1 Overview.- 1.1 Introduction.- 1.2 This Volume's Contents.- 2 Automobile Exhaust Gas Emissions.- 2.1 Origin of Automobile Exhaust Gas Emissions.- 2.1.1 Chemistry of Engine Combustion.- 2.1.2 Typical Main Components of Automobile Exhaust Gas.- 2.1.3 Calculation of Mass Concentration in Volume Concentrations.- 2.1.4 Formation of Soot Particles.- 2.2 Evaporation and Fueling Emissions.- 2.2.1 Hydrocarbon Emission Sources of a Motor Vehicle.- 2.2.2 Evaporation Emissions.- 2.2.3 Fueling Emission.- 2.3 Legislation.- 2.3.1 Historical Development.- 2.3.2 Legislation from the Present Viewpoint.- 2.4 Present Condition of the Exhaust Pipe Exhaust Emissions of Passenger Vehicles.- 2.5 Emission Prognosis for Germany (Calculated in 1990).- 2.5.1 Overview.- 2.5.2 Parameters.- 2.5.3 Calculation Method.- 2.5.4 Results.- 2.5.5 Consequences.- 3 Natural and Anthropogenic Emissions on a Global and Country-Related Scale and the Resulting Pollutant Concentrations in the Atmosphere.- 3.1 Introduction.- 3.2 Sources and Source Strengths of Individual Trace Gases.- 3.2.1 Hydrocarbons.- 3.2.2 Carbon Monoxide.- 3.2.3 Carbon Dioxide.- 3.2.4 Nitrogen Oxides.- 3.2.5 Sulfur Dioxide.- 3.2.6 Ozone.- 4 Air Quality Control.- 4.1 Dispersion Models.- 4.1.1 Street Canyon Model.- 4.1.2 Highway Model.- 4.2 Scenarios for the Assessment of Air Quality Situations.- 4.3 Scenario Definitions.- 4.4 Pollutant Concentrations in Street Canyons.- 4.5 Measured Air Quality Values.- 4.5.1 Street Canyon.- 4.6 Air Quality Maps.- 4.7 Conclusion.- 5 Effects.- 5.1 Introduction.- 5.2 Legislation.- 5.3 Effect on Humans, Significance of Dose.- 5.4 Using the Effect of Carbon Monoxide (CO) on Humans as an Example.- 5.5 Carcinogenic Substances.- 5.6 Methods of Effect Research.- 5.6.1 In-Vitro Tests.- 5.6.2 In-Vivo Tests.- 5.6.3 Problems of In-Vitro and In-Vivo Examinations.- 5.7 Research Projects and Results in Chronological Order.- 5.7.1 Experiments with Gasoline Engine Exhaust Gas (a UBA/FAT Project).- 5.7.2 Test with Diesel Engine Exhaust Gas (a Volkswagen/Audi Project).- 5.7.3 Experiments with Gasoline and Diesel Engine Exhaust Gas, Gasoline Engine with and without Three-Way Catalytic Converter, Diesel Engine Exhaust with and without Soot Particles (a CCMC Project).- 5.7.4 Worldwide Projects.- 5.7.5 Joint Research Program (JRP) in the Federal Republic of Germany.- 5.8 Forest Damage.- 5.8.1 General Remarks.- 5.8.2 The Terms Acid and Alkaline.- 5.8.3 Hypothesis for the Explanation of Tree Diseases.- 5.9 Global Environmental Pollution.- 5.9.1 Natural Greenhouse Effect.- 5.9.2 Anthropogenic Contribution.- 5.9.3 Increase in the CO2 and Methane Concentrations in the Atmosphere.- 5.9.4 Effects.- 5.9.5 Critical Remarks.- 6 Measuring Methods and Measuring Instruments.- 6.1 Absorption spectroscopy.- 6.1.1 Introduction.- 6.1.2 Theoretical Basis.- 6.1.2.1 Types of Spectra.- 6.1.2.2 Energy - Frequency Correlation.- 6.1.2.3 Electron Band Spectra.- 6.1.2.4 Vibrational Spectra.- 6.1.2.5 Pure Rotational Spectra.- 6.1.2.6 Rotational-Vibrational Spectra under Normal Conditions.- 6.1.3 Lambert-Beer law.- 6.1.4 Nondispersive Infrared Measuring Method (NDIR).- 6.1.4.1 Operating Principle of the NDIR Measuring Instrument.- 6.1.4.2. Principle of Multicomponent Measurement acc. to the Gas Filter Correlation Method.- 6.1.4.3 Electronics.- 6.1.5 Nondispersive Ultraviolet Analyzer (NDUV) for NO.- 6.1.6 Microwave Gas Analysis.- 6.1.7 Fourier-Transform-Infrared Spectroscopy (FTIR Spectrometer).- 6.1.7.1 Principle and Method.- 6.1.7.2 Assessment of Fourier Transform Spectroscopy for Measuring Automobile Exhaust Gases.- 6.1.8 Semiconductor-Diode-Laser (SDL) Spectrometer as Selective Emitter.- 6.2 Ionization Methods.- 6.2.1 General Observations.- 6.2.2 Flame Ionization Detector (FID).- 6.2.2.1 Operating Principle.- 6.2.2.2 The Mechanism of Ion Formation.- 6.2.2.3 Assessment of FID Instruments.- 6.3 Chemiluminescence Analyzer.- 6.3.1 Principle.- 6.3.2 Method and Measuring Instrument.- 6.4 Oxygen Measuring Methods.- 6.4.1 General Observations.- 6.4.2 Paramagnetic Measuring Methods.- 6.4.2.1 Torsion Balance Method.- 6.4.2.2 Differential Pressure Methods.- 6.4.3 Electrochemical Oxygen Measurement.- 6.5 Chromatographic Methods.- 6.5.1 Basics.- 6.5.2 Gas-Solid Chromatography (GSC).- 6.5.3 High-Performance-Liquid-Chromatography (HPLC).- 6.6 Mass Spectrometry (MS).- 6.6.1 Basic Observations.- 6.6.2 Inlet System.- 6.6.3 Electron Impact Sources.- 6.6.4 Ion Optics.- 6.6.5 Mass Separation Systems.- 6.6.5.1 Static Separation Systems.- 6.6.5.2 Dynamic Separation Systems.- 6.6.6 Ion Cyclotron Resonance (ICR) Spectrometer.- 6.6.7 Mass Resolving Power.- 6.6.8 Exemplary Result.- 6.6.9 GASP - Gas Analysis by Sampling Plasma.- 6.6.9.1 Basic Observations.- 6.6.9.2 Principle.- 6.6.10 Time-of-Flight Mass Spectrometer.- 6.6.11 Tunable Laser Ion Source for TOF-MS.- 6.6.12 Assessment of Mass Spectrometry.- 6.6.13 Gas Chromatography/Mass Spectrometry (GC/MS).- 7 Measurement of Unregulated Exhaust Gas Components and Diesel Exhaust Gas Particles.- 7.1 Legislative Situation with regard to Unregulated Components.- 7.2 Sampling.- 7.2.1 Sampling from Undiluted Exhaust Gas.- 7.2.1.1 Total Flow Method.- 7.2.1.2 Partial Flow Method.- 7.2.2 Sampling from Diluted Exhaust Gas.- 7.2.2.1 Isokinetic Sampling from the Dilution Tunnel.- 7.2.2.2 Collection in Sample Bags.- 7.2.2.3 Adsorption and Absorption.- 7.2.2.4 Automatic Sampling System.- 7.3 Sample Treatment and Analysis.- 7.3.1 General.- 7.3.2 Analysis of Gaseous Exhaust Components without Preceding Treatment.- 7.3.3 Combined Gas Chromatography/Mass Spectrometry (GC/MS).- 7.3.4 Further Analytical Procedures.- 7.4 Emission Values of Some Unregulated Exhaust Gas Components.- 7.5 Summary of the Order of Magnitude of Emission Results.- 7.6 Measurement of Diesel Particles.- 7.6.1 Measuring Procedure.- 7.6.2 Measurement Results.- 7.6.3 Particle Bound Substances.- 7.6.4 Elementary Composition of Particles.- 7.6.5 Influence of Different Parameters.- 7.6.6 Determination of the Density Function of Aerodynamic Particle Diameters.- 8 Vehicle Exhaust Emission Tests.- 8.1 Introduction.- 8.2 Test Techniques.- 8.2.1 Overview of the Test Process.- 8.2.2 Specified Test Fuels.- 8.2.3 Driving Cycle.- 8.2.3.1 Remarks.- 8.2.3.2 Development of Driving Cycles.- 8.2.3.3 Assessment and Comparison Criteria.- 8.2.3.4 Results of Test Runs.- 8.2.3.5 Proposal for a New Worldwide Standard Driving Cycle.- 8.2.4 Driver.- 8.2.5 Chassis Dynamometer.- 8.2.5.1 Remarks.- 8.2.5.2 Resistive Forces on Vehicles on the Chassis Dynamometer.- 8.2.5.3 Resistive Forces for Vehicles driven on the Road.- 8.2.5.4 Procedure for Calibrating the Test Stand.- 8.2.6 Exhaust Emission Sampling System.- 8.2.6.1 Remarks.- 8.2.6.2 CVS Calibration.- 8.2.6.3 Checking the Overall System.- 8.2.7 Quantitative Analysis of the CVS Gas Samples.- 8.2.8 Calibration Gases.- 8.2.8.1 Principles.- 8.2.8.2 Legislation.- 8.2.8.3 Calibration Gases in Cylinders.- 8.2.9 Final: Calculation of the Measurement Results.- 8.2.9.1 US-75 Test.- 8.2.9.2 Calculation of the Fuel Consumption.- 8.2.10 Measuring the Fuel Evaporation Emission in the SHED Test.- 8.3 A New Proposed Exhaust Emission Test System.- 9 Vehicle Exhaust Emission Testing Procedures - Overview and Criticism.- 9.1 Regulated Procedures.- 9.1.1 Monitoring the Automobile Manufacturer.- 9.1.2 Monitoring the Automobile Owner.- 9.1.3 Lack of Standardized Procedures.- 9.2 Statistical Errors.- 9.3 Operational Characteristics.- 9.4 Systematic Errors, Round Robin Tests.- 9.5 Analysis of Systematic and Random Errors.- 9.5.1 Both Error Types.- 9.5.2 Influence of Parameters of the FTP on Overall Uncertainty.- 9.5.3 Total Safety Margin.- 9.6 Certification Testing.- 9.6.1 European Procedure.- 9.6.2 US Procedure.- 9.7 Assembly Line Testing.- 9.7.1 European Test, Inspection by Variables.- 9.7.2 Assembly Line Testing in the USA, 49 States, Attributive Method.- 9.7.3 California Assembly Line Testing, Inspection by Variables.- 9.7.4 Discussion of Existing Assembly Line Test Procedures.- 9.8 Interrelationship between Certification, Assembly Line, and Field Monitoring Tests.- 9.9 Monitoring the Vehicles in Use.- 9.9.1 Introduction.- 9.9.2 Summary.- 9.9.3 Short Tests.- 9.9.4 System Check (Parts Check).- 9.9.5 The AU in Germany.- 9.9.6 On-Board Diagnosis (OBD).- 9.10 Proposal for a New Logical Test Procedure.- 10 Exhaust Emission Measuring Techniques - Quo Vadis?.- 10.1 General Aspects.- 10.2 On-Board Measuring Procedures.- 10.3 Outlook.
