Contents Preface for Second Edition vil Preface for First Edition ix 1.0 Vehicle Emissions and Air Pollution : 1.1. Introduction, 1 1.2 Carbon Monoxide, 3 1.3 Nitrogen Oxides, 4 14 Photochemical smog. $ 15 Unbumed Hydrocarbons and Photochemical Reactivity. 6 1.6 Ozone, 6 1,7 Particulate Mater, 9 1.7.1 Ultrafine Partictes, 10 1.8 Summary of Hest Pfft, 11 1.9 Ait Quality Standards, 12 1.9.1 Ait Quality beds, 1) 1,10 Global Warming. 15 References, 17 2.0 Genesis of Engine Emissions 9 Pay ‘Combustion Genersted snd Other Exxemasor, 19 2.2 Carbon Monoxide, 23 2.3 Nitrogen Oxides, 24 2.3.1 Kinetics and Modeling of Thermal NO Formation, 25 23.2 Dependcace of NO Formanon on Temperature sad (03). 26 2.3.3 NO formation in Sl engses, 29 2.3.4 NO formabon in Cl eaginss, 31 23.5 Formation of NO; 37 12.4 Unbumed Hydrocarbon, 38 2.4.1 HC Emissions from SI Engines, 39aid Content 2.4.2 HC Emissions from CI Engines, 53 2.5 Soot and Particulate Formation, $6 2.5.1 Characteristics and Composition of Particulates, $7 2 Soot Formation Mechanisms, 60 2.5.3 Diesel smoke, 68 2.5.4 Particle Size Distribution and Ultrafine Particles (UEPs), 68 2,6 NO,-Particulate Trade-off, 74 37 LiNeet of SI Engine Design and Operating Variables, 75 2.7.4 Design Parameters, 75 2.7.2 Residual Gas Dilution and Exhaust Gas Recirculation (EGR), 7g 2.7.3 Operating Variables, 81 2.7.4 Fuel Injection and In-Cylinder Liquid Fuel during Warm-up, 82 2.7.5 Summary, 85 ine Design and Operating Variables, 85 2.8.1 Combustion Chamber Parameters, 85 2.8.2 Fuel Injection Variables, 89 2.8.3 Operational Parameters, 89 2.8.4 Exhaust Gas Recirculation, 91 2.8.5 Fuel Quality, 93 2.8.6 Summary, 94 References, 95 3.0 Emission Test Procedures and Standards 101 3.1 Test Cycles for Light and Medium Duty Vehicles, 101 3.1.1 USEPA Emission Test Cycle, 102 3.1.2 European Emission Test Procedure, 104 3.1.3. Worldwide Harmonized Light Duty Test Cycle (WLTC), 106 3.2 Test Cycles for Heavy Duty Vehicle Engines, 107 3.2.1 US Test Procedure, 107 3.2.2. European Heavy Duty Engine Emission Test Procedure, 109 3.2.3. Worldwide Harmonized Heavy Duty Test Cycles, 112 3,2. Test Cycles for Motorcycles and WMTC, 115 3.4 Evaporative Emission Test Procedures and Standards, 117 3.4.1 USEPA Evaporative Test Procedure, 117 3.4.2 EU Evaporative Test Procedure, 119 3.4.3 The US Evaporative Emission Standards, 120 3.5 Emission Standards for Light Duty Vehicles, 121 3.5.1 US Standards, 121 3.5.2 European Standards, 124 3.5.3 Others, 125 3.6 Emission Standards for Heavy Dutv Eneines. 126Content xii 3.6.2 unopoan Standards, 128 3,7 Motoreyele Emission Standards, 101 3.8 Fmission Measurement: Instrmentation and Methods, 142 3.8.1 NDIR Analyzers, 132 3.8.2. Plame lonization Detector and Non-Methane Cutter, 134 3.8.3) NMHC Measurement, | 3.8.4 Chemiluminescence Analyzer (CLA), 136 3.8.5 Oxyyen Aniilyzer, 137 3.8.6 Formaldehyde Measurement, 139 3.8.7 Constant Volume Sampling, 140 3.9 Diesel Smoke Measurement, 141 3.10 PM Mass Emissions, 142 3.11 Measurement of Particle Size and Numbers (PN), 145 3.11.1 Electrical Mobility Analysers for Particle S 3.11.2 Condensation Particle Counter (CPC), 150 3.11.3 Particle Measurement Programme (PMP) Protocol, 152 References, 155 ¢ Distribution, 147 4,0 Emission Control in SI Engines 157 4,1 Engine Design Parameters, 157 4.1.1 Compression Ratio, 158 4.1.2 Cylinder Size and Combustion Chamber Shape, 159 4.1.3. Fuelling System, 160 4.1.4 Variable Valve Timing and Lift, 162 4.2.5 Downsizing and Pressure Charging, 166 4.2. Add-On Systems for Emission Control within the Engine, 167 4.2.1. Positive Crankcase Ventilation (PCV) System, 167 4.2.2 Evaporative Emission Control, 169 4.2.3. Exhaust Gas Recirculation, 171 4.3. Thermal Exhaust Aftertreatment, 175 4.4 Catalytic Exhaust Aftertreatment, 177 44.1 Catalyst, 177 4.4.2. Catalyst Substrate/Support, 178 4.4.3 Washcoat, 184 4.4.4 — Converter Housing, 185 4.45 — Types of Catalytic Converter, 185 4.4.6 Oxidation Catalytic Converters, 187 4.4.7 Reducing Catalytic Converters, 188 4.4.8 ‘Three-Way Catalysts, 189 4:49 Zone-Conted 3- Way Catalysts, 194 4.4.10 Catalysts for Control of Cold Start HC, 196CHAPTER 1 Vehicle Emissions and Air Pollution 1.1 INTRODUCTION Emissions from automobiles were identified as the main contributors to urban air pollution by studies in California for the first time during 1950s. Photochemical reactions between unburned hydrocarbons and nitrogen oxides emitted mostly by vehicles were found responsible for production of a host of secondary pollutants including ozone and other oxidants in atmosphere. The ‘brown haze’ apps above the ground level in the Los-Angeles area as a result of the photochemical reactions between the vehicular hydrocarbons and nitrogen oxides emissions, was termed as ‘photochemical smog’. All vehicles and combustion devices using hydrocarbons and their derivatives as fucl contribute to air pollution. The amount of pollutants emitted by the combustion devices depend mainly on their design, operating conditions and the fuel characteristics. Initially, vehicular air pollution was considered primarily a problem of the US and European cities where emissions control legislations were brought-in during late 1960s to early 1970s. However, due to increase in vehicle population in the cities all over the world, vehicle emission controls are now being implemented in most countries and are being progressively tightened. 7 Worldwide vehicle population trends are shown in Fig. 1.1 [1, 2]. ‘The global vehicle populat excluding motorcycles increased from about 127 million in 1960 to 1,114 million in the year 2012. The distribution of vehicles per 1000 persons in the different geographical regions across the world for the year 2009 is given in Table 1.1. As expected, the USA with 828 vehicles for every 1000 persons has the highest vehicle ownership followed by Canada and the Western Europe, Africa has the lowest vehicle to Population ratio in the world that stood only at 25 vehicles per 1000 persons in that year and is lower by factor of nearly 33 compared to the USA. Next lowest vehicle ownership is in the Midille Haxt Avia, Population of vehicles (minimum four wheels) is projected to grow close to nearly 2080 million by the year 2030 [3]. The largest growth is expected in the non-OECD South and South: Last Asian count including China where the vehicles numbering around 65.7 million in the year 2002 would reach clove to 682 million by the year 2030. In the year 2010, worldwide motorcycles numbered around 455 million compared to 782 million ears and other light duty vehicles [2], Of all the motorcycles, Asia uecounted for 79% market share, next being the Europe with just 8,5%, Since the year 2000, due to tightening of emiasion regulationy the 2+ Stroke engine has been almost completely phased out from motor cycles and now acrons the world almoat all new motorcycles are powered by 4airoke gal ine sng, Since 1970, progressively stringent vehicle emission regulations have bee emente developed countries lke the USA, Burope and Japan, but will vehicle conibute night wo ri air pollution, In the USA, during 1995 highway and off-highway vehicles eontsibuted 40 to 50 % of the ‘otal volatile organie compound (VOC) emissions, 50 % of NO, and 80 10 90 % of curhon monoxide2 Akin Hniewlons i ion Agency IS Environmental Protection Agency Inpent embiion regulations, ee hea 0, equal to 38% and en eet ae ae inibution a highway vehieles to mS te ocean VOE (USEPA) extinaten pt the san naan af higy Nb al i si cnn) enon 22% in the Not it me ci ory. The lve valor by themselves contributed abou - ons at the end of 20" cont ‘ iil 0, ond pou ie eta 1600 Carn Commercial Vehicles AMotorcyclos 1400 § 1200 4 1000 800 600 400 200 Vehicle Registrations, ma 7070 "1960" 4990) 2000 2010 Year espn tWide vehicle population, In the Year 2012, cars: 724 million and © 309 million, (1, 2} nt tons fatty Asie (Middle Buty “nada “enitral and Sout America, unburned fuel/ hydrocarbons 1). Ng the mobile go le matter (py urces, diesel vehicles are the saitsions. Vehicles also ey 8 UPON the sulphup "mit sulphur di- and tri- the engine fuel, As mentioned earlier,‘Vehicle Emissions and Air Pollution 3 some of the vehicle emissions in atmosphere produce other harmful chemicals, known as the secondary pollutants. The main secondary pollutants are: oxidants like ozone; nitrogen dioxide (NO;) and total suspended particulates (TSP) including host of other organic compounds like peroxy-acetyl nitrate (PAN). Fig. 1.2. shows the linkage between vehicle emissions and the air pollutants. A few more substances associated with fucl’s chemical composition that are emitted by the vehicles have come under control due t0 their toxic effects, These compounds known as ‘Air Toxies’ are: benzene, 1-3 butadiene, poly-organic matter (POM), formaldehyde and acetaldehyde. Carbon dioxide is not a pollutant for local environment but it is a greenhouse gas (GHG). It is estimated that COs is responsible for about 50% of the total global warming effects. Presently, as most of the vehicles operate on hydrocarbon fuels, these emit significant amounts of carbon dioxide. Besides, methane another GHG is contributed by the natural gas vehicles through exhaust emissions and leakage from the gas production, transport and distribution systems. The sources and adverse health and environmental effects of vehicle emissions arc discussed below. Emissions Pollutants Ho > Onidants No, NO2 SO, SO, PM TSP CO eee OO! Figure 1.2. Vehicle emissions and resulting air pollutants, 12 CARBON MONOXIDE Carbon monoxide is formed during combustion due to deffcieney of oxygen, Iti but is highly toxic, On inhalation it is rapidly absorbed by lungs and combi noe vi hn oes a blood forming carboxy-hemoglobin. CO has 200 to 240 times more affinity than oxygen to ie bin aia hemoglobin [5]. The CO-hemoglobin complex is far more stable than oxy-homoglobin, Thus, exposane 0 reduces oxygen carrying capacity of the blood to body tissues, ‘The decrease in supply of open ie and netoxieation, damages tissues and els and adverse effets are higher wag nee OF OXYER due an nervous system as these have higher oxygen demand. The toxic effects of CO depend Cyne er “sPonute time and concentration as shown in Fig, 1.3 (6) ‘spend both on the ¢ early signs of CO poisoning are shortness of breath, rapi i rated judgment ie., confusion and lack of motor coordination, These ee Nadache, dizziness, dirs supply of oxygen to brain tse, 0 condition called "hops Nawsen 2m result due ren’ May appear later. Exposure to high CO concentrations or for a longer period ve? YO™iting, and " pulmonary edema, lows of consciousness and eventually to deur Reve4 MA lead to cending + I the exposure duration and4 Engine Emissions loss of consciousness and : threshold, loss leath my i ir is higher than the thres 1° moval of the a conentaton of CO in th ext of CO een asa dissociation of oe occur within a short period f time. Trento r O9 94 ox i xy i ing hij adminis fl en and correct the tissue hy from the ait having high CO aT hn ten, can combine wih OXY Oxia, hemoglobin to hemoglobin. can cor 100 ny He Ze a! gh; courscourrce il iv oa a THROBBING HEADACHE Cc : F Rag (A & ASRS : ¥ F 35 S| Nosmwerou : L - “ i 10 100 EXPOSURE (Hours) Figure 1.3 Toxicity of carbon monoxide [6] 1.3. NITROGEN OXIDES Oxides of nitrogen, NO und NO; are formed during combustion at high temperatures. In inter! combustion (IC) engines, NO is the prineipal oxide of nitrogen formed. The concentration of NOz is sous cnpice runition (SI) engine emissions (less than 2 percent of total nitrogen oxides), but is high in dies! edison, est {10m about 10 t0 20 percent. NO- is a strong oxidant and in the presence of ultraviolet radiations leads to formation of ozone via NO; — photolysis ns belows HE ad NO, +hv + NO+0 0+0,+M>0,4M_ (2) body needed to absorb the energy of reaction, 4 roca: Ht has an ivitating odour and low solubility, Hence, it reaches d2=P ch emp Qneentrations, NO; may produce mild irritation in upper respiratory sure i In asthmatic perso, ao yed it aqueous medium of wan eo POMTE May trigger asthmatic atinekee When nitrogen oxides got dissolve us throat lining, they produce nitrous and nitric acids. In in the nose and iVehicle Emissions and Air Pollution 5 these acids cause immediate irritation to the mucosa of the respiratory trac. Si SSy appear as eye irritation. In the lungs, reactions include cou, sity of gas reaches lungs, it may cause acute bronchitis, weeks after the acute pulmonary reaction, a chronic inflammation of lungs may result leading to lung fiosis. Such @ Progressive process may lead to respiratory failure. An association between NOs and repeated respiratory infections in children has been established. Nitrogen oxides too like CO react with blood hemoglobin [5]. A number of nitrogen containing ces react with hemoglobin oxidizing iron to its ferric state (Fe), This chemical state of iron may form methemoglobin. a black pigment like substance. Methemoglobin does not combine reversibly with oxygen, hence reducing oxygen carrying capacity of the blood to tissues, It also resulis in destruction of rod blood cells. When the concentration of methemoglobin exceeds 10% of the total hemoglobin level, Unis coloration of skin (cyanosis) is caused in the affected person due to lack of oxygen. At higher concentrations, symptoms like shortness of breath, weakness and headache may occur. The symptoms on exposure fo nitrogen oxides develop in a slow but harmful way. The major signs of exposure include development of bluish skin particularly of lips, fingers and toes, 14 PHOTOCHEMICAL SMOG lar symptoms igh and bronchospasm. If a sufficient pulmonary edema and even death. Several Photochemical smog, initially known, as ‘Los Angeles Smog’ is a brownish-gray haze caused by reactions into atmosphere between hydrocarbons and nitrogen oxides in the presence of solar ultraviolet naiations. It consists of a variety of organic compounds, ozone and nitrogen oxides trapped above the gomd level due to temperature inversion. The photochemical smog is characterized by an unpleasant odour given by some gaseous pollutants formed in atmosphere. The vehicles contribute most of the nitrogen oxides in urban air. Nitrogen dioxide that is emitted in air gets dissociated into nitric oxide (NO) aad atomic oxygen (O) on absorption of energy from ultraviolet radiations. The atomic oxygen combines ‘ith molecular oxygen (O,) forming ozone (03). Unburned hydrocarbons are also present in urban air as 2 result of incomplete combustion of hydrocarbon fuels, and evaporation of liquid fuels and solvents. The ‘VOCs other than methane, which include hydrocarbons and their derivatives, in presence of sunlight ‘tndergo a chain of chemical reactions with nitrogen oxides to form photochemical smog. A simplified Todel of photochemical smog formation includes the NO; photolytic cycle that comprises of reactions (11) and (1.2) and a third reaction (1.3) is given below: w NO, +hv + NO+O 0+0,+M—+0,+M NO +0, + NO; +0, eu The i redicted by the above reactions however, are well below the Saale Te eens eae to corer with the measured ozone levels is provided by the ‘ons present in the atmosphere. The hydrocarbons participate in atmospheric reactions leading to formation of NO;, The very reactive atomic oxygen, O produced in photolytie cycle attacks hydrocarbons for example the olefins. Ovone ean also react with the hydrocarbon molecules but the reaction with O is "uch faster. The olefin is broken at double bond, gives a free hydrocarbon radical (R’), which then, reacts With 03 to form peroxy* radicals (ROO'). The peroxy" radicals react with NO to form NO; in addition to Produced by the photolytic cycle. These reactions proceed as below:6 Engine Emissions 0+ Olen SR +RO (lay R* +0, = ROO uy ROO" + NO > NO, + RO a Qs These reactions keep on repeating leading to significant amount of NO; formation itt ai » Several oy species ike aldehyee Mowing general reaction, reacti i other chem fons procend fo generate intermaiate radicals and other < Hydrocarbons RH) may react with NO and oxygen to produce PAN by the fol RH+NO+0, > NO, +PAN (uy All the shove reactions may be expressad as a general global reaction given below, co —Suntight_. s SHNO, + Organic compounds (Ls) For an urban area to experien of unbumed hytrocarboas includi thst the polluzats are not widely are: NO.. ‘ources of emissions. Movement of ait s9, that Teadily provide free olefin family hydrocarbons eer i E*PONSibe for shout yen Of total reactivity of egg eMeNE, Isp cencntaton of he pg Sy depends a Photoe : that are present also 4 fect es ts in the atino: t is emi $ PORE he aca eh 8 upset ee Tost levee eMtited, The other pata OC ina even eornannl® 8 ozone frm results fron att Measure of the effect gta VOC * sft of various Voce cenne REE wi concentration of Ut formation has been measure entene, 1, 3 butadiene, and its reactivin a 'Y Per se, but ad existing sphere Where jet M80 on the already existine‘chicle Emissions and Air Pollution 7 environmental chamber experiments as mentioned earlier, However, the fact that these effects also depend on the environment where the VOCs react implies that the quantitative ozone impacts in the atmosphere will not necessarily be the same as those measured in the laboratory. He used computer ai shed models to estimate the effect of 2 VOC on ozone in atmosphere. Photochemical reaction mechanisms for atmospheric reactions of 118 VOCs were used to calculate their effects on ozone formation under various NO, concentration conditions in model scenarios representing 39 different urban areas, Ozone impacts of VOCs were quantified by use of "incremental reactivity”. This is defined as the change in ozone caused by adding an arbitrarily small amount of the test VOC to the emissions in the given urban area atmospheric conditions, divided by the amount of test VOC added. Some compounds ‘were seen to cause the formation of 10 or.more additional molecules of ozone per carbon atom reacted, either directly or through its effects on reactions of other compounds. Some other VOCs caused almost no ozone formation when they reacted, or even caused ozone formation to be reduced. ; Table 1.2 Photochemical Reactivity of Hydrocarbons (General Motor Seale) [7] Hydrocarbon Relative Reactivity CI-Cé paraffins 0 Acetylene Benzene C4 and higher paraffins 2 Monoalkyl benzenes Ortho- and para-dialkyl benzenes Cyclic paraffins Ethylene 7 Meta- dialkyl benzenes Aldehydes 1-olefins (except ethylene) 10 Diolefins Tri- and tetraalkyl benzenes Intemally bonded olefins 30 Internally bonded olefins with substitution at 100 double bond cyclo-olefins Carter [8] defined a number of indices for reactivity based on the ozone formation potential of hydrocarbons. Some of the reactivity indices used by him are given below: Incremental reactivity: Change in ozone formed caused by adding a VOC to the initia ancl emited base reactive organic gas (ROG), divided by the amount of VOC added. ‘ 7 Relative Reactivity: The incremental reactivity of the VOC divided by the incremental reactivity of ixture, Sea Talative reactivity based on the effect of the VOC on the maximum ozone formed. Integrated Oy Reactivity: Incremental or relative reactivity based on the efeet concentration integrated over time, Ozone Yield Reactis of the VOC on the Oy8 Engine Emissions rbons based on ozone yield in units of grams r tal reactivity data of some nydroontbons eae $ hea Of famed pera at VOC reputed by Cater [8] ae given of O; forme: Table 1,3 Carter's Relative Reactivity of Some VOCs [8] VOC wg VOC - = Cyclohexane eee 0.015 Acetytenes Methane nas Acetylene Bie 0.48 Methylacetylene Saas 1.02 Aromatics eae 1.04 Benzené 7 0.98 Toluene n-octane 0.60 Ethyl Iso-butane 1.21 o-Xylene 1so-pentane 138 p-Xylene Iso-octane 0.93 m- Xylene Cyelopentane 24 1,3,5-Trimethylbenzene Methyleyclopentane 28 Naphthalene Cyclohexane 1.28 Styrene Ethyl-cyclohexane 19 Alcohols and Esters Alkenes Methanol Ethene 74 Ethanol Propene , 94 2-Propyl Alcohol |-Butene 89 Isopropyl Alcohol 1-Pentene 62 n-Butyl Alcohol 3-Methyl- 1-Butene 62 Dimethyl ether I-Hexene 44 MTBE {ee 2 Trans-2-Butene 10.0 puedes and Ketones Peni 1a ‘ormaldehyde 2-Hexenes 67. Acetaldchyde 3-Octenes 33 Acetone 1,3 Butadiene 10.9 Benzaldchyde Isoprene a Phenol one 9.1 16 OZONE zone is colourless », 18 a strong Oxidant us rene layer, Which acts as for ie iiig Properties ig fy ful "The .01 t0 0, rita ae oo Pom I 28 ittitation “nehosonstiton eet and hy 0 like : ili inthe abe in cota Water and alkalis, Ozone ‘olet rays, owevars Stratosphere, it forms a lifesaving ozote hreshold of ozone gat S€OUNd level Ozone due to its highly co) fang upon individu, ranges from ier UBBS. Ozone like ott "flow to lungs and ventlatot ys reduction in a m Produces symptoms like coud!Vehicle Emissions and Air Pollution 9 dzyness of throat and chest discomfort [5]. These effects will subside when exposure is discontinued. Eye jmitation may also be caused by exposure to ozone. Exposure to 0.2 ppm of ozone for three hours produces vision disorders like visual acuity, decreases night vision and disturbs balance of muscles controlling position of eye [9]. The adverse effects of ozone increase substantially in presence of sulphur Goside and are much more than the effect of cither pollutant separately. 4.7 PARTICULATE MATTER Particulates are fine solid or liquid particles suspended in air. Vehicles emit particulate matter both in the solid and liquid phase. Solid particles emitted by vehicles are made mainly of carbonaceous matter (soot) consisting of a small fraction of inorganic substances. Different types of liquid phase substances also are sisorbed on the solid particles, During engine start up and warming particularly in cold weather, the beavy hydrocarbons in the exhaust gas may condense to form ‘white smoke’. The diesel engines operating at light loads and the small two -stroke spark ignition engines employing total loss lubrication system are the main sources of liquid phase particulate emissions. When lead antiknocks were used, the g2soline-fuelled, spark ignited (SI) engines emitted solid lead containing particles. Use of lead antiknocks in gasoline has been phased out now almost throughout the world due to toxicity of lead and poisoning of catlytic converters employed for emission control. Use of unleaded gasoline has resulted in very low paniculate emissions, just about 20 mg/km, from the 4-stroke gasoline engine vehicles without catalytic converters. The SI engines may also emit the carbon particles when operating on over-rich mixtures. With the inroduction of gasoline direct injection (GDI) or direct injection stratified charge (DISC) spark ignited engines, PM emission regulations for gasoline engines have also been introduced from Euro 5b regulations of 2011. Diesel engine is one of the principal sources of solid carbon particles (soot) emitted in air. In 24dition, other diffusion combustion systems like gas and steam turbines, and liquid fired furnaces also emit solid carbon (soot) particles. The particulate emissions from diesel engines consist of unburned soot, soluble organic substances derived from fuel and lubricating oil, ash particles coming from burt oil 2dditives and engine wear particles. The major source of particulate emissions in diesel engines is heterogeneous mode of combustion where fine soot particles are generated, These fine soot particles grow 2nd agglomerate as the combustion progresses. Later, during expansion and in the exhaust system hea bydrocerbons from fuel and oil, sulphates produced from combustion of fuel sulphur, and water are zhsorbed on the soot core of particles. The pre-control light duty diesel vehicles emitted particulates Sypically in the range of 0.2 to 0.6 g/km, The pre-1990 heavy-duty direct injection diesel engines had Paniculate emission rates of 0.5 to 1.5 g/kW-h. : : Penticles having diameter smaller than 2.5 ym constitute more than 90% mass of the total particulate matter emitted by the diesel engines. According to Stokes’ law, settling time is inversely proportional to the square of particle diameter. ‘The rate at which the fine particles settle down is, very low and these remain airbome for several days. The particles of less than 2.5 jm are of main concer as they take long time to settle, remain airborne for days and reach the respiratory system of the human beings through breathing. Small particles particularly those of less than O.tyum dia., are too small to be trapped in the upper portion of lungs and penetrate deep into lungs. The particles larger than 2,5 jm settle down fast and ate also easily filtered and retained by the upper respiratory system. Hence, inrger than 2.5 pm particles are i Paeseg pene beth cad due to two reasons: (i) They ean penetrate deep into lungs and deposit affecting performance of lungs adversely, and (ii) These ean have synergistic effect with other Pollutants present in air, Sulphur oxides and water combining together produce sulphuric acid that maybe10 Engine Emissions einogens like polycyclic aromatic hydrocarbon, an 7 ‘articles arried to lungs, Car adsorbed on soot particles and eo ibe carried to lungs and cause cancer. (PAR) when adsorbed on soot particles can also be carri 1.7.1 Ultrafine Particulate Matter Until recently, lations for PM emission from vehicles have focused on ene the mass of Py emitted, However, more and more toxicological research shows that mass of PM alone is not sufficieny to measure health risks of exposure to particulate matter, Adverse health effects of PM depend also on other parameters including size, number and surface area, i ae “The particulate matter emitted by the engines consists of a wide range of particle sizes from about 3 rm (nanometre) aerodynamic diameter up to 10 jum dia, Fig. 1.4 shows the number of particles, their surface area and mass. for different.particle size ranges emitted in a typical engine exhaust [10]. The deposition rate in respiratory system (alveolar and trachea-bronchial) for different particle sizes is also shown on Fig. 1.4. The particles of less than 100 nm aerodynamic diameter are defined as ultrafine particles (UFPs).The contribution of ultrafine particles to mass of PM emissions in the engine exhaust js not significant. The mass of'a single 2.5 jim particle would be the same as that of nearly 2.0 million UFPs of 20 nm size. Further, the geometric surface area increases by a factor of 125 when the same mass of 2.5 um dia. particles is contained in 20 nm dia, UFPs. 02 1 Nanoparticles, Fine Particles Dp <50 nm PMps — H Dp <2.5 ym Sao Ultrafine Particles 98 ) Op <100 nm, PMyo £3 on 83 § Bes 3 £5 3 =S 04 8 E~ 005 6 2 02 ° 100 Particle Diameter, nm 70,000 distributions in ‘syste B iT a 1. ystem (Alveolar + Trachea. Bronchial)[ O diesel engine exhaust, Deposition rates are for respiratoryVehicle Emissions and Air Pollution 11 particles in their deposition patterns in the lung, clearance mechanisms, and in their potential for transmission from the lung (o other tissues in the body. Fig. 1.4 shows that the deposition rate of UFPs in respiratory system is several times higher than that of fine particles (100 nm to 2.5m dia.) Health Effects Institute (HEN), Boston, USA in their study of the year 2013 [11] observed that although some studies show evidence of adverse UFP effects, yet overall the available evidence does not strongly suggest that short-term exposures to UFPs have the effects that are highly different from those of larger particles, such as PM 24, The available data from toxicological studies in animals, human exposure and epidemiologic studies so far have not provided consistent findings on the effects of exposure of human population to typical ambient levels of UFPs. Further, the studies are not able to clearly bring out whether UFPs have effects that are independent of those of other related pollutants, which are present in engine exhaust and in atmosphere along with UFPs. The HEI however, concludes with the caution; The fact that the currem database of experimental and epidemiologic studies does not support strong and consistent conclusions about the independent effects of UFPs on human health does not mean that such effects, as one part of the broader effects attributable to PM2.5, can be entirely ruled out"{\1] Although there are many sources of UFPs in the atmosphere, vehicle exhaust is the major contributor to UFP concentrations in cities, particularly near the main roads. Diesel vehicles not equipped with particulate filters are the main contributors of UFPs. Recently, the production of cars powered by the GDI engines also known as DISC or spark-ignited direct injection (SIDI) engine to improve fuel economy has been increasing and nearly 50% of new cars in the USA provide GDI engine as an option. The GDI engines emit substantially higher number of UFPs compared to port fuel injection (PFI) engines currently the most common engine used in gasoline cars. The regulatory bodies are planning action to protect against UFPs in addition to the existing mass- based PM standards. The European Union (EU) has implemented the world’s first particle number (PN) limits, in addition to the limits on the mass of PM emitted by new vehicles. European Union limits the number of particulate (PN) emissions for light duty vehicles starting with Euro 5b regulations of 2011 and for heavy duty vehicles from Euro 6 regulations of 2013. In the USA, stringent emissions standards for PM mass emissions for new heavy duty diesel engines were implemented in 2007, dramatically reducing PM emissions through the use of diesel particulate filters (DPFs). The US standards for PN emissions are also in offing, 1.8 SUMMARY OF HEALTH EFFECTS Adverse effects of various pollutants originating from vehicles are summarized in Table 1.4. Table 1.4 ‘Adverse Health Effects of Principal Pollutants (5, 9] Pollutants ‘Short-term health effects Long-term health effects 9 s Fificulty In breathing, chest tightness, Impaired lung function, increased Ozone Soreness, coughing, chest discomfort, Development ‘of emphysema, pulmonary edema ape me EN cape12 Engine Emissions bili Many constituents especially Poly- PAL. aN PM Tnereased Susceptibility to other Mae ee etc eee carcinogenic, contribute to silicosis, brown lung : function when oxidants s creased asthma altacks Reduced lung ‘Sulphates: Increased asthma atta eapee " i a of eyanosis especially at Sitrogen dion Similar to those of ozone but observed at Developmen ; ee lips, fingers and toes, adverse changes in — cell structure of lung wall Carbon mononide Headache, shortness of breath, dizziness, Effects on brain and central nervous impaired judgment, lack of motor system, nausea, vomiting, cardiac and coordination pulmonary functional changes, loss of consciousness and death TOO 1.9 ATR QUALITY STANDARDS in air but also on the period of e: concentration of pollutants over a period xposure, the air qualit Primary standards: These provi i i 3 3 Provide public healt ‘Sensitive’ roups such as ast ts raat d Protection, thmatics, children, and , which includes protect Ith of the elderly persons, ne ganizations have by i and th the effects on health and ent SO¥ETal ti saat the year 2014 and the Sreco™mended by the World Health Pollutants, Telated to Vehi eeame available, The seas 88 more and more evidence of ‘ganization guideti air quality standards revised uP ” "Pe}venin Table 5," "Pdted in the year 2005 for the icle e1Vehicle Emissions and Air Pollution 13 Table 1.5 US Standards and WHO Air Quality Guidelines [12-14] ——————— To aS Pollutant Averaging Time ___ NAAQS ofthe USA“ WHO guidelines, Level , ug/m’ Application ne/m? CO 15 minutes 7 7 700,000 30 minutes - 7 60.000 T hour P: 40,000 (35 Not to be exceeded more than 30.000 ppm)* once per year S hours $:10,000 (9 ppm) 10,000 Thour P:190 (0.100 ppm) 98th percentile of I-hour 200 daily maximum levels, averaged over 3 years annual P and $:100 (0.053 Annual mean 40 ppm) Ozone Shour P and S: 150 (0.075 Annual fourth-highest daily 100 ppm) ** maximum 8-hr concentration, averaged over 3 years Sulphur 10 minutes: - 300 dioxide 1 hour P: 65 (0.025 ppm) 99th percentile of I-hour : daily maximum (concentrations, averaged over 3 years) 3 hour S: 1300 (0.5 ppm) Not to be exceeded more than - ‘once per year 24 hour = - 20 PMs 24 hour PandS: 35 98th percentile, averaged over 25 3 years Annual P:12 ‘Annual mean, averaged over 10 S15 3 years PMio 24 hour - 30 Annual Pand $ : 150 Not to be exceeded more than 20 ‘once per year on average over 3 years Lead 3 months rolling P and S: 0.15 ‘Not to be exceeded - avg. Annual u P= Primary standards, S= Secondary standards,” gives in (the limits specified by the USEPA standards **EPA revoked in 1997 the 1-hour ozone standard (0.12 ppm, not to be exceeded more than once per year). 1.9.1 Air Quality Index As age to the receptors, a system to denote the effect of several pollutants by cae eames as Air Quality Index (AQN) has been devised. An air quality index is used by the government and environmental agencies to inform to the public, the current status of pollution in air or how polluted it is forecast to become. ‘As the AQI increases, a larger percentage of the population is likely to experience more and more severe adverse health fics. Different countries have defined their own air quality indices corresponding to their national air quality standards. The AQI is computed from14 Engine Emissions ir quality monitoring equipment or obtained from an ap the concentration of pollutants neue ae a ay idee values are typically aps imo sever ee eat ciate given a quilty level designation, a color code, and a standard public hea rages. Each re developed an Ait Quality Index that is grouped into six categoria a5 sven in aby eee an increasing level of heallh Gncer 9 the AQI increases [15]. An AQI value below, - represents “good” and over 300 represents a “hazardous" air quality. bitrue Poel tort ad : JSEPA defined AQL is based on the five criteria pollutants, which are: ; See cars est ooenes ills dielde ad nite diside A AO value of 100 generaly respond to the level forthe polltant specified by the NAAQS. The US Clean Ait Act 1 930 ruins EPA to review the national air quality standards every five years to take into account the mation svailable on health effects. The Air Quality Index is accordingly adjusted from time to time taking into account these changes Table 1.6 Air Quality Index System of USEPA AQI values Health concern level Colour code a. 51-100 Moderate Yellow 101-150 Unhealthy for sensitive groups Orange 151-200 Unhealthy Red 00 Very unhealthy Purple 301-500 Hazardous Maroon Table 1.7 ‘Ql for Different Pollutant Levels 15, 16] Or COCh iti O3 O; NO; (1 hr average) (8 hr (br my Ppm Average) average) ppb 0-50 Pas, Een Si-100 00-44 101-159 os —— 54-100 201-300 101-360 301-400 361-649 401-500 650-1249 1250-1649 1650 ~2049 d so on, the air quality ‘QI categories there is‘Vehicle Emissions and Air Pollution 15 discontinuity as the AQT changes by one unit, The pollutant concentration is converted to AQK by the following equation; (9) where: T=AQl C= the pollutant concentration the higher pollutant concentration in the AQI category the lower concentration in the AQI category. Iy = the higher AQI value in the category corresponding to Cy 1, = the lower AQI value in the category corresponding to Cy, For example, if an air quality monitor records 22.0 jig/m? as the 24-hour average of PM: concentration. using Table 1.7 the AQI from Eq. 1.9 is: 100 - 51 35.4— 12.1 (22.0 - 12.1) +51 = 718 The calculated AQI of 71.8 corresponds to air quality in the “Moderate” category. When multiple pollutants are measured at a monitoring site, the largest of AQI value obtained amongst all the criteria pollutants is reported for the location. The ozone AQI between 100 and 300 is reported by selecting the larger of the two AQIs which are computed with a I-hour ozone and 8- hour ozone concentrations. AQL values of 301 or greater are calculated with I-hour ozone concentrations. I-hour SO: values do not define AQI values greater than 200. AQI values of 201 or greater are computed with 24-hour SO. concentrations ‘AQI can increase due to increase in emissions such as during rush hour traffic or if there is forest fire in the upwind direction. These can also increase from a lack of dilution of air pollutants as a result of ‘weather conditions or temperature inversion. On a day when the AQI is computed to be ut a high level due to high concentration of any one or more pollutants, the government agencies may advise the sensitive groups, such as the elderly, children, and those with respiratory or cardiovascular problems to 2v0id outdoor physical exercises. In case the concentration of fine particles, PM is high increasing the AQI level, the government agencies may recommend the use of masks to keep fine particles from entering the Jungs. It may further, encourage voluntary measures to reduce emissions, such as using Public transportation instead of personal vehicles. During a period of very poor air quality when the AQL indicates the hazardous conditions, the agencies may take emergency measures like ordering closure of ‘major emitters like coal burning industries to reduce emissions until the hazardous conditions subside, 1.10 GLOBAL WARMING The Intergov emal Panel on Climate Change (IPCC) reported in 2013, that that the earth's average surface compara reed by approximately 0.9°C during the period L880 and 2012, (17) Increase in car's surge temperaure. is nearly 11°C relative 10 the preindustcial (ie 1730-1800) mean ‘emperature, In the 20" century alone global temperature inereased by 0.6 °C, most of which occurred during the lst forg decades of the century and this bas been attributed mainly to human aetivities, [PCC Predicted that by the end of the 2Ist century the global mean surface temperature relative 0 the 1986-°C if stringent mitigation steps are taken and 2.6 2005 average is likely to rise a further 0.3 0 1.7°C if stringent mitigat p 26% the globe. The effets include arise in Sea levels due to meting of ee in the Arete and thermal xan of water, a change in the amount and pattern of rainfall, sparaion of blenlcal oes ay melting retreat of glaciers, extreme weather events ¢.g., droughts, heavy rainfall, The wane oe ‘at Waves and loss of habitats due to floods and inundation by the rising sea, The shifting of environm temperature and climate from year to year could cause decrease in crop yields and threat to food Security, It may also result in extinction of certain species of flora and fauna, : Icis generally accepted that the global warming has been caused by increase in the concentration of greenhouse gases (GHGs) in the atmosphere and increased level of human activities, Major greenhouse The wakcr atc NaPour, carbon dioxide, methane, nitrous oxide (N30), chlorofluorocarbons and ozone The ‘water vapours although have the highest greenhouse effect, but it is not manmade and its te, ent ‘accumulation and removal from the atmosphere is fist, Directly radiated from earth : 40, Solar radiations absorbed by Earth: 235°Wime Heat and energy in the atmosphere nme { The Greenhouse | Effect The solar radiati : lations at unhindered at the wave lengin. .« mis this energy gnOsPheric gases, TES OF the visible light ¥ the preenhonss gis OMBEE Wavelength Me earth's Surface ang ® “Ough atmosphere relative atmosphere, This iy’ Which in ut resented thermal radiate it The earth's surface tH! : sorbed on carth’s surf ca paouse effect, The wos Of the nergy te intrared radiation is absorb eae ett Tadiated back se Nd energy ee *VETARE solay BY back to earth's surface and 10 and 0 'ed back ta g ergy radiat ‘ar radiations the greeny cuttB°® to a mean eee ate sh ed 10 ¢, s 0) 4 rth fr in Wim? received by & }OUse Bases back to eeetature of abe - The acl raansphere due to greenhouse eft earth’s sung lation iat Pa weep the Earth’s [3 sphere resale sorey abso increase of the‘Vehicle Emissions and Air Pollution 17 surface temperature above what it would be in the absence of the greenhouse gases. In fact, this is a natural process that keeps the earth warm enough for the life form to survive. But, if the earth's surface temperature rises due to accumulation of greenhouse gases or other reasons beyond acceptable limit effects on global climate and environment are predicted to be disastrous for human beings, their hal and other living beings. A departure from a reference value or long-term average temperature is termed as ‘temperature ‘anomaly’. A positive ‘anomaly’ indicates that the observed temperature was warmer than the reference value, while a negative ‘anomaly’ indicates that the observed temperature was cooler than the reference value. Projections using different climatic models have been made on the change in global temperatures from the past several centuries up to the end of 21" century and beyond. Large number of variables, unknowns and varying assumptions made in climatic computations result in significant variations in the projected global temperatures. Figure 1.6 shows projections on temperature anomaly with reference to the year 2000 temperatures in a business-as-usual scenario. The projections made by different climatic models are included in the shaded region shown on Fig. 1.6. The predictions for the year 2100 vary by as much as 2°C. its ats 5 - oO 3 5 28 : 2 = Lo a ULI AU a 42 2 1900 1950 2000 2500 2100 Year Figure 1.6 Global warming projections by climatic models. Adpated from [18] As the transport accounts for a significant share of the global fossil fuel combustion, the related major greenhouse gas, CO, emissions from transport account for nearly 17% share of global CO: emissions. Methane is another GHG that is contributed by the road transport as worldwide a large number of natural £48 vehicles are in operation. The nitrous oxide emission in relatively small amounts is also’ contributed by the road vehicles, The greenhouse gas emissions from the road vehicles and their potential effect on global warming and the measures to reduce the GHG emissions are sussed in detail later in Chapter 7. REFERENCES. 1. World Trends in Vehicle Population, en.wikipedia org/viki/Moror vehicle