Atmospheric Environment 136 (2016) 134e143

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Atmospheric Environment
journal homepage: www.elsevier.com/locate/atmosenv

Unregulated emissions from light-duty hybrid electric vehicles

R. Suarez-Bertoa*, C. Astorga**
European Commission, Joint Research Centre (JRC), Institute for Energy and Transport (IET), Sustainable Transport Unit, 21027 Ispra, VA, Italy

h i g h l i g h t s

NH3, ethanol and acetaldehyde emissions are in the same range of gasoline vehicles.

Regulated emissions are in the same range as gasoline vehicles.

Higher regulated and unregulated emissions were observed at 7  C than at 23  C.

The battery state of charge strongly impacts the plug-in hybrid emissions.

a r t i c l e i n f o a b s t r a c t

Article history: The number of registrations of light duty hybrid electric vehicles has systematically increased over the
Received 27 January 2016 last years and it is expected to keep growing. Hence, evaluation of their emissions becomes very
Received in revised form important in order to be able to anticipate their impact and share in the total emissions from the
17 April 2016
transport sector. For that reason the emissions from a Euro 5 compliant hybrid electric vehicle (HV2) and
Accepted 18 April 2016
Available online 20 April 2016
a Euro 5 plug-in hybrid electric vehicle (PHV1) were investigated with special interest on exhaust
emissions of ammonia, acetaldehyde and ethanol. Vehicles were tested over the World harmonized
Light-duty Test Cycle (WLTC) at 23 and 7  C using two different commercial fuels E5 and E10 (gasoline
Keywords:
Vehicle emissions
containing 5% and 10% vol/vol of ethanol, respectively). PHV1 resulted in lower emissions than HV2 due
Plug-in hybrid to the pure electric strategy used by the former. PHV1 and HV2 showed lower regulated emissions than
WLTC conventional Euro 5 gasoline light duty vehicles. However, emissions of ammonia (2e8 and 6
Ammonia e15 mg km1 at 22 and 7  C, respectively), ethanol (0.3e0.8 and 2.6e7.2 mg km1 at 22 and 7  C,
Cold start emissions respectively) and acetaldehyde (~0.2 and 0.8e2.7 mg km1 at 22 and 7  C, respectively) were in the
same range of those recently reported for conventional gasoline light duty vehicles.
© 2016 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND
license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction
Hybrid electric vehicles (HEVs) have been presented as a
promising approach to reduce the emissions of pollutants from
vehicle exhaust. HEVs registrations has continuously increased
over the last years, reaching share of 1.4% of all new car sales in the
EU in 2014, which is more than twice the registrations of 2011
(ICCT, 2014). Hybrid electric vehicles comprise two alternative
powertrains: an internal combustion engine (ICE) combined with
an electric motor that includes an energy storage system recharged
by the vehicle means (ICE, regenerative braking, etc.). There are
three hybrid electric configurations: parallel, series and parallel/
* Corresponding author.
** Corresponding author.
E-mail addresses: ricardo.suarez-bertoa@jrc.ec.europa.eu (R. Suarez-Bertoa),
covadonga.astorga-llorens@jrc.ec.europa.eu (C. Astorga).
series. Parallel design uses both ICE and electric motor to move the
vehicle, using the ICE as the main power source and the electric one
to assist according to the driving condition. In this configuration,
the battery provides energy to the vehicle through an electric
motor, which acts also as generator, recharging the battery (Çag
atay
Bayindir et al., 2011). Series configuration uses the ICE as generator,
supplying electricity to the electric motor, which provides the en-
ergy needed to move the vehicle, and recharging the battery
(Hannan et al., 2014). In the case of parallel/series hybrid vehicles a
power split device allows moving the vehicle using only the IEC, or
the electric motor or even both simultaneously.
Plug-in hybrid electric vehicles (PHVs), equipped with an elec-
tric powertrain and a battery pack which can be directly charged
from the electric grid, have been recently introduced. The PHVs
allow for pure electric driving under certain conditions. While
running in pure electric mode there is no exhaust emission. While
PHVs generally have higher power electric motor and higher

http://dx.doi.org/10.1016/j.atmosenv.2016.04.021
1352-2310/© 2016 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
 R. Suarez-Bertoa, C. Astorga / Atmospheric Environment 136 (2016) 134e143
battery capacity than HEVs, some HEVs (non-plugin) also allow
operation in pure electric mode. The main difference between HEVs
and PHVs is the external charging capability. In Europe, PHVs reg-
istrations increased from a few hundred in 2011 to nearly nine
thousand in 2012. The number of PHVs registrations tripled from
2012 to 2013. This growth cooled down from 2013 to 2014, showing
an increase of 30% (Christian Thiel and Dilara, 2015).
Previous works reported that hybrid electric vehicles present
improved energy efficiency and lower pollutants emissions
compared to conventional vehicles (Fontaras et al., 2008; Alvarez
and Weilenmann, 2012). As a consequence of the fast introduc-
tion of the HEVs and PHVs in the market, evaluation of their
regulated and unregulated pollutant emissions becomes very
important in order to be able to anticipate their impact and share in
the total emissions from the transport sector.
Low temperatures typically lead to higher vehicular emissions,
especially for conventional gasoline vehicles (Dardiotis et al., 2013).
Most of these emissions take place during the cold start, which is
the period elapsing from the start of the ICE until hot engine
operation and optimal temperature of the catalytic converter
(hereinafter catalyst) are reached. Alvarez et al. suggested that the
influence of low ambient temperatures on regulated emissions
from hybrid electric vehicles equipped with a spark ignition engine
is similar to that of conventional gasoline vehicles (Alvarez and
Weilenmann, 2012). Combustion engine and after-treatment
could then be affected by the presence of an electrical motor and
an energy storage system that supply the needed energy during the
low speed regime of the vehicle, delaying and/or modifying the
vehicle cold start.
Ammonia (NH3), ethanol and acetaldehyde are pollutants that
can be present in vehicle exhaust (Bishop and Stedman, 2015;
Clairotte et al., 2012; Durbin et al., 2007; Graham et al., 2008;
Karavalakis et al., 2014; Suarez-Bertoa et al., 2014, 2015a,b).
While NH3 emissions are linked to the use of three-way catalyst in
conventional gasoline vehicles, emissions of ethanol and acetal-
dehyde are related to the use of ethanol containing blends. NH3 is
classified under the European dangerous substances directive (67/
548/EEC) as toxic, corrosive and dangerous for the environment. It
is a precursor of atmospheric secondary aerosols (Behera and
Sharma, 2010; Pope et al., 2002). Its reaction with nitric and sul-
furic acid leads to the formation of atmospheric secondary aerosols,
namely, ammonium nitrate and ammonium sulfate (Behera and
Sharma, 2010; Pope et al., 2002). The deposition of the ammo-
nium salts leads to hypertrophication of waters and acidification of
soils with negative effects on nitrogen-containing ecosystems
(Bouwman et al., 2002; Erisman et al., 2003; Sutton et al., 2000).
Acetaldehyde is classified as probable carcinogenic by the US
Department of Health and Human Services, and ethanol is an at-
mospheric precursor of acetaldehyde and peroxyacetyl nitrate
(PAN) (Millet et al., 2010, 2012). Furthermore, acetaldehyde is
classified as a hazardous air pollutant by the U.S. EPA (U.S. EPA), and
its subsequent oxidation can lead to production of ozone (O3) and
PAN. Hence, these two compounds are also associated with urban
air pollution (Durbin et al., 2007; Graham et al., 2008; Andrade
et al., 1998).
Hybrid electric and plug-in hybrid vehicles are expected to take
over a large fraction of the vehicle market thanks to their low en-
ergy consumption and low CO2 emissions. Therefore, it is of major
importance to understand how these new technologies and im-
provements impact on the emissions under different conditions
(e.g., temperature, fuel, battery state of charge). In that frame, the
present work presents the first comprehensive study of the exhaust
emissions (regulated pollutants, CO2, NH3, acetaldehyde and
ethanol) from a HEV (parallel, mild hybrid) and a PHV (series-
parallel, full hybrid), both spark ignition and Euro 5 compliant, over
135
the world harmonized light-duty test cycle (WLTC), which is
considered to be representative of real world driving conditions.
This test cycle will be used for type approval of light-duty vehicles
(LDVs) in the European Union and potentially other countries who
are signatories of the agreements to the United Nations Economic
Commission for Europe (UNECE) (UNECE, 2015). The new step
(Euro 6c) of the EU legislation will be implemented for new types
on September 2017 and for new vehicles on September 2018. The
vehicles were tested at 23  C and also at 7  C to study the effect of
low ambient temperature. This temperature was chosen since it is
used during the low temperature emissions test, also known as
Type 6 test (European Commission, 2008). Finally, two different
commercial fuels E5 and E10 (gasoline containing 5% and 10% vol/
vol of ethanol, respectively) were used to evaluate if different
ethanol content in commercial fuel blends could influence the
emissions of these type of vehicles.
2. Experimental
A plug-in hybrid electric vehicle (PHV1) and a hybrid electric
vehicle (HV2), both Euro 5 compliant ((EC) No 692/2008)
(European Commission, 2008), were tested (see technical details in
Table 1) over the WLTC in the Vehicle Emission Laboratory (VELA)
at the European Commission Joint Research Centre Ispra, Italy using
a certified chassis dynamometer (see Fig. 1 for test cell configura-
tion). The VELA facility comprises a climatic test cell with controlled
temperature and relative humidity (RH) to simulate a variety of
ambient conditions (temperature range: 10 to 35  C; RH range:
50e80%). Tests were performed on a chassis dynamometer (inertia
range: 454e4500 kg), designed for two and four-wheel drive light-
duty vehicles (LDVs) (two 1.22 m roller benches e MAHA GmbH,
Germany). The emissions were fed to a Constant Volume Sampler
(CVS, Horiba, Japan) using a critical Venturi nozzle to regulate the
flow (CVS flow range: 3e30 m3 min1). A series of thermocouples
monitored the temperature of the oil, cooling water, exhaust, and
ambient conditions. A universal exhaust gas oxygen (UEGO) type
sensor was connected to the tailpipe to follow the air to fuel ratio.
Vehicles were kept inside the climatic cell under the described
conditions for a 24 h soaking period.
All tests were performed following the WLTC which is a cold
start driving cycle. The vehicle and its components (oil, coolant,
catalyst, etc) must be at 23 or 7  C, ± 1  C, at the beginning of the
test cycle. The driving cycle consists of four phases with different
speed distributions (see Fig. 1) and it intends to be representative of
the real world driving conditions being based on real world vehicle
journeys from several countries. The length of the entire cycle is
1800 s and is comprised of the low speed (589 s), medium speed
(433 s), high speed (455 s) and extra-high speed (323 s) phases. It
reaches a maximum speed of 131.3 km h1 and is about 23.3 km
long. Three different driving cycles have been developed on the
basis of the vehicle’s power-to-mass ratio and its maximum speed,
Table 1
Fleet general features.
Denomination PHV1 HV2
Internal combustion engine Spark ignition Spark ignition
Type by drivetrain layout Series- Parallel Parallel
Type by level of hybridization Full hybrid Mild hybrid
EU emission standard Euro 5 Euro 5
After-treatment TWC TWC
Engine displacement (cm3) 1798 1497
Engine power (kW) 73 97
Odometer (km) 3546 9969
Three-Way Catalyst (TWC)
136 R. Suarez-Bertoa, C. Astorga / Atmospheric Environment 136 (2016) 134e143

Fig. 1. WLTC (top) and schematic diagram of the experimental setup (bottom).

to represent three different vehicle classes. The vehicle tested in the
present study pertains to class 3 (power/mass >34 kW/ton), which
is the highest power class. Fig. 1 illustrates the version WLTC 5.3 of
the speed profile applicable for this class of vehicle (Marotta et al.,
2015).
Battery pack level of charge was recorded by the on-board
diagnosis (OBD) and expressed as the percent remaining level of
charge for the battery, which is commonly known as the battery
state of charge (SOC) (SAE, 2014). Tests were performed using the
vehicles with the battery system at their maximum SOC. While the
PHV1 was charged using its own plug connected to the electrical
grid, the battery of HV2 was charged to its maximum using a car
battery charger. Therefore, the performed tests could be considered
as the best case scenario, and for the PHV1 it is an example of the
emissions resulting from a PHV that is used after a typical overnight
charging period reaching it maximum SOC. Even though measured,
the effect that the battery SOC has on vehicles emissions is not
within the scope of the present study. The number and type of tests
need for the type approval of these vehicles over the WLTC is still
under discussion at international level.
2.1. Fuel blends
The EU has set a 10% renewable energy share in the transport
sector to be complied with by 2020 (2009/28/EC) (EC, 2009). In
2010, the use of renewable energy by the transport sector was
4.70% and the 91% of this share was covered by biofuels (European
Commission, 2013). The latest version of the principle European
gasoline (EN228) standards allows blending up to E10 (gasoline
containing up to 10% volume of ethanol). E5 (gasoline containing up
 R. Suarez-Bertoa, C. Astorga / Atmospheric Environment 136 (2016) 134e143 137

to 5% vol/vol of ethanol) and E10 are the most common ethanol
blends in Europe as today and have been formalised in the CEN EN
228 standard for motor gasoline. Ethanol, even at low concentra-
tions in motor gasoline, is known to impact both the fuel con-
sumption and emissions from vehicles. Volumetric fuel
consumption generally increases when running in ethanol/gasoline
blends because ethanol has lower energy content per litre
compared to conventional hydrocarbon gasoline.
2.2. Analytical instrumentation
Fig. 3a). During tests at 7  C, PHV1 used the ICE during most of the
phase 1, then run as pure electric during the phase 2, and after the
second 1200 (phase 3) it used both IEC and pure electric mode, as it
did at 23  C. This shows a clear effect of the low temperature on
PHV1 performance. Hence, in order to assure a good drivability, the
plug-in vehicle, PHV1, used the ICE during the first part of the cycle
when tested at 7  C (see Fig. 3a). HV2, however, run using the ICE
during most of the WLTC at the two temperatures (see Fig. 3b). For
this reason, PHV1 presented significantly lower CO and NOx
emissions than HV2.

The regulated gaseous emissions were measured using standard

methodologies defined by the light-duty vehicle Global Technical
Regulation (GTR). An integrated setup (MEXA-7400HTR-LE,
HORIBA) analyzes diluted gas from a set of Tedlar bags connected to
the CVS (Automatic Bag Sampler, CGM electronics) using non-
dispersive infrared (for CO/CO2), a chemiluminescence (for NOx)
and a heated (191  C) flame ionization detector (FID; for THC). The
GTR specifies globally harmonized performance-related equipment
specifications and test procedures (UNECE, 2015). The tests were
done following the World-harmonized Light-duty vehicle Test
Procedure (WLTP) (UNECE, 2015). More than twenty gaseous
compounds contained in the raw exhaust (e.g. NO, N2O, CH4, NH3,
CH3CHO, CH3CH2OH) were monitored at 1 Hz acquisition frequency
by a High Resolution Fourier Transform Infrared spectrometer (FTIR
e MKS Multigas analyzer 2030-HS, Wilmington, MA, USA). The
method and instrument are described in more detail in the litera-
ture (Clairotte et al., 2012; Suarez-Bertoa et al., 2015c), therefore,
only a brief description is given here. The device consists of a silicon
carbide source (at 1200  C), a multipath cell (optical length: 5.11 m),
a Michelson interferometer (spectral resolution: 0.5 cm1, spectral
range: 600e3500 cm1) and a liquid nitrogen cooled mercury
cadmium telluride detector (MCT). A second set of analyzers,
similar to the one used for gaseous regulated emission measure-
ment was directly connected to the vehicle’s exhaust pipe allowing
a time-resolved (at 1 Hz) measurement of THC, NOx and CO/CO2
from the raw exhaust. CO, CO2 and NOx measurements from these
analyzers were used to synchronize the FTIR time-resolved signal
(for more information see Clairotte et al., 2012 (Clairotte et al.,
2012)). The raw exhaust flow was determined by subtracting the
flow of dilution air introduced into the tunnel, measured with a
Venturi system, to the total flow of the dilution tunnel, measured by
a sonic Venturi (Horiba). Mass flows were derived from the exhaust
gas flow rates (m3 s1) and from the measured concentration
(ppmv). Emission factors (EFs, mg km1) were calculated from the
integrated mass flow and the total driving distance of the WLTC
(23.3 km).

3. Results and discussion

3.1. Regulated gases emissions

Fig. 2 illustrates the EFs of the regulated gases obtained for two
fully charged Euro 5 hybrids, PHV1 and HV2, fueled with E5 and E10
blends and tested over the WLTC at 23 and 7  C. Regulated pol-
lutants EFs over the WLTC are summarized in Table 2, EFs from each
of the four phases (low, medium, high and extra-high speed) are
shown in Tables S1 and S2 in the supplementary material. PHV1
and HV2, regulated emissions were well below Euro 5 limits
(Regulations 715/2007/EC and 692/2008/EC) at all studied
conditions.
PHV1 run on pure electric mode during the first 1200s of the
WLTC (WLTC 1800s) when tested fully charged at 23  C. These Fig. 2. Regulated compounds emission factors (mg km1) over the WLTC. Hatched bar
1200s correspond to a distance of 10 km, which was the maximum plots refer to experiments at 7  C. Error bars represent maximum semi-dispersion
autonomy of the vehicle battery at pure electric operation (see from two tests.
138 R. Suarez-Bertoa, C. Astorga / Atmospheric Environment 136 (2016) 134e143

PHV1’s THC and NMHC emissions were similar than those of
HV2 at 23  C, and higher at 7  C. THC and NMHC are typically
emitted during the cold start. As soon as the ICE kicked in, THCs
started being emitted, a similar behavior to that presented by
conventional gasoline vehicles (Dardiotis et al., 2013). Overall, very
similar emissions were obtained from tests performed using E5 and
E10 blends for each vehicle. Higher emissions were always
observed at 7  C.
In Europe, vehicles manufacturers will have to guarantee that
their entire LDV fleet does not emit on average more than
95 g km1 of CO2 by 2020 (EU, 2014). PHV1 emitted on average
52 ± 4 and 52.0 ± 0.8 g km1 and of CO2 when tested at 23  C with
E5 and E10 respectively. CO2 tailpipe emissions from PHV1 were 1.5
times higher during the tests at 7  C. HV2 emitted on average
133.4 ± 0.8 and 133.7 ± 0.3 g km1 at 23  C with E5 and E10
respectively. HV2’s CO2 tailpipe emissions were 1.2 times higher at
7  C.
THC and CO EFs of PHV1 and HV2 are similar to those reported
for a Euro 4 compliant HEV tested over the NEDC at 21  C and 27  C
by Fontaras et al. (Fontaras et al., 2008). NOx emissions, however,
were respectively 2 times and more than 30 times lower for HV2
and PHV1, compared to the Euro 4 hybrid electric vehicle reported
in that study.
EFs of all regulated compounds were substantially lower for the
PHV1 and the HV2 than those reported by Marotta et al. (Marotta
et al., 2015) for a fleet of Euro 5 and Euro 6 gasoline LDVs tested
over the WLTC at 23  C. The largest differences were observed in
the case of the PHV1 whose NOx emissions were more than 80
times lower than the average of the gasoline fleet. THC and CO
emissions from HV2 and PHV1 were 2e7 times lower than those
reported for the gasoline LDVs. While CO2 emissions from HV2 at
23  C were similar to the average of the gasoline fleet reported in
that study, those from PHV1 were 3 times lower. Regulated emis-
sions from PHV1 and HV2 were also lower than what reported for a
Euro 5 flex-fuel vehicle (FFV) running in E5 over the WLTC at 23  C
by Suarez-Bertoa et al. (Suarez-Bertoa et al., 2015a). However, THC,
CO and CO2 emissions from PHV1 and HV2 were similar to those for
the FFV when the vehicles were tested at 7  C (NOx emissions
were respectively 15 and 5 times lower for PHV1 and HV2
compared to the FFV).
3.2. Unregulated emissions
NH3, acetaldehyde and ethanol exhaust emissions from PHV1
and HV2 fueled with E5 and E10 blends and tested over the WLTC at
23 and 7  C were measured on-line with a high resolution FTIR at
the vehicles’ tailpipe. EFs of these three pollutants are summarized
in Tables 2 and 3. As already explained, hybrid electric vehicles
comprised an electric powertrain combined with an ICE, which in
the case of PHV1 and HV2 is a spark ignition engine. Like any recent
spark ignition vehicle, both vehicles were also equipped with a
TWC as after-treatment system. In TWC NH3 is produced, through a
mechanism that involves NO and molecular hydrogen (H2), right
after catalyst light-off (Bradow and Stump, 1977). H2 is formed on
the catalyst from a water-gas shift reaction between CO and water
or via steam reforming from hydrocarbons (Whittington et al.,
1995). Not surprisingly, the two studied hybrid electric vehicles
presented NH3 emissions while running in the ICE at all studied
conditions (see Table 2, Figs. 3 and 4).
PHV1 run on pure electric mode for 1200 s before using the ICE
at 23  C. For that reason emissions of NH3 were not observed until
the very end on the WLTC. HV2 uses the ICE from the very begin-
ning, and during most part of the WLTC. Furthermore, HV2’s cata-
lyst lights off after a few seconds. Longer request of the ICE and
sooner catalyst light-off led to higher NH3 emissions from HV2 than
from PHV1 at all studied conditions (see Table 2). In general, NH3
formation over the catalyst is enhanced at low lambda (air/fuel
ratio), also known as rich combustion, where conditions are
reductive and higher concentrations of CO and H2 are present
(Whittington et al., 1995; Czerwinski et al., 2010). The studied ve-
hicles tended to run on rich conditions (air/fuel ratio < 1) for a
longer period at 7  C than at 23  C (see Figures S1-S4 of the
supplementary material). As a consequence, the NH3 emissions of
PHV1 and HV2 were approximately 2 times higher at 7  C than at
23  C for both E5 and E10 fuel blends (see Table 2). The same trends
were already reported in previous studies for conventional gasoline
LDVs (Suarez-Bertoa et al., 2014, 2015c; Heeb et al., 2006; Huai
et al., 2003). Since NH3 emissions are not regulated for LDVs,
lambda control aims at reducing NOx and CO emissions.
PHV1 presented lower NH3 emissions using E10 (7 ± 4 and
11.1 ± 0.9 mg km1 at 23 and 7  C, respectively) than using E5
blend (1.9 ± 0.6 and 6 ± 1 mg km1 at 23 and 7  C, respectively).
This could arise as a consequence of PHV1’s longer rich combustion
present during the tests performed using E5 compared to those
using E10. HV2 presented similar air/fuel ratio with both blends,
which lead to similar NH3 emissions at 7  C (13 ± 2 and
15.4 mg km1, for E5 and E10, respectively) and slightly higher NH3
emissions for E10 at 23  C (6.1 ± 0.3 and 8.0 mg km1 for E5 and
E10, respectively). Higher emissions of CO and lower emissions of
NO (NH3 precursors) were present at conditions where higher
emissions of NH3 were observed. Therefore, as suggested by Kean at
al. (Kean et al., 2009) and Livingston et al. (Livingston et al., 2009),
CO emissions from gasoline vehicles are indicative of NH3 forma-
tion over the catalyst at expenses of NO (Kean et al., 2009;
Livingston et al., 2009). Even though PHV1 and HV2 showed
lower regulated emissions than gasoline LDVs, their NH3 EFs were

Table 2
Regulated and unregulated emission factors (mg km1, *CO2 emission factor (g km1)) over the WLTC at 23 and 7  C. In parentheses, maximum semi-dispersion.

PHV1 HV2

23  C 7  C 23  C 7  C

E5 E10 E5 E10 E5 E10 E5 E10

THC 9 (±2) 6.8(± 0.1) 108 (±5) 98 (±5) 12.9 (±0.8) 13 (±1) 79 (±6) 76 (±3)
CH4 1 (±1) 0.7 (±0.1) 3.5 (±0.3) 3.3 (±0.3) 1.0 (±0.1) 1.2 (±0.1) 3.8 (±0.3) 3.6 (±0.1)
NMHC 7.8 (±0.6) 6.1 (±0.0) 104 (±5) 95 (±5) 11.9 (±0.7) 11 (±1) 75 (±6) 72 (±3)
CO 80 (±22) 62 (±4) 323 (±52) 363 (±56) 206 (±23) 238 (±25) 568 (±36) 623 (±5)
NOx 0.4 (±0.7) 0.5 (±0.0) 5 (±2) 3.7 (±0.5) 7 (±2) 7.8 (±0.3) 13.5 (±0.3) 12.0 (±0.2)
CO*2 g/km 52 (±4) 52.0 (±0.8) 77.3 (±0.1) 79 (±3) 133.2 (±0.8) 133.7 (±0.7) 164.5 (±0.2) 157.9 (±0.1)
NH3 7 (±4) 1.9 (±0.6) 11.1 (±0.9) 6 (±1) 6.1 (±0.3) 8.0 (±0.0) 13.0 (±2) 15.4 (±0.0)
Ethanol 0.3 (±0.3) 0.8 (±0.1) 2.6 (±0.1) 7.2 (±2.7) 0.6 (±0.1) 0.7 (±0.0) 3.1 (±0.1) 7.0 (±0.9)
CH3CHOa 0.1 (±0.0) 0.2 (±0.1) 1.8 (±0.0) 2.7 (±0.0) 0.2 (±0.1) 0.2 (±0.1) 0.8 (±0.0) 1.4 (±0.1)
a
Acetaldehyde; Euro 5 spark ignition emission limits (mg km1) at 20e30  C over the New European Driving Cycle (NEDC): THC ¼ 100; NMHC ¼ 68; CO ¼ 1000; NOx ¼ 60.
 R. Suarez-Bertoa, C. Astorga / Atmospheric Environment 136 (2016) 134e143 139

Fig. 3. Exhaust flow (Flow TP; m3 min1) and NO, CO and NH3 emission rates (g s1) of (a) PHV1 and (b) HV2 over the WLTC (grey) at 23  C (left plots) and 7  C (right plots) at full
SOC.

within the range reported in previous studies for Euro 5 spark Ethanol and acetaldehyde exhaust emissions of conventional
ignition vehicles at 23 and 7  C (Suarez-Bertoa et al., 2014; Kean vehicles have been shown to be associated to uncombusted ethanol
et al., 2009; Livingston et al., 2009). fraction from the fuel blends. Ethanol and acetaldehyde EFs are
140 R. Suarez-Bertoa, C. Astorga / Atmospheric Environment 136 (2016) 134e143

Fig. 3. (continued).

summarized in Table 2. Emissions of ethanol and acetaldehyde all conditions. Once the catalyst reached the optimal operating
were present during the cold start and until the catalyst light-off at temperature, the emissions of these unregulated compounds were
 R. Suarez-Bertoa, C. Astorga / Atmospheric Environment 136 (2016) 134e143
Table 3
Total cold start emissions (g) of ethanol and acetaldehyde (CH3CHO) using E5 and E10 blends at 23 and 7  C. In parentheses, maximum semi-dispersion.
PHV1
23  C 7  C
E5 E10 E5
Ethanol 5.6 (±5.3) 15 (±3) 59 (±1)
CH3CHO 1.9 (±0.0) 3.8 (±0.0) 41.6 (±0.7)
Fig. 4. Ammonia emission factors (mg km1) over the WLTC. Hatched bar plots refer to
experiments at 7  C. Error bars represent maximum semi-dispersion from two tests.
below the detection limit. Emissions of acetaldehyde and ethanol
were affected by ambient temperature, increasing at 7  C (see
Table 2). Similar EFs of ethanol and acetaldehyde were observed
during the tests performed using E5 and E10 at 23  C for two
studied HEVs (see Table 2). Emissions were higher for E10 than for
E5 at 7  C. Together, emissions of ethanol and acetaldehyde
accounted, on average, for about 5 and 10% of THC emitted when
using E5 and E10, respectively. Of those, 81e99% were emitted
during the cold start. The cold start period of the vehicle was
defined based on the legislation for heavy duty vehicles (EC No 582/
2011) (EC, 2009), which considers the period elapsing from the
start of the test until the coolant temperature reaches 70  C for the
first time as the cold start. This period lasted about 1300 s (18.8 km)
at 23  C and 1600 s (20.4 km) at 7  C for PHV1 and 360 s (1.9 km)
at 23  C and 380 s (2.3 km) at 7  C for HV2. Cold start of PHV
depends on the pure electric mode strategy implemented. Since EFs
are expressed as mass distance1, cold emissions that take place
later in the WLTC (e.g. emissions from PHV1), are divided by a
higher number (kilometres covered). Therefore, EFs would result to
be lower even at equal emitted mass. For that reason, cold start
emissions are also reported as total emissions (see Table 3).
Similar acetaldehyde EFs were reported for a fleet of gasoline
LDVs tested over the Federal Test Procedure (FTP) driving cycle
(fleet average 0.4 ± 0.1 mg km1) by Durbin et al. (Durbin et al.,
2007) and for a flex-fuel vehicle (FFV), also tested over the FTP
using E10 and a gasoline blend containing 5.7% ethanol,
(0.6 ± 0.4 mg km1) by Karavalakis et al. (Karavalakis et al., 2012).
Suarez-Bertoa et al. (Suarez-Bertoa et al., 2015a) reported similar
ethanol (1 mg km1) and higher acetaldehyde (3 mg km1) EFs for a
FFV tested over the WLTC using hydrous and anhydrous E10 blends.
PHV1 and HV2 fueled with E5 were also tested using an 88%
battery SOC to be able to probe for changes on their emissions
arising from a different SOC. While no changes were observed for
141
HV2
23  C 7  C
E10 E5 E10 E5 E10
159 (±9) 12 (±3) 13 (±4) 67 (±7) 130 (±4)
63.2 (±0.0) 5.0 (±0.3) 5 (±2) 19.5 (±0.4) 32 (±1)
HV2 at 88% SOC compared to full charge SOC, a drastic increase of
NOx, CO, CO2 and NH3 emissions was obtained from PHV1 (see
Fig. 5). At 88% SOC, NH3, CO and CO2 emissions from PHV1 were
more than 2 times higher, and NOx were 6 times higher than those
obtained at full charge SOC. The reason for this increase was a
change on the powertrains use strategy. As explained, PHV1 run on
pure electric mode for 10 km when tested at battery full charge
SOC. However, at 88% battery SOC, the ICE is used for most part of
the WLTC, leading to much higher emissions. Since THC are
emitted, during cold start, i.e., from the ignition of the ICE until the
catalyst light-off, and this took place within the time-frame of the
WLTC at the two studied SOC, THC emissions did not vary at the
different battery SOC. These results suggest that PHVs performance
and emissions may depend on their battery SOC.
4. Conclusions
Regulated and unregulated emissions from one light duty
hybrid electric vehicle (HV2) and one plug-in hybrid electric vehicle
(PHV1) have been studied over the WLTC using E5 and E10 fuel
blends.
Results suggest that, as for conventional gasoline vehicles, low
ambient temperatures lead to higher emissions of regulated and
unregulated pollutants. Furthermore, no significant differences
were observed for the regulated emissions when vehicles were
tested using either E5 or E10. PHV1 resulted in lower emissions
than HV2 due to pure electric strategy of the former, which relied
on the continuous use of battery for up to 10 km of the WLTC.
However, since THC were emitted at cold start, both vehicles
showed similar THC emissions.
While no changes were observed for HV2 when tested at 88%
battery SOC instead of full charge SOC, PHV1 resulted in much
higher emissions of NOx, CO, CO2 and NH3 at 88% SOC than at full
charge SOC. Suggesting that PHVs may performed differently ac-
cording to their battery SOC. THC emissions were not affected by
the battery SOC. These important differences in the observed
emissions and behavior shed light on the fundamental unlikeness
between the two technologies, plug-in electric hybrid and electric
hybrid, which are often seen (and studied) as the same category.
NH3 emissions presented variations depending on fuel blend
used. Thus, NH3 emissions from PHV1 were higher with E5 than
with E10 at both 23  C (7 ± 4 and 1.9 ± 0.6 mg km1, for E5 and E10,
respectively) and 7  C (11.1 ± 0.9 and 6 ± 1 mg km1, for E5 and
E10, respectively).
Ethanol and acetaldehyde emissions were similar during the
tests performed using E5 and E10 at 23  C, and higher for E10 than
for E5 at 7  C. These two compounds accounted for about 5%
(using E5) and 10% (using E10) of THC emitted. Acetaldehyde
average EFs (0.2 ± 0.1 and 1.7 ± 0.8 mg km1, at 23 and 7  C,
respectively) were similar to those reported in the literature for
gasoline and flex-fuel vehicles.
PHV1 and HV2 showed lower regulated emissions than con-
ventional Euro 5 gasoline LDVs. However, their NH3, ethanol and
acetaldehyde EFs were in the same range reported for these vehi-
cles at 23 and 7  C using E5 and E10 blends. Hence, although
142 R. Suarez-Bertoa, C. Astorga / Atmospheric Environment 136 (2016) 134e143
Fig. 5. PHV1 exhaust flow (Flow TP; m3 min1) and emission rates (g s1) of NO, CO,
NH3 over the WLTC (grey) at 23  C at 88% SOC.
hybrid electric vehicles are presented as an alternative to reduce
exhaust emissions, this is only true for the regulated pollutants.
Disclaimer
The opinions expressed in this manuscript are those of the au-
thors and should in no way be considered to represent an official
opinion of the European Commission.
Acknowledgements
The VELA staff is acknowledged for the skilful technical assis-
tance, in particular M. Cadario, R. Colombo, G. Lanappe, P. Le Lijour
and M. Sculati.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.atmosenv.2016.04.021
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