Article

pubs.acs.org/est

The Eects of Neat Biodiesel and Biodiesel and HVO Blends in Diesel
Fuel on Exhaust Emissions from a Light Duty Vehicle with a Diesel
Engine
Adam Prokopowicz,*, Marzena Zaciera, Andrzej Sobczak,, Piotr Bielaczyc, and Joseph Woodburn

Institute of Occupational Medicine and Environmental Health, Koscielna 13, 41-200 Sosnowiec, Poland
School of Pharmacy with Division of Laboratory Medicine in Sosnowiec, Medical University of Silesia, Poniatowskiego 15, 40-055
Katowice, Poland

BOSMAL Automotive Research and Development Institute Ltd, Sarni Stok 93, 43-300 Bielsko-Biala, Poland

S Supporting Information
*

ABSTRACT: The inuence of fatty acid methyl esters (FAME) and

hydrotreated vegetable oil (HVO) diesel blends on the exhaust emissions
from a passenger car was examined. The impact of FAME for the cold
urban phase (UDC) was increased CO and HC emissions, probably due
to blend physical properties promoting incomplete combustion. The
HVO blend caused the lowest CO and HC emissions for the UDC. NOx
emissions did not change signicantly with the fuel used, however the
UDC was characterized by lower NOx emission for FAME blends.
Particle emissions were highest with standard diesel. Emissions of
carbonyl compounds increased as fuel biodiesel content increased,
especially during the UDC. HVO in diesel fuel decreased carbonyl
emissions. Formaldehyde and acetaldehyde were the most abundant
carbonyl compounds in the exhaust gas. Total particle-bound PAH
emissions were variable, the emission of heavier PAHs increased with
blend biodiesel content. The HVO blend increased emission of lighter PAHs. Nitro-PAHs were identied only during the UDC
and not for all blends; the highest emissions were measured for pure diesel. The results showed that emission of nitro-PAHs may
be decreased to a greater extent by using biodiesel than using a HVO blend.

consumption needs.4,5 The transesterication process decreases

the viscosity and increases the cetane number and heating value
in comparison to the feedstock, so FAMEs properties do not
dier signicantly from petroleum diesel fuel, and may be used
in unmodied diesel engines. However, the high percentage of
unsaturated bonds in the fatty acids structure causes biodiesel
to be more prone to oxidation compared to diesel, which
decreases its long-term stability properties. Much research has
indicated that their addition to diesel fuel reduces the toxicity of
exhaust emissions by lowering the emission of particulate
matter, carbon monoxide, and total hydrocarbons, although
some increase in emission of nitrogen oxides is observed.69
Hydrotreated vegetable oil (HVO) is another renewable fuel
for diesel engines, which is produced from vegetable oils and
composed mainly of liquid paranic hydrocarbons. A pathway
to their production is conventional hydrotreating catalysis, in
which hydrogen is used to remove oxygen atoms and double
bonds from the structure of triglicerides. The physical and

INTRODUCTION
In the past decade interest in usage of renewable fuels has
increased sharply, due to limited fossil fuel resources and the
opportunity to reduce greenhouse gas emissions. This also
involves transport fuels, which for example, in the EU, have the
highest contribution to general energy consumption (about
40%) and of which 56% originate from renewable sources.1 In
the case of diesel engines, commonly used both in heavy
transportation vehicles and passenger cars, fatty acid methyl
esters (FAMEs), known as biodiesel, are the main biocomponents which are blended and used with conventional petroleum
diesel fuel.2 FAMEs are produced mainly by transestrication of
vegetable oils such as soybean, rapeseed, and palm oils with
glycerol as a byproduct in an alkali-catalyzed process.3 Although
methanol and ethanol are most frequently used as a alcohol, the
former is mainly employed because of its low cost and
physicochemical advantages but, in contrast to ethanol,
methanol originates mostly from fossil feedstock. Production
may lead to the presence of some catalyst poisons in biodiesel,
like Na, K, or P. The fats for FAME production also may
originate from postfrying oils, waste animal fats, or microalgae
oil, which fulll the greenhouse gas emission criteria better than
edible vegetable oils and do not compete with food
2015 American Chemical Society

Received:
Revised:
Accepted:
Published:
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February 5, 2015
April 30, 2015
May 20, 2015
May 20, 2015
DOI: 10.1021/acs.est.5b00648
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Table 1. Main Physicochemical Properties of the Test Fuelsa
fuel parameter
density at 15 C (kg/dm3)
viscosity at 40 C (mm2s)
ash point (C)
sulfur content (ppm)
cetane number
water content (ppm)
CFPP C
E250 (evaporated at 250 C)
[% v/v]
E350 (evaporated at 350 C)
(% v/v)
T95(95% vol. evaporated at)
(C)
LHV (MJ/kg)
PAHs (% m/m)
a

B0 (100%
DF)

B7 (93.1% DF + 6.9%
FAME)

B15 (85% DF + 15%

FAME)

B30 (70% DF + 30%

FAME)

B100(100%
FAME)

HVO30 (70% DF +
30% HVO)

0.836
2.632
59.5
8.0
55.2
70
28
38.7

0.838
2.637
61.0
7.1
52.5
82
27
41.1

0.842

0.847

0.816
2.737

25

17

0.875
4.64
178
6.0
56.1
350
8

98.8

95.7

339.8

347.5

42.6
3.0

37.0

42.9

2.2

17

DF, diesel fuel; FAME, fatty acid methyl esters; HVO, hydrotreated vegetable oil.

condition, which may change the emission prole of most

harmful pollutants, probably due to the higher viscosity and
lower volatility of biodiesel in comparison to conventional
diesel fuel. Concerning paranic fuels, it was observed that
emission of formaldehyde and PAHs can decrease with this
fuel.16,19
Diesel engine operation is very sensitive to fuel properties;
crucially, a number of physical properties change when
biodiesel or paranic fuel are added to diesel fuel. Thus,
changes in emissions may not be just due to the change in
chemical composition, but also to changes in other properties
such as density, volatility, and cetane number.20
The purpose of the present study was a comparison of
regulated and unregulated (carbonyl, PAH and nitro-PAH
compounds) emissions in relation to fuels containing dierent
proportions of FAMEs and HVO in diesel fuel. The European
legislative NEDC test cycle (Supporting Information page S3),
introduced in Directive 98/69/EC, was selected as a
representative test for this study. The emission tests were
performed on a chassis dynamometer and conducted on a
passenger car equipped with a modern direct injection
turbocharged diesel engine meeting Euro 4 emission standards.

functional properties of this fuel are very comparable to

petroleum diesel fuel so their importance increases, including
the possibility of usage as aviation fuel.10 However, aside from
cold ow properties, which may be improved by alkane
isomerization, due to its low lubricity and high cetane number it
is not recommend to use HVO blends with concentrations
above 50% in diesel fuel.11 The sooting reduction tendency
observed in the same study indicated potential reductions in
particulate matter (PM) emissions in most recent model year
vehicles.
The toxicity of exhaust emission and changes in the prole of
emitted pollutants when using renewable fuels is a very
important issue, due to the inuence on air pollution and the
attending possible health eects. Diesel engine exhaust consists
of many toxic compounds and has been classied in group 1,
according to IARC, as carcinogenic to humans.12 Despite many
studies which concern the emissions prole using biodiesel,
most of them were conducted with test engines under steady
state driving condition, and not on in-use cars, operating with
exhaust after treatment devices over transient cycles, for
example the New European Driving Cycle (NEDC). A recent
investigation indicated a marginal increase in HC, CO, and PM
emission under these conditions, due to certain physical
properties of biodiesel blends and cold-start occurring in the
cycle.13 However, previous studies showed signicant increases
in CO, HC, and even PM when using biodiesel blends and pure
biodiesel, which was explained by higher viscosity and lower
volatility of these fuels in comparison to conventional diesel
fuel.14,15 In turn, usage of paranic biofuels caused reductions
of emissions of these pollutants under similar test conditions.16
There are, however, growing concerns regarding unregulated
pollutants emitted from diesel engines, which mostly include
carbonyl compounds, polycyclic aromatic hydrocarbons
(PAHs), and their nitrated derivatives (nitro-PAHs). Recent
studies have reported increasing carbonyl compound emissions
with increased biodiesel content in the diesel fuel, which is in
agreement with the majority of investigations conducted in
engine test cells.17,18 In turn, the emission of PAHs was shifted
toward lighter PAH compounds and was clearly dependent on
the feedstock origin for FAME production, showing that
oxidized fuel increased emissions of some PAHs and nitroPAHs compared to when using standard diesel fuel.13
Moreover, these emissions were aected by the cold-start

MATERIAL AND METHODS

The experiment was carried out on midsize passenger car of
European manufacture, produced in 2009 and with a
compression ignition engine of displacement 1920 cm3. The
vehicles engine also featured typical technology for a Euro 4
diesel passenger car: a turbocharger, cooled exhaust gas
recirculation controlled by an air ow meter, and a commonrail fuel injection system with high-pressure injectors. A diesel
particulate lter was not present, but an oxidation catalyst was
tted, again, typical for a Diesel car meeting the Euro 4
standard. The emission tests were carried out in BOSMALs
Emission Testing Laboratory using an AVL48 single roll
chassis dynamometer. This chassis dynamometer is situated
within a climatic chamber (Supporting Information Figure S1).
As per the European legislative test method, the test
commenced from a cold start at a temperature of 20 C to
30 C (24 C was targeted) with the oil, coolant and all
elements of the engine at ambient temperature (24 C 2 C).
The vehicle speed versus time plot for the NEDC is presented
in the Supporting Information in Figure S2. Each test on each
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Figure 1. Relative emissions of CO, HC, NOx, PM, CO2, and absolute values of fuel consumption for the fuels tested. * p < 0.05.

A HORIBA CVS 7400S system with a full-ow dilution

tunnel and DLS 7100EPM sampling system, a set of HORIBA
MEXA HTRLE and the HORIBA VETS7000NT management
system were all used to measure exhaust emission levels.21 An
average dilution ratio of 1:20 and 1:10 was used during UDC
and EUDC phases, respectively. Fuel consumption was
calculated by the carbon balance method.

blend was performed in triplicate. Six dierent fuels were used,

whose general compositions and densities with some others
parameters are listed in Table 1. Pure petroleum diesel fuel,
neat rapeseed methyl ester (RME) and B7 were purchased
from PKN ORLEN. Pure HVO produced using NExBTL
technology was obtained from Neste Oil Oyj. In addition,
conventional diesel was blended to obtain the remaining fuels
(B15, B30, HVO30).
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Table 2. Regulated emissions over the NEDC (UDC + EUDC)a
emissions (mg/km)
NEDC

CO2 emission (g/km)

UDC

EUDC

fuel

CO

NOx

HC

PM

CO

NOx

HC

PM

CO

NOx

HC

PM

NEDC

UDC

EUDC

B0
B7
B15
B30
B100
HVO30

121
159
145
167
426
59

221
211
219
220
211
224

30
36
40
45
97
25

33
29
29
26
16
30

323
428
391
448
1152
154

257
234
241
249
206
266

69
83
90
103
246
51

34
32
27
25
31
30

4
4
4
4
4
5

201
197
207
204
213
200

8
8
11
12
10
10

33
27
31
26
8
31

162.8
164.3
161.4
163.4
169.7
161.9

214.0
212.1
207.9
211.3
226.9
207.3

133.4
136.7
134.6
135.7
136.6
135.6

Euro 4 limits (mg/km): CO 500; NOx 250; (NOx+HC) 300; PM 25.

a near-linear relationship between this reduction and the

increase in the H/C ratio of the fuel. However, the main reason
for the observed reduction is probably the lower boiling point,
which has a benecial impact on complete vaporization of the
fuel in the combustion chamber at low load and cold start
conditions.11In turn, Lim et al. indentied the increased cetane
number with HVO addition to diesel fuel as an important factor
for reducing the CO emission level.30During the EUDC phase,
emissions of CO were at a very low level, due to the high
eectiveness of the vehicles diesel oxidation catalyst at
removing CO, and comparable for all tested fuels. No
reductions in CO emissions during the EUDC phase were
observed for any of the fuels containing FAME, nor for HVO
blend.
A similar tendency as for CO emission was observed for total
HC emissions, which were also the highest in the case of B100
in the UDC phase. In reference to conventional diesel fuel, a
signicant increase occurred also for B30, but for the other
biodiesel blends, the increase in HC emissions was only
marginally signicant. As reported previously, benzene was the
most abundant among the light aromatic hydrocarbons, and
benzene emissions showed a similar trend to that of total HC.31
This trend was especially visible during the UDC phase and it is
undoubtedly the result of the cold start conditions and the
physicochemical parameters of fuels containing FAME. Diesel
engine cold start is aected by many interacting processes
during mixture formation inside the cylinder that lead to
autoignition and combustion. Emissions during DI diesel
engine cold-start and warm up are signicant for overall
emissions, (however not as signicant as in a spark-ignition
engine), since the conditions for fuel atomization, mixture
formation and combustion are poor.32 Moreover, aftertreatment devices (e.g., an oxidizing catalyst) do not work eectively
under these conditions. A previous investigation concerning
HC emissions when using standard diesel fuel indicated that
during the rst of the four elementary phases of the UDC, this
emission is 100150% higher than during the last elementary
phase of the UDC.33 Poorer atomization and vaporization due
to the higher density, viscosity and boiling point of FAME and
its blends than for pure petroleum diesel fuel lead to an increase
in HC emissions during the UDC, which during the following
EUDC phase did not show such a signicant dierentiation
(only for B30, marginally). As discussed by Giacoumis and coworkers,9 a diesel oxidation catalyst may seem to operate less
eciently with biodiesel and biodiesel blends not only under
cold conditions, but also throughout the whole cycle. The
reason for this behavior is the lower biodiesel exhaust gas
temperature causing lower available exhaust gas thermal energy.
It was evident that HC emissions decreased for the HVO30

Carbonyl compounds in the engine exhaust gas were

determined using 2,4-dinitrophenylhydrazine (2,4-DNPH)
method after collection of diluted exhaust in Tedlar bags.
Particle bound PAHs and nitro-PAHs collected onto Pallex
(T60A20) lters were determined by HPLC with uorescence
detection and GC-MS method, respectively.14,15
Methodological details and QA/QC data including recoveries, precision and accuracy for carbonyl, PAH and nitro-PAH
compounds are presented in the Supporting Information,
(pages S3S4 and Table S1).
t test analyses were used to assess dierences in emission
results. P values <0.05 were considered statistically signicant.

RESULTS AND DISCUSSION

The emission results of three biodiesel blends, as well as neat
biodiesel and the HVO blend were related to petroleum diesel
fuel and presented in Figure 1 as mean values with standard
errors. The gures show the results for both phases, that is, the
UDC and the EUDC, as well as for the complete NEDC cycle
(UDC+EUDC). Additionally, Figure 1 shows the fuel
consumption during all cycles. Measured emission values are
listed in Table 2.
For the vehicle under test, the addition of FAMEs to the fuel
lead to an increase in CO emissions during the UDC phase.
The increase was particularly evident for neat biodiesel, for
which the level was over three times that of conventional diesel
fuel. This was probably the result of poor atomization and
vaporization of fuels containing FAMEs during cold-start and
engine warm up, due to their higher viscosity and density in
comparison to diesel fuel. This trend is in contrast to most
investigations, which used steady-state conditions,2428
although the opposite trend has also been observed.29
Reduction of CO emission was explained mainly by the oxygen
content of ester molecules and the more complete combustion
that results. Nevertheless, results similar to those presented
here were obtained during the UDC by Fontaras et al.14 and
Macor et al.,18 who also attributed this result to higher blend
viscosity and poor atomization during cold start conditions.
Karavalakis et al.13 investigated the inuence of cold start on
CO emission and noted only a marginal increase within the
uncertainty range of the measurement method, and even a
signicant decrease in the case of some biodiesel blends. In this
study, only the HVO30 blend was characterized by lower CO
emissions, which were reduced by more than half in
comparison to emissions from diesel fuel. The HVO30 fuel
had the lowest density, which would conrm the inuence of
the physical properties of this fuel on the combustion processes.
Zervas16 investigated pure aliphatic fuels and also obtained
signicantly lower CO emissions during the NEDC, indicating
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vehicle speed increases.13,14,18 No signicant dierences in NOx

emission were observed for HVO30 fuel. Nevertheless, a slight
increase in NOx emission was observed during the UDC phase
in comparison to diesel fuel. This could indicate a tendency
toward some increase in NOx emissions, as shown in a previous
study using pure paranic fuels.16
PM emissions for each the biofuels, both FAME and HVO
blends, decreased in comparison to emissions when using
conventional diesel fuel. The highest reduction was observed
for pure biodiesel during the EUDC phase. Specically, PM
emissions during the UDC phase decreased by 8.7% for B7, by
20.6% for B15, by 27.5% for B30, by 9.9% for B100 and by
11.8% for HVO30. However, due to the high variability of the
PM emission results for some fuels, these reductions were only
statistically signicant for the B15 and B30 blends over this test
cycle. PM emissions during the EUDC phase decreased by
16.5% for B7, by 5.2% for B15, by 18.6% for B30, by 76.3% for
B100, and by 5.2% for HVO30. These results are consistent
with the majority of comparable observations, where signicant
reductions in PM emissions were obtained for fuel with FAME
content and pure paranic fuel.19,34 This reduction is
attributed to the presence of oxygen in biodiesel as well as
the absence of aromatic hydrocarbons and sulfur in this fuel.38
HVOs sulfur content is also very low since, (similarly to
FAME) it is produced from raw vegetable material. Additionally, it was observed that all aromatics have a higher PM
formation tendency than parans.40 This may explain the PM
reduction in the case of HVO blend, however, the opposite
tendency was also obtained and was attributed to the improved
cetane number in comparison to diesel fuel, resulting in a
reduction of the premixed combustion region, while diusion
combustion increases.30 As shown by Happonen and coworkers39 even higher PM emissions reductions are possible by
blending HVO fuel with a suitable oxygenate. The relatively
small reduction in PM emission for B100 during the UDC
phase was probably caused by cold start and the physical
properties of FAME. Substantial CO and HC emission using
neat biodiesel indicates poor combustion under cold start
conditions and hence an increase in PM emission is to be
expected. This could lead to nearly 10 times higher PM
emission using B100 in comparison to base diesel or low
biodiesel blend, as observed in previous studies over the UDC
phase.41,42
The CO2 emissions were comparable in most of the
emissions tests performed. For all test fuels (excluding B100),
a slight decrease in CO2 emission was observed in relation to
diesel fuel during the UDC phase; however, this decrease was
statistically signicant only for the B15 and HVO30 blends. In
turn, CO2 emission signicantly increased (by 6%) for B100
during this phase, which indicated that high contents of
biodiesel may lead to evident increases in CO2 emissions,
similar to those for B50 and B100 in the study by Fontaras et
al.,14 where CO2 emissions for those blends increased by 9 and
14%, respectively over the same driving cycle. In the EUDC
phase a statistically insignicant increase (12%) was found
regarding CO2 emissions for fuel with biodiesel and HVO
content. No increases in the variability of the CO2 emission
measurements with increasing biodiesel content in fuel were
observed, as reported by Karavalakis et al.,13 who observed less
repeatable engine operation using biodiesel blends. Fuel
consumption showed similar trends as CO2 emissions, with
the highest values noted for B100. In the UDC phase fuel
consumption was very comparable for all fuels tested excluding

blend, by over 50% in comparison to the value for diesel fuel

during the UDC, which indicates very good atomization and
vaporization of this fuel, even during cold start and warmup.
This fuel had the lowest density among all test fuels, which
suggests an impact of certain physical parameters on the HC
emission level. Similarly as for CO, Karavalakis et al.13 analyzed
the inuence of cold-start condition on HC emission and in
fact found a lack of any relationship between the amount of
FAMEs in the fuel (up to 30%) and HC emissions.
Nevertheless, as with CO emissions, most published studies
report reductions in HC emissions using biodiesel, which has
been attributed to the higher oxygen content of fuels blended
with biodiesel, resulting in more complete combustion. A
similar eect was obtained by the addition of other oxygenated
blending components and compared to rapeseed methyl estersdiesel blends containing the same oxygen concentration.34 In
turn, Balesteros et al.35 did not observe any dierences in HC
emissions during urban driving conditions, whereas during
extra-urban conditions emissions decreased with increasing fuel
FAME content. Reductions in HC emissions in comparison to
diesel fuel ranging from over 20 to over 40% using B5, B20, and
B30 were observed in other studies during the EUDC.15Our
results did not show any signicant reductions in HC
emissions, even during the EUDC, which is consistent with
previous studies performed by Macor et al.18 and Fontaras et
al.14 using a Euro 3 diesel engine.
Formation of NOx is inuenced by the fuel oxygen content
and the local gas temperature. Pure biodiesel (B100) contains
approximately 10% oxygen by weight. However, for the vehicle
under test a slight decrease of NOx emission in the complete
NEDC cycle was observed (ranging from 15% for all fuels
containing FAME) and was caused by the decreased emission
of NOx during the UDC phase. During the EUDC slight and
statistically insignicant increases were observed for the biofuel
blends, excluding the B7 blend (for which NOx emission
decreased negligibly). Unexpectedly, the highest reduction
during the UDC phase was obtained for neat biodiesel. It is
interesting why such a large decrease in NOx emission
occurred, considering the fact that in the literature mainly
increases in NO x emission using biodiesel are reported.13,14,26,27,36 This unexpected trend indicates that it is
also likely that NOx formation is caused, at least in part, by the
physical properties of fuels which can inuence the performance of the fuel injection system. These properties are
especially important during cold start, inuencing the formation
of airfuel mixture and its combustion, as suggested by
Fontraras et al.14 Hotter and higher engine load tests than the
NEDC are usually characterized by higher emissions of NOx at
which point biodiesel and its blends increase this emission in
comparison to conventional diesel. It was also reported that
during idle and acceleration modes the NOx emissions for the
vehicle fuelled with B20 and B30 were much higher than those
using the base diesel fuel and B5 fuel.15 Hence, it is possible
that that the many changes in vehicle speed during the UDC
lead to lower NOx emissions over this cycle. Bergthorson and
Thomson summarize that the so-called biodiesel NOx eect,
which manifests itself in dierent eects on NOx emissions, is
the result not so much of basic fuel chemistry issues, but rather
the physical and chemical properties of the fuel on the
performance of an individual diesel engine.37 Excluding B100,
the UDC phases of all tests were characterized by higher
emissions of NOx than the EUDC phases, which is consistent
with most studies indicating a decrease in NOx emissions when
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precursors participating in photochemical smog formation.

Among the 15 carbonyl compounds determined, only 2,5dimethylbenzaldehyde was not identied in any of the exhaust
samples. Individual results are presented in the Supporting
Information (Table S2). Formaldehyde and acetaldehyde were
the most abundant for each fuel used, with a prevalence of
formaldehyde over acetaldehyde observed. The highest
emissions were observed over the UDC cycle, which may be
attributed to the cold-start condition at the beginning of that
cycle, during which fuel combustion is incomplete and the
oxidation catalyst has not reached its light-o temperature.
Similar observations were reported by Macor et al.18 with Euro
3 diesel engines, whereas Karavalakiset al.17and Fontaraset al.14
probably did not observe such high emission during the UDC
cycle; however, only emissions for the complete NEDC were
shown, which were at levels comparable to those observed over
the other (Artemis) hot driving cycle. A Similar level of
formaldehyde and acetaldehyde emission rates were presented
by Nelson et al. for an older type of vehicle produced before
2000.47 In this study, total carbonyl emissions increased with
increasing biodiesel content in the fuel under every driving
condition, as shown in Figure 2. Such an increase has been

B100, for which it increased signicantly (on average 14%).

The values for the EUDC phase were more varied and showed
a global trend toward higher fuel consumption for all test fuels
in comparison with diesel fuel. Nevertheless, a signicant
dierence was found only for B100 which showed 10% higher
value compared with diesel. However, for the entire NEDC
cycle a signicant increase in fuel consumption appeared not
only for B100, but also for B30 and HVO30, increasing by 2.4%
in both cases. These results are in agreement with the
observations found in most previous studies, which explained
this phenomenon in terms of the lower heating value of FAME
compared with pure diesel fuel.36 However, there are studies
which support the opposite trend, linking it to an improvement
in volumetric combustion eciency due to the structural
oxygen content in FAME,4345 which is rather surprising, given
the much lower energy density of such a fuel. The signicant
increase in fuel consumption over the entire NEDC with using
HVO30 blend can be attributed to the lower heating value on a
volumetric basis. Although HVO fuel has a greater heating
value on a mass basis, its presence in fuel decreases the energy
content on a volumetric basis due to its lower density. As a
consequence, higher volumetric consumption may be expected
for HVO blends because both diesel injection systems and fuel
dispensing systems deliver fuel by volume, not by mass.11
However, this may be partly compensated by higher mass-based
energy content due to the higher hydrogen to carbon ratio of
HVO in comparison with diesel fuel.
The results indicate that changes in fuel physical properties
due to the addition biodiesel or paran may aect substantially
diesel emission levels. Parameters such as density and viscosity
play a signicant role in diesel emissions due to the inuence
on air-fuel mixture formation. Especially density has been
studied extensively and it was shown that higher fuel density
increased emissions of HC, CO, NOx, and PM.20 Since FAME
addition increased the density and viscosity of the base diesel
fuel, it may cause emissions to deteriorate, particularly during
cold start and engine warm-up. A similar inuence may be
exerted by the higher boiling point or back-end volatility, which
is highly correlated with fuel density. However, the eect of
increased density and viscosity on diesel engine emissions are
probably compensated to a great extent by the higher cetane
number of FAME and its oxygen content, which are
traditionally factors improving the combustion process. This
leads to the reductions in HC, CO, and PM emissions observed
in many studies, but mostly during hot engine operation. HVO
fuel as a blending component decreased the density of diesel
fuel and only slightly increased the fuel viscosity, so that the
values are close to those of conventional diesel fuel. HVO is
characterized by a very high cetane number in comparaison to
pure diesel fuel, reecting its propensity for autoignition. In
conjunction with the lower boiling points of the HVO blend, its
nal properties lead to more complete combustion, also during
cold engine condition and despite the lack of oxygen atoms in
the fuel.
Carbonyl Emissions. Carbonyl emissions when using
biodiesel remain an important issue due to many observations
that biodiesel use could signicantly increase emission of both
aldehydes and ketones with established toxic properties such as
formaldehyde, acetaldehyde, acrolein, and acetone. Formaldehyde is classied by the International Agency for Research
of Cancer (IARC) as a human carcinogen (Group 1);
acetaldehyde as possibly carcinogenic to humans (Group
2B).46Additionally, carbonyl compounds are important ozone

Figure 2. Total carbonyl emissions for the test fuels over the UDC,
EUDC, and complete NEDC cycles. * p < 0.05.

observed in the majority of studies performed and was usually

linked to the presence of oxygen in the ester group of FAME.
However, the opposite trend has also been found and was
explained by more complete combustion of biodiesel than
diesel, due to the need to combust more reduced substances
with diesel fuel.48 Nelson et al.47 studied emissions from
dierent conventional diesel fuels and concluded that formaldehyde and acetaldehyde are largely formed in the
combustion process from fuel fragments produced in the initial
oxidative pyrolysis of the fuel, and this fragments are largely
derived from the major constituents of the fuels. Hence,
combustion conditions such as local stoichiometry and
temperature may largely determine their formation. The
highest emission was found for B100 in the case of all carbonyl
compounds except acetone, for which the highest value was
obtained when pure diesel fuel was used. This upward trend
was observed for most of the carbonyl compounds, but only
during the UDC cycle. The EUDC was characterized by much
lower emissions, which was the result of eective combustion
and full catalyst eciency.49 However, even during the EUDC
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PAHs originate mainly from incomplete combustion of fuel and

lubricating oil, and also from pyrosynthesis of lower molecular
mass hydrocarbons. PAH molecules containing 45 benzene
rings are the most harmful PAH compounds, and are
exclusively bonded to exhaust particles. Nitro-PAH are direct
or indirect products of incomplete fuel combustion. The
majority of these compounds are formed by reactions of parent
PAH with NOx in the gas phase and rapidly adsorbed onto
particulate matter. Some nitro-PAH are characterized by higher
mutagenicity and carcinogenicity in comparison to unsubstituted PAH molecules. A number of studies have conrmed the
presence of nitro-PAH in extracts of diesel particulate matter,
among which 1-nitropyrene, 2-nitrouorene, and 3-nitrouoranthene are the most commonly detected compounds.51
During the tests, the highest emission was measured for light
PAHs such as acenaphthene and uorene, which emission was
determined as a sum of these compounds, and subsequently for
uoranthene, pyrene, benzo(a)anthracene and chrysene.
Individual results are presented in Supporting Information
Table S3. Acenaphthene and uorine were the most abundant
compounds among the PAH emitted, and emissions were lower
when using fuels containing biodiesel compared to diesel fuel,
with a single exception: a slight increase for B30 during the
EUDC cycle. Emission of lower and medium molecular weight
PAHs such as phenanthrene, which dominated in some
previous studies,52,53 anthracene, uoranthene, and pyrene
decreased for B7 and increased for the higher biodiesel blends,
compared to diesel fuel. In turn, emissions of benzo(a)anthracene and chrysene, after decreasing for both B7 and B15,
increased slightly for the B30 blend. However, the emission of
heavier PAHs was usually higher for biodiesel blends than for
pure diesel fuel. Unexpectedly, use of B100 led to lower
emissions of the lighter PAHs and usually the highest emission
of heavier and most toxic PAH molecules such as bezeno(k)uoranthene, benzo(a)pyrene, benzo(g,h,i)perylene, and
indeno(1,2,3-c,d)pyrene. This is in contrast to most previous
studies, which found a decrease in emission of heavier PAH
molecules with biodiesel,13,17,18,52,5456 although the opposite
tendency- or lack of response - has also been observed.53,57 The
increased toxicity of particulate from pure biodiesel use was also
shown by Kooter et al.s58 in a mutagenicity test, despite the
strong decrease in the weight and number of particles emitted.
The prole of emitted PAH was similar for the UDC and the
EUDC with acenaphthene and uoranthene dominant, but
emission during the EUDC was signicantly lower than during
the UDC phase, as reported by Ballesteros and co-workers.56
Similar to Kooter and co-workers work,58 a gradual increase in
most PAH emission was observed with an increase in biodiesel
content in the blends. This observation is especially reected by
the total PAH emissions shown in Figure 3. Work by
Karavalakis et al.13 indicated the opposite trend, with the
exception of oxidized biodiesel blends, whose use resulted in
substantial increases in PAH emissions compared to diesel fuel.
Nevertheless, the amount of PAH emitted was much lower in
our study in comparison to the aforementioned study. For the
B30 blend the total PAH emission exceeded emission from
pure diesel fuel and was the highest among all biodiesel
containing test fuels. Macor and co-workers18 also obtained
higher emission of total PAH with B30 compared to diesel fuel,
but a substantial decrease was observed in the case of emission
of heavier PAHs with this blend. The results indicate that
physical and chemical fuel properties probably inuence the
combustion process and consequently the formation of

cycle, formaldehyde emission increased with increased biodiesel

content in the fuel. Emissions of other carbonyl compounds
increased or decreased with biodiesel blends during the EUDC,
but were still highest using B100 fuel. In none of the tests
performed in this study was it found that emission of heavier
carbonyls increased with use of pure diesel fuel, as reported
elsewhere.14,17 Benzaldehyde emission, which could be
expected to be the highest when using pure diesel fuel, due
to its high level of aromatic compounds, was also the highest
for B100 fuel. Similar results were obtained for other aromatic
aldehydes such as o-tolualdehyde, p-tolualdehyde, and particularly for m-tolualdehyde. The latter was the most abundant,
which indicated that it was the prevalent product of incomplete
fuel combustion among all aromatic carbonyl compounds. In
contrast, in all tests the HVO30 blend caused the lowest
carbonyl compound emissions among the test fuels in both the
UDC and EUDC. In relation to pure diesel fuel, emission of the
most abundant formaldehyde and acetaldehyde decreased by
49.2 and 46.5%, respectively, whereas total carbonyls decreased
by 47.4% for the complete NEDC cycle. Such a substantial
reduction in carbonyl emissions may be attributed to the high
eectiveness of combustion in respect to this fuel. Pure HVO is
a mix of liquid paranic hydrocarbons, whose addition
improves combustion even during cold-start and engine
warm-up. This is probably a result of improved properties for
atomization and volatilization of the HVO blend due to the
lower density and boiling temperature of this fuel. As shown in
the literature, lower fuel density and back-end volatility have a
great impact on decreasing CO and total hydrocarbons
emissions, which indicates higher combustion eciency during
diesel engine operation. Moreover, pure HVO has a very high
cetane number (>70) and its addition to diesel fuel increases
the cetane number linearly. It was found that increased cetane
number also reduced emissions of HC and CO, probably due
to improvement of ignition performance.30Another cause for
the observed reduction may be a decrease in concentration of
precursors for carbonyl compound formation and the degree of
molecular unsaturation. The ability of paranic fuel to reduce
emission of carbonyl compounds was also found in some earlier
studies. Yuan et al.50 evaluated emissions from a heavy-duty
diesel engine in a transient test using a paranic and biodiesel
blend and they obtained a signicant reduction of carbonyls in
exhaust gases, equaling 24% and 30% for 20% and 5% biodiesel
paranic blend, respectively. Zervas et al.16tested two types of
paranic fuel and also obtained signicant reductions of
formaldehyde, acetaldehyde and total carbonyl compounds,
which reached 69% and 89% in comparison to when using
conventional diesel fuel.
PAH Emissions. PAH emissions in vehicular diesel exhaust
are the focus of much attention because many of these
compounds have been identied as potential cancer causing
compounds. According to IARC, there is sucient evidence of
the carcinogenicity of benzo(a)pyrene in humans (group 1A).
Additionally, dibenzo(a,h)anthracene, benzo(a)anthracene,
benzo(b)uorantene, benzo(k)uorantene, chrysene, and
indeno(1,2,3-c,d)pyrene are recognized as animal carcinogens
(IARC groups 2A and 2B). Regarding diesel exhaust emissions,
there are especially suitable conditions for adsorption of these
compounds on simultaneously emitted particulate matter. Very
ne particulate matter containing particles <2.5 m in diameter
plays a particular role in this process. The particles contain
mainly soot, which formed carbon complexes with products of
incomplete combustion, which are adsorbed onto the surface.
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Environmental Science & Technology

formation of nitro-PAHs when biodiesel is present in the fuel,

although Huang et al.59 observed increasing emission of one
nitro-PAH species (5-nitroacenaphthene) with biodiesel, but
only during idling. In spite of the similar quantity of total PAH
emitted using the B30 and HVO30 blends, conditions for
formation of nitro-PAHs were better in the case of HVO30
than for B30. This might be because HVO is more similar in
terms of structure to pure diesel fuel than biodiesel is.

ASSOCIATED CONTENT

S Supporting Information
*

The methodological details (pages S3S4). Recoveries,

precision and accuracy of analytical methods (Table S1).
Carbonyl compound and PAH emissions for the test fuels over
the UDC, EUDC and complete NEDC cycles (Tables S2S3),
Nitro-PAH emissions for the test fuels over the UDC cycle
(Table S4). The chassis dynamometer used in this study, within
its climate chamber (Figure S1). The New European Driving
Cycle NEDC (UDC + EUDC) (Figure S2). The Supporting
Information is available free of charge on the ACS Publications
website at DOI: 10.1021/acs.est.5b00648.

Figure 3. Total PAH emissions for the test fuels over the UDC,
EUDC, and complete NEDC cycles.

individual PAHs, because despite the fact that biodiesel does

not contain PAH compounds, the addition of biodiesel to diesel
resulted in increased emission of most PAHs.
Using the HVO30 blend the total PAH emission was the
highest among all tested fuels, slightly exceeding emission using
B30 biodiesel blend. This was a consequence of the highest
emissions of lower molecular weight PAHs such as
acenaphthene, uorene, phenanthrene, and anthracene. In
contrast, the emission of the heaviest PAHs was usually at
the lowest level compared to the use of other tested fuels. Thus,
HVO30 fuel parameters such as lower density and boiling point
resulted in decreased formation of the most toxic PAHs
containing more than four rings, but increased emissions of
lighter PAH, which is dicult to explain. Perhaps if HVO
increases the cetane number and the diusion combustion
phase is longer, this may be a favorable condition to form more
stable polyaromatic compounds, particularly at low engine load.
Lim and colleagues30 also showed that the level of total PAH
was higher with HVO-blended diesel when compared to diesel
blended with an additive to produce a fuel with an equivalent
cetane number. In turn, Youn and co-workers19 found a
substantial potential for reducing PAH emission using paranic
fuel, which, when blended with biodiesel, signicantly
decreased exhaust PAH emissions and their toxicity equivalent
in comparison to diesel fuel.
Emissions of nitro-PAHs were not detectable during most
tests. These compounds were identied in exhaust particles
emitted during the UDC phase only, when using pure diesel
fuel, B7, B100 and HVO30 blends (Supporting Information
Table S4). The highest emission was found using pure diesel
fuel. Total nitro-PAH emissions for the test fuels decreased in
the following order: B0 > B7 > HVO30 > B100 and with B15
and B30 all of the 6 nitro-PAHs analyzed were below the limit
of detection. These decreasing nitro-PAH emissions with
biodiesel and biodiesel blends in comparison to diesel fuel is in
agreement with previous studies.13,17,58,59 The main reason for
this reduction was attributed to lower emission of nitro-PAH
precursors, that is, parent PAHs, which therefore resulted in the
higher emission of nitro-PAHs measured with oxidized
biodiesel blends, whose use were related to higher PAH
emissions than with diesel fuel. In this study a reduction was
found in most cases, despite the increase in emission of parent
PAHs. This may suggest less favorable conditions for the

AUTHOR INFORMATION

Corresponding Author

*Phone: +48326341195; e-mail: a.prokopowicz@imp.

sosnowiec.pl.
Author Contributions

The manuscript was written through contributions of all

authors. All authors have given approval to the nal version of
the manuscript.
Funding

This work was supported by the Polish Ministry of Science and

Higher Education, grant number N N404 311540.
Notes

The authors declare no competing nancial interest.

ABBREVIATIONS
CVS
constant volume sampling
EUDC Extra Urban Driving Cycle
NEDC New European Driving Cycle
UDC Urban Driving Cycle

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