Professional Documents
Culture Documents
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
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 4499
air quality that arise from gasoline-powered vehicle farmers and rural communities are equally as
emissions, specifically ground level ozone, toxic air important as the Canadian bio-economy grows.
pollutants, and carbon monoxide. In 1992, the US Low blend ethanol gasoline results in changes in
Clean Air Act implemented a wintertime oxyge- some vehicle tailpipe emissions. While individual
nated fuels program for cities with elevated ambient studies often showed contradictory results, gener-
concentrations of CO during the cold months. This ally, emissions of CO are reduced, effects on NOX,
program required 2.7% by weight of oxygen in NMHC and some air toxic emissions are generally
gasoline and the oxygenate of choice for this minimal, while emissions of formaldehyde and
program was ethanol (US EPA, 2007a). In Canada, acetaldehyde are increased compared to traditional
similar fuels were available, but were not mandated gasoline.
as in the USA. In 1995, the US Federal Reformu- Higher ethanol blends, up to 85% ethanol in
lated Gasoline (RFG) regulations were introduced. gasoline, have been available on a limited basis in
RFG is required by the US Clean Air Act in cities both Canada and the USA for many years. Since
with the worst smog pollution and other cities with these fuels cannot be used in conventional vehicles
smog problems may choose to use RFG. RFG is for several reasons, specially equipped flexible-fuel
currently used in 17 states and the District of vehicles are required (US EPA, 2007e). Interest in
Columbia and about 30% of gasoline sold in these higher blends has increased very recently with
the USA is reformulated (US EPA, 2007b). The the new US Energy Policy Act of 2005, and the
RFG regulations established emissions performance Renewable Fuel Standard which took effect in
requirements for gasoline and required an oxygen September 2007. This program is designed to
content of at least 2% by weight. This regulation significantly increase the volume of renewable fuel
also served to enhance energy security by extending that is blended into gasoline with the primary
the gasoline supply with the use of domestically motivation of energy security. Renewable fuels also
produced and renewable energy sources. California offer lifecycle greenhouse gas emission reduction
has RFG regulations that are more stringent than opportunities.
the federal requirements and are intended to achieve As seen with low blend ethanol studies, individual
similar goals. The oxygenate of choice in federal E85 studies show conflicting results, but generally,
RFG was MTBE (methyl-t-butyl ether) (US EPA, E85 results in emission reductions for NOX, 1,3-
2007b) which accounted up to 87% of the oxygenate butadiene, benzene, and NMHC, emission increases
use. Ethanol was also used in RFG. Given the for formaldehyde and acetaldehyde and little
environmental concerns that have emerged concern- change (sometimes positive, sometimes negative) in
ing the detection of MTBE in groundwater and CO and NMOG emissions.
drinking water in the United States (McCarthy and This paper begins by presenting selected results of
Tiemann, 2001), many states have banned the use of two recent studies conducted at Environment
MTBE in RFG (US EPA, 2007c). In February Canada’s Emissions Research and Measurement
2006, the federal RFG regulations were amended Division. The first study (Baas and Graham,
to remove the requirement for oxygenate content 2006a, b, c) was conducted over 2 years (2004–05)
(US EPA, 2007d). With the US Energy Policy Act and involved four light duty gasoline vehicles of
of 2005, energy security (reducing the dependence different technologies operating on low blend
on foreign suppliers) has become the primary ethanol gasolines at two test temperatures (20 and
motivator for the use of ethanol in gasoline, as it 10 1C). The tailpipe emissions were characterized
can be produced domestically (US EPA, 2007f). for criteria pollutants (CO, NOX, NMHC, NMOG),
Canada has regulations controlling the level of greenhouse gases (CO2, CH4, N2O), and particulate
sulphur and benzene in gasoline (Environment matter (PM2.5). Detailed speciation was completed
Canada, 2007a). In December 2006, the government for non-methane hydrocarbons, carbonyl com-
announced that it intends to mandate a 5% by pounds, vapor phase organic acids, sulphur dioxide,
volume renewable fuel content based on the gaso- ammonia, polycyclic aromatic hydrocarbons, and
line pool, starting in 2010 (Environment Canada, particulate matter (organic and elemental carbon,
2007b). The primary environmental motivation for particle phase organic and inorganic ions). Eva-
the use of renewable fuels in gasoline in Canada is porative emissions at 20 1C were also quantified and
to achieve a reduction in lifecycle greenhouse gas characterized for NMHC. Only the criteria, green-
emissions. Economic motivators for Canadian 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 was collected over each test (FTP or US06). For
and Graham, 2006), conducted in November and the carbonyl compound analysis, dilute exhaust
December of 2005, involved paired flexible fuel and samples were collected on a per phase basis and
conventional vehicles with the objective to evaluate one dilution air sample was collected over each
changes in emissions due to flexible fuel vehicle sampling day.
(FFV) operation on gasoline and E85 as compared
to similar conventional vehicles operating on gaso- 2.2. Evaporative emissions
line. Emissions characterization included criteria
pollutants (CO, NOX, NMHC, NMOG) and green- For the low blend ethanol study, evaporative
house gases (CO2, CH4, N2O). Detailed speciation emissions were measured over the 1 h diurnal heat
was completed for NMHC and carbonyl com- build and hot soak cycles. The diurnal heat build
pounds. Since the results of individual studies often cycle simulated non-running emissions released as
contradict one another, we also present statistical fuel in the vehicle expands as a result of increases in
analyses of the results of these two studies, ambient temperature. The hot soak cycle simulates
combined with literature results, in order to present non-running emissions released after the vehicle has
a clearer picture of potential emissions changes due been running for a period of time. Although the
to use of either low ethanol gasolines or E85. vehicle has been turned off, residual heat from the
engine continues to heat the fuel system compo-
2. Methodology nents, causing evaporative emissions. Samples for
determining evaporative emissions were automati-
Many of the test procedures used in these two cally taken from the SHED at the end of each cycle.
studies are common and are summarized below. These samples were immediately directed to the
Differences between the two test programs, where automated analyzer. Separate samples for determin-
they exist, are noted. ing evaporative emissions of NMHC and ethanol
were drawn from the SHED and collected in
2.1. Tailpipe emissions TedlarTM bags.
Methane was determined and confirmation of have matching octane number, fuel sulphur content,
the C2 and C3 hydrocarbons was accomplished by and vapor pressure within each seasonal grade. For
simple gas loop injection onto a capillary column. A each seasonal grade, the test fuels included a base
Hewlett-Packard 6890 gas chromatograph equipped fuel containing no ethanol, a 20% ethanol tailor
with a gas sampling valve and a FID was used for blend, a 10% ethanol tailor blend, and a 10%
the analysis. ethanol splash blend. The splash blend fuels were
Nitrous oxide was determined using a Hewlett- made by simply ‘‘splash’’ blending a volume of
Packard 5890A Series II GC with an electron ethanol with the base fuel, resulting in lower
capture detector. sulphur, higher octane, and higher vapor pressure
The detection limits for each method and sample than the base fuel. Selected fuel properties are
type are summarized in the Supplementary material presented in Table 1. Complete fuel specifications
along with details of the analytical methods. are given in the Supplementary material.
Table 1
Low blend ethanol gasoline study fuel properties
for three repeats of the FTP with emissions ture for the MPFI vehicles. At 20 1C, there was no
characterization on consecutive days. statistical difference in CO, NOX, NMHC or
NMOG emissions between the two fuels for any
3. Results of the vehicles.
As shown in Fig. 1, fuel ethanol content did not
3.1. Low blend ethanol study affect the specific reactivity or ozone forming
potential of the exhaust from the MPFI vehicles.
The complete set of measured emission rates is For the GDI vehicle, increasing fuel ethanol content
provided in the Supplementary material. resulted in decreasing specific reactivity and ozone
ANOVA and regression analyses were used to forming potential of the exhaust.
identify and evaluate changes in emissions due to fuel
ethanol content. For the regression analysis, the 3.1.2. Air toxic emissions
emission rate was plotted as a function of fuel ethanol The FTP composite and US06 emission rates for
content and the slope of the regression line and its 95% each vehicle and fuel are shown in Fig. 2. The slopes
confidence limits were determined. If the confidence obtained from the regression analyses are presented
limits did not include zero, then the slope was in the Supplementary material. Formaldehyde and
considered statistically significantly different from zero. acetaldehyde emissions tended to increase, and 1,3-
The Caravan ‘‘flex fuel’’ operation during this butadiene and benzene emissions tended to decrease
testing program was found to be unreliable as with increasing ethanol content. The changes for
continuous monitoring of the on-board fuel ethanol formaldehyde, 1,3-butadiene, and benzene were not
sensor showed a fuel composition of zero ethanol statistically significant while the changes in acet-
for all test fuels. Therefore, it is possible that the aldehyde were nearly always statistically significant.
engine did not realize any specially designed engine The benzene response to change in ethanol content
parameters for ethanol fuel operation. should be considered with caution as the total
aromatics and benzene content of the fuels were
3.1.1. Criteria emissions different but did not change as a direct function of
The usual trends of generally increased emissions ethanol content as shown in Table 1.
on cold start and cold temperature operation and Referring to the Supplementary material, the
during aggressive driving were observed with these presence of ethanol in the fuel increased the
vehicles and will not be further discussed. formaldehyde and acetaldehyde emissions primarily
The FTP composite and US06 emission rates for during cold engine start and under aggressive
each vehicle and fuel are shown in Fig. 1. The slopes driving conditions, not usually for the hot start or
obtained from the regression analyses are presented stabilized driving. There were no statistically sig-
in the Supplementary material. A negative slope nificant differences in these air toxic emissions
was observed for CO, a positive slope for NOX, between the E10 and E10-splash fuels.
and a slope of approximately zero was observed For all vehicles, ethanol emissions were highest
for NMHC and NMOG; however, most of the for cold engine start. Once the catalyst was up to
observed trends were not statistically significantly normal operating temperature, ethanol emissions
different from zero. were essentially not measurable. Operation at cold
Referring to the per phase emission rates pre- temperature resulted in higher ethanol emission
sented in the Supplementary material, ethanol rates as compared to standard temperature and
blends tended to decrease the CO emissions and mainly affected cold engine start emissions. Rela-
increase the NOX emissions primarily during engine tively low ethanol emissions were present during
cold start and aggressive driving conditions for the some of the tests with E0 fuel, likely due to hang up
MPFI and GDI vehicles. There was minimal effect of ethanol in the vehicle fuel system. These findings
during hot engine start and stabilized driving. The indicate that the canister conditioning and vehicle
reason for the elevated NOX emissions from the preparation procedures minimized but did not
Sentra with E20 fuel at 10 1C for both the FTP completely eliminate fuel carry-over.
and US06 is not known.
Compared to the E10 tailor blend fuel, the splash 3.1.3. GHG emissions
blended E10 fuel resulted in 35–50% higher CO The FTP composite and US06 emission rates for
emissions during cold engine start at cold tempera- 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
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
(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
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
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)
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
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
4.0 100
3.5
Evap Specific Reactivity
10
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
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
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
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.
0.12 1.0
Cal. RFG 2
0.9
E85
FTP Formaldehyde (mg/km)
0.012 1.8
1.6
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)
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
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 4511
the test. For the FFV Caravan, regression analysis significance could be done for the changes resulting
showed that CO, NOX, and NMHC emissions from individual vehicle/fuel pairs. For each vehicle/
decreased and NMOG emissions increased during fuel pair, the relative change in emission rate
Phase 1 of the FTP as the sensor adjusted to the ((E10-Ref)/Ref) was calculated to minimize the
fuel composition. The Phases 2 and 3 trend lines effect of different emission control technologies.
showed no statistically significant change in emis- The relative change data was examined to determine
sions with fuel sensor change. For the Sebring, CO if it was normally or symmetrically distributed. The
and NOX emissions decreased as the sensor reading Kolmogorov–Smirnov goodness of fit test and Q–Q
increased during all three phases. These changes plots were used to compare each dataset to the
were not statistically significant for Phases 2 normal distribution. The skewness parameter was
and 3, but were statistically significant for Phase 1. also calculated. Descriptive statistics are summar-
For NMHC and NMOG, emissions increased ized in Table 3 and the relative changes for each
during Phase 1 but no change was observed during vehicle/fuel pair are provided in the Supplementary
Phase 2 or 3. material.
In all cases, the data were not normally dis-
4. Discussion tributed and almost always moderately to highly
skewed; therefore, the median value instead of the
We have reported the results of two studies that mean was used for quantifying the change due to
have examined the effect on emissions due to the use fuel. From the results of the entire dataset, all
of ethanol-blended gasolines. These two studies, like changes in emissions were statistically significant
other studies reported in the literature, are limited except for NOX, formaldehyde and the GHGs. For
(mainly for financial reasons) to a fleet of a few test the 31 or 32 tests for which individual tests for
vehicles. The question of how representative any significance could be done, only a few of the
one of these test vehicles is of the population from individual vehicles showed a statistically significant
which it is taken is always asked. As can be seen change for all pollutants except acetaldehyde.
from the literature reviews discussed below, results Because of the magnitude of the change in
from individual studies often show contradicting acetaldehyde emissions, 11 of the 31 vehicles
results, and one reason for this is the small fleet size showed statistically significant changes. These sta-
of any one study. In order to clear away some of tistically significant changes were in the same
these contradictions, we take the results of the direction as the entire dataset, and at least twice
current studies and combine them with the results the magnitude of the median value of the entire
reported in the literature to increase the fleet size. It dataset. The box plot shown in Fig. 9 illustrates
is expected that, as a result, a clearer picture of the these results.
effects on emissions will be obtained.
4.2. Literature review E85
4.1. Literature review E10
Direct comparisons between reference fuels and
Direct comparisons between reference fuels and E85 blends for FTP composite emission rates were
E10 blends for FTP composite emission rates were possible for four published studies (Benson et al.,
possible for two published studies (Knapp et al., 1995; Kelly et al., 1996; Winebrake and Deaton,
1998; Durbin et al., 2006) in addition to the results 1999; Black et al., 1998) in addition to the results
from this study. Changes in criteria emissions, air reported in this study. Winebrake and Deaton
toxic and GHG emissions (CO, NOX, NMHC, reported only toxic emissions. A total of 11
NMOG, formaldehyde, acetaldehyde, 1,3-buta- vehicle/fuel pairs were included in the dataset. The
diene, benzene, CO2, N2O, CH4) as a result of fuel relative changes for each vehicle/fuel pair are
change were analyzed. Knapp et al. did not report provided in the Supplementary material. The results
NMHC, NMOG, or GHG emission rates. Durbin from the literature for E85 were generally for older
et al. did not report N2O or CH4 emission rates. A vehicles than those in the E10 comparison and the
total of 43 vehicle/fuel pairs were available from present study.
these studies. The analysis described above for E10 was con-
For two of the three studies, individual test results ducted and the results are summarized in Table 3. In
were available for each vehicle, so tests for 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
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
4
Relative Change (E10-Ref)/Ref
-2
Acetald Butadiene CO Formald NMHC NOX
Benzene CH4 CO2 N2O NMOG
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.
60
2
-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 4515
statistically significant increases in NMHC (9%), managers of Natural Resources Canada and the
NMOG (14%), acetaldehyde (108%), 1,3-buta- Royal Canadian Mounted Police.
diene (16%), and benzene (15%) emissions, and The authors would also like to thank Dr. Thomas
no statistically significant change in NOX, for- Durbin for providing the individual test results for
maldehyde, CO2, CH4, or N2O emissions. the CRC E-67 study.
Kelly, K.J., et al., 1996. Federal test procedure emissions test US EPA, 2007c. State actions banning MTBE (statewide),
results from ethanol variable-fuel vehicle Chevrolet Luminas. EPA420-B-07-013, August 2007. /http://www.epa.gov/mtbe/
SAE Technical Paper Series, No. 961092. 420b07013.pdfS (accessed 4.09.07).
Knapp, K.T., et al., 1998. The effect of ethanol fuel on the US EPA, 2007d. Regulatory announcement: removal of refor-
emissions of vehicles over a wide range of temperatures. mulated gasoline oxygen content requirement and revision of
Journal of the Air and Waste Management Association 48, commingling prohibition to address non-oxygenated refor-
646–653. mulated gasoline. /http://www.epa.gov/otaq/regs/fuels/rfg/
Loo, J.F., Parker, D.T., 2000. Evaluation of a photoacoustic gas 420f06020.htmS (accessed 4.09.07).
analyzer for ethanol vehicle emissions measurement. Society US EPA, 2007e. E85 and flex fuel vehicles. /http://www.epa.gov/
of Automotive Engineers Technical Paper No. 2000-01-0794. smartway/growandgo/documents/factsheet-e85.htmS (accessed
McCarthy, J.E., Tiemann, M., 2001. CRS Report for Congress 4.09.07).
98-290: MTBE in Gasoline: Clean Air and Drinking Water US EPA, 2007f. Regulatory impact analysis: renewable fuel standard
Issues, Updated May 15, 2001. /http://www.ncseonline.org/ program. EPA420-R-07-004, April 2007. /http://www.epa.gov/
NLE/CRSreports/air/air-26.cfm#Back12S (accessed 1.08.07). otaq/renewablefuels/420r07004.pdfS (accessed 9.01.08).
US EPA, 2007a. MTBE in fuels. /http://www.epa.gov/mtbe/ Winebrake, J.J., Deaton, M.L., 1999. Hazardous air pollution
gas.htmS (accessed 4.09.07). from mobile sources: a comparison of alternative fuel and
US EPA, 2007b. Reformulated gas—basic information. /http:// reformulated gasoline vehicles. Journal of the Air and Waste
www.epa.gov/otaq/rfg/information.htmS (accessed 4.09.07). Management Association 49, 576–581.