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.     

Generation and characterization of four dilutions of diesel engine exhaust for a subchronic inhalation study

Exposure atmospheres for a rodent inhalation toxicology study were generated from the exhaust of a 2000 Cummins ISB 5.9L diesel engine coupled to a dynamometer and operated on a slightly modified heavy-duty Federal Test Procedure cycle. Exposures were conducted to one clean air control and four diesel exhaust levels maintained at four different dilution rates (300:1, 100:1, 30:1, 10:1) that yielded particulate mass concentrations of 30, 100, 300, and 1000 microg/m3. Exposures at the four dilutions were characterized for particle mass, particle size distribution (reported elsewhere), detailed chemical speciation of gaseous, semivolatile, and particle-phase inorganic and organic compounds. Target analytes included metals, inorganic ions and gases, organic and elemental carbon, alkanes, alkenes, aromatic and aliphatic acids, aromatic hydrocarbons, polycyclic aromatic hydrocarbons (PAH), oxygenated PAH, nitrogenated PAH, isoprenoids, carbonyls, methoxyphenols, sugar derivatives, and sterols. The majority of the mass of material in the exposure atmospheres was gaseous nitrogen oxides and carbon monoxide, with lesser amounts of volatile organics and particle mass (PM) composed of carbon (approximately 90% of PM) and ions (approximately 10% of PM). Measured particle organic species accounted for about 10% of total organic particle mass and were mostly alkanes and aliphatic acids. Several of the components in the exposure atmosphere scaled in concentration with dilution but did not scale precisely with the dilution rate because of background from the rodents and scrubbed dilution air, interaction of animal derived emissions with diesel exhaust components, and day-to-day variability in the output of the engine. Rodent-derived ammonia reacted with exhaust to form secondary inorganic particles (at different rates dependent on dilution), and rodent respiration accounted for volatile organics (especially carbonyls and acids) in the same range as the diesel exhaust at the lowest exhaust exposure concentrations. Day-to-day variability in the engine output was implicated partially for differences of several components, including some of the particle bound organics. Though these observations have likely occurred in nearly all inhalation exposure atmospheres that contain complex mixtures of material, the speciations conducted here illustrate many of them for the first time.     

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.     

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.     

Nucleation mode particles with a nonvolatile core in the exhaust of a heavy duty diesel vehicle

The characteristics of the nucleation mode particles of a Euro IV heavy-duty diesel vehicle exhaust were studied. The NOx and PM emissions of the vehicle were controlled through the use of cooled EGR and high-pressure fuel injection techniques; no exhaust gas after-treatment was used. Particle measurements were performed in vehicle laboratory and on road. Nucleation mode dominated the particle number size distribution in all the tested driving conditions. According to the on-road measurements, the nucleation mode was already formed after 0.7 s residence time in the atmosphere and no significant changes were observed for longer residence times. The nucleation mode was insensitive to the fuel sulfur content, dilution air temperature, and relative humidity. An increase in the dilution ratio decreased the size of the nucleation mode particles. This behavior was observed to be linked to the total hydrocarbon concentration in the diluted sample. In volatility measurements, the nucleation mode particles were observed to have a nonvolatile core with volatile species condensed on it. The results indicate that the nucleation mode particles have a nonvolatile core formed before the dilution process. The core particles have grown because of the condensation of semivolatile material, mainly hydrocarbons, during the dilution.     

A comparative investigation of ultrafine particle number and mass emissions from a fleet of on-road diesel and CNG buses

Particle number, particle mass, and CO2 concentrations were measured on the curb of a busy urban busway used entirely by a mix of diesel and CNG operated buses. With the passage of each bus, the ratio of particle number concentration and particle mass concentration to CO2 concentration in the diluted exhaust plume were used as measures of the particle number and mass emission factors, respectively. With all buses accelerating pastthe monitoring point, the results showed that the median particle mass emission from CNG buses was less than 9% of that from diesel buses. However, the median particle number emission from CNG buses was 6 times higher than the diesel buses, and the particles from the CNG buses were mainly in the nanoparticle size range. Using a thermodenuder to remove the volatile material from the sampled emissions showed that the majority of particles from the CNG buses, but not from the diesel buses, were volatile. Approximately, 82% of the particles from the CNG buses and 38% from the diesel buses were removed by heating the emissions to 300 degrees C.     

Source reconciliation of atmospheric gas-phase and particle-phase pollutants during a severe photochemical smog episode

A comprehensive organic compound-based receptor model is developed that can simultaneously apportion the source contributions to atmospheric gas-phase organic compounds, semivolatile organic compounds, fine particle organic compounds, and fine particle mass. The model is applied to ambient data collected at four sites in the south coast region of California during a severe summertime photochemical smog episode, where the model determines the direct primary contributions to atmospheric pollutants from 11 distinct air pollution source types. The 11 sources included in the model are gasoline-powered motor vehicle exhaust, diesel engine exhaust, whole gasoline vapors, gasoline headspace vapors, organic solvent vapors, whole diesel fuel, paved road dust, tire wear debris, meat cooking exhaust, natural gas leakage, and vegetative detritus. Gasoline engine exhaust plus whole gasoline vapors are the predominant sources of volatile organic gases, while gasoline and diesel engine exhaust plus diesel fuel vapors dominate the emissions of semivolatile organic compounds from these sources during the episode studied at all four air monitoring sites. The atmospheric fine particle organic compound mass was composed of noticeable contributions from gasoline-powered motor vehicle exhaust, diesel engine exhaust, meat cooking, and paved road dust with smaller but quantifiable contributions from vegetative detritus and tire wear debris. In addition, secondary organic aerosol, which is formed from the low-vapor pressure products of gas-phase chemical reactions, is found to be a major source of fine particle organic compound mass under the severe photochemical smog conditions studied here. The concentrations of secondary organic aerosol calculated in the present study are compared with previous fine particle source apportionment results for less intense photochemical smog conditions. It is shown that estimated secondary organic aerosol concentrations correlate fairly well with the concentrations of 1,2-benzenedicarboxylic acid in the atmospheric fine particle mass, indicating that aromatic diacids may be useful in the quantification of certain sources of secondary organic aerosol in the atmosphere.     

Effect of oxidation catalysts on diesel soot particles

The effect of a conventional oxidation catalyst and a novel particle oxidation catalyst (POC) on diesel particles is studied using identical methodology. Regulated particulate matter emission measurement is followed by analyzing soluble organic fraction. In addition, size distributions are measured using a partial flow sampling system with a thermodenuder as an option. A parallel ELPI-SMPS method is used to study the particle effective density and, further, the mass. Tests are conducted using a heavy duty diesel engine with a very low sulfur fuel. A decrease in particle mass was observed when using a catalyst. When using a conventional catalyst the decrease was attributed to the decrease of soluble organic fraction, while using POC the nonsoluble fraction was also found to decrease, by 8-38%. This observation is confirmed by particle number measurement, and POC was found to decrease the dry particle number concentration measured downstream of a thermodenuder by 13-28%. Further particle structure analysis indicated lower density values when using conventional catalyst or POC. The physical size of the particles was not changed noticeably over either catalyst--implying the soluble organic fraction was condensed onto the soot, filling the voids in the porous structure of soot agglomerates, when no catalyst is used.     

Ternary nucleation as a mechanism for the production of diesel nanoparticles: experimental analysis of the volatile and hygroscopic properties of diesel exhaust using the volatilization and humidification tandem differential mobility analyzer

The volatile and hygroscopic properties of diesel nanoparticles were simultaneously determined under a range of engine loads using the volatilization and humidification tandem differential mobility analyzer (VH-TDMA). Additionally, the VH-TDMA was used to measure changes in the hygroscopic behavior of the heterogeneously nucleated diesel nanoparticles as one or more semivolatile species were removed via thermal evaporation or decomposition. Particles produced at high loads exhibited high, dual-step volatility, while those particles produced at low loads were less volatile and exhibited continuous volatilization curves. The hygroscopic growth factor of the particles was shown to be load dependent with high-load particles exhibiting growth factors similar to that of ammonium sulfate. At 85% relative humidity, particles produced at moderate loads exhibited growth factors of approximately 1.1 while low-load particles were shown to be hydrophobic. Growth factors and volatilization temperatures measured for high-load particles clearly indicate that ternary nucleation is involved in particle formation.     

Effect of advanced aftertreatment for PM and NOx reduction on heavy-duty diesel engine ultrafine particle emissions

Four heavy-duty and medium-duty diesel vehicles were tested in six different aftertreament configurations using a chassis dynamometer to characterize the occurrence of nucleation (the conversion of exhaust gases to particles upon dilution). The aftertreatment included four different diesel particulate filters and two selective catalytic reduction (SCR) devices. All DPFs reduced the emissions of solid particles by several orders of magnitude, but in certain cases the occurrence of a volatile nucleation mode could increase total particle number emissions. The occurrence of a nucleation mode could be predicted based on the level of catalyst in the aftertreatment, the prevailing temperature in the aftertreatment, and the age of the aftertreatment. The particles measured during nucleation had a high fraction of sulfate, up to 62% of reconstructed mass. Additionally the catalyst reduced the toxicity measured in chemical and cellular assays suggesting a pathway for an inverse correlation between particle number and toxicity. The results have implications for exposure to and toxicity of diesel PM.     

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.     

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.     

Phase and size distribution of polycyclic aromatic hydrocarbons in diesel and gasoline vehicle emissions

Emission measurements were obtained for a variety of military vehicles at Hill Air Force Base (Ogden, UT) in November 2000 as part of a Strategic Environmental Research and Development Program. Aircraft ground support equipment vehicles using gasoline, diesel, and JP8 fuels were tested using chassis dynamometers under predetermined load. The exhaust from the tested vehicle was passed to a dilution tunnel where it was diluted 30-40 times and collected using Micro-Orifice Uniform Deposit Impactor (MOUDI) fitted with aluminum substrates, an XAD-coated annular denuder, and a filter followed by a solid adsorbent. All MOUDI substrates were analyzed for mass and for organic and elemental (EC) carbon by the thermal/optical reflectance method and for polycyclic aromatic hydrocarbons (PAHs) by GC/MS. Black carbon was measured with a photoacoustic instrument. The denuder and filter/solid adsorbent samples were analyzed for semivolatile PAH. Overall, there is more mass and higher EC contribution when the vehicle is run under higher load in comparison with the low load. However, older vehicles generally show more mass and EC emissions than newer vehicles, and there is a shift toward smaller particle sizes for the low load, which is most pronounced for newer vehicles. The particle-associated semivolatile PAHs and nonvolatile four-through six-ring PAHs are present predominantly on the submicron particles collected on MOUDI stages 0.1-0.18, 0.18-0.32, and 0.32-0.56 microm. For the low-load runs, the distribution of PAHs seems to be shifted toward smaller size particles. The gas-particle phase distribution of semivolatile PAHs depends also on the engine loading. For idle, not only are the more volatile two- and three-ring PAHs, from naphthalene to dimethylphenanthrenes, retained on the denuder portion, but also less volatile four-ring PAHs, such as fluoranthene and pyrene, are retained by the denuder at the 80-90% range, which implies that they are present predominantly in the gas phase. In contrast, for engines under high loads, a much larger portion of three- and four-ring PAHs are partitioned to the particle phase.     

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.     

Significance of semivolatile diesel exhaust organics for secondary HONO formation

The atmospheric origin of nitrous acid (HONO) is largely unknown despite its estimated importance as an OH source during daytime due to its rapid photolysis. Recently, primary HONO contained in automobile exhaust as well as secondary HONO formation on soot particles have been invoked as possible HONO sources, but none of them is able to account for the observed HONO to NOx ratios of up to 0.04 in the atmosphere. In this paper, we show that semivolatile and/or water-soluble species contained in diesel exhaust are significantly involved in secondary HONO formation. These species are not associated with soot when the exhaust exits the tailpipe. To quantify these species and to assess the reaction kinetics leading to HONO, experiments were performed in which filtered but hot diesel exhaust gas interacted with a glass surface as well as a water film mimicking dry and wet surfaces to which exhaust might be exposed. A fraction of 0.023 of the NOx emitted was heterogeneously converted to HONO, which is at least three times more than the primary HONO emissions by diesel engines and a fraction of 50 larger than HONO formed on diesel soot particles that do not contain the semivolatile organics.     

Size-resolved source apportionment of airborne particle mass in a roadside environment

Airborne particulate hopanes, steranes, and polycyclic aromatic hydrocarbons (PAHs) were measured in six size fractions < 1.8 microm particle diameter at one site upwind and two sites downwind of the Interstate 5 freeway in San Diego, CA. The smallest size fraction collected was exclusively in the ultrafine size range (D(p) < 0.1 microm; PM0.1). Size distributions of hopanes, steranes, and PAHs peaked between 0.10-0.18 microm particle aerodynamic diameter with a tail extending into the PM0.1 size range. This pattern is similar to previous dynamometer studies of hopane, sterane, and PAH size distributions emitted from gasoline- and diesel-powered vehicles. Size-resolved source profiles were combined to form an "on-road" profile for motor oil, diesel, and gasoline contributions to EC and OC. The resulting equations were used to predict source contributions to the size distributions of EC and OC in the roadside environment. The method successfully accounted for the majority of the carbonaceous material in particles with diameter < 0.18 microm, with significant residual material in larger size fractions. The peak in both the measured and predicted EC size distribution occurred between 0.1-0.18 microm particle aerodynamic diameter. The predicted OC size distribution peaked between 0.1-0.18 microm particle diameter, butthe measured OC size distribution peaked between 0.56-1.0 microm particle diameter, possibly because of secondary organic aerosol formation. Predicted OC concentrations in particles with diameter < 0.18 microm were greater than measured values 18 m downwind of the roadway but showed good agreement 37 m downwind. The largest source contributions to the PM0.1 and PM0.18 size fractions were different. PM0.18 was dominated by diesel fuel and motor oil combustion products while PM0.1 was dominated by diesel fuel and gasoline fuel combustion products. Total source contributions to ultrafine (PM0.1) EC concentrations 37 m downwind of the roadway were 44 +/- 6% diesel fuel, 21 +/- 1% gasoline, 5 +/- 6% motor oil, and 30% unknown. Total source contributions to ultrafine (PM0.1) OC concentrations 37 m downwind of the roadway were 46 +/- 5% diesel fuel, 44 +/- 5% gasoline, 20 +/- 15% motor oil with a slight overprediction (11%). Diesel fuel appears to make the single largest contribution to ultrafine (PM0.1) particle mass given the fleet distribution during the current experiment.     

Effect of engine load on diesel soot particles

This study concentrates on characterization of nonvolatile fraction of diesel particles. These particles have an impact on earth's radiation balance as well as on health effects of vehicle emissions. In addition to composition and size distribution of particles, an important factor affecting their health effects and properties and lifetimes in the atmosphere is their morphology. The effect of engine parameters on soot particle size distributions and also on particle morphology has been studied. It was found that the shape of the size distribution and also the structure of diesel particles depend on engine load. The number distributions were found to obey log-normal assumption. The width of the distribution increased with increasing engine load. The geometric standard deviations of measured distributions varied from 1.7 to 2.1. Simultaneously, the fractal dimension of particles decreased with increasing engine load. The values for mass fractal dimensions based on sealing of particle mass and mobility size were between 2.6 and 2.8. Both electron microscopy and measurements of aerodynamic size versus mobility size suggest that the morphology of particles in different size regimes vary, with the large particles being less compact than the small ones.     

Effects of dilution on fine particle mass and partitioning of semivolatile organics in diesel exhaust and wood smoke

Experiments were conducted to examine the effects of dilution on fine particle mass emissions from a diesel engine and wood stove. Filter measurements were made simultaneously using three dilution sampling systems operating at dilution ratios ranging from 20:1 to 510:1. Denuders and backup filters were used to quantify organic sampling artifacts. For the diesel engine operating at low load and wood combustion, large decreases in fine particle mass emissions were observed with increases in dilution. For example, the PM2.5 mass emission rate from a diesel engine operating at low load decreased by 50% when the dilution ratio was increased from 20:1 to 350:1. Measurements of organic and elemental carbon indicate that the changes in fine particle mass with dilution are caused by changes in partitioning of semivolatile organic compounds. At low levels of dilution semivolatile species largely occur in the particle phase, but increasing dilution reduces the concentration of semivolatile species, shifting this material to the gas phase in order to maintain phase equilibrium. Emissions of elemental carbon do not vary with dilution. Organic sampling artifacts are shown to vary with dilution because of the combination of changes in partitioning coupled with adsorption of gas-phase organics by quartz filters. The fine particle mass emissions from the diesel engine operating at medium load did not vary with dilution because of the lower emissions of semivolatile material and higher emissions of elemental carbon. To measure partitioning of semivolatile materials under atmospheric conditions, partitioning theory indicates that dilution samplers need to be operated such that the diluted exhaust achieves atmospheric levels of dilution. Too little dilution can potentially overestimate the fine particle mass emissions, and too much dilution (with clean air) can underestimate them.     

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.     

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.