-------
AIR POLLUTION ASPECTS
OF
ETHYLENE
Prepared for the
National Air Pollution Control Administration
Consumer Protection & Environmental Health Service
Department of Health, Education, and Welfare
(Contract No. PH-22-68-25)
Compiled by Quade R. Stahl, Ph.D.
Litton Systems, Inc.
Environmental Systems Division
7300 Pearl Street
Bethesda, Maryland 20014
September 1969
-------
FOREWORD
As the concern for air quality grows, so does the con-
cern over the less ubiquitous but potentially harmful contami-
nants that are in our atmosphere. Thirty such pollutants have
been identified, and available information has been summarized
in a series of reports describing their sources, distribution,
effects, and control technology for their abatement.
A total of 27 reports have been prepared covering the
30 pollutants. These reports were developed under contract
for the National Air Pollution Control Administration (NAPCA) by
Litton Systems, Inc. The complete listing is as follows:
Aeroallergens (pollens) Ethylene
Aldehydes (includes acrolein Hydrochloric Acid
and formaldehyde) Hydrogen Sulfide
Ammonia Iron and Its Compounds
Arsenic and Its Compounds Manganese and Its Compounds
Asbestos Mercury and Its Compounds
Barium and Its Compounds Nickel and Its Compounds
Beryllium and Its Compounds Odorous Compounds
Biological Aerosols Organic Carcinogens
(microorganisms) Pesticides
Boron and Its Compounds Phosphorus and Its Compounds
Cadmium and Its Compounds Radioactive Substances
Chlorine Gas Selenium and Its Compounds
Chromium and Its Compounds Vanadium and Its Compounds
(includes chromic acid) Zinc and Its Compounds
These reports represent current state-of-the-art
literature reviews supplemented by discussions with selected
knowledgeable individuals both within and outside the Federal
Government. They do not however presume to be a synthesis of
available information but rather a summary without an attempt
to interpret or reconcile conflicting data. The reports are
-------
necessarily limited in their discussion of health effects for
some pollutants to descriptions of occupational health expo-
sures and animal laboratory studies since only a few epidemic-
logic studies were available.
Initially these reports were generally intended as
internal documents within NAPCA to provide a basis for sound
decision-making on program guidance for future research
activities and to allow ranking of future activities relating
to the development of criteria and control technology docu-
ments. However, it is apparent that these reports may also
be of significant value to many others in air pollution control,
such as State or local air pollution control officials, as a
library of information on which to base informed decisions on
pollutants to be controlled in their geographic areas. Addi-
tionally, these reports may stimulate scientific investigators
to pursue research in needed areas. They also provide for the
interested citizen readily available information about a given
pollutant. Therefore, they are being given wide distribution
with the assumption that they will be used with full knowledge
of their value and limitations.
This series of reports was compiled and prepared by the
Litton personnel listed below:
Ralph J. Sullivan
Quade R. Stahl, Ph.D.
Norman L. Durocher
Yanis C. Athanassiadis
Sydney Miner
Harold Finkelstein, Ph.D.
Douglas A. Olsen, Ph0D.
James L. Haynes
-------
The NAPCA project officer for the contract was Ronald C.
Campbell, assisted by Dr. Emanuel Landau and Gerald Chapman.
Appreciation is expressed to the many individuals both
outside and within NAPCA who provided information and reviewed
draft copies of these reports. Appreciation is also expressed
to the NAPCA Office of Technical Information and Publications
for their support in providing a significant portion of the
technical literature.
-------
ABSTRACT
Ethylene does not appear to present a health hazard
to humans or animals. However, ethylene is a phytotoxicant
which disrupts the normal function of plant hormones and
growth regulators. The effects on plants include growth
reduction, epinasty, abscission of flower and leaves, and
dry sepal in orchids. Several incidents of plant damage from
ethylene air pollution have been reported. Furthermore,
ethylene undergoes photooxidation reactions with nitrogen
oxides, resulting in the formation of formaldehyde, carbon
monoxide, and ozone.
Ethylene air pollution has resulted primarily from
automobile exhaust and other combustion sources. However,
industrial emissions of ethylene can be a local source.
Ethylene is also evolved from plant life.
Ambient air concentration data are limited. Air samples
taken recently in California indicate that the average ethylene
concentration in large metropolitan areas ranges from 40 to
120 |ag/m3 , with maximums as high as 820 |_ig/m3 .
Industrial control methods applicable to other volatile
hydrocarbons are suitable for use with ethylene. Ethylene
emissions from automobile exhausts present a problem which,
although it is under study, has not yet been solved.
Economic losses have been reported among orchid growers
-------
in California and New York, and among cotton growers in
Texas.
Methods of analysis for ethylene have been reported in
the parts per billion range, using gas chromatographic
techniques.
-------
CONTENTS
FOREWORD
ABSTRACT
1. INTRODUCTION 1
2. EFFECTS 3
2.1 Effects on Humans . . . . 3
2.2 Effects on Animals ».... 3
2.2.1 Commercial and Domestic Animals ... 3
2.2.2 Experimental Animals 4
2.3 Effects on Plants . . ......... . . . . 4
2.3.1 Phytotoxicity „ ............ 5
2.3.2 Sensitivity of Plants „ . 6
2.3.3 Incidents of Plant Damage ..... 0 . 7
2.4 Effects on Materials ...... . 10
2.5 Environmental Air Standards . . 10
3. SOURCES 12
3.1 Natural Occurrence .............. 12
3.2 Production Sources 12
3.2.1 Pyrolytic Processes 13
3.3 Product Sources ...... 15
3.4 Other Sources 15
3.4.1 Automobile and Diesel Emissions .... 16
3.4.2 Incinerator Effluents ..... 18
3.4.3 Burning of Agricultural Wastes 19
3.5 Environmental Air Concentrations 19
4. ABATEMENT „ 22
5o ECONOMICS 23
6. METHODS OF ANALYSIS . 24
6.1 Sampling Methods 24
6.2 Qualitative and Semi-quantitative Determination
Methods . 24
6.3 Quantitative Determination Methods . <,.... 25
7. SUMMARY AND CONCLUSIONS 27
REFERENCES
APPENDIX
-------
LIST OF TABLES
1. Comparative Phytotoxicity of Unsaturated Carbon
Gases 8
2. American Industrial Hygiene Association Recommended
Standards for Ethylene 11
3. Ethylene Concentration in Automobile Exhaust .... 17
4. Concentration of Ethylene in Ambient Air 21
5. Major Organs of Various Plant Species Producing
Ethylene 41
6. Maximum Rates of Ethylene Production by Various
Fruits 43
7. Production of Ethylene in the United States, 1958-67. 44
8. Ethylene Consumption in United States, 1950, I960,
1970 45
9. Trends in Ethylene Consumption by End Use in the
United States 46
10. Ethylene in Diesel Exhaust 47
11. General Information and Properties of Ethylene ... 48
12. Summary of Reported Effects of Ethylene on Plants . . 49
13. U.S. Production of Ethylene 52
14. Ethylene Capacity by States 55
15. Ethylene Emissions from Burning of Agricultural
Wastes 56
-------
1 . INTRODUCTION
Ethylene (ethene), a colorless hydrocarbon gas of the
olefin series, is one of the major growth petrochemicals of
the United States and of the world. Ethylene is not toxic
to humans or animals, yet despite this fact, it presents a
considerable air pollution problem, for two reasons: (1) it
is a significant phyt o toxic ant , and (2) it contributes to
photochetnically produced air pollution.
Ethylene in the atmosphere has caused substantial dam-
age to several varieties of plants, the most notable of which
are commercially grown orchids and other commercial flowers.
Documented instances of commercial loss due to ethylene air
pollution are known. Although it does not directly attack
plant tissues like most other gaseous phytotoxicants, ethylene
interferes with the normal function of the plant hormones or
growth regulators. This fact is also applied beneficially for
the ripening of fruit crops .
Ethylene is the most abundant (based on mole volume) of
the photoreactive hydrocarbons in the lower atmosphere. Ethyl-
ene undergoes photochemical reactions with nitrogen oxides^' ^®'
19,47,70,86,95,103 and algo reacts with ozone. 18, 97
reactions may contribute to eye irritation in polluted atmo-
spheres. The major products in both reactions are formaldehyde
-------
and carbon monoxide. In addition, the photochemical reaction
of ethylene and nitrogen dioxide produces ozone; however, no
PAN (peroxyacetyl nitrate) type compound is observed. When
the reaction of ethylene-nitrogen dioxide is carried out in
the presence of sulfur dioxide, only a small amount of aerosol
is found and there is only a slight increase, if any, in the
amount of eye irritation. 41/42,47,95 rp-^g phot oox id at ion reac-
tivity of ethylene is less than other olefinic hydrocarbons
but greater than paraffins, acetylenes, and some aromatic hydro-
carbons.5'105
The major sources of ethylene production are the chemi-
cal industry and the exhaust from automobile engines. As the
total production from these two sources is predicted to increase
at a steady rate in the foreseeable future, air pollution by
ethylene is likely to increase, unless control procedures are
implemented.
The physical and chemical properties of ethylene are
tabulated in Table 11 in the Appendix.
-------
2. EFFECT S
2.1 Effects on Humans
At concentrations Which occur in the ambient atmosphere,
ethylene is not toxicologically significant, as it produces
no physiological effects on humans or animals. There are no
known local or systemic chronic or acute effects. However,
ethylene will undergo photooxidation reactions with nitrogen
oxides and other substances present in the atmosphere, resulting
in products which can have deleterious effects on humans.
At high concentrations, ethylene acts as a simple asphyxiant,
and can cause narcosis and unconsciousness. In the presence of
sufficient oxygen, ethylene acts as an anesthetic; concentrations
of 75 to 90 percent ethylene in oxygen have been used as
27,72,88
anesthetics in hospital surgery.
The only significant hazards in the industrial use of
ethylene are its flammability and the possibility of causing
asphyxia, due to lack of sufficient oxygen in the work atmo-
27,88
sphere.
2.2 Effects on Animals
2.2.1 Commercial and Domestic Animals
No information was found in the literature reviewed
concerning injury or death of domestic or commercial animals
from environmental exposures to ethylene.
-------
2.2.2 Experimental Animals
73
Luckhardt and Carter exposed several different species
of animals—including a mouse, rat, rabbit, guinea pig, and
kitten—to concentrations of 75 to 95 percent ethylene in oxygen
for periods ranging from 30 to 100 minutes. These doses acted
as an anesthetic and produced no notable side effects except
nausea, which disappeared after a short time.
57
Hirschfelder and Ceder studied the effect of ethylene
inhalation on the growth rate of rats. The rats were exposed
to ethylene at approximately 11,500,000 Lig/m3 (10,000 ppm)*
for 17 days (11 rats, 10 controls); 1,150,000 |jg/m3 (1,000 ppm)
for 63 days (11 rats, 11 controls); and 115,000 |~Lg/m3 (100 ppm)
for 45 days (5 £ats, 5 controls) and 72 days (11 rats, 11
controls). Hirschfelder and Ceder concluded, on the basis of
these experiments, that these concentrations of ethylene do
not appreciably affect the growth rate of rats. In addition,
ethylene added to the drinking water of rats had basically no
effect on the rats' growth rate.
27 54
According to Clayton and Platt, Harvey reported
similar results with inhalation experiments using guinea pigs.
81
The Merck Index gives 950,000 ppm (1,092,500,000 i-ig/m3 )
ethylene in air as the lethal concentration for mice.
2.3 Effects on Plants
Ethylene ranks as one of the most important phytotoxicants,
32,33,82,83,85 82
Middleton listed the phytotoxicants in
*1 ppm ethylene = 1,150 |-ig/m3 .
-------
descending order of importance as fluoride, ozone, sulfur
dioxide, oxidant, and ethylene. In California, however,
32,64 82
ethylene is considered the second or third most
important phytotoxicant.
2.3.1 Phytotoxicity
22,27,29,32,56,83
The effect of ethylene on plants is unique.
Most gaseous phytotoxicants cause direct, irreversible tissue
damage through a caustic action. Ethylene, on the other hand,
does not directly attack plant tissue, but rather, interferes
with the normal action of the plant hormones and growth
regulators. This interference results in morphogenetic and
physiological changes in the tissue.
Ethylene produces a wide variety of effects in plants.
Some of the important effects of ethylene on plants are:
(1) growth retardation; (2) epinasty (downward curvature in
the growth of leaves and shoots); (3) the abscission of leaves,
buds, and flowers; (4) irregular opening of flowers; (5)
senescence of leaves and flowers; (6) inhibition of elongation,
and preferential swelling of stems; (7) fading of flowers;
(8) blanching of chlorophyll; and (9) hastening of fruit-
ripening and coloration. Ethylene can cause plants to lose
their ability to orient normally with respect to gravity—
the stem assumes a horizontal position (horizontal nutation),
as do the secondary roots (plagiogeotropism), and normal growth
-------
movement (circumnutation) ceases. Ethylene may affect the
roots by inhibiting growth or may cause formation of lateral
roots.
Since orchids are a very sensitive crop, they are readily
affected by ethylene, and instances of economic losses from
25,27,82,83,84
ethylene pollution have often been reported.
Ethylene generally causes the sepals of orchids to wither and
dry without detectable injury to the petals or leaves. The
collapse of sepals, which has been termed "dry sepal," is most
commonly found with the white-flowered orchids, cattleya,
and phalaenopsis. This damage is rarely found with cymbidium,
cypripedium, or vanda orchids.
Ethylene also produces beneficial effects which are of
commercial importance. Probably the most important of these
are the ripening and coloring of fruit. 27» 52 »H5 The fruit
is generally exposed to ethylene concentrations of 2,300
to 23,000 Hg/rn3 of air (2 to 20 ppm) with continuous air
circulation. Ethylene has also been used in the branching
55.74 11,12
of celery and to accelerate the after-ripening of grain.
2.3.2 Sensitivity of Plants
In general, flower crops are more sensitive to ethylene
84
than agricultural crops. The most sensitive is the orchid,
particularly the white cattleya, which shows dry sepal injury
from as little as 24 hours of exposure to ethylene at 2,3
-------
25,36
(0.002 ppm). Other sensitive plants (showing symptoms
of injury at an ethylene concentration of 115 Mg/m" or 0.1 ppm)
25,27,29,69
include carnation, African marigold, sunflower,
tomato, Chenopodium album, potato, pepper, buckwheat, castor
bean, pea, and lemon. Plants that are resistant to ethylene
104
include grasses and lettuce. The phytotoxicity of ethylene
may be dependent upon temperature. Thms, roses were found to
be sensitive to low concentrations of ethylene only at certain
118
temperatures. At 70°F, petal fall occurs with ethylene
concentrations of 11,500 M-g/m (10.0 ppm) after 24 hours;
but at 50°F, no abscission occurs with the same concentration
and exposure time, nor at 41°F with 46,000 1-tg/m3 (40 ppm)
of ethylene after 168 hours.
Some other unsaturated carbon compounds will produce
29
responses similar to those caused by ethylene. Ethylene,
however, is a much stronger phytotoxicant than the others,
as shown in Table 1.
The reported effects and sensitivities of plants to ethylene
have been summarized in Table 12 in the Appendix.
2.3.3 Incidents of Plant Damage
The first recorded case of ethylene plant damage was
30
reported in 1908 by Crocker and Knight. Plants in green-
houses, particularly carnations and tomatoes, were damaged as
a result of the ethylene (3 to 4 percent) contained in the illum-
29 ,30
inating gas used to heat the greenhouses. The use of
-------
8
TABLE 1
COMPARATIVE PHYTOTOXICITY OF UNSATURATED CARBON GASES
29
Minimum Concentration of
Gas Producing Response (ppm)
Gas
Ethyl ene
Acetylene
Propylene
Carbon monoxide
Butyl ene
Sweet Pea^
0.2
250
1,000
5,000
Tomato^
0.1
50
50
500
50,000
aEffect noted: declination in sweet pea seedlings
(3-day exposures).
"Effect noted: epinasty in tomato petiole (2-day
exposures)-
-------
other heating methods eliminated this cause of ethylene plant
damage.
53
In 1957, Hall _et al_. reported damage to cotton and
other crops growing near a polyethylene factory in Texas. Air
samples taken at this location indicated that the ethylene
atmospheric concentration ranged from 560 to 3,450 j-ig/m
(0.04 to 3 ppm). Symptoms of injury were found on plants
as far as 4 miles downwind from the factory, although no
ethylene was detected in the atmosphere. On the basis of the
plant symptoms, however, it was believed that the concentration
of ethylene in the air must have exceeded 3,450 f-ig/m . The
most pronounced damage occurred near the factory and downwind
from the factory, the damage decreasing in extent with distance
from the source. The symptoms observed included epinasty,
growth retardation, early bud development, and abscission of
the buds and fruits that resulted in almost total loss in
yield in heavily damaged areas.
Ethylene air pollution in the San Francisco and Los
Angeles areas has caused much damage to greenhouse plants,
particularly orchids, carnations, snapdragons, and roses.
25,27,34,82
The damage usually occurred in winter during
periods of stable air conditions and light winds. Similar
injury to orchids has been observed in the New York City area
36
and is believed to be at least partly due to ethylene pollution.
-------
10
Economic losses resulting from these situations are discussed
in Section 5.
2.4 Effects on Materials
Ethylene is not known to corrode or stain material
surfaces.
2.5 Environmental Air Standards
88
According to Patty, "the maximum permissible limit
of ethylene in workroom air should not exceed 6,300 mg ethylene/m3
of air (6,300,000 ug/m3 ) (5,500 ppm), which is 20 percent of
the lower flammable limit. The threshold limit for ethylene
has been established at 1,150 mg/m3 (1,150,000 ug) (1,000 ppm)."
The American Industrial Hygiene Association has estab-
45
lished ambient air quality standards for ethylene. However,
these standards serve only as a guide, since sufficient knowl-
edge is not available at this time to adopt unequivocal
standards. The recommended standards are given in Table 2.
The State of California has adopted ambient air quality
standards for ethylene of 575 l-ig/m3 (0.5 ppm) for 1 hour or
25,62,106
115 Lig/m (0.1 ppm) for 8 hours. These are considered
"adverse" levels, based on the damage to vegetation. No
"serious" or "emergency" levels based on the effects on
humans have been set.
Russia has established the ambient air quality standard
63,106
for ethylene of 3,000 ug/m3 (2.3 ppm) for a 24-hour average.
The permissible standard for a 20-minute average is set at the
same value (3,000 Hg/m3).
-------
11
TABLE 2
AMERICAN INDUSTRIAL HYGIENE ASSOCIATION
RECOMMENDED STANDARDS FOR ETHYLENE45
Rural
Residential
Commercial
Industrial
1-hr
Uq/m3
287.5
575
862.5
1,150
Max*
ppm
0.25
0.50
0.75
1.00
8-hr
^/m3
57.5
115
172.5
230
Max*
ppm
0.05
0.10
0.15
0.20
*The rural concentrations should not produce adverse
effects in the most sensitive plants. The residential concen-
trations should produce only slight injury to the most sensi-
tive plants.
-------
12
3. SOURCES
3.1 Natural Occurrence
Ethylene is not normally found in deposits of petroleum
or natural gas.
However, ethylene is produced naturally from many, if not
all, types of plants. The ethylene can emanate from flowers,
37,38
fruits, leaves, and stems of a number of plant species.
20
Burg recently compiled an extensive list of plants known to
produce ethylene; these plants are listed in Table 5 in the
16
Appendix. Biale et al. obtained quantitative data on the
rates of ethylene production in various fruits (see Table 6
in the Appendix). According to these authors, fruits which
did not appear to evolve ethylene have subsequently been shown,
16,21
by a more sensitive gas chromatography analysis method, to
2
produce very small amounts. Akamine found that the vanda
orchid produces as much as 3,400 M-1/kg-hr of ethylene.
The importance of this biologically derived ethylene
in relation to the overall air pollution problem is not known
at this time. However, numerous examples are given in the
literature in which these emissions caused damage to plants
25,27,29
in greenhouses and during storage and shipment.
3.2 Production Sources
Ethylene is one of the major growth chemicals in the
23
United States and the world. The production in the United
States for 1967 was almost 12 billion pounds (see Table 7
-------
13
in the Appendix). The production has approximately doubled
in the last 6 years. This rapid growth rate is expected to
continue over the next decade at approximately 10 percent
90
per year. The demand for 1969 and 1971 is projected
1,46
to be 14.1 and 17.3 billion pounds, respectively-
Most of the ethylene produced today is consumed by the
producer; only about 25 to 33 percent of the total production
is sold to other users.
Presently there are 38 producers of ethylene in the United
States (see Table 13 in the Appendix). Over 55 percent of
the ethylene production is located in Texas (with 17 plants),
while Louisiana is responsible for 28 percent, with eight
plants (see Table 14 in the Appendix). The remaining plants
are distributed over nine States (including Puerto Rico).
Practically all commercial ethylene is manufactured by
the cracking of petroleum fractions or natural gas, usually
23
by means of a pyrolytic process. Small amounts are thus
recovered as a by-product of refinery catalytic cracking
operations. Some pure ethylene is manufactured from the
catalytic dehydrogenation of ethyl alcohol or ethyl ether.
3.2.1 Pyrolytic Processes
Any petroleum fraction, from ethane to heavy gas oil—
even to whole crude oil—can be used as the feedstock to
produce ethylene. Almost all of the available ethane obtained
-------
14
from natural gas liquids or from refinery gases is consumed
in ethylene production. Other feedstocks commonly used in the
United States are liquified petroleum gases (e.g., 95 percent
propane and 5 percent butane) and, to a lesser extent, naphtha
(crude oil fractions having the boiling range of 90° to 400°F).
Tne composition of the feedstock and the operating condi-
tions of the pyrolysis reactor determine the amount of ethylene
in the final product mixture. Generally, the pyrolysis is
conducted at nearly atmospheric pressures and at 1,300 to
1,600°F. Several types of reactor systems are used, including
23
the following: fired tubular heaters, pebble-bed heaters,
fluidized-bed cracking regenerative furnaces, the autothermic
cracking method, and the catarole catalytic process. The most
commonly used method has been the fired tubular heater, which
gives ethylene yields of from 24 to 48 percent conversion,
depending on the feedstock and conditions. There are many
by-products, including hydrogen, paraffins, olefins, diolefins,
and aromatic compounds, as well as minor contaminants such as
acetylene, propadiene, hydrocarbons, polymers, and acid gases.
Thus, recovery, separation, and purification are dependent upon
the type and quantity of the different products obtained.
Ethylene is recovered by fractional distillation at low
temperatures and high pressures, and less commonly, by solvent
44,73,92
extraction or absorption. Sometimes the ethylene is
used directly without purification.
-------
15
3.3 Product Sources
Ethylene is one of the most important petrochemicals in
23
the world. It is usod extensively as a raw material in the
manufacture of organic chemicals and plastics. One of the most
important products is polyethylene, a polymer of ethylene
used for packing films as well as for wire insulation, and
"squeeze" bottles. Other important chemicals produced from
ethylene include ethyl alcohol or ethanol, ethylene oxide,
ethylene glycol, ethyl chloride, ethylene dichloride, styrene
(via ethylbenzene), and linear alcohols. Table 8 in the
Appendix shows the consumption of ethylene in the United
States by products. Table 9 in the Appendix shows the major
end uses of these chemicals. Plastics have so far been the
major product of ethylene, and this use will probably continue
to increase in the future.
The proportion of ethylene in the atmosphere which
results from these particular sources in not known, except in
53
one isolated case. Hall et al. reported damage to cotton
from ethylene emissions from a polyethylene plant (see Section
2.3.3).
3.4 Other Sources
Ethylene may form as a by-product from incomplete combus-
tion of hydrocarbons and oiher organic substances. Thus,
ethylene has been found to be one of the components of auto-
mobile and diesel combustion emissions (exhaust and blow-by
-------
16
emissions)/ incinerator effluents, and agricultural waste
combustion gases.
3.4.1 Automobile and Diesel Emissions
Motor vehicle emissions are believed to be the major
source of ethylene pollution in California metropolitan areas.
24,25
In Los Angeles, the ethylene emission from automobile
exhaust has been estimated at 60 tons per day.
Several studies have been conducted to determine the
ethylene concentration in automobile exhaust in relation to
28,59,79,110
the engine operating mode. The data summarized
in Table 3 indicate that the ethylene concentration varies
considerably with the operating mode—with the deceleration
mode producing the most ethylene. In general, automobile
exhaust produces approximately 7.8 pounds of ethylene per ton
35
of gasoline consumed.
59
Hurn et al. studied the effect of different fuels on
the concentration of ethylene in the automobile exhaust. The
composition of the fuel was found to be an important variable
in the amount of ethylene produced. The data indicated that
the paraffin content—and to a lesser extent, the olefin con-
tent—were the main contributors to ethylene formation in the
exhaust.
80
McMichael and Sigsby studied the effect of hot and
cold starts in winter and summer using regular and premium
fuels. The results indicated that all these variables had
only a slight effect on e'thylene in the exhaust. The data
-------
TABLE 3
ETHYLENE CONCENTRATION IN AUTOMOBILE EXHAUST
Vehicle
1957 Dodge
1958 Chevrolet
1949 Oldsmobile
1949 Chevrolet
Forklift
Automobile
engine
Automobile
engine
Automobile
engine*3
1962 V-8
Concentration of Ethylene (ppm)
Idle
101
400
121
31a
66, 80, 194
200
188
81
390
Acceleration
55
105
208
166a
270
118
(15-30 mph)
103
(15-30 mph)
168-233
(15-60 mph,
25 sec)
Cruise
230
190
310
298a
170
133
(30 mph)
93
(30 mph)
304
(50 mph)
555
(40 mph, 2/3
max torque )
Deceleration
395a
870
1,030
(50-20 mph)
39
(50-20 mph)
989-2,050
(50-15 mph,
25 sec)
Simulated
Traffic Cycle
648
Reference
110
28
79
59
aTotal two carbon compounds.
bsame engine as above but engine modified by adding air injection, leaner
carburetor, and 10° spark retard.
-------
18
showed that generally ethylene was produced in somewhat
greater amounts (a) from cold starts rather than from hot
starts, (b) in winter rather than in summer, and (c) from
premium fuel rather than from regular fuel.
Although ethylene concentration in the blow-by emissions
of automobiles was found to be generally above 155,000
87,100
(100 ppm), it was over 310,000 ug/m (200 ppm) in many
cases. The concentration of ethylene was less from the blow-by
emissions than from the exhaust. Furthermore, the ethylene
concentrations varied less with different engine modes in
100
the blow-by emissions than in exhaust analyses.
Two studies reported the concentration of ethylene in
71,91
diesel exhaust. The results (see Table 10 in the Appendix)
indicate that the ethylene concentration is usually below 60,000
|-ig/m3(50 ppm) even under heavy loads.
3.4.2 Incinerator Effluents
Effluents of multiple- chamber incinerators usually
contain ethylene in concentrations of less than 11,500 |-ig/m3
49,97,113
(10 ppm). When an afterburner is used, the ethylene
49
concentration becomes nearly zero. Single-chamber incinerators
were found to have ethylene concentrations of 23,000 to 31,000
3 49
M-g/rn . However, inadequately designed incinerators may be
a major source of pollution, producing concentrations of
113
ethylene as high as 3,565,000 l-ig/m3 .
61
Jerman and Carpenter analyzed gas samples from the
-------
19
pyrolysis of solid municipal waste. The range of values for
the 24 samples was 460,000 to 39,330,000 ^g/m3 (400 to 34,200
ppm) with an average of 17,855,000 |-ig/ma (15,700 ppm). Thus,
poor or incomplete combustion of solid wastes may be an important
source of ethylene pollution.
3.4.3 Burning of Agricultural Wastes
Laboratory studies have been conducted to determine the
amount of ethylene emissions produced from burning of agri-
17,35
cultural wastes. These results are summarized in Table 15
in the Appendix. Field studies confirm that the laboratory
data are probably representative of normal field conditions.
The results show that moisture content, type of waste, and
location, can be variables that determine the amount of ethylene
that is produced. For comparison, automobile exhaust produces
approximately 7.8 pounds of ethylene per ton of gasoline, or
about 2 to 10 times more ethylene per ton than agricultural
35
wastes.
The wastes burned per year in the San Francisco Bay
area are as follows: 121,111 tons of fruit prunings, 1,632
35
tons of barley straw, and 28,140 tons of native brush.
3.5 Environmental Air Concentrations
Only limited data are available on the concentration of
ethylene in ambient air.
4,27,97
Several studies have been made in California.
-------
20
97
The data are summarized in Table 4. Scott et al. found
that the ethylene air concentration in South Pasadena, Calif.,
appears to correlate with the amount of automobile traffic
4
and with temperature inversions. A3tshuller and Bellar
collected extensive data on ethylene concentration in Los
Angeles for a total of 10 days in September and October 1961.
They also noted a peaking in ethylene concentration during
the heavy traffic hours, with these high values usually
persisting for at least one hour. The maximum for the day
generally ranged between 80 and 130 Hg/rn3. It is believed
that an unusually high value of 300 Hg/m3 found late one
afternoon was partly due to large forest fires north of Los
27
Angeles. In a 1967 article, Clayton and Platt reported
ethylene concentration for three metropolitan areas in
California (see Table 4). Although all pertinent information
was not given (no data on time, exact location of sampling,
or method of analysis), the data indicated a maximum concen-
tration for ethylene of 820 t-ig/m in Los Angeles.
-------
TABLE 4
CONCENTRATION OF ETHYLENE IN AMBIENT AIR
Location (California)
South Pasadena
South Pasadena
(at Pasadena Freeway)
Los Angeles
Los Angeles*
Oakland*
Ventura*
No. of
Samples
4
1
125
39
73
52
Date
12/56
12/31/56
9/12/61 to
11/14/61
( 4-month
period,
1967?)
(10-month
period/
1967?)
( 4-month
period,
1967?)
Concentration, ug/m3
Ranqe
290-580
820
110-150
Avq
410
50
120
40
63
Max
580
150
820
Reference
97
4
27
. . .1 ^
*Data given in ppm and converted to M-g by dividing by 2 and multiplying by 1.15,
-------
22
4. ABATEMENT
Ethylene is one of the many volatile hydrocarbons
present in the emissions from combustion engines, petroleum
refineries/ organic chemical plants, and incinerators.
Ethylene poses no peculiar control problem in these emissions
and, thus can be controlled by the methods generally used for
hydrocarbons. These methods include combustion techniques,
adsorption methods, and vapor recovery systems.
106
Stern discusses the techniques, cost, and efficiency
of the control methods for hydrocarbons employed by the petroleum
industry. No quantitative data directly pertaining to ethylene
emissions from industrial sources were found.
One of the major sources of ethylene air pollution—
automobile exhaust—has not yet been effectively controlled.
However, programs are in operation for studying the problem
of hydrocarbon emissions from automobiles as well as methods
for controlling those emissions.
Special control problems may be presented if ethylene
evolved from vegetation is an important source—particularly in
open fields. Ethylene given off by plant life in confined
areas—such as greenhouses, storage areas, and shipping con-
tainers—has been controlled by the use of brominated char-
3,50,51
coal.
-------
23
5. ECONOMICS
No information was found in the literature giving the
damage to humans, animals, or materials or the economic losses
resulting from ethylene air pollution. However, economic losses
due to plant damage from ethylene pollution have been reported.
The most significant economic damage is to commercial flower
crops, particularly orchids, carnations, roses, and snapdragons.
The flower crop loss from ethylene air pollution in the
San Francisco and Los Angeles areas has been reported to run
25
into the hundreds of thousands of dollars annually. In
the San Francisco area, the combined loss of three orchid
34
growers amounted to about $70,000 in 1959. In the Los
Angeles area, extensive and recurring injury to orchids since
the early 1950's has caused orchid production to be moved to
82
the rural areas, away from the ethylene pollution. Heck
56
et al. reported extensive damage to a cotton crop near a
polyethylene factory in Texas. Cotton downwind and within
one mile of the factory was almost totally lost. Ethylene,
which appears to be one of the components in New York air
pollution, causes damage to orchids in the vicinity of New
36
York.
No information was found on the economic costs of the
abatement of ethylene air pollution.
The production and consumption data for ethylene have
been discussed in Section 3.
-------
24
6. METHODS OF ANALYSIS
6.1 Sampling Methods
Ethylene samples can be collected by the grab sampling
13,35,71,113
method, i.e., collection into an evacuated container.
Gas chromatography or infrared spectroscopy methods of
analysis lend themselves to direct passing of the sample into
4,60,61
the instrument without use of collection containers.
99
Some authors report collecting ethylene in freeze traps,
117 107
in mercuric solution, and on silica gel.
There are no problems in the collection of ethylene
samples other than the normal difficulties in taking and
transferring samples. However, in cases in which both ethylene
and nitrogen oxides are present in large amounts (e.g., auto-
mobile exhaust), a reaction between the two substances may
occur in the sampling vessel. This very slow reaction can be
reduced to a negligible rate by diluting the sample with
dry nitrogen.
6.2 Qualitative and Semi-quantitative Determination Methods
A detector tube method has been described by Kitagawa
66
and Kobayashi which has a sensitivity of about 23,000 (-ig/m3
o
(20 ppm) with +_ 5 percent error when a 10 cm sample is used.
68,108
Another adsorbent was reported to detect approximately
10 Hg/m3 (0.01 ppm) ethylene by using a 3,000 cm sample
size, which is drawn through the tube at 100 cm3 per minute.
-------
25
A portable instrument has been reported to provide a
simple and reliable field method for estimating ethylene
concentration in the range of 5,700 to 230,000 |~ig/m3
108,109
(5 to 200 ppm). The air sample is drawn over mercuric
oxide at 285 C. The mercury vapor released by the ethylene
is passed over a strip of sensitized seleno-cyanate paper at
125°C. The length of the black coloration is used to estimate
the amount of ethylene present.
6.3 Quantitative Determination Methods
Gas chromatography methods have found widespread use
for determining the presence of ethylene as well as numerous
105
other hydrocarbons. Gas chromatography has gained wide
acceptance because it is a simple and rapid technique. With
the development of the new packed and open tubular columns,
automatic temperature programming, and new types of detectors—
particularly the flame ionization detector—one can obtain
rapid, efficient separation of many components with a sensitivity
in the ppb range and even lower. The commonly used gas ahromato-
graphic methods for detecting ethylene employ a silica gel
packed column at or near room temperature, with a flame
4,13,14,15,80,110
ionization detector. Other columns that
35 71 113
are ueed include alumina, dimethyl sulfolane, hexadecane,
61 67,79
polypak-2, multicolumn techniques, and open tubular
60,78
columns. Gas chromatography has been used to determine
-------
26
4,15,101 15,60,79,110
ethylene in air samples, automobile exhaust,
100 61 35
blow-by. municipal wastes, agricultural wastes, and
113
incinerator effluents. To increase the sensitivity of
13,43,48,113
this method, some authors also used trapping techniques.
Infrared spectroscopy has been used to determine ethylene
97 71,77,96,102
in air samples, automobile and diesel exhaust,
116
and incinerators. To obtain a greater sensitivity, very
97
long optical path lengths are needed (e.g., 300 meters),
generally maHing large samples necessary. The absorption
peak at 10.5 p. (952cm~l) is normally used, having a sensitivity
of greater than 0.1 ppm.
Ethylene concentration has been determined by mass
99 28,93,114
spectrometry in air samples and automobile exhaust.
A manometric technique has been used for determining
117
small amounts of ethylene. A mercuric perchlorate solution
containing the collected ethylene is acidified in a closed
system, and the released ethylene is determined by the change
in pressure. The sensitivity is approximately 0.2 ml of ethy-
lene per 2 ml of solution.
The chemical methods developed for quantitative determ-
7,8,9,76,85
ination of olefins are not generally applicable to
ethylene because of the lack of reactivity of the ethylene
and the low sensitivity of the product formed with ethylene.
-------
27
7. SUMMARY AND CONCLUSIONS
Ethylene does not appear to be toxic to humans or
animals or cause damage to materials in the concentrations
that have been found in air. In fact, 75 to 90 percent
ethylene in oxygen has been used as an anesthetic in hospital
surgery with no adverse side effects.
However, low concentrations of ethylene do have a
pronounced effect on plant life. Unlike most gaseous phyto-
toxicants, which attack the plant tissue, ethylene disrupts
the normal processes of the plant hormones or growth regulators.
This disruption results in morphoganetic and physiological changes
in the plant. The response to ethylene varies widely with
different species of plants. Some of the commonly observed
effects are growth reduction; epinasty; abscission of flowers,
buds, and leaves; discoloration; and abnormal growth patterns.
Another important aspect of ethylene air pollution is
the photooxidation products created by reaction of ethylene
with nitrogen oxides in the atmosphere. Although ethylene is
not as reactive as many other hydrocarbons, it is the most
abundant (on a mole basis) of the "reactive" hydrocarbons present
in the atmosphere. The major products formed from the photo-
oxidation of ethylene are formaldehyde and carbon monox-
ide.
The major source of ethylene air pollution in large
metropolitan areas appears to be emissions from combustion,
-------
28
particularly automobile exhaust. It has been estimated that
in Los Angeles/ ethylene emissions from automobile exhaust
amount to 60 tons per day. No information was found on the
contribution of industrial sources to ethylene pollution.
Approximately 55 percent of the commercial ethylene is
produced in Texas. Moreover/ in one case, a polyethylene factory
was shown to be a local source of ethylene pollution.
Ethylene is also produced by plant life. The importance
of this source is not known in the case of open fields, but
in confined areas such as greenhouses or plant storage con-
tainers, damage has been reported to certain species of plants,
particularly orchids.
Only limited information is available concerning the
amount of ethylene in the atmosphere. Air samples recently
taken in California indicate that the average ethylene concen-
tration for metropolitan areas ranges from 40 to 120 Mg/m
(0.04 to 0.1 ppm). The maximum value observed has been as
high as 800 Hg/m3 (0.7 ppm).
The methods used for control of volatile hydrocarbons
are applicable to ethylene. These include combustion, adsorp-
tion, and vapor recovery systems. No information was found
on the cost of abatement.
Economic losses from plant damage due to ethylene have
been reported in the literature. Greenhouse plants, particu-
larly orchids, appear to be most affected.
-------
29
Ethylene can be determined in the ppb range by the
available gas chromatographic techniques.
Based on the material presented in this report, further
studies in the following areas are suggested:
(1) Determination of the concentration of ethylene in
the ambient air of more cities than have been studied so
far, particularly in areas of high population density.
(2) Evaluation of the importance of commercial
sources, combustion sources (e.g.,automobiles, incinerators),
and biological sources to ethylene air pollution.
(3) Determination of the effects of ethylene on
different plant species under closely simulated ethylene
atmospheric conditions (i.e., dynamic conditions, concentra-
tions of ethylene varying with time, presence of other atmo-
spheric contaminants).
(4) Determination of the importance of photooxidation
reactions of ethylene in air pollution.
-------
30
REFERENCES
1. Aalund, L. R., Massive Ethylene Buildup Will Swamp Demand
in '69, Oil Gas J. ^6(28):21 (1968).
2. Akamine, E. K., Ethylene Production in Fading Vanda Orchid
Blossoms, Science 140;1217 (1963).
3. Akamine, E. K., and H. I. Sakamoto, Brominated Charcoal
to Prevent Fading of Vanda Orchid Flowers, Amer. Orchid
Soc. Bull. .20/-149 (1951).
4. Altshuller, A. P-, and T. A. Bellar, Gas Chromatographic
Analysis of Hydrocarbons in the Los Angeles Atmosphere,
J. Air Pollution Control Assoc. 1.3_(2):81 (1963).
5. Altshuller, A. P-, and I. R. Cohen, Structural Effects
on the Rate of Nitrogen Dioxide Formation in the Photo-
Oxidation of Organic Compound Nitric Oxide Mixtures in
Air, Intern. J. Air Water Pollution 7:787 (1963).
6. Altshuller, A. P-, and I. R. Cohen, Atmospheric Photo-
oxidation of the Ethylene-Nitric Oxide System, Intern.
J. Air Water Pollution 8;611 (1964).
7. Altshuller, A. P-, and S. F. Sleva, Spectrophotometric
Determination of Olefins, Anal. Chem. .3_3:1413 (1961).
8. Altshuller, A. P-, and S. F. Sleva, Vapor Phase Deter-
mination of Olefins by a Colorimetric Method, Anal. Chem.
_34_:418 (1962).
9. Altshuller, A. P., S. F. Sleva, and A. F. Wartburg,
Spectrophotometric Determination of Olefins in Concen-
trated Sulfuric Acid , Anal. Chem. J32.:946 (1960).
10. Altshuller, A. P-, et al., Products and Biological Effects
from Irradiation of Nitrogen Oxides with Hydrocarbons or
Aldehydes Under Dynamic Conditions, Intern. J. Air Water
Pollution 10:81 (1966).
11. Balls, A. K., and W. S. Hale, The Effect of Ethylene on
Freshly Ripened Wheat, Cejreal Chem. ,17_:490 (1940).
12. Balls, A. K., and W. S. Hale, Method of Treating Cereal
Grains, U.S. Patent 2,381,421 (August 7, 1945).
-------
31
13. Bellar, T. A., M. F. Brown, and J. E. Sigsby, Jr., Deter-
mination of Atmosphere Pollutants in the Part-Per-Billion
Range by Gas Chromatography (A Simple Trapping System for
Use with Flame lonization Detectors), Anal. Chem. 35;
1924 (1963).
14. Bellar, T. A., M. F. Brown, and J. E. Sigsby, Jr., Evalu-
ation of Various Silica Gels in the Gas Chromatographic
Analysis of Light Hydrocarbons, Environ. Sci. Technol.
.1(3) :242 (1967).
15. Bellar, T. A., et al., Direct Application of Gas Chromato-
graphy to Atmospheric Pollutants, Anal. Chem. 34(7):763
(1962).
16. Biale, J. B., R. E. Young, and A. J. Olmstead, Fruit
Respiration and Ethylene Production, Plant Physio1. 29;
168 (1954).
17. Boubel, R. W., E. F. Darley, and E. A. Schuck, Emissions
from Burning Grass Stubble and Straw, Paper 68-28 presented
at the 61st Annual Meeting of the Air Pollution Control
Assoc., St. Paul, Minn. (1968).
18. Bufalini, J. J., and A. P. Altshuller, Kinetics of Vapor
Phase Hydrocarbon-Ozone Reactions, Can. J. Chem. 43:
2243 (1965).
19. Bufalini, J. J., and J. C. Purcell, Nitrogen: Formation
by PhotooxLdation of Ethylene in the Presence of Its
Oxides, Science 150:1161 (1965).
20. Burg, S. P., The Physiology of Ethylene Formation, Ann.
Rev. Plant Physiol. JL3.:265 (1962).
21. Burg, S. P-, and E. A. Burg, Role of Ethylene in Fruit
Ripening, Plant Physiol. 37_:11°> (1962).
22. Burg, S. P., and E. A. Burg, Ethylene Action and the
Ripening of Fruit, Science 148:1190 (1965).
23. Caldwell, D. L., and I. Lichtenstein, "Ethylene" in Kirk-
Othmer Encyclopedia of Chemical Technology, vol. 8, 2nd
ed. (New York: Interscience, pp. 499-523, 1965).
24. California Standards for Ambient Air Quality and Motor
Vehicle Exhaust (Technical Report), California State Dept.
of Public Health, Berkeley (1961).
-------
32
25. California Standards for Ambient Air Quality and Motor
Vehicle Exhaust, Supplement No. 2 (Technical Report),
California State Dept. of Public Health, Berkeley (1962).
26. Cholak, J., Current Information on the Quantities of
Fluoride in Air, Food and Water, A.M.A. Arch. Ind. Health
21.:312 (1960).
27. Clayton, G. D., and T. S. Platt, Evaluation of Ethylene
as an Air Pollutant Affecting Plant Life, Am. Ind. Hyg.
Assoc. J. 28_(2):151 (1967).
28. Coulson, D. M., Hydrocarbon Compound-type Analysis of Auto-
mobile Exhaust Gases by Mass Spectrometry, Anal. Chem.
21:906 (1959).
29. Crocker, W., 'Physiological Effects of Ethylene and Other
Unsaturated Carbon-Containing Gases," Chapter 4, in Growth
of Plants (New York: Reinhold, 1948).
30. Crocker, W., and L. I. Knight, Effect of Illuminating
Gas and Ethylene Upon Flowering Carnations, Botan. Gaz.
46_:259 (1908).
31. Crocker, W., P. W. Zimmerman, and A. E. Hitchcock, Ethylene-
Induced Epinasty of Leaves, and the Relation of Gravity to
It, Contrib. Boyce Thompson Inst. 4_:177 (1932).
32. Darley, E. F., C. W. Nichols, and J. T. Middleton, Identi-
fication of Air Pollution Damage to Agricultural Crops
(Air Pollution Research Reveals Chemical Toxicants In-
juring Vegetation in Populous Areas of California),
Calif. Dept. Agri. Bull. 55_(1):11 (1966).
33. Darley, E. F., et al., Oxidant Plant Damage from Ozone-
Olefin Reactions, Preprint. Presented at 23rd Midyear
Meeting of The American Petroleum Institute's Division of
Refining, Los Angeles, Calif. (May 15, 1958).
34. Darley. E. F., et al., Plant Damage by Pollution Derived
from Automobiles, Arch. Environ. Health 6:761 (1963).
35. Darley, E. F., et al., Contribution of Burning of Agricul-
tural Wastes to Photochemical Air Pollution, J. Air Pol-
lution Control Assoc. 16_(12):685 (1966).
36. Davidson, 0. W., Effects of Ethylene on Orchid Flowers,
Proc. Am. Soc. Hort. Sci. 5_3_:440 (1949).
-------
33
37. Denny, F. E., Testing Plant Tissue for Emanation Causing
Leaf Epinasty, Contrib. Boyce Thompson Inst. 2.:341 (1935).
38. Denny, F. E., and L. P. Miller, Production of Ethylene
by Plant Tissue as Indicated by the Epinastic Response of
Leaves, Contrib. Boyce Thompson Inst. T_:97 (1935).
39. Dickinson, J. E., and R. E. Chass, Evaluation and Planning
Report on Estimate of Total Air Pollution Emissions from
Gasoline-Powered Vehicles in Los Angeles County, Los Angeles
Air Pollution Control District (July 15, 1958).
40. Doubt, S. L., The Response of Plants to Illuminating Gas,
Botan. Gaz. 63;209 (1917).
41. Doyle, G. J., Model Aerosols for Atmospheric Smog, Stanford
Research Inst., South Pasadena, Calif. (1961).
42. Doyle, G. J., N. Endow, and J. L. Jones, Sulfur Dioxide
Role in Eye Irritation, Arch. Environ. Health 3:55 (1961).
43. Eggertson, F. T., and F. M. Nelsen, Gas Chromatographic
Analysis of Engine Exhaust and Atmosphere Determination of
C2 to GS Hydrocarbons, Anal. Chem. 30.: 1040 (1958).
44. "Ethylene," in Encyclopedia of Science and Technology
(New York: McGraw Hill, 1966).
45. Ethylene in Community Air Quality Guides, Am. Ind. Hvg.
Assoc. J. 29_:627 (1968).
46. Ethylene Forecasts Conflict on Oversupply, Oil Gas J.
66J26):64 (1968).
47. Faith, W. L., Relative Reactivity of Hydrocarbons in
Photo-Chemical Smog Formation and Its Practical Implica-
tion, Preprint. Presented at the 59th Annual Meeting,
Air Pollution Control Assoc., San Francisco, Calif.
(1966).
48. Feldstein, M. , and S. Balestrieri, The Detection and
Estimation of Part Per Billion Concentrations of Hydro-
carbons, J. Air Pollution Control Assoc. 15_(4) :177 (1965).
49. Feldstein, M., et al., The Collection and Infrared Analysis
of Low Molecular Weight Hydrocarbons from Combustion
Effluents, Am. Ind. Hyg. Assoc. J. 20:374 (1959).
-------
34
50. Fischer, C. W., Jr., Calceolarias and Snapdragons Gas
Themselves, N.Y. State Flower Growers Bull. 52 (1949).
51. Fischer, C. W., Jr., Ethylene Gas a Problem in Cut
Flower Storage, N.Y. State Flower Growers Bull. 61
(1950).
52. Guide and Data Book for 1964 (New York: American Society
of Heating, Refrigerating and Air Conditioning Engineers,
Inc., 1964).
53. Hall, W. C., et al., Ethylene Production by the Cotton
Plant and Its Effect Under Experimental and Field
Conditions, Physiol. Plantarium 10;306 (1957).
54. Harvey, R. B., Artificial Ripening of Fruits and Vegetables,
Minn. Agri. Expt. Sta. Bull. 247;1 (1928).
55. Harvey, R. B., Effect of Ethylene on the Growth of Celery,
Proc. Am. Soc. Hort. Sci. J6_:141 (1930).
56. Heck, W. W., E. G. Pires, and W. C. Hall, The Effects of
a Low Ethylene Concentration on the Growth of Cotton,
J. Air Pollution Control Assoc. 11_(12)549 (1961).
57. Hirshfelder, A. D., and E. T. Ceder, Does Ethylene Affect
Rate of Growth or Action of Enzymes in Animals? Am. J.
Physiol. 91^:624 (1930).
58. Hitchcock, A. E., W. Crocker,- and P- W. Zimmerman, Effect
of Illuminating Gas on Lily, Narcissus, Tulip, and
Hyacinth, Contrib. Boyce Thompson Inst. 4_:155 (1932).
59. Hum, R. W., et al. , The Potpourri That Is Exhaust Gas,
J^jv. of Refining 42;657 (1962).
60. Jacobs, E. S., Rapid Gas Chromatographic Determination of
GI to CIQ Hydrocarbons in Automobile Exhaust Gas, Anal.
Chem. 3£:43 (1966).
61. Jerman, R. I., and L. R. Carpenter, Gas Chromatographic
Analysis of Gaseous Products from the Pyrolysis of Solid
Municipal Waste, J. Gas Chromatog. 6^(5):298 (1968).
62. Katz, M., Quality Standards for Air and Water, Occupational
Health Rev. 17.(1):3 (1965).
63. Katz, M., Recent Developments in Ambient Air Quality
Guides in Relation to Control of Atmospheric Effluents,
Pulp Paper Mag. Can. 69(4):60 (1968).
-------
35
64. Kendrick, J. B., et al., Plant Response to Polluted Air,
Calif. Agr. 12(8):9 (1956).
65. Kitagawa/ T., and Y. Kobayashi, Gas Analysis by Means of
Detector Tubes. III. Rapid Determination of Low Concen-
trations of Ethylene and Acetylene, J. Chem. Soc. Japan
56.:56 (1953).
66. Kitagawa, T., and Y. Kobayashi, Gas Analysis by Means of
Detector Tubes. VII. Rapid Method for the Determination
of Ethylene, J. Chem. Soc. Japan 56;448 (1953).
67- Klosterman, D. L., and J. E. Sigsby, Jr., Application of
Subtractive Techniques to the Analysis of Automotive
Exhaust, Environ. Sci. Tech. 1^:309 (1967).
68. Kobayashi, Y., Rapid Method for the Determination of
Low Concentrations of Ethylene by Means of a Detecting
Tube, Yuki Gosei Kagaku Kyokai Shi 14:137 (1957).
69. Largent, E. J., Metabolism of Fluorides in Man, A.M.A.
Arch. Ind. Health 21:318 (1960).
70. Leighton, P. A., Photochemistry of Air Pollution (New
York: Academic Press, 1961).
71. Linnell, R. H., and W. E. Scott, Diesel Exhaust Analysis,
Arch. Environ. Health 5:616 (1962).
72. Livingstone, H., Ethylene-Oxygen Anesthesia Proves
Satisfactory and Inexpensive, Mod. Hospital 43:112 (1934)-
73. Luckhardt, A. B., and J. B. Carter, The Physiologic Effects
of Ethylene, J. Am. Med. Assoc. §2:765 (1923).
74. Mack, W. B., The Action of Ethylene in Accelerating the
Blanching of Celery, Plant Physio 1. .2:102 (1927).
75. MacPhee, R. D., Use of Molybdates for Estimating the
Amount of Olefinic-Type Hydrocarbons in the Air, Anal.
Chem. 26_:221 (1954).
76. Mader, P. P., K. Schoenemann, and M. Eye, Detection of
Nonaromatic Unsaturates in Automobile Exhaust by Spectro-
photometric Titration, Anal. Chem. 33:733 (1961).
77. Mader, P- P-, et al., Effects of Fuel Olefin Content on
Composition and Smog Forming Capabilities of Engine
Exhaust, Air Pollution Control District, County of Los
Angeles, Calif. (1959).
-------
36
78. McEwen, D. J., Temperatures Programmed Capillary Columns
in Gas Chroma tog raphy, Anal. Chem. ^5_:1636 (1963).
79- McEwen, D. J., Automobile Exhaust Hydrocarbon Analysis
by Gas Chromatography, Anal. Chem. _38_:1047 (1966).
80. McMichael, W. F., and J. E. Sigsby, Jr., Automotive
Emissions After Hot and Cold Starts in Summer and Winter,
J. Air Pollution Control Assoc. 16/9):474 (1966).
81. The Merck Index, 8th ed. (Rahway. N. J.: Merck, 1968).
82. Middleton, J. T., Trends in Air Pollution Damage, Arch.
Environ. Health 8:19 (1964).
83. Middleton, J. T., and E. F. Barley, Plant Damage: An
Indicator of the Presence and Distribution of Air Pol-
lution, Bull. World Health Organ. (Geneva) 34(3) :477
(1966).
84. Middleton, J. T., L. 0. Emik, and O. C. Taylor, Air Quality
Criteria and Standards for Agriculture, J. Air Pollution
Control Assoc. 15_(10):476 (1965).
85. Nicksic, S. W., and R. E. Rostenback, Instrumentation for
Olefin Analysis at Ambient Concentrations, J. Air Pollution
Control Assoc. 11_:417 (1961).
86. Nicksic, S. W., J. Harkins, and B. A. Fries, A Radio-
tracer Study of the Production of Formaldehyde in the
Photo-Oxidation of Ethylene in the Atmosphere, Part II.
The Effect of Other Compounds on Yield and Conversion,
J. Air Pollution Control Assoc. JL4_:224 (1964).
87. Pattison, J. N., and E. R. Stephens, Composition of Auto-
motive Blowby Gases, Proceedings of the Technical Meeting,
West Coast Section, Air Pollution Control Assoc., 3rd,
Monterey, Calif. (1963).
88. Patty, F. A. (Ed.), Industrial Hygiene and Toxicology, vol.
II, 2nd ed. (New York: Interscience, 1963).
89. Pohraugh, P. W., Measurement of Small Concentration of
Ethylene and Automobile Exhaust Gases and Their Relation
to Lemon Storage, Plant Physiol. 18:79 (1943).
90. Prescott, J. H., Ethylene Imbalance Soon? Chem. Eng.
(Jan. 1969).
-------
37
91. Reckner, L. R., W. E. Scott, and W. F. Biller, The
Composition and Odor of Diesel Exhaust, Proc. Am. Petrol.
Inst. 4_5_:133 (1965) .
92. Rose, A., and E. Rose, The Condensed Chemical Dictionary
(New York: Reinhold, p. 390, 1966).
93. Rounds, F. G., P- A. Bennett, and G. J. Nebel, Some Effects
of Engine-Fuel Variables on Exhaust Gas Hydrocarbon Con-
tent, J. Air Pollution Control Assoc. 5_:109 (1955).
94. Sax, N. I., Dangerous Properties of Industrial Materials
(New York: Reinhold, p. 800, 1963).
95. Schuck, E. A., G. J. Doyle, and N. Endow, A Progress
Report on the Photochemistry of Polluted Atmospheres,
Stanford Research Institute, South Pasadena, Calif.
(1960).
96. Schuck, E. A., H. W. Ford, and E. R. Stephens, Air Pol-
lution Found. (Los Angeles) Rept. 26 (1958).
97. Scott, W. E., et al., Further Developments in the Chemistry
of the Atmosphere, Proc. Am. Petrol. Inst. ^7:171 (1957).
98. Seidman, G., Effects of Air Pollution on Plants, African
Violet Mag. 18_(3):44 (1965).
99. Shepherd, M., et al., Isolation, Identification and
Estimation of Gaseous Pollutants of Air, Anal. Chem.
21:1431 (1951).
100. Sigsby, J. E., Jr., and M. W. Korth, Composition of Blow-
by Emissions, Preprint. Presented at the 57th Annual
Meeting, Air Pollution Control Association, Houston, Tex.
Paper No. 64-72 (June 21-25, 1964).
101. Stephens, E. R., and W. E. Scott, Relative Reactivity of
Various Hydrocarbons in Polluted Atmospheres, Proc. Am.
Petrol. Inst. 4_2:665 (1962).
102. Stephens, E. R., et al., Auto Exhaust Composition and
Photolysis Products, J. Air Pollution Control Assoc.
S..-333 (1959).
103. Stephens, E. R., et al., Photochemical Reaction Products
in Air Pollution, Intern. J. Air Water Pollution 4_:79
(1961).
-------
38
104. Stern, A. C. (Ed.), Air Pollution, !_, 2nd ed. (New York:
Academic Press, p. 401, 1968).
105. Stern, A. C. (Ed.), Air Pollution. II, 2nd ed. (New York:
Academic Press, p. 116, 1968).
106. Stern, A. C. (Ed.), Air Pollution, III, 2nd ed. (New York:
Academic Press, pp. 55, 97, 666, 1968).
107. Stitt, F., and Y. Tomimatsu, Removal and Recovery of Traces
of Ethylene in Air by Silica Gel, Anal. Chem. 25:181
(1953).
108. Stitt, P., A. H. Tjensvold, and Y. Tomimatsu, Rapid
Estimation of Small Amounts of Ethylene in Air. Port-
able Instrument, Anal. Chem. 23_:1138 (1951).
109. Stitt, F. , Y. Tomimatsu, and A. H. Tjensvold, Deter-
mination of Ethylene in Gases, U.S. Patent No. 2,648,598
(August 11, 1953).
110. Swartz, D. J., K. W. Wilson, and W. J. King, Merits of
Liquified Petroleum Gas Fuel for Automobile Air Pollution
Abatement, J. Air Pollution Control Assoc. 13_:154 (1963).
111. Synthetic Organic Chemicals, U.S. Production and Sales,
U.S. Tariff Commission 1958-1967, U.S. Tariff Commission
(1968).
112. Threshold Limit Values for 1962, American Conference of
Governmental Industrial Hygienists, Cincinnati, Ohio
(1962).
113. Tuttle, W. N., and M. Feldstein, Gas Chromatographic
Analysis of Incinerator Effluents, J. Air Pollution
Control Assoc. 10_(6):427 (1960).
114. Walker, J. K., and C. L. O'Hara, Analysis of Automobile
Exhaust Gases, Anal. Chem. 26:352 (1954).
115. Winston, J. R., The Coloring or Degreening of Mature
Citrus Fruits with Ethylene, U.S. Dept. Agri. Circ. 960
(1955).
116. Yocum, J. E., G. M. Hein, and H. W. Nelson, Effluents
from Backyard Incinerators, J. Air Pollution Control
Assoc. 6^:84 (1956).
-------
39
117. Young, R. E., H. K. Pratt, and J. B. Biale, Manometric
Determination of Low Concentrations of Ethylene, Anal.
Chem. 24_:551 (1952) .
118. Zimmerman, P. W., A. E. Hitchcock, and W. Crocker, The
Effect of Ethylene and Illuminating Gas on Roses, Contrib,
Boyce Thompson Inst. 3:459 (1931).
-------
APPENDIX
-------
41
APPENDIX
TABLE 5
MAJOR ORGANS OF VARIOUS PLANT SPECIES PRODUCING ETHYLENE20
I. Flowers
broccoli
calceolaria
carnation
chrysanthemum
cotton
dahlia
dandelion
diplotaxis
gardenia
gladiolus
hollyhock
iris
larkspur
lilac
lily
lily of the
valley
marigold
orchid
pelargonium
petunia
rose
snapdragon
tulip
verbena
violet
II. Fruits
apple
avocado
banana
cantaloupe
cherimoya
cotton
eggplant
feijoa
grapefruit
green pepper
hawthorn
lemon
lime
loquat
mango
nectarine
orange
passion fruit
pea
peach
pear
pecan
persimmon
pineapple
plum
sapodilla
squa sh
tangerine
tomato
III. Leaves and Leafy Stems
asparagus
celery
dandelion
hollyhock
lettuce
milk thistle
onion
peony
potato
rhubarb
rose
spinach
tomato
Virginia creeper
yellow calla
IV. Seeds
lima bean
pea
-------
APPENDIX
42
TABLE 5
MAJOR ORGANS OF VARIOUS PLANT SPECIES PRODUCING ETHYLENE
(Continued)
V. Roots and Tubers
beet
kohlrabi
potato
radi sh
rutabaga
turnip
VI. Fungi
Blastomyces
dermatididis
Fulsarium
osysporum f.
lycopersicum
Penicillium
digitatum
Saccharomyces
cerevisiae
-------
APPENDIX
43
TABLE 6
MAXIMUM RATES OF ETHYLENE PRODUCTION BY VARIOUS FRUITS16
Fruit
Variety
Temp
C8H
hr
Tropical
Banana
Mango
Papaya
Pineapple
Subtropical
Avocado
Cherimoya
Feijoa
Lemon
Orange
Orange
Persimmon
Sapote
Temperate
Apple
Pear
Pear
Peach
Gros Michel
Ha den
Fuerte
Booth
Coolidge
Eureka
Valencia
W. Navel
Hachiya
Pike
Me Into sh
Bartlett
Bosc
Hale
20
20
25
25
20
20
20
25
25
20
20
20
20
20
20
20
4
Trace*
37
Trace*
88
186
50
Trace*
Trace*
Trace*
2
129
112
122
29
36
*Determined by more recent techniques.
-------
44
APPENDIX
TABLE 7
PRODUCTION OF ETHYLENE IN UNITED STATES, 1958-1967111
Year
1958
1959
1960
1961
1962
1963
1964
1965
1966
1967
Production
(1,000 Ibs)
4,149,233
5,099.056
5,448,094
5,655,785
6,282,908
7,517,552
8,641,202
9,569,885
11,241,085
11,854,515
Amount Sold
(1,000 Ib)
737,346
2,941,228
3,251,813
3,360,619
3,978,634
2,208,259
2,377,368
2,714,873
3,276,767
3,353,371
-------
APPENDIX 45
TABLE 8
ETHYLENE CONSUMPTION IN UNITED STATES, 1950, 1960, 197023
Derivative
Ethanol, synthetic
Ethyl chloride and
Ethylene dichloride
Ethyl en e oxide and
Glycol
Polyethylene
Styrene
Others
Total
1950
34
15
30
5
12
4
100
Percent of
Ethylene Consumption
1960
19
13
27
29
10
2
100
1970*
11
8
22
43
9
7
100
*Projected.
-------
APPENDIX
46
TABLE 9
TRENDS IN ETHYLENE CONSUMPTION
BY END USE IN UNITED STATES23
End Use
Percent of
Total Ethylene Growth
1950-1960 1960-1970*
Plastics and resins (e.g.,
polyethylene and polyester)
Detergents (straight
chain alcohols)
Antifreeze (ethylene glycol)
Ela stomer s (ethylene-
propylene rubber, styrene-
43.2
4.8
13.8
63.4
4.2
2.9
butadiene rubber)
Solvents (chlorinated
ethylene)
Additives (tetraethyl lead,
ethylene dibromide)
Synthetic fibers (polyesters)
Miscellaneous
2.7
8.8
3.5
1.2
22.0
100
5.8
6.9
0
1.5
15.3
100
*Projected.
-------
APPENDIX
47
TABLE 10
ETHYLENE IN DIESEL EXHAUST71'91
EPM
500
600
740
800
1,000
1,050
1,200
1,300
1,500
1,520
1,600
1,780
1,800
2,200
600 to
2,200
Load
0
0
0
c
1/4
Full
0
1/4
1/2
3/4
Full
c
0
1/4
1/2
3/4
Full
c
3/4
Full
c
0
1/4
1/2
3/4
Full
Full
0
Ethyl ene (ppm, dry basis)
4-cycle 2-cycle
engine3 engine*5
15
6.85, 10.1
16
12.2, 14.2
4.20, 7.2
40
8.93, 9.52
14
10 10
11 10.7, 21.0
14
30
13.7, 19.4
12
8
13
13
38
18.5, 14.2
23.9, 31.9
56
27.3, 29.6
13
12
12
21
44
30.2, 35.1
82.8
of rpm.
a6-cylinder, 300 Hp turbocharged.
t>6-cylinder, 220 Hp.
cioad provided by a club propeller; load a function
-------
48
APPENDIX
TABLE 11
GENERAL INFORMATION AND PROPERTIES OF ETHYLENE81
Synonyms
Molecular formula
Molecular weight
Normal state, color
odor
Boiling point (760 mm)
Melting point
Specific gravity
(liquid, QOC)
Vapor density (air = 1)
Water solubility
Flammability
Autoignition temperature
Explosive limits
Ethene, elayl, olefiant gas,
ether in
C2H4, CH2CH2, H2C=CH2
28.05 (85.63% carbon, 14?37%
hydrogen)
Colorless gas with sweet odor
-103.9° C
-169.4°C (solidifies at -181°C)
0.610
0.98
0.25 v/v* H20 (0°C)
0.11 v/v* H20 (25°C)
Burns with a luminous flame
543°C
Lower: 3% by vol in air
Upper: 34% by vol in air
*v/v = volume per volume.
-------
TABLE 12
SUMMARY OF REPORTED EFFECTS OF ETHYLENE ON PLANTS
Species
Vanda orchids
Antirrhinum ma jus
1.
Cattleya sp. orchids,
buds
Cattleya orchids
i^_
Cheno podium album
Dianthus caryophyllus
Faqopyrum saqittatum
(F. esculentum)
Gossypium hirsutum
Itelianthus annuus
Lathyrus odoratus
g*~
Lilium regale
Concentrati on
(ppm)
1
0.5
0,01
0.05
0.3
0.002
0.1
0.05
0.10
0.05
0.6
0.05
0.2
4.0
Exposure
Time (hr)
24
1
24
6
1
24
8
6
720
72
Effects or Comments
Fading of flowers
Abscission of flowers
Sepal tissue collapse
Sepal tissue collapse
Epinasty
Inhibited flower opening
Epinasty
Reduction in growth and yield
Epinasty
Epinasty
Growth retardation and epinasty
Reference
3
25
36
31
25
31
56
_
31
58
-------
APPENDIX
TABLE 12
SUMMARY OF REPORTED EFFECTS OF ETHYLENE ON PLANTS (Continued)
Species
Lycopersicon esculent vim
Narcissus sp.
Rosa sp.
Solamon tuberosum
Taqetes patula
Tulipa qesneriana
A i
Tomato
African marigold
Lemons
Cone ent r a t i on
(ppm)
0.1
2. 0
4.0
0.33
10.0
40.0
40.0
40.0
0.05
0.05
4.0
0.1
0.04
0.001
0.025-0.05
Exposure
Time (hr)
48
72
72
120
24
24
48
168
16
48
3 tci 4
Effects or Comments
Growth retardation
^~
Growth retardation
Growth retardation and lea£ curl
Epinasty and leaf abscission at
room temperature
Petal fall at 70°F, none at 32U,
40°, and 50°
Epinasty at 70UF
Epinasty and leat abscission at
70°F
No abscission at 41°F
Epinasty
Epinasty
Leaf roll
Leaf epinasty
Leaf epinasty of mature leaves
Leaf epinasty
Epinasty
Reference
31
58
118
38
31
58
29
89
(continued)
-------
APPENDIX
TABLE 12
SUMMARY OF REPORTED EFFECTS OF ETHYLENE ON PLANTS (Continued)
Species
Datura stramonium
Lycopersicum esculentum
Beqonia luminosa
Sweet peas
Concentration
(ppm)
0.1
0.2
8
0.1
0.4
Exposure
Time (hr)
Effects or Comments
Close to limit for response
Epinasty of leaves
Slight epinasty
Inhibited elongation of the
epicotyl
Production of triple response;
horizontal nutation and swelling
Reference
40
30
-------
TABLE 13
UNITED STATES PRODUCERS OF ETHYLENE
,90
Company
Location
Onstream in 1969
Estimated Annual and Considering
Capacity, 1968 for Early 1970'sa
(Million Pounds) (Million Pounds)
Allied Chem. Corp. and
Wyandotte Chems. Corp.
Amoco Oil Co.
Atlantic Richfield Co.
Celanese
Chemplex Co.
Cities Service Co. and
Columbian Carbon Co.
Commonwealth Oil Refining
Co., and PPG Industries,
Inc.
Continental Oil Co.
Petrochemical Dept.
Dow Chem. Co.
E.I. duPont de Nemours &
Co., Plastics Dept.
Eastman Kodak Co.
Texas Eastman Co., Div.
El Paso Natural Gas Co. and
Rexall Drug & Chem. Co.
Enjay Chem. Co.
B. F. Goodrich Chem. Co.
Gulf Oil Corp.
Jefferson Chem. Co.
Geismar, La.
Alvin, Tex.
Wilmington, Calif.
Bayport, Tex.
Clin£on, La.
Lake Charles, La.
Penuelas, P.R.
Lake Charles, La.
Bay City, Mich.
Freeport, Tex.
Plaquemine, La.
Orange, Tex.
Longview, Tex.
Odessa, Tex.
Baton Rouge, La.
Baytown, Tex.
Bayway (Linden), N.J.
Calvert City, Ky.
Cedar Bayou, Tex.
Port Arthur, Tex.
Port Neches, Tex.
600
100
500
420
750
(500)
1,000
500
170
1,400
610
750
450
400
1,000
90
175
250
400
425^
470
300
25
900
(continued)
-------
TABLE 13
UNITED STATES PRODUCERS OF ETHYLENE (Continued)
Company
Location
Estimated Annual
Capacity, 1968
(Million Pounds)
Onstream in 1969
and Considering
for Early 1970'sa
(Million Pounds)
Mobil Oil Corp.
Petrochemicals Div.
Monsanto Co., Hydrocar-
bons & Polymers Div.
National Distillers and
Chem. Corp., U.S. Indus-
trial Chems. Co.
Northern Natural Gas
Olin Mathieson Chem. Corp.
Chems. Div.
Phillips Petroleum Co.
Phillips Petroleum Co. and
Houston Natural Gas
Products Co.
Shell Oil Co.
Sinclair-Koppers Co.
Sun Oil Co.
SunOlin Chem. Co.
Union Carbide Corp. Chems.
and Plastics Operations
Div.
Beaumont, Tex.
Alvin, Tex.
Texas City, Tex.
Tuscola, 111.
Joliet, 111.
Brandenburg, Ky.
Sweeny, Tex.
Sweeny, Tex.
Deer Park, Tex.
Norco, La.
Torrance, Calif.
Houston, Tex.
Marcus Hook, Pa.
Claymont, Del.
Institute, W. Va.
Ponce, P.R.
Seadrift, Tex.
South Charleston, W. Va,
485
600
100
350
90
600
500
275b
500
75
500
225
350
20013
900
400
500
(500)
1,000
(500)
(50)
1,200
ui
OJ
(continued)
-------
APPENDIX
TABLE 13
UNITED STATES PRODUCERS OF ETHYLENE (Continued)
Company
Location
Estimated Annual
Capacity, 1968
(Million Pounds)
Onstream in 1969
and Considering
for Early 1970'sa
(Million Pounds)
Union Carbide Corp. Chems.
and Plastics Operations
Div.
Taft, La.
Texas City, Tex.
Torrance, Calif.
Whiting, Ind.
500
750b
150
275
1,200
aQuantities in parenthesis are under consideration for early 1970's.
t>May be shut down when new plant comes onstream.
CJl
-------
APPENDIX
55
TABLE 14
ETHYLENE CAPACITY BY STATES90
State
Texas
Louisiana
West Virginia
Illinois
Kentucky
California
Indiana
Delaware
Puerto Rico
New Jersey
Michigan
Total
Capacity
(Million Pounds)
9,095
4,630
750
350
340
325
275
225
200
175
170
16,535
Percent
55
28
4.5
2.1
2.1
2.0
1.7
1.4
1.2
1.0
1.0
100.0
Number of
Plants
17
8
2
1
2
3
1
1
1
1
1
38
-------
APPENDIX
TABLE 15
ETHYLENE EMISSIONS PROM BURNING OF AGRICULTURAL WASTES
Material
Blue grass
Perennial Rye grass
Bent grass
Annual Rye grass
Fescue grass
Orchard grass
Blue grass
perennial Rye grass
Bent grass
Annual Rye grass
Fescue grass
Orchard grass
Ethyl en e ( Ib/ton
of material)
2.4
1.4
0.9
0.6
1.2
0.7
1.2
3.4
3.1
0.6
1.8
1.8
2.1
2.3
Collection
Location ,
Willamette Valley,
Oregon
ii 11
H ii
n ii
n M
ii n
n n
n n
n n
t M
n n
n n
n n
n n
Comments
5% moisture, dry
6% moisture, dry
2% moisture, dry
9% moisture, dry
9% moisture, dry
15% moisture, dry
23% moisture, dry- green
71% moisture, dry-green
60% moisture, dry-green
20% moisture, dry-green
55% moisture, dry-green
66% moisture, dry-green
66% moisture, dry-green
47% moisture, dry-green
Reference
17
-------
TABLE 15
ETHYLENE EMISSIONS FROM BURNING OF AGRICULTURAL WASTES (Continued)
»
Material
Rice straw
Barley straw
Native brush
Cotton
Fruit primings
Native brush
Fir chips
Redwood chips
Fruit primings
Native brush
Ethyl en e ( Ib/ton
of material )
1.7
2.2
0.7
3.5
5.5
0.3
0.8
1.2
0.2
0.2
2.7
0.9
Collection
Location
San Joaquin Valley
California
n H
it n
M ii
n n
San Francisco Bay
Area, California
(1965)
n n
n n
n n
San Francisco Bay
Area, California
(1966)
n n
Comment s
Dry
Dry-green
Green
Reference
35
Ul
------- |