Photochemical Oxidants And Air Pollution: An Annotated Bibliography


PHOTOCHEMICAL OXIDANTS
AND AIR POLLUTION:
An Annotated Bibliography
PART 2. CATEGORIES G THROUGH N AND INDEXES
U. S. ENVIRONMENTAL PROTECTION AGENCY

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PHOTOCHEMICAL OXIDANTS
AND AIR POLLUTION:
AN ANNOTATED BIBLIOGRAPHY
PART II.
Office of Technical Information and Publications
Air Pollution Technical Information Center
U.S. ENVIRONMENTAL PROTECTION AGENCY
Air Pollution Control Office
Research Triangle Park, North Carolina
March 1971
For mle by tbe Superintendent of Documents, U.S. Government Printing Office
WuHhington, D.C., 20402 - Price >6.20 per set of 2 volumes. Sold insets only.

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The AP series of reports is issued by the Air Pollution Control Office to report
the results of scientific and engineering studies, and information of general interest
in the field of air pollution. Information reported in this series includes coverage
of APCO intramural activities and of cooperative studies conducted in conjunction
with state and local agencies, research institutes, and industrial organizations.
Copies of AP reports are available free of charge to APCO staff members, current
contractors and grantees, and nonprofit organizations - as supplies permit - from
the Office of Technical Information and Publications, Air Pollution Control Office,
U.S. Environmental Protection Agency, P.O. Box 12055, Research Triangle Park,
North Carolina 27709.
Air Pollution Control Office Publication No. AP-88

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CONTENTS
PART I.
INTRODUCTION		1
ANNOTATED BIBLIOGRAPHY
A- General		3
B.	Emission Sources		19
C.	Atmospheric Interaction		115
D.	Measurement Methods		269
E.	Control Methods		507
F.	Effects - Human Health 		595
PART II.
G.	Effects ¦ Plants and Livestock 		815
H.	Effects-Materials 		917
I.	Effects - Economic		921
J. Air Quality Measurements	 		925
K. Legal and Administrative		1019
L. Standards and Criteria		1045
M. Basic Science and Technology		1063
N. Social Aspects		1335
AUTHOR INDEX		1337
TITLE INDEX		1373
SUBJECT INDEX		1475
GEOGRAPHIC LOCATION INDEX 		1525
United States (States, Cities)		1525
Foreign (Countries, Cities) 		1527
111

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G. EFFECTS - PLANTS AND LIVESTOCK
00009
0. c. laylor
"OXIDANT" AIR POLLCJTAKTS AS PHYTOTOXICANTS. California
Univ., Riverside, Air Pollution Research Center. (Paper
64-91).. 1964. 13 pp..
This report attempts to outline soae of the advances made in the
identification and study of oxidi2ing toxicants other than ozone in
the "smog" complex and to indicate soae of the avenues of
research that are prerequisites to the establishment of effective
control measures. Assuming that the total elimination fro* the
atmosphere of oxidant-forming pollutants is not econonically
feasible, it Is essential that investigations be continued to
determine acceptable levels of the pollutants, to find resistant
plant materials and to search for chemical additives that might
offer protection to the vegetation.#*
00087
A.p. Bush, R.A. Glater, J. Dyer, G. Richards
THE EFFECTS OF EHGIUE EIHAQST OS THE ATMOSPHERE SHE* AUTCHOBXLES
ARE EQUIPPED WITH AFTERBURNERS. California Univ., Los
Angeles, Dept. of Engineering. (Kept. No. 62-63.) Dec. 1962.
38 pp.
CFSTI, DDC; AD 297976
In order to determine the probable composition of the atmosphere
aftrr automobile exhausts are controlled, tests were conducted
using the air pollution test facility on the campus at UCLA.
Automotive vehicles were studied with and without afterburners
using various concentrations of auto exhaust during simulated
driving cycles* The objective of the experimentation was to
simulate ambient atmosphere and to test this atmosphere for
contamination by exposing known sensitized plants to it and
testing its ability to produce human eye irritation. Indications
are that atypical plant damage reported is due to oxides of
nitrogens Fumigations showed that, in all instances of
elevated formaldehyde measurements, eye irritation resulted.#*
00121
H„ v. Feck, J. A. Dunning* and I., J. Bindavi
OZOHE: NONLINEAR RELATION OF DOSE ADD INJUR* III PLANTS.
Science 151, (3710) 577-8, Feb. 4, 1966.
Ozone produces a sigmoidal dose-injury response in sensitive
815

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tobacco and pinto bean. A definite threshold concentration and
presentation tiae are required before injury is initiated..
(Author)#*
0018U
E. Heggestad, F« R. Burleson, J.. T. Middleton, and
E. F.. Darley
LEAF INJURY OH TOBACCO VARIETIES RESULTING FROM OZONE, C20HATEE
HEXENE-1 AMD AMBIENT AIR OF METROPOLITAN AHEAS. Intern™ J.
Air Hater Pollution 8, 1-10, 1964.
Six tobacco varieties representing a range in susceptibility to
naturally occurring ozone fleck in field plots at Beltsville,
Maryland, were: (1) fumigated with ozone, (2) fumigated with
ozonated hexene-1,, and (3) exposed to ambient air at Riverside,
California. Prior to fumigation, all plants were grown in a
greenhouse with carbon-filtered air. Injury caused by ozone to
tobacco in fumigation studies could not be distinguished from
naturally occurring fleck in fields at Eeltsville. The
susceptibility of the six varieties to ozone fleck was very
similar at Riverside and Beltsville. When fumigated with
ozonated hexene-1, however, the injury occurred only on lower leaf
surfaces and the reactions of varieties were very different,. Some
injury to the lower leaf surface of young leaves, perhaps caused
by peroxyacetyl nitrate (PAH) was noted when plants were
exposed to unfiltered ambient air in a Biverside greenhouse.. So
injury occurred to any of the varieties of N. tabacum grown in the
greenhouse with carbon-filtered air.. The sequence of damage by
ozone and ozonated hexene-1 was from oldest to youngest leaves..
Ozone caused more damage to leaves at the bottom of the plant,
whereas ozonated hexene-1 injury was more severe about mid-plant.
Although ozone injury occurred cn tobacco exposed to ambient air
at Riverside and Beltsville, some differences in leaf damage and
plant sensitivity at these two widely separated geographic
locations are discussed*. (Author) #1
00229
J.T. Middleton AvJ. Haagen-Smit
THE OCCURRENCE, DISTRIBUTION, A8D SIGNIFICANT OF
PHOTOCHEMICAL AIR POLLUTION IN THE UNITED STATES, CANADA, AND
MEXICO. J.. Air Pollution Control Assoc., 11 (3) :129-13«,
War. 1961. {Presented at the 53rd Annual Meeting, Air
Pollution Control Association, Cincinnati, Ohio, Hay 22-26,
1960.)
The cracking of rubber, production of elevated oxidant and the
occurrence of both ozone and oxidant plant damage are shown to be
manifestations of photochemical air pollution., Geographic areas
considered are Los Angeles, San Rrancisco, Washington, D.c.;
urban and non-urban areas.##
816
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION

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0C232
C.C„ Black, J.?, Turner, Gitts, D.H.. Krogmann,
S.An Gordon
STUDIES ON PHOTOSYNTHETIC PROCESSES. II„ ACTION SPECTRA AND
COANTUH REQUIREMENT FOB TPIPHOSPHOPYEIDIHE NUCLEOTIDE REDUCTION
AND THE FORMATION OP ADENOSINE TRIPHOSPHATE BY SPINACH
CHLOROPLASTS. Biol. Chem. 237, (2J 580-3, Feb.. 1962
In this communication, the effect of monochromatic light on TPN
reduction and the associated formation of ATP in the spinach
chloroplast is described-. Data are also presented on the effect
of monochromatic light on the synthesis of ATP by the spinach
chloroplast in the presence of phenazine methosulfate. (Author}##
00235
F„H. Oliver
OH THE EFFECTS OF BRBAS TOG	UPOK CULTIVATED PLANTS, J- Roy»
Hort„ Soc,. 16, 1-59, 1893.	(The Second Report presented to
the Scientific Committee of	the Royal Horticultural Society,
Feb. 1893.. J
Author discusses the effect of foreign naterial emissions
associated with fog as they light cause damage to plants.. The
categories covered by author are: Remedial Measures to be
Taken; Behavior of Different classes of Plants (i»e.. ferns,
Honocotyledons* Dicotyledons); Effect of Reduced Illumination;
Changes which the Chlorophyll Undergoes in Leaves Injured by
Fog; Behavior of Flowers toward Fog and Certain of Its
Ingredients; Action of Pyridine and of Allied Bodies; and
Action of Pyridine and of Allied Bodies; and Action of Acid
and other Vapors-##
0C244
H«Wolf
MICROORGANISMS AND 0XIDIZIHG - TYPE AIR POLLUTION (DOCTOR'S
THESIS).. (For the degree of Doctor of Public Health#
California Div. Los Angeles.) 1965. 119 pp«
The possibility that oxidizing-type air poullution sight suppress
the viability of bacterial cells was investigated. Saspling
activities were conducted at the Azusa Station of the Los
Angeles County Air Pollution control District.
Micoorganisns indigenous to the air of the area were sampled
with an Andersen sampler. Bacteria and yeasts (together)
recovered during high-o*idant periods {total oxidant * greater
than 0.19 ppa) had a aedian equivalent diameter (WED) 0.3 aicrons
G. Effects • Plants and LivestocK
817

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greater than those recovered during low-oxidant periods (total
oxidant equal to or less than 0„19 ppn). This difference was not
considered significant since wind velocity was higher during high-
oxidant periods. Higher wind velocities effect a longer BED by
increasing the relative concentration of large-sized particles.
Although more organisms were recovered on the snail stage during
low-oxidant periods than during higb-oxidant periods, the level
of significance |0.8S) is low. Further, it was speculated that
sunlight light exert such an effect. Background studies shoved
gran-negative rods to be highly log-nornal in size distribution,
while gram-positive rods deviated fron normality. This deviation
of graa-positive rods was possibly due to the predominance
of two Morphological types, large spore-formers, and snail non-
spore-foriers„ Holds, including actinoaycetes, vere markedly
ncn-noraal in distribution. The highly log-normal distribution,
and absence of spore-f orating types, of the gran-negative rods
deserve special attention fros future investigators.. A
perweable-#e»brane technique was used to expose selected
¦icroorganisas to high-oxidant levels. (Author"s abstract)#*
00301
fu D» Thoaas
GAS DABAGZ TO PLANTS. Ann.. Rev. Plant Physiol. 2, 293-322,
1951.
A detailed review is given of gas daaage to plants with references
containing isportant bibliographies. Investigations on the
effects on vegetation of sulfur dioxide, other sulfur-containing
gases, halogens and hydrogen halides, nitrogen oxides, ammonia,
nercury vapor, and carbon coipounds are cited and results
discussed. Phytotoxicities of the different gases seen to depend
on (a) absorbability,, which is related to water solubility and
reactivity with the tissues; |b) acidity or alkalinity; (c)
oxidation or reduction reactions; (d) hormonal properties; and
(e) toxicity of the element itself, carbon monoxide, hydrogen
cyanide and hydrogen sulfide are of comparatively low
toxicity. Greater toxicity is evidenced by chlorine and sulfur
dioxide due to their rapid oxidizing or reducing properties.
The even greater toxicity of fluorine and iodine compounds is due
to their rapid absorption and inherent toxicity as elements in
themselves.. ##
00315
THE SBOG GBOB1EH ID LOS A8GE1ES COUNT!, LOB ANGELES.
Western Oil Gas Assoc. 70-1, 1954.
Close observations of damage in the field and comparisons with
damage occurring in the pnfiltered greenhouse were the basis of
th« studies of the various types of plant damage that occured in
818
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION

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the Los Angeles county area- After any one smog attack,
practically all of the several types of damage could be observed,
not only in a single field, but frequently even on a single plant.
At times, on the other hand, only one leaf out of a dozen on one
plant, or one plant in a row of plants, would be damaged.,
Similarly, although severe damage might occur in one field,
adjoining fields and surrounding areas were sometimes free of
damage. ##
00316
A„ R. Gregory
EFFECTS OF AIB POLIUTION OS ItlEIE CHOPS. Sorth Carolina
Univ., Chapel Hill, Dept., of Environmental Sciences and
Engineering. Hay 1964. pp. 21-3.
The effects of air pollution on edible crops should be
differentiated at the onset from the effects of air pollution
on vegetation in general. For example# sulfur dioxide
has a very pronounced effect on pine needles, but pine needles
are a minor food source. It has been variously estimated
by different authorities that the annual loss of vegetable
produce amounts to 40 to 60 million dollars. Although this
over-kill type of damage is very real to the vegetable producer
and is of great economic interest, it is of less concern
to those in public health. Their concern is with the damage
that alters the content s of crops but does not alter the
appearance sufficiently to prohibit their sale. This
results in threats to public health through the insidious
route of the gastro-intestinal tract. The alterations
in edible crops that ace usually not apparent to the
consumer fall into two categories: (1) loss of nutiirnts
such as vitamins, proteins* essential fatty acids, etc. and
(2) the addition of some substance to the food which is
toxic when absorbed from the gastro-intestinal tract.. The
loss of nutrients has been established in many cases.
Some of the substances which have been shown to produce
nutrient damage to produce are: ozone, nitcoolefins*
perocyacyl nitrates, nitrogen oxides, and ethylene. Of
probably greater importance to health now and assuredly in
the future is the addition of some toxic substance to the
produce* With the advent of possible atomic power plants. Be
was studied for toxicity and found to be extremely toxic„
It was found that Be taken up into bush beans was not only
toxic itself, but decreased the Cu content. In this way
it fell into the category of primary toxicant and also into the
category of nutrient depletor. Many other compounds also
fall into both categories, sith the many new insecticides,
herbicides and larvicides being manufactured, it has become
imperative to be aware of the problem of both the effect on
edibles of a toxicant and also its effect on the plant, that
is, loss of minerals, vitaiins, etc.##
G. Effects • Plants and Livastock
819

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00413
I.. J., Hindavi, J„ A. Dunning, C.S. Brandt
HOUPHOIOGICAL AND HICHOSCOPIAI CHANGES IN TOBACCO, EEAN, AND
PETUNIA LEAVES EXPOSED TO IRRADIATED AUTOHOBI1E EXHADST.
Phytopathology 55(1):27~30, Jan.. 1965.
Tobacco, Pinto bean, and petunia plants were shown to be useful
indicators of phytotoxicants produced fro# irradiated
automobile exhaust. Four distinct response patterns were
identified; these were considered indicative of 4 classes of
toxicants present in the irradiated exhaust. Toxicants in class 1
caused injury primarily in palisade cells of young leaves.
The upper leaf surface developed a water-logged appearance which
turned to reddish-brown, then light to dark, tan or bronze
depending on environmental conditions. Toxicants of class 2
produced an undersurface glazing on young leaves; spongy
parenchyma was typically affected. This pattern was similar
to the "snog" injury of southern California. Toxicants of
classes 3 and 4 injured the palisade cells, resulting in snail
dehydrated spots on the upper leaf surface. The 2 classes are
distinguished from each ether by the age of leaf tissue affected;
class 3 is apparent on the newly expanded leaf, whereas class 4 is
visible on nature to old leaves and is identical to ozone injury.
Other injury patterns such as pigmentation, crinkling, and
blistering may develop on the lower surface of young leaves 2-6
days after exposure to the exhaust**#
00433
S.. Kotaka, A„ P. Krueger and P« C. Andriese
SCHE OBSERVATION OS AIE-IOS-EHHAHCED IS08 CHLOROSIS IN EABIEi
(HOBDEUM VULGAHISJ SEEDLINGS. Plant Cell Physiol. (Tokyo)
Vol. 6i233-245, 1965,
The air ion effects on "active" and "residual" iron distribution
in barley seedlings were studied in the course of the development
of ironchlorosis in an iron-fxee culture tedium. Active oc
"acid soluble" iron plays an important role for chlorophyll
biosynthesis and is extxactable with 1.0 normal HC1 from dried
tissues and "residuai" or "acid insoluble" iron does not
participate in this chlorophyll formation process and is not
extracted with 1.0 normal HCU Ions of either charge induced a
significant decrease in active iron content which was associated
with a decrease in chlorophyll content, concomitantly, there
occurred an increase in both the residual iron and the cytochrome c
fractions. The increase in residual iron content may involve
not only cytochrome c but also other cytochromes and
iron-containing enzymeds as well. The authors have proposed a
hypothesis that the site of aix ion action in the experiments
reported may be the regulatory systems controlling iron metabolism
in the seed and young seedling. Through this action air ions
apparently divert more endogenous free-state iron to residual iron
820
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION

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(consisting of cytochromes and Fe-contaiuing eniymes) than to
active iron. Tracer experiments showed that air ions enhanced the
uptake of exogenous iron by early germination barley seeds.. The
increased incorporation of iron was not influenced by light-##
00577
A. P. Krueger, s„ Kotaka, and P. C« Andriese
STUDIES ON AIH-ION-ENHANCED IBOH CHLOROSIS. I„ ACTIVE AMD
HESIDUK1 lues. Intern. J. Biometeorol., 8{1):S-16, 196U,.
The effects of positive and negative air ions oti the active and
residual iron fractions of barley seedlings were studied during
the course of iron chlorosis* Active iron is that fraction
localized in the chloroplasts which dissolves in 1.0 N HCl and
participates in the biosynthesis of chlorophyll. Residual iron is
not soluble in 1.0 N HCl and is not concerned with the
biosynthesis of chlorophyll. Air ions of either charge induced a
significant decrease in active iron content which was
associated with a decrease in chlorophyll content.. Concoaitantly
there occurred an increase in both the residual iron and the
cytochrome c fractions of the seedlings. There is evidence that
the rise in residual iron content say involve not only cytochrome c
but also other cytochromes and iron-containing enzymes as vel3#
Ve have theorized that the site of air ion action in the
experiments reported may be the regulatory systems controlling iron
metabolism in the seed and young seedling. Through this action
air ions apparently divert endogenous free-state iron from
conversion to active iron and make it available for the production
of a number of iron containing compounds which are components of
the residual icon fraction* (Authors* abstract)##
00601
S. Kotaka, A*P.. Krueger P.C. Andriese
EFFECT OF AIR IOSS OK IAA COHTEBT OF BABLEY SEEDLINGS-
Plant cell Physiol. (ToXyol Vol. 6:711-9, 1965.
Exposure of barley seedlings (Hordeum vulgaris} growing in
sand and liquid cultures to either negatively- or positively-
ionized air results in increased growth in terms of integral
elongation, and fresh and dry weight increase. Dsing large
quantities of tissue and a modified method it was found that
free and bound IAA contents were not significantly modified
by exposure of seedlings to ionized air. It might be supposed
that an equilibrium between free and bound IAA was not modified
by exposure to air ions. (Author abstract)##
00604
A. P. Krueger, S. KotaJca, P. c. Andriese
G. Effects - Plants and Livestock
821

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THE EFFECT OF JIB CONTAINING 02 BINDS, 02 PLCS, C02 MINOS,
ANB C02 PIUS ON THE GROWTH OF SIEELINGS OF HOHDEtJM VOLGAFIS.
Intern- J. Biometeorl. Vol. 8 (1); 17-25, 196<*.
EguipBent was devised which permitted the addition of specific
gaseous ions to the atmosphere of plastic chambers in which
seedlings of HOFDEOS VUIGAHIS were grown in sand culture supplie
with chemically defined nutrient solutions.. Moderate
densities of 02 sinus or 02 plus ions (18000/ccj in air
containing an added 8* of 02 accelerated the growth rate.
A like number of C02 minus or C02 plus ions in air containing
81 of C02 inhibited growth, impeded the production of
chlorophyll and devitalized the young seedlings. Evidence is
presented that 02 minus and 02 plus stimulate the production
of cytochromes and other Fe-containing enzymes through their
action on the plant regulatory system responsible for the
control of Fe metabolism. The toxic effect of C02 Binus and
CC2 plus cannot be explained as yet.*#
0065U
I. Crdin
EFFECT OF AIB POLLUTANTS OH CELL BAIL METABOLISM.
Arch. Environ. Health Vol. 10(2)i189-19M, Feb- 1965-
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prevented by the addition cf ascorbate to the reaction mixture
Also NADP plus reductiob was maintained by adding either
excess photosynthetic pyridine nucleotide reductase (PPNR)
or heat inactivated PPNR preparations- Gassing the individual
components, chloroplasts or PPNR in the light or dark
prior to their use in a complete reaction* did not cause
inhibition-. (Author summary) ##
00696
A. cole and B. Katz
SUMMER OZONE CONCENTRATIONS IN SOUTHERN ONTARIO IN RELATION TO
PHOTOCHEMICAL ASPECTS AND VEGETATION DAMAGE- J.. Air
Pollution Control Assoc. Vol. 16:201-206, Apr. 1966.
(Presented at the 58th Annual Meeting, Air Pollution Control
Association, Toronto, Canada, June 20-24, 1965, Paper No.
65-113.,)
This paper describes an air pollution investigation at Port
Burwell, Ontario to determine the pollutant responsible for
fleck damage.. The study was part of a cooperative project with
groups representing the Canada Department of Agriculture, the
Meteorological Eranch of the Canada Department of Transport,
the Air Pollution Control Branch of the Ontario Department of
Health, and Imperial Tobacco Co. of Canada Ltd. In 1960 and
1961 the air pollution phase of the project Has undertaken by the
Occupational Health Division of the Department of National
Health and 8elfare.lt
00737
J.T., Hiddleton, L„0. Eaik, O.C„ Taylor
AIR QUALITY CRITERIA AND STANDARDS FOR AGRICULTORB„
J. Air Pollution Contorl Assoc., 18(10):476-«80, Oct. 1965.
(Presented at the SSth Annual Meeting, Air Pollution control
Association, Toronto, Canada, June 20-24, 19659)
Air pollution damage to crops is not only important for the
damage it causes agriculture but because vegetation damage is
a harbinger of air pollution problems affecting nan and his
well-being* Some of the effects of varying dosages of ethylene,
fluoride, ozone, PAN, and sulfur oxides on plants and animals
are given* Knowledge of the response of certain plants and
animals to specific air pollutants permits the establishment
of air quality standards for certain of these pollutants. The
importance of environmental conditions on host responses to
these several toxicants is also presented to illustrate the
need of stipulating environmental conditions as well as toxicant
dosages when establishing air quality criteria and
standards for the protection of the agricultural resource.##
G. Effects 'Plants and Llvsstock
823
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00775
fUR. Heck, J. A. Canning, I. J.' Bindawi
INTERACTIQBS OF BHVIBOBBESTA1 FACTQBS ON THE SEHSITIVIT? OF
PIA8TS TO AIR POLLOTIOH„ 0„ Air Pollution Control Assoc..*
15(111:511-515, Hot. 1965. (Presented at the 58th Annual
Meeting.. Air Pollution Control Association. Toronto,, Canada
June 20-2#, 1965.)
Before potential danage to vegetation can be adequately forecast,
even after an air pollution alert has been placed in effect, a
clear understanding of the interactions of environment on plant
sensitivity Bust be ascertained* This involves detailed
study of single factors and then nultiple factors using the
phytotoxicants in question. Factors studied or suggested included
light (quality, intensity,, and duration), temperature, carbon
dioxide concentration* huaidity, wind, soil aoisture, soil
aeration, nutrient levels, and soil texture. This paper presents
a review of the work relating plant injury to specific air
pollutants as conditioned by environaental conditions.
Preliminary research with ozone is discussed. (Author
abstract)**
00786
A.P« Krueger, S. Kotaka, P..C. Andriese
THE EFFECT OF ABNOBBALLY LOW COHCEMTHATICHS OF AIB I0HS OH THE
GFOSTH OP H0BDE0H VDLGABIS. Intern. J. Bioneteorol.,
9133:201-209, 1965.
A chaaber has been designed for growing seedlings in a
chenically defined aediua while laintaining thes in air containing
ca 30 plus and 30 sinus air ions/cu cm. Air-ion depletion
produces a significant reduction in growth of HOFDEOW VULGARIS
seedlings as measured by integral elongation, fresh weight and
dry weight. There is no gross change in chlorophyll production
but after 30 days of growth the plants have very soft leaves and
lack noraal rigidity. (Author abstract}*#
00950
S. fl. Dagger, Jr., J. Xoukol. and B. I. Palier
PHYSIOLOGICAL AND BIOCHEMICAL EFFECTS OF ATHOSPHEBIC OXIDAHTS OH
PLA8TS. 0. Air Pollution Control Assoc., 16(9) :«67-i)71„
Sept. 1966. {Presented at the 59th Annual Heeting, Air
Pollution Control Association, San Francisco, Calif., June
20-25, 1966, Paper So. 66-U7.)
Photocheaically produced oxidants in the atnosphere cause injury
824
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
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to plants primarily through inhibition of basic metabolic
processes. Plants vary in their response to the oxidants and this
variation Bust be dependent in part cn the variation in metabolic
activity with age or environmental conditions for growth, to a
large degree not understood. Data are presented In this paper to
show: (1) The changes in permeability of leaf tissue to
exogenous substrate and in catabolic utilisation of this substrate
after exposure of plants to ozone but before visible symptoms
appear; (2) The change in leaf carbohydrates as a result of
exposure to ozone; ^3) The protective effect of red light (700
villinicrons} during exposure of bean plants to peroxyacetyl
nitrate (PAN); |U) The correlation of sulfhydryl (SH) content
in bean leaf tissue with age of plants and light regime; and (5)
Effect of light regine and age of plants on incorporation of
C1U from Cl^-Pan by bean leaf tissue. (Author abstract}##
00953
Bi> E» Heggestad
OZONE as A TOBACCO T0XICART.. J. Air Pollution Control
Assoc.,, 16(12) : 6S1-69U, Dec., 1966. (presented at the 59th
Annual Meeting# Air Pollution Control Association, San
Francisco, Calif., June 20-25, 1966.)
Tobacco leaves nay develop many types of pathogenic and
nonpathogenic leaf spots, but not until 1958 vas it known that the
air pollutant ozone was the primary cause of a leaf spot on
tobaccc known as weather fleck or ozone fleck. Cigar-wrapper
tobacco which is grown under cotton cloth for shading is very
sensitive to ozone* This report presents most of the available
information on ozone as a tobacco toxicant.lt
CG961
I. J. Hindawi and A. P. Altshuller
PlMTt tlkttXGl CXBSUti TTOXSlfcHG* CT HMttl&SS,. Science
146(3643) :540-542, Oct. 23, i960..
The report that danage to petunia has been correlated with
the presence of aldehydes in the atmosphere is discussed in
relation to recent laboratory findings* Laboratory investigations
have shown that Irradiation of formaldehyde in air will not cause
plant damage to the varieties of petunia, pinto bean, and tobacco
wrapper used, even when nitrogen oxide is added to the system-
Irradiation of propionaldehyde in air does cause danage to these
plants,, Addition of nitrogen oxide to the irradiated
propionaldebyde-in-air system does not markedly increase damage.
(Author abstract)**
00963
Taylor, 0. C„, and 7. R. Baton
G. Effects - Plants and Livestock
825
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SUPPRESSION OP PLANT GROWTH EY NITROGEN DIOXIDE. Plant
Physiol. Vol- i»1:132-135. 1966. 9 cefs.
Nicotiana glutinosa and pinto bean seedlings (Phaseolus vulgaris)
were exposed for short periods |3 days or less) to high
concentrations of N02
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EVALUATION OF VEGETATION INJURY as AN AIR POLLUTION CRITERION.
J. Air Pollution Control Assoc- 15, (6) 266-9, June 1965.
Foliar markings on vegetation have proven a highly sensitive
criterion for the presence of many air pollutants; proper
evaluation of such effects can serve as a valuable and inexpensive
tool for delineating an air pollution condition- Injury symptoms
from fluoride, sulfur dioxide, photochemical oxidants and other
pollutants have been described and can te recognized by experienced
observers. Several factors Bust te considered in appraising
injury. These include a knowledge of the relative sensitivity of
plant species to various pollutants, the syndrome of injury on a
number of plants and species, and distribution and geographic
relation of affected plants to the suspected source. Background
information on cultural® environmental, disease and insect
conditions which night be responsible for, or modify, foliar
markings or chronic effects in question must also be understood.
For some pollutants a chemical analysis of foliage and air may
prove helpful.. When these factors are studied, the presence,
distribution and magnitude of an air pollution situation can be
evaluated, thus providing a sensitive criterion of air quality.
(Author abstract modified)##
01391
F,«„ Bent
DISPERSION AND DISPOSAL or ORGANIC MATERIALS IN THE ATHOSPHEHE.
Nevada Univ., Reno, Desert Research Inst., 10p., April 1966.
((Series No. 31.} Also: Intern. J. Biometeorol„
¦(Amsterdam), Vol. 11, 1967.
Author reiterates the sensitivity that plants have to smog and
shows that plants are used as an indicator of air pollution. Also
discussed, in general terms, are the roles that meteorological
conditions (in particular, haze) play in the health impairment of
individuals. Author concludes by stating there is a need for
additional study of the mechanisms in which volatile organic
substances may be involved in problems of human health.##
01398
G.fl. Hepting
AIB POLLUTION IHPACTS TO SOHE IHPOFTAKT SPECIES 07 PINJ.
0.. Air Pollution Control Assoc., 16(2}:63-65, Feb. 1966.
In the past, many species of pine have been severely damaged by
acute forms of air pollution associated with ore smelting.. Hore
recently, damage to ponderosa pine in the State of Washington has
been associated with atmospheric fluoride, and this species in
particular has also suffered sitcg damage in southern California.
In the East, whie pine has been declining in the vicinity of
G. Effects - Plants and Livestock
827
-------
certain soft-coal-burning power plants, and in one case downwind
ftoi an oil-burning power plant; also* throughout the Bast, an
atmospheric oxidant of unknown source has caused a type of needle
blight on white pine. Trash burners and city dump combustion have
led to the killing of certain pine species, leaving other
intermixed pine species unharmed™ Localized damage to white pine
front automobile exhaust has been observed. Differences in the
susceptibility of neighboring trees of the sane species to a
given air pollutant have been observed repeatedly. (Author
abstract) 4#
01421
En A.. Renser and H„ E« Heggestad
OZONE ASB SULFtJB DIOXIDE SYHEHGISB: ISJUHTT TO TOBACCO PLANTS.
Science, Vol.. 153: U2U-t25„ July 22, 1966»
Tobacco plants displayed ozone-type injury when exposed to
mixtures of ozone and sulfur dioxide at subthreshold
concentrations. The syndrone suggests synergism between ozone and
sulfur dioxide that lowers thresholds to injury; exposure to the
individual gases at the mixed-gas concentrations caused no
symptoms. (Author abstract)#1
01««9
A. P» Krueger, S. Kotaka, and P. C. Andriese
A STUDY OF THE H1CHAHISH OF AIR-IOH-IMDOCEO GBOWTH STIHULATIOH
IK HORDEDH VULGARIS. Intern, o. Biometeorol., 7(1):17-25,
1963.
Hordeum vulgaris seedlings grown in a chemically defined Fe-free
nutrient solution develop iron chlorosis. When the growth takes
place in unipolar ionized atmospheres of either charge the onset of
chlorosis is accelerated and this is accoapanied by the appearance
of large amounts of cytochrome c. Apparently the air ions cause
most of the limited store of Fe present in the seeds to be
utilized preferentially in the synthesis of cytochrome c and not
enough is available to support the normal biosynthesis of
chlorophyll. Rhen the seedlings are grown in a substrate
containing Fe and are exposed to ionixed air they do not develop
chlorosis but exhibit the typical ion-induced increase in growth
rate and an increased production of cytochrome c. Here the
supply of 7e is sufficient to provide for both the biosynthetic
processes. Ho evidence was found that a change in ratio o£ free
to bound indole-3-acetic acid accompanies the ion-induced
stimulation of growth. (Author abstract)if
01666
I.A. Leone, E* Brernan. B.H. Daines
828
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
what is in neh jehsey aih that CAUSES PLANT DAKAGE? Hew
Jersey Agr. 44, 11-3, Aug,. 1962
Air samples were taken in Carlstadt, Bordentown and at
New Brunswick, and S02,03 and 8C2 were determined daily
during a 4-hr period. Kith regard to S02, Carlstadt was the
most polluted. New Brunswick next, and Eordentown had the
lowest pollution. In Carlstadt and New Brunswick S02
often exceeded 0.1 pps which is believed to cause damage to
alfalfa, violets and crab apple, in all three locations
03 freguently exceed the 0.035 ppm which causes fleck on
tobacco and other more sensitive plants. N02 is a
constituent of some of the photochemical reactions which produce
Material toxic to plants. High barometric pressure and low
wind speed are associated with an increased air pollution load.*#
01697
S-. Kotaka, A..P. Krueger, P„c. Andriese, K. Nishizawa,
Ohuchi, H«. Takenobu, T Kozure
AIR ION EFFECTS ON THE OXYGEN CQNSOHPTION OF BAftLBY StBDlINGS.
Mature 208, (5015) 1112-3, Dec. 11, 1965.
Barley seeds (Hordeua vulgaris var. "Husashino") were soaked in
distilled water and aerated for 3-5 days. Germinated seeds with
several roots 1-2 ca long, but without an emerging coleoptile,
were placed on "Cashmiron11 wool noistened with distilled
water in a plastic Petri dish. Each of three dishes
containing 30 seeds was placed in a plastic ion chamber. The
seeds were exposed in the dark to air-ion densities of 4.5 times
10 to the 7th power (-) ion^/sg cm/ sec; 1.0 times 10 to the 7th
power {plus) ions /eq c*/ sec or to normal non-ionized air- At
stated intervals 5 seedlings were collected from each chamber
and their oxygen consumption was measured by conventional
manonetric methods at 30 C repeating each determination three
times.. Next, the seedlings were dried, first in an oven at 60 C,
then over calcium chloride in a desiccator, and they were weighed.
Even as early as 24 hr. after the start of exposure to air ions,
there was a clear-cut increase in oxygen consumption of the
treated seedlings as compared with the controls and the
percentage increase at each time-interval remained relatively
constant throughout the 96-hr* period of observation.
Evidently as increased oxygen consumption is a significant element
in the response of higher plants to treatment with air ions.*#
01728
I. Ordin and A. Altman
INHIBITION OF PHOSPHOGLUCOHDTASE ACTIVITY IN OAT C0LE0PTII.ES BY
AIR P0U0TANTS. Physiol. Flantarum 18, 790-7, 1965.
A marked inhibition of cellulose and o£ glucan biosynthesis
G. Effects-Plants and Livestock
829
-------
induced by the air pollutants fluoride, ozone and peroxyacetyl
nitrate »as found in oat coleoptile sections. It was
suggested that a cohod point of attack by these inhibitors might
fce phosphoglucowutase which catalyzes the interconversion of
glucose-6-phosphate and glucose-l-phosphate. Glucose-l-phosphate
is a probable precursor for glucan and cellulose biosynthesis.
Fluoride is known to inhibit plant phosphoglucomutase in vitro
more than the other enzynes involved in sucrose biosynthesis.
Photooxidation producing inactivation has been carried out with
pyre phosphoglucoaatase of aniaal origin. The influence of the
air pollutant oxidants both in vivo ana in vitro on this enzyme
is unknown. The purpose of this report is to present results
concerning the effect of these inhibitors on phosphogluccmotase
activity in oat coleoptile tissvse and the effects on enzyme
prepared from this tissue.##
C1800
H. Fi,. Daines# I. A. Leone, E. Brennan
AIR POLLUTION AS IT AFFECTS AGRICBITUBE IN ME» JSRSFT.
Rutgers - The The state Hniv«, Sew Brunswick,
Agricultural Experinent Station- {Bulletin 79«|„
Plant daaage in Hew Jersey fren sulfur dioxide, hydrogen
fluoride* herbicides, ozone, and from oxidants other than
ozone is discussed. Relevant literature is reviewed.##
01809
-J.T- Hiddleton
TRENDS IK AIE POUBTIOR EAHAGE. Arch. Environ, Health 8,
19-23, Jan. 196
-------
ROOTS., Soil sci. Soc. An. Proc. 28, (3J 305-8, June
196«.
The degree to which tomato leaves were altered following short
periods of reduced oxygen in the roct zone was studied in relation
to the following factors: apparent rate of photosynthesis,
susceptibility to ozone# and carbohydrates concentration. Seduced
rates of soil oxygen for 8 1/2 hours brought about a 50* decrease
in C02 fixation by plants, while shorter periods (3 hours) had
only a slight effect on ap-parent photosynthesis. However, the
short period of anaerobic treatment over the soil surface,
followed by normal soil aeration for 24 hours, reduced the
susceptibility of the plant to ozone damage by as much as 50X«
Carbohydrate analysis of leaf tissue for similarly treated plants
showed a 50* reduction in sucrose and 33* reduction in starch. It
is hypothesized that the anaerobic pretreatment brought about a
change in the root membrane permeability or a shift in metabolism
that promoted excretion of certain carbohydrates from the roots
which in turn changed the concentration of carbohydrates in the
leaves. (Author abstract)##
01905
f>. Thomson, W. H., Dugger, Jr., and R. L. Palner-
IlSECTS OP PEBOXYACITYL HITRATE ON UITFASTHOCTDBE OF
CHLOROPLASTS. Boton.. Gas- 126 (1) 66-72, 1965.
Electron-microscope studies of leaves fumigated and subsequently
damaged by peroxyacetyl nitrate revealed that the cfcloroplasts were
narkedly altered as the damage developed. The first noticeable
change was the appearance of small electron-dense granules in the
stroma. The granules increased in number until the stroma was
almost completely electron dense. Subsequently, "crystalline"
arrays of granules appeared, and the cbloroplasts became altered in
shape.. The granules seemed to fmse into rods and then into an
organized system of plates. Finally, the integrity of the
cellular membranes was disrupted, and the cell contents clumped
together in a large mass. The organized system of plates was
still present in this mass and even seemed to continue
developing. (Author abstract)It
02209
¦-!!«. Dugger, Jr., O.C. Taylor, E. Cardiff* C.R.
Thompson
STOHATAL ACTIOS II PLAUTS AS BELATED TO DAHAGB FROB
PQOTOCHEMICAX OXIDANTS. Plant Physiol., 37, 087-91, 1962-
The role of stovates, as a factor in controlling the injury to
G. Effects - Plants and Livestock
831
-------
plants from the photochemically produced pollutants, ozone and
peroxyacetyl nitrate (PAN)/ was investigated. Stomatal action
was quantitatively measured by determing the resistance of air
flov through the stomates with a Wheatstone bridge
resistance porometer. By a combination of measurements
involving apparent photosynthesis, transpiration, and degree of
leaf danage produced by the air pollutant oxidants it was
shown that: (A), Stomates open rapidly in the light, even after
a long dark period, and close slowly in the dark; (BJ ,
Transpiration rate from plants transferred froa the dark to the
light equals the rate of control plants in the light within 30
¦inutes; (C , The physiological age of bean plants and not the
degree of stomatal opening determines the susceptibility to the
two oxidants. Five and sis day old bean plants are not damaged by
ozone yet the stoiates are functional. Plants of this aqe are
¦ost susceptible to PAN damage; fEJ, Apparent photosynthesis
and degree of stomatal opening are not significantly reduced in
pinto bean by a 30 minute fumigation with ozone- The length of
the pre-fumigation dark period determines the extent of leaf danage
fro* this pollutant. The nature of ozone danage and the
protective acticn of a long pre-funigation dark period suggest that
the level of carbonhydrates in the leaves has soie role in
predisposing plants to daaage from this oxidant. (Author
summary) #•
02299
CUT. Hiddleton
FLIRT DAMAGE: AS ISDICATOB OF THE PRESENCE AND DISTRIBUTION OF
AID POIIOTION. Bullu World Health Organ. (Geneva)
34, <3) 477-80, 1966.
Air pollutants may damage plants and cause death or
destruction of tissue with visible pathological symptoms, reduce
growth, productivity, and commodity quality, and interfere with
biological processes without causing visible injury symptoms. The
contaainants responsible for damage may be either particulate or
gaseous in nature* The solid particles released into the
ataosphere are sometimes the cause of soiling of fruits and
vegetables, tissue daaage to exposed leaves and fruits, growth
reduction; in addition# they add a toxic burden to forage crops
used as feedstuffs for livestock. Liquid particles, such as acid
aerosols and toxic mists, are soaetiaes responsible for leaf
spotting. The greatest amount of daaage to animals and vegetation
is usually caused by gaseous air contaainants, which directly
injure plants and indirectly injure animals by the toxic effects
produced after the aniaal has consumed contaminated forage and
food supplements. This discussion of plant daaage symptoms and
responses has been directed to the qualitative aspects necessary
for assessing the presence and distribution of pollution. As to
the evaluation of the concentration and duration of exposure to
specific pollutants, experiaental systems are available, or can be
designed, to meet these specific quantitative needs once the
presence of given pollutants has been deterained.##
832
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
02313
S«,TR. Linzon
DAMAGE TO EASTEBW WHITE PISE BY SULFUR DIOXIDE* SEHlHATUFE-
IISSDE HEEDIE BLIGHT* ASD OZOKI. J. Air Pollution
Control Assoc* 16, |3) 140-ft, Bar. 1966.
Eastern white pine fPinus stobus 1.) forests were severely
damaged by atmospheric sulfur dioiide up to distances of 25 Biles
northeast of large skelters located in the Sudbury mining
district of Ontario. Damage to white pine was measured in terns
of foliage, bar*, and biological injuries, radial and volume
growth decrement, and tree mortality* The foliar symptoms of
sulfur dioxide injury on white pine trees sometimes resemble
those caused by a physiogenic disease, semimature-tissue needle
blight (abbreviated to SNB). Studies on the nature and
etiology of SHB were conducted in white pine forests in the
Upper Ottawa Valley, which are remote from smelter operations
which might pollute the atmosphere. These studies included
the determination of the role that naturally-occurring
atmospheric ozone plays in the occurrence of SNB. Differences
between the syiptcms of sulfur dioxide injury, SNB, and
ozone damage ace outlined. (Author abstract)*#
02371
effects of aih poilotahts on obgahisms otheb thah ban (*°®
Psac sOB-pANEt OH EIVIHCNHIST PCIIUTIOSJ. preprint. Public
Health Service, Hashington, C. C. , Div. of Air
Pollution 1965.
This paper reviews damage to vegetation by exhaust components,
industrial effluents and photochemistry. Author cites
evidence of damage to animals, under natural conditions, gained
£rom observation of cattle affected by fluorides. Agricultural
economic losses, as well as current and proposed research are
discussed*4t
02379
C» B„ Thompson.
THE TOTAL EFFECT OF Aia POI10TASTS OH BEABING CITBUS.
Preprint. 1965.
The three field installations of plastic covered greenhouse
established over bearing lemon and orange trees will be continued
for one, two and three years, respectively, until five years of
data are obtained at each installation on the effects of air
G. Effects - Plants and Livestock
833
-------
pollutants on fruit yield, leaf drop, fruit guality and storage
stability of fruit. More refined measurements of the more basic
responses of the trees, apparent photosynthesis, respiration and
transpiration will be made and correlated with the occurrence of
specific pollutants in the aii. The way in which oxidants cause
increased leaf drop will be studied- The effects of very low
levels of fluoride on- trees will be investigated to find out
whether or not there nay be a significant stimulation of the above
mentioned responses, especially fruit yield. The effect of
nitrogen dioxide will be examined in the fractions of one part per
million range® Interrelationships between the presence of air
pollutants and beneficial or deleterious insects will be examined.
An attempt will be made to determine threshold levels of
pollutants below which no injury occurs to plants, A concerted
effort will be made to overcome the excessive fruit abortion of
navel oranges by the application of antioxidants. Pesults of
some of the studies in the following categories are reported:
photosynthesis; fruit yield# transpiration; leaf carbohydrate
levels; anthrone reducing carbohydrates in citrus leaves; leaf
drop., (Author summary modified)##
02537
G. Seidman
EfEECTS OP SIB POLLUTION ON PLANTS.. African Violet Hag.. 18,
(3) Bar., 1965
The first indication of an air pollution problem is often the
injury that appears an comparatively sensitive vegetation., some
plants are more resistant than others to a given phytotoxicant.,
Plant injury from air pollution is caused primarily by the major
gaseous pollutants (sulfur dioxide, fluoride gases, ethylene, and
the components of the photochemical smog complex) and is
produced in various ways in urban or industrial areas. These
major.pollutants and several of the minor pollutants are
discussed in this paper.#•
02744
fi.. £.. Heggestad
BfTECTS 0? OZONE ON TOBACCO. Preprint- (Presented at staff
(leeting. Division of, Air Pollution, Public Health Service,
Washington, D«C., Dec- 3, I960.)
done has been established as the cause of tobacco weather
fleck. Connecticut shade-grown cigar-wrapper varieties were used
in these studies because fleck was first recognized as an economic
problem an wrapper tobacco, evidence was obtained to indicate
that the pollution source at Beltsville, Maryland, was
metropolitan Hashingtoa, B.C. 8hen used as pre-fumigation
834
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
cultural pcac-tices, mi» teaperatares ajid dark periods increases)
-------
plants receiving an "optiaua" nitrogen supply Here found to be aore
susceptible to ozone injury than those receiving deficient
or luxury supplies. Furtheraore, it was found on analyses of
the third oldest tobacco leaf that, while these
"optinua" plants shoved little or no increase in respiration
as a result of ozone in concentrations too lov to produce
visible injury, plants grown with deficient or excess nitrogen
shoved a significant increase in respiration under these
conditions.. The increase in respiration was accompanied by a
comparable and egually significant decrease in carbohydrate
content in the latter plants which was not apparent in plants
at the "optiaun" nitrogen supply, as well as an increase in total
nitrogen, protein-nitrogen* and anino-acid nitrogen. In
conclusion, it is suggested that the carbohydrate reserve built up
in plants grown with deficient nitrogen nutrition serves as
protection against the oxidative potential of ozone. Likewise, a
decrease in carbohydrate content below that of "optinua" plants
provides protection in plants grown with an overabundance of
nitrogen fertilization, through possibly by a more complex
aechanisnu {Author abstract} M
03094
0»c» Taylor,, I. A. Cardiff, J.D. Mersereau
APPARENT PHOTOSYNTHESIS AS A MEA5UKE OF AIR POLLUTION DABAGE.
0.. Air Pollution Control Assoc- 15, (4) 171-3, Apr*. 1965
{Presented at the Sixth Conference on Methods in Air
Pollution Studies, California Eept. of Public Health,
Berkeley, Calif. Jan. 6-7, 1964.)
A system has been developed to automatically aeasure the
effects of air pollutants in the aabient air on the rate of C02
exchange by intact leaves of citrus trees growing in the field. A
miniaturized systea utilizing the sane nondispersive infrared
C02 analyzer has been designed to study individually
the effects of different concentrations of air pollutants on
photosynthesis and respiration by plants. (Author
abstract)##
03098
B.lo Richards O.C. Taylor
SIGNIFICANCE OF ATMOSPHERIC OZOSE AS A PHlTOTQXICANT. J. Air
Pollution Control Assoc., t5, (5J 191-3, Bay 196S
Since the recognition of ozone as a aajor phytotoxicant
in crop plants in 19578 ozone type syaptoas have been observed
in a wide range of vegetation. These observations include leafy
vegetables, field, forage, and textile crops, also shrubs, broad-
leafed ornaaental, fruit and forest trees, and various conifers*
836
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
Yuaigation experiaents at various institutions have confirmed
the etiological relation of ozone in Many of these observations.
Such visible injuries fail to provide a reliable index to the
daaaging iipact of ozone on the nunerous plants affected. Hidden
injury or daaage by ozone at sub-necrotic levels has been
reported and experimentally established in a nuiber of crop
plants.. Evidence is available which indicates that citrus
varieties are so affected* and that auch of the citrus decline in
Southern California Bay be ozone induced. Photocheaically
induced ozone lay prove to be the aost persistent, if not the most,
difficult, of ataospheric phytotoxicants to control. Ozone type
injury has been reported froa eighteen different states, and from
Canada to Japan. (Author abstract)*#
03163
1. X. Iapens, D* B. Stewart, £• H. Allen, Jr., and
E. R» leaon
CIFPDSIVE RESISTANCES AT, AND TBANPIBATIQN BATES TBOH 1EAVES IN
SITU WITHIN THE VEGETATIVE CANOPY 01 A COBN CBOP. Dept. of
Agriculture, Ithaca, N.I., Plant, Soil and Nutrition Lab.
(Interia Sept. 66-1} (Task IVO-14501-B53A-08|„ June 1966.
26 PP.
CFSTI,DDC AD 638 3K6
At several heights and tiles of day within a crop of Zea Mays,
internal leaf diffusion resistance and external boundary layer
diffusion resistance were evaluated by aeasuring the tenperature of
a transpiring and a nontranspiring leaf (siaulated by covering both
sides of a nornal leaf with strips of polyethylene tape), and by
aeasuring the iaaediate air teaperature, huaidity and windspeed.
Both external boundary layer diffusion resistance and internal
leaf diffusion resistance increased with depth into the crop.
However, external boundary layer diffusion resistance generally
was less than 10% of internal leaf diffusion resistance. Profiles
of latent-heat flux density and source intensity of transpiration
showed that transpiration corresponded roaghly to foliage
distribution (with an upward shift) and were not siailar to the
profile of radiation abscrption« The data were coapared with heat
budget data. The two approaches yielded quite siailar height
distributions of transpiration per unit leaf area and total
transpiration resistance. The total crop resistance to
transpiration was ceapated as 0.027 ain/ca. This coapares well
with Bonteith"s values of 0.017 to 0.040 ain/ca for beans
(Phaseolus vulgaris 1.) <(17), and Liaacre's values of 0.015 to
0.020 ain/cn for turf. {Author abstract)##
03292
7. B« Burleson, e. B. Stephens, and Z. A. Cardiff.
THE PB0D0CTI0N OF PURE PIB01YACIL NITBATES. Preprint.
G. Effects - Plants ami Livestock
837
-------
^Presented at the Sixth Conference on Methods in Air
Pollution Studies, California Dept. of Public Health,
Berkeley, Calif., Jan. 6-7, 1961.)
Sane naturally occurring photocheaical products of "smog" were
first identified as "confound X" by Stephens efc al in 1956. In
1960, the first aeaber of the series was recognized as
peroxyacetyl nitrate tPAH) by Stephens et al. The C3
hoaologue, peroxypropionyl nitrate (PPNJ was reported in synthe-
tic mixtures by Stephens in 1961. Both the C2 and C3
homologues were detected in aabient air by fiarlay et al in 1963.
only froa synthetic preparations. The first 3 organic N con-
pounds have been synthesized and purified at the Air Pollution
Research Center, University of California, Riverside, for the
past several years. Plant fumigations have deaonstrated that
these compounds are capable of inducing injury synptons
indistinguishable £roa those caused by photochemical snog. They
are also powerful eye irritants. They have been identified (as a
class) in artificially irradiated dilute auto exhaust, and in
artificially irradiated aixtures of realistic concentrations of
pure hydrocarbon plus oxides cf nitrogen. The three purified
synthetics have been used in plant fumigation tudies, in eye
irritation studies, in physical and cheaical studies designed to
confirm the structure of the compounds, and in instrument design
and calibration. The principal problea in this preparation is the
extreae instability of these coapounds.##
03395
H.D. Thoaas
IFFECTS OF AIR POLLUTIOS OH PXASTS. World Health Organ.
Bonograph Ser. U6
-------
interfering with photosynthesis in concentrations 2 or 3 orders
of magnitude smaller than in the case of S02. With nast
species it is up to 10 tines as effective as S02. Fluoride
accumulated in the cells in sublethal amounts interferes with
photosynthesis as does sulfite* but whereas the latter is
deactivated by simple oxidation to sulfate, the former must be
removed by translocation, volatilization, or some obscure chemical
reaction# which makes much slower the recovery of the plant
functions after HF fumigation., there appears to be a
concentration of HF for each species below which "invisible
injury" does not occur. The 10s Angeles type smog is fairly
well understood as to its mode of formation and its phytotoxic
effects, but the actual compounds that cause these effects are
still unknown. The smog causes characteristic leaf lesions
which are quite different from those produced by other
pollutants, including ozone, which may be a constituent of the
smog. It also causes some "invisible" injury, visible
damage to crops in Southern and Northern California was
estimated at over $5 000 000 and $1 100 000 respectively,
annually, in 1956. {Author summary modified)*#
C3tt72
c«. s., Brandt
AIR POLLUTION BVVECTS ON VEGETATION. Conn. fled, 27, (8)
H8ft-6, Aug.. 1963.
The effects of air pollution particularly of sulfur dioxide,
fluorides and photochemical smog on plants are briefly reviewed.
The characteristic symptoms of air pollution injury to plants can
be useful tool in field surveys. Great care must be exercised in
using plants as indicators of aix pollution, because many factors
affect the symptoms, development, and interpretation of plant
indicators.*#
03195
1. Qrdin and B. P. Skoe
OZONE EFFECTS OH CELL NAIL »EtABClIS» OF AVINA COLEOPTILE
SECTIONS. Plant., Physiol. 39, <5) 751-5, Sept. 1964.
{Part of this work was reported at the Annual Meeting,
American Society of Plant Physiologists, Amherst, Mass.#
Aug. 26, 1963..)
Pretreatment of coleoptile tissue with 90 to 1«0 ppm by volume
of ozone resulted in a subsequent stimulation of glucose uptake
without destroying the final growth capacity of the tissue. This
phenomenon occurred at both 0«00001 m and Q«05 m external glucose
concentration. Cellulose synthesis and incorporation of C-1H
from C-1U labeled glucose into glucan components of the cell wall
were most readily inhibited by ozone treatment. Metabolism of
other cell wall components was affected much less under conditions
G. Effects • Plants and Livestock
639
-------
resulting in less than 50* inhibition of potential growth. The
relationship of ozone to other inhibitors of cell wall metabolism
and growth was discussed. It was suggested that ozone inhibition
of glucan and cellulose metabolism may be a factor in inhibition of
plant growth by ozone. (Author summary)##
03496
I. Or<3in, tl. J. Gather, b. P» Skoe, and G. nolle
HOLE OP AUXIM IS GROWTH OF IHHIBITOB-TREATED OAT COLEOPTILE
TISSUE. Physiol. Plantamm 19, 937-45, 1966„
The role of auxin in the recovery of plant tissue from oxidant
treatment was investigated*, Treatment of oat coleoptile sections
with concentrations of indoleacetic acid (IAA) or
2,4-dJ.chlorophenoxyacetic acid (2,4-D) optimal for normal growth,
folllowing pretreatment with moderately inhibiting levels of
peroxyacetyl nitrate (PAN) immediately accelerated recovery of
growth rate. In some cases inhibition was also less at
supraoptimal values of auxin. Treatment of ozone-pretreated
tissue with IAA or 2f«-D enhanced inhibition at high levels of
auxin and produced an optimal growth concentration level which was
lower than for sections not given ozone pretreatment. Auxin
treatment also reduced the degree of inhibition in fluoride and
iodoacetamide-pretreated sections.. Mechanisms by which
auxin-induced recovery from inhibition may occur are discussed.
(Author abstract)##
03531
C. R. Berry 1- A. Sipperton
OZOSE, A POSSIBLE CAUSE OP HHITB PIHE EMERGENCE TIPBUfi*.
Phytopathology 53, |5) 552-7, Bay 1963.
Attacks of white pine emergence tipburn occurred in
Pocahontas County, R. Va„, in summer, 1961, during a
period of high atmospheric oxidant concentration. Oxidant
concentrations as high as 6.5 pphm were recorded.. Potted
susceptible white pine ramets were protected from
emergence tip-burn by placing them in a chamber supplied
with air filtered through activated carbon. Typical disease
symptoms were produced on lamctc in the greenhouse* using
artificially produced oxidant at concentrations and exposure
times similar to those recorded in the field, thus
strengthening the thesis that an oxidant, probably ozone, is a
cause of emergence tipburn. fAuthor summary}##
03549
D. F«. Adams
840
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
AH AIB POLLUTION PH1TOTHON (A CCNTBCILBD ENVIBOBMEHT fACILITY
FOB STODIBS INTO THE EFFECTS OF AIR POLLUTANTS ON VEGETATION).
J- Air Pollution control Assoc., 11, <10J U70-6, Oct. 1961.
(Presentrd at the 5Uth Annual Meeting, Air Pollution Control
Association, New York City, June 11-15, 1961-J
The facilities described have been used in the study of the
influence of atmospheric fluoride pollution on plant response™
The design concepts and resultant equipment are equally
applicable to similar plant studies using other atmospheric
pollutants. Only relatively minor changes in the atmosphere-
producing equipment would be required., So-called field
conditions cannot be produced in a phytotron chamber since the
objective is one of a completely controlled plant environment..
However, numerous parameters such as (a) stem elongation
and diameter, fb) leaf size and development, (c) chlorophyll,
sugar, carbohydrate, and enzyme content, and (d) respiration
and photosynthetic rates, etc., readily respond to all phases of
the plant environment and thus introduce difficulties in
separating the response to these variables from that of the
air pollutant* Thus the availability of such an air
pollution pbytotron promises to eliminate much of the present
uncertainty involved in relating physiological and
biochemical measurements with air pollution*##
03573
8. H., Arnold.
THE LONGEVITY Of THE PRtTOTOXICAST PRODUCED FROM GASEODS OZONE-
OIEFIH R2ACTIOMS. Intern. J. Air Mater Foliation 2, 167-
7l», 1959.
Gaseous mixtures of an olefin and ozone were blown at constant
rate through a 32 ft. tube of uniform cross section* A snail
aguatic plant was placed at prescribed intervals within the tube.
The phytotoxicants produced from the o2oni2ation of bpth
3-heptene and 2-pentene were shewn to be unstable. The
distribution of plant damage within the exposure tube indicated the
longevity of the phytotoxicant. The reduction in chlorophyll
content of fumigated plants was used as a quantitative measure of
damage. The results suggest that the decay of the phytotoxicant
follows a first order or pseudo-first order reaction. The
half-life of the phytotoxicant from ozonated 3-heptene is 1/t hr
while the phytotoxicant from oicoated 2-pentene has a much
shorter half-life. This difference in stability can be
explained in terms of the "atwitterion" mechanism. (Author
abstract)##
03565
I. G. Brennan, l„ A. Leone, and R- H. Dailies
ATMOSPHERIC ALEIHYDIS BELATED TO PETUNIA LEAF DAMAGE. Science
143, ^3608} 818-20, Feb. 21, 196U-
G. Effects -Plants and Livestock
841
-------
Snowstorm petunias grown in the greenhouse developed a necrotic
banding of the actively expanding foliage characteristic of injury
ascribed to various photochemically produced pollutants in the
atmosphere. In this case the damage appeared to be related to the
high aldehyde content of the ambient air. Each time the aldehyde
concentration exceeded 0..20 parts per Billion for 2 hours, injury
appeared within a day or two. From July to September 1963 such
plant injury was observed on seven occasions. (Author abstract)##
03595
F. Darley, £• R. Stephens, J. T. fliddleton, and P.
I. Ranst
OXIDANT PLANT DAMAGE FHOH OZONZ-OLEFIN REACTIONS,. Intern.
Air Hater Pollution 1, 155-62, 1959 and Proc.. Am. Petrol.
Inst„, Sect. Ill 38, 313-22, 1958.. (Presented at the 23rd
Midyear Meeting,, American Petrcleuo Inst. Division of
Refining, Los Angeles, Calif, Hay 15, 1958.)
The reaction of ozone with five-, six-, and seven-carbon olefins
is quite rapid even in the gas phase at concentrations of a few
p.p«.m,. These reaction mixtures froduce a toxic material which
causes damage symptoms on pinto bean plants which are
indistinguishable from those attributed to oxidant-type air
pollution.. Ozonides, formed in snail yield by this reaction, are
stable materials which do not damage pinto beans in any way even
at concentrations higher than those arising in ozone-olefin
reaction mixtures or in outdoor air. Evidence was obtained that
the toxic material is unstable even at low concentrations in air.
Its half-life appears to be no more than a few min. This result
suggests that either a transitory ozone-olefln complex or an
unstable zwitter ion formed by its decomposition is the actual
toxic substance.. Attempts to ccnfizm this by adding excess
aldehyde or sulfur dioxide to scavenge the toxicant vere not
successful. (Author abstract)I#
03596
E. F» Barley, 8. H. Hugger, J. B. Hudd, L. Ordin,
0.. C. Taylor, and I. B. Stephens
PI A NT DAMAGE1 BY POLLUTION DERIVED FROM AUTOMO EILES. Arch.
Environ.. Health 6, 7.61-70, June 1963. {Presented at the Fifth
Session, Air Pollution Research Conference on "Effects of
Motor Vehicle Emissions on visibility and Vegetation,," los
Angeles, Calif., Sec. 6, 1961.)
Emissions from motor vehicles are now known to be the principal
source of the raw materials contributing to photochemical air
pollution in California. Some of the products of the reaction#
ozone, peroxyacyl nitrates, and the unidentified products of
opsone-olefin reactions, are very damaging to the leaves of a
842
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
variety of crop plants.. The injury that was once confined to
Ios Angeles County now occurs in many states and causes economic
loss estimated in excess of $25,000,000 annually. Ethylene,
one of the compounds found in the exhaust, is also very injurious
to several crops.. The ability of a given toxicant to incite
injury is dependent on the age of the leaf and the conditions of
illumination under which the plant is grown prior to, during, and
after fumigation.. In addition, the growth of plants, even in the
absence of visible injury, is laterially affected. Evidence is
presented to indicate that the chemical and physical systems
within the plant are disrupted by the phytotoxicants. {Author
summary) ##
036C8
J„ T« Hiddleton, J„ B«. Kendrick, Jr., £. F. Darley
AIR-BOBNE OXIDANTS AS PL ANT-DA HAG IMG AGENTS. Proc. Nat., Air
Pollution Sym., 3rd, Pasadena, Calif.., 1955. pp.. 191-8-
The relative susceptibility of seme plants to oxidants and
determination of the plant-damaging effects of hydrocarbon, ozone
and ozonated olefins are compared. The response of pinto beans
to air-borne oxidants occurring in the Los Angeles area
are described. The survey data were subjected to further analysi
by comparing the prercent of plants damaged at five stations
with the oxidant mean and maximum ranges observed. Data is
presented and show that the mean percent of plants damaged
increased with increasing oxidant maximum. Author states that
the experiment described is the first of its kind designed to
determine the relationship between plant damage and
oxidant level in the naturally polluted Los Angeles Basin.
The results of the study show that the frequency of damage to
plants is associated with the oxidant concentrations for both
oxidant maximum and daily oxidant mean.**
C3609
J- T. Hiddleton, J. B. Kendrick, Jr.., E. 7. Darley
AIR pollution DAHAGE TO AGBIcaiTOBAl CHOPS. laaca leaves
5<1J 86-11, Jan. 1955.
Significant damage of celery* spinach and lettuce was noted
in 1945 in the vicinity of Ios Angeles. Since these
symptoms were different from damage usually associated with
recognized pollutants, such as sulfur dioxide, fluoride,
chlorine and ammonia, investigations were made which revealed
that the toxicants causing this silvering and slight
glazing fallowed sometimes by a bronzed discoloration, ace
oxidized hydrocarbons. This phenomenon occurred only during
periods of reduced visibility due to inversions. Beiwareh
being conducted at the University of liverside was concerned
6. Effects * Plants and Liv«stock
-------
with how agricultural crops can be grows in an area receiving
polluted air masses, and to investigate chemical behavior
of pollutants using plants as assay method. These laboratory
investigations revealed that concentrations of oxidized
hydrocarbons as low as 0.1 pp» cause plant damage. These
observations corroborated those lade in the field showing
that damage to crop is directly proportioned to the length
of the pollution period, ftethods fcr protection of plants are
being studied and briefly discussed in this paper.*##
03610
Middleton, 0. B. Kendrick, Jr., E. F. Darley
AIR POLLUTION IHJTJRJ TO CROPS,. Calif-, Agr... 7 (11 J: 11-12,
1953-
Economic losses from air pollution injury on plants in Los
Angeles County alone exceeded $500,000 since 1949 when losses
were estimated to be 11179,495. The components identified
causing this damage were certain clefinic peroxides, found
when 020iie reacts with the vapors of unsaturated hydrocarbons
derived from gasoline and other petroleum products. Research
is in fzogtess to develop methods for the economic production
of agricultural crops in areas affected by air pollution.##
03611
T« Kiddleton
CLEAIR FOB GOOD CITBBS. Western Citrus Grower 1(6}:6-9,
June 1958. {Found in Hestern Fruit Grower 12, (6), June
1956„)
The adverse effects of polluted air on citrus crops are
reviewed- Included in the discussion are the effects of sulfur
dioxide, ozone, oxidants and fluorides. It is concluded
that abatement measures must be taken to protect agricultural
areas.,##
03612
J. T.. fliddletoo, B. 7. Darley, R. F.. Brewer
tSAHAGE TO ?SG£TATI0H FBOH POLL01ZD A3H0SPHBBES. J. Air
Pollution Control Assoc. 8, 9-15, 8ay 1958. (Presented at the
22nd Midyear fleeting, American Petroleum Inst. Division of
Refining, Philadelphia. Pa«# lay 14, 1957.)
644
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
Damage to vegetation from polluted atmospheres has been recognized
for aore than a century. Early interest in air pollution centered
largely on smoke and fumes from industrial Hastes, particularly
those of chemical manufacture, smelting, ceramic production*
and coal and petroleum conbustion effluents. Vegetation damage
has increased with industrialization and urban development.
Whereas the principal plant toxicants recognized several decades
ago were sulfur dioxide and fluorine, in the last decade a nev
group of airborne phytotoxicants has been described and
identified as oxidants. The principal source of these
oxidants is believed to be photolysis reaction products of auto
exhaust. Atmospheric contaminants responsible for damage
to vegetation may be described as particulates - such as
dusts and acid aerosols - and gases - such as sulfur dioxide,
halogens, oxidized organics, ozone, nitrogen dioxide, hydrogen
sulfide, ammonia, and carbon monoxide. Of these diverse
pollutants, gases generally cause more damage to plants than do
particulates.##
03613
T. Hiddleton A. 0. Paulus
THE IDENTIPICATIOB AND DISTRIBUTION OP *18 POLLUTANTS
THROUGH PLANT RESPONSE., A. A.. A. Arch. Ind. Health 14,
526-32, Dec.. 1956. (Taken from a paper presented at the 17th
Annual Meeting, Americas Industrial Hygiene Association,
Philadelphia, Pa., Apr. 23-27, 1956.)
This paper presents an annual summary of monthly tabulations
shoving plant damage occurring in 12 ot 51 counties. Regional
tabulations show that plant damage is limited to the
San Francisco Bay area and the coastal plain of
southern California. The areas reporting plant damage are
those of greatest population density. The toxicants responsible
for plant damage are recognized in decreasing order of importance
as oxidized hydrocarbons, ethylene and fluorides, sulfur dioxide
is of unusual occurrence and its distribution usually associated
with specific industrial wastes. It is generally believed that
ozcne is present in the urban areas of Los Angeles and San
Prancisco and responsible for a significant part of the total
atmospheric pollution. The wide-spread distribution of
ethylene and smog, or reaction products from the oxidation of
hydtocarons, emphasizes the need fox regional, research and
abatement programs.##
03615
J. T. Hiddleton
PHOTOCHEMICAL AIR POLLOTIOK CABAGE TO PLANTS* Ann. Fev.
Plant Physiol., No. 12:431-1)1)8, 1961.
The toxic components in photochemical air pollution are typically
G. Effects * Plants and Livestock
845
-------
the oxidation products of hydrocarbons and result either from
the dark reaction of ozone and olefins or the photolytic
reaction of nitrogen oxides and hydrocarbons in the presence
of sunlight. This paper describes the occurrence and
distribution of photochemical air pollution, enumerate seme of
the raw materials and products of these oxidation systems
responsible for plant damage, and indicate the biochemical,
physiological, and pathological effects of these
contaminants upon plants.*#
03616
J. T. fliddleton, A- S« Crafts, H„ P. Brewer, O. C.
Taylor
PLANT DAMAGE BT AIR POLLUTION- Calif. Agr„ 9-12, June 1956..
Xn many of the important growing areas of California the
production and quality of vegetables and crops are adversely
affected by air-borne toxicants such as ethylene, fluorides,
herbicides, oxidized hydrocarbons, ozone and sulfur dioxide.
Injury to plants by oxidized hydrocarbons (smog) is distinctly
different fro® crop damage by the other above named
precursors. Leaves of celery, lettuce, spinach, and some
other vegetables, and of flower crops and African violets
usually show silvering and glazing on their lower surfaces,
sonetines followed by a bronze or reddish discoloration..
Examples of the plant damage are shown in color photographs.
Visivle injury to all crops in the Los Angeles areas has caused
losses exceeding $3,000,000 annually since 1953. This does not
include economic losses fro reduced growth and lowered production
in the absence of visible injury.*#
03617
j„ T. niddleton
BESPOKSE Of PLANTS TO AIB P01LU1I0H. J. Air Pollution
Control Assoc. 6, (1) 7-9,50, Hay 1956.
This article compares the relative susceptibility of some
plants to oxidants to determine the plant-damaging effects of
hydrocarbon, ozone, and ozonated olefins, and to describe
the response of the pinto bean to air borne oxidants occurring
in the Los Angeles area- Plants vary in their susceptibility
to the reaction products from the oxidation of hydrocarbons. The
pinto bean has been selected as a test plant for measuring
the mechanisms of damage and seme of the effects of oxidized
hydrocarbons upon the life processes.. Controlled fumigations
have shown that the severity of plant damage varies with the ait
temperature. The atmosphere in los Aageles and San
Francisco has allegedly high concentrations of ozone. Tet
typical crop damage there is reproduced only by ozonated
olefins and not by ozone alone. Glasshouse grown crops can be
846
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
protected from damage by passing air through activated carbon
filters., The response of plants to air pollution depends upon
the type of pollutant present, its concentration, and the
length of exposure to it. The specific symptoms incited by
exposure to oxidants'cau be used to determine the presence at
ozonated olefins and ozone in polluted air masses.##
03618
E. R.. Stephens, E«. F„ Darley, 0» C. Taylor, W. E.
Scott
PHOTOCHEMICAL REACTION PROBtJCTS IS AIR PCLLaTIOH.. Intern. J-
Air water Pollution H„ {1/2) 79-100, 1961. (Presented at the
25th Hidyear fleeting, American Fetroleum Inst. Division of
Refiaing, Detroit, flick.# Way, 1% 1960.)
fhen low concentrations of simple olefins and nitrogen oxides
in air are irradiated with artificial svialigfct, th« olefin
molecule splits at the double bond. One end forms a carbonyl
compound, and the other yields a variety of products. Among these
is a highly oxidized, unstable organic nitrogen confound
previously described as compound X or peroxyacetyl nitrite (PAH)
and detected in polluted atmospheres. This compound has now been
purified by gas chromatographic techniques, and its
chemical, physical, anfl physiological properties have been
examined. At concentrations well below 1 p.p.m. in air,
this compound produces damage symptcms on plants, similar to those
observed from oxidant air pollation but different in some
respects from the phytotoxicant from ozone-olefin
reactions. Pin is the first pure compound isolated from
photochemical reaction mixtures which has been found to produce
the characteristic oxidant damage symptoms. It is also
a strong eye irritant at concentrations in the 1 p»p„itt. range
and is therefore probably responsible, along with acrolein and
fotn&ldeh'jd.e, for tfee imitation in photochemical air
pollution. (Author abstract!##
03626
C3626
6. H.. Todd
15P1CT O? LOW COHCEHTRATIOS Of 0Z0SE 0W THE EHZIHES CATAUSE,
PEROXIDASE, PAPAIN AMD UREASE* Physiol, Plantaru# 11»
151-63, "195B.
The present work concerns the action of ozone on enzymes* An
attempt has been made to estimate the actual quantity of ozone
required for ioactivation. The enzymes catalase, peroxidase,
Fapain and urease were treated in vitro with low concentrations of
ozone gas. Ride variations were found in the sensitivity of the
G. Effects -Plants and Livestock
847
-------
enzyaes to the inhibitor; action of the gas. Papain showed the
greatest sensitivity; the test required a much greater amount of
ozone for inactivation. Ccapari&ons of ozone and hydrogen
peroxide as inhibitors of papain and urease showed ozone to be 30
tiaes as effective as hydrogen peroxide on papain and 3 tiaes as
effective on urease. (Author suaaary aodified}*#
03627
G. B, Todd
IFFECT OF QZOSK AKD OZOKATED 1-HEXEBE OS RESPIRATORY AND
PHOTOSTBTHESIS OF LEAVES. Plant Physiol. 33, (6) 416-20,
Hot. 1958.
The treatment of Pinto bean leaves with either ozone or ozonated
hexene gas in air caused a rise in the respiration rate up to more
than four tiaes that of untreated control leaves. Plant responses
to the two gases were siailac. The rate of photosynthesis of
treated bean leaves was less than that of controls. Both the
amounts of stiaulation of respiration and the inhibition of
photosynthesis were directly related to the developaent of
visible injury symptoms in certain tissues of the bean leaves.
Mo stimulation of bean leaf respiration or inhibition of
photosynthesis occurred unless visible injury developed. However,
ozone caused a rise in the respiration rate of Valencia orange
leaves with so concomitant developaent of visible injury* Citrus
leaves gave no response until ozone concentrations approached those
required to produce visible injury symptoms. Treatment with
ozonated hexene at concentrations eliciting changes in
respiration and photosynthesis in bean leaves caused no change in
these processes in citrus leaves. A comparison of ozone- and
ozonated hexene*-treated bean leaves showed that the respiratory
quotients were not different from that of the control leaves.
(Author abstract}##
03628
G. K. Todd, J. T. Hiddleton, and B. F. Brewer
EFFECTS OF AIR POLLUTANTS: Calif. Agr« 7-8, It, July 1956.
SyaptoMs of plant daaage in the field can often be identified as
the effect of one or more air pollutants. However# the exact
aechaniaas whereby the plant is daaaged and the various
manifestations of daaage - after fumigation with air toxicants -
are not well understood, soae forage and vegetable crops, alfalfa
, coaaon bean, garden and sugar beet, lettuce, spinach, and
tcaato, grow and yield poorly in polluted atmospheres such as Los
Angeles and San Francisco. Reduced growth and production can
occur without leaf necrosis. Effects on plant life processes
were investigated. Treatment of the small aguatic plant, lenna
ot duckweed, with ozonated hexene and ozoae shoved a decrease in
chlorophyll content and reduced photosynthesis, studies on the
843
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
effects of ozonated hexene and ozone on the respiration of Xeaon
fruit showed respiratory stijulation, particularly upon treataent
with ozonated hexene. Changes in membrane perneability were
studied by exposing table beet, bean leaf and potato tuber tissue
to ozonated hexene. In the case of the beet tissue, the changes
brought about caused the anthocyanin pigment of the beet to
diffuse out when the tissue was placed ia viater. Ozonated
hexene first caused a decrease then followed by an increase in
perneability in the potato and bean tissues. Exposure to ozone
and ozonated gasoline caused reduction in growth of Kentia pains
and Todd Hexican avocado seedlings.##
03629
G» W. Todd
PHYSIOLOGICAL RESPOHSES OF PLANTS TO AIR POLLUTANTS. J.
*Fpl- Hutr. 10, 456-8, 1957. (presented at the 20th Annual
National Convention, Anerican Academy of Nutrition, Los
Angeles, Calif., 1956.)
The uechanisos whereby plants are damaged and the various ways in
which they nay show vaultestations after fumigation by air
pollutants are reviewed. The discussion is priaarily concerned
with the effects of ozone, ozonated unsaturated hydrocarbons,
naturally-occurring air pollutants in the Los Angeles basin, and
to a saall extent hydrogen fluoride.#*
03630
G- 0. Todd and tl. J. Garber
SOME EFFECTS OF AIR POLLOTARTS 0* THE GROWTH AND PRODUCTIVITY OF
PLANTS. Botan. Gaz.. 120, (2) 75-80, Dec. 1958.
Fuaigations with ozonated hexene caused a repression in growth of
bean plants (varieties Bed Kidney and Bountiful) even though
they showed no visible syaptoas of injuty. This effect was
evident fro® measurements of linear growth/ leaf area, fresh and
toy weights, and fruit production. Both priaary and trifoliolate
leaves failed to enlarge as inch as control leaves when treated
with ozonated hexene, although the treataent seeaed to have little
or no effect on the nuaber of leaves inititated. Primary leaves
on treated plants aged and ware lost preaaturely. Steas of plants
treated with ozonated hexene consistently had a higher water
content than did steas of control plants. The leaves did not
show this relationship. The height growth of pea plants
{variety Alaska) was slowed teaporarlly by as little as a
single half-hoar fuaigation with ozonated hexene, although treated
plants fully recovered and were growing normally 1 or 2 dayB later.
Ozone alone caused no repression of growth, and repeated
faaigations of pea plants with 1-hexane elicited no response.
(Author suaaary)#•
G. Effects •Plants and Livsstock
849
-------
036S5
B.i A. Bobrov
CORK FOBHATION IN TABLE BEIT LEAVES (BETA VULGARIS) IN
RESPONSE TO SMOG- Proc- Natl, Air Pollution 5ymp., 3rd
Pasadena, Calif.,, 1955. pp., 199-205
Table beet (Beta vulgaris) leaves produce an abnormal corklike
layer* the cicatrice, on their lower surface in response to snog.
This is due to a series of cross vails which cut in parallel to
the broad surface of the leaf in normally static, spongy nesophyll
cells., Following exposure to snog, a limited number of cells
surrounding the substomatal chambers on the loner leaf surface
become dehydrated.. Anthocyanin increases in the damaged areas and
lower epidermal cells nay collapse. The walls of the initially
damaged cells, those of the collapsed epidermal cells, and
intercellular spaces between become heavily suberized, sealing the
lower surface of the leaf. Sudan III stains this region readily
lover surface of the leaf* Sudan III stains this region readily.
This layer is properly designated the pseudocicatrice- All
and functional; the only abnormality is in the region of
accelerated suberization. The cells of the lover spongy oesophyll
in the immediate vicinity of damage begin to divide by tangential
vails to torn a cicatrice parallel to the flat surface of the
blade- These nev wails are at first pure cellulose, as they
grow older, they becone more and more heavily suberized. By
compression against one another as the mother cell continues to
form new walls above, a heavily suberized protective cork layer,
the cicatrice, is formed. This stimulation to unusual vail
formation in cells, which under normal conditions would not enlarge
or divide, is definitely in response to tissue trauma. Renewed
cellular activity cannot be biased directly on the toxicity of a
snog component. Indirectly, however, by causing the death of
some cells, it may induce chemical changes within the leaf, which,
in turn, induce the formation of cork. (Author summary)##
03696
R. B.. Glater, fU A. Solberg, and F- 0. Scott
A DEVELOPMENTAL STUDY OF THE IEAVES OF 8IC0TIAWA GtOTIKOSA AS
BELATED TO THEIR SHOG-SBHSITIVITY.. Am. J. Botany
1+9(9) :954-970, Oct. 1962.
Plants growing in the fields of Los Angeles County as well as
those experimentally fumigated in the laboratory shov gross
markings in response to smog which vary from species to species,
from a glistening appearance of the leaf undersurface due to a
temporary accumulation of water in the affected cells through
complete necrosis. I& dicotyledonous leaves, "silvering,"
••bronzing,w brown-black mottling or an increase in anthocyanin
may be seen« In monocotyledons, transverse banding, tan in color,
or longitudinal streaking of leaves are the usual responses. This
damage appears in a characteristic pattern on the leaves, different
850
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
fro® that produced by other phytotoxicants, Nicotiana glutinosa
plants were grovn in the air-filtered greenhouses at UCLA. The
normal anatomical development of the foliage was studied and
correlated with its susceptibility tc smog injury. On a given
plant, leaves of different ages show damage in different positions.
Very young leaves at the apex of the plant and old leaves at the
base of the plant are not sensitive. Expanding leaves between
young and old in age are sensitive; in this group a distinct
pattern of damage is discernible. Damage Barkings in the youngest
leaves appear only at the tip; in leaves somewhat older, close to
midblade; in fully mature leaves, only at the base. This
localization of damage is shown tc be correlated with the gradient
of cellular differentiation frcm tip toward base as the leaf
matures. Those cells which have just attained maximum size
(young mature) are sensitive; damage* therefore, is a function of
cellular development and maturity, ihe following anatomical
details were analyzed: (1) differentiation and distribution of
stomata and their opening and closing on both upper and lower
epidermal surfaces and (2) development of intercellular air spaces
in palisade and spongy parenchyma tissue. These studies indicate
that damage occurs in the region of the leaf where stomata have
just become functional and ambient polluted air can make direct
contact with interior leaf tissues by virtue of large substomatal
chambers and intercellular air spaces* (Author abstract)##
03697
R. A.. Bobrov
THE LEAF STRBCTDBE OP POA AHHO A KITH QBSERVfcTIOUS OH ITS SBOG
SEBSITIVITY IN IOS ANGELES COUHTT.. Am. J. Botany 42, t68-8«.
Bay 1955.
Annual bluegrass fPoa annua L„) is very sensitive to certain
pbytotoxic agents present in smog and might be useful as a bioassay
indicator plant. In the field, the characteristic response to
hydro-carbon-oxidation products is seen to be a tan spotting or
transverse banding limited to the region between tip and midblade
of susceptible leaves. This damage has been duplicated in the
laboraroty with synthetically-produced smog. Tissue damage Is
similar to that previously described in spinach, beets, oats and
other plants. The cells which are initially and most seriously
damaged are those surrounding the substomatal chambers.
Chloroplasts disintegrate, plasuolysis follows, and ultimate
total dehydration of damaged cells results in part or all of the
mesophyll tissue in affected areas becoming "mummified." Ia
plants having a high specific sensitivity to smog, damage is
correlated with stomatal distribution and activity, volume of
inter-cellular air space and age of cells. Localisation of
damage is related to the gradient of cellular differentiation from
tip to base in the linear leaf; the sensitive region is limited to
those cells which have just completed maximum expansion. (Author
summary)*#
03698
B* A. Bobrov
G. Effects • Plants ami Livestock
851
-------
USE OF PLANTS AS BIOLOGICAI IKBICATCBS OF SMOG IN THE AIB OF IOS
ANGELES COUNTY* Science, 121 (31U5):510-511, April 8, 1955.
Poa annua is considered a very reliable biological indicator for
atmospheric smog for several reasons: (i) the extreme sensitivity
of its cells to minute quantities of phytotoxic Materials; (ii)
its method of cellular differentiation from tip toward base in the
linear leaf with resulting narked transverse leaf banding; and
(iii) its ubiquity as a need in Los Angeles County, Baking a
naturally occurring check available in aany and scattered areas.
Work is in progress in an attmept to calibrate this plant as a
quantitative, as well as a qualitative, bioassay material. A
detailed account of the anatcmy of normal and snog damaged Poa has
been completed..**
03700
R. Bobrov
THE EFFECT OP SHOG OB THE ANATCSY OF OAT LEAVES.
Phytopathology U2t (10) 558-63, Oct. 1952.
Smog in the los Angeles area causes serious damage to the oat
crop. Daaage depends upon the normal anatomical pattern of the
parallel-veined leaf, upon the stromata as a portal of entry for
the harmful elements in the air, and upon the amount of internal
air space in the leaf. Initial daaage nay be observed
microscopically, as the cells directly lining the substomatal
chambers shrink. As acre and sore cells are affected,
longitudinal streaking of the leaves occurs, corresponding to the
position of the stoaatal zones. Ultimate browning and death of
the entire blade nay results. The extent of injury is in
proportion to the concentration of snog in the air. {Author
abstract)**
03961
W. K„ Heck and J. A.. Dunning
THE EFFECTS OF OZONE 01 TOBACCO ABD PIHTO BEAH AS CONDITIONED
BY 5EVERAI ECOICCICAI F1CT0BS. J. Air Pollution Control
Assoc. 17, <2) 112-1, Feb. 196?.
Environmental factors have a determining influence on the
sensitivity of plants to ozone as an air pollutant. The effect
of several environmental and related factors has been reported as
preliminary to a further study of multiple factor interactions and
eventual application to field conditions. Plants grown under a
short photoperiod and Ion light intensity are more sensitive to
ozone than those grown under a long photoperiod and a high light
intensity. The sensitivity of tobacco or pinto bean to ozone, as
an air pollutant, is increased by growing plants in a shortened
photoperiod under reduced light intensity and in a light potting
852
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
*ix.. Sensitivity also is influenced by CO concentration# time
of day, and age of plant at tine of exposure. Tobacco shows
cumulative development of injury when exposed to low concentration
intermittently over several days.##
04416
S. Rich
OZONE DAMAGE TO PLANTS.. Ann. Sev. PhytOpathol„ 2, 253*66,
1964.
The following aspects of ozone injury to plants are reviewed:
Natural sources of ambient ozone; what plant species are
susceptible; the symptoms produced; environmental predisposition;
Metabolic effects; and how plants nay be protected.##
04544
H. Stokinger
EFFECT OF AIP P0LL0TA8TS OH WILDLIFE, Conn, Hed. 27, (8)
487-92, Aug- 1963.
A review of information derived from both field and laboratory
investigations of the effects of air pollutants on terrestrial
animals indicates that (1) of all known air pollutants, economic
poisons pose the greatest current threat to the health of wildlife.
|2) inorganic substances, {certain heavy metals and fluorides),
account for limited and local injury to wildlife based on known
effects on domestic animals. <3> The hazard to wildlife is
chiefly from ingestion of the "fallout* of the air pollutant.
(4) Relative species susceptibility to specific air pollutants is
far from clear, but it vculd appear that the mammals are
considerably more susceptible than birds. (5) laboratory studies
have revealed three rather general phenomena associated with
exposure to air pollutants: a. Synergism, the exalted or
potentiated toxic effect of combination of certain air
pollutants: its converse, antagonism, in which the sommated
toxicity is either far less than predicted or nonexistent, b.
Tolerance and cross tolerance to pulmonary edema-producing
agents, c. The immunochemical response.•#
04576
3. H. digger, Jr., J. Koukol, R. 0. Seed,
B. L. Falser
EFFECT OF PEROlIACim SITUATE 0* C1«»02 HXMI0B BX SPIHACH
CBL0H0PLASTS AND PISTO BEAK PLANTS. Plant Physiol. 38, (4)
(168-72, July 1963.
G. Effects ¦ Plants and Livestock
853
-------
Photosynthetic C02 fixation in pinto fcean plants and is
intact spinach chloroplasts was inhibited by
peroxyacetyl nitrate, a component of
photochemical snog. Addition cf ascorbate to the chloroplast-
ccntaininq reaction aixtures virtually eliminated this
inhibition. Exposing the cblcrcplasts or other components of the
reaction, either separately or as a aixture, to peroxyacetyl
nitrate in the dark followed hy a light period without the
oxidant did not effect the C1402 fixation process,, This
inhibition in the intact plant, as well as in the chloroplast,
appears to be one of quantitative reduction ia the early products
of the photosynthesis and not a qualitative change. (Author
summary)##
0^582
H. E« Reggestad 1. Hiddleton
OZOKE IN HIGH C0NCEKTRATI08S AS CAtJSE OF TOBACCO LEAF TUJDHT„
Science 129„ J33U3) 208-9. 1959.
Evidence obtained by neans of rubber strip tests and on ozone
recorder indicates the presence of abnormal concentrations of
ozone in the atmosphere at tines. Excellent correlation
was obtained between appearance cf "weather fleck*1 in tobacco
and high values for ozone. The great similarity between lesions
occurring naturally and those produced by ozone In chambers also
indicates that ozone is the probable inciting agent of weather
fleck- Varietal differences exist, study of stoaatal action
helped to explain variation in leaf injury.##
0M68U
n. c. Ledbetter, P.. V. Zi*Bet»an, and A. E. Hitchcock
THE HISTOPATHOLOGIC AX. EFFECTS OF OZONE OH PIAHT FOI.IAGE,
Contcib. Boyce Thompson Inst. 20 (0) 275-82, Dec. 1959
Young plants of 32 species and varieties that were growing
vigorously in the greenhouse were exposed to otone at
concentrations of 0.1 to 1.0 in a circulating stream
of washed air. In descending order of susceptibility the plants
were tonato, bean {Pinto), tobacco (flaryland fla»aoth|,
spinach, potato, siartweed, stevia, tobacco (Vaaorr 48),
chrysantbeaua fPippis), bjrpericas, alfalfa, peanut, tobacco
(Turkish), sweet potato, sensitive plant, grape, verbena,
chrysantheaua, Jerusalem cherry, avocado, sugar-beet, strawberry.
Bint, and geraniaa. Tinder the conditions of this test, gladiolus,
kalanchoe, pepper, bean (Tendergreen), and piggy-back plant were
not visibly injured by concentrations up to 1v0 p.p.n. Foliage
injury appeared in vatying aiounts as dark stipples, light
flecks, necrotic patches, and general chlorosis. The dark
854
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
punctate markings were shown tc be flue to pigmentation and
thickening of cell sails in the palisade area. The light-
colored flecks were associated with a collapse of the
palisade cells without pigment formation. The necrotic areas
*©re found to consist of general injury to all cells between
and including the epidermis in the affected area. In general,
very young leaves that had no functional stomata were resistant to
ozone- The leaves become susceptible only as the stomata
become functional. In variegated coleus injury was largely
associated with the pigmented sectors presumably due to the
greater functioning and freguency of the stomata, or to the
greater sensitivity of these tissues to ozone. (Author summary)##
CT7C7
L» Crdin and H. A. Hall
STUDIES OS CELLULOSE S1KTHESIS BTf A CELL-PREE OAT COLEOPTILE
ENZYME SYSTEM: IHACTIVATIOK BY AIBBCFNE OXIDANTS. Plant
Physiol.. 42, (2) 205-12, Feb. 1967„
Particulate cell wall polysaccharide synthetase from oat
coleoptiles could use either guanosine diphosphate glucose or
uridine diphosphate glucose; the latter was a much more effective
glucose donor- The neutral polyner derived ftoa uridine
diphosphate glucose utilization yielded, after cellulase digestion,
mostly cellobiose and to a lesser extent a substance tentatively
identified as a mixed-linkage beta tr
-------
organelles and the cellular contents aggregated In the center of
the cells. The characteristic components of this aggregate were
reaains of the chlocoplast aeabrane systea and nuierous ordered
arrays of granules and fibrils. These changes were identical with
those previously observed in cells damaged by peroxyacetyl nitrate
and were probably related to the oxidation properties of both
molecules., In soae cells thefe was a disruption of the
organization of the grana within the chloroplasts. (Author
abstract)##
04853
C. R. Theapson, and O. C. Taylor
PLSTIC—COVERED GREESHOOSES SOPPLY CONTROLLED ATMOSPHERES 10 CITRUS
TREES. Trans. ASAE (A a. Soc. Agr. Ergrs.), 9(3):338-339,
312, 1966. 5 refs.
Details of a greenhouse for studies of air pollution (smog) on
individual fruitbearing citrus trees are described* A structure
was needed for this purpose that would endure for a minimum of five
years, would admit the entire solar spectrum, and would not become
excessively overheated when outside temperatures rose to 115 F.
After three years of operation, the durability and convenience of
the structores described are very satisfactory. No discoloration,
crazing or cracking of the plastic glazing listeria 1 is apparent,
paint on the aluainua is holding well. Repainting on some steel
surfaces was necessary after two years. Activated carbon and
liaestone for removing photochemical snog and fluorides,
respectively, froa the air streams aest be renewed about every 12
hoars. Soae minor damage was done by windstorms of 80 mph, which
was easily taken care of.##
C4998
B. EL Hull F» *. Vent
LIFE PROCESSES OP PLANTS AS AFFECTED BY AIR POLLUTION. Proc..
Natl* Air Pollution syitp.* 2nd, Pasadena, Calif.., 1952. pp.
122—8,,
Either natural smog or artificial smog produced by the
ozonization of 1* n-hezene or gasoline was used.. Plants used
included: alfalfa* var„ Chilian; sugar beet, var.. U.S. 22/3;
endive, var. Pink Ribbed; oats, var. Kanota; spinach, var-
Viroflay; asd toaato, var. San Jose Canner. A sensitive
biological assay for detection.of phytotoxic
constituents in the atmosphere is described. Differential
sensitivity of cotyledons and young foliage leaves to saog
injury was observed. The growth of alfalfa, and
especially of endive, has been greatly increased by carbon
filtration of the atmosphere. Tcaato plants" growth was very
856
PHOTOCHEMICAL OXIDANTS AMD AIR POLLUTION
-------
significantly greater in the carbon-filtered air. th
iron-zinc-steel wool filter *as practically as eff®, i
activated carbon, as indicated by the luxurious
five plants. The effect of sacg cn growth, transpiration/ an
stoaatal behavior was exaained. The effects of
illumination, huaidity, and soil noisture on the aeMitiv***
of the plants to smog was studied. The effect of
sulphate, stannous chloride and sucrose sprays upon tne
plants" susceptibility to snog injury was studied, x&e
sensitivity of several different species of plants ana or
different types of spinach to siog danage was investigated"*
04999
i. Bobrov
THE ANATOMICAL 1JFECTS OF ilH POIIOTION OH FIANTS-
8atl„ iir Pollution Syap., 2nd, Pasadena, bBcalif-, 1952.
pp.. 129-31.
The damaging effects on the leaf anatoay of SUS®®P**"® . he
crop plants were investigated* The leaf was S°? t.ti-hiv
the logial point of departure, since it alaost
aanifests physical response to snog within a very ^ f^llv
period. The structure of the aortal leaves wasvery
observed in order to enable detection of even J Ai,a «adfi
alteration in cell shape. *roa careful MJS
of the cellular structure of normal and d"ageM®"® J
possible to establsih the Microscopic anatomy of
Begardless of the nacroscopie picture of d«age. microscopic
studies indicate that the reaction of the cell to dents.
hydrocarbon-ozone products is the in all SU® P.
The plants studied were table beet, sugar beet,
lettuce, spinach, Swiss chard, endive, oats, an
05096
0. B» Hudd., and To T. Mcianus
PABTIC1PM10H 01 5QLIHYDBYL G800PS 1* F1TTY HCID SYNTHESIS BY
CHLOBOPIAST PHBP*H*TIOHS. Plant Physiol. 39, (1) 115-9, Jan.
196U..
Preparations of broken spinach chloroplasts incorporate acetate
and aalonate into long chain fatty acids* Avidln inhibits the
incorporation of acetate but not of aalonate. The ability to
catalyze the incorporation of these precursors declines as the
preparations age. This deterioration is associated with the
soluble enzymes, rather than the fragments of the chloroplasts.
The aging effect can be prevented to some extent by glutathione*
which also alters the composition of the labeled fatty acids,
favoring stearate and decreasing paImitate and oleate. sulfhydcyl
reagents fp-chloroaercuriben>oate, cadaiua ions* arsenitej inhibit
G. Effects 'Plants awl Linstock
857
-------
the incorporation of acetate and nalcnate into lipid. At higher
concentrations the sulfhydryl reagents inhibit the incorporation
into non-volatile water soluble ccasfcunds. The inhibition
by p-chloromercuribenzoate and cadmium ions can be reversed by
reduced glutathione.. The inhibition by arsenite is enhanced by
the presence of 2,3-dimercaptopropanol. (Author summary)##
05103
S. H.. Noble
THE RELATION OF PLANT EAilAGE TC FUEL COMPOSITION- Preprint..
(Presented at the Jcint Research Conference on Motor
Vehicle Exhaust Emissions and Their Effects, Los Angeles,
Calif., Dec. 5, 1961.)
Plants exposed to irradiated auto exhaust gases containing
initially less than 0.5 ppm of olefins and less than 2 ppw of NO
exhibit the sane symptoms of damage as do plants exposed to the
atmosphere in the Los Angeles area. The plants used in these
studies were Poa annua and petunia, var. Rosy Horn. The
symptoms observed were banding, necrosis, glazing, silvering, and
cellular plasmolysis in substonatal regions. Exposure time was 1
hour. Exposures were initiated at half bour intervals.. Poa
annua was the most useful plant because of its greater range,
simplicity of evaluation, and uniformity and also because a
larger number of plants could be used in a given space. The
length of exposure required fcr the production of maximum damage
appears to be related to the reaction rate of the fumigants, which
depends in part on fuel bromine number and on the concentrations
of the funigants. Differences in concentrations also produced
marked differences in the degree of danage. (Author abstract)##
05131
I. J. Hindawi
THE PBCDOCT OF PHOTOCHEHICAI REACTION AS REFLECTED ON VEGETATION
GRCWH IN BROOKLYN BOTANICAL GARDENS . Willowbrock, Hew York;
Roselle and Baycnne, New Jeraey. Preprint. (Presented at
the Cooper Onion Colloquim, Hew York city, Apr. 17, 1967.)
In an atteapt to observe ozone attack on sensitive vegetation
grown under controlled conditions, specially designed greenhouses
were located, from July 18, 1966* through October 5, 1966, in
New Tork and New Jersey. The test plants were grown tinder
hydroponic conditions in a verniculite support medium containing
prepared nutrient solution. The test plants were exposed to
ambient air by circulating fans designed to provide one complete
change of air volune every minute. Two plants of each of tobacco,
pinto bean, geranius* petunia, begonia, and cotton were placed in
each greenhouse. The type of damage that developed during
exposure to natural pollutants could be attributed to ozone and
858
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
PAN and also to interactions of low concentrations of these
toxicants and others.. It was found that the flante were
significantly »ore sensitive during the aid-porti t.
than at either extreme. In addition to tissue
growth of geranium, petunia, begonia and pinto b P comparable
at the four stations was severely sufF"ss®^* ?f5%-rhoii filters
plants grown in the control station with activa - .
had longer leaves, a wider stem, darker green co » study
generally sore vigorous growth appearance. Two y _ daoaae
and observation hive indicated definite evidence of plant daaage
front ozcne to PAN in the Metropolitan New York Ar a.
05279
F• D., H. HacDowall, £. I. BuXammal, and A.. f» w.
Cole
E1BECT CORRELATION OF AIH-POILUTIKG OZONE AND TOBACCO WEATHEP
FLECK „ can, j„ Plant Sci. (Ottawa) lift, 410-1, Sept„ 196U.
Influxes of polluted air and attacks of tobacco weather fleck in
southwestern Ontario were accurately forecast frcm the synoptic
weather pattern and frost considerations of mesoscale
neterological systems. However, the principal air pollutant*
czone, occurred daily at low concentrations that were often not
followed by corresponding amounts of damage. This difficulty was
¦largely removed by modi flea tic n of the dose tern with the
coefficient of evaporation. The latter may empirically represent
Physiological and physical factors affecting gas exchange. A
related downward flux of ozone night be important in determining
the amount of ozone available for absorption. The threshold doses
of air-polluting ozone and experimentally generated ozone were
approximately the sa««» {Author abstract}##
05342
Darley, e„ F«, Nichols, C« ». and Hiddleton, J. T.
IDENTIFICATION OP Alft POILOTIO* EKBiGE 10 AGBBCOMHIBAL CBOPS. (AIB
P0LIDTI0N HESEABCB REVEALS CHEMICAL TOXICANTS INJURING VEGETATION
I* POPBLO0S ABBAS OP CALIFORNIA.! Calif. Dep. Igri. Bull.,, 55(1)i11-
19, 1966..
The subject of this paper is the damage air pollution does to the
plants that, feed us, clothe us and please our aesthetic sense.
This damage is considerable. Estimates of visible damage to
agricultural crops amount annually to about $8 million in
California and approximately «18 million along the fctlantic
seaboard. Damage to vegetation has increased with
industrialization and urban development,, several decades ago
sulfur dioxide and fluorine were recognized as the principal plant
toxicants.. These two gases continue to be very important but within
the last 20 years a new group of to*ica.nts has been identified.
These are products of atmospheric photochemical reactions between
G, Effects-Plants and Umtock
-------
hydrocarbons and nitrogen oxides. The principal products of these
reactions are ozone and the peroxyacyl nitrates (FANs). The
distribution of plant damage in California shows that it occurs
cnly in recognized geographical areas which, in each instance, are
located within airsheds. Because damage to plants is often the
first indication of air pollution, it is important that the
surveillance of pollution damage to agriculture be continued* Such
information will help communities, in their planning, to take
cognizance of the relationship between the air ressource and the
community needs for commercial and industrial development, energy
production, fuel usage and transportation, agriculture, and forest
and recreation land. The air contaminants responsible for damage
nay be either particulate or gaseous in nature. The greatest
amount of damage to animals and vegetation is usually caused by
gaseous air contaminants which directly injure plants and
indirectly injure animals by the toxic effects produced after the
animal has consumed contaminated forage and food supplements.
05344
Barley, E. and Hiddleton, J. T.
PROBLEHS OF AIR POLLUTION IK PIANT PATHOLOGY. Ann. Rev.
Ehytopathcl.. 4, 103-18, 1966.
Air quality affects plant growth and development. Whereas oxygen
is necessary for aerobic plant respiration and carbon dioxide is
necessary for photosynthesis in green plants, a number of
pollutants nay alter plant metabolism and incite disease. It is
the purpose of this paper to enumerate some of the principal air
pollutants which adversely affect plant growth and reproduction, to
describe the diseases incited by them, and to identify some of the
problems of air pollution in phytopathological research. A primary
responsibility of the pathologist is to alert agriculturists of
impending air-pollution problems, so that social action may be
taken to insure the continued productivity cf crop, pasture, and
forestry enterprises. Another responsibility, because plants are
early indicators of an air pollution problem, is to assist public
health and resource agencies in the planning, conduct, and
evaluation of air-pollution abatement programs. Plant pathologists
must become increasingly concerned with the effects of air quality
on plant growth.
05362
Dugger, 9. H. Jr., Taylor, o. C., Cardiff, E., and Thompson, C.
H-
RELATIONSHIP BETWEEN CARBOHYDRATE CONTENT ADO SOSCEPTIBILII* OF
PISTO BEAU PLANTS TO OZONI BABAGE.
Proc. Am. Soc. Hort. Sci. 81, 304-15, 1962«
Evidence is presented to substantiate the hypothesis that ozone
damage to the leaves of pinto bean plants is associated with the
860
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
sugar concentration in the leaves at tine of exposure to ozone,
these are: (a) leaf daaage froa ozone nay be prevented by a dark
period sufficient to reduce the sugar content to a low level and
then reversed by supplying sugar to the leaves through leaf or cat
stem absorption; (b) plants grown in a 12 hour photoperiod and
susceptible to ozone daaage nay be protected by supplying
additional sugar through leaf cr root absorption; (c) young (less
than 7 days) and old leaves (greater than 14 days) are not daaaged
fey ozone and soluble sugars are high in these plants. Only when
the sugar level is reduced to a level less than about 4 ng/g fresh
"eight and not less than about 1.0 »g/g fresh weight will ozone
danage occur; and (d) young plants not susceptible to ozone and
containing a high level os sugar, are nade susceptible to the gas
fc? removing the cotyledons and reducing the soluble leaf sugars.
Eight day old plants with or without cotyledons, are equally
Managed by ozone and have the sane concentration of sugars. The
relationship of this hypothesis to previous reports on ozone daaage
tc plants is discussed with a view toward explaining the
variability in observed daaage is the field as well as greenhouse
studies.. (Authors" suaaary)
05<*20
Haines, H. H., I» A» Leon, and Brennan
MB POLLUTION AMD PL AST BSSP0H5* II) THE 80RTHEASTEHN UNITED
STATES- In: Agriculture and the Quality of Our
Environaent. Brady, V» Cu (ed.), American Association for
the Advanceaent of Science, Washington, D- C. AAAS-Pub-85,
P. 11-31, 1967. 56 refs. (Presented at the 133rd Meeting,
American Association for the Advanceaent of Science,
Washington, D. C. Sec. 1966«)
A review of pollutants that have been found to elicit plant
response is confined to the discussion of acid gabes, priaary
products of coabustion, and products of reactions occurring in the
atnosphere. Other topics discussed includes plant response as an
indicator of aeteorological conditions and the fuels used for heat,
light, and power.##
05422
Landau,
economic ASPECTS OF AIH P0IL0TI0B AS It RELATES TO AGHICDITU8E.
In: Agriculture and the Quality of Our Environaent.-Brady#
N. c. (ed), Aaeriesn Association for the Advanceaent of
Science, Washington, D. C, AAAS-Pub-85, p. 113-126, 1967.
23 refs* (Presented at the 133rd Meeting, Aaecican
Association for the Advanceaent of Science, Hashington, D. C.
Dec. 1966.)
A review of the econcaic considerations of air pollution daaage to
G. Effect* ¦ Plants and Livestock
861
-------
agriculture is presented.. Estimates of benefits and cots are
ahsoutely essential to the development of effective control
measures for air pollution* Tbe basis for the estimates of damage
to crops and livestock because cf phytotoxicants is vague and ill
defined, existing only for selected areas of the United States
and for damage to specific crops.. Hence, the overall
extrapolation is based on United data. The sources of
information for previous accounts of damage exist only for
geographically limited areas. Well-known court action such as
the Trail Smelter Case (British ColuntbiaJ and the Ducktown
Case (Tennessee] are the sources of information on extensive
local dasage. These and other cases illustrate the weakness of
this type of resolution of the problem of external diseconomy.
In the United States, laboratory studies of sulfur dionide have
generally been limited to acute effects that cause visible damage,
little concern has been manifested for chronic effects,
particularly if visible damage was not observed. Only very
recently, owing primarily to the stimulus of German research
findings, has interest developed over chronic or growth effects..
There is also a possibility of a potentially greater
nutritional threat to crops, which may not be currently reflected
in market prices. Because the existing national estimates of
crop damage have severe liiitaticns, a substantial underestimate
may result from their focus on observed damage. Should the
national estimates of crcp damage be needed, and they are needed
for legislative and political considerations, there will inevitably
be a long delay until reliable state and regional estimates on
which they must be based can be prepared.##
05485
V. M. Noble
AIR P0L1UTAHTSu lasca Leaves. 15 (1), 7-18 (Jan. 1965).
After years of careful study, sone of the coaponents of smog
have been sorted out. The more important ones, their effects on
vegatation, and a list of sensitive and resistant plants are
discussed. The components are peroxyacetyl nitrate, ozone,
ethylene, hydrogen fluoride, sulfur dioxide and aerosols.M
05558
H. A. Roderthiser
EFFECTS OF AIR POLLUTION 08 CHOPS AKD LIVESTOCK. Preprint.
(Presented at the National Conference on Air Pollution,
Bashlngton, D.C., Dec. 10-12, 1962, Paper D-3.)
The damage done by air pollutants is costly both to farmer and
consumer. The sensitivity of plants and trees to various
pollutants (fluoride, sulfur dicxide, PAH, and nitrogen oxides)
862
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
is discussed, with eaphasis on current and future research efforts
to erradicate these pollutants. Although there is no good aeasure
of the total national loss froa air pollution, fugures have been
published for soae localties. In Southern California, for
exaaple, loses of vegetation due to oxidants are thought to be
around 10 Billion dollars a year- This includes only the readily
demonstrated loses of vegetable crops downgraded because of
aarkings or left unpicked in the field. The general conclusion is
that air-pollution research in the field of agriculture a«st »ove
ahead before a greater gap is created in this area.##
05560
c„ R. Berry
EASTERN BHITE PIHS-EVEHGBEIB RCDIT08 07 AXB POLLUTION.
Preprint.. (Presented at the Second National conference on
Air Pollution* Washington. D.C., Dec. 12-14, 1966,.)
Six hundred healthy, 2-year-old seedlings were potted and taken
to Morgan County, Tenn., where they were installed near a power
plant known to be the sulfur dioxide source. After a year of
exposure, 106 of the trees had died, either froa handling, air
pollution damage, or both. Those surviving included 183 that were
free of daaage and 106 that were only slightly injured* These
were presumed resistant to sulfur dioxide and were taken to the
Alabana test area for exposure to fluorides. The regaining 202
trees showed serious daaage, so they were returned to the
recovery area in North Carolina. After a year of exposure in
Alabama, 15? injured trees were again reaoved and sent to Horth
Carolina for recovery. The regaining 26 seedlings still
appeared healthy* and they were presuned to be resistant to both
sulfur dioxide and fluorides. The healthy trees were aoved to
Beltsville, Hd., where they are still under exposure to
oxidants produced by heavy actor traffic. Although, the
exposure period is not over, and final figures say be different,
13 trees have been injured and 13 still appear healthy. It is
hoped that seedlings froa seed of superior trees will be inherently
resistant to daaage froa sulfur dioxide* fluoridss, oxidanta, and
other airborne toxicants* on the other hand, susceptible trees
that recover in the clean air in north Carolina say sake
excellent assay plants because of their desoostrated sensitivity to
oxidants at Beltsville. The results of these tests indicate
there is enough genetic variation is a large eastern white pine
population to provide biological indicators for specific toxicants.
05610
l* V. Heck
mST 1)1 JO BY IKDDCED Bt PHOTOCHMICAl BMCTIOS PRODUCTS OP
PHOmiM-MTHOGEM DIOXIDE 8XX1QRIS. J. Air pollution
G. Effects -Plant* ami Livastoek
863
-------
Control Assoc. 14(71:255-261, July 1664. (Presented at the
56th Annual Beeting, air Pollution Control Association*
Detroit* Mich., June 9-13, 1963.)
Plants developed typical ethylene- injury symptoas when fumigated
for 21 to 48 hr with ethylene or various combinations of ethylene,
acetylene, propylene and nitrogen dioxide. Khen propylene and
nitrogen dioxide were included in the gas mixture and the mixture
irradiated typical oxidant symptcns were recorded. Slight to
severe necrotic spotting, due to nitrogen dioxide, vas noted in a
as hr fuaigation at one ppm nitrogen dioxide and in a 21 hr
fuaigation at 3.5 ppa nitrogen dioxide. Twelve hour fumigations
using irradiated mixtures of ethylene, acetylene and propylene at
three concentrations (2,t, and 8 ppa) each in combination vith one
ppa of nitrogen dioxide gave typical oxidant damage vith only the
propylene-nitrogen dioxide mixtures.. From reported oxidant injury
syaptoas the propylene-nitrogen dioxide irradiated mixture
produced plant injury which is typical of both ozone and PAN.
The presence of other phytotoxicants vas not dicounted hut the
severity of injury, under the conditions used, made it difficult
to evaluate other possible types of oxidant damage. The
production of the phytotoxicants using various ratios of
propylene-nitrogen dioxide mixes vas determined using the Flants as
biological indicators- % ratio of one ppm N02 to 2-3 ppra
propylene produced the highest concentration of the phytotoxicants.
The effects of varying light and teaperature conditions during
the fuaigation period indicated that plants must be in the light
before they are sensitive to oxidant daaage and that a temperature
above or below noraal will reduce oxidant injury. Results stress
the need for studying the interrelations of oxidant injury and
various environmental factors. (Author"s sunoary)##
C5666
Brewer, B. F. Guilleaet, F„ B« and Creveling, B.. K.
INFLUENCE OF N-P-K FERTILIZATION CD INCIDENCE AND SEVER ITT OF
OXIDANT INJOHY TO RANGELES AND SPINACH.. Soil Sci. 92, (5) 298-301,
NOV. 1961m
The study reported in this paper was designed to further study the
influence of nitrogen supply and explore the possible effects of
potassium and phosphorus supply os the sensitivity of plants to
oxidant daaage.. Several Mangel seed (Burpee No. 5131) were planted
in 1-gallon cans filled with a previously fertilized soil-sand-peat
mixture. After emergence the plants were thinned to one plant per
can- Twelve different treatments, each replicated a times, were
used in a 3 % 2 x 2 factorial design consisting of 3 levels of N
and 2 each of P and Ko Two months after emergence, half the
plants, chosen at randon, were placed in a special greenhouse
fuaigation chamber and exposed to oxonated hexene. The remaining
nangels were placed in a duplicate fumigation chamber which
received activated-carbon-filtered air to reaove aabient oxidants.
At the end of 2 days, during which the one group of plants was
exposed to two 6-hour fumigations vith an average organic oxidant
concentration of 0»01 ppm.. all the plants (fuaigated and controls)
864
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
were returned to the sacg-free greenhouse where they were grown.
Thirty-six hours after fusigation was stopped the plants were
systematically examined tot incidence and severity of damage. A
siailar experiaent was conducted using spinach as the test flan.
A statistical analysis of the aangel funigaticn data indicate that
the severity of injury was wery significantly increased as the
nitrogen level was increased. There were also highly significant
interactions of nitrogen with phosphorus and between phosphorus and
potassiua on severity of injury, "the results of differential
fertilization on the sensitivity of spinach to ozone injury indi-
cate that increasing the nitrogen supply very significantly in-
creased both the incidence and the severity of ozone injury,
fertilization on the sensitivity of spinach to ozone injury.
05698
T. Freebairn and 0. C. Taylor
PBEVEBTIOK OP PlUT CUBUCE fBOH KR-EOBNE OXIETZIUG AGENTS..
Proc« la. Soc. Hort* Sci. 76, 693-9 (1960).
In 1956 alone, the estimated loss to growers froa the damaging
"gents in Los Angeles sacg (one of which was ozone) aaountea to
¦ore than $5,000,000. Therefore, it is iaportant to investigate
¦ethods for counteracting the effects of oxidizing agents on plants
»nd to understand the type of toxic reactions taking place.,
Under the right conditions vitaain C and reduced glutathione have
the capacity to prevent the damaging action of ozone on in tivo
and in vitro Metabolic processes.. The action of ozone on plant
«nd aniaai aitochondria has been shown to be presented and
by the addition of excess aaonnts of glutathione (reduced fora)
ascorbic acid. The application of vitaain C to the leaves or
roots of bean plants increased their tolerance to ozone
*«»igations„ For deaonatrating protection in the
12-day-old pinto bean plants, were transported froa Riverside to a
greenhouse in ttontebello and to field locations in *est Covina,
and Chino, California. They were exposed daring periods that
a*r pollution occurred in these locations. The solutions being
tested were prepared fresh before each spraying and were sprayed
on the beans daily during the exposure period as well as «•
day before the plants were transported to the field* The plants
were changed every three days, at which time the results
recorded. Coaaercially-grown petunia plants were "is?d "®f®r
glass at the field locations in both flats and saall aluainua
containers* The plants were usually about 6 to 8 weeks old when
*l»e tceataents were started. Analytical data indicated that a
spray application of reduced vitaain C to the foliage or plants
caused an increase in their vitaain c content, votassiua
aacorbate sprays partially protected pinto beans, petunias,
c«l«ry, roaaine lettuce, grapefruit, Cleopatra aandarin, «d
Saapson tangelo froa leaf injary caused by polluted air in ana
near los Angeles, in increase in the weight of and the nuaber
°f leaves on petunia plants was associated with the protection
9l»en fey the vitaain c treataents.t#
G. Effects-Plants and Livntock
-------
05723
Jo £.. Kendrick, Jrn, E. F., Darley, and J* T» Middleton
CHES0THBBAP7 TOB OXIDANT AND OZOKE IN CDC ED PHUT ERMAGE.
Intern- J« Air Rater Pollution 6, 391-U02 (1962).
* number of common fungicides, as well as antioxidants fro® the
rubber industry, were dusted and sprayed onto leaves of test
plants to determine their efficacy, as trell as their mode of
action, in protecting plants Iron subsequent exposure to ozone
and oxidants generated fro® ozcnated hydrocarbons.. Sot all
chemicals were egually effective* Some protected against both
ozone and oxidants, some protectee against one but not the other,
while some gave no protection.. The most effective materials
were dithiocarbaaates, mercaptcbenzothiozole and their derivatives#
while the least effective were amine derivatives. The degree of
protection was directly related to concentration of chemical,
longevity of protection was related to accumulated periods of
exposure to toxicants. Over a 10-hour accumulated exposure period
plants were significantly protected, although the degree of injury
gradually increased with exposure tine. In contrast, when several
days lapsed between application and exposure, the chemical was as
effective as when applied on the day of exposure, action of the
protectant was local and net systemic; the toxicant appeared to be
deactivated at the leaf surface. Leaves remained free of injury
only when the chemical was applied to the lower leaf surface and
then only on that portion actually covered with chemical. Some
degree of protection was achieved in field tests against
atmospheric oxidants as well as against those generated in the
laboratory. {Author abstract)t*
05724
J. B. Kendrick, Jr., I. I.. Sarley, J.. T» Middleton,
and A.. 0- Paulas
P1AST SBSPOUSE TO POZIOTED AIR. Calif. Agr. 10 (8), 9-10
<»ug., 1956) „
Field observations and controlled fumigation experiments have
shown that plants differ in their response to atmospheric
contamination by ethylene, herbicides, fluorides, sulfur dioxide,
and snog, or oxidised hydrocarbons. Controlled experiments have
also shown that plant response tc air pollution varies with species
and variety of plant, age of plant tissue, soil fertility levels,
soil moisture, air temperatures during the prefnaigation growth
period, and presence of certain agricultural chemicals on leaves.
Plants also vary in their susceptibility to sulfur dioxide, with
alfalfa, barley, and cotton damaged at comparatively low levels,
and citrus, corn, celery, and melons daaaged at much higher levels,
field observations show that young leaves are seldom narked during
periods of aggravated air pollatioa. The young, unexpanded leaves
are typically uninjured; the mature, expanded leaves are severely
866
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
injured; ana the old, so#e*hat it&the base"" the leaf.
In grasses, where the youngest tissue i intensity of injury
lujury first occurs at tip. gradjag o« aSS«s
toward th€ base of the leaf* Cld lcai compounds are
are seldom injured. Several groups of ch oxidized
capable of preventing injury to ? e applied to the
hydrocarbon fumigations the f heiono to the
lower surface of leaves. These sulfide groups, and
aithiocarhamate, ben«othiaicle, *?Ju?furai fungicides for the
have been used extensively as agricultura _ 9 che»icala for
control of many fungus diseases. «o ot tkj ^
this purpose are zineb—zinc ethyleivebisdithiocarD^ prots »>g»x«
protected from sericus injury***
05745
°cdiji, l. , o„ c« Taylor,, #b. e. p ropst, and E. A„ Cardiff
°SE OF ANTIOXIDANTS TO PHOTECT P1AHTS FBOM OXIDAST TTIPE JIB
POUutakts. Intettu Mr Pollution 6, 221-37 {19S2J,
Single dusts of nickel ai-H-butyl dithiocarbaaate (35 percent),
sine ethylenebis Idithiocarbaaate) (Zinei) {35 percent) cr
potassium ascorbate <6 percent) diluted with Pyra* ABB effectively
Stotecteft lettuce and endive plants froa a 2-hr. exposure to i ppn
ozone. These substances bad little or no effect on plants exposed
to damaging concentrations of peroxyacetyl nitrate* The caxbanates
protected Pinto beans fcom aibiftttt oxidants und«r conditions
suggestive of a relatively high ozone to peroxyacetyl nitrate land/
or hoaologuej ratio. {Author abstract)
0577«
Taylor, o. c., Dugger, V. 8», Cardiff* 1. *•# a»d Darley
B. J,
ISTBBACTIOI Of XIGHT AHD JLtHQSPHIBIC PHTOCHEBICJI. PRODUCTS
(*5»OG"| fITHIN PtASTS. Jtatur* 192 (#805} 81«-6 (Dec. 2, 196t.}
Slant dan age due to 02one and peroxyacetyl nitrate {PAH) was
studied, tinto beans and petunia plants *ere grown under the
following llgbt conditions! natural liglit in tie greenhouse, light
fto» cool white fluorescest lamps, light £to» Sylvania very aiga
output <*HO) fluorescent laaps, and darK ehaibers. The plants wese
G. Effects - Plants and Livestock B$7
-------
exposed to the oxidants for periods of thirty minutes or less and
returned to the pre-treatnent light condition. Syaptoas of oxidant
damage were usually aparent within four hours; however, assay of
daaage was mada 48 hours after exposure to the oxidants.
Sensitivity to ozone injury was increased by the low light
intensity while sensitivity to peroxyacetyl nitrate was increased
by the higher light intensity. In one series of experiaents, bean
plants were fuaigated with very high concentrations of PAN for 10
ainutes. The plants had been grown under the light and were
returned to the light after the 10 ainute fuaigatien, Darkness
during this short fuaigation period gave coaplete protection to
petunia as well as bean plants, while identical plants, fuaigated
in the light* were severly daaaged. Poroaeter measurements showed
that the resistance to air flow through the stonates during the
dark period was essentially unchanged# This indicated that the
observed results were related to the interaction of light and scae
product in the plant and not to the exclusion of PAN by closed
stonates.
05777
G. ». Todd B. Propst
CHANGES IN TRANSPIRATION AND PHOTOSiNTHETIC FATES OF VARIOUS
LEAVES DOSING TFEATHENT HITH 0Z0NATEE HEXENE OB OZONE GAS.
Physiol,. Flantarun 16, 57-65, 1963.
ffeasurenents were Bade on the rates of photosynthesis and
transpiration of bean, tcaato and coleus leaves during and
immediately following fuaigation with either ozone or ozonated
hexene gas. Both fumigants caused Marked decreases in the
rate of photosynthesis in all 3 species although in tonato
and coleus leaves, the reduction in photosynthesis took
place only during fuaigation with ozonated hexene gas and
afterwards the rate returned to normal. Ozone fumigation
caused decreases in transpiration but the decrease was not
as large as that obtained for photosynthesis. Transpiration
in tomato and coleus leaves shoved little response to ozonated
hexene gas although bean leaves responded in auch the sane way
as they did when they were treated with ozone alone. The white
portions of coleus leaves (where the green outer orttion had been
removed} were used for similar fuaigations and an increase in
respiration and a decrease in transpiration with ozonated
hexene was noted. There were no changes in transpiration froa
leaves following ozone fuaigaticns* increases ie respiration
after ozone and ozonated hexene fumigations were obtained for bean,
toaato and intact coleus leaves as had been reported previously
for bean leaves. It was postulated that part of the decrease
in growth (not accompanied by visible injury) obtained when
plants were treated with ozonated hexene gas light be due
directly to the reduction in photosynthesis* it would
not appear in the species tested that the nore resistant species
close their stoaates and thereby prevent the fuaigant froa
entering. (Author suaaary)M
868
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
05778
Todd, G» D. and Arnold, V. V.
iN EVALUATION OF HETHODS USED TO DETEHBINE INJURY TO WANT LEAVES
BY AIR POlLOTAHTSu Botan. Gaz. 123, (2J 151-4, Dec. 1961-
An evaluation was made of three Methods of analyzing the damage of
plant leaves alter exposure to ozone or ozonated hexene gas. A
visual estimate was made of the amount of leaf surface damaged.
The same plants were used for measurements of the change in fresh
weight and of chlorophyll content* The latter two measurements
were chosen because injury results in desiccation of parts of the
leaf and a loss of pigmentation. Also these would be a measure of
the actual amount of functional leaf material which was damaged*
It was found that losses in fresh weight were nearly proportional
tc losses of chlorophyll in injured leaves. The visual-rating
system appeared to be sensitive in the lower range of injury but
rather insensitive at the upper end of the range. The visual-
damage index appears to be logarithmic with respect to both
chlorophyll and fresh-weight changes. It was concluded that a
measurement of the change in either fresh weight or chlorophyll
content would give a better estimate of impairment of leaf
function, since the visual-damage system tends to overestimate the
flamage inflicted, particularly when only a small amount of leaf
surface is involved. ^Author summary)
05851
Katz and v. c. Shore
AIB poiumcs DAHAGE to VEGETATION- a. Air Pollation Control
Assoc,. 5 (3|, 1W-50. 182 |So*. 1955J- presented the
18th Annual Meeting, Air Pollution Control Association,
Detroit, Bich., Bay 22-26, 1955..J
The evidence in the present study on chlorophyll and pheophytin
conversion in conifer leaves indicates that acid gases, such as
sulfur dioxide in sufficiently high concentration, convert the
chlorophyll pigments into the corresponding pheophytins- This
process does not take place to an appreciable extent, however,
unless the threshold values for sulfite in the living cells is
exceeded.. The effect may be produced by either relatively short
exposures to high concentration of gas or more prolonged exposures
to lower concentrations. Transformation of an appreciable
proportion of chlorophyll to pheophytin is accompanied by visible
symptoms in the tissue, such as plasmolysis, shrinkage of cells,
And fading of the normal green color. Ihen these symptoms have
progressed to the post-mortem stage, there is of course no
chlorophyll or pheophytin left in the injured portions of affected
leaf tissue* The color say then turn red or reddish-brown if
anthocyanin pigments, associated with the appearance of large
amounts of sugar in the cells, are formed. Eventually such leaves
turn brown because of post-mortem oxidative changes. These color
G. Effects - Plants and Livestock
869
-------
changes are characteristic of conifecs. In other species, the
destruction of the chlorophyll, pheophytin, and other pigments in
the chlorcplasts results merely in the appearance of bleached or
ivory colored areas, as in cereals and alfalfa. In chlorotic
injury the affected tissue is deficient in chlorophyll, but the
extent of pheophytin conversion is not high, and such leaves may
recover their normal functions if plasmolysis has not taken place.
Prolonged exposure to sulfur dioxide below the threshold injurious
concentration has no appreciable effect on the chlorophyll content
of leaves, as shown by sample specinens from the inner and
intermediate fume zones of a stelter area. Deposits on leaves and
in stomata from smoke and ether aerosol contaiinants in an urban
environment may cause little, if any, discoloration but can result
in a reduction in the normal chlorophyll level-M
05902
Richards, B. L«, Hiddleton, J. 1. and Hewitt, W. B.
OZONE STIPPLE OP GRAPE LEAP. Calif. Agr. 13 (12), U. 11 (Dec..
1959) .
A study of ozone stipple of grape leaf shows that lesions on the
upper leaf surface and premature leaf fall occur on grapevines in
areas polluted by airborne ozone. The primary symptoms consist of
small, brown to black, discrete, dot-like lesions, which are easily
distinguished from the lesions of the other grape disorders because
of the stippled appearance on the upper surface of the leaf.. The
typical primary lesions vary in diameter from about 0.1 to 0.5 mm-
¦illiaeter-and are confined to groups of cells bounded by the
smallest veins. Large lesions result from coalescence of small
ones, and may measure up to 2.0 mm in diameter. Aggregates of these
minute spot-like lesions produce the typical stipple appearance.
05903
B.. L. Richards, J., T. Hiddletcn, and «- B. Hewitt
AIR POLLUTION UITH RELATION TO AGBOHOKIC CFCPS: V. OXIDANT
STIPPLE OF GRAPI. Agron.. J„ 50, 559-61 (1958). (Presented
at the 50th Anniversary fleeting# American Society of Aqroncmy,
Hov„ 20, 1957.)
small, brown to blacfc, discrete, punctate lesions occur on the
upper leaf surface of grape grown in areas polluted by air-borne
oxidants. The lesions are typically restricted to the palisade
layer and may be easily distinguished from other grape disorders
because of their stippled appearance. The disease can be incited
in grape by fumigation with ozene. Toxic ozone levels occur in
the polluted air mass above the Los Angeles and San Prancisco
areas where oxidant stipple is found, stipple has not yet been
seen in the grape producing areas in the Coacfaella, Napa,
Sacraaento, and San Joaquin valleys of California. Oxidant
870
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
stipple can be distinguished from smog-type oxidant injury due to
oxidized organics in that the upper leaf surface is stippled in
grape and there is no common and pronounced silvering or glazing
of the lower leaf surface as found an herbaceous crops and weeds in
and adjacent to affected vineyards. Leaf injury to grape due to
foliar fluoride accuiulaticn can be readily distinguished because
it is marginal red to brown in color, necrotic, and commonly
exhibits zonate markings.. Stipple can also be easily separated
frcm foliar salinity and drought injury* both of which produce
marginal and intercostal leaf necroses similar to those induced by
fluorides. Although ozone occasionally may cause leaf injury to
some plants particularly grasses, grown in areas receiving
naturally polluted air, it is unusual to note ozone damage to
agricultural crops; oxidant stipple cf grape is, therefore, a
unigue disease both in its symptcmology and etiology.,##
0 64 04
D. C, MacLean, D. C. McCune, 1. H. Weinstein, R. H.
Mandl, G. N. Woodruff
EFFECTS OF ACUTE HYDROGEN FLUORIDE AND NITROGEN DIOXIDE
EXPOSURES ON CITRUS AND ORNAMENTAL PLANTS OF CENTRAL
FLORIDA. Preprint. (Presented at the 60th Annual Meeting,
Air Pollution Control Association, Cleveland, Ohio, June
11-16, 1967, Paper No. 67-158.)
Six citrus varieties and six ornamental species of economic
importance to Central Flcrida were subjected to high
concentration-short duration exposures of gaseous hydrogen fluoride
(HF) or nitrogen dioxide (N02). Pose-fumigation observations
showed that the effects of acute pollutant exposures differ
markedly from those of chronic exposures. HF exposures of 0.5 to
10 ppn and durations of from 30 minutes to 8 hours induced tip,
marginal, and intercostal chlorosis and necrosis and abscission
ot leaves of most plants tested. Injury was most severe on, but
not limited to, young leaves. The effect of duration of exposure
had a greater influence on abscission of young citrus leaves than
did HF concentration. However, the effect of HF
concentration on foliar F accumulation could not be separated
from exposure time. N02 concentrations used ranged from 25 to
250 ppa for durations of froo 10 minutes to 8 hours. N02
damage was characterized by rapid tissue collapse, necrosis, and
defoliation. Injury was sporadic in appearance, affecting leaves
of all ages. The relative contributions or concentration and
duration to N02-induced injury were about equal. (Author
abstract)##
06417
L. Crdin, M.
PEROXYACETY L
A. Hall, B. Katz
NITRATE-INDUCED INHIBITION OF CELL HALL
G. Effects • Plants and Livestock
871
-------
METABOLISM. J. Air Pollution Ccntrcl Assoc., 17(12):811-
815, Dec. 1967. 11 refs, (Presented at the 60th Annual
Meeting, Air Pollution Control Assoc., Cleveland, Ohio,
June 11-16, 1967.)
Levels of PAN which inhibit oat ccleoptile section growth
reversibly, severely inhibit metabolism of cellulose and of cell
wall non-cellulosic polysaccharides. An enzyme in the
coleoptile cell walls which hydrolyzes some ot the non-cellulcsic
glucan was partially inactivated by direct PAN treatment ot
homogenized cell wall. Treatment of intact cells by PAN
also resulted in a partially inactivated enzyme. Ccleoptile
phosphoglucoautase was partially inactivated by treament with
PAH both in vitro and in vivc. After treatment of intact
cells with PAN, phosphoglucomutase associated with subcellular
particles was more severely inactivated than was soluble enzyme.
Uridine diphosphate glucose pyrophosphotylase from coleoptiles was
inactivated by PAN in vitro but not in vivo. A particulate
cellulose synthetase from coleoptiles was inactivated by
PAN both in vitro and in vivo. Since cell wall biosynthesis
and/or degradation are needed for expansion it is concluded that
PAN inhibition of these enzynes nay account for reduced cell
growth. (Authors* abstract)##
06447
F.. A„ Wood, D» B. Drummond, B. G. Wilhour, and D. D,
Davis
AN EXPOSURE CHAHBEB FOB STODYING 1HE EFFECTS OF POLLUTANTS ON
TFEES. Preprint. (Presented at the 63th Annual Fleeting, Air
Pollution Control Association, Cleveland, Ohio, Jane 11-16,
1967, Paper No* 67-38g.)
In order to study the effects of photochemical air pollutants such
as ozone and peroxyacetyl nitrate (PAN) on woody plants, a
chamber was selected and aodified to provide a uniform
concentration of fumigant throughout its interior, a high degree of
control of temperature and relative humidity, a size large
enough to accomodate five to ten-year old trees and interior
components resistant to corrosion by oxidants. This was
accomplished by modifying a Hodel H-2 Beach In Growth
Chamber., A preliminary evaluation of temperature, relative
humidity, and ozone concentration regimes within the chamber
revealed a 1 to 2»0 T fluctuation in temperature, 1 to 2 7
fluctuation in wet bulb temperature and a 5* fluctuation in ozone
concentration across the chamber. Fluctuations in dry bulb
temperature, wet bulb temperature, and ozone concentration at a
given point in time were plus or minus 0-5 F-plus or minus 1.2
F, plus or minus 0.5-1..0F, and plus or minus 5% respect!vely-
During fumigations, the system has performed satisfactorily.
06459
Thompson, c. R., J. 0. Ivie, and B.. D. Thomas
872
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
CONTINOOOS PECOPDIHG OP AIR POLLUTANTS AND THEIR EFFECTS ON
HEARING CITHUSn Preprint-, 1960
Decline in citrus production and fruit quality is reported by
growers during the past 15 years in the Los Angeles Basin.
Air pollution is considered to be a aajor factor contributing to
this problem. An industry-agriculture-local government-university
sponsored, cooperative study entitled the Agricultural Air
Research Program was begun in 1960 to assess the econonic effect
of various air pollutants, principally oxidants and fluorides, on
fruit yield, quality and tree growth- Measurements of
photosynthesis and transpiration are used to supplement the
longtime growth and yield observations. Automatic data recording
is provided for: (1) apparent photosynthesis by carbon dioxide
exchange: <2) plant transpiration; (3) nitrogen dioxide; (4) nitric
oxide: (5) ozone; 1(6) total oxidants; (7) fluorides; (8)
temperatures; (9) integrated sun light recording; (10) date, and
(11) time of day. »ith punch card recording, direct automatic
handling of the data on the 1620 IBB computer is possible.. The
initial experiment is being conducted at Upland, California on
2U lenon trees with six treatments as follows: (1) Clean Air;
(2) anbient air; (3) fluoride-free air; (U) ozone-free air; (5)
clean air with fluoride added; and (6) fluoride and ozone free air.
Four unenclosed trees serve as checks. Plans are underway for
similar experiments in other locations with both lemons and
oranges. {Authors* summary}#!
06U98
L„ Ordin, and B. Propst
EFFECT OF PHOTOCHEHICALLT PROBOCZD OXIDANTS OB GROWTH OF AVENA
CCLEOPTILE SECTIONS*. Plant Physiol., 36(3), 326-30, (day
1961)„
A vena coleoptile sections incubated in solutions through vhich
photochemically produced oxidant mixtures, ozone or peroxyacetyl
nitrate (PAN) are passed, display subsequent repressed growth in
fresh solutions to which auxin has been supplied. Treatment by
oxidant recording as l.tt ppm derived from an irradiated mixture of
trans-2-butene and N02 results in about 50% inhibition of
elongation. About 1..5 ppm PAH also inhibits growth to the same
degree or more. Approximately 170 ppa ozone produced comparable
magnitudes of inhibition. In all cases basal respiration was
inhibited little or not at all.. Although the concentrations dealt
with here are about tenfold above those found in the atmosphere
(200-fold for ozone) the results may be helpful in the
interpretation of mechanisms of growth inhibition in the field.
There are probably several reasons why high concentrations of
PAN are required to produce growth inhibition in Avena
coleoptiles while much lower concentrations affect more sensitive
intact plants. Although the ccleoptile is cutinized and has few
stomata, suggesting a transport barrier, there are indications that
root tissue which is neither cutinized nor suberized to any great
extent may be even less sensitive- Thus the answer is more likely
to lie either in the resistance of the cellular membranes
G. Effects - Plants and Livestock
873
-------
themselves to the uptake of the oxidants or in the presence of
reducing agents in the cell or, simply, less sensitive enzyme
systems. It was found that intact seedlings in the gas stream are
not more sensitive than sections flcating in water during gas
exposure- The lack of illumination during exposure may also be a
factor, since even sensitive petunia plants exposed in the dark to
C.5 ppm oxidant derived from an irradiated mixture were not
damaged.. ##
06500
1- ordin
EFFECT OF PEBOXYACETYL NITRATE CN GFOWTH £ CELL WALL
MET ABOLISH OF AVENA COLEOPTILE SECTIONS- Plant Physiol- 37
<5) , 603-8 (Sept. 1962). {Presented at the Annual fleeting,
Western Section American Society of Plant Physiologists,
Davis, Calif., June 22, 1961.,)
Indoleacetic acid induced growth of Avena coleoptile sections
which had been pretreated with 2.. 14 Fpm peroxyacetyl nitrate (PAN)
fcr 6 hours at pH 1 was inhibited 84JE during the tt-hour period
following fumigation- Production of C14C2 in indoleacetic
acid-free, carrier-free glucose solution (ca., 10 to the minus 5th
power B) was inhibited about 75* by the pretreatment while tctal
oxygen uptake was unaffected. Incorporation of C1H into
cellulose and into the acid soluble wall fraction was inhibited
90*„ Incorporation into other wall fractions was inhibited to a
lesser degree. Onder conditions of severe growth inhibition, a
marked decline relative to other sugars was found cf incorporation
of C14 into the galactnrcnic acid of the aqueous soluble vail
fractions. A relative decline was also observed in radioactive
xylose of the hot water soluble fraction and of the dilute alkali
soluble polysaccharide. Possibly the inhibition of growth by
PAN is associated with inhibition of metabolism of cellulose.
Inhibited metabolism of agueous-soluble pectin and of acid soluble
non-cellulosic polysaccharides Bay also account for restraint of
growth. flAuthor"s summary, Modified)#*
06557
I. A. Leone, E« Brennan, B„ H. Daises
PLANT LIPE AS AIH POLLUTION INDICATORS. Proc. Northeast.
Heed Control Conf. 18, H51-5 <196«)..
Plants display a particular talent for indicating the presence
of very low concentrations of pollutants in the atiosphere.
Agricultural people are concerned with two broad groups of
pollutants, the primary or single scurce emissions which are the
result of a particular industrial or fuel-utilizing process, and
the products of photochemical reactions which are the result of a
874
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
whole complex of combustive activities in urban areas. The
primary phytotoxic contaminants include hydrogen fluoride, chlorine
, sulfur dioxide,, ammonia* hydrogen sulfide, ethylene and
perhaps illuminating gas. The remarkable thing about these
phytotoxicants is that each one severely affects a particular
group of plants which is more or less tolerant to the other
pollutants. Eor that reason plant indicators are
very useful in diagnosing the specific gas or gases responsible
for an air pollution episode, if observed during their optimum
growth period..##
C7255
Thompson, C„ B_, o. C.. Taylor, M. D.. Thomas, and J..
0. Ivie
EFFECTS OF MB POLLUTANTS OS AFPABENT PHOTOSYNTHESIS ADD WATER USE
T?Y CITRUS TREES™ {(Environ., Sci. Tecbnol.,)) 1 (8) : 6UH-650,
Aug.. 1967u 20 refs-
Because of the Rajor damage to crops by air pollutants, studies
were begun to measure under field conditions, the effect of
various atmospheric phytotoxicants on agricultural crops in the
Upper Santa Ana Drainage Basin- There was question as to
whether photocheiical snog and/or fluorides were responsible for
major economic losses by the citric industry and if so, how much.
Commercially producing lemon and navel orange trees were tested to
determine the effects of ambient air pollutants which occur in the
Los Angeles basin on water use ^transpiration) and apparent
photosynthesis. The entire trees were enclosed in plastic
covered greenhouses and were supplied various fractions of the
atmosphere to find whether ozone, peroxyacyl nitrates, or
fluorides were causing deleterious effects. Nitric oxide was
added to the air in one treatment to reduce ozone selectively but
in so doing, nitrogen dioxide in amounts equal to the ozone was
formed. The results showed that the total photochemical smog
complex reduced the rate of water use by lemon trees and also
reduced the rate of apparent photosynthesis. Fluoride levels
occurring in the atmosphere caused no detectable effects-
Attempts to evaluate the separate effects of ozone and
peroxyacyl nitrates were unsuccessful. Seduction of the ozone
in the tree atmospheres by addition of nitric oxide failed to
overcome the reduced water use and lowered apparent photosynthesis.
(Author abstract modified)##
07453
Seidman, Gabriel and Wilson B. Figgan
S10MATAL MOVEMENTS: A YEABLY RHYTHM. Ereprint, Dept. of
Agriculture, Cincinnati, Ohio, Crops Besearch Div. and
Public Health Service, Cincinnati, Ohio, National Center
for Air Pollution Control, ((13>) p., ((1967)). 1U refs.
G. Effects-Plants and Livestock
875
-------
since the degree of stomatal opening may influence the arcunt of
air pollutant injury, a year-long study or daytime stomatal
movements was initiated, light, temperature, atmospheric pressure,
relative humidity, time of day, and month or year were the
parameters studied. Atmospheric pressure was considered because
it was felt that air pressure changes might affect the turgor ot
the guard cells and thus change tbe size of the stomatal pore.
Certified seeds of Phaseolus vulgaris, L., var. Pinto from
stock stored at room temperature were planted in a standard
peat-perlite mix and grown in the greenhouse and in the growth
chamber. Two plants were grown in each 4-inch plastic pet. The
pots were placed in a pan of Hcagland's solution. Plants in five
pets were started in the greenhouse, and an eyual number in the
growth chamber each day. in the greenhouse, atmospheric
pressure, light intensity, temperature, and relative humidity
baried from hour to hour during the day and from month tc month
during the year. In the growth chamber light intensity,
temperature, and photoperiod were held constant. If there were
actually daily and yearly rhythms in stomatal opening as a result
of photoperiod, temperature, or changes in light intensity only, no
rhythms or a reduced rhythm in the growth chamber would be
expected. Stomatal movements in plants grown under variable
greenhouse conditions as well as under constant growth chamber
conditions appear to be subject to seasonal rhythms. Stomates
of plants grown during the fall and winter months do not open as
wide as those grown during the spring and summer months.##
07*55
Tingey, David T„ and A- Clyde Hill
THE OCCOHHENCB OF PHOTOCHEMICAL PHYTOTOXICANTS IN THE SUIT LAKE
VALLEY. Preprint, Utah Oniv», Salt lake City, Dept-
of Botany, |{13)) p„ , April 21, 1967.. 17 refs.
To determine if photochemical ait pollutants were present in Utah
along the Wasatch front, ozone sensitive indicator plants
(Tobacco Bel-C and W-3) were grown at several locations in
Utah, Salt Lake, and the southern part of Davis Counties and
observed for injury development. These studies, which were
conducted over a seven year period, shoved that extensive ozone
injury developed on the indicator plants in the northern part of
Salt Lake County and the southern part of Davis County.
Injury was less severe and developed less frequently in the
northern part of Utah County, and injury was extremely rare in
the southern part of Otah Count;. Cursory observations of other
species shoved that both ozene and PAN injury symptoms
occasionally developed* To determine the concentrations of ozone
and PAN that are present in the atmosphere, ambient air
measurements were undertaken at the University of Utah, Air
Pollution Research Laboratory. The authors were particularly
interested in PAN measurements because atmospheric PAN
concentrations have not been reported in the literature. Results
of these analyses are discussed in this paper. A "Bast" ozone
analyzer that had been calibrated with potassium iodide was used to
measure ozone in the aabient air at the laboratory. Peroxyacetyl
nitrate was measured by the method of Parley et al. with
876
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
modifications suggested by Stephens- A 9-inch teflon column
packed with 5* carbcwar tOC on Cbromosorb H vas maintained at 22
deg in an insulated box cooled with a thermoelectric cooler. An
electron capture detector mounted in the box and connected to the
electrometer of a Villeins Model 600 D gas chromatograph was
used to determine the PAH concentration. Ozone vas measured
sporadically during 1965, and starting in June of 1966
continuous measurements have been made except for limited periods
when the analyzer vas needed for other studies. Two figures are
included showing the monthly average ozone concentrations and the
average hourly ozone concentrations for representative months. A
comparison is also made of the ozone concentrations found in the
areas.* #
075 CI
KouJcol, Jane and ». n. Dugger, Jr.
SHORT COMMUNICATION: ANTHOCYADIR P0RMATI0H AS A BFSPONSE TO
OZONE AND SHOG TBEATHENT IH BDHE* CRISPUS I. Plant Physiol.,
M2J7):1023-102U, July 1967. B refs.
"the red coloration which appears on the leaves of dock plants
(Pumex crispus 1.} after exposure to saog to ozone vas shown to
be due to the appearance of an anthocyanin. The leaves of
untreated plants did not contain detectable anthocyanin.
Furthermore, chlorosis did occur in treated plants. The
anthocyanin was isolated from the leaves of saog treated plants,
purified, and identified only as a cyanidin glucoside. (Authors'
summary) *#
C7610
Freebairn, Hugh To
THE PHEVENTICK OP AIR P0IIUT30N DAMAGE TO PLANTS BY THE USE OF
VITAMIN C SPHATS.. J. Air Pollution Control Assoc., 10(«}:31<*-
317, Aug. 1960. 10 refs. (Presented at the 52nd Annual Meeting,
Air Pollution Control Assoc., Los Angeles, Calif., June
21-26, 1959.)
The amount of protection which vitamin C provided for plants
against ozone and smog was investigated. In the laboratory, plants
were treated with ascorbate salt by addition to the solution
surrounding the roots of plants growing in water culture. The
plants were then fumigated with 7-10 ppm of ozone for 2 hours. Poa
annua plants growing in a greenhouse were sprayed with 0.040
potassium ascorbate for varying numbers of days before being
exposed to polluted air. Similar methods were used on other plants
and flowers grown under glass. Lettuce and spinach plants growing
commercially were sprayed in the field for one, two and five days
per week with potassium ascorbate. Smog attacks occurred about 20
days after spraying was initiated.. In these field tests no
significant amount of protection was obtained for the spinach;
G. Effects * Plants and Livestock
877
-------
however, a 66* protection was obtained for the lettuce with a 2
day/week application and an 82% protection with a 5 day/week
application. The results of the lab and field tests indicated that
vitamin C moved into the leaf cells of some plants and thereby
increased the tolerance of the cells to the damaginq agents in
smog„ The protection afforded by vitamin C in the lab from ozone
and in the field from air pollutants imflied that either 02one was
a damaginq agent in the field or that vitamin c was effective
against other toxic agents in the field.
07786
Hansbrougb, J., R.
AIR QUALITY AND FORESTRY. In: Agriculture and the Quality of
Our Environment. Brady, N. C.. (ed.), Norwood, Hass., Plimp-
ton Press, AA AS—Pub—05,,, p. 45-55, 1967. 25 rets., (Presented at
Beeting, American Association for the Advancement of Science,
Science, Washington, D. C. , «DEC» 1966..)
A review which cites examples cf injury to forests by specific ait
pollutants. The source and the nature of the pollutants are
discussed. Also, the contribution of trees in conbating the air
the 133rd» Meeting, American Association for the Advancement of
pollution problem is speculated on., As technology changes, trees
wherever they grow and for whatever purpose are increasingly
subjected to toxic substances in the atmosphere. There is a
considerable body of knowledge already available but it is dwarfed
by the magnitude of what is not yet known. More information on the
nature and source of air pollutants and their present and expected
impact on our forest and shade tree resource is necessary™
0786U
Krueger , A. P.. s. Kotaka„ K„ Nishizawa, Y. Kogure,
ft. Takenobu, Takenobuv and P. C„ Andriese
AIR ION EIFECTS OH THE GBOWTH OP THE SILKHORK (BOHBYX BORI
I.J» Intern. J. Bioneteorol., 10 <1> s29—38, 1966. 17 refs.
CFSTI/DDC: AC 6U6704
The exposure of silkworm eggs (BCflBYX MOBI L.J to unipolar ionized
atmospheres of either charge at 21 deg.. C and 26 deg. C induced
an earlier onset of hatching. Continued treatment of the larvae
produced the following physiological effects: (1) A narked
increase in the rate of larval growth; (2) Increased biosynthesis
of catalase, peroxidase and cytochrome c oxidase;
(3) Earlier onset of spinning; (4) A significant increase
in weight of cocoon at 24 deg. C and 26 deg~ C. At 24
deg. c treatment with either or (-) ions caused
a statistically valid increase in pupal weight but at 26 deg- C
this occurred only after (~) ion treatment. Exposure at both 2«
deg- C and 26 deg.. C to air ions of either charge resulted in
developsent of heavier silk layers but the increases were not
statistically significant. {Authors! abstract)
878
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
00843
Heck, Walter W., John A. Dunning, and Henry Johnson
DESIGN OF A SIMPLE PLANT EXPOSURE CHAMBER. preprint. Dept. 0±
Agriculture, Cincinnati, Ohio, Agricultural Research Service
and Public Health Service, Cincinnati, Ohio, National
Center for Air Pollution Ccntrcl, ((28))p., 1967. 3 refs.
(Presented at the 60th Annual Meeting, Air Pollution Control
Assoc., Cleveland, Ohio, June 12-16, 1967.
A variety of exposure chamber designs have teen used in the study
of the effects of phytotoxic air pollutants on vegetation.
Acceptability of a design is determined by the types of plants to
be studied and the purpose of the research. In any exposure
chanter, however, design is determined by the most desirable flow
characteristics, the toxicants to be used, and the degree ot
environmental control desired. A major consideration should be
versatility combined with simplicity. The chambers used in
studies at the National Center for Air Pollution Control
utilize a dynamic, negative-pressure, single-pass flow system with
uniformity of flow, toxicant nixing, and distribution in the
chamber. The simple design permits easy installation of numerous
chambers in a single air-handling system while still permitting
individual control of chambers. (Authors' abstract)##
091HI
Bichards, B. L., Sr., o. C. Taylor, and G» Fn Edmunds,
Jr„
OZONE NEEDLE MOTTLE OF PINE IN SOUTHERN CALIFORNIA. J. Air
Pollution Control Assoc., 18(2}:73-77# Feb. 1968.
The specific type of chlorotic Mottling in ponderosa pine
needles, as reported by various workers, justifies the assumption
that X-disease, needle dieback, cblccotic decline* and ozone
needle mottle in various pine species described in this paper are
one and the sane disease* Experimental production of chlorotic
needle mottling in pondetosa pine (Pinus ponderosa Laws) with
ozone-polluted ambient air and with synthesized ozone by niller
further justifies this basic assumption. Controlled fumigation
studies (1959 and 1960 at the Citrus Besearch and Agricultural
Experiment station, Biverside, Calif.} confirm needle mottle of
pine as a distinctive physiogenic disease, and atmospheric ozone as
the prime etiological factor. Basic experimental research
together with the wide range of field studies and observations by
the present authors have clarified the type and sequence in symptom
expression essential for diagnosis, and have greatly extended the
range of pine species visibly susceptible to atmospheric ozone.
Additional emphasis is placed on significance both of the ozone
needle mottle problem and of ozone as an economic factor in
forestry., (Authors" abstract) •*
G. Effects ¦ Plants and Livestock
879
-------
09317
E- 1. Sharp
ATHOSPHERIC IONS AND GERfllNATION CF OREDOSPOHES OP POCCINIA
STPIIFOHNIS. Science, 3880(156) : 1359-1360, April 6, 1968..
8 refs.
Ataospheric ions, identified by Mobility characteristics, were
associated with gemination of lycphilized uredospores of
Puccinia striiforais Rest, at Bozenan, Montana. Ions of
interaediate size were highest in concentration, and percentage
gemination of spores was lowest during periods conducive to air
pollution. In duplicate experiments at an isolated site near
Barrow, Alaska, essentially all ataospheric ions were snail ions
and the fungus spores were consistently gerainated near aaxiaua.
(Author's abstract)*•
10206
102067
Haut, H. Tan and H. Strataann
EXPERIHENTAL INVESTIGATION OP THE EFFECT OF NITHOGEN DICXIDE ON
PLANTS. Transaction of the Land institute of Pollution
Control and Soil conservation of the Land of North
Bhine-Restphalia, Essen. ((Schriftenreihe der Landesanstalt
fur Iaaissions- und Bodennutzungsschutz des Landes
Nordrhein-Hestfalen, Essen.)) Translated fron Geraan.. No.
7:50-70, 1968. <(25)) refs.
The effect of N02 on plants was studied. Because NO is
always present wherever there is 902# NO was also introduced
into the exposure chambers containing test plants. Included in
the tests were various dicotyledons, monocotyledons, conifers, and
deciduous plants. Syaptoas of daaage included necrosis, chlorosis,
striping, and spotting. The toxic tolerances of aany plants
are listed, along with specific daaage syaptoas for each. Effects
of stage of growth and soil conditions are considered.. The
concentrations of N02 which were damaging are compared to the
toxic concentrations of SO2 which have been thoroughly
studied is the past.M
10426
Billiae A. Feder
REDUCTION IB TOBACCO POLLEN GEBBINATION AND TOES ELONGATION,
IBDOCED BI LOI LEVELS OF OZONE. Science, 160(3832):1122, June
7, 196 8. 1 ref.
In a three part series of tests it was found that pollen o£
880
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
the ozone-sensitive tobacco variety Bel W-3 undergoes a
reduction in germination rate and tcbe elongation when exposed to
ozone.. In a first series of tests, pollen was exposed to ozone
(1 ppa) for up to 6 hours. Disks were removed from the
chamber after exposure of 30, 60, 120, 180, 240, or 360
ainutes. In the second series, the pollen was exposed to ozone
(0„1 ppm) for 5»5 and 2U hours. A third series consisted of
intact flovering plants exposed to ozone (0,1 pp«) Cor 2U hours in
a larger ozonating chamber in which ozone was generated by a
welsbach generator from charcoal-filtered ambient air. Pollen
was removed and allowed to germinate., As little as 0.1 part of
ozone per million for a 5„ 5-hour exposure period was sufficient
to cause a UO to 50 percent reduction in germination and a 50
percent reduction in pollen-tube elongation- Ozone caused
these effects to approximately the sane degree whether the
pollen was exposed to ozone in vitro or agar disks, or in
vivo when the intact plant is exposed. Exposure to ozone at a
concentration of 1.. 0 part per rillicn for more than 3 hours in
vitro completely prevented germination of Bel w-3 pollen-
-------
1 C690
Miller, Paul R. , John R. Parmeter, Jr., Briyitta H.
Flick, and Charles W. Martinez
OZONE DOSAGE RESPONSE OF FONDEBCSA PINE SEEELINGS. Preprint,
California Univ., Berkeley, Dept. of Plant Pathology,
lP8))P*» 1968, 18 refs. (Presented at the 61st Annual
Meeting of the Air Pollution Control Association, St* Paul,
Minn., June 23-27, 1968, Paper 66-191.)
Fumigation of three-year-old pcndercsa pine seedlings in
controlled environment chambers with the major oxidant, ozone, at
0.15, 0.30, or 0.45 ppm, 9 hours daily at 25C. and 2500 ft.-c,
reduced the apparent photosynthesis rate by 10, 70, and 85S
respectively after 30 days exposure. Fomigation with 0,30 ppm
ozone for 33 days depressed the cold perchloric acid extracted
polysaccharides of both current-and one-year-cld needles by «0*.
The 80S ethanol soluble sugar concentration of current year,
ozone-injured needles increased 16X, and that of the one-year-old
needles decreased slightly frcm the amount present immediately
before fuiigation. Both sugar and pclysaccharide fractions of
control plants maintained under identical conditions in
carbon-filtered air increased moderately. The increased sugar
ccntent of current-year, ozone-injured needles may be associated
with a reported increase in the relative participation of tnis
needle age in C1402 fixation after ozone injury. The ascorbic
acid content of healthy, curtent-jear needle tissue vas nearly half
that of older needle tissue. These results emphasize apparent
photosynthesis measurements as a sensitive index for assessing the
degree of ozcne injury tc exposed pines, and lead to an
interpretation of the etiology of chronic needle abscission of
pcndercsa pine culminating in death cf affected trf?es.##
10713
Irwin P. Ting, and W. M. Dugger, Jr.
FACTORS AFFECTING OZCKE SENSITIVITY AND SUSCEPTIBILITY OF
COTTON PLAKTS. Preprint, California Univ., Riverside,
Dept. of Lite Sciences, ((21))f., 196b. 18 refs. (Presented
at the 61st Annual Heeting of the Air Pollution Control
Association, St. Paul, Minn., June 23-27, 1968, Paper
68-128.)
The sensitivity of cotton to oaone was studied to ascertain
the diurnal time of ozone sensitivity of cotton leaves, the
ontogenetic period of susceptibility, and the role of
stomatal opening in sensitvity and susceptibility. Cotton
plants (Acala SJ-1 and Deltapins sBocth leaf) were grown
from seed in a greenhouse from July through December, 1967.
Five seeds were sown per pet; seedlings were thinned to cue per
pot. Plants were irrigated with cne-guarter strength
Hoagland's solution at weekly intervals. GreenhouEe
conditions with light intensities of 2-t X 100,000 ergs/sq. cn./
882
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
sec, day temperatures as high as 40 degrees c, and minimum night
temperatures of 15 degrees, gave plants with
fully expanded cotyledons after about 17 to 18 days and a fully
expanded first, true leaf after atout 20 to 21 days. Plants were
brought directly to the laboratory at mid-morning for
fumigations with ozone and returned to an environmental control
chamber in the laboratory for observation after 24 and 48 hours.
During development, successive leaves including cotyledons
passed through stages of ozone susceptibility. The precise
developmental stage of susceptibility seems to be somewhat before
leaves are fully expanded. In general, maximum susceptibility
seems to cccur at about 75?( of full expansion. Fully expanded
leaves or very young leaves apparently Mill not damage even
after exposures of 1 ppm ozone tor several hours. An important
environmental factor correlated with variability seems tc be
light. Sensitive plants pretreated Kith dark for 24 hours
or more lose their ozone sensitivity. Thus, complete darkness
seems to afford some degree cf protection. Stcmates open
after a few minutes exposure tc light. In the case of ozone
damage, however, plants seem to require several hours
pretreatment after a dark period before visible damage would
result on susceptible leaves. There was not a positive
correlation between leaf resistance (stcmatal opening) and
visible damage to ozone. There is a peak period of sensitivity
of susceptible leaves during mid-moinang.##
10965
B.E. Dethier, D.U. Lecher
ATMOSPHERIC POLLUTION BY OXIDANTS AND ITS EfFECT ON VEGETATION
IN A RURAL ENVIRONMENT. Trans. N.Y. Acad, Sci., 30 (6) :863-
868, Apr. 1968.
Annual losses to agriculture in the northeastern United States
have been previously estimated in excess of 18 million dollars
annually. Ozone and peroxyacyl nitrate (PAN) are presently
recognized as major oxidants causing plant damage. Investigation
of diurnal oxidant levels was initiated at Ithaca, New York,
in an attempt to correlate pollution damage to specific plant
varieties with recorded oxidant concentrations. Tobacco,
variety Bel-W3, which is highly sensitive and fairly specific
for ozone, and petunia variety, white cascade, which is very
sensitive to PAN and fairly specific for that toxicant, were
used in 1967. These plants were grown in carbon-filtered
air and were periodically set cut an the weather station area.
Sensitive seedlings of eastern white pine were also used as
indicator plants. Bast ozone meters with S02 scrubbers
and strip charts were used to monitor the ambient ozone
concentration. Observations started July 1, 1967, and
continued through December 1967. Hourly measurements of total
oxidants, temperature, relative humidity, wind direction and
velocity, and total incident solac radiation were taken twenty-four
hours a day and the data were subject to machine analysis.
(Authors* abstract)##
G. Effects -Plants and Livestock
883
-------
10978
H. W. DeKoning, Z. Jegier
A STUDY OF THE EFFECTS OF OZONE AND SULFUR DIOXIDE ON THE
FHOTOSYNTHESIS AND RESPIRATION CP EUGLENA GRACILIS. Atics.
Environ., 2 (<*) ; 321-326, July 1968
The effects of brief exposures to kncwn guantities of sulfur
dioxide and ozone on the photosynthesis and respiration of
Euglena gracilis, a unicellular algae grown in a completely
synthetic medium were studied. Photosyntheseis and respiration
were measured by means of their corresponding oxygen exchanges
using a polarographic electrode. Measurements were made with
Euglena cells that were suspended in bicarbonate buffer just
before exposure and for 24 hr. before exposure. Exposure to
either S02 or S03 lowers the rate of photosynthesis and
increases the rate of respiration.##
11010
Smith, tl. E.
THE INFLUENCE OF ATMOSPHERIC DISPEBSION ON THE EXPOSURE OF
PLANTS TO AIRBORNE POLLUTANTS. Phytopathology, 58 (8): 108£~1008,
Aug. 1968.
Variations in atmospheric dispersion and the typically nonuniform
distribution of pollutant sources cause wide fluctuations in
pollutant concentrations at a fixed point on the ground. These
variations in concentrations are usually correlated with other
neteorological parameters, tine of day, and the levels of other
pollutants. The details of this variability differ strikingly,
depending upon the relative location of the plants and the sources
and upon the climatology of the area in which the problem exists.
An outline of the magnitude and time scales of these fluctuations
is presented. Specific correlations with other (actors that may
be important in designing meaningful dosage tests for pollutants
are indicated, without tests that simulate conditions in the
normal atmospheres laboratory experiments will be misleading,
and apparent sensitivities may bear little relation to the
response of the plant in the field.««
11072
Heck, Walter W.
FACTORS EFFECTING THE RESPONSE Of PLANTS TO GXIDAHT AIR
POLLUTANTS, preprint, Dept. of Agriculture, Washington,
D. c., Agricultural Research Service and Public Health
Service, Washington, D. C., National Air Pollution Control
Administration, 9p., ((1968)). 6 lets.
884
photochemical oxidants and air pollution
-------
The effects of oxidants in general, including ethylene and
NOx on plants are discussed. The problems of chronic plant
damage and synergistic effects, such as those discovered for
ozone-S02 mixtures, are considered and are shown to be
difficult to detect and evaluate. Projections of ozone
concentration producing injury in various plants are presented, and
the topics of crop yield reduction and land use are briefly
covered.##
11157
Agriculture Research Council, London (England)
THE EFFECTS OF AIR POLLUTION OH ELANTS AND SOIL. 53P., 1967.
202 refs.
An account of recent trends in the emissions and concentrations of
smoke, deposited natter and sulphur dioxide in Britain and summa-
rises the information available on the effects of these pollutants
on plants and soil is given. The literature on the effects on
plants and soil of fluorides and of photochemical, or oxidant, smog
which soie people think sight be troublesome in this country in the
future. A note on the contamination of plants neat highways with
lead from the exhaust fumes of sotoi vehicles is also included.##
11320
1. Crdin, H.A. Hall, 0.1. Kindinger
OXIDANT-IMDUCED INHIBITIOB OF EHZYHES INVOLVED IN CELL HALL
POLYSACCHARIDE SYNTHESIS. Preprint, California Univ.,
Riverside, Dept. of Biochemistry and California Univ.,
Riverside Statewide Air Pollution Research Center, 12p.,
1966. 12 refs. (Presented at the Air Pollution Medical
Research conference, Denver, Colorado, July 22-2U, 1968,
Session V: Biochemical Effects of Air Pollutants, Paper 1.)
The effect of the oxidants, ozone and perocyacetyl nitrate, on
the enzymes phosphaglucomatase, UDP glucose
pyrophosphorglase and cellulose synthetase Has studied. Levels
of peroxyacetyl nitrate (PAN) or ozone which inhitit oat
coleoptile section growth reversibly, inhibited formation of
cellulose and of cell vail non-cellulosic polysaccharides. After
treatment of intact cells with PAH phosphoglucomutase associated
with subcellular particles has sore severely inactivated than was
soluble enzyme. A particulate cellulose synthetase from
coleoptile was inactivated by either ozone or PAN treatment of
oat coleoptiles. It was concluded that oxidant induced inhibition
ot one or more of these enzymes accounts for reduced
polysaccharide synthesis.##
G. Effects -Plants and Livestock
885
-------
1 1407
C.R. Thompson, O.C, Taylor
EFFECTS OF AIR POLLUTANTS ON GBOHT.H, LEAf DROP, FBUIT
CROP AND YIELD OF CITRUS TREES. Preprint, California Univ.,
Riverside, Statewide Air Pollution Besearch Center, ((J1))p.,
((1966)). <(17)) re£s.
Commercially producing lencn and navel oianye trees were studied
to determine the effects of the air pollutant complex, especially
photochemical oxidants and fluorides, in the Los Angeles Easin
on the following responses: growth as shown by increased tree
girth and weight of prunings; leaf drop as measured by (a) total
weight of dried leaves collected under the trees, and (b) the time
which rcarked leaves remained on randomly selected branches; fruit
drop; and yield of mature marketable fru.it. The results showed
that tree growth measured by increased girth and weight cf pruning
removed were not affected consistently by the experimental
treatments. The rate of leaf drop was significantly less fcr
lemon trees where carbon filtered air was supplied to the trees
versus the unfiltered treatments. A similar trend was present
in oranges but was not significant statistically. The percent
cf lemon leaves which reaained on selected branches of trees
receiving filtered air as compared to unfiltered treatments after
18 months was 72.t vs. Fruit drop in lemons is of minor
significance but in navel oranges represents a serious problem.
Comparisons of check trees, unfiltered and carbon filtered air
trees showed fruit drop to be 82.5, 59.7, and 39.6, respectively,
all percents of which are statistically different at the 1* level.
Yield o£ marketable fruit is also reduced significantly by
photochemical oxidants. (Authors' abstract, modified)##
11501
Millet, P. R„„ j„ a. Parmeter, Jr., and B. Flick
TEE EFFECTS OF OZOHE OB PHOTOSYNTHESIS OF FCJIDEFOS* PISE.,
Preprint, California Univ., Eerkeley, Dept.. of Plant
Pathology, ('(32)) p., (<1968))., 28 refs..
The effect of chronic, sublethal ozone fumigations on apparent
photosynthesis, chlorophyll loss, the relative participation of
different aged needle whorls. Hill reaction rate of isolated
chloroplasts and pattern of C1U labeling in the photosynthate
of container-grown ponderosa pine were investigated. A depression
of the rate of apparent photosynthesis of container-grown ponderosa
pine was observed both with and without significant decreases of
chlorophyll concentrations following ozone fumigations.
Seedlings with two annual coapleaents of adult needles indicated
a slight depression of C1402 uptake with a 26 and 24* chlorophyll
decrease coupled vith a 10* suppression of apparent photosynthesis
estimated by infrared C02 analysis. Comparisons of healthy and
ozone injured chloroplasts at a single, saturating light intensity
886
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
indicated that the control chloroplasts reduced 0..U21 uM
DCIP/hr./ng chlorophyll ccnpared to 0.101 for an ozone injured
chloroplast suspension with equal chlorophyll concentration. The
ozone exposed plant, from which chloroplasts were taken, exhibited
a severe chlorotic mottle. One year old and younger needles lost
an equivalent anount of chlorophyll* following ozone exposure,.
However, there was a decided change in the distribution of Clil in
the two needle ages. Trees with three and four year's needle
retention were fumigated foe U0 days. The changes in apparent
photosynthesis for ozone danage trees is indicated. It was
concluded that the observed depression of apparent photosynthesis
was not related to a najor change or blockage of the nornal pathway
of the carbon reduction cycle.fI
11581
Denser, H. A. and G. H. Hodges
VARIETAL TOLERANCE OF T0EACC0 TC OZONE DOSE BATE. Agron.
J.., 60 (4) :3U9-352r July-August, 1968.. 19 refs.
The relative degree of ozone injury to genetically susceptible and
resistant tobacco (Nicotiaoa tabacua L..J plants, was determined.
Egual ozone doses derived from three ozone concentrations and nine
exposure intervals were imposed on three tobacco varieties in
fumigation experiments, length of exposure determined relative
injury at 0.10 ppn, but ozone concentration controlled injury when
plants were exposed at 0.20 and 0.,30 ppn. Ozone-resistant cv.
"Eel-B* sustained less than "J0)1 total injury fron a 0.15 ppmhr
dose given at any of the three ozone concentrations. A 0., 15 ppnhr
dose, however* caused significantly greater injury to
ozone-susceptible cv. "Bel-iO* at the two higher ozone
concentrations. Ozone caused almost 40* leaf injury to Bel-B
when plants were exposed to a 0.30 ppnhr dose at 0..20 and 0.30 ppn,
but total injury renained near 10* when the 0.30 ppnhr dose was
given at 0..10 ppn. Results indicate that varietal response to
ozone is controlled by exposure interval and concentration rather
than ozone concentration independently. Ozone dose rate affected
the size of fleck lesions displayed by Bel-H3. Leaves exposed
for 6 hr at 0.10 ppn developed flecks four to six tines larger than
the flecks obtained after 1 hour at 0.30 ppn.it
117U8
Taylor, 0. Clifton
EFFECTS OF OXIDANX AIR POLLUTANTS. (Presented at the
Symposium on Air Quality Criteria, June 5, 1966.) J.
Occupational (led., 10 (9) :485-499, Sept. 1968. 50 refs.
The interaction of the three najcr oxidants present in snog
(ozone, pecoxyacetyl nitrate and H02) in their effects on plants
is discussed and the need for analyzing the effects of combined
G. Effects • Plants and Livestock
887
-------
and successive exposures to fluctuating concentrations is
emphasized. As reported initially by Schuck, high concentrations
of hydrocarbons and NO develop during the night, but about 30
ainutes after sunrise the NO is almost zero and N02 has reached
a peak; the peroxyacetyl nitrate level increases gradually after
sunrise, and the ozone increases sharply as the N02 drops
towards zero. Susceptibility of plants to injury from air
pollutants is determined both by the action of stonates (which
can exclude injurious levels of soie toxic agents) and by internal
biochemical or physiological factors. Estimation of economic loss
from air pollution is simple when the product is a leafy
vegetable, but becomes more difficult in other cases, especially
when confused with the effects of insects, drought diseases,
(including virus infections) and nutritional factors.**
12034
0. Dugger, Jr., and l„ P. ling
T8E EPPECT OP PEBOIYACETTL KITH ATE OH PLANTS- PHOTOBEDDCTIV f
REACTIONS AND SUSCEPTIBILITY Of El AN PLANTS TO PAH.
Phytopathology, 58 (8) : 1102-1107, Aug. 1968- 31 ref..
The affect of peroxyacetyl nitrate (FAN), a photochemical air
pollutant, on plants has been studied by a number of
investigators. A brief review of tbe literature is presented.
In this study of the photoredactive reactions and susceptibility
of bean plants to PAN, evidence is presented to show that
sulfhydryl compounds in bean plants are synthesi2ed in the
light, Sulfhydryl content in these plants is a function of plant
age, light quality, and photoperiod, strongly correlating with the
light-plant-PAN interaction resulting in phytotoxicity.
Results are also presented to suggest that the oxidant
interaction with plants is a function of the photoreductive
process that occurs in plants when in the light. The oxidative
characteristics of ozone and PAN are coapared with respect to
plaat daaagc.••
12042
Heggestad, H„ E„
DISEASES OP CROPS AMD 0HNAM1HTA1 PLANTS INCITED BY AIR
POLLUTANTS* Phytopathology, 58:1089-1097, Aug. 1968., 80 ref.
Air pollution injury to crop and ornamental plants is increasing
in the O.s.A. Estimates of annual losses to agriculture from
air pollutants, which ranged fcoa $150 to $500 million during the
decade 1951-1960, ace now $500 Billion. Although most of the loss
is due to growth suppression or chronic injury, it is the acute
injury that suggests the nature of the air pollutant and reveals
the distribution of the problea* Each pollutant tends to produce
its own pattern of injury, leaving graphic records of air pollution
888
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
episodes.. Photochemical oxidants, ethylene, sulfur dioxide,
fluoride, and other pollutants produce Barked reactions in various
types of plants. The recent developments and current research
trends in the assessment of these reactions are reviewed.*#
12043
Hepting, G. fU
DISEASES OF FOREST AND THEE CROPS CAUSED BY AIR POLLOTANTS.,
Phytopathology, 58 (8) : 1098-1101, Aug.. 1968. 25 Ref„
Air pollution is one of the increasing and ever-changing
environmental stresses to which trees, especially, are exposed.
The plant pathologists are developing a body of information which
will provide them with the means not only to protect trees from
damage due to air pollution but to establish trees as cheap,
abundant, selective,, and relatively permanent monitors of chronic
air pollution of a low level of intensity. Examples of damage
caused by identifiable sources are cited. As knowledge increases,
foresters and pathologists can apply principles of selective
planting which will place automobile fume resistant trees where
traffic is heavy, coal or oil fame resistant trees around power
plants and steel sills, and fluorine resistant trees around
aluminum ore reduction plants and phosphate processing
industries.ft
120U5
Johnson, H.
THE HIGH COST OF FOOL AIB. The Progressive Farmer, 4 pp.,
April 1968.
The President"s Science Advisory Committee reported in 1965
that air pollution damage to plants had been observed in 27 states,
the District of Colombia, Canada, and Hexico. Total damage
each year to crops in the United States is estimated at $500
million, feather fleck damage to tobacco, which is caused by
ozone, bas caused substantial crop loss in all producing states.
Sulfur dioxide, fluorine, ethylene, and photochemical smog axe
known to be harmful to plants. A research program to solve
unanswered questions, and a program to enforce the cleaning up of
pollution sources is urgently needed.it
12047
de Koning, fl» V. and Z. Jegier
Q0AMTITATIYI SBLATZOV BITMEH OZOKB COICBNTBATION ADD REDUCTION
OF PH0T0STM1HESIS OF ZUGLZRl GBACIIIS. Atmos. Environ.,
2(6)8615-616, Nov. 1968. 5 Kef.
G. Effects - Plants and Livestock
889
-------
The percentage reduction of photosynthesis is a logarithmic
function of the ozone concentration (0.. 2-1.0 ppm).. Chlorophyll
determinations following treatment with 0.8 ppnt ozone show a small
(5 per cent) loss of chlorophyll b and no loss of chlorophyll
a., (Author*s Abstract) t#
121U9
Heagle, Allen S.
EFFECT OF ICW-1EVEI OZONE FUMIGATIONS ON CKCWN HOST OF CATS.
Preprint, Public Health Service, Cincinnati, Chio, National Air
Pollution Control Administration, 10p., 1969 (?). 9 rets.
Exposure to 10 pphm ozone for 6 hr in the light 10 days afttt
infection significantly reduced the growth oi Puccinia corowta
uredia on the crown rust differential varieties of Avena sativa.
Urediospores produced on the plants that were exposed tc czcne
germinated as well, produced as many appressocia, and penetrated
stomates as well as spores produced on unexposed leaves.
Exposure on dry leaves to 20 pphm ozcne for 3 hr for 1-5 days
did not affect urediospore gerninaticn, appressoria formation,
and penetration. The suppression of the uredium developxent of
the crown dust fungus in this experiment was caused by ozone
levels commonly surpassed in many areas, suggesting that the
growth of this and possibly other plant parasites is affected by
photochemical air pollution. (Author abstract modified)
12155
Leone, Ida A., Eileen Brennan, and B. H. Daines
EFFECTS OF AIR POLLUTION ON VEGETATICil. Preprint, Air Pollution
Control Association, New York City, 6p., 1962. (Presented at
the Air Polltuion control Association, Hid-Atlantic states Section
fleeting, Wilmington, Del., Oct. 26, 1962.)
Phytotoxic pollutants are broadly catergorized as primary or
single source emissions and the products of photochemical
reactions arising frci urban expansion and vehicular traffic,
ftsong the primary contaminants, classified according to their
demonstrated order of toxicity to plants, are hydrogen fluoride,
chlorine, sulfur dioxide, amaonia, and hydrogen sulfide; to
these may be added ethylene and perhaps natural illuminating
gas. The acute and chronic types of injury caused by S02, the
earliest Known offender, and by hydrogen fluoride are described.
The latter is the most insidious of the phytotoxic pollutants,
since it is injurious to certain sensitive species at fractions
of a part per billion. The two most significant pollutants from
photochemical reactions are ozone, which generally attacks the
upper leaf surface of sensitive plants, and oxidized
hydrocarbons. The chief offender of the oxidized hydrocarbons
is peroxyacyl nitrate and its analogues. Plant injury from
specific pollutants can be diagnosed by particularly susceptible
890
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
species or indicators, by type of symptom, and by significant
emission sources in the vicinity. Air quality and meteorological
data from three New Jersey communities - carlstadt, New Brunswick,
and Bordentown - are briefly reviewed in relation to phytotoxic
episodes. Possibe control measures in combatting pollution
damage to plants include anti-oxidant sprays and the breeding of
resistant plant varieties.
12166
Frances A. Hood* John B.. Coppolino, Donald Davis, David
Drumflrond, and Bay Wilhour
AIR POLLUTION EFFECTS (IWTEIUJf PROGHESS SEPOPI,) Pennsylvania
State Univ.,, Oniversity Park, Center for Air Environment
Studies, ((95)) p.,, Jan.. 1969.. 4 refs.
An exposure system has been cenetructed out-of-dcors which will
permit the exposure of several hundred plants simultaneously to
low levels of ozone or peroxyacetylnitrate (PAN) for extended
periods of time, and a series of plant growth chambers for use in
studies of pre- and post-funigation environmental influences on
plant response have been purchased and checked out.
Approximately 9,000 seedlings of 34 different tree species have
been acgulred for exposure purposes and procedures have bees
developed for handling and maintenance of the plants..
Approximately 4,000 seedlings of the 34 species have been exposed
to 25 pphn ozone for 8 hours; 16 species were found sensitive.
Nine of the species were conifers, seven were hardvoods, and
Virginia pine, jack pine, Austrian pine, white ash, green ash,
and white oak were among the most sensitive. Symptoms that
developed on the 16 species were described in detail. Host of the
16 species were resistant during the first nonth following bud-
break.. Plants were sensitive foe periods of 6 to 14 weeks during
the growing season and they maintained about the sane level of
sensitivity as age of the current tissue increased. Virginia pine
and white ash were selected for intensive studies of the influence
of pre-, during, and post-funigation environmental regimes on
plant response to ozone. Preliminary studies indicate that high
temperatures and/or high relative humiditie during the pre- and/or
post-fumigation periods enhance the development of symptoms on
both species.##
12944
Applegate, Howard 6. and lane C. Durrant
SYNERGISTIC ACTION OP OZOHE-STJIFDB DIOXIDE 0» PEANUTS. Environ.
Sci. Techno 1., 3(8| :759-760, Aug. 1969. 8 refs..
Peanut plants were funigated with ozone and sulfur dioxide
singly and together. When applied separately, both gases
induced characteristic damage to th« plants. Ozone-induced
injury first occurred on hlgh-aoisture plants 24 to 48 hrs after
G. Effects - Plants and Livestock
891
-------
the start of furtigation. The mast aiature leaflets turned
chlorotic, starting at the middle and progressing toward the
nargin. Ultimately, while chlorotic but not necrotic, the
leaflets abscissed. Sulfur dioxide-induced injury occurred on
high-moisture plants if to 8 hrs after the start of fumigation.
The youngest leaftlets first turned a light tan, and later a
darker brown, along the margins.. If fumigation continued, the
necrosis progressed along the veins into the middle of the
leaflet,, The entire leaf abscissed when necrosis was complete.
A synergistic action not characteristic of individual gases was
found when the two gases were administered simultaneously.
Four to five hrs after fumigation, a chlorosis similar in color
to ozone injury alone appeared on the yousgest leaflets of
high-moisture plants. In conttast to the ozone-induced injury,
the chlorosis started at the margin and progressed slowly to
the midvein. After **6 to 50 hrs, the marginal chlorotic areas
turned a light tan similar in color to the sulfur dioxide-
induced injury. The necrosis progressed slowly inward and
ultimately the leaf abscissed*
1317U
POLLUTION DHAHFS WHITE PIKES. Agri. Bes., 18(2) Aug. 1969.
Air pollution is currently causing chlorotic dwarf disease in
the eastern white pine (Pinus strobus L..), an important lumber
source. Dwarfed pines have a sickly, mottled yellow color, are
much smaller than normal pines, and eventually die from the
disease. Investigations have established the contaminant as
either sulfur dioxide, ozone, or an interacting mixture of both
gases.. Dwarf-susceptible pines developed intense disease s;mptcm«
when exposed to mixtures of ozone and S02, each at a concentration
of 6 to 10 pphm. serious symptoas also developed in susceptible
pines exposed to 6 pphm S02. An Ohio survey reports over 30% of
the pines in plantations and io young natural stands have the
disease, and some pines were found to be genetically resistant to
chlorotic dwarf.
13T7t
POltCITroH DWAFFS WHITE PINES.
EFFECTS-PLANTS AHD LIVESTOCK:
pines, chlorotic dwarf disease
Air pollution is currently causing chlorotic dwarf disease in
the eastern white pine (Pinus strobus L.) , an important lumber
source. Dwarfed pines have a sickly, mottled yellow color, are
much smaller than normal pines, and eventually die from the
disease. Investigations have established the cont&ainamt as
either sulfur dioxide, o*one, or an interacting mixture of both
gases. Dwarf-susceptible pines developed intense disease symptoe*
Agri. Fes., 16(2) -.H, Aug. 1969.
Sulfur dioxide, Oione, White
892
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
when exposed to aixtures of ozone and S02, each at a concentration
ot 6 to 10 pphm. Serious symptoms also developed in susceptible
pines exposed to 6 pphn S02. An Ohio survey reports over 30* of
the pines in plantations and in young natural stands have the
disease, and some pines were found to be genetically resistant to
chlorotic dwarf.
11063
Hibben, C. II.
THE DISTINCTION BETBEEN INJUR 1 TO TH1E LEAVES BY OZONE AND
HESOPHYLL—FEEDING LEAFHOPPIHS. forest Sci., 15<2):15U-158, June
1967. 9 refs.
Both mesophy11-feeding leafhcppexs and ozone cause white flocks
on tbe leaves of a variety of herbaceous and woody plants, and
the superficial similarities between these syaptoss can lead to
incorrect diagnosis of leaf damage. Bhen contrasted
¦icroscopically and histologically on leaves of sngar maples,
flowering dogwood, and northern red oak, tbe phytotozic effects
of both agents were distinguished by differences in location,
configuration, color, and size of external injuries and by
characteristics of affected palisade parenchyma cells.
Predominate ozone symptoms were adaxial flecks 0.1 to 0.5 ma in
diameter, consisting of discolored parenchyma cells in the vein
islets, leafhopper-induced injuries were usually 0.25 to 1 an
in dianeter, white, and confined to the adazial surfaces of
leaves* They were characterized by fan-shaped sectors internized
with green tissue. Dogwood was acre resistant to 03 than naple
and oak. The three species displayed sinilar internal ozone
injuries: protoplast and cell wall collapse of palisade parenchyia
cells. Leafhopper feeding produced palisade parenchyma cells
devoid of recognizable contents. It is not known whether the sane
aechanical and/or physiological mecbaniss governs the sensitivity
of the palisade parenchyma cells to two such dissinilar irritants.
1H351
Reaver, G. 8. and H» o. Jackson
BU1TI0NSHIP BETHEEN BBONZING II WHITE BEANS Alb PHYTOTOXIC
LEVELS OF ATH0SPH2BXC OZONI IN 0BT1BI0. Can. J. Plant Sci.
(Ottawa), vol. 48:561-568, Nov. 1968. 13 refs.
studies on the effects of ozone were conducted in tbe laboratory
and at three field locations in Ontario. Controlled ezposure
studies indicated that white beans are sensitive to at least
8.4 pphn (parts per hundred >illion| ozone after 6 hrs of
exposure. The array of syaptoss include necrotic stipple
through disruption of the palisade parenchyia, chlorosis,
blanching# and leaf and pod abscission. Leaf naturity also
¦odified sensitivity to ozone* Concentrations of ozone as high
G. Effects • Plants and Livestock
893
-------
as 9 ppha were detected during aid-August in association with
the incidence of the bronzing disorder of white beans io three
regions of Ontario is 1965 and 1967.. The disorder is
characterized by the sudden appearance of a bronze-colored
necrotic stipple of pods and the upper surface of the leaf,
followed by chlorosis and abscission of both leaves and pods.
Conformity between field syaptcaatology of bronzing and the plants after
phytotoxic exposures, because of the progressive chlorosis and
abscission of both leaves and pods..
11826
Feder, William A. and Franklin J. caapbell
INFLUENCE OF LOU LEVELS OF OZONE ON FLOBEHING OF CARNATIONS.
Phytopathology, vol. 58:1038-1039, July 1968. 3 refs.
The effects of the exposure of carnations to low levels of ozoae
for a prolonged period were investigated in a controlled study.
Carnations grown in the presence of ozone at levels below
which visible injury usually appears were damaged: an average
level of 0.075 ppa for about 10 days depressed bud foraation
in Shite Sia carnations if the plants were exposed to the ozone
at the tiae of bud initiation. Exposure periods of eight weeks
at these ozone levels were requited before tip burn syaptoas
appeared, whereas such damage was evident only t»8 hr after
the plants were exposed to oxidant levels of Q.12-0»15 ppi
for an 8-hr period. No tip burn occurred in plants grown
in filtered air, in addition, plants in the ozone-charged
air vere bushier and shorter than the control group.
14962
Hill, A. c», H« Faclc, H. Treshow. 8. j. Downs, and L. G„
Transtrua
PI A NT INJUBY induces BT OZONE. Phytopathology, vol. 51:356-363,
June 1961. 18 refs.
phytotoxicity of ozone to 34 plant species was studied in
controlled-ataosphere greenhouses. Plants vere snbjected at
various stages of growth to 0-13-0.72 ppa ozone for 2-hour period®„
Injury syaptoas developed on 28 species. Soae of the aost
894
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
sensitive species were saall grains, alfalfa, spinach, and
tobacco. There was a general tendency for sensitivity to
increase with aaturity of tissue. Palisade cells were most
readily injured by ozone„ On plants with adaxial palisade
parenchyia, chlorot'ic spots and bleached necrotic areas
developed on the upper leaf surface. Injury was equally apparent
fron either leaf surface of plants vith undifferentiated
¦esophyll. Necrotic spots extending completely through the
leaf developed on plants with either aesophyll structure when
injury was severe. Ozone caused conspicuous tumors to develop
on broccoli leaves. Syaptoas siailar to those produced by
ozone fumigations were observed cn a wide range of plant species
growing near several large aetropolitan centers. (Author susaary
aodified)
14963
Menser, H. A., H„ £. Heggestad, and 0. E- Street
RESPONSE OF PLANTS TO AID POLLUTANTS.. II. EFFECTS OF OZONE
CONCENTRATION AND LEAF MATURITY ON INJOBY TO NICOTIANA TABACUH..
Phytopathology, 53 <11) :1304-1308, 1963. 21 refs..
The relation of ozone concentration, leaf aaturity, and
resistance of 4 tobacco varieties Has investigated by exposing
greenhouse plants to ozone in a carbon-filtered, funigation
chamber. Replicated, 2-hr experiments at 0.10, 0.16,
0.22, and 0.28 ppa ozone showed the <4 varieties exhibited 3
sensitivity levels. Bol-W3, a weather-fleck sensitive selection,
was injured at 0.10 ppa* while 0.22 ppa ozone was required to
dawage the fleck-resistant Bel-B variety. Ozone sensitivity
was inversely related to leaf aaturity, as determined by rate of
leaf expansion. Recently aature leaves were wore ozone-sensitive
than overaature or rapidly expanding leaves. Ozone lesions were
uniforaly distributed over the upper surface of recently nature
leaves; only tips of expanding leaves were daaaged. The
¦aturity-related pattern of injury in soae respects resenbled
Los Angeles snog injury to Nicotiana glutinoaa. (Author
suaaary aodified)
1M966
denser, H. 1.., Jr.# H» E* Heggestad, and J. 0. Grosso
CAftEON FILTER PHEVINTS OZONE FLECK AND PBEBATUHE SENESCENCE OF
TOBACCO LBAVES. Phytopathology, S6(4):466-467, April 1966.
? refs.
The purpose of this study was to investigate vith a charcoal
filter the relation of air pollution to ozone fleck and preaature
leaf senescence in the eastern USA where ozone concentrations
ace auch lower than those observed in southern California. Two
varieties of tobacco plants (Bel-U3 and were grown in
identical plastic covered chaabers that received either carbon-
6. Effects • Plants and Limtock
895
-------
filtered or aabient air. Maxima aeasured ozone concentrations
ranged between 2.0 and 8. 88 ppha in the aabient air chaaber,
there was no ozone in the filtered air chaaber. Neither ozone
fleck nor preiature leaf senescence developed on the leaves of
plants grown in air passed through the activated charcoal filter.
Plants grown in the aabient air displayed both flecking and
preaature senescence, and the syaftcas increased concomitantly.
Both Bel-B3 and Bel-B showed siailar tendencies toward preiature
leaf senescence, although displaying different susceptibility
thresholds. It is concluded that the leaf senescence observed
in the aabient air resulted froa initial destruction of tissue
by air-polluting ozone rather than froa poor aoisture conditions
ox inadequate nutrition, factors coaaonly associated with leaf
senescence.
14968
Daines, Bobcrt H.# Eileen Brennan, and Ida Leone
AIB POLLUTANTS AND PLANT BESPONSI. J. Forestry, 65(6) : 3ei-38*»_
Jane 1967. 15 refs.
The effects of a nuaber of acid gases and photocheaically-
produced pollutants on plants are described. A great variation
in susceptibility to daaage by such gases as fluorides and S02
exist both aaong plant species and within a single species.
Injury froa these gases occurs priaarily to younger leaves,
with little or no daaage shown by old leaves. Syaptoas usually
consist of aarginal and tip necrosis with accoapanying
discoloration of the affected areas. Liaited studies with
chlorine suggest that it is less phytotoxic than hydrofluoric
acid, requiring about 0.1 ppa to injure the sore sensitive
plants. Aaong the photocheaically-produced pollutants,
ozone has been known for aany years to be toxic to a wide variety
of plant species; ozone toxicity syaptoas appear as flecks,
stipple, streaks, spots, and tip necrosis. Injury appears on
¦ature leaves, with the oldest leaves of young plants and
¦iddle-aged leaves of old plants being aost susceptible.
Peroxyacetylnitrate (PAW) and its analogues are highly phytotoxic,
producing syaptoas called "silver leaf" and 41 leaf banding" in
California* the northeastern 0. 5., and other urbanized areas,
like ozone, these coapounds are believed to cause severe annual
econoaic losses in crop daaage. Investigations of daaage caused
by other photocheaical pollutants, naaely ozonated hydrocarbons,
bisulfite reaction products, and nitrogen dioxide, are briefly
sunaarized, and the aajor sources of all the pollutants
discussed are noted.
15266
Dass, H. C. and G. B. Reaver
H0DIFICATI01 07 OZONE DAMAGE TO PHASIOLOS VULGARIS BY
ANTIOXIDANTS, THIOLS AND SOLFHYSBTL BEAGENTS. Can. J. Plant
Sci.. (Ottawa), Tol. tt8s569-574, 1968. 13 refs.
896
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
The nechanisn of the "bronzing* effect of ozone on white beans
{Phaseolos vulgaris)p and the degree of protection, if any,
offered by various compounds, were investigated. Representative
cultivars of white bean were treated with selected antioxidants,
thiol coapounds, and sulfhydryl reagents and then exposed to
ozone under laboratory conditions, severity of the bronzing
disorder vas influenced by such treataents, as vas the activity
of peroxidase and lactic dehydrogenase enzymes. Dust applications
of the antioxidants* ascorbic acid and nickel-N-
dibutyldithiocarbaaate Markedly reduced ozone injury* the latter
compound being the aost effective. Decreased ozone sensitivity
was also noted following treatment of a susceptible and a
tolerant cultivar with the thiols cysteine hydrochloride and
glutathione. The severity of bronzing vas increased over that of
the control plants by the application of the sulfhydryl reagents
parachloroaercuribenzoate and R-ethyl aaleiaide. Necrotic
stipple of the upper surface of the laaina, a syaptoa associated
with the bronzing disorder, vas induced following treatment with
the sulfhydryl reagents without exposure to ozone. Ozone
fuaigation increased peroxidase activity and decreased lactic
dehydrogenase activity, siailar effects were observed fallowing
treataent with parachloroaercuribenzoate. Neither enzyae showed
response to the application of cysteine hydrochloride. The role
of protein sulfhydryls is discussed is relation to ozone daaage
and the bronzing disorder. tAvthor abstract aodified)
15332
Hibben, C. R. and G. Stotzky
EPPECTS OP OZONE ON THE GERMINATION OP FUNGUS SPORES. Can. J.
Microbiol,, 15 (10): 1187-1196, Cct. 1969. 37 refs.
To deteraine whether air pollutants increase plant infection by
fungi, an investigation was undertaken of the effects of low
concentrations cf ozone on the geraination of detached conidia,
ascospores, and sporangiospores froa 14 saprophytic and plant
pathogenic fungi. Geraination data were calculated for spores
on solid nedia, in liguid culture, and in a dry condition.
Detached spores varied in geraination after exposure on agar
to 10 to 100 pphm ozone for 1 to 6 hrs. Large pigmented scores
of chaetoaiua sp., Steaphyliui sarcinaeforae, S. loti, and
Alternaria sp. were insensitive to 100 pphm. Spores of
Trichoderna viride, Aspergillus terreus, A. niger, Penicilliun
egyptiacua, Botrytis allii, and Bhizopus stolonifer were reduced
in geraination priaarily by 50 and 100 ppha for the longer
exposures. Saall hyaline spores of Fusariun oxysporua,
Colletrotrichua lagenariun, Verticilliua alfco-atrua, and V.
dabliae were the aost sensitive; their geraination was prevented
or reduced by aost exposures to 50 and 100 ppha and occasionally
reduced by doses as low as 25 ppha for 4 and 6 hrs. Extended
exposures up to 28 hrs reduced geraination of A. Terreus, A.
niger* and P. egyptiacua spores to below 50* of the controls.
Lower doses of ozone soaetiaes atiaulated spore gecaination.
Fungus colonies aaintained in an ozone ataosphere bad abnoraal
growth characteristics. Ozone had little inhibitory effect on
air-dried spores or spores in a liquid aediua. (Author abstract
aodified)
6. Effects
-------
15382
Kotaka, S., A. P. Krueger, and E« c„ Andriese
THE EFFECT OF MB IONS ON LIGHT-INDUCEB SWELLING AND Dm-INDUCED
SHRINKING OF ISOLATED C HLO SOP LASTS. Intern.. J. Biometeorcl.
ILeiden), 12(2):85-92, I960. 9 refs.
Experiments were conducted to determine the effects of gaseous
ions on isolated spinach chloroplasts maintained in a
physiologically active state. Chloroplasts shrink when stored
in the dark for U8 hrs at 1 C and swell again when illuminated™
The rates of swelling and shrinking, determined by light-
scattering techniques, are increased by exposure to both positive
and negative air ions.. If chloroplasts are preilluminated for
30 min, the rate of shrinking of air-ion-treated chloroplasts
is increased, Vhen the chloroplasts are illuminated again, the
rate of swelling of air-ion-treated chloroplasts is lower than
that of controls. If 2.5 nH of adenosine triphosphate
{ATP) is added to the system upon the reillumination, the
swelling rate of ion-treated chloroplasts is markedly increased.
However, adenosine diphosphate JADP), p-nitropheny1 phosphate,
and inorganic phosphates are without effect. Prolonged
illumination (5000 foot candles for U8 hr) or the addition
of NaF inhibits the swelling and shrinking phenomenon. Exposure
of the chloroplasts in the presence of ATP to unipolar ionized
air of either charge at 4 C in the dark increases their
swelling and shrinking and ATPaee activities. These data
suggest that air ions stimulate ATP metabolism of isolated
chloroplasts.
15482
Seidman, Gabriel and Wilson B. Biggan
SIOJJATAL OPENING IK P1MT0 BEAM DORIHG DAYLIGHT HOUHS. Eotan.
Gaz., 130 (2):116-118, June 1969. 3 refs.
A year-long investigation of daytiue stcmatal movements of the
primary leaves of 11-day-old pinto tean plants was conducted.
New plants were used for each bihcurly reading. Light,
temperature, atmospheric pressure, relative humidity, time of
day, and month of year were the parameters studied. Stomatal
opening was measured with a modified Alvim pocometer on the
eleventh day after planting. Atmospheric pressure, light
intensity, temperature, and relative humidity varied during
the year in the greenhouse, but in the grovth chamber, light and
temperature were controlled. Cf all the variables, only the
coefficients for the month of the year and the hour of the day
were important in explaining the size variations in stonata of
growth chamber plants. After dawn, Etonatal opening increases
gradually and reaches a peak at noon in the greenhouse and at
2:00 p.a. in the growth chamber. In the greenhouse, the decrease
i« stoaatal opening at 2:00 p.m. was not statistically different
from noon, but the decrease in stcmatal size at 4:00 p.m. was
898
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
statistically different from both noon and 2:00 p.m. In the
growth chamber, stoiratal cpening at 4:00 p.m. was somewhat
smaller than at 2:00 p.m., but this difference was not
significant. This daily pattern was not explainable in terms of
the parameters that were examined in the growth chamber and the
greenhouse. Carbon dioxide concentrations, which varied
throughout the day, were highest at 8:00 a.m. and lowest at
U:0G p.m. The widest stomatal opening at midday did not
correspond to the lcwest carbon dioxide concentrations. It was
concluded that the findings indicate that endogenous factors
probably exert a greater influence on stomatal movement than
was demonstrated.
15192
Feder, Silliam A., Franklin Campbell, and Norman V. Butterfield
TIP BOPS, AN OXIDANT INCITED BESPONSE OF CARNATIONS. Plant
Disease Beptr., 51<9):793, Sept. 1967.
leaf tip burn was observed on greenhouse carnations in
Massachusetts and occurred only on the younger leaf tips of young
plants., the tips were killed and turned a straw brown color.
Symptoms extended frcm a few mm to 2-3 cm back from the tips
and were set off from the rest of the leaf by a sharp margin;
tissue below the burned tip was healthy. Damage was restricted
to the affected tips and persisted while the rest of the plant
continued to grow normally. Microscopic examination of the dead
leaf tips revealed no pathogens. The incidence of carnation tip
burn occurred within 24-48 hrs after a 3-day period during which
a high level of oxidant was recorded la the waltham, Bass,
area. Levels during this period exceeded 10 ppha for 4 hrs and
averaged over 6 pph» for the 72-hr period. Carnations growing in
air pollution study chambers in charcoal-filtered air were free
of tip burn, whereas those grown in chambers receiving unfiltered
air had a high incidence of tip burn- The evidence points to some
airborne toxicant as the apparent cause of tip burn. The high
oxidant level recorded just before the damage seemed to implicate
ozone as one possible cause of carnation tip burn* However* the
damage may actually be caused by a lixture of toxicants including
ozone™
15514
Taylor* 0. Clifton
IBPCHTANCI OF P1ROXTACHTYL NITRATE (PAN) AS A PHTT0T0XIC AIB
POLLUTANT™ Preprint. Air Pollution Control Assoc., Pittsburgh,
Pa., 23p., 1968. 25 refs. (Presented at the Air Pollution
Control Assoc., Annual Meeting, 61st, Saint Paul* Hinnesota,
June 1968, Paper 68-168.)
Peroiyacyl nitrates are a family of compounds resulting from
G. Effects - Plants and Livestock
899
-------
photochemical reactions between contaminants released to the
atHOsphere by coabustion of organic fuels. Peroxyacetyl nitrate
is the *ost abundant eeetei of this faaiily and is responsible
for seriojs plant injury in so»e polluted areas. Plant injury
has been recognized in at least 19 states and several foreign
countries, but econ atic loss causes greatest concern in California,
where levels of the toxicant frequently exceed those required
to produce plant injury. Characteristically, injury fron PAN
appears as glazing or bronzing of the lover leaf surface, but
the sympton syndrowe also includes tissue collapse, chlorosis,
and leaf drop- PAS inhibits activity of several eazyne systems
by attacking the sulfhydryl gccuF "hen enzyne extracts are
£a»igated in vitxo. PAH can produce visible sy*ptons when
sensitive plants are exposed for hoars to about 14 ppb„ other
Beobers of the faaiily (peroxypropionyl nitrate, percrybutrye
nitrate, ana perc*ybtenzojl nittate) at© sote tonic than PAru
Concentrations of 20 to 30 ppb PAH are cones in Riverside,
California, where a taxiius peak of 58 ppb was measured for oae
2-hour period.. Peaks as high as 54 ppb in Salt lake City and
210 ppb in Los Angeles, have been reported. Peroxyacyl nitrates
are also important eye irritants in atacspheres contasinated by
effluents froa organic conbustion.
15535
Price, Harvey Edward
THE 2PPBC1 OF 020HE 01 1TFIE PBODCCTIOB IS THE PtJBGUS
BILBIBTHOSPCBIOH SWITJDB. Utah Univ., Salt lake City, Dept. of
Bctaav, T1iss1b
-------
FACTOBS INFLUEHCING EXPBESSIOH or OXIDANT DAMAGE TO PLANTS.
Ann. Rev.. phytopathol., vol. 6:165-188, 1968. 101 refs.
The sensitivity of plants to oxidants, conditioned by a nuaber
of external factors to which the plants are exposed, was
reviewed,. Research supports the thesis that the stoaatal
apparatus mast be open before the phytotoxicant can enter the
sensitive aesophyll areas of the leaf and cause daaage* There
is both direct and indirect evidence to support the view that
the stoaata are only a pathway for the entrance of the pollutant,
and not the priaary aechanisa controlling injury. It was
suggested that the aechanisa which controls resistance of plants
to oxidant pollutants nay be siailar to the one which controls
resistance to other extreaes in the environaent. Plants are
aore sensitive when grown under a short photo period and at low
fertility levels, A long dark period prior to exposure increases
sensitivity. Plants grown under low light intensities are aore
sensitive to ozone and less sensitive to peroxyactyl nitrate
(PAN). low teaperatures for one to several days prior to
exposure or growth under drought conditions reduce sensitivity.
Sensitivity at tiae of exposure increases with increasing light
intensity and huaidity. Sensitivity of plants exposed under
natural conditions is affected aore by light intensity than by
tenperature.. High carbon dioxide levels at the tiae of
exposure reduce sensitivity. Plants exposed under any soil
conditions that produce a water stress in the plant show an
increased resistance. Injury froa PAN is aediated by a
light-sensitive systea within the plant, sulfur dioxide acts
synergistically with both oxone and nitrogen dioxide on sensitive
plant tissues. The presence of pathogens aay also affect
sensitivity as well as a slight change in the aicro-environaent
of a leaf. Plant sensitivity increases during aid-day exposure;
it is also affected by aaturity. (Author suaaary aodified)
15578
Ordin, I. and T~ L. Teng
PEBOXYACETYL NITHATE INDUCED INHIBITION OF GHEES PEA STER GROWTH.
Preprint, California Univ., Riverside* Dept. of Biocheaistry
and statewide Air Pollution Besearch Center* 11p.# 1968(7).
8 refs.
Preliainary data are reported for the effect of peroxyacetyl
nitrate (PAD) on growth and cell wall aetabolisa is steas froa
nine-day old peas. Gassing of intact plants in light with 2.4
ppa PAH for 11 hoars inhibited stea growth by 321. Decapitated
plants showed 45% inhibition of groHth but decapitated plants
treated simultaneously with 11 idoleacetic acid (IAA) and IX
gibberellic acid fGAJ showed only 15S inhibition. However,
danage to residual leaves was seen even on the horaone treated
plants. freataent of plants with 5.0 ppa PAN in darkness produced
neither leaf daaage nor inhibition of growth. Plant sections
treated with 2.7 ppa PAN adsorbed and respired added glncose
at control plant rates or slightly tore rapidly, bat cell vail
aetabolisa was inhibited. Excised sections exposed to 23 ppa PAN
G. Effects • Plants and Llmtock
901
-------
in darkness or in light grew less than controls when subsequently
placed in KC1 growth solutions. Added IAA reduced grovth
inhibition in these excised sections. The data suggest that intact
plant stems do not absorb enough PAH in darkness far their
metabolism or growth to be affected at levels affecting then in
light. The mechanism by which excised sections absorb PAN in
darkness presumably does not involve light,. The inhibition
of intact stem growth in the light might be due to an
insufficiency of auxin and/or nutrients leading in turn to
inactivation of growth-maintaining enzymes or to the formation
of inhibitory products from auxin which after transport react
with the enzyws. The role of endogenous auxin remains to be
investigated.
160S6
Dadd, N. J. F. and M. Efcert
FKEE RADICAL REACTIONS HODIFY CELLULAR DAMAGE. Nature, 221(5187):
1245-1246. March 29, 1969. 8 refs.
The properties of molecular species which are responsible tor cell
death in spores after irradiation were studied. Hadical groups
were recognized by their response to nitric oxide and oxygen
and titrated with these gases using both physical and biological
endpoints. Doses for E5H observations were 500 krad and those for
survival experiments varied from 1-10 krad given at 200 krad/min
and 3 krad/min respectively. ESB signals were ascribed to five
different radical groups. Groups I, II, and III were observed
within 10 nin of irradiation in N2, 02, and NO. In N2, group I
decays. In 02, group I, II and possible III decay, while group
IV grows at the expense ot the ethers. In NO, all but the
resistant group V decay. Group V radicals are recognized only
after decay of the other groups. The inactivation constant
for anoxic irradiation was increased by 02 post-treatment giving
full oxygen enhancement. In corresponding ESR experiments this
treatment initiates the formation of radical group IV and reduces
total radical population. Group I is not involved in the formation
of IV, but may be responsible for anoxic damage* Group IV is
correlated with the oxygen enhancement and may contain peroxy
radicals. Post-treatment with MO only removes the potential for
oxygen enhancement. Corresponding ESS experiments suggest that ttQ
prevent further biological damage by removing radical groups
1, II, and III. Although NO removes group IV, it does not reduce
the damage already caused by 02. NO and 02 interact faster with
the potential for oxygen enhancement during irradiation than in
post-irradiation treatment. Bates measured by ESB were slower
tban those found biologically. This suggests that the groups
are heterogeneous. The radicals of biological importance in
groups I and II react faster with 02 and NO than those of lesser
importance. Evidence showed that the potential for oxygen
enhancement does not reside only in initially produced species
but can be handed onto daughter species. Radical group IV
species responsible for oxygen enhancement, whereas group I
includes those responsible for irreversible damage produced in
anoxic conditions.
902
PHOTOCHEMICAL oxidants and air pollution
-------
162UU
Thomas, floyer D.
AIR POLLUTION WITH DILATION TO AGRONOMIC CROPS: I. GENERAL
STATUS OF RESEARCH ON THE EFFECTS OF AIB POLLUTION OK PLANTS.
Agron. J., vol. 50:545-550, 1956. 39 refs.
Plant damage caused by sulfur dioxide, fluorine compounds, and
smog is summarized. Sulfur dioxide causes two types of leal
injury: acute and chronic. The acute markings are marginal
or interveinal collapse areas; their color is usually ivory.
The chronic markings are areas cf limited cell injury but not
total collapse; the colors range from yellow to brownish-red to
white and represent fuaigaticn treatments or prolonged exposure
to low concentrations. No reduction in yields have been
demonstrated in plants exposed to sulfur dioxide unless there
was leaf injury. The fluoride pollution problem as two aspects:
direct injury to commercial and ornamental plants and the risk
of fluorosis in cattle and sheep exposed to contaminated
vegetation. Hydrogen fluoride and silicon tetrafluoride are
extremely toxic to a few plant species. Hydrogen fluoride in
ppb concentrations cause lesions resembling those due to sulfur
dioxide. Photosynthesis experiments, the results of which are
presented in tables and graphs, indicate that each crop has its
own threshold limit which varies from 5 ppb for gladiolus to
about 500 ppb for cotton. Smog damage to vegation is of two
kinds: that produced by London coal smoke or tog containing
sulfur dioxide; and Los Angeles smog, which is a mixture or
oxidants. California smog injury tends to appear as a band on
a leaf. Owing to the presence cf organic compounds, ozone damage
is rarely found in the field. The question remains open whether
leaf damage from London fog is due to sulfur dioxide or to other
toxicants.
16273
HacKnight, (lartha L.
THE EFFECT OF OZONE ON STOMA?Al APEBTUBE ANC TRANSPIRATION. Utah
Univ., Salt Lake city. Dept. cf Botany, Thesis (at), June 1968,
80p. 153 refs.
The effects of ozone on stomatal movement and transpiration were
investigated. Several species of plants were fumigated with ozone,
and stomatal aperatures were measured from leaf surface
impressions. Attached trifoliate leaves of Pinto beans were
enclosed in a small leaf chamber and were fumigated with ozone.
Tbe transpiration rate of the enclosed leaf was measured by
determining the difference in the relative humidity of the air
before entering, and after leaving, tbe leaf chamber. Ozone was
observed to cause stcmatal closure and the degree of closure varied
with the different plant species, since the degree of stomatal
closure for a given species varied inversely with the aacunt of
damage which subsequently appeared on the leaves, such ozone-
induced stomatal closure may afford the plant some measure of
G. Effects - Plants and Livestock
903
-------
protection iron damage by reducing further entrance of the toxicant
into the leaves. A 30-minute fumigation with 20-40 pphm ozone
caused a decrease in the transpiration rate of Pinto bean leaves.
Such a decrease in transpiration was inevitably followed by the
appearance of visible leaf damage. The age of the trifoliate
leaves was the most important factor in determining whether an
ozone-induced decrease in transpirate rate would be observed far
a given leaf. loung (3-8 days) and old (31-46 days) leaves showed
no transpiration decrease in response to ozone, whereas the medium
aged (19-24 days) leaves invariably displayed such a decrease.
The extent of the reduction in transpiration rate was dependent
upon ozone concentration, the season of the year, and the intensity
of light prior to fumigation. The time of fuoigation during the
day, the initial transpiration rate, the soil moisture, and the
presence of artificial lighting during growth, seemed to have no
effect on the extent of the transpiration decrease. The amount
of visible damage appearing on the leaf was related to light
intensity during and after fumigation, ozone concentrations, and
the season of the year. Leaf temperature was observed to be
inversely related to the transpiration rate. (Author abstract
modified)
16287
Tomlinson, Harley and Saul Rich
THE OZONE BESXSTANCE OF LEAVES AS BELATED TO THEIR SULFHYCBYi ANE
ADENOSINE TBIPHQSPHATE CONTENT. Phytopathology, vol. 58:808-810,
June 1968. 12 refs.
Experiments assessing the importance of sulfhydryl groups and
adenosine triphosphate in the ozone sensitivity of leaves are
reported. Ozonation lowered the sulfhydryl content of the
leaves of beans, spinach, and tobacco. Tobacco and bean leaves
treated vitb sulfhydry1-binding reagents, such as alpha-
iodoacetaaide and alpha-iodoacetic acid, developed symptoms
similar to those produced by ozcne. A tobacco variety resistant
to ozone was also more resistant to damage from sulfhydryl-
binding reagents than was a variety cf tobacco susceptible to
ozone. With leaves from the same tobacco plant, the older the
leaf, the more severely it was damaged by the sulfhydryl-fcinding
reagents. This parallels the pattern of susceptibility to ozone.
Ozonation also lowered tbe ATP content of bean leaves. Bean
leaves were made resistant to ozone by allowing them to take up
0.001 8 ATP through their petioles before ozonation. On tobacco,
the younger, more ozone-resistant leaves had higher concentrations
of both sulfhydryl groups and ATP than did the older, more
ozone-susceptible leaves. However, leaves of a tobacco variety
resistant to ozone contained lower concentrations of both
sulfhydryl groups and ATP than did comparable leaves of a tobacco
variety susceptible to ozone. (Author abstract modified)
16311
Brennan, Eileen and Ida A. Leone
SDPPHESSIOB OF OZONE TOXICITY SYMPTOMS IN VIBUS-INFECTED
904
photochemical oxidants and air pollution
-------
TOBACCO. Phytopathology, 50 (2):263-264, Feb. 1969. 12 refs.
Virus-free tobacco plants and those infected with tobacco mosaic
virus were exposed to ozone fumigations in an environmental
chamber. The objective was tc compare the response of normal and
virus-infected foliage ot tobacco with toxic concentrations of
ozone. Twelve nicotiana sylvestris plants, at the 6 to 8-leat
stage, were inoculated with tobacco mosaic virus (THV), and 12
were maintained as noninoculated controls. Both virus-infected
and virus-free plants were then exposed to 0.30 ppm ozone in a
fuaigation chamber for 3-6 hours. On the day following exposure
to ozone, typical symptoms of ozone toxicity always developed on
the virus-free plants, but never on those infected with THV.
Shorter time exposure showed less extensive damage to the healthy
plants, but again with no apparent damage to plants infected with
THV. Exposure of the virus-free tobacco plants caused visible
injury that was accompanied by certain biochemical changes that
were not observed in virus-infected plants. An increase in
respiration and nitrogen content and a decrease in carbohydrate
content of the foliage was observed. The mechanism of
protection of virus-infected plants provide against ozone is
unknown. The presence of the virus apparently hastens the
saturation of the tobacco plants. Other means that increase the
physiological age of the leaves may also offer protection.
16312
Tomlinson, Barley and Saul Bich
BELATING LIPID CONTENT AND FATTY ACID SYNTHESIS TO OZOKE INJUBY
OF TOBACCO LEAVES. Phytopathology, 59 (9):1284-1286, Sept. 1969.
10 refs.
Evidence is presented that fatty acid content may be a factor in
determining ozone resistance, and that tatty acid content
decreases in leaves exposed to ozone. Leaves of Nicotiana
tabacum were made more resistant to ozone injury by brushing
emulsions of lanolin, desylsuccinic acid, methyl palmitate,
palmitic acid, oleic acid, oc cottonseed oil onto the adaxial
surface. Effects of ozone on plants were produced by exposing
then to 1 ppm for one-half tc 1 hour. At the concentrations used,
these materials neither occluded nor caused abnormal movements of
the stomata. There was little difference in the total lipid
content of leaves from tobacco plants which were normally ozone
resistant oc ozone susceptible. However# there were significant
differences in their fatty acid content. Among plants of the
same variety or from genetically similar varieties, fatty acid
content was correlated witb ozone resistance. Tobacco leaves
exposed to ozone lost 60% of their saturated fatty acids, but
only 10* of their unsaturated fatty acids. (Author abstract
modified)
16313
Treshow, Hichael, Frances B, Harner, H. E. Price, and J. F.
Korselink
6. Effects >Plants and Liratock
90S
-------
EFFECTS OF CZCNE OH GROWTH, LIPID MET ABOLISH, AND SPOP.UL AT ION OF
FUNGI. phytopathology, 59 (9) .* 1223-122b, Seyt. 1969. 14 refs.
The possifcle effects of ozone on mycelial growth, spore production,
spore germination, and lipid metabolism were determined.
Fumigations with ozone at concentrations or 10 pphtn or more for
a hr repeated daily for 4 days suppressed radial growth and spore
production Qt Colletatrichum lindemuthiarmtn, the most sensitive
species studied. Neither radial nor mass growth of Alternaria
oleraceae, a more tolerant species, was inhibited by 60 pphm
oione, although spore production was significantly accelerated.
Since ozone did not affect spore viability, the inoculum
potential was greatly enhanced. Histological effects of ozone
included loss of pigmentation in C. lindemuthianum and abundant
formation of light-refractive globules in the hyphae. chemical
analyses of mycelial mats shoved an average 28% decrease ir.
neutral lipid content of czone-fumigated cultures. No differences
were detectable in fatty acid composition ot fumigated cultures.
While some lipids may have leaked into the substrate, it was
suspected that ozone penetrated into vital sites within the cell-
ozidizing sulfhydryl groups, thereby suppressing lipid synthesis.
The actual degree of suppression in fumigated hyphae may be
greater than indicated, since much of the mycelia analyzed grew
within the substrate and was not directly subject to ozone.
(Author abstract modified)
16354
Costonis, A. c. and W. A. Sinclair
RELATIONSHIPS OF ATMOSPHERIC OZONE TC NEEDLE BLIGHT OF EASTERN
WHITE FINE. Phytopathology, 59 (11): 1566-1571, Nov. 1969. 25
ref s.
A common needle blight of eastern white piae was found in field
and laboratory studies to be a syndrome of acute and chronic ozone
injury. Natural occurrences of acute symptoms on susceptible
field and potted trees were often related to specific prior
increases in aabient ozone concentration. Detection of this
relationship required needle elongation, so that new loci of injury
could be distinguished from older ones, ozone, administered at
tine-concentration combinations monitored in the atnosphere of a
rural pipe stand (3 pphm for 48 hr to 7 pphm for 4 hr), caused
acute injury to current-season needles on field and potted trees.
When sensitive trees were fumigated in a polyethylene chamber
in constant aist and sunlight (about 1.3^ cal/cu cm per ain) at
32-38 C, they were consistently aore severely injured than when
fuaigated with the saae concentration of ozone without mist
under a variety of other environaental conditions. New needles
ot sensitive field and potted trees remained nonsyaptomatic when
confined in polyethylene bags or when grown in charcoal-filtered
air. Acute synptons of ozone injury on sensitive needles of the
current seascn arise as silver flecks caused by collapse of
individual uesophyll cells beneath the staaatal surfaces of the
needles. These Bay coalesce to fori yellow to pink spots,
necrotic bands, and tip necrosis. Chronic symptoms are chlorosis
906
photochemical oxidants and air pollution
-------
and premature castzng of the elder foliage and slow growth of
trees. Individual trees vary greatly in sueceptibility tc ozone
injury. Susceptible trees are ircre sensitive during a 6- to 8-
week summer period when needles of the current seascn are
elongating. (Author abstract modified)
163 57
Otto, Harry U. and Robert H. Daises
GENESIS OF PHYTOTOXIC AIR P0LIU1AN1S AND THEIB IDENTIFICATION AND
MEASUREMENT EY CHEMICAL AND PfcOTOLOGIChi BE1H0DS. IEEE (Inst.
Elec. Ectron. Engrs.) Trans. Geosic, Electron., GE-8 (1) : 59-6*>,
Jan. 1970. 10b refs, (Presented at the First Annual Inter rational
Geoscience Electronics Symposium, Washington, D. C., April 1969.)
Phototoxic air pollutants derived from tombustion of fossil fuels
and from subsequent photochemical reactions in the atmosphere are
discussed. Among the major pollutants that adversely affect
vegetation are sulfur dicxide, ozone, peroxyacyl nitrate (PAN) and
analogs, nitrogen oxides, and ethylene. The chemical methods
currently employed to measure the occurrence of these pollutants
frequently lack specificity and sensitivity to specific pollutants.
In the absence of collabcrative testing, their reliability,
precision, and accuracy remain uncertain. Because the plant
kingdom serves as a constant atmospheric monitor, the chemical
methods should be supplemented by a study of plant response. Each
pollutant has its own spectrum of responding plant species aud each
produces a characteristic response for each species affected.
While man-made monitoring deviceE record exact chemical
concentrations unaffected by enviconnental factors and pollutant
mixtures, a plant responds biologically not only to concentrations,
but also to all other environmental factors that alter response,
i.e., humidity, soil moisture, light, temperature, etc. In
addition, the plant also responds to the total impact of the
pollution mixture.
16360
Broun, Leland B. and Clark 0. Eads
FACTORS AFFECTING THE APPEARANCE OF HOLLY OAKS IN SOUTHERN
CALIFORNIA. J. Econ. Entoicl., 62 (1): 11U-117, Feb. 1969. 5 refs.
The causes of the pcor appearance of mature holly caks, Quercus
ilex L, planted along parkways in San Marino, were investigated.
Tree foliage was sparse, and there also appeared to be a necrosis
and drooping of the small developing shoots. The new terminal
growth was associated with the presence of a leafhopper. Six
hydraulic sprays of oxydeaetonaethyl gave the best control of a
leafhopper, as coapared to list sprays of oxydesetoniethyl or
hydraulic sprays of DDT. No treatment yielded control of a
necrotic tip dieback that was attributed to the leafhopper. Dead
trees were felled and examined. Complete girdling by white fan-
G. Effects - Plants and Livestock
907
-------
shaped mycelial plaques under the coot bark and on the root bark,
black shoestring rhizonorphs of the oak root fungus Armillaria
mellea, were observed. Hot, dry Heather, and the possible
interaction of smog, also had very obvious effects o the
appearance of the trees. Following a smog alert, the trees had an
obvious reddish-brown hue added to their overall dark green
appearance. It was not possible tc correlate the appearance of
the trees with the irrigation practices of the property cwner
but the soil under the tree was dry and dusty. The most important
interacting factors contributing to the decline of the oaks, and
their death in some cases, was found to be, in probable order of
importance, root rot infection; inadeguate irrigation; bet, dry,
smoggy weather; and the necrotic dieback.
16362
Hibben, Craig R.
OZONE TOXICITY TO SUGAR MAPLE. Phytopathology, 59 (10) : 1 023-11*28,
Cct. 1969. 36 refs.
Sugar maples exposed to ozone under laboratory and field conditions
were less sensitive to ozone than Pinto bean seedlings. The
threshold level for visible injury to maple foliageafter short
exposures was 20 to 30 pphm for 2 hr. Extended intermittent doses
as low as 10 pphm at 2 br/day fcr 11 days caused slight injury.
Trees treated in the field were injured by ozone only slightly
less than potted trees treated under artificial conditions, but
understory saplings in the shade were not injured by a high dose.
There was great tree-to-tree variability in sensitivity.
Ozone caused disruption and collapse of palisade parenchyma cells
and adaxial flecks in the vein islet tissue; bifacial scorch
developed following exposure to higher doses. Immature leaves were
not injured by high doses. Ozone caused leaf abscission only
after severe injury by the higher doses. It sometimes induced
chlorosis on field trees but never caused twig dieback. Total
lipids in some ozone-injured cells were reduced, but no gross
changes in the lignin, cellulose, pectic, or starch constituents
of the cells were detected. There was no evidence of natural ozone
damage to trees when the external and histologic symptoms induced
experimentally were compared with those observed on sugar maples
growing in urban and roadside environments. It was concluded that
ozone is not an important causal factor in the etiology of sugar
maple dieback. (Author abstract modified)
16517
Tingey, David Thomas
FOIIAB ABSORPTION OF NITROGEN DICXIDE. Utah Univ., Salt Lake City,
Cept. of Botany, Thesis (HA), June 1968, U6p. 50 refs.
The uptake rate of nitrogen dioxide and its effects on
photosynthesis, transpiration, and stomatal closure in alfalfa
908
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
and oats here studied. Factors affecting the absorption rate,
such as concentration of N02, duration of exposure, light and
darkness, were evaluated- The results showed that alfalfa and oats
atsorbed N02 from the air in excess of 150 microliters N02/sg m
ground area/min when exposed to 2M ppha NC2. Nitrogen dioxide
uptake by alfalfa and oats decreased with tine when the plants were
exposed to 16 and 24 pphm N02, but remained constant when the
plants were exposed to 8 pphm N02. In artificial light, the
absorption rate of N02 decreased when artificial light intensity
was decreased; but when sunlight intensity was reduced, there was
no effect on N02 absorption, nitrogen dioxide absorption by
alfalfa in the dark was 40 microliters ti02/sg m ground area/nin
when exposed to 16 pphm N02 with a gradual increase in the uptake.
Oats exposed to 16 pphm N02 in the dark showed an erratic uptake
behavior with no evident trend. Nitrogen dioxide assimilation
showed a correlation to light intensity, probably because light
intensity influenced stonatal behavior. Carbon dioxide
assimilation and transpiration exhibited similar responses.
Nitrogen dioxide absorption data indicated that plants under
proper conditions should be able to remove a significant portion
of N02 from the air. The concentrations required to cause visible
damage to alfalfa was N02 with 200 pphm in the dark and 400 pphm
in the light. Oats required 600 pphm in the light and 800 pphm
in the dark. When oats and alfalfa were exposed to 8,16, and
21 pphm N02 for 4 hours, there was no reduction in photosynthetic
rate or transpiration. These same concentrations did not induce
stomatal closure. (Author abstract modified)
16617
Dost, Frank N., 0. J. Beed, and C. H. Hang
INORGANIC FLUORIDE PROPELLENT OXIDIZERS. VOLUME II. EFFECTS
UPON MICROORGANISMS, FISH, AND PLANTS. Oregon State Univ.,
Corvallis, Science Research Inst., Contract AF 33 (615J-1767,
Pro j. 6302, Task 630204, AMRL-TB-187 (vol II), 59p., Nov. 1S68.
7 refs.
CFSTI, DSC: AD 684176
The effects of the inorganic fluoride oxidizing agents (chlorine
trifluoride, chlorine pentaflucride, bromine pentafluoride, oxygen
difluoride, nitrogen trifluoride, and tetrafluorohydrazine) upon
selected species of microorganisms, fish, and plants were studied.
Interhalcgens were directly injected into water in a closed vessel
to provide a reaction mixture. The biological activity of
accidentally released chemical agents cannot be studied without
considering their reactions with soil, the atmosphere, and the
agueous phase of the environment. Hhether gaseous intoxicants
can contact biological species resident in aquatic media or soil
depends on the probabilities of dispersion of any given gas and
for its affinity for and/or reactivity with the physical substrate.
Each of the compounds studied is a candidate oxidizer for missile
propulsion. In acute exposure cf less than 1 hour, the
interhalogens, as gases, were destructive to plants at atmospheric
concentrations of 10-30 ppm; in agueous solution, they were lethal
to fish and microorganisms at concentrations of 10-25 micrograms
fluoride per milliliter. The latter effects resulted from
formation of inorganic acids and various oxidizing species, either
G. Effacts - Plants and Livestock
909
-------
of which is lethal alone and which can te neutralized by basic
compounds and reducing agents and by filtration through soil.
Oxygen difluoride was toxic to plants at concentrations in air as
lew as 1.5 ppm over a 30-min exposure period tut had no efiect
upon aquatic species. Nitrogen trifluoriae and
tetrafluorohydrazine are nearly innocuous to nonmaniicalian
organisms. (Author abstract modified)
167 Ct
Brennaa, Eileen and Ida A. leone
SUPPRESSION OF OZONE TOXICITY SYMPTCHS IN VIRUS-INFECTED TCEACCC.
Phytopathology, 59 (2):263-264, Feb. 1969. U rets.
Virus-free tobacco plants and those infected with tobacco cosaic
virus were exposed to ozone fumigations in an environntenta 1
chamber. A comparison of the effects of the czone revealed that
virus-free plants showed marked necrosis after exposure, while
infected plants exposed under the same conditions showed no
necrosis, in some tests run during the summer months, both
virus-free and virus-infected plants were equally damaged on
exposure to ozone. At present the mechanism cf protection that
virus-infected plants provide against ozone is not known. The
presence of the virus apparently hastens the maturation of the
tobacco plants. However, high N content or biochemical changes
induced by the virus may account for the resistance of infected
tissue to ozone damage.
169C6
Eussell, C.
EFFECT OF NITRIC OXIDE AND HYDROGEN SULPHIDE ON RADIATION
SENSITIVITY OF SPORES OF BACILLUS MEGATERIUM IN SUSPENSION.
Experientia, 22(2):B0-B1, Feb. 1966. 9 refs.
The effect of nitric oxide and hydrogen sulfide cn the radiation
sensitivity of wet spores in a buffered suspension was determined.
There was a slight sensitization by BO when present during
irradiation at a concentration of 0.5% NO in N2. Above that
concentration, the sensitivity of B. megaterium spcres decreased,
being below that in N2 when 100* NO was used. Sensitivity was
much lower when irradiation took place in H2S. The enhancement
of sensitivity due to pretreatment with NO required a minimum of
12 hours contact with the gas. Four observations showed that the
surviving fraction after irradiation in N2 was unaltered by
subsequent contact with 100* NO for 30 minutes. It was concluded
that the effects of NO on wet spores was qualitatively similar
to that found with a suspension of vegetative bacteria. The far
qreater protection shown by H2S may be a reflection of damage
inflicted by NO upon the metabolism of the cell, making it more
radiation sensitive.
910
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
16950
Dugger, H. K.
RESEARCH INVESTIGATING INTERACTION EETWEEN ATKOSPHEBIC OXILiAM'S
AND LIGHT IN PLANT SYSTEflS. Preprint, 8p., 1968 (3). 20 refs.
Research is proposed for continuing studies on the effect of
peroxyacetyl nitrate (PAN) on the fhotosynthetic mechanism and
the components of the Electron Transport System by using a
dual wave band spectrophotometer. Earlier research on the
effect of the guality of light in PAN damage to plants shewed
that red light (660 millimicrons) can induce damage response
in bean plants while far red light (700 millimicrons) induces
protection. Sulfhydryl (SH) compounds in bean plants are
synthesized in the light; a strong correlation exists between
the effect of plant age, light guality, and photoperiod on
SH content on susceptibility of the plants to PAN damage.
Also under investigation is the inhibitory effect of PAN on
cyclic phctcphosphorylation by chloioplasts from Black Valentine
bean leaves; inhibition in either the dark or the light
increases linearly as the PAN is increased, but complete
inhibition does not occur in the light; the ligh inhibition
requires more PAN than does the dark. In addition to a
continuation of the physiological studies on the SH content
of bean plants, research is being started to describe the
changes at the molecular level responsible foe the change in
the SH content of bean plants, particularly the increase
due to light. Other topics under investigation are the
effects of oxidants, especially ozone, on anthocyanin biosynthesis,
and permeability and carbohydrate metabolism changes induced ay
ozone.
16974
Certli, J. J.
EFFECT OF SALINITI ON SUSCEFTIEILIXY OF SUNFLOWER P1ASTS TO SMOG.
Soil Sci.r 87 (5);249-25 1, 1950. 10 refs.
Experiments which demonstrate a relationship between salinity
of nutrient medium and susceptibility of sunflower plants to smog
are reported. The materials and the methods are described. The
effect of smog on leaves of sunflower plants which were growing
in solutions of different salinities or at different moisture
tension is illustrated. The lost severe injury occurred on
recently natured leaves; young leaves at the growing points
resisted smog. The damage was concentrated more on the apical
parts on young leaves, while on slightly older leaves, the large
central areas were injured; on even cider leaves, the heaviest
damage was observed on the basal parts. The injury on opposite
leaves was strikingly symmetrical. Both salinity and high
moisture tension increased the resistance of sunflower plants to
smog injury. Plants grown in a 1-strength Hoagland solution
frequently shoved more than 50* of the leaf areas chlorotic or
G. Effects -Plants and Livestock
911
-------
necrotic; in an 8-strength solution, there was no visible damage.
Such results were obtained consistently during every siuog period.
Similar patterns of injury resulted inhen the plants were exposed
to sulfur dioxide or the oxides of nitrogen.
17038
Koeppe, David E. and Raymond J. Miller
LIAD EFFECTS ON COBS MITOCHONDRIAL BESPIBAIION. Science,
167 (3923) .*1376-1378, March 1970. 7 refs.
Oxidation of exogenous nicotinamide adenine dinucleotide and
succinate by corn mitochondria was measured as a function of lead
chloride concentration. Concentrations of 50-60 nicromoles/1
stimulated oxidation of exogenous reduced nicotinamide adenine
dinucleotide by 17
-------
17093
Stolzy, L. H., 0. C. Taylor, J. ietey, and X. E. Szuszkiewicz
INFLUENCE OF SOIL-OXYGEN DIFFUSION HATES ON SUSCEPTIBILITY 01
1CMAT0 PLANTS TO AIH-BORNE OXIDANTS. Soil Sci., 9 1 (3) : 15 1-155,
March 1961. 9 refs. (Paper No. 1254, University of California
Citrus Experiment Station, Riverside, California.)
A study was undertaken to determine whether oxygen conditions in
the soil-root envisonment influence plant susceptibility to
danage by air-borne oxidants. The materials and methods used are
described. The tomato plants subjected to the two low-oxygen
treatments could be visually separated from the plants in the
higher oxygen treatments the day after the oxygen treatments were
applied. The plants in the low partial-pressure treatments had
thick, dark green leaves; during afternoons, progressively more
wilting vas observed. Plants growing in the 10-mm. Hg.
treatments appeared to be almost normal in growth in comparison to
the control plants. In the 0-10-mm treatments, no new rootlets
appeared along the plexiglass bottom during the 80-hour period.
In the remaining treatments, the number of rootlets approximately
doubled during this period. Maximum- damage after fumigation ny
peroxyacetyl nitrate (PAN) or ozone always occurred on the most
recently matured leaves. In cases of severe damage on recently
matured leaves, there was always £ome damage to the apical parts
of the young leaves, with no apparent damage to older mature
leaves. Tissue damage was the main damage from fumigations with
both PAN and ozone in the high oxygen treatments. Silvering and
glazing were characteristic of leaf damage at a low level of
ozone fumigation. Soil oxygen diffusion rates taken in field
plots show that limited oxygen supply to plants could affect the
susceptibility of plants to air-borne oxidant damage under field
conditions.
17C97
Taylor, Gordon S. and Saul Rich
ANT10ZONANT-TREATED CLOTH PROTECTS TOBACCO FHOH FLECK. Science,
vol. 135:928, 1962. 2 refs.
Laboratory experiments protecting tobacco plants from ozone
damage by the use of cloth treated with antiozonants were
described, lasts showed that tobacco is protected by enclosing
groups of plants completely in tents of cloth treated with
4,4*-dioctyl diphenylamine in butyl latex. The treated cloth
also reduces the amount of fleck on adjacent, open plants.
Spraying the antiozonant on the walls of a previously untreated
tent prevents subsequent flecking of plants within the tent.
(Author abstract modified)
G. Effects - Plants and Limtock
913
-------
17109
Maclean, David C., Delbert C. flcCune, Leonard H. Weinstein,
Bichard H. Haudl, and Gecrge H. Sccdruff
EFFECTS OF ACUTE Hit EBOGEN FLUOFIDE AND NITROGEN DIOXIDE EXPOSURES
ON CITRUS AND ORNAMENTAL PLANTS OF CENTRAL FLORIDA. Environ.
Sci. Technol., 2 (6)June 1968. 11 tefs.
Six citrus varieties and six ornamental species of econcrcic
importance to central Flcrida were subjected to high
concentration-short duration exposures of gaseous hydrogen
fluoride or nitrogen dicxide. Postfumigation observations showed
that the effects of acute pollutant exposures differed rcarkealy
from those of chronic exposures. Hydrogen fluoride exposures ot
0.5 to 10 ppm for periods of from 0.5 to 8 hours induced tip,
marginal, and intercostal chlorosis and necrosis, and abscission
of leaves of most plants tested. Symptoms were most severe cn,
but not limited to, young leaves. The effect of duration of
exposure had a greater influence on abscission at young citrus
leaves than did HF concentration. However, the effect of HF
concentration on foliar F accumulation could not be separated from
exposure time. The N02 concentrations used ranged from 25 to 250
ppm for periods of from 10 minutes to 8 hours. Nitrogen dioxide
damage was characterized by rapid tissue collapse, necrosis, and
defoliation. Symptoms were sporadic in appearance, affecting
leaves of all ages. The relative contributions of concentration
and duration to N02 induced injury were about equal. (Author
abstract modified)
17210
Kctaka, Sadao and Albert P. Krueger
STUDIES CN THE AIH-ION-INDUCED GROWTH INCREASE IN HIGHER
PLANTS. In: Advancing Frontiers cf Plant Sciences. Lokesh
Chandra (ed.), vol. 20, New Delhi (India), Impex India,
1968, p. 115-208. 57 refs.
Preliminary studies were conducted on the effect of gaseous
ions on higher plant growth. The influence of ionized
oxygen and carbon dioxide cn the growth of barley and the
influence of reduced-ion-air on the growth of Hordeum
vulgaris was determined. Exposures cf oat, barley, lettuce,
pea, and maize seedlings to unipolar ionized atmospheres
of either negative cr positive charge produced statistically
significant growth stimulation. The extent of growth increase
was related to atmospheric ion density. Analytical data shoved
that no significant alterations in composition developed in
the ion-treated oat or barley. Moderate densitites of 02(-)
and 02 ( + ) (18,000 ions/ml) in air containing an added 8* 02
accelerated the growth rate under laboratory conditions.
Approximately the same number of C02 (-) and C02 (+) ions in air
containing 8% CC2 inhibited growth, impeded the production of
chlorophyll, and devitalized young seedlings, studies were
914
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
also conducted on the biochemical mecharnsBs of aii-iou-induceQ
growth increase in higher plants. Experiments included air
ion effects on free and bound IAA, studies on air-ion-enhanced
preparation of iron-chlorotic seedlings, and air ion effects
cn iron .incorporation intc early germinating seeds. Equiliciium
between free and bound IAA in barley was not displaced by
exposure to air ions. Hordeum vulgaris seedlings grown in a
chemically defined iron-free nutrient solution developed iron
chlorosis. When the growth tcok place in unipolar ionized
atmospheres of either charge, the onset of chlorosis was
accelerated and accompanied by the appearance of large amounts
of cytochrome c. When the seedlings were grown in a substrate
containing iron and were exposed to ionized air, they did not
develop chlorosis but exhibited the typical ion-induced increase
in growth rate and an increased production of cytochrome c. Air
ions enhanced incorporation of iron into early germinating
fcarley seeds. The synthetic mechanism of the iron-containing
enzymes and heme in air-ion-treated plants is being investigated.
17227
Cochinget, L. S., F. V. Bender, F. 1. Fox, and H. V. Heck
CHLCROTIC DHABF OF EASTERN WHITE PIKE CAUSED BY AN OZONE AND
SULPHUR DIOXIDE INTERACTION. Nature, 225 (523 1}:U76, Jan. Jt,
1970. 6 refs.
The interaction of ozone and sulfur dioxide causes characteristic
symptoms of chlorotic dwarf disease on susceptible eastern white
pine (Pinus strobus I.J. Sensitive and resistant white pine rawets
were exposed to 10 pphm of sulfur dioxide, 10 pphm of ozone, or
to mixtures of the two (each in a concentration of 10 pphm). The
pines were fumigated for 4-8 hr each day, five days a week, for
4-8 weeks. Symptoms were not observed on any resistant ramets
or sensitive control plants, chlorotic dwarf symptoms of flecking,
occasionally accompanied by a shedding of older needles, were
noted on most sensitive exposed plants. There was little or no
injury to plants treated with one of the gases and moderate injury
in those treated with the gasecus mixture. The percentage of
mottling on current needles and the premature drop of older needles
exposed to the mixture far exceeded the damage to those treated
with one gas. This strongly suggests that the two pollutants act
synergistically on sensitive white pine plants.
18041
Taylor, 0. C.
IRPOHTANCB OF PEROXlf ACETYL NITRATE (PAN) AS A PHYTOTOXIC AIR
POLLUTANT. J. Air Pollution Control Assoc., 19(5)j347-351,
Way 1969. 25 refs.
Peroxyacyl nitrates are a family of compounds which result from
G. Effects -Plants and Livestock
915
-------
photochemical reactions between contaminants released to the
atmosphere by combustion of organic fuels. Peroxyacetyl nitrate
(PAN) is the most abundant member of this family and is responsible
for serious injury in some polluted areas. Plant injury has been
recognized in at least 19 states and several foreign countries
but economic loss has caused greatest concern in California.
Characteristically, injury from PAN appears as glazing or bronzing
of the lower leaf surface but the symptom syndrome may also include
tissue collapse, chlorosis, and leaf drop. PAN inhibits activity
of several enzyme systems by attacking the sulfhydryl group when
enzyme extracts are fumigated in vitro. PAN may produce visible
symptoms when sensitive plants are exposed for 4 hours to about
1U ppb. Other chemical members cf the family are more toxic than
PAN. Concentrations of 20 to 30 ppb PAN occur frequently at
Riverside, California, and a maximum peak of 58 ppb was measured
for one 2-hour period. Peaks as high as 54 ppb were reported at
Salt Lake City, and 210 ppb at Los Angeles, California. (Author's
Abstract)
06499
I. Ordin and B. Propst
EfPECT OP AIB-BOFNE OXIDANTS ON BIOLOGICAL ACTIVITY OP
INDOLEACETIC ACID- Botan. Gaz. 123(3}, 170-5 (Mar. 1962).
This investigation concerns the effects of some of the known
atmospheric pollutants, namely ozone, peroxyacetyl nitrate (PfcH),
and ultraviolet-irradiated mixtures of olefin and N02 on
indolacetic acid in vitro. It is apparent from the results that
air-borne oxidants such as PAN and ozone can inactivate IAA in
vitro. Hhether such a mechanism of inactivation is of importance
in the living plant cannot be answered fully at present. Ascorbic
acid prevented the inactivation of IAA by chemically reducing
the oxidant level in the solutions. The residual ascorbate, or
its decomposition products, in the growth solutions exerted a
slight subsequent inhibitory action on coleoptile growth. This
observation does not agree with the results of other investigators.
Since the concentration of ascorbate was much higher in the
present experiments than that used by other investigators, it is
possible that the growth-stimulating range was exceeded in the
present investigation. The failure of IAA activity to recover
despite low residual amounts of FAR or ozone in solution and,
¦ore particularly, despite the addition of ascorbate to the
previously treated solutions indicates that the inactivation is
not similar to that caused by H202 or peroxides. In the
peroxide-induced inactivation, there is an apparent Interference
with the bioassay rather than an irreversible change. In the case
of inactivation by ozone or PAN the change is irreversible as
shown by the changes in ultraviolet spectra. Some light on this
irreversible inactivation is shed by the ultraviolet spectra.
They show that the change in IAA caused by ozone and PAN is
probably a ring alteration.**
916
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
H. EFFECTS - MATERIALS
00115
P. 1. Ajax, C. J. Conlee, and J. B. Upham
THE EFFECTS OF *18 POLLUTION OH DYED FABRICS* J. Air
Pollution Control Assoc. 17,(4) 220-4, April 1967.
This report details results froa the first 6 months of a 2-year
study began in February 1965 by The Aaerican Association of
Textile Chemists and Colorists and the Public Health service
to evaluate the effects of air pollution upon dyed fabrics.
Groups of 69 dye-fabric combinations representing widely used
dyes have been exposed in light-free cabinets to ambient
environments at urban and rural sites at Chicago, Washington,
D.C., Tacoaa, and Los Angeles, and at urban sites at
Cincinnati, Phoenix, and Sarasota* Results from consecutive
3-aonth seasonal exposures and controlled-environnent exposures
utilizing irradiated and nonirradiated automobile exhaust for
short duration show an extreae fading on one guarter of the
dyed-fabrics, a higher fading at urban compared with rural sites on
susceptible fabrics, and a marked effect upon the dyed fabrics by
the photochemical by-products of automobile exhaust. {Author
abstract)~%
02270
C. H- Giles
THE FADING OP COLOORIHG HATTERS. J. Appl. Chem. (London) IS,
541-50, Dec. 1965. (Presented at the Second International
Conference, international Inst, foe Conservation (I.C.C.),
Delft, Netherlands, July 7, 1964.)
This paper describes most of the influences which affect the
peraanence of colouring matters, yet in making practical
suggestions for prolonging the life of auseua specimens little
can be added to the recoamendations made by Russell C Abney 77
years ago. If th* specimens are coloured with organic
colouring aatters, store them in a dry, clean, acid-free and
oxygen-free atmosphere, and allow them to be illuminated in the
weakest acceptable light, without ultraviolet radiation, for the
shortest practicable time. (Author conclusion)••
917
-------
02911
V. So Salvia
EFFECT OF AIR POLLUTANTS OH DYED FABRICS„ J„ Air
Pollution Control Assoc- 13, <9) 416-22, Sept. 1963..
(Presented at the 56th Annual Meeting, Air Pollution Control
Association, Detroit, Hich. , June 9-13, 1963, Paper No.
63-84.)
The fading of dyes through cheaical reaction with atmospheric
contaminants has been responsible for conplaints from air pollution
areas. Oxides of nitrogen and ozone are contaminants which have
beeen established as reactants. Sulfur dioxide is the source of
absorbed acid which can accelerate the reactions.. The fading of
dyes by ozone takes place in air pollution and in rural areas.
The contribution of air pollution to increased ozone and
oxidant concentrations is demonstrated in service exposure fadings.
Sunlight fastness results are shown to require consideration of
simultaneous change due to atmospheric contaminants.. Exposure
to irradiated auto exhaust gases under controlled conditions gives
fading results which are equivalent to service exposures in Los
Angeles.•#
04320
Jaffe, L» S.
THE EFFECTS OF PH0T0CHEHICAL OXIDANTS ON HATERIALS. J. Air
Pollution Control Assoc. 17(6):375-378, June 1967„
The deterioration of materials exposed to photochemical smog, in
particular to the oxidants and ozone contained therein, are
reviewed. One of the earliest indications of photochemical
oxidants was the excessive cracking of rubber products- it has
been demonstrated that this excessive cracking of rubber is
caused by ozone formed in the photochemical smog formation process,
other materials known to deteriorate under atmospheric
photochemical smog conditions are textiles and certain dyed
fabrics, particularly under conditions of high humidity. Loss of
tensile strength of cotton textiles when wet or moist, and similar
fading of these dyed fabrics, particularly under high humidity,
can be produced by laboratory exposure of these textiles to pure
ozone. Depending on the formulation of the rubber, cracking
under stress can be readily detected within 3/4 hr when
atmospheric oxidants levels are as low as 0.03 ppm. Natural and
certain synthetic rubbers are particularly vulnerable- These
rubbers when stressed show cracking when exposed to 0.0 2 ppm ozone
for about 1 hr. Ozone effects on asphaltic materials are reported
also» 1AM##
918
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
AS233
P,. J, Hearst
VOLATILE PEOTODEGR A CATION ?Bt>DOCTS O"? ORGfcSIC COATTSSS.. Saval
Civil Engineering tab., Pott Hueneme, Calif. July 196fU 36
pp. (Technical 8ept» (So. H. U60.)
Various clear and pigmented te^icle fills nece irradiated in air
*ith a nercury arc and a xenon arc. Ihe volatile pfcotodegradation
products were identified by infrared spectroscopy. The coatings
included alkyd, oil, Tinyl-alkyd, vinyl copolymer, partially
hydrolyzed vinyl copolfoer, polyvinyl acetate, epoxy-anine, and
epoxy-polyanide films. The aajcr product froa all filas vas
carbon dioxide. Eleveti other products or types of products *ere
obtained, as well as some unidentified products. The addition of
pigments decreased the yields of almost all the products-,
However, the yields of different products were affected in
difEerent degrees by -pig Dentation* and this difference may in part
te related to the penetration of the light responsible for the
^reduction of aaafc particular product, {iatfcor abstract)
0,90 ui
Salvia, V. S.
EiliTICS OF fiT«&SPiUBiC CUNTftjaKAStlS AM Oiuai 10 LlJiilTfAST&tiJi.
Sb. Dyestuil j-eptr. , 'Jcl^ Jan. c, 1964.
refs» (Pnasecteil at tii« American IsiocadtitiiL ot Textile Cne»-
ists ajici Colorists Convention, e-ostou, ridiis., Nov. 1, 1V6J.)
The eitect ot atmospheric contanindnts-oxidts of nitrogen, suitur
diotid-e and ozcne-in causing d »e taiiiaj, is snotiti toe various ijoa
or cotton, raytio. c^lon, acetate^ pcj-^eat^c, dccylics avid «oci.
Data is prtisticted or, thre^-iftotstrh ^rotccxed tree sun-
light in Los An9«le£, Cdlitamid, an area of high SG2 low SC2
and high ozcut; Illinois, mCQcvdt*. «02« i.igii Sui uiiu
ion oione; Phoejiix, krxiCTiA, a saiuj-yht testing station at aoii-
etate ozoiio, tract I>u2 or soiT hut lov fcumdity; dad i'dtasotj,
Tlorida, a sucliqht testing statics ti noueiute oaore, trace
NQ2 or 502, but hiyti huiridity. The ^oteatial contribution ot
atmospheric contaminants as a variable in the iighttasttiese test-
ing is shown iu a series ot dyes ex^csed ausuitaneoualy iti ptra^tuce
and absence of sunlight. Ihe experimental results are used to
explain certain variations in ligbttastness results obtained by the
&ATCC ifl eKfosac&s at ca&stiut auefaet oi 1. alleys, tsquivsieut
temperatures ami humidity hat in diiiereut localities. The jjhccao-
nena ox oaone iadiu^ are discussed iron tfta atandpoict of cccur-
r«ace, vulnerable dy«s, cheaical reaction, and effect of hu»iaity.
ixposure to irradiated auto exhaust gases m a laboratory chamber
xepresewtiug * cowbiration ot «C2 djjd ozone duplicates the L-cts
Angeles exposuce cesuits, *!be inyestigatioxis have led tc tnx&Q
recoamendatioi-s ia AVfCC test frocedores Much should qxvn truer
correlation between service results and rtceeierated test wethods:
K. Eflects -Materials
919
-------
A) a test procedure for ozone lading; B) tne use of higher humid-
ities in testing of dyes on cotton, rayou and uylon to ozone and
oxides ot nitto
-------
I. EFFECTS - ECONOMIC
09313
IKE BISING COSTS. Hach. Des. , 39<17):23-2U, July 20, 1967.
Damage from air pollution both direct and indirect has been
estimated at 65 dollars per person per year, or 11 billion dollars
annually. Agricultural losses ace estimated at 325 pillion
dollars annually. A single day of smog in California a few years
ago reportedly ruined an entire lettuce crop. On the eastern
seaboard, pollution is said to destroy 18 million dollars of crops
each year.. Atmospheric corrosion frcm sulfuric-acid mist has been
reported to do about 6 Million delists danage per year in New
York City alone. The costs of control, although a snail per-
centate of the 11 billion dollars'total, are also significant.
The petroleum industry is reported to spend 18 million dollars
annually on air pollution control out of a total capital outlay of
350 nillion dollars. The major steel manufacturers in the
Chicago area entered into a 8-yr agreement with the local re-
gulatory agency to prevent some 68,000 tons of dust annually from
entering the atmosphere. The estimated total cost of the program
is 50 million dollars. Research efforts into better detection and
control seem pitifully small in comparison to the total damage
estimate. Federal Government research allocations will approach
18 million dollars in 1968. The anticipated expenditures at the
Federal level to achieve goals in reduction of pollutant levels
and in establishing air quality criteria are estimated at 130
million dollars over the next several years.
10985
H. Heckler
COST ESTIMATING- AZS HANDLIHG EQUIPMENT FOE CONTAMINATION
CONTROL. Air Conditioning, Heating, Ventilating
65(7):37—40, July 1968.
Cost-capacity relationships can be used to help select the
optimum mechanical systets during preliminary budget studies. The
steps in this factoring process are defined and some examples of
their applications are presented.it
921
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11815
Garet, Ronald, Richard Drapkin, and Andrew Schaeffer
THE ECONOMIC EFFECT OF OZONE ON HOUf MAINTENANCE COSTS IN THE
LOS ANGELES BASIN. In: Air Pollution Project: An Educational
Experiment in Self-Directed Research, Summer 1968. Associated
Students of the California Inst, of Tech., Pasadena, p. 223-
254, 1968. 1« refs.
EFFECTS-ECONOMIC: Ozone, Eccncnic losses, Hoire maintenance
The effect of ozone on home and car maintenance costs in the
Los Angeles Basin was researched by mailing 10,000 surveys to
residents of Glendale in southern California and Mountain
View in Northern California. Ihe goal was to determine the
percentage frequencies with which residents of a city with
little ozone repaired and replaced common household items,
fan belts, and automobile tires as compared to those frequencies
in a community with high ozone concentration. Preliminary
analysis of 2400 returns show definite differences between
Glendale and Hountain View, due probably in part or whole to
ozone. The differences range from a few to several hundred
percent. They indicate that the cost of air pollution to
individuals in the Los Angeles Basin greatly exceeds the
sixty dollars per year estimate of the California State Air
Besources Board.
12170
Parr ish, E. H.
EFFECTS OF AI? POLLUTION PSOPEFTY DAMAGE AND VISIBILITY. Preprint,
Puguesne Light Co., Pittsburgh, Pa., 12p., 1963. (Presented at
the Pennsylvania Air Pollution Control Inst., Pennsylvania state
Univ., University Park, Pa., Sept. 9-13, 1963.)
EFFECTS-ECONOMIC: Materials deterioration, Visibility, Economic
losses
The cost of air pollution in the continental (J. S. is in excess
of six billion dollars a year. This is the cost of permitting and
tolerating air pollution—not the cost of abatement, enforcement,
research, or personal suffering. Si* billion is the loss in
property or property values and the increased burden of maintenance
and premature replacement. The following is a possible breakdown
of the different classes of material that fall prey to air
pollution: masonry - stones, concrete, brick; wetals in all forms -
structural, eouipment, hardware; decorative and protective coatings;
vegetation; textiles, rubber, plastics, leather, paper, insulation;
property values, art, sculpture, architecture, historical
artifacts, visibility reduction is also a result of air pollution.
These eight topics are briefly discussed to show the manner in
which air pollution effects each one.
922
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
Norton, S. G.
HSE OF SULPHATE TURPENTINE AS A CHEMICAL RAW MAT3PTAL. TAPPI,
120 (7) : (Sfi, Feb. 19«b. (Presented at the Byproducts Committee
ot the Technical Assoc. of the Pulp and Paper Industry,
Savannah, Ga., Oct. IS— 1 , 194<*.)
uwtrjcT^-^COKO^IC: Solvents, By-product recovery, Sulfates
The alpha and beta pinenes that are derived from the crude sulfate
turpentine obtained as a by-product from the sulfate process
can he used in the production of »any new commercial synthetics,
factions involved in the creation of these materials include
isomerization, hydration, dehydration, esterit'ication, ,
etherification, oxidation, and polymerization. Examples of
commercially produced pinene synthetics are isecticides,
solvents, pine oil, cough remedies, perfume bases,
and placticizers. Many other products are awaiting introduction;
all indicate an unlimited market for crude sulfate turpentine
as long as its price remains stable and moderate.
I. Effects - Economic
923
-------
J. AIR QUALITY MEASUREMENTS
00110
R. I. Larsen
DETERMINING SOORCE REDUCTION HEEDED TO BEET AIR QUALITY
STANDARDS. Proc. (Part I) Intern. Clean Air Cong.,
London, 1966. (paper HI/8.) pp. 60-1.
Air pollutant concentrations can be expressed as a function of
location, averaging tine, and frequency that a certain
concentration is exceeded* Concentration data can be used with
ait quality standards to calculate the overall source reduction
needed to aeet a standard. The calculations can be refined to
consider the effects of future growth, rural background
concentrations, secondary pollutants arising fron photochemical and
other atnospheric interactions, and the contribution fron each
source or source type in a city. (Author)~#
00017
AIR QUALITY DATA. (ANNOAL REPORT
NETWORK). Public Health service,
of Air Pollution, 52p.
?0R 1962) (NATIONAL AIR SAMPLING
Cincinnati, Ohio Div.
This report contains sunnaries of sir quality data for
particulate and gaseous pollutants obtained fron samples collected
by stations of the National Air Sampling Network during 1962.
Included also are data obtained by the analysis of selected
particulate sanple* collected during the period 1958-1961. For
the first tine data fro* state Air Sanpling Network report.
This is a logical step, as procedur«s are standard and data are
comparable. The following state networks provided data for
inclusion in this 1962 report: Maryland, Massachusetts,
Montana, Texas, and Hashington. (Author)##
00005
S. Hochheiser, S. 1. Horatman, and 6. A. Tate, Jr.
A PILOT STUDT OP III POLLUTION IN BIRMINGHAM, ALABAMA
(BIDE-ANGLE TIEN OT BIRMINGHAM FROM V0LCINS STATUS). Public
Health Service, Cincinnati, Ohio, Div„ of Air Pollotion.
Hay 1962, 68p..
925
-------
Air samples were collected foe measurement of dustfall,
suspended particulates, smoke shade, sulfur dioxide, nitrogen
oxides, total oxidants, carbon monoxide and hydrogen sulfide.
Air pollution data obtained during the summer phase of the study
can be considered as representative. Mean values of gaseous
pollutants were: S02, 0.01 ppm; nitrogen oxides, 0.0U ppm;
oxidants, 0„03 ppm; CO, 1.B ppm. Maximum levels measured
were: S02, 0„18 ppm; nitrogen oxides, 0»1U ppm, oxidants, 0.. 1U
ppm; CO, 12„5 ppm.. Mean values for particulate pollutants,
measured daring the fall study, were: dustfall,
76 tons/sq.mi./mo.; smoke concentration, 1.5 cohs/1000 linear ft„;
suspended particulates, 113 micrograms/cu.m. Maximum levels were:
dustfall, 121 tons/sq„mi-/mo.; smoke concentration, 6.2 cohs/1000
linear ft.; suspended particulates, 279 micrograms/cu.m. Mean
values measured during the summer study were: dustfall, 49.3;
smoke concentration, 0.6; suspended particulates 106. Maximum
levels were: dustfall 95..6; smoke concentration, 3.0; suspended
particulates, 206. Substantially higher levels of particulate and
gaseous pollutants were recorded in the fall, indicating that
emissions resulting from the combustion of fuels for industrial,
commercial and domestic space heating contribute significantly to
over-all air pollution during the heating season-#*
000«1
W.F. Ashe
HEALTH EPFECTS OF ACOTE AIB POLLUTION EPISODES. Ohio State
Oniv., Columbus, School of Medicine. (Presented at the
national Conference on Air Pollution, Washington, D.C.,
Nov. 1958.) Nov. 19, 1958, 9p.
Air pollution can and has produced serious illness anrt even
death. However, since all industrial cities, the world over,
produce air pollution in tons per day all the time, and since there
are only a handful of authenticated episodes of acute illness
due to it, one must conclude that acute illness and/or death due
to air pollution is unusual. The situation which produces
dangerous air pollution is a particular kind of weather which is
predictable. The prediction and prevention of air pollution
episodes must be approached with utmost caution.##
00050
G.Welsh
AIR POLLUTION IB THE NATIONAL CAPITAL AHEA. Public
Health Service, Washington, D.C., Div. of Air Pollution,
July 1962. 48p»
CFSTI: PB168314
This appraisal of air pollution problems in the Metropolitan
Washington Area had three objectives: (1) To review and
evaluate the existing and potential air pollution problems of the
Metropolitan Area. (2) To review briefly air pollution control
926
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
activities presently being conducted by the respective local
governmental agencies* <3) To develop recommendations for the
guidance of local officials in meeting existing and future air
pollution problems* The scope of the study was limited to
consideration of available information regarding air pollution,
including: activities which cause pollution, evidence of pollution
levels, Meteorological and topographical influences on dispersion
of pollutants, local air pollution control activity, and other
00136
G. Arnold and E. Edgerley
ORB AN DEVELOPMENT IN AIR POLLUTION BASIKS - AN APPEAL TO THE
PLANNERS FOR HELP,, J. Air Pollution Control Assoc. 17, (4>
235-7, Apr. 1967. {Presented at 59th Annual Meeting, Air
Pollution Control Association, San Francisco, Calif., June
20-24, 1966.)
Onder local inversion conditions, an air basin holds a great mass
of cool air like water in a saucer, forming a quasi-closed system
that holds pollutants within. Orban centers in such basins tend
to stagnate, like the constrained air itself. Understanding the
air circulation patterns in these air basins is essential to air
resource management and urban planning. A practical
recommendation from the planners would be to locate urban centers
at higher elevations, where effluents are dispersed by swift winds
that are relatively free of surface friction. Airline pilots
would be overjoyed to find excellent visibility at airports
distributed on the mesas. Control officials and meteorologists
appeal to the metropolitan planners to help reverse the trend that
has brought congestion and pollution to our low-lying trade
terminals* (Author abstract)*#
00149
J. F. Clarke, and R. B. Faoro
AN EVALUATION OF C02 HEASOBBHBHTS AS AH INDICATOR OF AIR
P0LL0TI0N. J.. Air Pollution Control Assoc. 16, (4) 212-8,
Apr. 1966.
Measurements of ambient CO2, made at the Continuous Air
a rural location near Cincinnati are presented and evaluated to
determine the significance of C02 data in urban air quality
monitoring programs. Through analysis of rural CO2 data and
evaluation of combustion sources by means of a diffusion model,
it is demonstrated that the variation of urban C02 concentrations
around the prevailing atmosphere background level results from
combustion and noncombustion {natural) sources. The concentration
from natural sources can be substantial and in fact override the
combustion sources. Because it is not yet practical to predict
the contribution of natural sources to urban C02 concentrations,
data obtained for this gas have only limited utility as an index of
air quality, significant statistical relationships between CO2
J, Air Quality Measurements
927
-------
data and air quality measurements foe summer months are shown to
result from similar meteorological effects rather than similar
sources. A seasonal and spatial variation of these relationships
is postulated and subseqnently demonstrated by analysis of C02
and air quality measurements from New Orleans, Louisiana, and
St. Louis, Missouri • E. Scott and V. F. Siller
THE COHPOSITIOR AID ODOR OF DIESEL EXHA0ST. Proc. An.
Petrol* Inst. 45(111):133-147r Hay 1965. (Presented at the
30th Hidyear Meeting, American Petroleum Inst. Division of
Refining# Hontreal, Canada# Ray 10, 1965.)
928
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
Sampling and analysis techniques are described for determining
light hydrocarbons, oxides of nitrogen, formaldehyde, acrolein,
total aldehydes, total particulate, and polycyclic aromatic
hydrocarbons in diesel exhaust.. Using the technigues described,
results are reported on the composition of exhaust from two diesel
engines, a two- and a four-cycle, under a variety of operating
conditions. Smoke ratings using different techniques are also
reported and compared to total particulate results. No
correlation was found between smokemeter ratings and particulate
loadings at other than black smoke conditions. Human panel
observations of exhaust odor are being made as part of a
continuing program, but no panel data are reported* (Authors*
abstract)*#
00321
Rn I. larsen, C. E. Simmer, D. A. Lynn, K. 6.
Bleuel
AHALYZIHG AIR POLLDTAIT COHCBHTRATIOH AMD DOSAGE DATA. J.
Air Pollution Control Assoc. 17, (2) 85-93, Feb. 1967.
(Presented at the 59th Annual fleeting of the Air Pollution
Control Association* San Francisco, Calif., June 20-24,
1966, Paper Ho. 66-93.)
Continuous air pollutant concentration data have been
analyzed for carbon Monoxide, hydrocarbons, nitric oxide,
nitrogen dioxide, nitrogen oxides, oxidant, and sulfur
San Francisco, and Washington for years 1962 through 1964.
Concentrations are approximately lognormally distributed
for all pollutants in all cities for all averaging tines.
Haximum concentration is inversely proportional to averaging
tiae to an exponent. Air pollutant dosage (concentration
tiaes tiae) above various threshold concentrations has been
computed for all of the pollutants in all of the cities for
year 1964. equations have been developed froa these analyses
to predict the freguency of occurrence of air pollutant
dosages of various intensities as a function of the geometric
mean and standard geometric deviation. An example is shown
for predicting the number of occurrences of sulfur dioxide
dosages that sight cause acute plant daaage. (Author)#*
00435
fl. I. Larsen
A METHOD FOB DBTEHNIKING SOURCE REDDCTIOR REQUIRED TO HEET AIR
QUALITY STANDARDS. J. Air Pollution Control Assoc.
11(2)171-76, Feb. 1961.
A computer program was written to calculate arithmetic and
geometric correlation and regression between any two variables for
various periods of time, location, and condition of solar
radiation. Two thousand correlation coefficients and the
associated regression limes of best fit were calculated to explore
the interrelationships between variables. The summary punched
J. Air Quality Measurements
929
-------
cards were the input to this computer program. The purpose of
those analyses is to show the frequency of occurrence of various
values of oxidant, eye irritation, and visibility; to indicate the
equations relating these pollutant effects to concentration of
carbon monoxide; and to show the usefulness of this information
for predicting removal of precursor, as measured by carbon
monoxide, necessary to obtain given levels of improved air
quality-##
00UH5
R. Tsuge, K. Ogava and K. Sakai
RELATION OF ATHOSPHERIC COHTA RIHATIOU WITH AIB TOTIS.
Mitsubishi Denki Giho (Tokyo) HO(3):U62-466, Har. 1966.
Text in Japanese
Air ions were found to have close relationship with contamination
of air» There are several methods to measure the degree of
contamination. Ion density meters, digital dust waters, and gas
detectors are employed to obtained numerical indication of
positive ions* negative ions, dust and C02. As a result of
investigation, it is confirmed that the quantity of air ions is
correlated to the quantity of dust in the atmosphere. (Author
summary) ##
00526
Kiddleton* T.
COHTBOI OF EFVIBOHHBWT - SCOKOHIC ASP TECHROIOGICAI PROSPECTS.
Preprint. In: Environ. Improvement: Air, Water, Soil,
pp. 53-71, Oct. 1966.. (Presented at the Dept„ of Agriculture
on or about May 24, 1966)
Ban's exploitation of land, water, and air has caused serious
pollution of his environment, not only affecting man but other
living organisms, quality of the land, water* and air resources.
Hot only must large sums of money be spent to restore the
quality of man's environment, but it must be done quickly. The
quality of air is determined by the uses made of air and by the
pollutants injected into it by man. Vhile some air contamination
results from pesticides and chemical manufacturing the greatest
degradation results from the use of air to support combustion.
Principal pollutants from combustion for the development of
energy and the propulsion of motor vehicles, and the manufacture of
goods are liquid and solid particles* oxides of S and s, organic
vapors, C02 and CO. The pollutant released in
largest quantities throughout the nation is S02, amounting to
23*300,000 tons a year. The quality o£ air within a given air
shed depends upon the nature of pollutants* the quality of the air
supply and the geographical and meteorological factors affecting
the movement and dispersal of contaminants. One result of
multiple pollution sources is the combination of h oxides and
organic vapors in the presence of sunlight* resulting in
photochemical air pollution i.e. ozone* peroxyacetyl nitrate
930
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
(PAN), aldehydes, and organic acids. The resulting pollution
effects are metal corrosion, building and fabric deterioration,
cracking of rubber, visibility reduction, forest and agriculture
damages, livestock Injury health problems, and the spoiling of air
environment. The recognized importance of these effects, the
recognition of air pollution as a social problem, and the
enactment of legislation to control air quality has occurred at
both state and national levels.4#
00528
H. E» Hatchard
PORTLAND'S HEW AID QUALITY CONTROL PROGRAM. Preprint.
(Presented at the Second Annual fleeting. Pacific northwest
International Section, Air Pollution Control Association,
Portland, Oreg., Nov. 5-6, 196U-)
After ten years of developmental steps, the city of Portland
is moving forward rapidly to implement the new Air Quality
Control Code. The new registration program will produce a large
quantity of detaild information regarding community sources. The
ten dollar fee is helping to finance the initial program costs.
The relatively large numbers of complaints received are being
investigated and where violations are found, corrective action is
forthcoming. Many long-standing smoke and other particulate
source problems are being controlled. In the future, increased
emphasis will be placed upon the control of local geographical
areas within the City. This approach will be balanced with a
planned community-wide control of similar industrial, commercial
and public sources. Additional public informational activities
are needed to develop support for the necessary changes to improve
Portland's air guality conditions. (Author's summary)M
0053«l
c. B. Robinson, W. L. Meadows, and J. j. Henderson
AIR POLLUTION PATTERNS IN THE GREATER BIRHINGBAH AREA..
Preprint. 1965«
In 1962, the Alabama Respiratory Disease and Air Pollution
Study was initiated to determine the prevalence of various
pulmonary disorders and to relate these findings with air quality
data. This paper describes part of the aerometric effort begun in
December 1963 in the Greater Birmingham Area, samples for
analysis of suspended particulate, dustfall, sulfation, and 24-hour
gases (nitrogen dioxide, sulfur dioxide, and aldehydes) were
collected routinely from 21 stations located primarily in
residential areas. The sampling network, analytical methods, and
statistical procedures used are discussed. Air quality results
are presented with emphasis on spatial and temporal variations.
(Authors* abstract)«t
J. Air Quality Measurements
931
-------
00644
C«. K. Copley, Jr. and H. C. Hitchell
AIR Q0ALITT OP THE ST. 100IS HETRCPOLITAN REGION. Preprint.
(Presented at the 58th Annual Heeting, Air Pollution Control
Association, Toronto, Canada, June 20-24, 1965, Paper Bo.
65-137..)
The St.. Louis Metropolitan region is an interstate area of
about 2500 square Biles consisting of 3 counties, St. Louis,
St., Charles and Jefferson and the City of St. Louis in
Missouri, and 3 counties, Honroe, St. Clair and Madison in
Illinois. It has a population of about 2 Billion and a widely
diversified coaaercial and industrial aake-up. t is also a
transportation hub. As a part of the Interstate Air Pollution
Study, a cooperative project of the 0.S. Public Health
Service and 10 local area agencies, a large variety of air
saapling networks were operated in the region collecting data far
in excess of a year. Saapling stations for particulate natter
included 41 dustfall, 16 Hi-vol, 12 AISX and 1 pollen; for
gaseous pollutants, * seguential 502, 20 winter 24 hour S02 and
9 suaaer oxidant. In addition, 36 corrosion testing stations were
operated for 16 aonths and a CAHP station for 4 nonths. This
paper reviews the large voluae of data collected by these
sampling networks in comparison with findings of other studies and
suggested air quality standards. (Author abstract)#*
00666
A.T. Porde D.Ho ffatbeson
THE DESIGN AND OPERATION Of A HUNICIPAL AIR P0LL0TI0N
SDHVET. Preprint. (Presented at the 5Bth Annual fleeting.
Air Pollution Control Association, Toronto, Canada, June
20-24, 1965, Paper Ho« 65-80.)
A municipally conducted air pollution survey has been carried
out in Hamilton, Ontario over the past ten years. The
results of the survey are considered in so«e detail, and
conclusions drawn. Soae observations concerning the design
and operation of an area survey are aade.t*
00680
D. H. Hatheson, b. E. Sunn, and J. wingfield
OZONE LEVELS AT HAMILTON, ONTARIO. Preprint. (Presented at
the 58th Annual Seeting, Air Pollution Control Association,
Toronto* Canada, June 20-24, 1965, Paper No. 65-115.)
The presence of oxone or other oxidants in normal and polluted
atmospheres is receiving increasing attention, even in northern
cities where polluted ataospheres are noraally cheaically reducing
932
PN0T0CHEMICAL OXIDANTS AND AIR POLLUTION
-------
in character. Only United inforaation is available concerning
the concentration of ozone and the temporal pattern of its
occurrence in Canada* although there is accumulating evidence
that its presence nay be a factor in certain agricultural damage in
Southern Ontario* In 1961 a Meteorological air pollution
research study was began at Hanilton, under a federal Health
Grant. Hamilton is a particularly appropriate site for this
study since it is a large industrial city, located on the lake
where its weather is subject to lake influences. The 300-ft high
Niagara escarpment passes through the city and Materially affects
the transport and dilution of pollutants through modification of
the wind pattern* The project includes the operation of a 200-ft
Meteorological tower, and air pollution aeasareaents at a nunber
of sites, of soiling index, aerosol loadings, S02, nitrogen
oxides, total oxidants and ozone. Observations in the period
April 1963 to December 196ft, inclusive are reported. Hamilton
is an industrial city of 280,000 population with 325,000 people in
the Metropolitan area. The predoainating industries are two large
basic steel plants, producing two-thirds of Canada*s output.
In addition, there is a wide variety of other industries,
including electrical, chenical and Machinery Manufacturing. The
city is located on the south shore of Burlington Bay and Lake
Ontario at the western tip of the lake. A large proportion of
the city, including the Industrial area, is on a level plain- The
Niagara escarpnent passes through the city froa east to west, and
about one-half of the residential area of the city is on the upper
level, since the predonlnant winds are vest and south-west, the
industry is favorably located as far as the city is concerned for
dispersion of its air-polluting emissions over the lake.##
00698
R. B. Faoro
A STODT OP SAHPLE ATEBAGIBO TIHES ABD PEAX-T0 BE** PATIOS FOB
GASEOUS POLLUTANTS. Preprint. {Presented at the, 58th Annual
fleeting. Air Pollution Control Association, Toronto, Canada,
June 20-24, 1965, Paper Bo. 65-90.)
The purpose of this paper is to deaonatrate the effect of sasple
averaging tiae upon ne&sureaents of air quality, frequency
distributions of concentrations of selected gaseous pollutants,
based on data froa the Continuous AirBonitoring Program, are
presented. An analysis of the ratio of peak-to-sean
concentrations shows the relationships between this ratio and such
factors as season, tiae of day, and atmospheric stability.
(Author abstract)• •
00730
B.B. Ilgenfriti, J.p. Shively, B.B* Krienke
SOBTETIBG AI8 QUALITY At BOS CHIHICA1 COBPABT (AIB POLLUTION
COWTBOl BBOIBEEFS EXPLAIN). Air Eng., 7 (10):20-28, Oct. 1965
(Presented at the 58th Annual Beeting, Air Pollution Control
Association, Toronto, Canada, June 20-24, 1965.)
I Air Quality Measurements
933
-------
Jin 18-station surrey program was established in 195B for
Midland, Michigan* headquarters of The Dow Chemical Company
and location of the Midland Division. This site contains
a chemical complex with over 500 organic and inorganic chemical
processes. Measurements of dustfall sulfation* sulfur dioxide,
suspended dust, stain index, chlorides, hydrocarbons and corrosion
are recorded and correlated with Meteorological data. Air
Pollution complaint data are also recorded both within the plant
and in the community and fori a part of this surveillance
program- (Author's abstract) t*
00739
C.E. zimmer F.I. Larsen
CA1CTJLATIHG AIB QtHUITT AflD ITS C08TB0L. J. Air Pollution
Control Assoc.., 15(12):565-572r Dec. 1965. (Presented at the
58th Annual Meeting, Air Pollution Control Association,
Toronto, Canada, Jane 20-24, 1965.)
Air quality is shown as a function of averaging tines of five
minutes to one year for carbon monoxide, hydrocarbons, nitric
oxide, nitrogen dioxide, nitrogen oxides, oxidant, and sulfur
dioxide in Chicago# Cincinnati, Los Angeles, New Orleans,
Philadelphia, San Francisco, and Washington, D. C.
Concentrations are approximately lognormally distributed for all
pollutants in all cities for all averaging times- Maximum
concentration is inversely proportional to averaging tine to an
exponent. The exponent is a function of the standard geometric
deviation. General air guality and control parameters are derived
and shown for one exaaple, nitrogen oxides in Washington, D. C.
These values are compared to one air guality standard. (Authors*
abstract)##
00781
L. Friberg B. Bylander
SCIENTIFIC BASIS FOB S0HE B3DICAI AIB QUALITY GUIDES. J.
Air Pollution Control Assoc. 15, (11) 531-4, Wov. 1965.
An attempt to develop medical air guality guides was recently
made in Sweden* Even if air pollution is presented in only
fairly saall amounts, problems frequently arise especially
concerning nuisance reactions. Present regulations do not provide
a basis for a standardized treatment of air pollution problems.
The national air pollution situation was discussed and a survey
of the literature was performed to collect data concerning
current air pollutants. For sulfur dioxide a 30 day value of
eight pphm and a two hour value of 25 pphm was recommended*
It was further recommended to keep the carbon monoxide
concentration as low as possible with as eight hour value of 30
ppm as an absolute maximum. For carcinogenic and mutagenic
substances it was also recommended to keep the values as low as
possible. Although available data did not support complete
medical guides in all cases it was decided rather to have the above
approximations than to leave the air pollution situation
uncontrolled. (Author abstract)**
934
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
00802
2.H. Williaas
AN ATMOSPHERIC SDRVBY OF CHILLI*ACK, BRITISH COLOMBIA.
Preprint. 1963.
A one-year study of the air pollution level of the City of
Chilliwack has been conpieted. Methods employed and data
collected for dustfall, sulfation rates* soiling index,
hydrogen sulfide, oxidants and total hydrocarbons are
presented* Difficulties experienced in the deternination of
very low oxidant levels are discussed* The results obtained
indicate that the City is particularly free of air pollutants
and thus will serve as a suitable base for comparative
studies on the relationship between air pollution and other
factors in the prevalence of certain chronic respiratory diseases.
(Author abstract)##
00847
J.D. Hilliaas W.G. Edaisten
AN AIR RESOURCE HASAGEHEHT PLAX I0R THE IA5HVILLE METROPOLITAN
ARIA- Public Health Service, Cincinnati, Ohio, Div„ of
Air Pollution* Sept. 1965. 160 pp.
GPO: 822-811-8, HE»: 999 AP - 18
This report is based on the numerous technical and scientific
papers resulting from a aajot study of air pollution and effects
nade in Nashville, Tennessee, by the Public Health Service,
Vanderbilt University, and state and local agencies during
1958-59. These papers have been suppleaented by field
investigations to complete the background information needed for
preparation of an air resource aanageaent prograa plan. The
report saaaarizes a nuaber of the technical and scientific papers
and uses all of the* to develop new concepts as well as unify new
and old approaches to air pollution control in preparation
of the air resource aanageaent prograa plan. Air quality
goals and the aeans to reach those goals are suggested.
Supporting data are provided and aethodology adapted for relating
air quality goals to control of eaissions. Methods for predicting
air pollutant levels by ase of aatheaatical aodels are presented.
Public opinion survey results and their iaplications for the air
resource aanageaent prograa are given. The report has specific
use for developaent of an air resource aanageaent prograa in
Vashville and general use for program developaent and reference
in aany other places, (luthor abstract)##
00913
A. Harsh, (Ed.)
SOLED* DIOXIDE AS A1 ATH0SPHE8IC POLIDTAHT. Rational Society
for Clean Air, London, 196«, 32p.
J. Air Quality MwsuramwttJ
935
-------
Author discusses such sulfur dioxide problems as: Sources and
Extent of Solfur Dioxide Pollution; Effects of S02 on
Huaans and Plant tutorial; Removal of S02 froa Floe Gases;
Dispersion by Temperature, Telocity and Weight; Seduction of
Eaissioas through Iaproved efficiency aad Technical
Developments; Control of Emissions by Begulation of Etiel
Usage, lathor states ia conclusion that the problea of SQ2 in
the ataoaphere is one that callas for a variety of controlling
solutions. It is apparent there is bo prospect in the immediate
future of entirely elininating this gas, bat that, through the
aeatis that have been indicated auch can be done to reduce the
total emissions and to reduce its concentrations in the air.##
01010
A FBPOFT TO THE LEGISLATURE OR AIB POLLOTIOH 18 COLORADO.
Colorado State Dept. of Public Health, Denver. Feb. 5,
1964„ 66 pp.
» series of studies by the State Departaent of Public Health,
local health departments and other interested agencies and
groups led to the present Colorado Air Pollution Lav calling
for the State Departaent of Public Health to study the air
pollution problea and to recoaaend anbient air standards and
control measures. Colorado is experiencing a rapid growth of
population* urbanisation and sources of air pollution, and
aeteorological and topographical features over auch of the state
are conducive to the developaent of serious air pollution
conditions* With the assistance of the Colorado Air Pollution
Advisory Coaaittee, the State Dept. of Public Health has
recoaaended standards for anbient air quality in the State. Air
quality aonitoring prograas in six of Colorado's largest cities
vere conducted and auch infornation about the extent and nature
of the air pollution problea was obtained. Three aonitored
areas (Denver Betropolitan Area, Boulder and Pueblo)
definitely do not aeet the aabient air quality standards
established and one (Grand Junction) night not aeet the
standards, the geographical air pollution basins of the areas
that do not aeet the standards have been outlined, with the
exception of Boulder. The geographical boundaries for Boulder
will be determined at an eacly date. Measures for the abatement
of air pollution within the State have been recoaaended and are
listed* (Author suaaary)#t
01017
S. S„ Grisvold
COHOTHITT COIT80L O? A IB POIIOTIOI-POTSIITIAIS A»D LIHITS.
Arch* Environ. Health Tol 9i606-608, Hov„ 1964. {Presented
at the Aaericau Medical Association Congress on Environmental
Health Problems, Chicago, 111., Hay 1-2, 1964.)
Curtailaent of vehicular pollution* coabined with a largescale
control ptograa for stationary sources, such as is now operating
loa Angeles, can reduce pollution ia any coat unity to the point
936
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
where it is no longer a significant problem. Thus* the limitation
upon air pollution control, if there be any, cannot be said to be
technical. Is the limitation then economic? In Los Angeles,
these objections were disregarded and the economic effect upon
industry of the most stringent air pollution control program in the
world did not cause a ripple. Ignorance and apathy are the real
limitations upon the control of air pollution. A community
endures air pollution because it lacks leadership and the will to
act. The public does not understand, and the community leaders,
for one reason or another, are placing higher values upon what vie
have seen are specious arguments that air pollution can not be
controlled, or costs too much to control. The potential for
controlling pollution is adequate for present problems. The only
real limitation upon a successful air pollution program is the
failure to understand and act in time,. Members of the medical
profession have an important responsibility in seeing that this
potential is recognized and these limitations overcome.##
01041
An Bihl| Jr.
NEN YORK STATE* S CLASSIFICATIONS - AMBIENT AIH QUALITY
OBJECTIVES SYSTEH. J. Air Pollution Control Assoc. Vol.
15:|11J 519-522, Mov. 1965-
The air pollution potential of any area is directly related to its
population and economic development. In New York state, this
pollution potential ranges from that existing in the sparsely
inhabited recreational zones to that prevailing in the densely
populated and/or heavily industrialized areas. No one set of air
quality standards or objectives can be developed which can
reasonably be applied on a statewide basis. A classifications-air
quality objectives system has been adopted by the State Air
Pollution Control Board for application in New York state.
In accordance with this system, specific aceas can be classified
in one of 16 categories. Air quality objectives, in keeping with
each classificatioa are designed to protect health and to proaote
the maximum coafort and enjoyment and use of property consistent
with the needs of the area concerned. The systeo was
developed by the staff with the assistance of a council of
technical advisors. Units of Measurement related to the aost
important effect of specific contaminants are utilized. Hethods
of sampling and analysis are specified. The details of the
classifications-objectives system, the place of the system in the
state*s air resource management plan, the manner in which each
segment of the state after study will be classified, and how
attainment will be evaluated are described. (Author abstract]##
01095
C. E. Zimmer and G. A. Jutze
AN EVALOATION OF COmiOOOS AI* QUALITY OAT A. -I. Air
Pollution Control Assoc. 11, (7) 262-6, Jul; 1964.
iPresented at the 56th Annual Meeting, Air Pollution control
Association* Detroit, Rich., June 9-13, 1963.)
J. Air Quality MeasuramMts
937
-------
Sulfur dioxide data fron the Continuous Air Honitoring
Prograa fCAHP) for 6 cities are evaluated in relation to the
following tvo objectives: (1) provide an indication of the levels
of atmospheric pollution by gaseous contaainants that can be
correlated with health and econoaic effects and (2) determine the
optiaua sampling tine for studies of this type. Frequency
distributions of five-ainute concentrations were conputed for both
the su«aer and winter aonths for the 6 cities. Present analyses
indicate that the optiaua averaging time (saapling interval)
for sulfur dioxide is 30 *in or less. The frequency of
occurrences of events of varying lengths of tine in which the
5-min concentrations of S02 exceeded levels specified in
suggested air quality standards was conputed. Zt is concluded
that deternination of simple excesses of a standard is insufficient
to neasure the seriousness of an air pollution event. Future
work will be directed towards computation of measures of the total
dosage over specified tine intervals for all of the 6 gases now
•onitored by CAMP.**
01202
H. Nolan
A SUBVBT OF AIH POLLUTION IS COHiSDSITIES ABOUND THE JOHN F_
KENNEDY INTERNATIONAL AIRPORT (5ept« - Oct- 1964).
Public Health Service, Cincinnati, Ohio, Div. of Air
Pollution. June 1966. 82 pp.
GP0,HSB: 826-792-2
A 1-aonth air-quality study was conducted in the coanunities
adjacent to John ?• Kennedy Airport in Queens and Nassau
Counties, New Tort, fron Septeaber 2*» to October 2H, 1964,
Eight saapling stations were located in the area, limited
aeasureaents of particulate Batter and hydrocarbons, and odor
observations yielded sone evidence to indicate that aircraft
operations contributed a saall aaeunt to particulate and
hydrocarbon concentrations and to odor occurrence. Concentrations
of particulates, odors, and hydrocarbons at the saapling stations
were substantial and caae froa aany sources in the metropolitan
area. Thus, the saall variations that occurred in aeasured air
guality were not significantly correlated to aircraft enissions on
a statistical basis. The nnaber and percentage of jet aircraft
using water injection daring takeoff decreased narkedly froa
1963 to 1964 at the J« 7. Kennedy Airport; therefore, snoke
emissions caused by water injection hare been reduced, this
downward trend is expected to continue. Meteorological conditions
during the study were near noraal for this period of the year-
Poor conditions for ataospheric dispersion were experienced for a
5-day period; however, no prolonged severe ataospheric stagnation
occurred. Therefore, air contaainant concentrations that would
exist under extreaely adverse meteorological conditions could not
be aeasuted. The llaited, aodest studies did not show any
difference in the characteristics of particulates enitted froa jet,
diesel, or gasoline engines.*•
938
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
01257
K. Biersteker, H. DeGra&f, and A. G. Nass
INDOOR AIR POLLUTION IN HOTTERDAH HOMES. Intern- J- Air
Water Pollution 9, 343-50, 1965.
800 paired samples of indoor and outdoor smoke and S02
concentrations of 60 Rotterdam hones were studied in an effort to
throw more light on the role that indoor air pollution may play in
epidemiology,, it was found that shaking increased the amount of
smoke found in living rooms and the data suggest that never houses
tend to have less S02 in the living rooms than older houses, on
the average living rooms contained approximately 80 per cent of the
smoke and 20 per cent of the S02 measured simultaneously
outdoors during 24 hr periods. The probability of having more
S02 in the living room than outdoors is estimated at less than
2 per cent of the days, but the findings of constant high S02 in
one living room in this small sample may mean that faulty chimneys
and heaters may play a bigger role in air pollution mortality
during fogs than so far has been suspected. (Author abstract}##
01270
H. Katz
QUALITY STANDARDS FOR KIR AND WATER. Occupational Health Rev.
(Ottawa) 17(1) s3-8, 1965. (Presented at the Occupational
Health and Safety Conference, Canadian Congress of Labour,
North Bay, Ontario, Nov. 16, 1964).
Author reiterates air quality standards and threshold limit values
for gases and vapors
-------
01591
AIR POLLUTION HEASOBEHEHTS 07 THE NATIONAL AIR SAMPLING
HETWOBK - ANALTSES OP SBPENDED PAPTICDLATES 1963. Public
Health Service, Cincinnati* Ohio, Div. of Air Pollution.
1965. 90 pp.
In 1963 the National Air Sampling Neteork encompassed some
200 stations. This report presents the results of analyses
performed on samples collected at these stations in 1963 and
also results of analyses performed in 1963 on some samples
collected in previous years. These results are tabulated
in the Summary Table. Host pollutant levels are reported
as geometric means (designated hereafter as *neans*) for
reasons discussed in Appendix A. Where it is not feasible
to calculate the geometric parameters, arithmetic means are used.
(Author summary modified)9#
01770
7. An Bell, Jr.
SHOBT-TEBH AIP POLLDTION STUDIES. Civil Eng. N.T. 33,
4 0-51, Feb. 1963.
Air pollution studies designed to measure the concentration of
oxidants, carbon monoxide, sulfur dioxide, aittic oxide and
nitrogen dioxide in the cities of Washington, D. c. , Lynchburg,
Virginia, Tucson, Arizona, Phoenix, Arizona and Fresno,
California are discussed. The area surveys are conducted over a
short term time period and author elucidates the advantages and
disadvantages of this approach.**
01782
J„J. Schueneman
AIB POLLUTION PROBLEMS AND COKTROL PROGHAHS IN THE 0KITED
STATES. J. Air Pollution Control Assoc. 13, (3) 116-25
Har- 1963. {Presented at the 55th Annual Beeting. Air
Pollution Control Association, Chicago, 111., Hay 20-24,
1962
There is ample information at hand that the air pollution problems
before us are of major importance. These range all the way from
excessive flustfall at a home located across the road from a
portable asphaltic road mix plant in a rural area to the complex
and extensive problems of the megalopolis of the eastern seaboard.
It is also clear that inadeguate attention is being given
to these problems. While today we seem to be "getting by" with
the misuse of our air resources, it appears that the rate of
growth of oar country will surely force us to conserve and
manage our air resources, whether we want to or not. The growth
940
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
of oar country is fast and seems to take no special prodding but
the growth of our air pollution control prograns takes years and
a lot of "doing." The time to start has passed. While some
states and communities have started* a further major increase in
efforts is required if we are not to find ourselves in the year
2000 with cities sore blighted than were St. Louis, Pittsburgh,
and their brethren, 25 years ago. (Author abstract)*#
01829
1. J. Basbagill
*IR COHTAMISAWT HEASUHEHEHTS AT ROOSEVELT FIELD, HASSAO C00HTT,
HEU TORMJAHUAHT - FBBFUAFT 1964). Public Health Service,
Cincinnati, Ohio, Div. of Air Pollution. July 1965. 53 pp.
Based on the meteorological conditions observed, contaminant
levels Measured during the study may be considered typical for this
site during the winter Months. Since there were no cases of
severe atmospheric stagnation during the study, measurement of
maximum contamination levels was not possible. Conclusions based
on the data obtained in this study are: (1) Particulate aatter
contamination as indicated by soiling index aeasurenents was
"heavy" to "extremely heavy" about 9% of the tiae; this Indicates
that air contamination froa emission of small-sized particulates
should be reduced. {2) S02 concentrations were excessive.
Action to control emission of this contaainant should be
considered* <3) CO and oxides of nitrogen concentrations were
soaewhat greater than desirable. (4) Photochemical smog was not
present, nor was it expected at this tiae of year. It is
recommended that the existing air monitoring program be expanded.
The number of sampling sites should be increased and aeasureaent
of other contaminants should be initiated. These data will
indicate seasonal variations in pollution, measure the
effectiveness of air resource management programs, document
long-tern trends of air quality as related to changes in the
nature of contaainant sources# and relate air contanination to its
effects. Because air contanination does not recognise political
boundaries, this air aonitoring program and other aspects of the
air resource management program should extend throughout the
entire county. Data from surrounding jurisdictions should be
considered also.#*
01830
8. R. Brice and J. B. Ludwig
TBI DISTRIBUTION OT TIHICOLAt AIB POtlBTIOB I* THIS 0SITED STATES.
Preprint. (Presented at the 58th Annual Heeting, Air
Pollution Control Association, Toronto, Canada, June
20-24, 1965, Paper 65-21.)
The contribution of automotive vehicular emissions to air
pollution and the magnitude of the effects of these emissions have
been well documented in Los Angeles County and to a lesser
extent throughout the State of California. Data are
J. Air Quality Measurements
941
-------
presented which show the presence of photochemical "s*og" and
prevalence of "saog1" in eastern coaaunities is not as high as in
Los Angeles; however# evidence fro* most large cities where
ataospheric pollutants have been Measured shows soae photochemical
activity with production of oxidants throughout the year and severe
"snog" when adverse aeteorological conditions occur. Plant damage
of the types associated with photochemical pollutants has been
observed in iiany areas throughout the country and further indicates
the presence of adverse levels of aotor-vehicle-derived
pollutants. Source surveys in a number of cities in the United
States show that aotor vehicles are responsible for very
appreciable aaounts of the total emissions of hydrocarbons,
nitrogen oxides* and carbon monoxide. The facts presented
clearly point to potential problems under current conditions and
problems of increasing severity as population densities and use of
notor vehicles increase. {Author abstract)**
01864
SIXTH ANHUAL RBP08T OP THE A0CKIAKD AIB POLLOTIOH RESEARCH
COMMITTEE. {Annual Sept. 1965). Auckland Air Pollution
Research Coaaittee# Rev Zealand Bar. 31* 1965. 42 pp.
This is the Sixth Annual Report of the Auckland Air
Pollution Research Coaaittee presented to the Local
Authorities of Hetropolitan Auckland# and it sunaarises the
first 3 years of the planned 5 year survey. The aain work
of the Coaaittee has been in three fields. The first field has
been a continued study of the aeteorological and topographical
conditions that affect air pollution in the Metropolitan area.
Inversion conditions which contribute to concentration of
pollutants in certain areas, exist guite frequently during the
night, particularly in autumn and winter. Bovever, present
records show that these conditions do not persist during the day,
so that emulative concentrations are avoided. The second field
has been the continuation of the five-year Metropolitan air
pollution survey# now in its third year. The records continue to
indicate that no aajor problea yet exists. The third field
concerns ataospheric pollution by aotor vehicles. Records
indicate that the position is satisfactory, even though the ratio
of vehicles to population in Auckland is siailar to that in
Los Angeles where a serious pollution problea is known to exist.
Hew and aodern equipment, including an infra-red gas analyser,
have been used in obtaining these records. Pollution figures
have been obtained in city streets and in offices at various
locations above street level. Saoke froa heavy diesel vehicles
is the aain adverse feature, and this is particularly evident in
the Newmarket results. This points to the need in a number of
cases for better aaintenance of transport fleets# and regular
checks on their operating efficiency. {Author introduction)##
01912
0. A. Lynn and T. B. BcHullen.
AIR POLLOTIOH II SIX HAJOR 0.5. CITIES AS MEASURED BY THE
COBTISDOtJS AIR HOIITORIHG PROGRAH (CAHP|. J. Air Pollution
942
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
Control Assoc. 16, 186-90, Apr. 1966* (Presented at the
58th Annual fleeting* Air Pollution Control Association,
Toronto, Canada, Jane 20-21, 1965, Paper No* 65-92.)
Data obtained by the Continuous Air Honitoring Program
(CARP) in six cities daring 2 years are summarized. Six
gaseons pollutants were monitored in Cincinnati, Chicago, New
Orleans, Philadelphia, San Francisco, and Washington, D.C.
during 1962 and 1963. The data serve as a basis for describing
several contrasts aad similarities in the nature of air pollution
experienced in six cities, which represent a broad geographical and
cliaatological range of urban environments. Specific topics
covered are: typical pollutant levels, patterns of daily and
seasonal variations, and unusual phenomena such as atnospheric
stagnation periods and photochemical snog formation. {Author
abstract}*#
01949
P. v. Hildebrand and R. L« Stockman
AID QUALITY IB CIAUK COUNTY, WASHINGTON. Washington State
Dept. of Health, Olympia, Division of Environmental Health.
7U PP.
This is a report on a community air pollution survey which began
Peb. 1, 1961 and which was conducted in cooperation with the
Clark County Air Pollution committee and the Clark-Skamania
Health District. The following findings, and conclusions, are
given- Clark County air pollution problems are primarily
restricted to localized areas in the immediate vicinity of specific
sources. Existing nuisance conditions and the potential for an
area-wide problem in the near future warrant corrective and
preventive action on the part of the community. Air pollution
concentrations in Portland, Oregon axe demonstrably higher than
those measured in Clark County leading to the conclusion that
area-wide pollution in the County will increase as community
development progresses. Air pollution effects that can be
established include fallout of solid materials, odor, soiling, and
esthetic considerations. Heating and transportation make
significant contributions to the total problem. Gaseous emissions
and concentrations have sot been studied sufficiently to establish
their effects upon the community, local legislation is presently
inadeguate to control th* problem on either a corrective or
preventive basis. This report recommends that an air pollution
control district, as provided for by the lavs of the state of
Washington, be established encompassing Clark County and the
cities of Vancouver and Camas.**
01981
A. P. Altshu Her and I- Cohen
THE GAS PHASE REACTIONS 07 HITBOGEI OXIDES VITH OIBFIVS.
intern. 0, Air Water Pollution ft, (1/21 55-69, 1961.
(Presented at the 13«th Annual fleeting, American Chemical
Society, Chicago, 111., Sept. 1958)
J. Air Quality Measuromants
9*3
-------
The nature of the condensation products formed in the gas phase
reactions of nitrogen dioxide and nitric oxide with pentene-1,
2-methylbutene-2, and 2-methylbutadiene-1,3 vas investigated,
the reactants were combined at partial pressures in the range of
0.1 to 2.5 nm with the total pressure at one atmosphere. The
products were determined by infrared and ultraviolet spectroscopy
and colorimetry. The condensates included primary and
secondary nitro compounds and alkyl nitrates, strong hydroxyl
and singld bond carbon to oxygen stretching vibrations indicate th*
presence of either nitroalcohols or simple aliphatic alcohols
formed through oxidation reactions. Carbonyl stretching
frequencies observable in some of the reactions support the
conclusion that a portion of the reactants disappear
by qxidation rather than by nitration processes^ The available
results do not indicate the presence of appreciable amounts of
tert.-nitrocompounds, conjugated nitro-olefins, or
gem-dinitroalkanes. The reactivities of the olefins with the
nitrogen oxides are in the decreasing order:
2-methylbmtadiene-l,3, 2-nethylbutene-2» pentene-1. {Author
abstract) #»
02179
L. E. Hiemeyer.
S OH HER SUH - CIHCIIMTI SHOG: A FECENT INCIDENT. J. Air
Pollution Control Assoc. 13 (8) 381-4, Aug. 1963.
Three conditions are considered necessary for the formation of
photochemical air pollution: sources emitting air pollution, slow
atmospheric dispersal of pollutants, and solar radiation. As we
have seen, all three conditions were fulfilled in Cincinnati on
the 16th and 18th of Hay. The city acted as the source of
pollution. Probably the greatest contributors were the city's
inhabitants as they came into the city by car and bus to begin
their daily routine. The stagnated anticyclone that dominated the
region, with its attendant clear skies, light winds, and
we11-developed radiation inversion, brought about slow atmospheric
dispersal of pollution and permitted the sun"s rays to act on the
contaminated air mass without obstruction. The intense solar
radiation did produce the photochemical reactions, but also
produced enough surface heating to mix the contaminated air mass
to heights well above 5000 feet-alleviating, to a degree, the high
concentrations that occurred before inversion breakup. The
meteorological conditions that brought about this incident,
although not frequent in southern Ohio, nay be expected
periodically* These conditions can lead to excessively high
pollution levels if the sources of contaminants remain at their
present number or increase in quantity.**
02241
*.H. Perry B.C. Tabor
IATI0IAL AIB SAHPLIHG SZTV01K MEAS0BEHEBT OP S02 ADD -H02.
Arch. Environ. Health 4, 254-64, Har. 1962. (Presented at
the Industrial Hygiene Foundation of America, Inc.,
Pittsburgh, Pa., Oct. 25-26, 1961).
944
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
The air in the cities participating in the NASH is currently
monitored for sulfur dioxide and nitrogen dioxide. The
sulfur dioxide method used by the Network psssesses good
collection efficiency and sufficient sensitivity for the levels
encountered, slight losses of pollutant say occur in the
inlet system and on aging of the solution after collection;
these losses are minimized by periodic replacement of the
prefilters and prompt analysis of all samples on receipt from the
field, the nitrate solutions collected in the nitrogen dioxide
aethod have adequate stability, and no significant influence is
exerted by the inlet system. The aethod is necessarily empirical
because of low collection efficiency and incomplete knowledge of
the reactions involved in the conversion of mixtures of oxides of
nitrogen to the nitrite ion* (Author summary}*#
02317
9.J. Basbagill J„l. Dallas
AID QO11ITT IN BOSTON, HASSACHDSETTS (NOVEHBER-DBCEHBER 1963).
Public Health Service, Cincinnati, Ohio, Div. of Air
Pollution* Nov* 1964. 55 pp.
A short-term air contamination pilot study was conducted using a
mobile air-sampling laboratory* This laboratory, designed and
constructed by the Technical Assistance Branch, Division of
Air Pollution, Public Health service, contains continuous
automatic equipment for monitoring air quality, manual air-sampling
equipment# meteorological instrumentation, and laboratory
facilities. This mobile laboratory was used to: (1) obtain
comprehensive measurements of gaseous and particulate air
contaminants at a single test site, (2) train air-contamination
investigators in the application of methodology, <3) evaluate and
compare air-contamination measurement techniques, and (1) enhance
public awareness of the air-contamination problem to encourage
support for local air-contamination control and monitoring
programs.##
02340
AIR QUALITY DATA FROM THE NATIONAL AIR SAMPLING NETWORKS AND
CONTRIBUTING STATE AND LOCAL NETNORK5 1964-1965. Public
Health Service, Cincinnati, Ohio, Division of Air
Pollution pp. 128, 1966.
The Air Quality Section of the Public Health Service's
Division at Air Pollution, with the assistance and cooperation
of state and local agencies, carries on a variety of air sampling
activities to obtain information about air quality in the Baited
States. This report summarizes data gahtered during 1964 and
1965 at nearly 300 stations that gathered bi-weekly samples of
suspended particulate natter, about 30 stations that gathered
bi-weekly samples of two gaseous pollutants, and another seven
stations that continuously monitored six gaseous pollutants.
J. Air Quality Measurement*
946
-------
suspended particulates and soiling index* This volume also
continues the policy of including summaries of data contributed by
state and local agencies that operate their own air sampling
networks. This effort to bring together in one publication as
much air quality data as possible is particularly important in
light of the continuing rapid expansion of state and local
sampling activities. In addition to the basic data on suspended
particulates and gases, data on several fractions of the
particulate matter are included herein. (Author abstract)##
023 61
H. B» Landsberg
AIB POLLUTION AND OBBAN CLIHATE. Proc. Intern.
Biometeorol. Congr. 618-56, 1966» (Partial paper presented at
the Third International Biometeorological Congress, Pau,
France, Sept. 2-7, 1963.)
In this general review of air pollution in relation to
meteorology, the author states that, although atmospheric
motions are* in general, sufficient to dilute pollutants to a
tolerable level, there is a high probability that once in three
years a major pollution episode can be expected. Vith increased
population, higher degree of industrialization and greater traffic
densities of motor vehicles, the diluting and self-cleansing
properties will become more and more taxed so that the
frequency of adverse pollution episodes is likely to
increase.•#
02370
S.*Duckworth E. Kupchanko
*11 AWALTSIS: THE STAIDADD DOSAGE-AREA PBODDCT. J. Air
Pollution Control Assoc. 17, (6) 379-83, June 1967.
(Presented at the 59th Annual Meeting, Air Pollution Control
Association, San Francisco, Calif., June 20-24, 1966, Paper
66-94.)
The dosage-area product (DAP) i« offered as • feasible,
lov-cost, and operationally useful data analysis output, it
is in essence a smog index obtained by multiplying the
contaminant dosage by the geographical area affected. Thus it
represents the intensity and extent of an air pollution
episode. The basic concepts of dosage and dosage-area, and
some standard constraints for obtaining reproducible index
values are discussed, several practical uses of the DAP smog
index are illustrated. It can be readily computed from a daily
map shoving the areal extent of contaminant dosage. The
DAP Snog Index is recommended as a feasible aid in presenting
and analyzing past, current, and future air quality conditions.
It is suggested for use in studies ot smog patterns* pollutant
trajectories# smog experience, pollutant treads, and smog
forecasting.#•
946
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
021131
F. a. Bell, Jr., B. S. Burke, P. F. Pero, E. E.
Thacker, B.. Z„ Hidmer, J. 6. Williams, Jr.
AIR POLLUTIOH HEASUREHBWT STUDY 15 RICHMOND, VIRGINIA, JASUABY
18-24, 1962. Virginia State Sept* of Health, Richmond
Bureau of Air Pollution Control and the Public Health
Service, Washington, D. C. , Div. of lir Pollution. 1962.
20 pp.
This study was undertaken for the purpose of obtaining an initial
estimate of gaseous pollution levels together with particulate
natter levels and meteorological variables, and for
introducing air pollution Measurement techniques to State and
local personnel. In general the gaseous concentrations were low
except for sulfur dioxide, the source of which were the emissions
from coabustion of sulfur-bearing fuel, mostly fro* coal. Data
and figures are given.#*
02822
s. Hochheiser and R. E. Retzel
AIP P0L1DTI0H SBISUBMESTS IV INDIANAPOLIS (JUWE-JULY 1963).
Public Health Service, Cincinnati, Ohio, Div. of Air
Pollution and Bureau of Air Pollution Control, Indianapolis,
Ind. 67 pp., July 1964
The Indianapolis Bureau of Mr Pollution Control and the
Division of Air Pollution, U.S. Public Health Service
conducted a joint air pollution study in June and July 1963. &
aobile air sampling laboratory was used in the study. This
laboratory contains continuous automatic equipment for
monitoring air guality, aanual air sampling equipment,
meteorological instmnentationf and laboratory facilities- This
aobile laboratory is used mainly to (1) obtain comprehensive
measurements of gaseous and particulate air pollutants at a single
test site in various communities; {2) train air pollution
investigators in the application of methodology^ (3) evaluate and
coapara air pollution measurement techniques, and f
-------
02623
S- Hochheiser, H. Nolan* and H. J. Dunsmore
AIH POLLUTION MEASURESENTS IN DOQUESNE, PENNSYLVANIA (SEPTEHBEB
OCTOBER 1963). Public Health Servicer Cincinnati, Ohio,
Dir. of Air Pollution and Allegheny County Health Dept.,
Duguesne, Pa., Bureau of Air pollution Control. Oct.
1964. 37 pp.
Air pollution levels are of sufficient aagnitude to justify
further planning and development of the air resource management
prograa serving the Duguesne area. Pollution due to particulate
natter is a major problem. Atmospheric particulate
concentration exceeded 290 aicrograas per cubic aeter 50 percent
of the tiae. Pollution due to sulfur dioxide is also a major
problea. Hourly sulfur dioxide levels reached 0.66 ppn during
a period of relatively poor ataospheric ventilation.
Photochemical-type smog vas not detected nor was it expected
during the fall season. The potential of photochemical snog in
Duguesne is greatest during the suaaer months. The resources
available should be increased to perait a aore extensive air
resource aaaageaent prograa. A continuing air aonitoring prograa
should be instituted at strategic sampling sites throughout the
area to determine seasonal and yearly treads of pollution, and to
provide inforaation upon which to base control prograa decisions.it
02825
T. E. Kreichelt and E. W. Dahle# Jr.
AIR POLLUTION HEASOBEHBNTS IN BALTIMORE, HD. (H ARCH AND APRIL
1964). Public Health Service, Cincinnati, Ohio, Div. of
Air Pollution and Baltiaore city Health Dept., Hd., Bureau
of industrial Hygiene, Nov. 1964. 58 pp.
GPO: 817-288-2
Air pollution concentrations measured in this brief study are
sufficiently great to justify further planning and development of
an air resource aanageaent prograa in the Baltiaore area.
Conclusions based on the Halted data of this study are as
follows; Pollution due to particulate matter is higher than
desirable. Ataospheric particulate concentrations exceeded 200
aicrograas per cubic aeter 5 out of 36 days of the study or 14
percent of the tiae. Soiling index vnlnea were rated as "heavy"
or greater daring 22 percent of the study period. Pollution due
to sulfur dioxide is soaetiaes a problem. The average sulfur
dioxide concentration during the study was 0.06 ppn but did reach
an hourly concentration of 0.24 ppn. Photocheaical-type snog was
neither detected nor expected daring the spring season* The
relatively large concentrations of oxides of nitrogen,
hydrocarbons, and aldehydes present suggest, however, that
photochenically produced snog nay be a problen during the sunner
aonths with the occurrence of greatest intensity and longest
duration of sunlight. (Author conclusion nodified)I•
948
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
02832
a. E. Newell, H. W. Brandli, end 0. 1. Widen
CONCENTRATION 07 OZONE IN SURFACE AIR OVER GREATER BOSTON IK
1965. J. Appl. Heteorol. 5, <5) 740-1, Oct. 1966.
One of the conclusions of an investigator studying the global
o2one was that further systematic neasurements of surface ozone at
a number of sites over the globe would be of great value in
consideration of stratospherictropospheric exchange processes.
Objections were raised to a proposed network of surface ozone
stations because Measurements made near a city can be contaminated
with oton« produced locally by the action of sunlight on
autoaobile and industrial exhausts. The gross results of a
one-year period of Monitoring surface ozone in the relatively
well-ventilated region of Greater Boston, are considered with
respect to the general circulation of ozone in the atmosphere and
its possible use as a tracer of the vertical transfer of energy
from the troposphere to the stratosphere. At present pollution
levels, ocone of stratospheric origin can be Monitored in a
reasonably well-ventilated city. The proposed network, therefore,
seeas quite feasible. These observations will continue for
several years.«t
02840
G. B. Welsh and T. E. Kreichelt
CLEAN AIR FOB CHATTANOOGA. Public Health Service, Atlanta,
Ga», (Region IT) and Public Health Service, Cincinnati,
Ohio, Div. of Air Pollution. July 1964, 77 pp.
The results of United investigations, based on air' quality data
obtained during a 30-day sampling period, other available air
quality data, evaluation of existing information related to the
air pollution problem and a review of the present air pollution
control program are presented. Of primary concern in Chattanooga
are improper combustion of coal and fuel oil, particulate
materials, odors, and fly ash. The sources are industrial,
domestic, solid waste and open burning, and motor vehicles,
local meteorological and topographical factors contribute to the
accuaulatioa of air pollution in Chattanooga, tow-level
inversions occur frequently {about 35 percent of the total hours
per year). Although Chattanooga has had a smoke abatement
program since 1935 and some progress has been made, there is an
apparent need for a more comprehensive air pollution control
program*••
03001
THE AUCKLAND IIS POLLOTION RBSB1RCH COMMITTEE (SEVENTH ANNUAL
KEPT. FOP TEAR ENDING HAS. 31, 1966.) lackland lir
Pollution Research Committee, New Zealand. 33 pp., 1966
J. Air Quality Musurements
949
-------
The conclusion of the fourth annual survey in Auckland, New
Zealand, Is that no significant increases in air pollution
have occurred in the last year. The specific areas of
consideration are: (1) smoke levels, (2) odors, and (3) pollution
by notor vehicles. The report reflects an increased awareness by
the public of the air pollution problem and is exemplified by the
adoption of smoke regulations.*#
03004
J-M. Brown F.D. Maddox
AB APPRAISAL OF THE AIR RESOURCE OF METROPOLITAN BALTIMORE.
Maryland state Dept. of Health, Baltimore and Public
Health Service, Cincinnati, Ohio, Div. of Kir Pollution.
(Bept. No. 165-33.} June 1965. 111 pp.
Report includes a discussion of the topographical characteristics
of the Baltimore, Maryland area and a review of past data
on air pollution control and air pollution potential.
Recommendations for a comprehensive study leading to an air
resource management program are presented. Specific topics
in the report {as they relate to the Baltimore metropolitan area}
are these: <1) present pollution levels, (2} sources of air
pollution, industrial and non-industrial sources, (3)
meteorological aspects of air pollution, and (4) the
administration of a future control program.ft
03024
SUMMARY OF DATA FROM THE CORTIROOOS AIR MONITORIMG PROGRAM.
Public Health service, Cincinnati, Ohio, Division of Air
Pollution* Oct. 1965. 16 pp.
This report contains data gathered faring 1962, 1963, and 1964,
with the data from 1964 presented more extensively than
data from the earlier years. The annual average
concentrations, the maximum and minimum monthly average
concentration, and the maximns daily concentration of the several
pollutants sonitored are summarized. The minimum daily
average concentration ««¦, in each case, below the minimum
concentration detectable by the instrusents* The following
summaries ace contained in tables* 1964 average and maximum
pollutant levels in greater dsttil for the several cities.
Relative cumulatively frequency distributions for 1961 3f basic
CAMP data rscoreded at 5-sinmte intervals, and similar
distribution of data for 1962 and 1963. These frequency
distributions permit the ready determination of the
concentration that «as exceeded only 5 percent of the tine, the
median concentration. Total oxidant data for 1964 in the
fors of the number and percent of day when the macisum hourly total
oxidant concentration equalled or exceeded 0.15, 0.10 and 0.05
ppn, and the average and maximum soiling index levels for 1964.##
950
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
03027
J. D» Williams, P. D. Kaddox, T. 0. Harris, C. H.
Copeley, Jr., and W. Vand Dokkenburg, Jr.
IMTEBSTATE A IB POIIUTIOB STOM PBASB II PROJECT REPORT. VI.
EFFECTS OF 1IH POLLOTIOS. Public Health Service,
Cincinnati, Ohio, Vational Center for Air Pollution Control
66 pp., Dec. 1966
The Air Quality Goals Subcommittee, appointed under provisions
of item 5-1-5 of the Interstate Air Pollution study Phase
II Project Agreesent, reviewed literature, met with
consultants is the air pollution effects field, and selected air
quality goals for consideration by the Project Executive
Committee. The Committee limited its consideration to goals
because it does not have authority to adopt air quality standards,
a function restricted to legally constituted governmental agencies.
The Committee does, however, by approving this report, accept the
consensus of professional and technical personnel. The
explanations of effect levels presented herein were prepared by the
staff of the Public Health Service Technical Assistance
Branch who utilized the advisory resources available within the
Division of Air Pollution. The effects of air pollution as a
program element, is only one part of an air resources management
program. Air pollution effects, air-quality levels, and pollutant
emissions are the major program elements that provide the basis
for air quality goals. Actually, if no consideration were given
to the length of tine needed to reach goals or to the priorities of
community needs, air pollution effects would be the only program
element to be considered in establishing goals. Suggested goals
are listed and are based on the air quality (indicating major
types and amounts of pollutants present) as well as actual and
anticipated effects of air pollutants in the Interstate Air
Pollution Study area* The effects of air pollution have been
considered in this report from the viewpoint of a consultant whose
task has been the development of a set of goals that will meet the
future need of the area. Some of the quantitative relationships
between effects and air quality levels have not yet been
established, but enough is known that a guide for a constructive
air resource management program has been provided for the
Interstate Air Pollution Study area. This guide is intended
to serve the needs of the study area only, and is not intended to
have general application.*#
031 Oft
H.C- Bohlers H. Feldstein
IB?ESTIGATIOB TO DFTBMXtfS TBI POSSIBLE HEED FOR A REQ0IATI0B OS
ORGAIIC COMPOUND EBISSIORS FBOH STATIORART SOBRCBS IB THE SAB
FBAbciSCO BAT ABBA. J. Air Pollution Control Assoc. 15,
(5) 226-9, Bay 1965.
On the basis of evidence presented, it is concluded that
photochemical smog is a major air pollution problem in the San
J. Atr Quality Measurements
-------
Francisco Bay Area. Attempts should be nade to reduce
the intensity of photocheaical snog effects by controlling the
eaission of organic coapounds to the atmosphere. In order
to reduce the intensity of photocheaical snog effects in the
Bay Area, it is estiaated that an 80 percent total reduction of
organic material eaitted to the ataosphere is necessary. The
nitrogen oxide problea needs clarification. Because of the
complexity of the photocheaical saog reaction in open atmospheres,
technical answers to all phases of the problea are not available.##
03006
B. L. Hecham, •)* S. A Been, B. W. Slater, Jr.
A PILOT STODY OF AIB QUALITY IN WINSTON-SALEH, NORTH CABOLIHA
-------
period beginning in September, 1959. In addition to providing
surveillance data, the program was to serve both research and
instructional purposes in Sanitary Engineering at The
University of Arizona. The U.S.P.H.S., through its
Region XX office* and the Arizona State Health
Department were to cooperate by rpoviding technical
consultation, sow air pollution equipment loans, and certain
aanpower assists. The project was to be conducted within the
framework of the Engineering Experiment Station of The
University of Arizona. The period of sampling extended froa
September 10, 1959 through June 14, 1960 During the
regular sampling days throughout the sampling period, observations
were made for oxidants, nitrogen dioxide, nitric oxide, sulfur
dioxide, carbon dioxide, and particulate natter. The period
of testing extended fron 7 A.H. through 3 P.M. Beginning
January 1, 1960, the D. S. Public Health Service
established a National Air Saipling Network Station at The
University of Arizona. Operation of this station involves
collecting a 24-hour High Volume air saaple tvice a month and
sending it to the Robert A. Taft Sanitary Engineering Center,
Cincinnati, Ohio, far analysis. Although the gaseous pollutant
levels could not be considered as high levels of pollution when
compared to a city such as Los Angeles, it should be pointed
out that the population of Los Angeles is approximately twenty
tines that of Tuscon. Data from -the U«S* Public Health
Service's Rational Air Saapliag network (an average of
141 cities) over the two-year period of 1957 and 1958 showed an
average pollution of 130 micrograms per cubic meter for the
Tucson area for the subject sampling period, oxidant
concentrations compared very favorably with other cities.4#
03*09
6. J. Raschka
AH APPRAISAL 07 AIR POLLUTION II MINNESOTA. Hinnesota Dept.
of Health* Minneapolis, (In cooperation with the Public
Health Service.) Jan. 1961. 78 pp.
This appraisal of the air pollution situation in Hinnesota
arose froa a growing concern about air pollution problems
in the state. Increasing requests for information and assistance
registered with the State Department of Health Service were
obtained concerning nothods of conducting a survey which
would establish the nature and extent of the air pollution
problea in the state and indicate what activity is needed on the
part of tho state aad local governments in aeeting the
problea. Data used in preparing this report were obtained
by interviews, direct observation, questionnaires, limited
air saapliag, and review of existing information. The appraisal
was made froa October 1959 to July 1960.#*
J. Air Quality Measurements
953
-------
03126
E., C„ Tabor, J. E. Heeker, and J. H. Leavitt.
AIR POLLUTION IN ST. BERNARD, OHIO. Public Health
Service, Cincinnati, Ohio, Div. of Air Pollution,1958. 17 pp.
HE*
Hn area survey was conducted in St. Bernard, Ohio. It vas
determined that the levels of suspended particulates and crude
organics were considerably higher than that in downtown
Cincinnati for the sane days. The average levels of 270
Micrograms of suspended particulate per cubic meter of air and
65*5 micrograms of crude organics per cubic meter of air were
sonewhat higher than for other coaaunities of size comparable to
St. Bernard. Nitrate and sulfate concentrations also were
slightly higher. The highest levels of sulfur dioxide, while not
high enough to be of great concern, were associated with northerly
winds. On several occasions the level of oxides of nitrogen was
high enough to be detectable by the odor. The large amount of
aliphatic hydrocarbons in the organic natter was very unusual. It
was considerably higher than that from any other coaaunity in the
United States for which siailar measurements have been reported.
The soiling power of the air was higher when the wind blew from
the North.**
03133
F# A. Bell, i3r., 6. Bisel, «3r., T« N. HusHower,
to B„ Perry, P. J. Schuette, and E. Vihman.
FUESNO AIR POLLUTION STUDY. Public Health Service,
Washington, D. C-, Div. of Air Pollution; California
State Dept. of Public Health, Berkeley; and Fresno County
Health Dept., Calif. July 1960. 25 pp.
HEW
Haze and other air pollution effects have occurred in the
Central Valley of California. In order to answer questions
regarding present pollution levels and to estimate the future
pollution potential of an area which is Just beginning to
experience air pollution, Fresno was selected as a representative
growing Metropolitan area of the Central Valley. Air pollution
concentration levels together with visibility reduction
aeasnreaents and subjective observations indicate that
photocheaical smog occurs in the Fresno area. The Fresno rural
station in Kerney Park had ftisi particulate matter results
which were in general higher than the results at the Fresno city
station. AISI particulate Batter results indicate that episodes
of air pollution occur widely throughout the Valley. Comparisons
of average results froa stations at Feesno, at Kearney Park,
Sacramento, Stockton and Bakersfield show that the ftisi
results were two to tone tiaes higher for the December 3-9 period
than for the September 10-17 period for all stations. An
estiaate of pollutants being emitted to the atmosphere indicates
that aotor vehicles are the a*in end most significant sources of
sB09~foraing raw aaterlals in the Fresno area.t*
954
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
03434
F. A. Bell, Jr., R., J, Beck, J- H. Shrimp, and
Be Welsh*
A PILOT STODT OF AIR POLIOTIOfl IK WASHIRGTOB. D.C. Public
Health service, Washington, c», Div. of tic Pollution.
Dec. 8, 1960. 19 pp.
HEW
The study covered seven days, including one weekend, and one
all-night sampling period for intensive air pollution sampling.
The period covered was December 2 through December 8, 1960,
from 9:00 AH to 5:00 ph. The all-night saapling period
covered 9:00 AH, December 5 through 9:00 At), Deaember 6.
The gas and particulate pollutants under test were selected to
be indicative of the general air pollution of the area. Oxidant,
nitrogen dioxide, nitric oxide, carbon aonoxide, smoke and
particulate were sampled. Visibility measurements to ground level
objects were taken every hour. The roof of the seven-story
District of coluaiba Municipal Center Building, 300 Indiana
Avenue, N.W., was selected as the saapling site. The following
equipment was used in the study: Multiple gas saapling
apparatus; High voluae particulate sampler; AISI autoaatic
saoke sampler; and Sepctronic "20" analyzer.##
03441
CLEAR XI* FOB CALIFORBIA flBlTlAI BIPOOT Of TUB AIB POLltJTIOK
STODT PROJECT, CALIFORBIA STATE DIPT. OF PUBLIC HEALTH).
California state Dept. of Public Health, San Francisco.
Bar., 1955. 60 pp.
This is an early survey report of the air pollution situation in
California. The body of knowledge, available at that tine, on
the growing problems of polluted air is discussed and a plan for
action outlined. Attention is focussed on the air pollution
problea in the Los Ang«les area, where eye irritation, plant
damage and other haraful effects, such as discomfort, decreased
visibility and nuisance occur aost frequently* Recommendations to
state and local Governmental authorities, to universities and
other research organisations, to the Industry and public are made.#
03453
POLLUTION OF THE ATHOSPHSBE II THI DETROIT BITER ABBA.
International Joint Commission, Detroit Biver Area, Air
Pollution. 1960. 273 pp.
The air is being polluted on both sides of the international
boundary to an extent that is detriaental to the general welfare of
J. Air Quality Measurements
955
-------
the citizens in communities along the Detroit River and to
property interests. Vessels plying the waters of the Detroit
Fiver, particularly the hand-fired coal-burning vessels,
contribute seriously to pollution of the air over, and in the
vicinity of, the cities of Detroit and vindsor and other
communities along the river on both sides. Industrial, domestic
and transportation activities on land contribute to the overall
pollution of the air to a much greater extent than vessels plying
the river if consideration is given only to average pollution
levels over the entire study area. Continued surveillance should
be maintained and some form of continuing regulation should be
enforced to ensure that there is no appreciable lapse in the
performance achieved under the voluntary control program. For
vessels of sufficient cargo-carrying capacity, the costs of
conversion to either automatic stoking or oil firing would be
repaid within a reasonable number of years. At an average cost of
about $85,000 per vessel, the above conversion program for 200
vessels would entail a total expenditure of about $15,000,000.
For the larger hand-fired vessels, there are insufficient
resources available in equipment and manufacturing facilities to
meet the problem of the immediate conversion of large numbers of
hand-fired vessels to more modern firing methods; a reasonable time
period should be allowed for the installation of such equipment.
The costs of the remedial measures necessary for abatement of air
pollution from vessels should be borne solely by the owners of such
vessels.##
03454
H. c. Cope, Chairman.
SHOKB *TO KB POliOTIOH - HZ1 TO** - HOT JBBSET. Interstate
Sanitation Commission, Hew York City. Feb. 195B, 95 pp.
Pollution in the metropolitan area was studied by: aerial
reconnaissances and photography; and surveys in the communities.
Significant information was collected on: relationships of
meteorology, visibility and pollution; interstate movement of
pollution as indicated by releasing tracer dust in one state and
collecting in the other; amoant of vehicle exhaust fumes and
other organic materials in the air; sulfur dioxide
concentration on Staten Island, and oxone on Staten Island and
in Carteret, V.J,; effects of the polluted atmosphere on health,
vegetation, materials and transportation; and a study and
evaluation was made of existing laws in the State of Hew York,
Sew Jersey and Connecticut, and other jurisdictions. Kir
pollution originating in regions of Hew York and Hew jersey
within the Hew Tork Metropolitan Area is interstate in
character, affects public health and comfort adversely, and damages
property, flhile the control and abatement of air pollution at its
sources is the primary obligation of the states, counties or
municipalities in which it originates, the problems of interstate
air pollution cannot be solved wholly by governmental agencies
independently of one another. The abatement of existing
interstate air pollution and the control of future Interstate air
pollution is of prime importance to the persons living and industry
located in the area affected thereby, and can best be accomplished
through the cooperation of the states involved, by and through a
956
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
coiiaon agency or instrumentality. An interstate instrumentality,
employing the administrative practices followed by the Interstate
Sanitation Commission in the abatement of interstate water
pollution, should be created to deal with the problems of
interstate air pollution, crafts of proposed legislation to neet
the situation described in this report should reflect folly the
opinions and needs of Many agencies, local governing bodies,
members of the legislatures, representatives of industry, and of
the public. There has been insufficient tine between the
completion of the study and the submission of this report to afford
opportunity to interested agencies to express their views on the
form which legislation to abate interstate air pollution should
take.«#
03458
D. H. Keagy and J. J. Schueoeaan
MB POLLOTIOU IK TBI BIBRIHGTOH, ALABARA, ABEA. Public Health
Service, Cincinnati, Ohio, Div. of Air Pollution. (Bept-
Ho. A58-8.) Hay 1958. 80 pp.
HEH: A58-8
The purposes of this survey were to: (1.) Review the existing
and potential air pollution situations. (2.) Review existing air
pollution control activities; and (3.) Develop recoaaendations
for organization, staff, facilities, program, and legislation
relative to air pollution control activities. The scope of the
study was limited to consideration of available inforaation
relative to air pollution including: types of activity which
cause pollution, evidences of pollution levels, meteorological and
topographical influences on the dispersion of pollutants, existing
or authorized governaental activity for control of air pollution,
and other relevant coaaunity characteristics. The study area was
the boundary of Jefferson County.tt
03462
E. B« Leake, 8. B. Shaffer, and J. A. Verssen
SOHHABY OF AIB POLLOTIO* DATA FOR LOS A1GSLES COUNTY. Los
Angeles County Air Pollution Control District, Calif.,
Engineering Div.
laission concentrations of pollutants for Los Angeles,
California are given. The levels cited are a result of the
Board of Supervisors of Los Angeles giving the authority
to the Air Pollution Control District - County of Los
Angeles. Also included are sixtytvo <62) industrial control
programs started in the Los Angeles area, along with the dates
installed and the cost.##
J. Air Quality Measurements
957
-------
03466
®• P* Sa B. HcKfi0f F* A* Bsll| Jr«, ftnd R«
S. Carter
AIB POLLUTION IB GEORGIA* Georgia State Dept. of Public
Health, Atlanta, Industrial Hygiene Service; Public Health
Servicer Cincinnati, Ohio, Div. of Air Pollution; April
962.. 35 pp„
CFSTI: PB 168 312
During recent years air pollution has come to the forefront
nationally as a major problem of man*s environment because of its
nuisance, property danage and other effects, and because of its
potential in jury to health. In 1959 a survey of industrial air
pollution in Georgia, carried out by the Georgia Department of
Public Health, shoved the existence of a number of significant
air pollution problems due to emissions from industrial plants.
Emission of air pollutants has been increasing in Georgia from a
variety of sources including automotive vehicles, burning refuse
dumps, home and commercial heating plants and other sources, in
addition to industrial sources. These increased emissions have
resulted in a mounting number of air pollution problems.
Therefore, a statewide survey was undertaken to provide a
current assessment of air pollution in Georgia and to develop
recommendations for necessary action.#*
03468
H. D. High, R« 6. Slater, and G. G. Costantino
A PILOT STODY OP AIB P0II0TI08 IV PBOVIDEUCI, SBODE ISLAND.
Public Health Service, Cincinnati, Ohio, Robert A. Taft
Engineering Center. (Rept. Ho. A62-15,) June 1962. U9 pp.
HESi A62-15
This study covered two equal periods of 15 sampling days each.
Samples were collected for determination of sulfur dioxide,
nitric oxide, nitrogen dioxide, carbon monoxide, and total
oxidants, on a bi-hourly basis, visibility from the sampling site
was determined on the same schedule; photographs were taken to
document visibility restrictions. Particulate pollution levels
were monitored continuously in three ways. Soiling index was
determined with the AISI strip filter paper sampler with a
tt-hour sampling tine; suspended particulates were collected on a
24-hour basis for determination of total weight; and a single
dustfall sample was collected over the entire period of each
phase of the study. Methods of measurement are described in the
appendix, and the primary sources of pollutants are listed.#*
03505
a. D» Home do and J. H. Tillman
AIB POLLUTION II THE EL PASO, TEXAS ABBA. El Paso City -
County Health Onit, Texas. 1959, 104 pp.
958
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
The primary purpose of this study was to obtain basic scientific
air pollution data concerning the type, extent, source, and effect
of the waste from industry and other air pollution in the El
Paso area. Another purpose was to determine the need and nature
of a permanent air pollfition control program* The scope of the
program was limited by two factors; the gathering of those samples
which were within our leans to analyze and the collection of
pollutants commonly found in any city.**
03511
AIB MONITORING AND SAMPLING NETWORKS (PROCEEDINGS OF THE 1959
SEMINAR). Public Health Service, Cincinnati, Ohio, Div of
Air Pollution. (Sept. A60-3.J. 1960. 143 pp.
HEW: A60-3
The objective of the seminar was to exchange views among people
engaged in the operation of air sampling and monitoring networks
for the purpose of gaining information on the objectives,
organization, operation of networks, and the analysis and
utilization of data obtained from their operation. Specific
topics reviewed are: (1) state and local networks, <2) selection
of sampling sites, (3) equipping sampling stations, (4)
laboratory support needed, and (5) interchange and release of
data.#*
03512
6. B. Welsh
AN APPRAISAL 0? AIR POLLUTION IN SPARTANBORG, SOOTH CAROLINA
-------
(lesults of a one-week air pollution survey in Lynchburg,
Virginia, revealed the following: 1. The levels found give a
clear indication that Lynchburg has an air pollution problem. 2.
The levels found for soiling capacity and particulate natter
indicate the presence of a general smoke problem. 3„ The
visibility standard for ambient air of the California state
Health Department {less than three miles at less than 70 percent
relative humidity) was exceeded on six days, another indication of
high particulate levels and smoke. 4. A combination of
meteorological conditions, including low wind speed, temperature
inversion, and a haze layer at the top ria of the James River
Valley were noted on February 15, The highest levels of general
air pollution for the entire sampling period occurred during this
period and appear to be attributable to the contained
¦eteorological conditions. 5. The high level of sulfur dioxide
is comparable to levels found in aany large population centers or
highly industrialized areas. The levels for sone of the gaseous
pollutants are about average for urban areas; however, under
conditions of low wind speed and temperature inversion, they nay
accumulate until auch higher levels are reached.##
03701
Cholak, L. J. schafer, V. J. Younker, and D. W.
Teager
THE RELATIONSHIP BETBE2S SDL70B DIOIIDE AMD PARTICULATE BATTER IN
TBI ATMOSPHERE. An. Ind. Hyg. Assoc. J. 19, (5) 371-7,
Oct. 1958. (Presented at the 19th Annual Reeting, Aaerican
Industrial Hygiene Association, Atlantic City, H.J., Apr.
24, 1958.)
The purpose of this aerometric survey was to study the
relationship between the selected pollutants in the natural
photochemical formation of the oxidant type smog- This paper
describes the features and the patterns of occurrence of
particulate matter and sulfur dioxide as observed in Cincinnati
since 1946. The findings obtained in the survey permit
interesting comparisons with those obtained in earlier surveys.*#
03714
J. Cholak and L. J. Schafer
THE COHCSITBA1XOVS Of OXIDABT (OIOHB) AID HITBOGEN DIOXIDE IN
THE AIB OF CXVCIIMTX, OHIO. la. Ind. Byg. Assoc. J.
21, 452-8, Dec., 1960. (Presented at the 21st Annual Neeting,
American Industrial Hygiene Association, Bochester, If- T.,
Apr. 25-20, 1960.|
The purpose of this paper is to describe observations concerning
the concentrations of oxidant, nitrogen dioxide and nitric oxide.
The frequencies of the occurrence of certain average hourly
concentrations of oxidant and nitrogen dioxide in the air at the
three stations and of nitric oxide at the Avondale station are
illustrated graphically. Higher concentrations of oxidant were
960
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
found in the Avondale section of the city. Values in excess of 1
ppha occurred 50% of the tine at the Avondale station, 38% of
the tine at the perineter residential station (French Park) and
only 26% of the tine at the downtown station* in average hourly
concentration is excess of 10 ppha was never reached at the
downtown station and occurred only 0*01 and 0.05% of the tine at
the French Park and Avondale stations respectively. The
order of rank of the three stations with respect to the levels of
concentration of nitrogen dioxide differed fron that shown by the
oxidant* The levels of concentration were higher in the downtown
area, and decreased in the air at the two residential areas in
accordance with their distance froa the central core area of the
city. Concentrations of nitrogen dioxide# averaging less than 1
ppha per hour were found 01% of the tine at the French Park area,
19% of the tiae at the Avondale station and only 2% of the tine
at the downtown station. Data on nitric oxide were collected for
several Months during 1950 and 1959 only at the Avondale station*
These data indicate that the average hourly concentration in
Avondale was less than 1 ppha for 84% of the tiae. Average
hourly concentrations in excess of 10 ppha occurred only 0.5% of
the tiae.*#
03715
3. Cholak, L. J» Schafer, D. Teager, and H. J. Toanker
GASEOUS C01TAKINANTS II THE AT10SPHBHE* A.H.A. Arch. Ind.
Health 15, 198-206, Har. 1957. (Presented at the Air
Pollution Syaposiua, 130th Resting# Aaerican Cheaical
Society, Atlantic City, ?*0., Sept. 17-21, 1956.)
This paper deals with the concentrations of oxidant, nitrogen
dioxide, aulfur dioxide, and carbon aonoxide found in the air in
the course of prolonged tests daring three seasons of the year*
The concentration of sulfur dioxide in the air of Cincinnati
varied with the season. It was. lowest during the suaaer when the
coabustion of solid fuel was at a ainiaua. The level of
concentration of oxidant as recorded by the potassiaa iodide
recorder varied Inversely with the concentration of the sulfur
dioxide present. The highest levels of concentration were found
during the sanae* season. The oxidant usually reached its aaxiaua
value during the afternoon and was lowest during the night. The
concentration of oxidant in the ataosphere of Cincinnati ranged
between 0.2 ppha and 6 ppha. The diurnal fluctuation in the
concentrations of aitrogen dioxide indicated that the
concentrations were generally higher at night than during the
daytiae* The lowest levels of concentration were found during
periods when the oxidant reached its highest value* The levels
of concentration of aitrogen dioxide ranged between 0*2 and 9.5
ppha* The concentration of carbon aonoxide in the air during all
three periods was very near the Halt of detection of the aethod
eaployed, being below 1 ppa generally.#*
J. Air Quality Measuremsnts
961
-------
037 25
C„ p„ Hosier
HATtlRAL RADIOACTIVITT (RADOH-222) A8D AIR POLLUTION
HEAS0FEHEMT5 IS RASHHTGTO* , D«. C. J. Appl. Heteorol. 5, (5J
653-62, Oct* 1966.
Atmospheric concentrations of radon (Rn222) were measured at
urban* suburban and rural sites in the Washington, B.C.,
metropolitan area during a stagnant weather regime in aid
August 1965. An analysis of air quality data, radon
concentrations and meteorology indicates that the stagnant veather
conditions vhich lead to the accumulation of smoke, haze and
gaseous pollutants in the air, are conducive to the
accumulation of radon in the lover atmosphere. During
maximum stagnation radon concentrations were 2-4 times higher
than normal; the high levels of natural radioactivity reflect
the limited volume of air available for dilution, caused
by a restriction to vertical mixing that prevailed
throughout the stagnant period. This case study suggests
that higk concentrations of natural radioactivity will be
indicative of air pollution potential conditions existing in the
atmosphere.* Also# air guality data indicated that heavy
rains and vigorous mixing associated with a squall line were
ineffective in cleansing or displacing, for a significant length
of time, the polluted air mass. (Author abstract)it
03863
A. L* chaney
IHVISTIGATIOHS TO DETECT THE ATMOSPHERIC COIVERSIOR 07 SULFUR
DIOXIDE TO SDLP0R TFIOXIDE* Proc. Am* Petrol. Inst.,
Sect. Ill- 38, 306-12, 1958. {Presented at the 23rd
Hidyear Meeting, American Petroleum Inst. Division of
Refining Los Angeles, Calif., Bay 15, 1958.)
In the gaseous state, the sulfur dioxide is only very slowly
oxidized to sulfur trioxide. It has been suggested that in the
presenece of fog and particulate-matter catalysts, this
oxidation may be greatly accelerated. If oxidation does occur,
both sulfate and acidity of the partial&te matter should increase.
Because nitrate is frequently also present in significant
quantities, its relationship to acidity should also be known.
Techniques have been developed for testing this hypothesis
in the Los Angeles area. Particulate matter was collected
and weighed in two separate fractions based on particle si2e, and
aqueous extracts of it were prepared for determination of
acidity, sulfate, and nitrate. Larger particles were
collected by dry impingement and the subaicron size by filtration
through membrane filters. Pog droplets, if present,
would be in the first fraction* Simultaneous sampling for
sulfur dioxide concentration was carried out by a highly sensitive
and. specific procedure. The sampling period was one hour, and
provision was made for automatic collection of several successive
962
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
samples at intervals throughtout a 2t»~hour period. These samples
were sufficient in size for measurement of both total weight and
weight of the water-soluble fraction. Chemical determinations
in the microgram range were utilized for the sulfate, nitrate#
and acidity measurements. The sulfur dioxide was usually
very low in concentration and was not well correlated with
sulfate level, other sources besides sulfur dioxide may be
required to account for the sulfate levels found in the
particulate matter. A large fraction of the particulate matter
was found to be water solublef particularly in the
submicron fraction, and it contained acidity which could not be
accounted for in terms of the sulfate and nitrate levels found.
(Author abstract modified)*t
04173
G„ P.. Gushchin, I. I. Romashkina, and o. N. Chemyakina
SOVIET STATIOK DATA OB TOTAl ATMOSPHERIC OZOSE POP 196 3.
s.s«R. literature on Air Pollution and Related
Occupational Diseases, S. S. Levins, Vol. 13. (Part II -
Atmospheric Ozone. Data presented at the May 21-23, 1963
Conference on Atmospheric Ozone.) pp. 235-75« 1965. Buss.
|Tr.|
CFSTI: TT 6662191
Total atmospheric ozone data recorded by 21 Soviet stations
during 1963 are listed in tables, consisting of observation data,
number of observations, and total ozone. Vibrations in the
aerosol layer still affect ozone measurement results. The results
were obtained in direct sunlight. Data were obtained with the
universal ozonometer, and with the Dobson spectrophotometer.,*#
04325
P. L. Meadows, J. J. Henderson, and C. B. Robison
AIR POLL0TIOH PATTERKS IR SIXTEEN ALABAMA CITIES. Preprint.
1967.
In 1962, the Alabama Respiratory Disease and Air Pollution
study was initiated to determine the prevalence of various
pulmonary disorders and to relate these findings with air quality
data. This paper describes pact of the aerometric effort begun
in October 1962 in 16 Alabama cities. Samples for analysis of
suspended particulate, dustfall, sulfation, and 2U-hour gases
(nitrogen dioxide and sulfur dioxide) were collected routinely from
26 stations in the 16 cities. The study is described and
statistical procedures are discussed, lix quality results «re
presented with emphasis on spatial and temporal differences between
cities in the study and comparisons are made with other studies.
Tables and diagrams give details oa the 16 cities surveyed.
(Author abstract modified)ft
J. Air Quality Mea$urwiwits
963
-------
04348
I.. A. Pipperton
OZORE AHD OZOHE PRECBBSOBS I* THE ATS0SP8EBE OF CHAPEL HILL,
NORTH CAROLINA. J. Geophys. Res. 70, (20) 5009-15,
Oct. 15, 1965.. {Presented at the International Atmospheric
Ozone Symposium, Albuquerque, II. Hex., Aug, 31-Sept. 4,
1964„)
Seventeen continuous 24-hour samples of ozone were obtained in
the community air of Chapel Rill, N.C* The readings vere
made over the period of a year with a Hast ozone meter. The
The over-all range was 0.0 to 13.0 pphm« The daily ranges varied
from 0.0-0.1 to 6*4-13.0. Atmospheric sampling for a
number of pollutants revealed the fact that the air of Chapel
'ill was intermediate in cleanliness between rural and,urban air.
Ambient air was captured in three different systems, two glass
and one Hylar, and irradiated with artificial light or sunlight.
Of 29 samples, irradiation caused an apparent ozone synthesis in
25* Four of these case» were confirmed with a Regener
ox;Insinescent ozone meter. Of the 21 increases measured with the
Mast ozone aeter alone, 9 were greater than 1.2 pphm. The
differential of 1.2 pph« was established as the confidence level
of the Hast instrument by evaluation in this laboratory.*#
04546
A. Turk c. J. D'Angio
COMPOSITION OF natural FRESH AIE. J. Air Pollution control
Assoc. 12, (1) 29-33, Jan. 1962. (Presented at the 54th Annual
Meeting, Air Pollution Control Association, New York City,
June 11-15, 1961.)
Certain outdoor atmospheres considered to be pleasant are
usually referred to as "fresh". In an effort to determine the
specific components responsible for the sensory effect of
"freshness", the present investigation was undertaken. The
organic vapor content of three typically "fresh" atmospheres,
mountain, forest and seashore, was anlayzed. The forest and
seashore atmospheres were chemically characterized by the
presence of aromatic ethers, and some unsaturated material.
The mountain atmosphere was found to be too low in concentration
of organic matter to be analyzed. The method of sampling and
analysis described lends itself to applications in
meteorological surveys.##
04562
K. Kawamura and S. Sakvrai
THE CONTEST OT THE ATHOSPHERIC BITROGEi DIOXIDE I* THE S0B01B
OF TOKYO. Heteorol., Geophys. 14, (3-4) 214-24, Dec. 1963.
964
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
The concentration of H02 in the ambient air was observed at the
western suburb of Tokyo for the period from September 1960 to
August 1961, using an automatic gas sampler. The results of
determination revealed that U02 concentration shoved a narked
diurnal variation in winter with two maxima respectively at about 3
hours after sunrise and at about 2 hours after sunset, and two
¦iniaa respectively at sunrise and in the afternoon. The tine of
occurrence of the afternoon minimum varied greatly day to day,
while those of the dawn minimum and of the evening maximum did not
change greatly, falling on most of days within the range of plus
and ninus one hour froa the monthly average. The norning peak was
always lower than that in the evening and no norning maximum was
observed often in summer as well as on windy days in other seasons.
The nonthly aiean concentration of H02 at night was higher than
that at day and the maximum values of 78 and 51 aicrograas
N02/CO m were observed in Deceaber respectively,, The diurnal
variation In H02 seeas to be attributable to the combination of
meteorological conditions and photochemical effect. (Author
abstract)##
09616
J.. E„ Dickinson
MR QDALITT OP LOS ANGELES COUHTY (TECHNICAL PFOGBESS SEPORT
VOLUME II). Los Angeles County Air Pollution Control
District, Calif. Feb. 1961. 306 pp.
Voluae II of the Technical Progress Deport is concerned with
chronicling the air monitoring progran of the Los Angeles
County Air Pollution Control District between 1951 and 1959.
Topics covered include: Chemistry of the Ataosphere; Air
Aonitoring; Evaluation of snog Effects Dfcta; Estimation of
Total Air Pollution in Los Angeles County; Utilization and
Analyses of Total Air Pollution Data. Hithout the data
accumulated as the result of the sampling programs of 1951-57 it
would not have been possible to discover the unique problems
involved with Los Angeles snog and to determine what kind of
control measures would be needed to abate them. Thus, it was
possible (1) to identify in the ataosphere the contaminants
considered to be the most important with regard to photochemical
smog formation theory; |2) to establish their approximate
concentration ranges; (3) to confirm theories of photochemical
snog formation and transport; and to define the areas of the
Basin most severely affected by smog and the areas in which nost
of the contaminant sources were concentrated. Correlation
between meteorological trends and smog occurrence, without
radical change in emission concentrations, indicate the
importance of weather conditions to smog occurrence*##
04651
B. To Comains R. E. Waller
OBSERVATIONS EHOH A TEW-TEAK-STODT OP POLLUTION AT A SITE IB THE
CITY op LOffDon. Atmos. Environ* 1, <1| 49*68, Jan. 1967.
J. Air Quality Mtasuramants
965
-------
As part of an extensive study of the effects of air pollution
on health, measurements of pollution have been nade at a site in
London for nore than ten years. The results of daily
measurements of the concentration of snoke and sulfur dioxide
nade throughout that period and of nore frequent measurements
nade during episodes of high pollution are reported. These
show a reduction in the annual Mean and peak concentrations pf
snoke during the ten year period, but there have not been
any significant changes in the concentrations of sulfur
dioxide* Occasional neasurenents of a vide range of other
pollutants are also reported and results from a series of
neasurenents of polycyclic aronatic hydrocarbons indicate
a decline in the concentration of this potentially
carcinogenic component of pollution in London. (Author
abstract modified)*~
0HB31
New York State Air Pollution Control Board, Albany. 1965.
15 pp.
AIK POLUJTIOR/CHEHURG COURTY (SUPPLEMENT TO COMPREHENSIVE
AREA SURVEY REPORT SOMBER ONE (GREATER ELBIRA).
Since the degree of air pollution is low in this rural portion of
Chemung County, proper steps would be taken to insure
continuing low levels of air contaninants. All new sources of air
pollution can be controlled by adherence to rules and regulations
promulgated by the Hew York state Air Pollution control
Board in 1962* Local officials, in cooperation with the Board,
can insure new sources or Modifications to existing sources and
neet minimum requirements as established by the Board. Rules
and regulations for this area should be nade at the same tine as
those for Greater Elnira, using anbient air guality objectives
as promulgated by the Board. Hhen applying the anbient air
guality objectives, both the present survey area and Greater
Elnira should be classified as one region. In this manner, all
of Chenung County nay have a uniforn set of rules and
regulations at the sane tine. Refuse disposal practices should be
reviewed in each conaunity. Open burning of refuse by private
individuals should be prohibited and central collection
instigated. Disposal should be properly-operated, sanitary
landfills or any other acceptable nethod. (Author sumnary)##
0486#
New York state Air Pollution Control Board Albany. 196#„
96 pp.
AIR POLLUTION - NIAGARA COUNTY ICOHPREHENSIVE AREA SURVEY
Report nuaber three).
The objectives of this study are to define the nature and extent
of the air pollution potential in Niagara County so as: (1j To
provide information by which rules and regulations can be
906
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
established for the control of existing air pollution; (2) To
provide technical data needed for implementation of a practical
and reasonable air pollution abatement program; (3) To assess the
effectiveness of existing controls and determine what steps must
be taken by governnental. agencies to control both existing and
potential air pollution; and (4) To provide background data needed
to check the effectiveness of any future control program™##
04996
H. Katz
sources OP POILOTIOH. proc. Rati. Air Pollution
Synp.r 2nd, Pasadena, Calif., 1952. pp. 95-105
The wind and cloud conditions in the Detroit River area for
five years are summarized. Sulfur dioxide was measured by
antometers. Hydrogen sulfide, chlorine, oxides of nitrogen,
and ammonia were sampled. Suspended particulates were
collected.. The distribution of dust fall components is
tabulated. About twenty metallic elements were identified by
x-ray diffraction of suspended particulates. Community
health surveys covering morbidity and mortality records and
accounting for ethnic and socioeconomic factors are outlined.##
05008
Dew Tork State Air Pollution Control Board, Albany. (Feb.
1966.) 132 pp.
AIR POLLUTIOW/THE HID-HUDSOW: GREENE, 0L5THR, ROCKLAND,
COLOMBIA,DUTCHESS (COHPREHEHSIVI AREA SURVEY REPORT HUHBER SIX).
A comprehensive study of the air pollution potential in the Bid-
Hudson area was undertaken as a cooperative effort by the
Columbia, Durchesa, Rockland, and Ulster County Health
Departments, and the State Health Departments Oneonta
District office (for Greene county) and Hiddletown District
Office (for Beacon City). The objective of the study was to
define the nature and extent, and causes and effects, of the air
pollution potential in the Hid-Budson area. Both industrial and
nonindustrial air pollution were studied by conducting an inventory
of possible air contaminant sources and determining contaminant
emissions within each county. The inventory was supplemented by
an atmospheric sampling network consisting of 41 stations located
throughout the five counties.##
05010
Hew Tork state Air Pollution Control Board, Albany. (July
1958.) 76 pp.
A REVIEW OF AIR POLX.UTIOR IX HE* YORK STATE.
J. Air Quality MMSurammts
967
-------
This report contains current knowledge of air pollution problems
affecting He* Tork State. Previous study results are
summarized and more important factors influencing air pollution in
the state are discussed. The nature and types of air contaminants
their effects* and the elements of air pollution legislation are
considered. Study areas for future activities of the Air
Pollution Control Board and priorities for action are proposed.#
05095
F. A. Bell, Jr., and G. B. Welsh
METROPOLITAN WASHINGTON COUNCIL OF GOVBfiNMi: N1S • OXIDANT SAMPLING
SBTWOKK (ANNUAL BEP08T OCT. 1961-SEPT. 1962). Public Health
Service, Washington, D. C., Division or Air Pollution.
(Oct. 25, 1962.) 28 pp.
Photochemical smog, which arises primarily icon the action of
sunlight an automotive fumes in the atmosphere, has been
demonstrated to be a significant problem in the Washington
metropolitan area, without the institution at appropriate
automotive or other control measures, increasing population anil
numbers of automotive vehicles will cause the photochemical smog
problem to become progressively more sevece. The maximum oxidant
level of 0.41 parts per million (ppw), measured at the D.C.
Municipal Center Building Station, is about one-third the
maximum (phenophthalin oxidant) concentration measured in Los
Angeles County, but this cannot be interpreted to nean that
photochemical smog in Washington is necessarily one-third as
severe as it is in Los Angeles County because of the
differences in sampling freguency and analytical procedures. Ten
days with an oxidant level of .25 ppm or more, the level at wnich
some eye irritation is noted, were recorded at one or more Network
stations during the first years' operation. With the exception
of the Prince Georges County Health Department Station, all
stations have reported one or more days with oxidant index o± .25
ppm or higher. However, on the average th E.C. Municipal
Center Building Station appears to have the highest oxidant
concentrations. During the first year of operation oxidant levels
showed a definite seasonal cycle, low concentrations during cold
months, and higher concentrations during warmer months, one or
more days of eye irritating levels occurred in Hay, June, July,
August, September, and October but none during the other months
of the year. The first years* operation has shown that, given
a modest amount of technical assistance and coordination, useful
air pollution surveillance data can be gathered for a metropolitan
area with a minimum expenditure for manpower time, equipment,
ana supplies.*#
05110
1. J. Hamming, 8. D. HacPhee, and J. R„ Taylor
COSTARIHAST COSCMTRMIOHS I* THE ATMOSPHERE CP LOS IHGElSS
C00HTY . J. Air Pollution Control Assoc. 10, (1) 7-16, 93,
Feb. 1960.
968
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
The primary purpose of this study was to analyze long-term
pollution trends as measured by the Los Angeles air monitoring
network. Except for work in England on a distinctly different
type of air pollution problem, there ace £ev data available which
span any appreciable number of years. The District's
monitoring was accomplished with 24-hr recording devices- Its
usefulness is justified primarily as a protection and warning
Measure. A by-product of this operation is the generation of data
from which pollution can be studied. The findings may be
summarized as follows: (1) During the three-year period, 1956-59,
the general level of CO rose. The rise in CO of one ppm per
year was not reconciled with weather or other pollution factors.
The rise in N02 was small and trends are available only from
1957. S02 varied slightly without changing its general level.
Particulates declined during 1956 and 1957 which could have been
due in part to the District's incinerator ban. A preliminary
study on the basis of comparable weather factors appeared to
justify this conclusion. The oxidant, eye irritant, and plant
toxicant declined in 1956 and 1957 from a high in 1955, but
exhibited a slight upturn in 1958. Winds and inversions appear
to the determining factors for trends in eye irritant, oxidant and
plant toxicant. {2) la examining the monthly average data used as
the basis for the trend lines, it was observed that certain
contaminant and weather factors could be grouped together.
Monthly averages for primary, or Type I factors exhibited annual
peaks in midwinter. These were CO, hydrocarbons, N02,
particulates, S02 (not perfect fit), frequency of morning
surface inversions, and the inverse of 1600-1900 PST windspeeds.
In addition, the Type I contaminants are known to yield bimodal
diurnal variations. Secondary, or Type II, entities showed
annual peaks in the autumn# and single daily peaks. These
included aldehydes, eye irritant, oxidant, plant toxicants, ozone
alerts, restricted visibility, the frequency of Rule 57 Days, and
the inverse of 24-hr average windspeeds. Both the yearly and the
diurnal cycles confirm the distinction between Type I and Type
II contaminants. (Author conclusions modified)##
05111
3m Cholak, L. J* schafer, and D« V. Yeager
THE CONCEBTRATIOR OF OZONE III TBI ATMOSPHERE OF C BUT AIM AHEHICAN
CITIES . J. Air Pollution Control Assoc. 227-32, 248
(Feb. 1956|. (Presented before a session on smoke and fumes,
20th Midyear Meeting, American Petroleum last.. Division of
St. Louis, So., Hay 10, 1955.)
The previous reported results of the analytical survey for the
first year are reviewed and the results of a new continuous
long-term investigation in Vashington, D. c. are presented.
The determination of oxidant in the atmosphere of 10 Eastern and
Midwestern American cities by the method used in the Los
Angeles area demonstrates that the concentration of oxidant, as so
determined and recorded, varies inversely with the concentration of
sulfur dioxide present in the atmosphere* The levels of
concentration of oxidant were generally so low as not to lend
themselves to correlation with meteorologic variables. The
photochemical production of ozone which appears to have occurred in
J. Air Quality Measurements
969
-------
los Angeles and vicinity could not be confirmed in this
investigation» Mo levels of concentration of oxidant above those
which have been recorded as normal in other investigations were
observed, except in Charleston, w. va., during a period of
heavy fog. The levels of concentration of the oxides of nitrogen
found in these observations bear no demonstrable relationship to
the density of motor traffic. Relatively high concentrations of
the oxides of nitrogen were observed at times, but their effect on
of oxidant* as recorded instrumentally, could not be established
with accuracy. The levels of concentration of carbon monoxide in
the atmosphere, so far as this was investigated, appeared to vary
vith the density of motor traffic. The concentration during the
day generally reached its peak during the period of maximum
traffic, but on other days it remained at a uniform level
throughout the day.##
05112
Rogers, L. H.
NITHIC OXIDE AND NITROGEN DIOXIDE IN THE LOS ANGELES ATHQSPHERE»
J. Air Pollution Control Assoc. 8(2), 124-8, Aug. 195R.
{Presented at the 132nd National fleeting, American Chemical
Society, New Torlt City, Sept. 8-13, 1957.)
The objective of the studies reported here was to identify the
interrelationships between NO, N02, OXIDANT AND OXIDANT
precursor in the Los Angeles atmosphere. A four-channel
instrument was used to monitor the atmosphere, except for the
oxidant studies where a different instrument was used. The
instrument included a U-channel Brown strip chart recorder which
made successive readings on a special 7-cell colorimeter. The
colorimeter provided a means of measuring the reaction from 4
absorbing columns, one for each of the atmospheric components..
N02'*as measured after contacting the air with modified Griess
reagent; NO plus NO2 was measured by first converting NO
to N02 with a controlled concentration of osone, and measuring
the total N02 with modified Griess reagent: oxidant was
measured with 20% neutral KI; oxidant precursor was measured by
first passing the air sample through a SO 1. Pyrex flask
irradiated with four mercury arc lights, and then into a
contacting column containing 201 neutral KI. Average oxidant
precursor shoved a greater value than oxidant both day and night,
although the Maximum was about the same for both components in the
middle of the day. Oxidant precursor was distinctly greater
during the hours when the sun*s intensity diminished, and at night.
A minimum was observed at 5 to 6 A. M* The average
oxidant-forming power of the atmosphere, as measured by the
oxidant precursor valves, averaged more than 15 pphm. NO was
found to occur at larger concentrations than NO2 during the
night, but a reversal occurred during the daylight hours.
Horeover, there were two maxima for both components at about
8 A.8. and again about 6 to 10 F.n., vith two minima: One in
the middle of the day at about 11 A.M„ to 2 P.a. and in the
early morning at about 4 to 6 A.M. The minimum observed in the
middle of the day occurred at the same time as the maximum oxidant
value measured. The rough parallelism between No. and N02
concentrations at night suggests that Y02 is being formed from
MO, presumably by the reaction 2WO + 02 yields 2*02.##
970
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
05196
G. B. Bell, and S» E. Waggoner
* FIELD STUDY OF AIR POLLOTIOR IS THE LOWER 5ACRAHENTO VALLEY
DTJRIHS THE 1960 FALL SEASOK. California State Dept. of
Public Health, Berkeley, Bureau of Air Sanitation and
California Oniv„, Los Angeles, Division of Agricultural
Sciences. 72 pp. {Nov* 1961).
The objectives established for this study included: the analysis
of Sacramento's photochemical snog episodes during the 1960 fall
season for possible relationship to agricultural burning; the
comparative evaluation of the particulate natter brought to
Sacramento by down~valley winds when significant aaounts of
agricultural burning occurred and when little or no burning
occurred; the measurement of concentrations of oxidant,
hydrocarbon, and particulate Batter which characterized various
pollution events occurring during the I960 fall season; the
documentation of meteorological conditions which prevailed during
recognizable pollution events for comparison with sinilar
conditions when little or no agricultural burning occurred; and,
the better understanding of the principles involved and
interrelationships of agricultural burning and meteorology which
combine to produce visible air pollution*##
05200
J. Palomba, Jr.
DENYER HETROPOLITAS ABBA AIB SAHPLIKG SURVEY. Colorado State
Dept. of Public Health, Denver, sept. 1961. 28 pp.
The report points out that an air pollution problem exists in the
Denver Metropolitan Area in a sufficient degree to merit further
intensified action. This report serve as a cornerstone upon which
a sound program can be built; this will involve further study and
evaluation of the problem, and an adequate control program. Based
on results of this study, it is recommended that: <1) An emission
inventory be conducted in the Denver Hetropolitan Area; (2) A
continuing air monitoring program should be established for
determination of gaseous and particulate pollution levels; and (3)
Enabling legislation should be adopted to provide for an air
pollution control district properly empowered to establish and
enforce rules and regulations applicable to the entire Denver
Metropolitan Area.##
05277
B. j. steigerwald, L. V. Weinberger, and D. A. Lynn
A IS loss IV URBAff ATHOSPHEREm A.I.Ch.E. (American Inst..
Chemical Engineers.) Preprint. (Presented at the Symposium
on particulates and Air Ions, 55th Annual fleeting, American
Inst, of Chemical Engin«er*, Chicago, 111., Dec. 2-6, 1962.)
J. Air Quaffty Measurements
-------
Air ions (charged molecules, molecular aggregates, or snail
particles in air) are a constituent of all natural atmospheres.
Many qualitative observations have been reported of differences
in the atmospheric ion content of rural and urban air. The
investigation reported in this paper attempted to better define
the difference in air ion characteristics between urban and rural
locations and to relate ion differences quantitatively to type,
degree, and source of air contamination. Results indicate that
urban air contains high concentrations of intermediate and large
ions and very low concentrations of small ions compared to rural
air. The concentration of positive large ions was used to study
quantitatively the relationship between air contaminants and
atmospheric ions. The data were analyzed statistically by
correlation and regression methods- Variations observed in
temperature, humidity, and S02 at ambient concentrations had no
effect on large ions. Large-ion concentrations correlated only
slightly with particulate concentration as determined by
reflectance measurements but correlated very strongly with
variations in atmospheric lead concentration, used as an indicator
of automobile exhausts. It appears that in complex urban
atmospheres air contamination from automobile exhaust is the
dominant factor in the alteration of natural atmospheric ion
levels.#*
05336
C. E. Schumann and c. it. Gruber
AIB QUALITY DATA-1966. Cincinnati Dept. of Safety, Ohio,
Div. of Air Pollution Control and Heating inspection*
-------
is used mainly for domestic heating and oil for large industrial
plants. The types of coal used and their sulfur contents are
tabulated, along with soot-eaission concentrations. Hourly,
daily, and seasonal changes in S02 concentration and soot fall-
out are tabulated for various areas of the city. Data on air
pollution from automotible exhaust is also tabulated. Visibility
during the winter between 7 and 10 A.fl. and 4 and 8 P. II. is
significantly reduced. Economic losses and citizens complaints
are categorized*M
05481
AHBIEHT AIR: GOIIFOHD COUNTY, WORTH CAROLINA- Guilford
County Health Dept., Greenboro, N.C., Division of
Environmental Health. 1966. 52 pp.
The purpose of this report was to provide factual infornation
for the citizens and government of Guilford County for use
in the development of a program to control air quality in the
area. The County covers an area of 691 sg. Biles and has a
population of 246,520 <1960 census statistics). Industrial
activities include: textile, wood products, machinery and metal
products, food products, mineral products, printing and
publishing, paint, chemical and fertilizer manufacturing.
Pollutants resulting from these activities include: dusts, fines,
fumes, smokes, organic vapors, odors* and gases. Sampling
data for the year between 1964 and 1966 were obtained by the
following methods: high volume samplers for suspended
particles, dustfall jar sampling for dusts, AISI tapes for
soiling index measurements, and gas samplers for S02, NO and
KQ2. The sampling data are tabulated for the various
pollutants. Estimated fuel usage in the County for the year
of 1965 is tabulated, estimated sulfur content for coal was
0.9* and I-OX for commercial and domestic use, and
industrial use, respectively. Meteorological aspects here
pertaining to air pollution are also reported. .Results indicated
that an undesirable concentration of air pollution existed, based
on levels established in other sections of the nation. More
detailed and concentrated efforts are needed on gaseous sampling
for achieving meaningful conclusions.#•
05499
R. Katz
AIR POLLUTION III CANADA. Proc. Clean Air Conf. , Univ.
Hew South Vales 1, 23-40 (1962).
Air pollution trends in Canada, as in other countries, are
influenced by the growth and distribution of population and
industry. Increasing efforts have been made by industry and
government agencies to control the emissions of sulphur
compounds from smelting, oil refining and sour natural gas
processing operations through the recovery of useful by-
products such as sulphuric acid and fertilizer products or
elemental sulphur. A number of elemental sulphur plants have been
erected within recent years to utilize the hydrogen sulphide
J, Air Quality Measurements
973
-------
recovered from the purification of sour natural gas for
pipeline distribution systems. These sulphur plants vary in
daily capacity fron less than 300 to over 1000 long tons.
Research at the federal level in Canada on the toxic, effects
of air contaminants and related problems of sampling, methods
of analysis and identification axe centralized largely within the
Occupational Health Division of the Department of National
Health and Welfare. Divisional activities are organized into
two main units of environmental assessment and biological
studies* increasing number of industrial companies
are becoming aware of the importance of air pollution as a
factor in existing and new manufacturing operations. This
enlightened attitude on the part of management has resulted
in the undertaking of air pollution surveys before and after
the construction of their plants, in the assessment of sources
of emission to abate or eliminate air pollution problems and in
studies to determine the suitability of various sites from an air
pollution control standpoint.**
05500
J. L„ Sullivan
PARTICOLATE AND GASJOUS P0U.0TI0N IN NEB SODTH WALES CITIES.
Proc. Clean Air Conf», Dniv. New South Wales, Vol. 1#
I6p», 1962, Paper 1.
Measurements of smoke density, sulphur dioxide and oxidant
levels have been made in New South Vales on a routine basis
since 1958. Smoke densities were found to be high by the
standards of American cities but low is comparison to Great
Britain. During the months of winter the measured smoke
density was above 4 coh units pec thousand linear feet for
approximately 1/3 to 1/2 of the total time and levels above
10 coh units per thousand linear feet occurred on aost
winter atornings. Sulphur dioxide varied from approximately 1 to 6
parts per hundred million and extreme levels reached only
10-12 parts per hundred million on the basis of 29 hour
samples. The peak hourly concentration measured was 37.0 parts
per hundred million, though higher readings were observed in the
vicinity of specific sources. Is one case a peak of 13.5 parts
per million was recorded. Oxidant concentrations, measured by
absorption in neutral potassium iodine, varied between the
normal background of 0.02 ppv and 19 ppm. Higher concentrations
of smoke were observed to occur during anti-cyclonic conditions
when a moist maritime flow of air produced stable lapse rates
over the coastal area. The extreme smoke density levels were
associated with these conditions during the winter months and
cold drainage currents from the Dividing Range. The
meteorological factors associated with higher oxidant
concentrations have not yet been established in Sydney.
4Author abstract)**
05551
McRullen, Thomas B., rensterstock. Jack C., Faoro, Robert B. and
Smith, Raymond
974
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
AIR QUALITY AND CHARACTERISTIC COHHONITY PARAMETERS. J. Air
Pollution Control Assoc., 18(8):5»5-5U9, August 1968. (Presented
at the 60th Annual Meeting, Air Pollution Control Association
Cleveland, Ohio, June "11-16, 1967, Paper 67-26.)
Statistical correlations between all pairs of 16 selected air
quality Measurements and 13 selected community parameters for 66
standard Metropolitan statistical areas have been calculated*
tested for significance, and reviewed for meaningful relationships.
Of special interest are the correlations between the sulfate
fraction of suspended particulate natter and the use of sulfur-
containing fuels (r equal 0.66), between ambient sulfur dioxide and
the use of sulfur containing faels (r equal 0.85), between the lead
fraction of suspended particulates and annual purchases of gasoline
-------
This paper summarizes the aethods, the results, and sone
preliminary indications and conclusions employed in the survey.
& aajor purpose of the snrvey wa? to aonitor presumably important
variables so as to provide a aore adequate basis for diagnosis of
the general problem. Pinto beans were used to aeasure the plant
damaging effects of smog. Also measured were oxidants, nitrogen
dioxide, hydrocarbons, carbon monoxide, aldehydes, sulfur dioxide,
particulates, and meteorological factors. Soae of the
recommendations derived froa the survey are that aore complete
meteorological measurements be obtained, that plant damage as a
measure of smog be given more extensive study, and that a minimum
of ftt monitoring stations be established in the Los Angeles Basin..##
05627
V. E. Scott, E. R. Stephens, P. L. Hanst, and F. C.
Doerr
FOSTHER DEVELOPMENTS IS THE CHEHISTRY OP THE ATWOSPHBRB.
Preprint. fPresented at the Session on Air Pollution,
22nd Midyear fleeting, American Petroleum Inst., Division of
Refining, Philadelphia, Pa., Rat 14, 1957u|
The technique of long-path IR spectroscopy is currently being
used at the Pranklin Institute both for direct studies of
atmospheric pollution and for laboratory experiments. With the
field instrument, concentrations of most of the important
pollutants in the Los Angeles atmosphere were measured as a
function of time and meteorological conditions* These studies
supported the general picture of atmospheric pollutants and their
reactions which was developed from laboratory studies both at
The franklin Institute and in other laboratories,
laboratory studies Indicated the concentrations of HQ and H02
would be quite low in smog. The organic nitrogen compound,
identified as perotyacyl nitrite, was a prominent product in the
laboratory studies, and it was predicted that this compound would
be found in the smog. Both of these conclusions were confirmed by
atmospheric analysis. The presence of ozone, long used as the
primary smog indicator, was also confirmed. Air analyses for
several major pollutants, made after sundown, showed a close
similarity to an analysis of diluted automobile exhaust and to an
analysis of air taken near a heavy traffic center.. Several
compounds whose presence in polluted air has been suspected were
found to be below the limit of detectability. Among these were
H2Co, HH03 and CH30R. Reaction products of 03 with
olefins at low concentration <30 ppm to 60 ppm) were identified as
aldehydes, CO, C02, water, and, from propylene and 2-pentene,
ketone- Other products of the reaction between 03 and the
higher olefins were indicated. Yield of CO and C02 indicated
a definite connection between chain length and the decomposition of
products. Several pure ozonides were prepared at low temperature,
and their infrared spectra recorded. In some cases the
decomposition products were determined.t#
976
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
05652
Anderson, D. 0., flilliaas, I. H., ana Ferris, B. G., jr.
THE CHILLIVACK BESPIBATOBY SOBVIY, 1963: PAST II- AEBOHBTBIC
STUDY. Can. (led. Assoc. J. 92, 954-61, Hay 1, 1965.
A study of the quality of the aabient air at Chillivack, British
Columbia, vas conducted froa Ray 1963 to April 1964. Heasurements
of dustfall, sulfation, hydrogen sulfide, oxidants and total
hydrocarbons were aade by a network of five saapling stations. The
results of this survey indicated that Chillivack was relatively
free froa any air pollution and would therefore be a suitable
control for a study of the relationship between comaunity air
pollution and respiratory disease.
06141
THE PBESEHT STATUS OF AIB POIIUTIOM IS OSAKA CITY. Kuki Seijo
{Clean Air - J. Japan Air Cleaning Assoc., Tokyo}
Data on air pollution for the city of Osake from 1960 to 1966 are
given in tables and graphs as follows: 1.) neteorological data on
teaperature, huaidity wind velocity, and wind direction gathered
froa the Osaka Meteorological Observatory, Itaai Airport, and
Yao airport. 2.) Quantities of heavy oil, coal, coke, and gas
used in Sakai and Osake in February, 1964. 3.) Yearly vari-
ations of dust fall in eight places for five years |1960 through
1964) are tabulated for exaaple, an over-all decrease froa 24-5
tona/sq. ka./aoath in 1960 to 18.9 tons/sq„ ka./aonth in 1964).
The concentration of floating dust in 1965 vas froa 0.0 to 1.8
vestaent in public and private facilities for the control of air
ag/cu. tu/day with peaks around 8 A.a. and 8 P.H. 4.) Tearly
and hourly variations of S02 and S03 concentration in 26
places In the city indicating that the aaount is increasing (0.95
ag/100 sq. ca./day in 1960 to 1.35 ag/100 sq.ca./day in 1964. 5.)
Pollution by autosobile exhaust at two heavy traffic circles
|11,000 cars/hr) indicated ia*iaun instantaneous values of C02
eaission were 4.6 ppa and CO eaission 85 ppa. Averages for
S02, 102, HO, HCRO, and ozone were also tabulated. 6.) Tearly,
aonthly, and hourly concentrations of saog are tabulated indicating
peaks are highest around 9 A.h. and when the wind is no core
than 1*3 a/sec* 8«) Visibility data is illustrated on a nap of
the city.**
06150
B. Sakabe, B. Soda, T. Ratsuaura, X* Honaa, and K.
Kosaki
AIB POIlOTIOl ST0DT AT HEAVT TBAFFIC BOAD. (Bull. Hatl.
Inst. Indust. Health, (Kawaskai, japan)| (4J 72-6, 1960. Jap*
1 report is given of the hourly aeasureaents of air pollutants
between 8 A.R. and 7 P.M. on Hareh 3 and 4, 1960 at a heavy
traffic circle ia Tokyo. The aeteorological conditions were:
teaperature 5 to 15 deg« e« huaidity 38 to 78fr and wind
J. Air Quality Measurements
977
-------
velocity 1 to » m/sec. The pollutants measured and methods of
measurement are as follows: CO (Kitagawa-type tester), S02
(Thomas* Method), HCHO (Sodium Hydrogen Sulfite and
Chromatropic Acid Sodium Salt Method), and NO and N02
(Okasa-Toda Method).. The results are tabulated and graphs of
the hourly variation are given. The average findinqs were CO,
2.5 to 20.0 pptn; S02, 0„02 to 0.097 ppm; HCHO, 0.035 to 0.2
ppm; and NO plus N02, 0.008 to 0.032 ppm. The highest
concentrations were found between 8 and 10 A.H. and between 6 and
7 P.M.##
06169
B. I* Brabets, C. K. Hersh, and fl« J. Klein
OZONE KEASUBEHENT SBBVEY IB COHHEBCIAX, JET AIRCRAFT. J.
Aircraft 4 (1), 59-64 (Peb. 1967). (Also published as report
AD 600360 by IIT Research Inst., Chicago, 111., Contract
ARDS-608, TB-ADS-5, 54 p.. Hot. 1963.)
The purpose of this survey was 1) to measure accurately ozone
concentration in commercial jet aircraft cabins and/or flight crew
compartments on flights above 25,000 ft in order to obtain a
12-month statistical evaluation with emphasis on seasonal and
meteorological correlations, and 2) to locate and chart the
ozone-enriched air masses in order to obtain further meteorological
correlations and to establish any abnormal conditions that result
in exposure to large ozone concentrations. The ozone
concentration in aircraft was measured during 285 commercial jet
flights between September 1, 1962 and August 31, 1963. These
flights ranged over all segments of the Onited States and
included sections of Canada and the North Atlantic., All types
of commercial jet aircraft currently employed by air carriers were
monitored. The ozone measurements recorded on each flight were
evaluated, and the data were correlated graphically to show
seasonal variations. The maximum continuous ozone exposure
encountered on a domestic flight was 20 or more parts per hundred
million (pphm) by volume for 140 win; the maximum on a northern
flight was between 20 and 30 pphm for 4 hr; the highest
concentration encountered was 35 to 40 pphm for 20 min. The most
significant finding was that little or no ozone was detected on
flights below the tropopause. At or above the tropopause, the
internal concentration was usually above 5 pphm; in most cases it
was above 10 ppha«M
06192
Hiura, T. K. Kimra, K. Kimotsuki. H. Okusa, a.
Tada, and T. Sawano
COMPARISON OF THE CONCENTRATION OF SUSPENDED PARTICULATE BATTER
AND GASEOUS POLLUTANTS BETWEEN INDOOR AIR AND OUTDOOR AIB IN URBAN
AREA, fto&o Kogatoa (J, Sci. Labour Tokyo) , 41 (10), 493-500 (1965).
Jap. (Tr.)
The concentration of suspended particulate matter and gaseous
pollutants of indoor and outdoor air in Tokyo was determined at
several locations including factories# business machine rooms and
978
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
offices* The concentration of suspended particulate natters was
deternined by Roken Type long ten recording iapactor and gas
analysisfor S02, N02, and HCHO of indoor and outdoor air was
carried oat at the sane tine. The electromicrographs revealed that
most of the particulate natter in the urban area was nicrofine,
seeming to be carbon particles and some mist particles* The
concentration of suspended particulate natter of the outdoor air in
the urban area ranged fro* 0.05 to 0..5 ng/cu n and that of the
indoor air in air conditioned rooms ranged from 0.01 to 0..3 ng/cu.
n. The attenuation efficiency of an air filter with electrostatic
precipitator for suspended particulate natter was high. The
concentration of 502 of the indoor air was lower than that of
outdoor air, but the differences were not narked in cases of N02
and HCHO. (Authors* abstract, nodified)
06290
Public Health Service, Cincinnati, Ohio, National Center
for Air Pollution Control
WASHIHGTOH, D. C., HBTROPOLITAH ABBA AIH POLLUTION ABATEMENT
ACTIVITY. ((212)) p., Nov. 1967. 18 refs.
From February 1967 to August 1967 the Public Health Service
conducted a technical investigation in the Washington, B.C.,
netropolitan area to provide information that could form a
basis for recommendations for abatenent in accordance
with the tenets of the Clean Air Act. The results are
presented of the 1967 investigation and the methods, techniques,
and procedures are described. In concert with cooperative
regional and local agencies* an air quality network was establish-
ed, an enissions inventory was conducted, extensive neteorological
data were acquired, air pollution effects on vegetation and
various naterials were investigated, aod special data processing
and summarization techniques were developed. The boundaries
for' the activity conforned to the Hetropolitan
Washington council of Governments" area which includes the
District of Colunbia; the Maryland counties of Montgomery and
Prince Georges; the Virginia counties of Arlington,
Fairfax, Loudoun, ana Prince Villian; and the independent
cities of Alexandria, Talis church, and Fairfax.**
06551
A. Goetx
VISIBILITY 8ESTRICTI0H BT PHOTOCHEMICAL ABROSOL FORMATION.
Preprint. (Presented at the Air Pollution Research
Conference, Los Angeles, Calif., Dec. 6, 1961.)
Photochemical aerosol formation is caused by the tenporary
accumulation of reaction products from certain atmospheric trace
components upon nucleating particulates and results in their
substantial size increase. These reactions require the
coexistence of certain unsaturated hydrocarbon types (e.g.
J. Air Quality Measurtmrnts
979
-------
olefins), oxidizing gas traces, such as >0, N02, 03), and
irradiation in the 320 - 400 Hill!micron range of the sun spectrum.
The presence of additional S02 traces can enhance significantly
the aerosol formation. The final size of these aerosol particles
depends on that of the nucleating particles present prior to
photo-activation, on their concentration, and that of the reaction
products. Such smog aerosols are predominantly in the diameter
range between 0.3 micron -1.0 micron with a freguency about
inversely proportional to the particle volume and of a
concentration of 10 to the 9th power to 10 to the 10th power per cu
m. Us this size range is practically not subject to fallout by
gravity and also coincides with the optically visible wave-lengths,
such aerosols are most effective (Hie-type) light scatterers and
cause lasting, strong visibility restriction. The relation of the
latter to the particle growth is discussed in some detail.
(Author's abstract)##
06559
NATIONAL AIR SURVEILLANCE NETWORKS ANNUAL TABULATIONS - 1966.
Public Health Service, Cincinnati, Ohio, National Center
for Air Pollution Control (Jane 1, 1967)„ 207 pp.
A complete tabulation is provided of 1966 HASti*s data. The
tabulations are arranged in alphabetical order by states and
include: Suspended Particulates, (141 Stations); Gas
network, <52 Stations); and Lead Candle Network (Sulfation
Kate), (24 Stations). No analysis of the data is presented*
Analyses will be included in the Annual Report.*#
06700
NATIONAL AIR SURVEILLANCE NETWORKS - FIRST QUARTER TABULATION
1967. Public Health service, Cincinnati, Ohio, National
Center for Air pollution control. (1967). 217 pp.
The data obtained by tbe National Air sampling Network
(NASN) during the first guarter of 1967 are presented. The
tabulations are arranged in alphabetical order by state and include
data on suspended particulate, S02 and N02.#•
06701
NATIONAL AIR SURVEILLANCE NETWORKS CONTINUOUS AIR MONITORING
PROGRAM <1966 DATA TABULATIONS AND SUNiARIES FOR CHICAGO,
CINCINNATI, DENVER, PHILADELPHIA, ST. LOUIS, AND WASHINGTON,
D.C.). Public Health service, Cincinnati, Ohio, National
Center for Air Pollution Control. (1966). 551 pp.
The Continuous Air Honitoring Program is the National Air
surveillance Network which operates six continuous monitoring
stations in major cities throughout the country. The data
tabulations la this booklet are summaries of hourly concentrations
of gaseous pollutants and 2-hourly summaries of soiling index
levels during 1966. Also enclosed is a brief summary of monthly
means and maxima, and annual frequency distributions of data from
all stations.**
980
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
06707
SUMMARY OF 1964-1965 AIR QUALITY MEASUREMENTS. 90th
Congress ("Air Pollution—1967, Part 3 (Ale Quality Act")
Senate Committee on Public works, Washington, D.C.,
subcommittee on Ail and Water Pollution, April 19, nay 2-U,
8-10, 1967.) p. 129801306.
Air pollution surveillance activities conducted by the National
Center for Air Pollution Control include a nationwide network
of stations equipped for periodic measurement of suspended
particulate matter and, in some instances, such gaseous pollutants
as sulfur dioxide and nitrogen dioxide; a six-city network of
stations eguipped for continuous measurement of several gaseous
pollutants; and a relatively new network of stations designed to
provide a general indication of effects of air pollution on various
types of materials in interstate regions- Data from both the
periodic and continuous air sampling stations are discussed.#*
06723
j« So Rader
DATA ACQUISITION SYSTEMS IS AIR QUALITY. Symp. Environ.
Measurements, Cincinnati, Ohio, 1963, (PUS Publ. Ho.
999-AP-15.) (July 1964)„ pp» 107-23.
Two major automated data acquisition systems are now being used in
the United States for air guality measurements. These systems,
operated by the Los Angeles County Air Pollution Control
District and by the U.S. Public Health Service (Continuous
Air Monitoring Program) , are reviewed in details plans for
automated data handling by the California State Health
Department are discussed briefly. Design and operation of these
systems are reviewed in terms of sampling, detection, recording,
data validation, and data display. (Author's summary)it
06719
I. Kodama
AIR POLLUTION II KAVAGAIA PREFECTURE. Kuki Seijo (Clean
Air - J. Japan. Air Cleaning Assoc., Tokyo) U, <2) 23-9,
July 1966* Jap.
The Ranaqawa prefecture with aft area of 2361 sq. km and a
population of 4,430,000 has 60% of its population and 66.5* of its
factories concentrated in the cities of Yokohama and Kawasaki.
There are 1270 factories and facilities generating dust and soot
in these cities. The meteorological conditions in the cities are
described. The yearly variation of dust fall in industrial,
semi-industrial, business* and residential areafcfor 1957 to 1965
is graphed shoving mm average of 26.5 tons/sg. km month In the
industrial area of Kawasaki, 17.3 ia the semi-industrial area,
12.5 is the business section, and 9.2 in the residential area*
J. Air Quality Mtfsuitmffib
MT
-------
The dust fall consisted vainly of Pe203, CaO, and SOI. The
hourly variation of floating dust indicated a peak in the
afternoon. The greatest concentration was found in December.
Maps of the tvo cities are included shoving the concentration
of sulfur oxide in suaaer and winter. Graphs shoving the
amount of snog, which has been increasing remarkably in summer,
show the variation between the saog and the concentration of air
pollutants.. As for autosobile exhaust, the hourly variation of
CO concentration is given along with the nuaber of cars at that
tine. The effect of pollution on visibility is discussed. The
number of days in which the restriction of visibility is severe
is three tines as itany as 20 years ago.#*
06760
N. Saruta
AIR POLLOTIOH IN NORTHERN KYUSHU. Kuki seijo (Clean Air -
J» Japan Air cleaning Assoc., Tokyo) (2) 35-U5, JulyB
1966* Jap..
A preliminary investigation of air pollution in northern Kyushu
vas started in 1952 and studies on existing conditions have been
carried out since 1959. The yearly and Monthly amounts of dust
fall and S02 in the five wards of northern Kyushu are
tabulated for 1959 through 1965* The results show decrease in
dust fall (from 26.49 to 20.73 tons/sg. ca./aonth) and in increase
in SO2 (froa 0.25 to 0.6# ag/100 cc/day). Tabulations of dust
fall and S02 are given for the industrial, business, and
residential sections* The Pe203 present in red saoke has also
been Measured and averages between 2.0 and 2.8g/sg. a/nonth.
Heasureaents of 3,4-benzopyrene and coaponents of autonobile
exhaust such as CO, S02, Pb, NO, and N02 are also
tabulated for the five wards.**
06788
(STUDIES OF AIR POLLUTION 18 THE DEPARTHENT OF THE SEINE IN 1965.
PAST 3. CONDITIONS AT 0SLT AIRPORT.) Etudes de Pollution
Ataospherigae dans le Departeaent de la Seine en 1965.
Troisieae Partie. operation "Aerodroae d'Orly."
laboratoire Municipal de la Prefecture de Police, Paris,
France. (Apr.. 1966.J pp. 1-2, 9, 11, 13-7. Fr-
The results of an air pollution study aade at Orly Airport
at the reguest of the aedical services at the airport are given.
The survey covered the exposure to ground personnel and an
investigation of the components of the fuel and emissions froa
jets. The investigation was conducted by a Mobile air
pollution laboratory located at the field during the study* In
general, the pollution was ne9lible, the emissions froa the jets
were not a aatter of concern, but there was a nuisance hazard to
workers on piston planes* The carbon aoaoxide was determined
by infra-red absorption with aa average reading recorded every
IS ain» The averages ranged from 0.5 to 19 ppa. The other
contaainants that were determined included carbon dioxide, nitric
oxide, nitrogen dioxide, sulfur dioxide, aldehydes, lead, 3,4-
982
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
benzopyrene, toluene, xylene, and benzene, and in all cases the
results were much loner than those obtained in various stations
in Paris. Both on the basis of analyses ude on ambient air and
on emissions from jets there is little evidence of air pollution at
Orly Airport in Paris.**
06872
K. 1. Shesterikova P. N. strogal*shchikova
ATMOSPHERIC POIttJTIOS BT RITROGBR OXIDES. (Zagryaznenie
atmosfernogo vozdukha okislami azota.) Hyg. Sanit. (Gigiena i
Sanit.) 30 (5), 232-3 (Hay 1965). Buss. (Tr.)
Determinations of nitrogen oxides concentration over the streets
in Chelyabinsk, Russia, during peak traffic hours vere
compiled. In 51* of the samples, nitrogen oxides exceed
the maximum permissible concentration (0.3 mg/cu n). The lowest
concentrations of nitrogen oxides are found at two points, where
the traffic density is lower and the broad streets are
situated on an elevation, therefore in a well ventilated
position.#*
06948
CRITERIA FOR AIR QUALITY ADD BET BOOS OF IBASUBEHEJfT. World
Health Organization, Geneva, Switzerland. (Repfe» Ro.
DHO/1P/23.) (Presented at the Inter-Regional Symposium,
Geneva, Switzerland, Aug. 1963.) (Sept. 10, 1963). 20 pp.
An Inter-Regional Symposium on Criteria for Air Quality and
Hethods of Heasurement was convened in Geneva from 6-12
August 1963. Twenty experts in the field of air pollution fron
15 countries in the American and European Regions of WHO
presented technical papers and participated in the discussions.
The symposium discussed the rationale for selecting air quality
criteria in Hember countries, the role of epidemiological surveys
in establishing guides to air quality, and studies on effects
indirectly related to hua&a well-being, Bocfa as damage to
vegetation, soiling of surfaces, and reduction in visibility. The
Symposium also defined the areas In which further research is
needed to produce data that will serve as a sound basis for
establishing guides to air quality} the participants eapfcasized the
need for agreement on methods of measurement that, even If not
identical, yield comparable data* Topics discussed (1) General
considerations; (2) Rationale for selecting air quality criteria;
(3) Role of epidemiological aid aeroaetricsacveys; (4) Damage to
vegetation# soiling of surfaces and visibility redaction; (5)
medical studies needed for the improvenent of data relating to
guides to air quality; (6f needs for the standardization of Methods
of sampling and analysis of ambient air pollutants* (?) need for
international collaboration and agreement on air quality criteria
and methods of MasusMMBt.t*
J. Air Quality Meaiurerowts
983
-------
06960
E. W. Dahle, Jr.
AflBUAI. REPORT Of THE BORBAO OF IHDOSTHIAl HTGIEBE, 1966.
Baltlnore City Health Dept., Bd., Bureau of Industrial
Hygiene. (1966). 15 pp.
Some results of industrial hygiene investigations are cited.
The atmospheric monitoring program is discussed and the resalts
of sampling for oxidants, aldehydes, nitrogen dioxide, and dust
fall are graphed. Complaints involving air pollution are
tabulated.#*
06977
AIB RESOURCES IB THE HID-IIIIAiETTE VAIIEY. Kid-Willamette
Valley Air Pollution Authority, Salem, Oreg. (Dec. 1966).
80 pp.
In October of 1965, a survey and sampling prograa was initiated
to determine the quality of air within the five counties of
Benton, linn* Harion, Polk and Yamhill. Phase I of this
smrvey was accomplished by location of major sources of air
pollution, identification of amounts and kinds of pollutants
and, with meteorological data, establishment of dispersal and
disposition patterns of pollution. Sources of pollution in the
ftid-Hi11amette Valley consist mainly of combustion of
fuels for heat and power, process emissions, and industrial and
community solid waste disposal praetive. Other sources of
lesser significance at this time include auto exhaust emissions
and agriculture and forest management practices. Intermittent
build up of suspended particulates occurs during inversion periods
throughout the year. Any month of the year in Salem will see
inversions two of every three mornings. In conclusion, the
early findings in the study do not indicate the need for a crash
program of air pollution control* There is a strong indication
that unless a preventive program is initiated to cope with the
expansion and growth of communities and industries, the quality
of the air supply will rapidly deteriorate.##
07083
Jaffe, 1. s. and H. D. Bstes
OZORB II HIGH-A1TIT0DB AIRCRAFT CABXBS. Arch. Environ.
Health, 9261-71v July 1961
An analysis of osone at high altitudes was undertaken to assess
the naturtt of the osone problem in relation to current jet aircraft
and particularly the planned supersonic air transport (5ST{.
ozone is present in significant quantities in the atmosphere
starting above the tropopause and in toxic concentrations in the
stratosphere reaching a peak at about 70,000-90,000 ft. The
ambient ozone concentration varies with geographic latitude, season
984
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
of the fear* and meterological factors. The exact cabin
concentrations of ozone in various types of current jet aircraft at
different altitudes are being studied in relation to these factors
to detemine whether or not an environmental health problem
actually exists, particularly for aircrews. High anbient ozone
concentrations of 5 - 10 ppm are found at altitudes of 65,000 -
80,000 ft. through which the SST will cruise. The air used for
cabin pressurization passes t
-------
07120
Louv, C. V.. and E. C, Halliday
FTUST HEPOHT 0« ATMOSPHERIC OXIDASE M1ASORBHENTS IH THE TOWNS OF
PRETORIA, DDFBAIC AND JOHANNESBURG.. S. African Ind. Chera.,
18(111:218-221, Rov* 1963. 19 refs.
A short survey was made of the oxidant level in the atmospheres
of Pretoria, Durban and Johannesburg, Sooth Africa. It was
necessary to make control measurements in the country, av*y from
town pollution influences. These measurements were made at
Hammanskraal. Assessment of oxidant (including ozone, peroxides
and nitrogen oxides) in the air was done by a slightly modified
version of the standard phenolphthalin method as applied by the
U.S. Public Health Service foe Air Pollution work.
Averages of oxidant concentration for Pretoria, Durban and
Johannesburg are of the same order of magnitude. Average oxidant
concentration for the country atmosphere is slightly hiqher than
that of any of the three towns. The average atmospheric oxidant
concentrations obtained for Pretoria, Durban and Johannesburg
compare favourably with other large towns in America and Europe
and are at present substantially below the pollution level at which
unfortunate biological effects can be experienced.##
07166
K. Horiuchi
A STUDT 0* THE STATUS Q00 OF AIR POIIOTION IH JAPAIL Osaka
City Bed. J. (Japan) 10 (1):181-200 (196
-------
or haze-type snog is discussed* the yearly variation of the
nunber of "snog days" is graphed indicating seasonal influences,,
Snog decreases in winter bat increases in sunner and fall. The
current status of air pollution in Tokyo is also covered vith
respect to dust and soot fall, floating dust, sulfuric acid,
nitrogen oxides, hydrocarbons, and lead compounds, flea sure merit of
dust and soot fall in Tokyo began in 1955 and yearly variations
are graphed through 1965* Dust fall reaches a peak between
February and Hay and then again in August and September.
These peaks are related to the aeteorological influence of strong
winds in spring and large aaounts of rain in spring and late
sunnier. Therefore, July and December are considered the best
tines to investigate air pollution without neteorological
influence, lengthy discussion is given to daily and hourly
variations of pollution peaks in urban, industrial, and suburban
areas.##
07239
Hinowa, T.
PRESENT CONDITION OP AIR P01L0TI0N IN YOKOHAHA AREA. Fuki
Seijo {Clean Air, J. Japan. Air Cleaning Assoc.) {Tokyo)
3{4}:5-10, 1965. Text in Japanese
A systematic investigation of air pollution in Yokohama was
started in 1957* The hourly, daily, and aonthly variations in
concentration of pollutants are tabulated. The nunber of "snog
days" is graphed fro* 19*16 to 1964 showing an increase beginning in
1955 with the present total being twice as great as before 1954.
Studies of S02 concentration indicate that it was twice as great
in 1964 as in 1957. The aaount of dust fall appears to be
decreasing, especially ia the industrial area; it dropped fron 70
tons/sq. km. no nth in 1956 to 18 tons/sq. kau/aonth in 1964.
There has been little change, however, in coaaercial and
residential areas. Honthly variations of saog indicate that the
condition occurs nore readily in winter than in sunaer; the largest
dwst fall level occurs at the end of spring and the beginning of
suaaer and is smallest at the end of fall and the beginning of
winter. Floating dust and S02 concentrations are greatest fxoa
December to Febraary. Saog in winter has two peaks: the
higher one between 8 and 9 A.8. and the other between 8 and 9
P.M.; in sanaer there is usunlly one peak between 5 and 9 A.H.
Sulfur oxides and floating dusts show two peaks, depending on
aeteorological conditions. Sulfur dioxide concentration depends
nore on wind velocity than do floating dust and soot, osoally
502 concentration is not high when wind velocity is greater than
5 a/sec* The effects of sunlight on air pollution are also
discussed. According to seasuretent, the absorbed ultraviolet
radiation was aboQt 50* for an 502 concentration of 0.85.##
07245
T. Sekigawa
I0*s III AIR. II. Knkl seijo {Clean Air, J. Japan* Mr
Cleaning Assoc*) {Tokyo) 3 <3I» "6-50 (1965). Jap.
J. Air Quality Measuramwto
987
-------
A study was made on the physical aspects of air pollution in
realtion to the present situation In cities and according to
methods of measurement of very snail particles. In the center of
Tokyo, the ratio of dusts present according to particle sizes of
19 plus or minus 2 microns, 7.5 plus or Minus 0.3 microns, and 0.9
plus or minus 0*1 Microns is 1:1.3:15.2:103. The distribution of
particles 0«9 plus or Minus 0.1 Microns in size is given. The
study of extreMely saall particles (less than 0.1 micron) has not
been extensive. Methods of Measurement generally used are the
coagulation Method (density of fog generated by the particle is
measured), the diffusion coefficient Method (Strokes-Cunningham
equation used to calculate the particle size from the diffusion
coefficient! » anfl the charge separation Method (particle size
obtained froM Mobility of the charged particle). An illustration
given of floating dust and polluted air Measured indoors by the
mobility spectrum. For measuring the weight of floating dusts,
an automatic recording-type impactor was used and for measuring ion
concentration, the H H-type large size ion meter was used.
Hourly variations of floating dust concentration indoors and out
are graphed as well as variations of small ions based on
temperature, humidity, and wind direction. In connection with the
ion spectrum, small and medium ions can be separated clearly in
clean air, but the spectrum becomes continuous as pollution
increases. Roughly speaking, the quantity of small ions present
is inversely proportional to the amount of dust in the air.
(tedium size ions increase as humidity increases.##
07371
Hayashi, S.
THE PHESEHT SITOATIOB Of C00BTBB J1MS0RES FOB P0BLIC HOISANCE IH
JAP Alt. Text in Japanese. Kukl Seijo (Clean Air - J.
Japan Kir Cleaning Assoc.,) (Tokyo) # 1(1): 8-12, 1964.
General information on public nuisance in connection with the
rapid development of industry in Japan is given. As for the
present status of air pollution# the amount of dust fall, so2,
and automobile exhaust are investigated. Dust fall and S03
measured at 296 places is tabulated where the maximum dust fall is
137 tons/sq. km* per month (in northern Kyushu) and the minimum is
2 tons/sq.. km. per month, and for S03 the maximum is 2.7
mg/100 sq. cm. per day. In 1962* the maximum SO2 value of 0.23
ppm/hr was recorded and a concentration of 0.1 ppm/hr lasted for
19 hours in Tokyo. As for automobile exhaust, an instant CO
value of 10 to 20 ppm has been recorded very often and a maximum
of H02 was found between 0.02 to 0.05 ppm* i "public nuisance
prevention** law has been established mainly for the three largest
industrial areas, but some prefectures will not enforce it.##
07390
A. J* Lynch, E. J. Bowmer, A. sykanda, J. H. Smith,
J. H. Emslie
COHPABISOH OF HBTBOBOLOGT AID AIB QUALITY BETRBEB TWO COHHtJHITIES
II BBITISH C0L0BBIA—A PRELIHIIABT 1ZP0BT. Can. J. Public
988
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
Health '(Toronto), 58^6) :241-248, June 1967. 16 refs.
(Presented at the Anna- Beeting. Air Pollut. Contr. Ass.,
Pacific northwest Int. Sect., Seattle, Bash., hot. 3-4,
1966-)
Two series of saapling stations have been established to
develop methods for the comparison of aeteorological and air
quality findings in an area exposed to the contaainants fron kraft
pulp and paper mills with an unpolluted control area*
The clinate was aaritiae in both towns and there were inversions
in both valleys in both winter and summer. The preliminary
report covers the methods used in establishing the
saapling stations and the aeteorological observations and
analyses made between Oct. 1965 and Jane 1966. Six
stations were established in the polluted town and three in the
control town in industrial, commercial, and residential locations.
The Study will continue until larch, 1968 with additional
aeteorological and air guality aeasureaents.
Preliainary values show the dust fall is the polluted town
varying from 20 to 50 tons per sg mile and froa 4 to 10 tons
per sg aile in the control town. A secondary object of this
study was to relate the concentration of air contaainants to
the incidence of respiratory disease and to assess the long-
term effects on health of low concentrations of contaainants.#*
0V446
C. B. Robison, J. C. chaabers, J. w. Bates
DBFIWHG THE PHOBIEH OF AIB POLIOTIOH III METROPOLITAN
BIRHIHGHAH, ALABAMA* Preprint, Jefferson County Dept. of
Health, Ala., <(32>| p., June 1967. 15 refs.
The air pollution problea in Metropolitan Birmingham,
Alabaaa is presented. The results and recommendations of
previous and current studies of air pollution in Jefferson
County are coapiled. Possible aethods of air pollution
control are also discussed. The topography of the Birmingham
area is irregular, consisting of ridges vith intervening valleys.
The city proper is in a valley. The main cliaatic effect
of the topography is that during winter aonths it produces
extreme temperature inversions and rather low minimum teaperatures.
The range of annual averages of suspended particulate aatter
in the 10 station saapling network varied froa 72 to 281
microgram/cu. a. Results show that 20* of the tiae suspended
particulate aatter in Jefferson County exceeds 265
aicrograa/ca. a. The annual averages for dustfall range from
9.5 tons/sg. ai./ao to 87.8 tonVsg ai./ao. Sulfation levels
are generally rather low in Jefferson county, sulfur dioxide
levels are generally low year round with the winter season
having the highest concentrations. Nitrogen dioxide was the only
gaseous pollutant found in any significant quantities with the
range of daily levels being 0.7 to 62.7 parts per hundred million.
Daily aldehyde lebels ranged from 0 to 9*0 parts per hundred
aillion. Air pollution coaes froa four main sources:
|1) Domestic, <2) Transportation, (3| Commercial and <
-------
coaaercial and Industrial. Industrial sources account for
approximately 98* of the particulate emissions, 881 of the
gaseous emissions and 53% of the hydrocarbon emissions from
stationary sources. In comparison with stationary sources
transportation contributes only slightly to the particulate
matter., The results of the public opinion survey shoved that
54% of the people within the City of Birmingham and an average of
42% of the people outside the city limits vere annoyed or affected
adversely in som way by air pollution, t#
07478
Vmitriev, H. 1.. and 0. X. Yurasova
COHTEHT OP THE PRODUCTS OF THE RADIOLYSIS OF AIR IH THE WORKING
CHAMBERS OP A POWERFUL GAHHA TJHIT» ((K voprosu o soderzhanii
produktov radioliza vozdukha v raboehikh kaaerakh moshchaykh
gamma-ustanovok.)) HT9* Sanit. (English Translation of:
Gigiena i Sanit.), 32 (3):442-447, Harch 1967. 10 refs.
CFSTI: TT 67-51109/1
The degree of formation of ozone and nitrogen oxides in the air of
the working chamber of a powerful gamma-unit was investigated.
The ozone was determined from the decomposition of potassium
iodide, while the nitrogen oxides were deternined by Griess*s
reaction as modified by Gorodetskii (1960). The nitrogen oxides
were determined at the worksite in the respiratory zone of the
operator at a distance of 1.5 - 3a from the irradiator, 1 Bin after
its immersion in water and the entry of people into the working
chamber. With an air change factor of 10 vol/min, the
plenum-exhaust ventilation of the working chaaber of the gaana-unit
reduces the concentration of nitrogen oxide at the worksites to
0.04 - 0.9 ag/CTU which is 1/5 - 1/100 of the naxinua
permissible concentration. Considerable concentrations of ozone
were found in the space between the irradiator planes at the moment
of irradiation. With an irradiation tiae of 20 nin and
dose rates of 300 to 600 rad/sec, the concentrations were 0.21 to
1.92 mg/cu» a.« when the plenum-exhaust ventilation was turned
off. Vhan it was working, the concentration of ozone decreased
to 0.34 - 0.84 ag/cu. a., which is still above the maximum
peraissible concentration for industrial premises. In cases where
it is necessary to exclude the ha-raful effects of oxone on the
irradiated material, the ventilation calculations should take into
account the high concentration of ozone near the irradiator.##
07529
S. Hayasbi
PUBLIC KUXS&HCE PROBLEM ARC ITS COBRTERBEAS0RE IR TOKKAICHI
CITT. Text in Japanese. Koki Seijo (Clean Air, J.
Japan. Air Cleaning Assoc.* Tokyo) Japan Air Cleaning
Assoc. (Tokyo)# 2<3): 1-18, 1965.
In a study of the environmental conditions of Tokkaiehi City,
it was found that the amount of soot and dust fall has been
990
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
decreasing, but SO2 and SO3 concentration axe increasing. The
¦tin section of the Yokkaichi industrial area is made up of tiro
large industries containing a power station using only heavy oil.
One of the problems to be considered is the poor city planning
which does not take into, account existing meteorological
conditions,. Investigations were made on soot and dust fall,
sulfur oxides, H25, H02, H03, and Cl. Methods of
sampling, places sampled, and duration of tests are tabulated.
The British standard deposit gage was used for dust fall, the
high-volume air sampler fox floating dusts, and the Pb02
aethod for SO2 measurement. The aaxiaum quantity of dust fall
¦easured between Deceaber 1962 and October 1963 was 40.99
tons/eg. ka aonth. The yearly variation is graphed showing the
inclination toward decrease* The highest average value
of S02 determined was 2 ag/day. The range of value is vide in
Yokkaichi city. The ratio of SQ2 i S03 was shown to be
sore than 1:1. itedical investigations were also performed on
30,000 people. The guantity of dust and soot fall and S02
is tabulated fox 20 places with the corresponding occurrences
of colds, bronchitis, emphysema, heart disease, eye disease, and
allergic dermatitis. The relation betwsen so2 concentration
and the occurrence of throat disease, colds, eaphyseaa, and
bronchitis for children op to 4 years of age and for people over
50 is graphed indicating a notable relation.##
07712
Braveraan, H. H.
TBEBDS AID LEVELS Of AIR POLLOTIOB ID MEW YOBK CITY. Aa.
Ind. Hyg. Ass/c. J. 28 (3):291-293, Hay-June 1967. 6 refs.
The Bureau of Laboratories of the Department of Air
Pollution Control of lew York City has maintained a
comprehensive monitoring program of significant parameters of air
pollution for over ten years. Trends and levels of concentrations
of gases and particulates over this period are presented.
Comparisons of the coacentrations of gaseous pollutants with
their threshold limit values (UV| present a novel perspective of
their significance. Gaseous pollutants that emanate chiefly
from motor vehicles for which adequate control devices were not in
use, continued to show a slight upward trend. Particulates
continue to show a slight downward trend* Evidence is presented
which demonstrates that more significant values nay be achieved
when absolute concentrations of gaseous pollutants are compared
with theix respective threshold level values.#*
08067
Alkire, 0. J. and C. a. Byes
AIB QUALITY SDHVEY IT SELECTED SITES ON THE HAJfFORD PROJECT.
Battelle-Horthwest, Bichland, Bash., Pacific Boxthwest Lab.,
contract AT(»5-1»-1B30, 16p., *ov. 1967. 9 refs.
CFSTI; BBBL-561
J. Air Quality MMSurtmwts
991
-------
The concentration of five potentially significant air pollutants
(S02, NO, B02, HCHO, and H2S) was aeasured at selected
sites ob the Hanford Project during the period Hay 17, 1967,
through July 11, 1967. The observed concentration of these gases
was below the detection linit nost of the tiae, but significant
levels of nitrogen oxides and sulfur dioxide were observed at some
sites part of the tine. Downwind of a cheaical separations plant,
nitrogen oxides (BO * 102) were above detection Halts <0*01
ppa) about 30* of the tiae. Peak MO * *0*2 COBCERTBATIOHS
ranged to 0*36 ppa* and hourly averages ranged to 0.12 ppa-
Average sulfur dioxide concentrations were less than or equal to
background 96* of the tine at two sites* and 89% of the tine at a
third site. Aldehydes and hydrogen sulfide were not detected
above background during the survey. (Authors' abstract)**
0B161
Kalyuzhayi, D. V., S. A. Davydov, I. G. Dukarskaya, and H. B.
Aksel*rod
ATROSPHBBIC AIR P0LL0TI0I BITH SOIEOB DIOXIDE FR0R MINING BOCK
DUMPS. In: Survey of 0. S. s. B« literature on Air pollution and
Belated Occupational Diseases. Translated fron Bussian by B. S.
Levine*. Rational Bureau of Standards* Washington, D. C., Inst., for
Applied Tech.* Vol. 3* p, 171-176, Hay 1960.
CFSTI: TT 60-21*75
Elission of sulfur dioxide into the air was caused gy the oxidation
of sulfur coapounds present la duaped coal and waste rock. The
intensity of waste rock burning in rock duaps and the quantity of
sulfur dioxide liberated depended upon the cheaical coaposition of
the coal and the wasterock, the height of rock duaps, the duration
of their accuaulation aeteorolegical conditions, etc. In nines
with an intensive burning of waste rock and with high rock dunps
increased concentrations of sulfur dioxide were found up to 1500 a
fron the source. In nines with low and slow burning duaps*
diffusion of sulfur dioxide did not extend beyond 750 a. Sanitary
clearance cones between rock dunps and residential quarters should
be 500-1500 n wide* depending on the intensity of dunps* burning,
the direction of prevailing winds, and the cheaical coaposition of
the coal and of the waste-rock. The nethod of filling in eaptied
coal veins* or fbutovka*! should be put into wide practice in coal
nining by organisations concerned with this problen. This should
eliminate further duap heap accuaulatioas. Baste rock should also
be used for filling in of ravlnos. Extinguished dunps should be
planted with appropriate shrubs and trees.
08267
SeCorso, S. H., c. E. Hussey* and ft. J. Aabrose
SHOKBIESS CORBOSTIOB IB 0II-BUBBIB6 GAS IBBBIBBS. American
Society of Sechanical Engineers* Paper 67-PHR-5, 8p>, 1967.
Ill refs. (Presented at the ISMI-IEBI joibt pobbb gebbbatiob
Conference* Detroit* Mich.* Sept. 24-26* 1967.)
992
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
The smoke particles generated by gas turbines burning fuel oil are
in the worst possible size category from the point of view of
visibility. Because of the small size of these smoke particles,
entrapment techniques involving internal separation* or washing
will tend to be ineffectual. This is confirmed by the fact that
laboratory tests showed no change in smoke level after passage
proportions of air entry at various stages of the eombustor.
through a heavy coolant spray, significant reduction in snoke
level has been accomplished on a coabuster design by changing the
the proportions of air entry at various stages of the eombustor-
Certain additives have been found to be effective in reduction of
smoke. They were most effective in producing a noticeable change
in smoke level at the lower ssoke numbers (i.e., at the lighter
smoke levels). This redaction of additive effectiveness with
increasing smoke may be rationalized on the basis that the action
of the additive is reaction-rate limited. Some of the physical
laws relating to visibility and transmissibility have also been
briefly examined. So major effect of fuel type is thus far
noticeable on our combustors over a rather broad range fuel type.
ashm
08297
Spinazzola, JL., I. Harraccini, G. Devoto, and s. Zedda
DISTHIBDTIOI OP SEVERAL VOLATILE TOXIC PRODUCTS WHICH ARE
IlDICATOttS OF AIR P0LL0TI0S IS THE CITY OF CAGLIABI. BOTE I.
SITftOGBS DIOXIDE. ((Studio sol ccaportaneato di alcnni prodotti
tossici volatiii quale indice di inquinamento atmosferico nella
citta" di Cagliari* Sota I* Gil ossidi axoto.)} Text in
Italian. Folia Bed. < la pies) , 49(81 :569-579* Aug. 1966. 19 refs.
Measurements of the level of nitrogen dioxide were made at 18
locations from B A.fl. to 8 P. (!., from Dec. 1, 1965 to July 15,
1966. Selective samplers were placed 150 and 200 cm above street
level at each monitoring location and sampled 60 1/hr of air. NO2
was present at levels ranging from 0.0018 to 0.0470 ppm. The
highest level is seen at street corners with traffic lights (0.0470
and 0.0316 ppm) and la areas with congested traffic (0.0330-0.0200
ppm). Areas with light traffic did not exceed 0.0090 ppm. Levels
generally reach a peak during rush hours. The results are compared
with those from other studies in Naples, Milan, and Bologna. It is
concluded that the probable source of S02 is the combustion of
diesel oil or gasoline.
08301
Bush, Albert F*, Asce, fl. and Sottage, H. B.
CARBOS DIOXIDE IS IS ISDICATO* OF 1IR POLLOTIOS. Proc. Am. Soc.
Civil Engrs., J. Sanit. Bag. Div„, 93
-------
Program (CAHP) stations in San Francisco and Los Angeles. Data
were obtained also froa San Diego. Sufficient continuous data were
obtained fron March 1964 to Feb. 1965 fron the Los Angeles analyzer
to allow a comparative analysis of C02 with other indicators
Measured by CAHP--CO# (JO, H02, Ox and S02. Since all the data were
obtained at the Vest Coast, S02 concentrations did not reach
sufficient intensity to be significant* The chemical and
¦eteorological relationships of the above pollutants were also
determined. Data froa a mobile C02 unit are presented as they
relate to a freeway study, a residential heating study# and an
ocean study. The results show that carbon dioxide is a good
indicator of cheaical air quality in the urban atmosphere. In
absoute magnitude it indicates the levels of the other indices of
air pollution. Seasonal norms of each variable are reflected in
corresponding seasonal norms for C02v and daily exposure patterns
as well as diurnal patterns indicate approxiaate levels of other
indices* The gross meteorological pattern of the atmosphere is also
reflected in the daily build-up of C02. Recommendations include a
different layout for freeway construction to reduce air pollution#
¦ore rugged* siapler and fully automotive instruaents for measuring
C02# and continuous Measurement of atmospheric C02 at Weather
Bureau stations throughout the United States.
08327
Robison, Charles 6.# Frederick L. Meadows, and John J.
Henderson
ALABAMA RESPIRATORY DISEASE AND AIR POLLUTION STUDY* II- AIF
POLLUTION PATTERNS IN THE GREATER BIRMINGHAM AREA. Arch.
Environ. Health# Vol. 15# p. 703-727# Dec. 1967. 22 refs.
In 1962# the Alabama Respiratory Disease and Air Pollution
Study was initiated to determine the prevalence of various
pulaonary disorders and to relate these findings to air quality
data. This paper describes part of the aerometric effort begun in
December 1963 in the Greater Birmingham Area. Samples for
analysis of suspended particulate# dustfall, sulfation, and
24-hour gases (nitrogen dioxide# sulfur dioxide# and aldehydes}
were collected routinely froa 21 stations located primarily in
residential areas. Annual cumulative frequency distributions for
suspended particulate, dustfall# sulfation# nitrogen dioxide# and
sulfur dioxide displayed a log-normal distribution. Aliphatic
aldehydes were found to be noraally distributed. Suspended
particulate and dustfall levels were extremely high in certain
locations throughout the area. The annual mean for suspended
particulates from this network mas 125 microgram/cu a, which is
considerably higher than the national urban mean, seasonal means
at several stations often exceeded 200 microgram/cu m* The annual
mean for dustfall was 22 tons/sq. ai/ao# which is higher than the
annual mean reported in either Nashville or St. Louis. This
annual mean reflects the influence of seven stations in very clean
areas# which consistently reported seasonal means less than IS
tons/sg. ai/ao. Sulfation and sulfur dioxide levels shoved
similar seasonal patterns. For the entire network, both of these
pollutants were found in relatively low concentrations. The
annual mean for sulfation was 0.16S03/100 ag. cm/day# and for
sulfur dioxide# 0.2 pphm. The nitrogen dioxide annual mean for
994
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
the 21 stations was 7.1 pphm, which is higher than levels found in
most HASH cities. Seasonal means for nitrogen dioxide varied
less than those for other gaseous pollutants. The annual mean
for aliphatic aldehyde was 1.4 pphn. Aldehyde sampling has been
done on a very limited basis In the United States and
consequently no data are available to compare with these 24-hour
concentrations. (Authors' summary)##
08485
flasek, Vaclav
THE EFFECT OF SOLAN RADIATION OS THE PRESENCE OF 3,4-BENZOPYRENE
IK INDUSTRIAL EXHAUSTS. ({Vliv slunecniho aareni na
pritomnost 3,4-benzpyrenu v exhalacich.)) Text in Czech. Chea.
Prumysl (Prague), 17(2):99-103, 1967. 30 refs«
The determination of polycyclic hydrocarbons in industrial
exhausts and in the atmosphere has become increasingly important
in recent years. The main interest is focoused on carcinogenic
substances, particularly on 3,4-benzopyrene. In the present
study, 3-4-benzopyrene was determined from samples obtained by
passing air through filter paper in the vicinity of a coking plant
in which coal tar products formed during carbonization leak into
the atmosphere. At the same time the intensity of solar radiation
was recorded with a Robitzsch pyranograph. The results showed
that the intensity and duration of solar radiation had no effect
on the content of 3,4-benzopyr«ne in the atmosphere and in the dust
in the vicinity of the source* The discharge of tar products
into the atmosphere must be controlled by changing the technology,
e.g., by improving equipment seals and using steam injection to
reduce the vapor pressure inside the equipment. Tables and
graphs.#*
08722
Sandberg, J. S.
CONTAMINANT AND WEATHER SOHBARY, NOVEMBfcK 1967. Bay Area Air
Pollution Control District, San Francisco, Calif. 3p. 1967.
A general description of the weather is presented. Daily mean
wind speed, maximum temperature, sunshine, and ventilation are
given. Oxidants, particulates, and carbon monoxide are discussed
on a "day-by-day" basis. Daily carbon monoxide concentrations And
oxidant concentrations are given for eleven areas in and around
San Francisco.##
09008
6. Jaccard, E. 2. Pilet
STUDY OF THE ATMOSPHERIC POLLUTION III M£ CI2X Of LAUSANNE.
((Etude de la pollution ataospfeecigue de la ville de
Lausanne.)) Institut de biologie et de physiologic vegetans
J. Air Quality Measurements
995
-------
de 1' Universite de Lausanne, <*fip.» ((1960)). Translated £rom
French. Joint Publications Research Service, Washington
D. C. , H-b980-D, 48p., tan. 16, 196B.
Measurements were conducted from October 1965 to September 1966
of sulphurous anhydride (S02) and carbon monoxide. The
analyses were completed by a systematic study of various
sensitive biological tests in the presence of polluted air. S02
was measured by two methods; gravimetric measurement and
measurement by an automatic recording apparatus which measures
electrical conductivity. Carbon monoxide was measured with
the Uras apparatus, which measures infrared ray absorption.
Biological tests were run by making measurements of pine
needles and lentil seeds. Oust was measured with membrane
filters, using gravimetric analysis. Germs were measured with the
same apparatus used for dust, then seeded on solid culture
medium, fcesults are tabulated. The titer of absorbed S02
is ouch higher in winter than in summer. In summer, the
diurnal S02 titer is higher than the nocturnal titer. The
CO titer varies during the day, the diurnal titer being almost
double that of the nocturnal titer. So results are given for
winter measurements. Those for summer are diagrammed. It is
concluded that foreign gases are present in air currents from
aeraticn openings and act on the growth and metabolism of the
nearby pine needles and lentil plants. The dust titer was
found to be relatively low in the city. The increase in total
germ titer was in direct ratio with the occupation of work
locations and of streets. A mobile laboratory is described.!#
09018
Hess, W.
SQNHABT OF THE ATBOSPHEBIC STUDIES II THE CITT OF ZURICH BETWEEH
1961 HID 1965. Z. Praeventivmed. (Zurich), 11 (2) : 14U-156,
1966. 5 refs. Translated from German. Joint Publications
Besearch Service, Washington, D. C., BH3942-D, 14p., Jan.
12, 1968.
Measurements of CO, S02, and BO* concentrations were made
at several important intersections of hear; traffic.
Carboxyhemoglobin concentrations were measured in the blood of
traffic officers and were correlated with CO s«asaresents. The
concentrations of the various pollutants floetasted within a wide
range and depended on the density of traffic and meteorological
conditions.##
09209
Schusnenann, J. J.
ISSIGHHEff? BEPOBT. ftIB POLLOTIOW TEHEBAI. AB IBTBODUCTOBY
SOBVET OF THE PBOBIEHS AID SORE SUGGESTED ACTIVITIES. World
Health Organisation, Geneva (Switzerland), 49p., Sept.
13-0ct. 1, 1965. 3 refs.
996
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
A project was to®gun in the city of Teheran which consisted of
these tiio parts: 1. A short tern study of the aain recognized
sources of air pollution in the city with the ain of identifying
their causes and recommending appropriate technical and
aduinistrative Measures for their abatement. 2. A long-tern
snail scale study of air pollutants and their effects on the
community vith the aia of training staff and developing
technigues for More intensive future studies. Information
corresponding to these two parts is presented.fi
09250
H. V. Dbisch, 7. Nilsson
AH AIR POLLUTION STUDY IN STOCKHOIH 1963/1964 AND 1964/1965.
((Luft£ororeningsundersokningarna i Stockholm 1963/1964 ocb
1964/1965.)) Text in Swedish. Nord. Hyg. Tidskr., 48(1); 13-
16, 1967. 3 refs.
At the centrally situated church of St. Clara, in Stockholm,
S02, N02, and air-borne dust levels Mere monitored at 3
different levels above ground. The accompanying figures show, for
S02, weekly means, cumulative frequency distributions for 2-hr.
values, annual variations expressed in monthly means, and an
example of the correlation between the wind direction and the
pollution level. Air pollution is high in downtown Stockholm,
ranging from traces of S02 in the sumael- months, to almost 15
p.p.h.m. during Decenber-Janurary. The ordinary height for
smoke stacks may be unacceptable.#*
09268
Aldaz, Luis
SURFACE AIR RADIOACTIVITY AID OZORS AT ARORDSER-SCOTT STATION
(90 deg. Sm), ANTARCTICA. latore (Paris}, 215(5102»:722-723,
Aug* 12, 1967.
Two ambient ataospheric tracers were studied. ozone was measured
by tvo types of instruaents, a cheailuainescent device, and a wet
cheaical detector: airborne radioactivity (fission products) was
also continuously aeasured. The monthly aeans of the ozone
aeasureaents from 1962 to 1965 and of tJie radioactivity
¦easureaents froa 1959 to 1965 are graphically illustrated. The
radioactivity aad ozone levels show a yearly oscillation; the
respective oscillations are opposite in phase* The phase
difference noted at the South Pole differs froa that
previously reported for the aiddie lattitudes of the northern
heaisphere where the tiae difference between the seasonal aaxima
for the saie two tracers is approximately one south, with the
radioactivity peak lagging.I*
J. Air Quality Meawrtmwrts
997
-------
09280
Public Health Service, Washington, D. C., National Center
for Air Pollution Control, and health Research Council, New
York, N. Y.
SURVEY OF AIR MONITOHING ACTIVITIES IN NJbH YCBK METROPOLITAN
AfiEA. 7 Op., Dec. 1, 1967.
This survey took place during the period January 9-27, 1967.
The consolidated Edison Company of New York, the Interstate
Sanitation Commission, the Lony Island Lighting Company, the
State of New Jersey, N. Y. City Department of Air
Pollution Control, N. Y. University, Public Service Gas and
Electric Company (N. J.), Nassau and Westchester Counties,
and the U. S. Public Health Service were included. The
pollutants measured were: sulfur dioxide, carbon monoxide, oxides
of nitrogen, hydrocarbons, oxidants, hydrogen sulfide and
aldehydes. summaries of the mcnitcring activities of the various
agencies measuring specific pollutants are tabulated. These
contaminants have been arbitrarily classified into three classes;
each of which are discussed from the standpoint of physical or
chemical properties and the method used for their collection.
The purpose was to provide a current appraisal of air
monitoring activities in the greater New York Metropolitan area
as of July 1, 1967.##
09391
Spinazzola, A., L« Harraccine, 1., and 6. Devoto
FIBST OBSEBVATIOBS OH IIP POLLUTIOH IB THE CITT OF CAGLIARI.
B1HAVIOB OF HITBOOS VAPOBS AHD OF ABHOHIA. (Primi rilievi sull*
inquinaaento ataosferico della citta* di Cagliari. Comportamanto
del vapori nitrosi e dell*aaoniaca.) Text in Italian. Bass.
Bed. Sarda, :295-300, 1966.
Boucly air saaples of 60 liters are taken from 8t00 A..H. to
8:00 P.M. at «l test sites in Cagliari. The nitrons oxides were
detected using the Saltmn aethod; the aaaonia levels were de-
tected using the Jacobs aethod. levels of nitrons oxides ranged
froa 0„002 to 0.060 p.p.a., with peaks froa 8:00-9:00 A.H., noon
to 2:00 P.(I. and froa 7:00-8:00 P.B. Levels of aaaonia ranged
froa 0.088 to 0.400 p.p.a. with no detectable dlarnal peaks.
09004
Damilano, S.
LEVELS OF S0LPH0B DIOXIDE BEGISTEBED I* BOLCGB1 DORIKG THE WIHTEB
1965-1966, BT HEARS OF THOIAS ATTTOHETEB. (fLivelli di
anidride solforosa registrati a Bologna aell'inverito 1965-1966
mediante 1* autonetro di Thoaas.)) Text in Italian. Bnovi
Ann. Igiene Hicrobiol. (Boae), 17<5|:
-------
Continuing a ten-year progran for the study of air pollution in
Bologna, measurements using the Thomas Autometer were carried
out from October <1965 through April 15, 1966„ According to the
results, expressed in terns of sulphur dioxide levels, air
pollution in the city reaches a peak (up to 0«65 S02 units)
during the vintertine and is highest in the absence of
precipitation or during low temperatures. Its exclusive source is
domestic heating. On the whole, air pollution is not yet a
problem for this city.##
09tn»5
Comprehensive Planning Bureau, Japan, Osaka Runicipal office
AIB OVER OSAKA CITT. 93P. , 1967
The location, geographical features, population, manufacturing,
and administration of Osaka City are discussed. An extensive
discussion of the measurement of air pollution is presented. The
sampling networks and measurement of dustfall, sulfur dioxide,
suspended particulate matter, automobile exhaust gases, and
meteorological parameters are discussed in detail. A survey of
air pollution sources in Osaka City is summarized.##
09467
Rosen, J. M.
SIMULTANEOUS DUST AND OZONE SCU HIDINGS OVER JIG Fill AND CENTRAL
ARER1CA. Rinnesota Univ., Minneapolis, school of Physics
and Astronomy, Contract Nonr-7 10 (22) , AP-25, 219p., Aug.
1967. {(56)) refs.
CFSTI, DDC: AD 6S8546
simultaneous soundings of ozone and sub-micron dust over North
and Central America are reported. The results show considerably
more dust in the equatorial stratosphere tba» in the middle lati-
tude stratosphere. The relative aaxieum An the dust concentration
observed near the level of the tropopause and as far north as 60
deg. is attributed to an equatorial dust source. The occasional
appearance of a secondary dust maximum immediately above the mid-
latitude tropopause is attributed to a torn of transport othec than
that of eddy diffusion* The structure in the ozone and dust pro-
files appears to be highly correlated in the lower mid-latitude
stratosphere. A quantitative model is (reseated describing the
production and transport of dust in the stratosphere. The methods
and equipment enployedare described. Theoretical vertical aud
horizontal diffusion models are also considered in detail.tl
09577
Craxford, S. 8. and W. I- P. «. fleatheriy
AIR POLLUTION IN GREAT BRITAIN - PAST, PRESENT AND FUTURE.
(08IGINAL SCIENTIFIC PAPIB.) Preprint, Warren Spring Lab.,
J. Air Quality Measurements
m
-------
Stevenage, 0. K., Hinistry of Technology, 20p., 1966. (Pre-
sented at the 36th International Congress of Industrial Chemis-
try, Brussels, Sept. 1966.)
The distribution of the major air pollutants - grit and dust,
smoke, and sulphur dioxide - throughout Great Britain is examined
in relation to the pattern ot emissions, and trends over the past
decade and sore have been worked cut. Using this material as a
basis, estimates can be made o± the further improvements that can
be brought about in the next few years. Hucli ot the data used wero
obtained from the National Survey ot smoke and sulfur dioxide,
which is described in detail.
09590
Public Health Service, Washington, o. c., national Center
for Air Pollution Control
PARKEHSBUBG, WEST VIRGINIA, MARIETTA, OHIO AIR POLLUTION ABATEMENT
ACT1VIT?. U7p., March 1967. ((38)) rets.
An investigation of air pollution in the interstate area
encompassing Hariette, Ohio, Parkersburg, West Virginia, ana
Vienna, Nest Virginia was conducted. The average concentrations of
suspended particulates Measured in the three major population
centers was in excess of 150 micrograms per cubic meter with
maximum daily values in excess of 500 micrograms per cubic meter.
The average value tor 2-hour sulfur dioxide measurements nade at
three locations was approximately 0.02 part per million parts of
air. At the Vienna station, however, a daily average .concentration
of 0.10 part of sulfur dioxide per million parts of air was
exceeded 3.4 percent of the time. Short-term concentrations
approached one part sulfur dioxide per million parts of air at
various times. Sensitive vegetation exposed in Vienna developed
injury that was attributed to the synergistic action of ozone ana
sulfur dioxide in low-level combination. Damage to indigenous
vegetation from sulfur dioxide and fluorides was also observed.
Atmospheric corrosion of ferrous metals was not abnoraally high,
tarnishing of silver plate indicated, however, that the presence of
gaseous sulfides is consistent with reported complaints of odor
nuisance. Pros an inventory of emissions of sulfur oxides and
particulate pollutants it is estimated that more than 123,000,000
pounds of sulfur oxides and 25,000,000 pounds of particulate
pollutants are emitted each year from sources in the survey area.
Approximately 85 percent of the sulfur oxide and 55 percent of the
particulate natter are emitted frcm sources in Ohio, and 15 percent
of the sulfur oxides and 45 percent of the particulate matter from
sources in Rest Virginia. Eight point sources account for almost
98 percent of the total sulfur oxides and 94 percent of total
particulate emissions. Mathematical applications of diffusion
theory were used to estimate the relative contributions of specific
sources.
1000
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
09598
Louneman, "• A«, 1. A. Bel lac, and a. P. Altsbuller
AROMATIC HYDROCARBONS IN THE AIMOSPHhuE Ci 'IHE LCS ANGELES
BASIN. Public Health Service, Cincinnati, Ohio, National
Center for Air Pollution Control, ((22)) p., Jan. 196b. 18
refs.
Gas chromatographic analyses fee aromatic hydrocarbons were made
in Los Angeles during the tall of 1966. A concentration tech'
nigue permits analysis for hydrocarbons ranging from benzene to
ten-carbon aromatics. These measurements maxe it possible to re-
late the levels of aromatic hydrocarbons to atmospheric photochemi-
cal reactivity. Concentrations of aromatics averaged 0. 106 ^ig
during this period; the-naxinun concentration was 0.33 ppm.
Toluene, the most abundant aromatic hydrocarbon, constituted 35
to 40 percent of the total concentration ot aromatics. The more
reactive dialkyl- and triallcy lbenzenes constituted 40 percent ot
the aromatics measured, Ratios of many of the aromatic hydrocar-
bons to each other varied considerably within the same day as well
as on different days. Analysis of the ratios suggested a signifi-
cant contribution iron solvent losses. Ratios of hydrocarbon to
nitrogen oxides were related to the observed oxidant concentra-
tions. (Authors' abstract)##
09743
Roberts, D. P.
SHORT TERR CORHOIITT AIR POLLUTION STUDIES IN TRRRES58B.
Occupational Health Rev. (Ottawa), 19(1-2):11-15, 1967. 3
refs.
Short-ten stadias of air pollution in eight Tennessee towns
selected on the basis of geographic location and population - less
than 40*000 people ace described. The studies indicated that at
least sose of the towns had significant levels of particulate
air pollution as seasured by weight of such particulates and by
soiling potential of the particles. It was also found that the
gaseous pollutants aeasared were of no ianediate concern in towns
of this site. (Author's abstract, aodified)**
11028L
Colueci, Joseph H. and Charles R. Be ye nan
CARCINOGENIC AIR POU.0TAHTS IN RELATION TO AUTOMOTIVE TRAFFIC IS
HEH 10SK. Preprint, General Rotors Research Labs., Warren,
Rich., Dept. of Fuels and Lubricants, HP-GJja-777, 3 2p., 196b.
33 refs. (Presented at the 61st Annual Resting, Air Pollution
Control Association, St. Paul, Sinn., dune 23-27, 1968,
Paper 68-71.)
i. Air Quality Measurements
1001
-------
Sampling for particulates and carbon monoxide was carried out . cities, and more than reported for several European
cities.
1122ft
Venezia, H. and G. Ozolins
INTERSTATE AIR POLIOTIOM STUDY PHASE II PROJECT REPORT. II.
AIR P0LLUTA1T EHISSIOW IR7E8T0RT. Public Health Service,
Cincinnati, Ohio, Rational center for Air Pollution Control,
50p. , Dec. 1966. <(50)| refs.
An emission inventory was conducted during 1963-196U as part of
the St* Louis - East St. Louis Interstate Air Pollution
Study. The Study covered an area of 3,567 square miles and
Included the City of St. Louis and the six surrounding
counties - St. Louis, St. Charles, and Jefferson Counties in
Missouri and Hadison, St. Clair, and Honroe Counties in
Illinois, (lore than 95 percent of the population and alaost all
of the industrial activity are located in the 400 square miles of
the centrally located urbanized part of the Study area. The
pollutant emission data presented can be alaost entirely attributed
to this urbanized portion of the area. Population density and
land-use saps, which provide an excellent index to the areal
distribution of most pollutant emissions, are presented. The
pollutants considered in this survey are those emitted in large
quantities from a variety and multitude of sources dispersed
throughout the area. Included are aldehydes, carbon monoxide,
hydrocarbons, nitrogen oxides {calculated as nitrogen dioxide),
sulfur oxides (calculated as sulfur dioxide}, particulates, and
benzofa)pyrene. The enissions of other pollutants are generally
associated with a specific process or operation and in general, are
not distributed throughout the community. (Authors* abstract,
modified}**
1002
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
11267
Public Health Service# Cincinnati, Ohio, Div. of
Air Pollution.
FOUR-YEAS SDHBAB? OF DATA FROM THE COKTIHHOOS AIR HOSITOHING
PROGRAH-
Preprint, ((23))p., Aug. 1966.
Continuous air Monitoring data gathered during 1962 - 1965 is
sunnarized. Aablest atmospheric concentrations of siz gaseous
air pollutants fron several major anerican cities are given.
These include sulfur dioxide, nitric oxide, nitrogen dioxide,
total oxidants, total hydrocarbons, and carbon aonozide, and
sailing index values. Sunsaries by city and year are given of
the annual average concentrations, the naxinun and ainimnn
nonthly average concentrations, and the maxinun daily average
concentration of the several pollutants Monitored.*#
113 i>3
Public Health service, Durham, N.C., National Air
Pclltuian Control Administration
AIS QUALITY DATA fHOB NATIONAL A1K SAHPLIaG NETWORKS AND
CONTRIBUTING STATE AM> LOCAL NETWOfiriS 196b jiiilTION. HAPCA-
Pub-APTU-68-9, 157p., 1S643.
Sunisaries and analyses in addition to basic data tabulations ate
presented. National summaries of pollutant levels, and figures
illustrating variations in the levels of gaseous pollutants are
presented. Data are given on the following topics: suspended
particulates; organic particulates; radioactivity; nonmetallic
inorganic particulates; metals; soiling iudex; gaseous pollutants;
and Measurement from the Colorado State network.##
11U59T
Shirai, Toshiaki, Shuichi H«*eda, Hirosi TakaHashi,
Toshihiro Ozawa, Takao Owuro and Takashi Kawakani
PHOTOCHEMICAL OXIDATIOM OP StJlFDR DIOXIDE III ATMOSPHERE.
Translated from Japanese. Kogyo Kagaku Zasshi, Vol. 65, p.
1906, 1962,, 20 refs. (Presented at the 15th Annual Meeting of
the Japanese Chemical society in April, 1962}*
The concentration distribution of S02 and total oxides of salfar
In the area of ZaO aselting plant in Yaukata Ken were
determined. The concentration ratio of S02 to total sulfur
oxides decreased with increasing distance. This clearly indicated
that S02 was oxidized in the atnosphere. The intensity
ratios of solar radiation seasored in fine weather in the ZaO and
Tokyo areas agreed extresely well is the range of the wavelength
J. Air Quality Measurements
1003
-------
400 nu to 320au. However, there was a big difference below
320nu. Froa experiaents vith a aercury laap it was found that the
photocheaical oxidation of S02 vas a first order reaction and
that the rate constant increased with an increase in ataospheric
moisture. ParaBeters tabulated for 10 to 32 different aeasurement
locations include: concentration of S02 and of total sulfur
oxides; teaperatare; wind direction and speed; weather; and
correlation of total sulfur oxides with distance from the slag
dunp pollution source.##
11615
Rowakowski, Paul
LOniNESCENT SHORE GEHEHATIOR FUSIBILITY STODY (PINAL REPORT)-
Missouri Research Labs., Inc., St. Louis, Bo., Contract
H61339-67-C-009 5, Task 5709, KAVTRADEVCEH 67-C-0095-1, 25p,,
Hay 1968.
CPSTIl DDC *0 675503
The nethods, test results and conclusions that comprise the effort
of expanding the potential of a saoke generating device into the
reala of fluorescent response are described. In order to satisfy
the reguireaents generated in this task, several areas of
investigation were included in this prograa. To deternine
sources of fluorescent response and to ascertain the state of the
art, literature was surveyed. The next step involved a study of
the saoke generating device to deternine the potential and the
liaitations of the saoke generating aechanisa. When the nost
promising candidates for fluorescence had been procured, they were
tested in the apparatus varying the solvent and the concentration.
This physical testing proapted farther work, using procured and
tested and when the aost proaising foraulations were ascertained,
the stability of the fuel and the characteristics of the saoke
cloud were deteraiaed. The feraents. (Author's suaaary,
aodified)#»
11627
Lahaann, Erdwin, Juergen Uestpbal, Kurt Daaaschke, and Margot
Luebke
CONTINUOUS OZONE MEASUREMENTS IN A HEAVILY 1RAVELLED STREET,
(Kontinuierliche Ozon-rtessungen in einer verkehrsreichen
Strasse). Text in Geraan. Gesundh. Inge., tJ9(5): 1U4-1U7,
1968. 12 refs.
At two measuring stations in Berlin, continuous ozone aeasureaeuta
were taken froa the sassier of 1966 to the sunaer of 1967. The
first measuring station was located in a busy street in Berlin
Steglitz, The air saaples were taken at 20 a and soaetiaes also
at 2 a* The second station was in a guiet area without traffic;
the saaples were takes at 10 a* The results show that in the
busy Schlosstrasse, aaxiaua ozone concentration was about
5 ppha. Of the total auaber oc individual aeasureaents, 8.6*
1004
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
exceeded 1 pphm and only 2% exceeded 2 pphn. The maximum daily
average was i»i£ pphm. Higher ozone concentrations were measured
in summer than in winter. The average ozone concentrations in
the traffic-tree area were much higher than those in the busy
street. Comparison of the diurnal variations of ozone
concentration at the two stations clearly shows the influence
of traffic. In the traffic-free area# the ozone concentration
rises from a maximum between 5 and 6 a.m. to a maximum between
2 and 3 p.m. and gradually subsides again. In the busy
Schlosstrasse, the ozone concentration drops to a minimum
between 7 and 8 a.m. At this time, which coincides with the
morning rush hour, the ozone concentration was just half as high
as that in the traffic-free area.
11775
S. s. Brar, D. K. Nelson, P. F. Gustafson
measurement of ozone in subface jib at abgonne national
Laboratory. In: Biological and Medical Besearch Division
Snnual Report 1968. Argonne National Lab., 111., ANL-7409,
p. 290-291, Dec. 1967. 4 refs.
CFSTI: TID-H500
Ozone studies in ground level air were initiated as part of the
Environmental Studies Program at Argonne, Illinois. A
recording, ozone-sensing meter detects ozone by oxidation of
potassium iodide, figures and tables give the daily average
values of ozone at Argonne in parts per billion against time in
days from mid-Hay to mid-September 1967. The data are too
limited to allow a correlation with meteorological variables or to
identify any seasonal variations. Typically, ozone
concentration iu air begins to rise early in the morning, builds
up to a maximum past mid-day, and falls to a low level by evening,
vhere it remains through the night.t#
12117
Nader, John S.
CONTINUOUS GAS HONXTQBING OF URBAN Alfl BY THE U.S.P.H.S. Preprint,
Instrument Society of America, Pittsburgh, Pa., 9p., 1961. 7 refs.
(Presented at the Instrument Society ot America Instrument*-
Automation Conference, los Angeles, Calif., Sept. 15, 1961.)
In September 1961, the D. S. public Health service initiated a
program of continuous gas monitoring of urban air* Objectives of
the program were to obtain information on the effects of gaseous
emissions from auto exhaust on the health of persons in a large
urban area and to determine optimum frequency sampling and duration
of sampling intervals, pata was provided by stations in Chicago,
Cincinnati, New Orleans, Philadelphia, San Francisco, Washington,
0. C., Los Angeles, and Detroit. The stations were located as close
as possible to the center of each city's business district; at each
station, ambient air was sampled within 10 to 15 ft above ground
J. Air Quality Measuremts
1008
-------
level. Identical instrumentalioii has been selected tor the cities
to eliminate instrunent difference a£ a varying parameter.
ColorimetEJ-C analyzers are specified for uitri oxide, nitrogen
dioxide, and total oxidants; conductometcic for suljEur dioxide,
coulonetric for 03, infrared foe.carbon monoxide; and flame
ionization for hydrocarbons. Analytical data obtained in
monitoring are presented in the fcrra of continous strip-chart
recordings. To overcome the problem of handling strip-chart data,
a digital punch-tape recctaer has lieeti incorporated with each
strip-chart recorder.
12360
Massachusetts Dept. of Public Health, ooston, Air Use Management
Program
SPECIAL REPORT Ctf THE INVESTIGATION AND STUDY OF MB QUALITY IN THE
METROPOLITAN (BOSTON) AIS POUUTICN COATKOL DI3TFICT 1965- 1966
UNDER CHAPTER 89 OF THE RESOLVES Cf iy&£i. imp., Sept. 16, 196B.
22 rets.
Atmospheric contamination in the Boston metropolitan area was
intensively investigated by the Bassacusetts Department of Public
Healtn, ibe principle aims of the study were to determine the
sources, extant, and nature of atmospheric contaminants ia bostou
and its surrounding communities; the variation in concentration of
the contaminants with respect tc tijoe, location, topography, and
meteorological variables; the effects of such pollution; the types,
locations, and strengths of significant emission sources; and the
requirements of a continuing program of atmospheric monitoring
and air pollution control All sampling measurements are presented
in the for® of tables and bar diagrams. fleaus tor reducing the
potential tor occurrence of pollution levels of certain
contaminants are discussed.
126«»9
9. H. Cock
AIS POILOTIOR HBASUREBE1TTS IK AUSTRALIA. A SURVEY OF CURRENT
HCTHODS AMD DEVELOPHESTS. Clean Ait fj. Clean Air Soc.
Australia, Hew Zealand), 2(3):10-13, Sept. 1968. 9 Refs.
Air pollution measurements in Australia are at present restricted
almost solely to deposit gauge and smoke and sulphur dioxide
surveys. These are being carried out to an appreciable extent in
only three States, Tiz. Sew South Dales. Victoria and South
Australia. The deposit gauge is considered as a tool for
first order of magnitude measurements only. It sould
therefore be replaced by instruments, the results from which can
be correlated, on a daily basis at least, with meteorological
data for the more easy identification of source pollution. Such
an instrument is being used by the shire of Altona in
Victoria. {Author's Summary# •)
1006
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
11180
Gordon, Robert J., Henry Rayrsohn, and Raymond d. Ingels
C2-C5 HYDROCARBONS IN THE 10S ANGELES ATHOSPHERE. Environ. Sci-
Technol«, 2(12):1117-1120, Dec. 1968. 12 refs.
A joint stady was carried out in Los Angelas in the fall of 1967
to define nore closely the actual concentration of oxides of
nitrogen and various hydrocarbons in the atmosphere on days of
differing smog intensity. Part of the study involved gas
chromatographic analysis for light hydrocarbons, ethane to
isopentane, at two sites* Almost 700 samples were run during 46
days. Averages were presented for the hourly sa spies subdivided
into groups of high or low oxidant develop®ent. Light paraffins,
especially propane, were found in concentrations too high to be
ascribed to auto exhaust, but their source was not pinpointed,
the average morning concentration of oxidant at various locations
was closely similar, hour by hour, in spite of large differences
in the levels of primary pollutants. The ratios of acetylene
and high olefins to nitrogen oxides were found -to be higHex than
the average in exhaust generated in a test cycle on a dynamometer.
14534
COHHISSION OH EARTH, WATER AND AIR, ROTTERDAM. Annual Report
1968. (Verslag over het jaar 1968). Text in Dutch» 72p.
This report deals with the soil, water, and air pollution
problems in the vicinity of Rotterdam. Thirty-three cases
of soil pollution reported in 1968 were vainly due to leakage
in underground tanks and pipes. The average chlorine content
at low tides at the measuring station of the Horingerdi'jk
reservoir was 139 mg/1, 7 mg/1 lower than in 1967. The level
of air pollution during 1968 was sore or less constant in
comparison with 1967. A study of the 1218 bronchitis complaints
of aale civil servants indicated that bronchitis occurs with
increasing frequency in the age group above 40 and especially
above 60. A study of chronic bronchitis and asthma in
elenentary school children in two sections of Rotterdam indicated
that in crosswijk, 5.5% of 455 children had chronic bronchitis
and 2.2% had asthma. In Hillegersberg, 1.0% of 480 children
had chronic bronchitis and 1.7% had asthma. Heasurenents of
precipitation, smoke, polycyclic hydrocarbons, CO, ozone, N02,
and sulfur oxides are presented. The saoke meter results show
a usual saoke content of 100 micrograms/eu a or more during
long periods of aist which occur during the winter aonths. in
the first and fourth guarters, the polycyclic hydrocarbon values
were auch smaller than those of 1964. of 174 saaples of carbon
aonoxide, 18 were more than 30 ppmj in 1967, only one sample was
higher than 30 ppm. The highest lead content was 1.5 micrograms/
ci m. Oxone content of the air was less than 20 micrograms/eu a
on cloudy days. Nitrogen oxide concentration ranged from 100-
150 aicrograas/cu a. Ninety-one days were recorded with S02
content equal to or greater than 350 micrograms/cQ a* and 89
days were recorded with saoke content equal to or greater than
250 micrograms/eu m» The declining tendency for saoke pollution
was attributed to the increasing use of natural gas.
J. Air Quality Measurements
1007
-------
1H776
lahaann, Erdwin
STUDIES OP AIR POLLUTION CADSED BT MOTOR VEHICLES.
(Dntersuchungen ueber Luftveranreinigungen durch den
Kraftverkehr)- Text in Geraan. Schriftenreihe Vec. Nasser Boden
Lufthyg. (Berlin), no. 28, 80p., 1969. 123 refs.
A neasuring station for deteraining the extent of air pollution
caused by aotor vehicles was erected in front of the city hall
in Rest Berlin, considered to be the busiest point in the city.
The Oras infrared analyzer was nsed for continuous neasurement
of CO and C02 concentrations 75 ca above the ground; ozone was
continuously aeasnred at 2 and 20 a with a unit developed by
Oaaaschke nnd Luebke based on liberation of broaine fron a
potassina broaide solution by ozone. For continuous seasureaent
of hydrocarbons at 75 cn, a Beckaan 109A analyzer was used.
Discontinuous saapling was eaployed for aeasureaent of NO, S02,
foraaldehyde, and phenols. A high voluae saapler was used for
deteraination of the total dust concentration. Traffic counts
were conducted throughout the aeasureaent period, and the driving
cycles were deterained. The results are listed in detail in
nuaerous tables and diagraas* The influence of aeteorological
factors such as wind direction and speed, huaidity, temperature,
and pressure is discussed. The aaziaua half-hourly average CO
concentration was 60 ppa with concentration peaks in the morning
and afternoon rush hours. Haxiaua C02 concentration was soaewhat
less than 500 ppa and thus only 50* higher than the natural C02
concentration of the ataosphere. No dangerous ozone concentrations
were aeasnred. All V02 concentrations were below 0.2 ag/cu m..
Peak S02 concentrations occurred in between rush hoars, which
indicates that they are due to doaestic heaters. A linear
relationship between the various pollutants was found. The
results of these aeasureaents are coapared with results in the
literature.
15161
Yeaater lobora
SOBHAHY OF AIR POILOTABTS LETBLS III THSBE AIR HONITORING
STATIONS IN TOKYO, 1968. (Tokyotonai 3 chiten no taikiosea
sokuteiao sokatei kekka no gaiyo). Text in Japanese. Kuki seijo
(Clean Air-J* Japan Air Cleaning Assoc., Tokyo), 7(3):45-61,
Oct. 1969.
Outlines of naaerons figures, charts, and indices obtained by
the air monitoring stations at three locations in Tokyo froa
January to Deceaber of 1968 are reported. The purpose of these
aonitoring activities was to deteraine exact and accurate
pollutant levels in conjunction with traffic situations at the
thrss aoaitoring station points. Measureaents were aade of seven
pollutants wsing an aatoaatic recorder. The tested pollutants
were S02, carbon aonoxide, NO, N02, dusts, foraaldehyde, and
total oxides; traffic sitaatioa wes recorded siaultaneously.
1008
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
The average values aeasured ware classified into hourly, daily,
Monthly, and yearly rates, and each maximum and minimum rate
vas reported. The relationship between traffic status and
pollutant levels vas obtained by the regression expression
nethod. The quantities of CO, S02, and HCHO showed the existence
of a relationship, but WO2 and atmospheric dust did not show a
particular relationship. The interrelationship between each
pollutant level is reported and suBnarized. The general tendency
of the pollutant levels determined for the past five years showed
that both carbon monoxide and atmospheric dust were increasing,
while nitrogen oxides remained almost the saae and S02 decreased.
15173
Tononura, Hasaharu, Nobuo Taaate, and Kusuo Tsuji
OBSEBYATIONS OF AIR POLLUTION tITH THE AID OF AUTOMATIC CONTINUOUS
ANALYSERS. II. BELATIONSHIP A BONG THE CONCERTSATIOSS OP VARIOUS
KINDS OF POLLUTANTS IN ATH0SP8EBE. (Senxoku sokutei kirokukei ni
yoru taiki osen no kenkyu (dai 2 ho) Taikichu ni okeru osenbutsu
kan no sokan kankei ni tsuite). Text in Japanese. Eisei
Shikensho Hokoka (Bull. Natl. Inst. Hyg. Sci., Tokyo), no. 85:35-
t»0# 1967. 4 refs.
In a study conducted from January through December in 1964, air
pollution in Tokyo was deternined. The relationships between the
concentrations of various kinds of pollutants, such as CO, S02,
NO, N02, and dust particles, were determined as a function of
their concentrations in the air. The pollutants were collected in
three heavy traffic areas in Tokyo: Kasuaigaseki, Itabashi, and
Shinjuku. A previous survey indicated that a relationship sight
exist among the atmospheric contaminants originating from
autoaotive exhaust gases. To evaluate this possibility,
correlation coefficients between the concentrations of C0-S02 and
CO-NO were calculated using data froa the automatic and continuous
analysers. The correlation coefficients revealed that a nearly
perfect linear relationship exists between both sets of
contaminants* For CO-NO2 and S02-N02, no significant
relationships could be obtained. It was concluded that formulas
could be used to estiaate the concentrations of some pollutants,
primarily those originating from automotive exhaust gases.
(Author abstract modified)
15212
Gibson, J. A. B., J. tm Hichards, and J. Doeherty
BOCLEAB HADIATION IN THE ENVIBONHENT - BETA AND GAItHA-BAY DOSE
BATES AND AIB IONIZATION FBOR 1951 TO 1968. J. Atmospheric
Terrest. Phys., 31(9):1183-1196, Sept. 1969. 33 refs»
The dose rates and ate ionisation due to beta and gamaa radiation
were measured continuously over open grassland at Stove* Berkshire,
England from 1961 to 1968* The measurements are compared to the
dose rates calculated from the radioactivity deposited froa nuclear
J, Air Quality Mtosuremants
1009
-------
weapon tests for the purpose of estimating dose rates back to 1951.
These data are reguired for estimating possible biological-effects
on Ran and for studies of the electrical potential gradient in the
atmosphere. Dose rates from natural sources were also considered
and calculations and measurement of dose rates from cosmic rays,
radioactivity in the soil and the air are included. The results
from gamma radiation from fallout at 1 aeter shov a good
correlation between measurement and calculation. The maximum dose
rates occurred soon after the weapon tests of 1958, 1961, with
levels up to 3.6 microrads/hr. The corresponding maximum levels
for beta radiation at 1 meter were 40 microrads/hr. These levels
must be modified to allow for attentuation by clothing before they
can be applied to man, but the ionization of the atmosphere can be
directly related to the potential gradient.. The corresponding
natural levels are 3*4 microrads/hr for cosmic rays, 3.7
microrads/hr for gamma radiation from air and soil, 1.U
microrads/hr for beta radiation, and 1.4 ion pairs/cc/sec for
alpha radiation in air. The total natural ionization at Grove
is 7.7 ion pairs/cc/sec* These calculations may be applied to
other locations by allowing for the differences in the
radioactive content of the ground and air, barometric pressure
(cosmic radiation), latitude (cosmic radiation and fallout), and
rainfall (fallout). (Author abstract modified)
15557
lahmann, Erdwin* JBergen Westphal, Kurt Damaschke, and tiargot
luebke
COHTIWOOOS OZOBE HHSBB3HEJTS I* h BBMlll TBftY ELL ED STREET.
(Kontinuierliche Ozon-Messungen in einer verkehrsreichen
Strasse). Text in German., Gesundh. Ingr. , 89(5) : 1UU-147,
1968. 12 refs.
At two measuring stations in Berlin, continuous ozone measurements
were taken froa the summer of 1966 to the summer of 1967. The
first measuring station was located on a busy street in Berlin
Steglitz. The air samples were taken at 20 m and sometimes also
at 2 m. The second station was in a quiet area without traffic;
the samples were taken at 10 m„ The results show that in the
busy Schlosstrasse, maximum ozone concentration was about
5 pphm. Of the total number of individual measurements, 8-6%
exceeded 1 pphm and only 21 exceeded 2 pphm. The maximum daily
average was 3.2 pphm. Higher ozone concentrations were measured
in summer than in winter. The average ozone concentrations in
the traffic-free area were much higher than those in the busy
street. Comparison of the diurnal variations of ozone
concentration at the two stations clearly shows the influence
of traffic. In the trafficfree area, the ozone concentration
rises froa a minimum between 5 and 6 a.m. to a maximum between
2 and 3 p.m. and gradually subsides again, in the busy
Schlosstrasse, the oxone concentration drops to a minimum
between 7 and 8 a.m. At this time, which coincides with the
morning rush hoar* the ozone concentration was just half as high
as that in the traffic-free area.
1010
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
15610
Odaira, Toshio
AIR POLLUTION FBOH HOTOR VEHICLE GASE5 III TOKYO A SO OSAKA.
{Dai toshi ni okeru jidosha haiki gas ni yoru taiki osen no
jittai).. Text in Japanese. Kogai to Taisaku (J. Pollution
Control), 5<5) : 337-353, 1969. 17 refs.
Various pollutant concentrations were determined near highways
and surrounding areas in Tokyo and Osaka. A large amount of
carbon monoxide was found near the highways, and gradually
decreased in the surrounding areas. The difference in the height
of the pollutant between the highway and surrounding areas could
not be measured to 100 ¦ if the wind was slow and natural
convections occurred. The carbon monoxide concentration was
found to be related to traffic density* The four pollutant
patterns differed from each other in the dust content, sulfur
dioxide and nitrogen dioxide content, caxbon monoxide and nitric
oxide content, and ozone content. The average CO was 3 to
8 PPVyr; however, 40 to 50 ppe/hr was not rare. In the middle of
the city, over 10 ppa/hr was measured 27% of the tine, tn the
districts that were 100 to 200 yards fron the highway, the monthly
average was 5 to 6 ppa, but 30 to 50 ppa/hr sometimes occurred.
In winter, this became serious. Nitric oxide concentrations were
0..05 to 0.25 ppi along the highway; N02 was estimated to be less
than 0„05 ppm, Tor the surrounding districts, HO was 0.05 to 0.15
ppa in winter and 0.01 to 0»05 ppa in soaaer. Hydrocarbons
averaged 2 ppa/ao along the highway. Carbon monoxide, BO, and
the hydrocarbon concentration curve changed during the day.
Oxidants averaged 0.02 to 0.06 ppa/ao and soaetlaes 0.14 to
0.25 ppa/hr. These measurements reveal that photochemical snog
is important in Tokyo. Lead was 3 to 9 ag/cu m along the highway
and 0.7 to 5 ag/cu a in the surrounding districts.
15726
Bichaeier, J.
THE VHimoH or THE 1AT?*A1 SHlli ASD HSGE 108 COHCEHT8ATIO*
INDOORS. {Das Verhalten der natuerlichen Klein - und
Grossionenkonzentration in geschlossenen Baeuaen). Text in
German. Intern. J. Biometeorol., 13{1) I5V-60, 1969. 20 refs.
The small and large ion concentration was measured in a normal
room with open or closed windows, in a windowless room, and in a
windowless metal shielded rooa* k particle counter and a dot
recorder were used, in the first room, the large ion
concentration was higher by an open window, fluctuating betwean
500 and 8000 1/ca a* It vaa at a aaximua ia th« morning and
afternoon, and subsided over the weekend. The maximum value
coincided with the higher air pollution caused by the aorning mad
afternoon traffic rush hoars. The stall ion concentration was
higher by a closed window. Xa the windowless rooa, the small
ion concentration was on th« average soaewhat higher than in the
room with windows; the larg* ion concentration was lower, when
J. Air Quality WM$urwTiwts
ion
-------
the door of the rooa vas open, the large ion concentration
increased; the small ion concentration decreased. Zn the metal
screened room, the small ion concentration vas three times as
large as in the open air. Opening the door for a longer period
of time increased the large ion concentration.
15740
Stewart, s. s. and D. H. Bilk en
EFFECT OF SHADE OK ATMOSPHERIC OXIDAHTS
-------
choice. Concentrations of suspended particulates were greater than
the ambient air standard of 200 niccograms/cu ra 28% of the time.
The sulfur dioxide ambient air standard was 0.2 pput for 24 hr and
0.4 ppra tor any JO niin period. Sulfur dioxiue readings monitored
during the survey were less than or eyual to 0.15 ppm 971 of
the tine. Concentrations were greater than 1.0 ppm for 30-minute
averages on two occasions. Concentrations of greater than 0.5 ppm
for one hour were found less than 0»2& of the tine. Carbon
monoxide values ranged frogs 0 to 18 ppm, depending on traffic
volume. The ambient air standard was not set. Standards for total
hydrocarbons were not set either, but hourly averages ranged from
0-10 ppm. it was concluded that the El Paso area has an air
pollution problem and the major pollutants are particulate matter,
sulfur dioxide, carbon monoxide, and total hydrocarbons, promotion
of air pollution control and control methods were recommended,
as well as legislation restricting emissions. Tables are given
tor industrial and metropolitan emission inventories, soiling
index, steel plate corrosion, and particle size distribution.
Climatology, topography, and aeteorological parameters are
discussed.
16274
Lagutin, Ye. 1.
N£H DATA QM THE CHEMICAL COMPOSITION OF ATMOSPHERIC PRECIPITATIONS
IN NORTHERN TIEN SHAN* (Novyye dannyye o khimicheskom sostave
atmosternykh osadkcv severnogo Tyan'-Shanya). Text in Russian*
Doklady Akaa. Nauk SSSR, 173(6): 1426-1429, 1967. 3 refs.
The value of measureaents of the chemical composition of
atmospheric precipitations to studies ot the metamorphosis of
ground water under the intluqnce gt many natural factors as well
as of that of air in the vicinity of modern industrial cities is
stressed. A Table of the chemical composition of 19 samples of
snow and one of rain is given, collected on stated days at stated
locations in the Northern Tien Shan region lying within the
confines of the Kirghiz S»5»B* The concentrations of
microcoaponents in atmospheric precipitations were determined by
subjecting their dry residues to spectral analysis. The
composition of the samples is given in terms at milligrams per
liter of HSi03 and of the following ions; HCOJf-j, 304(2-),
Cl{-), Ca{2+), Mg{2+), Na{+), and K (+) , as weil as in the form of
a 'chemical composition formula'. The total ion concentration,
in milligrams per liter, and the hydrogen ion concentration,
expressed in terss of pH value, ace also given. Six aaaplea were
collected on March 4, 1965 at 6 elevations above sea level between
1000 and 350Q meteva in 500-meter steps on the northern slope or
the Kirghiz range bordering the Chuyskbasin in the south. Five
samples were collected at two~weefc interval# between Sept. 1 and
Oct. 30, 1957, on the eastern shore of the Xssyk-Kol lake in the
Kokbel creek valley of the Czhergalan river basin.
J. Alt Quality MMwramwta
-------
16684
Chovin, P.
AIB POLLUTION STUDIES IN PARIS AND CUTLYIN(i UISTRICTS IN 19t>7.
1. OPERATION 'CAfiBON MONOXIDE", 2. OPEBATION •GARAGES', 3.
OPERATION 'MODTEAFN 65SE, RAILHCAD STATION1, 4. OPERATION 'LOOP OF
ThE SEINE1. (Etudes de pollution atmosphei lc^ue a Paris et aans
les departements peripheriques en 1967. 1 - Operation 'Monoxyde
de Carbone", 2 - Operation 'Garages', 3 - Operation 'Gare
Hontparnasse', 4 - Operation 'Boucle de la Jieine'). Text in
French. Prefecture de Police, Paris (France), Lab. Central,
Sept. 58,J37/D-PA, 8Qp., June 1966. 10 rets.
Results are reported of field studies of CO-pcllution of air due
to exhaust gases from wotor vehicles in 1) central Paris, trance
(operation 'Carbon Monoxide') and 2) at air inlets and cutlets of
three underground parking garages (operation 'Garages'); 3) of
air pollution by a variety of pollutants in tae motor taxi hall
of the new Hontparnasse station in Paris (operation 'Gare
Hontparnasse*); as well as 4) of dust settling near the ground in
the Seine river bend between Santerte and Vilieneuve-la-Garenne
in the north-west part ot the Departement de la Seine (operation
•Boucle de la Seine'). In 1), a total of 15,216 air samples were
collected at 317 sites shewn en the city map; 235 (1.54% ot all)
samples had a carbon aionoxide content of more than 100 volume ppin
at 129 of the sites. The average CO-concentration in the jear
1967 was 25.9 volume ppm (a rising trend since I960)* In 2), in
addition to the study of the effect of the presence ot the
garage ventilating system on the CO-concentration in its
neighborhood, a search for the acst representative locations of
air sampling stations at different levels of an underground
garage was undertaken. In 3), continuing a study beyun in
1966, a laboratory van was stationed on July 29, 30, and 31, 1967
in the central part of the hall and the CO-, N02- and NO-
concentrations in air, and the Pb-content of dust collected in
fitered were determined analytically and the concentration of
benzo-3,4pyrene in this dust was determined tluorospectroscopicaliy.
As a result ot a modification of the originally installed
ventilating system of the hall made after the 1966 tests, air
pollution bad diminished. In 4), continuing a study begun in
1959, dust from air was collected on 30 cm diameter settling
dishes, at 22 sites. The material collected by a aish during
one month consisted of water, insoluble dust particles (cinders
and benzo-3,4pyrene) as well as water soluble dusts (sulfates,
chlorides, and calcium compounds). The amounts of these were
determined and referred to an area of 100 sq o per month, lhe
average monthly total amounts of dust collected at the 22 sites
are shown. The results are evaluated statistically and are
presented in the form of monttily averages and histograms. At one
site the amounts ot benzo-3,4pyrene were consistently
exceptionally high; 7 new settling dishes installed at sites close
tc and surrounding a suspected saui.ee had four times higher
amounts of benzo-3,4pyrene than any of the 21 other sites. This
pinpointed a charcoal and aspnalt processing plant as the most
probable source.
1014
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
16843
Stephens, Edgar B. and Frank H. Eurleson
DISTRIBUTION OF LIGHT HYDROCARBONS IN AMBIiiKT AIF. J. Air
Pollution Control Assoc., 19 (\2) :929-9J6, Dec. 1969. 10 rets.
The diversity of hydrocarbons which are present in ambient
polluted air provide a potentially rich source of information
concerning the nature of this type of pollution. Measurements
of the relative amounts of various hydrocarbons can be correlated
with the various possible sources. Since hydrocarbon reactivities
vary widely it is also possible to estimate the extent to which
various individual hydrocarbons have reacted. Except for sauries
taken deliberately near sources of hydrocarbon pollution these air
samples invariably resemble auto exhaust with an addition
of natural gas and of C3-C5 paraffins which resemble gasoline
vapor. Samples taken in industrial areas ana near the sooke
plume trcn a brush tire showed distinctive differences in
composition. During the snog season in the fall of 196ti gooa data
were obtained of "typical" or "representative" samples of light,
medium and heavy smog. These show the expected depletion of more
reactive hydrocarbons in a much more convincing way than before.
By comparing these distributions with composition in unreacted
samples and by making use of data trcm bottle irradiations, it
was possible to estimate the contribution of the various
hydrocarbons in terms of "amount reacted.*' The amounts of higher
hydrocarbons present and reacted were also estimated from gasoline
composition. (Author's Abstract)
16927
Kanitz, S.
POSSIBLE FOEMATION OF ' PH010CHEBICA1 SflCli' IS IT ALY : SXNThtSIS A NU
DETERMINATION ,OF PESOXi ACYLNITB ATES IN THii L.A dOS ATOfl Y AND IN THE
0UTD0Qf AIR OF GENOA. (Possibilita ai formazione dello 'smog
totochimico» m Italia; sintesi e determiaazioiie di
perossiacilnitrati in laboratorio e nella atwosfera libera a
Geaova). Text in Italian. Gicrn. Igiene tied. Prevent. (Genoa),
8 (3);3<4-33U, Kay-June 1967. 19 refs.
An experiment was conducted with gas chrosotogcaphy to determine
the possible presence of peroxyacetylnitrate (PAN) in the
atmosphere above Genoa. The presence of this substance would
indicate the existence of secondary air pollutants of the
photochemical type, such as are found in Los Angeles smog. The
PAN used as a standard was synthesized by photolysis from a
mixture of ethyl nitrite and oxygen. Isolation of the PAN by gas
chroaotography took place in a Teflon column filled with 5A
Cariowax 400. Samples of the atmosphere were taken on sunny days,
with an absence of wind and a relative humidity below 40X, at the
edge of a heavily traveled and highly congested highway. A second
experiment checked the possibility of obtaining PAN by;irradiating
the exhaust of an 8-cycle motor of European manufacture and using
high-test gasoline, irradiation took place in a 2-liter pyrex
J. Air Quality Measurements
1015
-------
tube, using a aercury vapor 0? lamp tor periods of as much as 90
ninutes. Experimental results revealed that the maximum level of
PAN measured at Genoa is 0.33 ppb, which represents about 1/100 ot
the maximum to be found in sdch a location as Riverside,
California. Analysis of the irradiated exhaust tumes also
revealed the presence of PAN. Seme of the chrcnatograms showed
peaks that were strongly suspected of representing
peroxypropylnitrate and peroxybutylnitrate, but this was not
absolutely confirmed.
17068
Tokyo Inst, of Technology (Japan), Kiyoura Lab.
ABATEMENT QF AIR POLLUTION I - (1) SULfHOH DI0XID1S. (Ayusan
haigasu ni yoru kogai bojo ho). Text in Japanese. Kogai to
Taisaku {J. Pollution Control) , 1 (1) :S5-5tt, April 15, 1965.
Sulfur- or sulfide-containing matter produces sulfurous acid gas
when heated by air or oxygen. There is a danger of air 'pollution
occurring if the density of sulfurous acid gas in air exceeds 0.3
ppa for long periods. Katz and his staff studied damage from
sulfurous acid gas emitted by a zinc and lead refinery at Trail
B. C. to woods in the basin of Columbia River. They found smoke
pollution most prevalent in the spring. Smoke pollution occurs
immediately if gas density is high. According to zimmerman, the
permissible limit of sulfurous acid gas is not 0.3 but 0.7 ^pat.
Haines and his members experimentally determined that sulfuric
acid mists from 30 to 65 ppm did little damage to alfalfa, sugar,
beets, etc., even after tour hours. For tour days in December,
1950, London was covered by a thick smog with a sulfurous acid
gas content of 0.6 to 0.8 ppm; the death rate was nine tines higher
than usual. Sulfur dioxide is a colorless gas that is
catalytically oxidized to sulfuric acid* Sulfuric acid is sharply
reduced in water; sulfur dioxide melts in cold water.
17096
Selegean, Elena, H. Cucu, C. Anghelescu, I. Ardeleanu, C.
Botezatu, H. Dargenta, A. Lucinescu, olimpia Popa, Zamfira
Stanescu, and N. Manea
INVESTIGATIONS ON SHE OXIDIZING POTENTIAL QF IHE AIR IK <1 lOVUS
1* THE SOCIALIST BEPUBLIC OF FDWASIA. (Cercetari cu privire la
potentialul oxidant al aerului din 4 orase din Republica
Socialista Romania) . Text in Romanian. Igiena (Bucharest),
15(9):533-S39, 1966. 16 tefs.
The oxidizing potential of the air in 4 towns in Rumania was
investigated over a period of 3 years. In 2 towns with large oil
refineries, high 03 concentrations were found, particularly on
sunny, summer days. This was probably due to the photochemical
oxidation of the pollution emitted into the atmosphere* (Author
summary modified)
1016
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
17106
Endo, Syosaku, Tetautaro Kohgo, Tatsunon Oyake, Naoki Sugawara,
and Toshiko Sakamoto
STUDIES ON THE URSA N ATMOSPHERIC POLLUTION Bi AUTOMOTIVE EXHAUJI
GAS IN THE CITIES OF HOKKAIDO. (PAKT id). ON THii IN V ilSTIGAl'IOa I J,
OTAKU CITY. (Hokkaido no toshi ni ckeru jiuosha haiki gasu no
taiki osen ni tsuite (dai 2 ho) otarushi ui okeru cbosa kekka ni
tsuite). Text an Japanese. Hckkaidc-ritsu Lisei Kenkyushoho,
no. 18:143-149, June 1968. 11 rets.
The urban atmospheric pollution caused by automotive exhaust
in Otaru was investigated. The measurement of dusts, carbon
monoxide, sulfur dioxide, nitric oxide, nitrogen dioxide, lead,
and 3,U-benzopyrene and the number of vehicles were carried out
at 4 places along the rqadside. The road at joints A and b was
narrow, at points C and D, it was wide. It was cloudy and calui
at points A and B, and was clear and windy at points C and D. riore
vehicles passed by points A and B, with a maximum c£ 2000/hr at B.
The concentration ot all the pollutants were higher at point ii
with the exception ot S02. The maximum concentrations were listta.
It was concluded that the atmosphere at the point B was more
contaminated than points in the cities ot Kushiro and Asahikawa
which were previously investigated. (Author abstract modixieu)
17210
Odaira, Toshio
BEVIES ON AIR POLLUTANTS CONCENTRATIONS AbD THEIR CCRftfcL ATIGNS ON
THE BASIS OF AIP POLLUTION PHINOBINA. (Osengensho karamitd
taikiosen shitsunodc to sogokan no kankei). Text in Japanese.
Taiki Osen Kenkyu (J Japan, Soc*, Air Pollution), 3 (3):167-178,
Dec. 1, 1969. 3 rets.
Data on pollutant concentrations, atmospheric temperature at an
elevation of 107 m, and wind direction and speed, obtained in
Tokyo during August and December, 1967, were statistically
analyzed. Although concentrations of various air pollutants can
be determined in accordance with combinations of factors such as
weather, topography, source intensity, etc, the effects of the
latter were not analyzed concretely. Pollutants which shuwea
similar pollution patterns (concentration frequencies) were
grouped together. Four groups were found: particulates, carton
monoxide and nitric oxide, sulfur dicxioe ana nitrogen dioxiae,
and ozone. It was assumed that the pollution pattern varied from
group to group. Particulate concentration was monitored by a
digital dust meter, a tape light reflection index, and a tape
light transmission index. Particulate concentration was twice as
high in winter as in summer, and unaffected by wind direction.
The CO concentration was three times as high in winter as in
summer. A correlation was found between SO2 and N02
concentrations and between CO and NO. The oxidant showed a
concentration pattern different from the other three groups. It
is concluded that it is possible to forecast air pollution by
applying multiregressjon techniques or a simultaneous eguation of
two-step estimation to analyzers of sources, local weather,
pressure distribution, etc.
J. Aif Quality Measurements
1017
-------
K. LEGAL AND ADMINISTRATIVE
00169
A. J. Benline
1965 ANNUAL REPOPT - DEPARTMENT OP AIR POLLUTION CONTBOL - CITY
or NEW yofk. Dept. of Air Pollution Control News 8, (5)
Apr. 1966. U0 pp.
LEGAL r, ADMINISTRATIVE: Health impairment, Mew York City,
Pollutants, ?ir Quality Measurement Programs, Control
agencies
City ot New York, Department of Air Pollution Control,
Annual Report for 1965, describes Sew York city air pollution
progress as it relates to administration and personnel;
engineering; public opinion; types of pollution; Beans and methods
to curtail air pollution.##
00206
CONTROL OT AIR POLLDTIOS 0BIG3RATIRG EFCM FEDERAL IBSTALLATIONS
AND STANDARDS EY THI SECRETARY OP HEALTH, EDUCATION, AMD WELFARE
IKPLEMERTXNG THE OBJECTIVES PRESCRIBED BY THE ORDER. EXECUTIVE
ORDER 11282. Dept. of Health, Education, and Welfare,
Washington, B.C. Hay 26. 1966. 6 pp.
The article specifies the overall pclicy, procedures for new
federal facilities and buildings, and objectives for federal
facilities and buildings insofar as air pollution control is
concerned. In addition, standards to be used in this new order
are delineated by Secretary Gardner- The categories to which
the article alludes are: coabustion of fuels. Stacks, Storage
and handling of fuels and ash, and disposal of trash. In each
instance ace specified Units and means to aeasure the amount of
pollutant covered by the above categories.##
00225
V.G., HacKenzie K- flieger
1019
-------
THE CLEMS MR ACT AHBNDHENTS USD SOLID WAST£ DISPOSAL ACT OF
1965 (P. L. 89-272). Health, Education, and Welfare
Indicators.. Hot. 1965., 15 pp.
The Clean Air Act Amendments and Solid Haste Disposal Act
provide important new tools to help forge a comprehensive attack
on the growing national problem of community air pollution.
Under the clean Air Act of 1963, the Department of Health,
Education, and Welfare has undertaken the formation of a
national prograa for the prevention and control of air pollution.
The Amendments to the Clean Air Act and the Solid Waste
Disposal Act will enable the Department to carry its efforts
further in several of the most critical areas of the complex
probleu of air pollution.##
00359
HcKee, J# £.
AIR POLLUTION CONTROL - ECONOMIC IMPACT OF GROWING
PHOBLEfl. Trusts and Estates. Feb. 1964. 5 pp.
Author discusses the general paraaeters of air pollution
and how it has changed over the years. Categories treated
are : Magnitude of the Air Pollution Problem; Establishment
of Local Agencies; Standards and Criteria; Motor Vehicle
Control; Power Plants; Federal Government's Role in
Pollution; and the General Extent and Mature of the Air
Scllution Problem.*#
CC897
B.P. Halbos
(THE STRUGGLE AGAINST AIR POLLUTION IN HEW YORK. REGULATIONS
ADD OBSERVATIONS ON THEIR APPLICATIONS.J La Lutte Contre
La Pollution de l'Air a New York. Hegleaentation et
Observations sur 1®Application. Pcllut Atacs. {Paris)
8 (29);3A-U7, Jan.-flar. 1966.
Two leaflets which were published and which concern the general
aethods to be used in New York's fight against air pollution are
summarized. The first leaflet, published on October 1, 1964,
gives the "New Code" for the control of air pollation, which
includes the control aethods, standards to be aet for discharges,
the rules for installing and maintaining aachinery and
appliances* and the standards of fuels to be used. The second
leaflet, June 22, 1965, is the technical report of the Special
enquiry comaittee on Air Pollution, and gives the results of the
measures pot into effect against the different polluting agents
in New York, the evaluation of discharges froa different
sources, and the role of the varicus aunicipal administrations set
1020
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
up for the control and surveillance of the vork. (Author
summary)*#
01211
J. A. Maga
AIR RESOURCE MANAGEMENT IN THE SIM PRANCISCO BAT AREA.
(California state Dept. of Public Health, Bureau of Air
Sanitation!. California Oniv., Berkeley, Znst. of
Governmental Studies. 1965. 42 pp.
Author reviews the problems of air pollution in the San
Prancisco Bay Area, stressing the need for effective air
quality standards. Topics covered is the report (all germane to
the San Francisco Area) are: Air Pollution in the Metropolis;
the concept of Air Resource Management; Weather, Topography
and the Regional Air Resource; Air Pollution and its Effects;
Air Pollotion and its Relationship to other Regional
Problems; a regional approach to the Control of Air Pollution;
Control Programs in the Bay Area; and the outlook for the
Bay Area.#*
01567
H. Barge
EMISSION CONTROL - A SUPRA-NATIONAL CONCERN IN OUR TECHNICAL
AGE. (Immissionsschutz, Sine Ufcerstaaticbe
Geaeinschaftsaufgabe in Unserem Technischen Zeitalter.) Z*
SozialoeKonomie, No. (614.7)1-8, 1966.
Local so2 warnings; guide lines; and limit values are critically
discussed with emphasis on the situation in Northern
Rbine-Pestphalia. The need for independent evaluations and
supra-national regulations are stressed for the vest European
community. The economic and sociological as veil as the
biological aspects of the problem are discussed. The need for
continuous measurements is underscored.**
01600
R. A. Tenezia
THE INTERSTATE AIR POLLUTION STOOtj ST. LOUIS - EAST ST. LCDIS
METROPOLITAN AREA. Public Health service, Cincinnati,
Ohio, Div* of Air Pollution* {Presented at Missouri Public
Health Association Convention, Kansas City, Hay 11, 1965.)
1965» 22 pp.
The Interstate Air pollatien Stud; o$ tin St. Louis - East
K. L«|*t and Administrative
10 «
-------
St. louis Metropolitan area is described. The study was in
keeping with the ait resource Management concept. Dustfall,
suspended particulates, soiling index, sulfur dioxide, oxidants,
odors, carbon monoxide, hydrocarbons, nitrogen oxide, nitrogen
dioxide, sulfur dioxide, ozone, and visibility vere measured.
The effects indicated by steel corrosion, nylon and cotton
deterioration, asthma, opinion surveys, and complaints vere
examined. An emission inventory, meteorology, fluorescent
tracer diffusion, diffusion nodels, economic losses, legal
aspects, and public relations were studied during the study.##
01853
A CCSHPILATICH OF AHEIEBT MS QUALITY STASDAitttS AND OBJECTIVES.
Preprint* 1965.
Ambient air guality objectives describe a level of air
quality designed to protect people from adverse effects of
air pollution, and they are intended further to promote maximum
comfort and enjoyment and use of property consistent with the
economic and social veil-being of the community. The
Regional Ambient Air Quality objectives of Rev York State
Air Pollution Control Board are outlined and standards for
ambient air guality and photochemical pollution adopted by the
California State Board of Public Health are listed.
Colorado's air pollution control act of 1964 and Oregon*s Stat*
Sanitary Authority Administration Order are also given,
as Nell as Regulations from San Francisco Bay Area Air
pollution Control District of Hay 1960, and from Florida.
Exposure limits from Vest Germany and O.S.S.R. are also
listed.*t
C2170
6. A. Jutze and E. C. Tabor.
THE CONTINUOUS BIS MOMITORIBG PROGRAM. J. Air Pollution
CONTROI ASSOC. 13, (6) 278-80, JOVE 19GJ. (PSSSIWTID AT THE
55th Annual Meeting, Air Pollution control Association,
Chicago, 111., May 20-24, 1962.)
Authors diecuss the continuous Air Monitoring Program
tCARP) with particular emphasis on the sampling equipment it
utilizes.t#
02376
AIR RESOURCE MAMAGBMSV? PROGRAM 50UTBWESTBRH OBIO-HORTHERM
1022
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
KES1UCK1. preprint. Published as report: *ir Resource
Management Program for Southwestern Ohio-northern
Kentucky, Mar. 1967, 51 Fp« SIC - NK (Southwestern Ohio -
Northern Kentucky) air Pollution Survey, Cincinnati, Ohio,
SWO - NK technical Committee, 1966.
The primary purpose of this report is to assist the citizens and
governments of southvestern Ohio and norther Kentucky in
understanding the nature of their air pollution problem and in
developing a course of action - an air resource management program
- to assure desirable air quality both now and in the future.
This report is the culmination of over a year of study and effort
under the title. Southwestern Ohio - Northern Kentucky
(SWC-NKJ Air Pollution Survey- The survey, established by
formal agreement on March 31# 1965, brought together governmental
officials, interested citizens, and industrial leaders from both
sides of the Ohio River to consider a problem common to them all
and to propose a solution, of necessity, common to them all. This
report also presents a general discussion of the air pollution
problem and applies to it the ideal methodology for solving the
problem, the air resource management concept. Various aspects of
the air pollution problem in the project area are summarized from
Technical Committee reports to provide background for the
program proposal. The current status of control is also covered*
03353
DIGEST OF MUNICIPAL AIF POIIUTICN ORDINANCES. Pittsburgh
Univ., Pa., law Center. (PHS Publication No„ 982.) 1962.
520 pp.
Begulations, ordinances and their administration regarding
allowable concentration for air pollutants arc presented.
Enforcement procedures, inspection procedures, and penalties for
violation of specific regulations arc presented for urban areas.
Air pollution control starts with the premise that no one has the
right to use the atmosphere as a receptor of wastes in a manner
which will adversely affect the health, comfort or property of
others.~#
03359
AIH POLLUTION IN NED Y01K CITY ^INTERIM TECHNICAL FEPT.
H-970)• New York City Council, Special committee to
Investigate Air Pollution. June 22, 1965* 74 pp.
Authors cover the following topics of air pollution as the; relate
to N«v tor* city: <1) air quality -a statistical analysis*
{2) The effects of air pollution on health as well as agricultural
K. Legal and Administrative
1023
-------
and plant life, (3) The major sources of air pollution in New
York City, covering categories such as fuel combustion in
stationary sources, vehicular exhaust, refuse combustion,
industrial processes, and emission calculation, (M) The influence
of weather, (5) and Analysis of air pollution control program.##
03850
T. Kartell!
(THE CONTBIBDTION OP LOCAL AEHINISTRATICNS ID THE FIGHT AGAINST
ATHOSPHEBIC P0L10TICB. II Contribute delle Amministrasioni
Locali Alia Lotta Contra 1*Inquinaoenta Atmosferico. ?umi
Polveri (Milan) 6, (9) 231-14, Sept- 1966. Text in It.
The local administrations should set forth the following
directives: 1) Direct studies must be made to ascertain the
local conditions that cause air pollution. These studies must
also be made at successive tine intervals. 2) Legislative
decrees related to the problems of air pollution must be
applied., The local regulations must be brought up to date.
3) Besearch and the application of favorable solution for
urban centers and for the regulation of cehieular traffic must
be undertaken. 4) Propaganda for the field of sanitary
education must be initiated. A comparison between the causes of
air pollution in various geographical districts of Italy are
mentioned.##
04752
SJIOG SIGNALS. Environ. Sci. Technol. 1 (1) 31-8, Jan. 1967.
The review is concerned with the growing interest in the
pollution problem and evidences of a willingness on the part of the
public to act. The interest in air pollution at various
technical meetings and conferences held recently show that there
is a change in the attitude of indifference. He are losing the
fight against pollution because neither government nor industry has
moved forward with the vigor and determination required. So one
escapes the responsibility for contributing to air pollution.
Do one can escape the consequences of a polluted atmosphere
and all will have to pay for the abatement. The motorist
buying a 1968 car will pay a direct charge for air pollution
control. The switch from high- to low-sulfur fuel in New York
City will cost $12 million a year or $1.50 per capita. Based
on an expenditure of $850 million pec year for the installation
and operation of equipment And disposal of collected pollutants,
the cost would be only 0.11* of the gross national product,
land, air, and water resources must be exploited to support
a constantly increasing papulation concentration while being
expected to assimilate the steadily expanding spectrum of wastes
being generated and released.#*
1024
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
05128
A. A. Boussel and H. Stephany
COITINEMTAL BEPOHT: BtJROPE. proc. Intern, clean Air
Cong.,, loud on, 1966, {Part 1). (Paper 11/6). pp 29-34 and
J. Air Pollution Control Assoc. 16, (11) 583-6, Nov. 1966..
Air pollution by industry, domestic heating, and Motor vehicles
is a result of the local overburdening of the ataosphere which
occurs in industrialized and densely populated countries.. Areas
of a guestionable quality of air are chiefly localised in the
congested areas of fliddle Europe and progressive development of
urbanization and Industrialization currently increases the
endangering of life and property by aore and more densely spread
emission sources. Neither the hygienic control of the ataosphere
is sufficiently developed nor are the effects of cosplex air
pollutions satisfactorily studied. A survey on European air
pollution control legislation shows how far already the conclusions
have been drawn froa the reported facts. (Author abstract
aodified)#1
05571
?. N. Prenkiel
AIH POLLUTION IB THE GB01IHG C0RR08ITT. Proc. Syap, Cleaner
Air Urban Areas* Philadelphia, Pa. pp. 1-15 (1956).
Like any living being, a living coMMunity breathes. Its
autonobiies, railroads* hoie heaters* rubbish disposals, industry,
power plaats....all inhale air and exhale polluted air into the
ataosphere. Here, Or. Treakiel discusses Methods for stu^yiilg
the relative contributions of various pollution sources to a
community's pollution problea, the increase of pollution in a
growing coaaunity, and the effectiveness of certain nethddB for
reducing pollution. He explains how a Mathematical treatment can
clarify the Interplay aaong the Many features of a coamunity that
contribute to its general air pollution problem -the location and
density of pollution sources, meteorological conditions, community
geography, and control Measures, the sain object of these
Mathematical studies, he points out* is to determine the probable
patterns that pollution will take, and the contribution of each
source to the pollutant concentration at Mn? given location. He
cites a study of this sort Made using as anexample of Los
Angeles County. This mathematical treatment, or "model", then
helps determine what Measures must be taken when atmospheric
pollution threatens to reach eaergency levels, how effective
various pollution control plans Might be, what effect a new source
night have on the pattern of concentration, forecasts of patterns
that would result from contemplated urban expansion, and the effect
of urban planning on predicated pollution levels.##
K. Legal and Adminiiteitiv#
>025
-------
06124
Wiethaup, H
SMOG ALARM AND LEGISLATION. Dec Siogalarm in Rechtlicher Sicht-
(Zentr. Aerosol-Forsch. (Stuttgart)) 13, (5-6) 501-8, Bay 1967.,
Ger .
In the state of North Rhine Hestphalia, Germany, there are
presently in effect four legislative acts concerning air pollution.
For incidents of severe smog conditions they provide for:
compulsory change-over to fuels low in sulfur for industrial
enterprises Quitting aore than 200 kg of sulfur dioxide per hour;
banning motor traffic from certain areas; lavs and regulations to
administer and enforce the anti-air pollution acts. The author
questions the necessity for these rather stringent laws since snog
conditions in the area concerned are extremely rare; so far, snog
has never been persistent or particularly obnoxious and is not
known to have caused damage to human health, animal, or plant life.
Caution and vigilance, however, axe being exercised and cooperation
of the industrial and private community is helpful.
06146
V. Rayher* and J. T. Biddleton
THE CASE FOR CLEAR AIR (SPECIAL REPORT). Mill Factory 80,(U)
*1-56, Apr. 1967.
The introdoction in the for* of a series of questions put to Dr.
Middleton is of special interest in indicating the forward thrust
oC the Federal government in air pollution control since he is the
Director of the Rational Center foe Air Pollution Control
which has the responsibility for the administration of the Federal
air pollution control lavs and regulations. His ansvers indicate
vigorous activity by the Federal authorities where local authori-
ties fail to act. The Major provisions of the proposed &ir
Quality Act of 1967 are outlined as well as the existing Federal
authority under the Clean Air Act of 1963* With this back-
ground of increased Federal activity and especially with the
issuance of emission standards, this definitive review continues
with an outline of the various types of air pollutants, their
sources, and the accepted aethods of control. In the section
covering what is being done by industry today, examples are given
of the control measures in effect at a rubber processing plant, a
cement plant, steel plant, and a foundry.##
06188
larsen, Ralph I.
1026
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
DETERMINING BEDOCED-EHISSION GOALS SEEDED TO ACHIEVE AIP QUALITY
GOALS—A HYPOTHETICAL CASE™ J. Air Pollution Control Assoc.,
17(12);E23-829, Dec. 1967. 37 refs. Presented at the Annual
Meeting, Air Pollution Control Assoc., Cleveland, Ohio, June 11-16,
1967-)
Air management steps involved in determining reduced-emission goals
include determining the effects of various pollutant concentrations
on nan, animals, plants, and property; deciding which effects to
prevent; selecting ambient air guality goals that will prevent
these effects; measuring and evaluating pollutant concentrations
from sources and in the ambient atmosphere; calculating overall
source reductions needed to achieve selected ambient air guality
goals; and finally, determining reduced-emission goals for
the various source types. Exaiples are cited of the various
decisions and actions involved in determining a set of reduced-
emission goals for stationary and mobile combustion sources.
06349
AMBIENT AIH QUALITY OBJECTIVES - PAHT 500 {STATUTOBY AUTHCBITYI
PUBLIC HEALTH LAW. 1271, 1276). New York State Air
Pollution Control Board, Albany, Dec. 11, 196ft, 11 pp..
Ambient air guality objectives are tabulated for various
pollutants. The objectives vary according to subregions which
are determined by land usen Included is a list of references for
the sampling and analytical methods employed in the measurement of
particulates, sulfur dioxide, hydrogen disulfide, fluorides,
beryllium, oxidants,, carbon monoxide, and sulfuric acid mist.t*
0673ft
COMMONWEALTH 07 PESHSII.VASIA, DEPARTMENT 01 HEALTH, AIR POLLUTION
commission, ambient A IB QUALITY CMTERIA. 90tb Congress "Air
Pollution—1967, Part IV (Air Quality Act)" senate
Committee on Public Works, Washington, D.C., subcommittee on
Air and Water Pollution, May 15-10, 1967.) p. 2396-7.
Ambient air quality criteria ace tabulated as set forth in section
5 (f) (8) of the Pennsylvania Air Pollution Control Act of
January 8, I960* P.L. 2119. These criteria were adopted on
April 25, 1967 by the Ait Pollution Commission. Included in
the tabulation ares particulates, lead, beryllium, fluorides,
sulfur dioxide, carbon monojtide, and others. References are
provided for the sampling and analytical methods employed for
each pollutant.**
K. Legal and Administrative
1027
-------
0675U
(EXCERPTS FROM THE ANNUAL REPORT FOB 1964 01 THE STATE
INSTITUTE FOB THE PRESERVATION OF CLEAN AIR AND AGRICULTURAL
LAND.) Aus den Jahresbericht 1964 der Landesanstalt fur
Immissions- und Bodennutzungsschutz. Reinhaltung der Luft im
Land Nordrheim-Westfalen (3) 39-48, 1965. Ger»
A survey was made of the activities of an agency of the State of
Worth Rhine-Vestfalia concerned with air pollution problems.
Air pollution control programs ace described, in particular the
first, second, and third program for measuring S02 and dust
concentrations. Instrumentation for measuring SC2, F, H2S,
N02, and HH3 is mentioned. Some practical results of
reducing the emission in various industrial plants are presented,
aostly of the metal and coal-using industries. Extensive
experiments have been made to determine harmful effects of air
pollutants on plants. A list of plants ordered according to their
susceptibility is given.«*
07072
n. E. McLouth and J„ P, Terry
AIR POLLUTION CONTROL AT CAPE KENNEDY. {(Am. Ind. Hyg.
Assoc. J.)) 26 (2), 172-6 (Apr. 1965). (Presented at the
American Industrial Hygiene Conference, Philadelphia, Pa.,
Apr. 26-30, 1961.)
larger missiles and the increased use of toxic propellants require
effective planning and operations to prevent the development of
major air pollution problems. At Cape Kennedy Air Force
station, large-scale air-borne sources are of an instantaneous
rather than a continuous nature. Significant air contamination
sources include missile exhaust, aborts, spills of volatile
propellants, disposal of toxic materials, and normal industrial or
transportation activities. Abatement techniques incorporating
equipment design, operations support, and environmental studies are
discussed. Special emphasis is given controls, test data, and
problems associated Mitb the titan XX missile program.
(Authors" abstract)*#
07483
Maher, G. R.
AIR POLLUTION REGULATION OF NOMVEBXCOLIB, ORGANIC-SOLVENT
IBISSIOHS BY HQS MIGILES RULE 66. J* As. oil chemists
Soc» 44(8):340A, Aug. 1967. (Presented at the AOCS
Short Course, East Xansing, Mich., Aug. 29-Sept. 1, 1966.)
1028
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
In an effort to control sources emitting organic solvents into
the atmosphere, the Air Pollution Control District of Los
Angeles County, Calif,, successfully secured passage of Bale
66 into law. Rule 66 specifically relates to the control of
organic solvent emissions from stationary sources, the major
contributor to the 550-ton daily emission of organic solvents was
industrial# commercial, and residential painting. Organic
solvent-containing products axe to be controlled as follows. 1.
A maximum of 5X by volume of olefinic or cycloolefinic organic
solvents nay be present. 2. % maximum of 8X by volume of arcaatic
organic solvents having eight cr more carbon atmos may be used.
3. Ketone organic solvents having a branched chain structure* such
as methyl iso-butyl ketone, are limited to a maximum of 20X by
volume. (». A maximum of 20* by volume of toluene may be used.
5. Ethylbenzene, an aromatic organic solvent with eight carbon
atmos, was given a special statue and alloved a maximum of 20X by
volume. 6. Trichloroethylene is restricted to a maximum of 20%
by volume.##
01519
Chass, Robert L.# Hichael Pratch, and Arthur A. Atkisson
THE AIR POLLUTION DISASTER—PREYEXTIC1I FHOGBAM OF LOS ARGELES
CCONTYo J. Air Pollution Control assoc., 8(1):72-81, May
1956. (Presented at the 50th Annual fleeting, Air Pollution
Control Assoc., St. Louis, Ho.* June 2-6, 1957.)
The objectives of the L..A. disaster prevention program are as
follows: (1) To identify the specific contaminants present in smog
which are capable of inducing health disturbances. (2) To
establish concentration standards for these contaminants which
provide a safe margin in the event of adverse meteorological
conditions which would tend to concentrate their dosage in the
los Angeles Basin and to prevent feheir rapid dispersion and
evacuation from populated areas. (3) to establish means of
measuring continuously the presence of these critical contaminants
in the Los Angeles atmosphere, (4) To establish emergency
methods which may be implemented in the event measured
concentrations approach the standards established as potentially
harmful to the public* The approach used to attain each of these
objectives is described.##
07550
Philadelphia Dept. of Public Health, Pa.
AID POLLUTION PBOH JOEL COHBUSTIOS PROCESSES IS PHILADELPHIA-
Preprint, 8p., Sept. 1966.
The combustion of fuels is the greatest single source of air
pollutant emissions within a metropolitan area. As much as 80% of
K. Legal ami Administratis
-------
the total weight of pollutants discharged to the ataosphere result
fros the burning of fuels fox electrical power generation, for
industrial and coanercial heat and power, for doaestic heating, and
for vehicular power. The purpose of this report is to suanarize
the present status of the problei in Philadelphia and to reconxend
necessary regulations and other action required to deal with the
problem.##
07597
Heller, A.
BAXIHUK PERMISSIBLE COHCIHTRATICHS JOB MB POLLUTION IN THE
FEDERAL REPUBLIC OF GERM SHI. Preprint, Federal Inst, of
Hygiene for Water, Soil and Air, Berlin, Germany, 10p.f 1963.
(Presented at the Inter-Regicnal Syaposiua on criteria for
Air Quality and Methods of Neasurenent, Geneva, Switzerland,
Aug. 6-12, 1963, Paper Ho. »HO/*P/8„)
An advisory coanittee set up by the Federal Governaent gives
expert advice on the proposals of the clean Air Conmission of
the Association of Geraan Engineers regarding peraissible
emissions as well as on the aaxiaua concentrations of "inaissions"
- the MIK values - for various air pollutants. The task of the
Verein Deutscher Ingenieure Coaaission is to set scientific
and technical bases for appropriate air pollution control Measures.
The main task of the Coaaissien is to draft recoaaendations for
new technical regulations as a basis for the deteraination and
control of air pollution, as follows: Miniaua requirements
regarding the concentration and precipitation of dqsts and gases
in the ataosphere, bases for calculating the distribution of dusts
and gases and for deteraining the required height of chianeys,
limits to the eaission of dust and gas froa sources of air
pollution, and procedures for aeasuring dusts and gases. The
provisions recoaaended for Qxaaining applications for licences to
establish new plants or to alter existing plants are reviewed.
Enforceaent of these regulations will depend on the local
situation, especially the existing pollution load. They will also
depend on the extent to which further pollution could occur,
without exceeding the tolerance liait or the HlK-value for the
aost sensitive aaong the reaction partners, whether huaan being,
anisal or plant/ and on the technical processes of the industrial
plant in question. In principle, all reasonable technical and
econoaic possibilites for purifying waste gases should be
exploited in equal fashin by aiailar industrial plants. Finally,
industry should be prepared to bear more far-reaching demands
regarding waste-gas reaoval, if a licence for a new industrial
plant or for the extension of an existing plant is to be issued in
an area already polluted. HIK-values have been set and are
discussed fox; sulfur dioxide, hydrogen sulfide, some nitrous gases
and chlorine.##
07766
Missouri Air Conservation Coaaission, Jefferson City
1030
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
AIB QUALITY STANDARDS AND AIB POLLUTION CONTBOL REGULATIONS FOR THE
SI. LOUIS METROPOLITAN AREA. Preprint, 46 p., Feb. 22, 1S67.
Allowable maximum average concentrations for various periods of
time are listed for major pollutants such as S02 ana suspended
particulates. Among the topics covered in the 24 regulations are:
Restriction of Emission of Particulate Matter from Industrial
Processes; Open Burning Bestrictions< Restriction of Emissions of
Sulfur Dioxide from Ose of Fuel; and Control of Odors frcjn
Processing of Animal Hatter.
07877
Downing, George
A BEPOBT ON AIB POLLUTION AND AIB PCILDTIOH CONTBOL IN
CLEVELAND* Preprint, 1956 Onion Commerce Building, Cleveland, Ohio,
U76)) P». sept. 21, 1967. 44 refs»
The contents are: (1) a brief survey of the national air pollution
crisis; (2) a survey of the air pollution crisis in Cleveland; (3)
statistics on the Cleveland pollution problem and how they are
obtained; (4) the major sources of air pollution in Cleveland#
effectiveness of present measures for their control,
recommendations for future control; and general observations. A
report of the National Center for Air Pollution Control on Relative
Severity of Air Pollution in the 65 standard metropolitan
statistical areas, August, 1967; Table on air pollution in 302 u.
s. cities prepared fay the Division of Air Pollution of the Public
Health Service, 1966; and little Hoover Commission Report on
Division of Air Pollution Control of the City of Cleveland,
January, 1967 are appended.
08194
Kalyuzhnyi, D. Y. I. Kostoveskii, S. A. Davydov,
and K. E. Aksel*rod
EFFECTIVENESS 07 SANITAB! CLEARANCE ZONES BETWEEN INDUSTRIAL
ENTERPRISES AND RESIDENTIAL QUARTERS.. Gigiena i Sanit., No.
1:9-12, 1952., Translated from Russian by B. S. Levine,
0. S. S. S. Literature on lie Pollution and Belated
Occupational Diseases, Vol* j, p. 179-183, Aug. I960*
CPSTI: T TT 60-21913
Results of atmospheric air studies in the vicinity of chemical
and metallurgical plants demonstrated that dust, sulfur dioxide,
hydrogen sulfide and nitric oxide vece absorbed from polluted air
by suitable types of plant life to a considerable degree. It is
recommended that in creating intervening sanitary clearance zones
provisions should be made for planting suitable trees and other
types of plant life. ISi#
K. Ligal and Administratis
1031
-------
08463
floss, Laurence W.
SIZING OP ANTI-POLUJTIO-N LEGISLATION CheB. Eng.,
71415)s191-196, July 17, 1967. 18 refs.
At instigation of Federal Govecnaent, states are working rapidly
toward effective standards for regulating quality of water and air.
Standards for water will depend primarily on authoritative
technical opinion and will vary according to local conditions.
Standards for air quality will come increasingly under direction
of Federal Governaent and will tend to be more uniform from
locality to locality. Air control, state laws and regulations,
Bunicipal laws and regulations and the pattern for the future are
air pollution topics discussed. Other topics dealing with water
pollution are discussed.*4
08554
Dorn, Warren N.
ROLE 66 - A PAST OF TOTAL AIR POILDTIO* CONTROL. S.A.I. (Soc.
Autoaotive Engrs.J, Preprint 670807, 2p.f 1967. (Presented at
the Aeronautic 6 Space Engineering and Hanufacturing fleeting,
Los Angeles, Calif-, Oct. 2-6, 1967.)
The part Bale 66 plays in total air pollution control in Los
Angeles County is explained. Backgrcund naterial on the control of
visible emissions, sulfur, hydrocarbons, and aotor vehicle
eaissicns is presented. Finally, the background and acceptance of
Rule 66 is described. (Authorls abstract}
08556
Lunche, Robert G.
COMPLYING WITH SOLVENT CONTROL LEGISLATION. S.A.E. (S0oc„ Auto-
Botive Engrs.l* Preprint 670B10, 3p.» 1967. (Presented at the
Aeronautic G Space Engineering and Hanufacturing Meeting, Los
Angeles, Calif., Oct. 2-6, 1967.)
CoBpliance with Los Angeles County solvent control legislation
be achieved by treataent of the organic eaissions resulting fron
solvent usage, converting to less photocheiically reactive
solvents, or changing the process. An engineering perait systea
and an enforceaent inspection frograa ensure that control equipment
to treat the effluent is designed for the required efficiency and
operated in coafliance with the law. (Authorts abstract)
09137
Cyrankiewicz* J.
1032
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
PERMISSIBLE CONCERTRATION OF AIF FOIlOTION. Dziennik Ostaw
(Warsaw)# Wo. 42:103-10## Oct. 8# 1966. Translated from
Polish. Joint Publications Besearch Service, Washington,
D. CB-9119-D# 3p*# Jan. 30, 1968.
Maxima allowable concentrations of S02« B2S04, vox,
H2S, CO, gasoline# dust# and CS2 in "special protection
areas" and "protected areas** in Poland are outlined. Special
protection area includes areas of health resorts and health
protection areas, national parks# and reservations of natural
resources. Protected area includes other terrains of the land,
with the exception of land occupied by manufacturing establishments
or other sources of pollution and protective zone areas.
Exceptions for a specified period can be granted in the following
cases: 1} Difficulties involved in the installation of air
purification facilities in the manufacturing establishments due
to exceptionally high investment costs, lack of opportunities to
find a producer of such eguipaent or appropriate technical nethods.
2) Excessive agglomeration of manufacturing establishments in a
given area, which causes air pollution in excess of the permissible
concentration in spite of the utilization of appropriate
purification facilities. 3) When it is necessary to build in a
given area a new manufacturing establishment which will result
in exceeding the permissible concentration of air pollution in
spite of the fact that the most adequate equipment has been
installed to reduce the pollution.##
09281
California Rotor Vehicle Pollution Control Eoard# Los Angeles
SHOGj THE SIIE81 SNEHT. (F00BTH BIEHHIAL BIPQBT FOB CALEBCAB TEABS
1965-66.) 32p.# Jan. 1967.
California has led the world in the fight for cleaner air* nowhere
are found such dynamic and aggressive programs, both on local and
Statewide levels* Howhere are there more dedicated men and women
engaged in the effort. Admittedly# the automobile is a major
factor in befouling our atmosphere. The ultimate solution to the
motor vehicle pollution problem may lie in a completely redesigned
automobile engine or in a new motive power source. The Baaed has
thoroughly examined these possibilities, such as the turbine and
battery-powered car# and is encouraged for the future# perhaps a
decade hence. Bat, until that time# the State must proceed with
its present plans to reduce auto-created pollution with workable
control systems or engine modifications. Through sustained#
persistent efforts by a determined Administration# State
Legislature# and Board# the automobile industry has acknowledge and
complied with California!s leadership. Today# emission control is
a fundamental factor in automobile engineering. For the first time
all the worldls engine designers are hard at work on the problem.
Today# emission control is |built-in#| not fadded on#| to every
Detroit product. This represents a phenomenal advance in the space
of six and a half years. It will continue to result in a better
product for the California cat purchaser. All new California
automobiles now come equipped with both crankcase and exhaust
K. Lop) and Administrative
1033
-------
eaissi.cn control systems. The Highway Patrol is Baking random
roadside checks to cake sure that motorists are complying with the
law, and the Department of dotor Vehicles has co-operated in
carrying out the necessary registration procedures for controlled
vehicles. Stricter emission standards must be applied in 1970.
Oxides of nitrogen control systems will be incorporated into
existing controls, if they are in harmonj with hydrocarbon and
carbon monoxide controls. Evaporative losses must also fce reduced,
with a consequent economic saving to the motorist* The Board is
actively seeking and hopes to find a simple portable measurement
device far all emissions. This would simplify annual emission
Inspection for all vehicles. There is so doubt that as time passes
emission reduction systems will improve rapidly. The art and
science of emission control are still is their infancy* but moving
ahead.
09285
H. Rolozin
JEDEFAX PISC1I POLICY IS Alt POIIOIIOM CODTBOl. (PREPARED
DlicOSSlOH.) Preprint, itassachusetts Univ., Boston, Dept.
of Economics, 4p., 1966 (Presented at the National
Conference on Air Pollution, Washington, 0. c., Dec. 12-14,
1966.)
Important questions to consider in determining policies on
air pollution are hov much is presently known about
polluted air, how extensive are damages and whether the damages are
progressive and irreversible. Policy recommendations would be
different if time were not of the essence and damages were
remediable. Measurement technigues are confined to direct
effects of high levels of contamination. It is recommended that
priority be given to research on measuring indirect and insidious
effects of low level exposures of long duration. The air
pollution problem poses the need for serious considerations
of alternatives to influence management decisions. Research
is required to determine if effective control will not
ultimately demand basic modification of traditional
government-industry relations. It is recommended that air
pollution authorities be given the authority and resources
to pay for air pollution filtering and control devices or
bear the cost of modifying existing equipment. In return
authorities would receive the right through public commissions to
participate in corporate decisions affecting emission of
pollutants.*#
09765
Minnesota State Board of Health, Minn.
A RBPOtT 0* I IB POUOTIOH I» aiUTIESOlA. MSBH-X-172, p. 1-27,
July 31, 1966.
1034
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
Air pollution is of increasing significance in the state and
requires the attention of the State* The legal problems of
authority, obligations and jurisdiction are complex and reguire
careful deliberation for their resolution. Prolonged deliberation
should not delay the establishment of a state control program.
Existing state laws are sufficient for the initial establishment of
a technical air pollution ccntrcl program by the State Board of
Health if adeguate funds are made available.
10327
McKee, John W.
TRENDS IN THE CONTROL OF PHOTOCHEMICAL SMOG IN THE LOS ANG£,L£S
EASIN. J. Invircn. Sci. , 11 (3) June 1968. 12 refs.
The general background of the snog problem is considered,
together with the effect of various emission standards on the
projected output of unburned hydrocarbons in the Los Angeles
basin and the effect of car pools, simple traffic patterns, and a
rapid transit district. Current and planned California emission
standards are not liJcely to solve the photochemical smog problem in
the Los Angeles basin until the late 1980's or early 198C's.
Emission controls are a long-range solution, just as the
development of unconventional fewer plants for automobiles is a
long-range solution, installation of control devices for
crankcase blovby emission when used cars are transferred (torough a
dealer) is net an effective solution and should be abandoned. The
traffic pattern has a very sensitive effect on the amount of
unburned hydrocarbons released by motor vehicles, if the
recommended 1960 emission standards ace not established or not met
and no significant changes are made in traffic pattern, the level
and extent of air pollution will probably increase in southern
California. Car pools when employed with the current emission
standards are the most immediately effective approach to a
solution, pools should be advocated on only those days when smog
cs potentially severe. Unobstructed freeway driving should be
encouraged, and start-stop driving should be discouraged,
particularly in the metropolitan core. If new traffic pattern
surveys show that staggered work hours are useful, they could be
instituted on potentially smoggy days, tlany partial solutions,
such as mass rapid transit, staggered work hours, and car pools,
may begin to be noticeably effective in the middle 1980's if
implemented simultaneously.*#
1Q992
Okita, Toshiichi
COHCE8TBATIOH OF SBLlATE AMD OTHEB ISORGAHIC MATERIALS IH IOG ABB
clcuD BATIB AND IN AEROSOL. J. Heteorol. SCC. Japan/
46 (2):120-126, April 1968.
Measurements were made of sulfate and other inorganic materials
K. Legal and Administrative
1035
-------
in tog and cloud water in 1963. It was found that in cumulus
clouds above Kt. Norifcura, sulfate was in the form of ammonium
sulfate and sulfuric acid. In upslcpe fog at Shiobara, and in
stratus cloud which covered Mt. Tsukuba, suliate was supposed to
be combined with some metals in addition to ammonium ions. During
the periods of September 1962 to February 1963, and of July to
December 1966, separate samplings of large and giant particles
were made in Tokyo by means of a high volume cascade impactor.
It was found that the weight ratio of S04—/S02 was above
0.12 at relative humidity above 55*, wind velocity below U m/sec
and visibility below 5 Ki,. It seems that atmospheric humidity is
an important factor for the atmospheric oxidation of S02. The
relationship of the amounts of sulfate and ammonium
was studied. These studies indicate that various weather and
environmental conditions affect the atmospheric oxidation of SQ2.
The atmospheric concentration of hydrogen ion contained in aerosol
was usually below 3 x .01 ug/cu m except on October 26, 1966, when
the atmospheric concentration of hydrogen in large particles was
1.7 to 7.5 ug/cu m heavy smog. (Author's abstract)##
11QC4
Schmidt, F. H.
METEOHOLOGICAL ASPECTS OF ATMOSPHERIC POLLUTION AMD ATMOSPHERIC
CHEKIS1BY. Atmos. Invircn., 2 (4):423-U26, July 1968.
Discussions are made in this repcrt on the following topics:
network c£ stations for measuring background pollution; sampling
techniques from the meteorological point ot view; meteorological
factors influencing the dispersion of atmospheric pollution;
boundary layer observations; special pollutants; forecasting
pollution problems.##
11074
Chass, R. L., Krenz, H. E., and Dickinson, J. £.
AH APPRAISAL OF RULE 66 OF THE 10S ANGELES COUNTY AIB POLLUTION
CONTROL DISTBICT. Preprint, Los Angeles Ccunty Air Pollu-
tion Control District, 22p., 1968. (Presented at the 61st
Annual fleeting of the Air Pollution Control Association, St.
Paul, Binn., June 23-27, 1968, Paper 68-46.)
Emissions of organic solvents to the atmosphere of Los Angeles
County Air Pollution Control District (APCD) are currently
estimated at 600 tons per day. In order to reduce these emissions
Rule 66 was enacted on July 28, 1966, after more than a year of
joint effort by industry and the APCD. The provisions of rules
66, 66.1, and 66.2 are explained as well as how their enforcement
will affect industry and the entire community, and discusses the
methods being utilized by industry to bring its various operations
into compliance. (Authors* abstract, modified)
1036
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
11090
Scofield, Francis
THE PAINT INDUSTRY APPROACH TO SOLVENT EMISSION CONTROL.
Preprint, National Paint, Varnish and lacguer Assoc., p.,
1968.
The National Paint, Varnish, and Lacguer Association
established a snog chamber for the use of the paint industry, to be
devoted entirely to solvents used in coatings. The chamber is
currently operating and meaningful data are being collected. The
objectives include: the determination of smog-forming
tendencies of solvents which had not been previously examined, and
which are not currently controlled; the examination of solvents
currently controlled, as members of a class (such as branched-chain
ketones) although nc tests had been run on the specific compound;
study of the products of baking ovens; and study of the
smog-forming reaction, to relate structure to smog-forming
tendency. Some policies, contributions, and positions of the
association are also described.#t
11400
Public Health Service, Arlington, Va,, National Air
Pollution Control Administration
REPORT 70S CONSULTATION ON THE $AN ffiANCISCO BAY AREA
AIR QUALITY CONTflOL REGION. 46p., Dec. 1968. 25 Eefs.
"Air quality control regions" axe designated to provide a basis
for the establishment of air guality standards and the
inplementation of air quality control programs, A study of the
San Francisco Bay Area has btien conducted. The Region
boundaries proposed in this repcct reflect consideration of
available and pertinent data. Data ptesented are evaluation of
urban factors, (land use, population, transportation, governmental
organizations) and engineering factors, (emission Inventory and
meteorological data).##
114211
Eilers, h.
A IK POLLUTION.. IV. 1LEST AND ALABB REGULATIONS Iff SOUS
FOREIGN CITIES. ((traalcaaamheids- en alarastelsels in enkele
buitenlandse steden.)) Translated from Dutch. Ingenieur,
80(10) :G33-G38# March 8, 1968. 17 refs.
Air pollBtion alert and alarm regulations in Ingolstadt, and the
K. LeiaJ and Administrative
1017
-------
tJrhr am, Germany, New Kork city, and Los Angeles
County are discussed in detail, tabulated and compared. The
differences in predominant types of pollution - eg photooxidation
in los Angeles, S02, soot, etc. in New York, and S02 in the
Urhr area - are noted, with a detailed explanation of the
complexities of los Angeles smog and of the various alarm stages
used. The possibility and desirability of introducing an alarm
system in the Netherlands is discussed. With increased
motorization, the chance for damage to horticultural districts is
increasing, and an alara systea, resulting in the limitation of
traffic under unfavorable conditions, ma; be required.**
1173t
Haga, John A.
CONSIDERATIONS IN ESTABLISHING ABBIENT AXB QUALITY STANDARDS.
J. Occupational Red., 10 (8):408~413, Aug. 1968.
Some of the factors ta be considered in the establishment ot air
quality standards by the U.S.P.{.S. or state and local
governments are the purposes and uses of such standards, the degree
of understanding regarding the effects c£ pollutants on the
environment, and the existence of usable data on the concentration
of contaminants in the ambient air. a distinction is drawn
between air quality standards and air quality criteria on which
they are based, as well as between air quality standards and
emission standards which serve as the direct basis for control.
It is pointed out that ambient air quality standards are generally
much lower than threshold limit values for occupational exposure,
and that careful attention must be paid to the relationship between
effects of air pollutants and concentration. An air monitoring
program is an essential part of any developmental work towards the
establishment of air quality standards. Among the potential
effects to be taken into consideration are those on human health,
vegetation and livestock; irritation to the senses, and impairment
of visibility; soiling, unpleasant odors and other esthetic
effects. The experience of the State of California in the
establishment of air quality standards is briefly reviewed, with
emphasis on the three-level approach ("emergency", "serious", and
"adverse" levels) and the "oxidant index*'.*#
11810
Staisey, Consuelo E.
A HISTORY OF SMOG CONTBOI LEGISLATION. In: An Educational
Experiment in Self-Direct Research, Summer 1968. Associated
Students of the California Inst, of Tech., Pasadena, p. 137-156,
1968. 27 refs.
The activity of California state and local governments with
respect to abatement of smog in the Los Angeles area is reviewed.
In 1953, the first year of state action. Assembly bills were passed
authorizing the establishing of emission standards and air quality
1038
PHOTOCHEMICAL 0XI0ANTS AND AIR POLLUTION
-------
standards. No direct control measures ior vehicular exhaust were
instituted during the 1950*s, but important changes occurred, Los
Angeles County abandoned the concept of local control in favor of
the alternative goal of state control. In 1960, the State Motor
Vehicle Pollution Control Board was created and assigned the
responsibility of testing and certifying automobile emission
control devices. The impact of this legislation was noticeable:
major car corporations began installing crankcase devices on cars
to be sold in California. Strong legislative interest like that
demonstrated in 1960 did not reoccur until 1963, when a bill was
introduced which proposed a system for the installation and
inspection of motor vehicle control devices. Subsequent amendments
relating to cost and enforcement procedures seriously weakened the
bill. The Pure Air Act of 1968 similarly sidestepped the issue
of enforcement and lowered the cost ceiling on car exhaust devices,
thereby reducing development prospects, if clean air is restored
to the Los Angeles area, it may be as the result of other bills
that give serious consideration to alternatives to the internal
combustion engine.
11811
Roberts, Thomas B.
AN CVEBVIEM OF THE POLITICS OF AIR POLLUTION CONTBOL. In*. Air
Pollution Project: An Educational Experiment in Self-Directed
Research, Summer 1968. Associated Students of the California
Inst, of Tech., Pasadena, p. 157-168, 1968. 35 refs.
The failure of the California legislature to enact a stringent
smog control till is examined in terms of rural opposition,
bureaucratic indifferences, and pressure groups representing the
automobile industry. Also discussed is the lack of coordination
between three departments with crucial control responsibilities;
the California Air Resources Board, which is responsible for the
certification of control devices and emission standards; the
California Highway Patrol Department, which licenses and inspects
the official installation-inspection stations for control devices;
and the California Department of Public Health, which issues
recommendations for air quality standards. These agencies, which
adopt varying and sometimes contradictory regulations and policies,
are unable to collaborate on imaginative alternative pollution
policies. The development of a smog control policy is additionally
hindered by the hostility between the Air Besource Board and the
Los Angeles County Air Pollution Control District. As a solution
to the smog problem, a massive public education campaign- is
proposed to inform the public of the economic, medical,
psychological and aesthetic costs of air pollution. Motorists
must be willing to maintain their smog control devices before and
after inspection.
13366
Japan, prime Minister's Office.
K. Legal and Administrative
1039
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1969 WHITE PAPER ABOUT POBLIC RUISAKCES. (Kogai hakusho) ..
Text in Japanese. (Prepared in collaboration with 11 ministries
and agencies, Government of Japan, for submission to the
Japanese Diet). Tofcyc, Printing Bureau of the Ministry of
financer 1969, 230p.
This report summarizes the status, monitoring techniques, and
management, including lavs, cf air and water pollution, noise
and vibration, and soil erosion in Japan in April 1969..
Particulate air pollutants in Japan are of four types: falling
dust, vbich contains large particles and includes soot from
burning coal or muddy dust; sulfur oxides, which are becoming
increasingly important because of the increasing use of
petroleum in recent years; floating dust, which has very small
particles and includes mainly molecules of netallic compounds
from burning materials and carbohydrates; and engine exhaust gas
containing CO, N02. hydrocarbons, and aldehydes. The amount of
falling and/or floating dust has been gradually decreasing with
the decreasing use of coal, especially in large Industrial
cities. At the same tiAe, sulfur oxides, especially S02, have
been gradually increasing and hate the highest concentration
(¦ore than 1.5 mg S03/100 sq cm/day} in Kawasaki, Yokohama,
Hagoya, Tokyo, Osaka, Huxoran, and Yokkaichi. Among the harmful
effects of polluted air on the human body, the ill effects on
the respiratory tract (especially on the lungs) are most
important, chronic bronchitis, bronchial asthma, pulmonary
emphysema, pulmonary fibrosis, pulmonary cancer, and cor
pulmonale are the main lung diseases induced by polluted air.
3, 4-Benzopyrene, which is a component of automobile exhaust gas,
was experimentally proved to be carcinogenic. In nay 1962, the
law entitled 'Provisions on the emission of smoke1 was
established to control the ambient air system, and three large
city groups (Tokyo-Yokohama, Osaka-Kobe, and Kitakyushu) were
designated as air-polluted areas. Several cities, including
Yokkaichi, were subsequently designated. This law was improved
in Day 1968, especially from the viewpoint of prevention. A law
which sets limits for automobile exhaust-gas emissions has also
been in force since September 1966. Air pollution is monitored
in Japan at sore than 170 points. In recent years, several
techniques of preventing air pollution have been devised with
varying success: use of activated carbon or activated manganese
dioxide to reduce S02 concentrations; quantitative and
qualitative measurement of air pcllution severity using a
simulation model of a polluted area; modification of internal-
cokbustion engines; and development of electric automobile
engines*
15605
Berlndan, Cornelia
IHTEH-RBLATIOH BEfWlElf AIR POtlOTIOI AMD OPES SPACES, AS A
PRINCIPLE FOB THE PROTECTION 07 INDUSTRIAL OBBAN CENTRES.
(Interrelation pollution atmospherique et espaces verts en tant
gue principe protecteur des villes industrielles). Text in
French* Pollut. Atmos. (Paris), 11 (13}:143-153. July-Sept. 1969»
59 refs.
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
The use of vegetation foe the protection of residential areas
fro* air pollutants emitted by neighboring industrial plants
is reviewed. K table listing the principal (smog and its
constituents), secondary (aerosols and oxides) and other gaseous
aerosol, or particulate pollutants is given. Pertinent research
concerns the effect of pclluted air on vegetation, And the effect
of vegetation on ataospheric air, particularly on polluted air..
\ table of phytotoxic effects of industrially polluted air is
provided with respect to 267 subspecies of plants, as rated in
Roaania, Poland, OSSR, Germany, Holland, Bulgaria, Austria, and
Sweden. The capacity of retaining airborne dust by 12 species
of trees is also tabulated. The capacity of plants to retain
pollutant gases is discussed. The aerodynamic effects of tree
plantings and their role in dust retention and as wind
deflectors are pointed out. Illustrations of the use of green
belts for protection of residential areas from polluted air
based on studies Bade in the United States, Holland,
Czechoslovakia, and Bunania are given. General principles which
govern the layout of protective zones of vegetation in industrial
urban centers are provided*
16504
BrocKe, S.
MEASURES ADOPTED IN WEST GERMAN! FOR COMBATING THE EMISSION OF
S02 INTO THE ATMOSPHERE. (Nisure per combattere l'ingiissicne dell*
S02 nell'atnosfera adottate nella Germania Occidental®). Text in
Italian. Riv. Coabust., 22 (7/8):397-401, July-Aug. 1969.
(Presented at the *Le grandi Centrali lermoelettriche e nucleari
ed i probleml dell*inguicamento ataosferico, Tavola Rotonda, Rome,
April 4, 1968.)
Sources of ataospberic sulfur dioxide pollution in Hest. Germany
are distributed as follows: thermoelectric plants, 35ft;
industrial installations, 47*; and domestic uses, 18*. In North
Rhine-fiestphalia, the S02 level is measured every 14 days at
5000 check points, over an area of 5000 square kilometers* This
province, which produces 50% of Germany's electricity, 80* of its
iron and steel, and 50* of its cfceaicals, has a snog warning
system based on 12 special measuring points, at 2*5 mg/cu m, a
preliminary alert is given# while at 5 mg/cu a of S02, the
authorities are to infora industries to switch to low-sulfur fuels,
and aotor traffic is to be restricted from 6-10 a.m. and 4-8 p.a.
This provincial government has spent more than 6 Billion DM
(about 1.5 aillion dollars) on studying desulfarizing procedures.
Experimental projects include: the Reinluft process; lime/doloaite
absorption; 'airborne ash-lignite*; activated carbon; the Siemens
process (using iron oxides); the Grille process (using special
aetallic oxides); the Sulfacid process; and experiments with wet
processes, with special attention to methods of regenerating the
washing solution. Desulfurizing the fumes froa an electric plant
increases the cost of each kilowatt hour by an estimated 4-10%.
Certain by-products of the desulfarizing process are much in
demand. No danger exists of saturating the market with
sulfuric acid, ammonias sulfate, gypsum, or calcium sulfite.
K. Lagal and Administrative
1041
-------
It all the sulfur dioxide produced German thermoelectric plants
were made into sulfuric acid, it uould fill only 60% ot current
demands for the acid.
16736
Cleary, Graham J.
A STATUS REPCfiT: AIR POIIOTICS! CGS180L IN AUSTRALIA. J. Air
Pollution Control Assoc., 19 (7):U90-496, July 1969. 13 lefs.
All but one of the Australian States now have legislation to
control air pollution. These ate similar in broad principle and
rely upon the system of prior approval and the use of emission
limits. At the present time Victoria is the only state with
legislation providing for the recycling of crankcase vent gases
on motor cars. Methods being used to control pollution and
future outlook and needs are discussed. At least 65 percent of
the crude oil requirements should be net by indigenous low sulfur
oil by 1975. This fact and the imminent supply of natural gas to
the four major cities and to the centers of heavy industrial
development should result in a narked reduction in sulfur dioxide
concentrations. A major outstanding problem is the lack of air
pollution considerations in planning at regional and local
government levels. (Author's Abstract)
16799
Sparrow, Christopher J., A. ?. Skam, and N. G. Thorn
THE GROWTH AMD HOftK OF THE AUCKIA8E AIR POLLUTION RESEARCH
COMMITTEE. Clean Air (J. Clean Air Soc. Australia New Zealand),
3(1)13-12, March 1969, 23 refs.
Some of the important characteristics of the Auckland Urban Area
are briefly described prior to a discussion of the formation and
organization of the Auckland Air Pollution Besearch committee.
The work of the committee is described and a summary of the results
vhich have been obtained from its air sampling network is
presented. The committee has cartied out a considerable amount
of research into local meteorological conditions and results to
date are commented on. (Author's Abstract)
17188
Hashimoto, Hichio
STATUS 0? AIR POLLUTION BY BOXIODS ADD OFFENSIVE GASES ABE THEIfl
CQS1B0L EHOGBABHES. (Yugai gasu to niyocu osen no genjo to sono
taisaku ni tsuite). Text in Japanese. Kogai to Taisaku (J.
Pollution Control), 2 (7) Aug. 15, 1966.
A procedure for the adequate control of noxious gases, some of
1042
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
which are not yet covered by legislation, is discussed. Though
dust fall is decreasing as a ccnseguence of regulatory control,
noxious and offensive gases are increasing in many industrial
areas. The Labor Standard Law of 1947 provides for the control of
working environments in the interest of worker health, but is no
lcnger consistent with the present state of industrial pollution
which poses a hazard for persons living in the vicinity of plants.
The 1948 law regulating agricultural chemicals is concerned cnly
with preventing injuries to feeble and livestock caused by the
unrestricted use ot chemicals; it dees not consider the
contribution of the chetticals to air pollution. High pressure
gas control, fire prevention, Bining, and other laws are subject
to the same criticism. What is characteristic of these control
laws is that they do net specify total noxious gas emission nor
the relationship between a gas and its effect. The Smoke Dust
Control Law is intended to condensate for these shortcomings; it
now deals with sulfurous gas, anhydrous sulfuric gas with hydrogen
fluoride, hydrogen sulfide, selenium oxide, hydrogen chloride,
nitrogen dioxide, sulfur dioxide# hydrogen cyanide, carbon
disulfide, ammonia, phosgene, and silicon tetcafluoride. More
offensive gases are to be covered by the law.
18024
ILLINOIS MOVES A10NG IN fIGHT JOB CLEAH AIB. LEGISLATIVE STUDX
COMMITTEE RECOMMENDS AIR QUALITY STANDARDS. Environ. Sci.
Technol., 3 (<») : 319-320, April 1969.
The Joint Air Pollution Study Committee of the Illinois General
Assembly, began work in 1967. They have issued a final report
calling for the following courses of action: Establishment of
a Department of Environmental Pollution Control; abolishment of
the present nine man air pollution control board; appointment of
a superintendent of air pollution control; and endorsement of
nine ^recommendations for air quality standards.
K. Legal and Administrative
1043
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L. STANDARDS AND CRITERIA
00157
Haga, John A. and John 9. Kinosian
MOTOR VEHICLE EMISSION STANDARDS - PRESENT AND F0T0PE.
In: vehicle Emissions, Part II, SAE Progress in
Technology Series, Vol- 12, New York, Society of Automotive
Engineers, Inc., 1966, p« 297-306- 10 refs. (Presented at the
SAE Automotive Engineering Congress, Detroit, Mich.., Jan.
10-14, 1966.J
In California, the state Dept. of Public Health has
established motor vehicle emission standards for exhaust
hydrocarbons, carbon monoxide and snoke; for fuel tank and
carburetor evaporative losses; and for crankcase hydrocarbon
emissions- The data on which the standards are based and the need
for improved measurement procedures are discussed. At this time,
exhaust emission standards for oxides of nitrogen and for odor are
being considered as additional standards. Future standards may
rate hydrocarbon emissions according to their smog potential.
Another possible change that is discussed is to specify the
quantity rather than the concentration of pollutants that may be
emitted fro* the exhaust of motor vehicles.##
00411
K. Horn
(THE PFOBLEH OF HTGIJSHICAILT PERMISSIBLE IIHITING COUCBBTKATIOSS
OF AIR POllUTION.) Zur Frage der Bygienisch zulassigen
Grenzkonzsntrationen fur luf tverunreinigungen.. Angev.
Heteorol. (Berlin) 5 (Special Issue) :39-43, 1965. Text in
Ger.
The problem of determining permissible limits of air pollution is
discussed. After listing four categories of pollution ranging
from decreased visibility and injury to sight and swell to acute
illness and possibly deati, the aorthor states, that pollution
should be kept below the limit* of the first category. Be
distinguishes between limits permissible in a factory area
and in a residential area, the first being higher. Permissible
limits for 40 cbemicalB established in 1963 for single
occurrences and aver«g« 24 hour concentrations for East
Germany are tabulated^#*
01007
E. T- Blomguist
TOW
-------
FEDERAL ACTIVITY IN DEVEIOPING Alt) COALITY CRITERIA. J. Air
Pollution Control Assoc- 16(10| :530-1, Oct. 1966. (presehted
at the 59th Annual Heeting, Ait Pollution Control
Association* San Francisco, Calif., June 20-25, 1966, Paper
Ho. 66-91„)
Documentation of air quality criteria for the oxides of sulfur
and photochemical oxidants is discussed. Physical and
chemical properties, the sources of the pollutants and their
concentrations in the atmosphere, methods of measurement, chemical
reactions in the atmosphere, and associated effects on visibility,
materials, vegetation, man and animals Mere the sain objectives of
the literature review studies and tabulations.#*
011U9
v. w. stalker and c„ B.. Robinson
A J1STH0D FOB BSISG AIR POLIDTIOS HEASDRESESTS AHD PUBLIC OPISION
TO ESTABLISH AHEIBHT AIR QUALITY STANDARDS . J. Air Pollution
Control Assoc. 17, (3) 112-1, Harch 1967. (Presented at the
59th Annual fleeting. Air Pollution Control Association,
San Francisco, Calif., June 20-25, 1966, paper 66-95,)
A household emission and opinion survey was conducted in
Jefferson County, Alabama, to provide information that could be
correlated vith air quality data. A 21-station air sampling
network was operated for one year previous to the opinion survey.
Public attitude toward air pollution as a general nuisance in
metropolitan Birmingham can apparently be estimated from
dustfall, and to some extent, from suspended particulate levels.
Based on public opinion versus ambient air pollutant level
correlations, and assuming that no more than one-third of the
people should be adversely affected by air pollution, it was found
that ambient particulate levels should not exceed 30 tons/sg.
mi./mo., as dustfall nor 150 micro gs/cu. » as suspended
particulate matter. When dustfall reaches HO tons/sg. mi./mo. or
suspended particulate natter reaches 230 micro gs/cu* m, 50% of the
households say that air pollution has become a general nuisance.
(Author summary}M
01100
J. A* Wag a
CONSIDERATIOHS IV SETTING STARDARDS FOR OXIDES OF HITROGBV.
J. Air Pollution Control Assoc., 15(12| S561-561, Dec. 1965.
Since 1959 the California Department of Public Health has held
responsibility for setting standards for ambient air quality for
motor vehicle emissions. The need for standards for oxides of
nitrogen involves consideration both of direct effects and effects
resulting from participation in photochemical smog reactions.
This paper discusses the various effects of concern and describes
1046
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
the department's prograa for establishing air quality standards
which will becoae the basis for vehicle emission standards and
serve as guides for control of other sources of oxides of
nitrogen. {Author abstract)**
01955
J. F. Goldsnith
SOHE IMPLICATIONS OF AMBIENT AIB COAIITY ST AN DAB DS. Arch.
Environ.. Health 4, 151-67, Feb. 1962. (Based in part on a
paper presented at the 54th Annual Meeting, Air Pollution
Control Association, New York City, June 13, 1961.)
Author discusses the parameters of the air quality standards in
California, starting with the efforts in 1959 and updating the
progress to 1962. Allowable concentrations of oxidants are given;
a general discussion of health based on air guality studies is
given and, the general policy cf California air quality
standards is reviewed.**
02418
AMBIENT AM QUALITY OBJECTIVES - CLASSIFICATIONS SYSTEM. New
York state pollution Control Board, Albany 1964. 14 pp.
Article contains the adoptions cf anbient air quality
objectives for New York State*•#
03007
CALIFORNIA STANDARDS FOB AMBIENT Ali QUALITY AND BQTO? VEHICLE
EXHAUST (TECHNICAL *BPT.| California State Dept. of Public
Health, Berkeley. 1959. 129 pp«
The salient points in the table of contents ares I. The
standards and their significance.. II. Technical bases for
standards for the quality of ambient air. III. The technical
bases for motor vehicle exhaust standards. In establishing the
standards, an attemft was made to deternine what effects the
various pollutants were known to have at various levels of
concentration on human health aad confort, on animals, and
plants, and on visibility. The resulting air quality
standards together with data concetningmotor vehicle emissions
and tbeir reactions then became tbe bases for setor vehicle
exhaust standards. Tbe air standards do not establish a fine line
below which is good air and above which is bad air. They indicate
L. Standards and Criteria
1047
-------
the approximate point at which air under some circumstances may
produce undesirable effects.##
C 35 83
CALIFORNIA STANDARDS FOP AMBIENT AIF AND BOTCH VEHICLE EXHAUST
(TECHNICAL E EPT-)., California State Dept.. of Public Health,
Berkeley.. 1959- 16 pp..
These standards are presented as a yardstick which may be
applied in maintaining and improving air quality. A graded set of
ambient air standards was established which recognized the
relationship between the seriousness of the effect of the pollutant
and the urgency of control. Three levels of air pollutants were
defined: adverse, serious, and emergency. The standards cf motor
vehicle exhaust contaminants are: hydrocarbons-275 ppm by volume
as measured by a hexane-sensitized nondispersive infrared
analyzer: carbon monoxide-1.5* by volume measured by a
nondispersive infrared analyzer. The exhausts are to te measured
during an eleven-mode operating cycle.##
05037
E. G. Giel
DEVELOPMENT OF AIP COALITY CRITERIA. Symp. Bio-Environmental
Engineering, Texas, 1961.. pF- 63-72.
There is an important distinction between air quality standards
and air quality criteria. Air quality standards are defined as
levels of atmospheric contanination by specific pollutants or
conbinations of pollutants prohibited under laws or ordinances
enforced by municipal or State governments or regional agencies
established by them and empowered with regulatory authority.
Federal criteria, as called for in the Clean Air Act of 1963,
are seen as recommended levels of air contamination expressed in
terns of the adverse effects they can be expected to produce on man
his property,, and his environment* Such criteria would be based
on the best available scientific information and would serve to
guide municipal. State, and regicnal control agencies in the
adeptien of air quality standards and source emission
limitations. Recommended levels of air pollutants should never
be in a range which could adversely affect any segment of the
population.. Air quality criteria will have to be developed in
full recognition of the fact that certain individuals and groups
are unusually susceptible tc acute as well as chronic injury from
certain air pollutants. Another consideration is based on the
fact that animals and plants are, in some instances, more
susceptible than human beings to specific pollutants, in
developing criteria, consideration may need to be given to the
protection of the most susceptible target, whether it be animal or
plant life. Air quality criteria will have to be uniform for all
regions of the country, regardless of their current pollution
1048
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
levels. Standards and source emission litoitations, mentioned
earlier, may vary in accordance with local prevailing conditions,
but the criteria of air quality must be concerned with the
protection of health and welfare under any circumstances.. it
should be noted that air quality criteria will have to take into
account various synergistic interference, and Basking effects of
combinations of pollutants in the atmosphere.. Thus an acceptable
level of S02 when considered alcne nay be * parts per million,,
but when S02 is present in conjunction with suspended particulate
natter, only one tenth * parts per Billion may be acceptable-##
05293
Pennsylvania state Dept. of Health, Harrisburg, Air Pollu-
tion Commission. (Apr. 25, 1967). 5 pp.
iPBIENl AIR QUALITY CBITE8IA.
In accordance with Section 5 (f) (8) of the Pennsylvania Air
Pollution Control Act, the Act of January 8, 1960, P., L»
2119, on April 25, 1967 the Air Pollution Commission adopted
the Ambient Air Quality Criteria, which will be used by the
Commission in: 1. Evaluating the results of community air
pollution studies conducted by the Department of Health. 2.
Eetermining the need for air pollution control regulations in
regions of the Conaonwealth to achieve these objectives. 3..
Developing rules and regulations in accordance with Section 5
(f) (2) of the Pennsylvania Air Pollution Control Act. The
sampling and analytical procedures employed to measure ambient
levels of contaminants are tc be consistent with obtaining accurate
results which are representative of the conditions being
evaluated.##
055U5
Jaffe, I.. S.
HEW-PHS COMMUNITY AIR QUALITY CRITERIA (FOB PHOTOCHEMICAL
OXIDANTS)., Preprint. 1965
The community air quality criteria are based on technical and
scientific considerations and concepts. The particular values in a
set of criteria are based on recoided effects resulting from
specific pollutant time-concentrations exposures on mat, plants,
animals and/or materials. These criteria are intended to serve as
guides to communities, metropolitan areas, regions, states, and
other geographic or political subdivisions in the development of
their air quality standards. The complexities of society will
require the making of many decisions which involve balancing of
judgement between health and other social "benefits" to be derived
from clean air and the "risks" cf economic and sociological costs
to achieve such benefits. The specific air quality standards
developed by an area, no doubt, will reflect such considerations
L. Standards and Criteria
1049
-------
through assessment and evaluation of the degree and severity of the
detrimental effects the government of the area is willing to
tolerate versus the social effects and economic costs of attainint
that level of pollution (or clean air.) The Public Health Service
recommends that Level I of the criteria be regarded as the minimum
goal or objective in establishing .the community air guality
standards {in order to aaintain the effectiveness of human
resources and long range economic strength)* Level I is a measure
of "first effects" of the pollqtantfs} which produce a transient,
probably reversible biological effect on nan, plants or animals, or
socially significant visibility, whichever is evidenced first. It
is the minimal known level of effect - the lowest level of a
pollutant at which a physiological response or physical or other
effect occurs; below these concentrations and exposure tines no
direct or indirect physiological seguelae have been effectively
measures. This level does not carry the connotation that it
represents desirable community air guality, but it provides a
modest safety factor for personal health insofar as present
knowledge has determined. Levels II ("Adverse**), III
I**Serious"), and IV <"E*ergency«) are defined. ASH
06513
PERMISSIBLE COHCEKTHATIONS OP SI1F0US GASES. (Baxiaale
Isissions-Konzentrationeo (BIK) Sitrose case.) VDI
national Conference on Air Pollution, Washington, D„c«,
De . 10-12, 1962«) •(Dec. 1962).. 13 pp. Ger. (Tr.)
The TCI Specifications for Permissible Imaission
Concentrations (PIC) concern the determination of limit values
for given types of air pollution. For purposes of comparison,
the PIC-values are always confronted by the permissible
workplace concentrations (PRC-valuel of the respective gas,
aerosol, or dust, i.e„,the present limit value for the mean
concentration of the substance in the respiratory air at the
work-place per 8-hour shift. The information is outlined under
the headings of: Occurrence of Hitrosylsulphuric Acid;
Properties of nitrous Gases; Effects of Vitcous Gases; and
Sxposure Limits.#*
06B85
Gol*dberg, 8- s.
HIGIEHIC CBXTBBIA Of AIB PDBIT* I* BCW11TBD 1B1I5 (ACCORDING
10 HAT28IALS or THI 62I1VA SIJSPOSIOB). ((0 Jcriteriyakh
gigienicheskoi otsenki chistoty ataosfernogo vozdukha naseleanykh
seat)) (
-------
In recent years there has been a steady increase in hygienic
research on air in populated areas.. The need for planning of
¦easures for the control of atnospheric pollution is beconing
increasingly argent. The necessity for an international
discussion of this subject, which would be a starting point for all
measures undertaken for the sanitary protection of urban air* led
the florid Health Organization to convene an interregional
synposiun in Geneva froa the 6th to the 12th of August* 1963,
which was devoted to criteria for the quality of ataospheric air
and aethods of its investigation* The discussion was centered on
the Maxima permissible concentrations of haraful substances in
urban air.. After a lively discussion* the syaposium adopted
Prof. V. A. Ryazanov's proposal to establish a unified scale
of standards for the quality of air by verging together the Soviet
and Aaerican standards. In this way* an international scale
for the atnospheric pollution has been established for the first
tine. The synposiu* drew up recommendations on the trend is
medical research on the effect of atnospheric pollution on the
health of the population, and a further elaboration of criteria and
standards of atmospheric air quality in populated areas,
participants at the symposium also noted the necessity for the
further development of scientific research on the mechanism of
development of fibrotic pulmonary reaction induced by atmospheric
pollutants, and for studies of the reaction of the mucosa of the
respiratory tract, ciliary activity, etc. The synposiun pointed
out the necessity for paying special attention to studies of new
synthetic chemicals which contaminate the atmosphere vhen
discharged by industrial enterprises or when used in the
household, as in the case of disinfectants.##
C7197
BECOHMEHDATIOHS 70S ALLOSABII COKCEMBATION (1966.) Kaki Seijo
(Cle^n Air - J. Japan Air Cleaning Assoc., Tokyo)
d(4):62-66, 1966. Text in Japanese.
A report is given by a coaaittee of the Japanese Association of
Industrial Health on "Allowable concentration". The values of
allowable concent ration are worked oat for a healthy jtan working
8 hr per day doing moderate work. Proper consideration oust be
given to cases in which nore than 8 hr of exposure take place# more
than one pollutant is involved, or the concentration of pollutants
increases suddenly daring the work schedule. Included is a
discussion on dust measurement. It is important to measure dusts
having a Stokes radius of less than 5 microns, especially at a
height of 1 to 1*5 a froa the ground. The relation between the
source of dust and the point of measurement is illustrated.**
07490
Suzuki,
OH THE PEBHISSIELE COHCESTSWIC1 CI AIB P0L1UTAHTS 18 SOBE
L. Standards and Criteria
1051
-------
CCUNTFIES*. Text in Japanese.. J. Jap. Petrol.. Inst.
Tokyo, 7||2):87-91 Feb- 196«„ D refs-
There are no "international" permissible values of air pollutant
concentrations at present. The maximum allowable concentrations
and their methods of determination differ between countries.
Values obtained in the Soviet Union, Czechoslovakia, West
Germany, and the United States are compared. The values of
permissible concentration are very lew in the Soviet Union, even
seemingly impossible of realization. Permissible values for 32
substances are tabulated. In West Germany, the values are
expressed by HIK (Haximale Imiseion (Concentration)
recommended by the VDI fVerein Deutscher ingenieure).
According to definition,, the "Imissicn" value is the
concentration of the elements found undesirable for "normal air"..
With HIK, only S02, nitrogen oxides, H2S, and chlorine are
regulated. Consideration of exposure time is also given.
Values obtained in Czechoslovakia are for 16 materials
determined as was done in the Soviet Union.. As for the United
States, present methods of establishing HAC (Maximum Allowable
Concentration) are described. ValueE for S02 determined in
California are tabulated.**
C7604
Rossano, August T.., Jr.
ANALYSIS AND COHPASISOH OP AVAILABLE DATA OB AIR QUALITY CRITERIA
IH MEHEEB COUNTRIES.. Preprint, Washington Univ., Seattle,
Dept., of Civil Engineering, 22p., 1963. 12 refs. (Presented
at the Inter-Regional Symposium cn criteria for Air Quality
and Hethods of Heasurement, Geneva, Switzerland, Aug. 6-12,
1963, Paper No. BHO/AP/11.)
Air quality standard-setting activities of Great Britain, West
Germany, USSR, Czechoslovakia, and the United States are reviewed.
In addition, an analysis and comparison is made of criteria and
maximum allowable concentrations developed by these countries..
Other countries of western Europe with th« exception of Vest
Germany and Czechoslovakia have not adapted air quality standards.
In general the control of air pollution in Europe relies heavily
upon regulations prohibiting the discharge of pollutants which may
endanger the public health, be detrimental to safety,, crops and
public monuments or constitute a public nuisance. Air quality
standards for six specific gases have been developed by the Western
German Commission., Czechoslovakia and Russia have established air
quality standards for a large number of pollutants, in general
their valves are similar.. In the United States definite progress
in developing air quality standards has been made in only 2 states,
are similar. In the United States definitive progress in
developing air quality standards bas been made in only two states,
Oregon and California. The air quality standards in Oregon
pertain only to suspended particulate matter. The most extensive
development of air quality standards in the United States bas
occurred in California. Direct comparisons between ambient air
quality standards of the various countries are not feasible because
1052
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
the objective and criteria are different and the selected tine
exposure period varies in each country. The USSR standards are
based primarily on human sub-ccncious thresholds while those of
California, and to a great extent Rest Germany, are based on human
conscious thresholds. This vide difference in standards is due in
part to differences in medical and public health philosophy as to
what constitutes a threat to health and well-being-
07605
Pliddleton, John T.
AIR QUALITT CRITERIA ASSOCIATED BITH VISIBILITY RBDOCTIOU, SOILAGE
AND DAMAGE TO VEGETATION. Preprint, California Univ., River-
side, Air Pollution Research Center, 1Up., 1963,, (Presented
and Methods of Measurement* Geneva, Switzerland, Aug. 6-12,
1963- Paper So.. WHO/AP/15.J
Particulate loading of the atmosphere is primarily responsible for
reduction in visibility. The amount of visibility reduction* in
turn, is due to the nature of the particle. The criterion for
visibility is perhaps best given in terms of visible distance at a
specific relative humidity.. Air quality criteria for soilage may
be developed where specific contaminants have direct effects upon
particular Materials, since in general the soilage of goods is a
function of multiple actions, air quality criteria for soilage ate
difficult of description and perhaps of lessened general utility.
Air quality criteria for visible effects of vegetation damage can
be developed for those toxicants which have direct effects, such as
sulfur dioxide, ethylene, nitrogen dioxide, peroxyacyl nitrates,
and ozone. Air quality criteria for fluorides cannot now be
determined because of the multiplicity of factors which control
the rate of accumulation and the subsequent effect of fluoride upon
plant tissues. Levels of fluoride responsible for damage to
livestock can be established and a criterion based on this is
feasible.
08U20
Brodovicz, Bey A.
AIR QOAIXT? CRITERIA 70S PIBHSTIVASIA. J. Air Pollution
Control Assoc*# 18(1):21*23, Jan. 1968. 4 refs.
In late 1965 the Pennsylvania Air Pollution commission
appointed a Council of Technical Advisors to ftevelop air
quality criteria. Recently this Council set forth its
recommendations for ten pollutants. The philosophy of the
council is expressed. The major difficulties and rationale are
mentioned. The recommendations are given and the potential use
of the criteria is also explained. The establishment of firm
guidelines of air qiality is based solely on consideration of
effects both on health and aesthetics. The criteria are broken
L. Standards and Criteria
1053
-------
into two distinct groups; air basin average and single point
measurement.. the pollutants included: 1, Suspended
particulates (total), 2. Settled particulates (total), 3« lead
(tentative), 4. Berylliaa, 5. Sulfates (as H2S0U), 6.
Sulfuric acid mist, 7„ Plucrides (total soluble, as HP), 8.
Sulfur dioxide, 10« Oxidants, 11. Hydrogen sulfide, and 12«
carbon monoxide.M
08679
Kaga, John A. and J, R. Goldsmith
STANDARDS FOR AIR QUALITY IN CALIFORKIA. J. Air Pollution Con-
trol Assoc., 10 (6):453-455, 467, Bee. 1960. 8 refs. (Presented
at the 53rd Annual Meeting, Air Pollution Control Assoc.,
Cincinnati, Ohio, Hay 22-26, 1960.)
The 1959 State legislature required that the California State
Department of public Health adop and publish standards for the
quality of the air of the State. The act also provides that the
standards say be amended from tine to time and that they shall be
adopted after public hearings. Concentrations for four substances
—ozone, oxides of nitrogen, sulfur dioxide and carbon monoxide—
were established in 1955 by the Los Angeles County Air Pollu-
tion Control District as part of an alert system. Following
adoption of the State air quality standards, that. District
amended the carbon monoxide alert values to include a concentration
and time of exposure. The procedures for the adoption of the stan
dards are detailed. Three levels of air pollutants were thus
selected as follows: 1. Adverse level - Level at which there
will be sensory irritation, damage to vegetation, reduction in
visibility, or similar effects.2. serious Level-Level at which
there will be alteration of bodily function or which is liJcely to
lead to chronic disease. 3. Emergency Level ~ Level at which it
is likely that acute sickness ox death in sensitive groups of pec-
sons will occur. The three levels were not merely different
degrees of severity but each represents qualitatively different
effects. The concentrations that were used represent that was con
sidered to be the lowest values at which the defined effect could
be experienced by sensitive receptors. The standards that were
established by the Department are given, standards were set only
for substances on which it was felt there were sufficient data. In
addition, a number of footnotes are included. Some of these foot-
notes cover substances for which actual standards in the near
future. One of the considerations of the Legislature in requir-
ing air quality standards was that they would be used to determine
standards for motor vehicle exhaust emissions. The "oxidant
index" and carbon monoxide levels in the air guality standards had
a direct and important bearing on standards for motor vehicle
exhaust emissions that were also developed by the Department.
09259
Hat2, Borris
T054
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
RECENT DEVELOPMENTS IN AMBIENT AIR QUALITY GUIDES IM RELATION TO
CONTROL OF ATMOSPHERIC EFFLUENTS. Pulp Paper Nag. Can.
(Gardenvale), 69{U):60~66, Feb. 16, 1968. 11 refs. (Presented
at the 3rd Paper Industry Air Stream Improvement Conference,
Vancouver, B.C., Oct. 23-26, 1967.)
Major sources of air pollutants are discussed, as well as the need
for control of emissions using source emission standards and
ambient air quality criteria. Criteria for air quality reflect
the nature and magnitude of effects cf air pollutants upon the
atmospheric environment in general and on visibility, safety,
health of nan or animals, vegetation and property. These criteria
state four levels of pollutant concentration and exposure periods
according to the differing effects on the exposed population or
receptors, rangin from no direct or indirect influence to symptoms
that nay be merely adverse, or serious, or of emergency
proportions. Ambient air quality guides and standards adopted
by several countries are tabulated for C02, CL2, ethylene,
HC1, H2S, oxides of nitrogen, ozone or oxidant, CS2, and
S02. Those of the state of California, state of New
York, west Germany, Czechoslovakia, U.S.A., and the U.S.
S.R., are reviewed. Air quality standards established in the
U.S.S.R. are more stringent than those formulated in West
Germany, the U.S.A. (California), and elsewhere, Maximum
allowable concentrations for some atmospheric pollutants
(industrial) in the U.S.S.B. are also tabulated, including As,
Cr03, Pb, Mn, and soot. A brief summary is given of Canadian
activities and the salient features of the Ontario Air Pollution
Control Act. The existence of these standards implies that
stricter measures will be enforced to control emission sources in
the future.*#
10485
Larsen, Balph 1.
A NEW MATHEMATICAL MODEL OF AID POLLUTANT CONCENTRATION, AVERAGING
TIME,AND FREQUENCY, Preprint, Public Health Service,
Cincinnati, Ohio, National Center for Air Pollution Control,
24p., 1968. 13 refs. (Presented at the 61st Annual fleeting of
the Air Pollution control Association, St. Paul, Hinn.,
June 23-27, 1968. Paper 68147.)
Continuous air pollutant concentration data have been analyzed for
carbon monoxide, hydrocarbons, nitric oxide, nitrogen dioxide,
nitrogen oxides, oxidant, and sulfur dioxide in 6 United States
cities for 3 years. These data have been used to develop a
mathematical model to express pollutant concentration as a function
of averaging time and frequency. The two essential features of the
model are derived from data analyses indicating that (1)
concentrations are approximately legnormally distributed for all
pollutants in all cities for all averaging times and (2) median
concentration is proportional to averaging time to an exponent*
Applications of this model to problems involving pollutant effects,
air quality criteria, and air quality standards are shown. Air
guality standards should be based on the prevention of certain
L. Standards and Criteria
-------
combinations of concentrations and exposure durations that nay cause
various undesirable effects. It is also recommended that air gualit
standards specify maximue concentrations that are not to be exceeded
more often than a stated frequency/ commensurate with the undesitabl
effects to be avoided, the pollutant involved, and the averaging
time. In comparing air guality in a community to the standard, the
calculated expecte value based on real air guality data and the moae
presented herein, would be used. (Author's summary)
114 m
K. Biersteker
FRESH AIR QUALITY STANDARDS. (Kwaliteitsnormen
Euitenlucht.) Translated from Dutch. T. See. Geneesk., No.
46:166-176, 1968. 58 refs.
Fresh air guality standards in different nations are reviewed.
Considerable differences exist because the hazards of air
pollution are assessed differently. However, the
differences in clean air specifications appear to disappear as the
maximum permissible impurity concentrations become gradually
lover. The Committee for Soil, Hater and Air in Rotterdam
developed standards which have nc legal significance but help
government and industry to establish clean air policies.
These standards are tabulated for chlorine, hydrogen fluoride,
carbon monoxide, ozone, nitrogen dioxide, sulfur dioxide, hydrogen
sulfide and sulfuric acid—with comparable standards shewn for
West Germany, Russia, and the United States. The permissible
S02 concentration in California is higher than in Europe.
This is due to the tact that S02 plays a minor role in summer
fog formation. In Europe, however, fog occurs in the winter and
is accompanied by high SQ2 and smoke concentrations.
Another notable difference in air quality standards is that the
Russians have unrealistically high standards for clean air while
in Western Europe air is considered as a raw material which
should be left in a reasonably good condition for the next
consumer. Air guality directives, being used for the city of
Rotterdam, and air pollution alarm systems used for Los
Angeles and proposed for Kev Ifcrk, are discussed.**
12029
COflSBSXXY AIR QUALITY GUIDES. AIDE BIDES. Am. Ind. Byg.
Assoc. J*, 29(5):505-512, Sept.-Oct. 1968. 53 ref„
the multi-disciplinary backgrounds and professional competencies
within the American industrial Hygiene Association have been
utilized to the fullest in the preparation of a series of asbient
air quality guides* These are intended to be concise, and
therefore are offered as single compounds, recognizing that other
factors such as potentiation, antagonism, or other effects
associated with mixtures, will create special problems from place
to place and from time to time, the effects of which must be
1956
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
individually evaluated- These guides are based on present
scientific knowledge; as new data become available* the recommended
threshold values are subject to change. The literature relating
to the subject matter of each cf the ambient air quality guide
series is constantly being reviewed, and when indicated, new guides
are prepared. (Author® s Abstract)##
12030
K. Biersteker
AIE QUALITY STANDARDS. Tijdsch. Soc. Geneesk., U5 (5) :166-175,
(1968). Text in Dutch. 58 ret.
A review of ambient air guality standards is given. The values
differ widely, partly due to differences in methodology, partly
due to differences between oxidizing and reducing pollution.
The values are gradually getting closer, however, as tine so far
has lowered them every time a new set of values has been published.
Rotterdam used air guality guides for several pollutants. The
values have no legal value but help to give industry and control
agencies something to base their plans on. (Author's
Abstract)##
13527
Thomas, Moyer D.
REACTIVITIES OF SMOG CO&SOMEBTS ABE CENTRAL ISSUE 18 SETTIIiG
CONTROL STANDARDS. Environ. Sci. Technol., 3 (7) :«S29-633, July
1969. (Presented at the 156th national ACS meeting, Atlantic '
City, N. J., 1969.)
Photochemical smog contains nitrogen oxides, ozone, ozonated
olefins and other organic compounds. Nitrogen oxides react witli
organic compounds to form noxious gases which are injurious to
vegetation and are strong eye irritants. Maximum concentrations
of nitric oxide and nitrogen dioxide occur during peak traffic
hours. Ozone is phytotoxic, causing upper surface necrosis,
stippling, and mottling. Human respiratory functions are adversely
affected by 0.3 to 0.5 ppm ozone. Peroxyacyl compounds are said
to be 200 tiies more irritating than formaldehyde and it also
affects plants. Some of the polynuclear hydrocarbons are
carcinogenic. Concentrations of remedial measures are presented.
Discussion by D. B. dimmer: Unlike air pollutants which originate
from imperfections in the combustion process, nitric oxide is a
basic and necessary product of efficient power production'in ' :
internal combustion' engines. It is uncertain whether reducing
nitric oxide concentrations would reducephotochemical snog. The
benefits are rather nebulous and costs ace very concrete. Reaction
rates, in addition to emission levels, should be considered in "
formulating regulations. Discus sitt-h by A.'s P; Altshullenfitfst v*
nitrogen oxides present iir automobile and stationary sources 'art61
in the form of nitric oxide, indicating that nitrog«n dioxi.de is- r:
L. Standards and Critwlt
-------
due to photochemical oxidation. The bulk of experimental data
indicates that all photochemical air pollutants except nitrogen
dioxide ate much reduced by hydrocarbon control, cost vs benefits
should be considered in establishing controls.
1*#75
Huenigen, Edmund and Wolfgang Prietsch
OB THE PROBLEM OF LIMITING 2MSSI0N OF TOXICANTS BY HOTCF
VEHICLES IK EUROPE. (Zun Problem der Begrenzung der
Schadstoffemission bei Jtraf tf ahxxeugen in Europa)„ Text in
German. uotortech. Z. (Stuttgart), 30(7) :256-259, July 1969..
24 refs.
Maximum allowable emission concentrations in exhaust from motor
vehicles in Europe are presently being Mocked out by an
organization of the Onited nations, the European Economic
Commission. it has been suggested that the MAC values be
determined by the * European driving cycle exhaust gas test" (BFA).
Maximum allowable concentrations in the atmosphere have been set
by individual European countries.. A table compares the values
set by the German Democratic Republic, tbe German Pederal
Republic, and Russia and shows that the limits are far more
stringent in the GPR. The toxicclogical importance of carbon
monoxide, hydrocarbons, and nitrogen oxides in each country will
form the basis for working out uniform European limits. Based
on the HAC for CO and on the premise that the MAC values should
correspond to the toxicological importance of the pollutants,
the HAC ratio for CO, hydrocarbons, and nitrogen oxides is
1:1.9:0.1. As measurements skew, at present only CO emissions
need to be limited. Tbe other toxicants will not be limited
until more measurements have brought detailed information
concerning the relationship between emissions and air pollution.
Limitations of CO emissions during idling is urgently needed.
14634
Dmitriyev, M« T-
APPLIED ASPECTS OP TBE HADIATIOB CHEBISTBI OP A KTHOGEN-OXXGES
SYSTEM. {Prikladnyye voprosy radiatsioanoy khimii sisteay
azotkislorod). Text in Russian. Zh. Prikl. (Chin.*
-------
6 Or based on nitrate ion, or 1.2 Mr based on nitrite ion;
OoOS-O.4 Br is recoaaended for purification of tap vater;
Q«05-1„2 Br for vater under field conditions, and 1 Mr for spring
vater. The maxim* permissible dose for aaaonia is 0.U nr.
Haxiaua peraissible doses for foodstuffs are as follows: liguids-
1-2 Mr, aoist foods-11 Br, frcaen foeds-15 Br, dry concentrates-
95 Be.
1U772
Reaver, Weill K.
ATHOSPHBBIC COHTABINAHTS AHD STANDARDS,. STATDS REPORT. J.
Occupational Med., 11(9):»55-U61, Sept- 1969. 23 refs.
The Federal Air Quality Act of 1967 furnishes the methodology for
the abateaent of air pollution. Its provisions include the
designation of air quality control regions and the issuance
of air quality criteria and control technology documents,
which vlll be followed by the prcaulgation of aabient air
standards and emission standards at regional, state, and local
levels- The ataospheric pollutants of current major concern
ate sulfur oxides, particulates, nitrogen oxides, hydrocarbons,
oxidants, carbon nonoxide, flucrine,- and lead. Their toxic
and other deleterious effects, exhibited at various
concentration-tise exposures, can be related to levels reached
by the individual contaainants in the air of cities. While
such an evaluation does not allow for possible interactions
between pollutants, it appears that sulfur dioxide, oxidants,
and carbon aonoxide aay be baraful to huaan health when the
agents are concentrated, as In focal areas of emission or
during sustained aeteorologic inversions. Gains to be
achieved by controlling these and other contaainants during non-
peak conditions are probably derived frca aesthetic# economic,
and welfare benefits rather than health. Abateaent procedures
should eliminate rises in pollutant levels beyond the average
ranges generally present in urban anbient air. (Author cuaaary
aodified)
15336
Feldstein, Hilton
AIB pollution; BAY ABBA. Clin- Toxicol., 2(3)S307-317, Sept.
1969.
A review of air pollution probleas in the San Francisco area is
followed by a discussion of eaission standards established by the
Bay Area Pollution Control District and the duties of the State
Air Resources Board. Areavide pollution probleas are the
reduction in visibility caused primarily by submicron pariculate
aatter and the photoch«alcal smog, whose priaary effects are
eye irritation, plant daaage» and visibility redaction that
L, Standards and Criteria
1059
-------
is caused by photochemical reaction between nitrogen oxides and
organic compounds. Emission of solid materials is controlled
by two types of standards, one limiting the opacity of sBoke
to Ringelmann 2 and another permitting no sore than 0-3 grains
of solid material per cu ft of gas to be emitted from certain
industrial operations and no wore than 0.2 grains per cu ft from
commercial incinerators. Hhiie sulfur oxide emissions are
controlled by setting maximum stack emissions limits, industrial
sources must also monitor ground-level concentrations, other
regulations limit the emission of photochemically reactive olefins
and aromatic compounds froa industrial sources. Control of
automobile emissions is under the Air Resources Board, which is
currently developing air quality standards for 11 air basins in
California. State emission standards are given for the years
1966 to 197«i, and the tons per day of pollutant emissions in the
Bay Xrea are listed according to their sources.
16518
California State Dept. of Public Health, Berkeley, Eureau of Air
Sanitation
HE* AND REVISED WOTCR VEEICLB STA8DARDS ADOPTED. Clean Air
Quart,, 8{U);1-27, Dec. 1961*.
California's 1970 emission standards for motor vehicles reduce
hydrocarbon exhaust levels from 275 to 180 ppm by volume and
carbon monoxide exhaust levels frcm 1.5 to 1.0 percent by volume.
The crankc&se hydrocarbon standard is lowered from 0.15 to 1.10
percent of the supplied fuel. For the first time the following
standards are included for fuel tank and carburetor hot soak
emissions respectively: 6 g/day; and 2 g/day. Approximately
95% of hydrocarbon losses are ncv covered by emission standards.
However, further improvements is the standard are anticipated.
It is hoped that the hydrocarbon standards can be eventually
stated in terms of the reactive compounds producing photochemical
snog. Also under consideration is a standard for nitrogen
oxides. As the result of a prolonged smog attack in September and
October 196H, three Southern California cities experienced more
than 20 *adver3e* days when the total oxidant exceeded C.15 for one
hour oc longer. Unless emissions of pollutants, particularly
those from automobiles, are curbed, further severe smog episodes
will occur. The state Motor Vehicle Pollution control Board has
given its approval to the Chrysler exhaust control system. Current
studies of carbon dioxide contamination from engine compartments
show CO concentrations in closed cars of 100 to 200 ppm. Although
exposure to these levels fox two hours or longer could adversely
affect a commuter's carboxyhemoglcbin level, the CC levels are
sot likely to be influenced by controlling hydrocarbon and carbon
monoxide emissions with afterburners. Levels of oxidants,
nitrogen oxides, carbon monoxide, and sulfur dioxides recorded by
state monitoring stations are tabulated.
16820
Pitts,
-------
ENVIRONMENTAL APPRAISAL: OXIDANTS, HiDBGCAfiBCNS, AND OXIEES OF
NITBOGEN. J. Ait Pollution Control Assoc., 19 (9):658-669, Sept.
1969. 5b refs.
The relationship between criteria, standards, and control of air
pollutants involve complex multidisciplinary interactions. Their
overall impact on the public health and welfare is directly
related to the confidence level held by members of government,
industry, and universities in the validity of the data upon which
these criteria are based. The Environmental Appraisal section of
the preliminary draft of the Air Quality Criteria Document
"Photochemical Oxidant" prepared by the State of California,
Department of Public Health, is reviewed. In general, it is a
thoughtful and extensive effort to present the current status of
information concerning the physical and chemical aspects of
photochemical oxidant. Suggestions as to how it might be extended,
revised or updated are presented along with a brief discussion
of two new research areas of possible interest, singlet molecular
oxygen as a possible environmental oxidant and the photochemistry
ot mixed lead halides in the ataosphere. This article is followed
with a discussion by Bichard D. Cadle. (Author's Abstract)
L. Standards and Criteria
1061
-------
M. BASIC SCIENCE AND TECHNOLOGY
OOOOI
A. P. Altshuller and I. F, Cohen
ATMOSPHERIC PHOTOOXIDATIOR OF THI ETBYIENB—NITRIC OXIDE STSTEH.
Intern* J+ Sir Rater Pollution# Vol. 8: 611-632, 1964.
Because ethylene is not only a phytotoxicant but also is reactive
in the photochemical type of air pollution, a detailed study has
been made of the photooxidation of ethylene-nitrogan oxide fixtures
in air. The effects were deterlined of varying the concentrations
of ethylene between 0«1 and 5 ppm and of nitric oxide between 0.2
and 10 ppm on the rate of ethylene consumption, the rate of
nitrogen dioxide formation and on the yields of various products*
The greater part of the ethylene consumed could be accounted for
in the products as formaldehyde or carbon monoxide. Xt was not
possible to obtaina nitrogen balance in this system, although a
snail amount of methyl nitrate Has produced. Ethylene-nitrogen
oxide mixtures react rapidly in static irradiations at reactant
concentrations below 0.5 ppm. For example, photooxidation of a
mixture initially containing 0»2 ppm of ethylene and 0.2 ppm of
nitric oxide resulted in a nitrogen dioxide peak in 30 mia and half
conversion of ethylene in about 80 min.. At egual ratios of
reactants, ethylene-nitric oxide mixtures actually ace more
reactive at lower concentrations of reactants. in order to
explain the experimental results it appears that free radical chain
reactions must be postulated. A discussion of various
mechanistic reaction steps is given. (Author}##
00031
S. B, Bebbert and P. Ausloos
TRIPLET-STATE ENERGY T8AHSEEB FBCM ACETOME TO ALIPHATIC
ALDEHYDES IN THE GAS PHASE* J, Al. Cham. Soc., Vol.
66: 4603-4807, Nov. 20, 196
-------
can transfer its triplet-state energy to form a triplet excited
aldehyde molecule, it is shown that the electronically excited
aldehyde molecule formed in such an energy-transfer procdss shows
the sane nodes of decomposition as in the direct photolysis. The
energy-transfer process does not occur in the presence of oxygen
and decreases in probability with an increase in temperature.
(Author)*#
0003Kt
0„J.. Bufalini A.P. lltshuller
THE EFFECT OF TEHPEBATDBE OS PBOTOCHEHICiL SROG fllACTIOHS.
Intern, J. Air Rater Pollution, Vcl 7:"769-711r 1963»
Results of measurements wade for the photo-oxidation of
trans-2-butenenitric oxide in air and for 1,3,5-
tpiwethylbenzene-nitric oxide in air are discussed. The
initial concentrations of the teactants in the two systems were as
follows: trans-2-butene, 10 ppm; nitric oxide, it.2 pp»;
1,3,5-trimethylbenzene, 6 ppm; nitric oxide, 3 ppa» The
conversion tines far bath systems decreased by approximately
a factor of two and the rates increased by a factor of two when
the temperature was increased f rem 20 to 40 degrees. The
conversion tine at the nitrogen dioxide maximum and the rate of
half-conversion of nitric oxide to nitrogen dioxide are
two independent measures of reactivity which give good agreement
on a relative basis. Siailarly which give good agreement on a
relative basis, similarly on a relative basis, good agreement
is obtained on the times at which the hydrocarbon reaches half of
its initial concentration and the normalized rates at these times
in the reaction although they do represent somewhat different
measures of reactivity. The results from these two systems
should not be taken as indicating that temperature changes are
independent of the nature of the hydrocarbon used as a
reactant. The investigation showed that temperature
difference of a few degrees can cause measurable changes in
photo-oxidation rates.##
00053
B» J- Ayen *«S, Hg
CATALYTIC REDUCTION OF HITBIC OXIDE Bt CJIBBOH HOKOXIDE.
Intern., J. Air (rater Pollution Vol- 10:1-13, Oct. 11, 19fi5
Fate data for the catalytic reduction of HO with CO were
obtained using a flow reactor operated differentially at
atmospheric pressure and at temperatures of 160, 200, 220 and 240
c„ Nitric oxide and carbon monoxide partial pressures
were varied from 0.005 to 0.05 atm using helium as a diluent to
bring the total gas flow to 2000 cc/mia, A dual site mechanism
was postulated for the reaction in which the rate determining
step was a surface reaction between adjacently adsorbed CO and
1064 PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
NO molecules. From the data, rate and adsorption constants
were evaluated foe the corresponding rate expression. This
expression is of practical use in the design of a catalytic
converter to removre oxides of nitrogen from automotive exhaust
gases and other exhaust streams. (Author)#*
00058
R„S. lipscn
BEVIEU OF OXIDATION OF P0LTCYC1IC, AROMATIC HYDROCARBONS.
National Eureau of Standards, Washington* D.C., Division of
Physical Chemistry-(UBS Hept. 8363„) (MBS with PHS
support..) May 27, 1964. 89pp.
A survey has been made of the literature on the oxidation of
polycyclic, aromatic hydrocarbons. Information has been assembled
on (1) the oxidants effective in the oxidation of such hydrocar-
bons, (2) the relative reactivity of the hydrocarbons, (3| the
conditions under which oxidation proceeds, (4) the chemical
mechanisms involved when such oxidations occur, and (5) the
products formed., t*athor)##
00069
Cm Orr, Jr., 8.P. Hendrix, T.K. Hurd, H.J. Corbett
INTERACTION OF SUBBICBON SHOG PARTICISS AMD VAPORS (FINAI
REPT«|« Georgia Inst, of Tech., Atlanta, Engineering
Experiment Station. Dec 31, 1961. 94 pp.
The purpose of this investigation was to determine the physical
effect of organic solvent vapors on aerosols having particle
radii in the range of 0.01 to 0.1 micron. To accomplish this,
an ion counter was employed to determine the particle size
distribution of various aerosols both in the presence of pare gases
and in the presence of gases containing foreign vapors. The sice
distributions were established as functions of vapor concentration.
Systems consisting of aerosolized particulates (listed first}
and a vapor (listed second) such as ammonium iodide and alcohol,
camphor and alcohol, poly(methyl aethacrylate) and methyl ethyl
ketone increased in particulate size With an increase in vapor
concentration below relative humidities of 100% while systems Of
stearic acid and turpentine, carbon and benzene, graphite and
benzene, paraffin and hexane, and napthalene and gasoline shoved
no size change below the saturation joint. Except for the systems
of graphite and benzene and carbon and benzene, the particulates
vere soluble to a measurable extent in theligaidphaseof the
vapor with which they were paired. From the results of this
investigation it may be concluded that: (1> particulate
aerosols that are soluble in volatile organic solvents'
incease in si2e with increase in «olv*at vapor concentrations.
The extent of the site change nay be predicted from theoretical
M. Basic Scieuct and Technology
1065
-------
considerations. <2) In general, the grteater the solubility of
the aerosol material the lower will be the relative humidity at
which significant growth will cccur. (3) For materials
with a relatively low solubility (less than approximately 5* by
weight) relative huniBities in excess of 100* are required for
growth if the nuclei size is cf the order of 0..01 micron diameter,
(it) An ion counter affords an excellent means for analyzing
aerosol particulate radii in the range from 0.01 to 0.1 micron..##
00101
E. P. Koutsoukos and K. Nobe
CATALYTIC COMBUSTION OP HYDROCARBONS. IV. EFFECT OF PREPARATION
METHOD ON CATALYTIC ACTIVITY. California Univ., Los Angeles,
Dept.. of Engineering- (Report No. 64-12«) Feb. 1964. 46 pp.
CFSTI: AD 601026
Five types of CuO catalysts were prepared in this study by
varying the amount of KOH used in the precipitation of
Cu(OH)2 from aqueous Cu(N03)2 solutions. The rate of the
catalytic combustion of ethylene was used as a measure of the
activity of these catalysts.. Overall rate expressions of the
form r eguals kp sub E to the Nth power were used to
correlate the experimental data. An average reaction order of
0«60 provided the best correlation of all the. kinetic data- The
experimental data indicated that the temperature required for a
given conversion decreased with increasing amounts of KCH used in
the preparation of the catalyst (up to 25* greater than
stoichiometric). The BET surface area and mechanical strength
of the catalyst increased with increasing KOH used. Using the
specific rate constant per unti surface area as a measure of
activity it was found that the catalytic activity of CuO
decreased with increasing pH (or amount of KOH used).
Comparison of the activity of the stoichiometric catalyst
prepared in this investigation with the activity of cupric
oxide-alumina (1:1) catalyst studied by Accomazzc for the same
reaction proved greatly in favor of pure CuO. (Author)##
00119
D. E„ Ventworth, E» Chen, and J. E. Lovelock
THE PtJLSE-SAHPLIMG TECHKICOE FOB THE STUDY OF ELECTRON-ATTACHMENT
PHEKOMFNA. J. Phys«. Chen. 70, (2) 445-58, Feb- 1966.,
A stndy of the parameters characterizing the electron-capture
detector operated in the pulse-sampling mode was carried out. The
pulse width, approximately 0.4 microsec., applied voltage, -50v„,
and the pulse period approximately 1000 nicrosec., necessary to
collect all of the electrons and to achieve a steady state when
argon-10* methane is used as a carrier gas were determined. It
was assumed that the electrons acguired a thermal distribution when
no potential was applied to the cell and that the results were
1066
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
independent of the pulse potential examined up to 80 v.. A kinetic
model of the processes occurring within the electron-capture
detector operated in the pulse-sampling node has been proposed-
For the case in which the electron-capturing species is capable of
forming a stable negative ion (in contrast to dissociative
electron capture), the system of differential eguations was solved
using the steady-state approximation. From this solution, one can
obtain the previously defined electron capture coefficient in terms
of the constants for the processes proposed in the model. In
certain cases one can obtain values for the rate constants and/or
the electron affinity of the molecule from the temperature
dependence of this electron-capture coefficient- Evidence is
given for the validity of the proposed model, and the magnitude of
the rate constants and the electron affinities are
given for several arcvatic hydrocarbons. (Author)#*
00128
K. W. Egger and s., w. Benson
NITRIC OXIDE AND IODINE CATALYZED ISCMEBIZATION OF OLEFINS.
VI. THEBHODYNAHIC DATA FROM EQQILIBRIUM STUDIES OF THE
GEOMETRICAL AND POSITIONAL ISOHERIZATION OF N-PENTENES.. J„ Abu
Chem. Soc™ 88, 236-40, Jan. 20, 1966.,
The eguilibrium of the iodine catalyzed gas phase isomerization
of 1-pentene and 2-pentene was studied over a temperature range
from 110.5 to 335.3 degrees. The measured values for constants of
both the positional and the geometrical isometizations yield
straight lines when plotted vs. 1/^ (degree K). Entropy and
enthalpy values were derived by application of least-square fits
of data to linear equations using a standard computer regression
program yield with standard errors (for a mean temperature of
500 K..] The data can be equally well fitted to both linear and
quadratic equations. The data for the heats of isomerization are
in very good agreement with values calculated from the dal;a on the
heat of formation reported by Prcsen and Rossini and quoted in
the API tables. The entropy differences between the isomers
obtained from the direct experimental data agree reasonably veil
with the comparative estimates of Kilpatrick, et al. Values for
partial group contributions and corrections thereof were
calculated from the data of this work and results reported
earlier from related studies on n-butenes and 1,3-pentadienes.
They are in excellent agreement with earlier estimates.*#
00161
C. A. Arrington, W.. Brennen, G. P.. Glass* J. V.
Michael, and H- NiJci
REACTIONS OF ATOMIC OXYGEN WITH ACETYLENE (I) KINETICS AND
HECHAM1SHS. Harvard Dniv., Cambridge, Mass., Dept. of
Chemistry- Har. 1965. 28 pp.
CTSTI: AD 464329
M. Basic Science and Technology
1067
-------
The rocn temperature reaction of acetylene with atonic oxygen has
been studied in a moderately fast flow system. The course of the
reaction was followed using both the Bendix T.o. F. nass
Spectrometer and a photometric method. The major products of the
reaction were carbon monoxide and hydrogen. Large amounts of
atonic hydrogen were also observed, the reaction scheme presented
is consistent with the results obtained. The rate of the overall
reaction is determined by the first initial step in which atomic
oxygen adds to acetylene to yield an excited complex which then
undergoes unimolecular decomposition to give triplet methylene*
The rate constant for this initial reaction was measured, at rocm
temperature as <8.9 plus or minus 2.8)x10 to -14th power
cc./molecules,, sec. The activation energy was less than 1
fecal../mole. Experiments with acetylene-d2 have established the
specific reactions which constitute the major pathway by which
triplet methylene, produced in the first initial step is consumed.
(Author abstract)##
00231
J.W. Newton
EVIEENCE FOB A FUNCTIONAL BISULPHIDE IN PHOTOPHOSPHOBYLATION.
Nature, 195 (1839):3H9-351, July 28, 1962.
The investigation reported here was prompted by results of
immunochemical studies on chromatophores of photosynthetic
bacteria and by the finding that the photochemical apparatus of
Bhodospirillum rubrnm yielded serologically univalent
fragments after disulphide scission. The presence of these cell
particles of a repeating antigenic sub-structure with individual
determinant groups spaced between each pair of disulphides was
therefore indicated. Production of the univalent subunits of
chromatophores can be brought about by treatment with sulphite,
heavy metals under alkaline conditions, mercaptans, or sonic
oscillation, since the antigens under consideration are placed
in the chromatophore daring photosynthetic growth, and since the
photophosphorylaticn system appears in the chrcmatophore under
these conditions, the possibility of a functional involvement of
these structural disulphides in photcphosphorylation has been
examined. (Author's abstract)#*
00238
E.B„ Stephens, F.B. Burleson, E.A. Cardiff
THE PRODUCTION OP PORE PIBOXYACYL NUBATES. J. Air
Pollution Control Assoc. 15, (3) 87-9, Har. 1965. (Presented
at Sixth Conference on Methods in Air Pollution Studies,
California State Dept. of Public Health Berkeley, Jan. 6-7,
196H-)
Three different reaction systems have been used to prepare the
first three members of the PAN homologous series Two of these
involve photolysis by ultraviolet black light lamps and one is a
1068
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
dark reaction. All are carried out In the gas phase: (1)
Photolysis of dilute (100 ppm) mixtures of a symmetrical olefin
(e.. g.,, 2 butene) with eigher nitric cxide or nitrogen dioxide
in dry oxygen or air. This was the original method and it most
closely resembles the way in which these compounds are formed
in polluted atmospheres. (2) Photolysis of dilute alkyl nitrite
in oxygen.. This is the preferred method for PAS and PPH.
It was successful for the preparation of the four carbon
homologue- (3) The dark reaction of the appropriate aldehyde with
UC2 and 03 at low concentration in oxygen. This is the
preferred method for the preparation of the four carbon
hcmologue.. The starting material is n-fcutyraldehyde. In all
cases the sain e gas chromatographic procedure is used for
purification. (Author)##
CC3S3
A« Padwa D. Cruurine
PH0I0LYT1C DESOLPHURIZATION OF DIBENZO YLSTIIBENE
EPISULPHIDE,, Chen. Ccmmun. <21) 506-7, Nov- 10, 1965.
The photo-extrusion of sulphur from dibenzoylstilbene
episulphide (I) by ultraviolet light filtered through
Pyrex glass is described. Irradiation of trans-dibenzoyl-
stilbene episulphide (I) with a Pyrex filter in benzene
as solvent afforded a mixture of cis- and trans-dibenzoyl-
stilbene (II and III) in high yield. The photolysis was
followed by infrared spectroscopy and was essentially
complete in 30-60 min. The photodesulphurization is
markedly stereospecific. Consideration of the isomeric
distribution of the olefin obtained in a number of photolyses
and the irradiation time demonstrated at least 90* stereo-
selective removal of sulphur from (I) to give (XXX).
Increasing the time of the irradiation gave a slightly higher
proportion of the cis-olefin but resulted in a diminished
overall yield of the olefinic material* The lower yields
can be attributed to a competing side reaction which predominates
at longer photolysis time- The loss of sulphur from the
episulphide upon photolysis is Bast simply explained
by asBusing a cleavage of the C alpha-S bond of
the three-membered ring followed by loss of atonic sulphur- The
light absorbed by (I) possesses sufficient energy to effect
a carbon-sulphur bond vleavage.1#
00354
I. F. Phillips H« I. Schiff
MASS-SPECTROBETRIC STUDIES OP ATCHIC REACTIONS. V- THE
REACTION 07 UITBOSBB ATOMS WITH KC2* J. Chea- Phys*
42, (9) 3171-1* Hay 1. 1965.
The reaction of N atoms with N02 was studied is % fast
flow system, using a mass spectrometer to monitor the
M. Basic Science and Technology
-------
composition of the reaction mixutre.. The rate constant
for removal of N02 by N was found to be 1»8 plus or minus
0.2 to the -11th power cc/nol/sec. By a combined mass-
spectrcmetric and photometric method the relative contributions
of the different primary reactions were determined as follows
(errors shown are standard deviations): N plus N02 YIELDS
R20 plus 0 (0.43 plus or sinus 0..04) ; N plus N02 yields
2NO (0933 plus or iiinus 0907) ; N plus N02 yields
N2 plus 02 (0..10 plus or minus 0„12); N plus N02 yields
N2 plus 20 (0.13 plus or minus 0.11)„ (Author)##
00355
A. Padwa
PHOTOCHEMICAL TRANSFORMATIONS OF A BETA, GAMMA EPOXY KETCNE.
J, Anu Chen. Soc. 87, 4205-7, 1965.
In contrast to exhaustive studies cencerned with the
photochemistry of alpha, beta epoxy ketones there has been
no attempt, to date, to examine the Fhototcansformations of the
related beta, gamma acyl oxide system. Although a formally
analogous rearrangement occurs, the mechanism of the
transformation is markedly different.
trans-1,4-Diphenyl-3-buten-1-one one (I) was prepared by
trans-1,tt-diphenyl-2-butene-l,
-------
00356
H. Kristinsson G. B. Griffin
PHOTOCYCLIZATION OF 3,3-EIHlTHU-1-PHENYLBBTE8E-1.
A NOV El PHOTOISEDCED 1,2-MITHYI BIGBATIOH. J. An. Chen.
Soc. 88, (2) 378-9, Jan. 20, 1966.
The first example of a photoinduced 1,2-methyl migration in a
simple hydrocarbon systen is reported* A mixture (1.3:1) of cis-
and trans-3,3-dimethyl-1-phenylbutene-1 (la and lb,
respectively) was synthesized. A photoeguilibrium between la and
lb was established rapidly under the irradiation conditions, and
therefore separation was deemed unnecessary. Irradiation of X
in benze (0.1 0) for 70 hr afforded almost exclusively
2,3-dimethy1-4-pbenylbutene-1 (II). The primary products
in this photoreaction are presumably cis- and
trans-2,2,3-trimethyl-1-phenyl-cyclopropane (IVa and b,
respectively). That IVa and IVb are intermediates in the
conversion of I to II is supported by the observation that the
isomeric cyclopropanes
-------
The absorption of ozone in the 9.0 aicron region of the
infrared spectrum, due to transitions fro» the ground state to the
v sub 1 and v sub 3 states, has been studied. This report gives
the numerical results of an analysis of the spectrua including
transition frequencies and perturbed intensities ordered by
guantuit number and by frequency. Calculated and observed
spectral controas are included. (Authors)t#
0CK17
E. DeBary, 8. Braun, K. Bullrich
TABLES BELATED TO LIGHT SCATTERING IB A TOBBID ATMOSPHEBE
(VOLUME 1). office of Aerospace Beseatch, Bedford, Mass-,
Air force Cambridge Besearch labs,, Bedford, Mass., Office
of Aerospace Research (Reft. Re. AFCRI,~65-710 (1) and
Special Repts., So. 33.) pp„ 1-351„ Sept. 1965.
CFSTI,DDC: AD 62887ft
The tables present the results of coaputations of the intensity
and the degree of polarization of sky radiation and radiation
scattered by a unit voluae of air containing natural aerosols.
The tabulated data are based upon new values of the scattering
functions i to the base 1 and i to the base 2 and the scattering
cross sections derived using the Die theory with ¦ egual 1.5.
in the case of primary scattering of radiation, the results are
valid for a turbid ataosphere. The tables of the scattering
coefficients and optical thickness# the absolute scattering
functions, the intensities, and the degrees of polarization are
conputed for various wavelengths between 0.4 and 1.2 aicroas
and for discrete scattering angles between 0 and 180 degrees.
{Author abstract)#*
00565
Story, Paul R. and John H. Burgess
020B0IISI5. EV1DEBCB POB CABBCJI1 OXIDE TIOTQKBRIfcATIOH AND FOR
1,3-DIP01AB JDDITIOS TO 01BF1HS. J. A*. Chea. See.,
89(22) 15?26*"5727, Oct,, 25, 1967. 12 refs.
Evidence of the existence of carbonyl oxides is based on their
reaction with alcohols to for* alkoxy hydroperoxides. Studies
report evidence for 1,3-dipolai addition of carbonyl oxides to
aldehydes but none such for the siailar addition to olefins.
Evidence is presented for 1,3-dipolar addition of a carbonyl oxide
to an olefin and further, that the olefin is a vinyl hydroperoxide,
forated in the ozonolysis reaction by tautoaerization of the
carbonyl oxide. Dpon exaaination of the reaction aixture froa the
ozonolysis of tetraaethyletfcylene vith gas and liguid
chromatography, one of the aajee products was found to be
peroxyhydroperoxide. A structural assignaent was given to the
cobpound on the basis of information obtained froa the infrared
absorption and nuclear aagoetic resonance aeasureaents along with
1072
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
observation of various other reactions. It was also established
that the other product obtained from the ozonolysis reaction was
hydroxyacetone. The isolation of hydroxyacetone. and peroxy
hydroperoxide was thought to be good evidence for the
tautomerization and subsequent rearrangement of carbonyl oxides.
However, the structure assigned as peroxy hydroperoxide has now
been found to be incorrect. Although the evidence for carbonyl
oxide tautonerization stands, the evidence for carbonyl oxide
addition to an olefin is not valid. The structures are presented
along with newly found proof for elimination of the original one.##
00608
E. Allen, Ju N. Pitts, 0r>»
THE VAEOB PHASE REACTION OF METHYL BADICALS WITH
C80T0NALD5HTDE. J» Phys. Chen., 70 (6) : 1691-1694 , June 1966.
13 refs»
The reaction of crotonaldehyde (fcut-2-en-1-al) with methyl
radicals (produced by the photolysis of acetone at 3130 A) at
temperatures in the range 120 to 250 degrees has been investigated.
The major products of the reaction were carbon monoxide,
propylene, four isomeric butenes, methane, hydrogen, and ethane in
decreasing order of abundance. The mechanism of the formation
of products is discussed. An expression for the rate constant of
the displacement reaction is presented.##
C0612
E. Kiescher
ANALYSIS OF THE SPECTRUM OF THE NITRIC OXIDE MOLECULE
(ANNUAL SCIENTIFIC REPORT NO. 2). Basel Univ.,
(Switzerland), Sept. of Physics. (Bept. No. AFCRL-66-35.)
Oct. 2, 1965., 16 pp«
CFSTI, DDC: AD 628 818
The absorption spectrum of the fourth isotope HI5018 was
photographed with high resolution between 1770 and 1380 angstrom
units. With medium resolution spectra of the four different
isotopes N14016, N15016, N14018, N15018, have been obtained
down to wavelengfcts beyend 1300 angstrom units. New
Rydberg-states ns, up, nd, nf... are reported. Data for a lower
vibrational level of the 12 sigma plus non-Rydberg state are
given. The former non-Rjdberg state P2 pi is discussed
and it is suggested to assign it as level v equal 1 of the
12 pi state. (Author abstract##
00663
S.E. Epstein
PHOTO ACTIVATION OF POZ.YNUCIEAB HYDROCARBONS. Arch. Environ.
M. Basic Sciencfl and Technology
-------
Health Vol. 10(2):233-239, Feb. 1965. (Presented at the
Seventh Annual Air Pollution Hedical Research Conference,
Los Angeles, Calif.m Feb. 10-11, 1964.}
This review presents some incomplete studies having three
principal objectives: fl) to study photodynamic mechanisms as a
parameter of activity of polynuclear carcinogens; (2) to determine
the nature of the correlation existing between photodynamic and
carcinogenic activities in the class of polynuclear compounds;
and <3) to determine whether the degree of photodynamic activity of
crude organic mixtures, such as air pollutants, could provide a
useful and rapid biological measure of presumptive carcinogenic
hazard to man, attributable to pclynuclear compounds. Prior to
separate consideration of these three objectives, the basic
techniques used in these studies were briefly described.*#
00700
I.e. Hisatsune
HITROGEN OXIDES - NECESSITY FOB ft SYSTIBATIC APPROACH
IB THEIR STUDIES. Preprint,. {Presented at the 58th Annual
fleeting. Air Pollution Control Association, Toronto, Canada,
June 20-24, 1965, Paper No. 65-169.)
The nitrogen oxides, oxyacids, and ocyhalides, most of which
ace highly reactive and thermodynamically unstable, can be
identified conveniently from their infrared absorption spectra.
However, there are numerous coincidences in the positions of the
absorption bands of these molecules, and they have lead
often to incorrect assignment of the spectra. Systematic studies
of the vibrational spectra of these compounds have eliminated
these difficulties, and characteristic spectra of many of
them have been identified. Progress in these studies
and in the use of the spectra data to determine thermodynamic
properties are reviewed. (Author abstract)##
00916
E. J. Baum, J. K. S. Van, and J. K. Pitts, jr.
REACTIVITY OF EXCITED STATES. ISIHAflOLECDL AH HYDBOGEN AT OH
ABSTRACTIOB IN SUBSTITUTED BUTlttCPBSSOSES. J. Am. Chen.
Soc., 88(12):2652-2659, June 20, 1966. (Presented in part at
the Symposium on Structure and Photochemistry of Excited
States, 1
-------
several para-substituted derivatives is highly sensitive to the
electron-donating character of the substituent and to the nature of
the lovest triplet state* Thus at 3130 A, 25 degrees, and in
several solvents. Phi sub II drops froa 0.42 and 0.39 in
butyrophenone and p-methylbutyrophenone, respectively, to 0..00 in
the p-NH2, p-OH, and p-C6H5 derivatives. Energy-transfer
and spectroscopic studies indicate that the photoreaction proceeds
froa the lovest triplet state of these ketones and that this state
is n, pi (asterisk) for reactive and Pi, Pi(asterisk) for
unreactive ketones. p-Bromo- and o-hydroxybutyrophenone do not
undergo photocycloeliminaticn. The former eliminates bromine
atoms with a quantum yield of 0.25» The latter photoenolizes in a
reaction siiilar to that observed for o-hydroxy- and
o-methylbenzophenone. The photocycloelimination reaction is
temperature dependent with an activation energy of about 2
kcal/aole for butyrophenone. {Author abstract}#*
00917
E. J» Baum and s„ Pitts, Jr.
IKTRAHOLECULAR EHERGY TRANSFER: PH0T0E1IBIBATIOH OF HALOGEN
ATOKS FRCfl AFCHATIC KETOB1S. 0. Che*. Phys., Vol.
70:2066-2067, 1966.
Photochemical reaction of bromine atom photoelimination in
p-bromobutyrophenone, a previously unreported reaction in
ring-substituted aromatic ketones, i$ discussed. The results
obtained indicated that photoelimination of halogen atoms was
quite general for aromatic ketones substituted in th« ring with Br
and I.••
00923
J. B. Pitts, Jr., J. H. Sharp, and s. I. Chan
EFFECTS OF BAVE1EHGTB AID TEHPER&TQRE OM PRIBART PROCESSES IN TBS
PHOTOLYSIS OF MITHOGEK DIOXIDE ABB A SPECTHOSCQPIC-PHOTOCHE«ICAl
DETERBI1ATIOS OF TBI DISSOCIATIC* EBERGY. J. Chea. Phys.,
40(12):365S-3662, June 15, 1964.
The quantum yields of oxygen production in the photolysis of
nitrogen dioxide have been determined at a series of wavelengths at
room temperature and as a function of temperature at 3660, 4047,
and 4358 A. These values mere satisfactorily correlated with the
extent of dissociation into M0 and 0 atoms by Mans of 02
tracer techniques. On the basis of the above correlation and
inert gas experiments, a general mechanism is proposed for the
photolysis of H02 fro* 3130 to 4047 A.. Temperature effects are
discussed in terms of a theoretical calculation based on the
population of the rotational energy levels of W02. This leads
to a spectroscopic-photochemical determination of the dissociation
energy of *02 in good agc««maat with that calculated from
thermodynamic data. (Author abstract)#*
M. Basic Sciancs and Technology
10*6
-------
00925
J. K. S. Han, B. N« KcCormick, E« J. Baum, and
J. N. Pitts, Jr.
THE ROIES OP MOLECULAR STBDCTUBE AND ENVIBONHERT IN THE REACTIVITY
0? EXCITED STATES, J. An. Chem.. Soc. 07 (20): <4409-tt«H K,
Oct. 20, 1965* (Presented at the Syaposium on Structure and
Photochemistry of Excited States, 149th National fleeting of
the Anerican Chemical Society, Detroit, Mich,., Apr. 1965.)
The importance of nolecular structure and environment in the
reactivity of excited states was discussed and demonstrated by a
study of two model photochemical systems in both conventional
liquid medium and solid potassium brcnide Matrix. The two
photochemical systems are the dinerization of anthracenes, which
is a biaolecular reaction involving a Pi, Pi (asterisk)
excited singlet and a ground-state monomer, and the
cyclo-elimination process (type-II split) of butyrophenones,
which is a unimolecular decomposition involving an n,
pi(asterisk)triplet state. (Author abstract)#*
00939
J. 0. Bufalini and E. B» Stephens
THE THE?HAL OXIDATION OF BITFIC OXIDE IN THE PFESENCE 0*
ULTRAVIOLET LIGHT. Intern- J. Air Hater Pollution, No.
9:123-128, 1965.
The kinetics of the thermal oxidation of nitric oxide in air have
been studied in the parts per million range under static and
dynamic conditions. The results shown that the third order rate
constant for the oxidation of nitric oxide with oxygen is (1.80
plus or minus/0.21) x 10 to the fourth power I square/mole
square/sec. Bith the presence of ultraviolet light and nitrogen
dioxide, the simple third order rate expression does not adequately
describe the system. A mechanism is given that describes the
system under these conditions. (Author abstract)##
01026
Foote, J.K., H. H. Halloa, and J. N. Pitts, Jr.
THE VAPOR PHASE PHOTOLYSIS OF BENZENE AT 1849 A- J. Am.
Chen. Soc., 68(16):3698-3702, Aug. 20, 1966. 28 refs.
The quantum yield of disappearance of benzene vapor at 1849
degrees is 0.9 plus or minus 0.3. The major irradiation product
appears to be a valence isomer cf benzene, tentatively identified
as "benzvalene". Addition of dilaent N2 reduces the rate of
formation of the product but, op to 50mm total pressure, increases
its maximnm concentration. Small amounts of fragmentation
1076
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
products* i.e. methane, ethane, ethylene, and acetylene, are also
observed as well as considerable amounts of pclyireric or
carbonaceous deposit on the cell walls. These products nay be
formed in the secondary photolysis of "benzvalene". (Author
abstract) ##
Q1075
A. P.. Altshuller and I« B. Cohen
ATMOSPHERIC REACTIONS OP PROPIONALDEHYDE IN AIR MIXTURES.
Atmos. Environ.. Vol. 1(3):319-25 (Hay 1967.)
A type of oxidant that has not been Identified previously is
present in atmospheric-type systems. It has not yet been shown
whether ethyl hydroperoxide or ether n-alkyl hydroperoxides are the
phytotoxicants formed when aldehydes are photooxidized. These
experimental results suggest that aldehyde reactions can become
increasingly important if atmospheric concentrations of nitrogen
oxide are reduced to low levels. (Author summary modified)**
01102
J. S» Arnold, P* <3,. Browne, E. A. Ogryzlo
THE REE EMISSION BANDS 0? HOLECUIAB OXYGEN. Photochem,
Photobiol., Vol.U:963-969# 1965.
CFSTI,DDC• AD 63181«
The temperature dependence and the absolute emission intensity of
the 63tOA band of molecular oxygen have been measured. The
results indicate that the emitting pair of molecules is not bound
and possesses a radiative half life of about 25 msec. The
implications of these results on some chemiluminescent reactions
are discussed* (Author abstract)*#
01112
P. Varanasi and J. L. Lauer
A REDETERMINATION OF THE INTEGRATED INTENSITY 07 THE 15, HICBON
HANDS 01 CABBON DIOXIDE « J. Quant. Spectro. Radiative
Transfer, Tol.6:127-130* 1966.
The integrated intensity of the 15 micron bands of carbon dioxide
at room temperature was determined by the self-broadening technique
using gas pressures op to 10 atm. Great care was taken to
eliminate stray light and to measure the geometric cell length at
every pressure- A value of 200 pins or minus 10 cm to the -2
power atm to the -1 power was obtained. (Author abstract)*#
M. Basic Science and Technology
1077
-------
01186
M. C„ Rani and S. G. leviae
PHOTOCHEMISTRY OF 2-ALKYIAKIHOPHEUCXAZ-3-0NES« North
Carolina State Bniv., Baleigh, Dept. of Chemistry. 1965„
17 pp„
CFSTI.CDC: AD 631 366
As a continuation of 2 previous studies in photochemistry of
2-dialkylamino-phenoxaz-3-ones has been investigates. Id general
these compounds have been found to be more photo-reactive than the
corresponding «oncalkylanino-phenoxaz-3-ones. The-
diBethyla*inopheno*ai-3-one H underwent photochemical denethyla-
tion. Irradiation of the 2-pclyirethyleneirainophenoxaz-3-ones gave
different products depending upon the size of the
polymethyleneinine ring. The phenoxazones 9, 11, and 12 gave
novel pentacyclic conpounds 23, 25, and 26 respectively, stable
dihydrophenojtaz-3-ones have been obtained by the reduction of
conpounds 10, 11, and 12. (Author abstract)##
01210
J. N„ Pitts, Jr., J. Kn s. Ran, and E. a. schuck
PBOTOCHEBICAL STUDIES II AN AIKA1I HALICE MATBIX. I. An
O-nitrobenzaldehyde Actino»eter and Its Application to a
Kinetic Study of the Photoreduction of Benzophenone by
Benzhydrol in a Pressed Potassiu# Bromide Disk., J. Am.
Chen. S0Cn 86, 3606-10, Sept. 20, 196<4.
The feasibility of quantitative photochemical studies in a solid
KBr "pellet" of the type custoaarilj used for ID studies
was investigated. Irradiation vac by filtered 0V light at an
angle to the "analyzing" IB bean fro* the IB spectrophotcaeter.
An actisoaeter consisting of o-nitrobenzaldehyde dispersed in the
KBr disk was developed to neasure light intensities and was
used to obtain roon temperature guantu* yields in the system
benzophenone-benzhydrol siailarly dispersed in KBr* IB
spectroscopy was used to identify products and determine reaction
rates by repetitive scanning in situ. In the photoreduction of
benzophenone by benzhydrol at 3340 A., the value of phi for
benzophenone disappearance was a function of benzhydrol
concentration and approached unity at high concentrations.
Benzhydrol disappeared by an apparent first-order law. Assuming
a simple mechanism, the ratio of the rate constants for the
deactivation vs. the reduction of excited benzophenone tc form
ketyl radicals was 0.0125 fole/1,. of KBr. Addition of
naphthalene to the "pellet" reduced the phi of benzophenone
disappearance. The ratio of the rate constants k5/k3 for
naphthalene "quenching'1 vs. reduction of benzophenone by benzhydrol
was estimated at about SO. These experimental findings indicate
that photoreduction In the KBr matrix proceeds via triplet
benzopbenbfte, as in liquid solutions. "Blending" benzophenone
TD78
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
I
-------
and benzhydrol with KBr and foraing disks at a pressure of 4800
p.s.i.. by the usual pelletizing technique seems to result in a
uniformly dispersed "solid solution.* (Author abstract modified)*#
01233
P.. Ausloos and a. S. Rebbert
PH0T0ELIHIWATI01 OF ETHYLENE PROH 2-PEHTAH01IE. J. Am„ Chem.
Soc- 86, pp. 4512, 1964.
Author reports additional information concerning photoelimination
of olefins from carbonyl-containing compounds. Measurements of
the light emission were observed in the energy transfer process
in the photolysis of 2*pentanone. Authors conclude the
probability that at any given wavelength the same process will
occur fron either a triplet or a single state say depend on the
structure of the compound under consideration.*#
01241
H. A. Accoaazzo and K« Robe
CATAITtlC COBBOStlOS OF C1 10 C3 HIDiQCABBQBS. Ind. Eng.
Chen. Prod- Bes. Develop. 4, <«) 425-30, Oct. 1965.
{Presented at the 149th Meeting Aaerican Chemical Society,
Division of Petrolena Chemistry* Detroit, Hich. , Apr. 1965.)
The catalytic coabustion kinetics of methane* ethane, ethylene,
acetylene, propane* propylene, fropadiene, pcopyne, and
cyclopropane ob CuOiA1203 has been investigated at initial
hydrocarbon concentrations between 182 and 1450 ppa in the
teaperature range 140 to 590 C«# and at gqis flow rates of 160#
275, and 525 liters per hour IBIP. The correlation considered
teaperature gradients along the bed and external diffusion of
reactant to the catalyst surface. The predicted results agreed
within 15* of the experimental resnlts at the higher flow rates
between 10 and 80* conversion. Hethane was the aost difficult
hydrocarbon to oxidize and acetylene was the easiest, in
general, increase in carbon nuaber decreased the teaperatnre
necessary for a given conversion. lor a given carbon nuaber, the
reguired teaperature decreased with degree of sataration. The
combustion products were essentially only carbon dioxide and water.
The saae catalyst bed was used for approximately 1000 hones with
no loss in activity* (Author abstract)**
01318
H.J.tU Stevenson, D.B. Sanderson, A.P. AltshuHer
FOHHATIOK OF PBOTOCHBHICII AZBOSCIS. intern. J. Air wattrf,
Pollution, Vol* 9:367-75, June 1965. (Presented at the
Aaerican Industrial Association Conference, Philadelphia, Pa,
April 29, 1964.)
M. Basic Science and Ttchnotofy
-------
Aerosol was produced photochemically by irradiation of a number
of hydrocarbon-nitrogen dioxide mixtures, some requiring sulfur
dioxide. In those reactions not requiring sulfur dioxide, its
addition increased the aerosol production in most cases, Mixtures
of hydrocarbons gave more aerosol than expected from their
production individually. Shorter wavelength illumination had
little effect indicating that sulfur dioxide activation is
unimportant. The size of the aerosol depended upon the
conditions of the experiment. {Author abstract)##
01579
?„C. Alley L« An Bipperton
THE EFFECT OF TEHPEBATDHE OS PBOTCCHEHICAL OXIDANT PFODUCTION IS
A BENCH SCALE REACTION SYSTEH. J. Air Pollution Control
Assoc.., Vol- 11:581-584, Dec. 1961. (Presented at the
54th Annual Meeting, Air Pollution Control Association*
Hew York City, Jane 11-15, 1961.)
The tabulated results of nine irradiation runs are given for
olefin and nitrogen dioxide mixtures. The oxidant production
is shown as a function of tine of irradiation and temperature.
Oxidant production was calculated by subtracting the initial
oxidant reading before the lights were turned on from the oxidant
reading at the particular sample interval. The peak oxidant
production was approximately doubled for each 10 degree
temperature increase. The average hydrocarbon reaction rate
for each four-hour irradiation period is plotted against
temperature. The rate increased sharply as the reaction
temperature increased from 13.5 to 25 C, then decreased slightly
AS THE TEHPEKATUBE INCREASED TO 35.0 C. P80H THESE HESOLTS IT
is concluded that the peak oxidant production occurring during the
irradiation of olefin and nitrogen dioxide mixtures is dependent
on the reaction temperature. The magnitude of this temperature
effect is of the sane order as that which would be predicted for
a thermal reaction.#*
01632
J. A. Yingiello and H. B. Schlecbter
SYNTHESIS AND CYCLIZ&TION 07 THE THHEE ISOMERIC 2-BENZY1PHENYL
PJHID1I KETONES. J. Org. Chem. 28, 2048-50; Sept. 1963.
{Presented before the Division of Organic Chemistry,
Southeastern Regional fleeting, American Chemical Society,
Richmond, Va., Nov. 1959.)
A considerable number of studies have been made regarding the
rates of the acid-catalyzed aromatic cyclodehydration of ketones;
these studies included only ketones containing one basic group,
the carbonyl function pf the ketone., Substituents on the ketone
were restricted to alkyl groups and halogen atoms. The
cyclization behavior of ketones containing a group more strongly
1080
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
proton accepting than the Xetonic carbonyl would test a possible
limitation of the Bradsher-type aromatic cyclodehydration
reaction.. Protonation of the substituent might retard formation
of the carbonium ion needed for cyclization. This' inference
actually does not exist since all three isomeric 2-benzylphenyl
pyridyl ketones are cyclized at a faster rate than
2-benzylbenzophenone by the usual hydrobromic acid-acetic
acid-water mixture.##
016118
E.. Horganroth and J. G. Calvert
THE PHOTOLYSIS OF 1,1*-AZ0-N-BUTANE VAPOR; THE REACTIONS OF
THE N-B0TY1» Preprint, presented before the Division of
Physical Chemistry, 149th National fleeting# American Chemical
Society, Detroit, Mich.r Sept. 1964.}
The vapor phase photolysis of 1,1#-azo-n-butane, at 3660 A was
investigated as a function of reactant pressure, temperature, light
intensity, and added gas. The sequence of listed reactions is
consistent with observed results. With the assumption that the
rate constant for the reaction, 2n~C4H9 yields n-C4H18 is
2.2 x 10 to the 13th power cc/mole-sec, and that for the reaction,
-------
hydrogen abstraction from n-pentane, assuming the activation
energies for the back reactions to be equal (HI attack or pentyl
and pentadienyl radicals), one obtains 15.4 plus or minus 1 kcal../
sole for the resonance e-nergy in the pentadienyl radical-
This value is only 25* larger than the allyl stabilization energy-
These stabilization energies are discussed in terns of a simple
model of three-electron bonds and related to energies in the
benzene system.
-------
017 47
J.C.S. Cities
THE PHOTOOXIDATIOS Of BYDSOCABBQKS. Hercules Chem. (531 19-23,
Sept. 1966.
After a brief discussion of photooxidation theory, photoinitiated
oxidation in the presence and absence of light absorbers is
described.. The effect of imparities on photooxidation of
hydrocarbons is discussed. The theory of charge-transfer
absorption by hydrocarbon-oxygen systems is examined. Other
charge-transfer initiated reactions are aentioned. It is
concluded that charge-transfer is of little significance in the
photooxidation of polyolefins. Governing factors for degradation
of these resins are imparities and additives. Charge-transfer,
however, may be responsible for photooxidation of hydrocarbons and
sulfides in the ataosphere. The author believes that the
hypothesis of photcinitiation by charge-transfer will lead to an
extension of knowledge of reactions occurring in the ataosphere.,##
01787
H.A* Guillory H.S. Johnston
IMFF1BID ABSOBPTIOH BT PEHOXT-KITBOCEH TSIOXIDE PBEB BAEXCA1
119 TBS GAS PHASE. a. Chen. Phys. U2, (7) 2457-61, Apr. 1,
1965.
In the course of studying the lev-pressure thermal oxidation of
nitric oxide by oxygen, a new absorption band occurring on the
shoulder of the P branch of nitric oxide at 18U0 cm was observed.
The new absorption band was shown to be first order with respect
to both nitric oxide and oxygen. The variation of this absorption
band with time indicated that it was probably due to the free-
radical intermediate present in this system, and was assigned to
peroxy-nitrogen trioxide. The structural assignment ootto,
rather than the syanetrical nitrate radical is based on the
absorption frequency and by a comparison with frequencies expected
for 00X0 and syasetrical 103. By assuaing a value for the
absorption coefficient of 00H0, which is presumably formed by
the rapid reversible reaction 02 * MO equilibrium OOKO,
thermodynamic data concerning CORO and the equilibrium
constant were estimated. (Author abstract)##
01801
A. Goetx
PABARETEBS FOR BIOC0L10IDAL HAITEB IF THE ATMOSPHERE.
Proc« Atmos. Biol. Conf. 79-97, 1965.
M. Basic Sclenci and Technoloty
1083
-------
Basic problems of tracing live iratter in atmosphere hinge
primarily on physical leans available for converting this specific
form of natter from highly dispersed airborne state into one
of much greater compactness at the sensor device, as its
ability to produce a signal depends necessarily upon amount of
specific matter available to it« An equally basic condition
is avoidance of viability interference fcy process of
precipitation- Parameters guiding this effort can be derived
from properties of aerocolloidal matter in general: of the
particulates, to be considered more or less permanent atmospheric
constituents, the upper size limit lies for the biosphere
at kinetic (Stokes0) diameters (between 5 and 8 microns), but
decreases rapidly with altitude, whereas the lover limit for
stable particulates of significant frequency appears to be
at approximately 0..05 micron.. This si2e range embraces, thus,
about two decades and includes bacterial cells, spores, virus-like
forms, but excludes from permanent suspension pollen, seeds,
etc. Aerocolloidal matter in the average represents but 10
to the minus 7 power to 10 to the minus 8 power of suspending gas
mass and amounts to a numerical concentration of 10 to the 6th
power to 10 to the tenth power/cubic meter of which the
biocolloidae components can be assumed to be only a minute
fraction (equal to or less than 10 to the minus 5 poweer
fraction (egual to or less than 10 to the minus 5 power)» While
upper kinetic size limit is determined by high fallout rates,
steeply declining frequency for smallest sizes is partly due
to increase of chemical activity - and thus instability - caused
by high surface curvatures (Kelvin relation), and partly due to
their physical (Brcwnian) mobility which promotes
coalescence. As most important for preservation of
viability, interaction of the particulates with potentially
reactive molecular traces in their gaseous environment is
discussed, especially under photactivating conditions. A similar
factor concerns viability interference by contact within close-
packed sample precipitates and becomes of major significance
whenever coexistent particulates are carriers of photochemical
reaction products (such as aldehydes, ozonates, etc-) which are
likely to produce toxic effects. Constitution of natural
aerocolloids - particularly regarding their organo-soluble
and thermally metastable components - is discussed and
illustrated. (Author abstract)*#
01833
P. Ausloos and S. 6. Lias
H2-TBAHSFEB REACTIONS Iff THE GAS-PHASE BADIOLYSIS 0?
HYDROCAHBOMS. J. Chenu Phys. 43, (1) 127-35, July 1, 1965.
The radiolysis of cyclohexaoe has been investigated in the
presence of varying concentrations of acetylene, ethylene,
propylene, butene, and cyclopropane. On the basis of a number of
observations, it is concluded that, in all cases, the H2-transfer
reaction C sub n H sub ¦ plus cyclo-C6H12 plus yields C sub n
H sub ¦ plus 2 does take place. Mo extensive rearrangement
occurs in the collision complex. For instance, a transfer of H2
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
to CD3CDCD2 results exclusively in the formation of
CD3CDHCD2H, while an H2 transfer to (CD2)3 leads to the
formation of CD2HCD2CD2H- Relative rate constants for the
transfer of an H2 molecule to CH3CHCH2, 1-CUH8, iso-CUH8,
2-C4H8, C2H2 are, respectively, 1.00, 0.68, 0«27# 0..10, 0.11,
and 0..072. Similar variations in the relative rate constants of
the H2-transfer reaction C sub n H sub n (plus) cyclo-C6Hl2
yields C sub n H sub m plus 2 plus C6H10 plus are noted.. The
following additional information was derived in the course of the
study: (1) When cyclopentane or n-pentane is substituted for
cyclohexane in the reaction mixture, the H2-transfer reaction
again occurs. Under comparable experimental conditions, the
probability of the H2-transfer reaction is proportional to the
yield of the parent ion as derived from the 70-ev mass-spectral
cracking patterns. (2) An increase in the pressure of
cyclopentane, from 12.7 to 210 nm, leads to approximately a 50*
increase in the yield of the parent ion of cyclopentane. (3) The
parent cyclohexane ion undergoes a charge transfer to NO at a
rate which is comparable to the rates of the H2-transfer
reactions. 02 does not interact with the parent ion. (4) The
cyclopropane-d sub 6 parent ion reacts with cyclo-C6H12 to form
CD3CDHCD2H, indicating that this ion acquires the propylene
ion structure prior to or during reaction. (Author abstract)##
01875
B. F. Erunelle, J. Em Dickinson, a ad 9. J. Hamming
INFECTIVESESS OF ORGANIC SOLVENTS IS PHOTOCHEMICAL SHOG
FORMATION (SOLVENT PROJECT, FINAL HEPT„)» Air Pollution
Control District, Los Angeles County, Calif-, Evaluation
and Planning Div. July 1966.. 188 pp»
The principal objective of this study, the determination in an
environmental chamber of the smog-forming potentials of individual
organic solvents likely to be emitted to the atmosphere, was
accomplished and it is no* possible to reach certain conclusions
based on these data. By compound types, the effects to which each
solvent group was found to contribute can be summarized as follows:
(1) Aromatic hydrocarbons, except benzene, contribute
substantially tc aerosol formation, rapid 03 formation, eye
irritation and total aldehyde formation. (2) Chlorinated
hydrocarbons exhibit almost greater 03 forming activity than
the aromatics. Eye irritation was moderate to severe, depending
upon the test conditions, and aerosol formation was negligible.
On the basis of an experiment with tetrachloroethylene (8 pp«0
and NO (2 ppm), alone, it is concluded that most of the activity
of the mixed chlorinated solvent nay be attributed to
trichloroethylene. (3) Aliphatic hydrocarbons
-------
acetone (8 ppir) and HO <2ppa) showed little activity by this
compound with respect to ozone formation or aerosol formation, and
only very slight eye irritation was indicated. Data indicate that
the branched ketones are considerably more reactive than
straight-chain ketones. (5) Alcohols are the least active class
of compounds tested.##
01878
F. Cramarossa and H. S. Johnston
INFFAHID ABSORPTION BY STfMREIRICAL N03 FFEE RADICAL IN THE
GAS PHASE., J. Chen.. Phys. 43, 12) 727-31, July 15, 1965„
A new infrared absorption band between 1325 and 1375 cm to the
minus one power has been observed in the N205-03 system at lew
pressure in as 80-it path-length cell* In such systems the
presence of the synaetrical N03 free radical is yell kticwn in
terms of its visible absorption spectrun, which varies in the
unusual way of Kss(N205) to the one third power (03) to the
one third power*, The new infrared band lies at a frequency just
below that for the antisyaaetric stretch of the symmetrical
planar nitrate ion; the absorption optical density varies as
{ N 2 0 5) to the one third power <03) to the one third power;
and the new absorption has been assigned to the synaetrical N03
free radical. {Author abstract)##
C108O
K. Egger and S» R. Benson
IODINE AND NITRIC OXIDE CATALYZED ISOMEHIZAHON OF OLEFINS.
V., Kinetics of the Geometrical Isonerization of
1,3-Pentadiene, a Check on the Bate of Rotation about single
Bonds, and the lllylic Resonance Energy. J. An. Chen. Sac.
87, (15) 3314-9, Aug. 5, 1965.
The kinetics of the nitric oxide catalyzed* hoaogeneous, gas
phase isonerization of 1,3-pentadiene have been studied over a
temperature range between 126 and 326 degrees. Analysis of the
data shows that the rate-controlling step in the NO-catalyzed
geometrical isoaerization of pentadiene is the rotation about the
single bond in the intermediate radical. Iodine is shown to form
a auch acre stable interaediate radical, and results indicate that,
in the 12-catalyzed system, tbe addition reaction of I atoms is
rate controlling. The rotational rate constant log kc was
calculated to be (11.5 Flus or ainus 0.3) - (5.3 plus or minus
1„0)/theta sec. compared to (11.2 - |3.8)/theta sec.) as
reported earlier for the iodine catalyzed cis-trans isonerization
of 2-butene. (Author abstract modified)*#
1086
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
018 81
K. W. Egger and S.. W. Benson
NITRIC OXIDE AND IODINE CATALYZED ISOMERIZATION OF OLEFINS.
IV. Thermodynamic Data from Equilibrium Studies of the
Geometrical Isonerization of 1,3-Pentadiene.. J- An. Chen..
Soc. 87, (15) 3311-**, Aug*, 5, 1965.
The measurement of eguilibriua constants of the iodine-catalyzed
gas phase reactions of olefins and their parent hydrocarbons has
been shown to be a very simple, direct, and valuable method to
determine precise differences in the thermodynamic properties of
the reactants. Applied to the eis-trans isonerization of
1,3-pentadiene, the present paper reports an appreciable amount of
side reactions and considerable difficulties in product separation.
This result is in contrast to the clean-cut experiments on the
isomerization of 2-butene. The important two side reactions, the
polymerization of 1,3-pentadiene and the formation of diiodide in
the lower temperature range, are shown to be a consegnence of the
considerably more stable radical intermediate formed with
1,3-pentadiene compared to 2-butene., The HO-catalyzed system
showed excellent reproducibility and no measurable side reactions.
M02 gave rise to the same difficulties obtained with the iodine
catalysis.. This is to be expected from the C-OHO bond
strength of about 5*1 kcal. •#
01888
B. E*. Bebbert and P.. Auslccs
QUENCHING OF THE TRIPLET STATE OF ACETONE AM> BIACETYL BY
AZOAIKAKES. J. Am. Chem. Soc» 87, (9) 1847-52, Hay 5, 1965.
It is shown that small concentrations of azoalkanes quench the
phosphorescence emitted by acetone and biacetyl, but they do not
affect their fluorescence- In the case of acetone the relative
quenching efficiencies of nitric oxide* azomethane, and oxygen ace
2.8:2.2:1.0 and for biacetyl the efficiencies of azoethane,
azomethane, nitric oxide, and oxygen ace 19:15:6.7:1.0. It is
suggested that the ketone molecule can transfer its triplet state
energy to form a triplet excited azoalkane molecule. The
photochemistry of the energy-transfer reaction was studied in order
to obtain additional information about the fate of the triplet
excited azoalkane molecule., A fraction of these triplet excited
molecules, formed by the energy transfer from acetone~d6,
decomposes into a nitrogen molecule and two alkyl radicals. The
remainder of the triplet axoalkane is collisionally deactivated to
the ground state. At 30 degrees and an acetone~d6 concentration
of 8 x 10 to the minus 3 mole/1.,, the quantum yield of nitrogen
formation is 0.31, independent of the concentration of
axomethane from 0.4 x 10 to the minus 4 to 8.8 x 10 to the minus
1 mole/1. The substitution of azometJiane-d6 or azoethane fox
axomethane under comparable conditions results la a decrease in the
M. Basic Science and Technology
-------
quantum yield of nitrogen while the quantua yield of carbon
noncxide is essentially constant. This indicates a longet
dissociative lifetime for the triplet a2o*etfaane-d6 or azoethane
compared to azomethane. -{Author abstract}##
01889
B. c« sahni and E„ J. DeLorenzo
ELSCTHOHIC STATES OP HOI.ICDLES. I. Self-Consistent Field
Calculations of the Ground, Ionized, and Excited States of
H2 and 02. J. Che*. Phys. U2, <10) 3612-20, May 15, 1965.
presented at the Syaposiua for Molecular structure and
Spectra, Ohio State Dniv., Coloatus, Ohio, June 196U.)
A nuaber of electronic states of »2 and 02 hate been
computed using the self-consistent-field-nolecular orbital
(SCF-tlO) set hod. The calculated ionization, excitation, and
total energies are compared with the available experlnental data,
as well as with those reported by other workers. (Author
abstractj ##
01961
6. F- McMillan, J. G. Calvert, and J. V. Pitts, Jr.
DETECTION ADD LIFETIME OF EMOX-ACET0SE IS THE PHOTOLYSIS OF
2-PENTAHONE VAPOB. J. ta. Chew.. Soc. 86. 3602-5, Sept. 20,
1964.
The formation of the enol for* of acetone in the "type II"
primary photochenical process in asethyl ketones containing
gaama-hydrogen atons has rec«ive& general acceptance in recent
years on the basis of published indirect evidence. In this work a
direct observation of the transient enol forn of acetone has been
made by infrared absorption during the photolysis of 2~pentanone.
The enol to keto conversion was studied by following both the
disappearance of the enol and the appearance of the keto forn using
long-path infrared techniques* The half-life of enal-acetone is
about 3.3 sin. at 21 degrees and 750-*». total pressure. The
ketonization process seeas to occur aainly at the reaction vessel
nail, photolyaes of 2->pentanone were also carried out in saall
reaction vessels pretreated with D20. In this case the
keto-acetone ultiaately produced is partly aonodeuterated, and a
partial exchange of the enol fori at the vessel wall is indicated;
this result is siailar to that reported by Srinivasan in
experiaents with 2-hexanone. The extent of exchange exhibits a
peculiar dependence on the residence tine in the cell which
cosplicates the interpretation of the ketonization step under these
conditions. (Author abstract}*#
1088
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
01978
A. P. Altshuller, I. B.. Cohen, S. F. Sleva, and S. 1.
Kopczynski
aib polldtick: phctooxication of abchatic hydbocabeohs..
Science 138, (3538) 4#2-3, Oct. 19, 1962.
A nunbcr of aromatic hydrocarbons participate as effectively as
the olefins in atmospheric photooxidation reactions in the presence
of nitrogen oxides and ultraviolet light. Judged both on the
basis of reactivity and concentrations in the atmosphere, the
aronatic hydrocarbons cannot be ignored as contributors to the
photochemical type of air pollution. (Author abstract)##
01990
A* Goetz and T. Kallai
THE SYNTHESIS OF DEFINED AEROSOI SYSTEMS- An. Ind. Hyg.
Assoc. J„ 2<», 153-61, Oct. 1963.
Instrumentation and procedures for the synthetic production of
photochemical aerosols within a laminar airflow along a tubular
channel are described. Special aicro-dosiaetry quantitatively
facilitates continuous addition of reactive trace coaponents
(hydrocarbons, NO, 802, 502) and of defined nucleating
particulates.. The flow is subsequently irradiated symmetrically
in the spectral range 1320-450 milliaicrons) in a special channel
section without temperature increase, at adjustable intensity
levels and exposure durations up to several tines solar intensity
at ground level. The resulting aerocolloidal coaponents are
analyzed with the Aerosol Spectrcaeter for deteraining the size
and aass distribution of the photoactivated particulates at various
reaction stages. Exaiples of sacg-type reactions between traces
of N02 and olefins, and of atodifications of natural aerosols, are
presented* (Author abstract)*#
02082
E. Savicki, T..W. Stanley, J. Pfaff, H. Johnson
SENSITIVE NEW METHODS FOB AUTOCATALYTIC SPECTHOPHOTOHETRIC
DETEHfllBATION OF NITSITE THROUGH FBEE-BADIC1L CHFOHOGEHS.
Anal. Chea. 35, (13) 2183-91, Dec. 1963.
Many of the aethods presented here are nore sensitive than
any described in the literature. A aolar absorptivity of
1,270,000 can be obtained in the l-aethyl-2-guinolone azine
procedure, while in aost other procedures aolar absorptivities
average over 200,000. the following reagents arc coapared:
l-aethyl-2-qninolone azine« 3-aethyl-2-benzothiaxolinone azine#
M. Basic Science and Technology
1089
-------
glycxal bis (NrN diphenylhydrazone), 3-methyl-2-
benzothiazolinone picrylbydrazone, phenothiazine, N,N,N",Nr-
tetramethyl-f»„
-------
produced in the liguid- and solid' phase photolysis of
CH3HgCB3-CD3HgCD3 nixtures, it was concluded that cage
recombination of aethyl radicals does take place, contrary to the
conclusions reached in as earlier worJe by Derbyshire and
Steacie* no evidence could he obtained for hot aethyl radical
effects in the liguid-phase photolysis of diaethylnercury.
{Author abstract)*#
02258
G. A.. Oldershaw and R„ J* Cvetanovic
PHOTOCHEMICAL A EDITION OP HYDBOGEH BBOBIDB TO 2-BOTENE IB THE
GAS PHASE. 0. Che a. Phys. 41, |11) 3639-W, Sec.. 1, 196^.
The relative rates of the photochemical addition of hydrogen
bromide to 2"butene, and of the simultaneous cis-trans
IsouerizatioB have been measured in the gas phase at 5<* C„
Similar but less extensive experiments have been carried oat with
1t2-dldeutera«tlxylen«» In this case* comparison of the rates with
the data in the literature indicates aucfa faster cis-trans
isomerizatlon than can be expected from the decomposition of
thermalized broaoethyl radicals. Alternative explanations of the
fast geometric iscmetization are briefly discussed.##
02286
c.P. penimore g.r. Jones
THE WATBH-CATALYZBD 0XIDATI0H OP CABBON MONOXIDE BY OXYGEN AT
HIGH TEMPERATURE. J. Phye. Chea» 61, 651*4, Hay 1967.
Ey sampling burnt gases fro* lean flat hydrocarbon flames at one
atmosphere pressure, the oxidation rate in the presence .of anpie
water at 1700-200QK is determined to be - 1/(02} (dln<(CO)/dt)
+ 1„2 x 10 to the 9tfc pover e to the -2*,000/j?T/(«oles/1)/sec.
In burnt gas froa CO flanes containing very little water,
-dln(C0>/dt is independent of oxygen and roughly proportional
to water. The slower rate of comparatively dry CO flases Is
raised toward the value appropriate to hydrocarbon flames, by adding
hydrogen to the CO. A partial mechanism is suggested which is
consistent with these results. (Author abstract)#*
023 09
G. K« So bo lev
HIGH-TEHPERATURE OXIDATIO* AMD BDBVING OP CABBOB HOKOXIDE.
Synptf Combust., 7th, London# Oxford, 1958. 386-91. 1959.
The purpose of this study was to measure the rate of burning of
CO in the flaae front, using the results of normal flane
W. Basic ki»nc« and T&chnolojy
1091
-------
velocity measurements foe this purpose, and simultaneously to sake
direct measurements of the rate of oxidation of CO in the after-
burning zones of the sane flames* A comparison of the data
obtained by these two independent methods will evidently be of
theoretical and of practical value.. ~~
02328
B. C« Gunton and T„ Shaw,,
AHBIPOLAR DTFFDSIOH AND ELFCTRON ATTACHMENT IN NITRIC OXIDE IN THE
TEHPERATOBE RANGE 196 TO 358 K„ Phys. Rev- 1U0f (3A)
A748-A755, NOV. 1, 1965.
CFSTI, DDC AD 631223
Ambipolar diffusion and electron attachment rates were measured in
nitric oxide at pressures fro* 0.01 to 16 Torr and at temperatures
from 196 to 358 K. The gas was photoionized by single pulses of
ultraviolet radiation, at and near Lyman alpha from a hydrogen
lamp. Pulse lengths ranged from 10 to 300 microsec and
ionization levels were kept low to reduce electron-ion
recombination. Bates for the latter process are reported in a
separate paper. Electron loss rates were measured by a microwave-
cavity method used to record the decay following a single ionizing
pulse. Ion identification was made by a mass spectrometer which
sampled the ions diffusing through a small hole in the wall of the
microwave cavity. Oltrahigh-vacuum techniques were used in gas
purification and in production and measurements of ionization-
The diffusion results are to some extent consistent with theory
of diffusion of electrons and a single positive ion species in the
presence of negative ions. The mass-spectrometer observations
indicate that NO plus is the dominant positive ion in
photoionized NO at all pressures. The principal negative ion
observed with the mass spectrometer was N02(-)* and no NO(-) or
H02{-) ion were detected. Direct attachment ot N02, present
as a minute impurity, seems unlikely; the N02(-) ion may be
formed by rapid charge transfer from a primary negative icn or by
an attachment reaction involving rearrangement. (Author abstract
modified)*•
02337
D. Phillips.
PH0T0LYTIC PROCESSES II PERFIOOHOCYCIOBOTANCNE VAPOR. J.
PHTSw CHEH. 70, <4) 1235-43, APR- 1966.
CFSTI, DDC AD 635437
The photolysis of pertluorocyclobutanone in the vapor phase at
3130, 3340, 3660, and 4047 A has been investigated.
Fluorescence and decomposition yields have been determined at the
four wavelengths and the effects of pressure and temperature upon
them stndied. Two modes of decomposition occur at the shortest
wavelengths and at high temperatures, one producing carbon
monoxide and pertluorocyclopropane, the other producing
1092
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
tetrafluoroethylene. & mechanism is proposed which explains the
results, and rate constants for reactions are determined.
Results indicate that about 7 kcal/mole excess vibrational energy
can be removed from the excited ketone by each collision with an
unexcited ketone molecule. (Author abstract)##
02412
A„ Goetz R. Pueschel
THE EFPECT OF NUCLEATING PARHCCLA1ES ON PHOTOCHEMICAL AEROSOL
FORHATION. J- AIR POLLUTION CONTROL ASSOC. 15, (3) 90-5.
Bar. 1965. (Presented at the Sixth Conference on Hethods
in Air Pollution studies, Eerkeley, Calif,, Jan- 6-7, 196a.)
The role of nucleating particulates in the formation of
photochemical aerosols was studied in a steady, laminar flow of
ultrafiltered air containing N02 and octene-1 in the
concentration range of: (30 - 170 ppm), when subjected to intense
irradiation under isothermal conditions. The particulates
consisted of monodisperse polystyrene latex (d equal 0.36 micron)
in concentrations similar to those in the atmosphere; the
irradiation intensity varied between: (6 - UO,000 lumne/liter) and
the mean exposure duration between 30 - 180 sec. Samples of the
flow, prior to and after its photoactivation, were withdrawn
either by an Aerosol spectrometer (AS) or by a Royco
Aerosol Photometer. The photoiietric data include all
colloidal components in the airborne state, whereas the counts
obtained from the AS-deposits refer only to tbe nucleated latex
particles.. The following pattern is evident: The
photochemical reaction yields fractional products (less than 3*)
which have the tendency to agglomerate (or polymerize) due
to their relatively low volatility—independent of the presence or
atsence of nucleating particulates. The growth process appears
principally different from that of fog formation by H2Q&-
condensation, where, for identical supersaturation, it is inversely
proportional to the nuclear concentration. In the absence
of nuclei, antomicleation, i.e. self-agglomexation, occurs
at a much lesser reaction rate and higher photon demand. The
growth rate of the nuclei, when present, depends on the
concentration of the oxidation catalyst (N02). Under
identical conditions the mass of nuclear accumulant is directly
proportional to the concentration of the reactive hydrocarbon,
while the growth rate depends on the light intensity and tbe
exposure duration- The findings indicate that density and nature
of particulate matter present in an air mass prior or during
photo-activation are, aside from the chemical reactant levels,
of major significance in aerosol formation. (Author abstract
modified)i#
02«U3
HTDHOCARBON - AIR FUEL CELLS. General Electric Co., Lynn,
Mass., Direct Energy Conversion Operation. (Technical
Summary Rept™ So. 8, July 1-Dec» 31, 1965). 266p„, 1965
CFSTI AD 479005
M. Basic Science and Technology
1093
-------
Detailed information is presented on a continuing research and
development program to develop a direct hydrocarbon oxidation-air
fuel cell technology. Current work included research on
electrochemical oxidation processes, electrocatalysts,
electrolytes, electrode structures, and fuel cell life testing..
Multi-pulse potentiodynamic techniques have been further developed
for analyzing hydrocarbon surface processes. Performance of fuel
cell systems with hydrogen fluoride and phosphoric acid
electrolytes have been studied for high performance
hydrocarbon oxidation.. Boron carbide and carbon have been
successfully employed as substrates for high surface area platinum
and the results and application to Teflon-bonded electrodes are
reported- A variety of modified Teflon-bonded developmental
electrodes were evaluated. (author abstract)##
024U5
G. w.. Griffin
PHOTOCHEMISTRY OP UNSATURATED CARBONYL DERIVATIVES AND RELATED
SMALL HIHG SYST2HS (TIDAL SEPT. JULY 1, 1963-DEC. 31, 1965.,)
Tulane Univ., New Orleans, La., Dept. of Chemistry
(AROD Bept. No.. 4375i11.J28 pp„# June 1, 1966
CESTI AD 635217
The photofragmentation of a variety of snail ring homo- and
heterocyclic systeis including cyclopropanes, epoxides, aziridines,
oxaziranes and spisulfides are studied. The photorearrangement of
cyclopropanes to olfins and the photoinduced conversion of
cyclopropenes to indenes also are examined. The studies are
complementary and those parameters which determine the reaction
course are defined in each case. For exanple, it is of interest
to determine why certain cyclopropanes fragment to carbenes and
others simply rearrange to isomeric olefins. Many of those
reactions described have synthetic utility and heretofore
inaccessible systems now have been synthesized. The
photofragmentation of stilbene oxide is illustrative and appears
to be the method of choice for preparing phenylcarbenes and thus
phenylcyclopropanes and cyclopropenes.##
02d46
K« 0. Hartnan and I. C- Hisateune
ISEBARED SPECTHOB 0? CARBOH DIOXIDE ANION RADICAL. J„ Chen.
PHTS. 44(5} 1913—8, MR- 1, 1966.
CFSTI„DBC AC 635357
Pressed alkali halide disks of infrared spectroscopy have been
used as matrices to trap and to stabilize the carbon dioxide anion
free radical.. The radical was generated by exposing disks
containing the formate ion to solid solution to gaciita rays from a
cobalt source. The ESB, the ultraviolet, and the infrared
spectra of the radical have been identified* ?ro» the carbon*12
1094
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
arid-13 isotopic frequencies of the antisyaaetric CO-bond
stretching infrared band* a valence angle of 127 degrees plus or
minus 8 degrees was calculated for this radical. The radical
reacted with water to produce bicarbonate and formate
ions. (Author abstract)••
02U56
A.V. Phelps W„H. Kasner
STUDIES AND EXPERIMENTAL WORK ON
OCCURRING IN ATMOSPHERIC GASES.
Pittsburgh. Pa. (Technical Kept.
May 1966
ATOMIC COLLISION PROCESSES
Hestinghouse Research Labs-,*
AFVL-TB-66-34.) pp. 73„
Temperature dependent recombination studies in nitrogen have
been conducted over the range 200-480 Kv yielding a
coefficient of (2.9 plus or minus 0.3) x 10 minus 7/cua/sec.
for the recombination of N2f«) ions and electrons. The
observed temperature dependence is quite small, being
adequately described by the relation T to minus *02. Several
sodifications have been cade on the flow system used in the
study of associative detachment in 02 minus 0 mixtures. In
subsequent studies a reaction resembling associative detachaent
has been observed. While preliminary tests were being
conducted on the rf Bass spectrometer which is to be used
on the flow system* a brief study of negative ion-molecule
reactions was made. Rate coefficients for several of these
reactions were measured. A summary of the results of a
calculation of momentum transfer and inelastic cross sections for
electrons in oxygen is presented. The computed momentum
transfer cross section is in satisfactory agreement with electron
beam results bat it differs significantly from the cross section
obtained at thermal energies from microwave experiments.
(Author abstract)4#
02464
H. Sjogren E. Lindholm
IOSIZATIO* MID DISSOCIATIVE IONIZATION OF 02 AFTER ELECTRON
AND IMPACT. Royal Inst, of Tech., Stockholm# Sweden,
Dept of Physics, (scientific Hept. 4 and Hept. AFCRL-66-
436.) 08C. 15, 1965. 24 PP.
The ionization of 02 warn investigated by using charge
exchange in a double mams spectrometer. The breakdown graph
was constructed. A break in the electron impact ionization
efficiency curve is explained as being due to ion-aoleeol*
reactions between excited o plusor minus ions formed in as
ion/pair process, and 02. It was shown that the cross sections
must be very small for the reaction, 0*- J4S) + 02 yields
0+02 plus or minus since the cross sections for the
corresponding reaction vith Si plus or minus are small.
Implications for the aeronomy ars discussed. (Author abstract)#*
M. Basic Science and Technology
109$
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02472
S.S.. Bilks
PHELIMINABY STUDIES ON LIGHT-INDUCED CABBON MONOXIDE IN CLOSED
ENVIRONMENTS. School of Aerospace Medicine, Brooks
AFB, lex.. Aerospace Medical Division. Sept. 1963. 9 pp.
CFSTI, DDC AD 420946
Experimental data is presented concerning the effects of solar
light upon certain classes of organic substances which may be
components of the sealed environment of space vehicles. Many
materials such as organic plastics, pigments, insulating
material, etc-, will, when exposed to light in the presence of
oxygen, liberate a number of toxic end products such as carbon
monoxide, aldehydes, acids and certain hydrocarbons. In a
sealed environment these agents may reach levels toxic to human
beings during a long sojourn in a sealed system. Therefore,
along with products that may result from thermal and
electrical activity (motors, generators, etc.), these products
may constitute a considerable hazard in sealed environments.
{Author abstract)##
02489
J. K« S. Van and J« N» Pitts, i3r.
A SPECTROSCOPIC INVESTIGATION 0? THE REACTION BETREBN IODINE AND
CYCLOP80PXLAMINE. Tetrahedron Letters, 44:3245-50, 1964
The reaction between iodine and cyclopropylamine in n-heptane
solution was studied spectroscopically. Preliminary results
suggest that 1:1 charge-transfer complex between iodine and
cyclopropylamine was formed first; subseguently precipitation of
white crystals of a 2:1 cyclopropylamine-iodine complex,
C3H5NH2)2 12 (A)* occurred. Evidence suggests that the
solid product (A) has probably an ionic structure*##
02493
0. K. S. Man, L. D« Hes&, and J. N. Pitts, Or.
1BEE-BACICAL ADDITION TO AZOBENZENE IN CDMENE SOLUTION.
ELECTRON PARAMAGNETIC RESONANCE SPECTBA OF SOME LONG-LIVED
RADICAL INTEBMEDIATES. J. Am. Chem. Soc. 86, 2069-70, 1964
A degassed solution of azonbezene in cumene was irradiated at room
temperature in the microwave cavity of Varian V 4500 e.p.r.
spectrometer with 100-kc. field modulation. Light source was a
PEK mercury high pressure lamp equipped with filters which
absorbed wave lengths shorter than VOOOA. At room temperature
irradiation, a spectrum was observed with an intensity dependent
upon the initial concentration of azobenzene. The spectrui is a
1096
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
triplet, each component of which contains 4 groups of lines with
intensities following a 1:3:3:1 binominal distribution. Each of
the groups is further split Into 3 lines. The radical structure
consistent with observed spectrum is composed of the azobenzene and
cuaene structures Joined at a nitrogen atom and the tert-carbon
atom.. Experimental coupling constants and experimental and
theoretical spin desnities are tabulated. Separate experiments
on a larger scale in which the reaction was subjected to liquid
chromatography resulted in N,N«-Dephenyl-N-(1-aethyl-1-
phenylethyl) hydrazine being eluted. Its identity was confirmed
by IP and n.m.r. analysis.##
C 2494
H„ W„ Johnson, Jr., J. N» Pitts, Or,, and M. Burleigh*
POSSIBLE FCBMATION OF CROSSED PINACOLS IN THE PHOTOLYSIS OF
BENZOPHENOME MIXTURES. Chen. Jnd. (London) 1IW3„ 196ft
Bacuum degassed binary mixtures of benzophenone, ft,ft
dichlorobenzophenone and 4,ft-dimethoxybenzophenone in 3:1
tenzeneisopropyl alcohol solvent at room temperature were
photolysed using a Hanovia Type A mercury are filtered to remove
radiation below 30001. Equiaolar and eguiabsorbance solutions
were studied with no significant difference in the
results. No crossed pinacol was found in the photolysed mixtures
of ft,U-diaethoxybenzophenone with benzophenone or 4,ft
dichlorobenzophenone. However, an equimolar Mixture of ft,ft"-
dichlorobenzophenone with benzophenone (0., 53m} yielded 15-20% of
the "crossed*1 pinacol, the balance being a mixture of the
symmetrical pinacols. Since both ketones are being excited by the
incident radiation, the non-formation of "crossed1* pinacols in two
of the three cases studied indicates that transfer of the
excitation energy from one ketone to the other is occurring. This
transfer may occur in excited state of the ketones, or it could
occur as a hydrogen atca transfer in the ketyl radical
intermediates. The elegant demonstration of triplet transfer by
Hammond and others makes this mechanism an attractive one;
experimental justification is being sought.##
02ft96
0. Pitts, Jr., E. Au Schuck, and J. K« S. Wan.
PHOTO BE DUCT ION OP 2* 2-DIPHENYL-L-PIC8YLHYDHAZYL (DPPH) IB
HYDROCARBONS.. J. Am. Chea., Soc. 86, 296-7, Jan. 20, 196ft..
Preliminary results of an e.p.r. investigation of the photo-
induced abstraction of hydrogen atoms from hydrocarbons by 2,2-
diphenyl-l-picrylhydrazyl .(DPPH) are reported. Light absorption
by DPPH solutions at 3130 A was determined by using the
photochemical disappearance of benozphenone and the formation of
acetone in isopropyl alcohol as the actinometer. In the dark no
diminution of e.p.r. signal intensity was observed. During
irradiation the signal decreased according to the first-order rate
law.. An equation for determining the reaction rates of DPPH in
different hydrocarbon solvents using the quantum yield is given.##
M. Basic Science and Technology
1097
-------
02498
J. K. S. Han, E. A. Schuck, J. K. Foote, and J. H.
Pitts, Jr.
THE FQBHATION OF 1KIBOTXLIOOOASHOKIUK IODIDE IN THE UHANYI
PHOTOSENSITIZED REACTION WITH TETBABUTYLAHMCMIUB IODIDE. Can
J. Chea. 42, 2029-31, 1964
The reaction of tetrabutylaaaoniua iodide in aqueous solution
sensitized by uranyl nitrate is reported and is disclosed a
photochemical lethod for preparing tributyliodoaaaonium iodide.
When an aqueous solution ef uranyl nitrate and tetrabutylamaoniua
iodide (I) was irradiated at rooa tenperature with the 3660 A
line froa a aercury vapor laap, a black precipitate was formed.
In the absence of light, no precipitation was observed. The
identity of the precipitate as tributyliodoanmoniua iodide
(C4H9)3IH (+JI (-) (II), was confirmed by elenentary analysis,
molecular weight deteraination, infrared and nuclear magnetic
resonance (n.a.r.) analyses. The nolecular weight was found
experiaentally to be 442: calculated for II is 439. The IB
spectrua was consistent vith that expected for II. The n.m.r.
spectrum exhibits three coaplex nultiplets centered on r values of
A, 8.90, B, 8.40 and C, 6.75; with integrated areas being in the
ration 1.55:2:1. Peak A can be assigfted to the aethyl protons
(9B), peak B to the aethylene protons (12H), and peak C to the
protons (6H) adjacent to the nitrogen atom. The OV spectrum
taken in ethanol solution showed an absorption onset at 5000 A
with aaxiaa at 3650 and 3200 A. The product II exists at rooa
temperature as a black powder vith a aelting point of 65-68 c.
The coapound is stable at least up to 135 C, and exhibits a
reversible theraochrcaic phenoaenon (fron black to yellow) when
waraed to 88 C or higher. The IB spectra of both color foras
do not show any drastic changes. The experinental data obtained
to date are insufficient to establish the entire reaction
aechanisa, but seen to suggest that oxidation of the iodide ion is
sensitized by the photoexcited uranyl ions, leading to an iodine
atoa and solvated electron. Bte direct photolysis of a aqueous
solution of I also was carried out by light shorter than 3000 A.
A black precipitate of II was recovered together with soae free
iodine.•#
02503
J- G.. At wood
ABSORPTION OF LIGHT IK GASES,. Perkin-Elmer Corp., Norwalk,
Conn., Electro-Optical Div. (PE Engineering Bept. No.
6361) 38 pp. 1966.
Two methods of measuring optical molecular absorptivities in gases
were studied. An acoustic Method was pushed experiaentally to a
sensitivity of 10 to the -5 power/cm absorptivity. The second
oethod, a laser illuainated "spectrophoae", is now being
investigated. Both aethods use a Q-swiiched ruby laser,
tunable froa pulse to pulse over a 2A range, as the excitation
1098
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
source. Absorbed light causes a temperature rise and expansion of
the gas sample. In the acoustic method the expansion starts
cylindrically propagating sound disturbances. These are focused
by acoustic nirrors onto a membrane detector. n the spectrophone
¦ethod the gas sanple is enclosed in a sealed glass tube. The
gas expansion causes a pressure rise which is transmitted to the
aeabrane detector through a short duct. The nembrane is one
reflector of a near confocal resonator, illuminated by a freguency
stable gas laser, snail aembrane displacements are detected
as fringe notion across a sensing prism by two photomultiplier
tubes. Large displacements are averted by a servo loop which
applies the photomultiplier difference signal to electric grids,
forcing the aeabrane to stay within one order of the resonator.
The loop feedback signal is a calibratable measure of the gas
optical aolecular absorptivity at the wavelength of the ruby laser
pulse. One practical problen of the acoustic method is the high
freguency and transient nature of the signal. The longest
wavelength is twice the laser beaa diameter, so the signal
frequencies are 300 kHz and higher. The membrane oust be very
thin to respond to such high frequencies and its displacement is
typically less than 1ft. The aeabrane reflectivity cannot be made
greater than 60%, so the resonator fringes have low finesse.
These practical difficulties make shot noise in the fringe-reading
photometer, rather than Brawnian noise the limit of performance.
In the spectrophone, high freguency problems are avoided. The
observation time is 30 milliseconds, set by thermal diffusion from
the gas sanple to the tube walls. The nembrane can be much
thicker and still have a 12abd2/10 displacement for a typical
pressure rise of 1 dyne/sg cm.. Initial experiments indicate great
sensitivity with the spectrophone. (Author abstract)##
02504
02504
V. D. Baiaaonte, D. H. Snelling, and E. J. Bair
VIBRATIONAL ENERGY OF OZONE DOSING PHOTOLYTIC EXPLOSION.
J. Chen. Phys. 44, (2) 673*82, Jan. 15, 1966.
CFSTI, DDC AD 633291
Following a short photolysis of the proper energy the absorption
spectrua in the region of the ozone Uv system, a continuum
centered at about 2550 A» broadens'and shifts toward longer
wavelength as the reaction proceeds. Kinetic neasuceaents of this
shift over a period of 200 nicrosecs following a mild photolysis
flash of 12 nicrosecs duration in 0*5 Torr pure ozone are
interpreted in terns of population of ozone vibrational energy
states by exchange of energy with vibrational!? excited oxygen
formed during the exotheraic decomposition. Considerable 02-03
vibrational equilibration occurs within 50 aicrosecs. A
semi-empirical model which correlates the ozone vibrational
teaperature and the observed data is discussed in relation to the
over-all energetics of ozone decoaposition. (Author abstract)##
M. Basic Science and Technology
1099
-------
02508
D- G. Clifton
APPROXIMATE THERMODYNAMIC FUNCTIONS FOB THE K02(G) IOff
(TECHNICAL SEPT.), General Hotors Corp., Santa Barbara,
Calif.., 6(1 Defense Research labs,, Aerospace Operations
Califn. Defense Research Labs., Aerospace Operations Dept.,
Bay 1966. 13 pp.
DDC AD 48*1367
Approximate values for the free-energy function, enthalpy
function, entropy, and constant-pressure heat capacity have been
computed and tabulated for the temperature range from 300 K
to 6000 R for the N02 (g) ion* {Author abstract)#*
C2517
D. narsh and J« Heicklen
FH0T00XID AT ION OF PERFLOOROETHfL IODIDE AND PBRFLOORO-N-PROPYL
IODIDE. Aerospace Corp., El Segundo, Calif., lab.
Operations. Apr. 1966. 11 pp.
DDC: AD !»8391«J
Perfluoroethyl iodide and perflucro-n-pcopyl iodide were
photolyzed in the presence of oxygen. In both cases, the major
product is CF20. In the C2F51 system, it is produced with a
quantum yield of about 2.0. CV3CF0 is also produced, but is
100 times less important. With HI present, the oxidation is
drastically modified, and the H02 intermediate must live at least
10 to the 7th sec. (Author abstract)ft
02528
T. F. Thomas aad C. Steel
PBOTOIfllTIATIOH OF UNIHOIECOLAB REACTIONS. THE PHOTOLYSIS CF
2,3-DIAZABICYCLO (2. 2.1) HEPT-2-ENE.. J.. Am. Chem. Soc.
87, <23) 5290-3, Dec. 1965
The gas-phase photolysis of 2,3-diazabicylo(2.2.1)hept-2-ene (I)
with 337-millimicrons light has been investigated in the pressure
range 10-1000 microns. The variation in the yields of hydrocarbon
products, bicycle(2.1.0) pentane <11} , cydopentene (III), and
1,3-cyclopentadiene (IV), with pressure is consistent with the
initial formation of "hot" II which can either be deactivated or
isomerized to "hot" III. The latter can either undergo
unisolecular decomposition to yield IT or be deactivated.
Changing the wave length of irradiation from 313 to 33ft
millimicrons changed the relative yields of the products in a
manner consistent with this "hot" molecule mechanism.
-------
02531
R., So Johnston and J.. Heicklen
PR0TCCHEHICAL OXIDATIONS. Ill, ACETONE- Jo An.. Chenu
Soc. 86, imS-SU, Oct.. 20, 1964.
The tocii-temperature photocxidation of acetone (0..25 to 17 nm.)
in oxygen (0.09 to 9«7 mm.} with continuous UV radiation above
2200 A. was studied by the method outlined in. part I of this
series; observations were made by leaking the reaction mixture
directly into the electron beam of the mass spectrometer during
photolysis., The principal products of the reaction were H2C0,
H20 CH30H, and CH300H; minor products were CH3COOH,
HC30OCH3, and higher molecular weight products which were
probably CH3COCHO and CH3C0CH20B.. Eecause of the
cracking pattern of the reactants, it was impossible to establish
the presence or absence of CHI, C0# CH2C0, and CO2.
From the identified products at least 1ft free radicals are
inferred to be intermediates in this system.. An exhaustive and
impartial examination of all possible radical-radical
disproportionation and recombination reactions indicates that the
data excluded a large number of possible reactions but that 140
reactions could still be occurring* Formaldehyde, so far as
these studies gc, could be formed by 39 different reactions.
Thus, this experimental method cannot give a complete mechanism,
nor can any method that simply analyzes all molecular products.
(Author abstract)##
02535
H. s» Johnston and J. Heicklen
PHOTOCHEMICAL OXIDATIONS.. IV. ACETAIMHTDE. J. Am. Chem.
Soc.. 86, 4254-8, Oct„ 20, 1964..
The rocm-temperature photocxidation of acetaldehyde (0.4 to 18
mm-) in oxygen (1»0 to 9-2 nm.,) with continuous uv radiation above
2200 A was studied by the method outlined in part I of this
series. Observations were made ty leaking the reaction mixture
directly into the electron beam of the mass spectrometer during
photolysis. The principal products of reaction were CH30H
and presumably CO and C02; other products were H20, CH20,
HCOOH, CH300H, CH3C00H, CB300CH3, and probably
CH3C (0)OOG. Because of the cracking pattern of the
reactants, it was impossible to establish the presence or absence
of CH4, CH2CO, CO, and C02.. Oxidation of the primary
radicals, CH3 and HCO, leads to CH300, CH30, HO, and
B02, and probably HCO(00| and HCG0n. There are at least six
radicals in this system that can disproportionate in 36 ways and
undergo other reactions. Thus this reaction is much too
complicated for its mechanism to be revealed merely by analysis of
all products, (Author abstract)*#
M. Basic Science and Technology
Itoi
-------
02731.
PARTIAL OXIDATION PRODUCTS FORMED DURING COMBUSTION (SIXTEENTH
PROGRESS HEPT- JULY 1 TO DEC. 31, 1966.) California Inst* of
Tech., Pasadena, chemical Engineering Lab. 1966. 16 pp..
During the period covered by this report, primary effort was
directed to the investigation of the effect of the nature of fuels
upon the formation cf the residual quantities of the oxides of
nitrogen and upon the microscopic nature of the perturbations
resulting therefrom. Tables summarize results of these studies.
Table I sets forth the experimental conditions in connection
with the investigation of the behavior of the propane-air and the
n-butane-air system. In Table II, the composition of the
reaction products of the ethane-air system propane-air and
n-butane-air systems are summarized. The analysis of the
perturbations in normal stress obtained in connection with the
propane-air and ethane-air systems is given in Table III.
Plans for continuation of these studies upon the renewal of the
Public Health Service Grant So. AP-00108-08 are discussed.
02761
H-H. Reamer B. H. Sage
OSCILLATOR'S COMEUSTIOB AT ELEVATED PRESSURES- Preprint., 1966.
The effect of combustion conditions upon the magnitude of the
perturbations in normal stress and in total light intensity
have been investigated in a cylindrical combustor 1„0 in. in
diameter and approximately 24 in. in length. The results
are presented in graphical and tabular form. The quantities of
oxides of nitrogen for a number of combustion conditions have been
included.. {Author abstract)*#
C2788
G. A.. LutZ
PHOTOCHEMISTRY - A GROWING TECHNOLOGY. Battelle Tech. Rev.
15 (11) 11-5, Nov. 1966,,
This discussion has reviewed some of the technological
achievements that are making photochemistry increasingly important
as a production tool. The article has also demonstrated that
photochemistry has developed into a methodology of delivering exact
amounts of energy that can be used for chemical syntheses, some of
which are now the bases of industrial processes. A critical
appraisal of the current research effort, and of the developments
and processes that have emerged, suggests that photochemistry will
be of increasing significance in a number of industrial fields.
Thus, it will be important in the manufacture of new chemicals and
chemical intermediates for fibers, foods, drugs, solvents
catalysts, polymers, and insecticides, and for chemical processes
useful in information copying, storage, and retrieval systems.it
1102
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
02817
S. G.. Cohen
ACTION OF MEECAPTAH AND DISULFIDE IN HYDROGEN ATOM EXCHANGE
REACTIONS. Brandeis Univ.,, Haltham, Bass,, Dept. of
CHEMISTRY (REPT. NYO-2499-16„) BAY 24« 1965. 25 PP.
CFSTI NYO 2199-16
Bercaptan and disulfide forn systems very effective in
transferring hydrogen atoas to and from free radicals with rate
constants of 0.001 - 0«0001 H/sec. Photochemical and high energy
radiation processes nay convert an initially stable system to one
containing free radicals formed by transfer of hydrogen atoms froa
one molecule tc another. Thus both combination and
disproportionation of the reaction, K plus NH2 yielding HH
plus NH, radicals are thernodynanically favorable processes* but
combination reactions lead to the usually observed products.
When mercaptan and disulfide are present, they lead to the
disproportionaticn products, returning the system to its initial
state. Being used repeatedly, each HH. plus AS yielding fl
plus ASH yielding NH2 plus AS. aolecule of sulfur compound
nay negate the consequences of aany quanta, or afford protection
against radiation damage. They nay also lead to products
different frcB both the starting aaterials and the usual products.
In free radical and photochemical systeas in which transfer of a
hydrogen atom is a chain-propagating step and radical combination
is terminating, the aercaptan disulfide may provide striking
catalysis, in all cases* the reactions of the sulfur coapouads do
not exclude the usual reactions but are competitive with the a-
(Author conclusions modified)»#
02837
C. S„ Tuesday
THE ATMOSPHERIC PHOTOOXIDATION OF TBANS-BDTEBB-2 ASD NITRIC
OXlDSfl General Rotors Research labs., Barren, Rich. 1961.
35 pp., (Presented at the international Symposium on Chemical
Reactions in the lower and Opper Atmosphere, San Francisco,
Calif-, Apr. 16-20, 1961.)
To elucidate the mechanism of the atmospheric photochemical
reactions of olefins and nitrogen oxides, the reactions that occur
upon the irradiation of oxygen-nitrogen mixtures containing several
parts per millicn of nitric oxide ^nd trans-butene-2 were
investigated. Trans-butene-2 was nsed as a model olefin because
of its symmetry and relatively rapid reaction rate. The effects
of several variables on the rates of trans*butene~2 disappearance
and nitrogen dicxide formation were determined together with the
effect of these variables on the concentrations of reaction
products. Reaction variables investigated include nitric oxide,
nitrogen dioxide, trans-butene-2, and oxygen concentrations as
well as light intensity and total pressure. A reaction scheme is
proposed to rationalize the observed effects these reaction
variables have on the rates of trans-butene-2 and nitric exide
M. Basic Sconce and Technology
1103
-------
photooxidation and on the concentrations of reaction products.
The experimental results support the general conclusion that a
free radical chain reaction initiated by the reaction of oxygen
atoms with trans-butene-2 is very important in the atmospheric
photo-oxidation of trans-butene-2 and nitric oxide.##
02838
9. A. Glasson, and C. S. Tuesday
THE ATHOSPHEBIC THEHMAL OXIDATION IN NITHIC OXIDE. General
Motors Research labs., Darren, Bich. 1963. 14 pp.
(Presented in part at the IttHth National Meeting, American
Chemical Society, Los Angeles, Calif., Apr. S, 1963.)
The kinetics of the thermal oxidation of NO in oxygen nitrogen
mixtures have been determined in the parts-per-nillion range by
long-path infrared spectrophotometry. The results of this
investigation indicate that the reaction is second-order in NO,
first-order in oxygen, and independent of the concentration of
added N02, with a third-order rate constant, at 23 C, of
1.57 (plus or minus .09) times 10 to the minus 9 power per
(sq ppm - mnj« It is concluded that the kinetics of the thermal
oxidation of NO are adeguately described by a simple third-order
rate law and do not require the complexities suggested by
Treacy and Daniels. In addition, it was found that there is
no effect on the rate of the thermal oxidation due to either
{a} addition of several olefins or |b) photolysis of the product
N02. (Author abstract)##
02851
E. B.. Stephens
THE BOLE OF OXYGEN ATOMS IN THE ATHOSPHEBIC BEACTION OF OLEFINS
WITH NITRIC OXIDE. Intern. Air Hater Pollution 10,
(11-12) 793-803, Dec. 1966.
The photoconversion of nitric oxide to nitrogen dioxide in the
presence of olefin at low concentrations in air was studied with
two objectives: (1) to test the hypothesis that oxygen atoms
ace the principal reagents attacking the olefin in the absence of
ozone; and (2) to determine the average number of nitrogen dioxide
molecules formed for each molecule of olefin consumed to see
whether the conversion has the aspects of a chain reaction. On
the basis of the O-atomshypotheais it is predicted that the
rate of oxidation of a given olefin should be proportional
to the produce of the light intensity and the nitrogen dioxide
concentration. It should not be affected by the addition of
a second olefin. This was found to be nearly true for a wide
variety of reaction conditions. About one to two nitrogen
dioxide dioxide molecules were formed for each iiolecule of propene
oxidized.##
1104
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
02853
Y„ Masuda, M. Kuratsune
PHOTOCHEMICAL OXIDATION OF BENZO(A) PYRENE. Intern.. J, Air
Rater Pollution (Presented at the 23rd Annual Meeting,
Japanese Cancer Association, Tokyo, Japan, Nov. 11, 1964.) 10
(11-12) : 805-11, Dec.. 1966.
Benzo(a)pyrene dissolved in benzene was irradiated by UV
light of wave length greater than 280 millicrons.. Oxygen
was present in the benzene. The irradiation product was
fractionated by aluiina coloan chromatography, isolating
three crystalline compounds. These compounds were determined
as 6,12-benzo(a)pyreneguinone, 1, 6-benzo(a)pyreneguinone and
3,6-benzo(a)-pyrenequinone by their melting points, data of
elementary analysis, and IB as well as UV absorption
spectra. AA##
02899
J. F. van der Hal
CONCENTRATING DILUTE AEROSOLS BY ELECTROSTATIC HETHODS.
National Defence Research Organization TNO, Rijswijk,
Netherlands, Cheiical Lab. (Rept. 1966-12.} 20 pp., June
1966.
DDC AD 488229
A first attempt was made to develop a method by which aerosols can
be concentrated, using electrostatic principles. Plastics were
given an electrostatic charge by sudden removal of the plastic from
a high voltage source. The aerosol was precipitated on the
charged plastic. The concentration of the precipitated aerosol
was determined with an electron-microscope. The reproducibility
of this tentative method is reasonably good, compared with methods
based on other electrostatic phenomena. In the present stage, the
method is insufficiently sensitive; this might be improved by
optimalization of the experimental conditions. (Author summary)#*
02904
A. Goetz
HETHODS FCH MEASURING PARTICLE COMPOSITION IN PHOTO-ACTIVATID
AEROSOLS . J. Air Pollution control Assoc. 14, (6) 213-9,
June 1964, (Presented at the 56th Annual Meeting, Air
Pollution Control Association, Detroit, Mich., June 9-13,
1963-)
Author discusses the basic processes and mechanisms which cause
the photochemical formation of aerosols, that is which effect the
conversion of certain atmospheric constituents from the gaseous
into the aerocolloidal state. Author demonstrates that it is
M. Basic Science and Technology
1105
-------
possible to study the formation and decay of such aerocolloidal
systems in considerable detail, particularly as to the quantitative
relationships between the photochemical partners.##
03009
P„ de Kayo
THE PHOTOCHEMISTRY OF UNSATURATE SYSTEMS CONTAINING HETEHO ATOflS
OTHEF THAN OXYGEN (PINAL KEPT® SEPT.. 1965-MAY 1966)..
Western Ontario ODiv„, London, Canada, Dept.. of
Chemistry. 6 pp.# 1966
This report presents a summary of a study of the products and
mechanisms of reactions wherein unsaturated systems containing
nitrogen or sulfur are photolyzed. Included are studies of
(1) the photocheaical Beckmann rearrangement, (2) the general
heteroaton transfer, <3) coumalin dinerization, and (4) the
photolytic decomposition of B-ketosulphones.##
03016
J.. F. Kelso
THE PHODOCTION OP ATOMIC OXYGEN BY THE THERMAL DECCBPOSITION OF
OZONE- Ballistic Besearch Labs.., Aberdeen Proving
Ground, Hd„, interior Ballistics Lab.. (BRL dept. No.
1323) 2H pp., June 1966
To study the reactions of atonic oxygen it is desirabe to have
a supply that is free of metastable energetic species of
molecular and atomic oxygen which are formed in discharged
oxygen and because fo their side reactions can lead to serious
errors in calculations. Therefore, the homogenous, thermal,
gas phase decomposition of dry ozone was tried and found to be
a satisfactory source if the residence time of ozone in the
furnace is carefully regulated by furnace length and carrier
gas flow, followed by rapid cooling of the products of
decomposition- (Author abstract}##
030 20
E. Hiescher
ANALYSIS OF THE SPECTBUB Of TBE NITRIC OXIDE MOLECULE
(1INAL SCIENTIFIC BEPT.}.. Basel Univ., Switzerland, Inst*
of Physics. (Bept. No. ATCHL-66-U40) 7 pp. Bar. 31, 1966.
The experimental studies of the spectrum of the NO molecule are
reviewed. A short description cf the observed 3 delta states
and of Bydberg-complexes is given. Problems left for future work:
on the NO spectrum are discussed.##
1106
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
03066
D. Durant and G» P. HcHillan.
ENERGY DISTRIBUTION OF PHOTOCHEMICAHY GENERATED T-PENTOXY
RADICALS.. J„ Phys« Chen. 70 |9) 2709-13, Sept. 1966.
Previous studies on excited alkoxy radicals formed in
photochemical processes were extended to the t-pentoxy species,
which is Hell known to decoapose by two parallel paths. The
ratio of rate constants k sub 1/k sub 2 was estimated to be 10fc at
114 degrees froi experiaents on pyrolysis of t-pentyl nitrite..
For radicals foraed by photolysis of this compound, k sub 1/k sub
2 depends strongly on the absorbed wavelength but does not reach
the expected liiiting value of 104 at the longest wavelength
which could be studied. The dependence of quantum yields at
3660 A on pressure of an added scavenger, nitric oxide, showed
that the k sub 1/k sub 2 obtained frca photocheaical experiments
could be accounted for quantitatively by a contribution from
excited radicals and a contribution identical with the ratio for
unexcited radicals, obtained from pyrolysis experiments. These
results provide United justification for the "alpha method" often
used in kinetic treatment of excited radical effects.
Quantvm-yeild measurements at high pressures of added nitric
oxide suggest preferential removal of excited radicals of lower
energy and disclose a bread energy distribution of the excited
radicals. {Author abstract)#*
03107
R.W. Boubel I.A. Ripperton
OXIDES OF NITROGEN AND tJNBURNBD HYDROCARBONS PRODUCED DURING
CONTROLLED COMBUSTION. J. Air Pollution Control Assoc. 15,
(6) 270-3, June 1965.
A diffusion flame burner was operated to determine the effect of
several parameters on the quantity of NOx and unburned
hydrocarbons produced* The statistical analysis indicated
the unburned hydrocarbon eaissions to be dependent upon the
rate of heat release in the system, the amount of excess
combustion air, the fuel molecular structure, and the
interaction between the fuel structure, and the amount of excess
air. The NOx emissions reached a maximum at the conditions
which yielded minimum unburned hydrocarbon emissions. Multiple
regressions were made which yielded predicting equations for
both the unburned hydrocarbon and the.*
SOx for the apparatus used- (Author abstract]##
03im
B.A. Glasson C.S. Tuesday
HYDROCARBON REACTIVITY AND TBI KINETICS OF THE ATHOSPHBRIC
PHOTOOXIDATIOM OF NITRIC OXIDE. General Motors Corp.,
M. Basic Science and Technology
-------
Barren, Rich., Fuels and Lubricants Dept. (Research
Publication GHH-586) Aug.. 15, 1966. 23 pp. (Presented at
the 59th Annual Meeting, Air Pollution Control
Association, San Francisco, Calif., June 20-24, 1966.)
The reactivity in the atmospheric photooxidation of NO has
recently been determined for a large number of hydrocarbons. To
aid in the application of these hydrocarbon reactivity
measurements, the kinetics of the atmospheric photooxidation
were studied. The hydrocarbon investigated covered a vide
range of reactivities and structures and included: 2,3-dinethyl-2-
butene, 2-methyl-2-butene, 2-methyl-t-pentene, propylene,
sesitylene, and n-hexane. The rate of NO photooxidation
increases less than linearly with hydrocarbon concentration for
all the hydrocarbons studied. The degree of non-linearity,
however, varied vith hydrocarbon structure and
reactivity. The effect of the DC and the N02
concentrations on the rate of NO photooxidation also depended
somewhat on hydrocarbon structure and reactivity. For all of
the hydrocarbons studied, however, the NO photooxidation rate
increased linearly with increased light intensity. The effect
of complex hydrocarbon mixtures on the rate NO photooxidation
was investigated using 3 commercial gasolines. The NO
photooxidation rates measured for these mixtures agreed within
experimental error with calculated rates based on
chromatographic analyses of the gasolines and the reactivity in
NO) photooxidation of the individual hydrocarbons in the
gasolines. {Author abstract)##
03149
S. An Clough and F. X. Kenizys
C0RI0LX5 INTERACTION IN THE ND1 AND N03 FUNDAMENTALS OF OZONE.
0. CHEB- PHIS- <{29 1855-61, BAR. 1, 1966.
CFSTI, DEC AD 638825
The du sub 1 and nu sub 2 vibration rotation spectrum of ozone in
the 9«0 aicron region was analyzed. The 2 vibration states are
coupled through a Coriolis tern, iY sub 13P sub y, and a
second-order distortion term# -X sub 13 (PsubxPsubz plus
PsubxPsubzPsubx), in the Hamiltonian. The interaction was
treated by numerically diagonalizing the secular determinant for
the 2 states with the coupling included. The effect of the
interaction of the intensities was considered and absorption
contours calculated in satisfactory agreement with experiment.
Rith the distortion parameters fixed to the groundstate values,
the constants were obtained.##
03150
CATALYTIC COHBtSTICN OF CABEON BCBCXIDE ON COPPER 07IDE (EFFECT
OF VATS8 VAPOR)« Ind. Eng. Che*, Process Design
Develop. 5 (3) 214-7, July 1966.
1108
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
The effect of water vapor on the catalytic combustion of carbon
monoxide on copper oxide was investigated. The water vapor
content in the carrier gas stream was varied from 0 to 3000 pprc
with the total gas flow maintained constant at 400 hr (NTPJ at
temperatures ranging from 70 to 130 C., The initial concentration
of carbon monoxide was varied from 500 to 1500 ppm. The reaction
was first order for water vapor concentrations of 300 ppm* and
above and 0*U order in the absence of water vapor. The combustion
rate of carbon monoxide was strongly affected by small changes
in water vapor concentrations when the total water vapor content
was less than 800 ppm. {Author abstract)##
03160
Kimura o. Tada, K. Kunotsuki, and K. Nakaaki
ON THE GENEBATIOH OF S0LFDFIC ACID BIST FHOM S01FUH DIOXIDE IN THE
ATMOSPHERIC AIB. J. Sci. labour 41, (10) 510-11, Oct- 1965.
Experimental studies are reported on the simulated oxidation of
sulfur dioxide in atmospheric air* It was observed that the
higher the air current velocity, and the higher the relative
humidity, the more marked the decrease of S02 concentration.
Sulfuric acid studies showed that it is produced by oxidation of
S02 in the air and that the coexistence of N02, 03 or H202
enhances the production of H2S04. Microscope studies of the
sulfuric acid list formed by S02 oxidation revealed that the
presence of particulate natter contributes to the formation of the
acid mist. Electron microscope studies substantiated experimental
results by showing that samples of city air contained particles
similar to sulfuric acid mist particles obtained experimentally..##
C3177
H. Sjogren
FOFMATIOM O? CARBON DIOXIDE JOltS AFTSH E1ECTB0N ABB ION IMPACT.
Boyal Inst, of Tech., Sweden, Dept. of Physics. March 15,
1966. 18 pp.
The ionization of C02 was investigated in a double mass
spectrometer, and the breakdown graph was constructed. The
appearance potential of o plus formed in dissociative charge
transfer is shown to be 22-4 eV, while the electron impact value
is 19.5 eV. The discrepancy is explained according to
Higner-Vitmer correlation rules. A break in the electron
impact ionization efficiency curve is explained as being due to
charge exchange between CO plus ions, formed in the
dissociative charge transfer, and C02. (Author abstract}*#
M. Basic Science and Technology
-------
03179
I. Spialter and J.. D.. Austin.
THE CLEAVAGE OF SILASES EY OXIDES OF NITROGEN- J. Am.. Chem.
SOC,, 86, 1828, 1966.
CFSTI, EDC AD 638836
The cleavage of silanes by oxides of nitrogen is reported.
Triethylsilane reacts excthermally with N02 to yield
triethylsilanol and hexaethyldisiloxane. In a separate
experiment, under similar conditions, triethylsilanol readily
gave the dehydration product, hexaethyldisiloxane. The
silicon-silicon bond in hexamethyldisilane is also cleanly cleaved
by No 2 to hexamethyldisiloxane in 95% yield- Rupture of the
silicon-alkyl bond was observed when tetraethylsilane was allowed
to react with N02. The principal products obtained were
hexaethyldisiloxane and acetic acid. Under similar conditions,
hexaethyldisiloxane yielded hexaethylcyclotrisilcxane,
octaethylcyclctetrasiloxane, and octaethyltrisiloxane. The
silicon-aryl bond was also cleaved in trimethylphenylsilane by NO
2 to produce hexamethyldisiloxane and nitrobenzene- When all of
the phenyl group had been removed from silicon, the vapor phase
chromatogram of the crude reaction product did not show the
presence of any polysilcxane components other than the disiloxane.
The rate of cleavage of an ethyl group from hexaethyldisiloxane by
N02 was slow compared to that from tetraethylsilace. However,
all other cleavage reactions proceeded readily and with
exothermicity at room temperature to give reaction products in good
<90*) yields. NOo cleaved triethylsilane to triethylsilanol at
room temperature., MO also produced the silanol with complete
reaction in less than 6 ht, whereas N20 gave only 10* conversion
after 6 hr» It appears that the oxides of nitrogen behave
similarly toward organosilanes, but with differeing degrees of
activity, i.e., in decreasing order of reactivity, NOx, N03,
NO, and much slower N20»#1
03184
An Y. Dng and H. I. Schiff-
THE PHOTOLYSIS OP C02 AT 170 A- Can. J. Chem. 44, 1981-
91, 1966.
The apparatus used to study the photolysis contained a
collimatlng region which minimized the effect of divergent light,
and permitted the temperature of the cell and lamp to be controlled
separately.. Analytical sensitivity was such that conversions less
than 0..2X were possible. Although CO and 02 were the only
stable products, the CO/02 ratios were higher than those
required by mass balance. The product yields were found to be
independent of C02 pressure and to be linear with irradiation
time at 25 c„ At higher temperatures the quantum yields
decreased and at 200 C were no longer linear functions of
mo
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
irradiation time. The 02 yields decreased when CO Mas added,
the effect increasing with teaperature. The overall guantum
yield was less than unity. Reactions were observed with CH4,
H2, and H20 when these vere added in snail amount. These
results indicated the presence of a reactive species* capable of
promoting back reactions and of being adsorbed on the walls. A
mechanism is suggested which best fits the results and which
postulates C03 as the reactive species. (Author abstract)##
03186
G. wettermark.
HIGH INTENSITY PHOTOLYSIS STUDIES OP ACETONE AND SOBE ALIPHATIC
ALDEHYDES- Arkiv Kemi 18, (1) 79, Apr. 12, 1961.
CFSTI, DDC AD 639939
The vapor phase photolyses of acetone, acetaldehyde,
propionaldehyde, n-butyraldehyde end isobutyraldehyde were
investigated at very high light intensities. High intensity flash
light sources were used. Analyses for all major products were
made on samples which were exposed to unfiltered light ia a
cylindrical reaction vessel, in the present case 1800 joules were
discharged in this apparatus, giving absorbed intensities of the
order of 10 to the 25th F°*er guanta/sec/liter with a flash period
of 10 nicrosec. The stoichiometry of the products showed that all
important constituents were Measured. By using a very intense
point-discharge, quantum yields for the formation of the main
products were determined in parallel light. The samples
absorbed light in the absorption band around 280 aicrosec.
Flashes of 100,000 joules, which gave absorbed intensities of the
order of 10 to the 29th power guanta/sec/litre were used
throughout. The absorbed light dose vas calculated from a
knowledge of the various quantities involved. Thus the spectral
distribution of the light emitted from the discharge was
determined. in all cases the samples were subjected to one
single flash. The product yields were determined by gas
chromatography using a flame ionization detector or a high
sensitivity thermal conductivity detector. Helium was added in
some experiments in order to deternine the influence of the
reaction temperature on the product yields* It was found that
reactions which are first order with respect to radical"
concentration could be satisfactorily eliminated. This resulted
in a striking simplification of the reaction schemes and has led to
new information concerning the primary photochemical mechanisms and
the reactions of the formed radicals.#!
*
03343
HYDF0CA8B0M - AIR FOIL CUIS {SBEX-AN80AL TECHNICAL SOHWART
REPORT NO. 9f J AH. 1 - dOli 30, 1966)* General Electric
Co., tynn, nass„
-------
directed towards the understanding of the complex processes
occurring at hydrocarbon anodes. Surface species were identified
as partially dehydrogenated radicals derived from fuel, cracking
products and partially oxygenated species* Some are particularly
refractory and contribute to limitations on performance. In all
cases, the anodic performance is strongly influenced by the
adsorption rate, the ability of the catalyst to promote
cracking, and the reaction of C{1) radicals with water.
Accumulation of the refractory species results in the lowering
of maximum currents. For economic reasons, long term goals
indicate the use of non-platinoid electrocatalysts in fuel cell
electrodes. At present, work is being concentrated on more
effective utilization of the noble metals, especially Pt, Pt-Ru,
Pt-Ir, and ternary alloys of Pt, Bu and Au were evaluated as
high area catalysts in thin porous electrodes, with 85* H3P04
electrolyte, and propane and octane fuels. None showed
significant improvement over Pt used alone. Better results with
these alloys were obtained with H2-C0 fuel mixtures.
Electrodes: Emphasis in this area is on the development of
electrode structures which employ the catalysts developed from the
above mentioned research. Basic electrode structure is the thin
proous Niedrach-Alford types, Hajor effort was directed toward
B4C supported catalysts. Rulti-Component Fuels: Plans are to
include research on mixtures of saturated hydrocarbons, olefins,
aromatic hydrocarbons as well as the reference fuel of octane.
Electrolytes: The principal electrolyte has been concentrated
H3P04. HP was used as an alternate electrolyte and did not
show the same tendency to cycle as the H3P04 electrolyte.##
03349
I.. Cu Hisatsune.
STRUCTURES OF SOME OXIDES OF HITBOGEN (SOHMAHY PBOGBESS SEPT.
OCT. 27, 1965 - DEC. 31, 1966). Preprint. Dec. 31, 1966.
The kinetic study of the third order reaction between NO and
02 was completed* Partial pressures of MO and 02 were varied
from one to 200 mm and one to 170 mm respectively, and mole ratios
of these reactants were chosen so that the final partial pressures
of the reaction product N02 were between one and 14 mm.
Nitrogen gas was used as diluent in order to maintain essentially
a constant total pressure (near 480 mm) during the reaction. The
reaction was followed by recording the changes in the absorption
intensity of the 1640 cm-1 N02 IS fundamental band* Kinetic
runs were made with one reactant in excess, and the resulting
experimental data gave pseudo first or second order rate plots
which were linear over 80 to 90 percent of the reaction. The
temperature dependence of the rate constants was studied between 4
and 55 C. In this case, both the reaction cell and the reactant
storage bulbs were maintained at constant temperature. From the
tabulated experimental data a rate constant foe this third order
reaction was obtained: k ¦ (6.18 + or - 0.20)x103 exp<+0„50 + or -
0.40 kcal/mole)/BT) liter 2 / mole 2 -sec where the estimated
uncertainties are maximum errors. Kinetic studies on the
H0—C12 and N0-Br2 systems were initiated. In the case of the
chloride system, the reaction was found to be influenced by
fluorescent light but not by the IB light source. Tentative
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
values of the rate constant at 22.7 C were found to be 19.6 + or -
0.7 and (7..92 ~ or - 0.42) * 1000 liter 2/mole 2 - sec respectively
for the chloride and the bromide.*#
03356
A. H. Taylor
OZONE PREPARATION AND STABIIITY IN HIGH CONCENTRATIONS (VOLUME
2 BIBLIOGRAPHY) (FINAL SEPT.). Air Reduction Sales Co»,
Murray Hill, N.J., Dept. of Research and Engineering.
Sept* 22, 1949.. 234 pp«
CFSTI, DDC 639200
The literature references and abstracts which are assembled in
this bibliography have been located through formal searches of
abstract journals listed in the appropriate Table below, and in
general are limited (a) to those appearing during the last third
of the century of active interest in ozone, and (b) to selected
topics of immediate application. It was apparent at the outset
that much of the early work would either be superseded by more
accurate observations or be guoted by later workers. It was
also expected that if use should indicate the advisability of so
doing, additional material could be added at will to a bibliography
which was flexible in arrangement, in its present state of
development (Sept. 22, 1949) the ozone bibliography represents a
careful formal search of the Chemical Abstracts Indexes from
1917 through 1948 plus searches in the individual numbers which
have appeared thus far in 1949. Since insufficient information on
the toxicity of ozone was available solely fcon Chemical
Abstracts, additional searches back to 1910 were made in the
various aedical abstract journals. In the course of the above
efforts and by legacy from previous searches, a number of earlier
and pertinent references have been obtained and are included.
(Author introduction modified)*#
03361
B. H., Sage
FORMATION OF OXIDES OF NITROGEN DURING COMBUSTION AT ITHOSPHEHIC
PRESSURE. Preprint., 1966..
Experimental measurements were made of the perburbations in
monochromatic and total optical intensity. Supplemental
measurements of the perturbations is normal stress were nade. All
of the aeasureaents were carried out at a natural gas mixture ratio
of approximately 0.88 stoichioaetrlc. The composition of the
products of reaction is set forth. The aole fraction of oxides of
nitrogen as well as the principal components including carbon
dioxide, oxygen and carbon monoxide are included. A significant
variation exists in the perturbations in noraal stress and in
monochroaatic intensity with respect to tine. The perturbations
in monochroaatic intensity see* to undergo more
variation than do the perturbations in noraal stress* For the
most part the frequency of the perturbations in noraal stress and
M. Basic Science and Technology
-------
in monochromatic intensity, corresponding to the wavelengths of
carbon dioxide and water, is substantially egual. A limited
number of measurements were made in the upper part of the coabustor
with regard to the perturbations in optical intensity.. The
relative magnitude was comparable to the perturbations encountered
near the flameholder^ Comparisons are presented of the
perturbations in normal stress and the perturbations in
monochromatic intensity corresponding to the emission of carbon
dioxide at two different time scales. The variations in the
stability of the two types of perturbations are markedly different.
The frequencies of these perturbations are closely allied and
appear to offer credence to the assumption that they are directly
related. A similar comparison is made for the perturbations in
monochromatic intensity of the wavelength corresponding to the
emission of water» Again, the irregularities of the fluctuations
in the nature of the perturbations in monochromatic intensity, as
compared to the relatively regular perturbations in normal
stress, are evident-##
03428
C.. S. Tuesday,,
THE ATMOSPHERIC PHOTOOXIDATICS CF OLEFINS: THE IFFICT OF
NITROGEN OXIDES. General Hotcrs Research Labs, Warren,
Mich., 1961, 25 pp. (Presented at the Conference on Hotor
Vehicle Exhaust Emissions and Their Effects, Los Angeles,
Calif., Dec. 5-7, 1961.) (Bept. No. GHS-355.)
The role of the oxides of nitrogen in the atmospheric
photooxidation of olefins was further investigated. A previous
study from this laboratory indicated, among other things, that the
photooxidation of trans-2-butene was both promoted and inhibited
by nitric oxide depending upon the concentration. To explain and
extend this observation, the effects of various concentrations of
NC2 and NO on the photooxidation rates of propylene,
isobutene, trans-2-butene, and 2,3 dimethyl-2-butene were
determined together with the effects of NO concentration on
reaction products. The olefins investigated differed not only in
photooxidation rate for a particular N02 concentration but also
in the dependence of this rate on the initial concentration of
N02. Initial increases in N02 concentration increased the
photooxidation rate of all the olefins studied. When the initial
N02 concentration was increased further each olefin behaved
differently. The photooxidation rates of trans-2-butene and
tetramethylethylene increased with increasing concentrations of
NO up to a maximum rate. Further increases in the initial
concentration of NO reduced the photooxidation rate of both these
olefins,. Further increases in NO concentration inhibit the
olefin photooxidation rate by decreasing the concentration of ozone
and the rate of the ozone-olefin reaction* The decreased rate of
ozone plus olefin reaction also decreases the rate and amount of
compound X formation since compound X is apparently formed by
further reactions of some of the products of the ozone plus olefin
reaction. The role of the oxides of nitrogen in the atmospheric
photooxidation of olefins is guite complex. NO promotes or
inhibits olefin photooxidation depending upon the ratio of
reactants.. N02 promotes or inhibits olefin photooxidation
1114
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
depending both on the relative concentration of reactants and the
nature of the olefin.**
03446
B. H. Croon and E. 9. ley he.
THEBHODX8AMXC, THANSPOHT, ADO ftC* PH0P1BTIES JOB THE PRODUCTS
OF HETHANE BOBBED IN OXIGEN-SNBICHED AID* National
Aeronautics and space administration, Langley Station
Haaptoii, Va.., Langley Research Center. (Bept. No. NASA
SP-3035.) 1966. 90 PP.
CFSTI, NASA: SP-3035
In testing materials for resistance to extremely high-temperature
oxidizing environdents, large-scale hypersonic test facilities for
simulating flight environments to which some of these materials may
be exposed are used. Combustion heating of a high-pressure
airstrean is one of the approaches used in this simulation. It is
scaetiaes desirable to Maintain burning in a test gas in order to
deteraine the effect of oxidation on materials in the test gas-
As combustion-product oxygen percentages approaching those in air
(20* by vol) are required, the need for data on the properties of a
combustion-heated, oxygen-enriched test medium is obvious. The
present paper presents results of the data obtained on the
properties of nethane burned with oxygen-enriched air. These
include calculations to deteraine the composition and the
thermodynamic, transport* and flow properties (including noraal-
shock properties) of gas aixtures. These properties are computed
for sethane burned in ait enriched vith oxygen so as to aaiatain
approximately 20% oxygen in the conbustion products. Results are
presented for egulvaleace ratios of 0-315, 0.380, 0.425, 0.480, and
0.525, for pressures varying fro* 0„0001 to 1000 atmospheres and
for temperatures froa 100 B f56K) to 6000 B (3300K). fAnthor
symmary) *1
03464
B. Gorden* Or. and ?. Ausloos
VAPOR-PHASE PHOTOLYSIS 07 IOBHIC ACID. J* Phys. Chei. 65,
1033-7, June 1961.
The direct photolysis and the photosensitized decomposition of
BCOOH and DCOOH were investigated in the presence and absence
of radical scavengers. The results indicate, in contrast to those
of earlier investigation** that besides reactions I and IX which
involve intramolecular rearrangements HCOOH plus bv equals 920
plus CO (I) and HCOOH plus hv equals H2 plus C02 (II)
radical-producing primary processes *ust be considered as well.
2t will be shown that prccess HC00H plus hv egualsHCO plus
OH is the »ost important source of free radicals in the direct
photolysis of focftic acid. The effect of tetperature on the rate
M. Basic Scltncft and Tectaolo#
1115
-------
of formation of the products was investigated in some detail.
Above 200 degrees three different chain processes vera found to
occur: (aj K plus HC00H equals H20 plus HCO, HCO eguals
H plus CO;
-------
wcrkers to this ion was found to belong to water, but a new
fundamental was observed beyond the spectral range studied
previously. Frequencies of the fundamentals have been assigned
and confirmed by normal coordinate analysis. Some infrared data
on isotopic hyponitrous acids have also been obtained™ The acid
appears to have a C(2h) symmetry in the solid state™ (Author
abstract)##
035221
5. C., Cookson
aSYHWETHIC ELECTRONIC TRANSITIOHS AND PHOTOCHEHISTM. (Final
Technical Status Report). Southampton Oniv., England, Dept.
of Chemistry- Nov. 1965. 1<» pp.
DDC: AD 479 2«I0
Sigma to slgma transitions of organic compounds have been observed
for the first tine in the region of 210 to 260 millimicrons*
Delocalisation of the signa electron requires a chain of H atoms,
the first and fourth having p orfcitals parallel with the sigma
bond joining the second and third- Examples are reported amongst
unsaturated ketones, unsaturated amines and amino-ketones.
The circular dichroism of 3 alpha- and 3
beta-phenyl-2»2 - ethylenedithic-chclestane and of seme conjugated
oximes is reported. The sign cf rotation of the latter depends on
the helicity of the chromophore in the same way as for alpha, beta
unsaturated ketones. DV irradiation of hexamethylcyclohexane -
1,3,5-trione results in successive decarbonylation and
beta-diketone - enol - lactcne rearrangements.. Photochemical
isomerisation of four optically active camphenones involves
intramolecular migration of the carbonyl group from one end to the
other of the olefinic group, converting the bicyclo (2,2,1)
heptenone into the bicyclo 13*2*0} heptenone system. The
photoproducts show the high values of delta E characteristic of
extensive mixing of n to pi and pi to pi transitions. {Author
abstract)##
03551
P.. Ausloos and E.. Burad.
THE FLUORESCENCE AND PHOSPHORESCENCE OF TRIFWJOB ACETONE VAPOR.
0- Phys. Chem. 65, 1519-21, 1961..
The fluorescence and phosphorescene of trifluoroacetone has been
investigated at 2652, 2804, 3025, 3130 and 3341 A* The effect of
concentration and temperature cn the yields of triplet and single-
state emissions are comparable to those observed for acetone. The
emissions from 2-butanone and 2-pentanone have been investigated
briefly- Both compounds phosphoresce very weakly and their
fluorescence yields are nearly identical with those .observed for
acetone and trif luoroacetone.. |Author abstract)##
M. Basic Science and Technology
1117
-------
03559
F. E. Pebbert and P. J, Ausloos.,
COWPXICATIRG PACTOSS IN THE GAS PHASE PHOTOLYSIS OF AZOMETHANE.
J.. Phys. Cheir,. 67, 1925-8, 1963,
In a recent publication of the gas phase photolysis of
azonethane, Toby and Weiss suggested a new ethane-producing
reaction: 2CH3V2 yields C2H6 plus 2N2 (a). On the other
side, Pebbert and Ausloos presented evidence for the formation of
ethane by a unimolecular elimination from azonethane CH3N2CH3
plus hv yields C2H6 plus N2 (b)n The present study was
undertaken in order to determine if the pressure trends observed by
Toby and Seiss could not at least be partly accounted for ty the
occurrence of primary process (fc)» It is thought that an answer
to this question, as well as to other related problems, could be
most readily obtained by photolyzing equimolar mixtures of
CH3N2CH3-CD3N2CD3« It was ccnlcuded that reaction (a),
which has been proposed by Toby and Weiss to account for the
observed pressure effect, has net been clearly established.##
03560
E. Febbert and P. Auslcos..
INTRAMOLEC0LAF FEAFFANGEflENTS IN THE SOIID PHASE PHOTOLYSIS OF
4-B£THyL-2~HEXANONE AND SEC-BOTYL ACETATE. J. Chen. Phys.
37, (5) 115B-9, Sept.. 1, 1952.
The photolysis of
-------
nitrite ace not accurate and shculd be regarded as relative rates,
only. The quantum fields of ethyl nitrite and acetaldehyde
formation extrapolated to zero time are 0.139 and 0-094,
respectively. In the liquid phase at 0 degrees, oxygen is no
longer a product. Ethyl nitrite and acetaldehyde are still the
main products with small amounts of methyl nitrite. The
distribution of products at low conversions is: acetaldehyde,
53.6*; ethyl nitrite, 46.0*; and methyl nitrite, 0„4JE.ti
03563
K. T.. Whitby, D„ A. Lundgren, and R. C. Jordan.
HOMOGENOUS ABROSOL GENERATORS. Minnesota Univ.,
Minneapolis, Dept. of Mechanical Engineering. (Technical
Rept. No. 13.) Jan. 1961. 53 pp.
Two aerosol generators capable of generating essentially
homogeneous, monodisperse, spherical, and electrically neutral
solid particles of dye have bees developed. These are an
atomizer-impactor combination theoretically capable of generating
particles ranging in mass median size from 0.02 to 0.5 nicrons, and
a spinning disk generator capable of generating particles from
about 0..5 to 20 microns in size. Research during the development
of these generators has shown that under many conditions of
operation the particles produced are electrically charged to a
substantial fraction of the maximum equilibrium charge. This
charge is neutralized by a unique ion genrator which reduces the
charge to a few percent of the aaximum. The generators were
developed using methylene bine in water or In ethyl alcohol.
However# due to the aany advantages of fluorescent aerosols, an
effort is being made to adapt the gen?ators to make satisfactory
fluorescent particles, satisfactory particles are now being
generated from a mixture of methylene blue and comeerclal
enerated from a mixture of methylene blue a commercial
uranine dissolved ia alcohol. The sensitivity of modern
fluorescent measuring techniques Is great enough so that these
aerosol genrators may be used to accurately evaluate gas cleaners
at airflows of several thousand cubic feet per minute and
efficiencies of 99.9% or greater. (Author summary)• •
03575
R. R. Austin, R. H. lewis, and R. Donaldson, Jr.
A NEW ATMCSPHEBE IRRADIATION CHAMBER*. Intern! J. Air Water
Pollution «# (304) 237-«6, 1961.
The irradiation of atmospheric saaples of air with ultraviolet
light produces oxidants when hydrocarbons and nitrogen dioxide are
present and thus permits a measurement of the saog-foraing
potential of the air. * new high irradiation intensity chamber
using fluorescent ultraviolet lamps has bees developed. Data are
given for the irradiation of «cne hydrocarbons in air in the
M. Basic Sclwc® and Technology
-------
presence of nitrogen dioxide- Some data are also given for
atmospheric samples. The performance of the new chamber is
compared to that of the fifty-liter chanters which have beet in use
in the past- The chanber vclune is eight liters. Power required
has been reduced from 1600 watts in the fifty-liter chamber to
160 watts- Oxidant levels produced at the same sampling rate on
atmospheric samples are approximately equivalent to the levels
produced in the fifty-liter chaster. (Author abstract)##
036 2t+
S. S* Thomas J. G. Calvert
TUB PHOTOOXIDATION OP 2,2»-AZOISOBOTAME AT 25 C. 0. Am.
Chen Soc. 84, 4207-12, Hov. 20, 1962.
A rate of the photooxidation of 2,2 '-azoisobutane has been made
in an oxygen-rich atmosphere at 25 degrees. Long-path infrared
spectrophotometry was used to identify the major products
of the tert-butyl free radical-oxygen reaction as acetone,
formaldehyde, tert-butyl hydroperoxide and tert-butyl
alcohol; methanol and carbon dioxide were minor products.
Seasonably good mass balances were obtained. From a
consideration of the initial rates of product formation and
a2oisobutane disappearance, a detailed mechanism was proposed.
The results suggested that for this oxygen-rich system at 25
degrees the radical-radical dispropcrtionation reactions are
the origin of hydroperoxide and alcohol products, and that
B-abstraction from azoisobutane, formaldehyde or other H-
containing products in the system was unimportant here. The
rate data are consistent with a value of about 5 sec. for the
first-order rate constant for the decomposition of the
tert-butoxyl radical at 25 degrees. (Author abstract)#*
03682
Fu Altshuller and A. F.. iartburg
ULTHAVIOLET DETERMINATION OF BITBCGEK DIOXIDE AS HXTRITE ION.
Anal, Ches. 32, 174-177, Feb- 1960.
h method for determining nitrogen dioxide concentrations in the
0.01 weight X range and above uses ultraviolet absorption at 355
millimicrons of the nitrite ion formed when nitrogen dioxide is
absorbed in aqueous alkaline solutions of potassium or sodium
hydroxide. The absorption masimun of nitrite ion at 211
millimicrons with an absorptivity of 5800 aole millimicrons liter
cm. offers possibilities for determining nitrogen dioxide
concentrations in the parts per million range. A synthetic
mixture of nitrogen dioxide in nitrogen, in a gas cylinder, was
analyzed by both ultraviolet analysis and a gravimetric procedure
involving absorption of nitrogen dioxide in aqueous potassium
hydroxide solution in a series of bubblers. Grab samples were
absorbed in alkaline solution, and then analyzed by ultraviolet
analysis, the results of the ultraviolet analyses by both methods
of collection were in good agreement* giving a nitrogen dioxide
concentration of 3-4 weight J™ The gravimetric procedure gave
somewhat lower results. (Author abstract)##
1120
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
038071
THE CHLOBINE OXIDATION OF SOIFUF C-CMEOaMDS IN CI LOT I AQCEOOS
SOLUTION.. National Council foi Stream Improvement, Inc.,
New York City. (Atmospheric Pollution Technical Bulleting
18.) June 1963™ 16 pp.
Oxidation of sulfide in agueous solution requires between 2 and
3.4 moles of C12 per mole of sulfide* depending upon conditions
and the fraction of the sulfide oxidized. Oxidation of all the
sulfide present requires at least 2.35 moles of C12 per mole of
sulfide. Sulfate is a major product- Complete oxidation of
methyl aercaptan in neutral or acid solutions requires between 2.4
and 3.3 noles of C12 per Bale of mercaptan. Under basic
conditions, methyl mercaptan apparently reacts to form an
intermediate which, in turn, appears to oxidized by C12 once all
the mercaptan has reacted. Formation of the suspected
intermediate requires some 1.5 moles of C12 per mole of
mercaptan, but a total of about 2.6 moles of C12 per mole of
mercaptan must be added before the first trace of excess C12 can
be detected. All attempts to identify the products of these
reactions failed—probably because the concentrations involved
were below the sensitivity limits of the tests used. Oxidation of
dimethyl sulfide required 1.8 moles C12 per mole of sulfur.
Oxidation of dimethyl disulfide required S.2 moles of C12 per
mole of disulfide—equivalent to 2.6 moles of C12 per mole of
sulfur. All of the C12 oxidations were rapid enough to be
complete before iodine was added. This means that the oxidations
of inorganic sulfides and mercaptans required less than one minute
and oxidation of the organic sulfides took less than five
minutes-tt
03968
Cadle, Richard D. and Hargaret Ledford
THE BEACTION OP OZONE WITH HYDHOGEN SULFIDE. Intern. J. Air
Sater Pollution# 10|1>s25-30, Jan. 1966. 7 refs.
The gas phase reaction of ozone with hydrogen sulfide in a
mixture of oxygen and nitrogen serving as carrier gas has been
investigated. The only products found were sixifur dioxide and
water, and the stoichicsetry corresponded approximately to the
equation: H2S plus 03 yields H2C plus S02. The reaction
kinetics were investigated with a flew system, and a method was
developed Cor titrating with nitric oxide the ozone remaining
after reaction with hydrogen sulfide. The reaction has orders
near zero and 1.5 in hydrogen sulfide and ozone respectively, and
follows a given rate law. It is at least partially
heterogeneous. The results can be used to set an upper limit for
the rate of this reaction in the atmosphere. (Authors" abstract,
modified)#*
M. Basic Science and Technology
1121
-------
03969
J. G. Christian and 0„ E. Johnson
CATALYTIC COHEDSTION OF ATMOSPHERIC CONTAMINANTS OVEB HOPCALITE.
Intern., j„ Air Water Pollution 9, (1/2) 1-10, Feb. 1965,
Catalytic combustion studies shewed Hopcalite, an unsupported
coprecipitate ot copper and manganese oxides, to provide
substantially complete oxidation at ca. 300 c of vapors of several
types of hydrocarbons, oxygenated compounds, nitrogen compounds,
and halogenated compounds. The lower aolecular weight
hydrocarbons proved resistant to oxidation; methane was oxidized
only to the extent of 30 per cent even at 400 C. The organic
nitrogen compounds produced the theoretical amount of C02 as well
as appreciable amounts of nitrous oxide (N20)., Aamonia
produced 70V nitrous oxide at 315 C, and about 2* nitrogen dioxide
(N02)« The decomposition of organic halogen conpounds ranged
from slight in the case cf Frecn-12 to virtually conplete for
methyl chloroform- Xn addition, new organic balides were formed
by the oxidation of nethyl chloroform and Freon-11. There is at
least partial retention of halogen on the catalyst when
Freon-114B2 and Freon-11 are decomposed. Aerosols of
dioctylphthalate, a hydrocarbon-type lubricating oil, and a
triarylphosphate ester lubricant were quantitatively oxidized by
Hopcalite at 300 c« (Author abstract)ft
03985
IU C« Salooja
STUDIES OF COHBDSTION PROCESSES LEAEIHG TO IGSITIOH OF SOME
OXYGES DEBIVATIVES OF HtDBOCAHBOHS.. Combust* Flame 10, (1)
11-21, March 1966,
The pre-flame and ignition behaviors of several related
oxygen drivatives of hydrocarbons, acetic acid, nethyl formate,
nethyl acetate, ethyl acetate, nethyl propionate, propionic acid,
ethyl formate, acetyl acetone, and acetic anhydride were
investigated* Mechanisms proposed to explain observed
differences are discussed in relation to: (1) a carbonyl group
causes greater activation cf adjacent alkyl groups than
does an oxygen atoa in an ether linkage; (2) peroxy radicals
foraed in the initial stages of oxidation can readily undergo
1,5 and 1,6 intraaolecular transfer; (3} the oxygen atoa in the
carbonyl group tends to fori hydrogen bonds intraaolecularly.
Sith acetic acid, the coabustion process appeared acre
exothermic than of any hydrocarbons studied. Methyl fornate
ignited at a auch lower temperature than acetic acid, with
explosive violence; also greater amounts of methane ana
aethanol were produced than by acetic acid at corresponding
pre-flame stages: 9hile C02 is foraed in greater amounts than
CO froa methyl formate, the reverse is true with nethyl acetate.
Xn comparison with methyl acetate, ethyl acetate began to oxidize
at a slightly higher teaperatare but ignited at a considerably
lower temperature with explosive violence. In coaparison
1122
PHOTOCHEMICAL OXIDANTS AMD AIR POLLUTION
-------
with ethyl acetate, aethyl propionate began to oxidize at a lower
temperature but its extent of reaction increased less with
temperature, and it eventually ignited at a higher temperature.
Methyl propionate produced aore C02 th an CO until slightly
below ignition temperature than fthyl acetate. Analysis of
gaseous oxidation products of propionic acid and ethyl fornate
shoved that acetaldehyde was foraed in larger amounts froa
propionic acid and ethylene was foraed in larter amounts froa ethyl
foraate. Biacetyl trast to hydrocarbons oxidizing in the "low
temperature** region, biacetyl oxidation in the low teaperature
region. Acetic anhydride was even more reactive than biacetyl and
shoved no zone of negative teaperature coefficient. In its
oxidative degradation, CO was foraed in considerable aaounts
before any consuaption of 02 could be detected.##
03986
B. JL, Davies 0.. B. Scully
CARBON F0HHATI0B FROB AB0NATIC HYDB0CABB0HS XI.. Combust.
FlAHE 10, (2) 165-70, JTJII 1966.
Previous work on the yields of carbon black froa aronatic
hydrocarbons by injection of their vaponrs into the products of
coabustion of a rich towns gas-air preaixed flame has been
continued. Yields froa toluidines are higher than froa
aniline. The yields froa cresols are the saae as froa
phenol, the addition of oxygen to benzene and toluene decrease
the yields, which eventually become the saae, indicating
preferential oxidation of the side chain* The *02 group in
nitrobenzene does not alter the amount of soot foraed relative
to that froa benzene. Acetylene forms soot such less
readily than benzene. Cyclepentadiene does not form soot, but
indene does so readily. Styrene, ethylbenzene and
naphthalene have also been studied. fAuthor summary)##
04155
*. D. Feshetov
Aerosol obigib of atmosphbbxc ozoue (a hypothesis*-
D.S.S.B. literature on Air Pollution and Belated
Occupational Diseases, B. S. levine. Vol. 13. (Part I-
Atmospheric ozone. Results of D.S.S.B. international
Geophysical Year Studies Presented at the Oct. 2B-31, 1959
Conference. Beports and Resolutions.) pp. 73-85. 1961. Buss.
<|Tr.)
CPSTIS TT 66 62191
The aodern theory of photochemical ataospheric ozone origin fails
to explain soae facts and ozone properties. For instance, in the
south, where ultraviolet radiation is greater the amount of ozone
is smaller than in northern regions, where radiation arrival Is
considerably less, and during the polar night is nonexistent* It
M. Basic Sclsnca and TftChnolofy
1123
-------
also fails to explain annual changes in ozone content with a
maximum at the end of winter and beginning of spring, and high
ozone content in the lower portion of the stratosphere ana
troposphere, since that portion of ultraviolet radiation* which
generates atonic oxygen* is absorbed totally above the 20-km level.
It is also difficult to explain the appearance of special ozone
maximum observed sometines in the tropopause, or the considerable
fluctuations in ozone content associated with weather conditions.
It is conceivable that atmospheric ozone is also generated under
the effect of other factors, which, in a number of cases, may be
highly important. A hypothesis is presented on the generation of
atmospheric ozone by atmospheric aerosols fron water and
atmospheric oxygen during selective sorption and desorption at the
aerosol surface. {Author introduction modified)##
01171
0.. ha Rozental
STRDCttJUM OZOBE H0LEC01E HGDEIS. U.S.S..R. literature on
Air Pollution and Belated Occupational Diseases, B. s«
Levine, Vol. 13- (Part II - Atmospheric Ozone. Data
Presented at the Hay 21-23, 1963 Conference on Atmospheric
Ozone.) pp. 225-9. 1965. Huss. (Tr.)
CFSTI: TT 6662191
A clear concept of the ozone molecule structure might advance the
solution of the atmospheric ozcne problem. Four configurations
of atomic centers had been proposed in the past for the ozone
molecule, each of a different symmetrical type. The
inconsistencies of each proposed model are brought out in this
report and proof is offered in favoi of an absolutely nonsymmetric
model, the kind of which had not been considered before. Proof
of the acceptability of a nonsymmetric model amounts to a strictly
numerical calculation procedure which involves 1) analysis of the
infrared ozone spectrum, 2} study of the energy levels in the case
of an assumed motion of the third atom, and 3) accurate
determination of dynamic coefficients.##
042281
P. Goldfinger, G„ Buybrechts, and l. Meyers
THE CH10FIHE PHOTOSENSITIZED OXIDATICH OP HYDHOCAFBOHS AT L0»
TIHPEBATDFE fFISAL TICHMICAX SEPT.). University Libre
de Bruxelles, Belgium, Laboratoire de Chimie Physique.
Jan.. 1966. 30 pp.
The study of the chlorine photosensitized oxidation of
trlchloroethylene has been completed. A mechanism has been
proposed for this reaction where dichloroacetyl chloride is the
main reaeton product and the rate constants of the relevant
elementary reaction steps were estiiated. This together with
preceding studies on the oxygen effect on the photochlorination
of ethane and trlchloroethylene has led to a reaction theory which
seeas to be of general validity. la the second part of this
1124
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
report a new reaction theory of chlorine photosensitized
oxidation of hydrocarbons i£ presented which describes many of
the kinetic investigations that have been carried out by the
present work and reported in the literature. Due to the
diversity of radicals in the reaction mechanism and the
formation of different Froflucts not sufficiently unreactive, the
reaction mechanism is not in final form and more experimental
work is needed. (Author abstract)##
04277
N. Cohen and Heicklen
BEACTION OF NO(A2SIGMA) SITU C02« Aerospace Corp,, El
Segundo, Calif.
-------
0 U285L
E.. J. Poziomek
PHOTOCHEHISTKY OF H5TEF0CYCIIC CCOFODNDS (A LITERATOPE SOBVEY.)
Army Edgevood Arsenal, Hd. # Physical Research Lab..
(Kept. EASP 100-Un) Sept. 1966. 35 pp.
DOC: AD 1188-239
The literature on the photochemistry of heterocyclic compounds
was surveyed with a particular interest in pyridine chemistry.
This listing of references was compiled as a result of
searching volumes n^ to 61 of Chemical Abstracts under the
headings light, photochemistry, and pyridine.*t
0*1286
K„ F«. Preston and R. j. Cvetancvic
OS THE P0SSI81! COKTHIBTJTIOH OP A HOIECOLAB MBCHANISH TO THE
PHOTODECOBPOSniO* OF tUTBOGEK DIOXIDE. Can„ J. Chen.
2VU5-8, 1966..
CFSTI, DDCj AO 6U2-U55
The determination of the extent of 0~atop exchange during the
photolysis of mixtures of N02 and 02(36} at 2537 Angstrom units
and at other wavelengths has been investigated. This method is
based on the underlying assumption that only free oxygen atoms are
capable of exchange with 02(36) while other potential
intermediates {such as, for example, N02) are not. The
exchange reaction is therefore used as a test for the
involvement of free oxygen atoms in the photolysis of N02„*#
0«t29«
E. To Seo and D. T. Sawyer
ELECTROCHEMICAL OXIDATIOH OF DISSOLVED SDLPHOR DIOXIDE AT
PLATINUM ADD GOLD EIECTSODES. Ilectrochim. Acta 10, 239-52,
1965-
The electrochemical oxidation of dissolved sulphur dioxide
has been studied at platinum and gold electrodes using
voltanmetric* chronopotenticmetxic and galvanostatic measurements-
The effects of electrode pre-conditioning and solution pH on
the mechanism and the Kinetics of the electrode reaction have
been determined- Oxidation of sulphur dioxide occurs by two
mechanisms, one a pure electron-transfer process and the other a
chemical oxidation by electro!ytically formed metal oxide.
Hitb an activated platinum electrode the electron-transfer
mechanism is the predominating process. The electron-transfer
process is also predominant at an active gold electrode. For
this process the rate-controlling step as well as the over-all
process is a two-electron oxidation. (Author abstract)##
1126
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
cuicu
Putcell, T. C. and I. R. Cohen
PflOTOOX1DATION OP FORMALDEHYDE AT LOB PARTIAL PRESSURES CF
ALDEHYDE. Environ* Sci. Technol„, 1 (1OJ:845-846, Oct. 1967.
11 refs.
Although the photooxidation of aldehyde has been investigated in
recent years, the bulk of the work has been carried oat at
relatively high concentrations of aldehyde and the need far sore
detailed investigations at lov reactant concentrations helped to
initiate this investigation. Pormaldehyde at concentrations
ranging fro* 1 to 30 ppn in air was irradiated in reaction
containers fabricated from fluorinated ethylene-propylene
copolymer. The irradiations Mere carried out at 23 ~ or - 1 C.
nixed banks of sunlight fluorescent (wavelength maximum^ at 3100
A) and blacklight fluorescent lamps (3600 A) were ordinarily
used. Formaldehyde-air Mixtures in PEP containers were also
subjected to solar radiation during the summer and fall months.
Concentrations of formaldehyde were determined by a modification
of the chronotropic acid method. R202 concentrations were
determined by the 8-guinolinol and catalysed KI methods.
Colorimetric observations revealed no peroxy acid in the reaction
vessel, this suggests that performic acid has only transient
existence if it is involved at all. On the other hand, the only
identifiable oxidant produced in the photooxidation system was
hydrogen peroxide.##
04407
E. Peck and B. H. Khanna
DISPERSION OF BITBOGEH. J. Opt. Soc. Am. 56, (8) 1059-63,
Aug. 1966.
The refractivity of nitrogen gms has been measured, with high
relative precision, at vacuum wavelengths from 4679 a to 20 586
A. The Absolute value of refractivity for 5462 A, reduced to
one atmosphere at 0 C., is 0.0002991. A dispersion formula
fitting the data well at 15 C. is 10 to the 8th power
(n-1) = 6497.378 + 3073864.9/(144 sigsa squared), where sigma is
wave number in reciprocal microns. This is compared to
Svensson's dispersion formula for air. Alternative dispersion
formulas are discoursed. Quantities related to dispersion are
duduced: mean absorption frequency, effective total oscillator
strength, dielectric constant, Verdet constant, and Rayleigh
scattering coefficient. (Author abstract)##
04410
H. Steinberg
03 AND H02 FGBMATIOS 8T IFHADIAT10! OF A 82-02 GAS HIXTOS1
IK A IL0WIHG STSTEM AT BlIVATBD PRESSURES* Brookhaven national
M. Basic Sciatic* and Technofofy
1W7
-------
Lab., TJpton, N.Y. (Rept. No. BSI50017(T-43fl») Sept„
1966. 19 pp.
The aift was to develop information on the yield of ozone and
nitrogen dioxide pec unit energy deposited in the systen, and on
the radiation chenical kinetics in the flow reactor. This
information is desired in order tc determine the feasibility of the
application of cheac-nuclear reactors to the synthesis of oxone
from oxygen or air, and to the fixation of nitrogen from
nitrogen-oxygen Mixtures. The results of operating a flow systea
constructed on stainless steel with a 7911 N2 and 211 02 gas
aixture in a Co60 ganna radiation field at an intensity of
675,000 rads/br, indicate that at 68 atn pressure and 30 c a
naximum G(N02) value of 1.18 at a concentration of 89 pp», N02
is obtained. Only N02 can be detected for residence tines
equivalent to doses above 1.35 aegarads. it higher flov rates and
thus shorter residence tines, the N02 concentration and yield
decreases and 03 begins to appear. A G(03) value of 4.68 at an
03 concentration of 22 ppa vas reached. Belov a residence tiae
eguivalent to a dose of 400,000 rads, only 03 is present vith the
N02 decreasing to belov detectable limits. Increasing the
pressure fros 68 to 680 ata appears to have a saall decreasing
effect on the N02 yield and a larger increasing effect on the
03 yield.. It
0H429
B. H. Eortner
AN TXP2RIHINTAL STDDT OP THE DEIONIZATION OF 80 FIDS.
General Electric Co., Philadelphia, Pa., Missile
and Space Div. (Scientific Pept. No. 1.) (Bept. Ho.
AFCR1-65—391») Apr. 1965- 30 pp.
DDC, AD 619-252
An experiiental study of the deionization of NO plus vas
carried out. The ions were forged by a Penning effect
collision between aetastable argon atoas and NO aolecules.
The process vas efficient. The deionization process vas a
combination of the dissociative recombination NO(plus) plus
e yields H plus 0 and the autual neutralisation NO(plusJ
plus N02 (-} yields NO Ins N02, the N02(-) being foraed
by a three-step process —- Penning dissociation of NO,
3-body formation of N02 froa 0 and NO, and 3-body
attachaent to N02. If all the deionization were doe to the
NO(plus) plus e reaction the rate constant found vould
be 2 x 10 to the 7tb power plus or - 0.5. Seasonable
assumptions allow a crude estiaate of the NO (plus}
plus N02 rate constant of 2 x 10 to the -8th pover plus or ainus
1. (Author abstract) ##
0W37
A. v.. Phelps v. H. Kasner
STUD* AND EXPERIMENTAL ViOBK ON ATOMIC COLLISION PHQCBSSBS
OCCURRING IN ATHOSPBEBIC GASIS. Nestinghouse Research Labs,,
7128
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
Pittsburgh, Pa,., Atomic and Molecular Sciences Kesearch and
Development. (Technical Progress Letter 1*5=) tB®search
Memo 66-6E2-Gases-Hl.) Feb. 28, 1966- 5 pp.
DDC, AD U80800
Initial tests using single micrcwave power pulses on S2 - Ne gas
fixtures indicated agreement within 1* between the rooa temperature
recombination coefficients for N2 plus ions and electrons
obtained via the single pulse and recurrent modes of operation,
Using the glass-aluminum flow tube, destruction of negative
oxygen ions in 0-02 mixtures has been observed when the atonic
oxygen discharge source is operating. During tests with the mass
spectrometer in mixtures of CO-02 H2-02 and B0-02,
reactions consistent with associative detachment were observed-##
04U54
A. A. Armstrong, Jr. and B. K. Walsh
SADIATICN-INDUCED OXIDATIOS OP HYDSCCAHBOHS. North Carolina
State Univ., Raleigh, Dept. of Textile Chemistry. {Sept.
So. OBO-634.) July 15, 1965- <40 pp.
CFStI, OBO-634
The radiation-induced oxidation of ethane, propane and isobutane
was studied in a flow-type reactor using hydrogen bromide as a
catalyst. A Cobalt-60 source (Gammacell 220} was used for the
irradiation, the exposure dose rate inside the reactor was
approximately 180000 r./hr- In the oxidation of ethane, a
G-value of 800 was obtained for the production of acetic acid.
An increase in total flow rate of ethane to the reactor increased
the production rate of acetic acid. The most pronounced effect
was noted from an increase in pressure. An increase in the rate
of production of acetic acid of 8 times was obtained by increasing
the total pressure from 1 to 1 at a.. In the oxidation of propane,
a G-value of 10,000 was obtained for the production of acetone.
Increases in total flow rate did not affect the rate of
production. An increase in total pressure up to 3 atm. increased
the rate of production of acetcne but decreased the rate above
that. At 4 atm., corrosion products were deposited on the reactor
surface which accounted for the decrease in the rate of production
of acetone. Xn the oxidation of isobutane, the products were
t-butyl bromide, methyl brcaide and water, the expected products
of t-butjl hydroperoxide and di-t-butyl peroxide as reported by
other investigators were not present. The radiation-induced
oxidation of propane to acetone was the only reaction studied that
gave a G-value high enough to lcck promising. Although the
radiation-induced oxidation of propane to acetone looked attractive
from the standpoint of radiation yield, it now is impractical from
an economic viewpoint. (Author abstract)##
01156
B„ o« Doepker and P. Auelcos
PHOTOIYSIS OF CTCL0BDTAHH At PHOtON ENERGIES BELOH ABD ABOVE
M. Basic Science and Technology
-------
THE IONIZATION ENERGY.. 0. Chenu Phys. 13 (11) 3814-9, Dec.
1, 1965.
The photolysis of cyclo-C4H8 and cf cyclo-C4H8-cyclo-C4D8
mixtures was investigated at 1470 and 1236A in the absence and
presence of NO. In addition, a secies of experiments carried
out in which H2S was used as a free-radical interceptor in the
photolysis of cyclo-C4D8 at 1236 A.. Approximately 90* of the
observed products can be accounted for by the primary process:
C4H8+hv yields 2C2H4. The extent to which the internally
excited ethylene formed in this process will decompose further
increases with diminishing pressure and wavelength. The
photolysis of cyclobutane was investigated at energies above the
ioni2ation energy (I.E»*10«3eV), using the argon resonance lines
at 11.54 and 11.72 eV. It is shewn that when NO is added to
the system, cis-2-butene, trans-2-butene, and 1-butene are major
products. These butenes are, however, not produced when
NO (I.E.=9..25 eV) is replaced by 02 (I.E.^12.1 eV) and are
only formed in trace amounts when no additives are present. It
is suggested that the parent icn acguires the olefinic structure
and undergoes charge exchange with NO. (Author abstract)##
04465
H. Harrison and D. El. Scattergood
OFFER LIMITS TOR CHEHILOMINESCENCE FROH SINGIE COLLISIONS OF 03
BITH NO, CO, H2S, ASD CS2. Boeing Scientific Research
Labs-, Seattle, Hash., Geo-Astrophysics Lab. (Rept. No.
Dl-82-0480«) Jan. 1966. 26 pp.
DDC-AD 630 017
Double nodulated, crossed molecular beam experiments were
performed which permit upper limits to be set for the production of
light from single, thermal energy collisions of ozone with NO, CO,
B2S, and CS2. Minimum detectable signals were limited by
background light levels from a temperature sensitive surface
reaction involving ozone, tilth the apparatus walls cooled by
liguid nitrogen, this reaction still generated a partially single-
modulated detector noise whose dc ccunt rate as 100/sec. Bean
densities were determined with an electron-ionizatlon
stagnation detector, operated at 20 cps, and photomultiplier
luminous efficiency was measured by comparison with a standard
lamp.#*
0»«75
S. Posner and J. Bennick
PREPARATION OF I*SOLOBI,S AIHOSOLS CONTUSING HIXED TISSION
PRODUCTS. Lovelace Foundation for Hedical Education and
Research, Albuguerqae, H. Hex., Dept. of Aerosol Physics.
(Sept. Ho. LF-31.) July 1966. 14 pp.
CFSTI
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
The preparation of an insoluble aerosol containing nixed fission
products, using an ion exchange of uranyl nitrate with
montmorillonite clay is described. Ion exchange of an enriched
solution of uranyl nitrate to clay particles is accomplished by
adsorption. After spheroidizing by encapsulation the
•xcvhanged Material is sealed in a guartz vial and irradiated
for 12 hours in a thermal column of the omega Rest Reactor at
&os Alamos, lev Hexico. Evaluation by gamma ray
spectroscopy reveals the quantitative fission product inventory
for the exposure period; calculation indicated an approximate 26
per cent uptake of nranylions by the clay* Results indicate this
method to be feasible and practicable and future studies will
include evaluation of particle size versus ion uptake, fission
product build-up for various exposure times and pilot runs of
terosolization for exposure to animals. (Author abstract)#*
04528
A. v. Phelps and R. H. Rasner
STUDY AND EXPEHIJIEHTAL 10RK OH ATOMIC COLLISION PROCESSES
OCCURRING IN 1THOSPHERIC GASES. lestinghouse Research Labs.,
Pittsburgh, Pa., Atomic and Holecular Sciences Research and
Development.. Aug. 31, 1965.. 4 pp«
The major portion ot the present report period was spent studying
the temperature dependence of recombination in H2-He mixtures
under conditions where *2 + is the dominant ion specie. These
measurements were confined to the temperature range 205 to 455 K.
The upper end of the temperature range was limited by the
presence of impurity ions in the afterglow- The observed
recombination coefficients range from (3.0 plus or minus 0-2} x 10
to the sinus 7th power cc/sec at 205 K to (2*8 plus or minus
0.2) x 10 to the minus 7th power cc/sec at 455 K, the limits of
error representing the scatter of the data and not the absolute
accuracy of the measurements. At a given temperature the results
show no systematic dependence on the nitrogen or neon pressures.
Temporal mass analysis indicates similar decay rates for the N2+
icns and for the electrons over the major portion of the afterglow
period. Host of the report period was spent in obtaining data
with the rf mass spectrometer which will be used with the flow tube
for ion identification. Further studies on C02-02 mixtures
yielded a reaction rate of 1.3 x 10 to the minus 29th power sq.
cc/sec for the three body conversion of 02- to C04- and a rate
of 1„3 x 10 to the minus 28th power sq. cc/sec for the conversion
of o- to C03-. Mixtures of nitrcgen and oxygen were also
investigated but no complex negative ions wer*detected. In pure
water vapor no attachment was observed for E/p less than 8
v/cm/Torr, but for I/p greater than 8 V/cm/Torr seven
negative ions, H-, 0H-,
-------
ACTIVATES CARBON* (flplyw Adscrbcwanego Tlenu Na Wlasnosci
Katalityczne Hegla Aktywowanego.) Boczniki Chemii 35,
999-1008, 1961.. Pol. B Pr. (Tr„)
The catalytic properties of activated carbon in the H2S
oxidation reaction were studied and compared with the results
obtained by using carbon previously desorbed and saturated with
oxygen after desorption. The composition of oxidation products
and the effect of moisture content on this composition were
determined.. Comparison of the available information on oxygen
adsorption on carbon pores with the results obtained in the present
work indicates that the prevailing views can be supplemented with
a working hypothesis which would reguire comprehensive
confirmation: prior to being used as a catalyst for H2S
oxidation, carbon adsorbs oxygen in its pores, which in part is
bound irreversibly in the form of C(x}0(y) surface complexes..
The amount of the resultant cciflexes depends on the oxygen
concentration in the gas surrounding the carbon. The
oxygen contained in the gas from which H2S is being removed is
adsorbed on carbon reversibly. It undergoes instant activation,
which increases with tine. The degree of this activation depends
on the amount of surface C(x|0(y) complexes formed on the
catalyst pore surfaces. These complexes have varying stability,
and strong desorption at 450 C causes most of then to be
decomposed. The oxidation of S2J-) to S4(+) in accordance the
scheme, 2H2S ~ 302 = 2S02 ~ 2H20, depends not only on the
H2S:Q2 ratio in the reaction Mixture, but is greatly affected
by the noisture content of the medium, a circumstance mentioned by
Courtyn The assumption that coplete oxidation of H2S
proceeds through co«bined reactions and 2S02 + UH2S = 6S ~
4H20 constitutes a postulate which gees further than Prettre's
assumptions. These conclusions derive both from an analysis of
previous results and from the fact that at H2S:02 * 1:0..625
oxygen-containing sulfur compounds are obtained in the reaction
products. This ratio is considerably lower than that predicted by
Prettre.M
04578
I. C. Hisatsune
TBERMODIHABIC PF0PEBTIES Of SOHI OXIDES OF SITBOGEN.
0„ Phys. Che*. 65, 2249-53, Dec. 1961.
Available spectroscopic and structural data were used to
calculate the thermodynamic functions for N03, N203, H204
and V205, and dissociation equilibria of these oxides. For the
H205 dissociation, the necessary functions for N03 radical were
estimated from vibrational frequencies calculated with
Orey-Bradley force constants. These data together with those
obtained from other sources lead to the estimated properties for
ideal gases at one atmosphere and 25 degrees. (Author abstract
modified)••
1132
PHOTOCHEMICAL OXIDANTS ANO AIR POLLUTION
-------
CH580
I. c» Hisatsune, J..P. Devlin, Y. Vada
VIEBATIONAL SPECTBTJH ANE STRUCTUBE OF N205. Spectrochiliu
Acta 18, 16U1-53, 1962.
The infrared spectrum of N2o5 in the 2-35 micron region was
obtained in the gas and solid phases. In the solid phase, the
temperature dependence of the spectrum and the changes in the
spectrum accompanying the covalent to ionic transformation of the
molecule were observed. Infrared and Raman data are
consistent with the 02N0NO2 structure with a bent central
N - O - S group. These data give nc indication of the
relative orientation of the nitro groups. However, the data
do suggest that in the gas phase the potential barrier against
internal rotation of the nitro groups is low- Both entropy
calculation and approximate ncrital coordinate calculation
show that the N - 0 - N angle deformation frequency may fce
about 85/cm. (Author abstract}M
04563
0. Heicklen, and H« S« Johnston
PHOTOCHEMICAL OXIDATIONS.. II. MTHYI IODIDE. J. Am. Chem.
Soc. 8tf03C-9, 1962.
The room-temperature photo-oxidation of methyl iodide (0.2 to
3-0 mm.) in oxygen (0.030 to 10 dbi.) with continuous UV
radiation above 2200 A. was studied. Observations were made by
leaking the reaction mixture directly into the electron beam
of the mass spectrometer daring photolysis. The principal
products of reaction were 12, H2C0, CH3CH and under
some conditions CH300H; minor products were H20, C02,
PCOOH, CH300CH3 and CB30I. Because of the
cracking pattern of the reactants and major products and the
background air peaks, it was impossible to establish the
presence or absence of CHU, CO and HI. There are
conflicting claims in the literature as to whether methyl
radicals react with oxygen according to CH3 + 02 (~ H) -
CH302 (+ HJ (followed by the Vaughn mechanism) or CH3 +
02 = H2C0 ~ HO (Followed by HC attack on loosely
bound hydrogen atoms). This stud; indicates botjj processes do
occur, with the first being more important under conditions used
here. It seems probable that oxygen molecules abstract hydrogen
atoms from CH30 radicals to produce H2CO and H02. A
fairly complete and internally consistent mechanism is developed
for the initial reaction, typically the reaction of about 0.0001
or 0.001 of the methyl iodide. Is the reaction progresses,
inhibition caused by CH3 + 12 equals CH3I + I becomes
very pronounced* radicals abstract from H2C0, a large number of
other secondary reactions seem to occur* and the mechanism proposed
is regarded as exemplary rather than established. In terms of the
relatively simple initial reaction, many ratios of constants are
evaluated. (Author abstract)#•
Ml. Bwic Sctenc* and Techndlogy
1J33
-------
04626
D~ B„ Coughanowr and F» E. Krause
THE BE ACTION OP S02 AND 02 IN AQUEOUS SOLUTIONS OF MNS04,
Ind. Eng. Chem. Fundamentals 4, (1) 61-6, Feb. 1965..
An experimental investigation Has made to determine the rate of
reaction of sulfur dioxide and oxygen in aqueous solution
containing manganous sulfate as a catalyst. The catalyst was
varied from 0 to 15 p. p. m» of MnS04 in a batch method, and from
100 to 10,000 in a flow method. The temperature was 25 C«
The reaction is zero order with respect to both sulfur dioxide and
oxygen- The concentration of nanganous sulfate has a large effect
on the rate of reaction; frcm 0 to 100 p.,p.m. of manganous sulfate,
the reaction rate constant, k, is proportional to the square of the
catalyst concentration, but above 100 p.p.nu, k increases less
rapidly up to about 500 p.p.. ro., after which X increases very
slowly with catalyst concentration. The reaction is easily
inhibited by very small amounts of contaminant.##
04633
P.. A. Leightcn
SOHE REMARKS ON THE NITRIC OXIDE — NITROGEN DIOXIDE CONVERSION..
Preprint. (Presented at the Air Pollution Research
Conference on "Atmospheric Reactions," Univ. of southern
California, Los Angeles, Calif., Dec. 5, 1961.,)
Ni.tric oxide-nitrogen dioxide photochemical conversion theory is
reviewed. It has been almost universally postulated that the
products of oxygen-olefin and possibly ozone-olefin reactions,
which promote the above mentioned conversion, are free radicals.
The extent to which these reactions produce radicals and the
nature of the radicals produced in air have not been established.
Other unresolved questions pertaining to this conversion reaction
involve reaction kinetics and reactant concentrations.##
04653
J., H.. Singer, E„ B. Cook, ». E. Harris, V. R. Rowe,
J. Grumer
FLAME CHARACTERISTICS CAUSING AIR POLLUTION: PRODUCTION OF OXIDES
OF NITROGEN AND CARBON MONOXIDE. Bureau of Mines,
Pittsburgh, Pa. (Presented at the Symposium on Combustion
Reactions of Fossil Fuels, 152nd National Meeting,
American Chemical Society, Sew York city, Sept. 11-6, 1966
and at the Basic Research Symposium, Chicago, 111., Mar*
14, 1967..) 40 pp.
1134
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
Concentrations of nitrogen oxides and carbon monoxide in
combustion gases of lean* stoichiometric, and rich propane-air
flames are predicted from theoretical kinetic and
thermodynamic calculations. Experimental values are higher
than the theoretical by factors of 2 to 7. Lowering the
primary flame temperature with cold flue gas reduces the nitric
oxide and increases the carbon monoxide concentrations.
Cooling rates of 5500 degrees to 10,000 degrees P/sec starting
at about 3500 degrees H maintain the nitric oxide in the
primary combustion zone at the initial value and do not
prevent oxidation of the carbon monoxide.#*
04668
L. Slater Bo ft. Dilie
PARTIAL CCBBOSTION OP HESIDUAL JtJELS. Chen. Eng. Progr. 61,
(11J 65-8, Hov„ 1965.
Partial oxidation of residual fuel oils produces high
purity synthesis gas containing hydrogen* carbon monoxide, carbon
dioxide, methane, and only minor traces of impurities. The
methane concentration in the synthesis gas produced at
elevated pressures corresponds to equilibrium conditions*
Although the studies of the process have been made at pressures
up to 1,500 lb/sq in gauge, there have been no indications that
this pressure can net be increased several fold- The soot
produced from heavy oils is water-nettable, has oil adsorption
numbers of 150 to 500 lb/100 lb, and has specific surface areas
of 100 to 1,200 sq i/g. The oil adsorption number of the soot
increases directly with the steam/oil ratio in the feed to the
synthesis gas generator. {Author conclusions}#*
01771
L. J. E. Hofer, P. Gussey, and B. B. Anderson
SPECIFICITY OF CATALYSTS FOB THE OXIDATION OF CABBOH HOSOXIDE
ETHYLENE SIXT0BES« J. Catalysis 3, (1-6) 451-60, 1964.
(Presented at the Catalysis Club Spring Symposium, Pittsburgh
Pa., Hay 10, 1963.)
The specificity of 5 different catalysts for the ocidation of
ethylene and carbon monoxide was determined in a microcatalytic
reactor at temperatures from 50 to 600 C. On all 5 catalysts
CO oxidized more readily than ethylene. Complete removal of
CO occurred on th« cobalt oxide at room temperature, on the
copper oxide-chromium oxide on alumina catalyst at 100 C, on both
copper oxide and iron oxide at 200 C« and on chromium oxide at 450
C. On cobalt oxide, iron oxide, chromium oxide, and the copper
oxide-chromium oxide on aluminum oxide the presence of CO
enhanced the oxidation of ethylene. Conversely the presence of
ethylene inhibits the oxidation of CO markedly in the case of
cobalt oxide and iron oxide. Significant chemisorption at any
M, Basic Science and Technology
1138
-------
temperature was not observed for chromium oxide or copper oxide.
The other 3 catalysts shoved significant quantities of
chenisorption for both ethylene and CO. Hith chromium oxide,
ferric oxide, and cobalt oxide, hydrogen was produced in amounts up
to 2% of the hydrogen in the initial ethylene. (Author abstract)#
04801
E„ Hatijevic, K. F. schultz, and M. Kerker
LIGHT SCATTERING OF COATED AEHOSOLS. II- SCATTERING BY
LIHOLESIC ACID AEBOSOLS. 3. Colloid Sci. 17, 26-38,
Jaru 1962.. (Presented at the 140th fleeting, American
Chemical Society, Chicago, 111., Sept. 1961.)
Linolenic acid aerosols exhibiting higher order Tyndall spectra
and comparable in monodispersity to monodisperse sulfur sols have
been prepared reproducibly using silver chloride nuclei* Particle
size distributions can be obtained precisely by analysis of the
light-scattering data and when apEropriate precautions in
sampling are observed, excellent agreement with electron microscope
counts is found. Samples axe fixed for electron microscopy by
treatment with 0s04„ The influence of boiler temperature,
nuclei concentration, and dilution of the aerosol upon the light
scattering and particle size distribution has been considered.
¦(Author abstract)##
04831
Betryman, Earl 1. and Arthur Levy
KINETICS OF SOLFOF—OXIDE FOBHATICR 18 FLAflES : II. LOU P8ESSUHE
H2S FLAMES. J. Air Pollution Control Assoc., 17(12i:
800-806, Dec. 1967. 18 refs. (Presented at the 60th Annual
Heeting, Air Pollution Control Assoc., Cleveland, Ohio,
June 11-16, 1967.)
The microstructure of 0.1- and 0.05- atmosphere, lean
H2S-02-N2 flames is developed using the mass-spectcometric
flame-sampling technique. The flame mechanism developed is in
agreement with that determined frcm an earlier study on 1-atm H2S
flames. The formation of S02 appears to be primarily related
to the production of SH and the ensuing oxidation steps SH plus
02 equals SO ~ OH and SO ~ 02 ® S02 ~ O. Bhile there
is some question whether so2 formation occurs via an SO OR AND
S20 intermediate, the present study does not give direct support
to the role of 320 in the oxidation mechanism. However, the
presence of significant quantities of fees sulfur in the pre-flame
zone may be indicative of S20 formation via SO ~ S yields
S20, and, possibly, via the disproportionation of SO, 3SO
yields S20 * S02. Kinetic analyses of some of the pre-flam®
reactions indicate an apparent activation energy of 17,300
calocies/mole for th« decomposition of H2S. The actual
1136
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
initiation process in the flane mechanise requires further
exatiination.. The specific rate for the reaction step H2S + o =
OH + SH is given by k6 =» 1.45 x 10 15 exp (-6600/BI) cn3 mole
-1 sec-1, and the specific rate for the oxidation of SO, SO +
02 = S02 + O, is gives by k5 35 5..2 X 10 It exp (-19,300/BT)
cm3 aole-1 sec-1. (Authors0 abstract)##
04863
E. A. Schuck and E. S. Stephens
QUANTUM YIELDS DOHING DILUTE GAS
IB THE 3500 A. REGION- Environ.
Feb. 1967..
PHASE PHOTOLYSIS OF ETHYL NITHIIB
Sci. Technol. 1, 138-43,
Parts per Billion concentrations of ethyl nitrite (EtONO) were
photolyzed in the absence and presence of added nitrogen or NO.
The light source employed had its intensity maximum at 3500 A.
with 851 of its energy confined to the 3300 to 3750 A. region.
The phi was usually nuch less than unity and decreased as the
concentration of EtONO or added gas was increased. Above an
initial EtONO of 20 p.p.m», or in the presence of added gases,
the reaction followed a pseudo first-order rate law. In the
absence of added gases and at initial EtONO concentrations,
which were nuch less than 20 p. p.m..„ the reaction tended to follow
a second-order relationship. A aechanistic approximation of the
results can be obtained by assuaing the existence of two egually
important priaary processes. These are cleavage at the BO-NO
bond and foraation of an excited state., Recombination of the
initial fragaents from B0-N0 bond cleavage and collisional
deactivation of the excited state appear to be iaportant
secondary reactions. The choice between these two priaary steps
nay involve the rotational iscaers. Product analysis showed that
80% of the carbon was in the fora of CH3CH0 and 20* as EtOH.
Thus, intramolecular rearrangeoeut of the excited cis-isoner nay
be the najor source of the CH3CHO. (Author abstract
Modified)##
04870
PHOTOLYSIS OF SITRGOBN COMPOUNDS. Natl. Bur. Std* (U.S.)
Tech., News Gull. 51, (4) 72-4, Apr. 1967.
In order to precisely define the aacunt of energy available to
NO in this investigation of the photolysis of nitrogen compounds,
gaseous nitrogen coipounds and aixtures were irradiated with
aonochroaatic light. Fluorescence of the excited species was
obtained by passing a streaa cf saajle gas through a reaction
cbaaber across whiclithe exciting light was directed. Reactions of
a variety of aixtures and pressures of N20, N02, NO, 02,
and BN3 WERE STODIED UNDER RADIATION AT 1216*1, A MXTUBE CP
1165 A, 1tt70 A and wavelenghts greater than 1600 A..
1236 and 1165 A, 1470 A and »a«elenghta greater tban 1600
Fluorescence of excited NO was obtained in beta and ganna bands
M. Basic Sciwce and Technology
1T37
-------
corresponding to different energy levels of excited NO- The
beta band of NO fluorescence was obtained by photolysis of pure
N20, but was replaced by gamma-band fluorescence with the
introduction of even sm^ll amounts of NO for all exciting
radiations except those of wavelengths greater than 1600 A. The
suggested sequence of reactions originating from N20 and the N20
and NO mixtures with the emission of beta and gamma radiation
respectively are discussed. The photodecomposition of the
triatomic molecules N02 and N0C1 was studied by observations
of the rotational and vibrational distribution of excited NO.
In this study both beta and gasma bands were given off by N02
subjected to the 1165 ft - 1236 A mixture and to 1295 A; only
the gamma bands were given off by NCC1 subjected to the same
radiations.##
0U878
G„ n.. Fichter, H» C. Biesev and B. H. Sage
OXIDES OF NITBOGEN IN COMBUSTION. Premixed Flaae. Combust.
Flame 6, (1) 1-8„ Mar. 1962..
This investigation was undertaken to determine the effect of
combustion conditions in premixed flames upon the formation of the
oxides of nitrogen- Heasurements were made of the residual
guantity of the oxides of nitrogen in samples taken as a function
of the spatial position in a cylindrical combustor™ The
influence of mixture ratio and of rate of flow of the reactants for
a premixed, natural gas-air flame was studied. In addition the
apparent temperature and mole fraction of carbon dioxide, oxygen
and carbon monoxide were determined as a function of spatial
position in the combustor. It was found that the local
perturbation of pressure encountered in the combustion was one of
the principal factors in increasing the residual quantities of
oxides of nitrogen in the products of reaction. The results are
presented in graphical and tabular form.#!
C4913
J.. B» Olin and B. B. Sage
AN EXPERIMENTAL STODT OF THE FOBHAIICN AND DECOMPOSITION CP NITBIC
OXIDE. J. Che*. Eng. Data 5, <1) 16-20, Jan. 1960.
The experimental conditions for each of 65 tests upon the
nitrogen-oxygen system and the initial and final compositions for
the 65 tests are tabulated. The influence of the maximum
apparent temperature upon the residual nitric oxide ratio is
indicated schematically for compositions containing 0..U mole
fraction nitrogen, 0*2 mole fraction oxygen, and 0.4 mole
fraction helium. A markedly higher nitric oxide ration for the
same maximum apparent temperature was found for the tests in which
the light piston was used (initial sample pressure of approx*
1..16 p.s.i.)., Data for an initial sample pressure of
approximately a.62 p.s.i. shows much less, if any, difference
1138
PHOTOCHEMICAL OXIDANTS AMD AIR POLLUTION
-------
between the behavior with the light and the heavy piston*
Variation in the nitrogen-oxygen ratio bad relatively snail
influence upon the relationship of the residual nitric oxide ratio
to the maximum apparent temperature. Approach to chemical
equilibrium in the ballistic piston was established from a series
of tests *ade with the piston weighing 3.29 pounds,, Measurements
were made upon mixtures which contained equal sole fractions of
nitrogen and oxygen with 0.8 mole fraction helium and mixtures
which contained 0.2 sole fraction nitric oxide with 0.. 8 mole
traction helium. The residual nitric oxide ratio resulting from
the nitric oxide-helium sample decreased with an increase in the
maximum apparent temperature. On the other hand, the residual
nitric oxide ratio in the mixture of nitrogen and oxygen
increased with an increase in the maximum apparent temperature..##
C4914
B. R. Sakaida, B„ G. Sinker, *. L« Wang, and I. H«
Corcoran
CATALYTIC DECCHEOSITION 07 SITBIC OXIDE. A.I.Ch.E. (Am.
Inst. Chei. Sngrs.} J. 7, (4) 658-63, Dec. 1961.
Catalytic decomposition of nitric oxide st a concentration of
0.404 and 0.432% by volume in nitrogen was studied in a
tubular flow reactor*. The packing consisted of alumina pellets
impregnated with 0.1* by weight of platinum oxide and 3„0I by
weight of nickel oxide. Tests were conducted at pressures of 1
to 15 atm. and temperatures feci 800 to 1,000 F. A rate
equation correlating the data as a function of temperature,
pressure, and compositions was developed. A reaction mechanism
compatible with the rate equation is proposed. The rate of the
heterogeneous decomposition of nitric oxide over a platinum-nickel
catalyst supported on activated alumina was found to be second
ordier with respect to nitric oxide, retarded by atomic oxygen# and
further retarded by the excess nitrogen in the system. The rate
equation is applicable for the decomposition of nitric oxide
present in nitrogen at concentrations of less than 0.5% within the
temperature range of 800 to 1,000 F. and a pressure range of 1 to
15 atm.##
04926
K. C. Salooja
IBF1UEHCE OF POIASSIUB CHIOBIDE OK CCHBUSTIOH PROCESSES LEADING
TO IGBITIOH. Combust. Flame 10, (1) 45-9. Bar., 1966.
Combustion studies were carried cut on the following hydrocarbons:
pentane, hexane, 2-aethylpentane, 2,2-dimethylbutane, iso-octane,
cyclohcxane and methylcyclehexane. The oxygenated compounds
studied included acetic acid, methyl formate, propionic acid,
ethyl formate, methyl acetate* acetaldehyde, acetone, diethyl
•tfeer, isopropasol and methanol., Besults are reported for only
M. Basic Science and Technology
1139
-------
one of the hydrocarbons studied* namely pentane, because the
behavior of different hydrocarbons was generally similar. KCl
markedly inhibited the oxidation process at all stages leading to
ignition.. In narked contrast tc its effect on hydrocarbons,
KCl promoted the pre-flame oxidation of acetic acid, propionic
acid, methyl formate, ethyl fermate, methyl acetate and acetone-
It markedly inhibited the combustion of methanol and isopropanol.
The effect of KCl on the ignition of acetic acid and acetone
vas not studied since these compounds ignite well above 600 C, but
with propionic acid and the esters studied KCl strongly inhibited
the onset of ignition despite its promoting effect on their
pre-flame oxidation. The promoting effect on the oxidation of
carbonyl compounds, particularly the lowering of the temperature
at which oxidation commences, suggests a direct reaction between
KCl and carbonyl coxpounds. Another observation is that, in
contrast to the behavior in the clean vessel, KCl generally
causes more C02 to form than CO. Under the experimental
conditions, KCl does not significantly catalyse the combustion
of CO to C02. Therefore, the greater formation of C02 must
arise from attachment of oxygen to the carbonyl progenitor of
CO. The inhibiting effect of KCl on the combustion of
hydrocarbons would seem to arise primarily from its effect on
HC2 radicals formed prior to the appearance of carbonyl
intermediates. The absence of any B2C2 in the products in
KCl-coated vessels supports this view.**
00965
P. H. Krupenie
THE BAUD SPECTROH 0? C&BBOI H0S0XIDE. National Bureau of
Standards, Washington, D.C., national standard Reference
Data Series 5. July 8, 1966.. 93 pp.
The present work, first in a series on diatonic molecules, follows
the approach of Lofthus and is devoted to a single molecule.
This report includes a comprehensive review of the literature on
the spectrum of CO, CO(+), and CC(2*} in the gas phase, and a
compilation of critically evaluated numerical data on band
positions, molecular constants, energy levels, potential
energy curves, and other molecular properties derived from t}ie
spectrum. Estimates of reliability are given where possible.
Papers from which the tabulated data have been extracted are
discussed in the text of this report. Early data of presumably
low precision have been included in the tabulations only where
better or more recent data are not available. The references
cited constitute a critical bibliography rather than an exhaustive
one,##
04967
Y. K., la Her
THE PREPARATION, COLLECTION, AID HEASURE8BHT OP AEROSOLS.
Proc. Rati. Air Pollution Symp., 1st, Pasadena, Calif.,
19«9. pp. 5-13,,
1140
PHOTOCHEMICAL OXIDANTS AND AI R POLLUTION
-------
In the study of aerosols, many difficulties are imposed hy
variations in particle size.. These difficulties may be avoided
by working with monodisperse liquid aerosols; in this paper, it
implies preparations whose size distribution does not deviate by
more than 10* from the mean value. The preparation and optical
properties of monodisperse aerosols are described in detail.
Included are an analysis of light scattering properties; use of
the Hie theory; polarization techniques; optical obscuration by
monodisperse fogs; filtration of aerosols; the forward angle
Tyndallometer; and an evaluation of the cascade iapactor,,##
04992
A.. Haagen-Smit, C. E. Bradley, E» M. Fox
FORMATION OF OZONE IN LOS ANGELES SBOG., ProC. Natl. Air
Pollution Symp«, 2nd, Pasadena, Calif.., 1952. pp« 54-6..
When bent pieces of rubber were exposed to sunlight in the
presence of oxygen and nitrogen dioiide no cracking took
place.. Rubber cracked in nitrogen dioxide in air but not when
the air was filtered through charcoal. Rubber cracked
in 3-methylheptane and H02 in air but not when either was used
alone; it cracked when introduced to a mixture exposed to
sunlight for several hours. Ozone was identified as the rubber-
cracking material.. Bubbec cracked in some organic acids
photooxidized with N02 in air; ozone was again isolated
and identified. Rubber cracked in gasoline photooxidized with
N02 in air. Ozone formed when 4-n-nonene was photooxidized
with N02 in air. Biacetyl in air cracked rubber when
exposed to sunlight; ozone was identified. Rubber also cracked
with biacetyl and K02 in air« Rubber cracked in butyl nitrite
in air exposed to sunlight. The concentrations of the organic
materials and of N02 were of the same order as those found
in Los Angeles smog-##
05043
I.. B. King
BBCOJIBINATION OF I0HS IS J1ABIS EFFECT 01 TIMFEBATOBE. Texaco
Experiment Inc., Richmond# Va« (Sept. Nos. AP05R-463,
TP-165A, and EXP 2789) Aug. 1, 1961. 5 pp.
The effect of temperature on the recombination rate of ions in a
hydrocarbon-air flame is pc«sented and the results compared with
predictions based on present-day theories. Measurements were
conducted with an alternate-probe technique in a propane-air flame
burning on a Heker-type burner 5.5 c* in diameter. Two probes of
different length, mounted at right angles to each other cn a common
shaft (the t*o probes being in a plane perpendicular to the shaft),
entered the flame from the side* parallel to the flame front. By
measuring current first with one probe, then with the other, and
substracting the t*o readings, it was possible to determine the ion
concentration in the center of the flame. An ion-ion process
agreeing with the Iangevin prediction is indicated.#*
M. Basic Scitnct and Technology
1141
-------
05047
N.. F. Bukherjee, n„ R„ James, H., s. Hummers, E.
Eyring, and T. Bee
STUDIES TO DETERMINE THE HECHAKISH CP PRODUCTION AND REMOVAL OP
ELECTRONS IN ELAMES. {Utah Univ., Salt Lake City..) (Sept.
No. A7BMD-TR61-1 Aug.. 8, 1961 37 pp.
Probable chain reactions and mechanism for the formation of the
most abundant positive ions are summarized. A steady state
analysis of reactions reveals a number of important conditions
that must be fulfilled for the nest abundant ion formation.
Approximate values for the maximum and minimum concentrations of
the most abundant ion with respect to oxygen are obtained. A
semi-theoretical method is used to calculate the concentration of
the most abundant ion in hydrocarbon-oxygen or hydrocarbon-air
flames. Experimental studies have been performed on the effect
of ultra-violet light on icn concentration in flames. Research
has also been started on the effect of the degree of unsaturation,
state of oxidation, and length of the carbon chain on ionization
of various hydrocarbons in a hydrogen-oxygen flame.
05051
E. S.. Rabinovitch, and D. N. Setser
U RIHOLECULAR DECOMPOSITION AND S011E ISOTOPE EFFECTS OF SIKPLE
AIKANES AND ALKYL RADICALS. Washington Univ.., Seattle, Dept.
of Chemistry and Kansas State Univ.., Manhattan, Dept. of
Chemistry. June 1, 1964. 142 pp.
A theoretical study is reported on the nature of unimolecular
reactions, their dependence on the energy parameters of the
systems involved (photo-chemical or thermal}, and their dependence
on molecular structure. The relevant aspects of the RRKM
formulation for uninolecular reactions are discussed. Emphasis is
placed upon the present status of the theory, and the best
techniques for carrying oat ccmputations. Characteristics of
various model hydrocarbon-type molecular species which are used
in theoretical calculations are outlined. Kinetic isotope
affects are considered and model calculations presented for
hydrogen-deuterium substitution., consideration of reaction
processes shows that a given hydrocarbon species can be produced
at many different pressures, in a variety of energy states and with
various hydrogen-deuterium isotopic compositions. Specific rate
constant relationships to experimental parameter are discussed.
The behavior of some CJ1J-CJ1) alkancs and alkyl radicals are
calculated as examples of highly important practical systems. It
is hoped this will provide useful insights into experimental
situations.#*
1142
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
05058
D» E. Van Sickle and B» R. flayo
OXIDATION OF UNSATURATED HYEBOCABEGNS (FINAL BEPT. OCT„ 1,
1961-SEPT- 30, 1963). Stanford Besearch Inst., Henlc Park,
Calif., Jan* 10, 1964.. 6 pp»
Besearch effort for the last two years us directed principally
toward product studies of low temperature, liquid-phase olefin
oxidations- Fare hydrocarbons were utilized where possible, azo
initiators employed, and conversions limited to 5*„ Correlation
of the hydroperoxide produced with the remaining products found
and assignment of relative rates for two chain propagation
reactions were attempted. A secondary effort was the study of
autocatalysis in oxidation. Cyclopentene was chosen as a model
compound, since its oxidation mechanism is the simplest of the
olefins studied- Decomposition and initiating properties of
hydroperoxides also received attention™ (Author introduction
modified}##
05099
T. S. Nagarjunan, J. G. Calvert
THE PHOTOOXIDATION OF CABB0F HONOXIDE ON ZINC OXIDE. J. Phys.
Chen,. 68, (1) 17-26, Jan. 1964.
The photooxidation of carbon monoxide on zinc oxide solid has been
studied in experiments at 0 degrees. ZnO with presorbed oxygen
was irradiated with 3660-A. light in the presence of CO gas.
C02 was formed in the irradiated system, while its rate of
formation in the dark was negligible. The reaction was studied
under varied conditions: the temperature at which the oxygen was
presorbed on the ZnO, the pressure of oxygen during the
presorption, the pressure of CO gas, the time of irradiation,
and the intensity and the wave length of the absorbed light. The
results confirm that oxygen is adsorbed in at least three different
forms on ZnO in an amount which depends on the temperature of the
treatment. Two of these types of adsorbed species of oxygen react
with CO to form CO2 on irradiation, while the third type is
inactive. The three types may be 02(-), O(-), and 0(2-), with
the first two the active forms. CO appears to react either from
the gas phase or from a weakly adsorbed state. The reaction may
occur through two different reaction paths, one much faster than
the other. The guantun efficiency of the C02 formation varies
from 0.001 at high intensities to greater than 0.1 at low
intensities at 3660 A. Some aspects of the detailed
mechanism are considered. From these and other results some
speculation is given concerning the contribution of photooxidations
sensitized on suspended solid particulates to the chemistry of the
polluted atmosphere. There is a high probability that such
reactions are of little importance in the usual polluted
atmosphere. (S28author abstract)
atmosphere. (Author abstract)##
M. Basic Sciencfl and Technology
1143
-------
05100
J. N. Pitts, Jr., H. N. Johnson, and T. Kuvana
STRUCTURAL EFFECTS IN THE PHOTOCHEMICAL PROCESSES OF KETOHES
IK SCLUTICN . -«J. Phys. Chem. 66, 2456-61 (Dec. 1962).
(Presented at the Symposium on Reversible Photochemistry
Process, Durham, N.C., Apr.. 1962.)
The primary objective of this investigation was to checX the
effect of substituent groups and location of substitution on the
photoreduction of a series of benzophenone derivatives- The
behavior of a series of hydroxy, methoxy, amino, and
chlcroben2ophenones in the photopinacol reaction was studied using
product isolation, UV spectroscopy, phosphorescence,
fluorescence, and EPH spectroscopy- Results and correlations
derived from these studies are discussed herein. Some of these
include the following: Ortho substitution by a number of
functional groups has a pronounced effect on the "go - no go"
photoproperties of the benzopbenone derivatives. Replacing the
OH or the CHS by aethoxy or carboxy restored the
intermolecular hydrogen atom abstracting power of the benzophenone.
This suggests that the deactivating effect of o-OH,NH2, NHCH3,
and methyl groups is due to their tendency to form reversible
photoenols. Ten and 21-hour irradiation at room temperature of
degassed 0.01 H solutions of p-aminobenzophenone in isopropyl
alcohol using a medium intensity mercury lamp produced no
significant permanent changes, strong phosphorescence was noted
during irradiation in the rigid medium at 77 K., and EPtt
resonance signal due to the triplet state of 4-aminobenzophenone
was observed. Long-lived phosphorescence was also observed for
p-dimethylamino and p,p"-bis(dimethylamino) benzophenone. EPB
studies of these and other para-substituted compounds are in
progress. A preliminary report on a similar study in the
anthraguinone system is included.*#
05204
Nicolet
NITROGEN OXIDES IH THE CHEHOSPHIBB,. Pennsylvania State Oniv.,
University Park* Dept« of Electrical Engineering- Dec. 10,
1964., 32 pp» (Scientific Bept. No. 227„) (Rept. Ho.
APCHI-64-939.)
A study is made of the various reactions in which nitrogen oxides
are involved in the chemosphere. The hydrogen compounds do not
play an important role, and it is found that the essential
aeronomic reactions depend on czone and atomic oxygen. Thus, the
ratio nitrogen dioxide-nitric oxide can be determined. The
absolute values of the N02 and DO concentrations depend on the
dissociation of molecular nitrogen in the chemosphere. The
chemical conditions cannot be applied in the aesosphere since the
life-time of NO is relatively lcng, and a downward transport is
involved. Very special assumptions concerning chemical reactions
would be necessary to reconcile the photochemical picture and the
observational results. The introduction of ionic reactions,
considered in an accompanying paper, will lead to a correct
interpretation. {Author abstract)##
1144
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
O5208L
T. J. Wallace, and N. Friedman
FONDAMENTAL INV ESTIGATION OF THE CATALYTIC DEGRADATION OF
HYDPOCARBCN FDEIS (FIRST QUART!RIY FBOGBESS REPT» FEB. 16-MAY
16, 1965.) esso Research and Engineering Co., Linden, N»
J., Process Research Div.. Bay 16, 1965- 30 pp. {Kept- No.
1)..
The reactivity of dilute solutions of benzaldehyde phenyl
hydcazone (EPH) and tolyl phenyl hydrazone (TPH) in benzene
toward molecular oxygen has been determined at 25 to 30 c« and
one atmosphere presEure of oxygen. Both hydrazones oxidized
readily under these conditions with TPH being more reactive than
EPH, This reactivity difference is probably due to the
electron-donating capabilities of the methyl group. It suggests
that electron-attracting groups will decrease the reactivity of
the initial hydrazone but accelerate the decomposition of the
peroxide which is formed,. The stoichiometry of the above
reactions was determined. Each mole of oxygen consumed reacts
with one mole of hydrazone to produce one mole of peroxide. The
disappearance of the hydrazone is best represented by a pseudo
first order kinetic plot„ Gccd reproducibility of the rate
constants was observed. The rate-determining step is, most
likely, hydrogen atom and cumere in benzene at 25 to 30 C.
About 8 to 10$ oxidation of each hydrocarbon was observed under
these mild conditions., In the absence of BPH, no oxidation of
indene vas observed over a 72 hour period. Infrared data show
that indene is converted to products which contaih a carhonyl
linkage., To date, attempts to oxidize tetralin have been
unsuccessful- (Author abstract)#»
05226
E.. Ferht, and R. A« Back
THE REACTION OF ACTIVE NITBOGEN WITH HIXIDRES OF ETHYLENE AND
NITRIC OXIDE . Can. a. Chem. 43, 1B99-904, 1965. {Presented
at the Annual conference. Chemical Inst, of Canada,
Kingston, June 1964, S,F»C„ No. 8406.)
The reaction of active nitrogen, produced in a condensed
discharge at 1 mm pressure, with mixtures of ethylene and nitric
oxide has been studied with mixtures ranging in composition from
pure ethylene tc pure nitric oxide.. The sun of HCN ~ 14N15N
produced from mixtures of C2H4 and 15NO remained constant and
equal to the HCN produced from pure C2H4 for NO
concentrations up to SO vole *. As more NO was added, this sum
rcse towards the value of 14N15S produced from pure 15NO„
These data appear to lend support to the HCN yield from
ethylene as the true measure of nitrogen atom concentration. It
is suggested that 15N0 also undergoes a concerted reaction with
excited 14N14R molecules, to produce 14N15N, and that these
excited molecules can quenched by collision with ethylene or
methane without consuming nitrogen or forming HCN. (Author
abstract)
M. Basic Science and Techrrology
1145
-------
05246
C. S.. Nairaan,, M. Y. Dewolf, and J.. Schwartz
STUDIES OP THE EFFECT OF LASER RADIATION ON CHEMICAL ACTIVATION
AND VAPOR FOG NUCLEATION (QUARTER1Y PROGRESS REPT. NO. 1).
Mithras, Inc.., Cambridge, Mass. Nov. 1964. 17 pp« (Kept.
No. MC 64-110-R1.)
The first objective is the study of various effects of laser
radiation upon vapor and liquid systems comprised of, but not
limited to, the simulant dimethyl methylphosphonate (DMMP) on air
components or both. The second objective is to obtain basic
information on the condensation of vapor or aerosol fogs as a
result of laser radiation. The chemical shifts, coupling
constants, and relaxation times of the methyl and methoxy protons
in DMMP have been measured by nuclear magnetic resonance (NHR)
techniques. Effects of focused and unfocused, Q-switched and
non-Q-switched laser radiation on methanol vapor in a continuously
sensitive cloud chamber have been studied; a much less intense
laser beam can produce condensation fcy incidence on a suitable
surface than is required to produce tracks directly with a
focused beam. A cloud chamber has been tested with low vapor
pressure materials, such as water, to determine the modifications
that are necessary, in order to study DUMP in the cloud chamber.
From NBR studies, it was concluded that background information
about the conventional 8MB spectrum and relaxation times is both
essential and measurable- (Author abstract)
05248
Newhall, H» K.
CHEMICAL EQUILIBRIUM PROPERTIES OF AMMONIA-AIR COMBUSTION PRO-
DUCTS- California Univ., Berkeley, Dept. of Mechanical En-
gineering. (Rept. Nos. TR-1 and HPS-64-4.} «DEC„ 1, 1964.
80 pp.
Results of the machine calculated thermodynamic properties of
reacted ammonia and air are presented. The resulting properties
are available to use as is or for further utilization in predicting
air breathing engine performance, where the fuel is ammonia..
The principal portion of this report is embodied in the tabulation
of species distribution and thermodynamic properties- Included
are ammonia—air mixture equivalence ratios ranging from 0.2 to
1.4, where 1.0 represents chemically correct. The range of ratios
allows for application to Otto, Diesel or Brayton cycles. All
numerical results are based ufob the products of combustion
resulting from the reaction of one pound of air with the reguisite
weight of ammonia.. In the determination of product composition,
the following chemical species were considered to exist in chemical
equilibrium: C02, CO, 820, H2, NO, OH, N2, 02, H,
N, 0 and &r. While traces of additional components might
theoretically exist, their concentrations would be so small as to
1146
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
be negligible for the purpose of this work. All basic
thermodynamic data employed in this work has been obtained from the
Joint Ar»y, Navy, Air-Force Thermochemical Tables, which is
presently the most universally accepted source of theraio-chemical
data. Two previously developed digital computer programs, one of
them being for air fuel ratios greater than stochicmetric
proportion, were used for determination of products over a wide
range of temperatures, pressures and fuel-air ratios. For each
pair of temperature and pressure values selected, the following
data is presented: (1) Chemical composition of products of
combustion; (2) Internal energy of products of combustion; (3)
Entropy of products of combustion; and (4) Volume of products of
combustion.
05253
A. T« Phelps, and G. J. Schulz
ATOMIC COLLISION PROCESSES HELATIHG TO THE IONOSPHERE,.
Restinghouse Besearch Labs., Pittsburgh, Pa., Dept. of
Physics. (Dec. 3, 1964.) 3 pp.. (Research Memo. 64-9E2-113-
¦ 3.)
I. Bass Spectrometer with Ion Telocity Filter: In the
course of work on the production of O(-) fro* CO it was found
that, apart from the sain resonance capture peak in the
cross-section occurring at about 10 evf small subsidiary peaks
exist at higher energies, but below the threshold for pair
production, presumably due to processes of the type e+ CO * C(-)
+ C (electronically excited). 21.. High Pressure Mass
Spectrometry: The mechanisms cf formation of 9 (4+) and 0 (3+)
ions in ion-nolecale interactions in N2 were investigated further.
The results indicated that the M4+) ion is formed through
processes involving (2); Ne82S)
-------
Developments in several aspects cf this research are discussed:
(I) Charge Transfer in N2, 02 and DC - Through improvements
in design and experimental technique ion energy measurements dovn
to 20 ev were Bade. The damaging effects of space charge fields
which increase with decreasing energy, were minimized by arranging
so that the path length traversed by the low energy ions would be
small. The influence of the slow-ion collection field on the
primary ions was diminished through redesign of the electrode
structure in the interaction region. Oxygen Atom Source
Development - In rf discharge Mas used for dissociating oxygen
molecules; design of the discharge tube is disucssed. charge
Transfer in Atomic - Oxygen - Apparatus for this investigation
is discussed. The ions Here produced in an electron bombardment
ion source and vere focused and magnetically mass-analyzed before
arrival at the experimental chamber and additional focusing and
collimation vere provided before intersection of the neutral beam
by the ion beam. Cross sections for the charge transfer between
atomic oxygen and N (plus), N2fcplus), and 02 (plus) ions are pre-
sented. Ion - Molecule Beacticn Studies - Modulated crossed
beam techDigues are being applied to the study of ion-molecule
reactions of the general type X (plus) Y2 egual XT (plus) plus Z
The apparatus is discussed. At the present the signal resulting
from the reaction O(plus) plus N2 egual NOPlus) plus N is be-
lov the noise level, but improvements in the apparatus should make
this and similar reactions observable.#*
0526?
H. A. Taylor, and D. S. Sethi
BITFIC OXIDE PHOTOLTSIS (FIMAI DIPT.). Sew York Dniv-, p8n.y.
(Aug., 31, 1965.} 4 pp. (Sept. No. CD 68018.)
An Aerograph gas chromatograph was used with a millivolt range
recorder. The absorbent was a six inch column of silica gel, used
at room temperature with helium as the carrier gas at flow rates in
the range of 60-65 ml/min. Samples were injected using a
gas-sampling value connected directly to a vacuum system, pressures
being measured on an octoil manometer. In elution, N2, NO and
H02 were removed in the first ten minutes and H20 around twenty
minutes.. The 10 and W02 peaks were not always separable, the
one appearing as a shoulder on the ether peak at some
concentrations bat the retention of the H20 permitted easy
separation and therefore recognition. By calibrating standard
mixtures of *2, SO, S02 and H20, a lover limit for the
detection of 1120 vas established at 10 to the-Bth power mole..
Some twenty photolyses of *0 at 1070 A were made and the
products analysed by the new procedure. None of these shoved any
H20. Since there appeared to be some small variation in the
retention time of 1120 from sample to sample of the calibrating
standards, the photolysis product analysis was sandwiched between
two standard runs. Mo H20 peak appeared. In an effort to
increase the concentration of WC2 with which N atoms night
react during photolysis, small amounts of oxygen were added to the
>0 before photolysis. Still bo 820 could be found. Finally,
small amounts of >20 were added initially to the NO and the
mixture photolyzed at 1470 A. The products after the run
contained no H20. It is apparent that during the period of the
1148
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
photolysis any N20 that night be produced was decomposing* It
is to be concluded that the N20, suEFected in the earlier work
reported in the accompanying reprint, was actually C02 and that
under the experimental conditions with a duration of photolysis
of from 15 to 20 minutes no H20 is present among the final
products. Khile definitely answering the question of the presence
of N20 in the system studied earlier# it must be realized that
another question is posed in its place, namely, if the duration of
the photolysis were shortened, could N20 be found among the
products before its decomposition. To investigate this, as well
as to attempt to answer the guestion of the effect of a change in
the duration of photolysis, a research assistant has undertaken as
his doctoral problem, BO photolysis at 1470 A by a flow method.#
C5268
E. B. Stephens
AESOHPTIVES FOB INFHAHED DETERMINATION OF PEBOXYACYL NI-
TBATES. Anal.. Chem. 36 (4), 928-9 Apr- 1964).
As it has become apparent that the atsorptivities given in the
published PAN spectrum are too low by a factor of about two,
probably because of some error in measurement of the concentration,
new measurements were made and are reported. Because these
compounds are highly explosive, the determination of their
atsorptivities presented special problems. Two independent
methods were eventually developed. In the first, a
pressure-volume technigue (PV), a glass bulb of known volume on a
vacuum line was filled with a measured pressure of PAN vapor.
This was brought to one atmosphere with nitrogen and then swept
into the long patch cell {volume, 640 liters; filled with air at
atmospheric pressure). This produced a concentration of a few
parts per million which gave sufficient absorption for
measurement at a path length of 120 meters« This technique
eventually yielded reproducible results for the first two members
of the series, PAH and PPN. The vapor pressure of PBN is
too low to apply this technigue with available equipment. The
second technigue consisted of filling a lambda pipet (5 microliter}
with the liguid, then allowing this to vaporize into the
circulating system of the long path cell. This also gave a
concentration of about 2 p.p.m» and was quite reproducible. The
densities of the liquids were estimated to be 1„2 grams per ml.
since they sink in water but float on concentrated potassium
iodide solution- Molecular weights were taken. This
technigue was successful for PPS and PBN bat a single attempt
to apply it to PAN failed because the sample exploded while
being vaporized into the cell- For PPN both techniques were
applied and satisfactory agreement was obtained. A mixture of
PAN in nitrogen was found to contain 7230 p.p.m. by diluting
100- or 200-ml« samples into the long path cell, i 10-ci. gas
cell was then flushed with this mixture at atmospheric pressure
and the complete spectrum |3 to 15 microns) recorded using a
Perkin-Elmer double grating spectrophotometer at a slit program
of 10.00,, The absorptivities were in good agreement with those
obtained at 120 meters- The absorptivities of PPN and PEN
measured in the 10-cm. cell were calculated assuming the value at
12,. 58 microns to b« tha same as that found at 120-meter path-
Because of its lower vapor pressure the PBN spectrum was weaker
than the others and therefore somewhat less accurate.##
M. Basic Sciencfl and Techno logy
1149
-------
05286
On F. Devlin? and I,, c. Hisatsune
DREY-BRADLEY POTENTIAL CONSTANTS IN NITEOSYI AND NITRYL HALIDES..
Spectrochim* Acta. 17, 206-17, 1961.
The Urey-Bradley force field has been used to calculate the
vibrational force constants in NOF, NOC1, NOBr, N02F and
N02C1.. Befined force constants using hacionic frequencies of
N0C1 and N02 molecules containing isotopic nitrogen atoms have
also been evaluated* The transfer of Urey-Eradley force
constants from N20i» and NOX ro N02X yielded reasonably good
results except for the N - F stretching mode in N02F.. For
the nitryl fluoride a possible change in assignment is suggested
from the present calculations. (Author abstract)t#
C5288
I. C« Hisatsune,, and K„ H» Hhee
THE INFRARED SPECTRUM OF N203- (In: Advances in Molecular
Spectroscopy.) Proc.. Fourth Intern- Meeting of Molecular
spectroscopy, 1959. 3, 989-98, 1962»
The infrared spectrum of a mixture of N203 and N20U vas
studied in the liquid phase frcm 2 to 25 microns and in the solid
phase from 2 to 35 microns, both at low temperatures. By
comparing this spectrum with that of pure N204 in the same
phases, absorption bands belonging to H203 were identified. A
tentative assignment of all but three of the fundamental
vibrations in N203 is presented.. (Author abstract)##
05289
I» C. Hisatsune, J. P. Devlin, and p8y. wv8ada
INFRARED SPECTRA OF SOHE OBSTABLE ISOMERS OF if204 AND N203-
0„ Chem. Phys„ 33, (3) 71<»-9, Sept. 1960.
The temperature dependence of the infrared spectra of N204 and
N203 in the solid phase at liquid-nitrogen temperatures has been
investigated. From these spectra of both 14M and 15N isotopic
molecules, absorption bands vfaicb may be assigned to unstable
isomers of these nitrogen oxides have been identified. A
reasonable interpretation of these absorption bands can be made by
assuming the existence of two unstable forms of N20« and one of
S2Q3. (Author abstract)I#
1150
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
05302
A. Levy and E. L» Merry man
S03 FOHMATION IN H2S FLARES. J. Eng. Power
87, («) 374-8, Oct,. 1965. (Presented at the Winter Annual
Meeting, American Society of Mechanical Engineers, New
York City, Nov- 29-Dec. 3, 196«.)
The microstructure of H2S-02 flames was developed in terns of
composition and temperature profiles. With the aid of these
profiles* rates of formation of S02 and S03 are reported and
discussed.. With the aid of kinetics and thermodynamic data
developed for the principal reaction steps, it is shown that a
major part of the S03-problem may be related to the O-atcm
oxidation of S02 in the flame. These fundamental studies of
thermochemical reactions provide the basic information needed as
the next step in understanding how reactions in flames and on
surfaces affect external corrosion and deposits in boiler
furnaces. {Author abstract)##
05325
long* P..
FOBBATIOH OF POLYCYCLIC AROMATIC HYDROCARBONS DOBISG INCOMPLETE
CCHBOSTION. {Progress Rept. Oct. 1, 1964-flar- 31, 1967).
Birmingham Univ., England. {Bar- 1967}. 37 pp.
This report comprises three parts: part I: discusses the
development of a rapid analytical method for polycyclic aromatic
hydrocarbons in soots. Extraction with CHCI3 was followed by
column chromatography and then by programmed temperature gas
chromatography, with UV spectrophotometry. Certain polycyclic
aromatics thus identified* have not been reported hitherto in the
literature on soots from hydrocarbon flames* investigations were
made on diffusion flames in which various concentrations of 02 in
02-N2 and 02-Ar mixtures as oxidant were used. In other
experiments oxygen and other additives were introduced into the
fuel supply. The effects on the formation of total soot,
carbonaceous residue, CHCI3 soluble material and polycyclic
aromatics are discussed. Part II: An investigation was made of
the concentrations of stable species in the pyrolysis zone and
particularly in the luminous zone of propane and ethylene diffusion
flames burning on a Wolfhard-Parker type of burner. The effects of
02, H2 and C2H2 as additives to the fuel and of 02 and N2 to the
air stream were examined. Besults shoved that the sooting rate is
related to the C2H2 present in the luminous zone for the C2H4
flames, part III: An investigation was made of the polycyclic
aromatic hydrocarbons associated with the soot in pre-aixed C2H2-02
flames operating at 20 mm. Hg« On the assumption that the
concentration of polycyclic aromatics in the soots collected at
increasing heights in the flame represents the state of affairs in
the flame, it appears that the polycyclic aromatics ate formed
principally in a lower temperature region of the flame than that
corresponding to "carbon** foraatipn. Results also indicate that
C2H2 is important in carbon formation in C2H4 and C3H8-air
diffusion flames. (Author summary modified)
M, Basic Science and Technology
1151
-------
05333
Purcell, 1.. C. and I. P. Cohen
PHOTO-OXIDATION OF HYDROCABEOKS IN THE PRESENCE Of ALIPHATIC
KETONES. Atmos., Environ-, 1 (6):689-692, Nov.. 1967. 16 refs.
Products of photooxidation reactions involving ketone-hydrocarbon
mixtures are reported. Reaction mixtures vere prepared in plastic
bags fabricated from fluorinated ethylene-propylene plastics.
The containers were irradiated by fluorescent lamps with intensity
maximum at 3100 A. The ketones and/or hydrocarbon mixtures
consisted of: acetone, acetone-2-methyl-1-butene, and diethyl
ketone.. The percentage conversions, after 1,2, and 3 hours of
irradiation* of 2-methyl-butene-1 and acetone as a function of
ratio of ketone to olefin shoved that the acetone conversion is
essentially constant, whereas olefin conversions increase with
increasing ratio. Extrapolation of zero ratios of ketone to
olefin indicates an inexplainable background reaction at longer
conversion tines. As with the aldehyde-olefin systems, the rate
of consumption of olefin increased at longer reaction tines. The
ketone conversion rates are virtually constant. Past oxidants
such as ozone or peroxy acid were not detected. Alkyl
hydroperoxide was identified as a slow oxidant product. The
portion of these products due to the ketone photooxidation and that
due to the olefin has not yet been determined. A mechanism often
cited to explain the photooxidation of ketones involves a
free-radical scheme.I*
05351
Cole, ft. and Shulman, H. I.
THE ADSORPTION OP S01F0B DIOXIDE EI DRY IOH EXCHANGE
BES1NS.. Clarkson Coll., of Technology, Potsdam, N. Y., Dept. of
Chemical Engineering. I960* 19 pp. (Published in part in Ind.
Eng. Chem- 52, (10) 859, Oct. 1960.)
Adsorption-equilibrium data were cbtained for the adsorption of
sulfur dioxide from air-sulfur dioxide mixtures onto dry ion
exchange resins. The resins are shown to compare favorably with
those adsorbents in commercial use with regard to their adsorptive
capacity-temperature characteristics. Isosteric heats of
adsorption are tabulated. Isotherms and characteristic carves
representing the equilibrium data are presented.. (Author abstract)
05378
Rinura, K« K. Kimotauki, 0. Tada, and K. Nakaaki
OH THE ATMOSPHERIC OXIDATION OP S0IIUR DIOXIDE. Bodo Kagatu J. Sci.
labour, Tokyo. 41 (10), 501-11, 1965. Jap„ (Tr.)
Basic studies were conducted on the behavior of S02 which is aost
1152
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
representative of gaseous atmospheric pollutants, and the effect of
atmospheric conditions were followed. The first study vas to
follow the tine changes in the decrease in 502 concentration within
a sealed container especially with respect to the rate of air flow,
humidity, or presence of particulate natter. It was found that
high air circulating rate or high humidity increased the rate of
decrease in S02 concentration.. This rate also was greater when
particulate natter was present than when there was none. This
¦teans that the oxidation of S02 is favored by high circulating
rate, high humidity, or the presence of particulate natter.
Qualitative and quantitative tests were conducted on the fornation
of sulfuric acid by the atmospheric oxidation of S02 or by the
reaction of S02 with other gases present in the atmosphere. A
known concentration of S02 was generated into a 27 cu m chamber,
and the H2S04 mist generated was analysed. This was followed by
studies of the reactions between S02 and other gases in 20 1 and 5
1 reaction bottles under fixed conditions, and the products of
these gaseous reactions were analyzed. The results verified the
production of H2504 from S02. It was found that there vas much
greater production of H2S04 fron S02 when other gases such as N02,
ozone, or H202 were present rather than s02 alone. The H2S
04 mist produced from SO2 was observed under a microscope, and
it was verified that liquid droplets (H2S04) were being formed in
the atmosphere. It was found that the presence of particulate
natter greatly accelerated H2S04 production. It vas found that
the atmosphere of an urban area also contains particles similar to
the mist formed in the experiments. This vas verified by electron
microscopy.. (Author summary)
05423
Benson, S» t).. and G. S„ Haugen
THE HECHANISH OF THE HIGH-TEBPEFATUBE REACTIONS BETWEEN C2H2
AND HYDB0GEN„ J. Phys. Chen., 71(13):4404-4411, Dec. 1967.
24 refs«
The observed high-temperature rates of isotope exchange between
C2H2 and D2 have been interpreted in teems of a radical
mechanism. The chain propagation steps for the system are D +
C2H2 yields C2HD ~ H and H + D2 yields D + HD. The
lover temperature addition kinetics to form C2H4 are fitted very
well by a related chain with the same initiation and termination
but a different propagation* The theoretical steady- state rate
expression, derived from the radical mechanism, adequately
predicts the observed rates at temperatures greater than 1400 deg
K.. The problem of attainment of steady state during the short
time interval of the experiment and the catalytic effect of traces
of oxygen and organic impurities on the induction period are
discussed. {Authors* abstract, modified)##
0 5425
Shaw, B., r. H. Cruickshank, and S. V. Benson
THE REACTION Of »ITRIC OXIDE WITH 1,3- AND
1,4-CYCLOHEXAUDIEVES. J. Phys. Chen., 71(13):4538-4543 Dec.
1967. 16 refs.
M. Basic Science and Technology
1153
-------
The gas-phase reactions cf nitric oxide with 1,3- and
1 ,4-cyclohexadiene have been studied in a Pyrex reaction vessel
between 306 and 359 deg. Initial pressures were varied:
1,3-CH, 3-57 torr; 1,U-CH, 10-71 torr; and NO, 61-436 torr.
No pressure change cobId be detected. Products identified by gas
chromatography and mass spectrometry were water, nitroux oxide,
benzene, and traces (about 10* of the benzene) of cyclohexene.
Good mass balances were obtained for the hydrocarbons, but the
water analyses were erratic and the nitrous oxide was less than
given by the stoichiometric equation.. The rate of production of
benzene was unaffected by increasing the surface to volume ratio
20 times and was first order in cyclohexadiene and nitric oxide-
The rate-determining step is given. (Authors" abstract,
modified) ##
C5091
Stephens, E~ B»
TBE FORMATION OF MOLECULAR OXYGEN BY ALKALINE HYDBOLYSIS OF
PEBOXYACETYL NITBATE. Atmos. Environ. 1„ 19-20, 1967.
Alkaline hydrolysis of peroxyacetyl nitrate (PAN) vapor was
found to produce Molecular oxygen in sole for mole yield. This
accounts for the oxygen which was missing in the hydrolysis experi-
ments of Nicksic, Harkins and Mueller. The hydrolysis equation
05611
S. W. Nicksic, J. Harkins, and 6. A. Fries
A RADIOTRACER STODY OF THE PRODUCTION OF FORMALDEHYDE IN THE
PHOTO-OXIDATION OF ETHYLENE IN THE ATMOSPHERE (PART IT—THE
tfFECT OF OTHER COMPOUNDS ON YIELD AND CONVERSION). J. Air
Pollution Control Assoc.. 11, (6) 22K-8, June 1961..
In this study, the tracer procedure was used to study some aspects
of the effect of composition of the irradiated Mixture on .the
amount of formaldehyde produced from ethylene, the latter being the
dominant olefin in auto exhaust. The irradiation chamber
contained oxidants, N02» CH20, hydrocarbons and aerosols.
Oxidant, nitrogen dioxide, and aerosols were measured in order to
obtain a more complete monitoring record of the reaction.
Chemical formaldehyde and radiochemical formaldehyde measurements
together with gas chromatographic determination of hydrocarbons,
were used to establish yields and conversion. Results showed:
(1) Ethylene gives more formaldehyde in the presence of oxygenates
and certain aromatics because the reactions are faster; the
fraction converted, however, remains constant. The guantitative
aspects of the effect of oxygenates remain to be studied. (2)
Formaldehyde yield from ethylene irradiated alone depends on the
nitric oxide-hydrocarbon ratio,. (3} In the presence of other
olefins, the nitric oxide dependency is much less.. (4) Production
of formaldehyde from ethylene is not influenced by other olefins
1154
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
except tor the nitric oxide effect. In reference to changing
composition of exhaust, oxygenates can be expected to increase
formaldehyde formed daring photo-oxidations, but it is not yet
possible to state how big the effect night be. The removal of
olefins will probably affect formaldehyde prodaction in proportion
to the extent of removal. Removal of other olefins will not
affect the reactions of ethylene per se except for the nitric
oxide-hydrocarbon ratio effect.#*
05613
Levine, R« F- Hamilton, and E., Si eon
ATHOSPBERIC PHOTOCHEHICAt BEACTIONS OF HALOGENS AND BtJTYL
HALIDES. J* Air Pollution Control Assoc.*
14(6):220-223, Jane 1964. (Presented at the 56th Annual
meeting. Air Pollution Central Assoc., Detroit, Hich.,
June 9-13, 1963.)
this investigation was oriented toward delineation of the
interactions involved in the chemical inhibition of smog exhibited
by iodine and to a much lesser extent by the other halogens.
Apparatur used for handling and irradiating polluted atmospheric
air was a 500 cu ft chamber enclosed by a "flylar" polyester film
1 nl thick- The chamber is mounted on large casters allowing
positioning of the unit for optimum sunlight exposure. When
thermal (dark} reactions are studied# the entire chamber is rolled
into a large, light tight, thermostatically controlled oven.
Other details concerning the laboratory procedure are given. The
results of these tests show that neither temperature, over the
range of about 100 to 200 P, nor sunlight greatly influences the
reaction ratio of 03 with iodine 2, and that sunlight has a much
greater effect on the reaction rates of the halogens with 03 than
does temperature. The qualitative rates of halogen-ozone
reactions in purified air in sunlight are i.odine 2 greater than
Er2 greater than C12. The effectiveness of iodine 2 in
reducing 03 in a smoggy atmosphere is enhanced over its effect on
03 in purified air, whereas the effectiveness of Br2 and C12 in
quenching siog 03 is diminished. The effectiveness of Br2 in
reducing 03 is inhibited by the presence of both saturated and
unsaturated hydrocarbons, whereas the iodine 2-03 reaction is
unaffected.**
C5628
E. Briner, fU Pfeiffer, and 6. Kalet
A CONTBIBUTIOH TO THE STUDY 01 PEROXIDATION OP NITJtOGEN
OXIDE-III (THE INCREASE IN TBI SSEED OP HITBOGEN OXIDE
PEROXIDATION AT VERY LOR TEBPERATORES). J. Chim. Phys.
(Paris) (Translated as JPBS S-8527-I.,) 21, 25-44 (1924). Fr„
(Tr.)
The process of peroxidation of nitrogen oxide, whose speed
increases as the reaction tempesatuxe drops, is a purely chemical
M. Basic Science and Technology
-------
process in flat contradiction with the general rule that the
speed of a reaction increases with the rise in temperature. A
systenatic study of this phenomenon, measuring the reaction speed
at increasingly low temperatures was conducted. By means of
suitable apparatus and operating methods, the process of
peroxidation over a temperature range from plus 75 deg.. tc minus
190 deg., was observed. For various temperatures within that
range, the absolute constants of speed as veil as the temperature
coefficients were determined. To shew clearly the influence of
temperature as it occurs in practice on nitrous gases, whose
composition is generally given in percentages of NO by volume,
the values for the relative constants and the half-reaction times
for various temperatures above and below 0 deg were calculated.
The half-reaction times are particularly interesting to consider,
since because of the formation cf N2C3 they indicate good
conditions for recovering nitrcus mixtures, To bring out the
effect of refrigeration at minus 183 deg. and for a mixture
containing 1% HO in air, a mixture about the same as the gas from
an arc furnace, the half-reaction time is 5 8 times shorter than
at ordinary temperatures. Intense refrigeration of the nitrous
gases will thus make it possible to reduce the volume of oxidation
chambers by very large proportions.##
05641
A. Goetz, 0. Preining, and T. Kallai
tHE HETASTABILITT OF HATORAL AKE ORBJN AEROSOLS. Geofis.
*ura Appl. (Milano) 50, <3j 67-80, 1961.
the principle of the sampling method of submicron aerosols with
the Aerosol Spectrometer is briefly described and the analytic
procedures for deriving the frequency-size distribution from
photo-oicrographic particle counts and microphotonetric light
scattering measurements of identical areas of the particle deposit.
After initial analysis the deposits were exposed to elevated
temperature (80 C) for several hours and re-analyzed. Four
^representative aerosol types, originating from the high sea, the
shore, vegetation, and metropolitan smog are analyzed in this
manner for the range (0.2 micron = to or less than a - to or less
than 1.3 microns).. All show a very marked decrease, even
disappearance of the smallec particles d less than 0.,5 micron) and
shrinkage of the larger particles |d less than 1 micron). By far
the largest effect is observed for the smog aerosols. This
volatility appears to be caused by either evaporation of the
particle substance or by the gradual oxidation of its organic
components into more volatile products (C02, H20). (Authors"
summary)*#
0E643L
H- H. Reamer
PARTIAL OXIDATION PRODUCTS lOBflJD DUH1MG COHEUSTION. Preprint.
1966,
1166
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
Cueing the period covered by this report, primary effort was in
the investigation of the effect of the fuel employed upon the
characteristic perturbations and the residual quantities of the
oxides of nitrogen. The experimental conditions encountered in
connection with the investigation of the behavior of the
propane-air and the n-butane-aii system are given. The average
reaction pressure vas approximately U1 p.s« i..a. The composition
of the products of reaction for the ethane-air, propane-air#
n-butane-air and natural gas-air systems are tabulated. All the
measurements involving natural gas-air, ethane-air, propane-air
and n-butane-air, were carried cut at a stoichiometric mixture
ratio of approximately 0.93. Variation in the perturbations of
normal stress and the frequency, as a function of the molecular
weight of the fuel are reported. The quantities of residual
oxides of nitrogen increased rapidly with an increase in molecular
vt from that of the natural gas-air system to that of the
ethane-air system and progressively increased with further
increases in molecular wt. to propane and n-butane. On the other
hand, the perturbations in the double amplitude of the normal
stress decreased progressively with an increase in molecular wt» of
the fuel. Phase relationships between the upper and lower ports
were almost exactly 180 degrees.. The freguency was approximately
5C9 cycles per sec in the case of the natural gas-air system. An
increase to 521 cycles per sec was found for the ethane-air system
and a small decrease to 518 and 516 cycles per sec for the
propane-air and the n-butane-air systems respectively was observed.
The analysis of the perturbations in normal stress obtained in
connection with the propane-air and ethane-air systems is
included. It is apparent, as in the case of the ethane-air
system, that a phase relationship slightly reater than 180 degrees
exists between the upper and lower ports, again confirming that the
primary nature of the perturbations involved a longitudinal wave..##
05824
1. G. Wayne
OH THE HECHANXSM OP PHOTO-OXIDATIOH IN SMOG- Preprint.
(Presented at the Jcint Research Conference on Motor
Vehicle Exhaust Emissions and Their Effects, Los Angeles,
Calif., Dec. 5, 1961).
The action of sunlight on urban atmospheres contaminated with auto
exhausts promotes oxidation of hydrocarbons and. NO and eventual
accumulation of 03. Same very intriguing problems of'chemical
mechanisms are presented by these reactions* It is the purpose
of this paper to subject to an elementally kinetic analysis some of
the proposed reaction schemes and to introduce a mechanism which
shows promise of explaining certain features of the photooxidation
process. Experiments have established that the oxidant material
is mainly 03. The various hydrocarbons present in automobile
exhaust disappear at different rates; olefins in general react mare
rapidly than paraffins, and mcst olefins react more rapidly than
ethylene, which is the predominant olefin in auto exhaust.
Relevant information available from experiments involving the
irradiation of synthetic atmospheres containing Ion concentrations
of hydrocarbons and oxides of nitrogen has presented reasoning
M. Basic Science and Technolofy
1157
-------
leading to the conclusion that react chains are very probably
involved in these systeis., Briefly, the reasoning is that, since
N02 is the only likely primary absorber of actinic light
products, hydrocarbons are probably involved by reaction with the
oxygen atoms produced in the photolysis of N02; but since the
rate of accumulation of products is sometimes faster than the
estimated rate of reaction between hydrocarbon molecules and
oxygen atoms, each appropriate oxygen atom collision must lead to
several subsequent steps, i.e.., to a chain of reactions. Such a
chain might promote the conversion cf NO to N02 in either of
two ways: by direct consumption of NO, or by consumption of
molecular oxygen to form 03.. Kinetic implications of chain
mechanisms of 3 different types cf examined: (1) A mechanism
offered by Saltzman, in which chains are initiated by free
radicals formed in a hydrogen abstraction reaction by oxygen atoms;
(2) A scheme suggested by Leighton incorporating some suggestion
of Schuck and Doyle; (3) A new hypothetical mechanism,
serving to illustrate the possible conseguences of a chain-
tranching step. Further study, particularly of the relative
rates of photooxidation of citric oxide and olefins in systems with
very little nitrogen dioxide, should provide evidence bearing on
the importance of branching chains in the urban photochemical smog
system.#•
05849
N.. A. Renzetti and G. J„ Doyle
THE CHEMICAL NATDBE OF THE PARTICULATE IS IRRADIATED AUTOMOBILE
EXHAUST- J- Air Pollution Control Assoc. 8 (H), 293-6
(Eeb. 1959).
The Los Angeles smog is characterized by its several
manifestations namely, eye irritation, crop damage, reduced
visibility, and high ozone concentrations, since automobile
exhaust is the major contributor to the pollution of the Los
Angeles atmosphere, its relaticn to all aspects of smog formation
is of prime importance. There have teen three studies of the
chemical nature of the particulate in non-irradiated auto exhaust.
This is believed to be the first report on the nature of
photochemically generated aerosol in auto exhaust. All of the
aerosol collected for the chemical analyses was generated under
similar conditions. The irradiated chamber was first flashed with
pure air and then auto exhaust at 5000 or 7200 ppa by volume was
allowed to enter the chamber after passing through the inlet
filter- As soon as steady state concentrations were reached, the
chamber irradiation lamps were turned on. The experiments were
dynamic in nature with 1-hr residence time for the mixture in the
chamber daring which period the irradiation took place.. The
aerosol under study was that generated essentially in a stirred
flow reactor. The runs lasted up to 9 hr in order to collect
samples of sufficient size for the standard microanalytical
techniques to be used in the analyses* Hicrocombustion technique,
microanalytical chemical techniques and infrared absorption
spectrum measurements are reported. Irradiated auto exhaust
appears to be the principal source of nitrate, sulfate, lead, and
organic compounds in the particulate matter of Los Angeles smog.
1158
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
Further, these findings explain the higher values of nitrate and
sulfate found in Los Angeles and other similar West Coast
cities in comparison with other cities.. Assuming six Million
gallons of gasoline are consumed in auto engines per day in Los
Angeles* about one ton per day of ncn-irradiated particulate and
at least 10 tons per day of photochemically generated particulate
are present in a typical s*og„##
05904
Bebbert, B« E. and Slagg* H-
PRIBABI PROCESSES IS THE PBOTOCHIDICAL DECOMPOSITION Of
JUTHCALKANES. Bull. Soc.. Chin. Beiges (Brussels) <71) 709-21, 1962.
The present work includes a detailed investigation of the gas and
liquid phase photolyses of nitromethane and nitroethane. The main
purposes were to determine the primary process or processes
occurring for both compounds and to investigate seconfary
reactions. Nitromethane and nitroethane were photolyzed in the
liquid and gaseous phases in order to distinguish the various
possible primary processes occurring for each compound. In the
case of nitromethane* a free radical split Has postulated to
account for the products as CH3802 + hv ¦ ¦ CH3 ~ K02„ 7or
nitroethane* there are at least two priaary processes occurring*
namely C2H5N02 ~ hv « C2m ~ BONO = C2H5 + H02» Various second-
ary reactions are discussed fcr both compounds.
06068
S. Nicfcsic, Jm Bar kins, a in fl P. K. BOellet
S0HE ANALYSES FOB PAH AND STODIES 07 ITS STBUCT0HE-
Atmospheric Environ. 1|1& :11-18 <(1967).
The methods described by the author previously (Hethods for
Heasuring the Concentration and studying the Structure of
Compound X in Synthetic Preparations, presented at the 7th
Conference on Methods in Air Pollution Studies, Los Angeles,
California, January 25-26, 1965) were used to obtain structural
information on this compound. AlXaline hydrolysis, hhr studies*
and neutron activation analyses for oxygen content were used.
The quantitative conversion of PAS to nitrite and acetate by
alkaline hydrolysis suggested that the coapound was the mixed
anhydride of nitrons acid and acetic acid* but the oxygen content
was much too high to support this structure* PAW la
sufficiently stable at aabient conditions in carbon tetrachloride
and benzene to permit a study of its reactions in solution* The
quantitative conversion of PAD in the presence of sodium
hydroxide to acetate ion and nitrite ion mast mean either that the
coapound contains the nitrite group or that the nitrite is in jbow
way formed accompanied by the evaluation of oxygen. Direct oxygen
analyses performed to data indicate that the molecule contains at
least 5 atoms of oxygen* but the data do not preclude the
possibility of still higher oxygen content. Perhaps a
M. Basic Science and Technology
1159
-------
relationship between PAN and nitrogen trioxide exists since the
latter is known to dissolve in alkalis with complete conversion to
nitrite (Sidgwick, The Chemical Elements and their Compounds,
Volume I, p 688, Clarendon Press, Oxford, 1950).. The
two-£old activity in depressing the freezing point of benzene and
the conversion to methylacetate in the presence of sodium
hydroxide require further study. Nuclear magnetic resonance
provides a convenient and direct observation of the solution
chemistry of this unusual molecule.##
06102
K. Endow, G.. J. Doyle, and J» 1. Jones
THE NATURE OF SCHE HODEL PHOTOCHEHICAL AEROSOLS* J. Air
Pollution Control Assoc. 13 |4), 141-7 (Ape. 1963).
(Presented at the 55th Annnal Meeting, Air Pollution Control
Association, Chicago, 111., Hay 20-2U, 1962.)
To obtain greater knowledge of the chemical nature of that part of
smog which reduces visibiligy, its significance to health and
its formation in model aerosols were generated by the
photo-oxidation of a single hydrocarbon, by nitrogen oxides and, in
mcst instances, by the co-photooxidation of a third
component-sulfur dioxide. The model aerosols are the result of
the same type of process which undoubtedly takes place in the
atmosphere, but the complexity of the reactions is considerably
reduced and the chemical composition is more closely controlled.
Evidence from infrared spectra of precipitated model aerosols
formed by the photo-oxidation of lower olefin homologs-nitrogen
oxides-sulfur dioxide mixtures at 50* relative humidity indicated
that the principal constituent of the aerosol was sulfuric acid.
Other analytical data, micrccheaical elemental analysis, spot
tests, and the like, gave support to the belief that the
principal constituent of these aerosols was sulfuric acid- In
addition to sulfuric acid, the aerosols contained a smaller
concentration of nitrite-type material. Height loss studies of
precipitated aerosols indicated either that portions of the
condensed aerosol materials were volatile or that the aerosol was
unstable and a decomposition product was volatile.##
06189
liu, K. T. Whitby, and H- s. yu
OS THE THEORY OF CHARGING OF AEROSOL PABTICIES BY UNIPOLAR IONS IN
THE ABSENCE OF AN APPLIED ELECTRIC FIELD. J„ Colloid Interface Sci.
23 <3), 367-78 {Bar- 1967).
The charging of aerosol particles by unipolar ions in a gaseous
medium and in the absence of an applied electric field has been
analyzed from the standpoint of the kinetic theory* The result has
been cellared and found to show good agreement with the
experiemental data, when the mean thermal speed of the corona ions
1160
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
used in the charging experiments is taken as 1-18 X 10*000 cm„/sec.
This is equivalent to assuming a value of 460 for the molecular
weight of the ions. The molecular weight thus determined and the
measured nobility of the ions of 1«1 sq. cm./volt-sec. at
atmospheric pressure both tend tc support the vie* that the corona
ions used in the charging experiments are molecular clusters foraed
by the interaction of the charge and dipole nsonent of the molecules
in the cluster.. However, the exact nature of these molecular
clusters could not be determined frcm the measurements made. The
experimental data show that the charging process is unaffected by
the mean free path of the ions and hence by pressure. This is in
agreement with the result of the theoretical analysis based upon
the method of kinetic theory of gases and is in variance with
theories based upon the macroscopic diffusion of ions.. It has also
been shown that the predicted increase in the particle charging
rate in HurphyBs analysis is entirely the result of neglecting the
curvature of the free path cf ions in the vicinity of a charged
particle. The correct equation* taking into account the curvature
of the ion free path, agrees with an equation first derived by
Dhite.. The failure of the theories based upon the solution of the
continuous steady-state diffusion equation to account for the
experimental facts has been shown to be due to the low
concentration of ions normally encountered in any aerosol charging
process and the essentially discontinuous nature of the charging
process.. (Authors" conclusions)
06236
Goetz, A..
THE SYNTHETIC PRODUCTION OP AEROCOLtCIDS AND THEIR QUANTITATIVE
EVALUATION* Proc- Nat. Cof. Aerosols, 1st, liblice, 1962.. (1964)u
pp.. 153-68..
The experimental efforts towards an understanding of the basic
processes which cause the fomation of aerosols indicate that these
reactions cannot easily be studied in quantitative detail
under static conditions it large exposure chambers* It appears
preferable to use for detailed studies of such reactions a
continuous, dynamically steady flew to which the various reagent
components are added, and which is sampled at various defined
reaction stages. The reliability of many such dynamic procedures
depends on the degree to which the physical conditions of the flow
system and the reaction kinetics therein can be kept constant over
extended test period« The method and instrumentation described in
this paper intended to over come these difficulties, ic particular
to facilitate the systematic study of synergistic effects in
aerocolloidal systems.
06320
E„ s« Pishburne, D.. R. Bergbauer, R. Edse
THE cmiOTTIC DBCORPOSITICK OP SITBO0S CUBE MB TBI THERMAL
EICCMPOSITION OP NITROGEN DIOXIDE. Ohio State Univ.,
Columbus, Aeronautical and Jtstronautical Research Labs.
M. Basic Science and Techtpiogy
1181
-------
(Aug.. 1965), 35 pp.. (Pept. AH1 65-169.,} (Contract AF
33(657-8951.) (Project 7065.)
CFSTI, DDC: AD 622692
The reaction between atonic oxygen and N20 has been studied
at temperatures ranging from 1500 to 2100 K. The atomic oxygen
in this study was generated by either the thermal decomposition
of N02 or the thermal decomposition of ozone. To determine
the amount of atomic oxygen released in the thermal
decomposition of N02 it was necessary to study this
decomposition in detail.. This study was conducted also at
temperatures ranging from 1500 to 2000 K and over a wide
range of concentrations and pressures. The reaction rates
obtained for the various steps in the decomposition of N02
are in general agreement with those obtained by other
investigators. The reaction of nitrous oxide in the presence
of N02 with Ar as the diluent was studied to determine if
the oxygen released in the decomposition of N02 would accelerate
the decomposition of N20* Ho noticable acceleration was
observed. Hany experiments were conducted with a H20 mole
fraction of 0..02 and 03 mole fractions varying between 0..005 and
0.06.» In these experiments the diluent was molecular oxygen.
The presence of atomic oxygen definitely produced an increase in
the rate of decomposition of H2C.. It is found that the
reaction between atomic oxygen and 820 is pressure dependent.. It
is shows that the different rate constants obtained by other
investigators may be reasonably explained on the basis of a
pressure dependent step in the reaction mechanism.. (Author
abstract)##
06418
C. Crr
THE ISF10ESCE OP ELECTROSTATIC IEFECTS OS TBE DISPEHSIOM Of
POWDERS, Preprint. (Presented at the 60th Annual Meeting,
Air Pollution control Association, Cleveland, Ohio, June
11-16, 1967, paper Ho. 67-116.)
The objective of this study is to relate the electrostatic
charging characteristics of powders upon dispersion to the
stability of the resulting aerosol. Present information does
net conclusively establish to what extent electrostatic charging
enhances or degrades the dispersics of a powder and whether or sot
the resulting aerosol is more or less stable. Tests designed to
measure the frictional charging characteristics cf powders
relative to ambient conditions are discussed. An apparatus was
devised in which pwders could be made to slide across solid
surfaces, indicating the charging developed. The presence of
certain gases (S02, C02, N02) altered the charging of a
number of powders. The influence of B02 was particularly
evident. Its effect was purely physical in many cases, for
evacuating a powder restored its original charging
characteristics. Various powders and mixtures of powders are
being dispersed into an aerosol chamber with the charge generated
upen dispersion and the decay rate of the aerosol being
1162
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
measured. The most interesting effect uncovered so far, although
it should not be unexpected, is that two powders that normally
charge due to frictional effects with opposite sign will produce no
net charging when nixed in the proper proportion*##
06t73L
Eonner, B.. H„
BE ACTION RATI DATA FOR SOME NITFOGEN/OXYGEN SPECIES. Rocket
Propulsion Establishment, Westcott, England, RPE-TH-U25,
24p., 1966.
DDC: AD80B585
Reaction rate data for sixteen gas phase reactions involving
species composed of nitrogen and oxygen are presented. The
sources of the data presented in each table are given as
references, together with brief indications how the data were
obtained.
C6H77
0. F., Carleton
STUEIES OF HETASTABLE HOIECOLBS OF ATMOSPHERIC INTEREST (FINAL
REPT. JUNE 1, 196U-ADG. 31,1966)* Smithsonian Astrophysical
Observatory, Caibridge, Mass., {Oct. 1966). 52 pp.. (Rept.
Mo. AFCRL-66—717.)
CESTI, DDC: AD 642 851
The work described in this report has focused on the study of
metastable states of atoms and molecules of atmospheric interest.
The technique was to form a thermal molecular beam and produce
metastables in the beam by electron bombardment. The metastables
drifted along with the beam, and were observed to decay in flight,
to collide with other molecules in a low pressure gas cell, and
to strike metal surfaces (with subsequent ejection of electrons).
The following observations were made: (1} N2 metastables excite
the gamma bands of No with a rate of about IX of the
momentum-transfer collision rate, populating only low vibrational
levels. (2) A long-lived 02 metastable state around 10.8 ev
reported by others apparently does not exist (but rather belongs
to impurities in the 02).. (3) long-lived metastable molecules
can effuse directly from a region containing a short duration
( a few msec) afterglow of R2 and (U) Excited N2 molecules
can maintain their excitation after collision with a teflon
surface, with a reflection coefficient of WO* + or- 20*» A
theoretical estimate of the mode of deca; of long-lived metastables
shows that electric dipcle radiation resulting from spin-orbit
coupling will almost always dominate magnetic quadrupole radiation.
{Author abstract modified)
M. Basic Scimce and Technology
1163
-------
06612
R- Penndorf
HIE SCATTERING COEFFICIENTS FOR SELECTED AEROSOL SIZE
DISTRIBUTIONS (FINAL REPT,. APR. 1, 1964 - OCT. 31, 1965).,
ATCO Corp.., Wilmington, Hass.,, Research and Development Div.
(Rept. Nos.i RAD-TB-65-39 and APCRL-65-836.) (Oct. 31, 1965J .
17 pp..
Formulas are derived for volume scattering coefficients
applicable to aerosols. Different types o£ size distribution for
the aerosol, such as normal distribution, log-normal distribution,
and exponential distribution, are assumed. Nominal results
obtained by the author and those published in the literature are
given and discussed. The volune scattering coefficients become
smooth functions.. The size distribution is very wide. Hence,
simpler mathematical formulation can be used than those obtained
from the exact Hie theory. However, only the number of aerosol
particles can be obtained frcs an evaluation of experimental data,
but details of the size distribution cannot be extracted from
experimental data. (Authorus abstract)##
06646
Go Porter and P.. Suppan
PRIMARY PHOTCHEWICAl PROCESSES IN ARCHATIC BOLECULES.. {PART
14. COMPARATIVE PHOTOCHEMISTRY CF AROMATIC CARBONYL COMPOUNDS).
Trans. Faraday Soc.v (528), 3375-83, Dec. 1966.
Quantum yields of photoreducticn are correlated with
spectroscopically determined energy levels of lowest singlet and
triplet states for a range of aromatic cacbonyl compounds. The
interpretation of reactivity in terms of electron density
distribution in the excited states, which was given earlier for
benzophenose derivatives. Is equally applicable to benzaldehydes,
acetophenones, and tc carbonyl derivatives of naphthalene and
anthracene.. The photochemistry of these compounds depends only on
the nature of the lowest triplet state, or the lowest singlet state
if intersystem crossing is not efficient (in the anthracene
derivatives and in ortho-, hydroxy- and a»ino-compounds|„ Both
the hydrogen-abstraction and the double-bond addition processes
involve essentially the approach of a negative charge towards the
carbonyl oxygen.. If the oxygen atom is negatively charged, there
will be an energy barrier increase from the n—-pi* state to
I—Pi* states and become greater with increasing CT character
of these states..##
06698
R„ W., Hum, B. Dimitriades, and R» D. Fleming
HOW HYDROCARBON TYPES DETERMINE SUGG-JOBBING POTENTIAL 07 EXHAUST
GASES. S.A.E. (See. AutCiCt. b8eng.) J. 74 (2), 59-61
{Feb. 1966).
1164
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
Relationships between automobile exhaust gas reactivity under
irradiation and composition of unburned hydrocarbons in the
exhaust was studied over a wide range of fuels and driving
conditions, indices measured were: rate at which NO is
converted to N02; oxidant formation; and formaldehyde formation.
These were correlated with concentrations of; unsaturates
plus oxygenates; non-aromatic unsaturates plus oxygenates; and
non-aromatic unsaturates plus oxygenates* less acetylene and
propylene.. Correlation between conposition and chemical
reactivity is not consistent, oxidant formation is constant
within experimental error limits. Variability in the rate of
KQ2 formation is considered to be due to variations in
composition, including variations in molecular weight, within each
of the general classifications with which reactivity correspondence
was sought. Inherently low precision of the analytical method may
be at fault for the «¦ or - 34* scatter shown in
formaldehyde-fornation data* For exhaust samples of similar
origin Ithat is, the same fuel), a fairly well defined correlation
exists between reactivity and composition. Extracting all or part
of the unsaturates and oxygenates from exhaust samples does tend
to reduce their reactivity. Nitrogen oxides also play a complex
role in determining reactivity. In a hydrocarbon-nitrogen oxides
mixture, reactivity is more or less a monotonic function of the
hydrocarbon concentration, but its dependence on nitrogen oxides
is not monotonic.. Comparing the reactivity of two exhaust samples
, therefore, means taking account not only of reactive hydrocarbon
concentrations, but also their ratios to nitrogen oxides, as well
as the direction in which the hydrocarbon to nitrogen oxides ratio
affects reactivity.##
06719
Harkness, A. c. and F. E. Hurray
GAS PHASE OXIDATION OF HETHTL HEHCAP1Intern. 3. Air
Hater Pollution, Vol. 10, p. 245-251, 1966.. 8 refs.
The reaction between methyl mercaptan and oxygen in the gas phase
has been examined in the temperature range 201 to 275 c. sulfur
dioxide is the chief product of the reaction, being formed together
with methane at the start of the reaction. Other products of the
reaction are carbon monoxide, carbon dioxide, hydrogen,
formaldehyde and methanol. In the presence of excess oxygen,
complete conversion to sulfur dioxide is obtained quickly at 275
C. At lower temperatures and lower oxygen content much of the
sulfur remains unaccounted for.. In confirmation of previous votk
the rate of reaction was found to be strongly accelerated by oxygen
and to be inhibited by mercaptan.##
06720
A. 0. Fatiadi
EFFECTS OF TEKFEFAT0PE AMD OF BITBAVIOIET HAEIAT10# ON PYHENt
AES0RBID ON GAB DEN SOIL. Environ.. Sci. Technol. 1 (7) ,
570-2 (July 1967) *
M. Basic Scltnce and Ttckiioiofy '
T16S
-------
Irradiation of pyrene adsorbed on garden soil for 2U0 hrs at 32
degrees gave a mixture of products that could be separated by
thin-layer and coluirn chromatography,. Eight compounds were
formed, and five have been identified: 1,1"-bipyrene, 1*6- and
1,8-pyrenedionesr and 1,6- and 1 ,8-pyrenediols. When the pyrene
adsorbed on garden soil was stirred in the dark for 240 hrs at 32
degrees, the yield of 1,1#-bipyrene was lowered (from 4 to 6X) to
0„3*, and only traces of the two diones were formed; on treatment
in the dark at 110 degrees for only 8 hrs, dione yields were
increased to 2..5*. When cthei particulates (silica gel,
alumina, Florisil, etc.) vere used instead of garden soil,
1,1'-bipyrene was not formed- Experiments in which
radical-capture agents were incorporated showed lower yields of
1,1"-bipyrene, indicating that the reaction with ultraviolet
irradiation involves a free-radical mechanism. The yield of the
diones was unchanged with these agents present, suggesting that
they are formed by attack of adsorbed oxygen on photo-excited
pyrene molecules., Irradiation cf pyrene in the crystalline
form without soil did not produce 1,1"bipyrene.. No attempt was
made to follow quantitatively the input of energy during the
irradiation of pyrene on soil (a heterogeneous reaction); from the
practical standpoint, however, the main objective of this study
was to trace the fate of pyrene cn soil, as a representative
reaction cf a series of polycyclic, aromatic hydrocarbons
(carcinogenic and non-carcinogenicj« (Author abstract)#*
0695U
H„ S. Johnston, G„ £,. Mcgraw, 1. 7. Paukert, I. W.
Richards, and J. Van Den Eogaerde
MOIECOIAP-MODOLATION SPECTROMETRY I. NEW HETHOD FOR OBSERVING
INFRARED SPECTHA C? FREE RADICALS. Proc. Hat'l Academy
Sci.., US 57 (5), 11U6-53 (May 1967).
in complex chemical reactions involving three or more free
radical intermediates, it is impossible to deduce a unique mec-
hanism merely by chemical analysis of all products and reactants.
The most promising source of information is spectroscopic
observation of the free radical intermediates. The flash
photolysis method obtains infrared spectra, producing high
concentrations of the intermediate radicals by subjecting the
parent gas to a short intense pulse of energy* There are
limitations to this method which are improved upon by the molecular
modulation technique. Here the photolyzing light is turned off
and on continually, modulating slightly the concentration of the
reactants, intermediates, and products. When the concentration of
a chemical species is varied periodically, absorption which is due
tc this species is used to modulate a transmitted infrared team
intensity.. Thus when scanning through the spectrum, the light
intensity is modulated only when one passes through that region
characteristic of a particular reaction member. This method
gives the vibrational spectra and the lifetime of the radical.*#
1166
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
C6980
A. Ju Fatiadi
SEPARATION OF PYFENEDIONES BY COIUHN CHHOHATOGPAPHY. J.
Chromatog. 20, 319-24 (1965)u
Pure 1*6 - 1,8 and 4,5 pyrenediones vie re needed as reference
compounds in connection with studies on the photochemical
oxidation of pyrene» The procedure reported by Vollnann for
the preparation and separation of 1,6 and 1,8 pyrenediones
involves a laborious series of processes. After tests with a
variety of adsorbents and solvents, it was found that 1,6 and 1,8
pyrenediones, in an oxidation mixture obtained from purene, are
separated directly on a column of silica gel with glacial acetic
acid as an eluate. The final purification of 1,6 pyrenedione
was accomplished on a column of activated aluvina with benzene as
a solvent. The composition of each eluted fraction was
checked by thin layer chromatography. The infrared and 1)V
spectra of the purified diones and of 1-0x0-6,7
phenalenedicarboxylic acid anhydride were recorded.##
07082
Jchnstone, H. p. and A. Boll
AIR POLLUTION . „ . FORHATIGN OF
Eng. Chen., 52(10):861-863, Oct.
the 136th Meeting, Div. of Rater
N.J., Sept* 1959..)
SULFURIC ACID IB FOGS., Ind.
1960. 15 refs» (Presented at
and Hastes, Atlantic City,
The formation of sulfuric acid from dilute sulfur dioxide in the
presence of artificial fogs nucleated by small particles of
manganese and iron salts vas studied. The effects of the presence
of inert salt nuclei and of inhibitors in air along with the
catalytic nuclei on the rate of reaction and formation of the
acid when relative humidity of air is below saturation, but above
the critical value at which saturated solutions of the salts exist
were also noted. Laboratory experiments with artificial fogs
forned in controlled atmospheres show that oxidation of sulfur
dioxide in air at concentrations corresponding to those in
combustion gases diluted 10 to 1000 times takes place rapidly when
catalytic nuclei ar« present, concentrations of acid up to 50 mg
per cubic meter are formed in a few minutes. High concentrations
of inert nuclei decrease rate of formation, but do not stop the
reaction. The fastest rate is with catalytic aerosol at relative
humidities just below 100V.#*
07085
Sharp, H», T. Kuwana, A. Csfcorne, and J. S. Pitts,
Jr..
SOHE ELECTHON SPIN RESONANCE STUDIES ON OLTBAVXOLBT IRRADIATED
M. Basic Science and Technology
1167
-------
SOLUTIONS OP AHTHRAQOINONE AND BENZOPHENONE. Reprinted from
Chen. Ind„, p„ 508-509, Hatch 17, 1962- 9 refs.
Elucidation of the photo-chemical reduction mechanisms of
anthraguinone and benzophenone in alcohol solutions has led to the
investigation of possible free radical intermediates or products
by electron spin resonance (F.S.B.J methods. A free radical
anion was produced photochemically at room temperatures by
irradiating a solution of 0.0006 B anthraquinone in lithium
hydroxide methanol. The overall band width of the E.S.It.
signal was 11..0 gauss. Definite configurations! proton
assignments could not be made. In neutral solutions of
methanol at room temperatures the irradiation of anthraquinone did
not produce an E.S.R. signal- When the temperature mas lowered
to minus 190 deg C. a broad singlet was obtained with no
hyperfine structure. The signal disappeared when the sample was
warmed to minus 150 deg C» At low temperatures the "reactivity"
of the radical is lessened. In the photochemical reduction of
benzophenone to benzpinacol, the irradiation of a degassed
solution of benzophenone in iscpropyl alcohol gives rise to an
"intermediate" species with an absorption maximum at ca»330 to
3400A. An attempt was made to detect this "intermediate" by
E.S.R.. The benzophenone solution was irradiated for various
intervals of time. After each irradiation, the solution was
examined by both ultraviolet and E«. 5«R« spectrometry . In no
case was an E.S.R. signal obtained.* However, when the
temperature was lowered to minus 150 deg C. and solution was
irradiated directly in the cavity of the instrument, a resonance
was observed, which disappeared rapidly at minus 100 deg C» The
E..S.P. spectrum for the isopropanol radical was not observed,
although it may be masked by the broad ban. It can be seen in
certain photosensitised systems irradiated at low temperatures.
Further work is in progress toward elucidating the intermediate(s)
present in the photolysis of benzophenone-I#
071 ce
Renzetti, V. A. and 6. J. Doyle
PHOTOCHEBICAL AEROSOL POBHATIOH III StlLFUB DIOXIDE-HYDROCARBON
SYSTEMS. Intern. J. Air Hater Pollution, 2:327-345, June
1960. 31 refs. (Presented at the Int. Clean Air Conf.,
London, Engl-, Oct. 20-2
-------
The high sulfate content of the particulate natter and low
gaseous sulfur dioxide concentrations observed in the Los
Angeles snog are consistent with the findings of this
laboratory program. (Authors* summary, modified)#*
074U5
J. B« Mudd, T.. To Hcflanus
PRODUCTS OF THE BEACTIOH OF PEB0XYACITY1 SITBITE WITH SULFHYDRYL
COMPOUNDS. Preprint, California Univ., Riverside,, Dept..
of Biochemistry and Statewide Air Pollution Research Center,
f (1 a|) p. 1967..
The proportion of oxidation and acetylation of sulfbydryl groups
by peroxyacetyl nitrate was investigated. The compounds chosen
for study were glutathione, coenzyme A, and reduced pancreatic
ribonuclease. It was expected that these studies would
elucidate the mechanism of toxicity of the peroxyacyl nitrates
found in polluted urban atmospheres. Peroxyacetyl nitrate
reacts with reduced glutathione producing eguimolar amounts of
oxidized glutathione and S-acetyl glutathione. Reaction of
peroxyacetyl nitrate with reduced coenzyme A results in the
formation of coenzyme A disulfide, accounting for 30-409 of the
reacted sulfhydryl. The remaining products can be separated
by ion exchange chromatography and are probably higher oxidation
states. There is no evidence of formation of S-acetyl coenzyme
A. The distribution of products obtained by treatment of
coenzyme A with peroxyacetyl nitrate is similar to that
obtained by treatment with hydrogen peroxide. Treatment of
proteins with peroxyacetyl nitrate has not provided any
evidence of acetylation of sulfhydryl groups. The formation
of intramolecular disulfides by treatment of reduced ribonuclease
with peroxyacetyl nitrate is apparent. Mo evidence was
obtained in favor of intermolecular disulfide bonds.##
07450
Sage, B. H»
PARTIAL OXIDATICB PRODUCTS FOBBED FUBIHG COHBUSTIOH (
PARTIAL OXIDATION PRODUCTS FOBBED DDBXHG COHBUSTIOH (SEVENTEENTH
PROGRESS REPORT: JAHUABY 1 TO JDHE 30, 1967). Preprint,
California Inst- of Tech., Pasadena, Chemical Engineering
Lab., ((31))p., 1967.
The monocbromator and collimator employed in the atmospheric
cobbustor, reported under the 15th progress report have been
adapted to the pressure combustor* Results obtained after changes
are reported. Tables and diagrass are presented.##
M. Basic Science and Technology
-------
07458
Benson, S„ 9., and G. fi« Haugen
MECHANISMS FOB SOME HIGH-TEHPERATOBE GAS-PHASE REACTIONS OF
ETHYLENE, ACETYLENE, AND BOTADIENE.. J„ Fhys. Chen.,
71 (6):1T35-17«6, Hay 1967,
Sufficient information concerning the rate parameters of the
individual propagation and ternination steps of radical reactions
now exists so that it is possible to predict the kinetic behavior
of a chain mechanism with better than order-of-magnitude
reliability. This precision cones from the similarities that
exist between the A factors and activation energies of homologous
reactions. In particular, the creditability of a proposed chain
mechanisn for the high-temperature gas-phase reaction of
unsaturated hydrocarbons can be tested by comparing the observed
kinetic behavior with that predicted by the mechanism. A
pyrolytic chain was proposed that adequately describes the
experimentally observed high-temperature hydrogenation of acetylene
and also the high-temperature pyrclysis of ethylene. The
propagation steps representing the formation of the major products
of these systems are diagrammed. The minor product in both
systems is 1,3-butadiene. In the pyrolysis of ethylene, the side
reaction accounts for the production of butadiene. In the case of
the hydrogenation of acetylene, a concurrent chain is responsible
for the side products. {Authors" abstract, modified)##
07463
Harrison, Arthur P»« Jr., and Vivian E« Raabe
FACTORS INFLUENCING THE PHOTODYNAHIC ACTION OF BENZO A PYRENE ON
ESCHERICHIA COLI.. J. Bacterid™, 93 J2) *.618-626, Feb- 1968.
23 refs.
Death of Escherichia coli resulted when a buffer suspension vas
exposed simultaneously to colloidal benzo a pyrene (BP) and
355-milliaicrons illumination. Neither hydrocarbon nor
illumination alone caused death; oxygen had to be present. The
survival curve had a shoulder, and then death proceeded
exponentially with time. Death rate was independent of
temperature between 6 and 32 C. The duration of the shoulder,
however, decreased slightly with increase in temperature. The
shoulder was not due to delay in BP entering the cell. Death
was influenced by the composition of the medium in which the cells
were grown prior to illumination. The amount of BP bound to the
cells was determined after three ethyl alcohol-ether extractions.
Appreciable binding occurred in the presence of 355-milliaicrons
illumination with air, and relatively little binding occurred under
nitrogen; very little binding occurred in the dark with nitrogen or
air.. At the outset, rate of binding under illumination with air
was not temperature-dependent, but with time it became strongly
temperature-dependent. Binding under illumination with nitrogen
was temperature-independent. Bound BP was associated primarily
with cell protein. Cells in growth medium resisted death and
1170
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
BP binding. At 21 and 32 C, deoxyribonucleic acid damage
occurred during exponential death.. No damage was detected at 21
and 32 C in the dark with BP* under illumination in absence of
Bp, or under illumination with BE in a nitrogen atmosphere.
(Authors" abstract)it
07488
Sekigawa, T»
IONS IN AIR (I). Text in Japanese. Kuki Seijo
(Clean air - J. Japan Air Cleaning Assoc., Tokyo),
3(2):26-30, 1965. 12 refs.
Ion size distribution, ion production, ion distribution,
ionization equilibrium, and annihilation of ions are discussed.
Ions can be extremely large, as in the case of snow or raindrops,
or very small like charged molecules. In the distribution curve
by Junge, ions greater than 0.00001 cm (0.1 micron) follow the
"inverse triple ratio law". In this paper, only small ions are
covered, i.e. those produced by electrolytic dissociation of
radioactive materials, cosmic rays, ultraviolet rays, short wave
radiation, separation of liquids, and corona discharge. Small
ions axe created when % single electron attaches itself to a
molecule. The mobility of positive ions is 0.9 to 1„7 sq. co./V
sec. In the atmosphere near the surface of the earth, there are
more positive ions than negative, with a ratio of about 1.1 to
1.2* In clean atmosphere there usually are from 300 to 10QO
positive small ions per cc. and from 200 to 800 negative small ions
per cc. The positive ion and radioactive aerosol concentrations
in clean and polluted air are compared in a table. The hourly
variation in ion concentration is graphed indicating that the
medium size ion has a p«ak around 1 P.H. The number of ions
present varies because of recombination of positive and negative
ions or attachment to other particles. When the production and
annihilation of ions are balanced, the ionization equilibrium state
is reached..**
07495
Ciborowski, J. and B. Pohorecki
THE EFFECT OF EIECTRICAL DISCHARGES ON SUBLIMATION CONDENSATION.
Int. Chem. Eng.# 7(1):4859, Jan. 1967. 46 refs.. Translated
from Chem. Stosowana, Vol. 2B, p. 159-182, 1966.
The effect of electrical discharges on the condensation of vapor
at temperatures below the triple point has been studied. A
simplified schematic diagram of the apparatus used is presented.
It was composed basically of a saturator, a heater, a superheater,
an ionizer, and a condensation chamber* The condensation was
carried out by mixing a hot stream of gas containing vapors of the
condensing component (naphthalene) with a stream of cold inert: gas.
It was concluded that: the existence of a considerable effect of
electrical discharges on the course of sublimation condensation has
been established. This effect is based primarily on
M. Basic Science sird Technology
1171
-------
intensification and simultaneous stabilization of the course of
the progress- The effect of discharges on the condensation
process depends on the type of discharge. This effect is
considerable in the case of spark discharges, but in the case of
corona discharges it was not observed at all„ The magnitude of
the effect observed depends to a snail degree on the voltage (if
it is large enough for spark discharges to occur). This
magnitude also depends on the thermodynamic parameters of the
system; however* no dependence on the flow rate of the gas
through the ionizer was observed (within the investigated limits of
changes of this value). The effects of electrical discharges on
the condensation process can be explained by the formation of a
larger number of active condensation nuclei, which facilitate
nucleation of the new phase.##
C74 98
Hughes, A. N.« M. D. Scheer, and H. Klein
THE REACTION BETWEEN 0<3P| AND CONDENSED 01EFINS BEICW 100
DEG K„ J. Phys.. Chen.., 70 (3) : 798-805, March 1966.
The addition of oxygen atoms to condensed simple olefins has
been studied in the 77 to 90 deg K temperature range. The
ground-state 0<3P) atoms were generated in the gas by
dissociation of 02 on rhenium or tungsten surfaces heated to 2300
deg K.» At 90 deg K and cxygen pressures below 10 ntorr, the
major products were found to be the unfragmented epoxides and
carbonyls. Above 50 mtorr, ozonides and oxygenated products
characteristic of rupture at the double bond were observed. Above
100 mtorr only the ozonides and their fragments were produced. At
77 deg K, the ozonolysis reaction occurred at much lower oxygen
pressures, comparison of these results with those obtained in
the gas phase at 300 deg K indicates that the low-temperature
environment efficiently removes the. excess energy from the excited
biradical forced in the primary act of 0 atom addition to the
double bond. In all cases studied, fragmentation was less
extensive than the comparable gas phase process. (Authors"
abstract)##
07499
Johnston, H„ s.. and ?. Cramarossa
BIGHII COMPLEX PHOTOCHEHICA1 SECHARISHS. Advance. Photochem.,
Vol.. 14, p. 1-2U, 1966. 16 refs.
In a kinetic or photochemical system involving three or more
free-radical intermediates, one can never deduce the mechanise by
any method that merely analyzes for all the final products and the
reactants. The reason for this indeterminacy is very
straightforward: there are simply more elementary reactions than
1172
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
observed products.. The Beer-Ianbert lav, properties of odd and
even numbers, and simple differential and integrated rate equations
are utilized in the interpretation of data for highly complex
photochemical systems. In the photolysis of propionaldehyde the
molecular split occurs to soae extent, bat the principal mode of
decomposition is into two radicals. Radical-radical reactions
are of two kinds, recombination and disproportionation* For
the recombination, there are six reactions and six different
products.. For the dispropcrtionaticns, there are nine
reactions but only six products (one of which is the reactant).
Each of the products is produced by three different reactions;
thus a kinetic study based on analysis of products alone will never
characterize any of the reactions. Notations for expressing the
number of reactions* products and radicals, the rate of destruction
of radicals, half-tine of radicals, rate of radical-reactant
reaction, rate of destruction of reactant, and the rate of radical-
radical and radical-molecule reactions are determined.. A
photochemical reaction may involve a chain reaction, or products
may be formed almost entirely from radical-radical reactions.,
chain reactions are favored by high reactant concentration, low
light intensities, and large rate constants for radical-molecule
reactions (high temperature, lev activation energy) » At a given
light intensity and reactant concentration, a reaction might
be non-chain at low temperature and a chain reaction with
substantially different products at high temperature. Typically,
photocheaists report quantum yield, the ratio of molecules of
products formed to photons absorbed. This taking of ratios
throws away the absolute value of the light absorption rate. A
photochemical reaction involving three or more radicals may be
simplified by careful selection of light intensity,
reactant pressures, or temperature. Three cases are considered:
Photolysis of Acetaldehyde, Photolysis of Acetone, and
Photooxidation of Acetone. In the photolysis of acetone,
simplification has been achieved but in the photoxidation of
acetone such simplification seems to be out of sight.##
07500
Jchnston, Harold D., and Julian Heicklen
PHOTOCHEMICAL OXIDATIONS. III. ACITOSE. J. Am. Che«u
Soc., Vol. 86, p.. 42«9-«25U, Oct- 20, 196U.
The room-temperature phctooxidation of acetone (0.25 to 17 mm.}
in oxygen (0.09 to 9.7 mm) with continuous ultraviolet radiation
above 2200 A., has been tudied,, Observations were made by leaking
the reaction mixture directly into the electron beam of the mass
spectrometer during photolysis. The principal products of the
reaction were H2CO, H20, CH30H, and CH300H; minor
products were CH3COOH, HCOOB, CH300CH3, and higher
molecular weight products *hich were probably CH3C0CH0 and
CH3COCP20H. Because of the cracking pattern of the
reactants, it was impossible to establish the presence or absence
of CH4, CO, CH2C0, and C02» From the identified products
at least 1U free radicals are inferred to be intermediates in this
system. An exhaustive and impartial examination of all possible
M. Basic Science and Technology
1173
-------
radical-radical disproportionation and recombination reactions
indicates that the data exclude a large number of possible
reactions but that 1U0 reactions could still be occurring.
Formaldehyde, so far as these studies go, could be formed by 39
different reactions. Thus, this experimental method cannot give
a complete mechanism, nor can any method that simply analyzes all
molecular products™ (Authors' abstract, modified)##
07505
Hudd, J. E.
BIOCHEMICAL EFFECTS OF SIR POLLUTANT OXIDANTS (PROGRESS REPORT
SEPTEMBER 1, 1965-AUGUST 11, 1967). Calif. Univ.,
Riverside, (26)p„, Aug. 11, 1967. 24 refs.
In order to tetter define the toxicity of ozone, its reactions
with amino acids and proteins were studied under conditions closely
approximating physiological conditions, that is, in agueous
buffered solutions. Ozone was generated by passing oxygen through
an apparatus producing a silent electric discharge. Solutions of
amino acids and proteins were exposed to ozone by permitting the
gas to bubble through the solutions from a capillary tip.. The
following order of susceptibility of amino acids to oxidation by
ozone was found: cysteine, methionine, tryptophan, tyrosine,
histidine, cystine, and phenylalanine. The oxidations of
tyrosine and histidine were dependent on pR, being greater under
alkaline conditions. The oxidation of pancreatic ribonuclease by
ozone resulted in a decrease in enzyraic activity. The amino acid
residues most affected by treatment with ozone were
tyrosine and histidine. Reaction of avidin with ozone caused
changes in the absorbance spectrum characteristic of the
tryptophan residues. The biotin binding capacity of avidin was
lost after treatment of avidin with ozone. The studies
reported herein cannot be used to predict the effect of ozcne on
lipoprotein membranes, and it remains for direct experiment to
ascertain whether the lipid or the protein of biological aieatranes
is first damaged by ozone.
-------
carbony1 compounds with olefins. The s-trans-1-acetylcyclohexene
¦as found to react with isobutylene to form
cis-1-acetyl-2-nethylallycyclohexane without side reactions.
Several s-cis enones were found to be photochenically reactive.
Some general rules are presented which summarize existing
observations for this class of reactions.*#
07512
Slater, David H.„ Susan S. Collier, and Jack G. Calvert
TUB PHOTOLTSIS OP I,!"-A20IS0BDTANE VAPOR AT 3660 A; THE
REACTIONS OP THE ISOBUTYL FREE RACICAL. Preprint, Ohio State
Dniv., Columbus, Evans Chen. Lab., (25) p„, (1967)..
(Presented at the Robert Livingston Photochen. Symposium,,
Minneapolis, Minn., Hay 9, 1967 and 154th Nat. Meeting, Aner.
Chen.. Soc«, Chicago* 111., Sept. 1967.}
The vapor phase photolysis of IjV-azoisobutane was studied in
experiments at wavelength 3660 A and at various temperatures and
pressures. The product rate data fit well the suggested reaction
schene involving an excited azoisobutane molecule and reactions of
the isobutyl free radical. The ratio of rate constants for the
disproportionation and conbination reactions of the isobutyl
radical was estimated to be 0.075 plus or minus 0..007 (25-168 deg) .
Rate constants for the H-aton abstraction and the decomposition
reactions of the isobutyl radical were derived. Trcn the effects
of pressure and tenperature on the guantua yield of nitrogen, an
estinate was obtained for the rate constant for the excited
az/-solecule decomposition reaction. If the excited singlet were
the reactant, then fluorescence emission should be observable from
the azoisobutane. No enission was detectable even in experiments
at -180 deg*##
07513
Siedlewski, J„ and S. Trawinski
THE MECHANISM OF CATALYTIC OXIDATION ON ACTIVATED CARBON.. VIII.
THE RELATIONSHIP BETWEEN THE CONCENTRATION OF FREE RADICALS OF
CARBON AND IIS CATALYTIC ACTIVITY IN THE OXIDATION OF H2S AND
SC2.. Text in Polish, soczniki Chen.., No. 6, p. 1083-1090,
1966. 18 rets. Engl, transl. Intern. Chen. Engl., 7(1):35-39,
1967.
The concentration of free radicals in carbons obtained as a result
of the carbonisation of organic substances depends on the
carbonization temperature. A naxinun nunber is obtained in the
tenperature range of 550-700 deg. depending on the type of
substance carbonized. The nunber reaches 10 to the 20th power
free radicals per gran. At a tenperature of about 1200 deg their
number diminishes by two orders of magnitude. The catalytic
activity of semiconductors, which include low-tenperature carbons
(obtained at tesperatures below 900 deg), depends on anong others,
the crystal structure and the electric conductivity. In the
range of teuperatures in which there is a variation of the
M. Basic Science and Technology
1175
-------
concentrations of free radicals in low-teaperature carbons, the
crystal structure and the electric conductivity vary
simultaneously. The catalytic activity of those carbons can
depend on the variation of both of these parameters, the
oxidation of H2S and S02 on saaples of carbon obtained as a
result of carbonization of saccharose at a temperature of 1200 deg
and of activation with oxygen at teaperatures of 450 deg and 850
deg indicates that those carbons had a siailar crystal structure,
the same electric conductivity, and identical concentrations of
free radicals. They differed only in the number of superficial
oxides formed on their surfaces as a result of chemical activation
by oxygen. The purpose of the present work was to find the
connection between the concentration of free radicals in carbon
and its catalytic activity in the oxidation og H2S and S02.
The number of microaoles of oxidation product foraing per sq. m of
surface of the carbon in a specific tiae is taken as a measure of
catalytic activity. The heating of carbon vith previously formed
free radicals causes a reduction in the number of radical active
centers on the surface and a decline of its activity in the
oxidation of H2S and S02.#*
07517
Wong, Edgar 1., Andrew E. Potter# Jr., and Frank E.
Eelles
REACTION FATES OF CARBON MONOXIDE WITH HYDROXY! RADICALS AND
0X7GEN ATGflS. National Aeronautics and Space Administration,
Cleveland, Ohio, Lewis Research Center. NASA Tech. Note.
TN D-4162, 18 p., Sept. 1967. 28 refs.
CFSTI
A mass spectrometer stirred reactor technique was used to
measure the rates of reaction of carbon monoxide with hydroxyl
radicals and with oxygen atoms. For the carbon monoxide and
hydroxyl reaction in the temperature range of 310 deg to 611 deg
K, the rate constant based on C02 production was 4.2 plus or
minus 0.8 x 10 to the 11th power exp (->1200 plus or minus 300/RT)
cubic centimeters per mole per second. The rate near roca
temperature is lower than other values reported recently. The
activation energy of 1200 calories per aole (5000 j/aole) is in
good agreement with recent estiaates, For the carbon monoxide
and oxygen reaction, an upper liait value for its rate constant
based on C02 production was estimated to be U x 10 to the 13th
power cubic centimeters squared per aole squared per second at 500
deg k.. Since the carbon aonoxide and hydroxyl reaction is
considerably faster than the carbon monoxide and oxygen reaction,
trace impurities giving rise to hydroxyl interfere with carbon
monoxide and oxygen rate measurements, and may be responsible for
the large differences in rate constants reported by various
investigators for this reaction..*#
07607
stein, K. C., J. J, Feenan, G. P. Thompson, J.. F.
Schultz, L. Ju E« Rofer, and R. B. Anderson
1176
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
THE OXIDATION OF HYDROCARBONS ON SIHELE OXIDE CATALYSTS.. J. Air
Pollution Control Assoc.., 10 (0) : 275-281, Aug- 1960. 2 refs..
(Presented at the 52nd Annual fleeting. Air Pollution control
Assoc.., Los Angeles* Calif., June 21-26, 1959..)
A large number of catalysts have been laboratory tested for the
oxidation of various hydrocarbons for the purpose of developing
catalysts which nay be suitable for oxidizing hydrocarbons in
automobile exhaust gas. A large number of catalysts were tested
using the rapid microcatalytic- chromatographic technique. A group
of eight hydrocarbons was selected for study, comprising n-pentane,
isopentane, pentene-2, pentyne-1, n-hexane, cyclohexane, 2,3 -
dimethylbutane, and benzene. Many oxides of some of the metals of
groups IB, VB, VIB, VIIB, and VIII of the periodic table were
selected., A list selected from the oxides used, together with their
B.E.T. surface areas and x-ray diffraction data is shown in Table
I„ Results show that: branched hydrocarbons are more difficult to
oxidize than normal hydrocarbons; ease of oxidation increases with
molecular weight in homologous series; unsaturated aliphatic
hydrocarbons are more easily oxidized than the corresponding
paraffins; in comparing open chain and cyclic compounds having the
same number of carbon atoms, reactivity toward oxidation probably
decreases according to the sequence; the most active single oxide
catalysts were found to be the oxides o£ cobalt, nickel, manganese,
chromium, cerium, titanium* and iron. It is conceivable that
different forms or preparations of the same oxide would have
different activities. The microcatalytic - chromatographic
technigue has proved to be a very convenient means for rapid
screening in oxidation stadies. It is to be recommended where a
large number of catalysts or reactant& are to be investigated or
where a wide range of temperatures is to be used.
07620
Suter, H.. F.
HANGE OF APPLICABILITY OF CATAHTIC F0HE BURNERS. J. Air Pollu-
tion Control Assoc., 5{3|:173-175, 184, Nov. 1955. (Presented
at the 48th Annual Meeting, Air Pollution Control Assoc.,
Detroit, Mich., flay 22-26, 1955„)
A more detailed exposition of the mechanism of vapor-phase
catalytic oxidation is presented. Catalytic oxidation proceeds
through 3 steps: adsorption on the active surface; chemical
reaction; and, desorption. During adsorption turbulence will assist
in the diffusion process and shapes of catalyst supports promoting
laminar flow should be avoided. The clearance between active
surfaces should be small. The general field of applicability for
vapor-phase oxidation in the air pollution control field lies in
streams containing combustible matter at concentrations below the
lower limit of explosibility. The limitations may be physical,
chemical, oc practical and economic. Honcombustible inorganic
solids are not affected by the catalyst, and should be absent from
the stream lest they accumulate and cover the active surface. The
material to be oxidized must yield innocuous products in order to
serve the purposes of air pollution control. Specific catalyst
M. Basic Sciance and Technoloty
1177
-------
poisons aust be absent, catalytic oxidation units are not bought
"off-the-shelf" but arc specially designed for various
applications.
07681
Fontijn, Arthur and Daniel E. Posner
NO + 0 CHE HI LUMINESCENT BEACTION USING ADIAEATICALLY EXPANDED
NITBIC OXIDE- Virginia Univ.., Charlottesville, Dept., of
No. N8- Technical Sept. No« AC-6-P, 7p„, Jan. 1967..
18 refs.
CPSTI, DDC: AD 647978
The rate constant for the cheailuminescent reaction SO + o yields
1902 * hv has recently been observed fro* upper-atmospheric chemical
releases and simulated releases in a Ion-density wind tunnel to be
several orders of magnitude higher for adiabatically expanded than
for "normal" NO. In this note, it is shown that this enhancement
can be attributed to the presence of clustered NO based on super
saturation calculations and recent mass spectrometric gas-sampling
data., these clusters allow the normal three-body excitation step
to be replaced by a two-body step for which the observed rate
constant is shown to be quite reasonable. (Authors" abstract,
modified}
07717
Heicklen, Julian and Norman Cohen
THE HOLE OP NITRIC OXIDE IN PHOTOCHEMISTRY. Aerospace Corp., El
Segunda, Calif.., Contract AP 04 (695) -1001, Rept, SSD-TB-66-19G and
TH-1001 (2250-40)-4, 301p. , Oct. 1966. 464 refs..
CDC: AD 808580
The gas phase chemistry of nitric oxide is reviewed for reactions
of importance below about 300 c. Included are reactions of
vibrationally and electronically excited NO and the reactions of NO
with stable molecules, electronically excited molecules, atoms,
ions, and free radicals. The fate of nitroso compounds is also
discussed. A bibliography containing 464 references is listed.
(Authors" abstract, modified)
07791
Benson, S. S«.
MECHANISM OF THE DIELS-AIDES HEACTICNS OP BUTACI ENI. J. Chem.
Phys„, 46(12):4920-4926, June 15, 1967.
Kinetic data on the pyrolysis of 1,5-cyclooctadiene to give
butadiene and 4-vinyl cyclohexene by parallel paths are analyzed
and shewn to be quantitatively consistent with a common biradical
1178
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
precursor, the octadien-2,6„-diyl-1,8 biradical. It is further
shown that these data are in excellent agreement with independent
studies of the reverse reactions; pyrolysis of 1-vinyl cyclohexene
to butadiene and the dimerization of butadiene, A fourth study of
the pyrolysis in solution of 1,2-diviuyl cyclobutane to give
butadiene, 1,5-cyclooctadiene, 4-vinyl cyclohexene, and
cis-trans isomerization is shown to fit the same scheme with only
¦inor modifications in two of the rate constants. The analysis
lends support to the 12.6-kcal assignment of the allyl
stabilization energy. It also resolves an apparent anomaly in the
rate parameters for the reverse Diels-Alder pyrolyses of
cyclohexene,, 3-nethyl cyclchexene, and 4-vinyl cyclohexene.
Arrhenius parameters for all the elementary rate constants are
assigned and shovn to be reasonable compared to similar
processes. Important rotation-controlled rates in the scheme are
examined and conclusions drawn about the contributions of
different rotoaeric forms of the biradical. {Author"s abstract)##
07798
Hess, X. D.., J. L. jacobson. It. Scbaffuer, and J. If. Pitts, Jr.
STRUCTURE 1SD REACTIVITY IB TUB VABQB-PHASE PHOTOLYSIS OF KETONES.
T. ALIPHATIC CYCLOPROPYL AH8 OIEFIHIC KETONES. J. Am. Chem. Soc.,
89(15| x368lt-3688, July 19, 1967. 3H refs.
Vapor-phase irradiations of the aliphatic cyclopropyl and olefinic
ketones, methyl cyclopropyl ketone(I), 1-cyclopropyl-2-
propanone (II), l-cyclopropyl-3-butanone (IT), and 1-penten-4-
bone (III) at 3T20 A and 120 degrees have been carries out.
Quantum yields of yields of carbon monoxide
from the type x split are 0.04 for ke-
tone I, 0.88 for ketone II, 0.71 for ketone IV and 0.60 for
III. Other primary photochemical processes in these ketones are
the isomerization of cyclopropane in connpounds I and II, and
the type II split in compound IV. The data from these reactions
together with previously reported results provide the basis for a
coherent evaluation of the relationship between structure and
photoreactivity in the vapor phase at 3130A and 120 degrees of the
two series of closely related aliphatic and cyclic ketones which
possess cyclopropyl and double bonds, respectively, in the alpha,
beta and gamma positions to the carbonyl group. (Authors)
abstract, modified)
07806
Alley, C.
A BENCH SCALE REACTION SISTEf! 70S MEASURING ATMOSPHERIC SMOG
POTENTIAL- Preprint, Clemson Univ., S« C., Chemical Engineering
Sept., <(10p»)), 1966. (Presented at the 21st Annual Instrument
Society of America Conference 6 Exhibit, Mew York City, Oct* 2#-27,
1966, Paper Np„ 11.3-1-66.)
Photochemical smog results when the atmosphere contains certain
hydrocarbons and oxides off nitrogen and is irradiated under
M. Basic Scleras and Technology
-------
favorable conditions of temperature and humidity* If smog control
efforts are to be successful, the complex series of reactions by
which snog is produced oust be completely understood from a
standpoint of reaction mechanism and kinetics. This paper
describes a bench scale photo-chemical reaction system for
simulating the processes occurring when a polluted atmosphere is
irradiated by sun light. The flexibility of the system as well as
the capabilities and limitations of several existing pollutant
monitoring devices are discussed.. (Author) s abstract)
07866
Cohen, Saul G.
EFFECTS OF MEBCAPTANS AND DISULFIDES ON PH0T0CHEHICA1 AND HIGH
ENERGY BADIATION INEUCED REACTIONS. Brandeis Univ., Waltham, Mass.,
Dept.. of Chemistry, Contract No. AT (30-1) 2499, 19p., Nov. 1, 1966.
CFSTI: NYO 2499-20
The nature of photochemical and radiation induced reactions and of
their retardation and inhibition fcy mercaptans were studied. The
proposed mechanism of inhibition of photochemical and radiation
induced reactions by mercaptans involves rapid transfer of hydrogen
atom from mercaptan to an intermediate radical and from an
intermediate radical to thiyl radical. In the benzophenone-2-
propanol system the intermediate radicals, (CeK5)2COH I and
.(CH3)2COH II are reconverted tc the starting materials,
benzophenone and 2-propanol respectively, inhibition resulting.
This mechanism would require that if these radicals I and II were
formed from benznydrol and acetone they would still be converted by
the sulfur compounds to benzophenone and 2-propanol. inhibition
would not results but the system would be transformed. This has
been demonstrated confirming the mechanism of action of sulfur
compounds. Additional experiments have been carried out on the
photoreduction of aminobenzophenones in acidic aqueous 2-propanol«
Photoreduction at 313 micron of p-dimethylaminobenzophenone in
111 2-propanol-water, 6N in HCL, leads to the pinacol
with quantum yield of about 0„3 Photoreduction of U-
benzoylphenyltrimethylammonium chloride at 313 m micron in 1:1 2-
propanol-water leads to the Finacol- with quantum yield of 0.64..
other water soluble ketones are being studied. Preliminary
experiments indicate that a tertiary amine is an excellent
photoreducing agent for 4-benzoylbenzoic acid in aqueous medium,
although the tertiary amine is not very effective in photoreduction
of benzophenone in benzene.
07883
levy, Arthur, E. L« Merrynan, and T. Beid
MECHANISMS Of FORMATION OF SDtFCF OXIDES IN COBBDSTION. Preprint,
Battelle Memorial Inst.. Columbus, Ohio, (("2))p., ((1967)).
43 refs. (Presented at the symposium on Air Pollution Control
Through Applied Combustion Science, 16th Annual meeting,
American Inst, of Chemical Engineers, New York City, Nov,
26-30, 1967.)
1180
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
The chemistry of sulfur oxidation processes is reviewed with
respect to the kinetics and mechanisms of the various processes
involved* Oxidation processes examined are those for sulfur,
hydrogen sulfide, carbon disulfide, methyl sulfide, and methyl
nercaptan. Detailed examination of the kinetics and mechanism of
oxidation of hydrogen sulfide is made based on slow reaction, fast
{explosion) reaction, flash photolysis, and flame microstructure
studies of hydrogen sulfide-oxygen systems. Special attention is
given to the role of the lcwer oxides, SO and S20, in developing
the mechanisms of S02 formation. The interaction of S02 in hydrogen-
oxygen explosions and in flame processes and the homogeneous
formation of S03 in flames via the removal of oxygen by S02 are
also reviewed. The slow, pre-explosion reactions of H2S and 02
appear to suggest a process whereby the partial oxidation product
SO is produced. This is substantiated in part by the energetics of
various pre-explosion studies and by some of the flame kinetics-
On the other hand, the role of so or S2o has not been substantiated
in an unqualified manner by any of the investigations to date.
Therefore it cannot be stated with certainty whether only one or
both species are the precursors to S02 formation. Understanding
the oxidation of the organic sulfur compounds, such as the
mercaptans and the sulfides, is sketchy. Different mechanisms are
suggested, but the evidence is still fragmentary, he homogeneous 0-
atom oxidation of S02 in combustion appears to be well-affired.
New laboratory tools, fresh experimental approaches, and inventive
thinking will all lead to an even better understanding of the
complicated fashion in which sulfur reacts with oxygen.
08056
K. H. Homann
CARBON FORMATION IS PHEMIXIE UftHES* Combust. Yla»e,
11(4):265-286, Aug. 1967. 48 refs.
Certain aspects of gas phase carbon formation in premixed flames
are reviewed with the object of stimulating discussion and future
work in the field. Among the experimental facts discussed are
the appearance of fuel-rich flames, limits of carbon formation,
temperature dependence of the limit of carbon formation,
pressure dependence of the formation limit and the yield of carbon,
hydrocarbon intermediates, reaction products from the pyrolysis
of acetylene and benzene, particle formation and growth. There
follows a discussion of the route of carbon formation with further
comments on the influence of additives and electric fields,
(Author*s abstract, modified)14
08105
B. S. Juvet, Jr.. R. t. Tanner, 0. C. T« Tsao
PHOT0LYTIC DEGRADATION AS A MEANS OF ORGANIC STRUCTURAL
DETERMINATION.. J„ Gas Chromatog., 5(1)-:15-21, Jan. 1967.
15 refs..
Difficulty reported by many authors obtaining reproducible results
M. Basic Science and Technology
-------
in intec-laboratory studies using the pyrolysis-gas chromatographic
technique prompted an investigation of other, more reproducible,
methods of sample decomposition* The method chosen was mercury-
sensitized photolytic decomposition because of the
simplicity of the experimental technique, the simplicity of the
fragmentation patterns, the predictability of the decomposition
products, and the availability of ultraviolet light sources
in many well-equipped laboratories. This proved to be a
particularly fortunate choice since, not only are results
highly reproducible, but Frel*n,inary work led to the discovery
that functional groups present in a sample may be identified by
characteristic constants related to the retention of certain
irradiation product peaks called homologous peaks and common peaks,
eliminating the need for identification of the decomposition
products in evaluating the structure of the sample. In this
paper, the procedure is discussed in detail and the decomposition
product retention parameters are tabulated for aldehydes,
ketones, alcohols, esters, and ethers., (Authors' abstract) ##
08254
Harkness, C.. and F„ E» Murray
HEACTION BETWEEN BETHYL SULFIDE JKD CXYGEN IN A STATIC SYSTEH.
Atnos Environ., 1 ft) :U 91-U97, July 1967* 3 refs.,
Methyl sulfide and oxygen react explosively at temperatures as
low as 210 Cn At 195 C the non-explosive reaction exhibits an
initiation stage and a main stage. The rate of the main stage as
determined from pressure-time curves is linearly dependent on
initial oxygen pressure but substantially independent on initial
methyl sulfide pressure.. The extent of the initiation stage is
reduced by increase in the oxygen pressure. The chief oxidation
products are sulfur dioxide and carbon monoxide. Even with an
excess of oxygen not all methyl sulfide reacts. (Authors"
abstract)##
08353
Hoare, E» E.. and o. A. Hhytock
PHOTQ-CXIBATIOH OP DIETHYL KETONE VAPOR. Can.. 0. Chenu
'(Cttawa), Vol- 45, p„ 28U1-28J45, 1967. 9 refs.
Results from studies of the photo-oxidation of diethyl ketone are
reported. Quantum yields of the products of the reaction of
diethyl ketone when photclyzed in the presence of oxygen with
eight of 3130A were studied as a function of time at 150 and 100
C. The reaction products were mostly the same as those from the
photo-oxidation of methyl ethyl ketone, in addition, propionic
acid and ethylene were products at 150 and 100 c, while trace
amounts of acetone and methyl ethyl ketone were detected at 150 C„
The variety of the reaction products and the absolute values of
their quantum yields indicate that the reaction is a complex chain
reaction of short length. The primary photolysis split is well
established.. The chain reacticn must be caused by hydrogen
abstraction from the ketone molecule by a radical during which
two types of 3-Fentanonyl radical say be formed.##
1182
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
08558
Hamming, Walter J*
PHOTOCHEMICAL REACTIVITY OF SOLVENTS. S.A.E. (Soc. Automotive
Engrs.), Preprint 670809, lUp. , 1967,, 5 refs. (Presented at the
Aeronautic & Space Engineering and Manufacturing Meeting, los
Angeles, Calif., Oct. 2-6, 1967.,)
Evaluative studies of relative photochemical reactivities of
various organic solvents for purposes of emission control are
reported. Solvents include olefins, xylenes and other arooatics of
comparable weight, toluene, branched ketones, tri- and
tetrachloroethylene; benzene, and saturated halogenated
hydrocarbons. Criteria used to judge relative photochemical
reactivity were mainly eye irritation and ozone formation. Initial
judgments based on these standards were also invluenced by aerosol
formation, aldehyde production, and effect of test substances on
rate of conversion of NO to H02* The results of the entire study
show clearly that xylene is more reactive than toluene and some
olefins. However, the latter, as a group, appear to have the
greatest photochemical reactivity of all hydrocarbon types. Normal
ketones,, such as methyl ethyl ketone, are slightly reactive, but
branched ketones, such as methyl isotutyl ketone, are somewhat more
reactive than their normal isomers. Chlorinated ethylenes, except
perchloroethylene, appear to be photochemically active to a degree
roughly comparable with branched ketones and toluene. Alcohols and
aldehydes are less reactive than toluene; and branched
hydrocarbons, cyclic paraffins, and normal paraffins, still less
so* Benzene, perchloroethylene, saturated halogenate hydrocarbons
and acetone appear virtually unreactive. The results of this study
clearly demonstrated that both the guantity of organic solvent
emissions in los Angeles County and their overall photochemical
reactivity were such that a reduction was necessary. The results of
the studies were utilized to construct Bule 66 for the control of
organic solvent emissions in Loe Angeles County.
08572
Sunavala, P- P.
COMPUTATIONS ON INCOMPLETE COMBUSTION J. Mines, Metals Fuels
(Calcutta), 15(8) :2a2-2«
-------
balances method employs the development of equations for carbon,
hydrogen, oxygen, and nitrogen balances in the fuel gas and the
flue gases in teras of the unknown parameters which can be
evaluated. The ratio of nm to the third power blast furnace gas to
no to the third power coke oven gas in mixed gas practice can be
calculated. Pro the straight combustion of any fuel gas, relations
obtained, depending on the carbon, hydrogen and oxygen, as veil as
the carbon and nitrogen balances, ar e given. Equations are
provided for the air/fuel and flue and flue gas/fuel gas ratio by
volume, if the hydrogen, oxygen and nitrogen balances are employed.
CS62Q
Schumann, G.
INVESTIGATI08 OF BACIOACTIVE AEROSOIS„ (Unterschungen an
radioaktiven Aerosolen.)
Text in German. Chen. Ingr. Tech. (Veinheim), 39(16):966~971,
Aug. 25, 1967. 21 refs.
The mathematical relationships involved in the accumulation of
radioactive atoms and ions on atmospheric aerosols were derived as
a function of their particle size. These calculations should also
be useful for non-radioactive atoms and ions of similar particle
size. As an expansion of the experiments the accumulation of
polydispersive room and free air aerosols was examined. A Goetz
aerosol spectrometer was used fot this purpose. The measurements
presented difficulties not encountered with the monodispersive
aerosols.
08623
Gentry, J. and J. B. Brock
UNIPOLAB DIFFUSION CHARGING OP SJIALI AEPOSOl PAPTICIES. J. Cheou
Phys.., 47 (1) ;64-69, July 1, 1967.
A theory for unipolar diffusion chargin of snail aerosol
particles is developed for the ftee-molecule and transition
regions.. The free-molecule theory is, of course, exact within the
restrictions imposed on the physical system. The theory for the
transition regions is based on the Knudsen iteration solution of a
relaxation model of the Boltzmann equation, insufficient
experimental data are available to permit detailed comparison with
the developed theories. (Authors# abstract}
086145
Lichtenstein, Stanley
INSIDE AIH POIIDTIOH—THE VIEW fFCH SBS. Ind. Heating, 34(7): 1250,
1252, 1254, 1258, 1260, July 1967. Also: Air Eng., 9(11):12-15,
Nov. 1967«
Investigations by U.S. Bureau of Standards are finding out what
1184
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
happens to estimated total of 140 million tons of pollutants fed
into atmosphere annually by motor vehicles, industry, power plants,
space heating and refuse disposals. Various methods used in
studies of air pollution are discussed. Several scientific teams
Baking important contributions to air pollution are listed.
08700
Albright, Lyle F.
COMMERCIAL VAPOB PHASE PROCESSES FOE PABTIAL OXIDATION OF LIGHT
PABAFFINS. Chem. Eng., 74 (17):165-171, Aug. 14, 1967. 18 refs.
Reactors for the manufacture of oxygenated compounds operate
adiabatically - and, for sense processes, nonisothermally, while in
others isothermmally. The operating characteristics for these
processes; the methods of reacting, separating, recovering, and
recycling the various feed, product and byproduct streams;
important features in the design and operation of nonisothermal and
isothermal reactor systems are discussed.
08705
Kolsaker, P., and P. S. Bailey
OZONATION OF COMPOUNDS OF THE TlfPB AR-CH=CH-G; OZONATION IN METH-
ANOL. Acta Chem. Scand., 21(2):537-546, 1967.
The ozonation of some substituted cinnanic esters and acids and of
p-propenyl anisole was carried out in methanol at - 78 deg. and the
resulting solutions were subjected to decompositions under neutral,
acid, and basic conditions. The yields of decomposition products
indicate that a reaction between the initially formed methoxy hydro
peroxides and aldehydes takes (lace to some extent prior to the
decomposition. The yield of phenols follows the order migratory
aptitudes generally accepted. Acid decomposition gave the highest
yield of phenols. Easic decomposition gave only the normal
cleavage products, viz. acids and aldehydes. Decomposition paths
are discussed. (Author Abstract)
08717
Christian, Larry 0.
RADAR CROSS SECTIONS FOB TOTALLY REFLECTING SPHERES.
Atmospheric Sciences Lab., Hhite Sands Missile Range,
N. Hex., Task 1Vo250016Al26, FCCK-5142, 25p., Aug.
1967, 5 refs.
CFSTI, DDC: AD 659327
The backscatter efficiency factors (radar cross section divided
ty geometrical cross section) for totally reflecting spheres have
been calculated using exact Hie theory. The results are
M. Basic Science and Technology
-------
presented both in tabular and graphical form for the size parameter
(circufference of sphere divided by wavelength of incident
radiation! range from 0.01 to 19.95 in increments of 0»01„
Comparison between these theoretical calculations and experimental
neasuremefits shows very close agreement (less than or egual to
H.iJ* difference) in five of seven cases. (Author's abstract}##
08B27
Wei, Kei, Jean-Claude Hani, and J„ U. Pitts, Jr.
THE FGBBVriCH OF POLYENIC EIALBIFYDES IH THE PHOTOOXIDATIOH 01
PURE 1IQ0ID BENZEN. J. An. Cheat. Soc. , 89 {16) : H225-4227,
Aug. 2, 1967. 1U refs..
The photooxidation of dty» liquid benzene, has been investigated
and among the several products that were formed, two polyenic
dialdehydes; trans, trans-2«4-hexadienedial (aucondialdehyde, 1}
and 2,4,6,8,10-dodecapentaenedial, IZ, were isolated.
Onfiltered radiation frcs a medium-pressure mercury lamp was used
to irradiate at rooi temperature pure, dry, liguid benzene through
which oxygen vis continuously bubbled. The irradiated benzene was
chromatographed twice on silica gel, giving three fractions. The
first fraction eluted with an 80:20 pentane-ether solution,
contained nucondialdehyde (I). The second fraction, eluted with
a 70:30 pentane-ether solution, contained dialdehyde II.
Infrared, ultraviolet, and mr techniques were used to determine
the physical and spectroscopic properties of I and 11.
Confirmatory evidence was obtained by aass spectrometry and by
microhydrogenation which, in the case of II, yielded a product
identical with an authentic sample of 1,12-dodecanediol« The
physical and spectroscopic properties of the products,
specifically infrared spectrum comparisons, confirm the all-trans
configurations for both compounds. Results suggest that benzene
ring opening by oxygen may alsc be involved*##
C8829
Simonaitis, R.,, G.. B. cowell and J« Pitts, Jr.
PWOTOSEDOCTIOH OP CYCIOPBNTA NOSE AND CYCLOHBXANOME. Tetrahedron
letters. No. 38:3751-3754, 1967. 10 refs.
Quantitative correlations of structure and reactivity in the
internolecular and intramolecular photoreduction (Type II
process) of ketones are being intensively investigated. A
guantitative comparison of the rates of hydrogen abstraction frcm
isopropyl alcohol by cyclopentancne and cyclohexanone is reported.
The method employed is the guenching with isopropyl alcohol{IPA)
of the isomerization to the unsaturated aldehydes. Results
confirm that most of the isomerization occurs from the triplet
state of both compounds. An eguation is derived from the
reaction mechanism that yields information on the following: (1)
The guantum yield of the aldehyde in the absence of IPA, and in
the presence of IPA, (2) the lifetime of the excited triplet,
and (3} the rate constant for the hydrogen abstraction state.
The results are evaluated and correlated.##
1186
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
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08845
Altshuller, A- P., 5. L„ Kopczynski, V. A. Lonneman,
T. i„ Becker, and D. Wilson
PHOTOOXIDflTIOlf OP PROPYLENE WI1H NITROGEN OXIDB IN THE PHESENCE
CF SOLFOH DIOXIDE- Preprint, Public Health Service,
Cincinnati, Ohio, National Center for Air Pollution Control,
((10))p., J|1967J ) « 13 refs.
The photooxidation of 2 ppm of propylene and 0-5 ppm of nitrogen
oxide vas investigated under dynamic flow conditions with sulfur
dioxide present in the reaction mixtures at concentrations from 0«0
to 1.2 FEB. Application of the statistical *t* test shoved no
significant differences in rates of consumption of propylene and
nitrogen oxide or in yields of oxidant, peroxyacetyl nitrate,
formaldehyde, and acetaldehyde among tests at the various levels of
sulfur dioxide, including zero ppm. Amounts of sulfur dioxide
consuned in the reactions ranged from 25 to 60ft* Although a
sulfur balance was not obtained# appreciable amounts of sulfate
were measured as a product of the oxidation of the sulfur dioxide*
On the basis of previous investigations* the sulfate is believed
to be present as sulfuric acid aerosol. These results suggest
that appreciable levels of oxidant may occur in urban atmospheres
even when high concentrations of sulfur dioxide are present.
(Authors* abstract)it
08877
Hess, I.. 0. and J. N. Pitts, Jr.
STRUCTURE AND REACTIVITY IS THIS VAFCB-PHASE PHOTOLYSIS OF
KETONES,. IV„ CICLOPROPYL AND OLEFINIC CYCLIC KETONES.,
J. Am. Chea. Soc., 89(9) : 1973-1979, April 26, 1967. 32 refs,.
Vapor-phase irradiation of bicyclo((3.1»0))hexan-3-one (I) and
3-cyclopentenone (III) at 3130 and 2380-2654 A results in the
formation of carbon monoxide and hydrocarbon products with high
quantum efficiencies, phi (sub CO) eguals 0..77 and 0.87 for I
and II, respectively# under a variety of experimental
conditions. The hydrocarbon products from I and 1,4-pentadiene
(major)r vinylcyclopropane, and 1,3-butadiene, while III gives
almost exclusively butadiene (phi (sub CO) eguals 0.88) over a
wide range of temperatures. In contrast, irradiation of
bicyclo | (3.1«0))hexan-2-one (II) and 2-cyclopentenone(IV) under
identical conditions produces only trace amounts of CO and no
detectable hydrocarbons. However, compound II does undergo a
photoinduced rearrangement to form 3-methyl-2-cyclopentenone. The
cyclopropyl and double-bond groups were found to exhibit similar
effects on the modes of photoreactivity of these four cyclic
ketones.. Either of these groups conjugated with the carbonyl
chromophoxe stabilize the ketone, whereas their location in the
homoallylic position greatly facilitates photodecomposition.
(Authors" abstract)##
M. Basic Sconce and Technology
m;
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09030
B. A„ lombos, P. Sauvageau, C. Sandorfy
THE ELECTRONIC SPECTRA OF NOREAI PARAFFIN HYDROCAREONS..
Chen.. Phys. letters (Amsterdam) * Vol. 1, p. U2-U3, Harch-
April 1967. 3 refs..
The far ultraviolet absorption spectra of the normal paraffin
hydrocarbons from CI to C8 were photoelectrically recorded with
a double bean instrument down to 1150 A under 0.2 A
resolution- An attempt is made to interpret the spectra in terms
of Mulliken's united a tea treatment of the excited states
of methane and ethane. (Authors' abstract)##
09031
E. A. Loafcos, P. Sauvageau, C. Sandorfy
THE FAB—ULTRAVIOLET SPECTRA OF BRANCHED CHAIN PARAFFINS.
Chen. Phys. Letters (Amsterdam), Vol. 1, p. 221-223, 1967.
U refs.
CFS1I, DDC: AD 661478
The far ultraviolet spectra of gaseous isobutane, isopentane and
neopentane were measured up to 1150 angstroms. They are compared
to the related nornal isomer in each case. A tentative
interpretation of the spectra i£ given. (Authors* abstract)#*
0903«L
F. B. Page
A STUD* OF THE STABILITY OF GASSCOS NEGATIVE IONS.
(FINAL TECHNICAL REPORT.) Aston Oniv., Birmingham,
England, Dept. of Chemistry, Contract DA-91-591-E0C-3870,
Proj. 2001U50B13B, t(136))p.# Feb. 1967. 15 refs.
CPS1I; AD 82251V
The nodes of formation, occurrence# and in particular the
stability of gaseoufi negative ions was determined by the magnetron
technique. Included is a description of the apparatus used# the
eleventary theory of the method, and a comprehensive list of the
stabilities of ions studied during the past three years.#1
090U6
Sage, E. H.
PARTIAL OXIDATION PRODUCTS FOBBED DURING COUBQSTIOS.
(EIGHTEENTH PROGRESS REPORT: 0UIT 1 TO DECEH'BDR 31, 1967.)
Preprint, California Instu of Tech.., Pasadena, Chemical
Engineering Lab., ({65)) p., 1967., ((21}) refs..
1188
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
The modifications Id the pressure combustor were found to function
satisfactorily and have permitted measurements of both the
perturbations in normal stress and the perturbations in total and
monochromatic optical intensity,, Experimental activities have
been limited primarily to obtaining information concerning the
perturbations in total and monochromatic optical intensities
utilizing air and natural gas as fuel,. Results are presented in
several tables.. To more fully explain the behavior in the
pressure combostor, a set of routine computer programs to permit
the prediction of the composition of the products of reaction for
any mixtures of air and any hydrocarbon was completed.. The
calculations have been carried out for varying rates of heat less
from the combustor. The exit temperature from the combustor Has
computed in this fashion. It was also computed from the rate of
flow of gas through the converging-diverging nozzle at the exit of
the combustor.. Bather good agreement was obtained between these
widely different means of evaluating the exit temperature. The
complicated behavior of the perturbations in normal stress at the
two ends of the combustor is depicted. The behavior depicted can
be explained by the difference in temperature at the two ends of
the combustor and the markedly greater radial temperature
distributions near the exit of the combustor. Furthermore, the
velocity of wave propagation is somewhat different at the same
point in the combustor depending on the direction of propagation as
a result of the local momentum velocity of the gases. A
manuscript derived from the work upon the oscillatory combustion in
the pressure combustor, has been completely reworked. A
significant amount of additional experimental information was
included., The revised manuscript which covers all of the
experimental work that has been completed with the pressure
combustor for the air-natural gas system, is appended..##
09077
ttarneck, Peter and J, 0. Sullivan
BBACTIOHS OP ID OXYGEH ATOMS IV. KIACTIOHS KITH *20, H2
AKr C02. In: International Conference on Photochemistry
Held at Hunches, September 6-9, 1967, Part I, preprints.
ISax-Plank-lnstitut fuer Kohlenforschung, Muelhei» as dec
Ruhr, West Germany, p. 94-112, Sept. 1967. 26 refs.
CFSTI: PB 176466
Ozone quantum yields from mixtures of oxygen with N20, H2 and
C02, photolyzed at 1470 A, are investigated to determine
relative rates of reaction of ID oxygen atoms with the admixed
gases. The data are expressed with respect tc the rate of
reaction with C02 for comparison with similar data obtained by
Cvetanovic from the photolyses cf N2C and BQ2. Order of
magnitude agreement Is observed. (Authors' abstract)*#
09078
Cadle, R. D- and F. E.. GraViek
PHOTOCHEMISTRY OP THE SYSTEM KETBRE-80-H2. In: International
Conference on Photochemistry Held at Munchen, September 6-9,
M. Basic Science and Technology
1189
-------
1967,Part I, Preprints- Hax-Planck-Institut fuer Kohlenforschung,
Huelheim an der Ruhr, West Germany, p. 113-125, Sept.. 1967.
CFSTI: PE 176166
Nitric oxide has been found tc react rapidly with singlet methylene
produced by the photolysis of ketene and possibly also with excited
Ketene, judging from the ratios ethylene produced/ketene reacted.
The presence of nitric oxide prevented the formation of methane and
ethane when ketene-N0-H2 mixtures were irradiated at room
temperature or 200 C. The products resulting from the presence
of nitric oxide were all of low molecular weight, judging from the
mass spectra. Eight products were separated using gas
chromatography and their mass and infrared spectra determined.
Only one, hydrogen cyanide, was definitely identified- (Authors)
abstract)
09079
K- F. Preston, R. J. Cvetanovic
THE PHOTOOXIDATION OF B0TESE-1 EY NITROGEN DIOXIDE AT SHORT
WAVI-LIHGTHS.. In: International Conference on
Photochemistry Held at Munchen, September 6-9, 1967, Part I,
Preprints., flax-Planck-Institut fuer Kohlenforschung,
fluelheia an der Ruhr, West Germany, p- 166-192« Sept- 1967-
17 refs..
CFSTI: PE 176466
The photooxidation of butene-1 by nitrogen dioxide has been
studied at 2288 A and at longer wavelengths- Frcm the measured
effects of additions of inert and other gases on the product
yields it is concluded that 1D2 oxygen atoms participate in the
photooxidation at 2288 A- Ground state oxygen atoms, produced by
the photodissociation of N02 and possibly by quenching of
C(1D) by the olefin* are also important in the
photooxidatiin at 2286 A, and are believed to give rise to
practically all of the observed yields of the addition porducts,
n-butanal and 1,2 epaxybutane. The indications are that the
reaction of C(1D) with butene-1 at total pressures below one
atmosphere yields very little stabilized addition product.
(Authors" abstract)M
09C80
Peter Borrell, P. Cashmore
THE ONSENSITISED ((SIC)) PHOTOLYSIS OF EUT-1-ENE AT 18U9 A„
In: International Conference on Photochemistry Held at
ftunchen, September 6-9, 1967, Part I, Preprints. Max-
PlanJc-lnstitut fuer Kohlenforschung, Huelheim an der
Ruhr, West Germany, p.. 193-210, Sept. 1967. 16 refs.
CFSTI: PE 176466
On photolysis at 1849 A„ but-1-ene yields 25 hydrocarbon
products and a solid polymer. In order to elucidate the
1190
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
mechanism, the effects of addled gases, time* pressure of reactant
gas and temperature were investigated. A free radical mechanise
is postulated in which there are six primary reactions to
account for the products and their relative yields. The two
major primary reactions are clevage of the C-C and C-H
bonds in the Beta position to the double bond in a 6:1 ratio.
Addition of foreign gases to the system caused a decrease in
the product yield which was shown to be due to guenching of the
reaction- This is attributed to the collisional deactivation
of an excited state intermediate of which the
decomposition lifetine has been estimated to lie within the
values of 2..6 to 6,,4 x 10 to the minus 10th power sec.
(Authors" abstract)#»
09082
Paul Suppan
SOLVES? AMD TEMPERATURE EFFECTS IN THE PHOIOBBDOCTICH OF
KETONES. In: International Conference on Photochemistry
Held at Munchen, September 6-9, 1967, Part XI, Preprints.
Hax-Plank-Institut fuer Kohlenfojcscbung, Kuelheim an der
Buhr, Best Germany, p. 643-658, Sept. 1967. 15 refs.
CFSTI: PB 176466
The dependence of the guantum yield of photoreduction on
solvent polarity and on temperature has been investigated for a
number of substituted aromatic ketones. An interpretation in
terms of the dipole moments in excited states to account for
the solvent effect is discussed. From the temperature effect
it is suggested that the different reactivities of n-pi*, pi-pi*,
and CT states is related to an activation energy. (Author's
abstract)##
09087L
CONCLUSIONS OF THE SYMPOSIUM OB THE PHYSICO-CHEMICAL
TRANSFORMATION SULPHUR COMPOUNDS IK THE ATMOSPHERE ARD THE
FORMATION OF ACID SMOGS, MAINZ/GEBMANY, JUNE 8TH/9TH,
1967. Organisation for Economic Co-operation and Development,
Paris (France) DAS/CSI/67.99, 7 p.. Jab. 17, 1968
The processes of oxidation and transfomaticn of sulphur compounds
in the atmosphere are briefly discussed.. The catalysed oxidation
of so2 in fog droplets or on aerosol particles is one of the
important processes. The controlling factor of S02 oxidation in
fog is the oxidation rate within the droplets which is rather high
in the presence of small amounts of catalyst. Removal of SQ2
by rainout and washout is also rathec efficient. Sources ot
further information on these subjects, as well as on measureptant
methods and air guality data, are mentioned*##
M. Basic Science and Technology
T191
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09172
Pejack, Edwin R-, and Henry 8. TelXoff
EFFECTS OF A TRANSVERSE ELECTRIC FIELD ON THE CHARACTERISTICS
AND HEAT TRANSFER OF A DIFFUSION FLAME. Ohio State Univ„, Re-
search Foundation, Columbus, Contract DA-31-12H-ASO-D-246,
Pro;}. 1364, TR-8, 13Up., Hov. 1967. 52 refs..
CFSTI, DDC: AD 664180
Effects of a transverse electric field on a parallel flow
diffusion flame in a flat combustion chamber were investigated.,
Various mixtures of propane, nitrogen, and air were introduced
separately at the base of an experimental combustion chamber and
burned in a diffusion flame sheet located between flat walls of
the chamber which served as anode and cathode. The electrode
walls were instrumented to measure the local heat transfer rate,
local current density, and pressure. It was found that the
application of a voltage difference across the electrodes moved
ions out of the burning zone and resulted in a current at the
electrode vails. The heat transfer rate near the base of the
flame was considerably increased on the cathode and decreased on
the anode; at positions further from the base of the flame the
electric effect was lessened. Flame distortion was thought to
be caused by electrically induced gas motion derived from a
gradient in current density in the flow direction and by the
onset of an electrically induced flame flickering. An analysis
of the products of combustion revealed that the applied electric
field acted to increase the amount of unbtirnt solid carbon and
decrease the quantities of unburnt fuel and carbon monoxide.
(Authors" abstract)##
09186
P. V., Danckwerts, K. W. Hctfeil
THE ABSORPTION OF CARBON DIOXIDE INTO AQUEOOS AMINE SOLUTIONS AND
THE EFFECTS OF CATALYSIS- Trans. Inst. Chen. Engrs.
(London). 45(1):32-H9r Jan.-Feb. 1967- 46 refs.
fihen carbon dioxide is absorbed by aqueous amine solutions, a
fast reaction leads to the formation of amine carbamate. This is
followed by a slow reaction in the bulk of the liquid, leading
to partial hydrolysis of carbamate to bicarbonate. When
the second reaction is complete the pressure of carbon dioxide is
lover and the concentration of free amine higher. The addition of
a catalyst, such as sodium arsenite, speeds up the second
reaction and may thereby increase the rate of absorption and
the capacity of the absorbent. Calculations are compared with
the results of absorption measurements in a stirred cell.
The agreement is good and indicates that the mechanism
assumed for the absorption process is correct. A catalyst
can substantially increase the rate of absorption ai»4 the
capacity of the solution when the ratio (moles carbon dibxide
absorbed/moles amine initially present) is greater than 1/2.
1T92
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
This night form the basis of an economic industrial process for
carbon dioxide absorption* (Authors" summary)##
C9200
Tipson, P.. S„, A. Cohen,, and A„ J.. Fatiadi
AIF POLLUTION STUDIES., In: Robert Schaffer (ed.)„
Organic Chemistry- July 1966 through June 1967,
National Bureau of Standards, Washington, D. C.,,
SES-TN-427, 11p..» Oct- 1967-
Studies have teen conducted on polycyclic aromatic hydrocarbons
and certain of their oxidation products.. A description is given
here of the detection of impurities in commercial preparations of
polycyclic aromatic hydrocarbons.. The procedures used to
purify these preparations are discussed,. The presence of an
impurity in zone refined anthracene was demonstrated.. Upon
isolation with the use of thin-layer chromatography, carbazole
vas found to be an impurity. Upon re-examination by thin-layer
chromatography two ether impurities Mere discovered- A diner
of anthracene, 9«9:10,IQ-bianthr&cene, vas prepared. Its
ultraviolet and infrared spectra were recorded. In order to
establish specifications cf purity for anthracene as a possible
standard a comparison vas made between three commercial samples
of anthracene: high purity, synthetic and zone-refined. It was
shown that the synthetic anthracene is the purest of the three
samples. Fluorene was similarly studied..##
09267
Doepfcer, F» 0., S.. G.. Lias, and P« Ausloos
PHOTOLYSIS OF CYCLOPENTANE AT 1470, 1236, AND 1048-1067 A.
J. Chen. Phys.„ 46( 11) :4340-4346, June 1, 1967. 23 refs..
The photolysis of cyclopentane has been investigated at
wavelengths of 1470, 1236, and 1048-1067 angstroms* The primary
process, which is the elimination of a hydrogen mole from
cyclopentane, is of major importance at 1470 angstroms but its
quantum yield diminishes at shorter wavelengths where processes
involving c-c cleavage becomes more predominant. The products
formed in the gas-phase photolysis of cyclo-C5-DlO-B2S
mixtures and in the solid-phase photolysis of cyelo-C5H10
indicate that the excited cyclopentane molecule undergoes ring"
opening to form a 1-pentane molecule- is the gas phase, the
internally excited 1-pentane decomposes to form methyl and ethyl
radicals. At 1048-1067 angstroms, ionization is extensive, on
the basis of an isotopic analysis of the propane formed in the
photoionization of C5D10-C5H10-O2 mixtures the pattern of the
dissociation of the parent ion is determined, fragmentation of
the parent ion diminishes with an increase in pressure. The
collisional deactivation process is more pronounced for the
M. Basic Science and Technology
1593
-------
perdeuterated than for the Fe*Frct0Jiated cyclopentane ion.. The
data also indicate that a fraction of the parent ions undergoes
ring opening to for» cis or trans-2pentene as a final product.
(Authors* Abstract)tt
09398
Georgii, H. and E. Kleinjung
BE1ATI0NS BETWEEN THE CHEMICAL COMPOSITION OF ATMOSPHERIC AESOSOL
PAHTICLES ASD THE CONCENTHATIOH OF NATURAL ICE NUCLEI.. J. Fech.
Atnospheriques, 3 (1):115-156, Oct.-Dec. 1967, 20 refs*
Simultaneous measurements of ice nuclei. Aitken nuclei, and large
particles nere Bade during 1961 at the Taunus observatory on Ht.
Kleiner Fledberg and also in a suburb of Frankfurt, chemical
analyses were nade for several components of the atmospheric
aerosols: SOI, N03, CI, Na, K, Ca, and NH1 ions„ Aitken nuclei, do
not participate in the freezing process in supercooled clouds at
temperatures above -21 deg. C. and the majority of ice nuclei
activated at temperatures above -20 deg„ C. are in the size-range
0.2-2»0 nicron radius. Thus, only large and giant nuclei are
isportant for ice nucleation above -21 deg. C. The authors
conclude that the city of Frankfurt constitutes a very productive
source of large particles and Aitken nuclei, but the nuclei
produced in the polluted atnosphere of the Main valley are
activated only at lov temperatures which are of little interest to
cloud physics. Furthermore, if Aitken nuclei are assumed to
coagulate upon the large particles to cover their surfaces, then a
residence tiae of 10 hrs. in a polluted atmosphere would be
sufficient to contaminate the surfaces of these large particles,
and thus lead to a deactivation of potential ice nuclei.
09037
Sazonov, L. A., and S» V. Artanonov
INVESTIGATION OF THE MBCHANTS* OF THE OXIDATION OF CARBON
MONOXIDE OB LANTHANUM OXIDE- Kinetika i Kataliz, 8 (3) :516-550,
Bay-June 1967,, 6 refs.
The mechanisn of the oxidation of CO on lanthanua oxide in the
temperature region 300-420 degrees was investigated using
radioactive carbon C14* Belov 300 degrees, the reaction
proceeds with an activation energy E1 eguals 3 kcal/mole and is
acconpanied by canplete adsorption of the Co2 formed on the
Surface of the oxide. In the region of 300-100 degrees, the
limiting step is desorption of C02 with an activation energy E2
equals 19 kcal/aole; below 100 degrees, the Halting step is the
rate of cbemisorption with E3 eguals El eguals 3 kcal/mole, it
is believed that the oxidation of CO proceeds through a stage of
formation of a complex of the type C03 with an activation energy
of the dissociation C03 yields C02 plus 0= equal to 10
kcal/aole. (Authors11 abstract) *#
1794
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
094411
Mueller, R. J. and P. B. Stickney
EVALDATING THE RELIABILITY OF AN ACCELERATED TEST FOR QUALIFYING
CZONE-PROTECTIVE WAXES. (FINAL PROGRESS REPORT.) Battelle
Memorial Inst., Columbus, Ohio, Columbus Labs., Contract
DA-28-043-AMC-00496-|E) , ((43))P»* March 30, 1967.
DDC: AD 824072
The reliability of an accelerated test for qualifying
ozone-protective waxes is evaluated. Thirty waxes were screened
in an accelerated laboratory test using a styrene-butadiene rubber
(SBR) composition to determine their ability to protect against
ozone cracking. Ten waxes were incorporated into SER-jacketed
cable for outdoor exposure tests, the results of which were
correlated with accelerated laboratory tests. The conclusions
reached were: The accelerated ozone test developed is not
adequate for qualifying czone-protective waxes. Mandrel-wrapped
cable is more susceptible to cracking than dumbbell specimens.
In the round-robin progran to evaluate the reproducibility of the
accelerated test among laboratories, good reproducibility was
obtained when the laboratories followed the procedure carefully.
Outdoor exposure tests showed a wide variation, even among
approved waxes, in their ability to protect against cracking.
Correlation between accelerated tests and outdoor exposure was
limited., An accelerated test developed for SBR should be
usable with neoprene or natural rubber with litter oc no
modification.#*
09576
Hisatsune, I. C.
ESTIMATION OF THE ISOHER1ZATIOK BATE OF NITBO0S ACID. J. Phys.
Chem., 72(1):269-271, Jan. 1966. 9 refs.
The rate constant for the unimolecular isomerization of cis -
nitrous acid to the trans acid has been calculated by using the
transitionstate model. The ooe'dinensional potential-energy
function for the barrier to internal rotation of the HO group and
the necessary force constants and structural parameters of the
transition complex were obtained from an earlier infrared study of
isotopic nitrons acids. Quantum correction arising from the
penetration of the potential barrier does not appear to be
important. The isomerization half-life is about three orders of
magnitude shorter than that of the fornation of the acids from NO,
102, and H20* (Author's abstract, modified)
09719
Darwent, B. deB., B. L» Vadlinger, and Mary John Allard
TBI PHOTOCHEMICAL DECOMPOSITION OF HYDROGEN SULFIDE. THE REACTIONS
OF HYDROGEN ATOMS AND HS RAEICALS. J. Phys. Chen*, 71 (7):2346-
2347, June 1967. 10 refs.
M. Basic Science and Technology
-------
The photolysis of H2S as a means of studying the reactions of H
atoms hinges on the assumptions that the H atoms produced by the
photolysis do not contain a significant amount of excess energy and
that the HS radicals disappear without producing H or H2. The
above assumptions have been examined by observing the effect of a
large excess of inert gas
-------
Numerical data on air pollutants are compiled and tabulated foe a
broad range of problems. The effects of pollutants on human
health, plants and livesotck are presented. Characteristics and
chemical composition of the atmosphere and its pollutants are
compiled- Data on emission sources of pollutants and their
distribution at various periods of time in different locales are
presented* Other categories covered are air dispersion of small
organisms* biological effects of gaseous ions, and spacecraft and
nuclear submarine atmospheres.
10027
Hidalgo, Alberto F. and Clyde Orr, Jr.
HCBOGEKEOUS NOCLEATION OF SODIUH CHLORIDE SOLUTIONS., Ind. Eng.
Chen Fundamentals, 7(1) :79-83, Feb. 1968. 14 refs.
Experimental confirmation of the thecry of homogeneous nucleation
for electrolyte solutions is demonstrated by an analysis of the
behavior at 25 deg.C. of an aerosol composed of supersaturated sodiu
chloride solution droplets 0.01 to 0.1 micron in diameter™ (The ter
homogeneous applies to systems devoid of foreign nuclei.) The
humidity of the air with which the aerosol was in equilibrium was
adjusted to attain a series of droplet supersaturation states.
Nucleation and crystallization of the droplets subsequently ensued,
being detected by an ion counter that permitted following the size o
the aerosol particulates as a function of tine at specific relative
humidities. The behavior of the aerosol could be attributed to
homogeneous nucleation because only a small proportion of the
droplets contained foreign nuclei when they were formed on sub
division of the original liquid. The time for nucleation was found
to be a logarithmic function of the electrolyte activity as theory
predicts. (Authors* abstract)
10037
Chia, Vu-sun, Joan Jacobs, and B. H« Sage
OSCILLATORY COMBDSTION AT ATMOSPHERIC PRESSURE K0S0CHR0MATIC AND
TOTAL OPTICAL INTENSITY.{TECHNICAL REPORT.) California Inst. of
Tech., Pasadena, Chemical Engineering Lab., Ms-ft236» 35 p., 1968. 8
refs»
A number of measurements were made upon the perturbations in
monochromatic and optical intensity, in the course of oscillatory
combustion of air and natural gas at atmospheric pressure. These
measurements were obtained as a function of mixture ratio and, to a
more limited extent, of the effect of changing the effective length
of the combustor. As would be expected, the maximum perturbations i
monochromatic intensity corresponded closely to the maximum
perturbations in normal stress. Variations in the length of the
combustor influenced materially the magnitude of the perturbations i
normal stress. These changes in length also caused a similar
fluctuation in the monochromatic intensities which corresponded to
M. Basic Science and Technology
1197
-------
the vave lengths of water and carbon dioxide- At corabustor lengths
corresponding to nonoscillatory combustion, the perturbations in
optical intensity are approximately equal to the standard deviation
of the measurements. This is characteristic of the poison
distribution such as often is experienced in nonoscillatory tuchulen
combustion. {Authors* introduction)
10011
Goetz, Alexander and olgierd J. Klejnot
TRANSFORMATION OF GASEOGS REACTIVE HYDRCCARECNS INTO AEHOCOLLOIDS
01TEAVI01ET IRBAEIATION„ j» Air Pollution Control Assoc., 17
(9) :600-603„ Sept. 1967.,
A substantial variety of hydrocarbons, particularly the reactive
types, can be converted from the gaseous into the aerocolloidal stat
by brief exposure to uv-irradiaticru The procedure for evaluating
the capacity of various hydrocarbons to form aerocolloids, and thus
to define the difference between non-reactive and reactive types, is
illustrated. Two sensoring devices were utilized; an aerosol
photometer and a moving slide impactor. A summary includes these
observations: the aerocclloid formation by ultraviolet exposure is
due to intermediate oxidation states of the molecules vith a high
tendency to polymerize into sub micron particulates™ High humidity
levels increase the reaction rate and thus the aerosol formation.
The characteristic difference between saturated and unsaturated HC
types is the much lesser VO-reactivity of the former. This method
permits the tracing of organic components in the open atmosphere. I
promises to facilitate the sinple and rapid discrimination between
the neutral and potentially reactive HC types.
1Q013
Levy, Authur and Earl L. Rerryaan
SOLTUR-OXIDE POBMATXON IH CAFBOWYI SULFIDE FLAMES. Preprint,
Battelle Memorial Inst., Columbus, Ohio. Columbus Labs.,
(26)p., (1968)« 10 refs„
Oxidation processes in lew pressure (1/10 a*m) carbonyl sulfide
flames are examined. Two distinct reaction zones are noted, first,
zone in which carbon monoxide and sulfur dioxide are formed, and
second, a zone in which the caibcn monoxide oxidation is completed.
Kinetic analysis suggests that the initial step is the abstraction o
a sulfur atom by an oxygen molecule. The rate constant for this
reaction is calculated.
10015
Semeth, Andras and Robert p. Sawyer
THE OVERALL KINETICS OF HIGH TEKEERATURI METHANE OXIDATION IN A
1198
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
FICM REACTOR- California Univ., Berkeley, Division of Ther-
mal Systems, 68-2, 20p», (1968) - 20 refs.
The rate of methane consumption in an oxidation reaction was
Measured in a non-isothermal flow reactor in the temperature range o
1180-1282 deg„ K- The reaction was monitored by mass spectromet-
ry analysis. The following overall rate expression was found va-
lid, however, only for temperatures greater than 1200 deg. K» The
result is in reasonable agreement with data measured by another
method in the high temperature range. (Authors" abstract modified)
10066
Shaw, J. T. and P. D. Green
OXIDATION OF S0IPHDB DIOXIDE 19 AIR AT 950 DIG C:
CO-OPERATIVE INFLUENCES OP CARBON HONOXIDE AND NITRIC OXIDE.
Nature, 211 (5054):1171-1172, Sept. 10, 1966- 8 refs-
The oxidation of sulfur compounds in fuel during composition to
form sulfur dioxide and the further oxidation of this to sulfur
trioxide gives rise to the probles* of corrosion, specifically in
boilers. The part played by oxides of nitrogen and carbon, both
of which occur influe gases frcn normal fuels, and their influence
on the oxidation of sulfur dioxide in a clean system has been
investigate a,. A marked effect on sulfur trioxide production was
found when nitric oxide and carbon monoxide were present together.
The experiment is described.**
10078
Chermack, X. A. t«d.)
SUBHARY 01 THE CONFIBENCE OH THE OPTICAL PROPERTIES OF AEROSOLS,
15-17 OCTOBER 1964, New York Dniv., Bronx, Research Div.,
Contract DA 36-039-AHC-03«H1-
-------
Tex. Dept. of Biology and Biophysical Sciences, 10p.., April
Dept. of Biology and Biophysical Sciences, 10 pu, April 8, 1968. 10
8, 1966. 1 refs.
Both labelled acetate and stearate were found to serve as
precursors for the formation of hydrocarbons in Chlcrella
pyrenoidosa.. Acetate incorporation was inhibited in the dark. Of
particular interest was the observation that the carbon skelton. of
stearic acid could be converted into heptadecane but not into the
predominant monounsaturated C17 hydrocarbon- This study presents th
first evidence that straight- chain fatty acids serve as precursors
for short-chain saturated hydrocarbons. (Authors" abstract}
10129
flurn, S.r Basil Diaitriades, and 8. D. Fleming
EFFECT OF HYDHOCAHEON TYPE OF BEACTIVITY OF EXHAUST GASES. In:
Vehicle Emissions, part II, SAE Progress in Technology Series, Vo.,
12, New York, Society of Automotive Engineers, Inc., 1966, p. 1-9.,
6 refSo (Presented at the Mid-Year Meeting, Society of Automotive
Engineers, Chicago, 111., Kay 1965.)
Unburned hydrocarbons and other products of combustion are
recognized as contributors to photochemical air pollution. The
work reported here was a first approach in finding an expression of
exhaust gas guality—or compositional characteristic—that
would associate directly with the photochemical activity of the
composite sample. Olefins, aroaatics, and partial oxidation
products have been cited as the principal smog precursors in
exhaust gas.. However, results of this study indicate that for the
general case, collective deterainaticn of these classes provides
and unreliable indication of reactivity. The findings are expected
to be useful in further development of methods to measure — or
predict — the air polluting potential of exhaust gas with
increased reliability. (Authors abstract)
10108
6. V. Bozenberg
PHYSICAL FBIKCIFLES OP THE SPEC1FCSC0PI OP IIGHT-SCATTERIBG
SUBSTANCES. (Pizicheskiye csacvy spectroskopii
svetorasseivayushchikh veshchestv.) Text in Russian. Osp.
Piz. Hauk, 91 (4):569-608, April 1967. 123 refs.
The present paper is an expanded version of a lecture
presented to the All-Unicn spectroscopy Conference at Moscow
State University in February 1965. Directed chiefly to'*...
experimentalists untutored in the subtleties of mathematical
theory", it originates in the author's ccsplaint that only a
dozen or so of the hundreds of papers produced annually on the
spectroscopy of light-scattering materials satisfy present-day
methodological requirements. After tracing the reasons for this
failure, he reviews the state of the art under the following
1200
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
headings: general principles of absorption spectroscopy of
optically homogeneous specimens, and the spectral function
of transmission; the spatial and ctructural functions of
transmission for heterogeneous medium without scattering, and
methods of emersion and compression; light propagation in a
scattering medium, and the transfer matrix and its relation to the
parameters of the medium; a general statement of the problem of
spectral analysis of aacroscopically homogeneous light-scattering
bodies; and concrete methods fcr spectroscopy of light-scattering
substances. In the last category, these methods are discussed:
a narrow directional beam; methods based on low-frequency
scattering; spectroanalytic use of measurements of the light
field within a scattering medium; spectroscopy of thick layers
of scattering materials with small specific absorption;
luminescence analysis; and other irethcd£.<#
10422
A. K. Chatterjee, and B. K. Maarumdar
METHYL GROUPS 111 COAL. Fuel, H7 (2);93-102, March 1968.
13 refs.
The contention that methane formed during low temperature
pyrolysis (600 degrees C) owes its origin almost exclusively
to the methyl groups in coal and that such methane formation
(including small proportions of ethane) represents the maximum or
true measure of the methyl content is re-examined in the light
of the pyrolysis behaviour of nitro-coals. Nitration is
believed by the authors to cause selective oxidation of the
methyl groups to carboxyl groups (apart from the introduction of
a considerable proportion of nitro-groups in coal). It has now
been found that such nitro-coals on pyrolysis at 600 degrees C
yield no methane and little cf ether hydrocarbons, but much
carbon dioxide, the volume of which after due
corrections appears to be of a magnitude similar to that of
the methane obtainable by pyrolysis at 600 degrees C of the
corresponding untreated coals. Further, nitro-coals by
reductive decarboxylation followed by thermal decarboxylation
at 350 degrees C for completeness yield a volume of carbon
dioxide virtually egual to that of the methane obtainable
by pyrolysis of the untreated coals. These findings appear to
confirm the authors' previous hypothesis of the origin of methane
during pyrolysis at 600 degrees C, and hence the validity of
assessment from this of the methyl content in coals.*#
10507
Schuetz, Alfred
THE ELECTBICAL CHARGING OF AIBOSOIS. Staub (English translation
27 <12|:21-32, Dec. 1967, 2« refs.
CFSTI: TT 67-51H08/12
The most important charging mechanisms for aerosols and the
magnitude of the electrical charge of an individual particle are
M. Basic Science and Technology
1201
-------
discussed. Charging by diffusion is solely governed by the thermal
notion of ions in the gas envelope surrounding the particle,
charging by ion bombardment in the electrical field is effected in a
unipolar ionization zone* e.g., in a corona discharge. A further
possibility of particle charging consists in the direct contact of
the particles with electrodes carrying a potential. The charging of
particles can be accomplished by contact-electrical processes,
whereby the magnitude decisive for electrical charging is the contac
potential between the two contacting materials. In the stirring-up
of deposited dust electrical charging is solely effected by the
separation of the contact points between the particles, as well as
between the particles and their support. Atomization of liquids is
discussed as another method for charging dispersed particles
{positive or negative).
10512
sinonaitis, R. and J.. N. Pitts, Jr»
PHOTOCREH1STBY OF GAB A-BUTYRCLACTONE IN THE LIQUID PHASE. Pre-
print California Oni*„, Biverside, Dept. of Chemistry, 18p.,
41965/J
The photolysis of gama-butyrolactone was investigated in the
liquid phase with the 2537A line of a mercury resonance lamp. The
major products were allylfornate, succlnaldehyde, cyclopropane, and
carbon dioxide with quantum yields at 25 deg.. C of the 0.23, 0.06,
0.013 and 0*015, respectively. Prom product quenching data, it is
suggested that triplet-triplet energy transfer from gama
butyrolactone to cls-butene, transbutene, cyclohexene and biacetyl
occurs at a diffusion controlled rate and that the allylformate and
cyclopropane originate from one state, probably a triplet, but that
succxnaldehyde originates from a different state.. Added isopropyl
alcohol quenched the formation of allylformate and cyclopropane, but
acetonitrile as a solvent had no effect on their yields over the
concentration range of 0.3-16.0 moles/liter. An increase in
temperature from 25 deg. C to 98 deg. C increased the yields of
succlnaldehyde and cyclopropane and decreased the yield of
allylfornate, but the sum of the guantum yields of these products
remained relatively constant. (Authors* abstract)
10519
Cowell, Gawin W. and Janes Pitts, Jr.
PHOTOCHEMICAL STUDIES IN RIGID MATRICES. II- A STUDY OF THE
PHOTOCHEMICAL REACTIVITY OF ANTHRACENE IN POLYSTYRENE AND THE
DEVELOPMENT OF AS O-NITFOBENZAIDEBYDE ACTIHOMETEF IN
POLYMETHYLMETHACRYLATE. Preprint, California Univ., Biverside,
Dept. of Chemistry, {19}p., (1967/).
The photochemistry of o-nitrobenzaldehyde and anthracene in rigid
polymer films has been studied at 25 deg. and 3340 and 3660A. o
Nitrobenzaldehyde "dispersed* in polymethylmethacrylate, M.W. <
20,000 plus or minus 3,000, undergoes the well known photo
isomerization to o-nitrosobeazoic, the guantum yield being 0.05 plus
1202
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
or minus 0.06. fiithin experimental error, this is the same as in
fluid solutions and in the pure sold.. In view of the stability and
convenience of this system, its use as an actinometer in the spectra
region 2800-410011 is envisaged. Anthracene "dispersed* in
polystyrene, U.S. < 47,000 plus or minus 4,000, undergoes
photodinerizaticn at a rate ouch reduced fton that in fluid solution
or in a potassium bromide pellet. The nature of the 'dispersion' of
the nathracene in the film differs significantly from its state in
potassium bromide Matrices. In the presence of oxygen, the major
part of the photochemical reaction leads to the formation of the
photooxide of anthracene. Kinetic and mechanistic details are
discussed. (Authors" abstract)
10522
Pratt, David Terry
COMBUSTION OF AHMONIA AMD AID IB A NELL-STIRBED REACTOR,
Thesis (Ph.D), California Univ., Berkeley, Coll. of
Engineering, May 1968, 106p. £2 cefs.
An adiabatic, veil-stirred reactor was used to determine the
over-all chemical reaction rate constants for the near-
homogeneous, gas-phase combustion of ammonia and air. The
overall reaction rate for ammonia-air combustion in a back-mixed
combustion system can be veil represented by an Arrhenius
equation. The experimentally obtained activation energy,
pre-exponential factor, fuel and oxygen reaction orders do not
agree veil vith those reported from earlier investigations.
Such values appear to depend on the pressure, temperature,
reactant concentrations and diluent employed in the various
studies. with aging of the zirconium dioxide reactor vails,
the slov oxidation reaction regime became more evident and
persistent, and slov oxidation data were not reproducible after
a few hours of operation* on the other hand, fast oxidation
conditions were reproducible. This seems to imply clearly that
the wall plays an important role in the slov oxidation
reaction mechanism. The maximum attainable loading, for an inlet
temperature of 400 degrees K, vas 20 times less than maximum
loadings obtained vith hydrocarbon fuels at the same inlet
temperature. Blowout limits can be corrected effectively for
inlet temperatures varying from 300 degrees K to 500 degrees K«~#
10907T
Lunge, G„ and E. Berl
HITROGEH OXIDES ABD TRB IE&C CHABBlB BfiOCESS. II. BIHAVIOR
OF A MIXTUBE OF G1SXS* PBESOMABIY NO t 802, IH C0HCEKT1ATEE
S0LF0BIC ACID ADD soDXOlt HiEFOXiti 1/5 JU | (Ontersuchungen
ueber Stickstoffoxyde und ueber den Bleikammerprozess. II.
Verhalten eines Gasgemisches von der ungefaehren Zusammensetzung
NO ~ H02 gegen konz. Schwefelaaeurt und 1/5-b«
Natronlaoge.)) Translated fro* Geriaiu 2. Angev. Chew.
(Heinheim), 19*19):857-869, Bay 1906*
M. Basic Seism;* and Technology
1203
-------
The behavior of a gas mixture containing NO and N02 in
sulfuric acid and sodium hydroxide was investigated with the result
that for analytical purposes sulfuric acid is the only absorption
liquid for this gas mixture. Also the behavior of nitrogen oxide
in the presence of oxygen and water was studied together with the
kinetics of nitrogen oxide oxidation with oxygen or air. The
kinetic curves indicated that the reaction 2N0+02=H20t takes
place at a constant rate which indicates that the oxidation takes
place directly without foxmaticn of H203 as an intermediate.#f
10S10T
Hautefeuille# P. and 0. Chappuis
PARANITRIC ACID. ((Sur l*acide pernitrigue.)) Translated from
French. Camp. Bend. (Paris), 94:1111-111ll, 1862.
Nitrogen peroxide formed when czcne is prepared by electric
discharge in dry air was further investigated. The rate at which
the peroxide is formed was studied by spectroscope. Also its
conversion into another cxide was studied by pressure measurements*
The present article published in 1882 has historical significance
and deals with the formation of nitrogen oxides by electrical
discharge.##
1091IT
BodensteiD, W.
THE SATE 07 THE REACH OH BETtiEES NITRIC OXIDE ABD OXTGEH.
(Die Geschwindigkeit der Beakticn zwischen stickoxyd und
Sauerstoff.) Translated from German. Elektrochem. angev.
physik. Chemie (Reinheim), 24 (13/14):183-201, July 1, 1918. 30
refs.
The oxidation of nitric oxide with oxygen was studied kinetically
fcy pressure recordings at temperatures from 0 to 90 degree C.
The reaction took place Bearding to the third order process 2N0
+ 02 = 2V02. The rate was independent of N02, H20 and
S02 admixtures. The experiments proved that Raschig was
incorrect when he assumed that BO is first rapidly oxidized to
K203 which is then slowly converted to N02.##
1C912T
Bodenstein, Rax
THE SPEED OF THE COHBINATIOB OF HITRIC OXIDE AHD 0XTGEN. ((Die
Geschwindigkeit der Vereiningung von Stickoxyd und sauerstoff.)
stoff.)) Z. angev. Chen. (Heinhein), 31:145-148, July 30, 1918.
The reaction rate of nitric oxide with oxygen was determined by
batch experiments. The conversion rate was determined from the
measured pressure change. Experiments were also made to
1204
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
elucidate possible side reactions and catalytic effects. The
result of the stud; indicates that the reaction takes place
according to the trimolecular equation 2 NO + 02 = 2 N02 and
not as suggested by Bascbig by a twc stage reaction with N203
as an intermediate.##
1C913I
Bodenstein, flax
FORMATION AND DECOMPOSITION 01 1HE HIGHER OXIDES OF HITBCGEN.
((Bildung und Zersetzung der hoheren Stickoxyde.)) Translated
from German. Z. Physik. Chen. (Ieipzig), 99:68-123, 1922.
19 refs.
The formation and decomposition of higher nitrogen oxides was
studied by determining the equilibrium constants of the reactions
2N02 yields N204 in the temperature range of 9-115 degree c
and 2N02 yields 2H0 + 02 in the range of 220-550 degree C.
Expressions for the logarithm of the equilibrium constants as a
function of temperature were obtained. Also the rate constants of
the reaction 2N0 + 02 - 2HC2 was determined in the temperature
range of 14C-39G degree C. Beaction mechanisms are discussed.it
10917T
Gevitz, H. So and «• Volker
INHIBITION OF PHOTOSYNTHESIS BY CARBON MONOXIDE AND SUSPENSION
OP THE CARBON MONOXIDE INHIEITION BX LIGHT. (Hemmung der
Photosynthese durch Kohlenozyd und Aoghebung der
Kohlenoxydhemmung durch Licht„) (Translated from German).
Naturforsch,, (Tuebingen), 18b:6H9-653, Aug., 1963» 5 refs.
Experiments with chlcrella pyienoidosa in an atmosphere of
C02-argon and CC2-C0 were made to study the inhibition of
photosynthesis by carbon monoxide.. It was found that cells
grcwn in light show inhibition of photosynthesis by carbon
monoxide,. Inhibition is reversible and depends on the CO and
02 partial pressures. Also the effect of the spectral
characteristics of light on the inhibition of photosynthesis was
studied. The experiments indicated that in photosythesis an
enzyme is involved which has an effective group containing iron.
This enzyme transports oxygen in photosynthesis. Carbon monoxide
inhibits photosynthesis by binding the iron in the enzyme. The
absorption spectrum of the carbon of the photosynthesis was
determined* The carbon monoxide compound can be split by light
and thus inhibition is stopped.*#
11050
E. F, Stephens
CHEHISTR* OF AT80SPHEB1C OXIDANTS. Preprint, California
M. Basic Science and Technology
1205
-------
Dniv., Riverside, Statewide Air Pollution Research Center,
12p., 1968. 15 ref£. (Presented at the 61st Annual Heeting of
the Air Pollution Control Association, St. Paul, Minnesota,
June 23-27, 1968, Paper 68-57.)
All of the important oxidants in polluted air are formed there by
chemical reactions which occur among the primary pollutants.
The most abundant of these oxidants is ozone which is formed in a
cycle involving nitric oxide, nitrogen dioxide, atmospheric oxygen,
and hydrocarbons. This czone is test understood, not as a
reaction product, but as an intermediate in steady state
concentration between formation and disappearance reactions.
Hydrocarbons permit accusulaticn of ozone by reacting to
scavenge the nitric oxide which would otherwise remove the ozone.
The amount of ozone which can be formed in ambient polluted air is
limited to about one ppm because these scavenging reactions
become less effective when the nitric oxide concentration
becomes very small. The peroxyacl nitrates are a group of
oxidants which result frcm reactions between oxides of nitrogen
and organic pollutants. Olefinic and aromatic hydrocarbons make
the largest contribution to PAN formation; saturates
contribute little if any. the role of nitrogen dioxide and other
oxidizing agents is also discussed. (Author's abstract)##
111J47
Fatiada, A. J.
PERIODIC ACID, A NOVEL OXIDANT OF PCLYCYCIIC, AROMATIC HYDROCAR-
BONS. J. Res. Nat. Bur. Std. A, 72A {<») :341-350, July-
Aug. 1968.
Certain polycyclic, aromatic hydrocarbons can be oxidized with
periodic acid in aprotic solvents containing a small proportion of
water. A unique, two-fold character of response to periodic acid by
these hydrocarbons has been found: (1) production of a coupling
reaction through a radical intermediate ((conversion of pyrene into
1,1'.bipyrene, and fluorene into 1,2-bis (2,2'-biphenylylene
ethylene)) or (2) conversion into guinones by a two-equivalent
oxidation mechanism that does net involve a radical
intermediate {(acenaphthenem andtracen, anthrone,
benz((a)) anthracene, naphthalene, and phenanthrene)). Little or
no reaction was observed when oxidation was attempted with sodium
metaperiodate instead of periodic acid. Electron-spin rescnance
revealed no radical intermediate in the oxidation of malonic acid
with either periodic acid or sodium periodate. (Author's abstract)
11188
Hindsor, N* V *, and 0. B. Novak
STUDIES Of RADIATIONLESS TRANSITIONS IN CORCNEHE USING NANOSECOND
IASER FH010L1SIS AND SPECTFCSCCFI. Preprint, TRW Systems,
Bedondo Beach, Calif. Chemical Sciences Dept.,(18)p., 1968.
20 refs. (Presented at the International Conference on Molecu-
lar Luminescene Loyola Dniv., Chicago, 111.,Aug. 20-23,1968.)
CFSTI: AD 672997
1206
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
Be have used the technique cf nanosecond laser photolysis and
spectros g spectroscopy to observe absorption from both the lowest
excited singlet state SI, and the lowest triplet state II, of
coronene. The technigue employs a Q-switched ruby laser to produce
both a 30 usee pulse at 347 nm for excitation, plus, at the same
tine, a laser-induced spark which provides a background continuum
for absorption spectroscopy. Tine-resolved spectra are obtained
with an image converter camera. tie have observed new transient
absorption bands for coronene at 520 and 380 no and attribute these
to absorption by the Si state. The new bands locate previously
unobserved higher singlet level cf g parity* These bands decay over
a period of several hundred nanoseconds and are concomitantly
replaced by absorption bands characteristic of the lowest triplet
state, thus providing a pictoral record of the process of
intersystem crossing. He have alsc obtained the T-T absorption
spectrum of coronene in epoxy plastic out to 1.14 microns using a
doutle-beam cross-irradiation technique. New maxima in the infra-
red serve to locate th energies of three low-lying excited triple
levels. From the energy level data we believe that in coronene
intersystem crossing from higher singlet states to the triplet
manifold may occur, tie discuss how our kinetic observations of the
decay of the lowest excited singlet and the build-up of the lowest
triplet state bear on a recently proposed stationary state model of
radiationless transitions. {Authors* abstract)
11205
liu, Benjamin Y. H.
RECENT AEROSOL RESEARCH - UNIVERSITY OP MINNESOTA PARTICLE
TECHNOLOGY LABORATORY. Preprint, Minnesota Vniv.,
Minneapolis, Particle Technology Lab., ((12))p., 1968. ((23))
refs„ (Presented at the 61st Annual Meeting of the Air
Pollution Control Association, St. Paul, Minn», June 23-28,
1968, paper 126„)
A summary of research studies on methods for the generation,
measurement and sampling of aerosols is presented. Theoretical
and experimental research of the electrical charging of aerosol
particles by gas ions, the size distribution of atmospheric
aerosols, aerosol formation in high-temperature plasmas and from
molten metal, and the basic properties of chain aggregate smoke
particles are discussed.##
11210
Miller, William J.
FLAME IONIZATION AND C0HBDSTI01 INHIBITION. (TECHNICAL REPORT
RC. 1.) Aerocheu Research Labs, t Inc. , Princeton, N.J*
CST-102, TP-151, 23p«, Jan- 17 refs-
The inhibition of spherically symmetrical low-pressure CHI or
C2H2/02 diffusion flames by a variety of additives has been
studied. The relative efficiencies of the compounds studied have
M; Basle Science and Technology
1207
-------
been found to be very nearly the sane as in 1-atm flames. A
detailed examination of the effects of CC14, Fe(C0)5, and
Cr02Cl2 upon ion content and emission spectra has been made and
the results interpreted in terras of previously postulated
correlations between the ability of a given compound to reduce
electron concentrations and its effectiveness as a flame inhibitor.
No such correlation was found to exist and it has been concluded
that for these flames no causal relationship exists between the
two phenomena. The relatively large inhibition efficiencies of
Fe(C0)5 and CR02C12 are attributed to in situ ultrafine
particle formation downstream of the flame front and their
subsequent diffusion into the reaction zone. The formation of
these particles is indicated by icn profiles of nucleating species;
the presence of the particles in the reaction zones of inhibited
flames is further evidenced by the emission of continuum radiation.
The dominance of diffusional over convective mass transport is the
characteristic of the system which accounts for its susceptibility
inhibition by these compounds.. (Author's summary)#*
11239
S. Susan, 0. H. Slater, and J. G. Calvert
THE 2H0T0CHEMSTBY OF THE A30AIKANES. Preprint, Ohio State
[Jniv», Columbus, Evans Chemical lab., ((29))p., ((1968))„
((34)) refs.
The photochemistry of the azoalkanes has been the subject of many
studies in several laboratories. The major interest developed
because of their attractiveness as free radical sources. The
first absorption band lies in the accessible near ultraviolet, and
in the gas phases a large fraction of the light~absorbing molecules
decompose to form free radicals. In the gas phase photolysis
of azoalkanes of higher complexity, a significant fraction of the
light-excited molecules do not decompose# but are stabilized by a
second order kinetic process which is often termed "collisional
deactivation". A description of the photochemistry of 1, 1fl-
azoisobutane is given. A kinetic study of the products of the
gas phase photolysis of 1,1*azoisobutane is presented.##
11243
Bobert D„ HcCuigg, and Jack 6. Calvert
THE PHOTODBCOHPOSITION OF CH20, CD20, CHDO, AND CH20-CD20
11IITUHES AT XENON FLASH LA BP INTENSITIES. Preprint, Ohio
State Oniv., Columbus, Ohio, Evans Chemical lab., ((33))p.,
1965. (Presented at the 149th fleeting, American Chemical
Society, Symposium on Structure and Photochemistry of
Excited States, Detroit, Mich., April 1965.)
The volume and composition of the gaseous products of the
photolyses of the pure formaldehydes, CH20, CD20, and CHDO,
and mixtures CB20 and C820, were determined in experiments
at various xenon flash lamp intensities, pressures of aldehyde.
1208
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
temperatures, and at selected wavelength regions of the aldehyde
absorption. The only products of the formaldehyde photolysis
detected in these experiments were carbon monoxide and
hydrogen. The average value of the ratio of the total hydrogen
-------
A study has been made of the photooxidation of 1,1'azoiscbutane
in experiments at 3660 A and full mercury arc and at temperatures
fro# 308 to H05 degrees K. The data prove the unimportance of
energy transfer and singlet oxygen involvement for this
system. The rates of products and their quantum yields are
consistent with a mechanism involving the reactions of the
isobutyl free radical with oxygen- The product distribution
suggests that the isobutylperoxyl and/or isobutoxyl free radicals
are unstable toward a decomposition reaction even at 308
degrees K for our conditions (Authors* abstract)##
11249
T. Naveneeth Rao, Susan S. Collier, and Jack G. Calvert
PBIttABY PHOTOPHYSICAL PB0CESS2S IS THE FHOTOCEHISTRY OP 50LFU8
DIOXIDE AT 2875 A. Preprint, Ohio State Univ., Columbus,
Evans Chemical lab., ((25})p«, 1968- 16 refs. (Presented at the
156th National American Chemical Society Meeting, Atlantic
City, K. J., Sept. 1968„)
The quantum yields of fluorescence and phosphorescence of sulfur
dioxide excited by 2875 A radiation and the guantum yields of
S02-sensiti2ed biacetyl phosphorescence have been measured in
pure sulfur dioxide and in its mixtures with small amounts of
biacetyl. From the variation of functions of these quantum
yields with varied experimental parameters and the previously
published lifetime data for singlet and triplet sulfur dioxide
molecules, values of the rate constants (in 1-mole-sec units) for
all of the individual primary photophysical processes in sulfur
dioxide photolysis have been determined" (Authors* abstract
modified)**
11279
Jaffe, sigmund and Fritz s. Klein
ISOTOPIC EXCHANGE BEACTIONS OF ATOMIC OXYGEN PFODtJCED BY THE
PHOTOIYSIS OF N02 AT 3660 A. Trans.. Faraday Soc.
62(527), Part II, pp. 3135-31H1, Nov.. 1966. 26 refs-
Isotopically labelled atmoic oxygen, produced by the photolysis
of N1302 at 3660 angstroms, was allowed to react with CO,
C02 H20, 02 and COC12, respectively. The rates and
mechanisms of the exchange reactions are discussed. The
specific rate constants were determined for the process™#*
11533
Foote, Christopher S»» and Shi-Yin Wcng
ON THE QUESTION OF TBO BEACTIVE OXYGEN SINGLETS. Preprint,
California Bniv., Los Anqelee, Eept. of Chesistry, 10p.,
((1968)). 13 refs.
1210
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
Research work into the mechanism of fhotooxidati.cn reactions
involving excited singlet and triplet molecular oxygen is
presented. The mechanism of the reactions is approached by the
study of dye-bleaching reaction kinetics-##
11742
Simecek, A., A. Begner, and J. Vosolsobe
KINETICS 2ND MECHANISM OF SOLPHOR DIOXIDE OXIDATION OH A VANADIUM
CATALYST. I. INFLOENCIS OF THE OXYGEN PARTIAL PBESSUHE ON THE
BATE OF OXIDATION. Collection Czech. Chen. Commun.(Prague),
33(7):2162-2168, 1968. 44 refs.
The rate of oxidation of S02 on a vanadiua catalyst (6* V205
by weight and a molar R2C;V2C5 ratio 4.0, supported on
kieselguhr, with a specific surface area of 2 m2/g, a pore volume
of 0.28 cc/g, and mean pore radius of 2880A) at 460-520 deg C
vas measured in a differential reactor with gas recirculation; the
proportions of S02 and 02 in the inlet gas were varied from
7-15% and.from 5-24.5*, respectively. The reaction rate, which
decreased rapidly with time under all conditions, increased
uniformly with both increasing temperature and increasing 02
concentration. The reaction was found to be first order with
respect to oxygen, indicating that the rate-determining step is
probably the reaction of 02 with the catalyst. The apparent
activation energy was calculated to tie 29.0-36.6 kcal/aole,
decreasing with increasing degree of conversion.#9
11770
Ballod, A. P., S. I. Holehanovo, and V. Ya. Shtern
HECHANISM OF THE VAIOOH-PBASE INTERACTION OF ALKANES WITH
MITBOGEN DIOXIDE. (THE KINETICS AND CHEMICAL PECULIARITIES OF
THE SLCK BEACTION C3H8-N02). Keftekhimiya (Bussia), 7(1):115-123,
1967. 20 refs. Translated from Bussian. Ministry of Technology,
Orpington Kent, England, TIL Beports Centre, TIL/T 5757, Aug.
1968.
CFSTI: N68-31918
The kinetics and chemical peculiarities of the slow nitration
reaction between propane and nitrogen dioxide were studied under
static conditions in a vacuum apparatus. The determination of
reaction orders vas performed by observing the relationship
between the initial reaction speed, and the concentration of one
of the reactants, with constant concentration of the other
reactant. The speed of the reaction was determined
photometrically from the consumption of the nitrogen dioxide;
the development of the reaction was determined from the
logarithmic carve of the relationship between the initial
reaction speed and the partial pressures of propane and nitrogen
dioxide. The orders of the slow reaction were found to be
temperature dependent: at 225 and 250 deg, the order according
M. Basic Science and Technology
1211
-------
to C3HB vas 1.0: at 300 and 350 deg, the order according to C3H3
was 0.75 and according tc H02, 1.6. The effective activation
energy of the reaction was 30,000 plus or minus 2000 cal/mol at
200-350 deg. At 250 deg, the end products of the slow reaction
were nitro-alkanes which underwent further transformations at
350 deg. Intermediate products of the slow reaction were
acetaldehyde, isopropyl alcohol, and methyl nitrite. Acetone
was formed by secondary reactions; it did not experience any
further transformation.
11771
Vogh, J. H. and B. Dimitriades
effect of hc/nox ratio oh photcchebical beactivit* of aoto
EXHAUST. Preprint, ((17)) p„ , April 9-14, 1967. (Presented at
American Chemical Society, Div. of Hater, Air, and Raste
Chemistry, Miami, Fla., April 9-14, 1967.)
An attempt to define the reactivity-HC-HOx relationship
guantitatively failed to produce conclusive results because of
lack of adeguate precision. The contention is expressed that at
the present tine laboratory data are the best source of information
available to evaluate ccntrol efforts. Furthermore, agreement
among various laboratories, i.e. various experimental systems,
provides the only criterion for judging the validity and usefulness
of the laboratory data. The precision of the
reactivity-measurement results is determined by factors other than
those associated with the analytical methodology.
Humidity variation might be an important factor. On this basis
humidity control in irradiation-chamber work is imperative. At
extremely low hydrocarbon levels there are indications that
significant photochemical oxidant levels would still be
produced. A detailed study of the photochemical reactivity of
hydrocarbon/HOx systems as a function of concentrations of
HC and NOx at levels belcw 0.2 ppm would be of interest.
(Authors' summary, modified)##
11783
liu, Benjamin T. H. and Hsu-Chi Teh
EFFECT OF PRESS0BE AND ELECTRIC FIELD 0M THE CHARGING OF A1BOSOL
PAHTICLES. (SECTION III). Minnesota Univ., Minneapolis, Dept. of
Bechanical Engineering, AEC Contract AT(11-1)-1248, Pub. COO-
1248-13, 57p., Sept. 1967. 12 refs. (Presented at the
International Conference on the Universal Aspects of Atmospheric
Electricity 4th, Tokyo, Japan, Hay 13-18, 1968.)
The electric charge acguired by particles of an aerosol containing
unipolar gaseous ions was measured over a wide range of conditions.
Honcdisperse aerosols of Di-octyl phthalate with surface median
radii from 0.026 to 0.565 micron were used. Pressure was varied
from 0.075 atn to 0.96 atn, the intensity of the applied electric
field was varied from 372 volts/cm to 2000 volts/cm, and the
1212
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
product N (o)t was varied fron approximately 400,000 to 30,000,000,
where N (o) is the concentration of ions in number of ions per cc
of air, and t is the charging tine in seconds. The experimental
data were compared with various charging theories previously
reviewed by Liu and Yeh and the results indicated that none of the
theories gave an entirely satisfactory account of the experimental
data over its entire range. However, the best agreement was
obtained with the theory of liu and Yeh, thus indicating that this
theory gives an essentially correct description of the charging
process. (Author abstract modified)
11784
liu, Benjamin Y. H. and Hsu-Chi Yeh
ON THE THEORY OF CHARGING OF AEBOSOL PARTICLES IN AN ELECTRIC
FIEID. Minnesota Univ., flinneapolis, Particle Technology lab.,
AEC Contract Pub. COO-1248-12, 32p., Sept. 1967- 12 refs.
Theories for the charging of aerosol particles by unipolar gaseous
ions were reviewed and a new theory taking into account both the
random thermal motion of the ions and the motion of ions induced
by an applied electric field was developed. The theories were
compared vith the experimental data of Hewitt; the results
indicated that the new theory developed shows the best agreement
with the experimental data over the entire range of conditions
covered by the data, for particle size ranging from 0.09 to 0.46
micron radius, for electric field intensities ranging from 300
volts/cm to 10800 volts/cm, and for product N(o) t, ranging
from approximately 1,000,000 to 5C,CC0,0O0, where S(o) is the
concentration of ions in number of ions per cc, and t is the
charging time in seconds). The methods of predicting the
magnitude of electric charge acquired by aerosol particles are
of considerable practical importance in the design and operation
of devices such as electrostatic precipitators, electrostatic
aerosol samplers, electrogasdynasic power generators, and
aerosol particle counters and classifiers based on electrostatic
principles. (Author abstract modified)
11796
Pullman, Ira
FREE RADICAL PRODUCTION IN BI0ICGICALLY SIGNIFICANT COMPOUNDS.
In: Biological Effects of Radiation and Belated Biochemical
and Physical Studies. (Progress Report). Slcan-Kettering Inst,
for Cancer Research, New York, Div. of Eiophysics, AEC contract
AT (30-1)910, 2p., Sept. 30, 1968.
A method is described for obtaining values of the hyperfine
coupling constants of the negative ions of selected polycyclic
hydrocarbons of biological interest. The electron spin resonance
spectra of these compounds are too complex to be completely
resolved, so it is difficult tc assign unambiguous coupling
M, Basic Science and Technology
1213
-------
constants based on comparison with a theoretical stick program in
which the lines have zerc width. In an experimental program, a
simulated Lorentz line shape experimental spectrum is being
computed by an IBM 1800 from a given set o£ coupling constants.
The natural line width, the modulation amplitude of the
spectrometer, and the output time constant of the spectrometer are
taken into account. The method reduces the ambiguity in the
assignment of coupling constants. Experimental and calculated
hyperfine coupling constants for benzo(a)pyrene negative icn are
tabulated. The data to be obtained for different hydrocarbon
negative ions will serve as a check on various semi-empirical
correlations between spin densities and coupling constants reported
for the simpler hydrocarbons.
11802
Omans, fit. s., s. A. Lesko, Jr., and P. 0. P. is'o
CHEHICAL LINKAGE OF THE 3,U-BEBZPTRENE TO OKA VIA FREE RJEICAL
REACTION. (A PRELIMINARY DEPORT). AEC Contract AT (30-1)-3538,
NYO-3538-11, Conf.-681016-2, 6f., March 1, 1968, 3 tefs.
A linkage between 3,4-benzpyrene (BF) and DNa was successfully
induced by iodine. Chromatographic analysis of the nucleotides
produced by hydrolysis of the BE~DNA complex indicated that a
majority of the counts followed the optical density, although
there was a radioactivity peak in the fractions which came through
with the void volume. Since mcst of the counts were removed by
cyclohexane, they are not chemically linked to the nucleotides.
It is hypothesized that the BP-DHA bond may be base labile, and
thus cleaved by the alkaline conditions needed for enzytatic
hydrolysis. This would lead to a free BP derivative in agueous
solution, far above its aguecus solubility, and the formation of
microcrystals or colloidal particles. At present, the nature
of the BP-DNA reaction product is not clear. Preliminary sucrose
gradient electrophoresis studies on the nucleotide mixture
indicates several components. One very strong peak of
radioactivity is found to migrate closely with the guanosine
monophosphate, suggesting that a reaction analogous to alkylation
of DNA occurs and involves the 7-position of guanine. In future
experiments, the role of free radicals in the reaction will be
followed by electron spin resonance.
1186ft
S.V. Benson, G.H. Haugen
A SI8PLE, SELF-COtf SI5TENT ILECTBQSTATIC (JCDEI FOR
QUANTITATIVE PREDICTION OF THE ACTIVITI0N ENERGIES OF FOUR-CENTER
reactions . Preprint, Stanford Research Inst., Henlo Park,
Calif., 27p., 1965. ((16)) refs. (Presented at the Fall 1965
Beeting of the Amer. Chen. See* in Atlantic city, N. J.)
The Eenson-Boce, semi-ion pair mcdel of the transition state
for four-center reactions is extended to include the metathesis
1214
PHOTOCHEMICAL OXIDANTS AND AIR POLLUTION
-------
reactions as veil as the addition reactions, X2 + olefin yields
product, and HX + olefin yields product. A siaple
electrostatic model of point dipoles is used which permits direct
calculation of the activation energies of these reactions. These
calculated values agree with a large number of experimental data to
within plus or minus 1.3 kcal/nole on the average and a maximum
deviation of 3.2 kcal/nole. It was found that the best fit could
be obtained by using rX-X +0.4 angstroms as the transition state
distance for all X-X bonds, vhere rX-X is the ground state
X-X distance. ?he dipole separation is obtained by adding 1.00
angstroms to the rX-X distance where X-Y is the bond being
formed. This leads to a physically reasonable as well as a self-
consistent model. Values are given for about 40 reactions
involving H, F, ci, Br, I. 1 simple point charge
correction is included to account for the earkownikoff Rule.
Attention is directed to the astonishingly low energies reguired
tc produce semi-ion pair states in olefins and the conseguences for
olefins chemistry. (Authors* abstract)t#
11872
Patiadi, I. J.
0X1SATI0S PRODUCTS Of PEBYLENE. National Bureau of Standards,
Washington, D. C., TN-427, p. 12*16, Oct. 1967. 6 refs.
Cure reference compound* of perylene, particularly the various
oxidation products, mere needed in connection with a study of
the products resulting from photochemical reactions of perylene
adsorbed on various particulates. The preparation of
1,12-peryleneguinone and 4,9-dihydroxy--3,10~peryleneguinone are
described. The 1,12-dione was obtained by a published procedure
involving cyclisation of 2,2'-dihydroxy-1,1'-binaphthyl with
aluminum chloride, to give 1,12-perylenediol which was then
oxidized with air and lead dioxide to give crude
1,12-peryleneguinone. This process was not very efficient, as the
desired dione is a labile compound which is difficult to purify.
Preliminary values for peaks in its ultraviolet and visible
spectra are given in a table. Preparation of 4,9-dihydroxy-3, 10-
peryleneguinone involved heating a solution of 3,4,9,10-tetranitro-
perylene in concentrated sulfuric acid at 140 C for six hours.
The product was recrystallized from nitrobenzene to give lustrous,
blue crystals, melting at 483-485 C (with sublimation and some
decompostion). Preliminary values for peaks in its ultraviolet
and visibe spectra are given in a table.
11888
A. A. Eorisov
THE THEBHAL DECOMPOSITION Of 820 AT HIGH TEHPERATOHES.
((Termicheskoye razlozhenye H2C pri vysokikh temperaturakh,))
Text in Bussian. Kinetika i Katalia, 9(3):482-489, 1968.
12 refs.
M. Basic Science andTeehnology
1215
-------
Changes in the concentration of N20, N2, 02, and MO with
tine during the decomposition of N2C (2 or 5* in neon) behind
reflected shock waves in a percussion tube at 1800-2300 degrees K
oere determined using a tine-flight mass spectrometer. The system
of differential equations describing the kinetics of this reaction
was solved, and values were deteriined from experimental data for
the reaction constants of the reactions: N20 + M = 0 + M,
N2C + 0 = N2 + 02, and N20 + 0 = 2N0. The rates
of the 2nd and 3rd reaction were found to be egual, and the
relative heights of the peaks for MO and 02 were found to remain
constant during the entire reaction period, independent of
pressure and temperature. The concentration of NO increased
uniformly with time* Although both N2/N20 and 02/N20
increased with time, the value of the ratio N2/02 decreased
rapidly during the first 100 microseconds, indicating an initial
predominance of the first of the 3 eguations. The reaction rate
for this catalytic decomposition is about 100 times as high as
that for the other two reactions.##
11959
Zocher, H. and H. Kautsky
LUMINESCENCE CUBING CHEHICA1 REACTIONS. Naturwissenschaften
(Berlin), vol. 11:194-199, 1923* 10 refs. Translated from German.
14p.
Chemiluminescence of the silicalhydroxide Si202B2 was studied and
the simultaneous occurrence of fluorescence was established. -
Studies of temperature effect from 100 C to -86 C were made. The
chemiluainescence as well as fluorescence is explained on the basis
of guantum considerations. Studies were made of the
chemiluminescence reaction of oxydisilin with potassium permanganate
ae revealed through the fluorescence of a number of attendant
pigments.
11965
Goehring, B. and I. Darge
A PROCESS FOH DETERMINING SULFATE IN TBI PRESENCE Of SORE
DISTURBING CATIONS. (Bin Verfahren zur Bestimmung von Sulfat bei
Anwesenheit einigex stoerender Katicnen). Z. Anal. Chen., vol.
125:18C-184, Nov. 9, 1942. 10 refs. Translated from German.
Franklin Inst. Research tabs., Philadelphia, Pa., Science
Info. Services, 9p.
A method is described for separating disturbing cations, such as
Ca(IX), Fe (III), Al(III), or Cr(III), from a sulfate-containing
solution by means of a synthetic resin exchanger. Resins which
are themselves strongly acid because they contain aromatic
nuclear sulfo acid groups and can therefore exchange metal ions
for hydrogen ions appear especially suitable for this purpose,
as in the reversible reaction CaS04 plus H2 exchangee yields
H2S04 plus Ca exchanger* Sulfate solutions can be completely
1216
PHOTOCHEMICAL OXIDANTS ANO AIR POLLUTION
-------
freed froa disturbing cations by filtering then over the
exchanger, provided the solution is not too strongly acid (pH
value of at least 1.5). The sulfate ion is not retained by the
exchanger in quantities which can still be detected by the usual
analytical methods. Separation by this technique is rapid and
convenient and of satisfactory accuracy.
1 2041
Glueck, A. R. and C. N« Kenney
THE KINETICS OF THE OXIDATION OP SOLPHUB DIOXIDE OVER HOLTEN
SALTS. Chen. Eng. Sci. , 23{10>;1257-1265, Oct. 1968. 1U refs.
Kinetic experiients on the oxidation of S02 over molten
potassium pyrosulphate at teaperatures below 380 degrees C in the
presence of V205 are discussed. The rate of reaction is first
order in S02 and zero order in oxygen partial pressure. The
velocity constant is 1.0 x 10 to the ainus 7 nole en/2 atm/1 sec/1
at 377 degrees C and the activation energy is 10.8 kcal.
Possible mechanisms are given.. (Author's Abstract)**
12046
Kistiakowsky, G. B. and T. A. Halter
PHOTOLYSIS OF KETBNE BY 2139-1 HADIATION. J. Phys. Chen.,
72 (12) :3952-3958, Nov. 1968. 27 ref.
The photolysis of ketene by the radiation of aainly 2139-A
wavelength was investigated over a vide range of ketene pressures
and radiation intensities in a static systen. The effects of
snail additions of oxygen and of large excess of n-butane vas also
studied. The guantun yield of CO foraation in ketene alone is
about 2 and is nearly ox completely pressure independent. The
other aain product is ethylene, whose quantum yield is about 0.8.
Snaller yields of H2, C2R2, and C2H6 were also obtained,
and their dependence on pressure and radiation intensity was
studied. Also several C3 and C4 hydrocarbons are forned
whose yields increase with the degree of deconposition, so that
they are attributed to reactions with the priaary products of
photolysis. A polyaer fila is slowly forked on the irradiated
surfaces of the cells* The experiaental results are consistent
with the conclusion that the priaary reaction is the decomposition
of ketene into CO and CB2. About 701 of the aethylene
forned reacts with ketene foraing CO and C2H
-------
insertion of methylene, forming pentanes. Also CHI, C2H6, and
butenes are observed which are attributed to an abstraction
reaction by Methylene to for* CH3 and CtH9 radicals. When
oxygen is added to ketene alcne or to mixtures of ketene and
n-butane, all products which have been attributed to free-radical
reactions disappear. These results make it probable, although
they dc not prove it, that the 2139-6 radiation causes the
formation of two kinds of methylene in about a 7:3 ratio, which
behave kinetically as the singlet and triplet states of methylene
formed by near-ultraviolet radiation but possess higher excess
energy. (Author's Abstract)##
12142
Stevenson, H. J. R., D. E. Sanderson, and A. P. Altshuller
SOME EFFECTS OP SOLFUH DIOIIDE OK FORMATION OF PBOTOCHEHICAL
AEROSOLS. Preprint, American Industrial Hygiene Assoc., Detroit,
Bich., Hvp., 1961*. 13 refs. (Presented at the Conference of the
American Industrial Hygiene Association, Philadelphia, Pa.,
April 29, 1964.)
Aerosol was photochemically produced by the irradiation of a
number of hydrocarbon-nitrogen dioxide mixtures, some requiring
sulfur dioxide. In the reactions not reguiring sulfur dioxide,
the addition of S02 increased the aerosol production.
Trans-2-butene required S02 for aerosol production, but
cyclohexene did not. When both hydrocarbons were present in the
photochemical reaction with U02, the amount of aerosol was greater
than that produced by the cyclohexene alone. The cyclohexene
appeared to perform a role for the trans-2-butene similar to the
role played by sulfur dioxide. Six- and seven-carbon olefins,
whether cyclic or straight chain, all produced aerosols without
the presence of S02 and produced more aerosol when S02 was added.
It appeared reasonable that 3-beptene produced less aerosol than
the 1-heptene in the absence of S02 because of the smaller
molecular fragment on reaction. The 3-heptane reacted more
rapidly than the 1-heptene because of the internal position of
the double bond, and the increase of aerosol on addition of S02
was greater for 3-heptene than for 1-heptene. Shorter wavelength
illumination had little effect, an indication that photochemical
activation of S02 is not responsible for its ability to react in
photochemical smog production. At 50% humidity, less aerosol was
produced than at OX, and the length of residence time had opposite
effects on the quantity of aerosol produced, depending upon the
speed of the reaction. The size of the aeroscl produced depended
upon the conditions of the experiment, ffhen sulfur dioxide was
present, the aerosol was smaller and more numerous.
12169
J. N. Pitts, Jr., and J. K» S. Van
THE PHOTOCHEMISTRY 0? KSTORES AND ALDEHYDES. Preprint,
California Cniv., Riverside, Dept.. of Chemistry, 103p. , Dec*,
1964„ 272 refs.
1218
PHOTOCHEMICAL OXtOANTS AND AIR POLLUTION
-------
With the development of nodern experimental techniques,
particularly in analysis of complex mixtures by liquid-gas
chromatographic methods,, photochemistry has assumed an increasing
importance in studies of free radical reactions, energy transfer
processes and the synthesis of new and unique organic compounds.
Perhaps the «ost widely studied class of compounds, historically
and today, is that containing the carbonyl chromophore. The
absorption spectra of most carbonyl conpounds fall in the
experimentally readily accessible region of the ultraviolet where
quarta has high transmission and mercury arcs produce strong ling
emission spectra. In order to obtain a thorough understanding
of the photochemistry of a given system, one must elucidate the
entire "life history" of the photoprocess; this includes the
primary process (es) and all secondary reactions in the system.##
12171
Downs, Alan B.
ATflOSPHEBIC TBAKSMISSION OF LIGHT FOB CLEAB AID AND FOG IN THE
SP1CTBAL BEGIOH 0.35 TO 1.10 MICB0M5. Ballastic Research Labs.
Aberdeen Proving Ground, Hd., BDT and E Proj. IH523801A286,
BBL HB—1561, 45p., April 1964. 12 refs.
CFSTI, DOC: AD 444333
A method for determining light transmission in an ideal atmosphere
with humidity ranging fro* 0.1 to 100 times ten to the minus
6 g/cu cm at -40 to +60 C over path lengths of 1000 to 5000 ¦ is
described. Horizontal light paths near sea level and wavelength
intervals of 0.05 micron over the range 0.35-1*10 micron were
used. Hodification of the model to account for the presence of
fog is explained. Transmissions are given for varying amounts of
fog over path lengths op to 200 m. This same method does not
apply to base because of small droplet size and consequent
wavelength dependence; hence visual approximation are
substituted.
12216
Wells, Hichael G.
MONTH CABLO ANALYSIS OF SEABCBLIGH1 SCA1TERIHG HBASOBEMESTS.
Badiation Besearch Associates, Inc., Fort Worth, Tex., OAS Contract
F19628-67-C-0298, Proj. 7621, Task 762107, Unit 76210701, AFCBL-68-
0311, BBA-T87, 17p., Bay 31, 1968. 5 refs. (Presented at the
Annual Meeting of the Optical Society of Aaerica, 1967, paper
ThD 20.)
CFSTI, DDC: AD 675153
A Honte C