Bioresource Technology 101 (2010) 654–667

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Life cycle evaluation of emerging lignocellulosic ethanol conversion technologies

Sabrina Spatari a,*, David M. Bagley b, Heather L. MacLean c
a
Drexel University, Civil, Architectural, and Environmental Engineering, 3141 Chestnut Street, Philadelphia, PA 19104, USA
b
University of Wyoming, Department of Civil and Architectural Engineering, 1000 E. University Avenue, Department 3295, Laramie, WY 82071, USA
c
University of Toronto, Department of Civil Engineering and School of Public Policy and Governance, 35 St. George Street, Toronto, Ontario, Canada M5S 1A4

a r t i c l e i n f o a b s t r a c t

Article history: Lignocellulosic ethanol holds promise for addressing climate change and energy security issues associ-
Received 28 January 2008 ated with personal transportation through lowering the fuel mixes’ carbon intensity and petroleum
Received in revised form 30 March 2009 demand. We compare the technological features and life cycle environmental impacts of near- and
Accepted 14 August 2009
mid-term ethanol bioconversion technologies in the United States. Key uncertainties in the major pro-
Available online 16 September 2009
cesses: pre-treatment, hydrolysis, and fermentation are evaluated. The potential to reduce fossil energy
use and greenhouse gas (GHG) emissions varies among bioconversion processes, although all options
Keywords:
studied are considerably more attractive than gasoline. Anticipated future performance is found to be
Biofuels
Lignocellulosic ethanol
considerably more attractive than that published in the literature as being achieved to date. Electricity
Life cycle assessment co-product credits are important in characterizing the GHG impacts of different ethanol production path-
Uncertainty analysis ways; however, in the absence of near-term liquid transportation fuel alternatives to gasoline, optimizing
Monte Carlo analysis ethanol facilities to produce ethanol (as opposed to co-products) is important for reducing the carbon
intensity of the road transportation sector and for energy security.
Ó 2009 Elsevier Ltd. All rights reserved.

1. Introduction To support these recent policy initiatives and, more broadly, to

Ethanol from lignocellulosic feedstocks has received much re-
cent attention for its potential role as a light-duty vehicle fuel
due to volatile crude oil prices, ethanol’s potential to reduce North
America’s dependence on imported petroleum, and recent policies
to reduce the carbon intensity of transportation fuels and to in-
crease the production of biofuels (Solomon et al., 2007; Sperling
and Yeh, 2009). The importance of biofuels in the United States
was reflected in the Energy Policy Act (US Congress, 2005) and
more recently in the Energy Independence and Security Act (EISA),
which calls for further increasing the use of these fuels in transpor-
tation, and requiring the use of lignocellulose-based fuels begin-
ning in 2010 (US Congress, 2007). Lignocellulosic ethanol
possesses environmental and resource conservation advantages
over both petroleum-based fuels and corn-derived ethanol, includ-
ing potentially lower life cycle greenhouse gas (GHG) emissions
and reduced usage of fossil fuel resources, particularly imported
petroleum (Fu et al., 2003; Sheehan et al., 2003; Spatari et al.,
2005; Farrell et al., 2006). Production of the fuel could stimulate
rural economic development (Kim and Dale, 2004), and ethanol
is compatible with existing light-duty vehicles in blends with gas-
oline at low (10%) and high (85%) volumes.
make progress in improving the environmental performance of our
light-duty vehicle transportation system, a suite of emerging tech-
nologies for converting lignocellulosic feedstocks to ethanol is un-
der development at laboratory, pilot, and demonstration scales
(Wyman et al., 2005a; Eggeman and Elander, 2005; Aden et al.,
2002; US DOE, 2007). The technologies consist of different pre-
treatment methods (Wyman et al., 2005a; Mosier et al., 2005)
and enzymatic hydrolysis and fermentation orientations (Lynd
et al., 2002). As these developing technologies may differ in their
feedstock requirements as well as process energy and chemical in-
puts, they exhibit a range of life cycle energy and environmental
performance, an aspect that has not been discussed in detail in
the literature (Spatari, 2007).
Life cycle assessment (LCA) studies have shown environmental
and social benefits associated with lignocellulosic ethanol and its
use in light-duty vehicles compared to gasoline and corn ethanol
fueled vehicles (e.g., Spatari et al., 2005; Sheehan et al., 2003). To
date, most studies have focused on modeling the upstream agricul-
tural processes in specific geographic locations as well as the end
uses and have considered only a limited set of feedstocks in addi-
tion to a single pre-treatment-conversion technology. Further-
more, these published estimates are based on ASPEN simulations
of commercial scale nth plants.1 While it is important to examine

1
* Corresponding author. Tel.: +1 215 571 3557; fax: +1 215 895 1363. Industrial facilities that have overcome cost and performance penalties of the
E-mail address: spatari@drexel.edu (S. Spatari). first-of-a-kind (pioneer) facilities.

0960-8524/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2009.08.067
 S. Spatari et al. / Bioresource Technology 101 (2010) 654–667 655

the predicted best case scenarios, it is also useful to understand per-
formance to date and evaluate the transition from present to future
performance.
Another gap in most published LCA studies is that they have not
accounted for the impacts associated with the production and use
of pre-treatment chemicals, enzymes and nutrients used in the
conversion process (see MacLean and Spatari (2009)).
Lignocellulosic ethanol has been attracting much attention due
to its promise of assisting governments to make progress on reduc-
ing GHG emissions from the transportation sector (Farrell et al.,
2006). In spite of this attention there are, as yet, no commercial lig-
nocellulose-to-ethanol facilities, and there is considerable uncer-
tainty regarding preferred technologies and their operating
parameters. Therefore, the objectives of this paper are (1) to con-
duct LCAs of lignocellulosic ethanol production from a larger set
of bioconversion technologies than has been previously examined;
(2) to investigate how uncertainties in technological performance
affect life cycle results through combining LCA with Monte Carlo
simulation; (3) to include in the LCA the upstream impacts associ-
ated with chemicals utilized in the conversion processes; and (4) to
understand, especially, the predicted ethanol yields, co-product
electricity, fossil energy input and environmental emissions factors
including GHG emissions for the technologies examined both in the
near-term (c. 2010) and mid-term (c. 2020) using LCA. The research
demonstrates a life cycle approach/framework that is expected to
be useful to researchers and technology developers as well as gov-
ernment entities (e.g. US Department of Energy) in estimating the
life cycle performance of technologies under development.
The technologies selected for study in this research are not
meant to represent the full set of technologies under development
(or their performance), ‘nor does their selection for modeling imply
endorsement by the authors.
2. Methods
We use LCA (ISO, 2006) to compare the energy and material in-
puts and environmental emissions associated with eight near-term
(c. 2010) and two advanced mid-term (c. 2020) lignocellulosic eth-
anol conversion technologies in the United States.
Normally LCA is conducted on the complete cycle of production
and use of a product; however, because we are comparing the
same product (ethanol), we limit the analyses to the production
stages, which include feedstock production and transport, and eth-
anol conversion. This is sometimes termed a well-to-(plant) gate
(WTG) analysis in the LCA literature of alternative fuels.
To allow comparison of the different technology scenarios, we
constructed LCA models with two different sets of input data.
One set of input data was developed from laboratory or process
development unit (PDU) scale data presented in the literature.
For models using this data set, we apply Monte Carlo analysis to
consider uncertainty in the predicted performance. The second
set of input data is generated from chemical plant designs simu-
lated by ethanol technology developers using Aspen Plus software.
The Aspen simulations generally represent conditions set to maxi-
mize ethanol production under specific operating conditions as-
sumed for future ‘‘nth” plants. For both sets of models, data for
feedstock production and transport as well as all energy and emis-
sions associated with fuels and chemicals used throughout the eth-
anol production life cycle were obtained from a combination of
public (Wang, 2007) and private (PE, 2004) sources.
We develop LCA models based on material and energy balances
to estimate the technological indicators, ethanol yield and electric-
ity co-production; and the resource–environmental impacts fossil
energy input, petroleum input, GHG emissions (carbon dioxide
(CO2), methane (CH4), and nitrous oxide (N2O)), air pollutants (car-
bon monoxide (CO), nitrogen oxides (NOx), non-methane organic
gases (NMOG), sulfur oxides (SOx), and particulate matter (PM10))
and solid waste.
2.1. Feedstock production, collection and transport
We consider corn stover (CS) and switchgrass (SG) feedstocks
for near-term LCA models. Life cycle data for the production, col-
lection, and transportation of the feedstock include the energy

Table 1
Feedstock and transportation to conversion facility data model parameters.

Description Values Notes and data source

Feedstocks
Corn stover (CS) – near-term
Yield (dry metric ton/ha/yr) 9.7 Wang (2007)
Collection (MJ/dry metric ton) 260 MJ/dry metric ton Assumes 2-pass system. 50% removal of CS for ethanol
conversion. All data as per Wang (2007)
Dry weight composition (%) Glucan 37.4, xylan 21.1 arabinan 2.9, galactan 2, mannan Sheehan et al. (2003)
1.6, lignin 18
Nutrient replacement (g/dry kg CS) N 5, P 1.8, K 9.2 Sheehan et al. (2003), Kim and Dale (2004)
N2O emissions Direct: 44.1 Direct and indirect emissions calculated using IPCC
(g N2O/dry metric ton CS) Indirect: 66.7 (1997); co-product allocation described by Spatari (2007)
Switchgrass (SG) – near-term (mid-term)
Yield (dry metric ton/ha/yr) 11.2 Wang (2007)
Fertilizers (g/dry kg SG) N 11.7, P 0.16, K 0.25 Wang (2007)
Herbicide (g/dry kg SG) Atrazine 0.031 Wang (2007)
Harvesting (MJ/dry metric ton SG) 260 All data as per Wang (2007)
Dry weight composition (%) Glucan 32.3 (37.4), xylan 21.4 (24.9) arabinan 2.9 (3.4), Near-term: normalized average for near-term reported by
galactan 0.9 (1.1), mannan 0.3 (0.3), lignin 17.5 (23.6) Laser et al. (2009)
Mid-term: Laser et al. (2009)
N2O emissions 1.5% of N-fertilizer applied Wang (2007), Wu et al. (2006)
C sequestration due to land use change (g 53,500 Wang (1999)
CO2/dry metric ton SG)
Transportation – near-term (mid-term)
Distance 130 km (170 km) roundtrip Based on facility capacity of 2000 dry metric ton/day
(5000 dry metric ton/day)
Truck Class 8b heavy-duty, 2.1 L/km
Fuels/electricity (applicable to feedstock Assume US national electricity grid (Wang 2007)
production and transport in each LCA
model)

Note: Mid-term switchgrass values are noted in parentheses.

656 S. Spatari et al. / Bioresource Technology 101 (2010) 654–667

and emissions associated with fertilizers, herbicides, and fuel to
operate harvesting equipment (Wang, 2007). For assumptions,
parameters and data sources on feedstock activities see Table 1.
Wang (2007) utilizes US data for the feedstock activities but does
not site specific feedstock collection areas or biofuel production
facilities. We follow this example due to the prospective nature
of this research and our focus on biofuel production, rather than
agricultural activities.
The model for CS collection assumes that 50% of the CS remains
on the soil for maintaining soil organic carbon (SOC) and minimiz-
ing erosion, and 50% is removed for ethanol conversion. The
amount of stover that can be sustainably removed in order to
maintain SOC, which in turn retains and recycles nutrients, im-
proves soil structure, enhances water exchange characteristics,
sustains microbial life and ultimately improves corn and subse-
quent stover yields, varies with agricultural practice and location.
Some have argued that all stover should remain on the soil (Lal,
2004) while others indicate that between 5 and 8 Mg/ha should re-
main on the land for till and no-till practices on continuous corn
production, respectively (Wilhelm et al., 2007). These latter two re-
moval rates correspond to approximately 48% and 18% stover re-
moval for the yields we assume (Table 2). Although we do not
examine variability in stover removal in this analysis, Spatari
(2007) examines varying this model parameter between 35% and
70% based on literature estimates with a Monte Carlo analysis over
the production and use cycle of ethanol. Nutrients are added to re-
place those present in the CS removed from the field as noted by
Sheehan et al. (2003) and Kim and Dale (2005). The CS feedstock
is collected in a two-pass system (Wang, 2007). Since estimates
of emissions of N2O associated with N-fertilizer use vary widely
(Sheehan et al., 2002; Wang, 2007), we use the IPCC (1997) method
to estimate these emissions and a co-product allocation procedure
from Sheehan et al. (2003) to allocate the emissions to the CS col-
lected and that remaining on the field.
The SG production data are taken from Wang (2007) and are
summarized in Table 1. Fertilizers and the herbicide atrazine are
added. Switchgrass is harvested using farming equipment specified
by Wu et al. (2006); the equipment is assumed to be identical for
near and mid-term applications. We assume N application rates
consistent with test plot studies (Vogel et al., 2002). Nitrous oxide
emissions from N application are calculated as discussed by Wu
et al. (2006). The deep-rooting system of SG when planted on crop-
land and pastureland in the ratio 39:61 is assumed to result in
additional sequestration of CO2 in the quantity 53,500 g/dry metric
ton SG as noted by Wang (1999), albeit, uptake of atmospheric CO2
can be offset by N2O release associated with N-fertilizer applied
(Conant et al., 2005). The additional CO2 uptake is associated with
the cultivation of SG when grown on cropland assumed to formerly

Table 2
LCA variable input specifications (variable range and statistics) used in near-term Monte Carlo simulations and near- and mid-term input specifications for Aspen simulations.

Variable Variable Monte Carlo simulation Aspen simulation

notation
Range Mean Statistic Distribution Near- Mid-
terma termd
Low 2.5th High 97.5th Point Point
percentile percentile values values
Feedstocks
Corn stover (CS)
Glucan fraction (g glucan/g CS) fglucan 0.306 0.381 0.361 SD = 0.035 Student T 0.374
Xylan fraction (g xylan/g CS) fXylan 0.159 0.216 0.196 SD = 0.015 Logistic 0.211
Switchgrass (SG)
Glucan fraction (g glucan/g SG) fglucan 0.268 0.375 0.334 SD = 0.023 Logistic 0.323 0.375
Xylan fraction (g xylan/g SG) fXylan 0.176 0.249 0.219 SD = 0.047 Student T 0.211 0.249
Pre-treatment
Dilute acid (NREL)
Hemicellulose conversion (g hemicellulose sugar/ cj 0.6 0.75 0.675 SD = 0.038 Normal 0.75 0.95
g hemicellulose)
Hydrolysis conversion (g glucose/g glucan) cj 0.616 0.654 0.635 SD = 0.0097 Normal 0.8 0.95
AFEX
Hemicellulose conversion cj 0.65 0.85 0.75 SD = 0.051 Normal 0.776 0.95
Hydrolysis conversion cj 0.9 1 0.95 SD = 0.0097 Normal 0.95 0.95
Fermentation
Glucose-to-ethanol conversion (fraction of Yglu_eth 0.85 0.95 0.90 SD = 0.026 Normal 0.92b 0.95
theoretical yield) 0.95c
Xylose-to-ethanol conversion (fraction of Yxyl_eth 0.5 0.90 0.70 SD = 0.103 Normal 0.85b 0.95
theoretical yield) 0.85c
Arabinose-to-ethanol conversion (fraction of Ya_eth 0.01 0.72 0.283 Mode = 0 Triangular 0b 0.95
theoretical yield) 0.85c
Galactose-to-ethanol conversion (fraction of Ygal_eth 0.01 0.72 0.283 Mode = 0 Triangular 0b 0.95
theoretical yield) 0.85c
Mannose-to-ethanol conversion (fraction of Yman_eth 0.01 0.72 0.283 Mode = 0 Triangular 0b 0.95
theoretical yield) 0.85c

Notes: SD, standard deviation.

a
Near-term Aspen simulations with the SG feedstock compositions were modified from simulations run with the CS feedstock to adjust for differences in cellulose,
hemicellulose, and lignin concentrations as was done in previous LCA models (Spatari et al., 2005). Yields of ethanol from glucose, xylose, arabinose, galactose, and mannose
for the near-term models were estimated for two scenarios, one in which the fermentation yield in the first line of each row was assumed, and one in which the fermentation
yields in the second line shown were assumed.
b
The Aspen simulations whereby only glucose and xylose are fermented (first line) were set to correspond to Aspen model simulations investigated by the CAFI group, and
summarized in Wyman et al. (2005a,b), and in costing models by Eggeman and Elander (2005), and represent plausible near-term ethanol yield estimates.
c
The Aspen simulations whereby all five sugars are fermented (second line) were set to correspond to Aspen model simulations reported by Aden et al. (2002) and
assumed by Sheehan et al. (2003) in their LCA model of corn stover, and represent more optimistic estimates of ethanol yields relative to the estimates shown in the first line.
d
A Monte Carlo simulation was not undertaken for the mid-term models due to the difficulty in assigning plausible probability distributions to the advanced SG feedstock
and mature CBP technology assumed in those models. Only the advanced SG feedstock was examined for the mid-term Aspen simulations based on the model design reported
by Laser et al. (2009).
 S. Spatari et al. / Bioresource Technology 101 (2010) 654–667
be used for corn production Wu et al. (2006). The CS and SG feed-
stocks are assumed to be transported to a 2000 dry metric ton/day
ethanol conversion facility.
In the mid-term model, the properties of the ‘‘advanced” SG
(adv SG) feedstock are taken from Laser et al. (2009). Laser et al. re-
ports a mature SG crop having higher fractions of cellulose, hemi-
cellulose and lignin, and a decline in ash, protein, and soluble
carbohydrate relative to a normalized average SG measured from
25 samples, owing to a late season single-cut harvest, which sup-
ports cell-wall growth (sources of cellulose and hemicellulose)
and lignin and advances in breeding relative to current SG samples.
Inputs of fertilizers and herbicide, as well as feedstock harvesting
energy demand and N2O emissions are assumed to be the same
as the near-term SG models as noted by Wu et al. (2006). Only
the feedstock transport distance is assumed to be greater for the
mid-term model due to the larger collection distance required for
a 5,000 dry metric ton/day advanced ethanol conversion facility.
2.2. Ethanol conversion: pre-treatment, hydrolysis, and fermentation;
and electricity co-production
To produce ethanol from lignocellulose via biochemical conver-
sion the cellulose and hemicellulose fractions are digested into
sugars using a pre-treatment followed by a hydrolysis process.
The sugars are in turn fermented to alcohol, while the lignin frac-
tion is separated and used as a source of energy to drive the pro-
cess. The portions of cellulose and hemicellulose not converted to
sugars, and the sugars not fermented to ethanol are directed to the
facility’s energy recovery equipment along with the lignin. Use of
the lignin fraction and other biosolids produced during conversion,
including the non-digested cellulose/hemicellulose fibres and
unfermented sugars, for process energy improves the attractive-
ness of lignocellulosic technology, as it greatly reduces process fos-
sil energy requirements (Aden et al., 2002). Fig. 1 summarizes the
processing steps involved in the bioconversion of lignocellulose to
ethanol for the LCA models developed in this research.
Feed handling Pre-treatment
system
Steam &
Electricity
Energy recovery:
steam &
electricity
Fig. 1. Plant design model for the biochemical conversion of lignocellulose to ethanol. Notes: The model assumes energy recovery for steam and electricity production from
lignocellulose fractions not converted to ethanol. Adapted from model designs described by Aden et al. (2002) and Laser et al. (2009). CBP, consolidated bioprocessing; SSCF,
simultaneous saccharification and co-fermentation.
657
We examine two possible pre-treatment technologies, dilute
sulfuric acid developed at the National Renewable Energy Labora-
tory (NREL) and ammonia fibre explosion (AFEX) developed by
Bruce Dale and colleagues at Michigan State University. These
technologies were selected for near-term LCA model development,
based on data availability, from a set of promising emerging tech-
nologies and in particular in the case of the NREL technology be-
cause it has been the most widely assumed technology modeled
in almost all published lignocellulose-to-ethanol LCAs. Further-
more, NREL’s process described by Aden et al. (2002) is the tech-
nology under investigation for Renewable Fuel Standard (RFS)
policy development. Both technologies employ solid–liquid sepa-
ration techniques to separate the lignin in the feedstock and direct
it to an energy recovery unit for steam and electricity generation.
Simultaneous saccharification and co-fermentation (SSCF) of the
two dominant sugars present in the feedstock, glucose and xylose,
and SSCF of all six-carbon (C6) and five-carbon (C5) sugars present
in the feedstock, are assumed for two sets of near-term models.
The mid-term technology LCA models assume the use of an ad-
vanced AFEX (adv AFEX) pre-treatment technology (relative to the
near-term AFEX) in combination with consolidated bioprocessing
(CBP) enzyme production and hydrolysis–fermentation technol-
ogy. CBP is under development at Dartmouth College by Lee Lynd
and colleagues.
The dilute sulfuric acid (NREL) pre-treatment process is
modeled from the process design by NREL (2001). The CS is treated
with dilute sulfuric acid at 190 °C and 177 psi, which releases
hemicellulose sugars into solution and prepares the cellulose for
hydrolysis. Flash cooling then removes degradation products from
the pre-treatment reaction directing them to wastewater treat-
ment, and solid and liquids are separated. The ion exchange unit
with ammonia eluant originally specified by Wooley et al. (1999)
for treating yellow poplar (YP) and included in the NREL (2001)
CS model along with overliming with the addition of lime, is re-
moved for our model based on a more recently published design
by Aden et al. (2002) which includes overliming only and not ion
exchange due to lower fractions of acetates and consequently
CBP
Enzyme
production
Wastewater
Ethanol recovery
treatment &
lignin separation
Hydrolysis &
fermentation
-SSCF
Syrup & solids
Ethanol
Finished
Electricity product
Lignin & biogas
Legend
System Boundary
Process
Flow
658 S. Spatari et al. / Bioresource Technology 101 (2010) 654–667

lower acetic acid by-product formation in CS versus YP, and a cost
savings for eliminating ammonia requirements. NREL has tested
the dilute acid technology at PDU scale at NREL. Additions of dilute
sulfuric acid, lime and other input chemicals to NREL pre-treat-
ment are noted in Table 3.
The AFEX pre-treatment process treats biomass with liquid
anhydrous ammonia (NH3) at moderate temperatures (60–
100 °C) and high pressure (250–300 psi) for five minutes, after
which time the pressure is rapidly reduced, causing an ‘‘explosion”
and allowing the cellulose and hemicellulose fibres to expand and
be more amenable to enzymatic hydrolysis. This makes the lignin
fraction soluble, and allows for nearly complete conversion of cel-
lulose and hemicellulose fibres to fermentable sugars (Teymouri
et al., 2005). Most NH3 is recovered and recycled (97.3%). NH3 to
dry biomass loadings of 1:1 are needed to ensure high sugar yields
and are assumed for the near-term models, however recent work
by Sendich et al. (2008) has shown that NH3 to dry biomass load-
ings as low as 0.3:1 do not compromise the sugar generation effi-
ciency as long as the NH3 is kept in the liquid phase. This latter
ammonia to biomass ratio is assumed in the mid-term models.
The technology has been tested at laboratory-scale. The AFEX
parameters used as input for the pre-treatment module of the
LCA models are summarized in Table 2 and chemical inputs in Ta-
ble 3. Aspen simulation values of the AFEX-pre-treated CS feed-
stock were provided by Eggeman (2005), who employed mean
estimates from CS pre-treatment laboratory tests conducted by
Teymouri et al. (2005).
Simultaneous saccharification and co-fermentation (SSCF) is
accomplished by combining the enzymatic hydrolysis of cellulose
to glucose process and the co-fermentation of C5 sugars (xylose
and potentially arabinose) and C6 sugars (glucose and potentially
mannose and galactose) process in one reaction vessel (Lynd,
1996; Lynd et al., 2002). To date, the co-fermentation of glucose
and xylose has been tested at bench and pilot scales successfully
with the organisms Saccharomyces cerevisiae (Hahn-Hägerdal
et al., 2001) and Zymomonas mobilis (Aden et al., 2002). While glu-
cose fermentation is a commercial-scale technology, xylose fer-
mentation to date has been performed under controlled
laboratory-scale conditions using genetically modified organisms
(Sheehan et al., 2003) and at demonstration scale (Iogen, 2007);
the simultaneous fermentation of arabinose, mannose, and galact-
ose using one organism has been successful at laboratory-scale,
producing high ethanol yields (Ingram et al., 1987, 1991), however
continued research effort is necessary to attain commercial-scale
fermentation of all cellulose and hemicelluloses sugars. At present,
arabinose remains the most difficult sugar to ferment. Mannose
and galactose can be fermented more easily to ethanol with the
appropriate organism (e.g., S. cerevisiae) as suggested by Mabee
(2006). Much research continues to improve the co-fermentation
of hexose and pentose sugars (Ingram et al., 1987, 1991; Lawford
and Rousseau, 1992, 2003). Our models assume use of cellulase en-
zymes produced from Trichoderma reesei.
During CBP enzyme production, hydrolysis and fermentation of
all sugars take place in one reaction vessel using one organism for
enzyme production and fermentation of all C5 and C6 sugars (Lynd,
1996; Lynd et al., 2002; Laser et al., 2009). To date no single organ-
ism can perform all functions required by CBP technology, for
example, the cellulase producing enzyme (T. reesei) we assume in
our near-term models does not ferment sugars to ethanol. Like-
wise, the fermentative organism we assume (Z. mobilis) does not
produce cellulases, and other potential ethanol-producing organ-
isms either produce low ethanol yields or grow under aerobic con-
ditions (Lynd, 1996). However, researchers at Dartmouth College
continue to conduct metabolic engineering research to develop
such an organism (Lynd et al., 2002). The models developed for
CBP assume such an organism exists and that it is used for both
enzyme production and fermentation. The mid-term models are
assumed to represent high attainment of technological perfor-
mance in the bioconversion of lignocellulose to ethanol.
The variables used as input for the pre-treatment, hydrolysis
and fermentation modules of the near-term LCA models are sum-
marized in Table 2, including the values employed in the Monte
Carlo analysis (developed from laboratory and PDU-scale data),
and the values used in the nth plant Aspen simulations. Inputs into
the mid-term models, which only employ single-point values from
the Aspen simulation, are summarized in Table 2. The equations
developed for the LCA models are described in Section 2.4.
2.3. Chemical inputs, electricity credits, and model designations
A series of cradle-to-gate modules that detail the chemical load-
ings used in pre-treatment, hydrolysis, and fermentation were
developed for the two near-term (NREL–SSCF and AFEX–SSCF)
and one mid-term (adv-AFEX–CBP) ethanol conversion processes

Table 3
Data for chemical input to ethanol conversion unit operations.

Conversion process Chemical Chemical input Assumptions and data sources

(kg/dry metric ton feedstock)
NREL–SSCFa H2SO4 26 Chemical loading specifications for H2SO4, LPG, cellulase and DAP taken from
Ca(OH)2 29 (NREL, 2001); for Ca(OH)2 taken from Sheehan et al. (2002). Chemical LCI data
LPG 0.2 sets taken from GaBi (PE, 2004). Chemical inputs are assumed for CS and SG
Cellulase 9.2 models
DAP 1.9
AFEX–SSCF NH3 20 Chemical loading specifications taken from MSU data (Teymouri et al., 2005;
LPG 0.2 Eggeman, 2005). Chemical LCI data sets taken from GaBi (PE, 2004). Chemical
Cellulase 9.6 inputs are assumed for CS and SG models
DAP 2.2
Advanced: AFEX–CBP NH3 8.1 Chemical loading specifications taken from Dartmouth College (Laser et al.,
DAP 2.2 2009) and Sendich (2006). LCI modules for all chemical and energy inputs taken
from GaBi (PE, 2004)
Cellulase production NH3 48 Input specifications (mass loadings) for each chemical and electricity input
(NH4)2 SO4 16 taken from NREL data on enzyme broth manufacture (Sheehan et al., 2002). The
CaO 58 broth has a concentration of 83.2 g cellulase/kg broth. LCI modules for all
Electricity (in MJ) 8.6 chemical and energy inputs, including electricity, taken from GaBi (PE, 2004).
LPG 0.2 The US national electricity grid mix is assumed
H2SO4 78

Notes: Diammonium phosphate ((NH4)2HPO4) is abbreviated as DAP; LPG, liquified petroleum gas; LCI, life cycle inventory; MSU, Michigan State University.
a
Sulfuric acid requirements specified in a design by Lloyd and Wyman (2005) call for significantly lower quantities (between 5 and 10 kg sulfuric acid/dry metric ton
biomass) than specified by NREL noted above.
 S. Spatari et al. / Bioresource Technology 101 (2010) 654–667 659

examined. Data on chemicals used were taken from the commer-
cial life cycle inventory database GaBi 4.2 (PE, 2004). Data on en-
zyme manufacture were not available in the database. Enzyme
manufacture can vary in its energy inputs and emission outputs
depending on the enzyme family and the energy mix in the loca-
tion of manufacture (Nielson et al., 2006). MacLean and Spatari
(2009) detail the chemical and energy inputs and GHG emissions
for near-term enzyme production. The mid-term CBP model does
not use this module because it is assumed to produce the enzymes
needed in-house. Chemical loadings and data sources are summa-
rized in Table 3. All models assume the co-production of electricity
and steam from the combustible biomass portions not used for
ethanol production, namely the lignin, biogas from the anaerobic
digester used for treating process wastewater, undigested solids
(hemicellulose/cellulose fibres), and unfermented sugars. All of
the steam and most of the electricity is used to operate the plant;
however, excess electricity not used by the plant may be exported
to the electricity grid. All near-term and one mid-term model(s) as-
sume conversion of residual biomass, using a combuster-boiler and
turbogenerator, known as Rankine (R) power generation, as speci-
fied in Aden et al. (2002); while one mid-term model assumes
steam and electricity production via the more efficient, relative
to Rankine, integrated gasification combined-cycle (IGCC) technol-
ogy specified by Laser et al. (2009). We assume that all excess elec-
tricity is sold to regional electricity grids in the vicinity of the
ethanol facility, but assume this electricity displaces electricity
from the average national US electricity grid since we do not define
specific plant locations. An electricity co-product credit is applied
following the system expansion method (ISO, 2006). We specify
the feedstock, pre-treatment, hydrolysis and fermentation pro-
cesses and energy recovery system abbreviations included in the
10 LCA models in Table 4.
2.4. LCA model equations
We develop a set of equations to estimate the technological,
environmental and energy metrics for the different technology
pathways shown in Table 4 based on the material balances of the
conversion processes shown in Fig. 1. All metrics are normalized
to the volumetric flowrate Q_ E (L/h) of ethanol produced in the con-
version facility, which is also the functional unit:
a X
5 from the biomass delivered. For near-term AFEX–SSCF pathways it
Q_ E ¼ M
_F  Y i  Y i E:
qEtOH i¼1
_ F represents the input mass flow rate of feedstock
In Eq. (1), M
(kg/h); a is the ethanol recovery efficiency following distillation,
taken as 99.4% and 99.7%, for near and mid-term models, respec-
tively; and qEtOH, is the density of ethanol (0.789 kg/L). The term
Yi is the yield (by weight) of sugar i, and Yi_E is the yield (by weight)
of ethanol from sugar i where i = 1 to 5 corresponds to glucose, xy-
lose, arabinose, galactose and mannose, respectively. The yield of
each sugar following pre-treatment for the hemicellulose sugars,
and hydrolysis for the glucose in the cellulose fraction is estimated
as follows:
Y i ¼ fi  cj  bk ; ð2Þ
where fi corresponds to the fraction of the sugar polymer in the
feedstock while cj is the conversion efficiency for converting each
sugar polymer to sugar where, j = 1 for converting glucan to glucose
during hydrolysis, and j = 2–5 for converting xylan to xylose, arab-
inan to arabinose, galactan to galactose and mannan to mannose,
respectively, in the pre-treatment step. The term bk is a stoichiom-
etric conversion parameter for the fermentation of each sugar to
ethanol. b1 and b2 correspond to six-carbon (C6) and five-carbon
(C5) sugars, respectively, and are determined by Eqs. (3) and (4):
MWC6
b1 ¼ cC6 ð3Þ
MWC6 polymer
;
MWC5
b2 ¼ cC5 ð4Þ
MWC5 polymer
:
In Eqs. (3) and (4) cC6 is the theoretical conversion of C6 sugars
to ethanol (0.511 g ethanol/g C6-sugar) and cC5 is the theoretical
conversion of C5 sugars to ethanol (0.504 g ethanol/g C5-sugar).
MWC6/MWC6_polymer (180/162) and MWC5/MWC5_polymer (150/132)
represent the fractions of molecular weights of the C6 sugars to su-
gar polymers and C5 sugar to C5 sugar polymers, respectively.
The material balance around the ethanol conversion facility as-
sumes that all combustible portions of the biomass that are not
converted to ethanol could be converted to electricity and sold to
the grid since the process steam and electricity requirements are
assumed to be fixed over different conversion efficiencies. Using
an overall material balance around the ethanol conversion facility,
we estimate the excess electricity (EEl) to be sold to the grid as
follows:
EEl ¼ cb Eb ÿ Ep ; ð5Þ
where cb is a coefficient developed from the Aspen simulation mate-
rial balances, that determines the conversion to electrical energy
ð1Þ is assumed to be 13%; for NREL–SSCF pathways, it is assumed to
be 16%; and for mid-term adv-AFEX–CBP it is assumed to be 29%
and 47% for the Rankine and IGCC electricity conversion processes,
respectively. Eb is the energy delivered to the boiler, described be-
low, and Ep is the fixed process energy and steam requirement used
by the ethanol conversion process; it is assumed to be 69,000 MJ/h

Table 4
Summary of lignocellulosic ethanol life cycle models and designations.

Model Designation Notes

T1 NREL-CS-2-SSCF-R NREL pre-treatment of CS with SSCF hydrolysis–fermentation of 2 sugars (glucose and xylose) and energy recovery via R
T2 AFEX-CS-2-SSCF-R AFEX pre-treatment of CS with SSCF hydrolysis–fermentation of 2 sugars and energy recovery via R
T3 NREL-SG-2-SSCF-R NREL pre-treatment of SG with SSCF hydrolysis–fermentation of 2 sugars and energy recovery via R
T4 AFEX-SG-2-SSCF-R AFEX pre-treatment of SG with SSCF hydrolysis–fermentation of 2 sugars and energy recovery via R
T5 NREL-CS-5-SSCF-R NREL pre-treatment of CS with SSCF hydrolysis–fermentation of 5 sugars (glucose, xylose, arabinose, mannose and galactose)
and energy recovery via R
T6 AFEX-CS-5-SSCF-R AFEX pre-treatment of CS with SSCF hydrolysis–fermentation of 5 sugars and energy recovery via R
T7 NREL-SG-5-SSCF-R NREL pre-treatment of SG with SSCF hydrolysis–fermentation of 5 sugars and energy recovery via R
T8 AFEX-SG-5-SSCF-R AFEX pre-treatment of SG with SSCF hydrolysis–fermentation of 5 sugars and energy recovery via R
T9 AFEX ad-SG-5-CBP-R Advanced AFEX pre-treatment of mid-term SG with CBP; fermentation of 5 sugars; and energy recovery via R
T10 AFEX ad-SG-5-CBP-I Advanced AFEX pre-treatment of mid-term SG with CBP; fermentation of 5 sugars; and energy recovery via IGCC

Notes: Pre-treatment systems: NREL = dilute acid, NREL technology; AFEX = ammonia fibre explosion, MSU technology; advanced AFEX ad = advanced AFEX technology, MSU
and Dartmouth College technology; Feedstocks: CS = corn stover, and SG = switchgrass, Hydrolysis–fermentation technologies; SSCF = simultaneous saccharification and co-
fermentation, and CBP = consolidated bioprocessing; Energy recovery: R = Rankine cycle, IGCC = integrated gasification combined-cycle.
660 S. Spatari et al. / Bioresource Technology 101 (2010) 654–667

for the AFEX–SSCF, 53,000 MJ/h for the NREL–SSCF, and 116,000 MJ/ ily have smaller ranges than those in Table 2 due to refinement in
h for the adv-AFEX–CBP production pathways, determined through design necessary for successful commercialization.
the Aspen simulations. Statistical distributions for the CS and SG feedstock fractions
The energy delivered to the boiler, Eb, is determined by the mass were generated with low/high ranges set to correspond to the
and energy content of the species delivered to the boiler. Eq. (6) 2.5th and 97.5th percentiles (95% confidence interval) in Table 2.
estimates Eb as the difference between the total energy in the input The compositions of 15 CS samples and 57 SG samples were ana-
biomass (MiLHVi) and the weighted average of the sugars con- lyzed to obtain the values (NREL, 2001). The hemicellulose and
verted to ethanol and their LHV. Therefore, at higher ethanol yields, hydrolysis conversion yields (values denoted as c) were assumed
less of the biomass is available for conversion to electricity. to be normally distributed. For NREL pre-treatment, the means
were set to those reported in laboratory studies (Aden et al.,
X
n X
5
Eb ¼ Mi LHV i ÿ M F
LHV E Yi
Yi E: ð6Þ 2002), as was the 2.5th percentile value for c2 while the 97.5th per-
i¼1 i¼1 centile value for c2 was set to the NREL (2001) Aspen simulation
value. The standard deviation for c1 was set equal to that of the
We model the technological performance of the different etha-
AFEX c1. For AFEX pre-treatment, the means, 2.5th and 97.5th per-
nol conversion facilities using the metrics ethanol yield YE (L/dry
centile values were taken from experimental data (Teymouri et al.,
metric ton, Eq. (7)) and electricity co-production EEl (MW, Eq.
2005).
(5)). The life cycle resource–environmental metrics are the fossil
The fermentation yield values for glucose and xylose were esti-
energy input, Efos, and the petroleum input, Epet (MJ/L ethanol,
_ GHG , and air pollutant emissions for dif- mated from a sensitivity analysis conducted by Aden et al. (2002)
Eq. (8); GHG emissions, M
_ j (g constituent/L ethanol, Eq. (9); and and normal distributions were assumed. The yield values for arab-
ferent pollutant species, M
_ SW (kg solid waste/L ethanol, Eq. (10)): inose, galactose and mannose were assumed to have triangular dis-
solid waste generation, M
tributions with the modes equal to 0 and the high values arising
Q_ E from the design case of Aden et al. (2002) and also used by Sheehan
YE ¼ ð7Þ et al. (2003). The triangular distributions may be overly conserva-
_F
;
M
tive for galactose and mannose but reflect that the fermentation
X
n X
n reactor will be less likely to be optimized for these low concentra-
ei;j
Ei ¼ ð8Þ tion sugars (Mabee, 2006). Both Aden et al. and Sheehan et al. re-
Q_ E
;
i¼1 j¼1 flect up-to-date experimental observations conducted by NREL
using the Z. mobilis organism. However, there are other organisms
where e is the energy input needed (MJ/h) for each step of the life
(e.g., recombinant Escherichia coli KO11 and K. oxytoca developed
cycle, i corresponds to fossil energy (i = 1) and petroleum (i = 2),
by Dr. Lonnie Ingram from the University of Florida) that have
and j corresponds to different inputs across the life cycle (e.g., farm-
achieved, at laboratory-scale, ethanol yields in the 90–95% range
ing energy, fertilizers, process chemicals).
for all sugars. We revisit this salient point in Section 3.4 when
X
n X
n
mi;j we discuss model sensitivity, and pre-treatment and fermentation
_i¼
M ð9Þ technology choices.
Q_ E
;
i¼1 j¼1
The Monte Carlo simulations employed 10,000 runs, for the
where m is the emission rate (g/h) for each step of the life cycle, near-term models only. We exclude a Monte Carlo analysis of
i = 1–6 corresponds to emissions of GHGs (weighted CO2, N2O, uncertainty for the mid-term pathways due to insufficient data
and CH4 in g CO2 equivalent), CO, NOX, NMOG, SOX, and PM10 to for assigning plausible variable ranges and probability distribu-
air; and j corresponds to emissions of each air emission species i tions for those technologies at this time.
associated with inputs across the life cycle:
X
n
mSW;i 3. Results and discussion
_ SW ¼
M ð10Þ
Q_ E
:
i¼1 We present results of technical and environmental metrics
Here, mSW,i corresponds to solid waste emissions from the ethanol developed for the ten near- and mid-term LCA models. Near-term
conversion process only. results are presented both as stochastic and point estimates based
The life cycle metrics calculated in Eqs. ()(8)–(10) include the on the Monte Carlo and Aspen simulation results, respectively. We
subtraction of an electricity co-product credit determined through discuss differences between the point and stochastic estimates in
Eq. (5). Section 3.3. Air pollutant emissions, solid waste generation and
the two mid-term technology model results are presented only
as point estimates based on the Aspen simulations. All model re-
2.5. Monte Carlo analysis
sults, unless otherwise specified, are presented as well-to-gate
(WTG), including all activities up through the ethanol production
Because lignocellulosic ethanol conversion technologies are not
step.
yet at commercial scale there is considerable uncertainty sur-
rounding the performance of these facilities. To examine this
uncertainty we obtained data on input variables reflecting perfor- 3.1. Ethanol yield and co-product electricity
mance that has been achieved at laboratory and/or PDU scale as re-
ported in the literature. We use Monte Carlo simulation to generate Ethanol and electricity co-product yields for the ten lignocellu-
stochastic distributions of performance metrics estimated through losic ethanol pathways are shown in Figs. 2 and 3, respectively. In
Eqs. (5), (7), and (8). Table 2 presents the values of the variables all near-term cases, ethanol yields are higher for the AFEX models
and the statistical distributions for each variable for the Monte Car- (T2, T4, T6, T8) than for the NREL models (T1, T3, T5, T7), whether
lo analysis. We selected the variable settings based on actual per- SG or CS is the feedstock. This is due to higher pre-treatment and
formance reported in the literature up to the time of our study. hydrolysis yields; and consequently, lower co-product electricity
Because the data used in the Monte Carlo analysis come from lab- for the AFEX cases since more of the feedstock is devoted to etha-
oratory-scale studies they are not meant to represent operating nol production. While the Aspen model results show that CS etha-
parameters for commercial-scale facilities, which would necessar- nol yields are consistently higher than those of SG for all models

450
Aspen model, Nth plant
400
Yield (L/Mg)
350
300
250
200
150
T1 T2 T3 T4 T5
Fig. 2. Near- and mid-term model pathway ethanol yields. Notes: Near-term
stochastic estimates based on Monte Carlo simulation are presented as box-plots.
The top of the box represents the 75th percentile, the middle line represents the
median (50th percentile) and the bottom of the box represents the 25th percentile.
The whiskers correspond to the 2.5th and 97.5th percentiles. Near and mid-term
results shown as single-point estimates are based on Aspen simulations of nth
plants.
140
Aspen simulation Nth plant
Co-product Electricity (MW)
120
100
80
60
40
20
0 to ÿ50 (Aspen Models) and ÿ350 to ÿ290 (median stochastic anal-
T1 T2 T3 T4 T5 T6
Fig. 3. Near- and mid-term model pathway electricity co-product yields. Notes:
Near-term stochastic estimates based on Monte Carlo simulation are presented as
box-plots. The top of the box represents the 75th percentile, the middle line
represents the median (50th percentile) and the bottom of the box represents the
25th percentile. The whiskers correspond to the 2.5th and 97.5th percentiles. Near
and mid-term results shown as single-point estimates are based on Aspen
simulations of nth plants.
shown, when variations in glucan and xylan concentrations are ta-
ken into consideration, as shown in the stochastic estimates, etha-
nol yields do not vary significantly between the feedstocks with
the pre-treatment system held constant. Mid-term models, which
use the adv-SG feedstock, assume comparatively higher concentra-
tions of cellulose, xylan, and lignin (the main source for thermal,
electrical, and co-product energy) relative to the near-term SG
feedstock (see Table 1), as the authors assume improved composi-
tional yields due to maturation of the energy crop and a late season
single-cut harvest (Laser et al., 2009). This, along with the high
conversion efficiencies assumed in pre-treatment, hydrolysis, and
fermentation with the mature CBP technology (Table 2) is the
cause for the increase in both ethanol yield as well as electricity
production. The higher electricity production capacity is also due
to the larger plant capacity (5000 dry metric tons/day) assumed
in the mid-term relative to the near-term (2000 dry metric tons/
day).
Both Aspen simulation and stochastic results indicate that at
higher ethanol yields, electricity production is lower due to con-
verting more of the biomass to ethanol rather than to electricity.
The stochastic estimates show this pattern more pointedly over a
range: ethanol yields at the upper percentile (97.5th) correspond
to electricity yields at the lower percentile (2.5th), with the reverse
true at the low ethanol/high electricity yield end, a pattern result-
ing from the assumption that any leftover biomass not converted
S. Spatari et al. / Bioresource Technology 101 (2010) 654–667 661
to ethanol (i.e., in the form of a concentrated sugar syrup), can
be converted to electricity. While there may be limitations in con-
verting the syrup to electricity in practice, and likely a different
process design would be utilized if a facility were to be optimized
for electricity rather than ethanol production, we assume the en-
ergy present in the syrup can be converted with the same effi-
ciency as other solids from the biomass in Eq. (6), in order to
estimate the potential for use of all residual biomass for excess
electricity.
When comparing near and mid-term Aspen simulation results,
ethanol yield and co-product electricity both increase due to the
T6 T7 T8 T9/T10
compositionally advanced SG feedstock and mature technology.
Among the mid-term models, with its high efficiency, the IGCC en-
ergy recovery/electricity generation technology outperforms the
Rankine. Jin et al. (2009) studied a suite of IGCC technologies and
found that IGCC, while requiring higher capital expenditure rela-
tive to Rankine, could sell electricity at a lower cost with the same
internal rate of return due to its higher generating efficiency.
3.2. Life cycle fossil energy and petroleum input and greenhouse gas
emissions
We present WTG (ethanol production life cycle) fossil energy
input (Fig. 4), petroleum input (Fig. 5), and GHG emissions
(Fig. 6), respectively, for the ten lignocellulosic ethanol pathways.
All models assume relatively low fossil energy inputs throughout
the life cycle and include a credit for the electricity co-product,
which is why most results are negative. To provide as an example
a quantitative estimate of WTG GHG emissions (all presented in g
CO2 eq./L of ethanol), the near-term AFEX models range from ÿ170
T7 T8 T9 T10 ysis) while the near-term NREL models range from ÿ600 to ÿ250
(Aspen models) and ÿ1380 to ÿ1300 (median stochastic analysis).
The fossil energy input and GHG emissions are both lower
(more negative) for NREL pre-treatment systems due to the larger
electricity credit. This observation would not be obvious without
examining how fossil energy inputs and GHG emissions vary with
ethanol yields. The credits result from off-setting fossil energy and
GHG emissions from the US national electricity generation mix,
which uses mostly coal (approximately 56%) and other fossil en-
ergy inputs (natural gas and some crude oil), a technique following
the ISO (2006) system expansion co-product allocation method,
and one employed in most LCAs of lignocellulosic biofuels (e.g.,
Kim et al., 2009). Therefore, from a resource and climate change
perspective, in comparing the two pre-treatment processes, using
5
Aspen simulation Nth plant
Fossil Energy Input (MJ/L)
0
-5
T8 T9
T2 T4 T6
-10
T10
-15
-20
T7
T1 T3 T5
-25
Fig. 4. WTG fossil energy inputs for near- and mid-term model pathway. Notes:
Near-term stochastic estimates based on Monte Carlo simulation are presented as
box-plots. The top of the box represents the 75th percentile, the middle line
represents the median (50th percentile) and the bottom of the box represents the
25th percentile. The whiskers correspond to the 2.5th and 97.5th percentiles. Near
and mid-term results shown as single-point estimates are based on Aspen
simulations of nth plants.
662 S. Spatari et al. / Bioresource Technology 101 (2010) 654–667
1.6
Petroleum Input (MJ/L)
1.2
0.8
0.4
Aspen simulation Nth plant
0 3.3. Simulation results and Monte Carlo analysis
T1 T2 T3 T4 T5 T6 T7
Fig. 5. WTG petroleum inputs for near- and mid-term model pathway. Notes: Near-
term stochastic estimates based on Monte Carlo simulation are presented as box-
plots. The top of the box represents the 75th percentile, the middle line represents
the median (50th percentile) and the bottom of the box represents the 25th
percentile. The whiskers correspond to the 2.5th and 97.5th percentiles. Near and
mid-term results shown as single-point estimates are based on Aspen simulations
of nth plants.
200
GHG emissions (g CO2 eq./L)
-200
-600
T2 T6
T4
-1000
-1400
-1800
T1 T3 T5 T7
-2200
Aspen model, Nth plant
Fig. 6. WTG GHG emissions for near- and mid-term model pathway. Notes: Near-
term stochastic estimates based on Monte Carlo simulation are presented as box-
plots. The top of the box represents the 75th percentile, the middle line represents
the median (50th percentile) and the bottom of the box represents the 25th
percentile. The whiskers correspond to the 2.5th and 97.5th percentiles. Near and
mid-term results shown as single-point estimates are based on Aspen simulations
of nth plants.
more of the input biomass to produce electricity rather than etha-
nol decreases total fossil energy consumption and GHG emissions
per liter of ethanol output, an observation that is consistent with
results from literature (Wyman, 1994; Larson, 2006; Zhang et al.,
2007). It does not affect total petroleum consumption appreciably
(Fig. 5), which is in accordance with results of Farrell et al. (2006),
who show that petroleum consumption is not significant in the
ethanol life cycle, whether commercial-scale corn or future ligno-
cellulosic ethanol technologies are considered. For energy security
however, the higher ethanol yields achieved through the use of the
AFEX–SSCF production pathways, while not reducing total fossil
energy input and GHGs as much as the NREL–SSCF pathways, could
allow for greater displacement of gasoline if a large supply of bio-
mass is available to produce ethanol in the US in the range of bil-
lions of gallons, important for energy security.
In comparing mid-term with near-term Aspen simulation re-
sults, when the Rankine electricity conversion system (T9) is em-
ployed, fossil energy inputs as well as GHG emissions decline
slightly relative to those of the AFEX–SSCF models (T2, T4, T6,
and T8), but increase slightly relative to those of the NREL–SSCF
models (T1, T3, T5, and T7). On the other hand, using IGCC electric-
ity conversion (T10) reduces fossil energy and GHG emissions rel-
ative to all near-term Aspen simulation results (T1–T8) due to its
large electricity credit. Stochastic fossil energy and GHG emissions
for NREL–SSCF models are lower than the mid-term IGCC model at
the median and 2.5th percentile. Only petroleum input declines for
the mid-term technologies relative to all near-term technologies,
and more so for the IGCC than for the Rankine pathway. This is pri-
marily due to the petroleum input not being significantly affected
by the credit, therefore it is not negative for any of the Aspen sim-
ulations shown. Additionally, petroleum input does not change
appreciably with improvements in ethanol yield, nor does it de-
pend on the pre-treatment system or the feedstock selected, as it
only varies from 1.2 to 1.4 MJ/L for all near-term models.
T8 T9 T10
With few exceptions, the Aspen model point-estimates fall out-
side of the 95% confidence interval (CI) resulting from the Monte
Carlo analysis of fossil energy input and GHG emissions. This is be-
cause many of the values of the model variables reported in the lit-
erature based on recent experimental measurements indicate
lower performance than that assumed in the Aspen simulations.
In other words, the Aspen simulation values are not close to the
medians and in many cases lie outside of the 95% CI range specified
in the Monte Carlo models (see Table 2). The NREL Aspen model
designs assume hemicellulose and hydrolysis conversions higher
than those that have been measured experimentally to date as re-
ported in the literature (the latter being selected as mean values in
T9
the Monte Carlo analysis). The dilute acid pre-treatment system
T8
tested at PDU-scale by NREL has not reported the high hemicellu-
T10 lose and hydrolysis conversion efficiencies that are noted in their
Aspen model (Aden et al., 2002; Sheehan et al., 2003). In contrast,
for certain AFEX model results, the Aspen point estimates lie with-
in the 95% CI due to researchers having demonstrated sugar yields
from hemicellulose and cellulose feedstock fractions in the labora-
tory that are in line with those in the Aspen model. Of all near-term
models, only Aspen model estimates for the T4 model lie close to
the interquartile range. It is important to recognize, however, that
the NREL pre-treatment technology does not represent all dilute
acid pre-treatment performance; Lloyd and Wyman (2005) and
Wyman et al. (2005a,2005b) report higher hemicellulose sugar
and glucose yields (comparable to AFEX results) than those of NREL
(Sheehan et al., 2003; Aden et al., 2002) when testing CS substrates
with dilute sulfuric acid at laboratory-scale (comparable to AFEX
laboratory-scale results). We compare some technological differ-
ences between NREL pre-treatment and results from Lloyd and
Wyman (2005) and AFEX in Section 3.4. In addition, progress in
the field that was not reported in peer-reviewed literature up to
the time of this study is not reflected in our analysis. Comparing
technologies that are at an early stage of technological develop-
ment is a challenge, in particular because it is difficult to account
for how efficiency improvements in the technologies may evolve
at the laboratory, pilot, or commercial scales.
Aspen simulation results in Fig. 2 indicate that ethanol yields
increase by 9–12% when comparing one pre-treatment system
(e.g., AFEX) with one feedstock (e.g., CS) in the two sugar versus
five sugar fermentation cases. On the other hand, when examining
the stochastic results, there is hardly a difference between two and
five sugar fermentation. This is due in part to the conservative
probability distributions assigned to the fermentation of the three
minor sugars, arabinose, galactose, and mannose in the Monte Car-
lo simulation. We applied a conservative probability distribution
for arabinose, the pentose sugar with the highest concentration fol-
lowing xylose, because of the difficulty in fermenting it with the
organism Z. mobilis reported in literature (Sheehan et al., 2003).
This would not be the case if a different organism were used, one
shown, at laboratory-scale, to ferment at high yields all sugars
(e.g., those developed by Ingram et al., 1987, 1991). What remains
uncertain at this time is how those organisms, whose success has
been demonstrated at laboratory-scale, may perform in terms of
 S. Spatari et al. / Bioresource Technology 101 (2010) 654–667
yield and cost at commercial scale. We use the same distribution
for galactose and mannose fermentation since conditions in the
SSCF unit operation would more likely be set to optimize for glu-
cose and xylose fermentation (Mabee, 2006), which are in much
higher concentrations in the feedstock.
All near-term models were sensitive to the xylose fermentation
yield due to its high standard deviation (Table 2) in the stochastic
estimates, indicating that it is likely among the most important
conversion variables requiring improved reliability in order to raise
ethanol yields. Following glucose, xylose is the most important su-
gar for fermentation because of its concentration in herbaceous
feedstocks. While there has been progress in developing organisms
to ferment xylose (Lawford and Rousseau, 2003; Sheehan et al.,
2002), it remains a reaction process that has yet to be practiced
at commercial scale. For this reason, the probability distribution
for xylose fermentation (normal distribution with mean set at
0.70 g ethanol/g xylose and larger standard deviation relative to
that employed for glucose fermentation) assumed in this research
was more conservative than if industrial-scale xylose fermentation
were practiced today, which would enable the selection of higher
mean xylose-to-ethanol yields with tighter distributions as was as-
sumed for the glucose fermentation variable, which is based on
industrial-scale experience. A larger standard deviation for xylose
fermentation is also consistent with the sensitivity analysis that
examined its effect on ethanol selling price by Aden et al. (2002).
Overall, the most robust results presented in Figs. 2–6 are the
near-term stochastic estimates. These ethanol production path-
ways make use of plausible ranges and probability distributions
determined from laboratory results in combination with published
results from literature for setting the input variables that deter-
mine ethanol yields and life cycle resource/environmental metrics.
The mid-term models incorporating mature lignocellulosic ethanol
technology, while showing more promise in life cycle fossil energy
and GHG emissions reductions than the near-term models, require
additional research and development before we could assign cred-
ible variable ranges and probability distributions with confidence.
3.4. Co-product credit sensitivity
In view of energy and climate change impacts, the near-term,
lower ethanol-yielding technologies achieve the best performance
of all pathways shown in Figs. 4 and 6 due to exhibiting the lowest
total fossil energy requirements and GHG emissions over the fuel
production cycle. This apparent performance is due to the inclu-
sion of the electricity co-product credit. The credit assumes that
the electricity produced by the ethanol facility above that which
is required for the facility itself can be sold to the national US grid.
Under the system expansion method of co-product allocation, the
ethanol is credited with the energy use and emissions that would
otherwise be associated with producing the same amount of elec-
tricity using the average US electricity generation mix. Since the US
mix is heavily reliant on fossil fuels, mostly coal, ethanol receives
significant fossil energy use and emissions credits, resulting in neg-
ative fossil energy input and GHG emissions for ethanol production
as shown in Figs. 4 and 6. Furthermore, the wide 95% CI shown for
those same results is largely due to the electricity credit itself. The
electricity credit magnifies the negative fossil energy input and
GHG emissions by a factor of 2–3 due to the large quantities of
both fossil energy and GHG emissions assumed to be displaced.
Since little electricity is generated in the US from petroleum
(4.2%), the credit has little impact on that metric (Fig. 5). Inclusion
of the credit furthermore raises the question of whether, from a re-
source and climate change mitigation perspective, the biomass
would be better utilized for displacing coal-derived electricity, an
observation that is consistent with results from literature (Wyman,
1994; Larson, 2006; Zhang et al., 2007). This latter point however,
663
holds additional uncertainties, including those related to electricity
markets, decision makers’ goals, policies, etc., not accounted for in
the results presented herein. Moreover, the assumption of includ-
ing a co-product credit itself carries uncertainty because these eth-
anol plants do not exist and therefore secure markets for the co-
products also do not exist. When evaluating future lignocellulosic
ethanol facilities, the question of allocating a credit for the electric-
ity co-product is uncertain due to uncertainties in the regional
electricity markets (future generation mixes and transmission
capabilities) into which the co-product would be sold. We assumed
a credit based on the US national average mix. However, if the co-
product were sold into regions with higher/lower fractions of coal-
based electricity, the credit would be more/less pronounced.
To examine the effects of electricity credits on life cycle GHG
emissions, and to demonstrate the effect that improved dilute acid
pre-treatment and fermentative organism choice has on WTG life
cycle GHGs, we introduce Fig. 7, which shows GHG emission re-
sults for select near-term and mid-term pathways. In Fig. 7 we
introduce an additional case (L–W) that utilizes laboratory-scale
dilute acid pre-treatment measurements from Lloyd and Wyman
(2005) along with fermentative organisms selected that are on
par with those used in CBP. The L–W case is comparable to the
near-term CS-AFEX (T6) case with respect to scale-up (from labo-
ratory measurement) and in its use of purchased enzymes, and
to the CBP models in its use of high-yielding fermentative organ-
isms (95% conversion of all sugars to ethanol). The L–W case
demonstrates high performance of dilute acid pre-treatment
technology both in sugar and ethanol yields and net GHG
emissions.
When electricity credits are not considered, the uncertainty
range tightens considerably over the 95% CI, and also the higher
ethanol-yielding pathways have lower GHG emissions, the mid-
term mature system (T9/T10) emitting the least of all pathways
shown. Among the near-term processes that do not assume elec-
tricity credits, the AFEX technologies perform somewhat better
than the NREL ones under uncertainty, but probably more signifi-
cantly, the stochastic estimates lie close to the Aspen simulation
estimates, therefore attesting to the promising performance of that
technology to date at laboratory-scale.
1000
Near-term Mid-term/
Advanced
GHG emissions (g CO2 eq/L)
500
T9/T10
0
L-W
CS
-500
T9
T6 T8
-1000
T10
-1500
T5
-2000
T7
Stochastic w elec. Stochastic w/o elec. Aspen model elec. Aspen model w/o elec.
Fig. 7. WTG GHG emissions including and excluding electricity co-product credits
in near and mid-term time frames. Notes: Two cases are shown for each near-term
technology: stochastic as box-plots over the 95% CI; and point estimates based on
Aspen models. In the mid-term/advanced technology case we include an Aspen
model pathway (L–W CS) that uses laboratory-scale dilute acid pre-treatment
experimental data by Lloyd and Wyman (2005) and high fermentative yields of all
sugars, comparable to the CBP cases T9 and T10. The ‘L–W CS’ case is based on a
2000 dry metric ton/day facility; 96% conversion of cellulose to glucose; 85%
conversion of hemicellulose to xylose, arabinose, galactose and mannose; pur-
chased enzymes; and ethanol yield 400 L/dry metric ton.
664 S. Spatari et al. / Bioresource Technology 101 (2010) 654–667

3.5. LCA model comparison with published results
We compare our stochastic SG model results, as well-to-tank
(WTT) results, to assess differences in the ethanol conversion mod-
ule, with those of GREET 1.7 (Wang, 2007), a publicly available
peer-reviewed and widely cited LCA model that includes a herba-
ceous crop-based lignocellulosic ethanol pathway (which assumes
feedstock production identical to that for SG modeled in this work)
that utilizes dilute acid pre-treatment followed by biochemical
SSCF conversion (Table 5). The WTT results include those for the
WTG (presented up to this point in the paper) but additionally in-
clude fuel transportation and distribution. We exclude electricity
credits from all pathways in Table 5 in order to assess input contri-
butions to each metric.
The GREET results are modeled after NREL processes and as-
sume relatively high ethanol yields and much lower electricity
co-products (as they are based on the nth plant design discussed
earlier) compared with our models. Model T8, our process with
the highest ethanol yield and lowest electricity capacity, shows re-
sults closest to those of GREET; however, even with T8 the esti-
mated electricity co-product exceeds that of GREET by more than
a factor of three. Our mean environmental results are noticeably

Table 5
Comparison of mean well-to-tank stochastic ethanol conversion models with GREET herbaceous crop model.

Yield (L/dry metric ton) Electricity Co-producta (MW) Electricity co-product (kWh/L) Fossil energy (MJ/L) Petroleum (MJ/L) GHG (g CO2 eq/L)
T3 210 ± 34 43 ± 5 2.5 ± 0.7 8.3 ± 1.2 3.1 ± 0.5 790 + 131/ÿ113
T4 290 ± 43 25 ± 6 1.1 ± 0.4 7.7 ± 1 2.2 ± 0.3 600 + 92/ÿ80
T7 220 ± 35 42 ± 5 2.3 ± 0.6 8.1 ± 1 3.0 ± 0.4 770 + 124/ÿ109
T8 290 ± 45 24 ± 6 1.0 ± 0.2 7.6 ± 1 2.2 ± 0.3 590 + 92/ÿ78
GREET 380 5 0.15 3.2 1.6 360

Notes: Model results do not include a co-product credit. GREET pathway is for 100% herbaceous (switchgrass) feedstock.
a
Electricity capacity for the GREET model was calculated from the electricity yield (kWh/gal), ethanol yield, and assuming a 2000 dry metric ton/day facility (GM/Argonne,
2005).

Table 6
Air pollutant emissions associated with feedstock (production, collection, and transport), process conversion, and electricity credit.

T1 T2 T3 T4 T5 T6 T7 T8 T9 T10
Air (g/L ethanol)
Carbon monoxide
Feedstock 0.5 0.5 0.7 0.6 0.5 0.4 0.6 0.5 0.4 0.4
Process 2.8 2.7 3.1 3.0 2.5 2.4 2.8 2.7 0.0 0.0
Electricity credit ÿ0.6 ÿ0.3 ÿ0.7 ÿ0.4 ÿ0.4 ÿ0.2 ÿ0.5 ÿ0.3 ÿ0.4 ÿ0.7
WTG 2.8 2.8 3.1 3.2 2.6 2.6 2.9 3.0 0.1 ÿ0.2
Nitrogen oxides
Feedstock 1 0.9 1 0.9 0.9 0.8 1 0.8 0.6 0.6
Process 3 3.0 3.3 3.3 2.7 2.7 3.0 3.0 0.1 0.1
Electricity credit ÿ3.3 ÿ1.8 ÿ3.9 ÿ2.3 ÿ2.4 ÿ1.2 ÿ3.2 ÿ1.8 ÿ2.1 ÿ4.0
WTG 0.7 2.1 0.4 1.9 1.2 2.3 0.8 2.1 ÿ1.4 ÿ3.3
Sulfur oxides
Feedstock 0.5 0.5 0.2 0.2 0.5 0.4 0.2 0.2 0.1 0.1
Process 4.0 1.6 4.3 1.8 3.5 1.5 4.0 1.6 0.07 0.07
Electricity credit ÿ6.2 ÿ3.5 ÿ7.4 ÿ4.3 ÿ4.5 ÿ2.3 ÿ6.0 ÿ3.3 ÿ3.9 ÿ7.5
WTG ÿ1.7 ÿ1.4 ÿ2.9 ÿ2.4 ÿ0.5 ÿ0.4 ÿ1.8 ÿ1.5 ÿ3.7 ÿ7.3
NMOG
Feedstock 0.2 0.2 0.4 0.3 0.2 0.2 0.3 0.3 0.2 0.2
Process 3.5 1.6 3.8 1.8 3.1 1.4 3.5 1.6 0.09 0.09
Electricity credit ÿ0.3 ÿ0.2 ÿ0.3 ÿ0.2 ÿ0.2 ÿ0.1 ÿ0.3 ÿ0.1 ÿ0.2 ÿ0.3
WTG 3.4 1.6 3.8 1.9 3.1 1.5 3.5 1.8 0.1 0.0
PM10 to air
Feedstock 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.08 0.08
Process 0.05 0.03 0.05 0.03 0.04 0.03 0.05 0.03 0.01 0.01
Electricity credit ÿ0.5 ÿ0.3 ÿ0.6 ÿ0.4 ÿ0.4 ÿ0.2 ÿ0.5 ÿ0.3 ÿ0.3 ÿ0.6
WTG ÿ0.3 ÿ0.1 ÿ0.4 ÿ0.2 ÿ0.2 ÿ0.06 ÿ0.3 ÿ0.1 ÿ0.2 ÿ0.5
NMOG disaggregated (process only)
Furfural 1.5 0 1.7 0 1.3 0 1.5 0 0 0
HMF 0.2 0 0.2 0 0.1 0 0.2 0 0 0
Ethanol 0.5 0.5 0.6 0.5 0.5 0.4 0.5 0.5 0.07 0.07
Acetic acid 1.1 0.9 1.2 1.0 0.9 0.8 1.1 0.9 0 0
Total 3.3 1.4 3.6 1.5 2.9 1.2 3.3 1.4 0.07 0.07

Solid (g/L ethanol)

Solid waste 340 210 370 240 300 190 340 220 88 88

For AFEX systems, including AFEX–SSCF and AFEX–CBP (T9 and T10), process-related emissions of PM are not monitored, rather the emissions shown result from process
inputs (cellulase production, and chemical and fuel inputs). Notes: HMF, hydroxymethylfurfural; NMOG, non-methane organic gases; WTG, well-to-gate.
 S. Spatari et al. / Bioresource Technology 101 (2010) 654–667
higher than those of GREET: 85–155% (fossil energy), 35–100%
(petroleum), and 60–120% (GHGs). While all models we develop
assume the same feedstock production, collection and transport
module as in GREET, our ethanol yields are considerably lower,
thus requiring more fossil energy input per L of ethanol produced,
and we additionally account for primary energy and emissions
associated with process chemicals used in ethanol conversion.
The GREET model considers only the energy associated with the
fuel used directly in the ethanol conversion facility, that used for
operating forklifts and estimates an input of 0.06 MJ/L (213 BTU/
gal) of primary fossil energy input (Wang, 2007). Our models in-
clude the life cycle energy inputs and emission outputs of replace-
ment pre-treatment chemicals (quantities of chemicals not
recovered in the process), enzymes, and nutrients, in addition to
the fuel for operating forklifts; and estimate a primary fossil energy
input into and GHG emission from ethanol conversion of between
1.6 and 2.7 MJ/L and 180–205 g CO2 eq./L, respectively. Both lower
ethanol yields (and uncertainty therein) and the addition of pro-
cess chemical input energy and emissions give rise to differences
in this study’s lignocellulosic ethanol pathway results in relation
to the GREET pathway.
3.6. Air pollutant and solid waste impacts
Table 6 shows WTG model air pollutant emissions and solid
waste generation. In all near-term scenarios (T1–T8), the ethanol
conversion process dominates emissions of CO, NOx, SOx, and
NMOG. Even when factoring in the electricity credit reduction,
the ethanol conversion (process)-related emissions of the four pol-
lutants dominate. This result is consistent with earlier work by
Spatari et al. (2005), which did not include an electricity credit.
With the addition of air pollutant controls on the energy recovery
equipment, all air pollutants noted above would be reduced over
the fuel production cycle, although they could still be significant
at the feedstock collection and transport steps. Mid-term air pollu-
tant emissions are also lower than near-term models due to higher
ethanol yields, lower chemical loadings, and in situ enzyme pro-
duction. The near-term boiler/combustor design specified by Aden
et al. (2002), which we use in all near-term models, releases high
SOX emissions originating from sulfur in the feedstock, and lacks
emission control for that species (Sheehan et al., 2002). This issue
was addressed by Laser et al. (2009) in the CBP design, and would
need to be included in future improvements of near-term process
designs, as it would result in a better life cycle profile for ethanol.
Installation of emission controls at ethanol conversion facilities
would be expected to be required to limit emissions; they would
increase the cost of production and would increase the facility’s de-
mand for energy, which is produced on-site. This would change the
electricity co-product output, and associated credits, but would
likely not have a large impact on the carbon profile of the fuel life
cycle.
The emissions of NMOG in Table 6 show that the AFEX pre-
treatment system emits less NMOG overall, and in particular no
aldehydes, because it is an alkali pre-treatment system (Sendich,
2006); whereas NREL’s pre-treatment generates some cyclic alde-
hydes (furfural and hydroxymethyl furfural (HMF)) when hemicel-
lulose reacts with dilute acid. Of the aldehyde emissions produced
in the NREL Aspen design, more than half are sent to the wastewa-
ter treatment system, but some stay with the pre-treated slurry
and migrate through to various water recycle streams, a fraction
of which is used to wash the incoming feedstock, where they vol-
atilize, and where emission controls would need to be installed. All
other air pollutant emissions, aside from NMOG, are roughly equiv-
alent between the NREL and AFEX pre-treatment systems for the
ethanol conversion process. It is when co-product credits are taken
into consideration, that the NREL system emits lower quantities of
665
NOx, SOx, and PM10, but approximately the same quantity of CO.
The NREL models generate higher quantities of solid waste for
landfilling due to the by-product formation of gypsum, which is
not produced with AFEX pre-treatment, and which is specified
for disposal by landfill in the Aspen simulation. Through changes
in feedstock composition and ethanol yield improvements, the
mid-term technology, which employs the advanced AFEX technol-
ogy, reduces solid waste generation per L of ethanol produced rel-
ative to the near-term AFEX-pre-treated models.
4. Conclusions
Exploration of domestic, renewable energy alternatives for
light-duty vehicles has been motivated by stakeholders’ acknowl-
edging the need for decreasing the demand for imported crude
oil and decarbonizing the fuel mix, as well as more generally, the
need for near and mid-term improvements to the sustainability
of personal transportation. As shown in this research, lignocellu-
lose-based ethanol produced through a set of emerging conversion
technologies offers promise for making progress toward both en-
ergy security and climate change mitigation goals. The research
quantifies the resource investments (e.g., fossil, petroleum energy)
required to convert two potential feedstocks to ethanol utilizing
specific near and mid-term pre-treatment and hydrolysis–fermen-
tation technologies. Greenhouse gas and air pollutant emissions
associated with the technologies are also quantified. The technolo-
gies examined are found to exhibit differences in both technologi-
cal and life cycle environmental performance. Surprisingly and
perhaps counter-intuitively, low ethanol-yielding conversion tech-
nologies outperform, in terms of fossil energy inputs and GHG
emissions, even the highest yielding mature mid-term technolo-
gies when credits, based on the US national electricity generation
mix, are assumed to be displaced by the ethanol facility’s electric-
ity co-product. However, outside of biomass-based fuels, there are
no near-term low carbon liquid fuel alternatives for light-duty
vehicle transportation available at reasonable cost. Converting bio-
mass to ethanol is an option for reducing the carbon intensity of
the sector while making progress toward energy security goals.
Further reduction of the carbon intensity of lignocellulosic ethanol
is possible by lowering carbon emissions along its supply chain, for
example, using biobased fuels in farm equipment and for transport
(MacLean et al., 2000) and expanding the cadre of biorefinery prod-
ucts, such as producing process chemicals such as ammonia from
anaerobic digester gas.
When examining the uncertainty in the performance of an eth-
anol technology based on published data and comparing this to the
best estimate of performance of an nth plant developed through
Aspen simulation, the difference in environmental performance is
considerable. Most publicly available LCA models (e.g., GREET) as-
sume technology performance and associated ethanol yields that
reflect nth plant performance. This assumption necessarily affects
resource and environmental metrics as they are allocated to the
unit of fuel produced.
Monte Carlo analysis represents a formal mechanism for appro-
priately making predictions from uncertain input, which is a rele-
vant analytical approach for evaluating lignocellulosic ethanol due
to the technologies’ state of development. However, the results of
the Monte Carlo analysis are only as robust as the data and proba-
bility distributions that go into the analysis. When additional data
on pre-treatment, hydrolysis and fermentation yields reported at
laboratory and pilot-scale become available, it will be possible to
improve predicted life cycle performance of lignocellulosic ethanol
technologies further. We recognize that the technologies examined
herein represent a small sample from a larger pool of technologies
that are improving with time due to the dynamic nature of the
666 S. Spatari et al. / Bioresource Technology 101 (2010) 654–667
lignocellulosic ethanol field. The technologies we selected for
investigation may have improved through additional research
and development and continued industry initiatives since the time
of data collection for this study.
Most importantly, in spite of the variability and uncertainty in
technological and environmental performance we report for the
lignocellulosic ethanol pathways, all of these technologies offer a
positive (fossil) energy gain and a substantial opportunity to re-
duce GHG emissions relative to gasoline and corn ethanol, fuels
that are predominantly used in light-duty vehicles on the roads
today.
Acknowledgements
We thank Dr. Bruce Dale of Michigan State University and Dr.
Lee R. Lynd of Dartmouth College for providing data used in this re-
search and the Natural Sciences and Engineering Research Council
(Canada), AUTO21 Network Centre of Excellence and Government
of Ontario Early Researcher Award for financial support.
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