Effect of potassium on a model soot combustion: Raman and HRTEM evidences

The effect of potassium on the oxidation of a model carbonaceous material (Printex U, namely, soot for brevity) has been investigated under isothermal conditions. For this purpose, Raman spectroscopy, Transmission Electron Microscopy (TEM), and Brunaure, Emmet, Teller surface area characterization have been applied to investigate structural changes occurring during soot oxidation both in the presence and in the absence of potassium. The Raman spectra of the model soot during combustion showed that oxidation preferentially involves the amorphous carbon fraction of the soot and only subsequently it affects the more ordered sp² domains. However, in the K-doped Printex U the oxidation of both the amorphous and more ordered sp² structures occurs concurrently. These findings have been confirmed by TEM analysis and explain the observed higher combustion activity of K-containing sample.

Copyright © 2016 American Association for Aerosol Research     

Volatility characterization of nanoparticles from single and dual-fuel low temperature combustion in compression ignition engines

This work explores the volatility of particles produced from two diesel low temperature combustion (LTC) modes proposed for high-efficiency compression ignition engines. It also explores mechanisms of particulate formation and growth upon dilution in the near-tailpipe environment. The number distribution of exhaust particles from low- and mid-load dual-fuel reactivity controlled compression ignition (RCCI) and single-fuel premixed charge compression ignition (PPCI) modes were experimentally studied over a gradient of dilution temperature. Particle volatility of select particle diameters was investigated using volatility tandem differential mobility analysis (V-TDMA). Evaporation rates for exhaust particles were compared with V-TDMA results for candidate pure n-alkanes to identify species with similar volatility characteristics. The results show that LTC particles are mostly comprised of material with volatility similar to engine oil alkanes. V-TDMA results were used as inputs to an aerosol condensation and evaporation model to support the finding that smaller particles in the distribution are comprised of lower volatility material than large particles under primary dilution conditions. Although our results show that saturation levels are high enough to drive condensation of alkanes onto existing particles under the dilution conditions investigated, they are not high enough to allow homogeneous nucleation of these same compounds in the primary exhaust plume. Therefore, we conclude that observed particles from LTC operation must grow from low concentrations of highly nonvolatile compounds present in the exhaust.

Copyright © 2016 American Association for Aerosol Research     

Development and evaluation of a catalytic stripper for the measurement of solid ultrafine particle emissions from internal combustion engines

Abstract

Solid particle number vehicle exhaust measurements necessitate an aerosol conditioning system that removes efficiently volatile particles, does not create artifacts, and minimizes solid nucleation particle losses. Here, we present the development and evaluation of a catalytic stripper (CS) based on a unique dual-function monolithic reactor that oxidizes hydrocarbons and stores sulfur material. The CS was tested for its tetracontane particle removal efficiency, sulfur adsorption capacity with sulfur dioxide, and particle penetration with solid CAST-generated particles. The optimal operation conditions were examined including different aerosol flows and configurations, i.e., as a stand-alone device and as part of a volatile removal system with a hot and a cold dilution stage upstream and downstream of the CS, respectively. The CS managed to comply with current legislation requirements for solid particle number measurements down to 23?nm as a stand-alone device and showed great potential as part of a volatile particle removal (VPR) system for measurements at least down to 10?nm. Finally, we compared the performance of two VPR systems that use the developed CS (VPR-CS) and an evaporation tube (VPR-ET), respectively. Our results suggest that the VPR-CS exhibits higher volatile removal efficiency without creating artifacts while the particle losses are lower with the VPR-ET. Nevertheless, when measuring solid nucleation particles generated by a diesel engine with the VPR-CS, the measurement uncertainty was very low due to its high particle penetration fractions.     

Characterization of structure of single particles from various automobile engines under steady-state conditions

The effective density ρ_eff of particles emitted from various types of automobile engines was measured using a differential mobility analyzer (DMA)–aerosol particle mass analyzer method, and their morphology was investigated via transmission electron microscopy analysis. The measured exhaust particles were particles emitted from diesel engines (DEs), gasoline direct injection spark ignition (DISI) engines, gasoline port fuel injection (PFI) engines, and liquefied petroleum gas (LPG) engines. ρ_eff and the morphology of the particles were measured after classification with the DMA, and six electrical mobility diameters D_m ranging from 30 to 300 nm were selected. ρ_eff was found to decrease as D_m increased for all particles. A morphological study showed that DE and DISI particles were mainly agglomerates and PFI and LPG particles were mainly nonagglomerates. Numbers and diameters of the primary particles in the agglomerates showed no systematic differences between DE and DISI particles at a given D_m. Rather, the primary particle diameter d_p increased with increasing D_m of the agglomerates; the empirical relationship between the two diameters was found to be d_p = 8.498ln(D_m) – 12.781 for DE and DISI particles. The core (elemental carbon) diameters in the primary particles of the DE particles increased as D_m increased and were estimated to range from 8.5 nm for D_m = 70 nm to 22.1 nm for D_m = 300 nm. Although the primary particle diameter and core diameter depend on D_m, the organic coating (shell) thickness, which ranged from 5.1 to 7.4 nm, was found to be independent of D_m.

Copyright © 2016 American Association for Aerosol Research     

Hydroxyl radical formation and soluble trace metal content in particulate matter from renewable diesel and ultra low sulfur diesel in at-sea operations of a research vessel

Reactive oxygen species, including hydroxyl radicals generated by particles, play a role in both aerosol aging and PM2.5 mediated health effects. We assess the impacts of switching marine vessels from conventional diesel to renewable fuel on the ability of particles to generate hydroxyl radical when extracted in a simulated lung lining fluid or in water at pH 3.5, for samples of engine emissions from a research vessel when operating on ultra-low sulfur diesel (ULSD) and hydrogenation-derived renewable diesel (HDRD). Samples were collected during dedicated cruises in 2014 and 2015, including aged samples collected by re-intercepting the ship plume. After normalizing to particle mass, particles generated from HDRD combustion had slightly to significantly (5–50%) higher OH generation activity than those from ULSD, a difference that was statistically significant for some permutations of year/fuel/engine speed. Water soluble trace metal concentrations and fuel metal concentrations were similar, and compared to urban Los Angeles samples lower in soluble iron and manganese, but similar for most other trace metals. Because PM mass emissions were higher for HDRD, normalizing to fuel increased this difference. Freshly emitted PM had lower activity than the “plume chase” samples, and samples collected on the ship had lower activity than the urban reference. The differences in OH production correlated reasonably well with redox-active transition metals, most strongly with soluble manganese, with roles for vanadium and likely copper and iron. The results also suggest that atmospheric processing of fresh combustion particles rapidly increases metal solubility, which in turn increases OH production.

Copyright © 2017 American Association for Aerosol Research     

Effective density and volatility of particles sampled from a helicopter gas turbine engine

The effective density and size-resolved volatility of particles emitted from a Rolls-Royce Gnome helicopter turboshaft engine are measured at two engine speed settings (13,000 and 22,000 RPM). The effective density of denuded and undenuded particles was measured. The denuded effective densities are similar to the effective densities of particles from a gas turbine with a double annular combustor as well as a wide variety of internal combustion engines. The denuded effective density measurements were also used to estimate the size and number of primary particles in the soot aggregates. The primary particle size estimates show that the primary particle size was smaller at lower engine speed (in agreement with transmission electron microscopy analysis). As a demonstration, the size-resolved volatility of particles emitted from the engine is measured with a system consisting of a differential mobility analyzer, centrifugal particle mass analyzer, condensation particle counter, and catalytic stripper. This system determines the number distributions of particles that contain or do not contain non-volatile material, and the mass distributions of non-volatile material, volatile material condensed onto the surface of non-volatile particles, and volatile material forming independent particles (e.g., nucleated volatile material). It was found that the particulate at 13,000 RPM contained a measurable fraction of purely volatile material with diameters below ～25 nm and had a higher mass fraction of volatile material condensed on the surface of the soot (6%–12%) compared to the 22,000 RPM condition (1%–5%). This study demonstrates the potential to quantify the distribution of volatile particulate matter and gives additional information to characterize sampling effects with regulatory measurement procedures.

Copyright © 2017 American Association for Aerosol Research     

Understanding particles emitted from spray and wall-guided gasoline direct injection and flex fuel vehicles operating on ethanol and iso-butanol gasoline blends

Traffic-related pollutants are an ever-growing concern. However, the composition of particle emissions from new vehicle technologies using relevant current and prospective fuel blends is not known. This study tested four current and up-and-coming vehicle technologies with nine fuel blends with various concentrations of ethanol and iso-butanol. Vehicles were driven on both the federal test procedure (FTP) and the unified cycle (UC). Additional tests were conducted under steady-state speed conditions. The vehicle technologies include spray-guided gasoline direct injection (SG-GDI), wall-guided gasoline direct injection (WG-GDI), port-fuel injection flex fuel vehicle (PFI-FFV), and a wall-guided GDI-FFV. The fuels consisted of 10–83% ethanol and 16–55% iso-butanol in gasoline. The composition of soot, water-insoluble mass (WIM), water-soluble organic mass, and water-insoluble organic mass (WIOM), and OM was measured. The majority of emissions over FTP and UC were water-insoluble (>70%), and WIOM contributes mostly to OM. PFIs have lower soot and particulate matter (PM) emissions in comparison to the WG-GDI technology even while increasing the renewable fuel content. SG-GDI technology, which has not penetrated the market, show promise as soot and PM emissions are comparable to PFI vehicles while preserving the GDI fuel economy benefits. The WIM fraction in GDI-FFV consistently increased with increasing ethanol concentration. Lastly, the impact of the future vehicle emissions and traffic pollutants is discussed. SG-GDI technology is found to be a promising sustainable technology to enhance fuel economy and also reduce PM, soot, and WIM emissions.

Copyright © 2017 American Association for Aerosol Research     

Influence of waste cooking oil biodiesel on the nanostructure and volatility of particles emitted by a direct-injection diesel engine

To reduce air pollution and the reliance on fossil fuel, biodiesel has been widely investigated as an alternative fuel for diesel engines. The purpose of this study is to investigate the influence of waste cooking oil (WCO) biodiesel on the physical properties and the oxidation reactivity of the particles emitted by a diesel engine operating on WCO biodiesel as the main fuel. Experiments were conducted on a direct-injection diesel engine fueled with biodiesel, B75 (75% biodiesel and 25% diesel on volume basis, v/v), B50, B20, and diesel fuel, at five engine loads and at an engine speed of 1920 rev/min. Particulate samples were collected to analyze the particulate nanostructure, volatility, and oxidation characteristics. Biodiesel or low-load operation leads to smaller primary particles and more disordered nanostructures having shorter and more curved graphene layers. It can be found that particles from biodiesel, blended fuels, or low-load operation have higher volatile mass fractions and faster oxidation reaction rates than particles from diesel or heavy-load operation. The higher oxidation reaction rates are due mainly to the smaller particle size, the more disordered nanostructure, and the higher volatile mass fraction. It is also found that changes in primary particle size and particulate nanostructure are not directly proportional to the biodiesel content, while changes in particulate volatility and particulate oxidation reactivity are proportional to the biodiesel content. The use of biodiesel can enhance particulate oxidation reactivity and the regeneration of soot particles in an after-treatment device.

Copyright © 2016 American Association for Aerosol Research     

Application of a FIGAERO ToF CIMS for on-line characterization of real-world fresh and aged particle emissions from buses

On-line chemical characterization of real-world particle emissions from 13 transit buses was performed using a chemical ionization mass spectrometer (CIMS) equipped with a filter inlet for gases and aerosols (FIGAERO). In addition to the fresh emissions the emissions were artificially aged using a potential aerosol mass reactor (Go:PAM). The buses studied were running on different fuel types (diesel, compressed natural gas, and rapeseed methyl ester) and exhaust after-treatment systems (selective catalytic reduction (SCR), exhaust gas recirculation (EGR), and a three-way catalyst). When evaluating emissions from passing exhaust plumes using the FIGAERO ToF-CIMS, two technical features were highlighted from this work, the use of high mass calibrants and the factor enhancement method to be able to filter important compounds from mass spectra including hundreds of species. Here, acetate was used as the reagent ion to enable detection of highly oxygenated species in the exhaust particle emissions with potential high toxicity and/or secondary organic aerosol formation (SOA) potential. The acetate ionization scheme accounted for 4% to 46% of the total emitted particulate mass through identification of 61 species in the spectra. For aged emission the various fuel types provided overlapping species that could explain up to 19% of the aged emissions. This is hypothesized to come from the oxidation of engine lubrication oil, thus a common source for various fuels which was further supported by laboratory measurements. Specific markers from the SCR technology, such as urea oxidation products and further byproducts from hydrolysis were identified and attributed to reactions of isocyanic acid.

Copyright © 2019 The Author(s). Published with license by Taylor &; Francis Group, LLC     

Size and volatility of particle emissions from an ethanol-fueled HCCI engine

A scanning mobility particle sizer was used to determine the size, number, and mass concentration of particle emissions from an ethanol-fueled homogeneous charge compression ignition (HCCI) engine. Semi-volatile particle composition was characterized using tandem differential mobility analysis (TDMA). Variable temperature thermal conditioning was used to gain insight into particle volatility and a catalytic stripper was used to determine the solid particle distribution. Four engine conditions were evaluated, including low to moderate range loads and motoring (deceleration, coasting). Results indicated that aerosol from a fully premixed HCCI engine under firing conditions is formed almost entirely via nucleation of semi-volatile material originating from the lubricating oil. TDMA analysis indicated 98% of total particle volume evaporated below 100°C. Results pointed towards homogeneous nucleation of precursors derived from the organic species in the lubricating oil, possibly in combination with a sulfur species. The motoring condition, with no fuel injected, exhibited the highest number and mass concentrations. During motoring, there was poor sealing leading to increased atomization of oil and associated ash emissions. Emissions were lower during firing with better sealing and much less atomization, but evaporation of the most volatile fractions of the lubricating oil still led to significant PM emissions consisting of nearly entirely semi-volatile particles containing very little ash.

© 2017 American Association for Aerosol Research     

Tailpipe emission characteristics of PM2.5 from selected on-road China III and China IV diesel vehicles

Eighteen China III and IV diesel vehicles, including light-duty diesel trucks (LDDTs), medium-duty diesel trucks (MDDTs), heavy-duty diesel trucks (HDDTs) and buses, were tested with real-world measurements using a portable emission measurement system (PEMS). The emission factors (EFs), chemical components and surface morphology of emitted particles from these vehicles were characterized. Measured features included organic carbon (OC), elemental carbon (EC), water soluble ions (WSIs) and trace elements of PM_2.5. The modelling system MOtor Vehicle Emission Simulator (MOVES) was also employed to estimate the PM_2.5 EFs from these vehicles. Carbonaceous content made up 35.8–110.8% of PM_2.5, the largest contribution of all the determined chemical components; WSIs and elements accounted for less than 10%. The average PM_2.5 EFs of MDDTs and HDDTs were 0.389 g·km^?1 and 0.115 g·km^?1, respectively, approximately one order of magnitude higher than that of LDDTs. The PM_2.5 EFs of China III buses were much lower than those of China III MDDTs and HDDTs, indicating that the inspection maintenance program (I/M) system was carried out effectively on public diesel vehicles. Moreover, the chemical composition of 9.2–56.2% of the PM_2.5 mass emitted from China IV diesel trucks could not be identified in the present study. It was possible this unidentified mass was particle bound water, but this hypothesis should be confirmed with further measurements. The SEM images of PM_2.5 samples presented a loose floc structure. In addition, the trends of variation of estimated PM_2.5 EFs derived from the MOVES simulation were essentially consistent with those of tested values.

Copyright © 2018 American Association for Aerosol Research     

Chemical characterization of particulate emissions from diesel engines: A review

This review examines the chemical properties of particulate matter (PM) in diesel vehicle exhaust at a time when emission regulations, diesel technology development, and particle characterization techniques are all undergoing rapid change. The aim is to explore how changes in each of these areas impact the others. Particle composition is of central interest to the practical issues of health effects, climate change, source apportionment, and aerosol modeling. Thus, the emphasis here is to identify the emerging questions and examine how they can be addressed. As regulations drive down the allowed tailpipe emission levels, advances in engine and aftertreatment technology have made it possible to substantially reduce PM emissions. Besides the reduction in level, new technologies such as diesel particulate filters (DPFs) and selective catalytic reduction (SCR) can also affect the physical and chemical properties of PM. This in turn introduces new analytical demands that must address not only the issue of sensitivity, but also of specificity. New methods of aerosol chemical analysis are described that address these needs, improve our understanding of particle composition, and provide critical insight into the current issues surrounding motor vehicle PM emissions and their environmental impact.     

Physical characterization of particulate emissions from diesel engines: a review

Properties of particles emitted from diesel engines and the consequences of these properties for sampling and measuring the particles are reviewed. The influence of aftertreatment devices such as particle traps and catalytic converters on particle properties is demonstrated. Based on the particle properties and results from health effect studies, requirements to metrics, and measurement systems, for example, for type approval testing, are discussed. This discussion is limited to physical properties. Special attention is given to the volatile fraction. We show that care has to be taken when designing the sampling and dilution system, because this step decisively influences what happens with the volatile material, which may remain in the gas phase, condense on solid particles, or form new particles by nucleation. If nucleation occurs, particles formed in the sampling lines may dominate the particle number concentration. A selection of systems for dilution, conditioning and measuring is shown. Systems to determine number, mass, and surface concentrations, size distributions, and carbon concentration are discussed. The discussion is focused on systems developed or adapted recently for the physical characterization of diesel particles.     

Properties of water-soluble and insoluble particulate matter emitted from dewatered sewage sludge incineration in a pilot-scale ash melting furnace

Emission of inorganic particulate matter (PM) from the incineration of dewatered sewage sludge has been investigated in a novel ash melting furnace. The sludge containing 79 wt% water was incinerated in an oxygen-enriched atmosphere at the primary temperature of 1400 °C, and its unburned volatile was combusted at 1100 °C in a secondary combustion chamber. A 13-stage low-pressure-impactor and the conventional impinger methods were employed for PM sampling at the outlet of the secondary combustion chamber. The results indicate that, PM is dominated by volatile and semi-volatile elements including Br, Cl, P, S, Na, K, Zn, As, Cu, Mn and Ni. Less refractory elements were found. PM has two major fractions: <0.22 and ?0.22 μm. Their chemical forms as well as water solubility are different between two fractions. The majority of Br, nearly half of Cl, and 40% of S and P are present in the small fraction. They are mostly water-soluble due to the association with alkali elements and heavy metals. The water-insoluble calcium sulfate and calcium/iron phosphate were, however, found in the large fraction of PM. Regarding the cations, the water solubilities of Na, K, Mn and Ni are close to their proportions partitioned into the small fraction of PM, since their water-soluble species were preferentially formed in this fraction. A relatively weak correlation for Al, Ca and As, while no such a correlation were found for Cu, Zn and Fe, due to the complex compounds formed for them.     

Long-term sensor measurements of lung deposited surface area of particulate matter emitted from local vehicular and residential wood combustion sources

Abstract

Lung deposited surface area (LDSA) is a relatively new metric that has been argued to be more accurate at predicting health effects from aerosol exposure. For typical atmospheric aerosol, the LDSA concentration depends mainly on the concentration of ultrafine particles (e.g. vehicular exhaust emissions and residential wood combustion) and therefore optical methods cannot be used to measure and quantify it. The objective of this study was to investigate and describe typical characteristics of LDSA under different urban environments and evaluate how a diffusion charging-based Pegasor AQ Urban sensor (Pegasor Ltd., Finland) can be used as an alternative to optical sensors when assessing local combustion emissions and respective LDSA concentrations. Long-term (12?months) sensor measurements of LDSA were carried out at three distinctly different measurement sites (four sensor nodes) in the Helsinki metropolitan area, Finland. The sites were affected mainly by vehicular exhaust emission (street canyon and urban background stations) and by residential wood combustion (two detached housing area stations). The results showed that the accuracy of the AQ Urban was good (R² = 0.90) for the measurement of LDSA when compared to differential mobility particle sizer. The mean concentrations of LDSA were more than twice as high at the street canyon (mean 22 µm² cm^?3) site when compared to the urban background site (mean 9.4 µm² cm^?3). In the detached housing area, the mean concentrations were 12 µm² cm^?3, and wood combustion typically caused high LDSA peaks in the evenings. High correlations and similar diurnal cycles were observed for the LDSA and black carbon at street canyon and urban background stations. The utilization of a small-scale sensor network (four nodes) showed that the cross-station variability in hourly LDSA concentrations was significant in every site, even within the same detached housing area (distance between the two sites ～670?m).     

Theory and practice in using Fourier transform infrared spectroscopy to detect hydrocarbons in emissions from gas turbine engines

This paper describes the procedures used to detect hydrocarbons in emissions from gas turbine engines using non-intrusive Fourier Transform Infrared (FTIR) spectroscopy. The basic theory of FTIR is described together with the spectroscopic concepts necessary to be able to perform observations of hydrocarbons (HC). The processes of identification and quantification of the compounds present in combustion gases from infrared spectra are described and these techniques are applied to laboratory experiments using kerosene fuel burners. The results of field trials where exhausts from commercial aircraft were studied and unburnt hydrocarbons features in the C-H stretch region were measured are discussed. Quantitative measurements of HC were performed using the hexane equivalent concentration technique.     

The simultaneous reduction of nitric oxide and soot in emissions from diesel engines

Recent studies demonstrate that the decomposition of nitric oxide on a soot molecule forms surface nitrogen and oxygen. The surface nitrogen can be recombined to gaseous N₂ while the surface oxygen desorbs from the soot molecule as CO. This non-catalytic conversion of gaseous NO into N₂ is investigated using density functional theory, transition state theory and a kinetic Monte-Carlo (kMC) simulation. The results are validated against experiments. A mechanism for the conversion of NO to N₂ on a soot surface is explored. The geometries of the intermediate stable species as well as the transition states were optimized to identify the different reaction steps. The forward and backward reaction rate of each intermediate reaction is calculated applying transition state theory. A kMC simulation using the current rates and intermediate species demonstrates feasible mechanisms for the conversion of NO to N₂ on a soot surface. It is also suggested that a portion of NO is trapped on the soot surface and this increases during the reaction and blocks the active carbon sites inhibiting further reactions. By combining different theoretical techniques in a multi-scale model, we are able to describe the conversion of soot in the presence of NO accurately.     

Photoacoustic and photothermal spectroscopy — novel tools for the analysis of particulate matter

Measurments on powders using photoacoustic (PAS) and photothermal (PTS) spectroscopic techniques are described. These methods avail themselves of the heat that is generated in a sample upon irradiation, which can be used to analyse and identify the sample through its absorption spectrum.Three different techniques have been used to extract the required information: (i) By having the specimen inside a chamber, illuminating it through a window and recording the resulting pressure variations; (ii) similarly, only having the sample outside the chamber but in contact with a membrane in the chamber wall: (iii) by measuring the extra thermal emission from the object when heated upon illumination. The advantages of using PAS and PTS methods to powder analysis are presented, and their applications to in-stream measurements of particulate solid properties are discussed.