Relationship between particle mass and mobility for diesel exhaust particles

We used the aerosol particle mass analyzer (APM) to measure the mass of mobility-classified diesel exhaust particles. This information enabled us to determine the effective density and fractal dimension of diesel particles as a function of engine load. We found that the effective density decreases as particle size increases. TEM images showed that this occurs because particles become more highly agglomerated as size increases. Effective density and fractal dimension increased somewhat as engine load decreased. TEM images suggest that this occurs because these particles contain more condensed fuel and/or lubricating oil. Also, we observed higher effective densities when high-sulfur EPA fuel (approximately 360 ppm S) was used than for Fischer-Tropsch fuel (approximately 0 ppm S). In addition, the effective density provides the relationship between mobility and aerodynamic equivalent diameters. The relationship between these diameters enables us to intercompare, in terms of a common measure of size, mass distributions measured with the scanning mobility particle sizer (SMPS) and a MOUDI impactor without making any assumptions about particle shape or density. We show that mass distributions of diesel particles measured with the SMPS-APM are in good agreement with distributions measured with a MOUDI and a nano-MOUDI for particles larger than approximately 60 nm. However, significantly more mass and greater variation were observed by the nano-MOUDI for particles smaller than 40 nm than by the SMPS-APM.     

Effect of fuel injection pressure on a heavy-duty diesel engine nonvolatile particle emission

The effects of the fuel injection pressure on a heavy-duty diesel engine exhaust particle emissions were studied. Nonvolatile particle size distributions and gaseous emissions were measured at steady-state engine conditions while the fuel injection pressure was changed. An increase in the injection pressure resulted in an increase in the nonvolatile nucleation mode (core) emission at medium and at high loads. At low loads, the core was not detected. Simultaneously, a decrease in soot mode number concentration and size and an increase in the soot mode distribution width were detected at all loads. Interestingly, the emission of the core was independent of the soot mode concentration at load conditions below 50%. Depending on engine load conditions, growth of the geometric mean diameter of the core mode was also detected with increasing injection pressure. The core mode emission and also the size of the mode increased with increasing NOx emission while the soot mode size and emission decreased simultaneously.     

Size analysis of automobile soot particles using field-flow fractionation

Soot particles emitted from various automobile engines are analyzed for size distributions using field-flow fractionation (FFF). Soot samples are prepared for FFF analysis using a three-step procedure, where a layer of soot particles is focused between the layers of n-hexane and water, followed by dispersing of particles in water containing 0.05% Triton X-100. The mean diameters determined by FFF show similar trends with those obtained from dynamic light scattering (DLS) and scanning electron microscopy (SEM). Data from FFF are also compared with those from an on-line scanning mobility particle sizer (SMPS). SMPS size distributions extend further to larger size than those of FFF distributions, which indicates the three-step sample preparation procedure effectively disaggregates the agglomerated particles. Although the amount of particulate matter (PM) emitted from a heavy-duty diesel engine is much higher than that from a light-duty diesel engine, the size distributions of soot particles show no significant difference between heavy- and light-duty diesel engines. The engine-operating mode (engine speed and load rate) does not seem to affect significantly the size distribution of soot particles. It was found that the PM from a turbocharged diesel engine contains a higher percentage of particles smaller than 100 nm than an engine with a naturally aspirated (NA) air-inhalation system. As for gasoline engines, the PM collected after the catalytic converter has a narrower size distribution than those collected before and has a higher percentage of particles smaller than 100 nm.     

On-road measurement of particle emission in the exhaust plume of a diesel passenger car

Particle size distributions were measured under real world dilution conditions in the exhaust plume of a diesel passenger car closely followed by a mobile laboratory on a high speed test track. Under carefully controlled conditions the exhaust plume was continuously sampled and analyzed inside the mobile laboratory. Exhaust particle size distribution data were recorded together with exhaust gas concentrations, i.e., CO, CO2, and NO(x), and compared to data obtained from the same vehicle tested on a chassis dynamometer. Good agreement was found for the soot mode particles which occurred at a geometric mean diameter of approximately 50 nm and a total particle emission rate of 10(14) particles km(-1). Using 350 ppm high sulfur fuel and the standard oxidation catalyst a bimodal size distribution with a nucleation mode at 10 nm was observed at car velocities of 100 km h(-1) and 120 km h(-1), respectively. Nucleation mode particles were only present if high sulfur fuel was used with the oxidation catalyst installed. This is in agreement with prior work that these particles are of semivolatile nature and originate from the nucleation of sulfates formed inside the catalyst. Temporal effects of the occurrence of nucleation mode particles during steady-state cruising and the dynamical behavior during acceleration and deceleration were investigated.     

Role of lubrication oil in particulate emissions from a hydrogen-powered internal combustion engine

Recent studies suggest that trace metals emitted by internal combustion engines are derived mainly from combustion of lubrication oil. This hypothesis was examined by investigation of the formation of particulate matter emitted from an internal combustion engine in the absence of fuel-derived soot. Emissions from a modified CAT 3304 diesel engine fueled with hydrogen gas were characterized. The role of organic carbon and metals from lubrication oil on particle formation was investigated under selected engine conditions. The engine produced exhaust aerosol with log normal-size distributions and particle concentrations between 10(5) and 10(7) cm(-3) with geometric mean diameters from 18 to 31 nm. The particles contained organic carbon, little or no elemental carbon, and a much larger percentage of metals than particles from diesel engines. The maximum total carbon emission rate was estimated at 1.08 g h(-1), which is much lower than the emission rate of the original diesel engine. There was also evidence that less volatile elements, such as iron, self-nucleated to form nanoparticles, some of which survive the coagulation process.     

Collection of ultrafine diesel particulate matter (DPM) in cylindrical single-stage wet electrostatic precipitators

Long-term exposures to diesel particulate matter (DPM) emissions are linked to increasing adverse human health effects due to the potential association of DPM with carcinogenicity. Current diesel vehicular particulate emission regulations are based solely upon total mass concentration, albeit it is the submicrometer particles that are highly respirable and the most detrimental to human health. In this study, experiments were performed with a tubular single-stage wet electrostatic precipitator (wESP) to evaluate its performance for the removal of number-based DPM emissions. A nonroad diesel generator utilizing a low sulfur diesel fuel (500 ppmw) operating under varying load conditions was used as a stationary DPM emission source. An electrical low-pressure impactor (ELPI) was used to quantify the number concentration distributions of diesel particles in the diluted exhaust gas at each tested condition. The wESP was evaluated with respect to different operational control parameters such as applied voltage, gas residence time, etc., to determine their effect on overall collection efficiency, as well as particle size dependent collection efficiency. The results show that the total DPM number concentrations in the untreated diesel exhaust are in the magnitude of approximately108/cm(3) at all engine loads with the particle diameter modes between 20 and 40 nm. The measured collection efficiency of the wESP operating at 70 kV based on total particle numbers was 86% at 0 kW engine load and the efficiency decreased to 67% at 75 kW due to a decrease in gas residence time and an increase in particle concentrations. At a constant wESP voltage of 70 kV and at 75 kW engine load, the variation of gas residence time within the wESP from approximately 0.1 to approximately 0.4 s led to a substantial increase in the collection efficiency from 67% to 96%. In addition, collection efficiency was found to be directly related to the applied voltage, with increasing collection efficiency measured for increases in applied voltage. The collection efficiency based on particle size had a minimum for sizes between 20 and 50 nm, but at optimal wESP operating conditions it was possible to remove over 90% of all particle sizes. A comparison of measured and calculated collection efficiencies reveals that the measured values are significantly higher than the predicted values based on the well-known Deutsch equation.     

Characterization of diesel particles: effects of fuel reformulation, exhaust aftertreatment, and engine operation on particle carbon composition and volatility

Diesel exhaust particles are the major constituent of urban carbonaceous aerosol being linked to a large range of adverse environmental and health effects. In this work, the effects of fuel reformulation, oxidation catalyst, engine type, and engine operation parameters on diesel particle emission characteristics were investigated. Particle emissions from an indirect injection (IDI) and a direct injection (DI) engine car operating under steady-state conditions with a reformulated low-sulfur, low-aromatic fuel and a standard-grade fuel were analyzed. Organic (OC) and elemental (EC) carbon fractions of the particles were quantified by a thermal-optical transmission analysis method and particle size distributions measured with a scanning mobility particle sizer (SMPS). The particle volatility characteristics were studied with a configuration that consisted of a thermal desorption unit and an SMPS. In addition, the volatility of size-selected particles was determined with a tandem differential mobility analyzer technique. The reformulated fuel was found to produce 10-40% less particulate carbon mass compared to the standard fuel. On the basis of the carbon analysis, the organic carbon contributed 27-61% to the carbon mass of the IDI engine particle emissions, depending on the fuel and engine operation parameters. The fuel reformulation reduced the particulate organic carbon emissions by 10-55%. In the particles of the DI engine, the organic carbon contributed 14-26% to the total carbon emissions, the advanced engine technology, and the oxidation catalyst, thus reducing the OC/EC ratio of particles considerably. A relatively good consistency between the particulate organic fraction quantified with the thermal optical method and the volatile fraction measured with the thermal desorption unit and SMPS was found.     

Size-dependent volatility of diesel nanoparticles: chassis dynamometer experiments

We analyzed the size-dependent volatility of nanoparticles in a diameter range of 30-70 nm in diesel exhaust emissions. The test system included a medium-duty diesel truck on a chassis dynamometer, a single-stage dilution tunnel, a tandem differential mobility analyzer (TDMA) equipped with an electric furnace, and a condensation particle counter. The size shifts of monodispersed diesel nanoparticles under changing furnace temperatures were measured by TDMA in the gas phase. Together with the reduction of average particle size and volume, we observed the development of bimodal size distributions resulting from the separation between semivolatile and nonvolatile species as the furnace temperature was increased. While 91-98% of the particles were found to be semivolatile species by total volume during the idling engine condition, only 6-9% were semivolatile during the one-half engine load condition. We also found that smaller particles contained a larger fraction of semivolatile species.     

Influence of diesel fuel sulfur on nanoparticle emissions from city buses

Particle emissions from twelve buses, operating alternately on low sulfur (LS; 500 ppm) and ultralow sulfur (ULS; 50 ppm) diesel fuel, were monitored. The buses were 1-19 years old and had no after-treatment devices fitted. Measurements were carried out at four steady-state operational modes on a chassis dynamometer using a mini dilution tunnel (PM mass measurement) and a Dekati ejector diluter as a secondary diluter (SMPS particle number). The mean particle number emission rate (s(-1)) of the buses, in the size range 8-400 nm, using ULS diesel was 31% to 59% lower than the rate using LS diesel in all four modes. The fractional reduction was highest in the newest buses and decreased with mileage upto about 500,000 km, after which no further decrease was apparent. However, the mean total suspended particle (TSP) mass emission rate did not show a systematic difference between the two fuel types. When the fuel was changed from LS to ULS diesel, the reduction in particle number was mainly in the nanoparticle size range. Over all operational modes, 58% of the particles were smaller than 50 nm with LS fuel as opposed to just 45% with ULS fuel, suggesting that sulfur in diesel fuel was playing a major role in the formation of nanoparticles. The greatest influence of the fuel sulfur content was observed at the highest engine load, where 74% of the particles were smaller than 50 nm with LS diesel compared to 43% with ULS diesel.     

Kinetics of diesel nanoparticle oxidation

The technique of high-temperature oxidation tandem differential mobility analysis has been applied to the study of diesel nanoparticle oxidation. The oxidation rates in air of diesel nanoparticles sampled directly from the exhaust stream of a medium-duty diesel engine were measured over the temperature range of 800-1140 degrees C using online aerosol techniques. Three particle sizes (40, 90, and 130 nm mobility diameter) generated under engine load conditions of 10, 50, and 75% were investigated. The results show significant differences in the behavior of the 10% load particles as compared to the 50 and 75% load particles. The 10% load particles show greater size decrease at temperatures below 500 degrees C and significant size decrease at temperatures between 500 and 1000 degrees C in a non-oxidative environment, indicating release of adsorbed volatile material or thermally induced rearrangement of the agglomerate structure. Activation energies determined are 114, 109, and 108 kJ mol(-1) for the 10, 50, and 75% load particles, respectively. These activation energies are lower than for flame soot (Higgins et al. J. Phys. Chem. A 2002, 106, 96), but the preexponential factors are lower by 3 orders of magnitude, and the overall oxidation rates are slower by up to a factor of 4 over the temperature range studied. Possible reasons for the differences are discussed in the text.     

Reductions in particulate and NO(x) emissions by diesel engine parameter adjustments with HVO fuel

Hydrotreated vegetable oil (HVO) diesel fuel is a promising biofuel candidate that can complement or substitute traditional diesel fuel in engines. It has been already reported that by changing the fuel from conventional EN590 diesel to HVO decreases exhaust emissions. However, as the fuels have certain chemical and physical differences, it is clear that the full advantage of HVO cannot be realized unless the engine is optimized for the new fuel. In this article, we studied how much exhaust emissions can be reduced by adjusting engine parameters for HVO. The results indicate that, with all the studied loads (50%, 75%, and 100%), particulate mass and NO(x) can both be reduced over 25% by engine parameter adjustments. Further, the emission reduction was even higher when the target for adjusting engine parameters was to exclusively reduce either particulates or NO(x). In addition to particulate mass, different indicators of particulate emissions were also compared. These indicators included filter smoke number (FSN), total particle number, total particle surface area, and geometric mean diameter of the emitted particle size distribution. As a result of this comparison, a linear correlation between FSN and total particulate surface area at low FSN region was found.     

Size-dependent mixing characteristics of volatile and nonvolatile components in diesel exhaust aerosols

Mixing characteristics of particles of different volatilities from a diesel engine were studied with two tandem differential mobility analyzers (TDMAs) and an aerosol particle mass analyzer (APM). In both TDMA systems, a heater was located in the aerosol path between the first and second DMAs. Diesel exhaust particles that were size-selected in the first DMA were passed through the heater, and the change in particle size due to loss of volatile components was determined by the second DMA. On the basis of the volatility measurements, the particles could be separated into two overlapping modes that varied in peak diameter and magnitude depending on the engine operating conditions. Particles in the smaller size mode were almost completely volatile, while those in the larger size mode contained a nonvolatile core. The TDMA data inversion technique used here allowed accurate determination of the mixing ratios of the two types of particles. These data were in turn used to validate a simple fitting method that uses two log-normal curves to obtain the mixing ratios. In some experiments, the APM was used downstream of a TDMA to directly measure the particle mass loss due to evaporation. The loss determined bythe TDMA-APM system was significantly greater than that calculated from mobility size changes measured solely with the TDMA. The TDMA-APM results were used to calculate the size-dependent mass concentrations of volatile and nonvolatile components for particles in the size range from 70 to 200 nm.     

Influence of real-world engine load conditions on nanoparticle emissions from a DPF and SCR equipped heavy-duty diesel engine

The experiments aimed at investigating the effect of real-world engine load conditions on nanoparticle emissions from a Diesel Particulate Filter and Selective Catalytic Reduction after-treatment system (DPF-SCR) equipped heavy-duty diesel engine. The results showed the emission of nucleation mode particles in the size range of 6-15 nm at conditions with high exhaust temperatures. A direct result of higher exhaust temperatures (over 380 °C) contributing to higher concentration of nucleation mode nanoparticles is presented in this study. The action of an SCR catalyst with urea injection was found to increase the particle number count by over an order of magnitude in comparison to DPF out particle concentrations. Engine operations resulting in exhaust temperatures below 380 °C did not contribute to significant nucleation mode nanoparticle concentrations. The study further suggests the fact that SCR-equipped engines operating within the Not-To-Exceed (NTE) zone over a critical exhaust temperature and under favorable ambient dilution conditions could contribute to high nanoparticle concentrations to the environment. Also, some of the high temperature modes resulted in DPF out accumulation mode (between 50 and 200 nm) particle concentrations an order of magnitude greater than typical background PM concentrations. This leads to the conclusion that sustained NTE operation could trigger high temperature passive regeneration which in turn would result in lower filtration efficiencies of the DPF that further contributes to the increased solid fraction of the PM number count.     

Nucleation particles in diesel exhaust: composition inferred from in situ mass spectrometric analysis

Mass spectrometric measurements of size and composition of diesel exhaust particles have been performed under various conditions: chassis dynamometer tests, field measurements near a German motorway, and individual car chasing. Nucleation particles consisting of volatile sulfate and organic material could be detected both at the chassis dynamometer test facility and during individual car chasing. We found evidence that if nucleation occurs, sulfuric acid/water is the nucleating agent. Low-volatile organics species condense only on the preexisting sulfuric acid/water clusters. Nucleation was found to depend strongly on various parameters such as exhaust dilution conditions, fuel sulfur content, and engine load. The latter determines the fraction of the fuel sulfur that is converted to sulfuric acid. The organic compounds (volatile and low-volatile) condense only on preexisting particles, such as both sulfuric acid nucleation particles and larger accumulation mode soot particles. On the latter, sulfuric acid also condenses, if the conditions for nucleation are not given. The overall ratio of sulfate to organic (volatile and low-volatile) is also strongly dependent on the engine load. It was found that the production of nucleation particles even at high engine load can be suppressed by using low-sulfur fuel.     

Characteristics of SME biodiesel-fueled diesel particle emissions and the kinetics of oxidation

Biodiesel is one of the most promising alternative diesel fuels. As diesel emission regulations have become more stringent, the diesel particulate filter (DPF) has become an essential part of the aftertreatment system. Knowledge of kinetics of exhaust particle oxidation for alternative diesel fuels is useful in estimating the change in regeneration behavior of a DPF with such fuels. This study examines the characteristics of diesel particulate emissions as well as kinetics of particle oxidation using a 1996 John Deere T04045TF250 off-highway engine and 100% soy methyl ester (SME) biodiesel (B100) as fuel. Compared to standard D2 fuel, this B100 reduced particle size, number, and volume in the accumulation mode where most of the particle mass is found. At 75% load, number decreased by 38%, DGN decreased from 80 to 62 nm, and volume decreased by 82%. Part of this decrease is likely associated with the fact that the particles were more easily oxidized. Arrhenius parameters for the biodiesel fuel showed a 2-3times greater frequency factor and approximately 6 times higher oxidation rate compared to regular diesel fuel in the range of 700-825 degrees C. The faster oxidation kinetics should facilitate regeneration when used with a DPF.     

Mutagenicity of diesel engine exhaust is eliminated in the gas phase by an oxidation catalyst but only slightly reduced in the particle phase

Concerns about adverse health effects of diesel engine emissions prompted strong efforts to minimize this hazard, including exhaust treatment by diesel oxidation catalysts (DOC). The effectiveness of such measures is usually assessed by the analysis of the legally regulated exhaust components. In recent years additional analytical and toxicological tests were included in the test panel with the aim to fill possible analytical gaps, for example, mutagenic potency of polycyclic aromatic hydrocarbons (PAH) and their nitrated derivatives (nPAH). This investigation focuses on the effect of a DOC on health hazards from combustion of four different fuels: rapeseed methyl ester (RME), common mineral diesel fuel (DF), SHELL V-Power Diesel (V-Power), and ARAL Ultimate Diesel containing 5% RME (B5ULT). We applied the European Stationary Cycle (ESC) to a 6.4 L turbo-charged heavy load engine fulfilling the EURO III standard. The engine was operated with and without DOC. Besides regulated emissions we measured particle size and number distributions, determined the soluble and solid fractions of the particles and characterized the bacterial mutagenicity in the gas phase and the particles of the exhaust. The effectiveness of the DOC differed strongly in regard to the different exhaust constituents: Total hydrocarbons were reduced up to 90% and carbon monoxide up to 98%, whereas nitrogen oxides (NO(X)) remained almost unaffected. Total particle mass (TPM) was reduced by 50% with DOC in common petrol diesel fuel and by 30% in the other fuels. This effect was mainly due to a reduction of the soluble organic particle fraction. The DOC caused an increase of the water-soluble fraction in the exhaust of RME, V-Power, and B5ULT, as well as a pronounced increase of nitrate in all exhausts. A high proportion of ultrafine particles (10-30 nm) in RME exhaust could be ascribed to vaporizable particles. Mutagenicity of the exhaust was low compared to previous investigations. The DOC reduced mutagenic effects most effectively in the gas phase. Mutagenicity of particle extracts was less efficiently diminished. No significant differences of mutagenic effects were observed among the tested fuels. In conclusion, the benefits of the DOC concern regulated emissions except NO(X) as well as nonregulated emissions such as the mutagenicity of the exhaust. The reduction of mutagenicity was particularly observed in the condensates of the gas phase. This is probably due to better accessibility of gaseous mutagenic compounds during the passage of the DOC in contrast to the particle-bound mutagens. Concerning the particulate emissions DOC especially decreased ultrafine particles.     

Understanding the difference in oxidative properties between flame and diesel soot nanoparticles: the role of metals

The purpose of this paper is to address the differences observed in the oxidative kinetics between flame and diesel derived soots. In particular, it has been observed that flame soot has a significantly higher activation energy for oxidation than does diesel soot. The hypothesis tested in this paper is that metals, possibly coming from lubricating oils, within diesel generated soot particles may be responsible for this effect. This is supported by the fact that addition of metal additives to diesel fuel is shown to have no effect on the activation energy of soot oxidation. The subject of this paper lies in testing the hypothesis by adding metal directly to a flame and extracting oxidation kinetics. Using a high temperature oxidation tandem differential mobility analyzer (HTO-TDMA) we extract particle size dependent kinetics for the oxidation of flame-derived soot doped with and without iron. We found that indeed addition of iron to a flame reduced the activation energy significantly from approximately 162 +/- 3 kJ/mol to approximately 116 +/- 3 kJ/mol, comparable with diesel engine generated soot with an activation energy approximately 110 kJ/mol. These results are consistent with the idea that small quantities of metals during diesel combustion may play an important role in soot abatement.     

Single particle characterization of ultrafine and accumulation mode particles from heavy duty diesel vehicles using aerosol time-of-flight mass spectrometry

The aerodynamic size and chemical composition of individual ultrafine and accumulation mode particle emissions (Da = 50-300 nm) were characterized to determine mass spectral signatures for heavy duty diesel vehicle (HDDV) emissions that can be used for atmospheric source apportionment. As part of this study, six in-use HDDVs were operated on a chassis dynamometer using the heavy heavy-duty diesel truck (HHDDT) five-cycle driving schedule under different simulated weight loads. The exhaust emissions were passed through a dilution/residence system to simulate atmospheric dilution conditions, after which an ultrafine aerosol time-of-flight mass spectrometer (UF-ATOFMS) was used to sample and characterize the HDDV exhaust particles in real-time. This represents the first study where refractory species including elemental carbon and metals are characterized directly in HDDV emissions using on-line mass spectrometry. The top three particle classes observed with the UF-ATOFMS comprise 91% of the total particles sampled and show signatures indicative of a combination of elemental carbon (EC) and engine lubricating oil. In addition to the vehicle make/year, the effects of driving cycle and simulated weight load on exhaust particle size and composition were investigated.     

The effects of the catalytic converter and fuel sulfur level on motor vehicle particulate matter emissions: light duty diesel vehicles

Wind tunnel measurements and direct tailpipe particulate matter (PM) sampling are utilized to examine how the combination of oxidation catalyst and fuel sulfur content affects the nature and quantity of PM emissions from the exhaust of a light duty diesel truck. When low sulfur fuel (4 ppm) is used, or when high sulfur (350 ppm)fuel is employed without an active catalyst present, a single log-normal distribution of exhaust particles is observed with a number mean diameter in the range of 70-83 nm. In the absence of the oxidation catalyst, the high sulfur level has at most a modest effect on particle emissions (<50%) and a minor effect on particle size (<5%). In combination with the active oxidation catalyst tested, high sulfur fuel can lead to a second, nanoparticle, mode, which appears at approximately 20 nm during high speed operation (70 mph), but is not present at low speed (40 mph). A thermodenuder significantly reduces the nanoparticle mode when set to temperatures above approximately 200 degrees C, suggesting that these particles are semivolatile in nature. Because they are observed only when the catalyst is present and the sulfur level is high, this mode likely originates from the nucleation of sulfates formed over the catalyst, although the composition may also include hydrocarbons.     

Diesel engine exhaust emission: oxidative behavior and microstructure of black smoke soot particulate

Soot particulate collected from a Euro III heavy duty diesel engine run under black smoke conditions was investigated using thermogravimetry, transmission electron microscopy, electron energy loss spectroscopy, and X-ray photoelectron spectroscopy. The characterization results are compared with those of commercial carbon black. The onset temperature toward oxidation of the diesel engine soot in 5% O2 is 150 degrees C lower than that for carbon black. The burn out temperature for the diesel engine soot is 60 degrees C lower than that of the carbon black. The soot primary particles exhibit a core-shell structure. The shell of the soot particles consists of homogeneously stacked basic structure units. The commercial carbon lamp black is more graphitized than the diesel engine soot, whereas the diesel engine soot contains more carbon in aromatic nature than the carbon black and is highly surface-functionalized. Our findings reveal that technical carbon black is not a suitable model for the chemistry of the diesel engine soot.