Evaluation of Solid Particle Number Sensors for Periodic Technical Inspection of Passenger Cars.

Following the increase in stringency of the European regulation limits for laboratory and real world automotive emissions, one of the main transport related aspects to improve the air quality is the mass scale in-use vehicle testing. Solid particle number (SPN) emissions have been drastically reduced with the use of diesel and gasoline particulate filters which, however, may get damaged or even been tampered. The feasibility of on-board monitoring and remote sensing as well as of the current periodical technical inspection (PTI) for detecting malfunctioning or tampered particulate filters is under discussion. A promising methodology for detecting high emitters is SPN testing at low idling during PTI. Several European countries plan to introduce this method for diesel vehicles and the European Commission (EC) will provide some guidelines. For this scope an experimental campaign was organized by the Joint Research Centre (JRC) of the EC with the participation of different instrument manufacturers. Idle SPN concentrations of vehicles without or with a malfunctioning particulate filter were measured. The presence of particles under the current cut-off size of 23 nm as well as of volatile particles during idling are presented. Moreover, the extreme case of a well performing vehicle tested after a filter regeneration is studied. In most of the cases the different sensors used were in good agreement, the high sub-23 nm particles existence being the most challenging case due to the differences in the sensors' efficiency below the cut-off size.

Comparisons of Laboratory and On-Road Type-Approval Cycles with Idling Emissions. Implications for Periodical Technical Inspection (PTI) Sensors.

For the type approval of compression ignition (diesel) and gasoline direct injection vehicles, a particle number (PN) limit of 6 × 1011 p/km is applicable. Diesel vehicles in circulation need to pass a periodical technical inspection (PTI) test, typically every two years, after the first four years of circulation. However, often the applicable smoke tests or on-board diagnostic (OBD) fault checks cannot identify malfunctions of the diesel particulate filters (DPFs). There are also serious concerns that a few high emitters are responsible for the majority of the emissions. For these reasons, a new PTI procedure at idle run with PN systems is under investigation. The correlations between type approval cycles and idle emissions are limited, especially for positive (spark) ignition vehicles. In this study the type approval PN emissions of 32 compression ignition and 56 spark ignition vehicles were compared to their idle PN concentrations from laboratory and on-road tests. The results confirmed that the idle test is applicable for diesel vehicles. The scatter for the spark ignition vehicles was much larger. Nevertheless, the proposed limit for diesel vehicles was also shown to be applicable for these vehicles. The technical specifications of the PTI sensors based on these findings were also discussed.

On-road emissions of passenger cars beyond the boundary conditions of the real-driving emissions test.

Passenger cars are an important source of air pollution, especially in urban areas. Recently, real-driving emissions (RDE) test procedures have been introduced in the EU aiming to evaluate nitrogen oxides (NOx) and particulate number (PN) emissions from passenger cars during on-road operation. Although RDE accounts for a large variety of real-world driving, it excludes certain driving situations by setting boundary conditions (e.g., in relation to altitude, temperature or dynamic driving). The present work investigates the on-road emissions of NOx, NO2, CO, particle number (PN) and CO2 from a fleet of 19 Euro 6b, 6c and 6d-TEMP vehicles, including diesel, gasoline (GDI and PFI) and compressed natural gas (CNG) vehicles. The vehicles were tested under different on-road driving conditions outside boundaries. These included 'baseline' tests, but also testing conditions beyond the RDE boundary conditions to investigate the performance of the emissions control devices in demanding situations. Consistently low average emission rates of PN and CO were measured from all diesel vehicles tested under most conditions. Moreover, the tested Euro 6d-TEMP and Euro 6c diesel vehicles met the NOx emission limits applicable to Euro 6d-TEMP diesel vehicles during RDE tests (168 mg/km). The Euro 6b GDI vehicle equipped with a gasoline particulate filter (GPF) presented PN emissions < 6 × 1011 #/km. These results, in contrast with previous on-road measurements from earlier Euro 6 vehicles, indicate more efficient emission control technologies are currently being used in diesel and gasoline vehicles. At the same time, the results suggest that particular attention should be given to CO and PN emissions of certain types of vehicles when driven under dynamic conditions, and possibly additional work is necessary. In particular, the emissions of CO (measured in this study during the regulated RDE test, but without an emission limit associated to it) or PN from PFI vehicles (presently not covered by the Euro 6 standard) showed elevated results in some occasions. Emissions of CO were up to 7.5 times higher when the more dynamic tests were conducted and the highest PN emissions were measured from a PFI gasoline vehicle during dynamic driving. Although based on a limited sample of cars, our work points to the relevance of a technology- and fuel-neutral approach to vehicle emission standards, whereby all vehicles must comply with the same emission limits for all pollutants.

Reducing the exhaust emissions of unregulated pollutants from small gasoline engines with alkylate fuel and low-ash lube oil.

We report exhaust emissions of regulated and unregulated gaseous compounds (aromatic, oxygenated, and nitrogen-containing compounds), particle mass and soot content for a series of 5 utility hand-held machines typically used in gardening and forestry operation in Europe. The engines were tested in the Vehicle Emissions Laboratory of the European Commission - Joint Research Centre. Two fuels, standard and alkylate fuel (trace content of aromatics), and 2 lubricant oils (semi-synthetic and low-ash) were used. With the standard fuel, we observed average emissions from 8 g/h up to 103 g/h of hydrocarbons and from 162 g/h up to 275 g/h of carbon monoxide (regulated compounds). A consistent fraction of aromatics was identified in the exhaust: 5-10 g/h of toluene and 1.7-3 g/h of benzene for the 2-stroke engines (below 0.6 g/h for the 4-strokers). The use of the alkylate fuel resulted beneficial in the reduction of several chemical species, in particular all the monitored aromatics (70-100% reduction) and the soot content of the emitted particles (27-90% reduction). These reductions can mitigate the adverse health effects of some toxic or carcinogenic compounds (e.g. toluene and benzene) especially for professional users with high exposure risk. The use of the low-ash lube oil had a lower impact than the fuel change and was engine- and compound-specific. The carbon monoxide emission limit reduction and the introduction of the alkylate fuel would be already feasible actions based on this study and existing scientific literature.

Evaluation of NOx emissions of a retrofitted Euro 5 passenger car for the Horizon prize "Engine retrofit".

The Horizon 2020 prize for the "Engine Retrofit for Clean Air" aims at reducing the pollution in cities by spurring the development of retrofit technology for diesel engines. A Euro 5 passenger car was retrofitted with an under-floor SCR (Selective Catalytic Reduction) for NOx catalyst in combination with a solid ammonia based dosing system as the NOx reductant. The vehicle was tested both on the road and on the chassis dynamometer under various test cycles and ambient temperatures. The NOx emissions were reduced by 350-1100 mg/km (60-85%) in the laboratory depending on the test cycle and engine conditions (cold or hot start), except at type approval conditions. The reduction for cold start urban cycles was < 75 mg/km (< 15%). The on road and laboratory tests were inline. In some high speed conditions significant increase of ammonia (NH3) and nitrous oxide (N2O) were measured. No effect was seen on other pollutants (hydrocarbons, carbon monoxide and particles). The results of the present study show that retrofitting high emitting vehicles can significantly reduce vehicle NOx emissions and ultimately pollution in cities.

Evaluation of Measurement Procedures for Solid Particle Number (SPN) Measurements during the Periodic Technical Inspection (PTI) of Vehicles.

Periodic technical inspection (PTI) of vehicles guarantees safety and environmental compliance during their lifetime. Particulate matter emissions of diesel vehicles are controlled with opacity measurements. After the introduction of diesel particulate filters (DPFs), particulate matter emissions have drastically decreased and the sensitivity of the opacity method is questioned. Several countries have already or are planning to introduce a solid particle number (SPN) method at their PTI that will either substitute or complement opacity measurements. However, there are differences in the measurement procedures and the limit values. In this study, we compared the different approaches and investigated topics which are still not well defined, such as the uncertainty of the SPN-PTI instruments, repeatability of the procedures, impact of the DPF fill state, and the correlation between type-approval SPN emissions and SPN concentrations during PTI tests. Finally, we compared the SPN-PTI instruments with the opacity meters. Our results showed that SPN-PTI measurements can detect tampered and defective DPFs. We also made suggestions on the measurement procedures and the concentration limit.

Driver models for the definition of safety requirements of automated vehicles in international regulations. Application to motorway driving conditions.

UN Regulation 157, the first global regulation regarding the type-approval of Automated Driving Systems (ADS), has been adopted in 2021. In it, safety performance requirements are being defined for vehicles of automation Level 3, according to the SAE J3016, with a limited Operational Design Domain (ODD). In particular, for three types of events that are related to motorway driving, two models are provided to distinguish between preventable traffic scenarios, for which the ADS is expected to avoid an accident, and unpreventable traffic scenarios, for which accidents cannot be avoided and the ADS can only mitigate their severity. The models recreate the short-term behavior of a driver who reacts to an emergency. Two possible actions are predicted: either no reaction or full braking when danger is identified. In the present paper the two models are analyzed and compared with two additional models: an industry proposed model, the Responsibility Sensitive Safety framework (RSS), and the Fuzzy Safety Model (FSM) proposed by the authors. As in the case of the two regulation models, also the RSS, although more sophisticated, assumes that the possible reaction by the driver is binary. This approach neglects the ability of a human driver to drive defensively and anticipate possible risks. Defensive drivers, indeed, may use comfortable decelerations in anticipation, to avoid finding themselves in an emergency situation. The FSM uses fuzzy logic to mimic this behavior. Results show that anticipation plays a very important role to reduce the number of unpreventable traffic scenarios. In addition, by validating the classification capabilities of the four models with real traffic data, the FSM proved to be the most suitable of the investigated models. On the basis of these results, the FSM has been included in the proposal for amending UN Regulation 157, thus allowing to set higher safety standards for the first automated vehicles that will be introduced into the market.

Effect of Low Ambient Temperature on Emissions and Electric Range of Plug-In Hybrid Electric Vehicles.

Plug-in hybrid electrical vehicles (PHEVs) are generally considered to be a cleaner alternative to conventional passenger cars. However, there is still very limited information available regarding criteria pollutant emissions from these vehicles. This paper shows, for the first time, the emissions of criteria pollutants, unregulated pollutants, and CO2 and also electric range from two very different PHEVs, one Euro 6 parallel plug-in hybrid and one range-extended battery electric vehicle (BEVx), applying the new world harmonized light-duty test procedure at ambient temperatures equal to 23 and -7 °C. The impact of using a cabin air heating system on vehicle electric range and emissions at cold temperature has also been studied. Cold ambient temperatures and, to a larger extent, the use of heating systems have been shown to lead to a pronounced negative impact on emissions and shorter electric ranges. Results also show that modern PHEVs can emit similar, or even higher, levels of pollutants (e.g., particle number) as Euro 6 conventional gasoline and diesel vehicles.

Impact of cold temperature on Euro 6 passenger car emissions.

Hydrocarbons, CO, NOx, NH3, N2O, CO2 and particulate matter emissions affect air quality, global warming and human health. Transport sector is an important source of these pollutants and high pollution episodes are often experienced during the cold season. However, EU vehicle emissions regulation at cold ambient temperature only addresses hydrocarbons and CO vehicular emissions. For that reason, we have studied the impact that cold ambient temperatures have on Euro 6 diesel and spark ignition (including: gasoline, ethanol flex-fuel and hybrid vehicles) vehicle emissions using the World-harmonized Light-duty Test Cycle (WLTC) at -7 °C and 23 °C. Results indicate that when facing the WLTC at 23 °C the tested vehicles present emissions below the values set for type approval of Euro 6 vehicles (still using NEDC), with the exception of NOx emissions from diesel vehicles that were 2.3-6 times higher than Euro 6 standards. However, emissions disproportionally increased when vehicles were tested at cold ambient temperature (-7 °C). High solid particle number (SPN) emissions (>1 × 1011 # km-1) were measured from gasoline direct injection (GDI) vehicles and gasoline port fuel injection vehicles. However, only diesel and GDI SPN emissions are currently regulated. Results show the need for a new, technology independent, procedure that enables the authorities to assess pollutant emissions from vehicles at cold ambient temperatures. Harmful pollutant emissions from spark ignition and diesel vehicles are strongly and negatively affected by cold ambient temperatures. Only hydrocarbon, CO emissions are currently regulated at cold temperature. Therefore, it is of great importance to revise current EU winter vehicle emissions regulation.

NOx, NH3, N2O and PN real driving emissions from a Euro VI heavy-duty vehicle. Impact of regulatory on-road test conditions on emissions.

Euro VI emission standards for heavy-duty vehicles (HDVs) introduced for the first time limits for solid particle number (PN) and NH3 emissions. EU regulation also includes a Portable Emissions Measurement System (PEMS) based test at type approval, followed by in-service conformity (ISC) testing. A comprehensive study on the real-time on-road emissions of NOx, NH3, N2O and PN from a Euro VI HDV equipped with a Diesel Oxidation Catalyst (DOC), a Diesel Particle Filter (DPF), a Selective Catalytic Reduction (SCR) system and an Ammonia Oxidation Catalyst (AMOX) is presented. Our analyses revealed that up to 85% of the NOx emissions measured during the tests performed are not taken into consideration if the boundary conditions for data exclusion set in the current legislation are applied. Moreover, it was found that the highest NOx emissions were measured during urban operation. Analyses show that a large fraction urban of operation is not considered when 20% power threshold as boundary condition is applied. They also show that cold start emissions account for a large fraction of the total NOx emitted. Low emissions of PN (2.8×1010 to 6.5×1010#/kWh) and NH3 (1.0 to 2.2ppm) were obtained during the on-road tests, suggesting effectiveness of the vehicle's after-treatment (DPF and AMOX). Finally, a comparison between speed-based (as currently defined by Euro VI legislation) and land-use-based (using Geographic Information System (GIS)) calculation of shares of operation was performed. Results suggest that using GIS to categorize the shares of operation could result in different interpretations depending on the criteria adopted for their definition.

Intercomparison of real-time tailpipe ammonia measurements from vehicles tested over the new world-harmonized light-duty vehicle test cycle (WLTC).

Four light-duty vehicles (two diesel, one flex-fuel, and one gasoline vehicle) were tested as part of an intercomparison exercise of the world-harmonized light-duty vehicle test procedure (WLTP) aiming at measuring real-time ammonia emissions from the vehicles' raw exhaust at the tailpipe. The tests were conducted in the Vehicle Emission Laboratory (VELA) at the European Commission Joint Research Centre (EC-JRC), Ispra, Italy. HORIBA, CGS, and the Sustainable Transport Unit of the Joint Research Centre (JRC) took part in the measurement and analysis of the four vehicles' exhaust emissions over the world-harmonized light-duty vehicle test cycle class 3, version 5.3 using a HORIBA MEXA 1400 QL-NX, a CGS BLAQ-Sys, and the JRC Fourier transform infrared spectrometer, respectively. The measured ammonia concentrations and the emission profiles revealed that these three instruments are suitable to measure ammonia from the vehicles' raw exhaust, presenting no significant differences. Furthermore, results showed that measurement of ammonia from the vehicle exhaust using online systems can be performed guaranteeing the reproducibility and repeatability of the results. While no ammonia was detected for any of the two diesel vehicles (even though, one was equipped with a selective catalytic reduction system), we report average ammonia emission factors 8-10 mg/km (average concentrations 20-23 ppm) and 10-12 mg/km (average concentrations 22-24 ppm) for the flex-fuel and gasoline vehicles, respectively.

Electrocatalytic dihydrogen evolution mechanism of [Fe2(CO)4(kappa(2)-Ph2PCH2CH2PPh2)(mu-S(CH2)3S)] and related models of the [FeFe]-hydrogenases active site: a DFT investigation.

A DFT study of protonation thermodynamics in H(2)-evolving biomimetic catalysts related to [FeFe]-hydrogenases active site is presented here. Taking as a reference system the electrocatalytic dihydrogen evolution mechanism recently proposed for the synthetic assembly [Fe(2)(CO)(4)(kappa(2)-Ph(2)PCH(2)CH(2)PPh(2))(mu-S(CH(2))(3)S)] (a, which is able to release H(2) after having undergone monoelectron reduction steps and three sequential protonation reactions), we show how the reduction of model complexes to oxidation states lower than those observed in [FeFe]-hydrogenases cofactor leads to a protonation regiochemistry that has no counterpart in the enzymatic mechanism of H(2) production. In particular, double protonation of the metal centers turned out to be disfavored in a by up to 12.5 kcal mol(-1) with respect to alternative protonation paths; as for the regiochemistry of triple protonation, the formation of eta(2)-H(2) adducts is disfavored by at least approximately 25 kcal mol(-1). Structural analysis of the theoretical models also revealed that over-reduction of synthetic complexes, though necessary for observing H(2) evolution from the currently available biomimetic electrocatalysts, can generally impair their structural integrity. Possible approaches for the modulation of protonation regiochemistry are then proposed; in particular, it turned out that a targeted use of sigma-donating ligands showing low basicity can favor double protonation of iron centers.