Polycyclic Aromatic Hydrocarbons Evaluation of Sources and Effects (1983) / Chapter Skim
Currently Skimming:
1 POLYCYLIC AROMATIC HYDROCARBONS FROM MOBILE SOURCES AND THEIR ATMOSPHERIC CONCENTRATIONS
1 POLYCYLIC AROMATIC HYDROCARBONS FROM MOBILE SOURCES AND THEIR ATMOSPHERIC CONCENTRATIONS
Pages 1-52
The Chapter Skim interface presents what we've algorithmically identified as the most significant single chunk of text within every page in the chapter.
Select key terms on the right to highlight them within pages of the chapter.
From page 1... ...
Owing to the increased fuel mileage of gasolinefueled vehicles, the increasing use of diesel-fueled vehicles, and overall efforts at energy conservation, it is possible that diesel-fuel consumption could outstrip gasoline consumption in two decades. TYPES OF MOBILE SOURCES AND THEIR RELATIVE IMPORTANCE The term "mobile source" represents a broad range of vehicle classifications with considerable differences in miles traveled, amount and type of fuel consumed, exhaust emission rate, and location of fuel use.
|
From page 2... ...
Diesel particulate-emission rates are about two orders of magnitude greater than those associated with catalyst-equipped spark-ignition vehicles.25~51~9 Comparative emission factors are discussed later, but it is evident from Table 1-3 that there is already extensive use of diesel-engine vehicles in this country, and it will be well into the l990s, if ever, before light-duty diesel particulate emission becomes equivalent in tonnage to the particulate material from heavy-duty diesel-eng~ne vehicles nationwide.12,13,44 1-2
|
From page 3... ...
In diesel engines, there is an excess of oxygen with combustion temperatures in the vicinity of 2000°C. Exhaus t temperatures for spark-ignition engines are commonly between 400 and 600°C, but diesel exhaust is typically at 200-400°C (except at high load factors)
|
From page 4... ...
Studies of particle-size distribution of spark-ignition and diesel exhaust particulate material show mass-median aerodynamic diameters of 0.1-0.25 ~m.20~36~63 More than 90% of the mass is in particles less than 1 Am in diameter.72 Larger particles presumably result from deposition of particulate material on and later release from the walls of the exhaust system. Resuspended road dust, roadbed material, and tire particles result in particle sizes of about 8 Am in median diameter, which can account for as much as 10t of the measured vehicular respirable particulate mass in near-road measurements.68~72 Spark-ignition vehicles with oxidation catalysts emit particulate material that is mostly aqueous sulfuric acid droplets with organic compounds presumably adsorbed on droplet surfaces.
|
From page 5... ...
By combining the PAHs collected in each of the condensers with the PAHs collected on the filter, one obtains a better quantitative assessment of PAR emission. Results from filter-only dilution-tunnel studies are used to provide a qualitative description of PAHs in exhaust, and condenser-study results are used to provide quantitative emission rates.
|
From page 6... ...
. The quantitative emission rates have not been determined.37~38 Diesel-exhaust particulate material has been the subject of extensive study in the last 5 yr.
|
From page 7... ...
and for light-duty and heavy-duty diesel vehicles.6~6~~39~90~9{ For the other categories of mobile sources, the estimate of total PAH emission can be based on the heavy-duty spark-ignition or heavy-duty diesel emission rate per gallon of fuel consumed and the total fuel consumption of the category (railroads, aircraft, etc.~. When more than one value for a particular PAH emission rate is available for a source category, the micrograms-per-gallon-of-fuel figures are averaged.
|
From page 8... ...
The 70X contribution of the non-motor-vehicle sources to the 1-nitropyrene emission may be an artifact of the method used for calculating emission rates, inasmuch as 1-nitropyrene from sources other than passenger cars and trucks has not been investigated.
|
From page 9... ...
Using the current BaP emission rates, we have calculated the motor-vehicle BaP emission for the year 2000 and listed the results in Table 1-12. The 24 metric tons of BaP represents an 11% decrease from the 1979 value of 27 metric tons and reflects the benefit of catalyst-equipped spark-ignition passenger cars over their noncatalyst counterparts, which is partially offset by the incursion of diesel vehicles.
|
From page 10... ...
Calculations of BaP total motor-vehicle emission tonnage, urban fractions, and inhalation exposures for the year 2000 have assumed no changes from the present fuel-specific emission rates for the various motor-vehicle categories. Even modest particulate-emission controls (50t 1-10
|
From page 11... ...
Control of diesel particulate material has received much attention recently. The light-duty diesel particulate-emission standard of 0.6 g/mi that went into effect for the 1982 model year was achieved by most diesel manufacturers through engine modifications.
|
From page 12... ...
If diesel-particle control devices are successfully developed and used on light- and heavy-duty diesel vehicles, reductions in the PAN emission factor by at least a factor of 2, and conceivably a factor of 10 or better, could be realized. Cost estimates of the diesel-particle control techniques are premature; the technology of choice has not yet been determined.
|
From page 13... ...
S Energy Consumption, 1979a Enprgy Content, Consumption Energy Source 104 BTU/unit 1015 BTU Quantity Oil 9.8/gal 34.2 3.5 x 1011 gal Coal 1.3/lb 15.6 1.2 x 1012 lb Natural gas 0.1/ft 20.4 2.0 x 101 ft3 Hydrogenerat ion Nuclear power 3.1 2.7 Wood 1.0/lb 0.17 1.7 x 101° lb Other -- 0.12 Total 76 aData from Motor Vehicle Manufacturers Association.60 1-13
|
From page 14... ...
TABLE 1-2 Uses of Major Crude-Oil Fractions in the United States, l97ga Consumption, 109 gal Distillate Residual Destination Gasoline Oil Oil Otherb Residential -- 17 -- 0.8 0.1 0.1 Commercial Industrial Electric utility Oil company Farm Military Rail r ~ ~ 9 6~2 2 ~ 1 22 1.1 3.3 1.3 4.3 0 9 0.2 -- 4.9 0.01 Marine -- 2.1 7.7 Highway vehicles104.2 8.66 Off-highway vehicles1.6 3.4 -- Other5.5 1.8 1.0 100.0 Totals e112.6 58.3 50.3 101.0 f141.9 66.4 56.7 106.5 aData from Motor Vehicle Manufacturers Associations and National Petroleum News.61 bIncludes jet fuels, kerosene, lubricants, asphalt, etc. CCombined total for residential and commercial categories.
|
From page 15... ...
TABLE 1-3 Mileage and Fuel Consumption, 1979 Mileage, Fuel Consumption, Fuel User Fuel 10~° mi/yr 109 gal/yr Highway vehicles: Passenger cars Gasoline 112.9 79.0 Diesel 1.1 0.81 Trucks Gasoline 28.8 23.2 <33,000 lb Diesel 0.59 0.74 Trucks Gasoline 0.34 1.1 >33,000 lb Diesel 6.4 15.9 Buses Gasoline 0.30 0.41 Diesel 0.31 0.62 Motorcycles Gasoline 2.2 0.44 Other: Railroads Diesel -- - 4.4 Ships Gasoline -- 0.93 Diesel -- 8.7 Aircraft Gasoline -- 0.77 Jet -- 22.0 Farm vehicles Gasoline -- 1.3 Diesel -- 4.3 Military vehicles Diesel -- 0.85 Other Gasoline -- 5.4 Diesel -- 3.5 Totals Gasoline 152.9 112.6 Diesel -- 39.8 J t -- 22.0 aI) ata from Jambekar and Johnson,46 Motor Vehicle Manufacturers Association,60 National Petroleum News,61 and Shelton.82~83 1-15
|
From page 16... ...
High-altitude and California emission rates are different. bThe 50,000-mile emission rates are calculated from zero-mile rate by addition of term that takes account of EPA-projected deterioration rate of vehicle combustion and emission-control systems.
|
From page 17... ...
TABLE 1-5 Summary of Gaseous Hydrocarbons Emitted from Vehicles All n-alkanes from e-butane through n-hexacosane Four methyl-subetituted butanes Ten methyl- and ethyl-substituted pentanes and 11 cyclopentanes Eleven methyl- and ethyl-substituted hexanes and 35 cyclohexanes Fifteen methyl- and ethyl-substituted heptanes Five methyl-substituted octanes One methyl-substituted nonane One methyl-substituted de cane One methyl-substituted undecane Decalin and two methyl-substituted decalins Two Clo alkanes Eleven Cll alkanes Nine C12 alkanes Th i r teen C 13 alkanes E levee C 14 alkane s Eight Cls alkanes Eight C16 alkanes Five Cl7 alkanes Three Gig alkanes Seven methyl-substituted butenes and two methyl butadienes Eighteen pentenes and pent adiene Fourteen hexenes Six heptenes Four octenes Decene and dodecene through heneicosene Seven cyclic olefins Seventy-one alkyl-substituted benzenes Eight styrenes and the three xylenes Fourteen indans and three indenes Twenty-eight alkyl-substituted naphthalenes Three alkylthiophenes and two benzothiophenes Two alkylsulfides and one alkylamine Six nonaromatic alcohols and eight aromatic alcohols Eighteen aliphatic and aromatic aldehydes Six furans, 17 ketones, and six organic acids 1-17
|
From page 18... ...
TABLE 1-6 Qualitative Analysis of Nonpolar and Moderately Polar Fractions of Diesel Particulate Extract Approximate Concentration in Oldsmobile Extract, ~ _ Com ounds P Nonpolar fractions: Phenanthrenes and anthracenes Methylphenanthrenes and methylanthracenes Dimethylphenanthrenes and dimethylanthracenes Pyrene Fluoranthene Methylpyrenes and methylfluoranthenes Chrysene Cyclopenta~cd~pyrene Benzo~ghi~fluoranthene Benz~aJanthracene Benzo~a~pyrene Other PAHs, heterocyclics Hydrocarbons and alkylbenzenes Total, nonpolar fractions Moderately polar fractions OAU 1~ - Fluorenones Methylfluorenones Dimethylfluorenones Anthrones and phenanthrones Methylanthrones and methylphenanthrones Dimethylanthrones and dimethylphenanthrones Fluoranthones and pyrones Benzanthrones Xanthones Methylxanthones Thioxanthones Methylthioxanthones 1-18 600 1, 400 3, 000 1,700 1,400 800 100 20 100 500 40 30, 000 500 000 , 4, 000 400 200 1, 600 1,600 1,300 1,200 200 300 200 1, 600 900 539, 700 13,500
|
From page 19... ...
TABLE 1-6 (continued) Compound PAH carboxaldehydes: Fluorene carboxaldehydes Methyl fluorene carboxaldehydes Phenanthrene and anthracene carboxaldehydes Methylanthracene and methylphenanthrene carboxaldehydes Dimethylanthracene and dimethylphenanthrene carboxaldehydes BaA, chrysene, and triphenylene carboxaldehydes Naphthalene dicarboxaldehydes Dimethylnaphthalene carboxaldehydes Trimethylnaphthalene carboxaldehydes Pyrene and fluoranthene carboxaldehydes Xanthene carboxaldehydes Dibenzofuran carboxaldehydes PAH acid anhydrides: Naphthalene dicarboxylic acid anhydrides Methylnaphthalene dicarboxylic acid anhydrides Dimethylnaphthalene dicarboxylic acid anhydrides Anthracene and phenanthrene dicarboxylic acid anhydrides Hydroxy PAHs: Hydroxyfluorene Methylhydroxyfluorene Dimethylhydroxyfluorene Hydroxyanthracenes and hydroxyphenanthrenes Hydroxymethylanthracenes and hydroxymethylphenanthrenes Hydroxydimethylanthracenes and hydroxydimethylphenanthrenes Hydroxyfluorenone Hydroxyxanthone Hydroxyxanthene 1-19 Approximate Concentration in Oldsmobile Extract, ppm 1,600 400 2,600 1,600 400 400 300 300 1,000 1,600 600 400 3,000 1, 000 500 600 1,400 400 1,500 600 900 1,300 2,000 1,300 1, 000 11,200 5,100 10,400
|
From page 20... ...
TABLE 1-6 (continued) Compound PAN quinones: Fluorene quinones Methylfluorene quinones Dimethylfluorene quinones Anthracene and phenanthrene quinones Me thy lanthracene and methylphenanthrene quinone8 Fluoranthene and pyrene quinine Naphthotl,8-cd~pyrene 1,3-dione Nitro PAHs: Nitrofluorenes Nitroanthracenes and nitrophenanthrenes Nitrofluoranthenes Nitropyrenes Me thylni tropyrenes and me thylnitrofluoranthenes Other oxygenated PAHs: 700 600 500 1,900 2,000 200 600 30 70 10 150 20 8,000 PAN carryover from nonpolar fraction: 6,000 Phthalates, HO contaminants: Total, moderately polar fractions Approximate Concentration in Oldsmobile Extract, ppm 6,500 300 8,000 6,000 30,000 1-20 30,000 91,000
|
From page 21... ...
TABLE 1-7 Nitroarenes Indicated in Diesel-Exhaust Particulate Extracts Mononitroarenes: Nitroindene Nitroacenaphthylene Nitroacenaphthene Nitrobiphenyl Nitrofluorene Nitromethylacenaphthylene Nitromethylacenaphthene Nitromethylbiphenyl Nitroanthracene Nitrophenanthrene Nitromethylfluorene Nitromethylanthracene Nitromethylphenanthrene Nitrotrimethylnaphthalene Nitrofluoranthene Nitropyrene Nitro(C2-alkyl~anthracene Nitro(C2-alkyl~phenanthrene Nitrobenzofluorene Nitromethy~fluoranthene Nitromethylpyrene Nitro(C3-alkyl~anthracene Nitro(C3-alkyl~phenanthrene Nitrochrysene Nitrobenzoanthracene Nitronaphthacene Nitrotriphenylene Nitromethylnaphthacene or Nitromethylchrysene Nitromethylbenzanthracene Nitromethyltriphenylene Nitrobenzopyrene Nitroperylene Nitrobenzofluoranthene 1-21 Polynitroarenes: Dinitromethylnaphthalene Dinitrofluorene Dinitromethylbiphenyl Dinitrophenanthrene Dinitropyrene Trinitropyrene Trinitro(Cs-alkyl~fluorene Dinitro(C6-alkyl~fluorene Dinitro(C4-alkyl~pyrene Nitro-oxyarenes: Nitronaphthaquinone Nitrodihydroxynaphthalene Nitronaphthalic acid Nitrofluorenone Nitroanthrone Nitrophenanthrone Nitroanthraquinone Nitrohydroxymethylfluorene Nitrofluoranthone Nitropyrone Nitrofluoranthenequinone Nitropyrenequinone Nitrodimethylanthracene carboxaldehyde Nitrodimethylphenanthrene carboxaldehyde Other nitrogen compounds: Benzocinnoline Methylbenzocinnoline Phenylnaphthylamine (C2-Alkyl~phenylnaphthylam~ne
|
From page 23... ...
cr .
|
From page 24... ...
0 \ ~ ~ ~ ~ ~ lo ~ ~ ~ ~ A ~ - ~ ~ ~ us - ~ ~ At ~-~ 0 us ~ - lo ~ - ~ ~ At ~ ~ lo A cc ~ ~ ~ ~ or so rid ~ 0 0 ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ `0 ~ ~ ~ ~ 0 0 cot ~ cry _ cat cat 0 ~ ~_ _ 0 us ~4 - ~ ~ 0 o A, D o At: o ~4 0` 1 a, a: O .
|
From page 25... ...
Benzota~pyrene from mobile sources is therefore about 0.2% of total PAHs .
|
From page 26... ...
TABLE 1-1 1 Contributions of Mobile-Source Categories to PAH and 1-Nitropyrene Emission, 1979 PAH Emission, 1-Nitropyrene Emission, Category % % Motor vehicles: Passenger cars: Noncatalyst 29.1 0.9 Oxidation catalyst 3.8 0.6 Diesel 0.6 1.3 Trucks, <33,000 lb: Spark-ignition 14.7 0.5 Diesel 0.6 1.2 Trucks, >33,000 lb: Spark-ignition 0.7 0.02 Diesel 11.8 -25.1 Buses: Spark-ignition 0.3 0.01 Diesel 0.6 1.0 Motorcycles 0.3 62.5 0.01 30.6 Other mobile sources.
|
From page 27... ...
EM 'e a, on · ~c to to to O _1 o ~ a, a]
|
From page 28... ...
To use these values with emission factors other than 1 g/mi (or 1 g/min) , multiply the concentration factor by the actual emission factor in grams per mile (or grams per minute for idle conditions)
|
From page 31... ...
TABLE 1-16 Calculation of Benzo~a~pyrene Inhalation Exposure for 1979 Benzo~a~pyrene Benzo~a~pyrene Concentration, Inhalation,a Exposure SituationExposure Timeng/m ng Typical roadway2 min17.2 0.4 tunnel Severe roadway2 min43.7 0.9 tunnel Typical street8 h1.3 6.5 canyon, 1,600 veh/h Severe street20 min4.3 0.9 canyon, 2,400 veh/h Severe expressway2 h7.7 ~ 9.6 Beside expressway14 h0.2 1.8 Total exposure aBased on inhalat ion rate o f 15 maid . bCorresponds to daily average atmospheric BaP concentration of 1.3 ng/m3 [(20.1 ng/d)
|
From page 32... ...
Adapted from Kulp et al.49 Based on manufacturers' sales projections (on-road fuel economy based on actual sales)
|
From page 33... ...
//~, to cr c c ~ o cL J {D C 0~ C C CL Cat \ J ~hi.
|
From page 35... ...
Influence of sampling filter type on the mutagenicity of diesel exhaust particulate extracts. Atmos.
|
From page 36... ...
Effects of fuels and dilution ratio on diesel particulate emissions. SAE Technical Paper 790417.
|
From page 37... ...
Salmeen. Diesel exhaust treatment devices: Effects on gaseous and particulate emissions and on mutagenic activity.
|
From page 38... ...
Characterization of particulate emissions from in-use gasoline fueled motor vehicles, pp.
|
From page 39... ...
Lofroth, G Comparison of the Mutagenic Activity from Diesel and Gasoline Powered Motor Vehicles to Carbon Particulate Matter.
|
From page 40... ...
Hunt. The analysis of nitrated polynuclear aromatic hydrocarbons in diesel exhaust particulates by mass spectrometry/mass spectrometry tech niques, pp.
|
From page 41... ...
The measurement and analysis of the physical character of diesel particulate emissions. SAE Technical Paper 760131.
|
From page 42... ...
Benzo~a~pyrene Emissions from Gaso 1 ine and Die se 1 Automob iles . SAE Technical Paper 790419 .
|
From page 43... ...
typhimurium procedures) by Guerin _ al.13 Of several crude oils and shale- and coal-derived petroleum substitutes showed the petroleum-substitute mutagenicities to be equal to or 10-100 times greater than those of petroleum products.
|
From page 44... ...
Numerous other studies cited in the review described the carcinogenic potential of crude oils from various locations when tested in animals. The review by gingham et al.
|
From page 45... ...
USED ENGINE OIL The 1972 NRC study26 on particulate polycyclic organic matter (POM) reported findings in the literature that BaP emission increased as the vehicle aged and oil consumption increased from 1,600 mi/qt to 200 mi/qt and that the BaP preferentially concentrated in the crankcase.
|
From page 46... ...
In Table 2-6, the emission rates for inte~=ediate-sized coal, oil, or gas units using different firing methods show that the under-feed coal-stoker units emit all 10 PAHs at the higher rates. The EPA Industrial Environment Research Laboratory, Research Triangle Park, N.C.
|
From page 47... ...
from an urban automobile traffic tunnel, from ambient air, and from the bench (push side) of a steel-mill coke oven (see Figure 2-1~.
|
From page 48... ...
Hazards of exposure to the particulate matter in chimney-cleaning are recognized to be associated with not only skin exposure, but also inhalation. The carcinogenic health hazards associated with chimney-cleaning were reviewed by Bagchi and Zimmerman.1 The number of housing units burning wood was estimated by DeAngelis et al.,9 using 1970 U.S.
|
From page 49... ...
In some circumstances, wood-burning can be the largest combustion source for various atmospheric pollutants in urban areas. For example, the contribution of wood-burning emission products to atmospheric PAHs in Telluride, Colorado, has been estimated by Murphy et al.25 Telluride is a small community in a valley with poor ventilation and with large temperature inversions.
|
From page 50... ...
The concluding remarks of the 1981 NRC report The Recovery of Energy and Materials from Solid Waste27 stated "that the technologies for energy recovery were still under development and that the most highly developed and least risky was mass burning, but that other technologies were being tested." The solid waste from residential, commercial, and institutional sources amounted to 130 million metric tons in 1976 and is projected to increase to 180 million tons by 1985.48 In EPA's 1971 review42 of the literature on municipal incineration, the findings of Hangebrauck et al.14 (Table 2-15) showed the emission of 10 PAHs from municipal and commercial units burning wastes from households, grocery stores, and restaurants.
|
From page 51... ...
In the 1976 report, it was noted that wild forest fires consume about 3 times as much fuel as prescribed fires and produce about 3 times as much particulate matter per ton of fuel burned as prescribed fires. On the average, prescribed fires consume 3 tons of fuel per acre (range, 1-10 tons/acre)
|
From page 52... ...
A high percentage of PAHs is removed from municipal water by flocculation and sedimentation of suspended particulate matter. The chlorination process removes a large percentage of residual PAN contamination (the amounts removed by this process are discussed elsewhere in this report)
|
Key Terms
This material may be derived from roughly machine-read images, and so is provided only to facilitate research.
More
information on Chapter Skim is available.