Particle size measurements of automotive diesel emissions

The automative diesel engine has long been acknowledged as being “dirtier” than the spark ignition engine and its particulate emissions may be carcinogenic. Possible solutions to the diesel emission problem are combustion modification or aftertreatment devices. Selection of candidate aftertreatment devices requires knowledge of the physical and chemical properties of the particles, including particle morphology, size distribution, mass concentration and emission rates in the exhaust gas stream. The study reported here represents the first of a series of experiments designed to characterize the exhaust emissions and test various aftertreatment devices. This paper deals only with the particulate characterization phase of the program. Results of size distribution, particle concentration and mass emission rate measurements for a 5.71 displacement Oldsmobile diesel engine are given for a variety of engine operating conditions.     

Mutagenic and carcinogenic potency of extracts of diesel and related environmental emissions: Study design, sample generation, collection, and preparation

A major diesel emissions research program has been initiated by the U.S. Environmental Protection Agency to assess the human health risk associated with increased use of diesel automobiles. This program is intended to establish the mutagenic and carcinogenic potency of complex organics associated with diesel particles as well as comparative particle-bound organics from other environmental emissions for which human epidemiological data are available. The mobile source samples selected for this study were collected from a heavy-duty diesel engine, a series of light-duty diesel passenger cars, and a gasoline catalyst automobile. The comparative source samples incorporated into the study were cigarette smoke condensate, coke oven emissions, roofing tar emissions, and benzo(a)pyrene. The samples were tested using three mutagenic assays and four carcinogenic assays as prescribed by a test matrix. This report describes the study design, particle generation, and sample collection and preparation. A brief summary of the bioassays is also included.     

Salmonella/microsome mutagenicity assays of exhaust from diesel and gasoline powered motor vehicles

Motor vehicle exhaust from prechamber injection diesel and gasoline powered passenger cars, sampled during US FTP 1973 test cycles and comprising both particulate matter and compounds condensable at ambient temperature, has been assayed for mutagenicity in the Salmonella/microsome test. Mutagenic components were to a large extent active in the absence of the mammalian microsomal preparation. The mutagenicity of both particulate matter and condensate from diesel exhaust and condensate from gasoline exhaust was decreased in the presence of the microsomal preparation whereas the mutagenicity of particulate matter from gasoline exhaust was enhanced by microsomal activation. A comparison between the investigated diesel and gasoline exhaust samples shows that the mutagenic effect in the Salmonella test of the diesel exhaust is more than ten times higher than that of the gasoline exhaust. Fractionation with respect to polarity indicates that the mutagenic components mainly are distributed in neutral aliphatic, aromatic, and oxygenated fractions. Tests for mutagenic monofunctional nitroarenes by an anaerobic assay indicate that such compounds at most are marginally present in the exhaust samples as compared with their presence in airborne particulate matter collected in an urban environment.     

Deposition and biological availability of diesel particles and their associated mutagenic chemicals

To estimate the human health risk of inhaled diesel particles, it is necessary to know their deposition and retention in the respiratory tract and the rate of dissociation of mutagenic compounds associated with the particles. The deposition of a chain aggregate aerosol of ⁶⁷Ga₂O₃ with size and shape characteristics similar to diesel exhaust particles has been evaluated using Beagle dogs. Approximately one-third of the inhaled activity is deposited in the respiratory tract with most of the particles deposited in the lung. The mutagenic activity present in dichloromethane, dog serum, dog lung lavage fluid, saline, dipalmitoyl lecithin (DPL) and albumin following incubation of these fluids with diesel exhaust particles was determined in the Ames Salmonella system. As observed by other investigators, large quantities of mutagenic activity were removed by dichloromethane. A very small amount of mutagenic activity was removed by the serum and lavage fluid over a 3-day incubation period. No activity was detected following elution with the other solvents. The finding that minimal mutagenic activity could be demonstrated in the biological media following incubation with diesel exhaust particles may be due to a lack of removal of mutagens from the particles or an inactivation of removed mutagens by protein binding or other processes.     

Performance of a twin cylinder diesel engine in dual fuel mode using woody biomass producer gas

Due to energy crisis and shortage of fossil fuel, there is a growing interest in alternative fuel for internal combustion engine. Producer gas presents a very promising alternative fuel to diesel since it is a renewable and clean burning fuel having properties similar to that of diesel. In this study, a twin cylinder dual fuel diesel engine is experimentally optimized for maximum diesel saving and lower emissions, without any undue vibration of engine using woody biomass producer gas. The test is carried out to study the performance and emission parameters of the engine in diesel mode and dual fuel mode at different gas flow rates under different load conditions. The study reveals that maximum diesel savings is found to be 83% at optimum gas flow rate and 8 kW load. Carbon monoxide, hydrocarbon and carbon dioxide emissions in dual fuel mode were higher compared with diesel mode at all test ranges. However, the main pollutants, such as nitrogen oxide and smoke, decrease substantially in the dual fuel mode compared with the diesel mode. Lower brake thermal efficiency and higher brake-specific energy consumption as well as exhaust gas temperature are observed in dual fuel mode compared with diesel mode.     

Enhanced susceptibility to infection in mice after exposure to dilute exhaust from light duty diesel engines

A series of experiments was conducted in which groups of mice were first exposed for various durations to diluted exhaust from light duty diesel engines and then briefly to an infectious aerosol generated by nebulizing cultures of a bacterial pathogen (Streptococcus). Typically, postinfection mortality was significantly greater in groups exposed to exhaust than in their corresponding control groups exposed to purified air only. Data of recent diesel and of past diesel- and catalyst-treated gasoline engine exhaust experiments suggest a somewhat greater excess mortality from (enhanced susceptibility to) bacterial infection in mice exposed to diesel exhaust than in those exposed to catalytic gasoline exhaust. Limited data on acute tests of NO₂ and acrolein vapor alone suggest that the infectivity-enhancing effect of diesel exhaust could be accounted for in large part by these components. Exposures to diesel exhaust, NO₂, or acrolein did not enhance the mortality response to a viral pathogen (A/PR8-34).     

Facilities for diesel exhaust studies

It is the major intent of this report to examine the animal inhalation facilities at the EPA Health Effects Research Laboratory in Cincinnati, Ohio, associated with the exposure to the exhaust of diesel-powered equipment. The facility serves as a center for toxicologic evaluation, in relevant animal models, of potentially hazardous environmental pollutants from diesel engine exhaust. Briefly, the entire engine exhaust is mixed with filtered and conditioned air in a dilution tube. That diluted exhaust enters a large volume mixing chamber and a portion passes through dynamic flow irradiation chambers (to simulate sunlight) and is then conducted to animal exposure chambers. The system provides nonirradiated exhaust in the same concentration (directly from the mixing chamber) and also filtered, conditioned ambient air for control animal exposure. The major physical components of the diesel emission system include: air purifiers, animal exposure chambers, engine-dynamometers, irradiation chambers, monitoring instrumentation and data acquisition systems.     

Thermal barrier coated diesel engine running on biodiesel: a review

Thermal barrier coated diesel engine, also known as low heat rejection (LHR) engine have offered the promise of reducing heat rejection to the engine coolant and increase the combustion temperature which results in increase of thermal efficiency, decrease of fuel consumption and emission rate of the engine. Biodiesel derived from the vegetable oils are a promising alternative fuel for diesel fuel. The viscosity of vegetable oil after transestrification is still higher than that of diesel fuel. The various researchers have reported that the energy of the biodiesel could be released more efficiently with the concept of LHR engine. In the case of LHR engine running on different biodiesel blends, almost all experimental studies has predicted improved performance. This paper analyses and discussed the operating conditions under which the experimental studies are carried out and the factors which affect thermal efficiency and exhaust emissions in LHR engine.     

Performance studies of a low heat rejection engine operated on non-volatile vegetable oils with exhaust gas recirculation

During recent decades, considerable effort has been expended world-wide to reduce dependency on petroleum fuels for power generation and transportation through the search for suitable alternative fuels that are environmentally friendly. In this respect, vegetable oils are a promising alternative to diesel fuel. However, the high viscosity, poor volatility and cold flow characteristics of vegetable oils can cause some problems such as injector coking, severe engine deposits, filter gumming and piston ring sticking and thickening of lubrication from long-term use in diesel engines. These problems can be eliminated or minimised by transesterification of the vegetable oils to form monoesters. Although transesterification improves the fuel properties of vegetable oil, the viscosity and volatility of biodiesel are still worse than those of petroleum diesel fuel. The performance of a diesel engine with such biodiesel operation can be improved further with the concept of the low heat rejection (LHR) engine. In the LHR engine, combustion surfaces on the pistons, cylinder walls and valves can be coated with ceramic materials. The objective of this study was to apply the LHR engine concept for improving engine performance when either honge biodiesel, known as honge oil methyl ester (HOME), or neem biodiesel, known as neem oil methyl ester (NOME) oils was used as an alternative fuel. For this purpose, experiments were conducted on a single cylinder, four-stroke, direct injection, water-cooled compression ignition engine using diesel, HOME and NOME oils at different injection timings of 19, 23 and 27° before top dead centre (BTDC) with and without the induction of exhaust gas recirculation (EGR). The percentage of EGR was varied from 5 to 20% in steps of 5%. The results showed that specific fuel consumption and brake thermal efficiency were improved for both of the biodiesel fuels in the LHR engine. An EGR of 10% resulted in better performance with trade-off between oxides of nitrogen and hydrocarbons/carbon monoxide emissions and hence 10% EGR is taken as the best of the range from 5 to 20%. However, readings with other EGR ratios are not reported.     

Genotoxicity of syrian hamster lung cells treated in vivo with diesel exhaust particulates

Polycyclic aromatic hydrocarbons extracted and concentrated from diesel exhaust particulates have been shown to be mutagenic and carcinogenic, but attempts to induce pulmonary tumors through chronic inhalation of diesel exhaust by experimental animals have failed. We have attempted to resolve this incongruity by measuring chromosomal damage in lung tissue of chronically exposed hamsters, using the highly sensitive test for genotoxic chemical agents, sister chromatid exchange (SCE) analysis. To determine the degree of responsiveness of the test system to both diesel exhaust particulates and benzo(a)pyrene (BaP), these agents were instilled intratracheally into anesthetized hamsters as suspensions in 0.25 ml volumes of Hank's balanced salt solution (HBSS). Lung tissues from these animals were subsequently cultured in vitro and chromosomes from the resulting cell divisions were scored for exchanges of chromatin between sister chromatids. Control animals, treated weekly with 0.25 ml of BSS for 10 weeks, showed an average value of 12 SCE's per cell, while animals treated weekly with 200 ng BaP over a 10-week period showed an average of 17 SCE's per cell. HBSS, given as a single treatment, also produced an average of 12 SCE's per cell in control animals, but animals treated with a single instillation of 12.5 μg BaP showed an average SCE value of 19. These data confirmed that the procarcinogen BaP can be metabolically activated by lung cells in vivo and also demonstrated the efficacy of using this technical approach to study the effect of chemical mutagens that enter the lungs. Diesel exhaust particulates, administered in a range from 0 to 20 mg per hamster over a 24 h exposure period, produced a linear SCE dose-response ranging from 12 to 26 SCE's per metaphase. This curve suggested that a concentration of 3 mg of diesel particulates per hamster would not produce a statistically significant increase in SCE's above control values. One group of 8 hamsters, chronically exposed to diesel exhaust particulates for 3 months showed an average of 12 SCE's per cell. This was equivalent to a set of 5 control animals which also showed an average of 12 SCE's per cell. Although the scope of this study was limited, the data demonstrated that diesel exhaust particulates can induce genotoxic damage but a 3-month exposure to 6 mg/m³ of diesel exhaust particulates was insufficient to produce measurable mutagenic changes in lung cells. This negative response is consistent with the results from other studies in which similar exposures failed to produce pulmonary tumors.     

Diesel particulate extracts in bacterial test systems

The Ames bacterial mutagenicity test system was used to evaluate parameters which may affect the mutagenic activity of diesel particulate extracts. The optimal extraction conditions, extractability of mutagens by simulated biological fluids and the effect of collection method were investigated. The role of solvent was examined by extracting diesel particles with methanol, acetone, cyclohexane, ethyl acetate, n-hexane, dichloromethane, benzene and a benzene-ethanol mixture. Of these, the dichloromethane extract exhibited the highest activity in the Ames test, although methanol yielded the largest extractable mass. Diesel particles were also extracted by dimethyl sulfoxide (DMSO) and four other simulated biological fluids for 48 h at 25, 37, and 45°C to study the effects of temperature. The mutagenic activity of the DMSO extract began to decline at temperatures higher than 37°C after 8 h of incubation. Fetal calf serum was the only simulated biological fluid which eluted mutagenic activity from the particles. No activity was detected in the 0.5% bovine serum albumin, simulated lung surfactant and saline extracts. Diesel particles collected by electrostatic precipitation (ESP) and filtration were studied. The mutagenic activities of both extracts were comparable when expressed as revertants per mg of particle. After the extracts were separated into nine fractions by a solvent partitioning scheme, the majority of the activity was found in the neutral-nonpolar II, neutral polar, strong acid and weak acid fractions. The acid salt fraction from the ESP sample was inactive. These results demonstrate that differences in the extraction conditions can result in differences in the mutagenic activity of diesel particulate extract. Since the mutagens in the extracts are not readily extractable by simulated biological fluids, the question of bioavailability of mutagens in diesel particles must be considered in the final assessment of their potential effects in biological systems and organisms.     

Mutagenic and carcinogenic potency of extracts from diesel related environmental emissions: Simultaneous morphological transformation and mutagenesis in BALB/c 3t3 cells

Particulate extracts from six different environmental emission sources were assayed for genotoxic activity in mouse BALB/c 3T3 clone A31-1 cells. All compounds were tested simultaneously for both transforming and mutagenic (induction of ouabain-resistance) potential with and without exogenous metabolic activation in the form of a 9000 × g postmitochondrial hepatic supernatant fraction from Aroclor-1254 induced Fischer 344 rats. Dichloromethane particulate extracts from the exhaust of two light duty diesel engines (Oldsmobile and Nissan), one heavy duty diesel engine (Caterpillar) and one late model gasoline engine (Mustang II) were assayed in an identical manner to particulate extracts from the emissions of a roofing tar pot and a coke oven. No clear dose-dependent responses were observed, but several of the samples showed significant transforming and mutagenic activity. A qualitative ranking system showed the activity of these particulate extracts for either mutagenesis or transformation was: coke oven = Mustang II gasoline engine > Nissan diesel engine > roofing tar. Particulate extracts from the Oldsmobile diesel engine and the Caterpillar diesel engine showed essentially no activity.     

Physical characterization of diesel exhaust particles in exposure chambers

Since the deposition of particulate in the respiratory system is strongly influenced by particle size, a correct assessment of this parameter is important for any inhalation experiment studying the potential health effects of air pollutants. Measuring the distribution of particles according to their aerodynamic diameter and mechanical mobility diameter is crucial in analyzing the deposition of submicron particles in the lower respiratory system. Cascade impactor measurements of diluted diesel exhaust in 12.6 m³ animal exposure chambers in the GMR Biomedical Science Department showed that the mass median aerodynamic diameter of the aerosol was 0.2 μm with 88% of the mass in particles smaller than 1 μm. Diffusion battery measurements showed that the mass median mechanical mobility diameter was about 0.11 μm. Transmission electron micrographs of particles deposited on chamber surfaces revealed both agglomerates and nearly spherical particles. The particles in these chambers are similar in size and shape to diesel particles described elsewhere. The flux of diesel particles to food surfaces was measured. Calculations of the expected daily dose by inhalation and by feeding showed that the “worst case” dose by feeding was only about one-tenth the dose by breathing.     

Mutagenic and carcinogenic potency of extracts of diesel and related environmental emissions: Summary and discussion of the results

The proposed conversion from gasoline powered automobiles to diesel powered vehicels has prompted the Environmental Protection Agency to evaluate the potential health effects associated with exposure to diesel emissions. At present, there is no direct epidemiological link between this exposure and human health. Therefore, a research program was constructed to compare the health effects associated with diesel emissions with those from other emission sources for which epidemiological information was available. The emission sources chosen were cigarette smoke, roofing tar, and coke oven. An additional comparative emission source which was a gasoline catalyst engine. Respirable particles from a variety of combustion sources have the potential of being carcinogenic and mutagenic. The objective of these studies was to determine the relative biological activity of the organic material adsorbed on these particles in both in vitro mutagenesis and in vitro and in vivo bioassays. The organic extracts from the following series of emission sources were quantitatively bioassayed in a matrix of tests for their carcinogenic and mutagenic activity: (1) a light-duty Oldsmobile diesel 350 engine; (2) a heavy-duty Caterpillar diesel engine; (3) a light-duty Nissan engine; (4) a Volkswagen Rabbit diesel engine; (5) cigarette smoke; (6) roofing tar; (7) coke oven; and (8) a gasoline catalyst Mustang. The test matrix consisted of the following bioassay: reverse mutation in Salmonella typhimurium; mitotic recombination in Saccharomyces cerevisiae; DNA damage in Syrian hamster embryo cells (SHE); sister chromatid exchange in CHO cells; gene mutation in L5178Y mouse lymphoma cells, Balb/c 3T3 mouse embryo fibroblasts and CHO cells; viral enhancement of SHE cells; oncogenic transformation in Balb/c 3T3 cells; and skin tumor initiation in SENCAR and C57 black mice. The results of this test matrix are discussed.     

Control strategies for particulate emissions from vehicular diesel exhaust

The advantages and disadvantages of several possible control strategies for particulate emissions from vehicular diesel exhaust are discussed. The evaluation of the potential usefulness of the various control strategies is based on available data concerning the mass loading and particle size distribution and on anticipated control standards. Several studies have been made on devices for removing particulate emissions from vehicular diesel exhaust. These studies, which include the techniques of filtration, wet scrubbers, and electrostatic precipitation, are summarized. A comparison of the various control devices is made based on such factors as size, efficiency, and maintenance requirements.     

Metaphase analysis, micronuclei assay, and urinary mutagenicity assay of mice exposed to diesel emissions

Female Swiss mice were exposed 8 h/day to diesel exhaust for 1, 3, and 7 weeks. Urine was collected overnight for 4 days prior to sacrifice while the mice continued to be exposed for eight hours during the day. The presence of mutagens was determined by the Ames Salmonella test. One hour prior to sacrifice each mouse received 1 mg/kg colcemide. After sacrifice, the marrow from each femur was obtained. The marrow from one femur was used to prepare slides for metaphase analysis and the other for micronuclei assay. Other mice received IP 50 mg/kg cyclophosphamide 24 h prior to sacrifice or 1 μmole/kg benzo(a)pyrene in each of four daily doses prior to sacrifice and served as positive controls. The Ames Salmonella assay of the unconcentrated urine after 1, 3, and 7 weeks and concentrated urine after 7 weeks exposure to diesel exhaust did not significantly vary from clean air controls. In the micronucleus test, and metaphase analysis, cyclophosphamide produced a strong positive response and the 7 week diesel exposure was not different from clean air controls.     

Evaluation of techniques used in the preparation of diesel extract samples for mutagenicity studies

Diesel exhaust particles were used to compare methods and techniques used in the preparation of particulate matter for microbial mutagenesis testing. Investigated in this study were extraction, concentration, and solvent exchange methodologies as they affected recovery of mutagenic material from diesel samples using a Salmonella typhimurium plate incorporation assay. Solvent removal methods applicable for use in determining the mass concentration of extracts were also evaluated. Results indicated that particle samples Soxhlet extracted with dichloromethane yielded higher levels of mutagenic activity than did comparative samples utilizing sonication. No difference was seen between rotary evaporation or Kuderna-Danish macro concentration of extracts to volumes > 50 mL. In comparison of micro concentration techniques to volumes < 10 mL, vortex evaporation was found to be more efficient than a modified micro Kuderna-Danish method in recovery of mass and mutagenicity. Solvent exchanged samples were found to yield higher recoveries of mutagenic activity than samples taken to dryness and then reconstituted in the bioassay solvent. A dry mass weighing procedure utilizing desiccation was found to be more acceptable than either the use of an infrared heat lamp or nitrogen blowdown for solvent removal.     

Studies on the use of low-volatile non-edible oils in a thermal barrier-coated diesel engine

Owing to the ever-increasing vehicle population, the consumption of diesel fuel in the transportation, agricultural and industrial sectors has increased at an alarming rate. This has led to rapid fossil fuel depletion, ozone depletion and environmental degradation, which have become a serious concern. Search for alternative renewable and clean energy fuel sources to mitigate the emissions of greenhouse gases is continuing, and attempts to find different techniques for efficient utilization of these fuels are also undertaken. Biodiesel being an oxygenated fuel obtained from vegetable oils has received greater attention over the years as a promising alternative to diesel fuel. However, vegetable oils exhibit high viscosity, poor volatility and poor cold-flow characteristics. These characteristics can cause the following problems in the engine when run for a longer duration: injector coking, severe engine deposits, filter gumming, piston ring sticking and thickening of lubrication. These problems can be eliminated or minimized by adopting suitable fuel processing techniques to obtain biodiesels from vegetable oils. The fuel processing techniques vary widely, which include transesterification, supercritical methanolysis, ultrasonic and continuous microwave-assisted transesterification methods. In the present study, the transesterification method is effectively used to obtain biodiesels from non-edible oils of honne and cotton seed. The biodiesels obtained from these oils were used in the unmodified diesel engine to check their feasibility as diesel engine alternatives. Different thermal barrier coatings (TBCs) were applied on the piston, cylinder head, and inlet and exhaust valve surfaces of the diesel engine in order to make it a fully adiabatic engine. The engine with such TBCs is called a low heat rejection engine. For the present study, the TBC of partially stabilized zirconia (PSZ) and aluminium oxide (Al₂O₃) were selected. Finally, the performance of the diesel engine fuelled with different biodiesels in both conventional and thermal barrier-coated modes was compared. The thermal barrier-coated engine with the PSZ version showed better performance with increased nitric oxide emissions when compared with the Al₂O₃ coating.     

Electron paramagnetic resonance spectrometry of diesel particulate matter

Electron paramagnetic resonance (EPR) spectrometry has been used to study diesel particulate matter. The EPR signals for a graphitized carbon black and particles collected from two different diesel engines have been compared. Variations in the line widths and signal intensities due to various chemical and physical pretreatments of the particles were observed. The EPR signals for the diesel particulates were shown to be sensitive to oxygen, nitric oxide, nitrogen dioxide, and ultraviolet and visible radiation. These results suggest that EPR may be a convenient means for characterizing particles from different sources or for demonstrating particle reactivities. The demonstrated photochemical reactivities of the airborne particles have significant environmental health implications.     

Mutagenic and carcinogenic potency of diesel and related environmental emissions: Salmonella bioassay

Due to the expected increase in the percentage of diesel vehicles in the United States, the Environmental Protection Agency must evaluate the health effects associated with exposure to diesel emissions. Respirable particles from a variety of combustion sources have the potential of being carcinogenic and mutagenic. The objective of these studies was to determine the relative biological activity of the organic material adsorbed on these particles in in vitro mutagenesis bioassays. The organic extracts from the following series of emission sources were bioassayed in the Salmonella assay for mutagenic activity: (1) a light-duty Oldsmobile diesel 350 engine; (2) a heavy-duty Caterpillar diesel engine; (3) a light-duty Nissan engine; (4) a Volkswagen Rabbit diesel engine; (5) cigarette smoke; (6) roofing tar; (7) coke oven; and (8) a gasoline catalyst Mustang. This paper provides a comparison of these sources within the Salmonella bioassay and also demonstrates how bacterial systems can be used as a quality assurance measure in in vivo testing.