-------
The composition data are presented in the 5-class reactivity format
in Table 3-52.
As shown in Table 1-3, the photochemical reactivity of diesel exhaust
is considerably higher than of gasoline powered vehicle exhaust. This is
the effect of, primarily, a higher fraction of class V compounds, as shown
in Table 3-53. This seems to conflict with the generally held view that
diesels are "cleaner" than conventional power plants. However, Table 3-54
shows that although the reactivity of diesel exhaust is higher than that
of gasoline powered vehicles, the mass emission rate, on a per mile basis,
is much lower.
TABLE 3-53. COMPARISON OF THE ORGANIC EMISSIONS
FROM GASOLINE AND DIESEL POWERED
VEHICLES *
Mole %
Gasoline Diesel
Class I
Class II
Class III
Class VI
Class V
28
0
30
19
23
0
0
24
6
57
*See Table 1-3
TABLE 3-54. COMPARISON OF THE MASS HYDROCARBON
EMISSION RATES FROM DIESEL POWERED
VEHICLES AND GASOLINE POWERED
PASSENGER CARS [49]
Hydrocarbons
Formaldehyde
Aliphatic Aldehydes
(as CH20)
Acrolein
Diesel (gm/mi)
0.29
0.015
0.020
0.013
Gasoline (gm/mi)
2.68
0.075
0.082
0.060
3-72
-------
3.4.5 Aircraft
Jet Aircraft
The organic emission characteristics of gas turbine (jet) powered
aircraft are unusual in two major respects. First, the organic emission
rate (Ibs/hr) is highest at the lowest fuel flow rate, whereas for most
combustion devices the reverse is most often true, [50], [51]. Second,
the low power, idle mode is used for the majority of the time the engines
are running and the aircraft is in the Los Angeles basin.
Table 3-55 shows the relative emission rates and the time in each
operating mode for a typical landing-takeoff cycle, [52]. According to
the table almost all of the emissions occur during the taxi-idle portion of
the cycle. This indicates that hydrocarbon composition data obtained at
the idle power setting would be a very good approximation of the composition
of the total hydrocarbons emitted by gas turbine engines during the time
that the aircraft is in the air basin. This period excludes most of the
climb and approach and all of the cruise portion of the flight.
TABLE 3-55 FRACTION OF HYDROCARBON EMISSIONS OCCURRING
IN EACH OPERATING MODE
Mode
Taxi -idle
Takeoff-climbout
Approach
Relative Emission'
Rate, [53]
16.2
1.2
1.0
Minutes in Each
Mode, [52]
26
3
4
% of Total* Organics
Emitted in Each
Operating Mode
98%
1%
1%
100%
*
These percentages apply to the organic emissions occurring in
the vicinity of the airport and consequently excluded emissions
that occur during the high altitude, en route phase of the flight.
3-73
-------
Table 3-56 shows the distribution of organics in the exhaust of
a turbine engine. These data are assumed to be representative of gas
turbine engines in general since it is known that the composition of
the hydrocarbons tend not to vary substantially from turbine to turbine,
[50], although the mass emission rate does, [54]. Note that the hydro-
carbons are distributed only by carbon number (i.e., number of carbon atoms
in the molecule and not by compound type). The overall mole fraction of
aldehydes are, however, shown. This set of data was chosen in the absence
of any definitive hydrocarbon emission study, [50].
Since these data are the most detailed available, it was necessary to
make a working approximation of the composition of the compounds associated
with each carbon number. These approximations were made on the basis of
what seemed reasonable; there is, however, no data available to verify them.
These approximations are shown in Table 3-57. Note that in all three cases,
the total aldehyde fraction nearly matches the measured values as shown in
Table 3-56. Table 3-58 shows the variation in hydrocarbon emissions for
each class of compounds with variation in operating mode.
TABLE 3-56. DISTRIBUTION OF THE ORGANICS IN GAS TURBINE
EXHAUST, [53]
Mole % of Total Organics
CARBON NUMBER
1
2
3
4
5
6
7
8
9
10
IDLE
TAKEOFF
APPROACH
11
11
38
33
33
3-74
-------
TABLE 3-56. DISTRIBUTION OF THE ORGANICS IN GAS TURBINE
EXHAUST [53] (Continued)
11 9
12 8
13 7
14 5
15 3
16 2
17 1
18 1
19+ 4
5
4
4
5
40 3
3
4
3
30
5
4
3
4
59 4 /
3
4
3
27
> 57
Weight % Aldehydes
relative to total 10% 30% 57%
hydrocarbons
Relative mass 16.2 1.2 1.0
emission rate
TABLE 3-57. APPROXIMATE DISTRIBUTION OF ORGANIC TYPES
BY CARBON NUMBER CATEGORY
Mole %
Carbon Number Type of
Category Compounds
1-3
-6
Paraffins
Acetylene
Olefins
Aldehydes
Paraffins
Olefins
Aldehydes
Benzene
Taxi -idle
Mode
7
1
2
1
7
2
1
1
Takeoff
Mode
2
0
0
1
2
1
2
0
Approach
Mode
1
0
1
3
1
0
3
1
3-75
-------
TABLE 3-57. APPROXIMATE DISTRIBUTION OF ORGANIC TYPES BY
CARBON NUMBER CATEGORY (Continued)
7-10
11 +
Paraffins
Olefins
Aldehydes
Primary and
Secondary alkyl
benzenes
Di alkyl Benzene
Paraffins
Olefins
Aldehydes
Mono. Tertiary
benzene
Primary and
Seconday alkyl
benzenes
Di alkyl benzenes
19
7
4
4
4
12
8
4
4
4
4
17
7
3
3
3
6
12
17
6
6
6
17
3
7
3
3
23
6
17
0
5
6
Tri-and Tetra-alkyl
benzenes
4
looT
6
"lOOT
0
^fOOT
TABLE 3-58
VARIATIONS IN THE COMPOSITION OF THE ORGANIC
EMISSIONS FROM GAS TURBINE (JET) AIRCRAFT 'ENGINES
WITH POWER SETTING [53]
Class
Class
Class
Class
Class
I
II
III
IV
V
Taxi -idle mode
9
4
38
16
33
~loo%
Takeoff-Climbout mode
2
6
25
18
49
nra
Approach mode
2
0
41
17
40
1M«
3-76
-------
Table 3-59 shows the composition of gas turbine exhaust organics.
These data were derived from Table 3-57 and weighted to account for
the fraction of time spent in each operating mode. Note that the
aliphatic aromatic ratio is about two to one, which agrees well with
data from two other jet engines at a total of five different power
settings, [50].
Although the fuels used in diesels and jet engines are chemically
similar, it would be expected that the composition of the exhaust hydro-
carbons would be substantially different due to the fundamental differences
in the combustion processes. In a diesel engine the fuel can continue
to burn for some time after the combustion products leave the combustion
cylinder. This would tend to result in lower molecular weight hydrocarbons
being emitted since the combustion would be more complete. In a gas turbine,
however, the hot combustion products must be cooled prior to passing through
the turbine blades. This is done by quenching the exhaust gases with
several volumes of relatively cool ambient air. Since this lowers the
temperature well below the temperature at which combustion can occur, com-
bustion effectively stops.
Piston Aircraft
Since reciprocating aircraft engines are fundamentally similar to
gasoline powered automobile engines, and since the fuel burned is similar,
it is expected that the composition of the hydrocarbons emitted would,
likewise, be similar. However, since aircraft engines are not subject to
emission controls, if automotive emissions were to be used to model air-
craft emissions, the lack of such controls had to be considered.
The organic composition data presented in Table 3-60 is the same as
that for an uncontrolled automobile engine, [55]. Since reciprocating aircraft
engines contribute a very small fraction of the total hydrocarbon emissions,
the effect of any errors that result from using the automotive approximation
is also small.
3-77
-------
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3-79
-------
3.5 DATA SUMMARY
The data presented in this chapter are subject to some limitations
which should be well understood before they are used for any other
purposes:
The data, in the strictest sense, apply only to the Los Angeles
AQCR; how the composition of the emissions from each source type
vary from one region to another is not known.
Some of the composition data are quite old.
Some of the data are estimates and not actual test results.
Tables 3-61 through 3-63 summarize the organic composition data for
2-Class, 5-Class and 6-Class reactivity schemes. In the 2-Class scheme,
the mole percent of compounds from stationary sources that fall in Class I
(unreactive) range from 0% to 100%. If the dry cleaning and degreasing
categories are omitted, the range is 4% to 90%. (The emissions from
dry cleaning and degreasing are unusual in that they are very simple
mixtures which contain only one or two classes of compounds). Conversely,
the reactive components comprise 10% to 96% of the total on a mole basis.
There does not appear to be any valid generalization regarding the fraction
of the hydrocarbons that are reactive for stationary sources.
The reactive mole fraction for mobile sources ranges from 67% to
95%. The range for exhaust emissions from gasoline powered vehicles and
equipment and diesel powered vehicles is 72% to 87% reactive mole fraction.
In the summary of the 5- and 6-Class schemes, the most notable
feature is the very small fraction of compounds, from all sources, that
fall into Class II of these schemes.
The mole fraction of methane for all sources varies from 0% to 78%
With the exception of petroleum production, fuel combustion, and waste
burning, the maximum fraction is 11%. The result is, that with the
exception of these three source types, there are only very small differences
between the 5- Class and the 6- Class reactivity schemes.
3-80
-------
TABLE 3-61 DISTRIBUTION OF ORGANIC COMPOUNDS IN A
2-CLASS REACTIVITY SCHEME
SOURCE CATEGORY
STATIONARY SOURCES - FUELS AND
COMBUSTION
Petroleum Production & Refining
Petroleum Production
Petroleum Refining
Gasoline Marketing
Underground Gasoline Storage
Tanks
Automobile Gasoline Tank Filling
Fuel Combustion
Waste Burning & Other Fires
STATIONARY SOURCES - ORGANIC CHEMICALS
Surface Coating
Heat Treated
Air Dried
Dry Cleaning
Petroleum Based Solvents
Synthetic Solvent (PCE)
Degreasing
TCE Solvent
1,1,1-T Solvent
Printing
Rotogravure
Flexi graphic
Industrial Process Sources
Rubber & Plastic Manufacturing
Pharmaceutical Manufacturing
Miscellaneous Chemical Manu-
facturing
MOBILE SOURCES
Light Duty Gasoline Powered Vehicles
Exhaust Emissions
Evaporative Emissions
Heavy Duty Gasoline Powered Vehicles
Exhaust Emissions
Evaporative Emissions
Other Gasoline Powered Equipment
Exhaust Emissions
Evaporative Emissions
Diesel Powered Vehicles
Aircraft
Jet
Diston
Mole %
CLASS I
84
11
18
4
90
74
20
14
0
100
0
100
16
19
16
34
44
28
5
28
5
28
5
13
9
34
CLASS II
16
89
82
96
10
26
80
86
100
0
100
0
84
81
84
66
56
72
95
72
95
72
95
87
91
66
3-21
-------
TABLE 3-62 DISTRIBUTION OF ORGANIC COMPOUNDS IN A
5-CLASS REACTIVITY SCHEME
SOURCE CATEGORY
STATIONARY SOURCES - FUELS AND COMBUSTION
Petroleum Production & Refining
Petroleum Production
Petroleum Refining
Gasoline Marketing
Underground Gasoline Storage Tanks
Automobile Gasoline Tank Filling
Fuel Combustion
Waste Burning & Other Fires
STATIONARY SOURCES - ORGANIC CHEMICALS
Surface Coating
Heat Treated
Air Dried
Dry Cleaning
Petroleum Based Solvents
Synthetic Solvents
Degreasing
TCE Solvent
1,1, 1-T Solvent
Printing
Rotogravure
Flexigraphic
Industrial Process Sources
Rubber & Plastic Manufacturing
Pharmaceutical Manufacturing
Miscellaneous Chemical Manufacturing
MOBILE SOURCES
Light Duty Gasoline Powered Vehicles
Exhaust Emission
Evaporative Emissions
Heavy Duty Gasoline Powered Vehicles
Exhaust Emissions
Evaporative Emissions
Other Gasoline Powered Equipment
Exhaust Emissions
Evaporative Emissions
Diesel Powered Vehicles
Aircraft
Jet
Piston
CLASS I
84
11
18
4
90
74
20
14
0
100
0
100
16
19
16
34
44
28
5
28
5
28
5
13
9
34
CLASS 11
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
1
0
0
0
0
0
0
0
0
4
0
Mole %
CLASS III
16
67
60
69
3
7
28
52
94
0
0
0
61
8
24
5
29
30
58
30
58
30
58
24
38
23
CLASS IV
0
8
0
9
1
3
50
29
5
0
100
0
23
73
7
60
18
19
21
19
21
19
21
6
16
10
CLASS V
0
14
22
18
6
16
2
5
1
0
0
0
0
0
52
0
9
23
16
23
16
23
16
57
33
33
3-82
-------
TABLE 3-63 DISTRIBUTION OF ORGANIC COMPOUNDS IN A
6-CLASS REACTIVITY SCHEME
Mole %
CLASS 0
SOURCE CATEGORY CCH4)
STATIONARY SOURCES - FUELS AND COMBUSTION
Petroleum Production & Refinfnq
Petroleum Production
Petroleum Refining
Gasoline Marketing
Underground Gasoline Storage Tanks
Automobile Gasoline Tank Filling
Fuel Combustion
Waste Burning & Other Fires
STATIONARY SOURCES - ORGANIC CHEMICALS
Surface Coating
Heat Treated
Ai r Dried
Dry Cleaning
Petroleum Based Solvents
Synthetic Solvents
Degreasing
TCE Solvent
1 ,1 ,1-T Solvent
Printing
Rotogrovure
Flexgraphic
Industrial Process Sources
Rubber 8 Plastic
rlanufacturing
Pharamaceuti-cal Manufacturing
Miscellaneous Chemical Manufacturing
MOBILE SOURCES
Light Duty Gasoline Powered Vehicles
Exhaust Emissions
Evaporative Emissions
Heavy Duty Gasoline Powered Vehicles
Exhaust Emissions
Evaporative Emissions
Other Gasoline Powered Equipment
Exhaust Emissions
Evaporative Emissions
Diesel Powered Vehicles
Aircraft
Jet
Piston
64
2*
3
0
78
59
2
0
0
0
0
0
0
0
0
0
0
10
0
10
0
10
0
11
2
18
CLASS I
20
9
15
4
12
15
18
14
0
100
0
100
16
19
16
34
44
18
5
18
5
18
5
2
7
16
CLASS II
0
0
0
0
0
0
0
0
0
0
0
0
0
0
1
1
0
0
0
0
0
0
0
0
4
0
CLASS III
16
67
60
69
3
7
28
52
94
0
0
0
61
8
24
5
29
30
58
30
58
30
58
24
38
23
CLASS IV
0
8
0
9
1
3
50
29
5
0
100
0
23
73
7
60
18
19
21
19
21
19
21
16
16
10
CLASS V
0
14
22
18
6
16
2
5
1
0
0
0
0
0
52
0
9
23
16
23
16
23
16
57
33
33
Estimated to be 1/3 of the C^ C., paraffin emissions for this category
3-83
-------
3.6 REFERENCES
1. Private communication, Robert Murray, Los Angeles County Air Pollution
Control District, Los Angeles, California, February 2, 1975.
2. Private communication, James Daley, Standard Oil Company, El Segundo,
California, February 12, 1975.
3. Private communication, Sanford Meiss, Los Angeles County Air Pollution
District, Los Angeles, California, November 1974; internal document
titled "Summary-Survey Questionnaire, Hydrocarbon Emissions."
4. Private communication, E. W. Mertens, Chevron Research Corporation,
Richmond, California, February 12, 1975.
5. Private communication, Jack Remnet, Atlantic Richfield Corporation,
Wilmington, California, February 12, 1975.
6. Private Communication, Morris Goldberg, Environmental Protection
Agency Region IX, San Francisco, California, January 31, 1975.
7. Private communication, Sanford Weiss, Los Angeles County Air Pollution
Control District, Los Angeles, California, January 23, 1975.
8. Private communication, Robert Murray, Los Angeles County Air Pollution
Control District, Los Angeles, California, January 31, 1975.
9. Profile of Air Pollution - 1971, Los Angeles County Air Pollution
Control District, Los Angeles, California, 1971.
10. Air Pollution Engineering Manual, 2nd Ed., John A. Danielson, Environ-
mental Protection Agency, Research Triangle Park, N.C., May 1973.
11. R. L. Martin and J. C. Winters, "Determination of Hydrocarbons in
Crude Oil by Capillary-Column Gas Chromatography," Analytical Chemistry.
Vol. 35, Ho. 12, pg. 1930-33, November 1963.
12. A. C. Stern, Air Pp11ution-Volume 3, 2nd Edition, Chapter 34, Academic
Press, New York, 1968.
13. W. N. Sanders and J. B. Maynard, "Capillary Gas Chromatographic
Method for Determining C3-C [sic] Hydrocarbons in Full Range Motor
Gasolines," Analytical Chemistry, Vol. 40, No. 3, pg 527-535, March
1968.
14. Private communication, Los Angeles County Air Pollution Control
District, November 1974, internal document titled "Liquid and Equili-
brium Vapor Analysis (APCD)-Test No. C-1840," August 9, 1972.
15. Private communication, Henry flayrsohn, California Air Resources
Board, El Monte California, January 23, 1975.
3-84
-------
16. "Gasoline Modification-Its Potential as an Air Pollution Control
Measure in Los Angeles County," joint project, California Air
Resources Board, Los Angeles County Air Pollution Control District,
and Western Oil and Gas Association, November 1969.
17. John C. Trijonis, An Economic Air Pollution Control Model-Application;
Photochemical Smog in Los Angeles County in 1975, Ph.D. Thesis,
California Institute of Technology, Pasadena, California, May 1972.
18. Stephen S. Visher, Climatic Atlas of the United States, Harvard
University Press, Cambridge, Mass., 1954.
19. Climatic Atlas of the United States, U. S. Department of Commerce,
June 1968.
20. Private communication, Howard W. Linnard, California State Air
Resources Board, March 1975.
21. M. R. Brunelle, J. E. Dickinson and W. J. Hamming, Effectiveness
of Organic Solvents in Photochemical Smog Formation, Los Angeles
County Air Pollution Control District, July 1966.
22. Rules and Regulations. Los Angeles County Air Pollution Control
District.(no date)
23. Private communication, Sanford Weiss, Los Angeles County Air Pollu-
tion Control District, January 1975.
24. Private communication, Charles Finnegan, Ameritone Paint Corporation,
Los Angeles, California, January 1974.
25. Private communication, Raymond J. Connor, Assistant Technical Director,
National Paint & Coating Association, Washington, D.C., Nov. 5, 1974.
26. Private communication, Fred Thoits, Environmental Protection Agency
Region IX, October 1974; data contained in letter from B. A. Thomas,
Office Manager, Ashland Chemical Company, Santa Fe Springs, California,
dated February 19, 1974.
27. Private communication, William Ellis, Chevron Research Company, El
Segundo, California, January 1975.
28. Private communication, Fred Thoits, Environmental Protection Agency
Region IX, October 1974; data contained in letter from E. E. Loveland,
Region Technical Service Manager, AMSCO Division, Union Oil Company
of California, LaMirada, California, dated March 21, 1974, and
AMSCO Product Bulletin 140 Solvent 66/3.
29. Private communication, Fred Thoits, Environmental Protection Agency
Region IX, October 1974; data contained in letter from Chevron
Research Company, El Segundo, California, date unknown.
3-85
-------
30. Private communication, Fred Thoits, Environmental Protection Agency
Region IX; October 1974, data contained in a document from the
Shell Oil Company which gives specifications for solvents distributed
west of the Rocky Mountains.
31. Private communication, George Thomas, Los Angeles County Air Pollu-
tion Control District, February 1975.
32. Private communication, George Rhett, Los Angeles County Air Pollu-
tion Control District, February 1975.
33. Private communication, George Thomas, Los Angeles County Air Pollu-
tion Control District, "APCD Organic Solvent Inventory for 1965,"
February 1975.
34. Private communication, Robert Thomas and Jerry Smernott, Ashland
Chemical Company, Santa Fe Springs, California, January 1975.
35. Private communication, E. E. Loveland, Region Technical Service
Manager, AMSCO Division of Union Oil Company of California, La Mirada,
California, January 1975.
36. R. D. Fleming, "Effect of Fuel Composition of Exhaust Emissions
from a Spark-Ignition Engine," U.S. Department of the Interior,
Bureau of Mines, Report of Investigations #7423. (no date)
37. E. E. Wigg, R. J. Champion, and W. L. Peterson, "The Effect of Fuel on
Hydrocarbon and Oxygenate Emissions," Society of Automotive Engineers
Report #720251, presented to the Automotive Engineering Congress,
Detroit, Michigan, January 10-14, 1972.
38. B. Dimitriades, B. H. Eccleston, and R. W. Hum, "An Evaluation of
the Fuel Factor Through Direct Measurement of Photochemical Reactivity
of Emissions," J. APCA. Vol. 20, No. 3, pg. 150-160, March 1970.
39. J. S. Ninorniya and B. Biggers, "Effects of Toluene Content in Fuel
on Aromatic Emissions in the Exhaust," J. APCA. Vol. 20, No. 9,
pg. 603-611, September 1970.
40. J. M. Heuss, G. J. Nebel, and B. A. O'Alleva, "Effects of Gasoline
Aromatic and Lead Content on Exhaust Hydrocarbon Reactivity,"
Environmental Science and Technology, Vol. 8, No. 7, pg. 641-647,
July 1974.
41. K. T. Dishart and W. E. Harris, "The Effect of Gasoline Hydrocarbon
Composition on Automotive Exhaust Emissions," Proc. Am. Petroleum
Inst. Div. Refin., Vol 48, pg. 612-642, 1968.
42. W. E. Morris and K. T. Dishart, "Effect of Automotive Emission
Requirements on Gasoline Characteristics," ASTM Special Technical
Publication 487, pg. 63-93, presented at the Seventy-third Annual
Meeting, American Society for Testing and Materials, Toronto,
Ontario, Canada, June 21-26, 1970.
3-86
-------
43. Private communication, Henry Mayrsohn, California Air Resources
Board, El Monte, California, November 1974; results of tests of
automotive hydrocarbon emissions in two long highway tunnels.
44. Private communication, Henry Mayrsohn, California Air Resources
Board, El Monte, California, January 1975.
45. Private communication, William MacBeth, Los Angeles County Air
Pollution Control District, January 23, 1975.
46. C. W. Spicer and A. Levy, "The Photochemical Smog Reactivity of
Diesel Exhaust Organics," report to the Coordinating Research Council
from Battelle Columbus Laboratories, May 1975.
47. (a) "Chemical Identification of the Odor Components in Diesel Engine
Exhaust," Final Report to CRC and PHS, PHS Contract No. PH 22-68-20,
CRC Project No. CAPE-7, July 1969,
(b) "Chemical Identification of the Odor Components in Diesel Engine
Exhaust," Final Report to CRC and HEW, HEW Contract No. CAP-22-69-63,
CRC Project No. CAPE 7-68, June 1970,
(c) "Chemical Identification of the Odor Components in Diesel Engine
Exhaust," Final Report to CRC and EPA, EPA Contract No. EHSD 71-18,
CRC Project No. CAPE 7-68, June 1971 ; as reported in Reference 46.
48. Private Communication, P. Levins, Arthur D. Little, Inc., 1974, as
reported in Reference 46.
49. K. J. Springer, "Emissions from a Gasoline- and Diesel-Powered
Mercedes 220 Passenger Car," report to EPA, Contract No. CPA-70-44,
June 1971, as reported in Reference 46.
50. R. H. Groth and D. J. Robertson, "Reactive and Unreactive Hydro-
carbon Emissions from Gas Turbine Engines," APCA #74-89, presented
at the 67th Annual Meeting of the Air Pollution Control Association,
Denver, Colorado, June 9-13, 1974.
51. K. H. Becker and J. Schurath, "Photo-Oxidation of Aircraft Engine
Emissions at Low and High Altitudes," Institut fur Physikalisch
Chemie der Universitat Bonn, W. Germany, AGARD-CP-125.
52. "Compilation of Air Pollution Emission Factors," AP-42, Second Addi-
tion, Environmental Protection Agency, April 1973.
53. J. 0. Chase and R. W. Hum, "Measuring Gaseous Emissions from an
Aircraft Turbine Engine," SAE #700249, presented at the Society of
Automotive Engineers National Air Transportation Meeting, New York,
April 20-23, 1970.
54. A. W. Wilson, "Detailed Exhaust Emission Measurements of Three
Different Turbofan Engine Designs," AGARD Conference Proceedings,
No. 125, April 9-13, 1974, AGARD-CP-125.
3-87
-------
55. W. E. Morris and K. T. Dishart, "Influence of Vehicle Emission
Control Systems on the Relationship Between Gasoline and Vehicle
Exhaust Hydrocarbon Composition," Effect of Automotive Emission
Requirements on Gasoline Characteristics, ASTM Special Technical
Publication 487, presented at the Seventy-third Annual Meeting
American Society for Testing and Materials, Toronto, Ontario,
Canada, 21-26 June 1970, pg. 63-94.
Back g r o u n d Ma ten' a 1:
Petroleum Refining
R. L. Martin, John C. Winters, and J. A. Williams, "Composition of
Crude Oils by Gas Chromatography: Geological Significance of Hydro-
carbon Distribution," Proc. 6th World Petrol Congr, Sect V, Paper
13, Frankfurt, Germany, 1963.
I. A. Musayev, et. al., "Investigations of the Chemical Composition
of Middle Distillates of Sulphur Bearing Crude Oil of the USSR,"
Proc. 6th World Petrol, Congr., Sect. V, Paper 21, Frankfurt,
Germany, 1963.
L. L. Laster, "Atmospheric Emissions from the Petroleum Refining
Industry," Environmental Protection Agency, Research Triangle Park,
N.C., August 1973, PB 225-040, EPA-650/2-73-017.
Waste Burning and Other Fires
W. N. Tottle and M. Feldstein, "Gas Chromatographic Analysis of
Incinerator Effluents," J. APCA. Vol. 10, No. 6, December 1960.
E. F. Darley, et. al, "Contribution of Burning of Agricultural Waste
to Photochemical Air Pollution, J. APCA, Vol. 11, No. 12, December 1966.
R. L. Sterburg, et. al., "Field Evaluation of Combustion Air Effects
on Atmospheric Emissions from Municipal Incinerators," J. APCA, Vol.
12, No. 2, February 1962.
R. W. Gerstle and D. A. Kemnitz, "Atmospheric Emissions from Open
Burning," J. APCA. Vol. 17, No. 5, May 1967.
R. W. Babel, E. F. Darley, and E. A. Schuck, "Emissions from Burning
Grass Stubble and Straw," J. APCA, Vol. 19, No. 7, July 1969.
R. L. Sterburg, et. al., "Effects of High Volatile Fuel on Incinerator
Effluents," presented at the 53rd Annual Meeting of APCA, Netherland
Hilton Hotel, Cincinnati, Ohio, May 22-26, 1960.
Gasoline Powered Vehicles
Effect of Automobile Emission Requirements on Gasoline Characteristics,
ASTM Special Technical Publication 487, a Symposium presented at the
Seventy-third Annual Meeting, American Society for Testing and Materials,
3-88
-------
B. Dimitriades, B. H. Eccleston, and R. W. Hum, "An Evaluation of
the Fuel Factor Through Direct Measurement of Photochemical Reactivity
of Emissions," J. APCA, Vol. 20, No. 3, March 1970.
E. E. Wigg, R. J. Campion, W. L. Peterson, "The Effect of Fuel Hydro-
carbon Composition on Exhaust Hydrocarbon and Oxygenate Emissions,"
Society of Automotive Engineers Paper #720251, presented at the
Automotive Engineering Congress, Detroit, Mich.
B. Dimitriades and T. C. Wesson, "Reactivities of Exhaust Aldehydes,"
U. S. Department of the Interior, Report of Investigations 7527,
May 1971.
R. D. Fleming, "Effect of Fuel Composition on Exhaust Emissions from
A Spark-Ignition Engine," U. S. Department of Interior, Report of
Investigations #7423. (No Date).
J. S. Ninomiya and B. Biggers, "Effects of Toluene Content in Fuel
on Aromatic Emissions in the Exhaust," J. APCA, Vol. 20, No. 9,
September 1970.
J. M. Heuss, G. J. Nebel, and B. A. D'Alleua, "Effects of Gasoline
Aromatic and Lead Content on Exhaust Hydrocarbon Reactivity,"
Environmental Science and Technology, Vol. 8, No. 7, July 1974.
Diesel Exhaust Emissions
L. R. Reckner, W. E. Scott, and W. F. Biller, "The Composition and
Odor of Diesel Exhaust," Proc. of the Amer. Petroleum Institute, 48,
133-144, 1965.
E. W. Landen and J. M. Perez, "Some Diesel Exhaust Reactivity Infor-
mation Derived by Gas Chromatography," Society of Automotive Engineers
740530, presented at the Combined Commercial Vehicle and Fuels and
Lubricants Meetings, Chicago, Illinois, June 17-21, 1974.
H. R. Taliaferro, J. 0. Becker, and T. 0. Wagner, "Atmospheric Pollu-
tion from Diesel Engines," presented at the Seventh World Petroleum
Conf., Mexico City, April 1967.
H. C. Lord, et. al., "Measurement of Exhaust Emissions in Piston and
Diesel Engines by Dispersive Spectroscopy," J. APCA, Vol. 24, No. 2,
February 1974.
3-89
-------
4.0 SOURCE REACTIVITY RATINGS AND
REACTIVE ORGANIC INVENTORIES
This chapter synthesizes the information presented in previous chapters
to derive source reactivity ratings and reactive emission inventories for
organic sources in the Metropolitan Los Angeles AQCR. Section 4.1 presents
source molar reactivities for each of the 2-, 5-, and 6- group reactivity
classification schemes. Section 4.2 gives corresponding source weight
reactivities. Finally, Section 4.3 combines the source reactivity ratings
with the total organic inventory to arrive at reactive organic inventories
according to the 2-, 5-, and 6- group schemes. Each section includes a
discussion of the principal features in the numerical results.
4.1 SOURCE MOLAR REACTIVITIES
Table 4-1 lists source molar reactivities for each of the 17 types of
stationary sources and 9 types of mobile sources considered in this study.
The source molar reactivities are presented for the 2-, 5-, and 6-group
reactivity classification schemes. These reactivities have been cal-
culated from the source organic composition data summarized in Table 3-63
and from the reactivity factors for the 2-, 5-, and 6-group schemes listed
in Table 1-2. It should be re-emphasized that the reactivities based on
the 5- and 6-group schemes are relative, and that the scales for these
schemes have been chosen such that auto exhaust retains the same absolute
rating for all three classification schemes.
Several features of Table 4-1 deserve special comment. The raost
important result is that molar reactivities are fairly uniform among
4-1
-------
TABLE 4-1. SOURCE MOLAR REACTIVITIES FOR THE
2-, 5-, AND 6- GROUP SCHEMES
SOURCE CATEGORY
STATIONARY SOURCES: ORGANIC FUELS
AND COMBUSTION
Petroleum Production and Refining
Petroleum Production
Petroleum Refining
Gasoline Marketing
Underground Service
Station Tanks
Auto Tank Filling
Fuel Combustion
Waste Burning & Fires
STATIONARY SOURCES-ORGANIC CHEMICALS
Surface Coating
Heat Treated
Air Dried
Dry Cleaning
Petroleum Based Solvent
Synthetic Solvent (PCE)
Degreasing
TCE Solvent
1,1, 1-T Solvent
Printing
Rotogravure
Flexigraphic
Industrial Process Sources
Rubber S Plastic Manf.
Pharmaceutical Manf.
Miscellaneous Operations
MOBILE SOURCES
Gasoline Powered Vehicles
Light Duty Vehicles
Exhaust Emissions
Evaporative Emissions
Heavy Duty Vehicles
Exhaust Emissions
Evaporative Emissions
Other Gasoline Powered Equipment
Exhaust Emissions
Evaporative Emissions
Diesel Powered Motor Vehicles
Aircraft
Jet
Piston
WEIGHTED AVERAGE
OF ALL SOURCES
2-GROUP
SCHEME
.16
.89
.82
.96
.10
.26
.80
.86
1.00
.00
1.00
.00
.84
.81
.84
.66
.56
.72
.95
.72
.95
.72
.95
.87
.91
.66
0.70
SOURCE MOLAR REACTIVITIES
5-GROUP
SCHEME
.19
.71
.71
.78
.20
.37
.70
.69
.66
.10
.95
.10
.62
.76
.97
.64
.53
.72
.80
.72
.80
.72
.80
1.02
.88
.74
0.66
6-GROUP
SCHEME
.12
.71
.71
.79
.12
.32
.70
.69
.66
.10
.95
.10
.o2
.76
.98
.64
.53
.72
.80
.72
.80
.72
.80
1.01
.88
.72
0.66
4-2
-------
most of the source types. Twenty-one of the 26 major source types have
molar reactivities in the range .66 to 1.00 for the 2- group scheme, .62
to 1.02 for the 5-group scheme, and .62 to 1.01 for the 6-group scheme.
Only five types of sources have very low molar reactivity: petroleum
production, fuel combustion, waste burning & fires, synthetic dry cleaning
solvent (PCE), and 1,1,1-T degreasing. Each of these categories have large
fractions of emissions in Class I of the reactivity classification scheme.
The reason for the general uniformity is that the emissions from
many sources tend to consist largely of compounds in Classes III and IV of
the reactivity classification scheme (See Table 3-63). This provides for
a general homogeneity of source molar reactivities. The fractions which
tend to occur in Classes 0, I and V lead to some deviations in individual
source reactivity ratings, but these deviations are not very great (with
the five exceptions noted above).
Another significant feature of the source molar reactivity listing
is that the reactivities for the 5-group and 6-group schemes are nearly
identical. The reader is reminded that the difference between the 5-group
and 6-group schemes is that methane is assigned a molar reactivity of .1
in the 5-group scheme but is assigned zero reactivity in the 6-group
scheme. Basically, the only sources which are affected by this change are
petroleum production, fuel combustion, and waste burning & fires.
Methane is a significant portion of the emissions from each of these three
source types.
Relative source molar reactivities are significantly different for
the 2-group and 5-group schemes. The 5-group rating has been calibrated so
that light duty vehicle exhaust (.72) is the same in each scheme. Ratings
for other gasoline engines, degreasing solvents, pharmaceutical manufacturing,
and miscellaneous chemical manufacturing also remain about the same for each
scheme. However, relative reactivity ratings with the 5-group scheme are
significantly lower than with the 2-group scheme for sources involving
evaporated gasoline, surface coatings, petroleum dry cleaning solvent,
4-3
-------
and printing solvents. On the other hand, relative reactivity ratings
become greater with the 5-group scheme for petroleum production, fuel
combustion, waste burning, rubber/plastic manufacturing, diesels, and
aircraft.
4.2 SOURCE WEIGHT REACTIVITIES
Source weight reactivities (SWR ) for the k-group scheme are calculated
from source molar reactivities according to the formula,
k MWex
SWRK = e
MW
where
SMR = the (k-group) source molar reactivity of the source in question,
MW = the average molecular weight of auto exhaust,
cX
and MW = the average molecular weight of the source in question. The
above formula has been chosen so that auto exhaust will again have a re-
activity of .72. All other sources will have source weight reactivities
relative to auto exhaust in proportion to reactive moles per unit weight of
emissions. It should be noted that source weight reactivity for the 2-group
scheme is not the per cent by weight of reactive emissions (See Section 1.1).
Table 4-2 lists the source weight reactivities for each of the 17 types
of stationary sources and 9 types of mobile sources considered in this study.
Also listed for comparison are the source molar reactivities and the average
source molecular weights.
The source weight reactivities show about the same overall uniformity
as the source molar reactivities. For instance, the most reactive 21 of the
26 source types have weight reactivities in the range .52 to .98 for the 2-
group scheme and .60 to .92 for the 5-group scheme. Similar ranges for source
molar reactivities are .66 to 1.00 and .62 to 1.01, respectively.
As with the source molar reactivities, there is little difference between
the 5-group and 6-group schemes, with the exception of petroleum production,
fuel combustion, and waste burning and fires. Also, there again is a signifi-
cant change in relative source reactivities between the 2-group and 5-group
schemes.
4-4
-------
TABLE 4-2 SOURCE WEIGHT REACTIVITIES FOR THE
2-, 5-, AND 6- GROUP SCHEMES
SOURCE CATEGORY
STATIONARY SOURCES: ORGANIC FUELS
AND COMBUSTION
Petroleum Production and Refining
Petroleum Production
Petroleum Refining
Gasoline Marketing
Underground Service
Station Tanks
Auto Tank Filling
Fuel Combustion
Waste Burninq & Fires
STATIONARY SOURCES-ORGANIC CHEMICALS
Surface Coating
Heat Treated
Air Dried
Dry Cleaning
Petroleum Based Solvent
Synthetic Solvent (PCE)
Degreasing
TCE Solvent
1,1, 1-T Solvent
Printing
Rotogravure
Flexigraphic
Industrial Process Sources
Robber & Plastic Manf.
Pharmaceutical Manf.
Miscellaneous Operations
MOBILE SOURCES
Gasoline Powered Vehicles
Light Duty Vehicles
Exhaust Emissions
Evaporative Emissions
Heavy Duty Vehicles
Exhaust Emissions
Evaporative Emissions
Other Gasoline Powered Equipment
Exhaust Emissions
Evaporative Emissions
Diesel Powered Motor Vehicles
Aircraft
Jet
Piston
WEIGHTED AVERAGE
OF ALL SOURCES
SOURCE MOLAR REACTIVITIES
2-GROUP 5-GROUP 6-GROUP
SCHEME SCHEME SCHEME
.16 .19 .12
.89 .71 .71
.82 .71 .71
.96 .78 .79
.10 .20 .12
.26 .37 .32
.80 .70 .70
.86 .69 .69
1.00 .66 .66
.00 .10 .10
1 . 00 .95 .95
.00 .10 .10
.34 .02 .62
.81 .76 .76
.84 .97 .98
.66 .64 .64
.56 .53 .53
.72 .72 .72
.95 .80 .80
.72 .72 .72
.95 .80 .80
.72 .72 .72
.95 .80 .80
.87 1.02 1.01
.91 .88 .88
.66 .74 .72
0.70 0.66 Q.66
AVERAGE
MOLECULAR
WEIGHT
29
93
58
74
25
33
82
87
126
166
132
134
82
57
73
75
80
69
91
69
91
69
91
89
121
56
71.9
SOURCE WEIGHT REACTIVITIES
2-GROUP 5-GROUP 6-GROUP
SCHEME SCHEME SCHEME
.38 .45 .29
.66 .53 .53
.98 .84 .84
.90 .73 .74
.28 .55 .33
.54 .77 .67
.67 .59 .59
.68 .55 .55
.55 .36 .36
.00 .04 .04
.52 .50 .50
.00 .05 .05
.69 .52 .52
.98 .92 .92
.79 .92 .93
.61 .59 .59
.48 .46 .46
.72 .72 .72
.72 .61 .61
.72 .72 .72
.72 .61 .61
.72 .72 .72
.72 .61 .61
.67 .79 .78
.52 .50 .50
.81 .91 .89
0.67 0.64 0.63
4-5
-------
The most important feature of Table 4-2 is the difference in relative
ratings of various sources for molar vs. weight reactivities. Sources with
high average molecular weight are of lesser relative importance for weight re-
activity. For instance, TCE degreasing solvent is one of the most reactive source
categories according to molar reactivity but is one of the least reactive
categories according to weight reactivity. Other sources that have weight
reactivities that are notably lower than molar reactivities are petroleum
refining, surface coating, dry cleaning, rotogravure printing, evaporative
emissions from automobiles, diesels, and jet aircraft. Sources with low average
molecular weight become of greater relative importance in terms of weight
reactivity. For instance, the relative weight reactivities of petroleum
production, fuel combustion, and waste burning & fires are more than twice
their molar reactivities. Other sources with low average molecular weights
(and higher weight reactivities) are underground service station tanks,
flexigraphic printing, and piston aircraft.
4.3 REACTIVE EMISSIONS
Reactive emissions are computed as a product of total weight emissions
times source weight reactivity. A molar reactive emission scale directly
proportional to the weight reactive emission scale can be calculated by multi-
plying total molar emissions by source molar reactivity. Table 4-3 presents
reactive weight emissions for the 2-, 5-, and 6- group reactivity classifi-
cation schemes. Also presented are the percentage contributions of each
source type to total reactive emissions. Table 4-3a is in English units,
while Table 4-3b is in metric units.
Table 4-3 illustrates that the percentage contribution of some sources
changes significantly when reactivity factors are added to total organic
emissions. For instance, petroleum production constitutes 2.3% of total
weight emissions but only 1.4%, 1.7%, and 1.1% of 2-, 5-, and 6- group
reactive emissions, respectively. Synthetic dry cleaning solvent (PCE)
comprises 1.0% of total organic emissions by weight but only, 0.0%, 0.1%,
and 0.1% of reactive emissions for the three reactivity schemes, respectively.
1,1,1-T solvent comprises 3.6% of total organics but only 0.0%, 0.3%, or 0.3%
of reactive organics. Rubber and plastic manufacturing accounts for 1.6% of
total emissions but 1.9%, 2.3%, or 2.4% of reactive emissions. Underground
4-6
-------
TABLE 4-3. REACTIVE EMISSION INVENTORIES FOR
THE 2-, 5-, AND 6- GROUP SCHEMES
(English Units)
SOURCE CATEGORY
STATIONARY SOURCES: ORGANIC FUELS
AND COMBUSTION
Petroleum Production and Refining
Petroleum Production
Petroleum Refining
Gasoline Marketing
Underground Service
Station Tanks
Auto Tank Filling
Fuel Combustion
Waste Burning & Fires
STATIONARY SOURCES-ORGANIC CHEMICALS
Surface Coating
Heat Treated
Air Dried
Dry Cleaning
Petroleum Based Solvent
Synthetic Solvent (PCE)
Degreasing
TCE Solvent
1,1, 1-T Solvent
Printing
Rotogravure
Flexigraphic
Industrial Process Sources
Rubber 8 Plastic Manf.
Pharmaceutical Manf.
Miscellaneous Operations
MOBILE SOURCES
Gasoline Powered Vehicles
Light Duty Vehicles
Exhaust Emissions
Evaporative Emissions
Heavy Duty Vehicles
Exhaust Emissions
Evaporative Emissions
Other Gasoline Powered Equipment
Exhaust Emissions
Evaporative Emissions
Diesel Powered Motor Vehicles
Aircraft
Jet
Piston
TOTAL
TOTAL EMISSIONS
TONS/DAY % OF TOTAL
62 2.3
50 1.9
48 1.8
104 4.0
23 0.9
41 1.6
14 0.5
129 5.0
16 0.6
25 1.0
11 0.4
95 3.6
31 1.2
15 0.6
42 1.6
16 0.6
83 3.2
780 30.0
481 18.5
285 10.9
67 2.6
110 4.2
22 0.8
12 0.5
20 0.8
22 0.9
2604 lOOiS
REACTIVE EMISSIONS
REACTIVE TONS/DAY*
2-GROUP 5-GROUP 6-GROUP
SCHEME SCHEME SCHEME
24 28 18
33 27 27
47 40 40
94 76 77
6 13 8
22 32 27
988
88 71 71
966
0 1 1
6 5 5
0 5 5
21 16 16
15 14 14
33 39 39
10 9 9
40 38 38
562 562 562
346 293 293
205 205 205
48 41 41
79 79 79
16 13 13
899
10 10 10
18 20 20
1749 1660 1641
PERCENT OF TOTAL
2-GROUP 5-GROUP 6-GROUP
SCHEME SCHEME SCHEME
!* 1.7 1.1
1.9 1.6 1.6
2.7 2.4 2.4
5.4 4.6 4.7
0.3 0.8 0.5
1.3 1.9 1.6
0.5 0.5 0.5
5.0 4.3 4.3
0.5 0.4 0.4
0.0 0.1 0.1
0.3 0.3 0.3
0.0 0.3 0.3
1.2 1.0 1.0
0.8 0.8 0.8
1.9 2.3 2.4
0.6 0.5 0.5
2.3 2.5 2.3
32.1 33.9 34.2
19.8 17.7 17.9
11.7 12.3 12,5
2.7 2.5 2.5
4.5 4.8 4.8
0.9 0.8 0.8
0.5 0.5 0.5
0.6 0.6 0.6
1.0 1.2 1.2
100% 100% 100%
* To convert to reactive ton moles per day, multiply by 0.0145
4-7
-------
TABLE 4-3. REACTIVE EMISSION INVENTORIES FOR (continued)
THE 2-, 5-, AND 6- GROUP SCHEMES
(Metric Units)
SOURCE CATEGORY
STATIONARY SOURCES- ORGANIC FUELS
ftND COMBUSTION
Petroleum Production and Refining
Petroleum Production
Petroleum Refining
Gasoline Marketing
Underground Service
Station Tanks
Auto Tank Filling
Fuel Combustion
Waste Burning $ Fires
STATIONARY SOURCES-ORGANIC CHEMICALS
Surface Coating
Heat Treated
Air Dried
Dry Cleaning
Petroleum Based Solvent
Synthetic Solvent (PCE)
Deqreasing
TCE Solvent
1,1, 1-T Solvent
Printing
Rotogravure
Flexigraphic
Industrial Process Sources
Rubber & Plastic Manf.
Pharmaceutical Manf.
Miscellaneous Operations
MOBILE SOURCES
Gasoline Powered Vehicles
Light Duty Vehicles
Exhaust Emissions
Evaporative Emissions
Heavy Duty VEhicles
Exhaust Emissions
Evaporative Emissions
Other Gasoline Powered Equipment
Exhaust Emissions
Evaporative Emissions
Diesel Powered Motor Vehicles
Aircraft
Jet
Piston
TOTAL
TOTAL EMISSIONS
METRIC * OF
TONS/DAY TOTAL
56 2.3
45 1.9
44 1.8
94~ 4.0
21 0.9
37 1.6
13 0.5
117 5.0
15 0.6
23 1.0
10 0.4
86 3.6
28 1.2
14 0.6
38 1.6
15 0.6
75 3.2
707 30.0
436 18.5
258 10.9
61 2.6
100 4.2
20 0.8
11 0.5
18 0.8
20 0.9
2362 100%
REACTIVE EMISSIONS
REACTIVE METRIC TONS/DAY*
2-GROUP 5-GROUP 6-GROUP
SCHEME SCHEME SCHEME
21 25 16
30 24 24
43 36 36
85 69 70
5 12 7
20 29 24
8 7 7
80 64 64
855
0 1 1
5 5 5
044
19 15 15
14 13 13
30 35 35
988
36 34 34
510 510 510
314 266 266
186 186 186
44 37 37
72 72 72
15 12 12
7 9 9
999
16 18 18
1586 1505 H87
PERCENT OF TOTAL
2-GROUP 5-GROUP 6-GROUP
SCHEME SCHEME SCHEME
1-4 1.7 1.1
1.9 1.6 1.6
2.7 2.4 2.4
5.4 4.6 4.7
0.3 0.8 0.5
1.3 1.9 1.6
0.5 0.5 0.5
6.0 4.3 4.3
0.5 0.4 0.4
0.0 0.1 0.1
0.3 0.3 0.3
0.0 0-3 0.3
1.2 1.0 1.0
0.9 0.8 0.9
1.9 2.3 2.4
0.6 0.5 0 5
2.3 2.3 2.3
32.1 33.9 34.2
19.8 17.7 17.9
11.7 12.3 12.5
2.7 2.5 2.5
4.5 4.8 4.8
0.9 0.8 0.8
0.5 0.5 0.5
0.6 0.6 0.6
1.0 1.2 1.2
ioo« loor, 100%
To convert to reactive metric ton moles per day, multiply by 0.0145
4-8
-------
service station tanks constitute 1.8% of total emissions but 2.7%,2-^
or 2.4% of reactive omissions.
The relative contribution of exhaust emissions from gasoline engines is
not significantly affected by using reactivity criteria. The contribution
from exhaust of all gasoline engines (LDV's, HDV's, and other equipment)
is 45.1% of the total organic inventory. Using the 2-, 5-, and 6- group
schemes, the contribution to reactive organics is 48.3%. 51.0% and 51.5%
respectively.
Likewise, the relative contribution of evaporative emissions from
gasoline engines (LDV's, HDV's, and other equipment) is not significantly
altered. These emissions contribute 21.9% to the total organic inventory
and 23.4%, 21.0% & 21.2% to reactive inventories based on the 2-, 5-,
& 6- group schemes, respectively.
All in all, the impact of using various reactivity criteria to compute
relative source contributions is certainly less than dramatic. Generally,
the total organic inventory is quite similar to each of the three reactive
inventories. The only notable differences occur among minor source types.
The overall similarity between the nonreactive and reactive inventories
may be a preliminary indication that a general policy of indiscriminate
control (with special considerations for only a few sources) is an appropri-
ate strategy for organics. However, it is premature to adopt this conclusion.
Chapter 6 will perform more in-depth analyses in order to determine the
costs and benefits involved in applying reactivity criteria to organic
control policy.
4-9
-------
5.0 EMISSION REDUCTION STRATEGIES FOR ORGANIC SOURCES
The previous chapter derived reactivity ratings for organic emission
sources in the Metropolitan Los Angeles AQCR. These reactivity ratings are
important to organic control policy because they allow a selective approach
to be taken in formulating emission reduction strategies. The present
chapter determines source emission reductions based on reactivity criteria
and compares these results to strategies based on indiscriminate control of
organics.
This chapter is organized in three sections. Section 5.1 discusses
the overall degree of reactive organic control that is required to attain
the national air quality standard for oxidant in the Los Angeles region.
It is found that substantial uncertainty surrounds present estimates for
degree of control required and that even 100% control of man-made sources
may not be sufficient to attain the oxidant air quality standard. An over-
all reduction of reactive organics by 90% is selected as an arbitrary target
level for the purposes of this study. Section 5.2 describes guidelines for
determining individual source emission reductions which attain a given over-
all degree of control. These guidelines include economic efficiency principles
as well as criteria which can be used when economic data are unavailable.
Section 5.3 determines emission reductions for individual organic source
categories for the Metropolitan Los Angeles AQCR. The emission reductions
are determined both for indiscriminate control and control based on reactivity
ratings.
5.1 OVERALL DEGREE OF REACTIVE HYDROCARBON CONTROL REQUIRED FOR LOS ANGELES
Considerable uncertainty surrounds the relationship between ambient
oxidant levels and precursor emission levels. This uncertainty has resulted
in an ongoing controversy concerning the percentage reduction in reactive
organic emissions that would be necessary to achieve the national ambient
air quality standard for oxidant in the Los Angeles region. On one hand,
it can be argued that background sources of reactive hydrocarbons are
sufficiently large to produce violations of the oxidant standard in Los Angeles
even if all man-made hydrocarbon sources were completely eliminated. At the
5-1
-------
opposite extreme, it has been contended that the present new car control
program may attain the oxidant air quality standard in Los Angeles in the
early 1980's [1], even though the associated reduction in total regionwide
organic emissions will be only about 60% from 1972 levels.
In this study, it will not be possible to resolve the issue concerning
the degree of reactive organic emission reduction required for Los Angeles.
However, to put some light on the issue, the problem will be reviewed below
using the results of several recent oxidant air quality analyses. This
review will indicate that the overall reactive organic reduction for Los
Angeles should be at least 85% and probably as high as 95%.
There are several factors leading to uncertainty concerning the overall
reduction in reactive organic emissions that is required to attain the
oxidant standard. A principal factor is the lack of a reliable modelling
methodology for relating oxidant concentrations to HC and NO precursors.
X
Three general modelling approaches have been followed: smog chamber simulation,
statistical/empirical analysis of aerometric data, and mathematical physico-
chemical modelling. Presently, each approach involves very significant
limitations. Here, the results of several empirical and smog chamber models
will be reviewed to summarize existing evidence pertaining to the degree of
reactive organic control needed for Los Angeles.
A second important area of uncertainty involves background levels, both
for hydrocarbons and for ozone. A very recent study indicates that about
12 to 13%* by weight of nonmethane organics in the Los Angeles atmosphere are
from "geogenic" sources, [2]. The existence of this background level limits
the oxidant reductions that can be achieved by controlling the source categories
listed in the man-made emission inventory. Existing air quality models do
not account for the background organic level.
Present air quality models also neglect background ozone contributions.
Natural background ozone apparently occurs in the range of .01 to -06 PPM [3],
a significant level compared to the .08 PPM air quality standard. However,
neglecting background ozone in modelling the Los Angeles urban atmosphere is
probably not important since NO emissions in Los Angeles tend to suppress ozone
levels to nearly zero during the night. Before the photochemical reactions
* The results of reference [2] have been modified slightly by Deluding
organic solvent and other miscellaneous contributions which were neglected
in that study.
5-2
-------
begin in the morning, ozone concentrations in Los Angeles are typically less
than .01 PPM. In reviewing the modelling studies below, background hydrocarbon
and ozone contributions will be neglected.
A third area of uncertainty in calculating required reactive organic
reductions involves the role of NO . Ambient oxidant levels depend on
A
emission levels of both organics and nitrogen oxides. The degree of organic
emission reductions that is necessary to achieve the oxidant standard will
depend on the level of NO emissions. In the analysis below, it will be
A
assumed that NO concentrations will remain at 1972 levels. This assumption
A
appears reasonable in light of recent emission projections for Los Angeles
which indicate that the reductions in NO from motor vehicles will be nearly
A
cancelled by increases in NO from other sources during the 1970's, [4].
A
A final area of uncertainty involves oxidant measurement techniques.
It has been found that Los Angeles County APCD procedures yield oxidant
values that frequently differ substantially from measurements made with
EPA procedures,[5]. Some of the empirical models reviewed below use
data taken with the EPA procedure, while others use Los Angeles APCD
data. The results of the various empirical models should be standardized
to a single monitoring method. Since sufficient information to perform a
rigorous standardization is not available, the models will be used here
in their original form. Accordingly, the discrepancies in the aerometric
data base should be noted as a potential source of error in the analysis
presented below.
5.1.1 Review of Oxidant/Precursor Models
This section reviews the results of six oxidant/precursor methodologies
which have been applied to the Los Angeles region. The first four models
involve emm'rical analyses of aerometric data; the last two models are based
on smog chamber simulation. Each model is reviewed specifically with respect
to the overall degree of reactive organic control that is indicated for
attaining the oxidant standard in the Los Angeles region. As noted above,
it will be assumed that total NO emissions remain fixed at the 1972 level
A
in calculating required reactive organic reductions.
EPA Los Angeles Aerometric Model
Schuck and Papetti [6], used the "upper limit" approach to analyze the
relationship between maximal one hour oxidant and hydrocarbons. They pro-
duced two types of upper limit curves for the Los Anqeles reqion. The first
5-3
-------
type, illustrated in Figure 5-1, is equivalent to the EPA Appendix J approach,
[7], [8]. For each of the three locations listed in Figure 5-1, the solid
line represents the upper limit of daily maximum one hour oxidant values
that are associated with various concentrations of 6-9 a.m. nonmethane
hydrocarbons.* The daily maximum oxidant levels and the early morning
hydrocarbon levels represent data taken at the same location from 1968 to
1971. The dashed lines in Figure 5-1 are extrapolations of the upper
limit curves to zero based on data from other large U.S. cities which ex-
perience lower hydrocarbon concentrations than Los Angeles.
Figure 5-2 illustrates the second type of upper limit curve derived
for the Los Angeles region. This curve gives the upper limit of daily maximal
oxidant levels measured anywhere in the basin for various values of 6-9
a.m. nonmethane hydrocarbons averaged over 8 stations in the basin. This
figure is based on 1971 data only.
Using Figures 5-1 and 5-2, Schuck and Papetti calculated the overall
degree of reactive hydrocarbon control needed to attain the .08 PPM oxidant
standard in the Los Angeles region. Figure 5-1 indicated that 93% control
was required from the 1971 emission level. Figure 5-2 implied 91% control
from the 1971 level. These levels of control were calculated by noting the
maximal oxidant level in 1971 (point A in Figure 5-2), finding the associated
maximal NMHC level (point A'), and then determining the degree of control
(to point B ) required to attain the ambient standard (point B). Allowing
for emission reductions which occurred between 1971 and 1972, the corresponding
degrees of control from 1972 emission levels would still be approximately
93% and 91% respectively.
To put the results of the EPA upper limit model in perspective, it is
useful to note some of the sources of error in the analysis. The following
list summarizes the main limitations:
t The upper limit model is subject to inaccuracies in the aerometric
data base for oxidant and total hydrocarbons. Calculating NMHC
levels from total hydrocarbon levels introduces another source of
error.
*Nonmethane hydrocarbons were not actually measured as such. Rather, non-
methane hydrocarbons were computed from total hydrocarbon measurements
according to the formula,
NMHC = .7 (THC-1.3).
. 5-4
-------
.6Q
D_
0-
X
o
DC:
ZD
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in
LU
z:
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<
2 3 4
6-9 A.M. NONMETHANE HYDROCARBONS (PPMC)
Figure 5-1. Upper Limit Curves for Three Stations in the
Metropolitan Los Angeles AQCR, [e]
5-5
-------
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t The role of NOX in oxidant formation is neglected. The present
upper limit curves may no longer be appropriate if the
HC/NOX emission ratio is altered.
t Relating oxidant concentrations to 6:00-9:00 A.M precursor concen-
trations neglects the role of post 9:00 A.M. emissions ia oxidant
production.
The EPA Appendix J approach (Figure 5-1) does not account for trans-
port. Early morning precursor and afternoon oxidant measurements
at one location are likely associated with two different air masses.
The modified approach (Figure 5-2) does account for transport,
but only in an approximate, aggregated way.
The effect of meteorological variables is not accounted for. The
observed relationship of max oxidant to hydrocarbons may be spurious
in the sense that it may be due to a mutual correlation with un-
accounted for meteorological variables.
The upper limit curves are not defined in a statistically meaningful
manner. Likewise, the calculation of degree of control required
neglects statistical considerations.
Chevron Research Company Aerometric Model
Merz, Painter, and Ryason [9] used regression analysis to examine the
relationship between oxidant and early morning precursor levels at downtown
Los Angeles. They regressed max daily one hair oxidant against 6 to 9 a.m.
concentrations of NO and THC. To minimize meteorological variations, and
A
therefore to minimize spurious oxidant/precursor dependencies due to mutual
interrelations with metorological variables, data were entered only for the
months of August, September, and October.
Using log-linear regression on three months of data for eight years
(1962-1969), they obtained the result,
N0v THP
In OX = 2.6 + .150 In + .542 In , (5-1)
where [OX] = pphm, [NOV] = pphm, and [THC] = ppmC.* Making the simple
/\
assumption that 50 percent of THC is non-methane HC, they concluded that
In OX = 2.98 + .150 In - + .542 In - . (5-2)
This equation served as a basis for the "smog diagram" illustrated in
Figure 5-3.
* The numerical constants, 17.5 and 4.6, are the geometric average values
5-7
for NOV and THC.
A
-------
1.0
a.
a.
.10
CTi
ID
.01
6-9 A.M. NONMETHANE HYDROCARBONS (PPMC)
Figure 5-3. Chevron Research Smog Diagram for August-October in
Downtown Los Angeles, [9]
5-8
-------
Using the smog diagram and a statistical analysis of pollutant con-
centrations, the Chevron group calculated the degree of NMHC control that
would be required to reduce violations of the 10 pphm California oxidant
standard to less than 9 hours per year (.1% of all hours) in downtown
Los Angeles. They concluded that, for fixed NO emissions, NMHC emissions
/\
would need to be reduced by 93% from the levels of the late 1960's. From
1972 NMHC emission levels, which are lower than levels of the late sixties,
the corresponding degree of control would be 91%.
To reduce violations of the federal oxidant standard (8 pphm) to one
hour per year at all locations in the Metropolitan Los Angeles AQCR would
require significantly greater hydrocarbon emission control than the case
investigated by the Chevron group. As a first guess, one would expect
that 91% degree of control for the Chevron case would imply at least 95%
control for the more stringent case of attaining the federal standard in
the entire air basin.
It is interesting to note that the simple log-linear regression used
by Merz, Painter, and Ryason indicated that NO reductions would have a
X
slight but beneficial impact on oxidant air quality. This is in contrast
to the results of the three models which follow in this discussion. These
three models, two based on aerometric data and one on smog chamber data,
indicate that NO emission reductions would probably have an adverse effect
}\
on oxidant air quality.
With three exceptions, the Chevron study involves the same limitations
as the Schuck and Papetti analysis or the EPA Appendix J analysis. These
exceptions are as follows:
t The Chevron study does include NOV as well as HC.
A
The Chevron analysis minimizes meteorological interferences in
the oxidant/precursor relation by restricting input data to
three months of the year.
In the Chevron study, the required degree of control is determined
in a more statistically meaningful manner.
California Air Resources Board Aerometric Analysis
Kinosian and Paskind [10] examined the relationship between oxidant and
precursors at four locations in the Metropolitan Los Angeles AQCR. They used
5-9
-------
ambient data for 6-9 A.M. THC and NOV concentrations and for max-hourly
A
oxidant concentrations measured at the same station. The data base consisted
of measurements for July through September from 1969 to 1972.
THC measurements were converted to NMHC estimates using correlations estab-
lished between THC and NMHC at two Los Angeles monitoring sites.
At each location, the data were grouped according to various early
morning HC concentrations. For each HC level, a regression was run between
oxidant levels and NO concentrations. The resulting curves, giving expected
A
oxidant levels as functions of early morning HC and NO concentrations, are
A
illustrated in Figure 5-4.
The results of Figure 5-4 cannot be used in a straightforward manner
to calculate the overall degree of hydrocarbon control required for the Los
Angeles Region. The curves in Figure 5-4 refer to expected max one-hour
oxidant during the summer months and not the oxidant level that would occur
(for given NMHC and NO concentrations) under worst case meteorology (e.g.
A
intense sunlight, persistent inversion, etc.). However, the results of
Kinosian and Paskind can be used to obtain some insight into the level of
early morning NMHC required for standard attainment. The curves indicate
that, at a high oxidant such as Asuza, oxidant levels up to .15 PPM can
be produced by 6-9 A.M. NMHC levels of .3 PPMC. Even taking an optimistic
approach and assuming that max oxidant is proportionally related to NMHC
below .3 PPMC,* the Asuza results imply that NMHC levels of .16 PPMC or lower
would be required to attain the federal standard at that site.
Maximal 6-9 A.M. NMHC levels at Asuza were about 4 PPMC in 1972,
[10], [11]. A reduction to .16 PPMC would therefore be equivalent to
96% overall degree of control from the 1972 level. This percentage re-
duction figure may be conservative since a constant NO emission level
X
could imply that the HC/NOV ratio for greatest oxidant formation will no
A
longer occur in the atmosphere (i.e. for very low NMHC levels, morning NO
A
levels may be all to the right of the peak of the curves in Figure 5-4).
However, counterbalancing that argument, %% reduction may be too low since
the Kimosian and Paskind curves are not for worst case meteorology.
* This is optimistic since the curves indicate that max oxidant reductions
are distinctly less than proportional to NMHC reductions for all the data
above .3 PPMC NMHC concentration.
5-10
-------
DOWNTOWN LOS ANGELES
(3.6)
6-9 a.m.
Total and (Non-Methane)
Hydrocarbon Cone., ppmc
10 20 30 40 50 60 7
6-9 a.m. Oxides of Nitrogen Cone., pphm
20
a
n
g
8 15
o
u
10
ANAHEIM
7 (3.6)
6 (3.0)
(0.4)
6-9 a.m
Total and (Non-Methane)
Hydrocarbon Cone., ppmc
~fd 20"30"40"
6-9 a.m. Oxides of Nitrogen Cone., pphm
AZUSA
35
.§30
o
o
15
'10-.
I
5-
3 (0.8)
2'(0..3)
i 6-9 a.m.
Total and (Non-Methane)
Hydrocarbon Cone., ppnc
0 10 20 30 40
6-9 a.m. Oxides of Nitrogen Cone., pphm
SAN BERNARDINO
6-9 a.m.
Total and (Non-Methane)
Hydrocarbon Cone.,ppmc
0 10 20 30 40
6-9 a.m. Oxide* of Nitrogen Cone., pphm
Figure 5-4. California Air Resources Board Aerometric
Results, Relationship Between 6-9 A.M. NO ,
6-9 A.M HC, and Max-Hour Oxidant Concentrations
at Selected Sites, [10]
5-11
-------
The limitations in using the Kinosian and Paskind results to calculate
overall degree of NMHC control are similar to those associated with the
Shuck and Papetti analysis. The reader is referred to the previous listing
of those limitations.
Environmental Quality Laboratory Aerometric Model
Trijonis [12] used a stochastic model to examine the relationship of
oxidant levels in central Los Angeles to hydrocarbon and nitrogen oxide
emission levels. For given HC and NO emission levels, he determined the
X
joint distribution of morning HC* and NO concentrations (7:30-9:30 averages)
X
at downtown Los Angeles from five years of Los Angeles APCD monitoring data
(1966-1970). He also determined the probability that mid-day oxidant would
violate the state standard (.10 PPM for one hour) as a function of the
morning concentrations. For oxidant, an average was taken of maximum one-
hour values between 11:00 A.M. and 1:00 P.M. at downtown Los Angeles,
Pasadena, and Burbank, weighted according to wind speed and direction, so
that the maximum oxidant would correspond as closely as possible to that
in the air mass that had been over downtown in the morning. The joint
morning HC/NO distribution and the probability of a standard violation as
X
a function of morning precursor levels were determined separately for
summer and winter.
By assuming that the joint HC/NO distribution responds linearly to
J\
emissions and that the oxidant standard violation function remains constant
as emissions levels change, Trijonis calculated the expected number of days
per year that mid-day oxidant in central Los Angeles would exceed the state
standard as a function of HC and NOV emission levels. Figure 5-5 summarizes
A
the results.
The Environmental Quality Lab aerometric model implies that (for fixed
NO emissions) a 90% reduction in reactive hydrocarbon emissions from the
/\
1972 level is necessary to attain the California oxidant standard (.10 PPM
for 1 hour) mid-day in the central Los Angeles area. To meet the more
stringent federal oxidant standard (.08 PPM for 1 hour) at all times of
the day and throughout the entire AQCR should require a significantly
* The HC measurements were adjusted for natural background methane using
the empirical formula derived by EPA for Los Angeles.
5-12
-------
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5-13
-------
greater degree of control. As a first guess, at least 95% reactive hydro-
carbon control would appear to be necessary to attain the federal standard
throughout the basin.
The EQL oxidant model involves many of the same limitations as the
other aerometric analyses, (see discussion of Schuck and Papetti model).
However, there are several improvements:
t The role of NO (as well as hydrocarbons) is explicitly
examined.
Transport is accounted for.
Interferences in the oxidant/precursor relation from inter-
correlations with meteorological variables are reduced by
split analyses for summer and winter.
t The results are stated in a statistically well defined manner.
The price of these improvements is that the application was restricted to
only mid-day ozone in central Los Angeles.
EPA Smog Chamber Model
Dimitriades [13], [14] investigated the relationship of oxidant to pre-
cursors using the results of laboratory smog chamber experiments conducted
with auto exhaust. Figure 5-6 summarizes his analysis of emission reduction
requirements for attaining the NAAQS for oxidant and nitrogen dioxide. HC
and NO concentrations in the shaded regions (to the left of line ab or
A
below line be) yield less than .08 PPM oxidant after six hours of irradiation
equivalent to Los Angeles sunlight. NO concentrations below line df imply
A
attainment of the national NOp standard (.05 PPM, annual average). Point g
in the Figure represents the maximal yearly one hour levels of HC and NO
A
measured in Los Angeles during the early 1970's, [11].*
A cursory examination of Figure 5-6 would lead to the following con-
clusions concerning the degree of control required for standard attainment:
For present NO levels, the OX standard could be attained at point
h, equivalent to a 65% HC reduction from levels of the early 1970's.
t Both the OX and N0? standards could be attained at point e, equivalent
to a 90% HC and 74% NOV reduction from levels of the early 1970's.
/\
*In Dimitriades1 original paper, £13], point g was given at typical con-
centrations measured in the Los Angeles region rather than yearly maximal
one-hour concentrations.
5-14
-------
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5-15
-------
However, as Dimitriades points out, the above argument misses a subtle, but
very important point, [14]. The ratio of NO to HC in the ambient atmos-
/\
phere varies from day to day and is often considerably different than the
average emission ratio, (see Figure 5-7 for example).* For a constant HC
value, measured NOV concentrations can vary by a factor of 5 or more. Thus,
X
the ambient NO concentration that is associated with the yearly maximal HC
X
concentrations may be much less than the yearly maximal NO concentration.
X
Since lowering NO (at either point h or point e) increases oxidant in
J\ ~~ ~
Dimitriades1 diagram, the fluctuations in the ambient HC and NO ratio imply
/\
that a greater degree of HC control is needed than would be the case if a
constant HC/NO ratio existed in the atmosphere. Assuming that, on the day
X
of maximal HC concentration, the NOV concentration can be as few as one fifth
.X
the maximal NO concentration, the overall degree of HC control required
A
would be represented by point hr rather than point h. For maximal HC concen-
trations, NO concentrations could range anywhere from h" to h1. The degree
X
of HC control for OX standard attainment implied by this argument would be
94% from levels of the early 1970's.
As was the case with aerometric models, smog chamber models are subject
to several limitations. The laboratory smog chamber is a very simplified
model of the complex processes that occur in the atmosphere. Smog chambers
do not simulate the effect of continuous addition of fresh precursor emissions
as the day proceeds. Laboratory experiments do not include carry-over effects
from previous day smog reactions and may not be of sufficient time duration
to represent atmospheric reactions occurring for periods up to 10 hours on a
single day. Smog chambers do not simulate the simultaneous effect of several
dynamic meteorological process that occur on smoggy days in Los Angeles
(e.g. turbulent diffusion, transport to regions with greater mixing height,
diurnal solar radiation pattern, etc.). Also, the interactions of pollutants
with the ground may be much different than the wall effects which occur in
the smog chamber. Finally, auto exhaust or other laboratory test hydro-
carbons may not adequately approximate the reactive hydrocarbon mixtures found
in real atmospheres.
* The fluctuations in measured HC/NO ratio are not completely understood.
Some of the fluctuation may be due to variance in the stationary source
areas (HC intensive vs. NOX intensive areas) that the air mass has en-
countered. Some may be due to the dependence of evaporative emissions on
temperature. Some of the fluctuation may result from a dependence of the
HC/NOX ratio in auto exhaust on ambient temperature and relative humidity.
5-16
-------
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*
5 10
HC CONCENTRATION (PPMC)
[Adjusted for Natural Background Methane)
Fiaure 5-7 Distribution of Morning Precursor Concentrations in
' Downtown Los Angeles, [4] (7:30 - 9:30 averages)
5-17
-------
APCD Smog Chamber Model
Hamming, Chass, Dickinson, and MacBeth [ 1 ] of the Los Angeles County
APCD used smog chamber tests with auto exhaust to examine the relationship
between oxidant and precursors. Figure 5-8 presents the relationship they
found between max one hour oxidant (after five hours irradiation) and initial
HC and NOV levels. Point a in Figure 5-8 represents the maximal HC and
A
NO concentrations found in Los Angeles in the early 1970's.
/\
A cursory examination of Figure 5-8 indicates that the NAAQS for oxidant
can be met (at present NO levels) by reducing HC levels to point b, a 73%
X
overall degree of HC control. However, the above argument assumes that
maximal ambient HC concentrations will be associated with maximal ambient
NO concentrations. As noted previously (under the discussion of Dimitriades1
/\
results), the ambient HC/NO ratio varies substantially from day to day,
X
and the NO concentration that is associated with yearly maximal HC levels
X
may be much less than the yearly maximal NO concentration. Since lowering
X
NO at point b increases oxidant. the fluctuations in the ambient HC/NO
X ~ ^ - - - x
ratio imply that a greater degree of HC control is needed than that associated
with point b. Allowing for this effect, the necessary degree of control
becomes point c, 92% HC control. For maximal HC concentrations at point c,
NOV concentrations could range anywhere from c to d.
X
The above conclusion (that 92% HC control is required to attain the
OX standard in the Los Angeles region) should be contrasted with the con-
clusion reached by Hamming et. al. from Figure 5-8. The Los Angeles APCD
staff indicated that the present California new car control program for
light-duty vehicles alone would attain the oxidant standard in the Los
Angeles region in the early 1980's, even though the reduction in total
region wide reactive HC emissions would be only about 60%. The analysis
by Hamming et. al. differs from the present analysis in two respects. First,
the APCD staff assumed that maximal yearly HC concentrations would be
associated with maximal yearly NO concentrations. Accordingly, they would
/\
contend that the line cd should be represented only by point c. Second,
the APCD assumed that only light-duty vehicle emissions would participate
in the formation of maximal smog levels. They argue that downtown Los
Angeles, where maximal precursor levels are experienced, is subjected to
negligible influence from sources other than light-duty vehicles and that
5-18
-------
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X
X
X .45
' /
'
/ / / / /
I ' I
I I
.35
X
X
X
X
X
X
X
i -,
I I \
i \
\ \
\ ^
.30
.20
.5
1.0 1.5
HYDROCARBONS IR-2, (PPM)
2.0
h
0
4-
10
15
20
HYDROCARBONS, (PPMC)
Figure 5-8. Los Angeles APCD Diagram of Max
Ozone Concentrations vs. Precursor
Concentrations, [1]
5-19
-------
no growth in vehicle use will occur in the downtown area. Although total
HC emissions in the metropolitan Los Angeles AQCR will be reduced by only
60% in the early 1980's, the APCD calculates that light-duty vehicle HC
emissions (with no growth in miles travelled) will be reduced by 87% in
the downtown Los Angeles area from the early 1970's to the early 1980's.
As noted earlier, there are important limitations in using smog chamber
results to determine control requirements for real atmospheres. The reader
is referred to the discussion of these limitations in the previous section.
5.1.2 Conclusions with Respect to Required Emission Reductions
Table 5-1 summarizes the conclusions reached by the examination of
alternative oxidant/precursor models in the previous section. The degree
of RHC control required (according to our interpretation of each model)
is listed for the six models. The estimates of required RHC control obtained
from the alternative models are notably similar; the values range from 91%
to greater than 95%. The apparent agreement among the models should be viewed
with some caution. First, all models were subject to our interpretation
which may differ from other interpretations. For instance, we assumed that
maximal atmospheric HC levels could be associated with a wide range of NO
A
levels rather than with maximal NO levels alone. Variance in the ambient
/\
TABLE 5-1. ESTIMATES OF REQUIRED DEGREE OF RHC CONTROL FOR
OX STANDARD ATTAINMENT IN THE METROPOLITAN LOS
ANGELES AQCR *
TRW's Interpretation of Degree of RHC
Model Control Implied by the Model
EPA Los Angeles Aerometric Model [6] 91-93%
Chevron Research Company Aerometric
Model [9] > 95%
California Air Resources Board
Aerometric Analysis [10] 96%
Environmental Quality Laboratory
Aerometric Model [12] > 95%
EPA Smog Chamber Model [13] 94%
LA County APCD Smog Chamber Model [ 1 ] 92%
*In calculating the required degree of RHC control, NO emissions
were assumed to remain constant at the 1972 emission levels.
5-20
-------
HC/NO ratio (for fixed emission levels) implies a greater degree of control
X
is necessary than if a constant ratio were assumed. Second, although there
are six alternative models, four are aerometric approaches founded on the
same data base and two are smog chamber approaches. Errors or biases in one
aerometric model may be shared by the other aerometric models. Similarly,
the two smog chamber models have certain approximations and limitations in
common. Thus, the uncertainty in the required degree of control may be much
greater than indicated by the variance in the numbers presented in Table 5-1.
It should be emphasized that the models reviewed above do not account for
contributions from background reactive hydrocarbons, e.g. the geogenic hydro-
carbons noted by Crabtree and Mayrsohn, [2]. The existence of background
reactive hydrocarbon sources would imply a greater degree of control is re-
quired for man-made sources. Since the required degree of overall control
is so severe (91 to >95%), and since background contributions may be sub-
stantial (up to 13% of total ambient reactive hydrocarbons by weight), a
strong argument can be made that even 100% control of the man-made emission
inventory will not achieve the oxidant air quality standard in Los Angeles.
This argument is highlighted in a very recent paper by Duckworth and
McMullen,[15].
The above discussion of the degree of reactive hydrocarbon control
required for Los Angeles presents a more pessimistic conclusion than would be
reached by the "linear rollback" model. Linear rollback is based on the
arbitrary assumption that oxidant levels are directly proportional to reactive
hydrocarbon emission levels. The linear rollback model indicates that only
85% reactive hydrocarbon control is required for Los Angeles.
In summary, a great deal of uncertainty surrounds the degree of reactive
hydrocarbon control that is necessary to achieve the NAAQS for oxidant in the
Los Angeles region. A review of aerometric and smog chamber models indicates
that at least 90%, and possibly much higher, control will be required. If
background hydrocarbon contributions are accounted for, it appears that even
100% control of man-made sources may not be sufficient.
In view of the uncertainty as to required degree of control, and in view
of the potential impossibility of ever attaining the oxidant standard, this
report will not derive source emission reductions aimed at actual attainment
5-21
-------
of the oxidant standard. Rather, for illustrative purposes, 90% reactive
hydrocarbon control (for man-made contributions) will be selected as an
arbritrary target level. Reactivity criteria will be used to calculate
individual source emission reductions corresponding to the overall target
level of 90%.
5.2 GUIDELINES FOR DETERMINING INDIVIDUAL SOURCE EMISSION REDUCTIONS
The previous section discussed the overall degree of reactive organic
control that would be required to attain the federal oxidant standard in
the Metropolitan Los Angeles AQCR. Noting the uncertainties concerning
the required degree of emission control and the possibility that even 100%
control of man-made organic sources might be insufficient, 90% was arbitrarily
chosen as a control target level for the purposes of this study. Having
selected an objective for the overall degree of control, the problem remains
as to how to allocate emission reductions among individual sources in at-
taining the overall control level. This section discusses general principles
for determining individual source reductions.
Section 5.2.1. points out that the determination of individual source
control levels is a classical economic problem. Economic efficiency criteria
which govern this allocation problem are described. These criteria are
discussed for two cases, indiscriminate control of hydrocarbons and control
based on reactivity.
The cost data required to determine source emission reductions based
on economic criteria are often unavailable. Section 5.2.2 discusses how
source reductions can be allocated in the absence of cost information.
Again, both indiscriminate control and control based on reactivity are
considered.
5.2.1 Economic Efficiency Principles
The problem of selecting individual source emission reductions that
will attain a given level of overall air quality is a classical economic
problem. Simply stated, economics is the study of how best to allocate
scarce resources among alternative ends in order to attain given objectives.
In the problem at hand, we would like to allocate control expenditures among
5-22
-------
various emission sources in such a way that we minimize total social cost*
in attaining a given air quality objective.
Economic theory provides one basic principle for insuring that the
allocation of control expenditures is cost efficient. This is the "equality
of marginal cost" condition. Let us define the marginal air quality control
cost for a source as the extra control cost that will be incurred in attaining
one unit of air quality improvement by reducing that emission source. The
economic efficiency principle states that the marginal air quality control
cost must be the same for all sources. The necessity of this condition in
order to minimize total air quality control cost can be proven by a simple
contrapositive argument. If the marginal air quality control cost for some
source A were less than for some source B, the total social control cost
would be lessened (while maintaining the same air quality) by increasing
the degree of control on A while relaxing the degree of control on B.
If it is assumed that one ton of emissions from any source has the same
impact on air quality (e.g. the indiscriminate approach to controlling hydro-
carbons), the marginal air quality control cost condition applies directly to
marginal emission reduction costs. Figure 5-9 illustrates this principle
for two hypothetical sources (Source I and Source II). For each source,
Figure 5-9 presents a total cost curve and marginal control cost curve.
The marginal cost curve is simply the negative of the derivative of the
total cost curve.
In this hypothetical situation, total emissions are 6 tons per day at
the uncontrolled level, 4 tons from Source I and 2 tons from Source II.
In order to minimize the total cost of emission control, emission reductions
should be carried out such that marginal emission control costs remain the
same for each source. For instance, to achieve a 75% overall reduction,
Source I should be reduced to point A (.75 tons per day) while Source II
should be reduced to point A'(.75 tons per day). To achieve a 90% overall
reduction, Source I should be controlled to point B (.25 tons per day) while
* Actually, the distribution of costs among various economic sectors may
also be an important policy consideration. However, the distribution of
costs can always be adjusted ex post facto by appropriate transfer payments
(e.g. subsidies or taxes). Here we will just address the efficiency
criteria of minimizing total resource cost to society.
5-23
-------
TOTAL EMISSION REDUCTION COST CURVES
$3000
SOURCE I
$2000.
in
o
o
$1000.
$300
SOURCE II
$2000. .
$1000. .
Uncontrolled
Emission Level
J.
1 2 3
Emissions (tons/day)
MARGINAL EMISSION REDUCTION COST CURVES
Uncontrolled
Emission Level
1 2
Emissions (tons/day)
$3000--
SOURCE I
_Equaljty_of_J|1argi_n_al_Contrpl_Co^t _
(90% Overall Control)
_ E_gua_h'ty _of Mar£inal_Cojitro!__C2St_
(75% Overall Control)
SOURCE II
$2000- -
$1000- -
1 2 3
Emissions (tons/day)
1 2
Emissions (tons/day)
Figure 5-9 . Total and Marginal Control Cost Curves for
Two Hypothetical Emission Sources
5-24
-------
TOTAL [.'MISSION REDUCTION COST CURVES
$3000
$2000--
o
-------
Source II should be controlled to point B'(.35 tons per day). In this case,
Source I is always assigned a greater percentage reduction than Source II
because Source I generally exhibits lower marginal control costs.
For the above example, points A-A and B-B were determined by a graphical
trial and error technique. In general, the problem of determining cost
efficient source emission reductions from individual source control cost
curves is a nonlinear mathematical programming problem, [16]. This problem
can be approximated by a linear programming problem if piecewise linear
total control cost curves are used, [16], [17], [18]. Solutions for real
air basins have been obtained using the linear programming approach, [16]» [17].
If there is a source-to-source variation in the air quality impact of a
given tonnage of emissions, then the marginal cost rule should apply to
"effective" emissions rather than total emissions. For instance, if re-
activity criteria are considered for hydrocarbons, the efficiency principle
would demand that the marginal cost of reactive emission reductions be equal
for all sources. If it were assumed that Source I has a weight reactivity
of 0.5 and Source II has a weight reactivity of 1.0 in the hypothetical
example above, then the appropriate marginal cost curves would be as shown
in Figure 5-10. Of course, accounting for reactivity would alter the relative
degrees of control required for each source, (compare points C-C' to A-A and
D-D* to B-B' ). The concept of "effective" emissions might be used for other
pollutants (e.g. S0~, NO , TSP, etc.) if the spatial distribution of emissions
C. /\
produces source-to-source variations in air quality impact per ton. For
instance, tall stack or nonurban emissions might be weighted less than
ground level or urban emissions.
5.2.2 Source Emission Reductions in the Absence of Control Cost Information
The previous section discussed economic guidelines for determining
individual source reductions which attain a given overall degree of control.
To apply these guidelines requires knowledge of the relationship between
control costs and emission reductions for each source. Such cost information
is often unavailable, and it is useful to discuss rules for allocating
individual source emission reductions when cost knowledge is lacking.
5-26
-------
First, let us consider the case where emissions from all sources have
the same impact (per ton) on air quality, e.g. the indiscriminate approach
to organic control. In this case, it is reasonable and equitable (in the
absence of control cost data for individual sources) to allocate the same
degree of control to each source. Thus, if C were the overall degree of
control required, individual source emission reductions would each be
specified by
E° - E
! U C for i=i N, (5-3)
where
E. = weight emissions from the ith source before control,
E.J = weight emissions from the ith source after control,
and N = total number of sources.
Of course, equation (5-3) would automatically insure that the overall degree
of control would be C since, by simple linearity,
N
Total emissions after control = E E-
N
= E (E°-E°C) by (5-3)
N
= (1-C)ZE°
= (1-C)(total emissions before control)
Next let us examine the case of source-to-source variation in the air
quality impact per ton of emissions. For instance, let us consider the use
of reactivity criteria in organic control, with SWR. representing the source
weight reactivity for the ith source. In the absence of control cost in-
formation, there appears to be one* simple and reasonable control allocation
5-27
-------
rule that accounts for varying reactivities. This rule is that each source
should be controlled so that the fraction of emissions remaining is inversely
proportional to the reactivity of the source, or stated symbolically,
E
for 1=1,...,N, (5-4)
o SWR.
Ei
In this case, the constant (K) is determined by insuring that the overall
degree of reactive organic control is C. This is accomplished as follows:
TC _ total reactive emissions after control
total reactive emissions before control
N
E SWR.E.
1=J _ ___
" N
£ SWR.E?
_2i! - by (5-4)
= K/SWR0
where
SWR° = average source weight reactivity before control
* The reader will find that other control allocation rules are either overly
complex or yield unreasonable results. For instance, the simple rule that
"each source be controlled in proportion to its reactivity" may require
that more than 100% control be established for some sources.
5-28
-------
Thus, we have,
K = (l-C)SWR0. (5-5)
Combining equations (5-4) and (5-5) yields the following control allocation
rule*.
L - 0-C)SWR° . for i=l N (5-6)
Eo SMRi
5.3 EMISSION REDUCTIONS FOR ORGANIC SOURCES IN THE
METROPOLITAN LOS ANGELES AQCR
Section 5.1 discussed the overall degree of reactive organic control
required to attain the national oxidant standard in the Metropolitan Los
Angeles AQCR. Section 5.2 presented guidelines for allocating emission
reductions among individual sources in achieving a given degree of overall
emission control. These guidelines included economic efficiency criteria
(Section 5.2.1) as well as equity criteria which could be used in absence
of economic data (Section 5.2.2). Based on these results, the present
section determines individual emission reductions for organic sources in
the Metropolitan Los Angeles AQCR.
The use of economic efficiency guidelines in establishing individual
source control levels requires knowledge of the relationship between emission
reductions and control costs for each source category. For this study of
organic control in Los Angeles, emission control cost curves are not available
for most source types. Some information exists concerning the cost of
specific controls for major source types [16], but present data are insuffi-
cient to establish complete cost curves in most cases. To assemble detailed
control cost information is not possible within the resources allocated to
this project. Thus, the equity criteria of Section 5.2.2 will be used to
allocate control among individual sources rather than the economic efficiency
criteria of Section 5.2.1.
Table 5-2 summarizes control requirements for individual organic source
categories in the Metropolitan Los Angeles AQCR. These control requirements
are based on the arbitrary target level of 90% overall reactive organic control
5-29
-------
Allowable emissions and percent reductions are listed for indiscriminate
organic control as well as for control based on three reactivity classifi-
cation schemes: the 2-group, 5-group, and 6-group schemes (see Chapters
1 and 4 for descriptions of these reactivity scales).
For indiscriminate organic control, source emission reductions are
calculated from equation (5-3); accordingly, each source is reduced by 90%.
For each reactivity classification scheme, source emission reductions are
determined from equation (5-6). As evidenced by Table 5-2, sources with
high reactivity are assigned the greatest emission reductions. The two
sources with extremely low reactivity, PCE drycleaning and 1,1,1-T degreasing,
are actually assigned increased emissions (over uncontrolled levels) by
formula (5-6).
A very notable feature of Table 5-2 is that emission reductions are
quite stringent for nearly all source categories under each reactivity scheme.
Twenty-one of the twenty-six source categories are allocated degrees of con-
trol ranging from 85% to 94% by all three reactivity schemes. Three other
source categories (petroleum production, stationary source fuel combustion,
and petroleum based dry cleaning solvent) are allocated somewhat lesser
control levels, generally about 80%. As noted above, PCE dry cleaning and
1,1,1-T degreasing are allowed to increase emissions.
The general uniformity in the degree of control assigned to most source
categories is a result of two factors. First, as discussed in Chapter 4,
there is a uniformity in reactivity ratings among most source categories.
Second, the very stringent degree of overall control (90%) requires that
almost all sources be controlled to very high levels.
Table 5-3 lists individual source emission reductions for various degrees
of .overall control, ranging from 10% to 95%. These have been computed from
equation (5-6), with source weight reactivities based on the 5-group re-
activity classification scheme. At high levels of overall control (>50%),
the general uniformity of control requirements among most source categories
is again apparent. At very low levels of overall control (<20%), several
source categories with low reactivity are allowed to increase emissions
according to formula (5-6).
5-30
-------
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5-31
-------
TABLE 5-3. INDIVIDUAL SOURCE EMISSION REDUCTIONS
FOR VARIOUS DEGREES OF OVERALL CONTROL
(ACCORDING TO THE 5-GROUP SCHEME)
,- SOURCE CATEGORY
/
STATIONARY SOURCES: ORGANIC FUELS
AND COMBUSTION
Petroleum Production and Refining
Petroleum Production
Petroleum Refining
Gasoline Marketing
Underground Service
Station Tanks
Auto Tank Filling
Fuel Combustion
Waste Burning * Fires
STATIONARY SOURCES ORGANIC CHEMICALS
Surface Coating
Heat Treated
Air Dried
Dry Cleaning
Petroleum Based Solvent
Synthetic Solvent (PCE)
Degreasinq
TCE Solvent
1,1 ,1-T Solvent
Printing
Rotogravure
Flexigraphic
Industrial Process Sources
Rubber 8 Plastic Hanf.
Pharmaceutical Manf.
Miscellaneous Operations
MOBILE SOURCES
Light Duty Vehicles
Exhaust Emissions
Evaporative Emissions
Heavy Duty Vehicles
Exhaust Emissions
Evaporative Emissions
Other Gasoline Powered Equipment
Exhaust Emissions
Evaporative Emissions
Diesel Powered Motor Vehicles
Aircraft
Jet
Piston
-27
-8
31
21
-4
24
0
-5
-63
-1340
-18
-1052
-10
40
38
0
-25
20
0
20
0
20
0
25
-15
36
PERCENT REDUCTIONS FOR
20*
-15
4
40
30
9
29
14
7
-44
-1180
0
-924
0
47
45
13
-11
29
16
29
16
29
18
33
0
45
30%
0
16
46
38
17
41
21
19
-25
-1020
9
-796
13
53
52
25
2
38
27
38
27
38
27
42
10
50
40*
15
28
54
47
30
51
36
30
-6
-860
27
-668
26
60
57
38
17
47
37
47
37
46
36
50
26
59
VARIOUS
50*
29
40
63
56
43
59
43
42
13
-700
36
-540
39
67
64
44
30
56
48
55
48
55
45
58
35
64
DEGREES
60%
44
52
69
65
52
66
57
53
31
-540
45
-412
52
73
71
56
45
64
53
65
58
65
59
67
50
73
OF OVERALL
70Z
58
64
77
74
65
76
64
65
44
-380
64
-284
65
80
79
69
58
73
69
73
69
74
68
75
60
77
CONTROL
80%
71
76
85
83
78
83
79
77
63
-220
73
-156
74
87
86
81
7?
82
79
82
79
82
77
83
75
86
90%
85
88
92
91
87
93
86
88
81
-60
91
-28
91
93
93
87
86
91
90
91
90
91
91
92
85
91
95«
94
94
96
95
96
95
93
94
94
20
91
36
94
03
98
94
93
96
95
95
94
95
95
96
95
95
5-32
-------
5.4 REFERENCES
1. W. J. Hamming, R. L. Chass, J. E. Dickinson, and W. G. MacBeth, "Motor
Vehicle Control and Air Quality, The Path to Clean Air for Los Angeles",
Paper by the Los Angeles County Air Pollution Control District, Presented
at the 66th Annual Meeting of the Air Pollution Control Association,
Chicago, Illinois, June 1973.
2. H. Mayrsohn and J. Crabtree, "Source Reconciliation of Atmospheric
Hydrocarbons", California Air Resources Board Division of Technical
Services, Paper Submitted to Atmospheric Environment, March 1975.
3. U. S. Environmental Protection Agency, "Air Quality Criteria for Photo-
chemical Oxidants", Publication No. AP-63, March 1970.
4. J. C. Trijonis, G. Richard, K. Crawford, R. Tan, and R. Wada, "An
Implementation Plan for Suspended Particulate Matter in the Los Angeles
Region", Prepared for the Environmental Protection Agency, Contract
No. 68-02-1384, TRW Environmental Services, Redondo Beach, California,
March 1975.
5. W. B. DeMore, "LAAPCD Method More Accurate, ARB More Precise",
California Air Resources Board Bulletin, Vol. 5 No. 11, December 1974.
6. E. A. Schuck and R. A. Papetti, "Examination of the Photochemical Air
Pollution Problem in the Southern California Area", EPA Internal Working
Paper, May 1973.
7. Federal Register, Volume 36, No. 158, August 14, 1971
8. E. A. Schuck, A. P. Altshuller, D. S. Barth, and G. B. Morgan, "Relation-
ship of Hydrocarbons to Oxidants in Ambient Atmospheres", Journal of
the Air Pollution Control Association. Vol 20, No. 5, May 1970.
9. P. H. Merz, L. J. Painter, and P. R. Ryason, "Aerometric Data Analysis -
Time Series Analysis and Forecast and an Atmospheric Smog Diagram",
Atmospheric Environment, Vol. 6, p. 319, 1972.
10. 0. R. Kinosian and J. J. Paskind, "Hydrocarbons, Oxides of Nitrogen,
and Oxidant Trends in the South Coast Air Basin, 1963-1972", California
Air Resources Board - Division of Technical Services, Internal Working
Paper.
11. California Air Resources Board Division of Technical Services, "Ten
Year Summary of California Air Quality Data, 1963-1972", January 1974.
12. J. C. Trijonis, "Economic Air Pollution Control Model for Los Angeles
County in 1975", Environmental Science and Technology. Vol. 8, No. 9,
September 1974.
5-33
-------
13. B. Dimitriades, "Effects of Hydrocarbons and Nitrogen Oxides on Photo-
chemical Smog Formation", Environmental Science and Technology, Vol. 6
1972.
14. B. Dimitriades, "Development of an Oxidant Abatement Strategy Based on
Smog Chamber Data", Internal Working Paper, EPA Chemistry and Physics
Laboratory, August 1973.
15. S. Duckworth and R. VI. McMullen, "Can We Ever Meet the Oxidant Standard?",
Presented at the 68th Annual Meeting of the Air Pollution Control
Association, Boston, Massachusetts, June 1975.
16. J. C. Trijonis, An Economic Air Pollution Control Model - Application:
Photochemical Smog in Los Angeles County in 1975, Ph.D. Thesis,
California Institute of Technology, May 1972.
17. R. Kohn, "A Linear Programming Model for Air Pollution Control:
A Pilot Study of the St. Louis Airshed, Journal of Air Pollution
Control Association, Vol. 20, 1970, pp. 78-82.
18. S. E. Atkinson and D. H. Lewis, "A Cost Evaluation of Alternative Air
Quality Control Strategies," EPA Report No. EPA-600/5-74-003,
January 1974.
5-34
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6.0 EVALUATION OF ALTERNATIVE APPROACHES
TO ORGANIC EMISSION CONTROL
The present chapter briefly evaluates the benefits and costs associated
with using reactivity criteria to formulate organic control strategies.
The basic benefit in using reactivity criteria in organic emission control
consists of increased flexibility. Reactivity criteria introduce the
possibility of selective emission control as a potentially advantageous
alternative to the less flexible approach of indiscriminate control. The
costs of using reactivity criteria are extra administrative and testing
expenditures. This chapter provides a very approximate assessment of these
benefit/cost trade-offs.
Three alternative approaches to organic control will be considered
here, indiscriminate control and two reactivity based policies. Indiscrim-
inate control neglects source-to-source variations in reactivity. The first
reactivity based policy involves establishing emission standards for each
source category based on reactivity ratings. In this policy, emission
standards are to be achieved by reducing total emissions. The second
reactivity based policy also establishes emission standards based on
reactivity. However, the second policy allows standards to be attained by
substitutive controls* as well as by total emission reductions.
Section 6.1 evaluates the benefits and costs of the first reactive
policy as compared to indiscriminate control. Section 6.2 assesses the
extra benefits and costs of the second reactive policy as compared to the
first reactive policy. Section 6.3 provides a brief summary and discussion
of the trade-offs.
6.1 ORGANIC EMISSION STANDARDS BASED ON REACTIVITY WITH NO SUBSTITUTIVE CONTROLS
The first level of sophistication in applying reactivity criteria to
organic control policy is to establish emission standards for various source
* Substitutive control for an organic emission source involves the re-
placement of reactive constituents with less reactive organics so as
to lower the reactivity rating of the source.
6-1
-------
categories based on present reactivity ratings. Sources with high reactivity
would be assigned a greater degree of control than sources of lesser re-
activity (see Table 5-2 for example). Each emission source category would
be required to attain the standards by reducing total emissions, not by
substituting less reactive compounds for more reactive compounds.
This type of reactivity based strategy would have the benefit of
concentrating emissions reductions among the most reactive sources. This
would allow a given reduction in reactive emissions to be attained with
lesser control of total emissions than would be called for by indiscriminate
organic control. In essence, more total hydrocarbons would be emitted
(while maintaining the same air quality) by adopting this reactivity based
approach. Of course, the reactivity based strategy would also involve
extra costs as compared to the indiscriminate approach. These would be
the administrative and testing costs involved in determining reactivities
for various source categories. The benefits and costs of applying this
approach to reactive organic control in the Metropolitan Los Angeles AQCR
are discussed in Sections 6.1.1 and 6.1.2, respectively.
6.1.1 Benefits of the Reactivity Based Strategy with No Substitutive Controls
There is only one rigorous way to assess the economic benefits of
establishing organic emission standards based on reactivity. The cost of
attaining the stipulated emission reductions for each source category
should be determined for both the reactivity based strategy and the in-
discriminate strategy. The total cost of control (the sum of the costs
for all sources) should then be compared for the two strategies. The
economic benefit of the reactivity based approach, as compared to the
indiscriminate approach, would be the savings in total strategy control
costs.
In order to perform this assessment of economic benefits, information
on emission reduction costs would be required for every source category.
This is exactly the same type of control cost information that is necessary
to allocate source emission reductions based on economic efficiency
criteria (see Section 5.2.1). As noted in Chapter 5, these cost data are
not available for most organic source categories in the Metropolitan Los
Angeles AQCR. Thus, we cannot perform a rigorous analysis of the economic
6-2
-------
benefits of a reactivity based approach for the same reason that we could
not use economic efficiency guidelines in allocating individual source
emission reductions.
Fortunately, the results of Tables 5-2 and 5-3 allow a simplified
interpretation of the economic benefits associated with the reactivity
approach. Table 5-2 indicates an obvious saving from the reactivity based
approach at 90% control; 148 more tons per day of emissions are allowed
with the (5-group) reactivity based strategy than with the indiscriminate
strategy. The benefit from the reactivity based approach is the expenditure
that is saved by not having to control this 148 tons/day.
A close examination of Table 5-2 reveals that the 148 tons/day saving
essentially involves only two sources, PCE dry cleaning and 1,1,1-T
degreasing. These sources are allowed to emit 162 tons per day under the
5-group reactivity strategy, whereas they would be allowed only 13 tons/day
under the indiscriminate strategy. Although there are some source-to-source
variations in control levels among the other 24 source categories, the other
24 categories as a whole are controlled by 90% in the reactivity based
strategy as well as in the indiscriminate strategy. Thus, for 90% overall
control, the benefit from the reactivity based strategy is essentially that
PCE dry cleaning and 1,1,1-T degreasing need not be controlled.
An analysis of the results of Table 5-3 indicates that the above con-
clusion also holds for other degrees of control (from 10% to 95%). The
24 source categories (sources other than PCE dry cleaning and 1,1,1-T
degreasing) as a whole are controlled to the same degree in the reactivity
based strategy as in the indiscriminate strategy. Thus, the one basic
benefit from the reactivity approach is not controlling the two source
categories of very low reactivity. This is apparently a consequence of
the general uniformity in reactivity ratings among the other 24 source
categories.
6.1.2 Costs of the Reactivity Based Strategy with No Substitutive Controls
This section will consider the program requirements and associated
program costs of adopting reactivity based organic emission regulations.
The discussion of program requirements consists of an outline of the basic
activities that are necessary for the implementation and operation of
6-3
-------
reactivity based emission regulations. The costs of these activities are
described only in a very qualitative way. Since it is very difficult to
estimate costs accurately, showing probable upper and lower bounds seems
most appropriate. It is, in fact, difficult to assess accurately what the
costs of past programs have been, [1].
For the purposes of this discussion, it is assumed that the regulations
will apply to each type of industry based on the industry average reactivity,
not on the reactivity of individual plants. That is, the average reactivity
for all the plants in an industry will be used to establish emission regu-
lations for each individual plant in that industry. It is also assumed
that the regulations will be administered by a local governmental unit,
such as a county Air Pollution District. Another tacit assumption is
that a suitable reactivity scale will exist that includes all types of
compounds.
There are two types of program requirements and costs for implementing
reactivity based emission regulations. The first includes those activities
that are performed only once, (or only occasionally), such as determining
the composition of the organic emissions for the various source types. The
second involves continuing operating activities, such as enforcement.
Prior to establishing new regulations, compositional data on the
emissions from each type of organic source must be obtained. As evidenced
by Chapter 3, the open literature probably will not provide sufficient data
to determine compositions accurately enough for regulatory purposes. This
indicates that a substantial test program will be necessary. The test
program will have to analyze the composition of a statistically significant
number of each type of source in order to account for the differences that
exist between one plant and another in the same type of industry.
It should be noted that obtaining composition data for some source types
will probably have to be performed separately for each jurisdictional area,
since previous emission regulations may vary from area to area. Previous
emission regulations in some areas may have altered source compositions from
the norm (see Section 3.3.1 which describes how the composition of paint
solvents is different in Los Angeles than elsewhere in the nation because
6-4
-------
of local regulations). The mix of process type may also vary from area
to area.
In the present case, emission regulations will be met by total emission
reductions and not by substitutive controls. Thus, the enforcement function
will be essentially the same as the case of indiscriminate control. Accord-
ingly, enforcement costs will be the same as for indiscriminate control.
Table 6-1 shows the approximate costs of the activities necessary to
establish reactivity based emission regulations. For the present case,
the costs are essentially just the expenses of determining source compositions.
Also shown in Table 6-1 are the annualized, initial costs amortized
over 5 years and 20 years. The 5 year values are shown because it is possible
that the regulations will be reviewed every 5 years in order to determine
changes in the composition of the emissions as changes in technology occur.
The 20 year values are shown for the case where 5 year reviews are not
conducted. A basic assumption in Table 6-1 is that the necessary source testing
and analysis would be contracted to the private sector. This seems the
most likely approach since the tests would only be performed on one occasion
and would require expensive and specialized equipment which would not be
necessary for normal control agency operations.
TABLE 6-1. ESTIMATED COSTS FOR ESTABLISHING REACTIVITY
BASED ORGANIC EMISSION REGULATIONS
Program Requirement Composition Data
Initial Cost $50,000 to $500,000
(100 to 500 tests
at $500 to $1,000
per test)
Annualized Cost
Over 5 Years* $13,200 to $131,900 Per Year
Annualized Cost
Over 20 Years* $5,900 to $58,700 Per Year
/_J \
* Using I = I \ n+i")n-l + ] / ' wnere i = 10°^ Onterest rate),
n = years lifetime of the program, In = the original cost, and In =
annualized cost.
6-5
-------
6.2 ORGANIC EMISSION STANDARDS BASED ON REACTIVITY WITH SUBSTITUTIVE CONTROLS
The second reactivity based approach to organic emission control allows
substitutive control measures in addition to establishing emission standards
based on reactivity. Allowing substitutive control measures increases the
number of potential control options. Extra benefits are accrued from this
approach whenever the substitutive control options are less expensive than
emission reduction controls. Increased costs with this approach result
from additional administrative and testing requirements. The extra benefits
and costs of applying this second reactivity based strategy to the Metropolitan
Los Angeles AQCR are discussed in Sections 6.2.1 and 6.2.2, respectively.
6.2.1 Benefits of the Reactivity Based Strategy with Substitutive Controls
An accurate evaluation of the benefits from allowing substitutive con-
trols would require detailed documentation of substitutive control alter-
natives and emission reduction control alternatives for each source category.
Benefits would arise whenever substitutive control measures (either alone
or in conjunction with emission reduction measures) allow a given degree
of control to be attained at less expense than pure emission reduction
measures. These benefits should be summed over all source categories.
As noted previously, the data to perform a comprehensive cost analysis
of alternative control options are not available for most source categories.
In the absence of data for a thorough evaluation, we can only describe the
potential benefits in a qualitative manner. The discussion below gives
a very general assessment of potential benefits from substitutive controls.
An examination of the source categories in the present organic inventory
for Los Angeles reveals two cases where substitutive controls have yielded
substantial reductions in reactivity. These are the substitution of 1,1,1-T
degreaser for TCE degreaser and the substitution of PCE dry cleaning solvent
for petroleum based dry cleaning solvent. 1,1,1-T degreaser has weight
reactivities of .00, .05, and .05 according to the 2-group, 5-group, and
6-group classification schemes, respectively, while TCE degreaser has weight
reactivities of .52, .50, and .50. PCE dry cleaning solvent has weight
reactivities of .00, .04, and .04, while petroleum dry cleaning solvent
rates at .55, .36, and .36. In each case, a synthetic solvent (1,1,1-T or
PCE) was used to perform the substitution.
6-6
-------
Because of APCD Rule 66, some substitution control has also been
carried out among other solvent categories, in particular air dryed sur-
face coating. However, from the present reactivity ratings of these other
solvent sources (see Table 4-2) it does not appear that the reductions in
reactivity were very large (at least as measured by the oxidant reactivity
schemes used here). For instance, air dried surface coating still rates
at .68, .55 and .55 according to the 2-group, 5-group and 6-group schemes.
These values are nearly as great as the average reactivity for all sources.
It is interesting to note that, in this case, one petroleum based solvent
was substituted for another petroleum based solvent.
As a gross generality, it appears that large reductions in reactivity
cannot usually be achieved by substituting one petroleum product for
another. To attain large reductions in reactivity apparently requires
major substitution of Class I compounds for compounds in Classes III to V.
This would usually be practical only by switching to synthetic solvents
(e.g., PCE dry cleaner or 1,1,1-T degreaser) or by converting to gaseous
fuels (e.g., methane or methanol). Substitution of Class II compounds
does not generally seem practical because Class II compounds are rare.
Substitution of one petroleum product for another would usually be
restricted to replacing Class IV and V compounds (e.g., olefins and
aromatics) by Class III compounds (e.g., C. parafins). Table 6-2
illustrates that replacement of all Class IV and V compounds with Class
III compounds would not have extreme effects on the reactivities of
solvents, gasoline engine exhaust or evaporated gasoline.
The conclusion that substituting one petroleum product for another
will generally not yield substantial reductions in reactivity is also
supported by the uniformity in source weight reactivities noted in
Section 4.2. Table 4-2 illustrated that reactivity ratings changed
little among all the varied uses of petroleum solvents and petroleum
fuels. Among sources involving petroleum based solvents or fuels,
weight reactivities varied only from about .5 to .9.
It should be noted that substitution of low reactivity compounds
may not be feasible for many petroleum based solvents if these solvents
are to retain their utility. For instance, the substitution of lesser
6-7
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reactives in surface coatings (under APCD Rule 66) has already been
carried out to the extent that further substitutions might produce
deterioration in performance. Thus, not only will substitution of lower
reactivity petroleum compounds have limited effect, but also it may be
costly in terms of performance losses.
To summarize, the utility of substitutive controls in attaining
substantial reductions in reactivity will be mostly limited to the use of
synthetic solvents or gaseous fuels which have near zero reactivity. The
substitution of lesser reactive petroleum products (e.g., C. paraffins)
for highly reactive petroleum products (e.g., aromatics) will usually not
result in major reductions in source reactivities and may be associated
with high costs in terms of product performance. Accordingly, the
benefit from allowing substitutive controls will be most significant for
sources where synthetic solvents or gaseous fuels are a viable control
measure.
6.2.2 Costs of the Reactivity Based Strategy with Substitutive Controls
This section considers the extra program requirements and program
costs of allowing substitutive controls. The extra program requirements
(in addition to those described in Section 6.1.2) are increased labora-
tory and field test capabilities. The increased costs are for additional
equipment and personnel.
The type of regulation being discussed allows compliance by sub-
stitution of low reactivity compounds for high reactivity ones as well
as by emission reduction measures. Because of this, the allowable
emissions would have to be recalculated each time the process causing
the emissions changes.
The additional program requirements involve upgrading laboratory and
field test capabilities and increasing the number of tests to be run.
Although most air pollution control agencies already have some labora-
tory facilities, in most cases, they would not have the necessary
equipment or personnel to conduct the much more sophisticated analyses
that this type of enforcement program would require. Similarly, the
actual taking of the sample at the emission source would be more com-
plicated and would probably require new equipment. Since the number
6-9
-------
of source tests would most likely be increased, the number of source
test personnel would probably have to be increased also.
Since the composition of the emissions from each individual source would
become important, the field testing requirements might become prohibitive
if only the local agency could certify the composition and thereby set
the legal mass emission rate. Because of this, it is probable that
provisions would be made in the law which would allow qualified private
testing labs to conduct the testing and analysis at the expense of the
plant operator. This would be to the advantage of both the agency and
the operator in the cases where a large backlog of testing was forcing
the operator to comply with more restrictive mass based regulations.
It is also conceivable that a dual system could be instituted whereby
a mass emission rate is set for all sources in a given type of industry
subject to being made less restrictive when analysis showed that the
reactivity was sufficiently low. In this case, the burden of proof
would lie with the operator. Under this system the costs to the control
agency would be reduced since the testing costs would be transferred to the
source operators.
Table 6-3 shows the anticipated additional costs for enforcing
regulations which allow substitution of low reactivity compounds for
high reactivity ones. These costs are calculated based on the assumption
that all tests are conducted by the control agency.
6.3 IMPLICATIONS OF THE BENEFIT/COST EVALUATION
The previous two sections briefly evaluated the costs and benefits
associated with alternative approaches to organic control policy in Los
Angeles. Section 6.1 compared indiscriminate organic control to a re-
activity based policy which establishes emission standards based on present
source reactivities but which does not allow substitutive controls. It
was noted that the reactive policy generally would yield the benefit of
concentrating emission reductions among the most reactive sources. This
would allow more total organics to be emitted for a given degree of over-
all control. However, for Los Angeles, this benefit translated only into
relaxing controls on PCE dry cleaning and 1,1,1-T degreasing. The extra
administrative and testing costs for this reactive strategy (over an
6-10
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indiscriminate control policy) were estimated to be about $10,000 to
$100,000 on an annualized basis.
Section 6.2 compared the first reactivity based policy to a second one
which establishes emission standards based on reactivity and allows sub-
stitutive controls. The extra benefit of this policy (as compared to the
first reactive policy) consisted of increased flexibility in selecting among
alternative control measures. The increase number of control options intro-
duced the possibility of reducing the costs of control. For organic sources
in Los Angeles, it was noted that large reductions in reactivity probably
could not be attained by substituting one petroleum product for another.
The benefits of substitutive controls apparently would be substantial only
for those sources which could attain very low reactivity by conversion to
synthetic solvents or gaseous fuels. The extra costs of this reactive policy
(as compared to the first reactive policy) were estimated to be about
$100,000 to $250,000 on an annualized basis.
Definitive recommendations concerning organic control policy cannot
be made based on the brief benefit/cost assessment performed above. However,
the following simple control policy does aopear to have general merit in
light of the above results. Since emission reductions according to re-
activity based schemes are close to 90% for nearly all sources (for 90%
overall control), organic control policy in Los Angeles should require large
emission reductions for nearly all sources. Variations in degree of control
among these sources should be dictated more by technical feasibility con-
siderations than by reactivity considerations. Exceptions to this general
rule should be made only for sources of extremely low reactivity. PCE
drycleaning and 1,1,1-T degreasing now qualify as exceptions according to
the reactivity classification schemes used in this report. By the use of
substitutive controls, other source categories may qualify as exceptions in
the future. These exceptions are likely to involve only sources which convert
to synthetic solvents or gaseous fuels.
6-12
-------
6.4 REFERENCES
1. "The Cost of Clean Air - Annual Report of the Administrator of the
Environmental Protection Agency to the Congress of the United States
in Compliance with Public Law 91-604, The Clean Air Act, as Amended",
Document #93-40, 22-4470, 1973.
2. Private Communication, Ron Ketchum, Los Angeles County Air Pollution
Control District, Los Angeles California, June 9, 1975.
6-13
-------
APPENDIX A
COMPUTATION OF AVERAGE SOURCE MOLECULAR WEIGHTS
Tables A-l through A-26 show the actual or estimated molecular weights
of the compounds or groups of compounds emitted by the various emission
sources. In the cases where sufficiently detailed data v,ere available
the actual molecular weights were determined either, in the case of a
single compound, by recording the published molecular weights or, in the
case of a group of compounds, by recording the appropriately weighted
average molecular weight. Uhere composition estimates were required, the
molecular weights were estimated by determining the molecular weight of an
average compound. The average compound used was signified by the notation
(C ) where n_ is the number of carbon atoms in the molecule. In the case of
halogenated compounds, the notation (C Cl ) was used where m is the
number of chlorine atoms in the molecule.
The average molecular weight shown in each table was determined by
calculating a weighted average based on the mole fraction of each type of
compound as listed in the appropriate tables in Sections 3.2.1 and 3.4.5.
The following shows the tables which apply to each source type:
STATIONARY SOURCES -
FUELS AND COMBUSTION
Petroleum Production and Refining Table
Petroleum Production A-l
Petroleum Refining A-2
Gasoline Marketing
Underground Gasoline Tanks A-3
Automobile Gasoline Filling A-4
Fuel Combustion A-5
Waste Burning and Other Fires A-6
A-l
-------
STATIONARY SOURCES -
ORGANIC CHEMICALS
Surface Coating Table
Heat Treated A-7
Air Dried A-8
Dry Cleaning
Petroleum Based Solvents A-9
Synthetic Solvents A-10
Degreasing
TCE Solvent A-ll
1,1,1-T Solvent A-12
Printing
Rotogravure A-13
Flexigraphic A-14
Industrial Process Sources
Rubber and Plastic Manufacturing A-15
Pharmaceutical Manufacturing A-16
Miscellaneous Chemical Manufacturing A-17
MOBILE SOURCES
Light Gasoline Powered Vehicles
Exhaust Emissions A-18
Evaporative Emissions A-19
Heavy Duty Gasoline Powered Vehicles
Exhaust Emissions A-20
Evaporative Emissions A-21
Other Gasoline Powered Equipment
Exhaust Emissions A-22
Evaporative Emissions A-23
Diesel Powered Vehicles A-24
Aircraft
Jet A-25
Piston A-26
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APPENDIX B
ADDITIONAL SUPPORT DATA FOR COMPOSITION ESTIMATES
Tables b-1 through B-18 present additional documentation to support
the composition data shown in Sections 3.2.1 through 3.4.5.
TABLE B-1 COMPOSITION OF THE VAPORS FROM UNDERGROUND GASOLINE
STORAGE TANKS [1]
Compound
Methane
Ethane
Ethyl ene
Propane
Propylene
Isobutane
n-Butane
Isobutene )
Butene-1 (
trans-2-Butene
cis-2-Butene
3-Methyl 1-butene
Isopentane
n-Pentane
1 -Rente ne
2-Methyl 1-butene
2-Pentene
2 ,2- Dimethyl butane
2-Methyl 2-butene
2,3 Dimethyl butane)
2-Methyl pentane J
Cyclopentane
3-Methyl pentane
n-Hexane
2,4-Dimethyl pentane)
2,3-Dimethyl pentane j
n-Heptane
Octene isomers
Benzene
Toluene
1 ,3-Dimethyl benzene )
1 ,4-Dimethyl benzene (
\ '
Mole " *
Vent Vapors from Regular
Grade Gasoline Storage Tank
3.47
1.93
0.37
0.90
0.17
2.06
6.24
0.37
0.40
0.31
3'22J 6.43+
3.2l)
3.49
0.32
0.63
0.68
0.28
1.00
1.50
0.42
0.69
0.55
0.08
0.02
0.01
0.07
0.01
Vent Vapors from Premium
Grade Gasoline Storage Tank
3.09
1.66
0.63
0.56
0.10
2.52
7.26
0.32
0.36
0.32
2'93J 5.86+
2.93J
2.99
0.24
0.49
0.43
0.29
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