Combustion of diesel fuel from a toxicological perspective

I. Origin of incomplete combustion products
  • P. T. J. Scheepers
  • R. P. Bos
Review Articles


Since the use of diesel engines is still increasing, the contribution of their incomplete combustion products to air pollution is becoming ever more important. The presence of irritating and genotoxic substances in both the gas phase and the particulate phase constituents is considered to have significant health implications. The quantity of soot particles and the particle-associated organics emitted from the tail pipe of a diesel-powered vehicle depend primarily on the engine type and combustion conditions but also on fuel properties. The quantity of soot particles in the emissions is determined by the balance between the rate of formation and subsequent oxidation. Organics are adsorbed onto carbon cores in the cylinder, in the exhaust system, in the atmosphere and even on the filter during sample collection. Diesel fuel contains polycyclic aromatic hydrocarbons (PAHs) and some alkyl derivatives. Both groups of compounds may survive the combustion process. PAHs are formed by the combustion of crankcase oil or may be resuspended from engine and/or exhaust deposits. The conversion of parent PAHs to oxygenated and nitrated PAHs in the combustion chamber or in the exhaust system is related to the vast amount of excess combustion air that is supplied to the engine and the high combustion temperature. Whether the occurrence of these derivatives is characteristic for the composition of diesel engine exhaust remains to be ascertained. After the emission of the particles, their properties may change because of atmospheric processes such as aging and resuspension. The particle-associated organics may also be subject to (photo)chemical conversions or the components may change during sampling and analysis. Measurement of emissions of incomplete combustion products as determined on a chassis dynamometer provides knowledge of the chemical composition of the particle-associated organics. This knowledge is useful as a basis for a toxicological evaluation of the health hazards of diesel engine emissions.

Key words

Diesel exhaust Combustion Soot particles Particle-associated organics Polycyclic aromatic hydrocarbons 


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  1. Abbass MK, Williams PT, Andrews GE, Bartle KD (1987) The aging of lubricating oil, the influence of unburnt fuel and particulate SOF contamination. Society of Automotive Engineers paper no. 872085Google Scholar
  2. Abbass MK, Andrews GE, Williams PT, Bartle KD, Davies IL, Tanui LK (1988) Diesel particulate emissions: pyrosynthesis of PAH from hexadecane. Society of Automotive Engineers paper no. 880345Google Scholar
  3. Abdelnasser M, Hyland M, Jespersen ND (1986) Synthesis of mutagenic compounds in crankcase oils. Environ Sci Technol 20:145–149Google Scholar
  4. Amann CA, Stivender DL, Plee SL, MacDonald JS (1980) Some rudiments of diesel particulate emissions. Society of Automotive Engineers paper no. 800251Google Scholar
  5. Aoyagi Y, Kamimoto T, Matsui Y, Matsuoka S (1980) A gas sampling study on the formation processes of soot and NO in a DI diesel engine. Society of Automotive Engineers paper no. 800254Google Scholar
  6. Barbella R, Bertoli C, Ciajolo A, D'Anna A (1988) Soot and unburnt liquid hydrocarbon emissions from diesel engines. Combust Sci Technol 59:183–198Google Scholar
  7. Behymer TD, Hites RA (1985) Photolysis of polycyclic aromatic hydrocarbons adsorbed on simulated atmospheric particulates. Environ Sci Technol 19:1004–1006Google Scholar
  8. Braddock JN, Perry Jr NK (1986) Gaseous and particulate emissions from gasoline- and diesel-powered heavy duty trucks. Society of Automotive Engineers paper no. 860617Google Scholar
  9. Bradow RL (1982) Diesel particle and organic emissions: engine simulation, sampling, and artifacts. In: Lewtas J (ed) Carcinogenic and mutagenic effects of diesel engine exhaust. Elsevier Science, Amsterdam, pp 33–50Google Scholar
  10. Choudhury DR (1982) Characterization of polycyclic ketones and quinones in diesel emission particulates by gas chromatography/mass spectrometry. Environ Sci Technol 16:102–106Google Scholar
  11. Clark CR, Henderson TR, Rover RE, Brooks AL, McClellan RO, Marschall WF, Naman TM (1982) Mutagenicity of diesel exhaust particle extracts: influence of fuel composition in two diesel engines. Fundam Appl Toxicol 2:38–43Google Scholar
  12. CONCAWE (1987) Diesel fuel quality and its relationship with emissions from diesel engines. CONCAWE, The HagueGoogle Scholar
  13. Cuthbertson RD, Shore PR, Sundström L, Heden PO (1987) Direct analysis of diesel particulate-bound hydrocarbons by gas chromatography with solid sample injection. Society of Automotive Engineers paper no. 870626Google Scholar
  14. Dolan DF, Kittelson DB, Pui DYH (1980) Diesel exhaust particle size distribution measurement techniques. Society of Automotive Engineers paper no. 800187Google Scholar
  15. Draper WM, Phillips J, Zeller HW (1988) Impact of a barium fuel additive on the mutagenicity and polycyclic aromatic hydrocarbon content of diesel exhaust particulate emissions. Society of Automotive Engineers paper no. 881651Google Scholar
  16. Du C-J, Kittelson DB, Zweidinger RB (1984) Measurement of polycyclic aromatic compounds in the cylinder of an operating diesel engine. Society of Automotive Engineers paper no 840364Google Scholar
  17. Egebäck KE, Bertilsson BM (1983) Chemical and biological characterization of exhaust emissions from vehicles fueled with gasoline, alcohol, LPG and diesel. National Swedish Protection Board, report no. snv pm 1635Google Scholar
  18. Encyclopædia Brittanica (1984) The new Encyclopædia Brittanica, 15th edn. Encyclopædia Brittanica, ChicagoGoogle Scholar
  19. Grimmer G (1979) Sources and occurrence of polycyclic aromatic hydrocarbons. In: Egan H (ed) Environmental carcinogens. Selected methods of analysis, vol 3. Analysis of polycyclic aromatic hydrocarbons in environmental samples. IARC Publ no 29. IARC, Lyon, pp 31–125Google Scholar
  20. Grimmer G, Hildebrandt A (1975) Investigations on the carcinogenic burden by air pollution in man. XIII. Assessment of the contribution of passenger cars to air pollution by carcinogenic polycyclic hydrocarbons. Zentralbl Bakt Hyg 161:104–124Google Scholar
  21. Groblicky PJ, Begeman CR (1979) Particle size variation in diesel exhaust. Society of Automotive Engineers paper no. 790421Google Scholar
  22. Hampton CH, Pierson WR, Schuetzle D, Harvey TM (1983) Hydrocarbon gases emitted from vehicles on the road. 2. Determination of emission rates from diesel and spark-ignition vehicles. Environ Sci Technol 17:699–708Google Scholar
  23. Hare CT (1986) The effects of diesel fuel properties on particulate emissions. In: Lee SD, Schneider T, Grant LD, Verkerk PJ (eds) Aerosols. Lewis, Chelsea, pp 501:514Google Scholar
  24. Hare CT, Baines TM (1979) Characteristics of particulate and gaseous emissions from two diesel automobiles as functions of fuel and driving cycle. Society of Automotive Engineers paper no. 790424Google Scholar
  25. Hare CT, Springer KJ, Bradow RL (1976) Fuel and additive effects on diesel particulate development and demonstration of methodology. Society of Automotive Engineers paper no. 760130Google Scholar
  26. Hayano S, Jang-Ho L, Furuya K et al. (1985) Formation of hazardous substances and mutagenicity of PAH produced during the combustion process in a diesel engine. Atmos Environ 19:1009–1015Google Scholar
  27. Henderson TR, Royer RE, Clark CR, Harvey TM, Hunt DF (1982) MS/MS analysis of diesel emissions and fuels treated with NO2. J Appl Toxicol 2:231–237Google Scholar
  28. Henderson TR, Sun JD, Li AP et al. (1984) GC/MS and MS/MS studies of diesel exhaust mutagenicity and emissions from chemically defined fuels. Environ Sci Technol 18:428–434Google Scholar
  29. Herr JD, Dukovich M, Lestz SS, Yergey JA, Risby TH, Tejada SB (1982) The role of nitrogen in the observed direct microbial mutagenic activity for diesel engine combustion in a single-cylinder DI engine. Society of Automotive Engineers paper no 820467Google Scholar
  30. Hisamatsu Y, Nishimura T, Tanabe K, Matsushita H (1986) Mutagenicity of the photochemical reaction products of pyrene with nitrogen dioxide. Mutat Res 172:19–27Google Scholar
  31. Huisingh J, Bradow R, Jungers R et al. (1987) Application of bioassay to the characterization of diesel particle emissions. In: Waters MD, Nesnow S, Huisingh JL, Sandhu SS, Claxton L (eds) Application of short-term bioassays in the fractionation and analysis of complex environmental mixtures. Plenum, New York, pp 382–418Google Scholar
  32. IARC (1989) IARC monographs on the evaluation of carcinogenic risk to humans. Diesel and gasoline engine exhausts and some nitroarenes. IARC, LyonGoogle Scholar
  33. Iida N, Suzuki Y, Sato GT, Sawada T (1986) Effects of intake oxygen concentration on the characteristics of particulate emissions from a D.I. diesel engine. Society of Automotive Engineers paper no. 861233Google Scholar
  34. Israel GW, Zierock K-H, Mollerhauer K (1982) Größenverteilung und chemische Zusammensetzung der Partikelemissionen verschiedener Dieselmotoren. VDI-Berichte 429:279–286Google Scholar
  35. Jensen TE, Hites RA (1983) Aromatic diesel emissions as a function of engine conditions. Anal Chem 55:594–599Google Scholar
  36. Jensen TE, Richert JFO, Cleary AC, LaCouse DL, Gorse Jr RA (1986) 1-Nitropyrene in used diesel engine oil. J Am Pollut Control Assoc 26:1255–1256Google Scholar
  37. Kamimoto T, Aoyagi Y, Matsui Y, Mastuoka S (1980) The effects of some engine variables on measured rates of air entrainment and heat release in a DI engine. Society of Automotive Engineers paper no. 800253Google Scholar
  38. Lach G, Winckler J (1988) Specific problems of sampling and measuring diesel exhaust emissions. Society of Automotive Engineer paper no. 881763Google Scholar
  39. Lehmann E, Rentel K-H, Allescher W, Homann R (1989) Gefährliche Arbeitsstoffe GA33: Messung der beruflichen Exposition gegenüber Dieselabgas. Bundesanstalt für Arbeitsschutz, DortmundGoogle Scholar
  40. Li AP, Royer RE, Brooks AL, McClellan RO (1982) Cytotoxicity of diesel exhaust particle extracts — a comparison among five diesel passenger cars of different manufacturers. Toxicology 24:1–8Google Scholar
  41. Lies K-H (1989) Unregulated motor vehicle exhaust gas components. Volkswagen AG, Wolfsburg MacDonald JS, Plee SL, D'Arcy JB, Schreck RM (1980) Experimental measurements of the independent effects of dilution ratio and filter temperature on diesel exhaust particulate samples. Society of Automotive Engineers paper no. 800185Google Scholar
  42. Manabe Y, Konouchi T, Wakisaka T, Tahra I, Ohnishi Y (1984) Mutagenic 1-nitropyrene in wastewater from oil-water separating tanks of gasoline stations and in used crankcase oil. Environ Mutagen 6:669–681Google Scholar
  43. Mayer WJ, Lechman DC, Hilden DL (1980) The contribution of engine oil to diesel exhaust particulate emissions, Society of Automotive Engineers paper no. 800256Google Scholar
  44. Meyer JP, Grimmer G (1974) Einflüsse PAH-haltiger and PAH-freier Kraftstoffe auf die Emission von polycyclischen aromatischen Kohlenwasserstoffen eines Kraftfahrzeugs mit Ottomotor im Europa-test. DGMK-Forschungsbericht 4547, II, HamburgGoogle Scholar
  45. Moriske HJ, Rüden H (1988) Polare neutrale organische Verbindungen (POCN) im Stadtaerosol. Mitteilung: Vergleichende Untersuchungen von Emissions- und Immissionsstäuben in Berlin (West) Zentralbl Bakt Hyg 185:452–468Google Scholar
  46. Murayama T, Miyamoto N, Chikahisa T, Yamane K (1986) Effects of combustion and injection systems on unburnt HC and particulate emissions from a DI diesel engine. Society of Automotive Engineers paper no. 861232Google Scholar
  47. Nelson PF (1989) Combustion-generated polycyclic aromatic hydrocarbons in diesel exhaust emissions. Fuel 68:283–286Google Scholar
  48. Olah GA, Narang SC, Olah JA (1981) Nitration of naphthalene and remarks on the mechanism of electrophilic aromatic nitration. Proc Natl Acad Sci USA 78:3298–3300Google Scholar
  49. Pipho MJ, Ambs JL, Kittelson DB (1986) In-cylinder measurements of particulate formation in an indirect injection diesel engine. Society of Automotive Engineers paper no. 860024Google Scholar
  50. Plee SL, MacDonald JS (1980) Some mechanisms affecting the mass of diesel exhaust particulate collected following a dilution process. Society of Automotive Engineers paper no. 800186Google Scholar
  51. Rosenkranz HS, Mermelstein R (1985) The genotoxicity, metabolism and carcinogenicity of nitrated polycyclic aromatic hydrocarbons. J Environ Sci Health 3:221–272Google Scholar
  52. Ryan TW, Storment JO, Wright BR, Waytulonis R (1981) The effects of fuel properties and composition on diesel engine exhaust emissions — a review. Society of Automotive Engineers paper no. 810953Google Scholar
  53. Saito T, Tolureo N, Katoh T (1982) Analysis of factors affecting the formation of major mutagenic substances in diesel particulate extracts. Society of Automotive Engineers paper no. 821244Google Scholar
  54. Schuetzle D (1983) Sampling of vehicle emissions for chemical analysis and biological testing. Environ Health Perspect 47:65–80Google Scholar
  55. Schuetzle D, Frazier JA (1986) Factors influencing the emission of vapor and particulate phase components from diesel engines. In: Ishinishi N, Koizumi A, McClellan RO, Stöber W (eds) Carcinogenic and mutagenic effects of diesel engine exhaust. Elsevier Science, Amsterdam, pp 41–63Google Scholar
  56. Schuetzle D, Skewes LM, Fisher GE, Levine SP, Gorse Jr RA (1981) Determination of sulfates in diesel particulates. Anal Chem 53:837–840Google Scholar
  57. Serageldin MA (1981) Soot formation in small flames. Society of Automotive Engineers paper no. 811197Google Scholar
  58. Stärk G, Stauff J, Miltenburger HG, Stumm-Fischer I (1985) Photodecomposition of 1-nitropyrene and other direct-acting mutagens extracted from diesel exhaust particulates. Mutat Res 155:27–33Google Scholar
  59. Steenlage R, Rijkeboer RC (1985) Oriënterende metingen van de emissie van schadelijke en hinderlijke organische verbindingen afkomstig van gemotoriseerd wegverkeer. TNO, Delft, Report no. G 1115Google Scholar
  60. Stenberg U, Alsberg T, Westerholm W (1983) Emission of carcinogenic components with automobile exhausts. Environ Health Perspect 47:53–56Google Scholar
  61. Truex TJ, Pierson WR, McKee DE (1980) Sulfate in diesel exhaust. J Environ Sci Technol 14:1118–1121Google Scholar
  62. Uyehara OA (1980) Effect of burning zone A/F, fuel H/C on soot formation and thermal efficiency. Society of Automotive Engineers paper no. 800093Google Scholar
  63. Van Beckhoven LC (1991) Effects of fuel properties on diesel engine emissions — a review of information available to EEC-MVEG group. Society of Automotive Engineers paper no. 910608Google Scholar
  64. Wade WR (1980) Light-duty diesel NOx-HC-particulate trade-off studies. Society of Automotive Engineers paper no. 800335Google Scholar
  65. Wade WR, Jones CM (1984) Current and future light duty diesel engines and their fuels. Society of Automotive Engineers paper no. 840105Google Scholar
  66. Weidmann K, Menrad H, Reders K, Hutcheson RC (1988) Diesel fuel quality effects on exhaust emissions. Society of Automotive Engineers paper no. 881649Google Scholar
  67. Westerholm R, Alsber T, Strandell M et al. (1986) Chemical analysis and biological testing of emissions from a heavy duty diesel truck with and without two different particulate traps. Society of Automotive Engineers paper no. 860014Google Scholar
  68. Williams PT, Bartle KD, Andrews GE (1986a) The relation between polycyclic aromatic compounds in diesel fuel and exhaust particulates. Fuel 65:1150–1158Google Scholar
  69. Williams R, Sparacino C, Petersen B, Bumgarner J, Jungers RH, Lewtas J (1986b) Comparative characterization of organic emissions from diesel particles, coke oven mains, roofing tar vapors and cigarette smoke condensate. Int J Environ Anal Chem 26:27–49Google Scholar
  70. Williams PT, Andrews GE, Bartle KD (1987) The role of lubricating oil in diesel particulate and particulate PAH emissions. Society of Automotive Engineers paper no. 872084Google Scholar
  71. Williams PT, Abbass MK, Tam LP, Andrews GE, Ng KL, Bartle KD (1988) A comparison of exhaust pipe, dilution tunnel and road side diesel particulate SOF and gaseous hydrocarbon emissions, Society of Automotive Engineers paper no. 880351Google Scholar
  72. Yamaki N, Kohno T, Ishiwata S (1986) The state of the art on the chemical characterization of diesel particulates in Japan. In: Ishinishi N, Koizumi A, McClellan RO, Stöber W (eds) Carcinogenic and mutagenic effects of diesel engine exhaust. Elsevier Science, Amsterdam, pp 17–40Google Scholar
  73. Yoshida E, Nomura H, Sekimoto N (1986) Fuel and engine effects on diesel exhaust emissions. Society of Automotive Engineers paper no. 860619Google Scholar
  74. Zweidinger RB (1982) Emission factors from diesel and gasoline powered vehicles: correlation with the Ames test. In: Lewtas J (ed) Toxicological effects of emissions from diesel engines. Elsevier Science, Amsterdam, pp 83–96Google Scholar

Copyright information

© Springer-Verlag 1992

Authors and Affiliations

  • P. T. J. Scheepers
    • 1
  • R. P. Bos
    • 1
  1. 1.Toxicology DepartmentUniversity of NijmegenNijmegenThe Netherlands

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