions, as compared to the conventional Caravan
operating on E85 showed a statistically significant operating on Certification fuel. The CH4 change was
decrease in N2O emissions but no change in CH4 almost significant at the 0.05 level (p-value ¼ 0.058).
 ARTICLE IN PRESS
4510 L.A. Graham et al. / Atmospheric Environment 42 (2008) 4498–4516

350 12
Cal. RFG 2
300 E85 10

FTP CH4 (mg/km)

FTP CO2 (g/km)

250
8
200
6
150
4
100

50 2

0 0
Conv Caravan FFV Caravan FFV Sebring Conv Caravan FFV Caravan FFV Sebring

25

20
FTP N2O (mg/km)

15

10

0
Conv Caravan FFV Caravan FFV Sebring

Fig. 7. Greenhouse gas emissions for conventional and flexible fuel vehicles operating on Cal. RFG 2 fuel and E85.

Caravan Sebring
70 90
80
Fuel Sesnor (%Ethanol)
Fuel Sesnor (%Ethanol)

60
70
50
60
40 50
30 40
30
20
20
10 10
0 0
0 100 200 300 400 500 0 100 200 300 400
Accumulation (km) Accumulation (km)

Fig. 8. Fuel sensor change by mileage accumulation. Solid symbols indicate fuel exchange or top-up prior to mileage accumulation to
reach that point.

The FFV Caravan, when operating on E85, showed 3.2.4. Fuel sensor behavior
a statistically significant increase in CH4 emissions Fig. 8 shows how the FFVs’ sensors changed as
and no statistically significant change in N2O mileage accumulated. The FFV Caravan’s sensor,
emissions, as compared to operation on Certification over 356 km, changed from 0% to 64%. The FFV
fuel. The N2O change was almost significant at Sebring’s sensor, over 273 km, changed from 0% to
the 0.05 level (p-value ¼ 0.084). The FFV Sebring 83%. Fig. 1a and b in the Supplementary material
also showed a statistically significant increase in shows linear trend lines fit to the measured emission
CH4 emissions and a statistically significant decrease rates as a function of fuel sensor reading. All tests
in N2O emissions, as compared to operation on shown in these figures were conducted on E85 and
Certification fuel. the sensor reading was recorded at the beginning of
 ARTICLE IN PRESS
L.A. Graham et al. / Atmospheric Environment 42 (2008) 4498–4516
the test. For the FFV Caravan, regression analysis
showed that CO, NOX, and NMHC emissions
decreased and NMOG emissions increased during
Phase 1 of the FTP as the sensor adjusted to the
fuel composition. The Phases 2 and 3 trend lines
showed no statistically significant change in emis-
sions with fuel sensor change. For the Sebring, CO
and NOX emissions decreased as the sensor reading
increased during all three phases. These changes
were not statistically significant for Phases 2
and 3, but were statistically significant for Phase 1.
For NMHC and NMOG, emissions increased
during Phase 1 but no change was observed during
Phase 2 or 3.
4. Discussion
We have reported the results of two studies that
have examined the effect on emissions due to the use
of ethanol-blended gasolines. These two studies, like
other studies reported in the literature, are limited
(mainly for financial reasons) to a fleet of a few test
vehicles. The question of how representative any
one of these test vehicles is of the population from
which it is taken is always asked. As can be seen
from the literature reviews discussed below, results
from individual studies often show contradicting
results, and one reason for this is the small fleet size
of any one study. In order to clear away some of
these contradictions, we take the results of the
current studies and combine them with the results
reported in the literature to increase the fleet size. It
is expected that, as a result, a clearer picture of the
effects on emissions will be obtained.
4.1. Literature review E10
Direct comparisons between reference fuels and
E10 blends for FTP composite emission rates were
possible for two published studies (Knapp et al.,
1998; Durbin et al., 2006) in addition to the results
from this study. Changes in criteria emissions, air
toxic and GHG emissions (CO, NOX, NMHC,
NMOG, formaldehyde, acetaldehyde, 1,3-buta-
diene, benzene, CO2, N2O, CH4) as a result of fuel
change were analyzed. Knapp et al. did not report
NMHC, NMOG, or GHG emission rates. Durbin
et al. did not report N2O or CH4 emission rates. A
total of 43 vehicle/fuel pairs were available from
these studies.
For two of the three studies, individual test results
were available for each vehicle, so tests for
4511
significance could be done for the changes resulting
from individual vehicle/fuel pairs. For each vehicle/
fuel pair, the relative change in emission rate
((E10-Ref)/Ref) was calculated to minimize the
effect of different emission control technologies.
The relative change data was examined to determine
if it was normally or symmetrically distributed. The
Kolmogorov–Smirnov goodness of fit test and Q–Q
plots were used to compare each dataset to the
normal distribution. The skewness parameter was
also calculated. Descriptive statistics are summar-
ized in Table 3 and the relative changes for each
vehicle/fuel pair are provided in the Supplementary
material.
In all cases, the data were not normally dis-
tributed and almost always moderately to highly
skewed; therefore, the median value instead of the
mean was used for quantifying the change due to
fuel. From the results of the entire dataset, all
changes in emissions were statistically significant
except for NOX, formaldehyde and the GHGs. For
the 31 or 32 tests for which individual tests for
significance could be done, only a few of the
individual vehicles showed a statistically significant
change for all pollutants except acetaldehyde.
Because of the magnitude of the change in
acetaldehyde emissions, 11 of the 31 vehicles
showed statistically significant changes. These sta-
tistically significant changes were in the same
direction as the entire dataset, and at least twice
the magnitude of the median value of the entire
dataset. The box plot shown in Fig. 9 illustrates
these results.
4.2. Literature review E85
Direct comparisons between reference fuels and
E85 blends for FTP composite emission rates were
possible for four published studies (Benson et al.,
1995; Kelly et al., 1996; Winebrake and Deaton,
1999; Black et al., 1998) in addition to the results
reported in this study. Winebrake and Deaton
reported only toxic emissions. A total of 11
vehicle/fuel pairs were included in the dataset. The
relative changes for each vehicle/fuel pair are
provided in the Supplementary material. The results
from the literature for E85 were generally for older
vehicles than those in the E10 comparison and the
present study.
The analysis described above for E10 was con-
ducted and the results are summarized in Table 3. In
all cases, the datasets were not normally distributed
 4512
Table 3
Summary of descriptive statistics and results of test for significance for relative changes in emissions due to the use of ethanol blended fuels

CO NOX NMHC NMOG Formaldehyde Acetaldehyde 1,3- Benzene CO2 N2O CH4
Butadiene

(a) E10 fuel

Minimum (%) 82 58 17 14 83 26 83 71 2.4 30 45
1st quartile (%) 31 15 0 5 8 68 3 5 0.0 7 21
Median (%) 16 3 9 14 5 108 16 15 0.6 2 9
3rd quartile (%) 0 18 22 21 30 160 44 29 1.4 5 1
Maximun (%) 70 77 50 66 137 486 267 85 3.3 16 19
Total N 43 43 43 43 43 43 43 43 43 43 43

L.A. Graham et al. / Atmospheric Environment 42 (2008) 4498–4516

Missing data 0 1 11 12 1 1 1 1 11 35 35
Mean (%) 15 4 11 15 13 129 28 12 0.6 3 12
S.D. (%) 28 26 18 19 40 107 63 31 1.2 16 22
Skewness 0.086 0.506 0.490 1.004 1.166 1.859 2.035 0.127 0.209 1.00 0.48
Shape of distribution Fairly Moderately Fairly Highly Highly skewed Highly skewed Highly Fairly Fairly Highly Fairly
symmetric skewed symmetric skewed skewed symmetric symmetric skewed symmetric

ARTICLE IN PRESS
Kolmogorov–Smirnov 0.502 0.462 0.776 0.458 0.337 0.267 0.111 0.782 1.782 2.782 3.782
test (p-value)
Normality Not normal Not normal Not Not Not normal Not normal Not Not Not Not Not
normal normal normal normal normal normal normal
Wilcoxon signed-rank 0.0004 0.5035 0.0035 0.0002 0.0689 0.0000 0.0043 0.0075 1.0075 2.0075 3.0075
test (p-value)
Significance of change Significant Not significant Significant Significant Not significant Significant Significant Significant Not Not Not
(a ¼ 0.05) significant significant significant

CO NOX NMHC NMOG Formaldehyde Acetaldehyde 1,3-Butadiene Benzene

(b) E85 fuel

Minimum (%) 69 60 87 41 5 1275 89 94
1st quartile (%) 43 50 55 13 55 2005 82 82
Median (%) 8 45 48 5 73 2540 77 76
3rd quartile (%) 31 34 39 35 102 3821 59 60
Maximum (%) 62 13 7 74 164 4967 0 50
Total N 11 11 11 11 11 11 11 11
Missing data 3 3 1 3 0 0 3 3
Mean (%) 5 42 45 12 80 2855 64 72
S.D. (%) 51 15 24 39 44 1189 31 15
Skewness 0.161 0.843 0.662 0.407 0.400 0.512 1.590 0.177
Shape of distribution Fairly symmetric Moderately Moderately Fairly Fairly symmetric Moderately Highly skewed Fairly
skewed skewed symmetric skewed symmetric
Kolmogorov–Smirnov 0.863 0.966 0.790 0.878 0.871 0.719 0.380 0.910
test (p-value)
Normality Not normal Not normal Not normal Not normal Not normal Not normal Not normal Not normal
Wilcoxon signed-rank 0.7422 0.0078 0.0039 0.5469 0.0010 0.0010 0.0170 0.0078
test (p-value)
Significance of change Not significant Significant Significant Not Significant Significant Significant Significant
(a ¼ 0.05) significant

L.A. Graham et al. / Atmospheric Environment 42 (2008) 4498–4516
4
Relative Change (E10-Ref)/Ref
-2
Acetald
Benzene
Fig. 9. Box plot showing relative change in emissions with fuel change from reference fuel to E10 for combined data from published
studies and this study.
and also generally not symmetrically distributed.
Statistically significant changes in emissions were
found for all pollutants except CO and NMOG.
Individual test data were available for between three
and seven vehicles for each pollutant, allowing
individual tests for significance to be done (see
Supplementary material). Since the changes in
emissions were generally much larger than seen
for E10, the sign and magnitude of the individual
tests for significance agree quite well with what
the entire dataset suggests. The exception to this
trend is CO, which showed a much wider variation
in effect. Upon closer examination, it appears
that the older vehicles (Tier 0 and older) have
different CO and NMOG responses than newer
vehicles (Tier 1 and newer). Four of the five older
vehicles showed large increases in CO emissions,
while the newer vehicles showed a decrease in
CO emissions of similar magnitude. Three of
these five older vehicles also showed a greater
increase in NMOG emissions than the decrease
shown by the newer vehicles. The box plot in
Fig. 10 illustrates these results. These changes were
generally consistent with those used by Jacobson
in a recent assessment of potential health effects
of widespread E85 use in the USA (Jacobson,
2007).
ARTICLE IN PRESS
4513
Butadiene CO Formald NMHC NOX
CH4 CO2 N2O NMOG
5. Conclusions
The results of two recent studies on the effects on
tailpipe and evaporative emissions of low blend
ethanol gasolines and E85 were presented. The
results from these two studies were combined with
published literature results to better assess the effect
of ethanol on vehicle emissions.
The results of the low blend ethanol gasoline
study suggests that up to 20% ethanol can lead to
statistically significant reductions in FTP composite
emissions of CO, statistically significant increases
in NOX and acetaldehyde emissions, and no change
in NMHC, NMOG, formaldehyde, 1,3-butadiene,
Benzene, or GHG emissions. The magnitude of the
change appears to depend on vehicle technology
for the four vehicles studied. Much smaller changes
were observed for US06 emissions. Operation at
cold temperature tended to increase the magnitude
of the emissions and the magnitude of the changes
but not, in general, the direction of the changes.
Low blend ethanol gasolines showed no statistically
significant effect on evaporative NMOG emissions.
While changes in the detailed composition of the
tailpipe and evaporative emissions were observed
(increases in acetaldehyde and ethanol, decreases
in gasoline hydrocarbons), there appeared to be
 ARTICLE IN PRESS
4514 L.A. Graham et al. / Atmospheric Environment 42 (2008) 4498–4516

60
2

Relative Change (E85-Ref)/Ref 40

0

-1

20
-2
Benzene Butadiene CO Formald NMHC NMOG NOX

-20
Acetald Benzene Butadiene CO Formald NMHC NMOG NOX

Fig. 10. Box plot showing relative change in emissions with fuel change from reference fuel to E85 for combined data from published
studies and this study.

no net effect on the specific reactivity of the was adjusting to the fuel composition and these
emissions. There were also no statistically signifi- results show that CO and NOX emissions can be
cant differences in emissions from the E10 and higher while NMHC and NMOG emissions can
E10-splash fuels, except during cold temperature be lower while the fuel sensor is adjusting to the
cold start where an increase in CO emissions was correct fuel composition. The differences are largest
observed. during cold start but in some cases are observed
The results of the E85 study indicate that the only during all phases of the test.
statistically significant difference in emissions between For low blend ethanol fuels and E85, unburned
the conventional Caravan and the FFV Caravan ethanol was found almost exclusively during cold
certified to the same emission standard and operating and hot engine start portions of the test, when the
on certification fuel was a 23% decrease in NOX catalytic converter was cold, not during stabilized
emissions for the FFV Caravan. Operation of the operation or during aggressive driving, when the
FFV Caravan and the FFV Sebring on E85 resulted catalytic converter was hot. Ethanol was found in
in statistically significant increases in formaldehyde the evaporative emissions during the low blend
(86–117%), acetaldehyde (1300–5000%) and methane ethanol study and increased with increasing ethanol
emissions (37–49%); statistically significant decreases content. The difference in RVP of the E10 and E10-
in CO (37–60%), NOX (32–47%), NMHC (3–45%), splash blends did not appear to increase ethanol or
benzene (58–72%) emissions and no statistically NMOG evaporative emissions.
significant changes in NMOG, 1,3-butadiene, CO2, When reviewing the conclusions of each study
or N2O emissions. Results also suggest that it takes individually, contradictory results are often found.
some time for the fuel oxygen sensor to respond to But, when all available data for a particular ethanol
the step change in change fuel composition that blend is considered as a single dataset, as done in
occurred on fuel exchange from certification fuel this paper, the following general conclusions can be
to E85. It appeared that for both vehicles, the drawn.
observed changes in fuel composition during As compared to reference fuels with no ethanol,
300+ km mileage accumulation were associated with operating on E10 blends generally result in:
fuel exchange or top-up followed by mileage accu-
mulation, not just mileage accumulation. Limited  statistically significant decreases in CO emissions
emissions testing was conducted while the fuel sensor (16%),
 ARTICLE IN PRESS
L.A. Graham et al. / Atmospheric Environment 42 (2008) 4498–4516
 statistically significant increases in NMHC (9%),
NMOG (14%), acetaldehyde (108%), 1,3-buta-
diene (16%), and benzene (15%) emissions, and
 no statistically significant change in NOX, for-
maldehyde, CO2, CH4, or N2O emissions.
The increase in benzene emissions may seem
curious as one may expect a dilution effect pro-
portional to the ethanol content. This may result
from differences in benzene and/or total aromatic
content of the reference and E10 fuels as not all
fuels were splash blends of ethanol with the
reference fuel.
As compared to reference fuels with no ethanol,
operating on E85 generally results in:
 statistically significant decreases in NOX (45%),
NMHC (48%), 1,3-butadiene (77%), and
benzene (76%) emissions,
 statistically significant increases in formaldehyde
(73%) and acetaldehyde (2540%) emissions, and
 no statistically significant change in CO, CO2, or
NMOG emissions.
While each of the individual studies generally
followed the trends suggested by the analysis of the
aggregated datasets, some differences in conclusions
were found. This finding reinforces the importance
of having a large enough vehicle fleet to minimize
influences of a single vehicle on the conclusions
drawn and to increase the ability to detect smaller
changes.
Acknowledgements
The authors would like to acknowledge the vehicle
testing and chemistry laboratory staff of Environment
Canada’s Emissions Research and Measurement Divi-
sion for their efforts in conducting the emissions testing
and analyses reported in this paper. Funding for the
low blend ethanol study was provided by Natural
Resources Canada’s Program for Energy Research
and Development and Environment Canada. Vehicles
for this study were provided by Transport Canada’s
Advanced Technology Vehicle program (Nissan Sentra
and Mitsubishi Dion) and by Natural Resources
Canada (FFV Caravan).
Funding for the E85 study was provided by
Natural Resources Canada and the federal fleet
managers’ Federal Vehicles Initiative (FVI). Vehi-
cles for this study were provided by the federal fleet
4515
managers of Natural Resources Canada and the
Royal Canadian Mounted Police.
The authors would also like to thank Dr. Thomas
Durbin for providing the individual test results for
the CRC E-67 study.
Appendix A. Supplementary materials
Supplementary data associated with this article
can be found in the online version at doi:10.1016/
j.atmosenv.2008.01.061.
References
Baas, C., Graham, L.A., 2006a. Emissions from 4 different light
duty vehicle technologies operating on low blend ethanol
gasoline—tailpipe greenhouse gas emissions. Environment
Canada ERMD Report 04-27A, 2004.
Baas, C., Graham, L.A., 2006b. Emissions from 4 different
light duty vehicle technologies operating on low blend
ethanol gasoline—tailpipe regulated and unregulated gaseous
emissions (CO, NOX, THC, NMHC, NMOG, ethanol,
carbonyls, VOC). Environment Canada ERMD Report
04-27B.
Baas, C., Graham, L.A., 2006c. Emissions from 4 different light
duty vehicle technologies operating on low blend ethanol
gasoline—diurnal and hot soak evaporative emissions (etha-
nol, NMOG and speciated NMHC). Environment Canada
ERMD Report 04-27D.
Belisle, S., Graham, L.A., 2006. Comparison of emissions
of conventional and flexible-fuel vehicles operating on
gasoline and E85 fuels. Environment Canada, ERMD Report
#05-39.
Benson, J.D., et al., 1995. Emissions with E85 and gasolines in
flexible/variable fuel vehicles—the auto/oil air quality im-
provement research program. SAE Technical Paper Series,
No. 952508.
Black, F., et al., 1998. Alternative fuel motor vehicle tailpipe and
evaporative emissions composition and ozone potential.
Journal of the Air and Waste Management Association 48,
578–591.
Durbin, T.D., Miller, J.W., Pisano, J.T., Younglove, T.,
Sauer, C.G., Rhee, S.H., Huai, T., 2003. The effect of fuel
on NH3 and other emissions from 2000–2001 model year
vehicles. Final Report CRC Project E-60, May 2003.
Durbin, T.D., et al., 2006. Effects of ethanol and volatility
parameters on exhaust emissions. CRC Project No. E-67.
Coordinating Research Council, Inc., Alpharetta, GA.
Environment Canada, 2007a. Fossil fuels. /http://www.ec.gc.
ca/cleanair-airpur/Fuels-WS0E66B313-1_En.htmS (accessed
4.09.07).
Environment Canada, 2007b. Renewable fuels. /http://www.
ec.gc.ca/cleanair-airpur/Bio_Fuels-WSCD7D0FD7-1_En.htmS
(accessed 4.09.07).
Jacobson, M.Z., 2007. Effects of ethanol (E85) versus gasoline
vehicles on cancer and mortality in the United States.
Environmental Science and Technology 41, 4150–4157.
 ARTICLE IN PRESS
4516 L.A. Graham et al. / Atmospheric Environment 42 (2008) 4498–4516
Kelly, K.J., et al., 1996. Federal test procedure emissions test
results from ethanol variable-fuel vehicle Chevrolet Luminas.
SAE Technical Paper Series, No. 961092.
Knapp, K.T., et al., 1998. The effect of ethanol fuel on the
emissions of vehicles over a wide range of temperatures.
Journal of the Air and Waste Management Association 48,
646–653.
Loo, J.F., Parker, D.T., 2000. Evaluation of a photoacoustic gas
analyzer for ethanol vehicle emissions measurement. Society
of Automotive Engineers Technical Paper No. 2000-01-0794.
McCarthy, J.E., Tiemann, M., 2001. CRS Report for Congress
98-290: MTBE in Gasoline: Clean Air and Drinking Water
Issues, Updated May 15, 2001. /http://www.ncseonline.org/
NLE/CRSreports/air/air-26.cfm#Back12S (accessed 1.08.07).
US EPA, 2007a. MTBE in fuels. /http://www.epa.gov/mtbe/
gas.htmS (accessed 4.09.07).
US EPA, 2007b. Reformulated gas—basic information. /http://
www.epa.gov/otaq/rfg/information.htmS (accessed 4.09.07).
US EPA, 2007c. State actions banning MTBE (statewide),
EPA420-B-07-013, August 2007. /http://www.epa.gov/mtbe/
420b07013.pdfS (accessed 4.09.07).
US EPA, 2007d. Regulatory announcement: removal of refor-
mulated gasoline oxygen content requirement and revision of
commingling prohibition to address non-oxygenated refor-
mulated gasoline. /http://www.epa.gov/otaq/regs/fuels/rfg/
420f06020.htmS (accessed 4.09.07).
US EPA, 2007e. E85 and flex fuel vehicles. /http://www.epa.gov/
smartway/growandgo/documents/factsheet-e85.htmS (accessed
4.09.07).
US EPA, 2007f. Regulatory impact analysis: renewable fuel standard
program. EPA420-R-07-004, April 2007. /http://www.epa.gov/
otaq/renewablefuels/420r07004.pdfS (accessed 9.01.08).
Winebrake, J.J., Deaton, M.L., 1999. Hazardous air pollution
from mobile sources: a comparison of alternative fuel and
reformulated gasoline vehicles. Journal of the Air and Waste
Management Association 49, 576–581.