Diesel particle filter and fuel effects on heavy-duty diesel engine emissions

The impacts of biodiesel and a continuously regenerated (catalyzed) diesel particle filter (DPF) on the emissions of volatile unburned hydrocarbons, carbonyls, and particle associated polycyclic aromatic hydrocarbons (PAH) and nitro-PAH, were investigated. Experiments were conducted on a 5.9 L Cummins ISB, heavy-duty diesel engine using certification ultra-low-sulfur diesel (ULSD, S ≤ 15 ppm), soy biodiesel (B100), and a 20% blend thereof (B20). Against the ULSD baseline, B20 and B100 reduced engine-out emissions of measured unburned volatile hydrocarbons and PM associated PAH and nitro-PAH by significant percentages (40% or more for B20 and higher percentage for B100). However, emissions of benzene were unaffected by the presence of biodiesel and emissions of naphthalene actually increased for B100. This suggests that the unsaturated FAME in soy-biodiesel can react to form aromatic rings in the diesel combustion environment. Methyl acrylate and methyl 3-butanoate were observed as significant species in the exhaust for B20 and B100 and may serve as markers of the presence of biodiesel in the fuel. The DPF was highly effective at converting gaseous hydrocarbons and PM associated PAH and total nitro-PAH. However, conversion of 1-nitropyrene by the DPF was less than 50% for all fuels. Blending of biodiesel caused a slight reduction in engine-out emissions of acrolein, but otherwise had little effect on carbonyl emissions. The DPF was highly effective for conversion of carbonyls, with the exception of formaldehyde. Formaldehyde emissions were increased by the DPF for ULSD and B20.     

Variability of particle number emissions from diesel and hybrid diesel-electric buses in real driving conditions

A linear mixed model was developed to quantify the variability of particle number emissions from transit buses tested in real-world driving conditions. Two conventional diesel buses and two hybrid diesel-electric buses were tested throughout 2004 under different aftertreatments, fuels, drivers, and bus routes. The mixed model controlled the confounding influence of factors inherent to on-board testing. Statistical tests showed that particle number emissions varied significantly according to the after treatment, bus route, driver, bus type, and daily temperature, with only minor variability attributable to differences between fuel types. The daily setup and operation of the sampling equipment (electrical low pressure impactor) and mini-dilution system contributed to 30-84% of the total random variability of particle measurements among tests with diesel oxidation catalysts. By controlling for the sampling day variability, the model better defined the differences in particle emissions among bus routes. In contrast, the low particle number emissions measured with diesel particle filters (decreased by over 99%) did not vary according to operating conditions or bus type but did vary substantially with ambient temperature.     

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.     

Time resolved characterization of diesel particulate emissions. 1. Instruments for particle mass measurements

The measurement of diesel vehicle exhaust particulate mass is currently accomplished using filter collection methods according to the Code of Federal Regulations (CFR). Such filter methods limit time resolution to a minimum of several minutes, making it impossible to study emissions during transient operating conditions. Extensive testing of five different measurement methods has demonstrated that fast response measurements of diesel exhaust particulate mass concentrations, consistent with CFR filter measurements, are feasible using existing technology. The measurement principles of choice are the real time weighing of exhaust samples as implemented in the tapered element oscillating microbalance (TEOM) and the measurement of light scattering from exhaust particles as implemented in the DustTrak nephelometer. Each of these two instruments has distinctive strengths. The TEOM excels in the area of constant calibration, independent of vehicle. For the DustTrak, this calibration varies by vehicle. On the other hand, the DustTrak has an excellent signal-to-noise ratio, freedom from interference due to other exhaust sample properties, good time resolution, and simplicity. The strengths of the two measurement methods are complimentary, so an obvious suggestion is to integrate them. The nephelometer would obtain a fast response signal, with near real time calibration provided by the microbalance.     

Effects of diesel particle filter retrofits and accelerated fleet turnover on drayage truck emissions at the Port of Oakland

Heavy-duty diesel drayage trucks have a disproportionate impact on the air quality of communities surrounding major freight-handling facilities. In an attempt to mitigate this impact, the state of California has mandated new emission control requirements for drayage trucks accessing ports and rail yards in the state beginning in 2010. This control rule prompted an accelerated diesel particle filter (DPF) retrofit and truck replacement program at the Port of Oakland. The impact of this program was evaluated by measuring emission factor distributions for diesel trucks operating at the Port of Oakland prior to and following the implementation of the emission control rule. Emission factors for black carbon (BC) and oxides of nitrogen (NO(x)) were quantified in terms of grams of pollutant emitted per kilogram of fuel burned using a carbon balance method. Concentrations of these species along with carbon dioxide were measured in the exhaust plumes of individual diesel trucks as they drove by en route to the Port. A comparison of emissions measured before and after the implementation of the truck retrofit/replacement rule shows a 54 ± 11% reduction in the fleet-average BC emission factor, accompanied by a shift to a more highly skewed emission factor distribution. Although only particulate matter mass reductions were required in the first year of the program, a significant reduction in the fleet-average NO(x) emission factor (41 ± 5%) was observed, most likely due to the replacement of older trucks with new ones.     

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.     

Particle emissions from diesel passenger cars equipped with a particle trap in comparison to other technologies

Tail pipe particle emissions of passenger cars, with different engine and aftertreatment technologies, were determined with special focus on diesel engines equipped with a particle filter. The particle number measurements were performed, during transient tests, using a condensation particle counter. The measurement procedure complied with the draft Swiss ordinance, which is based on the findings of the UN/ECE particulate measurement program. In addition, particle mass emissions were measured by the legislated and a modified filter method. The results demonstrate the high efficiency of diesel particle filters (DPFs) in curtailing nonvolatile particle emissions over the entire size range. Higher emissions were observed during short periods of DPF regeneration and immediately afterward, when a soot cake has not yet formed on the filter surface. The gasoline vehicles exhibited higher emissions than the DPF equipped diesel vehicles but with a large variation depending on the technology and driving conditions. Although particle measurements were carried out during DPF regeneration, it was impossible to quantify their contribution to the overall emissions, due to the wide variation in intensity and frequency of regeneration. The numbers counting method demonstrated its clear superiority in sensitivity to the mass measurement. The results strongly suggest the application of the particle number counting to quantify future low tailpipe emissions.     

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.     

Quinone emissions from gasoline and diesel motor vehicles

Gas- and particle-phase emissions from gasoline and diesel vehicles operated on chassis dynamometers were collected using annular denuders, quartz filters, and PUF substrates. Quinone species were measured using O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine derivatization in conjunction with gas chromatography-mass spectrometry and high-performance liquid chromatography-mass spectrometry. Nine quinones were observed, ranging from C6 to C16. New species identified in motor vehicle exhaust include methyl-1,4-benzoquinone, 2-methyl-1,4-naphthoquinone (MNQN), and aceanthrenequinone. Gas-phase motor vehicle emissions of quinones are also reported for the first time. Six gas-phase quinones were quantified with emission rates of 2-28 000 microg L(-1) fuel consumed. The most abundant gas-phase quinones were 1,4-benzoquinone (BON) and MNQN. The gas-phase fraction was > or = 69% of quinone mass for light-duty gasoline emissions, and > or = 84% for heavy-duty diesel emissions. Eight particle-phase quinones were observed between 2 and 1600 microg L(-1), with BQN the most abundant species followed by 9,10-phenanthrenequinone and 1,2-naphthoquinone. Current particle-phase quinone measurements agree well with the few available previous results. Further research is needed concerning the gas-particle partitioning behavior of quinones in ambient and combustion source conditions.     

Carbonyl emissions from gasoline and diesel motor vehicles

Carbonyls from gasoline-powered light-duty vehicles (LDVs) and heavy-duty diesel-powered vehicles (HDDVs) operated on chassis dynamometers were measured by use of an annular denuder-quartz filter-polyurethane foam sampler with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine derivatization and chromatography-mass spectrometry analyses. Two internal standards were utilized based on carbonyl recovery: 4-fluorobenzaldehyde for < C8 carbonyls and 6-fluoro-4-chromanone for > or = C8 compounds. Gas- and particle-phase emissions for 39 aliphatic and 20 aromatic carbonyls ranged from 0.1 to 2000 microg/L of fuel for LDVs and from 1.8 to 27 000 microg/L of fuel for HDDVs. Gas-phase species accounted for 81-95% of the total carbonyls from LDVs and 86-88% from HDDVs. Particulate carbonyls emitted from a HDDV under realistic driving conditions were similar to concentrations measured in a diesel particulate matter (PM) standard reference material. Carbonyls accounted for 19% of particulate organic carbon (POC) emissions from low-emission LDVs and 37% of POC emissions from three-way catalyst-equipped LDVs. This identifies carbonyls as one of the largest classes of compounds in LDV PM emissions. The carbonyl fraction of HDDV POC was lower, 3.3-3.9% depending upon operational conditions. Partitioning analysis indicates the carbonyls had not achieved equilibrium between the gas and particle phases under the dilution factors of 126-584 used in the present study.     

Effect of diesel oxidation catalysts on the diesel particulate filter regeneration process

A Diesel Particulate Filter (DPF) regeneration process was investigated during aftertreatment exhaust of a simulated diesel engine under the influence of a Diesel Oxidation Catalyst (DOC). Aerosol mass spectrometry analysis showed that the presence of the DOC decreases the Organic Carbon (OC) fraction adsorbed to soot particles. The activation energy values determined for soot nanoparticles oxidation were 97 ± 5 and 101 ± 8 kJ mol(-1) with and without the DOC, respectively; suggesting that the DOC does not facilitate elementary carbon oxidation. The minimum temperature necessary for DPF regeneration was strongly affected by the presence of the DOC in the aftertreatment. The conversion of NO to NO(2) inside the DOC induced the DPF regeneration process at a lower temperature than O(2) (ΔT = 30 K). Also, it was verified that the OC fraction, which decreases in the presence of the DOC, plays an important role to ignite soot combustion.     

Effect of truck operating weight on heavy-duty diesel emissions

Heavy-duty diesel vehicles are substantial contributors of oxides of nitrogen (NO(x)) and particulate matter (PM) while carbon monoxide and hydrocarbon (HC) emissions from diesel vehicles receive less attention. Truck emissions inventories have traditionally employed average fuel economy and engine efficiency factors to translate certification into distance-specific (g/mi) data, so that inventories do not take into account the real effects of truck operating weight on emissions. The objective of this research was to examine weight corrections for class 7 and 8 vehicles (over 26 000 lb (11 793 kg) gross vehicle weight) from a theoretical point of view and to present a collection of original data on the topic. It was found by combining an empirical equation with theoretical truck loads that the NO(x) emissions increased by approximately 54% for a doubling of test weight. Emissions data were gathered from specific tests performed using different test weights and using various test schedules, which can consist of cycles or routes. It was found experimentally that NO(x) emissions have a nearly linear correlation with vehicle weight and did not vary much from vehicle to vehicle. NO(x) emissions were also found to be insensitive to transient operation in the test schedule. The observed trends correlate well with the theory presented, and hence, the NO(x) emissions can be predicted reasonably accurately using the theory. If NO(x) data were considered in fuel-specific (g/gal) units, they did not vary with the test weight. HC emissions were found to be insensitive to the vehicle weight. CO and PM emissions were found to be a strong function of weight during transient operation. Under transient operation, the CO emissions value increased by 36% for an increase in test weight from 42 000 (19 051 kg) to 56 000 lb (25 401 kg). However, CO and PM were found to be insensitive to the vehicle weight during nearly steady-state operation.     

On-road emissions of PCDDs and PCDFs from heavy duty diesel vehicles

This work characterized emission factors of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/Fs) from on-road sampling of three heavy duty diesel vehicles (HDDVs) under experimental conditions of city and highway driving; idling operation; high (>400 ppm) and low (<5 ppm) sulfur (S) fuels; and high mileage and rebuilt engine testing. Emission factors, homologue profiles, and isomer patterns were compared to determine whether the experimental conditions had an impact on PCDD/F emissions, or whether these conditions were uninfluential in determining a fleet-representative emission factor. For a single HDDV tested under conditions of a high mileage engine, a newly rebuilt engine, and the newly rebuilt engine with low S diesel fuel, emission factors were 0.023 (+/- 0.022), 0.008 (+/- 0.002), and 0.016 (+/- 0.013) ng toxic equivalency (TEQ)/km, respectively. These results may infer some limited condition-specific differences in PCDD/F emissions, but these differences do not appear to have a significant effect on the HDDV emission factor. An older HDDV with mechanical fuel controls resulted in a single test value of 0.164 ng TEQ/km, significantly higher than all other results. Observed differences in emission factors, homologue profiles, and TEQ-related isomer patterns from this on-vehicle sampling and others' tunnel sampling suggest limitations in our present characterization of fleet PCDD/F emissions.     

Ultrafine PM emissions from natural gas,oxidation-catalyst diesel,and particle-trap diesel heavy-duty transit buses

This paper addresses how current technologies effective for reducing PM emissions of heavy-duty engines may affect the physical characteristics of the particles emitted. Three in-use transit bus configurations were compared in terms of submicron particle size distributions using simultaneous SMPS measurements under two dilution conditions, a minidiluter and the legislated constant volume sampler (CVS). The compressed natural gas (CNG)-fueled and diesel particulate filter (DPF)-equipped diesel configurations are two "green" alternatives to conventional diesel engines. The CNG bus in this study did not have an oxidation catalyst whereas the diesel configurations (with and without particulate filter) employed catalysts. The DPF was a continuously regenerating trap (CRT). Particle size distributions were collected between 6 and 237 nm using 2-minute SMPS scans during idle and 55 mph steady-state cruise operation. Average particle size distributions collected during idle operation of the diesel baseline bus operating on ultralow sulfur fuel showed evidence for nanoparticle growth under CVS dilution conditions relative to the minidiluter. The CRT effectively reduced both accumulation and nuclei mode concentrations by factors of 10-100 except under CVS dilution conditions where nuclei mode concentrations were measured during 55 mph steady-state cruise that exceeded baseline diesel concentrations. The CVS data suggest some variability in trap performance. The CNG bus had accumulation mode concentrations 10-100x lower than the diesel baseline but often displayed large nuclei modes, especially under CVS dilution conditions. Partly this may be explained by the lack of an oxidation catalyst on the CNG, but differences between the minidiluter and CVS size distributions suggest that dilution ratio, temperature-related wall interactions, and differences in tunnel background between the diluters contributed to creating nanoparticle concentrations that sometimes exceeded diesel baseline concentrations when driving under load. The results do not support use of CVS dilution methodology for ultrafine particle sampling, and, despite attention to collection of tunnel blanks in this study, results indicate that a protocol needs to be determined and prescribed for taking into account tunnel blank "emissions" to obtain meaningful comparisons between different technologies. Of critical importance is determining how temperature differences between tunnel blank and test cycle sampling compare in terms of background particle numbers. Total particle number concentrations for the minidiluter sampling point were not significantly different for the two alternative technologies when considering all the steady-cycle data collected. Concentrations ranged from 0.8 to 3 x 10(6) for the baseline bus operating on ultralow sulfur fuel, from 0.5 to 9 x 10(4) for the diesel bus equipped with the CRT filter, and from 1 to 8 x 10(4) particles/cc for the CNG bus.     

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 altitude on heavy-duty diesel truck on-road emissions

On-road measurements of carbon monoxide, hydrocarbons, and nitric oxide from 5772 heavy-duty diesel trucks at five locations in the United States and Europe show slightly increasing emissions with increasing altitude. The result for nitric oxide showed a statistically significant increase of 4.1 +/- 1 gNO/kg of fuel consumed/km increase in altitude. The increases for CO and HC were also statistically significant.     

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.     

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.     

Prediction of in-use emissions of heavy-duty diesel vehicles from engine testing

A model of a heavy-duty vehicle driveline with automatic transmission has been developed for estimating engine speed and load from vehicle speed. The model has been validated using emissions tests conducted on three diesel vehicles on a chassis dynamometer and then on the engines removed from the vehicles tested on an engine dynamometer. Nitrogen oxide (NOx) emissions were proportional to work done by the engine. For two of the engines, the NOx/horsepower(HP) ratio was the same on the engine and on the chassis dynamometer tests. For the third engine NOx/HP was significantly higher from the chassis test, possibly due to the use of dual engine maps. The engine certification test generated consistently less particulate matter emissions on a gram per brake horsepower-hour basis than the Heavy Duty Transient and Central Business District chassis cycles. A good linear correlation (r2 = 0.97 and 0.91) was found between rates of HP increase integrated over the test cycle and PM emissions for both the chassis and the engine tests for two of the vehicles. The model also shows how small changes in vehicle speeds can lead to a doubling of load on the engine. Additionally, the model showed that it is impossible to drive a vehicle cycle equivalent to the heavy-duty engine federal test procedure on these vehicles.