Resolving Ultraviolet-Visible Spectra for Complex Dissolved Mixtures of Multitudinous Organic Matters in Aerosols.

Light-absorbing organic aerosols, referred to as brown carbon (BrC), play a vital role in the global climate and air quality. Due to the complexity of BrC chromophores, the identified absorbing substances in the ambient atmosphere are very limited. However, without comprehensive knowledge of the complex absorbing compounds in BrC, our understanding of its sources, formation, and evolution mechanisms remains superficial, leading to great uncertainty in climatic and atmospheric models. To address this gap, we developed a constrained non-negative matrix factorization (NMF) model to resolve the individual ultraviolet-visible spectrum for each substance in dissolved organic aerosols, with the power of ultrahigh-performance liquid chromatography-diode array detector-ultrahigh-resolution mass spectrometry (UHPLC-DAD-UHRMS). The resolved spectra were validated by selected standard substances and validation samples. Approximately 40,000 light-absorbing substances were recognized at the MS1 level. It turns out that BrC is composed of a vast number of substances rather than a few prominent chromophores in the urban atmosphere. Previous understanding of the absorbing feature of BrC based on a few identified compounds could be biased. Weak-absorbing substances missed previously play an important role in BrC absorption when they are integrated due to their overwhelming number. This model brings the property exploration of complex dissolved organic mixtures to a molecular level, laying a foundation for identifying potentially significant compositions and obtaining a comprehensive chemical picture.

Ammonia storage and slip under steady and transient state in close-coupled SCR.

The close-coupled selective catalytic reduction (cc-SCR) catalyst is an effective technology to reduce tailpipe NOx emission during cold start. This paper investigated the optimal ammonia storage under steady and transient state in the cc-SCR. The study showed that a trade-off between NOx conversion efficiency and ammonia slip is observed on the pareto solutions under steady state, and the optimal ammonia storage is calculated with ammonia slip less than 10 µL/L based on the China Ⅵ emission legislation. The rapid temperature increase will lead to severe ammonia slip in the transient test cycle. A simplified 0-D calculation method on ammonia slip under transient state is proposed based on kinetic model of ammonia adsorption and desorption. In addition, the effect of ammonia storage, catalyst temperature and temperature increasing rate on ammonia slip are analyzed. The optimal ammonia storage is calculated with maximum ammonia slip less than 100 µL/L according to the oxidation efficiency of ammonia slip catalyst (ASC) downstream cc-SCR. It was found that the optimal ammonia storage under transient state is much lower than that under steady state in cc-SCR at lower temperature, and a phase diagram is established to analyze the influence of temperature and temperature increasing rate on optimal ammonia storage.

Remarkable nucleation and growth of ultrafine particles from vehicular exhaust.

High levels of ultrafine particles (UFPs; diameter of less than 50 nm) are frequently produced from new particle formation under urban conditions, with profound implications on human health, weather, and climate. However, the fundamental mechanisms of new particle formation remain elusive, and few experimental studies have realistically replicated the relevant atmospheric conditions. Previous experimental studies simulated oxidation of one compound or a mixture of a few compounds, and extrapolation of the laboratory results to chemically complex air was uncertain. Here, we show striking formation of UFPs in urban air from combining ambient and chamber measurements. By capturing the ambient conditions (i.e., temperature, relative humidity, sunlight, and the types and abundances of chemical species), we elucidate the roles of existing particles, photochemistry, and synergy of multipollutants in new particle formation. Aerosol nucleation in urban air is limited by existing particles but negligibly by nitrogen oxides. Photooxidation of vehicular exhaust yields abundant precursors, and organics, rather than sulfuric acid or base species, dominate formation of UFPs under urban conditions. Recognition of this source of UFPs is essential to assessing their impacts and developing mitigation policies. Our results imply that reduction of primary particles or removal of existing particles without simultaneously limiting organics from automobile emissions is ineffective and can even exacerbate this problem.

Advances in emission control of diesel vehicles in China.

Diesel vehicles have caused serious environmental problems in China. Hence, the Chinese government has launched serious actions against air pollution and imposed more stringent regulations on diesel vehicle emissions in the latest China VI standard. To fulfill this stringent legislation, two major technical routes, including the exhaust gas recirculation (EGR) and high-efficiency selective catalytic reduction (SCR) routes, have been developed for diesel engines. Moreover, complicated aftertreatment technologies have also been developed, including use of a diesel oxidation catalyst (DOC) for controlling carbon monoxide (CO) and hydrocarbon (HC) emissions, diesel particulate filter (DPF) for particle mass (PM) emission control, SCR for the control of NOx emission, and an ammonia slip catalyst (ASC) for the control of unreacted NH3. Due to the stringent requirements of the China VI standard, the aftertreatment system needs to be more deeply integrated with the engine system. In the future, aftertreatment technologies will need further upgrades to fulfill the requirements of the near-zero emission target for diesel vehicles.

Humidity-Dependent Phase State of Gasoline Vehicle Emission-Related Aerosols.

The phase states of primarily emitted and secondarily formed aerosols from gasoline vehicle exhausts were investigated by quantifying the particle rebound fraction (f). The rebound behaviors of gasoline vehicle emission-related aerosols varied with engines, fuel types, and photochemical aging time, showing distinguished differences from biogenic secondary organic aerosols. The nonliquid-to-liquid phase transition of primary aerosols emitted from port fuel injection (PFI) and gasoline direct injection (GDI) vehicles started at a relative humidity (RH) = 50 and 60%, and liquefaction was accomplished at 60 and 70%, respectively. The RH at which f declined to 0.5 decreased from 70 to 65% for the PFI case with 92# fuel, corresponding to the photochemical aging time from 0.37 to 4.62 days. For the GDI case, such RH enhanced from 60 to 65%. Our results can be used to imply the phase state of traffic-related aerosols and further understand their roles in urban atmospheric chemistry. Taking Beijing, China, as an example, traffic-related aerosols were mainly nonliquid during winter with the majority ambient RH below 50%, whereas they were mostly liquid during the morning rush hour of summer, and traffic-related secondary aerosols fluctuated between nonliquid and liquid during the daytime and tended to be liquid at night with increased ambient RH.

Morphology and composition of particles emitted from a port fuel injection gasoline vehicle under real-world driving test cycles.

Traffic vehicles, many of which are powered by port fuel injection (PFI) engines, are major sources of particulate matter in the urban atmosphere. We studied particles from the emission of a commercial PFI-engine vehicle when it was running under the states of cold start, hot start, hot stabilized running, idle and acceleration, using a transmission electron microscope and an energy-dispersive X-ray detector. Results showed that the particles were mainly composed of organic, soot, and Ca-rich particles, with a small amount of S-rich and metal-containing particles, and displayed a unimodal size distribution with the peak at 600 nm. The emissions were highest under the cold start running state, followed by the hot start, hot stabilized, acceleration, and idle running states. Organic particles under the hot start and hot stabilized running states were higher than those of other running states. Soot particles were highest under the cold start running state. Under the idle running state, the relative number fraction of Ca-rich particles was high although their absolute number was low. These results indicate that PFI-engine vehicles emit substantial primary particles, which favor the formation of secondary aerosols via providing reaction sites and reaction catalysts, as well as supplying soot, organic, mineral and metal particles in the size range of the accumulation mode. In addition, the contents of Ca, P, and Zn in organic particles may serve as fingerprints for source apportionment of particles from PFI-engine vehicles.

Potential of secondary aerosol formation from Chinese gasoline engine exhaust.

Light-duty gasoline vehicles have drawn public attention in China due to their significant primary emissions of particulate matter and volatile organic compounds (VOCs). However, little information on secondary aerosol formation from exhaust for Chinese vehicles and fuel conditions is available. In this study, chamber experiments were conducted to quantify the potential of secondary aerosol formation from the exhaust of a port fuel injection gasoline engine. The engine and fuel used are common in the Chinese market, and the fuel satisfies the China V gasoline fuel standard. Substantial secondary aerosol formation was observed during a 4-5hr simulation, which was estimated to represent more than 10days of equivalent atmospheric photo-oxidation in Beijing. As a consequence, the extreme case secondary organic aerosol (SOA) production was 426±85mg/kg-fuel, with high levels of precursors and OH exposure. The low hygroscopicity of the aerosols formed inside the chamber suggests that SOA was the dominant chemical composition. Fourteen percent of SOA measured in the chamber experiments could be explained through the oxidation of speciated single-ring aromatics. Unspeciated precursors, such as intermediate-volatility organic compounds and semi-volatile organic compounds, might be significant for SOA formation from gasoline VOCs. We concluded that reductions of emissions of aerosol precursor gases from vehicles are essential to mediate pollution in China.

Experimental study on filtration and continuous regeneration of a particulate filter system for heavy-duty diesel engines.

This study investigated the filtration and continuous regeneration of a particulate filter system on an engine test bench, consisting of a diesel oxidation catalyst (DOC) and a catalyzed diesel particulate filter (CDPF). Both the DOC and the CDPF led to a high conversion of NO to NO2 for continuous regeneration. The filtration efficiency on solid particle number (SPN) was close to 100%. The post-CDPF particles were mainly in accumulation mode. The downstream SPN was sensitively influenced by the variation of the soot loading. This phenomenon provides a method for determining the balance point temperature by measuring the trend of SPN concentration.

Secondary aerosol formation from a Chinese gasoline vehicle: Impacts of fuel (E10, gasoline) and driving conditions (idling, cruising).

Chassis dynamometer experiments were conducted to investigate the effect of vehicle speed and usage of ethanol-blended gasoline (E10) on formation and evolution of gasoline vehicular secondary organic aerosol (SOA) using a Gothenburg Potential Aerosol Mass (Go: PAM) reactor. The SOA forms rapidly, and its concentration exceeds that of primary organic aerosol (POA) at an equivalent photochemical age (EPA) of ~1 day. The particle effective densities grow from 0.62 ± 0.02 g cm-3 to 1.43 ± 0.07 g cm-3 with increased hydroxyl radical (OH) exposure. The maximum SOA production under idling conditions (4259-7394 mg kg-fuel-1) is ~20 times greater than under cruising conditions. There was no statistical difference between SOA formation from pure gasoline and its formation from E10. The slopes in Van Krevelen diagram indicate that the formation pathways of bulk SOA includes the addition of both alcohol/peroxide functional groups and carboxylic acid formation from fragmentation. A closure estimation of SOA based on bottom-up and top-down methods shows that only 16%-38% of the measured SOA can be explained by the oxidation of measured volatile organic compounds (VOCs), suggesting the existence of missing precursors, e.g. unmeasured VOCs and probably semivolatile or intermediate volatile organic compounds (S/IVOCs). Our results suggest that applying parameters obtained from unified driving cycles to model SOA concentrations may lead to large discrepancies between modeled and ambient vehicular SOA. No reduction in vehicular `SOA production is realized by replacing normal gasoline with E10.

Particulate emissions from gasoline direct injection engines: A review of how current emission regulations are being met by automobile manufacturers.

Gasoline direct injection (GDI), which is one of the fuel injection technologies extensively used in internal combustion engines, is a viable alternative for port fuel injection technology in premium gasoline (petrol)-run vehicles; furthermore, it provides a better fuel economy, higher thermal efficiency, and greater power output. However, the particulate emissions ejected from modern GDI engines are an environmental and health hazard. As a result, stringent emission legislations are imposed on the production/incorporation of GDI engines. This study reviews the particle masses (PMs) and particle numbers (PNs) of various GDI engines. The backgrounds and highlights of current and future PM emission regulations (Euro 5-6 and China 5-6 GDI engine legislations) are discussed. In addition to the effects of cold-start and oxygenated fuel on PM emissions, this paper also reviews the impacts of engine parameters. Another area of discussion is the particulate filter technology as a solution for pollution control. Concerns about PM emissions from GDI engines are conceptually similar to those about emissions from diesel engines. Finally, this paper discusses the technical and commercial aspects of the use of the particulate matter control technology of GDI engines, such as particulate gasoline filters, as dedicated GDI filtration devices.

Effects of hysteresis window on contact angle hysteresis behaviour at large Bond number.

Contact angle hysteresis, defined as the difference between advancing and receding contact angles, is an important phenomenon in multiphase flow on a wetting surface. In this study, a modified pseudo-potential lattice Boltzmann (LB) multiphase model with tunable surface tension is proposed, which is further coupled with the geometrical formulation contact angle scheme to investigate the motion of droplets invoking the contact angle hysteresis. We focus on the dynamic behaviour of droplets driven by a body force at the Bond number ranging from 1 to 6, which is defined as the ratio of the body force to the capillary force. The droplet morphology change is examined by varying (i) the Bond number and (ii) the hysteresis window. Results show the droplet morphology evolution can be classified into different stages, including stretch, relaxation, and equilibrium. The droplet oscillation phenomenon at large Bond numbers at the equilibrium stage is observed for the first time. In addition, it is found that such oscillation can lead to the breakup and/or coalescence of droplets when the surface waves spread on the top of the droplet. Furthermore, there is slight oscillation of the normalized length, width and height at the equilibrium stage for the neutral hysteresis window while more dramatic oscillation will appear for the hydrophobic hysteresis window.

Overview of polyoxymethylene dimethyl ether additive as an eco-friendly fuel for an internal combustion engine: Current application and environmental impacts.

The combustion of conventional fuels within the transportation sector is a crucial driver of global warming and produces a number of harmful emissions. To decrease these adverse factors, the development of synthetic fuels produced from renewable energy sources via the catalytic conversion of carbon dioxide (CO2) and hydrogen (H2) has progressed significantly. Eco-friendly fuels have a reduced impact on the environment throughout their production and use cycles. In recent years, the use of polyoxymethylene dimethyl ethers (PODEn) as fuels has received an increasing amount of attention, owing to their engine performance and reduced environmental impact. The specific target of this paper is to systematically review the field of PODEn application-based additives as fuel for internal combustion engines. The background and highlights of current and future applications of PODEn are also discussed, and the challenges associated with the use of this additive are also briefly reviewed. A number of studies have shown that the use of fuel mixtures with up to 10% PODE3-4 can have a significant impact on the reduction of engine emissions. PODEn have been shown to reduce the emissions of soot, particulates, CO, and HC under different parameters and working conditions, although NOx and brake-specific fuel consumption (BSFC) emissions have been found to increase. Additionally, PODEn can be produced from natural gas or electric power via CO2 activation in a sustainable manner, which represents a significant benefit with regard to the use of oil-based products. Finally, fossil fuels blended with PODEn can be easily ignited and burned at stoichiometric conditions.

Optimization of gasoline hydrocarbon compositions for reducing exhaust emissions.

Effects of hydrocarbon compositions on raw exhaust emissions and combustion processes were studied on an engine test bench. The optimization of gasoline hydrocarbon composition was discussed. As olefins content increased from 10.0% to 25.0% in volume, the combustion duration was shortened by about 2 degree crank angle (degrees CA), and the engine-out THC emission was reduced by about 15%. On the other hand, as aromatics content changed from 35.0% to 45.0%, the engine-out NOx emissions increased by 4%. An increment in olefins content resulted in a slight increase in engine-out CO emission, while the aromatics content had little effect on engine-out total hydrocarbon (THC) and CO emissions. Over the new European driving cycle (NEDC), the THC, NOx and CO emissions of fuel with 25.0% olefins and 35.0% aromatics were about 45%, 21% and 19% lower than those of fuel with 10.0% olefins and 40.0% aromatics, respectively. The optimized gasoline compositions for new engines and new vehicles have low aromatics and high olefins contents.

Combination of biodiesel-ethanol-diesel fuel blend and SCR catalyst assembly to reduce emissions from a heavy-duty diesel engine.

In this study, the efforts to reduce NOx and particulate matter (PM) emissions from a diesel engine using both ethanol-selective catalytic reduction (SCR) of NOx over an Ag/Al2O3 catalyst and a biodiesel-ethanol-diesel fuel blend (BE-diesel) on an engine bench test are discussed. Compared with diesel fuel, use of BE-diesel increased PM emissions by 14% due to the increase in the soluble organic fraction (SOF) of PM, but it greatly reduced the Bosch smoke number by 60%-80% according to the results from 13-mode test of European Stationary Cycle (ESC) test. The SCR catalyst was effective in NOx reduction by ethanol, and the NOx conversion was approximately 73%. Total hydrocarbons (THC) and CO emissions increased significantly during the SCR of NOx process. Two diesel oxidation catalyst (DOC) assemblies were used after Ag/Al2O3 converter to remove CO and HC. Different oxidation catalyst showed opposite effect on PM emission. The PM composition analysis revealed that the net effect of oxidation catalyst on total PM was an integrative effect on SOF reduction and sulfate formation of PM. The engine bench test results indicated that the combination of BE-diesel and a SCR catalyst assembly could provide benefits for NOx and PM emissions control even without using diesel particle filters (DPFs).

Catalytic performance of Ag/Al2O3-C2H5OH-Cu/Al2O3 system for the removal of NOx from diesel engine exhaust.

The selective catalytic reduction (SCR) of NOx by C(2)H(5)OH was studied in excess oxygen over Ag/Al(2)O(3) catalysts with different Ag loadings at lab conditions. The 4% Ag/Al(2)O(3) has the highest activity for the C(2)H(5)OH-SCR of NOx with a drawback of simultaneously producing CO and unburned THC in effluent gases. An oxidation catalyst 10% Cu/Al(2)O(3) was directly placed after the Ag/Al(2)O(3) to remove CO and unburned THC. Washcoated honeycomb catalysts were prepared based on the 4% Ag/Al(2)O(3) and 10% Cu/Al(2)O(3) powders and tested for the C(2)H(5)OH-SCR of NOx on a diesel engine at the practical operating conditions. Compared with the Ag/Al(2)O(3) powder, the Ag/Al(2)O(3) washcoated honeycomb catalyst (SCR catalyst) has a similar activity for NOx reduction by C(2)H(5)OH and the drawback of increasing the CO and unburned THC emissions. Using the SCR+Oxi composite catalyst with the optimization of C(2)H(5)OH addition, the diesel engine completely meets EURO III emission standards.

[Effects of fuel properties on the performance of a typical Euro IV diesel engine].

With the purpose of establishing diesel fuel standard for China National 4th Emission Standard, as one part of Beijing "Auto-Oil" programme, engine performance test has been done on a typical Euro IV diesel engine using eight diesel fuels with different fuel properties. Test results show that, fuel properties has little effect on power, fuel consumption, and in-cylinder combustion process of tested Euro IV diesel engine; sulfate in PM and gaseous SO2 emissions increase linearly with diesel sulfur content increase; cetane number increase cause BSFC and PM reduce and NOx increase; T90 decrease cause NOx reduce while PM shows trend of reduce. Prediction equations of tested Euro IV diesel engine's ESC cycle NOx and PM emissions before SCR response to diesel fuel sulfur content, cetane number, T90 and aromatics have been obtained using linear regression method on the base of test results.