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Review
Department of Molecular Biosciences and Bioengineering (MBBE), University of Hawaii at Manoa, 1955 East-West Road, Agricultural Science Building 218, Honolulu, HI 96822, USA
Department of Civil and Environmental Engineering (CEE), University of Michigan Ann Arbor, 1351 Beal Ave., 107 EWRE Bldg, Ann Arbor, MI 48109-2125, USA
c
State Institute of Agricultural Engineering and Bioenergy, University of Hohenheim, Garbenstrasse 9, Stuttgart 70599, Germany
d
Department of Environmental Engineering, Tongji University, Shanghai 200092, PR China
b
h i g h l i g h t s
Anaerobic biorefineries are a new approach for producing biobased products.
Most organic substrates can be used as feedstocks for anaerobic biorefineries.
Large-scale biorefineries have the potential to maximize economic benefit.
Small-scale anaerobic biorefineries improves living quality in developing countries.
a r t i c l e
i n f o
Article history:
Received 3 February 2016
Received in revised form 11 March 2016
Accepted 12 March 2016
Available online xxxx
Keywords:
Anaerobic digestion
Biorefinery
Bioenergy
Value-added products
Organic feedstocks
a b s t r a c t
Anaerobic digestion (AD) has been in use for many decades. To date, it has been primarily aimed at treating organic wastes, mainly manures and wastewater sludge, and industrial wastewaters. However, with
the current advancements, a more open mind is required to look beyond these somewhat restricted original applications of AD. Biorefineries are such concepts, where multiple products including chemicals,
fuels, polymers etc. are produced from organic feedstocks. The anaerobic biorefinery concept is now gaining increased attention, utilizing AD as the final disposal step. This review aims at evaluating the potential significance of anaerobic biorefineries, including types of feedstocks, uses for the produced energy, as
well as sustainable applications of the generated residual digestate. A comprehensive analysis of various
types of anaerobic biorefineries has been developed, including both large-scale and household level
applications. Finally, future directives are highlighted showing how anaerobic biorefinery concept could
impact the bioeconomy in the near future.
2016 Elsevier Ltd. All rights reserved.
Contents
1.
2.
3.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Potential feedstocks for an anaerobic biorefinery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.
Lignocellulosic biomass. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.
Municipal solid waste (MSW). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3.
Animal manure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.4.
Food wastes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Large-scale anaerobic biorefinery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.
Biogas. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.
Digestate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.1.
Carbohydrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.2.
Lignin. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.3.
Solid residues . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3.
Liquid effluent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Corresponding author.
E-mail address: khanal@hawaii.edu (S.K. Khanal).
http://dx.doi.org/10.1016/j.biortech.2016.03.074
0960-8524/ 2016 Elsevier Ltd. All rights reserved.
Please cite this article in press as: Sawatdeenarunat, C., et al. Anaerobic biorefinery: Current status, challenges, and opportunities. Bioresour. Technol.
(2016), http://dx.doi.org/10.1016/j.biortech.2016.03.074
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1. Introduction
The global total primary energy consumption was reported
around 524 Quadrillion Btu (QBtu) in 2010 (Energy Information
Administration (EIA), 2013). The energy consumption is expected
to increase by nearly 50% by 2050 due to growing demand from
emerging nations such as India, China, and Brazil among others.
Currently, fossil-based fuels supply over 85% of world energy
demands. The excessive use of fossil fuels has also been linked to
several environmental issues, especially greenhouse gas (GHG)
emissions and local and regional air quality degradation. The CO2
emissions from the combustion of fossil fuels alone contributes
to more than 90% of energy-related GHG emissions (International
Energy Agency (IEA), 2015). Moreover, energy security is also a
major concern for countries that rely on imports of fossil energy
resources. In the recent years, renewable energy technologies
(e.g., wind, solar, hydro, and biomass) have been promoted to
address environmental issues such as climate change and local
air quality degradation, as well as energy insecurity. The
renewable-based power generation in 2014 increased to 128 GW
which is over 40% higher than renewable power generation in
2010 (IEA, 2015). Among the various renewable energy sources,
biomass has so far been the largest single source currently being
used, especially in developing countries where biomass (e.g., firewood, crop residues, and cattle dung) is used as a primary energy
source for heating and cooking.
Anaerobic digestion (AD) is one of the most promising biotechnologies for converting diverse organic substrates, ranging from
high solid feedstocks (i.e., animal manure, food wastes, municipal
solid waste, and lignocellulosic biomass), as well as municipal
and industrial wastewaters, to energy-rich biogas (Khanal, 2008).
Although AD technology had primarily been developed and
adopted for waste stabilization, in recent years, AD process has
been widely adopted for bioenergy production. Over 14,000 commercial AD plants are already in operation in Europe, while Germany alone has more than 8000 plants (EBA, 2014). The
produced biogas is used for combined heat and power (CHP) generation, and/or upgraded to biomethane to be used as transportation fuels, or injected into natural gas grid.
In developing nations, AD processes are becoming immensely
popular for conversion of organic wastes (e.g., animal manures,
food wastes, agri-residues, etc.) into biogas. The biogas serves as
a clean energy for cooking and lighting in rural households. The
residuals after digestion, commonly known as bioslurry, serve as
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an organic fertilizer for crop production and as a fish feed for aquaculture application (Surendra et al., 2014). There have been several
successful examples of implementation of biodigester technologies
in developing countries in Asia including Nepal, Vietnam, Bangladesh, Cambodia, and Laos among others. Using biogas for CHP generation or transportation fuels is a well-established process in
developed countries. However, producing biogas alone might not
be economically competitive, especially due to the volatility of
market and price indexes of fossil fuels (Surendra et al., 2015).
One approach to circumvent this problem is to identify and explore
alternative products/chemicals apart from bioenergy production
by adopting the biorefinery approach. The biorefinery concept is
analogous to a traditional petrochemical refinery in which multiple
products are produced from crude petroleum. According to the
National Renewable Energy Laboratory (NREL), a biorefinery is a
facility that integrates biomass conversion processes and equipment to produce fuels, power, and chemicals from biomass. Thus,
such approach aims at maximizing the profit by producing low volume high-value products while meeting the energy needs by producing low-value high volume fuels. The anaerobic biorefinery is
one of the biorefinery concepts, in which AD serves as a centerpiece to produce high-value, but low volume products (i.e., chemicals and drop-in biofuels to enhance economic viability of the
system) and high-volume but low value products (i.e., heat, electricity, and conventional transportation biofuels) to achieve energy
security. Recently many studies have discussed the biorefinery
concept in general, but there exists only limited studies primarily
focusing on the anaerobic biorefinery (Maclellan et al., 2013;
Surendra et al., 2015). This review provides an overview of the
anaerobic biorefinery concept and critically examines the recent
advancements in anaerobic biorefineries. Moreover, this review
also highlights the challenges and opportunities associated with
both commercial and small-scale anaerobic biorefineries, and outlines directions for future research and development.
Table 1
The composition of selected lignocellulosic biomass.
Biomass
Cellulose (%)
Hemicellulose (%)
Lignin (%)
References
Corn stover
Wheat straw
Switch grass
Rice straw
Napier grass
Barley straw
Miscanthus
Coffee pulp
Paper waste
39.7
37.9
37.1
35.0
45.7
37.5
38.0
35.0
11.9
29.9
21.8
29.9
26.7
33.7
25.3
18.5
46.3
1.0
8.9
22.1
17.6
13.3
20.6
26.1
20.9
18.8
33.0
Please cite this article in press as: Sawatdeenarunat, C., et al. Anaerobic biorefinery: Current status, challenges, and opportunities. Bioresour. Technol.
(2016), http://dx.doi.org/10.1016/j.biortech.2016.03.074
Malaysia
Kuala Lumpur
China
Beijing
Shanghai
Shenzhen
United States
References
(kg/capita/day)
Organic waste
Paper
Plastic
Glass
Metal
Textile fiber
Wood
1.2
74
21
NA
NA
NA
0.98
63.4
66.7
40
11.1
4.5
17
12.7
20
13
1.8
2.7
5
0.3
0.3
3
2.5
1.8
5
1.8
1.2
NA
14.5
27.4
12.7
4.6
8.9
8.7
6.3
EPA (2013)
Palestine
Nablus district
0.82
65.1
9.1
7.6
2.9
2.8
3.1
NA
Thailand
1.15a
35.9
20.7
15.9
9.9
3.8
2.5
NA
Based on the municipality that has the population between 10,000 and 50,000 people.
bio-based products/chemicals (e.g., organic acids, bioplastic, succinic acid, citric acid, lactic acid etc.). The lignocellulosic biomass
has a potential to significantly contribute to global demand of
renewable energy and biobased products (Kumar et al., 2008). It
has been reported that globally more than 200 billion dry metric
ton of biomass can be produced per year while 1.4 billion dry tons
of such biomass can be produced in the U.S. alone (Khanal, 2008).
Lignocellulosic biomass is primarily composed of polymers in plant
cell walls including cellulose, hemicellulose, pectin, and lignin
along with small amounts of other organic compounds such as proteins and lipids, and minerals (Frigon and Guiot, 2010). Cellulose is
a long linear chain of homopolysaccharides of b-D-glucopyranose,
which link to each other by b-(1-4)-glycosidic bonds (Kumar
et al., 2008). Cellulose has two different structural forms, the crystalline and amorphous. The crystalline structure has a high packing
density resulting from hydrogen bonding. The complexity of this
form creates a resistance to biological degradation and significantly reduce its accessibility to cellulose degrading enzymes
(Brown, 2003). Hemicellulose is another form of heteropolysaccharides present in plant cell walls. The monomers of this compound
include hexose, pentose, deoxyhexose, and some acidic sugars. A
lower degree of polymerization and amorphous structure makes
hemicellulose more vulnerable to chemical, thermal, and biological
degradation than cellulose (Cherubini, 2010). Lignin is a nonpolysaccharide component in a lignocellulose structure, which fills
up the space between cellulose and hemicellulose, and acts as a
binder. The monomer of lignin is a phenylpropane-based compounds consisting of aromatic alcohols namely; coniferyl, sinapyl,
and coumaryl alcohol. Typically, lignin provides rigidity to plant
cell wall and is more resistant to biological degradation than to cellulose and hemicellulose. In AD of lignocellulosic feedstocks, lignin
usually remains undigested. Lignin can be used to produce energy
(i.e., heat and electricity) via thermochemical processes and various bio-based products (i.e., biopolymer and vanillin among
others) via chemical processes (Surendra et al., 2015). The composition of a selected lignocellulosic biomass is presented in the
Table 1.
2.2. Municipal solid waste (MSW)
MSW is the refuse generated during daily activities from residential and business areas. The characteristics of MSW depend
on many factors, including but not limited to, the source, location,
season, the economic and population growth status, urbanization,
and life style of people (Cheng and Hu, 2010). Karthikeyan and
Visvanathan (2012) estimated that the global MSW generation
Please cite this article in press as: Sawatdeenarunat, C., et al. Anaerobic biorefinery: Current status, challenges, and opportunities. Bioresour. Technol.
(2016), http://dx.doi.org/10.1016/j.biortech.2016.03.074
Table 3
The characteristics and energy potential of animal manure.
Animal
Total
solids (%)
Organic
carbon (%)
Total
nitrogen (%)
Ammonia
nitrogen (%)
Methane
potential (mL/gVS)
Energy
value (kJ/kgTS)
References
Cattle
Dairy
Swine
Poultry
1430
6.512.6
NA
4.213.2
10.359.7
0.40.8
NA
0.41.1
1.05.8
0.00.2
NA
0.10.6
0.21.8
139.8
242.7
253.8
291.0
NA
15,863
19,156
13,832
Bernal
Bernal
Bernal
Bernal
1533
2270
et
et
et
et
al.
al.
al.
al.
(2009),
(2009),
(2009),
(2009),
Ro
Ro
Ro
Ro
et
et
et
et
al.
al.
al.
al.
(2007),
(2007),
(2007),
(2007),
Table 4
The amounts of animal manure annually generated in selected countries.
Location
Year
Annual amount
Unit
United States
England and Wales
China
Japan
Thailand
2005
2000
2010
2011
1997
31.8
112.0
2816.0
84.0
3.9a
Million
Million
Million
Million
Million
References
dry metric tons
wet metric tons
wet metric tons
wet metric tons
dry metric tons
From cattle, swine, and chicken, and assuming that manure is generated 365 days/year.
Please cite this article in press as: Sawatdeenarunat, C., et al. Anaerobic biorefinery: Current status, challenges, and opportunities. Bioresour. Technol.
(2016), http://dx.doi.org/10.1016/j.biortech.2016.03.074
Source
Country
TS (%)
VS (% TS)
Soluble
CODa (g/L)
Total
carbohydrate (% TS)
Total
protein (% TS)
Total
fat (% TS)
TKN
(gN/L)
References
Dining hall
Biowaste digestion plant
Fruit and vegetable markets,
household, and juices centers
University canteen
S. Korea
UK
India
67.8
24.8
15.0
94.0
92.9
88.5
NA
98.2
NA
37.6
NA
NA
NA
NA
6.87
NA
NA
8.5
NA
7.4
1.1
China
19.7
17.0
NA
NA
17.3
29.9
NA
wastewaters to municipal and farm wastes could be used as feedstocks in an anaerobic biorefinery to produce biogas with concomitant generation of digestate (i.e., solid residue and liquid effluent).
The digestate could be further processed to plethora of biobased
products and chemicals. The anaerobic biorefinery concept is illustrated in Fig. 1. Bozell and Petersen presented a revised list of top
ten building block chemicals which can be derived from lignocellulosic biomass, including ethanol, furans, glycerol and derivatives,
hydrocarbons, lactic acid, succinic acid, hydroxypropionic acid/
aldehyde, levulinic acid, sorbitol, and xylotol (Bozell and
Petersen, 2010). Details of derivatives from these platform chemicals and their production pathways are found elsewhere (Choi
et al., 2015). Combinations of biochemical and thermochemical
technologies have been adopted for the conversion of biomass to
building block chemicals, biofuels, biomaterials, animal feed, and
fertilizer.
The potential resource recovery through AD from three output
sources (i.e., biogas, digestate, and liquid effluent) is discussed in
following section.
Fig. 1. Schematic of large-scale anaerobic biorefinery for producing biofuels and biobased products.
Please cite this article in press as: Sawatdeenarunat, C., et al. Anaerobic biorefinery: Current status, challenges, and opportunities. Bioresour. Technol.
(2016), http://dx.doi.org/10.1016/j.biortech.2016.03.074
3.1. Biogas
Biogas is the prime product of AD. On one hand, AD helps
reduce the volume of organic wastes with a small environmental
footprint and energy consumption; and on the other hand, GHGs,
especially CH4 are effectively captured and utilized.
Individual or combinations of various types of organic wastes
could be used as a feedstock for AD. Besides energy crops, wastes
that need to be managed (e.g., waste activated sludge, MSW, food
waste, agricultural and food processing wastes/wastewater, animal
manure etc.), residues from biofuel processing industries also have
high potential as an AD feedstock. For instance, residues of
bioethanol distillation from sugarcane and corn, known as stillage
and vinasse, respectively, have high potential to be used as AD
feedstocks. However, stillage and vinasse are rich in carbon content, requiring the addition of nutrients to optimize the carbon to
nitrogen (C/N) ratio. In practice, co-digestion with nutrient-rich
feedstocks like cattle manure to adjust C/N ratio to 2030:1 have
been widely applied (Khanal, 2008). Other operational parameters
such as pH, total volatiles fatty acids to total alkalinity (VFA/ALK)
ratio, ammonia, etc., should also be maintained within the recommended range for efficient digestion. The potential methane yields
from various organic feedstocks can be found in Table 3 and
Sawatdeenarunat et al. (2015). Utilization of the produced biogas
has been commercialized in a wide range of applications. The most
common industrial-scaled application is heat and electricity generation using a combined heat and power (CHP) unit. Electrical and
thermal conversion efficiencies of CHP unit are around 40% and
50%, respectively (Pschl et al., 2010). In case of anaerobic digester
fed with sulfur-rich substrate, the presence of hydrogen sulfide
(H2S) in the biogas at a concentration higher than 250 ppm could
be detrimental to the CHP unit. Thus, the H2S in biogas has to be
removed to a value below 250 ppm prior to feeding to the CHP
engine. Various methods for H2S removal, such as pressure swing
adsorption (PSA), water pressure absorption, ferric oxide adsorption, alkaline absorption, biological filtration, and micro-aeration
have been studied and commercialized. Besides H2S, biogas impurities such as CO2, ammonia, moisture, and particulates can be
removed to obtain CH4 content greater than 95% in a process called
biogas cleaning and upgrading. PSA, absorption by scrubbing,
membranes, and cryogenic separation have been applied for biogas
upgrading process at commercial-scale plants. Upgraded biomethane could be used as transportation fuel in the form of compressed natural gas (CNG) or liquid natural gas (LNG) or injected
into a natural gas grid. More details on biogas production and utilization can be found in Budzianowski (2016).
Apart from using biogas as a renewable energy resource for heat
and electricity generation as discussed above, biogas could be converted to methanol, which is a building block of many high-value
industrial chemicals including anhydride, ethylene, polyols and
other aromatic compounds (Ruchle et al., 2016). This concept of
low-volume, high-value conversion pathway for biogas or syngas
(H2 + CO) to liquid fuels and chemicals through chemical and biological conversions has gained significant interest in recent years
(Munasinghe and Khanal, 2011). Overall, biogas production from
organic wastes is an intrinsic merit of AD technology. However,
adapting biorefinery concepts into the utilization of biogas could
open up ideas for research and development in conversion pathways for a variety of higher-value biogas derivatives.
3.2. Digestate
The effluent (digestate) from an anaerobic digester can be separated into liquid and solid streams. The solid stream primarily
consists of suspended solids and undigested residues. Depending
on substrate type and operating condition of the digester, the com-
Please cite this article in press as: Sawatdeenarunat, C., et al. Anaerobic biorefinery: Current status, challenges, and opportunities. Bioresour. Technol.
(2016), http://dx.doi.org/10.1016/j.biortech.2016.03.074
Market demand
(million metric tons/year)
Conversion pathway
Derivatives
Applications
Ethanol
86.0
Polymerization
Polyethylene (PE)
Polypropylene (PP)
Polyethylene terephthalate (PET)
Ethylene glycol
Fuels
Plastic industries
Oxidation
Furans (furfural,
hydroxymethylfurfural (HMF))
0.3
Glycerol
2.0
Polymerization
Oxidation
Plastic industries
Textile fibers
Antifreezes, coolant, solvents
Hydrogenation
Biopolymers
Fumaric acid
Furoic acid
Furandicarboxylic acid
Furfuryl alcohol
Plastic industries
Chemical industries
Hydrogenolysis
Oxidative dehydration
Chemical industries
Plastic industries
Coating
Fuels (jet fuel, diesel, gasoline)
Chemical industries
Biohydrocarbon
NA
Lactic acid
0.4
Polymerization
Polylactic acid
Plastic industries
Succinic acid
0.05
Dehydration
Acrylic acid
Hydrogenation
Plastic industries
Coating
Chemical and plastic industries
Oxidation
Polymerization
Maleic acid
Fumaric acid
Polyester polyols
Dehydration
Acrylic acid
Hydroxypropionic acid
NA
Chemical industries
Adhesives
Coating
Plastic industries
Coating
Levunic acid
NA
Hydrogenation
y-Valerolactone
Fuel additives
Sorbitol
1.7
Oxidation
Chemical industries
Hydrogenolysis
Succinic acid
Acetyl acrylic acid
Diols (ethylene/propylene glycols)
Hydrogenolysis
Chemical industries
Xylitol
0.1
Chemical industries
biopolymers (e.g., bioplastic, resins and adhesives) pose a potentially very interesting opportunity for a lignin biorefinery.
Bozell et al. (2007) reported a technology for lignin utilization
which produces aromatic compounds, including phenols,
benzenetoluenexylene (BTX) and lignin monomers through
catalysis and selective oxidation processes. Although the demands
for such products are high, lack of technical experience and high
energy costs have hindered the commercialization of ligninbased high-value chemicals production.
3.2.3. Solid residues
Besides the lignin utilization via thermo-chemical processes,
the whole solid fibers after the solidliquid separation of the digestate could be used for the production of bio-oil and biochar via
pyrolysis. Bio-oil can also be produced by hydrous pyrolysis in
which thermal decomposition takes place in the presence of water
known as hydrothermal treatment. Biochar is mainly used as a soil
conditioner, which has been found to be effective in carbon sequestration thereby reducing net carbon dioxide emissions. There is an
economic tradeoff between bio-oil and biochar production which
depends on the market price for the product and the type of pyrolysis method used (Pandey et al., 2015).
3.3. Liquid effluent
Ammonium and phosphates are the major nutrients present in
the liquid effluent from AD process. As mentioned earlier, the traditional practice of applying the liquid effluents as ferti-irrigation
has environmental issues when applied in excess, and thus land
application of the liquid effluent must be carefully regulated.
Please cite this article in press as: Sawatdeenarunat, C., et al. Anaerobic biorefinery: Current status, challenges, and opportunities. Bioresour. Technol.
(2016), http://dx.doi.org/10.1016/j.biortech.2016.03.074
Please cite this article in press as: Sawatdeenarunat, C., et al. Anaerobic biorefinery: Current status, challenges, and opportunities. Bioresour. Technol.
(2016), http://dx.doi.org/10.1016/j.biortech.2016.03.074
Acknowledgements
This project is being supported by funding from the Sun Grant
Western Regional Center at Oregon State University through a
grant provided by the United States Department of Transportation
(Sub-award # TO013G-J).
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