Using the Multicomponent Aerosol FORmation Model (MAFOR) to Determine Improved VOC Emission Factors in Ship Plumes.

International shipping's particulate matter primary emissions have a share in global anthropogenic emissions of between 3% and 4%. Ship emissions of volatile organic compounds (VOCs) can play an important role in the formation of fine particulate matter. Using an aerosol box model for the near-plume scale, this study investigated how the changing VOC emission factor (EF) for ship engines impacts the formation of secondary PM2.5 in ship exhaust plumes that were detected during a measurement campaign. The agreement between measured and modeled particle number size distribution was improved by adjusting VOC emissions, in particular of intermediate-, low-, and extremely low-volatility compounds. The scaling of the VOC emission factor showed that the initial emission factor, based on literature data, had to be multiplied by 3.6 for all VOCs. Information obtained from the box model was integrated into a regional-scale chemistry transport model (CTM) to study the influence of changed VOC ship emissions over the Mediterranean Sea. The regional-scale CTM run with adjusted ship emissions indicated a change in PM2.5 of up to 5% at the main shipping routes and harbor cities in summer. Nevertheless, overall changes due to a change in the VOC EF were rather small, indicating that the size of grid cells in CTMs leads to a fast dilution.

Exhaust particle number and composition for diesel and gasoline passenger cars under transient driving conditions: Real-world emissions down to 1.5 nm.

Recent recommendations given by WHO include systematic measurements of ambient particle number concentration and black carbon (BC) concentrations. In India and several other highly polluted areas, the air quality problems are severe and the need for air quality related information is urgent. This study focuses on particle number emissions and BC emissions of passenger cars that are technologically relevant from an Indian perspective. Particle number and BC were investigated under real-world conditions for driving cycles typical for Indian urban environments. Two mobile laboratories and advanced aerosol and trace gas instrumentation were utilized. Our study shows that passenger cars without exhaust particle filtration can emit in real-world conditions large number of particles, and especially at deceleration a significant fraction of particle number can be even in 1.5-10 nm particle sizes. The mass concentration of exhaust plume particles was dominated by BC that was emitted especially at acceleration conditions. However, exhaust particles contained also organic compounds, indicating the roles of engine oil and fuel in exhaust particle formation. In general, our study was motivated by serious Indian air quality problems, by the recognized lack of emission information related to Indian traffic, and by the recent WHO air quality guidance; our results emphasize the importance of monitoring particle number concentrations and BC also in Indian urban areas and especially in traffic environments where people can be significantly exposed to fresh exhaust emissions.

Using an oxidation flow reactor to understand the effects of gasoline aromatics and ethanol levels on secondary aerosol formation.

Fuel type and composition affect tailpipe emissions and secondary aerosol production from mobile sources. This study assessed the influence of gasoline fuels with varying levels of aromatics and ethanol on the primary emissions and secondary aerosol formation from a flexible fuel vehicle equipped with a port fuel injection engine. The vehicle was exercised over the LA92 and US06 driving cycles using a chassis dynamometer. Secondary aerosol formation potential was measured using a fast oxidation flow reactor. Results showed that the high aromatics fuels led to higher gaseous regulated emissions, as well as particulate matter (PM), black carbon, and total and solid particle number. The high ethanol content fuel (E78) resulted in reductions for the gaseous regulated pollutants and particulate emissions, with some exceptions where elevated emissions were seen for this fuel compared to both E10 fuels, depending on the driving cycle. Secondary aerosol formation potential was dominated by the cold-start phase and increased for the high aromatics fuel. Secondary aerosol formation was seen in lower levels for E78 due to the lower formation of precursor emissions using this fuel. In addition, operating driving conditions and aftertreatment efficiency played a major role on secondary organic and inorganic aerosol formation, indicating that fuel properties, driving conditions, and exhaust aftertreatment should be considered when evaluating the emissions of secondary aerosol precursors from mobile sources.

Effects of driving conditions on secondary aerosol formation from a GDI vehicle using an oxidation flow reactor.

A comprehensive study on the effects of photochemical aging on exhaust emissions from a vehicle equipped with a gasoline direct injection engine when operated over seven different driving cycles was assessed using an oxidation flow reactor. Both primary emissions and secondary aerosol production were measured over the Federal Test Procedure (FTP), LA92, New European Driving Cycle (NEDC), US06, and the Highway Fuel Economy Test (HWFET), as well as over two real-world cycles developed by the California Department of Transportation (Caltrans) mimicking typical highway driving conditions. We showed that the emissions of primary particles were largely depended on cold-start conditions and acceleration events. Secondary organic aerosol (SOA) formation also exhibited strong dependence on the cold-start cycles and correlated well with SOA precursor emissions (i.e., non-methane hydrocarbons, NMHC) during both cold-start and hot-start cycles (correlation coefficients 0.95-0.99), with overall emissions of ∼68-94 mg SOA per g NMHC. SOA formation significantly dropped during the hot-running phases of the cycles, with simultaneous increases in nitrate and ammonium formation as a result of the higher nitrogen oxide (NOx) and ammonia emissions. Our findings suggest that more SOA will be produced during congested, slow speed, and braking events in highways.

Shipping Remains a Globally Significant Source of Anthropogenic PN Emissions Even after 2020 Sulfur Regulation.

Shipping is the main source of anthropogenic particle emissions in large areas of the globe, influencing climate, air quality, and human health in open seas and coast lines. Here, we determined, by laboratory and on-board measurements of ship engine exhaust, fuel-specific particle number (PN) emissions for different fuels and desulfurization applied in shipping. The emission factors were compared to ship exhaust plume observations and, furthermore, exploited in the assessment of global PN emissions from shipping, utilizing the STEAM ship emission model. The results indicate that most particles in the fresh ship engine exhaust are in ultrafine particle size range. Shipping PN emissions are localized, especially close to coastal lines, but significant emissions also exist on open seas and oceans. The global annual PN produced by marine shipping was 1.2 × 1028 (±0.34 × 1028) particles in 2016, thus being of the same magnitude with total anthropogenic PN emissions in continental areas. The reduction potential of PN from shipping strongly depends on the adopted technology mix, and except wide adoption of natural gas or scrubbers, no significant decrease in global PN is expected if heavy fuel oil is mainly replaced by low sulfur residual fuels. The results imply that shipping remains as a significant source of anthropogenic PN emissions that should be considered in future climate and health impact models.

Particle growth with photochemical age from new particle formation to haze in the winter of Beijing, China.

Secondary aerosol formation in the aging process of primary emission is the main reason for haze pollution in eastern China. Pollution evolution with photochemical age was studied for the first time at a comprehensive field observation station during winter in Beijing. The photochemical age was used as an estimate of the timescale attributed to the aging process and was estimated from the ratio of toluene to benzene in this study. A low photochemical age indicates a fresh emission. The photochemical age of air masses during new particle formation (NPF) days was lower than that on haze days. In general, the strongest NPF events, along with a peak of the formation rate of 1.5 nm (J1.5) and 3 nm particles (J3), were observed when the photochemical age was between 12 and 24 h while rarely took place with photochemical ages less than 12 h. When photochemical age was larger than 48 h, haze occurred and NPF was suppressed. The sources and sinks of nanoparticles had distinct relation with the photochemical age. Our results show that the condensation sink (CS) showed a valley with photochemical ages ranging from 12 to 24 h, while H2SO4 concentration showed no obvious trend with the photochemical age. The high concentrations of precursor vapours within an air mass lead to persistent nucleation with photochemical age ranging from 12 to 48 h in winter. Coincidently, the fast increase of PM2.5 mass was also observed during this range of photochemical age. Noteworthy, CS increased with the photochemical age on NPF days only, which is the likely reason for the observation that the PM2.5 mass increased faster with photochemical age on NPF days compared with other days. The evolution of particles with the photochemical age provides new insights into understanding how particles originating from NPF transform to haze pollution.

Physical Characteristics of Particle Emissions from a Medium Speed Ship Engine Fueled with Natural Gas and Low-Sulfur Liquid Fuels.

Particle emissions from marine traffic affect significantly air quality in coastal areas and the climate. The particle emissions were studied from a 1.4 MW marine engine operating on low-sulfur fuels natural gas (NG; dual-fuel with diesel pilot), marine gas oil (MGO) and marine diesel oil (MDO). The emitted particles were characterized with respect to particle number (PN) emission factors, PN size distribution down to nanometer scale (1.2-414 nm), volatility, electric charge, morphology, and elemental composition. The size distribution of fresh exhaust particles was bimodal for all the fuels, the nucleation mode highly dominating the soot mode. Total PN emission factors were 2.7 × 1015-7.1 × 1015 #/kWh, the emission being the lowest with NG and the highest with MDO. Liquid fuel combustion generated 4-12 times higher soot mode particle emissions than the NG combustion, and the harbor-area-typical lower engine load (40%) caused higher total PN emissions than the higher load (85%). Nonvolatile particles consisted of nanosized fuel, and spherical lubricating oil core mode particles contained, e.g., calcium as well as agglomerated soot mode particles. Our results indicate the PN emissions from marine engines may remain relatively high regardless of fuel sulfur limits, mostly due to the nanosized particle emissions.

Characterization of laboratory and real driving emissions of individual Euro 6 light-duty vehicles - Fresh particles and secondary aerosol formation.

Emissions from passenger cars are one of major sources that deteriorate urban air quality. This study presents characterization of real-drive emissions from three Euro 6 emission level passenger cars (two gasoline and one diesel) in terms of fresh particles and secondary aerosol formation. The gasoline vehicles were also characterized by chassis dynamometer studies. In the real-drive study, the particle number emissions during regular driving were 1.1-12.7 times greater than observed in the laboratory tests (4.8 times greater on average), which may be caused by more effective nucleation process when diluted by real polluted and humid ambient air. However, the emission factors measured in laboratory were still much higher than the regulatory value of 6 × 1011 particles km-1. The higher emission factors measured here result probably from the fact that the regulatory limit considers only non-volatile particles larger than 23 nm, whereas here, all particles (also volatile) larger than 3 nm were measured. Secondary aerosol formation potential was the highest after a vehicle cold start when most of the secondary mass was organics. After the cold start, the relative contributions of ammonium, sulfate and nitrate increased. Using a novel approach to study secondary aerosol formation under real-drive conditions with the chase method resulted mostly in emission factors below detection limit, which was not in disagreement with the laboratory findings.

Strategies To Diminish the Emissions of Particles and Secondary Aerosol Formation from Diesel Engines.

Particle emissions and secondary aerosol formation from internal combustion engines deteriorate air quality and significantly affect human wellbeing and health. Both the direct particle emissions and the emissions of compounds contributing to secondary aerosol formation depend on choices made in selecting fuels, engine technologies, and exhaust aftertreatment (EAT). Here we study how catalytic EATs, particle filtration, and fuel choices affect these emissions concerning heavy-duty diesel engine. We observed that the most advanced EAT decreased the emissions of fresh exhaust particle mass as much as 98% (from 44.7 to 0.73 mg/kWh) and the formation of aged exhaust particle mass ∼100% (from 106.2 to ∼0 mg/kWh). The composition of emitted particles depended significantly on the EAT and oxidative aging. While black carbon typically dominated the composition of fresh exhaust particles, aged particles contained more sulfates and organics. The fuel choices had minor effects on the secondary aerosol formation, implicating that, in diesel engines, either the lubricant is a significant source of secondary aerosol precursors or the precursors are formed in the combustion process. Results indicate that the utilization of EAT in diesel engines would produce benefits with respect to exhaust burden on air quality, and thus their utilization should be promoted especially in geographical areas suffering from poor air quality.

Particle emissions of Euro VI, EEV and retrofitted EEV city buses in real traffic.

Exhaust emissions from traffic significantly affect urban air quality. In this study, in-traffic emissions of diesel-fueled city buses meeting enhanced environmentally friendly vehicle (EEV) and Euro VI emission limits and the effects of retrofitting of EEV buses were studied on-road by chasing the buses with a mobile laboratory in the Helsinki region, Finland. The average emission factors of particle number (PN), particle mass (PM1) and black carbon mass (BC) were 0.86·1015 1/kgfuel, 0.20 g/kgfuel and 0.10 g/kgfuel, respectively, for EEV buses. For Euro VI buses, the emissions were below 0.5·1015 1/kgfuel (PN), 0.07 g/kgfuel (PM1) and 0.02 g/kgfuel (BC), and the exhaust plume concentrations of these pollutants were close to the background concentrations. The emission factors of PM1 and BC of retrofitted EEV buses were at the level of Euro VI buses, but their particle number emissions varied significantly. On average, the EEV buses were observed to emit the largest amounts of nanocluster aerosol (NCA) (i.e., the particles with size between 1.3 and 3 nm). High NCA emissions were linked with high PN emissions. In general, results demonstrate that advanced exhaust aftertreatment systems reduce emissions of larger soot particles but not small nucleation mode particles in all cases.

Heavy Duty Diesel Exhaust Particles during Engine Motoring Formed by Lube Oil Consumption.

This study reports high numbers of exhaust emissions particles during engine motoring. Such particles were observed in the exhaust of two heavy duty vehicles with no diesel particle filter (DPF), driven on speed ramp tests and transient cycles. A significant fraction of these particles was nonvolatile in nature. The number-weighted size distribution peak was below 10 nm when a thermodenuder was used to remove semivolatile material, growing up to 40 nm after semivolatile species condensation. These particles were found to contribute to 9-13% of total particle number emitted over a complete driving cycle. Engine motoring particles originated from lube oil and evidence suggests that these are of heavy organic or organometallic material. Particles of similar characteristics have been observed in the core particle mode during normal fired engine operation. Their size and chemical character has implications primarily on the environmental toxicity of non-DPF diesel and, secondarily, on the performance of catalytic devices and DPFs. Lube oil formulation measures can be taken to reduce the emission of such particles.