Hindawi

International Journal of Energy Research

Volume 2023, Article ID 3040073, 11 pages
https://doi.org/10.1155/2023/3040073

Research Article
Influence of Fuel Oxygenation on Regulated Pollutants and
Unregulated Aromatic Compounds with Biodiesel and n-
Pentanol Blends

Nadir Yilmaz ,1 Francisco M. Vigil ,2 Alpaslan Atmanli ,3 and Burl Donaldson4

1
Department of Mechanical Engineering, Howard University, Washington DC, USA
2
Los Alamos National Laboratory, New Mexico, USA
3
National Defense University, Ankara, Turkey
4
Department of Mechanical Engineering, New Mexico State University, New Mexico, USA

Correspondence should be addressed to Alpaslan Atmanli; alpaslan.atmanli@gmail.com

Received 15 February 2023; Revised 28 March 2023; Accepted 4 April 2023; Published 17 April 2023

Academic Editor: Sanjay Basumatary

Copyright © 2023 Nadir Yilmaz et al. This is an open access article distributed under the Creative Commons Attribution License,
which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

It is very important to determine the polycyclic aromatic hydrocarbon (PAH) emissions caused by the use of renewable fuels in
diesel engines and to know the possible damages. This study investigates the emissions (regulated and unregulated) of biodiesel/n-
pentanol mixtures, which are free of aromatic content, with emphasis on PAH formation and an examination of toxicity to public
health and the environment. Engine failures caused by wetstacking are also discussed. Biodiesel/n-pentanol fuel mixtures with
alcohol concentrations of 5%, 20%, and 35% by volume (v/v) served as test fuels in a compression ignition engine. A five-gas
analyzer was used to measure hydrocarbon (HC), carbon monoxide (CO), and nitrogen oxide (NOx) emissions. Polycyclic
aromatic hydrocarbons were detected and measured using gas chromatography-mass spectrometry (GC-MS). Against the
baseline diesel fuel, the biodiesel/n-pentanol fuel blends and neat biodiesel reduced NOx emissions and produced significantly
fewer PAHs and toxicity, confirming the significance of the aromatic content of the fuel. Biodiesel reduced total PAHs by
48.02% and the addition of 5% n-pentanol to biodiesel further decreased total PAHs by 21.26%. The total toxicity (BaPeq
(benzo[a]pyrene equivalent)) as a result of biodiesel was 83.49% less than diesel. The addition of n-pentanol to biodiesel
further reduced toxicity by 59.15%, 57.89%, and 48.33% for BPen5, BPen20, and BPen35 blends, respectively. In addition, n-
pentanol was shown to be effective for reducing total PAH emissions, as well as heavier PAHs, which have greater
carcinogenicity and pose a greater likelihood of engine damage from wetstacking when running in low-load conditions at cold
temperatures.

1. Introduction It is believed that diesel engines are among the greatest

Government regulations and increased competition in the
automotive industry have driven the development of new
engine technologies with a focus on fuel economy and emis-
sions reduction [1]. The high thermal efficiency of diesel
engines is due to their high expansion ratio and lean com-
bustion, which enables heat dissipation by the excess air
[2]. Although these performance characteristics make diesel
engines attractive for widespread adoption, they also pro-
duce higher emissions of CO, NOX, particulate matter
(PM), unburned HC, and life cycle carbon dioxide (CO2).
sources of NOx and smoke pollution [3]. Although all engine
manufacturers regulate such emissions, petroleum fuels fre-
quently face supply issues and see a resulting increase in
cost. Finding better renewable energy sources is becoming
more important as alternative fuels from those renewable
sources can be used as an attractive method to reduce
NOx, smoke, and CO2 emissions [4].
For nearly half a century, research has been continuing
to find sustainable alternative fossil-based fuels for automo-
tive and aerospace applications [5]. The focal point of
research to find fossil fuel alternatives has been oxygenated
2 International Journal of Energy Research
fuels and bioalcohols [6, 7]. Biodiesel has potential as a suit-
able replacement for fossil-based fuels because it is biode-
gradable, sustainable, and environmentally friendly. Due to
these attributes, it is becoming widely used and researched
around the world. Neat biodiesel is commonly used, or it is
mixed with diesel fuel at specific blend ratios. The oxygen
content of biodiesel lowers the in-cylinder temperature and
reduces emissions, which greatly affects engine combustion
performance [5]. More importantly, biodiesel has fewer of
the harmful aromatic compounds usually present in fossil
fuels and has almost no sulfur. However, biodiesel produc-
tion from feedstocks presents risks to food security. There-
fore, biodiesel manufactured using inedible or waste oils
has become an attractive option for use in diesel engines.
When using biodiesel straight, or in a mixture with diesel,
negative effects such as freezing and high NOx emission
can occur due to its properties. The integration of bioalco-
hols into biodiesel fuel blends has gained popularity because
it compensates for these disadvantages and has the potential
to lead to a greater adoption rate of biofuels. Properties such
as density and viscosity of biodiesel fuel blends can be ame-
liorated with the addition of alcohol [8, 9].
In determining the type of alcohol for use with compres-
sion ignition engines, a high carbon number is key to the sta-
bility of the mixture and combustion performance. One of
the high-carbon alcohols, n-pentanol, has been at the fore-
front of associated research due to its heat of combustion,
flame speed, higher cetane number, viscosity, lower ignition
temperature, and reduced corrosion risk [10–12]. In all stud-
ies in the literature regarding biodiesel and n-pentanol mix-
tures, it is shown that n-pentanol absorbs more heat during
evaporation since it has a lower heat of combustion and
higher LHE. The premixed and diffusion combustion stages
are improved through the use of an oxygen-rich alcohol such
as n-pentanol [13]. Thus, mixing n-pentanol with biodiesel
or diesel improves fuel performance, while decreasing regu-
lated emission species [14, 15]. Such benefits show promise
for reducing dependance on diesel fuel and help protect
the environment. Unlike regulated emissions, unregulated
emissions or polycyclic aromatic hydrocarbons (PAHs)
require more rigorous analytical chemistry techniques for
analysis, detection, and quantification. The International
Agency for Research on Cancer (IARC) and the United
States Environmental Protection Agency (EPA) identified
17 compounds as carcinogens; these are the PAHs discussed
in this study [16–18]. In addition, the formation of PAHs
causes excessive harm to the operation of the engine, such
as wetstacking. PAHs are pervasive environmental pollut-
ants created, for the most part, by poor combustion in diesel
engines. PAH formation is associated with cold burning as a
result of low load operation, as noted in the literature [19].
Yilmaz and Donaldson [20] reported that elevated PAH
emissions were observed as the equivalence ratio decreased
during low load operations and greater PAH emissions were
anticipated as the fuel/air ratio increased in the fuel-rich
region. In another study, high PAH production was found
in studying the combustion of coal and tire in a steady flow
reactor at various temperatures [21]. Such studies have con-
cluded that higher air consumption or reactor temperatures
lead to decreased PAH generation at the same equivalence
ratio. Therefore, for engine applications, wetstacking is
observed during low load operations and cold temperatures
[22, 23]. For these reasons, unregulated diesel emissions
must be investigated, especially while also assessing the via-
bility of alternative fuels.
In the literature, there are several studies investigating
the production of PAHs from biodiesel. Tsai et al. [24]
investigated the particle matter (PM) and PAH emissions
and showed that 20% biodiesel fuel blends reduced total-
PAHs, total-BaPeq, and PM, compared to diesel, irrespective
of engine load. Correa and Arbilla [25] conducted a PAH
emission study focusing on neat diesel and diesel/biodiesel
and stated that diesel/biodiesel reduced some PAHs. How-
ever, some other PAH compounds increased with biodiesel
addition, such as trimethyl benzene, phenanthrene, and
ethyl benzene. The evaluation of sustainably sourced, long-
chain, ether-oxygen additives in terms of regulated and
unregulated engine emissions was performed by Wu et al.
[26]. Long-chain ethers reduced gaseous PAH emissions by
25%-44%, particulate PAH emissions by 39%-67%, and
PAH toxicity was reduced by 32%-55%. The corpus of
research to date shows that alternative biofuels containing
oxygen in their molecule (such as FAMEs) can reduce PAHs
and PM emissions [27]. As previously mentioned, biodiesel
can be mixed with alcohols to eliminate their poor fuel prop-
erties and potentially reduce PAH emissions. However, stud-
ies in the literature on the emissions from blended
alternative fuels have primarily examined the regulated
emissions of such blends, while only a limited number of
studies have investigated the PAH formation which results
from use of biodiesel-alcohol mixtures. Guan et al. [28]
showed that diesel/biodiesel and diesel/biodiesel/ethanol
can decrease PM emissions and the total PAH concentration
at high and low engine loads. Furthermore, in the study of
Choi et al. [29], it was emphasized that as the use of oxy fuels
increases, they may increase the precursors of PAH forma-
tion (e.g., benzene or toluene) in diesel combustion. Yilmaz
and Davis studied PAH generation from biodiesel fuel
blends containing n-butanol, biodiesel, and diesel and
reported significant reduction in PAH emissions for biodie-
sel and blended fuels. It was also noted that the addition of
10% n-butanol (by volume) to biodiesel decreased PAHs;
however, rates above 10% led to increasing levels of PAHs
[30]. In another study, Yang et al. [31] found that fuel blends
containing a larger pentanol concentrations had less partic-
ulate phase PAH compounds and benzo[a]pyrene equivalent
in comparison to biodiesel.
In the current literature, there is insufficient information
on PAH emissions from combustion of biodiesel/alcohol
fuel blends, and it is necessary to fill the research gap on
the generation of PAHs and associated toxicity levels result-
ing from the utilization of oxy-fuels in diesel engines. The
purpose of this research is to examine aromatic-free biodie-
sel/n-pentanol fuel blends and evaluate their effects on HC,
CO, and NOx and distribution of PAH, PAH, concentration
in the exhaust and toxicity. Emphasis is placed on the forma-
tion of PAHs, high and low-ring PAH distributions and tox-
icity. The motivations for this focus are the significant
International Journal of Energy Research 3

Sampling line
Flow controller

Electronic scale Vacuum pump Exhaust gas analyzer

Test ... Absorbent resin

Fuel ...
... Fuel line cartridge
... Valve

Filter holder

Exhaust line

Thermocouple
Diesel engine
(Onan DJC)

Loading unit

Control panel

Figure 1: Engine test facility and PAH sampling.

repercussions on public health, nature, and engine failure Table 1: Test engine specifications.
(i.e., wetstacking) from PAHs.
Engine type Onan diesel generator
2. Materials and Methods Type DJC
Bore (mm) 82.55
2.1. Engine Test Conditions and Test Fuels. An Onan DJC Stroke (mm) 92.08
compression ignition engine was operated at 1800 rpm Displacement (cm3) 1970
(±1 rpm) with an electric load ranging from idle to 9 kW
Number of cylinders 4
(±0.005 kW). Details of the engine setup and specifications
can be found in Figure 1 and Table 1. Number of cycles 4 cycle
No. 2 diesel and n-pentanol (Amyl alcohol, m% ≥99.80, Compression ratio 19 : 1
CAS No. 74-41-0) and waste oil biodiesel were used as test Max output (kW) 12
fuel components. Waste oil biodiesel, sourced from dis- Max speed (rpm) 1800
carded cooking oil and compliant with ASTM D6751, was Intake system Natural aspirated
used in this study. Analysis of the biodiesel showed that its Fuel injection system Indirect
composition was 81.40% unsaturated fatty acids and
Injection pump type PSU model
13.28% saturated fatty acids, with the remaining content
being other fatty acid components. Biodiesel, diesel, and bio- Injection pressure (MPa) 13.1
diesel/n-pentanol test fuels with n-pentanol concentrations Injection timing (BTDC) 18 °CA
of 5% (low), 20% (medium), and 35% (high) (v/v) were eval-
uated as the test fuels. Two-fuel mixtures were prepared
using the splash blending method. The prepared binary mix- sample, tests were conducted in triplets for higher accuracy
tures were called BPen5 (95% Biodiesel+5% n-pentanol), and experimental confidence.
BPen20 (80% Biodiesel+20% n-pentanol), and BPen35
(65% Biodiesel+35% n-pentanol). 2.2. Sample Collection and Analysis of PAH Emissions. The
Table 2 lists the common properties of the test fuels. An rate of PAH sampling was 10 liters per minute (no dilution)
emission analyzer (model EMS 5002-5) was used to quantify for three hours at the idle mode. Filtering of exhaust samples
the NOx, CO, and HC content in the engine exhaust gas. utilized a multistep method; first, a 2 μm pore diameter poly-
Measurement ranges and resolution for these gas con- tetrafluoroethylene (PTFE) filter paper was used, followed by
stituents can be found in Table 3. For each experimental a 50 mg/100 mg Amberlite XAD-2 resin cartridge which was
4 International Journal of Energy Research

Table 2: Test fuel properties.

Fuel/ Density (g/ Lower heating value Cetane Kinematic viscosity (mm2/s) Flash point Cloud point CFPP
property ml) (Mj/kg) number at 40°C (°C) (°C) (°C)
Diesel 0.818 44.8 54 2.95 74 -12 -21
Biodiesel 0.855 40.5 52 4.57 126 -8.1 -13.2
n-Pentanol 0.815 34.94 20 2.89 49 — -40
BPen5 0.853 40.02 51.20 4.48 104.6 -9.3 -15.3
BPen20 0.847 39.43 45.60 4.17 98.7 -11.2 -17.6
BPen35 0.841 38.69 42.59 3.76 94.12 -12.5 -18.2

Table 3: Engine test facility ranges and resolutions.

Item Quantity Range Accuracy

Rotary encoder Speed 0-6000 rpm ±1 rpm
Loading unit (electrical resistance) Load 1000/5000 W ±5 W
HC 0–2000 ppm ±4 ppm
Exhaust gas analyzer CO 0–10 vol.% ±0.06 vol.%
NO 0–5000 ppm ±25 ppm

Table 4: GC-MS thermal program. mation in diesel engines [32]. In this context, the causes of
NOX emission examined in this study are based on the ther-
GC-MS: HP 5890/5971A
Instrument details mal (Zel’dovich) NOX mechanism. As shown in Figure 2,
Column: DB5-MS
NOX emissions increased with higher engine loads. On aver-
Injection volume 1 μL age, neat biodiesel produced 2.87% fewer NOX emissions
Injection temperature 300°C than neat diesel. n-Pentanol generates a cooling effect in
Hold 70° for 1 min the combustion chamber because of its latent heat of evapo-
ration (LHE) and lower heating value (LHV) values, which
Heat from 70-200°C at 70°C/min
lead to lower NOx emissions [33–35]. Biodiesel blends con-
Thermal program Hold 200°C for 2 min
taining n-pentanol at concentration of 5%, 20%, and 35%
Heat 200-300°C at 7 °C/min resulted in NOX emission reductions of 13.71%, 26.3%, and
Hold 200°C for 10 min 11.86%, respectively, when compared to neat biodiesel. The
ignition delay time is increased at higher loads, leading to
premixed combustion of which n-pentanol improves, result-
ing in a reduction of the cooling effect [36, 37]. Although the
targeted at the collection of more volatile species. An inter- ignition delay time is increased at higher loads, the residence
nal standard containing 2 μg anthracene (D10, 98%) was time is reduced at high temperatures, producing less NOX
added to each sample for isotope dilution mass spectrometry [6]. In addition, blends with higher oxygen contents result
(IDMS). High-performance liquid chromatography (HPLC) in lower flame temperatures in oxygen-rich zones [22].
grade hexane (5 mL) was used for extraction of PAHs. Overall, the biodiesel test fuel containing 20% n-pentanol
Washing of samples was performed with the addition of was the most successful at reducing NOX emissions. These
5 mL n-hexane and filtering through a 500 mg Na2SO4/ results concur with comparable testing found in literature
500 mg alumina column. A 1 : 1 mixture of HPLC grade ben- [38–40].
zene and acetonitrile was used to recover the washed sam-
ples, which were then concentrated using nitrogen 3.1.2. HC Emissions. It is seen in Figure 3 that neat biodiesel
blowdown. Each PAH was then identified and measured increased HC emissions by 25.37% compared to diesel. The
using GC-MS according to a selected ion monitoring dominating factors that contribute to HC emissions are fuel
(SIM) process (Table 4). properties, air-fuel ratio (AFR), fuel injection parameters,
and engine operating conditions [41]. Higher viscosity and
density cause the formation of lean zones during the premix
3. Results and Discussion combustion phase. The biodiesel/n-pentanol fuel blends
3.1. Regulated Emissions with n-pentanol concentrations of 5%, 20%, and 35%
increased average HC emissions by 5.42%, 6.22%, and
3.1.1. NOx Emissions. The thermal (Zel’dovich) NOX mech- 2.86%, respectively. The increase in HC emission results is
anism provides the most important effect on total NOX for- caused by incomplete combustion and higher oxygen
International Journal of Energy Research 5

700

600

NOx (ppm) 500

400

300

200

100

0
0 3 6 9
Engine load (kW)
D100 BPen20
B100 BPen35
BPen5

Figure 2: Correlation between NOx emissions and engine load for fuel blends.

6
HC (ppm)

2
0 3 6 9
Engine load (kW)

D100 BPen20
B100 BPen35
BPen5

Figure 3: Correlation between HC emissions and engine load for fuel blends.

content of the fuel blends [42, 43]. Of the test fuels, the 20%
n-pentanol concentration blend produced the highest HC
emissions. An elevation in temperature in the last phase of
combustion may be caused by greater n-pentanol concentra-
tions, leading to decreased HC emissions. Lower cetane
number and higher LHE of n-pentanol create a quenching
effect [44]. In addition, a long burning time can result in
higher HC emissions because it creates a weak outer flame
zone within the combustion chamber [45, 46].
3.1.3. CO Emissions. Multiple factors contribute to the pro-
duction of CO emissions including AFR and temperature
[30, 47–49]. Results shown in Figure 4 indicate that poor
air-fuel mixtures at low engine loads contribute to the pro-
duction of CO while lower production of CO at medium
loads can be attributed to more complete combustion. How-
ever, increased CO production at high loads is due to richer
fuel mixture zones [50]. Compared to diesel, neat biodiesel
produced an average of 39.63% high CO emissions.
6 International Journal of Energy Research

0.125

0.100

CO (%) 0.075

0.050

0.025

0.000
0 3 6 9
Engine load (kW)

D100 BPen20
B100 BPen35
BPen5

Figure 4: Correlation between CO emissions and engine load for fuel blends.

1.00

0.90
Relative concentration of aromatic rings (%)

0.80

0.70

0.60

0.50

0.40

0.30

0.20

0.10

0.00
D100 B100 BPen5 BPen20 BPen35

2 Rings 4 Rings
3 Rings 5+ Rings

Figure 5: Relative contribution of PAH by number of aromatic rings.

Increased CO emissions for biodiesel are caused by poor 35% n-pentanol fuel blend increased the formation of CO
atomization due to biodiesel’s high viscosity and density by 19.55%. Particularly at higher loads, CO formation
[30, 48, 51]. The low rate of evaporation of biodiesel/n-pen- increases because of the lower in-cylinder temperature [22].
tanol fuel blends with concentrations of 5% and 20% leads to
a high rate of CO oxidation to CO2 at high loads, causing a 3.2. Unregulated Emissions
cooling effect, as evidenced by the 17.97% and 3.49%
decrease in CO emissions, respectively. Similar tend CO 3.2.1. Distribution of PAHs. The 17 types of PAHs that this
emission trends have been reported in other studies investi- study is centered on are those recommended by the EPA [15].
gating higher alcohol fuel blends [47, 48, 52]. However, in Of the 17 PAHs, seven were below the detection limit, ace-
contrast to the 5% and 20% n-pentanol fuel blends, the naphthene, anthracene-D10, anthracene, benzo[b]fluoranthene,
International Journal of Energy Research 7

Table 5: Exhaust gas PAH concentration.

Total PAHs (μg/m3)

PAHs Number of rings
D100 B100 BPen5 BPen20 BPen35
Naphthalene 2 1.93 0.76 0.84 1.63 1.82
Acenaphthylene 2 0.21 0.25 0.55 0.83 0.90
Fluorene 2 0.59 0.22 0.15 0.14 0.12
Phenanthrene 3 1.19 0.66 0.23 0.01 0.02
Fluoranthene 3 0.29 0.18 0.08 0.03 0.00
Pyrene 4 0.40 0.31 0.06 0.01 0.01
Benzo[a]anthracene 4 0.00∗ 0.01 0.00∗ 0.00∗ 0.00∗
Chrysene 4 0.09 0.07 0.01 0.00∗ 0.01
Benzo[k]fluoranthene 4 0.00∗ 0.01 0.00∗ 0.00 0.00∗
Benzo[a]pyrene 5 0.01 0.00∗ 0.00∗ 0.00∗ 0.00∗
∗
Undetected.

5.00

4.50

4.00
Total PAH emissions (ug/m3)

3.50

3.00

2.50

2.00

1.50

1.00

0.50
0.00
D100 B100 BPen5 BPen20 BPen35

Figure 6: Total PAH emissions.

indeno[1,2,3-c,d]pyrene, dibenzo[a,h]anthracene, and benzo[-
g,h,i]perylene. As shown in Figure 5, PAHs from biodiesel/
n-pentanol fuel blends, biodiesel, and diesel primarily com-
prised of two-ring, three-ring, and four-ring aromatic struc-
tures. Biodiesel/n-pentanol fuel blends significantly decreased
the amount of the three- and four-ring aromatic compounds
compared to neat biodiesel, indicating that n-pentanol addi-
tion decreases both the total PAHs and the percentage of
high ring aromatic compounds [22]. Diesel was the only fuel
that produced a 5-ring PAH compound (see Table 5). Naph-
thalene, acenaphthylene, and acenaphthene, all low molecular
PAHs, were common to all test fuels. Phenanthrene and fluo-
ranthene, both medium molecular weight PAHs, were sec-
ondary compounds for diesel and biodiesel. Biodiesel/n-
pentanol blends produced only small amounts of fluoran-
thene and phenanthrene. Incorporation of engine oil to the
combustion process may contribute to the formation of these
PAHs, as well as boiling points and incomplete combustion
[53–55].
Diesel was the only test fuel to produce benxo[a]pyrene,
which is a heavy PAH and is of concern because heavy PAHs
have been linked to carcinogenic and teratogenic effects. It
has been noted in the literature that higher PAHs contribute
to engine failure [56]. The Type of PAHs produced and
reduction of higher ring PAHs should be prioritized along
with total PAH formation when investigating modes of die-
sel engine failure. n-Pentanol fuel blends decreased the gen-
eration of high ring PAHs, meaning that these fuel blends
exhibited optimal performance characteristics compared to
diesel or biodiesel in terms of their effects on engine lifecycle.
Heavier PAHs can condensate and form deposits on tight-
tolerance engine components, causing engine failure [30].
3.2.2. PAH Concentration in Exhaust Gas. Total PAH emis-
sions of the fuels are given in Figure 6, and their concentra-
tions are given in Table 5. According to Figure 6, the
maximum total PAH generation was observed in diesel
blends with a concentration of 4.73 μg/m3.
Lower molecular weight PAHs (naphthalene, acenaph-
thylene, etc.) are typically found in diesel fuel as a result of
diesel’s chemical structure; however, reactions that occur
during combustion produce higher-ring PAHs [19, 27, 28].
The formation of unsubstituted compounds and the genera-
tion of particles with greater aromatic content are promoted
8 International Journal of Energy Research

18.00
16.00
14.00
12.00

BaPeq (ng/m3) 10.00

8.00
6.00
4.00
2.00
0.00
D100 B100 BPen5 BPen20 BPen35

Figure 7: The toxicity distribution of test fuels.

Table 6: Toxicity BaPeq (ng/m3) concentration in exhaust.

Toxicity BaPeq (ng/m3)

PAHs Number of rings
D100 B100 BPen5 BPen20 BPen35
Acenaphthylene 2 0.211 0.246 0.555 0.933 0.999
Fluorene 2 0.593 0.223 0.153 0.137 0.199
Phenanthrene 3 1.194 0.660 0.227 0.015 0.062
Fluoranthene 3 0.288 0.180 0.082 0.000 0.000
Pyrene 4 0.403 0.305 0.065 0.032 0.099
Benzo[a]anthracene 4 0.000 0.919 0.000 0.006 0.010
Chrysene 4 0.094 0.065 0.011 0.004 0.014
Benzo[k]fluoranthene 4 0.046 0.077 0.000 0.000 0.000
Benzo[a]pyrene 5 13.378 0.000 0.000 0.000 0.000

at high temperatures [57–59]. Total PAH emissions are
heavily influenced by PAHs from the engine oil and fuel par-
ticipating in the combustion process and pyrosynthesis of
PAHs during combustion [60, 61]. Combustion is the pri-
mary source for the formation of higher molecular weight
PAHs. Lower molecular weight PAHs originate principally
from unburned fuel. Compared to diesel, biodiesel showed
a 48.02% reduction in total PAH emissions. Among 17 pri-
ority PAHs (Table 5), particularly pyrene, fluoranthene,
phenanthrene, fluorene, and naphthalene were noticeable
in this decrease. The excess oxygen and aromatic-free chem-
ical structure of biodiesel is the likely reason for the decrease
in PAH emissions. The chemical structure of biodiesel is
such that it does not innately contain aromatic components;
however, the combustion reactions can initiate PAH forma-
tion mechanisms, including Diels-Alder [57, 62]. Polyunsat-
urated fatty esters are easily affected by chemical reactions
related to the generation of PAHs [63]. In comparison to
biodiesel, BPen5 decreased the total PAH emission by
21.26%. Like biodiesel, n-pentanol lacks aromatic content,
but the aforementioned factors caused the formation of
PAHs in biodiesel-n-pentanol blends. However, with higher
n-pentanol concentrations, an increase of 7.93% and 17.03%
was recorded in total PAH emissions for BPen20 (2.66 μg/
m3) and BPen35 (2.88 μg/m3) fuels, respectively, compared
to biodiesel. Additional PAH accumulation may be caused
by engine lubricant residues from the prior cycle. This accu-
mulation is associated with the cooling of the in-cylinder
temperature resulting from the addition of alcohol with
higher LHE to the fuel blend. Additionally, low cetane num-
ber fuels with slow combustion and decreased adiabatic
flame temperature generate greater quantities of PAHs com-
pared to fuels that exhibit quicker combustion and larger
cetane numbers [64]. In view of various pathways for PAH
formation, exceedingly oxygen-rich conditions may have a
negative effect on combustion and lead to decreased chemi-
cal reactivity, which causes reordering of radicals in the igni-
tion zone and optimal radical formation for PAH occurrence
[53, 55]. Thus, parameters including oxygen content, cetane
number, and LHE significantly affect combustion perfor-
mance and formation of PAHs, as well as regulated emis-
sions. Overall, although blend ratios of n-pentanol
exceeding 20% elevated total PAHs in comparison to biodie-
sel, biodiesel-n-pentanol significantly reduced PAH emis-
sions and higher-ring PAHs as compared to diesel. The
optimal fuel that minimized total PAH production was
95% biodiesel and 5% n-pentanol.
3.2.3. Toxicity in PAH Emissions. The carcinogenicity of
PAH emissions is defined as toxic equivalent factor (TEF)
values. The weighted BaPeq (benzo[a]pyrene equivalent
(ng/m3)) of each aromatic compound is calculated based
International Journal of Energy Research
on the TEF [53, 64, 65]. The toxicity distribution of PAH
emissions is shown in Figure 7, and toxicity BaPeq (ng/m3)
concentration in exhaust is given in Table 6.
Acenaphthylene, fluorene, phenanthrene, pyrene, and
chrysene are measurable PAHs amongst all fuel blends.
The BaPeq toxicity due to using diesel fuel was determined
to be 16.20 ng/m3. This result means that diesel has the high-
est toxicity, measured in the five aromatic rings of Benzo[a]-
pyrene (13.37 ng/m3), which forms as a result of diesel fuel
between 300°C and 600°C and listed as a Group 1 carcinogen
by IARC [16, 18].
It is shown in Table 6 that most species measured in large
quantities (two and three aromatic rings) have minimal BaPeq
contribution. Because of the quantity and ordering of high-
ring PAHs, diesel is more hazardous than biodiesel in terms
of toxicity. The total BaPeq due to biodiesel (2.67 ng/m3) was
83.49% less than that due to diesel. Biodiesel is a renewable
fuel, but the combination of reactants that form at high tem-
peratures in the diesel engine combustion process can cause
toxicity [19, 30]. In comparison to biodiesel, toxicity was
reduced with BPen5 (1.09 ng/m3), BPen20 (1.12 ng/m3), and
BPen35 (1.38 ng/m3) fuels, 59.15%, 57.89, and 48.33%, respec-
tively. Overall, the total BaPeq was minimized by BPen5, while
all of the biodiesel-n-pentanol blends significantly reduced the
toxicity as compared to biodiesel and diesel.
4. Conclusions
For wide-range adoption of biodiesel and alcohol mixed
fuels, it is essential to examine such fuel combinations for
regulated emissions, as well as unregulated emissions for
low and high concentrations of n-pentanol. This investiga-
tion filled gaps in existing studies and reports the impact
of biodiesel-n-pentanol fuel mixtures on regulated pollut-
ants, total PAHs, toxicity, and the formation of specific rings
that cause wetstacking or engine failure. Biodiesel/n-penta-
nol fuel mixtures decreased NOX emissions as compared to
biodiesel due to a cooling effect caused by lower LHV and
higher LHE. With regard to unregulated emissions (i.e.,
PAHs), the following noteworthy outcomes have been
observed:
(i) The Diels-Alder PAH formation mechanism may
be caused by reactions that occur during combus-
tion despite the fact that biodiesel does not contain
aromatic components due to its chemical structure.
However, biodiesel and biodiesel-n-pentanol
blends, which are free of aromatic compounds, sig-
nificantly reduced the formation of PAHs, pointing
out the importance of the aromatic content of the
fuel
(ii) Of the 17 analyzed PAHs, three were below the
detection limit. BPen5 consisted of 80% two, 16%
three, and 4% four aromatic rings, BPen20 had
98% two and 2% three aromatic rings, and BPen35
had 98% two, 1% three, and 1% four aromatic rings
(iii) Compared to diesel fuel, biodiesel showed a 48.02%
reduction with total PAH emissions of 2.46 μg/m3.
9
The biodiesel/n-pentanol fuel blend with a 5% n-
pentanol concentration further decreased the total
PAH emission by 21.26%, making BPen5 the best
blended fuel in terms of minimizing total PAHs.
However, higher n-pentanol concentrations caused
7.93% and 17.03% increase in total PAH emissions
for BPen20 (2.66 μg/m3) and BPen35 (2.88 μg/m3)
fuels, respectively, as compared to biodiesel
(iv) There was a substantial decrease in toxicity for
BPen5 (1.09 ng/m3), BPen20 (1.12 ng/m3), and
BPen35 (1.38 ng/m3) fuels, 59.15%, 57.89, and
48.33%, respectively. BPen5 showed the best reduc-
tion among the mixtures not only in total PAH
emissions but also in toxicity as compared to all
fuels
Overall, biodiesel/n-pentanol blends significantly
reduced total PAHs, toxicity, and the higher-ring PAHs,
making such blends advantageous over diesel for human
health, the environment, and engine operation at low load
or cold operating conditions.
Data Availability
The data used to support the findings of this study are avail-
able from the corresponding author upon request.
Conflicts of Interest
The authors declare that they have no conflicts of interest.
References
[1] P. Singh, C. S. R. Varun, and N. Kumar, “A review on method-
ology for complete elimination of diesel from CI engines using
mixed feedstock,” Renewable and Sustainable Energy Reviews,
vol. 57, pp. 1110–1125, 2016.
[2] B. L. Salvi, K. A. Subramanian, and N. L. Panwar, “Alternative
fuels for transportation vehicles: a technical review,” Renew-
able and Sustainable Energy Reviews, vol. 25, pp. 404–419,
2013.
[3] D. Singh, D. Sharma, S. L. Soni et al., “A comprehensive review
of biodiesel production from waste cooking oil and its use as
fuel in compression ignition engines: 3rd generation cleaner
feedstock,” Journal of Cleaner Production, vol. 307,
p. 127299, 2021.
[4] P. Tamilselvan, N. Nallusamy, and S. Rajkumar, “A compre-
hensive review on performance, combustion and emission
characteristics of biodiesel fuelled diesel engines,” Renewable
and Sustainable Energy Reviews, vol. 79, pp. 1134–1159, 2017.
[5] J. M. Bergthorson and M. J. Thomson, “A review of the com-
bustion and emissions properties of advanced transportation
biofuels and their impact on existing and future engines,”
Renewable and Sustainable Energy Reviews, vol. 42,
pp. 1393–1417, 2015.
[6] B. R. Kumar, S. Saravanan, D. Ranad, and A. Nagendran, “Use
of some advanced biofuels for overcoming smoke/NOx trade-
off in a light-duty DI diesel engine,” Renewable Energy,
vol. 96, pp. 687–699, 2016.
10
[7] M. Lapuerta, O. Armas, and J. Rodríguez-Fernández, “Effect of
biodiesel fuels on diesel engine emissions,” Progress in energy
and combustion science, vol. 34, no. 2, pp. 198–223, 2008.
[8] B. R. Kumar and S. Saravanan, “Use of higher alcohol biofuels
in diesel engines: a review,” Renewable and Sustainable Energy
Reviews, vol. 31, no. 60, pp. 84–115, 2016.
[9] N. Yilmaz, A. Atmanli, M. J. Hall, and F. M. Vigil, “Determina-
tion of the optimum blend ratio of diesel, waste oil derived bio-
diesel and 1-pentanol using the response surface method,”
Energies, vol. 15, no. 14, p. 5144, 2022.
[10] Y. Di, C. S. Cheung, and Z. Huang, “Experimental investiga-
tion on regulated and unregulated emissions of a diesel engine
fueled with ultra-low sulfur diesel fuel blended with biodiesel
from waste cooking oil,” Science of the Total Environment,
vol. 407, no. 2, pp. 835–846, 2009.
[11] B. M. Vinod, M. K. Madhu, and R. G. Amba Prasad, “Butanol
and pentanol: the promising biofuels for CI engines - a
review,” Renewable and Sustainable Energy Reviews, vol. 78,
pp. 1068–1088, 2017.
[12] N. Yilmaz and B. Donaldson, “Modeling of Chemical Pro-
cesses in a Diesel Engine With Alcohol Fuels,” ASME. J. Energy
Resources Technology, vol. 129, no. 4, pp. 355–359, 2007.
[13] W. Zhao, J. Yan, S. Gao, T. H. Lee, and X. Li, “The combustion
and emission characteristics of a common-rail diesel engine
fueled with diesel, propanol, and pentanol blends under low
intake pressures,” Fuel, vol. 307, article 121692, 2022.
[14] A. K. Agarwal, “Biofuels (alcohols and biodiesel) applications
as fuels for internal combustion engines,” Progress in energy
and combustion science, vol. 33, no. 3, pp. 233–271, 2007.
[15] A. Datta and B. K. Mandal, “Engine performance, combustion
and emission characteristics of a compression ignition engine
operating on different biodiesel-alcohol blends,” Energy,
vol. 125, pp. 470–483, 2017.
[16] L. A. Courter, A. Luch, T. Musafia-Jeknic et al., “The influence
of diesel exhaust on polycyclic aromatic hydrocarbon-induced
DNA damage, gene expression, and tumor initiation in Sencar
mice in vivo,” Cancer Letters, vol. 265, no. 1, pp. 135–147, 2008.
[17] US Department of Health and Human Services Public Health
Service, Toxicological Profile for Polycyclic Aromatic Hydrocar-
bons, Atlanta, Georgia, 1995.
[18] US EPA, Provisional Guidance for Quantitative Risk Assess-
ment of Polycyclic Aromatic Hydrocarbons (PAH), US Envi-
ronmental Protection Agency, Office of Research and
Development, Office of Health and Environmental Assess-
ment, Washington, DC, 1993.
[19] N. Yilmaz and A. B. Donaldson, “Evidence of PAH production
under lean combustion conditions,” Fuel, vol. 86, no. 15,
pp. 2377–2382, 2007.
[20] N. Yilmaz and A. Burl Donaldson, “Experimental and compu-
tational investigation of PAH production in a diesel engine as a
function of load,” in SAE Technical Paper 2006, vol. 1, p. 1977,
USA, 2006.
[21] Y. A. Levendis, A. Atal, and J. B. Carlson, “On the correlation
of CO and PAH emissions from the combustion of pulverized
coal and waste tires,” Environmental Science & Technology,
vol. 32, no. 23, pp. 3767–3777, 1998.
[22] N. Yilmaz, F. M. Vigil, and B. Donaldson, “Fuel effects on PAH
formation, toxicity and regulated pollutants: detailed compar-
ison of biodiesel blends with propanol, butanol and pentanol,”
Science of the Total Environment, vol. 849, article 157839,
2022.
International Journal of Energy Research
[23] N. Yilmaz, F. M. Vigil, A. Atmanli, and B. Donaldson,
“Detailed analysis of PAH formation, toxicity and regulated
pollutants in a diesel engine running on diesel blends with n-
propanol, n-butanol and n-pentanol,” Energies, vol. 15,
no. 17, p. 6487, 2022.
[24] J. H. Tsai, S. J. Chen, K. L. Huang et al., “PM, carbon, PAH, and
particle-extract-induced cytotoxicity of emissions from a die-
sel generator fueled with waste-edible-oil-biodiesel,” Aerosol
and Air Quality Research, vol. 12, no. 5, pp. 843–855, 2012.
[25] S. M. Correa and G. Arbilla, “Aromatic hydrocarbons emis-
sions in diesel and biodiesel exhaust,” Atmospheric Environ-
ment, vol. 40, no. 35, pp. 6821–6826, 2006.
[26] S. Wu, J. Bao, Z. Wang, H. Zhang, and R. Xiao, “The regulated
emissions and PAH emissions of bio-based long-chain ethers
in a diesel engine,” Fuel Processing Technology, vol. 214, article
106724, 2021.
[27] I. Sadiktsis, H. J. Koegler, T. Benham, C. Bergvall, and
R. Westerholm, “Particulate associated polycyclic aromatic
hydrocarbon exhaust emissions from a portable power gener-
ator fueled with three different fuels - a comparison between
petroleum diesel and two biodiesels,” Fuel, vol. 115, pp. 573–
580, 2014.
[28] C. Guan, C. S. Cheung, X. Li, and Z. Huang, “Effects of oxygen-
ated fuels on the particle-phase compounds emitted from a
diesel engine,” Atmospheric Pollution Research, vol. 8, no. 2,
pp. 209–220, 2017.
[29] B. Choi, X. Jiang, Y. K. Kim et al., “Effect of diesel fuel blend
with n-butanol on the emission of a turbocharged common
rail direct injection diesel engine,” Applied Energy, vol. 146,
pp. 20–28, 2015.
[30] N. Yilmaz and S. M. Davis, “Polycyclic aromatic hydrocarbon
(PAH) formation in a diesel engine fueled with diesel, biodiesel
and biodiesel/n-butanol blends,” Fuel, vol. 181, pp. 729–740, 2016.
[31] K. Yang, L. Wei, C. S. Cheung, C. Tang, and Z. Huang, “The
effect of pentanol addition on the particulate emission charac-
teristics of a biodiesel operated diesel engine,” Fuel, vol. 209,
pp. 132–140, 2017.
[32] N. Yilmaz and M. Ukaoma, “Impact of biodiesel and propanol
blends on engine performance, regulated emissions and PAH
formation,” International Journal of Energy Research, vol. 46,
no. 15, pp. 23433–23448, 2022.
[33] H. Chen, B. Xie, J. Ma, and Y. Chen, “NOx emission of biodie-
sel compared to diesel: higher or lower?,” Applied Thermal
Engineering, vol. 37, pp. 584–593, 2018.
[34] S. M. Palash, M. A. Kalam, H. H. Masjuki, B. M. Masum, I. M.
Rizwanul Fattah, and M. Mofijur, “Impacts of biodiesel com-
bustion on NO _x_ emissions and their reduction approaches,”
Renewable and Sustainable Energy Reviews, vol. 23, pp. 473–
490, 2013.
[35] N. Yilmaz and B. Donaldson, “Combined effects of engine
characteristics and fuel aromatic content on polycyclic aro-
matic hydrocarbons and toxicity,” Energy Sources, Part A:
Recovery, Utilization, and Environmental Effects, vol. 44,
no. 4, pp. 9156–9171, 2022.
[36] M. Nabi, “Theoretical investigation of engine thermal effi-
ciency, adiabatic flame temperature, NO _x_ emission and
combustion-related parameters for different oxygenated
fuels,” Applied Thermal Engineering, vol. 30, no. 8-9,
pp. 839–844, 2010.
[37] N. Yilmaz, F. M. Vigil, and B. Donaldson, “Effect of diesel and
propanol blends on regulated pollutants and polycyclic
International Journal of Energy Research
aromatic hydrocarbons under lean combustion conditions,”
Environmental Progress & Sustainable Energy, vol. 42, no. 2,
article e14020, 2022.
[38] D. Babu and R. Anand, “Effect of biodiesel-diesel- _n_ -penta-
nol and biodiesel-diesel- _n_ -hexanol blends on diesel engine
emission and combustion characteristics,” Energy, vol. 133,
pp. 761–776, 2017.
[39] K. Nanthagopal, B. Ashok, B. Saravanan, D. Patel,
B. Sudarshan, and R. Aaditya Ramasamy, “An assessment on
the effects of 1-pentanol and 1-butanol as additives with Calo-
phyllum inophyllum biodiesel,” Energy Conversion and Man-
agement, vol. 158, pp. 70–80, 2018.
[40] N. Yilmaz, A. Atmanli, and M. Trujillo, “Influence of 1-
pentanol additive on the performance of a diesel engine fueled
with waste oil methyl ester and diesel fuel,” Fuel, vol. 207,
pp. 461–469, 2017.
[41] N. Yilmaz, E. Ileri, and A. Atmanli, “Performance of biodiesel/
higher alcohols blends in a diesel engine,” International Jour-
nal of Energy Research, vol. 40, no. 8, pp. 1134–1143, 2016.
[42] F. Payri, V. R. Bermudez, B. Tormos, and W. G. Linares,
“Hydrocarbon emissions speciation in diesel and biodiesel
exhausts,” Atmospheric Environment, vol. 43, no. 6,
pp. 1273–1279, 2009.
[43] N. Yilmaz, F. M. Vigil, and B. Donaldson, “Effect of n-butanol
addition to diesel fuel on reduction of PAH formation and reg-
ulated pollutants,” Polycyclic Aromatic Compounds, pp. 1–15,
2022.
[44] N. Yilmaz, A. Donaldson, and A. Johns, “Some perspectives on
alcohol utilization in a compression ignition engine,” SAE Inter-
national Journal of Fuels and Lubricants, vol. 1, p. 3135, 2005.
[45] A. Atmanli, “Comparative analyses of diesel-waste oil biodiesel
and propanol, n-butanol or 1-pentanol blends in a diesel
engine,” Fuel, vol. 176, pp. 209–215, 2016.
[46] L. Zhua, Y. Xiaob, C. S. Cheungb, C. Guana, and Z. Huang,
“Combustion, gaseous and particulate emission of a diesel
engine fueled with n-pentanol (C5 alcohol) blended with waste
cooking oil biodiesel,” Applied Thermal Engineering, vol. 102,
pp. 73–79, 2016.
[47] L. Li, J. Wang, Z. Wang, and J. Xiao, “Combustion and emis-
sion characteristics of diesel engine fueled with diesel/biodie-
sel/pentanol fuel blends,” Fuel, vol. 156, pp. 211–218, 2015.
[48] Y. Ma, R. Huang, S. Huang, Y. Zhang, S. Xu, and Z. Wang,
“Experimental investigation on the effect of n-pentanol blend-
ing on spray, ignition and combustion characteristics of waste
cooking oil biodiesel,” Energy Conversion and Management,
vol. 148, pp. 440–455, 2017.
[49] N. Yilmaz and S. M. Davis, “Diesel blends with high concen-
trations of biodiesel and n-butanol: effects on regulated pollut-
ants and polycyclic aromatic hydrocarbons,” Process Safety
and Environmental Protection, vol. 166, pp. 430–439, 2022.
[50] A. Atmanli and N. Yilmaz, “Comparative assessment of differ-
ent diesel engines fueled with 1-pentanol and diesel blends,”
Environmental Progress & Sustainable Energy, vol. 40, no. 5,
p. e13663, 2021.
[51] N. Yilmaz and S. M. Davis, “Formation of polycyclic aromatic
hydrocarbons and regulated emissions from biodiesel and n-
butanol blends containing water,” Journal of Hazardous Mate-
rials, vol. 437, p. 129360, 2022.
[52] M. Channappagoudra, K. Ramesh, and G. Manavendra,
“Comparative study of standard engine and modified engine
11
with different piston bowl geometries operated with B20 fuel
blend,” Renewable energy, vol. 133, pp. 216–232, 2019.
[53] G. Karavalakis, V. Boutsika, S. Stournas, and E. Bakeas, “Bio-
diesel emissions profile in modern diesel vehicles. Part 2: effect
of biodiesel origin on carbonyl, PAH, nitro-PAH and oxy-
PAH emissions,” Science of the Total Environment, vol. 409,
no. 4, pp. 738–747, 2011.
[54] Y. C. Lin, W. J. Lee, and H. C. Hou, “PAH emissions and
energy efficiency of palm-biodiesel blends fueled on diesel gen-
erator,” Atmospheric Environment, vol. 40, no. 21, pp. 3930–
3940, 2006.
[55] K. Phoungthong, S. Tekasakul, P. Tekasakul, and M. Furuuchi,
“Comparison of particulate matter and polycyclic aromatic
hydrocarbons in emissions from IDI-turbo diesel engine
fueled by palm oil-diesel blends during long-term usage,”
Atmospheric Pollution Research, vol. 8, no. 2, pp. 344–350,
2017.
[56] N. Yilmaz and A. B. Donaldson, Examination of causes of wet-
stacking in diesel engines, SAE Technical Papers, 2005.
[57] J. G. Ge, H. Y. Kim, S. K. Yoon, and N. J. Choi, “Reducing vol-
atile organic compound emissions from diesel engines using
canola oil biodiesel fuel and blends,” Fuel, vol. 218, pp. 266–
274, 2018.
[58] G. Karavalakis, G. Fontaras, D. Ampatzoglou et al., “Effects of
low concentration biodiesel blends application on modern
passenger cars. Part 3: impact on PAH, nitro-PAH, and oxy-
PAH emissions,” Environmental Pollution, vol. 158, no. 5,
pp. 1584–1594, 2010.
[59] N. Yilmaz, A. Atmanli, F. M. Vigil, and B. Donaldson, “Com-
parative assessment of polycyclic aromatic hydrocarbons and
toxicity in a diesel engine powered by diesel and biodiesel
blends with high concentrations of alcohols,” Energies,
vol. 15, no. 22, p. 8523, 2022.
[60] G. Karavalakis, G. Dedes, E. Bakeas, G. Fontaras, S. Stournas,
and Z. Samaras, The effect of biodiesel on PAHs, nitro-PAHs,
and oxy-PAHs emissions from a light vehicle operated over
the European and the Artemis driving cycles, SAE Technical
Paper, 2009.
[61] Y. C. Lin, T. Y. Wu, W. C. Ou-Yang, and C. B. Chen, “Reduc-
ing emissions of carbonyl compounds and regulated harmful
matters from a heavy-duty diesel engine fueled with paraf-
finic/biodiesel blends at one low load steady-state condition,”
Atmospheric Environment, vol. 43, no. 16, pp. 2642–2647,
2009.
[62] G. Karavalakis, G. Deves, G. Fontaras, S. Stournas, Z. Samaras,
and E. Bakeas, “The impact of soy-based biodiesel on PAH,
nitro-PAH and oxy-PAH emissions from a passenger car
operated over regulated and nonregulated driving cycles,”
Fuel, vol. 89, no. 12, pp. 3876–3883, 2010.
[63] P. Tan, Y. Zhong, Z. Hu, and D. M. Lou, “Size distributions,
PAHs and inorganic ions of exhaust particles from a heavy
duty diesel engine using B20 biodiesel with different exhaust
aftertreatments,” Energy, vol. 141, pp. 898–906, 2017.
[64] E. B. Bakeas and G. Karavalakis, “Regulated, carbonyl and
polycyclic aromatic hydrocarbon emissions from a light-duty
vehicle fueled with diesel and biodiesel blends,” Environmental
Science-Processes & Impacts, vol. 15, no. 2, pp. 412–422, 2013.
[65] N. Yilmaz, M. Rafiei, and B. Donaldson, “Effect of diesel and
pentanol blends on PAH formation and regulated pollutants,”
Biofuels, vol. 14, no. 3, pp. 293–301, 2023.