Renewable Energy xxx (2016) 1e9

Contents lists available at ScienceDirect

Renewable Energy
journal homepage: www.elsevier.com/locate/renene

Unregulated emissions and health risk potential from biodiesel (KB5,

KB20) and methanol blend (M5) fuelled transportation diesel engines
Avinash Kumar Agarwal a, *, Pravesh Chandra Shukla b, Chetankumar Patel a,
Jai Gopal Gupta a, Nikhil Sharma a, Rajesh Kumar Prasad a, Rashmi A. Agarwal a
a
b

Engine Research Laboratory, Department of Mechanical Engineering, Indian Institute of Technology Kanpur, Kanpur 208016, India
Department of Civil Engineering, Indian Institute of Technology Kanpur, Kanpur 208016, India

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 25 December 2015
Received in revised form
5 March 2016
Accepted 16 March 2016
Available online xxx

Diesel engine emissions consist of several harmful gaseous species, some of which are regulated by
stringent emission norms, while many others are not. These unregulated emission species are responsible for adverse environmental impact and serious health hazards upon prolonged exposure. In this
study, a four-cylinder, 1.4 l, compression ignition (CI) engine was used for characterization of unregulated
gaseous exhaust emissions measured at 2500 rpm at varying engine loads (0, 25, 50, 75 and 100%). The
test fuels investigated were Karanja biodiesel blended with diesel (KB5, KB20), methanol blended with
diesel (M5) and baseline mineral diesel. Fourier transform infrared (FTIR) emission analyzer was used to
measure unregulated emission species and raw exhaust gas emission analyzer was used to measure
regulated emission species in exhaust. Results show an increasing trend for some of the unregulated
species from blends of biodiesel such as formaldehyde, acetaldehyde, ethanol, n-butane however
methane reduced upon using these oxygenated fuel blends except methanol, compared to baseline
mineral diesel. Nevertheless, no signicant changes were observed for sulfur dioxide, iso-butane, n-octane, n-pentane, formic acid, benzene, acetylene and ethylene upon using biodiesel and methanol blends.
2016 Published by Elsevier Ltd.

Keywords:
Unregulated emissions
Karanja biodiesel
Methanol
Fourier transform infrared spectrometry
Aldehydes

1. Introduction
Biofuels have emerged as a renewable substitute for conventional petroleum based fossil fuels, for both on-road and off-road
vehicles and stationary power generators [1]. Biodiesel and primary alcohols are the most accepted biofuels. Vegetable oils
contain triglycerides, which react with primary alcohols in the
presence of a suitable catalyst such as KOH or NaOH, under
appropriate reaction conditions to yield methyl esters and glycerol.
This process is known as transesterication. Biodiesel is a diesel like
oxygenated renewable fuel, which has ~11% (w/w) oxygen [1,2]. On
the other hand, primary alcohols are also oxygenated fuels, which
can be blended with mineral diesel in lower concentrations. Alcohols can be produced by fermentation of sugarcane juice and other
renewable resource such as biomass and waste products, which are
readily available in rural areas. It has been reported in several
studies that alcohol blends with diesel are superior to mineral

* Corresponding author.
E-mail address: akag@iitk.ac.in (A.K. Agarwal).

diesel in terms of higher efciency and lower emissions [1,3]. Diesel

engines can accept up to 20% methanol blended with diesel easily
with either little or no engine hardware modications [4,5]. One of
the main concerns related to diesel engines is the emissions of
particulate matter (PM) and oxides of nitrogen (NOX), with minor
emissions of unburnt hydrocarbons (HC) and carbon monoxide
(CO). Diesel particulates mainly consist of elemental carbon and
organic carbon (EC/OC) along with sulfates and ash. Volatile organic
carbon (VOC) and unburned hydrocarbons (HC) present in the
diesel engine exhaust consist of several harmful hydrocarbon
species. Apart from regulated gaseous emissions, diesel exhaust
consists of a large number of unregulated species as well. Some of
these unregulated emissions include alkanes, aldehydes, benzene,
toluene, xylene (BTX), alcohols and ketones.
Correa and Arbilla, 2008 [6] carried out experiments using
castor oil derived biodiesel blended (2, 5, 10 and 20% v/v) with
diesel for detecting unregulated emissions and they reported
increased formaldehyde (2.6%, 7.3%, 17.6%, 35.5%) and acetaldehyde
(1.4%, 2.5%, 5.4%, 15.8%) emissions from biodiesel blends compared
to baseline diesel. However, Peng et al., 2008 [7] reported 23%
reduction in formaldehyde emissions for 20% (v/v) waste cooking

http://dx.doi.org/10.1016/j.renene.2016.03.058
0960-1481/ 2016 Published by Elsevier Ltd.

Please cite this article in press as: A.K. Agarwal, et al., Unregulated emissions and health risk potential from biodiesel (KB5, KB20) and methanol
blend (M5) fuelled transportation diesel engines, Renewable Energy (2016), http://dx.doi.org/10.1016/j.renene.2016.03.058

A.K. Agarwal et al. / Renewable Energy xxx (2016) 1e9

oil biodiesel blend. Karavalakis et al., 2009 [8] investigated unregulated emissions in Athens driving cycle (ADC) and new European
driving cycle (NEDC) using rapeseed and palm biodiesel blends (5,
10 and 20% v/v) fuelled engine. They observed increased formaldehyde emissions from both biodiesel's blends, while palm biodiesel blend resulted in reduced aldehyde emissions. Di et al., 2009
[9] investigated various unregulated emissions from a diesel engine
-vis baseline
fuelled by waste cooking oil biodiesel blends vis-a
mineral diesel. They reported that formaldehyde, 1,3-butadiene,
toluene and xylene emissions decreased whereas acetaldehyde and
benzene emissions increased with increasing biodiesel blending.
He et al., 2009 [10] reported that formaldehyde emission contribution was 46.2% and 62.7% in carbonyl emissions from soybean
based biodiesel and diesel respectively in a diesel engine experiment. They also observed signicant amount of acetaldehyde,
acrolein, and acetone among unregulated emissions. Karavalakis
et al., 2009 [11] measured unregulated emissions in ADC & NEDC
driving cycles from soy based biodiesel blends (5, 10 and 20% v/v)
vis-
a-vis mineral diesel. They reported that carbonyl emissions
were relatively lower from biodiesel blends. In another study, it was
reported that carbonyl emissions were not affected by lower biodiesel blends [12]. Magara-Gomez et al., 2012 [13] compared
emissions from soybean biodiesel blends (B50, B100) and beef
tallow biodiesel blends (BT50, BT100) with baseline mineral diesel.
They reported signicant reduction in unregulated emissions such
as toluene, ethylbenzene and xylene emissions. 23, 42 and 40%
reduction in formaldehyde emissions were observed from B50,
-vis mineral diesel.
B100 and BT100 respectively vis-a
Some studies [14e17] also reported unregulated emissions from
alcohol blends fuelled diesel engines. Chao et al., 2000 [14] investigated methanol containing additives blended diesel (0, 5, 8, 10
and 15% v/v) in a heavy-duty diesel engine. They observed relatively higher carbonyl emissions and other unregulated emissions
such as acrolein, benzaldehyde. Cheung et al., 2009 [4] also reported higher emissions of acetaldehyde, formaldehyde and
methanol emissions from biodiesel-methanol blends (BM5, BM10
and BM15) compared to baseline diesel. They reported that 1,3butadiene and benzene emissions were relatively lower from
biodiesel-methanol blends, while toluene and xylene were similar
to that of mineral diesel. Zhang et al., 2010 [18] found decreasing
trend of ethyne, ethylene and 1,3-butadiene emissions upon
applying diesel/methanol (10, 20 and 30% fumigation methanol)
compound combustion scheme on a four-cylinder diesel engine.
They reported higher emissions of benzene, toluene, xylene, unburned methanol and formaldehyde with increasing methanol
concentration in the test fuel. Table 1 shows the health effects of
various unregulated emissions from diesel engines, which are
fuelled by mineral diesel, biodiesel and diesel-alcohol blends. This
table helps one understand the associated health and environmental costs of using different fuels, including renewable fuels.
In the present study, various unregulated emissions were
measured in the exhaust from a CI engine, which was fuelled by
Karanja biodiesel blended with diesel (KB5, KB20), methanol
blended with diesel (M5), and baseline mineral diesel. This study
brings out some important inferences in terms of unregulated
emissions emitted by the alternative fuelled engines in real-time. It
is also well known that various unregulated organic compounds
present in the engine exhaust undergo secondary chemical reactions in the environment and form secondary and tertiary pollutants. Real-time measurement of exhaust provides information
about the primary organics and hydrocarbons emitted by the engine. No study has been performed so far on the real-time measurements of unregulated emissions for these alternative fuels.

2. Experimental setup and methodology

A four cylinder, water-cooled, naturally aspirated, transportation diesel engine was used in this experimental study. Test
engine produces rated torque of 85 Nm at 2500 rpm engine speed.
Technical specications of the engine are given in Table 2. The fuel
injection system consists of a rotary fuel injection pump and solenoid injectors. Fig. 1 shows the schematic of the experimental
setup.
Experiments were performed on a diesel engine, which was
fuelled by mineral diesel, biodiesel blends (KB5, KB20) and methanol blended (M5) with diesel. Emissions were measured for
regulated and unregulated species using a raw exhaust gas emission analyzer (Horiba; EXSA 1500) and a Fourier transform infrared
(FTIR) emission analyzer (Horiba; MEXA 6000FT-E) respectively.
FTIR spectrometry was used for obtaining infrared absorption
spectrum of high resolution by a combination of an interferometer
and high-speed Fourier transform. CO and CO2 were measured by
using non-dispersive infrared (NDIR) measurement principle. Total
hydrocarbons (THC) were measured by ame ionization detection
(FID) analyzer and NOX was measured by Chemiluminescense
(CLD) analyzer. Both emission analyzers were equipped with a
heated exhaust gas sampling system, which was maintained at
191
C as per the norms of US Environmental Protection Agency
(USEPA) in order to avoid condensation of moisture and high
boiling point hydrocarbons during sampling. Detailed specications of the regulated and unregulated emission measurement instruments are given in our previous paper [40].
Before sampling the exhaust, engine was operated for 10 min at
every engine operating condition, in order to obtain thermally
stable condition of the engine. After achieving the thermal steady
state, exhaust gas samples were drawn simultaneously for regulated and unregulated gaseous species measurement. Exhaust
samples were drawn at ve engine loads (0, 25, 50, 75 and 100%) at
the rated torque speed of 2500 rpm. Each data point represents an
average of 60 consecutive measurements and standard deviation is
shown in the plots.
3. Results and discussion
The main concern remains in diesel engines is the dilemma of
PM and NOx trade-off. There are several hydrocarbon species present in the diesel engine exhaust, which are carcinogenic and
mutagenic in nature and lead to serious problems in human body
upon prolonged exposure. These hydrocarbon species condense on
the condensate sites (generally nano-particles) present in the engine exhaust and form very harmful aerosols, when they are
released into the environment via the engine tail-pipe. Therefore, it
is necessary to characterize various emission species from diesel
engines, especially when they are being used with alternative fuels
such as biodiesel and primary alcohols and compare their potential
toxicity with baseline mineral diesel. In this section, experimental
results are discussed in two separate sections namely regulated
emissions and unregulated emissions.
3.1. Regulated gaseous emissions
Emissions of CO, HC, NOX (NO, N2O and NO2), which comprises
of nitric oxide (NO), nitrogen dioxide (NO2), nitrous oxide (N2O) in
the exhaust have been compared and discussed in this section for
the test fuels used in this study.
3.1.1. Carbon monoxide (CO) and unburnt hydrocarbon emissions
(HC)
All the blended fuels resulted in slightly higher CO emission

Please cite this article in press as: A.K. Agarwal, et al., Unregulated emissions and health risk potential from biodiesel (KB5, KB20) and methanol
blend (M5) fuelled transportation diesel engines, Renewable Energy (2016), http://dx.doi.org/10.1016/j.renene.2016.03.058

A.K. Agarwal et al. / Renewable Energy xxx (2016) 1e9

Table 1
Health and environmental effects of unregulated emission species [19e39].
Unregulated emission species

Possible health and environmental effect

Methane
(CH4)






GHG with greenhouse index 21 times that of CO2.

Simple asphyxiant, when inhaled.
Leads to headache, dizziness, weakness, nausea, vomiting, and loss of consciousness.
Inhalation causes euphoria, drowsiness, narcosis, asphyxia, cardiac arrhythmia, and uctuations in blood pressure.




























Simple asphyxiant, when inhaled.

Causes fatigue, dizziness, headache, and nervous system damage.
Affects central nervous system.
Causes erythema, hyperaemia, swelling, pigmentation, and anoxia.
Burning sensation accompanied by itching, and blisters.
Giddiness, vertigo, skin redness and rashes, brain irritation or apnoeic anoxia.
Causes throat and lungs problems, and headache.
Causes headache, drowsiness, dizziness, nausea, weakness and unconsciousness.
Causes irritation to respiratory system, alters carbohydrate metabolism.
Acts as ozone formation agent.
Causes suffocation, dizziness, headache, unconsciousness, and nausea.
Inhalation results in high blood pressure, ts and abnormal heart rhythms.
Drowsiness, dizziness, rapid or irregular heart-beats, headaches, tremors, confusion, unconsciousness, and carcinogenic to humans.
Chromosomal aberrations in human peripheral lymphocytes.
Irritation in eyes, nose, and throat, coughing, and skin irritation.
Considered as human carcinogen, asthma-like respiratory problems.
Affects pregnancy and reproductive system.
Irritation of skin, eyes, mucous membrane, throat, respiratory tract, nausea, vomiting and headache.
Probable carcinogen.
Causes teary eyes, running nose, coughing, sore throat, bronchitis, shortness of breath, pulmonary edema, liver and kidney damage.
Burns tissue and membrane of the skin, and respiratory tract.
Causes unconsciousness.
Affects formation of anti-diuretic hormones, leading to brain disability.
Affects nervous system of developing embryo and foetus.
Higher concentration (>100 ppm) causes danger to life and health.
Burning sensation in nose and throat, breathing difculties, and severe airway obstructions.

n-butane
(n-C4H10)
Iso-butane
(iso-C4H10)
Normal pentane
(n-C5H12)
Normal octane
(n-C8H18)
Ethylene
(C2H4)
Acetylene
(C2H2)
Benzene
(C6H6)
Formaldehyde
(HCHO)
Acetaldehyde
(CH3CHO)
Formic acid
(HCOOH)
Ethanol
(C2H5OH)
Sulphur dioxide
(SO2)

Table 2
Technical specications of the test engine.
Particulars

Specications

Make/Model
Number of cylinders
Bore/Stroke
Fuel injection pump
Capacity
Rated power
Rated torque
Compression ratio
Firing order

Tata/Indica 1.4 L
4, Inline
75 mm/79.5 mm
Rotary fuel injection pump
1405 cc
53.5 PS @ 5000 rpm
85 Nm @ 2500 rpm
22:1
1-3-4-2

slightly higher CO emission compared to other fuels. In general, CO

emission decreased towards intermediate loads and then increased
to reach maxima at full load for all test fuels. KB20 has moderately
higher CO emission at lower loads compared to baseline mineral
diesel. KB20 has slightly higher viscosity, which results in larger
size distribution of fuel spray droplets, relatively more inefcient
fuel-air mixing and higher degree of incomplete combustion at
lower loads, which leads to slightly higher CO emission. At 75 and
100% loads, higher in-cylinder temperature promoted higher
evaporation of biodiesel spray droplets. This helped in achieving
relatively higher degree of complete combustion, which reduced

Fig. 1. Schematic of the experimental setup.

compared to baseline mineral diesel at lower loads (Fig. 2a). While

no signicant difference was observed for CO emission at higher
loads amongst all test fuels. At 75% and 100% loads, M5 resulted in

-vis mineral diesel. In addition,

CO emission from KB20 vis-a
inherent fuel oxygen [2] of biodiesel also helped in CO reduction.
CO2 emission increased with increasing engine load (Fig. 2b) and its

Please cite this article in press as: A.K. Agarwal, et al., Unregulated emissions and health risk potential from biodiesel (KB5, KB20) and methanol
blend (M5) fuelled transportation diesel engines, Renewable Energy (2016), http://dx.doi.org/10.1016/j.renene.2016.03.058

A.K. Agarwal et al. / Renewable Energy xxx (2016) 1e9

Fig. 2. Carbon monoxide (CO), Carbon dioxide (CO2) and unburnt hydrocarbons (HC)
in the exhaust.

concentration varied from 3.5% to 11% from no load to full load. All
test fuels showed similar trend for CO2 emission, which indicated
no loss in engine performance for alternate test fuels used in this
study.
Fig. 2c shows that mineral diesel emitted lower HC at lower
loads, while blends of biodiesel and M5 emitted higher HC emissions. At higher loads, mineral diesel emitted relatively higher HC
emissions compared to other test fuels [41]. Lower evaporation of
biodiesel at lower loads resulted in slightly higher HC emissions
from biodiesel blends. Again, increased in-cylinder temperature at
higher loads and fuel oxygen content of biodiesel led to reduction in
HC emissions. Similarly, use of M5 also led to lower HC emissions
due to inherent oxygen content of methanol. Fig. 2d shows the
moisture (H2O) content in the engine exhaust for all test fuels. H2O
is a by-product of combustion. All test fuels showed same trend of
moisture content in the exhaust. It is desirable to have highest
possible concentration of moisture and CO2 for higher thermal efciency and lower emissions, for a given engine power output.
3.1.2. Oxides of nitrogen
Fig. 3 shows NO, NO2, and N2O emissions measured by FTIR
analyzer (Fig. 3aec) and total NOX emissions measured by Chemiluminescense analyzer (Fig. 3d) for all test fuels. NO emission
increased as the engine load increased and reached maxima at full
load for all test fuels (Fig. 3a). NO formation in the combustion
chamber is a temperature dependent phenomenon. Since the peak
in-cylinder temperature increased with increasing engine load, NO
formation also increased [42,43]. NO2 emission was higher at lower
engine loads (Fig. 3b). Engine emitted ~50 ppm NO2 at no load,
when fuelled by mineral diesel, which becomes negligible at full

Fig. 3. Oxides of nitrogen in the exhaust.

load. Other test fuels showed slightly lower NO2 emission

compared to mineral diesel. NO2 concentration reduced with
increasing engine load, suggesting that NO2 emission reduced as
the peak in-cylinder temperature increased. NO2 is a paramagnetic
compound and is also a key component participating in secondary
aerosol formation. NO2 plays a major role in formation of ground
level ozone (smog) [44], therefore, it is desirable to have lower NO2
emissions in the engine exhaust. Fig. 3c shows the N2O emission,
which remains almost negligible for all loads for all test fuels. N2O is
a strong greenhouse gas and has global warming potential ~310
times that of CO2 (EPA, 2010). Fig. 3d shows NOx emissions, which
were almost similar to NO emission trend for all test fuels. At higher
engine loads, NOx emissions were moderately lower for biodiesel
blends compared to M5 and baseline mineral diesel. Raheman and
Phadatare, 2004 [45] also reported ~26% lower NOx emissions from
Karanja biodiesel and blends compared to baseline mineral diesel.
3.2. Unregulated emissions
Emissions of various unregulated species in the exhaust have
been compared and discussed in this section for all the test fuels
used in this study. For convenience, they are segregated in different
categories.
3.2.1. Saturated hydrocarbon compounds
Traces of several saturated hydrocarbons such as methane (CH4),
n-butane (n-C4H10), n-pentane (n-C5H12) and n-octane (n-C8H18)
were emitted in the engine exhaust and were measured by the FTIR
emission analyzer. Fig. 4a shows that the concentrations of
methane were negligible at lower engine loads but they were signicant at 75% and 100% engine loads for all test fuels. For 100%

Please cite this article in press as: A.K. Agarwal, et al., Unregulated emissions and health risk potential from biodiesel (KB5, KB20) and methanol
blend (M5) fuelled transportation diesel engines, Renewable Energy (2016), http://dx.doi.org/10.1016/j.renene.2016.03.058

A.K. Agarwal et al. / Renewable Energy xxx (2016) 1e9

all test fuels, which reduced to approximately 2 ppm at full load.

The reduction in n-octane occurred due to superior oxidation at
higher temperatures at high engine loads.
3.2.2. Unsaturated hydrocarbons
Fig. 5 shows the emission of acetylene (C2H2) and ethylene
(C2H4) from all test fuels. Acetylene emission increased at higher
engine loads (Fig. 5a). In the engine exhaust, acetylene acts as a
precursor for the formation of pyrolyzed compounds and aromatic
compounds. Therefore, it is desirable to have lower emission of
acetylene. Emission of ethylene was in the range of 5e10 ppm at no
load (Fig. 5b), which decreased towards the intermediate load and
again slightly increased at full load.

Fig. 4. Saturated hydrocarbon emissions in the exhaust.

load, methane concentration in the exhaust was in the range of

15e30 ppm, depending on the test fuel used. Methane is a strong
greenhouse gas and its greenhouse index is 21 times that of CO2. Its
emission is highest for M5, followed by mineral diesel, KB5 and
KB20 at full load. It has been reported that methane can be produced by thermal cracking of longer chain-length hydrocarbons.
The increasing concentration of methane at higher engine load
might be due to methane formation at higher in-cylinder temperatures [46].
n-butane emission was ~40 ppm (Fig. 4b) at no load for all test
fuels except mineral diesel, which was ~25 ppm. As the engine load
increased, concentration of n-butane decreased and at full load, it
was 5e10 ppm for all test fuels. Biodiesel blends emitted slightly
higher n-butane compared to mineral diesel. Possibly, mineral
diesel consists of longer chain hydrocarbons (C16), which were
more prone to fragmenting into smaller species (such as n-butane)
in presence of biodiesel, possibly due to its molecular oxygen. isobutane was also observed in very low concentration for all test
fuels, which decreased with increasing engine load (Fig. 4c).
However n-pentane concentration in the engine exhaust increased
with increasing engine load (Fig. 4d). At lower loads, n-pentane
emission was relatively higher for M5 compared to other test fuels.
n-octane emission (Fig. 4e) was maximum (~10 ppm) at no load for

3.2.3. Aldehydes and alcohols

KB5 and KB20 showed slightly higher formaldehyde (HCHO)
emissions at lower engine loads compared to mineral diesel
(Fig. 6a). In general, HCHO emission was higher at lower loads and
reduced with increasing engine load for all test fuels. HCHO is a
product of partial combustion of fuel and lubricating oil in the
combustion chamber. At lower engine load, in-cylinder temperature is relatively lower, which leads to lower evaporation of fuel and
higher degree of incomplete combustion of fuel droplets. As the
engine load increased, higher in-cylinder temperature promoted
oxidation of formaldehyde (Fig. 6a), resulting in reduction in its
concentration with increased engine load. For KB20, formaldehyde
emission was ~23 ppm at no load, which reduced to ~6 ppm at full
load. Acetaldehyde is the main organic species responsible for the
formation of secondary organic aerosols (SOA).
In this study, Acetaldehyde was in the range of ~15e28 ppm at
no load (Fig. 6b), which reduced to ~4 ppm at full load. Overall
acetaldehyde emission was higher at no load and reduced for
higher loads, similar to the results reported by He et al., 2003 [47]. It
seems that formation of aldehydes is also temperature dependent,
which reduces with increased temperature. KB20 showed slightly
higher acetaldehyde emission for all operating conditions.
Methanol emission was not detected for all test fuels, even from
M5. Ethanol emission showed detectable quantity (~10 ppm) at
lower loads however it reduced to 0e2 ppm at full loads for all test
fuels (Fig. 6c). Ethanol emission at lower engine loads indicated that
ethanol formed during combustion, which re-burnt at higher engine loads. Cheung et al., 2008 [15] gave the same reasoning for
reduction in ethanol traces at elevated combustion chamber temperature. As far as test fuels are concerned, there were no

Fig. 5. Unsaturated hydrocarbon emissions in the exhaust.

Please cite this article in press as: A.K. Agarwal, et al., Unregulated emissions and health risk potential from biodiesel (KB5, KB20) and methanol
blend (M5) fuelled transportation diesel engines, Renewable Energy (2016), http://dx.doi.org/10.1016/j.renene.2016.03.058

A.K. Agarwal et al. / Renewable Energy xxx (2016) 1e9

acid (H2SO4) in presence of moisture. The presence of sulfuric acid

in the exhaust acts as an ingredient for condensation of volatile
materials [48], which promotes particulate formation having
higher organic carbon content. Therefore, it is desirable to have
lower SO2 emission in the engine exhaust. Presence of sulfur in the
fuel is also responsible for poisoning of the catalyst present in the
after-treatment devices [48].
Fig. 7b shows that traces of formic acid were ~2 ppm. Benzene
emission was also found to be in quite low concentration, up to
~4 ppm (Fig. 7c). Bermudez et al., 2011 [46] reported that aromatic
species like benzene form due to pyrolysis at higher temperature
and pressure conditions of the combustion chamber. Pyrolysis
happens because of insufcient oxygen availability, which helps in
partially oxidizing fuel carbon into several unburnt hydrocarbon
products, including benzene. Benzene is a known carcinogenic
compound and its emission is undesirable.
Apart from the above discussed emission species, ethane (C2H6),
propylene (C3H6), propane (C3H8), 1,3-butadiene (1,3-C4H6),
isobutylene (iso-C4H8), iso-pentane (iso-C5H12), acetic acid
(CH3COOH), toluene (C7H8), ammonia (NH3) were also measured.
These results are not reported individually, however they are
shown in section 3.2.5.

Fig. 6. Aldehydes and alcohols emissions in the exhaust.

signicant differences at similar operating conditions.

3.2.4. Sulfur dioxide (SO2), formic acid (HCOOH) and benzene

(C6H6)
Sulfur dioxide (SO2) emission was less than 5 ppm for all test
fuels at all operating conditions (Fig. 7a). Sulfur is present in diesel,
which forms SO2 after combustion. SO2 promotes formation of
sulfur trioxide (SO3), which eventually gets converted to sulfuric

3.2.5. Other unburnt hydrocarbons

Emission norms regulate the hydrocarbon emissions from the
vehicles. However it is also important to evaluate the fraction of a
particular hydrocarbon species in HC. Higher concentration of a
particular hydrocarbon species can cause higher toxicity of the HC,
depending on their toxic potential. Fig. 8 shows the fraction of individual unregulated species measured in this study. It was
observed that the emissions of certain hydrocarbon species were in
higher fraction in HC such as formaldehyde, n-butane, acetaldehyde etc. particularly at lower loads. Fraction of most of the
detected species reduced in HC with increasing engine loads except
methane, n-pentane and acetylene. However fraction of unidentied species increased drastically at higher engine loads. This indicates that combustion leads to formation of few higher molecular
weight species in signicant quantity from all test fuels. Operating
conditions near 50%e75% loads resulted in lowest HC concentrations (except diesel at 75% load). For mineral diesel, fraction of
unidentied compounds was observed to be signicantly higher
compared to other test fuels at higher engine loads. This showed
superiority of alternate fuels over the mineral diesel for reduction
in emission of compounds with higher molecular weight. It was
observed that n-butane contributed a signicant fraction in hydrocarbons at lower and intermediate engine loads from mineral
diesel. Formaldehyde and acetaldehyde emissions were seen in
signicant concentrations for all test fuel at lower engine loads,
which reduced with increasing load.
The concentration of unidentied hydrocarbon compounds
from M5 was signicantly higher at lower engine loads. One point
should be noted that M5 emitted highest traces of methane
compared to other test fuels. The presence of methyl group in
methanol leads to higher emission of methane from M5.
4. Conclusions
Experimental investigation were conducted for nding out
several unregulated emission species such as nitrous oxide, formaldehyde, acetaldehyde, formic acid, n-butane, n-pentane,
methane, acetylene etc. Important conclusions made from the
experimental results are:

Fig. 7. Emission of sulfur dioxide (SO2), formic acid (HCOOH) and benzene (C6H6) in
the exhaust.

1. All test fuels lead to increase in CO emission at higher engine

loads. Higher fuel quantity injected at higher engine load

Please cite this article in press as: A.K. Agarwal, et al., Unregulated emissions and health risk potential from biodiesel (KB5, KB20) and methanol
blend (M5) fuelled transportation diesel engines, Renewable Energy (2016), http://dx.doi.org/10.1016/j.renene.2016.03.058

A.K. Agarwal et al. / Renewable Energy xxx (2016) 1e9

Fig. 8. Fraction of unregulated emissions in HC in the exhaust.

resulted in higher degree of incomplete combustion. HC emissions were observed to be higher from alternative fuels used in
this study at lower engine loads. However these alternative fuels
resulted in reduction in HC emissions at higher engine loads.
This depicted that alternative fuels are superior for higher engine outputs, especially for HC emissions. NOx emissions were
observed to be marginally lower from alternative test fuels.
2. Hydrocarbon emissions are regulated by the emission regulatory bodies. These hydrocarbons are mixtures of several
different organic species. Each organic species has different
toxicity behavior, depending on its toxic potential. Therefore it is
important to evaluate the emission of most harmful individual
organic species. In this study, some detected hydrocarbons such
as methane, n-pentane and acetylene were observed to be in
higher trace concentrations at increasing loads. On the other
hand, trace concentrations of n-butane, formaldehyde, acetaldehyde, and ethanol decreased with increasing engine load. No
denite trend was observed for ethylene, sulfur dioxide, formic
acid, benzene, iso-butane and n-octane emissions.
3. Biodiesel blends emitted lower trace concentrations of methane
while M5 emitted higher trace concentration of methane vis-a-

vis baseline mineral diesel. Methane has signicantly higher

GHG potential therefore biodiesel is a superior fuel for diesel
engine. Aldehyde is also a major carcinogenic compound, and
biodiesel blends emitted higher trace concentration. Therefore
biodiesel is advantageous from the point of view of emission of
some species however it has disadvantage of higher trace
emissions of some other organic species.
4. Detected organic species were compared among total hydrocarbons, which indicated that the fraction as well as absolute
concentration of detected hydrocarbon species reduced signicantly at higher engine loads. Apart from this, the fraction of
unidentied hydrocarbons increased drastically at full load for
all test fuels, which subsequently lead to increased HC emissions
at higher engine loads. Higher emissions of unidentied hydrocarbon species indicate formation of higher molecular
weight organic species at higher engine loads.
Overall, this study gave an insight into unregulated emissions
from blends of alternative fuels (KB5, KB20 and M5). Though the
species evaluated in this study are not regulated by the emission
regulations worldwide, they certainly cause several harmful effects,

Please cite this article in press as: A.K. Agarwal, et al., Unregulated emissions and health risk potential from biodiesel (KB5, KB20) and methanol
blend (M5) fuelled transportation diesel engines, Renewable Energy (2016), http://dx.doi.org/10.1016/j.renene.2016.03.058

A.K. Agarwal et al. / Renewable Energy xxx (2016) 1e9

depending on their toxic properties. It is also emphasized in this

study that even minor concentrations of some species may be more
harmful compared to some of the regulated species, which are
emitted in higher concentrations. This study is helpful in drawing a
landscape of unregulated species from different alternate fuels and
conventional fuels.
Acknowledgements
Authors would like to acknowledge Mr. Roshan Lal of Engine
Research Laboratory, IIT Kanpur for his valuable help in conducting
the experiments.
References
[1] A.K. Agarwal, Biofuels (alcohols and biodiesel) applications as fuels for internal
combustion engines, Prog. Energy Combust. Sci. 33 (2007) 233e271.
[2] H. Jung, D.B. Kittelson, M.R. Zachariah, Characteristics of SME biodiesel-fueled
diesel particle emissions and the kinetics of oxidation, Environ. Sci. Technol.
40 (2006) 4949e4955.
ndez, J.M. Arnal, J. Go
 mez, M.P. Dorado, A comparison of
[3] J. Campos-Ferna
performance of higher alcohols/diesel fuel blends in a diesel engine, Appl.
Energy 95 (2012) 267e275.
[4] C. Cheung, L. Zhu, Z. Huang, Regulated and unregulated emissions from a
diesel engine fueled with biodiesel and biodiesel blended with methanol,
Atmos. Environ. 43 (2009) 4865e4872.
[5] M.R. Chao, T.C. Lin, H.R. Chao, F.H. Chang, C.B. Chen, Effects of methanolcontaining additive on emission characteristics from a heavy-duty diesel engine, Sci. Total Environ. 279 (2001) 167e179.
[6] S.M. Correa, G. Arbilla, Carbonyl emissions in diesel and biodiesel exhaust,
Atmos. Environ. 42 (2008) 769e775.
[7] C.Y. Peng, H.H. Yang, C.H. Lan, S.M. Chien, Effects of the biodiesel blend fuel on
aldehyde emissions from diesel engine exhaust, Atmos. Environ. 42 (2008)
906e915.
[8] G. Karavalakis, S. Stournas, E. Bakeas, Effects of diesel/biodiesel blends on
regulated and unregulated pollutants from a passenger vehicle operated over
the European and the Athens driving cycles, Atmos. Environ. 43 (2009)
1745e1752.
[9] Y. Di, C. Cheung, Z. Huang, Experimental investigation on regulated and unregulated emissions of a diesel engine fueled with ultra-low sulfur diesel fuel
blended with biodiesel from waste cooking oil, Sci. Total Environ. 407 (2009)
835e846.
[10] C. He, Y. Ge, J. Tan, K. You, X. Han, J. Wang, et al., Comparison of carbonyl
compounds emissions from diesel engine fueled with biodiesel and diesel,
Atmos. Environ. 43 (2009) 3657e3661.
[11] G. Karavalakis, S. Stournas, E. Bakeas, Light vehicle regulated and unregulated
emissions from different biodiesels, Sci. Total Environ. 407 (2009) 3338e3346.
[12] G. Fontaras, G. Karavalakis, M. Kousoulidou, L. Ntziachristos, E. Bakeas,
S. Stournas, et al., Effects of low concentration biodiesel blends application on
modern passenger cars. Part 2: impact on carbonyl compound emissions,
Environ. Pollut. 158 (2010) 2496e2503.
[13] K.T. Magara-Gomez, M.R. Olson, T. Okuda, K.A. Walz, J.J. Schauer, Sensitivity of
hazardous air pollutant emissions to the combustion of blends of petroleum
diesel and biodiesel fuel, Atmos. Environ. 50 (2012) 307e313.
[14] H.R. Chao, T.C. Lin, M.R. Chao, F.H. Chang, C.I. Huang, C.B. Chen, Effect of
methanol-containing additive on the emission of carbonyl compounds from a
heavy-duty diesel engine, J. Hazard. Mater. 73 (2000) 39e54.
[15] C. Cheung, Y. Di, Z. Huang, Experimental investigation of regulated and unregulated emissions from a diesel engine fueled with ultralow-sulfur diesel
fuel blended with ethanol and dodecanol, Atmos. Environ. 42 (2008)
8843e8851.
[16] X. Pang, Y. Mu, J. Yuan, H. He, Carbonyls emission from ethanol-blended
gasoline and biodiesel-ethanol-diesel used in engines, Atmos. Environ. 42
(2008) 1349e1358.
[17] L. Zhu, C. Cheung, W. Zhang, J. Fang, Z. Huang, Effects of ethanolebiodiesel
blends and diesel oxidation catalyst (DOC) on particulate and unregulated
emissions, Fuel 113 (2013) 690e696.
[18] Z. Zhang, C. Cheung, T. Chan, C. Yao, Experimental investigation on regulated
and unregulated emissions of a diesel/methanol compound combustion engine with and without diesel oxidation catalyst, Sci. Total Environ. 408 (2010)
865e872.
[19] M.D. Ford, Clinical Toxicology, WB Saunders Company, 2001.
[20] USEPA, Inventory of US Greenhouse Gas Emissions and Sinks, 1994.
[21] R. Snyder, Ethel Browning's Toxicity and Metabolism of Industrial Solvents,
Elsevier Amsterdam, 1987.
[22] Worldwide A, Documentation of the TLVs and BEIs with Other Worldwide
Occupational Exposure ValuesdCD-ROMd2003, 2003. Cincinnati, OH.
[23] R.H. McKee, D. Herron, M. Saperstein, P. Podhasky, G.M. Hoffman, L. Roberts,
The toxicological properties of petroleum gases, Int. J. Toxicol. (2013), http://
dx.doi.org/10.1177/1091581813504225.

[24] E. Bingham, B. Cohrssen, C.H. Powell, Patty's Toxicology, in: Toxicological Issues Related to Metals, Neurotoxicology and Radiation Metals and Metal
Compounds, Vol. 2, John Wiley and Sons, 2001.
[25] IPCS C, International Chemical Safety Card on Isopentane, April 1994. Available from, as of October. 2006;11.
[26] A. Hamilton, H. Hardy, Cyanides. Industrial Toxicology Acton, Mass: Publishing Sciences Group Inc, 1974, pp. 221e228.
[27] E. Grosjean, R.A. Rasmussen, D. Grosjean, Ambient levels of gas phase pollutants in Porto Alegre, Brazil, Atmos. Environ. 32 (1998) 3371e3379.
[28] Hazardous Substance Fact Sheet: Iso-butylene, New Jersey Department of
Health,
1999.
http://web.doh.state.nj.us/rtkhsfs/factsheets.aspx?
lanenglish&alphA&carcinogenFalse&newFalse (accesed on 22.06.15).
[29] Hazardous Substance Fact Sheet: Acetylene, New Jersey Department of
Health,
2009.
http://web.doh.state.nj.us/rtkhsfs/factsheets.aspx?
lanenglish&alphA&carcinogenFalse&newFalse (accesed on 22.06.15).
[30] Hazardous Substance Fact Sheet: Octane, New Jersey Department of Health,
2010.
http://web.doh.state.nj.us/rtkhsfs/factsheets.aspx?
lanenglish&alphA&carcinogenFalse&newFalse (accesed on 22.06.15).
[31] R.L. Melnick, J. Huff, 1, 3-butadiene: Toxicity and Carcinogenicity in Laboratory Animals and in Humans. Reviews of Environmental Contamination and
Toxicology, Springer, 1992, pp. 111e144.
[32] Toxicological Prole for Benzene, US Department of Health and Human Services, Agency for Toxic Substances and Disease Registry, Atlanta, GA, 2007.
[33] M.J. Ellenhorn, D.G. Barceloux, Diagnosis and Treatment of Human Poisoning.
Medical Toxicology, 1997, pp. 609e610.
[34] Series I. Environmental health criteria 89. Indoor air.5:4.
[35] US Environmental Protection Agency, Health Assessment Document for
Acetaldehyde, US EPA, Research Triangle Park, NC, 1987.
[36] M. Sittig, Handbook of Toxic and Hazardous Chemicals, 1981.
[37] Hazardous Substance Fact Sheet: Acetic Acid, New Jersey Department of
Health,
2007.
http://web.doh.state.nj.us/rtkhsfs/factsheets.aspx?
lanenglish&alphA&carcinogenFalse&newFalse (accesed on 22.06.15).
[38] Hazardous Substances Data Bank (HSDB, Online Database). National Toxicology Information Program, National Library of Medicine, Bethesda, MD,
1993.
[39] Indian standard (IS 14273), Automotive vehicles e exhaust emissions
egaseous pollutants from vehicles tted with compression ignition engines.
India, Method Meas. (1999).
[40] A.K. Agarwal, P.C. Shukla, J.G. Gupta, C. Patel, R.K. Prasad, N. Sharma, Unregulated emissions from a gasohol (E5, E15, M5, and M15) fuelled spark ignition
engine, Appl. Energy 154 (2015) 732e741.
[41] A. Dhar, A.K. Agarwal, Performance, emissions and combustion characteristics
of Karanja biodiesel in a transportation engine, Fuel 119 (2014) 70e80.
[42] A.K. Agarwal, A. Dhar, Experimental investigations of performance, emission
and combustion characteristics of Karanja oil blends fuelled DICI engine,
Renew. Energy 52 (2013) 283e291.
[43] J.B. Heywood, Internal Combustion Engine Fundamentals, Mcgraw-hill, New
York, 1988.
[44] J.H. Seinfeld, S.N. Pandis, Atmospheric Chemistry and Physics: from Air
Pollution to Climate Change, John Wiley & Sons, 2012.
[45] H. Raheman, A. Phadatare, Diesel engine emissions and performance from
blends of karanja methyl ester and diesel, Biomass Bioenergy 27 (2004)
393e397.
[46] V. Bermdez, J.M. Lujan, B. Pla, W.G. Linares, Comparative study of regulated
and unregulated gaseous emissions during NEDC in a light-duty diesel engine
fuelled with Fischer Tropsch and biodiesel fuels, Biomass Bioenergy 35 (2011)
789e798.
[47] B.-Q. He, S.-J. Shuai, J.-X. Wang, H. He, The effect of ethanol blended diesel
fuels on emissions from a diesel engine, Atmos. Environ. 37 (2003)
4965e4971.
[48] P. Eastwood, Particulate Emissions from Vehicles, John Wiley & Sons, 2008.

Nomenclature
KOH: Potassium hydroxide
NaOH: Sodium hydroxide
HC: Hydrocarbon
CO: Carbon monoxide
CO2: Carbon dioxide
BTX: Benzene, toluene, xylene
NOX: Oxides of nitrogen
ADC: Athens driving cycle
NEDC: New European driving cycle
THC: Total hydrocarbons
FTIR: Fourier transform infrared
NDIR: Non-dispersive infrared
FID: Flame ionization detection
CLD: Chemiluminescense detection
H2O: Water
NO: Nitric oxide
NO2: Nitrogen dioxide
N2O: Nitrous oxide
CH4: Methane

Please cite this article in press as: A.K. Agarwal, et al., Unregulated emissions and health risk potential from biodiesel (KB5, KB20) and methanol
blend (M5) fuelled transportation diesel engines, Renewable Energy (2016), http://dx.doi.org/10.1016/j.renene.2016.03.058

A.K. Agarwal et al. / Renewable Energy xxx (2016) 1e9

n-C4H10: n-Butane
iso-C4H10: iso-Butene
n-C5H12: n-Pentane
n-C8H18: n-Octane
C2H2: Acetylene
C2H4: Ethylene
HCHO: Formaldehyde
CH3CHO: Acetaldehyde
C2H5OH: Ethanol
SO2: Sulfur dioxide
HCOOH: Formic acid
C6H6: Benzene
H2SO4: Sulfuric acid
SO3: Sulfur trioxide

C2H6: Ethane
C3H6: Propylene
C3H8: Propane
1,3dC4H6: 1,3-Butadine
iso-C4H8: iso-Butylene
iso-C5H12: iso-Pentane
CH3COOH: Acetic acid
C7H8: Toluene
NH3: Ammonia
EPA: Environmental Protection Agency
GHG: Greenhouse gas
CH3OH: Methanol
HNCO: Isocynic acid

Please cite this article in press as: A.K. Agarwal, et al., Unregulated emissions and health risk potential from biodiesel (KB5, KB20) and methanol
blend (M5) fuelled transportation diesel engines, Renewable Energy (2016), http://dx.doi.org/10.1016/j.renene.2016.03.058