International Journal of Environmental Science and Technology

https://doi.org/10.1007/s13762-021-03552-3

ORIGINAL PAPER

Comparison of waste plastic fuel, waste cooking oil biodiesel,

and ultra‑low sulfur diesel using a Well‑to‑Exhaust framework
S. S. Alam1   · P. R. Churkunti1 · C. Depcik1

Received: 8 May 2021 / Revised: 1 July 2021 / Accepted: 12 July 2021

© Islamic Azad University (IAU) 2021

Abstract
The conversion of plastic solid waste and waste cooking oil into useful alternative fuels, e.g., waste plastic fuel and biodiesel,
respectively, helps mitigate waste accumulation and minimize the dependence on fossil fuels, like ultra-low sulfur diesel
(aka diesel). This study aims to assess the potential environmental impacts of both waste-derived fuels with the help of a
scalable Well-to-Exhaust life-cycle analysis (functional unit = 1 kg of fuel) conducted within a university campus (control
volume) with well-defined boundaries. The performance of both fuels is assessed on a Well-to-Pump (fuel fabrication) and
Pump-to-Exhaust (end-use) basis, and their summation is used to present the life cycle impact of each fuel comparative to
diesel. The findings reveal that diesel worsens the local air quality and significantly contributes to global warming. In contrast,
waste plastic fuel appears to have a relatively lower impact on the air quality index and global warming, suggesting that its
production near urban areas could help mitigate plastic waste accumulation and environmental pollution while boosting the
local economy. On the other hand, biodiesel emerges as a relatively cleaner fuel and shows significantly lower emissions,
especially during its fabrication. Therefore, its manufacture and end-use can be decoupled to enhance the economics of the
process. Finally, its lowest overall carbon dioxide emissions hint that its use could be instrumental in lowering greenhouse
gas emissions.

Keyword  Environmental impact · Biodiesel · Life cycle analysis · Plastic solid waste · Waste cooking oil · Waste plastic
fuel

Abbreviations FTIR Fourier transform infrared

AQI Air quality index spectroscopy
ASTM American Society for Testing and FU Functional unit
Materials GHG Greenhouse gases
BSFC Brake-specific fuel consumption GREET Argonne National Laboratory
CFR Code of Federal Regulations Greenhouse Gases, Regulated
CH4 Methane Emissions, and Energy Use in
CI Compression–ignition Transportation
CO Carbon monoxide GWP Global warming potential
CO2 Carbon dioxide H2O Water
EPA Environmental Protection Agency HCHO Formaldehyde
EtW Exhaust-to-Wheels ISO International Organization for
FID Flame ionization detector Standardization
LCA Life cycle analysis (or
assessment)
Editorial responsibility: Maryam Shabani. LCIA Life cycle impact analysis
LDDV Light-duty diesel vehicle
* S. S. Alam
ssalam@ku.edu LHV Lower heating value
MECHO or ­CH3CHO Acetaldehyde
1
Department of Mechanical Engineering, University MPG Miles per gallon
of Kansas, 1530 W 15thStreet, 1109A Learned Hall, N2O Nitrous oxide
Lawrence, KS 66045‑7609, USA

13
Vol.:(0123456789)

NO Nitric oxide
NO2 Nitrogen dioxide
NOx Nitrogen oxides
NRP-ULSD Non-recycled plastic ultra-low
sulfur diesel
O3 : Ozone
PM Particulate matter
PSW Plastic solid waste
PtE Pump-to-Exhaust
PtW Pump-to-Wheels
ROHR Rate of heat release
SOx Sulfur oxides
TDC Top dead center
THC Total hydrocarbon
ULSD Ultra-low sulfur diesel
VOC Volatile organic compounds
WCO Waste cooking oil
WPF Waste plastic fuel
WtP Well-to-Pump
WtW Well-to-Wheels
Introduction
Plastics and edible cooking oils are indispensable con-
sumer goods that produce non-biodegradable elementary
wastes (e.g., plastic solid waste (PSW) and waste cooking
oil (WCO), respectively) as they approach their end of life.
Due to the large production volumes of plastics and cook-
ing oils, waste generation and accumulation have become
a significant problem. These wastes are disposed of via
standard disposal techniques, such as landfilling and incin-
eration, and/or might undergo recycling to recover useful
content (Yaakob et al., 2013; Benavides et al., 2017; Fox
and Stacey, 2019). However, only 9% of the PSW has been
recovered from an estimated 6.3 billion metric tons over six
decades despite state-of-the-art methods (Lombardi et al.,
2015; National Geographic, 2018, Dec 20; Klemeš et al.,
2020). Subsequently, the non-recyclable plastic content that
is left pollutes the environment (Baggio et al., 2008; Al-
Salem et al., 2010; Lazarevic et al., 2010). Alternatively,
materials that are incinerated for landfill reclamation can
generate useful electricity (Gohlke and Martin, 2007), but
the use of fossil fuels in this process results in problematic
emissions (Al-Salem et al., 2010; Astrup et al., 2015; Lom-
bardi et al., 2015). Similar techniques cannot be employed
for WCO. Firstly, since WCO is not easily biodegradable,
its discharge into the public drainage system can cause
widespread soil pollution that can harm both flora and
fauna. Secondly, WCO recycling is not favorable due to its
carcinogenic effects in humans (Ishak and Kamari, 2019).
Finally, WCO composition and properties are a function
of the feedstock used and the cooking methods employed
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International Journal of Environmental Science and Technology
(Doğan, 2016). Therefore, like PSW incineration, it would
be difficult to quantify the gaseous emissions, resulting
from WCO incineration. Therefore, landfilling, recycling,
and incineration of WCO can harm the environment and are
generally prohibited (Keener et al., 2008; Williams et al.,
2012).
Due to the limitations of standard disposal techniques
and the associated risk of environmental harm, a waste-
to-fuel approach has gained traction over the last few
decades that has two advantages: a) reduction of the ele-
mentary waste content and b) use of the derived fuel for
power cogeneration. Among these techniques, waste plastic
pyrolysis and oil transesterification have emerged as rela-
tively simple processes to convert PSW into waste plastic
fuel (WPF) (Anuar Sharuddin et al., 2016; Churkunti et al.,
2016a, b) and WCO into biodiesel (Cecrle et al., 2012; Cor-
dero-Ravelo and Schallenberg-Rodriguez, 2018). Specifi-
cally, biodiesel fabrication from WCO feedstock helps in
avoiding controversy compared to vegetable oil use (Ishak
and Kamari, 2019). Therefore, both fuels are promising
alternatives to ultra-low sulfur diesel (ULSD). In general,
employing a waste-to-fuel methodology has a few major
incentives:
a. Net reduction of the emissions compared to conven-
tional fossil fuels due to negligible material and energy
requirements during elementary waste generation
(Morais et al., 2010; Peiró et al., 2010; Iglesias et al.,
2012; Tu et al., 2015).
b. Significant economic potential due to low procurement
costs and relatively high value of product (Chang et al.,
2014). A recent study in Australia revealed that waste
plastic pyrolysis had a 54% return-on-investment, sug-
gesting that the conversion of plastic waste into fuel is
economically viable (Ghodrat et al., 2019).
Therefore, it helps support several policy objectives,
including energy security, environment, and fuel qual-
ity (Chang et al., 2017). However, its adoption on a large
scale requires proper knowledge of the associated energy
and emissions, resulting from local waste feedstock genera-
tion, transportation, and conversion processes to make the
pathway feasible and sustainable. This is often achieved by
conducting a comprehensive life cycle assessment (alter-
natively, Life cycle analysis (LCA)) of the fuel where the
results are often presented on a Well-to-Wheels (WtW)
basis.
Typically, while conforming to the regulations defined
in ISO-14040 to 14,044 (International Organization for
Standardization, 2006; Anderson et al., 2018; Cheng et al.,
2018), several WPF LCAs have demonstrated that modern
pyrolysis techniques minimize solid waste and improve
energy efficiency while also reducing its environmental
International Journal of Environmental Science and Technology
impact (Lazarevic et al., 2010; Astrup et al., 2015; Lom-
bardi et  al., 2015). Pyrolysis is advantageous since it
reduces emissions by retaining sulfur, chlorine, alkali, and
heavy metals within the solid residues, while mitigating
the thermal nitrogen oxides ­(NOx) formation due to lower
operating temperatures and greater chemical reducing
conditions (i.e., rich combustion) as compared to incin-
eration (Malkow, 2004). Similarly, biodiesel LCAs show
a reduced environmental impact (Varanda et  al., 2011;
Sheinbaum-Pardo et al., 2013; Tan et al., 2015). In addi-
tion, the exhaust emissions from biodiesel-fueled internal
combustion engines have a lower carcinogenic content due
to the absence of sulfur and aromatic compounds in the
fuel (Chang et al., 2014; Cordero-Ravelo and Schallen-
berg-Rodriguez, 2018), thus making biodiesel relatively
less harmful to humans.
While these outcomes appear favorable toward waste-
derived fuels, it must be noted that LCAs usually neglect
process variability that can potentially skew the overall
outcome (Luo et al., 2009; Hennecke et al., 2013; Speck
et al., 2015). For example, existing biofuel LCAs often
utilize experimental combustion findings of others to
complete the analysis. The dissimilar combustion testing
methodologies (e.g., different engine compression ratios,
equivalence ratios, engine geometry, ambient conditions,
etc.) can potentially introduce an accidental bias in the
overall outcome (García-Martín et al., 2018; Patel et al.,
2019; Yesilyurt, 2019). Hence, LCAs of several fuels can-
not be compared directly to select the better alternative
fuel for a specific application (stationary versus transport)
or geographical location (Ardolino et  al., 2018; Aryan
et al., 2019). Furthermore, since LCAs present the emis-
sions on a WtW basis, e.g., gm/mile, they cannot be read-
ily adapted to fuels that are produced for stationary (e.g.,
power cogeneration) applications. In addition, the small
off-road engine (SORE) sector is significantly large and
is projected to grow 5% annually from 14.08 million units
in 2019 to 17.74 million units in 2026. Therefore, a ver-
satile LCA methodology is required that is applicable to
both stationary and transport engine applications while
also conforming to United States (US) Environment Pro-
tection Agency guidelines (40CFR-§1065.20) (Electronic
Code of Federal Regulations, 2018, Dec 21; Pulidindi and
Prakash, 2019). This is achievable by splitting the existing
WtW methodology into a Well-to-Exhaust (WtE) analysis,
followed by an Exhaust-to-Wheels (EtW) step to present
the results on an equivalent WtW or US EPA basis. Ulti-
mately, the WtE framework makes the LCA independent of
the fuel’s end-use and allows a direct comparison between
LCAs of different fuels.
In this vein, this paper demonstrates the development
and application of the WtE methodology to assess the
environmental impact of both the WPF and biodiesel
within a university campus. It is assumed that both plastic
and cooking oil wastes are generated, collected, treated,
and converted into respective fuels on-campus, and their
respective LCAs encompass on-campus energy use and
emissions. Then, the Argonne National Laboratory Green-
house Gases, Regulated Emissions, and Energy Use in
Transportation (GREET) (Wang, 1996) software is used
to model the pertinent on-campus processes involved in
fuel production and evaluate their respective Well-to-
Pump (WtP) energy and emissions footprint. Simultane-
ously, their combustion performance and Pump-to-Exhaust
(PtE) emissions are assessed on-campus with the same
generator engine (< 10 kW) at similar loads. Finally, both
the WtP and PtE efforts are combined to bring the waste-
derived fuels into a common and unique WtE framework
for a comparative life cycle impact analysis. Additionally,
WPF and biodiesel are compared with the ULSD and non-
recyclable plastic fuel (NRP-ULSD) pathways of GREET
for added contrast. Of note, as the name suggests, the
NRP-ULSD fuel is produced from a non-recyclable plas-
tic (NRP) feedstock.
Currently, WPF and biodiesel are considered popular
substitutes for ULSD due to their comparable combus-
tion characteristics. Both fuels hold a significant value
from the standpoint of waste reduction and economics.
However, it is difficult to select either fuel as the better
alternative to ULSD without accidental bias arising due to
dissimilarities in their production pathways. In this vein,
a comprehensive estimation of their respective life cycle
energy and emissions footprints with the popular WtW
methodology can reduce this bias. Unfortunately, a direct
comparison of these LCAs becomes increasingly difficult
when these fuels are produced for stationary applications
(e.g., power generation). Therefore, with the example of
WPF and biodiesel, this effort highlights the importance
of conducting a standardized LCA for alternative fuels
on a Well-to-Exhaust basis. The WtE methodology con-
forms to ISO guidelines and normalizes the results on a
­gramemissions/kgfuel basis to conform to US EPA directives.
Thus, it provides a common ground for a direct compari-
son irrespective of their intended use (e.g., transportation
versus stationary) that potentially simplifies the selection
of the better fuel for a given purpose or geographical loca-
tion. Along with the facilitation for direct comparison,
the detailed WtE analyses of WPF and biodiesel open up
avenues for process optimization to reduce their respec-
tive pathway energy use and resultant emissions. This
improves their overall performance and economics while
bolstering the reputation of both WPF and biodiesel as
cleaner ULSD substitutes. Finally, these WtE results can
be readily scaled further to the more widely used WtW
basis for transportation fuels providing modularity that
13

is potentially attractive from the standpoint of decision
making and policymaking.
Preliminary research on this project began at the Univer-
sity of Kansas (Lawrence) in 2015 and was finalized as a
manuscript in 2021 with an updated WtP analysis in GREET
2020 (latest version).
Materials and methods
Feedstocks and common Well‑to‑Pump components
The on-campus stationary and transportation processes
involved in the production of these fuels were modeled
in GREET 2020. Here, 134 kgs of PSW and 40 gallons of
WCO (primarily canola oil) are generated at different sites
on the university campus that sets the control volume for
the analysis (Fig. 1A). Of note, despite on-campus waste
feedstock generation (Fig. 1B), its energy and emissions
are excluded from the GREET model as per §1a, which
suggests that it is appropriate to include waste generation
and its related energy and emissions in the life cycles
of the primary feedstocks, e.g., plastic and edible cook-
ing oil. Then, PSW and WCO are transported 7.8 miles
around campus (Fig. 1C) from their respective collection
sites to the waste refinement centers (Fig. 1D) using a
Dodge Ram 1500 light-duty diesel vehicle (LDDV) with
100% urban and load shares for the GREET model. Addi-
tionally, the LDDV transports a standard 36 gallons of the
finished product (liquid fuel) over 1.1 miles (Fig. 1F) to a
Fig. 1  A Well-to-Exhaust
framework for on-campus
waste plastic fuel and biodiesel
production from accumulated
plastic solid waste and waste
cooking oil, respectively
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International Journal of Environmental Science and Technology
fueling station (Fig. 1H). Moreover, the energy consump-
tion of the auxiliary devices, e.g., electrical devices, such
as heaters and pumps, during waste refinement and fuel
production, is also included in the model and is assumed
to operate at full load (i.e., load factor = 1) to present the
worst-case scenario. In addition, these devices draw elec-
tricity from the grid that is generated and supplied by a
coal-fired thermal power plant and is represented by a
distributed US electrical mix in GREET. Finally, the spe-
cifics of the waste refinement (Fig. 1D) and fuel produc-
tion (Fig. 1E) processes are mentioned in the subsequent
subsections.
For model consistency and direct comparison of results,
1 kg of the fuel was selected as the functional unit (FU)
to present the results on a per-functional-unit basis. Fur-
thermore, the material properties listed in Table 1 were
used for mass and energy balances as well as conversions
(e.g., WCO gallon to kg). While the properties of waste
feedstock are taken from the literature (except WCO), the
liquid fuel properties were determined via the standard-
ized methods (American Society for Testing and Materials
(ASTM)) using a Koehler KV4000 Series Digital Constant
Temperature Kinematic Viscosity Bath KV4000 (ASTM
D445), 6200 PAAR Calorimeter (ASTM D240), Anton
Paar 5000 M DMA Density meter (ASTM D4052), and
OptiDist distillation unit (ASTM D86). Along with these
common WtP components in GREET, biodiesel and WPF
production pathways require specific components that are
described henceforth.
International Journal of Environmental Science and Technology

Table 1  Resource properties used in both the GREET model and WPF was determined using a Perkin Elmer Series II 2400 CHNS/O
combustion analysis (Kumar et al., 2011; Mangus et al., 2014; Obeid analyzer, whereas other values are taken from the literature
et  al., 2014; Sriningsih et  al., 2014). The chemical composition of

Property ULSD PSW WPF WCO Biodiesel (WCO) NRP NRP-ULSD

Density (kg/m3) 831 200 800.7 935.84 878 940.75 808.73

LHV [volumetric] (MJ/m3) 34,511.43 7140 37,064.4 33,371.1 31,792.38 41,675.2 34,864.35
LHV [mass] (kJ/kg) 41,530 - 46,289.99 - 36,210 - -
Sulfur Ratio (%) 0 - 0 0.02 0.02 0 0
Carbon Ratio (%) 87.1 78.33 86.17 76.64 75.56 86 87.1
Kinematic Viscosity (cSt) 2.268 - 2.91 - 4.85 - -
Dynamic Viscosity (cP) 1.885 - 2.33 - 4.25 - -
Cetane Number 42.3 - 71.88 - 52.8 - -

Fig. 2  Schematic of the biodiesel manufacturing plant highlighting the processes involved along with the quantitative description of their inputs
(both material and energy) and outputs

Biodiesel production
The on-campus biodiesel production has an operating
capacity of 40 gallons as shown in Fig. 2 (Iglesias et al.,
2012) where the WCO initially goes through continuous
thermal treatment and filtration steps to remove all impuri-
ties (approx. 2 gallons). Then, the refined oil (38 gallons)
is collected in a reactor where it reacts with 10 gallons of
methanol and 1100 gm of potassium hydroxide catalyst
at 65 °C for 6 h to form biodiesel (37.50 gals) along with
glycerol (10.64 gals). After removing glycerol from the mix-
ture via gravity separation, the resultant biodiesel is acid-
washed with a mixture of 10 gallons of water and 0.044
gallons of acetic acid (made from fermented and oxidized
carbohydrates (Adom and Dunn, 2016)) in two successive
cycles to remove any chemical or particulate impurities. A
third, and final, wash with 10 gallons of water followed by
4 h of drying with heating jackets results in 36 gallons of
well-refined biodiesel. Meanwhile, the wastewater is col-
lected after each wash and is recycled for reuse later. Of

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Fig. 3  Distillation process
schematic for the recovery of
methanol from crude glycerol.
A reflux column is employed
to increase the efficiency of the
distillation process
note, for the GREET model, the methanol used in this step
is assumed to be produced from US-produced natural gas
(Lee et al., 2016), whereas the potassium hydroxide comes
from the potassium chloride electrolysis (Lampert et al.,
2015). Finally, the recovered glycerol (~ 80% purity) under-
goes vacuum distillation for further purification as well as
to recover methanol from the mix that is fed back into the
biodiesel production loop to offset fresh methanol use in
subsequent batches.
As Fig. 3 shows, glycerol undergoes a, respectively, long
soak period (~ 7 h) where it is heated to 94 °C to remove
impurities while boiling off the methanol. Then, the metha-
nol vapors pass through a reflux column where condensed
methanol is separated from the stream. The remaining
vapors are allowed to pass through a crossflow condenser
(running ethylene glycol at 185 kg/s) for further condensa-
tion before finally collecting in a tank with ~ 97% purity.
Overall, the distillation process recovers approximately 20
vol.% of methanol while producing relatively pure glycerol
(> 95% purity).
WPF production process
A representative WtP analysis was performed for the WPF
used in prior combustion efforts because its technologi-
cal details were not available due to proprietary reasons
(Churkunti et al., 2016a, b). Both catalytic and thermal
pyrolysis processes were shortlisted as prospective path-
ways for WPF production. It is evident from literature
that the catalytic pyrolysis results in a higher yield of
WPF (Malik et al., 2021) with properties and combustion
13
International Journal of Environmental Science and Technology
characteristics close to ULSD (Kumar et al., 2011; Panda
and Singh, 2011; Obeid et al., 2014). However, the use of
an expensive catalyst for consistent product yield makes this
process cost-prohibitive (Malik et al., 2021). Furthermore,
since product yield is a function of successive cycles of
catalyst deactivation and regeneration, catalytic pyrolysis
can be highly nonlinear for modeling purposes. On the other
hand, thermal pyrolysis is relatively simple and has a com-
paratively low cost of operation. In addition, it is shown to
yield a fuel that meets the ASTM D975 and EN590 (Euro-
pean Committee for Standardization) specifications and is
directly suited for internal combustion engine use (Sharma
et al., 2014), thus making it an ideal choice for the repre-
sentative process selection. Therefore, based upon avail-
able literature (Obeid et al., 2014; Lombardi et al., 2015;
Chandran et al., 2019), it was modeled in GREET (as shown
in Fig. 4).
Initially, the 134 kg of PSW feedstock is flushed clean
with water to eliminate particulate contaminants. Then, it
is dried and shredded to a size of 4–5 mm in diameter to
increase its surface area for improved heat transfer charac-
teristics. Simultaneously, the reactor is purged with nitrogen
for 10 min at a rate of 0.20 L/min to maintain an inert envi-
ronment. Then, the shredded PSW is fed into a continuously
stirred reactor where it mixes with cement and gets heated to
500 °C (rate: 10 °C/min) at 1 bar (Singh et al., 2019). Here,
the slow heat addition results in a longer residence time that
lowers the mixture acidity and maximizes the liquid fuel
yield (est. 82 wt.%) with the rest being gas (est. 18 wt.%)
and a negligible quantity of biochar (Anuar Sharuddin et al.,
2016; Murthy et al., 2020). For offsetting the energy and
International Journal of Environmental Science and Technology

Fig. 4  Process schematic for WPF production from PSW along with syngas recovery and its use for power cogeneration

emissions requirement, the resulting syngas coproduct (Para-

schiv et al., 2009) assists in electricity cogeneration (~ 20%)
(Lombardi et al., 2015) to improve the overall effectiveness
of the process.

Engine testing for Pump‑to‑Exhaust (PtE) emissions

The PtE efforts include the testing of biodiesel, WPF, and

ULSD in an air-cooled Yanmar L100V engine at similar
loads (Langness et al., 2014). With a compression ratio of
21.2, this engine normally operates at 1800 rpm and 0.5,
4.5, 9.0, 13.5, and 18.0 Nm torque loads that correspond
to 0, 25, 50, 75, and 100% load setpoints, respectively.
With these runtime conditions, both pre-mixed and mix-
ing-controlled combustion phases are visible along with
the transition from one phase to another, which enables a
thorough combustion and emissions’ analysis for compara-
tive purposes. Additionally, a Dyne Systems Inc. Dymond
Series 12 Alternating Current regenerative dynamometer Fig. 5  Schematic showing the Well-to-Wheels (WtW) and Well-to-
equipped with an Inter-Loc VOCS controller modulates Exhaust (WtE) analysis. Of note, straightforward calculations can be
engine speed with load adjusted through the fuel injection used to convert WtE to WtW results
amount and offers precise engine speed control for accurate
and repeatable combustion analysis. The gaseous emissions, emissions are recorded separately by an AVL Smoke Meter
e.g., carbon dioxide ­(CO2), carbon monoxide (CO), water (model #415SE), thus completing the exhaust emissions’
­(H2O), nitric oxide (NO), nitrogen dioxide ­(NO2), nitrous analysis.
oxide ­(N2O), methane (­ CH4), formaldehyde (HCHO), and Using this test bench, ULSD combustion tests were con-
acetaldehyde ­(CH3CHO), are analyzed by an AVL SESAM ducted before other fuels to set the control and all subsequent
Fourier transform infrared spectroscopy (FTIR) emissions tests were normalized by matching their peak-pressure crank
analyzer (model #2030HY) connected to the engine exhaust. angles to ULSD. This removes the overshadowing effect of
The FTIR is also retrofitted with a flame ionization detector combustion phasing on the engine emissions (e.g., earlier
(FID) and a Magnos 106 oxygen sensor to detect the total combustion favors N ­ Ox formation via thermal N ­ Ox route)
unburned hydrocarbon and oxygen content in the exhaust and prevents erroneous comparisons. For each test, both the
stream, respectively. Finally, the particulate matter (PM) engine performance and combustion emissions data were

13

recorded after the engine achieved steady-state operation
(defined by downstream exhaust gas temperature change of
less than 1% in one minute). During data post-processing,
these data were converted to a brake-specific fuel consump-
tion basis and later modified to a per-functional-unit basis
for consistency with WtP results. However, the combined
WtE results (expressed as ­gmemission/kgfuel) can be converted
to the ­gmemission/kWhr basis mandated by the US EPA via
Eqn. (1). Besides, Fig. 5 and Eqn. (2) add a relatively simple
Exhaust-to-Wheels (EtW) path to convert the WtE results
into equivalent WtW analysis for fuels used in transporta-
tion engines.
[ gm ]
WtEEPA = WtEfuel ⋅ BSFC (1)
kW − hr
[ gm ] 𝜌fuel ⋅ WtEfuel
WtWfuel = (2)
mi MPG
where WtEEPA is the species emission in US EPA-approved
units ­(gmemission/kW-hr), BSFC is the brake-specific fuel
consumption during engine operation (­ kgfuel/kW-hr), WtE-
fuel is the Well-to-Exhaust emission in ­gmemission/kgfuel, ρfuel
is the fuel density (kg/m3), MPG is the fuel economy of the
vehicle (miles/gal), and WtWfuel is the equivalent Well-to-
Wheel emission ­(gmemission/mile).
Fig. 6  Energy values for NRP-ULSD, ULSD, biodiesel, and WPF; (a) comparison of the feedstock energy content and the energy required to
convert it to a useful fuel and (b) the energy content required by source
13
International Journal of Environmental Science and Technology
Results and discussion
Well‑to‑Pump results
Energy
The WtP results of Fig. 6a show the embedded energy con-
tent and external energy requirements of each fuel. It is
evident that while the embedded energy content increases
with biodiesel < ULSD < WPF < NRP-ULSD, the energy
requirement per kilogram follows NRP-ULSD < WPF < bio-
diesel < ULSD. Here, the upstream energy inputs, e.g., nat-
ural gas, heavy-butane-derived gasoline blendstock, etc.,
are primarily responsible for the, respectively, high-energy
consumption for ULSD. However, its coproducts, such as
unfinished oil and pet coke, can be used for in situ power
generation to offset its energy requirement while lower-
ing its emissions. Similarly, the char, fuel gas, and naph-
tha by-products of NRP-ULSD can also be used for power
cogeneration, thus resulting in the lowest overall energy
requirement.
Based on energy consumption, ULSD and NRP-ULSD
define the opposite extremes with ULSD consuming
6—7 × more energy than NRP-ULSD. On the other hand,
biodiesel and WPF consume similar amounts of energy
per functional unit, which is met, mostly, by natural
International Journal of Environmental Science and Technology
Fig. 7  Spider chart to show the different emissions from the WPF,
biodiesel, NRP-ULSD, and ULSD pathways. The values for each
emission category are normalized by their respective maximum to
give dimensionless values and predict an overall trend
gas-derived materials and coal energy. Specifically, for
biodiesel, natural gas consumption grows proportionally
to biodiesel volume due to the external methanol require-
ment (derived from natural gas). Despite its external meth-
anol use, the natural gas requirement of its pathway is still
approximately 16.2% lower than ULSD. Interestingly, the
biodiesel pathway consumes less coal energy comparative
to WPF due to its lower electricity requirement for heating
and power purposes, whereas the WPF pathway has the
highest coal energy consumption among the four fuels due
to its electricity use for heating the reactor (Fig. 6b). Due to
the assumption that a negligible amount of energy is used
during their feedstock generation along with their lack of
dependence on any crude oil-derived inputs, the overall
energy consumption of both biodiesel and WPF appears
to be lower than ULSD (0.3 ×).
Emissions
Figure 7 shows the influence of energy consumption on
emissions generated during production. It is observed
that the shale oil and bitumen use of the ULSD pathway
produce greater greenhouse gases (GHG, e.g., C ­ H4, ­CO2,
and ­N2O) and PM emissions due to the energy-intensive
upstream processes involved in their recovery from oil
sands in North America. Besides, bitumen is heated before
blending it with crude oil to produce a synthetic blend to
offset crude oil consumption. Since the energy required
for heating bitumen comes primarily from coal, it results
in a spike in GHG and PM emissions along with rising
CO emissions due to the lower combustion efficiency of
coal (Cai et al., 2015). These are further worsened by the
coal-dependent crude oil refining and subsequent distil-
lation processes. The greater GHG emissions comprise
mainly of ­C H 4 emissions that arise from the increased
consumption of natural gas and its derived products (e.g.,
Fischer–Tropsch naphtha) with C ­ O2 and N
­ 2O emissions
resulting from fuel combustion for energy and transpor-
tation (United States Energy Information Administration,
2011). In addition, the volatile content of ULSD results
in significant volatile organic compound (VOC) emissions
during the refining stage. Besides, the removal of sulfur
from crude oil releases sulfur oxides (SO, ­SO2) into the
atmosphere. Interestingly, ULSD production accounts
for the lowest overall ­NO x emissions as a result of the
increasingly enhanced process control technologies being
employed to reduce ­NOx emissions at the source to comply
with the Clean Air Act and its amendments (United States
Environmental Protection Agency, 2017a, b; United States
Energy Information Administration, 2018). Overall, ULSD
fares poorly across (nearly) all emission categories relative
to the other fuels.
Compared to ULSD, the GHG, PM, CO, and VOC emis-
sions for NRP-ULSD are significantly lower (by 73.5, 45.0,
64.0, and 56.5%, respectively). While these emissions are
primarily driven by natural gas and coal consumption, power
cogeneration results in lower overall energy requirements
and corresponding emissions. The VOC emissions are low-
ered due to the absence of volatile compounds in both the
feedstock and fabricated fuel. However, the pathway ­NOx
emissions are considerably higher due to its grid electricity
requirement (0.9 × ULSD) to sustain the pyrolysis process.
The greater S ­ Ox emissions arise from the sulfur-contami-
nated feedstock during pyrolysis.
On the other hand, the GHG, PM, and CO emissions
for WPF are 43.6%, 38.4%, and 66.0% lower than ULSD,
respectively, due to negligible emissions during PSW gener-
ation. Besides, its large external energy requirement results
in greater C
­ O2 and N­ 2O emissions (~ 2 ×) compared to both
biodiesel and NRP-ULSD. In addition, the coproduct allo-
cation on a mass-basis partitions the emissions more toward
the denser main product (WPF), resulting in higher emis-
sions per kilogram of WPF. Methane emissions are signifi-
cantly lower (0.1 ×) than ULSD due to its lower dependence
on natural gas-derived products for fuel fabrication. The
lower volatile content of PSW and the lack of the use of
volatile chemical compounds during the pyrolysis process
result in a significant reduction (~ 81.0%) of the pathway
VOC emissions as compared to ULSD. Unfortunately, WPF
production is accompanied by relatively higher S ­ Ox emis-
sions based on the sulfur contamination assumption. In
addition, WPF results in the worst overall N ­ Ox emissions
from the lack of precise process control (unlike ULSD) dur-
ing the thermal drying and pyrolysis processes.
13

For biodiesel, it appears that its GHG and CO emissions
are the lowest overall due to its, respectively, low energy
requirement (~ 0.3 × ULSD) and the coproduct method
employed in the pathway (Mackenzie et al., 2017). Mean-
while, methanol recovery and reuse also offset its emissions
by reducing grid energy requirements. Despite its lowest
overall emissions, fresh methanol use is solely responsible
for the relatively large PM emissions. In addition, methanol’s
volatility influences the pathway’s overall VOC emissions,
and it also puts out significant N
­ Ox during its upstream pro-
cesses. However, its N ­ Ox emissions are lower than WPF
and NRP-ULSD as a function of its relatively lower energy
consumption per kilogram of fuel, as well as the coproduct
mass-allocation method. The biodiesel pathway accounts
for the lowest overall ­SOx emissions that originate from the
assumption that a lack of process control leads to sulfur con-
tamination of the cooking oil during its use.
Pump‑to‑Exhaust results
The PtE results are presented for the full-load (18.0 N-m)
setpoint only to provide a worst-case emissions scenario.
Before analyzing the PtE results, it is important to under-
stand (in brevity) the impact of a few key parameters affect-
ing combustion in compression–ignition (CI) engines and
the resulting emissions.
Performance
Usually, CI combustion undergoes two distinct phases,
e.g., constant volume-like combustion (pre-mixed) phase
followed by a mixing-controlled (diffusion) burn. Gener-
ally, there is a trade-off between the magnitude and length
of these phases, as well as the production of the specific
emissions, which are mostly governed by the fuel proper-
ties (cetane number, viscosity, density, etc.), runtime condi-
tions, fuel injection system, etc., among other factors. Here,
the cetane number is a measure of the ignition delay of the
fuel with a lower cetane number signifying a longer igni-
tion delay that results in a greater pre-mixed burn phase
followed by a relatively shorter diffusion burn. Based on the
fuel properties listed in Table 1, the fuels would arrange as
ULSD > biodiesel > WPF in order of ignition delay period.
In addition, under lean equivalence ratios (runtime condi-
tions), greater pre-mixed combustion favors thermal ­NOx
formation. Consequently, ULSD would have the greatest
pre-mixed burn with a higher potential for ­NOx formation,
followed by biodiesel and WPF.
On the other hand, greater fuel viscosity and density
worsen the fuel atomization and mixing processes and
often result in jet overpenetration followed by impinge-
ment on relatively cooler surfaces with a greater pos-
sibility of the fuel getting trapped in crevices. All of
13
International Journal of Environmental Science and Technology
these factors lead to a longer diffusion burn where the
combustion of fuel-rich zones results in increased total
hydrocarbon (THC), CO, and PM emissions via incom-
plete combustion and carbon chain agglomeration. Based
on viscosity and density, the fuels would arrange as bio-
diesel > WPF > ULSD in terms of the length of diffusion
burn and products of incomplete combustion. In addition,
the presence of more double and triple bonds (e.g., poly-
unsaturated in the case of biodiesel) potentially delays the
breakdown of the fuel molecule but liberates more energy
upon bond dissociation, which affects the in-cylinder tem-
peratures. Moreover, the embedded oxygen content in the
fuel, e.g., biodiesel, also assists in combustion and influ-
ences the in-cylinder temperatures due to an elevated adia-
batic flame temperature. Finally, a common-rail fuel injec-
tion system injects fuel on a volumetric basis; therefore,
a greater amount of fuel with a low volumetric calorific
value is injected compared to a fuel with a high volumet-
ric calorific value, e.g., more biodiesel versus ULSD for
similar operating conditions.
The experimental outcomes are presented in Fig. 8, and
Fig. 8a shows a comparison of the in-cylinder pressure pro-
files within ± 20° of maximum brake torque timing (≈ 10°
after top dead center (TDC)). Here, after normalization of
the peak in-cylinder pressures, WPF and biodiesel have the
highest and lowest peak in-cylinder pressures, respectively,
with ULSD in between, primarily due to their mass-based
energy content. Furthermore, Fig. 8b provides the rate of
heat release (ROHR) information, which is critical for com-
bustion phasing assessment. It is observed that the fuels line
up as expected based on the magnitude of the pre-mixed
burn phase with ULSD > biodiesel > WPF. Due to the trade-
off between pre-mixed and diffusion burn durations based
on the fuel properties, WPF is observed to undergo the long-
est diffusion burn followed by biodiesel and ULSD. While
one would expect to see higher in-cylinder temperatures
for ULSD, Fig. 8c shows that WPF has the highest over-
all in-cylinder temperatures, whereas biodiesel and ULSD
have comparatively lower and similar temperatures. This is
primarily due to the following reasons: mass-based energy
content of the fuel, cetane number, and heat loss via wall
heat transfer.
It is important to note that the mass-based energy con-
tent of fuel has a significant impact on its combustion tem-
perature. Therefore, a fuel with higher energy content, e.g.,
WPF, would burn hotter than ULSD and biodiesel that have
comparatively lower energy contents. In addition, WPF’s
higher cetane number results in a smaller pre-mixed com-
bustion event that consumes approximately 8 wt. % of the
fuel by the time of ULSD ignition. Consequently, a larger
mass fraction of WPF undergoes a relatively longer diffu-
sion burn where a greater amount of energy is released at
later crank angles, which raises the end-gas temperatures.
International Journal of Environmental Science and Technology
Fig. 8  (a) In-cylinder pressure,
(b) rate of heat release, and (c)
in-cylinder temperature versus
crank angle for ULSD, WPF,
and biodiesel at 18.0 N-m load
A warmer in-cylinder residual is left behind due to valve
overlap, which further increases the charge temperature in
the subsequent cycle. On the other hand, a higher pre-mixed
burn sees a faster increase in in-cylinder temperatures, e.g.,
ULSD, which creates a significant delta between the com-
bustion zone and wall temperatures. Due to a smaller amount
of fuel burn combusting in the following diffusion burn, a
significant heat loss occurs via wall heat transfer, and as a
result, ULSD combustion is unable to reach WPF tempera-
tures later in the cycle.
Emissions
Following the combustion phasing trends, ULSD shows
higher ­NOx emissions followed by biodiesel and WPF as
listed in Table 2. Along with a greater pre-mixed burn,
the relative abundance of oxygen for combustion (experi-
mental Φ = 0.48) assists in ­NOx production via the thermal
route closer to the TDC. For biodiesel, in addition to the
significant pre-mixed burn, the liberation of the embedded
oxygen also potentially favors ­NOx production.
The results in Table 2 show that biodiesel emerges with
the worst THC and CO emissions due to its higher viscosity
and density. Additionally, CO emissions also form via C ­ O2
dissociation at higher temperatures, and biodiesel’s embed-
ded oxygen ramps up the dissociation by raising the end-gas
temperature via late fuel oxidation (Churkunti et al., 2016a,
b). Regarding ULSD, it has greater THC and CO emissions
than WPF due to the higher end-gas temperature observed
with WPF that promotes further oxidation of the unburnt
hydrocarbons and CO (Reşitoğlu et al., 2014). Regarding
PM emissions, the embedded oxygen content of biodiesel
lowers the production of PM emissions significantly by add-
ing oxygen to the fuel-rich core (Heywood, 1988; Depcik
et al., 2015). In addition, biodiesel’s significantly higher
VOC emissions lower the activation energy required for
PM oxidation (Qu et al., 2016). Therefore, PM emissions
have a greater potential to be oxidized later in the cycle. In
13
 International Journal of Environmental Science and Technology

contrast, a high saturated carbon bond content of WPF along
with a hotter burn lowers its PM emissions (Churkunti et al.,
2016a, b).
In addition to the major emissions, carbonyl emissions
(e.g., HCHO and MECHO) constitute the volatile emis-
sions during combustion. Often, these compounds are a
function of the fuel’s oxygen and ester content and ema-
nate from localized inefficient combustion zones where
the fuel decomposition–oxidation processes abruptly ter-
minate at an intermediate stage of a chemical reaction due
to a reduction in the localized temperature and oxygen
concentration (Man et al., 2016). Table 2 shows that the
VOCs are emitted in the order of biodiesel > ULSD > WPF
with formaldehyde being the primary constituent for
ULSD and WPF, whereas acetaldehyde governs VOC
emissions from biodiesel. The greater formaldehyde and
near-negligible acetaldehyde emissions from ULSD and
WPF align with the literature (Peng et al., 2008; Lea-
Langton et al., 2009). The lower VOC emissions from
ULSD are a result of a greater pre-mixed burn and higher
peak temperatures, which promote the oxidation of car-
bonyl compounds. On the other hand, the combustion of
WPF has uniformly high combustion chamber tempera-
tures and relatively long gas retention times that result
in lowered VOC emissions. For biodiesel, the attached
oxygen molecule improves combustion efficiency, sub-
sequently setting up ideal conditions for re-oxidation and
conversion of carbonyl species (Zarante et al., 2010; Li
et al., 2017). Therefore, its relatively higher VOC emis-
sions can be attributed to its greater viscosity that leads
to larger droplets, poorer atomization, and a longer time
for fuel injection. Despite its highest adiabatic flame tem-
perature, locally fuel-rich zones might be created that are
cooler than the overall combustion chamber. Hence, while
temperatures are large enough to promote formaldehyde
dissociation, these zones fail to deliver sufficient energy
for the dehydrogenation of acetaldehyde (Li et al., 2017).
Consequently, these zones are ideal for carbonyl species
production, and biodiesel is observed to have the highest
acetaldehyde emissions among the fuels.
The PtE C ­ O2 emissions are a function of combustion
efficiency, the amount of fuel used, and the fuel constitu-
ents (i.e., predominantly carbon content). Since all fuels
operated at combustion efficiencies around 99%, no real
impact on the PtE findings can be inferred from this infor-
mation. Due to its lower energy content, significantly more
biodiesel was used during the testing procedure as indi-
cated by the brake-specific fuel consumption (BSFC) data
(biodiesel: 240.60; WPF: 236.03; ULSD: 233.89; ­[gmfuel/
kWhr]). Moreover, an approximate chemical formula, i.e.,
­C17.8H32.9O2.0 for biodiesel, taken from Cecrle et al. (Cecrle
et al., 2012), indicates a significant carbon content in the
fuel. On a mass basis, the carbon content in biodiesel is
75.6%, whereas WPF and ULSD have 86.2% and 86.3%
(Table 1), respectively. Since C ­ O2 emissions are propor-
tional to the mass-based carbon ratio of the fuel (Mangus
et al., 2014), biodiesel produces the least amount of C ­ O2
emissions on a per-fuel-kg basis despite relatively greater
brake-specific consumption, as was found earlier by Tesfa
et al., (Tesfa et al., 2014).

Table 2  WtP, PtE, and WtE emission results for ULSD, WPF, biodiesel, and NRP-ULSD.
Species WtP PtE @ 18 N-m Torque WtE (WtP + PtE)

NRP-ULSD
NRP-ULSD
Biodiesel

Biodiesel

Biodiesel
ULSD

ULSD

ULSD
WPF

WPF

WPF

(est.)

0.11 0.09 0.46

VOC
0.33 0.06 0.10 0.14 (100, (100, (39, 0.44 0.15 0.55 0.25
(%HCHO, %MECHO)
0) 0) 61)
CO 0.57 0.20 0.19 0.20 5.56 4.97 5.64 6.13 5.17 5.82 5.76
NOx 0 0.43 0.36 0.38 19.97 17.51 18.19 19.97 17.94 18.55 20.35
PM 0.16 0.08 0.10 0.09 1.47 1.73 0.86 1.63 1.81 0.96 1.56
SOx 0.68 0.65 0.21 0.39 0.07 0.03 1.09 0.75 0.68 1.30 0.47
CH4 10.00 0.81 0.91 0.40 0.02 0.02 0.03 10.02 0.83 0.94 0.43
N2O 0.01 0.01 0.003 0.003 0.04 0.03 0.04 0.05 0.04 0.04 0.04
570.0 420.0 190.0 260.0 2215.7 2113.3 1879.3 2785.7 2533.3 2069.3 2475.7
CO2
0 0 0 0 9 8 1 9 8 1 9
THC ND ND ND ND 2.48 1.52 9.78 2.48 1.52 9.78 2.48

Colors red, black, and green delineate the performance of each fuel across the emissions spectrum with red and green signifying the highest and
lowest emissions, respectively, for the given emission species. On the other hand, black signifies the intermediate value
Note: Due to a lack of PtE emissions data for NRP-ULSD, the PtE values for ULSD are also used for NRP-ULSD assuming relatively similar
combustion performance. ND: Not Determined. Units: ­gmemissions/kgfuel

13
International Journal of Environmental Science and Technology
Finally, ­CH4 emissions from the tested fuels are relatively
low and their difference is, respectively, small making it dif-
ficult to determine any definitive PtE trend. This is not the
case with recorded ­SOx emissions in Table 2. The signifi-
cantly higher biodiesel ­SOx emissions as compared to WPF
(38 ×) and ULSD (15 ×) are an interesting outcome since
biodiesel is generally assumed to have lower sulfur content
than comparable fuels (Chhetri et al., 2008). The results sug-
gest the presence of sulfur compounds in the WCO feedstock
due to contamination from the cooking process. Further-
more, sulfur forms sulfate compounds during the biodiesel
production process and insufficient water-washing of bio-
diesel from a two-step acid–base process may leave residual
sulfates, subsequently resulting in elevated sulfur content
in the biodiesel (sometimes even greater than the US EPA
fuel specification for sulfur content (He et al., 2009)). In
addition, the relatively greater amount of biodiesel and fuel
oxidizer in the inducted charge during engine intake creates
ideal conditions for the combustion of sulfur and opens up
the reaction pathways leading to S­ Ox emissions (Choudhury
and Padak, 2017).
Well‑to‑Exhaust emissions and life cycle impact
assessment
Summing up the WtP and PtE results from Table 2 pre-
sents an overall WtE picture to assist in an accurate life
cycle impact assessment (LCIA) of each fuel. However, it
is advised to consider the NRP-ULSD data and compari-
sons with caution since its PtE results are borrowed from
ULSD, assuming that they both combust similarly. For the
LCIA, pollutant species are lumped together based on their
Fig. 9  Stacked bar chart to compare the life cycle gaseous emissions
of the different fuels. These gaseous emissions constitute the group of
gases that affect local air quality
environmental impact, e.g., CO, N ­ Ox, PM, S­ Ox, VOCs, and
THCs constitute a group of pollutants that have a major
impact on the air quality index (AQI), whereas the concen-
trations of ­CH4, ­N2O, and ­CO2 help in the determination of
the global warming potential (GWP).
Air Quality Index
The air quality index is a numerical scale that shows wors-
ening air quality as the number goes up and serves as an
indicator for air pollution and health-related concerns. To
compare fuel life cycle performance and evaluate their
effect on the AQI index, the effects of all AQI constitut-
ing species from each fuel life cycle need to be understood
and examined individually. For brevity, the stacked column
chart of Fig. 9 shows the AQI species for the fuels being
studied.
CO  Carbon monoxide is considered a harmful gas that read-
ily reacts with the red blood cells and hinders their oxygen-
carrying capacity that leads to tissue damage and eventually
death (at critical concentrations). The presence of CO in the
atmosphere poses a risk to the local population, and the use
of a fuel with the lowest overall CO emissions would prove
to be beneficial. In this regard, data from Table  2 along
with Fig.  9 reveal that the fuels arrange as ULSD > bio-
diesel > NRP-ULSD > WPF based on their overall CO emis-
sions. Specifically, WPF, NRP-ULSD, and biodiesel show
approximately 15.7, 6.0, and 5.1% reductions, respectively,
compared to the ULSD baseline. For WPF, the reduction
in CO emissions is dominated by the significant reductions
during its production. In addition, the combustion of WPF
also produces reduced CO emissions. Hence, the fabrica-
tion and use of WPF would appear to improve the local AQI
compared to other fuels, especially conventional transporta-
tion fuels such as ULSD.
NOx.  NOx emissions typically comprise NO and ­NO2 spe-
cies. Between the two, N ­ O2 is considered more toxic and
harmful for humans. In this vein, ­NOx poisoning in humans
causes respiratory issues and muscular paralysis, which,
in extreme cases, can also cause death by asphyxiation.
Considering this information for fuel selection, it appears
that WPF again shows promise as a ULSD alternative with
significantly reduced N
­ Ox emissions (approx. 10.2%). It is
closely followed by biodiesel with 7.1% reductions. While
WtP ­NOx emissions of biodiesel are lower than WPF, its
combustion results in greater ­NOx emissions comparatively
that worsen its overall ­NOx emissions. On the other hand,
NRP-ULSD production and use result in ­NOx emissions
greater than the baseline (ULSD). Therefore, these fuels
would reduce the local AQI in the following order: NRP-
ULSD > ULSD > biodiesel > WPF.
13

PM  Particulate matter comprises all solid and liquid par-
ticles (both organic and inorganic) in air, and exposure to
these particles is observed to cause respiratory symptoms,
irritation of the airways, and reduced lung and heart func-
tion in humans. Furthermore, smaller particles (< 2.5  µm)
are considered carcinogens as they can potentially perme-
ate through human skin. Therefore, PM reduction at the
source, e.g., the fuel, is a must, and in this regard, biodiesel
performs relatively better than the other fuels showing an
approximately 41.1% reduction in the overall PM emis-
sions (compared to ULSD). While its WtP PM emissions
are reduced, the longer diffusion burn and the presence of
embedded oxygen appear to reduce the PM production sig-
nificantly during combustion. Furthermore, NRP-ULSD
appears to be the next-best alternative with a 4.3% reduction
in PM emissions compared to ULSD. On the contrary, WPF
shows an 11.0% increase in PM emissions and emerges as
the worst PM polluter.
SOx  Oxides of sulfur are normally produced during the
combustion of sulfur-containing fuels. This family of gases
irritates the respiratory tract in humans and is responsible
for an increased rate of lung infections, asthma, and bron-
chitis. In addition, ­SOx gases carry the potential to oxidize
further under favorable conditions in the atmosphere. Their
oxidation results in the formation of sulfuric acid, which is
the precursor and a major contributor to the phenomenon
called acid rain. To keep S ­ Ox emissions under control, it
is imperative to select a transportation fuel with the least
embedded sulfur content. Therefore, from the WtE data,
NRP-ULSD tops the list with up to 37.3% reduction in
the overall ­SOx emissions followed by WPF with ~ 9.3%
reduction. However, biodiesel shows the worst ­SOx emis-
sions with ~ 73.3% greater emissions than ULSD. Here, it is
important to note that the ­SOx emissions from waste feed-
stock-derived fuels must be considered with caution due to
the sulfur contamination assumptions in place. Neglecting
the significant gains of using NRP-ULSD over ULSD based
on an assumption of similar PtE performance, WPF emerges
as a suitable alternative, and its use would potentially reduce
the ­SOx emissions and boost the local AQI.
VOC  Volatile organic compounds are carbon-based mol-
ecules emitted from certain solids and gases via evapora-
tion (mostly under ambient conditions) and later actively
participate in atmospheric photochemical reactions. These
reactions result in the formation of ground-level ozone that
reacts further with ­NOx and CO resulting in photochemi-
cal smog. Therefore, VOC emissions are regulated by US
EPA, and it is important to select the fuel with the least
VOC emissions. In this regard, WPF and NRP-ULSD show
65.9% and 43.2% reductions in VOC emissions compared
to ULSD. Since the methods involved in the production
13
International Journal of Environmental Science and Technology
of WPF and NRP-ULSD from PSW eliminate the use of
volatile compounds (e.g., methanol and ethanol), the WtP
VOC emissions for both fuels are significantly lowered.
Comparatively, the dependence of biodiesel production on
methanol results in elevated overall VOC emissions that
are found to be up to 25.0% greater than ULSD. Therefore,
biodiesel production and its subsequent use would worsen
the smog problem in regions with smog-favoring ambient
conditions.
THC  As described earlier, hydrocarbons of varying lengths
originate during combustion when the fuel avoids the flame
zones. Upon emerging from the engine exhaust, lighter
hydrocarbons either ascend or remain suspended in the air
and adversely affect human health, whereas heavier forms
often descend to the ground causing soil and water pollu-
tion. In smaller quantities, THCs often act as lung irritants;
however, they can also cause irregular heart rhythms, dam-
age to the kidneys or liver, seizures, and coma. In addition,
THCs can also react with other pollutants, such as N­ Ox and
­N2O, in the presence of sunlight to form ozone ­(O3) that
is the critical component of photochemical smog. To con-
trol and reduce THC emissions, fuels with reduced wall-
quenching characteristics are preferred. For example, the
lower density and viscosity of WPF enable better atomiza-
tion and reduce the length of the fuel jet. With a reduced
amount of fuel impinging on combustion chamber walls, the
scope of wall-quenching is minimized, thereby resulting in
a reduction of the THC emissions. From the analysis, WPF
shows a 38.7% decrease in THC emissions comparatively.
On the other hand, biodiesel shows an increase of 294.4%
in its THC emissions due to its greater density and viscosity
hindering its atomization post-injection and elongating the
fuel jet. Contrary to WPF, more biodiesel impinges on the
combustion chamber walls that increase wall-quenching and
THC emissions. Finally, since THC emissions could not be
recorded for the WtP stages of each fuel due to software
limitations, the borrowed combustion data of NRP-ULSD
(from ULSD) do not provide any useful information, and
caution is advised.
Global Warming Potential
In addition to the AQI, the GWP scale also helps in the fuel
selection based on its performance across the greenhouse
gas emissions’ spectrum that allows the determination of its
overall impact on local as well as global (ambient) tempera-
tures. The respective ­CH4, ­N2O, and ­CO2 emissions for each
fuel are shown in Fig. 10.
CH4  Methane is significantly more potent at trapping heat
within the Earth’s atmosphere compared to carbon dioxide,
which accelerates global warming and disrupts the climate
International Journal of Environmental Science and Technology

Fig. 10  The WtE emissions for

each fuel a) C
­ H4 and b) ­N2O,
and c) ­CO2

system. Since fuel production and use contribute to the
global ­CH4 emissions, the alternative fuel with the low-
est overall C­ H4 emissions is preferable over conventional
fossil fuels. Figure  10a illustrates that all alternative fuels
show a considerable decrease in C ­ H4 emissions compared
to ULSD. Specifically, compared to ULSD, NRP-ULSD
shows the greatest reduction with 95.7%, followed by WPF
(91.7%) and biodiesel (90.6%). Neglecting the PtE data for
NRP-ULSD, the major reduction in its ­CH4 emissions arises
from its lower consumption of external energy and maxi-
mized reutilization of its by-products for power cogenera-
tion. Similarly, WPF and biodiesel also benefit in this regard
from their reduced external energy consumption and power
cogeneration potential while showing almost similar ­CH4
PtE emissions.
N2O  Along with C ­ H4, nitrous oxide is a potent green-
house gas. Due to its role in stratospheric ozone deple-
tion (Fuhrman and Capone, 1991), ­N2O emissions need to
be controlled and effectively reduced at the source. Com-
paring the WtE performance of the fuels in Fig. 10b, it is
observed that the alternative fuels again outperform ULSD

Table 3  Simplified comparison Fuel Air quality index Global warming

of the fuels to ULSD based on potential
their impact on the air quality
index and the global warming CO NOx PM SOx VOC THC CH4 N2O CO2
potential. (Key: – better than
ULSD, – worse than ULSD) WPF ▼ ▼ ▲ ▼ ▼ ▼ ▼ ▼ ▼
Biodiesel ▼ ▼ ▼ ▲ ▲ ▲ ▼ ▼ ▼
NRP-ULSD (est.) ▼ ▲ ▼ ▼ ▼ ▲ ▼ ▼ ▼

13

in terms of ­N2O emissions. Specifically, WPF shows a
20.0% reduction, whereas both biodiesel and NRP-ULSD
show a 14.0% reduction. However, it is noteworthy that
the ­N2O emissions for biodiesel and NRP-ULSD during
the WtP stage are an order of magnitude smaller than both
WPF and ULSD.
CO2  Carbon dioxide occurs naturally in the Earth’s atmos-
phere. However, it is also emitted through human activities
and is considered the primary greenhouse gas that sets the
baseline for the GWP determination of other greenhouse
gases. Since fuel combustion in both transportation and
stationary engines is largely responsible for the C ­ O2 emis-
sions, it is imperative to select a fuel that produces the least
amount of C ­ O2 per kg of fuel. The data in Table  2 and
Fig.  10c show that the PtE C ­ O2 emissions can constitute
79.5% (ULSD)–90.8% (biodiesel) of the overall C ­ O2 emis-
sions. Here, biodiesel shows a significant reduction (25.7%)
in the overall ­CO2 emissions primarily due to its lower car-
bon content based on its chemical formula. Moreover, the
WtP ­CO2 emissions are also significantly lower relative to
other fuels, especially ULSD, due to its reduced dependence
on fossil fuel energy.
Finally, Table 3 provides a simplified comparison of the
alternative fuels across the emissions spectrum and their
impact on the air quality index as well as the global warming
potential relative to ULSD.
Conclusion
Waste-to-fuel conversion is an innovative means to reduce
waste accumulation and its harmful effects on the envi-
ronment. Specifically, it could help in the reduction of the
plastic and used edible cooking oil wastes while providing
alternative fuels for compression–ignition engines, thus
reducing the stress on the fossil fuel reserves. However,
since the involved processes require material and energy
inputs, they are responsible for emissions that can contrib-
ute to environmental pollution. Therefore, a life cycle anal-
ysis of each waste-to-fuel pathway becomes necessary to
determine the feasibility of the waste-to-fuel pathways and
the viability of the end-product as an alternative to ultra-
low sulfur diesel. In this vein, the Well-to-Exhaust (WtE)
method, which is based on the popular Well-to-Wheels
(WtW) life cycle analysis methodology, is a useful way to
evaluate the overall energy and emissions from the fuel’s
life cycle for use in both stationary and mobile compres-
sion–ignition engines while conforming to the ISO and US
EPA guidelines.
The WtP results of the analysis show that the emis-
sions from the pathways are proportional to its external
energy requirements. Furthermore, the energy required
13
International Journal of Environmental Science and Technology
for the manufacture of upstream raw materials results in
added emissions, e.g., methanol use (biodiesel) and natu-
ral gas/heavy butane blendstock (ULSD). In addition, the
pathway emissions are also governed by the fuel used for
energy generation, e.g., coal use (incomplete combustion
of coal results in elevated GHG, PM, and CO emissions).
Moreover, critical processes in the pathway, e.g., transes-
terification (biodiesel) and pyrolysis (WPF), appear to have
the largest share of emissions due to their greater energy
requirements. Furthermore, the use of some by-products,
e.g., syngas (WPF) or unfinished oil and pet coke (NRP-
ULSD), for power cogeneration appears to offset a signifi-
cant amount of external energy and associated fossil fuel
requirements. In addition, material recovery and reuse,
e.g., methanol (biodiesel), also appear to offset the emis-
sions by reducing the pathway’s dependence on external
methanol, which is a major polluter. Of note, the energy
and emissions’ offset in the model were achieved by using
a mass-based coproduct allocation method to express the
final results on a mass basis. While it is noteworthy that
the importance of the coproduct allocation method in the
overall analysis must be evaluated via sensitivity analysis, it
lies outside the scope of the current effort. In addition, other
assumptions including zero energy use in waste generation
and sulfur contamination of plastic and used edible cook-
ing oil wastes are also observed to influence the pathway
emissions.
On the other hand, the PtE analysis reveals that emis-
sions are a function of the fuel’s combustion characteristics
that are in turn a function of the fuel’s properties. While
normalization of the peak pressures minimizes the influ-
ence of the fuel properties on emissions, some influence
can still be observed from the scaled pre-mixed and diffu-
sion combustion processes. For example, greater viscosity
and density of the fuel appear to affect the jet penetration
and fuel atomization processes that result in incomplete
combustion of fuel-rich zones at later crank angles and pro-
mote THC, CO, and PM emissions. Moreover, the chemi-
cal makeup of the fuel is also observed to govern its PtE
emissions. Specifically, the embedded oxygen content of
the fuel (e.g., biodiesel) could potentially result in N ­ Ox
formation under favorable conditions, but also enhance the
oxidation of other species (e.g., PM) by adding oxygen
to the fuel-rich cores. Furthermore, the relatively lower
carbon content of the biodiesel molecule is responsible
for its comparatively lower ­CO2 emissions despite higher
brake-specific fuel consumption. Moreover, a fuel’s mass-
based energy content appears to influence the in-cylinder
temperatures significantly, e.g., WPF has higher overall
temperatures due to its higher energy content. However,
despite higher temperatures, WPF has the lowest PtE N ­ Ox
emissions since the temperatures do not peak at prime
crank angles, unlike ULSD that has higher pre-mixed
International Journal of Environmental Science and Technology
temperatures and thus produces greater ­NOx emissions.
Furthermore, ­CH4 emissions from all fuels were relatively
low and do not provide any definitive trend. However, S ­ Ox
emissions for biodiesel emerged to be significantly greater
than WPF and ULSD, perhaps due to the sulfur contami-
nation of feedstock assumption. This is an interesting out-
come since biodiesel is generally assumed to have a lower
sulfur content.
Summing up the WtP and PtE findings shows the WtE
performance of each fuel and reveals that ULSD is the
worst polluter among all fuels that contribute significantly
to climate change. Therefore, it is imperative to substitute
its use with an alternative fuel to mitigate any future harm.
In selecting the best fuel for a specified purpose, a life
cycle impact analysis on the WtE results demonstrates the
effect of major pollutants from each fuel on the environ-
ment by determining their impact on the air quality index
and the global warming potential. Specifically, based on the
overall impact on local air quality, WPF emerges as the bet-
ter fuel with significantly lower CO, N ­ Ox, ­SOx, VOC, and
THC emissions and is closely followed by biodiesel. How-
ever, owing to biodiesel properties, its production and use
may be detrimental to air quality in certain geographical
locations due to its high THC emissions. Based on global
warming potential, WPF offers significant reductions in
­CH4 and N ­ 2O emissions compared to ULSD and appears
promising as an alternative fuel. However, biodiesel shows
significantly lower WtP emissions, which suggests that
biodiesel production and use can be decoupled. In other
words, biodiesel can be produced in one geographical loca-
tion based on the availability of resources and raw materi-
als and can then be transported elsewhere for end-use. This
could potentially help economize the overall process. In
addition, biodiesel C­ O2 emissions are found to be the low-
est overall that indicates that its use could be instrumental
in lowering greenhouse gas emissions.
Acknowledgements  The authors would like to thank Dr. Edward F.
Peltier, Dr. Arkan D. Jalal, Mr. Daniel Tabakh, Mr. Charu Vikram
Srivatsa, Mr. Emilio Alverio, and Mr. Jesse Copp for providing useful
inputs at various stages of the current study.
Authors Contribution  Shah Saud Alam, Preetham Reddy Churkunti,
and Christopher Depcik performed conceptualization; Shah Saud Alam
and Preetham Reddy Churkunti were involved in methodology; Shah
Saud Alam and Preetham Reddy Churkunti contributed to formal anal-
ysis and investigation; Shah Saud Alam done writing—original draft
preparation; : Christopher Depcik and Shah Saud Alam were involved
in writing—review and editing; Christopher Depcik done supervision.
Funding  This research did not receive any specific grant from funding
agencies in the public, commercial, or not-for-profit sectors.
Declarations 
Conflicts of interest  The authors declare that they have no conflict of
interest.
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