Exergy, an International Journal 2 (2002) 283–294

www.exergyonline.com

Exergetic environmental assessment of life cycle emissions

for various automobiles and fuels
Jason J. Daniel a , Marc A. Rosen b,∗
a Department of Mechanical, Aerospace and Industrial Engineering, Ryerson Polytechnic University, 350 Victoria St., Toronto, ON, Canada M5B 2K3
b School of Manufacturing Engineering, University of Ontario, Institute of Technology, 2000 Simcoe Street North, Oshawa, ON, Canada L1H 7L7

Received 19 December 2001; received in revised form 16 April 2002

Abstract
This paper examines material emissions produced during thirteen fuel life cycles for automobiles, on mass and exergy bases. The masses
of fuel life cycle emissions are compared with the chemical exergies of these emissions. For the emissions data used, the chemical exergy
results suggest that compressed natural gas use in motor vehicles produces emissions that are the most out of equilibrium with the natural
environment, relative to all other fuel life cycle paths considered. It is also shown that diesel use in grid-independent hybrid electric vehicles
has the lowest chemical exergies of emissions of all thirteen fuel-vehicle combinations under consideration, suggesting a lower degree of
potential environmental impact. The exergy methodology presented for assessing the potential for environmental impact may help in the
development and design of transportation technologies that are more environmentally benign than those presently used.
 2002 Éditions scientifiques et médicales Elsevier SAS. All rights reserved.

1. Introduction assessments concentrate only on emissions produced during

The release of waste emissions into the natural environ-
ment can cause various types of environmental degradation,
which decrease quality of life and threaten sustainable de-
velopment. A major source of potentially harmful waste
emissions is the transportation sector. In the United States,
for example, the transportation sector has been estimated
to account for 26% of the total greenhouse gas [1], 77%
of carbon monoxide emissions, and 49% of nitrogen oxides
emissions [2].
Recently renewed interest in reducing dependence on
fossil fuels, coupled with increasing pressures to create
more environmentally benign modes of transportation, have
caused the automotive and fuel production industries to
investigate alternative fuel and vehicle technologies.
Given the large number of alternative fuels and new ve-
hicle technologies in development, it is useful to examine
the emissions produced during the full life cycle of the fuel
to better understand how new generations of vehicles will
impact the environment. Without accounting for the entire
fuel life cycle, the actual environmental impact associated
with vehicle use cannot be determined. Surprisingly, some
* Correspondence and reprints.
E-mail address: marc.rosen@uoit.ca (M.A. Rosen).
1164-0235/02/$ – see front matter  2002 Éditions scientifiques et médicales Elsevier SAS. All rights reserved.
PII: S 1 1 6 4 - 0 2 3 5 ( 0 2 ) 0 0 0 7 6 - 6
vehicle operation. This approach, however, is problematic.
For example, this approach can lead to the belief that the op-
eration of electric vehicles yields no fuel-related emissions
and therefore causes no impact on the environment. But this
is an erroneous conclusion, as upstream emissions are pro-
duced during feedstock recovery and production processes
for the vehicle fuel (electricity, here).
There is a variety of metrics for environmental impact
assessments associated with vehicle use. Some recent stud-
ies have attempted to assess the impact of vehicles on the
environment by performing a life-cycle assessment (LCA).
Often in a LCA, an inventory phase analyzes system in-
puts of energy and materials along with outputs of emissions
and wastes throughout the life cycle, usually as quantitative
mass loadings. An impact assessment phase then examines
these loadings in light of potential environmental issues us-
ing a mixed spectrum of qualitative and quantitative methods
[3]. There are often problems associated with moving from
the inventory phase to the environmental impact assessment.
Owens states that the constraints imposed by inventory’s loss
of spatial, temporal, dose-response, and threshold informa-
tion raise concerns about the accuracy of impact assessment.
In particular, Owens [3] notes that LCA results may have
limited value in the areas of local and/or transient biophys-
284 J.J. Daniel, M.A. Rosen / Exergy, an International Journal 2 (2002) 283–294

Nomenclature

CD conventional diesel N2 O nitrous oxide

CG conventional gasoline NOx oxides of nitrogen
CGV conventional gasoline vehicle SIDI spark ignition direct injection
CH4 methane SOx oxides of sulphur
CIDI compression ignition direct injection VMT vehicle mile traveled
CNG compressed natural gas
Symbols
CNGV compressed natural gas vehicle
CO carbon monoxide e specific exergy
CO2 carbon dioxide g specific Gibbs function
CRFG2 California Phase 2 reformulated gasoline G Gibbs function
E85 85% ethanol and 15% gasoline fuel blend by P pressure
volume R universal gas constant
EV dedicated electric vehicle T temperature
FFV flexible-fuel vehicle x mole fraction
FRFG2 Federal Phase 2 reformulated gasoline ν stoichiometric coefficient
GC grid-connected Subscripts
GI grid-independent
GREET Greenhouse gases, Regulated Emissions, and j j th reactant substance
Energy use in Transportation k kth product substance
HEV hybrid electric vehicle o property evaluated at the reference state
LPG liquefied petroleum gas Superscript
MTBE methyl tertiary butyl ether ch chemical
M85 85% methanol and 15% gasoline fuel blend
by volume

ical processes and issues involving biological parameters
(such as biodiversity, habitat alteration, and toxicity).
The conclusions of any LCA may be extremely sensitive
to the boundary conditions under which the study is con-
ducted [4]. For example, in a study by Maclean and Lave
[5], alternative fuel-powertrain options for internal combus-
tion engine automobiles (spark and compression ignited,
direct injected, and indirect injected engines fueled by con-
ventional and reformulated gasoline, reformulated diesel,
compressed natural gas and alcohols) were analyzed, and
compared using the metrics of fuel/engine efficiency, energy
use, pollutant discharges, and greenhouse gas emissions.
Criticisms were levied of this study by Brown and Seager
[4]; one criticism was that the boundary conditions appro-
priate for the Maclean and Lave study [5] may vary both
temporally and geographically (e.g., the price of gasoline).
A common approach taken in quantifying the impact a
process may have on the environment is to determine the
masses of the emissions created during the process. This
type of analysis is inadequate, as it does not take into
account the fact that certain emissions have greater impacts
on the environment than others. In the Maclean and Lave
study, it is reported that compressed natural gas (CNG)
vehicles have the best exhaust emissions performance while
direct-injection diesels have the worst (with a conventional
gasoline-fueled vehicle being the baseline). However, this
result does not take into account that while the CNG-fueled
vehicles may produce a lower mass of emissions than a
conventional gasoline-fueled vehicle, the emissions from
the CNG-powered vehicle may have a higher potential for
environmental impact.
An alternative assessment approach, which weights emis-
sion quantities by their environmental impact potentials, is
based on exergy analysis. The rationale for this approach
is that most emission streams contain some exergy, and
therefore are in disequilibrium with the environment. Such
emissions have the potential to disturb the equilibrium of the
environment [6,7]. The exergy (or potential to do work) of an
unconstrained emission of a substance is released to the envi-
ronment as the substance is brought to the reference state of
the environment. This exergy may be considered a measure
of the potential of a substance to impact the environment.
Others also have used exergy to examine environmental im-
pact [8–13].
As a consequence of the above arguments, this study ex-
amines the emissions produced during the fuel life cycle
using exergy methods. The objectives are to help identify
transportation fuels and technologies that are environmen-
tally problematic and to illustrate the benefits of the exergy
approach in environmental-impact assessments.
This paper is part of a broader program by one of
the authors into the use of exergy methods in efficiency
 J.J. Daniel, M.A. Rosen / Exergy, an International Journal 2 (2002) 283–294
improvement [14,15] and environmental assessments [6,7,
16–20]. More specifically, the present work extends the
initial work carried out for a limited set of transportation
vehicle options [21].
2. Background on exergy
The concept and application of exergy has been discussed
extensively [22–25]. Exergy is defined as the maximum
amount of work that can obtained when a thermodynamic
system or flow (e.g., matter, heat, work) is brought into
equilibrium with a reference environment. Exergy is a
measure of the potential of the system to cause change as
a result of the system not being in stable equilibrium relative
to the reference environment. Exergy analysis is most often
used to assess and improve the efficiencies of devices and
processes.
Exergy has also been reported to be a potentially effective
measure of the potential of a substance to impact the
environment [15,18,19].
In this study, we consider the waste emissions produced
during the fuel life cycle for automotive vehicles. These
wastes can be heat or matter. On a local level, heat emis-
sions can cause some environmental change. For example,
consider the cooling water outlet from a power plant, which
exits into a lake. At the pipe exit, local water temperatures
may be a few degrees higher than the average lake tem-
perature, and this phenomenon can affect nearby plant and
animal life. Usually, heat and thermomechanical exergy
material emissions (i.e., emissions that are in chemical
equilibrium with the local environment, but at a different
temperature and/or pressure) can be considered environ-
mentally benign [21]. Overall, the environment may be
considered a heat sink, with the contributions of heat emis-
sions to the temperature of the land, water and air in the
environment small compared to the effects of solar energy.
Emission streams at different pressures than the atmosphere
quickly expand or contract on entering the environment, and
in general have little or no impact on the biosphere. Of
course, the pressure difference does represent opportunity
for work, and could be utilized by a device such as a tur-
bine.
On the other hand, even small amounts of waste material
emissions entering the environment can cause great damage
to the biosphere due to chemical effects. Also, these material
emissions can be carried far from where they originate by
prevailing winds and other weather effects. Consequently,
chemical exergy correlates somewhat with the potential
for environmental impact. This study concentrates on the
chemical exergies of emissions produced during the fuel
life cycle, and neglects their thermomechanical exergies. For
simplification, gravitational fields, electromagnetic fields,
nuclear and surface effects, and kinetic energy and exergy
are neglected.
285
2.1. Reference environment
Exergy is evaluated with respect to a reference environ-
ment model. The reference environment model used often
is chosen to be similar to the natural environment, and
consists of substances commonly found in the atmosphere,
hydrosphere and lithosphere. Since the physical world is
complicated, simplifications are normally made in specify-
ing the characteristics of a reference environment model.
The reference environment is assumed to be a sink and
source for heat and matter, to be free of irreversibilities, to
have zero exergy, and to have constant intensive properties
which are not significantly affected as a result of any process
under consideration. The environment therefore is treated as
being is in an equilibrium state.
The natural environment is, of course, not in equilib-
rium, and its intensive properties vary both spatially and
temporally. Also, the environment contains plant and animal
life, which are not accounted for in models. Furthermore,
the exergy of the natural environment is not zero, as many
chemical reactions are blocked because at ambient condi-
tions the transport mechanisms to reach equilibrium are too
slow. In addition, changes in the real environment with time
may cause the model of the environment to be different,
or time varying. For example, the levels of CO2 in the at-
mosphere are not constant. Here, present levels of CO2 in
the atmosphere are used, rather than pre-industrial levels.
Consequently, the selection of a reference environment
model can be subjective, and the simplifications and ideal-
izations made in formulating a model can restrict the utility
and validity of an exergy analysis. However, this same sub-
jectivity allows an exergy analysis to be tailored to the actual
environment of a system being analyzed.
The reference environment chosen for this paper consists
of liquid water and saturated moist air in phase equilibrium
as well as the solids gypsum and limestone (see Table 1).
This environment is based on the work of Gaggioli and Petit
[26], with the only exception being the reference pressure is
considered to be 0.1 MPa rather than 1 atm to be consistent
with the JANAF Thermochemical Property tables [27], from
which some thermodynamic data is obtained.
Table 1
Characteristics of the reference environmenta
Gaseous phase Mole fraction
N2 0.7567
O2 0.2035
H2 O 0.0303
Ar 0.0091
CO2 0.0003
Condensed phases State
H2 O liquid
CaCO3 solid
CaSO4 · 2H2 O solid
T = 298.15 K, p = 0.1 MPa
a Adapted from Gaggioli and Petit [26].
286 J.J. Daniel, M.A. Rosen / Exergy, an International Journal 2 (2002) 283–294
Table 2
Specific chemical exergies of selected substancesa
Component Specific chemical exergy (kJ·kmol−1 )
CO 275 100
CH4 831 650
N2 O 106 880
CO2 19 870
NOx 55 600
SOx 313 400
a Data calculated from JANAF Thermochemical Tables [27]. NO is
x ganic compounds and particulate matter with a diameter of
assumed to be composed of nitrogen monoxide, and SOx is assumed
to be composed of sulfur dioxide [29,41] for specific chemical exergy
calculations.
2.2. Chemical exergy evaluation
Chemical exergy is equal to the maximum amount of
work that can be developed when a substance is brought
from the environmental state (where the temperature is To
and pressure Po ) to the reference state via processes involv-
ing heat transfer and exchange of substances exclusively
with the environment. The chemical exergy of a substance
depends on if the substance is found in the reference envi-
ronment. For determining the chemical exergy of gases in
the reference environment, it is first necessary to calculate
the work needed to obtain the components at standard pres-
sure from the partial pressure of the reference state. It then
follows that the specific chemical exergy of a substance is
given by
ech = RTo ln(Po /Poo )
where R is the universal gas constant, and Poo is the partial
pressure of the component in the reference state. Substances
not found in the reference environment develop work as they
react with substances in the reference environment to form
substances that are found in the reference environment. In
such cases, the specific chemical exergy is given by

ch,in
ch,out
ech = −Go − x i ei + x i ei
where Go is the Gibbs function of formation, which can be
written as
Go = (νk gk )products − (νj gj )reactants
Here νk and νj are the stoichiometric coefficients, gk and gj
are the molar Gibbs functions of formation, and j denotes
the j th co-reactant and k the kth product. The chemical
exergy for mixtures can be expressed as
ech = xi eich + RTo xi ln xi
Table 2 shows the specific chemical exergies of selected
substances considered in this study.
3. Methodology
In this study of fuel life cycle emissions of alternative
fuel and vehicle technologies, it is necessary to use “normal-
ized” data (i.e., data which has been put on a consistent and
comparable basis) so that reasonable comparisons of the dif-
ferent technologies can be made. The GREET (Greenhouse
gases, Regulated Emissions, and Energy use in Transporta-
tion) model, developed by the Center for Transportation
Research at Argonne National Laboratory, was chosen as
a source of the normalized data. For a given fuel/vehicle
combination, GREET calculates the fuel life cycle consump-
tion of energy (from all sources) and fossil fuels, and the
emissions of CO2 , CH4 , N2 O, CO, NOx , SOx , volatile or-
10 micrometers or less. GREET is used by various industries
(including the automotive industry), and has been found to
provide results that compare favorably to measured emission
data from non-affiliated sources. The accurate emissions
data and flexibility of the program to accept a variety of user
inputs makes GREET a worthy research tool. For example,
a recent study used GREET emission data to compare the
fuel life cycle emissions of trucks utilizing CIDI engines fu-
elled with LPG, CNG, and diesel [28]. Further information
on GREET is presented by Wang [29,30].
A modified version of GREET is used for this study
to calculate the chemical exergies of emissions in addition
to the masses of emissions produced during the fuel life
cycle. Due to difficulties quantifying the chemical exergies
of particulate matter and volatile organic compounds, these
substances are not considered in this study. See Wang
[30] for data regarding the masses of these emissions
produced during the fuel life cycles. Particulate matter
affects human health, and is responsible for soot and smoke
produced during certain processes (such as combustion
of fossil fuels). Volatile organic compounds are generally
composed of many different chemicals that do contain
chemical exergies. Unfortunately, the actual composition
is process dependent, and for many processes considered
in this study, the composition is not well defined. As a
result, the chemical exergies for volatile organic compounds
emitted during the fuel life cycles examined herein are not
quantified. Finally, although hydrocarbons can lead to smog
and ozone production, and therefore should be included in
environmental assessments, data on hydrocarbon emissions
normalized on the same basis as the other data presented
below could not be located (especially for the prevehicle
operation stages). For this reason, hydrocarbon emissions
are also not considered.
In this study, the fuel life cycle is taken to be composed
of three stages: feedstock, fuel and vehicle. The feedstock
stage encompasses processes used during feedstock recovery
through to feedstock delivery to the fuel production plant,
and includes recovery, transportation and storage of the en-
ergy feedstocks. The fuel stage encompasses fuel-production
activities between the delivery of the feedstock to the fuel
production plant, and the delivery of the fuel to the refueling
station. Activities in this stage include production, trans-
portation, storage and distribution of the fuel. The vehicle
stage begins after completion of the fuel stage, and includes
 J.J. Daniel, M.A. Rosen / Exergy, an International Journal 2 (2002) 283–294
fuel delivery to the refueling station through to the conver-
sion of the fuel to provide a service during vehicle operation.
This study concentrates on emissions of CH4 , CO,
CO2 , NOx , N2 O and SOx during the fuel life cycle of
many vehicles. Other hydrocarbons, particulate matter, and
volatile organic compounds are not considered.
Thirteen different fuel and vehicle combinations are
considered in this study, as shown in Table 3, where one or
more fuel types is shown for each vehicle type. The vehicles
considered are either commercially available or likely to
enter the market in the near future. All fuels considered are
currently commercially available. The following points are
made regarding the fuel vehicle combinations in Table 3:
• Spark-ignition, direct injection engines use highly-stra-
tified fuel delivery injected directly into the cylinder to
burn the fuel more efficiently.
• Compression-ignition, direct injection engines are more
fuel efficient than a comparable conventional spark-
ignition engine. This type of engine requires diesel-type
fuels that combust under compression, rather than in the
presence of a spark. However, these engines (and fuels)
usually produce higher levels of particulate matter.
• Flexible-fuel vehicles can run on straight gasoline, or on
a blend of gasoline and methanol/ethanol. In this study,
the flexible-fuel vehicles are assumed to be capable
of operating on up to 85% ethanol/methanol blended
with gasoline. Bi-fuel vehicles can operate on either
conventional gasoline or an alternative fuel (CNG, in
Table 3
Fuel-vehicle combinations considered
Vehicle type
Conventional spark ignition engine
Conventional CIDI engine
Bi-fuel
Dedicated alternative fuel
Flexible fuel
SIDI hybrid electric: Grid-connected
SIDI hybrid electric: Grid-independent
Grid-independent CIDI hybrid electric
Table 4
Fuels considered and their corresponding feedstock(s)
Fuel
Conventionala /reformulatedb gasoline
Conventional diesel
Compressed/liquefied natural gas
Liquefied petroleum gas
Ethanol
Methanol
Electricityc
a Assumes 2.0% MTBE volumetric content in conventional gasoline [42].
b Assumes 2.7% oxygen by weight in Federal Phase 2 reformulated gasoline, and 2.1% oxygen by weight in California reformulated gasoline [29]. MTBE
is selected to meet these requirements.
c Electricity generation mix is based on average US generation mix [36].
287
this study). This type of vehicle is well suited to areas
where alternative fuel depots are not widespread. On the
other hand, dedicated alternative fuel vehicles can only
use one type of fuel. However, the engine and emission
systems can be more finely tuned to the alternative fuel,
and therefore these vehicles can produce fewer vehicle
operation emissions than a flexible fuel vehicle or a bi-
fueled vehicle.
• Hybrid electric vehicles use both an on-board battery
and electric motor and an internal combustion engine
to propel the automobile. The batteries are charged
as the vehicle slows by using the electric motor(s)
as generators. Grid-connected hybrid vehicles can also
have their batteries recharged from the electrical grid
(whereas grid-independent hybrid vehicles have no
capability to do so).
Since some fuel types can have different feedstocks,
the selected feedstock for each fuel is indicated where
appropriate (see Table 4). Passenger cars, rather than light-
and heavy-duty trucks, are considered. Some examples of
advanced vehicular technologies include the General Motors
Impact electric vehicle, and the Toyota Prius and Honda
Insight, two gasoline-electric hybrid vehicles.
The fuel life cycles are chosen to approximate emissions
from passenger cars undergoing the US Federal Test Pro-
cedure [29]. The baseline conventional gas vehicle is taken
to be a passenger car with a fuel economy of 22.4 miles
per gallon (10.5 litres per 100 kilometers). Estimated fuel
Fuel types
Conventional, Federal reformulated, and California reformulated gasoline
Conventional diesel
Compressed natural gas
Compressed natural gas, liquefied petroleum gas, electricity
Methanol (M85 blend), ethanol (E85 blend)
California Phase 2 reformulated gasoline
Federal Phase 2 reformulated gasoline
Conventional diesel
Feedstock
Petroleum (100%)
Petroleum (100%)
Natural gas (100%)
Natural gas (60%), petroleum (40%)
Dry-milling corn (33%), wet-milling corn (67%)
Natural gas (100%)
Coal (53.8%), uranium (18.0%), natural gas (14.9%), hydropower, solar
energy and wind (12.3% collectively), petroleum (residual oil) (1%)
288 J.J. Daniel, M.A. Rosen / Exergy, an International Journal 2 (2002) 283–294
Table 5
Estimated fuel economies of the vehicles considereda
Vehicle/fuel type Miles per gallonb
(litres per 100 kilometers)
Baseline conventional gasoline vehicle: CG 22.4 (10.5)
Conventional gasoline vehicle: FRFG2 22.4 (10.5)
Conventional gasoline vehicle: CRFG2 22.4 (10.5)
CIDI vehicle: conventional diesel 30.2 (7.8)
Bi-fuel CNGV: CNG 20.2 (11.7)
Dedicated CNGV 20.8 (11.3)
Dedicated LPGV 22.4 (10.5)
M85 flexible fuel vehicle 23.5 (10.0)
E85 flexible fuel vehicle 23.5 (10.0)
Electric vehicle 67.2 (3.5)
Grid-connected SIDI HEV: grid operation 67.2 (3.5)
Grid-connected SIDI HEV: CRFG2 40.3 (5.8)
Grid-independent SIDI HEV: FRFG2 42.6 (5.5)
Grid-independent CIDI HEV: conventional diesel 44.8 (5.2)
a Adapted from Wang [29]. b Conventional gasoline equivalent gallon.
economies of other vehicle types examined in this study are
presented in Table 5.
Estimated vehicle stage emissions may not be indicative
of real vehicle emissions, as road type, driving behaviour
and engine temperature can greatly affect tail-pipe emissions
and fuel mileage [31]. Note that reduced fuel economy
can increase upstream emissions in the fuel life cycle, as
more fuel will have to be produced for the vehicle to travel
the same distance. Therefore, data presented herein likely
underestimates the real fuel life cycle emissions. However,
the use of estimated vehicular emissions based on the US
Federal Test Procedure facilitates consistent comparisons of
results.
3.1. CO2 sequestration during the E85 fuel life cycle
One of the alternative fuels considered in this study is E85
(85% ethanol and 15% conventional gasoline by volume).
The ethanol component can be formulated from several
biological feedstocks. For this study, corn is chosen as the
feedstock, to be consistent with current ethanol production
practice. Woody and herbaceous biomass can also be used
as ethanol feedstocks, but since they are used on a much
smaller scale and have not yet penetrated the market to the
same extent as ethanol from corn, they are not considered in
this study. Lynd et al. [32] reported in a recent study that
the central impediment to the widespread implementation
of biocommodity engineering is the general absence of low-
cost processing technology, and that biomass feedstocks are
available at a large scale and are cost-competitive with low-
cost petroleum on both mass and energy bases.
During natural plant respiratory processes that occur
during the growth of corn, CO2 is removed from the air. The
CO2 that is sequestered during the feedstock stage is applied
as a credit in this study to the other stages of the fuel life
cycle for ethanol. This is done to facilitate the calculations
of the chemical exergy of CO2 emissions. For the E85 FFV
fuel life cycle, approximately 248 g of CO2 is sequestered
in the feedstock stage (per vehicle mile traveled), and this
credit is applied as follows:
1(a). Fuel stage CO2 emissions 183 g
1(b). Fuel stage CO2 emissions after credit applied 0 g
2(a). Vehicle stage CO2 emissions 370 g
2(b). Vehicle stage CO2 emissions after remaining credit
applied 305 g
3. Total CO2 emissions for fuel life cycle 305 g
Although it is difficult to specify exactly where CO2
that is sequestered actually originates, this uncertainty is
not likely to significantly affect this study. The total CO2
released during the fuel life cycle, which is not impacted by
sequestration-related approximations, is more important to
the present results.
Wang et al. [33,34] give an overview on the biomass to
ethanol process, and summarize the assumptions and data
used in regards to the biomass to ethanol cycle, including
calculations for CO2 sequestration. However, a recent study
[17] suggests any CO2 credit should be applied with caution.
An analysis also should be done without CO2 credits, in
which case the E85 fuel life cycle appears to be the least
environmentally benign after the CNG fuel cycles using the
chemical exergy optic [35].
3.2. Non-combustion emissions
Emissions from non-combustion processes in the fuel
cycle are also estimated in this study. For liquid fuels,
emissions from fuel spillage during both feedstock transport
and storage and fuel transport, storage and distribution are
considered. During the production of petroleum-based fuels,
emissions from flaring and venting of gas in oil fields
are assessed, as are emissions from the refining process.
Methane emissions from natural gas pipeline transmissions
and emissions during processing are taken into account.
Furthermore, methane emissions from coal mining and
coal processing during coal-based electricity generation are
also incorporated into the model. During the production
process in which natural gas is converted to methanol,
the associated emission of carbon dioxide is calculated.
Finally, oxides of nitrogen and nitrous oxide emissions from
the nitrification/denitrification and washing out of nitrogen
fertilizers are estimated; this information is relevant during
feedstock production of corn for the ethanol component of
E85 fuel.
3.3. Electricity-generation mix
For dedicated electric vehicles, as well as grid-connected
HEVs, the mix of energy resources used for electricity gen-
eration can greatly affect the emissions produced during
the fuel life cycle. Table 4 lists the United States aver-
age electricity-generation mix, which is used to estimate
 J.J. Daniel, M.A. Rosen / Exergy, an International Journal 2 (2002) 283–294 289

emissions data in GREET and in this study. In actuality, grid-
connected HEVs and electric vehicles do not draw power
from the average electricity generation mix. However, due
to uncertainties in estimating regional electricity generation
mixes [36] and so as to make this study non-region specific,
the average electricity generation mix is used. To more accu-
rately determine the effects on the fuel life cycle emissions
changes for a particular location when internal combustion
engine vehicles are replaced with battery electric vehicles, a
thorough region-specific study is recommended. By doing
so, seasonal variables, regional electricity-generation mix,
and peak vs. off-peak electricity demand variables can be
accounted for. For example, one such study was performed
for the Lower Fraser Valley [37].
For the grid-connected hybrid vehicle, it is assumed that
30% of vehicle miles traveled are via grid electricity, with
on-board devices supplying the power for the remaining
70% of VMT [29].
4. Results and discussion
The emissions results, normalized to a per unit ve-
hicle mile traveled (VMT) basis, are presented for each
fuel/vehicle case in Figs. 1–8. The results are shown for the

Fig. 1. Mass of waste emissions produced during the feedstock stage per vehicle mile traveled. The vehicle type and fuel are shown where appropriate.

Fig. 2. Chemical exergies of waste emissions produced during the feedstock stage per vehicle mile traveled. The vehicle type and fuel are shown where
appropriate.
290 J.J. Daniel, M.A. Rosen / Exergy, an International Journal 2 (2002) 283–294
overall fuel life cycle and broken down into the three stages
comprising it. Each set of results is presented on mass and
chemical exergy bases. For the data base used for the calcu-
lations represented in the figures, see Wang [30].
Fig. 1 shows the masses of the emissions produced
during the feedstock stage per VMT. On a mass basis, CO2
is seen to be the dominant pollutant, except in the case
of E85 feedstock production, where CO2 is sequestered.
Nitrification/denitrification and washing out of the fertilizer
applied to the cornfield accounts for the relatively high N2 O
and NOx emissions produced during the E85 fuel cycle.
The feedstock stage for compressed natural gas produces
more CO2 than any of the other fuel-vehicle combinations
presented, as well as the most methane gas.
Fig. 2 presents the chemical exergies of the emissions
produced per VMT for the feedstock stage. In Fig. 2, it can
be seen that, although CH4 emission accounts for only a
small amount of the mass of emissions produced during the
feedstock stage, it is the most predominant emission from a
chemical exergy perspective. This result is due to methane’s
high specific chemical exergy and is especially significant
for the CNG feedstock stage (note the bi-fuel CNG vehicle
and the dedicated CNG vehicle results in Fig. 2). From the
chemical exergy view, the feedstock stage for E85 is the
most environmentally benign (as it also is in Fig. 1), but the
advantage is less obvious in Fig. 2 due to the contribution
of CO, NOx and especially CH4 . This observation is due
to the fact that these substances have much higher specific
chemical exergies than CO2 . In all cases, CO makes a larger
contribution to the total chemical exergies of emissions than
it does to the total mass of emissions.
Figs. 3 and 4 show the masses and chemical exergies,
respectively, of the emissions produced per vehicle mile
traveled during the fuel stage. Note that very few emissions
are produced for the E85 FFV, with those present including
Fig. 3. Mass of waste emissions produced during the fuel stage per vehicle mile traveled. The vehicle type and fuel are shown where appropriate.
mainly NOx , CH4 , SOx , and CO (although these cannot
be seen in Fig. 3 due to the scale of the graph). For each
of the fuel life cycles in Figs. 3 and 4, it is clear that
CO2 is the dominant pollutant on mass and chemical exergy
bases. The exception is the E85 FFV case, which exhibits
no CO2 emissions because the feedstock CO2 sequestration
credit has been applied. In Fig. 4, the chemical exergy
contributions from the emissions of CO, NOx , SOx and CH4
produced during the E85 FFV fuel stage are visible. These
emissions are shown to be more significant using the optic
of exergy rather than mass alone (see Fig. 3), due to their
relatively high specific chemical exergies. In fact, higher
chemical exergies of emissions are observed in Fig. 4 for
the fuel stage for the E85 FFV than for both the dedicated
LPG vehicle and the grid-independent diesel hybrid vehicle.
The perspective presented by these observations contrasts
notably with findings in Fig. 3. The fuel stage for the
dedicated electric vehicle produces the highest emissions,
but this finding is directly tied to the assumed electricity-
generation mix (which is presented in Table 4). The fuel
stage for this vehicle essentially involves the generation
of electricity. As a consequence of its dependence on the
electrical grid, the fuel stage for the grid-connected hybrid
vehicle produces more emissions on mass and chemical
exergy bases than the two grid-independent hybrid vehicles,
including higher levels of NOx , SOx and CO2 .
The masses of the emissions produced per VMT during
the vehicle stage are shown in Fig. 5. The dedicated electric
vehicle is seen to produce no emissions during this stage. In
reality, particulate emissions from brake and tire wear are
produced during vehicle operation, but particulate emissions
are not considered in this study. As in the feedstock and
fuel stages, it is seen in Fig. 5 that CO2 makes up the
majority of the masses of emissions. Carbon monoxide also
is notable in Fig. 5, but to a much smaller extent. Relatively
 J.J. Daniel, M.A. Rosen / Exergy, an International Journal 2 (2002) 283–294 291

small quantities are produced during the vehicle stage of
substances such as NOx , SOx , and CH4 and these are
not visible in Fig. 5. In general, the diesel vehicles under
consideration produce less CO and CH4 , but more NOx and
SOx (and particulate matter), compared to the other vehicles
that use spark ignition engines.
Fig. 6 shows the chemical exergies of emissions produced
per VMT in the vehicle stage. While CO only composes a
small fraction of the masses of emissions produced during
the vehicle stage, its contribution to the total chemical
exergies of emissions is seen in Fig. 6 to be much more
significant. Also, CH4 emissions, especially for the CNG
vehicles, become more significant from a chemical exergy
perspective than they are on a mass basis (see Fig. 5). Note
that due to the large contribution of CH4 to the chemical
exergies of emissions for CNG vehicles, these vehicles may
have a greater potential for environmental impact than all
other fuel-vehicle combinations under consideration for the
vehicle stage. This result contrasts greatly with the data
presented in Fig. 5, where the CNG vehicles appear to be the
most environmentally benign spark-ignition vehicles during
this stage (with the possible exception of the flexible fuel
E85 vehicle after the feedstock CO2 sequestration credit).
For the diesel vehicles, the emission contributions from NOx
and SOx are more notable in Fig. 6 than in Fig. 5.
Fig. 7 presents the total mass of emissions for the
entire fuel life cycle (i.e., the feedstock, fuel and vehicle
stages combined) as well as the contributions of each stage.

Fig. 4. Chemical exergies of waste emissions produced during the fuel stage per vehicle mile traveled. The vehicle type and fuel are shown where appropriate.

Fig. 5. Mass of waste emissions produced during the vehicle stage per vehicle mile traveled. The vehicle type and fuel are shown where appropriate.
292 J.J. Daniel, M.A. Rosen / Exergy, an International Journal 2 (2002) 283–294

Conventional vehicles fueled with reformulated gasolines
(US Federal and California) are seen in Fig. 7 to produce
more emissions than the life cycle for the same vehicle type
fueled with conventional gasoline. This result is attributable
to the fuel stage, where more resources have to be expended
on the reformulated gasoline in order for it to produce less
emissions when combusted. The vehicle-stage emissions
for the reformulated gasolines are slightly lower than the
conventional gasoline vehicle-stage emissions. The data in
Fig. 7 suggest that the fuel life cycle for the grid-independent
diesel hybrid vehicle is the most environmentally benign.
However, this study omits particulate matter, and diesel
vehicles generally yield more exhaust particulate matter than
comparable spark ignition vehicles.
Fig. 8 presents the total chemical exergies of emissions
for the entire fuel life cycle and the contribution of the feed-
stock, fuel and vehicle stages. From this exergy perspective,
the CNG vehicles are seen to have the potential to cause
greater environmental impact than the other fuel-vehicle
combinations under consideration in this study, due mostly
to the CH4 emissions produced during the fuel life cycle. As
reported by the National Risk Management Laboratory [38]
and the EIA [39], a large amount of CH4 emissions occurs
during the transmission and distribution of natural gas. It was
estimated that, for the feedstock and fuel stages methane

Fig. 6. Chemical exergies of waste emissions produced during the vehicle stage per vehicle mile traveled. The vehicle type and fuel are shown where
appropriate.

Fig. 7. Total mass of emissions produced during the fuel life cycle per vehicle mile traveled. The vehicle type and fuel are shown where appropriate.
 J.J. Daniel, M.A. Rosen / Exergy, an International Journal 2 (2002) 283–294
emissions, 26.6% occurs during the production of natural
gas, 11.6% during processing, 37.1% during transportation
and storage, and 24.5% during distribution [38]. However,
a study by Harrison et al. [40] maintains that an increase in
demand for natural gas would decrease the CH4 emission
rate as a percentage of natural gas production, especially in
the US where there is currently an excess capacity of trans-
mission and distribution systems. Additionally, it is assumed
the vehicle stage for natural gas-powered vehicles produces
ten times the CH4 emissions compared to the baseline CG
vehicle. Advancements in vehicle technologies are hoped to
reduce these emissions during vehicle operation, especially
if natural gas is heavily promoted as an alternative vehicle
fuel.
The fuel life cycle for the electric vehicle is seen to be
more environmentally benign than that for the E85 FFV or
the grid-connected hybrid vehicle. This result contrasts with
the mass analysis of Fig. 7, where the fuel life cycle for
the grid-independent diesel hybrid vehicle appears to be the
most environmentally benign.
5. Conclusions
The quantity exergy has characteristics that suggest it
may be usable as an indicator of potential for environmental
impact. The part of exergy that is the most significant en-
vironmental indicator is chemical exergy, since thermal and
mechanical (i.e., pressure related) emissions are relatively
benign. For two emissions streams, the one with greater
chemical exergy likely has the higher potential for environ-
mental impact. This impact is attributable to the fact that
having exergy implies a substance is in disequilibrium with
the environment, and is a function of the process or processes
Fig. 8. Total chemical exergy of emissions produced during the fuel life cycle per vehicle mile traveled. The vehicle type and fuel are shown where appropriate.
293
that bring or can bring the emission into equilibrium with the
natural environment.
Thirteen different fuel life cycle paths have been exam-
ined in this paper. From the chemical exergy perspective,
the fuel life cycle emissions for the two CNG vehicles are
the furthest out of equilibrium with the environment. Also,
the grid-independent CIDI hybrid vehicle has the lowest
emission chemical exergies, and thus may be the most en-
vironmentally benign (omitting volatile organic compounds,
particulate matter and hydrocarbon emissions).
Future work based on this type of assessment appears to
be meritted. Inclusion of the volatile organic compounds,
hydrocarbon and particulate matter emissions in future
studies would make the environmental assessment more
complete. Although this study concentrates on the fuel life
cycle of various alternative fuel and vehicle technologies,
use of a cradle-to-grave vehicle life cycle would enhance
the environmental assessment. Doing so would permit a
total life cycle analysis to be performed, which would better
estimate the total impact on the environment for a given fuel-
vehicle combination. For example, chemical components of
the batteries found in dedicated electric and hybrid electric
vehicles (such as lithium, nickel-cadmium, etc.) are highly
out of equilibrium with the environment; the disposal of such
materials becomes important at the end of the vehicle life.
A vehicle life cycle analysis combined with the fuel life
cycle would likely show electric and hybrid vehicles to be
less environmentally benign than a fuel life cycle analysis
alone would indicate.
The work reported here should help in resolving the
growing concern about the impacts of the transportation-
sector emissions on the environment, quality of life, and
sustainable development, and should assist efforts to inves-
tigate alternative fuels and advanced vehicle technologies,
in order to create more environmentally benign modes of
294 J.J. Daniel, M.A. Rosen / Exergy, an International Journal 2 (2002) 283–294
transport. This paper has demonstrated that the concept of
exergy may provide quantitative insights into the environ-
mental impact of fuel and vehicle technologies. The methods
and results presented in this paper can be applied to any
material stream, and thus may be applicable in other circum-
stances and applications.
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